JP3341353B2 - Medical equipment - Google Patents
Medical equipmentInfo
- Publication number
- JP3341353B2 JP3341353B2 JP11897893A JP11897893A JP3341353B2 JP 3341353 B2 JP3341353 B2 JP 3341353B2 JP 11897893 A JP11897893 A JP 11897893A JP 11897893 A JP11897893 A JP 11897893A JP 3341353 B2 JP3341353 B2 JP 3341353B2
- Authority
- JP
- Japan
- Prior art keywords
- medical device
- soft material
- medical
- soft
- present
- 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.)
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- Materials For Medical Uses (AREA)
Description
【0001】[0001]
【産業上の利用分野】本発明は、表面の摩擦係数の少な
い医療用具に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a medical device having a low surface friction coefficient.
【0002】[0002]
【従来の技術】従来より、ゴムのように弾性のある軟質
の材質からなる種々の医療用具が使用されている。しか
しながら、軟質の材質は、体内に挿入する場合に体内組
織に適合して形状を屈曲させたり変化させることができ
る点及び体内の組織に柔らかく接触する点で好ましい
が、摩擦抵抗は硬質の材質より大きくなり、摩擦による
体内組織の損傷が問題となる。すなわち、医療用具の摩
擦には、例えば、イントロデューサのように、皮膚から
血管に突き刺し、カテーテル等を血管に挿通するような
医療用具では、皮膚組織、筋肉組織及び血管を突き抜け
る際に軟質シース表面との摩擦が大きいと、それらの組
織を損傷し、また、シースを体内に長時間留置する場合
なども人体が揺れるたびに体内組織とシース表面との間
に摩擦が生じることによる損傷があり、留置途中の出血
又はシースを抜いた後の止血が困難になる場合もある。
また、薬液注入回路又は体液排出回路に使用されている
種々の水密性摺動面を有する医療用具、例えば、注射器
などのように水密性スライド表面を有するものは、液の
漏れと摩擦低減を両立させる必要のあるものがあり、軟
質であると水密性は向上するが、摩擦が増大するという
困難が生じる。2. Description of the Related Art Conventionally, various medical devices made of an elastic soft material such as rubber have been used. However, a soft material is preferable in that it can bend or change its shape in conformity with body tissue when inserted into the body, and is soft in contact with tissue in the body, but friction resistance is higher than that of a hard material. It becomes large, and the damage of internal tissues due to friction becomes a problem. That is, the friction of the medical device is, for example, in a medical device such as an introducer that pierces a blood vessel from the skin and penetrates a blood vessel with a catheter or the like, when the soft tissue surface penetrates the skin tissue, muscle tissue and the blood vessel. If the friction between the body and the body is large, the tissue may be damaged.In addition, even when the sheath is left in the body for a long time, there is damage caused by friction between the body tissue and the sheath surface every time the human body shakes, Bleeding during placement or hemostasis after removing the sheath may be difficult.
In addition, medical devices having various water-tight sliding surfaces used in a liquid injection circuit or a body fluid discharging circuit, for example, a device having a water-tight sliding surface such as a syringe can achieve both liquid leakage and friction reduction. There is something that needs to be done, and if it is soft, watertightness is improved, but difficulty arises in that friction increases.
【0003】[0003]
【発明が解決しようとする課題】本発明は、軟質材の変
形追従性を維持しながら、表面摩擦の少ない医療用具を
提供することを目的とするものである。SUMMARY OF THE INVENTION It is an object of the present invention to provide a medical device which has a low surface friction while maintaining the deformability of a soft material.
【0004】[0004]
【課題を解決するための手段】本発明者らは、医療用具
において、材質が柔らかいと表面摩擦が増加する現象に
着目して、医療用具の表面の摩擦を低減するために、医
療用具の表面のみを硬化させると、軟質材質の変形追従
性及び柔らかい接触感触を維持しながら摩擦を低減でき
ることを見いだしこの知見に基づき本発明を完成するに
至った。Means for Solving the Problems The present inventors have focused on the phenomenon that surface friction increases when the material of a medical device is soft, and to reduce the friction of the surface of the medical device, It has been found that, when only the material is cured, the friction can be reduced while maintaining the deformability of the soft material and the soft touch, and based on this finding, the present invention has been completed.
