JPH076942B2 - Ion-selective electrode - Google Patents
Ion-selective electrodeInfo
- Publication number
- JPH076942B2 JPH076942B2 JP62065216A JP6521687A JPH076942B2 JP H076942 B2 JPH076942 B2 JP H076942B2 JP 62065216 A JP62065216 A JP 62065216A JP 6521687 A JP6521687 A JP 6521687A JP H076942 B2 JPH076942 B2 JP H076942B2
- Authority
- JP
- Japan
- Prior art keywords
- ion
- selective electrode
- sensitive
- electrode
- polyurethane
- 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.)
- Expired - Lifetime
Links
- 239000000126 substance Substances 0.000 claims description 24
- 229920005749 polyurethane resin Polymers 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 10
- 229920001400 block copolymer Polymers 0.000 claims description 9
- -1 ethyleneoxy unit Chemical group 0.000 claims description 8
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 8
- 150000004985 diamines Chemical class 0.000 claims description 5
- 125000005442 diisocyanate group Chemical group 0.000 claims description 5
- 150000002009 diols Chemical class 0.000 claims description 5
- 239000004970 Chain extender Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 description 46
- 210000004369 blood Anatomy 0.000 description 13
- 239000008280 blood Substances 0.000 description 13
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- 239000012528 membrane Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 229920002635 polyurethane Polymers 0.000 description 8
- 239000004814 polyurethane Substances 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 229920003225 polyurethane elastomer Polymers 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 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 description 6
- 230000015271 coagulation Effects 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 3
- 208000007536 Thrombosis Diseases 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- DMKKMGYBLFUGTO-UHFFFAOYSA-N 2-methyloxirane;oxirane Chemical compound C1CO1.C1CO1.CC1CO1 DMKKMGYBLFUGTO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 108010067973 Valinomycin Proteins 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- FCFNRCROJUBPLU-UHFFFAOYSA-N compound M126 Natural products CC(C)C1NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC(=O)C(C(C)C)NC(=O)C(C)OC(=O)C(C(C)C)NC(=O)C(C(C)C)OC1=O FCFNRCROJUBPLU-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002555 ionophore Substances 0.000 description 2
- 230000000236 ionophoric effect Effects 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- SBHRWOBHKASWGU-UHFFFAOYSA-M tridodecyl(methyl)azanium;chloride Chemical class [Cl-].CCCCCCCCCCCC[N+](C)(CCCCCCCCCCCC)CCCCCCCCCCCC SBHRWOBHKASWGU-UHFFFAOYSA-M 0.000 description 2
- FCFNRCROJUBPLU-DNDCDFAISA-N valinomycin Chemical compound CC(C)[C@@H]1NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC(=O)[C@H](C(C)C)NC(=O)[C@H](C)OC(=O)[C@@H](C(C)C)NC(=O)[C@@H](C(C)C)OC1=O FCFNRCROJUBPLU-DNDCDFAISA-N 0.000 description 2
- 210000003462 vein Anatomy 0.000 description 2
- CXVOIIMJZFREMM-UHFFFAOYSA-N 1-(2-nitrophenoxy)octane Chemical compound CCCCCCCCOC1=CC=CC=C1[N+]([O-])=O CXVOIIMJZFREMM-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 1
- 239000005058 Isophorone diisocyanate Substances 0.000 description 1
- 229920012485 Plasticized Polyvinyl chloride Polymers 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000002785 anti-thrombosis Effects 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000601 blood cell Anatomy 0.000 description 1
- 230000023555 blood coagulation Effects 0.000 description 1
- 210000004204 blood vessel Anatomy 0.000 description 1
- VLMZBPWWBKGGHQ-UHFFFAOYSA-L calcium;dodecyl phosphate Chemical compound [Ca+2].CCCCCCCCCCCCOP([O-])([O-])=O VLMZBPWWBKGGHQ-UHFFFAOYSA-L 0.000 description 1
- 230000010351 cardiac pulsation Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000011532 electronic conductor Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000000338 in vitro Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 210000000265 leukocyte Anatomy 0.000 description 1
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical class CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- HNPFNYDBAOYNSY-UHFFFAOYSA-N oxirane;oxolane Chemical compound C1CO1.C1CO1.C1CCOC1 HNPFNYDBAOYNSY-UHFFFAOYSA-N 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000035790 physiological processes and functions Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920006264 polyurethane film Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000223 sodium ionophore Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は新規なイオン選択性電極に関するものである。
さらに詳しくいえば、本発明は、人体や血液に対する適
合性が良好で、生体関連の測定に好適な感応膜をもつイ
オン選択性電極に関するものである。TECHNICAL FIELD The present invention relates to a novel ion-selective electrode.
