JPH0438960A - Artificial blood vessel of polyvinyl alcohol and polyacrylic acid - Google Patents
Artificial blood vessel of polyvinyl alcohol and polyacrylic acidInfo
- Publication number
- JPH0438960A JPH0438960A JP2146935A JP14693590A JPH0438960A JP H0438960 A JPH0438960 A JP H0438960A JP 2146935 A JP2146935 A JP 2146935A JP 14693590 A JP14693590 A JP 14693590A JP H0438960 A JPH0438960 A JP H0438960A
- Authority
- JP
- Japan
- Prior art keywords
- water
- gel
- polyvinyl alcohol
- mechanical strength
- aqueous solution
- 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
- 239000004372 Polyvinyl alcohol Substances 0.000 title claims abstract description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 title claims abstract description 18
- 210000004204 blood vessel Anatomy 0.000 title claims description 20
- 239000002473 artificial blood Substances 0.000 title claims description 19
- 229920002125 Sokalan® Polymers 0.000 title claims description 12
- 239000004584 polyacrylic acid Substances 0.000 title claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920000642 polymer Polymers 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 230000032050 esterification Effects 0.000 claims abstract description 6
- 238000005886 esterification reaction Methods 0.000 claims abstract description 6
- 230000002785 anti-thrombosis Effects 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 210000001367 artery Anatomy 0.000 claims description 3
- 230000035699 permeability Effects 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 19
- 239000007788 liquid Substances 0.000 abstract description 9
- 238000007598 dipping method Methods 0.000 abstract description 8
- 229920001971 elastomer Polymers 0.000 abstract description 8
- 239000005060 rubber Substances 0.000 abstract description 8
- 150000002500 ions Chemical class 0.000 abstract description 7
- 238000000465 moulding Methods 0.000 abstract description 5
- 239000012528 membrane Substances 0.000 abstract description 4
- 230000008961 swelling Effects 0.000 abstract description 3
- 229920000058 polyacrylate Polymers 0.000 abstract 3
- 239000000499 gel Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 7
- 238000001879 gelation Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 239000004809 Teflon Substances 0.000 description 4
- 229920006362 Teflon® Polymers 0.000 description 4
- 208000007536 Thrombosis Diseases 0.000 description 4
- 239000003146 anticoagulant agent Substances 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 235000013373 food additive Nutrition 0.000 description 3
- 239000002778 food additive Substances 0.000 description 3
- 210000000056 organ Anatomy 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 210000003462 vein Anatomy 0.000 description 3
- 229920004934 Dacron® Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- NPERTKSDHFSDLC-UHFFFAOYSA-N ethenol;prop-2-enoic acid Chemical compound OC=C.OC(=O)C=C NPERTKSDHFSDLC-UHFFFAOYSA-N 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 229920003052 natural elastomer Polymers 0.000 description 2
- 229920001194 natural rubber Polymers 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000007675 cardiac surgery Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000001990 intravenous administration Methods 0.000 description 1
- 210000004731 jugular vein Anatomy 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、柔軟性・弾性・機械強さを有するゴム様のチ
ューブ状吸水性ポリマーに関し、また、この素材を用い
た人工血管に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a rubber-like tubular water-absorbing polymer having flexibility, elasticity, and mechanical strength, and also relates to an artificial blood vessel using this material.
在来の吸水性高分子ゲルは１粒状（イオン交換樹脂、住
人化学−のスミカゲル、三菱油化−のプラウエツトなど
）、板（膜）状、糸状のいずれかの形状をとり、かつ水
中での機械強度が弱く大荷重で破断しやすいものが多い
、水中でゴムのような高弾性と柔軟性・機械強度を有す
る板・膜状または糸状またはチューブ状の吸水性材料が
見当たらない。Conventional water-absorbing polymer gels take the form of particles (ion exchange resins, Sumikagel from Sumikagaku, Mitsubishi Yuka, etc.), plate (membrane), or filamentous shapes, and they are resistant to water in water. Many of these materials have low mechanical strength and are easily broken under heavy loads, and there are no plate/membrane-like, thread-like, or tube-like water-absorbing materials that have high elasticity, flexibility, and mechanical strength like rubber in water.
