WO2022024433A1 - Electrolyte analysis apparatus - Google Patents

Electrolyte analysis apparatus Download PDF

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Publication number
WO2022024433A1
WO2022024433A1 PCT/JP2021/007995 JP2021007995W WO2022024433A1 WO 2022024433 A1 WO2022024433 A1 WO 2022024433A1 JP 2021007995 W JP2021007995 W JP 2021007995W WO 2022024433 A1 WO2022024433 A1 WO 2022024433A1
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WIPO (PCT)
Prior art keywords
ion
electrode
cover
sample
unit
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PCT/JP2021/007995
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French (fr)
Japanese (ja)
Inventor
望 長谷川
悟郎 吉田
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株式会社日立ハイテク
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Priority to JP2022540001A priority Critical patent/JP7378628B2/en
Publication of WO2022024433A1 publication Critical patent/WO2022024433A1/en

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    • 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
    • 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
    • G01N27/416—Systems

Definitions

  • the present invention relates to an electrolyte analyzer.
  • the electrolyte analyzer is a device that measures the concentration of a specific electrolyte contained in the electrolyte solution of human blood, urine, etc., and measures the concentration using an ion-selective electrode.
  • a flow type electrolyte analyzer is known. In the flow type electrolyte analyzer, a sample solution obtained by directly diluting serum as an electrolyte solution or diluted with a sample diluent is supplied to an ion-selective electrode, and the liquid potential between the ion-selective electrode and the comparative electrode solution is measured. ..
  • a standard solution having a known electrolyte concentration is supplied to the ion-selective electrode, and the liquid potential with the comparative electrode solution is measured in the same manner as the serum (or sample solution). Then, the electrolyte concentration of serum (or sample solution) can be calculated from the two liquid potentials of the standard solution and the serum (or sample solution).
  • the ion-selective electrode used in such a flow-type electrolyte analyzer has a limited expiration date and the number of measurements, and requires regular replacement. Therefore, for example, when the ion-selective electrode reaches the expiration date during the analysis, the analysis cannot be performed until the ion-selective electrode is replaced with a new ion-selective electrode, resulting in a decrease in processing capacity.
  • Patent Document 1 in a biofluid analyzer including a sensor group composed of a plurality of electrochemical sensors, a plurality of sensor groups including the same electrochemical sensor as the sensor included in the sensor group are provided.
  • a biofluid analyzer is disclosed in which the sensors are arranged in parallel with each other and one of the sensor groups can be selected at the time of sample measurement.
  • the sample probe may interfere with the sample probe when opening the cover covering a plurality of sensors arranged in parallel. Therefore, it is necessary to interrupt the analysis when exchanging the sensors. There is a problem that the processing capacity is reduced.
  • the present invention has been made in view of the above, and an object of the present invention is to provide an electrolyte analyzer capable of exchanging an ion-selective electrode while suppressing a decrease in processing capacity.
  • the present application includes a plurality of means for solving the above problems, for example, a diluting tank for diluting a sample dispensed by a sample probe and a specific ion in the sample diluted in the diluting tank.
  • a plurality of electrode unit units each having an ion-selective electrode for measuring a concentration are provided, and at least one electrode unit among the plurality of electrode units is below the operating range of the sample probe and above the diluting tank.
  • a detachably arranged first cover having an opening provided for the probe portion to descend to the diluting tank, and above the ion-selective electrode in a range not below the operating range of the sample probe. It shall have a second cover that is detachably arranged so as to cover the above.
  • the ion-selective electrode can be replaced while suppressing the decrease in processing capacity.
  • FIG. 1 is a diagram schematically showing the overall configuration of the electrolyte analyzer according to the embodiment of the present invention.
  • a flow-type electrolyte analyzer using an ion-selective electrode (ISE: Ion Selective Electrode) (hereinafter, simply referred to as an electrolyte analyzer) will be described. ..
  • the electrolyte analyzer 100 operates the analysis unit 1 for measuring a specific ion concentration in a sample to be analyzed (for example, a patient's sample) and the operation of the entire electrolyte analyzer including the analysis unit 1. It is provided with a control unit 31 (control device) for controlling.
  • the analysis unit 1 includes a sample container 52 that houses the sample to be analyzed, and a plurality of electrode unit units that measure the ion concentration in the sample (in the present embodiment, the first and second electrode unit units 11 and 12). 2), the sample probe 22 that dispenses the sample contained in the sample container 52 into the first and second electrode units 11 and 12, and the comparison electrode that houses the comparative electrode solution.
  • the sample probe 22 is composed of a cover portion 22a provided so as to be rotatable in the horizontal direction around one end, and a probe portion 22b arranged so as to project downward from the other end of the cover portion 22a and extend. ing.
  • the sample probe 22 can be moved in the vertical direction, and the position of the probe portion 22b can be changed by rotating the cover portion 22a, and the sample container 52 and the first and second electrode portions can be moved in the vertical direction.
  • the sample is inserted into the units 11 and 12, and the sample is dispensed (suctioned and discharged) by a pump device (not shown).
  • a pump device not shown.
  • the position of the sample probe 22 the case where the sample is sucked from the sample container 52 is the position 22A, and the sample is dispensed (discharged) to the first electrode unit 11.
  • the case where the sample is dispensed (discharged) to the second electrode unit 12 is shown in parentheses as the position 22B, and the case where the sample is dispensed (discharged) to the second electrode unit 12 is shown in parentheses.
  • the first electrode unit 11 has a diluting tank 23a that dilutes the sample with the diluting liquid sent from the diluting liquid bottle 56a via the flow path, and ions of the diluted sample sent from the diluting tank 23a via the flow path. It has an ion-selective electrode group 24a composed of a plurality of ion-selective electrodes for measuring the concentration, and a comparison electrode 24b with which a comparative solution sent from the comparison electrode liquid bottle 55a via a flow path is in contact.
  • the ion-selective electrode group 24a is composed of a plurality of ion-selective electrodes for measuring ion concentrations such as sodium ion (Na +), potassium ion (K +), calcium ion (Ca ++), and chlor ion (Cl-), respectively. Has been done.
  • the sample probe 22 that sucks the sample contained in the sample container 52 at the position 22A moves to the position 22B and is discharged (dispensed) to the dilution tank 23a.
  • the diluting liquid of the diluting liquid bottle 56a is discharged to the diluting tank 23a via the diluting liquid bottle 56a by the liquid feeding mechanism 58a composed of a valve for opening and closing the flow path and a syringe for sucking and delivering the liquid.
  • the sample is diluted and stirred in the dilution tank 23a.
  • the sample diluted and stirred in the diluting tank 23a (hereinafter referred to as a sample solution) is sucked by the suction device 53a and sent to the ion-selective electrode group 24a via the flow path. Further, the comparative electrode liquid of the comparative electrode liquid bottle 55a is fed to the comparative electrode 24b via the flow path by the liquid feeding mechanism 57a.
  • the ion-selective electrodes and the comparison electrode 24b of the ion-selective electrode group 24a are combined with each other. Is electrically conductive. In this state, the potential difference between the comparative electrode 24b and each ion-selective electrode of the ion-selective electrode group 24a is measured, and the concentration of a specific ion contained in the sample solution is measured based on the obtained potential difference.
  • an ion-sensitive film having a property that the electromotive force changes according to the concentration of a specific ion in the sample solution is attached to each ion-selective electrode of the ion-selective electrode group 24a.
  • the ion-selective electrode outputs an electromotive force according to each ion concentration in the sample solution
  • the electromotive force between each ion-selective electrode of the ion-selective electrode group 24a and the comparative electrode 24b is acquired, and each of them obtains the electromotive force.
  • the ion concentration in the sample is calculated from the electromotive force acquired for the ion.
  • the measurement result is sent to the control unit 31, and is displayed, for example, on a display device (not shown).
  • a display device not shown.
  • the second electrode unit 12 has the same configuration as the first electrode unit 11. That is, the second electrode unit 12 has a diluting tank 23b that dilutes the sample with the diluting liquid sent from the diluting liquid bottle 56b via the flow path, and the diluted sample sent from the diluting tank 23b via the flow path. It has an ion-selective electrode group 24c composed of a plurality of ion-selective electrodes for measuring the ion concentration of the above, and a comparison electrode 24d to which a comparative solution sent from the comparison electrode liquid bottle 55b via a flow path is in contact with the liquid. ..
  • the sample probe 22 that sucks the sample contained in the sample container 52 at the position 22A moves to the position 22C and is discharged (dispensed) to the dilution tank 23b.
  • the diluting liquid of the diluting liquid bottle 56b is discharged to the diluting tank 23b via the diluting liquid bottle 56b by the liquid feeding mechanism 58b composed of a valve for opening and closing the flow path and a syringe for sucking and delivering the liquid.
  • the sample is diluted and stirred in the dilution tank 23b.
  • the sample diluted and stirred in the diluting tank 23b (hereinafter referred to as a sample solution) is sucked by the suction device 53b and sent to the ion-selective electrode group 24c via the flow path. Further, the comparative electrode liquid of the comparative electrode liquid bottle 55b is fed to the comparative electrode 24d via the flow path by the liquid feeding mechanism 57b.
  • each ion-selective electrode and the comparison electrode 24d of the ion-selective electrode group 24c are combined with each other. Is electrically conductive.
  • the potential difference between the comparative electrode 24d and each ion-selective electrode of the ion-selective electrode group 24c can be measured, and the concentration of a specific ion contained in the sample solution can be measured based on the obtained potential difference. ..
  • the measurement result is sent to the control unit 31, and is displayed, for example, on a display device (not shown).
  • the sample solution and the comparative electrode solution in the flow paths of the ion-selective electrode group 24c and the comparative electrode 24d are sucked by the aspirator 53b and discharged to the waste liquid reservoir 54.
  • FIG. 2 to 4 and 7 are top views schematically showing structural examples and arrangement examples of the first and second electrode unit in the analysis unit of the electrolyte analyzer, and FIG. 2 is an ion-selective electrode group.
  • FIG. 3 shows a state in which the cover is attached to the first electrode unit
  • FIG. 3 shows a state in which the ion-selective electrode group cover is removed
  • FIG. 4 shows a state in which the ion-selective electrode group is removed. Indicates that the diluting tank cover has been removed.
  • FIG. 8 is a side view schematically showing a structural example and an arrangement example of the first electrode unit in the analysis unit of the electrolyte analyzer, in which the probe is moved above the diluted layer, and FIG. The state in which the probe descends to the diluted layer is shown.
  • the sample probe 22 that dispenses a sample from the sample container 52 containing the sample to the electrode unit units 11 and 12 rotates and moves around a predetermined position of its longitudinal end as a rotation center axis. , Position 22A, position 22B, and position 22C.
  • the probe portion 22b located at the end opposite to the longitudinal end where the rotation center axis of the sample probe 22 is located accompanies the rotational movement of the sample probe 22.
  • the dilution tanks 23a and 23b are arranged so as to be located along the flow line drawn.
  • the ion-selective electrode groups 24a and 24c and the comparative electrodes 24b and 24d are located below the moving range of the sample probe 22 (that is, the operating range of the cover unit 22a). Is also arranged so as to be located on the outside. Further, the first electrode unit 11 is located closest to the sample container 52 (the position of the probe portion 22b of the sample probe 22 at the position 22A), and the second electrode unit 12 is located farthest from the sample container 52. Each is arranged.
  • the first electrode unit 11 is detachably arranged below the operating range of the sample probe 22 and above the diluting tank 23a with an opening provided for the probe 22b to descend to the diluting tank 23a.
  • the second electrode unit 12 has an opening provided above the dilution tank 23b, the ion-selective electrode group 24c and the comparison electrode 24d so that the probe portion 22c descends to the dilution tank 23b.
  • the first electrode unit 11 has a detachably arranged dilution tank cover 25 (first) having an opening provided for the probe portion 22b to descend to the dilution tank 23a.
  • a dilution tank 23a is provided below the cover), and as shown in FIG. 9, the probe portion 22b descends to the dilution tank 23a to dispense the sample.
  • the ion-selective electrode group cover 26 is attached to the first electrode unit 11 to cover the ion-selective electrode group 24a, and the solenoid lock is placed inside the ion-selective electrode group cover 26 (downward side and ion-selective electrode group 24a side). It has a receiver 26a. Further, a solenoid lock mechanism 11a is provided at a position corresponding to the solenoid lock receiver 26a in the structure of the first electrode unit 11 different from the ion-selective electrode group cover 26.
  • the solenoid lock mechanism 11a moves a part of the ion-selective electrode group cover 26 with respect to the first electrode unit unit 11 by projecting a part thereof based on an electric signal from the control unit 31 and engaging with the solenoid lock receiver 26a. Is restricted and fixed so that it cannot be removed (locked state). Further, the solenoid lock mechanism 11a causes the ion-selective electrode group cover 26 to be the first electrode unit 11 by retracting a part of the protrusion based on the electric signal from the control unit 31 from the solenoid lock receiving 26a side. On the other hand, it is in a removable state (unlocked state).
  • the solenoid lock mechanism 11a and the solenoid lock receiver 26a form an interlock in which the ion-selective electrode group cover 26 (second cover) can be fixed to the electrode unit 11.
  • the ion-selective electrode group cover 26 can be removed from the first electrode unit 11 as shown in FIG. By removing the ion-selective electrode group cover 26, the operator can access the internal components of the first electrode unit 11 such as the ion-selective electrode group 24a and the comparison electrode 24b.
  • the ion-selective electrode group 24a is detachably provided with respect to the first electrode unit 11, and can be removed from the ion-selective electrode group mounting portion 124a by an operator (see FIG. 4).
  • the operator can remove the ion-selective electrode group 24a that needs to be replaced based on the requirements such as the number of times of use, and attach a new ion-selective electrode group 24a to the ion-selective electrode group mounting portion 124a.
  • the ion-selective electrode group 24a can be replaced.
  • the ion-selective electrode group mounting unit 124a has a sensor function for detecting that the ion-selective electrode group 24a is normally mounted, and transmits the detection result to the control unit 31 by an electric signal. do. That is, the control unit 31 has a state in which the ion-selective electrode group 24a is mounted (see FIG. 3) and a state in which the ion-selective electrode group 24a is removed, depending on the detection result of the ion-selective electrode group mounting unit 124a (see FIG. 3). (See FIG. 4) can be determined.
  • the ion-selective electrode group cover mounting sensor that detects that the ion-selective electrode group cover 26 is normally mounted on the first electrode section unit 11 is attached to the first electrode section unit 11.
  • 11c and a lock mechanism operation detection sensor 11b for detecting that the solenoid lock mechanism 11a is operating (locked state) are provided.
  • the ion-selective electrode group cover mounting sensor 11c is, for example, a mechanical sensor that detects an object when pressed, and by arranging it at a position where it is pressed by the solenoid lock receiver 26a, the ion-selective electrode group cover 26 Detects that is mounted in the normal position.
  • the detection result of the ion-selective electrode group cover mounting sensor 11c is sent to the control unit 31 by an electric signal. That is, when the control unit 31 detects that the ion-selective electrode group cover mounting sensor 11c is pressed (see FIG. 2 and the like), the control unit 31 determines that the ion-selective electrode group cover 26 is mounted in a normal position. However, in the case of non-detection in which the pressing is not detected (see FIG. 3 and the like), it can be determined that the ion-selective electrode group cover 26 is not attached (or is not attached in the normal position).
  • the lock mechanism operation detection sensor 11b is, for example, a mechanical sensor that detects an object by being pressed (pushed in), and is arranged at a position where the solenoid lock mechanism 11a is pressed by protruding a part of the solenoid lock mechanism 11a. As a result, it is detected that the solenoid lock mechanism 11a is operating (locked).
  • the detection result of the lock mechanism operation detection sensor 11b is sent to the control unit 31 by an electric signal. That is, when the lock mechanism operation detection sensor 11b is detected to be pressed (see FIG. 2 and the like), the control unit 31 determines that the solenoid lock mechanism 11a is operating (is in a locked state). In the case of non-detection in which the press is not detected (see FIG.
  • FIG. 5 is a flowchart showing the processing contents in the electrolyte analyzer.
  • control unit 31 of the electrolyte analyzer 100 first determines whether or not the ion-selective electrode group 24a of the first electrode unit 11 needs to be replaced (step S100).
  • the necessity of replacement of the ion-selective electrode group 24a is determined by, for example, whether or not the number of times used for the measurement exceeds a predetermined limit number of times.
  • step S110 When the determination result in step S100 is YSE, that is, when it is determined that the ion-selective electrode group 24a needs to be replaced, the measurement process of the first electrode unit 11 is stopped (step S110).
  • the control unit 31 displays and sounds that the ion-selective electrode group 24a of the first electrode unit 11 needs to be replaced and that the measurement process by the first electrode unit 11 has been stopped.
  • step S120 By notifying the operator by such means (step S120) and retracting a protruding part of the solenoid lock mechanism 11a of the first electrode unit 11 from the solenoid lock receiver 26a, the lock is released (interlock release). (Step S130).
  • the ion-selective electrode group cover 26 of the first electrode unit 11 becomes removable, and the operator can access and replace the ion-selective electrode group 24a. Further, since the dilution tank cover 25 located below the movable range of the sample probe 22 is not removed, the sample probe 22 can pass above the first electrode portion unit 11 and the second electrode portion is moving. Dispensing of the sample to the unit 12 can be continued, and the measurement process can be continued. That is, by continuing the measurement process by the second electrode unit 12 without inhibiting the dispensing of the sample by the sample probe 22 into the second electrode unit 12, which does not require replacement of the ion-selective electrode group 24c. The ion-selective electrode group 24a of the first electrode unit 11 can be replaced while suppressing a decrease in processing capacity.
  • step S140 it is determined whether or not the exchange of the ion-selective electrode group 24a by the operator is completed.
  • the normal mounting of the ion-selective electrode group 24a is detected by the ion-selective electrode group mounting unit 124a, and the normal mounting of the ion-selective electrode group cover 26 is the ion-selective electrode group.
  • the cover mounting sensor 11c it is determined that the replacement is completed.
  • step S140 determines whether the exchange of the ion-selective electrode group 24a is not completed. If the determination result in step S140 is NO, that is, if the exchange of the ion-selective electrode group 24a is not completed, the processing of steps S110 to S130 is continued.
  • step S140 If the determination result in step S140 is YES, that is, if it is determined that the exchange of the ion-selective electrode group 24a is completed, then one of the solenoid lock mechanisms 11a of the first electrode unit 11 The portion is projected toward the solenoid receiving 26a to bring it into a locked state (interlock operation) (step S150).
  • step S160 it is determined whether or not the interlock has operated normally.
  • the operation determination of the interlock is performed based on the detection result from the lock mechanism operation detection sensor 11b.
  • step S160 If the determination result in step S160 is NO, the operator is notified of the content instructing the operation confirmation of the interlock by displaying on a display device (not shown) by the control unit 31 or by voice (step S161). The process returns to step S150.
  • step S160 If the determination result in step S160 is YES, the first electrode unit 11 is operated to start the measurement process (step S170), and the process ends.
  • step S200 it is determined whether or not the ion-selective electrode group 24c of the second electrode unit 12 needs to be replaced. If the determination result in step S100 is NO, that is, if it is determined that the ion-selective electrode group 24a does not need to be replaced, the operation of the first electrode unit 11 is continued and the measurement process is performed. continue. That is, the sample probe 22 sucks the sample from the sample container 52 at the position 22A and discharges it to the dilution tank 23a of the first electrode unit 11 or the dilution tank 23b of the second electrode unit 12 at the position 22B or 22C. By doing so, the measurement process by the first electrode unit 11 or the second electrode unit 12 is performed.
  • step S200 When the determination result in step S200 is NO, that is, when it is determined that the ion-selective electrode group 24c does not need to be replaced, the first electrode unit 11 and the second electrode unit 12 are operated. Continue and continue the measurement process. That is, the sample probe 22 sucks the sample from the sample container 52 at the position 22A and discharges it to the dilution tank 23a of the first electrode unit 11 or the dilution tank 23b of the second electrode unit 12 at the position 22B or 22C. By doing so, the measurement process by the first electrode unit 11 or the second electrode unit 12 is performed.
  • step S100 determines whether the ion-selective electrode 24a of the first electrode unit 11 needs to be replaced.
  • the measurement of the first electrode unit 11 is performed.
  • step S110 the determination in step S200 is performed.
  • the determination result in step S200 is YES, that is, when it is determined that the ion-selective electrode group 24c of the second electrode unit 12 needs to be replaced.
  • the second electrode unit 12 The measurement process is stopped (step S210), and thereafter, the same process as the process of steps S120 to S170 for the first electrode unit 11 is performed, and the process is completed.
  • the second electrode unit 12 has a solenoid lock mechanism 11a, a lock mechanism operation detection sensor 11b, and ion selectivity of the first electrode unit 11 shown in FIGS. 2 to 4 and 7. It has a configuration corresponding to each of the electrode group cover mounting sensor 11c and the solenoid lock receiver 26a, and the processing of steps S220 to S270 is performed using these, and the processing is completed.
  • the second electrode unit 11 in the state where it is not necessary to replace the ion-selective electrode 24c of the second electrode unit 12, the second electrode unit 11 is in operation during the second period.
  • the electrode unit 12 of the above is also operating, and the second electrode unit 12 is operating even during the period when the first electrode unit 11 is stopped.
  • the diluting tanks 23a and 23b for diluting the sample dispensed by the sample probe 22 and the ion for measuring a specific ion concentration in the sample diluted in the diluting tanks 23a and 23b are provided, and the first electrode unit 11 is below the operating range of the sample probe 22.
  • the processing capacity can be increased.
  • the ion-selective electrode group 24a can be replaced while suppressing the decrease.
  • the measurement process cannot be performed during the replacement of the ion-selective electrode group 24a, but the sample is dispensed into the diluting tank 23a and the sample is diluted / stirred in the diluting tank 23a. Can be continued.
  • This embodiment illustrates a case where the second electrode unit 12B of the analysis unit 1B of the electrolyte analyzer 100B has a dilution tank cover 28 and an ion-selective electrode group cover 29.
  • FIG. 6 is a top view schematically showing a structural example and an arrangement example of the first and second electrode unit in the analysis unit of the electrolyte analyzer of the present embodiment.
  • the same members as those in the first embodiment are designated by the same reference numerals, and the description thereof will be omitted.
  • the first and second electrode unit units 11 and 12B are the flow lines of the sample probe 22 for dispensing the sample from the sample container 52 containing the sample to the electrode units 11 and 12B (accurately). Is arranged so that the dilution tanks 23a and 23b are located along the flow line of the probe portion 22b). Further, in the first and second electrode unit units 11 and 12B, the ion-selective electrode groups 24a and 24c and the comparative electrodes 24b and 24d are located below the moving range of the sample probe 22 (that is, the operating range of the cover unit 22a). Is also arranged so as to be located on the outside. Further, the first electrode unit 11 is located closest to the sample container 52 (the position of the probe portion 22b of the sample probe 22 at the position 22A), and the second electrode unit 12B is located farthest from the sample container 52. Each is arranged.
  • the second electrode unit 12B is a detachably arranged diluting unit having an opening provided for the probe unit 22c to descend to the diluting tank 23b above the diluting tank 23b below the operating range of the sample probe 22.
  • the ion-selective electrode group 24c and the ion-selective electrode group 24c are detachably arranged so as to cover the upper part of the ion-selective electrode group 24c and the comparison electrode 24d in a range not below the operating range of the tank cover 28 (first cover) and the sample probe 22. It has a cover 29 (second cover).
  • the ion-selective electrode group cover 29 has a solenoid lock receiver 29a similar to the ion-selective electrode group cover 26. Further, the second electrode unit 12B has the same solenoid lock mechanism 12a as the first electrode unit 11. That is, the solenoid lock mechanism 12a and the solenoid lock receiver 29a form an interlock capable of fixing the ion-selective electrode group cover 29 (second cover) to the second electrode unit 12B.
  • the ion-selective electrode group cover mounting sensor that detects that the ion-selective electrode group cover 29 is normally mounted on the second electrode unit 12B is mounted on the second electrode unit 12B.
  • 12c and a lock mechanism operation detection sensor 12b for detecting that the solenoid lock mechanism 12a is operating (locked state) are provided.
  • first electrode unit 11 can be stopped and the second electrode unit 12B can continue to operate as in the first embodiment.
  • the measurement process cannot be performed during the replacement of the ion-selective electrode group 24c, but the sample is dispensed into the diluting tank 23b and the sample is diluted / stirred in the diluting tank 23b. Can be continued. Further, in the same procedure as the procedure for removing the second cover 26 of the first electrode unit shown in the first embodiment, the second cover 29 of the second electrode unit is placed below the probe portion 22b. Is not placed and does not interfere, so it can be removed independently.
  • the second covers 26 and 29 are removable in the first electrode unit 11 and the second electrode unit 12B has been described as an example.
  • the second covers 26 and 29 may be connected to the first electrode unit 11 and the second electrode unit 12B via a hinge mechanism or the like so as to be openable and closable.
  • the present invention is not limited to this, and for example, three or more electrode unit units are provided and the sample container 52 is provided.
  • the electrode unit located closest to the sample container 52 has a first cover and a second cover, and the electrode unit located farthest from the sample container 52 has a third cover. It may be configured.
  • the ion-selective electrode group cover mounting sensor 11c and the lock mechanism operation detection sensor 11b are mechanical sensors
  • the present invention is not limited to this, for example.
  • a laser type sensor or a sensor that makes a determination based on a camera image may be used.
  • the sensor function of the ion-selective electrode group mounting unit 124a and the ion-selective electrode group cover mounting sensor 11c determine whether or not the replacement of the ion-selective electrode group is completed.
  • the case where the replacement is performed based on the detection result of the above has been described as an example, but the present invention is not limited to this. It may be determined that the replacement of the sex electrode group is completed. However, even in this case as well, it is determined whether or not the ion-selective electrode group has been normally replaced based on the sensor function of the ion-selective electrode group mounting unit 124a and the detection result of the ion-selective electrode group cover mounting sensor 11c. Is preferable. Further, the operator may read an individual identification marker such as a bar code provided on the ion-selective electrode group to confirm that the electrode has been replaced with a new ion-selective electrode. good.
  • the present invention is not limited to the one including all the configurations described in the above-described embodiment, and includes the one in which a part of the configurations is deleted. Further, each of the above configurations, functions and the like may be realized by designing a part or all of them by, for example, an integrated circuit. Further, each of the above configurations, functions, and the like may be realized by software by the processor interpreting and executing a program that realizes each function.

