JPS6256976B2 - - Google Patents
Info
- Publication number
- JPS6256976B2 JPS6256976B2 JP55092379A JP9237980A JPS6256976B2 JP S6256976 B2 JPS6256976 B2 JP S6256976B2 JP 55092379 A JP55092379 A JP 55092379A JP 9237980 A JP9237980 A JP 9237980A JP S6256976 B2 JPS6256976 B2 JP S6256976B2
- Authority
- JP
- Japan
- Prior art keywords
- layer
- ion
- electrode
- selective
- water
- 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
Links
- 150000002500 ions Chemical class 0.000 claims description 86
- 239000003792 electrolyte Substances 0.000 claims description 40
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 37
- 150000003839 salts Chemical class 0.000 claims description 27
- 150000001450 anions Chemical class 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000007738 vacuum evaporation Methods 0.000 claims description 6
- 238000001771 vacuum deposition Methods 0.000 claims description 5
- 239000010408 film Substances 0.000 description 45
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 26
- 238000005259 measurement Methods 0.000 description 14
- 229910052709 silver Inorganic materials 0.000 description 14
- 239000004332 silver Substances 0.000 description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 13
- 239000001103 potassium chloride Substances 0.000 description 13
- 235000011164 potassium chloride Nutrition 0.000 description 13
- 239000000523 sample Substances 0.000 description 9
- 239000012488 sample solution Substances 0.000 description 9
- 229910021607 Silver chloride Inorganic materials 0.000 description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910001414 potassium ion Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000012086 standard solution Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 210000002966 serum Anatomy 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- -1 Ag 2 S Chemical class 0.000 description 3
- 108010010803 Gelatin Proteins 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 229920000159 gelatin Polymers 0.000 description 3
- 239000008273 gelatin Substances 0.000 description 3
- 235000019322 gelatine Nutrition 0.000 description 3
- 235000011852 gelatine desserts Nutrition 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000003456 ion exchange resin Substances 0.000 description 3
- 229920003303 ion-exchange polymer Polymers 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 108010067973 Valinomycin Proteins 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000000084 colloidal system Substances 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
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000009429 electrical wiring Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000011888 foil Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 150000003568 thioethers Chemical class 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
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- BXVSAYBZSGIURM-UHFFFAOYSA-N 2-phenoxy-4h-1,3,2$l^{5}-benzodioxaphosphinine 2-oxide Chemical compound O1CC2=CC=CC=C2OP1(=O)OC1=CC=CC=C1 BXVSAYBZSGIURM-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 102000007469 Actins Human genes 0.000 description 1
- 108010085238 Actins Proteins 0.000 description 1
- 229920000936 Agarose Polymers 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- MQIUGAXCHLFZKX-UHFFFAOYSA-N Di-n-octyl phthalate Natural products CCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCC MQIUGAXCHLFZKX-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229920002125 Sokalan® Polymers 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 239000013060 biological fluid Substances 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000003120 macrolide antibiotic agent Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000004584 polyacrylic acid Substances 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000001453 quaternary ammonium group Chemical group 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000000699 topical effect Effects 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 230000002087 whitening effect Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/333—Ion-selective electrodes or membranes
- G01N27/3335—Ion-selective electrodes or membranes the membrane containing at least one organic component
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Physical Vapour Deposition (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
Description
【発明の詳細な説明】
本発明は、イオン濃度測定用電極に関する。特
に本発明は、水性液、血液、血清などの体液中の
イオン濃度をポテンシオメトリカルに測定するた
めのイオン選択電極、その製造方法及びこの電極
を使用したイオン濃度測定用イオン電極集積板に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an electrode for measuring ion concentration. In particular, the present invention relates to an ion-selective electrode for potentiometrically measuring ion concentration in body fluids such as aqueous fluids, blood, and serum, a manufacturing method thereof, and an ion electrode stack plate for measuring ion concentration using this electrode. .
本発明で云う電極とは、一般に半電池或いは単
極と称せられているものと同一のものである。 The electrode referred to in the present invention is the same as what is generally called a half cell or a single electrode.
一般に生体液中のＫ，Na，Ca〓，Cl，
HCO3などの無機イオン濃度の測定は臨床医学
的に重要であり、そのために湿式法のイオン選択
電極を用いる方法が既に実施されている。 In general, K, Na, Ca〓, Cl,
Measuring the concentration of inorganic ions such as HCO 3 is clinically important, and a wet method using an ion-selective electrode has already been implemented for this purpose.
これらはいずれも針状の電極を生体液中に浸漬
して測定する形式のものであり、電極の保守、洗
浄、コンデイシヨニング、寿命、破損などの点で
管理が厄介であり、電極ヘツドを毎回カツプ中の
被検試料液に充分に浸漬する必要があるので、試
料液量は数百μ以上を必要とするものである。
かゝる不便を排除するために、電極をフイルム状
のドライタイプにして被検試料液をその上に点滴
する形式の電極フイルムが特開昭52−142584に又
電極を細いワイヤー状のドライタイプにまとめる
方法が特公昭52−47717および特開昭49−128793
に開示されている。特開昭52−142584によるイオ
ン選択電極フイルムは、絶縁性フイルムの上に金
属層、金属層の金属と同種の金属の水不溶性塩
層、水不溶性塩と共通の陰イオンをもつ水溶性塩
を溶解含有する親水性バインダーマトリツクスか
ら成る乾燥させた電解質層とイオン選択膜層をこ
の順に積層したドライタイプのものである。この
電極フイルムを一対にし、ブリツジで接続し、電
位差計につないだ後、試料液と標準液とをこの一
対の電極フイルム上にそれぞれ点滴し、電位差を
測定する事によつて試料液の濃度を知る事が出来
る。又特開昭49−128793には金属ワイヤーの上に
同心円状に金属ワイヤーと同種の金属の水不溶性
塩層、水不溶性塩と共通の陰イオンを含む電解質
層、イオン選択膜層がこの順に被覆されたソリツ
ドステートのイオン選択電極を用いて、該電極と
飽和甘コウ電極（対照電極として）とを電位差計
につないだ後試料液に該電極を浸漬して、電位差
を読む方法が記載されている。これらのドライタ
イプのイオン選択電極は、最上層のイオン選択膜
の種類を変えることによつて、夫々特定イオンの
測定が出来るもので、従つてＫ測定用、Na
測定用、Cl測定用、HCO3測定用の如く多く
の種類がある。 All of these methods use needle-shaped electrodes that are immersed in biological fluids for measurement, and are difficult to manage in terms of electrode maintenance, cleaning, conditioning, lifespan, and damage. Since it is necessary to sufficiently immerse the sample in the test sample liquid in the cup each time, the amount of sample liquid needs to be several hundred microns or more.
