JPH06331630A - Method for judging calibration result and method for dealing with calibration result - Google Patents

Abstract

PURPOSE:To determine whether or not calibration results are good without depending on human judgment by determining whether the calibration results are greater or smaller than preset upper and lower limit values corresponding to the measurement results of samples of known concentrations which are different when the samples are set in setting positions. CONSTITUTION:Samples of concentrations a0, a1, a2 (a0<1<a2) are sequentially set in pairs, and, if a measurement result obtained from one sample has been determined as being within a preset threshold range for upper and lower limits, it is determined whether or not determination has been made for all the samples. If determination has not been made for some of the samples, another sample is selected and it is determined whether or not its measurement result is within the threshold range. If determination has been made for all the samples, calibration is carried out to finish a series of processes. When any of the measurement results has been determined as being out of the threshold range, calibration abnormality is indicated and the process is finished. Should the third concentration a1 be misset to concentration a0, the measurement result corresponding to the concentration a0 is obtained which is out of the threshold range for the concentration a1, so calibration abnormality can surely be determined without necessitating human judgment.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for determining a calibration result and a method for processing a calibration result, and more specifically, it performs measurement in a state where samples of known concentrations different from each other are set, and based on the measurement result. The present invention relates to a new method for determining whether or not a calibration result (measurement result) is normal when calibrating a measuring device, and a new method for performing processing such as whether or not to adopt the calibration result based on the determination result. .

[0002]

2. Description of the Related Art Conventionally, in various measuring devices, in order to prevent occurrence of measurement error due to aging and measurement error due to lot change, measurement operation is performed using a sample of known concentration. Therefore, the calibration for compensating for the change with time based on the measurement result is performed prior to the actual measurement operation. Further, in such a measuring device, generally, since the measurement result of the measurement target substance is obtained based on the calibration curve given in advance and the actual measurement result, different known concentrations are obtained. The measurement operation is performed on each of the samples, and the calibration curve is corrected based on the plurality of measurement results. Furthermore, in order to efficiently perform calibration based on multiple samples, set samples with known concentrations different from each other in advance at predetermined positions, and perform sequential measurement operations on all the set samples. ing.

Therefore, by performing such a calibration before the actual measurement, it is possible to reliably compensate for changes over time and obtain highly accurate measurement results.

[0004]

However, since the samples having different known concentrations are set manually by the operator, the samples having different known concentrations are set at any sample setting position. In such a case, the measurement result obtained based on the erroneously set sample is calibrated as the measurement result for the sample of known concentration determined by the set position. As a result, there is an inconvenience that the measurement accuracy is rather lowered by performing the calibration. This is because a general worker has little knowledge about calibration, and therefore it is not possible to determine whether or not the calibration was normal by looking at the calibration result.

Even when the expert sees the calibration result and determines that the calibration is not normal, for example, until the calibration result which seems to be normal in view of the experience of the expert is obtained. Since the calibration is repeated, it takes a considerably long time in some cases, and there is a disadvantage that there is no guarantee that the calibration is absolutely normal. Furthermore, when an expert sees the calibration result and determines that the calibration is not normal, the calibration result may be artificially changed, but it is guaranteed that the changed calibration result is accurate. Since there is no such problem, there is an inconvenience that the accuracy of the measurement result cannot be guaranteed.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and provides a calibration result judging method capable of judging whether or not a calibration result is normal, without being influenced by arbitrary decision. The first purpose is to provide a calibration result processing method that can adopt a normal calibration result when the calibration result is not normal, and it is necessary to perform the calibration again. It is a third object to provide a calibration result processing method capable of identifying the sample set position where the calibration result is abnormal when there is a problem.

[0007]

In order to achieve the first object, the calibration result judging method according to claim 1 sets a sample of known concentration at a position where samples of known concentration different from each other should be set. In this state, each sample is measured, and the upper and lower limit values set in advance for at least one sample of known concentration and the corresponding measurement result are discriminated. This is a method of determining that the calibration result is abnormal when the value is out of the range of values.

In the calibration result judging method according to the second aspect of the present invention, each sample is measured in a state in which the samples of known concentration are set at the positions where the samples of known concentrations different from each other are set, and at least one known concentration is measured. The calibration curve set in advance corresponding to the sample is moved in parallel, the magnitude of the upper limit value of the movement amount and the parallel movement amount of the calibration curve are discriminated, and calibration is performed when the parallel movement amount exceeds the upper limit value. This is a method of determining that the result of the application is abnormal.

According to the calibration result judging method of the third aspect, in the state where the samples of known concentration are set at the positions where a plurality of samples of known concentrations different from each other should be set,
A method of measuring each sample, calculating the variation between the measurement results based on the samples that should have the same concentration, and determining that the calibration result is abnormal on the condition that the calculated variation is larger than a predetermined threshold value. Is.

In the calibration result judging method according to the fourth aspect of the present invention, the concentration of each sample is measured in the state where the sample having the known concentration is set at the position where the samples having the known concentrations different from each other are set, and the known results are different. Calculate the relative value between the measurement results based on the power sample, and determine that the calibration result is abnormal if the calculated relative value is outside at least one of the preset upper and lower limit values Is the way.

According to a fifth aspect of the present invention, the calibration result judging method is a method of adopting a slope change rate from a preset calibration curve as a relative value between measurement results based on samples which should have different known concentrations. The calibration result processing method according to claim 6 for achieving the second object is responsive to that the calibration result is determined to be abnormal by the method according to any one of claims 1 to 3. Then, the measurement results are sorted in a predetermined order in which samples of known concentration should be set.

According to a seventh aspect of the present invention, there is provided a calibration result processing method, wherein a sample having a known concentration is set in response to the fact that the calibration result is determined to be abnormal by any one of the first to third aspects. This is a method of omitting abnormal measurement results based on a predetermined order to be performed. Third above
The calibration result processing method according to claim 8 for achieving the object of (1), the measurement of each sample in a state in which a sample with a known concentration is set at a position where samples with known concentrations different from each other should be set. As a result of performing the above, in response to determining that the calibration result is abnormal by the method according to any one of claims 1 to 5,
Based on the residual measurement result excluding the measurement result based on at least one sample, it is determined whether the calibration result is abnormal by the method according to at least one of claims 1 to 5, and the calibration result is abnormal. In response to the determination result indicating that the calibration result is normal, the calibration result is determined again based on the residual measurement result excluding the measurement result based on the different sample, and the calibration result is normal. It is a method of displaying that the excluded sample is a sample not set at the position to be set, in response to the determination result shown.

[0013]

According to the calibration result determination method of claim 1, the measurement of each sample is performed in the state where the sample having the known concentration is set at the position where the samples having the known concentrations different from each other are set, The upper and lower limit values set in advance for the sample are compared with the measurement result, and if the measurement result is outside the range of both limit values, it is determined that the calibration result is abnormal. From
If a sample with a known concentration is set in the wrong position, the measurement result corresponding to the sample set in any position will be outside the limits of both limits, and it will be possible to calibrate without any artificial judgment. Can determine the abnormality of the application.

