JPH0396328A - Rubber plug for vial - Google Patents
Rubber plug for vialInfo
- Publication number
- JPH0396328A JPH0396328A JP1234391A JP23439189A JPH0396328A JP H0396328 A JPH0396328 A JP H0396328A JP 1234391 A JP1234391 A JP 1234391A JP 23439189 A JP23439189 A JP 23439189A JP H0396328 A JPH0396328 A JP H0396328A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- polyethylene
- vial
- sheet
- 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.)
- Pending
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 77
- 239000005060 rubber Substances 0.000 title claims abstract description 77
- -1 polyethylene Polymers 0.000 claims abstract description 39
- 239000004698 Polyethylene Substances 0.000 claims abstract description 34
- 229920000573 polyethylene Polymers 0.000 claims abstract description 34
- 239000003814 drug Substances 0.000 claims description 10
- 229940079593 drug Drugs 0.000 claims description 10
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 2
- 229920005549 butyl rubber Polymers 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 5
- 238000010030 laminating Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 3
- 239000002985 plastic film Substances 0.000 abstract description 3
- 244000043261 Hevea brasiliensis Species 0.000 abstract description 2
- 239000005062 Polybutadiene Substances 0.000 abstract description 2
- 229920005555 halobutyl Polymers 0.000 abstract description 2
- 229920003049 isoprene rubber Polymers 0.000 abstract description 2
- 229920003052 natural elastomer Polymers 0.000 abstract description 2
- 229920001194 natural rubber Polymers 0.000 abstract description 2
- 229920002857 polybutadiene Polymers 0.000 abstract description 2
- 229920002379 silicone rubber Polymers 0.000 abstract description 2
- 239000004945 silicone rubber Substances 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract 4
- 239000012634 fragment Substances 0.000 abstract 2
- 229920003051 synthetic elastomer Polymers 0.000 abstract 1
- 239000005061 synthetic rubber Substances 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 229920001903 high density polyethylene Polymers 0.000 description 3
- 239000004700 high-density polyethylene Substances 0.000 description 3
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Landscapes
- Closures For Containers (AREA)
- Laminated Bodies (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明はバイアル用ゴム栓に関し、さらに詳しくは超高
分子量ポリエチレンシ一トでゴム栓本体の容器口内面お
よび薬液に接する箇所がラミネートされてなるバイアル
用ゴム栓に関する．（従来の技術〕
従来、バイアル用ゴム栓としてゴム中の加硫促進剤、不
純物等が薬液中に滲出するのを防止するために、薬液に
接触するゴム栓面を耐薬品性を有するプラスチックシ一
トでラミネートしたバイアル用ゴム栓が知られている．
（特開昭５７−４７６３７号公報〉
かかるラミネートゴム栓に使用されるプラスチックシ一
トとしては通常バイアルのガラス面との滑性がよい弗素
樹脂が使用されてきた．（特公昭５４−９１１９号公報
）
〔発明が解決しようとする課題〕
しかしながら、最近弗素樹脂シートでラミネートされた
ゴム栓をバイアル容器の口部に打栓する際、バイアルの
容器口のガラス表面によって弗素樹脂シートが摩滅され
て弗素樹脂の端片がバイアル瓶中の薬液に混入し、弗素
樹脂が人体に薬液と共に経口される問題が生じている．
〔課題を解決するための手段〕
本発明者等はこれらの課題を解決するために、鋭意検討
した結果本発明に到達した．
すなわち、本発明はゴム栓本体の容器口内面および薬液
に接する箇所が、平均分子量１３０万〜５５０万のポリ
エチレンのシートでラミネートされてなるバイアル用ゴ
ム栓である．
また本発明は前記バイアル用ゴム栓において、ポリエチ
レンの分子鎖の一部が熱分解で分岐し、ゴムと部分架橋
してなるポリエチレンラミネートゴム栓である．
〔作用〕
本発明のバイアル用ゴム栓はゴム栓本体の容器口内面お
よび薬液との接触面が超高分子量ポリエチレンでラミネ
ートした構戒からなっており、該ポリエチレンが自己潤
滑性に冨んでいるので、ゴム栓がバイアル容器の容器口
に円滑に嵌入することができ、かつ耐摩耗性に富んでい
るので、バイアル容器へのゴム栓の打栓によっても、ポ
リエチレンが摩滅してその端片がバイアル容器中の薬液
に混入することはない。[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a rubber stopper for a vial, and more specifically, the present invention relates to a rubber stopper for vials, and more specifically, the rubber stopper body is laminated with an ultra-high molecular weight polyethylene sheet on the inner surface of the container mouth and the part that comes into contact with the drug solution. This article relates to a rubber stopper for vials. (Prior Art) Conventionally, in order to prevent vulcanization accelerators, impurities, etc. in the rubber from leaching into the chemical liquid as rubber stoppers for vials, the surface of the rubber stopper that comes into contact with the chemical liquid is covered with a chemical-resistant plastic material. Rubber stoppers for vials that are laminated in one piece are known.
