JPH04344454A - Electrode for detecting halogen ion - Google Patents
Electrode for detecting halogen ionInfo
- Publication number
- JPH04344454A JPH04344454A JP3116376A JP11637691A JPH04344454A JP H04344454 A JPH04344454 A JP H04344454A JP 3116376 A JP3116376 A JP 3116376A JP 11637691 A JP11637691 A JP 11637691A JP H04344454 A JPH04344454 A JP H04344454A
- Authority
- JP
- Japan
- Prior art keywords
- silver
- layer
- ion
- layers
- electrode
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052736 halogen Inorganic materials 0.000 title description 22
- 229910052709 silver Inorganic materials 0.000 claims abstract description 60
- 239000004332 silver Substances 0.000 claims abstract description 60
- -1 silver halide Chemical class 0.000 claims abstract description 46
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 150000002500 ions Chemical class 0.000 claims description 48
- 238000005259 measurement Methods 0.000 abstract description 9
- 238000005260 corrosion Methods 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 75
- 239000007788 liquid Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 239000010408 film Substances 0.000 description 11
- 238000001514 detection method Methods 0.000 description 9
- 230000000873 masking effect Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 230000002209 hydrophobic effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 229920002799 BoPET Polymers 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 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 3
- 230000000694 effects Effects 0.000 description 3
- 229920000515 polycarbonate Polymers 0.000 description 3
- 239000004417 polycarbonate Substances 0.000 description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 3
- 239000005020 polyethylene terephthalate Substances 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000000523 sample Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229920000742 Cotton Polymers 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical compound COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 210000004369 blood Anatomy 0.000 description 2
- 239000008280 blood Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000010292 electrical insulation Methods 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229920000728 polyester 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
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WHGNAMNBMWWOMM-UHFFFAOYSA-N 1-methoxy-3-[2-[2-(3-methoxyphenyl)phenoxy]phenyl]benzene Chemical compound COC1=CC=CC(C=2C(=CC=CC=2)OC=2C(=CC=CC=2)C=2C=C(OC)C=CC=2)=C1 WHGNAMNBMWWOMM-UHFFFAOYSA-N 0.000 description 1
- QMKKMTDCMBIHKH-UHFFFAOYSA-N 1-methoxy-4-[2-[2-(4-methoxyphenyl)phenoxy]phenyl]benzene Chemical compound C1=CC(OC)=CC=C1C1=CC=CC=C1OC1=CC=CC=C1C1=CC=C(OC)C=C1 QMKKMTDCMBIHKH-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 102000007469 Actins Human genes 0.000 description 1
- 108010085238 Actins Proteins 0.000 description 1
- 241000252147 Atractosteus spatula Species 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-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
- 108010026389 Gramicidin Proteins 0.000 description 1
- 229930191564 Monensin Natural products 0.000 description 1
- RMIXHJPMNBXMBU-QIIXEHPYSA-N Nonactin Chemical group C[C@H]([C@H]1CC[C@H](O1)C[C@@H](OC(=O)[C@@H](C)[C@@H]1CC[C@@H](O1)C[C@@H](C)OC(=O)[C@H](C)[C@H]1CC[C@H](O1)C[C@H](C)OC(=O)[C@H]1C)C)C(=O)O[C@H](C)C[C@H]2CC[C@@H]1O2 RMIXHJPMNBXMBU-QIIXEHPYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- YSMRWXYRXBRSND-UHFFFAOYSA-N TOTP Chemical compound CC1=CC=CC=C1OP(=O)(OC=1C(=CC=CC=1)C)OC1=CC=CC=C1C YSMRWXYRXBRSND-UHFFFAOYSA-N 0.000 description 1
- 108010067973 Valinomycin Proteins 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 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 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- PUFGCEQWYLJYNJ-UHFFFAOYSA-N didodecyl benzene-1,2-dicarboxylate Chemical compound CCCCCCCCCCCCOC(=O)C1=CC=CC=C1C(=O)OCCCCCCCCCCCC PUFGCEQWYLJYNJ-UHFFFAOYSA-N 0.000 description 1
- FBSAITBEAPNWJG-UHFFFAOYSA-N dimethyl phthalate Natural products CC(=O)OC1=CC=CC=C1OC(C)=O FBSAITBEAPNWJG-UHFFFAOYSA-N 0.000 description 1
- 229960001826 dimethylphthalate Drugs 0.000 description 1
- QHGRPTNUHWYCEN-UHFFFAOYSA-N dioctyl phenyl phosphate Chemical compound CCCCCCCCOP(=O)(OCCCCCCCC)OC1=CC=CC=C1 QHGRPTNUHWYCEN-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000003120 macrolide antibiotic agent Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- YAFOVCNAQTZDQB-UHFFFAOYSA-N octyl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(OCCCCCCCC)OC1=CC=CC=C1 YAFOVCNAQTZDQB-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 229920001059 synthetic polymer Polymers 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 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 1
- 238000007740 vapor deposition Methods 0.000 description 1
Landscapes
- Insulators (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は水性液、血液、血清等の
体液中のハロゲンイオン濃度をポテンシヨメトリカルに
測定するためのハロゲンイオン検出用電極、特に保存性
を改良したハロゲンイオン検出用電極に関するものであ
る。[Industrial Application Field] The present invention relates to a halogen ion detection electrode for potentiometrically measuring the halogen ion concentration in body fluids such as aqueous fluids, blood, and serum, and particularly for halogen ion detection with improved storage stability. It is related to electrodes.