More specifically, the present invention relates to an ion-selective electrode having a sensitive membrane suitable for human body and blood and suitable for biological measurement.
従来の技術 従来、イオン選択性電極としては、例えばポリ塩化ビニ
ル樹脂やエポキシ樹脂とイオン感応物質との混合物から
成る感応膜、あるいは漆とイオン感応物質との混合物か
ら成る感応膜と高級アルキルアンモニウム塩、高級アル
キルリン酸塩、金属キレート化合物、クラウンエーテ
ル、バリノマイシン、その他イオノフオアなどのイオン
感応物質を用いたものが知られている。2. Description of the Related Art Conventionally, as an ion selective electrode, for example, a sensitive film made of a mixture of polyvinyl chloride resin or epoxy resin and an ion sensitive substance, or a sensitive film made of a mixture of lacquer and an ion sensitive substance and a higher alkylammonium salt. , Higher alkyl phosphates, metal chelate compounds, crown ethers, valinomycin, and other ion sensitive substances such as ionophore are known.
しかしながら、このようなイオン選択性電極を生体関連
の計測、例えば臨床検査の目的で血液中の電解質イオン
の測定などに使用する場合、該感応膜が血液適合性や生
体適合性に劣るために、膜上に血栓が生成したり、生体
自体が膜に対し、強い組織反応を示すことが多く、ま
た、膜材料から生体に悪影響を及ぼす成分を流出するな
どの欠点を伴う。However, when such an ion-selective electrode is used for biological-related measurement, for example, measurement of electrolyte ions in blood for the purpose of clinical examination, the sensitive membrane is poor in blood compatibility and biocompatibility. In many cases, blood clots are generated on the membrane, the living body itself exhibits a strong tissue reaction with the membrane, and there are drawbacks such as the outflow of components adversely affecting the living body from the membrane material.
発明が解決しようとする問題点 本発明は、このような従来のイオン選択性電極が有する
問題を解決し、生体関連の測定などに好適に用いること
のできるイオン選択性電極を提供することを目的として
なされたものである。DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention solves the problems of such conventional ion-selective electrodes and provides an ion-selective electrode that can be suitably used for biological-related measurements and the like. It was made as.
問題点を解決するための手段 本発明者らは、生体関連などの測定に好適なイオン選択
性電極を開発するために鋭意研究を重ねた結果、特定の
ポリウレタン系樹脂が高分子材料の中で血液適合性に最
も優れ、かつ成分の流出もない上に、生体適合性にも優
れていることに着目し、感応膜として、このポリウレタ
ン系樹脂とイオン感応物質との混合物から成るものを用
いることにより、前記目的を達成しうることを見い出
し、この知見に基づいて本発明を完成するに至つた。Means for Solving the Problems The inventors of the present invention have conducted extensive studies to develop an ion-selective electrode suitable for measurement of bio-related matters, and as a result, a specific polyurethane-based resin among polymer materials Focusing on the fact that it has the best blood compatibility, no outflow of components, and excellent biocompatibility, and that the sensitive membrane is made of a mixture of this polyurethane resin and ion sensitive material. As a result, they have found that the above object can be achieved, and have completed the present invention based on this finding.
すなわち、本発明は、（Ａ）イオン感応物質と、（Ｂ）
ジイソシアネートと、両末端に水酸基を有し、エチレン
オキシ単位から成るセグメントを両端に有するブロック
共重合体と、低分子ジオール及び低分子ジアミンの中か
ら選ばれた少なくとも１種の鎖延長剤とを反応させて得
られる生体適合性ポリウレタン系樹脂との混合物から成
る感応膜を有することを特徴とするイオン選択性電極を
提供するものである。That is, the present invention comprises (A) an ion-sensitive substance and (B)
Reacting a diisocyanate, a block copolymer having hydroxyl groups at both ends and a segment consisting of an ethyleneoxy unit at both ends, and at least one chain extender selected from low molecular weight diols and low molecular weight diamines The present invention provides an ion-selective electrode having a sensitive film made of a mixture with the biocompatible polyurethane resin obtained by the above process.
以下、本発明を詳細に説明する。Hereinafter, the present invention will be described in detail.