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Abstract

The present invention comprises a plurality of electrode units (first and second electrode units 11, 12) respectively including dilution tanks 23a, 23b for diluting a sample dispensed by a sample probe 22 and ion-selective electrode groups 24a, 24c for measuring specific ion concentrations in the sample diluted in the dilution tanks 23a, 23b, wherein the first electrode unit 11 includes: a dilution tank cover 25 (first cover) which is detachably disposed and has an opening provided for a probe portion 22b above the dilution tank 23a to descend to the dilution tank 23a below the operating range of the sample probe 22; and an ion-selective electrode group cover 26 (second cover) detachably arranged so as to cover the upper part of the ion-selective electrode group 24a in a range not below the operating range of the sample probe 22. This makes it possible to replace the ion-selective electrode while reducing a decrease in processing capacity.

Description

電解質分析装置Electrolyte analyzer
　本発明は、電解質分析装置に関する。 The present invention relates to an electrolyte analyzer.
　電解質分析装置は、人体の血液、尿等の電解質溶液中に含まれる特定の電解質濃度を測定する装置であり、イオン選択性電極を利用して濃度測定を行うものである。電解質分析装置としては、例えば、フロー型電解質分析装置が知られている。フロー型電解質分析装置では、電解質溶液としての血清を直接、あるいは検体希釈液により希釈したサンプル溶液を、イオン選択性電極に供給し、イオン選択性電極と比較電極液との液間電位を測定する。続いて（又は測定に先立って）、イオン選択性電極に電解質濃度が既知である標準液を供給し、血清（又はサンプル溶液）と同様に比較電極液との液間電位を測定する。そして、標準液の液間電位と血清（又はサンプル溶液）の液間電位の２つの液間電位から血清（又はサンプル溶液）の電解質濃度を算出することができる。 The electrolyte analyzer is a device that measures the concentration of a specific electrolyte contained in the electrolyte solution of human blood, urine, etc., and measures the concentration using an ion-selective electrode. As the electrolyte analyzer, for example, a flow type electrolyte analyzer is known. In the flow type electrolyte analyzer, a sample solution obtained by directly diluting serum as an electrolyte solution or diluted with a sample diluent is supplied to an ion-selective electrode, and the liquid potential between the ion-selective electrode and the comparative electrode solution is measured. .. Subsequently (or prior to the measurement), a standard solution having a known electrolyte concentration is supplied to the ion-selective electrode, and the liquid potential with the comparative electrode solution is measured in the same manner as the serum (or sample solution). Then, the electrolyte concentration of serum (or sample solution) can be calculated from the two liquid potentials of the standard solution and the serum (or sample solution).
　このようなフロー型電解質分析装置で用いられるイオン選択性電極は、有効期限や測定回数などに制限があり、定期的な交換を必要とする。そのため、例えば、分析中にイオン選択性電極が有効期限を迎えた場合には、新しいイオン選択性電極に交換するまで分析を行うことができず、処理能力の低下を招いてしまう。 The ion-selective electrode used in such a flow-type electrolyte analyzer has a limited expiration date and the number of measurements, and requires regular replacement. Therefore, for example, when the ion-selective electrode reaches the expiration date during the analysis, the analysis cannot be performed until the ion-selective electrode is replaced with a new ion-selective electrode, resulting in a decrease in processing capacity.
　そこで、例えば、特許文献１には、複数個の電気化学的センサからなるセンサ群を具備した生体液分析装置において、上記センサ群に含まれるセンサと同一の電気化学的センサを含むセンサ群を複数個互いに並列に配置し、試料測定時にいずれかのセンサ群を選択可能に構成した生体液分析装置が開示されている。 Therefore, for example, in Patent Document 1, in a biofluid analyzer including a sensor group composed of a plurality of electrochemical sensors, a plurality of sensor groups including the same electrochemical sensor as the sensor included in the sensor group are provided. A biofluid analyzer is disclosed in which the sensors are arranged in parallel with each other and one of the sensor groups can be selected at the time of sample measurement.
特開平６－２７３３７２号公報Japanese Unexamined Patent Publication No. 6-273372
　しかしながら、上記従来技術においては、例えば、並列に配置した複数のセンサを覆うカバーを開ける際にサンプルプローブと干渉することが考えられるため、センサを交換する際には分析を中断する必要があり、処理能力の低下を招いてしまうという問題がある。 However, in the above-mentioned prior art, for example, it is conceivable that the sample probe may interfere with the sample probe when opening the cover covering a plurality of sensors arranged in parallel. Therefore, it is necessary to interrupt the analysis when exchanging the sensors. There is a problem that the processing capacity is reduced.
　本発明は上記に鑑みてなされたものであり、処理能力の低下を抑制しつつイオン選択性電極を交換することができる電解質分析装置を提供することを目的とする。 The present invention has been made in view of the above, and an object of the present invention is to provide an electrolyte analyzer capable of exchanging an ion-selective electrode while suppressing a decrease in processing capacity.
　本願は上記課題を解決する手段を複数含んでいるが、その一例を挙げるならば、サンプルプローブにより分注された試料を希釈する希釈槽と、前記希釈槽で希釈された試料中の特定のイオン濃度を測定するイオン選択性電極とをそれぞれ有する複数の電極部ユニットを備え、前記複数の電極部ユニットのうち少なくとも１つの電極部ユニットは、前記サンプルプローブの動作範囲の下方において前記希釈槽の上方にプローブ部が前記希釈槽まで下降するために設けられた開口部を有する着脱可能に配置された第１のカバーと、前記サンプルプローブの動作範囲の下方とならない範囲において前記イオン選択性電極の上方を覆うように着脱可能に配置された第２のカバーとを有するものとする。 The present application includes a plurality of means for solving the above problems, for example, a diluting tank for diluting a sample dispensed by a sample probe and a specific ion in the sample diluted in the diluting tank. A plurality of electrode unit units each having an ion-selective electrode for measuring a concentration are provided, and at least one electrode unit among the plurality of electrode units is below the operating range of the sample probe and above the diluting tank. A detachably arranged first cover having an opening provided for the probe portion to descend to the diluting tank, and above the ion-selective electrode in a range not below the operating range of the sample probe. It shall have a second cover that is detachably arranged so as to cover the above.
　処理能力の低下を抑制しつつイオン選択性電極を交換することができる。 The ion-selective electrode can be replaced while suppressing the decrease in processing capacity.
電解質分析装置の全体構成を概略的に示す図である。It is a figure which shows the whole structure of the electrolyte analyzer schematicly. 電解質分析装置の分析部における第１及び第２の電極部ユニットの構造例および配置例を概略的に示す上面図であり、イオン選択性電極群カバーが第１の電極部ユニットに装着されている状態を示す図である。It is a top view which shows the structural example and the arrangement example of the 1st and 2nd electrode part units in the analysis part of an electrolyte analyzer schematicly, and the ion-selective electrode group cover is attached to the 1st electrode part unit. It is a figure which shows the state. 電解質分析装置の分析部における第１及び第２の電極部ユニットの構造例および配置例を概略的に示す上面図であり、イオン選択性電極群カバーが取り外されている状態を示す図である。It is the top view which shows the structural example and the arrangement example of the 1st and 2nd electrode part units in the analysis part of an electrolyte analyzer schematicly, and is the figure which shows the state which the ion-selective electrode group cover is removed. 電解質分析装置の分析部における第１及び第２の電極部ユニットの構造例および配置例を概略的に示す上面図であり、イオン選択性電極群が取り外されている状態を示す図である。It is a top view which shows the structural example and the arrangement example of the 1st and 2nd electrode part units in the analysis part of an electrolyte analyzer schematicly, and is the figure which shows the state which the ion-selective electrode group is removed. 電解質分析装置における処理内容を示すフローチャートである。It is a flowchart which shows the processing content in the electrolyte analyzer. 第２の実施の形態の電解質分析装置の分析部における第１及び第２の電極部ユニットの構造例および配置例を概略的に示す上面図である。It is a top view schematically showing the structural example and the arrangement example of the 1st and 2nd electrode part units in the analysis part of the electrolyte analyzer of 2nd Embodiment. 電解質分析装置の分析部における第１及び第２の電極部ユニットの構造例および配置例を概略的に示す上面図であり、希釈槽カバーが取り外されている状態を示す図である。It is a top view schematically showing the structural example and the arrangement example of the 1st and 2nd electrode part units in the analysis part of the electrolyte analyzer, and is the figure which shows the state which the dilution tank cover is removed. 電解質分析装置の分析部における第１の電極部ユニットの構造例および配置例を概略的に示す側面図であり、イオン選択性電極群カバーが第１の電極部ユニットに装着されている状態を示す図である。It is a side view which shows the structural example and the arrangement example of the 1st electrode part unit in the analysis part of an electrolyte analyzer schematicly, and shows the state which the ion-selective electrode group cover is attached to the 1st electrode part unit. It is a figure. 電解質分析装置の分析部における第１の電極部ユニットの構造例および配置例を概略的に示す側面図であり、イオン選択性電極群カバーが第１の電極部ユニットに装着されている状態を示す図である。It is a side view which shows the structural example and the arrangement example of the 1st electrode part unit in the analysis part of an electrolyte analyzer schematicly, and shows the state which the ion-selective electrode group cover is attached to the 1st electrode part unit. It is a figure.
　以下、本発明の実施の形態を図面を参照しつつ説明する。 Hereinafter, embodiments of the present invention will be described with reference to the drawings.
　＜第１の実施の形態＞
  本発明の第１の実施の形態を図１～図５を参照しつつ詳細に説明する。 <First Embodiment>
The first embodiment of the present invention will be described in detail with reference to FIGS. 1 to 5.
　図１は、本発明の実施の形態に係る電解質分析装置の全体構成を概略的に示す図である。なお、本実施の形態においては、電解質分析装置の一例として、イオン選択性電極（ＩＳＥ：Ion Selective Electrode）を用いたフロー型電解質分析装置（以降、単に電解質分析装置と称する）を示して説明する。 FIG. 1 is a diagram schematically showing the overall configuration of the electrolyte analyzer according to the embodiment of the present invention. In the present embodiment, as an example of the electrolyte analyzer, a flow-type electrolyte analyzer using an ion-selective electrode (ISE: Ion Selective Electrode) (hereinafter, simply referred to as an electrolyte analyzer) will be described. ..
　図１において、電解質分析装置１００は、分析対象である試料（例えば、患者の検体など）の中の特定のイオン濃度を測定する分析部１と、分析部１を含む電解質分析装置全体の動作を制御する制御部３１（制御装置）とを備えている。 In FIG. 1, the electrolyte analyzer 100 operates the analysis unit 1 for measuring a specific ion concentration in a sample to be analyzed (for example, a patient's sample) and the operation of the entire electrolyte analyzer including the analysis unit 1. It is provided with a control unit 31 (control device) for controlling.
　分析部１は、分析対象である試料を収容する検体容器５２と、試料中のイオン濃度を測定する複数の電極部ユニット（本実施の形態においては第１及び第２の電極部ユニット１１，１２の２つの電極部ユニットを例示する）と、検体容器５２に収容された試料を第１及び第２の電極部ユニット１１，１２に分注するサンプルプローブ２２と、比較電極液を収容する比較電極液ボトル５５ａ，５５ｂと、希釈液を収容する希釈液ボトル５６ａ，５６ｂと、測定後に不要となった各溶液を廃液として収容する廃液溜め５４と、廃液を吸引して廃液溜め５４に排出する吸引器５３ａ，５３ｂとから概略構成されている。 The analysis unit 1 includes a sample container 52 that houses the sample to be analyzed, and a plurality of electrode unit units that measure the ion concentration in the sample (in the present embodiment, the first and second electrode unit units 11 and 12). 2), the sample probe 22 that dispenses the sample contained in the sample container 52 into the first and second electrode units 11 and 12, and the comparison electrode that houses the comparative electrode solution. The liquid bottles 55a and 55b, the diluted liquid bottles 56a and 56b containing the diluted liquid, the waste liquid reservoir 54 containing each solution that is no longer needed after the measurement as waste liquid, and the suction that sucks the waste liquid and discharges it to the waste liquid reservoir 54. It is roughly composed of vessels 53a and 53b.
