Odor measuring device, sensor element, and method for manufacturing same

Abstract

Provided are an odor measurement device capable of outputting a stable measurement result, a sensor element, and a method for manufacturing the same. An odor measurement device (100) is provided with a plurality of sensor elements (31), each sensor element (31) being provided with an electrode (313) having a first metal wiring (313A) and a second metal wiring (313B), and an odor substance acceptor layer (315) 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 odor substance acceptor layer (315) containing a resin composition, the resin composition contains a filler and a silicone resin composed of a T unit (R1SiO3 / 2) and a D unit (R12SiO2 / 2), wherein R1 is a monovalent hydrocarbon group having 1-10 carbon atoms.

Description

Technical Field

[0001] The present invention relates to an odor measuring device, a sensor element and a manufacturing method thereof. Background Art

[0002] With the development of information processing technology in recent years, if the sense of smell, which cannot be fully measured by machinery, can be digitized in some way, it can be expected to be used in a wide range of industrial fields. For example, in the medical field, nursing, preventive diagnosis, disease examination, etc. can be realized. In the environmental field, odor management in factories, etc. can be realized. In the field of biochemical gas utilization, fermentation process management, drainage treatment management, etc. can be realized. In the safety field, the precursor detection of sand and soil collapse, water damage, etc., the deterioration detection of engine oil and mechanical working oil, etc. can be realized. In addition, in the food field, it can be used for the ripening state detection of food materials such as plants and meat, process management of fermented foods such as alcohol, plant cultivation management, food production, storage, and quality management during the circulation process. In the marketing field, it can be used to make perfumes, body odor, fragrance environment, product fragrance, etc. So far, the detection method of specific gas substances (gases) has been achieved by high-precision and high-sensitivity measurement through semiconductor gas sensors, etc. At present, sensors with different response characteristics to various odors have appeared, and research on the components of receptors in sensors has begun.

[0003] The invention described in Patent Document 1 proposes a mechanism for detecting the adsorption of odor components on the surface of a conductive polymer by replacing the semiconductor of a semiconductor gas sensor with a conductive polymer. Patent Document 1 reports that it can detect odor components that are easily thermally decomposed and substances that do not undergo redox reactions on the surface of the sensor detection part.

[0004] In addition, Patent Document 2 focuses on the property that the resistance of a mixture of an organic polymer and a conductive substance changes when exposed to an organic gas. Patent Document 2 states that if a plurality of organic polymer / conductive substance combinations are prepared using various organic polymer components in the mixture and these combinations are used as resistor arrays in a sensor, the resistance changes when exposed to the same organic gas will be different. Patent Document 2 reports that by utilizing this, it is possible to identify odors by classifying the resistance change pattern with the type of odor (i.e., the organic gas mixture).

[0005] Furthermore, Patent Document 3 reports that the response speed of the sensor can be increased by adding a plasticizer to the organic polymer.

[0006] Patent Document 4 discloses a sensor having a receptor, wherein the receptor comprises RSiO 3 / 2structure, and a filler having a specific average primary particle size.

[0007] (Prior art literature)

[0008] Patent Document 1: Japanese Patent Application Laid-Open No. 11-23508

[0009] Patent Document 2: Japanese Patent Publication No. 11-503231

[0010] Patent Document 3: Japanese Patent Publication No. 2002-519633

[0011] Patent Document 4: Japanese Patent Application Publication No. 2022-26253 Summary of the invention

[0012] (Problems to be solved by the invention)

[0013] If the performance of the sensor element used in the odor measuring device changes and becomes unstable each time it is manufactured, it is impossible to stably produce the odor measuring device with a predetermined detection accuracy. In addition, if the sensor element of the odor measuring device is to be replaced with a new sensor element, it is desirable that the difference between the performance of the sensor element before the replacement and the performance of the sensor element after the replacement is small or no difference.

[0014] An object of one aspect of the present invention is to provide a smell measuring device, a sensor element and a method for manufacturing the same that are capable of outputting stable measurement results.

[0015] (Technical means to solve the problem)

[0016] The present inventors have conducted studies to achieve the above-mentioned object and have completed the present invention as a result.

[0017] That is, an odor measuring device according to one aspect of the present invention comprises a plurality of sensor elements, wherein the plurality of sensor elements comprises an electrode and an odor substance receptor layer, wherein the electrode comprises a first metal wiring and a second metal wiring separated from the first metal wiring, and the odor substance receptor layer is in contact with at least a portion of the first metal wiring and at least a portion of the second metal wiring, wherein the odor substance receptor layer comprises a resin composition, wherein the resin composition comprises a filler, and a T unit (R 1 SiO 3 / 2 ) and D unit (R 1 2SiO 2 / 2 ) is an organic silicone resin, wherein R 1 It is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0018] In one aspect of the present invention, a sensor element comprises an electrode and an odorant receptor layer, wherein the electrode has a first metal wiring and a second metal wiring separated from the first metal wiring, and the odorant receptor layer is connected to at least a portion of the first metal wiring and at least a portion of the second metal wiring, wherein the odorant receptor layer comprises a filler and a T unit (R 1 SiO 3 / 2 ) and D unit (R 1 2SiO 2 / 2 ) is an organic silicone resin, wherein R 1 It is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0019] In addition, a method for manufacturing a sensor element according to one aspect of the present invention comprises: a slurry preparation step of preparing slurry; an electrode configuration step of configuring an electrode having a first metal wiring and a second metal wiring separated from the first metal wiring on a substrate; a coating step of coating the slurry on a coating area including at least a portion of the first metal wiring and at least a portion of the second metal wiring; and a drying step of drying the slurry coated on the coating area to form an odorant receptor layer, wherein the slurry comprises a filler and a T unit (R 1 SiO 3 / 2 ) and D unit (R 1 2SiO 2 / 2 ) is an organic silicone resin, wherein R 1 It is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0020] (Effects of the Invention)

[0021] According to one aspect of the present invention, an object is to provide a smell measuring device, a sensor element and a method for manufacturing the same that can output stable measurement results. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 This is a schematic diagram of an example of the structure of an odor measuring device according to one embodiment of the present invention.

[0023] Figure 2 This is a top view of an example structure of a sensor element.

[0024] Figure 3 yes Figure 2 A cross-sectional view showing an example structure of a sensor element.

[0025] Figure 4 This is a functional block diagram of an example structure of an odor measuring device.

[0026] Figure 5 This is a flowchart of an example of a process flow in which the estimation device generates an estimation model.

[0027] Figure 6 This is a functional block diagram of an example structure of an odor measuring device.

[0028] Figure 7 This is a flowchart of an example of a process flow for estimating odor substances by the estimation device.

[0029] Figure 8 This is a block diagram showing an example of the structure of an odor measuring device according to another embodiment of the present invention.

[0030] Fig. 9 This is a schematic diagram of an example of the structure of an odor measuring device according to another embodiment of the present invention.

[0031] Fig.10 It is a top view of a structural example of a sensor chamber.

[0032] Fig.11 It is a cross-sectional view of a structural example of a sensor chamber.

[0033] Fig.12 It is a cross-sectional view of a structural example of a sensor chamber.

[0034] Fig.13 This is a top view of an example structure of a sensor element of the present invention.

[0035] Fig.14 This is a top view of an example structure of a sensor element of the present invention.

[0036] Fig.15 This is a flowchart of an example of a process of a method for manufacturing a sensor element.

[0037] Fig.16 This is a top view of an example of a substrate before slurry coating. DETAILED DESCRIPTION

[0038] [Implementation method 1]

[0039] An embodiment of the present invention is described below. In the present specification, "A to B" describing a numerical range means "A or more and B or less" unless otherwise specified.

[0040] In this specification, "odor substance" refers to a substance that can be adsorbed onto the odor substance receptor layer in a broad sense. Therefore, it also includes substances that are generally considered to be the cause of odor generation. Most "odors" contain multiple odor substances that are the cause of odor generation. In addition, there are substances that have not been identified as odor substances or odor substances that are not yet known. One embodiment of the present invention focuses on: depending on the type of odor substance, the amount of adsorption of the odor substance to the odor substance receptor layer will vary.

[0041] Here, in this specification, even if simply described as "odor substance", it may refer not only to each odor substance but also to an "odor substance aggregate" which may contain a plurality of odor substances.

[0042] The “odorant” is not particularly limited, and examples thereof include hexane, ethyl acetate, methanol, diethyl carbonate, toluene, d-limonene, camphan-2-one, cis-3-hexenol, β-phenylethanol, citral, L-carvone, γ-undecanolactone, eugenol, linalyl acetate, menthol, benzaldehyde, vanillin, hexanal, ethanol, amyl valerate, linalool, 2-propanol, and the like.

[0043] [1. Resin composition]

[0044] The resin composition of one embodiment of the present invention is a resin composition for forming an odorant receptor layer, which comprises a resin (A) and a filler (C). The resin (A) comprises a T unit (R 1 SiO 3 / 2 ) and D unit (R 1 2SiO 2 / 2 ) is a silicone resin. The resin composition may be a composition in which these components are uniformly present. In addition, the resin composition may further contain a surfactant (B) to serve as a dispersant for the filler (C).

[0045] <Resin (A)>

[0046] The resin (A) only needs to have film-forming properties that can be used to form an odorant receptor layer, and preferably exhibits interactions such as adsorption and dissolution with respect to specific odorants. In addition, the resin (A) preferably has physical properties (heat resistance, etc.) and chemical properties (compatibility with material gas and corrosion resistance, etc.) that are suitable for the use conditions of the odor sensor described later.

[0047] The silicone resin contained in the resin (A) may be a resin obtained by mixing a plurality of types of silicone resins composed of T units and silicone resins composed of D units.

[0048] (Silicone resin)

[0049] The silicone resin contains: a monofunctional M unit with three organic groups bonded to Si, a bifunctional D unit with two organic groups bonded to Si, a trifunctional T unit with one organic group bonded to Si, and a tetrafunctional Q unit without an organic group bonded to Si. The silicone resin contained in the resin (A) is composed of T units (R 1 SiO 3 / 2 ) and D unit (R 1 2SiO 2 / 2 ) constitutes, R 1It is a monovalent hydrocarbon group having 1 to 10 carbon atoms. In the present disclosure, a solid organic silicon crosslinked product at normal temperature and pressure (for example, normal temperature is 25±15° C., normal pressure is 1013 hPa) is referred to as an “organic silicon resin”.

[0050] The hydrocarbon group may be any of an aliphatic group and an aromatic group, and examples thereof include an alkyl group, an alkenyl group, an aryl group, an aralkyl group, etc. The alkyl group and the alkenyl group may be a straight chain or a branched chain.

[0051] Examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, various types of butyl, various types of pentyl, various types of hexyl, various types of heptyl, various types of octyl, various types of nonyl, and various types of decyl.

[0052] Examples of the aryl group include a phenyl group, a tolyl group, and a dimethylphenyl group.

[0053] Examples of the aralkyl group include benzyl, phenethyl, phenylpropyl, and phenylbutyl.

[0054] The T unit (R 1 SiO 3 / 2 ) and D unit (R 1 2SiO 2 / 2 ) is preferably a weight ratio of T unit:D unit=98:2~40:60. In addition, the weight ratio of T unit to D unit is more preferably T unit:D unit=95:5~50:50. When the weight ratio of T unit to D unit is within the above range, the resin composition has suitable flexibility and improved film-forming properties. It should be noted that if the weight ratio of T unit in the silicone resin is less than 50%, the mesh structure part in the silicone resin will become less, so that the reversibility of the adsorption and desorption of odor substances relative to the resin composition of the odor substance receptor layer will deteriorate.

[0055] Resin (A) may also contain other components besides silicone resin. As an example of other components that resin (A) can contain, silicone oil can be cited. In the present disclosure, silicone oil is a substance that has fluidity at room temperature and pressure (for example, room temperature is 25±15°C, and room pressure is 1013hPa) and is extended into a chain by siloxane bonds. Silicone resin can form a three-dimensional crosslinked structure by siloxane bonds through a crosslinking reaction. In contrast, silicone oil cannot form the crosslinked structure. From the perspective of improving the dispersibility of filler (C) in the resin composition, or from the perspective of improving the coating properties of the resin composition, silicone oil can be added to the resin composition. Silicone oil is particularly preferably silicone oil composed only of D units. There is no particular limitation on the type of functional groups as modified portions and other modified portions that have been capped that silicone oil has. Modified portions may have forms such as side chain type, two-end type, single-end type, and side chain two-end type. As the modified site, there can be mentioned amino, amine, epoxy, methanol, mercapto, carboxyl, methyl hydrogen, methacryloyl, acryloyl, phenyl, phenol, silanol, anhydride, vinyl, etc. As other modified sites, there can be mentioned polyester sites, polyether sites, alkyl sites, aralkyl sites, fluoroalkyl sites, higher fatty acid ester sites, higher fatty acid amide sites, etc. In the following description, the case where the "organic silicone resin" does not contain silicone oil is taken as an example for explanation.

[0056] <Surfactant (B)>

[0057] The surfactant (B) acts as a dispersant for the filler (C) described later. In addition, when the sensor element is formed by applying the resin composition, the surfactant (B) can improve the coating property of the resin composition. The surfactant (B) can be appropriately selected from known surfactants within the range of exerting the above-mentioned effect.

[0058] Examples of the surfactant (B) include anionic surfactants, cationic surfactants, amphoteric surfactants, and nonionic surfactants.

[0059] 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.

[0060] 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, eicosanoic acid, heneicosanoic acid, docosanoic acid, tricosanoic acid and tetracosanoic acid.

[0061] Examples of the alkyl group of the alkylsulfonic acid having 14 to 24 carbon atoms include tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl and tetracosyl.

[0062] Examples of the alkali metal contained in the alkali metal salt include sodium and potassium.

[0063] Examples of the cationic surfactant include quaternary ammonium halide salts having an alkyl group having 12 to 24 carbon atoms.

