JP2007077359A - Segmented polyurethane containing fluorine and silicon in main chain, medical device containing the polyurethane and biocompatible element containing the polyurethane - Google Patents
Segmented polyurethane containing fluorine and silicon in main chain, medical device containing the polyurethane and biocompatible element containing the polyurethane Download PDFInfo
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- 239000004814 polyurethane Substances 0.000 title claims abstract description 60
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 59
- 239000010703 silicon Substances 0.000 title claims abstract description 33
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 33
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 31
- 239000011737 fluorine Substances 0.000 title claims abstract description 31
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000000178 monomer Substances 0.000 claims abstract description 15
- 150000002009 diols Chemical class 0.000 claims description 52
- -1 2-hydroxyethoxy Chemical group 0.000 claims description 37
- 239000000203 mixture Substances 0.000 claims description 33
- 125000005442 diisocyanate group Chemical group 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- 210000004204 blood vessel Anatomy 0.000 claims description 7
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
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- OHLKMGYGBHFODF-UHFFFAOYSA-N 1,4-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=C(CN=C=O)C=C1 OHLKMGYGBHFODF-UHFFFAOYSA-N 0.000 claims description 3
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- SBJCUZQNHOLYMD-UHFFFAOYSA-N 1,5-Naphthalene diisocyanate Chemical compound C1=CC=C2C(N=C=O)=CC=CC2=C1N=C=O SBJCUZQNHOLYMD-UHFFFAOYSA-N 0.000 claims description 3
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- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical compound CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 claims description 3
- 238000005191 phase separation Methods 0.000 claims description 2
- XKJCHHZQLQNZHY-UHFFFAOYSA-N phthalimide Chemical compound C1=CC=C2C(=O)NC(=O)C2=C1 XKJCHHZQLQNZHY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 10
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- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
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- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
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- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- XAFJMCUBVZTMDB-UHFFFAOYSA-N 2-[4-[1,1,1,3,3,3-hexafluoro-2-[4-(2-hydroxyethoxy)phenyl]propan-2-yl]phenoxy]ethanol Chemical compound C1=CC(OCCO)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(OCCO)C=C1 XAFJMCUBVZTMDB-UHFFFAOYSA-N 0.000 description 2
- ZWPBNGQNJOSBGP-UHFFFAOYSA-N 3-[4-[1,1,1,3,3,3-hexafluoro-2-[4-(3-hydroxypropoxy)phenyl]propan-2-yl]phenoxy]propan-1-ol Chemical compound C1=CC(OCCCO)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(OCCCO)C=C1 ZWPBNGQNJOSBGP-UHFFFAOYSA-N 0.000 description 2
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- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- RWNKSTSCBHKHTB-UHFFFAOYSA-N Hexachloro-1,3-butadiene Chemical compound ClC(Cl)=C(Cl)C(Cl)=C(Cl)Cl RWNKSTSCBHKHTB-UHFFFAOYSA-N 0.000 description 2
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- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 description 2
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- Polyurethanes Or Polyureas (AREA)
Abstract
Description
本発明は、セグメント化ポリウレタンに関し、より詳細には、主鎖にフッ素およびケイ素を含有し、ミクロ相分離構造を有するセグメント化ポリウレタン、該ポリウレタンを含む医療用器具、および、該ポリウレタンを含む生体適合性要素に関する。 The present invention relates to a segmented polyurethane, and more particularly, a segmented polyurethane containing a fluorine and silicon in the main chain and having a microphase separation structure, a medical device including the polyurethane, and a biocompatible including the polyurethane Regarding sex elements.
現在、医療用材料の分野において、様々な用途に対応する新材料の開発が検討されており、その中でも、熱可塑性エラストマーの医療分野への応用が注目されている。熱可塑性エラストマーは、ゴム弾性を示すソフトセグメントと、架橋ゴムの架橋点に相当するハードセグメントから構成されるポリマーであり、架橋ゴムのように架橋剤等の配合剤が溶出することがないうえ、ハードセグメントに由来する熱可塑性によって加工性に優れるという利点があり、ポリスチレン系、ポリオレフィン系、ポリエステル系など様々な熱可塑性エラストマーが用途に応じて用いられている。 Currently, in the field of medical materials, the development of new materials corresponding to various applications is being studied, and among them, the application of thermoplastic elastomers to the medical field is attracting attention. The thermoplastic elastomer is a polymer composed of a soft segment showing rubber elasticity and a hard segment corresponding to the crosslinking point of the crosslinked rubber, and the compounding agent such as a crosslinking agent does not elute like the crosslinked rubber. There is an advantage of excellent workability due to the thermoplasticity derived from the hard segment, and various thermoplastic elastomers such as polystyrene, polyolefin, and polyester are used depending on applications.
その中でも、ポリウレタン系の熱可塑性エラストマーであるセグメント化ポリウレタンは、好適な機械的特性を有しており、さらに生体適合性が高いことから、様々な医療用器具に応用されている。 Among them, segmented polyurethane, which is a polyurethane-based thermoplastic elastomer, has suitable mechanical properties and has high biocompatibility, and is therefore applied to various medical devices.
上述した医療用器具のなかでも血液と直接接触する、人工心臓（心臓人工弁および人工心臓ポンプ）や大動脈バルーンなどには、特に高度な耐疲労性および弾性が要求され、そして何よりも特に高い抗血栓性が求められており、医療用材料としてより高い応用性を備えたセグメント化ポリウレタンの合成が求められていた。 Among the above-mentioned medical devices, artificial hearts (heart prosthetic valves and artificial heart pumps), aortic balloons, and the like that are in direct contact with blood are required to have particularly high fatigue resistance and elasticity, and particularly high resistance. There has been a demand for thrombogenicity, and there has been a demand for the synthesis of segmented polyurethane having higher applicability as a medical material.
本発明は、上記従来技術に鑑みてなされたものであり、本発明は、高い抗血栓性に加え、好適な弾性および耐疲労性を備えるセグメント化ポリウレタンを提供することを目的とする。 This invention is made | formed in view of the said prior art, and this invention aims at providing segmented polyurethane provided with suitable elasticity and fatigue resistance in addition to high antithrombogenicity.
