阅读说明：本技术 元件和用于制造元件的方法 (Component and method for producing a component ) 是由 菅原智明 名取润一郎 近藤玄章 驹井夕子 于 2020-09-30 设计创作，主要内容包括：一种元件包括一对电极,在该对电极之间的中间层,以及至少一层绝缘层。中间层含有包括未配对电子的硅化合物作为材料。中间层是可变形的。(An element includes a pair of electrodes, an intermediate layer between the pair of electrodes, and at least one insulating layer. The intermediate layer contains a silicon compound including unpaired electrons as a material. The intermediate layer is deformable.)

1. An element, comprising:

a pair of electrodes;

an intermediate layer between the pair of electrodes, the intermediate layer containing a silicon compound including unpaired electrons as a material, the intermediate layer being deformable; and

at least one insulating layer between the pair of electrodes.

2. The element according to claim 1, wherein the insulating layer has an elastic modulus of up to or higher than six times that of the intermediate layer.

3. The element according to claim 1 or 2, wherein the insulating layer comprises a resin having an aromatic ring in a straight chain or a side chain, and has an orientation.

4. The element according to any one of claims 1 to 3, wherein the intermediate layer contains particles having the unpaired electrons.

5. The element according to any one of claims 1 to 4, characterized in that the intermediate layer has at least one peak between g values of 2.04 to 1.98 when measured using an Electron Spin Resonance (ESR) spectrometer.

6. The element according to any one of claims 1 to 5, characterized in that the intermediate layer has at least one peak between g-values of 2.070 to 2.001, when measured using an Electron Spin Resonance (ESR) spectrometer at an ambient temperature of-150 ℃.

7. The element according to any one of claims 1 to 6 wherein the insulating layer has at least one peak between g values of 2.04 to 1.98 when measured using an Electron Spin Resonance (ESR) spectrometer.

8. A method for manufacturing a component, comprising:

at least one insulating layer is provided between a pair of electrodes, an intermediate layer is provided between the pair of electrodes, the intermediate layer contains a silicon compound as a material, the silicon compound includes unpaired electrons, and the intermediate layer is deformable.

9. The method for manufacturing a component according to claim 8, wherein the intermediate layer is subjected to a surface modification treatment in a state where the intermediate layer is in intimate contact with the insulating layer.

10. The method of manufacturing a component according to claim 9, wherein the intermediate layer is subjected to the surface modification treatment selected from corona discharge treatment, ultraviolet irradiation treatment and electron beam irradiation treatment.

Technical Field

The invention relates to a component and a method for producing the component.

Background

Techniques for converting vibration into electric energy for effective use have been proposed so far. Examples of the vibration include vibration of structures such as roads, bridges, buildings, and industrial machines, vibration of moving bodies such as automobiles, railway vehicles, and aircraft, vibration caused by human motion, and environmental vibration (wave and wind vibration energy) common in the environment.

Power generation methods for converting such vibration energy into electric energy are broadly classified into power generation methods using electromagnetic induction, power generation methods using piezoelectric elements, and power generation methods using electrostatic induction.

A method of using electromagnetic induction includes changing the relative positions of a coil and a magnet by vibration, and generating electricity by electromagnetic induction occurring on the coil. The method using the piezoelectric element mainly uses a ceramic piezoelectric element. This method utilizes a phenomenon that when the piezoelectric element is deformed by vibration, electric charges are induced on the surface of the piezoelectric element.

Methods using electrostatic induction typically use electret dielectrics that semi-permanently hold a charge. The relative position of the electret dielectric and the electrode located at a distance from the electret dielectric is changed by vibration or the like, whereby an electric charge is electrostatically induced on the electrode for power generation. Power generation facilities using such a principle are disclosed in, for example, japanese unexamined patent application publication No. 2017-135775 and japanese unexamined patent application publication No. 2017-126722.

In order to increase the amount of power generation of a power generation device using electrostatic induction, it is advantageous to make the dielectric thinner to increase the relative permittivity r. It is known that the power generation performance improves as the thickness of the intermediate layer decreases.

However, silicone rubber or the like used as the intermediate layer generally has extremely low tear strength as compared with resin or the like. If silicone rubber or the like is used as the intermediate layer and the intermediate layer is thinly formed to improve the power generation performance, defects may occur. This causes problems of an increased initial failure rate and low durability in the manufacturing process.

