Odor measuring device, sensor element, and manufacturing method thereof

Abstract

To provide a smell measuring device, a sensor element, and a method for manufacturing the devices which can output a stable measurement result.SOLUTION: The smell measuring device includes: a plurality of sensor elements (31) having an electrode (313) with a first metal wire (313A) and a second metal wire (313B) and a smell material reception layer (315) in contact with at least part of the first metal wire (313A) and part of the second metal wire (313B). The smell material reception layer (315) includes a resin composition and the resin composition includes a resin containing silicone resin made of a T unit (R1SiO3 / 2), a filler, and a surface active surfactant. R1 denotes a univalent hydrocarbon group with 1-10 carbon atoms.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to an odor measuring device, a sensor element, and a method for manufacturing the same. [Background technology]

[0002] With the recent development of information processing technology, if it were possible to quantify the sense of smell, which is one of the five human senses that cannot be fully measured mechanically, it is expected that it could be used in a wide range of industrial fields. For example, in the medical field, it would be possible to use it in nursing care and assistance, preventive diagnosis and disease testing, in the environmental field, odor management in factories, fermentation process management and wastewater treatment management in the field of biogas utilization, in the safety field, it would be possible to detect signs of landslides and floods, and to detect deterioration of engine oil and machine oil. In the food field, it could be used to detect the aging state of ingredients such as plants and meat, for example, process management of fermented foods such as alcoholic beverages, plant cultivation management, and quality control during the production, storage, and distribution of food, and in the marketing field, it could be used to produce cosmetics, body odor, fragrance environment, and the scent of commercial materials. Up until now, methods for detecting specific gaseous substances (gases) have been achieved with high accuracy and sensitivity using semiconductor gas sensors. Sensors with different response characteristics to various odors have been reported, and the composition of the receptors contained in the sensors has also been studied.

[0003] The invention described in Patent Document 1 proposes a mechanism for detecting the adsorption of odor substances 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 is possible to detect odor substances that are easily thermally decomposed and substances that do not cause an oxidation-reduction reaction on the surface of the detection part of the sensor.

[0004] Patent Document 2 also focuses on the property that the electrical resistance of a mixture of an organic polymer and a conductive material changes when exposed to an organic gas. Patent Document 2 describes that when a plurality of combinations of organic polymer / conductive material in which the organic polymer composition is different from that of the above mixture is prepared and these are used as an electrical resistance array in a sensor, the electrical resistance changes when exposed to the same organic gas are different for each combination. Patent Document 2 reports that this can be used to identify odors by attributing the pattern of electrical resistance changes to the type of odor (= organic gas mixture).

[0005] Furthermore, Patent Document 3 reports that the response speed of the sensor is improved by adding a plasticizer to the above organic polymer.

[0006] In Patent Document 4, RSiO 3 / 2 A sensor is disclosed having a receptor that includes a filler exhibiting a particular structure and a particular average primary particle size. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 11-23508 [Patent Document 2] Special Publication No. 11-503231 [Patent Document 3] Special Publication No. 2002-519633 [Patent Document 4] Patent Publication No. 2022-26253 Summary of the Invention [Problem to be solved by the invention]

[0008] If the performance of the sensor element applied to an odor measuring device changes with each production and is not stable, odor measuring devices with a predetermined detection accuracy cannot be stably produced. Furthermore, when replacing the sensor element of an odor measuring device with a new sensor element, it is desirable that there is little or no difference in performance between the original sensor element and the replaced sensor element.

[0009] An object of one aspect of the present invention is to provide an odor measuring device, a sensor element, and a manufacturing method thereof that can output stable measurement results. [Means for solving the problem]

[0010] As a result of investigations aimed at achieving the above object, the present inventors arrived at the present invention.

[0011] That is, an odor measuring device according to one embodiment of the present invention includes a plurality of sensor elements each including an electrode having a first metal wiring and a second metal wiring spaced apart from the first metal wiring, and an odorant receiving layer in contact with at least a portion of the first metal wiring and at least a portion of the second metal wiring, the odorant receiving layer including a resin composition, and the resin composition including a T unit (R 1 SiO 3 / 2 The silicone resin composition comprises a silicone resin, a filler, and a surfactant, 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0012] A sensor element according to one aspect of the present invention includes an electrode having a first metal wiring and a second metal wiring spaced apart from the first metal wiring, and an odorant receiving layer in contact with at least a portion of the first metal wiring and at least a portion of the second metal wiring, the odorant receiving layer including a T unit (R 1 SiO 3 / 2 The silicone resin composition comprises a silicone resin, a filler, and a surfactant, 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0013] A method for manufacturing a sensor element according to one aspect of the present invention includes a slurry preparation step of preparing a slurry, an electrode arrangement step of arranging an electrode having a first metal wiring and a second metal wiring spaced apart from the first metal wiring on a substrate, a coating step of coating the slurry on a coating region including at least a part of the first metal wiring and at least a part of the second metal wiring, and a drying step of drying the slurry coated on the coating region to form an odorant receiving layer, the slurry being a T unit (R 1 SiO 3 / 2 The silicone resin composition comprises a silicone resin, a filler, and a surfactant, 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms. Effect of the Invention

[0014] According to one aspect of the present invention, an object is to provide an odor measuring device, a sensor element, and a manufacturing method thereof that can output stable measurement results. [Brief description of the drawings]

[0015] [Figure 1] 1 is a schematic diagram showing an example of the configuration of an odor measurement device according to one embodiment of the present invention. [Diagram 2] FIG. 2 is a top view showing an example of the configuration of a sensor element. [Diagram 3] 3 is a cross-sectional view showing an example of the configuration of the sensor element shown in FIG. 2. [Figure 4] 1 is a functional block diagram showing an example of the configuration of an odor measurement device. [Diagram 5] 11 is a flowchart showing an example of a process flow in which the estimation device generates an estimation model. [Figure 6] 1 is a functional block diagram showing an example of the configuration of an odor measurement device. [Figure 7] 11 is a flowchart showing an example of a process flow in which the estimation device estimates an odor substance. [Figure 8] FIG. 2 is a block diagram showing an example of the configuration of an odor measuring device according to another embodiment of the present invention. [Figure 9]10 is a schematic diagram showing an example of the configuration of an odor measuring device according to another embodiment of the present invention. FIG. [Figure 10] FIG. 4 is a top view showing an example of the configuration of a sensor chamber. [Figure 11] FIG. 4 is a cross-sectional view showing an example of the configuration of a sensor chamber. [Figure 12] FIG. 4 is a cross-sectional view showing an example of the configuration of a sensor chamber. [Figure 13] FIG. 2 is a top view showing an example of the configuration of a sensor element of the present invention. [Figure 14] FIG. 2 is a top view showing an example of the configuration of a sensor element of the present invention. [Figure 15] 1 is a flowchart illustrating an example of a flow of a method for manufacturing a sensor element. [Figure 16] FIG. 2 is a top view illustrating an example of a substrate before slurry is applied thereto. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] [Embodiment 1] An embodiment of the present invention will be described below. Unless otherwise specified in this specification, "A to B" expressing a numerical range means "A or more and B or less".

[0017] In this specification, "odor substance" means a substance that can be adsorbed to an odor substance receiving layer in a broad sense. Therefore, it also includes substances that are not generally considered to be the cause of odor. "Odor" often contains multiple odor substances that cause it, and there are also substances that are not recognized as odor substances or unknown odor substances. One embodiment of the present invention focuses on the fact that the amount of odor substance adsorbed to the odor substance receiving layer differs depending on the type of odor substance.

[0018] In addition, even when the term "odor substance" is simply used in this specification, it may mean a "collection of odor substances" that may contain multiple odor substances, rather than an individual odor substance.

[0019] Examples of "odor substances" include, but are not limited to, hexane, ethyl acetate, methanol, diethyl carbonate, toluene, d-limonene, bornan-2-one, cis-3-hexenol, β-phenylethyl alcohol, citral, L-carvone, γ-undecalactone, eugenol, linalyl acetate, menthol, benzaldehyde, vanillin, hexanal, ethanol, pentyl valerate, linalool, and 2-propanol.

[0020] [1. Resin composition] The resin composition according to one embodiment of the present invention is a resin composition for forming an odorant receiving layer, which comprises a T unit (R 1 SiO 3 / 2 The resin composition includes a resin (A) containing a silicone resin consisting of a silicone resin formed of a compound represented by the general formula (I), a filler (C), and a surfactant (B). The resin composition may be a composition in which these components are uniformly present.

[0021] <Resin (A)> Resin (A) may have a film-forming property capable of forming an odorant receiving layer, and preferably exhibits an interaction such as adsorption or dissolution with a specific odorant. In addition, resin (A) preferably has appropriate physical properties (such as heat resistance) and chemical properties (such as compatibility with sample gas and corrosion resistance) according to the use conditions of the odor sensor described later.

[0022] Resin (A) is a T unit (R 1 SiO 3 / 2 The resin (A) may be a mixture of a silicone resin composed of T units and other silicone resins.

[0023] (Silicone resin) Silicone resins include monofunctional M units in which three organic groups are bonded to Si, difunctional D units in which two organic groups are bonded to Si, trifunctional T units in which one organic group is bonded to Si, and tetrafunctional Q units in which no organic groups are bonded. The silicone resin contained in resin (A) is a T unit (R 1 SiO 3 / 2 ), R1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms. In particular, the silicone resin of the present disclosure has a main chain including T units (R 1 SiO 3 / 2 In the present disclosure, a silicone cross-linked material that is solid at normal temperature and normal pressure (for example, normal temperature is 25±15° C. and normal pressure is 1013 hPa) is referred to as a “silicone resin.”

[0024] The hydrocarbon group may be either an aliphatic group or 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 either a straight chain or a branched chain.

[0025] Examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups.

[0026] Examples of the aryl group include a phenyl group, a toluyl group, and a dimethylphenyl group.

[0027] Examples of the aralkyl group include a benzyl group, a phenylethyl group, a phenylpropyl group, and a phenylbutyl group.

[0028] Resin (A) may contain other components besides silicone resin. Examples of other resins that may be contained in resin (A) include silicone oil. In the present disclosure, silicone oil has fluidity at room temperature and normal pressure (for example, room temperature is 25±15°C, normal pressure is 1013hPa), and is a chain of siloxane bonds. Silicone resin can form a three-dimensional crosslinked structure consisting of siloxane bonds by a crosslinking reaction, whereas silicone oil cannot form the above crosslinked structure. Silicone oil can be blended into the resin composition from the viewpoint of increasing the dispersibility of filler (C) in the resin composition or from the viewpoint of increasing the coatability of the resin composition. In particular, silicone oil is preferably a silicone oil whose main chain excluding the terminal group is composed only of D units. As the modified portion possessed by silicone oil, there is no particular limitation on the type of functional group or other blocked modified portion, and the modified portion may be in the form of, for example, a side chain type, both terminal type, one terminal type, or both terminal type of side chain. The modified moieties include amino groups, amines, epoxy groups, carbinol groups, mercapto groups, carboxyl groups, methylhydrogens, methacryl groups, acrylic groups, phenyl groups, phenol groups, silanol groups, carboxylic anhydrides, vinyl groups, etc. Other modified moieties include polyester moieties, polyether moieties, alkyl moieties, aralkyl moieties, fluoroalkyl moieties, higher fatty acid ester moieties, higher fatty amide moieties, etc. In the following description, the term "silicone resin" will be explained taking the case where it does not contain silicone oil as an example.

[0029] In the present disclosure, the silicone resin is preferably contained in an amount of 30 to 100% by weight, more preferably 50 to 100% by weight, based on the total amount of resin (A). By containing the silicone resin in the amount described above based on the total amount of resin (A), the resin composition has suitable flexibility and high film-forming properties. This allows the odorant receiving layer 315 to stably adsorb odorants.

[0030] <Surfactant (B)> The surfactant (B) acts as a dispersant for the filler (C) described below. The surfactant (B) can also improve the applicability of the resin composition when the sensor element is formed by applying the resin composition. The surfactant (B) can be appropriately selected from known surfactants within the range in which the above-mentioned action is exerted.

[0031] Examples of the surfactant (B) include anionic surfactants, cationic surfactants, amphoteric surfactants and nonionic surfactants.

[0032] 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.

[0033] Examples of the carboxylic acid having 10 to 24 carbon atoms include decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, pentadecanoic acid, nonadecanoic acid, icosanoic acid, henicosanoic acid, docosanoic acid, tricosanoic acid, and tetracosanoic acid.

[0034] Examples of the alkyl group contained in the alkylsulfonic acid having 14 to 24 carbon atoms include a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group, a docosyl group, a tricosyl group, and a tetracosyl group.

[0035] Examples of the alkali metal contained in the alkali metal salt include sodium and potassium.

[0036] Examples of the cationic surfactant include halide salts of quaternary ammonium having an alkyl group having 12 to 24 carbon atoms.

[0037] Examples of the quaternary ammonium having an alkyl group having 12 to 24 carbon atoms include tetrapropylammonium, tetrabutylammonium, tetrapentylammonium, tetrahexylammonium, dimethyldioctylammonium, didecyldimethylammonium, decyltrimethylammonium, dodecyltrimethylammonium, tridecyltrimethylammonium, hexadecyltrimethylammonium, methyltrioctylammonium, octyltrimethylammonium, tributylmethylammonium, octadecyltrimethylammonium, tetradecyltrimethylammonium, nonadecyltrimethylammonium, icosyltrimethylammonium, henicosyltrimethylammonium, heptadecyltrimethylammonium, and pentadecyltrimethylammonium.

