WO2011145411A1 - 導電膜、およびそれを用いたトランスデューサ、フレキシブル配線板 - Google Patents
導電膜、およびそれを用いたトランスデューサ、フレキシブル配線板 Download PDFInfo
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- WO2011145411A1 WO2011145411A1 PCT/JP2011/059184 JP2011059184W WO2011145411A1 WO 2011145411 A1 WO2011145411 A1 WO 2011145411A1 JP 2011059184 W JP2011059184 W JP 2011059184W WO 2011145411 A1 WO2011145411 A1 WO 2011145411A1
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- elastomer
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/09—Use of materials for the conductive, e.g. metallic pattern
- H05K1/092—Dispersed materials, e.g. conductive pastes or inks
- H05K1/095—Dispersed materials, e.g. conductive pastes or inks for polymer thick films, i.e. having a permanent organic polymeric binder
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- 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
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0445—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using two or more layers of sensing electrodes, e.g. using two layers of electrodes separated by a dielectric layer
-
- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06F—ELECTRIC DIGITAL DATA PROCESSING
- G06F3/00—Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
- G06F3/01—Input arrangements or combined input and output arrangements for interaction between user and computer
- G06F3/03—Arrangements for converting the position or the displacement of a member into a coded form
- G06F3/041—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
- G06F3/044—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means
- G06F3/0446—Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means by capacitive means using a grid-like structure of electrodes in at least two directions, e.g. using row and column electrodes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
-
- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N1/00—Electrostatic generators or motors using a solid moving electrostatic charge carrier
- H02N1/002—Electrostatic motors
- H02N1/006—Electrostatic motors of the gap-closing type
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/87—Electrodes or interconnections, e.g. leads or terminals
- H10N30/877—Conductive materials
- H10N30/878—Conductive materials the principal material being non-metallic, e.g. oxide or carbon based
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
- H05K1/162—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor incorporating printed capacitors
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0104—Properties and characteristics in general
- H05K2201/0133—Elastomeric or compliant polymer
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0242—Shape of an individual particle
- H05K2201/0245—Flakes, flat particles or lamellar particles
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0242—Shape of an individual particle
- H05K2201/0248—Needles or elongated particles; Elongated cluster of chemically bonded particles
Definitions
- the present invention relates to a conductive film suitable for stretchable electrodes, wiring and the like, a transducer using the same, and a flexible wiring board.
- an actuator using an elastomer has high flexibility, is lightweight, and is easy to be miniaturized, its use in various fields such as artificial muscles, medical instruments, fluid control, and the like is being studied.
- an electrode can be disposed on both sides in the thickness direction of an elastomer dielectric film to constitute an actuator.
- the dielectric film expands and contracts depending on the magnitude of the applied voltage. Therefore, the electrode is required to be stretchable according to the deformation of the dielectric film so as not to prevent the expansion and contraction of the dielectric film.
- Patent Document 1 an electrode is formed from a paste in which an oil or an elastomer is mixed with a conductive agent such as carbon black.
- Patent Document 2 discloses a paste in which flake-like silver particles and spherical silver particles are dispersed in a synthetic resin and an organic solvent.
- Patent Document 3 discloses a paste in which copper particles, a thermoplastic acrylic resin, a titanate coupling agent, and an organic solvent are mixed.
- Patent Document 4 discloses a paste obtained by mixing one or more binders selected from a synthetic rubber, a silicone resin and a thermoplastic polyester resin, and two kinds of scaly silver powders having different average particle sizes.
- the specific resistance of the elastomer is relatively large, about 0.1 to 1 ⁇ cm.
- the electrical resistance of the electrode or the wiring is high, the element is easily deteriorated due to heat generation due to the internal resistance.
- the responsiveness of the actuator may be reduced due to the generation of the reactance component in the high frequency region. Also, if the internal resistance is too high for the detection signal, the resolution of the sensor may be reduced.
- electrodes formed from commercially available silver paste have poor flexibility.
- the silver paste is obtained by filling a binder resin with silver powder.
- the modulus of elasticity of the formed electrode is high. For this reason, if it is greatly elongated, a crack will occur and the electrical resistance will increase significantly.
- the electrode of the actuator is formed of silver paste, the electrode can not follow the expansion and contraction of the dielectric film, which may inhibit the movement of the dielectric film.
- the elastic modulus of the binder resin is high.
- the paste is also not suitable as a material for forming a flexible electrode such as the above-described actuator or wiring.
- relatively large amount of silver powder needs to be filled in order to achieve the desired conductivity.
- the elastic modulus of the formed electrode becomes high, and the electrode does not easily follow the expansion and contraction of the dielectric film.
- cracks are likely to occur during elongation, leading to an increase in electrical resistance.
- the conductive film of the present invention comprises an elastomer and a metal filler filled in the elastomer, and the following conditions (A) and (B) are satisfied: It features.
- the reference number per 1 ⁇ m of the straight line is calculated by counting the number of the metal fillers having a length of 2 ⁇ m or more and the length of the longest part in the cross-sectional photograph that intersects each other by dividing the number by the length of the straight line
- the average value of the reference number in the straight line of the book is 0.8 (pieces / ⁇ m) or more, or the metal filler includes a flake-like filler having a thickness of 1 ⁇ m or less and an aspect ratio of 26 or more.
- the average value of the reference number is 0.4 (pieces / ⁇ m) or more.
- FIG. 1 shows a schematic view of a cross-sectional photograph of a conductive film for explaining the condition (A) in the present invention.
- FIG. 1 is a schematic view for explaining the calculation procedure of the reference number of conditions (A).
- FIG. 1 does not limit the conductive film of the present invention at all, including the size, shape, number, arrangement of the metal filler, thickness of the conductive film, and the like.
- the cross-sectional photograph 100 is obtained by photographing the cross section in the film thickness direction of the conductive film with a scanning electron microscope (SEM).
- SEM scanning electron microscope
- a number of metal fillers 102 are dispersed in the elastomer 101.
- the metal filler 102 is oriented in the left-right direction (the film development direction of the conductive film). Adjacent metal fillers 102 are in contact with each other. By connecting the plurality of metal fillers 102, a conductive path is formed in the elastomer 101.
- the number of the metal fillers 102 is x for the straight line ⁇ , y for the straight line ⁇ , and z for the straight line ⁇ .
- the reference number per 1 ⁇ m of each straight line is calculated by dividing each number by the length L ⁇ m of the straight line.
- the reference number in each straight line is x / L (number / ⁇ m), y / L (number / ⁇ m) and z / L (number / ⁇ m).
- an average value [(x + y + z) / (3L)] of three reference numbers is calculated.
- the obtained average value is 0.8 (particles / ⁇ m) or more, or 0.4 (particles / ⁇ m) or more and less than 0.8 (particles / ⁇ m).
- a flake-like (flaky) filler having a thickness of 1 ⁇ m or less and an aspect ratio of 26 or more To determine if it is included.
- An average thickness is employed as the thickness of the flake filler.
- the average value of the reference number is 0.8 (pieces / ⁇ m) or more, or the metal filler contains a flake-like filler having a thickness of 1 ⁇ m or less and an aspect ratio of 26 or more.
- the fact that the average value of the reference number is 0.4 (number / ⁇ m) or more indicates that the number of conductive paths is large. That is, it can be said that the conductive film is excellent in conductivity.
- the condition of (A) is an indicator of conductivity.
- FIG. 2 the schematic diagram of the cross-sectional photograph of the electrically conductive film for demonstrating the conditions of (B) in this invention is shown.