According to the calibration result judging method of the second aspect, at least one known sample is measured by measuring each sample in a state where the sample having the known concentration is set at the position where the samples having the known concentrations different from each other are set. When the calibration curve set in advance corresponding to the concentration sample is moved in parallel, the upper and lower limit values of the movement amount and the parallel movement amount of the calibration curve are discriminated, and the parallel movement amount exceeds the upper limit value. Since it is determined that the calibration result is abnormal, if the sample of known concentration is set at the wrong position, the parallel movement is performed based on the measurement result corresponding to the sample set at any position. The parallel movement amount of the obtained calibration curve exceeds the upper limit value, and the abnormality of the calibration can be surely judged without any artificial judgment.

According to the calibration result judging method of the third aspect, the measurement of each sample is carried out in the state where the samples of known concentration are set at the positions where a plurality of samples of known concentrations different from each other should be set, and the same measurement is performed. The accuracy of the calibration result is calculated by calculating the variation between the measurement results based on the sample that should be the concentration and judging that the calibration result is abnormal on the condition that the calculated variation is larger than a predetermined threshold value. When setting a plurality of samples of each known concentration in order to increase the, if the samples of different known concentrations are set, the measurement results based on these samples will vary greatly,
It is possible to reliably determine an abnormality in calibration without going through any artificial judgment.

According to the calibration result determination method of claim 4, the concentration of each sample is measured in the state where the sample of the known concentration is set at the position where the sample of the known concentration different from each other is set, and the different known concentration is measured. The relative value between the measurement results based on the sample should be calculated, and if the calculated relative value is outside the range of at least one of the preset upper and lower limit values, the calibration result is abnormal. Since the judgment is made, when the set positions of the samples of known concentration are wrong, the relative values of the measurement results based on these samples will be significantly different from the normal values, and artificial judgment will be required. A calibration abnormality can be reliably determined without passing through.

According to the calibration result determination method of the fifth aspect, the slope change rate from the preset calibration curve is adopted as the relative value between the measurement results based on the samples which should have different known concentrations. Therefore, if the set positions of samples with known concentrations are wrong, the rate of change in inclination based on the measurement results based on these samples will be significantly different from that in the normal case, and artificial judgment must be performed. It is possible to reliably determine an abnormality in calibration.

According to the calibration result processing method of claim 6, in response to the determination that the calibration result is abnormal by any of the methods of claims 1 to 5, the measurement result is Since samples of known concentration are sorted in a predetermined order that should be set, even if the sample setting position is wrong, there is no need to perform calibration again, and accurate calibration results can be obtained. it can. Of course, it is possible to prevent an increase in the required amount of the sample of known concentration used for the concentration measurement.

According to the calibration result processing method of claim 7, in response to the fact that the calibration result is judged to be abnormal by the method of any one of claims 1 to 5, Since abnormal measurement results are omitted based on the predetermined order in which
When an accurate calibration result can be obtained even if the measurement result is slightly reduced, it is not necessary to perform the calibration again, and an accurate calibration result can be obtained. Of course, it is possible to prevent an increase in the required amount of the sample of known concentration used for the measurement.

According to the calibration result processing method of claim 8, the measurement of each sample is performed in a state where the sample of known concentration is set at the position where at least three kinds of samples of known concentration different from each other should be set. As a result, claim 1
The method according to any one of claims 1 to 5, wherein in response to the determination that the calibration result is abnormal by any one of the methods, the measurement results based on the remaining measurement results except the measurement result based on at least one sample are used. It is determined whether or not the calibration result is abnormal by at least one method of 5, and in response to the determination result indicating that the calibration result is abnormal, the remaining measurement results excluding the measurement results based on different samples The sample which is not set at the position where the excluded sample should be set in response to the judgment result indicating that the calibration result is normal based on the Since it is displayed, it is accurate by repeating the measurement operation only for the sample that was not set at the position to be set. It is possible to obtain a calibration result, it is possible to significantly increase the workability of the calibration in the case as set miss occurs can shorten the time required as a whole. Of course, the required amount of sample of known concentration used for the measurement can be reduced.

[0021]

Embodiments will be described in detail below with reference to the accompanying drawings showing embodiments. FIG. 15 is a diagram schematically showing the sample setting position for calibration, in which the concentrations are a0, a1,
It is instructed that two samples of a2 (for example, a0 <a1 <a2) should be set in order two by two.

FIG. 1 is a flow chart for explaining an embodiment of the calibration result judging method of the present invention.
It waits until the measurement results based on all the samples are obtained in step SP1, and whether or not the measurement results obtained based on the sample of 1 in step SP2 is within the preset upper and lower limit values. If it is determined that the measurement result is within the range of both limit values, it is determined in step SP3 whether or not the determination in step SP2 has been performed for the measurement results corresponding to all the samples, and step SP2 If there is a sample for which the determination is not made, another sample is selected in step SP4,
The determination in step SP2 is performed again. Conversely, step S
When it is determined in P3 that the determination in step SP2 has been performed for the measurement results corresponding to all the samples, the calibration process (correction process based on the measurement result) is performed in step SP5, and the series of processes ends. . Further, when it is determined in step SP2 that the measurement result is out of the range of both limit values, in step SP6 it is displayed that the calibration is abnormal, and the series of processes is ended. Of course, in this case, the fact that the calibration should be performed again may be displayed, and the operator can be informed of what to do when the calibration result is abnormal.

Therefore, the concentration of the set sample is a
If 0, a0, a1, a1, a2, a2, there is no sample set-up error, so the measurement results obtained based on all samples fall within the limits of both limits, and the calibration result is normal. Then, the calibration process is performed as it is. However, when the concentration of the set sample is, for example, a0, a0, a0, a1, a2, a2, the concentration should be set as the third sample, even though the concentration of a1 should be set. Is set to a0, the measurement result corresponding to the concentration a0 is obtained, and the value is outside the range of both limit values corresponding to the sample of the concentration a1 (specifically, a value smaller than the lower limit value). Become. Therefore, it can be determined that the calibration result is abnormal, and it is possible to prevent the output of an incorrect measurement result based on the abnormal calibration result.

In this embodiment, it is determined whether or not the measurement results based on all the samples are within the range of the corresponding both limit values. For example, the setting of both limit values is simple. In order to realize, it is, of course, possible to determine whether or not the measurement result based on any of the samples is within the range of the corresponding limit values. However, in this case, it is preferable to use another discrimination method described later together.