生体の血管内面を被覆している内皮細胞を含む内膜は、図１に示されるような、いわゆる海島構造をとっていることがわかっており、生体の血管におけるこのようなミクロドメイン構造が何らかの理由で、血漿タンパクの血管内膜への吸着を抑制し、ひいては、血漿タンパクの吸着を契機としてなされる血栓の形成を阻害していると考えられる。一方、ポリテトラフルオロエチレン（以下、ＰＴＦＥという）のようなフッ素を含有するポリマー、および、ポリジメチルシロキサン（以下、ＰＤＭＳという）のようなケイ素を含有するポリマーは、いずれも表面エネルギーが低く、耐熱耐寒性、耐水耐薬品性、撥水撥油性、低摩擦係数、非粘着性、気体選択透過性、生体適合性、柔軟性および耐疲労性といった共通した性質を有する疎水性ポリマーとして知られている。そこで、本発明者らは、フッ素およびケイ素を含み、かつ、生体の血管内膜のドメイン構造に近似した、ドメインサイズの様々に異なったミクロ相分離構造をもつセグメント化ポリウレタンを合成することできれば、血漿タンパクの吸着をより好適に抑制して、高い抗血栓性を実現することができ、さらに加えて医療用材料としての好適な機械的特性を同時に実現しうると考えた。 The inner membrane containing endothelial cells covering the inner surface of a blood vessel in a living body is known to have a so-called sea-island structure as shown in FIG. For this reason, it is considered that the adsorption of plasma protein to the intima of the blood vessel is suppressed, and as a result, the formation of a thrombus caused by the adsorption of plasma protein is inhibited. On the other hand, a polymer containing fluorine such as polytetrafluoroethylene (hereinafter referred to as PTFE) and a polymer containing silicon such as polydimethylsiloxane (hereinafter referred to as PDMS) have low surface energy and are heat resistant. Known as a hydrophobic polymer with common properties such as cold resistance, water and chemical resistance, water and oil repellency, low coefficient of friction, non-adhesiveness, gas permselectivity, biocompatibility, flexibility and fatigue resistance . Therefore, the present inventors can synthesize a segmented polyurethane containing microphase-separated structures having various domain sizes, which contain fluorine and silicon, and approximate the domain structure of a living intima. It was considered that plasma protein adsorption can be more suitably suppressed to achieve high antithrombogenicity, and in addition, suitable mechanical properties as a medical material can be realized at the same time.
以上のような着想の下、本発明者らは、セグメント化ポリウレタンにおいて、含フッ素モノマーおよび含ケイ素モノマーを構成成分として、ドメインサイズの様々に異なったミクロ相分離構造を形成し、医療用材料として好適な表面特性、および機械的特性等を実現すべく、合成原料、組成比、合成方法を含めて様々な条件で鋭意検討を実施した。その結果、新規なセグメント化ポリウレタンの合成に成功し、本発明に至ったのである。 Under the above concept, the present inventors have formed microphase-separated structures with different domain sizes in the segmented polyurethane, using fluorine-containing monomers and silicon-containing monomers as constituents, and used as medical materials. In order to realize suitable surface characteristics, mechanical characteristics, etc., intensive studies were conducted under various conditions including synthetic raw materials, composition ratios, and synthesis methods. As a result, a novel segmented polyurethane was successfully synthesized and the present invention was achieved.
すなわち、本発明によれば、ジイソシアネートとフッ素を含むジオールとケイ素を含むジオールとをモノマーとするセグメント化ポリウレタンであって、ジイソシアネートとフッ素を含むジオールのウレタン重合からなるミクロドメインとジイソシアネートとケイ素を含むジオールのウレタン重合からなるミクロドメインとが相分離しているセグメント化ポリウレタンが提供される。前記ケイ素を含むジオールと前記フッ素を含むジオールの組成比（ケイ素／フッ素）は、１〜３とすることが好ましい。また、前記ケイ素を含むジオールは、オリゴジフェニルシロキサン、オリゴジメチルジフェニルシロキサン、オリゴテトラメチル−ｐ−シルフェニレンシロキサン、オリゴトリフルオロプロピルメチルシロキサン、およびオリゴジメチルシロキサンからなる群より選ばれる少なくとも１種であり数平均分子量が７００〜１７００のジオールとすることが好ましい。さらに、前記フッ素を含むジオールは、２，２−ビス〔４−（２−ヒドロキシエトキシ)フェニル〕ヘキサフルオロプロパン、２，２−ビス〔４−（３−ヒドロキシプロポキシ)フェニル〕ヘキサフルオロプロパン、２，２−ビス〔４−（４−ヒドロキシブトキシ)フェニル〕ヘキサフルオロプロパン、２，２−ビス〔４−（５−ヒドロキシペントキシ)フェニル〕ヘキサフルオロプロパン、２，２−ビス〔４−（６−ヒドロキシヘキソキシ)フェニル〕ヘキサフルオロプロパン、２，２−ビス〔４−（８−ヒドロキシオクトキシ)フェニル〕ヘキサフルオロプロパン、２，２−ビス〔４−（１０−ヒドロキシデコキシ)フェニル〕ヘキサフルオロプロパン、２，２−ビス〔４−（４−ヒドロキシフェノキシ)フェニル〕ヘキサフルオロプロパン、２，２−ビス〔４−（３−ヒドロキシフェノキシ)フェニル〕ヘキサフルオロプロパン、４，４’−(ヘキサフルオロイソプロピリデン)ビス〔Ｎ−(ヒドロキシメチル)フタルイミド〕、４，４’-(ヘキサフルオロイソプロピリデン)ビス〔Ｎ−(３−ヒドロキシプロピル)フタルイミド〕、４，４’−(ヘキサフルオロイソプロピリデン)ビス〔Ｎ−（４−ヒドロキシブチル)フタルイミド〕、４，４’−（ヘキサフルオロイソプロピリデン)ビス〔Ｎ−（５−ヒドロキシペンチル)フタルイミド〕、４，４’−（ヘキサフルオロイソプロピリデン)ビス〔Ｎ−（６−ヒドロキシヘキシル)フタルイミド〕、４，４’−（ヘキサフルオロイソプロピリデン)ビス〔Ｎ−（８−ヒドロキシオクチル)フタルイミド〕、４，４’−(ヘキサフルオロイソプロピリデン)ビス〔Ｎ−（１０−ヒドロキシデシル)フタルイミド〕、４，４’−(ヘキサフルオロイソプロピリデン)ビス〔Ｎ−（４−ヒドロキシフェニル)フタルイミド〕、４，４’−（ヘキサフルオロイソプロピリデン)ビス〔Ｎ−（３−ヒドロキシフェニル)フタルイミド〕、および４，４’−(ヘキサフルオロイソプロピリデン)ビス［Ｎ-(２-ヒドロキシエチル)フタルイミド]からなる群より選ばれる少なくとも１種のジオールとすることが好ましい。