JP6573257B2 - Measuring apparatus and measuring method - Google Patents

Description

  The present invention relates to a measurement apparatus and a measurement method suitable for analyzing a 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.

  Generally, a soil analyzer injects each soil extract into a plurality of test tubes while measuring with a graduated dropper, and then adds the reagent and diluent determined for each soil component to the test tubes. Inject and develop color. And it is measured by converting into a numerical value using a colorimetric table, a turbidimetric table, an absorptiometric method or the like.

  However, since the above-described measurement method needs to mix a reagent with each soil extract, the number of repetitive operations increases. Moreover, it is necessary to prepare a reagent according to the soil component to be measured, and the complexity is high.

  By performing soil analysis frequently, it is possible to perform fertilization design in consideration of the influence of the previous crop by performing detailed analysis for each field and analysis for each cropping. 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.

  However, it is difficult to increase the frequency of analysis due to the high complexity described above.

  There are several measurement methods that include such repetitive operations and measurement methods that approach a plurality of components from the same test solution, not limited to soil analysis. In recent years, a method for analyzing components by mixing a test solution and a reagent by a simple method to solve such a complexity has been proposed.

  For example, Patent Document 1 discloses a sample analysis chip used for detection and analysis of biochemical reactions. FIG. 16 is a plan view showing the sample analysis chip 100 described in Patent Document 1. FIG. As shown in FIG. 16, the sample analysis chip 100 has a plurality of wells 102 on a substrate 101 and a flow path for feeding a solution, for example, a liquid sample, to each well 102. The flow path has at least one main flow path 103 that communicates with each well 102 and further has a side path 105 that connects the main flow path 103 and the well 102 in order to send liquid to each well 102. An inlet (INLET) is formed at the end of the main flow path 103, and an outlet (OUTLET) that also serves as an air outlet / outlet is formed at the other end (INLET / OUTLET 107 in the figure).

  In the sample analysis chip 100, a liquid sample is introduced from this inlet (INLET 107), and the introduced liquid sample is sent from the main flow path 103 to the well 102, which is an inspection section, by centrifugal force. Then, the fed liquid sample is reacted with the reagent previously enclosed in the well 102, and the reaction is observed.

  Further, in the sample analysis chip 100, the connection port between the main flow path 103 and the well 102 has a width and a cross-sectional area so that the solution does not enter the well 102 before the sample analysis chip 100 is rotated. Furthermore, the outer peripheral wall surface of the well 102 is different in hydrophilicity from the inner peripheral wall surface. Accordingly, the reagent can be fixed to the outer peripheral side of the well 102, and the reagent is prevented from being mixed with the liquid sample before the sample analysis chip 100 is rotated and contaminated. In the sample analysis chip 100, the width of the main flow path 103 is narrow at the main flow path peak portion 103a and wide at the main flow path valley portion 103b. In this manner, the amount of liquid distributed to each well 102 can be controlled by increasing the width of the main flow path valley portion 103b.

  As described above, in the sample analysis chip 100 described in Patent Document 1, a plurality of types of specimens are simultaneously processed with the same reagent using a very small amount of a test solution, or conversely, a plurality of types of specimens are simultaneously processed with a plurality of types. Processing can be performed, and the time and labor required in the past can be greatly reduced.

JP 2012-185000 A (published September 27, 2012)

  However, in the sample analysis chip 100 disclosed in Patent Document 1, when analyzing a plurality of components contained in a liquid sample, measurement accuracy may be lowered due to the following problems.

  That is, in the sample analysis chip 100 disclosed in Patent Document 1, after mixing the liquid sample and the reagent, the absorbance is measured from the optical characteristics of the liquid sample, for example, the light transmission intensity. However, when gas is generated by the reaction between the liquid sample and the reagent when the liquid sample and the reagent are mixed, bubbles are generated. Alternatively, when the liquid sample and the reagent are mixed and stirred using centrifugal force or rotational acceleration / deceleration, bubbles are generated inside the liquid sample. For this reason, when the optical properties of the liquid sample are measured in a state where bubbles are present in the liquid sample, there is a problem that light is scattered and reflected due to the bubbles and the measurement accuracy is lowered.

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a measuring apparatus and a measuring method capable of performing accurate measurement even when bubbles are present in a measurement sample. is there.

  In order to solve the above-described problems, a measurement apparatus according to one embodiment of the present invention includes a measurement container including one or a plurality of measurement chambers that store a liquid, the measurement chamber, and the liquid stored in the measurement chamber. A measurement unit that measures light transmitted through the liquid, a stirring unit that stirs the measurement container, a liquid injection unit that injects the liquid into the measurement chamber, and the measurement unit, the stirring unit, and the liquid injection unit. A measuring unit including a bottom surface and a top surface whose inner walls are opposed to each other, and the top surface is a low-top surface that transmits light, and the periphery of the low-top surface And the high-top surface disposed at a position higher than the low-top surface with respect to the bottom surface, the control unit is configured such that the liquid injection unit is lower in liquid level than the low-top surface. A first liquid injection mode for injecting liquid into the measurement chamber so as to be in position, and the stirring The second liquid for injecting the liquid into the measurement chamber in which the liquid is injected by the first liquid injection mode and the liquid level at a position higher than the low ceiling surface. The injection mode and the first measurement mode in which the measurement unit measures the light transmitted through the measurement chamber and the liquid stored in the measurement chamber are performed.

  In order to solve the above-described problems, a measurement method according to one embodiment of the present invention includes one or a plurality of measurement chambers that store liquid, and the measurement chamber includes a bottom surface and a top surface whose inner walls face each other. In addition, the measurement includes a low-top surface through which the top surface transmits light, and a high-top surface that is positioned around the low-top surface and is positioned higher than the low-top surface with respect to the bottom surface. A measurement method using a container, wherein the measurement chamber and a measurement step of measuring light transmitted through the liquid stored in the measurement chamber, a stirring step of stirring the measurement vessel, and the liquid in the measurement chamber And a control step for controlling the measurement step, the agitation step, and the liquid injection step, wherein the control step includes a liquid level lower than the low ceiling surface in the liquid injection step. Injecting liquid into the measurement chamber In the liquid injection mode, the stirring mode in which the measurement container is stirred in the stirring step, and the liquid level is higher than the low ceiling surface in the measurement chamber into which the liquid has been injected in the first liquid injection mode. In this order, the second liquid injection mode for injecting liquid and the first measurement mode for measuring the light transmitted through the measurement chamber and the liquid stored in the measurement chamber in the measurement step are executed in this order. Features.

  According to one embodiment of the present invention, there is an effect of providing a measurement device and a measurement method that can perform measurement with high accuracy even when bubbles are present in a measurement sample. Furthermore, there is an effect of providing a measuring apparatus and a measuring method capable of improving the measurement accuracy by efficiently stirring the measurement liquid.

It is the schematic which shows the control system 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 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 upper direction, (b) is BB 'arrow sectional drawing of (a). It is. The state after mixing and stirring the measurement liquid 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 a flowchart which shows the procedure of the measurement using the said measuring apparatus. It shows a mode that a measurement liquid is inject | poured into the measurement chamber of the said measurement container, (a) is sectional drawing of the measurement chamber before a 1st liquid injection process, (b) is after a 1st liquid injection process. (C) is a cross-sectional view of the measurement chamber after the first stirring step, and (d) is a cross-sectional view of the measurement chamber 14 after the second liquid injection step. It is the schematic which shows the control system 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 control system 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. It is the schematic which shows the control system of the measuring apparatus which concerns on Embodiment 4 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 control system of the measuring apparatus which concerns on Embodiment 5 of this invention. It is a flowchart which shows the procedure of the measurement using the said measuring apparatus. It is a top view which shows the structure of the conventional measurement container.

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. 2 is a perspective view showing the configuration of the measuring apparatus 1A in the present embodiment. FIG. 3 schematically shows the outline of the measurement container 10, (a) is a front view of the measurement container 10 as viewed from above, and (b) is a cross-sectional view taken along the line AA ′ in (a). FIG.

  The measuring apparatus 1 </ b> A is for agitating and mixing the liquid in the measuring container 10 by rotating the measuring container 10 about 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 measuring device 1A includes a measuring container 10, a table 22, a drive mechanism 23 (stirring unit), a liquid injection device 24A (liquid injection unit), and an optical measurement mechanism 25 (measurement unit). I have. Although not shown in FIG. 2, the measuring apparatus 1A also includes a control unit 30A (see FIG. 1).

  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 sector shape with a virtual rotation axis 19 as the center, and the measurement container 10 has a disk-like structure as a whole. Each analysis cell 11 includes a liquid inlet 13 and a measurement chamber 14 so that the liquid injected from the liquid inlet 13 can be stored in the measurement chamber 14. Details of the measurement container 10 will be described later.

  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 measurement 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 (see FIG. 1). Thereby, the measurement container 10 rotates around the rotation shaft 19. As an example, the drive mechanism 23 can be composed of a stepping motor capable of pulse control.

  The liquid injection device 24 </ b> A is for injecting a liquid into the measurement container 10. The liquid injection device 24A includes a measurement liquid storage container (not shown) that stores a measurement liquid containing one or more measurement components to be measured. The measurement liquid is stored in the measurement liquid container before the measurement is started. The liquid injection device 24A injects the measurement liquid into the measurement container 10 according to an instruction from the control unit 30A. Specifically, the liquid injection device 24 </ b> A injects the measurement liquid into the measurement chamber 14 from the liquid injection port 13 of each analysis cell 11.

  The liquid injection device 24A may sequentially inject the measurement liquid into the liquid injection ports 13 of the respective analysis cells 11 or may inject the measurement liquid into the liquid injection ports 13 of all the analysis cells 11 at the same time.

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

  The optical measurement mechanism 25 measures the optical characteristics of the measurement liquid in the measurement chamber 14 of the measurement container 10 and analyzes the measurement components in the measurement liquid. As an example, the optical measurement mechanism 25 measures a measurement component in the measurement liquid by an 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 emits light to any one of the analysis cells 11 of the measurement container 10 set on the table 22 that is rotationally driven in accordance with an instruction from the control unit 30A. The light emitting unit 25a is disposed so as to be positioned above any one of the analysis cells 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 top | upper surface side measurement window 16a (it mentions later in detail) of the upper surface of the analysis cell 11 arrange | positioned below.

