JP2017198623A - Measuring apparatus and measuring method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a measuring apparatus and measuring method capable of accurately measuring a measured component in a measured liquid.SOLUTION: A measuring apparatus (1A) includes: a measurement container (10) including a first liquid storage chamber (14a) filled with a measurement reagent and a second liquid storage chamber (14b) that is not filled with the measurement reagent; a liquid injection device (24) including a first tube (24c) and a second tube (24d); an optical measurement mechanism (25); a calculation unit (31A); and a control unit (30A). The measuring apparatus executes a liquid injection trial mode, a liquid injection mode, and a first mixture measurement mode, and calculates the concentration of a measured component on the basis of the measurement result in the first mixture measurement mode.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a measurement apparatus and a measurement method suitable for analyzing a measurement component contained in a measurement liquid in sample analysis.

  For example, in the field of agriculture, analysis of soil components in the growing environment of crops is widely performed in order to manage the growing state of the crops.

  By frequently analyzing soil components, fertilization design can be performed in consideration of the influence of the previous crop by performing detailed analysis for each field and analysis for each planting. Moreover, about the crop with a long growth period, the timing and quantity of additional fertilization can be optimized by analyzing regularly with a shorter span. Therefore, an increase in yield and stabilization of quality can be expected by performing such soil analysis.

  In general, the soil analysis apparatus injects each soil extract into a plurality of test tubes while measuring with a graduated dropper. Thereafter, a measurement reagent and a diluting solution determined for each soil component are injected into a test tube, and a measurement sample is prepared by mixing the soil extract, the measuring reagent, and the diluting solution. The produced measurement sample is colored by the reaction of the soil components of the soil extract with the measurement reagent. Then, the optical characteristics of the measurement sample are measured by converting the degree of color development of the measurement sample that has developed color into a numerical value using a colorimetric table, a turbidimetric table, an absorptiometry, or the like.

  For example, Patent Document 1 discloses a measuring apparatus that measures the optical characteristics of a measurement sample using an absorptiometry.

  The liquid concentration measuring device 100 described in Patent Document 1 includes a light emitting unit 101, a light receiving unit 102, and a storage cartridge 103, as shown in FIG. The storage cartridge 103 is made of a transparent material, and is provided with a plurality of cells 104 that store a mixed solution of a soil extract and a reagent extracted from soil. The liquid concentration measuring device 100 measures the absorbance of the mixed solution when the light emitted from the light emitting unit 101 passes through the mixed solution in the storage cartridge 103 and is detected by the light receiving unit 102, and the soil component is measured by the spectrophotometric method. Is measuring the concentration.

  As shown in FIG. 12B, the storage cartridge 103 has a plurality of cells 104 arranged in a row. Each cell 104 contains a predetermined amount of reagent in advance and is sealed with a sticker. The liquid component analyzer 100 further includes an extract cartridge 105. In the extraction liquid cartridge 105, a plurality of cells 106 are arranged in a row so as to correspond to the plurality of cells 104. Each cell 106 has a dredging function as measurement, and contains a soil extract. Then, before the measurement, the storage cartridge 103 and the extraction liquid cartridge 105 are fitted by pushing the lower surface of the extraction liquid cartridge 105 into the upper surface of the storage cartridge 103 (in the direction indicated by the arrow in FIG. 12B). Thereafter, the bottom surface of the extraction liquid cartridge 105 is penetrated, and the soil extraction liquid stored in each cell 106 of the extraction liquid cartridge 105 is injected into the cell 104 of the storage cartridge 103 to produce a mixed liquid of the soil extraction liquid and the reagent. To do.

  As described above, in the liquid concentration measuring device 100, it is easy to prepare a mixed solution of the soil extract and the reagent, and the concentration of the soil component is measured by the absorptiometry, so that the measurement with high accuracy is performed. be able to.

JP 2007-46922 A (published February 22, 2007)

  Here, in the measurement of the measurement component by mixing the soil extract (measuring solution) and the reagent to color the mixed solution, the degree of coloration of the mixed solution changes rapidly depending on the amount of the soil extract. . For this reason, in order to accurately measure the concentration of the measurement component of the soil extract, it is necessary to inject an accurate amount of the soil extract into the measurement container.

  However, in the liquid concentration measuring instrument 100 disclosed in Patent Document 1, the storage cartridge 103 and the extraction liquid cartridge 105 are fitted, the bottom surface of the extraction liquid cartridge 105 is penetrated, and the soil extraction liquid is passed through the cell of the storage cartridge 103. By injecting into 104, the liquid mixture of a soil extract and a reagent is produced. In such a mixed liquid preparation method, there is a possibility that all the soil extract stored in each cell 106 of the extract cartridge 105 cannot be injected into the cell 104 of the store cartridge 103. As a result, the coloration degree of the mixed solution changes, and there is a problem that the concentration of the soil component cannot be measured accurately.

  The present invention has been made in view of the above problems, and an object thereof is to provide a measuring apparatus and a measuring method capable of accurately measuring a measurement component contained in a measurement liquid.

  In order to solve the above problems, a measurement apparatus according to one embodiment of the present invention includes one or a plurality of measurement chambers in which a measurement reagent that reacts with a measurement component in a measurement solution is sealed, and the measurement reagent is sealed. A measurement container including a non-liquid injection trial chamber, a liquid injection part for injecting a measurement liquid and a diluent into the measurement chamber and the liquid injection trial chamber, and a measurement liquid and dilution injected into the measurement chamber A measurement unit that measures transmitted light that has passed through a mixture of at least one liquid of the liquid and the measurement reagent, and a calculation unit that calculates the concentration of the measurement component in the measurement solution based on the measurement result of the measurement unit; And a control device for controlling the liquid injection part and the measurement part, wherein the liquid injection part is a first tube for sending the measurement liquid to the measurement container, and the dilution liquid is In a measuring container A liquid second tube, and the control section controls the liquid injection section so that the first tube and the second tube are filled with the measurement liquid and the dilution liquid, respectively. To execute a liquid injection trial mode in which the diluent and the measurement liquid are respectively injected into the liquid injection trial chamber through the first tube and the second tube, and after the liquid injection trial mode, By controlling the liquid injection part, the measurement liquid injection mode for injecting the measurement liquid into the measurement chamber via the first tube, and the measurement chamber for the measurement chamber via the second tube A liquid injection mode including a diluent injection mode for injecting a diluent is executed, and after the liquid injection mode, the measurement unit is controlled to enter the measurement chamber. A first mixture measurement mode for measuring transmitted light that has passed through the first mixture composed of the diluent, the measurement liquid, and the measurement reagent mixed in the first measurement mode, and the calculation unit is configured to perform the first mixture measurement mode. The concentration of the measurement component in the measurement liquid is calculated on the basis of the measurement result obtained in (1).

  In order to solve the above problems, a measurement method according to one embodiment of the present invention includes one or a plurality of measurement chambers in which a measurement reagent that reacts with a measurement component in a measurement solution is sealed, and the measurement reagent is sealed. A measurement method for calculating a concentration of a measurement component contained in a measurement liquid injected into the measurement chamber using a measurement container provided with a non-liquid injection trial chamber, wherein the measurement liquid is fed to the measurement container Through the first tube and the second tube so that the first tube and the second tube for feeding the diluted solution to the measurement container are filled with the measured solution and the diluted solution, respectively. A liquid injection trial step for injecting the diluent and the measurement liquid into the liquid injection trial chamber, and the measurement liquid with respect to the measurement chamber via the first tube after the liquid injection trial step. A liquid injection step for performing a measurement liquid injection step for injecting and a dilution liquid injection step for injecting the dilution liquid into the measurement chamber via the second tube; and after the liquid injection step, in the measurement chamber Based on the measurement result obtained by the 1st mixture measurement process which measures the transmitted light which permeate | transmitted the mixed 1st mixture which consists of the said dilution liquid, the said measurement liquid, and the said measurement reagent mixed, and the said 1st mixture measurement process And a calculation step of calculating the concentration of the measurement component in the measurement liquid.

  According to one aspect of the present invention, it is possible to accurately measure a measurement component contained in a measurement liquid.