　サンプルプローブ２２は、一端を中心として水平方向に回動可能に設けられたカバー部２２ａと、カバー部２２ａの他端から下方に突出して延在するように配置されたプローブ部２２ｂとから構成されている。サンプルプローブ２２は、上下方向に移動可能であり、カバー部２２ａを回動することでプローブ部２２ｂの位置を変えるとともに、上下方向に移動させることで検体容器５２や第１及び第２の電極部ユニット１１，１２への挿入を行い、図示しないポンプ装置によって試料の分注（吸引および吐出）を行う。なお、図１及び後述する図２～図４においては、サンプルプローブ２２の位置について、検体容器５２から試料を吸引する場合を位置２２Ａ、試料を第１の電極部ユニット１１に分注（吐出）する場合を位置２２Ｂ、試料を第２の電極部ユニット１２に分注（吐出）する場合を位置２２Ｃとして括弧書きで示している。 The sample probe 22 is composed of a cover portion 22a provided so as to be rotatable in the horizontal direction around one end, and a probe portion 22b arranged so as to project downward from the other end of the cover portion 22a and extend. ing. The sample probe 22 can be moved in the vertical direction, and the position of the probe portion 22b can be changed by rotating the cover portion 22a, and the sample container 52 and the first and second electrode portions can be moved in the vertical direction. The sample is inserted into the units 11 and 12, and the sample is dispensed (suctioned and discharged) by a pump device (not shown). In addition, in FIG. 1 and FIGS. 2 to 4 described later, regarding the position of the sample probe 22, the case where the sample is sucked from the sample container 52 is the position 22A, and the sample is dispensed (discharged) to the first electrode unit 11. The case where the sample is dispensed (discharged) to the second electrode unit 12 is shown in parentheses as the position 22B, and the case where the sample is dispensed (discharged) to the second electrode unit 12 is shown in parentheses.
　第１の電極部ユニット１１は、検体を希釈液ボトル５６ａから流路を介して送られる希釈液により希釈する希釈槽２３ａと、希釈槽２３ａから流路を介して送られる希釈された試料のイオン濃度を測定する複数のイオン選択性電極からなるイオン選択性電極群２４ａと、比較電極液ボトル５５ａから流路を介して送られる比較溶液が接液する比較電極２４ｂとを有している。イオン選択性電極群２４ａは、例えば、ナトリウムイオン（Ｎａ＋）、カリウムイオン（Ｋ＋）、カルシウムイオン（Ｃａ＋＋）、クロールイオン（Ｃｌ－）などのイオン濃度をそれぞれ測定する複数のイオン選択性電極から構成されている。 The first electrode unit 11 has a diluting tank 23a that dilutes the sample with the diluting liquid sent from the diluting liquid bottle 56a via the flow path, and ions of the diluted sample sent from the diluting tank 23a via the flow path. It has an ion-selective electrode group 24a composed of a plurality of ion-selective electrodes for measuring the concentration, and a comparison electrode 24b with which a comparative solution sent from the comparison electrode liquid bottle 55a via a flow path is in contact. The ion-selective electrode group 24a is composed of a plurality of ion-selective electrodes for measuring ion concentrations such as sodium ion (Na +), potassium ion (K +), calcium ion (Ca ++), and chlor ion (Cl-), respectively. Has been done.
　第１の電極部ユニット１１における測定処理では、まず、検体容器５２に収容された試料を位置２２Ａにおいて吸引したサンプルプローブ２２が位置２２Ｂに移動し、希釈槽２３ａに吐出（分注）される。続いて、流路の開閉を行うバルブや液体の吸引送出を行うシリンジなどで構成された送液機構５８ａにより、希釈液ボトル５６ａの希釈液が流路を介して希釈槽２３ａに吐出される。これにより、希釈槽２３ａにおいて試料が希釈・撹拌される。希釈槽２３ａで希釈・攪拌された試料（以降、試料溶液と称する）は、吸引器５３ａにより吸引されることで流路を介してイオン選択性電極群２４ａに送液される。また、送液機構５７ａにより、比較電極液ボトル５５ａの比較電極液が流路を介して比較電極２４ｂに送液される。 In the measurement process in the first electrode unit 11, first, the sample probe 22 that sucks the sample contained in the sample container 52 at the position 22A moves to the position 22B and is discharged (dispensed) to the dilution tank 23a. Subsequently, the diluting liquid of the diluting liquid bottle 56a is discharged to the diluting tank 23a via the diluting liquid bottle 56a by the liquid feeding mechanism 58a composed of a valve for opening and closing the flow path and a syringe for sucking and delivering the liquid. As a result, the sample is diluted and stirred in the dilution tank 23a. The sample diluted and stirred in the diluting tank 23a (hereinafter referred to as a sample solution) is sucked by the suction device 53a and sent to the ion-selective electrode group 24a via the flow path. Further, the comparative electrode liquid of the comparative electrode liquid bottle 55a is fed to the comparative electrode 24b via the flow path by the liquid feeding mechanism 57a.
　イオン選択性電極群２４ａに送液された試料溶液と比較電極２４ｂに送液された比較電極液とが接液することで、イオン選択性電極群２４ａの各イオン選択性電極と比較電極２４ｂとが電気的に導通する。この状態で、比較電極２４ｂとイオン選択性電極群２４ａの各イオン選択性電極との電位差を測定し、得られた電位差に基づいて試料溶液に含まれる特定のイオンの濃度を測定する。 When the sample solution sent to the ion-selective electrode group 24a and the comparative electrode solution sent to the comparison electrode 24b come into contact with each other, the ion-selective electrodes and the comparison electrode 24b of the ion-selective electrode group 24a are combined with each other. Is electrically conductive. In this state, the potential difference between the comparative electrode 24b and each ion-selective electrode of the ion-selective electrode group 24a is measured, and the concentration of a specific ion contained in the sample solution is measured based on the obtained potential difference.
　具体的には、例えば、イオン選択性電極群２４ａの各イオン選択性電極には、試料溶液中の特定のイオンの濃度に応じて起電力が変化する性質を持つイオン感応膜が貼り付けられている。イオン選択性電極は、試料溶液中の各イオン濃度に応じた起電力を出力するので、イオン選択性電極群２４ａの各イオン選択性電極と比較電極２４ｂとの間の起電力を取得し、各イオンについて取得した起電力から検体中のイオン濃度を演算する。 Specifically, for example, an ion-sensitive film having a property that the electromotive force changes according to the concentration of a specific ion in the sample solution is attached to each ion-selective electrode of the ion-selective electrode group 24a. There is. Since the ion-selective electrode outputs an electromotive force according to each ion concentration in the sample solution, the electromotive force between each ion-selective electrode of the ion-selective electrode group 24a and the comparative electrode 24b is acquired, and each of them obtains the electromotive force. The ion concentration in the sample is calculated from the electromotive force acquired for the ion.
　測定結果は、制御部３１に送られ、例えば、図示しない表示装置に表示される。イオン濃度の測定が終了すると、イオン選択性電極群２４ａ及び比較電極２４ｂの流路の試料溶液及び比較電極液が吸引器５３ａにより吸引され、廃液溜め５４に排出される。 The measurement result is sent to the control unit 31, and is displayed, for example, on a display device (not shown). When the measurement of the ion concentration is completed, the sample solution and the comparative electrode solution in the flow paths of the ion-selective electrode group 24a and the comparative electrode 24b are sucked by the aspirator 53a and discharged to the waste liquid reservoir 54.
　第２の電極部ユニット１２は、第１の電極部ユニット１１と同様の構成を有している。すなわち、第２の電極部ユニット１２は、検体を希釈液ボトル５６ｂから流路を介して送られる希釈液により希釈する希釈槽２３ｂと、希釈槽２３ｂから流路を介して送られる希釈された試料のイオン濃度を測定する複数のイオン選択性電極からなるイオン選択性電極群２４ｃと、比較電極液ボトル５５ｂから流路を介して送られる比較溶液が接液する比較電極２４ｄとを有している。 The second electrode unit 12 has the same configuration as the first electrode unit 11. That is, the second electrode unit 12 has a diluting tank 23b that dilutes the sample with the diluting liquid sent from the diluting liquid bottle 56b via the flow path, and the diluted sample sent from the diluting tank 23b via the flow path. It has an ion-selective electrode group 24c composed of a plurality of ion-selective electrodes for measuring the ion concentration of the above, and a comparison electrode 24d to which a comparative solution sent from the comparison electrode liquid bottle 55b via a flow path is in contact with the liquid. ..
　第２の電極部ユニット１２における測定処理では、まず、検体容器５２に収容された試料を位置２２Ａにおいて吸引したサンプルプローブ２２が位置２２Ｃに移動し、希釈槽２３ｂに吐出（分注）される。続いて、流路の開閉を行うバルブや液体の吸引送出を行うシリンジなどで構成された送液機構５８ｂにより、希釈液ボトル５６ｂの希釈液が流路を介して希釈槽２３ｂに吐出される。これにより、希釈槽２３ｂにおいて試料が希釈・撹拌される。希釈槽２３ｂで希釈・攪拌された試料（以降、試料溶液と称する）は、吸引器５３ｂにより吸引されることで流路を介してイオン選択性電極群２４ｃに送液される。また、送液機構５７ｂにより、比較電極液ボトル５５ｂの比較電極液が流路を介して比較電極２４ｄに送液される。 In the measurement process in the second electrode unit 12, first, the sample probe 22 that sucks the sample contained in the sample container 52 at the position 22A moves to the position 22C and is discharged (dispensed) to the dilution tank 23b. Subsequently, the diluting liquid of the diluting liquid bottle 56b is discharged to the diluting tank 23b via the diluting liquid bottle 56b by the liquid feeding mechanism 58b composed of a valve for opening and closing the flow path and a syringe for sucking and delivering the liquid. As a result, the sample is diluted and stirred in the dilution tank 23b. The sample diluted and stirred in the diluting tank 23b (hereinafter referred to as a sample solution) is sucked by the suction device 53b and sent to the ion-selective electrode group 24c via the flow path. Further, the comparative electrode liquid of the comparative electrode liquid bottle 55b is fed to the comparative electrode 24d via the flow path by the liquid feeding mechanism 57b.
　イオン選択性電極群２４ｃに送液された試料溶液と比較電極２４ｄに送液された比較電極液とが接液することで、イオン選択性電極群２４ｃの各イオン選択性電極と比較電極２４ｄとが電気的に導通する。この状態で、比較電極２４ｄとイオン選択性電極群２４ｃの各イオン選択性電極との電位差を測定し、得られた電位差に基づいて試料溶液に含まれる特定のイオンの濃度を測定することができる。測定結果は、制御部３１に送られ、例えば、図示しない表示装置に表示される。イオン濃度の測定が終了すると、イオン選択性電極群２４ｃ及び比較電極２４ｄの流路の試料溶液及び比較電極液が吸引器５３ｂにより吸引され、廃液溜め５４に排出される。 When the sample solution sent to the ion-selective electrode group 24c and the comparative electrode solution sent to the comparison electrode 24d come into contact with each other, each ion-selective electrode and the comparison electrode 24d of the ion-selective electrode group 24c are combined with each other. Is electrically conductive. In this state, the potential difference between the comparative electrode 24d and each ion-selective electrode of the ion-selective electrode group 24c can be measured, and the concentration of a specific ion contained in the sample solution can be measured based on the obtained potential difference. .. The measurement result is sent to the control unit 31, and is displayed, for example, on a display device (not shown). When the measurement of the ion concentration is completed, the sample solution and the comparative electrode solution in the flow paths of the ion-selective electrode group 24c and the comparative electrode 24d are sucked by the aspirator 53b and discharged to the waste liquid reservoir 54.
　図２～図４、図７は、電解質分析装置の分析部における第１及び第２の電極部ユニットの構造例および配置例を概略的に示す上面図であり、図２はイオン選択性電極群カバーが第１の電極部ユニットに装着されている状態を、図３はイオン選択性電極群カバーが取り外されている状態を、図４はイオン選択性電極群が取り外されている状態、図７は希釈槽カバーが取り外されている状態をそれぞれ示している。また、図８は、電解質分析装置の分析部における第１の電極部ユニットの構造例および配置例を概略的に示す側面図であり、プローブが希釈層の上方に移動した状態、図９は、プローブが希釈層まで下降した状態をそれぞれ示している。 2 to 4 and 7 are top views schematically showing structural examples and arrangement examples of the first and second electrode unit in the analysis unit of the electrolyte analyzer, and FIG. 2 is an ion-selective electrode group. FIG. 3 shows a state in which the cover is attached to the first electrode unit, FIG. 3 shows a state in which the ion-selective electrode group cover is removed, and FIG. 4 shows a state in which the ion-selective electrode group is removed. Indicates that the diluting tank cover has been removed. Further, FIG. 8 is a side view schematically showing a structural example and an arrangement example of the first electrode unit in the analysis unit of the electrolyte analyzer, in which the probe is moved above the diluted layer, and FIG. The state in which the probe descends to the diluted layer is shown.