The present invention has been achieved in view of the above, and an object of the present invention is to reduce an initial failure rate in a manufacturing process and improve durability in the case where an intermediate layer having low tear strength is thinly formed.

Disclosure of Invention

According to one aspect of the present invention, an element includes a pair of electrodes, an intermediate layer between the pair of electrodes, and at least one insulating layer. The intermediate layer contains a silicon compound including unpaired electrons as a material. The intermediate layer is deformable.

An aspect of the present invention provides an effect that if an intermediate layer having low tear strength is thinly formed, the initial failure rate in the manufacturing process can be reduced and the durability can be improved.

Drawings

Fig. 1 is a diagram schematically illustrating a cross section of an element according to an embodiment;

fig. 2 is a diagram schematically showing a cross section of a modification 1 of the element;

fig. 3 is a diagram schematically showing a cross section of modification 2 of the element;

fig. 4 is a diagram schematically showing a cross section of modification 3 of the element;

fig. 5 is a diagram showing an example of a pre-bending state in the operation of the bending tester for durability evaluation; and

fig. 6 is a graph showing an example of ESR measurement of the intermediate layer.

The drawings are intended to depict example embodiments of the invention, and should not be interpreted as limiting the scope of the invention. In the various figures, the same or similar reference numerals refer to the same or similar parts.

Detailed Description

This specification describes a system for building a library of template representations that an agent (e.g., a robotic agent) may use to interact with a physical environment. More specifically, the agent may use a library of template representations to infer the location of objects of interest in the environment using template matching techniques, and then interact with these objects of interest (e.g., by picking them up using a mechanical grasping device).

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.

As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.

In describing the preferred embodiments illustrated in the drawings, specific terminology may be resorted to for the sake of clarity. However, the disclosure of this patent specification is not intended to be limited to the specific terminology so selected, and it is to be understood that each specific element includes all technical equivalents that operate in a similar manner and achieve a similar result with the same function.

Embodiments of the present invention will be described in detail below with reference to the accompanying drawings. Embodiments of an element and a method for manufacturing the element will be described in detail below with reference to the accompanying drawings.

SUMMARY

Fig. 1 is a diagram schematically showing a cross section of an element 1 according to the present embodiment. The element 1 comprises a first electrode 2, a second electrode 3, an intermediate layer 4 and an insulating layer 5. The first electrode 2 and the second electrode 3 are opposed to each other. The intermediate layer 4 is located between the first electrode 2 and the second electrode 3 and is made of rubber or a rubber composition. An insulating layer 5 is located between the intermediate layer 4 and the second electrode 3. In other words, the element 1 includes the first electrode 2 as an upper electrode, the intermediate layer 4, the insulating layer 5, and the second electrode 3 as a lower layer, which are stacked in this order from above. As shown in fig. 1, the element 1 comprises an intermediate layer 4 and an insulating layer 5 in intimate contact with each other.

The element 1 may include a first electrode 2, an insulating layer 5, an intermediate layer 4, and a second electrode 3 stacked in this order.

The element 1 also comprises suitable other components. Examples will be described below.

Fig. 2 is a diagram schematically showing a cross section of a modification 1 of the element 1.

In the modification 1 shown in fig. 2, the element 1 includes a spacer 6 interposed between the first electrode 2 and the intermediate layer 4. Although not specifically shown, the element 1 may include a spacer 6 interposed between the second electrode 3 and the insulating layer 5.

If the first electrode 2, the insulating layer 5, the intermediate layer 4 and the second electrode 3 are stacked in this order, the element 1 may include a spacer 6 between the second electrode 3 and the intermediate layer 4 or between the first electrode 2 and the insulating layer 5.

Expanded microcapsules or unexpanded pine microspheres (Matsumoto Yushi-Seiyaku Co., Ltd.) may be used as the separator 6. Alternatively, the spacer 6 may be made of silicon rubber. The configuration with the spacers 6 facilitates the separate charging of the intermediate layer 4, whereby the electrostatic effect of the element 1 can be improved.

In the initial state, which is a stable state after manufacturing, the element 1 generally has no surface charge or internal charge. If a vertical load is applied to the intermediate layer 4 from the outside, the first electrode 2, which is initially separated from the intermediate layer 4 by the separator 6, repeatedly contacts and separates to cause separation charging.

