Calibration mechanism, sensor unit, and electrochemical measurement device

Abstract

To provide a calibration mechanism that enables a general user having no specialized knowledge to easily perform a calibration task, and that is able to be used repeatedly.SOLUTION: A calibration mechanism for an electrochemical measurement device comprises: a calibration solution holding unit that holds water and a calibration component forming a calibration solution that is for calibrating an electrochemical measurement device comprising an ion-selective electrode; and a water evaporation inhibiting unit that inhibits evaporation of the water from the calibration solution holding unit. The calibration solution holding unit is able to be detached from and reattached to the ion-selective electrode. The water evaporation inhibiting unit is able to be detached from and reattached to the ion-selective electrode together with the calibration solution holding unit.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a calibration mechanism that is attached to an ion selective electrode of an electrochemical measurement device, a sensor unit equipped with this calibration mechanism, and an electrochemical measurement device equipped with this sensor unit. [Background technology]

[0002] When using an ion selective electrode to measure the concentration of a specific ion present in a measurement target, in order to perform measurements as accurately as possible, a calibration procedure is performed to match the potential detected by the ion selective electrode with the ion concentration display value shown to the user by the electrochemical measurement device.

[0003] The calibration work of an electrochemical measurement apparatus as described above is a very troublesome task for a user who uses the apparatus for daily health management at home, and there is a risk that the calibration will not be performed correctly.

[0004] Therefore, as described in Patent Documents 1 and 2, a sensor unit is provided in which a sheet impregnated with a calibration solution is brought into contact with an ion-selective electrode, and this sensor unit is set in the main body of an electrochemical measurement device for calibration, and the sheet is then peeled off to measure the ion concentration in the measurement target. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 63-289444 [Patent Document 2] JP 2013-32945 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, such a conventional sensor unit needs to be replaced after each use, which is not economical. On the other hand, if you want to use this sensor unit repeatedly, you need to store the sheet impregnated with the calibration liquid in an appropriate environment, but this is difficult for general users without specialized knowledge, and there is a problem that the moisture evaporates from the calibration liquid impregnated in the sheet, changing the concentration of the components in the calibration liquid and making it impossible to perform calibration correctly.

[0007] The present invention has been made in consideration of such problems, and its main object is to provide a calibration mechanism that allows general users without specialized knowledge to easily perform calibration work and that can be used repeatedly. [Means for solving the problem]

[0008] That is, the calibration mechanism according to the present invention comprises: a calibration solution holding section for holding the calibration components and water constituting the calibration solution; a moisture evaporation suppression unit that suppresses evaporation of the moisture from the calibration solution holding unit, The calibration solution holding section is detachable from the ion selective electrode, and the water evaporation suppressing section is detachable from the ion selective electrode together with the calibration solution holding section.

[0009] According to the calibration mechanism configured in this manner, the calibration solution holding section and the water evaporation suppression section are attached and detached together, so that the calibration solution holding section is less likely to come into contact with the outside air, and water evaporation from the calibration solution holding section can be suppressed. As a result, the composition of the calibration solution, which is made up of calibration components and water held in the calibration solution holding section of the calibration mechanism, is less likely to change, so that even if a user does not have specialized knowledge, the calibration mechanism can be used repeatedly to accurately calibrate the electrochemical measurement device.

[0010] In a specific embodiment of the present invention, the calibration solution holding section is in a gel state, and the water evaporation suppressing section is a housing that houses the calibration solution holding section therein.

[0011] The water evaporation suppression section may be configured to be capable of housing an ion selective electrode therein so as to be in contact with the calibration solution holding section.

[0012] The calibration solution holding section may be solid, and the calibration solution holding section and the water evaporation suppressing section may be bonded to each other by an adhesive layer disposed therebetween.