(Japanese Unexamined Patent Publication No. 57-47637) As the plastic sheet used for such laminated rubber stoppers, fluororesin, which has good lubricity with the glass surface of the vial, has usually been used. (Japanese Patent Publication No. 54-9119) [Publication] [Problems to be Solved by the Invention] However, recently, when a rubber stopper laminated with a fluororesin sheet is plugged into the mouth of a vial container, the fluororesin sheet is abraded by the glass surface of the vial mouth. A problem has arisen in which the ends of the fluororesin get mixed into the medicinal solution in the vial, and the fluororesin is injected into the human body together with the medicinal solution. [Means for solving the problem] The present inventors have solved these problems. As a result of intensive studies, the present invention has been developed. Namely, the present invention provides a vial in which the inner surface of the container opening of the rubber stopper body and the area in contact with the drug solution are laminated with a sheet of polyethylene having an average molecular weight of 1.3 million to 5.5 million. In addition, the present invention is a polyethylene laminate rubber stopper in which, in the rubber stopper for vials, part of the molecular chain of polyethylene is branched by thermal decomposition and partially crosslinked with rubber. [Function] The present invention The rubber stopper for vials consists of a structure in which the inner surface of the container opening of the rubber stopper body and the surface that comes in contact with the drug solution are laminated with ultra-high molecular weight polyethylene.The polyethylene has a high self-lubricating property, so the rubber stopper is suitable for the vial. It can be fitted smoothly into the mouth of the container and is highly abrasion resistant, so even when a rubber stopper is put in the vial container, the polyethylene will wear away and the end pieces will be exposed to the drug solution in the vial container. There will be no contamination.
