WO2015079951A1 - 伸縮性電極、センサシート及び静電容量型センサ - Google Patents
伸縮性電極、センサシート及び静電容量型センサ Download PDFInfo
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- WO2015079951A1 WO2015079951A1 PCT/JP2014/080367 JP2014080367W WO2015079951A1 WO 2015079951 A1 WO2015079951 A1 WO 2015079951A1 JP 2014080367 W JP2014080367 W JP 2014080367W WO 2015079951 A1 WO2015079951 A1 WO 2015079951A1
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- electrode
- base material
- carbon nanotubes
- stretchable
- electrode body
- Prior art date
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Images
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01B—MEASURING LENGTH, THICKNESS OR SIMILAR LINEAR DIMENSIONS; MEASURING ANGLES; MEASURING AREAS; MEASURING IRREGULARITIES OF SURFACES OR CONTOURS
- G01B7/00—Measuring arrangements characterised by the use of electric or magnetic techniques
- G01B7/16—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge
- G01B7/22—Measuring arrangements characterised by the use of electric or magnetic techniques for measuring the deformation in a solid, e.g. by resistance strain gauge using change in capacitance
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01L—MEASURING FORCE, STRESS, TORQUE, WORK, MECHANICAL POWER, MECHANICAL EFFICIENCY, OR FLUID PRESSURE
- G01L1/00—Measuring force or stress, in general
- G01L1/14—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators
- G01L1/142—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators using capacitors
- G01L1/146—Measuring force or stress, in general by measuring variations in capacitance or inductance of electrical elements, e.g. by measuring variations of frequency of electrical oscillators using capacitors for measuring force distributions, e.g. using force arrays
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G5/00—Capacitors in which the capacitance is varied by mechanical means, e.g. by turning a shaft; Processes of their manufacture
- H01G5/01—Details
- H01G5/011—Electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Definitions
- the present invention relates to a stretchable electrode, a sensor sheet using the stretchable electrode, and a capacitive sensor.
- Patent Document 1 a wiring formed by drying a conductive paste made of a polyurethane dispersion and metal particles such as silver particles, and a flexible substrate are used. Proposed conductive members have been proposed.
- Patent Document 2 as a flexible electrode excellent in flexibility and conductivity, a carbon nanotube in which an elastomer is composed of carbon fibers having a diameter of 0.5 to 80 nm and the carbon fibers extend three-dimensionally from a central portion. There has been proposed a flexible electrode in which a continuous conductive path is formed.
- the stretchability as the conductive member is ensured, but the wiring portion responsible for the conductivity is formed using a conductive paste containing silver particles, so that the conductive member is stretched.
- the conductive path is cut and the electric resistance is greatly increased, or the variation in electric resistance is increased when the expansion and contraction is repeated.
- the flexible electrode described in Patent Document 2 although flexibility is ensured, it is inferior in stretchability, and the electrical resistance increases at the time of high elongation, or the electrical resistance varies when repeatedly stretched. was there.
- the present invention has been made in view of such circumstances, and its purpose is excellent in flexibility, stretchability, and conductivity, increase in electrical resistance at the time of stretching, and variation in electrical resistance at the time of repeated stretching.
- An object of the present invention is to provide a stretchable electrode capable of suppressing generation.
- the present inventors have found that the above object can be achieved by forming an electrode body using specific carbon nanotubes, and the present invention has been completed.
- the stretchable electrode of the present invention comprises a base material made of an elastomer composition and an electrode body integrated with the base material.
- the electrode body is formed using multi-walled carbon nanotubes having a fiber length of 50 ⁇ m or more.
- the multi-walled carbon nanotube preferably has a fiber diameter of 5 to 30 nm.
- the said elastic electrode can be used suitably for a sensor sheet.
- the sensor sheet of the present invention is a sensor sheet using the stretchable electrode of the present invention,
- the substrate is in sheet form, and the electrode body is provided on both sides of the substrate,
- the electrode main body provided on one surface of the substrate and the electrode main body provided on the other surface of the substrate are at least partially opposed to each other with the substrate interposed therebetween.
- the electrode body has a strip shape and is provided in a plurality of rows on both surfaces of the base material.
- the capacitance-type sensor of the present invention includes the sensor sheet of the present invention, a measurement unit, an electrode body provided in the sensor sheet, and an external wiring connecting the measurement unit.
- the portion of the electrode body provided on one surface of the base material and the electrode main body provided on the other surface of the base material facing each other with the base material interposed therebetween is used as a detection unit.
- the measuring means measures the amount of deformation strain by measuring a change in capacitance in the detection unit.
- the stretchable electrode of the present invention includes an electrode body formed using specific carbon nanotubes, it has high conductivity, an increase in electrical resistance when stretched, and an electrical resistance when repeatedly stretched. It has an excellent characteristic that the variation is extremely small.
- the sensor sheet of the present invention uses the stretchable electrode of the present invention having the above-described characteristics, a sensor excellent in measurement accuracy and long-term reliability can be provided. Since the capacitive sensor of the present invention includes the sensor sheet of the present invention, it is excellent in measurement accuracy and long-term reliability.
- (A) is a perspective view which shows typically an example of the elastic electrode of this invention
- (b) is the sectional view on the AA line of (a).
- (A)-(c) is sectional drawing which shows typically another example of the stretchable electrode of this invention, respectively. It is a schematic diagram for demonstrating an example of the shaping
- (A) is a plan view schematically showing an example of the sensor sheet of the present invention, and (b) is a cross-sectional view taken along the line AA of the sensor sheet shown in (a). It is a top view which shows typically an example of the electrostatic capacitance type sensor of this invention.
- FIG. 2 is an electron micrograph ( ⁇ 500) taken of highly oriented carbon nanotubes used in Preparation Example 1.
- 2 is an electron micrograph ( ⁇ 200000) taken of a highly oriented carbon nanotube used in Preparation Example 1.
- FIG. It is a schematic diagram for demonstrating the measuring method of the electrical resistance at the time of repeated expansion-contraction in an Example and a comparative example. It is a graph which shows the measurement result which measured the change of the electrical resistance with respect to repeated expansion-contraction in Example 1.
- FIG. It is a graph which shows the measurement result which measured the change of the electrical resistance with respect to expansion and contraction repeatedly in Example 2. It is a graph which shows the measurement result which measured the change of the electrical resistance with respect to repeated expansion-contraction in Example 3.
- the stretchable electrode of the present invention comprises a base material made of an elastomer composition and an electrode body made of carbon nanotubes integrated with the base material.
- the electrode body is formed using multi-walled carbon nanotubes having a fiber length of 50 ⁇ m or more.
- FIG. 1A is a perspective view schematically showing an example of the stretchable electrode of the present invention
- FIG. 1B is a cross-sectional view taken along line AA in FIG.
- an electrode body 102 formed using carbon nanotubes is laminated and integrated on the entire upper surface of a sheet-like substrate 101 made of an elastomer composition. ing.
- the substrate is made of an elastomer composition. Therefore, stretchability can be ensured.
- elastomer composition what contains an elastomer and another arbitrary component as needed is mentioned.
- the elastomer include natural rubber, isoprene rubber, nitrile rubber (NBR), ethylene propylene rubber (EPDM), styrene / butadiene rubber (SBR), butadiene rubber (BR), chloroprene rubber (CR), silicone rubber, and fluorine. Examples thereof include rubber, acrylic rubber, hydrogenated nitrile rubber, and urethane rubber. These may be used alone or in combination of two or more. Of these, urethane rubber and silicone rubber are preferable. This is because the permanent set (or permanent elongation) is small. Furthermore, urethane rubber is particularly preferable because it has excellent adhesion to carbon nanotubes compared to silicone rubber.
- the urethane rubber is formed by reacting at least a polyol component and an isocyanate component.
- Specific examples include, for example, an olefin urethane rubber having an olefin polyol as a polyol component, an ester urethane rubber having an ester polyol as a polyol component, an ether urethane rubber having an ether polyol as a polyol component, and a carbonate polyol.
- Examples thereof include carbonate-based urethane rubber having a polyol component and castor oil-based urethane rubber having a castor oil-based polyol as a polyol component. These may be used alone or in combination of two or more.
- the urethane rubber may be a combination of two or more polyol components.
- Examples of the olefin-based polyol include Epol (made by Idemitsu Kosan Co., Ltd.) and the like.
- Examples of the ester-based polyol include Polylite 8651 (manufactured by DIC).
- Examples of the ether polyol include polyoxytetramethylene glycol, PTG-2000SN (Hodogaya Chemical Co., Ltd.), polypropylene glycol, and Preminol S3003 (Asahi Glass Co., Ltd.).
- a chain extender, a crosslinking agent, a catalyst, a vulcanization accelerator and the like may be added to the reaction system as necessary.
- the elastomer composition may contain additives such as a plasticizer, an antioxidant, an anti-aging agent, and a colorant in addition to the elastomer.
- the said elastomer composition may contain another component further according to the use of a stretchable electrode.