[0013] A sensor unit including an ion selective electrode and the above-mentioned calibration mechanism, and an electrochemical measurement device including the above-mentioned sensor unit are also part of the present invention. Effect of the Invention

[0014] According to the present invention, it is possible to provide a calibration mechanism that allows general users without specialist knowledge to easily perform calibration work and that can be used repeatedly. [Brief description of the drawings]

[0015] [Figure 1] 1 is an overall schematic diagram of an electrochemical measurement apparatus according to one embodiment of the present invention; [Diagram 2] FIG. 2 is a schematic diagram showing a state in which the electrochemical measurement device according to the embodiment is used. [Diagram 3] FIG. 4 is a schematic diagram of an electrochemical measurements apparatus according to another embodiment of the present invention. [Figure 4] FIG. 4 is a schematic diagram of an electrochemical measurements apparatus according to another embodiment of the present invention. [Diagram 5] Schematic diagram of an electrochemical measurement device according to another embodiment of the present invention. [Figure 6] FIG. 5 is a schematic diagram showing the electrochemical measurement apparatus shown in FIG. 4 in use. [Figure 7] FIG. 13 is a schematic diagram showing an apparatus for electrochemical measurements according to another embodiment of the present invention. [Figure 8] FIG. 7 is a schematic diagram showing the electrochemical measurement apparatus shown in FIG. 6 in use. [Figure 9] FIG. 11 is a schematic diagram showing a sensor unit according to another embodiment of the present invention. [Figure 10]FIG. 13 is a schematic diagram showing an apparatus for electrochemical measurements according to another embodiment of the present invention. [Figure 11] FIG. 10 is a schematic diagram showing the electrochemical measurement apparatus shown in FIG. 9 in use. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] Hereinafter, an embodiment of the present invention will be described with reference to the drawings. <Basic configuration of the electrochemical measurement device according to this embodiment> The electrochemical measurement device 100 according to this embodiment, as shown in FIG. 1, measures the sodium ion / potassium ion concentration ratio, which is an electrochemical characteristic of a test liquid to be measured, and includes a sensor unit 1 having a sensor 11 that contacts the test liquid and detects an electrochemical signal corresponding to the electrochemical characteristic of the test liquid, and an information processing unit 2 that receives the electrochemical signal output from the sensor unit 1, processes it, and calculates the sodium / potassium ion concentration ratio.

[0017] In this embodiment, the sensor unit 1 includes, for example, two types of ion selective electrodes 111 each responding to different ions as the sensors 11, and a temperature sensor (not shown). In this embodiment, the sensor unit 1 is a composite type in which the above-mentioned multiple sensors 11 are formed on the same substrate such that the surfaces of the sensors 11 in contact with the sample solution are arranged on approximately the same plane.

[0018] In this embodiment, the two types of ion selective electrodes 111 described above are a sodium ion selective electrode 111N and a potassium ion selective electrode 111K. The sodium ion selective electrode 111N and the potassium ion selective electrode 111K have a structure as shown in FIG. 2, for example.

[0019] The sodium ion selective electrode 111N comprises a substrate 111Na, an internal electrode 111Nb made of, for example, a silver electrode formed on the substrate 111Na, an ion-sensitive membrane 111Nc attached to the internal electrode 111Nb, and an ion-electron conversion layer 111Nd attached between the internal electrode 111Nb and the ion-sensitive membrane 111Nc so as to be in contact with both, and disposed between the working electrode and the ion-responsive membrane to electrically connect them.

[0020] The sodium ion sensitive film 111Nc is formed by adding a plasticizer and a sodium ionophore to polyvinyl chloride (PVC), dissolving the resultant in an organic solvent such as tetrahydrofuran (THF), applying the solution by potting or inkjet printing, and then heating to evaporate the organic solvent to form a solid sodium ion sensitive film 111Nc. An example of the sodium ionophore is Bis(12-crown-4). The solution for forming the sodium ion sensitive film 111Nc may contain polyvinyl chloride (PVC) containing a plasticizer, sodium ionophore, and an ionic additive such as a phenyl borate ionic additive.