【0002】0002
【従来の技術】一般に、血液等のイオン濃度を測定する
には、試料液量が少なくて済むこと等からフイルム状の
ドライタイプの電極が用いられている。このような電極
は、特開昭52−142584号及び米国特許第 4,
053,381号に開示されているように、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ックスから成る乾
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
ものである。2. Description of the Related Art Generally, a film-like dry type electrode is used to measure the ion concentration of blood or the like because it requires only a small amount of sample liquid. Such electrodes are disclosed in Japanese Patent Application Laid-Open No. 52-142584 and U.S. Patent No. 4,
As disclosed in No. 053,381, a metal layer, a water-insoluble salt layer of the same kind of metal as the metal of the metal layer, and a water-soluble salt having a common anion with the water-insoluble salt are dissolved on an insulating film. A dried electrolyte layer containing a hydrophilic binder matrix and an ion-selective membrane layer are laminated in this order.
【0003】そして、この電極で試料液中のイオン濃度
を測定するには、電極2個を一対にし、ブリッジで連絡
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着し、電位差を測定す
る事によって行なう。[0003] In order to measure the ion concentration in a sample solution using this electrode, the two electrodes are paired, connected via a bridge, and connected to a potentiometer. This is done by placing each dot on a film and measuring the potential difference.
【0004】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って夫々特定イ
オンの測定が出来るもので、従って、K+測定用、Na
+測定用、Cl−測定用の如く多くの種類がある。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 and those for Cl- measurement.
【0005】以上のような電極の具体的な構成としては
、例えば、図7及び図8に示すように、中央に「V」字
状の溝1が穿設されたポリエステル支持体2に、2枚の
銀層3、3が溝1を挟んで両側全体に積層され、この各
銀層3に両端を残してそれぞれ塩化銀層4、4が積層さ
れ、そして両塩化銀層4、4の全面、銀層3の一部及び
溝1にハロゲン化トリアルキルアンモニウムを用いた1
枚のイオン選択層5が積層されている。As shown in FIGS. 7 and 8, the specific structure of the above-mentioned electrode is, for example, as shown in FIGS. Two silver layers 3, 3 are laminated on both sides with the groove 1 in between, silver chloride layers 4, 4 are laminated on each silver layer 3 leaving both ends, and the entire surface of both silver chloride layers 4, 4 is laminated. , 1 using trialkylammonium halide in a part of the silver layer 3 and the groove 1
Two ion selective layers 5 are stacked.
【0006】このような電極を作成するには、まず、ポ
リエステル支持体に銀層を蒸着した後、中央の銀層をポ
リエステル支持体部分を含んで除去する。そして、銀層
の両側部分を保護して残りの表面を塩化銀層にし、さら
に、塩化銀層及び銀層の一部の上にハロゲン化テトラア
ルキルアンモニウムを含有するイオン選択膜を設ける。[0006] To create such an electrode, first, a silver layer is deposited on a polyester support, and then the central silver layer including the polyester support is removed. Then, both sides of the silver layer are protected, the remaining surface is made into a silver chloride layer, and an ion selective membrane containing tetraalkylammonium halide is provided on the silver chloride layer and a part of the silver layer.
