JP5904374B2 - Method for manufacturing a medical device having a lubricious surface - Google Patents
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本発明は湿潤時における潤滑性、潤滑耐久性、保水性に優れ、かつ治療時における血液や抗癌剤の影響を受けることなく高度な潤滑性を有する医療用具の製造方法を提供するものであり、ガイドワイヤー，カテーテルなどの医療用具の表面の機能化に有用な発明である。The present invention provides a method for producing a medical device that is excellent in lubricity when wet, lubrication durability, water retention, and has high lubricity without being affected by blood or anticancer agents during treatment. This invention is useful for functionalizing the surface of medical devices such as wires and catheters.
医療分野において、気管、消化管、尿管、血管、その他の体腔、又は、組織に挿入されるカテーテル、イントロデューサーおよびこれらに挿入されるガイドワイヤーなどの医療用具は、挿入時に目的部位にアクセスするための操作性を向上し、血管内壁や粘膜などへの組織損傷を最小限にするためには、潤滑性を有する表面が必要である。その目的のために、基材表面に親水性化合物をコートして、湿潤時における潤滑性を向上している。 In the medical field, a medical device such as a trachea, digestive tract, ureter, blood vessel, other body cavity, or a catheter inserted into a tissue, an introducer, and a guide wire inserted therein accesses a target site at the time of insertion. In order to improve operability and minimize tissue damage to the blood vessel inner wall and mucous membrane, a surface having lubricity is required. For that purpose, the surface of the substrate is coated with a hydrophilic compound to improve the lubricity when wet.
これまで，基材表面をイソシアネート化合物で処理した後，メチルビニルエーテル・無水マレイン酸共重合化合物あるいはそのハーフエチルエステルをコートすることで，湿潤時に表面が潤滑性を発現するようにした医療器具（文献１）などが知られている。しかしながら，メチルビニルエーテル・無水マレイン酸共重合化合物のハーフエチルエステルは，疎水性のエステル結合であることから，乾燥状態で保存された医療器具を水に濡らしても，すぐに潤滑性を発現しにくいこと，また，大気中に短時間放置するだけで，潤滑性を消失するなど，保水性の面において大きな欠点がある。一方，メチルビニルエーテル・無水マレイン酸共重合化合物のジカルボン酸ナトリウム塩は，前記ハーフエチルエステルに対して，潤滑性，保水性の面において有利であるものの，治療時に血液や抗癌剤の影響を受けて、表面潤滑性が大きく低下する欠点を有している。 Up to now, after treating the base material surface with an isocyanate compound, it is coated with methyl vinyl ether / maleic anhydride copolymer compound or its half ethyl ester so that the surface exhibits lubricity when wet (references) 1) etc. are known. However, half-ethyl ester of methyl vinyl ether / maleic anhydride copolymer compound is a hydrophobic ester bond, so that even when a medical device stored in a dry state is wetted with water, it is difficult to immediately exhibit lubricity. In addition, there are major drawbacks in terms of water retention, such as loss of lubricity just by leaving in the atmosphere for a short time. On the other hand, the sodium salt of dicarboxylic acid of methyl vinyl ether / maleic anhydride copolymer compound is advantageous in terms of lubricity and water retention compared to the half ethyl ester, but is affected by blood and anticancer agents during treatment. It has a drawback that the surface lubricity is greatly reduced.
本発明の目的は、上記の問題点に鑑みてなされたもので，湿潤時の保水性が良好で，潤滑性、潤滑耐久性に優れ、かつ，多価金属イオン、抗癌剤などの影響を受けることなく、潤滑性能が高度に保持される医療用具を提供することを目的とする。 The object of the present invention has been made in view of the above problems, has good water retention when wet, excellent lubricity and durability, and is affected by polyvalent metal ions, anticancer agents, and the like. An object of the present invention is to provide a medical device that maintains a high level of lubrication performance.