- a stretchable electrode of the present invention when used as a sensor sheet for measuring a change in capacitance (hereinafter also referred to as a capacitance type sensor sheet), a dielectric filler such as barium titanate is used. You may contain. Thereby, the electrostatic capacitance C of a base material can be enlarged. As a result, the detection sensitivity of the capacitive sensor sheet can be increased.
- the elastomer composition contains a dielectric filler, the content of the dielectric filler in the elastomer composition is usually more than 0% by volume and about 25% by volume or less.
- the hardness of the base material may increase or permanent set may increase. Further, when molding a urethane rubber base material, the liquid viscosity before curing increases, so that it may be difficult to form a thin film with high accuracy.
- the electrode body is integrated with the base material, and is formed using multi-walled carbon nanotubes having a fiber length of 50 ⁇ m or more.
- the stretchable electrode of the present invention has an electrode body formed using such multi-walled carbon nanotubes having a long fiber length, so that it has excellent conductivity, and its electrical resistance hardly increases when stretched, and it is repeatedly stretched. It has an excellent characteristic that sometimes there is little variation in electrical resistance.
- the fiber length of the multi-walled carbon nanotube is less than 50 ⁇ m, the electrical resistance greatly increases as the stretchable electrode expands, and further, the electrical resistance varies when the stretchable electrode is repeatedly stretched. Becomes extremely large.
- the fiber length is preferably 100 ⁇ m or more.
- the preferable upper limit of the fiber length of the multi-walled carbon nanotube is 1000 ⁇ m. Multi-walled carbon nanotubes with fiber lengths exceeding 1000 ⁇ m are difficult to manufacture and obtain at present.
- the fiber length of the multi-walled carbon nanotubes exceeds 1000 ⁇ m
- the dispersion of the multi-walled carbon nanotubes tends to be insufficient, resulting in a conductive path. Is difficult to form, and there is a concern that the conductivity of the electrode body is insufficient.
- the lower limit of the average length of the multi-walled carbon nanotube is preferably 100 ⁇ m, and the upper limit is preferably 600 ⁇ m.
- the average length of the multi-walled carbon nanotube is within the above range, the electrical conductivity is excellent, the electrical resistance hardly increases at the time of stretching, and the variation in electrical resistance is small at the time of repeated stretching at a high level. It can be ensured more reliably.
- the fiber length of the multi-walled carbon nanotube may be measured from an observation image obtained by observing the multi-walled carbon nanotube with an electron microscope.
- the average length may be calculated based on, for example, the fiber lengths of 10 multi-walled carbon nanotubes randomly selected from the observed image of the multi-walled carbon nanotubes.
- multi-walled carbon nanotubes it is also important to use multi-walled carbon nanotubes as the carbon nanotubes.
- single-walled carbon nanotubes are used, even when carbon nanotubes have a long fiber length, the electrical resistance increases, the electrical resistance increases greatly when stretched, and the electrical resistance varies greatly during repeated expansion and contraction. Because.
- single-walled carbon nanotubes are usually synthesized as a mixture of metallic carbon nanotubes and semiconducting carbon nanotubes, the presence of these semiconducting carbon nanotubes increases the electrical resistance or the electrical resistance when stretched. It is speculated that this is a cause of a large increase in electric resistance and a large variation in electric resistance during repeated expansion and contraction.
- the metallic carbon nanotube and the semiconducting carbon nanotube are separated and only the single-walled carbon nanotube with a long fiber length is used, an electrode body having the same electrical characteristics as the electrode body according to the present invention can be obtained. The possibility of being formed is not denied. However, separation of metallic carbon nanotubes from semiconducting carbon nanotubes is not easy (particularly in carbon nanotubes having a long fiber length), and the separation of both requires complicated operations. Therefore, in this invention, the said electrode main body shall be formed using the multi-walled carbon nanotube also from the viewpoint of workability
- the number of layers is not particularly limited, and may be a double-walled carbon nanotube (DWNT) or a multi-walled carbon nanotube (MWNT) of three or more layers (in this specification, Both are simply referred to as multi-walled carbon nanotubes). Moreover, you may use together the multi-walled carbon nanotube from which the number of layers differs.
- DWNT double-walled carbon nanotube
- MWNT multi-walled carbon nanotube
- the fiber diameter of the multi-walled carbon nanotube is not particularly limited, but is preferably 5 to 30 nm.
- the fiber diameter is less than 5 nm, the dispersion of the multi-walled carbon nanotubes is deteriorated. As a result, the conductive path is not widened, and the conductivity of the electrode body may be insufficient.
- the number of carbon nanotubes may be reduced even with the same weight, and the conductivity may be insufficient.
- the average fiber diameter of the multi-walled carbon nanotube is not particularly limited, but is preferably 5 to 20 nm.
- the multi-walled carbon nanotube preferably has a carbon purity of 99% by weight or more.
- Carbon nanotubes may contain catalytic metals, dispersants, and the like in the production process.
- impurities components other than such carbon nanotubes are used, the decrease in conductivity or May cause variations in electrical resistance.
- the multi-walled carbon nanotubes may be those produced by a conventionally known production method, but those produced by a substrate growth method are preferred.
- the substrate growth method is a kind of CVD method, in which a carbon source is supplied to a metal catalyst applied on a substrate, and carbon nanotubes are grown on the substrate to produce carbon nanotubes.
- This substrate growth method is a production method suitable for producing carbon nanotubes having relatively long fiber lengths and uniform fiber lengths. Therefore, it is suitable as a method for producing a carbon nanotube used in the present invention, which has one technical feature of forming an electrode body using carbon nanotubes having a specific fiber length.
- the fiber length of the carbon nanotubes is substantially the same as the growth length of the CNT forest. Therefore, when measuring fiber length using an electron microscope, the growth length of a CNT forest should just be measured.
- the growth length of carbon nanotubes (CNT forest) The multi-wall carbon nanotubes on the substrate having a growth length of 50 ⁇ m or more may be used as multi-wall carbon nanotubes having a fiber length of 50 ⁇ m or more.
- the electrode body is formed using multi-walled carbon nanotubes having a fiber length of 50 ⁇ m or more. More specifically, for example, it is formed by applying a composition containing the above-mentioned multi-walled carbon nanotubes and a dispersion medium (hereinafter also referred to as a carbon nanotube dispersion) and then removing the dispersion medium by a drying treatment.
- a composition containing the above-mentioned multi-walled carbon nanotubes and a dispersion medium hereinafter also referred to as a carbon nanotube dispersion
- the said carbon nanotube dispersion liquid may contain only the said multilayer carbon nanotube other than a dispersion medium, it may contain other components other than a carbon nanotube with the said multilayer carbon nanotube.
- a binder component is mentioned, for example.
- the binder component can serve as a bridging material for multi-walled carbon nanotubes.
- the adhesion of the electrode body to the substrate and the strength of the electrode body itself can be improved.
- the scattering of the multi-walled carbon nanotubes can be suppressed when the electrode body is formed by the method described later, the safety at the time of forming the electrode body can be improved.
- binder component examples include butyl rubber, ethylene propylene rubber, polyethylene, chlorosulfonated polyethylene, natural rubber, isoprene rubber, butadiene rubber, styrene / butadiene rubber, polystyrene, chloroprene rubber, nitrile rubber, polymethyl methacrylate, polyacetic acid.
- examples include vinyl, polyvinyl chloride, acrylic rubber, styrene-ethylene-butylene-styrene block copolymer (SEBS), and the like. These may be used alone or in combination of two or more.
- SEBS styrene-ethylene-butylene-styrene block copolymer
- raw rubber in a state where natural rubber and synthetic rubber are not vulcanized
- the followability of the electrode body with respect to deformation of the base material during expansion and contraction can be improved.
- the binder component preferably has a solubility parameter (SP value [cal / cm 3 ) 1/2 ] close to the solubility parameter of the elastomer constituting the base material, and the absolute difference between the solubility parameters (SP value) of the two A value of 1 or less is more preferred. This is because the closer the solubility parameter, the better the adhesion between the substrate and the electrode body.
- the SP value is a value calculated by Fedors' estimation method.
- the binder component is preferably the same type as the elastomer constituting the substrate. This is because the adhesion between the substrate and the electrode body can be significantly improved.
- the carbon nanotube dispersion liquid includes, for example, additives for binder components such as a crosslinking agent, a vulcanization accelerator, and a vulcanization aid, an anti-aging agent, and a plasticizer. , Softeners, colorants and the like may be included.
- the said electrode main body contains a plasticizer and the said base material also contains a plasticizer, it is preferable that both plasticizer density
- the carbon nanotube dispersion liquid may contain carbon nanotubes other than multi-walled carbon nanotubes having a fiber length of 50 ⁇ m or more as long as the conductive properties of the electrode body to be formed are not impaired.
- the other components may not necessarily be contained, and the electrode body may be substantially composed of only multi-walled carbon nanotubes.
- the electrode body may be substantially composed of only multi-walled carbon nanotubes.
- the content of the multi-walled carbon nanotubes in the electrode body is not particularly limited as long as it is a concentration at which conductivity is exhibited, and when it contains a binder component, it varies depending on the type of the binder component.