[0021] The potassium ion selective electrode 111K comprises an internal electrode 111Kb, for example a silver electrode, formed on the substrate 111Ka, an ion-sensitive membrane 111Kc attached to the internal electrode 111Kb, and an ion-electron conversion layer 111Kd attached between the internal electrode 111Kb and the ion-sensitive membrane 111Kc so as to be in contact with both, and disposed between the working electrode and the ion-responsive membrane to electrically connect them.

[0022] The potassium ion sensitive film 111Kc is formed in the same manner as the sodium ion sensitive film 111Nc, except that a potassium ionophore is used, such as Bis (benzo-15-crown-5).

[0023] The ion-electron conversion layers 111Nd and 111Kd contain an ion-electron conversion material and an adhesive.

[0024] As the ion-electron conversion material, for example, a carbon microstructure can be used. The carbon microstructure may include, for example, one or more selected from carbon nanotubes, carbon nanofibers, carbon nanowalls, fullerenes, graphite, graphene, etc. In the present embodiment, carbon nanotubes are used as an example of the ion-electron conversion material.

[0025] The content of the carbon microstructure in the ion-electron conversion layer 121c is preferably 0.001 mass % or more and 12.0 mass % or less, more preferably 0.001 mass % or more and 0.02 mass % or less, and even more preferably 0.003 mass % or more and 0.01 mass % or less.

[0026] The adhesive preferably contains one or more selected from polyvinyl chloride (PVC), polystyrene, acrylate, polyvinyl butyral, polyamide, polyimide, polyurethane, polytetrafluoroethylene (PTFE), polysiloxane, copolymer of vinylidene fluoride and hexafluoropropylene (PVDF-HFP), and fluoropolysiloxane. These adhesives may be used alone or in combination. The adhesive may contain a plasticizer in addition to the above-mentioned components.

[0027] In this embodiment, the substrates 111Na and 111Ka constituting the sodium ion selective electrode 111N and the potassium ion selective electrode 111K are one and the same substrate, but the present invention is not limited to this.

[0028] Each of the sensors 11 is electrically connected to an electric circuit board or the like constituting the information processing unit 2 via lead wires or the like electrically connected to the internal electrodes 111Nb, 111Kb of each sensor 11, respectively.

[0029] The sensor unit 1 may be formed to surround from the side the entire area in which the surfaces of all of the aforementioned sensors 11 that come into contact with the sample solution are formed, and may be provided with a test liquid holder that holds the test liquid so that the test liquid comes into contact with the surfaces of all of the sensors 11.

[0030] The information processing unit 2 has an analog electrical circuit having a buffer, amplifier, etc., a digital electrical circuit having a CPU, memory, DSP, etc., an A / D converter, etc. interposed between them, and a housing for the information processing unit to accommodate these.

[0031] The information processing unit 2 functions as a data acquisition section (not shown) that acquires signals output from each sensor, and a calculation section (not shown) that calculates measurement values ​​such as potential difference and ion concentration ratio between the sensors 11 based on the acquired data, by the CPU and its peripheral devices working together in accordance with a predetermined program stored in memory. The information processing unit 2 may also perform functions such as a display section 21 that displays the measurement values ​​calculated by the calculation section and the state of the electrochemical measurement device, and an operation section 22 that has input buttons and the like for operating the electrochemical measurement device.

[0032] <Characteristic configuration of the electrochemical measurement device according to this embodiment> As shown in FIG. 1, the sensor unit 1 of this embodiment further includes a calibration mechanism 12 that can repeatedly bring a calibration liquid into contact with the sensor surface of the sensor 11 (the ion-sensitive membranes 111Nc, 111Kc of the two types of ion selective electrodes 111) and remove the calibration liquid from the sensor surface. The calibration mechanism 12 holds a calibration solution and includes a calibration solution holding section 121 arranged to contact the sensor surface of the sensor 11, and a moisture evaporation suppression section 122 that suppresses evaporation of moisture from the calibration solution holding section 121.

