JPH11114051A - Medical device having lubricating coating and method of manufacturing the same - Google Patents
Medical device having lubricating coating and method of manufacturing the sameInfo
- Publication number
- JPH11114051A JPH11114051A JP9286737A JP28673797A JPH11114051A JP H11114051 A JPH11114051 A JP H11114051A JP 9286737 A JP9286737 A JP 9286737A JP 28673797 A JP28673797 A JP 28673797A JP H11114051 A JPH11114051 A JP H11114051A
- Authority
- JP
- Japan
- Prior art keywords
- lubricating coating
- medical device
- solvent
- coating
- lubricating
- 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.)
- Granted
Links
- 238000000576 coating method Methods 0.000 title claims abstract description 84
- 239000011248 coating agent Substances 0.000 title claims abstract description 81
- 230000001050 lubricating effect Effects 0.000 title claims description 77
- 238000004519 manufacturing process Methods 0.000 title claims description 19
- 239000002904 solvent Substances 0.000 claims abstract description 36
- 239000004814 polyurethane Substances 0.000 claims abstract description 17
- 229920005862 polyol Polymers 0.000 claims abstract description 12
- 150000003077 polyols Chemical class 0.000 claims abstract description 12
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 10
- 150000008065 acid anhydrides Chemical class 0.000 claims abstract description 6
- 229920001577 copolymer Polymers 0.000 claims abstract description 6
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 229920002635 polyurethane Polymers 0.000 claims abstract description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 7
- 229920002803 thermoplastic polyurethane Polymers 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 11
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 abstract description 5
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 abstract description 5
- 230000002785 anti-thrombosis Effects 0.000 abstract description 4
- 239000000314 lubricant Substances 0.000 abstract description 2
- 230000021615 conjugation Effects 0.000 abstract 1
- 238000009736 wetting Methods 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 64
- 239000000243 solution Substances 0.000 description 43
- UPBDXRPQPOWRKR-UHFFFAOYSA-N furan-2,5-dione;methoxyethene Chemical compound COC=C.O=C1OC(=O)C=C1 UPBDXRPQPOWRKR-UHFFFAOYSA-N 0.000 description 18
- 229920001451 polypropylene glycol Polymers 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000007788 liquid Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 230000032683 aging Effects 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 229920005603 alternating copolymer Polymers 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- DSUFPYCILZXJFF-UHFFFAOYSA-N 4-[[4-[[4-(pentoxycarbonylamino)cyclohexyl]methyl]cyclohexyl]carbamoyloxy]butyl n-[4-[[4-(butoxycarbonylamino)cyclohexyl]methyl]cyclohexyl]carbamate Chemical group C1CC(NC(=O)OCCCCC)CCC1CC1CCC(NC(=O)OCCCCOC(=O)NC2CCC(CC3CCC(CC3)NC(=O)OCCCC)CC2)CC1 DSUFPYCILZXJFF-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000005461 lubrication Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 210000000056 organ Anatomy 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000011982 device technology Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は潤滑性被覆を有する
医療用具及びその製造方法に関し、特にカテーテルその
他やこれらの付属品等の医療用具の内の潤滑性被覆を有
する医療用具及びその製造方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a medical device having a lubricating coating and a method of manufacturing the same, and more particularly to a medical device having a lubricating coating in a medical device such as a catheter and other accessories, and a method of manufacturing the same. Things.
【０００２】[0002]
【従来の技術】医療用具技術の発展に伴い、その使用時
に特に器官や組織等の人体に対して高度の安全性を備え
た医療用具が必須となってきた。すなわち、例えば湿潤
時にその表面が潤滑性を有する医療用具として初めて開
示された特公平１−３３１８１号公報の技術をはじめと
して、潤滑性被覆を有する医療用具及びその製造方法に
関する文献は枚挙に暇がない程である。そして、最近公
開され「表面潤滑性付与剤」と題する発明に関する代表
的な文献として、例えば特開平５−３００９４０号公報
が挙げられる。2. Description of the Related Art With the development of medical device technology, a medical device having a high degree of safety, especially for a human body such as an organ or a tissue, has become indispensable when used. That is, for example, the technique disclosed in Japanese Patent Publication No. 1-33181, which was disclosed for the first time as a medical device having a lubricating surface when wet, and a literature on a medical device having a lubricating coating and a method for manufacturing the same have many times. Not so much. As a representative document relating to the invention recently disclosed and entitled "Surface lubricity imparting agent", for example, JP-A-5-300940 can be mentioned.
