WO2015115587A1 - 比較電極用内部液、比較電極及びガラス電極 - Google Patents
比較電極用内部液、比較電極及びガラス電極 Download PDFInfo
- Publication number
- WO2015115587A1 WO2015115587A1 PCT/JP2015/052633 JP2015052633W WO2015115587A1 WO 2015115587 A1 WO2015115587 A1 WO 2015115587A1 JP 2015052633 W JP2015052633 W JP 2015052633W WO 2015115587 A1 WO2015115587 A1 WO 2015115587A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electrode
- glass
- internal liquid
- methacrylate
- liquid
- Prior art date
Links
Images
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
- G01N27/301—Reference electrodes
-
- 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
- G01N27/302—Electrodes, e.g. test electrodes; Half-cells pH sensitive, e.g. quinhydron, antimony or hydrogen electrodes
-
- 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
- G01N27/36—Glass electrodes
Definitions
- the present invention relates to an internal liquid for a comparative electrode, a comparative electrode using the same, and a glass electrode used together with the comparative electrode.
- Patent Document 1 As an electrode used in a pH meter, for example, there is one shown in Patent Document 1, and in particular, as a comparative electrode used in this pH meter, a gel composition as shown in Patent Document 2 is used as an internal liquid. It has been.
- This gel composition can be produced by a relatively easy process by polymerizing a monomer in a solvent, and is expected to be applied to a wide range of uses including an internal solution for electrodes.
- the gel composition referred to here is a kind of dispersion, which means a semi-solid material system that has a high viscosity due to a dispersoid network but has lost its fluidity, and in a broad sense, a solid dispersion medium. Includes solid sols that are colloids.
- the above-described gel-like composition has a problem of poor durability, and the reference electrode using the gel-like composition as an internal liquid has a large liquid-liquid potential generated when the sample is alkaline. Minute measurement error may increase.
- the present invention has been made to solve the above-described problems, and its main problem is to improve the durability of the internal liquid for the reference electrode as compared with the conventional technique.
- the internal solution for a reference electrode according to the present invention contains a cross-linking agent having a plurality of functional groups excluding acrylamide and a copolymer of a monofunctional hydrophilic monomer excluding acrylamide. To do.
- Such an internal liquid for a comparative electrode contains a copolymer obtained by copolymerizing a crosslinking agent having a plurality of functional groups and a monofunctional hydrophilic monomer, a crosslinked structure is formed in the copolymerized one.
- the durability can be improved as compared with the conventional case.
- a highly toxic substance is used as a substance for the polymerization reaction, there is a risk in handling the manufacturing process and the manufactured internal liquid and the reference electrode using the same. Danger can be reduced.
- the cross-linking agent is preferably acrylate or methacrylate, and the hydrophilic monomer Is preferably acrylate or methacrylate.
- the internal liquid for the reference electrode is rich in pressure resistance and heat resistance.
- the crosslinking agent is a monomer having a plurality of functional groups. Examples include acrylates having a functional group, methacrylates having a plurality of functional groups, amines having a plurality of functional groups, and vinyl compounds having a plurality of functional groups. Preferably, it is an acrylate having a plurality of functional groups or a methacrylate having a plurality of functional groups.
- Examples of the acrylate or the methacrylate include glycerin diacrylate, polyalkylene glycol diacrylate, polyalkylene glycol triacrylate, and ethoxylated bisphenol A diester.
- Examples include acrylate, ethoxylated glycerin triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, polyalkylene glycol dimethacrylate, glycerin dimethacrylate, polyalkylene glycol triacrylate, and the like.
- examples of amines having a plurality of functional groups include triethylenetetramine, ethylenediamine, hexamethylenediamine, and dipropylenetriamine.
- Examples of vinyl compounds having a plurality of functional groups include divinylbenzene, butanediol divinyl ether, Examples include diethylene glycol divinyl ether.
- hydrophilic monomer examples include alkylaminoalkyl acrylates, polyhydric alcohol acrylates, and alkoxy ether derivatives thereof, acryloyloxyethyl succinic acid, acryloyloxyethyl acid phosphate, 2- (acryloyloxy) ethanesulfonic acid, acrylic 3-sulfopropyl potassium acid, alkylaminoalkyl methacrylate, polyhydric alcohol methacrylate, and alkoxy ether derivatives thereof, methacryloyloxyethyl succinic acid, methacryloyloxyethyl acid phosphate, 2- (methacryloyloxy) ethanesulfonic acid, methacrylic acid Examples include acid 3-sulfopropyl potassium.