以下実施例で本発明の一例を説明する．第１図および第
２図は本発明の夫々の一実施例を示すゴム栓をバイアル
容器に嵌大した際の説明図である．
図中１および１１はゴム栓本体、２および１２はバイア
ル容器、３および１３はポリエチレンシ一ト、４および
ｌ４は容器口内面、５および１５はゴム栓の薬液との接
触面、６はバイアル容器上端接触面、７はゴム栓の足部
を示す．
第１図は環状の足部７を有するゴム栓本体ｌの容器口内
面４および薬液との接触面５をポリエチレンシ一ト３で
ラミネートしてなるバイアル用ゴム栓である．
ゴム栓本体１の材料としてはブチルゴム、イソプレンゴ
ム、ブタジエンゴム、ハロゲン化プチルゴムシリコーン
ゴム等の合戒ゴムまたは天然ゴムが挙げられる．
このゴム栓本体１とラξネー卜するポリエチレンシ一ト
３の材料は、平均分子量は１３０〜５５０万好ましくは
２００〜５００万である（ＡＳＴＭ−０２８５７の粘度
法で測定）．平均分子量が１３０万未満であると、耐摩
耗性が悪くなり、ゴム栓がバイアル容器口に打栓する際
にポリエチレンシ一トが摩滅する傾向がある他に、ポリ
エチレンシ一トとゴムとの接着性が悪くなる傾向があり
、平均分子量が５００万を超えると シートへの加工性
が悪くなる傾向がある．更にこのポリエチレンの密度は
０．９３０〜１ ． ０００ｇ／ｃｄ、融点は１３４〜
１３７゜Ｃである．ポリエチレンシ一トは円柱形のポリ
エチレン戒形体の円周面を回転させながら、カッターで
薄くシート状に削りながら厚さ２０〜２００μ、好まし
くは３０〜１００μのシートを形成して製造する．この
ようにして或形したシートはポリエチレンを溶融戒形し
て得たシートと比較して内部歪みが少なくて好ましい．
第１図のゴム栓はＷ型の凹部を有する下部金型のバイア
ル容器の口部および薬液接触部の表面に相当する部分に
前記下部金型に戒型したポリエチレンシ一ト２を装填す
る．その上に未加硫ゴムを該金型の凹部を含む腔部に充
填した後、上部から円錐台形状の凹部を有する上部金型
で加熱、加圧することによって未加硫ゴムを加硫すると
ともに、ポリエチレンシ一トはポリエチレンの分子鎖の
一部が熱分解されて分岐し、それがゴムと架橋して接着
し、ゴム栓本体１にポリエチレンシ一ト３がラミネート
されたバイアル用ゴム栓が製造される。An example of the present invention will be explained in the following example. FIGS. 1 and 2 are explanatory diagrams showing one embodiment of the present invention when a rubber stopper is fitted into a vial container. In the figure, 1 and 11 are rubber stopper bodies, 2 and 12 are vial containers, 3 and 13 are polyethylene sheets, 4 and 14 are inner surfaces of the container mouth, 5 and 15 are contact surfaces of the rubber stoppers with the drug solution, and 6 is a vial. The top contact surface of the container, 7 indicates the foot of the rubber stopper. FIG. 1 shows a rubber stopper for a vial, which is made by laminating the inner surface 4 of the container mouth and the contact surface 5 with a drug solution of a rubber stopper main body 1 having an annular leg 7 with a polyethylene sheet 3. Materials for the rubber stopper body 1 include butyl rubber, isoprene rubber, butadiene rubber, halogenated butyl rubber, silicone rubber, and other rubbers or natural rubber. The material of the polyethylene sheet 3 that mates with the rubber stopper body 1 has an average molecular weight of 1.3 to 5.5 million, preferably 2 to 5 million (measured by the viscosity method of ASTM-02857). If the average molecular weight is less than 1,300,000, the abrasion resistance will be poor, and the polyethylene sheet will tend to wear out when the rubber stopper is plugged into the opening of the vial. Adhesion tends to deteriorate, and if the average molecular weight exceeds 5 million, processability into sheets tends to deteriorate. Furthermore, the density of this polyethylene is 0.930 to 1. 000g/cd, melting point is 134~
It is 137°C. A polyethylene sheet is manufactured by rotating the circumferential surface of a cylindrical polyethylene shape and cutting it into a thin sheet with a cutter to form a sheet with a thickness of 20 to 200 μm, preferably 30 to 100 μm. A sheet formed in this manner is preferable because it has less internal distortion than a sheet obtained by melt-forming polyethylene. In the rubber stopper shown in Figure 1, a polyethylene sheet 2 molded into the lower mold is loaded into a portion corresponding to the opening of the vial container and the surface of the chemical contact area of the lower mold, which has a W-shaped recess. After filling the cavity including the recess of the mold with unvulcanized rubber, the unvulcanized rubber is vulcanized by heating and pressurizing from the upper mold with a truncated cone-shaped recess. In the polyethylene sheet, a part of the molecular chain of polyethylene is thermally decomposed and branches, which cross-links and adheres to the rubber, and a rubber stopper for vials is formed by laminating the polyethylene sheet 3 onto the rubber stopper body 1. Manufactured.