　図２に示すように、試料を収容した検体容器５２から電極部ユニット１１，１２に試料を分注するサンプルプローブ２２は、自身の長手方向端部の所定の位置を回転中心軸として回転移動し、位置２２Ａ、位置２２Ｂ、位置２２Ｃの各位置間を移動できるよう構成される。第１及び第２の電極部ユニット１１，１２は、サンプルプローブ２２の回転中心軸の位置する長手方向端部とは反対側の端部に位置するプローブ部２２ｂがサンプルプローブ２２の回転移動に伴って描く動線に沿って希釈槽２３ａ，２３ｂが位置するように配置されている。また、第１及び第２の電極部ユニット１１，１２は、イオン選択性電極群２４ａ，２４ｃ及び比較電極２４ｂ，２４ｄがサンプルプローブ２２の移動範囲（すなわち、カバー部２２ａの動作範囲）の下方よりも外側に位置するように配置されている。また、検体容器５２（位置２２Ａにおけるサンプルプローブ２２のプローブ部２２ｂの位置）に最も近い位置に第１の電極部ユニット１１が、検体容器５２から最も離れた位置に第２の電極部ユニット１２がそれぞれ配置されている。 As shown in FIG. 2, the sample probe 22 that dispenses a sample from the sample container 52 containing the sample to the electrode unit units 11 and 12 rotates and moves around a predetermined position of its longitudinal end as a rotation center axis. , Position 22A, position 22B, and position 22C. In the first and second electrode unit units 11 and 12, the probe portion 22b located at the end opposite to the longitudinal end where the rotation center axis of the sample probe 22 is located accompanies the rotational movement of the sample probe 22. The dilution tanks 23a and 23b are arranged so as to be located along the flow line drawn. Further, in the first and second electrode unit units 11 and 12, the ion- selective electrode groups 24a and 24c and the comparative electrodes 24b and 24d are located below the moving range of the sample probe 22 (that is, the operating range of the cover unit 22a). Is also arranged so as to be located on the outside. Further, the first electrode unit 11 is located closest to the sample container 52 (the position of the probe portion 22b of the sample probe 22 at the position 22A), and the second electrode unit 12 is located farthest from the sample container 52. Each is arranged.
　第１の電極部ユニット１１は、サンプルプローブ２２の動作範囲の下方において希釈槽２３ａの上方に、プローブ部２２ｂが希釈槽２３ａまで下降するために設けられた開口部を有する着脱可能に配置された希釈槽カバー２５（第１のカバー）と、サンプルプローブ２２の動作範囲の下方とならない範囲においてイオン選択性電極群２４ａ及び比較電極２４ｂの上方を覆うように着脱可能に配置されたイオン選択性電極群カバー２６（第２のカバー）とを有している。また、第２の電極部ユニット１２は、希釈槽２３ｂとイオン選択性電極群２４ｃ及び比較電極２４ｄとの上方に、プローブ部２２ｃが希釈槽２３ｂまで下降するために設けられた開口部を有し、その他の部分を覆うように配置された第３のカバー２７を有している。また、図８に示すように第１の電極部ユニット１１は、プローブ部２２ｂが希釈槽２３ａまで下降するために設けられた開口部を有する着脱可能に配置された希釈槽カバー２５（第１のカバー）の下方に希釈槽２３ａを有し、図９に示すように
プローブ部２２ｂが希釈槽２３ａまで下降し、試料を分注する。 The first electrode unit 11 is detachably arranged below the operating range of the sample probe 22 and above the diluting tank 23a with an opening provided for the probe 22b to descend to the diluting tank 23a. The diluting tank cover 25 (first cover) and the ion-selective electrodes detachably arranged so as to cover the upper parts of the ion-selective electrode group 24a and the comparison electrode 24b within the range not below the operating range of the sample probe 22. It has a group cover 26 (second cover). Further, the second electrode unit 12 has an opening provided above the dilution tank 23b, the ion-selective electrode group 24c and the comparison electrode 24d so that the probe portion 22c descends to the dilution tank 23b. , Has a third cover 27 arranged to cover the other parts. Further, as shown in FIG. 8, the first electrode unit 11 has a detachably arranged dilution tank cover 25 (first) having an opening provided for the probe portion 22b to descend to the dilution tank 23a. A dilution tank 23a is provided below the cover), and as shown in FIG. 9, the probe portion 22b descends to the dilution tank 23a to dispense the sample.
　イオン選択性電極群カバー２６は、第１の電極部ユニット１１に装着されてイオン選択性電極群２４ａを覆う状態において、その内側（下方側であってイオン選択性電極群２４ａ側）にソレノイドロック受け２６ａを有している。また、第１の電極部ユニット１１のイオン選択性電極群カバー２６とは異なる構造部には、ソレノイドロック受け２６ａに対応する位置にソレノイドロック機構１１ａが設けられている。ソレノイドロック機構１１ａは、制御部３１からの電気信号に基づいて一部を突出させてソレノイドロック受け２６ａと係合させることにより、イオン選択性電極群カバー２６の第１の電極部ユニット１１に対する移動を制限して固定し、取り外しできない状態（ロック状態）とする。また、ソレノイドロック機構１１ａは、制御部３１からの電気信号に基づいて突出した一部をソレノイドロック受け２６ａ側から退避させることにより、イオン選択性電極群カバー２６を第１の電極部ユニット１１に対して取り外し可能な状態（ロック解除状態）とする。ここで、ソレノイドロック機構１１ａ及びソレノイドロック受け２６ａは、イオン選択性電極群カバー２６（第２のカバー）を電極部ユニット１１に対して固定可能なインターロックを構成する。 The ion-selective electrode group cover 26 is attached to the first electrode unit 11 to cover the ion-selective electrode group 24a, and the solenoid lock is placed inside the ion-selective electrode group cover 26 (downward side and ion-selective electrode group 24a side). It has a receiver 26a. Further, a solenoid lock mechanism 11a is provided at a position corresponding to the solenoid lock receiver 26a in the structure of the first electrode unit 11 different from the ion-selective electrode group cover 26. The solenoid lock mechanism 11a moves a part of the ion-selective electrode group cover 26 with respect to the first electrode unit unit 11 by projecting a part thereof based on an electric signal from the control unit 31 and engaging with the solenoid lock receiver 26a. Is restricted and fixed so that it cannot be removed (locked state). Further, the solenoid lock mechanism 11a causes the ion-selective electrode group cover 26 to be the first electrode unit 11 by retracting a part of the protrusion based on the electric signal from the control unit 31 from the solenoid lock receiving 26a side. On the other hand, it is in a removable state (unlocked state). Here, the solenoid lock mechanism 11a and the solenoid lock receiver 26a form an interlock in which the ion-selective electrode group cover 26 (second cover) can be fixed to the electrode unit 11.
　ソレノイドロック機構１１ａがロック解除状態である場合には、図３に示すように、イオン選択性電極群カバー２６を第１の電極部ユニット１１に対して取り外すことができる。イオン選択性電極群カバー２６を取り外すことにより、オペレータは、イオン選択性電極群２４ａや比較電極２４ｂなど、第１の電極部ユニット１１の内部の構成物にアクセスすることができる。 When the solenoid lock mechanism 11a is in the unlocked state, the ion-selective electrode group cover 26 can be removed from the first electrode unit 11 as shown in FIG. By removing the ion-selective electrode group cover 26, the operator can access the internal components of the first electrode unit 11 such as the ion-selective electrode group 24a and the comparison electrode 24b.
　イオン選択性電極群２４ａは、第１の電極部ユニット１１に対して着脱可能に設けられており、オペレータによってイオン選択性電極群装着部１２４ａから取り外すことができる（図４参照）。オペレータは、例えば、使用回数などの要件に基づいて交換が必要となったイオン選択性電極群２４ａを取り外し、新たなイオン選択性電極群２４ａをイオン選択性電極群装着部１２４ａに取り付けることで、イオン選択性電極群２４ａを交換することができる。なお、イオン選択性電極群装着部１２４ａは、イオン選択性電極群２４ａが正常に装着された状態であることを検知するセンサ機能を有しており、検知結果を電気信号によって制御部３１に送信する。すなわち、制御部３１は、イオン選択性電極群装着部１２４ａの検知結果によって、イオン選択性電極群２４ａが装着された状態（図３参照）と、イオン選択性電極群２４ａが取り外された状態（図４参照）とを判定することができる。 The ion-selective electrode group 24a is detachably provided with respect to the first electrode unit 11, and can be removed from the ion-selective electrode group mounting portion 124a by an operator (see FIG. 4). The operator can remove the ion-selective electrode group 24a that needs to be replaced based on the requirements such as the number of times of use, and attach a new ion-selective electrode group 24a to the ion-selective electrode group mounting portion 124a. The ion-selective electrode group 24a can be replaced. The ion-selective electrode group mounting unit 124a has a sensor function for detecting that the ion-selective electrode group 24a is normally mounted, and transmits the detection result to the control unit 31 by an electric signal. do. That is, the control unit 31 has a state in which the ion-selective electrode group 24a is mounted (see FIG. 3) and a state in which the ion-selective electrode group 24a is removed, depending on the detection result of the ion-selective electrode group mounting unit 124a (see FIG. 3). (See FIG. 4) can be determined.
　また、第１の電極部ユニット１１には、イオン選択性電極群カバー２６が第１の電極部ユニット１１に対して正常に装着された状態であることを検知するイオン選択性電極群カバー装着センサ１１ｃと、ソレノイドロック機構１１ａが動作していること（ロック状態となっていること）を検知するロック機構動作検知センサ１１ｂとが設けられている。 Further, the ion-selective electrode group cover mounting sensor that detects that the ion-selective electrode group cover 26 is normally mounted on the first electrode section unit 11 is attached to the first electrode section unit 11. 11c and a lock mechanism operation detection sensor 11b for detecting that the solenoid lock mechanism 11a is operating (locked state) are provided.
　イオン選択性電極群カバー装着センサ１１ｃは、例えば、押下されることで対象を検知する機械式センサであり、ソレノイドロック受け２６ａによって押下される位置に配置することで、イオン選択性電極群カバー２６が正常な位置に装着されていることを検知する。イオン選択性電極群カバー装着センサ１１ｃの検知結果は、電気信号によって制御部３１に送られる。すなわち、制御部３１は、イオン選択性電極群カバー装着センサ１１ｃの押下が検知された場合（図２等参照）には、イオン選択性電極群カバー２６が正常な位置に装着されていると判定し、押下が検知されない非検知の場合（図３等参照）には、イオン選択性電極群カバー２６が装着されていない（或いは、正常な位置に装着されていない）と判定することができる。 The ion-selective electrode group cover mounting sensor 11c is, for example, a mechanical sensor that detects an object when pressed, and by arranging it at a position where it is pressed by the solenoid lock receiver 26a, the ion-selective electrode group cover 26 Detects that is mounted in the normal position. The detection result of the ion-selective electrode group cover mounting sensor 11c is sent to the control unit 31 by an electric signal. That is, when the control unit 31 detects that the ion-selective electrode group cover mounting sensor 11c is pressed (see FIG. 2 and the like), the control unit 31 determines that the ion-selective electrode group cover 26 is mounted in a normal position. However, in the case of non-detection in which the pressing is not detected (see FIG. 3 and the like), it can be determined that the ion-selective electrode group cover 26 is not attached (or is not attached in the normal position).
　また、ロック機構動作検知センサ１１ｂは、例えば、押下される（押し込まれる）ことで対象を検知する機械式センサであり、ソレノイドロック機構１１ａの一部が突出することによって押下される位置に配置することで、ソレノイドロック機構１１ａが動作している（ロック状態となっている）ことを検知する。ロック機構動作検知センサ１１ｂの検知結果は、電気信号によって制御部３１に送られる。すなわち、制御部３１は、ロック機構動作検知センサ１１ｂの押下が検知された場合（図２等参照）には、ソレノイドロック機構１１ａが動作している（ロック状態となっている）と判定し、押下が検知されない非検知の場合（図３等参照）には、ソレノイドロック機構１１ａが動作している（ロック解除状態となっている）と判定することができる。また、制御部３１は、ソレノイドロック機構１１ａを動作させる電気信号を出力し、かつ、ロック機構動作検知センサ１１ｂの押下が検知されない場合には、ソレノイドロック機構１１ａの動作に異常が生じていると判定することができる。 Further, the lock mechanism operation detection sensor 11b is, for example, a mechanical sensor that detects an object by being pressed (pushed in), and is arranged at a position where the solenoid lock mechanism 11a is pressed by protruding a part of the solenoid lock mechanism 11a. As a result, it is detected that the solenoid lock mechanism 11a is operating (locked). The detection result of the lock mechanism operation detection sensor 11b is sent to the control unit 31 by an electric signal. That is, when the lock mechanism operation detection sensor 11b is detected to be pressed (see FIG. 2 and the like), the control unit 31 determines that the solenoid lock mechanism 11a is operating (is in a locked state). In the case of non-detection in which the press is not detected (see FIG. 3 and the like), it can be determined that the solenoid lock mechanism 11a is operating (in the unlocked state). Further, when the control unit 31 outputs an electric signal for operating the solenoid lock mechanism 11a and the pressing of the lock mechanism operation detection sensor 11b is not detected, it is said that the operation of the solenoid lock mechanism 11a is abnormal. It can be determined.
　以上のように構成した電解質分析装置１００の動作を図５を参照しつつ説明する。 The operation of the electrolyte analyzer 100 configured as described above will be described with reference to FIG.
　図５は、電解質分析装置における処理内容を示すフローチャートである。 FIG. 5 is a flowchart showing the processing contents in the electrolyte analyzer.
　図５において、電解質分析装置１００の制御部３１は、まず、第１の電極部ユニット１１のイオン選択性電極群２４ａの交換が必要か否かを判定する（ステップＳ１００）。イオン選択性電極群２４ａの交換の要否判定は、例えば、測定に用いた回数が予め定めた制限回数を超えたか否かで判定する。 In FIG. 5, the control unit 31 of the electrolyte analyzer 100 first determines whether or not the ion-selective electrode group 24a of the first electrode unit 11 needs to be replaced (step S100). The necessity of replacement of the ion-selective electrode group 24a is determined by, for example, whether or not the number of times used for the measurement exceeds a predetermined limit number of times.