本発明電極においては、感応膜材料として、イオン感応
物質と前記ポリウレタン系樹脂との混合物が用いられ
る。イオン感応物質としては、従来イオン選択性電極の
感応膜に慣用されているもの、例えばトリオクチルメチ
ルアンモニウム塩やトリドデシルメチルアンモニウム塩
などの高級アルキルアンモニウム塩、ドデシルリン酸カ
ルシウムなどの高級アルキルリン酸塩、金属キレート化
合物、クラウンエーテル、バリノマイシン、その他のイ
オノフオアなどの中から任意に選択して用いることがで
きる。In the electrode of the present invention, a mixture of an ion sensitive substance and the polyurethane resin is used as a sensitive film material. As the ion-sensitive substance, those conventionally used in the sensitive membrane of the ion-selective electrode, for example, higher alkylammonium salts such as trioctylmethylammonium salt and tridodecylmethylammonium salt, higher alkylphosphate salts such as calcium dodecylphosphate, The metal chelate compound, crown ether, valinomycin, and other ionophores can be arbitrarily selected and used.
一方、前記ポリウレタン系樹脂は、ジイソシアネート
と、両末端に水酸基を有し、エチレンオキシ単位から成
るセグメントを両端に有するブロック共重合体と、低分
子ジオール及び低分子ジアミンの中から選ばれた少なく
とも１種の鎖延長剤とを反応させて得られる。このジイ
ソシアネートとしては、例えば4,4′‐ジフエニルメタ
ンジイソシアネート（以下、MDIと略す）、トリレンジ
イソシアネート、ヘキサメチレンジイソシアネート、イ
ソホロンジイソシアネート、4,4′‐ジシクロヘキシル
メタンジイソシアネートなどを用いることができる。ま
た、前記ブロック共重合体としては、両末端に水酸基を
有し、エチレンオキシ単位すなわちCH2CH2Oから成
るセグメントを両端に有するものが用いられ、中間部分
のセグメントについては特に限定されないが、例えばプ
ロピレンオキシ単位、ポリジメチルシロキサン単位、テ
トラヒドロフラン単位からなるものなどが挙げられる。On the other hand, the polyurethane-based resin is at least one selected from diisocyanate, a block copolymer having hydroxyl groups at both ends and having a segment composed of an ethyleneoxy unit at both ends, and a low-molecular diol and a low-molecular diamine. Obtained by reacting with a chain extender of the species. As this diisocyanate, for example, 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, etc. can be used. Further, as the block copolymer, those having a hydroxyl group at both ends and having a segment composed of an ethyleneoxy unit, that is, CH 2 CH 2 O at both ends are used, and the intermediate segment is not particularly limited, For example, those comprising a propyleneoxy unit, a polydimethylsiloxane unit, a tetrahydrofuran unit and the like can be mentioned.
また、鎖延長剤として用いられる低分子ジオールとして
は、例えばエチレングリコールや1,4-ブタンジオールな
どが、また低分子ジアミンとしては、例えばエチレンジ
アミン、プロピレンジアミン、キシリレンジアミンなど
がそれぞれ挙げられる。Examples of the low molecular weight diol used as the chain extender include ethylene glycol and 1,4-butanediol, and examples of the low molecular weight diamine include ethylene diamine, propylene diamine, and xylylene diamine.
前記ポリウレタン系樹脂は、例えば前記ジイソシアネー
トと前記ブロック共重合体とを重付加反応させ、さらに
低分子ジオールあるいは低分子ジアミンを用い鎖延長反
応を行って高分子量化するなどの方法で製造される。The polyurethane-based resin is produced, for example, by a polyaddition reaction of the diisocyanate and the block copolymer, and a chain extension reaction using a low molecular diol or a low molecular diamine to increase the molecular weight.
本発明で用いるポリウレタン系樹脂の具体例としては、
MDI、両末端に水酸基を有するエチレンオキシド‐プロ
ピレンオキシド‐エチレンオキシドブロツク共重合体、
エチレンジアミンなどを原料として得られるポリウレタ
ン（以下、DPと略す）、MDI、ポリオキシテトラメチレ
ングリコール、両末端に水酸基を有するエチレンオキシ
ド‐ポリジメチルシロキサン‐エチレンオキシドブロツ
ク共重合体、エチレングリコールなどを原料として得ら
れるポリウレタン（以下、KPと略す）、MDI、両末端に
水酸基を有するエチレンオキシド‐テトラヒドロフラン
‐エチレンオキシドブロツク共重合体、エチレンジアミ
ンなどを原料として得られるポリウレタン（以下、IPと
略す）などが挙げられる。Specific examples of the polyurethane resin used in the present invention include:
MDI, ethylene oxide-propylene oxide-ethylene oxide block copolymer having hydroxyl groups at both ends,
Polyurethane obtained from ethylenediamine etc. as raw material (hereinafter abbreviated as DP), MDI, polyoxytetramethylene glycol, ethylene oxide-polydimethylsiloxane-ethylene oxide block copolymer having hydroxyl groups at both ends, ethylene glycol etc. Examples thereof include polyurethane (hereinafter abbreviated as KP), MDI, ethylene oxide-tetrahydrofuran-ethylene oxide block copolymer having hydroxyl groups at both ends, and polyurethane (hereinafter abbreviated as IP) obtained by using ethylenediamine as a raw material.
