Odor sensor

Abstract

To provide an odor sensor capable of accurately detecting an odor substance.SOLUTION: The odor sensor (30) includes an odor substance receiving layer (315) having a contact surface that comes into contact with a gas containing an odor substance and capable of interacting with the odor substance via the contact surface, A first device (31P) that outputs a first signal relating to a first change in state occurring in a smell material receiving layer, and a second device (31Q) that includes a smell material receiving layer having a contact surface covered with a covering part (316) and outputs a second signal relating to a second change in state occurring in the smell material receiving layer, wherein the covering part includes: The water vapor transmission rate is 0g / m2 / day / atm or more and 2. 0g / m2 / day / atm or less, and the oxygen transmission rate is 0cc / m2 / day / atm or more and 100cc / / day / atm or less. m2.SELECTED DRAWING: Figure 8

Description

[Technical Field]

[0001] The present invention relates to an odor sensor for performing measurements related to odorous substances. [Background technology]

[0002] Conventionally, odor sensors have been known that include a sensor element having a membrane or layer that adsorbs odorous substances contained in the odor emitted by a target.

[0003] For example, the odor sensor described in Patent Document 1 includes an adsorption film that adsorbs odorants, and a detection unit that has a metal oxide or nitride semiconductor element and detects changes in the adsorption state due to the odorants being adsorbed onto the adsorption film, with the adsorption film being compatible with a coating material and formed on the detection unit. Furthermore, the sensor described in Patent Document 2 detects changes in the optical properties of the core layer when a specific molecule to be detected is adsorbed, and detects the presence or absence of the specific molecule and the concentration of the specific molecule in the atmosphere in which the sensor is placed. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 2024-057732 [Patent Document 2] Japanese Patent Application Laid-Open No. 2006-090914 Summary of the Invention [Problem to be solved by the invention]

[0005] The output signal from an odor sensor that detects odorous substances is affected by the measurement environment. Therefore, in order to detect odorous substances accurately, it is desirable to appropriately evaluate the effect of the measurement environment on the output signal and correct the output signal.

[0006] One aspect of the present invention provides an odor sensor that can accurately detect odorous substances by appropriately evaluating the effect of the measurement environment on an output signal and correcting the output signal. [Means for solving the problem]

[0007] In order to solve the above-mentioned problems, an odor sensor according to one aspect of the present invention comprises a first element having a contact surface that comes into contact with a gas containing an odorant, an odorant receiving layer that can interact with the odorant through the contact surface, and outputs a first signal related to a first state change that occurs in the odorant receiving layer, and a second element having the odorant receiving layer whose contact surface is covered by a covering portion, and outputs a second signal related to a second state change that occurs in the odorant receiving layer, wherein the covering portion has a water vapor permeability of 0 g / m 2 / day / atm or more 2.0g / m 2 / day / atm or less, and the oxygen permeability is 0cc / m 2 / day / atm or more 100cc / m 2 / day / atm or less. [Effects of the Invention]

[0008] According to one aspect of the present invention, an odor sensor capable of detecting odorous substances with high accuracy can be provided. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a schematic diagram illustrating an example of the configuration of an odor sensor according to one embodiment of the present invention. [Figure 2] FIG. 2 is a top view showing an example of the configuration of a first element. [Figure 3] FIG. 3 is a cross-sectional view showing an example of the configuration of the first element shown in FIG. [Figure 4] FIG. 4 is a top view showing an example of the configuration of a second element. [Figure 5] FIG. 5 is a cross-sectional view showing an example of the configuration of the second element shown in FIG. [Figure 6] 1 is a graph showing the relationship between temperature and resistance value when measurements of odorous substances are performed using the first element and the second element. [Figure 7]1 is a graph showing time and resistance values ​​when measurements of odorous substances are performed using the first element and the second element. [Figure 8] 1 is a schematic diagram showing an example of the configuration of an odor measurement device according to one embodiment of the present invention. [Figure 9] FIG. 1 is a functional block diagram showing an example of the configuration of an odor measurement device. [Figure 10] 10 is a flowchart illustrating an example of a processing flow in which the estimation device generates an estimation model. [Figure 11] FIG. 1 is a functional block diagram showing an example of the configuration of an odor measurement device. [Figure 12] 10 is a flowchart showing an example of the flow of a process in which the estimation device estimates an odor substance. [Figure 13] FIG. 2 is a top view showing an example of the configuration of a first element of the present invention. [Figure 14] FIG. 2 is a top view showing an example of the configuration of a first element of the present invention. [Figure 15] FIG. 1 is a perspective view showing an example of the configuration of a first element of the present invention. [Figure 16] 1 is a schematic diagram showing a method for manufacturing a sensor substrate K-1 in an example of the present invention. [Figure 17] 1 is a schematic diagram showing a method for manufacturing a sensor substrate K-1 in an example of the present invention. [Figure 18] FIG. 2 is a schematic diagram showing the configuration of the front surface of a sensor substrate K-1 in an example of the present invention. [Figure 19] FIG. 2 is a schematic diagram showing the configuration of the rear surface of a sensor substrate K-1 in an example of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0010] [Embodiment] One embodiment of the present invention will be described below, but the present invention is not limited thereto. Furthermore, unless otherwise specified in this specification, the expression "A to B" representing a range of numerical values ​​means "A or more and B or less."

[0011] The odor sensor 30 according to the present invention includes a plurality of sensor elements 31. The sensor elements 31 include at least one first element 31P and at least one second element 31Q. In the following description, when there is no need to distinguish between the first element 31P and the second element 31Q, they will be referred to as "sensor elements 31."

[0012] The first element 31P has a contact surface that comes into contact with the odorant-containing gas and is equipped with an odorant receiving layer 315 that can interact with the odorant through the contact surface. The first element 31P is also capable of outputting a signal (first signal) related to a state change (first state change) that occurs in the odorant receiving layer 315. In this way, the first element 31P is a sensor element that can output a measurement value according to the type and concentration of the odorant that causes the odor being measured.

[0013] In this specification, "odor substance" broadly refers to a substance that can be adsorbed onto an odor substance receiving layer. Therefore, it also includes substances that are not generally considered to be odor-causing substances. "Odor" often contains multiple odor substances that cause it, and there are also substances that are not recognized as odor substances or unknown odor substances. One embodiment of the present invention focuses on the fact that the amount of odor substance adsorbed onto an odor substance receiving layer varies depending on the type of odor substance.

[0014] In addition, even when the term "odorous substance" is simply used in this specification, it may refer to a "collection of odorous substances" that may contain multiple odorous substances, rather than an individual odorous substance.

[0015] Examples of "odor substances" include, but are not limited to, hexane, ethyl acetate, methanol, diethyl carbonate, toluene, d-limonene, bornan-2-one, cis-3-hexenol, β-phenylethyl alcohol, citral, L-carvone, γ-undecalactone, eugenol, linalyl acetate, menthol, benzaldehyde, vanillin, hexanal, ethanol, pentyl valerate, linalool, and 2-propanol.

[0016] Furthermore, in this specification, "odorant receiving layer 315" refers to a layer that adsorbs the odorant to be recognized. The odorant receiving layer 315 is formed from a resin composition described below. The odorant receiving layer 315 may be provided as part of the sensor element 31. The second element 31Q has an odorant receiving layer 315 of the same composition as the first element 31P. Furthermore, the contact surface of the odorant receiving layer 315 of the second element 31Q is covered by a covering portion 316. The second element 31Q outputs a signal (second signal) related to a state change (second state change) that occurs in the odorant receiving layer 315.

[0017] The contact surface of the odorant receiving layer 315 of the second element 31Q is covered with the covering portion 316, which reduces the amount of odorant that interacts with the odorant receiving layer 315 through the contact surface. Therefore, the second element 31Q can output a measurement value that is affected by the temperature of the measurement environment but is less affected by the type and concentration of the odorant.

[0018] As described above, the odor sensor 30 includes the first element 31P and the second element 31Q. This allows the odor sensor 30 to output a measurement value based on the second signal of the second element 31Q and a measurement value based on the first signal of the first element 31P. Furthermore, by correcting the measurement value based on the first signal of the first element 31P using the measurement value based on the second signal of the second element 31Q, it is possible to measure odor substances using values ​​that are less affected by the environment.

[0019] [1. Resin composition] The resin composition according to one embodiment of the present invention is a resin composition for forming an odorant-receiving layer, and contains a resin (A) and a conductive carbon material (C). The resin composition may further contain a surfactant (B). The resin (A), surfactant (B), and conductive carbon material (C) will be described later with specific examples.

[0020] The sensor described in Reference 1 is believed to be capable of detecting odors composed of single compounds. However, many odors are mixtures of multiple substances. The sensor described in Reference 1 lacks the ability to distinguish odor components in the detection section, resulting in insufficient odor discrimination performance for mixtures. Reference 2 demonstrates that by utilizing the differences in the chemical structure of the conductive polymers used in the detection section, the detection section can differentiate its response to various compounds via each conductive polymer, enabling the recognition of odor mixtures. However, the chemical structures of conductive polymers are limited, making it difficult to sensitively separate the response of the detection section to any odor component, making it difficult to distinguish between odors composed of similar components. Reference 3 proposes a method using a mixture of organic polymers, plasticizers, and conductive substances as the detection material in the detection section, detecting the penetration of odor components into the organic polymer as a change in the electrical resistance of the mixture. Taking advantage of the fact that different organic polymers with different compositions allow different odor components to penetrate, multiple detection sections made of the above detection material containing organic polymers of different compositions can be arranged in parallel to form an array, enabling the recognition of odor mixtures. However, with the organic polymers and organic polymers containing plasticizers described above, even if multiple combinations of organic polymers and conductive materials are prepared, the difference in chemical properties between the organic polymers is small, so the odor discrimination performance is insufficient. These conventional technologies cannot accurately detect, for example, real odor patterns where multiple substances interact or real odor patterns caused by substances with unknown compositions.

[0021] The inventors of the present invention have focused on the fact that the electrical conductivity of a resin composition varies depending on the amount of odorant adsorbed to the resin composition, and that the adsorption process to the resin composition differs for each odorant. This led to the invention of a resin composition and a sensor element according to an embodiment of the present invention. The use of such a resin composition can improve odor discrimination performance. For example, it can discriminate between real odor patterns in which multiple substances interact, or even between real odor patterns caused by substances with unknown compositions.

[0022] <Resin (A)> The resin (A) contained in the resin composition according to one embodiment of the present invention is not particularly limited, but may be a urethane resin, a polyalkylene oxide, an acrylic resin, a fluorine group-containing resin, a vinyl polymer resin (for example, a butyral resin), a silicone resin, a polyamide resin, a polyester resin, or the like.

[0023] <Surfactant (B)> The resin composition according to one embodiment of the present invention may contain a surfactant (B) as described below. The surfactant (B) acts as a dispersant for the conductive carbon material (C) described below. The surfactant (B) can be appropriately selected from known surfactants as long as it exhibits the above-mentioned function. In one embodiment, the resin composition according to one embodiment of the present invention may not contain a surfactant (B).

[0024] Examples of the surfactant (B) include anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants.

[0025] Examples of the anionic surfactant include alkali metal salts of carboxylic acids having 10 to 24 carbon atoms and alkali metal salts of alkylsulfonic acids having 14 to 24 carbon atoms.

[0026] Examples of the carboxylic acid having 10 to 24 carbon atoms include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, pentadecanoic acid, nonadecanoic acid, icosanoic acid, henicosanoic acid, docosanoic acid, tricosanoic acid, and tetracosanoic acid.

[0027] Examples of the alkyl group contained in the alkylsulfonic acid having 14 to 24 carbon atoms include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a heneicosyl group, a docosyl group, a tricosyl group, and a tetracosyl group.

[0028] Examples of the alkali metal contained in the alkali metal salt include sodium and potassium.

[0029] Examples of cationic surfactants include halide salts of quaternary ammonium having an alkyl group having 12 to 24 carbon atoms.

[0030] Examples of the quaternary ammonium having an alkyl group having 12 to 24 carbon atoms include tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, dimethyldioctylammonium, didecyldimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium, tridecyltrimethylammonium, hexadecyltrimethylammonium, methyltrioctylammonium, octyltrimethylammonium, tributylmethylammonium, octadecyltrimethylammonium, tetradecyltrimethylammonium, nonadecyltrimethylammonium, icosyltrimethylammonium, heneicosyltrimethylammonium, heptadecyltrimethylammonium, and pentadecyltrimethylammonium.

[0031] Examples of the halide salt include fluoride salt, chloride salt, bromide salt, and iodide salt.

[0032] Examples of amphoteric surfactants include dimethyl(3-sulfopropyl)ammonium inner salts having an alkyl group with 10 to 22 carbon atoms, and N-alkyl-N,N-dimethylglycines having an alkyl group with 10 to 22 carbon atoms.

[0033] Examples of dimethyl(3-sulfopropyl)ammonium hydroxide inner salts having an alkyl group having 10 to 22 carbon atoms include decyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, undecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, dodecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, tridecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, tetradecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, and pentadecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt. Examples include hexadecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, hexadecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, heptadecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, octadecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, nonadecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, icosyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, heneicosyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, and docosyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt.

[0034] Examples of N-alkyl-N,N-dimethylglycines having an alkyl group with 10 to 22 carbon atoms include N-dodecyl-N,N-dimethylglycine and N-octadecyl-N,N-dimethylglycine.

[0035] Examples of nonionic surfactants include higher alcohol ethylene oxide adducts.

[0036] Examples of higher alcohols include 1-hexyl alcohol, 1-heptyl alcohol, 1-octyl alcohol, 1-nonyl alcohol, 1-decyl alcohol, 1-undecyl alcohol, 1-dodecyl alcohol, 1-tridecyl alcohol, 1-tetradecyl alcohol, 1-pentadecyl alcohol, 1-hexadecyl alcohol, 1-heptadecyl alcohol, and 1-octadecyl alcohol.

