JP2019218676A - Conductive material and electrical element and sensor having the same - Google Patents

Abstract

To provide a conductive material having excellent safety and conductivity and being inexpensive.SOLUTION: The problem can be solved by providing a conductive material having PEDOT-pTS or PEDOT-PSS attached to the surface of a base material containing paper. The conductive material can be used as a force sensing element, a separation operation discriminating element, and the like, and can be further used as a sensor using these elements.SELECTED DRAWING: None

Description

  The present invention relates to a conductive material, an electric element including the same, and a sensor including the element. More specifically, the present invention relates to a conductive material using paper as a base material, and to the electric element and the sensor. The electrical element and the sensor are, in particular, a haptic element and a haptic sensor whose electric characteristic values fluctuate when energized due to an external force, and a separation operation that is an element that identifies movement in a non-contact state based on the fluctuation of the electric characteristic value. It can be used as an identification element and a separation operation identification sensor.

  It is known that PEDOT-pTS (poly (3,4-ethylene-dioxythiophene) -p-toluenesulfonate) has high conductive performance among conductive polymers. On the other hand, the types of base materials to which PEDOT-pTS can be attached are limited. The present inventors have made an invention using silk as a substrate to which PEDOT-pTS is adhered, and have already applied for patents (Patent Documents 1 and 2).

  PEDOT-PSS (Poly (3,4-ethylenedioxythiophene) -polystyrenesulfonate) is also known as a conductive polymer having predetermined performance (Patent Documents 3 and 4).

WO2016 / 148249 International publication pamphlet WO2016 / 031872 International publication pamphlet WO2013 / 073693 International Publication Pamphlet JP 2014-108134 A

  The conductive material to which PEDOT-pTS using silk as a base material is adhered and the conductive material to which PEDOT-PSS using a predetermined base material is attached are easy to attach these conductive polymers. It is a very promising conductive material because it has excellent compatibility with living organisms as well as excellent conductivity and excellent conductive performance. However, there are problems such as the fact that silk is relatively expensive as a base material, the electric resistance value of silk itself is not so high, and it may not be optimal depending on the specific application.

  The present inventor has conducted studies for solving the above-described problems, and as a result, has found that paper is suitable as a target to which PEDOT-pTS or PEDOT-PSS is adhered. Paper is a cheaper biosafety material. In addition, since the electric resistance value of paper is generally higher than that of silk, for example, a haptic element or a sensor whose electric characteristic value fluctuates due to an external force, or a movement in a non-contact state, the electric characteristic value of the element. When used as a separation operation identification element or sensor, which is identified by the variation of the electrical characteristics, the variation width of the electrical characteristic value with respect to the external force and the variation of the operation is large, and is suitable for the application.

That is, the present invention firstly provides PEDOT-pTS (poly (3,4-ethylene-dioxythiophene) -p-toluenesulfonate) or PEDOT-PSS (Poly (3, Provide a conductive material to which 4-ethylenedioxythiophene) -polystyrenesulfonate) is attached (hereinafter, also referred to as a conductive material of the present invention),
Secondly, an electric element provided with the conductive material of the present invention (hereinafter, also referred to as an electric element of the present invention) is provided. A separation operation identification element (hereinafter also referred to as a separation operation identification element of the present invention), or a haptic element whose electric characteristic value fluctuates due to an external force (hereinafter also referred to as a haptic element of the present invention); To provide
Third, a force sensor including these electric elements and a detection unit electrically connected to the electric elements, wherein the detection unit detects an electric characteristic value or a change in the electric elements. And a sensor such as a separation operation identification sensor (hereinafter, also referred to as a sensor of the present invention).

  According to the present invention, an inexpensive conductive material having excellent safety and conductivity is provided. In particular, the electric sensor element of the present invention is used as a force sensor or a force sensor whose electric characteristic value fluctuates when energized due to external force, for example, because the electric resistance value of paper used as a base material is relatively high. In the case, or the movement of the non-contact state is identified by the variation of the electrical characteristic value in the element, when used as a separation operation identification element or a separation operation identification sensor, the change width of the electric resistance value with respect to the change of the external force is large, Suitable for such applications.

It is a drawing showing a test system of Example 1, (1) is an actual photographing base, and (2) is a schematic diagram. It is the drawing which showed expansion and contraction of the stitch by load typically. 6 is a drawing based on a real photograph showing a test system of Example 2 (II). 6 is a diagram showing the relationship between the weight (logarithmic scale) and the reduction ratio of the electric resistance value using the test result of Example 2 (II). FIG. 8 is a schematic diagram of a 4-channel force sensor used in a weight shift test of Example 3. It is the figure which showed the outline of the weight transfer test of Example 3, (1) shows the presence of the haptic element put on the chair, (2) schematically shows various movements of the panel on the chair. Is shown. 6 is a drawing showing the results of a weight shift test in Example 3. 13 is a view showing a state of mounting elements in a measurement test on chest movement in Example 4. It is the figure which showed that the respiratory waveform was extracted in the measurement test regarding the chest body movement of Example 4, (1) is a waveform including noise of body movement, and (2) is the body movement concerned This is a respiratory waveform extracted by removing noise, and (3) shows a detection screen of the respiratory waveform in the device. 19 is a schematic diagram of a test system using a finger related to the separation operation identification element of the fifth embodiment.

1. Conductive material of the present invention As described above, the conductive material of the present invention is a conductive material in which PEDOT-pTS or PEDOT-PSS is adhered to the surface of a base material containing paper. The following (1)-(2) provides the conductive material of the present invention.

(1) Substrate of conductive material The “substrate containing paper” may be a “substrate made of paper” or “a mixture of paper and a material other than paper”. You may. "A material in which paper and a material other than paper are mixed" refers to, for example, a case where fibers other than paper are present in the constituent fibers combined by twisting in a paper yarn. The case where the material is a paper covering yarn and the material of the core yarn is other than paper (for example, a polyurethane filament or the like) is also included. Further, in the case where the base material is a fabric, a case where a fabric, that is, a knitted fabric, a woven fabric, or the like is constituted by the paper yarn alone or a combination of the paper yarn and another type of yarn is also referred to as a “paper-containing base material”. Material ". The content ratio of the paper in the “base material containing paper” is 10% by mass or more, and may be 100% by mass, based on the entire base material. In particular, when the presence of paper is emphasized, the content is preferably 20% by mass or more.