たとえば、天然・合成ゴムは吸水性でなく、上記の粒状
ゲルは板や糸のような均質な固体の形態に成形できず、
またスミカゲルやプラウエツトの場合粒自体が水中でも
ろい、玉子ゴム化成■のアクアケルはゴム様の板である
が吸水に時間を要しゴムとしてややかたすぎる。高分子
電解質ゲル（メカ７″ケミカル・ゲル）の代表例である
ポリアクリル酸を主成分とするポリアクリル酸とポリビ
ニルアルコール系の１１＊（またはフィラメント）は水
中での機械強さ（最大張力）が従来は１００ｇｆ前後（
水中での応力＝１０ｋｇｆ／ａｄ）で膜の水中厚み０．
１ｍｍ前後を考慮すれば実用上強度があるとはい犬ない
。For example, natural and synthetic rubbers are not water-absorbing, and the granular gels mentioned above cannot be formed into homogeneous solid forms such as plates or threads.
In addition, in the case of Sumikagel and Purawetsu, the grains themselves are brittle in water, while Tamago Rubber Kasei ■'s Aquakel is a rubber-like plate, but it takes time to absorb water and is a little too hard to be considered rubber. Polyacrylic acid and polyvinyl alcohol based 11* (or filament), which is a typical example of polymer electrolyte gel (mecha 7" chemical gel), has mechanical strength (maximum tension) in water. Conventionally, it was around 100 gf (
Underwater stress = 10kgf/ad), the underwater thickness of the membrane is 0.
Considering the thickness of around 1mm, there is no doubt that it is strong enough for practical use.
吸水性ポリマーは、従来単に吸水効果のみ利用されてき
たが、吸水の際のゲル膨潤圧利用、塩・酸・アルカリ水
溶液の選択吸収の際のゲル膨潤・収縮による機械的仕事
利用、さらには２人体内での長期間埋め込み（人工臓器
の素材としての利用）などに応用発展される時、その機
械強度の点で不充分でありさらに強く安定した材料の開
発が必要であった。Water-absorbing polymers have conventionally been used only for their water-absorbing effect, but they can also be used to utilize gel swelling pressure when absorbing water, to utilize mechanical work through gel swelling and contraction when selectively absorbing salt, acid, and alkaline aqueous solutions. When applied to applications such as long-term implantation in the human body (used as a material for artificial organs), its mechanical strength was insufficient, and it was necessary to develop a stronger and more stable material.
一方２人工臓器、特に人工血管においては、従来。On the other hand, 2 artificial organs, especially artificial blood vessels, are conventional.
ナイロン、テフロン、ダクロンなどのプラスチック樹脂
が主として使用されているが、これらを含めて人工の材
料の今まで確認された全てに血栓が生じる欠点がある。Plastic resins such as nylon, Teflon, and Dacron are mainly used, but all of the man-made materials identified so far, including these, have the drawback of forming blood clots.
ダクロン製の平織り・メリヤス編みの人工血管と延伸ポ
リ四フッ化エチレン人工血管が現在、大中口径動脈、大
静脈用に臨床使用されているが、将来は、抗血栓材料を
開発して小口径動脈や中小静脈用の人工血管の開発が望
まれている。Dacron plain weave/stockinette artificial blood vessels and stretched polytetrafluoroethylene artificial blood vessels are currently in clinical use for large and medium caliber arteries and vena cava, but in the future, antithrombotic materials will be developed and small caliber artificial blood vessels will be used. The development of artificial blood vessels for arteries and small and medium veins is desired.
抗血栓材料の開発は９人工心臓ポンプの素材、心臓手術
用カテーテル、点滴用カニユーレなど多くの人工臓器や
医用機器に求められている。The development of antithrombotic materials is required for many artificial organs and medical devices, including materials for artificial heart pumps, cardiac surgery catheters, and intravenous cannulae.
本発明は、素材の開発とその一応用に関する。すなわち
、水または水溶液中で適度の弾性と機械強度を安定して
維持する吸水性高分子ゲルの管（中空の円管、その断面
の可変の場合を含む）の合成と加工法に関する。また、
この素材は抗血栓性を有するので、この円管（チューブ
）の人工血管への応用に関する。The present invention relates to the development of materials and one application thereof. That is, it relates to a synthesis and processing method for water-absorbing polymer gel tubes (including hollow circular tubes with variable cross-sections) that stably maintain appropriate elasticity and mechanical strength in water or aqueous solutions. Also,
Since this material has antithrombotic properties, the application of this circular tube to artificial blood vessels is concerned.