- the content is preferably 0.1 to 100% by weight.
- the conductivity of the electrode body can be improved. Therefore, the required conductivity can be ensured even if the electrode body is thinned. As a result, it becomes easier to make the stretchable electrode thinner or to ensure the flexibility of the stretchable electrode.
- the average thickness is preferably 0.1 to 10 ⁇ m.
- the electrode main body can exhibit excellent followability with respect to the expansion and contraction of the base material during expansion and contraction.
- the conductivity may be insufficient.
- the average thickness of the electrode body exceeds 10 ⁇ m, the stretchable electrode itself becomes hard due to the reinforcing effect of the carbon nanotubes, and the stretchability may be insufficient.
- the shape of the electrode body is a layer, the average thickness of the electrode body can be measured using a laser microscope (for example, VK-9510 manufactured by Keyence Corporation).
- the thickness direction of the electrode main body laminated on the surface of the base material is scanned in steps of 0.01 ⁇ m, and the 3D shape is obtained. After measuring the average height of the rectangular area of 200 ⁇ 200 ⁇ m in the area where the electrode layer is laminated on the surface of the dielectric layer and the area where the electrode layer is not laminated, the step of the average height is measured.
- the average thickness of the electrode body may be used.
- the shape of the stretchable electrode of the present invention is not limited to the shape shown in FIG. 1, and may be the shape shown in FIGS. 2 (a) to (c), for example.
- 2A to 2C are cross-sectional views schematically showing another example of the stretchable electrode of the present invention.
- the stretchable electrode 110 shown in FIG. 2A has a shape in which the electrode main body 112 is sandwiched between two sheet-like base materials 111a and 111b. In the stretchable electrode having such a shape, the electrode main body is less likely to be damaged by an external impact or the like.
- the stretchable electrode 120 shown in FIG. 2B has a shape in which two sheet-like base materials 121a and 121b and two layers of electrode main bodies 122a and 122b are alternately stacked. It has a multilayer structure.
- the number of layers is not limited to two as shown in FIG. 2B, and may be three or more.
- the upper and lower surfaces of the layered electrode body may be protected by a base material.
- the stretchable electrode 130 shown in FIG. 2C has a shape in which two rows of electrode bodies 132 a and 132 b are laminated on the upper surface of a sheet-like base material 131.
- a circuit pattern made of carbon nanotubes is formed as the electrode body. May be.
- the shape of the stretchable electrode of the present invention is not limited to the shape shown so far, and various shapes according to the design of the stretchable electrode can be adopted.
- the stretchable electrode of the present invention Since the stretchable electrode of the present invention has the above-described configuration, it is excellent in flexibility, stretchability, and conductivity, and increases in electrical resistance at the time of extension and extremely small variation in electrical resistance at the time of repeated stretching. It has excellent characteristics.
- the stretchable electrode is stretched 100% in the uniaxial direction from the non-stretched state, and then stretched and stretched with one cycle of returning to the non-stretched state for 1000 cycles. In each cycle after the second cycle, 100% Increase rate of electrical resistance with respect to non-stretching during elongation ([[Electrical resistance value when stretched 100%]-[Electrical resistance value when stretched without 0%]]]] / [Electrical resistance value when unstretched] ] ⁇ 100) is preferably small. Specifically, it is preferably less than 100%.
- the stretchable electrode has an electrical resistance of the electrode body at 100% elongation in the 1000th cycle with respect to the electrical resistance of the electrode body at 100% elongation in the 2nd cycle.
- Rate of change in electrical resistance [1000th cycle, electrical resistance value when 100% stretched] ⁇ [absolute value of 2nd cycle, electrical resistance value when 100% stretched]) / [2nd cycle, when 100% stretched]
- the electrical resistance value] ⁇ 100 is preferably small. Specifically, it is preferably 10% or less, and more preferably 5% or less.
- the reason why the electrical resistance in the second and subsequent cycles is considered as the evaluation target, not in the first cycle, is that the behavior of the electrode body during extension (first cycle) is extended from the unextended state (first cycle) ( This is because the variation of the electrical resistance is greatly different from the second and subsequent expansion / contraction. For this reason, it is presumed that the state of the multi-walled carbon nanotube constituting the electrode body is stabilized only after the stretchable electrode is produced and then stretched once. Therefore, when using the stretchable electrode of the present invention, it is preferable to stretch it at least once after production and then use it.
- the stretchable electrode is preferably as large as possible to withstand uniaxial tension when stretched in a uniaxial direction from a non-stretched state. Specifically, it is preferably 30% or more, more preferably 50% or more, further preferably 100% or more, and particularly preferably 200% or more. It is because it becomes possible to use for various uses by enlarging the said expansion
- the elongation rate that can withstand uniaxial tension refers to an elongation rate that is equal to or lower than the elongation at break in a tensile test based on JIS K 6251 and restores the original state after releasing the tensile load.
- an elongation rate that can withstand uniaxial tension is 100% or more, when it is stretched 100% in the uniaxial direction, it does not break and is restored to its original state after releasing the tensile load (ie, In the elastic deformation range).
- the elongation ratio that can withstand the uniaxial tension can be controlled by the design (material, shape, etc.) of the substrate.
- the stretchable electrode of the present invention is, for example, (1) a step of producing a substrate composed of an elastomer composition (hereinafter also referred to as “step (1)”), and (2) A step of applying a composition containing multi-walled carbon nanotubes having a fiber length of 50 ⁇ m or more and a dispersion medium to form an electrode body integrated with the substrate (hereinafter also referred to as “step (2)”) , It can manufacture by going through.
- the manufacturing method of a stretchable electrode is demonstrated in order of a process for an example of the stretchable electrode provided with the sheet-like base material and the layered electrode main body.
- a substrate made of an elastomer composition is produced.
- an elastomer (or a raw material thereof) is added to a chain extender, a crosslinking agent, a vulcanization accelerator, a catalyst, a dielectric filler, a plasticizer, an antioxidant, an antioxidant, a colorant, etc.
- a raw material composition containing the additive is prepared.
- a base material is produced by molding this raw material composition.
- molding method A conventionally well-known method can be used.
- the polyol component, the plasticizer and the antioxidant are weighed, mixed under stirring for a certain time under heating and reduced pressure, and mixed. Prepare the solution. Next, after measuring the mixed solution and adjusting the temperature, the catalyst is added and stirred with an agitator or the like. Thereafter, a predetermined amount of an isocyanate component is added, and after stirring with an agitator or the like, the mixed solution is immediately poured into the molding apparatus shown in FIG. A roll-wrapped sheet having a predetermined thickness is obtained. Then, a base material can be manufactured by carrying out a crosslinking reaction for a certain period of time in a furnace.
- FIG. 3 is a schematic diagram for explaining an example of a molding apparatus used for producing a sheet-like base material.
- the raw material composition 33 is poured into the gap between the protective films 31 made of polyethylene terephthalate (PET) that is continuously fed out from a pair of rolls 32, 32 that are spaced apart from each other. While proceeding with a curing reaction (crosslinking reaction) with the raw material composition 33 held in the gap, it was introduced into the heating device 34 and thermally cured with the raw material composition 33 held between the pair of protective films 31, A sheet-like base material 35 is formed.
- PET polyethylene terephthalate
- the base material may be prepared using a general-purpose film forming apparatus or film forming method such as various coating apparatuses, bar coaters, doctor blades, etc. after preparing the raw material composition.
- a general-purpose film forming apparatus or film forming method such as various coating apparatuses, bar coaters, doctor blades, etc. after preparing the raw material composition.
- Step (2) In this step, first, a composition (carbon nanotube dispersion) containing multi-walled carbon nanotubes having a fiber length of 50 ⁇ m or more and a dispersion medium is applied. Thereafter, the dispersion medium is removed by a drying process to form an electrode body integrated with the substrate.
- multi-walled carbon nanotubes are added to the dispersion medium.
- a coating liquid carbon nanotube dispersion liquid
- an existing disperser such as an ultrasonic disperser, a jet mill, or a bead mill may be used for dispersion.
- dispersion medium examples include toluene, methyl isobutyl ketone (MIBK), alcohols, water, and the like. These dispersion media may be used independently and may be used together 2 or more types.
- the concentration of the multi-walled carbon nanotube is preferably 0.01 to 10% by weight. If it is less than 0.01% by weight, the concentration of the multi-walled carbon nanotubes may be too thin, and it may be necessary to apply repeatedly. On the other hand, if it exceeds 10% by weight, the viscosity of the coating solution may become too high, and the dispersibility of the multi-walled carbon nanotubes may decrease due to reaggregation, which may make it difficult to form a uniform electrode body.
- the coating liquid is applied to a predetermined position on the surface of the substrate by spray coating or the like and dried.
- the coating solution may be applied after masking a position on the substrate surface where the electrode body is not formed.
- the drying conditions for the coating solution are not particularly limited, and may be appropriately selected according to the type of the dispersion medium, the composition of the elastomer composition, and the like.
- the method of applying the coating liquid is not limited to spray coating, and other methods such as screen printing and ink jet printing can also be employed.
