Sensor for evaluating swallowing movements

By combining resistance-changing conductive material with a single-layer structure and deep electrostatic fluid, a porous structure with multiple connection holes is formed, which solves the problems of existing capacity sensor detection accuracy and comfort, and realizes high sensitivity detection and comfortable wearing of slight changes in the throat during swallowing.

JP7663241B2Active Publication Date: 2025-04-16YAMAGATA UNIVERSITY
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Patent Information

Application Number
JP2022088653
Authority / Receiving Office
JP · JP
Patent Type
Patents
Current Assignee / Owner
Filing Date
2022-05-31
Publication Date
2025-04-16
Estimated Expiration
2042-05-31

AI Technical Summary

Technical Problem

The multi-layer structure of the existing capacity sensor results in reduced detection accuracy and poor comfort and long-term wear, making it difficult to accurately evaluate slight changes in the throat during swallowing.

Method used

The resistance-changing conductive material with a single-layer structure is used to form a porous structure with multiple connecting holes through the combination of deep electrostatic fluid and elastic resin material, thereby improving the flexibility and conductivity of the conductive material.

Benefits of technology

It realizes high sensitivity detection of slight changes in the throat during swallowing, improves wearing comfort and reduces the discomfort caused by long-term wearing.

✦ Generated by Eureka AI based on patent content.

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Abstract

To provide a deglutition movement evaluation sensor having high detection sensitivity as a sensor, providing a wearer with excellent comfort when being worn, and capable of greatly reducing discomfort when worn even when worn all the time.SOLUTION: A deglutition movement evaluation sensor 1 for evaluating movement of the larynx due to deglutition movement by a change in a resistance value, the sensor includes a resistance change-type conductive material 11 whose resistance value changes, for example, due to elongation or strain, and electrodes 12 formed at both ends of the resistance change-type conductive material 11 for measuring a resistance value changing due to the elongation or strain. The deglutition movement evaluation sensor is configured to measure the resistance value, with it worn on the body surface around the larynx.SELECTED DRAWING: Figure 1
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Description

[Technical field]

[0001] The present invention relates to a swallowing movement evaluation sensor for evaluating laryngeal movement caused by swallowing movement, and a method for manufacturing the swallowing movement evaluation sensor. [Background technology]

[0002] In recent years, the number of elderly people who die from aspiration pneumonia has been increasing due to the aging of the population, and as a countermeasure, evaluation of the movement of the larynx caused by swallowing has been carried out. Commonly known methods for this include measuring the swallowing sound generated during swallowing and measuring myoelectricity associated with muscle movement during swallowing.

[0003] On the other hand, since the above measurement method is susceptible to the influence of noise, as a technique for grasping the swallowing movement without being influenced by noise, for example, Patent Document 1 below discloses a technique for grasping the movement of the larynx caused by the swallowing movement by using a capacitance type sensor that measures the change in capacitance. Specifically, it describes that a capacitance type sensor is brought into contact with the body surface around the larynx, and the capacitance type sensor is used to measure the change in capacitance caused by the movement of the larynx that occurs when swallowing a food bolus, and the swallowing movement is grasped based on the measurement result.

[0004] The document also describes that the capacitance-type sensor has a sheet-shaped dielectric layer made of an elastomer composition, and a first electrode layer and a second electrode layer made of a conductive composition containing a conductive material and formed to face each other across the dielectric layer, and further describes that the opposing portions of the first electrode layer and the second electrode layer are used as a capacitance detection unit.

[0005] According to the capacitance type sensor described in Patent Document 1 below, the change in capacitance is measured based on the deformation state of the sensor body in the planar direction, so that the movement of the larynx that occurs during swallowing can be grasped without being affected by noise. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2017-119100 A Summary of the Invention [Problem to be solved by the invention]

[0007] However, the capacitance sensor described in Patent Document 1 has a multi-layer (three-layer) structure composed of a first electrode layer, a dielectric layer, and a second electrode layer, and the thickness and hardness of the multi-layer structure hinder accurate evaluation (understanding) of subtle changes in the larynx that occur during swallowing. In addition, the thickness and hardness of the sensor make it difficult to obtain a good fit, and there is room for improvement in terms of comfort when attached to the body surface around the larynx. Another problem is that the sensor is difficult to wear all the time due to the discomfort it causes when worn.

[0008] The present invention has been made in consideration of the above-mentioned problems, and aims to provide a sensor for evaluating swallowing movements that has high detection sensitivity as a sensor, is comfortable to wear, and can significantly reduce discomfort when worn even when worn all the time. [Means for solving the problem]

[0009] The swallowing movement evaluation sensor according to the present invention is a sensor for evaluating the movement of the larynx due to the swallowing movement by a change in resistance value, and includes a resistance-changing conductive material whose resistance value changes with stretching or distortion, and electrodes formed on both ends of the resistance-changing conductive material for measuring the resistance value that changes with stretching or distortion, The resistance variable conductive material has a porous structure in which a large number of pores are connected to each other, The device is characterized by its configuration that allows it to measure resistance values ​​when attached to the body surface around the larynx.

[0010] The swallowing movement evaluation sensor of the present invention may further include a stretchable substrate, which is a substrate having stretchability, and the resistance variable conductive material may be formed on the stretchable substrate, or the resistance variable conductive material may be formed on a peelable support substrate, which is a substrate that has been surface-treated to enable peeling, and then the resistance variable conductive material with the electrodes formed thereon may be peeled off from the peelable support substrate.

[0011] That is, the swallowing movement evaluation sensor according to the present invention has a very simple structure and uses a soft variable resistance conductive material whose resistance value can be measured by stretching or distortion, so that it is easy to obtain a comfortable fit when worn and has excellent followability to the movement of the larynx. Also, since the layer structure is composed only of a layer of variable resistance conductive material 11 (single layer structure), the thickness of the sensor body can be reduced compared to the three-layer structure of conventional capacitance type sensors, and therefore subtle fluctuations of the larynx (fluctuations in resistance value) that occur during swallowing can be accurately measured. thing For these reasons, it is possible to provide a swallowing movement evaluation sensor that has high detection sensitivity as a sensor, is comfortable to wear, and can significantly reduce discomfort when worn even when worn at all times.

[0013] Specifically, a deep eutectic liquid is produced by mixing a hydrogen bond accepting compound and a hydrogen bond donor compound, a base resin insoluble in the deep eutectic liquid is mixed with a curing agent to produce an elastic resin material ink, the deep eutectic liquid, the elastic resin material ink, and a conductive material are mixed to produce a self-phase separating conductive material ink formed by dispersing a mixed gel of the deep eutectic liquid and the conductive material in the resin, the electrodes are printed on the substrate, and further, a sensor portion pattern is printed using the self-phase separating conductive material ink so as to connect the electrodes, the resin in the self-phase separating conductive material ink formed as the sensor portion pattern is cured, and then the deep eutectic liquid in the ink in which the resin has been cured is evaporated to form the resistance variable conductive material having a porous structure in which a large number of pores are connected.

[0014] A layer of the conductive material is then formed on the inner walls of the connected pores, and a conductive path is formed along the inner walls of the pores on which the layer of conductive material is formed.

[0015] That is, according to the present invention, the deep eutectic liquid undergoes phase separation (self-separation) from the resin, and the phase-separated deep eutectic liquid is removed by evaporation to form pores along the inner walls of which a large number of conductive materials are densely packed (a layer of conductive material is formed).The presence of a large number of conductive materials densely packed along the inner walls of the connected pores (porous structure) allows efficient formation of conductive paths along these inner walls.