これらのポリウレタン系樹脂は、血液適合性、すなわ
ち、血液と接した場合に血栓の形成を抑制する性質に優
れている上に、赤血球破壊、血小板の機能低下、白血球
の一過性減少、補体の活性化などの血液生理機能に及ぼ
す影響が極めて少なく、さらに、人工心臓の材料として
広く用いられているように、生体適合性にも優れる上
に、例えば、DPでは7000万回の伸縮疲労試験（約２年間
の心臓拍動伸縮に相当する）にも耐えるなど、耐疲労性
を有している。These polyurethane-based resins have excellent blood compatibility, that is, the property of suppressing the formation of thrombus when they come into contact with blood, and at the same time, destroy red blood cells, reduce the function of platelets, transiently reduce white blood cells, complement It has very little effect on blood physiological functions such as activation of blood cells, and it has excellent biocompatibility as it is widely used as a material for artificial hearts. It has fatigue resistance such as withstanding (corresponding to cardiac pulsation for about 2 years).
このポリウレタン系樹脂と前記イオン感応物質との混合
割合については特に制限はなく、広い範囲内から適宜選
択することができるが、通常ポリウレタン系樹脂とイオ
ン感応物質との合計重量に基づき、該イオン感応物質の
量が0.001〜80重量％になるような割合で用いられる。The mixing ratio of the polyurethane resin and the ion-sensitive substance is not particularly limited and can be appropriately selected from a wide range. Usually, the ion-sensitive substance is mixed based on the total weight of the polyurethane-based resin and the ion-sensitive substance. It is used in such a proportion that the amount of the substance is 0.001 to 80% by weight.
本発明においては、ポリウレタン系樹脂とイオン感応物
質との混合性の向上、感応膜の化学的、機械的特性の改
善、得られるイオン選択性電極の応答特性や電気的特性
の改善などの目的で、該ポリウレタン系樹脂とイオン感
応物質との混合物に、所望に応じ他の第三成分物質、例
えばアルキルリン酸塩、エステル、エーテル、アルコー
ル、ケトンなどを添加し、感応膜を作成してもよい。In the present invention, for the purpose of improving the mixing property of the polyurethane resin and the ion-sensitive substance, improving the chemical and mechanical properties of the sensitive film, and improving the response properties and electrical properties of the resulting ion-selective electrode. If necessary, another third component substance such as alkyl phosphate, ester, ether, alcohol, ketone, etc. may be added to the mixture of the polyurethane resin and the ion sensitive substance to form a sensitive film. .
この感応膜の作成方法の１例として、適当な溶媒にポリ
ウレタン系樹脂を溶解し、これにイオン感応物質及び所
望に応じて添加される第三成分を混合したのち、この混
合物をガラス板などの平滑な板上に流延し、溶媒を揮発
させてフイルム状の膜を作成する方法を挙げることがで
きる。As an example of the method for preparing the sensitive film, a polyurethane resin is dissolved in a suitable solvent, and an ion sensitive substance and a third component added as desired are mixed with this, and then the mixture is mixed with a glass plate or the like. A method of casting on a smooth plate and volatilizing the solvent to form a film-like film can be mentioned.
このようにして得られたフイルム状の膜は所望の大きさ
に切り取られ感応膜として本発明のイオン選択性電極に
用いられる。第１図は該感応膜を用いて作成されたイオ
ン選択性電極の１例の断面図であつて、前記のようにし
て形成され、所望の大きさに切り取られた感応膜１は電
極本体４の先端に接着され、その内部に内部液２及びシ
ールド線５に接続した内部電極３を有する構造を示して
いる。The film-like film thus obtained is cut into a desired size and used as a sensitive film in the ion-selective electrode of the present invention. FIG. 1 is a cross-sectional view of an example of an ion-selective electrode formed by using the sensitive film. The sensitive film 1 formed as described above and cut into a desired size has an electrode body 4 The structure has an internal electrode 3 that is bonded to the tip of the internal electrode 3 and is connected to the internal liquid 2 and the shield wire 5 inside.