  The light receiving unit 25b is irradiated from the light emitting unit 25a to the top surface side measurement window 16a, passes through the analysis cell 11 and the measurement liquid, and is provided on the bottom surface side measurement window 16b on the lower surface of the analysis cell 11 (see FIG. 4. ) Is received, and the amount of transmission of the received light is measured. The light receiving unit 25b outputs the measured light transmission amount to the control unit 30A as spectrum data.

  The control unit 30A calculates the absorbance of the measurement liquid in the analysis cell 11 based on the spectrum data output from the light receiving unit 25b, and calculates the component concentration in the measurement liquid.

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

  As shown in FIG. 3A, the measurement container 10 is rotationally driven by the drive mechanism 23 (see FIG. 2) of the measurement apparatus 1A described above around the rotation axis 19 representing a virtual line. is there. Each analysis cell 11 is partitioned as shown by a broken line in the figure and does not communicate with each other. 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 one or plural.

  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 injection ports 13 are formed on the first circumference (on the same circumference) around the rotation shaft 19. Similarly, all the top surface side measurement windows 16a are formed along the outer edge of the measurement container 10 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. In the present embodiment, the entire measurement container 10 is 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 measurement chamber 14 formed in the flange portion, and the liquid inlet 13. It is formed from a flow path 15 connecting the measurement chamber 14.

  In each measurement chamber 14, a reagent 40 that reacts with a predetermined component among a plurality of components contained in the measurement liquid is sealed. In the flow path 15, an inclined surface 15 a is formed that descends from the liquid inlet 13 toward the measurement chamber 14 in the outer peripheral direction. As described above, the measurement container 10 has a configuration in which a plurality of liquid injection ports 13 are formed around the rotation shaft 19 and a measurement chamber 14 communicating with the flow channel 15 is formed on the outer peripheral side of each liquid injection port 13. ing.

  The six measurement 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, the 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 cross-sectional view taken along the line BB ′ of (a). FIG.

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

  The measurement chamber 14 is a space for storing the measurement liquid and measuring the amount of light transmitted through the measurement liquid. In each measurement chamber 14, a reagent 40 that reacts with a predetermined measurement component contained in the measurement liquid is sealed. For example, the reagent 40 in each measurement chamber 14 is a reagent that exhibits a color reaction with respect to a measurement component to be measured in each analysis cell 11. The reagent 40 may be set arbitrarily according to the measurement component, and is not particularly limited. For example, as a 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” mixed A solution etc. can be mentioned. When measuring other measurement components of the measurement liquid, a commercially available reagent 40 corresponding to the measurement component or the developed reagent 40 can be used. The reagent 40 may be a solid such as a powder or a liquid.

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

  Furthermore, the top surface 17 of the measurement 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 part of the circumferential direction among the ceiling surfaces 17 of the measurement chamber 14, and the high ceiling surface 17a is provided on both sides of 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 measurement chamber 14. A step is formed on the top surface 17, and the top surface 17 of the measurement chamber 14 has a shape in which a portion of the top surface-side measurement window 16 a that is a light transmission portion is dug down from the periphery thereof. 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 16 a and the bottom surface side measurement window 16 b of the measurement chamber 14 are formed along the outer edge of the measurement container 10 on the same circumference (second circumference) around the rotation axis 19. (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.

  One end of the flow path 15 is connected to the liquid inlet 13 and the other end is connected to the measurement chamber 14. In the flow path 15, an inclined surface 15 a is formed that descends from the liquid inlet 13 toward the measurement 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 measurement 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 measurement chamber 14 is formed. As a result, the measurement liquid introduced from the liquid injection port 13 can be smoothly guided to the measurement chamber 14 along the inclined surface 15 a without accumulating in the vicinity immediately below the liquid injection port 13. Furthermore, when the measurement liquid and the reagent 40 are mixed by the centrifugal force of rotation of the measurement container 10 described later, the measurement liquid is prevented from flowing back from the measurement chamber 14 to the liquid inlet 13, and the measurement liquid is measured. It is possible to prevent scattering to the outside of the container 10.

(Measures against bubbles generated in the measurement sample)
Next, countermeasures against bubbles generated in the measurement sample will be described with reference to FIG. FIG. 5 is a view schematically showing the state of the measurement chamber 14 after the measurement liquid and the reagent 40 (see FIG. 3) are mixed and stirred, and (a) is a front view of the analysis cell 11 as viewed from above. (B) is a cross-sectional view taken along the line CC ′ in (a).

  In the measurement apparatus 1A of the present embodiment, the measurement sample L1 is obtained by mixing and stirring the measurement liquid and the reagent 40 in the measurement chamber 14. The measurement apparatus 1A calculates the component concentration in the measurement liquid by measuring the optical characteristics of the measurement sample L1.

  When the measurement liquid and the reagent 40 are mixed, if a gas is generated by the reaction between the measurement liquid and the reagent 40, a bubble B is generated in the measurement chamber 14. Alternatively, when the measurement container 10 is rotated and the measurement liquid and the reagent 40 are mixed and stirred, bubbles B are generated inside the measurement sample L1.

  However, when optical measurement is performed in a state where the bubble B exists in the measurement chamber 14, there is a case where light is scattered and reflected due to the bubble 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 apparatus 1A of the present embodiment, the top surface 17 of the measurement chamber 14 is positioned at the periphery of the low ceiling surface 17b that transmits light and the low ceiling surface 17b, and the measurement chamber 14 with respect to the bottom surface 18 of the high ceiling surface 17a arrange | positioned in the position higher than the low ceiling surface 17b. As a result, as shown in FIG. 5B, in the state where the liquid level is higher than the high ceiling surface 17a, even if the bubbles B are generated in the measurement chamber 14, the generated bubbles B And is easily trapped in a space formed between the liquid surface of the measurement sample L1. 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, it is possible to prevent a decrease in measurement accuracy due to the presence of the bubbles B when measuring the optical characteristics of the measurement sample L1 by transmitting light through the low ceiling surface 17b. Therefore, it is possible to provide the measuring apparatus 1A that can perform measurement with high accuracy.

  Moreover, since the measurement container 10 is composed of six analysis cells 11, the concentration of a plurality of components can be measured simultaneously with one measurement container 10. Thereby, measurement time can be shortened.

(Measures against undissolved reagent 40 and insufficient stirring of measurement sample L1)
Next, stirring of the measurement sample L1 will be described with reference to FIG. As described above, in the measurement apparatus 1A, the measurement sample L1 is obtained by mixing and stirring the measurement liquid and the reagent 40 (see FIG. 3) in the measurement chamber 14.

  However, some types of reagent 40 are difficult to dissolve in the measurement solution. For example, when the measurement solution is a soil extract and the reagent 40 is a reagent for calculating the potassium concentration in the soil extract, the reagent 40 is difficult to dissolve in the soil extract. In addition, when the viscosity of the reagent 40 is high or when the combination of the measurement solution and the reagent 40 is not suitable, the reagent 40 is difficult to dissolve in the measurement solution. In such a case, the undissolved reagent 40 adheres to the inner wall of the measurement chamber 14. When the optical properties of the measurement sample L1 are measured, if the undissolved reagent 40 adheres to the inner wall of the measurement chamber 14, the undissolved reagent 40 does not react with the measurement liquid. For this reason, the measurement accuracy is reduced. Further, the measurement accuracy is also lowered when the measurement liquid is not sufficiently stirred and the measurement component is not uniformly dispersed in the measurement sample L1.

  Here, if the measurement container 10 is rotated around the rotation shaft 19, the measurement sample L <b> 1 moves inside the measurement chamber 14. In particular, in the vicinity of the liquid surface of the measurement sample L1, since the measurement sample L1 moves so as to wave, the movement amount of the measurement sample L1 increases. For this reason, mixing / stirring inside the measurement chamber 14 is promoted, and the undissolved reagent 40 can be dissolved to some extent or the measurement components can be uniformly dispersed.

  However, on the top surface of the measurement chamber 14, a high top surface 17a whose height from the bottom surface 18 is higher than the low top surface 17b is formed around the low top surface 17b whose height from the bottom surface 18 is relatively low. Has been. Further, as shown in FIG. 5B, the liquid surface of the measurement sample L1 is at a position higher than the low ceiling surface 17b. In such a state, even if the measurement sample L1 is agitated by rotating the measurement container 10, the movement of moving the measurement sample L1 to the left and right in the figure so as to wave is caused by the high ceiling surface 17a and the low ceiling surface 17b. It is hindered by the steps that are in between. As a result, since the stirring efficiency is lowered, it becomes difficult to dissolve the reagent 40 remaining undissolved by the stirring operation and to uniformly disperse the measurement components.

Therefore, in the measurement apparatus 1A of the present embodiment, the control unit 30A controls the drive mechanism 23, the liquid injection device 24A, and the optical measurement mechanism 25 to execute the following four steps.
(1) A first liquid injection step (first liquid injection mode) for injecting the measurement liquid into the measurement chamber 14 so that the liquid level is lower than the low ceiling surface 17b.
(2) A stirring step (stirring mode) in which the measurement container 10 is stirred.
(3) Second liquid injection step (second liquid injection) for injecting the measurement liquid into the measurement chamber 14 into which the measurement liquid has been injected in the first liquid injection step so that the liquid level is higher than the low ceiling surface 17b. mode).
(4) A first measurement step (first measurement mode) in which the measurement chamber 14 and the light transmitted through the measurement sample L1 accommodated in the measurement chamber 14 are measured.

  As described above, in the measurement apparatus 1A, the liquid level of the measurement liquid injected in the first liquid injection process is lower than the low ceiling surface 17b. As a result, when the stirring step is performed following the first liquid injection step, the measurement chamber moves so that the movement of the measurement liquid undulates without being hindered by the step existing between the high ceiling surface 17a and the low ceiling surface 17b. The inside of 14 can be moved freely. As a result, the moving amount of the measurement liquid inside the measurement chamber 14 is increased, so that the stirring efficiency is improved. Therefore, the undissolved residue of the reagent 40 can be suppressed by the stirring step, the reagent 40 can be dissolved in the measurement liquid, and the measurement components in the measurement liquid can be uniformly dispersed. Therefore, the measurement accuracy of the measurement apparatus 1A can be improved.

