JP6472631B2 - Electrochemical sensor and electrochemical measuring device - Google Patents

Description

  The present invention relates to an electrochemical sensor configured to include a reference electrode, a working electrode, and a counter electrode, and an electrochemical measurement device configured to include such an electrochemical sensor.

  For example, Patent Document 1 below analyzes the state of an electrolytic copper plating solution (hereinafter also referred to as “analysis target solution”) used when copper metal is embedded in a via hole or a trench provided in a printed circuit board or the like. An invention of a possible analyzer is disclosed. This analyzer is configured to be able to analyze the state of a liquid to be analyzed by an electrochemical measurement process using an electrochemical cell having a reference electrode, a working electrode (rotary electrode), and a counter electrode (counter electrode). Specifically, the analyzer includes the electrochemical cell described above, a rotation speed variable stirring unit that rotates a working electrode via a dedicated controller, and a voltage / current generator that supplies a measurement current to the electrochemical cell. And a multimeter that measures the potential of the electrochemical cell (electrode), a dedicated controller, a voltage / current generator, and a control computer that controls the operation of the multimeter and the like.

  When analyzing the analysis target liquid by the analyzer, first, the analysis target liquid is collected from the liquid tank in which the analysis target liquid is stored. Next, the collected analysis target liquid is poured into a beaker and set on a dedicated stand of the analyzer. At this time, the tip (lower end) of each electrode in the electrochemical cell is immersed in the analysis target liquid in the beaker. Subsequently, the analysis process is started by operating the keyboard of the control computer. As a result, under the control of the control computer, the working electrode is rotated and a current for measurement is supplied from the voltage / current generator to the electrochemical cell, and the potential of each electrode is measured by the multimeter (electrochemical). Execution of measurement process). Further, the control computer executes an analysis process for a predetermined analysis item based on the measurement result by the multimeter, and displays the analysis result on the display unit. Thereby, the operation | work which analyzes the state of a liquid to be analyzed is completed.

JP2009-299193A (pages 8-16 and 1-17)

However, the analyzers disclosed in the above-mentioned patent documents have the following problems to be solved. That is, in a conventional analyzer, an electrochemical measurement process is performed in a state where the lower end portion of each electrode is immersed in the analysis target liquid by collecting the analysis target liquid and pouring it into the beaker and setting the beaker on a dedicated stand. The structure which starts is adopted. Therefore, in the conventional analyzer, a location of a bath analyte fluid is liquid storage, when the location of the analyzer is away, after collecting the analyte solution, the analyte solution There is a current situation that a certain amount of time is required until the poured beaker is set on a dedicated stand (until the electrochemical measurement process can be started). For this reason, the conventional analyzer has a problem that it is difficult to analyze the state of the liquid to be analyzed in the liquid tank in real time.

  In this case, the analyzer with the dedicated stand removed from the analyzer is installed at the place where the liquid to be analyzed is stored, and each electrode of the electrochemical cell is used as the liquid to be analyzed in the liquid tank. By making it the state immersed directly, it becomes possible to analyze in real time the state of the analysis object liquid in a liquid tank. However, in an actual measurement site (for example, a plating treatment facility), there may be a plurality of liquid tanks for storing the liquid to be analyzed, so the liquid tank in which the liquid to be analyzed that requires analysis is stored. When an analyzer is provided for each, it is necessary to introduce a plurality of analyzers. For this reason, when such a structure is employ | adopted, the analysis cost (measurement cost) of an analysis object liquid (measurement object liquid) will rise.

  In addition, depending on the type of analysis target liquid (measurement target liquid), the electrodes used in this type of analysis apparatus (measurement apparatus) have a measurement capability when left in contact with the analysis target liquid for a long time. May change (deteriorate). Therefore, in this type of analyzer, since it is necessary to pull up the electrode from the liquid to be analyzed when not in use, when an analyzer is provided for each liquid tank, the liquid to be analyzed in the liquid tank The manufacturing cost of the analyzer increases as much as a mechanism for moving each electrode up and down is required.