In order to eliminate such inconvenience, an electrode film of the type in which the electrode is a film-like dry type and the test sample liquid is dripped onto it was developed in JP-A-52-142584, and a thin wire-like dry type electrode was developed. The method of summarizing it is shown in Japanese Patent Publication No. 52-47717 and Japanese Patent Application Publication No. 49-128793.
has been disclosed. The ion-selective electrode film disclosed in JP-A-52-142584 has a metal layer on an insulating film, a water-insoluble salt layer of the same kind of metal as the metal in the metal layer, and a water-soluble salt having a common anion with the water-insoluble salt. It is a dry type in which a dried electrolyte layer consisting of a dissolved hydrophilic binder matrix and an ion selective membrane layer are laminated in this order. After forming a pair of electrode films, connecting them with a bridge, and connecting them to a potentiometer, the sample solution and standard solution are dripped onto the pair of electrode films, and the concentration of the sample solution is determined by measuring the potential difference. I can know. Furthermore, in JP-A No. 49-128793, a water-insoluble salt layer of the same type of metal as the metal wire, an electrolyte layer containing the same anion as the water-insoluble salt, and an ion-selective membrane layer are coated concentrically on a metal wire in this order. A method is described in which a solid-state ion-selective electrode is used to read the potential difference by connecting the electrode and a saturated red electrode (as a reference electrode) to a potentiometer, and then immersing the electrode in a sample solution. ing. These dry type ion-selective electrodes can measure specific ions by changing the type of ion-selective membrane on the top layer.
There are many types, such as those for measurement, Cl measurement, and HCO 3 measurement.
しかし電極フイルムの使用に関して、いくつか
の困難性がある。その１つとして該電極フイルム
が測定中に電位の変動をおこし易く（以下電位ド
リフトと記す）、従つて結果が不正確になり、溶
液中のイオン濃度測定による分析シートとしては
極めて不満足なものである。又繰返し使用するこ
とが出来ず、１回きりの使用が限度であり測定毎
に高価な新しい電極フイルムを必要とし極めて不
経済であつた。又ドライタイプのイオン選択電極
針の使用に関しても多くの困難性がある。例えば
前記同様な電位ドリフトがおこり、更にこのタイ
プでは一般にサイズの大きい対照電極と一対にし
て使用することが必要である為、装置全体のサイ
ズが大きくなり、超ミクロ量（５〜50μ程度）
の被検液の測定に適用することが困難であつた。
従来のイオン選択電極針およびイオン選択電極フ
イルムはすべて多かれ少なかれドリフトをおこす
ので、このドリフト現象を最少限にし、且つ極く
微量の試験溶液の液滴（約50μ以下）で正確な
測定が得られ、更に経済性を考慮して繰返し使用
出来る電極、特に臨床化学検査分野で使用する分
析シートとして広範囲のイオンのポテンシヨメト
リツク測定に適した電極フイルムが望まれてい
る。 However, there are some difficulties with the use of electrode films. One of the problems is that the electrode film tends to cause potential fluctuations during measurement (hereinafter referred to as potential drift), resulting in inaccurate results and is extremely unsatisfactory as an analysis sheet for measuring ion concentration in a solution. be. Furthermore, it cannot be used repeatedly, and can only be used once, requiring a new expensive electrode film for each measurement, which is extremely uneconomical. There are also many difficulties in using dry type ion selective electrode needles. For example, the same potential drift as described above occurs, and in addition, this type of electrode must be used in pair with a reference electrode that is generally large in size.
It was difficult to apply this method to the measurement of test liquids.
All conventional ion-selective electrode needles and ion-selective electrode films drift to a greater or lesser degree, so it is possible to minimize this drift phenomenon and obtain accurate measurements with extremely small droplets (approximately 50μ or less) of the test solution. Furthermore, there is a need for an electrode that can be used repeatedly in consideration of economic efficiency, and in particular, an electrode film that is suitable for potentiometric measurement of a wide range of ions as an analysis sheet used in the field of clinical chemistry testing.
本発明者らは、上記の種々の欠点を解消するた
め鋭意研究を重ねていたが、イオン選択電極の構
成要素である電解質層として電解質の薄膜を用い
ることにより、上記の種々の欠点が解決され、特
に起電力の応答速度が早く、応答時間（平衡電位
の90％を示すまでの時間）が著しく短縮し、更に
電位ドリフトが激減し、しかも繰返し使用が出来
るので、イオン濃度を再現性良く正確に定量出来
ることを発見した。 The present inventors have conducted extensive research to eliminate the various drawbacks mentioned above, and found that the various drawbacks described above were resolved by using a thin electrolyte film as the electrolyte layer, which is a component of the ion-selective electrode. In particular, the response speed of the electromotive force is fast, the response time (time to reach 90% of the equilibrium potential) is significantly shortened, potential drift is drastically reduced, and it can be used repeatedly, making it possible to accurately measure ion concentrations with good reproducibility. We discovered that it is possible to quantify
本発明の目的は、電極ドリフトが極めて僅かな
又はドリフトのないイオン選択電極を提供するこ
とにある。 An object of the present invention is to provide an ion selective electrode with very little or no electrode drift.
本発明の他の目的は、高度な再現性があり、感
度の良いレスポンスを与えうるイオン選択電極を
提供することにある。 Another object of the present invention is to provide an ion selective electrode that can provide highly reproducible and sensitive responses.
本発明の他の目的は、１回の試料附着操作だけ
で１項目又は多項目のイオン濃度を測定し得るイ
オン選択電極集積板に適した電極を提供すること
にある。 Another object of the present invention is to provide an electrode suitable for an ion-selective electrode integrated plate that can measure one or multiple ion concentrations with just one sample application operation.
本発明の他の目的は、その使用の間に実質的に
なんの特別な取り扱いを必要としない全体がソリ
ツドステートのドライ電極を提供することにあ
る。 Another object of the invention is to provide an entirely solid state dry electrode that requires virtually no special handling during its use.
本発明の他の目的は、繰返し使用が出来ること
から経済的に安価なイオン選択電極を提供するこ
とにある。 Another object of the present invention is to provide an economically inexpensive ion selective electrode that can be used repeatedly.
本発明の他の目的は、本発明のイオン選択電極
の製造方法を提供することにある。 Another object of the present invention is to provide a method for manufacturing the ion selective electrode of the present invention.
本発明の他の目的は、本発明のイオン選択電極
の２個からなる対の、少くとも１種を対にして設
けてなる１種以上のイオン濃度測定用のイオン選
択電極集積板を提供することにある。 Another object of the present invention is to provide an ion-selective electrode stack plate for measuring the concentration of one or more ions, which comprises at least one pair of two ion-selective electrodes according to the present invention. There is a particular thing.
本発明の電極は、導電性金属の上に該導電性金
属の水不溶性塩の層、次に該水不溶性塩の金属と
共通の陰イオンを有する電解質の層、更にイオン
選択層が順次設けられたイオン選択電極におい
て、該電解質の層が真空蒸着法によつて設けられ
たバインダーを含まず、実質的に電解質のみから
なることを特徴とするイオン選択電極である。 The electrode of the present invention is provided with a layer of a water-insoluble salt of the conductive metal on a conductive metal, a layer of an electrolyte having a common anion with the metal of the water-insoluble salt, and an ion-selective layer. The ion selective electrode according to the present invention is characterized in that the electrolyte layer does not contain a binder provided by vacuum evaporation and consists essentially only of the electrolyte.