It is the schematic which shows the structure of the measuring apparatus which concerns on Embodiment 1 of this invention. It is a perspective view which shows the structure of the said measuring apparatus. The schematic structure of the measurement container of the said measuring apparatus is shown typically, (a) is the front view which looked at the measurement container from upper direction, (b) is the AA 'arrow directional cross section of (a). FIG. The schematic structure of the analysis cell of the said measurement container is shown typically, (a) is the front view which looked at the analysis cell from the upper part, (b) is a BB 'arrow cross section of (a). FIG. It is a flowchart which shows the procedure of the measurement using the said measuring apparatus. It shows a mode that a liquid is inject | poured into the 1st liquid storage chamber of a measurement container in the measurement using the said measuring apparatus, (a) is sectional drawing of the 1st liquid storage chamber before a dilution liquid injection | pouring process. (B) is a cross-sectional view of the first liquid storage chamber after the dilution liquid injection step, (c) is a cross-sectional view of the first liquid storage chamber after the first stirring step, and (d) is a measurement liquid. It is sectional drawing of the 1st liquid storage chamber after an injection | pouring process. The state after mixing and stirring the liquid sample and reagent of the said analysis cell is shown, (a) is the front view which looked at the analysis cell from upper direction, (b) is CC of (a). FIG. It is the schematic which shows the structure of the measuring apparatus which concerns on Embodiment 2 of this invention. It is a flowchart which shows the procedure of the measurement using the said measuring apparatus. It is the schematic which shows the structure of the measuring apparatus which concerns on Embodiment 3 of this invention. It is a flowchart which shows the procedure of the measurement using the said measuring apparatus. 1 shows a configuration of a conventional measuring device, (a) is a schematic diagram showing a configuration of a conventional measuring device, and (b) is a fitting between a storage cartridge provided in the conventional measuring device and an extract liquid cartridge. FIG.

Embodiment 1
Hereinafter, a measuring apparatus 1A according to Embodiment 1 of the present invention will be described with reference to FIGS.

(Configuration of measuring apparatus 1A)
The configuration of the measuring apparatus 1A in the present embodiment will be described with reference to FIGS. FIG. 1 is a schematic diagram showing the configuration of the measuring apparatus 1A. FIG. 2 is a perspective view showing the configuration of the measuring apparatus 1A. FIG. 3 schematically shows an outline of the measurement container 10, (a) is a front view of the measurement container 10 as viewed from above, and (b) is a view taken along line AA ′ in (a). It is sectional drawing.

  As shown in FIG. 2, the measuring apparatus 1 </ b> A stirs and mixes the liquid / solid in the measuring container 10 by rotating the measuring container 10 around the rotation shaft 19. Furthermore, the measuring apparatus 1A also has a function of measuring the optical characteristics of the liquid in the measuring container 10 and analyzing the components in the liquid.

  As shown in FIG. 2, the measurement apparatus 1 </ b> A includes a measurement container 10, a table 22, a drive mechanism (rotation drive unit) 23, a liquid injection device (liquid injection unit) 24, and an optical measurement mechanism (measurement unit) 25. And. Furthermore, as shown in FIG. 1, the measuring apparatus 1A includes a control unit 30A and a calculation unit 31A.

  As shown in FIGS. 3A and 3B, the measurement container 10 includes six analysis cells 11. The six analysis cells 11 are formed in a fan shape with a virtual rotation axis 19 as the center, and the measurement container 10 has a disk-like configuration as a whole. Each analysis cell 11 includes a liquid inlet and a first liquid storage chamber (measuring chamber) 14a or a second liquid storage chamber (liquid injection trial chamber) 14b, and the liquid injected from the liquid inlet 13 is supplied. It can be accommodated in the first liquid storage chamber 14a or the second liquid storage chamber 14b. Details of the measurement container 10 will be described later. In the following description, when the first liquid storage chamber 14a and the second liquid storage chamber 14b are not distinguished, they are described as the liquid storage chamber 14.

  In the following description, for the sake of convenience, the side on which the liquid inlet 13 is formed is referred to as the upper side (upper surface or top surface), and the opposite side (the back side of the measurement container 10) is referred to as the lower side (lower surface or bottom surface). It is assumed that gravity acts on the measurement container 10 from above to below.

  The table 22 is for mounting the measurement container 10. The table 22 is supported by being arranged at the top of the drive mechanism 23. On the surface of the table 22, a so-called D-cut columnar rotary shaft member, a stopper for fixing the measurement container 10, a claw, and the like are arranged. The central portion of the measurement container 10 is inserted into the rotating shaft member of the table 22. The rotating shaft member is arranged coaxially with the rotating shaft 19 of the measurement container 10. The table 22 has an opening formed in a region located below each liquid storage chamber 14 with the measurement container 10 set on the surface.

  The drive mechanism 23 rotationally drives the table 22 according to an instruction from the control unit 30A. As a result, the measurement container 10 rotates about the rotation shaft 19. Moreover, the drive mechanism 23 rotates the measurement container 10 around the rotating shaft 19 while accelerating or decelerating in accordance with an instruction from the control unit 30 </ b> A when performing a stirring process described later. As an example, the drive mechanism 23 can be composed of a stepping motor capable of pulse control.

  The liquid injection device 24 is for injecting a liquid into the measurement container 10. The liquid injection device 24 includes a measurement liquid storage container 24a that stores a measurement liquid to be measured, a dilution liquid storage container 24b that stores a dilution liquid for diluting the measurement liquid, and a measurement liquid from the measurement liquid storage container 24a. A first tube 24c for feeding liquid to the measurement container 10 and a second tube 24d for feeding the diluent from the diluent container 24b to the measurement container are provided. The measurement liquid is stored in the measurement liquid storage container 24a before the measurement is started. Further, the diluent storage container 24b stores the diluent before starting the measurement. In response to an instruction from the control unit 30A, the liquid injection device 24 injects the measurement liquid from the measurement liquid storage container 24a through the first tube 24c into the measurement container 10 and from the dilution liquid storage container 24b through the second tube 24d. The measurement liquid is injected into the measurement container 10. Specifically, the liquid injection device 24 injects the measurement liquid or the dilution liquid from the liquid injection port 13 of each analysis cell 11 into the first liquid storage chamber 14a or the second liquid storage chamber 14b. The dilution liquid is a solvent for diluting the measurement liquid, such as water (pure water).

  Note that the measurement liquid to be injected using the liquid injection device 24 may be adjusted by extracting in advance for measurement by the measurement device 1A, and the collected liquid sample is used as it is without adjustment. You may do.

  The optical measurement mechanism 25 measures the optical characteristics of the liquid sample in the liquid storage chamber 14 of the measurement container 10 and analyzes one or more measurement components contained in the liquid sample. As an example, the optical measurement mechanism 25 measures the components of the liquid sample by absorptiometry. The optical measurement mechanism 25 includes a light emitting unit 25a and a light receiving unit 25b. The measurement container 10 is disposed between the light emitting unit 25 a and the light receiving unit 25 b, and the light emitting unit 25 a is disposed above the measurement container 10 and the light receiving unit 25 b is disposed below the measurement container 10.

  The light emitting unit 25a irradiates one of the liquid storage chambers 14 of each analysis cell 11 of the measurement container 10 set on the table 22 that is rotationally driven according to an instruction from the control unit 30A. The light emitting unit 25a is arranged so as to be positioned above any one of the liquid storage chambers 14 of each analysis cell 11 of the measurement container 10 set on the table 22 that is rotationally driven. And the light emission part 25a irradiates light to the upper surface of the analysis cell 11 arrange | positioned below.

  The light receiving unit 25b irradiates the upper surface of the analysis cell 11 from the light emitting unit 25a, passes through the liquid storage chamber 14, receives light emitted from the lower surface of the analysis cell 11, and measures the transmission amount of the received light. . The light receiver 25b outputs the measured amount of transmitted light to the calculator 31A. The light receiving unit 25b is disposed below the light emitting unit 25a. The light receiver 25b outputs the measured amount of transmitted light to the calculator 31A as spectrum data.

  The control unit 30 </ b> A controls operations of the driving mechanism 23, the liquid injection device 24, and the light emitting unit 25 a of the optical measurement mechanism 25.

  The calculation unit 31A calculates the absorbance of the liquid sample in the liquid storage chamber 14 based on the light transmission amount (spectral data, measurement result) output from the light receiving unit 25b, and calculates the absorbance in the liquid storage chamber 14 from the calculated absorbance. The concentration of the measurement component in the liquid sample is calculated.

(Configuration of measurement container 10)
Next, the configuration of the measurement container 10 will be described with reference to FIG.

  As shown to (a) of FIG. 3, the measurement container 10 is rotationally driven by the drive mechanism 23 (refer FIG. 1, 2) mentioned above centering on the rotating shaft 19 showing a virtual line. Each analysis cell 11 is partitioned as shown by a broken line in the figure and does not communicate with each other.