- alkylaminoalkyl methacrylate examples include dimethylaminoethyl methacrylate and its quaternized product, diethylaminoethyl methacrylate and its quaternized product, dipropylaminoethyl methacrylate and its quaternized product, N, N, N-trimethyl- (2 -Hydroxy-3-methacryloyloxy) propylammonium chloride, and the like.
- alkylaminoalkyl acrylate examples include dimethylaminoethyl acrylate and its quaternized product, diethylaminoethyl acrylate and its quaternized product, dipropylaminoethyl acrylate and its quaternized product, N, N, N-trimethyl- (2 -Hydroxy-3-acryloyloxy) propylammonium chloride, and the like.
- examples of the polyhydric alcohol methacrylate and its alkoxy ether derivative include glycerin methacrylate and ethylene glycol methacrylate monomer.
- Specific examples of the ethylene glycol methacrylate monomer include polyethylene glycol monomethacrylate, methoxypolyethylene glycol monomethacrylate, and polyethylene glycol monomethacrylate. And methacrylate monomers.
- examples of the polyhydric alcohol acrylate and alkoxy ether derivatives thereof include glycerin acrylate and ethylene glycol acrylate monomers.
- Specific examples of the ethylene glycol acrylate monomer include polyethylene glycol monoacrylate, methoxypolyethylene glycol monoacrylate, and polyethylene glycol monoacrylate.
- Acrylate monomers such as
- the comparative electrode having the above-described internal liquid for the comparative electrode is also one aspect of the present invention. Further, the present invention includes a glass electrode that is used together with this comparative electrode and includes a response glass containing Me 2 O 3 (Me is a lanthanoid).
- the response glass contains at least a lanthanoid, a measurement error with respect to an alkaline sample is unlikely to occur, and a wide range of pH samples can be stably and accurately measured.
- the response glass contains Y 2 O 3 or Sc 2 O 3 . More specifically, if Y 2 O 3 is contained, durability can be improved while suppressing measurement errors for alkaline samples. Further, as long as it contains Sc 2 O 3, although the measurement error described above is readily released slightly, it is possible to particularly increase the effect of improving the durability.
- the present invention is based on the above-described glass electrode, a calculation unit that outputs measurement data indicating measurement results based on output values from the glass electrode and the comparison electrode, and measurement data output from the calculation unit.
- an electrochemical measurement device comprising a display unit for displaying the measurement result. If it is the electrochemical measuring device comprised in this way, the effect mentioned above can be acquired.
- the durability of the internal liquid for the reference electrode can be improved as compared with the conventional case.
- the electrochemical measurement apparatus outputs measurement data indicating measurement results such as pH of the sample based on the output values from the comparison electrode 3, the glass electrode 2, and the comparison electrode 3 and the glass electrode 2, for example.
- a computing unit such as a computer and a display unit (not shown) such as a display for displaying measurement results based on measurement data output from the computing unit are provided.
- the comparison electrode 3 is provided so as to surround the periphery of the glass electrode 2, and constitutes the composite electrode 1 integrally with the glass electrode 2.
- the glass electrode 2 includes a cylindrical glass electrode support tube 21, a response glass 22 provided at the tip of the glass electrode support tube 21, and an inner electrode 23 for glass electrode.
- the glass electrode support tube 21 accommodates the inner electrode 23 for glass electrode and is filled with, for example, a KCl solution having a pH of 7 as the inner liquid 24 for glass electrode.
- an Ag / AgCl electrode or the like is used, and one end side of the lead wire 4 is connected, and the other end side is connected to the cable 5 to be conducted to, for example, a pH meter main body (not shown).
- the response glass 22 is formed integrally with the glass electrode support tube 21 by being hermetically joined to the tip of the glass electrode support tube 21 by welding (thermal welding) or the like. More specifically, the response glass 22 of the present embodiment has a composition containing at least La 2 O 3 and additionally containing a smaller amount of Y 2 O 3 or Sc 2 O 3 than La 2 O 3 .