本発明者は鋭意検討した結果、上記目的は、下記（１），（２）により達成されることを見出し、本発明を完成するに至った。 As a result of extensive studies, the present inventor has found that the above object can be achieved by the following (1) and (2), and has completed the present invention.
（１）湿潤時に表面が潤滑性を有する医療用具を構成する基材の表面に、無水マレイン酸を一成分とする共重合化合物と一般式 ＲＯ−（ＣＨ２ＣＨ２Ｏ）ｎ−Ｈ（Ｒは炭素数１または２のアルキル基、ｎは２〜４の整数）で表される水酸基含有化合物との反応によって、共重合無水マレイン酸の５０〜１００モル％がハーフエステル化された無水マレイン酸共重合化合物を塗布、乾燥後、さらに、アルカリ処理することを特徴とする医療用具の製造方法。
（２）一般式 ＲＯ−（ＣＨ２ＣＨ２Ｏ）ｎ−Ｈで表わされる水酸基含有化合物において、Ｒのアルキル基の炭素数が１であり、ｎの数が３であることを特徴とする（１）に記載の医療用具の製造方法。 (1) on the surface of the substrate surface during the wetting constitute a medical device having a lubricious, a copolymer compound to one component of maleic anhydride with the general formula RO- (CH 2 CH 2 O) n-H (R alkyl group having 1 or 2 carbon atoms, n is by reaction with a hydroxyl group-containing compound represented by the integer from 2 to 4), a copolymer of 50 to 100 mol% of maleic acid half-esterified maleic anhydride A method for producing a medical device , characterized in that after the copolymer compound is applied and dried, it is further subjected to an alkali treatment .
(2) In the general formula RO- (CH 2 CH 2 O) a hydroxyl group-containing compound represented by n-H, a number of carbon atoms in the alkyl group of R 1, wherein the number of n is 3 ( The manufacturing method of the medical device as described in 1) .
本発明の目的は、各種基材表面に無水マレイン酸を一成分とする共重合化合物と一般式ＲＯ−（ＣＨ２ＣＨ２Ｏ）ｎ−Ｈで表される水酸基含有化合物との反応によって、共重合無水マレイン酸の５０〜１００モル％がハーフエステル化された無水マレイン酸共重合化合物をコーティングすることによって，優れた潤滑性、潤滑耐久性と保水性を付与するとともに、血液中あるいは抗癌剤の存在下においても高度な潤滑性、潤滑耐久性と保水性を有する医療器具を提供することにある。本発明に係る医療用具は湿潤時において、保水性が優れ，摩擦係数が低く，優れた潤滑性を有すると共に、実使用時における操作性に優れ、長期にわたり製品性能が変化することも無く，また，過酷な使用条件下においても潤滑性，潤滑耐久性、保水性を維持することが可能な医療用具が実現できる。The object of the present invention is to provide a copolymer by reacting a copolymer compound containing maleic anhydride as one component on the surface of various substrates with a hydroxyl group- containing compound represented by the general formula RO— (CH 2 CH 2 O) n—H. By coating maleic anhydride copolymer compound in which 50 to 100 mol% of polymerized maleic anhydride is half-esterified, it gives excellent lubricity, lubrication durability and water retention, and also exists in blood or anticancer agent The object is to provide a medical device having high lubricity, lubrication durability and water retention. The medical device according to the present invention has excellent water retention, low friction coefficient, excellent lubricity when wet, excellent operability in actual use, and product performance does not change over a long period of time. , A medical device capable of maintaining lubricity, lubrication durability and water retention even under severe use conditions can be realized.
