Electrolyte analysis device and abnormality determination method thereof

Abstract

Provided is an electrolyte analysis device capable of early detection of abnormalities in an ion-selective electrode, and an abnormality determination method therefor. The electrolyte analysis device according to the present invention includes an ion-selective electrode that generates a sample potential corresponding to the concentration of ions contained in a sample; a comparison electrode that generates a reference potential serving as a reference; and a concentration calculation section that calculates the concentration of ions based on the potential difference between the sample potential and the reference potential, characterized by further including an abnormality determination section that determines the presence or absence of an abnormality based on an evaluation value calculated using a detergent potential, which is a potential generated by the ion-selective electrode when a detergent is supplied.

Description

TECHNICAL FIELD

[0001] The present application relates to an electrolyte analysis device for analyzing an electrolyte component in a sample. BACKGROUND

[0002] The electrolyte analysis device is a device for analyzing an electrolyte component such as sodium (Na), potassium (K), chlorine (Cl) in a sample, and is used in inspection facilities and the like. In many electrolyte analysis devices, by measuring a potential difference between an ion selective electrode (ISE) that generates a potential corresponding to a specific ion concentration and a comparison electrode that generates a reference potential, the concentration of the electrolyte component in the sample can be obtained. These electrodes are consumables that reach the end of life in a prescribed period or number of uses, and are therefore periodically replaced.

[0003] Patent Document 1 discloses that, in order to manage the life of the electrodes, the replacement time of the electrodes is calculated based on parameters that indicate the performance of the electrodes measured at the time of device shutdown or startup. As the parameters, the potential difference between the ISE and the comparison electrode, the sensitivity to a certain ion, i.e., the slope, the deviation when measuring a certain concentration sample multiple times, i.e., the precision, the size of the shift from the expected value, i.e., the accuracy, and the like are cited.

[0004] PRIOR ART DOCUMENTS

[0005] PATENT DOCUMENT

[0006] Patent Document 1: Japanese Patent Laid-Open No. 2004-219352 SUMMARY

[0007] PROBLEMS TO BE SOLVED BY THE INVENTION

[0008] However, in Patent Document 1, only the sample for which the electrolyte is measured and the calibration solution are used to measure the parameters that indicate the performance of the electrodes, and this is not sufficient for detecting abnormalities in the ion selective electrode as early as possible.

[0009] Therefore, an object of the present application is to provide an electrolyte analysis device and an abnormality determination method thereof that can detect abnormalities in the ion selective electrode as early as possible.

[0010] MEANS OF SOLVING THE PROBLEMS

[0011] To achieve the above object, an electrolyte analyzing device according to the present application includes an ion-selective electrode that generates a potential corresponding to an ion concentration in a sample, a comparison electrode that generates a potential serving as a reference, and a concentration calculating section that calculates the ion concentration based on a potential difference between the sample potential and the reference potential, characterized by further including an abnormality determining section that determines the presence or absence of an abnormality based on an evaluation value calculated using a detergent potential, which is a potential generated by the ion-selective electrode when a detergent is supplied.

[0012] Further, the present application relates to an abnormality determining method for an electrolyte analyzing device including an ion-selective electrode that generates a potential corresponding to an ion concentration in a sample, a comparison electrode that generates a potential serving as a reference, and a concentration calculating section that calculates the ion concentration based on a potential difference between the sample potential and the reference potential, characterized by including a step of detecting a detergent potential, which is a potential generated by the ion-selective electrode when a detergent is supplied, a step of calculating an evaluation value using the detergent potential, and a step of determining the presence or absence of an abnormality based on the evaluation value.

[0013] Effects of Invention

[0014] According to the present application, it is possible to provide an electrolyte analyzing device capable of detecting an abnormality of an ion-selective electrode at an early stage. BRIEF DESCRIPTION OF DRAWINGS

[0015] Figure 1 is a diagram illustrating one example of the structure of an electrolyte analyzing device.

[0016] Figure 2 is a diagram illustrating one example of the structure of an ion-selective electrode.

[0017] Figure 3 is a diagram showing one example of a flow of the process of Embodiment 1.

[0018] Figure 4 is a diagram showing one example of a setting screen of a condition related to a stabilized potential.

[0019] Figure 5 is a diagram for explaining one example of an evaluation value.

[0020] Figure 6 is a diagram showing one example of a display screen when there is an abnormality in the deviation rate, i.e., Screen Example 1.

[0021] Figure 7is a diagram showing one example of a display screen when there is an abnormality in the high concentration region, that is, a screen example 2.