[0033] The calibration solution held in the calibration solution holding section 121 is composed of calibration components and moisture both held in the calibration solution holding section 121, and can be changed as appropriate according to the type of sensor provided in the sensor unit, but in this embodiment, a wide variety of calibration solutions that are typically used for span calibration when measuring sodium ion concentrations and potassium ion concentrations can be used. Specific examples include standard solutions with known sodium ion concentrations or potassium ion concentrations.

[0034] In this embodiment, the calibration liquid holding section 121 holds the calibration liquid, for example, by impregnating it therein. Examples of such a section include a hydrogel made by impregnating a substrate having a three-dimensional mesh structure or a porous substrate with water, which further contains a calibration component, a mesh-like section impregnated with a calibration liquid consisting of water and the calibration component, or a film-like section.

[0035] Natural or synthetic polymers can be used as the material of the base material constituting the calibration solution holding portion 121. Specific examples of these polymers include the following:

[0036] As the natural polymer, for example, one or more selected from the group consisting of alginic acid, chitosan, gelatin, collagen, hyaluronic acid, fibrinogen, silk fibroin, agarose, carrageenan, pectin, xanthan, cellulose, dextran, pullulan, lignin, starch, chondroitin sulfate, dermatan sulfate, heparin, keratin, elastin, pluronic acid, and cotton can be used.

[0037] As the synthetic polymer, for example, one or more selected from the group consisting of polyethylene glycol, polyacrylic acid, polyvinyl alcohol, poly(N-isopropylacrylamide), poly(2-hydroxyethyl methacrylate), polyurethane, polypropylene glycol, polyethyleneimine, polymethyl methacrylate, polycaprolactone, polylactic acid, and polyglycolic acid can be used.

[0038] The water evaporation suppression unit 122 is configured to suppress exposure of the calibration solution holding unit 121 to the outside air by housing the calibration solution holding unit 121 therein, and to suppress evaporation of water constituting the calibration solution from the calibration solution holding unit 121. The water evaporation suppression unit 122 in this embodiment is made of a material capable of suppressing evaporation of water, such as a resin that is impermeable to water, and is a cap-shaped housing that covers a substrate on which the sensor 11 is placed. More specifically, the water evaporation suppression unit 122 is a rectangular parallelepiped housing with one side open, and is configured to be fixed by a removable member such as a claw portion formed on the substrate of the water evaporation suppression unit 122 and / or the ion selective electrode 111 with the opening facing the sensor 11 side so that the calibration solution holding unit 121 housed therein can come into contact with the sensor 11, thereby sealing the calibration solution holding unit 121 inside with the sensor surface and the calibration solution holding unit 121 in close contact with each other.

[0039] The calibration liquid holding section 121 and the water evaporation suppressing section 122 described above are bonded to each other, and are configured so that the calibration liquid holding section 121 and the water evaporation suppressing section 122 can be removed together from the sensor 11. In this embodiment, an adhesive layer 123 is formed between the calibration liquid holding section 121 and the water evaporation suppressing section 122, and the calibration liquid holding section 121 and the water evaporation suppressing section 122 are bonded to each other by this adhesive layer 123. There are no particular limitations on the material that forms the adhesive layer 123 used when bonding the calibration liquid holding section 121 and the water evaporation suppressing section 122, and for example, a commercially available double-sided tape or a general-purpose adhesive such as epoxy silicone can be used.

[0040] <Electrochemical measurement method using the electrochemical measurement device according to this embodiment> The procedure for measuring the sodium ion / potassium ion concentration ratio in a sample solution using the electrochemical measurement device 100 configured in this manner is as follows.

[0041] In the electrochemical measurement method according to this embodiment, before performing a measurement using a sample solution with an unknown concentration of the ion to be measured as the test liquid, a standard solution that is a buffer solution with a known concentration of the ion to be measured is used as a calibration liquid to calibrate the measurement value of the electrochemical measurement apparatus 100.

[0042] In this embodiment, this calibration operation is performed with the above-mentioned calibration mechanism attached to the sensor 11 and the calibration liquid held in the calibration liquid holding section 121 in contact with the sensor surface of the sensor 11, as shown in Figure 2.