[0037] The number of moles of ethylene oxide added is preferably 5 to 50, more preferably 5 to 40, and even more preferably 5 to 30, from the viewpoint of odor discrimination performance.

[0038] The weight ratio of the resin (A) to the surfactant (B) [(A) / (B)] is preferably 1.0 to 50.0 from the viewpoint of odor discrimination performance.

[0039] The resin (A) and the surfactant (B) may or may not be compatible with each other.

[0040] From the viewpoint of dispersibility in the conductive carbon material (C), the surfactant (B) is preferably a nonionic surfactant. Furthermore, from the viewpoint of dispersibility in the conductive carbon material (C), the surfactant (B) preferably has at least one of an amide group, a primary amino group, a secondary amino group, and a tertiary amino group. Furthermore, from the viewpoint of dispersibility in the conductive carbon material (C), the surfactant (B) preferably has at least one of an oxyethylene chain, an oxypropylene chain, and a random or block structure of oxyethylene-oxypropylene. The random structure of oxyethylene-oxypropylene is a chain structure in which both oxyethylene and oxypropylene are irregularly linked. The block structure of oxyethylene-oxypropylene is a chain structure in which oxyethylene blocks formed by linking oxyethylenes and oxypropylene blocks formed by linking oxypropylenes are linked.

[0041] <Conductive carbon material (C)> A resin composition according to one embodiment of the present invention contains a conductive carbon material (C). In this specification, the conductive carbon material (C) refers to a carbon material having a volume resistivity of 0.1 Ω·cm or less. The resin composition is in a state in which the conductive carbon material (C) is dispersed in the resin (A). The conductive carbon materials (C) come into contact with each other to form conductive paths, thereby making the resin composition conductive.

[0042] Examples of the conductive carbon material (C) include carbon black, carbon nanotubes, and graphene.

[0043] Commercially available carbon black products include Ketjenblack EC (trade name manufactured by Akzo, Netherlands), Ketjenblack EC-300J (trade name manufactured by Lion Specialty Chemicals Co., Ltd.), Ketjenblack EC-600JD (trade name manufactured by Lion Specialty Chemicals Co., Ltd.), Seast G116, 116 (trade names manufactured by Tokai Carbon Co., Ltd.), Nitelon #10 (trade name manufactured by Nippon Steel Chemical Co., Ltd.), Denka Black (trade name manufactured by Denki Kagaku Kogyo Kabushiki Kaisha), and SUPER C-65 (product name manufactured by MTI Corporation, USA).

[0044] Commercially available carbon nanotubes include VGCF-H (product name manufactured by Showa Denko KK).

[0045] Commercially available graphene is manufactured by Sigma-Aldrich.

[0046] The conductive carbon material (C) is preferably in the form of fibers or spheres.

[0047] When it is fibrous, the fiber diameter is preferably 0.1 to 10 μm, more preferably 0.1 to 5 μm, and the fiber length is preferably 0.1 to 10 μm, more preferably 1 to 10 μm.

[0048] When the particles are spherical, the primary particle size is preferably 10 nm to 200 nm, and more preferably 20 nm to 150 nm.

[0049] Furthermore, from the viewpoint of conductivity in the resin composition and sensor sensitivity, the conductive carbon material preferably has a primary particle diameter of 100 nm or less. The particle diameter of the conductive carbon material can be determined by a known method. For example, the particle diameter of the conductive carbon material can be measured by observing the material with a transmission electron microscope (TEM) and analyzing the image using an image processing device (e.g., Keyence Digital Microscope VHX-700F). When the conductive carbon material is a known or commercially available product, the particle diameter may be a literature value or a catalog value.

[0050] The content of the conductive carbon material (C) is preferably 5 to 65% by weight relative to 100% by weight of the total of the resin (A), surfactant (B), and conductive carbon material (C), from the viewpoint of ensuring that the sensor element formed from the resin composition exhibits sufficient conductivity as an odor sensor and sufficient sensitivity as the odor sensor.

[0051] The resin composition may further contain other components in addition to the resin (A), surfactant (B), and conductive carbon material (C) described above, as long as the effects of the present invention are obtained. Examples of other components include a solvent (D). The other components can be suitably used as long as both the effects of the present invention and the effects of the other components are obtained.

[0052] The solvent (D) can be blended into the resin composition from the viewpoint of improving the compatibility between the resin (A) and the surfactant (B), improving the dispersibility of the conductive carbon material (C) in the resin composition, or improving the coatability of the resin composition. Examples of the solvent (D) include N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, ethyl butyrate, butyl butyrate, ethyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, toluene, and xylene.

[0053] The content of the solvent (D) in the resin composition can be determined appropriately from the above viewpoints. For example, from the viewpoint of coatability, the content of the solvent (D) in the resin composition is preferably 100 to 10,000 parts by weight per 100 parts by weight of the total of the resin (A), surfactant (B), and conductive carbon material (C).

[0054] <Method of manufacturing resin composition> A specific example of the method for producing a resin composition according to one embodiment of the present invention is as follows.

[0055] The resin composition is obtained as a slurry by mixing the resin (A), surfactant (B), conductive carbon material (C), and, if necessary, solvent (D) and kneading the mixture uniformly with a stirrer. When solvent (D) is added, the solvent (D) is distilled off from the resin composition. The solvent (D) may be distilled off from the resin composition produced by uniform mixing, or from the coating film produced during the production of the sensor element described below.

[0056] [2. First element 31P] The above-mentioned resin composition exhibits different changes in electrical conductivity over time when odorant A is adsorbed onto the resin composition than when odorant B, which is different from odorant A, is adsorbed onto the resin composition. By utilizing this property, it is possible to realize a first element 31P, which is a sensor element capable of detecting and identifying odorants.

[0057] The following describes the outline and effects of the first element 31P to which the resin composition according to one embodiment of the present invention is applied.

[0058] The first element 31P includes an odorant receiving layer 315 containing the resin composition described above, a first metal wiring 313A, and a second metal wiring 313B. In the following, when there is no need to distinguish between the first metal wiring 313A and the second metal wiring 313B, they may be referred to as metal wiring 313.

[0059] Here, first metal wiring 313A and second metal wiring 313B will be described with reference to Figures 2 and 3. Figure 2 is a top view showing an example of the configuration of first element 31P, and Figure 3 is a cross-sectional view showing an example of the configuration of first element 31P shown in Figure 2.

[0060] The first metal wiring 313A and the second metal wiring 313B are each metal wirings that function as electrodes for measuring changes in the electrical conductivity of the odorant receiving layer 315 (i.e., the resin composition). That is, the first metal wiring 313A and the second metal wiring 313B are spaced apart from each other, and the odorant receiving layer 315 is in contact with at least a portion of the first metal wiring and at least a portion of the second metal wiring. In one example, the first metal wiring 313A and the second metal wiring 313B are metal wirings that are not in direct contact with each other, and may be metal wirings that are approximately parallel to each other, as shown in FIG. 2.

[0061] As shown in FIG. 2, metal wiring 313 including first metal wiring 313A and second metal wiring 313B may be disposed on substrate 311. Substrate 311 may be a substrate such as glass epoxy commonly used in electronic circuits. Metal wiring 313 may be metal wiring such as copper or gold. When viewed perpendicular to the surface of the substrate, the thickness of each of first metal wiring 313A and second metal wiring 313B is preferably 10 μm to 2 mm, more preferably 10 μm to 1 mm. When viewed parallel to the surface of the substrate, the height, i.e., thickness, of each of first metal wiring 313A and second metal wiring 313B is preferably 1 μm to 100 μm, more preferably 10 μm to 50 μm. The distance between first metal wiring 313A and second metal wiring 313B is preferably 1 μm to 3 mm, more preferably 1 μm to 1.5 mm. The length of the metal wiring 313 is preferably 100 μm to 50 mm, and more preferably 500 μm to 30 mm.

[0062] Figure 3 shows a cross section taken along line AA in Figure 2. The odorant receiving layer 315 may be in contact with at least a portion of the first metal wiring 313A and at least a portion of the second metal wiring 313B. The odorant receiving layer 315 may be arranged to fill the area between the first metal wiring 313A and the second metal wiring 313B, as shown in Figures 2 and 3, for example.

[0063] If the electrical conductivity of the odorant receiving layer 315 (i.e., the electrical conductivity of the first element 31P) is low, it is desirable that the distance between the first metal wiring 313A and the second metal wiring 313B be a predetermined distance (e.g., 500 μm) or less.

[0064] The first element 31P can detect and distinguish various odorants by using a resin composition whose electrical conductivity changes differently over time when odorant A is adsorbed and when odorant B, which is different from odorant A, is adsorbed. In the odor sensor 30 described below, multiple first elements 31P each having a substrate 311 on which an odorant detection structure (metal wiring 313 and odorant receiving layer 315) is provided may be arranged. Each substrate 311 may be provided with multiple sets containing odorant receiving layers 315 of the same composition. When multiple first elements 31P are arranged, each first element 31P is provided with a constant-voltage power supply and a voltmeter. In the odor sensor 30, each substrate 311 may be provided with one odorant detection structure (metal wiring 313 and odorant receiving layer 315). Alternatively, in the odor sensor 30, multiple sets of odorant detection structures (metal wiring 313 and odorant receiving layer 315) may be arranged on a single substrate 311. In the latter case, a constant voltage power supply and a voltmeter are connected to each of the sets provided on the substrate 311 .

[0065] The compositions of the multiple odorant receiving layers 315 included in the odor sensor 30 may be the same or different. If the odor sensor 30 includes odorant receiving layers 315 with the same composition, the multiple odorant receiving layers 315 can each detect the same odorant. If the odor sensor 30 includes odorant receiving layers 315 with different compositions, each of the multiple odorant receiving layers 315 will respond differently to the odorant. In this way, by providing multiple sets of configurations for detecting odorants, the accuracy of odorant identification in the odor sensor 30 can be improved.

[0066] [3. Second element 31Q] The following describes the outline and effects of the second element 31Q to which the resin composition according to one embodiment of the present invention is applied.

[0067] The second element 31Q comprises an odorant receiving layer 315 containing the resin composition described above, a first metal wiring 313A, and a second metal wiring 313B. In addition to the odorant receiving layer 315, the second element 31Q also comprises a coating 316 that covers the odorant receiving layer 315. In the following, when there is no need to distinguish between the first metal wiring 313A and the second metal wiring 313B, they may be referred to as metal wiring 313.

[0068] FIG. 4 is a top view showing an example of the configuration of the second element 31Q, and FIG. 5 is a cross-sectional view showing an example of the configuration of the second element 31Q shown in FIG. 4. As shown in FIGS. 4 and 5, the second element 31Q has a covering portion 316 in addition to the same configuration as the first element 31P. The covering portion 316 covers the odorant receiving layer 315 and reduces desorption of odorants from the odorant receiving layer 315. The covering portion 316 has insulating properties and gas barrier properties against odorants. For example, the water vapor permeability of the covering portion 316 is 0 g / m 2 / day / atm or more 2.0g / m 2 / day / atm or less, and the oxygen permeability is 0cc / m 2 / day / atm or more 100cc / m 2 / day / atm or less. By setting the water vapor permeability and oxygen permeability of the covering portion 316 in this way, the covering portion 316 of the second element 31Q can reduce the amount of odorant, moisture, etc. that interacts with the odorant receiving layer 315 via the contact surface.

[0069] The water vapor permeability is a value measured in accordance with JIS K 7129B at 40°C and 90% RH (relative humidity). When water comes into contact with the odorant receiving layer 315, it may affect the output value of the sensor element 31. Here, in the second element 31Q, the water vapor permeability of the covering portion 316 is set as described above, thereby reducing the possibility of water coming into contact with the odorant receiving layer 315. This allows the second element 31Q to output a value that is less affected by moisture in the air.

[0070] The water vapor transmission rate of the covering portion 316 is preferably 0.1 g / m 2 / day / atm or more, preferably 0.2g / m 2 / day / atm or more. Also, 1.5g / m 2 / day / atm or less is preferable, and 1.0g / m 2 / day / atm or less is more preferable. If the water vapor transmission rate of covering portion 316 is within the above range, second element 31Q can output a value in which the influence of moisture in the air is reduced.

[0071] The oxygen permeability is a value measured in accordance with JIS K 7126-2 at 23°C and 0% RH. It is believed that many of the molecules contained in odorous substances are larger than oxygen. Here, by setting the oxygen permeability of the covering portion 316 as described above, it is possible to reduce the possibility that odorous substances larger than oxygen molecules will come into contact with the odorous substance receiving layer 315. As a result, the measurement value output by the second element 31Q can be affected by the surrounding environment, such as temperature, but is less affected by odorous substances present in the vicinity.

[0072] The oxygen permeability of the covering portion 316 is preferably 0.1 cc / m 2 / day / atm or more, preferably 0.5cc / m 2 / day / atm or more. Also, 80cc / m 2 / day / atm or less is preferable, 50cc / m 2 If the oxygen permeability of the covering portion 316 is within the above range, the possibility of odor substances larger than oxygen molecules coming into contact with the odorant receiving layer 315 can be reduced.

[0073] The covering portion 316 preferably has high thermal conductivity. For example, the thermal conductivity of the covering portion 316 may be 25.7 W / m / K or higher at 20°C. Thermal conductivity can be measured in accordance with ISO / CD22007-2 using a hot disk thermal conductivity method or the like. The temperature near the odorant receiving layer 315 when the second element 31Q performs a measurement, or the temperature of the odorant receiving layer 315 itself, can be set to be approximately the same as the temperature of the ambient environment of the first element 31P when the first element 31P performs a measurement. In the odor measuring device 100 incorporating the odor sensor 30 according to this embodiment, the measurement value of the second element 31Q is used to correct the measurement value of the first element 31P, thereby reducing the influence of the ambient environment, such as temperature, on the measurement value.

[0074] If a sticky substance comes into contact with the surface of the odorant receiving layer 315, the carbon components contained in the odorant receiving layer 315 may adhere to the sticky substance, potentially changing the composition of the odorant receiving layer 315. Here, by forming the covering portion 316 from a non-sticky film, at least in the portion that comes into contact with the odorant receiving layer 315, the effect of the covering portion 316 on the odorant receiving layer 315 can be reduced.