さらに加えて、前記ジイソシアネートは、２，４−トリレンジイソシアネート、２，６−トリレンジイソシアネート、１，４−フェニレンジイソシアネート、１，３−フェニレンジイソシアネート、１，５−ナフチレンジイソシアネート、２，６−ナフチレンジイソシアネート、３，３’−ジクロロ−４，４’−ジフェニルメタンジイソシアネート、１，４−キシリレンジイソシアネート、１，３−キシリレンジイソシアネート、４，４’−ジイソシアネート−３，３’−ジメチルジフェニルメタン、および４，４’−ジイソシアン酸メチレンジフェニルからなる群より選ばれる少なくとも１種のジイソシアネートとすることが好ましい。 That is, according to the present invention, a segmented polyurethane having a diisocyanate, a fluorine-containing diol, and a silicon-containing diol as monomers, the microdomain formed by urethane polymerization of the diisocyanate and fluorine-containing diol, the diisocyanate, and silicon is included. A segmented polyurethane is provided in which the microdomains comprising urethane polymerization of diols are phase separated. The composition ratio (silicon / fluorine) of the diol containing silicon and the diol containing fluorine is preferably 1 to 3. The silicon-containing diol is at least one selected from the group consisting of oligodiphenylsiloxane, oligodimethyldiphenylsiloxane, oligotetramethyl-p-sylphenylenesiloxane, oligotrifluoropropylmethylsiloxane, and oligodimethylsiloxane. A diol having a number average molecular weight of 700 to 1700 is preferred. Further, the fluorine-containing diol includes 2,2-bis [4- (2-hydroxyethoxy) phenyl] hexafluoropropane, 2,2-bis [4- (3-hydroxypropoxy) phenyl] hexafluoropropane, 2 , 2-bis [4- (4-hydroxybutoxy) phenyl] hexafluoropropane, 2,2-bis [4- (5-hydroxypentoxy) phenyl] hexafluoropropane, 2,2-bis [4- (6 -Hydroxyhexoxy) phenyl] hexafluoropropane, 2,2-bis [4- (8-hydroxyoctoxy) phenyl] hexafluoropropane, 2,2-bis [4- (10-hydroxydecoxy) phenyl] hexa Fluoropropane, 2,2-bis [4- (4-hydroxyphenoxy) phenyl] hexafluoropropane, 2, -Bis [4- (3-hydroxyphenoxy) phenyl] hexafluoropropane, 4,4 '-(hexafluoroisopropylidene) bis [N- (hydroxymethyl) phthalimide], 4,4'-(hexafluoroisopropylidene) Bis [N- (3-hydroxypropyl) phthalimide], 4,4 ′-(hexafluoroisopropylidene) bis [N- (4-hydroxybutyl) phthalimide], 4,4 ′-(hexafluoroisopropylidene) bis [ N- (5-hydroxypentyl) phthalimide], 4,4 '-(hexafluoroisopropylidene) bis [N- (6-hydroxyhexyl) phthalimide], 4,4'-(hexafluoroisopropylidene) bis [N- (8-hydroxyoctyl) phthalimide], 4,4 ′-(hexafluoroisopropylidene) bis [N -(10-hydroxydecyl) phthalimide], 4,4 '-(hexafluoroisopropylidene) bis [N- (4-hydroxyphenyl) phthalimide], 4,4'-(hexafluoroisopropylidene) bis [N- ( 3-hydroxyphenyl) phthalimide] and 4,4 ′-(hexafluoroisopropylidene) bis [N- (2-hydroxyethyl) phthalimide] are preferably used as at least one diol. In addition, the diisocyanate may be 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, 1,5-naphthylene diisocyanate, 2,6- Naphthylene diisocyanate, 3,3′-dichloro-4,4′-diphenylmethane diisocyanate, 1,4-xylylene diisocyanate, 1,3-xylylene diisocyanate, 4,4′-diisocyanate-3,3′-dimethyldiphenylmethane, And at least one diisocyanate selected from the group consisting of methylenediphenyl 4,4′-diisocyanate is preferred.
さらに、本発明によれば、前記セグメント化ポリウレタンを含む医療用器具が提供され、さらに加えて、本発明によれば、前記セグメント化ポリウレタンを含む、心臓人工弁、血管留置カテーテル、バルーンカテーテル、大動脈バイパスチューブ、人工血管、人工心臓ポンプ、大動脈バルーン、バイオセンサ、縫合糸、生体接着剤、歯科矯正用材料、人工皮膚などに代表される生体適合性要素が提供される。 Furthermore, according to the present invention, there is provided a medical device including the segmented polyurethane, and in addition, according to the present invention, a cardiac prosthetic valve, a vascular indwelling catheter, a balloon catheter, an aorta including the segmented polyurethane. Biocompatible elements represented by bypass tubes, artificial blood vessels, artificial heart pumps, aortic balloons, biosensors, sutures, bioadhesives, orthodontic materials, artificial skins and the like are provided.
上述したように、本発明によれば、高い抗血栓性に加え、好適な弾性および耐疲労性を備えるセグメント化ポリウレタン、該ポリウレタンを含む医療用器具、および、該ポリウレタンを含む生体適合性要素が提供される。 As described above, according to the present invention, there is provided a segmented polyurethane having high elasticity and fatigue resistance in addition to high antithrombogenicity, a medical device including the polyurethane, and a biocompatible element including the polyurethane. Provided.
