JP2891838B2 - Pharmaceutical and medical rubber stoppers and method of manufacturing the same - Google Patents
Pharmaceutical and medical rubber stoppers and method of manufacturing the sameInfo
- Publication number
- JP2891838B2 JP2891838B2 JP4330624A JP33062492A JP2891838B2 JP 2891838 B2 JP2891838 B2 JP 2891838B2 JP 4330624 A JP4330624 A JP 4330624A JP 33062492 A JP33062492 A JP 33062492A JP 2891838 B2 JP2891838 B2 JP 2891838B2
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- polyethylene
- weight
- ethylene
- rubber stopper
- 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.)
- Expired - Lifetime
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- Medical Preparation Storing Or Oral Administration Devices (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は医薬品用，医療用ゴム栓
に関する。詳しくは医薬品容器、医療用具用器具類の一
部に用いられる、ゴム状弾性体であって、日本薬局方、
厚生省告示等において規定される試験方の規格値、基準
値に適すると共に、製造工程においてはゴム栓の成形操
作、採用工程において取扱容易で操業しやすい医薬品
用，医療用ゴム栓及びその製造方法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rubber stopper for pharmaceuticals and medical use. Specifically, it is a rubber-like elastic body used for some pharmaceutical containers and medical equipment,
It is suitable for the standard value and standard value of the test method stipulated in the notification of the Ministry of Health and Welfare, the rubber stopper molding operation in the manufacturing process, the pharmaceutical and medical rubber stopper which is easy to handle and operate in the adoption process, and the manufacturing method thereof. .
【０００２】[0002]
【従来の技術】医薬品容器、医療用具用器具類に付随す
るゴム弾性体としては、天然ゴム（「ＮＲ」と略記す
る）、イソプレンゴム（「ＩＲ」と略記する）、ブタジ
エンゴム（「ＢＲ」と略記する）、スチレン・ブタジエ
ンゴム（「ＳＢＲ」と略記する）、イソプレン・イソブ
チレン共重合体（「ＩＩＲ」と略記する）、そしてＩＩ
Ｒのハロゲン化ゴム（「ＢＩＩＲ」，「ＣＩＩＲ」と略
記する）、熱可塑性エラストマー等が使用されている。
熱可塑性エラストマーには、スチレン・ブタジエン共重
合体並びに該共重合体の水素添加物を医薬品容器の栓体
とする技術がある（特開昭５９−２８９６５号公報、特
公昭５７−２６７８２号公報、特公平２−４２９６号公
報）。また、熱可塑性エラストマーとＩＩＲの混合物を
ゴム栓にした技術（特開昭５９−２８９６５号公報）、
ＩＩＲにフッ素ゴムを積層したゴム栓（特公昭６３−４
３１０４号公報、実開昭５５−４７８５０号公報）があ
る。さらには超高分子ポリエチレンシートでゴム栓面を
包んでなるゴム栓（特開平３−１４３４４６号公報、特
開平３−２７０９２８号公報、特開平３−９６３２８号
公報、特開平３−１４３４４６号公報、特開平４−２２
３６２号公報）がある。2. Description of the Related Art Natural rubber (abbreviated as "NR"), isoprene rubber (abbreviated as "IR"), and butadiene rubber ("BR") are used as rubber elastic bodies accompanying pharmaceutical containers and instruments for medical devices. Styrene-butadiene rubber (abbreviated as “SBR”), isoprene / isobutylene copolymer (abbreviated as “IIR”), and II
R halogenated rubbers (abbreviated as "BIIR" and "CIIR"), thermoplastic elastomers and the like are used.
As a thermoplastic elastomer, there is a technique of using a styrene-butadiene copolymer and a hydrogenated product of the copolymer as a plug for a pharmaceutical container (Japanese Patent Application Laid-Open No. 59-28965, Japanese Patent Publication No. 57-26782, JP-B-2-4296). In addition, a technique in which a mixture of a thermoplastic elastomer and IIR is made into a rubber stopper (JP-A-59-28965),
Rubber stopper with fluoro rubber laminated on IIR (JP-B-63-4)
3104, and Japanese Utility Model Laid-Open No. 55-47850). Further, rubber plugs obtained by wrapping a rubber plug surface with an ultra-high molecular weight polyethylene sheet (JP-A-3-143446, JP-A-3-270929, JP-A-3-96328, JP-A-3-143446, JP-A-4-22
No. 362).
【０００３】上記したいずれの従来技術もゴム栓の製造
工程での作業性が悪いが、未だ満足できる改善案がな
い。汎用工業用品では、タルク、またはタルクを界面活
性剤の乳濁液によりゴム表面の粘着性を改善して、ゴム
製品を製造している。医薬品用ゴム栓のような衛生ゴム
製品には汎用技術を適用することはできない。また、薬
の製剤の際のゴム栓の容器口への自動打栓作業性の改善
のために、ゴム栓の表面にシリコーン油系化合物を塗布
して滑りのよいゴム栓にする案があるが、近年シリコー
ン油は衛生上で問題視されてきている。本発明はこのよ
うな従来技術の問題点を解消し、特にゴム表面の粘着性
を改善ししかも各種公定書に定められた試験を満足でき
る衛生性を有し、且つ経済性を有する医薬品用，医療用
ゴム栓及びその製造方法を提供することを目的としてい
る。[0003] In any of the above-mentioned prior arts, the workability in the manufacturing process of the rubber stopper is poor, but there is still no satisfactory improvement plan. In general-purpose industrial products, talc or talc is improved in tackiness on a rubber surface with a surfactant emulsion to produce a rubber product. General-purpose technology cannot be applied to sanitary rubber products such as pharmaceutical rubber stoppers. There is also a plan to apply a silicone oil-based compound to the surface of the rubber stopper to make it a slippery rubber stopper in order to improve the workability of automatically popping the rubber stopper into the container opening when preparing the drug. In recent years, silicone oil has been regarded as a problem in hygiene. The present invention solves such problems of the prior art, and particularly improves the adhesiveness of the rubber surface and has a hygienic property that can satisfy the tests specified in various official documents, and is economically economical. An object of the present invention is to provide a medical rubber stopper and a method for manufacturing the same.