第２図は本発明のバイアル用ゴム栓の他の実施例で、円
柱状の挿入部を有するゴム栓零体１１の容器口内面１４
、薬液との接触面１５およびバイアル容器上端接触面６
にポリエチレンシー目３をラミネートしたバイアル用ゴ
ム栓をバイアル容器に嵌入した際の説明図である．
このバイアル用ゴム栓も第１図のバイアル用ゴム栓と同
じ方法で製造できるが、予め威形したゴム栓本体を接着
剤でポリエチレンシ一トと接着して製造してもよい．
実施例工
平均分子量４５０万のポリエチレン（三井石油化学社製
、ハイゼックス・ごリオン３４０Ｍ ）からなる円柱状
の戒形体をカッターで削って厚さ５０μのシートを得た
．このシートを円周内面に沿って、深さ４．５ｍの足部
の腔部を有する下部金型に威型し、第１図のようなポリ
エチレンシ一トからなる威形体を下部金型に装填した．
次いで未加硫ブチルゴムを下部金型の腔部に充填し、上
部金型で押圧し、温度１５０”Ｃに加熱してゴムを加硫
化するとともに、ポリエチレンシ一トをゴムと部分的に
架橋させて強固に接着させた．その結果、足部の長さ４
．５ｍバイアル容器口に嵌入する箇所の外径１２．７ｍ
ｍ、上蓋部の外径１９．０Ｍの第１図のような構造をし
たゴム栓を製造した．
このゴム栓を容器口の内径１２．３ｍｍのバイアル容器
に打栓して、バイアル容器を封緘した．この時ゴム栓本
体にラミネートしたポリエチレンシ一トが摩滅して、そ
の端片がバイアル容器内に落ちた件数を１０００個のゴ
ム栓とバイアル容器で試験した．その結果を第１表に示
す．
更にこのポリエチレンシ一トの鋼板上の動摩擦係数を第
１表に示す．
動摩擦係数はＡＳＴ？Ｉ−０１８９４に従って測定した
．比較例１
平均分子量２３万の高密度ポリエチレンを溶融して厚さ
５０μのシートを戒形した．このシートを実施例ｌと同
じ下部金型に或型し、それを下部金型に装填した．その
上から接着剤を塗布した後、予め下部金型の腔部の形に
戒型された加硫化ブチルゴムの戒形体を嵌め込み実施例
ｌと同じ寸法のゴム栓を戒形した．このゴム栓１０００
個と実施例１と同じ寸法のバイアル容器１０００個を用
いてゴム栓本体にラミネートした高密度ポリエチレンの
ＦＪ滅割合を実施例１と同様にして試験した．その結果
を第１表に示す．更に高密度ポリエチレンシ一トの動摩
擦係数も第１表に示す，
比較例２
厚さ５０μのポリ四弗化エチレンシ一トを実施例１と同
じ下部金型に戒型し、それを下部金型に装填した．次い
で未加硫ブチルゴムを下部金型の腔部に充填し、上部金
型で押圧し１６０゜Ｃで加熱して加硫化プチルゴムから
なるゴム栓本体にポリ四弗化エチレンシ一トがラミネー
トされた実施例１と同じ寸法のゴム栓を或形した．この
ゴム栓１０００個と実施例１で使用したバイアル容器１
０００個を用いて、ゴム栓本体にラごネートしたポリ四
弗化エチレンシートの摩滅割合を実施例１と同様にして
試験した．その結果を第１表に示す．更にポリ四弗化エ
チレンシ一トの動摩擦係数を第１表に示す。FIG. 2 shows another embodiment of the rubber stopper for vials of the present invention, in which the inner surface 14 of the container mouth of the rubber stopper zero body 11 having a cylindrical insertion portion is shown.