また、感応膜作成方法の別の例として、適当な溶媒にポ
リウレタン系樹脂を溶解し、これにイオン感応物質及び
所望に応じて添加される他の物質を混合したのち、この
混合物を金属製電極基体上に塗布して溶媒を揮発させ、
該基体表面に感応膜を形成する方法がある。第２図及び
第３図は、このようにして得られた表面に感応膜を有す
る金属製電極基体を用いて作成された本発明のイオン選
択性電極の異なつた例の断面図であつて、シールド線５
に接続された金属製電極基体６の表面に感応膜１が設け
られた構造を示し、４は電極本体である。As another example of the method for preparing a sensitive film, a polyurethane resin is dissolved in a suitable solvent, and an ion sensitive substance and other substances added as desired are mixed therewith, and then this mixture is mixed with a metal electrode. Coating on a substrate to volatilize the solvent,
There is a method of forming a sensitive film on the surface of the substrate. FIGS. 2 and 3 are cross-sectional views of different examples of the ion-selective electrode of the present invention prepared by using the metal electrode substrate having a sensitive film on the surface thus obtained, Shielded wire 5
4 shows a structure in which the sensitive film 1 is provided on the surface of the metal electrode substrate 6 connected to the electrode body 4.
さらに、本発明のイオン選択性電極においては、適当な
電極基体上に、スピナーコーテイング法によつて、ポリ
ウレタン系樹脂とイオン感応物質との混合物を塗布し、
感応膜を形成させたものを用いることができるし、ま
た、その他の種々の形態をとることもできる。具体的に
は、感応膜を膜状のまま用いて測定する例や、針状の微
小電極、管状のフロー型電極などの例を挙げることがで
きる。Furthermore, in the ion-selective electrode of the present invention, a mixture of a polyurethane resin and an ion-sensitive substance is applied onto a suitable electrode substrate by a spinner coating method,
It is possible to use one having a sensitive film formed thereon, and it is also possible to take various other forms. Specific examples include a measurement using a sensitive film as it is, a needle-shaped microelectrode, and a tubular flow-type electrode.
このようにして作成されたイオン選択性電極において
は、ポリウレタン系樹脂の中にイオン感応物質が完全に
保持された感応膜が用いられているので、測定しようと
する血液などの生体試料中の電解質濃度の変化が、該感
応膜によつて電位に変換され、これが電極の内部液又は
金属などの電子伝導体を介して、電極自体の電位として
発現する。In the ion-selective electrode thus prepared, a sensitive membrane in which an ion-sensitive substance is completely retained in a polyurethane resin is used, so that an electrolyte in a biological sample such as blood to be measured is used. The change in concentration is converted into a potential by the sensitive film, and this is expressed as the potential of the electrode itself via the internal liquid of the electrode or the electronic conductor such as metal.
発明の効果 本発明のイオン選択性電極は、感応膜の基材樹脂とし
て、血液適合性や生体適合性に優れ、かつ生体に悪影響
を及ぼすような成分の流出がない上に、耐疲労性にも優
れたポリウレタン系樹脂を用いているため、例えば血液
中の電解質イオンの計測など、生体関連の計測に好適に
用いられ、かつ寿命の長いものである。Effect of the Invention The ion-selective electrode of the present invention has excellent blood compatibility and biocompatibility as a base resin for a sensitive membrane, and has no outflow of components that adversely affect the living body, and also has fatigue resistance. Since it also uses an excellent polyurethane resin, it is suitably used for biological-related measurement such as measurement of electrolyte ions in blood and has a long life.
実施例 次に実施例により本発明をさらに詳細に説明するが、本
発明はこれらの例によつてなんら限定されるものではな
い。EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.
実施例１ 塩化物イオン選択性電極を次のようにして作成した。Example 1 A chloride ion selective electrode was prepared as follows.
塩化物イオン感応物質として、トリドデシルメチルアン
モニウム塩化物を、ポリウレタン系樹脂としてKPを用
い、イオン感応物質0.4g及びKP0.6gをテトラヒドロフラ
ン6gに溶解したのち、この溶液を、平滑なガラス板上に
置いた直径約3cm、高さ約3cmの円筒状のガラスリング内
に流し込み、液が洩れないように放置し、テトラヒドロ
フランを室温で揮発させて、膜厚0.4mmの感応膜を得
た。これを直径約1.2cmの円形に切り取り、ガラス管の
先端に接着することにより極めて簡単に作成することが
できる。接着にはKPをテトラヒドロフランに溶解した溶
液を使用することができる。第１図はこうして作成した
イオン選択性電極の構成を示したものである。Tridodecylmethylammonium chloride was used as the chloride ion sensitive substance, KP was used as the polyurethane resin, 0.4 g of the ion sensitive substance and 0.6 g of KP were dissolved in 6 g of tetrahydrofuran, and this solution was placed on a smooth glass plate. It was poured into a cylindrical glass ring having a diameter of about 3 cm and a height of about 3 cm, allowed to stand without liquid leakage, and tetrahydrofuran was volatilized at room temperature to obtain a sensitive film having a thickness of 0.4 mm. It can be made very easily by cutting it into a circle with a diameter of 1.2 cm and bonding it to the tip of a glass tube. A solution prepared by dissolving KP in tetrahydrofuran can be used for adhesion. FIG. 1 shows the structure of the ion-selective electrode thus prepared.