【０００４】[0004]
【課題を解決するための手段】本発明は上記課題を解決
する手段として、イソプレン−イソブチレン共重合ゴム
６０〜９０重量％と、エチレン−プロピレン共重合体お
よびポリエチレンから選ばれる一種以上３〜５０重量％
とを含有して成るゴム成形体表面に微粒子のポリエチレ
ンまたはポリプロピレンが付着層として形成されてなる
ことを特徴とする医薬品用，医療用ゴム栓を提供する。
本発明はさらに上記の本発明医薬品用，医療用ゴム栓の
製造方法も提供するものであり、第一の製造方法は、イ
ソプレン−イソブチレン共重合ゴム６０〜９０重量％
と、エチレン−プロピレン共重合体およびポリエチレン
から選ばれる一種以上３〜５０重量％とを含有して成る
ゴム表面に、微粒子のポリエチレンまたはポリプロピレ
ンの水又は溶剤液との混濁液を塗布もしくは浸漬した後
乾燥してゴム表面に微粒子層を均一に形成した配合ゴム
とし、該配合ゴムを加硫成形することを特徴とする。ま
た、本発明の製造方法の第二の方法は、イソプレン−イ
ソブチレン共重合ゴム６０〜９０重量％と、エチレン−
プロピレン共重合体およびポリエチレンから選ばれる一
種以上３〜５０重量％とを含有して成るゴム表面に、微
粒子のポリエチレンまたはポリプロピレンを均一に且つ
微粒子の重なりを少なく振りかけることにより該微粒子
をゴム表面に付着させ、その後加硫成形することを特徴
とする。According to the present invention, 60 to 90% by weight of an isoprene-isobutylene copolymer rubber and at least 3 to 50% by weight of at least one selected from an ethylene-propylene copolymer and polyethylene are provided. %
The present invention provides a rubber stopper for pharmaceutical and medical use, characterized in that fine particles of polyethylene or polypropylene are formed as an adhesion layer on the surface of a rubber molded product containing
The present invention further provides a method for producing the above-mentioned rubber stopper for medical use and medical use of the present invention, wherein the first production method comprises the step of preparing isoprene-isobutylene copolymer rubber at 60 to 90% by weight.
After applying or immersing a turbid liquid of water or a solvent of fine particles of polyethylene or polypropylene on a rubber surface containing 3 to 50% by weight of at least one selected from ethylene-propylene copolymer and polyethylene. It is characterized in that it is dried to form a compounded rubber in which a fine particle layer is uniformly formed on the rubber surface, and the compounded rubber is vulcanized. In the second method of the production method of the present invention, 60 to 90% by weight of an isoprene-isobutylene copolymer rubber is used.
Fine particles of polyethylene or polypropylene are uniformly sprinkled on the rubber surface containing 3 to 50% by weight of at least one selected from propylene copolymer and polyethylene, and the fine particles are adhered to the rubber surface by sprinkling the particles with little overlap. And then vulcanization molding.
【０００５】[0005]
【作用】本発明はゴム栓本体としては物理的特性、化学
的特性、衛生性の面で優れたイソプレン−イソブチレン
系共重合ゴム（ＩＩＲ）組成物を用い、このＩＩＲの表
面にポリエチレンまたはポリプロピレンの微粒子を付着
して極く薄い層を形成させることにより粘着性を改善
し、作業工程での取扱を容易にし、操作性向上により経
済性を高めたものである。The present invention uses an isoprene-isobutylene copolymer rubber (IIR) composition excellent in physical properties, chemical properties and hygiene as a rubber stopper body, and the surface of this IIR is made of polyethylene or polypropylene. The adhesiveness is improved by adhering fine particles to form an extremely thin layer, the handling in the working process is facilitated, and the economic efficiency is improved by improving the operability.
【０００６】本発明のゴム栓本体はＩＩＲを主成分と
し、これにエチレン−プロピレン共重合体およびポリエ
チレンの中から選ばれる一種以上を混合してなるゴム組
成物で形成されている。本発明のゴム栓に用いるＩＩＲ
は、不飽和度０．１〜２．５モル％、ムーニー粘度４０
〜８９、平均分子量３０〜６０万であり、酸素ガスの透
過性はＮＲの１／８、強酸、強アルカリ、アルコール
類、エステル類系溶媒に極めて強いゴム素材である。従
って、本発明ではＩＩＲの含有量を６０〜９０重量％と
多くすることにより、医薬品用，医療用ゴム栓として必
須の衛生性を高めている。The rubber stopper body of the present invention is formed of a rubber composition comprising IIR as a main component and a mixture of at least one selected from ethylene-propylene copolymer and polyethylene. IIR used for the rubber stopper of the present invention
Has a degree of unsaturation of 0.1 to 2.5 mol% and a Mooney viscosity of 40.