[0038] The halide salts include, for example, fluoride salts, chloride salts, bromide salts, and iodide salts.

[0039] Examples of amphoteric surfactants include dimethyl(3-sulfopropyl)ammonium inner salts having an alkyl group with 10 to 22 carbon atoms, and N-alkyl-N,N-dimethylglycines having an alkyl group with 10 to 22 carbon atoms.

[0040] Examples of dimethyl(3-sulfopropyl)ammonium hydroxide inner salts having an alkyl group having 10 to 22 carbon atoms include decyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, undecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, dodecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, tridecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, tetradecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, pentadecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, Examples of such ammonium hydroxide inner salt include hexadecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, heptadecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, octadecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, nonadecyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, icosyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, henicosyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt, and docosyldimethyl(3-sulfopropyl)ammonium hydroxide inner salt.

[0041] Examples of N-alkyl-N,N-dimethylglycines having an alkyl group having 10 to 22 carbon atoms include N-dodecyl-N,N-dimethylglycine and N-octadecyl-N,N-dimethylglycine.

[0042] Examples of nonionic surfactants include higher alcohol ethylene oxide adducts, etc. Examples of commercially available nonionic surfactants include AJISPER PB-822 (manufactured by Ajinomoto Fine-Techno Co., Ltd.) and polyvinylpyrrolidone (manufactured by Nippon Shokubai Co., Ltd.).

[0043] Examples of higher alcohols include 1-hexyl alcohol, 1-heptyl alcohol, 1-octyl alcohol, 1-nonyl alcohol, 1-decyl alcohol, 1-undecyl alcohol, 1-dodecyl alcohol, 1-tridecyl alcohol, 1-tetradecyl alcohol, 1-pentadecyl alcohol, 1-hexadecyl alcohol, 1-heptadecyl alcohol, 1-octadecyl alcohol, and sorbitan.

[0044] From the viewpoint of odor discrimination performance, the number of moles of ethylene oxide added is preferably 5 to 50, more preferably 5 to 40, and further preferably 5 to 30. For example, the number of moles of ethylene oxide added in IONET S-60V is 20.

[0045] From the viewpoint of dispersibility in the filler (C), the surfactant (B) preferably contains an ether structure, and among the ether structures, it is preferable that the surfactant (B) contains an AOA (alkylene oxide adduct) chain. An example of a surfactant containing an ether structure is IONET S-60V (manufactured by Sanyo Chemical Industries, Ltd.). Also, examples of surfactants containing an AOA chain are Disparlon DA-325 (manufactured by Kusumoto Chemical Industries, Ltd.) and IONET T-80V (manufactured by Sanyo Chemical Industries, Ltd.). Also, from the viewpoint of dispersibility in the filler (C), the surfactant (B) preferably has at least one of an amide group, a primary amino group, a secondary amino group, and a tertiary amino group. Also, from the viewpoint of dispersibility in the filler (C), the surfactant (B) preferably has at least one of an oxyethylene chain, an oxypropylene chain, and an oxyethylene-oxypropylene random structure or block structure. The random structure of oxyethylene-oxypropylene is a chain structure in which both oxyethylene and oxypropylene are randomly linked, while the block structure of oxyethylene-oxypropylene is a chain structure in which oxyethylene blocks formed by linking oxyethylenes and oxypropylene blocks formed by linking oxypropylenes are linked.

[0046] <Filler (C)> The filler (C) is preferably a conductive filler, for example, a metal filler such as nickel, gold, or copper, or a conductive carbon material, more preferably a conductive carbon material. A conductive carbon material is preferably used from the viewpoint of dispersibility of the filler in the resin composition. In this specification, the conductive carbon material means a carbon material having a volume resistivity of 0.1 Ω·cm or less. The above-mentioned resin composition is in a state in which the filler (C) is dispersed in a mixture of the resin (A) and the surfactant (B). The fillers (C) come into contact with each other to form a conductive path, which makes the resin composition conductive.

[0047] Examples of the conductive carbon material include carbon black, carbon nanotubes, graphene, etc. Carbon black is particularly preferred as the conductive carbon material.

[0048] Commercially available carbon black products include Ketjenblack EC (product name of Akzo, Netherlands), Ketjenblack EC-300J (product name of Lion Specialty Chemicals Co., Ltd.), Ketjenblack EC-600JD (product name of Lion Specialty Chemicals Co., Ltd.), Seast G116, 116 (product names of Tokai Carbon Co., Ltd.), Niteron #10 (product name of Nippon Steel Chemical Co., Ltd.), Denka Black (product name of Denki Kagaku Kogyo Kabushiki Kaisha), and SUPER C-65 (product name of MTI Corporation, USA).

[0049] Commercially available carbon nanotubes include VGCF-H (product name manufactured by Showa Denko KK).

[0050] Commercially available graphene products include those manufactured by Sigma-Aldrich.

[0051] The conductive carbon material is preferably in the form of fibers or spheres.

[0052] In the case of 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.

[0053] When it is spherical, the primary particle size is preferably 10 nm to 200 nm, and more preferably 20 nm to 150 nm.

[0054] In addition, the conductive carbon material preferably has a primary particle diameter of 100 nm or less from the viewpoint of conductivity in the resin composition and sensor sensitivity. The particle diameter of the conductive carbon material can be determined by a known method. For example, the particle diameter of the conductive carbon material can be measured by observing with a transmission electron microscope (TEM) and analyzing the image using an image processing device (for example, a digital microscope VHX-700F manufactured by Keyence). When the conductive carbon material is a known or commercially available product, the particle diameter may be a literature value or a catalog value.

[0055] The filler (C) may also be silica fine particles. In this case, the silica fine particles preferably have a primary particle diameter of 200 nm or less from the viewpoint of electrical conductivity in the resin composition and sensor sensitivity. The particle diameter of the silica fine particles can be determined by a known method. The particle diameter of the silica fine particles can be determined, for example, from a transmission electron microscope image as described above. When the silica fine particles are known or commercially available, the particle diameter may be a literature value or a catalog value.

[0056] <Composition of Resin Composition> The weight ratio of the resin (A) to the surfactant (B) in the resin composition [(A) / (B)] is preferably 1.0 to 50.0 from the viewpoint of the coating stability of the resin composition and the stability of the filler (C) in the resin composition. From the viewpoint of the stability of the filler (C) in the resin composition, the weight ratio (A) / (B) is more preferably more than 4.0, more preferably 4.5 or more, and more preferably 5.0 or more. From the viewpoint of the coating stability of the resin composition, the weight ratio (A) / (B) is more preferably 40.0 or less, and more preferably 30.0 or less.

[0057] The content of the filler (C) in the resin composition is preferably 5 to 30% by weight based on the total of 100% by weight of the resin (A), the surfactant (B) and the filler (C), from the viewpoint of the sensor element formed from the resin composition exhibiting sufficient conductivity as an odor sensor and sufficient sensitivity as the odor sensor. The content of the filler (C) based on the total of 100% by weight of the resin (A), the surfactant (B) and the filler (C) is more preferably 6% by weight or more, more preferably 7% by weight or more, from the viewpoint of further increasing the above-mentioned conductivity. Moreover, the content of the filler (C) based on the total of 100% by weight of the resin (A), the surfactant (B) and the filler (C) is more preferably 29% by weight or less, from the viewpoint of further increasing the above-mentioned sensitivity.

[0058] <Optional ingredients> The resin composition may further contain other components other than the above-mentioned resin (A), surfactant (B) and filler (C) within the range in which the effects of the present invention can be obtained. Examples of other components include a solvent (D). The other components can be suitably used within the range in which both the effects of the present invention and the effects of the other components can be obtained.

[0059] The solvent (D) can be added to the resin composition from the viewpoint of increasing the compatibility between the resin (A) and the surfactant (B), increasing the dispersibility of the filler (C) in the resin composition, or increasing the coatability of the resin composition. Examples of the solvent (D) include N-methyl-2-pyrrolidone, propylene glycol monomethyl ether acetate, ethyl butyrate, butyl butyrate, ethyl acetate, N,N-dimethylformamide, N,N-dimethylacetamide, toluene, and xylene.

[0060] The content of the solvent (D) in the resin composition can be appropriately determined from the above viewpoints. For example, from the viewpoint of coatability, the content of the solvent (D) in the resin composition is preferably 5 to 50 parts by weight per 100 parts by weight of the total of the resin (A), the surfactant (B), the filler (C), and the solvent (D).

[0061] <Method for producing resin composition> The resin composition is obtained as a slurry by mixing the resin (A), the surfactant (B), the filler (C), and, if necessary, the solvent (D) and kneading them uniformly with a stirrer. When the solvent (D) is added, the solvent (D) is distilled off from the resin composition. The solvent (D) may be distilled off from the resin composition produced by uniformly mixing, or may be distilled off from the coating film produced during the production of the sensor element described below.

[0062] <Main effects> In the above-mentioned resin composition, the electrical conductivity of the resin composition varies depending on the amount of odorant adsorbed in the resin composition. In addition, the adsorption process of the odorant to the above-mentioned resin composition differs for each odorant. For this reason, by forming a detection part to which the odorant can be adsorbed with the resin composition, it is possible to use it in a sensor element of an odor sensor. By using the resin composition, it is possible to improve the odor discrimination performance. For example, it is possible to discriminate a real odor pattern in which multiple substances interact with each other or a real odor pattern caused by a substance whose composition is unknown. In addition, the resin composition has excellent composition stability and coating stability of the resin composition. Therefore, the stability of the odor discrimination performance when used in a sensor element is improved.

[0063] It is believed that the sensor described in the cited document 1 can detect odors consisting of single compounds. On the other hand, many odors are mixtures of multiple substances. The sensor described in the cited document 1 does not have a function to distinguish the odor components in the detection unit, so the odor discrimination performance for mixtures is insufficient. In the cited document 2, it is shown that it is possible to recognize odors as mixtures by making the response of the detection unit to various compounds different through each conductive polymer by utilizing the difference in the chemical structure of the conductive polymer used in the detection unit. However, the chemical structure of the conductive polymer is limited, and it is difficult to separate the response of the detection unit to any odor substance with high sensitivity, and it is difficult to distinguish between odors consisting of similar components. In the cited document 3, a method is proposed in which a mixture consisting of an organic polymer, a plasticizer, and a conductive substance is used as a detection material in the detection unit, and the penetration of the odor substance into the organic polymer is detected as a change in the electrical resistance of the mixture. By utilizing the fact that the odor substances that penetrate are different when organic polymers of different compositions are used, it is possible to recognize odors as mixtures by using multiple detection units consisting of the above detection material containing organic polymers of different compositions in parallel to form an array. However, in the case of the above organic polymers and organic polymers containing plasticizers, even if multiple combinations of organic polymers and conductive materials are prepared, the difference in chemical properties between the organic polymers is small, so the odor discrimination performance is insufficient. These conventional techniques cannot accurately detect, for example, real odor patterns in which multiple substances interact with each other or real odor patterns caused by substances with unknown compositions.

[0064] [2. Sensor element 31] The above-mentioned resin composition exhibits different changes in electrical conductivity over time when odorant A is adsorbed to the resin composition and when odorant B, which is different from odorant A, is adsorbed to the resin composition. By utilizing this property, a sensor element 31 capable of detecting and identifying odorants can be realized.

[0065] The outline and effects of a sensor element 31 to which a resin composition according to one embodiment of the present invention is applied will be described below.

[0066] The sensor element 31 includes an odorant receiving layer 315 containing the above-mentioned resin composition, a first metal wiring 313A, and a second metal wiring 313B. In the following description, when there is no need to distinguish between the first metal wiring 313A and the second metal wiring 313B, they may be referred to as metal wiring 313.

[0067] In this specification, the term "odorant receiving layer" refers to a layer that adsorbs the odorant to be recognized. The odorant receiving layer is formed from the above-mentioned resin composition. The odorant receiving layer may be provided as a part of the sensor element according to an embodiment of the present invention.

[0068] Here, the first metal wiring 313A and the second metal wiring 313B will be described with reference to Fig. 2 and Fig. 3. Fig. 2 is a top view showing an example of the configuration of sensor element 31, and Fig. 3 is a cross-sectional view showing an example of the configuration of sensor element 31 shown in Fig. 2.

[0069] The first metal wiring 313A and the second metal wiring 313B are metal wirings that function as electrodes for measuring changes in the electrical conductivity of the odorant receiving layer 315 (i.e., the resin composition). That is, the first metal wiring 313A and the second metal wiring 313B are spaced apart from each other, and the odorant receiving layer 315 is in contact with at least a portion of the first metal wiring and at least a portion of the second metal wiring. In one example, the first metal wiring 313A and the second metal wiring 313B are metal wirings that are not in direct contact with each other, and may be metal wirings that are approximately parallel to each other, as shown in FIG. 2.