- FIG. 3 shows a schematic view in which one of the unit regions is enlarged. For convenience of explanation, the elastomer and the metal filler are omitted in FIG. Moreover, FIG. 2, FIG. 3 is a schematic diagram for demonstrating the unit area
- SEM scanning electron microscope
- the way of arranging the unit areas is not particularly limited. However, from the viewpoint of uniformly detecting the filling state of the metal filler in the film thickness direction and the film spreading direction, the same number (10 pieces ⁇ 10 pieces) of unit regions are arranged in the film thickness direction and the film spreading direction It is desirable that the area be a 20 ⁇ m square (see FIG. 2). However, it may be considered that ten unit regions can not be aligned in the film thickness direction, such as when the thickness of the conductive film is less than 20 ⁇ m. In this case, the remaining unit regions which can not be arranged in the film thickness direction may be arranged in addition to the film developing direction.
- condition of (B) of the present invention that the number of unit regions having an area ratio of 60% or more of the elastomer is 20 or more means that there are many elastomer components or there are many regions where elastomer components are continuously present. Indicates That is, the conductive film can be said to be flexible. Thus, the condition of (B) is an indicator of flexibility.
- the conductive path for obtaining the desired conductivity is efficiently formed in the conductive film satisfying the above conditions (A) and (B). That is, high conductivity is ensured with a smaller amount of metal filler.
- the conductive path can be controlled, and the metal filler can be unevenly distributed. As a result, it is possible to obtain a flexible conductive film having high conductivity and a small change in electrical resistance at the time of elongation.
- the transducer according to the present invention further comprises a dielectric film made of elastomer, a plurality of electrodes disposed via the dielectric film, and a wire connected to each of the plurality of electrodes. At least one of the electrode and the wiring comprises the conductive film of the present invention.
- a transducer is a device that converts one type of energy into another type of energy.
- the transducers include, for example, actuators, sensors, power generation elements, etc. that convert electrical energy and mechanical energy.
- at least one of the electrode and the wiring comprises the conductive film of the present invention. Therefore, when the member in which the electrode and the wiring are formed is deformed, the electrode and the wiring expand and contract following the deformation. For this reason, the movement of the transducer is less likely to be impeded by the electrodes and wiring. Further, in the electrode and the wiring formed of the conductive film of the present invention, the decrease in conductivity at the time of expansion is small, and even when the deformation is repeated, the heat generation due to the internal resistance is small. Therefore, the transducer of the present invention is excellent in durability.
- the flexible wiring board of the present invention is characterized in that at least a part of the wiring is made of the conductive film of the present invention.
- the wiring expands and contracts following the deformation of the base material. Even when the wiring is extended, the decrease in conductivity is small, and even when expansion and contraction are repeated, heat generation due to internal resistance is small. Therefore, the flexible wiring board of the present invention is excellent in durability.
- FIG. 5 is a cross-sectional view taken along the line V-V of FIG. 4; It is a cross-sectional schematic diagram of the actuator which is one Embodiment of the transducer of this invention, Comprising: (a) is an OFF state, (b) each shows an ON state.
- FIG. 12 is a cross-sectional view in the XII-XII direction of FIG. 25 is a SEM photograph of a cross section in the film thickness direction of the conductive film of Example 8.
- Capacitive sensor (transducer) 10 dielectric film 11a, 11b: electrode 12a, 12b: wiring 13a, 13b: cover film 14: connector 2: actuator (transducer) 20: dielectric film 21a, 21b: electrode 22a, 22b: Wiring 23: Power supply 3: Power generation element (transducer) 30: Dielectric film 31a, 31b: Electrode 32a to 32c: Wiring 4: Flexible wiring board 40: Base 41: Connector for front side wiring 42: Connector for rear side wiring 5: Actuator 50: dielectric film 51a, 51b: electrode 52: power source 53: displacement gauge 510a, 510b: terminal portion 530: marker 100: conductive film 101: elastomer 102: metal filler 01X to 16X: front side electrode 01X1 to 16X1: front side connection portion 01Y to 16Y: back side electrode 01 Y1 to 16Y1: Back side connection parts 01x to 16x: Front side wiring 01y to 16y: Back side wiring E: Unit area M: Measurement area
- the elastomer constituting the conductive film of the present invention may be one having rubbery elasticity at room temperature.
- an elastomer having a glass transition temperature (Tg) of ⁇ 10 ° C. or less is preferable because it is flexible.
- Tg of the elastomer is desirably ⁇ 20 ° C. or less, and further desirably ⁇ 35 ° C. or less.
- a midpoint glass transition temperature measured according to JIS K 7121 (1987) is employed as the glass transition temperature.
- the elastomer preferably has a functional group capable of hydrogen bonding.
- the hydrogen bondable functional group has high affinity to the metal filler. For this reason, interfacial peeling between the elastomer and the metal filler hardly occurs. Therefore, even when stretched, the conductive film is less likely to be cracked and the electrical resistance is also less likely to increase.
- functional groups capable of hydrogen bonding include ester groups, urethane bonds, urea bonds, halogen groups, hydroxyl groups, carboxyl groups, amino groups, sulfonic acid groups, ether bonds and the like. Among them, those having an ester group are desirable.
- the elastomer may be selected in consideration of mechanical load applied to the conductive film, temperature and humidity at which the conductive film is used, adhesion to the substrate, and the like.
- 1 type may be used independently and 2 or more types may be mixed and used.
- acrylic rubber, urethane rubber, hydrin rubber, silicone rubber and the like are suitable.
- Acrylic rubber has a low Tg compared to other rubbers because of its low crystallinity and weak intermolecular force. Therefore, it is flexible, has a good elongation, and is suitable for an electrode of an actuator or the like.
- As an acrylic rubber what contains 50 mol% or more of acrylic acid ester monomer units which have a C4 or more alkyl group is desirable.
- the alkyl group When the alkyl group is large (the number of carbon atoms is large), the crystallinity is lowered, so that the elastic modulus of the acrylic rubber becomes lower.
- urethane rubber is excellent in mechanical strength. For this reason, it is suitable for the use to which a dynamic load is added.
- hydrin rubber and silicone rubber are excellent in environmental stability. For this reason, it is suitable for the use with a large environmental change, such as temperature and humidity.
- the elastomer may contain additives such as a plasticizer, a processing aid, a crosslinking agent, a crosslinking accelerator, a crosslinking aid, an antiaging agent, a softener, a coloring agent and the like.
- a plasticizer can improve the processability of the elastomer and further improve the flexibility.
- known organic acid derivatives such as phthalic acid diester, phosphoric acid derivatives such as tricresyl phosphate, adipic acid diester, chlorinated paraffin, polyether ester and the like may be used.
- the crosslinking agent contributing to the crosslinking reaction, the crosslinking accelerator, the crosslinking assistant and the like may be appropriately determined according to the type of the elastomer and the like.
- the crosslinking agent contains sulfur
- the metal filler may be sulfided. Thereby, the electrical resistance of the surface of the metal filler may be increased, and the conductivity may be reduced. Therefore, as a crosslinking agent etc., it is desirable to use the compound which does not contain sulfur.
- the material of the metal filler filled in the elastomer is not particularly limited.
- silver, gold, copper, nickel, rhodium, palladium, chromium, titanium, platinum, iron, and alloys thereof may be appropriately selected from the viewpoint that the conductivity is higher than carbon black and hardly corroded.
- silver is preferable because of its low electrical resistance.
- carbon materials such as graphite and carbon black, metal oxides such as calcium carbonate, titanium dioxide, aluminum oxide and barium titanate, inorganic substances such as silica, resins such as acrylic and urethane, etc. are used. Just do it.