ポリビニルアルコールとポリアクリル酸の混合濃縮液（
前者の重量比が後者より大とし、前者のみの場合を含む
）を適当な芯を用いてディッピング成形し、１００℃か
ら１１０℃前後の空気温度の下で２時間以上熱処理（エ
ステル化）し７た管状ゲルは水中でのｉ７１！状態にお
いて、軟らかいゴムに類似の柔軟性・弾性・機械強度を
有する素材となる。従来の吸水性ヒドロゲルや吸水性ゲ
ルは、イオン交換樹脂などの粒状のゲルを除いて、水中
での機械強度が劣っており破断しやすかったが２本チュ
ーブ状ゲルは従来の膜状ケルの５倍ないしは１０倍以上
の破断強さを有する。ポリアクリル酸を含む場合は、メ
カノケミカル・アクチュエータとしての特性（酸・アル
カリ・塩を選択吸収して膨潤・収縮し１機械仕事を行う
こと〉も有する。吸水性ポリマーであるから、乾燥状態
から吸水し１１７１ｍする特性があり、ゲル膜内外を通
じて水や水溶液中の各種イオンを透過する特性もある１
機械強度の点での向上は、工業用・医用への本材料の応
用の実現性を高める。Mixed concentrate of polyvinyl alcohol and polyacrylic acid (
The weight ratio of the former is larger than the latter, and the former is included) is dip-molded using an appropriate core, and heat-treated (esterified) at an air temperature of about 100°C to 110°C for 2 hours or more. The tubular gel is i71 in water! In this state, it becomes a material with flexibility, elasticity, and mechanical strength similar to soft rubber. Conventional water-absorbing hydrogels and water-absorbing gels, with the exception of granular gels such as ion exchange resins, have poor mechanical strength in water and are prone to breakage. It has a breaking strength of 10 times or more. If it contains polyacrylic acid, it also has properties as a mechanochemical actuator (selectively absorbs acids, alkalis, and salts and swells and contracts to perform mechanical work).Since it is a water-absorbing polymer, it can be used in a dry state. It has the property of absorbing water up to 1171m, and also has the property of permeating various ions in water and aqueous solutions through the inside and outside of the gel membrane1.
The improvement in mechanical strength increases the feasibility of applying this material to industrial and medical uses.
本材料は、ポリビニルアルコール、ポリアクリル酸とも
食品添加物であって人体に無害であり、上述のように水
やイオンの吸収性・透過性があり、ゴムに近い機械伸度
があり、さらに抗血栓性が動物実験により確認できたの
で、その医用への応用の一つとして、抗血栓効果のある
人工血管となりうる０本発明は本チューブの人工血管へ
の応用である。Both polyvinyl alcohol and polyacrylic acid are food additives and are harmless to the human body.As mentioned above, this material has water and ion absorption and permeability, mechanical elongation close to that of rubber, and resistance. Since the thrombogenicity was confirmed through animal experiments, one of its medical applications is that it can be used as an artificial blood vessel with an antithrombotic effect.The present invention is an application of this tube to an artificial blood vessel.
（１）材料の合成・成形
ポリアクリル酸（市販品）を重量濃度５％の希釈水溶液
とする。また、ポリビニルアルコール（市販品、粉末）
を蒸留水に溶かし、５％水溶液とする。(1) Synthesis and molding of materials Polyacrylic acid (commercially available) was prepared as a diluted aqueous solution with a weight concentration of 5%. Also, polyvinyl alcohol (commercial product, powder)
Dissolve in distilled water to make a 5% aqueous solution.
この場合、上澄み液を士数回捨てて純度をあげ。In this case, discard the supernatant liquid several times to improve purity.
１００度Ｃ近い沸騰を透明になるまで繰り返せばポリビ
ニルアルコールの均質な水溶液ができる。二種の高分子
溶液をボリビ；、ルアルコールの重量比が大きい比率で
（ＰＡＡ： ＰＶＡ重量％−１：５以上］：１０ないし
はｉ：２０）、攪拌器で長時間（５−１５時間）点滴し
ながら混合する。混合液（５％濃度が実施上最適であっ
た）を乾燥器内で３５℃から４０℃で長時間濃縮させ（
約３−４週間）（濃縮器を用いれば時間短縮可能）、約
７０％濃度とする。A homogeneous aqueous solution of polyvinyl alcohol can be obtained by repeating boiling at nearly 100 degrees Celsius until it becomes transparent. The two types of polymer solutions were stirred in a stirrer for a long time (5-15 hours) at a high weight ratio of alcohol (PAA: PVA weight % - 1:5 or more):10 or i:20. Mix while dripping. The mixed solution (5% concentration was optimal in practice) was concentrated in a dryer at 35 to 40 °C for a long time (
(about 3-4 weeks) (time can be shortened by using a concentrator), to a concentration of about 70%.