If the element 1 does not include the spacer 6 as shown in fig. 1, the element 1 can generate a voltage by the movement of the electrode when the element 1 performs a bending operation in a triboelectric charged state.

The intermediate layer 4 is given charge retention defects such as unpaired electrons by energy treatment using electron beams, ultraviolet rays, or the like. The separate charged voltages inject charge into the charge retention defects. The stored charges and the electrodes are moved by or repulsive to an external load, whereby electric power can be generated. The intermediate layer 4 may contain particles having unpaired electrons. This causes the intermediate layer 4 to have more unpaired electrons, and they are one of the charge retention mechanisms, whereby high power generation can be maintained.

The intermediate layer 4 contains a silicon compound including unpaired electrons as a material, and is thus deformable. Examples of the intermediate layer 4 may include silicone rubber, modified silicone rubber and silica powder irradiated with high energy, such as electron beam, gamma ray and ultraviolet ray. The silicone rubber, modified silicone rubber, and the like used as the intermediate layer 4 generally have extremely low tear strength as compared with a resin and the like. If silicone rubber, modified silicone rubber, or the like is used as the intermediate layer 4, and the intermediate layer 4 is thinly formed for the purpose of improving the power generation performance, defects may therefore occur. In order to solve such a problem, in the present embodiment, the insulating layer 5 is located at a position in contact with the intermediate layer 4 to reduce the initial failure rate during manufacturing and improve durability.

Fig. 3 is a diagram schematically showing a cross section of a modification 2 of the element 1.

In the variant 2 shown in fig. 3, the element 1 also comprises an insulating layer 7 stacked on the first electrode 2.

Fig. 4 is a diagram schematically showing a cross section of modification 3 of the element 1.

In the modification 3 shown in fig. 4, the element 1 further includes an insulating layer 8 stacked on the second electrode 3.

Detailed Description

First and second electrodes

The material, shape, size, and structure of the first electrode 2 and the second electrode 3 are not particularly limited and may be appropriately selected depending on the intended purpose.

The materials, shapes, sizes and structures of the first electrode 2 and the second electrode 3 may be the same or different, but are preferably the same.

Examples of the material of the first electrode 2 and the second electrode 3 may include metal, carbon-based conductive material, conductive rubber composition, conductive polymer, and oxide.

Examples of the metal may include gold, silver, copper, aluminum, stainless steel, tantalum, nickel, and phosphor bronze. Examples of the carbon-based conductive material may include carbon nanotubes, carbon fibers, and graphite. Examples of the conductive rubber composition may include a composition containing a conductive filler and a rubber. Examples of the conductive polymer may include polyethylene dioxythiophene (PEDOT), polypyrrole, and polyaniline. Examples of the oxide may include Indium Tin Oxide (ITO), indium-zinc oxide (IZO), and zinc oxide.

Examples of the conductive filler may include carbon materials (e.g., ketjen black, acetylene black, graphite, Carbon Fibers (CF), Carbon Nanofibers (CNF), Carbon Nanotubes (CNT), graphene, etc.), metal fillers (gold, silver, platinum, copper, aluminum, nickel, etc.), conductive polymer materials (any derivatives of polythiophene, polyacetylene, polyaniline, polypyrrole, polyparaphenylene, and polyparaphenylene vinylene, or those doped with a dopant represented by an anion or cation of these derivatives), and ionic liquids. These may be used alone or in combination of two or more.

Examples of the rubber may include silicone rubber, modified silicone rubber, acrylic rubber, chloroprene rubber, polysulfide rubber, polyurethane rubber, butyl rubber, fluorosilicone rubber, natural rubber, ethylene-propylene rubber, nitrile rubber, fluorine rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene-diene rubber, chlorosulfonated polyethylene rubber, polyisobutylene, and modified silicone. These may be used alone or in combination of two or more.

Examples of the shape of the first electrode 2 and the second electrode 3 may include a thin film. Examples of the structure of the first electrode 2 and the second electrode 3 may include a fabric made of a fibrous carbon material layer, a nonwoven fabric, a knitted fabric, a mesh, a sponge, and a nonwoven fabric.