[0022] Figure 8 is a diagram showing one example of a display screen when there is an abnormality in the low concentration region, that is, a screen example 3.

[0023] Figure 9 is a diagram showing one example of a display screen when there is an abnormality in the predicted value of the divergence rate, that is, a screen example 4.

[0024] Figure 10 is a diagram showing a display example of the progress of the predicted value of the divergence rate.

[0025] Figure 11 is a diagram illustrating a determination of the presence or absence of an abnormality based on a combination of a plurality of evaluation values.

[0026] Figure 12 is a diagram showing one example of a display screen when there is an abnormality in the plurality of evaluation values, that is, a screen example 5. DETAILED DESCRIPTION

[0027] A preferred embodiment of an electrolyte analysis device of the present application will be described below with reference to the drawings. The electrolyte analysis device is a device that analyzes electrolytes, such as Na ions, K ions, Cl ions, and the like, contained in a test material such as blood and urine provided by a subject, and can be used alone or mounted on an automatic analysis device. The automatic analysis device on which the electrolyte analysis device is mounted is, for example, a biochemical automatic analysis device, an immune automatic analysis device, a mass spectrometry device, a coagulation analysis device, a device in which these are combined, or the like. In addition, in the following description and drawings, the same reference numerals are assigned to constituent elements having the same functional structure, and repeated description is omitted. Furthermore, the drawings are diagrams that schematically show the embodiment, and sometimes a practical object is simplified to be shown.

[0028] [Example 1]

[0029] Use Figure 1 One example of the structure of the electrolyte analysis device 100 will be described. The electrolyte analysis device 100 is roughly divided into a measurement section and a control section. The measurement section measures the potential of a test material and a standard solution after dilution as an electrolyte solution. The control section controls the operation of the measurement section, and calculates the ion concentration contained in the electrolyte solution based on the potential measured by the measurement section. Hereinafter, the measurement section and the control section will be described respectively.

[0030] The measurement section includes a dilution tank 3, a flow path 29, ion selective electrodes (ISEs) 4, 5, and 6, and a comparison electrode 7. In addition, the ion selective electrodes are, for example, an Na ISE section 4, a K ISE section 5, and a Cl ISE section 6.

[0031] The sample, the diluent, and the standard solution are supplied to the dilution tank 3. The sample is contained in the sample container 1, and is dispensed from the sample container 1 to the empty dilution tank 3 by the dispensing nozzle 2. The dispensed sample is diluted by further supplying the diluent to the dilution tank 3.

[0032] The diluent is contained in the diluent bottle 21, and is supplied from the diluent bottle 21 to the dilution tank 3 containing the sample by the action of the diluent syringe 10, the diluent first valve 17, and the diluent second valve 18. That is, in a state where the diluent first valve 17 is closed and the diluent second valve 18 is opened, the diluent is sucked into the diluent syringe 10, and thereafter, in a state where the diluent first valve 17 is opened and the diluent second valve 18 is closed, the diluent is discharged from the diluent syringe 10 to the dilution tank 3.

[0033] The standard solution is contained in the standard solution bottle 20, and is supplied from the standard solution bottle 20 to the empty dilution tank 3 by the action of the standard solution syringe 9, the standard solution first valve 15, and the standard solution second valve 16. That is, in a state where the standard solution first valve 15 is closed and the standard solution second valve 16 is opened, the standard solution is sucked into the standard solution syringe 9, and thereafter, in a state where the standard solution first valve 15 is opened and the standard solution second valve 16 is closed, the standard solution is discharged from the standard solution syringe 9 to the dilution tank 3.

[0034] The diluted sample and the standard solution as the electrolyte solution, and the comparison electrode solution contained in the comparison electrode solution bottle 19 are supplied to the flow path 29 by the action of the pipette syringe 8, the pinch valve 11, the first valve 12, the second valve 13, and the third valve 14. That is, by the pipette syringe 8 sucking in a state where the first valve 12 and the second valve 13 are opened and the pinch valve 11 and the third valve 14 are closed, the comparison electrode solution is supplied from the comparison electrode solution bottle 19 to the flow path 29. Thereafter, in a state where the first valve 12 is switched to closed and the pinch valve 11 is switched to opened, by the pipette syringe 8 sucking, the electrolyte solution is supplied from the dilution tank 3 to the flow path 29. The electrolyte solution and the comparison electrode solution form a liquid junction in the flow path 29. In the flow path 29, the Na ISE section 4, the K ISE section 5, and the Cl ISE section 6 as the ion selective electrode are connected to the electrolyte solution side, and the comparison electrode 7 is connected to the comparison electrode solution side.