[0016] In the swallowing movement evaluation sensor according to the present invention, the hydrogen bond accepting compound is preferably benzophenone, the hydrogen bond donating compound is preferably diphenylamine, the resin insoluble in the deep eutectic liquid is preferably a silicone resin, and the conductive material is preferably carbon particles. Furthermore, the silicone resin is preferably polydimethylsiloxane (PDMS).

[0017] In addition, the swallowing movement evaluation sensor according to the present invention is heated at a first temperature at which the deep eutectic liquid does not evaporate, thereby hardening the resin in the self-phase separation conductive material ink, and is further heated at a second temperature higher than the first temperature to evaporate the deep eutectic liquid. According to the present invention, the conductive path can be easily formed by such a heating process.

[0018] Furthermore, the swallowing movement evaluation sensor according to the present invention is provided with an adhesive layer on the surface where it is attached to the body surface around the larynx, allowing the swallowing movement evaluation sensor to be attached directly to the body surface, for example, like a bandage.

[0019] In addition, the swallowing movement evaluation sensor according to the present invention further includes a stretchable substrate, and a plurality of resistance-changing conductive materials are formed in an array on the stretchable substrate, which allows the movement of the larynx to be evaluated simultaneously at a plurality of locations, thereby enabling swallowing movement to be evaluated in more detail.

[0020] The swallowing movement evaluation sensor according to the present invention further includes a measurement circuit for measuring the change in resistance value, and a transmission circuit for wirelessly transmitting the measurement results by the measurement circuit. This allows the receiving side (receiving circuit side) to know the change in resistance value due to stretching or distortion, so that the receiving side can grasp the movement of the larynx due to swallowing movement even from a remote location.

[0021] In addition, in the present invention, a swallowing movement evaluation sensor capable of measuring a resistance value that changes due to stretching or strain when attached to a body surface around the larynx includes, for example, a step of producing a deep eutectic liquid by mixing a hydrogen bond accepting compound and a hydrogen bond donating compound, a step of producing a stretchable resin material ink by mixing a base agent of a resin that is insoluble in the deep eutectic liquid and a hardener, a step of producing a self-phase separation type conductive material ink in which a mixed gel of the deep eutectic liquid and the conductive material is dispersed in a resin by mixing the deep eutectic liquid, the stretchable resin material ink, and a conductive material, and A sensor for evaluating swallowing movement in which the resistance variable conductive material is formed on the stretchable substrate is produced by carrying out the following steps: printing two electrodes for measuring the resistance value on a stretchable substrate, and further printing a sensor portion pattern using the self-phase separating conductive material ink so as to connect the two electrodes; curing the resin in the self-phase separating conductive material ink formed as the sensor portion pattern, and then evaporating the deep eutectic liquid in the ink in which the resin has been cured, thereby forming a resistance variable conductive material having a porous structure in which a large number of pores are connected.

[0022] Furthermore, in the present invention, a swallowing movement evaluation sensor capable of measuring a resistance value that changes due to stretching or distortion when attached to a body surface around the larynx includes, for example, a step of producing a deep eutectic liquid by mixing a hydrogen bond accepting compound and a hydrogen bond donating compound, a step of producing an elastic resin material ink by mixing a base agent of a resin insoluble in the deep eutectic liquid and a hardener, a step of producing a self-phase separation type conductive material ink in which a mixed gel of the deep eutectic liquid and the conductive material is dispersed in resin by mixing the deep eutectic liquid, the elastic resin material ink, and a conductive material, and a peelable support substrate which is a substrate with a surface treatment that allows it to be peeled off. a step of printing two electrodes for measuring the resistance value on the support substrate, and further printing a sensor portion pattern using the self-phase separating conductive material ink so as to connect the two electrodes; a step of hardening the resin in the self-phase separating conductive material ink formed as the sensor portion pattern, and then evaporating the deep eutectic liquid in the ink from which the resin has hardened, thereby forming a resistance variable conductive material having a porous structure in which a large number of pores are connected; and a step of peeling off the resistance variable conductive material together with the electrodes from the peelable support substrate, thereby producing a sensor for evaluating swallowing movement in which the resistance variable conductive material itself serves as the sensor body.

[0023] By carrying out each of the above steps, it is possible to produce a sensor for evaluating swallowing movements that has high detection sensitivity as a sensor, is comfortable to wear, and can significantly reduce discomfort when worn even when worn all the time. Effect of the Invention

[0024] According to the present invention, it is possible to provide a sensor for evaluating swallowing movements that has high detection sensitivity as a sensor, is comfortable to wear, and can significantly reduce discomfort when worn even when worn all the time. [Brief description of the drawings]

[0025] [Figure 1] FIG. 1 is a schematic diagram showing an overview of a swallowing movement evaluation sensor according to the present invention. [Diagram 2]FIG. 2 is a flow chart showing an example of a method for manufacturing a swallowing movement evaluation sensor according to the present invention. [Diagram 3] FIG. 3 is a schematic diagram showing an example of a swallowing movement evaluation sensor according to the present invention. [Figure 4] FIG. 4 is a flow chart showing an example of a method for manufacturing a swallowing movement evaluation sensor according to the present invention. [Diagram 5] FIG. 5 is a diagram illustrating the mechanism of formation of a porous structure. [Figure 6] FIG. 6 is a schematic cross-sectional view showing the difference between a resistance variable conductive material produced by the method for producing a swallowing movement evaluation sensor according to the present invention and a conventional conductive resin. [Figure 7-1] FIG. 7-1 is a schematic diagram showing an example of another swallowing movement evaluation sensor. [Figure 7-2] FIG. 7-2 is a schematic diagram showing an example of pattern printing. [Figure 8] FIG. 8 is a diagram for specifically explaining the method for producing the swallowing movement evaluation sensor of the embodiment. [Figure 9] FIG. 9 is a diagram for specifically explaining the method for producing the swallowing movement evaluating sensor of the embodiment. [Figure 10] FIG. 10 is a diagram showing an example of flexibility of a swallowing movement evaluation sensor. [Figure 11] FIG. 11 is a graph showing the conductivity versus the concentration of a conductive material. [Figure 12] FIG. 12 is a diagram showing the sensitivity of the swallowing movement evaluation sensor produced by the manufacturing method of the example. [Figure 13] FIG. 13 is a diagram showing the evaluation results (sensitivity) of the swallowing movement evaluation sensor produced using a plurality of self-phase separation type conductive material inks. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] Hereinafter, an embodiment of a swallowing movement evaluation sensor according to the present invention will be described in detail with reference to the drawings. However, the present invention is not limited to this embodiment.

[0027] <Summary> 1 is a schematic diagram showing an overview of the swallowing movement evaluation sensor of this embodiment, where (a) is a top view and (b) is an A-A' cross-sectional view. As shown in FIG. 1, the swallowing movement evaluation sensor of this embodiment is a swallowing movement evaluation sensor 1 that is brought into contact with the body surface around the larynx (around the Adam's apple), and includes a resistance-changing conductive material (conductive resin) 11 whose resistance value changes with stretching or distortion, and electrodes 12 formed on both ends of the resistance-changing conductive material 11 to measure the resistance value that changes with stretching or distortion. In a state where the sensor is attached to the body surface around the larynx, the resistance value of the resistance-changing conductive material 11 is measured, and the movement of the larynx due to the swallowing movement is evaluated (grasped) based on the change in resistance value.

[0028] Specifically, the resistance value of the resistance variable conductive material 11 is measured in a state where a measurement circuit (not shown) is connected to the electrodes 12 formed on both ends of the resistance variable conductive material 11. That is, in this embodiment, the main body of the resistance variable conductive material 11 is used as a swallowing movement evaluation sensor for evaluating the movement of the larynx.

