Measuring device

Abstract

To solve the problem in which: in determining the composition ratio of a composition according to an infrared absorption method, proximity of absorption peaks of a plurality of substances that form the composition makes it difficult to acquire a calibration curve and makes it difficult to determine the composition ratio.MEANS FOR SOLVING THE PROBLEM: A measuring device acquires calibration curve candidates, for each of a plurality of combinations of wavelengths near an absorption wavelength and reference wavelengths, from an optical intensity obtained by measuring samples having existing composition ratios according to an infrared absorption method. The measuring device performs residual evaluation for the calibration curve candidates, and determines a calibration curve candidate in which the combination of the wavelengths is in an appropriate relationship as a calibration curve to be used, thereby holding a calibration curve that is determined according to a calibration curve acquisition method with which a composition ratio can be determined even if a composition has proximate absorption wavelengths, and determines the composition ratio of a composition by using the calibration curve held.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a measuring device that acquires and holds a calibration curve for detecting a composition ratio from observation results obtained by a plurality of observation means that change observed physical quantities by a multivariate analysis method in order to determine the composition ratio of a composition, and determines the composition ratio of the composition by multivariate analysis using the calibration curve. Furthermore, it relates to an operation method of the measuring device which is a computer, a program for causing the measuring device which is a computer to execute, and a storage device storing the program.

Background Art

[0002] When deriving a value B that has a correlation with a certain measured value A, when it is difficult or laborious to directly obtain the B from the measured value A, a calibration curve showing the relationship between the measured value A and the value B is obtained from the measured value A of a plurality of known value B samples measured in advance and the known value B of the measured samples, and used at the time of actual measurement.

[0003] Patent Document 1 discloses a concentration quantification device and a concentration quantification method capable of performing concentration quantification without using an internal standard sample while using a measurement system in which the scale fluctuates (when the measured amount of an unknown sample is n times (0 < n) the measured amount of a standard sample) with respect to linear residuals and scale factors, which are typical errors in quantification accuracy during concentration quantification.

[0004] In the concentration quantification device described in Patent Document 1, for concentration quantification, first, a pseudo-concentration is calculated from the measured amounts of a plurality of standard samples and the measured amounts of samples selected by the number of components from among the plurality of standard samples, a scale factor is calculated from the predetermined concentration of the standard sample and the pseudo-concentration, a corrected measured amount obtained by correcting the measured amount is calculated, and a calibration coefficient is calculated from the correlation between the predetermined concentration of the standard sample and the corrected measured amount. Then, next, the concentration of the unknown sample is calculated from the calculated calibration coefficient and the measured amount of the unknown sample.

Prior Art Documents

Patent Documents

[0005] Patent Document 1 Japanese Patent Application Laid-Open No. 2016-176939 Summary of the Invention Problems to be Solved by the Invention

[0006] In the concentration quantification device of the invention described in Patent Document 1, the concentration is obtained from the measurement amount using the calibration coefficient and the scale coefficient. These calibration coefficients and scale coefficients correspond to the calibration curve of the present invention. In Patent Document 1, since the calibration coefficient is determined so that the sum of squared residuals becomes extremely small, when a calibration curve candidate is obtained from the observation result of changing the observed physical quantity for a sample with a known composition ratio and the observed physical quantity, the calibration curve candidate with the extremely small sum of squared residuals is determined as the calibration curve to be actually used (hereinafter, the used calibration curve). There is a problem that Patent Document 1 does not describe whether the content of the combination of the levels of a plurality of conditions is physically considered when determining the used calibration curve, and it is not considered. Further, there is a problem that the used calibration curve is determined only under the condition that the sum of squared residuals becomes extremely small, and the bias of the distribution of other residuals is not considered.

[0007] Therefore, in the present invention, an observation result (e.g., light intensity) of changing an observed physical quantity (e.g., wavelength) for a sample with a known composition ratio is obtained, and a plurality of calibration curve candidates are obtained for each sample from the observed physical quantity and the observation result. As a result of selection using a residual evaluation rule and a selection rule (including physical rules), a calibration curve acquisition unit that determines a used calibration curve as the calibration curve to be used from within the calibration curve candidates is provided, a calibration curve holding unit that holds the calibration curve acquired by the calibration curve acquisition unit, and a composition ratio determination unit that determines the composition ratio of the composition using the held calibration curve. The measurement device can use the previously held calibration curve as the used calibration curve, but when the held calibration curve cannot be used for the measurement target, new calibration curve candidates can be obtained, and the used calibration curve can be determined and held. The labor and cost of obtaining a calibration curve using a separate device and recording the obtained calibration curve in the calibration curve holding unit can be saved.

[0008] Also provided is a measuring device having a calibration curve holding unit that holds a use calibration curve determined and acquired in advance without having a calibration curve acquisition unit, and a composition ratio determination unit that determines the composition ratio of the composition using the held use calibration curve. When the held calibration curve cannot be used for the measurement target, a calibration curve candidate can be acquired by newly measuring and calculating outside the measuring device to determine the use calibration curve, and the determined use calibration curve can be newly held in the measuring device.

[0009] Furthermore, provided are an operation method of the device which is a computer, a program for causing the device which is a computer to execute, and a storage medium storing the program.

[0010] By using the measuring device of the present invention, in particular, when the measurement target is a coating film using a black material with a low infrared reflectance, or in a coating film for measuring the solid content concentration (e.g., the positive electrode of a lithium-ion battery), when the material contains a material having an absorption peak close to the solvent to be measured, or when the two cases overlap, a calibration curve for short-term use can be obtained by the non-contact and non-destructive infrared absorption method, and a solid content concentration measurement result can be obtained. In the manufacturing line, on-site, high-frequency quality control solid content concentration measurements can be performed for all or sampled products, improving and maintaining the quality of parts, and suppressing the occurrence of defective or second-class products that do not meet the desired performance as products incorporating the parts.

[0011] Regarding a measuring device that uses a calibration curve, it is configured to output a measurement result using a calibration curve that is held in advance. Further, when the calibration curve held for the measurement target cannot be applied, a new calibration curve is obtained by conducting an experiment and performing calculations outside the measuring device, and the obtained calibration curve is newly held in the measuring device. However, in a multi-product production line or the like, if it is necessary to prepare a measuring device for each product type and operate multiple lines, or record a calibration curve in the measuring device each time the product type of a single line changes, this is inefficient in terms of cost and complexity. Therefore, for example, when the product type changes, the measuring device is configured to be able to obtain a calibration curve by using its own function or the function of an associated device, and the production efficiency will be increased if the obtained calibration curve can be immediately used. As an example of such a case, in a production line where it is desired to measure and control the composition ratio of a composition composed of multiple substances, a case where the substances constituting the composition are changed depending on the product type can be cited.

Means for Solving the Problem

[0012] In order to solve the problems related to the measuring device as described above, in the present application, as a first invention, A calibration curve acquisition unit (A) that acquires a calibration curve for detecting a composition ratio from observation results obtained by a plurality of observation means by a multivariate analysis method in order to determine the composition ratio of a composition, Observation result acquisition means (E) for acquiring a value indicating an observation result in which an observed physical quantity is changed for each of a plurality of samples having a known composition ratio, Calibration curve candidate acquisition means (F) for acquiring a plurality of calibration curve candidates for each sample from the value indicating the acquired observation result and the observed physical quantity for which the observation result was obtained, Rule holding means (G) for holding a rule for evaluating a residual for each of the acquired calibration curve candidates, Residual evaluation means (H) for performing residual evaluation using the held rule, Selection rule holding means (J) for holding a selection rule for selecting a calibration curve candidate for which the residual has been evaluated from the results of residual evaluation; Calibration curve determination means (G) for determining, as a calibration curve to be used, a predetermined calibration curve candidate using the held selection rule; A calibration curve acquisition unit (A) comprising: Calibration curve holding means (B) for holding the acquired calibration curve; Composition ratio determination means (C) for determining the composition ratio of the composition by multivariate analysis using the held calibration curve; A measuring apparatus having:

[0013] As a second invention, based on the first invention, Provided is a measuring apparatus, wherein the plurality of observation means are observations of the reflected light intensity (or absorbance, transmitted light intensity, absorbance + transmitted light intensity, which is the same hereinafter. The same applies hereinafter.) when light of a plurality of wavelengths is applied to a composition.

[0014] As a third invention, based on any one of the first or second inventions, The selection rule is such that when the composition is manufactured with a targeted composition ratio in advance, the wavelength of light for which a large change in the reflected light intensity is expected at the targeted composition ratio, and observations using light of wavelengths longer and shorter than that wavelength are included in at least a plurality of observation means. Provided is a measuring apparatus.

[0015] As a fourth invention, based on any one of the first to third inventions, The selection rule includes a rule of selecting observations of wavelengths for which the proportion affected by the change is low when the reflected light intensity of the composition changes due to factors other than the composition ratio. Provided is a measuring apparatus.

[0016] As a fifth invention, A method for obtaining a calibration curve for detecting a composition ratio from observation results obtained by a plurality of observation means by a multivariate analysis method for determining the composition ratio of a composition, A sample preparation step (d) of preparing a plurality of samples having known composition ratios; An observation result acquisition step (e) of obtaining a value indicating an observation result in which an observation physical quantity is changed for each prepared sample; A calibration curve candidate acquisition step (f) of acquiring a plurality of calibration curve candidates for each sample from the value indicating the acquired observation result and the observation physical quantity from which the observation result was obtained; A residual evaluation step (g) of performing a residual evaluation using a rule for evaluating a residual for each of the acquired calibration curve candidates; A used calibration curve determination step (h) of determining, as a calibration curve to use, a predetermined calibration curve candidate using a selection rule for selecting a calibration curve candidate for which the residual has been evaluated from the results of the residual evaluation; A calibration curve holding unit (B) that holds a calibration curve obtained by a calibration curve acquisition method comprising: A composition ratio determination unit (C) that determines the composition ratio of the composition by multivariate analysis using the held calibration curve; A measuring device having:

[0017] As a sixth invention, based on the fifth invention, Provided is a measuring device, wherein the plurality of observation means are observations of the reflected light intensity (or absorbance, transmitted light intensity, absorbance + transmitted light intensity, which is the same hereinafter. The same applies hereinafter.) when light of a plurality of wavelengths is applied to the composition.

[0018] As a seventh invention, based on the fifth or sixth invention, The selection rule is such that when the composition is manufactured with a preconceived target composition ratio, the wavelength of light for which a large change in the reflected light intensity is expected at the targeted composition ratio, and observations using light of wavelengths longer and shorter than that wavelength are included in at least a plurality of observation means. A measuring device is provided.

[0019] As an eighth invention, based on any one of the fifth to seventh inventions, The selection rule includes a rule of selecting an observation at a wavelength at which the ratio of being affected by the change is low when the reflected light intensity of the composition changes due to factors other than the composition ratio. A measuring device is provided.

[0020] Furthermore, there are also provided a method for operating a measuring device which is a computer according to the first to eighth inventions, and a program to be executed by the measuring device which is a computer. The program may also be recorded on a storage medium.

Advantages of the Invention

[0021] With the measuring device of the present invention having the above configuration, observation results (e.g., light intensity) with the observation physical quantity (e.g., wavelength) changed for a sample with a known composition ratio are obtained, and a plurality of calibration curve candidates are obtained for each sample from the observation physical quantity and the observation results. As a result of selection using a residual evaluation rule and a selection rule (including physical rules), there is provided a measuring device having a calibration curve acquisition unit that determines a calibration curve to be used as the calibration curve to be used from within the calibration curve candidates, a calibration curve holding unit that holds the calibration curve acquired by the calibration curve acquisition unit, and a composition ratio determination unit that determines the composition ratio of the composition using the held calibration curve. The measuring device can use a previously held calibration curve as the calibration curve to be used, but if the held calibration curve cannot be used for the measurement target, new calibration curve candidates can be obtained, and the calibration curve to be used can be determined and held. It is possible to save the labor and cost of obtaining a calibration curve using a separate device and recording the obtained calibration curve in the calibration curve holding unit.

[0022] There is also provided a measuring device having a calibration curve holding unit that holds a calibration curve to be used determined and obtained in advance without having a calibration curve acquisition unit, and a composition ratio determination unit that determines the composition ratio of the composition using the held calibration curve to be used. If the held calibration curve cannot be used for the measurement target, calibration curve candidates can be obtained by newly measuring and calculating outside the measuring device, the calibration curve to be used can be determined, and the determined calibration curve to be used can be newly held in the measuring device.

[0023] Furthermore, there can be provided a method for operating the device which is a computer, a program for causing the device which is a computer to execute, and a storage medium storing the program.

[0024] By using the measuring device of the present invention, particularly when the measurement target is a coating film made of a black material with a low infrared reflectance, or when measuring the solid content concentration of a coating film (e.g., the positive electrode of a lithium-ion battery) and the material has an absorption peak close to the solvent to be measured, or when the above two cases overlap, a calibration curve can be obtained in a short time by the non-contact and non-destructive infrared absorption method, and the solid content concentration measurement result can be obtained. In the production line, solid content concentration measurement for quality control can be performed frequently on-site, either for all products or for a sampled subset, which can improve and maintain the quality of components and suppress the occurrence of defective or second-class products that do not meet the desired performance as products incorporating these components.

[0025] Regarding those that utilize a calibration curve with a measuring device, it is configured to output a measurement result using the calibration curve held in advance. Also, when the calibration curve held for the measurement target cannot be applied, a new calibration curve is obtained by conducting experiments and calculations outside the measuring device, and the obtained calibration curve is newly held in the measuring device. However, in a multi-product production line, etc., if it is necessary to prepare a measuring device for each product type and operate multiple lines, or record the calibration curve in the measuring device every time the production product type changes on a single line, this is inefficient in terms of cost and complexity. Therefore, for example, when the production product type changes, the measuring device is configured to be able to obtain a calibration curve by using its own functions or the functions of associated devices, and the obtained calibration curve can be immediately utilized, which will increase production efficiency. As an example of such a case, in a production line where it is desired to measure and control the composition ratio of a composition composed of multiple substances, the case where the substances constituting the composition are changed depending on the production product type can be cited.

Brief Description of the Drawings

[0026]

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Modes for Carrying Out the Invention

[0027] <Premise for the description of all embodiments> <Regarding the hardware that can constitute the present invention> The measuring device of the present invention is an invention that in principle uses an electronic computer, but at least part of it is realized by software, also realized by hardware, and also realized by the cooperation of software and hardware. In this case, the software uses hardware resources to perform various operations and realizes various functions through the required data and information. It can be said that the information processing by software is specifically realized using hardware resources.

[0028] The hardware that realizes all or part of each component of the measuring device of the present invention is composed of an MPU including a CPU which is the basic configuration of a computer, a memory, a bus, an input / output device, various peripheral devices, a user interface, and the like. The various peripheral devices may include a storage device, an interface such as the Internet, Internet devices, LAN devices, Wifi (registered trademark) devices, a display, a display interface, a keyboard, a mouse, a speaker, a microphone, a camera, a video, a television, a CD device, a DVD device, a Blu-ray device, a USB memory, a USB memory interface, a removable type hard disk, a general hard disk, a projector device, an SSD, a telephone, a fax, a copier, a printing device, a movie editing device, various sensor devices, and the like.

[0029] Also, the measuring device of the present invention does not necessarily have to be configured by a single housing, and may be configured by communicatively coupling a plurality of housings. Also, the communication may be LAN, WAN, Wifi (registered trademark), Bluetooth (registered trademark), infrared communication, ultrasonic communication, near-field wireless communication (NFC), a mobile phone network, and furthermore, part of it may be installed across national borders.

[0030] <Satisfaction of the availability of the natural law of the present invention in all embodiments>

[0031] The measuring device of the present invention functions in cooperation with a computer and software. The measuring device of the present invention obtains a calibration curve for detecting the composition ratio from the observation results obtained by a plurality of observation means that change the observed physical quantity by a multivariate analysis method in order to determine the composition ratio of the composition, from the results of observing a sample with a known composition ratio using a plurality of observation means that change the observed physical quantity. A plurality of calibration curve candidates are obtained from the results of observations by a plurality of observation means, the residual is evaluated for each calibration curve candidate, and from the results of the residual evaluation, the calibration curve candidate for which the residual has been evaluated is selected and determined as the calibration curve using a predetermined calibration curve candidate, and the process is performed on a computer. Since the observation means for determining the composition ratio of the composition using the observation results obtained by changing the observed physical quantity is an observation means that conforms to physical laws (for example, infrared absorption method, etc.), the present invention is an invention that utilizes natural laws.

[0032] <Hardware Configuration>

[0033] FIG. 7 shows the overall conceptual configuration of the measuring device (0700) of the present invention and, as an example using the measuring device (0700), the case of in-line measurement of the solid content concentration of a positive electrode active material slurry, which is a mixture of a positive electrode active material and a solvent containing a positive electrode active material coated on a positive electrode substrate, in the positive electrode manufacturing process of a lithium-ion battery. As the positive electrode active material, a general positive electrode active material for a lithium-ion battery can be used. The positive electrode active material slurry, which is a mixture of a positive electrode active material and a solvent containing a positive electrode active material, is, for example, a mixture of a positive electrode active material (e.g., NCM; lithium nickel cobalt manganese oxide), a binder (e.g., PVdF; polyvinylidene fluoride), a conductive aid (e.g., acetylene black), and a solvent (e.g., NMP; N-methyl-2-pyrrolidone). As the positive electrode substrate (0730) on which the positive electrode active material slurry is coated, for example, Al foil is used. In FIG. 7, the positive electrode active material slurry is applied to the surface of the Al foil drawn from the raw material roll (0731) on the right side using known means such as a syringe or a slit coater (positive electrode active material coater (0734)), and the solid content concentration of the coating film is measured by the measuring device (0700) before drying with the heater (0732). After measuring the solid content concentration of the coating film, the solvent is volatilized with the heater (0732) and the dried film is wound up by the winding roller (0733).

[0034] As an example of the conceptual configuration of the measuring device of the present invention, as shown in FIG. 7 which shows an example of a measuring device using the infrared absorption method, a light source (0720) that irradiates infrared rays, and a filter disk (0721) provided with a plurality of filters that limit the light from the light source (0720) to a specific wavelength, and an optical system (0722) that irradiates infrared rays to the measurement object composed of a mirror (a plane mirror, a concave mirror, a convex mirror in the figure, may include a lens) and guides the reflected light to the sensor (0723), a sensor (0723) that receives the infrared rays reflected from the positive electrode active material slurry coating film applied to the positive electrode substrate (0730) (Al foil) which is the measurement object, a calibration curve acquisition unit (A) (0701) that acquires a calibration curve based on the light intensity received by the sensor (0723), a calibration curve holding unit (H) (0708) that holds the calibration curve, and a composition ratio determination unit (J) (0709) that determines the composition ratio of the composition (the solid content concentration of the coating film in the example of FIG. 7) by multivariate analysis using the held calibration curve, and a calculation board (0724).

[0035] The measuring device (0700) may also be configured as a measuring device, to which a display device (0754) that displays the composition ratio output from the calculation board (0724), a PC (0752) and a server device (0751) that acquire the composition ratio from the calculation board (0724) via the Internet line (0750) are connected.

