JPH0416216Y2 - - Google Patents
Info
- Publication number
- JPH0416216Y2 JPH0416216Y2 JP1986191498U JP19149886U JPH0416216Y2 JP H0416216 Y2 JPH0416216 Y2 JP H0416216Y2 JP 1986191498 U JP1986191498 U JP 1986191498U JP 19149886 U JP19149886 U JP 19149886U JP H0416216 Y2 JPH0416216 Y2 JP H0416216Y2
- Authority
- JP
- Japan
- Prior art keywords
- gel
- internal
- electrode
- liquid
- internal liquid
- 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
- 239000007788 liquid Substances 0.000 claims description 64
- 239000011148 porous material Substances 0.000 claims description 16
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 230000000052 comparative effect Effects 0.000 claims description 5
- 239000012777 electrically insulating material Substances 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000499 gel Substances 0.000 description 16
- 238000000034 method Methods 0.000 description 13
- 239000000758 substrate Substances 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000010292 electrical insulation Methods 0.000 description 4
- 235000015110 jellies Nutrition 0.000 description 4
- 239000008274 jelly Substances 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- -1 polyethylene terephthalate Polymers 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- 108010010803 Gelatin Proteins 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 239000000783 alginic acid Substances 0.000 description 2
- 235000010443 alginic acid Nutrition 0.000 description 2
- 229960001126 alginic acid Drugs 0.000 description 2
- 229920000615 alginic acid Polymers 0.000 description 2
- 150000004781 alginic acids Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008273 gelatin Substances 0.000 description 2
- 229920000159 gelatin Polymers 0.000 description 2
- 235000019322 gelatine Nutrition 0.000 description 2
- 235000011852 gelatine desserts Nutrition 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000003020 moisturizing effect Effects 0.000 description 2
- 229920000058 polyacrylate Polymers 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 239000005020 polyethylene terephthalate Substances 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007767 bonding agent Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 239000008278 cosmetic cream Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229920002050 silicone resin Polymers 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical group [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Description
【考案の詳細な説明】
〔産業上の利用分野〕
本考案は、溶液のPHなどのイオン濃度を測定す
る場合において、測定電極に対する基準電極とし
て使用される比較電極に関する。[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a reference electrode used as a reference electrode for a measurement electrode when measuring ion concentration such as pH of a solution.
前記イオン濃度を測定するときに使用される比
較電極として、例えば、電気絶縁材からなる支持
板内に内部電極が埋め込み状に設けられて、この
内部電極にリード部が接続され、かつ前記内部電
極に接触させてKCl溶液などからなる内部液が封
入状に支持体に設けられるとともに、コルク多孔
体、セラミツク多孔体、または綿などの多孔体か
らなる液絡部を、前記内部液に接触させて支持板
に取付けてなるシート型比較電極が知られてい
る。また、特開昭47−7749号公報や特開昭52−
11091号公報に開示されたように、支持パイプ内
に内部電極を設けてなる比較電極においては、そ
の内部液をゲル状または硬化性高分子材料に含浸
させることも知られている。
As a comparison electrode used when measuring the ion concentration, for example, an internal electrode is provided embedded in a support plate made of an electrically insulating material, a lead part is connected to this internal electrode, and the internal electrode is An internal liquid such as a KCl solution is provided on the support in an enclosed manner, and a liquid junction made of a porous material such as a porous cork, a porous ceramic, or a porous material such as cotton is brought into contact with the internal liquid. A sheet-type reference electrode attached to a support plate is known. Also, JP-A-47-7749 and JP-A-52-
As disclosed in Japanese Patent No. 11091, it is also known that in a comparative electrode in which an internal electrode is provided within a support pipe, a gel-like or curable polymeric material is impregnated with the internal liquid.
前記従来のシート型比較電極は、その全体構成
から内部液の量が少なく、かつこの内部液に接触
した液絡部は多孔性物質で構成されているから、
この液絡部のために内部液が流出するなどして失
われる。このように内部液の量が減少すると、内
部液の補充は困難であり、かつ多孔体からなる液
絡部に目詰まりなどが生じるから、イオン測定時
における指示が不安定になるなどの問題が発生す
る。
The conventional sheet-type reference electrode has a small amount of internal liquid due to its overall structure, and the liquid junction in contact with this internal liquid is made of a porous material.