-89, an average molecular weight of 300,000-600,000, and a permeability to oxygen gas of 1/8 of NR, a rubber material which is extremely resistant to strong acids, strong alkalis, alcohols, and esters. Therefore, in the present invention, by increasing the content of IIR to 60 to 90% by weight, the hygiene essential for rubber stoppers for pharmaceuticals and medical use is enhanced.
【０００７】また、ＩＩＲにエチレン−プロピレン共重
合体およびポリエチレンの一種以上を配合する理由は、
成形ゴム表面に微粉末のポリエチレンまたはポリプロピ
レンの微粉末を付着させるだけで、その表面に層として
固定できるようになるからである。これによりゴム表面
の粘着性と衛生性の両者を一挙に改善できたものであ
る。本発明に用いるエチレン−プロピレン共重合体とし
ては、エチレン−プロピレンランダム共重合体、エチレ
ン−プロピレンブロック共重合体、エチレン−プロピレ
ン共重合ゴム（ＥＰＭ）、エチレン−プロピレン−ジエ
ン三元共重合ゴム（ＥＰＤＭ）などが挙げられる。エチ
レン−プロピレンランダム共重合体としては例えばプロ
ピレン含有量７０〜９８重量％、メルトフローレート
（ＭＦＲ）０．５〜２０ｇ／１０分温度２３０℃測定、
のエチレン−プロピレンランダム共重合体が挙げられ
る。エチレン−プロピレンブロック共重合体としては、
例えばプロピレン含有量７０〜９３重量％でＭＦＲ２．
０〜３０ｇ／１０分温度２３０℃測定、のエチレン−プ
ロピレンブロック共重合体が挙げられる。ＥＰＤＭのジ
エン系化合物として例えばエチリデンノルボルネン、ジ
シクロペンタジエン、１，４−ヘキサンジエンがあり、
不飽和度はヨウ素価で５〜３６、ＥＰＭ，ＥＰＤＭとも
にプロピレンの含有量は２０〜５０重量％、ムーニー粘
度（ＭＬ1+4 ）１００℃で２０〜１２０のものが挙げら
れる。ポリエチレンとしては、高密度ポリエチレン（融
点１００〜１３６℃）、直鎖状低密度ポリエチレン（融
点１００〜１３０℃）、超高分子量ポリエチレン（融点
１３０〜１３６℃）が挙げられる。The reason why one or more of ethylene-propylene copolymer and polyethylene are blended in IIR is as follows.
This is because a fine powder of polyethylene or polypropylene, which is a fine powder, can be fixed to the surface of the molded rubber simply by adhering it to the surface. As a result, both the adhesiveness and hygiene of the rubber surface can be improved at once. Examples of the ethylene-propylene copolymer used in the present invention include an ethylene-propylene random copolymer, an ethylene-propylene block copolymer, an ethylene-propylene copolymer rubber (EPM), and an ethylene-propylene-diene terpolymer rubber ( EPDM) and the like. Examples of the ethylene-propylene random copolymer include a propylene content of 70 to 98% by weight, a melt flow rate (MFR) of 0.5 to 20 g / 10 minutes, and a temperature of 230 ° C.
Ethylene-propylene random copolymer. As the ethylene-propylene block copolymer,
For example, when the propylene content is 70 to 93% by weight and the MFR2.
An ethylene-propylene block copolymer having a temperature of 0 to 30 g / 10 minutes and a temperature of 230 ° C is exemplified. EPDM diene compounds include, for example, ethylidene norbornene, dicyclopentadiene, and 1,4-hexanediene;
The degree of unsaturation is 5 to 36 in iodine value, the content of propylene in both EPM and EPDM is 20 to 50% by weight, and the Mooney viscosity (ML 1 + 4 ) is 20 to 120 at 100 ° C. Examples of polyethylene include high-density polyethylene (melting point 100 to 136 ° C), linear low-density polyethylene (melting point 100 to 130 ° C), and ultrahigh molecular weight polyethylene (melting point 130 to 136 ° C).
【０００８】本発明のＩＩＲゴム組成物においては、Ｉ
ＩＲ１００重量部に対して、エチレン−プロピレン共重
合体の配合量は５〜５０重量部が好ましい。また、ＩＩ
Ｒ１００重量部に対してポリエチレンの配合量は３〜４
０重量％が好ましい。この範囲より少ない場合は、表面
に付着したポリエチレン，ポリプロピレンが剥離して、
薬、薬液中に汚物として混入する。また上記範囲を越え
て配合したゴムは、注射針を刺した際に針口が大きくな
り、薬液が漏れ出て、衛生上問題を起こす。[0008] In the IIR rubber composition of the present invention, I
The amount of the ethylene-propylene copolymer is preferably 5 to 50 parts by weight based on 100 parts by weight of IR. Also, II
The amount of polyethylene is 3 to 4 based on 100 parts by weight of R.
0% by weight is preferred. If less than this range, polyethylene and polypropylene attached to the surface will peel off,
Contaminated as dirt in medicines and chemicals. In addition, rubber compounded beyond the above range has a large needle opening when a syringe needle is pierced, causing leakage of a drug solution and causing a hygienic problem.
【０００９】本発明においてＩＩＲにエチレン−プロピ
レン共重合体、ポリエチレンを混合する操作は、イター
ナルミキサーなどの加熱、加圧装置を使用して混合し、
更に一軸または二軸押出機を通して混練して、単なる混
合物ではなくアロイ化まで均一に混合したものが好まし
い。In the present invention, the operation of mixing the ethylene-propylene copolymer and polyethylene with the IIR is performed by using a heating and pressurizing device such as an internal mixer.