本発明は医療用具を構成する各種基材表面に、無水マレイン酸を一成分とする共重合化合物と一般式 ＲＯ−（ＣＨ２ＣＨ２Ｏ）ｎ−Ｈ で表される水酸基含有化合物との反応によって、共重合無水マレイン酸の５０〜１００モル％がハーフエステル化された無水マレイン酸共重合化合物を基材表面に強固に固定化していることを特徴とする医療用具の製造方法である。具体的には，無水マレイン酸とメチルビニルエーテルの交互共重合化合物などを，一般式 ＲＯ−（ＣＨ２ＣＨ２Ｏ）ｎ−Ｈで表される水酸基含有化合物（Ｒは炭素数１または２のアルキル基、ｎの数は２〜４の整数）と反応させて得られたエステル結合を有する無水マレイン酸共重合化合物を基材表面にコートする方法などが採用しうる。Ｒのアルキル基の炭素数は１または２の時に、潤滑性、保水性、潤滑耐久性のすべてが良好であり、特に炭素数が１の場合に最も潤滑性、保水性、潤滑耐久性が優れる。また、Ｒが３より大きくなると疎水性が強くなり、潤滑性、保水性が劣る。ｎの数は１〜５の時に潤滑耐久性が優れ、また、変成された無水マレイン酸共重合化合物自体の粘着性が小さいことから、生産工程における工程通過性が良好である。一方、ｎの数が６以上と大きくなるに従って、製品表面の粘着性が増加し、工程通過性および製品品質に大きな問題を生じる。The present invention various substrate surfaces constituting the medical device, the reaction of the copolymerized compound to one component of maleic anhydride with the general formula RO- (CH 2 CH 2 O) a hydroxyl group-containing compound represented by the n-H by a method for producing a medical device, characterized in that 50 to 100 mole percent of copolymerized maleic anhydride is tightly fixed to the half-esterified maleic acid copolymer compound substrate surface anhydride. Specifically, an alternating copolymer of maleic anhydride and methyl vinyl ether is converted into a hydroxyl group- containing compound represented by the general formula RO— (CH 2 CH 2 O) n—H (R is an alkyl having 1 or 2 carbon atoms). A method of coating the surface of the base material with a maleic anhydride copolymer compound having an ester bond obtained by reacting with the group, the number of n being an integer of 2 to 4 may be employed. When the carbon number of the alkyl group of R is 1 or 2, the lubricity, water retention and lubrication durability are all good, and when the carbon number is 1, the lubricity, water retention and lubrication durability are most excellent. . Further, when R is larger than 3, the hydrophobicity becomes strong, and the lubricity and water retention are inferior. When the number of n is 1 to 5, the lubrication durability is excellent, and the modified maleic anhydride copolymer compound itself has low adhesiveness, so that the process passability in the production process is good. On the other hand, as the number of n increases to 6 or more, the tackiness of the product surface increases, resulting in significant problems in process passability and product quality.
一般式 ＲＯ−（ＣＨ２ＣＨ２Ｏ）ｎ−Ｈで表される水酸基含有化合物としては，ジエチレングリコールモノメチルエーテル，トリエチレングリコールモノメチルエーテル，テトラエチレングリコールモノメチルエーテル，ジエチレングリコールモノエチルエーテル，トリエチレングリコールモノエチルエーテル，テトラエチレングリコールモノエチルエーテルが挙げられる。中でも、特に好ましくは、トリエチレングリコールモノメチルエーテルである。The general formula RO- (CH 2 CH 2 O) a hydroxyl group-containing compound represented by the n-H, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, diethylene glycol monoethyl ether, triethylene glycol monoethyl Examples include ether and tetraethylene glycol monoethyl ether. Among these, triethylene glycol monomethyl ether is particularly preferable.