- the metal filler is flake-like (flake-like) or needle-like with a thickness of 1 ⁇ m or less, from the viewpoint of increasing the contact area between the fillers to improve the conductivity, and the anisotropy oriented in the film spreading direction It is desirable to include a filler.
- the anisotropic filler may be disposed in the elastomer such that the longitudinal direction thereof is substantially parallel to the film development direction.
- the average particle size of the anisotropic filler is not particularly limited, but is preferably, for example, 2.5 ⁇ m or more and 20 ⁇ m or less.
- the average particle size is less than 2.5 ⁇ m, the overlapping area between the fillers is reduced, and thus the electrical resistance tends to increase at the time of elongation.
- it is larger than 15 ⁇ m, the flexibility of the conductive film is reduced.
- a value measured by “Microtrac particle size distribution measuring apparatus UPA-EX150 type” manufactured by Nikkiso Co., Ltd. is employed as the average particle size of the metal filler.
- the reason for setting the thickness of the flake-like anisotropic filler (hereinafter appropriately referred to as “flake-like filler”) to 1 ⁇ m or less is as follows. That is, in order to form a conductive path in an elastomer using a flaky filler, it is necessary to fill the elastomer with a predetermined number or more of flaky fillers. Here, if the thickness of the flake-like filler is reduced, the total mass of the flake-like filler to be filled decreases even if the flake-like filler is used by the same number. In addition, the volume fraction of the flake-like filler in the elastomer also decreases.
- the thickness of the flake filler is set to 1 ⁇ m or less. More preferably, it is 0.5 ⁇ m or less.
- the "thickness" of the flake filler is the average thickness of one filler.
- the flake filler it is desirable to include a filler having an aspect ratio of 26 or more. As the aspect ratio is larger, the fillers are likely to overlap with each other, and a conductive path is more likely to be formed.
- the maximum length of the flake-like filler in the conductive film can be measured as follows. First, the polymer component is removed from the conductive film, and the metal filler (including the flake filler) is taken out. Then, a SEM photograph of the metal filler taken out is taken, and the maximum length of the flake filler is measured from the SEM photograph.
- the average thickness of the flake-like filler in the conductive film can be measured as follows. First, the metal filler extracted from the conductive film is embedded with epoxy resin. Next, the embedded sample is cut in the thickness direction of the metal filler, and a SEM photograph of a cross section of the sample is taken. And an average thickness is computed by carrying out image analysis of the cross-sectional image of the flake shaped filler in the said SEM photograph.
- the metal filler in addition to the above-mentioned anisotropic filler, various fillers having different shapes and sizes can be used. Among them, it is desirable to use a massive filler having an average particle diameter of 0.1 ⁇ m to 1.5 ⁇ m in combination.
- “bulk” includes not only spherical shapes, substantially spherical shapes (elliptical shapes, oval shapes (a shape in which a pair of opposing hemispheres are connected by a cylinder), etc.), and irregular shapes with irregularities on the surface.
- the anisotropic fillers in contact with each other are sheared at the contact surface during elongation. Therefore, the flexibility of the conductive film may be reduced.
- the massive filler intrudes between the anisotropic fillers. Then, the anisotropic filler is localized. Thereby, shearing between anisotropic fillers is reduced, and a decrease in flexibility is suppressed.
- the average particle size of the massive filler is desirably 0.1 ⁇ m or more and 1.5 ⁇ m or less.
- the average particle size is less than 0.1 ⁇ m, the specific surface area is increased, the reinforcing property is increased, and the flexibility of the conductive film is reduced. 0.3 ⁇ m or more is more preferable.
- it is larger than 1.5 ⁇ m, it is difficult to enter the gap of the anisotropic filler.
- the content ratio of the anisotropic filler and the massive filler be 2: 1 to 50: 1 in mass ratio.
- the conductive film of the present invention satisfies the following conditions (A) and (B).
- A) On a cross-sectional photograph taken in the film thickness direction taken by a scanning electron microscope, three straight lines extending in the film thickness direction are drawn 3 ⁇ m apart in the film spreading direction, and each straight line intersects the straight line Counting the number of metal fillers having a maximum length of 2 ⁇ m or more in a cross-sectional photograph, and dividing the number by the length of the straight line to calculate the reference number per 1 ⁇ m of the straight line, three straight lines
- the average value of the standard number of particles is 0.8 (particles / ⁇ m) or more, or the metal filler contains flake-like fillers having a thickness of 1 ⁇ m or less and an aspect ratio of 26 or more, and the average value of the standard number Is 0.4 (piece / ⁇ m) or more.
- the conductive film of the present invention filled with the metal filler so as to satisfy the above conditions (A) and (B) has high conductivity even if the filling amount of the metal filler is relatively small.
- the filling amount of the metal filler is desirably less than 45 vol% when the volume of the conductive film is 100 vol%. More preferably, it is less than 42 vol%, and more preferably less than 38 vol%.
- the conductive film of the present invention is formed, for example, by kneading a polymer (including an additive as appropriate) of an elastomer component and a metal filler by a pressure kneader such as a kneader or a Banbury mixer, two rolls, three rolls or the like.
- the conductive material can be manufactured by molding or extrusion.
- a metal filler is first added to a solution in which a polymer of an elastomer component is dissolved in a solvent with a predetermined additive, and the mixture is stirred and mixed to prepare a conductive paint.
- the prepared conductive paint can be applied to a substrate or the like and dried by heating to manufacture.
- the crosslinking reaction of the elastomer may be allowed to proceed.
- a method of applying the conductive paint various methods already known can be adopted. For example, in addition to printing methods such as inkjet printing, flexographic printing, gravure printing, screen printing, pad printing and lithography, dip method, spray method, bar coat method and the like can be mentioned. For example, when the printing method is adopted, it is possible to easily separate the application part and the non-application part. Also, printing of large areas, thin lines, and complicated shapes is easy. Among the printing methods, the screen printing method is preferable because a high viscosity conductive paint can be used, the thickness of the coating can be easily adjusted, and the metal filler is easily oriented.
- the thickness of the conductive film of the present invention may be appropriately determined according to the application.
- the thickness of the conductive film is used from the viewpoint of miniaturizing the elastomer sensor or actuator and minimizing the influence on the deformation of the dielectric film. Should be thin.
- the thickness of the conductive film is desirably 4 ⁇ m to 1000 ⁇ m. More preferably, it is 10 ⁇ m to 50 ⁇ m.
- the conductive film of the present invention may be formed on the surface of a base material, a dielectric film or the like depending on the application.
- a base material the resin film etc. which have the flexibility which consist of polyimide, polyethylene, a polyethylene terephthalate (PET), a polyethylene naphthalate (PEN) etc. are mentioned, for example.
- PET polyethylene terephthalate
- PEN polyethylene naphthalate
- the elastic member includes a dielectric film in an actuator or the like.
- the thin film elastic member can be produced, for example, by applying a paint for forming the elastic member on a substrate having releasability, cutting it into a desired shape, and peeling it.
- the conductive film of the present invention is suitable for electrodes and wiring of a transducer, wiring of a flexible wiring board, and the like.
- an elastomer sensor, an actuator, and a power generation element will be described as an example of a transducer using the conductive film of the present invention, and then, an embodiment of a flexible wiring board will be described. Also in the transducer and the flexible wiring board of the present invention, it is desirable to adopt the preferred embodiment of the conductive film of the present invention described above.
- FIG. 4 shows a top view of the capacitive sensor.
- FIG. 5 shows a VV cross-sectional view of FIG.
- the capacitive sensor 1 includes a dielectric film 10, a pair of electrodes 11a and 11b, wires 12a and 12b, and cover films 13a and 13b.