The average thickness of the electrode is not particularly limited and may be appropriately selected depending on the intended purpose. The average thickness is preferably 0.01m to 1mm, more preferably 0.1m to 500m, in view of conductivity and flexibility. An average thickness of 0.01m or more provides suitable mechanical strength and improved conductivity. The average thickness of 1mm or less enables the power generation element to be deformed with good power generation performance.

Intermediate layer

The intermediate layer 4 is flexible.

The intermediate layer 4 satisfies at least one of the following conditions (1) and (2):

condition (1): when the intermediate layer 4 is pressed in a direction orthogonal to the surface of the intermediate layer 4, the amount of deformation of the intermediate layer 4 on the first electrode 2 side (one side) is different from the amount of deformation of the intermediate layer 4 on the second electrode 3 side (the other side); and

condition (2): the universal hardness (H1) when the first electrode 2 side of the intermediate layer 4 was pressed into 10m was different from the universal hardness (H2) when the second electrode 3 side of the intermediate layer 4 was pressed into 10 m.

The intermediate layer 4 can generate a large amount of electricity if both sides have different amounts of deformation or different hardnesses as described above. In the present invention, the amount of deformation refers to the maximum indentation depth of an indenter pressed against the intermediate layer 4 under the measurement conditions to be described below. The general hardness of the intermediate layer described above is merely a preferred example and is not limited to the above description.

The universal hardness was determined by the following method.

Measurement conditions

The measuring instrument is as follows: HM2000, manufactured by Fischer Instruments k.k.

Pressure head: square cone diamond pressure head with vertex angle of 136 degrees

Indentation depth: 10m

Initial load: 0.02mN

Maximum load: 100mN

Time to increase load from initial load to maximum load: 50 seconds

The ratio (H1/H2) of the universal hardness (H1) to the universal hardness (H2) is preferably 1.01 or more, more preferably 1.07 or more, and most preferably 1.13 or more.

There is no particular upper limit on the contrast ratio (H1/H2). For example, the ratio is appropriately selected according to factors such as the degree of flexibility required in the use conditions and the load in the use conditions, and is preferably 1.70 or less. H1 represents the general hardness of a relatively harder surface and H2 represents the general hardness of a relatively softer surface.

The material of the intermediate layer 4 is not particularly limited and may be appropriately selected depending on the intended purpose, and examples thereof may include rubbers and rubber compositions. Examples of the rubber may include silicone rubber, modified silicone rubber, acrylic rubber, chloroprene rubber, polysulfide rubber, polyurethane rubber, butyl rubber, fluorosilicone rubber, natural rubber, ethylene-propylene rubber, nitrile rubber, fluorine rubber, isoprene rubber, butadiene rubber, styrene-butadiene rubber, acrylonitrile-butadiene rubber, ethylene-propylene-diene rubber, chlorosulfonated polyethylene rubber, polyisobutylene, and modified silicone. These may be used alone or in combination of two or more. Among them, silicone rubber and modified silicone rubber are preferable.

The silicone rubber is not particularly limited as long as it is a rubber having a siloxane bond, and may be appropriately selected depending on the intended purpose. Examples of the silicone rubber may include dimethylsilicone rubber, methylphenylsilicone rubber, fluorosilicone rubber, and modified silicone rubber (e.g., acrylic-modified, alkyd-modified, ester-modified, and epoxy-modified silicone rubber). These may be used alone or in combination of two or more.

Examples of the rubber composition may include a composition containing a filler and a rubber. Among them, a silicone rubber composition containing silicone rubber is preferable because it has high power generation performance.

Examples of the filler may include organic fillers, inorganic fillers, and organic-inorganic composite fillers. The organic filler is not particularly limited as long as it is an organic compound, and may be appropriately selected depending on the intended purpose. Examples of the organic filler may include acrylic fine particles, polystyrene fine particles, melamine fine particles, fluorine resin fine particles such as polytetrafluoroethylene, silicone powder (silicone resin powder, silicone rubber powder and silicone composite powder), rubber powder, wood powder, pulp and starch. The inorganic filler is not particularly limited as long as it is an inorganic compound, and may be appropriately selected depending on the intended purpose.

Examples of the inorganic filler may include oxides, hydroxides, carbonates, sulfates, silicates, nitrides, carbon, metals and other compounds.