  As described above, the `` paper '' which is a main material of the base material of the conductive material of the present invention is produced by agglutinating plant fibers and, if necessary, other fibers, and its production method is known. In principle, plant fibers are obtained by beating or the like, dispersed in water or the like, scooped up, and dried to manufacture the fibers. As plant fibers, seed hair fibers such as cotton; bast fibers such as flax, hemp, jute, jujube, mitsumata, ganpi; conifer fibers such as spruce, fir, pine, larch; poplar, hippopotamus, beech, willow, eucalyptus, Hardwood fibers such as elm; leaf fibers such as abaca (manila hemp); rice fibers such as rice straw and wheat straw; and others, espart, reed, bamboo, bamboo grass, kumazasa and the like. Other fibers include polyamide fibers such as nylon, polyester fibers such as PET, acrylic fiber, aramid fiber, polyurethane fiber, carbon fiber, and the like, and are added as components of paper according to the properties of the fiber. In addition, components normally contained in paper other than fibers, for example, fillers such as talc, clay, calcium carbonate, and titanium dioxide, and glue are defined as components of the paper in the present invention. The above-mentioned "material other than paper", which is calculated separately from "paper-containing base material" separately from paper, is "externally combined" with "paper integrally configured". "Material", which is different from the "component contained in the integrally formed paper". As described above, the configuration of paper mainly composed of vegetable fibers is suitable for attaching PEDOT-pTS or PEDOT-PSS.

  Among the `` paper '' which is a main material of the base material of the conductive material of the present invention, Japanese paper has excellent hygroscopicity as a used material, and furthermore, the constituent fibers are long and the entangled state of the fibers is moderate. Therefore, it is preferable in that PEDOT-pTS or PEDOT-PSS is excellent in fixing property. The Japanese paper in the present invention is a paper substantially comprising bast fiber as a constituent fiber. Originally, Japanese paper is a paper made from the bast fiber (described above) as a raw material and made by the hand piling method using torsion (vegetable mucus). In the present invention, paper made by the mechanical plowing method is also used in the present invention. Include in "Washi". In addition, bast fibers and components other than vegetable batters, for example, chemical substances that substitute for batter, and other vegetable components, for example, those containing a mixture of kumazasa fibers and the like are also included in the “Japanese paper” of the present invention. .

  The substrate on which PEDOT-pTS or PEDOT-PSS is to be adhered may be paper in a thin and flat form (sheet shape) which is generally recognized, or may be yarn (paper yarn). . Further, a cloth based on a paper thread to which PEDOT-pTS or PEDOT-PSS is adhered may be used. It is also possible to attach PEDOT-pTS or PEDOT-PSS to a paper thread-based fabric (PEDOT-pTS or PEDOT-PSS is not attached).

The paper thread can be produced by chopping a sheet of paper that has already been produced, slitting the sheet, and twisting the slit paper. At the time of twisting, fibers or yarns other than paper, for example, silk, rayon, it is also possible to cross-twist with cotton yarn, it is also possible to use other types of yarn as a core material, at least the yarn surface It is necessary that the paper is exposed on the entire surface or a part thereof. The upper twist yarn used as the haptic element will be described later.
The thickness of the paper thread is not particularly limited and can be selected as needed within a range of about 0.1 μm to 3 mm, but is usually about 1 μm to 1 mm.

  The fabric, which is one embodiment of the conductive material of the present invention, is a fabric based on the above-described paper thread to which PEDOT-pTS or PEDOT-PSS is adhered, and specifically, a knit or a woven fabric.

  The mode of using the fabric as the conductive material according to the present invention is mainly used as a force sense element, and the detailed mode will be described later.

(2) Attachment of PEDOT-pTS to base material PEDOT-pTS (poly (3,4-ethylene-dioxythiophene) -p-toluenesulfonate) polymerizes pTS (p-toluenesulfonate) and EDOT (3,4-ethylenedioxythiophene) A conductive polymer formed by the reaction. For example, as a first attachment method, a paper-containing base material (mainly, a paper-mixed solution of an organic solvent solution containing an oxidizing component and pTS and EDOT) PEDOT-pTS can be adhered by performing contact adhesion to a sheet of paper or paper thread) by dipping or printing, and then performing a polymerization promotion treatment on the contact point. 1 or a variant thereof). As a second attachment method, (a) an attachment step of attaching a pTS solution containing an oxidized component and pTS to a paper-containing base material (mainly, sheet-like paper or paper thread); In (a), EDOT is further adhered to the substrate on which the oxidized component and pTS are adhered, and a polymerization reaction for generating PEDOT-pTS proceeds in these, whereby PEDOT-pTS can be adhered. (Second attachment method: a method disclosed in Patent Document 2).

<First attachment method of PEDOT-pTS>
In the first attachment method, by mixing the pTS solution and EDOT, the polymerization reaction of EDOT proceeds in the pTS-EDOT mixed solution, and PEDOT-pTS which is a high molecular polymer is formed. According to the following formula, the polymerization rate increases as the temperature rises, and if stored at a low temperature of the refrigerator level, the polymerization rate can be reduced and the time for the adhesion step can be secured. Although the oxidizing component is exemplified by Fe ^3+, it is not limited to this.

  In the first deposition method, "afterwards" means that the polymerization promotion treatment is performed at "simultaneous and subsequent" timings related to the timing at which the pTS-EDOT mixed solution contacts the substrate. Specifically, both timings may be substantially simultaneous, and a polymerization lag treatment may be performed by providing a time lag from the timing at which the pTS-EDOT mixed solution contacts the substrate. Further, for example, while maintaining the state in which the polymerization promoting treatment is performed on the surface of the base material, the pTS-EDOT mixed solution is contacted thereon, and the time lag is not substantially provided. In “afterwards”. The mixing ratio of the pTS solution and EDOT in the first deposition method is pTS solution: EDOT = 10: 1-100: 1, preferably 20: 1-40: 1 in volume ratio.

  pTS is known as a p-toluenesulfonic acid compound (salt or ester with p-toluenesulfonic acid (tosylic acid)) and is commercially available. The organic solvent that can be used as the solvent of the pTS solution is one that can dissolve pTS and oxidized components and the like, and preferably has good compatibility with the aqueous solvent. Specifically, a monohydric lower alcohol having 1 to 6 carbon atoms, specifically, methanol, ethanol, propyl alcohol, isopropyl alcohol, butanol, pentanol, or hexanol is used. The skeleton of carbon atoms constituting these monohydric lower alcohols may be linear, branched or cyclic, and may be used alone or in combination of two or more. It may be appropriately diluted with water before use. Among these, a monohydric lower alcohol having 1 to 4 carbon atoms, specifically, methanol, ethanol, propyl alcohol, isopropyl alcohol, or butanol is suitable as the organic solvent of the pTS solution.

