WO2023032296A1

WO2023032296A1 - Composition evaluation method, sensor and evaluation system

Info

Publication number: WO2023032296A1
Application number: PCT/JP2022/011683
Authority: WO
Inventors: 雄介川原; 弘志北
Original assignee: コニカミノルタ株式会社
Priority date: 2021-09-02
Filing date: 2022-03-15
Publication date: 2023-03-09
Also published as: JPWO2023032296A1

Abstract

The purpose of the present invention is to provide an evaluation method of a composition in which, during research and development, or on a production line, it is possible to perform overall evaluation of the state of the target composition without affecting the composition. This evaluation method of said composition involves: a step in which a light-emitting layer is prepared that contains a light-emitting substance which changes light emission behavior in response to the state of the composition; a step in which, in a state in which the light-emitting layer and the composition are brought into contact, the light-emitting layer is irradiated with excitation light and light emission information about the light emission substance is acquired; and a step in which the light emission information is analyzed on the basis of fluorescence fingerprint information acquired in advance, and the state of the composition is evaluated.

Description

Composition evaluation method, sensor, and evaluation system

The present invention relates to a composition evaluation method, a sensor for performing this, and an evaluation system.

In the past, data science was used in the downstream side of the supply chain in the manufacturing industry, that is, in fields such as sales, inventory management, accounting, and quality assurance. On the other hand, in recent years, there has been a demand for the utilization of data science also in fields such as product prototyping, development, research, and manufacturing on the upstream side. However, in order to adapt the data science to the upstream field of the manufacturing industry, it is important to understand the concept and use it properly.

For example, if we summarize all of the subject studies and behaviors, and cut them from the perspective of "regularity" and "correlation", we can see that the development of AI (Artificial Intelligence) has brought about great gains in recent years. , It is not a theoretical and highly regular academic field such as physics and electricity, but an area where there is no regularity such as images and purchasing behavior and solutions can be found only by correlation. In these areas, the use of AI is making dramatic progress in business expansion and problem solving.

On the other hand, in the field of technology development and research and development, until now, researchers have deduced rules and correlations from data obtained from experiments as a starting point, and the "hypothesis" that is conceived from this. It was important to set up and verify (abduction) it. In fields where hypotheses can be tested a small number of times to reach a theory, there is little merit in using AI. Examples of such areas include physics and electrical engineering. On the other hand, in fields that deal with low-molecular-weight compounds, polymer materials, biotechnology, etc., it is possible to formulate hypotheses, but the effects are often diverse, and it is easy for the hypotheses to fail or to take time to verify the hypotheses.

Here, there is a method of interpreting "inductively" as the opposite of "deductively" formulating hypotheses. In Industry 4.0, an inductive approach, rather than a priori hypothesis-making, predominates. Materials informatics adapts this inductive method to chemistry, materials, and compounding, and process informatics develops it into manufacturing processes. Simplistically speaking, it is important to "minimize abduction" in order to enjoy the benefits of AI in these fields. And it is the generation of data, not AI, that is driving the industrial digital transformation (DX). For example, it is essential to generate subtle differences and characteristics of target objects, fluids, and gases as binary data.

Here, the data used in the inductive interpretation method is data that is difficult to handle deductively by human thinking. It is scientific data etc. that have not been made. Furthermore, even scientific data with well-established grounds or sufficient meaning cannot be processed deductively by human thinking due to its complexity or large amount of information. scientific data are included in inductive data.

One of the inductive data is the fluorescence fingerprint. The fluorescence fingerprint is a method of acquiring a fluorescence spectrum while changing the excitation wavelength, and is a measurement method known since the 1970s. Foods contain a relatively large amount of components that emit fluorescence when exposed to excitation light. Therefore, fluorescence fingerprints are utilized in the field of food products for quality control and the like.

On the other hand, Patent Documents 1 and 2 propose a sensor whose tip carries a fluorescent substance or reagent whose fluorescence activity changes according to the concentration of a specific substance, a system including this, and the like.

WO 1999/023476 JP-A-02-183145

As mentioned above, there is a need for digital transformation even in the manufacturing industry that deals with low-molecular-weight compounds, polymer materials, and biotechnology fields, and the use of fluorescence fingerprints is conceivable to accelerate this. However, the fact is that fluorescence fingerprinting has hardly spread outside the food field. In fields other than food, one reason is that the measurement target does not contain a component that emits fluorescence.

Therefore, it is conceivable to mix light-emitting substances with raw material compositions, intermediate products, final products, etc. in product research and development and production lines. However, the addition of such substances may impair the quality of raw material compositions and products, and is not suitable.

The present invention is an evaluation method that can comprehensively evaluate the state of a composition without affecting the composition that is the object of manufacture or research in research and development of products and production lines. The purpose is to provide sensors and evaluation systems.

As an embodiment of the present invention, a step of preparing a light-emitting layer containing a light-emitting substance whose light-emitting behavior changes according to the state of the composition, and in a state where the light-emitting layer and the composition are in contact, the light-emitting layer A composition comprising a step of irradiating with excitation light to obtain luminescence information of the luminescent substance, and a step of analyzing the luminescence information based on fluorescence fingerprint information obtained in advance to evaluate the state of the composition. Provide a method of evaluating objects.

As one embodiment of the present invention, a light-emitting portion having a light-emitting layer containing a light-emitting substance whose light-emitting behavior changes according to the state of the composition, an excitation light source that emits excitation light for exciting the light-emitting substance, and and a detector that acquires information on light emitted by a luminescent substance, wherein the wavelength of the excitation light is a wavelength determined based on pre-obtained fluorescence fingerprint information.