Examples of the oxide may include silica, diatomaceous earth, alumina, zinc oxide, titanium oxide, iron oxide, and magnesium oxide.

Examples of the hydroxide may include aluminum hydroxide, calcium hydroxide and magnesium hydroxide.

Examples of the carbonate may include calcium carbonate, magnesium carbonate, barium carbonate, and hydrotalcite.

Examples of the sulfate may include aluminum sulfate, calcium sulfate and barium sulfate.

Examples of the silicate may include calcium silicate (wollastonite and xonotlite), zirconium silicate, kaolin, talc, mica, zeolite, perlite, bentonite, montmorillonite, sericite, activated clay, glass and hollow glass beads.

Examples of the nitride may include aluminum nitride, silicon nitride, and boron nitride.

Examples of carbon may include ketjen black, acetylene black, graphite, carbon fiber, carbon nanofiber, carbon nanotube, fullerene (including derivatives) and graphene.

Examples of the metal may include gold, silver, platinum, copper, iron, aluminum, and nickel.

Examples of other compounds may include potassium titanate, barium titanate, strontium titanate, lead zirconate titanate, silicon carbide, and molybdenum sulfide. The inorganic filler may be surface-treated.

As the organic-inorganic composite filler, any compound of a combination of an organic compound and an inorganic compound on a molecular level may be used without particular limitation.

Examples of the organic-inorganic composite filler may include silica-acrylic composite particles and silsesquioxane.

The average particle size of the filler is not particularly limited and may be appropriately selected depending on the intended purpose. The average specific size is preferably 0.01m to 30m, more preferably 0.1m to 10 m. The average particle size of 0.01m or more can improve power generation performance. The average particle size of 30m or less may make the intermediate layer 4 deformable to improve power generation performance.

The average particle size can be measured by a known method using a known particle size distribution measuring instrument such as Microtrac HRA (manufactured by Nikkiso co., ltd.).

The filler content is preferably 0.1 to 100 parts by mass, more preferably 1 to 50 parts by mass, per 100 parts by mass of the rubber. The content of the filler of 0.1 part by mass or more can improve the productivity. The filler content of 100 parts by mass or less may deform the intermediate layer 4 to improve the power generation performance.

The other components are not particularly limited and may be appropriately selected depending on the intended purpose. Examples may include additives. The contents of the other components may be appropriately selected without impairing the object of the present invention.

Examples of the additives may include crosslinking agents, reaction control agents, fillers, reinforcing materials, anti-aging agents, conductivity control agents, colorants, plasticizers, processing aids, flame retardants, ultraviolet absorbers, tackifiers, and thixotropic agents.

The method for preparing the material constituting the intermediate layer 4 is not particularly limited and may be appropriately selected depending on the intended purpose. For example, the rubber composition can be prepared by mixing the rubber, the filler, and other components, if necessary, and kneading and dispersing the mixture.

The method for forming the intermediate layer 4 is not particularly limited and may be appropriately selected depending on the intended purpose. For example, a film of the rubber composition may be formed by: the rubber composition is applied to the substrate by blade coating, die coating, dip coating, or the like, and then cured thermally or using an electron beam.

The average thickness of the intermediate layer 4 is not particularly limited and may be appropriately selected depending on the intended purpose. In view of deformation traceability, the average thickness is preferably 1m to 10mm, more preferably 20m to 10 mm. The average thickness in the preferred range enhances the film forming ability and does not interfere with deformation, so that satisfactory power generation can be performed. The silicone rubber layer as the intermediate layer 4 according to the present embodiment has a film thickness of 20 m.

The intermediate layer 4 preferably has insulating properties. As the insulating property, the intermediate layer 4 preferably has a volume resistivity of 108 Ω · cm or more, more preferably 1010 Ω · cm or more. The intermediate layer 4 may have a multilayer structure.

The insulating layer 5 (insulating layers 7 and 8) is desirably made of a resin having an aromatic ring in its straight chain or side chain, and has an orientation. In the present embodiment, the insulating layer 5 (insulating layers 7 and 8) is made of silicone rubber. By forming the insulating layer 5 (insulating layers 7 and 8) of a resin having an aromatic structure in which charges are not easily accumulated, the discharge of charges can be suppressed.

Next, the detailed structure of the element 1 will be described.