以下、本発明を具体的な実施の形態をもって説明するが、本発明は、後述する実施の形態に限定されるものではない。以下、本発明のセグメント化ポリウレタンの合成について順を追って説明する。 Hereinafter, the present invention will be described with specific embodiments, but the present invention is not limited to the embodiments described below. Hereinafter, the synthesis of the segmented polyurethane of the present invention will be described step by step.
本発明のセグメント化ポリウレタンは、含フッ素ジオールおよび含ケイ素ジオール、ならびに、ジイソシアネートをモノマーとして行なわれる重合反応により合成される。上記重合反応は、含ケイ素ジオール成分を含む主鎖部分を合成する工程と、含フッ素ジオール成分によって上記主鎖部分を鎖延長する工程の２段階でなされる。第１の工程において、含ケイ素ジオール成分とジイソシアネートが重合し、主鎖部分となる含ケイ素オリゴマーが形成される。続いて、第２の工程において、含フッ素ジオール成分とジイソシアネートが重合してなる含フッ素オリゴマーが、上記主鎖部分とウレタン結合して鎖延長し高重合体が形成される。この際、含ケイ素オリゴマーおよび含フッ素オリゴマーは、それぞれのセグメントごとに集まる傾向にあり、ミクロドメインを形成して相分離する。本発明のセグメント化ポリウレタンのこのミクロ相分離構造は、ドメインサイズの様々に異なったミクロ相分離構造を形成し、図１に示すような、生体の血管の内膜にみられる、いわゆる海島構造に非常に近似した構造を備えていると考えられる。 The segmented polyurethane of the present invention is synthesized by a polymerization reaction performed using fluorine-containing diol, silicon-containing diol, and diisocyanate as monomers. The polymerization reaction is performed in two stages: a step of synthesizing a main chain portion containing a silicon-containing diol component and a step of extending the main chain portion with a fluorine-containing diol component. In the first step, the silicon-containing diol component and diisocyanate are polymerized to form a silicon-containing oligomer that becomes the main chain portion. Subsequently, in the second step, the fluorine-containing oligomer formed by polymerizing the fluorine-containing diol component and the diisocyanate is urethane-bonded to the main chain portion to extend the chain to form a high polymer. At this time, the silicon-containing oligomer and the fluorine-containing oligomer tend to gather for each segment, and form microdomains to cause phase separation. This microphase-separated structure of the segmented polyurethane of the present invention forms microphase-separated structures with various domain sizes, and is a so-called sea-island structure as seen in the inner lining of a blood vessel as shown in FIG. It is thought that it has a very similar structure.
本発明のセグメント化ポリウレタンの合成においては、ジオール成分の組成比を、含ケイ素ジオール／含フッ素ジオール（モル比）＝１〜３とすることが好ましい。また、本発明においては、上記２種類のジオール成分のうち組成の比率が大きいものとジイソシアネートを先に重合して主鎖部分を合成することが好ましい。すなわち、本発明においては、含ケイ素ジオールとジイソシアネートを先に重合して主鎖部分を合成することが好ましい。ただし、組成比が、含ケイ素ジオール／含フッ素ジオール（モル比）＝１の場合については、含フッ素ジオールとジイソシアネートを先に重合して主鎖部分を合成することもできる。以下、本発明のセグメント化ポリウレタンの合成工程について、含ケイ素ジオールの組成の比率が大きい場合を例にとって詳細に説明する。 In the synthesis of the segmented polyurethane of the present invention, the composition ratio of the diol component is preferably silicon-containing diol / fluorine-containing diol (molar ratio) = 1 to 3. Moreover, in this invention, it is preferable to synthesize | combine a principal chain part by superposing | polymerizing previously a thing with a large composition ratio among the above-mentioned two types of diol components and diisocyanate. That is, in the present invention, it is preferable to synthesize a main chain portion by previously polymerizing silicon-containing diol and diisocyanate. However, when the composition ratio is silicon-containing diol / fluorine-containing diol (molar ratio) = 1, the main chain portion can be synthesized by polymerizing fluorine-containing diol and diisocyanate first. Hereinafter, the process for synthesizing the segmented polyurethane of the present invention will be described in detail by taking as an example a case where the composition ratio of the silicon-containing diol is large.
第１の工程は、両末端イソシアネートオリゴマーを合成する工程である。まず最初に、所定の触媒の存在下、ジイソシアネートと含ケイ素ジオールを所定の重合溶媒中で撹拌して、本発明のセグメント化ポリウレタンにおいて主鎖となる、ケイ素を含む両末端イソシアネートオリゴマーを合成する。本発明においては、上記触媒にジラウリン酸−ｎ−ブチルスズ（以下、ＤＢＴＤＬという）を用いることができる。また、用いる触媒は、全モノマー（ジイソシアネートおよび含ケイ素ジオール）に対して０．２ｗ／ｗ−％（（触媒重量÷全モノマーの重量）×１００、以下同じ）の量とすることが好ましい。また、本発明において、上記撹拌は、１００℃で２時間程度行なうことが好ましい。 The first step is a step of synthesizing both terminal isocyanate oligomers. First, diisocyanate and silicon-containing diol are stirred in a predetermined polymerization solvent in the presence of a predetermined catalyst to synthesize a silicon-containing both-end isocyanate oligomer that becomes a main chain in the segmented polyurethane of the present invention. In the present invention, dilauric acid-n-butyltin (hereinafter referred to as DBTDL) can be used as the catalyst. The catalyst used is preferably 0.2 w / w-% ((catalyst weight ÷ total monomer weight) × 100, the same applies hereinafter) with respect to the total monomers (diisocyanate and silicon-containing diol). In the present invention, the stirring is preferably performed at 100 ° C. for about 2 hours.