- the dielectric film 10 is made of urethane rubber and has a strip shape extending in the left-right direction.
- the thickness of the dielectric film 10 is about 300 ⁇ m.
- the electrode 11a has a rectangular shape. Three electrodes 11 a are formed on the upper surface of the dielectric film 10 by screen printing. Similarly, the electrode 11b has a rectangular shape. Three electrodes 11 b are formed on the lower surface of the dielectric film 10 so as to face the electrode 11 a with the dielectric film 10 interposed therebetween. The electrode 11 b is screen printed on the lower surface of the dielectric film 10. Thus, three pairs of electrodes 11a and 11b are disposed with the dielectric film 10 interposed therebetween. The electrodes 11a and 11b are made of the conductive film of the present invention.
- the wiring 12 a is connected to each of the electrodes 11 a formed on the top surface of the dielectric film 10.
- the electrode 11a and the connector 14 are connected by the wiring 12a.
- the wiring 12 a is formed on the upper surface of the dielectric film 10 by screen printing.
- the wirings 12b are connected to each of the electrodes 11b formed on the lower surface of the dielectric film 10 (indicated by dotted lines in FIG. 4).
- the electrode 11 b and a connector (not shown) are connected by the wiring 12 b.
- the wiring 12 b is formed on the lower surface of the dielectric film 10 by screen printing.
- the wirings 12a and 12b are made of the conductive film of the present invention.
- the cover film 13a is made of acrylic rubber, and has a strip shape extending in the left-right direction.
- the cover film 13a covers the top surfaces of the dielectric film 10, the electrode 11a, and the wiring 12a.
- the cover film 13 b is made of acrylic rubber and has a strip shape extending in the left-right direction.
- the cover film 13b covers the lower surface of the dielectric film 10, the electrode 11b, and the wiring 12b.
- the movement of the capacitive sensor 1 will be described.
- the capacitive sensor 1 when the capacitive sensor 1 is pressed from above, the dielectric film 10, the electrode 11a, and the cover film 13a are integrally bent downward.
- the compression reduces the thickness of the dielectric film 10.
- the capacitance between the electrodes 11a and 11b is increased.
- the change in capacitance detects deformation due to compression.
- the dielectric film 10, the electrodes 11a and 11b, the wirings 12a and 12b, and the cover films 13a and 13b are all made of an elastomer material. Therefore, the entire capacitive sensor 1 is flexible and expandable.
- the electrodes 11 a and 11 b and the wirings 12 a and 12 b can be deformed following the deformation of the dielectric film 10. Furthermore, the conductivity of the electrodes 11a and 11b and the wirings 12a and 12b is high, and the increase in electrical resistance is small even if the electrodes are extended.
- the responsiveness of the capacitive sensor 1 is good.
- the capacitance type sensor 1 of the present embodiment three pairs of electrodes 11a and 11b facing each other with the dielectric film 10 narrowed are formed.
- the number, size, arrangement and the like of the electrodes may be appropriately determined according to the application.
- FIG. 6 the cross-sectional schematic diagram of the actuator of this embodiment is shown.
- (A) shows an off state
- (b) shows an on state, respectively.
- the actuator 2 includes a dielectric film 20, electrodes 21a and 21b, and wirings 22a and 22b.
- the dielectric film 20 is made of urethane rubber.
- the electrode 21 a is disposed to cover substantially the entire top surface of the dielectric film 20.
- the electrode 21 b is arranged to cover substantially the entire lower surface of the dielectric film 20.
- the electrodes 21a and 21b are connected to the power supply 23 through the wirings 22a and 22b, respectively.
- Each of the electrodes 21a and 21b is made of the conductive film of the present invention.
- a voltage is applied between the pair of electrodes 21a and 21b.
- the film thickness of the dielectric film 20 becomes thinner.
- the dielectric film 20 extends in a direction parallel to the surfaces of the electrodes 21a and 21b, as indicated by white arrows in FIG. 6B.
- the actuator 2 outputs driving force in the horizontal and vertical directions in FIG.
- the electrodes 21a and 21b are flexible and expandable. Therefore, the dielectric film 20 can be deformed following the deformation. That is, the movement of the dielectric film 20 is less likely to be hindered by the electrodes 21a and 21b. Therefore, according to the actuator 2, larger force and displacement can be obtained. Furthermore, with regard to the electrodes 21a and 21b, the increase in electrical resistance is small even if they are elongated. Therefore, there is little heat generation due to the internal resistance, and the electrodes 21a and 21b are not easily deteriorated. That is, the actuator 2 is excellent in durability. In addition, when it is set as the laminated structure which laminated
- the power generation element 3 includes a dielectric film 30, electrodes 31a and 31b, and wirings 32a to 32c.
- the dielectric film 30 is made of urethane rubber.
- the electrode 31 a is disposed to cover substantially the entire top surface of the dielectric film 30.
- the electrode 31 b is disposed so as to cover substantially the entire lower surface of the dielectric film 30. Wirings 32a and 32b are connected to the electrode 31a.
- the electrode 31a is connected to an external load (not shown) via the wiring 32a. Further, the electrode 31a is connected to a power supply (not shown) via the wiring 32b. The electrode 31 b is grounded by the wiring 32 c.
- Each of the electrodes 31a and 31b is made of the conductive film of the present invention.
- the film thickness of the dielectric film 30 becomes thin, and between the electrodes 31a and 31b. Charge is stored in Thereafter, when the compressive force is removed, as shown in FIG. 7B, the dielectric film 30 contracts due to the elastic restoring force of the dielectric film 30, and the film thickness becomes thick. At this time, the stored charge is released through the wiring 32a.
- the electrodes 31a, 31b are flexible and expandable. Therefore, the movement of the dielectric film 30 is less likely to be hindered by the electrodes 31a and 31b.
- the increase in electrical resistance is small even if they are elongated. Therefore, even when the deformation is repeated, the heat generation due to the internal resistance is small. Therefore, the power generation element 3 is excellent in durability.
- FIG. 8 shows a top transparent view of the flexible wiring board of the present embodiment.
- the wires on the back side are indicated by thin lines.
- the flexible wiring board 4 includes a substrate 40, front side electrodes 01X to 16X, front side electrodes 01X to 16X, front side wires 01x to 16x, back side wires 01y to 16y, and a front side wire connector 41 and a rear side wiring connector 42 are provided.
- the base material 40 is made of urethane rubber and has a sheet shape.
- a total of sixteen front side electrodes 01X to 16X are arranged on the top surface of the base 40.
- the front electrodes 01X to 16X each have a band shape.
- the front electrodes 01X to 16X extend in the X direction (left and right direction), respectively.
- the front electrodes 01X to 16X are arranged in the Y direction (front-rear direction) so as to be substantially parallel to each other at predetermined intervals.
- Front side connection parts 01X1 to 16X1 are disposed at the left ends of the front side electrodes 01X to 16X, respectively.
- a total of 16 back side electrodes 01Y to 16Y are arranged on the lower surface of the base material 40.
- Each of the back side electrodes 01Y to 16Y has a band shape.
- Each of the back side electrodes 01Y to 16Y extends in the Y direction.
- the back side electrodes 01Y to 16Y are arranged in the X direction so as to be substantially parallel to each other at predetermined intervals.
- Back side connection portions 01Y1 to 16Y1 are disposed at front ends of the back side electrodes 01Y to 16Y, respectively.
- a detection portion for detecting a load or the like is formed by the portion (overlapping portion) where the front side electrodes 01X to 16X and the back side connection portions 01Y1 to 16Y1 intersect with the base material 40 interposed therebetween. ing.
- a total of sixteen front side wires 01x to 16x are arranged on the top surface of the base 40.