  The present invention has been made in view of such problems, and an electrochemical sensor and an electrochemical measurement device that can measure the state of a measurement target liquid in real time without causing an increase in the manufacturing cost and measurement cost of the measurement device. The main purpose is to provide

In order to achieve the above object, the electrochemical sensor according to claim 1 is a portable electrochemical sensor, comprising a reference electrode, a working electrode, a counter electrode, and an electrode holding part for holding each electrode, and the electrode The holding portion has a first insertion hole into which the reference electrode can be inserted, a second insertion hole into which the working electrode can be inserted, and a third insertion hole into which the counter electrode can be inserted. A first connecting fitting having a bottom cylindrical holding body, to which the inserted reference electrode is connected, a second connecting fitting to which the inserted working electrode is connected, and inserted A third connection fitting to which the counter electrode in a state of connection is connected is arranged in the holding portion main body so that the electrodes can be attached and detached. The holding portion main body is on the tip side of the electrodes. In the state where each part of Together with the holding configured to be able to respective electrodes, between circumferential surface and the inner surface of the first insertion hole of the reference electrode, between the circumferential surface and the inner surface of the second insertion hole of the working electrode, And the sealing member which seals between the surrounding surface of the said counter electrode, and the inner surface of the said 3rd insertion hole is each arrange | positioned in each said insertion hole, and each said electrode is inserted in each said insertion hole The entire portion on the tip end side that is configured to prevent the measurement target liquid from entering the holding portion main body from the respective insertion holes and protrudes from the bottom surface of the holding portion main body in each electrode. And the electrochemical measurement process about the said measuring object liquid can be performed in the state by which the site | part of the said bottom face side in the said holding | maintenance part main body was immersed in the said measuring object liquid .

  The electrochemical sensor according to claim 2 is the electrochemical sensor according to claim 1, wherein a signal processing circuit board connected to the electrodes via the connection fittings is accommodated in the holder main body. Yes.

  An electrochemical measurement apparatus according to a third aspect includes the electrochemical sensor according to the first or second aspect, and a measurement processing unit that performs an electrochemical measurement process via the electrochemical sensor.

The electrochemical sensor according to claim 1 is configured to be portable, and the electrode holding portion for holding the reference electrode, the working electrode, and the counter electrode is inserted with the first insertion hole and the working electrode into which the reference electrode can be inserted. A first connecting fitting including a bottomed cylindrical holding body having a second insertion hole capable of being inserted therein and a third insertion hole into which a counter electrode can be inserted formed on the bottom surface; A second connection fitting to which the working electrode is connected and a third connection fitting to which the counter electrode is connected are arranged in the holding portion body so that each electrode can be attached and detached. Between the peripheral surface of the electrode and the inner surface of the first insertion hole, between the peripheral surface of the working electrode and the inner surface of the second insertion hole, and between the peripheral surface of the counter electrode and the inner surface of the third insertion hole A sealing member that seals each electrode is disposed in each insertion hole, and each electrode is inserted into each insertion hole. Oite penetration of measured liquid to the holding portion main body from the insertion hole is blocked, the entire region of the holding portion front end portion which is protruded from the bottom surface of the body at each electrode, and the holding portion bottom of the main body An electrochemical measurement process is performed on the measurement target liquid in a state where the portion on the side is immersed in the measurement target liquid . The electrochemical measurement device according to claim 3 includes the electrochemical sensor described above and a measurement processing unit that performs an electrochemical measurement process via the electrochemical sensor.

  Therefore, according to the electrochemical sensor according to claim 1 and the electrochemical measurement device according to claim 3, it is not necessary to install an electrochemical measurement device for each location (measurement location) where the measurement target liquid is stored. In addition, the electrochemical measurement device can be transported to the measurement location, and each electrode of the portable electrochemical sensor can be directly immersed in the liquid to be measured to execute the electrochemical measurement process, resulting in an increase in measurement cost. In addition, the state of the liquid to be measured can be measured in real time. Further, since the electrochemical sensor is portable, each electrode can be kept out of contact with the measurement target liquid when not in use without providing a mechanism for moving each electrode up and down with respect to the measurement target liquid. Thereby, the situation where the useful life of an electrode becomes short at the time of non-use can be suitably avoided, without causing the manufacturing cost of an electrochemical measuring device to rise.

  According to the electrochemical sensor according to claim 2 and the electrochemical measurement device including the electrochemical sensor, the signal processing circuit board connected to each electrode via each connection fitting is accommodated in the holding unit main body. Therefore, signal processing can be performed by the processing circuit of the signal processing circuit board in the vicinity of each electrode, so that even if the electrochemical sensor is connected to the measurement processing unit by a somewhat long signal cable, accurate electrochemical measurement Processing can be executed.