[0064] As for the quaternary ammonium having an alkyl group having 12 to 24 carbon atoms, for example, tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, dimethyldioctylammonium, didecyldimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium, tridecyltrimethylammonium, hexadecyltrimethylammonium, methyltrioctylammonium, octyltrimethylammonium, tributylmethylammonium, octadecyltrimethylammonium, tetradecyltrimethylammonium, nonadecyltrimethylammonium, eicosyltrimethylammonium, heneicosyltrimethylammonium, heptadecyltrimethylammonium and pentadecyltrimethylammonium can be mentioned.

[0065] Examples of the halide salt include fluoride salts, chloride salts, bromide salts, and iodide salts.

[0066] Examples of the amphoteric surfactant include dimethyl(3-sulfopropyl)ammonium intramolecular salt having an alkyl group having 10 to 22 carbon atoms, and N-alkyl-N,N-dimethylglycine having an alkyl group having 10 to 22 carbon atoms.

[0067] Examples of the dimethyl(3-sulfopropyl)ammonium hydroxide inner salt 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, pentadecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, hexadecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, heptadecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, and octadecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt. Nonadecyldimethyl (3-sulfopropyl) ammonium hydroxide inner salt, eicosyldimethyl (3-sulfopropyl) ammonium hydroxide inner salt, heneicosyldimethyl (3-sulfopropyl) ammonium hydroxide inner salt, docosyldimethyl (3-sulfopropyl) ammonium hydroxide inner salt, and the like.

[0068] Examples of the N-alkyl-N,N-dimethylglycine having an alkyl group having 10 to 22 carbon atoms include N-dodecyl-N,N-dimethylglycine and N-octadecyl-N,N-dimethylglycine.

[0069] Examples of the nonionic surfactant include higher alcohol ethylene oxide adducts and the like.

[0070] Examples of the higher alcohol include 1-hexanol, 1-heptanol, 1-octanol, 1-nonanol, 1-decanol, 1-undecanol, 1-dodecanol, 1-tridecanol, 1-tetradecanol, 1-pentadecanol, 1-hexadecanol, 1-heptadecanol and 1-octadecanol.

[0071] 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 recognition performance.

[0072] From the viewpoint of dispersibility relative to filler (C), surfactant (B) preferably has at least one of amide group, primary amino group, secondary amino group and tertiary amino group. In addition, from the viewpoint of dispersibility relative to filler (C), surfactant (B) preferably has at least one of oxyethylene chain, oxypropylene chain and oxyethylene-oxypropylene random structure or block structure. It should be noted that the oxyethylene-oxypropylene random structure is a chain structure formed by irregular connection of oxyethylene and oxypropylene. In addition, the block structure of oxyethylene-oxypropylene is a chain structure formed by connecting oxyethylene blocks formed by connecting oxyethylene and oxypropylene blocks formed by connecting oxypropylene. As commercial examples of surfactant (B), Disparon DA-325, Disparon DA-375 and Disparon DA-234 (manufactured by Kusumoto Chemicals Co., Ltd.) and the like can be cited.

[0073] <Filler (C)>

[0074] Filler (C) is an inorganic material such as metals such as silicon dioxide and nickel powder, and conductive carbon materials. In this specification, conductive carbon materials refer to carbon materials with a volume resistivity of less than 0.1Ω·cm. The resin composition is a state in which filler (C) is dispersed in a mixture consisting of resin (A) and surfactant (B). The resin composition has conductivity by forming a conductive path through contact between fillers (C).

[0075] Examples of commercially available silica include organosilicic sols (IPA-ST, IPA-ST-UP, IPA-ST-ZL, DMAC-ST, MEK-ST, MIBK-ST, PMA-ST, and PGM-ST) manufactured by Nissan Chemical Co., Ltd.

[0076] Examples of the conductive carbon material include carbon black, carbon nanotubes, and graphene. As the conductive carbon material, carbon black is particularly preferred.

[0077] Commercially available products of carbon black include Ketjen Black EC (a trade name of Akzo of the Netherlands), Ketjen Black EC-300J (a trade name of Lion Specialty Chemicals Co., Ltd.), Ketjen Black EC-600JD (a trade name of Lion Specialty Chemicals Co., Ltd.), SEAST G116, 116 (a trade name of Tokai Tan Co., Ltd.), Nylon #10 (a trade name of Nippon Steel Chemical Co., Ltd.), DENKA BLACK (a trade name of Denki Kagaku Kogyo Co., Ltd.), and SUPER C-65 (a product name of MTI Corporation of the U.S.), etc.

[0078] Commercially available products of carbon nanotubes include VGCF-H (products of Showa Denko K.K.) and the like.

[0079] Commercially available products of graphene include products manufactured by Sigma-Aldrich Corporation.

[0080] The conductive carbon material is preferably in a fibrous or spherical shape.

[0081] When the fiber is in a fibrous form, 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.

[0082] When the particle is spherical, the primary particle size is preferably 10 nm to 200 nm, more preferably 20 nm to 150 nm.

[0083] In addition, from the viewpoint of the conductivity of the conductive carbon material in the resin composition and the sensitivity of the sensor, the primary particle size of the conductive carbon material is preferably less than 100nm. The particle size of the conductive carbon material can be obtained by a known method. For example, it can be observed by a transmission electron microscope (TEM), and an image processing device (such as a digital microscope VHX-700F manufactured by KEYENCE Co., Ltd.) is used to perform image analysis to measure the particle size of the conductive carbon material. If the conductive carbon material is a known article or a commercially available product, the particle size can be a value recorded in the literature or a value recorded in the product catalog.

[0084] <Components of Resin Composition>

[0085] From the viewpoint of coating stability of the resin composition and stability of the filler (C) in the resin composition, the weight ratio [(A) / (B)] of the resin (A) to the surfactant (B) in the resin composition is preferably 4.0 to 50.0. From the viewpoint of stability of the filler (C) in the resin composition, the weight ratio (A) / (B) is more preferably greater than 4.0, more preferably greater than 4.5, and more preferably greater than 5.0. In addition, from the viewpoint of coating stability of the resin composition, the weight ratio (A) / (B) is more preferably less than 40.0, and more preferably less than 30.0.

[0086] From the viewpoint of fully showing the conductivity of the odor sensor by the sensor element formed by the resin composition, and from the viewpoint of fully showing the sensitivity of the odor sensor, the content of the filler (C) in the resin composition is preferably 5 to 30% by weight relative to the total 100% by weight of the resin (A), the surfactant (B) and the filler (C). From the viewpoint of further improving the conductivity, the content of the filler (C) relative to the total 100% by weight of the resin (A), the surfactant (B) and the filler (C) is more preferably 10% by weight or more, and more preferably 15% by weight or more. In addition, from the viewpoint of further improving the sensitivity, the content of the filler (C) relative to the total 100% by weight of the resin (A), the surfactant (B) and the filler (C) is more preferably 25% by weight or less, and more preferably 20% by weight or less.

[0087] <Optional Ingredients>

[0088] The resin composition may also contain other components other than the resin (A), the surfactant (B) and the filler (C) within the scope of obtaining the effect of the present invention. Other components include, for example, a solvent (D). The other components may be appropriately used within the scope of obtaining both the effect of the present invention and the effect brought by the other components.

[0089] From the viewpoint of improving the compatibility between the resin (A) and the surfactant (B), improving the dispersibility of the filler (C) in the resin composition, or improving the coating property of the resin composition, a solvent (D) may be added to 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.

[0090] The content of the solvent (D) in the resin composition can be appropriately determined from the above-mentioned viewpoints. For example, from the viewpoint of coating properties, the content of the solvent (D) in the resin composition is preferably 100 to 10,000 parts by weight relative to 100 parts by weight of the total of the resin (A), the surfactant (B) and the filler (C).

[0091] <Method for preparing resin composition>

[0092] The resin composition is obtained by mixing a resin (A), a surfactant (B), a filler (C) and a solvent (D) as needed and uniformly kneading them into a slurry with a stirrer. When a solvent (D) is added, the solvent (D) is distilled off from the resin composition. The solvent (D) can be distilled off from the resin composition generated by uniform mixing, or from the coating film described later generated when the sensor element is manufactured.

[0093] <Main effects>

[0094] In the resin composition, the conductivity of the resin composition varies depending on the amount of odorous substances adsorbed on the resin composition. In addition, the adsorption process of the odorous substances to the resin composition varies for each odorous substance. Therefore, the resin composition is used to form a detection portion capable of adsorbing odorous substances, and the detection portion can be used as a sensor element of an odor sensor. By using the resin composition, the odor recognition performance can be improved. For example, it is also possible to identify the actual odor pattern under the interaction of multiple substances, or the actual odor pattern based on a substance with unknown components. In addition, the component stability of the resin composition and the coating stability of the resin composition are excellent. Therefore, the stability of the odor recognition performance when used for a sensor element can be improved.

[0095] Regarding the sensor described in Patent Document 1, it is believed that it can detect odors composed of a single compound. However, odors are mostly mixtures of multiple substances. In the sensor described in Patent Document 1, since its detection unit does not have the function of identifying odor components, the odor recognition performance of the mixture is insufficient. Patent Document 2 discloses that the detection unit can identify the odor of the mixture by making use of the difference in the chemical structure of the conductive polymer used in the detection unit to make the detection unit have different responses to each compound by means of each conductive polymer. However, the chemical structure of the polymer that exhibits conductivity is limited, so it is difficult to make the detection unit respond to any odor component with good sensitivity, making it difficult to distinguish and identify odors composed of similar components. Patent Document 3 proposes the following method: a mixture composed of an organic polymer, a plasticizer and a conductive substance is used as a detection material in the detection unit, and the resistance change of the mixture is detected to identify the penetration of the odor component into the organic polymer. If organic polymers of different components are used, the odor components that penetrate into them are also different. Taking advantage of this, a plurality of detection parts composed of the above-mentioned detection materials containing organic polymers of different components are arranged in parallel, and these detection parts are formed into an array, thereby being able to identify the smell of the mixture. However, in the case of organic polymers containing the above-mentioned organic polymers and plasticizers, even if multiple combinations of organic polymers and conductive substances are prepared, the odor recognition performance is insufficient due to the small difference in chemical properties between the organic polymers. According to these prior arts, for example, it is impossible to accurately detect the actual odor pattern under the interaction of multiple substances or the actual odor pattern based on substances with unknown components.

[0096] [2. Sensor element 31]

[0097] The conductivity of the resin composition changes differently over time depending on whether the resin composition adsorbs odor substance A or odor substance B different from odor substance A. By utilizing this property, a sensor element 31 capable of detecting and identifying each odor substance can be realized.

[0098] Hereinafter, the outline and effects of the sensor element 31 to which the resin composition according to one embodiment of the present invention is applied will be described.

[0099] The sensor element 31 includes an odorant receptor layer 315 containing the resin composition, a first metal wiring 313A, and a second metal wiring 313B. Hereinafter, the first metal wiring 313A and the second metal wiring 313B may be referred to as metal wiring 313 when not distinguishing between them.

[0100] In this specification, the "odorant receptor layer" refers to a layer that adsorbs an odorant to be identified. The odorant receptor layer is formed of the above-mentioned resin composition. The odorant receptor layer can be provided as a part of the sensor element of the embodiment of the present invention.

[0101] Here, combined Figure 2 and Figure 3 , the first metal wiring 313A and the second metal wiring 313B are described. Figure 2 is a top view of an example structure of the sensor element 31. Figure 3 yes Figure 2 A cross-sectional view showing an example structure of the sensor element 31 is shown.

[0102] The first metal wiring 313A and the second metal wiring 313B are metal wirings that function as electrodes to measure changes in the conductivity of the odorant receptor layer 315 (i.e., the resin composition). That is, the first metal wiring 313A and the second metal wiring 313B are separated from each other, and the odorant receptor 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 also be as follows: Figure 2 Shown are metal traces that are generally parallel to each other.

[0103] like Figure 2 As shown, the metal wiring 313 including the first metal wiring 313A and the second metal wiring 313B can also be arranged on the substrate 311. The substrate 311 can be a substrate such as glass epoxy resin commonly used in electronic circuits. The metal wiring 313 can be a metal wiring such as copper or gold. When viewed from a direction perpendicular to the substrate surface, the thickness of each of the first metal wiring 313A and the second metal wiring 313B is preferably 10μm to 2mm, and more preferably 10μm to 1mm. When viewed from a direction parallel to the substrate surface, the height, that is, the thickness of each of the first metal wiring 313A and the second metal wiring 313B is preferably 1μm to 100μm, and more preferably 10μm to 50μm. The interval between the first metal wiring 313A and the second metal wiring 313B is preferably 1μm to 1mm, and more preferably 1μm to 100μm. The length of the metal wiring 313 is preferably 10μm to 50mm, and more preferably 10μm to 30mm.

[0104] The metal wiring 313 may also be arranged on the package substrate 312 . Figure 3 It indicated Figure 2 AA section. Figure 3As shown, a package substrate 312 may be arranged on a substrate 311 such as glass epoxy resin, and a metal wiring 313 may be arranged on the package substrate 312. The package substrate 312 may be fixed to the substrate 311 using a plastic tape 314. In addition, the plastic tape 314 may also be used to mask the excess portion of the metal wiring 313, thereby adjusting the length of the exposed portion of the metal wiring 313. Here, the exposed portion of the metal wiring 313 refers to the portion of the metal wiring 313 that contacts the odorant receptor layer 315. The plastic tape 314 may also be an insulator used to adjust the length of the portion of the metal wiring 313 that contacts the odorant receptor layer 315.

[0105] The odorant receptor layer 315 may also 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. Figure 2 and Figure 3 As shown, the odorant receptor layer 315 may be arranged, for example, so as to fill the space between the first metal wiring 313A and the second metal wiring 313B.

[0106] When the conductivity of the odorant receptor layer 315 (ie, the conductivity of the sensor element 31 ) is low, the interval between the first metal wiring 313A and the second metal wiring 313B is preferably equal to or smaller than a predetermined distance (eg, 500 μm).