- the front side wires 01x to 16x each have a linear shape.
- the front side wiring connector 41 is disposed at the left rear corner of the base 40.
- the front side wirings 01x to 16x respectively connect the front side connecting portions 01X1 to 16X1 and the front side wiring connector 41.
- the upper surface of the base 40, the front electrodes 01X to 16X, and the front wirings 01x to 16x are covered with a front cover film (not shown) from above.
- the front side wirings 01x to 16x are made of the conductive film of the present invention.
- a total of 16 back side wires 01y to 16y are arranged on the lower surface of the base material 40.
- the back side wires 01y to 16y each have a linear shape.
- the backside wiring connector 42 is disposed at the left front corner of the base 40.
- the backside wirings 01y to 16y respectively connect the backside connectors 01Y1 to 16Y1 and the backside wiring connector 42.
- the lower surface of the base 40, the back side electrodes 01Y to 16Y, and the back side wires 01y to 16y are covered with a back side cover film (not shown) from below.
- the backside wirings 01y to 16y are made of the conductive film of the present invention.
- a computing unit (not shown) is electrically connected to the front side wiring connector 41 and the rear side wiring connector 42, respectively.
- the impedance in the detection unit is input to the calculation unit from the front side wires 01x to 16x and the back side wires 01y to 16y. Based on this, the contact pressure distribution is measured.
- the front side wires 01x to 16x and the back side wires 01y to 16y are flexible and expandable. Therefore, the substrate 40 can be deformed following the deformation of the substrate 40. Further, with regard to the front side wires 01x to 16x and the back side wires 01y to 16y, the increase in electrical resistance is small even if they are extended. Therefore, even when the deformation is repeated, the heat generation due to the internal resistance is small. Therefore, the flexible wiring board 4 is excellent in durability.
- the prepared elastomer composition was dissolved in a solvent ethylene glycol monobutyl ether acetate to prepare an elastomer solution.
- a predetermined silver powder was added to the elastomer solution as a metal filler, and the mixture was kneaded with a three-roll mill to obtain a conductive paint.
- the following three types of silver powder were appropriately used.
- Silver powder A "Nanomelt (registered trademark) Ag-XF" (Flake-like, average particle diameter about 5 ⁇ m, thickness about 0.2 ⁇ m, aspect ratio 25) manufactured by Fukuda Metal Foil & Powder Industry Co., Ltd.
- Silver powder B “FA-D-4” (flaked, average particle size about 15 ⁇ m, thickness about 0.9 ⁇ m, aspect ratio 16.7) manufactured by Dowa Electronics Co., Ltd.
- Silver powder C “AG2-1C” manufactured by Dowa Electronics Co., Ltd. (spherical shape, average particle size about 0.5 ⁇ m, aspect ratio 1).
- the produced conductive paint was applied to the surface of an acrylic resin substrate by a bar coating method. Thereafter, the substrate on which the coating film was formed was allowed to stand in a drying oven at about 150 ° C. for about 30 minutes to dry the coating film and promote the crosslinking reaction to obtain a conductive film.
- the thickness of the obtained conductive film was about 20 ⁇ m.
- Example 5 A conductive film was manufactured in the same manner as in Example 1 except that urethane rubber was used instead of acrylic rubber.
- urethane rubber "Nipporan (registered trademark) 5230" manufactured by Nippon Polyurethane Industry Co., Ltd. was used.
- a urethane rubber polymer was dissolved in a solvent without blending a crosslinking agent and a processing aid to prepare an elastomer solution.
- Example 6 A conductive film was produced in the same manner as in Example 1 except that the acrylic rubber was replaced by a hydrin rubber.
- a hydrin rubber As the hydrin rubber, "Epchromer (registered trademark) CG 102" manufactured by Daiso Co., Ltd. was used.
- an elastomer composition was prepared using 0.5 parts by mass of triazine thiol (manufactured by Wako Pure Chemical Industries, Ltd.) as a crosslinking agent, without blending a processing aid.
- Example 7 A conductive film was produced in the same manner as in Example 1 except that silicone rubber was used instead of acrylic rubber.
- silicone rubber “TSE-3351” manufactured by Momentive Performance Materials Japan Ltd. was used.
- a silicone rubber polymer was dissolved in a solvent to prepare an elastomer solution without blending a crosslinking agent and a processing aid.
- Example 8 A conductive film was produced in the same manner as in Examples 1 to 4 except that the type and the blending amount of the silver powder were changed.
- As silver powder two types of silver powder C and silver powder D manufactured by flattening spherical silver particles having an average particle diameter of 2 ⁇ m manufactured by a chemical reduction method using a ball mill were used.
- the particle shape of the silver powder D is flake-like, the average particle diameter is about 13 ⁇ m, the thickness is about 0.2 ⁇ m, and the aspect ratio is 65.
- Example 9 A conductive film was produced in the same manner as in Example 5 except that the same two types of silver powder as in Example 8 were used.
- Example 10 A conductive film was produced in the same manner as in Example 6 except that the same two types of silver powder as in Example 8 were used.
- Example 11 A conductive film was produced in the same manner as in Example 7 except that the same two types of silver powders as in Example 8 were used.
- Comparative Example 1 A conductive film having a thickness of about 20 ⁇ m was formed from a commercially available silver paste (“Dotite (registered trademark) FA-353N” manufactured by Fujikura Kasei Co., Ltd.).
- Tables 1 and 2 show the used elastomer, the type and the blending amount of the metal filler, and the like for Examples and Comparative Examples.
- the SEM photograph of the film thickness direction cross section of the electrically conductive film of Example 8 is shown in FIG.
- FIG. 9 in the conductive film of Example 1, it was confirmed that the flake-like fillers (silver powders A and B) in the elastomer were oriented in the film spreading direction (left and right direction).
- FIG. 13 in the conductive film of Example 8, a flake-like filler (silver having a large length in the film development direction and a large aspect ratio as compared with the conductive film of Example 1 (FIG. 9) Powder D) can be confirmed.
- volume resistivity of the conductive film was measured according to the parallel terminal electrode method of JIS K6271 (2008). At this time, a commercially available butyl rubber sheet (manufactured by Tigers Polymer Co., Ltd.) was used as a support made of an insulating resin for supporting the conductive film (test piece). Two types of measurement of volume resistivity were performed depending on the presence or absence of elongation. That is, one was measured in the natural state (without elongation), and the other was measured in the state of elongation at an elongation rate of 100%.
- the evaluation results of the conductive films of the example and the comparative example are summarized in the above Table 1 and Table 2.
- Tables 1 and 2 all of the conductive films of Examples 1 to 7 were subjected to the conditions (A) [average value of the reference number of 0.8 (pieces / ⁇ m or more)], and (B) The number of unit areas having an elastomer area ratio of 60% or more satisfies 20 or more.
- the conductive films of Examples 8 to 11 contain a flake filler (silver powder D) having a thickness of 0.2 ⁇ m and an aspect ratio of 65.
- the conductive films of Examples 8 to 11 contain the condition (A) [metal filler contains flake-like filler having a thickness of 1 ⁇ m or less and an aspect ratio of 26 or more, and the average value of the reference number is 0.4 / ⁇ m or more] and (B) [the number of unit areas having an elastomer area ratio of 60% or more is 20 or more] are satisfied. Therefore, the conductive films of Examples 1 to 11 are all flexible and have high conductivity. Moreover, even if it extends, the increase in electrical resistance is small.