このようにして作成した塩化物イオン選択性電極を塩化
ナトリウム水溶液に浸せきし、ダブルジヤンクシヨン比
較電極（オリオン社製）と該塩化物イオン選択性電極と
の間の電位差を測定し、応答特性を求めた。その結果を
第４図に示す。第４図は塩化物イオン濃度と電位差との
関係を示すグラフであり、この図から分かるように、本
発明のイオン選択性電極は10-5〜100Mの塩化物イオン濃
度の範囲内で塩化物イオン濃度を測定することができ
る。The chloride ion-selective electrode thus prepared was immersed in an aqueous sodium chloride solution, and the potential difference between the double-distance comparison electrode (manufactured by Orion Co.) and the chloride ion-selective electrode was measured to determine the response characteristics. I asked. The results are shown in FIG. Figure 4 is a graph showing the relationship between chloride ion concentration and potential difference, as can be seen from this figure, the ion selective electrode of the present invention is in the range of 10 -5 to 10 0 M chloride ion concentration The chloride ion concentration can be measured.
さらに、該イオン選択性電極の選択性について検討し
た。その結果を第１表に示す。Furthermore, the selectivity of the ion-selective electrode was examined. The results are shown in Table 1.
なお、選択性は公知の混合溶液法を用い、ニコルスキー
・アイゼンマン（Nicolsky-Eisenman）の式で定義され
る選択係数を算出して求めた。The selectivity was determined by using a known mixed solution method and calculating the selectivity coefficient defined by the Nicolsky-Eisenman equation.
実施例２ MDI、両末端に水酸基を有するエチレンオキシド‐プロ
ピレンオキシド‐エチレンオキシドブロツク共重合体
（平均分子量2000、エチレンオキシド単位含有量10重量
％）、スピログリコール、1,4-ブタンジオールを原料と
して得られたポリウレタン系樹脂（DP2）500mgと、イオ
ン感応物質としてのナトリウムイオノフオア50mg、2-ニ
トロフエニルオクチルエーテル450mg、テトラフエニル
ホウ酸ナトリウム2.5mgを、テトラヒドロフラン6gに溶
解して均一な溶液を調製した。この溶液を銅製パイプの
内側に塗布して感応膜を作成した。銅製パイプの外側に
はイオン感応物質を含まないポリウレタン系樹脂のエト
ラヒドロフラン溶液を塗布した。 Example 2 MDI was obtained by using ethylene oxide-propylene oxide-ethylene oxide block copolymer having hydroxyl groups at both ends (average molecular weight 2000, ethylene oxide unit content 10% by weight), spiroglycol, and 1,4-butanediol as raw materials. Polyurethane resin (DP 2 ) 500mg, sodium ionophore 50mg as ion-sensing substance, 2-nitrophenyl octyl ether 450mg, sodium tetraphenylborate 2.5mg are dissolved in tetrahydrofuran 6g to prepare a uniform solution. did. This solution was applied to the inside of a copper pipe to form a sensitive film. The outer surface of the copper pipe was coated with a solution of an etrahydrofuran polyurethane resin containing no ion-sensitive substance.
第５図はこのようにして作成したイオン選択性電極の構
造を示す断面図であり、１はイオン感応膜、７は金属製
パイプ、８はポリウレタン系樹脂膜、９はリード線であ
る。FIG. 5 is a cross-sectional view showing the structure of the ion-selective electrode prepared in this manner, wherein 1 is an ion sensitive film, 7 is a metal pipe, 8 is a polyurethane resin film, and 9 is a lead wire.
このイオン選択性電極を生体内の計測部分の血管とほぼ
同じ径になるように作成し、その両端にパイプを連結し
て、内部に液を通して、液中のナトリウムイオン濃度を
測定した。その結果を第６図に示す。第６図はナトリウ
ムイオン濃度と電位差との関係を示すグラフである。こ
の図から分かるように、該イオン選択性電極に、10-4〜
100Mの範囲のナトリウムイオン濃度を測定することがで
きる。This ion-selective electrode was made to have a diameter almost the same as that of a blood vessel in a measurement part in a living body, a pipe was connected to both ends thereof, and a liquid was passed through the inside to measure the sodium ion concentration in the liquid. The result is shown in FIG. FIG. 6 is a graph showing the relationship between sodium ion concentration and potential difference. As can be seen from this figure, the ion-selective electrode has 10 -4 ~
It can be measured sodium ion concentration in the range of 10 0 M.