[0070] As shown in FIG. 2, the metal wiring 313 including the first metal wiring 313A and the second metal wiring 313B may be disposed on the substrate 311. The substrate 311 may be a substrate such as glass epoxy generally used for electronic circuits. The metal wiring 313 may be a metal wiring such as copper or gold. The thickness of each of the first metal wiring 313A and the second metal wiring 313B as viewed from a direction perpendicular to the substrate surface is preferably 10 μm to 2 mm, more preferably 10 μm to 1 mm. The height, i.e., thickness, of each of the first metal wiring 313A and the second metal wiring 313B as viewed from a direction parallel to the substrate surface is preferably 1 μm to 100 μm, more preferably 10 μm to 50 μm. The interval between the first metal wiring 313A and the second metal wiring 313B is preferably 1 μm to 1 mm, more preferably 1 μm to 100 μm. The length of the metal wiring 313 is preferably 10 μm to 50 mm, and more preferably 10 μm to 30 mm.

[0071] The metal wiring 313 may be disposed on a seal substrate 312. FIG. 3 shows the AA cross section of FIG. 2. As shown in FIG. 3, the seal substrate 312 may be disposed on a substrate 311 such as glass epoxy, and the metal wiring 313 may be disposed on the seal substrate 312. A vinyl tape 314 may be used to fix the seal substrate 312 on the substrate 311. The vinyl tape 314 may also be used to adjust the length of the exposed portion of the metal wiring 313 by masking the excess portion of the metal wiring 313. Here, the exposed portion of the metal wiring 313 is the portion where the metal wiring 313 and the odorant receiving layer 315 contact each other. The vinyl tape 314 may also be an insulator for adjusting the length of the portion where the metal wiring 313 and the odorant receiving layer 315 contact each other.

[0072] The odorant receiving layer 315 may be in contact with at least a portion of the first metal wiring 313A and at least a portion of the second metal wiring 313B. The odorant receiving layer 315 may be arranged to fill the area between the first metal wiring 313A and the second metal wiring 313B, as shown in Figures 2 and 3, for example.

[0073] When the electrical conductivity of the odorant receiving layer 315 (ie, the electrical conductivity of the sensor element 31) is low, it is desirable that the distance between the first metal wiring 313A and the second metal wiring 313B be a predetermined distance (eg, 500 μm) or less.

[0074] The sensor element 31 is capable of detecting and identifying various odorous substances by applying a resin composition that exhibits different changes in electrical conductivity over time when odorous substance A is adsorbed and when odorous substance B, which is different from odorous substance A, is adsorbed.

[0075] The sensor element 31 may be a resistive element, a membrane-type surface stress sensor (MSS) type element, or a quartz crystal microbalance (QCM) type element. The measurement results of both the membrane-type surface stress sensor (MSS) type element and the quartz crystal microbalance (QCM) type element tend to vary due to slight differences in the amount of film material on the electrode or unevenness in thickness, and the variations in each manufacturing lot of the sensor element tend to be large. In addition, since the structure of the stress sensing part such as the cantilever is delicate in the membrane-type surface stress sensor (MSS) type element, there is a problem that if a large amount of slurry is applied at once to form a thick film, the stress sensing part is damaged and the yield is reduced. On the other hand, the resistive type element has relatively few of these problems, and from these points of view, it is preferable to use a resistive type element as the sensor element in the present invention.

[0076] <Method of manufacturing sensor element> The sensor element 31 can be manufactured by preparing the odorant receiving layer 315 using the resin composition according to the embodiment of the present invention described above. The odorant receiving layer 315 can be prepared by applying the aforementioned resin composition as a coating liquid and solidifying or curing the formed coating film. The application of the resin composition can be carried out using a known coating technique.

[0077] [3. Odor Sensor 30] The outline and effects of an odor sensor 30 employing a sensor element 31 will be described below with reference to Fig. 1. Fig. 1 is a schematic diagram showing an example of the configuration of an odor measuring device 100 including an odor sensor 30 employing a sensor element 31. Note that in the sensor element 31 shown in Fig. 1, the vinyl tape 314 is omitted for simplification.

[0078] The odor sensor 30 includes a sensor element 31 that detects an odor substance, a constant current source 32 (power supply), and a voltmeter 33 (measuring device).

[0079] The first metal wiring 313A and the second metal wiring 313B of the sensor element 31 are connected by a lead wire W. An example in which a constant current source 32 and a voltmeter 33 are provided on the lead wire W is shown in FIG.

[0080] 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.

[0081] The voltmeter 33 measures the potential difference generated between the first metal wiring 313A and the second metal wiring 313B when a constant current supplied from the constant current source 32 is supplied to the odorant receiving layer 315.

[0082] Although not a required component, the odor sensor 30 may further include a housing 34. The housing 34 is a container capable of containing air containing an odor substance. When the odor sensor 30 includes the housing 34, the sensor element 31 is disposed within the housing 34.

[0083] The housing 34 has an inlet 341 for introducing an odorant and an outlet 342 for discharging air containing the odorant. The odorant may be introduced by inserting filter paper P or the like soaked in the odorant into the housing 34 from the inlet 341, or by inserting air containing the odorant into the housing 34 from the inlet 341. The housing 34 is a container for containing air containing the odorant at a predetermined concentration (e.g., 200 ppm) or more.

[0084] Although not essential, an airflow generating fan 35 may be provided at the exhaust port 342 of the housing 34. The airflow generating fan 35 is for generating an airflow inside the housing 34 and discharging the gas inside the housing 34 from the exhaust port 342 to the outside of the housing 34.

[0085] The odor sensor 30 may include a constant voltage source (power supply) (not shown) instead of the constant current source 32, and an ammeter (measuring device) (not shown) instead of the voltmeter 33. In this case, the constant voltage source functions as a power supply for supplying power to the sensor element 31, and applies a constant voltage to the sensor element 31 via the lead wires. Meanwhile, the ammeter measures the value of the current flowing between the first metal wiring 313A and the second metal wiring 313B when a constant voltage is applied to the odorant receiving layer 315.

[0086] The odor sensor 30 outputs a measurement value that indicates the change over time in the electrical conductivity of the sensor element 31 before and after an odor substance is adsorbed to the sensor element 31. This makes it possible to detect and identify various odor substances.

[0087] [4. Odor measuring device 100] The odor sensor 30 described above can output the change over time in the electrical conductivity of the sensor element 31 for each odor substance when various odor substances are adsorbed to the sensor element 31. By applying this odor sensor 30, it is possible to compare the change over time in the electrical conductivity of the sensor element 31 when odor substance A is adsorbed to the sensor element 31 with the change over time in the electrical conductivity of the sensor element 31 when odor substance B is adsorbed to the sensor element 31. Based on such a comparison result, it is possible to realize an odor measurement device 100 that can estimate the odor substance adsorbed to the sensor element 31.

[0088] Furthermore, the odor measuring device 100 can estimate odor substances with high accuracy by using the estimation model 22 generated by machine learning. The estimation model 22 can be generated using learning data including a combination of measurement values ​​measured when each of a plurality of odor substances is adsorbed to at least one sensor element 31, and identification information unique to the odor substance that provided the measurement value.

[0089] The following describes the outline and effects of an odor measuring device 100 that uses the odor sensor 30. The odor measuring device 100 is a device that estimates the odor substance adsorbed to a sensor element 31 based on a change in electrical conductivity that occurs in the sensor element 31 to which the above-mentioned resin composition is applied.

[0090] First, the configuration of an odor measurement device 100 according to one embodiment of the present invention will be described with reference to Fig. 1. Fig. 1 is a block diagram showing an example of the configuration of the odor measurement device 100.

[0091] As shown in FIG. 1, the odor measurement device 100 includes an estimation device 10 and an odor sensor 30.

[0092] <Estimation device 10> The estimation device 10 is a device that estimates an odor substance detected by an 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 communicatively connected to the odor sensor 30. Specifically, the estimation device 10 performs estimation of an odor substance by analyzing a measurement value acquired from the odor sensor 30. The configuration of the estimation device 10 will be described later.

[0093] (Generation of estimated model 22) Next, the configuration of the odor measuring device 100 that performs the process of generating the estimation model 22 used to estimate odor substances, and the process of generating the estimation model 22 will be described with reference to FIGS. 4 and 5. FIG.

[0094] The estimation model 22 is generated by machine learning using learning data including a combination of measurement values ​​measured by the voltmeter 33 when each of a plurality of odor substances is adsorbed to at least one sensor element, and identification information specific to the odor substance that gave the measurement value. Here, the identification information specific to the odor substance may be, for example, the name, CAS number, and chemical formula of the odor substance.

[0095] (Configuration of the Estimation Device 10 (Generation of Estimation Model 22)) Fig. 4 is a functional block diagram showing an example of the configuration of the odor measuring device 100. For ease of explanation, the same reference numerals are given to members having the same functions as those explained in Fig. 1, and the explanation thereof will not be repeated.

[0096] As shown in FIG. 4, the estimation device 10 includes an input unit 15, a control unit 1, and a storage unit 2.

[0097] The input unit 15 is for accepting various input operations from a user, and may be, for example, a keyboard, a mouse, a touch panel, or the like.

[0098] The control unit 1 includes a measurement value acquiring unit 11 (acquiring unit), a change pattern analyzing unit 12 (analyzing unit), a learning control unit 13, and an estimation model generating unit .

[0099] The measurement value acquiring unit 11 acquires a measurement value from the voltmeter 33. The measurement value acquiring unit 11 also uses the acquired measurement value to calculate a value indicating the electrical conductivity of the sensor element 31 (e.g., resistance value, impedance, etc.). In the present disclosure, it is preferable that the measurement value acquiring unit 11 calculates a change in the resistance value of the odorant receiving layer. The measurement value acquiring unit 11 may acquire a measurement value from the voltmeter 33 at a predetermined time interval (e.g., 0.1 second interval).

[0100] The change pattern analysis unit 12 analyzes the change over time in the electrical conductivity of at least one sensor element 31. Using the resistance value calculated by the measurement value acquisition unit 11, the change pattern analysis unit 12 calculates a value indicating the amount of change in the electrical conductivity of the sensor element 31 due to the adsorption of an odorant. The change pattern analysis unit 12 generates data indicating a change pattern indicating the time change in the calculated amount of change in electrical conductivity. When the generated change pattern is a known odorant, the change pattern analysis unit 12 may store the generated change pattern in the change pattern database 21 (learning data) in association with identification information specific to the known odorant.

[0101] The learning control unit 13 reads out the change pattern database 21 from the storage unit 2 and controls the generation of the estimation model 22 by machine learning. Here, the change pattern database 21 is a database that includes combinations of measurement values ​​measured when multiple odor substances are adsorbed to the sensor element 31 and identification information unique to the known odor substances that provided the measurement values. The learning control unit 13 inputs the change pattern read out 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 according to the comparison result to the estimation model generation unit 14.

[0102] The estimation model generation unit 14 generates the estimation model 22 by a machine learning algorithm using the change patterns stored in the change pattern database 21. The estimation model generation unit 14 may be configured to generate the estimation model 22 by using a known supervised machine learning algorithm. Examples of machine learning algorithms that can be applied to the estimation model generation unit 14 include the k-nearest neighbor method, logistic regression, support vector machine, random forest, and neural network.

[0103] (Process for generating estimation model 22) Specific processes performed by each part of the control unit 1 will be described below with reference to Fig. 5. Fig. 5 is a flowchart showing an example of the flow of processes performed by the estimation device 10 to generate the estimation model 22.

[0104] First, the measurement value acquiring unit 11 acquires the voltage value V0 measured by the odor sensor 30 before the filter paper P soaked in the odor substance is inserted into the housing 34, and calculates the resistance value R0 (step S11). The resistance value R0 is preferably 200 to 10,000 Ω, more preferably 250 to 3,000 Ω, and most preferably 300 to 1,000 Ω.

[0105] Meanwhile, the input unit 15 accepts input of the name of a known odor substance that has been soaked into the filter paper P inserted in the housing 34 (step S12). The process of step S12 may be performed before step S11.

[0106] Next, the measurement value acquiring unit 11 acquires the voltage value V measured by the odor sensor 30 immediately after the filter paper P soaked with the known odor substance is inserted into the housing 34, and calculates the resistance value R (step S13).

[0107] Next, the change pattern analysis unit 12 calculates R / R0 using the resistance value R0 and the resistance value R (step S14). R / R0 is a value indicating the amount of change in electrical conductivity of the sensor element 31 due to the adsorption of a known odorant. The change pattern analysis unit 12 may calculate R-R0 instead of R / R0. The change pattern analysis unit 12 stores the change pattern of R / R0 over time in the change pattern database 21 in association with the name of the input known odorant (step S15).

[0108] If no change pattern has been stored for a given type of existing odor substance (NO in step S16), that is, if there is still insufficient data to use for machine learning, the process returns to step S11.

[0109] If a change pattern is stored for a predetermined type of existing odor substance (YES in step S16), the learning control unit 13 reads out the change pattern for the known odor substance stored in the change pattern database 21 and inputs it to the estimation model generation unit 14. The estimation model generation unit 14 generates an estimation model 22 by a machine learning algorithm using the change pattern stored in the change pattern database 21 (step S17).

[0110] The estimation model generation unit 14 stores the estimation model 22 generated by a predetermined machine learning in the storage unit 2 (step S18).