第２の工程は、第１の工程で得られたケイ素を含む両末端イソシアネートオリゴマーと含フッ素ジオールとを重合させ鎖延長する工程である。まず最初に、所定の触媒の存在下、含フッ素ジオールを所定の重合溶媒に混ぜて反応溶液を調整する。本発明においては、上記触媒にＮ−エチルモルホリン（以下、Ｎ−ＥＭという）を用いることができる。また、用いる触媒は、含フッ素ジオールモノマーに対して０．２ｗ／ｗ−％の量とすることが好ましい。続いて、第１の工程において調整した反応溶液を、一旦室温に戻して所定の溶媒で希釈した後、上述した含フッ素ジオール溶液を加えて所定時間反応させ鎖延長する。本発明において上記鎖延長工程は、１００℃で６時間程度行なうことが好ましい。 The second step is a step of extending the chain by polymerizing the both-end isocyanate oligomer containing silicon obtained in the first step and the fluorine-containing diol. First, a reaction solution is prepared by mixing a fluorinated diol with a predetermined polymerization solvent in the presence of a predetermined catalyst. In the present invention, N-ethylmorpholine (hereinafter referred to as N-EM) can be used as the catalyst. Moreover, it is preferable that the catalyst used shall be the quantity of 0.2 w / w-% with respect to a fluorine-containing diol monomer. Subsequently, after the reaction solution prepared in the first step is once returned to room temperature and diluted with a predetermined solvent, the above-mentioned fluorine-containing diol solution is added to react for a predetermined time to extend the chain. In the present invention, the chain extension step is preferably performed at 100 ° C. for about 6 hours.
なお、本発明においては、上述した重合溶媒として、４−メチル−２−ペンタノン（以下、ＭＰという）を用いることができ、また使用する溶媒量は、ポリマー濃度が最終的に３０−６０ｗ／ｖ−％（（全モノマーの重量÷使用した溶媒の全体積）×１００、以下同じ）となるよう調整することが好ましい。さらに、本発明のセグメント化ポリウレタンの合成反応においては、ジイソシアネートの物質量と、含ケイ素ジオールと含フッ素ジオールの物質量の和とが当量になるよう調整することが望ましく、また上記重合反応はすべて窒素雰囲気下で行なうことが望ましい。本発明のセグメント化ポリウレタンの合成反応式を下記に示す。式中、Ａはジイソシアネート、Ｂは含ケイ素ジオール、Ｃは含フッ素ジオールを示すものとする。 In the present invention, 4-methyl-2-pentanone (hereinafter referred to as MP) can be used as the above-described polymerization solvent, and the amount of the solvent used is such that the polymer concentration is finally 30-60 w / v. It is preferable to adjust to −% ((weight of all monomers ÷ total volume of solvent used) × 100, hereinafter the same). Furthermore, in the synthesis reaction of the segmented polyurethane of the present invention, it is desirable to adjust the amount of diisocyanate and the sum of the amounts of silicon-containing diol and fluorine-containing diol to be equivalent. It is desirable to carry out in a nitrogen atmosphere. The synthetic reaction formula of the segmented polyurethane of the present invention is shown below. In the formula, A represents a diisocyanate, B represents a silicon-containing diol, and C represents a fluorine-containing diol.
本発明のセグメント化ポリウレタンは、注射器ガスケット、血液バッグなどの各種医療用器具を始め、心臓人工弁、血管留置カテーテル、バルーンカテーテル、大動脈バイパスチューブ、人工血管、人工心臓ポンプ、大動脈バルーン、バイオセンサ、縫合糸、生体接着剤、歯科矯正用材料、および人工皮膚など、血液と直接接触する生体適合性要素に応用することが可能である。 The segmented polyurethane of the present invention includes various medical instruments such as syringe gaskets and blood bags, heart prosthetic valves, vascular indwelling catheters, balloon catheters, aortic bypass tubes, artificial blood vessels, artificial heart pumps, aortic balloons, biosensors, It can be applied to biocompatible elements that are in direct contact with blood, such as sutures, bioadhesives, orthodontic materials, and artificial skin.
以下、本発明のセグメント化ポリウレタンについて、実施例を用いてより具体的に説明を行うが、本発明は、後述する実施例に限定されるものではない。 Hereinafter, although the segmented polyurethane of this invention is demonstrated more concretely using an Example, this invention is not limited to the Example mentioned later.
（実施例１）
（１）セグメント化ポリウレタンの合成
本発明のセグメント化ポリウレタンの合成に際し、ジイソシアネート成分として、４，４’−ジイソシアン酸メチレンジフェニル（東京化成製、以下、Ａという）を用いた。４，４’−ジイソシアン酸メチレンジフェニルの化学式を下記に示す。
Example 1
(1) Synthesis of segmented polyurethane In the synthesis of the segmented polyurethane of the present invention, methylene diphenyl 4,4'-diisocyanate (manufactured by Tokyo Chemical Industry, hereinafter referred to as A) was used as the diisocyanate component. The chemical formula of methylenediphenyl 4,4′-diisocyanate is shown below.
ナスフラスコに４，４’−(ヘキサフルオロイソプロピリデン)ジフタル酸無水物（０．０４ｍｏｌ，１７．７６ｇ）とＮ，Ｎ−ジメチルアセトアミド（ＤＭＡｃ，６０ｍｌ）をとり、酸無水物が完全に溶けるまで室温でかき混ぜた。氷水温度（約５℃）に冷やした後、これにＤＭＡｃ（２０ｍｌ）とエタノールアミン（０．０８ｍｏｌ，４．８８ｇ）を混ぜた溶液を滴下して加え、２時間かき混ぜてアミド酸溶液を得た。還流管とディンスタークトラップを取り付け、トルエン（１６０ｍｌ）を加えて、１３５−１４０度で加熱しながら水（約１．４４ｍｌ）を共沸除去した。減圧ポンプを用いてＤＭＡｃおよびトルエンを留去した。残渣にエーテルを加えて粉砕し、沈殿物をろ別し、減圧乾燥してＣを得た。Ｃの合成反応式を下記に示す。 Take 4,4 ′-(hexafluoroisopropylidene) diphthalic anhydride (0.04 mol, 17.76 g) and N, N-dimethylacetamide (DMAc, 60 ml) in an eggplant flask until the acid anhydride is completely dissolved. Stir at room temperature. After cooling to ice water temperature (about 5 ° C.), a solution of DMAc (20 ml) and ethanolamine (0.08 mol, 4.88 g) was added dropwise thereto and stirred for 2 hours to obtain an amic acid solution. . A reflux tube and a Din Stark trap were attached, toluene (160 ml) was added, and water (about 1.44 ml) was removed azeotropically while heating at 135-140 degrees. DMAc and toluene were distilled off using a vacuum pump. Ether was added to the residue and pulverized, and the precipitate was filtered off and dried under reduced pressure to obtain C. The synthesis reaction formula of C is shown below.