[0036] Among the substances constituting the positive electrode active material slurry, those other than NMP which is a solvent are solutes which are solid components, and they are substances that remain as a film on the metal foil when the solvent volatilizes after coating. If the solid content concentration is different even when the positive electrode active material slurry is coated with the same film thickness, the resulting film thickness after solvent volatilization will be different, which will affect the final battery performance. Therefore, in a manufacturing site where the slurry is being continuously applied to a flowing part, it is important to manage the solid content concentration of the coated film in order to maintain quality. In order to obtain the composition ratio of the solute, it is necessary to obtain the composition ratios of the three types of materials, namely the positive electrode active material, the binder, and the conductive assistant, and three measurements are required. In the positive electrode active material slurry in this example, acetylene black is used as the positive electrode active material, and there is also a problem that the infrared reflectivity is small and it is difficult to measure.

[0037] Therefore, if the composition ratio of NMP as the solvent is determined, the solid content concentration can be determined as the ratio other than NMP. Since the number of measurements can also be reduced, it is effective. The calibration curve for measuring NMP by the infrared absorption method and determining the solid content concentration of the coating film will be a calibration curve in which the solid content concentration has a negative correlation with the measured value of NMP.

[0038] The acquisition of the composition ratio is performed by utilizing the property that the functional group of the solvent substance (e.g., NMP) in the coating film absorbs specific wavelengths of infrared rays. Since the ratio of infrared rays absorbed by the solvent changes according to the film thickness and the ratio of the solvent, a plurality of coating films with known compositions are measured in advance, the ratio of the solvent in the coating film is obtained from the light intensity, and a calibration curve used to obtain the solid content concentration, which is the remaining ratio, is determined and held.

[0039] The method for obtaining the calibration curve will be described in detail later. A plurality of candidates for wavelengths near the absorption wavelength of the solvent and reference wavelengths for measuring the light intensity for reference are selected, and filters that transmit light for each of the wavelengths are set on a filter disk (0721). A plurality of samples with known composition ratios, which are the compositions to be measured, are prepared, and measurements are performed for each filter (wavelength) prepared for each sample. Since manually exchanging the filters is laborious, it is preferable to configure such that when a sample is set, the filter is automatically set, and when the measurement with a filter of one wavelength is completed, it is switched to the next filter, enabling automatic measurement at all wavelengths. More preferably, the samples can also be automatically exchanged. The filter disk (0721) in FIG. 7 has filters for each wavelength fitted into holes provided on the same circumference within the disk, and is rotated as necessary to insert the desired filter into the optical path from the light source. The filter disk (0721) may be provided with a through-hole for use when no filter is used.

[0040] In addition, when the positive electrode substrate (0730) transmits infrared rays, a configuration similar to the above example can be achieved by installing a reflector (not shown) below the positive electrode substrate (0730) in FIG. 7 and guiding the reflected light to the sensor (0723). Alternatively, the sensor (0723) may be arranged on the side opposite to the light source with the positive electrode active material thin film and its positive electrode substrate (0730) interposed therebetween, and configured to measure the transmitted light.

[0041] In the above example, in the positive electrode manufacturing process of the lithium ion battery, the case of obtaining a calibration curve candidate at the manufacturing site and determining the calibration curve to be used for measuring the solid content concentration of the coating film immediately after applying the positive electrode active material slurry to the positive electrode substrate was described. For example, the same applies when a calibration curve candidate for a predetermined measurement target (in the above example, for measuring the solid content concentration of the active material of the lithium ion battery) is obtained at the factory manufacturing the measuring device of the present invention, the calibration curve to be used is determined, and the measuring device is shipped after being held in the calibration curve holding unit (H).

[0042] The calculated composition ratio is output to a user interface (UI) such as a display device (0754) or an Internet line (0750) (or a LAN line may also be used) via a USB, a LAN terminal, etc. It is sent to the server device (0751) and the PC (0752) via the Internet line (0750). It can also be configured to output to a PC or a server device by connecting to a LAN line without directly connecting to the Internet line. In that case, a gateway and a firewall can be further connected to the LAN line and configured to connect to the Internet line via the gateway and the firewall. Although only the Internet line is shown in the figure, the same effect can be obtained with only the LAN line or both the LAN line and the Internet line.

[0043] FIG. 8 is a diagram showing an example of the hardware configuration of the arithmetic board, which is the computer of the present invention shown in FIG. 7. Taking the case of a configuration according to an embedded system as an example, the hardware configuration of the arithmetic board in the device of the present invention will be described with reference to FIG. 8. Since FIG. 8 is a diagram for explaining the hardware configuration, descriptions of individual programs and data are omitted. Note that the hardware of the computer part of the device of the present invention may have a configuration according to a known PC. When a server is used in the system including the device of the present invention, the server may have a configuration according to a known PC.

[0044] FIG. 8 is a conceptual diagram showing the hardware configuration of the computer part (hereinafter sometimes abbreviated as the embedded system) in the measuring device (hereinafter sometimes abbreviated as this device) of each embodiment of the present invention. As shown in the figure, this device includes an MPU, a non-volatile memory (for example, ROM, SSD, HDD, flash memory, etc.), a main memory (e.g., DRAM, SRAM, etc.), a LAN I / F (I / F: interface) for connection with a control PC, a recording meter, etc., and an interface "USB, I 2 C, SPI, etc." for connection with a control module, etc., and a system bus (thick line in the figure) for performing signal transmission and reception between them. Further, it is also connected to "infrared sensors, arithmetic boards" via "USB, I 2 C, SPI, etc.".

[0045] <Hardware: MPU> "MPU" is an abbreviation for Microprocessor Unit, and refers to an integrated circuit in which a microprocessor, a CPU, a memory, an input / output interface, a timer, an interrupt controller, etc. are integrated around the microprocessor. The integrated circuit is often manufactured in a form integrated on one chip. Examples of functions to be integrated include, in addition to the above examples, a CPU, a flash memory, a memory I / F, an AD converter, a PLL (Phase-Locked Loop), a LAN I / F, a USB I / F, I 2It is possible to integrate a CI / F, SPI I / F, power control I / F, graphic function, floating-point calculation unit, etc. For example, if a LAN I / F is integrated, there is no need to prepare a control IC for the LAN I / F other than the MPU. The MPU in Fig. 8 is an example in which a memory I / F and a graphic function are integrated with the CPU.

[0046] <Hardware: Non-volatile Memory> As non-volatile memory mounted on an embedded system, EP-ROM, EEP-ROM, flash memory, or SSD is used as ROM. An HDD can also be used, but there are restrictions on vibration resistance and shock resistance.

[0047] The non-volatile memory stores firmware, which is a basic program for operating the embedded system and controlling the hardware. The firmware is read into the main memory, expanded, and executed in the same way as other programs. Also, when a non-volatile memory is implemented in the MPU, the firmware may be stored in the non-volatile memory on the MPU side and operated on the non-volatile memory. This can reduce the amount of main memory mounted and used.

[0048] The "device driver" stored in the non-volatile memory is software used to operate hardware interfaces such as LAN and USB. At execution time, it is read into the main memory, expanded, and executed. Also, when a non-volatile memory is implemented in the MPU, the device driver may be stored in the non-volatile memory on the MPU side and operated on the non-volatile memory. This can reduce the amount of main memory mounted and used. The specifications and configuration of the firmware and device driver are determined when the configuration of the computer part incorporated in this device (including various I / F configurations) is determined.

[0049] In addition, the non-volatile memory stores other software necessary for operating this device, which is read into the main memory, expanded, and executed at execution time.

[0050] <Hardware: Main Memory: Volatile Memory> The main memory is used as a work memory when executing various software during the operation of the embedded system. Therefore, DRAM or SRAM with high operating speeds such as reading and writing is used. In particular, SDRAM and DDR SDRAM in DRAM are widely used and mass-produced for PCs and mobile devices, and are easily available.

[0051] Each functional block described in the following embodiments can be realized by any of hardware, software, or both hardware and software. Specifically, if an embedded system is used, MPU, main memory, bus, non-volatile memory, input devices such as operation buttons used for information input, mouse, touch panel, electronic pen used specifically for touching the touch panel, joystick or pointer position input device similar to joystick, and other external peripheral devices, etc. Hardware components, as well as interfaces for those external peripheral devices, communication interfaces such as LAN terminals, image processing circuits, wireless communication interfaces, driver programs for controlling those hardware, and other application programs, etc. can be mentioned. In particular, plotters, data recording devices, personal computers for data acquisition or device control, server devices for data acquisition, wired and wireless networks and interfaces, etc. are used.

[0052] Through the arithmetic processing of the MPU according to the program deployed on the main memory, data input from input devices and other interfaces and held in memory or hardware is processed and stored, or instructions for controlling the above-mentioned hardware and software are generated. Here, the above program may be realized as a plurality of modularized programs, or may be realized as one program by combining two or more programs.

[0053] In addition, the present invention can also be partially configured as software. Furthermore, a storage medium on which such software is recorded is naturally included in the technical scope of the present invention (the same applies throughout this specification, not limited to this embodiment).

[0054] <Regarding the terms used in the present invention of the application>

[0055] In this specification, the term "association" is used to mean that, in addition to the case where two or more pieces of information are directly associated, it also includes the case where two or more pieces of information are indirectly associated via one or more other pieces of information. Indirect association is not necessarily limited to association within one device (a device with a single housing), and also includes cases where it is associated across multiple devices.

[0056] "Based on" includes both the case of relying on the object itself and the case of relying on the object after some processing has been done to the object. For example, "obtaining a calibration curve based on light intensity" may mean obtaining the "calibration curve" using the "light intensity" itself obtained by measurement, or obtaining the "calibration curve" using the value obtained by substituting the "light intensity" obtained by measurement into a mathematical formula.

[0057] <Overview of Embodiment 1> Mainly Claim 1 The measuring device of Embodiment 1 acquires observation results in which an observation physical quantity is changed for a plurality of samples with known composition ratios, obtains a plurality of calibration curve candidates for each sample from the value indicating the observation result and the observation physical quantity for which the observation result was obtained, determines the calibration curve to be used by means of residual evaluation and others, and is configured to determine the composition ratio of the composition using the determined calibration curve to be used.

[0058] <Functional Configuration of Embodiment 1> Fig. 1 shows a conceptual configuration diagram of the measuring device according to Embodiment 1. The measuring device (0100) according to Embodiment 1 includes a calibration curve acquisition unit (A) (0101) having an observation result acquisition means (B) (0102), a calibration curve candidate acquisition means (C) (0103), a residual evaluation rule holding means (D) (0104), a residual evaluation means (E) (0105), a selection rule holding means (F) (0106), and a used calibration curve determination means (G) (0107), a calibration curve holding unit (H) (0108), and a composition ratio determination unit (J) (0109).

[0059] Note that the above schematic structure is an example for implementing the present invention, and the structure may be appropriately omitted or a new structure may be added within a range not conflicting with the problems to be overcome by the present invention and its effects. The same applies to the descriptions after Embodiment 1.

[0060] <Description of the Configuration of Embodiment 1> <Calibration Curve Acquisition Unit (A) (0101) of Embodiment 1> The "calibration curve acquisition unit (A)" (0101) has an observation result acquisition means (B) (0102), a calibration curve candidate acquisition means (C) (0103), a residual evaluation rule holding means (D) (0104), a residual evaluation means (E) (0105), a selection rule holding means (F) (0106), and a used calibration curve determination means (G) (0107), and is configured to acquire a calibration curve for detecting a composition ratio from observation results obtained by a plurality of observation means by a multivariate analysis method in order to determine the composition ratio of the composition.

[0061] A composition is a substance composed of one or more substances mixed together, and alloys, aqueous solutions, colloidal solutions, gases, etc. are applicable. The composition ratio of a composition is the ratio of one or more substances constituting the composition to the whole composition. When the composition is solid, the composition ratio is the weight ratio or weight% of the constituent substances, and when it is liquid, it is the weight ratio or weight%, or the volume ratio or volume%. When the composition is gas, the composition ratio is the volume ratio or volume%.

[0062] Multivariate analysis methods are a general term for statistical methods used when multiple variables (or characteristics) affect each other. There are various multivariate analysis methods, and common methods include multiple regression analysis, principal component analysis, independent component analysis, factor analysis, cluster analysis, and the like.

[0063] Observation means are means for obtaining observation results, such as measurement, analysis, and observation. More specifically, it refers to the measurement of the light intensity of infrared rays with a predetermined wavelength by the infrared absorption method, the measurement of a spectrum indicating the light intensity over the entire predetermined wavelength range, the measurement of the radiation luminance of infrared rays emitted from an object, energy-dispersive X-ray analysis, the observation of the tensile strength of a composition, and the like. Multiple observation means refer to the case where a physical quantity to be observed (such as the wavelength of an electromagnetic wave, frequency, the amount of heat for heating an object, the acceleration voltage of an electron beam, the magnitude of a tensile force, etc.) is changed and observed multiple times with one observation means to obtain multiple observation results, or the case where observations are made with multiple observation means (changing the measurement method (infrared absorption method, chromatography, mass spectrometry, etc.)) to obtain multiple observation results. In the present invention, the former case is referred to.

[0064] A calibration curve is a so-called conversion function used to convert a value indicating an observation result into a value in a desired state. In the present invention, a calibration curve is used to determine the composition ratio of a composition from the value indicating the observation result.

[0065] To obtain a calibration curve, the calibration curve acquisition unit (A) (0101) includes an observation result acquisition means (B) (0102), a calibration curve candidate acquisition means (C) (0103), a residual evaluation rule holding means (D) (0104), a residual evaluation means (E) (0105), a selection rule holding means (F) (0106), and a used calibration curve determination means (G) (0107). Each means will be described below.

[0066] <Embodiment 1 Calibration Curve Acquisition Unit (A): Observation Result Acquisition Means (B) (0102)> The "observation result acquisition means (B)" (0102) is configured to acquire a value indicating an observation result obtained by changing the observation physical quantity for each of a plurality of samples having known composition ratios. The observation result acquisition means (B) may be configured to include the observation means, may be configured separately from the observation means, or may be configured to acquire the observation result from the observation means of a device different from the measuring device of the present invention. Examples of the observation means include infrared sensors such as pyroelectric type and thermoelectric power type, CCD, CMOS sensors, and phototubes. The observation means is not shown in FIG. 1.

[0067] For samples with known composition ratios, a plurality of levels are set for factors that are considered to affect the value indicating the observation result described below under the preparation conditions, and samples with a plurality of different composition ratios are prepared. For example, when a coating film obtained by applying a coating liquid in which a substance for forming the target film is dispersed in a solvent is used as a sample, the amount of the target substance (or the solid content concentration indicating the ratio contained in the coating film, or the composition ratio of the constituent substances in the solute when the solute consists of a plurality of substances, etc.) and the film thickness of the coating film are used as factors to set a plurality of levels, and corresponding samples are prepared.

[0068] In the example of the lithium-ion battery positive electrode manufacturing process shown in FIG. 7 above, the known composition ratio is the solid content concentration. Another example is the composition ratio of carbon and a binder that holds carbon on a substrate in a coating film obtained by applying and drying a solution containing the binder.

[0069] An observed physical quantity is a physical quantity used in an observation means to observe a sample and obtain an observation result. "Observation" in a broad sense is carried out by electromagnetic waves, and the observed physical quantity means the frequency (or wavelength) of the electromagnetic waves used in the observation. For example, when using an observation means (infrared absorption method) of irradiating a sample with infrared rays, detecting the infrared rays emitted from the sample, and observing (measuring) the light intensity, the observed physical quantity is the wavelength at the time of measuring the light intensity, and the observation result is the said light intensity. For the measurement of infrared rays, infrared sensors used in known infrared absorption methods such as pyroelectric type and thermoelectric power type can be used. In this example of the infrared absorption method, the observation result with the changed observed physical quantity is the light intensity measured by changing the wavelength to be measured. In order to select an absorption wavelength, which is a wavelength specifically absorbed by a substance or a functional group contained in a substance, and a reference wavelength for reference of the state of the light source and the sample, measurements are carried out by changing the absorption wavelength and the reference wavelength.

[0070] As another example, when irradiating a sample with laser light and observing the degree of temperature rise on the irradiated sample surface, the observation means is temperature measurement, the observed physical quantity is the energy density of the laser light, the irradiation time, or the type (wavelength) of the laser light, and the observation result is the radiant luminance of infrared rays. From the obtained infrared radiant luminance, it is possible to convert to temperature or calculate the rate of temperature rise using a calibration curve. The reference wavelength is a wavelength that is far enough away not to be affected by the decrease in light intensity due to the absorption peak of the target substance to be measured, and it is preferable to select a wavelength that is not more than 10 times the half-value width of the absorption peak away so as not to be too far from the absorption wavelength. More than one reference wavelength can also be used.

[0071] The value indicating the observation result may be the value of the observation result itself obtained by the observation means by changing the observed physical quantity, or may be a value obtained based on the observation result with the changed observed physical quantity. For example, it may be a value calculated using a predetermined formula from a plurality of observation results obtained by changing the observed physical quantity.

[0072] In the example where the above infrared absorption method is used as the observation means, measuring the reference wavelength in addition to the absorption wavelength is to eliminate the influences other than the light absorption peculiar to the measurement target substance. For example, it is due to the influences such as fluctuations in external light, measurement distance, dust in the optical path, surface roughness of the composition being measured, fluctuations in the absolute value of the light quantity due to external factors such as variations and fluctuations in the luminance of the irradiation light source, and variations and fluctuations in the sensitivity of the sensor. Since it is considered that the reference wavelength is also affected by the above external factors in the same way as the absorption wavelength, the above influence is canceled by the measurement result at the reference wavelength.

[0073] <Embodiment 1 Calibration Curve Acquisition Unit (A): Calibration Curve Candidate Acquisition Means (C) (0103)> The "calibration curve candidate acquisition means (C)" (0103) is configured to acquire a plurality of calibration curve candidates for each sample from the value indicating the acquired observation result and the observation physical quantity from which the observation result is obtained. Note that the plurality of calibration curve candidates may be configured to be acquired for each combination of a plurality of observation physical quantities instead of for each observation physical quantity.

[0074] In the infrared absorption method which is an example of the above observation means, for samples with known composition ratios, the measurement wavelength (absorption wavelength, reference wavelength) which is the observation physical quantity was changed, and the light intensity (observation result) at each measurement wavelength was measured. From the known composition ratios and the measurement results of the light intensities at a plurality of changed measurement wavelengths, a plurality of calibration curve candidates for each combination of the measured absorption wavelength and reference wavelength are acquired. The acquired calibration curve candidates are calibration curves for obtaining the composition ratio from the measurement results of the light intensities for each combination of the measured absorption wavelength and reference wavelength, and are candidates for selecting the calibration curves to be actually used for measuring samples with unknown composition ratios. Examples of the method from the acquisition of candidates to the determination of the calibration curves to be used will be described later.

[0075] <Embodiment 1 Calibration Curve Acquisition Unit (A): Residual Evaluation Rule Holding Means (D) (0104)> The "residual evaluation rule holding means (D)" (0104) is configured to hold a residual evaluation rule which is a rule for evaluating the residual for each of the acquired calibration curve candidates.

[0076] Examples of the residual evaluation rules include a rule of increasing the priority of a calibration curve candidate with a small sum of squared residuals obtained by squaring and summing the residuals of each data used for obtaining the calibration curve candidates, a rule of increasing the priority of a calibration curve candidate with a small mean squared residual obtained by dividing the sum of squared residuals by the number of data used for obtaining the calibration curve candidate (particularly used when the number of observation results differs for each changed observed physical quantity), and a residual evaluation rule of increasing the priority of a calibration curve candidate with a small sum of squared residuals (or mean squared residual) obtained from the calibration curve candidate obtained by excluding data of some levels of factors of sample preparation conditions or / and observed physical quantities and the excluded data. Using the sum of squared residuals (or mean squared residual) obtained from the calibration curve candidate obtained by excluding a part of the data and the excluded data is for preventing overfitting when obtaining the calibration curve candidate using all the data and for verifying the calibration curve candidate.