  Hereinafter, details of the processing of the control system of the measuring apparatus 1A will be described.

(Processing of control system of measuring apparatus 1A)
FIG. 1 is a schematic diagram showing a control system of the measuring apparatus 1A. As shown in FIG. 1, the measuring apparatus 1A includes a control unit 30A. The control unit 30A controls operations of the drive mechanism 23, the liquid injection device 24A, and the optical measurement mechanism 25, and executes the above-described steps.

  Specifically, in the first liquid injection step and the second liquid injection step, the liquid injection device 24A performs measurement of each analysis cell 11 of the measurement container 10 via the liquid injection port 13 according to an instruction from the control unit 30A. The measurement liquid is injected into the chamber 14.

  In the stirring process, the drive mechanism 23 rotates the table 22 in accordance with an instruction from the control unit 30A. Thereby, the measurement container 10 rotates around the rotation shaft 19. The drive mechanism 23 rotates the measurement container 10 while accelerating and decelerating around the rotation shaft 19.

  In addition, the aspect of the stirring in the stirring process is, for example, (a) an aspect in which the measurement container 10 rotates and stirs in one direction around the rotation shaft 19 and (b) rotates with acceleration and deceleration. Examples include an aspect of stirring, (c) an aspect of alternately rotating and stirring in one direction and the opposite direction, and (d) an aspect of reciprocating left and right without rotating the measurement container 10.

  In the first measurement process, the light emitting unit 25a of the optical measurement mechanism 25 irradiates the measurement chamber 14 of the measurement container 10 with light according to an instruction from the control unit 30A. The light receiving unit 25b is irradiated from the light emitting unit 25a to the top surface side measurement window 16a, passes through the measurement chamber 14, receives light emitted from the bottom surface side measurement window 16b of the measurement chamber 14, and transmits the received light. Measure the amount. The light receiving unit 25b outputs the measured light transmission amount to the control unit 30A as spectrum data. The control unit 30A calculates the absorbance of the measurement sample L1 in the measurement chamber 14 based on the spectrum data output from the light receiving unit 25b, and obtains the measurement result of the component of the measurement sample L1 in the measurement chamber 14.

  As shown in FIG. 1, in the measuring apparatus 1A of the present embodiment, the control unit 30A includes a first liquid injection amount control unit 31 and a second liquid injection amount control unit 32. The first liquid injection amount control unit 31 controls the amount of measurement liquid (first liquid injection amount) injected into the measurement chamber 14 in the first liquid injection step. The second liquid injection amount control unit 32 controls the amount of measurement liquid (second liquid injection amount) injected into the measurement chamber 14 in the second liquid injection step.

  More specifically, the first liquid injection amount control unit 31 includes a first liquid injection amount storage unit 31a, and the second liquid injection amount control unit 32 includes a second liquid injection amount storage unit 32a. . The first liquid injection amount storage unit 31a stores the amount of liquid injected into the measurement chamber 14 in the first liquid injection process. The second liquid injection amount storage unit 32a stores the amount of liquid injected into the measurement chamber 14 in the second liquid injection step.

  In the first liquid injection step, the first liquid injection amount control unit 31 supplies the liquid injection device 24A with the amount of measurement liquid stored in the first liquid injection amount storage unit 31a into the measurement chamber 14. Give instructions. In the second liquid injection step, the second liquid injection amount control unit 32 causes the liquid injection device 24A to inject the amount of measurement liquid stored in the second liquid injection amount storage unit 32a into the measurement chamber 14. Give instructions.

(Measuring method of measuring apparatus 1A)
Next, a measurement method using the measurement apparatus 1A will be described with reference to FIGS. FIG. 6 is a flowchart showing a measurement procedure using the measurement apparatus 1A. FIG. 7 shows a state in which the measurement liquid is injected into the measurement chamber 14 of the measurement container 10 in the measurement using the measurement apparatus 1A, and (a) is a cross section of the measurement chamber 14 before the first liquid injection step. (B) is a cross-sectional view of the measurement chamber 14 after the first liquid injection step, (c) is a cross-sectional view of the measurement chamber 14 after the first stirring step described later, and (d) is the first view. It is sectional drawing of the measurement chamber 14 after 2 liquid injection | pouring processes.

  As shown in FIG. 6, first, in response to an instruction from the first liquid injection amount control unit 31 of the control unit 30A, the liquid injection device 24A prepares the amount of measurement liquid stored in the first liquid injection amount storage unit 31a. It inject | pours into the measurement chamber 14 of the measurement container 10 (S1, 1st liquid injection | pouring process).

  Here, the amount of the measurement liquid injected in the first liquid injection step will be described with reference to FIG.

  As shown in FIG. 7A, the measurement chamber 14 is preliminarily sealed with a reagent 40 that reacts with a predetermined component among a plurality of measurement components contained in the measurement liquid.

  When the amount of measurement liquid stored in the first liquid injection amount storage unit 31a is injected into the measurement chamber 14 in the first liquid injection step, as shown in FIG. The surface is at a position lower than the low ceiling surface 17b. That is, the amount stored in the first liquid injection amount storage unit 31a is such that the liquid level of the measurement liquid is lower than the low ceiling surface 17b. Since the shape and volume of the measurement chamber 14 are known in advance, the first liquid injection amount storage unit 31a may store an amount such that the liquid level of the measurement liquid is lower than the low ceiling surface 17b. it can.

  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 to stir the measurement liquid and the reagent 40 inside the measurement chamber 14 (S2, first stirring step). (Stirring mode)).

  As shown in FIG. 7B, the liquid level of the measurement liquid injected in the first liquid injection process is lower than the low ceiling surface 17b. That is, a space in which no measurement liquid exists is formed between the liquid level of the measurement liquid and the low ceiling surface 17b. Thereby, at the time of a 1st stirring process, the motion of a measurement liquid moves freely inside the measurement chamber 14 so that it may wave, without being disturbed by the level | step difference which exists between the high ceiling surface 17a and the low ceiling surface 17b. be able to. As a result, the moving amount of the measurement liquid inside the measurement chamber 14 is increased, so that the stirring efficiency is improved. Therefore, the undissolved residue of the reagent 40 can be suppressed by the stirring step, the reagent 40 can be dissolved in the measurement liquid, and the measurement components in the measurement liquid can be uniformly dispersed.

  Next, according to an instruction from the second liquid injection amount control unit 32 of the control unit 30A, the liquid injection device 24A causes the amount stored in the second liquid injection amount storage unit 32a (the liquid level to be lower than the low ceiling surface 17b). A measurement liquid of a high amount) is injected into the measurement chamber 14 of the measurement container 10 (S3, second liquid injection step).

  The amount of the measurement liquid injected in the second liquid injection step is such that the liquid level of the measurement liquid is higher than the low ceiling surface 17b as shown in FIG. That is, the amount stored in the second liquid injection amount storage unit 32a is such that the liquid level of the measurement liquid is higher than the low ceiling surface 17b. Since the shape and volume of the measurement chamber 14 are known in advance, the second liquid injection amount storage unit 32a may store an amount such that the liquid level of the measurement liquid is higher than the low ceiling surface 17b. it can.

  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 to stir the measurement liquid and the reagent 40 inside the measurement chamber 14 (S4, second stirring step). (Stirring mode)). Thereby, the measurement sample L1 in which the reagent 40 is uniformly dissolved in the measurement liquid is obtained.

  Next, optical measurement is performed using the optical measurement mechanism 25, and the amount of light transmitted through the measurement sample L1 is measured (S5, first measurement step).

  In the first measurement step, the amount of light transmitted through the measurement chamber 14 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 measurement chamber 14, and the bottom surface side measurement window 16b in this order, and the transmitted light is received by the light receiving unit 25b. To enter. The light receiving unit 25b receives the incident light, and outputs transmission amount data of the received light to the control unit 30A.

  Finally, the control unit 30A calculates the concentration of the measurement component (S6). Specifically, the control unit 30A stores in advance data on the amount of light transmitted through a mixed solution of the measurement liquid (dilution liquid) and the reagent 40 that do not include the measurement component. The control unit 30A transmits data of the amount of light transmitted through the measurement sample L1 input from the light receiving unit 25b, and transmission of light transmitted through the liquid mixture of the diluent and the reagent 40 stored in advance in the control unit 30A. The absorbance of the measurement sample L1 is calculated from the quantity data. Then, the control unit 30A calculates the concentration of the measurement component contained in the measurement liquid from the calculated absorbance of the measurement sample L1.

  As described above, in the measurement apparatus 1A according to the present embodiment, the top surface 17 of the measurement chamber 14 is positioned at the periphery of the low ceiling surface 17b that transmits light and the low ceiling surface 17b, and the bottom surface of the measurement chamber 14 18 and a high ceiling surface 17a disposed at a position higher than the low ceiling surface 17b. Then, after the measurement liquid is injected by the second liquid injection step, the liquid level of the measurement liquid is higher than the low ceiling surface 17b.

  Thereby, even if the bubble B is generated in the measurement chamber 14, the generated bubble B is easily trapped in the space formed between the high ceiling surface 17a and the liquid surface of the measurement sample L1. As a result, the entrapment of the bubbles B into the space between the low ceiling surface 17b and the bottom surface 18 is reduced. Therefore, it is possible to prevent a decrease in measurement accuracy due to the presence of the bubbles B when measuring the optical characteristics of the measurement sample L1 by transmitting light through the low ceiling surface 17b.

  Further, in the measuring apparatus 1A, the liquid level of the measurement liquid injected in the first liquid injection process is positioned lower than the low ceiling surface 17b. Thereby, at the time of a 1st stirring process, a measurement liquid moves so that the inside of the measurement chamber 14 may wave. As a result, the moving amount of the measurement liquid inside the measurement chamber 14 is increased, so that the stirring efficiency is improved. Therefore, the undissolved residue of the reagent 40 can be suppressed by the stirring step, the reagent 40 can be dissolved in the measurement liquid, and the measurement components in the measurement liquid can be uniformly dispersed. Therefore, the measurement accuracy of the measurement apparatus 1A can be improved.

[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.

  The measurement apparatus 1B in the present embodiment is different from the measurement apparatus 1A in that the diluent is injected into the measurement container in the first liquid injection step. The dilution liquid is a solvent for diluting the measurement liquid, such as water (pure water).