Due to this liquid junction, the internal liquid leaks out and is lost. When the amount of internal liquid decreases in this way, it is difficult to replenish the internal liquid, and the liquid junction made of porous material becomes clogged, leading to problems such as unstable indications during ion measurement. Occur.
また、前記各特許公開公報に開示された支持パ
イプを用いた比較電極は、その内部液をゲル状な
どにして減少を防いでいる。しかし、この比較電
極の内部液の量は、前記シート型比較電極の内部
液に比してかなり多くなるから、内部液の含浸対
象であるゲル状または硬化性高分子材料自体に、
化学的及び機械的な強度が不足すると、比較電極
の洗浄時に内部液が流出したり、内部液そのもの
が崩れるおそれがあり、形状の維持に問題があ
る。 Further, in the comparison electrode using a support pipe disclosed in each of the above-mentioned patent publications, the internal liquid is made into a gel state or the like to prevent the liquid from decreasing. However, since the amount of the internal liquid of this comparative electrode is considerably larger than that of the sheet-type comparative electrode, the internal liquid is impregnated with the gel-like or curable polymer material itself.
If the chemical and mechanical strength is insufficient, there is a risk that the internal liquid may leak out during cleaning of the reference electrode or the internal liquid itself may collapse, causing problems in maintaining the shape.
本考案は、上記のような問題を解決するもので
あつて、前記シート型比較電極における少量の内
部液の減少を防ぐことが可能であり、かつ多孔体
からなる液絡部に目詰まるなどが生じることを防
ぐことが可能な比較電極をうることを目的とす
る。 The present invention solves the above-mentioned problems, and is capable of preventing a small amount of internal liquid from decreasing in the sheet-type reference electrode, and also prevents clogging of the liquid junction made of a porous body. The purpose is to provide a reference electrode that can prevent this from occurring.
本考案の比較電極は、電気絶縁材からなる支持
板内に内部電極が埋め込み状に設けられて、この
内部電極にリード部が接続され、かつ前記内部電
極に接触する内部液が支持体内に設けられ、この
内部液に接触する多孔体からなる液絡部が支持板
に設けられたシート型の比較電極において、前記
内部液がゲル状にされ、かつ化学的に安定した親
水性高分子多孔体に、空気中に放置してもドライ
アウトしないゲル組成体を含浸させてなるゲル含
浸親水性高分子多孔体で前記液絡部が構成された
ことを特徴とする。
The reference electrode of the present invention has an internal electrode embedded in a support plate made of an electrically insulating material, a lead part connected to the internal electrode, and an internal liquid in contact with the internal electrode provided in the support. In a sheet-type reference electrode in which a support plate is provided with a liquid junction made of a porous material that contacts this internal liquid, the internal liquid is made into a gel and a chemically stable hydrophilic polymer porous material is used. Preferably, the liquid junction is made of a gel-impregnated hydrophilic polymer porous material impregnated with a gel composition that does not dry out even when left in the air.
本考案の前記比較電極は、内部液をゲル状にす
ることで、その乾燥や流出を防ぎ、かつこのゲル
状の内部液は比較的少量であつて一定の形状を維
持することが可能であるから、内部液とリード部
などとの電気的接続を確実にする。そして、多孔
体からなる液絡部の各孔部を、それに含浸させた
ゲル組成体が閉鎖して、前記内部液が減少するこ
とをより確実に防止する。また、前記ゲル組成体
が多孔体の目詰まりを阻止するとともに、多孔体
に常に湿潤状態を維持させて、精度よくイオン濃
度の測定を可能にする。
The reference electrode of the present invention has a gel-like internal liquid to prevent it from drying out or flowing out, and the gel-like internal liquid is in a relatively small amount and can maintain a constant shape. to ensure electrical connection between the internal liquid and the lead parts. The gel composition impregnated therein closes each hole of the liquid junction made of a porous body, thereby more reliably preventing the internal liquid from decreasing. In addition, the gel composition prevents clogging of the porous body and keeps the porous body constantly moist, allowing accurate measurement of ion concentration.
本考案の比較電極の第１実施例を第１〜３図に
示したPH用のシート型複合電極について説明す
る。
A first embodiment of the comparative electrode of the present invention will be described with respect to a sheet-type composite electrode for PH shown in FIGS. 1 to 3.