As another embodiment, a light-emitting portion having a light-emitting layer containing a light-emitting substance whose light-emitting behavior changes according to the state of the composition, an excitation light source for emitting excitation light for exciting the light-emitting substance, and the light-emitting substance and a detector for acquiring information on the light emitted by the , wherein the luminescent material is a material selected based on pre-obtained fluorescence fingerprint information.

As an embodiment of the present invention, the sensor and an information processing unit that analyzes the light information acquired by the detection unit by fluorescence fingerprint information acquired in advance and evaluates the state of the composition. provide the system.

According to the above composition evaluation method, it is possible to comprehensively evaluate the state of the composition in various production lines, trial production, and research without affecting the target composition. Moreover, according to the above sensor and evaluation system, the above evaluation method can be performed efficiently.

FIG. 1 is a diagram showing the flow of one embodiment of the composition evaluation method of the present invention. FIG. 2 is a diagram showing a flow of a modification of one embodiment of the composition evaluation method of the present invention. FIG. 3 is a diagram showing the flow of the luminescent material selection process. FIG. 4 is a schematic diagram showing an example of the structure of the sensor of the present invention. FIG. 5A is a fluorescence fingerprint of a composition containing a recyclable cycloolefin polymer and FIG. 5B is a fluorescence fingerprint of a composition containing a non-recyclable cycloolefin polymer used in the examples of the present invention.

Hereinafter, the present invention will be described in detail by taking one embodiment as an example. However, the invention is not limited to these embodiments.

1. Composition evaluation method The composition evaluation method of the present embodiment is a method for evaluating various performances and properties of the composition, such as determining the quality of the composition, specifying the degree of deterioration, and determining the production area and lot. is. In general, when the structure and properties of a substance to be measured are known, it is easy to select test conditions, reagents, etc., according to the substance as a target. On the other hand, evaluation is difficult when the composition contains a plurality of substances that interact in a complex manner, or when a plurality of components contribute to the properties and performance of the composition. According to the method of the present embodiment, it is possible to comprehensively evaluate the performance, properties, etc. of a composition that is difficult to evaluate by a general method.

Here, the composition to be evaluated by the composition evaluation method of the present embodiment may contain two or more components, and may be, for example, foods or various industrial products. Further, as will be described in detail later, the composition is required to sufficiently interact with the light-emitting substance in the light-emitting layer, so the composition is preferably a fluid, more preferably a gas or a liquid, and particularly preferably a liquid. In addition, the timing of performing the evaluation method of the composition of the present embodiment may be the product trial production, development, or research process, and the process of testing the production line of the product (within the test plant) or the production of the prototype. It may be a process (within a pilot plant), a product manufacturing process, or a product quality inspection process. Moreover, it may be a manufacturing process, a storage process, a quality control process, or the like of an agricultural product or its processed product.

The evaluation method of the composition of the present embodiment includes, for example, as shown in the flow chart of FIG. A step S12 of bringing the light-emitting layer and the composition into contact with each other and irradiating the light-emitting layer with excitation light to obtain light emission information of the light-emitting substance (hereinafter also referred to as a “light emission information obtaining step”). and a step S13 (hereinafter also referred to as an “evaluation step”) of analyzing the luminescence information based on the fluorescence fingerprint information obtained in advance and evaluating the state of the composition.

The evaluation method of the composition of the present embodiment may have steps other than these, if necessary. For example, as shown in the flow chart of FIG. 2, there is a step S10 of selecting a light-emitting material to be used for the light-emitting layer (hereinafter also referred to as a "light-emitting material selection step") before the step S11 of preparing the light-emitting layer. may A mode in which the luminescent material selection step S10 is performed before the luminescent layer preparation step S11 will be described below. However, this embodiment is not limited to this aspect.

(Luminescent substance selection process)
In the luminescent material selection step S10, a luminescent material to be used for the luminescent layer prepared in the luminescent layer preparation step S11, which will be described later, is selected. Specifically, as shown in the flowchart of FIG. 3, a plurality of samples containing a plurality of compositions in different states and a plurality of types of candidate luminescent substances are prepared (S101). Then, sample fluorescence fingerprints are acquired for the plurality of samples (S102). Furthermore, based on the sample fluorescence fingerprint information, a luminescent material to be used for the luminescent layer is determined (S103).

In the sample preparation step S101, first, a plurality of compositions in different states are prepared. Here, "different states" means that the properties, performance, etc. are different, and in the evaluation method of the present embodiment, it is appropriately selected according to what properties and performance are to be evaluated. . For example, when evaluating the taste and flavor of food, an ideal composition (good product) and a composition with inferior taste and flavor (defective product) are prepared. In addition, when evaluating product lots and production areas, a plurality of compositions with different properties are prepared. Furthermore, when judging the state of polymerization of monomers in the manufacturing process, a plurality of compositions having different degrees of polymerization are prepared. It should be noted that the performance or property to be evaluated in the evaluation step S13, which will be described later, does not need to be one, and may be plural. When evaluating multiple performances and properties, multiple compositions may be prepared for each performance and property.