[0043] When the user turns on the power of the electrochemical measurement apparatus 100 with the calibration mechanism 12 still attached to the sensor 11, the electrochemical measurement apparatus 100 automatically starts the calibration operation. When the calibration process is completed, the display unit 21 displays a message urging the user to remove the calibration mechanism 12 from the sensor 11 and to bring the sensor 11 into contact with the test liquid.

[0044] After this display is displayed, the user removes calibration mechanism 12 from sensor 11 in a manner similar to opening a cap. At this time, calibration mechanism 12 may be completely removed, or, as shown in Fig. 2, one end of the housing constituting moisture evaporation suppression section 122 may be fixed to the housing for the information processing unit by a hinge or the like so that it can be easily opened and closed. In this case, the hinge or the like can be said to correspond to a detachable member. Next, an appropriate amount of the test liquid is dropped onto the test liquid holder 12 so that the test liquid comes into contact with the sodium ion sensitive film 111Nc and the potassium ion sensitive film 111Kc.

[0045] When the test liquid is dropped, an electromotive force corresponding to each ion concentration is generated between the test liquid and the ion-electron conversion layers 111Nd, 111Kd arranged in place of the internal liquid in the sodium ion sensitive membrane 111Nc and the potassium ion sensitive membrane 111Kc. This electromotive force is detected as a potential difference (voltage) between the potential of the test liquid detected by the internal electrode 111Nb of the sodium ion selective electrode 111N and the internal electrode 111Kb of the potassium ion selective electrode 111K, and based on the detected signal, a calculation section included in the information processing unit 2 calculates these potential differences and an ion concentration ratio based on this potential difference based on a known method, and the calculated concentration ratio is displayed on the display section 21.

[0046] Next, the display unit 21 displays a message urging the user to rinse the sensor 11 with water or the like, wipe off any water droplets, and then reattach the calibration mechanism 12. When the user attaches the calibration mechanism 12 to the sensor 11, the series of measurement steps is completed.

[0047] <Effects of this embodiment> The electrochemical measurements apparatus 100 according to this embodiment configured as above can provide the following advantages.

[0048] Since calibration is performed automatically before measurement, the user does not have to go through the trouble of performing calibration himself / herself. Furthermore, a moisture evaporation suppression section 122 that suppresses the suppression of moisture from the calibration solution holding section 121 is provided, and this is removable from the sensor 11 together with the calibration solution holding section 121. Therefore, even when it is removed from the sensor 11, the entire calibration solution holding section 121 is not exposed to the outside air, and the evaporation of moisture from the calibration solution holding section 121 can be suppressed as much as possible.

[0049] Since the water evaporation suppression section 122 is a housing that houses the calibration solution holding section 121 inside, the surface of the calibration solution holding section 121 is less likely to be exposed to the outside air, and water evaporation can be further suppressed.

[0050] While the calibration mechanism 12 is attached to the sensor 11, the calibration liquid held in the calibration liquid holding section 121 is in contact with the sensor surface, so that the calibration time can be shortened and the measurement value can be stabilized compared to when calibration or measurement is started when the sensor 11 is in a dry state.

[0051] Since no internal liquid is required for the common electrode 112, and furthermore, solid ion-electron conversion layers 111Nd, 111Kd that perform the function of the internal liquid instead of an internal liquid are used for the ion selective electrodes 111N, 111K, a housing for holding the internal liquid is not required, and the sensor unit 1 can be made thinner than conventional ones.

[0052] <Other embodiments of the present invention> The present invention is not limited to the above-described embodiment. In the above-described embodiment, the moisture evaporation suppression unit serves as a housing and houses the calibration liquid holding unit inside. However, the present invention is not limited to this. The moisture evaporation suppression unit may be something like a flexible packaging material, or the plate-shaped or film-shaped moisture evaporation suppression unit and the plate-shaped or film-shaped calibration liquid holding unit may be bonded to each other, and both the moisture evaporation suppression unit and the calibration liquid holding unit may be configured to be attached and detached to the sensor using, for example, a detachable member such as a fixing band provided separately from the moisture evaporation suppression unit.