- the surface of the substrate may be pretreated in order to improve the adhesion between the substrate and the electrode body.
- the electrode body and the base material formed using the multi-walled carbon nanotube have extremely excellent adhesion, it is sufficient between the base material and the electrode body without any pretreatment. Adhesion can be ensured.
- a stretchable electrode having a shape as shown in FIGS. 1 and 2C can be manufactured.
- various coating apparatuses, bar coaters, doctors, etc. The raw material composition can be applied by using a general-purpose film forming apparatus such as a blade or a film forming method, and then thermally cured.
- a sheet (base material) obtained by cross-linking or semi-cross-linking the raw material composition for preparing the base material is separately prepared, and manufactured by laminating the base material having the electrode body formed on one surface. It is also possible to do.
- semi-crosslinking it may be completely crosslinked after lamination.
- the base body is first prepared, and then the electrode body is formed thereon. And another base material are sequentially laminated by the method described above to produce a stretchable electrode having a multilayer structure.
- Such a stretchable electrode of the present invention can be suitably used as a sensor sheet, for example.
- the use of the stretchable electrode of the present invention is not limited to the sensor sheet, and other than the conductive wiring material, the dielectric elastomer type actuator or generator, and further, the place where the stretchable flexibility is required. It can be used for various applications such as various signal lines and low-power power lines.
- the sensor sheet of the present invention is a sensor sheet using the stretchable electrode of the present invention
- the substrate is in sheet form, and the electrode body is provided on both sides of the substrate,
- the electrode main body provided on one surface of the substrate and the electrode main body provided on the other surface of the substrate are at least partially opposed to each other with the substrate interposed therebetween.
- the electrode main body is provided on both surfaces of the base material, and the electrode main body provided on one surface of the base material and the electrode main body provided on the other surface include the base material. At least part of the surface is opposed. Therefore, the stretchable electrode of the present invention constitutes a capacitor having the base material as a dielectric layer.
- the capacitance of the portion facing the base material of the electrode body changes due to expansion and contraction of the dielectric layer (base material) and the electrode body following the dielectric layer (base material). Therefore, by measuring this change in capacitance, for example, it can be suitably used for a capacitance sensor that detects the amount of deformation and the like.
- the electrode body may have a strip shape, and may be provided in multiple rows on both surfaces of the base material.
- the deformation strain distribution and the surface pressure distribution can also be measured by detecting the deformation strain amount for each of the portions facing each other with the substrate interposed therebetween.
- FIG. 4A is a plan view schematically showing an example of the sensor sheet of the present invention
- FIG. 4B is a cross-sectional view taken along line AA of the sensor sheet shown in FIG.
- a sensor sheet 1 shown in FIGS. 4A and 4B is a capacitive sensor sheet, and a plurality of rows laminated on a sheet-like dielectric layer 2 and the surface (front surface) of the dielectric layer 2.
- the strip-shaped front electrode layers 01A to 16A, a plurality of rows of strip-shaped back electrode layers 01B to 16B stacked on the back surface of the dielectric layer 2, and external wiring provided at one end of the front electrode layers 01A to 16A are connected.
- portions where the front electrode layers 01A to 16A and the back electrode layers 01B to 16B are opposed to each other with the dielectric layer 2 interposed therebetween are detection units C0101 to C1616.
- the detection unit code “CXXX” correspond to the front electrode layers 01A to 16A
- the lower two digits “ ⁇ ” indicate the back electrode layers 01B to 01B. Corresponding to 16B.
- the front electrode layers 01A to 16A each have a strip shape, and a total of 16 layers are laminated on the surface of the dielectric layer 2.
- the front-side electrode layers 01A to 16A each extend in the X direction (the left-right direction in FIG. 4A).
- the front-side electrode layers 01A to 16A are respectively arranged so as to be substantially parallel to each other at a predetermined interval in the Y direction (vertical direction in FIG. 4A).
- the back-side electrode layers 01B to 16B each have a strip shape, and a total of 16 layers are laminated on the back surface of the dielectric layer 2.
- the back-side electrode layers 01B to 16B are arranged so as to be substantially orthogonal to the front-side electrode layers 01A to 16A, respectively, when viewed from the front-back direction (thickness direction of the dielectric layer). That is, the back side electrode layers 01B to 16B each extend in the Y direction. Further, the back side electrode layers 01B to 16B are spaced apart from each other at predetermined intervals in the X direction, and are arranged so as to be substantially parallel to each other.
- the detection part will be arrange
- the front electrode layer and the back electrode layer are formed independently, there are a front side electrode and a back side electrode for each detection unit. Therefore, in order to detect the capacitance of the detection unit, 256 ⁇ 2 512 is used. Book wiring is required.
- the front electrode layer and the back electrode layer are formed of a plurality of rows of strips arranged in parallel. When the electrode layers are arranged so as to be substantially orthogonal when viewed from the front and back direction, 32 wires of 16 + 16 are sufficient for detecting the capacitance of the detection unit. For this reason, the detection units are efficiently arranged as described above.
- the dielectric layer 2 corresponds to the base material in the stretchable electrode of the present invention, and the front electrode layers 01A to 16A and the back electrode layers 01B to 16B. Each corresponds to an electrode body in the stretchable electrode of the present invention.
- the sensor sheet 1 having such a configuration is connected to a measuring unit to form a capacitive sensor, and each of the 16 wires is switched by an external switching circuit, thereby detecting 256 detection units.
- the capacitance of each detection unit can be measured while switching one by one.
- information such as distortion distribution in a sensor sheet, a distortion position, and surface pressure distribution, can be detected based on the capacitance of each detection part.
- the average thickness of the dielectric layer is to increase the capacitance C and improve the detection sensitivity, and to improve the followability to the measurement object.
- the thickness is preferably 10 to 1000 ⁇ m, and more preferably 30 to 200 ⁇ m.
- the dielectric constant at normal temperature of the dielectric layer is preferably 2 or more, and more preferably 5 or more. When the dielectric constant of the dielectric layer is less than 2, the capacitance C becomes small, and sufficient sensitivity may not be obtained when used as a capacitance type sensor.
- the outer shape such as the average thickness, width, and length of the dielectric layer (base material), the front electrode layer, and the back electrode layer (electrode body) is appropriately determined depending on the application of the sensor sheet used. Design changes are possible.
- the sensor sheet of the present invention may be a sensor sheet having only one detection portion in the sheet where the front electrode layer and the back electrode layer are opposed to each other with the base material interposed therebetween.
- the Young's modulus of the substrate is preferably 0.1 to 1 MPa. If the Young's modulus is less than 0.1 MPa, the substrate is too soft, high quality processing is difficult, and sufficient measurement accuracy may not be obtained. On the other hand, if the Young's modulus exceeds 1 MPa, the base material is too hard, and when the deformation load of the measurement object is small, the deformation operation of the measurement object is hindered, and the measurement result may not match the measurement purpose. .
- the base material has a hardness using a type A durometer in accordance with JIS K 6253 (JIS A hardness), 0 to It is preferably 30 ° or 10 to 55 ° in terms of hardness (JIS C hardness) using a type C durometer according to JIS K 7321. If the C hardness is less than 10 °, the base material is too soft, making high-quality processing difficult, and sufficient measurement accuracy may not be ensured. On the other hand, if it exceeds 55 °, the base material is too hard. Therefore, when the deformation load of the measurement object is small, the deformation operation of the measurement object is hindered, and the measurement result may not match the measurement purpose.
- the structure of the sensor sheet of this invention is not necessarily limited to the structure shown to Fig.4 (a), (b),
- an insulating layer on the surface layer side of a front side electrode layer and / or a back side electrode layer ( A shield electrode layer for removing crosstalk noise via a dielectric layer) may be formed so as to cover the detection portion.
- the sensor sheet having such a configuration can be made into a capacitive sensor by connecting each of the front side electrode layer and the back side electrode layer to a measuring means via an external wiring.
- the capacitance type sensor of the present invention comprises the sensor sheet of the present invention, measurement means, electrode bodies (the front electrode layer and the back electrode layer) provided in the sensor sheet, and external wiring for connecting the measurement means.
- the portion of the electrode body provided on one surface of the base material and the electrode main body provided on the other surface of the base material facing each other with the base material interposed therebetween is used as a detection unit.
- the deformation distortion amount is measured by measuring a change in capacitance in the detection unit.
- FIG. 5 is a plan view schematically showing an example of the capacitive sensor of the present invention.
- a capacitive sensor 201 shown in FIG. 5 includes the sensor sheet 1 using the stretchable electrode of the present invention shown in FIG. 4, external wirings 202 and 203, and measuring means 204.
- Each of the front side connection portions 01A1 to 16A1 of the sensor sheet 1 is connected to the measuring means 204 via an external wiring 203 in which a plurality of (16) wires are bundled, and each of the back side connection portions 01B1 to 16B1.
- the external wiring only needs to be connected to one end of the front electrode layer and the back electrode layer, but may be connected to both ends depending on circumstances.