- the comparative electrode 3 includes a substantially cylindrical glass-made comparative electrode support tube 31, a liquid junction portion 32 penetrating in the thickness direction on the distal end side of the comparative electrode support tube 31, and a reference electrode inner electrode 33. Is provided.
- the tip of the comparison electrode support tube 31 is hermetically connected by welding (thermal welding) or the like in the vicinity of the connection portion between the glass electrode support tube 21 and the response glass 22.
- the comparison electrode support tube 31 is provided so as to surround the outer periphery of the glass electrode support tube 21, and in a portion (space) sandwiched between the inner side of the comparison electrode support tube 31 and the outer side (outer periphery) of the glass electrode support tube 21,
- the reference electrode inner electrode 33 is accommodated and filled with a reference electrode inner liquid 34 described later.
- An Ag / AgCl electrode or the like is used for the inner electrode 33 for the comparison electrode.
- one end side of the lead wire 4 is connected, and the other end side is connected to the cable 5.
- a pH meter body (not shown) is made conductive.
- the liquid junction portion 32 is formed by sealing a porous sintered body in a hole provided in advance in the outer peripheral wall of the reference electrode support tube 31 and opening a pinhole in the porous sintered body with a laser or the like. Has been.
- the liquid junction part 32 may be configured to form a small through hole in the reference electrode support tube 31 so that the internal liquid 34 for the reference electrode described later exhibits a liquid junction effect.
- the electromotive force corresponding to the pH difference is generated between the glass electrode internal liquid 24 and the sample, and the electromotive force is converted into glass.
- the pH of the sample can be measured.
- the internal liquid 34 for the reference electrode of the present embodiment is a gel produced by copolymerizing a monofunctional hydrophilic monomer and a crosslinking agent having a plurality of functional groups.
- the cross-linking agent and the hydrophilic monomer having a plurality of functional groups described above are substances excluding acrylamide and methacrylamide.
- the crosslinking agent examples include those having a plurality of polymerizable double bonds and those having a plurality of functional groups having reactivity in the molecule.
- the crosslinking agent is a monomer having a plurality of functional groups, and an acrylate having a plurality of functional groups, a methacrylate having a plurality of functional groups, an amine having a plurality of functional groups, and a vinyl compound having a plurality of functional groups.
- Examples of the acrylate or the methacrylate include glycerin diacrylate, polyalkylene glycol diacrylate, polyalkylene glycol triacrylate, ethoxylated bisphenol A diacrylate, ethoxylated glycerin triacrylate, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, poly Examples include alkylene glycol dimethacrylate, glycerin dimethacrylate, and polyalkylene glycol triacrylate.
- examples of amines having a plurality of functional groups include triethylenetetramine, ethylenediamine, hexamethylenediamine, and dipropylenetriamine.
- Examples of vinyl compounds having a plurality of functional groups include divinylbenzene, butanediol divinyl ether, Examples include diethylene glycol divinyl ether.
- hydrophilic monomer examples include alkylaminoalkyl acrylates, polyhydric alcohol acrylates, and alkoxy ether derivatives thereof, acryloyloxyethyl succinic acid, acryloyloxyethyl acid phosphate, 2- (acryloyloxy) ethanesulfonic acid, acrylic 3-sulfopropyl potassium acid, alkylaminoalkyl methacrylate, polyhydric alcohol methacrylate, and alkoxy ether derivatives thereof, methacryloyloxyethyl succinic acid, methacryloyloxyethyl acid phosphate, 2- (methacryloyloxy) ethanesulfonic acid, methacrylic acid Examples include 3-sulfopropyl potassium acid.
- alkylaminoalkyl methacrylate examples include dimethylaminoethyl methacrylate and its quaternized product, diethylaminoethyl methacrylate and its quaternized product, dipropylaminoethyl methacrylate and its quaternized product, N, N, N-trimethyl- (2 -Hydroxy-3-methacryloyloxy) propylammonium chloride, and the like.
- alkylaminoalkyl acrylate examples include dimethylaminoethyl acrylate and its quaternized product, diethylaminoethyl acrylate and its quaternized product, dipropylaminoethyl acrylate and its quaternized product, N, N, N-trimethyl- (2 -Hydroxy-3-acryloyloxy) propylammonium chloride, and the like.