[0075] For example, the covering portion 316 may include a film having insulating and gas barrier properties. Specifically, a film having insulating and gas barrier properties and no adhesive properties may be used as the covering portion 316, and the odorant receiving layer 315 may be covered with the covering portion 316. In this case, the covering portion 316 may be further covered with a fixing layer (not shown), and the covering portion 316 may be fixed on the odorant receiving layer 315. Note that a film having insulating properties means that the volume resistivity of the film is 10 6 This means that the resistance is Ω·cm.

[0076] The fixing layer may be made of any material that can stably fix the covering portion 316 to the odorant receiving layer 315. For example, the fixing layer may be formed by applying a solder resist to the covering portion 316 and then irradiating it with UV light. Alternatively, the covering portion 316 may be covered with tape or adhesive as a fixing layer. Such a fixing layer is preferably made of a material with high thermal conductivity, such as copper metal tape or polyimide tape.

[0077] The second element 31Q may have a covering 316 made of a non-adhesive film that has insulating and gas-barrier properties, and the covering 316 may be fixed by an adhesive fixing layer, or may have other configurations. For example, in the second element 31Q, a portion of the covering 316 may be the fixing layer. Specifically, the second element 31Q may have a covering 316 made of an adhesive tape that has insulating and gas-barrier properties. It is preferable to avoid contact of adhesive substances with the odorant receiving layer 315. Therefore, if the covering 316 is made of adhesive tape, it is preferable that the portion of the covering 316 that comes into contact with the odorant receiving layer 315 is non-adhesive. For example, the non-adhesive side of the tape or a non-adhesive film may be attached to the tape that serves as the covering 316 so as to face the odorant receiving layer 315. Alternatively, the tape used as the covering portion 316 may be configured so that only the portion that does not come into contact with the odorant receiving layer 315 is adhesive.

[0078] For example, a film layer with gas barrier properties can be used as the covering portion 316. The film layer with gas barrier properties is a film layer with an oxygen permeability of 100 cc / m 2 A film layer with a permeability of 1000 kJ / day / atm or less can be used. Specific examples of materials used for such film layers include PTFE (polytetrafluoroethylene), PVDC (polyvinylidene chloride), EVOH (ethylene vinyl alcohol polymer), aluminum oxide coating, silicon oxide coating, nylon (polyamide) film, PE (polyester) film, PET (polyethylene terephthalate) film, PEN (polyethylene naphthalate) film, EAA (ethylene-acrylic acid copolymer) film, PVB (polyvinyl butyral) film, Saran (Saran Wrap®), BOPP (biaxially oriented polypropylene) film, COC (cyclic olefin copolymer) film, EVA (ethylene-vinyl acetate copolymer) film, PC (polycarbonate) film, PI (polyimide) film, thermoplastic polyester-based hot melt adhesive, and plasticized polyvinyl chloride (PVC). The gas barrier properties of a film layer can also be determined by taking water vapor permeability into consideration. For example, a film layer with gas barrier properties has an oxygen permeability of 100 cc / m or less. 2 / day / atm or less, and the water vapor transmission rate is 2.0g / m 2 A film layer having a viscosity of 1 / day / atm or less can be used. Specific examples of such a film layer include a general-purpose film such as PP or PET, on which aluminum, silicon oxide, alumina oxide, or the like is vapor-deposited, PTFE, and EVOH. In one embodiment, the film layer may be formed by laminating multiple materials. The laminated materials may be the same or different. The number of film layers is not particularly limited, and may be, for example, 2 to 5 layers. For example, the film layer may be formed by laminating polyimide, PTFE, and polyimide in this order.

[0079] Alternatively, a multilayer laminate film having substantially improved gas barrier properties by forming a multilayer structure using materials that have a certain degree of gas barrier properties but do not have a high gas barrier properties may be used as the covering portion 316. Examples of materials for such films include polyurethane. Specifically, the multilayer laminate film as the covering portion 316 may be formed by laminating EVOH, PVDC, or the like onto PP, PE, PET, PVC, PLA, or the like.

[0080] Furthermore, when a conductive material is used as the material for the covering portion 316, the covering portion 316 includes a layer formed of the conductive material as well as a layer formed of an insulating material. For example, when a metal-deposited film or a metal foil laminate film is used as the covering portion 316, the covering portion 316 includes an insulating layer in addition to a layer formed of such a metal. Examples of such metals include aluminum, gold, and silver.

[0081] Furthermore, when a material that has gas barrier properties but is vulnerable to water is used as the material for the covering portion 316, the covering portion preferably has a layer formed of that material and a layer formed of a material that is difficult for water to permeate and that covers the layer formed of the material that is vulnerable to water. An example of a layer formed of a material that is vulnerable to water is a PVOH (polyvinyl alcohol) film.

[0082] In addition, in the second element 31Q, the surface of the odorant receiving layer 315 may be protected by a covering 316 formed of an air layer and a material with high thermal conductivity. For example, the covering 316 may include an air layer and a plate material covering the air layer. Furthermore, the thermal conductivity of the plate material may be 25.7 W / m / K or more under a temperature condition of, for example, 20°C.

[0083] Here, sensor chamber 60, in which first element 31P and second element 31Q are provided, may include a spacer for forming a passage for passing the gas phase within sensor chamber 60. By sandwiching a metal plate material around second element 31Q in a portion of the spacer, a layer of air and covering portion 316 including the plate material covering the layer of air can be formed. As a result, second element 31Q, which is covered by the air layer and plate material as covering portion 316, is not affected by "heat transfer only." On the other hand, first element 31P, which does not have covering portion 316, is not covered by the plate material and the layer of air, and is therefore affected by "odor substances and heat transfer."

[0084] The covering portion 316 may also include a laminate film. For example, the second element 31Q may have a covering portion 316 in which only the odorant receiving layer 315 and the metal wiring 313 are vacuum-laminated. In this case, the odor measuring device 100 does not need to include the sensor chamber 60.

[0085] The covering portion 316 may also include at least one of paraffin and a hot-melt adhesive. For example, the second element 31Q may have a solid material (e.g., a melting point of 60 to 120°C) disposed on the surface of the odorant receiving layer 315, which has a melting point in a temperature range equal to or higher than the temperature of the environment in which the sensor element 31 is used, and the material is heated at a high temperature to form an insulating protective film as the covering portion 316. For example, a resin for a glue gun may be used as the hot-melt adhesive.

[0086] When measuring a specific odorant, the first element 31P and the second element 31Q may exhibit the same resistance value or different resistance values. If the first element 31P and the second element 31Q exhibit the same resistance value, the difference in resistance value when sample gas is applied to both the first element 31P and the second element 31Q can be obtained to calculate only the resistance value change due to the odor components contained in the sample gas. Even if the first element 31P and the second element 31Q exhibit different resistance values, by calculating the difference in resistance value between the first element 31P and the second element 31Q beforehand when sample gas is not applied, it is possible to calculate only the resistance value change due to the odor components contained in the sample gas in a similar manner. Alternatively, the difference in resistance value at each time for both the first element 31P and the second element 31Q can be calculated, for example, by calculating the difference between the baseline and peak top of the resistance value, and then calculating only the resistance value change due to the odor components contained in the sample gas.

[0087] [4. Odor Sensor 30] Below, the outline and effects of the odor sensor 30 employing the first element 31P and the second element 31Q will be described with reference to Figures 1 and 8. Figure 8 is a block diagram showing an example of the configuration of the odor sensor 30 employing the first element 31P and the second element 31Q.

[0088] The odor sensor 30 includes a first element 31P that detects odorous substances, a second element 31Q that obtains a value for correcting the measurement value of the first element 31P, a constant voltage power supply 32 (power supply), and a voltmeter 33 (measuring device).

[0089] The first metal wiring 313A and the second metal wiring 313B of the sensor element 31 are connected by a lead wire W. Fig. 8 shows an example in which a constant voltage power supply 32 and a voltmeter 33 are connected to the lead wire W.

[0090] The constant voltage power supply 32 is a power supply for supplying power to the sensor element 31. The constant voltage power supply 32 supplies a constant voltage via lead wires to the sensor element 31. The voltage value supplied by the constant voltage power supply 32 is 0.5V to 10V, for example, 2.5V or 5.0V.

[0091] The voltmeter 33 measures the potential difference that occurs between the first metal wiring 313A and the second metal wiring 313B when a constant voltage supplied from the constant voltage power supply 32 is supplied to the odorant receiving layer 315.

[0092] The odor sensor 30 includes an amplifier (not shown) in front of the voltmeter 33 in the circuit for measuring odor substances, and the amplifier amplifies the acquired signal and supplies it to the voltmeter 33.

[0093] In addition, the odor sensor 30 is equipped with a reference circuit in addition to the circuit for measuring odor substances, and the voltmeter 33 acquires the difference (potential difference) between the value acquired in the circuit for measuring odor substances and the value acquired in the reference circuit as a voltage value.

[0094] Although not an essential component, the odor sensor 30 may further include a housing 34. The housing 34 is a container capable of containing air containing odorous substances. When the housing 34 is included, the sensor element 31 is placed inside the housing 34.

[0095] The housing 34 has an inlet 341 for introducing an odorant and an outlet 342 for discharging air containing the odorant. The odorant may be introduced by introducing filter paper or the like soaked in the odorant into the housing 34 through the inlet 341, or by introducing air containing the odorant into the housing 34 through the inlet 341. The housing 34 is a container for containing air containing the odorant at a predetermined concentration (e.g., 200 ppm) or more.

[0096] Although not essential, an airflow generating fan 35 may be provided at the exhaust port 342 of the housing 34. The airflow generating fan 35 is used to generate an airflow inside the housing 34 and to exhaust gas inside the housing 34 from the exhaust port 342 to the outside of the housing 34.

[0097] The odor sensor 30 may include a constant current source (power supply) (not shown) instead of the constant voltage power supply 32, and an ammeter (measuring device) (not shown) instead of the voltmeter 33. In this case, the constant current source functions as a power source for supplying power to the sensor element 31, applying a constant current to the sensor element 31 via lead wires. Meanwhile, the ammeter measures the value of the current flowing between the first metal wiring 313A and the second metal wiring 313B when a constant current is applied to the odorant receiving layer 315. Both the first metal wiring 313A and the second metal wiring 313B can function as electrodes. Hereinafter, when the metal wiring 313 functions as an electrode, it may be referred to as the "electrode 313."

[0098] The odor sensor 30 outputs a measurement value that indicates the change over time in the electrical conductivity of the first element 31P and the second element 31Q corresponding to the first element 31P before and after an odor substance is adsorbed to the first element 31P, making it possible to detect and distinguish various odor substances.

[0099] 5. Odor Measuring Device 100 When various odor substances are adsorbed to the first element 31P, the odor sensor 30 described above can output the change in the electrical conductivity of the first element 31P over time for each odor substance. The odor sensor 30 can also output the change in the electrical conductivity of the second element 31Q over time. By applying this odor sensor 30, it is possible to compare the change in the electrical conductivity of the first element 31P over time when odor substance A is adsorbed to the first element 31P with the change in the electrical conductivity of the first element 31P over time when odor substance B is adsorbed to the first element 31P. Based on the results of such comparisons, an odor measurement device 100 can be realized that can estimate the odor substance adsorbed to the first element 31P.

[0100] Furthermore, the odor measurement device 100 can estimate odor substances with high accuracy by using an estimation model 22 generated by machine learning. The estimation model 22 can be generated using training data including a combination of a time-varying pattern of the electrical conductivity of the first element 31P based on measurements taken when each of a plurality of odor substances is adsorbed onto the first element 31P, and identification information unique to the odor substance. The time-varying pattern of the electrical conductivity of the first element 31P is generated based on values ​​obtained by correcting measurements taken when each of a plurality of odor substances is adsorbed onto at least one first element 31P using measurements taken when the second element 31Q is used.

[0101] The following describes the outline and effects of an odor measurement device 100 that uses the odor sensor 30. The odor measurement device 100 is a device that estimates the odor substance adsorbed to the first element 31P from the change in electrical conductivity that occurs in the first element 31P and the second element 31Q to which the above-mentioned resin composition is applied.

[0102] The odor measuring device 100 of this embodiment separately comprises a sensor chamber 60 equipped with a plurality of sensor elements 31 (hereinafter also referred to as a "sensor element group 31"), and a target sample receiving section 50 into which a target sample containing an odorant is introduced and which contains a gas containing the odorant generated from the target sample. The plurality of sensor elements 31 includes at least one first element 31P capable of outputting a measurement result corresponding to the odorant contained in the first gas, and at least one second element 31Q capable of outputting a measurement result in which the influence of the odorant is reduced. In this embodiment, each sensor element 31 included in the sensor element group 31 will be simply referred to as a "sensor element 31."

[0103] The odor measurement device 100 of this embodiment employs a configuration in which the gas containing the odor substance inside the target sample receiving section 50 is pushed toward the sensor chamber 60 using another gas (carrier gas). In this embodiment, the gas inside the target sample receiving section 50 when the target sample is introduced into the target sample receiving section 50 (i.e., the gas containing the odor substance to be detected) is referred to as the first gas. On the other hand, the carrier gas used to push the first gas toward the sensor chamber 60 is referred to as the second gas.

[0104] Fig. 1 is a schematic diagram of an odor measurement device 100. As shown in Fig. 1, the odor measurement device 100 includes an odor sensor 30, a target sample receiving unit 50, a sensor chamber 60, a gas supply unit 80, and an estimation device 10. The odor measurement device 100 may further include an adjustment unit 51. The odor measurement device 100 may further include an estimation device 10a.

[0105] 1 shows, as an example, an example in which gas flows from gas supply unit 80 to target sample receiving unit 50 and sensor chamber 60 in that order. Gas supply unit 80, target sample receiving unit 50, and sensor chamber 60 are each connected by a tube.