- the measuring unit 204 includes a power supply circuit, an arithmetic circuit, a capacitance, a measurement circuit, a pixel switching circuit, a display device, and the like as necessary.
- Specific examples of the measuring unit 204 include an LCR meter and the like.
- the change amount ⁇ C of the capacitance is detected from the capacitance C before placing the measurement object and the capacitance C after placing the measurement object.
- the deformation strain amount can be obtained on the basis of the change amount ⁇ C, and the deformation strain distribution and the surface pressure distribution can be obtained on the basis of the deformation strain amount of each detection unit.
- the sensor sheet (stretchable electrode) has a high elongation rate and can be repeatedly stretched by 30% or more in one axial direction, and can follow the deformation and operation of a flexible measurement object. In addition, it is excellent in durability against stretching deformation and repeated deformation. Therefore, in the capacitive sensor provided with the sensor sheet, for example, the shape of the measurement object can be traced, or the movement of the measurement object can be directly detected.
- Preparation Example 1 Preparation of carbon nanotube dispersion (A-1)) Highly oriented carbon nanotubes manufactured by Taiyo Nippon Sanso, which are multi-walled carbon nanotubes manufactured by the substrate growth method (4 to 12 layers, fiber diameter 10 to 20 nm, fiber length 50 to 150 ⁇ m, carbon purity 99.5% ) 30 mg was added to 30 g of methyl isobutyl ketone (MIBK), and subjected to wet dispersion using a jet mill (Nanojet PAL JN10-SP003, manufactured by Joko), and a carbon nanotube dispersion A- having a concentration of 0.1% by weight. 1 was obtained.
- MIBK methyl isobutyl ketone
- FIG. 6 is one of the electron micrographs taken of the highly oriented carbon nanotubes used in Preparation Example 1.
- FIG. 7 is one of the electron micrographs taken of the highly oriented carbon nanotubes used in Preparation Example 1.
- Preparation Example 2 Preparation of carbon nanotube dispersion (A-2)
- Highly oriented carbon nanotubes manufactured by Taiyo Nippon Sanso Co., Ltd. multilayer carbon nanotubes having a fiber length of 10 to 20 nm, fiber length of 150 to 300 ⁇ m, carbon purity of 99, carbon fiber having a fiber length different from that of Preparation Example 1) 0.5%), and a carbon nanotube dispersion A-2 having a concentration of 0.1% by weight was obtained in the same manner as in Preparation Example 1 above.
- the average length and the average fiber diameter were calculated in the same manner as in Preparation Example 1. The average length was 298 ⁇ m and the average fiber diameter was 12.9 nm.
- Preparation Example 3 Preparation of carbon nanotube dispersion liquid (A-3)
- Highly oriented carbon nanotubes manufactured by Taiyo Nippon Sanso Co., Ltd. (4 to 12 layers, fiber diameter 10 to 20 nm, length 300 to 600 ⁇ m, carbon purity 99. 5%), and a carbon nanotube dispersion A-3 having a concentration of 0.1% by weight was obtained in the same manner as in Preparation Example 1 above.
- the average length and the average fiber diameter were calculated in the same manner as in Preparation Example 1. As a result, the average length was 591 ⁇ m and the average fiber diameter was 11.1 nm.
- Example 1 Hydrogenated hydroxyl group-terminated liquid polyolefin polyol (Epol, manufactured by Idemitsu Kosan Co., Ltd.) 100 parts by mass, high temperature lubricating oil mainly composed of alkyl-substituted diphenyl ether (Molesco High Lube LB-100, manufactured by MORESCO) 100 parts by mass Were weighed and mixed by stirring at 2000 rpm for 3 minutes using a rotation and revolution mixer (manufactured by THINKY). Next, 0.07 part by mass of a catalyst (Fomrez catalyst UL-28, manufactured by Momentive) was added to the resulting mixture, and the mixture was stirred for 1.5 minutes with a rotation and revolution mixer.
- a catalyst Fomrez catalyst UL-28, manufactured by Momentive
- Example 2 A stretchable electrode was obtained in the same manner as in Example 1 except that the carbon nanotube dispersion liquid (A-2) was used instead of the carbon nanotube dispersion liquid (A-1).
- Example 3 A stretchable electrode was obtained in the same manner as in Example 1 except that the carbon nanotube dispersion liquid (A-3) was used instead of the carbon nanotube dispersion liquid (A-1).
- Example 2 A stretchable electrode was obtained in the same manner as in Example 1 except that the carbon nanotube dispersion liquid (C) was used instead of the carbon nanotube dispersion liquid (A-1).
