JP2010153364A - Conductive film and transducer equipped therewith, and flexible wiring board - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a soft and expansible conductive film whose electric resistance is hardly increased during elongation, an to provide a flexible transducer and a flexible wiring board. <P>SOLUTION: The conductive film includes an elastomer having hydrogen bond capable functional groups, and having a glass transition temperature (Tg) of -10°C or lower, a flake or needle shaped first metal filler filled in the elastomer, and a massive second metal filler. The first metal filler is oriented in the film developing direction of the conductive film. The transducer includes at least either an electrode or a wire formed of the conductive film. At least part of the wire of the flexible wiring board is formed of the conductive film. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an electrode that can be expanded and contracted, a conductive film suitable for wiring and the like, a transducer including the conductive film, and a flexible wiring board.

  For example, as a means for detecting the deformation of a member, the magnitude of a load acting on the member, etc., development of a flexible sensor using a conductive resin or an elastomer has been advanced. In addition, actuators using polymer materials such as dielectric elastomers are highly flexible, lightweight, and easy to miniaturize, so their use in various fields such as artificial muscles, medical instruments, and fluid control is being studied. . For example, an actuator can be configured by sandwiching a dielectric film made of a dielectric elastomer between a pair of electrodes (see, for example, Patent Documents 1 and 2).

  These flexible sensors and actuators are required to be able to follow electrodes and wiring in the deformation of a substrate made of an elastomer or the like, a dielectric film, or the like. That is, for example, in an actuator, the dielectric film expands and contracts depending on the applied voltage. For this reason, it is desirable that the electrodes arranged on the front and back of the dielectric film can be expanded and contracted according to the expansion and contraction of the dielectric film so as not to hinder the movement of the dielectric film. For these reasons, a conductive material in which conductive carbon or metal powder is mixed with a binder such as an elastomer is currently used for electrodes and wiring.

  For example, as a conductive material that can be formed into a thin film, Patent Document 3 introduces a conductive composition in which a metal powder is blended with a polyolefin resin. Patent Document 4 introduces a conductive paste in which two types of scaly silver powders having different average particle diameters are blended with synthetic rubber.

JP 2008-070327 A Special table 2003-506858 Japanese Patent Laid-Open No. 2002-100377 JP 2005-166322 A

  The specific resistance of conductive carbon is relatively large, about 0.1 to 1 Ωcm. For this reason, when a conductive material in which conductive carbon is blended in a binder such as an elastomer is used, there is a problem that the electrical resistance of the electrode or the like increases. When the electrical resistance of the electrode or the like is high, the element is likely to deteriorate due to heat generated by the internal resistance. In addition, the responsiveness of the actuator may be reduced due to the generation of reactance components 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.

  In addition to being able to expand and contract, electrodes and wiring are also required to have a small change in electrical resistance when stretched. In this regard, a commercially available silver paste in which silver powder is blended with a binder resin is poor in flexibility. That is, in addition to the high elastic modulus of the binder itself, the silver paste is highly filled, so the elastic modulus of the silver paste is high. For this reason, if extension is large, a crack will occur and electric resistance will increase remarkably. In addition, when used as an electrode of an actuator, the expansion and contraction of the dielectric film cannot be followed, and the movement of the dielectric film may be hindered.

  Moreover, according to the electroconductive composition described in the said patent document 3, polyolefin resin is used for a binder. Since the polyolefin resin has a high elastic modulus, the conductive composition is poor in flexibility. For this reason, when used for an electrode of an actuator, the expansion and contraction of the dielectric film cannot be followed and the movement of the dielectric film may be hindered. Further, when the conductive composition is stretched, the binder and the metal powder are easily peeled off. For this reason, cracks are likely to occur during stretching, and the electrical resistance increases.

  On the other hand, the conductive paste described in Patent Document 4 is formed by blending scaly silver powder with synthetic rubber. Since the silver powder has a scaly shape, the contact area between the silver powders is large. Therefore, an increase in electrical resistance during expansion is suppressed to some extent. However, since the packing density of the silver powder per unit volume is low, a gap is easily generated between the silver powders. Therefore, the electrical resistance becomes large at the time of extension. In this case, when the filling amount of the silver powder is increased, the elastic modulus of the conductive paste is increased. Therefore, the flexibility of the conductive paste is reduced, and cracks are likely to occur during stretching.

  This invention is made | formed in view of such a situation, and makes it a subject to provide the electrically conductive film which is soft and can be expanded-contracted and an electrical resistance does not increase easily at the time of expansion | extension. Another object of the present invention is to provide a flexible transducer and a flexible wiring board by using such a conductive film.

  (1) In order to solve the above-mentioned problem, the conductive film of the present invention is filled with an elastomer having a functional group capable of hydrogen bonding and having a glass transition temperature (Tg) of −10 ° C. or less. The flaky or acicular first metal filler and the massive second metal filler are characterized in that the first metal filler is oriented in the film development direction. 1).

  The binder in the conductive film of the present invention is an elastomer having a functional group capable of hydrogen bonding and having a Tg of −10 ° C. or lower. The functional group capable of hydrogen bonding has high affinity for the first metal filler and the second metal filler (hereinafter collectively referred to as “metal filler”). For this reason, interface peeling between the elastomer and the metal filler is unlikely to occur. Therefore, even when stretched, cracks are unlikely to occur in the conductive film of the present invention, and electrical resistance is also unlikely to increase. In addition, an elastomer having a Tg of −10 ° C. or lower has a low elastic modulus and is flexible. For this reason, the electrically conductive film of this invention is excellent in the followable | trackability with respect to deformation | transformation of a base material, a dielectric film, etc. Further, even when the metal filler is highly filled, flexibility can be maintained.