  Of the six analysis cells 11, five analysis cells 11 are provided with a first liquid storage chamber 14a as a measurement chamber, and the remaining one analysis cell 11 has a second liquid storage chamber 14b as a liquid injection trial chamber. I have. In the first liquid storage chambers 14a of the five analysis cells 11, measurement reagents 40a to 40e having different types, amounts, or types and amounts are respectively enclosed. The measurement reagent is not sealed in the second liquid storage chamber 14b of the remaining one analysis cell 11. In the present embodiment, six analysis cells 11 are formed, but the number of analysis cells 11 is not limited. That is, the number of analysis cells 11 may be two or more (that is, if there are at least one analysis cell including the first liquid storage chamber 14a and at least one analysis cell including the second liquid storage chamber 14b). Good). Moreover, in the following description, when the measurement reagents 40a to 40e are not distinguished, they will be described as the measurement reagent 40.

  On the upper surface of each analysis cell 11, a liquid inlet 13 and a top surface side measurement window 16a are formed. In the measurement container 10, the liquid inlet 13 is formed on the inner peripheral side, and the top surface side measurement window 16a is formed on the outer peripheral side. All the liquid inlets 13 are formed on the second circumference (on the same circumference) around the rotation shaft 19. Details of the analysis cell 11 will be described later.

  In addition, the material which comprises the measurement container 10 (analysis cell 11) is not specifically limited. In order to make the measurement container 10 inexpensive, it is preferable that the whole is made of a highly transparent synthetic resin. The measuring container 10 of the present embodiment is entirely made of highly transparent polystyrene.

  As shown in FIG. 3B, the cross section of the measurement container 10 has a hat shape, and a space is formed from the hat-shaped head portion to the flange portion. Thereby, the analysis cell 11 becomes a container shape. Specifically, the space in the analysis cell 11 includes a liquid inlet 13 formed on the upper surface of the analysis cell 11 corresponding to the head, a liquid storage chamber 14 formed in the flange portion, and a liquid inlet 13. And a flow path 15 connecting the liquid storage chamber 14.

  The channel 15 is formed with an inclined surface 15a that descends from the liquid inlet 13 toward the liquid storage chamber 14 in the outer peripheral direction. Thus, the measurement container 10 has a configuration in which a plurality of liquid inlets 13 are formed around the rotation shaft 19 and a liquid storage chamber 14 communicating with the flow path 15 is formed on the outer peripheral side of each liquid inlet 13. It has become. The six liquid storage chambers 14 are arranged on the same circumference around the rotation axis 19 in one plane perpendicular to the rotation axis 19.

  In addition, the shape of the cross section of the measurement container 10 is not limited to a hat shape, For example, other shapes, such as a column shape, may be sufficient.

  Next, details of the structure of the analysis cell 11 will be described with reference to FIG. FIG. 4 schematically shows an outline of the analysis cell 11, (a) is a front view of the analysis cell 11 as viewed from above, and (b) is a view taken along the line BB ′ in (a). It is sectional drawing.

  As shown in FIG. 4A, the liquid inlet 13 is an opening for introducing a measurement liquid or a dilution liquid into the liquid storage chamber 14. The liquid inlet 13 is connected to a flow path 15 that connects the liquid inlet 13 and the liquid storage chamber 14, and the measurement liquid or the diluted liquid introduced into the liquid inlet 13 is stored in the liquid via the flow path 15. It is introduced into the chamber 14.

  The first liquid storage chamber 14a is a space for storing the measurement liquid or the dilution liquid and measuring the amount of light transmitted through the first mixture that is a mixture of the measurement liquid, the dilution liquid, and the measurement reagent 40. . In each first liquid storage chamber 14a, measurement reagents 40a to 40e of different types, amounts, or types and amounts are sealed. The measurement reagents 40a to 40e are reagents that react with predetermined components among a plurality of components contained in the measurement liquid. For example, the measurement reagents 40a to 40e in each first liquid storage chamber 14a are reagents that exhibit a color reaction with respect to the measurement components measured by each analysis cell 11, and the measurement reagents 40a to 40e correspond to the measurement components. It can be set arbitrarily and is not particularly limited. For example, as a measuring reagent 40 for measuring the concentration of Mg component in soil analysis, “xylidyl blue + Triton X-100 + triethanolamine + sodium sulfate + GEDTA + tetraethylenepentamine + disodium hydrogen phosphate + sodium hydroxide solution” A mixed solution etc. can be mentioned. The measurement reagent 40 may be a solid such as a powder or a liquid.

  As shown in FIG. 4B, the inner wall of the liquid storage chamber 14 includes a top surface 17 and a bottom surface 18 that face each other.

  Furthermore, the top surface 17 of the liquid storage chamber 14 includes a high top surface 17a and a low top surface 17b. The high ceiling surface 17a is located above the low ceiling surface 17b. That is, a step is provided between the high ceiling surface 17a and the low ceiling surface 17b. The low ceiling surface 17b is provided in the center portion in the circumferential direction of the ceiling surface 17 of the liquid storage chamber 14, and the high ceiling surface 17a is provided on both sides in the circumferential direction of the low ceiling surface 17b. .

  A top surface side measurement window 16 a is provided on the low surface 17 b of the top surface 17. Further, a bottom surface side measurement window 16 b is provided on the bottom surface 18 of the liquid storage chamber 14. A step is formed on the top surface 17, and the top surface 17 of the liquid storage chamber 14 has a shape in which a portion of the top surface side measurement window 16 a that is a light transmitting portion is dug down from the surroundings. That is, the high ceiling surface 17a whose height from the bottom surface 18 is higher than that of the low ceiling surface 17b is formed around the low ceiling surface 17b whose height from the bottom surface 18 is relatively low. The top surface side measurement window 16a and the bottom surface side measurement window 16b are provided so as to overlap each other when viewed from above (or below). The top surface side measurement window 16a and the bottom surface side measurement window 16b of the liquid storage chamber 14 are formed on the same circumference around the rotation axis 19 along the outer edge of the measurement container 10 (see FIG. 3).

  The measurement container 10 is provided for analyzing the measurement liquid based on the light transmitted from the top surface side measurement window 16a to the bottom surface side measurement window 16b. For this reason, at least the top surface side measurement window 16a and the bottom surface side measurement window 16b need only be made of a transparent material such as silicone, glass, polycarbonate, or acrylic. As described above, in the present embodiment, the entire measurement container 10 is made of highly transparent polystyrene. Thus, when the measurement container 10 is formed of a light transmissive material (particularly a transparent material), it is not necessary to separately provide the top surface side measurement window 16a and the bottom surface side measurement window 16b, and the top surface side measurement window 16a and A bottom side measurement window 16 b is integrated with the measurement container 10.

  The flow path 15 has one end connected to the liquid inlet 13 and the other end connected to the liquid storage chamber 14. The channel 15 is formed with an inclined surface 15a that descends from the liquid inlet 13 toward the liquid storage chamber 14 in the outer peripheral direction. The inclined surface 15 a is formed from the liquid inlet 13 to the bottom surface 18 of the liquid storage chamber 14. That is, the height of the inclined surface 15a gradually decreases from the liquid inlet 13 toward the outer peripheral direction of the analysis cell 11 in which the liquid storage chamber 14 is formed. As a result, the measurement liquid or dilution liquid introduced from the liquid inlet 13 can be smoothly guided to the liquid storage chamber 14 along the inclined surface 15a without accumulating near the liquid inlet 13. ing. Furthermore, when the measurement liquid or dilution liquid and the measurement reagent 40 are mixed by the centrifugal force of rotation of the measurement container 10 described later, the measurement liquid or dilution liquid flows backward from the liquid storage chamber 14 to the liquid inlet 13. This can prevent the measurement liquid or the dilution liquid from being scattered outside the measurement container 10.

(Accuracy of the amount of liquid injected into the measurement container)
Next, the accuracy of the injection amount of the measurement liquid or diluent into the measurement container will be described. In the measurement of the measurement component by mixing the measurement liquid, the dilution liquid, and the measurement reagent and coloring the liquid mixture, the degree of coloration of the liquid mixture depends on the amount of the measurement liquid and the dilution liquid, that is, the dilution rate. To change. For this reason, in order to accurately measure the concentration of the measurement component of the measurement liquid, it is necessary to inject an accurate amount of the measurement liquid and the dilution liquid into the measurement container so that the dilution rate is accurate.

  For example, when the liquid injection device includes a tube for supplying liquid to the measurement container and injects the liquid into the measurement container via the tube, if foreign matter such as air (bubbles) exists in the tube, An accurate amount of the measurement liquid or dilution liquid cannot be injected into the measurement container.