- Example 1, 2 and 4 the conductivity in the natural state was high. Moreover, when Example 1, 2 and 4 is compared, the number of objects of condition (B) is small in this order. Along with this, the elastic modulus became higher in the order of Examples 1, 2 and 4. In other words, the flexibility decreased. For this reason, in Examples 2 and 4, although the volume resistivity in the natural state is smaller than that in Example 1, the volume resistivity after elongation is larger.
- the conductive film of Example 3 contains only flake-like filler (silver powder A: about 0.2 ⁇ m) having a very thin thickness.
- the conductivity of the conductive film of Example 3 is secured despite the small filling amount (volume ratio) of the metal filler.
- a thin anisotropic filler is used, a conductive path can be efficiently formed in the elastomer even with a small amount of filling.
- the elastic modulus of the conductive film of Example 1 using acrylic rubber was lower than that of the conductive films of Examples 5 to 7 using urethane rubber or the like.
- the difference in elastic modulus is also apparent when Example 8 is compared with Examples 9-11.
- the conductive films of Examples 8 to 11 contain flake-like fillers (silver powder D) having a large aspect ratio. Since the aspect ratio is large, the fillers are easily in contact with each other. Thereby, a conductive path can be efficiently formed in the elastomer. Therefore, the conductivity of the conductive films of Examples 8 to 11 was high even if the filling amount of the metal filler was small.
- Comparative Example 2 used a flaky filler (silver powder B: about 0.9 ⁇ m) having a greater thickness compared to Example 3. For this reason, when the filling amount of the metal filler is 31 vol%, a sufficient conductive path can not be formed, and it is considered that the volume resistivity is increased. Moreover, in Comparative Example 3, of the two conditions, (A) is satisfied but (B) is not satisfied. That is, in the case of Comparative Example 3, the conductivity is high but the flexibility is poor. Therefore, although the volume resistivity in the natural state was small, a crack was generated at the time of elongation, and the volume resistivity increased significantly. Further, in Comparative Example 4, neither of the conditions (A) and (B) is satisfied. In Comparative Example 4, although the volume resistivity in the natural state was small, the volume resistivity increased at the time of elongation.
- the applicability to the flexible wiring board was evaluated about the electrically conductive film of an Example and a comparative example. That is, when the volume resistivity of the conductive film in a stretched state at an elongation rate of 100% is 1 ⁇ 10 ⁇ 2 ⁇ cm or less, it can be applied (shown by ⁇ in Tables 1 and 2), 1 ⁇ 10 When it exceeded -2 ⁇ cm, it was evaluated that it was not applicable (same, it shows by x mark). As a result, as shown in Tables 1 and 2, it was confirmed that the conductive films of the examples were all suitable for flexible wiring boards.
- FIG. 12 shows a cross-sectional view in the XII-XII direction of FIG.
- the actuator 5 includes a dielectric film 50 and a pair of electrodes 51a and 51b.
- the dielectric film 50 is in the form of a circular thin film having a diameter of 70 mm and a thickness of 50 ⁇ m.
- the dielectric film 50 is disposed in a biaxially stretched state at a stretch rate of 50%.
- the stretch ratio is a value calculated by the following formula (II).
- the pair of electrodes 51 a and 51 b are arranged to face each other in the vertical direction with the dielectric film 50 interposed therebetween.
- the electrodes 51a and 51b have a circular thin film shape with a diameter of about 27 mm and a thickness of 20 ⁇ m, and are arranged substantially concentrically with the dielectric film 50.
- the electrodes 51a and 51b are made of the conductive film of the embodiment or the comparative example.
- a terminal portion 510a that protrudes in the radial direction is formed at the outer peripheral edge of the electrode 51a.
- the terminal portion 510a has a rectangular plate shape.
- a terminal portion 510b that protrudes in the radial direction is formed at the outer peripheral edge of the electrode 51b.
- the terminal portion 510b has a rectangular plate shape.
- the terminal portion 510 b is disposed at a position facing the terminal portion 510 a by 180 °.
- the terminal portions 510a and 510b are each connected to the power source 52 via a conductor.
- a marker 530 is attached to the electrode 51a in advance. The displacement of the marker 530 was measured by the displacement gauge 53, and was used as the displacement amount of the actuator 5.
- a voltage of an electric field strength of 40 V / ⁇ m was applied to measure the amount of displacement.
- the electric field strength is a value obtained by dividing the applied voltage by the thickness of the dielectric film.
- the displacement rate was calculated by the following equation (III) from the measured displacement amount.
- Displacement rate (%) (displacement amount / radius of electrode) ⁇ 100 (III)
- the response is good (shown by ⁇ in Table 1 and Table 2), and when it is less than 4%, the response is poor (same, shown by x And evaluated.
- the flexible actuator is used, for example, as an artificial muscle for industrial, medical, and welfare robots, a small pump for cooling or electronic parts, a medical instrument, and the like.
- the conductive film of the present invention is suitable for the electrode, wiring and the like of such a flexible actuator. Moreover, it is suitable also for electrodes of an elastomer sensor such as a capacitance type sensor, wiring, and the like. In addition to the power generation element, it is also suitable for electrodes of flexible transducers that emit light, heat, color, etc., wiring, and the like.
- the conductive film of the present invention is also useful for flexible wiring boards and the like used in wearable devices and the like.
- the conductive film of the present invention is excellent in flexibility and conductivity. Therefore, it can be used for members that require electrical control and flexible contact. For example, it is suitable for an electrode layer and surface layer of a developing roll, charging roll, transfer roll, sheet feeding roll, toner layer forming member, cleaning blade, charging blade and the like used in OA (Ofice Automation) equipment such as laser beam printer.