[0053] Furthermore, as shown in Figs. 3(a) to (c), for example, the calibration solution holding section may be laminated on a plate-shaped or film-shaped water evaporation suppressing section, and the calibration solution holding section may be formed to a size that can cover the sensor surface of the sensor 11 (for example, the surface of each ion-responsive membrane or salt bridge that comes into contact with the sample solution), and the water evaporation suppressing section may be formed to be slightly larger than the calibration solution holding section so that the outer edge of the water evaporation suppressing section is located outside the outer edge of the calibration solution holding section. In this case, by pressing the calibration mechanism against the sensor with the calibration solution holding section arranged so that it touches the sensor surface, the outer edge of the water evaporation suppressing section located outside the calibration solution holding section is pressed against the surface of the sensor (for example, the substrate) and comes into contact with the sensor. Therefore, a sensor adhesive section 122a that fixes the water evaporation suppressing section to the sensor by bonding it to at least a part of the outer edge of the water evaporation suppressing section that comes into contact with the sensor may be provided, and an adhesive layer may be formed on the sensor adhesive section 122a to fix the calibration mechanism with the calibration solution holding section pressed against the sensor surface. In FIG. 3, the sensor adhesive portion 122a is formed around the entire circumference of the outer edge of the water evaporation suppression portion, but the present invention is not limited to this. A plurality of sensor adhesive portions 122a may be formed at intervals, or a ring-shaped portion (e.g., C-shaped) with a missing portion may be formed. From the viewpoint of facilitating repeated attachment and detachment of the calibration mechanism to the sensor, it is preferable to use, for example, an epoxy silicone adhesive as the adhesive for forming the adhesive layer. In this embodiment, the calibration liquid holding portion may be a plate or film-shaped portion, or the calibration liquid holding portion may be a gel-like portion, and the calibration liquid holding portion may be laminated on the water evaporation suppression portion in a state of being molded into a layer. The water evaporation suppression portion and the calibration liquid holding portion may be bonded to each other via an adhesive layer, or the calibration liquid holding portion itself may have adhesiveness, and the calibration liquid holding portion may be disposed so as to be in direct contact with the water evaporation suppression portion without an adhesive layer or an adhesive member such as a double-sided tape.In this embodiment, in order to make it easier to repeatedly attach and detach the calibration mechanism to and from the sensor, a part of the edge of the outer edge of the moisture evaporation suppression portion described above may be left as a trigger portion 122b that serves as a trigger when peeling off the part that is not adhered to the sensor surface, and in this embodiment, this trigger portion functions as the attachment / detachment member in this embodiment.

[0054] In the above-described embodiment, the electrochemical measurement device measures the sodium ion / potassium ion concentration ratio, which is an electrochemical property of the test liquid to be measured. However, the present invention is not limited to this, and may measure, for example, the sodium ion concentration and / or the potassium ion concentration of the test liquid. In this case, for example, as shown in FIG. 3(b) and FIG. 4, a common electrode 112 that functions as a reference electrode for the sodium ion selective electrode 111N and the potassium ion selective electrode 111K may be provided.

[0055] The common electrode 112 includes a substrate 112a, an internal electrode 112b made of, for example, a silver electrode and disposed on the substrate 112a, a salt bridge layer 112c attached to the internal electrode 112b, and an ion-electron conversion layer 112d disposed between the internal electrode 112b and the salt bridge layer 112c to electrically connect them. In this embodiment, the ion-electron conversion layer 112d has the same composition as the above-mentioned ion-electron conversion layers 111Nd and 111Kd. The compositions of the ion-electron conversion layers 111Nd, 111Kd, and 112d do not all need to be the same, and may be different from each other.

[0056] The salt bridge layer 112c contains, for example, a hydrophobic ionic liquid and an adhesive. The hydrophobic ionic liquid may be any known one, for example, any one described in WO2021 / 177178A1, particularly P 444 MOEBETI (tributyl(2-methoxyethyl)phosphonium bis(pentafluoroethanesulfonyl)imide) and the like can be used.