On the other hand, in the sample preparation step S101, a plurality of candidate luminescent substances that may be used as luminescent substances in the luminescent information acquisition step S12, which will be described later, are prepared. As used herein, the term “luminescent substance” may be any substance that can emit light when irradiated with light in the luminescence information acquisition step described later and whose luminous behavior changes depending on the state of the composition. Note that "the light emission behavior changes" means that the peak wavelength of the light emitted by the substance changes, the intensity of the emitted light changes, or the spectrum of the emitted light changes. Light emitted by a light-emitting substance is usually fluorescence or phosphorescence generated by excitation of the light-emitting substance.

Examples of luminescent substances (candidate luminescent substances) whose luminescence behavior changes depending on the state of the composition include substances that hydrogen bond with components in the composition, substances that interact with π-π, and the like. Such light-emitting substances (candidate light-emitting substances) may be inorganic substances, organic substances, metal complexes, or the like. Examples of inorganic materials that can be used as luminescent materials (candidate luminescent materials) include YAG phosphors, quantum dot phosphors, thermochromic materials such as _VO2 , Ag nanoparticles, and the like. Examples of organic materials that can be used as luminescent materials (candidate luminescent materials) include fluorescent materials such as coumarins and perylenes. Examples of metal complexes that can be used as light-emitting substances (candidate light-emitting substances) include phosphorescent materials such as Eu (europium) complexes and Ir (iridium) complexes. In addition, compounds that interact with water and change the emission intensity depending on its concentration, and compounds that have optical anisotropy, become cis-type when irradiated with ultraviolet rays and become trans-type when irradiated with visible light, and have a switching function. Compounds and the like can also be used as light-emitting substances (candidate light-emitting substances). In addition, these light-emitting substances (candidate light-emitting substances) may have a group (eg, Si--O--R) for covalent bonding with a binder in the light-emitting layer, which will be described later. Alternatively, for example, a light-emitting substance obtained by bonding the above inorganic substance, organic substance, metal complex, or the like with silane coupling may be used.

Then, in step S101 of preparing a sample, the plurality of compositions and the plurality of candidate luminescent substances are mixed or brought into contact to prepare a sample. Note that the ratio of the composition in the sample to be prepared to the candidate luminescent substance, etc., is appropriately selected. Moreover, you may mix these using a solvent etc. as needed. Furthermore, it is not necessary to mix the composition and the candidate luminescent material so long as they are sufficiently contactable. Also, when preparing the samples, it is preferable to also prepare samples that do not contain the candidate luminescent material, ie samples that consist of the composition alone or the composition and solvent alone.

The number of samples to be prepared in the sample preparation step S101 is not particularly limited, and is appropriately selected according to the number of different types of compositions and the number of candidate luminescent substances. A plurality of samples can be prepared by the following method, but is not limited to this method. For example, each well of a 96-well plate contains 95 candidate luminescent substances. The one remaining well is without candidate luminescent material. Then, the first composition (eg, good product) is added to each of the 96 wells. Similarly, another plate is prepared with 95 candidate luminescent substances in each well, and a second composition (eg, reject) is added to each of the 96 wells. As a result, 192 samples can be prepared, and further samples may be prepared using the third composition, the fourth composition, or the like. Each candidate light-emitting substance may be composed of only one compound, or may be a mixture of two or more compounds.

After preparing the plurality of samples, a step of obtaining a fluorescence fingerprint (also referred to herein as a "sample fluorescence fingerprint") is performed for each of the samples (step S102). The method of acquiring the sample fluorescence fingerprint is not particularly limited, and can be performed, for example, as follows. First, each sample is irradiated with excitation light of a specific wavelength from an excitation light source. Then, the wavelength and intensity of light (fluorescence or phosphorescence) emitted by the sample when irradiated with the excitation light are measured. The wavelength of the excitation light is then shifted by a desired width (eg 10 nm) and the wavelength and intensity of the light are similarly measured. By repeating these steps, data on the wavelength of the excitation light and the wavelength and intensity of the light emitted by the sample (luminescent substance) are obtained. Then, by converting these into three-dimensional data, a sample fluorescence fingerprint is obtained. The sample fluorescence fingerprint referred to in this specification may be created based on the wavelength and intensity of light emitted by the sample (luminescent substance), for example, based on the wavelength and intensity of phosphorescence emitted by the sample (luminescent substance). It may be created by

It should be noted that the wavelength of the excitation light used to obtain the sample fluorescence fingerprint is appropriately selected according to the type of candidate luminescent substance, the type of composition, and the like. For example, when a substance that can be excited by visible light is used as the candidate light-emitting substance, visible light is used as the excitation light. On the other hand, when a substance that can be excited by ultraviolet light is used as the candidate light-emitting substance, ultraviolet light is used as the excitation light.

In addition, although the light source of the excitation light is not particularly limited, it is a supercontinuum light source (a broadband pulse light source that emits strong light in phase over a very wide wavelength range using the nonlinear effect of optical fibers, and is called an "SC light source"). is also called) or an LED. With these light sources, the amount of light can be increased, making it easier to obtain a clear fluorescence fingerprint of the sample. Note that a sample fluorescence fingerprint may be obtained by combining a plurality of light sources.

On the other hand, the wavelength and intensity of fluorescence emitted by each sample can be measured with a spectrofluorometer or the like. Measurements may be made using multiple spectrofluorometers.

Furthermore, a device that creates a sample fluorescence fingerprint from the wavelength of excitation light and the wavelength and intensity of light emitted by a candidate luminescent substance, that is, a device that converts these data into three-dimensional data, is a general information processing device such as a personal computer. etc.