第１〜３図において、１１は電解物質を含有す
る溶液中に浸漬しても十分に高い電気絶縁性を有
する材料であるポリエチレンテレフタレートから
なる基板である。この基板１１を構成する材料と
しては、他のポリエチレン、ポリプロピレン、ア
クリル、ポリふつ化エチレンなどの有機高分子材
料、または石英ガラス、パイレツクスなどの無機
材料も挙げることができる。 In FIGS. 1 to 3, reference numeral 11 denotes a substrate made of polyethylene terephthalate, which is a material that has sufficiently high electrical insulation even when immersed in a solution containing an electrolytic substance. Examples of the material constituting the substrate 11 include other organic polymeric materials such as polyethylene, polypropylene, acrylic, and polyfluorinated ethylene, and inorganic materials such as quartz glass and Pyrex.
前記基板１１の上面には、電気良導体である
Ag、Cu，Au、Ptなど及びこれらの合金などの
内から選ばれた金属またはその金属を含むペース
ト、あるいはIrO2、SnO2などの半導体を、真空
蒸着法、CVD法などの物理的メツキ法、または
電解法、無電解法などの化学的メツキ法、あるい
はシルクスクリンーン法、凸版法、平板法などの
印刷法によつて、内外二対の電極１２Ａ，１２
Ｂ，１３Ａ，１３Ｂが形成されている（本例は、
基板１１の上面をグラフト加工及びシランカツプ
リグ剤などによるアンカー処理を行つてから、
Agペーストをシルクスクリーンして形成してい
る）。 The upper surface of the substrate 11 is a good electrical conductor.
Metals selected from Ag, Cu, Au, Pt, etc. and their alloys, pastes containing these metals, or semiconductors such as IrO 2 and SnO 2 are coated with physical plating methods such as vacuum evaporation and CVD. , or by a chemical plating method such as an electrolytic method or an electroless method, or a printing method such as a silk screen method, a letterpress method, or a flat plate method, the two pairs of inner and outer electrodes 12A, 12 are formed.
B, 13A, 13B are formed (in this example,
After grafting the upper surface of the substrate 11 and anchoring with a silane coupling agent,
(It is formed by silk-screening Ag paste).
そして、電極１２Ａ，１２Ｂ，１３Ａ，１３Ｂ
のそれぞれにおける、基板１１の端縁側の端部が
そのままリード部１４Ａ，１４Ｂ，１５Ａ，１５
Ｂとされ、かつ外側の一対の電極１２Ａ，１２Ｂ
の各他端の円形部分が、例えば、AgClなどの電
極材料で被覆されて（前記と同様に、物理的メツ
キ法または化学的メツキ法あるいは印刷法などに
よる）内部電極部１６Ａ，１６Ｂとされ、内側の
一対の電極１３Ａ，１３Ｂの各他端間に、サーミ
スタなどによる温度補償用電極部１７が設けられ
ている。 And electrodes 12A, 12B, 13A, 13B
The end portions on the edge side of the substrate 11 in each of the lead portions 14A, 14B, 15A, 15
B, and a pair of outer electrodes 12A, 12B
The circular portions at each other end are coated with an electrode material such as AgCl (by physical plating method, chemical plating method, printing method, etc. as described above) to form internal electrode portions 16A, 16B, A temperature compensation electrode section 17 such as a thermistor is provided between each other end of the pair of inner electrodes 13A, 13B.
１８は基板１１の上面に設けられた支持層で、
これは基板１１と同様に、十分に高い電気絶縁性
を有する材料（本例は、ポリエチレンテレフタレ
ート）からなり、かつ基板１１に形成された内部
電極部１６Ａ，１６Ｂのそれぞれと重なる位置
で、支持層１８に貫通孔１９，２０が形成され、
かつ支持層１８の表面において、前記貫通孔１９
の周囲に所定大きさの凹陥部２１が設けられてい
る。 18 is a support layer provided on the upper surface of the substrate 11;
Like the substrate 11, the support layer is made of a material having sufficiently high electrical insulation (polyethylene terephthalate in this example), and is placed at a position overlapping each of the internal electrode portions 16A and 16B formed on the substrate 11. Through holes 19 and 20 are formed in 18,
And on the surface of the support layer 18, the through hole 19
A recessed portion 21 of a predetermined size is provided around the periphery.