[0035] In the Na ISE section 4, the K ISE section 5, and the Cl ISE section 6, a potential corresponding to the concentration of the Na ion, the K ion, and the Cl ion contained in the electrolyte solution supplied to the flow path 29 is respectively generated, and is transmitted to the control section via the wiring 28. Regarding the Na ISE section 4, the K ISE section 5, and the Cl ISE section 6, the following will be described using the Na ISE section 4 as an example. Figure 2The reference potential is generated in the comparison electrode 7 and sent to the control section via the wiring 28.

[0036] The control section includes an amplifier 22, an A / D converter 23, a computer 24, a keyboard 25, a monitor 26, and a memory 27. The amplifier 22 amplifies the potential difference between the potential generated in each of the Na ISE section 4, the K ISE section 5, and the Cl ISE section 6 and the reference potential, and sends it to the A / D converter 23. The A / D converter 23 converts the sent potential difference from an analog signal to a digital signal and sends it to the computer 24. The computer 24 calculates the concentrations of Na ions, K ions, and Cl ions contained in the diluted sample using the sent digital signal. The calculated concentrations are displayed on the monitor 26.

[0037] The calibration curve stored in the memory 27 is used for the calculation of the concentrations. The calibration curve is generated in advance based on the potential difference obtained by measuring the concentrations of Na ions, K ions, and Cl ions in solutions whose concentrations are known by the measuring section. Data related to the sample, the measurement conditions in the measuring section, and the like can be input via the keyboard 25 as an input device. The diluted sample and the standard solution can be alternately supplied to the flow path 29, and the respective potential differences can be repeatedly measured. By alternately repeating the measurement of the diluted sample and the standard solution, the measurement error can be reduced.

[0038] Using Figure 2 The ion-selective electrodes, i.e., the Na ISE section 4, the K ISE section 5, and the Cl ISE section 6, will be described. The Na ISE section 4 has an electrode 4a, a Na-selective membrane 4b, and a housing 4c. The housing 4c is a plastic-made box, the rod-shaped electrode 4a is inserted from the upper surface, the Na-selective membrane 4b is provided inside, and an electrode solution is filled therein. The Na-selective membrane 4b is a membrane that selectively permeates Na ions. The electrode 4a detects the potential generated in the electrode solution by the Na ions that have permeated the Na-selective membrane 4b. The potential detected by the electrode 4a is sent via the wiring 28a. The Na ISE section 4 is connected to the flow path 29 so that the Na-selective membrane 4b is brought into contact with the electrolyte solution flowing in the flow path 29 in the direction of the arrow A.

[0039] The K ISE section 5 and the Cl ISE section 6 have the same structure as the Na ISE section 4, and have an electrode 5a, a K-selective membrane 5b, a housing 5c, and an electrode 6a, a Cl-selective membrane 6b, and a housing 6c, respectively. The K-selective membrane 5b is a membrane that selectively permeates K ions, and the Cl-selective membrane 6b is a membrane that selectively permeates Cl ions. The K ISE section 5 and the Cl ISE section 6 are also connected to the flow path 29 in the same manner as the Na ISE section 4.

[0040] Foreign matters such as proteins, organic matters, and bacteria falling from the atmosphere in the sample are included in the electrolyte solution flowing through the flow path 29. Such foreign matters adhere to the Na-selective membrane 4b and the like or are accumulated on the inner wall or the connection portion of the flow path 29, thereby reducing the response and the sensitivity of the Na ISE portion 4, the K ISE portion 5, and the Cl ISE portion 6. Therefore, in order to maintain the analysis performance of the electrolyte analysis device 100, the flow path 29 and the Na ISE portion 4 and the like are periodically cleaned.

[0041] However, even if the periodic cleaning is performed, it is difficult to completely remove the foreign matters adhering to the Na-selective membrane 4b and the like, and an abnormality occurs in a predetermined period or a predetermined number of uses, and the replacement of the Na ISE portion 4 and the like is required. The replacement of the Na ISE portion 4 and the like requires time, effort, and materials, and it is desirable to detect an abnormality as early as possible. Therefore, in Embodiment 1, since the ions contained in the detergent used in the cleaning have a high concentration, the state of the Na ISE portion 4 and the like is determined on the basis of the evaluation value calculated using the potential measured at the time of the cleaning, and an abnormality is detected as early as possible.