【0007】[0007]
【発明が解決しようとする課題】しかしながら、上述し
た従来の電極は、室温で放置した場合に2〜3ヶ月で腐
食が始まり、電位を測定しようとして銀面にプローブを
接触させても十分な電気的接合ができずに測定ができな
かった。[Problems to be Solved by the Invention] However, when the conventional electrodes mentioned above are left at room temperature, they begin to corrode within 2 to 3 months, and even when the probe is brought into contact with the silver surface to measure the potential, it is difficult to generate enough electricity. Measurement could not be carried out because the target bond could not be formed.
【0008】本発明は以上の問題点を解消し、長期間保
存しても銀面の腐食が生ぜず、安定な電位測定のできる
ハロゲンイオン検出用電極を提供することを目的とする
。SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and provide an electrode for detecting halogen ions that does not cause corrosion of the silver surface even after long-term storage and is capable of stable potential measurement.
【0009】[0009]
【課題を解決するための手段】本発明者は、上記目的を
達成するために銀層の腐食に付いて鋭意研究し、その原
因が、イオン選択層が銀層と一部分(図中a部)接触し
ていることであることを見出した。[Means for Solving the Problems] In order to achieve the above object, the present inventor has conducted extensive research into the corrosion of the silver layer, and found that the cause of the corrosion is that the ion selective layer is partially connected to the silver layer (part a in the figure). I found out that this is due to contact.
【0010】本発明は、以上の知見により始めて完成さ
せられたもので、支持体の上に銀層、ハロゲン化銀層及
びイオン選択層を積層した電極において、イオン選択層
を銀層に接触しない状態で設けことを特徴として構成さ
れている。The present invention was first completed based on the above findings, and is based on an electrode in which a silver layer, a silver halide layer, and an ion selective layer are laminated on a support, in which the ion selective layer does not come into contact with the silver layer. The feature is that it is provided in a state.
【0011】本発明のハロゲンイオン検出電極は、イオ
ン選択層が銀層と接触しない状態で設けられている。塗
布によりイオン選択層を銀層と接触しない状態で設ける
には、ギーサー巾を制御することで塗布液の粘度とイオ
ン選択層をハロゲン化銀層の巾より設けることが出来る
。The halogen ion detection electrode of the present invention is provided with the ion selection layer not in contact with the silver layer. In order to provide the ion selective layer by coating without contacting the silver layer, by controlling the Giesser width, the viscosity of the coating solution and the width of the silver halide layer can be adjusted to provide the ion selective layer.
【0012】本発明の電極に用いられる支持体は、電極
の他の部分を支持することができ、電気絶縁性で電気的
に不活性な性質をもつ材料から構成できるものであれば
、その材料には特別の制限はなく、広く公知の材料から
選択して用いることができる。好ましいのは、セルロー
スアセテート、ポリエチレンテレフタレート、ポリカー
ボネート、ポリスチレン等の膜形成性ポリマーから構成
したものである。支持体は、一般に約0.05ないし0
.5mmの厚さに形成するのが好ましい。[0012] The support used in the electrode of the present invention can be made of a material that can support other parts of the electrode and is electrically insulating and electrically inert. There are no particular restrictions on the material, and a wide variety of materials can be selected and used. Preferred are those constructed from film-forming polymers such as cellulose acetate, polyethylene terephthalate, polycarbonate, and polystyrene. The support generally has a thickness of about 0.05 to 0.
.. It is preferable to form it to a thickness of 5 mm.
【0013】銀層は、真空蒸着等により設けることがで
きる。銀層の上に設けられるハロゲン化銀層は、従来公
知の方法で設ける事が出来る。例えば、ハロゲン化銀を
真空蒸着する方法、銀層をK2Cr2O7−HX溶液或
いはK3 Fe(CN)4〕−NaOH−KX溶液(X
:ハロゲン、例、塩素、臭素、沃素)で処理して銀をハ
ロゲン化物に変える方法、ハロゲン化銀−水性保護コロ
イド乳化物を塗布する方法等がある。これらの内、銀を
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。[0013] The silver layer can be provided by vacuum deposition or the like. The silver halide layer provided on the silver layer can be provided by a conventionally known method. For example, silver halide is deposited under vacuum, the silver layer is deposited in a K2Cr2O7-HX solution or a K3Fe(CN)4]-NaOH-KX solution (X
There are a method of converting silver into a halide by treatment with halogen (eg, chlorine, bromine, iodine), a method of coating a silver halide-aqueous protective colloid emulsion, etc. Among these, the one in which silver is treated with a K2Cr2O7-HX solution has the best stability.