  The oxidizing component contained in the pTS solution is not particularly limited as long as it can activate the polymerization reaction into PEDOT-pTS in the pTS-EDOT mixed solution, and examples thereof include transition elements and halogens.

  As the transition element, a first transition element such as iron, titanium, chromium, manganese, cobalt, nickel, and zinc; a second transition element such as molybdenum, silver, zirconium, and cadmium; a third transition element such as cerium, platinum, and gold Is exemplified. These transition elements may be used as a simple metal or a metal salt. Among these, it is preferable to use a first transition element such as iron and zinc.

The content of the oxidizing component in the pTS solution differs depending on the type of the oxidizing component used, and is not particularly limited as long as the above-mentioned polymerization reaction can be activated. For example, in the case of ferric ion (Fe ³⁺ ), the amount of ferric chloride is preferably 1 to 10% by mass, more preferably 3 to 7% by mass, based on the solution. . If this content is too large, the progress of the polymerization reaction will be fast, but it will be difficult to remove iron in the subsequent steps, and if it is small, the progress of the polymerization reaction will be slow.

  The content of pTS serving as a dopant in the pTS solution is preferably 0.1 to 10% by mass, more preferably 0.15 to 7% by mass, and particularly preferably 1 to 6% by mass with respect to the solution. %, Most preferably 2-5% by weight.

  EDOT is known as 3,4-ethylenedioxythiophene and is commercially available. EDOT is liquid at room temperature and water-soluble, and can be appropriately diluted with an aqueous solvent such as water.

  In the pTS solution, the effect of the present invention is impaired quantitatively or qualitatively, for example, the adhesion of the pTS-EDOT mixed solution to the base material containing paper and the conductive performance of the completed conductive material are not substantially impaired. As long as there is no other component, other components can be blended as needed.

  Such other components include, for example, glycerol, polyethylene glycol-polypropylene glycol polymer, ethylene glycol, sorbitol, sphingosine, and phosphatidylcholine, preferably glycerol, polyethylene glycol-polypropylene glycol polymer, and sorbitol. Or two or more of these.

  In addition, cationic surfactants such as quaternary alkyl ammonium salts and alkyl pyridinium halides; anionic surfactants such as alkyl sulfates, alkyl benzene sulfonates, alkyl sulfosuccinates, and fatty acid salts; polyoxyethylene, polyoxyethylene Nonionic surfactants such as oxyethylene alkyl ether; natural polysaccharides such as chitosan, chitin, glucose and aminoglycan; sugar alcohols and dimethyl sulfoxide.

  At room temperature, in the pTS-EDOT mixed solution, gelation of the solution due to the above polymerization reaction proceeds. For this purpose, it is preferable that the step of removing excess gelling polymer attached to the substrate is performed after the contact with the mixed solution. For example, the base material separated from the liquid mixture can be removed by physical means such as vibration, air blowing, and contact with a roller. When the step of removing the excess gelling polymer is not performed after the polymerization reaction is performed, after the mixed solution is prepared, the contact between the base material and the mixed solution is performed in a short time, and the preparation of the mixed solution is performed. There is a restriction that the contact should be made in a short time afterwards. Specifically, the contact by the contact should be completed within 5 minutes, more preferably within 1 minute after the preparation of the pTS-EDOT mixed solution. In the case of performing the above-mentioned step of removing the excess gelling polymer, even at room temperature, there is practically no time restriction of the adhesion step due to this contact, and after the preparation of the pTS-EDOT mixed solution, Can take a deposition time of 10 minutes or more, more preferably 15 minutes or more, to sufficiently attach PEDOT-pTS to the substrate. Even if the time of the adhering step is 40 minutes or more, the effect of accelerating the adhering to the prolonged step is not recognized due to the progress of gelation.

  The adhesion by contact in the first adhesion method is preferably performed by dropping, spraying, dipping, transferring, or applying.

  As the polymerization accelerating treatment in the first attachment method, a heat treatment can be mentioned. As the heat treatment, (α) contact with a heat radiator at 50-90 ° C. in the polymerization promoting portion, (β) contact with hot air set so that the polymerization promoting portion is at 50-90 ° C., (γ) For example, contact with a heating atmosphere of 50 to 90 ° C. in a constant temperature bath or the like may be used.

  The contact of the heat radiator at 50 to 90 ° C. in the above (α) is preferably performed for a heating time of 3 to 10 minutes, particularly preferably for 3 to 6 minutes, and most preferably for 4 to 6 minutes.

  When the polymerization promoting portion (β) is in contact with hot air set at 50 to 90 ° C., the time is preferably 3 to 10 minutes, particularly preferably 4 to 6 minutes.

  In the case of the heating atmosphere set to be 50 to 90 ° C. in the above (γ), 3 to 10 minutes is preferable, and 4 to 6 minutes is particularly preferable.

  After the heat treatment, the substrate is taken out of the solution, washed with water, more preferably distilled water or deionized water, and then dried in a thermostatic oven, hot air or warm air, sunlight, or the like.

  Further, for example, in the first attaching method, the attached portion of the pTS-EDOT mixed solution due to contact with the base material is formed as a drawing design on a part of the base material plane, so that the "attached portion is less likely to bleed". The characteristics of the first method can be utilized. The drawing design is different from simple one-sided attachment, and encompasses simple figures such as circles and triangles, various depictions such as animal and plant pictures, and portraits, characters, and patterns.