  The elastomer is filled with two types of metal fillers. One of the first metal fillers has a flake shape (flaky shape) or a needle shape. The other second metal filler has a lump shape. Here, the “bulk shape” includes a spherical shape, a substantially spherical shape (an elliptical sphere, an oval sphere (a shape in which a pair of opposing hemispheres are connected by a cylinder), and the like, and an indefinite shape having an uneven surface.

  The flaky or needle-shaped first metal filler is oriented in the direction of development of the conductive film. That is, the first metal filler is disposed in the elastomer so that the longitudinal direction is substantially parallel to the film development direction. For this reason, 1st metal fillers overlap and a contact area is large. Therefore, the conductivity of the conductive film is high. However, in the case of only the flaky or needle-like first metal filler, a gap is likely to be generated between the first metal fillers, and the electrical resistance is increased when the conductive film is stretched. In addition, the elastic modulus is high and flexibility is impaired. Therefore, when a massive second metal filler is mixed with the first metal filler, the second metal filler enters a gap between the first metal fillers. As a result, a conduction path is ensured even during extension, and an increase in electrical resistance is suppressed. Moreover, the elastic modulus of a electrically conductive film falls and a softness | flexibility improves by mixing a block-shaped 2nd metal filler. Thus, by using two types of metal fillers having different shapes, a flexible conductive film having high conductivity even when stretched can be formed.

  FIG. 1 and FIG. 2 show the filling state of the metal filler before and after stretching in the conductive film of the present invention as a model. 1 and 2 are schematic diagrams for explaining the action of the metal filler, including the mixing ratio of the first metal filler and the second metal filler, the shape and number of the metal filler, etc. The conductive film of the invention is not limited at all.

  As shown in FIG. 1, in the conductive film 100, the first metal filler 102 and the second metal filler 103 are dispersed in the elastomer 101. The first metal filler 102 has a flake shape and is oriented in the direction of development of the conductive film 100. The second metal filler 103 has a spherical shape. A second metal filler 103 is disposed in a gap between adjacent first metal fillers 102. In the conductive film 100 before stretching, a conductive path is formed by contact of the first metal filler 102 and the second metal filler 103. On the other hand, as shown in FIG. 2, when the conductive film 100 is stretched in the left-right direction (the dotted line frame in FIG. 2 indicates the state before stretching in FIG. 1), the gap between the first metal fillers 102. Becomes larger. However, the second metal filler 103 has entered the gap. For this reason, even when extended, the contact state between the first metal filler 102 and the second metal filler 103 is maintained, and a conduction path is secured. Therefore, an increase in electrical resistance during expansion is suppressed.

  (2) A transducer according to the present invention is characterized in that the conductive film according to the present invention is provided as at least one of an electrode and a wiring (corresponding to claim 11).

  A transducer is a device that converts one type of energy into another type of energy. The transducer includes, for example, an actuator and a sensor that perform conversion between electric energy and mechanical energy. According to the transducer of the present invention, at least one of the electrode and the wiring is made of the conductive film of the present invention. Therefore, even when the member on 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 difficult to be hindered by the electrode or the like. In addition, in an electrode or the like, there is little decrease in conductivity when stretched, and even when it is repeatedly deformed, heat generation due to internal resistance is small. Therefore, the transducer of the present invention is excellent in durability.

  (3) In the flexible wiring board of the present invention, at least a part of the wiring is made of the conductive film according to any one of claims 1 to 10 (corresponding to claim 14).

  According to the flexible wiring board of the present invention, the wiring expands and contracts following the deformation of the base material. Even if the wiring is extended, there is little decrease in conductivity, and even when the 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.

It is a schematic diagram which shows the filling state of the metal filler before the expansion | extension in the electrically conductive film of this invention. It is a schematic diagram which shows the filling state of the metal filler after the expansion | extension in the same electrically conductive film. It is a top view of the capacitive type sensor which is one Embodiment of the transducer of this invention. It is IV-IV sectional drawing of FIG. It is a cross-sectional schematic diagram of the actuator which is one Embodiment of the transducer of this invention, Comprising: (a) shows an OFF state, (b) shows an ON state, respectively. It is a cross-sectional schematic diagram of the electric power generation transducer which is one Embodiment of the transducer of this invention, Comprising: (a) is at the time of expansion | extension, (b) shows the time of contraction. It is an upper surface transmission figure of the flexible wiring board which is one Embodiment of this invention. 2 is an electron micrograph of a cross section of the conductive film of Example 1. FIG.

  Hereinafter, embodiments of the conductive film, the transducer including the conductive film, and the flexible wiring board of the present invention will be described in order.

<Conductive film>
The elastomer constituting the conductive film of the present invention has a functional group capable of hydrogen bonding, and has a glass transition temperature (Tg) of −10 ° C. or lower. The functional group capable of hydrogen bonding has high affinity with the metal filler described later. For example, ester group, urethane bond, urea bond, halogen group, hydroxyl group, carboxyl group, amino group, sulfonic acid group, ether bond and the like can be mentioned. Of these, those having an ester group are desirable. Moreover, the glass transition temperature (Tg) of an elastomer is -10 degrees C or less. Those having a Tg of −10 ° C. or less have rubber-like elasticity at room temperature and high flexibility. Moreover, since crystallinity will fall when Tg becomes low, the breaking elongation of an elastomer will become large. That is, it becomes easier to expand. From such a viewpoint, it is desirable that the Tg of the elastomer is −20 ° C. or lower, and further −35 ° C. or lower.