[0042] Use Figure 3 One example of the processing flow of Embodiment 1 will be described in steps.

[0043] (S301)

[0044] The computer 24 causes the dispensing nozzle 2, the pipette injector 8, and the like to operate, and supplies the detergent for cleaning to the flow path 29. Specifically, the detergent is dispensed from the detergent rack containing the detergent to the dilution tank 3 through the dispensing nozzle 2, and the detergent in the dilution tank 3 is supplied to the flow path 29 by the pipette injector 8 in a state where the first valve 12 and the third valve 14 are closed and the pinch valve 11 and the second valve 13 are opened. The detergent dispensed into the dilution tank 3 can be supplied to the flow path 29 as it is, or can be supplied after being diluted by a diluent. In addition, the detergent is a solution in which the concentrations of Na ions, K ions, and Cl ions are about 1000 times those of the sample and the standard solution, and, for example, a solution containing sodium hypochlorite and sodium hydroxide is used.

[0045] (S302)

[0046] The computer 24 measures the potential of the detergent in the flow path 29 by the Na ISE portion 4, the K ISE portion 5, and the Cl ISE portion 6, and calculates the ion concentration on the basis of the measured potential.

[0047] (S303)

[0048] The computer 24 causes the straw injector 8 or the like to act to discharge the detergent from the flow path 29. Specifically, in a state where the first valve 12 and the third valve 14 are closed and the pinch valve 11 and the second valve 13 are opened, the detergent in the flow path 29 is sucked by the straw injector 8, and in a state where the third valve 14 is switched to be opened and the second valve 13 is switched to be closed, the detergent is discharged from the straw injector 8. By the provision of the detergent to the flow path 29 in S301 and the discharge of the detergent from the flow path 29 in S303, one cleaning is performed.

[0049] (S304)

[0050] The computer 24 determines whether the suction and discharge of the detergent reach a prescribed number of times. If the prescribed number of times is reached, the process proceeds to S305, and if the prescribed number of times is not reached, the process returns to S301. The prescribed number of times is set to a number of times at which the flow path 29 or the ISE section 4 for Na, the ISE section 5 for K, and the ISE section 6 for Cl are sufficiently cleaned, for example, 15 times. That is, if 15 times is set as the prescribed number of times, 15 cleanings and the potential measurement in S302 are performed.

[0051] (S305)

[0052] The computer 24 calculates a deviation rate VR for evaluating carryover, for example, using the following equation, based on the potential measured in S302.

[0053] VR = (V1 - Vave) / Vave... (Equation 1)

[0054] Here, V1 is the potential measured at the time of the first cleaning, and Vave is the average of the potentials after stabilization. In addition, the potential after stabilization refers to a potential after the potential value measured at the time of cleaning reaches a certain level.

[0055] When the solution in the flow path 29 is replaced, for example, when the standard solution that fills the flow path 29 before cleaning is replaced with the detergent at the time of cleaning, the standard solution as the solution before replacement remains in the flow path 29, generating so-called carryover. The greater the degree of deterioration of the ion-selective electrode or the degree of leakage of the solution from the connection portion with the flow path 29, the greater the amount of the standard solution as the solution before replacement remains. In addition, the amount of the standard solution decreases each time the cleaning is repeated, reaching a certain level.

[0056] Therefore, the evaluation of the residue is performed using the potential immediately after the standard solution is replaced with the detergent, i.e., VI, the average of the potential at the time when the amount of the standard solution is reduced to a certain level by the multiple washing, i.e., Vave, and the deviation ratio VR calculated according to (Formula 1). That is, the larger the deviation ratio VR, the greater the degree of deterioration of the ion-selective electrode or the more the leakage of the solution from the connection portion of the ion-selective electrode and the flow path 29. The calculated deviation ratio VR is stored in the memory 27 as one of the evaluation values for determining the presence or absence of abnormality.

[0057] The potential after stabilization can be specified based on the number of washings and the change in the potential. In the case of being based on the number of washings, three or more potentials measured after three or more washings are specified as the potential after stabilization. For example, in the case where the prescribed number of times is 15, the potentials measured at the 13th to 15th washings are the potential after stabilization. In the case of being based on the change in the potential, the potentials successively measured, of which the difference between the potential measured at the nth washing and the potential measured at the (n+1)th washing is within a prescribed range and the difference between the first potential and the last potential is within a prescribed range, are specified as the potential after stabilization. The conditions related to the potential after stabilization, such as the selection of the number of washings and the change in the potential, can be set by the operator.