  In performing the first attachment method, masking or spraying can be performed to more precisely create a drawing design on the base material. The masking process is a process in which a portion where the conductive polymer is not attached is covered with a mask in advance. In this mask processing mode, in the first deposition method, before the pTS-EDOT mixed solution is deposited by contact with the base material, a mask process is performed on a portion except for the portion to be deposited, and then at least the deposition process is performed. The mask is removed after the contact with the mixed solution at a predetermined place and the polymerization promotion treatment is further performed.

  As a specific example of the mask treatment, for example, application of an anti-staining paste or beeswax as a masking agent can be mentioned. Examples of the paste-resistant paste include starch paste such as regular glue paste, corn starch paste and sweet potato starch paste; rubber paste; seaweed paste such as seaweed paste; and other various pastes. Starch paste is suitable as the anti-staining paste. The concentration of the anti-dyeing paste (mass powder mass / water mass) at the time of use is not particularly limited, but is generally 3 to 5 mass%. Removal of the paste paste can be performed by washing with water. Also suitable are beeswax, which is wax from beehives. When used, it is usually used by directly heating and melting. The beeswax is removed by melting again by heating.

<Second method of attaching PEDOT-pTS>
In the second attachment method, first, an oxidizing component and pTS as a dopant are dissolved in an organic solvent solution, and a base material containing paper is immersed in the organic solvent solution (pTS solution).

  The organic solvent that can be a solvent of pTS and the oxidizing component contained therein are the same as the above-mentioned “organic solvent and oxidizing component of pTS solution in the first attachment method”. The “other components” that can be contained in the pTS solution are the same as the “other components in the pTS solution of the first attachment method” described above.

The content of the oxidizing component in the pTS solution differs depending on the type of the oxidizing component used, and is not particularly limited as long as the above-mentioned polymerization reaction can be activated. For example, in the case of ferric ion (Fe ³⁺ ), the ferric chloride is preferably 1 to 10% by mass, more preferably 3 to 7% by mass, based on the pTS solution. If this content is too large, the progress of the polymerization reaction is fast, but it is difficult to remove iron in the subsequent step, and if it is too small, the progress of the polymerization reaction is slow.

  The content of pTS serving as a dopant in the pTS solution is preferably 0.1 to 10% by mass, more preferably 0.15 to 7% by mass, and particularly preferably 1 to 6% by mass with respect to the solution. %, Most preferably 2-5% by weight.

  In the second attachment method, next, EDOT as a monomer is added to the PTS solution in which the above-described base material is immersed, and then at 50-100 ° C., preferably for 10 minutes to 60 minutes, and more preferably for 50 minutes. Heating is carried out at 80 ° C. for 10-40 minutes, very preferably at 60-80 ° C. for 10-30 minutes. After heating, the substrate is taken out of the solution, washed with water, more preferably distilled water or deionized water, and then dried in a thermostatic oven, hot air or warm air, sunlight, or the like.

  The used amount ratio of the pTS solution and EDOT in this step is pTS solution: EDOT = 10: 1-100: 1, preferably 20: 1-40: 1 in volume ratio.

(3) Attachment of PEDOT-PSS to a substrate PEDOT-PSS (Poly (3,4-ethylenedioxythiophene) -polystyrenesulfonate) is obtained by immersing a substrate containing paper in a conductive solution containing PEDOT-PSS. The PEDOT-PSS adhered to the substrate is electrochemically polymerized and fixed by applying the current by moving the substrate between the electrodes while vertically lifting the substrate from the conductive solution. (Patent Document 3). Further, a resin composition in which PEDOT-PSS and a binder resin are mixed is attached to a yarn to which stretchability has been imparted, and can be attached by solidifying or polymerizing by drying, heating, heating, or the like (Patent Document 4). ). Alternatively, the substrate is made conductive by adsorbing the water-soluble / solvent dispersion obtained by dispersing PEDOT-PSS finely divided (average particle size is about 10 microns) in a solution / solvent on the substrate. Is possible (the method of the fifth embodiment).

(4) Properties of Conductive Material The conductive material of the present invention produced in this manner has high biocompatibility, can be produced relatively inexpensively, and has an essential base material of paper. It has the characteristic that the original electric resistance value (including impedance) is high, and the fluctuation range of the current value, the resistance value, and the electric capacitance value when energized as a conductive material is large. From this feature, it is suitable for use as a force sense element to be described later and use as a separation operation identification element. In addition, by selecting a high-concentration dispersion in the form of fine particles of PEDOT-PSS described above and increasing the adhesion density to the substrate, thereby lowering the electrical resistance value, the potential measurement from inside the muscle or from the skin surface It is also possible to use it for the use as an electrode element for use.

2. Electric element of the present invention The electric element is a unit for performing some electric role, for example, an electrode element acting as a biological electrode or the like, a haptic element as a medium for detecting external force by an electric signal , And a separation operation identification element described later.

(1) Biological electrode element When the electric element of the present invention is in the form of a "biological electrode", it is roughly classified into (a) a surface electrode element or (b) a puncture electrode element.

(A) In the case of a surface electrode element, the area of the electrode element that can be in contact with the skin is preferably 0.25 to 100 cm ² , and in particular, the shape of the electrode element is “thread-like” or “sheet-like”. Is preferable.

(B) In the case of a puncture electrode element, an embodiment having a structure in which the electrode element is directly inserted into a living tissue may be mentioned. In this case, the shape of the electrode element is typically a linear shape or a needle shape, and the tip of the shape can be inserted into a living body. The contactable surface area of the puncture electrode element with the living tissue is preferably 0.0004 to 0.02 cm ² .

  These bioelectrode elements can be suitably used for a myoelectric sensor system or an electroencephalogram sensor system.

  Non-substantial portions of the bioelectrode element, for example, conductive material, insulating material, conductive connector, cover material for covering the element, adhesive material for attaching the element to another object, cushion material or filling for protecting the element Materials and the like are also included in the electric element of the present invention.

(2) Haptic element The “haptic element” is an element of a higher concept of the pressure-sensitive element, and detects the magnitude and fluctuation of an external force applied to the element as an electrical characteristic value.

  “External force” is typically a pressing force or a pulling force. The “electric characteristic value” is a voltage value, a current value (including both direct current and alternating current), an electric resistance value (including an impedance value), or a capacitance value. In the present invention, the electric resistance value or the capacitance value Preferably, a value is used.