  As a method for injecting the measurement liquid and the dilution liquid into the measurement container so that the dilution rate is accurate in order to solve the above problem, it is considered to increase the amount of the measurement liquid and the dilution liquid injected into the measurement container. It is done. However, when the amount of the measurement liquid and dilution liquid to be injected into the measurement container is increased, the amount of the measurement reagent sealed in the measurement container is also required to be large. Since the measurement reagent is expensive, if the amount of the measurement reagent enclosed in the measurement container is increased, the cost is increased.

Therefore, in the measurement apparatus 1A in the present embodiment, the control unit 30A controls the liquid injection device 24 and the optical measurement mechanism 25 to execute the following three steps.
(1) By controlling the liquid injection device 24 so that the first tube 24c and the second tube 24d are filled with the measurement liquid and the dilution liquid, respectively, via the first tube 24c and the second tube 24d. A liquid injection trial step (liquid injection trial mode) for injecting the diluent and the measurement liquid into the second liquid storage chamber 14b.
(2) A measurement liquid injection process (measurement liquid injection mode) for injecting a measurement liquid into the first liquid storage chamber 14a via the first tube 24c by controlling the liquid injection device 24 after the liquid injection trial process. And a liquid injection process (liquid injection mode) including a diluent injection process (dilution liquid injection mode) for injecting a diluent into the first liquid storage chamber 14a via the second tube 24d.
(3) By controlling the optical measurement mechanism 25 after the liquid injection step, the first mixture M1a to M1e composed of the diluent, the measurement liquid, and the measurement reagent mixed in the first liquid storage chamber 14a is transmitted. 1st mixture measurement process (1st mixture measurement mode) which measures each transmitted light.

  Furthermore, in the measurement apparatus 1A, the calculation unit 31A calculates the concentration of the measurement component in the measurement liquid based on the measurement result obtained in the first mixture measurement step.

  As described above, in the measurement apparatus 1A, before the measurement liquid and the dilution liquid are injected into the first liquid storage chamber 14a in which the first mixture measurement process is performed, the second measurement is performed via the first tube 24c and the second tube 24d. A diluent and a measurement liquid are injected into the liquid storage chamber 14b so that the first tube 24c and the second tube 24d are filled with the measurement liquid and the dilution liquid, respectively.

  Thereby, since the first tube 24c and the second tube 24d are filled with the measurement liquid and the diluent, respectively, the first liquid storage is performed via the first tube 24c and the second tube 24d in the liquid injection process. When the diluent and the measurement liquid are injected into the chambers 14a, accurate amounts of the dilution liquid and the measurement liquid can be injected into each first liquid storage chamber 14a. As a result, the measurement liquid and the dilution liquid can be injected into each first liquid storage chamber 14a so that the dilution rate is accurate, and the concentration of each measurement component of the measurement liquid can be calculated with high accuracy.

(Measuring method of measuring apparatus 1A)
Next, a measurement method using the measurement apparatus 1A will be described in detail with reference to FIGS. FIG. 5 is a flowchart showing a measurement procedure using the measuring apparatus 1A. FIG. 6 shows a state in which the liquid is injected into the first liquid storage chamber 14a of the measurement container 10 in the measurement using the measuring apparatus 1A, and (a) shows the first liquid before the diluent injection process. It is sectional drawing of the storage chamber 14a, (b) is sectional drawing of the 1st liquid storage chamber 14a after a dilution liquid injection | pouring process, (c) is the 1st liquid storage chamber 14a after the 1st stirring process mentioned later. It is sectional drawing, (d) is sectional drawing of the 1st liquid storage chamber 14a after the measurement liquid injection | pouring process mentioned later.

  As shown in FIG. 5, first, according to an instruction from the control unit 30A, the liquid injection device 24 injects the measurement liquid into the second liquid storage chamber 14b through the first tube 24c, and then through the second tube 24d. The diluent is injected into the second liquid storage chamber 14b (S1, liquid injection trial process). In the liquid injection trial step, the diluent and the measurement liquid are injected into the second liquid storage chamber 14b so that the first tube 24c is filled with the measurement liquid and the second tube 24d is filled with the dilution liquid.

  Next, according to an instruction from the control unit 30A, the liquid injection device 24 injects the diluent into each first liquid storage chamber 14a via the second tube 24d (S2, diluent injection process). As described above, since the second tube 24d is filled with the diluent in the liquid injection trial step, an accurate amount of the diluent is injected into each first liquid storage chamber 14a in the diluent injection step. can do.

  Here, the amount of the diluent injected into the first liquid storage chamber 14a in the diluent injection process will be described with reference to FIG.

  As shown in FIG. 6A, a measurement reagent 40 that reacts with a predetermined measurement component contained in the measurement liquid is sealed in the first liquid storage chamber 14a in advance. Then, when the diluent is injected into the first liquid storage chamber 14a in the diluent injection process, as shown in FIG. 6B, the level of the diluent is lower than the low ceiling surface 17b. That is, the amount of the diluent injected in the diluent injection step is such that the liquid level of the diluent is lower than the low ceiling surface 17b. Since the shape and capacity of the first liquid storage chambers 14a are known in advance, the control unit 30A supplies each of the first liquid storage chambers 14a with an amount of the diluent that is lower than the low ceiling surface 17b. Can be instructed to inject.

  Next, in response to an instruction from the control unit 30A, the drive mechanism 23 rotates the measurement container 10 around the rotation shaft 19, and agitates the diluted solution and the measurement reagent 40 inside the first liquid storage chamber 14a (S3, First stirring step).

  In the first stirring step, as shown in FIG. 6B, the liquid level of the diluent injected in the diluent injection step is lower than the low ceiling surface 17b. That is, a space in which no diluent exists is formed between the liquid surface of the diluent and the low ceiling surface 17b. As a result, during the first stirring step, the movement of the dilution liquid is free from the inside of the first liquid storage chamber 14a so as to undulate without being hindered by the step existing between the high ceiling surface 17a and the low ceiling surface 17b. Can be moved to. As a result, the moving amount of the dilution liquid inside the first liquid storage chamber 14a is increased, and the stirring efficiency is improved. Therefore, the undissolved residue of the measurement reagent 40 can be suppressed by the first stirring step, and the measurement reagent 40 can be dissolved in the diluted solution. As a result, as shown in FIG. 6C, the measurement reagent 40 is dissolved in the diluent, and each first liquid storage chamber 14a has a second mixture that is a mixture of the diluent and the measurement reagents 40a to 40e. M2a to M2e are respectively produced.

  Next, according to an instruction from the control unit 30A, the liquid injection device 24 injects the measurement liquid into each first liquid storage chamber 14a via the first tube 24c (S4, measurement liquid injection process). As described above, since the first tube 24c is filled with the measurement liquid in the liquid injection trial process, an accurate amount of the measurement liquid is injected into each first liquid storage chamber 14a in the measurement liquid injection process. can do.

  Through the measurement liquid injection process, as shown in FIG. 6D, each first liquid storage chamber 14a has a first mixture M1a to M1e, which is a mixture of the measurement liquid, the diluent, and the measurement reagents 40a to 40e. Produced. The amount of the measurement liquid to be injected in the measurement liquid injection step is an amount at which the liquid levels of the first mixtures M1a to M1e are higher than the low ceiling surface 17b. Since the shape / capacity of the first liquid storage chamber 14a is known in advance, the control unit 30A supplies each first measurement liquid in an amount such that the liquid levels of the first mixtures M1a to M1e are higher than the low ceiling surface 17b. An instruction can be given to inject into the liquid storage chamber 14a.

  Next, in response to an instruction from the control unit 30A, the drive mechanism 23 rotates the measurement container 10 about the rotation shaft 19, and supplies the diluted solution and the measurement reagent 40 (first mixtures M1a to M1e) and the measurement solution to the first. The liquid is stirred inside the liquid storage chamber 14a (S5, second stirring step). Thereby, in each first liquid storage chamber 14a, first mixtures M1a to M1e in which the measurement reagents 40a to 40e are uniformly dissolved in the diluent and the measurement liquid are respectively produced.

  Next, according to an instruction from the control unit 30A, optical measurement is performed using the optical measurement mechanism 25, and the amounts of light transmitted through the first mixtures M1a to M1e accommodated in the first liquid storage chambers 14a are respectively determined. Measure (S6, first mixture measurement step).

  In the first mixture measurement step, the amount of light transmitted through the first liquid storage chamber 14 a of the measurement container 10 rotating around the rotation shaft 19 is measured by the drive mechanism 23. Specifically, the light emitted from the light emitting unit 25a according to an instruction from the control unit 30A is transmitted through the top surface side measurement window 16a, the first liquid storage chamber 14a, and the bottom surface side measurement window 16b in this order, and the transmitted light is transmitted. The light is incident on the light receiving unit 25b. The light receiving unit 25b receives the incident light, and outputs transmission amount data (measurement result) of the received light to the calculation unit 31A.