[0107] When a resin composition whose conductivity changes with time differently depending on whether odor substance A or odor substance B different from odor substance A is adsorbed is applied to the sensor element 31, the sensor element 31 can detect or identify various odor substances.

[0108] As the sensor element 31, a resistive element, a membrane-type surface stress sensor (MSS) element, or a quartz crystal microbalance (QCM) element can be used. Whether it is a membrane-type surface stress sensor (MSS) element or a quartz crystal microbalance (QCM) element, if there is a slight error and / or uneven thickness of the film material on the electrode, the measurement result will change, so there is a tendency for the deviation between the sensor elements of each manufacturing batch to be large. In addition, with respect to the membrane-type surface stress sensor (MSS) element, since the structure of the stress sensing part such as the cantilever is very fine, if a large amount of slurry is applied at one time to form a thick film, there is a problem that the stress sensing part is damaged and the yield is reduced. On the other hand, these problems are less likely to occur in resistive elements, so from this point of view, it is preferred that the sensor element in the present invention adopts a resistive element. In addition, as the filler (C) of the resistive element, it is preferred to use a conductive carbon material.

[0109] <Method for manufacturing sensor element>

[0110] The sensor element 31 can be manufactured by using the resin composition of the embodiment of the present invention to manufacture the odorant receptor layer 315. The odorant receptor layer 315 can be manufactured by applying the resin composition in the form of a coating liquid and curing or hardening the formed coating film. The coating of the resin composition can be implemented by a known coating technique.

[0111] [3. Odor sensor 30]

[0112] The following, combined Figure 1 The outline and effects of the odor sensor 30 using the sensor element 31 will be described. Figure 1 1 is a schematic diagram of an example of the structure of an odor measurement device 100 equipped with an odor sensor 30, in which a sensor element 31 is used. Figure 1 In the illustrated sensor element 31 , the plastic tape 314 is omitted for clarity.

[0113] The odor sensor 30 includes a sensor element 31 for detecting an odor substance, a constant current source 32 (power source), and a voltmeter 33 (measuring device).

[0114] The first metal wiring 313A and the second metal wiring 313B of the sensor element 31 are connected to each other through a wire W. Figure 1 An example in which the lead wire W is connected to the constant current source 32 and the voltmeter 33 is shown.

[0115] The constant current source 32 is a power source for supplying power to the sensor element 31. The constant current source 32 supplies a constant current (for example, a direct current of 1 mA) to the sensor element 31 via a lead wire.

[0116] The voltmeter 33 measures the potential difference generated between the first metal wiring 313A and the second metal wiring 313B when the constant current supplied from the constant current source 32 is supplied to the odorant receptor layer 315 .

[0117] The odor sensor 30 may further include a housing 34 , but the housing 34 is not an essential structure. The housing 34 is a container that can enclose air containing odor substances. When the housing 34 is provided, the sensor element 31 is disposed in the housing 34 .

[0118] The housing 34 has an inlet 341 for introducing odor substances and an outlet 342 for discharging air containing odor substances. The odor substances can be introduced by inserting filter paper P or the like impregnated with odor substances into the housing 34 from the inlet 341, or by blowing air containing odor substances into the housing 34 from the inlet 341. The housing 34 is a container for enclosing air containing odor substances at a predetermined concentration (e.g., 200 ppm) or more.

[0119] The airflow generating fan 35 may be disposed at the outlet 342 of the housing 34 , but the airflow generating fan 35 is not essential. The airflow generating fan 35 is used to generate airflow in the housing 34 or to discharge the gas in the housing 34 to the outside of the housing 34 through the outlet 342 .

[0120] In addition, the odor sensor 30 may include a constant voltage source (power source) not shown in the figure instead of the constant current source 32, and an ammeter (measuring device) not shown in the figure instead of the voltmeter 33. In this case, the constant voltage source functions as a power source for supplying power to the sensor element 31, and applies a constant voltage to the sensor element 31 via the lead wire. On the other hand, the ammeter measures the current value flowing between the first metal wiring 313A and the second metal wiring 313B when the constant voltage is applied to the odorant receptor layer 315.

[0121] The odor sensor 30 outputs a measurement value indicating a temporal change in the conductivity of the sensor element 31 before and after the odor substance is adsorbed to the sensor element 31. Thus, various odor substances can be detected or identified.

[0122] [4. Odor measuring device 100]

[0123] When various odor substances are adsorbed on the sensor element 31, the odor sensor 30 can output the temporal change of the conductivity of the sensor element 31 for each odor substance. According to the odor sensor 30, the temporal change of the conductivity of the sensor element 31 when the sensor element 31 adsorbs the odor substance A can be compared with the temporal change of the conductivity of the sensor element 31 when the sensor element 31 adsorbs the odor substance B. Thus, the odor measuring device 100 can be realized which can estimate the odor substance adsorbed on the sensor element 31 based on the comparison result.

[0124] Furthermore, the odor measuring device 100 can perform high-precision odorant estimation by using the estimation model 22 generated by machine learning. The estimation model 22 can be generated by measuring a measurement value when each of a plurality of odorants is adsorbed on at least one sensor element 31, combining the measurement value with the inherent identification information of the odorant causing the measurement value, including the combination in the learning data, and generating the estimation model using the learning data.

[0125] Hereinafter, the outline and effects of the odor measuring device 100 using the odor sensor 30 will be described. The odor measuring device 100 estimates the odor substance adsorbed on the sensor element 31 based on the change in conductivity of the sensor element 31 including the resin composition.

[0126] First, combine Figure 1 The structure of the odor measuring device 100 according to one embodiment of the present invention will be described. Figure 1 This is a block diagram showing an example structure of the odor measuring device 100 .

[0127] like Figure 1 As shown, the odor measurement device 100 includes an estimation device 10 and an odor sensor 30 .

[0128] <Estimation Device 10>

[0129] The estimation device 10 is a device for estimating the odor substance detected by the odor sensor 30. The estimation device 10 is, for example, a computer and includes a CPU and a memory (not shown). The estimation device 10 is connected to the odor sensor 30 in a communicable manner. Specifically, the estimation device 10 analyzes the measurement value obtained by the odor sensor 30, thereby performing the estimation of the odor substance. The structure of the estimation device 10 will be described later.

[0130] <Generation of Estimation Model 22>

[0131] Next, combine Figure 4 and Figure 5, the structure of the odor measurement device 100 and the generation process of the estimation model 22 when performing the generation process of the estimation model 22 for estimating odor substances are described.

[0132] The estimation model 22 can be generated by causing at least one sensor element 31 to adsorb each of a plurality of odor substances, measuring a measurement value by a voltmeter 33, combining the measurement value with the inherent identification information of the odor substance causing the measurement value, including the combination in learning data, and performing machine learning using the learning data. Here, the inherent identification information of the odor substance may be, for example, the name of the odor substance, the CAS number, and the chemical formula.

[0133] (Configuration of Estimation Device 10 (Generation of Estimation Model 22))

[0134] Figure 4 is a functional block diagram of an example of the structure of the odor measuring device 100. Figure 1 Components having the same functions as those described above are marked with the same reference numerals and will not be described in detail.

[0135] like Figure 4 As shown, the estimation device 10 includes an input unit 15 , a control unit 1 , and a storage unit 2 .

[0136] The input unit 15 is used to receive various input operations from the user, and may be, for example, a keyboard, a mouse, a touch screen, or the like.

[0137] 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 14 .

[0138] The measurement value acquisition unit 11 acquires the measurement value from the voltmeter 33. In addition, the measurement value acquisition unit 11 uses the acquired measurement value to calculate a value (e.g., resistance value, impedance, etc.) indicating the conductivity of the sensor element 31. In the present disclosure, it is preferred that the measurement value acquisition unit 11 calculates the change in resistance value of the odorant receptor layer. The measurement value acquisition unit 11 may also acquire the measurement value from the voltmeter 33 at a predetermined time interval (e.g., 0.1 second interval).

[0139] The change pattern analysis unit 12 analyzes the change in conductivity of at least one sensor element 31 over time. The change pattern analysis unit 12 calculates the value of the conductivity change amount of the sensor element 31 due to the adsorption of the odor substance using the resistance value calculated by the measurement value acquisition unit 11. The change pattern analysis unit 12 generates data representing a change pattern, wherein the change pattern represents the change in conductivity change amount over time calculated. If the generated change pattern means a known odor substance, the change pattern analysis unit 12 may associate the generated change pattern with the inherent identification information of the known odor substance and store them in the change pattern database 21 (learning data).

[0140] The learning control unit 13 reads the change pattern database 21 in the storage unit 2, and controls the generation process of the estimation model 22 based on machine learning. Here, the change pattern database 21 includes a combination of the measurement value measured when the sensor element 31 adsorbs a plurality of odor substances, and the inherent identification information of the known odor substances that caused the measurement value. The learning control unit 13 inputs the change pattern 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 made according to the comparison result to the estimation model generation unit 14.

[0141] The estimation model generation unit 14 generates the estimation model 22 by using the change pattern in the change pattern database 21 through a corresponding machine learning algorithm. The estimation model generation unit 14 may also use a known machine learning algorithm with a teacher to generate the estimation model 22. As machine learning algorithms applicable to the estimation model generation unit 14, for example, k-nearest neighbor method, logistic regression, support vector machine, random forest, neural network, etc. can be cited.

[0142] (Processing of Generating Estimation Model 22)

[0143] The following, combined Figure 5 The specific processing performed by each unit of the control unit 1 will be described. Figure 5 This is a flowchart of an example of a process flow for the estimation device 10 to generate the estimation model 22 .

[0144] First, the measured value acquisition unit 11 acquires the voltage value V0 measured by the odor sensor 30 before the filter paper P impregnated with the odorant is inserted into the housing 34, and calculates the resistance value R0 (step S11). The resistance value R0 is preferably 200 to 10000Ω, more preferably 250 to 3000Ω, and most preferably 300 to 1000Ω.

[0145] On the other hand, the input unit 15 receives an input operation of the name of the known odor substance impregnated on the filter paper P inserted into the housing 34 (step S12). The processing of step S12 may be performed before step S11.

[0146] Next, the measured value acquisition unit 11 acquires the voltage value V measured by the odor sensor 30 immediately after the filter paper P impregnated with the known odor substance is inserted into the housing 34, and calculates the resistance value R (step S13).

[0147] Then, the change pattern analysis unit 12 uses the resistance value R0 and the resistance value R to calculate R / R0 (step S14). The value of R / R0 represents the amount of conductivity change caused by the adsorption of the known odor substance on the sensor element 31. Here, the change pattern analysis unit 12 can also calculate R-R0 instead of calculating R / R0. The change pattern analysis unit 12 associates the change pattern of R / R0 over time with the input known odor substance name and stores them in the change pattern database 21 (step S15).

[0148] If the change pattern of the known odor substance of the specified type has not been stored ("No" in step S16), that is, if the data for machine learning is insufficient, the process returns to step S11.

[0149] If the change pattern of the known odor substance of the specified type is already stored ("Yes" in step S16), the learning control unit 13 reads the change pattern of the known odor substance stored in the change pattern database 21, and inputs it to the estimated model generation unit 14. The estimated model generation unit 14 applies the change pattern stored in the change pattern database 21 to the machine learning algorithm, and generates the estimated model 22 through the machine learning algorithm (step S17).

[0150] The estimation model generation unit 14 stores the estimation model 22 generated through predetermined machine learning in the storage unit 2 (step S18 ).

[0151] Although in Figure 4 and Figure 5 In the example shown, the estimation model 22 is generated by the estimation device 10, but the present invention is not limited thereto. For example, the same data as the data in the change pattern database 21 may be provided to an external computer having the same functions as the learning control unit 13 and the estimation model generation unit 14 but different from the estimation device 10, and the estimation model 22 may be generated by the computer.

[0152] (Estimation of odorous substances)

[0153] Next, combine Figure 6 as well as Figure 7Next, the configuration and estimation process of the odor measurement device 100a when estimating odor substances using the estimation model 22 will be described.

[0154] (Configuration of Estimation Device 10a (Execution of Estimation Process))

[0155] Figure 6 is a functional block diagram of an example of the structure of the odor measuring device 100a. Figure 1 and Figure 4 Components having the same functions as those described above are marked with the same reference numerals and will not be described in detail.

[0156] like Figure 6 As shown, the estimation device 10a includes a control unit 1a, a storage unit 2a, and an output unit 18. Figure 6 Shows the Figure 4 The estimation device 10 shown is a configuration example in which the estimation device 10 is used for odorant estimation processing. Figure 4 The estimation device 10 and Figure 6 The estimating devices 10a shown may be computers having the same hardware configuration.

[0157] The output unit 18 is used to present the estimation result to the user, and may be, for example, a display, a speaker, a lamp, etc.

[0158] 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 .

[0159] The estimation unit 16 estimates the odor substance based on the analysis result of analyzing the measurement value obtained from the odor sensor 30 using the estimation model 22 .

[0160] The output control unit 17 controls the output unit 18 to output the estimation result.

[0161] (Presumption Processing)

[0162] The following, combined Figure 7 The specific processing performed by each unit of the control unit 1a will be described. Figure 7 This is a flowchart of an example of the processing flow of estimating odor substances by the estimating device 10a.

[0163] First, the measured value acquisition unit 11 acquires the voltage value V0 measured by the odor sensor 30 before the filter paper P impregnated with the odorant is inserted into the housing 34, and calculates the resistance value R0 (step S1).

[0164] Next, the measured value acquisition unit 11 acquires the voltage value V measured by the odor sensor 30 immediately after the filter paper P impregnated with the unknown odor substance (ie, the estimation target) is inserted into the housing 34, and calculates the resistance value R (step S2).

[0165] Then, the change pattern analysis unit 12 calculates R / R0 using the resistance value R0 and the resistance value R (step S3 ).

[0166] Next, the estimation unit 16 estimates the unknown odorant from the temporal variation pattern of R / R0 based on the estimation model 22 (step S4).