Further, it is preferable that the mixture is kneaded through a single-screw or twin-screw extruder, and is not simply a mixture but uniformly mixed until alloying.
【００１０】本発明では上記のように混練したゴム組成
物からゴム栓本体を成形するが、その表面にポリエチレ
ンまたはポリプロピレンの微粉末を付着させる。この際
使用するポリエチレン，ポリプロピレンの微粒子粉末
は、ＩＩＲに配合したポリエチレン，ポリプロピレンと
同種類である。ポリプロピレンは結晶性のものでもよ
い。ポリエチレン，ポリプロピレンともに特に細かい粉
末が好ましい。In the present invention, a rubber stopper main body is formed from the rubber composition kneaded as described above, and a fine powder of polyethylene or polypropylene is adhered to the surface of the main body. The fine particles of polyethylene and polypropylene used at this time are of the same type as the polyethylene and polypropylene blended in the IIR. The polypropylene may be crystalline. Particularly fine powders are preferable for both polyethylene and polypropylene.
【００１１】ポリエチレン又はポリプロピレン微粉末の
配合ゴム表面への付着には、粉末品を溶媒、例えば水、
アルコール類、エステル類の乳濁液にして、ゴムシート
表面に塗布またはゴムシートを浸漬し、ゴムシート表面
に厚さ０．１ｍｍ以下の層を形成し、粒子の重なりを少
なくし、好ましくは単分子膜にする。乾燥した後に、ゴ
ム栓を金型中で架橋、成形する。また、配合ゴム表面
に、微粒子のポリエチレン又はポリプロピレンを均一に
塗布し粒子の重なりの少ない膜とし、その後にゴム表面
に該粒子層を付着させた後に、金型内に架橋成形する方
法もある。[0011] To adhere the polyethylene or polypropylene fine powder to the compounded rubber surface, the powdered product is mixed with a solvent such as water,
An emulsion of alcohols or esters is formed, and the rubber sheet is coated or dipped on the surface of the rubber sheet to form a layer having a thickness of 0.1 mm or less on the surface of the rubber sheet. Make a molecular film. After drying, the rubber stopper is crosslinked and molded in a mold. There is also a method in which fine particles of polyethylene or polypropylene are uniformly applied to the surface of the compounded rubber to form a film with less particle overlap, and then the particle layer is adhered to the rubber surface, followed by crosslinking and molding in a mold.
【００１２】本発明を複雑な形状のゴム栓例えば凍結乾
燥製剤用ゴム栓に適用する場合、例えば栓の脚部には特
開昭６１−２７２１３４号公報に提案されるようにフッ
素樹脂フィルムを積層し、フランジ部に本発明に従い表
面にポリエチレン，ポリプロピレンの微粉末層を形成す
ることが好ましい。When the present invention is applied to a rubber stopper having a complicated shape, for example, a rubber stopper for a freeze-dried preparation, for example, a fluororesin film is laminated on the legs of the stopper as proposed in JP-A-61-272134. Preferably, a fine powder layer of polyethylene or polypropylene is formed on the surface of the flange according to the present invention.
【００１３】[0013]
【実施例】以下本発明を実施例を挙げて説明するが、本
発明はこれに限定されるものではない。 （実施例１〜１４及び比較例１〜７）下記表１、表２に
示す配合で、ＩＩＲ〔ＥＸＸＯＮ Ｂｕｔｙｌ ３６５
（商品名、Ｅｓｓｏ ｃｈｅｍｉｃａｌ Ｌｔｄ）不飽
和度２．０モル％、ＭＬ1+8１００ ４１〜４９〕に表
１〜表３に示すエチレン−プロピレン共重合体及び／ま
たはポリエチレンを二本ロールで混合し、更に一軸押出
機で温度１５０〜１８０℃で加圧下に約２分間混練し、
樹脂をアロイ化した。別に加硫剤、加硫助剤はＩＩＲの
親ゴム混合物（ｍａｓｔｅｒ ｂａｔｈ）にして、該ア
ロイ化物にロールで均一に混合して、厚さ約８ｍｍのシ
ートにロール分出しする。得られたシート面を微粉末の
ポリエチレンまたはポリプロピレン（表面層と称す）の
アルコール乳濁液（３５重量％）にて浸し、乾燥してゴ
ムシート表面に均一な微粒子層を形成する。図２に示す
ゴム栓脚形の凹部を有する下金型面上に得られた配合ゴ
ムシートを置き、フランジ形の凹部を有する上金型にて
温度１５０℃で２０分間加圧してゴム栓を成形する。次
に金型より出し、洗浄、乾燥してゴム栓を得る（本発明
品）。また、表３に示す配合で同様に操作して比較品ゴ
ム栓を作成した。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. (Examples 1 to 14 and Comparative Examples 1 to 7) IIR [EXXON Butyl 365] with the composition shown in Tables 1 and 2 below
(Trade name, Esso Chemical Ltd) Unsaturation 2.0 mol%, ML 1 + 8 100 41-49] and ethylene-propylene copolymer and / or polyethylene shown in Tables 1 to 3 mixed with two rolls And further kneaded with a single screw extruder at a temperature of 150 to 180 ° C. under pressure for about 2 minutes,
The resin was alloyed. Separately, a vulcanizing agent and a vulcanizing aid are made into a IIR-rubber mixture (master bath), uniformly mixed with the alloy by a roll, and rolled out into a sheet having a thickness of about 8 mm. The obtained sheet surface is immersed in a fine powder of an alcohol emulsion (35% by weight) of polyethylene or polypropylene (referred to as a surface layer) and dried to form a uniform fine particle layer on the rubber sheet surface. The resulting compounded rubber sheet is placed on the lower mold surface having a rubber stopper leg-shaped recess shown in FIG. 2 and pressed at a temperature of 150 ° C. for 20 minutes in an upper mold having a flange-shaped recess to remove the rubber stopper. Molding. Next, it is taken out of the mold, washed and dried to obtain a rubber stopper (the product of the present invention). In addition, the same operation was performed with the composition shown in Table 3 to prepare a rubber stopper for comparison.