  As the elastomer, one type may be used alone, or two or more types may be mixed and used. For example, acrylic rubber, urethane rubber, hydrin rubber and the like are suitable. Especially, since acrylic rubber has low crystallinity and weak intermolecular force, Tg is lower than other rubbers. Therefore, it is flexible and has good elongation, and is suitable for an electrode of an actuator. As an acrylic rubber, what contains 50 mol% or more of acrylate monomer units having an alkyl group having 4 or more carbon atoms is desirable. 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.

  Further, the elastomer may contain additives such as a plasticizer, a processing aid, a crosslinking agent, a vulcanization accelerator, a vulcanization aid, an antiaging agent, a softening agent, and a colorant. For example, when a plasticizer is added, the processability of the elastomer is improved and the flexibility can be further improved. As the plasticizer, 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 elastomer is filled with a first metal filler and a second metal filler. The first metal filler has a flake shape or a needle shape. Further, the first metal filler is oriented in the film development direction of the conductive film. Although the average particle diameter of a 1st metal filler is not specifically limited, For example, it is desirable to set it as 2.5 micrometers or more and 15 micrometers or less. When the average particle diameter is less than 2.5 μm, the area where the first metal fillers overlap with each other becomes small, so that the electrical resistance tends to increase during stretching. On the other hand, when it becomes larger than 15 μm, the flexibility of the conductive film is lowered. In the present specification, a value measured by “Microtrack particle size distribution measuring device UPA-EX150 type” manufactured by Nikkiso Co., Ltd. is adopted as the average particle size of the metal filler.

  The aspect ratio of the first metal filler is desirably 5 or more and 25 or less. When the aspect ratio is less than 5, the area where the first metal fillers overlap with each other is small, so that the electrical resistance is likely to increase during stretching. On the other hand, when it becomes larger than 25, the flexibility of the conductive film decreases. Here, the aspect ratio is the ratio of the longest diameter to the shortest diameter of the metal filler (longest diameter / shortest diameter). In this specification, as the longest diameter and shortest diameter of the metal filler, values obtained by observing the metal filler with an electron microscope and taking a photographed electron micrograph are adopted.

  The second metal filler has a lump shape. Although the average particle diameter of a 2nd metal filler is not specifically limited, For example, it is desirable to set it as 0.1 micrometer or more and 8 micrometers or less. When the average particle size is less than 0.1 μm, the specific surface area is increased, so that the reinforcing property is increased and the flexibility of the conductive film is lowered. 0.3 μm or more is more preferable. On the other hand, if the thickness is larger than 8 μm, the second metal filler is difficult to enter the gap between the first metal fillers, so that it is difficult to form a conduction path. Therefore, the electrical resistance tends to increase during stretching. In addition, as the average particle diameter of the second metal filler is smaller, the desired conductivity can be ensured with a smaller amount. Therefore, the softness | flexibility of an electrically conductive film improves by the part which the filling amount of a 2nd metal filler reduces.

  The aspect ratio of the second metal filler is desirably 1 or more and 5 or less. If the aspect ratio is greater than 5, the second metal filler is less likely to enter the gap between the first metal fillers, making it difficult to form a conduction path. Therefore, the electrical resistance tends to increase during stretching. In addition, the flexibility of the conductive film also decreases.

  The kind of metal filler is not particularly limited. From the viewpoint that the conductivity is higher than that of carbon black and hardly corrode, for example, silver, gold, copper, nickel, rhodium, palladium, chromium, titanium, platinum, iron, and alloys thereof may be appropriately selected. Among these, silver is preferable because of its low electric resistance. Moreover, you may use the filler which coat | covered the surface of the particle | grains which have a defined shape with the metal. In this case, the specific gravity of the metal filler can be reduced as compared with the case where the metal filler is used alone. Therefore, sedimentation of the metal filler when the paint is formed is suppressed, and dispersibility is improved. Further, by processing the particles, various shapes of metal fillers can be easily produced. Moreover, the manufacturing cost of a metal filler can be reduced. As a metal to coat | cover, the metal suitable as a metal filler enumerated above can be used. The particles may be made of 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, and the like.

  Moreover, what is necessary is just to determine the filling amount of a 1st metal filler and a 2nd metal filler so that desired electroconductivity may be obtained. For example, it is desirable to set it as 300 to 1500 mass parts with respect to 100 mass parts of an elastomer. More preferably, it is 400 parts by mass or more and 1000 parts by mass or less. Here, the blending ratio of the first metal filler and the second metal filler may be determined in consideration of the elastic modulus of the conductive film, the effect of suppressing the increase in electrical resistance during stretching, and the like. For example, it is desirable that the mass ratio of the first metal filler and the second metal filler is 30: 1 to 1: 5. That is, you may mix | blend a 1st metal filler and a 2nd metal filler by 1: 1. Moreover, when mix | blending an excess of a 1st metal filler rather than a 2nd metal filler, it is good to make the compounding quantity of a 1st metal filler into 30 times or less of the compounding quantity of a 2nd metal filler. Alternatively, when the second metal filler is added in excess of the first metal filler, the amount of the second metal filler is preferably 5 times or less the amount of the first metal filler. In particular, the mass ratio of the first metal filler and the second metal filler may be 1: 1, or the first metal filler may be blended slightly more.