前記支持層１８は、例えば、スクリーン印刷
法、または十分に高い電気絶縁性（例えば、
10MΩ以上）を備えた接合剤（例えば、ポリオレ
フイン系、シリコンレジン系など）を用いて熱融
着手段で形成する。なお、支持層１８の上面は、
グラフト加工及びシランカツプリグ剤などによる
アンカー処理をあらかじめ行つておくことが適す
る。 The support layer 18 can be formed, for example, by screen printing or by a method having a sufficiently high electrical insulation property (for example,
10MΩ or more) using a bonding agent (e.g., polyolefin type, silicone resin type, etc.) by heat fusion means. Note that the upper surface of the support layer 18 is
It is suitable to perform graft processing and anchor treatment using a silane coupling agent or the like in advance.
２２は支持層１８の貫通孔１９に装填して、前
記内部電極部１６Ａに接触させたゲル状内部液
で、このゲル状内部液は、例えばAgcl過飽和の
3.3M−KClに燐酸緩衝液を加えてなる基本的な
内部液に、ゲル化剤（例えば、寒天、ゼラチン、
ニカワ、アルギン酸、各種アクリル系吸水性ポリ
マーなど）とゲル蒸発防止剤（例えば、グリセリ
ン、エチレングリコールなど）とを添加して、例
えば円盤状に形成したものである。 Reference numeral 22 denotes a gel-like internal liquid that is loaded into the through-hole 19 of the support layer 18 and brought into contact with the internal electrode portion 16A.
A gelling agent (e.g. agar, gelatin,
Glue, alginic acid, various acrylic water-absorbing polymers, etc.) and a gel evaporation inhibitor (eg, glycerin, ethylene glycol, etc.) are added to form a disc-shaped product.
前記ゲル状内部液２２は、例えば、加熱でペー
スト状にして、それをスクリーン印刷法により、
自由状態で上面が支持層１８の上面よりも若干突
出する状態で貫通孔１９に充填されている。そし
て、所要の大きさに形成された平板状の選択性イ
オン応答膜２３を、ゲル状内部液２２の上に重ね
る状態で密着させて、ゲル状内部液２２を封入状
態にしてPH測定電極Ｐを構成している。 The gel-like internal liquid 22 is made into a paste by heating, for example, and then printed using a screen printing method.
The through hole 19 is filled with the upper surface slightly protruding from the upper surface of the support layer 18 in a free state. Then, the flat selective ion response membrane 23 formed to the required size is brought into close contact with the gel-like internal liquid 22 in an overlapping manner, and the gel-like internal liquid 22 is sealed in the PH measuring electrode P. It consists of
２４は選択性イオン応答膜２３の周囲部を支持
層１８に固着する高分子接着剤で、これは十分に
高い電気絶縁性を有するもので、例えばシランカ
ツプリング剤などを使用する。 Reference numeral 24 denotes a polymer adhesive for fixing the peripheral portion of the selective ion response membrane 23 to the support layer 18, which has sufficiently high electrical insulation properties, such as a silane coupling agent.
２５は支持層１８に形成された前記貫通孔２０
に挿入して取付けられたゲル含浸親水性高分子多
孔体で、これが比較電極Ｒの液絡部兼内部液部分
として機能する。そして、前記ゲル含浸親水性高
分子多孔体２５は、化学的に安定な親水性高分子
粒体を焼結成形してなる親水性高分子多孔体、例
えば、ポリオレフインと同程度の機械的強度を有
し、かつ変化性処理によつて親水性を付与したオ
レフイン系ハイポリマー粉体の焼結成形体（例え
ば、サンフアインAQ：商品名 旭化成社製）
に、空気中に放置してもKClが析出したり、前記
多孔体表面の湿潤さを失うことがない、所謂ドラ
イアウトしないゲル組成体を含浸させてなるもの
である。 25 is the through hole 20 formed in the support layer 18
The gel-impregnated hydrophilic polymer porous body is inserted and attached to the reference electrode R, and this functions as a liquid junction portion and an internal liquid portion of the reference electrode R. The gel-impregnated hydrophilic porous material 25 is a hydrophilic porous material formed by sintering chemically stable hydrophilic polymer particles, and has mechanical strength comparable to that of polyolefin, for example. A sintered compact of olefin-based high polymer powder that has the same properties and has been given hydrophilic properties through a variable treatment (for example, Sanhuain AQ: trade name, manufactured by Asahi Kasei Corporation)
Furthermore, it is impregnated with a gel composition that does not cause KCl to precipitate or lose moisture on the surface of the porous body even when left in the air, so-called a non-dry-out gel composition.