After obtaining a sample fluorescence fingerprint for each sample, the information of these sample fluorescence fingerprints (also collectively referred to herein as “sample fluorescence fingerprint information”) is collected, and based on the sample fluorescence fingerprint information, a plurality of A luminescent substance suitable for the desired evaluation of the composition is determined from among the candidate luminescent substances (step S103). Specifically, the sample fluorescence fingerprints of each sample were compared, and depending on the state of the composition, the candidate luminescent substance that showed a large difference in the sample fluorescence fingerprint, the wavelength of the excitation light, and the candidate luminescent substance emitted. Identify the wavelength of light, etc. Then, the specified candidate luminescent substance is selected as the luminescent substance of the luminescent layer to be used in the luminescent information acquisition step S12, which will be described later. Note that in this step, only one light-emitting substance may be selected, or two or more light-emitting substances may be selected. Also, a plurality of light-emitting substances may be selected according to the evaluation items of the composition.

The method of comparing multiple sample fluorescence fingerprints in this step is not particularly limited, and multiple sample fluorescence fingerprints may simply be superimposed and compared. On the other hand, the sample fluorescence fingerprint information may be reduced to a lower dimension by statistical analysis processing, parameterized so as to directly represent the characteristics of each state of the composition, and compared. Examples of statistical analysis processing methods include multivariate analysis and data mining. Specific examples thereof include data structure analysis, discriminant analysis, pattern classification, multidimensional data analysis, regression analysis, machine learning, and the like.

The above data structure analysis includes principal component analysis, factor analysis, correspondence analysis and independent component analysis. The discriminant analysis includes linear discriminant analysis or nonlinear discriminant analysis. Linear discriminant analysis includes canonical discriminant analysis, and nonlinear discriminant analysis includes decision tree.

Examples of the above pattern classification include cluster analysis and multidimensional scaling. The regression analysis includes linear regression and nonlinear regression. Here, linear discriminant analysis includes Partial Least Square (PLS) regression, simple regression analysis, multiple regression analysis and principal component regression, and nonlinear discriminant analysis includes logistic regression and regression tree.

　The above machine learning includes neural networks, self-organizing maps, group learning, and genetic algorithms. Any analytical method may be used for the statistical analysis, as long as it is a technique that enables more accurate analysis of the composition.

(Emitting layer preparation step)
In the light-emitting layer preparation step, a light-emitting layer containing a light-emitting substance is prepared. The light-emitting layer may have any shape or structure as long as it can emit light while in contact with the composition in the step of obtaining light emission information, which will be described later. For example, the light-emitting layer may be arranged at the tip of the optical fiber, or may be arranged on one surface of a light-guiding planar member such as glass.

According to a probe or the like in which a light-emitting layer is arranged at the tip of an optical fiber, light is guided to the light-emitting layer via the optical fiber, and light emitted by a light-emitting substance in the light-emitting layer is transmitted to a detection device or the like via the optical fiber. be able to. Therefore, detection can be performed efficiently. A case where the light-emitting layer is arranged at the tip of the optical fiber (probe) will be described below as an example, but the present embodiment is not limited to this aspect.

An example of the structure of the sensor including the probe is shown in FIG. The sensor 200 has a probe 21, a light source 22, a detector 23, and

cables

210a and 210b connecting these.

The probe 21 only needs to have a light guide member 21a and a light emitting layer 21b containing a light emitting material disposed at the tip of the light guide member 21a. The light-emitting substance included in the light-emitting layer 21b is, for example, the light-emitting substance selected in the above-described light-emitting substance selection process.

Here, the light guide member 21a may be any member as long as it can guide the light (fluorescence or phosphorescence) emitted by the light-emitting substance in the light-emitting layer 21b to the detection section 23 side. The light guide member 21a can guide the excitation light for exciting the light-emitting substance in the light-emitting layer 21b emitted by the light source 22 to the light-emitting layer 21b side, and the light-emitting substance in the light-emitting layer 21b emits light. A member capable of guiding light (fluorescence or phosphorescence) to the detection section 23 side is preferable because the excitation light can be reliably applied to the light-emitting substance.

The light guide member 21a may be an optical fiber, and may be composed of one type of optical fiber, for example. In this case, the optical fiber guides the excitation light from the light source 22 to the light emitting layer 21b side and guides the light (fluorescence or phosphorescence) emitted by the light emitting substance from the light emitting layer 21b side to the detection section 23 side. On the other hand, the light guide member 21a may be composed of multiple types of optical fibers. In this case, the light guide member 21a includes an optical fiber for guiding the excitation light from the light source 22 to the light emitting layer 21b side, and for guiding the light (fluorescence and phosphorescence) emitted by the light emitting substance from the light emitting layer 21b side to the detection section 23 side. optical fibers, respectively. However, from the viewpoint of space saving, it is preferable that the light guide member 21a is made of one type of optical fiber.

Cables

210a, 210b and the like may be arranged between the light guide member 21a of the probe 21 and the light source 22 or the detection section 23 as necessary.

On the other hand, the light emitting layer 21b may be arranged at least at the tip of the light guide member 21a (probe 21), and may be arranged so as to cover the entire light guide member 21a, for example. The light-emitting layer 21b may be a layer containing only a light-emitting substance. Examples of layers containing only luminescent materials include monolayers such as porous films and self-assembled monolayers. Such a monomolecular film may cover the entire tip of the probe, or, for example, may cover the tip of the probe in a sea-island pattern, that is, partially. However, from the viewpoint of strength, etc., it is preferable that the luminescent material is a layer bound to the light guide member 21a by a binder.