本発明の電極は、導電性金属の上に、直接或い
は、該金属の上に該金属の水不溶性塩の層を設け
てから、バインダーを含まず実質的に該水不溶性
塩の陰イオンと共通の陰イオンを有する電解質の
みからなる層を真空蒸着法によつて設け、しかる
後イオン選択層を設けることによつて製造され
る。 The electrode of the present invention is prepared by providing a layer of a water-insoluble salt of the metal directly on the conductive metal, or by providing a layer of the water-insoluble salt of the metal on the conductive metal, and then forming a layer containing no binder and substantially common to the anion of the water-insoluble salt. It is manufactured by providing a layer consisting only of an electrolyte having anions of 1 by vacuum evaporation, and then providing an ion selective layer.
本発明の二種以上のイオン濃度測定用のイオン
選択電極集積板は、電気絶縁性表面を有する支持
体上に、上記の本発明の２個の電極からなる対の
少くとも２種を、その各電極端部が互いに短絡し
ないだけの間隔をおいて互いに近接するよう配置
してなるものである。 The ion-selective electrode stack plate for measuring the concentration of two or more ions of the present invention comprises at least two of the above pairs of two electrodes of the present invention on a support having an electrically insulating surface. The end portions of the electrodes are arranged close to each other with a spacing sufficient to prevent short-circuiting.
本発明の電極はフイルム状であつても良いし、
或いは針状又はワイヤー状であつても良い。 The electrode of the present invention may be in the form of a film,
Alternatively, it may be needle-shaped or wire-shaped.
本発明の電極を構成する物質としては、前記の
公報等によつて公知の電極に使用されている物質
と同じものが使用される。即ち導電性金属として
は例えば銀、銅、白金、金等、又これ等金属の水
不溶性塩としては例えばAgX（Ｘ：Cl，Br，
Ｉ）、Ag2S，Cu2Sの様なハロゲン化物、硫化物
等がある。水不溶性塩の陰イオンと共通の陰イオ
ンを有する電解質としては例えばカリウム、ナト
リウム、カルシウムのハロゲン化物或いは硫化
物、例えばKCl，NaCl，K2S等がある。イオン選
択層は有機物質からなるイオンキヤリヤーを含有
する疎水性有機バインダーから成るものである。
イオンキヤリヤーとしてはバリノマイシン、環式
ポリエーテル、テトララクトン、マクロリドアク
チン、エンニナチン群等がある。疎水性有機バイ
ンダーとしては薄膜を形成し得る疎水性の天然又
は合成高分子、例えばセルロースエステル、ポリ
塩化ビニル、ポリ塩化ビニリデン、ポリアクリロ
ニトリル、ポリウレタン、ポリカーボネート等が
ある。又イオン選択層としては、イオン交換樹脂
を使用する事も出来る。イオン交換樹脂として
は、例えばスルホン基、カルボキシル基を有する
重合体から成るカチオン交換樹脂、第１，２，３
級アミン又は第４アンモニウム基を有する重合体
から成るアニオン交換樹脂がある。更に具体的な
例としてはスルホン化ポリスチレンが挙げられ
る。 The materials constituting the electrode of the present invention are the same as those used in the known electrodes, such as in the above-mentioned publications. That is, examples of conductive metals include silver, copper, platinum, gold, etc., and examples of water-insoluble salts of these metals include AgX (X: Cl, Br,
I), halides such as Ag 2 S, Cu 2 S, sulfides, etc. Examples of electrolytes having an anion common to the anion of the water-insoluble salt include halides or sulfides of potassium, sodium, and calcium, such as KCl, NaCl, and K 2 S. The ion selective layer consists of a hydrophobic organic binder containing an ion carrier of organic material.
Examples of ion carriers include valinomycin, cyclic polyethers, tetralactones, macrolide actins, and enninatin groups. Hydrophobic organic binders include hydrophobic natural or synthetic polymers capable of forming thin films, such as cellulose esters, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polyurethane, polycarbonate, and the like. Further, an ion exchange resin can also be used as the ion selective layer. Examples of ion exchange resins include cation exchange resins made of polymers having sulfone groups and carboxyl groups;
There are anion exchange resins made of polymers having secondary amines or quaternary ammonium groups. A more specific example is sulfonated polystyrene.
金属は針状、ワイヤ状或いは金属の箔、フイル
ム状としては或いは又適当な支持体例えばガラ
ス、プラスチツク、セラミツクス、紙等の上に設
けた金属層として使用する。層の形成には従来公
知の方法を適用する事が出来る。即ち例えば、銀
を蒸着する方法、無電解メツキによる方法、写真
材料に使用されている様なハロゲン化銀−水性保
護コロイド乳化物層を設けて、露光−現像を行
い、例えばゼラチンを含む金属銀層を形成する方
法がある。針状或いはワイヤ状のものは一般に直
径0.1〜２mm程度であり箔、フイルム、支持体上
の層として使用する時は厚さは一般に50nm〜20
μｍである。 The metal is used in the form of needles, wires, metal foils, films, or as a metal layer on a suitable support such as glass, plastic, ceramics, paper, etc. Conventionally known methods can be applied to form the layer. That is, for example, by depositing silver, by electroless plating, by providing a silver halide-aqueous protective colloid emulsion layer such as those used in photographic materials, and exposing and developing, for example, metallic silver containing gelatin is formed. There is a method of forming layers. Needle-shaped or wire-shaped materials generally have a diameter of about 0.1 to 2 mm, and when used as a layer on a foil, film, or support, the thickness is generally 50 nm to 20 mm.
It is μm.
導電性金属の上に設けられる水不溶性塩の層も
従来公知の方法で設ける事が出来る。即ち塩を真
空蒸着する方法、金属層をK2Cr2O7−HX溶液或
いはK3〔Fe（CN）6〕−NaOH−KX溶液（Ｘ：ハ
ロゲン）で処理して金属をハロゲン化物に変える
方法、不溶性塩−水性保護コロイド乳化物を塗布
する方法等がある。この中、金属をK2Cr2O7−
HX溶液で処理したものが安定性の点で最もすぐ
れている。水溶性塩層の厚さは一般に50nm〜10
μｍである。 The water-insoluble salt layer provided on the conductive metal can also be provided by a conventionally known method. That is, a method of vacuum evaporating a salt, and treating the metal layer with a K 2 Cr 2 O 7 -HX solution or a K 3 [Fe(CN) 6 ]-NaOH-KX solution (X: halogen) to convert the metal into a halide. method, and a method of applying an insoluble salt-aqueous protective colloid emulsion. Among these, metal is K 2 Cr 2 O 7 −
The one treated with HX solution has the best stability. The thickness of the water-soluble salt layer is generally 50nm ~ 10
It is μm.