　ステップＳ１００での判定結果がＹＳＥの場合、すなわち、イオン選択性電極群２４ａの交換が必要であると判定した場合には、第１の電極部ユニット１１の測定処理を停止し（ステップＳ１１０）、第１の電極部ユニット１１のイオン選択性電極群２４ａの交換が必要であり、第１の電極部ユニット１１による測定処理を停止したことを、制御部３１の図示しない表示装置への表示や音声等によりオペレータに報知するとともに（ステップＳ１２０）、第１の電極部ユニット１１のソレノイドロック機構１１ａの突出した一部をソレノイドロック受け２６ａから退避させることにより、ロック解除状態（インターロック解除）とする（ステップＳ１３０）。 When the determination result in step S100 is YSE, that is, when it is determined that the ion-selective electrode group 24a needs to be replaced, the measurement process of the first electrode unit 11 is stopped (step S110). The control unit 31 displays and sounds that the ion-selective electrode group 24a of the first electrode unit 11 needs to be replaced and that the measurement process by the first electrode unit 11 has been stopped. By notifying the operator by such means (step S120) and retracting a protruding part of the solenoid lock mechanism 11a of the first electrode unit 11 from the solenoid lock receiver 26a, the lock is released (interlock release). (Step S130).
　このとき、第１の電極部ユニット１１のイオン選択性電極群カバー２６は取り外し可能となり、オペレータはイオン選択性電極群２４ａにアクセスして交換することが可能となる。また、サンプルプローブ２２の可動範囲の下方に位置する希釈槽カバー２５は取り外さないため、サンプルプローブ２２が第１の電極部ユニット１１の上方を通過可能であり、可動中である第２の電極部ユニット１２への試料の分注を継続することができ、測定処理を継続することができる。すなわち、イオン選択性電極群２４ｃの交換が必要でない第２の電極部ユニット１２へのサンプルプローブ２２による試料の分注を阻害せずに第２の電極部ユニット１２による測定処理を継続することで、処理能力の低下を抑制しつつ第１の電極部ユニット１１のイオン選択性電極群２４ａを交換することができる。 At this time, the ion-selective electrode group cover 26 of the first electrode unit 11 becomes removable, and the operator can access and replace the ion-selective electrode group 24a. Further, since the dilution tank cover 25 located below the movable range of the sample probe 22 is not removed, the sample probe 22 can pass above the first electrode portion unit 11 and the second electrode portion is moving. Dispensing of the sample to the unit 12 can be continued, and the measurement process can be continued. That is, by continuing the measurement process by the second electrode unit 12 without inhibiting the dispensing of the sample by the sample probe 22 into the second electrode unit 12, which does not require replacement of the ion-selective electrode group 24c. The ion-selective electrode group 24a of the first electrode unit 11 can be replaced while suppressing a decrease in processing capacity.
　続いて、オペレータによるイオン選択性電極群２４ａの交換が終了したかどうかを判定する（ステップＳ１４０）。交換の終了判定は、例えば、イオン選択性電極群２４ａの正常な装着がイオン選択性電極群装着部１２４ａによって検知され、かつ、イオン選択性電極群カバー２６の正常な装着がイオン選択性電極群カバー装着センサ１１ｃによって検知された場合に、交換終了と判定することにより行う。 Subsequently, it is determined whether or not the exchange of the ion-selective electrode group 24a by the operator is completed (step S140). In the determination of the end of replacement, for example, the normal mounting of the ion-selective electrode group 24a is detected by the ion-selective electrode group mounting unit 124a, and the normal mounting of the ion-selective electrode group cover 26 is the ion-selective electrode group. When it is detected by the cover mounting sensor 11c, it is determined that the replacement is completed.
　ステップＳ１４０での判定結果がＮＯの場合、すなわち、イオン選択性電極群２４ａの交換が終了していない場合には、ステップＳ１１０～Ｓ１３０の処理を継続する。 If the determination result in step S140 is NO, that is, if the exchange of the ion-selective electrode group 24a is not completed, the processing of steps S110 to S130 is continued.
　また、ステップＳ１４０での判定結果がＹＥＳの場合、すなわち、イオン選択性電極群２４ａの交換が終了したと判定した場合には、続いて、第１の電極部ユニット１１のソレノイドロック機構１１ａの一部をソレノイド受け２６ａ側に突出させてロック状態（インターロック稼働）とする（ステップＳ１５０）。 If the determination result in step S140 is YES, that is, if it is determined that the exchange of the ion-selective electrode group 24a is completed, then one of the solenoid lock mechanisms 11a of the first electrode unit 11 The portion is projected toward the solenoid receiving 26a to bring it into a locked state (interlock operation) (step S150).
　続いて、インターロックが正常に動作したかどうかを判定する（ステップＳ１６０）。インターロックの動作判定は、ロック機構動作検知センサ１１ｂからの検知結果に基づいて行う。 Subsequently, it is determined whether or not the interlock has operated normally (step S160). The operation determination of the interlock is performed based on the detection result from the lock mechanism operation detection sensor 11b.
　ステップＳ１６０での判定結果がＮＯの場合には、インターロックの動作確認を指示する内容の上方を、制御部３１の図示しない表示装置への表示や音声等によりオペレータに報知し（ステップＳ１６１）、ステップＳ１５０の処理に戻る。 If the determination result in step S160 is NO, the operator is notified of the content instructing the operation confirmation of the interlock by displaying on a display device (not shown) by the control unit 31 or by voice (step S161). The process returns to step S150.
　また、ステップＳ１６０での判定結果がＹＥＳの場合には、第１の電極部ユニット１１を稼働して測定処理を開始し（ステップＳ１７０）、処理を終了する。 If the determination result in step S160 is YES, the first electrode unit 11 is operated to start the measurement process (step S170), and the process ends.
　また、ステップＳ１００での判定結果がＮＯの場合には、第２の電極部ユニット１２のイオン選択性電極群２４ｃの交換が必要か否かを判定する（ステップＳ２００）。なお、ステップＳ１００での判定結果がＮＯの場合、すなわち、イオン選択性電極群２４ａの交換が必要無いと判定された場合には、第１の電極部ユニット１１の稼働を継続し、測定処理を継続する。つまり、サンプルプローブ２２により、位置２２Ａにおいて検体容器５２から試料を吸引し、位置２２Ｂまたは位置２２Ｃにおいて第１の電極部ユニット１１の希釈槽２３ａまたは第２の電極部ユニット１２の希釈槽２３ｂに吐出することで、第１の電極部ユニット１１または第２の電極部ユニット１２による測定処理を行う。 If the determination result in step S100 is NO, it is determined whether or not the ion-selective electrode group 24c of the second electrode unit 12 needs to be replaced (step S200). If the determination result in step S100 is NO, that is, if it is determined that the ion-selective electrode group 24a does not need to be replaced, the operation of the first electrode unit 11 is continued and the measurement process is performed. continue. That is, the sample probe 22 sucks the sample from the sample container 52 at the position 22A and discharges it to the dilution tank 23a of the first electrode unit 11 or the dilution tank 23b of the second electrode unit 12 at the position 22B or 22C. By doing so, the measurement process by the first electrode unit 11 or the second electrode unit 12 is performed.
　ステップＳ２００での判定結果がＮＯの場合、すなわち、イオン選択性電極群２４ｃの交換が必要無いと判定された場合には、第１の電極部ユニット１１と第２の電極部ユニット１２の稼働を継続し、測定処理を継続する。すなわち、サンプルプローブ２２により、位置２２Ａにおいて検体容器５２から試料を吸引し、位置２２Ｂまたは位置２２Ｃにおいて第１の電極部ユニット１１の希釈槽２３ａまたは第２の電極部ユニット１２の希釈槽２３ｂに吐出することで、第１の電極部ユニット１１または第２の電極部ユニット１２による測定処理を行う。 When the determination result in step S200 is NO, that is, when it is determined that the ion-selective electrode group 24c does not need to be replaced, the first electrode unit 11 and the second electrode unit 12 are operated. Continue and continue the measurement process. That is, the sample probe 22 sucks the sample from the sample container 52 at the position 22A and discharges it to the dilution tank 23a of the first electrode unit 11 or the dilution tank 23b of the second electrode unit 12 at the position 22B or 22C. By doing so, the measurement process by the first electrode unit 11 or the second electrode unit 12 is performed.
　また、ステップＳ１００での判定結果がＹＳＥの場合、すなわち、第１の電極部ユニット１１のイオン選択性電極２４ａの交換が必要であると判定した場合には、第１の電極部ユニット１１の測定処理を停止する（ステップＳ１１０）のと並行して、ステップＳ２００での判定を行う。そして、ステップＳ２００での判定結果がＹＥＳの場合、すなわち、第２の電極部ユニット１２のイオン選択性電極群２４ｃの交換が必要であると判定した場合には、第２の電極部ユニット１２の測定処理を停止し（ステップＳ２１０）、以降、第１の電極部ユニット１１に対するステップＳ１２０～Ｓ１７０の処理と同様の処理を行い、処理を終了する。すなわち、第２の電極部ユニット１２は、図示を省略するが、図２～図４及び図７に示す第１の電極部ユニット１１のソレノイドロック機構１１ａ、ロック機構動作検知センサ１１ｂ、イオン選択性電極群カバー装着センサ１１ｃ、ソレノイドロック受け２６ａにそれぞれ対応する構成を有しており、これらを用いてステップＳ２２０～Ｓ２７０の処理を実施し、処理を終了する。 Further, when the determination result in step S100 is YSE, that is, when it is determined that the ion-selective electrode 24a of the first electrode unit 11 needs to be replaced, the measurement of the first electrode unit 11 is performed. In parallel with stopping the process (step S110), the determination in step S200 is performed. When the determination result in step S200 is YES, that is, when it is determined that the ion-selective electrode group 24c of the second electrode unit 12 needs to be replaced, the second electrode unit 12 The measurement process is stopped (step S210), and thereafter, the same process as the process of steps S120 to S170 for the first electrode unit 11 is performed, and the process is completed. That is, although not shown, the second electrode unit 12 has a solenoid lock mechanism 11a, a lock mechanism operation detection sensor 11b, and ion selectivity of the first electrode unit 11 shown in FIGS. 2 to 4 and 7. It has a configuration corresponding to each of the electrode group cover mounting sensor 11c and the solenoid lock receiver 26a, and the processing of steps S220 to S270 is performed using these, and the processing is completed.
　このように、本実施の形態において、第２の電極部ユニット１２のイオン選択性電極２４ｃを交換する必要が無い状態においては、第１の電極部ユニット１１が動作している期間には第２の電極部ユニット１２も動作しており、また、第１の電極部ユニット１１が停止している期間においても第２の電極部ユニット１２は動作している。 As described above, in the present embodiment, in the state where it is not necessary to replace the ion-selective electrode 24c of the second electrode unit 12, the second electrode unit 11 is in operation during the second period. The electrode unit 12 of the above is also operating, and the second electrode unit 12 is operating even during the period when the first electrode unit 11 is stopped.
　以上のように構成した本実施の形態における効果を説明する。 The effect of the present embodiment configured as described above will be explained.
　従来技術においては、例えば、並列に配置した複数のセンサを覆うカバーを開ける際にサンプルプローブと干渉することが考えられるため、センサを交換する際には分析を中断する必要があり、処理能力の低下を招いてしまうという問題があった。 In the prior art, for example, it is possible to interfere with the sample probe when opening the cover covering a plurality of sensors arranged in parallel, so that it is necessary to interrupt the analysis when replacing the sensor, and the processing capacity is increased. There was a problem that it caused a decline.
　これに対して本実施の形態においては、サンプルプローブ２２により分注された試料を希釈する希釈槽２３ａ，２３ｂと、希釈槽２３ａ，２３ｂで希釈された試料中の特定のイオン濃度を測定するイオン選択性電極群２４ａ，２４ｃとをそれぞれ有する複数の電極部ユニット（第１及び第２の電極部ユニット１１，１２）を備え、第１の電極部ユニット１１は、サンプルプローブ２２の動作範囲の下方において希釈槽２３ａの上方に、プローブ部２２ｂが希釈槽２３ａまで下降するために設けられた開口部を有する着脱可能に配置された希釈槽カバー２５（第１のカバー）と、サンプルプローブ２２の動作範囲の下方とならない範囲においてイオン選択性電極群２４ａの上方を覆うように着脱可能に配置されたイオン選択性電極群カバー２６（第２のカバー）とを有するように構成したので、処理能力の低下を抑制しつつイオン選択性電極群２４ａを交換することができる。 On the other hand, in the present embodiment, the diluting tanks 23a and 23b for diluting the sample dispensed by the sample probe 22 and the ion for measuring a specific ion concentration in the sample diluted in the diluting tanks 23a and 23b. A plurality of electrode unit units (first and second electrode units 11 and 12) having selective electrode groups 24a and 24c, respectively, are provided, and the first electrode unit 11 is below the operating range of the sample probe 22. The operation of the diluting tank cover 25 (first cover) detachably arranged above the diluting tank 23a and having an opening provided for the probe portion 22b to descend to the diluting tank 23a, and the sample probe 22. Since it is configured to have an ion-selective electrode group cover 26 (second cover) detachably arranged so as to cover the upper part of the ion-selective electrode group 24a in a range not below the range, the processing capacity can be increased. The ion-selective electrode group 24a can be replaced while suppressing the decrease.
　また、第１の電極部ユニット１１では、イオン選択性電極群２４ａの交換中には測定処理を行うことはできないが、希釈槽２３ａへの試料の分注および希釈槽２３ａにおける試料の希釈・攪拌を継続することができる。 Further, in the first electrode unit 11, the measurement process cannot be performed during the replacement of the ion-selective electrode group 24a, but the sample is dispensed into the diluting tank 23a and the sample is diluted / stirred in the diluting tank 23a. Can be continued.
　＜第２の実施の形態＞
  本発明の第２の実施の形態を図６を参照しつつ説明する。 <Second embodiment>