本発明において、各種無水マレイン酸共重合化合物、特に、メチルビニルエーテル・無水マレイン酸共重合化合物が好ましく用いられるが、これらの化合物中の無水マレイン酸を、ＲＯ−（ＣＨ２ＣＨ２Ｏ）ｎ−Ｈ で表される水酸基含有化合物によって、５０〜１００モル％の範囲で反応させて用いることができる。特に好ましい範囲は、６０〜９０モル％であり、潤滑性、保水性、潤滑耐久性、耐多価金属イオン性、耐抗癌剤性の総合性能において優れる。５０モル％未満では本発明の効果が小さくなり、十分な耐多価金属イオン性、耐抗癌剤性が得られない。In the present invention, various maleic anhydride copolymer compounds, particularly methyl vinyl ether / maleic anhydride copolymer compounds, are preferably used. The maleic anhydride in these compounds is represented by RO— (CH 2 CH 2 O) n—. Depending on the hydroxyl group- containing compound represented by H 2, it can be used in a range of 50 to 100 mol%. A particularly preferable range is 60 to 90 mol%, which is excellent in overall performance of lubricity, water retention, lubrication durability, polyvalent metal ion resistance and anticancer drug resistance. If it is less than 50 mol%, the effect of the present invention will be small, and sufficient multivalent metal ion resistance and anticancer drug resistance will not be obtained.
本発明における無水マレイン酸共重合化合物と架橋剤を上記の配合組成で混合した溶液を作成し、この溶液に浸漬する方法、溶液を塗布する方法、溶液を噴霧する方法など、従来から一般に採用されている方法を用いることができる。 A method in which a maleic anhydride copolymer compound and a crosslinking agent in the present invention are mixed in the above-described composition is prepared, and a method of immersing in this solution, a method of applying a solution, a method of spraying a solution, etc. have been generally employed. Can be used.
上記のコーティング溶液に用いられる溶剤としては、アセトン、メチルエチルケトンなどのケトン系溶剤、メタノール、エタノール、イソプロパノールなどのアルコール系溶剤、テトラヒドロフランあるいはそれらの混合溶剤、など汎用的な有機溶剤が使用しうる。これらの溶剤に、０．３〜８重量％、好ましくは０．５〜５重量％の濃度に溶解してコーティング溶液を調製する。 As the solvent used in the coating solution, a general-purpose organic solvent such as a ketone solvent such as acetone or methyl ethyl ketone, an alcohol solvent such as methanol, ethanol or isopropanol, tetrahydrofuran or a mixed solvent thereof can be used. A coating solution is prepared by dissolving in these solvents at a concentration of 0.3 to 8% by weight, preferably 0.5 to 5% by weight.
上記のコーティング溶液に浸漬した後、乾燥し、引き続き、６０〜１３０℃の温度で１０〜３００分の加熱処理を行う。 After being immersed in the above coating solution, it is dried and subsequently subjected to a heat treatment at a temperature of 60 to 130 ° C. for 10 to 300 minutes.
さらに、アルカリ溶液に浸漬し、エステル結合を有する無水マレイン酸共重合化合物のカルボキシル基をアルカリ塩にすることで、潤滑性、潤滑耐久性および保水性の優れた医療用具の製造が可能となる。このアルカリ処理に用いられるアルカリとしては、上記カルボキシル基をアルカリ塩へ変換する目的を達成できるアルカリであれば使用可能であるが、潤滑性、潤滑耐久性、保水性の点から、特に、水酸化ナトリウム、水酸化カリウムの水溶液、アルカリ金属アルコキサイドのアルコール溶液などで処理するのが最も良い結果を与える。また、アルカリ処理後、水、生理食塩水などで十分洗浄を行い、アルカリを完全に除去することが好ましい。 Furthermore, by immersing in an alkaline solution and converting the carboxyl group of the maleic anhydride copolymer compound having an ester bond to an alkali salt, it is possible to produce a medical device excellent in lubricity, lubrication durability and water retention. As the alkali used for the alkali treatment, any alkali can be used as long as it can achieve the purpose of converting the carboxyl group into an alkali salt. In particular, from the viewpoint of lubricity, lubrication durability, and water retention, hydroxylation can be performed. Treatment with an aqueous solution of sodium, potassium hydroxide, an alcohol solution of an alkali metal alkoxide, etc. gives the best results. Moreover, it is preferable to thoroughly remove the alkali by thoroughly washing with water, physiological saline or the like after the alkali treatment.