  The conductive film of the present invention is, for example, a conductive material obtained by kneading a polymer for an elastomer (including appropriate additives) and a metal filler with a pressure kneader such as a kneader or a Banbury mixer, a two-roller, etc. It can be manufactured by mold molding or extrusion molding. First, a metal filler is added to a solution obtained by dissolving a polymer for an elastomer in a solvent together with a predetermined additive, and the mixture is stirred and mixed to prepare a conductive paint. Next, the prepared conductive paint can be applied to a substrate or the like and dried by heating. In this case, the crosslinking reaction for the elastomer may be allowed to proceed during heating.

  Here, various known methods can be employed as the method for applying the conductive paint. For example, in addition to printing methods such as inkjet printing, flexographic printing, gravure printing, screen printing, pad printing, and lithography, dipping, spraying, bar coating, and the like can be given. For example, when a printing method is employed, it is possible to easily separate the applied part and the non-applied part. Also, printing of large areas, thin lines, and complicated shapes is easy. Among the printing methods, a screen printing method is preferable because a conductive paint having a high viscosity can be used and the coating thickness can be easily adjusted.

  In order to improve the orientation of the first metal filler in the conductive film, the formed conductive film may be subjected to processing such as hot pressing and stretching.

  What is necessary is just to determine the thickness of the electrically conductive film of this invention suitably according to a use. For example, when the conductive film of the present invention is used as an electrode or wiring of an elastomer sensor or actuator, the thickness of the conductive film is reduced from the viewpoint of minimizing the size of the elastomer sensor or actuator and minimizing the influence on the deformation of the dielectric film. Is desirable to be thin. For example, the thickness of the conductive film is preferably 4 μm or more and 1000 μm or less. More preferably, they are 10 micrometers or more and 50 micrometers or less.

  Moreover, what is necessary is just to form the electrically conductive film of this invention in the surfaces, such as a base material and a dielectric film, according to a use. Examples of the substrate include a flexible resin film made of polyimide, polyethylene, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), or the like. In addition, when the electrically conductive film of this invention is formed in the surface of the elastic member made from an elastomer, the effect that a softness | flexibility is high and an electrical resistance cannot increase easily at the time of expansion | extension can be exhibited more. Here, the elastic member includes a dielectric film in an actuator or the like. The thin-film elastic member can be manufactured, for example, by coating a paint for forming the elastic member on a substrate having releasability, and then cutting it into a desired shape and peeling it off.

  The conductive film of the present invention is suitable for transducer electrodes and wiring, flexible wiring board wiring, and the like. Hereinafter, first, embodiments of an elastomer sensor, an actuator, and a power generation transducer will be described as examples of a transducer including the conductive film of the present invention, and then an embodiment of a flexible wiring board will be described. In the transducer and flexible wiring board of the present invention, it is desirable to employ the preferred embodiment of the conductive film of the present invention described above.

<Elastomer sensor>
An embodiment of a capacitive sensor will be described as an example of an elastomer sensor using the conductive film of the present invention for electrodes and wiring. First, the configuration of the capacitive sensor of this embodiment will be described. FIG. 3 shows a top view of the capacitive sensor. FIG. 4 is a sectional view taken along the line IV-IV in FIG. As shown in FIGS. 3 and 4, the capacitive sensor 1 includes a dielectric film 10, a pair of electrodes 11a and 11b, wirings 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 μm.

  The electrode 11a has a rectangular shape. Three electrodes 11a are formed on the upper surface of the dielectric film 10 by screen printing. Similarly, the electrode 11b has a rectangular shape. Three electrodes 11b are formed on the lower surface of the dielectric film 10 so as to face the electrode 11a 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 arranged with the dielectric film 10 in between. The electrodes 11a and 11b are made of the conductive film of the present invention.

  The wiring 12a is connected to each of the electrodes 11a formed on the upper surface of the dielectric film 10. The electrode 11a and the connector 14 are connected by the wiring 12a. The wiring 12a is formed on the upper surface of the dielectric film 10 by screen printing. Similarly, the wiring 12b is connected to each of the electrodes 11b formed on the lower surface of the dielectric film 10 (indicated by a dotted line in FIG. 3). The electrode 11b and the connector (not shown) are connected by the wiring 12b. The wiring 12b 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. Similarly, the cover film 13b 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.

  Next, the movement of the capacitive sensor 1 will be described. For example, when the capacitive sensor 1 is pressed from above, the dielectric film 10, the electrode 11a, and the cover film 13a are united and curved downward. The thickness of the dielectric film 10 is reduced by the compression. As a result, the capacitance between the electrodes 11a and 11b increases. By this capacitance change, deformation due to compression is detected.

  Next, the function and effect of the capacitive sensor 1 of the present embodiment will be described. According to the capacitive sensor 1 of the present embodiment, 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. For this reason, the entire capacitive sensor 1 is flexible and can be expanded and contracted. Moreover, since the electrodes 11a and 11b can be expanded and contracted, they can be deformed following the deformation of the dielectric film 10. Furthermore, even if the electrodes 11a and 11b and the wirings 12a and 12b are expanded, the increase in electric resistance is small. For this reason, the responsiveness of the capacitive sensor 1 is good. In the capacitive sensor 1 of the present embodiment, three pairs of electrodes 11a and 11b facing each other with the dielectric film 10 narrowed are formed. However, the number, size, arrangement, etc. of the electrodes may be appropriately determined according to the application.