[0077] <Embodiment 1: Calibration Curve Acquisition Unit (A): Residual Evaluation Means (E) (0105)> The "residual evaluation means (E)" (0105) is configured to perform residual evaluation using the held residual evaluation rule.

[0078] The evaluation of the residuals is performed, for example, for each of the obtained calibration curve candidates, using the residuals that are the differences between the known composition ratios of the measured (observed) samples and the predicted composition ratios predicted using the calibration curve candidates from the observation results obtained from the samples.

[0079] <Embodiment 1: Calibration Curve Acquisition Unit (A): Selection Rule Holding Means (F) (0106)> The "selection rule holding means (F)" (0106) is configured to hold a selection rule for selecting a calibration curve candidate whose residuals have been evaluated from the results of the residual evaluation.

[0080] As selection rules, rules determined based on the observed physical quantity during observation, rules determined based on the evaluation result of the bias of the residual, and rules combining the two types of rules can be considered. Although multiple selection rules can be considered, in addition to using them individually, one or more selection rules may be combined and used. The combination method and combination order of the selection rules can also be selection rules. Specific examples of the selection rules will be introduced in some of the following Examples 3 and 4. As an example of the selection rule, priority is given so that the priority of the calibration curve candidate with a smaller sum of squared residuals or mean squared residuals from the result of the residual evaluation is higher by the residual evaluation rule, and from the calibration curve candidate with the higher priority, based on the observed physical quantity (for example, combination of wavelengths) for which the calibration curve candidate was obtained, a rule for determining the calibration curve to be used can be considered.

[0081] <Embodiment 1 Calibration Curve Acquisition Unit (A): Used Calibration Curve Determination Means (G) (0107)> The "Used Calibration Curve Determination Means (G)" (0107) is configured to determine the used calibration curve as the calibration curve for using a predetermined calibration curve candidate using the held selection rule.

[0082] <Embodiment 1 Calibration Curve Holding Unit (H) (0108)> The "Calibration Curve Holding Unit (H)" (0108) is configured to hold the acquired calibration curve.

[0083] The calibration curve held in the calibration curve holding unit (H) (0108) is not limited to one and may be one or more. For example, a user who purchases the measuring device of the present invention can determine and hold calibration curves for each measurement target species to be measured by the user (for example, measurement target species A, measurement target species B,...). When the user switches the conditions of the production line and changes the measurement target species, it can be configured to select and use the calibration curve held according to the measurement target species. For this purpose, when determining and holding the calibration curve to be used, it is further held in the calibration curve holding unit (H) in association with the calibration curve identification information for identifying the calibration curve, and further has a calibration curve selection unit for selecting the calibration curve for determining the composition ratio. The composition ratio determination unit (J) can be achieved by being configured to determine the composition ratio of the composition by multivariate analysis using the calibration curve associated with the selected calibration curve identification information.

[0084] When holding the calibration curve in the calibration curve holding unit (H), it is preferable to further associate and hold one or more pieces of calibration curve attribute information, which is attribute information regarding the calibration curve (such as the name of the measurement target substance, measurement target substance identification information, measurement conditions, calibration curve determination time information, calibration curve determination location information, calibration curve acquirer identification information, calibration curve acquisition condition information (such as the type of usage rule), etc.) with the calibration curve identification information. When the measurement conditions are included in the calibration curve attribute information, it can be configured to further have a measurement condition setting unit that acquires the measurement conditions from the calibration curve attribute information during measurement using the calibration curve and automatically sets the measurement conditions in the measuring device.

[0085] <Embodiment 1 Composition Ratio Determination Unit (J) (0109)> The "composition ratio determination unit (J)" (0109) is configured to determine the composition ratio of the composition by multivariate analysis using the held calibration curve.

[0086] As described above, by the functions of the respective parts constituting the measuring device of the present invention, a calibration curve used when determining the composition ratio of a composition by multivariate analysis can be determined from among a plurality of calibration curve candidates obtained for each sample from the value indicating the monitoring result obtained by changing the observed physical quantity and the observed physical quantity from which the observation result was obtained. In the measuring device configured as in Embodiment 1, at the actual measurement site, a plurality of samples having known composition ratios are measured in advance to obtain calibration curve candidates, and after using a residual evaluation rule among them, a used calibration curve, which is the calibration curve to be used, can be determined using a selection rule. Note that instead of measuring samples having known composition ratios for each measurement batch to determine the used calibration curve, the used calibration curve determined in the past may be held in the calibration curve holding unit (H) and used when measuring a similar composition.

[0087] <Specific Example up to Determination of Used Calibration Curve in Embodiment 1> <In the Case of Positive Electrode Active Material Slurry in the Lithium Ion Battery Positive Electrode Manufacturing Process of Embodiment 1>

[0088] For measures against global warming, electric vehicles have attracted attention and their production volume has increased significantly in recent years. Since lithium ion batteries are used in electric vehicles, the production volume of the batteries has also increased significantly in the same way. As one of the manufacturing methods of the positive electrode of a lithium ion battery, a positive electrode active material slurry, which is a mixture of a positive electrode active material (e.g., NCM: lithium nickel cobalt manganate), a binder (e.g., PVdF; polyvinylidene fluoride), a conductive assistant (e.g., acetylene black), and a solvent (e.g., NMP; N-methyl-2-pyrrolidone), is applied to a strip-shaped metal foil to form it.

[0089] Among the substances constituting the positive electrode active material slurry, those other than the solvent NMP are solid components, which remain as a film on the metal foil when the solvent volatilizes after coating. If the solid content concentration is different even when the slurry is coated with the same film thickness, the resulting film thickness after solvent volatilization will be different, which will affect the final battery performance. Therefore, in the manufacturing site where the slurry is being coated onto continuously flowing components, managing the solid content concentration of the coated film is important for maintaining quality. The infrared absorption method, which uses the characteristic light absorption wavelength of functional groups and the like contained in the materials constituting the components for solid content concentration measurement, can measure the infrared light intensity non-destructively in a short time and is a measurement method that satisfies the above conditions.

[0090] Taking the measurement of the solid content concentration of the coating film in the positive electrode manufacturing process of the lithium-ion battery shown in FIG. 7 as an example, the method for obtaining the calibration curve of the present invention will be specifically described.

[0091] <Embodiment 1 Conventional Problems in the Positive Electrode Manufacturing Process of Lithium-Ion Batteries> As the positive electrode active material of the lithium-ion battery, a general positive electrode active material of a lithium-ion battery can be used. For example, as described above, a slurry obtained by mixing lithium nickel cobalt manganate as the active material, PVdF as the binder, acetylene black as the conductive assistant, and NMP as the solvent is coated on an Al foil substrate to form the positive electrode. In the manufacture of lithium-ion batteries, if the solid content concentration is different even when the positive electrode active material slurry is coated with the same film thickness, the resulting film thickness will be different, which will affect the final battery performance. However, for the reasons described below, it was not possible to measure the solid content concentration in the production line immediately after coating, and the judgment was made based on the performance evaluation of the battery after the product was completed. Therefore, even positive electrodes that should have been removed as inherently insufficient quality had to be treated as good products and used in product assembly for commercialization, making it difficult to stably manufacture batteries that meet the desired performance.

[0092] To measure the solid content concentration of the coating film obtained by coating the positive electrode active material slurry in the production line, the infrared absorption method can be a candidate for quality control inspection because it is non-contact and non-destructive. However, there were the following problems. (1) Insufficient transmitted light intensity and reflected light intensity Since acetylene black, which is one of the materials constituting the positive electrode active material slurry for manufacturing a lithium-ion battery positive electrode, is black, the coating film becomes black, and the transmitted light intensity and reflected light intensity of infrared rays are extremely small. (2) Proximity of the absorption wavelength of the solvent and the solute material When measuring the film thickness (solid content concentration) immediately after coating (before drying) by the infrared absorption method, it is difficult to directly measure the solid content concentration of a mixture of multiple substances. Therefore, the ratio of NMP, which is the solvent, is obtained, and the rest is calculated as the solid content concentration. However, as shown in Fig. 9, the infrared absorption wavelengths of NMP, which is the solvent, and PVdF, which is the binder, are close to around 3.4 μm and around 3.3 μm (spectra of each alone. PVdF is that in the solid state. Source: NIST Chemistry WebBook. https: / / webbook.nist.gov / chemistry), making it difficult to measure only NMP.

[0093] The problem in (1) above, that is, the small light intensity of infrared rays due to transmission and reflection from the coating film, can be countered by providing a preamplifier that amplifies the signal from the infrared sensor. Regarding (2), as will be described below, it was solved by a calibration curve acquisition method in which a calibration curve candidate is acquired and then the calibration curve to be used is determined from among the calibration curve candidates.

[0094] <Embodiment 1 Method for obtaining the calibration curve to be used: Pre-measurement: Measurement wavelength> For a user who has purchased the measuring device of the present invention, regarding the method of irradiating infrared rays to the measurement target in their own production line as shown in Fig. 7 and obtaining the solid content concentration of the coating film (before drying) on the Al foil, which is the base material, a method for obtaining a calibration curve for measuring the solid content concentration of the coating film of the positive electrode active material slurry manufactured on the production line will be described at the production line. As described above, since the solid content concentration cannot be directly obtained, the ratio of the solvent is obtained and the solid content concentration is calculated by subtracting that ratio from the whole.

[0095] In the measuring device shown in FIG. 7, instead of a spectroscope for wavelength switching, it is configured to be able to switch a plurality of types of filters on the short wavelength side and the long wavelength side from the absorption wavelength of the substance to be measured, centering on the absorption wavelength of the substance to be measured. The configuration having a spectroscope is costly, and there is also a problem that the light intensity of the desired wavelength becomes small because the light is divided for each wavelength whether it is the case of splitting the light irradiated to the measurement object or the case of splitting the reflected light from the measurement object (or a combination of both). When it is desired to increase the light intensity of the reflected light as much as possible, it is better to adopt a configuration without using a spectroscope. In the configuration example shown in FIG. 7, since the composition of the measurement object contains acetylene black and has a low reflectance, due to the above two problems, it is configured without a spectroscope.

[0096] In the measurement, infrared rays of a predetermined wavelength are applied to the coating film using a filter, and the reflected light is detected by a sensor to obtain the light intensity of the reflected light. It is preferable that the device is configured such that the filter of the wavelength to be used is automatically set during the measurement. In the case of pre-measurement, after setting the sample and pressing the measurement start button, it is preferable to configure the device to automatically measure the reflected light intensity corresponding to all types of filters while rotating a disk equipped with a plurality of filters to switch the filters. The wavelength to be irradiated is the absorption wavelength of NMP, which is the solvent contained in the coating film to be measured, and light of a wavelength shorter than or / and longer than the absorption wavelength is also irradiated as a reference wavelength, and the light intensity of the reflected light is measured respectively. Measuring the light intensity at the latter reference wavelength is to determine whether the ratio of the solvent has decreased or increased when the light intensity of the reflected light at the absorption wavelength increases or decreases each time of measurement, or whether it is due to other factors (such as the irradiation light from the light source, the sensitivity of the sensor, the influence of dust in the optical path, etc.), and to exclude the influence of such factors.

[0097] If the value of the absorption wavelength specific to the material contained in the measurement target in advance is known from literature or the like, two or three types near that wavelength are used as candidates for the absorption wavelength, and several types of wavelengths are selected on the shorter wavelength side and the longer wavelength side of the absorption wavelength, and the corresponding filters are set on the filter disk in Fig. 7. The best combination of wavelengths (combination of absorption wavelength and reference wavelength) within the selected wavelengths is narrowed down by the method described later, and among the calibration curve candidates for calculating the solid content concentration from the light intensities measured using each wavelength, which one to use is determined. Along with the determination of the calibration curve to be used, the combination of the absorption wavelength candidates and reference wavelength candidates used in the measurement is determined as the wavelength combination for actual measurement.

[0098] The filter disk in Fig. 7 is a disk with a plurality of circular holes (e.g., 9 holes) on concentric circles of a disk that rotates around the central axis, and filters with different transmission wavelengths are fitted into them. During measurement, the filter disk is rotated, and the filter of the required wavelength is appropriately selected and automatically inserted into the optical path from the light source. Fig. 10 shows 9 types of wavelengths as examples of absorption wavelengths and reference wavelengths. It has 3.39μm and 3.43μm, which are wavelengths near the absorption wavelength of 3.4μm of NMP. For the 3.39μm filter, two types of filters with different half-value widths are provided. Note that the types of the filters to be set are not limited to 9.

[0099] <Embodiment 1 Method for obtaining calibration curve for use: Preliminary measurement: Measurement sample> In order to select the set of wavelengths to be used in the actual measurement, for samples with known specifications such as the composition ratio, solid content concentration, and coating film thickness in the solute, the light intensity of the reflected light is measured for each of the 9 types of wavelengths. For this purpose, samples with combinations of levels as shown in Fig. 11 were prepared. The levels are the levels of three factors: the level (3 levels) of changing the ratio of NMP as the solvent and PVdF close to the absorption wavelength in the solute, the level (5 levels) of changing the solid content concentration, and the level (3 levels) of changing the film thickness applied to the substrate, resulting in 45 types of level combination samples.

[0100] <Embodiment 1 Method for obtaining calibration curve for use: Preliminary measurement: Ratio calculation value> As described above, since the absorption peak of NMP is around 3.4 μm, among the nine wavelengths shown in Fig. 10, three wavelengths near 3.4 μm, namely 3.39 μm (two types with half-value widths of 87 nm and 138 nm) and 3.43 μm, were taken as candidate absorption wavelengths, and the light intensity was measured using two wavelengths from the remaining six wavelengths as reference wavelengths (Fig. 12). When one of the three candidate absorption wavelengths is selected as the absorption wavelength, the remaining two wavelengths may also be treated as candidates for the reference wavelength.

[0101] When it cannot be said that the light intensities of the reference wavelengths arranged on the short-wavelength side and the long-wavelength side with respect to the absorption wavelength are substantially equal, there is a concern that the error from the baseline of the spectrum will increase when obtaining the absorbance from the light intensity at the absorption wavelength of the measurement target substance NMP. When there are two reference wavelengths, if both wavelengths on the shorter wavelength side or the longer wavelength side with respect to the absorption wavelength are used, there is a similar concern that the error will increase. If the baseline is approximately constant in the region including the absorption peak, two wavelengths may be selected on the short-wavelength side or the long-wavelength side.

[0102] Furthermore, the contribution degrees of the two reference wavelengths are set.

[0103] Especially when there is an absorption peak of PVdF near the short-wavelength side of the absorption peak of NMP to be measured as shown in Fig. 9, the light intensity measurement result will be a value according to the spectrum synthesized from the spectra of NMP and PVdF. The spectrum of NMP is almost horizontal on both sides of the absorption peak at the absorption wavelength of 3.4 μm, while the spectrum of PVdF has a slightly downward slope in transmittance (the light intensity decreases as going to the long-wavelength side) centered around the absorption peak near 3.3 μm. Therefore, one wavelength on each side of the absorption wavelength of 3.4 μm is used as the reference wavelength, but the two reference wavelengths are not treated equally, and they are weighted by multiplying the contribution degrees respectively. The contribution degrees of the two wavelengths are from 0 to 1 in steps of 0.1, and are configured such that the sum of the two contribution degrees is 1. Therefore, the contribution degree can take 11 values (note that it is not limited to steps of 0.1). Therefore, considering the contribution degree, the combination of the absorption wavelength and the reference wavelength is the absorption wavelength of 3 wavelengths × the reference wavelength combination 6 C2 × The degree of contribution of 11 types = 3 × 15 × 11 = 495 types.

[0104] Absorption wavelength λ abs The light intensity measured using the light of abs is Y_λ 1 The light intensity measured using the light of the reference wavelength λ 1 is Y_λ 2 The light intensity measured using the light of the reference wavelength λ 2 If we set it as such, the relationship of the light intensities at the three wavelengths related to the ratio of the solvent NMP is expressed by the following formula 1 using the coefficients a 1 and a 2 . R NMP = 1 - Y_λ abs / (a 1 Y_λ 1 + a 2 Y_λ 2 ) Formula 1 As described above, in the above formula 1, a 1 + a 2 = 1. Formula 1 is a value obtained by using the light intensities at two reference wavelengths and correcting the light intensity at the absorption wavelength in order to exclude the influence of external factors (0 < R NMP < 1). And if the film thickness of the coating film is constant, R NMP is correlated with the ratio containing NMP.

[0105] Since the ratio of the solvent NMP and the solid content concentration in the coating film coated with the positive electrode active material slurry has a relationship where they add up to 1, the calibration curve candidate between R NMP of formula 1 correlated with the ratio of NMP and the solid content concentration will be obtained hereafter. Since the correlation between R NMP and the solid content concentration is a negative correlation, the calibration curve candidate will be a downward-sloping straight line on the right shoulder as shown in FIG. 14 described later.

[0106] As an example, 30 out of 495 results obtained by calculating the ratio values for samples with a coating film thickness of 100 μm for each solid content concentration using the above formula 1 from the measurement results in FIG. 12 are shown in FIG. 13.

[0107] <Embodiment 1 Method for obtaining calibration curve: Pre-measurement: Ratio calculation value and solid content concentration> For each ratio of PVdF and coating film thickness, for each combination of wavelengths, the ratio calculation value R expressed by Equation 1 NMP and the relationship with the solid content concentration of the measured sample are plotted as a graph with the horizontal axis: ratio calculation value R NMP and the vertical axis: solid content concentration. Fig. 14 shows, as an example, a graph showing the relationship between the ratio calculation value and the solid content concentration at a film thickness of 100 μm for the wavelength combination described in the top row of Fig. 13. Such graphs can be obtained for 495 types of wavelength combinations as described in the above calculation for each coating film thickness. For each graph, in the example of this lithium-ion battery positive electrode, an approximation line is drawn as a linear approximation. This approximation line is a calibration curve candidate for the wavelength combination. Depending on the system for obtaining the calibration curve candidate, an n-th order approximation such as a quadratic or cubic approximation may be used instead of a linear approximation.

[0108] <Embodiment 1 Method for obtaining calibration curve: Pre-measurement: Residual evaluation and selection of calibration curve to be used 1> Using the calibration curve candidate, the solid content concentration predicted for the ratio calculation value R NMP is obtained, and the sum of squares of the differences (residuals) from the measured values or / and the mean square error of the residuals is calculated. Fig. 15 shows the results corresponding to Fig. 13. In Fig. 15, the sum of squares of the residuals is shown in the rightmost column of the table. Considering the magnitude of the sum of squares of the residuals or / and the mean square error of the residuals and the magnitude relationship of the three selected wavelengths (absorption wavelength and two reference wavelengths), the calibration curve to be used is selected. The magnitude relationship of the wavelengths when two reference wavelengths are used means that one reference wavelength is located on the shorter wavelength side and one on the longer wavelength side with respect to the absorption wavelength, and the absorption wavelength is located between the two reference wavelengths.

[0109] <Embodiment 1 Method for obtaining calibration curve: Selection of calibration curve to be used 2: Cross-validation> <Embodiment 1 Method for obtaining calibration curve: Selection of calibration curve to be used 2: Excluding part of measurement data> When a calibration curve is obtained using all the measurement data, overfitting may occur due to the calibration curve candidates. When overfitting occurs, there is a possibility that the deviation becomes large and the residual becomes large for newly measured data. Cross-validation is performed to prevent overfitting. For each factor, calibration curve candidates are obtained by excluding some of the measurement data for each level. For the exclusion of the above data, about 20 to 40% of the number of levels of the measurement samples is excluded. For example, for the levels shown in FIG. 11, when there are three levels such as the ratio of PVdF and the film thickness, one level is excluded, and when there are five levels such as the solid content concentration, one or two levels are excluded.