以下に本発明に係る具体的な実施例および比較例について、より詳しく説明するが、本発明は以下の例に限定されるものではない。
＜親水性化合物１＞Specific examples and comparative examples according to the present invention will be described in more detail below, but the present invention is not limited to the following examples.
<Hydrophilic compound 1>
メチルビニルエーテル・無水マレイン酸共重合化合物＜ＩＰＳ社製ＧＡＮＴＲＥＺ−ＡＮ−１６９＞の無水マレイン酸をトリエチレングリコールモノメチルエーテルによって８０モル％変性した部分エステルの３重量％ＭＥＫを調製した（コーティング溶液＜１＞）。
＜親水性化合物２＞Methyl vinyl ether / maleic anhydride copolymer compound <GANTREZ-AN-169 manufactured by IPS Co., Ltd.> 3 wt% MEK of a partial ester obtained by modifying 80 mol% of maleic anhydride with triethylene glycol monomethyl ether was prepared (coating solution <1 >).
<Hydrophilic compound 2>
メチルビニルエーテル・無水マレイン酸共重合化合物＜ＩＰＳ社製ＧＡＮＴＲＥＺ−ＡＮ−１６９＞の無水マレイン酸をトリエチレングリコールモノメチルエーテルによって４０モル％変性した部分エステルの３重量％ＭＥＫ溶液を調製した（コーティング溶液＜２＞）。
＜親水性化合物３＞A 3 wt% MEK solution of a partial ester obtained by modifying maleic anhydride of methyl vinyl ether / maleic anhydride copolymer compound <GANTREZ-AN-169 manufactured by IPS> with triethylene glycol monomethyl ether was prepared (coating solution <2>).
<Hydrophilic compound 3>
メチルビニルエーテル・無水マレイン酸共重合化合物＜ＩＰＳ社製ＧＡＮＴＲＥＺ−ＡＮ−１６９＞の無水マレイン酸をジエチレングリコールモノメチルエーテルによって８０モル％変性した部分エステルの３重量％ＭＥＫ溶液を調製した（コーティング溶液＜３＞）。
＜親水性化合物４＞Methyl vinyl ether-maleic acid copolymer compound was prepared 3 wt% MEK solution of 80 mol% modified partial ester of maleic anhydride by the di- ethylene glycol monomethyl ether <IPS Corporation GANTREZ-AN-169> (coating solution <3>).
<Hydrophilic compound 4>
メチルビニルエーテル・無水マレイン酸共重合化合物＜ＩＰＳ社製ＧＡＮＴＲＥＺ−ＡＮ−１６９＞の無水マレイン酸をエタノールによって８０モル％変性した部分エステルの３重量％ＭＥＫ溶液を調製した（コーティング溶液＜４＞）。
＜実施例１＞A 3 wt% MEK solution of a partial ester obtained by modifying 80 mol% of maleic anhydride of a methyl vinyl ether / maleic anhydride copolymer compound <GANTREZ-AN-169 manufactured by IPS> with ethanol was prepared (coating solution <4>).