【0014】ハロゲン化銀層の厚さは一般に50nm〜
10μm、好ましくは50nm〜1μmである。[0014] The thickness of the silver halide layer is generally from 50 nm to
It is 10 μm, preferably 50 nm to 1 μm.
【0015】銀層の一部を電気接続端子として機能させ
るために、側端近傍をハロゲン化金属に変換させない方
法として、公知のレジストを塗布してマスクする方法、
「Research Disclosure」誌、#1
9445(1980年6月号)に開示されているアルカ
リで除去できるレジストを塗布してマスクする方法、特
開昭56−33537に開示されているニッケルまたは
クロムの厚さ5nmないし20nmの蒸着薄膜を設けて
マスクする方法、パラジウムの厚さ1.5nmないし1
5nmの蒸着薄膜またはインジウムの3nmないし20
nmの蒸着薄膜を設けてマスクする方法、被膜剥離性を
有する、例えばフロンマスク(古藤産業製)等を用いて
マスクする方法等を適用することができる。In order to make a part of the silver layer function as an electrical connection terminal, a method of masking by applying a known resist to prevent the vicinity of the side edges from being converted into metal halide;
"Research Disclosure" magazine, #1
9445 (June 1980 issue), a method of masking by applying a resist that can be removed with an alkali, and a method of masking by applying a resist that can be removed with an alkali, a method of masking by applying a resist that can be removed with an alkali, and a method of masking a thin film of nickel or chromium with a thickness of 5 nm to 20 nm, as disclosed in JP-A-56-33537. Method of providing and masking, palladium thickness 1.5 nm to 1
5 nm vapor deposited thin film or 3 nm to 20 nm of indium
A method of masking by providing a vapor-deposited thin film of nm thickness, a method of masking by using a removable film such as a Freon mask (manufactured by Furuto Sangyo), etc. can be applied.
【0016】イオン選択層は、特定のイオンを選択する
ことができ、好ましくは参照液又は被検液と接触する以
前の乾燥状態において電気絶縁性であればよい。上記「
特定のイオンを選択することができる」とは、特定のイ
オンのみを選択的に透過または感応する場合のみならず
、特定のイオンが測定に充分な時間差をもって他の測定
対象外の物質から選択され得る場合も含む。又、イオン
選択層に用いる物質によっては、イオン交換を通じて液
中のイオン活性変化に対応するポテンシオメトリカルな
レスポンスを測定し、結果的に特定イオンを選択したと
同等の機能を発現する場合も、本発明では「特定のイオ
ンを選択することができる」という。[0016] The ion selective layer can select a specific ion, and preferably is electrically insulating in a dry state before coming into contact with the reference liquid or test liquid. the above"
"Specific ions can be selected" refers not only to cases in which only specific ions are selectively transmitted or sensitive, but also to cases in which specific ions are selected from other non-measurable substances with a sufficient time difference for measurement. Including cases where you get it. Additionally, depending on the material used in the ion-selective layer, potentiometric responses corresponding to changes in ion activity in the liquid may be measured through ion exchange, resulting in the same function as selecting a specific ion. In the present invention, it is said that "a specific ion can be selected".
【0017】本発明のイオン選択電極は検体液および必
要に応じて用いられる参照液体がともに水性液体である
ので、イオン選択層は水不溶性でなければならない。イ
オン選択層は水不溶性であれば親水性でも疎水性でもよ
いが、好ましくは疎水性である。[0017] In the ion-selective electrode of the present invention, since both the sample liquid and the optional reference liquid are aqueous liquids, the ion-selective layer must be water-insoluble. The ion selective layer may be hydrophilic or hydrophobic as long as it is water insoluble, but is preferably hydrophobic.