[0058] Using Figure 4 An explanation of the setting screen of the conditions related to the potential after stabilization is performed. The setting screen 400 includes a number of washings selection button 401, a change in potential selection button 402, a number of times setting section 403, and a potential setting section 404, and is displayed on the monitor 26.

[0059] When the operator selects the number of washings, the number of washings selection button 401 is clicked. If the number of washings selection button 401 is clicked, the number of times setting section 403 becomes operable. In the number of times setting section 403, the number of times specified as the potential after stabilization is set.

[0060] When the operator selects the change in the potential, the change in potential selection button 402 is clicked. If the change in potential selection button 402 is clicked, the potential setting section 404 becomes operable. In the potential setting section 404, the allowable value of the difference between the potential measured at the nth washing and the potential measured at the (n+1)th washing, and the allowable value of the difference between the first potential and the last potential are set.

[0061] Return to Figure 3 the explanation of

[0062] (S306)

[0063] The computer 24 calculates the average of the ion concentration of the detergent based on the average of the potential after stabilization found in S305. The calculated average is stored in the memory 27 as one of the evaluation values for determining the presence or absence of abnormality.

[0064] (S307)

[0065] The computer 24 causes the dispensing nozzle 2, the pipette injector 8, and the like to act, and repeatedly supplies and discharges the adjusting agent to the flow path 29. The supply and discharge of the adjusting agent are performed in the same manner as the supply of the detergent in S301 and the discharge of the detergent in S303. The adjusting agent is a solution that makes the inner wall of the flow path 29, which has become hydrophobic due to the supply of the detergent, have hydrophilicity, and a solution containing a protein is used.

[0066] (S308)

[0067] The computer 24 causes the standard solution injector 9, the pipette injector 8, and the like to act, and supplies the standard solution to the flow path 29. Specifically, first, in a state where the first valve 15 for the standard solution is closed and the second valve 16 for the standard solution is opened, the standard solution is drawn from the standard solution bottle 20 to the standard solution injector 9. Then, in a state where the first valve 15 for the standard solution is switched to be opened and the second valve 16 for the standard solution is switched to be closed, the standard solution is discharged from the standard solution injector 9 to the dilution tank 3. Next, in a state where the first valve 12 and the third valve 14 are closed and the pinch valve 11 and the second valve 13 are opened, the standard solution in the dilution tank 3 is supplied to the flow path 29 by the pipette injector 8.

[0068] (S309)

[0069] The computer 24 measures the potential of the standard solution in the flow path 29 by the Na ISE section 4, the K ISE section 5, and the Cl ISE section 6, and calculates the ion concentration on the basis of the measured potential.

[0070] (S310)

[0071] The computer 24 causes the pipette injector 8 and the like to act, and discharges the standard solution from the flow path 29. The discharge of the standard solution from the flow path 29 is performed in the same manner as the discharge of the detergent in S303. By the supply of the standard solution to the flow path 29 in S308 and the discharge of the standard solution from the flow path 29 in S310, one washing is performed.

[0072] (S311)

[0073] The computer 24 determines whether or not a difference between the potential measured in S309 and a potential measured last time, that is, a last difference, is within a prescribed range, for example, within ±0.2 mV. If the last difference is within the prescribed range, the process proceeds to S312, and if the last difference is not within the prescribed range, the process returns to S308. That is, if the last difference is not within the prescribed range, as the washing is insufficient, the washing based on the supply and discharge of the standard solution is performed again to the flow path 29.

[0074] (S312)

[0075] The computer 24 calculates an average value of the ion concentration of the standard solution from a plurality of values of the ion concentration calculated in S309. The calculated average value is stored in the memory 27 as one of the evaluation values for determining the presence or absence of an abnormality.

[0076] (S313)

[0077] The computer 24 calculates a predicted value of the deviation rate VR(N+1) of the next time from the deviation rate VR(N) of the present time calculated in S306 and the deviation rate VR(N-1) calculated last time, for example, using the following equation.

[0078] VR(N+1) = VR(N) + {VR(N) + VR(N-1)}... (Equation 2)

[0079] In addition, N = 1 and VR(0) = 0 are set immediately after the ion-selective electrode is replaced. That is, the predicted value of the deviation rate of the next time VR(2) is calculated as 2 · VR(1).