  In the haptic element of the present invention, the yarn constituting the fabric (knitted or woven fabric) which is the base material of the element used for the haptic device is preferably a “twisted yarn” (uptwist yarn).

  The term “twisting” is a concept corresponding to “primary twisting” (twisting applied to a single yarn) in a twisted yarn. Twisting when two or more single yarns are twisted into one yarn. Say. The number of single yarns to be twisted in the present invention is not particularly limited, but is two (double yarn), three (three yarns), or four (four yarns)), and more. Can be used. The presence or absence of the primary twist in the single yarn is not particularly limited. Further, as the upper twisted yarn, single twisted yarn, various twisted yarn, piece twisted yarn, wall twisted yarn, and the like can be selected, and there is no particular limitation. In addition, the number of twists of the upper twist is a strong twist of 1000 or more and less than 2500 T / m, even if the number of twists is a sweet twist of 10 or more and less than 500 T / m, a middle twist of 500 or more and less than 1000 T / m. Alternatively, an extremely strong twist of 2500 T / m or more may be used. In the present invention, a filament yarn such as polyurethane is used as a core yarn, and a `` covering '' in which another single yarn is wound single or double or more is included as a ply twist. include.

  For example, if attention is paid to the electric resistance value, PEDOT-pTS or PEDOT-PSS constituting the pressed portion of the fabric adheres due to the pressing force applied to the vertical surface (thickness direction) or the tensile force in the plane. In the twisted upper yarn, the substantial increase in the cross-sectional area described above occurs. In addition, the apparent cross-sectional area may increase due to the yarns to which PEDOT-pTS or PEDOT-PSS adheres to each other due to the pressing force or the pulling force.

  Further focusing on the capacitance value, by applying a pressing force in the thickness direction or a tensile force in a plane, the PEDOT-pTS or the PEDOT-PSS forming the pressed portion of the fabric between the twisted yarns to which the PEDOT-PSS is attached. When the space volume fluctuates, the capacitance of the portion also fluctuates.

  In addition, in this case, all the yarns whose cross-sectional area increases or decreases or the yarns related to the fluctuation of the space volume between the yarns are top-twisted yarns as long as the change in the movement by the above mechanism can be detected at the fabric level. No need.

  As described above, as the upper twisted yarn, for example, a single twisted yarn, a multiple twisted yarn, a piece twisted yarn, a wall twisted yarn, or the like can be selected, but a single twisted yarn, a multiple twisted yarn, or a piece twisted yarn is preferable. The single twisted yarn is an upper twisted yarn obtained by aligning one or two or more single yarns and twisting them with a right twist or a left twist. The ply-twisted yarn is an upper-twisted yarn obtained by aligning two or more single-twisted yarns (in principle, a sweet-twisted yarn or a medium-twisted yarn) and twisting the yarn in the opposite direction to the single-twisted yarn. The piece twisted yarn is an upper twisted yarn obtained by drawing two or more single twisted (strong twisted) yarns and twisting them in the direction opposite to the single twist. In these three types of upper twisted yarns, the side surfaces of the constituent single yarns approach each other due to the tensile force, and the desired apparent yarn cross-sectional area can be increased.

  In addition to the change involving the shape elastic recovery of the apparent cross-sectional area of the apparent twisted yarn itself, the external force in a predetermined direction is applied to the haptic element, so that the shape of the knitted or woven fabric changes according to the magnitude of the external force. When the yarns to which the PEDOT-pTS or PEDOT-PSS adheres newly contact each other and stop applying the force, the shape of the field changed by the external force returns to the original shape elasticity recovery. It is preferable to have the property both when the electric resistance value is used as an index and when the capacitance value is used as an index. That is, when a pressing force in the thickness direction is applied to the plane of the knitted or woven fabric, the plane is pulled in the thickness direction, and at this time, a new contact state between the yarns constituting the knitted or woven fabric is generated. It is preferable that the contact state is released when the pressing force is released when the pressure is released, and that the contact state returns to the original state. Further, when a pulling force acts on the edge of the knitted or woven fabric, the force pulls the plane in the lateral direction, and at that time, a new contact state is created between the yarns constituting the knitted or woven fabric, When the pulling force is released, the contact state is preferably released, and the elastic member has a shape elastic recovery property that returns to the original state. If the knit or woven fabric is excellent in shape elasticity recovery, the hysteresis in the force sense element of the present invention can be reduced, which is preferable.

  The knitted or woven fabric may be a single layer or a multilayer. Even if it is a single layer, it is possible to provide an overlap between the yarns in the thickness direction by knitting and weaving, and by applying an external force to the overlap in the thickness direction, the apparent appearance of the yarns is obtained. The upper cross-sectional area can be increased, and the volume of space between the yarns can be varied.

  A knitted fabric (knit) is basically a fabric made of a single thread, and is a fabric made of a loop (a stitch) of a thread formed by successively hooking a thread on a thread loop. Warp and weft are not used, as in woven fabrics. In general, knitted fabrics are more woven than woven fabrics because of the "increase in apparent cross-sectional area inside the yarn" and the "increase in apparent cross-sectional area due to the overlapping of the side surfaces of the yarns" between the yarns, or " It is possible to more easily cause the "fluctuation in the space volume between the yarns" for the same external force.

  The knitted fabric used in the present invention is not particularly limited, and may be a machine knitting machine (a flat knitting machine, a warp knitting machine, a circular knitting machine, a tricot knitting machine, a Raschel knitting machine, a Miranese knitting machine, a rubber knitting machine, an interlock knitting machine, or the like). ), Bar needle knitting, hook needle knitting, Afghan knitting and the like. The organization of the knitting is not limited, for example, flat knitting, kanoko knitting, rubber knitting, pearl knitting, tack knitting, transfer knitting, knitting, double knitting, double-sided knitting, swing knitting, perelin knitting, floating knitting, pile knitting , Attached thread knitting, Rope knitting, Intersia, Wrap knitting, Non-run organization, Chain knitting, Single tricot knitting, Single cord knitting, Single atlas knitting, Second stitch knitting, Single satin knitting, Single velvet knitting, Plain tricot knitting, Double atlas Knitting, double cord knitting, half tricot knitting, reverse half, Queen's cord knitting, satin tricot knitting, double tricot knitting, velvet knitting, shell knitting, knot knitting, sword knitting, warp thread insertion knitting, marqueet, dropping plate structure, net knitting , Miranese knitting, warp weft inserting knitting, weft inserting knitting and the like.