[0167] The output control unit 17 controls the output unit to output the estimation result (step S5).

[0168] [Implementation method 2]

[0169] Although the odor sensor 30 having a single sensor element 31 is described in the above embodiment, the odor sensor 30 may also have two or more sensor elements 31. For example, the odor sensor 30b may also have sensor elements 31 and 31b having different resin compositions in the odor substance receptor layer 315. Figure 8 Provide explanation. Figure 8 FIG. 1 is a block diagram of an example of the structure of an odor measuring device 100b according to another embodiment of the present invention. Figure 1 Components having the same functions as those described above are marked with the same reference numerals and will not be described in detail.

[0170] For example, Figure 8 The odor measurement device 100b shown includes odor sensors 30, 30b and an estimation device 10b. The odor sensor 30b includes a sensor element 31 and a sensor element 31b, but the resin composition used in the odor substance receptor layer 315 of the sensor element 31 and the resin composition used in the odor substance receptor layer 315b of the sensor element 31b may be different.

[0171] The estimation device 10b may be a computer having the same hardware structure as the estimation devices 10 and 10a. The estimation device 10b obtains and analyzes a first measurement value and a second measurement value, respectively. The first measurement value is a measurement value measured by the voltmeter 33 when the constant current source 32 supplies a constant current to the sensor element 31, and the second measurement value is a measurement value measured by the voltmeter 33b when the constant current source 32b supplies a constant current to the sensor element 31b.

[0172] By having a plurality of sensor elements in which resin compositions having different odorant adsorption characteristics are used in the odorant receptor layer, the odor measuring device 100b can simultaneously estimate a plurality of odorants. Here, in addition to using the sensor element of one embodiment of the present invention, a sensor element in which the odorant receptor layer does not contain a surfactant (B) can also be used.

[0173] In addition, when the odor measuring device 100b is used, the first change pattern, which is the change in conductivity of the sensor element 31 for each known odor substance, and the second change pattern, which is the change in conductivity of the sensor element 31b for each known odor substance, can be obtained. The estimation model 22 can also be generated by machine learning using both the first change pattern and the second change pattern. The odor measuring device 100b estimates the odor substance using the estimation model 22 generated in this way, and can therefore identify each odor substance more accurately.

[0174] [Implementation method 3]

[0175] An embodiment of the present invention will be described in detail below.

[0176] Regarding the odor measuring device 100b of the second embodiment, an example is described in which a filter paper P impregnated with an odor substance is inserted into a housing 34 having two sensor elements (i.e., sensor elements 31 and 31b) built therein. However, this example cannot control the timing when the odor substance reaches the sensor elements 31 and 31b, or cannot adjust the concentration of the odor substance. In contrast, the odor measuring device 100c of the present embodiment includes a sensor chamber 60 and a target material receiving part 50 that are independent of each other, and the sensor chamber 60 includes a plurality of sensor elements (hereinafter referred to as a sensor element group 31A), and a target material containing an odor substance is introduced into the target material receiving part 50, and a gas containing an odor substance generated from the target material is contained in the target material receiving part 50. In the present embodiment, each individual sensor element included in the sensor element group 31A may be simply referred to as a "sensor element". In addition, in the present embodiment, the target material receiving part 50 and the sensor chamber 60 correspond to the odor sensor 30 and the odor sensor 31 of the first and second embodiments.

[0177] The odor measuring device 100c of this embodiment adopts a scheme of using another gas (carrier gas) to push the gas containing the odor substance inside the target material receiving part 50 to the sensor chamber 60. In this embodiment, the gas inside the target material receiving part 50 when the target material is introduced into the target material receiving part 50 (that is, the gas containing the detection target odor substance) is called the first gas. On the other hand, the carrier gas used to push the first gas to the sensor chamber 60 is called the second gas.

[0178] Fig. 9 is a schematic diagram of the odor measuring device 100c. Fig. 9 As shown in FIG. 1 , the odor measuring device 100 c includes a target material receiving unit 50 , a sensor chamber 60 , a gas supply unit 80 , and an estimation device 10 b .

[0179] As an example, Fig. 9 The example in which the gas flows from the gas supply part 80 to the target material receiving part 50 and the sensor chamber 60 in sequence is shown. The gas supply part 80, the target material receiving part 50 and the sensor chamber 60 are connected to each other through a pipe.

[0180] The target material receiving part 50 can receive the target material containing the odorous substance and hold the first gas therein. The target material receiving part 50 includes: a first opening 501 for the second gas to flow into the target material receiving part 50, and a second opening 502 for the first gas and the second gas to flow out of the target material receiving part 50. Here, the target material receiving part 50 may also include a material introduction port 503 described later.

[0181] exist Fig. 9 In the figure, the first opening 501 is arranged at the upper portion of the target material receiving portion 50 as seen in the figure, and the second opening 502 is arranged at the lower portion of the target material receiving portion 50 as seen in the figure, but it is not limited thereto. For example, the positions of the first opening 501 and the second opening 502 can also be appropriately set according to the types and combinations of the odor components contained in the first gas. For example, the position of the first opening 501 and the position of the second opening 502 can be changed according to 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. In addition, Figure 8 Likewise, the target material receiving portion 50 may include an airflow generating fan 35 therein.

[0182] The target material receiving section 50 includes a material introduction port 503 for receiving a liquid or solid target material. Fig. 9 In, with Figure 8Similarly, a scheme of introducing a filter paper P impregnated with an odorous substance as the target material is shown. The target material receiving section 50 may also include a setting section (not shown) for setting the target material. When the target material is a liquid, the setting section may be a cup for holding the liquid, and when the target material is a solid, the setting section may be a dish for placing a stationary object. The target material may also be introduced into the target material receiving section 50 from the sample inlet 503 in a gaseous state as the first gas. In this way, the target material receiving section 50 can receive a liquid or solid target material, and thus the concentration of the odorous substance in the first gas can be adjusted. For example, for the same odorous substance, the concentration of the odorous substance in the first gas can be easily adjusted.

[0183] The inner side surface of the target material receiving portion 50 may also be provided with a raw material that is inactive to odor substances. The raw material that is inactive to odor substances refers to a raw material that does not significantly change the concentration of various odor substances contained in the gas delivered to the sensor chamber 60. The raw material that is inactive to odor substances is, for example, a raw material that is difficult for odor substances to adsorb or dissolve. Examples of raw materials that are inactive to odor substances include glass, metal, and resin. When metal is used, stainless steel (SUS) is preferred. When resin is used, fluorine-based resins, polypropylene (PP), polyethylene (PE), ABS resin, and polyethylene terephthalate (PET) are preferred.

[0184] If the inner surface of the target material receiving portion 50 is a material that adsorbs the odorant contained in the first gas, the adsorption of the odorant in each part may affect subsequent measurements.

[0185] If the inner side surface of the target material receiving portion 50 is a raw material that is inactive to the odorant as described above, the possibility that the raw material on the inner side surface reacts with the odorant contained in the first gas or that the odorant is adsorbed on the inner side surface can be reduced. Therefore, the possibility that the odorant contained in the first gas supplied to the sensor chamber 60 changes during the process of being contained in the target material receiving portion 50 or the concentration of the odorant becomes weaker can be reduced.

[0186] Since the odor measuring device 100c includes the target material receiving part 50, even if the target material is liquid or solid, the concentration of the first gas in the target material receiving part 50 can be made uniform before the first gas is sent to the sensor chamber 60. In addition, since the odor measuring device 100c includes the target material receiving part 50, the first gas can be sent to the sensor chamber 60 at a constant flow rate. Therefore, even when the odor measuring device 100c repeatedly performs measurement, the first gas can be sent to the sensor chamber 60 under the same conditions each time, so that stable measurement can be repeatedly performed.

[0187] The internal volume of the target material receiving part 50 is preferably not less than 1 times and not more than 100 times the internal volume of the sensor chamber 60. In particular, the internal volume of the target material receiving part 50 is preferably larger than the internal volume of the sensor chamber 60. The internal volume of the target material receiving part 50 is more preferably not less than 2 times and not more than 80 times the internal volume of the sensor chamber 60. The internal volume of the target material receiving part 50 is further preferably not less than 4 times and not more than 60 times the internal volume of the sensor chamber 60. When the internal volume of the target material receiving part 50 is not less than 1 times the internal volume of the sensor chamber 60, the concentration of the odor substance in the sensor chamber 60 can be appropriately adjusted, so that the measurement result of the sensor provided in the sensor chamber 60 can be stably output. In addition, when the internal volume of the target material receiving part 50 is not more than 100 times the internal volume of the sensor chamber 60, the measurement result of the sensor can be stably output, and the size of the odor measuring device 100c can be compactly reduced.

[0188] If the volume of the target material receiving part 50 is less than 1 times the volume of the sensor chamber 60, the odor substances generated in the target material receiving part 50 will become diluted in the sensor chamber 60, which may cause the sensor's measurement sensitivity to decrease. In addition, if the volume of the target material receiving part 50 exceeds 100 times the volume of the sensor chamber 60, the overall size of the odor measuring device 100c may increase due to the excessive volume of the target material receiving part 50.

[0189] Fig. 9 In FIG. 1 , as an example, an example is shown in which the internal volume of the target material receiving portion 50 is 8 times the internal volume of the sensor chamber 60 .

[0190] For example, if the inner side surface of the tube body 93 is made of a raw material that adsorbs odorous substances contained in the first gas, subsequent measurements may be affected by the adsorption of odorous substances by various parts. In this regard, it is preferred that the inner side surface of the tube body 93 used to guide the first gas from the target material receiving portion 50 to the sensor chamber 60 is provided with a raw material that is inactive to odorous substances, similar to the inner side surface of the target material receiving portion 50. Examples of raw materials that are inactive to the first gas include glass, metal, and resin. When metal is used, stainless steel (SUS) is preferred. When resin is used, fluorine-based resins, polypropylene (PP), polyethylene (PE), ABS resin, and polyethylene terephthalate (PET) are preferred.

[0191] The target material receiving part 50 can also be attached and detached with respect to the tube body 92 and the tube body 93. In this way, the target material receiving part 50 can be attached and detached, so that when the previous measurement is completed and the next measurement is to be performed, it is not necessary to purge the inside of the target material receiving part 50 and a new target material receiving part 50 can be directly replaced. In this way, the odor measuring device 100c can perform multiple measurements in a short time.

[0192] In addition, since the target material receiving part 50 can be loaded and unloaded, the target material receiving part 50 into which the target material is introduced can be kept at a predetermined temperature by the heat preservation chamber provided separately from the odor measuring device 100c. Thus, for example, even if the adjustment part 51 described later cannot be provided in the odor measuring device 100c, the odor measuring device 100c can adjust the temperature of the target material receiving part 50.

[0193] The regulating part 51 regulates at least one of the temperature and humidity of the first gas contained in the target material receiving part 50. When the regulating part 51 regulates the temperature, the regulating part 51 is, for example, a heater or a cooler. In this case, the regulating part 51 may be a structure that covers the entire target material receiving part 50. In addition, when the regulating part 51 regulates the humidity, the regulating part 51 is, for example, a humidifier or a dehumidifier. The regulating part 51 may regulate at least one of the temperature and humidity for each type of the first gas, and may also change at least one of the temperature and humidity at predetermined intervals during the measurement of the same first gas.

[0194] The adjustment unit 51 adjusts at least one of the temperature and humidity of the first gas in the target material receiving unit 50, so that the odor measuring device 100c can, for example, deliver the first gas to the sensor chamber 60 under conditions that match the type of the first gas (gas weight, volatility, etc.). In addition, through the above-mentioned adjustment, the odor measuring device 100c can deliver the first gas with a stable concentration to the sensor chamber 60, thereby improving the measurement accuracy.

[0195] The gas supply unit 80 is connected to the first opening 501 of the target material receiving unit 50 , and delivers the second gas into the target material receiving unit 50 , thereby pushing the first gas from the target material receiving unit 50 into the sensor chamber 60 .

[0196] A valve 81 may be provided between the gas supply unit 80 and the target material receiving unit 50. By opening and closing the valve 81, the start and stop of the supply of gas from the gas supply unit 80 can be regulated.

[0197] As described above, the gas supply unit 80 pushes the gas from the first opening 501 side of the target material receiving unit 50 to send the first gas into the sensor chamber 60, so the pressure in the sensor chamber 60 is positive. Therefore, the odor measuring device 100c can obtain a stable measurement result. In addition, since the second gas can be delivered by opening and closing the valve 81, the odor measuring device 100c can push the first gas from the target material receiving unit 50 to the sensor chamber 60 at any timing. Therefore, in the odor measuring device 100c, when the odor substance contained in the first gas is repeatedly measured using the sensor element group 31A, the shape reproducibility of the waveform output by each sensor element can be improved.

[0198] The second gas may be an inert gas or air. Examples of the inert gas include argon and nitrogen. If the second gas is an inert gas, the gas supply unit 80 may be a gas cylinder.

[0199] In addition, if 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 material receiving unit 50, the odor measuring device 100c may also include, for example, an activated carbon filter on the first opening 501 side of the target material receiving unit 50.

[0200] The odor measuring device 100c may further include a mass flow controller on the first opening 501 side of the target material receiving part 50, more specifically, between the valve 81 and the gas supply part 80. The odor measuring device 100c with this structure can deliver the first gas from the target material receiving part 50 to the sensor chamber 60 at a constant flow rate, so that the sensor elements of the sensor element group 31A can output stably.

[0201] The estimation device 10b has the same function as the estimation device 10b of the second embodiment. If the sensor chamber 60 further includes a sensor element 31c in which a resin composition different from the sensor element 31 and the sensor element 31b is used in the substance receptor layer 315, the estimation device 10b can further obtain and analyze the measurement value measured by the voltmeter when a constant current is supplied to the sensor element 31c. In addition, the estimation device 10b can also display the measurement value itself, the waveform obtained by plotting the measurement value, and the estimation result of the unknown odor substance based on the estimation model. In addition, for a gas containing multiple odor substances, the estimation device 10b can also display a numerical value and a graph to indicate the change in the existence ratio of each odor substance.