[0029] The swallowing movement evaluation sensor 1 of this embodiment may be one in which the resistance-changing conductive material 11 is formed on a stretchable substrate (stretchable substrate) (first embodiment), or one in which the resistance-changing conductive material 11 is formed on a peelable support substrate, which is a substrate with a peelable surface treatment, and then the resistance-changing conductive material 11 on which the electrodes 12 are formed is peeled off from the peelable support substrate (second embodiment). Specifically, the swallowing movement evaluation sensor 1 in the first embodiment is composed of a stretchable substrate, the resistance-changing conductive material 11, and the electrodes 12 on both ends of the material, while the swallowing movement evaluation sensor 1 in the second embodiment is composed of the resistance-changing conductive material 11 and the electrodes 12 on both ends of the material.

[0030] The swallowing movement evaluation sensor 1 of this embodiment is a rectangular sheet-type sensor (shaped like a bandage) that covers the Adam's apple area, and preferably has a longitudinal length in the range of 20 mm to 100 mm and a lateral length in the range of 2 mm to 10 mm. The swallowing movement evaluation sensor 1 may be attached in any direction as long as it can cover the Adam's apple area, and is preferably attached in, for example, a direction parallel to or perpendicular to the swallowing direction.

[0031] As described above, the swallowing movement evaluation sensor 1 of this embodiment has a very simple structure and uses a soft material (resistance-changing conductive material 11) whose resistance value can be measured by stretching or distortion, so that it is easy to obtain a comfortable fit when worn and has excellent followability to the movement of the larynx. In addition, since the layer structure is composed only of a layer of resistance-changing conductive material 11 (single-layer structure), the thickness of the sensor body can be reduced compared to the three-layer structure of conventional capacitance-type sensors, and therefore subtle fluctuations of the larynx (fluctuations in resistance value) that occur during swallowing can be accurately measured. thing For these reasons, the swallowing movement evaluation sensor 1 of this embodiment has high detection sensitivity as a sensor, is comfortable to wear, and can significantly reduce discomfort when worn even when worn at all times.

[0032] <Production of a sensor for evaluating swallowing movements (1)> Fig. 2 is a flow chart showing an example of a method for producing a swallowing movement evaluation sensor of this embodiment (first production method), and here, as an example, the swallowing movement evaluation sensor 1 shown in the above-mentioned first embodiment is produced. Fig. 3(a) is a schematic diagram showing an example of the swallowing movement evaluation sensor 1 produced by the production method shown in Fig. 2.

[0033] In the manufacturing method (first manufacturing method) of the sensor for evaluating swallowing movement of this embodiment, first, a hydrogen bond accepting compound and a hydrogen bond donating compound are mixed to generate a deep eutectic liquid (DEL), which is a pore forming material for forming a porous structure (pores, voids) in the resistance variable conductive material 11 (step S1).

[0034] Next, a base resin insoluble in DEL and a secondary agent (curing agent) are mixed together to produce an elastic resin material ink (step S2).

[0035] Next, the DEL produced in step S1, the elastic resin material ink produced in step S2, and a conductive material are mixed to produce a self-phase-separating conductive material ink 11' in which a mixed gel of the DEL and conductive material is dispersed in the resin (step S3).

[0036] Next, two electrode patterns are printed on the stretchable substrate 13 as extraction electrodes (electrodes 12) (step S4), and further, a sensor portion pattern is printed using the self-phase-separating conductive material ink 11' produced above so as to connect the two electrode patterns (step S5).

[0037] Then, the resin in the self-phase-separating conductive material ink 11' formed as the sensor portion pattern is hardened by pre-annealing (early heating treatment) (step S6), and then the DEL in the ink with the hardened resin is evaporated by post-annealing (later heating treatment) to form a resistance-variable conductive material 11 having a porous structure (step S7), thereby producing a swallowing movement evaluation sensor 1 in which a resistance-variable conductive material 11 is formed on a stretchable substrate 13.

[0038] In this embodiment, the self-phase-separating conductive material ink 11' is generated (step S3) by mixing the DEL generated in step S1, the elastic resin material ink generated in step S2, and the conductive material, but the process of generating the self-phase-separating conductive material ink 11' is not limited to this as long as a mixed gel of the DEL and the conductive material is dispersed in the resin. For example, the order of the processes in steps S1 and S2 may be reversed, or a mixed gel of the DEL and the conductive material may be generated in advance, and then the mixed gel may be mixed with the elastic resin material ink to generate the self-phase-separating conductive material ink 11'.

[0039] In addition, in this embodiment, when the volume resistivity of the resistance variable conductive material 11 is compared with the volume resistivity of the electrode 12, the volume resistivity of the electrode 12 is smaller than that of the resistance variable conductive material 11 by two or more orders of magnitude.

[0040] <Production of a sensor for evaluating swallowing movements (2)> On the other hand, in this embodiment, the resistance change type conductive material 11 itself can be used as the swallowing movement evaluation sensor 1 (the second embodiment described above). Fig. 4 is a flow chart showing an example of a manufacturing method (second manufacturing method) for the swallowing movement evaluation sensor of this embodiment, and here, as an example, the swallowing movement evaluation sensor 1 shown in the second embodiment is manufactured. Fig. 3(b) is a schematic diagram showing an example of the swallowing movement evaluation sensor 1 manufactured by the manufacturing method shown in Fig. 4.

[0041] In FIG. 4, the process of producing the self-phase separating conductive material ink 11' and the processing of steps S5 to S7 are similar to those in the above-mentioned manufacturing method (1) of a swallowing movement evaluation sensor.

[0042] For example, in the second manufacturing method, after producing the above-mentioned self-phase separating conductive material ink 11', two electrode patterns (elastic conductive paste) are printed on a peelable support substrate 13' as extraction electrodes (electrodes 12) (step S4'), and further, a sensor portion pattern is printed using the self-phase separating conductive material ink 11' so as to connect the two electrode patterns (step S5).

[0043] Then, after performing the annealing treatments of steps S6 and S7, in the second manufacturing method, the resistance variable conductive material 11 is peeled off together with the electrode pattern (electrodes 12) from the peelable support substrate 13' (step S8), thereby producing a swallowing movement evaluation sensor 1 in which the resistance variable conductive material 11 itself serves as the sensor body.

[0044] In the second manufacturing method for producing the swallowing movement evaluation sensor 1 of the second embodiment (see FIG. 3(b)), for example, the process of printing an electrode pattern may not be performed in step 4', and after peeling the resistance variable conductive material 11 from the peelable support substrate 13' in step 8, the electrodes 12 may be formed on both ends of the resistance variable conductive material 11. Here, resistance As the electrodes 12 formed on both ends of the change-resistant conductive material 11, for example, thin copper wires or the like may be directly bonded with a conductive adhesive.

[0045] <Detailed Description> The swallowing movement evaluation sensor 1 of this embodiment and a manufacturing method for the swallowing movement evaluation sensor 1 will be described in further detail below.

[0046] <Hydrogen bond donor compound> The hydrogen bond donor compounds (HBD) are compounds having hydrogen atoms involved in hydrogen bonds. Examples of the hydrogen bond donor compounds include diphenylamine, urea, thiourea, 1-methyl urea, 1,3-dimethyl urea, 1,1-dimethyl urea, acetamide, benzamide, ethylene glycol, glycerol, adipic acid, benzoic acid, citric acid, malonic acid, oxalic acid, phenylacetic acid, phenylpropionic acid, succinic acid, tricarballylic acid, and the like. Examples include trifluoroacetamide, MgCl2·6H2O, 2,2,2-trifluoroacetamide, and hexanediol.