[0106] [Target sample receiving section 50] The target sample receiving section 50 can receive a target sample containing an odorant and retain a first gas. The target sample receiving section 50 has a first port 501 through which a second gas entering the target sample passes, and a second port 502 through which the first and second gases exiting the target sample can pass. In FIG. 1 , the first port 501 is located at the top of the target sample receiving section 50 and the second port 502 is located at the bottom of the target sample receiving section 50, but this is not limiting. For example, the positions of the first port 501 and the second port 502 can be appropriately set depending on the type and combination of odor components contained in the first gas. For example, the positions of the first port 501 and the second port 502 may be changed depending on whether the weight per unit volume (i.e., specific gravity) of the odor components contained in the first gas is heavier or lighter than that of the second gas. 8, the target sample receiving section 50 may be provided with an airflow generating fan 35 therein.

[0107] The target sample receiving unit 50 includes a sample inlet 503 for receiving a liquid or solid target sample. The target sample receiving unit 50 may also include a mounting unit (not shown) for mounting the target sample. If the target sample is a liquid, the mounting unit may be a cup for holding the liquid, or if the target sample is a solid, the mounting unit may be a Petri dish on which the solid is placed. The target sample may be introduced into the target sample receiving unit 50 in a gaseous state as a first gas through the sample inlet 503. In this way, since the target sample receiving unit 50 can receive a liquid or solid target sample, it is possible to adjust the concentration of the odorant in the first gas. For example, even if the odorant is the same, it is easy to adjust the concentration of the odorant in the first gas.

[0108] The inner surface of the target sample receiving section 50 may be lined with a material that is inactive to odorants. A material that is inactive to odorants is a material that does not significantly change the concentration of each odorant contained in the gas sent to the sensor chamber 60. For example, a material that is inactive to odorants is a material that odorants are unlikely to adsorb or dissolve into. Examples of materials that are inactive to odorants include glass, metal, and resin. When using metal, stainless steel (SUS) is preferred, and when using resin, fluorine-based resin, polypropylene (PP), polyethylene (PE), ABS resin, and polyethylene terephthalate (PET) are preferred.

[0109] If the inner surface of the target sample receiving portion 50 is made of a material that adsorbs the odorous substances contained in the first gas, the odorous substances may be adsorbed to each portion, which may affect subsequent measurements.

[0110] Since the inner surface of the target sample receiving portion 50 is made of a material that is inactive to odorants, the risk of the material of the inner surface reacting with the odorants contained in the first gas, or the odorants being adsorbed onto the inner surface, is reduced. Therefore, the risk of the odorants contained in the first gas supplied to the sensor chamber 60 changing while contained in the target sample receiving portion 50, or the concentration of the odorants being diluted, is reduced.

[0111] Whether the target sample is a liquid or a solid, the odor measurement device 100 is provided with the target sample receiving section 50, thereby making the concentration of the first gas uniform within the target sample receiving section 50 before sending the first gas into the sensor chamber 60. Furthermore, by providing the target sample receiving section 50, the odor measurement device 100 is able to push the first gas into the sensor chamber 60 at a constant flow rate. This allows the odor measurement device 100 to send the first gas to the sensor chamber 60 under the same conditions each time, even when measurements are performed repeatedly, thereby enabling repeated, stable measurements.

[0112] The volume of the target sample receiving section 50 is preferably 1 to 200 times the volume of the sensor chamber 60. In particular, the volume of the target sample receiving section 50 is preferably larger than the volume of the sensor chamber 60. The volume of the target sample receiving section 50 is more preferably 2 or more times the volume of the sensor chamber 60, and even more preferably 4 or more times. Furthermore, the volume of the target sample receiving section 50 is preferably 100 or less times the volume of the sensor chamber 60, and even more preferably 60 or less times. By making the volume of the target sample receiving section 50 1 or more times the volume of the sensor chamber 60, the concentration of odor substances in the sensor chamber 60 is appropriately adjusted, and measurement results by the sensor provided in the sensor chamber 60 are stably output. Furthermore, by making the volume of the target sample receiving section 50 200 or less times the volume of the sensor chamber 60, it is easier to adjust the temperature and humidity within the target sample receiving section 50, which allows the sensor measurement results to be stably output and the odor measurement device 100 to be compact.

[0113] If the volume of the target sample receiving section 50 is less than one time the volume of the sensor chamber 60, the odor substances generated in the target sample receiving section 50 may be diluted in the sensor chamber 60, resulting in a decrease in the measurement sensitivity of the sensor. Furthermore, if the volume of the target sample receiving section 50 is more than 200 times the volume of the sensor chamber 60, the volume of the target sample receiving section 50 may be too large, reducing the uniformity of the concentration, temperature, and humidity of the first gas. This may make it impossible to deliver the first gas to the sensor chamber 60 under the same conditions when repeated measurements are performed. Furthermore, the overall size of the odor measurement device 100 may become larger.

[0114] FIG. 1 shows an example in which the volume of the target sample receiving portion 50 is eight times the volume of the sensor chamber 60 .

[0115] For example, if the inner surface of the tubular body 93 is made of a material that adsorbs odorous substances contained in the first gas, the odorous substances may be adsorbed to various parts, potentially affecting subsequent measurements. Therefore, it is preferable that the inner surface of the tubular body 93, which guides the first gas from the target sample receiving section 50 to the sensor chamber 60, be made of a material that is inactive to odorous substances, similar to the inner surface of the target sample receiving section 50. Examples of materials that are inactive to odorous substances include glass, metal, and resin. When using metal, stainless steel (SUS) is preferred, and when using resin, fluorine-based resin, polypropylene (PP), polyethylene (PE), ABS resin, and polyethylene terephthalate (PET) are preferred.

[0116] The target sample receiving section 50 may be configured to be detachable from the tubular bodies 92 and 93. In this way, since the target sample receiving section 50 is detachable, when the previous measurement is completed and the next measurement is to be performed, a new target sample receiving section 50 can be attached without purging the inside of the target sample receiving section 50. This allows the odor measuring device 100 to perform multiple measurements in a short period of time.

[0117] Furthermore, because the target sample receiving section 50 is detachable, the target sample receiving section 50 into which the target sample has been introduced can be maintained at a desired temperature using a temperature-retaining chamber separate from the odor measurement device 100. This allows the odor measurement device 100 to adjust the temperature of the target sample receiving section 50, even if, for example, the adjustment section 51 described below cannot be provided in the odor measurement device 100.

[0118] [Adjustment section 51] The adjustment unit 51 adjusts at least one of the temperature and humidity of the first gas contained in the target sample receiving unit 50. When the adjustment unit 51 adjusts the temperature, the adjustment unit 51 is, for example, a heater or a cooler. In this case, the adjustment unit 51 may be configured to cover the entire target sample receiving unit 50. When the adjustment unit 51 adjusts the humidity, the adjustment unit 51 is, for example, a humidifier or a dehumidifier. The adjustment unit 51 may adjust at least one of the temperature and humidity for each type of first gas, or may change at least one of the temperature and humidity at predetermined time intervals during measurement of the same first gas.

[0119] By the adjustment unit 51 adjusting at least one of the temperature and humidity of the first gas in the target sample receiving unit 50, the odor measuring device 100 can send the first gas to the sensor chamber 60 using conditions according to, for example, the type of the first gas (gas weight, volatility, etc.). Furthermore, this allows the odor measuring device 100 to send the first gas at a stable concentration to the sensor chamber 60, improving the accuracy of the measurement.

[0120] [Sensor Chamber 60] The sensor chamber 60 is a space that houses the sensor element 31 for measuring odor substances. The sensor chamber 60 is connected to the second port 502 of the target sample receiving portion 50. Specifically, the sensor chamber 60 includes a gas supply port 601 and a gas exhaust port 602, and the second port 502 of the target sample receiving portion 50 is connected to the gas supply port 601.

[0121] The sensor chamber 60 includes at least one first element 31P capable of outputting a measurement result corresponding to an odorant contained in the first gas, and at least one second element 31Q capable of outputting a measurement result in which the influence of the odorant is reduced. Note that multiple first elements 31P may be provided. When multiple first elements 31P are provided, each of the multiple first elements 31P may have a different resin composition as the odorant receiving layer 315. That is, the sensitivity and specificity of each of the multiple first elements 31P to the odorant may differ. The sensor chamber 60 of FIG. 1 includes, as an example, a first element 31P and a first element 31Pb, but is not limited thereto. The sensor chamber 60 of FIG. 1 may also include a first element 31Pc having an odorant receiving layer 315 made of a resin composition different from that of the first elements 31P and 31Pb. First element 31P and first element 31Pb can output measurement results corresponding to the same odorant contained in the first gas, but the measurement results output by each element are different. The measurement results corresponding to the odorant are, for example, measurement results corresponding to the concentration of the odorant. In the following description, when there is no need to distinguish between first elements 31P, 31Pb, 31Pc, and first element 31Pd (described later), these will be collectively referred to as "first element 31P."

[0122] The sensor chamber 60 may be provided with any combination and arrangement of first elements 31P each having a different resin composition as the odorant receiving layer 315. The sensor chamber 60 may also be provided with multiple first elements 31P each having the same resin composition as the odorant receiving layer 315.

[0123] Here, the first element 31P and the first element 31Pb may be sensor elements capable of outputting measurement results corresponding to different odor substances. For example, the sensor chamber 60 may be provided with a first element 31P capable of outputting measurement results corresponding to an odor substance contained in a first gas, and a first element 31Pb capable of outputting measurement results corresponding to a second odor substance different from the odor substance contained in the first gas. For example, the odor sensor 30 may include first elements 31P and 31Pb whose odor substance receiving layers 315 use different resin compositions.

[0124] By providing multiple first elements 31P in which resin compositions with different odorant adsorption properties are used in the odorant receiving layer 315, the odor measuring device 100 can simultaneously perform estimations for multiple odorants. In addition to the first element 31P according to one embodiment of the present invention, a first element 31P in which the odorant receiving layer 315 does not contain surfactant (B) may also be used.

[0125] Furthermore, by using the odor measurement device 100, it is possible to obtain, for each known odor substance, a first change pattern indicating the change in the electrical conductivity of the first element 31P and a second change pattern indicating the change in the electrical conductivity of the first element 31Pb. The estimation model 22 may be generated by machine learning using both the first change pattern and the second change pattern. The odor measurement device 100 estimates odor substances using the estimation model 22 generated in this way, and therefore can more precisely identify each odor substance.

[0126] Additionally, at least one second element 31Q is provided in the sensor chamber 60. The second element 31Q has the same odorant receiving layer 315 as the first element 31P, as well as a covering portion 316. The other configuration of the second element 31Q is the same as that of the first element 31P. If a single odor measuring device 100 includes multiple first elements 31P with different resin compositions, only one second element 31Q having an odorant receiving layer 315 corresponding to one of the multiple first elements 31P may be provided. Alternatively, if a single odor measuring device 100 includes multiple first elements 31P with different resin compositions, multiple second elements 31Q having odorant receiving layers 315 corresponding to each of the first elements 31P may be provided.

[0127] When only one second element 31Q is provided in the sensor chamber 60, the correction value derived from the data obtained from the first element 31P and the second element 31Q having an odorant receiving layer 315 of the same composition as the first element 31P can also be used for environmental correction of the measurement values ​​of the first element 31P having an odorant receiving layer 315 of a different composition.

[0128] The second element 31Q also outputs a measurement value in the same manner as the first element 31P. Here, since the second element 31Q has a coating 316, the odorant is not desorbed from the odorant receiving layer 315 of the second element 31Q. Therefore, the measurement value output by the second element 31Q is a value that is influenced by the temperature of the measurement environment, etc., while being less influenced by the odorant.

[0129] The odor measurement device 100 corrects the measurement result from the first element 31P with the measurement result from the second element 31Q, analyzes the corrected result, and uses the corrected result to estimate the odor substance. This allows the odor measurement device 100 to more accurately identify odor substances based on values ​​that reduce the influence of the environment on the measurement result.

[0130] 1 includes a plurality of sensor elements 31 arranged in a 4×4 array, as an example. The number of sensor elements 31 and the manner in which the sensor elements 31 are arranged are not limited. The total number of sensor elements 31 included in the sensor chamber 60 is also not particularly limited, and may be, for example, 2, 16, or 64. When a plurality of sensor elements 31 are arranged in a 4×4 array, for example, one sensor element 31 may be a second element 31Q and the other sensor element 31 may be a first element 31P. Note that the breakdown of first elements 31P and second elements 31Q included in the plurality of sensor elements 31 is not limited to this.

[0131] The material of the inner surface of sensor chamber 60 is preferably a material that is inactive to odorants, similar to target sample receiving section 50. Examples of materials that are inactive to odorants include glass, metal, and resin. When metal is used, stainless steel (SUS) is preferable, and when resin is used, fluorine-based resin, polypropylene (PP), polyethylene (PE), ABS resin, and polyethylene terephthalate (PET) are preferable. When the material of the inner surface of sensor chamber 60 is a material that adsorbs odorants contained in the first gas, adsorption of the odorants into sensor chamber 60 may reduce the amount of change in output from first element 31P in subsequent measurements, potentially preventing odor measuring device 100 from performing accurate measurements.

[0132] [Multiple sensor elements 31 (sensor element group 31)] The plurality of sensor elements 31 may comprise a thin film. As an example, the odorant receiving layer 315 in Figures 2 and 3 is a thin film.

[0133] One possible mode for sending the first gas containing an odorant into the sensor chamber 60 is to install a vacuum pump on the gas outlet 602 side of the sensor chamber 60 and use the vacuum pump to draw the gas into the sensor chamber 60 from the gas supply port 601 side of the sensor chamber 60. However, if the sensor elements 31 and 31b are equipped with thin films, negative pressure within the sensor chamber 60 may cause the thin films to expand, preventing the sensor elements 31 and 31b from outputting stable measurement results. In the odor measurement device 100 according to this embodiment, the gas supply unit 80 pushes the gas from the sensor chamber 60 and the first port 501 side of the target sample receiving unit 50 to send the first gas into the sensor chamber 60, so the pressure within the sensor chamber 60 is positive. Therefore, the odor measurement device 100 can obtain stable measurement results even if multiple sensor elements 31 are equipped with thin films.