電解質層は、従来、バインダーを使用して電解
質を含む薄膜を設けていたが、本発明者らは、バ
インダーを使用しないで電解質のみから成る層を
設ける事によつて、バインダーを有するものに比
べて極めて優れた性能を有するイオン選択電極を
得る事が出来たのである。電解質層は真空蒸着法
によつて形成される。真空蒸着法によると極めて
好ましい結果が得られる。真空蒸着は、一般に
10-4〜10-7Torrの真空度に於て行う。電解質層の
厚さは一般に0.1〜2.5ｇ／m2である。 Conventionally, the electrolyte layer used a binder to provide a thin film containing electrolyte, but the present inventors created a layer consisting only of electrolyte without using a binder. As a result, we were able to obtain an ion-selective electrode with extremely excellent performance. The electrolyte layer is formed by vacuum evaporation. Vacuum deposition gives very favorable results. Vacuum deposition is generally
It is carried out under a vacuum degree of 10 -4 to 10 -7 Torr. The thickness of the electrolyte layer is generally between 0.1 and 2.5 g/ m2 .
本発明の電解質層の上に設けるイオン選択層
は、従来公知の方法で設ける事が出来る。例えば
イオンキヤリヤーを溶媒に溶解させたものをバイ
ンダー溶液中に溶解或いは分散させたものを上記
電解質層に塗布、乾燥させる。イオンキヤリヤー
濃度は一般に0.05〜２ｇ／m2、イオン選択層の厚
さは約125μｍ以下好ましくは５〜50μｍであ
る。 The ion selective layer provided on the electrolyte layer of the present invention can be provided by a conventionally known method. For example, an ion carrier dissolved in a solvent and dissolved or dispersed in a binder solution is applied to the electrolyte layer and dried. The ion carrier concentration is generally from 0.05 to 2 g/m 2 and the thickness of the ion selective layer is less than about 125 μm, preferably from 5 to 50 μm.
本発明に於ては水不溶性塩及び電解質層間に中
間層を設けて、金属層の金属と電解質陰イオンと
が互いに接触するのを防止すると電極の未使用時
及び使用時の安定性が改良される。即ち、使用前
の保存中に於ける層の白色化及び使用時の電位の
変動が無くなる。中間層は陰イオンを通さない無
機物質、有機物質の層からなり、層の厚さは、陰
イオンの通過を防止し得る程度、例えば膜形成能
を有する有機重合体層であれば一般に0.8〜10
ｇ／m2であるが20ｇ／m2位にする事も出来る。膜
形成能のある有機重合体としては、疎水性、親水
性の重合体が使用出来るが、一般にはポリビニル
アルコール、ゼラチン、アガロース、脱イオン化
ゼラチン、ポリアクリルアミド、ポリビニルピロ
リドン、ポリアクリル酸ヒドロキシエチル、ポリ
メタクリル酸ヒドロキシエチル、ポリアクリル酸
等が使用される。 In the present invention, by providing an intermediate layer between the water-insoluble salt and the electrolyte layer to prevent the metal of the metal layer and the electrolyte anion from coming into contact with each other, the stability of the electrode when not in use and when in use is improved. Ru. That is, whitening of the layer during storage before use and fluctuations in potential during use are eliminated. The intermediate layer is composed of a layer of an inorganic material or an organic material that does not allow anions to pass through, and the thickness of the layer is generally 0.8 to 0.8 to an extent that can prevent the passage of anions, for example, if it is an organic polymer layer with film-forming ability. Ten
g/m 2 , but it is also possible to make it 20g/m 2nd place. Hydrophobic and hydrophilic polymers can be used as organic polymers with film-forming ability, but generally polyvinyl alcohol, gelatin, agarose, deionized gelatin, polyacrylamide, polyvinylpyrrolidone, polyhydroxyethyl acrylate, and Hydroxyethyl methacrylate, polyacrylic acid, etc. are used.
本発明の電極は、金属層上に直接、塗布或いは
真空蒸着によつて電解質層を設け、その上にイオ
ン選択膜を設ける事によつて作成する事も出来
る。金属例えば銀は電解質例えばKClと反応して
水不溶性のAgCl層を形成し、Ag／AgCl／KCl／
イオン選択層から成る電極になる。 The electrode of the present invention can also be produced by providing an electrolyte layer directly on a metal layer by coating or vacuum deposition, and then providing an ion selective membrane thereon. Metals such as silver react with electrolytes such as KCl to form a water-insoluble AgCl layer, forming Ag/AgCl/KCl/
The electrode consists of an ion-selective layer.
電極は、試料溶液によつて自己の各層間でのシ
ヨートが起らない様にする為に、イオン選択層だ
けを露出して他は水が浸透しない様に水非浸透性
の電気絶縁性被膜で保護する事が必要である。 The electrode is coated with a water-impermeable electrically insulating coating that exposes only the ion-selective layer and prevents water from penetrating the rest, in order to prevent shoots from occurring between the layers due to the sample solution. It is necessary to protect it.
本発明の電極は、特開昭52−142584の電解質層
がバインダーと電解質から成るイオン選択電極に
比べて、応答速度が早く、応答時間が著しく短
い。更に、電位ドリフトは極めて小さく、又繰り
返し使用が出来る。本発明の電極によればイオン
濃度を再現性良く正確に定量出来るので高い精度
が要求される分析に使用出来る。本発明の電極
は、上記特開昭52−142584の電極に比して電解質
層にバインダーを使用しないので製造工程が簡単
であり、又経済的にも有利である。 The electrode of the present invention has a faster response speed and a significantly shorter response time than the ion-selective electrode disclosed in JP-A-52-142584, in which the electrolyte layer is composed of a binder and an electrolyte. Furthermore, the potential drift is extremely small and it can be used repeatedly. According to the electrode of the present invention, the ion concentration can be accurately determined with good reproducibility, so that it can be used for analysis that requires high accuracy. The electrode of the present invention does not use a binder in the electrolyte layer compared to the electrode of JP-A-52-142584, so the manufacturing process is simpler and it is also economically advantageous.
本発明の電極は、実開昭55−64759に記載され
たイオン選択電極集積板として使用するのに適し
ている。即ち、電気絶縁性表面を有する支持板の
上に、本発明の電極の２つから成る対の少くとも
１対をその各電極端部が互いに短絡しないだけの
間隔をおいて互いに近接する様配置し、イオン選
択電極集積板とする。こゝで少くとも２対の相異
なる種類のイオンを選択し得る電極を使用すれば
液体試料を支持体上の電極の配置された部分の中
心部に１回付着させるだけで多項目のイオン濃度
を定量する事が出来る。この集積板の具体例を実
施例６に示す。 The electrode of the present invention is suitable for use as an ion-selective electrode stacking plate as described in Utility Model Application Publication No. 55-64759. That is, on a support plate having an electrically insulating surface, at least one pair of two electrodes of the present invention is arranged close to each other with a distance sufficient to prevent the ends of each electrode from shorting each other. Then, it is used as an ion-selective electrode integrated plate. By using an electrode that can select at least two pairs of different types of ions, multiple ion concentrations can be obtained by simply depositing the liquid sample once on the center of the part where the electrodes are placed on the support. can be quantified. A specific example of this integrated plate is shown in Example 6.