[0047] <Hydrogen bond accepting compounds> The hydrogen bond acceptor (HBA) is a compound (salt, etc.) having an unshared electron pair (lone pair) involved in hydrogen bonding. Examples of the hydrogen bond accepting compound include benzophenone, choline chloride (ChCl), methyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, zinc chloride (ZnCl2), N-ethyl-2-hydroxy-N,N-dimethylethanaminium chloride, 2-(chlorocarbonyloxy)-N,N,N-trimethylethanaminium chloride, N-benzyl-2-hydroxy-N,N-dimethylethanaminium, and the like.

[0048] <Creation of deep eutectic liquid> Either or both of the hydrogen bond donor compound and the hydrogen bond acceptor compound usable in this embodiment may be solid at room temperature (e.g., 25°C). In this embodiment, such a hydrogen bond donor compound and a hydrogen bond acceptor compound are mixed in a predetermined ratio (e.g., molar ratio) to cause a eutectic melting point depression, thereby generating a deep eutectic liquid (DEL), which is a compound in a liquid state at room temperature (e.g., 25°C), as a pore forming material for forming a porous structure in the resistance variable conductive material 11. This DEL is also known as a deep eutectic solvent (DES), for example.

[0049] Here, the molar ratio of "hydrogen bond donor compound:hydrogen bond acceptor compound" when mixing the hydrogen bond donor compound and the hydrogen bond acceptor compound is not particularly limited as it depends on the types (combination) of the hydrogen bond donor compound and the hydrogen bond acceptor compound, and examples of the ratio include 1:1, 2:1, 1:2, etc.

[0050] Furthermore, the mixing time (reaction time) when mixing the hydrogen bond donor compound and the hydrogen bond accepting compound is not particularly limited, but is preferably 10 to 30 minutes, and may be, for example, about 15 minutes.

[0051] For example, a deep eutectic solvent may be produced by mixing solid (powdered) diphenylamine as a hydrogen bond donor compound and solid (powdered) benzophenone as a hydrogen bond accepting compound in a molar ratio of 1:1.

[0052] It should be noted that the deep eutectic liquid is not limited to this, and may be one that is generated by mixing another hydrogen bond accepting compound with a hydrogen bond donating compound. Other deep eutectic liquids include, for example, one produced by mixing choline chloride (ChCl) and urea (urea) in a molar ratio of 1:2, one produced by mixing choline chloride (ChCl) and thiourea (thiourea) in a molar ratio of 1:2, one produced by mixing choline chloride (ChCl) and 1-methyl urea (1-methyl urea) in a molar ratio of 1:2, one produced by mixing choline chloride (ChCl) and 1,3-dimethyl urea (1,3-dimethyl urea) in a molar ratio of 1:2, one produced by mixing choline chloride (ChCl) and 1,1-dimethyl urea (1,1-dimethyl urea) in a molar ratio of 1:2, one produced by mixing choline chloride (ChCl) and acetamide (acetamide) in a molar ratio of 1:2, one produced by mixing choline chloride (ChCl) and benzamide (benzamide) in a molar ratio of 1:2, one produced by mixing choline chloride (ChCl) and ethylene glycol (ethylene glycol ... glycol in a molar ratio of 1:2; choline chloride (ChCl) and glycerol; choline chloride (ChCl) and adipic acid in a molar ratio of 1:1; choline chloride (ChCl) and benzoic acid in a molar ratio of 1:1; choline chloride (ChCl) and citric acid in a molar ratio of 1:1; choline chloride (ChCl) and malonic acid in a molar ratio of 1:1; choline chloride (ChCl) and oxalic acid in a molar ratio of 1:1; choline chloride (ChCl) and phenylacetic acid in a molar ratio of 1:1; choline chloride (ChCl) and phenylpropionic acid in a molar ratio of 1:1. Choline chloride (ChCl) and succinic acid (succinic acid) are mixed in a molar ratio of 1:1.one produced by mixing choline chloride (ChCl) and tricarballylic acid in a 1:1 molar ratio, one produced by mixing choline chloride (ChCl) and MgCl2·6H2O in a 1:1 molar ratio, one produced by mixing methyltriphenylphosphonium bromide and glycerol, one produced by mixing methyltriphenylphosphonium bromide and ethylene glycol, one produced by mixing methyltriphenylphosphonium bromide and 2,2,2-trifluoroacetamide, one produced by mixing benzyltriphenylphosphonium chloride and glycerol, one produced by mixing benzyltriphenylphosphonium chloride and ethylene glycol Examples of the hydrogen bond donor compound include a hydrogen bond acceptor compound and a hydrogen bond donor compound. Examples of the hydrogen bond acceptor compound include a hydrogen bond donor compound and a hydrogen bond donor compound. Examples of the hydrogen bond acceptor compound include a hydrogen bond donor compound and a hydrogen bond donor compound. Examples of the hydrogen bond acceptor compound include a hydrogen bond donor compound and a hydrogen bond donor compound. Examples of the hydrogen bond acceptor compound include a hydrogen bond donor compound and a hydrogen bond donor compound. Examples of the hydrogen bond acceptor compound include a hydrogen bond donor compound and a hydrogen bond donor compound. Examples of the hydrogen bond acceptor compound include a hydrogen bond donor compound and a hydrogen bond donor compound. Examples of the hydrogen bond acceptor compound include a hydrogen bond donor compound and a hydrogen bond donor compound. Examples of the hydrogen bond acceptor compound include a hydrogen bond donor compound and a hydrogen bond donor compound. Examples of the hydrogen bond acceptor compound include a hydrogen bond donor compound and a hydrogen bond donor compound. Examples of the hydrogen bond acceptor compound include a hydrogen bond donor compound and a hydrogen bond donor compound. Examples of the hydrogen bond don ...

[0053] The deep eutectic liquid (DEL) of this embodiment preferably has a boiling point higher than the curing temperature of the resin (resin insoluble in the deep eutectic liquid) added to this deep eutectic liquid and lower than the heat resistance temperature of this resin. In this embodiment, the heat resistance temperature of the resin is not only a temperature at which the cured resin maintains its shape without being damaged, such as by decomposition or embrittlement, but may also include a temperature at which the cured resin remains partially even if it is accompanied by some deformation due to softening. For example, when this resin is polydimethylsiloxane (PDMS), the DEL preferably has a boiling point of 60°C to 150°C, and particularly preferably has a boiling point of 80°C to 150°C.

[0054] <Production of elastic resin material ink> In this embodiment, the resin material (elastic resin material ink) to be added (mixed) to the deep eutectic liquid is not particularly limited as long as it is a resin that is insoluble in the deep eutectic liquid, and examples of such resin include silicone-based resins, aromatic polyester biodegradable plastics (for example, BASF's product name: Ecoflex (registered trademark), etc.), ABS resins, polyethylene (PE), polyvinylidene fluoride (PVDF), etc.

[0055] Examples of silicone resins include polydimethylsiloxane (PDMS), polyphenylmethylsiloxane (PMPS), and polydiphenylsiloxane (PDPS).

[0056] Among silicone resins, PDMS can be preferably used. PDMS is produced by a crosslinking reaction between a siloxane oligomer (base material) and a siloxane crosslinking agent (curing agent). This crosslinking reaction may be, for example, a reaction in which chloroplatinic acid (H2PtCl6) is used as a catalyst and the materials are mixed at 80°C for 1 hour.