【0005】すなわち、本発明は、 (1)ショア硬度80A〜65Dの高分子物質製医療用
具の表面層に架橋剤を反応させることにより、元の表面
より固い表面を形成して、該表面にシリコーンオイルを
塗布したことを特徴とする体内に挿入する軟質材料の医
療用具、 (2)ショア硬度80A〜65Dの高分子物質製医療用
具の表面に架橋剤を反応させることにより、元の表面よ
り固い表面を形成したのち、プラズマ処理によって、表
面を活性化して、該表面にシリコーンオイルを塗布した
ことを特徴とする体内に挿入する軟質材料の医療用具、 (3)シリコーンオイルが重合度100〜20000の
ポリジメチルシロキサンである第1項又は第2項記載の
体内に挿入する軟質材料の医療用具、 (4)プラズマ処理がコロナ放電による低温プラズマ処
理である第2項記載の体内に挿入する軟質材料の医療用
具、 (5)高分子物質がポリウレタンである第1項、第2
項、第3項又は第4項記載の体内に挿入する軟質材料の
医療用具、及び (6)医療用具がカテーテルである第1項、第2項、第
3項又は第4項記載の体内に挿入する軟質材料の医療用
具、を提供するものである。本発明が適用できる医療用
具は、使用態様において、人体組織と医療用具表面との
摩擦が人体組織の損傷を起こす恐れのある医療用具、例
えば、カテーテル、イントロデューサ、シースその他の
体内に挿入する軟質材質の医療用具に適用することがで
きる。また、人体組織の接触しない医療用具では、輸液
回路等の体内への液体注入回路、人工心臓回路等の循環
回路又は体液排出回路等に用いられるシリンジ等の水密
性摺動面を有する医療用具に適用することができる。本
発明の軟質高分子物質製医療用具とは、合成又は天然の
軟質高分子物質を材質とするものであり、軟質樹脂及び
ゴム物質等の通常、医療用具に用いられる樹脂、例え
ば、ポリウレタン樹脂、ナイロン樹脂等の軟質樹脂並び
にポリイソブレン、ポリウレタン等のゴム物質の医療用
具を使用することができ、特にポリウレタン樹脂製が好
ましい。本発明において、軟質高分子物質とは、同一の
材質の厚さ10mmの試験片によるショア硬度が80A以
上でありかつ65D以下の高分子物質を示す。That is, the present invention provides: (1) a surface layer of a medical device made of a polymeric material having a Shore hardness of 80A to 65D, which is reacted with a crosslinking agent to form a harder surface than the original surface, A medical device of a soft material to be inserted into the body, which is coated with silicone oil; and (2) a surface of a medical device made of a high molecular substance having a Shore hardness of 80A to 65D is reacted with a cross-linking agent, so that the surface of the medical device becomes higher than the original surface. After forming a hard surface, the surface is activated by plasma treatment, and the surface is coated with silicone oil. A medical device made of a soft material to be inserted into the body, characterized in that (3) the silicone oil has a polymerization degree of 100 to 3. The medical device of soft material to be inserted into the body according to item 1 or 2 which is 20,000 polydimethylsiloxane, (4) plasma treatment is performed at low temperature by corona discharge 3. The medical device made of a soft material to be inserted into the body according to item 2, which is a plasma treatment, (5) The medical device according to items 1 and 2, wherein the polymer substance is polyurethane.
Item, a medical device made of a soft material to be inserted into the body according to Item 3 or 4, and (6) a medical device is a catheter according to Item 1, 2, 3, or 4 wherein the medical device is a catheter. A soft material medical device to be inserted. The medical device to which the present invention can be applied is a medical device in which the friction between the human body tissue and the surface of the medical device may cause damage to the human body tissue in the use mode, for example, a catheter, an introducer, a soft material to be inserted into a sheath or other soft body. It can be applied to medical devices made of materials. In addition, medical devices that do not come into contact with human body tissue include medical devices having a water-tight sliding surface such as a syringe used for a liquid injection circuit into the body such as an infusion circuit, a circulation circuit such as an artificial heart circuit, or a body fluid discharge circuit, and the like. Can be applied. The medical device made of a soft polymer material of the present invention is made of a synthetic or natural soft polymer material, and is usually used for a medical device such as a soft resin and a rubber material, such as a polyurethane resin. Medical tools made of a soft resin such as a nylon resin or a rubber substance such as polyisobrene or polyurethane can be used, and a polyurethane resin is particularly preferable. In the present invention, the soft polymer substance refers to a polymer substance having a Shore hardness of 80A or more and 65D or less by a 10 mm thick test piece of the same material.