実施例 １
純度99・９％の銀４ｇをタングステンバスケツ
トに容れ、厚さ100μｍのポリエチレンテレフタ
レート（PET）フイルム（15×12cm）を真空蒸
着装置内に上記蒸発物から約30cmの距離を隔てて
円弧状に配置したのち、装置を操作して真空度５
×10-5Torrのもとに上記銀をモニターが蒸着量
７ｇ／m2を指示するまで蒸着した後、このフイル
ムの両端（12cm巾の辺）にビニルテープ（巾１
cm）をはりつけた。次いで純度99.5％の塩化銀３
ｇをタングステンバスケツト蒸発源に入れ、真空
度５×10-5Torrのもとでその試料に対しモニタ
ーが蒸着量2.5ｇ／m2を指示するまで蒸着を行つ
た。更にこの上に純度99.5％の塩化カリウムをタ
ングステンバスケツト蒸発源に入れ真空度５×
10-5Torrのもとで塩化カリウムをモニターが蒸
着量1.5ｇ／m2を指示するまで真空蒸着した。次
にこのPETフイルム上に蒸着したAg／AgCl／
KCl多層膜上に、乾燥膜厚25μｍとなる様に次の
カリウムイオン選択層を塗布し乾燥してカリウム
イオン選択電極フイルムを作成した。Example 1 4 g of silver with a purity of 99.9% was placed in a tungsten basket, and a polyethylene terephthalate (PET) film (15 x 12 cm) with a thickness of 100 μm was placed in a vacuum evaporation apparatus at a distance of about 30 cm from the evaporated material. After arranging it in an arc, operate the device to achieve a vacuum level of 5.
After evaporating the above silver under ×10 -5 Torr until the monitor indicates a deposition amount of 7 g/m 2 , vinyl tape (width 1
cm) was attached. Next, silver chloride 3 with a purity of 99.5%
g was placed in a tungsten basket evaporation source, and evaporation was performed on the sample under a vacuum degree of 5 x 10 -5 Torr until the monitor indicated a deposition amount of 2.5 g/m 2 . Furthermore, put potassium chloride with a purity of 99.5% on top of this in a tungsten basket evaporation source and vacuum at 5x.
Potassium chloride was vacuum deposited under 10 −5 Torr until the monitor indicated a deposition amount of 1.5 g/m 2 . Next, Ag/AgCl/
The following potassium ion selective layer was coated on the KCl multilayer film to a dry film thickness of 25 μm and dried to prepare a potassium ion selective electrode film.
カリウムイオン選択層組成
ポリビニルクロリド（ゼオン103EP−８：
日本ゼオン株式会社製：平均重合度800） 2.0ｇ
ジオクチルフタレート 5.0ｇ
バリノマイシン 0.04ｇ
テトラヒドロフラン 22.5ｇ
次に、電極フイルムのビニルテープをはがした
後、１×６cmの大きさに切断して電極フイルムチ
ツプを作成した。 Potassium ion selective layer composition Polyvinyl chloride (Zeon 103EP-8: Nippon Zeon Co., Ltd.: average degree of polymerization 800) 2.0 g Dioctyl phthalate 5.0 g Valinomycin 0.04 g Tetrahydrofuran 22.5 g Next, after peeling off the vinyl tape of the electrode film, Electrode film chips were prepared by cutting into pieces of 1 x 6 cm.
得られた電極フイルムチツプを一対にし第１図
の如く、かたん糸からなるブリツジで接続し、電
位差計（デジタルPHメータ、HM−15A、東亜電
波工業(株)製）につないだ後Ｋを含む標準液と試
料液とを夫々の電極フイルム上に滴下し、電位差
計の起電力を測定したところ、カリウムイオンに
対する半対数的な線型応答が観察された。曲線の
傾きはカリウムイオン濃度１桁当り57mVであつ
た。試料液の点滴後電位が最終指示値（平衡電
位）に達するまでに要する時間は１分以内であつ
た。又点滴後60分を経過しても平衡電位の変化が
なく、極めて安定していた。 The obtained electrode film chips were made into a pair and connected with a bridge made of simple thread as shown in Fig. 1, and then connected to a potentiometer (digital PH meter, HM-15A, manufactured by Toa Denpa Kogyo Co., Ltd.), and then K was connected. When the standard solution and sample solution were dropped onto each electrode film and the electromotive force was measured with a potentiometer, a semi-logarithmic linear response to potassium ions was observed. The slope of the curve was 57 mV per digit of potassium ion concentration. The time required for the potential to reach the final indicated value (equilibrium potential) after instillation of the sample solution was within 1 minute. Furthermore, there was no change in the equilibrium potential even after 60 minutes had passed after the instillation, and it was extremely stable.
第１図に於て１は支持体、２は金属銀層、３は
塩化銀層、４は塩化カリの層、５はＫを選択す
るイオン選択層、６は標準液滴、７は試料液滴、
８はブリツジ、９は電位差計である。 In Figure 1, 1 is a support, 2 is a metallic silver layer, 3 is a silver chloride layer, 4 is a potassium chloride layer, 5 is an ion selective layer that selects K, 6 is a standard droplet, and 7 is a sample solution. drop,
8 is a bridge, and 9 is a potentiometer.
金属銀針を使用して、上記したのと同様に蒸着
法を用いて第２図に示した様な電極針を作成し
た。第２図に於て２は金属銀針、３〜９は第１図
のものと同じである。 An electrode needle as shown in FIG. 2 was prepared using a metal silver needle and the same vapor deposition method as described above. In FIG. 2, 2 is a metal silver needle, and 3 to 9 are the same as those in FIG.
実施例 ２
蒸着したAg層を重クロム酸カリウム７ｇ、塩
酸（36％）５ｇと水１から成る溶液中で25℃に
於て45秒開処理して塩化銀層を作成した以外は実
施例１に記載のようにして電極フイルムＡを作成
した。実施例１と同様にして電気化学的応答を測
定したところ、カリウムイオン濃度１桁当り
55mVであつた。Example 2 Example 1 except that the deposited Ag layer was subjected to an open treatment at 25° C. for 45 seconds in a solution consisting of 7 g of potassium dichromate, 5 g of hydrochloric acid (36%), and 1 portion of water to create a silver chloride layer. Electrode film A was prepared as described in . When the electrochemical response was measured in the same manner as in Example 1, it was found that per one digit potassium ion concentration,
It was 55mV.
実施例 ３
実施例１に於て、塩化銀層を設けた後、この層
の上に15％のポリビニルアルコール（ゴーセノー
ルGL−03鹸化度86.5〜89.0Mol％、４％水溶液20
℃における粘度3.5±0.5cps日本合成化学工業(株)
社製）水溶液を塗布して乾燥し、膜厚５ｇ／m2の
中間層を設けた以外は、実施例１と同様にして電
極フイルムを作成した。このものを相対湿度55
％、25℃に６日放置した後、実施例１と同様にし
てＫイオン濃度測定を行い、製造後直ちに使用
した実施例１と全く同様の結果が得られた。Example 3 In Example 1, after providing a silver chloride layer, 15% polyvinyl alcohol (Gosenol GL-03 saponification degree 86.5 to 89.0 Mol%, 4% aqueous solution 20
Viscosity at °C 3.5±0.5cps Nippon Gosei Chemical Industry Co., Ltd.