[0110] Verification is performed by obtaining the mean square error of residuals (or the sum of squared residuals) between the excluded data and the predicted values for the excluded data obtained using the calibration curve candidates. Among the calibration curve candidates with a small mean square error of residuals for each combination of measurement wavelengths, those with an appropriate magnitude relationship of the combination of measurement wavelengths are selected. The appropriate magnitude relationship of the combination of measurement wavelengths means the magnitude relationship in which the reference wavelengths are located on the short wavelength side and the long wavelength side with respect to the absorption wavelength as described above.

[0111] <Embodiment 1 Acquisition method of calibration curve: Selection of calibration curve to be used 2: Residual evaluation and determination of calibration curve to be used> As described above, in order to avoid overfitting, cross-validation was performed in which a calibration curve was created by excluding some levels and verified with the data of the excluded levels. FIG. 16 shows the mean square error of residuals for each combination of wavelengths, and shows 30 of the results arranged in ascending order. FIG. 17 shows the 30 results as a bar graph (the numbers on the horizontal axis correspond to the order at the left end of FIG. 16). The combination of wavelengths with the smallest mean square error of residuals is the absorption wavelength λ abs is 3.39 μm, the half-value width is 138 μm, the reference wavelength λ 1 is 3.70 μm (contribution coefficient 0.1), and the reference wavelength λ 2 is 2.10 μm (contribution coefficient 0.9). This combination is for the absorption wavelength λ abs (079 μm), the reference wavelengths λ 1 (3.70 μm) and λ 2(2.10 μm) is a desirable combination of wavelengths located on the long-wavelength side and the short-wavelength side.

[0112] In this way, the calibration curve to be used is determined and obtained from among the calibration curve candidates. The above has been described by taking as an example the method for obtaining a calibration curve when using the infrared absorption method for measuring the solid content concentration, but it can also be applied to other systems. For example, X-ray diffraction data is obtained at different angles, diffraction data is obtained, and calibration curve candidates for estimating the parameters of the crystal structure are generated. Examples such as selecting the optimal calibration curve by residual evaluation and cross-validation are also conceivable.

[0113] A user who has purchased the measuring device of the present invention can determine the calibration curve to be used by the method as described above, measure the solid content concentration of the coating film of the positive electrode active material slurry with respect to the positive electrode actually manufactured on his / her own production line, and perform quality control.

[0114] <Embodiment 1 Flow of Processing> FIG. 2 is a flowchart of the operation method of the measuring device which is a computer according to Embodiment 1. As shown in this figure, in the measuring device according to Embodiment 1, there are a calibration curve acquisition step (a) (S0201), an observation result acquisition sub-step (b) (S0202) and a calibration curve candidate acquisition sub-step (c) (S0203) within the calibration curve acquisition step (a) (S0201), a residual evaluation rule holding sub-step (d) (S0204), a residual evaluation sub-step (e) (S0205), a selection rule holding sub-step (f) (S0206), a calibration curve to be used determination sub-step (g) (S0207), a calibration curve holding step (h) (S0208), and a composition ratio determination step (j) (S0209). In FIG. 2, in order to obtain a predetermined number k of calibration curve candidates and determine the calibration curve to be used from among them, in the calibration curve acquisition step (a) (S0201), the observation result acquisition sub-step (b) (S0202) and the calibration curve candidate acquisition sub-step (c) (S0203) are repeatedly executed k times.

[0115] Here, the operation method of the measuring device which is a computer is The calibration curve acquisition step (a) (S0201) performs the following processes from (S0202) to (S0207) to determine the composition ratio of the composition, and acquires a calibration curve for detecting the composition ratio from the observation results obtained by a plurality of observation means by a multivariate analysis method. Initialize the number of iterations n for obtaining k calibration curve candidates to n = 1. The observation result acquisition sub-step (b) (S0202) within the calibration curve acquisition step (a) (S0201) performs a process of acquiring values indicating observation results obtained by changing the observed physical quantity for a plurality of samples having known composition ratios. The calibration curve candidate acquisition sub-step (c) (S0203) within the calibration curve acquisition step (a) (S0201) performs a process of acquiring a plurality of calibration curve candidates for each sample from the values indicating the acquired observation results and the observed physical quantity for which the observation results were obtained. If the number of iterations n for obtaining calibration curve candidates is not equal to the predetermined number k (less than k), add 1 to the number of iterations n for obtaining calibration curve candidates and return the process to before the observation result acquisition sub-step (b) (S0202). If it is equal to k, proceed to the next step. The residual evaluation rule holding sub-step (d) (S0204) within the calibration curve acquisition step (a) (S0201) performs a process of holding a residual evaluation rule, which is a rule for evaluating the residual for each of the acquired calibration curve candidates. The residual evaluation sub-step (e) (S0205) within the calibration curve acquisition step (a) (S0201) performs a process of performing residual evaluation using the held residual evaluation rule. The selection rule holding sub-step (f) (S0206) within the calibration curve acquisition step (a) (S0201) performs a process of holding a selection rule for selecting a calibration curve candidate for which the residual has been evaluated from the results of the residual evaluation. The calibration curve determination sub-step (g) (S0207) within the calibration curve acquisition step (a) (S0201) performs a process of determining a calibration curve to use a predetermined calibration curve candidate using the held selection rule. The calibration curve holding step (h) (S0208) performs a process of holding the acquired calibration curve. The composition ratio determination step (j) (S0209) performs a process of determining the composition ratio of the composition by multivariate analysis using the calibration curve that has been held. This is an operation method for causing a measuring device, which is a computer, to execute such a series of processes.

[0116] <Embodiment 1 Description of Hardware> The hardware configuration of the computer part of the measuring device in the present Embodiment 1 will be described with reference to FIG. 3.

[0117] FIG. 3 is a diagram showing the hardware configuration of the computer part in the present Embodiment 1. As shown in this figure, an example of the computer part in the present embodiment includes an "MPU" that performs various arithmetic processes, a "main memory", a "non-volatile memory" that holds various programs and data (information), a "user I / F", a "USB, I 2 C, SPI, etc.", and a "LAN I / F". For example, an "infrared sensor" is connected via "USB, I 2 C, SPI, etc.". And they are interconnected by a "system bus" indicated by thick lines in the figure to perform transmission, reception, and processing of information. Note that this computer part can also have a configuration similar to a known PC as described above.

[0118] Various programs and data (information) stored in the non-volatile memory are expanded into the main memory when the system is started, and are configured such that, upon receiving an execution instruction, the MPU sequentially performs operations using the data according to the programs.

[0119] When the system is started, various programs and data (information) stored in the "non-volatile memory" are read out and expanded and stored in the "main memory", and at the same time, a work area that is also the working area of the program is provided. By receiving an execution instruction, the "MPU" sequentially performs operations on the data using the program. Note that a plurality of addresses are assigned to each of this "main memory" and "non-volatile memory", and the programs executed by the "MPU" can exchange data with each other by specifying and accessing the addresses, and perform processing.

[0120] In this embodiment, the programs stored in the "main memory" are a calibration curve acquisition program (a), an observation result acquisition sub-program (b), a calibration curve candidate acquisition sub-program (c), a residual evaluation rule holding sub-program (d), a residual evaluation sub-program (e), a selection rule holding sub-program (f), a used calibration curve determination sub-program (g), a calibration curve holding program (h), and a composition ratio determination program (j). In addition, values indicating observation results, calibration curve candidates, rules, selection rules, calibration curves to be used, composition ratios, etc. are stored in the "main memory" and "non-volatile memory".

[0121] The "MPU" executes the calibration curve acquisition program (a) stored in the "main memory" to execute the observation result acquisition sub-program (b) stored in the "main memory" to obtain values indicating observation results in which the observed physical quantity is changed for a plurality of samples having known composition ratios, execute the calibration curve candidate acquisition sub-program (c) stored in the "main memory" to obtain a plurality of calibration curve candidates for each sample from the values indicating the observation results obtained and the observed physical quantity for which the observation results were obtained, repeatedly execute the observation result acquisition sub-program (b) and the calibration curve candidate acquisition sub-program (c) until a predetermined number k of calibration curve candidates are obtained, A residual evaluation rule, which is a rule for evaluating the residual for each calibration curve candidate obtained by executing the residual evaluation rule holding subprogram (d) stored in the "main memory", is held. The residual evaluation is performed using the residual evaluation rule held by executing the residual evaluation subprogram (e) stored in the "main memory". A selection rule for selecting a calibration curve candidate whose residual has been evaluated from the results of the residual evaluation is held by executing the selection rule holding subprogram (f) stored in the "main memory". A calibration curve to be used is determined as a calibration curve for using a predetermined calibration curve candidate by executing the used calibration curve determination subprogram (g) stored in the "main memory" and using the held selection rule. A calibration curve for detecting the composition ratio is obtained from the observation results obtained by a plurality of observation means with the multivariate analysis method. Then, the obtained calibration curve is held by executing the calibration curve holding program (h) stored in the "main memory". Then, the composition ratio of the composition is determined by multivariate analysis using the held calibration curve by executing the composition ratio determination program (j) stored in the "main memory". Then, the determined composition ratio is output to a display device via "USB, I2C, SPI, etc.", or output to another PC or server device through a LAN line or the Internet via the "LAN I / F".

[0122] <Effect of Embodiment 1> By using the method of obtaining a calibration curve for determining the composition ratio from the observation results obtained by a plurality of observation means that change the observed physical quantity by the multivariate analysis method, the measurement device of the first embodiment can obtain a calibration curve candidate at the measurement site and determine the calibration curve to be used even in a system where it is difficult to determine the composition ratio because the observation results are difficult to obtain, and can determine the composition ratio of the composition.

[0123] <Outline of Embodiment 2> Mainly Claim 2 In the measuring device of Embodiment 2 based on Embodiment 1, the plurality of observation means are configured to observe the reflected light intensity (or the absorbance or the transmitted light intensity, which is the same hereinafter) when light of a plurality of wavelengths is applied to the composition.

[0124] <Embodiment 2 Functional Configuration> In the measuring device of Embodiment 2 based on Embodiment 1, the functional configuration is the same as that of the measuring device of Embodiment 1 shown in FIG. 1. The difference is that the plurality of observation means observe the reflected light intensity (or the absorbance or the transmitted light intensity, which is the same hereinafter) when light of a plurality of wavelengths is applied to the composition. The following describes the differences.

[0125] By measuring (observing) the reflection intensity when light of a plurality of wavelengths is applied to the composition and observing the phenomenon that the reflection intensity decreases at a specific wavelength, the presence of a functional group that absorbs the light of the specific wavelength can be known (infrared absorption method). When the types of substances constituting the composition are known and the composition ratios are unknown, the composition ratios can be estimated by observing the degree of decrease in the reflection intensity at the absorption wavelengths specific to each of the constituent substances. When the light irradiated on the composition is transmitted and not reflected, the light intensity of the transmitted light may be measured, or a reflecting mirror may be installed in the optical path after the composition is transmitted to measure the light intensity of the light that is transmitted through the composition again.

[0126] <Embodiment 2 Process Flow> The operation method of the measuring device, which is a computer of Embodiment 2 based on Embodiment 1, is the same as the flowchart showing the operation method of the measuring device, which is a computer of Embodiment 1 shown in FIG. 2. Since the differences have been described above, the description is omitted.

[0127] <Embodiment 2 Hardware Description> The hardware configuration of the measuring device, which is a computer of Embodiment 2 based on Embodiment 1, is the same as the schematic diagram of the hardware configuration of the measuring device, which is a computer of Embodiment 1 shown in FIG. 3. Since the differences have been described above, the description is omitted.

[0128] When the measurement device of Embodiment 2 uses the infrared absorption method, it can obtain a calibration curve from the observation results using light with different wavelengths for the composition ratio of the composition.

[0129] <Overview of Embodiment 3> Mainly Claim 3 The measurement device of Embodiment 3 based on either one of Embodiments 1 or 2 has the same functional configuration as the measurement device of Embodiment 1 (or Embodiment 2 based on Embodiment 1) shown in FIG. 1. When determining the calibration curve to be used in the used calibration curve determination means (G) of the measurement device of Embodiment 3, when the composition is manufactured with a predetermined target composition ratio, the wavelength of light for which a large change in the reflected light intensity is expected at the target composition ratio, and observations using light with wavelengths longer and shorter than that wavelength are included in at least a plurality of observation means, which is different from Embodiment 1 or 2. Hereinafter, the different used calibration curve determination means (G) and the differences will be described.

[0130] <Functional Configuration of Embodiment 3> <Used Calibration Curve Determination Means (G) of Embodiment 3> The "used calibration curve determination means (G)" is configured to determine, as the calibration curve to use, a predetermined calibration curve candidate using the selection rule that when the composition is manufactured with a predetermined target composition ratio among the held selection rules, the wavelength of light for which a large change in the reflected light intensity is expected at the target composition ratio, and observations using light with wavelengths longer and shorter than that wavelength are included in at least a plurality of observation means.

[0131] The measuring device of Embodiment 3 is particularly used when detecting the composition ratio of a composition by measuring the light intensity of a predetermined wavelength by the infrared absorption method. When applying the measuring device of the present Embodiment 3 to the infrared absorption method, the absorption wavelength specific to the substance for which the composition ratio is to be determined is the "wavelength of light for which a large change in the reflected light intensity is expected for the target composition ratio". The light of wavelengths longer and shorter than that wavelength is set to wavelengths located on both sides of an absorption peak having the absorption wavelength at the bottom in a spectrum showing the light intensity in the entire wavelength range centered on the absorption wavelength. It is preferable that the light of the short wavelength and the long wavelength is light having a wavelength that does not cross the valley of the absorption peak (at least separated by more than the half-value width of the absorption peak) in the spectrum.

[0132] It is also possible to use not two but two or more reference wavelengths as described above. Even when using two or more, at least one reference wavelength is selected on either the short wavelength side or the long wavelength side with respect to the absorption wavelength.

[0133] The reason for preferably selecting reference wavelengths from both the short wavelength side and the long wavelength side with respect to the absorption wavelength will be described below. The decrease in light intensity other than the infrared absorption of the measurement target substance may vary depending on the wavelength. For example, due to the absorption of other substances such as moisture in the optical path, dust in the optical path, the surface roughness of the sample, and the difference in the content ratio of the components of the composition for each sample, the light intensity may change between the short wavelength side and the long wavelength side of the absorption wavelength λ abs . An example of a case where the decrease in light intensity other than the infrared absorption is not constant in the wavelength range near the absorption wavelength including the absorption wavelength of the measurement target substance is shown in the spectral schematic diagram of FIG. 18. FIG. 18 is a diagram with the wavelength on the horizontal axis and the transmittance on the vertical axis. The transmittance and the change in light intensity in the explanation so far are almost synonymous.

[0134] In FIG. 18, the transmittance is higher on the short wavelength side. Assuming that the wavelengths λ a and λ a ' on the short wavelength side are used as reference wavelengths, the ratios of the decrease in light intensity other than the infrared absorption (decrease in transmittance) at λ a and λ a ' are (1 - T a ) and (1 - T a') on the long wavelength side, λ b , λ b 'Similarly, (1-T b ), (1-T b In the example of FIG. 18, the decrease in light intensity other than that caused by infrared absorption is larger on the long wavelength side (1-T a )<(1-T b ). Therefore, in the spectrum of Figure 18, the transmittance decreases toward the longer wavelength side, which is thought to be due to the fact that the transmittance is decreasing due to the stronger influence of factors other than infrared absorption by the substance being measured. In this example where the baseline slopes downward to the right, the decrease in transmittance other than infrared absorption at the absorption wavelength of the substance being measured is expressed as U(λ abs ), then (1-T a )<1-U(λ abs )<(1-T b ) relationship.

[0135] Using the ratio calculation formula in Equation 1 above, R NMP When calculating the ratio, the light intensity in Equation 1 can be treated as the same as the transmittance. The ratio calculation formula shown in Figure 18 is written in terms of transmittance rather than light intensity. 1 , T 2 On the short wavelength side, λ a , λ a When λ ' is substituted, the decrease in transmittance due to factors other than infrared absorption is underestimated, and the proportion of NMP is overcalculated. b , λ b 'T 1 , T 2 If you substitute this in, the proportion of NMP will be underestimated. a (λ a ' is also acceptable), and λ on the long wavelength side b (λ b By using a reference wavelength of 1000 nm or 1000 nm (or 1000 nm), the influence of the decrease in light intensity at both wavelengths other than the infrared absorption of the substance to be measured can be taken into account. The absorption peak height at the absorption wavelength of the substance to be measured can be obtained more accurately from Equation 1, which multiplies the light intensity at both wavelengths by the contribution (a value between 0 and 1, and the sum of the contributions of both wavelengths is 1).

[0136] When selecting the reference wavelength, the spectrum of the measurement object should be measured using a spectroscope and determined considering the position of the absorption wavelength. However, the configuration of a measurement device having a spectroscope has problems such as high cost, and in either the case of splitting the light irradiated to the measurement object or the case of splitting the reflected light from the measurement object (or a combination of both), since the light is split for each wavelength, the light intensity of the desired wavelength becomes small. When it is desired to increase the light intensity of the reflected light (or transmitted light) from the measurement object as much as possible, it is better to adopt a configuration without using a spectroscope. In order to address these problems, when the measurement device of the present invention has a configuration without a spectroscope, the shape of the spectrum of the composition of the measurement object becomes unknown. Therefore, for the absorption wavelengths known from literature or the like as described in the above description of the present invention, one or more candidate wavelengths of the reference wavelength are set on the short wavelength side and the long wavelength side respectively. A sample with a known composition ratio is measured, and the calibration curve candidate to be used is determined from the residual evaluation of the calibration curve candidates. The selection rule at the time of determining the calibration curve used in the third embodiment is a rule for selecting a calibration curve in which at least one or more reference wavelengths are selected from the short wavelength side and the long wavelength side respectively.

[0137] <Embodiment 3 Processing Flow> The operation method of the measurement device which is a computer of Embodiment 3 based on Embodiment 1 or Embodiment 2 is the same as the flowchart showing the operation method of the measurement device which is a computer of Embodiment 1 shown in FIG. 2 and has the same steps. The difference is the calibration curve determination sub-step (g) as described above.