[0202] The sensor chamber 60 is a space for accommodating the sensor element group 31A for measuring odor substances. The sensor chamber 60 is connected to the second opening 502 of the target material receiving part 50. Specifically, the sensor chamber 60 has a gas supply port 601 and a gas exhaust port 602, and the second opening 502 of the target material receiving part 50 is connected to the gas supply port 601.

[0203] The sensor chamber 60 has a plurality of channels, and a plurality of sensor elements capable of outputting the corresponding measurement results of the odor substances contained in the gas are arranged in the channels. Thus, the time required from the start of the gas being fed into the sensor chamber to the time when the plurality of sensor elements stably output the measurement results can be shortened. In addition, the plurality of sensor elements are finely divided by the plurality of channels, so that the airflows in the channels measured each time are less turbulent and uneven, thereby achieving high measurement accuracy.

[0204] Fig.10 FIG. 6 is a top view of a structural example of the sensor chamber 60. Fig.10 , a sensor chamber 60 having four channels (ie, channel 61 , channel 62 , channel 63 , and channel 64 ) is shown. The first gas can be supplied from the target material receiving portion 50 to each of the channels 61 to 64 .

[0205] In each of the multiple channels (channels 61 to 64), multiple sensor elements that output different measurement results for each odor substance may also be configured. The multiple sensor elements that output different measurement results for each odor substance may also be sensor elements that have different resin compositions as their material receptor layers. That is, the sensitivity and detection specificity of the multiple sensor elements configured in the same channel to the odor substance may be different. Fig.10 As an example, the sensor chamber 60 may have a second embodiment ( Figure 8 ) is not limited to the sensor element 31 and the sensor element 31b described in the figure. For example, the sensor element 31 and the sensor element 31b can both output the corresponding measurement results of the same odor substance contained in the first gas, but the measurement results output by each sensor element can also be different. In addition, the sensor element 31 and the sensor element 31b can also each output the corresponding measurement results of different odor substances. The corresponding measurement results of the odor substance are, for example, measurement results corresponding to the concentration of the odor substance. By configuring a plurality of sensor elements that output different measurement results for each odor substance in each of a plurality of channels, the odor measuring device 100c can detect the odor substance flowing through a single channel by using sensor elements with different sensitivities and detection specificities. As a result, the odor measuring device 100c can comprehensively detect the odor substance based on the different plurality of measurement results.

[0206] In addition, Fig.10 Among them, similar to the channel 61, in the channel 62, a plurality of sensor elements (such as sensor elements 31c and 31d, etc.) capable of outputting corresponding measurement results of the odor substances contained in the first gas are arranged. In the channel 63, a plurality of sensor elements (such as sensor elements 31e and 31f, etc.) capable of outputting corresponding measurement results of the odor substances contained in the first gas are arranged. In the channel 64, a plurality of sensor elements (such as sensor elements 31g and 31h, etc.) capable of outputting corresponding measurement results of the odor substances contained in the first gas are arranged. The resin compositions used in the substance receptor layers 315 of these plurality of sensor elements may also be different from each other.

[0207] Here, the detection specificities of some of the sensor elements among the sensor elements 31 to 31h for the odor components may also be the same. That is, for example, if the sensor element group 31A arranged in the sensor chamber 60 includes n sensor elements, then m types (m < n) of sensor elements can be arranged. In addition, the detection specificities of some of the plurality of sensor elements arranged in the same channel for the odor components may also be the same.

[0208] In addition, the sensor chamber 60 may also have channels 61 to 64, and a plurality of sensor elements may also be arranged in each of the channels 61 to 64. In this case, the plurality of sensor elements arranged in each of the channels 61 to 64 constitute the sensor element group 31A. For example, 4 sensor elements can be arranged in the channel 61 and 10 sensor elements can be arranged in the channel 62.

[0209] If different numbers of sensor elements are arranged in each of the channels 61 to 64, it is preferable that the difference in the number of sensor elements arranged in each of the channels 61 to 64 is 10 or less. By making the difference in the number of sensor elements arranged in each channel 10 or less, it is possible to alleviate the inconsistency in the detection timing of the odor substances by the sensor elements that may be caused by the channel conditions. In addition, by making the difference in the number of sensor elements arranged in each of the channels 61 to 64 10 or less, the odor measuring device 100c can complete the odor measurement in a short time.

[0210] Each channel is respectively connected to a pipe body 93 used to supply the first gas into the internal space of the sensor chamber 60. As Fig.10 shown, the channels 61, 62, 63 and 64 are all connected to one pipe body 93.

[0211] In addition, the cross-sectional area of ​​each channel perpendicular to the supply direction of the first gas from the tube body 93 can be smaller than the cross-sectional area perpendicular to the axial direction of the tube body 93. As a result, the flow rate of the first gas supplied from the target material receiving part 50 when flowing through each channel can be higher than the flow rate when flowing through the tube body 93. As a result, the measurement time difference between the sensor element arranged near the gas supply port 601 and the sensor element arranged near the gas discharge port 602 can be minimized, so that the odor measuring device 100c can perform high-precision measurement.

[0212] In addition, the gas in each internal space of the channel is preferably ventilated within 1 second from the start of the first gas supply. The start time of the first gas supply refers to when the first gas reaches the gas supply port 601. In addition, the ventilation of the gas in the internal space refers to the flow of the first gas supplied from the gas supply port 601 to the gas outlet 602. In this way, by allowing the gas in each internal space of the channel to be ventilated within 1 second from the start of the first gas and the second gas supply, the deviation in the timing of the first gas contacting each sensor element can be reduced, so that the odor measuring device 100c can perform measurements stably. In addition, by allowing the gas in each internal space of the channel to be ventilated within 1 second from the start of the first gas and the second gas supply, the odor measuring device 100c can complete odor measurement in a short time.

[0213] The flow rate of the first gas flowing through each internal space of the channel is preferably 0.1 cm per second or more and 100 cm per second or less. In addition, the flow rate of the first gas flowing through each internal space of the channel is more preferably 1 cm per second or more and 50 cm per second or less. The flow rate of the first gas flowing through each internal space of the channel can be adjusted, for example, by the degree of pressurization of the gas supply unit 80 described later, or by the mass flow controller described later.

[0214] If the flow rate of the first gas flowing through the internal space of each channel is slow, the timing of the first gas contacting all the sensor elements in the sensor element group 31A may become larger. On the other hand, if the flow rate of the first gas flowing through the internal space of each channel is too fast, the sensor elements of the sensor element group 31A may vibrate due to the influence of the airflow, and the odor measuring device 100c may not be able to stably measure the odor. In addition, if the flow rate of the first gas flowing through the internal space of each channel is too fast, the adsorption of the odor substances contained in the first gas to the sensor elements of the sensor element group 31A may be hindered, and the odor measuring device 100c may not be able to perform correct odor measurement. In addition, if the flow rate of the first gas flowing through the internal space of each channel is too fast, the first gas in the target material receiving part 50 may be exhausted before the odor measuring device 100c enters stable measurement.

[0215] In this way, by setting the flow rate of the first gas flowing through the internal space of each channel to be 0.1 cm per second or more and 100 cm per second or less, the odor measurement device 100c can perform odor measurement stably.

[0216] Individual channels can also be configured side by side. Fig.10 In the embodiment, the channels 61 to 64 are arranged side by side. By arranging the channels side by side in this way, a larger channel arrangement space can be ensured in the odor measurement device 100c, and the overall size of the device can be designed to be compact.

[0217] Fig.11 is along Fig.10 Schematic cross-sectional view of the BB section. Fig.11 The channel 61 is composed of a side wall 610, a side wall 611 opposite to the side wall 610, a top plate 621, and a substrate 630 serving as the bottom surface of the channel.

[0218] Although Fig.11 , the sensor chamber 60 is shown in which the cross-sectional shape of the channel 61 is a quadrangular shape, but the cross-sectional shape of the channel 61 is not particularly limited. For example, the cross-sectional shape of the channel 61 may be an arc shape or a triangle shape.

[0219] The channel 61 and the channel 62 may be completely separated from each other by the side walls 611 and 612 so that gas does not flow in or out between the channel 61 and the channel 62 .

[0220] exist Fig.11 In the embodiment, although the structure in which two side walls (side wall 611 and side wall 612) are provided between the channel 61 and the channel 62 is shown as an example, the present invention is not limited thereto. For example, the channel 61 and the channel 62 may be separated by one side wall.

[0221] Although Fig.11 The entire sensor chamber 60 is formed as a whole, but is not limited to this structure. The entire sensor chamber 60 can be formed as a whole or can be formed separately by each of the multiple channels.

[0222] Fig.11In the sensor chamber 60, for example, the sensor element 31 may be provided on the substrate 630 which is the bottom surface of the channel 61, but the arrangement of the sensor element 31 is not limited thereto. For example, the sensor element 31 may be arranged based on the type of the target odor substance that the sensor element 31 can specifically detect. For example, the sensor element 31 may be provided on any one of the side wall 610, the side wall 611, and the top plate 621. Specifically, in the case where the odor substance is lighter than air, for example, the sensor element 31 may be arranged on the top plate 621. Thus, the sensor element 31 is arranged at a position suitable for the type of the odor substance, so that the odor measurement device 100c can perform high-precision measurement.

[0223] Although in Fig.11 In the sensor chamber 60 , each sensor element is provided on the substrate 630 , but a connector for connecting the substrate 630 and the sensor element may be further provided between the substrate 630 and each sensor element.

[0224] Each sensor element may be independently connected to the substrate 630 one by one. For example, the sensor elements may be connected to the substrate 630 one by one via a connector (e.g., IC pin). Thus, even if a single sensor element included in the sensor chamber 60 fails, the user can replace only the failed sensor element.

[0225] In addition, when detecting odor substances by using a plurality of sensor elements, the optimal combination of sensor elements used and the optimal arrangement of sensor elements differ depending on the type of odor substances. By connecting each sensor element independently to the substrate 630, each sensor element can be freely attached and detached. Therefore, in the odor measuring device 100c, it is possible to easily change the optimal combination of sensor elements and arrangement of sensor elements that match the odor substances.

[0226] The sensor element may be arranged at two or more positions among the substrate 630, the side wall 610, the side wall 611, and the top plate 621. Thus, the length of the channel 61 can be shortened compared to the case where the sensor element is arranged on only one surface, so the size of the odor measurement device 100c can be compact. In addition, since a plurality of sensor elements can be arranged at a position close to the gas supply port 601, the odor measurement device 100c can complete odor measurement in a short time compared to the case where the sensor elements are arranged one by one toward the gas discharge port 602.

[0227] Although in Fig.11 In the sensor chamber 60 , as an example, four channels are provided and one sensor element is arranged in each channel cross section, but the number of channels and the number of sensor elements in the channel cross section are not limited thereto. Fig.12: is a cross-sectional view of the sensor chamber 60a. As an example, the sensor chamber 60a has two channels (channel 61a and channel 62a). In addition, when looking at the cross section of the channel 61a, two sensors (i.e., the sensor element 31 and the sensor element 31c) are provided. In addition, in the sensor chamber 60a, as mentioned above, the sensor element can be arranged not only on the substrate 630, but also at two or more positions among the substrate 630, the side wall 610a, the side wall 613a and the top plate 621a. The arrangement of the sensor element in the channel 62a is the same as that of the channel 61a.

[0228] The raw material of the inner side surface of the sensor chamber 60 is also the same as the target material receiving portion 50, and is preferably a raw material that is inactive to the odorous substance. Examples of inactive materials include glass, metal, and resin. In the case of metal, stainless steel (SUS) is preferred. In the case of resin, fluorine-based resin, polypropylene (PP), polyethylene (PE), ABS resin, and polyethylene terephthalate (PET) are preferred. If the raw material of the inner side surface of the sensor chamber 60 is a raw material that adsorbs the odorous substance contained in the first gas, the sensor chamber may adsorb the odorous substance, which may reduce the variation in the output value of the sensor element during subsequent measurements, and the odor measuring device 100c may not be able to perform correct measurements.

[0229] The sensor elements of the sensor element group 31A may also include a thin film. As an example, Figure 2 and Figure 3 The odor substance receptor layer 315 is a thin film.

[0230] As a method for sending the first gas containing the odor substance into the sensor chamber 60, for example, a vacuum pump is provided on the gas outlet 602 side of the sensor chamber 60, and the odor substance is sent into the sensor chamber 60 from the gas supply port 601 side of the sensor chamber 60 by using the vacuum pump to evacuate the gas. However, when the sensor elements 31 and 31b have a thin film, if the pressure in the sensor chamber 60 is negative, the thin film may expand, and the sensor elements 31 and 31b may not be able to output stable measurement results. In the odor measurement device 100c of the present embodiment, the gas supply unit 80 pushes the gas from the first opening 501 side of the sensor chamber 60 and the target material receiving unit 50 to send the first gas into the sensor chamber 60, so that the pressure in the sensor chamber 60 is positive. Therefore, even if the sensor elements of the sensor element group 31A have a thin film, the odor measurement device 100c can obtain stable measurement results.

[0231] In addition, the thin film of the sensor element of the sensor element group 31A may contain a conductive carbon material, a resin composition, and a surfactant. The specific form of the sensor element will be described later.

[0232] [Sensor element]

[0233] The odor measuring device 100b of the second embodiment includes two sensor elements 31 and 31b. In the second embodiment, although no particular requirement is imposed on the unevenness of the shape, area, and thickness of the odorant receptor layers 315 and 315b of the sensor elements 31 and 31b, the less unevenness of the shape, area, and thickness of the odorant receptor layers 315 and 315b, the more preferably. This is because if the odorant receptor layers 315 and 315b of the plurality of sensor elements are uneven in shape, area, and thickness, it may be impossible to stably measure the odorant. Hereinafter, each odorant receptor layer is also simply referred to as an "odorant receptor layer".