In addition, the amount of the light-emitting substance in the light-emitting layer 21b is not particularly limited as long as it can sufficiently come into contact with the composition and can sufficiently emit light (fluorescence or phosphorescence) upon receiving excitation light. . The light-emitting layer 21b may contain only one kind of light-emitting substance, or may contain two or more kinds thereof. For example, when evaluating a plurality of performances and properties of the composition, one light-emitting layer 21b may contain a plurality of light-emitting substances for evaluating each performance and property. On the other hand, a plurality of probes 21 may be prepared for each luminescent substance, and the luminescence information acquisition step S12, which will be described later, may be performed using these probes. When a plurality of probes 21 are prepared, the luminescence information from each luminescent substance is not mixed, and it becomes easier to evaluate in the evaluation step S13 described later.

On the other hand, the type of binder contained in the light-emitting layer 21b is not particularly limited, but a material capable of transmitting excitation light for exciting the light-emitting substance and light emitted by the light-emitting substance is preferable. For example, an inorganic material such as silicone resin or an organic resin such as epoxy resin may be used. The light-emitting layer 21b may contain only one type of binder, or may contain two or more types of binders.

Here, the method of forming the light emitting layer 21b at the tip of the light guide member 21a is not particularly limited. For example, a luminescent material and a binder precursor (for example, triethoxysilane) may be mixed, applied around the light guide member 21a, and cured to form the luminescent layer 21b. At this time, only the binder precursor may be polymerized to cure the mixture, or the luminescent material and the binder precursor may be copolymerized to cure the mixture. A sol-gel reaction may be used for the polymerization, such as when the binder precursor is triethoxysilane. Alternatively, for example, an epoxy resin (polymer) or the like, a light-emitting substance, and a solvent may be mixed and applied around the light guide member 21a, and then the solvent may be removed to form the light-emitting layer 21b. In the case of forming a light-emitting layer consisting only of a light-emitting substance, a light-emitting substance having a group (—Si(OCH ₃ ) ₃ ) derived from a silane coupling agent is applied to the tip of an optical fiber by an inkjet method or the like. may be cured by polycondensation by a sol-gel reaction or the like. Alternatively, for example, the tip of the optical fiber may be immersed in a light-emitting substance having a group (—Si(OCH ₃ ) ₃ ) derived from a silane coupling agent, followed by polycondensation and curing. When the light-emitting layer is formed on a light-guiding planar member such as glass instead of the tip of the optical fiber, the same method can be used to form the light-emitting layer.

Here, the light source 22 that can be used for the sensor 200 is not particularly limited as long as it can irradiate light of a predetermined wavelength, and can be a supercontinuum light source, an LED, a white light source, or the like. Further, the light source 22 may include a filter for irradiating only a specific wavelength, a mechanism for adjusting the intensity of light, and the like.

On the other hand, the detection unit 23 only needs to be able to measure the wavelength and intensity of the light (fluorescence or phosphorescence) emitted by the light-emitting substance, and can be a spectrofluorophotometer, for example. The detection unit 23 may be connected to an information processing device (not shown) for analyzing the light emission information of the light emitting substance.

(Light emission information acquisition step)
In the luminescent information acquisition step S12, the luminescent layer prepared in the luminescent layer preparation step S11 described above, for example, the luminescent layer 21b of the probe 21 of the sensor 200 is brought into contact with the composition, and in this state, excitation light from the light source 22 is emitted. The light-emitting substance in the light-emitting layer 21b is irradiated.

The method of contacting the light-emitting layer 21b with the composition is not particularly limited, and for example, the light-emitting layer 21b may be immersed in the composition. Also, a composition may be applied to the surface of the light-emitting layer 21b.

Here, when the luminescence information acquisition step S12 is performed during the manufacture of the composition, the composition may be sampled and brought into contact with the luminescent layer 21b. That is, the light emission information acquisition step S12 may be performed offline. Alternatively, the luminescent layer may be immersed in the composition in the production line to bring them into contact. That is, the light emission information acquisition step S12 may be performed inline. In this embodiment, since the luminescent substance is immobilized on the surface of the probe, the possibility of contamination of the composition with the luminescent substance is extremely low, and the process of acquiring luminescence information can be performed even in-line.

Further, the wavelength of the excitation light with which the light-emitting layer 21b (light-emitting substance) is irradiated in the light-emitting information acquisition step S12 may be a specific wavelength with a large difference in the fluorescence fingerprint in the above-described light-emitting substance selection step S10. On the other hand, since a large amount of information can be obtained by irradiating light of a wide wavelength range as excitation light, light of a wide wavelength range may be sequentially irradiated while shifting the wavelengths. However, when performing the light emission information acquisition process inline, it is preferable to irradiate light of a specific wavelength from the viewpoint of efficiency.

In the luminescence information obtaining step S12, the light emitted by the luminous substance may be detected by a detection device or the like. . The luminescence information acquired by the detection unit 23 may be information that enables the composition to be evaluated in the evaluation step S13 described later. For example, it may be only the intensity of a specific wavelength emitted by a light-emitting substance, or the spectrum of light emitted by a light-emitting substance. The luminescence information acquired in this step may be information about fluorescence emitted by a light-emitting substance, or information about phosphorescence emitted by a light-emitting substance.