1 is a configuration diagram of an electrochemical measurement device 1. FIG. 2 is a cross-sectional view of a portable electrochemical sensor 3. FIG. 2 is a bottom view of the portable electrochemical sensor 3. FIG. 4 is another cross-sectional view of the portable electrochemical sensor 3. FIG. 3 is a cross-sectional view of the portable electrochemical sensor 3 with a reference electrode 21 removed from a casing 25. FIG.

  Hereinafter, embodiments of an electrochemical sensor and an electrochemical measurement device will be described with reference to the accompanying drawings.

  The electrochemical measurement apparatus 1 shown in FIG. 1 is an example of an “electrochemical measurement apparatus”, and includes a measurement apparatus main body 2 and a portable electrochemical sensor 3, and a plating solution Xa stored in a plating solution tank X. It is comprised so that the electrochemical measurement process about various "measuring liquids", such as these, can be performed.

  The measurement apparatus main body 2 is an example of a “measurement processing unit”, and includes an operation unit 11, a display unit 12, a control unit 13, and a storage unit 14. The operation unit 11 includes various operation switches for instructing measurement condition setting operations and measurement process start / stop, and outputs operation signals corresponding to these operations to the control unit 13. The display unit 12 displays the measurement result of the electrochemical measurement process calculated by the control unit 13 under the control of the control unit 13.

  The control unit 13 comprehensively controls the electrochemical measurement device 1. Specifically, the control unit 13 starts an electrochemical measurement process in response to an operation signal from the operation unit 11 and is output from the portable electrochemical sensor 3 which is an example of a “portable electrochemical sensor”. The measured value based on the sensor signal is stored in the storage unit 14. The control unit 13 analyzes the measurement value stored in the storage unit 14 to obtain an analysis result for a predetermined analysis item for the plating solution Xa, and stores the obtained analysis result in the storage unit 14. And displayed on the display unit 12. The storage unit 14 stores an operation program of the control unit 13, a measurement value calculated by the control unit 13, an analysis result obtained by analyzing the measurement value, and the like.

  The portable electrochemical sensor 3 is a sensor device capable of performing an electrochemical measurement process by a three-electrode method for measuring the state of the “measurement target liquid”. As shown in FIGS. , A working electrode 22, a counter electrode (counter electrode: counter electrode) 23, a signal processing circuit board 24, a casing 25, and a signal cable 26.

  In this case, in each drawing referred to in this specification, the reference electrode 21, the working electrode 22, and the counter electrode 23 are illustrated in the same shape and the same size in order to facilitate understanding of the configuration of the “electrochemical sensor”. In practice, however, electrodes having various shapes and sizes are employed for each of the electrodes 21 to 23 in accordance with the contents of the electrochemical measurement process to be performed and the type of the liquid to be measured. In addition, “connecting fittings 21c to 23c for connecting to the measurement circuit (in this example, the signal processing circuit board 24) are formed on the upper end portions of the electrodes 21 to 23, respectively. Since the specific configuration of 23 is publicly known, detailed description and illustration regarding components other than the connection fittings 21c to 23c are omitted.

  The signal processing circuit board 24 is an example of a “signal processing circuit board”, and constitutes a measurement circuit for performing an electrochemical measurement process together with the control unit 13 of the measurement apparatus main body 2. In this case, the portable electrochemical sensor 3 of this example is equipped with a potentiostat, an I / V conversion circuit, and the like for executing an electrochemical measurement process. The signal processing circuit board 24 is connected to the electrodes 21 to 23 while being accommodated in the casing 25, and is connected to the control unit 13 of the measuring apparatus main body 2 via a flexible signal cable 26. The

The casing 25 is an example of an “electrode holding unit”, and includes a casing body 31 and a sealing material 32. The casing body 31 is an example of a “holding body”, and is a chemical-resistant resin material (for example, various engineering plastics such as PEEK (polyether ether ketone) resin and PTFE (polytetrafluoroethylene) resin). Is formed into a cylindrical shape (an example of a “bottomed cylindrical shape”). The casing body 31 has an insertion hole H1 (an example of a “first insertion hole”) into which the reference electrode 21 can be inserted, and an insertion hole H2 (an example of a “second insertion hole”) into which the working electrode 22 can be inserted. , And an insertion hole H3 into which the counter electrode 23 can be inserted (an example of a “third insertion hole”) is formed in the bottom surface F, thereby holding the electrodes 21 to 23 inserted into the insertion holes H1 to H3. It is configured to be able to.