参考例 次に各試料について、以下の方法に従つて抗血栓性を調
べた。Reference Example Next, the antithrombotic property of each sample was examined according to the following method.
実施例１及び実施例２と同様に調製してポリウレタンエ
ラストマーKP及びDP2の10％のジメチルアセトアミド溶
液1mlを直径12mm、長さ10cmのすり合せふた付試験管に
入れ、ロータリーエバポレーターに接続して減圧回転
下、その内壁に均一にコーテイングする。1 ml of a 10% dimethylacetamide solution of polyurethane elastomers KP and DP2 prepared in the same manner as in Examples 1 and 2 was placed in a test tube with a lapping lid having a diameter of 12 mm and a length of 10 cm, which was connected to a rotary evaporator to reduce the pressure. Under rotation, coat the inner wall uniformly.
採取直後の健康人血液1mlづつ２本の試験管に入れ、37
℃に保ちながら、５分間経過後から30秒ごとにこの試験
管１本を45度傾斜させて流動状態を観察し、血液が全く
流動しなくなつてから、他の１本について同様な操作を
行い、この試験管内の血液が全く流動しなくなるまでの
経過時間をもつて試料の凝固時間とする。他方、ポリウ
レタンエラストマーをコーテイングしないガラス試験管
２本について、同じ操作で、ガラスの凝固時間を評価す
る。ガラスの凝固時間は、個体差はあるが、通常６〜14
分である。ガラス及び試料ポリウレタンエラストマーに
ついて５回以上のテストにより得られた値の平均値をも
つて凝固時間とする。抗血栓性の指標としては、ガラス
の凝固時間を１として各ポリウレタンエラストマーの凝
固時間の相対値で比較した。これらの結果を第２表に示
す。Immediately after collecting, put 1 ml of healthy human blood into 2 test tubes, 37
While keeping the temperature at ℃, after 5 minutes, tilt this test tube every 45 seconds to observe the flow state by tilting it at 45 degrees, and after the blood has stopped flowing at all, do the same operation for the other one. The time taken for the blood in the test tube to completely stop flowing is defined as the coagulation time of the sample. On the other hand, the glass coagulation time of two glass test tubes not coated with a polyurethane elastomer is evaluated by the same operation. Although the glass coagulation time varies depending on the individual, it is usually 6 to 14
Minutes. The coagulation time is obtained by averaging the values obtained by testing the glass and the sample polyurethane elastomer five times or more. As an index of antithrombogenicity, the coagulation time of glass was set to 1 and the relative values of the coagulation time of each polyurethane elastomer were compared. The results are shown in Table 2.
なお、比較のため、可塑化ポリ塩化ビニルについても試
験した。本発明のポリウレタンエラストマーの抗血栓性
が優れていることは明らかである。For comparison, plasticized polyvinyl chloride was also tested. It is clear that the polyurethane elastomer of the present invention has excellent antithrombogenicity.
別に、試料ポリウレタンエラストマーの10重量％ジメチ
ルアセトアミド溶液中に直径4mmの研磨されたステンレ
ス棒を浸せきして取出し、60℃で乾燥させて、ステンレ
ス棒表面にポリウレタン被膜を形成させる操作を繰り返
し行つて、所望の厚さにした後、エタノール液中に浸せ
きして、ステンレス棒を抜き去り、短かいチユーブを作
成する。Separately, dip a polished stainless steel rod having a diameter of 4 mm into a 10 wt% dimethylacetamide solution of a sample polyurethane elastomer, take it out, dry it at 60 ° C., and repeat the operation of forming a polyurethane film on the surface of the stainless steel rod. After adjusting the thickness to a desired value, it is dipped in an ethanol solution and the stainless rod is removed to form a short tube.
肉厚0.5mm、長さ17mm、内径4mmのチユーブを、成犬のけ
い静脈及び大たい部静脈中に埋入し、ドツプラー血流計
にて、埋入チユーブが、血液凝固にともなう血栓形成に
より閉塞するまでの時間（開存時間）を測定した。抗血
栓性の指標としては、参考例として試験したポリ塩化ビ
ニルの開存時間（30分以内）を１とした相対値により比
較した。これらを第２表に示す。A tube with a wall thickness of 0.5 mm, a length of 17 mm, and an inner diameter of 4 mm was embedded in the cervical vein and large vein of an adult dog, and the embedded tube was used to form a thrombus due to blood coagulation. The time until closure (patency time) was measured. As an index of antithrombogenicity, comparison was made by a relative value with the patency time (within 30 minutes) of polyvinyl chloride tested as a reference example being 1. These are shown in Table 2.