  In addition, since each first liquid storage chamber 14a is arranged on the same circumference around the rotation axis 19, by rotating the measurement container 10 around the rotation axis 19 by the drive mechanism 23, A plurality of measurements can be performed with one optical system (optical measurement mechanism 25).

  Finally, the calculation unit 31A calculates the concentration of the measurement component of the measurement liquid (S7). Specifically, the absorbances of the first mixtures M1a to M1e are calculated from the amounts of light transmitted through the first mixtures M1a to M1e measured in the first mixture measurement step.

  Next, the calculation unit 31A calculates the concentrations of the measurement components contained in the first mixtures M1a to M1e from the calculated absorbances of the first mixtures M1a to M1e, respectively. Next, the calculation unit 31A calculates the concentration of the measurement component contained in the measurement liquid by multiplying the calculated concentration of the measurement component contained in the first mixture M1a to M1e by the reciprocal of the dilution factor.

(Measures against bubbles generated in the first mixtures M1a to M1e)
Here, countermeasures against bubbles generated in the first mixtures M1a to M1e after the second stirring step are performed will be described in detail based on FIG. FIG. 7 schematically shows the state of the first liquid storage chamber 14a after the second stirring step, (a) is a front view of the analysis cell 11 as viewed from above, (b) It is CC 'line arrow sectional drawing of (a).

  When the measurement liquid and the measurement reagent 40 are mixed in the measurement liquid injection process, if gas is generated by the reaction between the measurement liquid and the measurement reagent 40, bubbles B are generated in the first liquid storage chamber 14a. Alternatively, when the measurement container 10 is rotated in the first stirring step and the second stirring step to stir and dissolve the measurement liquid and the measurement reagent 40, bubbles B are generated in the first liquid storage chamber 14a. End up.

  However, if the optical measurement is performed in a state where the bubbles B are present in the first liquid storage chamber 14a, there is a case where light scattering / reflection occurs due to the bubbles B and the measurement accuracy is lowered. In particular, if the bubble B exists in the measurement space S between the top surface side measurement window 16a and the bottom surface side measurement window 16b (bottom surface 18) shown in FIG. That is, the entrapment of the bubbles B into the top surface side measurement window 16a (low ceiling surface 17b) causes a decrease in measurement accuracy.

  In order to solve this problem, in the measurement container 10 of the present embodiment, the top surface 17 of the first liquid storage chamber 14a is positioned at the periphery of the low ceiling surface 17b that transmits light and the low ceiling surface 17b. The first liquid storage chamber 14a has a high ceiling surface 17a disposed at a position higher than the low ceiling surface 17b with respect to the bottom surface 18 of the first liquid storage chamber 14a. And after a measurement liquid is inject | poured by a measurement liquid injection | pouring process, the liquid level of 1st mixture M1a-M1e becomes a position higher than the low ceiling surface 17b.

  As a result, as shown in FIG. 7B, in the state where the liquid level is higher than the high ceiling surface 17a, even if the bubble B is generated in the first liquid storage chamber 14a, the generated bubble B is high. It is easily trapped in the space formed between the top surface 17a and the liquid surfaces of the first mixtures M1a to M1e. As a result, the entrapment of the bubbles B into the space between the low ceiling surface 17b and the bottom surface 18 (the measurement space S between the top surface side measurement window 16a and the bottom surface side measurement window 16b) is reduced. Therefore, when measuring the optical characteristics of the first mixtures M1a to M1e by transmitting light through the low ceiling surface 17b, it is possible to prevent a decrease in measurement accuracy due to the presence of the bubbles B.

  As described above, in the measuring apparatus 1A, before the measurement liquid and the dilution liquid are injected into the first liquid storage chamber 14a in which the first mixture measurement process is performed, the first tube 24c and the second tube 24d are used. The diluting liquid and the measuring liquid are injected into the two-liquid storage chamber 14b so that the first tube 24c and the second tube 24d are filled with the measuring liquid and the diluting liquid, respectively.

  Thereby, since the first tube 24c and the second tube 24d are filled with the measurement liquid and the diluent, respectively, the first liquid storage is performed via the first tube 24c and the second tube 24d in the liquid injection process. When the diluent and the measurement liquid are injected into the chambers 14a, accurate amounts of the dilution liquid and the measurement liquid can be injected into each first liquid storage chamber 14a. As a result, the measurement liquid and the dilution liquid can be injected into each first liquid storage chamber 14a so that the dilution rate is accurate, and the concentration of each measurement component of the measurement liquid can be calculated with high accuracy.

  In the measurement method described above, the dilution liquid injection step (S2) is performed, then the first stirring step (S3) is performed, and the measurement liquid injection step (S4) is performed. Is not limited to this. For example, the order of the diluent injection process and the measurement liquid injection process may be reversed. Further, without injecting the first stirring step, the dilution liquid and the measurement liquid are injected into the first liquid storage chamber 14a by the dilution liquid injection process and the measurement liquid injection process, and then the measurement container 10 is rotated to produce the first mixture. May be.

  Further, in the measurement apparatus 1A, the measurement reagents sealed in the first liquid storage chambers 14a of the five analysis cells 11 are measurement reagents of different types, amounts, or types and amounts, but the types and amounts are different. The same measurement reagent may be enclosed. However, the measurement reagents sealed in the first liquid storage chambers 14a of the five analysis cells 11 are different in type, amount, or different types and amounts, so that each first liquid storage chamber 14a has a different measurement reagent. Calculate the light absorption characteristics of the enclosed measurement reagents 40a to 40e, take into account the light absorption characteristics of the measurement reagents 40a to 40e, and calculate the concentration of the measurement component of the measurement liquid that reacts with each measurement reagent 40a to 40e. can do. As a result, the concentration of a plurality of measurement components contained in the measurement liquid can be calculated simultaneously with one measurement container 10.

[Embodiment 2]
The following will describe another embodiment of the present invention with reference to FIGS. For convenience of explanation, members having the same functions as those described in the embodiment are given the same reference numerals, and descriptions thereof are omitted.

  When using a soil extract as the measurement solution, first, the soil is put into a container containing an extraction solvent, and the container is vibrated to stir the soil and the extraction solvent. Thereby, a soil component is extracted to an extraction solvent and a soil extract is produced. Next, by filtering the produced soil extract, the soil in the soil extract is removed to obtain a measurement solution. However, even after the soil is filtered, the measurement solution has a slight amount of soil, and thus the measurement solution has a slight turbidity.

  If turbidity is present in the measurement liquid, when measuring the amount of light transmitted through the measurement liquid, a part of the light is reflected or scattered by the soil that is the cause of turbidity, so the light transmitted through the measurement is reduced. . As a result, there is a problem that the concentration of the measurement component of the measurement liquid calculated using the measured amount of transmitted light is higher than the concentration of the measurement component of the actual measurement liquid.

  Therefore, the measurement apparatus 1B in the present embodiment can accurately calculate the measurement component of the measurement liquid by considering the influence of turbidity existing in the measurement liquid.

(Configuration of measuring apparatus 1B)
The configuration of the measuring apparatus 1B in the present embodiment will be described with reference to FIG. FIG. 8 is a schematic diagram showing the configuration of the measuring apparatus 1B in the present embodiment.

  The measurement apparatus 1B has substantially the same configuration as that of the measurement apparatus 1A in Embodiment 1 (see FIG. 1), but the configurations of the control unit 30B and the calculation unit 31B are different as shown in FIG.

  The control unit 30 </ b> B controls operations of the driving mechanism 23, the liquid injection device 24, and the light emitting unit 25 a of the optical measurement mechanism 25.

  The calculation unit 31B calculates the absorbance of the liquid sample in the first liquid storage chamber 14a based on the light transmission amount data (spectral data) output from the light receiving unit 25b, and stores the first liquid from the calculated absorbance. The concentration of the measurement component in the liquid sample in the chamber 14a is calculated.

(Measuring method of measuring device 1B)
A measurement method using the measurement apparatus 1B will be described with reference to FIG. FIG. 9 is a flowchart showing a measurement procedure using the measurement apparatus 1B.

  In the measurement using the measuring apparatus 1B, as shown in FIG. 9, first, a liquid injection trial step (S1), a diluent injection step (S2), a first stirring step (S3), a measurement liquid injection step (S4), A 2nd stirring process (S5) and a 1st mixture measurement process (S6) are performed. Since these steps are the same as those described in the first embodiment, description thereof is omitted.