<Actuator>
An embodiment of an actuator using the conductive film of the present invention as an electrode will be described. FIG. 5 is a schematic cross-sectional view of the actuator of this embodiment. (A) shows an OFF state, and (b) shows an ON state. As shown in FIG. 5, the actuator 2 includes a dielectric film 20 and electrodes 21a and 21b. The dielectric film 20 is made of urethane rubber. The electrodes 21a and 21b are arranged on the front and back of the dielectric film 20, respectively. The electrodes 21a and 21b are connected to the power source 22 through wiring. When switching from the off state to the on state, a voltage is applied between the pair of electrodes 21a and 21b. The thickness of the dielectric film 20 is reduced by applying a voltage. Accordingly, 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. Thereby, the actuator 2 outputs the driving force in the horizontal and vertical directions in FIG.

  Here, the electrodes 21a and 21b are made of the conductive film of the present invention. Since the electrodes 21 a and 21 b can expand and contract, they can be deformed following the deformation of the dielectric film 20. That is, since the movement of the dielectric film 20 is not easily disturbed by the electrodes 21a and 21b, a larger amount of displacement can be obtained. Furthermore, even if the electrodes 21a and 21b are stretched, the increase in electrical resistance is small. Since the heat generated by the internal resistance is small, the electrodes 21a and 21b are not easily deteriorated. That is, the actuator 2 is excellent in durability. Note that a greater force can be generated when a laminated structure in which a plurality of dielectric films and electrodes are alternately laminated. As a result, the output of the actuator is increased, and the driven member can be driven with a greater force.

<Power generation transducer>
An embodiment of a power generation transducer using the conductive film of the present invention as an electrode will be described. In FIG. 6, the cross-sectional schematic diagram of the electric power generation transducer of this embodiment is shown. (A) shows the time of expansion, and (b) shows the time of contraction. As shown in FIG. 6, the power generation transducer 3 includes a dielectric film 30 and electrodes 31a and 31b. The dielectric film 30 is made of urethane rubber. The electrodes 31a and 31b are fixed to the front and back of the dielectric film 30, respectively. Conductive wires are connected to the electrodes 31a and 31b, and the electrode 31b is grounded.

  As shown in FIG. 6A, when the power generation transducer 3 is compressed and the dielectric film 30 is expanded in a direction parallel to the surfaces of the electrodes 31a and 31b, the film thickness of the dielectric film 30 is reduced, and the distance between the electrodes 31a and 31b is reduced. The charge is stored in Thereafter, when the compressive force is removed, the dielectric film 30 contracts due to the elastic restoring force of the dielectric film 30 as shown in FIG. At that time, electric charges are released and electric power is generated.

  Here, the electrodes 31a and 31b are made of the conductive film of the present invention. That is, the electrodes 31a and 31b can be expanded and contracted. For this reason, the movement of the dielectric film 30 is not easily disturbed by the electrodes 31a and 31b. In addition, in the electrodes 31a and 31b, there is little decrease in conductivity when stretched, and even when repeatedly deformed, heat generation due to internal resistance is small. Therefore, the power generation transducer 3 is excellent in durability.

<Flexible wiring board>
An embodiment of a flexible wiring board using the conductive film of the present invention for wiring will be described. In FIG. 7, the upper surface transparent view of the flexible wiring board of this embodiment is shown. In FIG. 7, the wiring on the back side is indicated by a thin line. As shown in FIG. 7, the flexible wiring board 4 includes a base material 40, front side electrodes 01X to 16X, front side electrodes 01X to 16X, front side wirings 01x to 16x, back side wirings 01y to 16y, and front side wiring connectors. 41 and a backside wiring connector 42.

  The base material 40 is made of urethane rubber and has a sheet shape. A total of 16 front side electrodes 01 </ b> X to 16 </ b> X are arranged on the upper surface of the base material 40. The front side electrodes 01X to 16X each have a strip shape. The front side electrodes 01X to 16X each extend in the X direction (left-right direction). The front-side electrodes 01X to 16X are arranged in the Y direction (front-rear direction) so as to be substantially parallel to each other at a predetermined interval. Front side connection portions 01X1 to 16X1 are arranged at the left ends of the front side electrodes 01X to 16X, respectively. Similarly, a total of 16 back-side electrodes 01Y to 16Y are arranged on the lower surface of the base material 40. The back side electrodes 01Y to 16Y each have a strip shape. The back-side electrodes 01Y to 16Y each extend 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 a predetermined interval. Back side connection portions 01Y1 to 16Y1 are arranged at the front ends of the back side electrodes 01Y to 16Y, respectively. As shown by hatching in FIG. 7, a detection unit that detects a load or the like is formed by a portion (overlapping portion) where the front side electrodes 01X to 16X intersect with the back side connection portions 01Y1 to 16Y1 with the base material 40 interposed therebetween. ing.

  A total of 16 front side wirings 01x to 16x are arranged on the upper surface of the substrate 40. The front side wirings 01x to 16x each have a linear shape. The front wiring connector 41 is disposed at the left rear corner of the base member 40. The front side wirings 01x to 16x connect the front side connection portions 01X1 to 16X1 and the front side wiring connector 41, respectively. Moreover, the upper surface of the base material 40, the front side electrodes 01X to 16X, and the front side wirings 01x to 16x are covered with a front side cover film (not shown) from above.