[0025]

[Embodiment 2] FIG. 2 is a flow chart for explaining another embodiment of the calibration result judging method of the present invention. In step SP1, it waits until the measurement results based on all the samples are obtained, and in step SP2, either The variation between the measurement results based on the two samples that should correspond to the concentration is calculated, and in step SP3, it is determined whether or not the calculated variation exceeds the preset limit value of the variation, and the variation is detected. When it is determined that the variation limit value is not exceeded, step SP4
In step SP5, it is determined whether or not the variations corresponding to the two samples that should correspond to all the concentrations have been determined. Two samples that should correspond to the concentration are selected, and the process of step SP2 is performed again.
On the contrary, when it is determined in step SP4 that the variation based on the measurement results corresponding to all the samples is determined, the calibration processing (correction processing based on the measurement result) is performed in step SP6 to perform a series of operations. The process ends. If it is determined in step SP3 that the variation exceeds the variation limit value, then in step SP7 it is displayed that the calibration is abnormal, and the series of processes ends.
Of course, in this case, the fact that the calibration should be performed again may be displayed, and the operator can be informed of what to do when the calibration result is abnormal.

Therefore, the concentration of the set sample is a
If 0, a0, a1, a1, a2, a2, there is no sample setting error, so the variation between the measurement results obtained based on all pairs of samples is less than or equal to the preset limit value of variation. , The calibration result is determined to be normal, and the calibration process is performed as it is. However, if the concentration of the set sample is
In the case of a0, a0, a0, a1, a2, a2,
As the third sample, the one with concentration a1 should be set, but the one with concentration a0 was set, so the measurement result based on the sample corresponding to concentration a0 and the sample with concentration a1 The variation with the measurement result based on the sample that should correspond to is large and exceeds the limit value of the variation, so it can be determined that the calibration result is abnormal, and the incorrect measurement result based on the abnormal calibration result is output. This can be prevented.

However, it is preferable to improve the determination accuracy by using the above determination method and / or the determination method described later together.

[0028]

[Third Embodiment] FIG. 3 is a flow chart for explaining still another embodiment of the calibration result judging method according to the present invention. In step SP1, the process waits until the measurement results based on all the samples are obtained, and then in step SP2, they are mutually called. A ratio (a kind of relative value) of the measurement results based on two samples that should correspond to different concentrations is calculated, and in step SP3, the calculated ratio is outside the preset upper and lower limit values. If it is determined that the ratio is within the limits of both limits, the ratios corresponding to two samples that should correspond to the concentrations of all the combinations are determined in step SP4. If there is a combination of samples for which the ratio has not been determined, it should correspond to the concentration of another combination in step SP5.
One sample is selected and the process of step SP2 is performed again. On the contrary, if it is determined in step SP4 that the ratios of the measurement results corresponding to all the combinations of samples have been determined, a calibration process (correction process based on the measurement results) is performed in step SP6 to perform a series of steps. Ends the process. Further, when it is determined in step SP3 that the ratio is out of the range of both limit values, it is displayed in step SP7 that the calibration is abnormal, and the series of processes is ended. Of course, in this case, the fact that the calibration should be performed again may be displayed, and the operator can be informed of what to do when the calibration result is abnormal.

Therefore, the concentration of the set sample is a
If 0, a0, a1, a1, a2, a2, there is no sample mis-setting, so the ratio of the measurement results obtained based on the samples corresponding to all the concentration combinations is below the preset limit value. Then, it is determined that the calibration result is normal, and the calibration process is performed as it is. However, if the concentration of the set sample is, for example, a
3 if 0, a0, a0, a1, a2, a2
Although the concentration of a1 should be set as the second sample, the concentration of a0 should be set. Therefore, the measurement result based on the sample corresponding to the concentration a0,
Since the ratio of the measurement result based on the sample that should correspond to the sample of the concentration a1 is smaller than the lower limit value, it can be determined that the calibration result is abnormal, and an incorrect measurement result based on the abnormal calibration result is output. Can be prevented. Further, since the ratio of the concentration measurement result based on the sample corresponding to the concentration a1 and the concentration measurement result based on the sample corresponding to the concentration a2 is larger than the upper limit value, similarly, the calibration result is It can be determined that there is an abnormality, and it is possible to prevent the output of an incorrect measurement result based on the abnormal calibration result.

In this embodiment, it is judged whether or not the ratio of the measurement results is outside the upper and lower limit values. However, in order to simplify the processing and the limit value setting, Only one of the limit values may be adopted. Of course, it is preferable to improve the determination accuracy by using the above determination method together.

[0031]

[Fourth Embodiment] FIG. 4 is a flow chart for explaining an embodiment of the calibration result processing method of the present invention.
When it is determined that the calibration result is abnormal as a result of performing the processing based on at least one of the flowcharts in FIGS. 1 to 3, in step SP1,
Based on the preset sample set position, the order based on the magnitude of the measurement results when the calibration is normal is extracted, and the measurement results based on all the samples are sorted in step SP2 by the order based on the extracted magnitude. And adopted as a normal calibration result,
A calibration process is performed in step SP3.

Therefore, the concentration of the set sample is a
1, a1, a0, a0, a2, a2, sample a1
Is larger than the measurement result based on the sample a0, and the measurement result based on the sample a1 is
Since it is smaller than the measurement result based on 2, the normal calibration result can be obtained by exchanging the measurement result obtained based on the sample a1 and the measurement result obtained based on the sample a0. As a result, it becomes unnecessary to perform the calibration again, and moreover, it becomes possible to output the accurate measurement result based on the normal calibration result. In the above embodiment, the measurement results are sorted only when it is determined that the calibration result is abnormal, but when the measurement result is obtained, it is determined whether the calibration result is normal or abnormal. It goes without saying that the sorting may be carried out without doing so, and then the determination as to whether it is normal or abnormal may be made.

[0033]

[Embodiment 5] FIG. 5 is a flow chart for explaining another embodiment of the calibration result processing method of the present invention, in which the measurement results are sorted in step SP1 and at least in steps SP2 of FIG. 1 to FIG. It is determined whether the calibration result is normal or abnormal by performing the process based on at least one flowchart. When it is determined that the calibration result is abnormal, the abnormal measurement result is detected in step SP3, all the measurement results except the detected abnormal measurement result are adopted in step SP4, and step SP5 At, the calibration process is performed based on the adopted measurement result. If it is determined in step SP2 that the calibration result is normal, the process of step SP5 is performed as it is. Therefore, the concentration of the set sample is, for example, a0,
In the case of a0, a0, a1, a2, a2, since the measurement result based on the third sample is abnormal, a normal calibration result can be obtained by omitting only the measurement result based on this sample. You can As a result, it is not necessary to perform the calibration again, and the workability of the calibration can be improved and the time can be shortened. Of course, it is possible to suppress an increase in the consumption of the sample.