  In the measurement using the measurement apparatus 1A of Embodiment 1, when calculating the concentration of the measurement component contained in the measurement liquid by absorbance measurement, the reagent 40 and the measurement liquid are mixed, and the measurement sample that is colored by mixing with the reagent 40 L1 was used.

  However, in the measurement sample L1 in which the reagent 40 and the measurement liquid are mixed, when the concentration of the measurement component is high, the degree of color development becomes high, which may exceed the range where the absorbance measurement can be performed. Therefore, in such a case, the concentration of the measurement component in the measurement sample L1 is reduced by mixing the measurement sample L1 obtained by mixing the reagent 40 and the measurement solution with the diluent. Thereby, the degree of color development of the diluted measurement sample L1 can be lowered, and the degree of color development can be set within a range where absorbance measurement can be performed.

  Therefore, in the measurement apparatus 1B of the present embodiment, the dilution liquid is injected in the first liquid injection process, and the measurement liquid is injected in the second liquid injection process, thereby reducing the concentration of the measurement component in the measurement sample, The degree is set within a range where absorbance measurement can be performed.

  Therefore, in the measurement apparatus 1B of the present embodiment, the configuration of the liquid injection apparatus 24B shown in FIG. 8 is different from the configuration of the liquid injection apparatus 24A of the measurement apparatus 1A of the first embodiment. That is, the liquid injection device 24B includes a measurement liquid storage container (not shown) that stores a measurement liquid that is a measurement target, and a dilution liquid storage container (not shown) that stores a dilution liquid for diluting the measurement liquid. ing. The diluent is injected into the diluent container before starting the measurement. The liquid injection device 24B injects the measurement liquid or the dilution liquid from the measurement liquid storage container or the dilution liquid storage container into the measurement container according to an instruction from the control unit 30B. Specifically, the liquid injection device 24B injects the measurement liquid or the dilution liquid from the liquid injection port 13 of each analysis cell 11 into the measurement chamber 14.

(Measuring method of measuring device 1B)
Next, a measurement method using the measurement apparatus 1B will be described with reference to FIGS. FIG. 8 is a schematic diagram showing a control system of the measuring apparatus 1B. FIG. 9 is a flowchart showing a measurement procedure using the measurement apparatus 1B. As shown in FIG. 8, the measuring apparatus 1B includes a control unit 30B.

  As shown in FIG. 9, first, according to an instruction from the first liquid injection amount control unit 31 of the control unit 30B, the liquid injection device 24B stores the amount (the liquid level is stored in the first liquid injection amount storage unit 31a). A dilution liquid) is injected into the measurement chamber 14 of the measurement container 10 (S11, first liquid injection step).

  Next, in response to an instruction from the control unit 30 </ b> B, the drive mechanism 23 rotates the measurement container 10 about the rotation shaft 19, and agitates the diluent and the reagent 40 inside the measurement chamber 14. Thereby, the reagent 40 is dissolved in the diluent (S12, first stirring step).

  Next, according to an instruction from the second liquid injection amount control unit 32 of the control unit 30B, the liquid injection device 24B causes the amount stored in the second liquid injection amount storage unit 32a (the liquid level to be lower than the low ceiling surface 17b). A measurement liquid or dilution liquid in a high position) is injected into the measurement chamber 14 of the measurement container 10 (S13, second liquid injection step).

  Here, the type of liquid injected into the measurement chamber 14 in the second liquid injection step will be described. In the measuring apparatus 1B, only the diluent is injected into at least one of the six measurement chambers 14 (see FIG. 3). Then, the measurement liquid and the remaining dilution liquid that has not been injected into the measurement chamber 14 in the first liquid injection process are injected into the other measurement chamber 14. Thus, a mixed solution R1 of the reagent 40 and the diluent is produced in the measurement chamber 14 into which only the diluent is injected in the second liquid injection step. In the second liquid injection step, the measurement sample L2 in which the measurement liquid, the diluent, and the reagent 40 are mixed is prepared in the measurement chamber 14 into which the measurement liquid has been injected. Since the measurement sample L2 is diluted with a diluent, the concentration of the measurement component in the measurement sample L2 is also diluted, so the degree of color development is small. As a result, even when the concentration of the measurement component in the measurement solution is high, the degree of color development is within a range where the absorbance measurement can be performed.

  Next, in response to an instruction from the control unit 30B, the drive mechanism 23 rotates the measurement container 10 about the rotation shaft 19. Thereby, in the measurement chamber 14 into which the measurement liquid is injected in the second liquid injection step, the measurement liquid, the diluent, and the reagent 40 are stirred, and the measurement sample L2 in which the reagent 40 is uniformly dissolved is produced. Moreover, in the measurement chamber 14 into which the diluent has been injected in the second liquid injection step, the diluent and the reagent 40 are agitated to produce a mixed solution R1 in which the reagent 40 is uniformly dissolved (S14, second agitation step). ).

  Next, optical measurement is performed using the optical measurement mechanism 25, and the amount of light transmitted through the measurement sample L2 and the mixed solution R1 is measured (S15, first measurement step).

  Finally, the concentration of the measurement component of the measurement liquid is calculated (S16).

  Here, in the measurement apparatus 1A of the first embodiment, the control unit 30A stores in advance data on the amount of light transmitted through the mixed liquid of the measurement liquid (dilution liquid) and the reagent 40 not including the measurement component. It was. Then, the control unit 30A transmits the light transmission amount data transmitted through the measurement sample L1 input from the light receiving unit 25b, and the light transmitted through the liquid mixture of the diluent and the reagent 40 stored in the control unit 30A in advance. The component concentration of the measurement liquid was calculated based on the permeation amount data.

  However, the state of the reagent 40 may change while it is sealed in the measurement container 10, and the amount of light transmitted through the mixed solution of the diluent and the reagent 40 stored in advance in the control unit 30 </ b> A There is a possibility that the data and the data of the amount of transmitted light that has actually passed through the mixture of the diluent and the reagent 40 may be different. As a result, the calculation accuracy of the concentration of the measurement component of the measurement liquid may be reduced.

  Therefore, in the measurement apparatus 1B of the present embodiment, the amount of light that has actually passed through the mixed solution of the diluent and the reagent 40 is measured. Specifically, as described above, in the second liquid injection step, the mixed solution R1 of the reagent 40 and the diluent is prepared in at least one measurement chamber 14. The mixed solution R1 does not contain the measurement component of the measurement liquid. The control unit 30B acquires data on the amount of light transmitted through the mixed solution R1 by the optical measurement mechanism 25. Next, the control unit 30B acquires data on the amount of light transmitted through the measurement sample L2 by the optical measurement mechanism 25. Then, the control unit 30B calculates the absorbance of the measurement sample L2 based on the transmission amount data of the light transmitted through the mixed solution R1 and the transmission amount data of the light transmitted through the measurement sample L2. Next, the control unit 30B calculates the concentration of the measurement component of the measurement sample L2 from the calculated absorbance of the measurement sample L2. Then, the control unit 30B calculates the measurement component of the measurement liquid from the calculated concentration of the measurement component of the measurement sample L2 and the ratio (dilution ratio) of the amount of the measurement liquid and the dilution liquid used for preparing the measurement sample. Calculate the concentration.

  Thus, in the measurement apparatus 1B, the diluent is injected into the measurement chamber 14 in the first liquid injection step, the measurement liquid is injected into at least one measurement chamber 14 in the second liquid injection step, and the remaining measurement chambers 14 are injected. Inject the diluent. Thereby, in the measurement chamber 14 into which the measurement liquid is injected in the second liquid injection step, the measurement sample L2 in which the measurement liquid, the diluent, and the reagent 40 are mixed is produced. As a result, since the concentration of the measurement component in the measurement sample L2 is diluted, the degree of color development can be reduced. Thereby, the color development degree of the measurement sample L2 can be set within a range where the absorbance measurement can be performed.

  In the measuring apparatus 1B, a mixed solution R1 of the reagent 40 and the diluent is prepared in at least one measurement chamber. Then, the amount of light transmitted through the measurement sample L2 and the mixed solution R1 is measured, and the absorbance of the measurement sample L2 is calculated based on the obtained amount of transmission. Thereby, the measurement component based on the measurement data of the transmission amount of the light transmitted through the measurement sample L2 and the data of the transmission amount of the light transmitted through the mixed solution of the diluent and the reagent 40 stored in advance in the control unit. The measurement accuracy can be improved as compared with the case of calculating the concentration of.

[Embodiment 3]
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.

  In the first liquid injection step, the measurement apparatus 1C in the present embodiment measures the amount of transmitted light after injecting the diluent into the measurement container, and based on the result of the transmission amount measurement, the second liquid injection step However, the point which controls the quantity of the dilution liquid and measurement liquid which are inject | poured into a measurement container differs from the measurement apparatus of other embodiment.

(Measuring method of measuring device 1C)
Next, a measurement method using the measurement apparatus 1C will be described with reference to FIGS. FIG. 10 is a schematic diagram showing a control system of the measuring apparatus 1C. FIG. 11 is a flowchart illustrating a measurement procedure using the measurement apparatus 1C. As shown in FIG. 10, the measuring apparatus 1C includes a control unit 30C.

  As shown in FIG. 11, first, in accordance with an instruction from the first liquid injection amount control unit 31 of the control unit 30C, the liquid injection device 24B stores the amount (the liquid level is stored in the first liquid injection amount storage unit 31a). A dilution liquid) is introduced into the measurement chamber 14 of the measurement container 10 (S21, first liquid injection step).

  Next, in response to an instruction from the control unit 30 </ b> C, the drive mechanism 23 rotates the measurement container 10 around the rotation shaft 19 and stirs the diluted solution and the reagent 40 inside the measurement chamber 14. Thereby, the reagent 40 is dissolved in the diluent (S22, first stirring step). Thereby, the mixed solution R2 of the reagent 40 and the diluent is produced in the measurement chamber 14.

  Next, optical measurement is performed using the optical measurement mechanism 25, and the amount of light transmitted through the mixed solution R2 is measured (S23, second measurement step (second measurement mode)).