【0018】イオン選択層として最も典型的なものは、
イオンキヤリヤー、イオンキヤリヤー溶媒および疎水性
有機バインダー(または、疎水性有機バインダーからな
るマトリックス)からなるものである。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、モネ
ンシン類、グラミシジン類、ノナクチン群、テトラフェ
ニルエーテル、3−メトキシフェニルフェニルエーテル
、4−メトキシフェニルフェニルエーテル、ジメチルフ
タレート、ジブチルフタレート、ジオクチルフタレート
、ジオクチルフェニルホスフェート、ビス(2−エチル
ヘキシル)フタレート、オクチルジフェニルホスフェー
ト、トリトリルホスフェート、ジブチルセパケート等が
ある。The most typical ion selective layer is:
It consists of an ion carrier, an ion carrier solvent, and a hydrophobic organic binder (or a matrix consisting of a hydrophobic organic binder). Ion carriers include valinomycin, cyclic polyether, tetralactone, macrolide actin, enninatine group, monensins, gramicidins, nonactin group, tetraphenyl ether, 3-methoxyphenylphenyl ether, 4-methoxyphenylphenyl ether, dimethyl Phthalate, dibutyl phthalate, dioctyl phthalate, dioctyl phenyl phosphate, bis(2-ethylhexyl) phthalate, octyl diphenyl phosphate, tritolyl phosphate, dibutyl sepacate, and the like.
【0019】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、ポリ塩化ビニルデン、ポ
リアクリロニトリル、ポリウレタン、ポリカルボネート
、塩化ビニル、酢酸ビニルコポリマー等がある。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, vinyl chloride, vinyl acetate. There are copolymers, etc.
【0020】イオンキヤリヤー、イオンキヤリヤー溶媒
、疎水性有機バインダーおよびそれらからなるイオン選
択層は、特開昭52−142584号公報、米国特許第
4,053,381号、同第 4,171,246号
及び同第 4,214,968号各明細書並びに「Re
search Disclosure」誌、報文No.
16113(1977年9月号)に記載の物質および技
術を用いることができる。The ion carrier, the ion carrier solvent, the hydrophobic organic binder, and the ion selective layer comprising them are described in Japanese Patent Application Laid-open No. 142584/1984, US Pat. No. 4,053,381, US Pat. No. 4,171, No. 246 and No. 4,214,968, as well as “Re
"Search Disclosure" magazine, Report No.
16113 (September 1977) can be used.
【0021】イオン選択層は、従来公知の方法で設ける
ことができる。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塗布、乾燥させる。イ
オンキヤリヤー濃度は、一般に0.05g〜10g/m
2、イオン選択層の厚さは、約3μm〜約125μm、
好ましくは5μm〜50μmである。The ion selective layer can be provided by a conventionally known method. For example, an ion carrier dissolved in a solvent is applied to a binder solution and dried. The ion carrier concentration is generally between 0.05g and 10g/m
2. The thickness of the ion selective layer is about 3 μm to about 125 μm,
Preferably it is 5 μm to 50 μm.
【0022】本発明のイオン選択電極を用いるイオン活
量の測定は、電位差測定に要求される液−液間のイオン
移動を生じさせ、かつ促進させるためのブリッジを溝に
よってへだてられた二個の電極間に橋渡して設け、各電
極(具体的には、イオン選択層あるいは保護層)上に被
膜液及び参照液を同時に滴下してイオン活量に応じた電
位変化を電位差計で読みとることにより行われる。Measurement of ion activity using the ion-selective electrode of the present invention is carried out by using two bridges separated by a groove to generate and promote the ion transfer between liquid and liquid required for potentiometric measurement. This is done by placing a bridge between the electrodes, dropping a coating liquid and a reference liquid simultaneously on each electrode (specifically, an ion selective layer or a protective layer), and reading the potential change according to the ion activity with a potentiometer. be exposed.
【0023】上記、ブリッジの素材としても公知の材料
を適用することができ、例えばボーラスペーパー(濾紙
・吸取紙)、バインダー、メンブラン、フィルター、コ
ットン材料(綿布)、増粘材とポリカーボネート又はポ
リアミドとの混合物の如き多孔性物質で形成される。ブ
リッジの好ましい例及びその設け方は、特開昭52−1
42584号(米国特許第 4,053,381、 4
,214,968及び 4,171,246に対応)、
同55−59326号、同55−71942号、同55
−20499号(米国特許第 4,148,936に対
応)、実開昭55−64759号などに記載されている
。[0023] Known materials can be used as the material for the bridge, such as bolus paper (filter paper/blotting paper), binder, membrane, filter, cotton material (cotton cloth), thickener and polycarbonate or polyamide. formed of a porous material such as a mixture of Preferred examples of bridges and how to provide them are disclosed in Japanese Patent Application Laid-Open No. 52-1
No. 42584 (U.S. Pat. No. 4,053,381, 4
, 214,968 and 4,171,246),
No. 55-59326, No. 55-71942, No. 55
-20499 (corresponding to U.S. Pat. No. 4,148,936), Japanese Utility Model Application Publication No. 55-64759, etc.