【０００３】これまでの開示技術の要点は、基材表面へ
の親水性ポリマーの各種重合手段、又は表面に形成した
反応性基と活性水素を持つ有機溶媒可溶性成分を含有す
る親水性ポリマーとを実質的に有機溶媒中で反応させ
て、基材表面に親水性を付与するものである。また、湿
潤潤滑性コーティングに関する技術は、その主要素材に
よって分類すると、「ガントレッツ系」、「ポリビニル
ピロリドン系」、「ポリエチレングリコール系」があ
る。そして、基材への固定方法としては、すべて、共有
結合、又はイオン結合等の化学反応を利用するものであ
る。なお、上述の「ガントレッツ」は、ＧＡＦ（ゼネラ
ル アニリン アンド フイルム コーポレーション）
社の商品名であるが、ポリ（無水マレイン酸−メチルビ
ニルエーテル）交互共重合体として、業界では広く慣用
されている材料物質名であるので、敢えて使用したもの
である。[0003] The point of the disclosed technology so far is to use various means for polymerizing a hydrophilic polymer on the surface of a substrate or a hydrophilic polymer containing a reactive group formed on the surface and an organic solvent-soluble component having active hydrogen. Substantially reacting in an organic solvent to impart hydrophilicity to the substrate surface. In addition, the technologies relating to the wet lubricating coating are classified into “Gantrez-based”, “polyvinylpyrrolidone-based”, and “polyethylene glycol-based” when classified according to their main materials. And, as a method for fixing to a substrate, all use a chemical reaction such as a covalent bond or an ionic bond. The above “Gantrez” is GAF (General Aniline and Film Corporation)
Although it is a trade name of a company, it is used as a poly (maleic anhydride-methyl vinyl ether) alternating copolymer because it is a material name widely used in the industry.
【０００４】上述のような従来の湿潤潤滑コートは、基
材の最外層に均一な層を形成し、その層が水に触れると
多量の水を吸収し、同時にヌルヌルした感触になるよう
なコーティングであった。このヌルヌルが湿潤潤滑性の
付与に対して重要な因子であり、これによって医療器具
の挿着時における例えば人体等に対する相対的な移動に
対して、人体の器官や組織に対して物理的なだけでなく
例えば抗血栓性のような生理的な円滑性をも付与するの
で、安全性の高い医療器具が達成できるようになる。[0004] The conventional wet lubricating coat as described above forms a uniform layer on the outermost layer of the substrate, and when the layer comes into contact with water, it absorbs a large amount of water and at the same time has a slimy feel. Met. This slimy is an important factor for imparting wet lubricity, so that it is only physically attached to the organs and tissues of the human body, for example, with respect to the relative movement with respect to the human body when the medical device is inserted. In addition, it also provides physiological smoothness such as antithrombotic properties, so that a highly safe medical device can be achieved.
【０００５】[0005]
【発明が解決しようとする課題】上述のように従来の潤
滑性被覆を有する医療用具及びその製造方法は、全述の
ように、基材への固定方法としてはすべて共有結合、又
はイオン結合等の化学反応を利用するものでるから、製
造方法が複雑であり、大幅なコストアップにつながると
いう問題があった。また、従来の湿潤潤滑コートは、当
然のことながら水を吸収した場合大きく膨潤するので、
表面に皺が発生したり、残留応力のために擦ると剥げ落
ち易い等の問題があった。また、このため潤滑性能の持
続性も十分とは言えない問題が解決できない状況であっ
た。As described above, the conventional medical device having a lubricating coating and the method of manufacturing the same all use a covalent bond or an ionic bond as a method of fixing to a base material, as described in all aspects. However, there is a problem in that the production method is complicated and the cost is greatly increased because the chemical reaction is used. Also, conventional wet lubricating coats naturally swell greatly when absorbing water,
There were problems such as wrinkles on the surface and easy peeling off when rubbed due to residual stress. In addition, the problem that the durability of the lubricating performance is not sufficient cannot be solved.
【０００６】[0006]
【課題を解決するための手段】本発明に係る潤滑性被覆
を有する医療用具は、不飽和結合を有する酸無水物の例
えば無水マレイン酸と非共役型ビニルモノマーの例えば
メチルビニルエーテルとの交互共重合体の溶液に、架橋
剤のポリオールの溶液を加え、これにポリウレタンの溶
液を加えて形成した潤滑性被覆用溶剤を医療用具の基材
表面に塗布して形成した湿潤潤滑層が微細な多孔性被膜
状のスポンジ体としたものである。ここで、前記ポリオ
ールはポリプロピレングリコールであり、前記有機溶媒
はテトラヒドロフランであることが好ましい。According to the present invention, there is provided a medical device having a lubricating coating comprising an alternating copolymer of an acid anhydride having an unsaturated bond such as maleic anhydride and a non-conjugated vinyl monomer such as methyl vinyl ether. A wet lubricating layer formed by applying a lubricating coating solvent formed by adding a solution of a crosslinking agent polyol to the coalesced solution and then adding a polyurethane solution thereto to the substrate surface of the medical device has a fine porosity. It is a sponge in the form of a film. Here, the polyol is preferably polypropylene glycol, and the organic solvent is preferably tetrahydrofuran.