, the contact surface 15 with the drug solution and the upper end contact surface 6 of the vial container.
FIG. 2 is an explanatory diagram of a vial rubber stopper laminated with a polyethylene seam 3 inserted into a vial container. This rubber stopper for vials can be manufactured by the same method as the rubber stopper for vials shown in Fig. 1, but it may also be manufactured by bonding a pre-shaped rubber stopper body to a polyethylene sheet with an adhesive. EXAMPLE A cylindrical shaped body made of polyethylene (HIZEX GOLION 340M, manufactured by Mitsui Petrochemical Co., Ltd.) having an average molecular weight of 4.5 million was cut with a cutter to obtain a sheet with a thickness of 50 μm. This sheet is molded into a lower mold having a foot cavity with a depth of 4.5 m along the circumferential inner surface, and a molded body made of polyethylene sheet as shown in Fig. 1 is molded into the lower mold. Loaded.
Next, unvulcanized butyl rubber is filled into the cavity of the lower mold, pressed with the upper mold, and heated to a temperature of 150"C to vulcanize the rubber and partially crosslink the polyethylene sheet with the rubber. The length of the foot was 4.
．． The outer diameter of the part that fits into the mouth of the 5m vial is 12.7m.
A rubber stopper with a structure as shown in Fig. 1 with an outer diameter of 19.0 m and an upper lid part was manufactured. This rubber stopper was plugged into a vial container with an inner diameter of 12.3 mm to seal the vial container. At this time, the polyethylene sheet laminated to the rubber stopper body was worn out and the end piece fell into the vial container. A test was conducted using 1000 rubber stoppers and vial containers. The results are shown in Table 1. Furthermore, the coefficient of dynamic friction of this polyethylene sheet on a steel plate is shown in Table 1. Is the coefficient of dynamic friction AST? Measured according to I-01894. Comparative Example 1 High-density polyethylene with an average molecular weight of 230,000 was melted to form a sheet with a thickness of 50 μm. This sheet was molded into the same lower mold as in Example 1, and loaded into the lower mold. After applying adhesive thereon, a shaped body of vulcanized butyl rubber, which had been previously shaped into the shape of the cavity of the lower mold, was fitted to form a rubber stopper with the same dimensions as in Example 1. This rubber plug 1000
The FJ removal rate of high-density polyethylene laminated to a rubber stopper body was tested in the same manner as in Example 1 using 1,000 vials having the same dimensions as in Example 1. The results are shown in Table 1. Furthermore, the coefficient of dynamic friction of the high-density polyethylene sheet is shown in Table 1. Comparative Example 2 A polytetrafluoroethylene sheet with a thickness of 50 μm was molded into the same lower mold as in Example 1, and the mold was placed in the lower mold. Loaded into. Next, unvulcanized butyl rubber was filled into the cavity of the lower mold, pressed with the upper mold and heated at 160°C to form a rubber plug body made of vulcanized butyl rubber and laminated with polytetrafluoroethylene sheet. A rubber stopper with the same dimensions as Example 1 was shaped. 1000 of these rubber stoppers and the vial container 1 used in Example 1
The wear rate of the polytetrafluoroethylene sheet laminated onto the rubber stopper body was tested in the same manner as in Example 1 using 000 pieces. The results are shown in Table 1. Furthermore, the coefficient of dynamic friction of polytetrafluoroethylene sheet is shown in Table 1.
第１表
第１表から明らかなように、本発明の実施例ｌのバイア
ル用ゴム栓は比較例のゴム栓と比較して、ゴム栓をバイ
アル容器口に打栓した時のシートの摩滅割合も少ない．
更に実施例１のシートはポリ四弗化エチレンシ一トから
なる比較例２のバイアル用ゴム栓に匹敵する優れた潤滑
性を有している。Table 1 As is clear from Table 1, the rubber stopper for vial of Example 1 of the present invention has a higher rate of sheet wear when the rubber stopper is plugged into the opening of the vial, compared to the rubber stopper of the comparative example. There are also few.