An electrode film was prepared in the same manner as in Example 1, except that an aqueous solution (manufactured by Co., Ltd.) was applied and dried, and an intermediate layer with a thickness of 5 g/m 2 was provided. Relative humidity 55
%, and after being left at 25°C for 6 days, the K ion concentration was measured in the same manner as in Example 1, and the results were exactly the same as in Example 1, which was used immediately after production.
実施例 ４
比較電極フイルムＢの作成
実施例２の電極フイルム作成過程において、
KCl層の代りに、次の組成物を乾燥塗布量が５
ｇ／m2になるように塗布して電解質層を設けた以
外は、実施例２の場合と同じようにして、比較電
極フイルムＢを作成した。Example 4 Creation of comparative electrode film B In the electrode film creation process of Example 2,
In place of the KCl layer, apply the following composition at a dry coating weight of 5
Comparative electrode film B was prepared in the same manner as in Example 2, except that the electrolyte layer was provided by coating at a concentration of g/m 2 .
電解質層塗布組成物
ポリビニルアルコール（ゴーセノールGL−03）
15ｇ
塩化カリウム 4.5ｇ
水 100ml
上記の如く作成した比較電極フイルムＢおよび
実施例２で作成した本発明の電極フイルムＡを用
いて、実施例２と同様にして試験を行い、液滴を
滴下してから60分間の起電力をそれぞれの試料に
ついて測定した。結果を第４図に示した。曲線Ａ
は実施例２に於て得られた電極フイルムＡを使用
した場合の曲線、曲線Ｂは比較電極フイルムＢを
使用した場合の曲線である。第４図から本発明の
電極フイルムは、電解質層を塗布した比較電極フ
イルムより起電力の応答速度（平衡電位に到達す
る時間）が早く、しかも電位−時間曲線が極めて
安定していることが判る。 Electrolyte layer coating composition polyvinyl alcohol (Gohsenol GL-03)
15g Potassium chloride 4.5g Water 100ml A test was conducted in the same manner as in Example 2 using the comparative electrode film B prepared as above and the electrode film A of the present invention prepared in Example 2. The electromotive force for 60 minutes was measured for each sample. The results are shown in Figure 4. Curve A
is a curve when electrode film A obtained in Example 2 is used, and curve B is a curve when comparative electrode film B is used. From FIG. 4, it can be seen that the electrode film of the present invention has a faster response speed of electromotive force (time to reach equilibrium potential) than the comparative electrode film coated with an electrolyte layer, and has an extremely stable potential-time curve. .
実施例 ５
実施例２において作成した本発明の電極フイル
ムＡと実施例４で得られた比較電極フイルムＢと
を使用して、電極フイルムの繰返し使用性を調べ
た。即ち第１図の如く、一対にした電極フイルム
チツプの一方にKCl標準液を滴下し、他の一方に
試料液を滴下して起電力を測定した後、液滴を
紙で全部吸取り、次に同じ濃度のKCl標準液及び
試料液をそれぞれの対応する電極フイルム上に滴
下して10分後の電位を測定する操作を10回繰返し
て、電極フイルムの繰返し使用性を調べた。その
結果本発明の電極フイルムの性能は、測定回数を
増やしても劣化が殆んどないことが判明した。Example 5 Using the electrode film A of the present invention prepared in Example 2 and the comparative electrode film B obtained in Example 4, the reusability of the electrode film was investigated. That is, as shown in Fig. 1, the electromotive force was measured by dropping a KCl standard solution onto one of a pair of electrode film chips and dropping a sample solution onto the other, then absorbing all the droplets with paper, and then The repeatability of the electrode films was investigated by repeating the operation of dropping KCl standard solution and sample solution of the same concentration onto each corresponding electrode film and measuring the potential after 10 minutes 10 times. As a result, it was found that the performance of the electrode film of the present invention hardly deteriorated even when the number of measurements was increased.
第５図は本発明の効果を示すものであり、曲線
Ａは実施例２で作成した電極フイルムＡを、曲線
Ｂは比較電極フイルムＢの繰返性を示したもので
ある。第５図によつて、本発明の電極フイルムは
繰返して使用することが出来るので実用的にも極
めてすぐれていることが判る。 FIG. 5 shows the effects of the present invention, in which curve A shows the repeatability of electrode film A prepared in Example 2, and curve B shows the repeatability of comparative electrode film B. From FIG. 5, it can be seen that the electrode film of the present invention can be used repeatedly and is therefore extremely superior in practical terms.
実施例 ６
本発明の電極をＫ，Na，Clの３項目の
イオン測定用のイオン選択電極集積板に使用した
例を示す。第３図に於て、厚さ１mmのアクリル樹
脂板１０の上に、本発明の電極フイルムからなる
３種の選択電極対、即ちＫ用11X，11Y；Na
用１２Ｘ，１２Ｙ；Cl用１３Ｘ，１３Ｙを図
示の如く、Ｘ，Y2点を包囲する形で放射状に配
置し、各電極のヘツドは直径約１cmの円内に集中
するようにしてある。各電極からの回路（図中の
太い実線で示されている。）は、支持板の一端に
設けられた接点端子１４Ｘ，１５Ｘ，１６Ｘ及び
１４Ｙ，１５Ｙ，１６Ｙに図中の太い実線で示さ
れる如く接続されている。つぎに、糸状又は帯状
ポーラスシートからなるブリツジ１７をダム（電
気絶縁性で水非浸透性材料からなる帯状突起）を
またぎ、Ｘ，Ｙ両点を結ぶ形で配置する。かくし
て３項目イオン測定用イオン選択電極集積板が形
成される。Example 6 An example will be shown in which the electrode of the present invention is used in an ion selective electrode assembly plate for measuring three ions: K, Na, and Cl. In FIG. 3, three selective electrode pairs made of the electrode film of the present invention are placed on an acrylic resin plate 10 with a thickness of 1 mm, namely, 11X for K, 11Y;
12X, 12Y for Cl; 13X, 13Y for Cl are arranged radially surrounding points X and Y2 as shown in the figure, and the heads of each electrode are concentrated within a circle with a diameter of about 1 cm. Circuits from each electrode (indicated by thick solid lines in the figure) are shown by thick solid lines in the figure at contact terminals 14X, 15X, 16X and 14Y, 15Y, 16Y provided at one end of the support plate. It is connected like this. Next, a bridge 17 made of a thread-like or band-like porous sheet is placed across the dam (a band-like protrusion made of an electrically insulating and water-impermeable material) and connecting both the X and Y points. In this way, an ion selective electrode integrated plate for three-item ion measurement is formed.
このイオン選択電極集積板を用いて血清中の３
項目イオンを測定するためには、電位差計に集積
板を次の方法で接続する。 Using this ion-selective electrode integrated plate, 3
To measure the topical ions, connect the integrating plate to the potentiometer in the following manner.