  The optical measurement mechanism 25 stores measurement data of the amount of light transmitted through the mixed solution R2 obtained in the second measurement step in the control unit 30C. The measurement data of the amount of light transmitted through the mixed solution R2 obtained in the second measurement step is used when calculating the concentration of the measurement component of the measurement liquid described later. Details will be described later.

  Next, according to an instruction from the second liquid injection amount control unit 32 of the control unit 30C, the liquid injection device 24B causes the amount stored in the second liquid injection amount storage unit 32a (the liquid level to be lower than the low ceiling surface 17b). A measurement liquid and a dilution liquid in a high position) are injected into the measurement chamber 14 of the measurement container 10 (S24, second liquid injection step). In the second liquid injection process, the measurement liquid and the remaining diluted liquid that has not been injected into the measurement chamber 14 in the first liquid injection process are injected. Thereby, the measurement sample L2 in which the measurement liquid, the dilution liquid, and the reagent 40 are mixed is produced in the measurement chamber 14. Since the measurement sample L2 is diluted with a diluent, the concentration of the measurement component in the measurement sample L2 is diluted, so the degree of color development is small. As a result, even when the concentration of the measurement component in the measurement solution is high, the degree of color development is within a range where the absorbance measurement can be performed.

  Next, in response to an instruction from the control unit 30 </ b> C, the drive mechanism 23 rotates the measurement container 10 about the rotation shaft 19. Thereby, the measurement liquid, the dilution liquid, and the reagent 40 are stirred, and the measurement sample L2 in which the reagent 40 is uniformly dissolved is produced (S25, second stirring step).

  Next, optical measurement is performed using the optical measurement mechanism 25, and the amount of light transmitted through the measurement sample L2 is measured (S26, first measurement step).

  Finally, the concentration of the measurement component of the measurement liquid is calculated (S27).

  Here, in the measuring apparatus 1B of the second embodiment, the mixed solution R1 of the reagent 40 and the diluent is produced in at least one measurement chamber 14. The mixed solution R1 does not contain the measurement component of the measurement liquid. Then, the amount of light transmitted through the measurement sample L2 and the mixed solution R1 was measured, and the concentration of the measurement component of the measurement liquid was calculated based on the obtained amount of transmission. Therefore, at least one analysis cell 11 out of the six analysis cells 11 must be used for measuring the amount of light transmitted through the mixed solution R1 of the reagent 40 and the diluent.

  On the other hand, in the measurement apparatus 1C of the present embodiment, the second measurement process is performed after the first stirring process, and the amount of light transmitted through the mixed solution R2 is measured. Then, after the second measurement process, a second liquid injection process is performed to inject the measurement liquid and the diluted liquid into the measurement chamber 14 of the measurement container 10. Thereby, it is not necessary to use the analysis cell 11 in order to calculate the concentration of the measurement component of the measurement liquid. Hereinafter, a method for calculating the concentration of the measurement component of the measurement liquid will be described in detail.

  In the measuring apparatus 1C, based on the amount of light transmitted through the mixed solution R2 measured in the second measurement step and the amount of light transmitted through the measurement sample L2 measured in the first measurement step, the measurement components of the measurement liquid The concentration of is calculated.

  However, in the first liquid injection step, the diluent is injected into the measurement chamber 14 so that the liquid level of the mixed solution R2 is lower than the low ceiling surface 17b. For this reason, the distance that the light passes through the mixed solution R2 in the second measurement step is the distance that the light passes through the measurement sample L2 in the first measurement step, that is, the distance from the low ceiling surface 17b to the bottom surface 18 of the measurement chamber 14. Is also shorter. Therefore, when calculating the concentration of the measurement component of the measurement liquid, the amount of light transmitted through the mixed solution R2 measured in the second measurement step cannot be used as it is. However, since the injection amount of the diluent in the first liquid injection step and the shape / capacity of the measurement chamber 14 are known in advance, from the bottom surface of the measurement chamber 14 after the first liquid injection step to the liquid level of the mixed solution R2. The distance is known in advance. The distance from the low ceiling surface 17b to the bottom surface 18 of the measurement chamber 14 is known in advance. Therefore, using the distance from the bottom surface of the measurement chamber 14 to the liquid surface of the mixed solution R2 after the first liquid injection step and the distance from the low ceiling surface 17b to the bottom surface 18 of the measurement chamber 14, the measurement is performed in the second measurement step. The amount of light transmitted through the mixed solution R2 can be corrected.

  Then, the control unit 30C, based on the corrected amount of light transmitted through the mixed solution R2 measured in the second measurement step and the amount of transmitted light transmitted through the measurement sample L2 measured in the first measurement step, The absorbance of the measurement sample L2 is calculated. Next, the control unit 30C calculates the concentration of the measurement component of the measurement sample L2 from the calculated absorbance of the measurement sample L2. Then, the control unit 30C calculates the measurement component of the measurement liquid from the calculated concentration of the measurement component of the measurement sample L2 and the ratio (dilution ratio) of the amount of the measurement liquid and the dilution liquid used for preparing the measurement sample. Calculate the concentration.

  The method for measuring the concentration of the component of the measurement liquid using the measurement apparatus 1C described above is particularly effective when the color of the solution is not colorless when the reagent 40 is dissolved in a liquid (diluent) that does not contain the measurement component. Become. As an example, a case where the concentration of Mg in the measurement liquid is measured will be described. The reagent 40 used for measuring the concentration of Mg has the property of turning yellow when dissolved in a liquid not containing the Mg component and red when dissolved in a liquid containing the Mg component. . As described above, in the measurement method using the measurement apparatus 1C, in the second measurement step, the amount of light transmitted through the mixed solution R2 of the diluent (for example, pure water) not containing Mg and the reagent 40 is calculated. Actually measure. And based on this measurement result, since the light absorbency of the measurement sample L2 which mixed the measurement liquid, dilution liquid, and reagent 40 containing Mg is calculated, the measurement liquid, dilution liquid, and reagent 40 containing Mg correctly. The absorbance of the measurement sample L2 mixed with can be calculated. As a result, the concentration of the Mg component in the measurement liquid can be accurately measured.

  As described above, in the measurement apparatus 1C of the present embodiment, the second measurement step of measuring the amount of light transmitted through the mixed solution R2 is performed after the first stirring step. And the density | concentration of the measurement component of a measurement liquid is calculated using the measured light transmission amount. Thus, measurement is performed based on the measurement data of the amount of light transmitted through the measurement sample L2 and the data of the amount of light transmitted through the mixed solution of the diluent and the reagent 40 stored in advance in the control unit 30C. Compared with the case of calculating the concentration of the component, the measurement accuracy can be improved.

  In the measuring apparatus 1B of the second embodiment, the analysis cell 11 is used to produce the mixed solution R1 of the reagent 40 and the diluent. However, in the measurement apparatus 1C of the present embodiment, the concentration of the measurement component of the measurement liquid is calculated using the amount of light transmitted through the mixed solution R2 after the first stirring step. Thereby, it is not necessary to use the dedicated analysis cell 11 in order to produce the mixed solution R1 of the reagent 40 and the diluting solution, and more types of measuring solutions can be analyzed.

[Embodiment 4]
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.

  The reagent 40 may be a highly viscous liquid. In such a case, in the first stirring step, all the reagents 40 cannot be dissolved in the diluent, and undissolved parts may be generated. Further, depending on the compatibility between the reagent 40 and the diluent, the reagent 40 may be difficult to dissolve in the diluent. Even in such a case, in the first stirring step, not all the reagents 40 can be dissolved in the diluent, and undissolved parts may be generated.

  When the reagent 40 remains undissolved, when measuring the amount of transmitted light in the first measurement step, a part of the light is reflected by the reagent 40 remaining undissolved, which may reduce the measurement accuracy.

  Therefore, the measurement device 1D in the present embodiment is different from the measurement devices in the other embodiments in that it is determined whether all the reagents 40 are dissolved in the diluent after the first stirring step.

  A control system of the measuring apparatus 1D will be described with reference to FIG. FIG. 12 is a schematic diagram illustrating a control system of the measurement apparatus 1D.

  As shown in FIG. 12, the measuring apparatus 1D includes a control unit 30D. The control unit 30D includes a third liquid injection amount control unit 33 and a fourth liquid injection amount control unit 34. The third liquid injection amount control unit 33 stores the amount of liquid to be injected in a third liquid injection step described later. The fourth liquid injection amount control unit 34 stores the amount of liquid to be injected in a fourth liquid injection process described later.

(Measuring method of measuring device 1D)
Next, a measurement method using the measurement apparatus 1D will be described with reference to FIG. FIG. 13 is a flowchart illustrating a measurement procedure using the measurement apparatus 1D.

  As shown in FIG. 13, first, in response to an instruction from the first liquid injection amount control unit 31 of the control unit 30D, the liquid injection device 24B stores the amount (the liquid level is stored) in the first liquid injection amount storage unit 31a. A dilution liquid of an amount lower than the low top surface 17b) is injected into the measurement chamber 14 of the measurement container 10 (S31, first liquid injection step).

  Next, in response to an instruction from the control unit 30 </ b> C, the drive mechanism 23 rotates the measurement container 10 around the rotation shaft 19 and stirs the diluted solution and the reagent 40 inside the measurement chamber 14. Thereby, the reagent 40 is dissolved in the diluent (S32, first stirring step). Thereby, the mixed solution R2 of the reagent 40 and the diluent is produced in the measurement chamber 14.

  Next, optical measurement is performed using the optical measurement mechanism 25, and the amount of light transmitted through the mixed solution R2 is measured (S33, second measurement step).

  Next, the control unit 30D determines whether all the reagents 40 are dissolved in the diluent (S34). Whether or not all the reagents 40 are dissolved in the diluent is determined as follows. That is, the control unit 30D is sealed in the measurement container 10 in the amount of dilution liquid stored in the first liquid injection amount storage unit 31a (the amount at which the liquid level is lower than the low ceiling surface 17b). The amount of transmitted light when the same amount of reagent 40 as the amount is dissolved is stored in advance. The control unit 30D compares all the light transmission amounts stored in advance with the light transmission amount transmitted through the mixed solution R2 measured in the second measurement step, whereby all the reagents 40 are dissolved in the diluent. Determine whether or not.