<Example 1>
ウレタン樹脂で被覆した血管造影用ガイドワイヤーの基材に、上記に調製したコーティング溶液＜１＞に浸漬することによって基材表面にコーティング溶液＜１＞を塗布し，乾燥し、潤滑剤を基材表面に固定した。その後，水酸化ナトリウムの水溶液中に浸漬処理した。さらに，水洗を行い，乾燥した。上記方法にて得られたワイヤーは水の中において優れた潤滑性を示した。また，このワイヤーを水の中において手で扱くことにより，潤滑性が消失するまでの手扱きの回数を測定したが３０００回まで潤滑性を維持し，潤滑耐久性が優れることが確認された。さらに、保水性にも優れ、ワイヤーを吸水させた後に大気中に５分間放置しても，十分な潤滑性を有しており，保水性の面においても優れていた。また、生理食塩水に塩化カルシウムを０．１重量％濃度に溶解した水溶液に、ワイヤーを１時間浸漬後、水洗した後、ワイヤーを水の中において手で扱くことにより，潤滑性が消失するまでの手扱きの回数を測定したが２６００回まで潤滑性を維持し、性能の低下はほとんど認められなかった。
＜実施例２＞The coating solution <1> is applied to the surface of the base material by immersing it in the coating solution <1> prepared above on the base material of the angiography guide wire coated with urethane resin, and the lubricant is applied to the base material. Fixed to the surface. Then, it was immersed in an aqueous solution of sodium hydroxide. Further, it was washed with water and dried. The wire obtained by the above method showed excellent lubricity in water. In addition, when this wire was handled by hand in water, the number of times that the lubrication was lost was measured, but it was confirmed that the lubricity was maintained up to 3000 times and the lubrication durability was excellent. . Furthermore, it was excellent in water retention, and even if it was allowed to stand in the air for 5 minutes after absorbing the wire, it had sufficient lubricity and was excellent in terms of water retention. Also, after immersing the wire in an aqueous solution of calcium chloride dissolved in physiological saline at a concentration of 0.1% by weight for 1 hour, washing with water, and then handling the wire in water, the lubricity is lost. The number of times of handling was measured, but the lubricity was maintained up to 2600 times, and almost no deterioration in performance was observed.
<Example 2>
ウレタン樹脂で被覆した血管造影用ガイドワイヤーの基材に、上記に調製したコーティング溶液＜３＞に浸漬することによって基材表面にコーティング溶液＜３＞を塗布し、乾燥して、潤滑剤を基材表面に固定した。その後，水酸化ナトリウムの水溶液中に浸漬処理した。さらに，水洗を行い，乾燥した。上記方法にて得られたワイヤーは水の中において優れた潤滑性を示した。また，このワイヤーを水の中において手で扱くことにより，潤滑性が消失するまでの手扱きの回数を測定したが２８００回まで潤滑性を維持し，潤滑耐久性が優れることが確認された。さらに、保水性にも優れ、ワイヤーを吸水させた後に大気中に５分間放置しても，十分な潤滑性を有しており，保水性の面においても優れていた。また、生理食塩水に塩化カルシウムを０．１重量％濃度に溶解した水溶液に、ワイヤーを１時間浸漬後、水洗した後、ワイヤーを水の中において手で扱くことにより，潤滑性が消失するまでの手扱きの回数を測定したが２５００回まで潤滑性を維持し、性能の低下はほとんど認められなかった。
＜比較例１＞Apply the coating solution <3> on the surface of the base material by immersing it in the coating solution <3> prepared above on the base material of the angiography guide wire coated with urethane resin, and dry it. Fixed to the material surface. Then, it was immersed in an aqueous solution of sodium hydroxide. Further, it was washed with water and dried. The wire obtained by the above method showed excellent lubricity in water. In addition, when this wire was handled by hand in water, the number of times of handling until the lubricity disappeared was measured, but it was confirmed that the lubricity was maintained up to 2800 times and the lubrication durability was excellent. . Furthermore, it was excellent in water retention, and even if it was allowed to stand in the air for 5 minutes after absorbing the wire, it had sufficient lubricity and was excellent in terms of water retention. Also, after immersing the wire in an aqueous solution of calcium chloride dissolved in physiological saline at a concentration of 0.1% by weight for 1 hour, washing with water, and then handling the wire in water, the lubricity is lost. The number of times of handling was measured, but the lubricity was maintained up to 2500 times, and the performance was hardly deteriorated.