Furthermore, the sheet of Example 1 has excellent lubricity comparable to the rubber stopper for vials of Comparative Example 2, which is made of polytetrafluoroethylene sheet.
本発明のバイアル用ゴム栓はバイアル容器口への打栓に
際して殆どゴム栓本体にラミネートしたシートが摩滅す
ることがないので、バイアル容器内の薬液中にプラスチ
ックシ一トの端片が混入することはない．また本発明の
バイアル用ゴム栓は潤滑性に優れているので、バイアル
容器口への打栓を円滑に行うことができ、強固に封緘す
ることができる．When the rubber stopper for vials of the present invention is plugged into the opening of the vial container, the sheet laminated to the rubber stopper body is hardly worn out, so there is no possibility that the ends of the plastic sheet will get mixed into the drug solution in the vial container. No. Furthermore, since the rubber stopper for vials of the present invention has excellent lubricity, it is possible to smoothly plug the opening of the vial container, and it is possible to seal it firmly.
第ｌ図および第２図は本発明の夫々の一実施例を示すゴ
ム栓をバイアル容器に嵌人した際の説明図である．
図中１およびｌ１はゴム栓本体、２およびＩ２はバイア
ル容器、３および１３はポリエチレンシ一ト、４および
ｌ４は容器口内面、５および１５はゴム栓の薬液との接
触面、６はバイアル容器上端接触面、７はゴム栓の足部
を示す．FIG. 1 and FIG. 2 are explanatory diagrams showing a rubber stopper fitted into a vial container, respectively, showing an embodiment of the present invention. In the figure, 1 and l1 are rubber stopper bodies, 2 and I2 are vial containers, 3 and 13 are polyethylene sheets, 4 and l4 are inner surfaces of the container mouth, 5 and 15 are contact surfaces of the rubber stoppers with the drug solution, and 6 is a vial. The top contact surface of the container, 7 indicates the foot of the rubber stopper.
Claims (2)
が、平均分子量１３０万〜５５０万のポリエチレンのシ
ートでラミネートされてなるバイアル用ゴム栓。(1) A rubber stopper for a vial, in which the inner surface of the container mouth of the rubber stopper body and the area in contact with the drug solution are laminated with a polyethylene sheet having an average molecular weight of 1.3 million to 5.5 million.
ゴムと部分架橋してなるポリエチレンラミネートゴム栓
である請求項１記載のバイアル用ゴム栓。(2) Some of the molecular chains of polyethylene branch due to thermal decomposition,
The rubber stopper for a vial according to claim 1, which is a polyethylene laminate rubber stopper partially crosslinked with rubber.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1234391A JPH0396328A (en) | 1989-09-07 | 1989-09-07 | Rubber plug for vial |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1234391A JPH0396328A (en) | 1989-09-07 | 1989-09-07 | Rubber plug for vial |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0396328A true JPH0396328A (en) | 1991-04-22 |
Family
ID=16970266
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1234391A Pending JPH0396328A (en) | 1989-09-07 | 1989-09-07 | Rubber plug for vial |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0396328A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05184642A (en) * | 1991-05-29 | 1993-07-27 | Kawasumi Lab Inc | Mouth of medical care container and medical care container |
| KR101892608B1 (en) * | 2017-02-22 | 2018-08-29 | 삼성의료고무주식회사 | Rubber Stopper for a medical Bottle and the manufacturing method thereof |
-
1989
- 1989-09-07 JP JP1234391A patent/JPH0396328A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05184642A (en) * | 1991-05-29 | 1993-07-27 | Kawasumi Lab Inc | Mouth of medical care container and medical care container |
| KR101892608B1 (en) * | 2017-02-22 | 2018-08-29 | 삼성의료고무주식회사 | Rubber Stopper for a medical Bottle and the manufacturing method thereof |
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