  When the first mixture measurement step (S6) is performed, next, an optical measurement is performed using the optical measurement mechanism 25 in accordance with an instruction from the control unit 30B, and the measurement liquid and dilution contained in the second liquid storage chamber 14b The amount of light transmitted through the liquid mixture is measured (S11, liquid mixture measurement step (liquid mixture measurement mode)).

  The light receiving unit 25b outputs measurement data of the amount of transmitted light that has passed through the mixed solution of the measurement solution and the diluted solution obtained in the mixed solution measurement step to the calculation unit 31B. The calculation unit 31B uses the measurement data of the amount of light transmitted through the mixture of the measurement liquid and the dilution liquid obtained in the first reference liquid measurement step when calculating the concentration of the measurement component of the measurement liquid described later. To do.

  Finally, the calculation unit 31B calculates the concentration of the measurement component (S12).

  Specifically, the absorbance due to the absorption of the turbidity of the measurement liquid is calculated from the amount of light transmitted through the mixed liquid of the measurement liquid and the dilution liquid measured in the mixed liquid measurement step. As described above, the measurement reagent 40 is not sealed in the second liquid storage chamber 14b. Therefore, the absorbance calculated from the amount of light transmitted through the mixed solution of the measuring solution and the diluted solution measured in the mixed solution measuring step is the absorbance due to the absorption of the turbidity of the measuring solution. Therefore, it is possible to calculate the absorbance due to the absorption of the turbidity of the measurement liquid from the amount of light transmitted through the mixture of the measurement liquid and the dilution liquid measured in the mixed liquid measurement step.

  Here, in the liquid injection trial step, when the diluent and the measurement liquid are injected into the second liquid storage chamber 14b, foreign matters such as air (bubbles) exist in the first tube 24c and the second tube 24d. There is a possibility that the amount of the dilution liquid and the measurement liquid injected into the second liquid storage chamber 14b is not necessarily accurate. However, the degree of coloration of the first mixture M1a to M1e changes rapidly depending on the amount of the measurement liquid and the dilution liquid, that is, the dilution rate, whereas the absorbance due to the turbidity of the measurement liquid is the second liquid storage chamber 14b. Since the measurement reagent 40 is not sealed in the tube, it does not change greatly depending on the dilution rate of the mixture of the measurement solution and the diluted solution. Therefore, the absorbance due to the absorption of turbidity in the measurement liquid can be calculated by the mixed liquid measurement step.

  Next, the calculation unit 31B calculates the absorbances of the first mixtures M1a to M1e from the amounts of light transmitted through the first mixtures M1a to M1e measured in the first mixture measurement step. Specifically, the calculation unit 31B calculates the absorbances of the first mixtures M1a to M1e in consideration of the absorbance due to the turbidity of the measurement liquid. Thereby, even if turbidity exists in the measurement solution, the influence of light absorption due to turbidity can be eliminated, so that the absorbance of the first mixtures M1a to M1e can be accurately calculated.

  Next, the calculation unit 31B calculates the concentrations of the measurement components contained in the first mixtures M1a to M1e from the calculated absorbances of the first mixtures M1a to M1e, respectively. Next, the concentration of the measurement component contained in the measurement liquid is calculated by multiplying the calculated concentration of the measurement component contained in the first mixture M1a to M1e by the reciprocal of the dilution factor.

  In the liquid injection trial step, the dilution liquid and the measurement liquid are injected into the second liquid storage chamber 14b so that the ratio of the amount of the dilution liquid and the measurement liquid becomes a constant ratio (for example, 1: 1). Thereby, the calculation part 31B can calculate the light absorbency by the turbidity of the measurement liquid in the fixed ratio. As a result, when calculating the absorbance of each of the second mixtures M2a to M2e, the absorbance due to turbidity at the dilution rate of each first liquid storage chamber 14a can be taken into consideration.

  Moreover, in this embodiment, although the liquid mixture measurement process was performed after the 1st mixture measurement process, it is not restricted to this. The mixed liquid measurement step may be performed between the second stirring step and the first mixture measurement step.

  As described above, in the measurement apparatus 1B according to the present embodiment, in addition to the measurement method according to the first embodiment, the liquid mixture of the measurement liquid and the dilution liquid is transmitted through the second liquid storage chamber 14b in which the measurement reagent 40 is not sealed. A mixed liquid measuring step for measuring the amount of transmitted light is performed. Then, the calculation unit 31B calculates the light absorbance due to the turbidity of the measurement liquid from the measurement result obtained in the liquid mixture measurement step, and when calculating the absorbance of the first mixtures M1a to M1e, the light due to the turbidity of the measurement liquid To eliminate the influence of the absorbance. Thereby, the light absorbency of 1st mixture M1a-M1e can be calculated correctly, and the density | concentration of the measurement component of a measurement liquid can be calculated accurately. In addition, since the liquid injection trial process and the mixed liquid measurement process can be executed in the second liquid storage chamber 14b, the measurement accuracy can be improved with a small number of processes, the measurement apparatus can be made compact, and the manufacturing cost can be reduced. It can be made to.

[Embodiment 3]
The following will describe another embodiment of the present invention with reference to FIG. 10 and FIG. For convenience of explanation, members having the same functions as those described in the embodiment are given the same reference numerals, and descriptions thereof are omitted.

  In addition to the absorbance after the reaction between the measurement reagent 40 and the measurement component in the measurement liquid, the intrinsic absorbance characteristic of the measurement reagent 40 is reflected in the measurement result of the absorbance of the measurement liquid. Therefore, when the intrinsic light absorption characteristic of the measurement reagent 40 is not taken into consideration, the concentration of the measurement component of the measurement liquid calculated using the measured amount of transmitted light is higher than the concentration of the measurement component of the actual measurement liquid. There is a problem of becoming.

  Therefore, the measurement apparatus 1C in the present embodiment can accurately calculate the measurement component of the measurement liquid by considering the influence of the intrinsic light absorption characteristics of the measurement reagent 40.

(Configuration of measuring device 1C)
The configuration of the measuring apparatus 1C in the present embodiment will be described with reference to FIG. FIG. 10 is a schematic diagram showing the configuration of the measuring apparatus 1C in the present embodiment.

  The measurement device 1C has substantially the same configuration as that of the measurement device 1A in Embodiment 1 (see FIG. 1), but the configurations of the control unit 30C and the calculation unit 31C are different as shown in FIG.

  The control unit 30C controls operations of the drive mechanism 23, the liquid injection device 24, and the light emitting unit 25a of the optical measurement mechanism 25.

  The calculation unit 31C calculates the absorbance of the liquid sample in the first liquid storage chamber 14a based on the light transmission amount data (spectral data) output from the light receiving unit 25b, and stores the first liquid from the calculated absorbance. The concentration of the measurement component in the liquid sample in the chamber 14a is calculated.

(Measuring method of measuring device 1C)
A measurement method using the measurement apparatus 1C will be described with reference to FIG. FIG. 11 is a flowchart illustrating a measurement procedure using the measurement apparatus 1C.

  In the measurement using the measuring apparatus 1C, as shown in FIG. 11, first, a liquid injection trial step (S1), a diluent injection step (S2), and a first stirring step (S3) are performed. Since these steps are the same as those described in the first embodiment, description thereof is omitted.

  When the first stirring step (S3) is executed, next, an optical measurement is performed using the optical measurement mechanism 25 according to an instruction from the control unit 30C, and the diluent and measurement stored in the first liquid storage chamber 14a are measured. The amounts of light transmitted through the second mixtures M2a to M2e, which are mixtures with the reagents 40a to 40e, are respectively measured (S21, second mixture measurement step (second mixture measurement mode)).

  The light receiving unit 25b outputs measurement data of the amount of light transmitted through the second mixtures M2a to M2e obtained by the second mixture measurement step to the calculation unit 31C. The calculation unit 31C uses the measurement data of the amount of light transmitted through the second mixtures M2a to M2e obtained in the second mixture measurement step when calculating the concentration of the measurement component of the measurement liquid described later.

  Next, a measurement liquid injection step (S4), a second stirring step (S5), and a first mixture measurement step (S6) are performed. Since these steps are the same as those described in the first embodiment, description thereof is omitted.

  Finally, the calculation unit 31C calculates the concentration of the measurement component (S22).

  Specifically, first, the calculation unit 31C calculates the intrinsic light absorption characteristics of the measurement reagents 40a to 40e from the amounts of light transmitted through the second mixtures M2a to M2e measured in the second mixture measurement step.