[0134] The thin film of the plurality of sensor elements 31 may also contain a conductive carbon material, a resin composition, and a surfactant.

[0135] [Gas supply unit 80] The gas supply unit 80 is connected to the first port 501 of the target sample receiving unit 50, and by sending a second gas into the inside of the target sample receiving unit 50, the first gas is sent from inside the target sample receiving unit 50 toward the sensor chamber 60.

[0136] A valve 81 may be provided between the gas supply unit 80 and the target sample receiving unit 50. By opening and closing the valve 81, the start and stop of gas supply from the gas supply unit 80 may be adjusted.

[0137] In this way, the gas supply unit 80 pushes the gas from the first port 501 side of the target sample receiving unit 50 to send the first gas into the sensor chamber 60, so the pressure inside the sensor chamber 60 is positive. This allows the odor measurement device 100 to obtain stable measurement results. Furthermore, because the second gas can be sent by opening and closing the valve 81, the odor measurement device 100 can send the first gas from the target sample receiving unit 50 toward the sensor chamber 60 at any timing. This allows the odor measurement device 100 to improve the reproducibility of the waveform shape output by each sensor element 31 when repeatedly measuring odor substances contained in the first gas using the sensor element group 31.

[0138] The second gas may be an inert gas or air. Examples of inert gases include argon and nitrogen. When the second gas is an inert gas, the gas supply unit 80 may be a gas cylinder.

[0139] Furthermore, when the second gas is air, the gas supply unit 80 may be a pump. In this case, in order to remove components that react with the first gas contained in the target sample receiving unit 50, the odor measuring device 100 may be provided with, for example, an activated carbon filter on the first port 501 side of the target sample receiving unit 50.

[0140] The odor measuring device 100 may further include a mass flow controller on the side of the first port 501 of the target sample receiving section 50, more specifically, between the valve 81 and the gas supply section 80. The odor measuring device 100 employing this configuration can send the first gas from the target sample receiving section 50 to the sensor chamber 60 at a constant flow rate, allowing the multiple sensor elements 31 to produce stable outputs.

[0141] 1 shows a configuration in which the first gas and the second gas leaving the inside of the target sample receiving section 50 pass through the pipe 93 and the sensor chamber 60, but this configuration is not limited to this. Because the target sample receiving section 50 of the odor measurement device 100 has a larger volume than the sensor chamber 60, it is not necessary to send all of the first gas inside the target sample receiving section 50 to the sensor chamber 60 during measurement. Furthermore, when the inside of the target sample receiving section 50 is purged with the second gas after measurement, the target sample receiving section 50 and the sensor chamber 60 do not need to be connected. Therefore, the odor measurement device 100 may be configured such that a valve (not shown) is provided in the pipe 93 so that the first gas and the second gas leaving the inside of the target sample receiving section 50 can be exhausted without passing through the sensor chamber 60.

[0142] [Estimation device 10] The estimation device 10 is a device that estimates odor substances detected by the odor sensor 30. The estimation device 10 is, for example, a computer, and includes a CPU and memory (not shown). The estimation device 10 is communicatively connected to the odor sensor 30. Specifically, the estimation device 10 performs odor substance estimation by analyzing measurement values ​​obtained from the odor sensor 30. If the sensor chamber 60 further includes a first element 31Pc whose odor substance receiving layer 315 uses a resin composition different from that of the first element 31P and the first element 31Pb, the estimation device 10 may further acquire and analyze measurements measured by a voltmeter by supplying a constant voltage to the first element 31Pc. In this case, the sensor chamber 60 may include multiple second elements 31Q. The odor substance receiving layer 315 of each of the multiple second elements 31Q may be made of the same resin composition as the first element 31P, the same resin composition as the first element 31Pb, or the same resin composition as the first element 31Pc. The estimation device 10 may also display the measurement values ​​themselves, waveforms plotting the measurement values, and estimation results of unknown odor substances based on an estimation model. The estimation device 10 may also display numerical values ​​and graphs showing changes in the abundance ratio of each odor substance in a gas containing multiple odor substances. The estimation device 10 may also generate an estimation model 22 used to estimate odor substances.

[0143] <Generation of Estimation Model 22> Next, the configuration of the odor measurement device 100 that performs the process of generating the estimation model 22 used to estimate odor substances, and the process of generating the estimation model 22 will be described with reference to FIGS. 9 and 10. FIG.

[0144] The estimation model 22 is generated by machine learning using training data including a combination of measurement values ​​measured by the voltmeter 33 when each of a plurality of odor substances is adsorbed onto at least one first element 31P, and identification information specific to the odor substance that provided the measurement value. Here, the identification information specific to the odor substance may be, for example, the name, CAS number, and chemical formula of the odor substance.

[0145] (Configuration of the estimation device 10 (generation of the estimation model 22)) Fig. 9 is a functional block diagram showing an example of the configuration of the odor measuring device 100. For ease of explanation, the same reference numerals are used to denote components having the same functions as those described in Fig. 1, and their description will not be repeated.

[0146] As shown in FIG. 9, the estimation device 10 includes an input unit 15, a control unit 1, and a storage unit 2.

[0147] The input unit 15 is for receiving various input operations from the user, and may be, for example, a keyboard, a mouse, a touch panel, or the like.

[0148] The control unit 1 includes a measurement value acquisition unit 11 (acquisition unit), a change pattern analysis unit 12 (analysis unit), a learning control unit 13, and an estimation model generation unit .

[0149] The measurement value acquiring unit 11 acquires a measurement value from the voltmeter 33. Furthermore, the measurement value acquiring unit 11 uses the acquired measurement value to calculate a value indicating the electrical conductivity of the sensor element 31 (for example, a resistance value, an impedance, etc.). The measurement value acquiring unit 11 may acquire the measurement value from the voltmeter 33 at predetermined time intervals (for example, every 0.1 seconds).

[0150] Furthermore, the measurement value acquiring unit 11 corrects the output value acquired from the first element 31P based on the measurement value acquired from at least one second element 31Q.

[0151] 6 is a graph showing the relationship between temperature and resistance when odorous substance measurements are performed using first element 31P and second element 31Q. In FIG. 6, resistance values ​​are plotted as a result of measurements performed for a predetermined period of time under multiple temperature conditions using sensor chamber 60 filled with nitrogen.

[0152] FIG. 7 is a graph showing the resistance versus time for the results of measurements of odorants performed using first element 31P and second element 31Q. FIG. 7 shows the change in resistance obtained based on the output values ​​from first element 31P and second element 31Q when the sensor chamber 60 is filled with nitrogen, then replaced with an odorant, and then replaced again with nitrogen. Specifically, five minutes after the start of measurement, the sensor chamber 60 is filled with nitrogen, 10 minutes after the start of measurement, the sensor chamber 60 is replaced with 10,000 ppm EtOH, and 15 minutes after the start of measurement, the sensor chamber 60 is replaced with nitrogen again. Note that the measurement only requires that the sensor element 31 is exposed to the odorant being measured; replacing with nitrogen is not required.

[0153] As shown in Figure 6, when the ambient temperature changed, the resistance values ​​measured for first element 31P and second element 31Q changed with almost the same slope. On the other hand, when the ambient gas was replaced with EtOH, the resistance value of first element 31P changed significantly, but the resistance value of second element 31Q remained almost unchanged from the resistance value in a nitrogen atmosphere. This is thought to be because first element 31P does not have coating 316, while second element 31Q has coating 316. In other words, the results shown in Figures 6 and 7 show that by including coating 316, second element 31Q is affected by temperature but is not affected by ambient odor substances (e.g., ethanol, etc.).

[0154] Therefore, when performing learning or estimation using the measurement results of the first element 31P and the second element 31Q, the measurement acquisition unit 11 adds a predetermined coefficient to the measurement output by the second element 31Q so that the results during the time period when the odorant is not adsorbed are approximately the same. This coefficient is set in advance based on the odorant receiving layer 315 and the temperature of the measurement environment, etc. This reduces the influence on the measurement results due to the second element 31Q having the covering portion 316, making it possible to compare the measurement results of the first element 31P and the second element 31Q. Furthermore, the measurement acquisition unit 11 uses the result value of the second element 31Q after adding the coefficient as a reference and calculates the measurement value of the first element 31P relative to the reference.

[0155] Note that the measurement value acquiring unit 11 may perform the correction using a method different from that described above. For example, if data is acquired over different time ranges for each of the first element 31P and the second element 31Q, the measurement results per temperature of the first element 31P and the second element 31Q will not be linearly approximated. Therefore, in such a case, a separate function is prepared and one of the measurement results is corrected to make the measurement results of the first element 31P and the second element 31Q comparable.

[0156] The change pattern analysis unit 12 analyzes the change over time in the electrical conductivity of at least one first element 31P. The change pattern analysis unit 12 calculates a value indicating the amount of change in the electrical conductivity of the sensor element 31 due to the adsorption of an odorant, using the resistance value calculated by the measurement value acquisition unit 11. The change pattern analysis unit 12 generates data indicating a change pattern that indicates the change over time in the calculated amount of change in the electrical conductivity of the first element 31P.

[0157] The change pattern analysis unit 12 generates a change pattern that indicates the change over time in the electrical resistance of the first element 31P using the measurement values ​​of the first element 31P corrected by the measurement value acquisition unit 11. This allows the change pattern analysis unit 12 to generate a change pattern that is less affected by the temperature of the measurement environment. Note that if a voltage is continuously applied to the sensor element 31, the obtained data will not be a linear approximation due to the effects of Joule heat, etc. Therefore, the above-described method is used, for example, when sampling and plotting data within the same unit time using the first element 31P and the second element 31Q.

[0158] When the change pattern analysis unit 12 acquires identification information indicating a known odor substance corresponding to a change pattern, the change pattern may be associated with identification information specific to the known odor substance and stored in the change pattern database 21 (learning data).

[0159] The learning control unit 13 reads the change pattern database 21 from the storage unit 2 and controls the generation of the estimation model 22 by machine learning. Here, the change pattern database 21 is a database containing combinations of change patterns obtained based on corrected values ​​of measured values ​​measured when multiple odor substances are adsorbed to the first element 31P, and identification information unique to the known odor substances that provided the measured values. The learning control unit 13 inputs the change patterns read from the change pattern database 21 to the estimation model generation unit 14. In addition, the learning control unit 13 compares the identification information of the odor substance corresponding to the change pattern input to the estimation model generation unit 14 with the estimation result output from the estimation model generation unit 14, and outputs a correction instruction to the estimation model generation unit 14 according to the comparison result.

[0160] The estimation model generation unit 14 generates the estimation model 22 by a machine learning algorithm using the change patterns stored in the change pattern database 21. The estimation model generation unit 14 may be configured to generate the estimation model 22 by using a known supervised machine learning algorithm. Examples of machine learning algorithms that can be applied to the estimation model generation unit 14 include the k-nearest neighbor method, logistic regression, support vector machines, random forests, and neural networks.

[0161] (Process for generating estimation model 22) The process of generating an estimation model 22 using the odor measurement device 100 will be described below with reference to FIG. 10. FIG. 10 is a flowchart showing an example of the process flow of the estimation device 10 of the odor measurement device 100 generating the estimation model 22. The estimation model 22 is generated by machine learning using training data including a combination of a change pattern obtained based on corrected values ​​of measurements taken by the voltmeter 33 when each of a plurality of odor substances is adsorbed onto at least one first element 31P, and identification information unique to the odor substance that provided the measurement value. Here, the identification information unique to the odor substance may be, for example, the name of the odor substance, a CAS number, a chemical formula, etc.

[0162] First, the measurement value acquisition unit 11 acquires the voltage value V0 measured at the first element 31P and the second element 31Q before the odorant is introduced into the target sample receiving unit 50, and calculates the respective resistance values ​​R0. The resistance value R0 obtained from the measurement results of the first element 31P is preferably 200 to 1000 Ω, more preferably 250 to 900 Ω, and most preferably 300 to 800 Ω. Then, the odorant is introduced into the target sample receiving unit 50 (step S1).

[0163] Meanwhile, the input unit 15 receives input such as the name of the known odor substance introduced into the target sample receiving unit 50 (step S2). The processing of step S2 may be performed before step S1.

[0164] Next, the measurement value acquiring unit 11 acquires the voltage value V measured in the first element 31P and the second element 31Q during the odor substance adsorption / desorption period, and calculates the respective resistance values ​​(step S3).

[0165] The measurement value acquiring unit 11 corrects the resistance value obtained from the first element 31P based on the resistance value obtained from the second element 31Q (step S4).

[0166] Next, the change pattern analysis unit 12 acquires information indicating the corrected measurement value of the first element 31P from the measurement acquisition unit 11. Based on this information, the change pattern analysis unit 12 generates corrected voltage value V or resistance change amount (ΔV) data (waveform or time-dependent change pattern) during the process before and after the odorant adsorption / desorption to the first element 31P (hereinafter referred to as the odorant adsorption / desorption period) (step S5).

[0167] Next, the change pattern analysis unit 12 associates the corrected change amount (ΔV) data (waveform or temporal change pattern) with the input name of the known odor substance and stores them in the change pattern database (step S6).

[0168] If no change patterns are stored for the predetermined types of existing odor substances (NO in step S7), that is, if there is still insufficient data to use for machine learning, the process returns to step S1.

[0169] If a change pattern is stored for a predetermined type of existing odor substance (YES in step S7), the learning control unit 13 reads out the change pattern for the known odor substance stored in the change pattern database 21 and inputs it to the estimation model generation unit 14. The estimation model generation unit 14 generates an estimation model 22 by machine learning based on the time-dependent change pattern (or feature extracted from the change pattern) stored in the change pattern database 21 (step S8).

[0170] The estimation model generation unit 14 stores the estimation model 22 generated by predetermined machine learning in the storage unit 2 (step S9).