[0057] The resins insoluble in these deep eutectic liquids may be any type that can be hardened by any method, such as a thermosetting resin that is hardened by heat, an ultraviolet-curable resin that is hardened by exposure to ultraviolet (UV) rays, or an electron-beam-curable resin that is hardened by exposure to electron beams.

[0058] <Creation of self-phase-separating conductive ink> In this embodiment, the above-mentioned DEL and elastic resin material ink (PDMS) are mixed with a conductive material and stirred to produce a self-phase separation type conductive material ink 11'.

[0059] The conductive material is not particularly limited, but for example, carbon-based particles such as carbon black (CB), graphite (GF), carbon nanotubes (CNT), carbon nanofibers (CNF), carbon nanowires (CNW), carbon fibers, and graphite are preferably used, and two or more of these may be included.

[0060] The conductive material may be metal particles made of metals such as gold, silver, copper, chromium, titanium, platinum, nickel, tin, zinc, lead, tungsten, iron, aluminum, etc., particles made of compounds containing these metals, particles made of conductive resin, composite particles such as particles made of resin coated with a conductive metal such as electroless nickel, etc., or metal nanowires (MNWs), metal fibers, etc.

[0061] For example, when DEL is mixed with an elastic resin material ink (PDMS) and a conductive material, the DEL undergoes phase separation (self-separation) from the resin, and a gel (gel droplets) of the DEL and conductive material is dispersed in the resin. In this way, a self-phase-separating conductive material ink 11' is produced in which gel droplets are dispersed in the resin. The self-phase-separating conductive material ink 11' is a black, opaque composite ink.

[0062] <Printing electrodes> In this embodiment, two electrode patterns (stretchable conductive paste) are screen-printed as extraction electrodes (electrodes 12) on the above-mentioned stretchable substrate 13 or peelable support substrate 13'. As the conductive paste, it is preferable to use, for example, silver (Ag) paste.

[0063] The material of the stretchable substrate 13 is preferably PDMS as described above, but is not limited thereto and may be other materials such as PEN (Polyethylene Naphthalate), Pl (Polyimide), PET (Polyethylene Terephthalate), PC (Polycarbonate), PU (Polyurethane), paper, cloth, etc. Also, as the peelable support substrate 13', a fluorine-modified glass substrate, a polyimide substrate (Upilex (manufactured by UBE)), etc. can be used.

[0064] In this embodiment, a silver paste is used as the conductive paste, but the present invention is not limited to this, and any conductive paste having elasticity, such as a copper paste or a carbon paste, can be used. As described above, the electrodes 12 are preferably printed by screen printing, but any printing method can be used as long as the electrodes 12 can be printed on the elastic substrate 13 or the peelable support substrate 13'.

[0065] <Formation of a layer of self-phase-separating conductive material ink> In this embodiment, for example, a sensor part pattern is printed using a self-phase-separating conductive material ink 11' by a printing method such as screen printing so as to connect two electrode patterns, thereby forming a layer (sensor part pattern) of the self-phase-separating conductive material ink 11' on the stretchable substrate 13 or the peelable support substrate 13'.

[0066] Fig. 5(a) is a schematic cross-sectional view in the thickness direction of a layer (sensor part pattern) of a self-phase-separating conductive material ink 11' printed on a stretchable substrate 13 or a peelable support substrate 13'. As shown in Fig. 5(a), in the layer of the self-phase-separating conductive material ink 11', DEL (e.g., DEL obtained by a mixed reaction of diphenylamine and benzophenone) phase-separates (self-separates) from a resin 21 (e.g., PDMS) that is insoluble in DEL, and thus a gel (gel droplets 22) in which DEL and a conductive material (e.g., CB) are mixed and present in the resin 21 in a dispersed state.

[0067] The formation of the layer of the self-phase-separating conductive material ink 11' is not limited to the above-mentioned screen printing, but may be formed by other forming methods, such as bar coating, spin coating, dip coating, or other coating methods, injection molding, etc. Such layer forming methods are used as techniques excellent in terms of mass productivity, large area, and patterning.

[0068] <Pre-annealing> In this embodiment, pre-annealing (pre-heating treatment) is performed on the layer of the self-phase-separating conductive material ink 11' printed on the stretchable substrate 13 or the peelable support substrate 13'. The temperature during pre-annealing is preferably a temperature at which the resin (thermosetting resin) 21 insoluble in DEL is cured and at which the DEL does not volatilize. For example, when DEL obtained by a mixed reaction of diphenylamine and benzophenone is used as the DEL and PDMS is used as the resin 21 insoluble in DEL, the pre-annealing temperature is preferably 60°C to 90°C, which is the temperature at which the PDMS starts to cure, and the pre-annealing time is preferably 30 minutes to 120 minutes. When PDMS is used, for example, the pre-annealing temperature may be 75°C and the pre-annealing time may be 60 minutes.

[0069] FIG. 5(b) shows a schematic cross-sectional view in the thickness direction of a layer of self-phase separation type conductive material ink 11″ that has been pre-annealed. In the layer of self-phase separation type conductive material ink 11″ that has been pre-annealed, the resin 21 that is insoluble in DEL is in a state where it has been hardened by pre-annealing (hardened resin 23). The layer of self-phase separation type conductive material ink 11″ that has been pre-annealed has a connected structure in which gel droplets 22 are connected to each other in the hardened resin 23.

[0070] If the resin 21 insoluble in DEL is not a thermosetting resin but is, for example, an ultraviolet curable resin, the ultraviolet curable resin may be cured by irradiation with ultraviolet rays instead of the pre-annealing. Similarly, if the resin 21 insoluble in DEL is, for example, an electron beam curable resin, the electron beam curable resin may be cured by irradiation with electron beams instead of the pre-annealing.

[0071] <Post-annealing> In this embodiment, post-annealing (later heat treatment) is performed on the layer of self-phase separation type conductive material ink 11'' that has been pre-annealed and cured. For example, when a DEL obtained by a mixed reaction of diphenylamine and benzophenone is used as the DEL and PDMS is used as the resin 21 that is insoluble in DEL, the post-annealing temperature is preferably 120°C to 150°C and the post-annealing time is preferably 30 minutes to 120 minutes. When PDMS is used, for example, the post-annealing temperature may be 140°C and the post-annealing time may be 30 minutes.

[0072] FIG. 5(c) shows a schematic cross-sectional view in the thickness direction of a layer of the self-phase-separating conductive material ink 11''' (i.e., the resistance-changing conductive material 11) that has been subjected to post-annealing. When post-annealing is performed, most of the DEL in the resistance-changing conductive material 11 is evaporated and removed. As a result, a porous structure in which a large number of pores 24 corresponding to the shape of the gel droplets 22 are connected to each other is formed in the resistance-changing conductive material 11. In addition, a large number of conductive materials 25 are densely present along the inner walls of the pores 24 in the resistance-changing conductive material 11. That is, a layer of the conductive material 25 is formed along the inner walls of the pores 24. Then, as shown in FIG. 5(c), the resistance-changing conductive material 11 has voids 26 surrounded by the densely present conductive materials 25. Since a large number of conductive materials 25 are densely present along the inner walls of the connected pores 24 (porous structure), an efficient conductive path (conductive path) can be formed along the inner walls. That is, by the mechanism of forming the porous structure shown in FIG. 5, it is possible to fabricate the resistance variable conductive material 11 having a porous structure in which efficient conductive paths are formed.