[0111] 4 and 5, the estimation device 10 generates the estimation model 22, but is not limited to this. For example, the estimation device 10 may provide an external computer different from the estimation device 10, which has the same functions as the learning control unit 13 and the estimation model generation unit 14, with the same data as the change pattern database 21 to generate the estimation model 22.

[0112] (Estimation of odor substances) Next, the configuration of the odor measuring device 100a that estimates an odor substance using the estimation model 22 and the estimation process will be described with reference to FIGS.

[0113] (Configuration of Estimation Device 10a (Execution of Estimation Process)) Fig. 6 is a functional block diagram showing an example of the configuration of an odor measuring device 100a. For ease of explanation, the same reference numerals are given to members having the same functions as those described in Fig. 1 and Fig. 4, and the description thereof will not be repeated.

[0114] As shown in Fig. 6, the estimation device 10a includes a control unit 1a, a storage unit 2a, and an output unit 18. Here, Fig. 6 shows a configuration example in which the estimation device 10 shown in Fig. 4 is used for odor substance estimation processing. That is, the estimation device 10 shown in Fig. 4 and the estimation device 10a shown in Fig. 6 may be computers having the same hardware configuration.

[0115] The output unit 18 is for presenting the estimation result to the user, and may be, for example, a display, a speaker, a lamp, or the like.

[0116] The control unit 1 a includes a measurement value acquiring unit 11 (acquiring unit), a change pattern analyzing unit 12 (analyzing unit), an estimating unit 16, and an output control unit 17.

[0117] The estimation unit 16 uses the estimation model 22 to estimate the odor substance from the analysis results obtained by analyzing the measurement values ​​obtained from the odor sensor 30.

[0118] The output control unit 17 controls the output unit 18 to output the estimation result.

[0119] (Estimation process) Specific processes performed by each part of the control unit 1a will be described below with reference to Fig. 7. Fig. 7 is a flow chart showing an example of the process flow when the estimation device 10a estimates an odor substance.

[0120] First, the measurement value acquiring unit 11 acquires the voltage value V0 measured in the odor sensor 30 before the filter paper P soaked with the odor substance is inserted into the housing 34, and calculates the resistance value R0 (step S1).

[0121] Next, the measurement acquisition unit 11 acquires the voltage value V measured by the odor sensor 30 immediately after inserting the filter paper P soaked with the unknown (i.e., the odor substance to be estimated) into the housing 34, and calculates the resistance value R (step S2).

[0122] Next, the change pattern analysis section 12 calculates R / R0 using the resistance value R0 and the resistance value R (step S3).

[0123] Next, the estimation unit 16 estimates the unknown odor substance from the pattern of change in R / R0 over time based on the estimation model 22 (step S4).

[0124] The output control unit 17 controls the output unit to output the estimation result (step S5).

[0125] [Embodiment 2] In the above embodiment, the odor sensor 30 including one sensor element 31 has been described, but the odor sensor 30 may include two or more sensor elements 31. For example, the odor sensor 30b may include sensor elements 31 and 31b in which the resin compositions used in the odorant receiving layer 315 are different from each other. This will be described with reference to FIG. 8. FIG. 8 is a block diagram showing an example of the configuration of an odor measuring device 100b according to another embodiment of the present invention. For ease of explanation, the same reference numerals are used for components having the same functions as the components described in FIG. 1, and the description thereof will not be repeated.

[0126] For example, the odor measuring device 100b shown in Fig. 8 includes odor sensors 30 and 30b and an estimation device 10b. The odor sensor 30b includes a sensor element 31 and a sensor element 31b, and the resin composition used in the odorant receiving layer 315 of the sensor element 31 and the odorant receiving layer 315b of the sensor element 31b may be different.

[0127] The estimation device 10b may be a computer having the same configuration as the estimation devices 10 and 10a. The estimation device 10b acquires and analyzes a first measurement value measured by a voltmeter 33 when a constant current is supplied from a constant current source 32 to a sensor element 31, and a second measurement value measured by a voltmeter 33b when a constant current is supplied from a constant current source 32b to a sensor element 31b.

[0128] By providing multiple sensor elements in which resin compositions with different odorant adsorption properties are used in the odorant receiving layer, the odor measuring device 100b can simultaneously perform estimations for multiple odorants. In addition to the sensor element according to one embodiment of the present invention, a sensor element that does not contain a surfactant (B) in the odorant receiving layer may be used in combination.

[0129] Furthermore, by using the odor measurement device 100b, it is possible to obtain a first change pattern indicating a change in the electrical conductivity of the sensor element 31 and a second change pattern indicating a change in the electrical conductivity of the sensor element 31b for each known odor substance. The estimation model 22 may be generated by machine learning using both the first change pattern and the second change pattern. The odor measurement device 100b estimates odor substances using the estimation model 22 generated in this way, and therefore is able to more precisely identify each odor substance.

[0130] [Embodiment 3] Hereinafter, one embodiment of the present invention will be described in detail.

[0131] The odor measuring device 100b of the second embodiment is an embodiment in which a filter paper P soaked with an odorant is introduced into a housing 34 having two sensor elements (i.e., sensor elements 31 and 31b) therein. In this configuration, it is not possible to control the timing at which the odorant reaches the sensor elements 31 and 31b, or to adjust the concentration of the odorant. Therefore, the odor measuring device 100c of the present embodiment is separately provided with a sensor chamber 60 having a plurality of sensor elements (hereinafter, sensor element group 31A), and a target sample receiving section 50 into which a target sample containing an odorant is introduced and into which gas containing the odorant generated from the target sample is contained. In this embodiment, the individual sensor elements included in the sensor element group 31A may be simply referred to as "sensor elements". In this embodiment, the configuration of the target sample receiving section 50 and the sensor chamber 60 corresponds to the odor sensor 30 and the odor sensor 31 of the first and second embodiments.

[0132] The odor measuring device 100c of this embodiment employs a configuration in which the gas containing the odor substance inside the target sample receiving section 50 is pushed toward the sensor chamber 60 by using another gas (carrier gas). In this embodiment, the gas inside the target sample receiving section 50 when the target sample is introduced into the target sample receiving section 50 (i.e., the gas containing the odor substance to be detected) is referred to as the first gas. Meanwhile, the carrier gas for pushing the first gas toward the sensor chamber 60 is referred to as the second gas.

[0133] Fig. 9 is a schematic diagram of an odor measurement device 100c. As shown in Fig. 9, the odor measurement device 100c includes a target sample receiving unit 50, a sensor chamber 60, a gas supply unit 80, and an estimation device 10b. The odor measurement device 100c may further include a regulator 51.

[0134] 9 shows, as an example, an example in which gas flows from gas supply unit 80 to target sample receiving unit 50 and sensor chamber 60 in that order. Gas supply unit 80, target sample receiving unit 50, and sensor chamber 60 are each connected by a tube.

[0135] The target sample receiving section 50 can receive a target sample containing an odorant therein and retain a first gas. The target sample receiving section 50 has a first port 501 through which a second gas entering the inside passes, and a second port 502 through which the first gas and the second gas leaving the inside can pass. The target sample receiving section 50 may also have a sample introduction port 503, which will be described later.

[0136] In FIG. 9, the first port 501 is installed at the top of the target sample receiving section 50, and the second port 502 is installed at the bottom of the target sample receiving section 50, but this is not limited thereto. For example, the positions of the first port 501 and the second port 502 may be appropriately set depending on the type and combination of odor substances contained in the first gas. For example, the positions of the first port 501 and the second port 502 may be changed depending on whether the weight per unit volume of the odor substance contained in the first gas (i.e., specific gravity) is heavier or lighter than that of the second gas. In addition, the target sample receiving section 50 may be provided with an airflow generating fan 35 inside, as in FIG. 8.

[0137] The target sample receiving section 50 has a sample introduction port 503 for receiving a liquid or solid target sample. FIG. 9 shows an embodiment in which a filter paper P soaked in an odorant is introduced as a target sample, as in FIG. 8. The target sample receiving section 50 may have a setting section (not shown) for setting the target sample. When the target sample is a liquid, the setting section may be a cup for holding the liquid, and when the target sample is a solid, the setting section may be a petri dish on which the solid is placed. The target sample may be introduced in a gaseous state as a first gas from the sample introduction port 503 into the target sample receiving section 50. In this way, since the target sample receiving section 50 can receive a liquid or solid target sample, it is possible to adjust the concentration of the odorant in the first gas. For example, even if the odorant is the same, it is easy to adjust the concentration of the odorant in the first gas.

[0138] A material inactive to odorants may be disposed on the inner surface of the target sample receiving portion 50. A material inactive to odorants is a material that does not significantly change the concentration of each odorant contained in the gas sent to the sensor chamber 60. For example, a material inactive to odorants is a material in which odorants are unlikely to be adsorbed or dissolved. Examples of materials inactive to odorants include glass, metal, and resin. When metal is used, stainless steel (SUS) is preferable, and when resin is used, fluorine-based resin, polypropylene (PP), polyethylene (PE), ABS resin, and polyethylene terephthalate (PET) are preferable.

[0139] If the inner surface of target sample receiving portion 50 is made of a material that adsorbs odorous substances contained in the first gas, the odorous substances may be adsorbed to various portions, which may affect subsequent measurements.

[0140] In this way, the inner surface of the target sample receiving portion 50 is made of a material that is inactive against odorants, thereby reducing the risk that the material of the inner surface will react with the odorants contained in the first gas, or that the odorants will be adsorbed onto the inner surface. This reduces the risk that the odorants contained in the first gas supplied to the sensor chamber 60 will change while contained in the target sample receiving portion 50, or that the concentration of the odorants will be diluted.

[0141] Even if the target sample is a liquid or solid, the odor measurement device 100c is provided with the target sample receiving section 50, thereby making the concentration of the first gas uniform in the target sample receiving section 50 before the first gas is sent to the sensor chamber 60. Furthermore, by providing the target sample receiving section 50, the odor measurement device 100c is able to push the first gas into the sensor chamber 60 at a constant flow rate. As a result, even when measurements are repeated, the odor measurement device 100c can send the first gas to the sensor chamber 60 under the same conditions each time, thereby enabling repeated and stable measurements to be performed.

[0142] The volume of the target sample receiving section 50 is preferably 1 to 100 times the volume of the sensor chamber 60. In particular, the volume of the target sample receiving section 50 is preferably larger than the volume of the sensor chamber 60. The volume of the target sample receiving section 50 is more preferably 2 to 80 times the volume of the sensor chamber 60, and more preferably 4 to 60 times the volume of the sensor chamber 60. By making the volume of the target sample receiving section 50 1 or more times larger than the volume of the sensor chamber 60, the concentration of the odorant in the sensor chamber 60 is appropriately adjusted, and the measurement result by the sensor provided in the sensor chamber 60 is stably output. In addition, by making the volume of the target sample receiving section 50 100 times or less the volume of the sensor chamber 60, the measurement result by the sensor is stably output, and the size of the odor measurement device 100c can be kept compact.

[0143] If the volume of the target sample receiving section 50 is less than one time the volume of the sensor chamber 60, the odorant generated in the target sample receiving section 50 may be diluted in the sensor chamber 60, which may reduce the measurement sensitivity of the sensor. If the volume of the target sample receiving section 50 is more than 100 times the volume of the sensor chamber 60, the volume of the target sample receiving section 50 may be too large, which may increase the overall size of the odor measuring device 100c.

[0144] FIG. 9 shows an example in which the volume of the target sample receiving portion 50 is eight times the volume of the sensor chamber 60.

[0145] For example, if the inner surface of the tube 93 is made of a material that adsorbs odorous substances contained in the first gas, the odorous substances may be adsorbed to various parts, which may affect the subsequent measurement. Therefore, it is preferable that a material that is inactive to odorous substances is arranged on the inner surface of the tube 93 that guides the first gas from the target sample receiving section 50 to the sensor chamber 60, similar to the inner surface of the target sample receiving section 50. Examples of materials that are inactive to the first gas include glass, metal, and resin. When metal is used, stainless steel (SUS) is preferable, and when resin is used, fluorine-based resin, polypropylene (PP), polyethylene (PE), ABS resin, and polyethylene terephthalate (PET) are preferable.

[0146] The target sample receiving section 50 may be configured to be detachable from the tubes 92 and 93. In this manner, since the target sample receiving section 50 is detachable, when the previous measurement is completed and the next measurement is to be performed, a new target sample receiving section 50 can be attached without purging the inside of the target sample receiving section 50. This allows the odor measuring device 100c to perform multiple measurements in a short period of time.

[0147] Furthermore, since the target sample receiving part 50 is detachable, the target sample receiving part 50 into which the target sample has been introduced can be kept at a desired temperature using a heat retention chamber separate from the odor measurement device 100c. This allows the odor measurement device 100c to adjust the temperature of the target sample receiving part 50, even if it is not possible to provide the adjustment part 51, which will be described later, in the odor measurement device 100c.

[0148] The adjustment unit 51 adjusts at least one of the temperature and humidity of the first gas contained in the target sample receiving portion 50. When the adjustment unit 51 adjusts the temperature, the adjustment unit 51 is, for example, a heater or a cooler. In this case, the adjustment unit 51 may be configured to cover the entire target sample receiving portion 50. When the adjustment unit 51 adjusts the humidity, the adjustment unit 51 is, for example, a humidifier or a dehumidifier. The adjustment unit 51 may adjust at least one of the temperature and humidity for each type of first gas, or may change at least one of the temperature and humidity at predetermined time intervals during measurement of the same first gas.