[0138] Here, the operation method of the measurement device which is a computer is, In the calibration curve acquisition step (a) (S0201), in order to determine the composition ratio of the composition, the following processes from (S0202) to (S0207) are performed to acquire a calibration curve for detecting the composition ratio from the observation results obtained by a plurality of observation means by a multivariate analysis method. Initialize the number of repetitions n for obtaining a predetermined number k of calibration curve candidates to n = 1. The observation result acquisition sub-step (b) (S0202) in the calibration curve acquisition step (a) (S0201) performs a process of acquiring values indicating observation results in which the observed physical quantity is changed for each of a plurality of samples having known composition ratios. The calibration curve candidate acquisition sub-step (c) (S0203) in the calibration curve acquisition step (a) (S0201) performs a process of acquiring a plurality of calibration curve candidates for each sample from the acquired values indicating the observation results and the observed physical quantity for which the observation results were obtained. When the number of calibration curve candidate acquisition repetitions n is not equal to the predetermined number k (less than k), add 1 to the number of calibration curve candidate acquisition repetitions n and return the process to before the observation result acquisition sub-step (b) (S0202). When it is equal to k, proceed to the next step. The residual evaluation rule holding sub-step (d) (S0204) in the calibration curve acquisition step (a) (S0201) performs a process of holding a residual evaluation rule, which is a rule for evaluating the residual for each of the acquired calibration curve candidates. The residual evaluation sub-step (e) (S0205) in the calibration curve acquisition step (a) (S0201) performs a process of performing residual evaluation using the held residual evaluation rule. The selection rule holding sub-step (f) (S0206) in the calibration curve acquisition step (a) (S0201) performs a process of holding a selection rule for selecting a calibration curve candidate for which the residual has been evaluated from the results of the residual evaluation. The calibration curve to be used determination sub-step (g) (S0207) in the calibration curve acquisition step (a) (S0201) uses, among the held selection rules, a selection rule that when the composition is one manufactured with a targeted composition ratio in advance, the wavelength of light for which a large change in the reflected light intensity is expected at the targeted composition ratio and observations using light of wavelengths longer and shorter than that wavelength are included in at least a plurality of observation means, to determine a calibration curve using a predetermined calibration curve candidate. The calibration curve holding step (h) (S0208) performs a process of holding the acquired calibration curve. The composition ratio determination step (j) (S0209) performs a process of determining the composition ratio of the composition by multivariate analysis using the calibration curve that has been held. This is an operation method for causing a measuring device, which is a computer, to execute such a series of processes.

[0139] <Embodiment 3 Description of Hardware> The hardware configuration of the measuring device, which is a computer of Embodiment 3 based on Embodiment 1 or Embodiment 2, is the same as the schematic diagram of the hardware configuration of the measuring device, which is a computer of Embodiment 1 shown in FIG. 3. Since the differences have been described above, the description is omitted.

[0140] The measuring device of the present Embodiment 3 includes at least a plurality of observation means for observing the wavelength of light for which a large change is expected in the reflected light intensity for a targeted composition ratio, and light having a longer wavelength and a shorter wavelength than that wavelength. By doing so, the light intensity, which is the result of observation at the absorption wavelength, which is the wavelength of light for which a large change is expected, can be corrected, and a more accurate observation result can be obtained.

[0141] <Embodiment 4 Outline> Mainly claim 4 The measuring device of Embodiment 4 based on any one of Embodiments 1 to 3 has the same functional configuration as the measuring device of Embodiment 1 shown in FIG. 1 (or Embodiment 2 based on Embodiment 1, Embodiment 3 directly or indirectly based on Embodiment 1). The measuring device of Embodiment 4 is different from Embodiments 1 to 3 in that the selection rule used when determining the calibration curve to be used in the used calibration curve determination means (G) includes selecting an observation at a wavelength at which the ratio affected by the change is low when the reflected light intensity of the light of the composition changes due to factors other than the composition ratio. Hereinafter, the differences in the different used calibration curve determination means (G) will be described.

[0142] <Embodiment 4 Functional Configuration> <Embodiment 4 Used Calibration Curve Determination Means (G)> The "calibration curve determination means (G)" is configured to determine, using a selection rule including a rule of selecting an observation of a wavelength with a low rate of being affected by a change when the reflection intensity of light of the composition changes due to factors other than the composition ratio among the held selection rules, a calibration curve using a predetermined calibration curve candidate as the calibration curve.

[0143] By using the selection rule of selecting an observation of a wavelength with a low rate of being affected by a change when the reflection intensity of light of the composition changes due to factors other than the composition ratio, it is possible to narrow down candidates for determining a calibration curve using a calibration curve candidate that is less affected by factors other than the composition ratio.

[0144] As a specific example when the reflection intensity of light of the composition (or the same applies to absorbance or transmitted light intensity) changes due to factors other than the composition ratio, it is a case of obtaining a calibration curve for detecting the solid content concentration as the composition ratio of a composition that is a solution in which a plurality of substances are mixed, like the positive electrode active material coating process of the lithium ion battery exemplified in Embodiment 1. The composition consists of one type of solvent and a solute containing a plurality of types of substances, and as a method for detecting the solid content concentration, the ratio of the solvent is obtained and the rest is calculated as the solid content concentration. In this example, when trying to measure the light intensity of the absorption wavelength of the solvent by the infrared absorption method, since at least one of the substances constituting the solute has an absorption wavelength close to the absorption wavelength of the solvent, the reflection intensity of light of the composition changes near the absorption wavelength. In such a case, a selection rule is used to determine, as the calibration curve, a calibration curve candidate obtained by measurement using a combination of wavelengths (absorption wavelength and reference wavelength) that is less affected by the absorption peak of the solvent.

[0145] <Embodiment 4 Calibration Curve Determination Means (G): Selection Rule: Residual Evaluation + Reference Wavelength> As selection rules, for example, a rule for determining a calibration curve using a calibration curve candidate with a small sum of squared residuals or mean squared residuals by residual evaluation can be considered. Further, for example, priority is given so that the priority of a calibration curve candidate with a smaller sum of squared residuals or mean squared residuals is higher from the results of residual evaluation by a residual evaluation rule, and from the calibration curve candidate with the higher priority, based on the observed physical quantity (for example, a combination of wavelengths) from which the calibration curve candidate was obtained, a rule for determining the calibration curve to be used can be considered. As an example based on the observed physical quantity, not only is the sum of squared residuals or mean squared residuals small, but for calibration curve candidates within the smallest 10, a rule for selecting a calibration curve candidate in which the reference wavelengths are arranged separated on the short wavelength side and the long wavelength side with respect to the absorption wavelength at which the light intensity was measured when the calibration curve candidate was obtained can be considered. In the above rule, a selection rule can also be considered in which the reference wavelength is a wavelength 1 to 10 times, preferably 2 to 10 times, away from the absorption wavelength by one half-width of the absorption peak.

[0146] <Embodiment 4 Calibration Curve Determination Means (G): Selection Rule: Reference Wavelength and Residual Bias> When there are a plurality of calibration curve candidates in which the reference wavelengths are separated on the short wavelength side and the long wavelength side with respect to the absorption wavelength, the one with the smaller sum of squared residuals or mean squared residuals is determined as the calibration curve to be used. Or as a selection rule, in addition to the criterion of a calibration curve candidate with a small sum of squared residuals or mean squared residuals, a yy plot created with the known composition ratio on the horizontal axis and the predicted composition ratio obtained from the calibration curve on the vertical axis, a residual plot created with the predicted composition ratio predicted from the calibration curve for the observation result on the horizontal axis and the residual on the vertical axis, or a qq plot created with the value of the quantile of the normal distribution corresponding to the predicted composition ratio predicted from the calibration curve for the observation result on the horizontal axis and the value obtained by dividing the residual for the observation result by the standard deviation of the residual on the vertical axis. A rule for excluding calibration curve candidates with a residual bias using one or more of these can be considered.

[0147] <Embodiment 4 Calibration Curve Determination Means (G): Selection Rule: Residual Bias: yy Plot> Regarding the yy plot, a straight line passing through the plotted data is obtained by the least squares method. The range of the known composition ratio is divided into three parts, and from the smaller known composition ratio, they are defined as regions A, B, and C. For each of the regions A, B, and C, the values of the predicted composition ratios for the known composition ratios are described using box plots. For the straight line obtained by the least squares method, check for the presence or absence of a region among regions A, B, and C that has a bias where more than half of the predicted composition ratios for which the box in the box plot (indicating the middle 50% of the predicted composition ratios) deviates in the same direction. For example, if only one of the regions has a bias, or if two of the regions and the remaining one region have biases on opposite sides with respect to the straight line obtained by the least squares method, a selection rule for determining that there is a bias can be considered. In the above description, the regions are divided into three, namely A, B, and C, but two or more are sufficient. Preferably, three or more. However, if it is divided too finely, it becomes difficult to judge the bias, so the number of regions to be divided is preferably five or less.

[0148] <Embodiment 4 Calibration Curve Determination Means (G): Selection Rule: Residual Bias: Residual Plot> Regarding the residual plot, the average value of the residuals is close to 0, the average of the residuals is half or less of the standard deviation of the residuals, preferably the average is 1 / 4 or less of the standard deviation of the residuals, and more preferably 1 / 10 or less of the standard deviation. Also, the residual plot may be corrected such that the vertical axis is the value obtained by dividing each residual by the standard deviation of the residuals with respect to the predicted composition ratio predicted from the calibration curve for the observation results. Then, it becomes easier to identify how much each residual deviates from the average based on the standard deviation σ centered around 0. For example, a rule can be considered where the condition for selection is that there are no residuals exceeding 3σ. Or, similar to the yy plot, when the predicted composition ratio on the horizontal axis is divided into two or more regions, for example, three regions, the average value of the residuals in each region is at the same distance from 0. The distance is at most the standard deviation of the residuals, preferably half or less, and more preferably 1 / 4 or less.

[0149] <Embodiment 4 Calibration Curve Determination Means (G): Selection Rule: Residual Bias: qq Plot> The qq-plot is created to determine whether two distributions to be compared are similar. When the two distributions arranged on the horizontal and vertical axes have similar distributions, the graph will be a straight line. If both the predicted composition ratio predicted from the calibration curve for the observation results and the residuals for the observation results are normally distributed, the graph will be a straight line; otherwise, if either is not normally distributed, the graph will not be a straight line but a curve. The qq-plot also preferably divides the region into two or more, preferably three or more, and observes the deviation and the magnitude of the variation from the straight line where the values on both axes are equal. When the straight line is divided into three or more regions, a rule can be considered such that if the deviation from the straight line in any region exceeds the 10th percentile of the normal distribution, it is determined that the bias is large.

[0150] <Embodiment 4 Use calibration curve determination means (G): Selection rule: Determination coefficient when the calibration curve is a straight line> When the calibration curve for the observation results is obtained by the least squares method using a linear approximation formula, the closer the determination coefficient is to 1, the smaller the deviation of the predicted composition ratio from the calibration curve. The determination coefficient is 0.9 or more, preferably 0.92 or more, and more preferably 0.95 or more.

[0151] <Embodiment 4 Flow of processing> The operation method of the measuring device, which is a computer of Embodiment 4 based on any one of Embodiments 1 to 3, is the same as the flowchart showing the operation method of the measuring device, which is a computer of Embodiment 1 shown in FIG. 2, and has the same steps. The difference is only the use calibration curve determination sub-step (g) as described above.

[0152] Here, the operation method of the measuring device, which is a computer, is The calibration curve acquisition step (a) (S0201) performs the following processing from (S0202) to (S0207) to determine the composition ratio of the composition, and acquires a calibration curve for detecting the composition ratio from the observation results obtained by a plurality of observation means by a multivariate analysis method. Initialize the number of iterations n for obtaining k predetermined calibration curve candidates to n = 1. The observation result acquisition sub-step (b) (S0202) in the calibration curve acquisition step (a) (S0201) performs a process of acquiring a value indicating an observation result obtained by changing the observation physical quantity for each of a plurality of samples having a known composition ratio. The calibration curve candidate acquisition sub-step (c) (S0203) in the calibration curve acquisition step (a) (S0201) performs a process of acquiring a plurality of calibration curve candidates for each sample from the value indicating the acquired observation result and the observation physical quantity from which the observation result was obtained. If the calibration curve candidate acquisition loop count n is not equal to the predetermined number k (less than k), add 1 to the calibration curve candidate acquisition loop count n and return the process to before the observation result acquisition sub-step (b) (S0202). If it is equal to k, proceed to the next step. The residual evaluation rule holding sub-step (d) (S0204) in the calibration curve acquisition step (a) (S0201) performs a process of holding a residual evaluation rule, which is a rule for evaluating the residual for each of the acquired calibration curve candidates. The residual evaluation sub-step (e) (S0205) in the calibration curve acquisition step (a) (S0201) performs a process of performing residual evaluation using the held residual evaluation rule. The selection rule holding sub-step (f) (S0206) in the calibration curve acquisition step (a) (S0201) performs a process of holding a selection rule for selecting a calibration curve candidate for which the residual has been evaluated from the result of the residual evaluation. The used calibration curve determination sub-step (g) (S0207) in the calibration curve acquisition step (a) (S0201) uses a selection rule including a rule of selecting an observation at a wavelength with a low rate of being affected by the change when the reflection intensity of the light of the composition changes due to factors other than the composition ratio, and determines a calibration curve to use a predetermined calibration curve candidate. The calibration curve holding step (h) (S0208) performs a process of holding the acquired calibration curve. The composition ratio determination step (j) (S0209) performs a process of determining the composition ratio of the composition by multivariate analysis using the held calibration curve. This is an operating method for causing a measuring device, which is a computer, to execute such a series of processes.

[0153] <Embodiment 4 Description of Hardware> The hardware configuration of the measuring device, which is a computer according to Embodiment 4 based on any one of Embodiments 1 to 3, is the same as the schematic diagram of the hardware configuration of the measuring device, which is a computer according to Embodiment 1 shown in FIG. 3. Since the differences have been described above, the description is omitted.

[0154] By using the measuring device of the present Embodiment 4, when the light reflection intensity of the sample, which is a composition, changes due to factors other than the composition ratio, it can be determined as a calibration curve using the calibration curve obtained by measurement using a wavelength with less influence from the change, and a more accurate composition ratio can be determined.

[0155] <Embodiment 5 Overview> Mainly Claim 5 The measuring device of Embodiment 5 acquires observation results obtained by changing the observed physical quantity for a plurality of samples with an existing composition ratio, obtains a plurality of calibration curve candidates for each sample from the value indicating the observation results and the observed physical quantity for which the observation results are obtained, determines and holds the calibration curve to be used by residual evaluation, and is configured to determine the composition ratio of the composition using the held calibration curve to be used.

[0156] <Embodiment 5 Functional Configuration> FIG. 4 shows a conceptual configuration diagram of the measuring device of Embodiment 5. The measuring device (0400) of Embodiment 5 includes a calibration curve holding unit (H) (0408) and a composition ratio determination unit (J) (0409). Although not shown, the measuring device of the present invention may be configured to include observation means, or may be configured to acquire observation results from observation means of a device separate from the measuring device of the present invention. Examples of the observation means include infrared sensors such as pyroelectric type and thermoelectric power type, CCD, CMOS sensors, and phototubes. The observation means is not shown in FIG. 5.

[0157] <Embodiment 5 Explanation of Configuration> The measuring device according to Embodiment 5 is configured to hold at least one calibration curve to be used. The held calibration curve is a calibration curve that has been determined and held in advance. For example, it is a calibration curve determined and held by the manufacturer that manufactured the measuring device of the present invention. The method for obtaining the calibration curve is a method for obtaining a calibration curve that detects a composition ratio from observation results obtained by a plurality of observation means by a multivariate analysis method in order to determine the composition ratio of a composition, and includes a sample preparation step (k), an observation result acquisition step (b), a calibration curve candidate acquisition step (c), a residual evaluation step (e), and a used calibration curve determination step (g). First, each step will be described for the method of obtaining the held calibration curve. Then, the calibration curve holding unit (H) (0408) and the composition ratio determination unit (J) (0409) that constitute the measuring device (0400) according to Embodiment 5 will be described.

[0158] <Embodiment 5 Sample Preparation Step (k)> The "sample preparation step (k)" performs a process of preparing a plurality of samples with known composition ratios. For factors that are considered to affect the observation results described later under the sample creation conditions, a plurality of levels are set, and samples with a plurality of types of composition ratios are prepared. For example, taking the coating film obtained by applying a coating liquid in which a substance for forming a target film is dispersed in a solvent as a sample, the amount of the target substance (or the solid content concentration indicating the ratio contained in the coating film, or the composition ratio of the constituent substances in the solute when the solute consists of a plurality of substances) and the film thickness of the coating film are used as factors to set a plurality of levels, and corresponding samples are created.

[0159] In the example of the lithium ion battery positive electrode manufacturing process shown in FIG. 7 above, the known composition ratio is the solid content concentration. Another example is the composition ratio of carbon and a binder that holds carbon on a substrate in a coating film obtained by applying and drying a solution containing the same.

[0160] <Embodiment 5 Observation Result Acquisition Step (b)> The "observation result acquisition step (b)" performs a process of acquiring a value indicating an observation result in which an observed physical quantity is changed for each prepared sample.

[0161] An observed physical quantity is a physical quantity used in an observation means to observe a sample and obtain an observation result. "Observation" is carried out by electromagnetic waves in a broad sense, and the observed physical quantity means the frequency (or wavelength) of the electromagnetic wave used in the observation. For example, when using an observation means (infrared absorption method) of irradiating a sample with infrared rays and detecting the infrared rays emitted from the sample and observing (measuring) the light intensity, the observed physical quantity is the wavelength at the time of measuring the light intensity, and the observation result is the light intensity. For the measurement of infrared rays, infrared sensors used in known infrared absorption methods such as pyroelectric type and thermoelectric power type can be used. In this example of the infrared absorption method, the observation result with the changed observed physical quantity is the light intensity measured by changing the wavelength to be measured. In order to select the absorption wavelength specific to a substance or a functional group contained in the substance and the reference wavelength for reference of the state of the light source and the sample, the measurement is performed by changing the absorption wavelength and the reference wavelength.

[0162] As another example, when irradiating a sample with laser light and observing the degree of temperature rise on the irradiated sample surface, the observation means is temperature measurement, the observed physical quantity is the energy density or irradiation time of the laser light or the type (wavelength) of the laser light, and the observation result is the radiant luminance of infrared rays. From the obtained infrared radiant luminance, it is possible to convert to temperature or calculate the rate of temperature rise using a calibration curve. The reference wavelength is a wavelength that is far enough away not to be affected by the decrease in light intensity due to the absorption peak of the measurement target substance, and it is preferable to select a wavelength that is not more than 10 times the half-value width of the absorption peak away so as not to be too far from the absorption wavelength. More than one reference wavelength can also be used.

[0163] The value indicating the observation result may be the value of the observation result itself obtained by the observation means by changing the observed physical quantity, or may be a value obtained based on the observation result with the changed observed physical quantity. For example, it may be a value calculated using a plurality of observation results obtained by changing the observed physical quantity.

[0164] In the example where the infrared absorption method is used as the observation means, measuring the reference wavelength in addition to the absorption wavelength is to eliminate the influences other than the light absorption peculiar to the measurement target substance. For example, it is due to the influences such as fluctuations in external light, measurement distance, dust in the optical path, surface roughness of the composition being measured, fluctuations in the luminance of the irradiation light source, fluctuations in the sensitivity of the sensor, and fluctuations in the absolute value of the light quantity caused by external factors. Since it is considered that the reference wavelength is also affected by the external factors in the same way as the absorption wavelength, the above-mentioned influence is canceled by the measurement result at the reference wavelength.

[0165] <Embodiment 5 Calibration Curve Candidate Acquisition Step (c)> "Calibration Curve Candidate Acquisition Step (c)" performs a process of acquiring a plurality of calibration curve candidates for each observation physical quantity from which the observation result is obtained, from the known composition ratio for each sample and the observation result obtained from the sample. Note that the plurality of calibration curve candidates may be processed so as to be acquired for each combination of a plurality of observation physical quantities instead of for each observation physical quantity.

[0166] In the infrared absorption method which is an example of the observation means, for samples with known composition ratios, the measurement wavelength (absorption wavelength, reference wavelength), which is the observation physical quantity, was changed, and the light intensity (observation result) at each measurement wavelength was measured. From the known composition ratio and the measurement results of the light intensities at a plurality of changed measurement wavelengths, a plurality of calibration curve candidates are acquired for each combination of the measured absorption wavelength and reference wavelength. The acquired calibration curve candidates are calibration curves for obtaining the composition ratio from the measurement results of the light intensities for each combination of the measured absorption wavelength and reference wavelength, and are candidates for selecting the calibration curve to be actually used for measuring samples with unknown composition ratios. Since the example of the method from the acquisition of the candidates to the determination of the calibration curve to be used is the same as the acquisition method already described in the above Embodiment 1, the description thereof is omitted.