[0073] The residual rate (%) of the DEL in the resistance variable conductive material 11 is defined as follows. Survival rate N(%)= ((DEL volume (ml) in the “layer of self-phase-separating conductive material ink 11” before post-annealing)-DEL volume (ml) evaporated by post-annealing) / DEL volume (ml) in the "layer of self-phase-separating conductive material ink 11'' before post-annealing) ×100

[0074] It is preferable that the residual rate N is 5% or less in the resistance variable conductive material 11. When the residual rate N of DEL is 5% or less, it is possible to form a resistance variable conductive material 11 having a high-quality porous structure, specifically, a resistance variable conductive material 11 having a porous structure in which stability is sufficiently ensured and the generation of outgassing due to DEL is suppressed to a level that does not adversely affect others.

[0075] In addition, the thickness of the resistance variable conductive material 11 produced by the manufacturing method of this embodiment is not particularly limited, but is preferably 20 μm to 2 mm, and may be about 100 μm as a specific example. The size (pore diameter) of each pore 24 is not particularly limited, but is preferably 1 μm to 500 μm in length, and more preferably 5 μm to 500 μm in length. The size (particle diameter) of the conductive material added in this manufacturing method is preferably 20 nm to 20 μm, for example.

[0076] In the resistance variable conductive material 11 produced by the manufacturing method of this embodiment, the porosity P is expressed as the total volume (apparent volume) of the resistance variable conductive material 11 V (μm 3 ), and the volume of the void is v (μm 3 ), it is defined as follows: Porosity P(%)=(v / V)×100

[0077] In the resistance variable conductive material 11, the porosity P is preferably 10% to 90%, and particularly preferably 30% to 60%.

[0078] Moreover, the extension rate U when the resistance variable conductive material 11 of this embodiment is extended is defined as follows, where M0 is the length before extension and M is the length after extension. Elongation rate U(%)=((M-M0) / M0)×100

[0079] In addition, in the manufacturing method of this embodiment, the self-phase-separating conductive material ink 11' can be produced by a simple operation such as mixing materials, and the resistance variable conductive material 11 having a porous structure can be produced by a simple operation of printing this ink and performing two-stage annealing. Therefore, according to this embodiment, it is possible to suppress an increase in manufacturing costs when manufacturing the resistance variable conductive material 11, that is, when manufacturing the swallowing movement evaluation sensor 1.

[0080] Furthermore, since the self-phase-separating conductive material ink 11′ produced in this embodiment can be printed, it is possible to realize a large area of ​​the resistance variable conductive material 11 by using a printing technique such as screen printing, and furthermore, it is possible to easily form any desired pattern.

[0081] <Comparison> 6 is a schematic cross-sectional view showing the difference between the resistance variable conductive material 11 produced by the production method of this embodiment and a conventional conductive resin, where (a) is a schematic cross-sectional view in the thickness direction of the resistance variable conductive material 11, and (b) is a schematic cross-sectional view in the thickness direction of the conventional conductive resin 101. Note that the conventional conductive resin 101 is produced by mixing a conductive material (e.g., CB or GF) with a resin (e.g., PDMS) and then heating the mixture without using DEL.

[0082] The resistance variable conductive material 11 has various advantages over the conventional conductive resin 101. For example, as shown in FIG. 6(a), the resistance variable conductive material 11 has voids 26, and a porous structure in which a large number of pores 24 are connected in a hardened resin 23 is formed. A large number of conductive materials 25 are densely present along the inner walls of the pores 24, forming a conductive path (conductive path) as shown by the arrow T1 in FIG. 6(a). That is, in the manufacturing method of this embodiment, the DEL phase-separates (self-separates) from the resin, and the liquid particles of the phase-separated DEL are removed by evaporation to form a conductive path (a self-separating conductive path along the porous structure). Usually, it is difficult to obtain such a self-separating conductive path using a conductive material, and a complicated process is required, but in this embodiment, such a self-separating conductive path can be easily formed.

[0083] 6(b), for example, conventional conductive resin 101 has no voids and conductive materials are randomly present in the resin, so that contact points between conductive materials form conductive paths as shown by arrows T2. In other words, the conductive resin 101 has limited conductive paths and is inefficient.

[0084] Moreover, the resistance variable conductive material 11 can have a lower percolation threshold value than the conventional conductive resin 101. From this point of view, in order for a sensor using the conductive resin 101 to obtain the same sensitivity as the swallowing movement evaluation sensor 1 of this embodiment, a large amount of conductive material must be contained in the conductive resin 101. That is, the swallowing movement evaluation sensor 1 of this embodiment can obtain good sensitivity with a smaller amount of conductive material than the sensor using the conductive resin 101, and therefore, an increase in manufacturing costs can be suppressed.

[0085] <Effects> As described above, the swallowing movement evaluation sensor 1 of this embodiment is a sensor for evaluating the movement of the larynx due to the swallowing movement by a change in resistance value, and includes, for example, a resistance-changing conductive material 11 whose resistance value changes with stretching or distortion, and electrodes 12 formed on both ends of the resistance-changing conductive material 11 to measure the resistance value that changes with stretching or distortion, and is configured to be able to measure the above resistance value when attached to the body surface around the larynx.

[0086] As described above, the swallowing movement evaluation sensor 1 of this embodiment has a very simple structure and uses a soft material (resistance-changing conductive material 11) whose resistance value can be measured by stretching or distortion, so that it is easy to obtain a comfortable fit when worn and has excellent followability to the movement of the larynx. In addition, since the layer structure is composed of one layer of resistance-changing conductive material 11 (single-layer structure), the thickness of the sensor body can be reduced compared to the three-layer structure of conventional capacitance-type sensors, and therefore subtle fluctuations of the larynx (fluctuations in resistance value) that occur during swallowing can be accurately measured. thing For these reasons, the swallowing movement evaluation sensor 1 of this embodiment has high detection sensitivity as a sensor, is comfortable to wear, and can significantly reduce discomfort when worn even when worn at all times.

[0087] In addition, by applying a gel-like adhesive to the surface of the swallowing movement evaluation sensor 1 to be attached to the body surface around the larynx in advance (providing an adhesive layer), the swallowing movement evaluation sensor 1 can be attached directly to the body surface, for example, like a bandage. In addition, when using a film-like adhesive (adhesive film) such as adhesive film Yuhada Permiroll (manufactured by Nitto Denko), the adhesive film (back side of the adhesive surface) may be attached to the surface of the swallowing movement evaluation sensor 1 to be attached to the body surface, or the swallowing movement evaluation sensor 1 may be formed on the adhesive film (back side of the adhesive surface). In this way, by providing an adhesive layer on the swallowing movement evaluation sensor 1, a swallowing movement evaluation sensor with excellent comfort that does not cause discomfort when worn can be obtained.

[0088] <Other embodiment (1)> In addition, as another embodiment applying the above embodiment, for example, the movement of the larynx may be simultaneously evaluated at a plurality of locations on the body surface around the larynx. Fig. 7-1 is a schematic diagram showing an example of another swallowing movement evaluation sensor applying the above swallowing movement evaluation sensor 1. In Fig. 7-1, the swallowing movement evaluation sensor 1' of this embodiment has a plurality of swallowing movement evaluation sensors 1, each of which is composed of an elastic substrate 13, a resistance-changing conductive material 11, and electrodes 12 at both ends thereof, arranged in an array.