【０００７】本発明に係る潤滑性被覆を有する医療用具
の製造方法は、不飽和結合を有する酸無水物の例えば無
水マレイン酸と非共役型ビニルモノマーの例えばメチル
ビニルエーテルとの共重合体、架橋剤のポリオール及び
ウレタン樹脂を所定比率で有機溶媒に溶解して潤滑性被
覆用溶剤を形成し、この潤滑性被覆用溶剤を医療用具の
基材表面に塗布してスポンジ状の微細多孔性被膜を形成
するものである。この場合、前記架橋剤のポリオールに
はポリプロピレングリコールを使用し、前記有機溶媒に
はテトラヒドロフランを使用するのが好適である。The method for producing a medical device having a lubricating coating according to the present invention comprises a copolymer of an acid anhydride having an unsaturated bond such as maleic anhydride and a non-conjugated vinyl monomer such as methyl vinyl ether; Polyol and urethane resin are dissolved in an organic solvent at a predetermined ratio to form a lubricating coating solvent, and this lubricating coating solvent is applied to the base surface of a medical device to form a sponge-like microporous coating. Is what you do. In this case, it is preferable to use polypropylene glycol as the polyol of the cross-linking agent and to use tetrahydrofuran as the organic solvent.
【０００８】また、前項の潤滑性被覆を有する医療用具
の１つの製造方法においては、使用する潤滑性被覆用溶
剤は液温を２０℃以下で形成し、この潤滑性被覆用溶剤
による医療用具の基材表面への塗布時の液温も２０℃以
下で浸漬・塗布して均一性被膜を形成することが必要と
なる。In one method for producing a medical device having a lubricating coating as described in the preceding paragraph, the lubricating coating solvent used is formed at a liquid temperature of 20 ° C. or lower, and the medical device is manufactured using the lubricating coating solvent. It is necessary to form a uniform coating by immersing and applying the liquid at a temperature of 20 ° C. or less at the time of application to the substrate surface.
【０００９】さらに、前前項の潤滑性被覆を有する医療
用具の別の製造方法においては、潤滑性被覆用溶剤の形
成において使用する無水マレイン酸とメチルビニルエー
テルとの共重合体の有機溶媒への所定比率溶液は、溶解
後この溶液を少なくとも７２時間放置して熟成溶液とし
たものを使用することが可能である。Further, in another method for producing a medical device having a lubricating coating according to the preceding item, the method for producing a solvent for a lubricating coating includes the step of converting a copolymer of maleic anhydride and methyl vinyl ether into an organic solvent. As the ratio solution, it is possible to use a solution obtained by allowing the solution to stand for at least 72 hours after dissolution to form an aging solution.
【００１０】[0010]
【発明の実施の形態】本発明による潤滑性被覆を有する
医療用具は、前述のような潤滑性被覆用溶剤を形成しこ
の潤滑性被覆用溶剤を、所定のコーティング法に従って
医療用具の表面に塗布することによって得られる。従っ
て、次に示す本発明の実施の形態の説明では、主として
２種類の標準的な潤滑性被覆用溶剤の製造方法及びコー
ティング方法についてそれぞれ述べる。DETAILED DESCRIPTION OF THE INVENTION A medical device having a lubricating coating according to the present invention forms a lubricating coating solvent as described above and applies the lubricating coating solvent to the surface of the medical device according to a predetermined coating method. It is obtained by doing. Therefore, in the following description of the embodiment of the present invention, mainly, two types of standard lubricating coating solvent production methods and coating methods will be described.
【００１１】［第１の実施形態］本実施形態において
は、１つの標準的製造方法及びそのコーティング方法に
ついて説明する。まず、無水マレイン酸とメチルビニル
エーテルの共重合体として市販されているガントレッツ
ＡＮ−１３９（ＧＡＦ社製：分子量ＭＷ；約４１，０
００）を溶媒の例えばテトラヒドロフラン（以下ＴＨＦ
と略称する）で溶解し、ガントレッツの７％ＴＨＦ溶液
を作製する。なお、ガントレッツのグレードはＡＮ−１
３９に限定されず、他の高分子タイプのものでもよい。
次いで、ポリウレタン樹脂（市販名，ＥＡ１００Ａ：以
下ＰＵＲと略称する）をＴＨＦで溶解し、ＰＵＲの５％
ＴＨＦ溶液を作製する。このＰＵＲとしてもテコフレッ
クスであれば、ＥＧ８５Ａ〜ＥＧ６５Ｄまで使用可能で
ある。さらに、架橋剤のポリプロピレングリコールの１
０％ＴＨＦ溶液を作製する。このポリプロピレングリコ
ールとしてはポリオールであればどれでもよいが、架橋
効率を上げるために分子量３０００、グリコールタイプ
のものを使用するのが好都合である。上述のガントレッ
ツの７％ＴＨＦ溶液、ＰＵＲの５％ＴＨＦ溶液及びポリ
プロピレングリコールの１０％ＴＨＦ溶液の３種の溶液
を潤滑性被覆用溶剤の原料として準備しておく。[First Embodiment] In this embodiment, one standard manufacturing method and its coating method will be described. First, Gantrez AN-139 (manufactured by GAF: molecular weight MW; about 41,0, commercially available as a copolymer of maleic anhydride and methyl vinyl ether)
00) as a solvent such as tetrahydrofuran (hereinafter THF)
To make a 7% THF solution of Gantrez. The grade of Gantrez is AN-1
It is not limited to 39, but may be another polymer type.