[0167] <Embodiment 5 Residual Evaluation Step (e)> "Residual Evaluation Step (e)" performs a process of evaluating the residual using a residual evaluation rule which is a rule for evaluating the residual for each of the acquired calibration curve candidates.

[0168] The evaluation of the residual is performed using the residual, which is the difference between the known composition ratio of the measured (observed) sample and the predicted composition ratio predicted using the calibration curve candidate from the observation results obtained from the sample, for each of the obtained calibration curve candidates, for example.

[0169] Examples of residual evaluation rules include a rule of calculating the sum of squared residuals obtained by squaring and adding the residuals of each data used for obtaining the calibration curve candidate and increasing the priority of the calibration curve candidate with a small sum of squared residuals, a rule of increasing the priority of the calibration curve candidate with a small mean squared residual obtained by dividing the sum of squared residuals by the number of data used for obtaining the calibration curve candidate (particularly used when the number of observation results is different for each changed observed physical quantity), and a residual evaluation rule of increasing the priority of the calibration curve candidate with a small sum of squared residuals (or mean squared residual) obtained from the calibration curve candidate obtained by excluding data of some levels of factors of sample preparation conditions or / and observed physical quantities and the data obtained by excluding the data. Using the sum of squared residuals (or mean squared residual) obtained from the calibration curve candidate obtained by excluding a part of the data and the data obtained by excluding the data is for preventing overfitting when obtaining the calibration curve candidate using all the data and for verifying the calibration curve candidate.

[0170] <Embodiment 5 Calibration Curve Determination Step (g)> The "calibration curve determination step (g)" performs a process of determining a calibration curve to use a predetermined calibration curve candidate using a selection rule for selecting a calibration curve candidate whose residual has been evaluated from the result of the residual evaluation.

[0171] Examples of the selection rule include a rule determined based on the observed physical quantity at the time of observation, a rule determined based on the evaluation result of the bias of the residual, and a rule combining the two types of rules. Although multiple selection rules are conceivable, in addition to using them individually, one or more selection rules may be combined and used. The combination method and combination order of the selection rules can also be selection rules. Since the selection rules have been described in Examples 3 and 4 above, the description is omitted in this example.

[0172] The method for obtaining the calibration curve to be used is the same as the specific example described in Embodiment 1, so the description is omitted in this Embodiment 5.

[0173] <Embodiment 5 Calibration Curve Holding Unit (H) (0408)> The "calibration curve holding unit (H)" (0408) is configured to hold the calibration curve obtained by the method for obtaining the calibration curve. The calibration curve obtained by a predetermined method, that is, performing from the sample preparation step (k) to the used calibration curve determination step (g), is held in the calibration curve holding unit (H).

[0174] In this Embodiment 5, the calibration curve is held in advance in the calibration curve holding unit (H) of the measuring device. For example, as described above, at the manufacturing manufacturer that manufactures the measuring device of the present invention, the calibration curve used when determining the composition ratio of the composition is determined and held in the calibration curve holding unit (H). The measuring device with the calibration curve held in this way (the held calibration curve is not limited to one) is sold to the user, and the user can measure the composition for which they want to determine (obtain) the composition ratio using the held calibration curve and determine the composition ratio.

[0175] Alternatively, the calibration curve can be determined by a measuring device having the calibration curve acquisition unit (A) described in Embodiment 1, output to the measuring device of Embodiment 5, and the measuring device of Embodiment 5 can be further provided with a calibration curve input unit to receive the input of the calibration curve output from the measuring device of Embodiment 1 and be configured to hold it in the calibration curve holding unit (H). For example, in a production line using one or a small number of measuring devices of Embodiment 1 and a large number of measuring devices of Embodiment 5, when trying to determine the composition ratio of a new composition for which the calibration curve is not held, the calibration curve can be determined by the measuring device of Embodiment 1 as described above and output to the measuring device of Embodiment 5, and it can also handle the determination of the composition ratio of the new composition.

[0176] <Embodiment 5 Composition Ratio Determination Unit (J) (0409)> The "composition ratio determination unit (J)" (0409) is configured to determine the composition ratio of the composition by multivariate analysis using the calibration curve that is held.

[0177] In the measuring device having the configuration of the fifth embodiment, instead of determining the calibration curve for use on-site during actual measurement as in the first embodiment, the calibration curve is held in advance in the calibration curve holding unit (H) of the measuring device as described above. A device equipped with a calibration curve acquisition unit for acquiring a calibration curve is connected to the measuring device of the fifth embodiment, and the calibration curve for use is determined using a sample with a known composition ratio and held in the calibration curve holding unit (H) of the measuring device of the present invention. Once a predetermined calibration curve (not limited to one, for example, an order from a customer of the destination, specifications determined by the manufacturer of the measuring device of the present invention, etc.) is held, the device equipped with the calibration curve acquisition unit can be configured to be removed. Also, when the measuring devices have the same specifications and individual differences in the measuring devices can be ignored (or tolerated), the calibration curve determined once can be configured to be copied and held in the calibration curve holding unit (H) of the measuring devices with the same specifications.

[0178] <Flow of processing in the fifth embodiment> FIG. 5 is a flowchart of the operation method of the measuring device which is a computer in the fifth embodiment. As shown in this figure, the measuring device of the first embodiment has a calibration curve holding step (h) (S0501) and a composition ratio determination step (j) (S0502). In FIG. 5, in order to acquire a predetermined number k of calibration curve candidates and determine the calibration curve for use from among them, the observation result acquisition step (b) and the calibration curve candidate acquisition step (c) are repeatedly executed k times.

[0179] Here, the operation method of the measuring device which is a computer is The calibration curve holding step (h) (S0501) is a method for obtaining a calibration curve that detects a composition ratio from observation results obtained by a plurality of observation means by a multivariate analysis method in order to determine the composition ratio of a composition. First, the number of repetitions n for obtaining a predetermined number k of calibration curve candidates is initialized to n = 1. In the sample preparation step (k) (SS0501), a process of preparing a plurality of samples with known composition ratios is performed. In the observation result acquisition step (b) (SS0502), a process of obtaining values indicating observation results in which the observed physical quantity is changed for each of the prepared samples is performed. In the calibration curve candidate acquisition step (c) (SS0503), a process of obtaining a plurality of calibration curve candidates for each sample is performed from the values indicating the obtained observation results and the observed physical quantity from which the observation results were obtained. When the number of repetitions n for obtaining calibration curve candidates is not equal to the predetermined number k (less than k), a process of adding 1 to the number of repetitions n for obtaining calibration curve candidates and returning the process to before the observation result acquisition step (b) (SS0502) is performed. When it is equal to k, the process proceeds to the next step. In the residual evaluation step (e) (SS0504), a process of performing residual evaluation is performed using a rule for evaluating the residual for each of the obtained calibration curve candidates. In the used calibration curve determination step (g) (SS0505), a process of determining, as the calibration curve to be used, a predetermined calibration curve candidate using a selection rule for selecting a calibration curve candidate whose residual has been evaluated from the results of the residual evaluation is performed, and the process of holding the calibration curve obtained by the method for obtaining a calibration curve is performed. The composition ratio determination step (j) (S0502) performs a process of determining the composition ratio of the composition by multivariate analysis using the held calibration curve. This is an operation method for causing a measuring device, which is a computer, to execute such a series of processes.

[0180] <Embodiment 5 Description of Hardware> The hardware configuration of the computer part of the measuring device in this Embodiment 5 will be described with reference to FIG. 6.

[0181] FIG. 6 is a diagram showing the hardware configuration of the computer part in the first embodiment. As shown in this figure, an example of the computer part in this embodiment includes an "MPU" that performs various arithmetic processes, a "main memory", a "non-volatile memory" that holds various programs and data (information), a "user I / F", and "USB, I 2 C, SPI, etc.", and a "LAN I / F". For example, an "infrared sensor" is connected via "USB, I 2 C, SPI, etc.". And they are interconnected by a "system bus" shown as a thick line in the figure to transmit, receive, and process information. Note that this computer part can also have a configuration similar to a known PC as described above.

[0182] Various programs and data (information) stored in the non-volatile memory are expanded into the main memory when the system is started, and are configured such that the MPU sequentially performs operations using the data according to received execution instructions.

[0183] When the system is started, various programs and data (information) stored in the "non-volatile memory" are read out, expanded, and stored in the "main memory", and at the same time, a work area that is also the working area of the program is provided. By receiving execution instructions, the MPU sequentially performs operations using the data by the program. Note that a plurality of addresses are respectively assigned to this "main memory" and "non-volatile memory", and the programs executed by the MPU can exchange data with each other and perform processing by specifying and accessing those addresses.

[0184] In this embodiment, the programs stored in the "main memory" are a calibration curve holding program (h) and a composition ratio determination program (j). Also, the calibration curve to be used, the composition ratio, etc. are stored in the "main memory" and the "non-volatile memory".

[0185] The "MPU" is A calibration curve acquisition method for detecting a composition ratio from observation results obtained by a plurality of observation means by a multivariate analysis method to determine the composition ratio of a composition by executing a calibration curve holding program (h) stored in a "main memory", the method comprising: a sample preparation step (k) of preparing a plurality of samples with known composition ratios; an observation result acquisition step (b) of obtaining values indicating observation results in which an observed physical quantity is changed for each of the prepared samples; a calibration curve candidate acquisition step (c) of obtaining a plurality of calibration curve candidates for each sample from the obtained values indicating the observation results and the observed physical quantity from which the observation results were obtained; a residual evaluation step (e) of performing a residual evaluation using a residual evaluation rule which is a rule for evaluating a residual for each of the obtained calibration curve candidates; and a used calibration curve determination step (g) of determining, using a selection rule for selecting a calibration curve candidate for which the residual has been evaluated from the results of the residual evaluation, a calibration curve to be used using a predetermined calibration curve candidate. The obtained calibration curve is held. Then, a composition ratio determination program (j) stored in the "main memory" is executed to determine the composition ratio of the composition by multivariate analysis using the held calibration curve. Then, the determined composition ratio is output to a display device via "USB, I2C, SPI, etc.", or output to another PC or server device through a LAN line or the Internet via a "LAN I / F".

[0186] <Effect of Embodiment 5> The measuring device of Embodiment 5 is a measuring device that holds a calibration curve obtained in advance by a calibration curve acquisition method for determining a composition ratio from observation results obtained by a plurality of observation means in which an observed physical quantity is changed by a multivariate analysis method, and determines the composition ratio of the composition using the held calibration curve. The composition ratio can be determined using the measuring device without acquiring a calibration curve at the location where the measuring device is used.

[0187] <Outline of Embodiment 6 Mainly Claim 6> In the measuring device of Embodiment 6 based on Embodiment 5, the plurality of observation means are configured to observe the reflected light intensity (or absorbance or transmitted light intensity, which is the same hereinafter) when light of a plurality of wavelengths is applied to the composition.

[0188] <Embodiment 6 Functional Configuration> In the measuring device of Embodiment 6 based on Embodiment 5, the functional configuration is the same as that of the measuring device of Embodiment 5 shown in FIG. 4. The difference is that the plurality of observation means observe the reflected light intensity (or absorbance or transmitted light intensity, which is the same hereinafter) when light of a plurality of wavelengths is applied to the composition. The differences will be described below.

[0189] By measuring (observing) the reflection intensity when light of a plurality of wavelengths is applied to the composition and observing the phenomenon that the reflection intensity decreases at a specific wavelength, the presence of a functional group that absorbs light of the specific wavelength can be known (infrared absorption method). When the types of substances constituting the composition are known and the composition ratios are unknown, the composition ratios can be estimated by observing the degree of decrease in the reflection intensity at the absorption wavelengths specific to each constituent substance. When the light irradiated on the composition is transmitted and not reflected, the light intensity of the transmitted light may be measured, or a reflecting mirror may be installed in the optical path after the composition is transmitted to measure the light intensity of the light transmitted through the composition again.

[0190] <Embodiment 6 Flow of Processing> The operation method of the measuring device which is a computer of Embodiment 6 based on Embodiment 5 is the same as the flowchart showing the operation method of the measuring device which is a computer of Embodiment 5 shown in FIG. 5. Since the differences have been described above, the description is omitted.

[0191] <Embodiment 6 Description of Hardware> The hardware configuration of the measuring device which is a computer of Embodiment 6 based on Embodiment 5 is the same as the schematic diagram of the hardware configuration of the measuring device which is a computer of Embodiment 5 shown in FIG. 6. Since the differences have been described above, the description is omitted.

[0192] When the measurement device of Embodiment 6 uses the infrared absorption method, it can obtain a calibration curve from the observation results using light with different wavelengths for the composition ratio of the composition.

[0193] <Overview of Embodiment 7> Mainly Claim 7 The measurement device of Embodiment 7 based on either one of Embodiments 5 or 6 has the same functional configuration as the measurement device of Embodiment 5 (or Embodiment 6 based on Embodiment 5) shown in FIG. 4. In the calibration curve determination step (g) for use in the method of obtaining the calibration curve held by the measurement device of Embodiment 7, when determining the calibration curve to be used, the selection rule used is that when the composition is manufactured with a predetermined target for its composition ratio, the wavelength of light for which a large change in reflected light intensity is expected at the target composition ratio, and observations using light with wavelengths longer and shorter than that wavelength are included in at least a plurality of observation means, which is different from Embodiment 5 or 6. Hereinafter, the different calibration curve determination step (g) and the differences will be described.

[0194] <Functional Configuration of Embodiment 7> <Calibration Curve Determination Step (g) for Use in Embodiment 7> The "calibration curve determination step (g)" is configured to determine, as the calibration curve to be used, a predetermined calibration curve candidate using the selection rule that, among the held selection rules, when the composition is manufactured with a predetermined target for its composition ratio, the wavelength of light for which a large change in reflected light intensity is expected at the target composition ratio, and observations using light with wavelengths longer and shorter than that wavelength are included in at least a plurality of observation means.

[0195] The measuring device of Embodiment 7 is particularly used when detecting the composition ratio of a composition by measuring the light intensity of a predetermined wavelength by the infrared absorption method. When applying the measuring device of Embodiment 7 to the infrared absorption method, the absorption wavelength specific to the substance for which the composition ratio is to be determined becomes the "wavelength of light for which a large change in reflected light intensity is expected for the target composition ratio". The light with a longer wavelength and a shorter wavelength than that wavelength is set to be wavelengths located on both sides of the absorption peak having the absorption wavelength as the valley bottom in the spectrum showing the light intensity in the entire wavelength range centered on the absorption wavelength. It is preferable that the light with a shorter wavelength and a longer wavelength is light having a wavelength that does not cross the valley of the absorption peak (at least separated by more than the half-value width of the absorption peak) in the spectrum.

[0196] It is also possible to use two or more reference wavelengths instead of two as described above. Even when using two or more, at least one reference wavelength is selected on either the shorter wavelength side or the longer wavelength side with respect to the absorption wavelength.

[0197] The reason why it is preferable to select reference wavelengths from both the shorter wavelength side and the longer wavelength side with respect to the absorption wavelength has been described in Embodiment 3, and thus the description is omitted in Embodiment 7.

[0198] <Embodiment 7 Process Flow> The operation method of the measuring device, which is a computer of Embodiment 7 based on Embodiment 5 or Embodiment 6, is the same as the flowchart showing the operation method of the measuring device, which is a computer of Embodiment 5 shown in FIG. 5, and has the same steps. The difference is only the use calibration curve determination step (g) (SS0505) in the acquisition method of the calibration curve held as described above.

[0199] Here, the operation method of the measuring device, which is a computer, is The calibration curve retention step (h) (S0501) is a method for obtaining a calibration curve that detects the composition ratio from the observation results obtained by a plurality of observation means by a multivariate analysis method in order to determine the composition ratio of the composition. First, the number of repetitions n for obtaining a predetermined number k of calibration curve candidates is initialized to n = 1. In the sample preparation step (k) (SS0501), a process of preparing a plurality of samples with known composition ratios is performed. In the observation result acquisition step (b) (SS0502), a process of obtaining values indicating the observation results obtained by changing the observation physical quantity for each of the prepared samples is performed. In the calibration curve candidate acquisition step (c) (SS0503), a process of obtaining a plurality of calibration curve candidates for each sample is performed from the values indicating the obtained observation results and the observation physical quantity from which the observation results were obtained. When the number of repetitions n for obtaining the calibration curve candidates is not equal to the predetermined number k (less than k), a process of adding 1 to the number of repetitions n for obtaining the calibration curve candidates and returning the process to before the observation result acquisition step (b) (SS0502) is performed. When it is equal to k, the process proceeds to the next step. In the residual evaluation step (e) (SS0504), a process of performing residual evaluation is performed using a rule for evaluating the residual for each of the obtained calibration curve candidates. In the used calibration curve determination sub-step (g) (SS0505), among the selection rules held, when the composition is one that was manufactured with a pre-targeted composition ratio, using the selection rule that the wavelength of light for which a large change in reflected light intensity is expected at the targeted composition ratio and observations using light of longer and shorter wavelengths than that wavelength are included in at least a plurality of observation means, a process of determining, as the calibration curve using a predetermined calibration curve candidate, the calibration curve obtained by the method for obtaining a calibration curve is performed, and a process of holding the calibration curve is performed. The composition ratio determination step (j) (S0502) performs a process of determining the composition ratio of the composition by multivariate analysis using the held calibration curve. This is an operation method for causing a measuring device, which is a computer, to execute such a series of processes.

[0200] <Embodiment 7 Description of Hardware> The hardware configuration of the measuring device, which is a computer according to Embodiment 7 based on Embodiment 5 or Embodiment 6, is the same as the schematic diagram of the hardware configuration of the measuring device, which is a computer according to Embodiment 5 shown in FIG. 6. Since the differences have been described above, the description is omitted.

[0201] The measuring device according to Embodiment 7 includes, in at least a plurality of observation means, the wavelength of light for which a large change is expected in the reflected light intensity for a targeted composition ratio, and observations using light with wavelengths longer and shorter than that wavelength. By doing so, the light intensity, which is the result of the observation at the absorption wavelength, which is the wavelength of light for which a large change is expected, can be corrected, and a more accurate observation result can be obtained.

[0202] <Overview of Embodiment 8> Mainly Claim 8 The measuring device according to Embodiment 8 based on any one of Embodiments 5 to 7 has the same functional configuration as the measuring device according to Embodiment 5 shown in FIG. 4 (or Embodiment 6 based on Embodiment 5, Embodiment 7 directly or indirectly based on Embodiment 5). In the calibration curve determination step (g) for use in the method for obtaining the calibration curve held by the measuring device according to Embodiment 8, the selection rule used when determining the calibration curve to be used includes a rule of selecting an observation at a wavelength at which the ratio affected by the change is low when the reflected light intensity of the light of the composition changes due to factors other than the composition ratio. This is different from Embodiments 5 to 7. Hereinafter, the differences in the different calibration curve determination steps (g) will be described.

[0203] <Functional Configuration of Embodiment 8> <Calibration Curve Determination Step (g) for Use in Embodiment 8> The "calibration curve determination step (g)" is configured to determine, using a selection rule that includes a rule of selecting an observation at a wavelength at which the ratio affected by the change is low when the reflected light intensity of the light of the composition changes due to factors other than the composition ratio among the held selection rules, a calibration curve to be used using a predetermined calibration curve candidate.