【００１４】得られた本発明品の実施例１〜８、比較品
の比較例１〜７について、下記に従いゴム性の滑性試験
及び微粒子数試験を行った。 ゴム栓の滑性試験：ゴム栓をフッ素樹脂板の上に置
き、該樹脂下の一旦を固定し、他の一端を一定の速度で
上昇するときにゴム栓は移動する。この移動始める角度
を測定する。移動開始角度が小さい程、滑性は大きい。 微粒子数（ゴム栓より発生する粒子数の試験）：
硬質ガラス瓶中にゴム栓１０個を入れ、無塵水３００ｍ
ｌを加えて容器口をフィルムで包み、手にて２回転／秒
程度にて約２０秒間振動する。その後１時間静置してか
ら光遮蔽型自動微粒子計測器（ＨＩＡＣ社製）にて水中
の微粒子の個数を測定する。なお、注射液中の５μｍ以
上の微粒子の存在は血管を閉塞する等の問題を起こすの
で、重要な試験項目となっている。各実施例、比較例の
配合、表面層の種類、ゴム栓の滑性（粘着性）、特殊試
験である微粒子数試験の結果を表１、表２、表３に合わ
せて示す。[0014] Examples 1 to 8 of the obtained product of the present invention and Comparative Examples 1 to 7 of comparative products were subjected to a rubber lubricity test and a fine particle count test as follows. Rubber stopper lubricity test: A rubber stopper is placed on a fluororesin plate, the lower part of the resin is fixed, and the other end moves at a constant speed when the rubber stopper moves. The angle at which this movement starts is measured. The smaller the movement start angle, the greater the smoothness. Fine particle count (test for the number of particles generated from rubber stoppers):
Put 10 rubber stoppers in a hard glass bottle, 300m in dust-free water
Then, the container opening is wrapped with a film and shaken by hand at about 2 revolutions / second for about 20 seconds. Then, after standing still for one hour, the number of fine particles in water is measured by a light shielding type automatic fine particle measuring device (manufactured by HIAC). In addition, the presence of fine particles of 5 μm or more in the injection solution causes problems such as obstruction of blood vessels, and is an important test item. Tables 1, 2 and 3 also show the formulations of the examples and comparative examples, the type of the surface layer, the lubricity (adhesion) of the rubber stopper, and the results of the special particle number test as a special test.
【００１５】[0015]
【表１】 [Table 1]
【００１６】[0016]
【表２】 [Table 2]
【００１７】[0017]
【表３】 [Table 3]
【００１８】なお、以上の表１、表２、表３中の1)〜1
2) は以下の通りを意味する。 1)架橋剤：１，１−ジ（ｔ−ブチルペルオキシ）−３，
３，５−トリメチルシリルシクロヘキサン〔日本油脂
（株）製〕 2)架橋剤：Ｎ，Ｎ′−ｍ−フェニレンビスマレイミド
〔川口化学（株）製〕 3)ＥＰＭ〔三井ＥＰＴ００４５（商品名）三井石油化学
工業（株）製〕、プロピレン含量５１重量％、ＭＬ1+4
１００℃ ３８ 4)ポリプロピレン〔フローブレン（商品名）製鉄化学工
業（株）製〕、融点１４６℃、篩試験ＡＳＴＭ No.８０
通過品 5)エチレン−プロピレンランダム共重合体〔三菱油化
（株）製〕、エチレン含有量３．４％、ＭＦＲ１５ｇ／
１０分、曲げ弾性率１０．５００ｋｇ／ｃｍ2 6)エチレン−プロピレンブロック共重合体〔ＢＪ４Ｈ
（商品名）三井東圧化学（株）製〕、エチレン含有量１
２重量％、ＭＦＲ２０ｇ／１０分 7)ＥＰＤＭ〔三井ＥＰＴ３０４５（商品名）三井石油化
学工業（株）製〕、プロピレン含量４７重量％、ＭＬ
1+4 １００℃ ３８、ヨウ素価１６ 8)ポリエチレン〔フローセンＵＦ（商品名）製鉄化学工
業（株）製〕、高密度法による製品、融点（ＡＳＴＭ
Ｄ２１１７）１０３〜１１１℃ 9)ポリエチレン〔ウルトゼックス（商品名）三井石油化
学工業（株）製〕、ＭＦＲ１８ｇ／１０分、ピカット軟
化点９２℃、（Ｌ−ＬＤＰＥ） 10) 超高分子量ポリエチレン〔ハイゼックスミリオン２
４０Ｍ（商品名）三井石油化学工業（株）製〕、融点
（ＡＳＴＭ Ｄ２１１７）１３５℃、篩試験ＡＳＴＭ N
o.８０通過品 11) 酸化チタン〔石原産業（株）製〕 12) タルク（滑石、含水ケイ酸マグネシウム）、ＦＤＡ
認可品である打粉に使用する中国タルクを使用 13) ゴム用クレー〔Ｂｕｒｇｅｓｅ Ｐｉｇｍｅｎｔ
（商品名）〕Incidentally, 1) to 1 in Tables 1, 2 and 3 described above.