【0006】本発明に用いる架橋剤は、医療用具に使用
されている軟質高分子物質に応じて適当な架橋剤を使用
することができる。架橋剤としては、多官能基を有する
化合物、脱水素により架橋結合を形成する化合物及び過
酸化物によるラジカル架橋の生成などを適用することが
できる。本発明の表面硬化方法は、軟質樹脂がウレタン
樹脂である場合に、ウレタン樹脂に適した架橋剤を表面
に含浸させて加熱して硬化させることができる。例え
ば、ウレタン樹脂表面の架橋剤としては、ポリオールと
イソシアナート、又はフッ素ガスを使用することがで
き、特に好ましい架橋剤はポリウレタン樹脂を構成する
モノマーと、同一のポリオールとイソシアナートのモノ
マー、又はオリゴマーである。これらを表面に接触させ
て、架橋反応を形成する方法によって表面の硬化を行う
ことができる。フッ素ガスの場合は単にガスを接触させ
るだけであり、ポリオールとイソシアナートは、ポリウ
レタン樹脂の表面層に含浸させてから直ちに加熱して架
橋反応を進行させる。また、ポリイソプレンなどの炭化
水素系ポリマーの場合には、過酸化物を溶解して溶剤を
表面に塗布して、直ちに加熱して表面の架橋反応を起こ
すことができる。これらの架橋剤の使用量を適度に調節
することによって、表面の硬度を最初の硬度(内部の硬
度)より適度に固くすることができる。このように、表
面を固くすることによって、医療用具の摩擦係数を大幅
に低減させることができる。しかし、表面の架橋を内部
の材質と比較してあまり大きくすると、本来当該材質に
期待されていた医療用具の柔軟性を喪失、又は表面層が
破損するので好ましくない。本発明において採用した架
橋条件を、医療用具と同一材質からなる厚さ10mmの試
験片に適用した場合に、最初のショア硬度より、すなわ
ち、内部の硬度より表面が固くなる架橋条件が望まし
い。例えば、ショア硬度80Aのものの場合には90A
程度に、60Dのものの場合は70D程度になることが
好ましい。この硬度の上昇が大きすぎると、軟質高分子
物質としての変形追従性及び柔らかい接触感触が低下す
る。さらに、硬くなった表面層が、破損又は潤滑剤の剥
離が生じ易くなる。また、硬度上昇が少ない場合には摩
擦の低減効果がない。[0006] As the cross-linking agent used in the present invention, an appropriate cross-linking agent can be used according to the soft polymer substance used in the medical device. As the cross-linking agent, a compound having a polyfunctional group, a compound forming a cross-linking by dehydrogenation, generation of radical cross-linking by peroxide, and the like can be applied. According to the surface curing method of the present invention, when the soft resin is a urethane resin, the surface can be cured by impregnating the surface with a crosslinking agent suitable for the urethane resin and heating. For example, as a cross-linking agent on the surface of the urethane resin, a polyol and an isocyanate, or a fluorine gas can be used. Particularly preferable cross-linking agents are a monomer constituting the polyurethane resin and a monomer or oligomer of the same polyol and isocyanate. It is. These can be brought into contact with the surface to cure the surface by a method of forming a crosslinking reaction. In the case of fluorine gas, the gas is simply brought into contact with the gas, and the polyol and the isocyanate are heated immediately after impregnating the surface layer of the polyurethane resin, so that the crosslinking reaction proceeds. In the case of a hydrocarbon-based polymer such as polyisoprene, a peroxide can be dissolved, a solvent can be applied to the surface, and heated immediately to cause a surface cross-linking reaction. By appropriately adjusting the amount of these crosslinking agents used, the surface hardness can be appropriately hardened from the initial hardness (internal hardness). Thus, by making the surface hard, the friction coefficient of the medical device can be significantly reduced. However, if the surface cross-linking is too large compared to the internal material, it is not preferable because the flexibility of the medical device originally expected for the material is lost or the surface layer is damaged. When the cross-linking conditions adopted in the present invention are applied to a 10 mm-thick test piece made of the same material as the medical device, the cross-linking conditions that make the surface harder than the initial Shore hardness, that is, the inner hardness, are preferable. For example, 90A in the case of a Shore hardness of 80A
In the case of 60D, it is preferably about 70D. If the increase in the hardness is too large, the deformability as a soft polymer substance and the soft touch feeling are reduced. Further, the hardened surface layer is liable to be broken or the lubricant to be peeled off. When the increase in hardness is small, there is no effect of reducing friction.