[0204] When the light reflection intensity of the composition changes due to factors other than its composition ratio, by using the selection rule of selecting the observation of wavelengths with a low ratio affected by the change, it is possible to narrow down as candidates for determining a calibration curve that uses a calibration curve candidate that is less affected by factors other than the composition ratio. Since this selection rule has been described in Embodiment 4 above, the description will be omitted in this Example 8.

[0205] <Embodiment 8 Flow of Processing> The operation method of the measuring device, which is a computer of Embodiment 8 based on any one of Embodiments 5 to 7, is the same as the flowchart showing the operation method of the measuring device, which is a computer of Embodiment 5 shown in FIG. 5, and has the same steps. The difference is only in the calibration curve determination step (g) (SS0505) in the acquisition method of the calibration curve held as described above.

[0206] Here, the operation method of the measuring device, which is a computer, is The calibration curve holding step (h) (S0501) is a method for obtaining a calibration curve for detecting the composition ratio from the observation results obtained by a plurality of observation means by a multivariate analysis method in order to determine the composition ratio of the composition. First, the number of calibration curve candidate acquisition iterations n for obtaining a predetermined number k of calibration curve candidates is initialized to n = 1. In the sample preparation step (k) (SS0501), a process of preparing a plurality of samples with known composition ratios is performed. In the observation result acquisition step (b) (SS0502), a process of obtaining values indicating the observation results in which the observed physical quantity is changed for each prepared sample is performed. In the calibration curve candidate acquisition step (c) (SS0503), a process of obtaining a plurality of calibration curve candidates for each sample from the values indicating the obtained observation results and the observed physical quantity from which the observation results were obtained is performed. When the number of calibration curve candidate acquisition iterations n is not equal to the predetermined number k (less than k), a process of adding 1 to the number of calibration curve candidate acquisition iterations n and returning the process to before the observation result acquisition step (b) (SS0502) is performed. When it is equal to k, proceed to the next step. In the residual evaluation step (e) (SS0504), a process of performing residual evaluation is performed using a rule for evaluating the residual for each of the obtained calibration curve candidates. In the calibration curve determination sub-step (g) (SS0505), among the selection rules held, when the light reflection intensity of the composition changes due to factors other than the composition ratio, a process of determining a calibration curve using a predetermined calibration curve candidate is performed using a selection rule including a rule of selecting the observation of a wavelength with a low rate of being affected by the change. A process of holding the obtained calibration curve is performed. The composition ratio determination step (j) (S0502) performs a process of determining the composition ratio of the composition by multivariate analysis using the held calibration curve. This is an operation method for causing a measuring device, which is a computer, to execute such a series of processes.

[0207] <Embodiment 8 Description of Hardware> The hardware configuration of the measuring device, which is a computer of Embodiment 8 based on any one of Embodiments 5 to 7, is the same as the schematic diagram of the hardware configuration of the measuring device, which is a computer of Embodiment 1 shown in FIG. 6. Since the differences have been described above, the description is omitted.

[0208] By using the measuring device of this Embodiment 8, when the light reflection intensity of the sample, which is a composition, changes due to factors other than the composition ratio, it is possible to determine a calibration curve using the calibration curve obtained by measurement using a wavelength with little influence by the change, and it is possible to determine a more accurate composition ratio.

[0209] <Description of Examples Using the Measuring Device of the Present Invention> It is also possible to configure to control other devices using the composition ratio of the composition determined by the measuring device of the present invention. Three examples of such control will be described below using the schematic configuration diagram of the lithium-ion battery positive electrode active material coating line shown in FIG. 19. First, the device configurations of the three examples will be described using FIG. 19 respectively, and then the controls of the three examples will be described respectively. Note that the following description is made according to the configuration of the measuring device of Embodiment 1, but the same effects can also be obtained by using the configuration of any one of Embodiments 2 to 4 based on Embodiment 1, Embodiment 5, or any one of Embodiments 6 to 8 based on Embodiment 5.

[0210] First, in the lithium-ion battery positive electrode active material coating line, an example of feedback to a kneader that kneads the positive electrode active material slurry, which is a mixture of a positive electrode active material containing a positive electrode active substance coated on an Al foil as a positive electrode substrate and a solvent, with the solid content concentration measured by the measuring device of the present invention.

[0211] Second, in the lithium-ion battery positive electrode active material coating line, an example of feedforward to the temperature control of the heater of a drying furnace that dries the coating film, with the solid content concentration measured by the measuring device of the present invention for the positive electrode active material slurry, which is a mixture of a positive electrode active material containing a positive electrode active substance coated on an Al foil as a positive electrode substrate and a solvent.

[0212] Third, in the lithium-ion battery positive electrode active material coating line, an example of feedforward to the conveyance speed at which the coating film passes through a drying furnace that dries the coating film, with the solid content concentration measured by the measuring device of the present invention for the positive electrode active material slurry, which is a mixture of a positive electrode active material containing a positive electrode active substance coated on an Al foil as a positive electrode substrate and a solvent.

[0213] <Examples of using the measuring device of the present invention: Example of device configuration: Differences from the configuration example of FIG. 7 common to the three examples>

[0214] FIG. 19 is based on FIG. 7. The difference between the measuring device (1900) of the present invention and the configuration of FIG. 7 is that the optical system (1922) is inclined at a predetermined angle θ with respect to the positive electrode substrate (1930). This is to reduce the detection of specular reflection in which the incident light is reflected from the surface of the coating film to be measured. The predetermined angle θ is preferably in the range of 12 degrees to 18 degrees with respect to the normal direction of the surface of the positive electrode substrate, and most preferably 15 degrees. In FIG. 19, the distance from the positive electrode substrate to be measured to the plane mirror of the optical system of the measuring device of the present invention is preferably about 250 mm (± about 20 mm). If it is too close, NMP volatilized from the coating film may adhere and the optical system may be contaminated. If it is too far, the light intensity of the reflected light will decrease. The distance of 250 mm is preferably appropriately set to an optimum value depending on the optical system of the measuring device, such as the diameter of the concave mirror.

[0215] The composition ratio from the composition ratio determination unit (J) (1909) of the arithmetic substrate (1924) is configured to be output to the kneading controller (1960), the temperature controller (1936), and the conveyance speed controller (1937) described later. In FIG. 7, the positive electrode substrate was configured to be uniformly coated on a member integrated from the raw material roller to the winding roller. However, in the configuration shown in FIG. 19, the positive electrode active material slurry is individually applied to the positive electrode substrates cut into a predetermined size. The predetermined size is the completed size of the positive electrode, a size slightly larger than the completed size of one positive electrode (a size that can be cut out after coating and drying), or a size including a plurality of positive electrodes (a size that can cut out a plurality of them after coating and drying).

[0216] In conjunction with the division of the positive electrode substrate, the conveying system also transfers the positive electrode substrate from the loader (1943) to the coating conveyor (1941), and the positive electrode active material coater (1934) individually coats the positive electrode substrate (1930) placed on the conveyor. The solid content concentration of the applied coating film is measured by the measuring instrument (1900) of the present invention. After the measurement, the positive electrode substrate with the coating film is temporarily stored in a buffer (1944) arranged between the drying conveyor (1942). The positive electrode substrate with the coating film stored in the buffer (1944) is appropriately transferred to the drying conveyor, basically following the first-in, first-out principle. The positive electrode substrate with the positive electrode active material film dried by the heater (1932) in the drying furnace (1938) is stored in the unloader (1945) and recovered. This is the difference from the conveying system shown in FIG. 7. Note that the means for transferring from the loader (1943) to the coating conveyor (1941), the transfer for storage from the coating conveyor (1941) to the buffer (1944), the transfer from the buffer (1944) to the drying conveyor (1942), and the transfer from the drying conveyor (1942) to the unloader (1945) (e.g., transfer robot) are not shown.

[0217] <Example 1 using the measuring device of the present invention: Control of the kneader in the lithium-ion battery positive electrode active material coating line> <Example 1 using the measuring device of the present invention: Example of device configuration: For kneading control> For the configuration shown in Fig. 7, the apparatus configuration for feedback control related to kneading of the positive electrode active material slurry added in the example of Fig. 19 includes a solute tank (1962) containing a solute material, a solvent tank (1963) containing a solvent material, a kneading controller (1960) that controls to send an amount according to a predetermined composition ratio of the solute and the solvent to a kneader (1961), and a kneader (1961) that sends the positive electrode active material slurry obtained by kneading the solute and the solvent to a positive electrode active material coater (1934). In Fig. 19, only one solute tank (1962) is shown, but when using a plurality of material substances such as a positive electrode active material (e.g., NCM; lithium nickel cobalt manganese oxide), a binder (e.g., PVdF; polyvinylidene fluoride), and a conductive assistant (e.g., acetylene black) as the solute, it can also be configured to have separate tanks for each (it is also possible to mix only the solutes in advance and store them in one tank as shown in Fig. 19). When kneading a composition using a solute composed of a plurality of substances or / and a solvent composed of a plurality of substances, the composition ratio of the substances constituting the solute and the composition ratio of the substances constituting the solvent can be configured to be sent from a server device (1951) or a PC (1952) that stores and executes a control program or the like to the kneading controller (1960) via an Internet line (1950) or a LAN line. It can also be configured to be directly input to the kneading controller (1960) in advance.

[0218] <Example 1 using the measuring device of the present invention: Kneader control: Solvent-solute ratio control> In a positive electrode active material coating line of a lithium ion battery, an example of feedback to a kneader that kneads a positive electrode active material slurry, which is a mixture of a positive electrode active material containing a positive electrode active substance coated on an Al foil as a positive electrode substrate and a solvent, with the solid content concentration measured by the measuring device of the present invention, will be described with reference to Fig. 19.

[0219] In the positive electrode active material coating line, the solid content concentration of the coating film is measured using the measuring device (1900) of the present invention. The solid content concentration obtained by the measurement is output from the composition ratio determination unit (J) (1909) to the kneading controller (1960). When it is higher than a predetermined solid content concentration, the kneading controller (1960) increases the amount of the solvent sent to the kneader (1961) or reduces the amount of the solute (when the solute is composed of a plurality of materials, the total amount of the plurality of materials). Conversely, when the solid content concentration is low, the kneading controller (1960) reduces the amount of the solvent sent to the kneader (1961) or increases the amount of the solute (when the solute is composed of a plurality of materials, the total amount of the plurality of materials).

[0220] <Example 1 of using the measuring device of the present invention: Example of determining the implementation of kneader control> The kneading controller (1960) can be configured to determine and perform the above control of the amounts of the solvent and the solute (i.e., control of the ratio of the solute to the solvent) according to the solid content concentration measurement result of one time. However, if it is determined to perform the control according to the measurement result of one time, it will react too sensitively to the influence of measurement variations and the like. Therefore, it is preferable to perform the control as in the following examples.

[0221] For example, for a given solid content concentration, the larger of the standard values is set as the upper limit value, and the smaller of the standard values is set as the lower limit value. Further, an upper threshold value and a lower threshold value are provided between the upper limit value and the lower limit value. The upper limit value and the lower limit value are defined as the solid content concentrations that must not be exceeded, and the upper threshold value and the lower threshold value inside them are provided for performing predetermined control when the measured solid content concentration reaches or exceeds them. Note that exceeding the lower limit value or the lower threshold value means falling below them across these values (the same applies hereinafter). If there are results of measuring the solid content concentration multiple times in advance, the upper threshold value is the value obtained by adding three times the standard deviation σ obtained from those results to the average of the measurement results, and the subtracted value is the lower threshold value. When there are no measurement results, the smaller of the differences from the upper limit value or the lower limit value for a given solid content concentration is regarded as 6σ, and the range corresponding to ±3σ is set as the range between the upper threshold value and the lower threshold value in the same manner as above. While there is a measured solid content concentration between the upper threshold value and the lower threshold value, the kneading controller (1960) determines that control of the amount of solvent and solute (i.e., control of the ratio of solute to solvent) is not performed.

[0222] Or, if it suddenly exceeds the threshold value when it does not show a tendency to approach the upper or lower threshold value (however, it does not exceed the upper limit value or the lower limit value), if the next measurement result returns within the threshold value range, it is determined that the above control is not performed. However, if the next measurement result also exceeds the threshold value in the same manner (however, it does not exceed the upper limit value or the lower limit value), it is an example of determining that the above control is performed. Another example is when the measurement result shows an upward or downward trend, and it can be predicted that the solid content concentration will exceed the upper threshold value or the lower threshold value before the kneading controller (1960) can adjust and reflect the ratio of the solvent and solute it sends out. In this case, it is an example of determining that the above control is performed.

[0223] When more strict management is required, such as for in-vehicle use, it may be configured to perform control in accordance with SPC (Statistical Process Control) defined in IATF16949. For example, calculate and hold the average of every five measurement results of the solid content concentration. Check the trend of the average value, and when the following situations occur, stop the device and temporarily exclude the parts with potential defects from the production line. Such situations include, for example, when there is a value exceeding the upper or lower threshold, when the average value shows a continuous upward or downward trend, and when it can be predicted that the ratio of the solvent to the solute sent out by the kneading controller (1960) will exceed the upper or lower threshold before it can be adjusted and reflected. Since there is a possibility that parts outside the standard value may still be good products, inspection can be carried out outside the line, and if they are good products, they may be returned to the line. When it is a continuous line or a single-piece material as shown in Fig. 7 and a part of it cannot be physically removed, the parts with potential defects can be marked or recorded so that they can be identified later, and then production can continue. Therefore, it is advisable to be equipped with a laser marker or the like.

[0224] Also, when it is obvious that the solid content concentration shows a tendency to deviate from the normal distribution (for example, when it is much more than 2 / 3, such as more than 90% within the range of ±1σ, or when it is much less than 2 / 3, such as less than 40% within the range of ±1σ), or when the results are continuously biased to the upper or lower side with respect to a predetermined solid content concentration (for example, when the results are continuously biased for 7 consecutive times), there may be an abnormality in the measuring device (1900) or the kneading controller (1960) of the present invention. Therefore, it is preferable to check and adjust them as soon as possible.

[0225] <Example 2 of Using the Measuring Device of the Present Invention: Temperature Control in the Lithium-Ion Battery Cathode Active Material Coating Line> <Example 2 of Using the Measuring Device of the Present Invention: Example of Device Configuration: for Temperature Control> For the configuration of FIG. 7, the device configuration for feedforward control of the temperature of the heater (1932) of the drying furnace (1938) for drying the coating film (solvent volatilization) on the positive electrode substrate (1930) added in the example of FIG. 19 consists of a thermometer (1935) (described as different because the thermometer is not shown in FIG. 7) that measures the temperature inside the drying furnace (1938) surrounded by the heater (1932) composed of the upper heater and the lower heater, and a temperature controller (1936) that outputs a control signal for heating to the heater (1932) based on the temperature information from the thermometer (1935) and the composition ratio (solid content concentration) output from the composition ratio determination unit (J) (1909) on the arithmetic board (1924). In FIG. 19, only one thermometer (1935) is shown near the upper heater, but it may be configured to have multiple thermometers arranged near the lower heater or the upper heater. Also, although the control signal output from the temperature controller (1936) to the heater (1932) is output to both the upper heater and the lower heater, it may be output to only one side. However, the reaction rate at which the output of the heater (1932) is adjusted for control and the temperature inside the drying furnace (1938) rises and falls is faster when the control signal is output to both heaters on both sides.

[0226] In FIG. 19, there is only one pair of upper and lower heaters (1932), but it may be configured to have multiple pairs. For example, the part that first heats the coating film immediately after coating is used as a heater for raising the temperature by 10 to 20 °C from the room temperature at the time of coating, and is treated as a leveling position for enhancing the uniformity of the film thickness distribution of the coating film, and then a two-stage configuration such as arranging a heater for drying is used. If the temperature profile is to be made gentle, a configuration can be adopted in which multiple stages of heaters with gradually increasing temperatures in steps are provided to reach the final drying temperature. A heater position with a lowered temperature for cooling can also be provided after these multiple heater pairs.

[0227] <Example 2 Using the Measuring Device of the Present Invention: Temperature Control: Drying Furnace Heater Output Control> In a drying furnace, NMP, which is a solvent in the coating film, is completely volatilized. However, if the solid content concentration is outside the predetermined range, for example, when the solid content concentration is low and the solvent ratio is high, there is a possibility that the solvent may not be completely volatilized and may remain in the drying furnace. If the solvent remains in the film after drying, there is a concern that it may lead to a serious accident when used as a lithium-ion battery product. Conversely, when the solid content concentration is high, drying may progress only on the surface or the adhesion to the positive electrode substrate may deteriorate. Therefore, in order to dry normally and completely, the heater output is adjusted according to the solid content concentration, and the temperature of the drying furnace is raised and lowered to achieve complete volatilization of the solvent. For this purpose, the composition ratio (solid content concentration) output from the measuring device of the present invention is fed forward, and a control signal for the heater output for temperature adjustment is output from the temperature controller (1936) to the heater (1932) of the drying furnace (1938).

[0228] In the positive electrode active material coating line, the measuring device (1900) of the present invention is used to measure the solid content concentration of the coating film. The solid content concentration obtained by the measurement is output from the composition ratio determination unit (J) (1909) to the temperature controller (1936). When it is higher than the predetermined solid content concentration, the temperature controller (1936) outputs a control signal to throttle the output to the heater (1932) and lower the temperature. When the temperature in the drying furnace drops, the drying of the film passing through the heater (1932) part becomes gentle and normalized, and drying only on the surface and deterioration of the adhesion to the substrate can be prevented. Conversely, when the solid content concentration is low, the temperature controller (1936) outputs a control signal to increase the output to the heater (1932) and raise the temperature. When the temperature of the heater rises, the temperature of the film passing through the heater (1932) part rises, the volatilization of the solvent is promoted, and complete drying can be achieved.

[0229] <Example 2 using the measuring device of the present invention: Temperature control: Drying furnace heater output control: Control implementation judgment example> The temperature controller (1936) can be configured to control the temperature of the heater (1932) according to the solid content concentration measurement result at one time. However, since temperature adjustment, especially temperature adjustment in the direction of decreasing temperature, tends to be slow to change, if it is determined to control the heater output according to the measurement result at one time, it may react overly sensitively to the influence of measurement variations, etc. Therefore, it is preferable to perform control that takes into account the transition of the solid content concentration measurement result and the temperature adjustment speed. Some examples are shown below.

[0230] For example, for a predetermined solid content concentration, the larger standard value is set as the upper limit value, and the smaller standard value is set as the lower limit value. Further, an upper threshold value and a lower threshold value are provided between the upper limit value and the lower limit value. The upper limit value and the lower limit value are set as the solid content concentration that should not be exceeded. The upper threshold value and the lower threshold value inside are provided for performing predetermined control when the measured solid content concentration reaches or exceeds them. If there are results of measuring the solid content concentration multiple times in advance, the upper threshold value is the value obtained by adding three times the standard deviation σ obtained from the results to the average of the measurement results, and the subtracted value is the lower threshold value. When there are no measurement results, the smaller difference between the upper limit value or the lower limit value and the predetermined solid content concentration is regarded as 6σ, and the range corresponding to ±3σ is set as the range between the upper threshold value and the lower threshold value in the same manner as above. This is an example where the temperature controller (1936) determines that the output control of the heater is not performed while the measured solid content concentration is between the upper threshold value and the lower threshold value.