Next, a polyurethane resin (commercial name, EA100A: hereinafter abbreviated as PUR) was dissolved in THF, and 5% of the PUR was dissolved.
Make a THF solution. As long as this PU is Tecoflex, EG85A to EG65D can be used. Furthermore, one of the crosslinking agents polypropylene glycol
Make a 0% THF solution. As the polypropylene glycol, any polyol may be used, but it is convenient to use a glycol type having a molecular weight of 3000 and a glycol type in order to increase the crosslinking efficiency. Three kinds of the above-mentioned Gantrez 7% THF solution, PUR 5% THF solution and polypropylene glycol 10% THF solution are prepared as raw materials for the lubricating coating solvent.
【００１２】次に、以上の３種の溶液を使用して形成す
る潤滑性被覆用溶剤の製造手順について述べる。まず、
ガントレッツの７％ＴＨＦ溶液１００（重量比）に対し
て、１０（重量比）のポリプロピレングリコールの１０
％ＴＨＦ溶液を添加する。添加後、充分に攪拌する。攪
拌により均一に溶液が得られたところで、これに１００
（重量比）のＰＵＲの５％ＴＨＦ溶液を加えて２０℃以
下の液温で攪拌することにより、潤滑性被覆用溶剤の製
造が完了する。この場合、液温が２０℃以上になると均
一性がなくなるので、攪拌後は冷蔵庫中で保管する。そ
して、この製造方法及び保管法で、得られた潤滑性被覆
用溶剤は１ケ月程度は変質しないことが確認されてい
る。Next, the procedure for producing a solvent for a lubricating coating formed using the above three kinds of solutions will be described. First,
Gantrez 7% THF solution 100 (weight ratio) and 10 (weight ratio) of polypropylene glycol 10
Add the% THF solution. After addition, agitate well. When a uniform solution was obtained by stirring, 100
A 5% THF solution of PUR (by weight) is added and stirred at a liquid temperature of 20 ° C. or less, whereby the production of the lubricating coating solvent is completed. In this case, if the liquid temperature is 20 ° C. or more, the liquid will not be uniform, and therefore, it is stored in a refrigerator after stirring. It has been confirmed that the lubricating coating solvent obtained by this production method and storage method does not deteriorate for about one month.
【００１３】この潤滑性被覆用溶剤を用いて、医療用具
の表面に潤滑性被覆をコーティングする要領を下記の工
程順にしたがって示す。 （１）温度制御が可能な潤滑被覆形成用の容器に所定量
の前述の潤滑性被覆用溶剤を入れ、溶剤を含む全体の系
の温度を２０℃以下に設定する。 （２）医療用具の基材として、例えばポリウレタン製の
カテーテルを潤滑性被覆用溶剤中に浸漬した後、５ｍ／
分以上の比較的速い速度で引き上げる。 （３）引上げ後、カテーテルの例えば端部に溜まった液
は、内腔から空気を吹き付けて飛ばしてやる。 （４）この状態で６０℃×４８時間、又は７０℃×２４
時間の熱処理を行う。 （５）その後、０．１ＮのＮａＯＨ水溶液に浸漬した
後、５ｍ／分以上の比較的速い速度で引き上げる。 （６）さらに蒸溜水で洗浄した後、６０℃×２４時間の
乾燥を行い、カテーテル表面への潤滑性被覆のコーティ
ングを終了する。A procedure for coating a lubricating coating on the surface of a medical device using the lubricating coating solvent will be described in the following order of steps. (1) A predetermined amount of the above-mentioned solvent for forming a lubricating coating is placed in a container for forming a lubricating coating capable of controlling the temperature, and the temperature of the entire system including the solvent is set to 20 ° C. or lower. (2) As a base material of a medical device, a catheter made of, for example, polyurethane is immersed in a solvent for lubricating coating, and then 5 m /
Pull up at a relatively fast speed of more than a minute. (3) After withdrawal, the liquid collected at, for example, the end of the catheter is blown off by blowing air from the lumen. (4) In this state, 60 ° C. × 48 hours, or 70 ° C. × 24
Heat treatment for a time is performed. (5) Then, after being immersed in a 0.1N NaOH aqueous solution, it is pulled up at a relatively high speed of 5 m / min or more. (6) After further washing with distilled water, drying at 60 ° C. for 24 hours is performed to complete the coating of the catheter surface with the lubricating coating.