  Woven fabric is a fabric made by combining warp and weft. The structure of the woven fabric used in the present invention is not particularly limited. For example, it can be used as a three-layer structure of plain weave, twill weave, and satin weave. Further, a three-dimensional structure may be changed or a combined structure obtained by changing or combining the three structures, or a single special structure or a woven structure. Furthermore, multiple woven fabrics such as a double woven fabric, a double woven fabric, a double woven fabric, a pile woven fabric, a towel woven fabric, and a tangled woven fabric may be used. As described above, the multiple woven fabrics can provide an overlap between the yarns in the thickness direction, and by applying an external force to the overlap in the thickness direction, the apparent cross-sectional area between the yarns can be reduced. It is possible to increase the amount of variation in the space volume formed between the yarns.

  The stitches or weaves are preferably uniform in the portions used as the haptic element in order to obtain the same overall sensitivity to external force.For example, in order to prevent the yarn from fraying, the closed stitch portions or It is also possible to provide the closed woven portion on the outer edge or the like of the knitted or woven fabric. Further, the stitches or the stitches can be adjusted in frequency or size in order to obtain appropriate sensitivity to external force. Increasing the stitch or texture increases the apparent cross-sectional area due to the overlapping of the constituent yarns, or the amount of variation in the space volume between the yarns tends to be suppressed, but the output per unit area as a force-sensing element It is possible to reduce the amount of information on the electric characteristic value, which can lead to data compression. Conversely, when the stitches are reduced, the apparent cross-sectional area due to the overlapping of the constituent yarns and the variation in the space volume between the yarns tend to increase. There is a possibility that the noise becomes excessive and a lot of noise is taken in.

The substantial part of the force-sensing element of the present invention, that is, the plane size of the knitted or woven fabric that is the part for detecting external force is difficult to distinguish from noise if it is too small, so in the case of an element that detects all directions of external force. Is preferably 1 cm ² or more. In the case of an element that detects only a predetermined direction of the external force, the length in the other direction may be narrower as long as the length in the predetermined direction is 1 cm or more. If the width is extremely wide, if the change in the local motion is small, the motion is masked by noise and detection becomes difficult. However, while reducing the size of the individual elements, they perform `` multi-channelization of the elements '' to distribute and arrange them over the entire range of detecting the movement of the object, and change the movement obtained from the individual elements, By fitting and plotting on the time axis, it is possible to detect a temporal change in the movement of the entire object. In this case, the size (planar size) of each element is preferably 1 cm ² or more as described above. The number of elements in the case of multi-channel is not particularly limited, and can be selected according to the size of the target and the like.

  As described above, even if the force sensor of the present invention is a one-channel type in which one device is electrically connected to a detection unit of a force sensor described later, two or more devices are electrically connected. Multi-channel type. In the device of the present invention, conventionally, even with respect to a large area weight fluctuation or the like that required excessive multi-channeling, for example, by increasing the area of the fabric to a certain extent, a single channel, or It became easy to reduce the number.

  Non-substantial part of the separation operation identification element, for example, conductive material, insulating material, conductive connector, cover material for covering the element, adhesive material for attaching the element to another object, cushion material for protecting the element, Fillers and the like are also included in the haptic element of the present invention.

(3) Separation operation identification element The “separation operation identification element” is an element that identifies a movement in a non-contact state by a change in an electrical characteristic value of the element. As the electric characteristic value, an electric resistance value or a capacitance value is preferable, and a capacitance value is most preferable.

  “Non-contact state” means that there is some gap between the element and the subject of the movement. Other elements according to the present invention, the element is brought into contact with the living body, the biological reaction and movement is to detect through the electrical characteristic value, while the separation operation identification element, on the contrary, When one element is placed away from the subject of movement (object), for example, when the distance is a space, the approach of the object causes a new electric field between the element and the object, This changes in accordance with the movement of the object, so that the capacitance value of the element changes. When the gap is between human skin and muscle (for example, when the element is placed on the skin and a change in blood flow is to be detected), an insulator is placed between the element and the skin. By intervening, it is possible to detect a change in the blood flow by detecting a change in the capacitance of the element according to the change due to the pulsation of the blood flow.

  As the separation operation identification element, the conductive material of the present invention is preferably made of a fabric (knitted or woven fabric) as in the case of the haptic element, and may be a multilayer fabric rather than a single layer. It is suitable. The yarn constituting the fabric includes the above-mentioned twisted yarn.

  Non-substantial part of the separation operation identification element, for example, conductive material, insulating material, conductive connector, cover material for covering the element, adhesive material for attaching the element to another object, cushion material for protecting the element, Fillers and the like are also included in the separating operation identification element of the present invention.

3. Sensor of the Present Invention The sensor of the present invention includes the electric element of the present invention (including a haptic element or a separation motion identification element) and a detecting unit electrically connected to the electric element. A sensor for detecting an electric characteristic value of the electric element.

(1) Force sensor or separation operation identification sensor When the sensor of the present invention is a force sensor or separation operation identification sensor, an electric characteristic value, preferably an electric resistance value or a capacitance value (in the case of a separation operation identification sensor) Is suitable for detecting fluctuations in the capacitance value, the voltage application unit is provided or can be connected to the voltage application unit. The voltage applying unit is a DC power supply such as a battery or an AC power supply such as a commercial power supply or a household power supply. If necessary, equipment generally used for an electric circuit such as a rectifier, a capacitor, a resistor terminal, a coil, a transistor, and a diode, an electronic circuit, a digital circuit, and the like may be provided.

  Fluctuations in the electric resistance value, the capacitance value, and the like in the haptic element or the separation operation identification element of the present invention are correlated with the force (force sensor element) applied to the element and the movement of the object (separation operation identification element). The detection unit quantitatively detects a change in an electric resistance value, a capacitance value, or the like in the device of the present invention, and thereby a force externally applied to the device of the present invention. And the movement of the object can be quantified. The detection unit may appropriately include a calculation processing unit for calculating this quantitative value. Further, by further providing a learning unit and performing machine learning, learned data on the movement of the detection target and fluctuations of the electric resistance value, the capacitance, and the like is created, and the movement of the new detection target is generated by the learning unit. It is possible to determine based on the learned data. Further, the learned data may be updated as appropriate.