  Next, the calculation unit 31C calculates the absorbances of the first mixtures M1a to M1e from the amounts of light transmitted through the first mixtures M1a to M1e measured in the first mixture measurement step. At this time, the calculation unit 31C calculates the absorbances of the first mixtures M1a to M1e based on the measurement results obtained in the second mixture measurement process, taking into account the influence of the absorbance characteristics of the measurement reagents 40a to 40e. To do. Thereby, the influence by light absorption of the measurement reagents 40a-40e can be excluded.

  Next, the calculation unit 31C calculates the concentrations of the measurement components contained in the first mixtures M1a to M1e from the calculated absorbances of the first mixtures M1a to M1e, respectively. Next, the calculation unit 31C calculates the concentration of the measurement component contained in the measurement liquid by multiplying the calculated concentration of the measurement component contained in the first mixture M1a to M1e by the reciprocal of the dilution rate.

  As described above, in the measurement apparatus 1C according to the present embodiment, in addition to the measurement method according to the first embodiment, between the dilution liquid injection trial process and the measurement liquid injection process, the dilution liquid injection process, the second mixture measurement process, , And in the second mixture measurement step, light transmitted through the second mixtures M2a to M2e, which are mixtures of the measurement reagents 40a to 40e and the diluent, are measured. Thereby, the intrinsic light absorption properties of the measurement reagents 40a to 40e can be calculated from the measurement results obtained in the second mixture measurement step. As a result, when calculating the absorbance of the first mixtures M1a to M1e, it is possible to eliminate the influence of the absorbance characteristics of the measurement reagents 40a to 40e. Thereby, the light absorbency of 1st mixture M1a-M1e can be calculated correctly, and the density | concentration of the measurement component of a measurement liquid can be calculated accurately.

[Summary]
The measuring apparatuses 1A to 1C according to the first aspect of the present invention include one or a plurality of measurement chambers (first liquid storage chambers 14a) in which measurement reagents 40 and 40a to 40e that react with measurement components in the measurement liquid are enclosed. , A measurement container 10 including a liquid injection trial chamber (second liquid storage chamber 14b) in which the measurement reagents 40 and 40a to 40e are not sealed, the measurement chamber (first liquid storage chamber 14a), and the liquid injection trial A liquid injection part (liquid injection device 24) for injecting a measurement liquid and a diluent into the chamber (second liquid storage chamber 14b), and the measurement liquid injected into the measurement chamber (first liquid storage chamber 14a) and In the measurement results of the measurement unit (optical measurement mechanism 25) that measures the transmitted light that has passed through the mixture of at least one of the diluents and the measurement reagents 40 and 40a to 40e, and the measurement result of the measurement unit (optical measurement mechanism 25) Base The calculation units 31A to 31C for calculating the concentration of the measurement component in the measurement liquid, and the control units 30A to 30C for controlling the liquid injection unit (liquid injection device 24) and the measurement unit (optical measurement mechanism 25), The liquid injection part (liquid injection device 24) includes a first tube 24c that supplies the measurement liquid to the measurement container 10, and supplies the dilution liquid to the measurement container 10. The control unit 30A-30C includes the second tube 24d, and the control units 30A to 30C include the liquid injection unit so that the first tube 24c and the second tube 24d are filled with the measurement liquid and the dilution liquid, respectively. By controlling the (liquid injection device 24), the liquid injection trial chamber (second liquid storage chamber 14) via the first tube 24c and the second tube 24d. ), The liquid injection trial mode in which the dilution liquid and the measurement liquid are respectively injected is executed, and after the liquid injection trial mode, the liquid injection unit (liquid injection device 24) is controlled to thereby control the first. A measurement liquid injection mode in which the measurement liquid is injected into the measurement chamber (first liquid storage chamber 14a) through the tube 24c, and the measurement chamber (first liquid storage chamber 14a) through the second tube 24d. ), A liquid injection mode including a dilution liquid injection mode for injecting the dilution liquid is executed, and after the liquid injection mode, the measurement section (optical measurement mechanism 25) is controlled to thereby control the measurement chamber (second measurement mode). Transmitted light that has passed through the first mixture M1a to M1e composed of the dilution liquid, the measurement liquid, and the measurement reagents 40 and 40a to 40e mixed in the one liquid storage chamber 14a) The first mixture measurement mode is measured, and the calculation units 31A to 31C calculate the concentration of the measurement component in the measurement liquid based on the measurement result obtained in the first mixture measurement mode. It is a feature.

  According to this feature, by executing the liquid injection trial mode before executing the liquid injection mode, the first tube and the second tube are filled with the measurement liquid and the diluent, respectively. As a result, in the liquid injection mode, when the dilution liquid and the measurement liquid are injected into the measurement chamber through the first tube and the second tube, an accurate amount of the dilution liquid and the measurement liquid are injected into the measurement chamber. Can do. As a result, the measurement liquid and the dilution liquid can be injected into the measurement chamber so that the dilution rate is accurate. Thereby, the calculation part can calculate the density | concentration of the measurement component of a measurement liquid accurately based on the measurement result obtained in the 1st mixture measurement mode.

  Therefore, it is possible to provide a measuring apparatus that can accurately measure the measurement components contained in the measurement liquid.

  The measurement apparatus 1B according to the second aspect of the present invention is the measurement apparatus 1B according to the first aspect, wherein the measurement unit (optical measurement mechanism 25) is configured such that the measurement liquid and the diluted liquid injected into the liquid injection trial chamber (second liquid storage chamber 14b). The control unit 30B controls the measurement unit (optical measurement mechanism 25), thereby controlling the liquid injection trial chamber (second liquid) in the liquid injection trial mode. The liquid mixture measurement mode for measuring the transmitted light that has passed through the liquid mixture of the dilution liquid and the measurement liquid injected into the storage chamber 14b) is further executed, and the calculation unit 31B is operated in the first mixture measurement mode. It is preferable that the concentration of the measurement component in the measurement liquid is calculated based on the obtained measurement result and the measurement result obtained in the mixed liquid measurement mode.

  According to said structure, the liquid mixture measurement process which measures the permeation | transmission quantity of the light which permeate | transmitted the liquid mixture of a measurement liquid and a dilution liquid is performed in the liquid injection | pouring trial chamber in which the measurement reagent is not enclosed. The calculating unit calculates the light absorbance due to the turbidity of the measurement liquid from the measurement result obtained in the mixed liquid measurement step, and when calculating the absorbance of the first mixture, the influence due to the light absorbance due to the turbidity of the measurement liquid. Eliminate. Thereby, the light absorbency of a 1st mixture can be calculated correctly and the density | concentration of the measurement component of a measurement liquid can be calculated accurately.

  In the measurement apparatus 1C according to aspect 3 of the present invention, in the aspect 1, the control unit 30C includes the dilution liquid injection mode and the measurement part between the liquid injection trial mode and the measurement liquid injection mode. By controlling the (optical measurement mechanism 25), the dilution liquid injected into the measurement chamber (first liquid storage chamber 14a) in the dilution liquid injection mode, and the measurement reagents 40 and 40a to 40e. A second mixture measurement mode that measures the transmitted light that has passed through the second mixtures M2a to M2e, and the calculation unit 31C includes the measurement result obtained in the first mixture measurement mode and the second mixture measurement mode. It is preferable that the concentration of the measurement component in the measurement liquid is calculated based on the measurement result obtained in (1).

  According to said structure, in the 2nd mixture measurement mode, the light which permeate | transmitted the 2nd mixture which is a mixture of a measurement reagent and a diluent is measured. Thereby, the calculation part can calculate the intrinsic light absorption characteristic of the measurement reagent from the measurement result obtained in the second mixture measurement mode. As a result, when calculating the absorbance of the first mixtures M1a to M1e, it is possible to eliminate the influence of the absorbance characteristics of the measurement reagent. Thereby, the light absorbency of a 1st mixture can be calculated correctly and the density | concentration of the measurement component of a measurement liquid can be calculated accurately.

  The measurement apparatuses 1A to 1C according to the fourth aspect of the present invention include the measurement chambers (first liquid storage chambers 14a) according to any one of the first to third aspects, and the measurement chambers (first liquid storage chambers 14a). In one liquid storage chamber 14a), different types of measurement reagents 40a to 40e, different amounts of measurement reagents 40a to 40e, or different types and different amounts of measurement reagents 40a to 40e are enclosed, and the calculation units 31A to 31A to 31C is preferably configured to calculate the concentration of the measurement component in each measurement liquid in the plurality of measurement chambers (first liquid storage chamber 14a).