また、前記ゲル組成体は、例えば、AgCl過飽
和の3.3M−KCl溶液に燐酸緩衝液を添加してな
る内部液に、アクリル系ポリマーを主成分とする
高保湿性の含水ゼリー（例えば、Ｕジエリー：商
品名 昭和電工社製）を溶解するとともに、寒
天、ゼラチン、ニカワ、アルギン酸などから選ん
だゲル化剤を添加してゲル化させたものである。 In addition, the gel composition may be prepared by adding a highly moisturizing jelly containing an acrylic polymer as a main component (for example, U jewelry) to an internal solution obtained by adding a phosphate buffer to a 3.3M KCl solution supersaturated with AgCl. ：Product name: manufactured by Showa Denko Co., Ltd.) is dissolved and gelatinized by adding a gelling agent selected from agar, gelatin, glue, alginic acid, etc.
そして、高保湿性の含水ゼリーとしての前記Ｕ
ジエリーは、元来は化粧用クリームなどのベース
剤として昭和電工社が開発したもので、アクリル
系ポリマーのNa塩を主成分とする透明な含水ゼ
リーである。これは他の水溶液に対する相溶性が
非常に高く、かつポリマー分子間の水素結合によ
るクラレイスト形成によつて、従来使用されてい
たグリセリンやプロピレングリコールなどの水分
蒸発防止剤に比べて、極めてすぐれた水分保持機
能を有するとともに、蒸気圧に対する平衡状態保
持機能も極めてすぐれている。したがつて、空気
中に長期間曝しておいてもドライアウトしない
で、十分な湿潤性を保持しうるとともに、たとえ
周囲空気の湿度が高い場合であつても、その空気
中の水分を吸着や露結することはほとんどないか
ら、その表面の湿潤状態を常に適度に保持するこ
とが可能な性質を備えている。 And the above-mentioned U as a highly moisturizing water-containing jelly
Jelly was originally developed by Showa Denko as a base agent for cosmetic creams, etc., and is a transparent water-containing jelly whose main ingredient is Na salt of an acrylic polymer. It has very high compatibility with other aqueous solutions, and due to the formation of Claraist formed by hydrogen bonds between polymer molecules, it has extremely superior moisture evaporation inhibitors compared to conventionally used moisture evaporation inhibitors such as glycerin and propylene glycol. In addition to having a holding function, it also has an extremely excellent ability to maintain an equilibrium state with respect to vapor pressure. Therefore, even if exposed to the air for a long period of time, it will not dry out and maintain sufficient moisture, and even if the surrounding air is humid, it will not adsorb or absorb moisture in the air. Since there is almost no dew condensation, it has the property of being able to keep its surface moist at all times.
この第１実施例は、前記基板１１と支持層１８
とで支持体を構成している。 This first embodiment consists of the substrate 11 and the support layer 18.
and constitute a support.
前記のように構成したシート型複合電極は、例
えば、AgCl過飽和の3.3M−KCl溶液に燐酸干渉
液を添加した内部液をゲル化してなるゲル組成体
を含浸したゲル含浸親水性高分子多孔体２５を使
用しているから、このゲル含浸親水性高分子多孔
体２５を比較電極Ｒの液絡部兼内部液とすること
ができる。したがつて、少量の内部液の配置を適
確にかつ容易に行うことが可能である。そして、
前記ゲル組成体は多孔体２５に含浸されているか
ら、そのゲル組成体は一定の形状を維持して内部
電極部１６Ｂに密着し、内部液としての作用を十
分に果たすとともに、液絡部を構成した多孔体２
５の目詰まりを阻止し、かつ液絡部に常に湿潤状
態を維持させるから、精度よくイオン濃度を測定
することが可能である。 The sheet-type composite electrode configured as described above is made of, for example, a gel-impregnated hydrophilic polymer porous body impregnated with a gel composition obtained by gelling an internal liquid obtained by adding a phosphoric acid interference solution to a 3.3M KCl solution supersaturated with AgCl. 25, this gel-impregnated hydrophilic polymer porous body 25 can be used as a liquid junction and an internal liquid of the reference electrode R. Therefore, it is possible to accurately and easily arrange a small amount of internal liquid. and,
Since the gel composition is impregnated into the porous body 25, the gel composition maintains a constant shape and adheres closely to the internal electrode portion 16B, fully acts as an internal liquid, and also protects the liquid junction. Structured porous body 2
Since the liquid junction is kept in a moist state at all times, it is possible to measure the ion concentration with high accuracy.