[0234] The sensor elements 31 and 31b of the second embodiment each include a single first metal wiring 313A and a single second metal wiring 313B as electrodes, and the two metal wirings are arranged in parallel with each other (see Figure 2 ). In addition, the sensor elements 31 and 31b of the second embodiment each include an odorant receptor layer 315, and the odorant receptor layer 315 fills the area between the first metal wiring 313A and the second metal wiring 313B. In addition to the sensor elements 31 and 31b, the sensor element group 31A may also include other sensor elements that are configured by different metal wiring (i.e., electrode) configurations and odorant receptor layer shapes from the sensor elements 31 and 31b. Here, the component referred to as the metal wiring 313 in the first and second embodiments is also referred to as the electrode 313.

[0235] The sensor element 31 includes an electrode 313 disposed on a substrate 311, and an odorant receptor layer 315 formed on the electrode 313. The shape of the odorant receptor layer 315 is circular or strip-shaped. When the shape of the odorant receptor layer 315 is circular, the diameter R of the circle may be greater than or equal to 0.2 mm and less than or equal to 10 mm. When the shape of the odorant receptor layer 315 is strip-shaped, the width W of the short side of the strip may be greater than or equal to 0.2 mm and less than or equal to 10 mm. Here, the strip-shaped refers to a plane shape mainly having a short side as width and a long side as length. When the shape of the odorant receptor layer 315 is circular, the diameter R of the circle is preferably greater than or equal to 1.5 mm and less than or equal to 2.7 mm. When the shape of the odorant receptor layer 315 is strip-shaped, the width W of the short side of the strip is preferably greater than or equal to 1.5 mm and less than or equal to 2.7 mm.

[0236] When the circle diameter R or the short side width W of the odorant receptor layers 315, 315b to 315d of the sensor elements 31, 31b to 31d included in the sensor element group 31A is within the above range, the odor measurement device 100c can stably perform measurement corresponding to the odorant.

[0237] When the diameter R of the odorant receptor layer 315 is smaller than 0.2 mm or the short side width W is smaller than 0.2 mm, the area for receiving the odorant is small, and the odor measuring device 100c cannot perform stable measurement.

[0238] In addition, when the diameter R of the odorant receptor layer 315 is larger than 10 mm or the short side width W is larger than 10 mm, the area of ​​a single sensor element is large, and it is necessary to increase the size of the sensor cavity 60 including the sensor element group 31A. If the size of the sensor cavity 60 is too large, it is difficult to uniformly diffuse the first gas containing the odorant into the sensor cavity 60, and the odor measuring device 100c cannot perform stable measurement.

[0239] Fig.13 31A is a top view of an example structure of a sensor element 31c included in the sensor element group 31A. The sensor element 31c includes electrodes 313 (first electrode 313C, second electrode 313D) arranged on a substrate 311, and a circular odorant receptor layer 315c formed on the electrode 313. The diameter R of the odorant receptor layer 315c is not less than 0.2 mm and not more than 10 mm. Fig.13 In the embodiment, as an example, the shape of the odorant receptor layer 315c provided in the sensor element 31c is an ellipse, but the present invention is not limited thereto. When the shape of the odorant receptor layer 315c is an ellipse, the average value of the short diameter and the long diameter may be greater than or equal to 0.2 mm and less than or equal to 10 mm. In addition, the shape of the odorant receptor layer 315c may be a perfect circle.

[0240] Fig.14 31 is a top view of an example of the structure of a sensor element 31d included in the sensor element group 31A. The sensor element 31d includes electrodes 313 (first electrode 313C, second electrode 313D) arranged on a substrate 311, and a strip-shaped odorant receptor layer 315d formed on the electrodes 313. The short side width of the odorant receptor layer 315d is not less than 0.2 mm and not more than 10 mm.

[0241] By having the above-described structure, the odor measurement device 100c can reduce the instability of the measurement result output caused by the variation in the shape and area of ​​the odor substance receptor layer of each sensor element, thereby being able to measure the odor substance with high accuracy.

[0242] The sensor element group 31A may include a plurality of sensor elements other than the sensor elements 31 and 31b to 31d. Fig. 9 In FIG. 5 , as an example, the sensor element group 31A is composed of 16 sensor elements, but the number of sensor elements is not limited to this.

[0243] The odorant receptor layers 315 , 315 b to 315 d included in the plurality of sensor elements 31 , 31 b to 31 d included in the sensor element group 31A may each contain a conductive carbon material, a resin composition, and a surfactant.

[0244] The content ratios of the conductive carbon material, the resin composition, and the surfactant may be different between the odorant receptor layers 315, 315b to 315d of the plurality of sensor elements 31, 31b to 31d included in the sensor element group 31A. When the content ratios of the conductive carbon material, the resin composition, and the surfactant included in the odorant receptor layer are different, the sensitivity and detection specificity of the sensor element to the odorant are also different.

[0245] As described above, the odor measurement device 100c includes a plurality of sensor elements having odor substance receptor layers that are different in the content ratios of the conductive carbon material, the resin composition, and the surfactant, and can detect a variety of odor substances.

[0246] The thickness of the odorant receptor layers 315, 315b to 315d of the sensor elements 31, 31b to 31d included in the odor measurement device 100c of this embodiment may be 0.1 μm to 1000 μm. The thickness of each odorant receptor layer may also be preferably 1 μm to 100 μm.

[0247] When the thickness of the odorant receptor layer of the sensor elements 31, 31b to 31d is within the above range, the output instability of the measurement result caused by the uneven thickness of the odorant receptor layer 315, 315b to 315d of each sensor element can be reduced, so that the odor measurement device 100c can measure the odorant with high accuracy.

[0248] If the thickness of the odorant receptor layer 315, 315b to 315d is less than 0.1 μm, it means that the value of the thickness is close to the particle size of the conductive carbon material dispersed in the odorant receptor layer, but this may not ensure the uniformity of the thickness of the odorant receptor layer, and the odor measuring device 100c may not be able to output stable measurement results. On the other hand, if the thickness of the odorant receptor layer 315, 315b to 315d is greater than 1000 μm, the diffusion time of the odorant in the odorant receptor layer becomes longer, and it is difficult for the odor measuring device 100c to measure the odorant with high accuracy.

[0249] When the thickness of the odorant receptor layers 315, 315b to 315d of the sensor elements 31, 31b to 31d is within the above range, the output instability of the measurement results caused by the uneven thickness of the odorant receptor layers of each sensor element can be reduced, and the odor measurement device 100c can measure the odorant with high accuracy.

[0250] The electrodes of the sensor elements 31, 31b to 31d included in the sensor element group 31A may each have a first electrode and a second electrode, and the first electrode and the second electrode may also be arranged in parallel lines, parallel curves, combs, or concentric circles. Regardless of the shapes of the first electrode and the second electrode, they are preferably arranged in line symmetry or point symmetry with each other. By configuring the first electrode and the second electrode in this way, the odor measurement device 100c can measure the odor substances contained in the gas with high accuracy.

[0251] Fig.13 The sensor element 31c has a first electrode 313C and a second electrode 313D. In addition, as an example, the first electrode 313C is composed of a metal wiring 313a and a metal wiring 313b, and the two metal wirings are arranged in a T-shape in a manner perpendicular to each other. Similar to the first electrode 313C, the second electrode 313B is also composed of two metal wirings 313c and 313d, and the two metal wirings are arranged in a T-shape in a manner perpendicular to each other. In addition, the first electrode 313A and the second electrode 313B are arranged in parallel lines in a manner that the metal wiring 313a and the metal wiring 313c are opposite to each other.

[0252] In particular, by configuring the first electrode 313C and the second electrode 313D to be opposite to each other in a T-shape, the first electrode 313C and the second electrode 313D can be set at an appropriate distance, thereby stabilizing the resistance value of the electrode. For example, when the electrodes are configured in a comb shape, the distance between the electrodes is short, so the resistance value of the electrode may become too small. In addition, by configuring the first electrode 313C and the second electrode 313D to be opposite to each other in a T-shape, there are no concave and convex parts of the electrode that may hinder the casting in the slurry casting area involved in the coating process of the sensor element manufacturing method described later, so the slurry is easy to cast. In addition, since the slurry is easy to cast, it has the effect of making the thickness of the odorant receptor layer constant after drying.

[0253] [Method for manufacturing sensor element]

[0254] The following is a method for manufacturing the various sensor elements 31, 31b to 31d used in the odor measurement device 100c. As the raw material of the odorant receptor layer 315, 315b to 315d of the sensor elements 31, 31b to 31d, slurries having various components can be used. Here, the viscosity of the slurry varies depending on the slurry component. In the case where the odorant receptor layer is formed by applying slurries of different viscosities in the same method, for example, if a low-viscosity slurry is used, it is easy to cast on the substrate, while on the other hand, if a high-viscosity slurry is used, it is difficult to cast on the substrate. In this way, when applying slurries of different viscosities in the same manufacturing method, the shape, area, thickness, etc. of the odorant receptor layer 315, 315b to 315d after drying will be uneven. It is difficult for the sensor elements 31, 31b to 31d manufactured using such an odorant receptor layer to stably measure the odorant. On the other hand, if the manufacturing method is changed according to the viscosity of the slurry, the shape, area, thickness, etc. are less likely to vary and a uniform odorant receptor layer 315, 315b to 315d can be obtained, but the manufacturing cost will increase.

[0255] The manufacturing method of this embodiment can manufacture a variety of sensor elements 31, 31b to 31d with less variation in shape, area and thickness even when using slurries of different compositions or viscosities. In addition, there is no need to change the manufacturing method depending on the viscosity, so the manufacturing cost can be reduced.

[0256] Fig.15 This is a process flow diagram for explaining a method for manufacturing various sensor elements 31, 31b to 31d used in the odor measurement device 100c. Here, a method for manufacturing sensor elements 31, 31b to 31d having an odorant receptor layer 315, 315b to 315d containing a surfactant is described as an example.

[0257] <Slurry Preparation Process>

[0258] First, a slurry containing a filler, a resin composition and a surfactant is prepared. The resin composition in the slurry contains a T unit (R 1 SiO 3 / 2 ) and D unit (R 1 2SiO 2 / 2 ) is a silicone resin. The mixing ratio of the filler, the resin composition and the surfactant can be appropriately set according to the sensitivity and detection specificity required for the odorant receptor layer. In addition to the filler, the resin composition and the surfactant, the slurry can also contain a solvent and an additive (S21).

[0259] <Electrode Arrangement Process>

[0260] Next, electrodes are arranged on the substrate (S22). The electrodes may include a first electrode (first metal wiring) and a second electrode (second metal wiring). The first electrode and the second electrode are spaced apart from each other. The first electrode and the second electrode may be arranged in parallel straight lines, parallel curves, combs, or concentric circles. In addition, regardless of the shapes of the first electrode and the second electrode, they are preferably arranged in line symmetry or point symmetry with each other. By arranging the first electrode and the second electrode in this way, the odor measuring device 100c can measure the odor substances contained in the gas with high accuracy.

[0261] Fig.13 and Fig.14 In the embodiment, as an example, one set of electrodes (the first electrode 313C and the second electrode 313D) is arranged on one substrate 311, but a plurality of sets of electrodes may be arranged side by side on one substrate.

[0262] <Area Delimitation Process>

[0263] Next, a coating area for coating each of the plurality of slurries is defined on the substrate provided with electrodes (S23). The coating area is an area that includes at least a portion of the first metal wiring and at least a portion of the second metal wiring. The coating area can be defined, for example, by providing a barrier agent. In addition, if the slurry is dripped from a nozzle during the coating process, the coating area can also be defined based on the nozzle diameter. Fig.16 3 is a schematic diagram of a substrate 311 after disposing a barrier agent M. The barrier agent M is disposed so as to define a coating region 330. The coating region 330 is a state where the substrate 311 is exposed.

[0264] The area of ​​the coating region 330 may be defined as the same size for each of the plurality of slurries. That is, even if the mixing ratios of the conductive carbon material, the resin composition, and the surfactant in each slurry are different, the area of ​​the coating region 330 to which the slurry is applied may be uniform. Thus, even if a plurality of slurries having different mixing ratios, i.e., different viscosities, are used, the area of ​​the plurality of odorant receptor layers after drying is less uneven.

[0265] Although Fig.16 The coating area 330 is circular as an example, but the shape of the coating area 330 is not limited thereto. The shape of the coating area 330 may also be circular or strip-shaped. Thus, a circular or strip-shaped odorant receptor layer can be formed.

[0266] When the coating area 330 is circular, the diameter of the circle may be greater than 0.2 mm and less than 10 mm. When the coating area 330 is strip-shaped, the short side length of the strip may be greater than 0.2 mm and less than 10 mm. Thus, a circular odorant receptor layer having a circle diameter of greater than 0.2 mm and less than 10 mm may be formed, and a circular odorant receptor layer having a strip-shaped short side length of greater than 0.2 mm and less than 10 mm may also be formed.

[0267] The configuration method of the barrier agent M is not particularly limited, and the following methods may be cited: screen printing the solder resist to a specified area and then curing the solder resist by UV; attaching a barrier agent film to a substrate; curing the barrier agent only in a specified area and then removing the uncured portion.

[0268] <Coating process>

[0269] Next, each of the plurality of slurries is applied to the coating region 330 (S24). Here, the slurry is applied to the coating region 330 that includes at least a portion of the first electrode and at least a portion of the second electrode. The slurry can be applied by a conventionally known method, such as dripping from a nozzle, spraying, or spin coating.

[0270] The viscosity of various slurries is different. The reason why the viscosity of each slurry is different is that, for example, the mixing ratio of the conductive carbon material, the resin composition and the surfactant is different. Slurries of different viscosities may have differences in casting behavior. However, in the coating process of this manufacturing method, since the coating area has been defined by the previous area definition process, the slurry will be coated within the specified area.