  In this case, with this type of “electrochemical measurement device”, it becomes difficult to obtain an accurate measurement value when the distance between the electrodes changes during the electrochemical measurement process. Therefore, the “insertion hole” formed in the “electrode holding portion” needs to be formed in a size that does not cause wobble in each inserted electrode. On the other hand, in this type of “electrochemical measurement device (electrochemical sensor)”, it is necessary to replace each electrode with a new electrode when the total execution time of the measurement process reaches a predetermined time. Each “insertion hole” needs to be formed slightly larger so that each electrode can be smoothly inserted and removed (detached) without damaging each electrode. Therefore, in the portable electrochemical sensor 3 of the present example, in order to allow the electrodes 21 to 23 to slide relative to the casing 25 without causing the wobbling of the electrodes 21 to 23 in the inserted state, the electrodes 21 to 23 are allowed to slide. The inner diameters of the insertion holes H1 to H3 are defined so that a very small gap (as an example, a gap of about 0.05 mm) is generated between the peripheral surface of the casing 23 and the inner surfaces of the insertion holes H1 to H3 of the casing 25. Has been.

Further, the casing main body 31 includes a circumferential surface of the reference electrode 21 and an inner surface of the insertion hole H1, a circumferential surface of the working electrode 22 and an inner surface of the insertion hole H2, and a circumferential surface of the counter electrode 23 and the insertion hole. Sealing material 32 that seals between the inner surfaces of H3 is disposed in each of the insertion holes H1 to H3. In this case, the sealing material 32 corresponds to a “sealing member”. As an example, an O-ring (an annular sealing material formed of an elastic resin having a circular cross section) or a V ring (a cross section is triangular or V An annular sealing material formed of a letter-shaped elastic resin) or the like. Thereby, in the portable electrochemical sensor 3 of this example, in the state which inserted each electrode 21-23 in each insertion hole H1-H3, the surrounding surface of each electrode 21-23, and the inner surface of each insertion hole H1-H3, Intrusion of “measuring solution” (plating solution Xa, etc.) into the casing body 31 is prevented through the above-described gap.

  Further, the signal processing circuit board 24 is accommodated in the casing body 31 and the connection fitting C1 for connecting the reference electrode 21 inserted in the insertion hole H1 to the signal processing circuit board 24 ("first" Connection bracket C2 (an example of “second connection bracket”) for connecting the working electrode 22 inserted in the insertion hole H2 to the signal processing circuit board 24, and the insertion hole H3. A connection fitting C3 (an example of a “third connection fitting”) for connecting the counter electrode 23 inserted into the signal processing circuit board 24 is provided. Thereby, in this portable electrochemical sensor 3, attachment / detachment of each electrode 21-23 with respect to the casing 25 (connection / disconnection of each electrode 21-23 with respect to the signal processing circuit board 24) is accept | permitted.

  When performing the electrochemical measurement process for the plating solution Xa (see FIG. 1) stored in the plating solution tank X, for example, using the electrochemical measurement device 1, first, the portable electricity The chemical sensor 3 is assembled. In this case, the working electrode 22 and the counter electrode 23 can be stored in a state of being attached (inserted) to the casing 25 (insertion holes H2 and H3 of the casing body 31). In case of using electrodes with “Silver / Silver Chloride Electrode” etc., store in a protective solution so as to prevent volatilization of liquids constituting the liquid passage and change in the amount of ions. It is necessary to take out the reference electrode 21 that is present from the protective liquid and attach it to the casing 25.

  Specifically, as an example, when the reference electrode 21 is attached to the casing 25, the insertion hole H1 formed in the bottom surface F of the casing body 31 in the casing 25 is inserted into the reference electrode 21 as shown in FIG. The end (upper end) on the side where the connection fitting 21c is formed is inserted in the direction of the arrow U. At this time, when the main body portion of the reference electrode 21 (the portion shown in the figure thicker than the connection fitting 21c) is in contact with the sealing material 32 in the insertion hole H1, the reference electrode is used by the sealing material 32. The clearance gap between the surrounding surface of 21 (main-body part) and the inner surface of the insertion hole H1 is obstruct | occluded. Further, by further sliding the reference electrode 21 in the direction of the arrow U with respect to the casing main body 31, the inserted connection fitting 21c is connected to the connection fitting C1 in the casing main body 31, as shown in FIG.