本発明のセグメント化ポリウレタンの合成を、ジオール成分ＢとＣの仕込み組成比を変えて行った。具体的には、ジオール成分の仕込み組成比を、Ｂ：Ｃ＝７：１、３：１、２：１、１：１としてそれぞれ合成を行った。なお、Ｂ：Ｃ＝１：１の仕込み組成については、ＢとＣの添加の順序を変えて２回行なった。合成に際し、重合溶媒にＭＰを使用し、溶媒量はポリマー濃度が最終的に３０−６０ｗ／ｖ−％となるよう反応ごとに変えた。また、すべての反応において、Ａの物質量と、ＢとＣの物質量の和とが当量になるよう正確に調整した。なお、操作はすべて窒素気流中で行い、ＢをＡに対し先に添加して重合反応させたのち、Ｃを添加して反応させるという順序で行った。 The segmented polyurethane of the present invention was synthesized by changing the charged composition ratio of the diol components B and C. Specifically, the synthesis was performed with the charged composition ratio of the diol component being B: C = 7: 1, 3: 1, 2: 1, 1: 1. Note that the charge composition of B: C = 1: 1 was performed twice by changing the order of addition of B and C. In the synthesis, MP was used as a polymerization solvent, and the amount of the solvent was changed for each reaction so that the polymer concentration was finally 30-60 w / v-%. In all the reactions, the amount of substance A and the sum of the amounts of substances B and C were adjusted to be equivalent. All the operations were performed in a nitrogen stream, and B was added to A first to cause a polymerization reaction, and then C was added to react.
併せて、仕込み組成比（Ｂ：Ｃ）＝１：０、０：１、および、仕込み組成比（Ｂ：Ｃ）＝１：３、１：７についても合成を行なった。合成反応の一例として、仕込み組成比がＢ：Ｃ＝２：１の場合の合成手順について、以下詳細に述べる。 In addition, synthesis was also performed for the feed composition ratio (B: C) = 1: 0, 0: 1 and the feed composition ratio (B: C) = 1: 3, 1: 7. As an example of the synthesis reaction, the synthesis procedure when the charged composition ratio is B: C = 2: 1 will be described in detail below.
まず、三口フラスコにＡ（９ｍｍｏｌ・２．２５ｇ）とＭＰ（６ｍｌ）をとり、Ａが完全に溶けるまで室温でかき混ぜた。これにＭＰ（１０ｍｌ）、Ｂ（６ｍｍｏｌ・７．１９ｇ）と触媒のＤＢＴＤＬ（０．０１９ｇ・モノマーＡ＋Ｂに対して０．２ｗ／ｗ−％）を混ぜた溶液を滴下して加えた。還流管を取り付け、１００℃で２時間かき混ぜて主鎖部分となる両末端イソシアネートオリゴマーを合成した。反応溶液を一旦室温に戻し、ＭＰ（３ｍｌ）で希釈した後、これに、ＭＰ（９ｍｌ）、Ｃ（３ｍｍｏｌ・１．５９ｇ）と触媒のＮ−ＥＭ（０．００３ｇ・モノマーＣに対して０．２ｗ／ｗ−％）を混ぜた溶液を滴下して加え、１００℃で６時間かき混ぜて鎖延長した。反応溶液を多量の水−メタノール混合液に投入し、生じた沈殿物をろ過して、水およびメタノールで交互に洗浄した後、減圧乾燥して本発明のセグメント化ポリウレタンを得た。 First, A (9 mmol · 2.25 g) and MP (6 ml) were placed in a three-necked flask and stirred at room temperature until A was completely dissolved. A solution prepared by mixing MP (10 ml), B (6 mmol · 7.19 g) and catalyst DBTDL (0.019 g · 0.2 w / w-% with respect to monomer A + B) was added dropwise thereto. A reflux tube was attached, and the mixture was stirred at 100 ° C. for 2 hours to synthesize both-end isocyanate oligomers serving as main chain portions. The reaction solution was once returned to room temperature and diluted with MP (3 ml), and then MP (9 ml), C (3 mmol · 1.59 g) and catalyst N-EM (0.003 g · monomer C 0%). .2 w / w-%) was added dropwise, and the mixture was stirred at 100 ° C. for 6 hours to extend the chain. The reaction solution was poured into a large amount of water-methanol mixture, and the resulting precipitate was filtered, washed alternately with water and methanol, and then dried under reduced pressure to obtain the segmented polyurethane of the present invention.
上述した他の仕込み組成比（Ｂ：Ｃ）＝７：１、３：１、１：１についても上記と同様の条件で合成を行った。なお、仕込み組成比（Ｂ：Ｃ）＝１：３、１：７の合成については、ＣをＡに対し先に添加して重合反応させたのち、Ｂを添加して反応させるという順序で行い、第１の工程は、Ｎ−ＥＭの存在下１００℃で６時間、第２の工程は、ＤＢＴＤＬの存在下１００℃で２時間、重合溶媒にはＭＰとＤＭＡｃの１：１混合溶液を用い、他は上記と同様の条件で反応を行った。仕込み組成比（Ｂ：Ｃ）＝１：０については、ＤＢＴＤＬの存在下１００℃で２時間、仕込み組成比（Ｂ：Ｃ）＝０：１については、Ｎ−ＥＭの存在下１００℃で６時間、他は上記と同様の条件で反応を行った。 The other charged composition ratios (B: C) = 7: 1, 3: 1, and 1: 1 were synthesized under the same conditions as described above. In addition, about the synthesis | combination of preparation composition ratio (B: C) = 1: 3, 1: 7, it carries out in order of adding C and reacting by adding C first to A, then adding B and making it react. The first step is 6 hours at 100 ° C. in the presence of N-EM, the second step is 2 hours at 100 ° C. in the presence of DBTDL, and a 1: 1 mixed solution of MP and DMAc is used as the polymerization solvent. The others were reacted under the same conditions as described above. For feed composition ratio (B: C) = 1: 0, 2 hours at 100 ° C. in the presence of DBTDL; for feed composition ratio (B: C) = 0: 1, 6 at 100 ° C. in the presence of N-EM The reaction was carried out under the same conditions as above except for time.