[0080] The calculated predicted value of the deviation rate of the next time VR(N+1) is stored in the memory 27 as one of the evaluation values for determining the presence or absence of an abnormality. In addition, the calculation of the predicted value of the deviation rate of the next time is not limited to (Equation 2). For example, the predicted value of the deviation rate of the next time VR(N+1) can be calculated by applying an extrapolation method to the deviation rates VR(1) to VR(N) of the times before the present time.

[0081] (S314)

[0082] The computer 24 determines the presence or absence of an abnormality on the basis of at least one of the evaluation values calculated in S305, S306, S312, and S313. In the case where there is an abnormality, a screen that notifies of the abnormality is displayed on the monitor 26.

[0083] Use Figure 5 The evaluation values will be described. Figure 5 As the evaluation values, the deviation rate of the potential of the detergent, the average value of the ion concentration of the detergent, the average value of the ion concentration of the standard solution, and the predicted value of the deviation rate are exemplified. In addition, for each evaluation value, an example of a normal range, a hypothetical abnormality content, and a screen example at the time of an abnormality are shown.

[0084] The deviation rate of the potential of the detergent is an evaluation value calculated in S305 and is used for the evaluation of the carryover. The normal range is set according to the rules of the detection facility, for example, less than 5%. In the case where the deviation rate of the potential of the detergent deviates from the normal range, it is determined that the carryover is large, the degree of deterioration of the ion-selective electrode or the leakage of the liquid from the connection portion with the flow path 29 is large, and a screen that notifies of the abnormality is displayed on the monitor 26. Figure 6The screen shown is Example 1. In Example 1, an abnormality in residue is indicated as an alarm name. Furthermore, a display prompts the operator to perform maintenance such as replacing the ion-selective electrode or cleaning the area around flow path 29.

[0085] The average ion concentration of the detergent is an evaluation value calculated in S306 and used for evaluating high-concentration areas. The normal range is set based on the detergent's ion concentration, for example, 5–7 (mol / L). If the average ion concentration of the detergent deviates from the normal range, it is determined that an anomaly exists in the high-concentration area, and an error is displayed. Figure 7 Example screen 2 is shown. In example screen 2, an abnormal high concentration area is indicated as an alarm name. Furthermore, a prompt is displayed to encourage the operator to replace the ion-selective electrode or maintain the device. As part of device maintenance, the operator checks the flow path 29 near the pipette syringe 8 for cracks, dirt, or blockages; if cracks, dirt, or blockages are found, the flow path 29 is repaired or replaced.

[0086] The average ion concentration of the standard solution is the evaluation value calculated in S312 and used for evaluating the low concentration region. The normal range is set according to the ion concentration of the standard solution, for example, 0.004–0.005 mol / L. If the average ion concentration of the standard solution deviates from the normal range, it is determined that there is an anomaly in the low concentration region, and an error is displayed. Figure 8 Example screen 3 is shown. In example screen 3, an abnormality in a low-concentration area is displayed as an alarm name. Furthermore, a prompt is displayed to encourage the operator to replace the ion-selective electrode or perform maintenance. Additionally, abnormalities in high-concentration areas are detected earlier than in low-concentration areas; therefore, if an abnormality occurs in a low-concentration area, an abnormality will also occur in a high-concentration area.

[0087] The predicted deviation rate is an evaluation value calculated in S313, used for evaluating the prevention and detection of residues. The normal range is set according to the rules of the detection facility, for example, less than 5%. If the predicted deviation rate deviates from the normal range, during the next cleaning, for example, if the electrolyte analyzer is cleaned 100 times per day, an abnormality in residues will be determined during the cleaning on the second day, and displayed. Figure 9 Example screen 4 is shown in the illustration. In example screen 4, the warning message "Caution: Leftovers" is displayed as an alarm name. Furthermore, a display prompts the operator to prepare for replacing the ion-selective electrode or for maintaining the device. The operator checks the inventory of the ion-selective electrode or orders one, preparing for its replacement. Moreover, the predicted value of the deviation rate is not limited to the next time; it can be calculated for subsequent predictions.

[0088] use Figure 10 This section illustrates the shift in the predicted value of the deviation rate using a visual example. Figure 10In this case, the vertical axis is the deviation rate, and the horizontal axis is the use (scheduled) day of the electrolyte analysis device 100, and the cleaning is performed every day, 8 / 2 is the last time, 8 / 3 is this time, and 8 / 4 is the next time. The predicted value of the deviation rate of the next time is calculated as A+Bx1 according to (Formula 2) from the deviation rate A of this time, and the difference B between the deviation rate of the last time and the deviation rate of this time. In addition, the deviation rate of the time after that can be calculated as A+Bx2, A+Bx3, A+Bx4, and so on by repeating (Formula 2). Figure 10 It is shown that, in the predicted value of the deviation rate of the next time, 8 / 4 to 8 / 6 are within the normal range, and 8 / 7 deviates from the normal range, and thus the operator plans to perform the preparation for replacing the ion selective electrode and the like.