[0089] The swallowing movement evaluation sensor 1' is fabricated as follows. For example, the steps (steps S4 and S5) of printing the electrode pattern and the sensor part pattern shown in FIG. 2 are performed multiple times to form a combined print pattern of a plurality of electrode patterns (electrodes 12) and a sensor part pattern (layer of self-phase separation type conductive material ink 11') in an array on the stretchable substrate 13. Then, the layer of self-phase separation type conductive material ink 11' formed in an array is subjected to pre-annealing (step S6) and post-annealing (step S7) shown in FIG. 2. This makes it possible to obtain a swallowing movement evaluation sensor 1' in which a plurality of swallowing movement evaluation sensors 1 (resistance change type conductive material 11) are formed in an array on the stretchable substrate 13. The other manufacturing methods are the same as those shown in FIG. 2. The number of the swallowing movement evaluation sensors 1 (resistance change type conductive material 11) arranged in an array is not limited to five as shown in FIG. 7-1, and may be any number as long as they are arranged in a range that covers the Adam's apple.

[0090] According to the swallowing movement evaluation sensor 1' shown in FIG. 7-1, the movement of the larynx can be evaluated simultaneously at a plurality of locations, so that the swallowing movement can be evaluated in more detail.

[0091] In this embodiment, the swallowing movement evaluation sensor 1' in which a plurality of swallowing movement evaluation sensors 1 are formed in an array on the stretchable substrate 13 is generated by performing the processes of steps S4 and S5 multiple times, but this is not limited to the above method. For example, as shown in Fig. 7-2, a stencil mask (screen mask) having the shapes of a plurality of sensor unit patterns or a stencil mask having the shapes of a plurality of electrode patterns may be used to perform screen printing for each pattern at once. This allows the swallowing movement evaluation sensor 1' in which a plurality of swallowing movement evaluation sensors 1 are formed in an array on the stretchable substrate 13 to be easily obtained in a short operation time.

[0092] <Other embodiment (2)> The swallowing movement evaluation sensor 1 and the swallowing movement evaluation sensor 1' may further include a measurement circuit for measuring the change in resistance value and a transmission circuit for wirelessly transmitting the measurement result. The measurement circuit may be configured, for example, as a general bridge circuit, in which case the change in resistance value is measured by replacing it with a change in voltage. The transmission method of the transmission circuit is preferably a known wireless communication method such as short-distance wireless communication BLE (Bluetooth Low Energy), NFC (Near Field Communication), wireless LAN (WI-FI), infrared communication, etc., and the transmission circuit transmits the measurement result by the measurement circuit to the outside by wireless communication.

[0093] This allows the receiving side (receiving circuit side) to know the change in resistance due to stretching or distortion, so that, for example, the movement of the larynx caused by swallowing can be grasped remotely at the receiving side. In other words, the movement of the larynx in daily life, including when eating and sleeping, can be continuously evaluated remotely. EXAMPLES

[0094] Next, examples of the swallowing movement evaluation sensor according to the present invention will be described, but the present invention is not limited to the following examples.

[0095] <1. Swallowing movement evaluation sensor of this embodiment> 8 and 9 are diagrams for specifically explaining the manufacturing method of the swallowing movement evaluation sensor of this embodiment. In this manufacturing method, benzophenone (manufactured by Tokyo Chemical Industry Co., Ltd.) (see formula (1) in FIG. 8) that is solid (powdered) at room temperature (about 25° C.) was prepared as the hydrogen bond accepting compound. In addition, diphenylamine (manufactured by Tokyo Chemical Industry Co., Ltd.) (see formula (2) in FIG. 8) that is solid (powdered) at room temperature (25° C.) was prepared as the hydrogen bond donating compound.

[0096] 8, benzophenone 31 and diphenylamine 32 were placed in a transparent container at room temperature (about 25° C.) in a molar ratio of 1:1, and the container was sealed with a lid. In the container, at a contact portion 33 between benzophenone 31 and diphenylamine 32, a reaction between the two proceeded.

[0097] Next, benzophenone 31 and diphenylamine 32 were heated at 90°C for 1 h to generate deep eutectic liquid (DEL) 34. This DEL 34 was a yellow transparent liquid. Note that heating at 90°C for 1 h is not essential, and the same liquid can be obtained by leaving it at room temperature (e.g., 25°C) for a long time.

[0098] Next, the main agent (siloxane oligomer) of polydimethylsiloxane (PDMS: manufactured by Dow Toray) and the secondary agent (curing agent: siloxane crosslinking agent) were poured into another transparent container in a ratio of 15:1, and the mixture was stirred using a rotation / revolution stirrer to produce elastic resin material ink 35.

[0099] Next, DEL 34, elastic resin material ink 35, and conductive material (carbon black (CB): Ketjen black, manufactured by Lion Specialty Chemicals) 36 were placed in a transparent container for ink production in a mass ratio of 1:1:0.04 (the ratio of SSCC-1 described later), and stirred for 10 minutes with a rotation / revolution stirrer to produce a black opaque self-phase separation type conductive material ink 37. The particle size of the carbon black (CB) 36 used was approximately 34 nm.

[0100] Next, a screen printer and a stretchable substrate (PDMS substrate) 41 were prepared, and two electrode patterns 42 were screen-printed on the PDMS substrate 41 using a conductive paste (see FIG. 9(a)). A stretchable silver (Ag) paste was used as the conductive paste.

[0101] Next, using the same screen printer and the self-phase separating conductive material ink 37 produced above, a sensor part pattern 43 (a layer of the self-phase separating conductive material ink 37) was screen printed on the PDMS substrate 41 so as to connect the two electrode patterns 42 (see FIG. 9(c)). Specifically, a stencil mask having the shape of the sensor part pattern 43 was placed on the PDMS substrate 41, and the self-phase separating conductive material ink 37 was applied therefrom with a squeegee (see FIG. 9(b)). As a result, the sensor part pattern 43, which is a layer of the self-phase separating conductive material ink 37, was formed so as to connect the two electrode patterns 42.

[0102] Next, a two-stage annealing process (pre-annealing and post-annealing) was performed on the sensor portion pattern 43 (layer of self-phase-separating conductive material ink 37) to produce a swallowing movement evaluation sensor 45 having two electrode patterns 42 and a resistance-changing conductive material 44 having a porous structure on a PDMS substrate 41.

[0103] Here, the two-stage annealing (pre-annealing and post-annealing) will be described. First, the sensor part pattern 43 printed on the PDMS substrate 41 was pre-annealed at 75° C. for 1 hour using a hot plate. In the sensor part pattern 43 that had been pre-annealed, the PDMS in the self-phase separation type conductive material ink 37 was cured.

[0104] After that, the sensor part pattern 43 that had been subjected to the pre-annealing was subjected to post-annealing at 140° C. for 30 minutes. The DEL in the hardened PDMS was evaporated and removed by the post-annealing, and a resistance-changing conductive material 44 having a porous structure was produced. In this way, a swallowing movement evaluation sensor 45 was produced in which the resistance-changing conductive material 44 was formed on the PDMS substrate 41 (see FIG. 9(c)).

[0105] The above manufacturing method resulted in a swallowing movement evaluation sensor 45 that has a very simple structure and excellent flexibility in terms of "stretching," "bending," "twisting," etc., as shown in Figure 10.

[0106] <2. Conventional conductive resin> The conventional conductive resin uses CB particles as the conductive material, and was produced by directly mixing the CB particles as the conductive material into PDMS (elastic resin material ink) without using DEL, and then heating it. The conventional conductive resin produced in this way does not have voids based on a self-phase separation structure, and the CB particles are randomly dispersed in the PDMS, as shown in Figure 6(b).