[0271] <Drying process>

[0272] Finally, the slurry applied to the coating area 330 is dried to form an odorant receptor layer (S25). The drying method of the slurry is not particularly limited, and for example, the slurry may be dried by heating at 100°C for 1 hour under normal pressure and then heated at 100°C for 1 hour under reduced pressure in a vacuum dryer.

[0273] In the drying process, the thickness of the odorant receptor layer after drying may be 0.1 μm or more and 1000 μm or less. The thickness of the odorant receptor layer after drying is preferably 1 μm or more and 100 μm or less. If the thickness of the odorant receptor layer is within this range, the sensor element can stably measure the odorant. If the thickness of the odorant receptor layer is less than 0.1 μm, it means that the value of the thickness is close to the particle size of the conductive carbon material dispersed in the odorant receptor layer, but this may not ensure the uniformity of the thickness of the odorant receptor layer, and the odor measuring device 100c may not be able to output a stable measurement result. On the other hand, if the thickness of the odorant receptor layer is greater than 1000 μm, the diffusion time of the odorant in the odorant receptor layer becomes longer, and it is difficult for the odor measuring device 100c to measure the odorant with high accuracy.

[0274] As described above, the manufacturing method of this embodiment includes a slurry preparation step, an electrode configuration step, an area definition step, a coating step, and a drying step. By adopting such a manufacturing method, even if a plurality of slurries having different mixing ratios of conductive carbon material, resin composition, and surfactant are used, a plurality of sensor elements 31, 31b to 31d with less unevenness in shape, area, and thickness of the odorant receptor layer 315, 315b to 315d can be manufactured. In addition, since there is no need to change the manufacturing method depending on the viscosity of the slurry, the manufacturing cost can be suppressed.

[0275] In particular, since the coating area is defined by the area definition process, the casting of the slurry droplets in the subsequent coating process is good. For example, when the coating area is defined by a barrier agent, the barrier agent-exposed portion and the barrier agent-free portion on the substrate have different surface roughnesses. The barrier agent-free portion has a large surface roughness and a small surface tension because the substrate is exposed. As a result, the casting of the slurry droplets in the exposed coating area of ​​the substrate is good.

[0276] In addition, since the coating area is configured by the area defining step, the casting of the slurry can be restricted in the subsequent coating step, so that the relative position relationship between the odorant receptor layer 315, 315b~315d and the electrode is constant. For example, when the coating area is defined by a barrier, there is a height difference at the boundary of the barrier, so the casting of the slurry is restricted, so that the relative position relationship between the odorant receptor layer 315, 315b~315d and the electrode is constant.

[0277] The region defining step is not essential, and the coating step may be performed without defining regions.

[0278] Regarding the production of the odorant receptor layers 315, 315b to 315d, after the odorant receptor layers 315, 315b to 315d are produced by coating the resin composition, electrodes in contact with the odorant receptor layers may be produced.

[0279] In the present disclosure, the slurry comprises a filler and a T unit (R 1 SiO 3 / 2 ) and D unit (R 1 2SiO 2 / 2 ) is used, so that the slurry has appropriate flexibility and has an effect of excellent film-forming properties. In addition, since the film-forming properties are improved, a plurality of sensor elements 31, 31b to 31d can be stably manufactured.

[0280] 〔Software-based implementation example〕

[0281] The control block (particularly the control unit 1 ) of the estimation devices 10 , 10 a , 10 b may be realized by a logic circuit (hardware) formed in an integrated circuit (IC chip) or the like, or may be realized by software.

[0282] When implemented by software, the estimation devices 10, 10a, and 10b include a computer that executes the commands of the software, i.e., the program, for implementing each function. The computer includes, for example, one or more processors and a computer-readable recording medium storing the program. In addition, in the computer, the processor reads the program from the recording medium and executes it, thereby achieving the purpose of the present invention. As the processor, for example, a CPU (Central Processing Unit) can be used. As the recording medium, not only "non-temporary tangible media" such as ROM (Read Only Memory) can be used, but also a storage tape, a storage disk, a memory card, a semiconductor memory, a programmable logic circuit, etc. can be used. In addition, a RAM (Random Access Memory) for developing the program can also be provided. In addition, the program can also be provided to the computer through any transmission medium (communication network and broadcast wave, etc.) that can transmit the program. Here, even if the form of the program is a data signal carried in a carrier wave that is embodied by electronic transmission, one aspect of the present invention can be achieved.

[0283] In addition, part or all of the functions of each control block can also be realized by a logic circuit. For example, an integrated circuit having a logic circuit that functions as each control block is also included in the scope of the present invention. In addition, the functions of each control block can also be realized by a quantum computer, for example.

[0284] In addition, each process described in the above embodiments may also be executed by AI (Artificial Intelligence). In this case, AI may be executed in the control device or in other devices (such as edge computers or cloud servers).

[0285] 〔Summarize〕

[0286] The odor measuring device 100, 100a to 100c of the first embodiment of the present invention comprises a plurality of sensor elements 31, 31b to 31d, wherein the plurality of sensor elements 31, 31b to 31d comprises an electrode 313 and an odor substance receptor layer 315, 315b to 315d, wherein the electrode 313 comprises a first metal wiring 313A and a second metal wiring 313B separated from the first metal wiring 313A, and the odor substance receptor layer 315, 315b to 315d is in contact with at least a portion of the first metal wiring 313A and at least a portion of the second metal wiring 313B, and the odor substance receptor layer 315, 315b to 315d comprises a resin composition, wherein the resin composition comprises a filler and a T unit (R 1 SiO 3 / 2 ) and D unit (R 1 2SiO 2 / 2 ) composed of an organic silicone resin, R 1 It is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0287] In the odor measurement devices 100, 100a to 100c of aspect 2 of the present invention based on aspect 1, the porosity x of the odorant receptor layer evaluated based on the cross-sectional SEM image of the odorant receptor layer may be 12%≤x≤30%.

[0288] In the odor measurement device 100, 100a to 100c of the third aspect of the present invention based on the first or second aspect, the resin composition may further contain a surfactant.

[0289] In the odor measuring device 100, 100a to 100c of aspect 4 of the present invention based on any one of aspects 1 to 3, the weight ratio of the T unit to the D unit of the silicone resin may be: T unit:D unit = 98:2 to 50:50.

[0290] The odor measurement device 100, 100a to 100c according to the fifth aspect of the present invention based on any one of the first to fourth aspects can also detect odor based on the change in the resistance value of the odor substance receptor layer.

[0291] In the odor measurement device 100, 100a to 100c according to aspect 6 of the present invention based on any one of aspects 1 to 5, the filler may be a conductive carbon material.

[0292] In the odor measurement devices 100, 100a to 100c according to the seventh aspect of the present invention based on the sixth aspect, the conductive carbon material may be carbon black.

[0293] The sensor element 31, 31b to 31d of aspect 8 of the present invention comprises an electrode 313 and an odorant receptor layer 315, 315b, wherein the electrode 313 comprises a first metal wiring 313A and a second metal wiring 313B separated from the first metal wiring 313A, the odorant receptor layer 315, 315b is in contact with at least a portion of the first metal wiring 313A and at least a portion of the second metal wiring 313B, and the odorant receptor layer 315, 315b comprises a filler and a T unit (R 1 SiO 3 / 2 ) and D unit (R 1 2SiO 2 / 2 ) of silicone resin, R 1 It is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0294] In the sensor elements 31, 31b to 31d of aspect 9 of the present invention based on aspect 8, the porosity x of the odorant receptor layer evaluated based on the cross-sectional SEM image of the odorant receptor layer may be 12%≤x≤30%.

[0295] The manufacturing method of the sensor element 31, 31b~31d of the embodiment 10 of the present invention includes: a slurry preparation step of preparing slurry; an electrode configuration step of configuring an electrode 313 having a first metal wiring 313A and a second metal wiring 313B separated from the first metal wiring 313A on a substrate; a coating step of coating the slurry on a coating area that includes at least a portion of the first metal wiring 313A and at least a portion of the second metal wiring 313B; and a drying step of drying the slurry coated on the coating area to form an odorant receptor layer 315, 315b~315d, wherein the slurry includes a filler and a T unit (R 1 SiO 3 / 2 ) and D unit (R 1 2SiO 2 / 2 ) composed of an organic silicone resin, R 1 It is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0296] In the method for manufacturing the sensor element 31, 31b to 31d according to aspect 10 of the present invention based on aspect 9, the porosity x of the odorant receptor layer evaluated based on the cross-sectional SEM image of the odorant receptor layer may be 12%≤x≤30%.

[0297] In the production method according to aspect 12 of the present invention based on aspect 10 or 11, the slurry may further contain a surfactant.

[0298] In the production method of aspect 13 of the present invention based on any one of aspects 10 to 12, the weight ratio of T unit to D unit in the silicone resin may be: T unit:D unit=98:2 to 50:50.

[0299] The present invention is not limited to the above-mentioned embodiments, and various modifications can be made within the scope of the technical concept of the present disclosure. Embodiments obtained by appropriately combining the technical means disclosed in the different embodiments are also included in the technical scope of the present invention.

[0300] According to the aspects of the present invention, it is possible to mechanically measure odor with high accuracy and high sensitivity. Therefore, the present invention can be widely used in various industrial fields requiring odor measurement, and can be expected to contribute to the 9th goal of the Sustainable Development Goals (SDGs) related to the foundation of industrial innovation and technological innovation.

[0301] <Example>

[0302] The present invention will be further described below by way of Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, "%" means % by weight, and "part" means part by weight unless otherwise specified.

[0303] The description of various materials used in Examples and Comparative Examples is as follows.

[0304] 〔Resin (A)〕

[0305] Silicone resin

[0306] The silicone resin mentioned here does not include silicone oil.

[0307] A1: 57.6 parts by weight of DOWSIL (registered trademark) RSN-0217 Flake Resin (manufactured by Dow Toray Co., Ltd.) and 14.4 parts by weight of DOWSIL (registered trademark) RSN-0255 Flake Resin (manufactured by Dow Toray Co., Ltd.) (the two silicone resins are mixed in a weight ratio of 4:1);

[0308] A2: 28.8 parts by weight of DOWSIL (registered trademark) RSN-0217 Flake Resin (manufactured by Dow Toray Co., Ltd.) and 43.2 parts by weight of DOWSIL (registered trademark) RSN-0255 Flake Resin (manufactured by Dow Toray Co., Ltd.) (the two silicone resins are mixed in a weight ratio of 2:3);

[0309] A3: DOWSIL (registered trademark) RSN-0255 Flake Resin (manufactured by Dow Toray Co., Ltd.);

[0310] A4: DOWSIL (registered trademark) RSN-0409HS Resin (manufactured by Dow Toray Co., Ltd.);

[0311] A5: 72 parts by weight of DOWSIL (registered trademark) RSN-0217 Flake Resin (manufactured by Dow Toray Co., Ltd.);

[0312] A6: Silicone resin

[0313] [Synthesis Example of Silicone Resin (A6)]

[0314] In a 500 mL flask, 18 g of water, 2 g of 28% ammonia water, and 80 g of 2-propanol were placed, and then 4.41 g of 3-furyltriethoxysilane was added, and the mixture was reacted at 80°C for 3 hours. After the reaction solution was air-cooled, the precipitate (containing the inorganic-organic hybrid solution) was filtered out by separation. The sample was thoroughly washed with ethanol and dried, and then dissolved in DMF to 10 mg / mL. A 2-propanol dispersion IPA-ST-ZL (Nissan Chemical Co., Ltd.) containing silica with an average primary particle size of 80 nm was prepared into a 10 mg / mL filler-containing solution with DMF, and the filler-containing solution was mixed with the inorganic-organic hybrid solution at a mixing ratio of 6:4 (containing the inorganic-organic hybrid solution: containing the filler solution) to obtain the target silicone solution. In addition, a portion of the silicone solution was used as a sample, and after drying it in an atmosphere at 100°C, its thermal weight loss rate was measured by the TGA method.

[0315] Silicone oil

[0316] A7: KF-351A (manufactured by Shin-Etsu Chemical Co., Ltd.) 18 parts by weight;

[0317] A8: KF-6002A (manufactured by Shin-Etsu Chemical Co., Ltd.) 18 parts by weight;

[0318] 〔Surfactant (B)〕

[0319] B1: Polyvinylpyrrolidone (PVP; manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)

[0320] B2: Amine salt of polyether phosphate (DISPARLON DA-325; manufactured by Kusumoto Chemicals Co., Ltd.)

[0321] 〔Packing (C)〕

[0322] C1: Silica (IPA-ST-ZL; manufactured by Nissan Chemical Co., Ltd.)

[0323] C2: Carbon black (SuperC65; manufactured by MTI Corporation)

[0324] C3: Carbon nanotube (VGCF-H; manufactured by Showa Denko K.K.)

[0325] [Solvent (D)]

[0326] D1: Butyl Butyrate

[0327] Examples and comparative examples of the resin composition are described below.

[0328] [Resin composition 1]

[0329] The following components were weighed in the following amounts into a sample bottle and mixed to obtain a mixture.

[0330] Silicone resin A1: 80 parts by weight

[0331] Filler C1: 20 parts by weight

[0332] Solvent D1: 400 parts by weight

[0333] The mixture was stirred at 2000 rpm for 20 minutes using a planetary mixer (ARE-310 manufactured by THINKY CORPORATION) to obtain slurry. The slurry obtained in this way was referred to as resin composition 1.

[0334] [Resin composition 2]

[0335] Resin composition 2 was prepared in the same manner as in resin composition 1 except that filler C2 was used instead of filler C1.

[0336] [Resin composition 3]

[0337] Resin composition 3 was prepared in the same manner as resin composition 1 except that the amount of resin A was changed to 72 parts by weight and 8 parts by weight of surfactant B1 was added as a surfactant.

[0338] [Resin composition 4]

[0339] Resin composition 4 was prepared in the same manner as resin composition 3 except that resin A was changed to 72 parts by weight, 8 parts by weight of surfactant B2 was added as a surfactant, and filler C2 was used instead of filler C1.