[0149] The adjustment unit 51 adjusts at least one of the temperature and humidity of the first gas in the target sample receiving unit 50, so that the odor measuring device 100c can send the first gas to the sensor chamber 60 using conditions according to, for example, the type of the first gas (such as the weight or volatility of the gas). This allows the odor measuring device 100c to send a first gas of a stable concentration to the sensor chamber 60, improving the accuracy of the measurement.

[0150] The gas supply unit 80 is connected to the first port 501 of the target sample receiving portion 50, and by sending a second gas into the inside of the target sample receiving portion 50, the first gas is sent from within the target sample receiving portion 50 toward the sensor chamber 60.

[0151] A valve 81 may be provided between the gas supply unit 80 and the target sample receiving unit 50. By opening and closing the valve 81, start and stop of gas supply from the gas supply unit 80 may be adjusted.

[0152] In this way, the gas supply unit 80 pushes the gas from the first port 501 side of the target sample receiving unit 50 to send the first gas into the sensor chamber 60, so the pressure inside the sensor chamber 60 is positive. This allows the odor measurement device 100c to obtain stable measurement results. In addition, since the second gas can be sent by opening and closing the valve 81, the odor measurement device 100c can send the first gas from the target sample receiving unit 50 toward the sensor chamber 60 at any timing. This allows the odor measurement device 100c to improve the reproducibility of the waveform shape output by each sensor element when repeatedly measuring an odor substance contained in the first gas using the sensor element group 31A.

[0153] The second gas may be an inert gas or air. Examples of the inert gas include argon and nitrogen. When the second gas is an inert gas, the gas supply unit 80 may be a gas cylinder.

[0154] Furthermore, when the second gas is air, the gas supply unit 80 may be a pump. In this case, in order to remove components that react with the first gas contained in the target sample receiving unit 50, the odor measuring device 100c may be provided with, for example, an activated carbon filter on the first port 501 side of the target sample receiving unit 50.

[0155] The odor measuring device 100c may further include a mass flow controller on the side of the first port 501 of the target sample receiving section 50, more specifically, between the valve 81 and the gas supply section 80. The odor measuring device 100c employing this configuration can send the first gas from the target sample receiving section 50 to the sensor chamber 60 at a constant flow rate, and the sensor elements of the sensor element group 31A can stably output.

[0156] The estimation device 10b has the same functions as the estimation device 10b of the second embodiment. When the sensor chamber 60 further includes a sensor element 31c in which a resin composition different from that of the sensor element 31 and the sensor element 31b is used in the substance receiving layer 315, the estimation device 10b may further acquire and analyze a measurement value measured by a voltmeter by supplying a constant current to the sensor element 31c. The estimation device 10b may also display the measurement value itself, a waveform in which the measurement value is plotted, and an estimation result of an unknown odor substance based on an estimation model. The estimation device 10b may also display a numerical value and a graph showing the change in the presence ratio of each odor substance for a gas containing multiple odor substances.

[0157] The sensor chamber 60 is a space for storing the sensor element group 31A for measuring odor substances. The sensor chamber 60 is connected to the second port 502 of the target sample receiving section 50. Specifically, the sensor chamber 60 includes a gas supply port 601 and a gas exhaust port 602, and the second port 502 of the target sample receiving section 50 and the gas supply port 601 are connected.

[0158] The sensor chamber 60 has multiple passages in which multiple sensor elements capable of outputting measurement results according to the odor substances contained in the gas are arranged. This can shorten the time required from when gas starts to be sent into the sensor chamber until all of the multiple sensor elements stably output measurement results. In addition, by finely dividing the multiple sensor elements by multiple passages, the variation in airflow turbulence for each measurement is reduced, and the measurement accuracy is improved.

[0159] Fig. 10 is a top view showing an example of the configuration of sensor chamber 60. Fig. 10 shows sensor chamber 60 having four passages (i.e., passage 61, passage 62, passage 63, and passage 64). The first gas can be supplied from target sample receiving portion 50 to each of passages 61 to 64.

[0160] A plurality of sensor elements that output different measurement results for each odorant may be arranged in each of the plurality of passages (passages 61 to 64). The plurality of sensor elements that output different measurement results for each odorant may be sensor elements that each have a different resin composition as a substance receiving layer. That is, the plurality of sensor elements arranged in one passage may have different sensitivities and detection specificities for the odorant. The sensor chamber 60 in FIG. 10 includes, as an example, the sensor element 31 and the sensor element 31b described in the second embodiment (FIG. 8) in the passage 61, but is not limited thereto. For example, the sensor element 31 and the sensor element 31b can output a measurement result corresponding to the same odorant contained in the first gas, but the measurement results output by each sensor element may be different. In addition, the sensor element 31 and the sensor element 31b may each output a measurement result corresponding to a different odorant. The measurement result corresponding to the odorant is, for example, a measurement result corresponding to the concentration of the odorant. By arranging multiple sensor elements that output different measurement results for each odor substance in each of the multiple passages, the odor measuring device 100c can detect odor substances passing through one passage using sensor elements with different sensitivities and detection specificities. This allows the odor measuring device 100c to comprehensively detect odor substances from multiple different measurement results.

[0161] 10, similar to the passage 61, a plurality of sensor elements (such as sensor elements 31c and 31d) capable of outputting a measurement result according to an odor substance contained in the first gas are arranged in the passage 62. A plurality of sensor elements (such as sensor elements 31e and 31f) capable of outputting a measurement result according to an odor substance contained in the first gas are arranged in the passage 63. A plurality of sensor elements (such as sensor elements 31g and 31h) capable of outputting a measurement result according to an odor substance contained in the first gas are arranged in the passage 64. These plurality of sensor elements may be sensor elements in which the resin composition used in the substance receiving layer 315 is different from one another.

[0162] Some of the sensor elements 31 to 31h may be sensor elements having the same detection specificity for odor substances. That is, for example, when the sensor element group 31A arranged in the sensor chamber 60 includes n sensor elements, m types of sensor elements (m < n) may be arranged. Also, some of the plurality of sensor elements arranged in the same passage may have the same detection specificity for odor substances.

[0163] Further, the sensor chamber 60 has passages 61 to 64, and a plurality of sensor elements may be arranged in each of the passages 61 to 64. In this case, the plurality of sensor elements arranged in each of the passages 61 to 64 constitute the sensor element group 31A. For example, 4 sensor elements may be arranged in passage 61 and 10 sensor elements may be arranged in passage 62.

[0164] When different numbers of sensor elements are arranged in each of the passages 61 to 64, the difference in the number of sensor elements arranged in each of the passages 61 to 64 is preferably 10 or less. By the difference in the number of sensor elements arranged in each passage being 10 or less, it is possible to reduce the variation in the timing at which odor substances are detected by the sensor elements, which may occur due to the passages. Also, since the difference in the number of sensor elements arranged in each of the passages 61 to 64 is 10 or less, the odor measuring device 100c can perform odor measurement in a short time.

[0165] Each of the passages is connected to a pipe body 93 for supplying the first gas into the internal space of the sensor chamber 60. As shown in FIG. 10, passages 61, 62, 63, and 64 are all connected to one pipe body 93.

[0166] Furthermore, the cross-sectional area of ​​each passage perpendicular to the supply direction in which the first gas is supplied from the tube 93 may be smaller than the cross-sectional area perpendicular to the axial direction of the tube 93. This allows the first gas supplied from the target sample receiving section 50 to pass through each passage at a faster flow rate than when passing through the tube 93. This minimizes the time lag in measurement between the sensor element arranged closer to the gas supply port 601 and the sensor element arranged closer to the gas exhaust port 602, allowing the odor measuring device 100c to perform highly accurate measurement.

[0167] Moreover, it is preferable that the gas in each internal space of the passage is replaced within 1 second after the supply of the first gas is started. The supply of the first gas is started, that is, when the first gas is supplied to the gas supply port 601. Moreover, the replacement of the gas in the internal space indicates that the first gas supplied from the gas supply port 601 reaches the gas exhaust port 602. In this way, by replacing the gas in each internal space of the passage within 1 second after the supply of the first gas and the second gas is started, the difference in the timing at which the first gas comes into contact with each sensor element is reduced, and the odor measuring device 100c can perform stable measurement. Furthermore, by replacing the gas in each internal space of the passage within 1 second after the supply of the first gas and the second gas is started, the odor measuring device 100c can perform odor measurement in a short time.

[0168] The flow rate of the first gas passing through each internal space of the passage is preferably 0.1 cm / sec or more and 100 cm / sec or less. The flow rate of the first gas passing through each internal space of the passage is more preferably 1 cm / sec or more and 50 cm / sec or less. The flow rate of the first gas passing through each internal space of the passage may be adjusted, for example, by the degree of pressurization of the gas supply unit 80 described later, or by a mass flow controller described later.

[0169] If the flow rate of the first gas passing through each internal space of the passage is slow, the timing difference between when the first gas touches all the sensor elements of the sensor element group 31A increases. On the other hand, if the flow rate of the first gas passing through each internal space of the passage is too fast, the sensor elements of the sensor element group 31A vibrate due to the influence of the air flow, and the odor measuring device 100c cannot stably measure the odor. Also, if the flow rate of the first gas passing through each internal space of the passage is too fast, the adsorption of the odor substance contained in the first gas to the sensor elements of the sensor element group 31A is hindered, and the odor measuring device 100c cannot accurately measure the odor. Also, if the flow rate of the first gas passing through each internal space of the passage is too fast, there is a risk that the first gas in the target sample receiving portion 50 will be consumed before the odor measuring device 100c can perform a stable measurement.

[0170] In this way, since the flow velocity of the first gas passing through each internal space of the passage is not less than 0.1 cm / sec and not more than 100 cm / sec, the odor measuring device 100c can stably perform odor measurement.

[0171] The passages may be arranged in parallel. In Fig. 10, the passages 61 to 64 are arranged in parallel with one another. By arranging the passages in parallel in this way, the odor measuring device 100c can secure space for arranging the passages, and the size of the entire device can be made compact.

[0172] Fig. 11 is a cross-sectional view that typically illustrates a cross section taken along line BB in Fig. 10. The passage 61 in Fig. 11 is composed of a side wall 610, a side wall 611 opposing the side wall 610, a ceiling 621, and a substrate 630 that is the bottom surface.

[0173] 11 shows sensor chamber 60 in which passage 61 has a rectangular cross-sectional shape, but there is no particular limitation on the cross-sectional shape of passage 61. For example, the cross-sectional shape of passage 61 may be a circular arc or a triangle.

[0174] The passages 61 and 62 are completely separated by side walls 611 and 612, and a configuration may be adopted in which gas cannot pass between the passages 61 and 62.

[0175] 11, as an example, there is a configuration in which two side walls (side wall 611 and side wall 612) are provided between the passage 61 and the passage 62, but this is not limiting. For example, the passage 61 and the passage 62 may be separated by a single side wall.

[0176] 11 is formed as a single unit, the present invention is not limited to this configuration. The entire sensor chamber 60 may be formed as a single unit, or each of the multiple passages may be formed as a separate body.

[0177] 11 includes the sensor element 31 on the substrate 630, which is the bottom surface of the passage 61, but the arrangement of the sensor element 31 is not limited thereto. The sensor element 31 may be arranged, for example, in consideration of the type of target odorant that the sensor element 31 can specifically detect. For example, the sensor element 31 may be arranged on any of the side wall 610, the side wall 611, and the ceiling 621. Specifically, when the odorant is lighter than air, the sensor element 31 may be arranged on the ceiling 621. In this way, by arranging the sensor element 31 in a location according to the type of odorant, the odor measuring device 100c can perform highly accurate measurements.

[0178] In FIG. 11, the sensor chamber 60 includes each sensor element on a substrate 630, and may further include a connector between the substrate 630 and each sensor element for connecting the substrate 630 and the sensor element.

[0179] Each sensor element may be independently connected to the substrate 630. For example, each sensor element may be connected to the substrate 630 via a connector (e.g., an IC pin). In this manner, even if a malfunction occurs in only one sensor element included in the sensor chamber 60, the user can replace only the malfunctioning sensor element.

[0180] In addition, when detecting odor substances using multiple types of sensor elements, the suitable combination of sensor elements to be used and the suitable arrangement of the sensor elements will differ depending on the type of odor substance. Since each sensor element is independently connected to the substrate 630 and each sensor element is detachable, the odor measuring device 100c can easily change the suitable combination and arrangement of sensor elements according to the odor substance.

[0181] The sensor elements may be disposed in two or more locations on the substrate 630, the sidewall 610, the sidewall 611, and the ceiling 621. This allows the length of the passage 61 to be shorter than when the sensor elements are provided on only one surface, making the size of the odor measuring device 100c more compact. In addition, since multiple sensor elements can be provided near the gas supply port 601, the odor measuring device 100c can perform odor measurement in a shorter time than when the sensor elements are arranged side by side facing the gas exhaust port 602.