[0107] <3. Conductivity versus concentration of conductive materials> In the manufacturing method of the swallowing movement evaluation sensor of this embodiment, the weight of PDMS was not changed, but the concentration (wt%) of carbon black (CB) relative to PDMS was changed to produce multiple (four here) swallowing movement evaluation sensors, and the conductivity (S / cm) of each swallowing movement evaluation sensor was measured. Figure 11 is a diagram showing the conductivity versus the concentration of the conductive material (CB), and the measurement results for the above four swallowing movement evaluation sensors are plotted in black circles (see "with DEL" in Figure 11). Note that a measuring device "Keithley Model DMM6500" was used to measure all the conductivity shown in Figure 11.

[0108] On the other hand, in the conventional conductive resin manufacturing method, we produced several conductive resins by changing the concentration (wt%) of carbon black (CB) relative to PDMS without changing the weight of PDMS, and measured the conductivity (S / cm) of each conductive resin. These measurement results are shown in the black square plots in Figure 11 (see "without DEL" in Figure 11).

[0109] As shown in Fig. 11, the swallowing movement evaluation sensor produced by the manufacturing method of this example had a high conductivity even with a low CB concentration. On the other hand, the conductive resin produced by the conventional manufacturing method required a significantly higher CB concentration to obtain the same level of conductivity as in this example.

[0110] From the above, it was found that the swallowing movement evaluation sensor manufactured by the manufacturing method of the present invention can achieve high conductivity with a smaller amount of conductive material than the conductive resin manufactured by the conventional manufacturing method.

[0111] <4. Sensitivity to elongation rate> FIG. 12 is a diagram showing the sensitivity of the swallowing movement evaluation sensor 45 (see FIG. 8 and FIG. 9) manufactured by the manufacturing method of this embodiment, where (a) shows the state of 0% elongation rate (upper side of FIG. 12) and the state of 100% elongation rate (lower side of FIG. 12), and (b) shows the electrical resistance change rate (sensitivity): R / R0 (%) with respect to the elongation rate (%). In FIG. 12(b), line n-1 shows the electrical resistance change rate: R / R0 (%) when the elongation rate (%) is increased for the swallowing movement evaluation sensor 45 as shown by the arrow t-1. Also, line n-2 shows the electrical resistance change rate: R / R0 (%) when the elongation rate (%) is decreased for the swallowing movement evaluation sensor 45 as shown by the arrow t-2. Here, R0 is the resistance value before stretching, and R is the difference between the resistance value before stretching and the resistance value after stretching.

[0112] As described above for the elongation rate U, the elongation rate (%) is defined as follows, where the length (in the elongation direction) before elongation is M0 and the length (in the elongation direction) after elongation is M: Elongation rate U(%)=((M-M0) / M0)×100

[0113] As the extension rate (%) of the swallowing movement evaluation sensor 45 increased, the electrical resistance change rate: R / R0 (%) smoothly increased as shown in n-1. As the extension rate (%) of the swallowing movement evaluation sensor 45 decreased, the electrical resistance change rate: R / R0 (%) smoothly decreased as shown in n-2. Furthermore, when the extension rate (%) increased and decreased, the electrical resistance change rate: R / R0 (%) was approximately the same, and it was found that the hysteresis was small. From the above, it can be seen that the swallowing movement evaluation sensor 45 exhibits good sensitivity and responsiveness to extension and contraction.

[0114] <5. Differences in sensitivity due to the composition of self-phase-separating conductive material ink> Regarding the swallowing movement evaluation sensor 45 produced by the manufacturing method of the present invention, multiple swallowing movement evaluation sensors were produced by changing the ratio of deep eutectic liquid (DEL), polydimethylsiloxane (PDMS), and conductive material (CB) when producing the self-phase separating conductive material ink, and their sensitivity was evaluated.

[0115] Fig. 13 is a diagram showing the evaluation results (sensitivity) of swallowing movement evaluation sensors made with multiple self-phase separation type conductive material inks. In Fig. 13, the ink SSCC-1 is self-phase separation type conductive material ink 37 produced by the above-mentioned production method, and the other self-phase separation type conductive material inks were produced in proportions of SSCC-2 to SSCC-7, and the sensitivity of the swallowing movement evaluation sensors made with each ink was evaluated.

[0116] As a result of the verification, the sensitivity of the swallowing movement evaluation sensor 45 made with the ink of SSCC-1 (self-phase separation type conductive material ink 37) was the best among all the sensors (sensitivity shown in FIG. 13: ◎). The sensitivity of the swallowing movement evaluation sensors made with the inks of SSCC-2 to SSCC-5 was lower than that of the swallowing movement evaluation sensor 45 (◎), but was still good (sensitivity shown in FIG. 13: ◯). The sensitivity of the swallowing movement evaluation sensor made with the ink of SSCC-6 was even lower, but was within the acceptable range (sensitivity shown in FIG. 13: △). The swallowing movement evaluation sensor made with the ink of SSCC-7 could not obtain the desired sensitivity due to poor film condition. That is, it is preferable that the ratio of DEL to PDMS and CB is in the range of 0.5 to 2.0 for PDMS:1, and the ratio of CB to DEL is in the range of more than 0.02 and not more than 0.08. Specifically, it was found that the higher the DEL, the higher the porosity, which tends to make the membrane of the swallowing movement evaluation sensor more fragile (brittle), but it was also found that this tendency can be adjusted by the amount of CB. For example, increasing the amount of CB increases the amount of carbon attached to the inner walls of the pores, mitigating fragility. On the other hand, even with a small amount of CB, high sensitivity can be obtained by adjusting the amount of DEL. [Explanation of symbols]

[0117] 1,1',45 Sensor for evaluating swallowing movements 11 Resistance-changing conductive material (conductive resin) 11',11'',11''' Self-phase-separating conductive material ink 12 electrodes 13 Stretchable substrate 13' Peelable support substrate 21,23 Resin 22 Gel Drops 24 Pore 25 Conductive Materials 26 void 31 Benzophenone 32 Diphenylamine 33 Contact part 34 Deep eutectic liquid (DEL) 35 Elastic resin material ink 36 Conductive materials (Carbon black (CB)) 37 Self-phase-separating conductive material ink 41 Stretchable substrate (PDMS substrate) 42 Electrode Pattern 43 Sensor part pattern 44 Resistive conductive materials 101 Conductive resin

Claims

1. A swallowing movement evaluation sensor for evaluating a movement of the larynx due to a swallowing movement based on a change in resistance value, A resistance variable conductive material whose resistance value changes due to elongation or distortion; Electrodes formed on both ends of the resistance variable conductive material in order to measure a resistance value that changes due to elongation or strain; Including, The resistance variable conductive material has a porous structure in which a large number of pores are connected to each other, The resistance value can be measured in a state where the device is attached to a body surface around the larynx. A sensor for evaluating swallowing movements.

2. A stretchable substrate, which is a substrate having stretchability; Further comprising: forming the resistance variable conductive material on the stretchable substrate; The swallowing movement evaluation sensor according to claim 1 .

3. forming the resistance variable conductive material on a peelable support substrate which is a substrate that has been surface-treated to be peelable, and then peeling the resistance variable conductive material having the electrodes formed thereon from the peelable support substrate; The swallowing movement evaluation sensor according to claim 1 .

4. A stretchable substrate, which is a substrate having stretchability; Further comprising: A plurality of the resistance variable conductive materials are formed in an array on the stretchable substrate; The swallowing movement evaluation sensor according to claim 1 .

5. A layer of adhesive is provided on the surface of the body around the larynx.

4. The swallowing movement evaluation sensor according to claim 2 or 3.

6. a measurement circuit for measuring the change in resistance; a transmitting circuit for wirelessly transmitting a measurement result by the measuring circuit; Further comprising:

5. The swallowing movement evaluation sensor according to claim 2, 3 or 4.

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