- copper foils 53 are attached to both ends of an electrode body 52 integrated with the base material 51 via conductive grease (not shown), and the electrode body 52 of the stretchable electrode 50 is attached. 2 sides are restrained by the resin frame 54, and the copper foils 53 attached to both ends of the electrode body 52 are connected to the multimeter 56 (manufactured by ADVANTEST, R6441C) 56 via the leads 55, and the space between the frames is After extending in the uniaxial direction (in the direction of the arrow in the figure), the expansion and contraction to return to the non-extended state was repeated, and the change in electrical resistance was measured. At this time, the distance between frames (see L in FIG. 8) was 50 mm. The measurement results are shown in FIGS.
- the stretchable electrode including the electrode body formed using the multi-walled carbon nanotube having a fiber length of 50 ⁇ m or more has excellent conductivity ( The electrical resistance itself was low), and there was almost no increase in electrical resistance when 100% stretched, and there was almost no variation in electrical resistance during repeated expansion and contraction.
- the example (Comparative Example 1) provided with the electrode body made of multi-walled carbon nanotubes having a short average length of about 10 ⁇ m, the conductivity is low, and the electrical resistance at the time of expansion and the electricity at the time of repeated expansion and contraction are reduced. The variation in resistance was remarkable.
- the example (Comparative Example 2) provided with the electrode main body made of single-walled carbon nanotubes the conductivity was low.
- the stretchable electrode of the present invention is used for various applications such as sensor sheets, conductive wiring materials, dielectric elastomer actuators, generators, and various signal lines and low-power power lines in places where stretch flexibility is required. Therefore, it can be suitably used as a sensor sheet such as a capacitive sensor that requires stretchability and flexibility.
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Abstract
Description
また、特許文献2に記載された柔軟電極では、柔軟性は確保されているものの、伸縮性に劣り、高伸長時に電気抵抗が増大したり、繰返し伸縮時に電気抵抗にバラツキが生じたりするとの課題があった。
上記電極本体は、繊維長さが50μm以上の多層カーボンナノチューブを用いて形成されていることを特徴とする。
また、上記伸縮性電極は、センサシートに好適に用いることができる。
上記基材はシート状であり、上記電極本体は上記基材の両面に設けられ、
上記基材の一方の面に設けられた電極本体と上記基材の他方の面に設けられた電極本体とは、上記基材を挟んで少なくとも一部が対向していることを特徴とする。
上記センサシートにおいて、上記電極本体は、帯状であって、上記基材の両面に複数列ずつ設けられている。
上記基材の一方の面に設けられた電極本体と上記基材の他方の面に設けられた電極本体との上記基材を挟んで対向している部分を検出部とし、
上記計測手段は、上記検出部における静電容量の変化を計測することにより、変形歪み量を測定することを特徴とする。
本発明の静電容量型センサは、本発明のセンサシートを備えているため、測定精度及び長期信頼性に優れる。
本発明の伸縮性電極は、エラストマー組成物からなる基材と、上記基材と一体化されたカーボンナノチューブからなる電極本体とを備え、
上記電極本体は、繊維長さが50μm以上の多層カーボンナノチューブを用いて形成されていることを特徴とする。
図1(a)、(b)に示す伸縮性電極100では、エラストマー組成物からなるシート状の基材101の上面全体にカーボンナノチューブを用いて形成された電極本体102が積層され、一体化されている。
上記エラストマー組成物としては、エラストマーと、必要に応じて他の任意成分とを含有するものが挙げられる。
上記エラストマーとしては、例えば、天然ゴム、イソプレンゴム、ニトリルゴム(NBR)、エチレンプロピレンゴム(EPDM)、スチレン・ブタジエンゴム(SBR)、ブタジエンゴム(BR)、クロロプレンゴム(CR)、シリコーンゴム、フッ素ゴム、アクリルゴム、水素添加ニトリルゴム、ウレタンゴム等が挙げられる。これらは単独で用いても良いし、2種以上併用しても良い。
これらのなかでは、ウレタンゴム、シリコーンゴムが好ましい。永久歪み(または永久伸び)が小さいからである。
更に、シリコーンゴムに比べ、カーボンナノチューブとの密着性に優れる点から、ウレタンゴムが特に好ましい。
また、上記ウレタンゴムは、2種以上の上記ポリオール成分を併用したものであってもよい。
また、上記エステル系ポリオールとしては、例えば、ポリライト8651(DIC社製)等が挙げられる。
また、上記エーテル系ポリオールとしては、例えば、ポリオキシテトラメチレングリコール、PTG-2000SN(保土谷化学工業社製)、ポリプロピレングリコール、プレミノールS3003(旭硝子社製)等が挙げられる。
また、上記ウレタンゴムを合成する際には、その反応系中に必要に応じて、鎖延長剤、架橋剤、触媒、加硫促進剤等を加えても良い。
具体的には、例えば、本発明の伸縮性電極を静電容量の変化を測定するセンサシート(以下、静電容量型センサシートともいう)として用いる場合には、チタン酸バリウムなどの誘電フィラーを含有してもよい。これにより、基材の静電容量Cを大きくすることができる。その結果、静電容量型センサシートの検出感度を高めることができる。
上記エラストマー組成物が誘電フィラーを含有する場合、上記エラストマー組成物中における誘電フィラーの含有量は、通常、0体積%より多く、25体積%以下程度である。
誘電フィラーの含有量が25体積%を超えると、基材の硬度が高くなったり、永久歪みが大きくなったりすることがある。また、ウレタンゴム製の基材を成形する際に、硬化前の液粘度が高くなるため薄膜を高精度で形成することが難しくなることがある。
本発明の伸縮性電極は、このような繊維長さが長い多層カーボンナノチューブを用いて形成された電極本体を備えているため、導電性に優れ、伸長時に電気抵抗がほとんど増大せず、繰り返し伸縮時に電気抵抗のバラツキが小さい、との優れた特性を有する。
一方、上記多層カーボンナノチューブの繊維長さの好ましい上限は1000μmである。繊維長さが1000μmを超える多層カーボンナノチューブは、現時点では、その製造、入手が困難である。また、多層カーボンナノチューブの繊維長さが1000μmを超えると、多層カーボンナノチューブの分散液を塗布して電極本体を形成する場合に、多層カーボンナノチューブの分散が不充分になりやすく、その結果、導電パスが形成されにくく、電極本体の導電性が不充分となることが懸念される。
上記多層カーボンナノチューブの平均長さが上記範囲内にあると、導電性に優れ、伸長時に電気抵抗がほとんど増大せず、繰り返し伸縮時に電気抵抗のバラツキが小さい、との優れた特性を高いレベルでより確実に確保することができる。
また、その平均長さは、例えば、多層カーボンナノチューブの観察画像から無作為に選んだ10箇所の多層カーボンナノチューブの繊維長さに基づき平均値を算出すればよい。
単層カーボンナノチューブを用いた場合には、繊維長さが長いカーボンナノチューブであっても、電気抵抗が高くなったり、伸長時に電気抵抗が大きく増大したり、繰り返し伸縮時に電気抵抗が大きくばらついたりするからである。これについては、単層カーボンナノチューブは、通常、金属性カーボンナノチューブと半導体性カーボンナノチューブとの混合物として合成されるため、この半導体性カーボンナノチューブの存在が、電気抵抗が高くなったり、伸長時に電気抵抗が大きく増大したり、繰り返し伸縮時に電気抵抗が大きくばらついたりする原因となっていると推測している。
なお、金属性カーボンナノチューブと半導体性カーボンナノチューブとを分離し、繊維長さの長い金属性の単層カーボンナノチューブのみを用いれば、本発明に係る電極本体と同様の電気特性を備えた電極本体を形成することができる可能性は否定されない。しかしながら、金属性カーボンナノチューブと半導体性カーボンナノチューブとの分離は容易ではなく(特に、繊維長さの長いカーボンナノチューブにおいて)、両者の分離には煩雑な作業が必要となる。そのため、本発明では、電極本体を形成する際の作業容易性、及び、経済性の観点からも上記電極本体を多層カーボンナノチューブを用いて形成されたものとしている。
上記繊維径が5nm未満では、多層カーボンナノチューブの分散が悪くなり、その結果、導電パスが広がらず、電極本体の導電性が不充分になることがある。一方、30nmを超えると、同じ重量でもカーボンナノチューブの本数が少なくなり、導電性が不充分になることがある。
また、上記多層カーボンナノチューブの平均繊維径は特に限定されないが、5~20nmが好ましい。
カーボンナノチューブは、その製造工程において、触媒金属や分散剤等が含まれることがあり、このようなカーボンナノチューブ以外の成分(不純物)を多量に含有するカーボンナノチューブを用いた場合、導電性の低下や、電気抵抗のバラツキを引き起こすことがある。
基板成長法は、CVD法の1種であり、基板上に塗布した金属触媒に炭素源を供給し、基板上でカーボンナノチューブを成長させてカーボンナノチューブを製造する方法である。この基板成長法は、比較的繊維長さが長く、かつ、繊維長さの揃ったカーボンナノチューブを製造するのに適した製造方法である。そのため、特定の繊維長さのカーボンナノチューブを用いて電極本体を形成することを技術的特徴の1つとする本発明で使用するカーボンナノチューブの製造方法として適している。