  The haptic element of the present invention, the detection unit, and the learning unit are electrically connected by wire or wirelessly.

  Note that the hysteresis can be corrected by resetting each measurement, that is, by applying a zero point correction for each measurement.

(2) Another form of sensor A part of the electric element of the present invention is provided with an injection mechanism for injecting a drug solution into the body, and can supply a drug solution corresponding to the action potential of the muscle or brain wave to the body. It is possible. For example, a tube for drug transport may be provided as an injection mechanism. Further, by making the drug transport means an osmotic pressure transfer in paper which is a base material of the electric element, the electrode element and the drug transport path can be integrated. As the drug, for example, when the electrical element of the present invention is used as a brain electrode, a drug that regulates central nervous activity, for example, a neurotransmitter such as glutamate, GABA, acetylcholine, or serotonin, or an NGF that relieves neuropathy Nerve growth factors, neurotrophic factors such as BDNF, GSNO (S-Nitrosoglutathione), and various hormones.

  The electric element of the present invention can be used for a myoelectric sensor system and an electroencephalogram sensor system. In this case, a living body electrode element (surface electrode or puncture electrode) or a separation operation identification sensor is used as an electrical element, but other mechanisms necessary for these sensor systems are provided. For example, in addition to electrical elements, amplifying unit, various stimulating units for obtaining evoked potentials, analyzing unit for analyzing, recording, adding, calibrating, etc., display for displaying the movement of myoelectricity and EEG by voice and video etc. Departments are provided as needed. Means for transmitting the electric signal may be wired or wireless.

  The myoelectric sensor system and the electroencephalogram sensor system can perform more detailed grasping of the muscle and brain states by synchronizing with other types of biological signals, respectively. Blood pressure, electrocardiogram signal, pulse oxy signal, muscle strength, joint angle, etc. can be combined and synchronized.

  With an electroencephalogram sensor system, it is also possible to synchronize electroencephalograms and myoelectric signals indicating eye movements. The electric element of the present invention is useful as a biological electrode in the case of the combination of the brain wave and the myoelectric signal.

  Hereinafter, examples of the present invention will be described.

[material]
Kanoko knitting using 240 denier (22th count) Japanese paper yarn (twisted with a twisted sweet twist: a temperature of 22 ° C., a humidity of 50%, and an expansion rate of 16%) as the base material of the conductive material of the present invention. (10 cm width, 50 stitches, 50 steps) An elastic fabric (30 cm × 30 cm) was obtained.

  As a pTS solution, a butanol solution containing iron (III) ions of a transition metal and pTS (CLEVIOS CB 40 V2 manufactured by Heraeus, about 4% by mass as iron (III) p-toluenesulfonate: “CLEVIOS”) Is a registered trademark). As EDOT, an aqueous solution of EDOT (CLEVIOS MV2 manufactured by Heraeus, EDOT: about 98.5% by mass: “CLEVIOS” is a registered trademark) was used.

  A mixed solution prepared by mixing EDOT with the above pTS solution was prepared, cooled to about 4 ° C., and the base material was immersed in the mixed solution at room temperature for 20 minutes. Thereafter, the immersed base material is taken out of the mixed solution, and two points on one side thereof are hung with a clip and suspended. The base material is exposed to the wind of a fan (strong wind) for 5 to 10 minutes, and dried while vibrating the base material with the wind. And further rubbing with a roller to remove excess gelling polymer adhered to the substrate by these steps.

  Next, the base material from which the gelled polymer had been removed was placed in a constant temperature bath at 70 ° C., heated for 5 minutes, and polymerized into PEDOT-pTS. Next, the polymer substrate was repeatedly washed with water twice, and then dried at 90 ° C. to obtain “a knitted paper made of PEDOT-pTS” (also referred to as a substrate in this example).

[Example 1] Load test for haptic element (I) The following load test was performed using the adhered substrate prepared in the above [Material] as a haptic element.

  As shown in FIG. 1 (FIG. 1 (1) is a photograph of the test system, (2) is a schematic diagram thereof), a cylindrical plastic (diameter 3 cm) with a load of 300 g is placed at three places (X , Y, Z). AH indicates a place where the terminal is installed. The stitches of the fabric used in this example have directionality, and the horizontal direction in FIGS. 1 (1) and (2) (left and right arrows in FIG. 1 (2)) is the vertical direction (FIG. 1 (2)). ), The extensibility is larger than that of the upper and lower arrows). When no load was applied, the electrical resistance in the left-right direction (left end to right end) with large extensibility was about 11 kΩ, and the electrical resistance value in the vertical direction (top to bottom) with small extensibility was 8 kΩ. It has been found that even when the distance between the terminals for measuring the electric resistance value is the same, the electric resistance value differs depending on the direction of the stitch. The stitches are deformed depending on the direction of extension (FIG. 2). FIG. 2 is an enlarged schematic view of a stitch corresponding to the direction in which the adhered base material of FIG. 1 is placed, and the lower part of FIG. 2 shows the deformation of the stitch when extended in the left and right arrow directions of FIG. Is shown.

  Table 1 is a set of AB, EG, AC, FH, and AD, and a resistance value when a terminal is installed and the above-mentioned weight is applied to any of X, Y, and Z. The results of the measurement are shown.

  From the results of Table 1, it was found that the change rate (decrease rate) of the electric resistance value shows some trends depending on the combination of the positions of the electrodes to be measured and the combination of the positions of the weights. For example, it is clear from the difference in the rate of change of the resistance value between A and B that it is possible to detect which position of the weight is in X, Y, or Z.

(II) Using the adhered substrate as a haptic element, the amount of decrease in the electrical resistance with respect to the change in the load in the vertical direction (Z direction) was examined.

  After the above attached base material cut into 7 cm × 7 cm was placed in the horizontal direction, both ends of the dough were sandwiched by clips. In a state where the cloth is stretched in the horizontal direction (X-Y direction), weights of 10 g, 20 g, and 50 g are respectively applied to the center (the position of “Y” in the above (I)), so that the cloth is placed in the vertical direction. The resistance value between the clips at both ends ("between AB" in (I) above) with respect to the load applied by the weight giving the displacement in the (Z direction) was measured including the case of 0 g load (FIG. 3-1). As a result, the 0 g load was 32.7 kΩ, the 10 g load was 20.0 kΩ, the 20 g load was 18.5 kΩ, and the 30 g load was 16.1 kΩ.