<Comparative Example 1>
ウレタン樹脂で被覆した血管造影用ガイドワイヤーの基材に、上記に調製したコーティング溶液＜２＞に浸漬することによって基材表面にコーティング溶液＜２＞を塗布し，乾燥して、潤滑剤を基材表面に固定した。その後，水酸化ナトリウムの水溶液中に浸漬処理した。さらに，水洗を十分に行い，乾燥した。上記方法にて得られたワイヤーは水の中において優れた潤滑性を示した。また，このワイヤーを水の中において手で扱くことにより，潤滑性が消失するまでの手扱きの回数を測定したが２８００回まで潤滑性を維持し，潤滑耐久性が優れることが確認された。さらに、保水性にも優れ、ワイヤーを吸水させた後に大気中に５分間放置しても，十分な潤滑性を有しており，保水性の面においても優れていた。しかしながら、生理食塩水に塩化カルシウムを０．１重量％濃度に溶解した水溶液に、ワイヤーを１時間浸漬後、水洗した後、ワイヤーを水の中において手で扱くことによって潤滑性が消失するまでの手扱きの回数を測定したが、６００回までに潤滑耐久性が低下していた。
＜比較例２＞Apply the coating solution <2> on the surface of the base material by immersing it in the coating solution <2> prepared above on the base material of the angiography guide wire coated with urethane resin, and dry it. Fixed to the material surface. Then, it was immersed in an aqueous solution of sodium hydroxide. Furthermore, it was washed thoroughly with water and dried. The wire obtained by the above method showed excellent lubricity in water. In addition, when this wire was handled by hand in water, the number of times of handling until the lubricity disappeared was measured, but it was confirmed that the lubricity was maintained up to 2800 times and the lubrication durability was excellent. . Furthermore, it was excellent in water retention, and even if it was allowed to stand in the air for 5 minutes after absorbing the wire, it had sufficient lubricity and was excellent in terms of water retention. However, after immersing the wire in an aqueous solution of calcium chloride dissolved in physiological saline at a concentration of 0.1% by weight for 1 hour, washing the wire, and then handling the wire in water until the lubricity disappears The number of times of handling was measured, but the lubrication durability had decreased by 600 times.
<Comparative Example 2>
ウレタン樹脂で被覆した血管造影用ガイドワイヤーの基材に、メチルビニルエーテル無水マレイン酸共重合化合物＜ＩＰＳ社製ＧＡＮＴＲＥＺ−ＡＮ−１６９＞の３重量％ＭＥＫ溶液に浸漬することによって、コーティングし，乾燥を行なって、潤滑剤を基材表面に固定した。その後，水酸化ナトリウムの水溶液中に浸漬し，処理した。さらに，水洗を十分に行い，乾燥した。上記方法にて得られたワイヤーは水の中において優れた潤滑性を示した。また，このワイヤーを水の中において手で扱くことにより，潤滑性が消失するまでの手扱きの回数を測定したが３０００回まで潤滑性を維持し，潤滑耐久性が優れることが確認された。さらに、保水性にも優れ、ワイヤーを吸水させた後に大気中に５分間放置しても，十分な潤滑性を有しており，保水性の面においても優れていた。しかしながら、生理食塩水に塩化カルシウムを０．１重量％濃度に溶解した水溶液に、ワイヤーを１時間浸漬後、水洗したワイヤーを水の中において手で扱くことにより，潤滑性が消失するまでの手扱きの回数を測定したが、２００回までに潤滑耐久性が低下していた。
＜比較例３＞An angiographic guidewire substrate coated with a urethane resin is coated by immersing it in a 3% by weight MEK solution of a methyl vinyl ether maleic anhydride copolymer compound <GANTREZ-AN-169 manufactured by IPS> and dried. In operation, the lubricant was fixed to the substrate surface. Then, it was immersed in an aqueous solution of sodium hydroxide and treated. Furthermore, it was washed thoroughly with water and dried. The wire obtained by the above method showed excellent lubricity in water. In addition, when this wire was handled by hand in water, the number of times that the lubrication was lost was measured, but it was confirmed that the lubricity was maintained up to 3000 times and the lubrication durability was excellent. . Furthermore, it was excellent in water retention, and even if it was allowed to stand in the air for 5 minutes after absorbing the wire, it had sufficient lubricity and was excellent in terms of water retention. However, by immersing the wire in an aqueous solution of calcium chloride dissolved in physiological saline at a concentration of 0.1% by weight for 1 hour and then handling the washed wire by hand in water, the lubricity disappears. The number of times of handling was measured, but the lubrication durability was lowered by 200 times.