各組成比における生成物についてゲル浸透クロマトグラフ（以下、ＧＰＣという）を行い分子量を決定した。ＧＰＣ分析は、送液ポンプ（Ｊａｓｃｏ・８８０−ＰＵインテリジェントＨＰＬＣポンプ）、カラムオーブン（Ｓｈｉｍａｄｚｕ・ＣＴＯ−２Ａ ＬＣ Ｉｎｊｅｃｔｏｒ ＳＩＬ-１Ａ）、カラム（Ｓｈｏｄｅｘ・ＧＰＣ ＫＤ−８０４）、検出器（Ｊａｓｃｏ・ＲＩ−２０３１ Ｐｌｕｓインテリジェント ＲＥ ｄｅｔｅｃｔｏｒ）およびレコーダー（Ｓｈｉｍａｄｚｕ・Ｃ−Ｒ６Ａ Ｃｈｒｏｍａｔｏｐａｃ）からなる装置を用いて、溶出液：Ｎ，Ｎ−ジメチルホルムアミド（ＤＭＦ）、流速：１．０ｍｌ／ｍｉｎ、カラム温度：４０℃の測定条件において行い、分子量の決定は、標準ポリスチレン換算で行った。下記表１に、各組成比の生成物の収率、還元粘度、およびＧＰＣ分析結果をまとめて示した。なお、表中、Ｍｎは、数平均分子量を、Ｍｗは、重量平均分子量を示す。 The product at each composition ratio was subjected to gel permeation chromatography (hereinafter referred to as GPC) to determine the molecular weight. GPC analysis was carried out using a liquid feed pump (Jasco 880-PU intelligent HPLC pump), a column oven (Shimadzu CTO-2A LC Injector SIL-1A), a column (Shodex GPC KD-804), a detector (Jasco RI- Using an apparatus consisting of a 2031 Plus Intelligent RE detector and a recorder (Shimadzu C-R6A Chromatopac), eluent: N, N-dimethylformamide (DMF), flow rate: 1.0 ml / min, column temperature: 40 ° C. The measurement was performed under measurement conditions, and the molecular weight was determined in terms of standard polystyrene. Table 1 below collectively shows the product yields, reduced viscosities, and GPC analysis results for each composition ratio. In the table, Mn represents the number average molecular weight, and Mw represents the weight average molecular weight.
上述した手順で合成したポリウレタンにつき、各組成比における生成物の表面特性、機械的特性および熱特性を評価した。以下、詳細に説明する。 The polyurethane synthesized by the above-described procedure was evaluated for the surface characteristics, mechanical characteristics and thermal characteristics of the product at each composition ratio. Details will be described below.
（実施例２）
（２）セグメント化ポリウレタンの特性評価
（ａ）表面特性
各組成比における生成物の水に対する平衡接触角、および臨界表面張力を求め、表面特性を評価した。水に対する平衡接触角は、以下の手順で求めた。まず、合成したポリウレタンをＤＭＡｃに溶かし、これをスライドガラス上に流延した後、５０℃で乾燥、さらに６０℃で２日間減圧乾燥させてフィルムを作成した。次に、上記フィルム表面にイオン交換水約２μｌを滴下し、１分３０秒後にその接触角をエルマＧ−１接触角計を用いて測定した。この測定を５回以上行い、その平均値を水に対する平衡接触角とした。
(Example 2)
(2) Characteristic evaluation of segmented polyurethane (a) Surface characteristics The equilibrium contact angle of the product with respect to water and the critical surface tension at each composition ratio were determined, and the surface characteristics were evaluated. The equilibrium contact angle with water was determined by the following procedure. First, the synthesized polyurethane was dissolved in DMAc, cast onto a slide glass, dried at 50 ° C., and further dried under reduced pressure at 60 ° C. for 2 days to form a film. Next, about 2 μl of ion-exchanged water was dropped on the film surface, and after 1 minute and 30 seconds, the contact angle was measured using an Elma G-1 contact angle meter. This measurement was performed 5 times or more, and the average value was defined as the equilibrium contact angle with respect to water.
引き続き、臨界表面張力を以下の手順で、Ｚｉｓｍａｎ法によって求めた。フィルム表面に、後述する表面張力γ既知の有機液体約２μｌを滴下し、1分３０秒後にその接触角をエルマＧ−１接触角計を用いて測定した。この測定を５回以上行い、その平均値を表面張力γの有機液体に対する接触角θとした。以下に示す１１種類の有機液体に対する接触角のｃｏｓθをそれぞれのγに対してプロットすると直線が得られた。この直線をｃｏｓθ＝１（θ＝０°）まで外挿して、それに対応するγを求め、そのγ値を臨界表面張力γcとした。上記有機液体には、エチレングリコール（γ＝４７．７）、1-ブロモナフタレン（γ＝４７．６）、ジエチレングリコール（γ＝４４．４）、ポリエチレングリコールＭｗ＝２００（γ＝４３．５）、１，３−ブタンジオール（γ＝３７．８）、ヘキサクロロ−１，３−ブタジエン（γ＝３６．０）、ジプロピレングリコール（γ＝３３．９）、ｎ−ヘキサデカン（γ＝２７．６）、ｎ−テトラデカン（γ＝２６．７）、ｎ−ウンデカン（γ＝２４．７）およびｎ−デカン（γ＝２３．９）を使用した。下記表２に、各組成比の生成物の水に対する平衡接触角、および臨界表面張力をまとめて示す。 Subsequently, the critical surface tension was determined by the Zisman method according to the following procedure. About 2 μl of an organic liquid having a known surface tension γ, which will be described later, was dropped on the film surface, and after 1 minute 30 seconds, the contact angle was measured using an Elma G-1 contact angle meter. This measurement was performed five times or more, and the average value was defined as the contact angle θ of the surface tension γ with respect to the organic liquid. When cos θ of contact angles for the following 11 kinds of organic liquids was plotted against each γ, a straight line was obtained. This straight line was extrapolated to cos θ = 1 (θ = 0 °) to obtain the corresponding γ, and the γ value was taken as the critical surface tension γc. Examples of the organic liquid include ethylene glycol (γ = 47.7), 1-bromonaphthalene (γ = 47.6), diethylene glycol (γ = 44.4), polyethylene glycol Mw = 200 (γ = 43.5), 1,3-butanediol (γ = 37.8), hexachloro-1,3-butadiene (γ = 36.0), dipropylene glycol (γ = 33.9), n-hexadecane (γ = 27.6) N-tetradecane (γ = 26.7), n-undecane (γ = 24.7) and n-decane (γ = 23.9) were used. Table 2 below summarizes the equilibrium contact angle with respect to water and the critical surface tension of the product of each composition ratio.