When the sensor 200 is used, the luminescence information may be acquired using only one probe 21, but a plurality of probes 21 having different types of luminescent substances may be prepared to acquire a plurality of luminescence information. may

Alternatively, a probe (not shown) that does not have the light-emitting layer 21b may be separately prepared to obtain the difference in light-emission information. Obtaining the difference means canceling the effects of various factors other than the item of interest and obtaining only the effect of the item of interest. This can increase the signal/noise ratio to useful information. Specifically, a probe 21 having a luminescent layer 21b and a probe whose luminescent layer does not contain a luminescent substance are prepared. Then, each of these is brought into contact with the composition, and in this state, the probe 21 is irradiated with light (excitation light) from the light source 22 . Light from each probe is detected by the detector 23 . After that, the data detected from the probe whose light-emitting layer does not contain the light-emitting substance is subtracted from the data detected from the probe 21 with the light-emitting layer 21b. Accordingly, noise can be removed, and luminescence information derived from the luminescence substance can be acquired more accurately.

Also, in the light emission information acquisition step S12, a plurality of data may be acquired at regular time intervals. By acquiring a plurality of data at regular time intervals, for example, the reaction speed, aging speed, fermentation speed, etc., drying speed, stability over time, etc. when manufacturing a specific product can be grasped over time.

(Evaluation process)
In the evaluation step S13, the luminescence information obtained in the luminescence information obtaining step S12 is analyzed based on the previously obtained fluorescence fingerprint information to evaluate the state of the composition. The fluorescence fingerprint information used in the evaluation step S13 may be the sample fluorescence fingerprint information obtained in the above-described luminescent material selection step S10, or may be separately obtained fluorescence fingerprint information.

For example, if the luminescent substance selection step S10 is not performed, a plurality of samples are prepared by mixing the luminescent substance and a plurality of compositions in different states in advance, and fluorescence fingerprints are obtained for each sample. . Information on these fluorescent fingerprints (fluorescent fingerprint information) may then be used for evaluation of the composition. The method for obtaining the fluorescent fingerprint information is the same as the method for obtaining the sample fluorescent fingerprint information in the luminescent material selection step S10 described above.

Here, in the evaluation step S13, the fluorescent fingerprint information obtained in advance and the luminescence information obtained in the luminescence information obtaining step S12 are collated to determine the state of the composition. At this time, as described above, only one performance or property of the composition may be evaluated, or a plurality of properties or performances may be evaluated. These comparisons can be performed by a general information processing device such as a personal computer.

Alternatively, a state estimation model may be created in advance, and the state of the composition may be specified by the estimation model. When there are many evaluation items for a composition, more appropriate evaluation can be performed by using a state estimation model.

The state estimation model can be created by machine learning the fluorescent fingerprint obtained in advance and the state of the composition corresponding to this. A known method can be used as the machine learning method. For example, for a composition in a specific state, multivariate analysis is performed using the fluorescence fingerprint as an explanatory variable and the state as an objective variable to obtain a similarity index. Similarity measures include cosine similarity, Pearson's correlation coefficient, deviation pattern similarity, Euclidean distance similarity, Morishita's similarity index, standard Euclidean distance similarity, Mahalanobis distance similarity, Manhattan distance similarity, and Chebyshev distance similarity. degree, Minkowski distance similarity, Jaccard coefficient similarity, Dice coefficient similarity, and Simpson coefficient similarity.

In the similarity index calculation process, on the premise that there is a correlation between the state of the composition, which is the objective variable, and the similarity index of the fluorescence fingerprint, the similarity index of the fluorescence fingerprint is calculated for a specific composition. This is then done for other compositions in different states. Then, an estimation model can be created by repeatedly executing and optimizing such that the error between the calculated similarity index and the actual state of the composition becomes small.

It should be noted that many analysis methods have been developed for 2D data. On the other hand, the fluorescence fingerprint described above is three-dimensional data of the wavelength of excitation light, the wavelength of light emitted by a luminescent substance, and the intensity of the light. Therefore, three-dimensional data may be developed two-dimensionally to perform multivariate analysis. For example, fluorescence fingerprints may be developed into two-dimensional data of wavelength conditions (combination of excitation wavelength and fluorescence wavelength) and fluorescence intensity, and multivariate analysis may be performed. In addition, meancentering, normalization, autoscale, second derivative, baseline correction, and smoothing are performed on the two-dimensionally unfolded fluorescence fingerprint. etc. may be performed. This allows us to emphasize the information contained in each data and scale the data from different samples. On the other hand, multivariate analysis may be performed on the three-dimensional data as it is.

In addition, if necessary, it is also possible to detect marker signals (combinations of excitation wavelengths and fluorescence wavelengths, etc.) that are important for estimation (changes significantly depending on the state of the composition) from the obtained similarity index. At this time, principal component regression, cluster analysis, discriminant analysis, SIMCA, multiple regression analysis, PLS regression analysis, PLS discrimination, SVM regression, SVM discrimination, RF regression, and / or RF discrimination are performed as multivariate analysis, and the marker signal is may be detected. In addition, marker signals are detected based on indicators that indicate the contribution rate of one or more of the regression coefficient, factor loading, loading, selectivityratio, variableimportanceinprojection, variable importance, and outofbagerror obtained by multivariate analysis to regression and discrimination. good too.