  Thus, the reference electrode 21 is connected to the signal processing circuit board 24 via the connection fitting C1, and the reference electrode 21 is held by the casing 25 (the sealing material 32 and the connection fitting C1 in the insertion hole H1). Become. In this case, in the state where the mounting of the reference electrode 21 to the casing 25 is completed, the direction of the arrow D (direction away from the casing 25: by the sealing material 32 that is in close contact with the peripheral surface of the reference electrode 21 (main body portion): Slide to (see FIG. 2) is restricted. Thereby, the unintentional dropping of the reference electrode 21 from the casing 25 is avoided. Thereafter, the working electrode 22 and the counter electrode 23 are mounted on the casing 25 in the same manner as the reference electrode 21 as necessary. Thereby, the assembly work of the portable electrochemical sensor 3 is completed.

  Next, after the portable electrochemical sensor 3 is connected to the measuring apparatus main body 2 via the signal cable 26, the upper end portion side portion of the casing 25 is gripped, and the portable electrochemical sensor 3 as shown in FIG. Is immersed in the plating solution Xa in the plating solution tank X. At this time, in the electrochemical measurement device 1 (portable electrochemical sensor 3) of this example, as described above, there is a gap between the peripheral surface of each electrode 21 to 23 and the inner surface of each insertion hole H1 to H3. Since it is blocked by the sealing material 32, the electrodes 21 to 23 are sufficiently immersed in the plating solution Xa without causing the plating solution Xa to enter the casing body 31. The entire surface can be in contact with the plating solution Xa.

  Thereafter, the operation unit 11 of the measurement apparatus main body 2 is operated to execute an arbitrary electrochemical measurement process. Thereby, the measurement result is displayed on the display unit 12 (not shown), and the state of the plating solution Xa in the plating solution tank X can be grasped in real time. Since the measurement principle of the electrochemical measurement process (as an example, the measurement process by the voltammetry method) and the analysis process of the state of the plating solution Xa based on the measurement result are well known, detailed description is omitted.

  Further, when the electrochemical measurement process is performed on the plating solution Xa in the plating solution tank X different from the plating solution tank X, the plating solution tank X storing the plating solution Xa that has completed the measurement process. Then, the portable electrochemical sensor 3 is pulled up, and the electrochemical measuring device 1 is transported to the place where the plating solution tank X for storing the next measurement target plating solution Xa is stored. Then, the measurement process for the plating solution Xa in the plating solution tank X is executed. It is possible to grasp the state of the plating solution Xa in each plating solution tank X in real time by sequentially executing such measurement processing for each plating solution tank X whose state of the plating solution Xa is to be analyzed. Become.

  On the other hand, as described above, by executing the measurement process a plurality of times, the total execution time of the measurement process (the total time of contacting each electrode 21 to 23 with the measurement target liquid) is set to a predetermined time. When the time has reached, the electrodes 21 to 23 that have reached the specified time are replaced with new electrodes 21 to 23 in order to obtain an accurate measurement value in the subsequent measurement process. At this time, the electrodes 21 to 23 to be replaced are slid with respect to the casing 25 as shown by arrows D in FIGS. 2 and 4 and extracted from the insertion holes H1 to H3, and the above-described portable electrochemical sensor 3 is assembled. The new electrodes 21 to 23 are attached to the casing 25 in the same procedure as the time. Thereby, it will be in the state in which the site | part except the removed electrodes 21-23 can be used continuously, and the electrochemical measurement process about another measuring object liquid can be performed.

  In this case, the applicant improves the analysis apparatus disclosed in Patent Document 1 described above prior to the development of the electrochemical measurement apparatus 1 described above, so that a single electrochemical measurement apparatus can be used in a plurality of liquid tanks. An electrochemical measurement device capable of sequentially performing electrochemical measurement processing for the liquids to be measured was prepared. Specifically, in the electrochemical measuring apparatus (not shown) prototyped by the applicant, components corresponding to the dedicated controller, the variable speed stirring unit and the dedicated stand are removed from the conventional analyzer, and the voltage / current By connecting a component (measurement processing unit) corresponding to a generator or a multimeter and an electrochemical sensor (electrochemical cell) with a flexible signal cable, the electrochemical sensor is held in the hand and the liquid tank It is possible to make it the state (state which can perform an electrochemical measurement process) where the front-end | tip part of each electrode was immersed in the measuring object liquid.