【0007】本発明に用いる潤滑剤は、人体に影響のな
いものであれば特に制限なく使用することができ、例え
ば、シリコーン、フッ素樹脂オリゴマー、流動パラフィ
ンなどの生理活性のないものを使用することができる。
特にシリコーンオイル又はフッ素系オリゴマーが本発明
に好適である。本発明に用いるシリコーンオイルとして
は、重合度100〜20000程度のジメチルポリシロ
キサン、フェニルメチルシロキサン、γ−トリフロロプ
ロピルメチルシロキサン及びシラノール基を有するもの
など変性ポリシロキサン等を使用することができる。ま
た、フッ素樹脂オリゴマーとしては、フッ素メタクリレ
ートオリゴマーやフッ素アクリレートオリゴマー等を使
用することができる。本発明医療用具の軟質高分子物質
の硬化表面に塗布した潤滑剤が脱離するのを防止するた
めに、本発明の医療用具の硬化表面にさらにプラズマ処
理好ましくはコロナ放電処理を行うことにより、高分子
物質表面にカルボキシル基又はカルボニル基などの極性
基を生成せしめて、これが樹脂表面の吸着力を増大させ
る。特に、ポリウレタン樹脂の場合には、カルボキシル
基の発生が容易で、表面の活性化が起こり易い。本発明
に用いるプラズマ処理は、上記樹脂塗装又はフイルム印
刷の前処理で行われている公知の方法、放電条件及び放
電設備を用いて実施することができる。本発明における
プラズマ処理は、例えば2電極を設置した真空空間に医
療用具を置き、該真空空間に微量の酸素、炭酸ガス又は
窒素を供給しながら、放電が発生するまで両電極間の電
圧を上げて、プラズマ放電を行い医療用具の樹脂表面を
活性化する。酸素又は炭酸ガスを導入したときは主とし
てカルボキシル基又はカルボニル基が表面分子に付加さ
れ、窒素ガスの場合は、前記の極性基以外に窒化物が表
面に付加される。また、コロナ放電処理としては、常圧
の空気存在下において、高電圧放電により、コロナ放電
を行い、その雰囲気下で医療用具の樹脂表面を活性化す
ることもできる。The lubricant used in the present invention can be used without any particular limitation as long as it does not affect the human body. For example, a lubricant having no biological activity such as silicone, fluororesin oligomer, or liquid paraffin can be used. Can be.
Particularly, silicone oil or fluorine-based oligomer is suitable for the present invention. As the silicone oil used in the present invention, dimethylpolysiloxane having a polymerization degree of about 100 to 20,000, phenylmethylsiloxane, γ-trifluoropropylmethylsiloxane, and modified polysiloxane such as those having a silanol group can be used. Further, as the fluororesin oligomer, a fluorine methacrylate oligomer, a fluorine acrylate oligomer or the like can be used. In order to prevent the lubricant applied to the cured surface of the soft polymer substance of the medical device of the present invention from desorbing, by further performing a plasma treatment, preferably a corona discharge treatment, on the cured surface of the medical device of the present invention, A polar group such as a carboxyl group or a carbonyl group is generated on the surface of the polymer substance, and this increases the adsorptive power on the resin surface. In particular, in the case of a polyurethane resin, generation of a carboxyl group is easy and activation of the surface is easy to occur. The plasma treatment used in the present invention can be performed by using a known method, discharge conditions, and discharge equipment which are performed in the above pretreatment of resin coating or film printing. In the plasma treatment in the present invention, for example, a medical device is placed in a vacuum space in which two electrodes are installed, and while a small amount of oxygen, carbon dioxide or nitrogen is supplied to the vacuum space, the voltage between the two electrodes is increased until a discharge occurs. Then, plasma discharge is performed to activate the resin surface of the medical device. When oxygen or carbon dioxide gas is introduced, a carboxyl group or a carbonyl group is mainly added to the surface molecule. In the case of nitrogen gas, a nitride other than the above-mentioned polar group is added to the surface. As the corona discharge treatment, corona discharge can be performed by high-voltage discharge in the presence of air at normal pressure, and the resin surface of the medical device can be activated in that atmosphere.