  When the control unit 30D determines that all the reagents 40 are dissolved in the diluent (Yes in step S34), the liquid injection device 24B is controlled by the instruction from the second liquid injection amount control unit 32 of the control unit 30B. The amount of measurement liquid stored in the two liquid injection amount storage unit 32a (the amount at which the liquid level is higher than the low ceiling surface 17b) is injected into the measurement chamber 14 of the measurement container 10 (S35, second liquid injection) Process). Thereby, the measurement sample L2 in which the measurement liquid, the dilution liquid, and the reagent 40 are mixed is produced in the measurement chamber 14.

  Next, in response to an instruction from the control unit 30D, the drive mechanism 23 rotates the measurement container 10 about the rotation shaft 19. Thereby, the measurement liquid, the dilution liquid, and the reagent 40 are stirred, and the measurement sample L2 in which the reagent 40 is uniformly dissolved is produced (S36, second stirring step).

  Next, optical measurement is performed using the optical measurement mechanism 25, and the amount of light transmitted through the measurement sample L2 is measured (S37, first measurement step).

  Finally, the concentration of the measurement component of the measurement liquid is calculated using the amount of light transmitted through the measurement sample L2 measured in the first measurement step (S38).

  On the other hand, when the control unit 30D determines that all the reagents 40 are not dissolved in the diluent (No in step S34), the liquid injection device is instructed by an instruction from the third liquid injection amount control unit 33 of the control unit 30D. 24B injects the amount of measurement liquid stored in the third liquid injection amount storage unit 33a into the measurement chamber 14 of the measurement container 10 (S39, third liquid injection step). The amount of the measurement liquid to be injected in the third liquid injection step, that is, the amount stored in the third liquid injection amount storage unit 33a is the liquid level of the liquid stored in the measurement chamber 14 after the injection. This is an amount that is slightly lower than the low top surface 17b. Specifically, the amount stored in the third liquid injection amount storage unit 33a is such that, for example, the distance between the bottom surface 18 and the liquid surface of the liquid stored in the measurement chamber 14 after injection is the bottom surface 18 and the low ceiling surface. The amount is 90% of the distance to 17b.

  Next, in response to an instruction from the control unit 30D, the drive mechanism 23 rotates the measurement container 10 about the rotation shaft 19. Thereby, a measurement liquid, a dilution liquid, and the reagent 40 are stirred (S40, 3rd stirring process).

  As described above, after the measurement liquid is injected in the third liquid injection step, the liquid level of the liquid stored in the measurement chamber 14 is slightly lower than the low ceiling surface 17b of the measurement chamber 14. . That is, a space in which no measurement liquid exists is formed between the liquid level of the measurement liquid and the low ceiling surface 17b. Thereby, at the time of a 3rd stirring process, the motion of a measurement liquid moves freely inside the measurement chamber 14 so that it may wave, without being disturbed by the level | step difference which exists between the high ceiling surface 17a and the low ceiling surface 17b. be able to. As a result, the moving amount of the measurement liquid inside the measurement chamber 14 is increased, so that the stirring efficiency is improved. Therefore, the remaining undissolved reagent 40 can be suppressed by the third stirring step, the reagent 40 can be dissolved in the measurement liquid and the diluted liquid, and the measurement components in the measurement liquid can be uniformly dispersed.

  Next, according to an instruction from the fourth liquid injection amount control unit 34 of the control unit 30D, the liquid injection device 24B causes the measurement liquid of the amount stored in the fourth liquid injection amount storage unit 34a to be measured in the measurement chamber of the measurement container 10. 14 (S41, fourth liquid injection step). The amount of the measurement liquid to be injected in the fourth liquid injection step, that is, the amount stored in the fourth liquid injection amount storage unit 34a is an amount at which the liquid level of the measurement liquid is higher than the low ceiling surface 17b.

  Next, according to an instruction from the control unit 30D, the drive mechanism 23 rotates the measurement container 10 around the rotation shaft 19 (S42, fourth stirring step). Thereby, in the measurement chamber 14, the measurement liquid, the dilution liquid, and the reagent 40 are stirred, and the measurement sample L2 in which the reagent 40 is uniformly dissolved is produced.

  Next, optical measurement is performed using the optical measurement mechanism 25, and the amount of light transmitted through the measurement sample L2 is measured (S43, first measurement step).

  Finally, the concentration of the measurement component of the measurement liquid is calculated using the amount of light transmitted through the measurement sample L2 measured in the first measurement step (S44).

  As described above, in the measurement apparatus 1D of the present embodiment, the amount of light transmitted through the mixed solution R2 is measured by performing the second measurement step after the first stirring step. And control part 30D determines whether all the reagents 40 were melt | dissolved in the dilution liquid in the 1st stirring process based on the permeation | transmission amount of the light which permeate | transmitted the measured mixed solution R2. And if it determines with all the reagents 40 not having melt | dissolved in the dilution liquid in the 1st stirring process, the control part 30D will have the liquid level of the liquid accommodated in the measurement chamber 14 from the low ceiling surface 17b of the measurement chamber 14. The measurement liquid is injected into the measurement chamber 14 so that the position is slightly lower. Thereafter, by stirring the liquid accommodated in the measurement chamber 14 and the reagent 40 in the third stirring step, the reagent 40 can be reliably dissolved in the diluent and the measurement liquid.

  Thereby, it can prevent that the melt | dissolution residue of the reagent 40 generate | occur | produces. Therefore, it is possible to prevent the measurement accuracy from being lowered in the first measurement process.

[Embodiment 5]
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.

  In the first liquid injection step, the measurement apparatus 1E in the present embodiment measures the amount of transmitted light after injecting the measurement liquid into the measurement container, and based on the result of the transmission amount measurement, the second liquid injection step However, the point which controls the quantity of the dilution liquid inject | poured into a measurement container and the measurement liquid differs from the measurement apparatus of other embodiment.

  A control system of the measuring apparatus 1E will be described with reference to FIG. FIG. 14 is a schematic diagram showing a control system of the measuring apparatus 1E.

  As shown in FIG. 14, the measuring apparatus 1E includes a control unit 30E. The control unit 30E includes a second liquid injection amount control unit 32. The second liquid injection amount control unit 32 includes a second liquid injection amount calculation unit 32b. The second liquid injection amount control unit 32 injects the diluted liquid of the amount calculated by the second liquid injection amount calculation unit 32b into the measurement chamber 14 in the second liquid injection step. Details will be described later.

(Measurement method of measuring device 1E)
Next, a measurement method using the measurement apparatus 1E will be described with reference to FIG. FIG. 15 is a flowchart illustrating a measurement procedure using the measurement apparatus 1E.

  As shown in FIG. 15, first, according to an instruction from the first liquid injection amount control unit 31 of the control unit 30E, the liquid injection device 24B stores the amount (the liquid level is stored in the first liquid injection amount storage unit 31a). A measurement liquid in an amount lower than the low ceiling surface 17b) is injected into the measurement chamber 14 of the measurement container 10 (S51, first liquid injection step).

  Next, in response to an instruction from the control unit 30E, the drive mechanism 23 rotates the measurement container 10 around the rotation shaft 19 and agitates the diluent and the reagent 40 inside the measurement chamber 14. Thereby, the reagent 40 is dissolved in the measurement liquid (S52, first stirring step). As a result, a mixed solution R3 of the measurement liquid and the reagent 40 is produced in the measurement chamber 14.

  Next, optical measurement is performed using the optical measurement mechanism 25, and the amount of light transmitted through the mixed solution R3 is measured (S53, second measurement step).

  The optical measurement mechanism 25 stores in the control unit 30E measurement data of the amount of light transmitted through the mixed solution R3 obtained in the second measurement step. The measurement data of the amount of light transmitted through the mixed solution R3 obtained in the second measurement step is used in the second liquid injection step.

  Next, in response to an instruction from the second liquid injection amount control unit 32 of the control unit 30E, the liquid injection device 24B supplies the amount of diluent calculated by the second liquid injection amount calculation unit 32b to the measurement chamber 14 of the measurement container 10. Injecting (S54, second liquid injection step).

  Here, a method in which the second liquid injection amount calculation unit 32b calculates the amount of the diluent to be injected into the measurement chamber 14 in the second liquid injection step will be described. When the amount of light transmitted through the sample is measured using the optical measurement mechanism 25 and the concentration of the measurement component of the sample is calculated from the measured amount of transmission, the optical measurement mechanism 25 can obtain an accurate measurement result. The component concentration range is limited to a certain range. Therefore, in order to accurately measure the amount of permeation in the first measurement step, the concentration of the measurement component contained in the sample to be measured should be within the component concentration range in which an accurate measurement result can be obtained. preferable.

  Therefore, in the measuring apparatus 1E, the second liquid injection amount calculating unit 32b first roughly calculates the concentration of the measurement component of the mixed solution R3 from the amount of light transmitted through the mixed solution R3 measured in the second measuring step. . The optical measurement mechanism 25 can roughly calculate the concentration of the measurement component of the mixed solution R3 even if the concentration of the measurement component of the mixed solution R3 is not within the component concentration range in which an accurate measurement result can be obtained. .

  Next, the second liquid injection amount calculation unit 32b calculates the amount of the diluent to be injected in the second liquid injection step based on the calculated concentration of the measurement component of the mixed solution R3. Then, the liquid injection device 24B injects the amount of diluent calculated by the second liquid injection amount calculation unit 32b into the measurement chamber 14 of the measurement container 10. As a result, the measurement chamber 14 is injected with the measurement liquid and the dilution liquid in such an amount that the concentration of the measurement component is within the component concentration range in which an accurate measurement result can be obtained.

  A method by which the above-described second liquid injection amount calculation unit 32b calculates the amount of diluent to be injected into the measurement chamber 14 in the second liquid injection step will be described using a specific example. In a certain reagent 40, the component concentration range in which an accurate measurement result can be obtained is 1 to 5 ppm. At concentrations outside this range, a rough concentration can be calculated, but an accurate concentration cannot be calculated. Here, it is assumed that the concentration of the measurement component contained in the mixed solution R3 measured in the second measurement step is about 8 ppm. From this result, the second liquid injection amount calculation unit 32b calculates the amount of diluent necessary for diluting the mixed solution R3, for example, twice. Then, the liquid injection device 24B injects the amount of the diluent calculated by the second liquid injection amount calculation unit 32b into the measurement chamber 14 of the measurement container 10 according to an instruction from the second liquid injection amount control unit 32. Thereby, the density | concentration of a measurement component can be settled in the component density | concentration range which can obtain an exact measurement result.