[0231] Another example is that when the measured value suddenly exceeds the threshold value without showing a tendency to approach the threshold value (however, it does not exceed the upper limit value or the lower limit value), if the next measurement result returns within the threshold value range, it is determined that the above control is not performed. If the next measurement result also exceeds the threshold value in the same manner (however, it does not exceed the upper limit value or the lower limit value), it is determined that the above control is performed. Or, when the measurement result shows an upward or downward trend and it can be predicted that the solid content concentration will exceed the upper threshold value or the lower threshold value before the temperature controller (1936) controls the heater output and adjusts the temperature of the drying furnace, it is an example of determining that the above control is performed.

[0232] When more stringent management is required, such as for in-vehicle use, it may be configured to be controlled by SPC (Statistical Process Control) of IATF16949. For example, calculate and hold the average of every five measured results of the solid content concentration. Check the trend of the average value. When the following situations occur, stop the device and temporarily exclude the objects with potential defects from the production line. Such situations include, for example, when there is a value exceeding the upper or lower threshold, when the average value shows a continuous upward or downward trend, and when it can be predicted that the solid content concentration will exceed the upper or lower threshold before the temperature of the drying furnace reaches the desired temperature according to the control signal output by the temperature controller (1936) and the output of the heater (1932) is increased or decreased. Since there is a possibility that the product is a good product if it does not deviate from the standard value, inspect it outside the line and return it to the line if it is a good product. When it is a continuous line or a single-piece material as shown in the figure and a part of it cannot be physically removed, the part with potential defects can be marked or recorded so that it can be identified later, and then production can continue. Therefore, it is advisable to be equipped with a laser marker or the like.

[0233] Also, when it shows a tendency clearly deviating from the normal distribution (for example, when it is much more than 2 / 3, such as more than 90% within the range of ±1σ, or when it is much less than 2 / 3, such as less than 40% of the results within the range of ±1σ), or when the results are continuously biased to the upper or lower side with respect to a predetermined solid content concentration (for example, when the results are continuously biased for 7 consecutive times), there may be an abnormality in the measuring device (1900) or the temperature controller (1932) of the present invention. Therefore, it is preferable to inspect and adjust them as soon as possible.

[0234] <Example 3 of Using the Measuring Device of the Present Invention: Conveyor Speed Control in the Lithium-Ion Battery Cathode Active Material Coating Line> <Example 3 of Using the Measuring Device of the Present Invention: Example of Device Configuration: Conveyor Speed Control> For the configuration of FIG. 7, in the example of FIG. 19, for drying the coating film on the positive electrode substrate (1930) added (volatilizing the solvent), the configuration related to the feed-forward control of the conveyance speed of the positive electrode substrate in the drying furnace (1938) section is provided with a conveyance speed controller (1937) for adjusting the conveyance speed of the positive electrode substrate (1930). The conveyance speed controller (1937) acquires the composition ratio output from the composition ratio determination unit (J) (1909) and controls the conveyance speed of the positive electrode substrate (1930). Slowing down the speed of the positive electrode substrate (1930) passing through the heater (1932) can increase the drying time of the positive electrode substrate (1930) in the drying furnace. Conversely, increasing the speed can shorten the drying time.

[0235] In FIG. 19, the positive electrode substrate (1930) separates the coating conveyor (1941) including the position for coating the positive electrode active material and the drying conveyor (1942) including the drying furnace, and a buffer (1944) is provided between the two conveyors so that the speed of the drying conveyor (1942) can be adjusted with respect to the conveyance speed of the coating conveyor (1941).

[0236] If it is configured to convey with a single conveyor from the loader (1943) to the unloader (1944) (although not using a conveyance conveyor, the configuration of FIG. 7 is equivalent), the speed during the coating of the positive electrode active material changes in conjunction with the increase or decrease in the conveyance speed in the drying furnace, and the coating film thickness becomes thinner or thicker according to the coating speed. Therefore, the conveyor is divided as in FIG. 19. When using an integrated positive electrode substrate as in FIG. 7, the positive electrode active material coater may be configured to have a mechanism for automatically adjusting the coating film thickness according to the conveyance speed (for example, automatically adjusting the distance from the positive electrode substrate and the discharge pressure of the positive electrode active material). <Example 3 using the measuring device of the present invention: Conveyance speed control: Drying furnace section conveyance speed control>

[0237] In the positive electrode active material coating line shown in Fig. 19, NMP, which is a solvent in the coating film, is completely volatilized in the drying furnace. However, if the solid content concentration is out of the predetermined range, for example, when the solid content concentration is low and the solvent ratio is high, there is a possibility that the solvent may not be completely volatilized and may remain in the drying furnace. If the solvent remains in the film after drying, there is a concern that it may lead to a serious accident when used as a lithium-ion battery product. Conversely, when the solid content concentration is high, drying may proceed only on the surface or the adhesion to the positive electrode substrate may deteriorate. Therefore, in order to dry normally and completely, the conveyance speed is adjusted according to the solid content concentration, and the drying time is increased or decreased to achieve complete volatilization of the solvent. For this purpose, the composition ratio (solid content concentration) output from the measuring device of the present invention is fed forward, and a control signal for the conveyance speed is output from the conveyance speed controller (1937).

[0238] In the positive electrode active material coating line, the measuring device (1900) of the present invention is used to measure the solid content concentration of the coating film. The solid content concentration obtained by the measurement is output from the composition ratio determination unit (J) (1909) to the conveyance speed controller (1937). When it is higher than the predetermined solid content concentration, the conveyance speed controller (1937) outputs a control signal to increase the conveyance speed to the drying conveyor (1942). When the conveyance speed increases, the passing time through the heater (1932) part becomes shorter and the drying of the film is normalized, and it is possible to prevent drying only on the surface and deterioration of the adhesion to the substrate. Conversely, when the solid content concentration is low, the conveyance speed controller (1936) outputs a control signal to decrease the conveyance speed to the drying conveyor (1942). When the conveyance speed decreases, the passing time through the heater (1932) part becomes longer, and the solvent in the film can be sufficiently volatilized to achieve complete drying.

[0239] As a result of adjusting the conveyance speed of the drying conveyor (1942), when there is a deviation in the conveyance speed from the coating conveyor (1941) in the previous stage, the quantity of the positive electrode substrate with a coating film delivered from the coating conveyor (1941) to the drying conveyor (1942) is adjusted using the buffer (1944) provided between the coating conveyor (1941) and the drying conveyor (1942). For example, when the conveyance speed of the drying conveyor (1942) becomes slower than that of the coating conveyor (1941), it is temporarily stored in the buffer (1944), and the quantity of the positive electrode substrate with a coating film transferred from the buffer (1944) to the drying conveyor (1942) is adjusted. When it is likely to exceed the allowable quantity of the buffer (1944), the quantity of the positive electrode substrate (1930) transferred from the loader (1943) to the coating conveyor (1941) is adjusted, and the interval between the positive electrode substrates is adjusted to be wider. When the coating by the positive electrode active material coater (1934) is temporarily stopped without flowing the positive electrode substrate (1930), the positive electrode active material may locally accumulate near the discharge syringe of the coater or the discharge port of the slit coater, and the coating film thickness of the first positive electrode substrate at the time of resuming coating may become thick or film thickness unevenness may occur. Since there is also a possibility of the above-mentioned coating film thickening and film unevenness occurring not only in the first substrate at the time of resuming coating but also in several consecutive substrates, it is preferable to apply regularly with an interval in the transfer of the positive electrode substrate to the conveyance conveyor rather than temporarily stopping the coating.

[0240] Conversely, when the speed of the drying conveyor (1942) is adjusted to be increased compared to the above example, since there is no particular concern about the retention of the positive electrode substrate with a coating film in front of the drying conveyor (1942), there is no need to adjust the transfer interval of the positive electrode substrate on the coating conveyor (1941) side.

[0241] <Example 3 using the measuring device of the present invention::Conveyance speed control: Example of judgment for control implementation> The conveyance speed controller (1937) can be configured to control the conveyance speed of the conveyance system according to the result of a single solid content concentration measurement. However, if it is determined to perform control according to the result of a single measurement, there is a possibility of reacting overly sensitively to the influence of measurement variations, etc., and it is preferable to perform control considering the trend of the solid content concentration measurement result and the speed at which the conveyance speed adjustment is reflected. Some examples are shown below.

[0242] For example, for a given solid content concentration, the larger standard value is defined as the upper limit value, and the smaller standard value is defined as the lower limit value. Further, an upper threshold value and a lower threshold value are provided between the upper limit value and the lower limit value. The upper limit value and the lower limit value are defined as solid content concentrations that must not be exceeded, and the upper threshold value and the lower threshold value inside them are provided for performing predetermined control when the measured solid content concentration reaches or exceeds them. If there are results of measuring the solid content concentration a plurality of times in advance, the upper threshold value is the value obtained by adding three times the standard deviation σ obtained from the results to the average of the measurement results, and the subtracted value is the lower threshold value. When there are no measurement results, the smaller difference from the upper limit value or the lower limit value for a given solid content concentration is regarded as 6σ, and the range corresponding to ±3σ is set as the range between the upper threshold value and the lower threshold value in the same manner as above. This is an example where the conveyance speed controller (1937) determines that conveyance speed control is not performed while there is a measured solid content concentration between the upper threshold value and the lower threshold value.

[0243] Another example is that when a threshold value is suddenly exceeded although there is no tendency to approach the threshold value (however, the upper limit value or the lower limit value is not exceeded), if the next measurement result returns within the range of the threshold value, it is determined that the above control is not performed. When the next measurement result also exceeds the threshold value in the same manner (however, the upper limit value or the lower limit value is not exceeded), it is determined that the above control is performed. Or, when the measurement result shows an increasing or decreasing tendency and it can be predicted that the solid content concentration will exceed the upper threshold value or the lower threshold value before the conveyance speed controller (1937) outputs a conveyance speed control signal and the conveyance speed in the drying furnace is adjusted, this is an example where it is determined that the above control is performed.

[0244] When more strict management is required, such as for in-vehicle use, it may be configured to be controlled by SPC (Statistical Process Control) of IATF16949. For example, calculate and hold the average of every five measurement results of the solid content concentration. Check the trend of the average value. When the following situations occur, stop the device and temporarily exclude the parts with potential defects from the production line. Such situations include, for example, when there is a value exceeding the upper or lower threshold, or when the average value shows a continuous upward or downward trend, and it can be predicted that the solid content concentration will exceed the upper or lower threshold before the conveying speed in the drying furnace reaches the desired conveying speed according to the control signal output by the conveying speed controller (1937). Since there is a possibility that the product is a good product if it does not deviate from the standard value, conduct inspection outside the line and return it to the line if it is a good product. When it is a continuous line or a single-piece material as shown in the figure and a part of it cannot be physically removed, it may be possible to continue production after marking or recording the parts with potential defects so that they can be identified later. Therefore, it is advisable to be equipped with a laser marker or the like.

[0245] Also, when it shows a tendency clearly deviating from the normal distribution (for example, when it is much more than 2 / 3, such as more than 90% within the range of ±1σ, or when it is much less than 2 / 3, such as less than 40% of the results within the range of ±1σ), or when the results are continuously biased to the upper or lower side with respect to a predetermined solid content concentration (for example, when seven consecutive results are biased), there may be an abnormality in the measuring device (1900) or the temperature controller (1932) of the present invention. Therefore, it is preferable to perform inspection and adjustment as soon as possible.

[0246] <Example of using the measuring device of the present invention: One or more combinations of Examples 1 to 3> Although the above three examples have been described individually, as shown in FIG. 19, the three examples can be configured to function simultaneously for one production line and to adjust each of the three controllers to operate simultaneously. In that case, in order to adjust the application and the degree thereof of the three control methods, the solid content concentration obtained from the composition ratio determination unit (J), the conveyance speed obtained from the conveyance speed controller, the temperature in the drying furnace (or the output of the heater) obtained from the temperature controller, the composition ratio obtained from the kneading controller, and based on the control rule which is a rule for determining which control method to use at what ratio, it can also be configured to further include a controller control unit that controls the kneading controller, the temperature controller, and the conveyance speed controller. The controller control unit can be provided on the arithmetic board (1924), or can be provided in the server device (1951) or the PC (1952).

[0247] Any one of the above-described three examples of control, or any combination of two of them, may be used. When using a combination of two, it is preferable to configure it to have a controller control unit as described above so as to adjust the application ratio of the control method.

[0248] <5. Effect> By means of the measuring device of the present invention having the above-described configuration, observation results (e.g., light intensity) in which an observed physical quantity (e.g., wavelength) is changed for a sample having a known composition ratio are obtained, and a plurality of calibration curve candidates are obtained for each sample from the observed physical quantity and the observation results. As a result of selection using a residual evaluation rule and a selection rule (including physical rules), there is provided a calibration curve acquisition unit that determines a calibration curve to be used as the calibration curve to be used from within the calibration curve candidates, a calibration curve holding unit that holds the calibration curve acquired by the calibration curve acquisition unit, and a composition ratio determination unit that determines the composition ratio of the composition using the held calibration curve. The measuring device can use a previously held calibration curve as the calibration curve to be used. However, when the held calibration curve cannot be used for the measurement target, new calibration curve candidates can be acquired, and the calibration curve to be used can be determined and held. It is possible to save the labor and cost of acquiring a calibration curve using a separate device and recording the acquired calibration curve in the calibration curve holding unit.

[0249] Further provided is a measuring device having a calibration curve holding unit that holds a calibration curve to be used that has been determined and acquired in advance without having a calibration curve acquisition unit, and a composition ratio determination unit that determines the composition ratio of the composition using the held calibration curve to be used. When the held calibration curve cannot be used for the measurement target, it is possible to acquire calibration curve candidates by newly measuring and calculating outside the measuring device, determine the calibration curve to be used, and newly hold the determined calibration curve to be used in the measuring device.

[0250] Furthermore, provided are an operation method of the device which is a computer, a program for causing the device which is a computer to execute, and a storage medium storing the program.

[0251] By using the measuring device of the present invention, in particular, when the measurement target is a coating film using a black material with a low infrared reflectivity, or when measuring the solid content concentration of a coating film (e.g., the positive electrode of a lithium-ion battery) in which a material having an absorption peak close to the solvent to be measured is included, or when the above two cases overlap, a calibration curve can be obtained in a short time by the infrared absorption method that can be performed non-contact and non-destructively, and the solid content concentration measurement result can be obtained. In the manufacturing line, solid content concentration measurement for quality control can be performed on-site, either in full or by sampling, at high frequency, improving and maintaining the quality of components and suppressing the occurrence of defective or second-grade products that do not meet the desired performance as products incorporating the components.

[0252] Regarding those that utilize a calibration curve with a measuring device, it is configured to output a measurement result using the calibration curve held in advance. Also, when the calibration curve held for the measurement target cannot be applied, a new calibration curve is obtained by conducting experiments and calculations outside the measuring device, and the obtained calibration curve is newly held in the measuring device. However, in a multi-variety production line, etc., if it is necessary to prepare a measuring device for each variety and operate multiple lines, or record a calibration curve in the measuring device every time the manufacturing variety of a single line changes, this is inefficient in terms of cost and complexity. Therefore, for example, when the manufacturing variety changes, the measuring device is configured to be able to obtain a calibration curve by using its own functions or the functions of the associated devices, and the production efficiency will be increased when the obtained calibration curve can be immediately utilized. An example of such a case is a manufacturing line where it is desired to measure and control the composition ratio of a composition composed of multiple substances, and the substances constituting the composition are changed depending on the manufacturing variety.

Explanation of Symbols

[0253] Measuring device... 0100 Calibration curve acquisition unit (A)... 0101 Observation result acquisition means (B)... 0102 Calibration curve candidate acquisition means (C) ··· 0103 Residual evaluation rule holding means (D) ··· 0104 Residual evaluation means (E) ··· 0105 Selection rule holding means (F) ··· 0106 Calibration curve determination means for use (G) ··· 0107 Calibration curve holding section (H) ··· 0108 Composition ratio determination section (J) ··· 0109

Claims

1. A calibration curve acquisition unit (A) that acquires a calibration curve for detecting a composition ratio from observation results obtained by a plurality of observation means by a multivariate analysis method in order to determine the composition ratio of a composition, Observation result acquisition means (B) for acquiring values indicating observation results obtained by changing an observed physical quantity for each of a plurality of samples having known composition ratios, Calibration curve candidate acquisition means (C) for acquiring a plurality of calibration curve candidates for each sample from the values indicating the acquired observation results and the observed physical quantity for which the observation results were obtained, Residual evaluation rule holding means (D) that holds a residual evaluation rule, which is a rule for evaluating a residual for each of the acquired calibration curve candidates, Residual evaluation means (E) for performing a residual evaluation using the held residual evaluation rule, Selection rule holding means (F) that holds a selection rule for selecting a calibration curve candidate for which the residual has been evaluated from the results of the residual evaluation, Used calibration curve determination means (G) for determining, using the held selection rule, a calibration curve to be used by using a predetermined calibration curve candidate, A calibration curve acquisition unit (A) comprising: A calibration curve holding unit (H) that holds the acquired calibration curve, A composition ratio determination unit (J) that determines the composition ratio of the composition by multivariate analysis using the held calibration curve, A measuring device having the above.

2. The plurality of observation means are observations of the reflected light intensity (or absorbance, transmitted light intensity, absorbance + transmitted light intensity, which is the same hereinafter. The same applies hereinafter) when light of a plurality of wavelengths is applied to the composition. The measuring device according to claim 1.

3. The selection rule is such that when the composition is manufactured with a preconceived target composition ratio, the wavelength of light for which a large change in reflected light intensity is expected at the targeted composition ratio, and observations using light of wavelengths longer and shorter than that wavelength are included in at least a plurality of observation means. The measuring device according to claim 2.

4. The selection rule includes a rule of selecting an observation at a wavelength at which the ratio affected by the change is low when the reflected light intensity of the composition changes due to factors other than the composition ratio. The measuring device according to claim 3.

5. A method for acquiring a calibration curve for detecting a composition ratio from observation results obtained by a plurality of observation means by a multivariate analysis method in order to determine the composition ratio of a composition, A sample preparation step (k) of preparing a plurality of samples having known composition ratios, An observation result acquisition step (b) of acquiring a value indicating an observation result obtained by changing an observed physical quantity for each of the prepared samples, ​ A calibration curve candidate acquisition step (c) for acquiring a plurality of calibration curve candidates for each sample from the value indicating the obtained observation result and the observed physical quantity from which the observation result was obtained; A residual evaluation step (e) for performing residual evaluation using a residual evaluation rule which is a rule for evaluating the residual for each of the obtained calibration curve candidates; A used calibration curve determination step (g) for determining, using a selection rule for selecting a calibration curve candidate for which the residual has been evaluated from the results of the residual evaluation, a calibration curve to be used using a predetermined calibration curve candidate; A calibration curve holding unit (H) for holding a calibration curve obtained by a calibration curve acquisition method comprising the above; A composition ratio determination unit (J) for determining the composition ratio of the composition by multivariate analysis using the held calibration curve; A measuring device having the above.

6. The measuring device according to claim 5, wherein the plurality of observation means is an observation of the reflected light intensity (or absorbance, transmitted light intensity, absorbance + transmitted light intensity, which is the same hereinafter. The same applies hereinafter.) when light of a plurality of wavelengths is applied to the composition.

7. The selection rule is such that, when the composition is manufactured with a preconceived target composition ratio, the wavelength of light for which a large change in the reflected light intensity is expected for the targeted composition ratio, and observations using light of wavelengths longer and shorter than that wavelength are included in at least a plurality of observation means. The measuring device according to claim 6.

8. The selection rule according to claim 7 includes a rule of selecting an observation of a wavelength for which the ratio affected by the change is low when the reflected light intensity of the composition changes due to factors other than the composition ratio. The measuring device described.

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