【0008】本発明のプラズマ処理を行った場合におい
ても、処理後の水に対する表面張力に基づく濡れ指数
が、30ダイン以上、好ましくは、40ダイン以上にな
ることが望ましい。本発明の表面処理による樹脂表面の
活性化の程度が大きいほど、潤滑剤塗布前の表面の潤滑
剤に対する吸着活性の維持期間が長くなる。通常のプラ
ズマ処理による場合は、長期間、例えば、6カ月程度の
表面活性維持期間があるので、表面活性化後、乾燥状態
で密封包装しておけば、使用直前に潤滑剤を塗布しても
表面活性が維持されるので、コーティングしていない医
療用具の状態で保存できる利点がある。プラズマ処理の
場合、表面活性が低下した場合は再度プラズマ処理を行
うことによって、再度長期間維持できる表面活性を復活
させることができる。[0008] Even when the plasma treatment of the present invention is performed, it is desirable that the wetting index based on the surface tension of water after the treatment be 30 dynes or more, preferably 40 dynes or more. The greater the degree of activation of the resin surface by the surface treatment of the present invention, the longer the period of maintaining the adsorption activity of the surface on the lubricant before the application of the lubricant. In the case of ordinary plasma treatment, there is a long term, for example, a surface activity maintenance period of about 6 months, so if the surface is activated, if it is sealed and packaged in a dry state, even if a lubricant is applied immediately before use, Since the surface activity is maintained, there is an advantage that the medical device can be stored in the state of an uncoated medical device. In the case of the plasma treatment, when the surface activity decreases, the plasma treatment is performed again, whereby the surface activity that can be maintained for a long time can be restored.
【0009】[0009]
実施例1 ショア硬度60Dのポリウレタンで形成されたカテーテ
ルの表面にポリテトラメチレングリコールとメチレンジ
フェニルジイソシアナートの混合物(モル比:NCO/
OH=2)を塗布し、90℃で24時間加熱した後、ポ
リジメチルシロキサンの原液に浸漬して、本発明に係る
カテーテルを得た。表面硬度を測定したところ、ショア
硬度70Dであった。別途成形した架橋処理をしないシ
ョア硬度70Dからなるポリウレタン製カテーテルに比
べて、遥かに柔軟性があり、かつ表面の滑り性も良好で
経皮的に体内へ挿入したところ、スムーズに挿入するこ
とができた。一方、前記架橋処理をしないショア硬度7
0Dからなるカテーテルのの場合は目的部位までスムー
ズに挿入できなかった。 実施例2 ショア硬度55Dのポリウレタンシースの表面にフッ素
ガスと窒素ガスの混合ガス(F2:N2=1:4)を30
分間室温で接触させた。後、1分間のコロナ放電処理を
行ない、直ちにポリジメチルシロキサンの原液に浸漬し
た。得られたチューブの表面はショア硬度65Dであっ
た。実施例1のカテーテルよりさらに柔軟性があり、表
面の滑りも良好であった。Example 1 A mixture of polytetramethylene glycol and methylene diphenyl diisocyanate (molar ratio: NCO /
OH = 2), heated at 90 ° C. for 24 hours, and immersed in a stock solution of polydimethylsiloxane to obtain a catheter according to the present invention. When the surface hardness was measured, the Shore hardness was 70D. Compared to a separately molded polyurethane catheter with a Shore hardness of 70D without cross-linking treatment, it is much more flexible and has a good surface slippery, and when inserted into the body percutaneously, it can be inserted smoothly. did it. On the other hand, a Shore hardness of 7 without the crosslinking treatment
In the case of a catheter made of 0D, it was not possible to smoothly insert the catheter into a target site. Example 2 A mixture gas of fluorine gas and nitrogen gas (F 2 : N 2 = 1: 4) was applied to a surface of a polyurethane sheath having a Shore hardness of 55D for 30 times.
Minutes at room temperature. Thereafter, a corona discharge treatment for 1 minute was performed, and the resultant was immediately immersed in a stock solution of polydimethylsiloxane. The surface of the obtained tube had a Shore hardness of 65D. The catheter was more flexible than the catheter of Example 1, and the surface slippage was good.