【００１４】なお、本実施形態において、ガントレッツ
の７％ＴＨＦ溶液１００に対して、１０のポリプロピレ
ングリコールの１０％ＴＨＦ溶液を添加し、攪拌により
均一に溶液が得られたところで、これに１００（重量
比）のＰＵＲの５％ＴＨＦ溶液を加えて２０℃以下の液
温で攪拌すること、さらに容器に所定量の前述の潤滑性
被覆用溶剤を入れ、溶剤を含む全体の系の温度を２０℃
以下に設定することが必須であるが、これは液温が２０
℃以上になると層分離を生じ、この状態でコーティング
しても持続性が十分に確保できなくなるからである。つ
まり被覆に均一性がなくなり、表面が若干粗になり艶消
しタイプになるからである。In this embodiment, a 10% THF solution of 10 polypropylene glycol was added to 100% of a 7% THF solution of Gantrez, and the solution was uniformly obtained by stirring. 5% THF solution of PUR in the above ratio) and stirring at a liquid temperature of 20 ° C. or less. Further, a predetermined amount of the above-mentioned lubricating coating solvent is put in a container, and the temperature of the entire system including the solvent is lowered to 20 ° C.
It is essential to set the following, but this is because the liquid temperature is 20
If the temperature exceeds ℃, layer separation occurs, and even if coating is performed in this state, sufficient durability cannot be ensured. In other words, the uniformity of the coating is lost, the surface becomes slightly rough, and a matte type is obtained.
【００１５】以上のように第１の実施形態によれば、潤
滑性被覆の基材への固定に何等の化学反応を必要としな
いで単に塗布膜を形成するだけで、潤滑（ヌルヌル）効
果とその持続性に優れた潤滑性被覆のコーティングが達
成される。ここで、吸水時のこの潤滑性被覆を走査型電
子顕微鏡のＳＥＭ像で観察したところ、写真の呈示は省
略するが、平均穴径が数１０μｍ〜数１００μｍのスポ
ンジ状の被膜であることが判明した。つまり、このよう
にスポンジ状（連続気泡）が形成されることによって、
水を吸収して膨潤しても基材との接着面に大きな応力集
中が起きなくなり、結果として、接着強度が大幅に向上
した。さらに、この場合内部の潤滑成分が徐々に表面に
拡散するようになり、このため潤滑成分を効率的に利用
できるようになったことによって、大幅に潤滑持続時間
が増大した。As described above, according to the first embodiment, the lubrication (null-null) effect and the lubrication (null-null) effect can be obtained by simply forming the coating film without any chemical reaction for fixing the lubricating coating to the substrate. A coating of a lubricious coating with excellent durability is achieved. Here, when this lubricating coating at the time of water absorption was observed with a scanning electron microscope (SEM) image, the presentation of photographs was omitted, but it was found that the coating was a sponge-like coating having an average hole diameter of several tens μm to several hundred μm. did. In other words, by forming a sponge-like (open cell) like this,
Even when water is absorbed and swelled, large stress concentration does not occur on the bonding surface with the substrate, and as a result, the bonding strength is greatly improved. Further, in this case, the internal lubricating component gradually diffuses to the surface, and thus the lubricating component can be used efficiently, thereby greatly increasing the lubricating duration.
【００１６】また、この効果は潤滑性被覆用溶剤（潤滑
性被覆コーティング剤といってもよい）の液温を２０℃
に保つことによる本実施形態特有の製造方法によるもの
であるが、架橋剤として用いたポリオールである水に溶
けないポリプロピレングリコールを採用したためである
ということがいえる。さらに、本実施形態で得られた潤
滑性被覆は、ヌルヌル性に優れたものとなっているが、
これは親水性部と同時に疎水性部を持たせたためであっ
て、つまり界面活性剤の機能特性を付与した湿潤潤滑性
コーティングとなっているからである。そして、このよ
うに基材表面に従来品よりも多量の水が膜に保持される
ことによって、生体適合性が増し、例えば抗血栓性が大
幅に改良された。This effect is achieved by increasing the temperature of the lubricating coating solvent (which may be referred to as a lubricating coating agent) to 20 ° C.
It can be said that this is due to the fact that a water-insoluble polypropylene glycol, which is a polyol used as a crosslinking agent, is employed. Furthermore, the lubricating coating obtained in the present embodiment has excellent slimy properties,
This is because a hydrophobic portion is provided at the same time as the hydrophilic portion, that is, a wet lubricating coating provided with functional properties of a surfactant. By holding a larger amount of water on the surface of the base material than in the conventional product on the membrane, biocompatibility was increased and, for example, antithrombotic properties were greatly improved.