この濃縮過程において減圧器中で減圧し濃縮液中の気泡
など液中の空気を除去する。また、液表面にできた膜は
除去する。また、ポリビニルアルコールのみ（５％濃度
）の濃縮液（約７０％濃度）も有効である。実施経験上
、７０％より低濃度（５０％など）ではディッピングの
回数が多くなり材料強度が低下し、より高濃度ではディ
ッピングが不可能になる。In this concentration process, the pressure is reduced in a pressure reducer to remove air in the concentrated liquid, such as air bubbles. Also, remove the film formed on the liquid surface. A concentrated solution (approximately 70% concentration) of only polyvinyl alcohol (5% concentration) is also effective. From practical experience, when the concentration is lower than 70% (such as 50%), the number of dipping increases and the material strength decreases, and when the concentration is higher, dipping becomes impossible.
この濃縮液を細長いガラス管（試験管）に移し。Transfer this concentrated solution to a long thin glass tube (test tube).
外径１−１０ｍｍ、長さ５０ １００ｍｍのテフロン・
チューブ（またはテフロン棒）をほぼ鉛直に濃縮液に差
し込み（ディッピングし）、室内で吊るして表面乾燥さ
せ、チューブ（芯）を上下反転させて再びディッピング
する。これを１回として２−５回所定の厚みが得られる
まで繰り返す（２−３回が適当である）、なお、ガラス
棒のような表面が滑らかな物は芯として不適当であり、
ディッピング回数が多いと表面に凹凸ができることがあ
る。Teflon with outer diameter 1-10mm and length 50-100mm.
Insert the tube (or Teflon rod) almost vertically into the concentrate (dip), hang it indoors to dry the surface, turn the tube (core) upside down, and dip again. Repeat this 2-5 times until the desired thickness is obtained (2-3 times is appropriate). Note that objects with smooth surfaces such as glass rods are not suitable as cores.
If the number of times of dipping is large, unevenness may be formed on the surface.
ディッピング終了後、芯（テフロン・チューブなど）付
きのまま、乾燥機内に吊るし、８０℃で３０分から１時
間、つぎに１００−１１０℃で２時間から２０時間位ま
でエステル化（熱処理）する、このエステル化によって
、ゲル化する０通常は１１０℃で３時間でゲル化するが
、後述する溶出試験合格には長時間の熱処理が必要とな
る。After dipping, the core (Teflon tube, etc.) is hung in a dryer and esterified (heat treated) at 80°C for 30 minutes to 1 hour, then at 100-110°C for 2 to 20 hours. Gelation occurs due to esterification. Usually gelation occurs at 110° C. in 3 hours, but a long heat treatment is required to pass the elution test described below.
（２） 引張試験
熱処理終了したサンプルを水に漬けると９表面のゲルが
膨潤して芯がとれ、中空のチューブ状のゲルができる。(2) Tensile test When the heat-treated sample is soaked in water, the gel on the surface swells and the core is removed, forming a hollow tube-shaped gel.
一端を固定し他端に荷重を吊るし、水中での荷重と伸び
の関係をチューブが破断するまで行う、実験の結果、膨
潤時のサンプル断面積２．６平方ｍ ｍから４．５平方
ｍｍの、ポリアクリル酸（ＦＡＡ）：ポリビニルアルコ
ール（ＰＶＡ）＝１：１０から１：２０．およびＰＶＡ
のみのサンプルについては、１ｋｇｆ以上の荷重にたえ
られ破断しなかった。縦弾性係数（ヤング率）は、低荷
重域で約２６ｋｇｆ／ｃｉ＝２６ＯＮ／ｃｎ！、高荷重
域で約８ ｋｇ ｆ／ｃｄ＝８ ＯＮ／ｃｄであった。As a result of an experiment, one end was fixed and a load was suspended from the other end, and the relationship between the load and elongation in water was investigated until the tube broke. , polyacrylic acid (FAA): polyvinyl alcohol (PVA) = 1:10 to 1:20. and PVA
As for the sample, it could withstand a load of 1 kgf or more without breaking. The longitudinal elastic modulus (Young's modulus) is approximately 26 kgf/ci = 26 ON/cn in the low load range! , approximately 8 kg f/cd = 8 ON/cd in the high load range.