  Next, in response to an instruction from the control unit 30E, the drive mechanism 23 rotates the measurement container 10 about the rotation shaft 19. Thereby, the measurement liquid, the dilution liquid, and the reagent 40 are stirred, and the measurement sample L2 which melt | dissolved uniformly is produced. (S55, 2nd stirring process).

  Next, optical measurement is performed using the optical measurement mechanism 25, and the amount of light transmitted through the measurement sample L2 is measured (S56, first measurement step).

  Finally, the concentration of the measurement component of the measurement liquid is calculated (S57). As described above, the concentration of the measurement component of the measurement sample L2 after the second stirring step is within the component concentration range in which an accurate measurement result can be obtained. For this reason, the density | concentration of the measurement component contained in a measurement liquid can be calculated correctly.

  As described above, in the measurement apparatus 1E of the present embodiment, in the first liquid injection step, the measurement liquid is injected into the measurement container to produce the mixed solution R3 of the measurement liquid and the reagent 40, and then the mixed solution in the second measurement step. The amount of light transmitted through R3 is measured. And based on the result of this permeation | transmission amount measurement, in the 2nd liquid injection | pouring process, the quantity of the dilution liquid and measurement liquid inject | poured into a measurement container are controlled. Thereby, the density | concentration of a measurement component can be settled in the component density | concentration range which can obtain an exact measurement result. Therefore, the concentration of the measurement component contained in the measurement liquid can be accurately calculated.

[Summary]
The measurement apparatuses 1A to 1E according to the first aspect of the present invention transmit the measurement container 10 including one or a plurality of measurement chambers 14 for storing the liquid, the measurement chamber 14 and the liquid stored in the measurement chamber 14. A measurement unit (optical measurement mechanism 25) for measuring the measured light, an agitation unit (drive mechanism 23) for agitating the measurement container 10, and a liquid injection unit (liquid injection device 24A) for injecting the liquid into the measurement chamber 14 24B), and a measurement device including the measurement unit (optical measurement mechanism 25), the stirring unit (drive mechanism 23), and the control units 30A to 30B that control the liquid injection unit (liquid injection devices 24A and 24B). The measurement chamber 14 includes a bottom surface 18 and a top surface 17 whose inner walls face each other, and the top surface 17 is positioned around the low ceiling surface 17b through which light is transmitted and the low ceiling surface 17b. , Against the bottom surface 18 A high ceiling surface 17a disposed at a position higher than the low ceiling surface 17b. The control units 30A to 30E include the liquid injection unit (liquid injection devices 24A and 24B), and the liquid surface includes the low ceiling surface 17a. A first liquid injection mode for injecting liquid into the measurement chamber 14 so as to be lower than the surface 17b; an agitation mode in which the agitation unit (drive mechanism 23) agitates the measurement container 10; and the first A second liquid injection mode for injecting liquid into the measurement chamber 14 into which the liquid has been injected in the liquid injection mode so that the liquid level is higher than the low ceiling surface 17b; and the measurement unit (optical measurement mechanism 25). Is configured to execute the measurement chamber 14 and a first measurement mode for measuring light transmitted through the liquid stored in the measurement chamber 14.

  According to this feature, the top surface of the measurement chamber is located at a low ceiling surface that transmits light, and at the periphery of the low ceiling surface, and is positioned higher than the low ceiling surface with respect to the bottom surface of the measurement chamber. And has a high sky surface. Thereby, even if bubbles are generated in the measurement container, the generated bubbles are easily trapped in the space formed between the high ceiling surface and the liquid surface of the liquid. As a result, the entrapment of bubbles in the space between the low ceiling surface and the bottom surface is reduced. Therefore, in the first measurement mode, it is possible to prevent a decrease in measurement accuracy due to the presence of bubbles when light is transmitted through the low-top surface and the optical characteristics of the liquid are measured. Therefore, there is an effect of providing a measurement container that can perform measurement with high accuracy.

  According to this feature, in the first liquid injection mode, the liquid is injected into the measurement chamber so that the liquid level is lower than the low ceiling surface. In other words, a space where no liquid exists is formed between the liquid level and the low ceiling. Thereby, in the stirring mode, the movement of the liquid can be freely moved in the measurement chamber so as to undulate without being hindered by a step existing between the high ceiling surface and the low ceiling surface. As a result, the amount of liquid movement in the measurement chamber is increased, so that the stirring efficiency is improved. Therefore, the measurement component or other components (liquid, solid) can be dissolved in the liquid by the stirring mode, and the measurement component or other components can be uniformly dispersed. Therefore, there is an effect of providing a measuring device that can improve the measurement accuracy.

  In the measurement apparatus 1B to 1E according to the second aspect of the present invention, in the first aspect, the liquid stored in the measurement chamber 14 includes a measurement liquid containing a measurement component and a dilution liquid for diluting the measurement liquid. The liquid injected into the measurement chamber 14 in the first liquid injection mode is one of the measurement liquid or the dilution liquid, and the liquid injected into the measurement chamber 14 in the second liquid injection mode is The other of the measurement liquid and the dilution liquid may be used.

  According to the above configuration, one of the measurement liquid and the dilution liquid is injected into the measurement chamber in the first liquid injection mode, and the other of the measurement liquid and the dilution liquid is injected into the measurement chamber in the second liquid injection mode. . Thereby, a mixed solution of the measurement liquid and the dilution liquid can be produced in the measurement chamber after the second liquid injection mode.

  In the measurement apparatus 1A to 1E according to the third aspect of the present invention, in the first or second aspect, the control units 30A to 30E are the amounts of liquid injected into the measurement chamber 14 in the first liquid injection mode. A first liquid injection amount control unit 31 for controlling one liquid injection amount; and a second liquid injection amount control for controlling a second liquid injection amount that is an amount of liquid injected into the measurement chamber 14 in the second liquid injection mode. It is preferable that the configuration includes the portion 32.

  According to the above configuration, by providing the first liquid injection amount control unit and the second liquid injection amount control unit, the amount of liquid injected into the measurement chamber in the first liquid injection mode and the second liquid injection mode is controlled. be able to. Accordingly, the amount of liquid injected into the measurement chamber in the first liquid injection mode and the second liquid injection mode can be accurately and appropriately set.

  In the measurement device 1A to 1C according to aspect 4 of the present invention, in the above aspect 3, the first liquid injection amount control unit 31 stores a first liquid injection amount storage unit 31a that stores the first liquid injection amount in advance. The second liquid injection amount control unit 32 includes a second liquid injection amount storage unit 32a that stores the second liquid injection amount in advance, and the first liquid injection amount control unit 31 includes In the first liquid injection mode, the first liquid injection amount stored in the first liquid injection amount storage unit 31a is injected into the measurement chamber 14, and the second liquid injection amount control unit 32 In the second liquid injection mode, the second liquid injection amount liquid stored in the second liquid injection amount storage unit 32 a may be injected into the measurement chamber 14.

  According to the above configuration, the first liquid injection amount control unit 31 includes the first liquid injection amount storage unit 31a. Thereby, the amount of liquid injected into the measurement chamber in the first liquid injection mode can be accurately and appropriately set. The second liquid injection amount control unit 32 includes a second liquid injection amount storage unit 32a. Thereby, the amount of liquid injected into the measurement chamber in the second liquid injection mode can be accurately and appropriately set.

  In any of the above-described aspects 1 to 4, the measurement apparatus 1A to 1E according to the aspect 5 of the present invention includes a reagent 40 preliminarily sealed in the measurement chamber 14, and the measurement container 10 is agitated. The reagent 40 and the liquid injected into the measurement chamber 14 by the liquid injection unit (liquid injection devices 24A and 24B) may be stirred.

  According to said structure, a reagent and the liquid inject | poured into the measurement chamber by the liquid injection | pouring part are stirred by carrying out stirring operation of the measurement container. Thereby, a reagent can be dissolved in a liquid.

  In the measurement device 1C to 1E according to the sixth aspect of the present invention, in the fifth aspect, the control units 30C to 30E are configured such that the measurement unit (optical measurement mechanism 25) is injected with the liquid in the first liquid injection mode. The configuration may be such that the measurement chamber 14 and the second measurement mode for measuring the light transmitted through the liquid stored in the measurement chamber 14 are executed.

  According to said structure, in the 2nd measurement mode, the light which permeate | transmitted the liquid mixture of the liquid inject | poured by 1st liquid injection mode and a reagent is measured. Thereby, the characteristics of the liquid injected in the first liquid injection mode and stored in the measurement chamber can be acquired.

  In the measurement apparatus 1E according to Aspect 7 of the present invention, in the Aspect 6, the liquid stored in the measurement chamber 14 includes a measurement liquid containing a measurement component and a dilution liquid for diluting the measurement liquid. The liquid injected into the measurement chamber 14 in the first liquid injection mode is the measurement liquid, and the liquid injected into the measurement chamber 14 in the second liquid injection mode is the dilution liquid, and the control The unit 30E may be configured to control the amount of the diluent to be injected into the measurement chamber 14 in the second liquid injection mode based on the measurement result of the second measurement mode.

  According to said structure, in the 2nd measurement mode, the light which permeate | transmitted the liquid mixture of the liquid inject | poured by 1st liquid injection mode and a reagent is measured. Thereby, the characteristics of the measurement liquid injected in the first liquid injection mode can be acquired. And based on the characteristic of this measurement liquid, the quantity of the dilution liquid inject | poured into a measurement chamber in 2nd liquid injection mode is controlled. Thereby, the dilution rate of a measurement liquid can be made into the dilution rate suitable for the measurement in a measurement process mode.

  In any of the above-described aspects 1 to 7, the control units 30A to 30E include the first liquid injection mode, the agitation mode, the second liquid injection mode, and the measurement devices 1A to 1E according to aspect 8 of the present invention. It is preferable that each mode of the first measurement mode is executed in this order.