【００１７】［第２の実施形態］本実施形態において
は、第１の実施形態とは別の標準的製造方法及びそのコ
ーティング方法について説明する。まず、前述のガント
レッツ ＡＮ−１３９を溶媒の例えばＴＨＦで溶解し、
ガントレッツの７％ＴＨＦ溶液を作製する。そして、こ
のガントレッツの７％ＴＨＦ溶液を室温で７２時間以上
放置したものをガントレッツの７％ＴＨＦ溶液の熟成溶
液として準備しておく。なお、ガントレッツのグレード
はＡＮ−１３９に限定されず、他の高分子タイプのもの
でもよい。次いで、ＰＵＲをＴＨＦで溶解し、ＰＵＲの
５％ＴＨＦ溶液を作製する。このＰＵＲとしてもテコフ
レックス（商品名）であれば、ＥＧ８５Ａ〜ＥＧ６５Ｄ
まで使用可能である。さらに、架橋剤のポリプロピレン
グリコールの１０％ＴＨＦ溶液を作製する。このポリプ
ロピレングリコールとしてはポリオールであればどれで
もよいが、架橋効率を上げるために分子量３０００、グ
リコールタイプのものを使用するのが好都合である。上
述のガントレッツの７％ＴＨＦ溶液の熟成溶液、ＰＵＲ
の５％ＴＨＦ溶液及びポリプロピレングリコールの１０
％ＴＨＦ溶液の３種の溶液を潤滑性被覆用溶剤の原料と
して準備しておく。[Second Embodiment] In this embodiment, a standard manufacturing method and a coating method different from the first embodiment will be described. First, the aforementioned Gantrez AN-139 is dissolved in a solvent such as THF,
Make a 7% THF solution of Gantrez. Then, a solution of this 7% THF solution of Gantrez left at room temperature for 72 hours or more is prepared as a maturing solution of the 7% THF solution of Gantrez. The grade of Gantrez is not limited to AN-139, but may be another polymer type. Next, the PUR is dissolved in THF to prepare a 5% THF solution of the PUR. If this PU is Tecoflex (trade name), EG85A to EG65D
Can be used up to. Further, a 10% THF solution of polypropylene glycol as a crosslinking agent is prepared. As the polypropylene glycol, any polyol may be used, but it is convenient to use a glycol type having a molecular weight of 3000 and a glycol type in order to increase the crosslinking efficiency. Aging solution of 7% THF solution of Gantrez described above, PUR
5% THF solution and polypropylene glycol 10
Three kinds of solutions of a% THF solution are prepared as raw materials of a solvent for a lubricating coating.
【００１８】次に、以上の３種の溶液を使用して形成す
る潤滑性被覆用溶剤の製造手順について述べる。まず、
ガントレッツの７％ＴＨＦ溶液の熟成溶液１００（重量
比）に対して、１０（重量比）のポリプロピレングリコ
ールの１０％ＴＨＦ溶液を添加する。添加後、充分に攪
拌する。攪拌により均一に溶液が得られたところで、こ
れに１００（重量比）のＰＵＲの５％ＴＨＦ溶液を加え
て攪拌することにより、潤滑性被覆用溶剤の製造が完了
する。この製造方法で得られた潤滑性被覆用溶剤は１ケ
月程度は変質しないことが確認されている。Next, the procedure for producing a solvent for a lubricating coating formed using the above three kinds of solutions will be described. First,
A 10% (by weight) of a 10% THF solution of polypropylene glycol is added to 100 (by weight) of an aging solution of Gantrez's 7% THF solution. After addition, agitate well. When a uniform solution was obtained by stirring, 100% (by weight) of a 5% THF solution of PUR was added and stirred to complete the production of the lubricating coating solvent. It has been confirmed that the lubricating coating solvent obtained by this production method does not deteriorate for about one month.
【００１９】この潤滑性被覆用溶剤を用いて、医療用具
の表面に潤滑性被覆をコーティングする要領を下記の工
程順によって示す。 （イ）任意の潤滑被覆形成用の容器に所定量の前述の潤
滑性被覆用溶剤を入れる。 （ロ）医療用具の基材として、例えばポリウレタン製の
カテーテルを潤滑性被覆用溶剤中に浸漬した後、５ｍ／
分以上の比較的速い速度で引き上げる。 （ハ）引上げ後、カテーテルの例えば端部に溜まった液
は、内腔から空気を吹き付けて飛ばしてやる。 （ニ）この状態で６０℃×４８時間、又は７０℃×２４
時間の熱処理を行う。 （ホ）その後、０．１ＮのＮａＯＨ水溶液に浸漬した
後、５ｍ／分以上の比較的速い速度で引き上げる。 （ヘ）さらに蒸溜水で洗浄した後、６０℃×２４時間の
乾燥を行い、カテーテル表面への潤滑性被覆のコーティ
ングを終了する。The procedure for coating a lubricating coating on the surface of a medical device using the lubricating coating solvent will be described in the following order of steps. (A) A predetermined amount of the above-mentioned solvent for a lubricating coating is put into an arbitrary container for forming a lubricating coating. (B) As a base material of a medical device, for example, a catheter made of polyurethane was immersed in a solvent for lubricating coating, and then 5 m /
Pull up at a relatively fast speed of more than a minute. (C) After being pulled up, the liquid collected at, for example, the end of the catheter is blown off by blowing air from the lumen. (D) In this state, 60 ° C. × 48 hours or 70 ° C. × 24
Heat treatment for a time is performed. (E) Then, after being immersed in a 0.1N NaOH aqueous solution, it is pulled up at a relatively high speed of 5 m / min or more. (F) After further washing with distilled water, drying at 60 ° C. for 24 hours is performed to complete the coating of the catheter surface with the lubricating coating.