A second embodiment of the present invention will be described with reference to FIG.
　本実施の形態は、電解質分析装置１００Ｂの分析部１Ｂの第２の電極部ユニット１２Ｂが希釈槽カバー２８とイオン選択性電極群カバー２９とを有する場合を例示するものである。 This embodiment illustrates a case where the second electrode unit 12B of the analysis unit 1B of the electrolyte analyzer 100B has a dilution tank cover 28 and an ion-selective electrode group cover 29.
　図６は、本実施の形態の電解質分析装置の分析部における第１及び第２の電極部ユニットの構造例および配置例を概略的に示す上面図である。図中、第１の実施の形態と同様の部材には同じ符号を付し、説明を省略する。 FIG. 6 is a top view schematically showing a structural example and an arrangement example of the first and second electrode unit in the analysis unit of the electrolyte analyzer of the present embodiment. In the figure, the same members as those in the first embodiment are designated by the same reference numerals, and the description thereof will be omitted.
　図６に示すように、第１及び第２の電極部ユニット１１，１２Ｂは、試料を収容した検体容器５２から電極部ユニット１１，１２Ｂに試料を分注するサンプルプローブ２２の動線（正確にはプローブ部２２ｂの動線）に沿って希釈槽２３ａ，２３ｂが位置するように配置されている。また、第１及び第２の電極部ユニット１１，１２Ｂは、イオン選択性電極群２４ａ，２４ｃ及び比較電極２４ｂ，２４ｄがサンプルプローブ２２の移動範囲（すなわち、カバー部２２ａの動作範囲）の下方よりも外側に位置するように配置されている。また、検体容器５２（位置２２Ａにおけるサンプルプローブ２２のプローブ部２２ｂの位置）に最も近い位置に第１の電極部ユニット１１が、検体容器５２から最も離れた位置に第２の電極部ユニット１２Ｂがそれぞれ配置されている。 As shown in FIG. 6, the first and second electrode unit units 11 and 12B are the flow lines of the sample probe 22 for dispensing the sample from the sample container 52 containing the sample to the electrode units 11 and 12B (accurately). Is arranged so that the dilution tanks 23a and 23b are located along the flow line of the probe portion 22b). Further, in the first and second electrode unit units 11 and 12B, the ion- selective electrode groups 24a and 24c and the comparative electrodes 24b and 24d are located below the moving range of the sample probe 22 (that is, the operating range of the cover unit 22a). Is also arranged so as to be located on the outside. Further, the first electrode unit 11 is located closest to the sample container 52 (the position of the probe portion 22b of the sample probe 22 at the position 22A), and the second electrode unit 12B is located farthest from the sample container 52. Each is arranged.
　第２の電極部ユニット１２Ｂは、サンプルプローブ２２の動作範囲の下方において希釈槽２３ｂの上方にプローブ部２２ｃが希釈槽２３ｂまで下降するために設けられた開口部を有する着脱可能に配置された希釈槽カバー２８（第１のカバー）と、サンプルプローブ２２の動作範囲の下方とならない範囲においてイオン選択性電極群２４ｃ及び比較電極２４ｄの上方を覆うように着脱可能に配置されたイオン選択性電極群カバー２９（第２のカバー）とを有している。 The second electrode unit 12B is a detachably arranged diluting unit having an opening provided for the probe unit 22c to descend to the diluting tank 23b above the diluting tank 23b below the operating range of the sample probe 22. The ion-selective electrode group 24c and the ion-selective electrode group 24c are detachably arranged so as to cover the upper part of the ion-selective electrode group 24c and the comparison electrode 24d in a range not below the operating range of the tank cover 28 (first cover) and the sample probe 22. It has a cover 29 (second cover).
　イオン選択性電極群カバー２９は、イオン選択性電極群カバー２６同様のソレノイドロック受け２９ａを有している。また、第２の電極部ユニット１２Ｂは、第１の電極部ユニット１１と同様のソレノイドロック機構１２ａを有している。すなわち、ソレノイドロック機構１２ａ及びソレノイドロック受け２９ａは、イオン選択性電極群カバー２９（第２のカバー）を第２の電極部ユニット１２Ｂに対して固定可能なインターロックを構成する。 The ion-selective electrode group cover 29 has a solenoid lock receiver 29a similar to the ion-selective electrode group cover 26. Further, the second electrode unit 12B has the same solenoid lock mechanism 12a as the first electrode unit 11. That is, the solenoid lock mechanism 12a and the solenoid lock receiver 29a form an interlock capable of fixing the ion-selective electrode group cover 29 (second cover) to the second electrode unit 12B.
　また、第２の電極部ユニット１２Ｂには、イオン選択性電極群カバー２９が第２の電極部ユニット１２Ｂに対して正常に装着された状態であることを検知するイオン選択性電極群カバー装着センサ１２ｃと、ソレノイドロック機構１２ａが動作していること（ロック状態となっていること）を検知するロック機構動作検知センサ１２ｂとが設けられている。 Further, the ion-selective electrode group cover mounting sensor that detects that the ion-selective electrode group cover 29 is normally mounted on the second electrode unit 12B is mounted on the second electrode unit 12B. 12c and a lock mechanism operation detection sensor 12b for detecting that the solenoid lock mechanism 12a is operating (locked state) are provided.
　その他の構成は第１の実施の形態と同様である。すなわち、これらにおいても、第１の実施の形態と同様に第１の電極部ユニット１１が停止し、かつ、第２の電極部ユニット１２Ｂが動作継続できる構成である。 Other configurations are the same as those in the first embodiment. That is, also in these cases, the first electrode unit 11 can be stopped and the second electrode unit 12B can continue to operate as in the first embodiment.
　以上のように構成した本実施の形態においても第１の実施の形態と同様の効果を得ることができる。 The same effect as that of the first embodiment can be obtained even in the present embodiment configured as described above.
　また、第２の電極部ユニット１２Ｂでは、イオン選択性電極群２４ｃの交換中には測定処理を行うことはできないが、希釈槽２３ｂへの試料の分注および希釈槽２３ｂにおける試料の希釈・攪拌を継続することができる。且つ、第１の実施の形態で示した第１の電極部ユニットの第２カバー２６を取り外す手順と同様の手順にて、第２の電極部ユニット第２カバー２９は、プローブ部２２ｂの下方には配置されておらず、干渉しないため、単独で取り外すことができる。 Further, in the second electrode unit 12B, the measurement process cannot be performed during the replacement of the ion-selective electrode group 24c, but the sample is dispensed into the diluting tank 23b and the sample is diluted / stirred in the diluting tank 23b. Can be continued. Further, in the same procedure as the procedure for removing the second cover 26 of the first electrode unit shown in the first embodiment, the second cover 29 of the second electrode unit is placed below the probe portion 22b. Is not placed and does not interfere, so it can be removed independently.
　＜その他の実施の形態＞
　本発明は上記の実施の形態に限定されるものではなく、その要旨を逸脱しない範囲内の様々な変形例や組み合わせが含まれる。 <Other embodiments>
The present invention is not limited to the above-described embodiment, and includes various modifications and combinations within a range that does not deviate from the gist thereof.
　（１）例えば、上記の実施の形態においては、第１の電極部ユニット１１および第２の電極部ユニット１２Ｂにおいて、第２のカバー２６，２９が着脱可能な場合を例示して説明したが、これに限られず、例えば、第２のカバー２６，２９をヒンジ機構などを介して第１の電極部ユニット１１および第２の電極部ユニット１２Ｂに接続し、開閉可能な構成としても良い。 (1) For example, in the above embodiment, the case where the second covers 26 and 29 are removable in the first electrode unit 11 and the second electrode unit 12B has been described as an example. Not limited to this, for example, the second covers 26 and 29 may be connected to the first electrode unit 11 and the second electrode unit 12B via a hinge mechanism or the like so as to be openable and closable.
　（２）また、上記の実施の形態においては、２つの電極部ユニットを備えた場合を例示して説明したが、これに限られず、例えば、３つ以上の電極部ユニットを備え、検体容器５２に最も近い位置に配置された電極部ユニットが第１のカバーと第２のカバーとを有する構成としたり、検体容器５２から最も離れた位置に配置された電極部ユニットが第３のカバーを有する構成としたりしても良い。 (2) Further, in the above embodiment, the case where two electrode unit units are provided has been illustrated and described, but the present invention is not limited to this, and for example, three or more electrode unit units are provided and the sample container 52 is provided. The electrode unit located closest to the sample container 52 has a first cover and a second cover, and the electrode unit located farthest from the sample container 52 has a third cover. It may be configured.
　（３）また、上記の実施の形態においては、イオン選択性電極群カバー装着センサ１１ｃやロック機構動作検知センサ１１ｂが機械式センサである場合を例示して説明したが、これに限られず、例えば、レーザ式のセンサやカメラ画像による判定を行うセンサを用いる構成としても良い。 (3) Further, in the above embodiment, the case where the ion-selective electrode group cover mounting sensor 11c and the lock mechanism operation detection sensor 11b are mechanical sensors has been described as an example, but the present invention is not limited to this, for example. , A laser type sensor or a sensor that makes a determination based on a camera image may be used.
　（４）また、上記の実施の形態においては、イオン選択性電極群の交換が終了したか否かの判定をイオン選択性電極群装着部１２４ａのセンサ機能及びイオン選択性電極群カバー装着センサ１１ｃの検知結果に基づいて行う場合を例示して説明したが、これに限られず、例えば、オペレータにより交換終了を明示する操作が制御部３１の図示しない操作装置等により行われた場合に、イオン選択性電極群の交換が終了したと判定しても良い。ただし、この場合においてもイオン選択性電極群装着部１２４ａのセンサ機能やイオン選択性電極群カバー装着センサ１１ｃの検知結果に基づいて、イオン選択性電極群が正常に交換されたかどうかを判定することが好ましい。また、オペレータにより、例えば、イオン選択性電極群に設けられたバーコードなどの個体識別標識の読み取りを行うことで、新規のイオン選択性電極に交換されたことを確認するように構成しても良い。 (4) Further, in the above embodiment, the sensor function of the ion-selective electrode group mounting unit 124a and the ion-selective electrode group cover mounting sensor 11c determine whether or not the replacement of the ion-selective electrode group is completed. The case where the replacement is performed based on the detection result of the above has been described as an example, but the present invention is not limited to this. It may be determined that the replacement of the sex electrode group is completed. However, even in this case as well, it is determined whether or not the ion-selective electrode group has been normally replaced based on the sensor function of the ion-selective electrode group mounting unit 124a and the detection result of the ion-selective electrode group cover mounting sensor 11c. Is preferable. Further, the operator may read an individual identification marker such as a bar code provided on the ion-selective electrode group to confirm that the electrode has been replaced with a new ion-selective electrode. good.
　＜付記＞
　なお、本発明は、上記の実施の形態で説明した全ての構成を備えるものに限定されず、その構成の一部を削除したものも含まれる。また、上記の各構成、機能等は、それらの一部又は全部を、例えば集積回路で設計する等により実現してもよい。また、上記の各構成、機能等は、プロセッサがそれぞれの機能を実現するプログラムを解釈し、実行することによりソフトウェアで実現してもよい。 <Additional Notes>
It should be noted that the present invention is not limited to the one including all the configurations described in the above-described embodiment, and includes the one in which a part of the configurations is deleted. Further, each of the above configurations, functions and the like may be realized by designing a part or all of them by, for example, an integrated circuit. Further, each of the above configurations, functions, and the like may be realized by software by the processor interpreting and executing a program that realizes each function.
　１，１Ｂ…分析部、１１…第１の電極部ユニット、１１ａ…ソレノイドロック機構、１１ｂ…ロック機構動作検知センサ、１１ｃ…イオン選択性電極群カバー装着センサ、１２，１２Ｂ…第２の電極部ユニット、１２ａ…ソレノイドロック機構、１２ｂ…ロック機構動作検知センサ、１２ｃ…イオン選択性電極群カバー装着センサ、２２…サンプルプローブ、２２ａ…カバー部、２３ａ，２３ｂ…希釈槽、２４ａ…イオン選択性電極群、２４ｂ…比較電極、２４ｃ…イオン選択性電極群、２４ｄ…比較電極、２５…希釈槽カバー、２６…イオン選択性電極群カバー、２７…第３のカバー、２８…希釈槽カバー、２９…イオン選択性電極群カバー、３１…制御部、５２…検体容器、５３ａ，５３ｂ…吸引器、５５ａ，５５ｂ…比較電極液ボトル、５６ａ，５６ｂ…希釈液ボトル、５７ａ，５７ｂ…送液機構、５８ａ，５８ｂ…送液機構、１００，１００Ｂ…電解質分析装置、１２４ａ…イオン選択性電極群装着部 1,1B ... Analysis unit, 11 ... First electrode unit, 11a ... Solvent lock mechanism, 11b ... Lock mechanism operation detection sensor, 11c ... Ion-selective electrode group cover mounting sensor, 12, 12B ... Second electrode unit Unit, 12a ... solenoid lock mechanism, 12b ... lock mechanism operation detection sensor, 12c ... ion-selective electrode group cover mounting sensor, 22 ... sample probe, 22a ... cover unit, 23a, 23b ... dilution tank, 24a ... ion-selective electrode Group, 24b ... Comparative electrode, 24c ... Ion-selective electrode group, 24d ... Comparative electrode, 25 ... Diluting tank cover, 26 ... Ion-selective electrode group cover, 27 ... Third cover, 28 ... Diluting tank cover, 29 ... Ion-selective electrode group cover, 31 ... Control unit, 52 ... Specimen container, 53a, 53b ... Aspirator, 55a, 55b ... Comparative electrode liquid bottle, 56a, 56b ... Diluted liquid bottle, 57a, 57b ... Liquid feeding mechanism, 58a , 58b ... Liquid feeding mechanism, 100, 100B ... Electrolyte analyzer, 124a ... Ion-selective electrode group mounting part