この値は、天然ゴムのヤング率１００Ｎ／（ｎと同じオ
ーダーであり、ゴムと類似の柔軟性と機械強度を有する
と判断できる。This value is on the same order as the Young's modulus of natural rubber, 100 N/(n, and can be judged to have flexibility and mechanical strength similar to rubber.
本チューブの水中でのクリープ試験によれば。According to the underwater creep test of this tube.
ＰＡＡ：ＰＶＡ＝１ ： １０，８０℃１時間、１００
℃３時間のエステル化、最大荷重１ｋｇｆ以上のサンプ
ルの荷重５００ｇｆでのクリープは１０％程度あり、約
３０分後に一定値に収束しており、材料として、定負荷
の下で安定している。PAA:PVA=1: 10, 80℃ 1 hour, 100
When subjected to esterification for 3 hours at °C and a sample with a maximum load of 1 kgf or more, the creep at a load of 500 gf was about 10%, and it converged to a constant value after about 30 minutes, indicating that the material is stable under a constant load.
（３） 抗血栓性試験
本チューブの一本（ＰＡＡ ： ＰＶＡ＝ １ ： １
０゜内径２ ｍ ｍ ）を９人工血管として、大の右側
頚静脈内に挿入し縫合糸で固定しく浜松医大の原田教授
と静岡大学電子科学研究科の木村元彦助手の協力を得て
）、−週間後に生存大から抽出したところ、縫合糸周辺
に一部血栓があったが、チューブには血栓はみとめられ
なかった。縫合糸による血流の乱れがあったと思われる
部分以外は血栓は生じてなく２本材料は抗血栓篩がある
と判断できる。（今後、さらに比較実験する必要がある
が、上記医師も有望と認めている）。(3) Antithrombotic test tube (PAA:PVA=1:1)
With the cooperation of Professor Harada of Hamamatsu Medical University and Assistant Professor Motohiko Kimura of the Graduate School of Electronic Science, Shizuoka University), 9 artificial blood vessels (0° internal diameter 2 mm) were inserted into the right jugular vein of the patient and fixed with sutures. When the surviving specimen was extracted after - weeks, there was some thrombus around the suture, but no thrombus was found in the tube. No thrombus was formed except for the area where the blood flow was thought to have been disturbed by the suture, and it can be concluded that the two materials have an anti-thrombotic sieve. (Further comparative experiments are needed in the future, but the above doctor agrees that it is promising.)
（４） 溶出試験
厚生省基準による人体内埋め込み用材料の溶出試験（サ
ンプル０．１ｇを１００ｃｃの蒸留水中に浸し５０℃ま
たは７０℃で２４時間放置後の溶出液１０ｃｃ中の過マ
ンガン酸カリ消′ｇｌ量が１．０ｃｃ以下を合格基準と
するもの）を日本シセーウソド社の協力により行った結
果、１１０℃３時間エステル化の本チューブの場合、過
マンガン酸カリ消費量が１１ １４ｃｃであったが、１
１０℃１５時間以上の本チューブの場合の過マンガン酸
カリ消費量は。(4) Elution test Elution test for materials to be implanted in the human body according to the standards of the Ministry of Health and Welfare (0.1 g of sample was immersed in 100 cc of distilled water, left at 50°C or 70°C for 24 hours, and potassium permanganate in 10 cc of the eluate was quenched. As a result of conducting a test with the cooperation of Nippon Shisei Usodo Co., Ltd., the consumption of potassium permanganate was 11 to 14 cc in the case of this tube, which was esterified for 3 hours at 110°C. ,1
What is the amount of potassium permanganate consumed when using this tube at 10°C for 15 hours or more?
０．１−０．２ｃｃとなった。長時間１００ないし１１
０℃での熱処理と、その途中で５０−７０℃での水洗を
数回挟む（各回、数時間その温度の水に漬け、水を取り
替える）ことによって、溶出量を基準以下に改善できる
。このような長時間熱処理によって本チューブの水中で
の機械強度はやや低下する傾があり、実験例では破断荷
重１１００ｋｇｆ以上（エステル化３時間）が９００ｇ
ｆ （同１５時間）となったが、この程度なら機械強度
は実用上充分である。It became 0.1-0.2cc. long time 100 to 11
By heat treatment at 0°C and washing with water at 50-70°C several times in between (soaking in water at that temperature for several hours each time and replacing the water), the amount of elution can be improved to below the standard. Due to such long-term heat treatment, the mechanical strength of this tube in water tends to decrease slightly, and in the experimental example, the breaking load of 1100 kgf or more (esterification for 3 hours) was 900 g.
f (15 hours), but this level of mechanical strength is sufficient for practical use.