【００２０】以上のように第２の実施形態によれば、潤
滑性被覆の基材への固定に何等の化学反応を必要としな
いで、単に塗布膜を形成するだけで、第１の実施形態の
場合と同様に潤滑（ヌルヌル）効果とその持続性に優れ
た潤滑性被覆のコーティングが達成される。ただ、第２
の実施形態による効果は第１の実施形態のそれと比較す
ると、持続性において若干劣るものの表面は非常にスム
ースであり、基材の生の表面（通常の押し出し表面）よ
りも光沢がよいというように、潤滑性被覆としての確実
性がある。ここで、吸水時のこの潤滑性被覆を走査型電
子顕微鏡によるＳＥＭ像で観察したところ、第１の実施
形態の場合と同様に、平均穴径が数１０μｍ〜数１００
μｍのスポンジ状の被膜が形成されていることが判っ
た。つまり、このようにスポンジ状（連続気泡）が形成
されることによって、水を吸収して膨潤しても基材との
接着面に大きな応力集中が起きなくなり、結果として、
接着強度が大幅に向上した。さらに、この場合内部の潤
滑成分が徐々に表面に拡散するようになり、このため潤
滑成分を効率的に利用できるようになったことによっ
て、大幅に潤滑持続時間が増大した。As described above, according to the second embodiment, the lubricating coating does not require any chemical reaction to fix it to the base material, but simply forms the coating film, and the first embodiment does not. As in the case of (1), a lubricating coating having excellent lubricating (slimy) effect and excellent durability can be achieved. Just the second
The effect of the second embodiment is slightly smoother than that of the first embodiment, but the surface is very smooth and has a higher gloss than the raw surface of the base material (normal extruded surface). , As a lubricious coating. Here, when this lubricating coating at the time of water absorption was observed with an SEM image by a scanning electron microscope, the average hole diameter was several tens μm to several hundreds as in the case of the first embodiment.
It was found that a sponge-like coating of μm was formed. In other words, since the sponge-like (open cells) are formed in this way, even when water is absorbed and swelled, a large stress concentration does not occur on the bonding surface with the substrate, and as a result,
The bonding strength has been greatly improved. Further, in this case, the internal lubricating component gradually diffuses to the surface, and thus the lubricating component can be used efficiently, thereby greatly increasing the lubricating duration.
【００２１】また、この効果は潤滑性被覆用溶剤の前述
のガントレッツの７％ＴＨＦ溶液を少なくとも７２時間
放置して熟成溶液を得たものを使用したことによる本実
施形態特有の製造方法によるものであるが、架橋剤とし
て用いたポリオールである水に溶けないポリプロピレン
グリコールを採用したためであるということも第１の実
施形態の場合と同様である。さらに、本実施形態で得ら
れた潤滑性被覆も、ヌルヌル性に優れたものとなってい
るが、これは基材表面に形成した潤滑性被覆に親水性部
と同時に疎水性部を持たせたためであって、つまり界面
活性剤の機能特性を付与した湿潤潤滑性コーティングと
なっている。そして、このように基材表面に従来品より
も多量の水が膜に保持されることによって、第１の実施
形態の場合と同様に生体適合性が増し、例えば抗血栓性
が大幅に改良された。This effect is also attributable to the production method unique to the present embodiment by using a 7% THF solution of the aforementioned Gantrez as a solvent for a lubricating coating and leaving it for at least 72 hours to obtain an aging solution. However, as in the case of the first embodiment, the reason is that the water-insoluble polypropylene glycol which is the polyol used as the crosslinking agent is employed. Furthermore, the lubricating coating obtained in the present embodiment also has excellent slimy properties, but this is because the lubricating coating formed on the base material surface has a hydrophilic part and a hydrophobic part at the same time. That is, it is a wet lubricating coating provided with the functional properties of a surfactant. Then, by holding a larger amount of water on the surface of the base material than the conventional product on the membrane, biocompatibility is increased as in the case of the first embodiment, and for example, antithrombotic properties are greatly improved. Was.