第４図は第２実施例を示し、内部液の配置に関
するものである。 FIG. 4 shows a second embodiment, which relates to the arrangement of the internal liquid.
第４図において、３０は前記第１実施例におけ
るPH測定電極Ｐのゲル上内部液２２と同組成のゲ
ル状内部液で、基板１１の下面側に配置されてい
る。そして、比較電極Ｒ側において、基板１１の
内部電極部１６Ｂと重なる位置に設けられた貫通
孔３１にも前記ゲル状内部液３０が充填されて、
このゲル状内部液３０が内部電極部１６Ｂに接触
している。 In FIG. 4, reference numeral 30 denotes a gel-like internal liquid having the same composition as the gel-like internal liquid 22 of the PH measuring electrode P in the first embodiment, and is disposed on the lower surface side of the substrate 11. Then, on the comparison electrode R side, the through hole 31 provided at a position overlapping with the internal electrode portion 16B of the substrate 11 is also filled with the gel-like internal liquid 30,
This gel-like internal liquid 30 is in contact with the internal electrode portion 16B.
そして、基板１１と支持層１８のそれぞれに、
互いに連通して貫通孔３２，３３が設けられて、
前記第１実施例におけるゲル含浸親水性高分子多
孔体２５と同構成のゲル含浸親水性高分子多孔体
３４を前記貫通孔３２，３３に挿入固定し、かつ
このゲル含浸親水性高分子多孔体３４を前記ゲル
状内部液３０に接触させて液絡部を形成してい
る。３５は底ケースである。他の構成は、前記第
１実施例と同じであるから、同符号を付して示し
た。 Then, on each of the substrate 11 and the support layer 18,
Through holes 32 and 33 are provided to communicate with each other,
A gel-impregnated hydrophilic polymer porous body 34 having the same structure as the gel-impregnated hydrophilic porous polymer body 25 in the first embodiment is inserted and fixed into the through holes 32 and 33, and this gel-impregnated hydrophilic polymer porous body 34 is brought into contact with the gel-like internal liquid 30 to form a liquid junction. 35 is a bottom case. Since the other configurations are the same as those of the first embodiment, they are indicated by the same reference numerals.
この第２実施例は、液絡部を構成するゲル含浸
親水性高分子多孔体３４が、ゲル状内部液３０を
介してリード部１２ｂに接続される。 In this second embodiment, a gel-impregnated hydrophilic polymer porous body 34 constituting a liquid junction is connected to a lead portion 12b via a gel-like internal liquid 30.
本考案の比較電極は、上記のように、支持板内
に埋め込み状に設けられた内部電極に接触する内
部液がゲル状にされ、かつ化学的に安定した親水
性高分子多孔体に、空気中に放置してもドライア
ウトしないゲル組成体を含浸させてなるゲル含浸
親水性高分子多孔体を前記ゲル状内部液に接触さ
せて液絡部を構成している。
As mentioned above, the reference electrode of the present invention has an internal liquid in contact with an internal electrode embedded in a support plate that is made into a gel, and a chemically stable hydrophilic polymer porous body that is filled with air. A gel-impregnated hydrophilic polymer porous body impregnated with a gel composition that does not dry out even when left inside is brought into contact with the gel-like internal liquid to form a liquid junction.
したがつて、比較的少量の内部液を内部電極に
確実に接触させて配置することが容易である。し
かも、液絡部を構成した前記高分子多孔体は親水
性であるから、その微細な各孔に対してゲル組成
体をスムーズに含浸させることができるから、そ
のほぼ全体を確実に湿潤させることができ、液絡
部の作用を確実に果たすことができる。しかも、
前記微細な各孔をゲル組成体で閉鎖しているか
ら、前記少量の内部液が減少することを長期間に
わたつて防ぐとともに、高分子多孔体に目詰りが
生じることを防ぐことが可能であり、イオン濃度
を精度良く測定することができる。 Therefore, it is easy to place a relatively small amount of internal liquid in reliable contact with the internal electrodes. Moreover, since the polymeric porous material that constitutes the liquid junction is hydrophilic, each of its minute pores can be smoothly impregnated with the gel composition, ensuring that almost the entire surface is wetted. This allows the liquid junction to function reliably. Moreover,
Since each of the minute pores is closed with a gel composition, it is possible to prevent the small amount of internal liquid from decreasing over a long period of time, and also to prevent clogging of the porous polymer body. ion concentration can be measured with high accuracy.