まず上記集積板はその接点端子１４Ｘ，１５
Ｘ，１６Ｘ，１４Ｙ，１５Ｙ，１６Ｙを経てそれ
に対応する電位差測定装置（例えばアナログ指示
型の電位差計）の接点ソケツト２０Ｘ，２１Ｘ，
２２Ｘ，２０Ｙ，２１Ｙ，２２Ｙにそれぞれ差込
むなど公知の方法で一操作で連結して電気的に接
続される。２３Ｘ，２３Ｙは接点切換機構部で、
同種のイオン選択電極にそれぞれ接続されるよう
接点を切換えうる構造を有しており、イオン選択
電極１１Ｘと１１Ｙ、１２Ｘと１２Ｙ、１３Ｘと
１３Ｙとの間の相対的電位差に基づく電流が電位
差測定装置に導かれるための回路を順次に切換え
るためのものである。第３図に示した集積板のた
めには、接点切換機構部としては、例えば２回路
３接点連動型スイツチを用いることができ、かつ
連動型スイツチを用いることが電位差測定のため
の接点切換操作の容易さおよび接点切換時の誤操
作（異なる種類のイオン選択電極間を接続する誤
り等）を防ぐために好ましい。 First, the above-mentioned integrated board has its contact terminals 14X, 15
X, 16X, 14Y, 15Y, 16Y to the contact sockets 20X, 21X, of the corresponding potential difference measuring device (for example, an analog indicating potentiometer).
22X, 20Y, 21Y, and 22Y, and are connected and electrically connected in one operation by a known method such as being inserted into each of 22X, 20Y, 21Y, and 22Y. 23X and 23Y are contact switching mechanism parts,
It has a structure in which the contacts can be switched so that they are connected to the same type of ion-selective electrodes, and the current based on the relative potential difference between the ion-selective electrodes 11X and 11Y, 12X and 12Y, and 13X and 13Y is detected by the potential difference measuring device. This is for sequentially switching the circuits that lead to the For the integrated board shown in FIG. 3, a 2-circuit, 3-contact interlocking type switch, for example, can be used as the contact switching mechanism, and it is preferable to use an interlocking type switch for contact switching operation for potential difference measurement. This is preferable for ease of operation and for preventing erroneous operations (such as erroneous connections between different types of ion selection electrodes) when switching contacts.
次に約50μの血清をＸ点上に滴下付着させ、
続いて約50μの混合イオン標準水溶液をＹ点上
に滴下付着させる。両液はダム１８により混合が
妨げられる。血清と標準液は各々がほぼ半円状に
拡つて各電極のヘツドをぬらし、同時にブリツジ
１７をも濡らして液ブリツジを形成し、血清中の
イオン濃度に対応する電位差が表れるので、回路
を順次切換えながら電位差測定装置における指示
値を読みとり、Ｋ，Na，Clの量を定量す
ることができる。 Next, drop about 50μ of serum onto the X point and deposit it.
Subsequently, approximately 50μ of a mixed ion standard aqueous solution is dropped onto the Y point. Both liquids are prevented from mixing by the dam 18. The serum and the standard solution each spread in an approximately semicircular shape and wet the head of each electrode, and at the same time wet the bridge 17 to form a liquid bridge, and a potential difference corresponding to the ion concentration in the serum appears, so the circuit is sequentially connected. The amounts of K, Na, and Cl can be determined by reading the indicated value on the potentiometer while switching.
本発明の実施の態様
１ 電解質層の厚さが0.1〜2.5ｇ／m2である特許
請求の範囲第１項に記載の電極。Embodiment 1 of the present invention The electrode according to claim 1, wherein the electrolyte layer has a thickness of 0.1 to 2.5 g/ m2 .
２ 導電性金属が銀、水不溶性塩がハロゲン化銀
である特許請求の範囲第１項に記載の電極。2. The electrode according to claim 1, wherein the conductive metal is silver and the water-insoluble salt is silver halide.
３ 電解質が塩化カリである特許請求の範囲第１
項に記載の電極。3 Claim 1 in which the electrolyte is potassium chloride
Electrodes described in Section.
４ 水不溶性塩層と電解質層の間に電解質の陰イ
オンを通さない物質からなる中間層を設けた特
許請求の範囲第１項に記載の電極。4. The electrode according to claim 1, further comprising an intermediate layer between the water-insoluble salt layer and the electrolyte layer, which is made of a substance that does not allow the anions of the electrolyte to pass through.
５ 中間層の厚さが0.8〜10ｇ／m2である実施の
態様第４項に記載の電極。5. The electrode according to embodiment 4, wherein the intermediate layer has a thickness of 0.8 to 10 g/ m2 .
６ 電極がフイルム状である特許請求の範囲第１
項に記載の電極。6 Claim 1 in which the electrode is in the form of a film
Electrodes described in Section.
７ 電極が針状或いはワイヤー状である特許請求
の範囲第１項に記載の電極。7. The electrode according to claim 1, wherein the electrode is needle-shaped or wire-shaped.
８ イオン選択層が疎水性有機バインダー中に有
機物質からなるイオンキヤリヤーを含有するも
のである特許請求の範囲第１項に記載の電極。8. The electrode according to claim 1, wherein the ion selective layer contains an ion carrier made of an organic substance in a hydrophobic organic binder.
９ イオン選択層がイオン交換樹脂から成るもの
である特許請求の範囲第１項に記載の電極。9. The electrode according to claim 1, wherein the ion selective layer is made of an ion exchange resin.
10 電解質層を電解質の真空蒸着によつて水不溶
性塩の層の上に形成する特許請求の範囲第２項
に記載の電極の製造方法。10. The method of manufacturing an electrode according to claim 2, wherein the electrolyte layer is formed on the water-insoluble salt layer by vacuum deposition of the electrolyte.
11 電解質層を、電解質の水溶液を水不溶性塩の
層の上に塗布する事によつて形成する特許請求
の範囲第２項に記載の電極の製造方法。11. The method of manufacturing an electrode according to claim 2, wherein the electrolyte layer is formed by applying an aqueous electrolyte solution onto the water-insoluble salt layer.
12 水不溶性塩層の上に電解質の陰イオンを通さ
ない物質からなる中間層を設けた後、電解質層
を設ける特許請求の範囲第２項に記載の電極の
製造方法。12. The method for manufacturing an electrode according to claim 2, in which the electrolyte layer is provided after providing an intermediate layer made of a substance that does not pass electrolyte anions on the water-insoluble salt layer.
13 イオン選択電極の２つから成る対の少くとも
２対が相異なる種類のイオンを選択し得る電極
である特許請求の範囲第３項に記載のイオン濃
度測定用イオン選択電極集積板。13. The ion selective electrode integrated plate for ion concentration measurement according to claim 3, wherein at least two of the two pairs of ion selective electrodes are electrodes capable of selecting different types of ions.