[0034]

[Sixth Embodiment] FIG. 6 is a flow chart for explaining still another embodiment of the calibration result processing method of the present invention. In the flow chart below, the actual measurement results are shown as S0, S1, ..., S5 (however, S0, S
, ..., S5 are, for example, sorted in ascending order), and samples with known concentrations are labeled X0, X1, X
2, the measurement results corresponding to the respective samples X0, X1, X2 are indicated by Y0, Y1, Y2, the parallel movement amount for correcting the standard calibration curve is indicated by α, and the upper limit of the parallel movement amount is indicated. The values are indicated by αmax, and the upper and lower limit values of the rate of change of the slope of the calibration curve when the reference calibration curve is corrected based on the measurement results of at least two types of known concentrations are indicated by βmax and βmin, respectively. , The limit value of the variation of the measurement results based on two or more samples of equal known concentrations to each other is indicated by CVmax, the upper and lower limit values of the measurement result Y0 are indicated by Y0max and Y0min, respectively, based on the measurement results Y0 and Y1. The lower limit of the obtained ratio is R0
1 min, the lower limit value of the ratio obtained based on the measurement results Y1 and Y2 is indicated by R12 min, based on the difference between the measurement results of the two kinds of known concentration samples and the measurement result of one known concentration sample. The upper and lower limit values of the obtained percentage are shown by Pmax and Pmin, respectively. Incidentally, Pm
ax and Pmin are upper and lower limit values that are effective only when the calibration curve is not included. Of course, in this case,
αmax, βmax, βmin do not apply. Also,
CVmax is only effective when making measurements based on multiple samples of the same known concentration. Furthermore, R12mi
n, βmax, and βmin are effective only when performing measurement based on two kinds of samples having known concentrations other than 0. Furthermore, when a linear approximation effective when the concentration measurement range is narrow is adopted, Y0max, Y0min, R01
min does not apply.

As a result of performing at least the processing based on at least one of the flowcharts of FIGS. 1 to 3 and the sorting processing of FIG. 4 in a state in which the samples are set at predetermined positions where the samples of three kinds of known concentrations should be set. If the calibration result is determined to be abnormal, the sample X with the lowest known concentration in step SP1
It is determined whether or not the measurement result Y0 based on 0 exists.
Specifically, the upper and lower limit values Y0max and Y0min of the measurement result Y0 based on the sample X0 having the lowest known concentration and the measurement results S0 and S based on all the samples actually set.
1 and S2 are compared, and both limit values Y0max,
When there is a measurement result included in the range of Y0min, the measurement result Y0 based on the sample X0 having the lowest known concentration
Is determined to exist.

When it is determined in step SP1 that the measurement result Y0 based on the sample X0 having the lowest known concentration exists, the lowest measurement result S0 and the highest measurement result S2 are respectively known in the lowest concentration in step SP2. The standard calibration curve is corrected assuming that the measurement result Y0 is based on the sample X0 of the concentration and the measurement result Y2 is based on the sample X2 of the highest known concentration, and the standard calibration curve is corrected.
In P3, it is determined whether or not the deviation amount α between the corrected calibration curve and the reference calibration curve is within the range of the upper limit value αmax.

If it is determined in step SP3 that the deviation amount α is within the range of the upper limit value αmax, in step SP4, the lowest measurement result S0 and the highest measurement result S2 are the lowest known concentrations. Is a measurement result Y0 based on the sample X0, and a measurement result Y2 based on the sample X2 having the highest known concentration, and the measurement result S1 based on the intermediate known concentration sample X1 is displayed as a series of processing. To finish.

When it is determined in step SP3 that the deviation amount α is outside the range of the upper limit value αmax, in step SP5, the lowest measurement result S0 and the highest measurement result S2 are known to have the lowest densities. The calibration curve serving as the reference is corrected assuming that the measurement result Y0 based on the sample X0 of the concentration and the measurement result Y1 based on the sample X1 of the intermediate known concentration, and the corrected calibration curve and the calibration based on the reference are corrected in step SP6. It is determined whether or not the deviation amount α from the line is within the range of the upper limit value αmax.

When it is determined in step SP6 that the deviation amount α is within the range of the upper limit value αmax, in step SP7, the lowest measurement result S0 and the highest measurement result S2 are the lowest known concentrations. The measurement result Y0 based on the sample X0 and the measurement result Y1 based on the sample X1 having the intermediate known concentration, and the measurement result S1 based on the sample X2 having the highest known concentration is displayed as a series of processes. To finish.

When it is determined in step SP6 that the deviation amount α is outside the range of the upper limit value αmax, in step SP8 it is displayed that an abnormal measurement result cannot be specified, and the series of processes is ended. . When it is determined in step SP1 that the measurement result Y0 based on the sample X0 having the lowest known concentration does not exist, the lowest measurement result S0 and the highest measurement result S2 are respectively set to the sample having the intermediate known concentration in step SP9. X
It is assumed that the measurement result Y1 based on 1 and the measurement result Y2 based on the sample X2 having the highest known concentration and the measurement result Y0 based on the sample X0 having the lowest known concentration are the upper and lower limit values Y0max and Y0min. The average value is assumed to be the measurement result Y0 based on the sample X0 having the lowest known concentration, and it is determined in step SP10 whether or not the above-mentioned assumed measurement results Y1 and Y2 are out of the corresponding limit values. (Specifically, the above-mentioned limit values αmax and βma
x, βmin, CVmax, Y0max, Y0min,
Of R01min, R12min, Pmax, and Pmin, the corresponding limit value is sequentially selected to determine whether or not it is outside the range of the limit value.) If it is determined to be out of the range, an abnormality is detected in step SP11. A series of processing is ended by displaying that no specific measurement result can be specified. vice versa,
When it is determined in step SP10 that the measurement results Y1 and Y2 are within the range of the limit value, the lowest measurement result S0 and the highest measurement result S2 in SP12 are the measurement results based on the intermediate known concentration sample X1. Y
1. The measurement result Y2 based on the sample X2 having the highest known concentration, and the measurement result S1 based on the sample X0 having the lowest known concentration are displayed as abnormal, and the series of processes is ended.

As is clear from the above, when the calibration results are judged to be abnormal as a result of performing the calibration based on the three samples having different known concentrations from each other, there is a very high probability that a sample set error or the like will occur. Therefore, when recalibrating, it suffices to set only the relevant sample and perform calibration, which improves workability during recalibration and reduces the time required. Can be shortened.