第１〜３図は本考案の第１実施例を示し、第１
図は分解斜視図、第２図は第１図の−線断面
図、第３図は第１図の−線断面図、第４図は
第２実施例の一部展開断面図である。
２５，３４……ゲル含浸親水性高分子多孔体。
1 to 3 show a first embodiment of the present invention.
The figure is an exploded perspective view, FIG. 2 is a cross-sectional view taken along the line -- in FIG. 1, FIG. 3 is a cross-sectional view taken along the line -- in FIG. 25,34...Gel-impregnated hydrophilic polymer porous material.
Claims (1)
込み状に設けられて、この内部電極にリード部が
接続され、かつ前記内部電極に接触する内部液が
支持体内に設けられ、この内部液に接触する多孔
体からなる液絡部が支持板に設けられたシート型
の比較電極において、前記内部液がゲル状にさ
れ、かつ化学的に安定した親水性高分子多孔体
に、空気中に放置してもドライアウトしないゲル
組成体を含浸させてなるゲル含浸親水性高分子多
孔体で前記液絡部が構成されたことを特徴とする
比較電極。 An internal electrode is provided embedded in a support plate made of an electrically insulating material, a lead portion is connected to the internal electrode, and an internal liquid that contacts the internal electrode is provided within the support, and the internal liquid comes into contact with the internal electrode. In a sheet-type reference electrode in which a liquid junction made of a porous material is provided on a support plate, the internal liquid is turned into a gel and left in a chemically stable hydrophilic polymer porous material in the air. A comparative electrode characterized in that the liquid junction is formed of a gel-impregnated hydrophilic polymer porous material impregnated with a gel composition that does not dry out even when exposed to water.
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1986191498U JPH0416216Y2 (en) | 1986-12-11 | 1986-12-11 | |
| US07/124,903 US4980043A (en) | 1986-12-11 | 1987-11-24 | Reference electrode |
| KR1019870013382A KR900005243B1 (en) | 1986-12-11 | 1987-11-26 | Referance electrode |
| CN87107350A CN1010254B (en) | 1986-12-11 | 1987-12-10 | Reference electrode |
| EP87118326A EP0271101B1 (en) | 1986-12-11 | 1987-12-10 | Reference electrode |
| DE3751746T DE3751746D1 (en) | 1986-12-11 | 1987-12-10 | Reference electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1986191498U JPH0416216Y2 (en) | 1986-12-11 | 1986-12-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6396458U JPS6396458U (en) | 1988-06-22 |
| JPH0416216Y2 true JPH0416216Y2 (en) | 1992-04-10 |
Family
ID=31145697
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1986191498U Expired JPH0416216Y2 (en) | 1986-12-11 | 1986-12-11 |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0416216Y2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1491519A1 (en) * | 2003-06-25 | 2004-12-29 | Mettler-Toledo GmbH | Process for treating a porous ceramic |
| JP4733588B2 (en) * | 2005-08-03 | 2011-07-27 | 国立大学法人京都大学 | Reference electrode, salt bridge and ion concentration measuring device using them |
| JP5291982B2 (en) * | 2008-05-07 | 2013-09-18 | 国立大学法人三重大学 | Liquid junction and method for manufacturing the same |
| JP2013160577A (en) * | 2012-02-03 | 2013-08-19 | Hioki Ee Corp | Electrochemical sensor and electrochemical measuring device |
| WO2013158985A1 (en) * | 2012-04-19 | 2013-10-24 | Luoxis Diagnostics, Inc. | Multiple layer gel |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS55167152U (en) * | 1979-05-18 | 1980-12-01 |
-
1986
- 1986-12-11 JP JP1986191498U patent/JPH0416216Y2/ja not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6396458U (en) | 1988-06-22 |
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