以上の生体外及び生体内試験結果から、本発明のポリウ
レタンエラストマーの抗血栓性が優れていることが分
る。 From the above in vitro and in vivo test results, it can be seen that the polyurethane elastomer of the present invention has excellent antithrombogenicity.
第１図、第２図、第３図及び第５図は、それぞれ本発明
のイオン選択性電極の異なつた構造の例を示す断面図で
あり、図中符号１はイオン感応膜、２は内部液、３は内
部電極、４は電極ボデー、５はシールド線、６は金属製
基体、７は金属製パイプ、８はポリウレタン系樹脂膜、
９はリード線である。 第４図及び第６図は、それぞれ本発明のイオン選択性電
極の実施例の応答特性を示すグラフである。1, FIG. 2, FIG. 3 and FIG. 5 are cross-sectional views showing examples of different structures of the ion-selective electrode of the present invention, in which reference numeral 1 is an ion-sensitive film, and 2 is an internal structure. Liquid, 3 is an internal electrode, 4 is an electrode body, 5 is a shield wire, 6 is a metal base, 7 is a metal pipe, 8 is a polyurethane resin film,
9 is a lead wire. 4 and 6 are graphs showing the response characteristics of the examples of the ion selective electrode of the present invention.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 山本 襄 大阪府池田市緑丘１丁目７−９ (72)発明者 山下 岩男 兵庫県川西市湯山台１丁目22−14 (56)参考文献 特開 昭58−2733（ＪＰ，Ａ) 特開 昭61−33644（ＪＰ，Ａ) ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Osamu Yamamoto 1-7-9 Midorigaoka, Ikeda-shi, Osaka (72) Inventor Iwao Yamashita 1-22-14 Yuyamadai, Kawanishi-shi, Hyogo (56) References 58-2733 (JP, A) JP-A-61-33644 (JP, A)
Claims (1)
アネートと、両末端に水酸基を有し、エチレンオキシ単
位から成るセグメントを両端に有するブロック共重合体
と、低分子ジオール及び低分子ジアミンの中から選ばれ
た少なくとも１種の鎖延長剤とを反応させて得られる生
体適合性ポリウレタン系樹脂との混合物から成る感応膜
を有することを特徴とするイオン選択性電極。1. An (A) ion-sensitive substance, (B) diisocyanate, a block copolymer having hydroxyl groups at both ends and having a segment consisting of an ethyleneoxy unit at both ends, a low-molecular diol and a low-molecular diamine. An ion-selective electrode having a sensitive film made of a mixture with a biocompatible polyurethane resin obtained by reacting with at least one chain extender selected from the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62065216A JPH076942B2 (en) | 1987-03-18 | 1987-03-18 | Ion-selective electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62065216A JPH076942B2 (en) | 1987-03-18 | 1987-03-18 | Ion-selective electrode |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63229356A JPS63229356A (en) | 1988-09-26 |
| JPH076942B2 true JPH076942B2 (en) | 1995-01-30 |
Family
ID=13280494
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62065216A Expired - Lifetime JPH076942B2 (en) | 1987-03-18 | 1987-03-18 | Ion-selective electrode |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH076942B2 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02231559A (en) * | 1989-03-03 | 1990-09-13 | Agency Of Ind Science & Technol | Field effect transistor type ion sensor |
| ES2173979T3 (en) * | 1994-11-14 | 2002-11-01 | Bayer Ag | THERMOPLASTIC POLYURETHANES SEGMENTED RANDOMLY AS A MATRIX FOR THE ELECTROCHEMICAL ANALYSIS OF IONS CA ++. |
| CA3070332A1 (en) * | 2019-04-30 | 2020-10-30 | Microtech Medical (Hangzhou) Co., Ltd. | Biosensors coated with co-polymers and their uses thereof |
| ES1289104Y (en) * | 2019-04-30 | 2022-06-28 | Microtech Medical Hangzhou Co Ltd | BIODETECTION SYSTEMS WITH BIOSENSORS COATED WITH COPOLYMERS AND THEIR USES. |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS582733A (en) * | 1981-06-30 | 1983-01-08 | Toshiba Corp | Ion selective electrode |
| JPS6133644A (en) * | 1984-07-25 | 1986-02-17 | 三菱レイヨン株式会社 | Living body electrode |
-
1987
- 1987-03-18 JP JP62065216A patent/JPH076942B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63229356A (en) | 1988-09-26 |
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