[0057] The adhesive preferably contains one or more selected from polyvinyl chloride (PVC), polystyrene, acrylate, polyvinyl butyral, polyamide, polyimide, polyurethane, polytetrafluoroethylene (PTFE), polysiloxane, copolymer of vinylidene fluoride and hexafluoropropylene (PVDF-HFP), and fluoropolysiloxane. These adhesives may be used alone or in combination. The adhesive may contain a plasticizer in addition to the above-mentioned components.

[0058] Normally, in order to obtain a reference potential, the common electrode 112 also requires an ion-electron conversion layer and an internal liquid. However, for example, by using the common electrode 112 having the internal electrode 112b made of Ag or the like as in this embodiment and by making the chloride ion activity of the standard solutions for zero calibration and span calibration the same, it is possible to make the ion-electron conversion layer and the internal liquid unnecessary components of the common electrode 112. The internal electrode 112b of the common electrode 112 may be made of a wide variety of materials, such as an electrode made of a metal other than an Ag electrode, an Ag / AgCl electrode, an Ag / AgBr electrode, or an Ag / AgI electrode.

[0059] For example, as shown in FIG. 5, the housing constituting water evaporation suppression section 122 may be capable of housing all of the other members constituting sensor unit 1 therein. 6, for example, a slit-shaped opening may be provided at one end in the longitudinal direction of the moisture evaporation suppression unit 122, which is a rectangular parallelepiped housing, and the substrate on which the sensor 11 is attached may be inserted and removed through this opening to attach and detach the calibration mechanism 12. With this configuration, the calibration solution holding unit 121 is covered by the moisture evaporation suppression unit 122 even while the calibration mechanism 12 is removed, and is therefore less likely to come into contact with the outside air, so that moisture evaporation from the calibration solution holding unit 121 can be more efficiently suppressed.

[0060] 7, the housing constituting the water evaporation suppression unit 122 may be integral with the housing for the information processing unit to form the housing for the entire electrochemical measurement apparatus 100. In this case, as shown in FIG 8, for example, a slide button 14 for sliding the sensor 11 to the outside of the housing may be provided as a removable member, and the sensor 11 may be exposed to the outside of the housing during measurement by the user operating this so that it can come into contact with the test liquid. In this case, it is preferable that the housing constituting the water evaporation suppression unit 122 and the housing for the information processing unit are made of the same material, and it is preferable to use a plastic having a certain degree of strength as the material.

[0061] 9, the calibration liquid holding section 121 may be made of a gel containing the calibration components constituting the calibration liquid and water, and the gel may be injected into the water evaporation suppression section 122 to form the calibration mechanism 12. In this case, the adhesive layer is not necessary. In this case, as shown in FIG. 9, the calibration mechanism 12 may be attached or detached by inserting the sensor 11 into the gel that is the calibration liquid holding portion 121 through a slit formed in the water evaporation suppression portion 122, or by removing the sensor 11 from the gel.

[0062] In a case such as that shown in Figure 9, it is preferable to configure the surface of sensor 11 to be as free of irregularities as possible so that the gel constituting calibration solution holding portion 121 can be removed from sensor 11 along with water evaporation suppression portion 122 when sensor 11 is removed from the slit, and to form the slit such that end portion 122c of water evaporation suppression portion 122 forming the slit comes into contact with sensor 11 when sensor 11 is inserted through the slit in water evaporation suppression portion 122, thereby forming the slit in a size and shape that will fit closely against the surface of sensor 11 when sensor 11 is removed from the slit.

[0063] As shown in Figure 10, the sensor unit may comprise a sensor 11, a calibration mechanism 12, and a flow block 13 capable of containing the test liquid therein, and the calibration mechanism 12 and the flow block 13 may be slidably mounted on a substrate provided on the sensor 11, as shown in Figure 11.