FIG. 7 is a flow chart for explaining another specific example of the calibration result processing method of the present invention. In the state where the samples are set at predetermined positions where two samples of two kinds of known concentrations should be set respectively. If at least the result of performing the processing based on at least one of the flowcharts of FIGS. 1 to 3 and the sorting processing of FIG. 4 is that the calibration result is abnormal, the two higher measurements in step SP1. Result S
The average value of S2 and S3 is set to the sample X1 of high known concentration.
Is assumed to be the measurement result Y1 corresponding to, and the measurement result S1 is assumed to be the measurement result Y0 corresponding to the sample X0 having a low known concentration, and one of the lower measurement result S1 and the addition average value are respectively determined in step SP2. It is determined whether or not it is within the range of the limit value (specifically, the above-mentioned limit value αm
ax, βmax, βmin, CVmax, Y0max,
Y0min, R01min, R12min, Pmax,
Among Pmin, the corresponding limit value is sequentially selected to determine whether or not it is outside the range of the limit value. same as below). Then, when it is determined that all of them are within the range of the limit value, in step SP3, it is displayed that the other lower measurement result S0 is abnormal, and the series of processes is ended.

When it is determined in step SP2 that at least one of them is outside the range of the limit value, the other measurement result S0 is adopted in place of the one measurement result S1 in step SP4, and the step S4 is executed. SP5
At S0, it is determined whether or not the above-mentioned average value is within the range of the limit value. Then, when it is determined that all of them are within the range of the limit value, in step SP6, it is displayed that one of the lower measurement results S1 is abnormal, and the series of processes is ended.

If it is determined in step SP5 that at least one of these is out of the range of the limit value, the two lower measurement results S in step SP7.
0, S1 is added to the sample X0 of known concentration of low concentration
In step SP8, it is determined whether or not one of the higher measurement result S3 and the average value is within the limit value range. Then, when it is determined that all of them are within the range of the limit value, in step SP9, it is displayed that the other measurement result S2 of the higher one is abnormal, and the series of processes is ended.

When it is determined in step SP8 that at least one of these is out of the range of the limit value, the one measurement result S3 is obtained in step SP10.
Instead of the above, the other measurement result S2 is adopted, and in SP11, it is determined whether S2 and the above-mentioned average value are within the limits. Then, when it is determined that all of them are within the range of the limit value, in step SP12, it is displayed that one of the higher measurement results S3 is abnormal, and the series of processes is ended.

If it is determined in step SP11 that at least one of these values is outside the range of the limit value, the processing based on the flowchart of FIG. 8 is performed. Figure 8
Measurement result S in step SP1 of the flowchart of FIG.
It is assumed that S2 and S3 are the measurement results corresponding to the low-concentration known concentration sample and the measurement result corresponding to the high-concentration known concentration sample, respectively, and whether S2 and S3 are within the range of the limit value in step SP2. Determine whether. If it is determined that both are within the range of the limit value, in step SP3 it is displayed that the measurement results S0 and S1 respectively corresponding to the samples X0 and X1 are abnormal, and the series of processes is ended. .

When it is determined in step SP2 that either of them is outside the range of the limit value, the measurement result S0 is adopted in place of the measurement result S2 in step SP4, and both of them are within the range of the limit value in step SP5. Or not. If it is determined that both are within the range of the limit value, the sample X is determined in step SP6.
The measurement results S1 and S2 corresponding to 0 and X1, respectively, are displayed as abnormal, and a series of processing is terminated.

When it is determined in step SP5 that either of the values is outside the range of the limit value, the measurement result S1 is adopted in place of the measurement result S3 in step SP7, and both are within the range of the limit value in step SP8. Or not. Then, when it is determined that both are within the range of both limit values, the sample X is determined in step SP9.
The measurement results S2 and S3 corresponding to 0 and X1, respectively, are displayed as abnormal, and the series of processing ends.

When it is determined in step SP8 that any of the values is out of the range of the limit value, step SP10.
At, the fact that an abnormal measurement result cannot be specified is displayed, and a series of processing ends. Therefore, when it is determined that the calibration result is abnormal, it is possible to identify one or two sample set errors, etc. with a fairly high probability. It suffices to set and to perform calibration, which can improve the workability at the time of recalibration and reduce the time required.

FIG. 9 is a flow chart for explaining still another specific example of the calibration result processing method of the present invention, in which three samples of known concentrations are set at predetermined positions where two samples should be set. As a result of at least the processing based on at least one of the flowcharts of FIGS. 1 to 3 and the sorting processing of FIG.
When it is determined that the calibration result is abnormal, it is determined in step SP1 whether or not the measurement result Y0 corresponding to the sample X0 having the low known concentration is present. If the measurement result is present, In step SP2, the arithmetic mean value of the two higher measurement results S4 and S5 and the arithmetic mean value of the two middle measurement results S2 and S3 are respectively taken as the measurement result Y2 corresponding to the sample X2 having a high known concentration and the intermediate value. Assuming that the measurement result Y1 corresponds to the sample X1 having a known concentration, it is determined in step SP3 whether or not one of the lower measurement result S1 and the average value is within the limit value range (specifically, , The above limit value αma
x, βmax, βmin, CVmax, Y0max, Y
0min, R01min, R12min, Pmax, P
Among min, the corresponding limit value is sequentially selected to determine whether or not it is outside the range of the limit value. same as below). Then, when it is determined that all of them are within the range of the limit value, in step SP4, it is displayed that the other lower measurement result S0 is abnormal, and the series of processes is ended. When it is determined in step SP1 that the measurement result Y0 does not exist, the process of the flowchart of FIG. 12 is performed.

If any of these is determined to be outside the range of the limit value in step SP3, the other measurement result S0 is adopted in place of one measurement result S1 in step SP5, and the lower measurement result is obtained in step SP6. It is determined whether the other measurement result S0 and the average value are within the limits. If it is determined that these are all within the limits, step SP
At 7, the lower one of the measurement results S1 is displayed as abnormal, and the series of processes is ended.

If it is determined in step SP6 that any of these is outside the range of the limit value, in step SP8 the higher average of the two measurement results S4 and S5 and the lower two of the measurement results. It is assumed that the addition average value of the results S0 and S1 is the measurement result Y2 corresponding to the high-concentration known concentration sample X2 and the measurement result Y0 corresponding to the low-concentration known concentration sample X0, respectively. It is determined whether or not the measurement result S3 and the average value are within the limits. Then, when it is determined that all of them are within the range of the limit value, in step SP10, it is displayed that the other intermediate measurement result S2 is abnormal, and the series of processes is ended.

If any of these is judged to be outside the range of the limit value in step SP9, the other measurement result S2 is adopted in place of one measurement result S3 in step SP11, and the intermediate result is obtained in step SP12. It is determined whether the other measurement result S2 and the arithmetic mean value are within the limits. If it is determined that these are all within the range of the limit value, step S
In P13, the fact that one of the intermediate measurement results S3 is abnormal is displayed, and a series of processing ends.