[0182] The sensor chamber 60 in FIG. 11 has, as an example, four passages, each with one sensor element disposed in the cross-sectional direction, but the number of passages and the number of sensor elements in the cross-sectional direction are not limited to this. FIG. 12 shows a cross-sectional view of the sensor chamber 60a. The sensor chamber 60a has, as an example, two passages (passage 61a and passage 62a). Also, the cross-sectional direction of the passage 61a has two sensors (i.e., sensor element 31 and sensor element 31c). Also, in the sensor chamber 60a, as described above, the sensor elements may be disposed not only on the substrate 630 but also in two or more locations on the substrate 630, the side wall 610a, the side wall 613a, and the ceiling 621a. The arrangement of the sensor elements in the passage 62a is similar to that in the passage 61a.

[0183] The material of the inner surface of the sensor chamber 60 is preferably a material that is inactive to odorants, similar to the target sample receiving section 50. Examples of inactive materials include glass, metal, and resin. When metal is used, stainless steel (SUS) is preferable, and when resin is used, fluororesin, polypropylene (PP), polyethylene (PE), ABS resin, and polyethylene terephthalate (PET) are preferable. When the material of the inner surface of the sensor chamber 60 is a material that adsorbs odorants contained in the first gas, the odorants adsorbed in the sensor chamber may reduce the amount of change in output from the sensor element in a subsequent measurement, and the odor measuring device 100c may not be able to perform an accurate measurement.

[0184] The sensor elements of the sensor element group 31A may include a thin film. As an example, the odorant receiving layer 315 in Figures 2 and 3 is a thin film.

[0185] As an example of sending the first gas containing an odorant into the sensor chamber 60, a vacuum pump may be installed on the gas exhaust port 602 side of the sensor chamber 60, and the gas may be drawn using the vacuum pump to send the odorant into the sensor chamber 60 from the gas supply port 601 side of the sensor chamber 60. However, if the sensor elements 31 and 31b have a thin film, the thin film may expand if the sensor chamber 60 is under negative pressure, and the sensor elements 31 and 31b may not be able to output a stable measurement result. In the odor measurement device 100c according to this embodiment, the gas supply unit 80 pushes the gas from the sensor chamber 60 and the first port 501 side of the target sample receiving unit 50 to send the first gas into the sensor chamber 60, so the pressure in the sensor chamber 60 is positive. Therefore, the odor measurement device 100c can obtain a stable measurement result even if the sensor element of the sensor element group 31A has a thin film.

[0186] 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. Specific embodiments of the sensor element will be described later.

[0187] [Sensor element] The odor measuring device 100b of the second embodiment includes two sensor elements 31 and 31b. In the second embodiment, the variation in the shape, area, and thickness of the odorant receiving layers 315 and 315b of the sensor elements 31 and 31b is not particularly specified, but it is preferable that the shape, area, and thickness of the odorant receiving layers 315 and 315b are each less variable. This is because if there is variation in the shape, area, and thickness of the odorant receiving layers 315 and 315b of multiple sensor elements, there is a risk that the odorant cannot be stably measured. Hereinafter, the odorant receiving layers are collectively referred to simply as "odorant receiving layers."

[0188] The sensor elements 31 and 31b of the second embodiment each include a first metal wiring 313A and a second metal wiring 313B as electrodes, and the metal wirings are arranged in parallel to each other (see FIG. 2). The sensor elements 31 and 31b of the second embodiment also include an odorant receiving layer 315 that 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 include a sensor element that is configured with a metal wiring (i.e., electrode) arrangement and an odorant receiving layer shape different from those of the sensor elements 31 and 31b. In addition, what was referred to as the metal wiring 313 in the first and second embodiments will hereinafter also be referred to as the electrode 313.

[0189] The sensor element 31 includes an electrode 313 arranged on a substrate 311 and an odorant receiving layer 315 formed on the electrode 313. The odorant receiving layer 315 is circular or strip-shaped. When the odorant receiving layer 315 is circular, the diameter R of the circle is 0.2 mm or more and 10 mm or less. When the odorant receiving layer 315 is strip-shaped, the width W of the strip in the short direction may be 0.2 mm or more and 10 mm or less. Here, strip-shaped refers to a surface shape having a width in the short direction and a length in the long direction. When the odorant receiving layer 315 is circular, the diameter R of the circle is preferably 1.5 mm or more and 2.7 mm or less. When the odorant receiving layer 315 is strip-shaped, the width W of the strip in the short direction is preferably 1.5 mm or more and 2.7 mm or less.

[0190] Since the diameter R or width W of the circle of the odorant receiving layer 315, 315b to 315d of the sensor element 31, 31b to 31d included in the sensor element group 31A is within the above-mentioned range, the odor measuring device 100c can stably perform measurements according to the odorant.

[0191] If the diameter R of the odorant receiving layer 315 is less than 0.2 mm, or the width W is less than 0.2 mm, the area for receiving the odorant will be small, and the odor measuring device 100c will not be able to perform stable measurements.

[0192] Furthermore, if the diameter R of the odorant receiving layer 315 is greater than 10 mm, or if the width W is greater than 10 mm, the area of ​​each sensor element becomes larger, and the size of the sensor chamber 60 including the sensor element group 31A becomes larger. If the size of the sensor chamber 60 becomes larger, it becomes difficult to uniformly diffuse the first gas containing the odorant within the sensor chamber 60, and therefore the odor measuring device 100c cannot perform stable measurement.

[0193] FIG. 13 is a top view showing an example of the configuration of one sensor element 31c included in the sensor element group 31A. The sensor element 31c includes an electrode 313 (first electrode 313C, second electrode 313D) arranged on the substrate 311, and a circular odorant receiving layer 315c formed on the electrode 313. The diameter R of the odorant receiving layer 315c is 0.2 mm or more and 10 mm or less. In FIG. 13, the shape of the odorant receiving layer 315c included in the sensor element 31c is elliptical as an example, but is not limited to this. When the shape of the odorant receiving layer 315c is elliptical, the average of the minor axis and the major axis may be 0.2 mm or more and 10 mm or less. The shape of the odorant receiving layer 315c may also be a perfect circle.

[0194] 14 is a top view showing an example of the configuration of one 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 receiving layer 315d formed on the electrodes 313. The length of the width in the short direction of the odorant receiving layer 315d is 0.2 mm or more and 10 mm or less.

[0195] By having the above-described configuration, instability in the output of the measurement result that may be caused by variations in the shape and area of ​​the odorant receiving layer of each sensor element is reduced, and the odor measuring device 100c can measure odorants with high accuracy.

[0196] The sensor element group 31A may include a plurality of sensor elements other than the sensor elements 31, and 31b to 31d. In Fig. 9, the sensor element group 31A is composed of 16 sensor elements as an example, but the number of sensor elements is not limited to this.

[0197] The odorant receiving layers 315, 315b to 315d of the multiple sensor elements 31, 31b to 31d included in the sensor element group 31A may each contain a conductive carbon material, a resin composition, and a surfactant.

[0198] The odorant receiving layers 315, 315b-315d of the multiple sensor elements 31, 31b-31d included in the sensor element group 31A may each have a different content ratio of conductive carbon material, resin composition, and surfactant. If the content ratio of conductive carbon material, resin composition, and surfactant contained in the odorant receiving layer differs, the sensitivity and detection specificity of the sensor element to the odorant will also differ.

[0199] As described above, the odor measuring device 100c is equipped with multiple sensor elements each having an odorant receiving layer with a different content ratio of conductive carbon material, resin composition, and surfactant, thereby being able to detect a wide variety of odorants.

[0200] The odorant receiving layers 315, 315b to 315d of the sensor elements 31, 31b to 31d included in the odor measuring device 100c according to this embodiment may have a thickness of 0.1 μm or more and 1000 μm or less. In addition, the thickness of each odorant receiving layer may be preferably 1 μm or more and 100 μm or less.

[0201] By having the thickness of the odorant receiving layer of the sensor elements 31, 31b to 31d within the above-mentioned range, instability in the measurement result output that may be caused by variations in the thickness of the odorant receiving layer 315, 315b to 315d of each sensor element is reduced, and the odor measuring device 100c can measure odorants with high accuracy.

[0202] If the thickness of the odorant receiving layer 315, 315b to 315d is less than 0.1 μm, the value will be close to the particle diameter of the conductive carbon material dispersed in the odorant receiving layer, so the uniformity of the thickness of the odorant receiving layer cannot be guaranteed, 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 receiving layer 315, 315b to 315d is greater than 1000 μm, the diffusion time of the odorant in the odorant receiving layer will be longer, making it difficult for the odor measuring device 100c to measure the odorant with high accuracy.

[0203] By having the thickness of the odorant receiving layers 315, 315b to 315d of the sensor elements 31, 31b to 31d within the above-mentioned range, instability in the output of the measurement results that may be caused by variations in the thickness of the odorant receiving layer of each sensor element is reduced, and the odor measuring device 100c can measure odorants with high accuracy.

[0204] The electrodes of the sensor elements 31, 31b to 31d included in the sensor element group 31A each have a first electrode and a second electrode, and the first electrodes and the second electrodes may be arranged in parallel lines, parallel curves, a comb shape, or a concentric circle shape. Regardless of which shape is adopted, the first electrodes and the second electrodes are preferably arranged in line symmetry or point symmetry with each other. By arranging the first electrodes and the second electrodes in this way, the odor measuring device 100c can measure odor substances contained in the gas with high accuracy.

[0205] The sensor element 31c of FIG. 13 has a first electrode 313C and a second electrode 313D. 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 so as to be perpendicular to each other. The second electrode 313B is also composed of two metal wirings 313c and 313d like the first electrode 313C, and is configured so as to be arranged in a T-shape so as to be perpendicular to each other. The first electrode 313A and the second electrode 313B are arranged in parallel lines so that the metal wiring 313a and the metal wiring 313c face each other.

[0206] The first electrode 313C and the second electrode 313D are arranged in a T-shape, so that the first electrode 313C and the second electrode 313D can be arranged at a suitable distance from each other, and the resistance value of the electrodes can be stabilized. For example, if the electrodes are arranged in a comb shape, the distance between the electrodes is short, and the resistance value of the electrodes may become too small. In addition, since the first electrode 313C and the second electrode 313D are arranged in a T-shape, in the application process of the manufacturing method of the sensor element described later, there is no uneven part of the electrode that may hinder the slurry from spreading in the area where the slurry spreads, so the slurry spreads easily. In addition, since the slurry spreads easily, the thickness of the odorant receiving layer after drying is uniform.

[0207] [Method of manufacturing sensor element] A manufacturing method for manufacturing a plurality of types of sensor elements 31, 31b to 31d used in the odor measuring device 100c will be described. The odorant receiving layers 315, 315b to 315d of the sensor elements 31, 31b to 31d may use slurries having various compositions as their raw materials, but the viscosities of the slurries differ depending on the composition of the slurries. When forming an odorant receiving layer by applying slurries with different viscosities using the same method, for example, a low-viscosity slurry is easily wetted and spread on the substrate, while a high-viscosity slurry is difficult to wet and spread on the substrate. In this way, when applying slurries with different viscosities using the same manufacturing method, the shape, area, thickness, etc. of the odorant receiving layers 315, 315b to 315d after drying will vary. It is difficult to stably measure odorants with the sensor elements 31, 31b to 31d manufactured using such an odorant receiving layer. On the other hand, if the manufacturing method is changed depending on the viscosity of the slurry, uniform odorant receiving layers 315, 315b to 315d can be obtained without variations in shape, area, thickness, etc., but the manufacturing costs will be higher.

[0208] According to the manufacturing method of this embodiment, it is possible to manufacture a plurality of types of sensor elements 31, 31b to 31d with little variation in shape, area, and thickness even when using slurries with different compositions, i.e., different viscosities. In addition, since it is not necessary to change the manufacturing method depending on the viscosity, it is possible to reduce manufacturing costs.

[0209] FIG. 15 is a flow chart for explaining steps of a manufacturing method for manufacturing the multiple types of sensor elements 31, 31b to 31d used in the odor measuring device 100c.

[0210] <Slurry preparation process> First, a slurry containing a filler, a resin composition, and a surfactant is prepared. The resin composition of the slurry contains T units (R 1 SiO 3 / 2 The silicone resin may be contained in an amount of 30 to 100% by weight of the entire resin. The mixing ratio of the filler, the resin composition, and the surfactant may be appropriately set according to the desired sensitivity and detection specificity of the odorant receiving layer. The slurry may contain a solvent and an additive in addition to the filler, the resin composition, and the surfactant (S21).

[0211] <Electrode placement process> 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. The first electrode and the second electrode may be arranged in parallel straight lines, parallel curved lines, a comb shape, or a concentric circle shape. In addition, regardless of which of the above shapes is adopted, it is preferable that the first electrode and the second electrode are arranged in line symmetry or point symmetry with each other. By arranging the first electrode and the second electrode in this manner, the odor measuring device 100c can measure odor substances contained in the gas with high accuracy.

[0212] As an example, in Figures 13 and 14, a pair of electrodes (first electrode 313C and second electrode 313D) is arranged on a single substrate 311, but multiple pairs of electrodes may be arranged side by side on a single substrate.

[0213] <Area definition process> Next, coating regions onto which the plurality of types of slurries are to be coated are defined on the substrate on which the electrodes are disposed (S23). The coating regions are regions including at least a portion of the first metal wiring and at least a portion of the second metal wiring. The coating regions may be defined, for example, by disposing a resist. Furthermore, in the coating step, when the slurry is dropped from a nozzle, the coating regions may be defined in accordance with the nozzle diameter. FIG. 16 is a schematic diagram of substrate 311 after resist M has been disposed. Resist M is disposed so as to define coating region 330. In coating region 330, substrate 311 is exposed.