2) means the following. 1) Crosslinking agent: 1,1-di (t-butylperoxy) -3,
3,5-trimethylsilylcyclohexane [manufactured by NOF Corporation] 2) Crosslinking agent: N, N'-m-phenylenebismaleimide [manufactured by Kawaguchi Chemical Co., Ltd.] 3) EPM [Mitsui EPT0045 (trade name) Mitsui Petrochemical] Industrial Co., Ltd.], propylene content 51% by weight, ML 1 + 4
100 ° C. 38 4) Polypropylene [FLOWBREN (trade name) manufactured by Iron Chemical Industry Co., Ltd.], melting point 146 ° C., sieve test ASTM No. 80
Passed product 5) Ethylene-propylene random copolymer (manufactured by Mitsubishi Yuka Co., Ltd.), ethylene content 3.4%, MFR 15 g /
10 minutes, flexural modulus 10.500 kg / cm 2 6) ethylene-propylene block copolymer [BJ4H
(Trade name) Mitsui Toatsu Chemical Co., Ltd.], ethylene content 1
7% EPDM [Mitsui EPT3045 (trade name) manufactured by Mitsui Petrochemical Industry Co., Ltd.], propylene content 47% by weight, ML
1 + 4 100 ° C. 38, iodine value 16 8) Polyethylene [Flocene UF (trade name) manufactured by Iron Chemical Industry Co., Ltd.], product by high density method, melting point (ASTM)
D2117) 103-111 ° C 9) Polyethylene (Ultzex (trade name) manufactured by Mitsui Petrochemical Industry Co., Ltd.), MFR 18 g / 10 minutes, Piccat softening point 92 ° C, (L-LDPE) 10) Ultra-high molecular weight polyethylene [Hizex Million 2
40M (trade name, manufactured by Mitsui Petrochemical Industries, Ltd.), melting point (ASTM D2117) 135 ° C, sieve test ASTM N
o.80 product 11) Titanium oxide (Ishihara Sangyo Co., Ltd.) 12) Talc (talc, hydrous magnesium silicate), FDA
Uses Chinese talc, which is used for approved flouring 13) Clay for rubber [Burgese Pigment
(Product name)〕
【００１９】得られた本発明品のうち実施例１、実施例
５、実施例１１、実施例１３、比較品のうち比較例３、
比較例７につき、第１２改正日本薬局方による試験、特
殊な衛生試験を行った。試験結果を表４に示す。Among the obtained products of the present invention, Example 1, Example 5, Example 11, Example 13 and Comparative Example 3 among the comparative products,
For Comparative Example 7, a test by the 12th revised Japanese Pharmacopoeia and a special hygiene test were performed. Table 4 shows the test results.
【００２０】[0020]
【表４】 [Table 4]
【００２１】表１〜表４に示すごとく、ＩＩＲにそれぞ
れＥＰＭ（実施例１）、ＥＰＤＭ（実施例４）、エチレ
ン−プロピレンランダム共重合体（実施例２）、エチレ
ン−プロピレンブロック共重合体（実施例３）を配合し
たものでは、ゴム表面にＰＰ層を形成することにより、
ゴム栓の滑性が高くなり、ゴム表面からの微粒子剥離は
認められなかった。また同様にＰＰの代わりに表面ＰＥ
層を形成したものでもゴム栓の粘着性がなくなり、ＰＥ
の微粒子の剥離がなく、衛生上良好であった。ゴム栓本
体のゴム組成を実施例１３または実施例１４のものと同
様にして、表面層を形成しなかった比較例１、比較例２
のゴム栓は、微粒子数は少ないが、粘着性が高く、自動
打栓装置にかけて作業することができない。また工業用
品、タイヤ、ベルトなどのゴム製品で一般的に行われる
ように表面層としてタルクを用いた比較例３、比較例４
では、ゴム栓から発生する微粒子数が多く、衛生ゴム製
品として問題を生じる。ゴム配合率については、比較例
４、比較例５、比較例６に示すようにＩＩＲ含有率を低
くしてエチレン−プロピレン共重合体、ポリエチレン等
を配合すると、ポリエチレン表面層を形成しても衛生的
なゴム栓は得られない、あるいは弾性のないゴム栓とな
ってしまう。クレーの配合量の多い比較例７の場合も同
様である。日本薬局方による衛生試験についても上記と
同様の結果になった。As shown in Tables 1 to 4, the IIR shows EPM (Example 1), EPDM (Example 4), ethylene-propylene random copolymer (Example 2), and ethylene-propylene block copolymer (Example 2). In the case of blending Example 3), by forming a PP layer on the rubber surface,
The lubricity of the rubber stopper became high, and no fine particles were separated from the rubber surface. Similarly, instead of PP, surface PE
Even if a layer is formed, the rubber stopper loses its adhesiveness and PE
There was no exfoliation of fine particles, and the hygiene was good. Comparative Example 1 and Comparative Example 2 in which the rubber composition of the rubber stopper body was the same as that of Example 13 or Example 14, and no surface layer was formed
Although the rubber stopper has a small number of fine particles, it has high adhesiveness and cannot be operated by using an automatic stoppering device. Comparative examples 3 and 4 using talc as a surface layer as generally performed for rubber products such as industrial articles, tires and belts.