[0089] Use Figure 11 that the combination of the presence or absence of abnormalities is determined based on a plurality of evaluation values. In addition, the high concentration region can detect abnormalities earlier than the low concentration region, and thus the combination of the presence or absence of abnormalities of the deviation rate of S305 and the high concentration region when the ion is provided in the detergent of high concentration is described.

[0090] Mode 1 is a case where the deviation rate and the high concentration region are normal, and the predicted value of the deviation rate is abnormal. In Mode 1, the screen example 1 illustrated in Figure 9 is displayed. In addition, in a case where the predicted value of the deviation rate is normal, the screen for notifying the abnormality is not displayed on the monitor 26. In addition, the high concentration region is normal, and thus the low concentration region is also normal.

[0091] Mode 2 is a case where the deviation rate and the high concentration region are abnormal. In Mode 2, in addition to the screen example 1 illustrated in Figure 6 for notifying the abnormality of the deviation rate, and the screen example 2 illustrated in Figure 7 for notifying the abnormality of the high concentration region, the screen example 5 illustrated in Figure 12 is also displayed. In the screen example 5, a plurality of errors are shown as the alarm name. In addition, the display for prompting the operator to replace or maintain the ion selective electrode, and to maintain the device is performed. In addition, in a case where the high concentration region is abnormal, there are a case where the low concentration region is abnormal, and a case where the low concentration region is normal.

[0092] Mode 3 is a case where the deviation rate is abnormal, and the high concentration region is normal. In Mode 3, the screen example 1 illustrated in Figure 6 is displayed. In addition, the high concentration region is normal, and thus the low concentration region is also normal.

[0093] Mode 4 is a case where the deviation rate is normal, and the high concentration region is abnormal. In Mode 4, the screen example 1 illustrated in Figure 7The illustrated screen example 2. Also, when there is an abnormality in the high-concentration region, there are a case where there is an abnormality in the low-concentration region and a case where there is no abnormality in the low-concentration region. In the case where there is an abnormality in both the high-concentration region and the low-concentration region, the screen example 5 can also be displayed Figure 12 The illustrated screen example 2. Also, when there is an abnormality in the high-concentration region, there are a case where there is an abnormality in the low-concentration region and a case where there is no abnormality in the low-concentration region. In the case where there is an abnormality in both the high-concentration region and the low-concentration region, the screen example 5 can also be displayed

[0094] The determination of the presence or absence of an abnormality based on a plurality of evaluation values is not limited to the combination of Figure 11 For example, the period elapsed from the replacement of each part of the electrolyte analysis device 100 can be used as an evaluation value together with the evaluation values calculated in S305, S306, S312, S313. Since the possibility of an abnormality occurring in a newly replaced part is low, the part that prompts maintenance can be selected depending on the length of the elapsed period after the replacement. For example, a screen display can also be performed to prompt maintenance of the part for which the elapsed time after the replacement exceeds a prescribed period.

[0095] With the above-described processing flow, the state of the ion-selective electrode and the like is determined based on the measurement value when the detergent in which ions are in a high concentration is supplied to the flow path 29, so an abnormality can be detected as early as possible. In addition, by enabling an abnormality to be detected as early as possible, the replacement preparation of the ion-selective electrode and the like can be performed in a planned manner, and the time, effort, and waste of materials required for the replacement and the like can be saved.

[0096] The above describes an embodiment of the present application. The present application is not limited to the above-described embodiment, and the structural elements can be modified within the scope of the gist of the application. In addition, a plurality of structural elements disclosed in the above-described embodiment can be appropriately combined. Also, several structural elements can be deleted from all the structural elements shown in the above-described embodiment.