When it is determined in step SP12 that any of these is out of the range of the limit value, in step SP14 the average value of the two intermediate measurement results S2 and S3 and the two lower measurement results are obtained. Assuming that the arithmetic mean value of S0 and S1 is the measurement result Y1 corresponding to the sample X1 having an intermediate known concentration and the measurement result Y0 corresponding to the sample X0 having a low known concentration, respectively, one of the high concentrations is measured in step SP15. It is determined whether the result S5 and the arithmetic mean value are within the limits. Then, when it is determined that all of these are within the range of the limit value, in step SP16, it is displayed that the other measurement result S4 of high concentration is abnormal, and the series of processes is ended.

If it is determined in step SP15 that any of these is out of the range of the limit value, the other measurement result S4 is adopted in place of the one measurement result S5 in step SP17, and the higher measurement result is obtained in step SP18. It is determined whether or not the other density measurement result S4 and the average value are within the limits. When it is determined that all of these are within the range of the limit value, one measurement result S5 of the high concentration is obtained in step SP19.
Is displayed abnormally, and a series of processing ends.

If it is determined in step SP18 that any of these is out of the range of the limit value, it is possible that two or more measurement results are abnormal. Therefore, the processing based on the flowchart of FIG. To do. In step SP1 of the flowchart of FIG. 10, the obtained measurement results S3, S4, and S5 are the measurement results Y0 corresponding to the low-concentration known concentration sample X0, and the measurement result corresponding to the intermediate-concentration known concentration sample X1. Y1 is assumed to be the measurement result Y2 corresponding to the sample X2 having a high known concentration, and it is determined in step SP2 whether these measurement results are outside the range of the limit value. In response, in step SP3 or step SP4, the determination result P1 indicating the above assumption and determination result is set to "NG" or "OK".

Next, in step SP5, the obtained measurement results S0, S4 and S5 are measured results Y0 corresponding to the low concentration known sample X0 and the intermediate measurement result corresponding to the known concentration sample X1. Y1 is assumed to be the measurement result Y2 corresponding to the sample X2 having a high known concentration, and it is determined in step SP6 whether these measurement results are outside the range of the limit value. In response, in step SP7 or step SP8, the determination result P2 indicating the above assumption and the determination result is set to "N".
Set to G "or" OK ".

Next, in step SP9, the obtained measurement results S0, S1, S5 are measured results Y0 corresponding to the low-concentration known concentration sample X0, and measurement results corresponding to the intermediate concentration known-concentration sample X1. Y1 is assumed to be the measurement result Y2 corresponding to the sample X2 having a high known concentration, and it is determined in step SP10 whether these measurement results are outside the range of the limit value. In response, step SP11 or step SP12
In the above, the determination result P3 indicating the above assumption and the determination result
Is set to "NG" or "OK".

Then, in step SP13, the obtained measurement results S0, S1, S2 are measured results Y0 corresponding to the low-concentration known concentration sample X0, and measurement results corresponding to the intermediate concentration known-concentration sample X1. Y1 is assumed to be the measurement result Y2 corresponding to the sample X2 having a high known concentration, and it is determined in step SP14 whether these measurement results are outside the range of the limit value. In response, step SP15 or step SP16
In the above, the determination result P4 indicating the above assumption and the determination result
Is set to "NG" or "OK".

As described above, the discrimination results P1, P2, P
After 3 and P4 are obtained, an abnormal measurement result can be specified based on the combination of the obtained discrimination results. In particular,
When P1 = P2 = OK and P3 = P4 = NG, the measurement result S2 corresponding to the sample X1 having a known intermediate concentration and the measurement result S3 corresponding to the sample X2 having a high known concentration are abnormal. (Normal S0 and S1 correspond to sample X0, S4 corresponds to sample X1, and S5 corresponds to sample X2). When P1 = P4 = NG and P2 = P3 = OK, the measurement result S1 corresponding to the low-concentration known concentration sample X0 and the measurement result S4 corresponding to the high-concentration known concentration sample X2 are abnormal ( Normal S0 corresponds to sample X0, S2 and S3 correspond to sample X1, and S5 corresponds to sample X2). When P1 = P2 = NG and P3 = P4 = OK, the measurement result S2 corresponding to the sample X0 having a low known concentration and the measurement result S3 corresponding to the sample X1 having a known intermediate concentration are abnormal. (Normal S0 is sample X0
, S1 corresponds to the sample X1, and S4 and S5 correspond to the sample X2). When only P1 is OK, it corresponds to the measurement result S0 corresponding to the sample X0 having a low known concentration, the measurement result S1 corresponding to the sample X1 having a known intermediate concentration, and the sample X2 having a known high concentration. The measured result S2 is abnormal (normal S3 corresponds to sample X0,
4 corresponds to sample X1 and S5 corresponds to sample X2).
When only P2 is OK, it corresponds to the measurement result S1 corresponding to the sample X0 having a low known concentration, the measurement result S2 corresponding to the sample X1 having a known intermediate concentration, and the sample X2 having a known high concentration. The measured result S3 is abnormal (normal S0 corresponds to sample X0, S4 corresponds to sample X1, and S5 corresponds to sample X2). When only P3 is OK, it corresponds to the measurement result S2 corresponding to the sample X0 having a low known concentration and the measurement result S3 corresponding to the sample X1 having a known intermediate concentration and the sample X2 having a known high concentration. The measurement result S4 is abnormal (normal S0 corresponds to sample X0, S1 corresponds to sample X1, and S5 corresponds to sample X1).
2). When only P4 is OK, it corresponds to the measurement result S3 corresponding to the sample X0 having a low known concentration and the measurement result S4 corresponding to the sample X1 having a known intermediate concentration and the sample X2 having a known high concentration. Measurement result S
5 is abnormal (normal S0 corresponds to sample X0, S1
Corresponds to sample X1 and S2 corresponds to sample X2).

FIG. 11 is a flow chart for explaining the processing when P1 to P4 are combinations other than the above. In step SP1, the obtained measurement results S0 and S5 correspond to the sample X0 of low known concentration. Measurement result Y
0, the measurement result Y2 corresponding to the sample X2 of high known concentration is assumed, and in step SP2, the deviation amount α from the reference calibration curve when the calibration curve is corrected based on this assumption is the upper limit value. It is determined whether or not it is within the range of αmax. Then, the shift amount α is the upper limit value αmax
If it is within the range, the process of the flowchart of FIG. 13 is performed.

When it is determined in step SP2 that the deviation amount α is outside the upper limit value αmax, in step SP3, the obtained measurement results S0 and S5 are used as the sample X0 of low known concentration. Assuming that the corresponding measurement result Y0 is the measurement result Y1 corresponding to the sample X1 having a known intermediate concentration, and in step SP4, the deviation amount α from the reference calibration curve when the calibration curve is corrected based on this assumption Is determined to be within the range of the upper limit value αmax. Then, the shift amount α is the upper limit value α
If it is within the range of max, the processing of the flowchart of FIG. 14 is performed.