【0024】本発明の電極が組み込まれる化学分析スラ
イドとしては、従来公知のスライドは総て可能であり、
例えば、特開昭58−211648号、特開昭62−9
264号公報に記載されている化学分析スライドがある
。[0024] As the chemical analysis slide in which the electrode of the present invention is incorporated, all conventionally known slides can be used.
For example, JP-A-58-211648, JP-A-62-9
There is a chemical analysis slide described in Publication No. 264.
【0025】[0025]
【作用】本発明のハロゲンイオン検出用電極では、イオ
ン選択層が銀層に接触しないことにより、銀層の腐食を
防止している。[Operation] In the halogen ion detection electrode of the present invention, the ion selective layer does not come into contact with the silver layer, thereby preventing corrosion of the silver layer.
【0026】[0026]
【実施例】本発明によるハロゲンイオン検出用電極の一
実施例を図1から図3に基づいて説明する。EXAMPLE An example of the electrode for detecting halogen ions according to the present invention will be described with reference to FIGS. 1 to 3.
【0027】図1は本発明によるハロゲンイオン検出用
電極の斜視図、図2は同上正面図、図3は同上平面図で
ある。FIG. 1 is a perspective view of a halogen ion detection electrode according to the present invention, FIG. 2 is a front view of the same, and FIG. 3 is a plan view of the same.
【0028】これらの図において、符号11は支持体で
、この支持体11の長手方向中央には「V」字状の絶縁
溝12が形成されている。支持体11の上面には、絶縁
溝12及びその近傍を残して銀層13、13が積層され
、この銀層13、13には、外側端部bを残して上面全
面にハロゲン化銀層14、14が積層されている。そし
て、このハロゲン化銀層14、14には、イオン選択層
15が各ハロゲン化銀層14、14のそれぞれの外側端
部cを残して全面に積層されている。In these figures, reference numeral 11 denotes a support, and a "V"-shaped insulating groove 12 is formed in the center of the support 11 in the longitudinal direction. Silver layers 13, 13 are laminated on the upper surface of the support 11, leaving the insulating groove 12 and its vicinity, and a silver halide layer 14 is laminated on the entire upper surface of the silver layers 13, 13, leaving the outer edge b. , 14 are stacked. An ion selective layer 15 is laminated over the entire surface of the silver halide layers 14, 14, except for the outer ends c of each silver halide layer 14, 14.
【0029】以上のようなハロゲンイオン検出用電極を
製造するには、図4に示すように、まず、銀層13を蒸
着により積層した支持体11を用意し(図4(a))、
次に、両側端に保護膜16を塗布するとともに、絶縁溝
12を穿設する(図4(b))。そして、所定の溶液で
処理して露出している銀層13の表面にハロゲン化銀層
14を形成し(図4(c))した後、保護膜16を除去
する(図4(d))。最後に、イオン選択層15をハロ
ゲン化層14の側端近傍を残した状態で塗布する(図4
(e))。そして、この積層体を所定の幅で切断し、電
極が完成する(図4(d))。In order to manufacture the electrode for detecting halogen ions as described above, as shown in FIG. 4, first, a support 11 on which a silver layer 13 is laminated by vapor deposition is prepared (FIG. 4(a)),
Next, a protective film 16 is applied to both ends, and an insulating groove 12 is bored (FIG. 4(b)). Then, a silver halide layer 14 is formed on the exposed surface of the silver layer 13 by treatment with a predetermined solution (FIG. 4(c)), and then the protective film 16 is removed (FIG. 4(d)). . Finally, the ion selective layer 15 is applied leaving the vicinity of the side edges of the halogenated layer 14 (Fig. 4
(e)). Then, this laminate is cut into a predetermined width to complete the electrode (FIG. 4(d)).
【0030】次に、以上のようなハロゲンイオン検出用
電極が組込まれる化学分析スライドの例を、図5及び図
6に基づいて説明する。図5は化学分析スライドの断面
図、図6は同上分解斜視図である。Next, an example of a chemical analysis slide incorporating the above-described electrode for detecting halogen ions will be explained based on FIGS. 5 and 6. FIG. 5 is a sectional view of the chemical analysis slide, and FIG. 6 is an exploded perspective view of the same.