- examples of the polyhydric alcohol methacrylate and its alkoxy ether derivative include glycerin methacrylate and ethylene glycol methacrylate monomer.
- Specific examples of the ethylene glycol methacrylate monomer include polyethylene glycol monomethacrylate, methoxypolyethylene glycol monomethacrylate, and polyethylene glycol monomethacrylate. And methacrylate monomers.
- examples of the polyhydric alcohol acrylate and alkoxy ether derivatives thereof include glycerin acrylate and ethylene glycol acrylate monomers.
- Specific examples of the ethylene glycol acrylate monomer include polyethylene glycol monoacrylate, methoxypolyethylene glycol monoacrylate, and polyethylene glycol monoacrylate.
- Acrylate monomers such as
- the pressure resistance and the heat resistance are higher than the conventional one, and for example, deterioration due to repeated steam sterilization can be reduced.
- the internal liquid 34 for reference electrodes of this embodiment can improve the measurement precision by reducing the liquid-liquid potential produced with respect to an alkaline sample compared with the past.
- the internal liquid for a reference electrode used in the present invention forms a gel.
- a monomer having a plurality of functional groups is used as a crosslinking agent, and the crosslinking agent and the monofunctional monomer are used.
- this structure prevents elution or swelling of the material even when repeated treatment at high temperatures. Durability can be imparted to repeated treatment at high temperatures.
- the resulting gel tends to be too hard and the stability against temperature change is deteriorated.
- the stability of the liquid potential, the repeated durability, and the stability against temperature change tend not to be sufficient.
- the monofunctional monomer is hydrophobic, the KCl solution cannot be retained, and the gel stability is deteriorated. Therefore, a hydrophilic monomer is used.
- the response glass 22 contains at least La 2 O 3 , it is difficult for errors to occur on the alkali side, and since it contains a small amount of Y 2 O 3 and Sc 2 O 3 in addition, durability is improved by strengthening the skeleton of the glass. Rise.
- durability can be improved while suppressing measurement errors with respect to an alkaline sample. Further, as long as it contains Sc 2 O 3, although the measurement error described above is readily released slightly, it is possible to particularly increase the effect of improving the durability. From this, by including these components suitably, as mentioned above, durability can be enhanced while suppressing errors on the alkali side.
- the response glass 22 becomes the thing excellent in heat resistance by containing Sc.
- the present invention is not limited to the above embodiment.
- the glass electrode 2 and the comparison electrode 3 are integrally formed, but a configuration in which these electrodes are separated may be used.
- the internal electrode 34 for a comparative electrode of the present invention will be specifically described including its manufacturing method and experimental results.
- the internal liquid 34 for the reference electrode according to this embodiment is obtained by copolymerizing a hydrophilic monomer and a crosslinking agent.
- Table 1 lists a sample x, which is a conventional internal liquid for a reference electrode, as a comparative example.
- the sample x is an electrode using a polymer gel, and no cross-linking agent is used.
- each sample of this example was produced by copolymerizing a hydrophilic monomer A or hydrophilic monomer B and a crosslinking agent A or a crosslinking agent B.
- hydrophilic monomer A and cross-linking agent A are added together with additives into a 3.0 mol / l-KCl solution to form a uniform solution, and then put into a glass tube for electrodes.
- the sample was obtained by heat treatment and copolymerization.
- the hydrophilic monomers A and B are monofunctional hydrophilic monomers excluding acrylamide and methacrylamide
- the hydrophilic monomer A of this example is glycerin monomethacrylate
- the hydrophilic monomer B is dimethylaminoethyl methacrylate. This is a quaternized product.
- the crosslinking agent A of a present Example is glycerol diacrylate
- the crosslinking agent B is a trimethylol propane trimethacrylate.
- additive A triethylenetetramine as additive A
- ammonium persulfate as additive B
- 2,2′-azobis [N- (2-carboxyethyl) -2-methylpropioamidine] hydrate as additive C Is used.