[0097] Explanation of Reference Numerals

[0098] 1: sample container, 2: dispensing nozzle, 3: dilution tank, 4: Na ISE section, 5: K ISE section, 6: Cl ISE section, 7: comparison electrode, 8: pipette, 9: standard solution injector, 10: diluent injector, 11: pinch valve, 12: first valve, 13: second valve, 14: third valve, 15: first standard solution valve, 16: second standard solution valve, 17: first diluent valve, 18: second diluent valve, 19: comparison electrode liquid bottle, 20: standard solution bottle, 21: diluent bottle, 22: amplifier, 23: A / D converter, 24: computer, 25: keyboard, 26: monitor, 27: memory, 28: wiring, 29: flow path, 100: electrolyte analysis device, 400: setting screen, 401: number of washings selection button, 402: potential shift selection button, 403: number of times setting section, 404: potential setting section.

Claims

1. An electrolyte analyzing device including: an ion-selective electrode that generates a potential corresponding to a concentration of an ion contained in a sample, i.e., a sample potential; a comparison electrode that generates a potential serving as a reference, i.e., a reference potential; and a concentration calculating section that calculates the concentration of the ion based on a potential difference between the sample potential and the reference potential, characterized by further comprising an abnormality determining section that determines the presence or absence of an abnormality based on an evaluation value calculated using a detergent potential, which is a potential generated by the ion-selective electrode when a detergent is supplied.

2. An electrolyte analyzing device including: an ion-selective electrode that generates a potential corresponding to a concentration of an ion contained in a sample, i.e., a sample potential; a comparison electrode that generates a potential serving as a reference, i.e., a reference potential; and a concentration calculating section that calculates the concentration of the ion based on a potential difference between the sample potential and the reference potential, characterized by further comprising an abnormality determining section that determines the presence or absence of an abnormality based on an evaluation value calculated using a detergent potential, which is a potential generated by the ion-selective electrode when a detergent is supplied.

3. The electrolyte analyzing device according to claim 1 or 2, characterized in that the abnormality determining section further calculates a predicted value of the divergence rate for the next time based on the divergence rate calculated this time and the divergence rate calculated last time, and displays the predicted value of the divergence rate.

4. The electrolyte analyzing device according to claim 1 or 2, characterized in that the abnormality determining section further uses, as the evaluation value, an average value of the ion concentration calculated based on the potential reached after a certain period of time from the time when the detergent potential is measured each time the detergent is repeatedly supplied and discharged.

5. The electrolyte analyzing device according to claim 1 or 2, characterized in that the abnormality determining section further uses, as the evaluation value, an ion concentration calculated based on a potential generated by the ion-selective electrode when a standard solution is supplied.

6. The electrolyte analyzing device according to claim 1 or 2, characterized in that a solution containing sodium hypochlorite or sodium hydroxide is used as the detergent.

7. An abnormality determining method, which is an abnormality determining method for an electrolyte analyzing device including: an ion-selective electrode that generates a potential corresponding to a concentration of an ion contained in a sample, i.e., a sample potential; a comparison electrode that generates a potential serving as a reference, i.e., a reference potential; and a concentration calculating section that calculates the concentration of the ion based on a potential difference between the sample potential and the reference potential. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ an ion-selective electrode that generates a potential corresponding to the ion concentration in a sample, i.e., a sample potential; a comparison electrode that generates a potential serving as a reference, i.e., a reference potential; a concentration calculation section that calculates the ion concentration based on a potential difference between the sample potential and the reference potential, the abnormality determination method characterized by comprising: a step of detecting a potential generated by the ion-selective electrode when a detergent is supplied, i.e., a detergent potential; a step of calculating a deviance rate as an evaluation value, from the detergent potential measured each time the detergent is repeatedly supplied and discharged; a step of determining the presence or absence of an abnormality based on the evaluation value, the deviance rate is calculated using the detergent potential measured when the detergent is supplied for the first time and an average value of the detergent potential after a certain level is reached during the period in which the detergent is repeatedly supplied and discharged.

8. An abnormality determination method, which is an abnormality determination method for an electrolyte analysis device including: an ion-selective electrode that generates a potential corresponding to the ion concentration in a sample, i.e., a sample potential; a comparison electrode that generates a potential serving as a reference, i.e., a reference potential; a concentration calculation section that calculates the ion concentration based on a potential difference between the sample potential and the reference potential, the abnormality determination method characterized by comprising: a step of detecting a potential generated by the ion-selective electrode when a detergent is supplied, i.e., a detergent potential; a step of calculating a deviance rate as an evaluation value, from the detergent potential measured each time the detergent is repeatedly supplied and discharged; a step of determining the presence or absence of an abnormality based on the evaluation value, a predicted value of the deviance rate next time calculated from the deviance rate calculated this time and the deviance rate calculated last time is used as the evaluation value. ​ ​ ​ ​

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