  Of these four electrical resistance values, the absolute value of the difference obtained by subtracting the electrical resistance value of each weight from the electrical resistance value of 0g weight “32.7 kΩ” is divided by the above “32.7 kΩ”. FIG. 3B is a graph showing a relationship between a value (vertical axis) in which the reduction ratio of the electric resistance value is defined as a percentage (%) and a logarithmic value (log10) (horizontal axis) of the weighted load.

  From FIG. 3-2, it was clarified that both values are in a positive correlation.

[Example 2] Body weight transfer test in sitting position using haptic element Four haptic elements (adhesive substrate was cut into 10 cm x 10 cm) by utilizing the correlation between load and variation shown in Example 1. The force sensor which can measure the difference of the load in the thickness direction individually and the change was measured in real time was fabricated (the dark square part in FIG. 4 is a channel (element)). , And the two lines derived from each element are conductive lines of the same material as the element.) This makes it possible to measure a load distribution and a change in the load from a measured load value applied to each channel (element).

  These four elements are ribbon-shaped conductive fiber electrodes obtained by attaching PEDOT-pTS to silk or Japanese paper fiber or the like, and are wired to an electric resistance value measuring instrument. The measuring instrument can represent a change over time of the electric resistance value as a waveform and record the waveform.

  The four electrodes are wired to the measuring instrument with conductive fiber electrodes such as silk or Japanese paper fiber. As shown in FIG. 5 (1), the force sensor is placed on a chair on which a cushion is laid, and a panel is seated thereon, and various postures are taken as shown in FIG. 5 (2). I got it.

  FIG. 6 shows a change over time of the electric resistance value with the weight shift at that time. The upper part of the vertical axis in FIG. 6 indicates that the weight is small. The point of time accompanied by a large weight shift is indicated by an arrow, but immediately after that, a large weight is applied.

[Example 3] Detection of respiratory waveform from chest motion measurement using a haptic element In this example, respiration detection is attempted. A device capable of presenting and storing changes in electrical resistance as waveforms via two terminals, with the above-mentioned adhesive base material fixed and arranged on a rubber band that can wind the chest. The change in the electric resistance value was measured (FIG. 7). As a result, as shown in FIG. 8 (1), although noise due to body movement and the like was recognized, a waveform recognized as a respiratory movement of the wearer appeared in a portion surrounded by an ellipse (FIG. 8 (2) ) (3)). It is also possible to obtain a clear respiratory waveform by removing noise by filtering or the like.

[Example 4] Examination as a separation operation discrimination element The above-mentioned attached base material (30 cm x 30 cm) was folded into four parts, and an LED (6000 millicandela (mcd) in the case of 20 mA), a terminal and a conductive wire were used. Electrically connected via In such a state, when the finger was brought close to the adhesion base material, the miniature lamp was turned on at a distance of about 15 cm, and the light became stronger and the capacitance of the system increased as the distance from the miniature lamp approached. This result indicates that the attached base material can be used as a separation operation identification element. A schematic diagram of this test system is shown in FIG.

[Example 5] Examination in PEDOT-PSS 50 ml of an aqueous dispersion of PEDOT-PSS was added to a cloth (size: 10 cm x 10 cm) made of Japanese paper yarn and shown in the beginning of [Material] above. After impregnating [OC series which is a low-resistance paint of Sepulzida (registered trademark: Shin-Etsu Polymer Co., Ltd.)] for about 2 hours and air-drying, the PEDOT-PSS-attached substrate ("PSS" in Tables 2 and 3 below) ) Was measured for the resistance value and the degree of expansion and contraction. As a comparison, an attachment substrate (size: 10 cm × 10 cm) to which PEDOT-pTS used in Example 1 was attached was used (shown as “pTS” in Tables 2 and 3 below). The extension of the base material is performed by placing each base material in the horizontal direction, sandwiching both ends of the fabric with clips, fixing one of the clips, and applying a weight to the clip on the side that is not fixed. The displacement in the horizontal direction (X direction) was measured with a caliper. The measurement of the electric resistance was performed at a position corresponding to AB in Example 1 (I).

  Table 2 shows the resistance value, and Table 3 shows the resistance change rate.

  From the results, it became clear that PEDOT-PSS can also be used as the conductive material of the present invention by attaching it to a paper material in the same manner as PEDOT-pTS. In addition, by using a dispersion of high-concentration PEDOT-PSS fine particles, it is possible to increase the adhesion density of PEDOT-PSS particles to a base material and lower the electric resistance value.

Claims (12)

  PEDOT-pTS (poly (3,4-ethylene-dioxythiophene) -p-toluenesulfonate) or PEDOT-PSS (Poly (3,4-ethylenedioxythiophene) -polystyrenesulfonate) adheres to the surface of the base material containing paper. Conductive material.   The conductive material according to claim 1, wherein the paper is Japanese paper.   The conductive material according to claim 1, wherein the base material is a paper thread or a fabric based on the paper thread.   The conductive material according to claim 4, wherein the fabric is a knit or a woven fabric including a paper thread.   The conductive material according to claim 4, wherein the knitted or woven fabric including the paper yarn is a yarn in which all or a part of the yarn constituting the knitted or woven fabric is twisted.   An electrical element comprising the conductive material according to claim 1.   The electric element according to claim 6, wherein the electric element is a separation operation identification element that identifies a movement in a non-contact state by a change in an electric characteristic value of the element.   The electric element according to claim 7, wherein the electric characteristic value is an electric capacitance value or an electric resistance value.   The electric element according to claim 6, wherein the electric element is a haptic element whose electric characteristic value varies when energized by an external force.   A sensor, comprising: the electric element according to claim 6; and a detection unit electrically connected to the electric element, wherein the detection unit detects an electric characteristic value of the electric element.   The sensor according to claim 10, wherein the electric element is a separation operation identification element.   The sensor according to claim 10, wherein the electrical element is a haptic element.

Images