【0031】これらの図において、符号21は支持枠板
で、この支持枠板21にハロゲンイオン検出用電極22
が固定されている。そして、この電極22の上面には、
水不浸透性部材23、多孔性液分配部材24及び液溜用
部材25が配設され、最上部にはブリッジ26が設けら
れた上蓋27が設けられている。In these figures, reference numeral 21 denotes a support frame plate, and a halogen ion detection electrode 22 is mounted on this support frame plate 21.
is fixed. Then, on the upper surface of this electrode 22,
A water-impermeable member 23, a porous liquid distribution member 24, and a liquid reservoir member 25 are provided, and an upper lid 27 is provided with a bridge 26 at the top.
【0032】実施例1
厚さ100μmのポリエチレンテレフタレート(PET
)フイルムに厚さ約800nmの銀を蒸着し、幅32m
m、長さ10cmに切り長さ方向に中心線に沿ってカッ
ター(NTカッターA−300型 日本転写紙K.K)
でフイルムを切り離すことなく、フイルムの表面のほぼ
中央に1本の切り傷(スクラッチ)状の絶縁溝を入れた
。テスターによる電気絶縁試験は完全な絶縁を示した。
次いで、この銀蒸着PETフイルムの長さ方向の両端に
幅5mmで液状マスク剤を塗布乾燥し、塩酸(36%)
5g、重クロム酸カリウム7g及び水1lからなる水溶
液で35℃にて60秒間処理(ハロゲン化処理)して銀
層の表面およびその近傍を塩化銀に変化させたのち、水
洗乾燥して液状マスク剤を除去した。Example 1 Polyethylene terephthalate (PET) with a thickness of 100 μm
) Silver is deposited to a thickness of approximately 800 nm on the film, and the width is 32 m.
m, cut into lengths of 10 cm along the center line in the length direction with a cutter (NT cutter A-300 type Nippon Transfer Paper K.K)
Without cutting the film, a single scratch-like insulating groove was made approximately in the center of the film surface. Electrical insulation test with a tester showed perfect insulation. Next, a liquid masking agent was applied to both lengthwise ends of this silver-deposited PET film in a width of 5 mm, dried, and then diluted with hydrochloric acid (36%).
5 g of potassium dichromate and 1 liter of water at 35°C for 60 seconds (halogenation treatment) to change the surface and vicinity of the silver layer to silver chloride, then washed with water and dried to form a liquid mask. The agent was removed.
【0033】そして、
VYNS
0.9gト
リオクチルメチルアンモニウムクロライド
1.35gジドデシルフタレート
0.03g
MEK
5gか
らなる溶液を、ハロゲン化銀層の端部を残して塗布し、
乾燥膜厚で28μmのクロルイオン選択層を形成した。[0033] And, VYNS
0.9g trioctylmethylammonium chloride
1.35g didodecyl phthalate
0.03g
M.E.K.
a solution consisting of 5 g is applied leaving the edges of the silver halide layer;
A chloro ion selective layer with a dry film thickness of 28 μm was formed.
【0034】実施例2
実施例1と同様な銀蒸着PETフイルム(幅32mm×
長さ2m)を6m/分の速さで銀蒸着フイルムの長手方
向に送りながら、カッターナイフをあてて銀蒸着PET
フイルムの長手方向に電気的絶縁が得られるまでの深さ
の絶縁溝を設けた。絶縁溝の深さは約1〜50μmの範
囲であった。Example 2 A silver vapor-deposited PET film (width 32 mm x
2m long) at a speed of 6m/min in the longitudinal direction of the silver-deposited film, using a cutter knife to remove the silver-deposited PET film.
Insulating grooves were provided in the longitudinal direction of the film to a depth sufficient to provide electrical insulation. The depth of the insulation trench ranged from approximately 1 to 50 μm.
【0035】塩化銀層及びクロルイオン選択層は実施例
1と同一である。The silver chloride layer and the chloro ion selective layer are the same as in Example 1.
【0036】比較例1
クロルイオン選択層と銀層とが接触する層構成である他
は、実施例1と同一である。Comparative Example 1 This was the same as Example 1 except that the layer structure was such that the chloro ion selective layer and the silver layer were in contact with each other.
【0037】比較例2
クロルイオン選択層と銀層とが接触する層構成である他
は、実施例2と同一である。Comparative Example 2 This was the same as Example 2 except that the layer structure was such that the chloro ion selective layer and the silver layer were in contact with each other.