  A total of 16 back-side wirings 01y to 16y are arranged on the lower surface of the substrate 40. The back side wirings 01y to 16y each have a linear shape. The backside wiring connector 42 is disposed at the left front corner of the base material 40. The back side wirings 01y to 16y connect the back side connection portions 01Y1 to 16Y1 and the back side wiring connector 42, respectively. Moreover, the lower surface of the base material 40, the back side electrodes 01Y to 16Y, and the back side wirings 01y to 16y are covered with a back side cover film (not shown) from below.

  Each of the front side wiring connector 41 and the back side wiring connector 42 is electrically connected to a calculation unit (not shown). The impedance in the detection unit is input from the front side wirings 01x to 16x and the back side wirings 01y to 16y to the arithmetic unit. Based on this, the surface pressure distribution is measured.

  Here, the front-side wirings 01x to 16x and the back-side wirings 01y to 16y are each made of the conductive film of the present invention. That is, the front side wirings 01x to 16x and the back side wirings 01y to 16y can be expanded and contracted, respectively. For this reason, it can be deformed following the deformation of the substrate 40. Further, in the front-side wirings 01x to 16x and the back-side wirings 01y to 16y, there is little decrease in conductivity during expansion, and even when repeatedly deformed, heat generation due to internal resistance is small. Therefore, the flexible wiring board 4 is excellent in durability.

  Next, the present invention will be described more specifically with reference to examples.

<Manufacture of conductive film>
[Examples 1 to 4]
First, 100 parts by mass of an acrylic rubber polymer (Nippon (registered trademark) AR51) manufactured by Nippon Zeon Co., Ltd. and 1 part by mass of a processing aid stearic acid ("Lunac (registered trademark) S30" manufactured by Kao Corporation) And 2.5 parts by mass of a crosslinking accelerator zinc dimethyldithiocarbamate (“Noxer (registered trademark) PZ” manufactured by Ouchi Shinsei Chemical Co., Ltd.), and ferric dimethyldithiocarbamate (manufactured by Ouchi Shinsei Chemical Co., Ltd.) "Noxeller TTFE") and 0.5 parts by mass were mixed with a roll kneader to prepare an elastomer composition (acrylic rubber a1). In addition, about one of the examples (Example 4), the acrylic rubber polymer (same as above) is 70 parts by mass, and the plasticizer adipic acid diester ("ADEKA Sizer (registered trademark) RS-107" manufactured by ADEKA Corporation) ) Was added to prepare an elastomer composition (acrylic rubber a2). Table 1 below shows the composition of the elastomer composition together with the Tg of the acrylic rubber polymer used.

  Subsequently, the prepared elastomer composition was dissolved in 312 parts by mass of a solvent, ethylene glycol monobutyl ether acetate, to prepare an elastomer solution. A predetermined amount of two kinds of silver powders having different shapes and the like as metal fillers were added to the elastomer solution, and kneaded with three rolls to obtain a conductive paint (the shape and the like of the silver powder are shown in Table 2 below). See Table 3).

  The produced conductive paint was applied to the surface of an acrylic resin substrate by a bar coating method. Thereafter, the base material on which the coating film was formed was allowed to stand in a drying furnace at about 150 ° C. for about 30 minutes to dry the coating film, and the crosslinking reaction was advanced to obtain a conductive film. The thickness of the obtained conductive film was 10 μm.

[Example 5]
The type of acrylic rubber polymer was changed to prepare an elastomer composition (acrylic rubber b1). First, three types of monomers were subjected to suspension polymerization to produce an acrylic rubber polymer. As monomers, n-butyl acrylate (BA), acrylonitrile (AN), and allyl glycidyl ether (AGE) were used. The blending ratio of the monomer was 97% by mass of BA, 1% by mass of AN, and 2% by mass of AGE. When the weight average molecular weight of the obtained acrylic rubber polymer was measured by gel permeation chromatography (GPC), it was about 800,000. Next, 100 parts by mass of the manufactured acrylic rubber polymer was mixed with the same additive as in Examples 1 to 3 to prepare an elastomer composition. A conductive film was produced from the prepared elastomer composition in the same manner as in Examples 1 to 4 above.

[Example 6]
An elastomer composition (acrylic rubber b2) was prepared in the same manner as in Example 5 except that the crosslinking accelerator was changed. As the crosslinking accelerator, ammonium benzoate was used (blending amount 0.5 parts by mass). A conductive film was produced from the prepared elastomer composition in the same manner as in Examples 1 to 4 above.

[Example 7]
An elastomer composition (acrylic rubber b3) was prepared in the same manner as in Example 5 except that the processing aid was not used and a crosslinking agent was used instead of the crosslinking accelerator. As the cross-linking agent, a modified aliphatic polyamine (“ADEKA HARDNER (registered trademark) EH-451N” manufactured by ADEKA Corporation) was used (blending amount: 7 parts by mass). A conductive film was produced from the prepared elastomer composition in the same manner as in Examples 1 to 4 above.

[Example 8]
An elastomer composition (acrylic rubber c) was prepared in the same manner as in Example 7 except that the type of the acrylic rubber polymer was changed. As the acrylic rubber polymer, the following two types of polymers were mixed and used. One is the acrylic rubber polymer (BA / AN / AGE) used in Examples 5-7 above. The other is an acrylic rubber polymer produced by suspension polymerization of 2-ethylhexyl acrylate (2EHA), acrylonitrile (AN), and allyl glycidyl ether (AGE). The blending ratio of the latter monomer was 97% by mass of 2EHA, 1% by mass of AN, and 2% by mass of AGE. The weight average molecular weight of the latter acrylic rubber polymer was about 800,000. 67 parts by mass of the former acrylic rubber polymer (BA / AN / AGE) and 33 parts by mass of the latter acrylic rubber polymer (2EHA / AN / AGE) were mixed to make 100 parts by mass. A conductive film was produced from the prepared elastomer composition in the same manner as in Examples 1 to 4 above.