  Therefore, in the electrochemical measuring device prototyped by the applicant, as in the electrochemical measuring device 1 described above, any liquid tank can be used without installing an electrochemical measuring apparatus (analyzer) for each liquid tank. After completing the electrochemical measurement process for the liquid to be measured stored in the tank, lift the electrochemical sensor from the storage tank and clean the surface of each electrode as necessary. It is possible to execute an electrochemical measurement process on the measurement target liquid in the liquid tank by immersing it in the measurement target liquid in the liquid tank.

  However, in the electrochemical measuring apparatus prototyped by the applicant, each electrode is placed on the measurement target liquid in the measurement container by setting the measurement container (beaker) into which the measurement target liquid (analysis target liquid) is poured on a dedicated stand. What is an electrochemical measurement device such as a conventional analysis device (an electrochemical measurement device in which the positional relationship between the liquid to be measured in the measurement container and each electrode of the electrochemical sensor is fixed) such as In contrast, by adopting a configuration in which each electrode is immersed in the liquid to be measured while holding the electrochemical sensor in the hand, depending on the user, each electrode of the electrochemical sensor may be immersed more deeply than necessary in the liquid to be measured. There was a case.

  In such a case, the liquid to be measured reaches the base end of each electrode through the gap between each electrode and the holder holding the electrode, and the base end of each electrode and the signal cable There is a possibility that the liquid to be measured comes into contact with the connection site. For this reason, the connection state (contact resistance) between each electrode and the signal cable changes, or depending on the type of the liquid to be measured, the connection part between the electrode and the signal cable is eroded by the liquid to be measured, resulting in a normal connection state. It may be difficult to maintain.

  On the other hand, in the electrochemical measuring device 1 (portable electrochemical sensor 3) of this example, as described above, the peripheral surfaces of the electrodes 21 to 23 and the inner surfaces of the insertion holes H1 to H3 in the casing body 31 The gap between the two is closed by the sealing material 32. Thereby, in the electrochemical measuring apparatus 1 (portable electrochemical sensor 3) of this example, each electrode 21-23 was fully immersed in the measuring object liquid until the bottom face F of the casing main body 31 contacted the measuring object liquid. Even in the state, a situation in which the liquid to be measured enters the casing body 31 from the gaps between the peripheral surfaces of the electrodes 21 to 23 and the inner surfaces of the insertion holes H1 to H3 is preferably avoided.

As described above, the portable electrochemical sensor 3 is configured to be portable, and the casing 25 that holds the reference electrode 21, the working electrode 22, and the counter electrode 23 includes the insertion hole H <b> 1 into which the reference electrode 21 can be inserted, A fitting having a bottomed cylindrical casing body 31 formed on the bottom surface F with an insertion hole H2 into which the working electrode 22 can be inserted and an insertion hole H3 into which the counter electrode 23 can be inserted, and to which the reference electrode 21 is connected C1, a connection fitting C2 to which the working electrode 22 is connected, and a connection fitting C3 to which the counter electrode 23 is connected are arranged in the casing body 31 so that the electrodes 21 to 23 can be attached and detached. Is between the peripheral surface of the reference electrode 21 and the inner surface of the insertion hole H1, between the peripheral surface of the working electrode 22 and the inner surface of the insertion hole H2, and between the peripheral surface of the counter electrode 23 and the inner surface of the insertion hole H3. Sealing material 32 for sealing the can from the insertion holes H1~H3 in the inserted state each disposed has been the electrodes 21 to 23 in the insertion holes H1~H3 into the insertion holes H1~H3 into the casing body 31 Intrusion of the measurement target liquid (plating liquid Xa) is prevented. Further, in this electrochemical measuring device 1, the above-described portable electrochemical sensor 3 and the “measurement processing unit (in this example, the signal processing circuit board 24 and the signal processing circuit board 24) that perform the electrochemical measurement processing via the portable electrochemical sensor 3”. A control unit 13) ".

  Therefore, according to the portable electrochemical sensor 3 and the electrochemical measuring apparatus 1, the place where the measurement target liquid is stored (for example, the installation place of the plating solution tank X where the plating solution Xa is stored: measurement) Even without installing an “electrochemical measurement device” for each location), the electrochemical measurement device 1 is transported to the measurement location, and the electrodes 21 to 23 of the portable electrochemical sensor 3 are directly immersed in the liquid to be measured. Since the electrochemical measurement process can be executed, the state of the measurement target liquid can be measured in real time without causing an increase in measurement cost. In addition, since the portable electrochemical sensor 3 is portable, the electrodes 21 to 23 are in contact with the measurement target liquid when not in use without providing a mechanism for moving the electrodes 21 to 23 up and down relative to the measurement target liquid. There can be no state. Thereby, the situation where the useful life of the electrodes 21-23 becomes short at the time of non-use can be avoided suitably, without causing the manufacturing cost of the electrochemical measuring device 1 to rise.