- FIG. 2 shows the experimental results of measuring the liquid-potential between the reference electrode 3 using each sample as the reference electrode internal liquid 34 and the reference reference electrode that has been confirmed to be stable over a wide range of pH. From this graph, it can be seen that, compared to the conventional sample x, the liquid potential is reduced in a wide pH range when samples a, b, c, d, and e are used. This tendency is particularly remarkable when the sample is alkaline.
- FIG. 3 the inter-liquid potential between the reference electrode 3 using each sample as the internal liquid 34 for the reference electrode and the reference reference electrode that has been confirmed to be stable over a wide range of pH is measured for each number of steam sterilizations.
- the experimental results are shown.
- the upper stage of FIG. 3 is an experimental condition where the sample is pH 9 and the lower stage is an experimental condition where the sample is 0.1 M NaOH. From this graph, compared to the conventional sample x, when using samples a, b, c, d and e, the liquid potential is stable regardless of the number of steam sterilizations, and the pressure resistance and heat resistance It can be seen that the performance is improved.
- FIG. 4 shows the results of experiments in which deterioration of sensitivity was observed by repeatedly putting the comparative electrode 3 using each sample as the internal liquid 34 for the comparative electrode and the glass electrode containing the internal liquid KCl into a sterilized autoclave (130 ° C.). .
- a glass electrode what was described in Table 2 is used.
- FIG. 5 shows the experimental results of observing fluctuations in the inter-liquid potential after immersion in a standard solution of pH 7 in a thermostatic bath at 25 ° C. From this graph, in the samples a and b of this example, the generation of the inter-liquid potential is suppressed even when the number of days elapses, and stable measurement can be performed by using these as the internal liquid 34 for the reference electrode. I understand that.
- Table 3 shows the results of comparing the color (appearance as a product) of each sample after steam sterilization of the reference electrode 3 using each sample as the reference electrode internal liquid 34.
- the color of the sample it is transparent before steam sterilization, and discoloration due to steam sterilization is not preferable in terms of the appearance of the product.
- the criteria for determining the stability described in the above table are ⁇ for inter-liquid potential fluctuations within ⁇ 6 mV, ⁇ for inter-liquid potential fluctuations within ⁇ 12 mV, and x for inter-liquid potential fluctuations of ⁇ 12 mV or more.
- the durability of the internal liquid for the reference electrode can be improved as compared with the conventional case.
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
- Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
Abstract
Description
なお、ここでいうゲル状組成物は、分散系の一種で、分散質のネットワークによって高い粘性を持ちながらも流動性を失った半固形状態の物質系を意味し、広義には固体分散媒のコロイドであるソリッドゾルを包含する。