[0340] [Resin composition 5]

[0341] Resin composition 5 was prepared in the same manner as in resin composition 4 except that silicone resin A2 having a weight ratio of T unit:D unit of 97:3 was used instead of silicone resin A1.

[0342] [Resin composition 6]

[0343] Resin composition 6 was prepared in the same manner as resin composition 4 except that silicone resin A3 having a weight ratio of T unit:D unit of 95:5 was used.

[0344] [Resin composition 7]

[0345] Resin composition 7 was prepared in the same manner as resin composition 4 except that silicone resin A4 having a weight ratio of T unit:D unit of 40:60 was used.

[0346] [Resin composition 8]

[0347] Resin composition 8 was prepared in the same manner as in resin composition 6 except that filler C3 was used instead of filler C2.

[0348] [Resin composition 9]

[0349] Resin composition 9 was prepared in the same manner as resin composition 6 except that the amount of resin A was changed to 54 parts by weight and 18 parts by weight of silicone oil A7 was added.

[0350] [Resin composition 10]

[0351] Resin composition 10 was prepared in the same manner as in resin composition 9 except that silicone oil A8 was used instead of silicone oil A7.

[0352] [Resin composition c1]

[0353] Resin composition c1 was prepared in the same manner as in resin composition 2 except that silicone resin A5 having a weight ratio of T unit:D unit of 100:0 was used instead of silicone resin A1.

[0354] [Resin composition c2]

[0355] Resin composition c2 was prepared in the same manner as resin composition 1 except that 60 parts by weight of silicone resin A6 having a weight ratio of T unit:D unit of 100:0 was used instead of silicone resin A1 and the amount of filler C1 was changed to 40 parts by weight.

[0356] Examples and comparative examples of the sensor element are described below.

[0357] [Sensor elements E1 to E12, comparative sensor elements E'-1, E'-2]

[0358] A package substrate including a group of two metal wirings was cut out from a package substrate (ICB-073; manufactured by Sunhayato Co., Ltd.) having a plurality of metal wirings at a pitch of 500 μm. Each of the cut package substrates was further cut so that the length of the metal wiring became 3.5 cm.

[0359] The cut package substrate was adhered to the glass plate with the metal wiring facing upward using double-sided tape. In addition, the excess portion of the metal wiring was masked using plastic tape so that the length of the exposed portion of the metal wiring was 3.0 cm. In this state, resin compositions 1 to 10 were applied to the exposed portion of the metal wiring using a rod coater (No. 4). After coating, the resin compositions were dried for 3 hours using a circulating air dryer at an air temperature of 100°C. After drying, the resin compositions were cooled to room temperature, and then the metal wiring having an odorant receptor layer was peeled off from the glass plate to obtain sensor elements (E-1) to (E-12) and comparative sensor elements (E'-1) and (E'-2). Regarding sensor elements (E-1) and (E-2), both were prepared using resin composition 1.

[0360] [Examples 1 to 12, Comparative Examples 1 and 2]

[0361] A housing having an inlet, a carrier gas inlet portion, and an airflow adjuster is manufactured, wherein the inlet is used to introduce the object to be measured (odor substance), and the carrier gas inlet portion and the airflow adjuster are used to form an airflow that allows the object to be measured to be evenly diffused. A lead wire for connecting the wiring terminal to the outside of the housing is welded to each of the eight sensor elements (E-1), and then the eight sensor elements (E-1) are set in the housing. For each sensor element (E-1), a 1mA constant current power supply and a voltmeter for measuring the voltage applied to the two terminals of the lead wire are connected to the end of the lead wire placed outside the housing. In this way, an odor sensor 1 having eight sensor elements (E-1) is formed.

[0362] The odor sensors 2 to 12, c1, and c2 were constructed in the same manner as the odor sensor 1, except that the sensor elements (E-2) to (E-12) and the comparative sensor elements (E'-1) and (E'-2) were used instead of the sensor element (E-1). The odor sensors 1, 4, and the odor sensor c2 used a membrane-type surface stress sensor (MSS) method, and the electromotive force from the sensor element was amplified by an amplifier using a SD-MSS sensor probe (manufactured by NIMS), thereby obtaining the output voltage of the odor sensors 1, 4, and the odor sensor c2. The odor sensors 2 and 5 used a quartz crystal microbalance (QCM) method, and the resonant frequency was measured by a frequency counter using a QA-A9M-AU (manufactured by Seiko EG&G), thereby obtaining the frequency change of the odor sensors 2 and 5.

[0363] 〔evaluate〕

[0364] [Determination of coefficient of variation ΔV]

[0365] For each of the odor sensors 1 to 12, c1, and c2, 5 mL of ethanol as the object to be measured was placed at the inlet of the odor sensor. Then, nitrogen as a carrier gas was made to flow from the carrier gas inlet to the housing provided with the sensor element at a flow rate of 1 L / min through the airflow adjuster, and then discharged to the outside. During this period, the measured value of the voltmeter connected to the sensor element was recorded by a computer. In this way, the voltage value of each of the 8 sensor elements in the odor sensor was measured. For each sensor element in each odor sensor, the maximum difference ΔV between the output voltage V0 before the introduction of the object to be measured and the voltage V during the introduction of the object to be measured was calculated. Then, the standard deviation σ and the average value μ of the 8 maximum difference ΔV data obtained from each odor sensor were calculated, and the ΔV variation coefficient (i.e., σ / μ) of the resin composition used to form the sensor element was obtained. For odor sensors 1, 4, and odor sensor c2, the output voltages V0 and V obtained from the MSS sensor element were obtained. As for the odor sensors 2 and 5, since the frequencies F0 and F obtained from the QCM sensor element are obtained, the calculation is performed using the frequencies F0 and F in the same manner as when V0 and V are used to obtain the coefficient of variation.

[0366] [Porosity Measurement Method]

[0367] The cross section of the sensor element provided in each of the odor sensors 1 to 12, c1, and c2, including the odor substance receptor layer and the odor substance transmission layer, was photographed and observed using a scanning electron microscope (SEM). The SEM observation conditions are as follows.

[0368] Manufacturer: HITACHI

[0369] Device: S-4800

[0370] Acceleration voltage: 1.0V

[0371] Current value: 10μA

[0372] When acquiring the SEM image, the image was adjusted within the range of contrast 3225 to 3275 and brightness 2025 to 2075 using the built-in application of the device.

[0373] The SEM images obtained by SEM were binarized using image analysis software. ImageJ software was used for the binarization. The binarization was performed in the order of "Gaussian Blur", "16bit", and "unsharp Mask", and then binarized using "threshold". The threshold value during the binarization was set to 50 grayscale to extract the area corresponding to the void in the SEM image, and then the ratio of the void area to the odorant receptor layer imaging area in the SEM image, that is, the odorant receptor layer void ratio, was calculated.

[0374] Table 1 shows the material components and physical properties of the resin compositions of the odor sensors 1 to 12 of Examples 1 to 12 and the odor sensors c1 and c2 of Comparative Examples 1 and 2.

[0375] [Table 1]

[0376]

[0377] In Table 1, "T unit: D unit" refers to the weight ratio between T unit and D unit. When the ΔV variation coefficient is 0.2 or less, preferably 0.15 or less, and more preferably 0.1 or less, the performance variation between the multiple sensor elements in a single odor sensor is sufficiently small, and it can be determined that there is no problem in practical use. From the viewpoint of reducing the performance variation, the smaller the ΔV variation coefficient, the more preferable it is.

[0378] 〔Comment〕

[0379] As shown in Table 1, all of the odor sensors 1 to 12 exhibited a ΔV variation coefficient that was not problematic in practical use or was preferable in practical use.

[0380] As shown in Table 1, the porosity x of odor sensors 4 to 9 evaluated based on the cross-sectional SEM image of the odor substance receptor layer is in the range of 12%≤x≤30%, and odor sensors 4 to 9 all exhibit a practically acceptable or practically preferred ΔV variation coefficient.

[0381] Comparison between Examples 1 to 12 and Comparative Examples 1 and 2 shows that the silicone resin in the resin compositions c1 and c2 included in the odor sensors c1 and c2 consists only of T units, so that the ΔV variation coefficients of the odor sensors c1 and c2 are large.

[0382] Comparison between Example 3 and Example 6 shows that a ΔV variation coefficient that is not a problem in practical use can be obtained regardless of whether the surfactant (B) is included or not. The odor sensor 6 of Example 6 exhibits a smaller ΔV variation coefficient because its resin composition 4 contains the surfactant (B).

[0383] According to the comparison between Examples 6 to 9, even if the weight ratio of the T unit:D unit of the silicone resin is different, a ΔV variation coefficient that is not a problem in practical use can be obtained. In particular, the weight ratio of the T unit:D unit of the silicone resin A3 included in the odor sensor 8 is T unit:D unit=95:5, so that the ΔV variation coefficient of the odor sensor 8 shows the minimum value.

[0384] A comparison between Examples 8, 11, and 12 shows that a ΔV variation coefficient that does not pose a practical problem can be obtained regardless of the presence or absence of silicone oil and even if the types of silicone oil are different.

[0385] From the comparison between Examples 1 and 2, and the comparison between Examples 4 and 5, it can be seen that even if the sensor types are different, a ΔV variation coefficient that does not cause any practical problems can be obtained.

[0386] From the comparison between Examples 8 and 10, it can be seen that even if the types of filler (C) are different, a ΔV variation coefficient that does not cause any practical problems can be obtained.

[0387] It can be seen that the filler and the T unit (R 1 SiO 3 / 2 ) and D unit (R 1 2SiO 2 / 2 ) can show a ΔV variation coefficient that is not a problem in practical use. That is, an odor measurement device equipped with such an odor sensor can output stable measurement results.

[0388] <Industrial Applicability>

[0389] The present invention can be effectively used as a medical odor recognition sensor, a gas detection odor recognition sensor, an agricultural odor recognition sensor, and other industrial and daily odor recognition sensors. For example, farmers can also use the odor recognition sensor to determine the maturity of fragrant crops, thereby managing the best harvest time. In addition, the odor recognition sensor can also be used to digitize the odor of products such as food or cosmetics to provide support for improving the efficiency of product development and stabilizing quality.

[0390] <Description of Reference Numerals>

[0391] 10, 10a, 10bS estimation device

[0392] 11 Measurement value acquisition unit (acquisition unit)

[0393] 12Change Pattern Analysis Department (Analysis Department)

[0394] 16 Presumption

[0395] 30, 30b Odor sensor

[0396] 31, 31b, 31c, 31d sensor element

[0397] 32, 32b constant current source (power supply)

[0398] 33, 33b Voltmeter (measuring equipment)

[0399] 100, 100a, 100b, 100c odor measuring device

[0400] 313 Metal wiring (electrode)

[0401] 313A No. 1 Metal Wiring

[0402] 313B Second Metal Wiring

[0403] 315, 315b Odor substance receptor layer

[0404] 313C 1st electrode

[0405] 313D 2nd electrode

[0406] 330 coating area

Claims

1. An odor measuring device comprising a plurality of sensor elements, the plurality of sensor elements comprising an electrode and an odor substance receptor layer, the electrode having a first metal wiring and a second metal wiring separated from the first metal wiring, the odor substance receptor layer being in contact with at least a portion of the first metal wiring and at least a portion of the second metal wiring, in, The odor substance receptor layer comprises a resin composition, The resin composition comprises a filler and R as a T unit. 1 SiO 3 / 2 and R as D unit 1 2SiO 2 / 2 The silicone resin composed of The R 1 It is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

2. The odor measuring device according to claim 1, wherein: The porosity x of the odorant receptor layer evaluated based on a cross-sectional SEM image of the odorant receptor layer is: 12%≤x≤30%.

3. The odor measuring device according to claim 1 or 2, wherein: The resin composition further includes a surfactant.

4. The odor measuring device according to any one of claims 1 to 3, wherein: The weight ratio of the T unit to the D unit of the silicone resin is: T unit:D unit=98:2-50:

50.

5. The odor measuring device according to any one of claims 1 to 4, wherein: The odor measuring device detects odor through the change in the resistance value of the odor substance receptor layer.

6. The odor measuring device according to any one of claims 1 to 5, wherein: The filler is a conductive carbon material.

7. The odor measuring device according to claim 6, wherein: The conductive carbon material is carbon black.

8. A sensor element comprising an electrode and an odorant receptor layer, wherein the electrode has a first metal wiring and a second metal wiring separated from the first metal wiring, and the odorant receptor layer is in contact with at least a portion of the first metal wiring and at least a portion of the second metal wiring, in, The odor substance receptor layer comprises a filler and R as a T unit. 1 SiO 3 / 2 and R as D unit 1 2SiO 2 / 2 The silicone resin composed of The R 1 It is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

9. The sensor element according to claim 8, wherein: The porosity x of the odorant receptor layer evaluated based on a cross-sectional SEM image of the odorant receptor layer is: 12%≤x≤30%.

10. A method for manufacturing a sensor element, comprising: A slurry preparation step, preparing slurry; An electrode configuration step of configuring an electrode having a first metal wiring and a second metal wiring separated from the first metal wiring on a substrate; A coating step of coating the slurry to a coating region that includes at least a portion of the first metal wiring and at least a portion of the second metal wiring; as well as a drying step of drying the slurry applied to the applied area to form an odorant receptor layer, in, The slurry comprises a filler and R as a T unit. 1 SiO 3 / 2 and R as D unit 1 2SiO 2 / 2 The silicone resin composed of The R 1 It is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

11. The sensor element according to claim 10, wherein: The porosity x of the odorant receptor layer evaluated based on a cross-sectional SEM image of the odorant receptor layer is: 12%≤x≤30%.

12. The manufacturing method according to claim 10 or 11, wherein: The slurry also includes a surfactant.

13. The manufacturing method according to any one of claims 10 to 12, wherein: The weight ratio of the T unit to the D unit of the silicone resin is: T unit:D unit=98:2~50:50.

Images