  Further, according to the portable electrochemical sensor 3 and the electrochemical measurement device 1, the signal processing circuit board 24 connected to the electrodes 21 to 23 through the connection fittings C1 to C3 is accommodated in the casing body 31. As a result, signal processing can be executed by the signal processing circuit board 24 in the vicinity of each of the electrodes 21 to 23, so that even if the portable electrochemical sensor 3 is connected to the control unit 13 by a somewhat long signal cable 26. Accurate electrochemical measurement process can be performed.

  Note that the configurations of the “electrochemical sensor” and the “electrochemical measurement device” are not limited to the configurations of the portable electrochemical sensor 3 and the electrochemical measurement device 1 described above. For example, instead of the measurement device main body 2 in the electrochemical measurement device 1 described above, a “measurement result recording device” and a “measurement result recording device” for recording measurement results of electrochemical measurement processing (measurement values of electrochemical measurement processing) "Processing device (personal computer, etc.)" that executes a process for analyzing the state of the liquid to be measured based on the measurement result recorded in "Measurement place (place where the liquid to be measured is stored)" In, only the process of recording the measurement result in the “measurement result recording device” is performed, and the measurement result is transferred to the “processing device” at an arbitrary timing. It is also possible to adopt a configuration for executing state analysis processing.

  Further, the portable electrochemical sensor 3 having the configuration in which the signal processing circuit board 24 is accommodated in the casing main body 31 has been described as an example. However, the “signal processing circuit (potentiostat or I / O) similar to the signal processing circuit board 24 is described. V conversion circuit, etc.) "can be arranged on the measuring device main body 2 side instead of the casing main body 31 (as a component on the" measurement processing unit "side to which the" electrochemical sensor "is connected). .

DESCRIPTION OF SYMBOLS 1 Electrochemical measuring apparatus 2 Measuring apparatus main body 3 Portable electrochemical sensor 13 Control part 14 Memory | storage part 21 Reference electrode 21c-23c Connection metal fitting 22 Working electrode 23 Counter electrode 24 Signal processing circuit board 25 Casing 26 Signal cable 31 Casing main body 32 Seal Material C1 to C3 Connection F F Bottom H1 to H3 Insertion hole X Plating solution bath Xa Plating solution

Claims (3)

A reference electrode, a working electrode, a counter electrode, and an electrode holding unit that holds each electrode,
The electrode holding portion has a first insertion hole into which the reference electrode can be inserted, a second insertion hole into which the working electrode can be inserted, and a third insertion hole into which the counter electrode can be inserted. A first connecting fitting to which the inserted reference electrode is connected, a second connecting fitting to which the inserted working electrode is connected, and A third connection fitting to which the counter electrode in the inserted state is connected is disposed in the holding portion main body, and is configured so that the electrodes can be attached and detached.
The holding portion main body is configured to be able to hold each electrode in a state where the tip portion side portion of each electrode protrudes from the bottom surface, and the peripheral surface of the reference electrode and the first insertion hole Sealing between the inner surface of the working electrode and the inner surface of the second insertion hole and between the outer surface of the counter electrode and the inner surface of the third insertion hole. member is configured to prevent infiltration of liquid to be measured from the respective insertion holes in a state in which each disposed has been the respective electrodes in the respective insertion holes are inserted in the respective insertion holes into the holder body,
In the respective electrodes, the measurement is performed in a state where the entire portion on the tip end side projecting from the bottom surface of the holding portion main body and the portion on the bottom surface side of the holding portion main body are immersed in the measurement target liquid. A portable electrochemical sensor configured to be capable of performing an electrochemical measurement process on a target liquid .   The electrochemical sensor according to claim 1, wherein a signal processing circuit board connected to the electrodes via the connection fittings is accommodated in the holding portion main body.   An electrochemical measurement apparatus comprising: the electrochemical sensor according to claim 1 or 2; and a measurement processing unit that performs an electrochemical measurement process via the electrochemical sensor.

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