  According to the above configuration, the measurement container includes a plurality of measurement chambers, and each of the plurality of measurement chambers has different types of measurement reagents, different amounts of measurement reagents, or different types and different amounts of measurement reagents. It is enclosed. Then, calculate the light absorption characteristics of the measurement reagents enclosed in each of the measurement chambers, take into account the light absorption characteristics of each measurement reagent, and calculate the concentration of the measurement component of the measurement liquid that reacts with each measurement reagent. Yes. Thereby, the density | concentration of the some measurement component contained in a measurement liquid can be calculated simultaneously with one measurement container.

  Measuring device 1A-1C which concerns on aspect 5 of this invention is provided with the rotation drive part (drive mechanism 23) which rotates the said measurement container 10 centering on the rotating shaft 19 in any one of the said aspects 1-3, The plurality of measurement chambers (first liquid storage chambers 14a) are preferably arranged on the same circumference around the rotation shaft 19.

  According to said structure, the some measurement chamber is arrange | positioned on the same periphery centering on a rotating shaft. Thereby, a plurality of measurements can be performed with one optical system by rotating the measurement container around the rotation axis by the rotation drive unit.

  The measurement method according to the sixth aspect of the present invention includes one or a plurality of measurement chambers (first liquid storage chambers 14a) in which measurement reagents 40 and 40a to 40e that react with measurement components in a measurement solution are sealed, and the measurement described above. Measurement liquid injected into the measurement chamber (first liquid storage chamber 14a) using the measurement container 10 including a liquid injection trial chamber (second liquid storage chamber 14b) in which the reagents 40 and 40a to 40e are not sealed. Is a first tube 24c for feeding the measurement liquid to the measurement container 10 and a second tube 24d for feeding a dilution liquid to the measurement container 10. With respect to the liquid injection trial chamber (second liquid storage chamber 14b) through the first tube 24c and the second tube 24d so as to be filled with the measurement liquid and the dilution liquid, respectively. After the liquid injection trial step for injecting the diluent and the measurement liquid, respectively, and after the liquid injection trial step, the measurement liquid is introduced into the measurement chamber (first liquid storage chamber 14a) via the first tube 24c. A liquid injection process for executing a measurement liquid injection process for injecting the dilution liquid and a dilution liquid injection process for injecting the dilution liquid into the measurement chamber (first liquid storage chamber 14a) via the second tube 24d; After the liquid injection step, the first mixture M1a to M1e composed of the dilution liquid, the measurement liquid, and the measurement reagents 40 and 40a to 40e mixed in the measurement chamber (first liquid storage chamber 14a) was permeated. Including a first mixture measurement step for measuring transmitted light and a calculation step for calculating the concentration of the measurement component in the measurement liquid based on the measurement result obtained in the first mixture measurement step. It is a symptom.

  According to the above feature, by performing the liquid injection trial step before the liquid injection step, the first tube and the second tube are filled with the measurement liquid and the diluent, respectively. Thus, in the liquid injection process, when the diluent and the measurement liquid are injected into the measurement chamber via the first tube and the second tube, an accurate amount of the dilution liquid and the measurement liquid are injected into the measurement chamber. Can do. As a result, the measurement liquid and the dilution liquid can be injected into the measurement chamber so that the dilution rate is accurate. Thereby, in a calculation process, based on the measurement result obtained at the 1st mixture measurement process, the concentration of the measurement ingredient of a measurement liquid can be calculated with sufficient accuracy.

  Therefore, it is possible to provide a measurement method capable of accurately measuring the measurement component contained in the measurement liquid.

  The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope shown in the claims, and embodiments obtained by appropriately combining technical means disclosed in different embodiments. Is also included in the technical scope of the present invention. Furthermore, a new technical feature can be formed by combining the technical means disclosed in each embodiment.

1A to 1C Measuring device 10 Measuring container 14a First liquid storage chamber (measuring chamber)
14b Second liquid storage chamber (liquid injection trial chamber)
19 Rotating shaft 23 Drive mechanism (Rotation drive unit)
24 Liquid injection device (liquid injection part)
24c 1st tube 24d 2nd tube 25 Optical measuring mechanism (measurement part)
30A-30C Control part 31A-31C Calculation part 40, 40a-40e Measuring reagent M1a-M1e 1st mixture M2a-M2e 2nd mixture

Claims (6)

A measurement container comprising one or a plurality of measurement chambers in which a measurement reagent that reacts with a measurement component in the measurement liquid is sealed, and a liquid injection trial chamber in which the measurement reagent is not sealed;
A liquid injection part for injecting a measurement liquid and a diluent into the measurement chamber and the liquid injection trial chamber,
A measurement unit that measures transmitted light that has passed through a mixture of the measurement reagent and at least one of the measurement liquid and the diluent injected into the measurement chamber;
Based on the measurement result of the measurement unit, a calculation unit that calculates the concentration of the measurement component in the measurement solution;
A measurement device comprising a control unit for controlling the liquid injection unit and the measurement unit,
The liquid injection part includes a first tube for feeding the measurement liquid to the measurement container, and a second tube for feeding the diluent to the measurement container,
The control unit
By controlling the liquid injection part so that the first tube and the second tube are filled with the measurement liquid and the diluent, respectively, via the first tube and the second tube, Execute a liquid injection trial mode in which the dilution liquid and the measurement liquid are respectively injected into the liquid injection trial chamber;
After the liquid injection trial mode, by controlling the liquid injection part, a measurement liquid injection mode for injecting the measurement liquid into the measurement chamber via the first tube, and via the second tube Performing a liquid injection mode including a diluent injection mode for injecting the diluent into the measurement chamber,
After the liquid injection mode, the measurement unit is controlled to measure transmitted light transmitted through the first mixture composed of the diluent, the measurement liquid, and the measurement reagent mixed in the measurement chamber. Run 1 mixture measurement mode,
The said calculation part calculates the density | concentration of the measurement component in the said measurement liquid based on the measurement result obtained in the said 1st mixture measurement mode, The measuring apparatus characterized by the above-mentioned. The measurement unit measures the transmitted light that has passed through the liquid mixture of the measurement liquid and the diluent injected into the liquid injection trial chamber,
The control unit controls the measurement unit to measure the transmitted light that has passed through the liquid mixture of the dilution liquid and the measurement liquid injected into the liquid injection trial chamber in the liquid injection trial mode. Execute liquid measurement mode further,
The calculation unit calculates the concentration of the measurement component in the measurement liquid based on the measurement result obtained in the first mixture measurement mode and the measurement result obtained in the liquid mixture measurement mode. The measuring apparatus according to claim 1. The control unit, between the liquid injection trial mode and the measurement liquid injection mode,
The diluent injection mode,
A second mixture measurement mode that measures the transmitted light that has passed through the second mixture of the dilution liquid injected into the measurement chamber and the measurement reagent in the dilution liquid injection mode by controlling the measurement unit. And run
The calculation unit calculates the concentration of the measurement component in the measurement liquid based on the measurement result obtained in the first mixture measurement mode and the measurement result obtained in the second mixture measurement mode. The measuring device according to claim 1, wherein A plurality of the measurement chambers are provided,
Each of the plurality of measurement chambers contains different types of measurement reagents, different amounts of measurement reagents, or different types and different amounts of measurement reagents.
The measurement apparatus according to claim 1, wherein the calculation unit calculates a concentration of a measurement component in each measurement solution of the plurality of measurement chambers. A rotation drive unit for rotating the measurement container about the rotation axis;
The measurement apparatus according to claim 4, wherein the plurality of measurement chambers are arranged on the same circumference around the rotation axis. Injection into the measurement chamber using a measurement container comprising one or a plurality of measurement chambers in which a measurement reagent that reacts with a measurement component in the measurement liquid is sealed and a liquid injection trial chamber in which the measurement reagent is not sealed A measurement method for calculating a concentration of a measurement component contained in a measured liquid,
The first tube for feeding the measurement liquid to the measurement container and the second tube for feeding the dilution liquid to the measurement container are filled with the measurement liquid and the dilution liquid, respectively. A liquid injection trial step of injecting the diluent and the measurement liquid into the liquid injection trial chamber via the tube and the second tube,
After the liquid injection trial step, the measurement liquid injection step of injecting the measurement liquid into the measurement chamber through the first tube and the dilution liquid is injected into the measurement chamber through the second tube A liquid injection process for performing a dilution liquid injection process, and
A first mixture measurement step for measuring transmitted light that has passed through the first mixture composed of the diluent, the measurement solution, and the measurement reagent mixed in the measurement chamber after the liquid injection step;
And a calculation step of calculating the concentration of the measurement component in the measurement liquid based on the measurement result obtained in the first mixture measurement step.

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