（ｂ）機械的特性
各組成比における生成物の引っ張り試験を行い、破断強度、破断伸び、および弾性率を求めて機械的特性を評価した。引っ張り試験には、Ｏｒｉｅｎｔｅｃ ＳＴＡ−１１５０、およびＯｒｉｅｎｔｅｃ ＡＲ−６０００（レコーダ）を用い、荷重レンジ：２−２０ Ｎ ４−４０％、引っ張り速度：５−５０ｍｍ／ｍｉｎ、チャート速度：３００−１０００ｍｍ／ｍｉｎの条件で測定した。上記引っ張り試験には、寸法が３０ｍｍ（ｈ）×３ｍｍ（ｗ）、膜厚が０．０３−０．１０ｍｍのフィルム試料を用い、上記フィルム試料は、ポリウレタンをＤＭＡｃに溶かし、その溶液をＢ過剰のポリウレタンについてはテフロン板上に、Ｃ過剰のポリウレタンについてはガラス板上に流延し、５０℃で乾燥したのち、さらに６０℃で２日間減圧乾燥させて作成した。下記表３に、各組成比の生成物の破断強度、破断伸び、および弾性率を示す。
(B) Mechanical properties A tensile test of the product at each composition ratio was performed, and the mechanical properties were evaluated by determining the breaking strength, breaking elongation, and elastic modulus. For the tensile test, Orientec STA-1150 and Orientec AR-6000 (recorder) were used, load range: 2-20 N 4-40%, tensile speed: 5-50 mm / min, chart speed: 300-1000 mm / min It measured on condition of this. For the tensile test, a film sample having dimensions of 30 mm (h) × 3 mm (w) and a film thickness of 0.03-0.10 mm was used. In the film sample, polyurethane was dissolved in DMAc, and the solution was excess B. The polyurethane of No. 1 was cast on a Teflon plate, and the polyurethane of C excess was cast on a glass plate, dried at 50 ° C., and further dried under reduced pressure at 60 ° C. for 2 days. Table 3 below shows the breaking strength, breaking elongation, and elastic modulus of the product having each composition ratio.
（ｃ）熱特性
各組成比における生成物について、熱分析を行い熱特性を評価した。熱分析は、熱重量測定および示差走査熱量測定によって行った。熱重量測定は、ＳＩＩ ＴＧ／ＤＴＡ６２００を用い、昇温速度：１０Ｋ／ｍｉｎ、雰囲気：N２（２５０ｍｌ／ｍｉｎ）の条件で測定した。示差走査熱量測定は、ＳＩＩ ＤＳＣ６２００を用い、昇温速度：１０Ｋ／ｍｉｎ、雰囲気：Ｎ２（３０ｍＬ／ｍｉｎ）の条件で測定した。下記表４に、各組成比の生成物における、全重量の５％重量が失われる温度（ＤＴ５）および全重量の１０％重量が失われる温度（ＤＴ１０）、ならびに、ガラス転移温度（Ｔｇ）をまとめて示す。
(C) Thermal characteristics The products at each composition ratio were subjected to thermal analysis to evaluate thermal characteristics. Thermal analysis was performed by thermogravimetry and differential scanning calorimetry. Thermogravimetry was performed using SII TG / DTA6200 under the conditions of a heating rate of 10 K / min and an atmosphere of N2 (250 ml / min). Differential scanning calorimetry was performed using SII DSC6200 under the conditions of a heating rate of 10 K / min and an atmosphere of N 2 (30 mL / min). Table 4 below shows the temperature at which 5% of the total weight is lost (DT 5 ) and the temperature at which 10% of the total weight is lost (DT 10 ), and the glass transition temperature (T g ) is shown together.
（溶解性）
各組成比における生成物について、以下の手順で溶解性試験を行い、種々の溶媒に対する溶解性を評価した。試験管に各組成比における生成物を約１ｍｇ入れ、これに溶媒１ｍｌを加えて一晩放置し、溶解の度合いを目視して評価した。下記表５に、完全に溶けたものを（＋＋）、一部溶けたもの、もしくは膨潤したものを（＋）、不溶のものを（−）として、溶媒ごとにまとめて示した。
(Solubility)
About the product in each composition ratio, the solubility test was done in the following procedures, and the solubility with respect to a various solvent was evaluated. About 1 mg of the product in each composition ratio was put in a test tube, 1 ml of a solvent was added thereto and left overnight, and the degree of dissolution was visually evaluated. Table 5 below collectively shows each solvent with (++) for completely dissolved, (+) for partially dissolved or swollen, and (-) for insoluble.
以上説明したように、本発明によれば、医療用材料として好適な表面特性（特に抗血栓性）、ならびに、好適な機械的特性、耐熱性、易加工性を併せもつ、セグメント化ポリウレタン材料が提供され、人工心臓、大動脈バルーン、大動脈バイパスチューブなどをはじめとする医療用器具のさらなる改良に資することが期待される。 As described above, according to the present invention, there is provided a segmented polyurethane material having both surface characteristics (particularly antithrombogenicity) suitable as a medical material, and suitable mechanical characteristics, heat resistance, and easy processability. It is expected to contribute to further improvement of medical devices including artificial hearts, aortic balloons, aortic bypass tubes and the like.
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