When it is determined in step SP4 that the shift amount α is outside the upper limit value αmax, in step SP5 it is displayed that an abnormal measurement result cannot be specified and the series of processes is terminated. FIG. 12 is a flow chart for explaining the processing in the case where the measurement result Y0 corresponding to the sample X0 having a low known concentration does not exist. In step SP1, the lowest measurement result S0 and the highest measurement result S5 are set to intermediate known values. Concentration sample X
Assuming that the measurement result Y1 based on 1 and the measurement result Y2 based on the sample X2 having the highest known concentration are the average values of the limit values Y0max and Y0min of the measurement result Y0 based on the sample X0 having the lowest known concentration. Assuming a measurement result Y0 based on the sample X0 having the lowest known concentration,
In step SP2, the above-mentioned assumed measurement result Y
It is determined whether or not 0, Y1, and Y2 are out of the range of the corresponding limit value. If it is determined that they are out of the range, it is displayed in step SP3 that an abnormal measurement result cannot be specified and a series of Ends the process. Conversely, step SP2
When it is determined that the measurement results Y0, Y1, Y2 are within the range of the limit value in step S4, the variation CV1 of the measurement results S0, S1 and the measurement result S are determined in step SP4.
The variation CV2 of S4 and S5 is calculated. Then, in step SP5, it is determined whether or not both the variations CV1 and CV2 are smaller than the variation limit value CVmax.
If both the variations CV1 and CV2 are small, the measurement results S2 and S3 corresponding to the sample X0 having a low known concentration in step SP6 are abnormal and normal S0 and S1 are obtained.
Indicates that the sample corresponds to the sample X1, and S4 and S5 correspond to the sample X2, and the series of processes ends.

When it is determined in step SP5 that any variation exceeds the variation limit value CVmax, it is determined in step SP7 whether only the variation CV2 exceeds the variation limit value CVmax, Only the variation CV2 is the limit value CVm of the variation
If it exceeds ax, in step SP8, the measurement results S2 and S3 corresponding to the low known concentration sample X0 and the measurement result S4 corresponding to the high known concentration sample X2 are abnormal and normal S0, S1 corresponds to the sample X1 and S5 corresponds to the sample X2, and the series of processes is ended. Variation CV2 in step SP7
Does not exceed the variation limit value CVmax, or the variation CV1 exceeds the variation limit value CVmax, it is determined in step SP9 that only the variation CV1 has the variation limit value CVmax. Dispersion C
If only V1 exceeds the variation limit value CVmax, the measurement results S2 and S3 corresponding to the low-concentration known concentration sample X0 and the measurement result S1 corresponding to the intermediate-concentration known concentration sample X1 are abnormal in step SP10. Then, it is displayed that normal S0 corresponds to the sample X1, and S4 and S5 correspond to the sample X2, and the series of processing ends.

Both variations CV in step SP9
When it is determined that both 1 and CV2 exceed the variation limit value CVmax, in step SP11, it is displayed that an abnormal measurement result cannot be specified, and the series of processing ends. FIG. 13 shows a sample X1 having a known intermediate concentration.
Is a flow chart for explaining the processing in the case where the measurement result Y1 corresponding to is not present.
Variation CV1 of measurement results S0 and S1 and measurement result S
The variation CV2 of S4 and S5 is calculated. Then, in step SP2, it is determined whether or not both variations CV1 and CV2 are smaller than the variation limit value CVmax.
If both variations CV1 and CV2 are small, the measurement results S2 and S3 corresponding to the sample X1 having the known intermediate concentration are abnormal in step SP3, and normal S0 and S1 are obtained.
Indicates that the sample corresponds to the sample X0, and S4 and S5 correspond to the sample X2, and the series of processing ends.

When it is determined in step SP2 that any of the variations exceeds the variation limit value CVmax, it is determined in step SP4 whether only the variation CV2 exceeds the variation limit value CVmax, Only the variation CV2 is the limit value CVm of the variation
If it exceeds ax, the measurement results S2 and S3 corresponding to the sample X1 of known intermediate concentration and the measurement result S4 corresponding to the sample X2 of high known concentration are abnormal and normal S0, S1 corresponds to the sample X0, and S5 corresponds to the sample X2, and the series of processing ends. Variation CV2 in step SP4
Does not exceed the variation limit value CVmax, or if the variation CV1 exceeds the variation limit value CVmax, only the variation CV1 in step SP6 determines the variation limit value CVmax. Dispersion C
If only V1 exceeds the variation limit value CVmax, the measurement result S1 corresponding to the sample X0 having a low known concentration and the measurement results S2 and S3 corresponding to the sample X1 having a known intermediate concentration are abnormal in step SP7. The normal S0 corresponds to the sample X0, and S4 and S5 correspond to the sample X2, and the series of processing ends.

Both variations CV in step SP6
When it is determined that both 1 and CV2 exceed the variation limit value CVmax, in step SP8 it is displayed that an abnormal measurement result cannot be specified, and the series of processes is ended. FIG. 14 is a flowchart for explaining the processing when the measurement result Y2 corresponding to the sample X2 having a high known concentration does not exist. In step SP1, the variation CV1 between the measurement results S0 and S1 and the measurement result S2.
The variation CV2 of S4 and S5 is calculated. Then, in step SP2, it is determined whether or not both variations CV1 and CV2 are smaller than the variation limit value CVmax.
If both variations CV1 and CV2 are small, the measurement results S2 and S3 corresponding to the sample X2 having a high known concentration are abnormal in step SP3, and normal S0 and S1 are obtained.
Indicates that the sample corresponds to the sample X0, and S4 and S5 correspond to the sample X1, and the series of processing ends.

If it is determined in step SP2 that any variation exceeds the variation limit value CVmax, it is determined in step SP4 whether only the variation CV2 exceeds the variation limit value CVmax. Only the variation CV2 is the limit value CVm of the variation
If ax is exceeded, the measurement result S4 corresponding to the sample X1 of known intermediate concentration and the measurement result S2 corresponding to the sample X2 of high known concentration in step SP5.
S3 is abnormal, and normal S0 and S1 correspond to the sample X0, and S5 corresponds to the sample X1, and the series of processing ends. Variation CV2 in step SP4
Does not exceed the variation limit value CVmax, or if the variation CV1 exceeds the variation limit value CVmax, only the variation CV1 in step SP6 determines the variation limit value CVmax. Dispersion C
If only V1 exceeds the variation limit value CVmax, the measurement result S1 corresponding to the low-concentration known concentration sample X0 and the measurement results S2 and S3 corresponding to the high-concentration known concentration sample X2 are abnormal in step SP7. The normal S0 corresponds to the sample X0, and S4 and S5 correspond to the sample X1, and the series of processing ends.