本チューブは、その濃縮液の粘着性と水分除去の遅いこ
となどから押出成形しにくいのが多量生産に向かず難点
である。一方、ディッピング成形によって、芯の長軸方
向に沿って高分子鎖が配向し、これが機械強度の向上に
寄与すると考えられる。デインピング成形は多量生産に
向かないが、アイスボンボンのゴム袋の製造例のように
多数の芯を同時に液浸する方法により生産効率を高めら
れる。This tube is difficult to extrude because of the stickiness of the concentrated liquid and the slow removal of water, making it unsuitable for mass production. On the other hand, by dipping molding, the polymer chains are oriented along the long axis direction of the core, which is thought to contribute to improving mechanical strength. Although deimping molding is not suitable for mass production, production efficiency can be improved by simultaneously immersing multiple cores in liquid, as in the production of rubber bags for ice bonbons.
吸水性ポリマーのゲル化は従来上として冷凍法によって
行われているが２本実施例によれば、冷凍法は数日を要
し、かつゲル化が不十分であった。Gelation of a water-absorbing polymer has conventionally been carried out by a freezing method, but according to the two examples, the freezing method required several days and gelation was insufficient.
濃縮液をディッピング成形しエステル化法にょるゲル化
が本発明の特徴である。A feature of the present invention is dipping molding of a concentrated liquid and gelation using an esterification method.
また９食品添加物である２人体に無害な、かつ水および
水中のイオンを吸収・透過する吸水性高分子を人工血管
に応用する点に特徴がある。在来の人工血管のように糸
を編んで多孔性を持たせる必要がなく、均質な膜（チュ
ーブ）壁を通じて水・イオンの出入りが可能になる。し
かも、抗血栓性と適度の機械強度が期待でき、従来不可
能であった中小口径の静脈にも応用できる人工血管とな
る可能性のある発明である。Another feature of this invention is that it uses a water-absorbing polymer, which is a food additive, and which is harmless to the human body and absorbs and permeates water and ions in water, to be applied to artificial blood vessels. Unlike conventional artificial blood vessels, there is no need to create porosity by weaving threads, and water and ions can enter and exit through the homogeneous membrane (tube) wall. Moreover, it is expected to have antithrombotic properties and appropriate mechanical strength, and this invention has the potential to become an artificial blood vessel that can be applied to veins of medium and small diameters, which was previously impossible.
４ 図面の説明 本発明の図および図説明は省略する。4 Explanation of drawings Figures and illustrations of the present invention will be omitted.
手続補正書（方式）
％式％
１、 事件の表示 平成２年 特許Ｈ第１４６９３５
号２、 発明の名称 ポリビニルアルコールとポリア
クリル酸管人工血管３、 補正をする者
事件との関係 特許出願人
５゜
補正の対象と内容
１、適正な願書
ハ、特許出願人の住所を正確に記載したもの。Procedural amendment (method) % formula % 1, Indication of case 1990 Patent H No. 146935
No. 2. Title of the invention Polyvinyl alcohol and polyacrylic acid tube artificial blood vessel 3. Relationship with the case of the person making the amendment Patent applicant 5. Subject and content of the amendment 1. Proper application form, Accurate address of the patent applicant What is written.
二、特許出願人の氏名を記載したもの。2. The name of the patent applicant.
ボ、特許出願人の記名のあとに朱肉を用いて鮮明に捺印
したもの４１、明細書の下記事項の不備を補正する旨を
記載した書面。(b) A document clearly stamped using vermilion ink after the name of the patent applicant41, and a document stating that the following deficiencies in the specification will be corrected.
４、図面の簡単な説明の欄 （注）削除すること。4. Column for brief explanation of drawings (Note) Please delete.
ゲル化が本発明の特徴である。Gelation is a feature of the invention.