また、重合反応させる物質として毒性の強い物質を用いた場合、製造工程および製造された内部液やこれを用いた比較電極の扱いに危険が伴うところ、毒性の強いアクリルアミドを除くことにより、そのような危険性を低減することができる。
さらに本発明は、この比較電極と共に用いられるものであって、Me2O3(Meはランタノイド)を含む応答ガラスを具備するガラス電極も包含する。
より詳細には、Y2O3を含むものであれば、アルカリ性の試料に対する測定誤差を抑えながら、耐久性を向上させることができる。また、Sc2O3を含むものであれば、上述の測定誤差は多少出やすくなるものの、耐久性を向上させる効果を特に大きくすることができる。
このように構成された電気化学測定装置であれば、上述した作用効果を得ることができる。
2 ・・・ガラス電極
22 ・・・応答ガラス
23 ・・・ガラス電極用内極
24 ・・・ガラス電極用内部液
3 ・・・比較電極
32 ・・・液絡部
33 ・・・比較電極用内極
34 ・・・比較電極用内部液
より詳細に本実施形態の応答ガラス22は、少なくともLa2O3を含み、その他にLa2O3よりも少量のY2O3やSc2O3を含む組成である。
なお、この液絡部32は、比較電極支持管31に小さな貫通孔を形成して、後述の比較電極用内部液34に液絡の作用を発揮させるように構成しても良い。
具体的に架橋剤は、複数の官能基を有するモノマーであり、複数の官能基を有するアクリレート、複数の官能基を有するメタクリレート、複数の官能基を有するアミン類、複数の官能基を有するビニル化合物などが挙げられる。該アクリレート又は該メタクリレートとしては、グリセリンジアクリレート、ポリアルキレングリコールジアクリレート、ポリアルキレングリコールトリアクリレート、エトキシ化ビスフェノールAジアクリレート、エトキシ化グリセリントリアクリレート、トリメチロールプロパントリアクリレート、トリメチロールプロパントリメタクリレート、ポリアルキレングリコールジメタクリレート、グリセリンジメタクリレート、ポリアルキレングリコールトリアクリレート、などが挙げられる。さらに、複数の官能基を有するアミン類としては、トリエチレンテトラミン、エチレンジアミン、ヘキサメチレンジアミン、ジプロピレントリアミンなどが挙げられ、複数の官能基を有するビニル化合物としては、ジビニルベンゼン、ブタンジオールジビニルエーテル、ジエチレングリコールジビニルエーテルなどが挙げられる。
また、本実施形態の比較電極用内部液34は、従来に比べてアルカリ性の試料に対して生じる液間電位を低減して測定精度を向上させることができる。
このことから、これらの成分を好適に含有させることにより、上述したように、アルカリ側での誤差を抑えつつ耐久性を高めることができる。
また、本実施例の架橋剤Aはグリセリンジアクリレートであり、架橋剤Bはトリメチロールプロパントリメタクリレートである。
なお、本実施例では添加剤Aとしてトリエチレンテトラミン、添加剤Bとして過硫酸アンモニウム、添加剤Cとして2,2‘-アゾビス[N-(2-カルボキシエチル)-2-メチルプロピオアミジン]ハイドレートを用いている。
このグラフから、従来のサンプルxと比較して、サンプルa、b、c、d及びeを用いた場合はいずれも幅広いpH領域において液間電位が低減していることが分かる。この傾向は、特に試料がアルカリ性の場合に顕著である。
このグラフから、従来のサンプルxと比較して、サンプルa、b、c、d及びeを用いた場合はいずれも蒸気滅菌の回数によらず液間電位が安定しており、耐圧性及び耐熱性が向上していることが分かる。
このグラフから、本実施例のサンプルa及びbは、日数が経過しても液間電位の発生が抑えられており、これらを比較電極用内部液34として用いることにより安定した測定が可能になることが分かる。
なお、サンプルの色に関していえば、蒸気滅菌前は透明であり、蒸気滅菌により変色してしまうと製品の外観上好ましくない。
Claims (7)
- アクリルアミドを除いた複数の官能基を有する架橋剤と、アクリルアミドを除いた単官能の親水性モノマーとを共重合させたものを含有することを特徴とする比較電極用内部液。
- 前記架橋剤が、アクリレート又はメタクリレートであることを特徴とする請求項1記載の比較電極用内部液。
- 前記親水性モノマーが、アクリレート又はメタクリレートであることを特徴とする請求項1又は2記載の比較電極用内部液。
- 請求項1乃至3のうち何れか一項に記載の比較電極用内部液を有する比較電極。
- 請求項4記載の比較電極と共に用いられるものであって、
Me2O3(Meはランタノイド)を含む応答ガラスを具備するガラス電極。 - 前記応答ガラスが、Y2O3又はSc2O3を含むことを特徴とする請求項5記載のガラス電極。
- 請求項5又は6記載のガラス電極と、
前記ガラス電極及び前記比較電極からの出力値に基づいて測定結果を示す測定データを出力する演算部と、
前記演算部から出力される測定データに基づいて、前記測定結果を表示する表示部とを具備していることを特徴とする電気化学測定装置。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15/115,610 US10145814B2 (en) | 2014-01-31 | 2015-01-30 | Internal solution for reference electrode, reference electrode, and glass electrode |
CN201580006778.6A CN105940296B (zh) | 2014-01-31 | 2015-01-30 | 比较电极用内部溶液、比较电极、玻璃电极以及电化学测定装置 |
JP2015560027A JP6603135B2 (ja) | 2014-01-31 | 2015-01-30 | 比較電極用内部液、比較電極及びガラス電極 |
EP15743191.7A EP3101414B1 (en) | 2014-01-31 | 2015-01-30 | Acrylamide-free electrochemical measurement apparatus with lanthanide glass electrode |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014-016958 | 2014-01-31 | ||
JP2014016958 | 2014-01-31 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015115587A1 true WO2015115587A1 (ja) | 2015-08-06 |
Family
ID=53757155
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/052633 WO2015115587A1 (ja) | 2014-01-31 | 2015-01-30 | 比較電極用内部液、比較電極及びガラス電極 |
Country Status (5)