[Example 9]
An elastomer composition (acrylic rubber d) was prepared in the same manner as in Example 7 except that the type of the acrylic rubber polymer was changed. The acrylic rubber polymer was produced by suspension polymerization of ethyl acrylate (EA), acrylonitrile (AN), and allyl glycidyl ether (AGE). The blending ratio of the monomers was 97% by mass of EA, 1% by mass of AN, and 2% by mass of AGE. The resulting acrylic rubber polymer had a weight average molecular weight of about 800,000. A conductive film was produced from the prepared elastomer composition in the same manner as in Examples 1 to 4 above.

[Example 10]
A urethane rubber polymer was used instead of the acrylic rubber polymer. First, 100 parts by mass of a urethane rubber polymer (Nipporan (registered trademark) 5193 manufactured by Nippon Polyurethane Industry Co., Ltd .: urethane rubber a) was dissolved in 312 parts by mass of a solvent, ethylene glycol monobutyl ether acetate, to prepare an elastomer solution. . Next, the electrically conductive film was manufactured from the prepared elastomer solution like the said Examples 1-4.

[Comparative Examples 1-4]
A conductive film was produced in the same manner as in Examples 1 to 4 except that the silver powder to be blended was one type. The used elastomer composition is the same acrylic rubber a1 as in Examples 1 to 3 above.

[Comparative Example 5]
A conductive film was produced in the same manner as in Example 10 except that the type of the urethane rubber polymer was changed. As the urethane rubber polymer (Toyobo Co., Ltd. "Byron (registered trademark) UR3200": urethane rubber b) was used.

Table 2 shows the types and amounts of the elastomers and metal fillers used in Examples 1 to 10. Similarly, Table 3 shows the types and amounts of elastomers and metal fillers used in Comparative Examples 1-5.

<Evaluation method>
The manufactured conductive film was evaluated for flexibility and conductivity. Hereinafter, each evaluation method will be described.

[Flexibility]
The conductive film was subjected to a tensile test according to JIS K7127 (1999). The shape of the test piece was test piece type 2. The elastic modulus of the conductive film was calculated from the obtained stress-elongation curve.

[Conductivity]
The 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 rubber sheet (“VHB (registered trademark) 4910” manufactured by Sumitomo 3M Limited) was used as an insulating resin support for supporting the conductive film (test piece). Two types of volume resistivity were measured depending on whether or not there was stretching. That is, one was measured in a natural state (no stretching), and the other was measured in a stretched state at a stretch rate of 200%. Here, the expansion rate is a value calculated by the following equation (I).
Elongation rate (%) = (ΔL ₀ / L ₀ ) × 100 (I)
[L ₀ : Distance between marked lines of test piece, ΔL ₀ : Increase due to extension of distance between marked lines of test piece]
<Evaluation results>
The evaluation results of the conductive films of Examples and Comparative Examples are shown in Tables 2 and 3 together with the types and amounts of the elastomers and metal fillers used. Moreover, the electron micrograph of the cross section of the electrically conductive film of Example 1 is shown in FIG. The details of the silver powder used in Tables 2 and 3 are as follows. Here, silver powder AC is contained in a 1st metal filler. Silver powders D to F are contained in the second metal filler.
Silver powder A: manufactured by DOWA Electronics Co., Ltd., product “FA-D-4” (flakes, average particle diameter of about 15 μm, aspect ratio of about 25).
Silver powder B: manufactured by DOWA Electronics Co., Ltd., product “FA-2-3” (flakes, average particle diameter of about 6 μm, aspect ratio of about 20).
Silver powder C: flaky, average particle diameter of about 2.5 μm, aspect ratio of about 5.
Silver powder D (silver-coated glass beads): Product “ES-6000-S7” (spherical, average particle diameter of about 8 μm, aspect ratio of about 1) manufactured by Potters Ballotini Co., Ltd.
Silver powder E: manufactured by DOWA Electronics Co., Ltd., product “AG2-1C” (spherical, average particle diameter of about 0.5 μm, aspect ratio of about 1).
Silver powder F: spherical, average particle diameter of about 0.3 μm, aspect ratio of about 1.

  FIG. 8 shows that in the conductive film of Example 1, flaky silver powder (first metal filler) is oriented in the film development direction. Moreover, it turns out that spherical silver powder (second metal filler) fills the gaps between the flaky silver powders.

  Moreover, as shown in Table 2, the conductive films of the examples all showed high conductivity. In addition, the increase in volume resistivity was small even during stretching. Moreover, about the electrically conductive film of an Example, all were confirmed that elongation is favorable. For example, the electrically conductive film of Example 4 which mix | blended the plasticizer had a lower elasticity modulus compared with the electrically conductive film of Examples 1-3 which did not mix | blend the plasticizer. Further, when the conductive film of Example 7 and the conductive film of Example 8 were compared, the conductive film of Example 8 in which a polymer having a lower Tg was mixed showed a lower elastic modulus. In addition, about the electrically conductive film of Example 10 which uses urethane rubber, the elasticity modulus became high compared with the electrically conductive film of Examples 1-9 which used acrylic rubber.