Both variations CV in step SP6
When it is determined that both 1 and CV2 exceed the variation limit value CVmax, in step SP8 it is displayed that an abnormal measurement result cannot be specified, and the series of processes is ended. As is clear from the above, if there is an abnormality in the calibration result, it is possible to identify the abnormal measurement result with considerably high accuracy.Therefore, when performing calibration again, set the minimum required sample. It only needs to be calibrated, which simplifies the work,
It is possible to reduce the time required for calibration and suppress the waste of the sample. Further, when the calibration is not performed again, only the normal measurement result can be adopted, so that there is an inconvenience that the number of adopted measurement results is reduced, but it is fatal that the abnormal measurement result is adopted. It is possible to prevent such inconvenience.

[0070]

As described above, according to the first aspect of the invention, when a sample having a known concentration is set at an incorrect position, the measurement result corresponding to the sample set at any position has a limit value. It is out of the range, and there is a unique effect that the abnormality of the calibration can be surely judged without any artificial judgment.

According to the second aspect of the invention, when a sample having a known concentration is set at an incorrect position, the calibration curve translated in parallel based on the measurement result corresponding to the sample set at any position is used. The parallel movement amount exceeds the upper limit value, and a unique effect that the abnormality of the calibration can be surely judged without any artificial judgment is exerted. According to the invention of claim 3, when a plurality of samples having different known concentrations are set in order to improve the accuracy of the calibration result, when the samples having different known concentrations are set, the measurement results based on these samples are set. Since there is a large variation, there is a unique effect that the abnormality of the calibration can be surely judged without any artificial judgment.

According to the fourth aspect of the invention, when the set positions of the samples of known concentrations are wrong, the relative values of the measurement results based on these samples are significantly different from the normal values, The unique effect is that the abnormality of the calibration can be surely determined without the need for artificial judgment. According to the invention of claim 5, when the set positions of the samples of known concentrations are wrong, the rate of change in inclination based on the measurement results based on these samples is significantly different from that in the normal case. The unique effect is that it is possible to reliably determine an abnormality in calibration without making a physical determination.

According to the sixth aspect of the present invention, even if the set position of the sample is wrong, it is not necessary to perform the calibration again, and an accurate calibration result can be obtained. It has a unique effect that it is possible to prevent an increase in the required amount of a sample having a known concentration used. According to the invention of claim 7, it is not necessary to perform the calibration again when an accurate calibration result can be obtained even if the measurement result is slightly reduced, and an accurate calibration result can be obtained. In addition, it has a unique effect of preventing an increase in the required amount of a sample having a known concentration used for measurement.

According to the invention of claim 8, an accurate calibration result can be obtained only by repeating the concentration measurement operation only for the sample which has not been set at the position to be set, and in the case where a setting error occurs. The workability of calibration in can be significantly improved and the time required as a whole can be shortened.
It has a unique effect that the required amount of the sample of known concentration used for the measurement can be reduced.

[Brief description of drawings]

FIG. 1 is a flowchart illustrating an embodiment of a calibration result determination method of the present invention.

FIG. 2 is a flowchart illustrating another embodiment of the calibration result determination method of the present invention.

FIG. 3 is a flow chart for explaining still another embodiment of the calibration result judging method of the present invention.

FIG. 4 is a flowchart illustrating an embodiment of a calibration result processing method according to the present invention.

FIG. 5 is a flowchart illustrating another embodiment of the calibration result processing method of the present invention.

FIG. 6 is a flow chart for explaining still another embodiment of the calibration result processing method of the present invention.

FIG. 7 is a flowchart illustrating a part of another specific example of the calibration result processing method of the present invention.

FIG. 8 is a flowchart illustrating the remaining part of another specific example of the calibration result processing method of the present invention.

FIG. 9 is a flowchart illustrating still another specific example of the calibration result processing method of the present invention.

FIG. 10 is a flowchart illustrating a condition setting process when there are two or more abnormal measurement results.

FIG. 11 is a flowchart illustrating a process when an abnormal measurement result cannot be specified only by setting the conditions shown in FIG.

FIG. 12 is a flowchart illustrating a process when there is no measurement result corresponding to a sample having a low known concentration.

FIG. 13 is a flowchart illustrating a process when there is no measurement result corresponding to a sample having a known intermediate concentration.

FIG. 14 is a flowchart illustrating processing when there is no measurement result corresponding to a high-concentration known-concentration sample.

FIG. 15 is a diagram schematically showing a sample set position for calibration.

Claims (8)

[Claims] 1. The measurement of each sample is performed in a state in which the sample of known concentration is set at the position where the sample of known concentration different from each other is set, and the sample is set in advance corresponding to at least one sample of known concentration. The calibration result is characterized by determining the magnitude between the upper and lower limit values and the corresponding measurement result, and judging that the calibration result is abnormal when the measurement result is outside the range of both limit values. Judgment method. 2. The measurement of each sample is performed in a state where the sample of known concentration is set at the position where the sample of known concentration different from each other is set, and the sample is set in advance corresponding to at least one sample of known concentration. The parallel calibration curve is moved, the magnitude of the upper limit value of the movement amount and the parallel movement amount of the calibration curve are discriminated, and if the parallel movement amount exceeds the upper limit value, it is determined that the calibration result is abnormal. A calibration result determination method characterized by the above. 3. A sample having a known concentration is set at a position where a plurality of samples having different known concentrations should be set, and each sample is measured. And determining that the calibration result is abnormal on the condition that the calculated variation is larger than a predetermined threshold value. 4. A relative value between measurement results based on samples having different known concentrations by measuring each sample with the samples having known concentrations set at positions where samples having different known concentrations should be set. A calibration result determination method characterized in that the calibration result is determined to be abnormal when the calculated relative value is outside at least one of the upper and lower limit values set in advance. . 5. The calibration result determination method according to claim 4, wherein the relative value between the measurement results based on the samples which should have different known concentrations is a rate of change in inclination from a preset calibration curve. 6. In response to the fact that the calibration result is determined to be abnormal by the method according to any one of claims 1 to 5, the measurement result is set in a predetermined order in which a sample having a known concentration is set. A calibration result processing method characterized by sorting into. 7. In response to the calibration result being determined to be abnormal by the method according to any one of claims 1 to 5, the abnormality is detected based on a predetermined order in which samples of known concentrations should be set. A calibration result processing method, characterized in that detailed measurement results are omitted. 8. Any one of claims 1 to 5 as a result of measuring each sample in a state where a sample with a known concentration is set at a position where at least three types of samples with known concentrations different from each other are set. The method according to at least one of claims 1 to 5, based on the residual measurement result excluding the measurement result based on at least one sample, in response to the calibration result being determined to be abnormal by the above method. Determines whether the calibration result is abnormal or not, and in response to the determination result indicating that the calibration result is abnormal, recalibrates based on the remaining measurement results excluding the measurement results based on different samples. The excluded sample is set in response to the judgment result indicating that the calibration result is normal, judging whether the result is abnormal. A calibration result processing method characterized by displaying that a sample has not been set at a proper position.