Country | Link |
---|---|
US (1) | US10145814B2 (ja) |
EP (1) | EP3101414B1 (ja) |
JP (1) | JP6603135B2 (ja) |
CN (1) | CN105940296B (ja) |
WO (1) | WO2015115587A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021117096A (ja) * | 2020-01-24 | 2021-08-10 | 東亜ディーケーケー株式会社 | 電気化学測定用の電極体 |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AT520779B1 (de) | 2017-12-21 | 2020-03-15 | Erba Tech Austria Gmbh | Referenzelektrode zur potentiometrischen Messung von Ionenkonzentrationen |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001255298A (ja) * | 2000-02-10 | 2001-09-21 | Hamilton Bonaduz Ag | 電気化学的な参照電極およびその使用 |
JP2004004011A (ja) * | 2002-03-27 | 2004-01-08 | Mettler Toledo Ag | ポリマー電解質ならびに電気化学測定用半電池およびその使用 |
JP2007524090A (ja) | 2004-01-28 | 2007-08-23 | メトラー−トレド アクチェンゲゼルシャフト | ポリマー電解質、電気化学的測定用の半電池、およびこれらの使用 |
JP2009288117A (ja) | 2008-05-30 | 2009-12-10 | Horiba Ltd | ガラス電極及びその応答ガラス |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3228647A1 (de) | 1982-07-31 | 1984-02-02 | Dr. W. Ingold KG, 6000 Frankfurt | Bezugselektrode oder einstabmesskette |
US5254634A (en) | 1990-07-20 | 1993-10-19 | Mitsubishi Kasei Corporation | Crosslinked copolymer particles and process for producing the same |
DE10243930A1 (de) * | 2002-03-08 | 2003-09-25 | Conducta Endress & Hauser | Vorrichtung zur Messung und Regelung des pH-Wertes eines Mediums |
JP4824489B2 (ja) * | 2006-07-03 | 2011-11-30 | 株式会社堀場製作所 | 参照電極、その参照電極を用いたイオン濃度測定装置、参照電極用内部液、参照電極用内部液のpH調節方法、及び塩橋 |
WO2008029895A1 (fr) * | 2006-09-06 | 2008-03-13 | Horiba, Ltd. | Électrode en verre et verre sensible destiné à ladite électrode |
MY165426A (en) * | 2007-12-21 | 2018-03-22 | Mimos Berhad | Reference electrode with immobilized internal electrolyte |
DE102011089707A1 (de) * | 2010-12-30 | 2012-09-13 | Endress + Hauser Conducta Gesellschaft für Mess- und Regeltechnik mbH + Co. KG | Halbzelle für elektrochemische Messungen, welche einen Polymer-Elektrolyten enthält |
JP5785741B2 (ja) * | 2011-03-03 | 2015-09-30 | 株式会社堀場製作所 | 測定装置 |
DE102012102321A1 (de) * | 2012-03-20 | 2013-09-26 | NMI Naturwissenschaftliches und Medizinisches Institut an der Universität Tübingen | Miniaturisierte ionenselektive Elektrode zweiter Art |
-
2015
- 2015-01-30 WO PCT/JP2015/052633 patent/WO2015115587A1/ja active Application Filing
- 2015-01-30 EP EP15743191.7A patent/EP3101414B1/en active Active
- 2015-01-30 JP JP2015560027A patent/JP6603135B2/ja active Active
- 2015-01-30 CN CN201580006778.6A patent/CN105940296B/zh active Active
- 2015-01-30 US US15/115,610 patent/US10145814B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2001255298A (ja) * | 2000-02-10 | 2001-09-21 | Hamilton Bonaduz Ag | 電気化学的な参照電極およびその使用 |
JP2004004011A (ja) * | 2002-03-27 | 2004-01-08 | Mettler Toledo Ag | ポリマー電解質ならびに電気化学測定用半電池およびその使用 |
JP2007524090A (ja) | 2004-01-28 | 2007-08-23 | メトラー−トレド アクチェンゲゼルシャフト | ポリマー電解質、電気化学的測定用の半電池、およびこれらの使用 |
JP2009288117A (ja) | 2008-05-30 | 2009-12-10 | Horiba Ltd | ガラス電極及びその応答ガラス |
Non-Patent Citations (1)
Title |
---|