- OA Arte Automation
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Abstract
Description
(A)走査型電子顕微鏡により撮影された膜厚方向の断面写真に、膜厚方向に延びる三本の直線を膜展開方向に3μmずつ離間して描き、各々の該直線ごとに、該直線と交わる該断面写真における最長部の長さが2μm以上の該金属フィラーの個数を数えて、該個数を該直線の長さで除することにより該直線1μm当たりの基準個数を算出した場合に、三本の該直線における該基準個数の平均値が、0.8(個/μm)以上である、または、該金属フィラーは厚さが1μm以下でアスペクト比が26以上のフレーク状フィラーを含み、該基準個数の平均値が0.4(個/μm)以上である。
(B)走査型電子顕微鏡により撮影された膜厚方向の断面写真に、2μm四方の単位領域が100個連なって形成される測定領域を設け、該単位領域ごとに、該エラストマーが占める面積を測定した場合に、該エラストマーの面積割合が60%以上である該単位領域の個数が、20個以上である。
2:アクチュエータ(トランスデューサ) 20:誘電膜 21a、21b:電極 22a、22b:配線 23:電源
3:発電素子(トランスデューサ) 30:誘電膜 31a、31b:電極 32a~32c:配線
4:フレキシブル配線板 40:基材 41:表側配線用コネクタ 42:裏側配線用コネクタ
5:アクチュエータ 50:誘電膜 51a、51b:電極 52:電源 53:変位計 510a、510b:端子部 530:マーカー
100:導電膜 101:エラストマー 102:金属フィラー
01X~16X:表側電極 01X1~16X1:表側接続部
01Y~16Y:裏側電極 01Y1~16Y1:裏側接続部
01x~16x:表側配線 01y~16y:裏側配線
E:単位領域 M:測定領域
本発明の導電膜を構成するエラストマーは、室温でゴム状弾性を有するものであればよい。例えば、ガラス転移温度(Tg)が-10℃以下のエラストマーは、柔軟なため好適である。また、Tgが低くなると、結晶性が低下するため、エラストマーの破断伸びが大きくなる。つまり、より伸長しやすくなる。したがって、エラストマーのTgは、-20℃以下、さらには-35℃以下であることが望ましい。本明細書では、ガラス転移温度として、JIS K7121(1987)に準じて測定した中間点ガラス転移温度を採用する。
(A)走査型電子顕微鏡により撮影された膜厚方向の断面写真に、膜厚方向に延びる三本の直線を膜展開方向に3μmずつ離間して描き、各々の直線ごとに、該直線と交わる断面写真における最長部の長さが2μm以上の金属フィラーの個数を数えて、該個数を該直線の長さで除することにより該直線1μm当たりの基準個数を算出した場合に、三本の直線における基準個数の平均値が、0.8(個/μm)以上である、または、該金属フィラーは厚さが1μm以下でアスペクト比が26以上のフレーク状フィラーを含み、該基準個数の平均値が0.4(個/μm)以上である。
(B)走査型電子顕微鏡により撮影された膜厚方向の断面写真に、2μm四方の単位領域が100個連なって形成される測定領域を設け、単位領域ごとに、エラストマーが占める面積を測定した場合に、エラストマーの面積割合が60%以上である単位領域の個数が、20個以上である。
本発明の導電膜を電極および配線に使用したエラストマーセンサの一例として、静電容量型センサの実施形態を説明する。まず、本実施形態の静電容量型センサの構成について説明する。図4に、静電容量型センサの上面図を示す。図5に、図4のV-V断面図を示す。図4、図5に示すように、静電容量型センサ1は、誘電膜10と、一対の電極11a、11bと、配線12a、12bと、カバーフィルム13a、13bと、を備えている。
本発明の導電膜を電極に使用したアクチュエータの実施形態を説明する。図6に、本実施形態のアクチュエータの断面模式図を示す。(a)はオフ状態、(b)はオン状態を各々示す。図6に示すように、アクチュエータ2は、誘電膜20と、電極21a、21bと、配線22a、22bと、を備えている。誘電膜20は、ウレタンゴム製である。電極21aは、誘電膜20の上面の略全体を覆うように、配置されている。同様に、電極21bは、誘電膜20の下面の略全体を覆うように、配置されている。電極21a、21bは、各々、配線22a、22bを介して電源23に接続されている。電極21a、21bは、いずれも本発明の導電膜からなる。
本発明の導電膜を電極に使用した発電素子の実施形態を説明する。図7に、本実施形態の発電素子の断面模式図を示す。(a)は伸長時、(b)は収縮時を各々示す。図7に示すように、発電素子3は、誘電膜30と、電極31a、31bと、配線32a~32cと、を備えている。誘電膜30は、ウレタンゴム製である。電極31aは、誘電膜30の上面の略全体を覆うように、配置されている。同様に、電極31bは、誘電膜30の下面の略全体を覆うように、配置されている。電極31aには、配線32a、32bが接続されている。すなわち、電極31aは、配線32aを介して、外部負荷(図略)に接続されている。また、電極31aは、配線32bを介して、電源(図略)に接続されている。電極31bは、配線32cにより接地されている。電極31a、31bは、いずれも本発明の導電膜からなる。
本発明の導電膜を配線に使用したフレキシブル配線板の実施形態を説明する。図8に、本実施形態のフレキシブル配線板の上面透過図を示す。なお、図8中、裏側の配線については細線で示す。図8に示すように、フレキシブル配線板4は、基材40と、表側電極01X~16Xと、表側電極01X~16Xと、表側配線01x~16xと、裏側配線01y~16yと、表側配線用コネクタ41と、裏側配線用コネクタ42と、を備えている。
[実施例1~4]
まず、二種類のモノマーを懸濁重合して、アクリルゴムポリマーを製造した。モノマーとしては、n-ブチルアクリレート(BA)と、アリルグリシジルエーテル(AGE)と、を用いた。モノマーの配合割合は、BAを98質量%、AGEを2質量%とした。得られたアクリルゴムポリマーの重量平均分子量を、ゲル浸透クロマトグラフィー(GPC)により測定したところ、約90万であった。また、アクリルゴムポリマーのTgは、-46℃であった。
銀粉末A:福田金属箔粉工業(株)製「ナノメルト(登録商標)Ag-XF」(フレーク状、平均粒子径約5μm、厚さ約0.2μm、アスペクト比25)
銀粉末B:DOWAエレクトロニクス(株)製「FA-D-4」(フレーク状、平均粒子径約15μm、厚さ約0.9μm、アスペクト比16.7)。
銀粉末C:DOWAエレクトロニクス(株)製「AG2-1C」(球状、平均粒子径約0.5μm、アスペクト比1)。
アクリルゴムに替えてウレタンゴムを用いた以外は、実施例1と同様にして、導電膜を製造した。ウレタンゴムとしては、日本ポリウレタン工業(株)製「ニッポラン(登録商標)5230」を用いた。また、架橋剤および加工助剤を配合せずに、ウレタンゴムポリマーを溶剤に溶解させて、エラストマー溶液を調製した。
アクリルゴムに替えてヒドリンゴムを用いた以外は、実施例1と同様にして、導電膜を製造した。ヒドリンゴムとしては、ダイソー(株)製「エピクロマー(登録商標)CG102」を用いた。また、架橋剤としては、トリアジンチオール(和光純薬工業(株)製)0.5質量部を用い、加工助剤を配合せずに、エラストマー組成物を調製した。
アクリルゴムに替えてシリコーンゴムを用いた以外は、実施例1と同様にして、導電膜を製造した。シリコーンゴムとしては、モメンティブ・パフォーマンス・マテリアルズ・ジャパン合同会社製「TSE-3351」を用いた。また、架橋剤および加工助剤を配合せずに、シリコーンゴムポリマーを溶剤に溶解させて、エラストマー溶液を調製した。
銀粉末の種類および配合量を変更した以外は、実施例1~4と同様にして、導電膜を製造した。銀粉末としては、上記銀粉末Cと、化学還元法により作製された平均粒子径2μmの球状銀粒子を、ボールミルを用いて扁平化して作製された銀粉末Dと、の二種類を使用した。銀粉末Dの粒子形状はフレーク状、平均粒子径は約13μm、厚さは約0.2μm、アスペクト比は65である。
実施例8と同じ二種類の銀粉末を使用した以外は、実施例5と同様にして、導電膜を製造した。
実施例8と同じ二種類の銀粉末を使用した以外は、実施例6と同様にして、導電膜を製造した。
実施例8と同じ二種類の銀粉末を使用した以外は、実施例7と同様にして、導電膜を製造した。
市販の銀ペースト(藤倉化成(株)製「ドータイト(登録商標)FA-353N」)から、厚さ約20μmの導電膜を形成した。
銀粉末の種類および配合量を変更した以外は、上記実施例1~4と同様にして、導電膜を製造した。