また、本発明においてカーボンナノチューブが基板成長法により製造されたものである場合、カーボンナノチューブの繊維長さは、CNTフォレストの成長長さと実質的に同一である。よって、電子顕微鏡を用いて繊維長さを測定する場合は、CNTフォレストの成長長さを測定すればよい。
本発明では、カーボンナノチューブとして繊維長さが50μm以上の多層カーボンナノチューブを使用することが重要であり、基板成長法により製造したカーボンナノチューブを使用する場合には、カーボンナノチューブの成長長さ(CNTフォレストの成長長さ)が50μm以上となった基板上の多層カーボンナノチューブを、繊維長さが50μm以上の多層カーボンナノチューブとして使用すればよい。
上記カーボンナノチューブ分散液は、分散媒以外に上記多層カーボンナノチューブのみを含有していてもよいが、上記多層カーボンナノチューブとともにカーボンナノチューブ以外の他の成分を含有していてもよい。
上記バインダー成分は、多層カーボンナノチューブのつなぎ材料としての役割を果たすことができる。上記バインダー成分を含有させることにより、電極本体の基材との密着性、及び、電極本体自体の強度を向上させることができる。さらに、後述した方法で電極本体を形成する際に多層カーボンナノチューブの飛散を抑制することができるため、電極本体形成時の安全性も高めることができる。
また、上記バインダー成分としては、生ゴム(天然ゴム及び合成ゴムの加硫させていない状態のもの)も使用することができる。このように比較的弾性の弱い材料を用いることで、伸縮時の基材の変形に対する電極本体の追従性も高めることができる。
なお、本発明において、上記SP値はFedorsの推算法により算出した値である。
上記バインダー成分は、特に基材を構成するエラストマーと同種のものが好ましい。基材と電極本体との密着性を顕著に向上させることができるからである。
ここで、上記電極本体が可塑剤を含有し、かつ、上記基材もまた可塑剤を含有する場合には、両者の可塑剤濃度は同一であることが好ましい。基材と電極本体と間での可塑剤の移行を防止し、これにより伸縮性電極における反りやシワの発生を抑制することができるからである。
また、上記カーボンナノチューブ分散液は、形成される電極本体の導電特性を損ねない範囲で、繊維長さが50μm以上の多層カーボンナノチューブ以外のカーボンナノチューブを含有していてもよい。
また、多層カーボンナノチューブの含有量を高めれば、電極本体の導電性を向上させることができる。そのため、電極本体を薄くしても要求される導電性を確保することができる。その結果、伸縮性電極を薄くしたり、伸縮性電極の柔軟性を確保したりすることがより容易になる。
これに対して、上記電極本体の平均厚さが0.1μm未満では、導電性が不足するおそれがある。一方、上記電極本体の平均厚さが10μmを超えるとカーボンナノチューブの補強効果により伸縮性電極自体が硬くなり、伸縮性が不充分となるおそれがある。
なお、電極本体の形状が層状である場合、電極本体の平均厚さはレーザー顕微鏡(例えば、キーエンス社製、VK-9510)を用いて測定することができる。
具体的には、例えば、基材の表面の一部に電極本体を積層した場合には、基材の表面に積層された電極本体の厚さ方向を0.01μm刻みでスキャンし、その3D形状を測定した後、誘電層の表面に電極層が積層されている領域及び積層されていない領域において、それぞれ縦200×横200μmの矩形領域の平均高さを計測し、その平均高さの段差を電極本体の平均厚さとすればよい。
図2(a)~(c)は、それぞれ本発明の伸縮性電極の別の一例を模式的に示す断面図である。
なお、電極本体が多層構造を有している場合、その層数は図2(b)に示したように2層に限定されず、3層以上であってもよい。また、層状の電極本体はその上下面が基材で保護されていてもよい。
勿論、本発明の伸縮性電極の形状は、ここまで図示した形状に限定される訳ではなく、伸縮性電極の設計に応じた種々の形状を採用することができる。
上記伸縮性電極は、無伸長状態から一軸方向に100%伸長させた後、無伸長状態に戻すサイクルを1サイクルとする伸縮を1000サイクル繰返した際、2サイクル目以降の各サイクルにおいて、100%伸長時の無伸長時に対する電気抵抗の増加率(〔[100%伸長時の電気抵抗値]-[無伸長時(0%伸長時)の電気抵抗値]〕/[無伸長時の電気抵抗値]×100)が小さいことが好ましい。具体的には、100%未満であることが好ましい。
従って、本発明の伸縮性電極を使用する際には、製造後、少なくとも1回は伸縮させ、その後使用することが好ましい。
上記伸長率を大きくすることで、種々の用途に使用することが可能となるからである。
一軸引張りに耐えられる伸長率とは、JIS K 6251に準拠した引張り試験において、破断時伸び以下の伸長率であって、かつ、引張荷重を開放後元の状態に復元する伸長率をいう。例えば、一軸引張りに耐えられる伸長率が100%以上であるとは、一軸方向に100%伸長させた際には破断に至らず、かつ、引張荷重を開放した後に元の状態に復元する(即ち、弾性変形範囲にある)ことを意味する。
上記一軸引張りに耐えられる伸長率は、基材の設計(材質や形状等)により制御することができる。
本発明の伸縮性電極は、例えば、
(1)エラストマー組成物からなる基材を作製する工程(以下、「工程(1)」ともいう)、及び、
(2)繊維長さが50μm以上の多層カーボンナノチューブ及び分散媒を含む組成物を塗布し、上記基材と一体化された電極本体を形成する工程(以下、「工程(2)」ともいう)、
を経ることより製造することができる。
以下、シート状の基材と層状の電極本体とを備えた伸縮性電極を例に、伸縮性電極の製造方法を工程順に説明する。
本工程では、エラストマー組成物からなる基材を作製する。
まず、原料組成物としてエラストマー(又はその原料)に、必要に応じて、鎖延長剤、架橋剤、加硫促進剤、触媒、誘電フィラー、可塑剤、酸化防止剤、老化防止剤、着色剤等の添加剤を配合した原料組成物を調製する。
次に、この原料組成物を成形することにより基材を作製する。ここで、成形方法としては特に限定されず、従来公知の方法を用いることができる。
具体的には、基材としてウレタンゴムを含む基材を成形する場合には、例えば、まず、ポリオール成分、可塑剤及び酸化防止剤を計量し、加熱、減圧下において一定時間撹拌混合し、混合液を調製する。次に、混合液を計量し、温度を調整した後、触媒を添加しアジター等で撹拌する。その後、所定量のイソシアネート成分を添加し、アジター等で撹拌後、即座に混合液を図3に示す成形装置に注入し、保護フィルムでサンドイッチ状にして搬送しつつ架橋硬化させ、保護フィルム付きの所定厚みのロール巻シートを得る。その後、さらに炉で一定時間架橋反応させることで基材を製造することができる。
本工程では、まず、繊維長さが50μm以上の多層カーボンナノチューブ及び分散媒を含む組成物(カーボンナノチューブ分散液)を塗布する。その後、乾燥処理にて分散媒を除去することにより、上記基材と一体化された電極本体を形成する。
次に、多層カーボンナノチューブを含む各成分を湿式分散機を用いて分散媒中に分散(又は溶解)させることより塗布液(カーボンナノチューブ分散液)を調製する。ここでは、例えば、超音波分散機、ジェットミル、ビーズミルなど既存の分散機を用いて分散させればよい。
0.01重量%未満では、多層カーボンナノチューブの濃度が薄すぎて繰返し塗布する必要が生じる場合がある。一方、10重量%を超えると、塗布液の粘度が高くなりすぎ、また再凝集により多層カーボンナノチューブの分散性が低下し、均一な電極本体を形成することが困難となる場合がある。
上記塗布液の乾燥条件は特に限定されず、分散媒の種類やエラストマー組成物の組成等に応じて適宜選択すればよい。
また、図2(a)に示したような形状の伸縮性電極を製造する場合には、例えば、上述した方法で基材の一面に電極本体を形成した後、各種コーティング装置、バーコート、ドクターブレードなどの汎用の成膜装置や成膜方法等を用いて上記原料組成物を塗布し、その後、熱硬化させることにより製造することができる。また、上記基材を作製するための原料組成物を架橋または半架橋させて得たシート(基材)を別途作製し、一の面に電極本体が形成された基材にラミネートすることにより製造することも可能である。半架橋の場合にはラミネート後に完全架橋させてもよい。
本発明のセンサシートは、本発明の伸縮性電極を用いたセンサシートであって、
上記基材はシート状であり、上記電極本体は上記基材の両面に設けられ、
上記基材の一方の面に設けられた電極本体と上記基材の他方の面に設けられた電極本体とは、上記基材を挟んで少なくとも一部が対向していることを特徴とする。
そして、本発明のセンサシートは、誘電層(基材)及びこれに追従する電極本体の伸縮により電極本体の基材を挟んで対向している部分の静電容量が変化する。そのため、この静電容量の変化を計測することにより、例えば、変形歪み量等を検出する静電容量センサに好適に使用することができる。
また、上記センサシートにおいて、上記電極本体は、帯状であって、上記基材の両面に複数列ずつ設けられていてもよい。この場合、基材を挟んで対向している部分毎に変形歪み量を検出することで、変形歪み分布や面圧分布を測定することもできる。
図4(a)は本発明のセンサシートの一例を模式的に示す平面図であり、(b)は(a)に示したセンサシートのA-A線断面図である。
センサシート1では、表側電極層01A~16Aと裏側電極層01B~16Bとが誘電層2を挟んで対向する部分(誘電層の厚さ方向で交差する部分)が検出部C0101~C1616となる。なお、検出部の符号「C○○△△」中、上2桁の「○○」は、表側電極層01A~16Aに対応し、下2桁の「△△」は、裏側電極層01B~16Bに対応する。
そして、各検出部の静電容量に基づき、センサシート内の歪み分布や歪み位置、面圧分布等の情報を検知することができる。
また、上記誘電層の常温における比誘電率は、2以上が好ましく、5以上がより好ましい。誘電層の比誘電率が2未満であると、静電容量Cが小さくなり、静電容量型センサとして使用した際に充分な感度が得られないことがある。
そして、本発明のセンサシートは、表側電極層と裏側電極層とが基材を挟んで対向する検出部をシート内に1箇所のみ有するセンサシートであってもよい。
上記C硬さが10°未満では、基材が軟らかすぎるため高品質な加工が難しく、充分な測定精度を確保することができない場合があり、一方、55°を超えると、基材が硬すぎるため、測定対象物の変形荷重が小さい場合に測定対象物の変形動作を阻害してしまい、計測目的に対して測定結果がそぐわないおそれがある。
上記基材の一方の面に設けられた電極本体と上記基材の他方の面に設けられた電極本体との上記基材を挟んで対向している部分を検出部とし、
上記検出部における静電容量の変化を計測することにより、変形歪み量を測定することを特徴とする。
図5は、本発明の静電容量型センサの一例を模式的に示す平面図である。
センサシート1の表側接続部01A1~16A1のそれぞれは、複数(16本)の配線が結束された外部配線203を介して計測手段204と接続されており、また、裏側接続部01B1~16B1のそれぞれは、複数(16本)の配線が結束された外部配線202を介して計測手段204と接続されている。
なお、外部配線は、図5に示すように表側電極層及び裏側電極層の片端にのみ接続されていればよいが、場合によっては両端に接続されていても良い。