In this case, the number of fine particles generated from the rubber stopper is large, which causes a problem as a sanitary rubber product. As shown in Comparative Example 4, Comparative Example 5, and Comparative Example 6, when the IIR content is reduced and an ethylene-propylene copolymer, polyethylene, or the like is blended, even if a polyethylene surface layer is formed, sanitary A typical rubber stopper cannot be obtained, or the rubber stopper has no elasticity. The same applies to Comparative Example 7 in which the amount of clay is large. The same result was obtained in the hygiene test by the Japanese Pharmacopoeia.
【００２２】以上の実施例、比較例に用いたゴム栓の製
法は、ゴムの金型を変えて適用する、あるいは特開昭６
１−２７２１３４号公報、特開昭６２−１７６４５０号
公報、特開平２−１２７５号公報等に記載される公知技
術のゴム栓に適用して、図４、図５に示す注射器の滑
栓、凍結乾燥用ゴム栓等を製造することができる。The method of manufacturing the rubber stopper used in the above Examples and Comparative Examples is applied by changing the rubber mold, or
The present invention is applied to rubber stoppers of the known art described in Japanese Patent Application Laid-Open Nos. 1-272134, 62-176450, 2-1275, etc. A rubber stopper for drying and the like can be manufactured.
【００２３】実施例１５ 下記表５に示す配合剤をゴム用２本ロールにて配合し、
厚さを約４ｍｍシートに分出し、そのゴム表面にポリエ
チレン粉末品（商品名ハイゼックスミリオン２４０Ｍ、
三井石油化学（株）製）を均一に散布し、過剰な粉を除
き、軟らかく圧してゴム表面に粉を粘着させた。Example 15 The compounding ingredients shown in Table 5 below were compounded with two rolls for rubber.
The thickness is divided into about 4 mm sheets, and a polyethylene powder product (trade name: HIZEX MILLION 240M,
(Mitsui Petrochemical Co., Ltd.) was evenly sprayed to remove excess powder, and pressed softly to adhere the powder to the rubber surface.
【００２４】[0024]
【表５】 [Table 5]
【００２５】次に図５のゴム線脚部を積層成形したゴム
栓を同型ゴム栓より深い金型窪に入れて、上記で得られ
たポリエチレン粉末を散布した生地を置き、その上にゴ
ム栓フランジ部の凹を有する上金型を置いて、温度１５
０℃で１５分間加圧することにより本発明のゴム栓が得
られる。架橋成形したゴム栓を洗浄、乾燥して、第１２
改正日本薬局方の衛生試験法に準拠した試験を行ったと
ころ、第１２改正日本薬局方の規格値に適合していた。Next, the rubber plug formed by laminating the rubber wire legs shown in FIG. 5 is put into a mold cavity deeper than the rubber plug of the same type, and the cloth obtained by spraying the polyethylene powder obtained above is placed thereon. Place the upper mold with the concave part of the flange,
Pressing at 0 ° C. for 15 minutes gives the rubber stopper of the present invention. The crosslinked rubber stopper is washed and dried, and
When a test was conducted in accordance with the revised Japanese Pharmacopoeia Hygiene Test Law, it was found to conform to the twelfth revised Japanese Pharmacopoeia standard.
【００２６】[0026]
【発明の効果】本発明の医薬品用，医療用ゴム栓及びそ
の製法は、ＩＩＲを主成分とし、エチレン−プロピレン
共重合体及び／またはポリエチレンを配合することによ
って成形ゴム表面にポリエチレン及び／またはポリプロ
ピレンの微粒の固定させ、ポリエチレンまたはポリプロ
ピレンの微粒子層の形成を可能としたものであり、この
ような微粒子層の形成により、表面粘着性が改善され製
造作業工程における操作性がよくなり一般的な簡単な装
置、作業で製造できるゴム栓となった。また微粒子層の
形成により衛生性が向上し、第１２改正日本薬局方、米
国局方、欧州局方その他の特殊且つ重要な衛生性試験に
合格できるゴム栓である。The rubber stopper for pharmaceuticals and medical use of the present invention and the method for producing the same are characterized in that the rubber is made of polyethylene and / or polypropylene on the surface of the molded rubber by blending ethylene-propylene copolymer and / or polyethylene with IIR as a main component. Of fine particles of polyethylene or polypropylene to form a fine particle layer. By forming such a fine particle layer, surface tackiness is improved, operability in the manufacturing process is improved, and general simple operation is achieved. It became a rubber stopper that could be manufactured by simple equipment and work. In addition, the rubber stopper improves hygiene by forming a fine particle layer, and can pass a special and important hygiene test of the Japanese Pharmacopoeia, the 12th revision, the United States Pharmacopeia and the European Pharmacopoeia.
【図１】はガラス容器に薬を充填した後、本発明のゴム
栓を打栓し、その上にアルミキャップを巻き締めて製品
とした状態を示す断面図である。FIG. 1 is a cross-sectional view showing a state in which a glass container is filled with a drug, a rubber stopper of the present invention is stoppered, and an aluminum cap is wound thereon to form a product.
【図２】は全表面に微粒子層を形成した本発明ゴム栓の
断面図である。FIG. 2 is a cross-sectional view of the rubber stopper of the present invention in which a fine particle layer is formed on the entire surface.
【図３】はプラスチック容器外郭支持体内部に本発明の
ゴム栓を入れ込み、その上に上ブタを載せ、ゴム栓と外
郭支持体、上ブタが溶着された状態を示す断面図であ
る。FIG. 3 is a cross-sectional view showing a state in which the rubber stopper of the present invention is placed inside a plastic container outer shell support, an upper pig is placed thereon, and the rubber stopper, the outer shell support and the upper pig are welded.