[0214] The size of the coating area 330 may be set to be the same for each of the multiple types of slurries. That is, even if the mixing ratios of the conductive carbon material, the resin composition, and the surfactant are different for each slurry, the area of ​​the coating area 330 for coating the slurry may be uniform. This reduces the variation in the area of ​​the multiple types of odorant receiving layers after drying, even if multiple types of slurries with different mixing ratios, i.e., different viscosities, are used.

[0215] 16 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 be circular or strip-shaped. This forms a circular or strip-shaped odorant receiving layer.

[0216] When the shape of the coating region 330 is circular, the diameter of the circle may be 0.2 mm or more and 10 mm or less, and when the shape of the coating region 330 is strip-shaped, the length of the strip in the short direction may be 0.2 mm or more and 10 mm or less. This forms a circular odorant receiving layer with a diameter of 0.2 mm or more and 10 mm or less, and a circular odorant receiving layer with a strip length in the short direction of 0.2 mm or more and 10 mm or less.

[0217] The method for applying the resist M is not particularly limited, but examples include a method of silk-screening the solder resist in a specified area and then UV-curing the solder resist, a method of attaching a resist film to a substrate, and a method of curing only the resist in a specified area and removing the uncured portion.

[0218] <Coating process> Next, each of the multiple types of slurries is applied to the application region 330 (S24). The slurry is applied to the application region 330 including at least a part of the first electrode and at least a part of the second electrode. The method for applying the slurry may be a conventionally known method, and the slurry may be dropped from a nozzle, sprayed, or spin-coated.

[0219] The viscosities of the multiple types of slurries are different from each other. The different viscosities of the slurries are caused, for example, by the different mixing ratios of the conductive carbon material, the resin composition, and the surfactant. Slurries with different viscosities may have different wetting and spreading patterns. However, in the coating step of this manufacturing method, since the coating area is defined by the previous area defining step, the slurry is applied to the defined area.

[0220] <Drying process> Finally, the slurry applied to the application area 330 is dried to form an odorant receiving layer (S25). The method for drying the slurry is not particularly limited, but may be, for example, a method of heating at 100°C for 1 hour at normal pressure, and then heating at 100°C for 1 hour while reducing the pressure in a vacuum dryer.

[0221] In the drying process, the thickness of the odorant receiving layer after drying may be 0.1 μm or more and 1000 μm or less. The thickness of the odorant receiving layer after drying may preferably be 1 μm or more and 100 μm or less. If the thickness of the odorant receiving layer is in the above range, the sensor element can stably measure the odorant. If the thickness of the odorant receiving layer is less than 0.1 μm, the value is close to the particle diameter of the conductive carbon material dispersed in the odorant receiving layer, so the uniformity of the thickness of the odorant receiving layer cannot be guaranteed, and there is a risk that the odor measuring device 100c cannot output a stable measurement result. On the other hand, if the thickness of the odorant receiving layer is greater than 1000 μm, the diffusion time of the odorant in the odorant receiving layer becomes longer, making it difficult for the odor measuring device 100c to measure the odorant with high accuracy.

[0222] As described above, the manufacturing method according to the present embodiment includes a slurry preparation step, an electrode arrangement step, an area definition step, a coating step, and a drying step. By adopting such a manufacturing method, even if multiple types of slurries with different mixing ratios of conductive carbon material, resin composition, and surfactant are used, multiple types of sensor elements 31, 31b to 31d with little variation in shape, area, and thickness of the odorant receiving 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, manufacturing costs can be reduced.

[0223] In particular, by defining the coating area in the area defining step, the droplets of the slurry can be well wetted and spread in the subsequent coating step. For example, when the coating area is defined by resist, the surface roughness of the substrate differs between the portion where the resist is present and the portion where the resist is not present. In the portion where the resist is not present, the substrate is exposed, so the surface roughness is large and the surface tension is small. This allows the droplets of the slurry to be well wetted and spread in the coating area where the substrate is exposed.

[0224] In addition, by arranging the application area in the area definition process, the spreading of the slurry is restricted in the subsequent application process, and the positional relationship between the odorant receiving layer 315, 315b-315d and the electrodes is constant. For example, if the application area is defined by resist, a step is generated at the resist boundary, restricting the spreading of the slurry, and the positional relationship between the odorant receiving layer 315, 315b-315d and the electrodes is constant.

[0225] The region defining step is not essential, and the coating step may be performed in a state in which the region is not defined.

[0226] In producing the odorant receiving layers 315, 315b to 315d, the odorant receiving layers 315, 315b to 315d may be produced by coating a resin composition, and then electrodes may be produced so as to be in contact with the odorant receiving layers.

[0227] In this disclosure, the slurry is represented by T units (R 1 SiO 3 / 2 The silicone resin (containing the silicone resin), the filler, and the surfactant provide the slurry with suitable flexibility and excellent film-forming properties. The improved film-forming properties also allow the sensor elements 31, 31b to 31d to be manufactured stably.

[0228] [Software implementation example] The control block (particularly the control unit 1) of the estimation devices 10, 10a, 10b may be realized by a logic circuit (hardware) formed on an integrated circuit (IC chip) or the like, or may be realized by software.

[0229] In the latter case, the estimation device 10, 10a, 10b includes a computer that executes instructions of a program, which is software that realizes each function. The computer includes, for example, one or more processors, and a computer-readable recording medium that stores the program. The object of the present invention is achieved by the processor reading the program from the recording medium and executing it in the computer. The processor may be, for example, a CPU (Central Processing Unit). The recording medium may be a "non-transient tangible medium", such as a ROM (Read Only Memory), a tape, a disk, a card, a semiconductor memory, a programmable logic circuit, or the like. The device may further include a RAM (Random Access Memory) that expands the program. The program may be supplied to the computer via any transmission medium (such as a communication network or a broadcast wave) that can transmit the program. Note that one aspect of the present invention may also be realized in the form of a data signal embedded in a carrier wave, in which the program is embodied by electronic transmission.

[0230] In addition, some or all of the functions of each of the control blocks can be realized by a logic circuit. For example, an integrated circuit in which a logic circuit that functions as each of the control blocks is formed is also included in the scope of the present invention. In addition, the functions of each of the control blocks can be realized by, for example, a quantum computer.

[0231] Furthermore, each process described in each of the above embodiments may be executed by AI (Artificial Intelligence). In this case, the AI ​​may be executed by the control device or another device (for example, an edge computer or a cloud server).

[0232] 〔summary〕 The odor measuring device 100, 100a to 100c according to the first aspect of the present disclosure includes a plurality of sensor elements 31, 31b to 31d each including an electrode 313 having a first metal wiring 313A and a second metal wiring 313B spaced apart from the first metal wiring 313A, and an odorant receiving layer 315, 315b to 315d 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 receiving layer 315, 315b to 315d includes a resin composition, and the resin composition is a T unit (R 1 SiO 3 / 2 (A) containing a silicone resin, (C) containing a filler, and (B) containing a surfactant, 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0233] In the odor measuring devices 100 and 100a to 100c according to embodiment 2 of the present disclosure, in embodiment 1, the silicone resin may be contained in an amount of 30 to 100% by weight based on the total weight of the resin (A).

[0234] In the odor measuring device 100, 100a to 100c according to aspect 3 of the present disclosure, in aspect 1 or 2, the odorant receiving layer may have a porosity x evaluated based on an SEM image of a cross section of the odorant receiving layer in the range of 12%≦x≦30%.

[0235] The odor measuring device 100, 100a to 100c according to the fourth aspect of the present disclosure in any one of the first to third aspects may detect an odor based on a change in the resistance value of the odorant receiving layer 315, 315b to 315d.

[0236] In the odor measuring device 100, 100a to 100c according to a fifth aspect of the present disclosure, in any one of the first to fourth aspects, the filler (C) may be a conductive carbon material.

[0237] In the odor measuring devices 100 and 100a to 100c according to a sixth aspect of the present disclosure, in the fifth aspect, the conductive carbon material may be carbon black.

[0238] The sensor element 31, 31b to 31d according to the seventh aspect of the present disclosure includes an electrode 313 having a first metal wiring 313A and a second metal wiring 313B spaced apart from the first metal wiring 313A, and an odorant receiving layer 315, 315b to 315d 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 receiving layer 315, 315b to 315d includes a T unit (R 1 SiO 3 / 2 (A) containing a silicone resin, (C) containing a filler, and (B) containing a surfactant, 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0239] A method for manufacturing the sensor element 31, 31b to 31d according to the eighth aspect of the present disclosure includes a slurry preparation step of preparing a slurry, an electrode arrangement step of arranging an electrode 313 having a first metal wiring 313A and a second metal wiring 313B spaced apart from the first metal wiring 313A on a substrate, a coating step of coating the slurry on a coating area including 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 receiving layer 315, 315b to 315d, wherein the slurry is a T unit (R 1 SiO 3 / 2 )), a filler (C), and a surfactant (B), 1 is a monovalent hydrocarbon group having 1 to 10 carbon atoms.

[0240] In the production method according to embodiment 9 of the present disclosure, in embodiment 8, the silicone resin may be contained in an amount of 30 to 100% by weight based on the total weight of the resin (A).

[0241] The present invention is not limited to the above-described embodiments, and various modifications are possible within the scope of the claims. Embodiments obtained by appropriately combining the technical means disclosed in the different embodiments are also included in the technical scope of the present invention.

[0242] According to the above-mentioned aspects of the present invention, it is possible to mechanically measure odors with high accuracy and high sensitivity. Therefore, the present invention is applicable to a wide range of industrial fields where odor measurement is required, and is expected to contribute to the achievement of Goal 9 of the Sustainable Development Goals (SDGs) on infrastructure for industry and innovation. EXAMPLES

[0243] The present invention will be further described below with reference to examples and comparative examples, but the present invention is not limited thereto. In the following, unless otherwise specified, % means % by weight and parts means parts by weight.

[0244] The various materials used in the examples and comparative examples are described below.

[0245] [Resin (A)] Silicone resin Here, the silicone resin does not include silicone oil.

[0246] A1: Silsesquioxane (DOWSIL RSN0217, manufactured by Toray Dow Co., Ltd.) A2: Silicone resin [Synthesis example of silicone resin (A2)] In a 500mL flask, 18g of water, 2g of 28% ammonia water, and 80g of 2-propanol were added to 4.41g of 3-furyltriethoxysilane, and the mixture was reacted at 80°C for 3 hours. After cooling the reaction solution in air, the precipitate was isolated by filtration (organic-inorganic hybrid-containing solution). The sample was thoroughly washed with ethanol, dried, and then dissolved in DMF to a concentration of 10mg / mL. A filler-containing solution prepared by dispersing silica with an average primary particle size of 80nm in 2-propanol dispersion IPA-ST-ZL (Nissan Chemical Products) to a concentration of 10mg / mL in DMF and mixing the aforementioned organic-inorganic hybrid-containing solution at a mixing ratio of 6:4 (organic-inorganic hybrid-containing solution: filler-containing solution) was obtained to obtain the desired silicone solution. In addition, a portion of the silicone solution was used as a sample, dried at 100°C in air, and the thermal weight loss rate was measured using TGA. Silicone oil A3: Polyether modified silicone oil (KF6020, Shin-Etsu Chemical Co., Ltd.) (main chain is D unit (R 1 2SiO 2 / 2 ) consisting of A4: Terminal hydroxyl group modified silicone oil (X-22-170DX, Shin-Etsu Chemical Co., Ltd.) (main chain is D unit (R 1 2SiO 2 / 2 ) consisting of [Surfactant (B)] B1: Disparlon DA-325 (Kusumoto Chemicals Co., Ltd.) (amine salt of polyether phosphate ester, containing AOA chain (ether structure)) B2: AJISPER PB-822 (manufactured by Ajinomoto Fine-Techno Co., Ltd.) (amino group-containing, nonionic) B3: IONET S-60V (manufactured by Sanyo Chemical Industries, Ltd.) (fatty acid ester of sorbitan, containing a sorbitol skeleton (ether structure)) B4: IONET T-80V (manufactured by Sanyo Chemical Industries, Ltd.) (ethylene oxide (EO) adduct of sorbitan fatty acid ester, containing AOA chain (ether structure)) B5: Polyvinylpyrrolidone (Nippon Shokubai Co., Ltd.) (nonionic) [Filler (C)] C1: Silica (IPA-ST-ZL, Nissan Chemical Co., Ltd.) C2: Carbon black (SuperC65, manufactured by MTI Corporation) [Solvent (D)] D1: Butyl butyrate Examples and comparative examples of resin compositions are shown below.

[0247] [Resin composition 1] The following components were weighed in the following amounts into a sample bottle to obtain a mixture.

[0248] Silicone resin A1 36 parts by weight Silicone oil A3 36 parts by weight Surfactant B1 8 parts by weight Filler C2 20 parts by weight Solvent D1 50 parts The mixture was stirred at 2000 rpm for 20 minutes using a planetary centrifugal mixer (ARE-310, manufactured by Thinky Corporation) to obtain a slurry, which was resin composition 1.