[0171] 9 and 10, the estimation device 10 generates the estimation model 22, but this is not limiting. For example, the estimation device 10 may provide the same data as the change pattern database 21 to an external computer different from the estimation device 10 that has the same functions as the learning control unit 13 and the estimation model generation unit 14, and have the computer generate the estimation model 22.

[0172] The process of generating the estimation model 22 may include data preprocessing and feature extraction. Furthermore, the machine learning for generating the estimation model 22 may use a machine learning algorithm.

[0173] (Feature extraction) The learning data for generating the estimation model 22 by machine learning may be the measured values ​​themselves or may be feature quantities extracted from the measured values. The feature quantities may be, for example, statistics, differential and integral values, peak detection values, or autocorrelation values. Examples of statistical quantities include the mean value, variance, maximum value, minimum value, the difference between the maximum and minimum values, and standard deviation. Examples of differential and integral values ​​include the differential value (the slope of a graph showing the change in measured values ​​over time) and the integral value (the area of ​​the region defined by the curve showing the change in measured values ​​and the horizontal axis (e.g., the time axis) in a graph showing the change in measured values ​​over time). Examples of peak detection values ​​include the number and height of peaks in the change in measured values ​​(e.g., change over time). Examples of autocorrelation values ​​include the difference in the change in measured values ​​(e.g., change over time). These feature quantities can be extracted from measured values ​​based on known methods.

[0174] (Pretreatment method) The training data for generating the estimation model 22 by machine learning may be used for machine learning without preprocessing, or may be used after predetermined preprocessing as necessary. Furthermore, if preprocessing is performed, it may be performed before, after, or both before and after the feature extraction. Preprocessing may be performed by known methods. Known methods include correction, noise removal, standardization, data transformation, smoothing, and data expansion. Examples of correction include integration, addition, subtraction, and division using output ratios, independent component analysis (ICA), or statistics based on the measurement results of a standard gas using multiple sensor elements or commercially available sensors (e.g., temperature sensors or humidity sensors). Examples of noise removal include removal of outliers, white noise, and other noise. Examples of standardization include normalization and regularization of features. Examples of data transformation include removal of data trends, frequency transformation, and logarithmic transformation. Examples of smoothing include taking a moving average and difference of data. Examples of data expansion include adding the same sample data (for example, adding data assuming a normal distribution), adding new sample data (for example, adding data related to the mixture ratio of vectors), and the like.

[0175] (machine learning algorithms) Machine learning algorithms applicable to the estimation model generation unit 14 include regression analysis, classification, tree, time series analysis, neural network, and clustering. Examples of regression analysis include logistic regression, Lasso regression, elastic net regression, support vector regression (SVR), linear regression, ridge regression, and ensemble regression. Examples of classification include k-nearest neighbor method, support vector classification (SVC), Naive Bayes classifier, stochastic gradient descent (SGD), and kernel approximation. Examples of trees include decision trees, regression trees, random forests, boosting (lightGBM, XGboost), and stacking. Examples of time series include AR, MA, ARIMA, and state space. Examples of neural networks include multi-layer perceptrons (MLPs), convolutional neural networks (CNNs), recurrent neural networks (RNNs), residual neural networks (ResNets), transformers, and graph neural networks (GNNs). Examples of clustering methods include Gaussian mixture models (GMMs), k-means, mini k-means, variational Gaussian mixture models (VBGMMs), and kernel approximation.

[0176] <Identification of odor substances> Next, the configuration of the odor measurement device 100a that estimates odor substances using the estimation model 22 and the estimation process will be described with reference to FIGS.

[0177] (Configuration of Estimation Device 10a (Execution of Estimation Process)) Fig. 11 is a functional block diagram showing an example of the configuration of the odor measuring device 100a. For ease of explanation, the same reference numerals are used to designate components having the same functions as those described in Fig. 1 and Fig. 9, and their description will not be repeated.

[0178] As shown in Fig. 11, the estimation device 10a includes a control unit 1a, a storage unit 2a, and an output unit 18. Here, Fig. 11 shows a configuration example in which the estimation device 10 shown in Fig. 9 is used for odor substance estimation processing. In other words, the estimation device 10 shown in Fig. 9 and the estimation device 10a shown in Fig. 11 may be computers with the same hardware configuration.

[0179] The output unit 18 is for presenting the estimation result to the user, and may be, for example, a display, a speaker, a lamp, or the like.

[0180] The control unit 1 a includes a measurement value acquisition unit 11 (acquisition unit), a change pattern analysis unit 12 (analysis unit), an estimation unit 16, and an output control unit 17.

[0181] The estimation unit 16 uses the estimation model 22 to estimate the odor substance from the analysis results obtained by analyzing the measurement values ​​acquired from the odor sensor 30.

[0182] The output control unit 17 controls the output unit 18 to output the estimation result.

[0183] (Estimation process) Specific processing performed by each unit of the control unit 1a will be explained below with reference to Fig. 12. Fig. 12 is a flowchart showing an example of the processing flow for the estimation device 10a to estimate an odor substance.

[0184] First, the measurement value acquisition unit 11 acquires the voltage value V0 measured in the first element 31P and the second element 31Q before the odor substance is introduced into the target sample receiving unit 50, and calculates the respective resistance values ​​R0. Then, an unknown odor substance (regardless of its properties) is introduced into the target sample receiving unit 50 (step S11).

[0185] Next, the measurement value acquiring unit 11 acquires the voltage value V measured in the first element 31P and the second element 31Q during the odor substance adsorption / desorption period, and calculates the respective resistance values ​​(step S12).

[0186] The measurement value acquiring unit 11 corrects the resistance value obtained from the first element 31P based on the resistance value obtained from the second element 31Q (step S13).

[0187] Next, the change pattern analysis unit 12 generates data (waveform or time-dependent change pattern) of the corrected voltage value V or change in resistance value (ΔV) before and after the adsorption and desorption of the unknown (i.e., the odor substance to be estimated) to the first element 31P (step S14).

[0188] Next, the estimation unit 16 acquires the time-dependent change pattern generated by the change pattern analysis unit 12. The estimation unit 16 estimates the unknown odor substance from the corrected time-dependent change pattern (or the feature amount extracted from the change pattern) based on the estimation model 22 (step S15).

[0189] The output control unit 17 controls the output unit to output the estimation result (step S16).

[0190] In the above embodiment, the estimation device 10 that generates the estimation model 22 and the estimation device 10a that estimates odor substances using the estimation model 22 have been described. Note that the estimation device 10 and the estimation device 10a may be separate devices or may be a single device.

[0191] <Configuration example of sensor element 31c> FIG. 13 is a top view showing an example of the configuration of one sensor element 31c included in the sensor element group 31. The sensor element 31c includes an electrode 313, which is a metal wiring arranged on a substrate 311, and a circular odorant receiving layer 315c formed on the electrode 313. The electrode 313 includes a first metal wiring 313C and a second metal wiring 313D. The first metal wiring 313C and the second metal wiring 313D are each metal wirings that function as electrodes for measuring changes in the electrical conductivity of the odorant receiving layer 315c. The diameter R of the odorant receiving layer 315c is 0.2 mm or more and 5 mm or less. In FIG. 13, the shape of the odorant receiving layer 315c included in the sensor element 31c is elliptical as an example, but is not limited thereto. If the shape of the odorant receiving layer 315c is elliptical, the average of the minor axis and the major axis may be 0.2 mm or more and 5 mm or less. The odorant receiving layer 315c may also be perfectly circular in shape.

[0192] FIG. 14 is a top view showing an example of the configuration of one sensor element 31d included in the sensor element group 31. The sensor element 31d comprises an electrode 313 (first metal wiring 313C, second metal wiring 313D) arranged on the substrate 311, and a strip-shaped odorant receiving layer 315d formed on the electrode 313. The length W of the short width of the odorant receiving layer 315d is 0.2 mm or more and 5 mm or less. In the following description, when there is no need to distinguish between the odorant receiving layers 315c and 315d, they will be collectively referred to as the "odorant receiving layer 315."

[0193] The electrodes of the sensor elements 31 included in the sensor element group 31 each have a first electrode and a second electrode, and the first and second electrodes may be arranged in the form of parallel lines, parallel curves, a comb shape, or concentric circles. Regardless of the shape of the first and second electrodes, it is preferable that they are arranged in line symmetry or point symmetry with each other. By arranging the first and second electrodes in this manner, the odor measuring device 100 can measure odor substances contained in gas with high accuracy.

[0194] Sensor element 31c in Fig. 13 has first metal wiring 313C and second metal wiring 313D. Furthermore, as an example, first metal wiring 313C is a first electrode composed of metal wiring 313a and metal wiring 313b, and the two metal wirings are arranged in a T-shape so as to be perpendicular to each other. Second metal wiring 313D is a second electrode composed of two metal wirings 313c and 313d, similar to first metal wiring 313C, and is configured so as to be arranged in a T-shape so as to be perpendicular to each other. Furthermore, first metal wiring 313C and second metal wiring 313D are arranged in parallel lines so that metal wiring 313a and metal wiring 313c face each other.

[0195] The first metal wiring 313C and the second metal wiring 313D are particularly arranged in a T-shape, which allows the first metal wiring 313C and the second metal wiring 313D to be located at a suitable distance from each other, thereby stabilizing the electrode resistance. For example, if the electrodes were arranged in a comb shape, the distance between the electrodes would be too short, which could result in the electrode resistance being too low. Furthermore, the first metal wiring 313C and the second metal wiring 313D are arranged in a T-shape, which allows the slurry to spread easily in the application process of the sensor element 31 (described later) because there are no uneven portions of the electrode that could hinder the slurry from spreading. Furthermore, the ease of spreading the slurry also contributes to a consistent thickness of the odorant receiving layer 315 after drying.

[0196] 15 is a perspective view showing an example of the configuration of one sensor element 31c included in the sensor element group 31. As shown in FIG. 15, in sensor element 31c, first metal wiring 313C and second metal wiring 313D are each connected to pins 317 at ends of the first metal wiring 313C and second metal wiring 313D that do not face each other. Pins 317 are conductive members for electrically connecting first metal wiring 313C and second metal wiring 313D to other components of the odor sensor 30. Although not shown, sensor elements 31c and 31d shown in FIGS. 13 and 14 also include pins 317 shown in FIG. 15.

[0197] <Method of manufacturing sensor element> The following describes a manufacturing method for manufacturing the various types of sensor elements 31 used in the odor measuring device 100. The odorant-receiving layer 315 of the sensor element 31 can use slurries with various compositions as its raw material.

[0198] (Slurry preparation process) First, multiple types of slurries with different mixing ratios of conductive carbon material and resin composition are prepared. The mixing ratio of the conductive carbon material and resin composition can be appropriately set depending on the desired sensitivity and detection specificity of the odorant receiving layer 315. In addition to the conductive carbon material and resin composition, the slurries may contain solvents, additives, and surfactants.

[0199] (Electrode placement process) Next, electrodes are arranged on the substrate. The electrodes may include a first electrode and a second electrode. The first electrode and the second electrode may be arranged in parallel straight lines, parallel curved lines, a comb shape, or concentric circles. In addition, regardless of which of the above shapes is adopted, the first electrode and the second electrode are preferably arranged in line symmetry or point symmetry with each other. Furthermore, it is more preferable that the first electrode and the second electrode are arranged in parallel straight lines or parallel curved lines. It is particularly preferable that the first electrode and the second electrode are arranged in a shape as shown in Figures 13 and 14. Specifically, first metal wiring 313C is preferably configured with two metal wirings (313a and 313c) arranged perpendicular to each other in a T-shape, second metal wiring 313D is preferably configured with two metal wirings (313c and 313d) arranged perpendicular to each other in a T-shape, and first metal wiring 313C and second metal wiring 313D are preferably arranged in parallel lines such that metal wiring 313a and metal wiring 313c face each other. By arranging the first metal wiring and second metal wiring in this manner, odor measuring device 100 can measure odor substances contained in gas with high accuracy.

[0200] As an example, in Figures 13 and 14, one set of electrodes (first metal wiring 313C and second metal wiring 313D) is arranged on one substrate 311, but multiple sets of electrodes may be arranged side by side on one substrate.

[0201] (Area definition process) Next, coating areas onto which the plurality of types of slurries are to be coated are defined on the substrate on which the electrodes are disposed. The coating areas may be defined, for example, by disposing a resist. Furthermore, if the slurry is dropped from a nozzle in the coating process, the coating areas may be defined to match the nozzle diameter. The resist M is disposed so as to define the coating areas 330. In the coating areas 330, the substrate 311 is exposed.

[0202] The size of the coating area 330 may be specified to be the same for each of the multiple types of slurries. That is, even if the slurries have different mixing ratios of the conductive carbon material and the resin composition, the area of ​​the coating area 330 for applying the slurries may be uniform. This reduces the variation in the area of ​​the multiple types of odorant receiving layer 315 after drying, even when multiple types of slurries with different mixing ratios are used.

[0203] The coated area 330 is circular as an example, but the shape of the coated area 330 is not limited to this. The coated area 330 may be circular or strip-shaped. This results in the formation of a circular or strip-shaped odorant receiving layer 315.

[0204] When the shape of the application area 330 is circular, the diameter of the circle may be 0.2 mm or more and 5 mm or less, and when the shape of the application area 330 is strip-shaped, the length of the strip in the short direction may be 0.2 mm or more and 5 mm or less. This results in the formation of a circular odorant receiving layer 315c with a diameter of 0.2 mm or more and 5 mm or less, and a circular odorant receiving layer 315d with a strip-shaped length in the short direction of 0.2 mm or more and 5 mm or less.

[0205] The method for applying the resist M is not particularly limited, but examples include a method of silk-screening the solder resist in a specified area and then UV-curing the solder resist, a method of attaching a resist film to a substrate, and a method of curing only the resist in a specified area and removing the uncured portion.