Then, the numerical value of the marker signal is estimated for a composition different from the composition for which the similarity index was obtained. After that, the data calculated by the estimation and the actual data are compared, optimization is repeatedly performed so that these errors are reduced, and a state estimation model that can estimate the state of the composition by a specific marker signal is obtained. may

Then, when such a state estimation model is created, the state of the composition can be evaluated by applying the luminescence information obtained in the luminescence information acquisition step to the state estimation model.

(others)
In the above description, the luminescent material selection step, the luminescent layer preparation step, the luminescent information acquisition step, and the evaluation step have been described. No process is required.

(effect)
As described above, in the evaluation method of the present embodiment, the state of the composition is evaluated based on fluorescence fingerprint information obtained in advance. According to the method, even if individual components in the composition are not specified or multiple substances in the composition interact in a complex manner, their properties and performance can be inductively captured and comprehensively can be evaluated. In other words, it is possible to evaluate the performance and characteristics of the composition without the need to perform a complicated component analysis on the composition, and even when the correlation between each component and the performance and characteristics is not clear. .

Also, by using fluorescence fingerprint information, even slight changes can be detected. Furthermore, the state of the composition can be comprehensively evaluated at an appropriate timing without affecting the composition in product research and development and production lines.

2. Sensors and Evaluation Systems The present invention also provides, in one embodiment, sensors that can be used in the evaluation methods described above. The sensor includes a light-emitting portion having a light-emitting layer containing a light-emitting substance whose light-emitting behavior changes according to the state of the composition, an excitation light source that emits excitation light for exciting the light-emitting substance, and light emitted by the light-emitting substance. For example, the light emitting unit, the excitation light source, and the detecting unit may not be connected. For example, the light-emitting portion may be a structure (probe) having an optical fiber and a light-emitting layer disposed at the tip of the optical fiber. It may be a structure having a light-emitting layer disposed on the surface member.

However, if the light-emitting part is the above-mentioned probe, it is preferable because it is easy to connect with the excitation light source and the detection part, the sensor is easy to handle, and it can be miniaturized. A sensor having such a probe will be described below as an example, but the sensor of this embodiment is not limited to this structure.

For example, as shown in FIG. 4, the sensor includes a light guide member 21a and a light emitting layer 21b disposed at the tip of the light guide member 21a and containing a light emitting substance whose light emission behavior changes depending on the state of the composition. a light source 22 that emits excitation light for exciting the luminescent substance; and a detector 23 that acquires information on the light emitted by the luminescent substance. The configuration of each of these members is the same as that of the sensor prepared in the light-emitting layer preparation step S12 of the evaluation method described above.

However, the wavelength of the excitation light emitted by the light source 22 in the sensor 20 is a wavelength determined based on the previously acquired fluorescence fingerprint information (mode 1), or the light-emitting substance is a wavelength determined based on the previously acquired fluorescence fingerprint information. It is a determined substance (aspect 2).

In the aspect 1, the pre-acquired fluorescence fingerprint information is obtained by mixing a specific light-emitting substance (the light-emitting substance contained in the light-emitting layer 21b) and a plurality of compositions having different states to prepare a plurality of samples. This is information when fluorescence fingerprints are obtained for each sample. By measuring the fluorescence fingerprints of each of these samples and comparing the fluorescence fingerprints with each other, it becomes clear what wavelength of excitation light is applied to make it easier to determine the change in state of the composition. Then, the wavelength at which the state change can be easily determined is determined as the wavelength of the excitation light emitted by the light source 22 . Therefore, according to the sensor 20 of aspect 1, the state of the composition can be grasped only by irradiating light of a specific wavelength as excitation light without using excitation light of a wide wavelength range.

On the other hand, the fluorescence fingerprint information obtained in advance in aspect 2 is obtained by mixing a plurality of candidate luminescent substances and a plurality of compositions in different states to prepare a plurality of samples, and obtaining fluorescence fingerprints for each of these samples. It is the information at the time of acquisition. Fluorescence fingerprints are obtained for each of these samples, and by comparing the fluorescence fingerprints, it becomes clear which candidate luminescent substance (luminescent substance) is used to make it easier to determine the state change of the composition. Then, a candidate light-emitting substance whose state change can be easily determined is determined as a light-emitting substance contained in the light-emitting layer 21b. Therefore, according to the sensor 20 of aspect 2, the difference in the state of the composition is likely to appear in the luminescence information from the light-emitting substance, and the state of the composition can be easily grasped.

In any aspect, the method for obtaining the fluorescent fingerprint is the same as the method described in the above-described luminescent substance selection step S10.

The present invention also provides, as an embodiment, an evaluation system having any one of the above sensors and an information processing unit. The information processing section of the evaluation system analyzes the luminescence information obtained by the detection section of the sensor based on the fluorescence fingerprint information obtained in advance, and evaluates the state of the composition. Here, the type of the information processing unit is not particularly limited, and a general information processing device such as a personal computer can be used.

Further, the fluorescence fingerprint information used by the evaluation system may be the fluorescence fingerprint information acquired to determine the wavelength of the excitation light of the sensor, or the fluorescence fingerprint information acquired to determine the luminescent substance of the sensor. may be Alternatively, the fluorescence fingerprint information obtained separately may be used.

Furthermore, in the evaluation system, the information processing unit may be made to acquire a state estimation model in advance by machine learning, and the composition may be evaluated using the state estimation model. The state estimation model can be created in the same manner as the state estimation model used in the composition evaluation method described above.

Specific examples of the present invention will be described below together with comparative examples, but the present invention is not limited to these.