[0064] When using the sensor unit configured in this manner, as shown in FIG. 11, when no measurement is being performed, the calibration mechanism 12 is arranged so as to be located on the sensor surface of the sensor 11, and when the configuration is completed, the calibration mechanism 12 and the flow block 13 slide on the substrate so that the flow block 13 is located on the sensor surface. In this state, the test liquid is supplied onto the sensor surface through the flow path formed in the flow block 13. When the measurement is completed, water for cleaning the sensor surface is shared with the flow block 13, and then the flow block 13 and the calibration mechanism 12 slide to their original positions. The sliding operation of the calibration mechanism 12 and the flow block 13 may be performed manually by the user, but the electrochemical measurement device 100 may be provided with a control unit, a drive unit, etc. (not shown) that control the calibration, measurement, and flow of the liquid, and the calibration and measurement may be performed automatically as long as the user turns on the power of the electrochemical measurement device 100. In this case, grooves, claws, recesses, etc. for sliding each block may be provided as detachable members.

[0065] In addition, some or all of the above-described embodiments and modified embodiments may be combined as appropriate, and it goes without saying that various modifications are possible without departing from the spirit of the invention. [Explanation of symbols]

[0066] 100 Electrochemical measurement device 1. Sensor unit 11 Sensors 12...Calibration mechanism 121...Calibration liquid holding part 122... Moisture evaporation suppression section 2. Information Processing Unit

Claims

1. a calibration solution holder for holding calibration components and water constituting a calibration solution for calibrating an electrochemical measurement device equipped with an ion selective electrode; a moisture evaporation suppression unit that suppresses evaporation of the moisture from the calibration solution holding unit, A calibration mechanism for an electrochemical measurement device, characterized in that the calibration solution holding section is detachable from the ion selective electrode, and the water evaporation suppression section is detachable from the ion selective electrode together with the calibration solution holding section.

2. 2. The calibration mechanism for an electrochemical measurement apparatus according to claim 1, further comprising a detachable member for attaching and detaching the water evaporation suppressing section and the calibration solution holding section to and from the ion selective electrode.

3. The moisture evaporation suppression part is in the form of a film, the calibration solution holding section is laminated on the water evaporation suppressing section, 3. The calibration mechanism for an electrochemical measurement device according to claim 1, wherein the water evaporation suppression section and the calibration solution holding section are arranged so that an outer edge of the water evaporation suppression section is positioned outward from an outer edge of the calibration solution holding section, and a sensor adhesive section that fixes the water evaporation suppression section and the calibration solution holding section to the ion selective electrode is formed on at least a portion of the outer edge.

4. the calibration solution holding section is gel-like, 2. The calibration mechanism for an electrochemical measurement apparatus according to claim 1, wherein the water evaporation suppression unit is a housing that houses the calibration solution holding unit therein.

5. 5. The calibration mechanism for an electrochemical measurement apparatus according to claim 4, wherein the water evaporation suppression section is configured to be capable of accommodating an ion selective electrode therein while being in contact with the calibration solution holding section.

6. the calibration solution holding unit is solid, 2. The calibration mechanism for an electrochemical measurement apparatus according to claim 1, wherein the calibration solution holding section and the water evaporation suppressing section are bonded to each other.

7. A sensor unit comprising the calibration mechanism for an electrochemical measurement apparatus according to any one of claims 1 to 6 and an ion selective electrode.

8. An electrochemical measurement device comprising the sensor unit according to claim 7.

9. a calibration solution holder for holding calibration components and water constituting a calibration solution for calibrating an electrochemical measurement device equipped with an ion selective electrode; a moisture evaporation suppression unit that suppresses evaporation of the moisture from the calibration solution holding unit, A method for calibrating an electrochemical measurement device, comprising the steps of: calibrating an electrochemical measurement device equipped with an ion selective electrode using a calibration mechanism for an electrochemical measurement device, characterized in that the calibration solution holding unit is detachable from the ion selective electrode, and the water evaporation suppression unit is detachable from the ion selective electrode together with the calibration solution holding unit.

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