また１食品添加物である１人体に無害な、がっ水および
水中のイオンを吸収・透過する吸水性高分子を人工血管
に応用する点に特徴がある。在来の人工血管のように糸
を編んで多孔性を持たせる必要がなく 、 均質ｆ：Ｍ
（チューブ）壁を通じて水・イオンの出入りが可能に
なる、しかも、抗血栓性と適度の機械強度が期待でき、
従来不可能であった中小口径の静脈にも応用できる人工
血管となる可能性のある発明である。Another feature is the application of water-absorbing polymers, which are food additives and are harmless to the human body, and which absorb and permeate water and ions in water, to artificial blood vessels. Unlike conventional artificial blood vessels, there is no need to knit threads to create porosity, and the result is a homogeneous f:M
(Tube) allows water and ions to enter and exit through the wall, and is expected to have antithrombotic properties and moderate mechanical strength.
This invention has the potential to become an artificial blood vessel that can be applied to small and medium-sized veins, which was previously impossible.
Claims (1)
液（またはポリメタアクリル酸水溶液）を前者の方が高
い重量比で混合した濃縮液、またはポリビニルアルコー
ルのみの濃縮液を、芯を用いてディッピング成形し、１
００度Ｃ前後で２時間以上熱処理（エステル化）してゲ
ル化した、水中での適度の柔軟性と機械強度のあるチュ
ーブ状吸水性高分子 ２ 上記チューブを動脈または静脈血管の一部の代用と
して用いる抗血栓性を特徴とし水透過性を有する人工血
管[Claims] 1. A concentrated solution obtained by mixing a polyvinyl alcohol aqueous solution and a polyacrylic acid aqueous solution (or a polymethacrylic acid aqueous solution) at a higher weight ratio, or a concentrated solution of only polyvinyl alcohol, using a wick. Dip and mold, 1
Tubular water-absorbing polymer with moderate flexibility and mechanical strength in water, gelled by heat treatment (esterification) at around 00 degrees Celsius for 2 hours or more 2. The above tube can be used as a substitute for a part of an artery or a venous blood vessel. Artificial blood vessels with water permeability and antithrombotic properties used as
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2146935A JPH0438960A (en) | 1990-06-04 | 1990-06-04 | Artificial blood vessel of polyvinyl alcohol and polyacrylic acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2146935A JPH0438960A (en) | 1990-06-04 | 1990-06-04 | Artificial blood vessel of polyvinyl alcohol and polyacrylic acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0438960A true JPH0438960A (en) | 1992-02-10 |
Family
ID=15418899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2146935A Pending JPH0438960A (en) | 1990-06-04 | 1990-06-04 | Artificial blood vessel of polyvinyl alcohol and polyacrylic acid |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0438960A (en) |
Cited By (29)
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|---|---|---|---|---|
| JPH08266615A (en) * | 1995-03-31 | 1996-10-15 | Agency Of Ind Science & Technol | Cell nonadhesive/nonproliferation medical supplies |
| JP2010018678A (en) * | 2008-07-09 | 2010-01-28 | Olympus Corp | Thermoreversible crosslinkable resin composition and soft tubular structural body using the composition |
| JP2010525154A (en) * | 2007-04-24 | 2010-07-22 | ザ・ジェネラル・ホスピタル・コーポレイション | PVA-PAA hydrogel |
| US8211125B2 (en) | 2008-08-15 | 2012-07-03 | Ethicon Endo-Surgery, Inc. | Sterile appliance delivery device for endoscopic procedures |
| US8241204B2 (en) | 2008-08-29 | 2012-08-14 | Ethicon Endo-Surgery, Inc. | Articulating end cap |
| US8252057B2 (en) | 2009-01-30 | 2012-08-28 | Ethicon Endo-Surgery, Inc. | Surgical access device |
| US8262655B2 (en) | 2007-11-21 | 2012-09-11 | Ethicon Endo-Surgery, Inc. | Bipolar forceps |
| US8262680B2 (en) | 2008-03-10 | 2012-09-11 | Ethicon Endo-Surgery, Inc. | Anastomotic device |
| US8262563B2 (en) | 2008-07-14 | 2012-09-11 | Ethicon Endo-Surgery, Inc. | Endoscopic translumenal articulatable steerable overtube |
| US8337394B2 (en) | 2008-10-01 | 2012-12-25 | Ethicon Endo-Surgery, Inc. | Overtube with expandable tip |
| US8353487B2 (en) | 2009-12-17 | 2013-01-15 | Ethicon Endo-Surgery, Inc. | User interface support devices for endoscopic surgical instruments |
| US8361112B2 (en) | 2008-06-27 | 2013-01-29 | Ethicon Endo-Surgery, Inc. | Surgical suture arrangement |