第１図及び第２図は、本発明の電極のフイルム
状のもの及び針状のものを使用した例を夫々模式
的に示したものであつて、１は支持体、２は金属
銀層（第１図）或いは金属銀針（第２図）、３は
塩化銀層、４は塩化カリの層、５はＫを選択す
るイオン選択層、６は標準液滴、７は試料液滴、
８はブリツジ、９は電位差計である。
第３図は、本発明の電極を使用した、多項目イ
オン測定用イオン選択電極集積板の例を示すもの
であつて１０は電気絶縁性支持板１１Ｘ，１１Ｙ
はＫイオン選択電極、１２Ｘ，１２ＹはNa
イオン選択電極、１３Ｘ，１３ＹはClイオン
選択電極、１４Ｘ，１５Ｘ，１６Ｘ，１４Ｙ，１
５Ｙ，１６Ｙは支持板上の電気接点端子、１７は
ブリツジ、１８はダム、１９は電位差測定装置、
２０Ｘ，２１Ｘ，２２Ｘ，２０Ｙ，２１Ｙ，２２
Ｙは電位差測定装置接続用ソケツト、２３Ｘ，２
３Ｙは接点接続切換機構、太い実線は電気配線回
路を表わし、つる巻状の実線（〓）は電位差計へ
の電気配線を表わす。
第４図は、本発明と従来公知の夫々の電極によ
る起電力と時間の関係を示すグラフである。
第５図は、本発明と従来公知の夫々の電極の起
電力と使用回数との関係を示すグラフである。
FIGS. 1 and 2 schematically show examples in which a film-like electrode and a needle-like electrode of the present invention are used, respectively, in which 1 is a support, 2 is a metallic silver layer ( (Figure 1) or a metal silver needle (Figure 2), 3 is a silver chloride layer, 4 is a potassium chloride layer, 5 is an ion selection layer for selecting K, 6 is a standard droplet, 7 is a sample droplet,
8 is a bridge, and 9 is a potentiometer. FIG. 3 shows an example of an ion selective electrode integrated plate for multi-item ion measurement using the electrode of the present invention, and 10 is an electrically insulating support plate 11X, 11Y.
is K ion selective electrode, 12X, 12Y are Na
Ion selective electrodes, 13X, 13Y are Cl ion selective electrodes, 14X, 15X, 16X, 14Y, 1
5Y and 16Y are electrical contact terminals on the support plate, 17 is a bridge, 18 is a dam, 19 is a potential difference measuring device,
20X, 21X, 22X, 20Y, 21Y, 22
Y is a socket for connecting a potential difference measuring device, 23X, 2
3Y represents a contact connection switching mechanism, the thick solid line represents an electrical wiring circuit, and the spiral solid line (ⓓ) represents electrical wiring to the potentiometer. FIG. 4 is a graph showing the relationship between electromotive force and time of the present invention and conventionally known electrodes. FIG. 5 is a graph showing the relationship between the electromotive force and the number of times of use of the present invention and conventionally known electrodes.
Claims (1)
の層、次に該水不溶性塩の陰イオンと共通の陰イ
オンを有する電解質の層、更にイオン選択層が順
次設けられたイオン選択電極において、該電解質
の層が真空蒸着法によつて設けられたバインダー
を含まず実質的に電解質のみからなることを特徴
とするイオン選択電極。 ２ 導電性金属の上に直接或いは該金属の上に、
該金属の水不溶性塩の層を設けてからバインダー
を含まず実質的に該水不溶性塩の陰イオンと共通
の陰イオンを有する電解質のみからなる層を真空
蒸着法によつて設け、しかる後イオン選択層を設
けることからなるイオン選択電極の製造方法。 ３ 導電性金属の上に該導電性金属の水不溶性塩
の層、次に真空蒸着法によつて設けられたバイン
ダーを含まない該水不溶性塩の陰イオンと共通の
陰イオンを有する電解質の層、更にイオン選択層
が順次設けられたイオン選択電極の２つからなる
対の少くとも１種を、その各電極端部が互いに短
絡しないだけの間隔をおいて互いに近接する様電
気絶縁性表面を有する支持板の上に配置してなる
イオン濃度測定用イオン選択電極集積板。[Claims] 1. A layer of a water-insoluble salt of the conductive metal on a conductive metal, then a layer of an electrolyte having an anion common to the anion of the water-insoluble salt, and then an ion-selective layer. An ion-selective electrode provided in the ion-selective electrode, wherein the electrolyte layer does not contain a binder provided by vacuum evaporation and consists essentially only of the electrolyte. 2 Directly on or on the conductive metal,
After providing a layer of the water-insoluble salt of the metal, a layer containing no binder and consisting only of an electrolyte having substantially the same anion as the anion of the water-insoluble salt is provided by a vacuum evaporation method. A method for manufacturing an ion selective electrode comprising providing a selective layer. 3. A layer of a water-insoluble salt of the conductive metal on top of the conductive metal, and then a layer of an electrolyte having a common anion with the anion of the water-insoluble salt, which does not contain a binder and is provided by vacuum evaporation. Further, at least one of the pairs of ion-selective electrodes each having an ion-selective layer sequentially provided thereon is coated with an electrically insulating surface such that the ends of each electrode are close to each other with a distance sufficient to prevent short-circuiting. An ion selective electrode integrated plate for measuring ion concentration, which is disposed on a support plate having an ion selective electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9237980A JPS5717852A (en) | 1980-07-07 | 1980-07-07 | Ion selective electrode, its production and ion selective electrode integrating plate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9237980A JPS5717852A (en) | 1980-07-07 | 1980-07-07 | Ion selective electrode, its production and ion selective electrode integrating plate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5717852A JPS5717852A (en) | 1982-01-29 |
| JPS6256976B2 true JPS6256976B2 (en) | 1987-11-28 |
Family
ID=14052784
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9237980A Granted JPS5717852A (en) | 1980-07-07 | 1980-07-07 | Ion selective electrode, its production and ion selective electrode integrating plate |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5717852A (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4504368A (en) | 1983-07-18 | 1985-03-12 | Eastman Kodak Company | Alkali metal ion-selective compositions and elements and a method of using same |
| DE3583697D1 (en) * | 1984-05-10 | 1991-09-12 | Fuji Photo Film Co Ltd | ION SELECTIVE ELECTRODE. |
| DE3585570D1 (en) * | 1984-06-20 | 1992-04-16 | Fuji Photo Film Co Ltd | ION SELECTIVE ELECTRODE. |
| US4615788A (en) * | 1984-06-20 | 1986-10-07 | Fuji Photo Film Co., Ltd. | Ion selective electrode and method of preparation thereof |
| DE3677181D1 (en) * | 1985-12-23 | 1991-02-28 | Hoffmann La Roche | WATER-FREE, SELECTIVE, ION-PENETABLE ELECTRODES FOR THE EXAMINATION OF CERTAIN IONS IN AQUEOUS SOLUTIONS. |
| DE4123348A1 (en) * | 1991-07-15 | 1993-01-21 | Boehringer Mannheim Gmbh | ELECTROCHEMICAL ANALYSIS SYSTEM |
| ES2953457T3 (en) | 2018-07-31 | 2023-11-13 | Univ Rovira I Virgili Urv | Device for selective potentiometric detection of potassium |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5564759U (en) * | 1978-10-27 | 1980-05-02 |
-
1980
- 1980-07-07 JP JP9237980A patent/JPS5717852A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5717852A (en) | 1982-01-29 |
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