[0206] (Coating process) Next, each of the multiple types of slurry is applied to the application area 330. The slurry can be applied by a conventionally known method, and may be dropped from a nozzle, sprayed, or spin-coated. The method of applying the slurry is particularly preferably dropped from a nozzle, and for example, the IMAGE By using a SUS metal needle nozzle (inner diameter 0.1 mmΦ, outer diameter 0.23 mm) with the MASTER350PCSmart, the desired coating shape can be obtained.

[0207] (drying process) Finally, the slurry applied to the application area 330 is dried to form the odorant receiving layer 315. The method for drying the slurry is not particularly limited, but for example, it can be heated at 100°C for 1 hour at normal pressure, and then heated at 100°C for 1 hour while reducing the pressure in a vacuum dryer.

[0208] (Method for forming the covering portion) In the second element 31Q, after the odorant receiving layer 315 is formed, a covering portion 316 is further formed. An example of a method for forming the covering portion 316 will be described below.

[0209] For example, if the covering portion 316 is formed using solder resist, first prepare a sufficient amount of resist to prepare a solution, and then compound an inorganic filler (e.g., silica 10-20 nm) to adjust the viscoelasticity of the resist. For example, the viscoelasticity of the resist is approximately 1000-10000 cP. Then, the covering portion 316 can be formed by applying the resist to the surface of the odorant receiving layer 315 of the second element 31Q using a scraper and UV-curing it.

[0210] Furthermore, if the coating portion 316 contains at least one of paraffin and hot melt adhesive, the coating portion 316 may be formed by placing a material on the odorant receiving layer 315 and applying heat above the melting point of the material to melt the material.

[0211] Furthermore, when the covering portion 316 is a film having insulating and gas barrier properties, the film may be cut to a size that can cover the odorant receiving layer 315 and ensure an area sufficient for bonding the film to the substrate 311, and then the film may be adhered using an adhesive or double-sided tape as a fixing layer to form the covering portion 316. When multiple second elements 31Q are produced, the covering portion 316 may be formed by covering multiple second elements 31Q together with a film. In this case, the fixing layer may bond the film to the substrate 311, or may bond a part of the sensor chamber 60 to the film.

[0212] <Software implementation example> The control block (particularly the control unit 1) of the estimation device 10, 10a may be realized by a logic circuit (hardware) formed on an integrated circuit (IC chip) or the like, or may be realized by software.

[0213] In the latter case, the estimation device 10, 10a includes a computer that executes instructions of a program, which is software that realizes each function. This computer includes, for example, one or more processors and a computer-readable recording medium that stores the program. The object of the present invention is achieved when the processor in the computer reads and executes the program from the recording medium. The processor may be, for example, a central processing unit (CPU). The recording medium may be a "non-transitory tangible medium," such as a read-only memory (ROM), a tape, a disk, a card, a semiconductor memory, or a programmable logic circuit. The device may also include a random access memory (RAM) for loading the program. The program may be supplied to the computer via any transmission medium capable of transmitting the program (such as a communication network or broadcast waves). Note that one aspect of the present invention may also be realized in the form of a data signal embedded in a carrier wave, in which the program is embodied by electronic transmission.

[0214] 〔summary〕 The odor measuring sensor according to a first aspect of the present disclosure comprises a first element having a contact surface that comes into contact with a gas containing an odorant, an odorant receiving layer that can interact with the odorant through the contact surface, and outputs a first signal related to a first state change that occurs in the odorant receiving layer, and a second element having the odorant receiving layer whose contact surface is covered by a covering portion, and outputs a second signal related to a second state change that occurs in the odorant receiving layer, wherein the covering portion has a water vapor permeability of 0 g / m 2 / day / atm or more 2.0g / m 2 / day / atm or less, and the oxygen permeability is 0cc / m 2 / day / atm or more 100cc / m 2 / day / atm or less.

[0215] In the odor measuring sensor according to aspect 2 of the present disclosure, in addition to aspect 1, the thermal conductivity of the covering portion at 20°C may be 25.7 W / m / K or more.

[0216] In the odor measuring sensor according to Aspect 3 of the present disclosure, in the above-mentioned Aspect 1, the covering portion may include a film having insulating properties and gas barrier properties.

[0217] An odor measuring sensor according to aspect 4 of the present disclosure may be configured such that, in aspect 1 above, the covering portion includes a layer of air and a plate material covering the layer of air, and the thermal conductivity of the plate material is 25.7 W / m / K or more at 20°C.

[0218] In the odor measuring sensor according to a fifth aspect of the present disclosure, in the first aspect, the covering portion may include a laminate film.

[0219] In the odor measuring sensor according to a sixth aspect of the present disclosure, in the first aspect, the coating may include at least one of paraffin and a hot melt adhesive. [Example]

[0220] The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, % means % by weight and parts means parts by weight.

[0221] The various materials used in the examples and comparative examples are described below.

[0222] <Resin (A)> A1: Polyamide resin (produced based on the method described in [Production Example 1-2 (Polyamide Resin A1)] below) A2: Butyral resin (product name: Mobital B75H, manufactured by Kuraray Co., Ltd.) A3: Silicone resin (trade name: DOWSIL RSN-0255 Flake Resin, manufactured by Dow Toray Industries, Inc.) <Surfactant (B)> B1: Amine salt of polyether phosphate ester (trade name: Disparlon DA-325, manufactured by Kusumoto Chemicals Co., Ltd.) <Conductive carbon material (C)> C1: Carbon black (product name: SuperC65, manufactured by MTI Corporation) <Solvent (D)> D1: N-methyl-2-pyrrolidone <Coating material (E)> E1: Aluminum vapor deposition barrier film (product name: VM-PET1310, manufactured by Toray Advanced Film Co., Ltd., water vapor permeability 0.7 g / m 2 / day / atm, oxygen permeability 0.7cc / m 2 / day / atm) E2-1: Moisture-proof cellophane sheet (60mm x 100mm, manufactured by Shimojima Co., Ltd.) E2-2: Solder resist repair liquid (AYC-L15GR, manufactured by Sanhayato Co., Ltd.) E2: Composite film of E2-1 and E2-2 (water vapor permeability 0.25 g / m 2 / day / atm or less, oxygen permeability 20cc / m 2 / day / atm) E3: Hot melt adhesive (product name: Aronmelt PES-111EE, manufactured by Toa Gosei Co., Ltd., water vapor permeability 0.7 g / m 2 / day / atm, oxygen permeability 3.2cc / m 2 / day / atm) E4: Polyvinyl chloride wrap (product name: Kitchenista Wrap 22cm x 30m box type, manufactured by Kitchenista Co., Ltd., water vapor permeability 420g / m 2 / day / atm, oxygen permeability 18000cc / m 2 / day / atm).

[0223] [Production Example 1-1] (Production of Polyester Resin P1) A mixture was obtained by charging 58.2 parts of 12-hydroxystearic acid and 441.8 parts of ε-caprolactone into a reaction vessel equipped with a stirrer, thermometer, heating / cooling device, nitrogen inlet tube, reflux condenser, dehydration tube with stopcock, and pressure reducing device. The temperature inside the reaction vessel was raised to 140°C over 4 hours under a nitrogen atmosphere, and the mixture was allowed to react for another 2 hours. The mixture was removed when the remaining amount of ε-caprolactone in the mixture was 1% or less. The removed resin was cooled to room temperature and then pulverized into particles to obtain polyester resin P1. The number average molecular weight (Mn) of polyester resin P1 was 2600 and the acid value was 21.7 mg KOH / g.

[0224] <Method for measuring number average molecular weight (Mn) and weight average molecular weight (Mv)> The number average molecular weight (Mn) and weight average molecular weight (Mv) were measured using gel permeation chromatography (GPC) (HLC-802A (manufactured by Tosoh Corporation)) under the following conditions. Columns: Two columns, G4000PWXL (manufactured by Tosoh Corporation) and G5000PWXL (manufactured by Tosoh Corporation), were arranged in series. Mobile phase: 20% acetonitrile (containing 50 mM lithium chloride) Flow rate: 0.8mL / min Column temperature: 40℃ Pump: L-6200 (Hitachi, Ltd.) Detector: L-3300 (RI: differential refractometer, manufactured by Hitachi, Ltd.) and L-4200 (UV-VIS: ultraviolet-visible spectrophotometer, manufactured by Hitachi, Ltd.) Sample solution: 0.5% by weight acetonitrile solution Sample injection volume: 200 μL.

[0225] <Acid value measurement method> The acid value was measured by the method specified in JIS K0070 (1992 edition).

[0226] [Production Example 1-2 (Production of Polyamide Resin A1)] A reaction vessel having the same configuration as that described in Production Example 1-1 was charged with 120 parts of xylene and 82.3 parts of a 20% aqueous solution of polyallylamine (trade name: PAA-03, manufactured by Nittobo Medical Co., Ltd., weight average molecular weight 3,000 parts). The mixture was sealed and heated to 160°C with stirring, and the distillate was removed using a dehydrator with a stopcock. During this time, the xylene in the distillate was separated from the water and returned to the reaction vessel. Then, 83.5 parts of the xylene solution of polyester resin P1 obtained in Production Example 1-1 was added, and stirring was continued at 160°C for 3 hours. After 3 hours, the xylene was removed using a pressure reducing device, yielding polyamide resin A1 having an acid value of 14.9 mgKOH / g and a weight average molecular weight of 10,200.

[0227] An example of producing a resin composition solution will be described below.

[0228] [Production Example 2 <Resin composition solution (S-1)>] The following components were weighed in the following amounts into a sample bottle to obtain a mixture.

[0229] Resin A1 (polyamide resin) 30 parts by weight Conductive carbon material C1 20 parts by weight Solvent D1 450 parts by weight The mixture was stirred at 2000 rpm for 20 minutes using a planetary centrifugal mixer (ARE-310 manufactured by Thinky Corporation), to obtain a resin composition solution (S-1) as a slurry.

[0230] [Production Example 3 <Resin composition solution (S-2)>] The following components were weighed out in the following amounts into a sample bottle, and a resin composition (S-2) was prepared in the same manner as for the resin composition solution (S-1).

[0231] Resin A2 (butyral resin) 30 parts by weight Conductive carbon material C1 20 parts by weight Solvent D1 450 parts by weight.

[0232] [Production Example 4 <Resin composition solution (S-3)>] The following components were weighed out in the following amounts into a sample bottle, and a resin composition (S-3) was prepared in the same manner as for the resin composition solution (S-1).

[0233] Resin A3 (silicone resin) 28.5 parts by weight Surfactant B1 2.5 parts by weight Conductive carbon material C1 19 parts by weight Solvent D1 450 parts by weight.

[0234] Table 1 shows the compositions and physical properties of the resin composition solutions S-1 to S-3.

[0235] [Table 1]

[0236] [Manufacturing of sensor substrate K-1] <Substrate manufacturing> 16 and 17 are schematic diagrams illustrating a manufacturing method for sensor substrate K-1 used in the examples. In this example, a glass cloth-based epoxy resin copper-clad laminate FR-4.0 (manufactured by Panasonic Electric Works Co., Ltd.) measuring 150 mm in length, 100 mm in width, and 1.0 mm in thickness was used, and sensor substrates (corresponding to substrate 311 in the embodiment) designed on the laminate were manufactured in 16 rows vertically and 16 columns horizontally (a total of 256 substrates) by the method described below, as shown in FIGS. 16 and 17. At this time, margins of 11 mm were secured on the top and bottom and 10 mm on the left and right.

[0237] <Wiring pattern design> 18 and 19 are schematic diagrams showing the configuration of the sensor substrate K-1 used in the examples. FIG. 18 shows the front surface (the surface on which the metal wiring 313 and odorant receiving layer 315 are arranged in FIG. 14) of the sensor element (corresponding to the odor sensor element 10 in the embodiment), and FIG. 19 shows the back surface (the surface opposite the front surface) of the sensor element. As shown in FIG. 16, the sensor substrate K-1 is 8 mm long and 5 mm wide. A total of 256 wiring patterns in which the T-shaped metal wirings (first metal wiring 313A and second metal wiring 313B) shown in FIG. 14 face each other were designed on the above-mentioned laminate. In the wiring pattern, the lengths of first metal wiring 313A and first metal wiring 313C were 2.5 mm, the lengths of second metal wiring 313B and second metal wiring 313D were 2 mm, the spacing between first metal wiring 313A and first metal wiring 313C was 1.5 mm, and the width of each metal wiring was 0.3 mm. Furthermore, as shown in Figures 18 and 19, circular conductive portions with a diameter of 1 mm were provided at the end of first metal wiring 313A not facing second metal wiring 313B and at the end of second metal wiring 313B not facing first metal wiring 313A, as portions into which conductive members (pins) for electrically connecting the metal wiring to other components of the odor sensor were inserted. In addition, similar circular conductive portions with a diameter of 1 mm were designed at positions corresponding to the above-mentioned ends on the back surface of the substrate.

[0238] <Through-hole manufacturing process> To mount pins (corresponding to pin 317 in the embodiment) on each sensor substrate, holes for through-holes were drilled in the circular conductive portions with a diameter of 1 mm using an NC drill machine. The drilled holes were subjected to electroless copper plating and then copper sulfate plating to form through-holes with a copper plating layer of 25 μm in thickness.

[0239] <Pattern formation process> Photosensitive dry film resist (product name: Photec RD-3025, film thickness 25 μm, manufactured by Showa Denko Materials Co., Ltd.) was attached to both sides of the sensor substrate using a roll laminator (pressure 0.4 MPa, temperature 110 °C, lamination speed 0.4 m / min). Then, ultraviolet light (wavelength 355 nm) was applied at 85 mJ / cm2 from the photosensitive dry film resist side through a negative photomask for the front side and a negative photomask for the back side in an ultraviolet exposure machine. 2 After irradiation, the unexposed photosensitive dry film resist was removed with a 5 wt% sodium carbonate solution at 35°C. The exposed copper foil was then removed by etching with a ferric chloride solution. The exposed photosensitive dry film resist was then removed with a 10 wt% sodium hydroxide solution at 35°C.