【図４】は本発明による滑栓を用いた注射器の断面図で
ある。FIG. 4 is a sectional view of a syringe using the stopper according to the present invention.
【図５】は凍結乾燥製剤のゴム栓として本発明を適用し
た一例を示し、栓の脚部はフッ素系樹脂フィルムを積層
し、フランジ部表面に本発明の微粒子層を設けたものの
部分断面図である。FIG. 5 shows an example in which the present invention is applied as a rubber stopper for a freeze-dried preparation, in which the legs of the stopper are laminated with a fluororesin film, and the fine particle layer of the present invention is provided on the flange surface. It is.
１ 表面層 ２ ゴム質部 ３ 本発明のゴム栓 ４ ガラス容器 ５ 薬 ６ アルミキャップ ７ 針刺し位置 ８ プラスチック外部支持体 ９ プラスチック上ブタ １０ 注射器外筒 １１ 注射器の押し棒 １２ 表面層を有する滑栓 １３ ゴム栓の脚部 １４ フッ素系樹脂フィルム １５ ゴム栓のフランジ部 DESCRIPTION OF SYMBOLS 1 Surface layer 2 Rubber part 3 Rubber stopper of the present invention 4 Glass container 5 Medicine 6 Aluminum cap 7 Needle stab position 8 Plastic external support 9 Plastic upper pig 10 Syringe barrel 11 Push rod of syringe 12 Slip stopper with surface layer 13 Rubber stopper leg 14 Fluorine resin film 15 Rubber stopper flange
Claims (3)
０〜９０重量％と、エチレン−プロピレン共重合体およ
びポリエチレンから選ばれる一種以上３〜５０重量％と
を含有して成るゴム成形体表面に微粒子のポリエチレン
またはポリプロピレンが付着層として形成されてなるこ
とを特徴とする医薬品用，医療用ゴム栓。1. An isoprene-isobutylene copolymer rubber 6
0 to 90% by weight and 3 to 50% by weight of at least one selected from ethylene-propylene copolymer and polyethylene, wherein fine particles of polyethylene or polypropylene are formed as an adhesion layer on the surface of a rubber molded product. A rubber stopper for pharmaceutical and medical use characterized by the following.
０〜９０重量％と、エチレン−プロピレン共重合体およ
びポリエチレンから選ばれる一種以上３〜５０重量％と
を含有して成るゴム表面に、微粒子のポリエチレンまた
はポリプロピレンの水又は溶剤液との混濁液を塗布もし
くは浸漬した後乾燥してゴム表面に微粒子層を均一に形
成した配合ゴムとし、該配合ゴムを加硫成形することを
特徴とする医薬品用，医療用ゴム栓の製造方法。2. An isoprene-isobutylene copolymer rubber 6
On a rubber surface containing 0 to 90% by weight and 3 to 50% by weight of at least one selected from ethylene-propylene copolymer and polyethylene, a turbid liquid of water or a solvent solution of fine particles of polyethylene or polypropylene is applied. A method for producing a rubber stopper for pharmaceutical or medical use, characterized by forming a compounded rubber in which a fine particle layer is uniformly formed on a rubber surface by coating or dipping and then drying, and vulcanizing the compounded rubber.
０〜９０重量％と、エチレン−プロピレン共重合体およ
びポリエチレンから選ばれる一種以上３〜５０重量％と
を含有して成るゴム表面に、微粒子のポリエチレンまた
はポリプロピレンを均一に且つ微粒子の重なりを少なく
振りかけることにより該微粒子をゴム表面に付着させ、
その後加硫成形することを特徴とする医薬品用，医療用
ゴム栓の製造方法。3. An isoprene-isobutylene copolymer rubber 6
Fine particles of polyethylene or polypropylene are sprinkled uniformly on the rubber surface containing 0 to 90% by weight and 3 to 50% by weight of at least one selected from ethylene-propylene copolymer and polyethylene and the overlap of the fine particles is reduced. By adhering the fine particles to the rubber surface,
Thereafter, vulcanization molding is carried out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4330624A JP2891838B2 (en) | 1992-12-10 | 1992-12-10 | Pharmaceutical and medical rubber stoppers and method of manufacturing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4330624A JP2891838B2 (en) | 1992-12-10 | 1992-12-10 | Pharmaceutical and medical rubber stoppers and method of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06169971A JPH06169971A (en) | 1994-06-21 |
| JP2891838B2 true JP2891838B2 (en) | 1999-05-17 |
Family
ID=18234748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4330624A Expired - Lifetime JP2891838B2 (en) | 1992-12-10 | 1992-12-10 | Pharmaceutical and medical rubber stoppers and method of manufacturing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2891838B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3033443B2 (en) | 1994-06-29 | 2000-04-17 | 信越化学工業株式会社 | Anti-reflective coating material |
| CA2386628C (en) * | 2002-05-16 | 2010-07-06 | Bayer Inc. | Hologen- and sulfur-free shaped articles comprising peroxide curable compounds of butyl rubber |
| CA2438024C (en) * | 2003-08-14 | 2013-05-28 | Bayer Inc. | Peroxide curable butyl formulations |
| JP2014170648A (en) * | 2013-03-01 | 2014-09-18 | Sumitomo Electric Ind Ltd | Sealing structure of sealed battery, and sealed battery |
| JP2017075236A (en) * | 2015-10-14 | 2017-04-20 | 株式会社ブリヂストン | Rubber composition and pneumatic tire prepared therewith |
-
1992
- 1992-12-10 JP JP4330624A patent/JP2891838B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH06169971A (en) | 1994-06-21 |
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