[0249] [Resin compositions 2, 9 to 12, resin composition C1] Resin compositions 2, 9 to 12, and resin composition C1 were prepared in the same manner as resin composition 1, except that the amounts of silicone resin A1, silicone oil A3, surfactant B1, and filler C2 were changed to the weight parts shown in Table 1, respectively.

[0250] [Resin composition 3] Resin composition 3 was prepared in the same manner as resin composition 1, except that silicone oil was not used and the amount of silicone resin A1 was changed to the parts by weight shown in Table 1.

[0251] [Resin composition 4] Resin composition 4 was prepared in the same manner as resin composition 1, except that silicone oil A4 was used instead of silicone oil A3.

[0252] [Resin composition 5] Resin composition 5 was prepared in the same manner as resin composition 1, except that surfactant B2 was used instead of surfactant B1.

[0253] [Resin composition 6] Resin composition 6 was prepared in the same manner as resin composition 1, except that surfactant B3 was used instead of surfactant B1.

[0254] [Resin composition 7] Resin composition 7 was prepared in the same manner as resin composition 1, except that surfactant B4 was used instead of surfactant B1.

[0255] [Resin composition 8] Resin composition 8 was prepared in the same manner as resin composition 1, except that surfactant B5 was used instead of surfactant B1.

[0256] [Resin composition C2] Resin composition C2 was prepared in the same manner as resin composition 1, except that silicone oil A3 and surfactant B1 were not used and the amount of silicone resin A1 was changed to the parts by weight shown in Table 1.

[0257] [Resin composition C3] Resin composition C3 was prepared in the same manner as resin composition 1, except that silicone oil A3 and surfactant B1 were not used, silicone resin A2 was used instead of silicone resin A1, and filler C1 was used instead of filler C2.

[0258] Examples and comparative examples of the sensor element are shown below.

[0259] [Sensor elements E-1 to E-14, comparative sensor elements E'-1 to E'-3] A seal substrate including a pair of metal wires was cut out from a seal substrate (ICB-073, Sanhayato Co., Ltd.) with multiple metal wires spaced 500 μm apart. The cut seal substrate was further cut so that the length of the metal wires was 3.5 cm.

[0260] The cut seal substrate was attached to a glass plate with double-sided tape so that the metal wiring was on top. In addition, vinyl tape was attached to mask the excess part of the metal wiring so that the length of the exposed part of the metal wiring was 3.0 cm. Resin compositions 1 to 12 and comparative resin compositions c1 to c3 were applied to the exposed part of the metal wiring using a bar coater (No. 4). After application, the resin compositions were dried for 3 hours in a wind dryer heated to 100°C. After drying, the resin compositions were cooled to room temperature, and the metal wiring with the odorant receiving layer was peeled off from the glass plate to obtain sensor elements (E-1) to (E-14) and comparative sensor elements (E'-1) to (E'-3). For sensor elements (E-3) to (E-5), three sensor elements (E-3) to (E-5) were produced using the same resin composition 3.

[0261] [Examples 1 to 14, Comparative Examples 1 to 3] A housing was created that had an inlet for introducing the sample (odor substance), and a carrier gas inlet and gas flow regulator for creating an airflow so that the sample would spread evenly. Lead wires for taking out the terminals to the outside were soldered to each of the eight sensor elements (E-1), and the eight sensor elements (E-1) were installed inside the housing. A 1 mA constant current power supply and a voltmeter for measuring the voltage across both terminals of the lead wires were connected to the ends of the lead wires taken out of the housing for each sensor element (E-1). In this way, an odor sensor 1 with eight sensor elements (E-1) was constructed.

[0262] Odor sensors 2 to 14 and c1 to c3 were constructed in the same manner as odor sensor 1, except that sensor elements (E-2) to (E-14) and comparative sensor elements (E'-1) to (E'-3) were used instead of sensor element (E-1). For odor sensors 4 and c3, a membrane-type surface stress sensor (MSS) method was used, an SD-MSS sensor probe (manufactured by NIMS) was used, and the electromotive force from the sensor element was amplified with an amplifier to obtain the output voltage. For odor sensor 5, a quartz crystal microbalance (QCM) method was used, a QA-A9M-AU (manufactured by Seiko EG&G) was used, and the resonant frequency was measured with a frequency counter to obtain the frequency change.

[0263] 〔evaluation〕 [Measurement of ΔV coefficient of variation] For each of the odor sensors 1 to 14 and C1 to C3, 5 mL of ethanol as a sample was placed in the inlet of the odor sensor. Then, nitrogen as a carrier gas was flowed from the carrier gas inlet into the housing in which the sensor element was installed at a flow rate of 1 L / min by a gas flow regulator, and discharged to the outside. During this time, the measured values ​​of the voltmeter connected to the sensor element were recorded by a computer. In this way, the voltage values ​​of each of the eight sensor elements in the odor sensor were measured. For each sensor element of each odor sensor, the maximum value ΔV of the difference between the output voltage V0 before the introduction of the sample and the voltage V during the introduction of the sample was calculated. Then, the standard deviation σ and the average value μ of the eight maximum value ΔV data obtained for each odor sensor were calculated, and the ΔV variation coefficient (=σ / μ) of the resin composition forming the sensor element was obtained. For the odor sensors 4 and c3, V0 and V were obtained for the output voltage obtained from the MSS sensor element. For the odor sensor 5, F0 and F were obtained for the frequency obtained from the QCM sensor element, and the variation coefficient was obtained by calculating in the same manner as for V0 and V, respectively.

[0264] [Porosity measurement method] The cross section of the sensor element of each of the odor sensors 1 to 14 and c1 to c3, including the odorant receiving layer and the odorant permeation layer, was observed and photographed by a scanning electron microscope (SEM). The SEM observation conditions were as follows: Manufacturer:HITACHI Equipment: S-4800 Acceleration voltage: 1.0V Current value: 10μA.

[0265] When acquiring SEM images, the contrast was adjusted between 3225 and 3275, and the brightness was adjusted between 2025 and 2075 using the built-in application.

[0266] The SEM images obtained by SEM were binarized using image analysis software. ImageJ was used for the binarization process. In this binarization process, the images were processed in the order of "Gaussian Blur", "16bit", and "unsharp Mask", and then binarized using "threshold". By setting the threshold value at this time to 50 in grayscale, the area corresponding to the voids in the SEM image was extracted, and the porosity, which is the ratio of the area occupied by the voids to the area of ​​the area captured in the SEM image of the odorant receptor layer, was calculated.

[0267] Table 1 shows the composition and physical properties of the resin composition materials of odor sensors 1 to 14 of Examples 1 to 14 and odor sensors c1 to c3 of Comparative Examples 1 to 3.

[0268] [Table 1]

[0269] In Table 1, "T units / D units" refers to the weight ratio of T units to D units contained in the silicone resin. If the ΔV coefficient of variation is 0.2 or less, preferably 0.14 or less, and more preferably 0.12 or less, it can be determined that the performance variation between the multiple sensor elements in the integrated odor sensor is sufficiently small and does not pose a problem in practical use. From the viewpoint of reducing the variation, the smaller the ΔV coefficient of variation, the more preferable it is.

[0270] [Consideration] As shown in Table 1, all of odor sensors 1 to 14 exhibit ΔV variation coefficients that are either acceptable for practical use or preferable for practical use.

[0271] Furthermore, as shown in Table 1, odor sensors 3, 5, and 9 to 10, whose porosity x evaluated based on SEM images of the cross sections of the odorant receiving layer is within the range of 12%≦x≦30%, all show ΔV coefficients of variation that are either acceptable for practical use or preferable for practical use.

[0272] Comparing Examples 1 to 14 with Comparative Example 1, it was found that the ΔV coefficient of variation of the odor sensor c1 having the resin composition c1 in which the weight part of the silicone resin A1 was less than 30 weight % relative to the total resin (A) was large.

[0273] Comparing Examples 1 to 14 with Comparative Examples 2 and 3, it was found that the ΔV coefficient of variation was large for odor sensors c2 and c3 comprising resin compositions c2 and c3 that did not contain a surfactant (B).

[0274] Comparing Examples 1 to 3, even when the part by weight of silicone resin A1 is different, a ΔV variation coefficient that does not pose a practical problem is obtained.

[0275] Furthermore, a comparison between Example 1 and Example 6 shows that even when the type of silicone oil contained in the resin (A) is different, a ΔV coefficient of variation that does not pose a practical problem is obtained.

[0276] Comparison of Examples 6 to 10 shows that even when the type of surfactant (B) is different, a ΔV coefficient of variation that does not pose a practical problem is obtained.

[0277] Comparing Examples 6, 8, and 9 with Example 10, the results of Examples 6, 8, and 9 in which the surfactant (B) contained in the resin composition had an ether structure showed smaller ΔV coefficient of variation of the odor sensor than the result of Example 10 in which the surfactant (B) contained in the resin composition did not have an ether structure. This shows that the ΔV coefficient of variation of the odor sensor can be reduced by adopting a configuration in which the resin composition contains a surfactant having an ether structure.

[0278] Furthermore, when Example 6 was compared with Examples 7 to 10, the odor sensor 6 (Example 6) provided with the resin composition 4 containing an amino group and an AOA chain had the smallest ΔV coefficient of variation.

[0279] Comparing Examples 1, 11, and 12, it is found that even when the parts by weight of the surfactant (B) are different, a ΔV coefficient of variation that is practically problem-free is obtained.

[0280] Comparing Examples 3 to 5, it was found that the ΔV coefficient of variation was practically acceptable even when the sensor methods were different. Furthermore, the ΔV coefficient of variation of odor sensor 3 of Example 3, which is a resistive sensor method, was smaller than odor sensor 4 using the MSS method and odor sensor 5 using the QCM method. In other words, odor sensors that use a resistive method to detect odors based on changes in the resistance value of an odorant receiving layer have smaller performance variations between multiple sensor elements.

[0281] Therefore, T units (R 1 SiO 3 / 2 It was found that an odor sensor having an odorant receiving layer containing a silicone resin, a filler, and a surfactant exhibits a ΔV coefficient of variation that is practically acceptable. In other words, an odor measuring device equipped with such an odor sensor can output stable measurement results. [Industrial Applicability]

[0282] The present invention is useful as an odor identification sensor for medical use, gas detection, agriculture, and other industrial and daily uses. For example, farmers can use the odor identification sensor to determine the maturity of fragrant crops and manage the optimal harvest timing. In addition, the odor identification sensor can be used to digitize the odors of products such as food and cosmetics, helping to improve the efficiency of product development and stabilize quality. [Explanation of symbols]

[0283] 10, 10a, 10b Estimation device 11 Measurement value acquisition unit (acquisition unit) 12 Change pattern analysis section (analysis section) 16 Estimation part 30, 30b Odor sensor 31, 31b, 31c, 31d Sensor elements 32, 32b Constant current source (power supply) 33, 33b Voltmeter (measuring instrument) 100, 100a, 100b, 100c Odor measuring device 313A 1st metal wiring 313B 2nd metal wiring 315, 315b Odorant receptor layer 313C 1st electrode 313D 2nd electrode 330 Application area

Claims

1. A plurality of sensor elements are provided, each of which includes an electrode having a first metal wiring and a second metal wiring spaced apart from the first metal wiring, and an odorant receiving layer in contact with at least a portion of the first metal wiring and at least a portion of the second metal wiring; The odorant receiving layer comprises a resin composition, The resin composition comprises a T unit (R １ SiO ３／２ A resin including a silicone resin, a filler, and a surfactant, The R １ is a monovalent hydrocarbon radical having 1 to 10 carbon atoms; Odor measuring device.

2. 2. The odor measuring device according to claim 1, wherein the silicone resin is contained in an amount of 30 to 100% by weight based on the total weight of the resin.

3. The odor measuring device according to claim 1 , wherein the odorant receiving layer has a porosity x of 12%≦x≦30%, as evaluated based on an SEM image of a cross section of the odorant receiving layer.

4. The odor measuring device according to claim 1 , wherein the odor is detected based on a change in the resistance value of the odorant receiving layer.

5. The odor measuring device according to claim 1 , wherein the filler is a conductive carbon material.

6. The odor measuring device according to claim 5 , wherein the conductive carbon material is carbon black.

7. an electrode having a first metal wiring and a second metal wiring spaced apart from the first metal wiring; An odorant receiving layer in contact with at least a portion of the first metal wiring and at least a portion of the second metal wiring; The odorant receiving layer is a T unit (R １ SiO ３／２ A resin including a silicone resin, a filler, and a surfactant, The R １ is a monovalent hydrocarbon radical having 1 to 10 carbon atoms; Sensor element.

8. A slurry preparation step of preparing a slurry; an electrode arranging step of arranging an electrode having a first metal wiring and a second metal wiring spaced apart from the first metal wiring on a substrate; a coating step of coating the slurry onto a coating region including at least a portion of the first metal wiring and at least a portion of the second metal wiring; A drying step of drying the slurry applied to the application area to form an odorant receiving layer, The slurry is made of T units (R １ SiO ３／２ The silicone resin composition comprises a silicone resin, a filler, and a surfactant, １ is a monovalent hydrocarbon radical having 1 to 10 carbon atoms; A method for manufacturing a sensor element.

9. The method according to claim 8, wherein the silicone resin is contained in an amount of 30 to 100% by weight based on the total weight of the resin.

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