See also references of EP3101414A4 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2021117096A (ja) * | 2020-01-24 | 2021-08-10 | 東亜ディーケーケー株式会社 | 電気化学測定用の電極体 |
JP7488444B2 (ja) | 2020-01-24 | 2024-05-22 | 東亜ディーケーケー株式会社 | 電気化学測定用の電極体 |
Also Published As
Publication number | Publication date |
---|---|
EP3101414B1 (en) | 2020-09-02 |
CN105940296B (zh) | 2019-10-18 |
US20170168003A1 (en) | 2017-06-15 |
EP3101414A4 (en) | 2017-10-11 |
JPWO2015115587A1 (ja) | 2017-03-23 |
JP6603135B2 (ja) | 2019-11-06 |
EP3101414A1 (en) | 2016-12-07 |
US10145814B2 (en) | 2018-12-04 |
CN105940296A (zh) | 2016-09-14 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Kong et al. | Muscle‐inspired highly anisotropic, strong, ion‐conductive hydrogels | |
JP4520999B2 (ja) | ポリマー電解質、電気化学的測定用の半電池、およびこれらの使用 | |
Liu et al. | A non‐ionic thermophilic hydrogel with positive thermosensitivity in water and electrolyte solution | |
Shahrokhian et al. | Nanocellulose/carbon nanoparticles nanocomposite film modified electrode for durable and sensitive electrochemical determination of metoclopramide | |
US10900925B2 (en) | Ion-selective electrode systems and methods utilizing same | |
JP2001255298A (ja) | 電気化学的な参照電極およびその使用 | |
JPH07167827A (ja) | イオン選択性センサおよびその形成方法 | |
US20230038845A1 (en) | Polymer Formulations for Anti-fouling Hydrogel Coatings | |
Fan et al. | Competitive cation− π interactions between small cations and polycations with phenyl groups in poly (cation− π) hydrogels | |
JP6603135B2 (ja) | 比較電極用内部液、比較電極及びガラス電極 | |
JP2008164319A (ja) | 電気泳動用乾燥媒体への試料の導入方法及びそのための器具 | |
JP4854502B2 (ja) | ヘモグロビン類の測定方法 | |
Wang et al. | An autofluorescent hydrogel with water‐dependent emission for dehydration‐visualizable smart wearable electronics | |
Dai et al. | Screen Printed Alizarin‐Based Carbon Electrodes: Monitoring pH in Unbuffered Media | |
Babaei et al. | A sensitive determination of acetaminophen in pharmaceutical preparations and biological samples using multi-walled carbon nanotube modified glassy carbon electrode | |
CN107102043B (zh) | 一种多壁碳纳米管/聚l-组氨酸修饰玻碳电极的制备方法及其在测定对苯二酚中的应用 | |
JP4413514B2 (ja) | ポリマー電解質ならびに電気化学測定用半電池およびその使用 | |
ES2776725T3 (es) | Biopolímeros hidrófilos eléctricamente activos | |
Dale et al. | Polarised liquid/liquid micro-interfaces move during charge transfer | |
Lee et al. | Synthesis and swelling behavior of thermosensitive IPN hydrogels based on sodium acrylate and N‐isopropyl acrylamide by a two‐step method | |
JPWO2016035752A1 (ja) | 参照電極用素子及びイオンセンサ装置 | |
Zhao et al. | Multifunctional sensors based on silicone hydrogel and their responses to solvents, pH and solution composition | |
Zanardi et al. | Development of a redox polymer based on poly (2-hydroxyethyl methacrylate) for disposable amperometric sensors | |
JP5335288B2 (ja) | ガラス電極及びその応答ガラス | |
JP4854638B2 (ja) | 安定型ヘモグロビンA1c値の測定方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15743191 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2015560027 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15115610 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2015743191 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2015743191 Country of ref document: EP |