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| US10092291B2 (en) | 2011-01-25 | 2018-10-09 | Ethicon Endo-Surgery, Inc. | Surgical instrument with selectively rigidizable features |
| US10098691B2 (en) | 2009-12-18 | 2018-10-16 | Ethicon Endo-Surgery, Inc. | Surgical instrument comprising an electrode |
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| US10258406B2 (en) | 2011-02-28 | 2019-04-16 | Ethicon Llc | Electrical ablation devices and methods |
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-
1990
- 1990-06-04 JP JP2146935A patent/JPH0438960A/en active Pending
Cited By (35)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH08266615A (en) * | 1995-03-31 | 1996-10-15 | Agency Of Ind Science & Technol | Cell nonadhesive/nonproliferation medical supplies |
| US8425505B2 (en) | 2007-02-15 | 2013-04-23 | Ethicon Endo-Surgery, Inc. | Electroporation ablation apparatus, system, and method |
| US10478248B2 (en) | 2007-02-15 | 2019-11-19 | Ethicon Llc | Electroporation ablation apparatus, system, and method |
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| US8262655B2 (en) | 2007-11-21 | 2012-09-11 | Ethicon Endo-Surgery, Inc. | Bipolar forceps |
| US8262680B2 (en) | 2008-03-10 | 2012-09-11 | Ethicon Endo-Surgery, Inc. | Anastomotic device |
| US8403926B2 (en) | 2008-06-05 | 2013-03-26 | Ethicon Endo-Surgery, Inc. | Manually articulating devices |
| US8361112B2 (en) | 2008-06-27 | 2013-01-29 | Ethicon Endo-Surgery, Inc. | Surgical suture arrangement |
| JP2010018678A (en) * | 2008-07-09 | 2010-01-28 | Olympus Corp | Thermoreversible crosslinkable resin composition and soft tubular structural body using the composition |
| US11399834B2 (en) | 2008-07-14 | 2022-08-02 | Cilag Gmbh International | Tissue apposition clip application methods |
| US10105141B2 (en) | 2008-07-14 | 2018-10-23 | Ethicon Endo-Surgery, Inc. | Tissue apposition clip application methods |
| US8262563B2 (en) | 2008-07-14 | 2012-09-11 | Ethicon Endo-Surgery, Inc. | Endoscopic translumenal articulatable steerable overtube |
| US8211125B2 (en) | 2008-08-15 | 2012-07-03 | Ethicon Endo-Surgery, Inc. | Sterile appliance delivery device for endoscopic procedures |
| US8241204B2 (en) | 2008-08-29 | 2012-08-14 | Ethicon Endo-Surgery, Inc. | Articulating end cap |
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| US8337394B2 (en) | 2008-10-01 | 2012-12-25 | Ethicon Endo-Surgery, Inc. | Overtube with expandable tip |
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| US10779882B2 (en) | 2009-10-28 | 2020-09-22 | Ethicon Endo-Surgery, Inc. | Electrical ablation devices |
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| US10098691B2 (en) | 2009-12-18 | 2018-10-16 | Ethicon Endo-Surgery, Inc. | Surgical instrument comprising an electrode |
| US10092291B2 (en) | 2011-01-25 | 2018-10-09 | Ethicon Endo-Surgery, Inc. | Surgical instrument with selectively rigidizable features |
| US10258406B2 (en) | 2011-02-28 | 2019-04-16 | Ethicon Llc | Electrical ablation devices and methods |
| US9883910B2 (en) | 2011-03-17 | 2018-02-06 | Eticon Endo-Surgery, Inc. | Hand held surgical device for manipulating an internal magnet assembly within a patient |
| US10206709B2 (en) | 2012-05-14 | 2019-02-19 | Ethicon Llc | Apparatus for introducing an object into a patient |
| US11284918B2 (en) | 2012-05-14 | 2022-03-29 | Cilag GmbH Inlernational | Apparatus for introducing a steerable camera assembly into a patient |
| US9788888B2 (en) | 2012-07-03 | 2017-10-17 | Ethicon Endo-Surgery, Inc. | Endoscopic cap electrode and method for using the same |
| US10492880B2 (en) | 2012-07-30 | 2019-12-03 | Ethicon Llc | Needle probe guide |
| US10314649B2 (en) | 2012-08-02 | 2019-06-11 | Ethicon Endo-Surgery, Inc. | Flexible expandable electrode and method of intraluminal delivery of pulsed power |
| US10342598B2 (en) | 2012-08-15 | 2019-07-09 | Ethicon Llc | Electrosurgical system for delivering a biphasic waveform |
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