【0038】試験I
方法;電極作成直後、ブリッジとしてカタン系を用いて
VERSATOL(103meq/l)を標準液とし、
Cl−イオン濃度が77meq/l、120meq/l
の溶液を測定した。
結果;実施例1、2及び比較例1、2とも測定データに
差は無かった。Test I Method: Immediately after electrode preparation, using Catan system as a bridge, VERSATOL (103 meq/l) was used as a standard solution,
Cl- ion concentration is 77 meq/l, 120 meq/l
The solution was measured. Results: There was no difference in the measured data between Examples 1 and 2 and Comparative Examples 1 and 2.
【0039】試験II
方法;電極作成後6ヶ月経過時において、試験1と同様
の方法で測定した。
結果;比較例1、2は測定不能であったが、実施例1、
2は正常に測定できた。Test II Method: Six months after electrode preparation, measurements were made in the same manner as in Test 1. Results: Comparative Examples 1 and 2 were unmeasurable, but Example 1 and
2 was successfully measured.
【0040】[0040]
【発明の効果】本発明は、1年以上の長期間保存しても
銀面の腐食が生ぜず、常に安定してハロゲンイオン濃度
を測定することができる。According to the present invention, the silver surface does not corrode even after long-term storage of one year or more, and the halogen ion concentration can always be measured stably.
【図1】本発明によるハロゲンイオン検出用電極の斜視
図。FIG. 1 is a perspective view of an electrode for detecting halogen ions according to the present invention.
【図2】本発明によるハロゲンイオン検出用電極の正面
図。FIG. 2 is a front view of an electrode for detecting halogen ions according to the present invention.
【図3】本発明によるハロゲンイオン検出用電極の平面
図。FIG. 3 is a plan view of an electrode for detecting halogen ions according to the present invention.
【図4】本発明によるハロゲンイオン検出用電極の製造
工程を示す図。FIG. 4 is a diagram showing the manufacturing process of a halogen ion detection electrode according to the present invention.
【図5】本発明によるハロゲンイオン検出用電極が組み
込まれる化学分析スライドの断面図。FIG. 5 is a cross-sectional view of a chemical analysis slide incorporating an electrode for detecting halogen ions according to the present invention.
【図6】本発明によるハロゲンイオン検出用電極が組み
込まれる化学分析スライドの分解斜視図。FIG. 6 is an exploded perspective view of a chemical analysis slide incorporating an electrode for detecting halogen ions according to the present invention.
【図7】従来のハロゲンイオン検出用電極の斜視図。FIG. 7 is a perspective view of a conventional halogen ion detection electrode.
【図8】従来のハロゲンイオン検出用電極の正面図。FIG. 8 is a front view of a conventional halogen ion detection electrode.
11…支持体 13…銀層 14…ハロゲン化銀層 15…イオン選択層 11...Support 13...Silver layer 14...Silver halide layer 15...Ion selective layer
Claims (1)
びイオン選択層を積層した電極において、イオン選択層
を銀層に接触しない状態で設けことを特徴とするハロゲ
ンイオン検出用電極1. An electrode for detecting halide ions, comprising a silver layer, a silver halide layer, and an ion selective layer laminated on a support, the ion selective layer being provided without contacting the silver layer.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3116376A JPH04344454A (en) | 1991-05-22 | 1991-05-22 | Electrode for detecting halogen ion |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP3116376A JPH04344454A (en) | 1991-05-22 | 1991-05-22 | Electrode for detecting halogen ion |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04344454A true JPH04344454A (en) | 1992-12-01 |
Family
ID=14685461
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP3116376A Pending JPH04344454A (en) | 1991-05-22 | 1991-05-22 | Electrode for detecting halogen ion |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04344454A (en) |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5810645A (en) * | 1981-07-13 | 1983-01-21 | Fuji Photo Film Co Ltd | Film-shaped ion selection electrode and ion concentration measuring device using the same |
JPS6426142A (en) * | 1987-07-22 | 1989-01-27 | Kyoto Daiichi Kagaku Kk | Ion electrode element |
-
1991
- 1991-05-22 JP JP3116376A patent/JPH04344454A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5810645A (en) * | 1981-07-13 | 1983-01-21 | Fuji Photo Film Co Ltd | Film-shaped ion selection electrode and ion concentration measuring device using the same |
JPS6426142A (en) * | 1987-07-22 | 1989-01-27 | Kyoto Daiichi Kagaku Kk | Ion electrode element |
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