【0010】[0010]
【発明の効果】本発明のコーティングした医療用具は、
軟質高分子物質によって形成されているので、変形追従
性及びソフトな接触感触を維持していながら、表面が内
部より固くなっているため摩擦が低減され、挿入し易い
上、体内組織を損傷しない利点がある。本発明の摩擦低
減効果は、硬化表面にさらに放電処理を行うことによっ
てコーティングされた潤滑剤が脱落しないので、長期間
維持することができる。The coated medical device of the present invention is
Since it is made of a soft polymer material, it has the advantage of not being damaged and the body tissue not being damaged because the surface is harder than the inside, while maintaining the deformation followability and soft touch feeling, friction is reduced and it is easy to insert. There is. The friction reducing effect of the present invention can be maintained for a long period of time because the coated lubricant does not fall off by further performing discharge treatment on the cured surface.
フロントページの続き (56)参考文献 特開 平2−289264(JP,A) 特開 平1−270872(JP,A) 特開 平4−285566(JP,A) 特開 平3−275070(JP,A) 特開 昭63−164956(JP,A) 特開 昭63−3866(JP,A) 特開 昭63−305875(JP,A) (58)調査した分野(Int.Cl.7,DB名) A61L 29/00 - 33/18 Continuation of front page (56) References JP-A-2-289264 (JP, A) JP-A-1-270872 (JP, A) JP-A-4-285566 (JP, A) JP-A-3-275070 (JP) JP-A-63-166496 (JP, A) JP-A-63-3866 (JP, A) JP-A-63-305875 (JP, A) (58) Fields investigated (Int. Cl. 7 , DB Name) A61L 29/00-33/18
Claims (6)
医療用具の表面層に架橋剤を反応させることにより、元
の表面より固い表面を形成して、該表面にシリコーンオ
イルを塗布したことを特徴とする体内に挿入する軟質材
料の医療用具。The method according to claim 1] reacting a crosslinking agent to the surface layer of the polymeric material made medical device of Shore hardness 80A~65D, to form a hard surface than the original surface, the silicone O to the surface
Soft material to be inserted into the body, characterized in that coated with yl
Charges medical tools.
医療用具の表面に架橋剤を反応させることにより、元の
表面より固い表面を形成したのち、プラズマ処理によっ
て、表面を活性化して、該表面にシリコーンオイルを塗
布したことを特徴とする体内に挿入する軟質材料の医療
用具。2. A surface of a polymeric medical device having a Shore hardness of 80A to 65D is reacted with a cross-linking agent to form a harder surface than the original surface, and then the surface is activated by plasma treatment. A medical device made of a soft material to be inserted into a body, characterized in that silicone oil is applied to the surface.
00のポリジメチルシロキサンである請求項1又は2記
載の体内に挿入する軟質材料の医療用具。 3. The silicone oil has a degree of polymerization of 100 to 200.
3. The polydimethylsiloxane of claim 1 or 2.
A medical device made of a soft material to be inserted into the body.
ズマ処理である請求項2記載の体内に挿入する軟質材料
の医療用具。 4. A low-temperature plasma processing using corona discharge.
3. The soft material to be inserted into the body according to claim 2, which is a zuma treatment.
Medical tools.
1、2、3又は4記載の体内に挿入する軟質材料の医療
用具。 5. The method according to claim 1, wherein the polymer is polyurethane.
Medical treatment of soft material to be inserted into the body according to 1, 2, 3 or 4
Tools.
2、3又は4記載の体内に挿入する軟質材料の医療用
具。 6. The medical device according to claim 1, wherein the medical device is a catheter.
Medical use of a soft material to be inserted into the body according to 2, 3 or 4
Utensils.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11897893A JP3341353B2 (en) | 1993-04-22 | 1993-04-22 | Medical equipment |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP11897893A JP3341353B2 (en) | 1993-04-22 | 1993-04-22 | Medical equipment |
Publications (2)
Publication Number | Publication Date |
---|---|
JPH06304244A JPH06304244A (en) | 1994-11-01 |
JP3341353B2 true JP3341353B2 (en) | 2002-11-05 |
Family
ID=14749995
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP11897893A Expired - Fee Related JP3341353B2 (en) | 1993-04-22 | 1993-04-22 | Medical equipment |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP3341353B2 (en) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5449747B2 (en) * | 2008-11-18 | 2014-03-19 | オリンパス株式会社 | Tube manufacturing method and tube |
JP4896245B2 (en) * | 2010-03-31 | 2012-03-14 | 朝日インテック株式会社 | Guide wire |
US20110301553A1 (en) * | 2010-06-04 | 2011-12-08 | Smiths Medical Asd, Inc. | Antimicrobial lubricant |
-
1993
- 1993-04-22 JP JP11897893A patent/JP3341353B2/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
JPH06304244A (en) | 1994-11-01 |
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