  According to said structure, a control part performs each mode of 1st liquid injection mode, stirring mode, 2nd liquid injection mode, and 1st measurement mode in this order. Thus, in the first liquid injection mode, the liquid is injected into the measurement chamber so that the liquid level is lower than the low ceiling surface. Thereby, in the stirring mode, the liquid and the solid inside the measurement container, or the stirring and dissolution of the liquid and the liquid can be efficiently performed. Then, in the second liquid injection mode, the liquid is injected into the measurement chamber so that the liquid level is higher than the low ceiling surface. Thereby, even if bubbles are generated in the measurement container, the generated bubbles can be easily trapped in the space formed between the high ceiling surface and the liquid surface of the liquid. Therefore, in the first measurement mode, it is possible to prevent a decrease in measurement accuracy due to the presence of bubbles when light is transmitted through the low-top surface and the optical characteristics of the liquid are measured.

  In the present invention, each mode may be automatically executed under the control of the control unit, or may be sequentially executed manually by an operator pressing a switch for each mode.

  The measuring devices 1A to 1E according to the ninth aspect of the present invention are the measuring devices 1A to 1E according to any one of the first to eighth aspects, in which the stirring unit (drive mechanism 23) rotates the measuring container 10 about the one rotation shaft 19. It is preferable that the measurement container 10 be agitated by being rotated while being accelerated / decelerated around the shaft 19.

  According to the above configuration, the liquid / reagent stored in the measurement chamber can be agitated by rotating the measurement container while accelerating / decelerating it about the center of one rotation axis.

  In the measurement apparatus 1A to 1E according to aspect 10 of the present invention, in the aspect 9, the one or more measurement chambers 14 are a plurality of measurement chambers 14, and the plurality of measurement chambers 14 include the rotation shaft 19. It is preferable that the plane is arranged on the same circumference centering on the rotation axis 19 in one plane perpendicular to the axis.

  According to said structure, the several measurement chamber is arrange | positioned on the same periphery centering on a rotating shaft in one plane perpendicular | vertical to a rotating shaft. As a result, by rotating the measurement container around the rotation axis, it is possible to perform a plurality of measurements with one measurement unit.

  A measurement method according to an aspect 11 of the present invention includes one or a plurality of measurement chambers 14 for containing a liquid, the measurement chamber 14 includes a bottom surface 18 and a top surface 17 whose inner walls face each other, and the top The surface 17 includes a low-top surface 17b that transmits light, and a high-top surface 17a that is located around the low-top surface 17b and that is positioned higher than the low-top surface 17b with respect to the bottom surface 18. A measurement method using the measurement container 10, the measurement step of measuring the measurement chamber 14 and the light transmitted through the liquid contained in the measurement chamber 14, the stirring step of stirring the measurement vessel 10, A liquid injection step for injecting the liquid into the measurement chamber 14; and a control step for controlling the measurement step, the stirring step, and the liquid injection step. Than low top surface 17b In the first liquid injection mode for injecting liquid into the measurement chamber 14 so as to be in the position, the agitation mode in which the measurement container 10 is agitated in the agitation step, and the liquid is injected in the first liquid injection mode. In the second liquid injection mode for injecting liquid into the measurement chamber 14 so that the liquid level is higher than the low ceiling surface 17b, and in the measurement step, the measurement chamber 14 and the measurement chamber 14 are accommodated. The first measurement mode for measuring the light transmitted through the liquid is executed in this order.

  According to this feature, the top surface of the measurement chamber is located at a low ceiling surface that transmits light, and at the periphery of the low ceiling surface, and is positioned higher than the low ceiling surface with respect to the bottom surface of the measurement chamber. A measuring container having a high top surface is used. Thereby, even if bubbles are generated in the measurement container, the generated bubbles are easily trapped in the space formed between the high ceiling surface and the liquid surface of the liquid. As a result, the entrapment of bubbles in the space between the low ceiling surface and the bottom surface is reduced. Therefore, in the first measurement mode, it is possible to prevent a decrease in measurement accuracy due to the presence of bubbles when light is transmitted through the low-top surface and the optical characteristics of the liquid are measured. Therefore, there is an effect of providing a measurement method capable of performing measurement with high accuracy.

  According to this feature, the first liquid injection mode, the agitation mode, the second liquid injection mode, and the first measurement mode are executed in this order. Thus, in the first liquid injection mode, the liquid is injected into the measurement chamber so that the liquid level is lower than the low ceiling surface. Thereby, in the stirring mode, the liquid and the solid inside the measurement container, or the stirring and dissolution of the liquid and the liquid can be efficiently performed. Then, in the second liquid injection mode, the liquid is injected into the measurement chamber so that the liquid level is higher than the low ceiling surface. In the first measurement mode, light is transmitted through the low-top surface and the optical characteristics of the liquid are measured. Therefore, there is an effect of providing a measurement method capable of improving measurement accuracy by efficiently stirring the liquid to be measured.

  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 1E Measuring device 10 Measuring container 14 Measuring chamber 17 Top surface 17a High ceiling surface 17b Low ceiling surface 18 Bottom surface 19 Rotating shaft 23 Drive mechanism (stirring unit)
24A, 24B Liquid injection device (liquid injection part)
25 Optical measurement mechanism (measurement unit)
30A to 30E Control unit 31 First liquid injection amount control unit 31a First liquid injection amount storage unit 32 Second liquid injection amount control unit 32a Second liquid injection amount storage unit 32b Second liquid injection amount calculation unit 40 Reagent

Claims (11)

A measurement container having one or more measurement chambers for containing liquid;
A measurement unit for measuring light transmitted through the measurement chamber and the liquid contained in the measurement chamber;
A stirring section for stirring the measurement container;
A liquid injection part for injecting the liquid into the measurement chamber;
A measuring device comprising a control unit for controlling the measuring unit, the stirring unit and the liquid injection unit,
The measurement chamber includes a bottom surface and a top surface whose inner walls face each other, the top surface is positioned around the low ceiling surface through which light passes, and the low ceiling surface is positioned with respect to the bottom surface. A high sky surface arranged at a position higher than the surface,
The controller is
A first liquid injection mode in which the liquid injection unit injects liquid into the measurement chamber so that the liquid level is lower than the low ceiling surface;
A stirring mode in which the stirring unit stirs the measurement container; and
A second liquid injection mode for injecting the liquid into the measurement chamber into which the liquid has been injected in the first liquid injection mode so that the liquid level is higher than the low ceiling surface;
The measurement apparatus, wherein the measurement unit executes the measurement chamber and a first measurement mode for measuring light transmitted through the liquid contained in the measurement chamber. The liquid stored in the measurement chamber includes a measurement liquid containing a measurement component, and a dilution liquid for diluting the measurement liquid,
The liquid injected into the measurement chamber in the first liquid injection mode is one of the measurement liquid or the dilution liquid,
The measurement apparatus according to claim 1, wherein the liquid injected into the measurement chamber in the second liquid injection mode is the other of the measurement liquid and the dilution liquid. The controller is
A first liquid injection amount control unit that controls a first liquid injection amount that is an amount of liquid injected into the measurement chamber in the first liquid injection mode;
The measurement according to claim 1, further comprising: a second liquid injection amount control unit that controls a second liquid injection amount that is an amount of liquid injected into the measurement chamber in the second liquid injection mode. apparatus. The first liquid injection amount control unit includes a first liquid injection amount storage unit that stores the first liquid injection amount in advance,
The second liquid injection amount control unit includes a second liquid injection amount storage unit that stores the second liquid injection amount in advance,
A first liquid injection amount controller configured to inject the liquid of the first liquid injection amount stored in the first liquid injection amount storage unit into the measurement chamber in the first liquid injection mode;
The second liquid injection amount control unit causes the second liquid injection amount liquid stored in the second liquid injection amount storage unit to be injected into the measurement chamber in the second liquid injection mode. Item 4. The measuring device according to Item 3. The measurement chamber is pre-filled with a reagent,
The measurement according to any one of claims 1 to 4, wherein the reagent and the liquid injected into the measurement chamber by the liquid injection unit are agitated by agitating the measurement container. apparatus.   The control unit causes the measurement unit to execute a measurement chamber into which liquid is injected in the first liquid injection mode and a second measurement mode in which light transmitted through the liquid stored in the measurement chamber is measured. The measuring apparatus according to claim 5. The liquid stored in the measurement chamber includes a measurement liquid containing a measurement component, and a dilution liquid for diluting the measurement liquid,
The liquid injected into the measurement chamber in the first liquid injection mode is the measurement liquid,
The liquid injected into the measurement chamber in the second liquid injection mode is the diluent.
The measurement apparatus according to claim 6, wherein the control unit controls an amount of a diluent to be injected into the measurement chamber in the second liquid injection mode based on a measurement result in the second measurement mode. .   The said control part performs each mode of the said 1st liquid injection | pouring mode, the said stirring mode, the said 2nd liquid injection | pouring mode, and the said 1st measurement mode in this order, The any one of Claims 1-7 characterized by the above-mentioned. The measuring device according to claim 1.   The said stirring part makes the said measurement container stir operation | movement by rotating the said measurement container around the said rotating shaft, accelerating / decelerating it centering on one rotating shaft. The measurement apparatus according to any one of the above. The one or more measurement chambers are a plurality of measurement chambers;
The measuring apparatus according to claim 9, wherein the plurality of measurement chambers are arranged on the same circumference around the rotation axis in one plane perpendicular to the rotation axis. Comprising one or more measuring chambers containing liquids;
The measurement chamber includes a bottom surface and a top surface whose inner walls face each other, the top surface is positioned around the low ceiling surface through which light passes, and the low ceiling surface is positioned with respect to the bottom surface. A measuring method using a measuring container having a high sky surface arranged at a position higher than the surface,
A measurement step of measuring light transmitted through the measurement chamber and the liquid contained in the measurement chamber;
A stirring step of stirring the measurement container;
A liquid injection step of injecting the liquid into the measurement chamber;
A control step for controlling the measurement step, the stirring step and the liquid injection step,
The control step includes
In the liquid injection step, a first liquid injection mode in which liquid is injected into the measurement chamber so that the liquid level is lower than the low ceiling surface;
In the stirring step, a stirring mode for stirring the measurement container;
A second liquid injection mode for injecting the liquid into the measurement chamber into which the liquid has been injected in the first liquid injection mode so that the liquid level is higher than the low ceiling surface;
In the measurement step, the measurement method is characterized in that the measurement chamber and the first measurement mode for measuring the light transmitted through the liquid stored in the measurement chamber are executed in this order.

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