【００２２】以上、第１の実施形態及び第２の実施形態
によって本発明の構成を詳細に説明したが、これらの実
施形態において示した例えばガントレッツの７％ＴＨＦ
溶液等の数値は一例であって、これらの数値に限定され
ないことはいうまでもない。また、医療用具の材料の一
例として示したポリウレタンも、これに限定されないも
のである。また、本発明は各種の医療用具の湿潤潤滑コ
ートに適用できるばかりでなく、これらの医療用具に対
する例えば抗菌コート等の形成方法に適用しても好適で
ある。The configuration of the present invention has been described in detail with reference to the first embodiment and the second embodiment. For example, the Gantrez 7% THF shown in these embodiments has been described.
The numerical values of the solution and the like are merely examples, and it is needless to say that the numerical values are not limited to these numerical values. Further, the polyurethane shown as an example of the material of the medical device is not limited thereto. Further, the present invention is not only applicable to wet lubricating coats of various medical devices, but is also suitably applied to a method of forming an antimicrobial coat or the like on these medical devices.
【００２３】[0023]
【発明の効果】以上のように本発明によれば、不飽和結
合を有する酸無水物と非共役型ビニルモノマーとの交互
共重合体、架橋剤のポリオール及びウレタン樹脂を所定
比率で有機溶媒に溶解して潤滑性被覆用溶剤を形成し、
この潤滑性被覆用溶剤を医療用具の基材表面に塗布して
スポンジ状の多孔性被膜を形成することにより潤滑性被
覆を有する医療用具を得るから、潤滑性被覆の基材への
固定に何等の化学反応を必要としないで単に塗布膜を形
成するだけで、潤滑効果とその持続性に優れた潤滑性被
覆のコーティングが達成される効果がある。As described above, according to the present invention, an alternating copolymer of an acid anhydride having an unsaturated bond and a non-conjugated vinyl monomer, a polyol as a crosslinking agent and a urethane resin in an organic solvent at a predetermined ratio. Dissolves to form a lubricant coating solvent,
This lubricating coating solvent is applied to the surface of the base material of the medical device to form a sponge-like porous film, thereby obtaining a medical device having a lubricating coating. By simply forming a coating film without the need for a chemical reaction, there is an effect that a lubricating coating excellent in lubricating effect and durability can be achieved.
Claims (2)
ビニルモノマーとの共重合体の溶液に、架橋剤のポリオ
ールの溶液を加え、これにポリウレタンの溶液を加えて
形成した潤滑性被覆用溶剤を医療用具の基材表面に塗布
して形成した湿潤潤滑層が微細な多孔性被膜状のスポン
ジ体であることを特徴とする潤滑性被覆を有する医療用
具。1. A lubricating coating formed by adding a solution of a polyol as a crosslinking agent to a solution of a copolymer of an acid anhydride having an unsaturated bond and a non-conjugated vinyl monomer, and then adding a solution of a polyurethane to the solution. A medical device having a lubricating coating, characterized in that a wet lubricating layer formed by applying a solvent for a medical device to a substrate surface of the medical device is a fine porous film-like sponge.
ビニルモノマーとの共重合体、架橋剤のポリオール及び
ウレタン樹脂を所定比率で有機溶媒に溶解して潤滑性被
覆用溶剤を形成し、この潤滑性被覆用溶剤を医療用具の
基材表面に塗布してスポンジ状の微細多孔性被膜を形成
することを特徴とする潤滑性被覆を有する医療用具の製
造方法。2. A lubricating coating solvent is formed by dissolving a copolymer of an acid anhydride having an unsaturated bond and a non-conjugated vinyl monomer, a crosslinking agent polyol and a urethane resin in an organic solvent at a predetermined ratio. A method for producing a medical device having a lubricating coating, wherein the solvent for lubricating coating is applied to the surface of a substrate of the medical device to form a sponge-like microporous film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28673797A JP4183023B2 (en) | 1997-10-20 | 1997-10-20 | Medical device having lubricious coating and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP28673797A JP4183023B2 (en) | 1997-10-20 | 1997-10-20 | Medical device having lubricious coating and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH11114051A true JPH11114051A (en) | 1999-04-27 |
| JP4183023B2 JP4183023B2 (en) | 2008-11-19 |
Family
ID=17708379
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP28673797A Expired - Fee Related JP4183023B2 (en) | 1997-10-20 | 1997-10-20 | Medical device having lubricious coating and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4183023B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012205846A (en) * | 2011-03-30 | 2012-10-25 | Nihon Covidien Kk | Medical instrument with lubricity and method for manufacturing the same |
| CN107754017A (en) * | 2016-08-22 | 2018-03-06 | 上海微创医疗器械（集团）有限公司 | Medical apparatus surface coating and application |
-
1997
- 1997-10-20 JP JP28673797A patent/JP4183023B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2012205846A (en) * | 2011-03-30 | 2012-10-25 | Nihon Covidien Kk | Medical instrument with lubricity and method for manufacturing the same |
| CN107754017A (en) * | 2016-08-22 | 2018-03-06 | 上海微创医疗器械（集团）有限公司 | Medical apparatus surface coating and application |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4183023B2 (en) | 2008-11-19 |
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