Claims (5)

  1. 　サンプルプローブにより分注された試料を希釈する希釈槽と、前記希釈槽で希釈された試料中の特定のイオン濃度を測定するイオン選択性電極とをそれぞれ有する複数の電極部ユニットを備え、
    　前記複数の電極部ユニットのうち少なくとも１つの電極部ユニットは、
    　前記サンプルプローブの動作範囲の下方において前記希釈槽の上方にプローブ部が前記希釈槽まで下降するために設けられた開口部を有する着脱可能に配置された第１のカバーと、
    　前記サンプルプローブの動作範囲の下方とならない範囲において前記イオン選択性電極の上方を覆うように着脱可能に配置された第２のカバーとを有することを特徴とする電解質分析装置。     A plurality of electrode unit units each having a diluting tank for diluting a sample dispensed by a sample probe and an ion-selective electrode for measuring a specific ion concentration in the sample diluted in the diluting tank are provided.
    At least one electrode unit among the plurality of electrode units is
    A detachably arranged first cover having an opening provided for the probe portion to descend to the dilution tank below the working range of the sample probe and above the dilution tank.
    An electrolyte analyzer comprising a second cover detachably arranged so as to cover above the ion-selective electrode in a range not below the operating range of the sample probe.
  2. 　請求項１記載の電解質分析装置において、
    　前記複数の電極部ユニットは、前記試料を収容した検体容器から前記電極部ユニットに前記試料を分注する前記サンプルプローブの動線に沿って前記希釈槽が位置するように配置され、
    　前記複数の電極部ユニットのうち少なくとも前記検体容器に最も近い位置に配置された前記電極部ユニットは、前記第１のカバーと前記第２のカバーとを有することを特徴とする電解質分析装置。     In the electrolyte analyzer according to claim 1,
    The plurality of electrode unit units are arranged so that the dilution tank is located along the flow line of the sample probe that dispenses the sample from the sample container containing the sample to the electrode unit.
    An electrolyte analyzer characterized in that the electrode unit unit arranged at least at a position closest to the sample container among the plurality of electrode units has the first cover and the second cover.
  3. 　請求項２記載の電解質分析装置において、
    　前記複数の電極部ユニットは、それぞれ前記第１のカバーと前記第２のカバーとを有することを特徴とする電解質分析装置。     In the electrolyte analyzer according to claim 2,
    An electrolyte analyzer, wherein each of the plurality of electrode unit has a first cover and a second cover, respectively.
  4. 　請求項２記載の電解質分析装置において、
    　前記複数の電極部ユニットのうち前記検体容器から最も離れた位置に配置された前記電極部ユニットは、前記希釈槽と前記イオン選択性電極との上方に
    プローブ部が前記希釈槽まで下降するために設けられた開口部を有し、その他の部分を一体的に覆うように配置された第３のカバーを有することを特徴とする電解質分析装置。     In the electrolyte analyzer according to claim 2,
    In the electrode unit unit arranged at the position farthest from the sample container among the plurality of electrode units, the probe unit descends to the dilution tank above the dilution tank and the ion-selective electrode. An electrolyte analyzer comprising an opening provided and a third cover arranged to integrally cover the other portions.
  5. 　請求項２記載の電解質分析装置において、
    　前記サンプルプローブおよび前記電極部ユニットの動作を制御する制御装置を備え、
    　前記少なくとも１つの電極部ユニットは、前記第２のカバーを前記電極部ユニットに対して固定可能なインターロックを有し、
    　前記制御装置は、前記少なくとも１つの電極部ユニットが測定を停止している場合に、前記第２のカバーの前記電極部ユニットからの取り外しを許容するように前記インターロックを制御することを特徴とする電解質分析装置。     In the electrolyte analyzer according to claim 2,
    A control device for controlling the operation of the sample probe and the electrode unit is provided.
    The at least one electrode unit has an interlock capable of fixing the second cover to the electrode unit.
    The control device is characterized in that the interlock is controlled so as to allow the removal of the second cover from the electrode unit when the measurement is stopped by the at least one electrode unit. Electrolyte analyzer.
PCT/JP2021/007995 2020-07-31 2021-03-02 Electrolyte analysis apparatus WO2022024433A1 (en)