また、上記センサシート(伸縮性電極)は、伸長率が高く、1軸方向に30%以上繰り返し伸長させることが可能であり、柔軟な測定対象物の変形や動作に追従することが可能で、かつ伸縮変形や繰り返し変形に対する耐久性に優れる。そのため、上記センサシートを備えた静電容量型センサでは、例えば、測定対象物の形をトレースしたり、測定対象物の動きを直接的に検知したりすること等ができる。
(調製例1:カーボンナノチューブ分散液(A-1)の調製)
基板成長法により製造した多層カーボンナノチューブである、大陽日酸社製の高配向カーボンナノチューブ(層数4~12層、繊維径10~20nm、繊維長さ50~150μm、炭素純度99.5%)30mgをメチルイソブチルケトン(MIBK)30gに添加し、ジェットミル(ナノジェットパル JN10-SP003、常光社製)を用いて湿式分散処理を施し、濃度0.1重量%のカーボンナノチューブ分散液A-1を得た。
走査型電子顕微鏡(HITACHI社製 S-4800)を用いて、調製例1で使用した高配向カーボンナノチューブを倍率500倍にて観察し、上記高配向カーボンナノチューブの平均長さ(CNTフォレストの成長長さの平均値)を電子顕微鏡画像に基づき算出した。
具体的には、図6に示したような電子顕微鏡写真においてCNTフォレスト部分を選択し、その部分の成長長さ(図6の例では、114μm)を測定し、平均値を算出した。
このとき、電子顕微鏡写真は複数枚撮影し、無作為に抽出した10箇所の成長長さの平均値を算出した。
調製例1で使用した高配向カーボンナノチューブの平均長さは102μmであった。
なお、図6は、調製例1で使用した高配向カーボンナノチューブを撮影した電子顕微鏡写真のうちの1枚である。
走査型電子顕微鏡(HITACHI社製 S-4800)を用いて、調製例1で使用した高配向カーボンナノチューブを倍率200000倍にて観察し、上記高配向カーボンナノチューブの平均繊維径を電子顕微鏡画像に基づき算出した。
具体的には、図7に示したような電子顕微鏡写真において単独で観察されるカーボンナノチューブを無作為に抽出し、そのカーボンナノチューブの繊維径(図7に示した例では12.9nm)を測定し、平均値を算出した。
このとき、電子顕微鏡写真は複数枚撮影し、無作為に抽出した10箇所の繊維径の平均値を算出した。
調製例1で使用した高配向カーボンナノチューブの平均繊維径は12.8nmであった。
なお、図7は、調製例1で使用した高配向カーボンナノチューブを撮影した電子顕微鏡写真のうちの1枚である。
多層カーボンナノチューブとして調製例1とは繊維長さが異なる、大陽日酸社製の高配向カーボンナノチューブ(層数4~12層、繊維径10~20nm、繊維長さ150~300μm、炭素純度99.5%)を使用し、上記調製例1と同様にして、濃度0.1重量%のカーボンナノチューブ分散液A-2を得た。
本例で使用した高配向カーボンナノチューブについて、調製例1と同様にして、平均長さ及び平均繊維径を算出したところ、平均長さは298μm、平均繊維径は12.9nmであった。
多層カーボンナノチューブとして調製例1とは繊維長さが異なる、大陽日酸社製の高配向カーボンナノチューブ(層数4~12層、繊維径10~20nm、長さ300~600μm、炭素純度99.5%)を使用し、上記調製例1と同様にして、濃度0.1重量%のカーボンナノチューブ分散液A-3を得た。
本例で使用した高配向カーボンナノチューブについて、調製例1と同様にして、平均長さ及び平均繊維径を算出したところ、平均長さは591μm、平均繊維径は11.1nmであった。
大陽日酸社製の高配向カーボンナノチューブに代えて、多層カーボンナノチューブであるナノシル社製、NC7000(繊維径9.5nm、平均長さ1.5μm、アスペクト比158、炭素純度90%)を用いた以外は、カーボンナノチューブ分散液(A-1)の調製方法と同様にして、濃度0.1重量%のカーボンナノチューブ分散液Bを調製した。
大陽日酸社製の高配向カーボンナノチューブに代えて、単層カーボンナノチューブであるスーパーグロースCNT(繊維径の中央値が約3nm、成長長さ500~700μm、アスペクト比約100,000、炭素純度99.9%、産業技術総合研究所提供)を用いた以外は、カーボンナノチューブ分散液(A-1)の調製方法と同様にして、濃度0.1重量%のカーボンナノチューブ分散液Cを調製した。
(1)水添水酸基末端液状ポリオレフィンポリオール(エポール、出光興産社製)100質量部、アルキル置換ジフェニルエーテルを主成分とした高温用潤滑油(モレスコハイルーブLB-100、MORESCO社製)100質量部を計量し、自転公転ミキサー(THINKY社製)を用いて2000rpmで3分間撹拌混合した。次に、得られた混合物に触媒(Fomrez catalyst UL-28、Momentive社製)0.07質量部を添加し、自転公転ミキサーで1.5分撹拌した。その後、イソホロンジイソシアネート(デスモジュールI、住化バイエルウレタン社製)11質量部を添加し、自転公転ミキサーで3分間撹拌し、1.5分間脱泡し、基材用の原料組成物を調製した後、これを図3に示した成形装置30に注入し、保護フィルムでサンドイッチ状にして搬送しつつ、炉内温度110℃、炉内時間30分間の条件で架橋硬化させ、保護フィルム付きの所定厚みのロール巻シートを得た。その後、80℃に調節した炉で12時間後架橋させ、層厚50μmの基材シートを得た。
次に、得られた基材シートを裁断し、90mm×90mm×50μmの基材と、90mm×60mm×50μmの基材とを1枚ずつ作製した。
さらに、基材用の原料組成物と同配合の組成物をトルエンに溶解した0.2重量%トルエン溶液を調製し、この0.2重量%トルエン溶液4gをプライマーとして電極本体上にスプレーコートで帯状に塗布し、100℃で30分間乾燥させた。このとき、電極本体の両端部(端部から8mmの部分)はスプレーコート前にマスクした。
また、スプレーコートは、エアブラシとして(エアテックス社製、KIDS-102)を使用し、ノズルは完全に閉じた状態から1回転分のみ解放し、ノズルの先端から塗布面までの距離を10cmとして行った。
その後、電極本体を挟み込むように、電極本体が形成された基材をもう1枚(90mm×60mm×50μm)の基材と貼り合わせて伸縮性電極を得た。
カーボンナノチューブ分散液(A-1)に代えて、カーボンナノチューブ分散液(A-2)を用いた以外は、実施例1と同様にして伸縮性電極を得た。
カーボンナノチューブ分散液(A-1)に代えて、カーボンナノチューブ分散液(A-3)を用いた以外は、実施例1と同様にして伸縮性電極を得た。
カーボンナノチューブ分散液(A-1)に代えて、カーボンナノチューブ分散液(B)を用いた以外は、実施例1と同様にして伸縮性電極を得た。
カーボンナノチューブ分散液(A-1)に代えて、カーボンナノチューブ分散液(C)を用いた以外は、実施例1と同様にして伸縮性電極を得た。
実施例及び比較例で得たそれぞれの伸縮性電極につき、図8に示した評価装置を用いて、無伸長状態から一軸方向(電極本体の長手方向)に100%伸長させた後、無伸長状態に戻すサイクルを1サイクルとする伸縮を1000サイクル繰返し行った。2~3サイクル目、10サイクル目、100サイクル目、500サイクル目及び1000サイクル目における電極本体の上記電気抵抗を測定した。
測定結果については、縦軸に抵抗(対数)、横軸に伸長率をプロットしたグラフとして図9~13に示した。更に、実施例1~3及び比較例1、2の伸縮性電極に関し、2サイクル目及び1000サイクル目のそれぞれの無伸長時(0%伸長時)及び100%伸長時の電気抵抗を下記表1に示した。
これに対し、平均長さが約10μmと短い多層カーボンナノチューブからなる電極本体を備えた例(比較例1)では、導電性が低く、また、伸長時の電気抵抗の増大や繰り返し伸縮時の電気抵抗のバラツキが著しかった。また、単層カーボンナノチューブからなる電極本体を備えた例(比較例2)では、導電性が低くかった。
2 誘電層
01A1~16A1 表側接続部
01A~16A 表側電極層
01B1~16B1 裏側接続部
01B~16B 裏側電極層
C0101~C1616 検出部
30 成形装置
31 保護フィルム
32 ロール
33 原料組成物
34 加熱装置
35 基材
50、100、110、120、130 伸縮性電極
51、101、111a、111b、121a、121b、131 基材
52、102、112、122a、122b、132a、132b 電極本体
53 銅箔
54 樹脂フレーム
55 リード
56 マルチメーター
201 静電容量型センサ
202、203 外部配線
204 計測手段
Claims (6)
- エラストマー組成物からなる基材と、前記基材と一体化された電極本体とを備え、
前記電極本体は、繊維長さが50μm以上の多層カーボンナノチューブを用いて形成されていることを特徴とする伸縮性電極。 - 前記多層カーボンナノチューブは、繊維径が5~30nmである請求項1に記載の伸縮性電極。
- センサシートに用いる請求項1又は2に記載の伸縮性電極。
- 請求項1~3のいずれかに記載の伸縮性電極を用いたセンサシートであって、
前記基材はシート状であり、前記電極本体は前記基材の両面に設けられ、
前記基材の一方の面に設けられた電極本体と前記基材の他方の面に設けられた電極本体とは、前記基材を挟んで少なくとも一部が対向していることを特徴とするセンサシート。 - 前記電極本体は、帯状であって、前記基材の両面に複数列ずつ設けられている請求項4に記載のセンサシート。
- 請求項4又は5に記載のセンサシートと、計測手段と、前記センサシートが備える電極本体及び前記計測手段を接続する外部配線とを備え、
前記基材の一方の面に設けられた電極本体と前記基材の他方の面に設けられた電極本体との前記基材を挟んで対向している部分を検出部とし、
前記計測手段は、前記検出部における静電容量の変化を計測することにより、変形歪み量を測定することを特徴とする静電容量型センサ。
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Also Published As
Publication number | Publication date |
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JP6494523B2 (ja) | 2019-04-03 |
KR20160091364A (ko) | 2016-08-02 |
EP3076402B1 (en) | 2022-06-08 |
JPWO2015079951A1 (ja) | 2017-03-16 |
TWI652697B (zh) | 2019-03-01 |
TW201528293A (zh) | 2015-07-16 |
US10184779B2 (en) | 2019-01-22 |
US20160377409A1 (en) | 2016-12-29 |
EP3076402A4 (en) | 2017-08-23 |
CN109990926A (zh) | 2019-07-09 |
EP3076402A1 (en) | 2016-10-05 |
JP2019091717A (ja) | 2019-06-13 |
JP6726781B2 (ja) | 2020-07-22 |
CN105765668A (zh) | 2016-07-13 |
CN105765668B (zh) | 2019-05-21 |
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