  On the other hand, as shown in Table 3, the volume resistivity of the conductive film of the comparative example was greatly increased when stretched. In other words, the conductivity was reduced during stretching. Moreover, about the electrically conductive film of the comparative example 5 which uses the urethane rubber whose Tg is -3 degreeC, although the filling amount of silver powder was small, the elasticity modulus became very high.

  Further, when the conductive film of Example 1 and the conductive film of Comparative Example 1 are compared, even if the total filling amount of the silver powder is the same, in the case of only flakes (Comparative Example 1), the elastic modulus is It became high. In addition, in the case of only the flake shape (Comparative Example 1), the volume resistivity at the time of expansion also greatly increased. This is considered to be because a gap was generated between the flaky silver powders due to the elongation, and the conduction path was cut off. Further, as can be seen in comparison with the conductive film of Comparative Example 2, the elastic modulus decreased when the filling amount of the silver powder was reduced. However, since the conductive film of Comparative Example 2 was filled with only flaky silver powder, the volume resistivity at the time of expansion increased significantly as described above. When the conductive film of Comparative Example 1 and the conductive film of Comparative Example 3 are compared, even if the filling amount of the flaky silver powder is the same, Comparative Example 3 has a smaller average particle diameter of the silver powder. The elastic modulus was low.

  From the above, it was confirmed that the electrically conductive film of the present invention has high flexibility and electrical conductivity, and it is difficult for the electrical resistance to increase even when stretched.

  Flexible actuators are used in, for example, artificial muscles for industrial, medical, and welfare robots, small pumps for cooling electronic parts, medical use, and medical instruments. The conductive film of the present invention is suitable for such flexible actuator electrodes and wiring. It is also suitable for electrodes and wiring of elastomer sensors such as capacitance type sensors. In addition to the power generation transducer, it is also suitable for electrodes, wiring, etc. of flexible transducers that emit light, generate heat, and color. Moreover, the electrically conductive film of this invention is useful also for the flexible wiring board etc. which are used for a wearable device etc.

  The conductive film of the present invention is excellent in flexibility and conductivity. For this reason, it can be used for members that require electrical control and flexible contact. For example, it is suitable for an electrode layer and a surface layer in a developing roll, a charging roll, a transfer roll, a paper feeding roll, a toner layer forming member, a cleaning blade, a charging blade and the like used in OA (Office Automation) equipment such as a laser beam printer.

1: Capacitance type sensor (elastomer sensor) 10: Dielectric film 11a, 11b: Electrodes 12a, 12b: Wiring 13a, 13b: Cover film 14: Connector 2: Actuator 20: Dielectric films 21a, 21b: Electrode 22: Power supply 3 : Power generation transducer 30: Dielectric films 31a, 31b: Electrode 4: Flexible wiring board 40: Base material 41: Front side wiring connector 42: Back side wiring connector 01X to 16X: Front side electrode 01X1 to 16X1: Front side connection portion 01Y to 16Y: Back side electrode 01Y1-16Y1: Back side connection part 01x-16x: Front side wiring 01y-16y: Back side wiring 100: Conductive film 101: Elastomer 102: First metal filler 103: Second metal filler

Claims (14)

An elastomer having a functional group capable of hydrogen bonding and having a glass transition temperature (Tg) of −10 ° C. or lower;
A flaky or needle-shaped first metal filler filled in the elastomer; a massive second metal filler;
Comprising
The conductive film characterized in that the first metal filler is oriented in the film development direction.   The conductive film according to claim 1, wherein the film thickness is 4 μm or more and 1000 μm or less.   The conductive film according to claim 1, wherein the conductive film is formed on a surface of an elastic member made of elastomer.   The conductive film according to claim 1, wherein the elastomer constituting the conductive film contains a plasticizer.   The conductive film according to any one of claims 1 to 4, wherein the elastomer constituting the conductive film is one or more selected from acrylic rubber, urethane rubber, and hydrin rubber.   The conductive film according to claim 5, wherein the acrylic rubber contains 50 mol% or more of an acrylate monomer unit having an alkyl group having 4 or more carbon atoms.   7. The conductive film according to claim 1, wherein the first metal filler has an average particle size of 2.5 μm to 15 μm and an aspect ratio of 5 to 25. 8.   The conductive film according to claim 1, wherein the second metal filler has an average particle size of 0.1 μm or more and 8.0 μm or less, and an aspect ratio of 1 or more and 5 or less.   The conductive film according to claim 1, wherein a filling amount of the first metal filler and the second metal filler is 300 parts by mass or more and 1500 parts by mass or less with respect to 100 parts by mass of the elastomer. .   The conductive film according to any one of claims 1 to 9, wherein a mixing ratio of the first metal filler and the second metal filler is 30: 1 to 1: 5 by mass ratio.   11. A transducer comprising the conductive film according to claim 1 as at least one of an electrode and a wiring.   A dielectric film made of an elastomer, a plurality of electrodes arranged via the dielectric film, and a wiring connected to each of the plurality of electrodes, according to a voltage applied between the plurality of electrodes The transducer according to claim 11, wherein the dielectric film is an actuator that expands and contracts.   A dielectric film made of an elastomer, a plurality of electrodes arranged through the dielectric film, and a wiring connected to each of the plurality of electrodes, and based on a change in capacitance between the plurality of electrodes The transducer according to claim 11, wherein the transducer is an elastomer sensor that detects deformation.   A flexible wiring board, wherein at least a part of the wiring is made of the conductive film according to any one of claims 1 to 10.