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JPH0466573U (en) * 1990-10-19 1992-06-11
JPH06273372A (en) * 1993-03-18 1994-09-30 Hitachi Ltd Organismic liquid analyzer
JP2000266757A (en) * 1999-03-18 2000-09-29 Hitachi Ltd Automatic analyzer
JP3107751U (en) * 2004-09-15 2005-02-17 株式会社日立ハイテクノロジーズ Drive unit separation type movable lid and electrolyte measuring apparatus including the same
JP2017156089A (en) * 2016-02-29 2017-09-07 株式会社日立ハイテクノロジーズ Electrolyte analyzer

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10566171B2 (en) 2016-03-25 2020-02-18 Technology Research Association For Future Additive Manufacturing Three-dimensional layer-by-layer shaping apparatus, three-dimensional layer-by-layer shaping apparatus control method, and three-dimensional layer-by-layer shaping apparatus control program

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0466573U (en) * 1990-10-19 1992-06-11
JPH06273372A (en) * 1993-03-18 1994-09-30 Hitachi Ltd Organismic liquid analyzer
JP2000266757A (en) * 1999-03-18 2000-09-29 Hitachi Ltd Automatic analyzer
JP3107751U (en) * 2004-09-15 2005-02-17 株式会社日立ハイテクノロジーズ Drive unit separation type movable lid and electrolyte measuring apparatus including the same
JP2017156089A (en) * 2016-02-29 2017-09-07 株式会社日立ハイテクノロジーズ Electrolyte analyzer

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