[0240] The negative photomask pattern used for the front side was a pattern in which the designed sensor substrate was arranged in 16 rows at 8 mm intervals in the vertical direction and 16 columns at 5 mm intervals in the horizontal direction.The negative photomask for the back side was a pattern in which circles with a diameter of 1 mm were arranged in positions that matched the circular parts of the negative photomask for the front side.

[0241] <Solder resist process> A two-component alkaline development type solder resist ink (product name: PSR-4000 AUS320 / CA-40 AUS320, manufactured by Taiyo Ink Mfg. Co., Ltd.) was pattern-printed on the front side area excluding the copper foil area, the through-hole area, and the strip-shaped odorant receiving layer 315 area (the area indicated by diagonal lines in Figure 18). A pattern was also printed on the back side area excluding the copper foil area and the through-hole area. The substrate was heated at 80°C for 30 minutes to dry temporarily, and then exposed to ultraviolet light (wavelength 355 nm) at 600 mJ / cm. 2 The unexposed areas were then removed with a 1% by weight aqueous solution of sodium carbonate at 35°C. The substrate was then heated at 150°C for 60 minutes to harden the solder resist ink. The solder resist formed on the sensor substrate can prevent the spread of the resin composition solution that will be applied in a later process.

[0242] <Surface treatment process> The sensor substrate was degreased, soft-etched, and acid-washed, and then immersed in a catalyst application solution (product name: ICP Accela COA, manufactured by Okuno Pharmaceutical Industries Co., Ltd.) for 5 minutes at 25°C. The substrate was then rinsed with water and immersed in an electroless Ni plating solution (product name: Top Nicoron SA-98-MLF, manufactured by Okuno Pharmaceutical Industries Co., Ltd., 100 ml, and product name: Top Nicoron SA-98-1LF, manufactured by Okuno Pharmaceutical Industries Co., Ltd., 55 ml, made up to 90°C) for 6 minutes to form a Ni coating with a thickness of 3 μm, and then washed with pure water.

[0243] Next, the sensor substrate was immersed in a displacement gold plating solution (product name: OL 2300, manufactured by Kojima Chemical Industries, Ltd.) at 85°C for 5 minutes to form a displacement gold coating of 0.05 μm thickness on the Ni coating, thereby obtaining a substrate in which the copper foil portion was covered with nickel and gold plating.

[0244] <V cut on the circuit board> Using a V-cutting machine, V-cuts were made on the substrate at intervals of 8 mm in length and 5 mm in width so that it could be separated into individual sensor substrates.

[0245] <Pin implementation> An IC terminal (product name: "Hybrid IC Terminal", manufactured by Mac Eight Corporation, φ0.6 mm, length 5 mm) was soldered to the fabricated through-hole. In this way, a total of 256 sensor substrates K-1 shown in Figures 18 and 19 were fabricated.

[0246] [Manufacturing Example 5 <Sensor Element P-1>] Using a 1μm PIPETMASTER manufactured by Musashi Engineering Co., Ltd., a Violamo Sakura tip (10μL capacity, polypropylene, stored in a dedicated rack) manufactured by Violamo was attached, and 10μL of the resin composition solution (S-1) prepared was aspirated from a container storing the resin composition solution (S-1). After aspirating, the pipette tip was placed on the edge of the container to drain the liquid, and then 0.2μL of the resin composition solution (S-1) was dispensed onto the prepared sensor substrate K-1, thereby applying it to the metal wiring portion. After application, the substrate was dried for 3 hours in a circulating air dryer heated to 100°C, and then cooled to room temperature to prepare a sensor element (P-1). The procedure of applying the resin composition solution (S-1) to the metal wiring portion and subsequent steps was repeated 20 times in succession, and 20 sensor elements (P-1) were prepared.

[0247] [Manufacturing Example 6 <Sensor element P-2>] The resin composition solution (S-2) was applied to the sensor substrate K-1 under the same conditions as in Production Example 5, and then dried to prepare 15 sensor elements (P-2).

[0248] [Manufacturing Example 7 <Sensor element P-3>] The resin composition solution (S-3) was applied to the sensor substrate K-1 under the same conditions as in Production Example 5, and dried to prepare 15 sensor elements (P-3).

[0249] [Example 1 <Second element (Q1-1)>] A second element (Q1-1) was obtained by cutting the covering material E1 to a size of 5 mm in length and 5 mm in width for one sensor element (P-1) produced in Production Example 5 and attaching it to the resin composition portion using double-sided tape. The above operation was repeated three times in total to produce three second elements (Q1-1).

[0250] [Example 2 <Second element (Q2-1)>] The sensor element (P-2) produced in Production Example 6 was subjected to the same operation as in Example 1 to produce three second elements (Q2-1).

[0251] Example 3: Second element (Q3-1) The sensor element (P-3) produced in Production Example 6 was subjected to the same operation as in Example 1 to produce three second elements (Q3-1).

[0252] [Example 4 <Second element (Q1-2)>] The coating material E2-1 was cut into a size of 5 mm in length and 5 mm in width. The cut coating material was attached to one sensor element (P-1) produced in Production Example 5 using double-sided tape so as to cover the resin composition portion, and then the coating material E2-2 was applied on top of the coating material to obtain a second element (Q1-2). The above operation was repeated three times to produce three second elements (Q1-2).

[0253] [Example 5 <Second element (Q2-2)>] The sensor element (P-2) produced in Production Example 6 was subjected to the same operation as in Example 4 to produce three second elements (Q2-2).

[0254] Example 6: Second element (Q3-2) The sensor element (P-3) produced in Production Example 6 was subjected to the same operation as in Example 4 to produce three second elements (Q3-2).

[0255] [Example 7 <Second element (Q1-3)>] A SUS plate (750 μm thick) with a square hole measuring 5 mm in length and 5 mm in width was placed on one sensor element (P-1) manufactured in Manufacturing Example 5 and fixed so that the resin composition portion was in the center. The coating material E3 was placed in the tank of a hot melt glue gun (product name: Hot Melt Glue Gun MS200, manufactured by Kaetsu Co., Ltd.) and the temperature was adjusted. The coating material E3 was extruded into the hole in the SUS plate, and the excess coating material was removed. After the coating material cooled and solidified, the SUS plate was peeled off to obtain a second element (Q1-3). The above procedure was repeated three times to produce three second elements (Q1-3).

[0256] Example 8 <Second element (Q2-3)> The sensor element (P-2) produced in Production Example 6 was subjected to the same operation as in Example 7 to produce three second elements (Q2-3).

[0257] Example 9 <Second element (Q3-3)> The sensor element (P-3) produced in Production Example 6 was subjected to the same operation as in Example 7 to produce three second elements (Q3-3).

[0258] Comparative Example 1 <Comparative element 2 (comparison Q1-1)> For one sensor element (P-1) manufactured in Manufacturing Example 5, the covering material E4 was cut into a size of 5 mm in length and 5 mm in width, and attached to cover the resin composition portion using double-sided tape to obtain a comparative second element (comparison Q1-1). The above operation was repeated three times in total to produce three comparative second elements (comparison Q1-1).

[0259] Comparative Example 2 <Comparative element 2 (comparison Q2-1)> The sensor element (P-2) produced in Production Example 6 was subjected to the same operation as in Comparative Example 1 to prepare three comparative second elements (Comparison Q2-1).

[0260] Comparative Example 3 <Comparative element 2 (comparison Q3-1)> The sensor element (P-3) produced in Production Example 6 was subjected to the same operation as in Comparative Example 1 to prepare three comparative second elements (Comparison Q3-1).

[0261] <Construction of an odor sensor> We created a housing equipped with a target sample receiving section with an inlet for introducing the sample (odor substance) and an aluminum block thermostatic bath for temperature control, a nitrogen gas cylinder for gas supply, a mass flow controller, and a sensor chamber. The volume of the target sample receiving section was designed to be five times the volume of the sensor chamber.

[0262] Lead wires for connecting the sensor terminals to the outside were soldered to each of the sensor elements (P-1) to (P-3), (Q1-1) to (Q3-3), and (comparison Q1-1) to (comparison Q3-13) to be evaluated, and the elements were placed in the sensor chamber. A 5V constant-voltage power supply and a 300Ω fixed resistor were connected in series to the ends of the lead wires connected to the outside of the sensor chamber for each of the sensor elements (P-1) to (P-3), (Q1-1) to (Q3-3), and (comparison Q1-1) to (comparison Q3-13), and a voltmeter was connected to measure the voltage across both terminals of the sensor element. In this way, multiple odor sensors were constructed, each having either the first element (P-1) to (P-3) and the second element (Q1-1) to (Q3-3) or the comparison second element (comparison Q1-1) to (comparison Q3-1). The correspondence between the odor sensor number and the sensor element number of the odor sensor is as shown in Tables 1 and 2.

[0263] [evaluation] <Measurement of resistance change (ΔV) when measuring ethanol 1> Odor sensors 1-9 and c1-c6 were each installed in a laboratory (temperature 25°C, humidity 50%), and 1 ml of ethanol was placed in the target sample receiving section. Then, nitrogen was introduced as a carrier gas from the carrier gas inlet into the chamber containing the sensor element at a flow rate of 1 L / min using a gas flow regulator, and the gas was discharged to the outside. During this time, the measurements of the voltmeter connected to the sensor element were recorded by a computer. Thus, the voltage values ​​of each of the three sensor elements in the odor sensor were measured. For each sensor element of each odor sensor, ΔV1 was calculated, which is the maximum difference between the output voltage V0 before the sample was introduced and the voltage V after the sample was introduced. Then, δ1 was calculated, which is the difference between the maximum value ΔV1-1 of the first element and the maximum value ΔV1-2 of the second element. Furthermore, μ1 was calculated, which is the average of the three difference δ data obtained for each odor sensor.

[0264] <Measurement of resistance change (ΔV) during ethanol measurement 2> The measurement was carried out on a different day from Measurement 1. The measurement method was the same as Measurement 1. In addition, the maximum value ΔV2-1 of the first element, the maximum value ΔV2-2 of the second element, the difference δ2, and the average value μ2 were calculated in the same manner as Measurement 1. The temperature in the laboratory during this measurement was 28°C and the humidity was 80%.

[0265] <Measurement environment dependence (μ1-μ2)> Using the above μ1 and μ2, the measurement environment dependency was evaluated as follows when ethanol was measured under different measurement conditions. First, the value of [μ1 - μ2] / μ1 was calculated for each sensor element. Since the absolute value of μ1 - μ2 is used, the value of [μ1 - μ2] / μ1 is 0 or greater. The calculated values ​​were then evaluated based on the following criteria: The smaller the calculated value, the less the sensor element is affected by the measurement environment, and the more accurately it can detect odor substances.

[0266] A: Less than 0.1 B: 0.1 or more, less than 1.0 C:1.0 or higher Table 2 shows the materials constituting the odor sensors of the Examples and Comparative Examples, as well as the measurement results obtained using the odor sensors.

[0267] [Table 2]

[0268] Table 2 shows that the water vapor permeability and oxygen permeability of the coating portion of the odor sensor of the Example were lower than those of the Comparative Example. Accordingly, the values ​​of ΔV1-2 and ΔV2-2 were also lower for the Example odor sensor than for the Comparative Example odor sensor. The Comparative Example odor sensor either had a high water vapor permeability and oxygen permeability of the coating portion, or did not have a coating portion, which allowed odor components to permeate, resulting in the large values ​​of ΔV1-2 and ΔV2-2. Furthermore, with regard to the dependence on the measurement environment, the odor sensors of the Example, which had low water vapor permeability and oxygen permeability, had low values, while the Comparative Example odor sensor had high values, indicating that it was significantly affected by the measurement environment.

[0269] From the above, it has been demonstrated that the odor sensor according to one embodiment of the present invention is capable of detecting odorous substances with high accuracy. [Industrial Applicability]

[0270] The present invention is useful as an odor identification sensor for medical, gas detection, agricultural, and other industrial and daily uses. For example, farmers can use the odor identification sensor to determine the maturity of fragrant crops and manage optimal harvest timing. Furthermore, the odor identification sensor can also be used to digitize the odors of products such as food and cosmetics, helping to improve the efficiency of product development and stabilize quality. [Explanation of symbols]

[0271] 10, 10a Estimation device 11 Measurement value acquisition unit (acquisition unit) 12 Change pattern analysis unit (analysis unit) 16 Estimation part 30 Odor Sensor 31 Sensor element 31P, 31Pc, 31Pc 1st element 31Q Second element 32, 32b Constant voltage power supply (power supply) 33, 33b Voltmeter (measuring equipment) 100, 100a Odor measuring device 313A, 313C 1st metal wiring 313B, 313D 2nd metal wiring 315, 315c, 315d Odorant receptor layer 316 Covering part 50 Target sample receiving section 51 Adjustment part 60 Sensor Chamber 80 Gas supply section 91, 92, 93, 94 Body 501 1st mouth 502 2nd mouth 503 Sample inlet

Claims

1. A first element has a contact surface that comes into contact with a gas containing an odorant, and an odorant receiving layer that can interact with the odorant through the contact surface, and outputs a first signal related to a first state change that occurs in the odorant receiving layer; The odorant receiving layer has a contact surface covered by a covering portion, and a second element outputs a second signal related to a second state change occurring in the odorant receiving layer. The covering portion is Water vapor permeability is 0 g / m ２ / day / atm or more 2.0g / m ２ / day / atm or less, Oxygen permeability is 0 cc / m ２ / day / atm or more 100cc / m ２ / day / atm or less, Smell sensor.

2. The thermal conductivity of the coating portion is 25.7 W / m / K or more at 20°C. The odor sensor according to claim 1 .

3. The covering portion is Films having insulating and gas barrier properties are included. The odor sensor according to claim 1 .

4. The covering portion is The invention includes an air layer and a plate material covering the air layer, The thermal conductivity of the plate material is 25.7 W / m / K or more at 20°C. The odor sensor according to claim 1 .

5. The covering portion is Including laminating film, The odor sensor according to claim 1 .

6. The covering portion is Contains at least one of paraffin and hot melt adhesive; The odor sensor according to claim 1 .

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