<Comparative Example 3>
ウレタン樹脂で被覆した血管造影用ガイドワイヤーの基材に、上記に調製したコーティング溶液＜４＞に浸漬することによって基材表面にコーティング溶液＜４＞を塗布し，乾燥を行ない、潤滑剤を基材表面に固定した。その後，水酸化ナトリウムの水溶液中に浸漬処理した。さらに，水洗を行い，乾燥した。上記方法にて得られたワイヤーは水の中において優れた潤滑性を示した。また，このワイヤーを水の中において手で扱くことにより，潤滑性が消失するまでの手扱きの回数を測定したが２５００回まで潤滑性を維持し，潤滑耐久性が優れることが確認された。また、生理食塩水に塩化カルシウムを０．１重量％濃度に溶解した水溶液に、ワイヤーを１時間浸漬後、水洗した後、ワイヤーを水の中において手で扱くことにより，潤滑性が消失するまでの手扱きの回数を測定したが２２００回まで潤滑性を維持し、性能の低下はほとんど認められなかった。しかしながら、ワイヤーを吸水させた後に大気中に２分間放置するだけで，潤滑性はかなり消失しており，３分後には完全に潤滑性は消失しており、保水性が大きく劣っていた。 Apply the coating solution <4> to the surface of the base material by immersing it in the coating solution <4> prepared above on the base material of the angiography guide wire coated with urethane resin, and dry it. Fixed to the material surface. Then, it was immersed in an aqueous solution of sodium hydroxide. Further, it was washed with water and dried. The wire obtained by the above method showed excellent lubricity in water. In addition, when this wire was handled by hand in water, the number of times that the lubrication was lost was measured, but it was confirmed that the lubricity was maintained up to 2500 times and the lubrication durability was excellent. . Also, after immersing the wire in an aqueous solution of calcium chloride dissolved in physiological saline at a concentration of 0.1% by weight for 1 hour, washing with water, and then handling the wire in water, the lubricity is lost. The number of times of handling was measured, but the lubricity was maintained up to 2200 times, and almost no deterioration in performance was observed. However, after the wire was absorbed in water and left in the atmosphere for 2 minutes, the lubricity disappeared considerably. After 3 minutes, the lubricity completely disappeared and the water retention was greatly inferior.
本発明により得られる技術によって、カルシウムイオンなど多価金属イオンに対しても優れた潤滑性、潤滑耐久性、保水性および耐多価金属イオン性を有するガイドワイヤーなどの医療用具を提供することが可能になった。特に、これまで、金属基材に無水マレイン酸共重合化合物をコーティングし、水酸化ナトリウムなどのアルカリで処理したガイドワイヤーは、血液や抗癌剤などによって潤滑性および潤滑耐久性が低下する傾向が強かったが、本発明に係るコーティング技術によって、これらの問題が解消され、新しい機能を有する医療用具などへの展開を含めた幅広い応用が期待できる。 By the technique obtained by the present invention, it is possible to provide a medical device such as a guide wire having excellent lubricity, lubrication durability, water retention and polyvalent metal ion resistance against polyvalent metal ions such as calcium ions. It became possible. In particular, until now, guidewires coated with a maleic anhydride copolymer compound on a metal substrate and treated with an alkali such as sodium hydroxide have had a strong tendency to decrease lubricity and lubrication durability due to blood and anticancer agents. However, with the coating technology according to the present invention, these problems are solved, and a wide range of applications including the development of medical devices having new functions can be expected.
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