(1) Selection of light-emitting substances Resin composition A (concentration of cycloolefin polymer a: 30 g/l) in which recyclable cycloolefin polymer a is dissolved in methylene chloride, and non-recyclable cycloolefin polymer b (cycloolefin A resin composition B (concentration of cycloolefin polymer b: 30 g/l) was prepared by dissolving polymer b (resin obtained by recycling cycloolefin polymer a multiple times) in methylene chloride. Then, the resin composition A and the resin composition B were mixed with 24 kinds of luminescent substances. The number of standard samples was 50, that is, 2 (resin compositions A and B) x 25 (24 types (number of luminescent substances) + 1 (no luminescent substance)). Then, fluorescence fingerprints were measured for each of these standard samples. Fluorescence fingerprints were measured with a commercially available spectrofluorophotometer (F-7000, manufactured by Hitachi High-Tech Science Co., Ltd.). The fluorescence fingerprint was measured by measuring the wavelength and intensity of the fluorescence emitted by the standard sample while shifting the excitation wavelength by 10 nm in the range of 250 nm to 700 nm. Fluorescent fingerprints were acquired by converting these into three-dimensional data.

The obtained fluorescence fingerprints were analyzed, the fluorescence fingerprints of resin composition A and resin composition B were compared, and the most changed luminescent substance (BASF IRGANOX 1076) and the characteristic excitation wavelength and emission wavelength (excitation wavelength: 320 nm/emission wavelength: 410 nm) was identified. In addition, there was no difference in the data without the luminescent substance. FIG. 5A shows a fluorescence fingerprint obtained using a light-emitting substance (IRGANOX1076 manufactured by BASF) for resin composition A, and FIG. 5B shows a fluorescence fingerprint obtained using a light-emitting substance (IRGANOX1076 manufactured by BASF). Shows fluorescent fingerprints.

(2) Fabrication of sensor A composition obtained by mixing an epoxy polymer and a light-emitting material (IRGANOX1076 manufactured by BASF) was applied to the end of an optical fiber to form a light-emitting layer with a thickness of 1 mm to fabricate a sensor. An optical fiber provided with an excitation light fiber and a detection light fiber was prepared. The excitation light fiber was connected to a light source capable of emitting light with a wavelength of 320 nm. On the other hand, the detection light fiber was connected to a detection unit (spectrofluorophotometer, F-7000, manufactured by Hitachi High-Tech Science Co., Ltd.).

(3) Evaluation of composition A resin composition C (concentration of cycloolefin polymer c: 30 g/l) was prepared by dissolving cycloolefin polymer c whose number of recycling times was unknown in methylene chloride. The end portion of the sensor was immersed in the resin composition C, and irradiated with light having a wavelength of 320 nm by an excitation light fiber. Fluorescence emitted by the light-emitting layer was detected with a spectrofluorometer through a detection light fiber. The obtained data was compared with the fluorescence fingerprint data by the information processing unit to determine whether or not the cycloolefin polymer c was recyclable.

This application claims priority based on Japanese Patent Application No. 2021-143165 filed on September 2, 2021. All contents described in the specification and drawings are incorporated herein by reference.

With the evaluation method of the composition of the present invention, it is possible to comprehensively evaluate the state of the composition in the research and development of products and in the production line without affecting the target composition. Therefore, it is useful for inspection, research, production, etc. of various compositions.

21 probe 21a light guide member 21b light emitting layer 22 light source 23

detector

210a, 210b cable

Claims

preparing a light-emitting layer containing a light-emitting substance whose light-emitting behavior changes depending on the state of the composition;
a step of irradiating the light-emitting layer with excitation light while the light-emitting layer and the composition are in contact with each other to acquire light emission information of the light-emitting substance;
a step of analyzing the luminescence information based on fluorescence fingerprint information obtained in advance to evaluate the state of the composition;
A method for evaluating a composition.
the light-emitting layer is disposed at the tip of an optical fiber or disposed on a light-guiding planar member;
A method for evaluating the composition according to claim 1 .
performing the step of acquiring the luminescence information in a production line of the composition;
A method for evaluating the composition according to claim 1 or 2.
Before the step of preparing the light-emitting layer,
preparing a plurality of samples containing a plurality of the compositions in different states and a plurality of types of candidate luminescent substances;
obtaining sample fluorescence fingerprint information for the plurality of samples;
selecting the luminescent material based on the sample fluorescence fingerprint information;
The method for evaluating the composition according to any one of claims 1 to 3, further comprising
determining the wavelength of the excitation light based on the sample fluorescence fingerprint information;
A method for evaluating the composition according to claim 4 .
a light-emitting portion having a light-emitting layer containing a light-emitting substance whose light-emitting behavior changes depending on the state of the composition;
an excitation light source that emits excitation light for exciting the luminescent substance;
a detection unit that acquires information about the light emitted by the light-emitting substance;
has
The wavelength of the excitation light is a wavelength determined based on pre-obtained fluorescence fingerprint information.
sensor.
a light-emitting portion having a light-emitting layer containing a light-emitting substance whose light-emitting behavior changes depending on the state of the composition;
an excitation light source that emits excitation light for exciting the luminescent substance;
a detection unit that acquires information about the light emitted by the light-emitting substance;
has
The luminescent substance is a substance selected based on pre-obtained fluorescence fingerprint information,
sensor.
a sensor according to claim 6 or 7;
an information processing unit that analyzes the light information acquired by the detection unit by fluorescence fingerprint information acquired in advance and evaluates the state of the composition;
A rating system.