実施例および比較例の導電膜について、膜厚方向断面のSEM写真を撮影し、(A)および(B)の条件を満たすか否かを調べた。まず、各導電膜をエポキシ樹脂で包埋し、ミクロトームにより膜厚方向の断面を切り出した。次に、当該断面のSEM写真を撮影した(倍率1000~5000倍)。SEM写真の例として、図9に、実施例1の導電膜の膜厚方向断面のSEM写真を示す。図10に、比較例1の導電膜の膜厚方向断面のSEM写真を示す。図13に、実施例8の導電膜の膜厚方向断面のSEM写真を示す。図9に示すように、実施例1の導電膜については、エラストマー中のフレーク状フィラー(銀粉末A、B)が、膜展開方向(左右方向)に配向していることが確認された。また、図13に示すように、実施例8の導電膜においては、実施例1の導電膜(図9)と比較して、膜展開方向の長さが大きくアスペクト比が大きいフレーク状フィラー(銀粉末D)が確認できる。
まず、SEM写真の略中央部分に、膜厚方向に延びる長さ10μmの三本の直線を、3μm間隔で描いた。次に、各々の直線ごとに、直線と交わり、かつ最長部の長さが2μm以上の金属フィラーの個数を数えた。続いて、得られた個数を直線の長さで除して、各々の直線ごとに、基準個数を算出した。そして、三つの基準個数の平均値を算出した。実施例および比較例の導電膜における、基準個数の平均値を、上記表1、表2にまとめて示す。
まず、SEM写真に、20μm四方の正方形の測定領域を設けた。次に、測定領域を、2μm四方の正方形の単位領域100個(10個×10個)に分割した。続いて、バイナリ画像解析ソフトを用いて、各単位領域を白黒のビットマップに変換した。そして、単位領域ごとに、エラストマーおよび金属フィラーの画素数から、エラストマーの占める面積割合を算出した。実施例および比較例の導電膜における、エラストマーの面積割合が60%以上の単位領域の個数を、上記表1、表2にまとめて示す。
実施例および比較例の導電膜について、柔軟性および導電性を評価した。以下、各々の評価方法について説明する。
導電膜について、JIS K7127(1999)に準じた引張試験を行った。試験片の形状は、試験片タイプ2とした。得られた応力-伸び曲線から、導電膜の弾性率を算出した。
導電膜の体積抵抗率を、JIS K6271(2008)の平行端子電極法に準じて測定した。この際、導電膜(試験片)を支持する絶縁樹脂製支持具として、市販のブチルゴムシート(タイガースポリマー(株)製)を用いた。体積抵抗率の測定は、伸長の有無により二種類行った。すなわち、一つは、自然状態(伸長なし)で測定し、もう一つは、伸長率100%で伸長した状態で測定した。ここで、伸長率は、次式(I)により算出した値である。
伸長率(%)=(ΔL0/L0)×100・・・(I)
[L0:試験片の標線間距離、ΔL0:試験片の標線間距離の伸長による増加分]
実施例および比較例の導電膜の評価結果を、上記表1、表2にまとめて示す。表1、表2に示すように、実施例1~7の導電膜は、いずれも、条件(A)[基準個数の平均値が0.8(個/μm)以上]、および(B)[エラストマーの面積割合が60%以上である単位領域の個数が20個以上]の両方を満たしていた。また、実施例8~11の導電膜は、厚さ0.2μm、アスペクト比65のフレーク状フィラー(銀粉末D)を含む。このため、実施例8~11の導電膜は、条件(A)[金属フィラーは厚さが1μm以下でアスペクト比が26以上のフレーク状フィラーを含み、基準個数の平均値が0.4(個/μm)以上]、および(B)[エラストマーの面積割合が60%以上である単位領域の個数が20個以上]の両方を満たしていた。したがって、実施例1~11の導電膜は、いずれも柔軟で、高い導電性を有する。また、伸長しても電気抵抗の増加は小さい。
実施例および比較例の導電膜を電極に用いたアクチュエータを作製し、アクチュエータの応答性を評価した。
延伸率(%)={√(S2/S1)-1}×100・・・(II)
[S1:延伸前(自然状態)の誘電膜面積、S2:二軸方向延伸後の誘電膜面積]
一対の電極51a、51bは、誘電膜50を挟んで上下方向に対向するよう配置されている。電極51a、51bは、直径約27mm、厚さ20μmの円形薄膜状を呈しており、各々、誘電膜50と略同心円状に配置されている。電極51a、51bは、実施例または比較例の導電膜からなる。電極51aの外周縁には、拡径方向に突出する端子部510aが形成されている。端子部510aは矩形板状を呈している。同様に、電極51bの外周縁には、拡径方向に突出する端子部510bが形成されている。端子部510bは矩形板状を呈している。端子部510bは、端子部510aに対して、180°対向する位置に配置されている。端子部510a、510bは、各々、導線を介して電源52に接続されている。
変位率(%)=(変位量/電極の半径)×100・・・(III)
そして、変位率が4%以上の場合には、応答性は良好(表1、表2中、○印で示す)、4%未満の場合には、応答性は不良(同、×印で示す)、と評価した。
Claims (12)
- エラストマーと、該エラストマー中に充填されている金属フィラーと、を含み、次の(A)および(B)の条件を満たすことを特徴とする導電膜。
(A)走査型電子顕微鏡により撮影された膜厚方向の断面写真に、膜厚方向に延びる三本の直線を膜展開方向に3μmずつ離間して描き、各々の該直線ごとに、該直線と交わる該断面写真における最長部の長さが2μm以上の該金属フィラーの個数を数えて、該個数を該直線の長さで除することにより該直線1μm当たりの基準個数を算出した場合に、三本の該直線における該基準個数の平均値が0.8(個/μm)以上である、または、該金属フィラーは厚さが1μm以下でアスペクト比が26以上のフレーク状フィラーを含み、該基準個数の平均値が0.4(個/μm)以上である。
(B)走査型電子顕微鏡により撮影された膜厚方向の断面写真に、2μm四方の単位領域が100個連なって形成される測定領域を設け、該単位領域ごとに、該エラストマーが占める面積を測定した場合に、該エラストマーの面積割合が60%以上である該単位領域の個数が、20個以上である。 - 前記金属フィラーの充填量は、導電膜の体積を100vol%とした場合の45vol%未満である請求項1に記載の導電膜。
- 前記金属フィラーは、厚さが1μm以下のフレーク状または針状であって、膜展開方向に配向する異方性フィラーを含む請求項1または請求項2に記載の導電膜。
- 前記金属フィラーは、さらに、平均粒子径が0.1μm以上1.5μm以下の塊状フィラーを含む請求項3に記載の導電膜。
- 前記異方性フィラーと前記塊状フィラーとの含有割合は、質量比で2:1~50:1である請求項4に記載の導電膜。
- 前記エラストマーは、水素結合可能な官能基を有し、ガラス転移温度(Tg)が-10℃以下である請求項1ないし請求項5のいずれかに記載の導電膜。
- 前記エラストマーは、アクリルゴム、ウレタンゴム、ヒドリンゴム、シリコーンゴムから選ばれる一種以上である請求項6に記載の導電膜。
- 前記アクリルゴムは、炭素数4以上のアルキル基を有するアクリル酸エステルモノマー単位を50mol%以上含む請求項7に記載の導電膜。
- 前記エラストマーの架橋には、硫黄を含む化合物が使用されていない請求項1ないし請求項8のいずれかに記載の導電膜。
- エラストマー製の弾性部材の表面に形成されている請求項1ないし請求項9のいずれかに記載の導電膜。
- エラストマー製の誘電膜と、該誘電膜を介して配置されている複数の電極と、複数の該電極と各々接続されている配線と、を備え、
該電極および該配線の少なくとも一方は、請求項1ないし請求項10のいずれかに記載の導電膜からなることを特徴とするトランスデューサ。 - 配線の少なくとも一部は、請求項1ないし請求項10のいずれかに記載の導電膜からなることを特徴とするフレキシブル配線板。
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KR101346416B1 (ko) | 2014-01-02 |
JPWO2011145411A1 (ja) | 2013-07-22 |
CN102483972B (zh) | 2013-10-23 |
EP2450911A1 (en) | 2012-05-09 |
EP2450911A4 (en) | 2013-04-17 |
US20120119626A1 (en) | 2012-05-17 |
CN102483972A (zh) | 2012-05-30 |
KR20130026514A (ko) | 2013-03-13 |
US8446075B2 (en) | 2013-05-21 |
JP5363592B2 (ja) | 2013-12-11 |
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