Example 1

As shown in fig. 1, the element 1 includes a first electrode 2 and a second electrode 3 as a pair of electrodes, a deformable intermediate layer 4, and an insulating layer 5. The intermediate layer 4 is located between the first electrode 2 and the second electrode 3. The insulating layer 5 is in intimate contact with the intermediate layer 4.

The intermediate layer 4 is a rubber or rubber composition layer formed by subjecting a silicone rubber member to a surface modification treatment based on corona discharge.

The silicone rubber member for the intermediate layer 4 was made of silicone rubber (KE-106 manufactured by Shin-Etsu chemical co., ltd., two-component transparent rubber) and had a thickness of about 20 m. In other words, the intermediate layer 4 includes a silicon compound as a material.

The silicone rubber member was formed by knife coating of the material silicone rubber and high temperature sintering at 120 ℃ for 30 minutes, followed by corona discharge treatment with an applied voltage of 100V and a cumulative energy of 500J/cm 2. The result was machined into a rectangular shape of 20mm50 mm. In the absence of surface treatment, no signal from unpaired electrons was observed. The silicone rubber member including the E 'center or the iron oxide shows a signal from the E' center or the iron oxide. Peroxide bonds were also detected by low temperature measurements.

By subjecting the intermediate layer 4 to a surface modification treatment based on corona discharge in a state where the intermediate layer 4 is in close contact with the insulating layer 5, unpaired electrons are easily generated in the intermediate layer 4. This enables high power to be generated.

The intermediate layer 4 is here a rubber or rubber composition layer containing a silicon compound as material. However, this configuration is not limiting. The intermediate layer 4 may be any layer containing a silicon compound as a material and having deformability. Deformability may include flexibility and rubber elasticity. More specifically, deformability refers to the degree of deformability to which the layer can be deformed by an external force applied by the user.

The first electrode 2 is patterned to be placed on the silicon rubber member.

In the present embodiment, an aluminum-deposited 12m PET film was used as the second electrode 3. The second electrode 3 is a continuous strip-like electrode in contact with the intermediate layer 4.

Now, the treatment methods according to other examples 2 to 7 and comparative examples 1 to 7 of the element 1 to be compared with the element 1 will be described below. Description of a portion overlapping with that of embodiment 1 will be omitted as appropriate.

Example 2

A member as in example 1 was manufactured by performing radiation treatment under the following conditions using an ultraviolet irradiation lamp (VL-215. C manufactured by Vilber Lourmat) instead of the corona discharge treatment in example 1: a wavelength of 254nm, a cumulative light amount of 300J/cm2, and a nitrogen atmosphere having an oxygen partial pressure of 5000ppm or less.

Example 3

Using an electron beam radiation source (a line-emitting low-energy electron beam source manufactured by Hamamatsu Photonics k.k. instead of the corona discharge treatment in example 1, a component was manufactured by performing radiation treatment under the following conditions as in example 1: an irradiation amount of 1MGy and a nitrogen atmosphere having an oxygen partial pressure of 5000ppm or less.

Example 4

As the silicone rubber member of the intermediate layer 4, rubber (DY35-2083 manufactured by Dow Corning Toray co., ltd) was used. The rubber includes iron oxide as a material, and thus includes unpaired electrons derived from iron oxide in its structure in addition to unpaired electrons generated from the silicon compound generated by the surface treatment.

The silicone rubber of intermediate layer 4 (DY35-2083) showed an E' center derived signal, and a broad ESR spectrum with a g value of 2.5 due to the presence of iron oxide.

Example 5

Example 5 includes electrodes fixed by different methods. Embodiment 5 is an example in which the electrode pairs 2 and 3 are each partially fixed to a film. Such electrodes 2 and 3 slide on the insulator film 5 and the intermediate layer 4 when bent.

Example 6

Embodiment 6 is an example using silicon rubber as the insulating layer 5. More specifically, KE-1950-70 was used as the silicone rubber of the insulating layer 5. The silicone rubber was diluted with 30% by weight toluene and applied to the aluminum deposited PET surface. The thickness was 20 m.

Example 7

Embodiment 7 is an example using silicon rubber as the insulating layer 5. More specifically, KE-1950-60 was used as the silicone rubber of the insulating layer 5. The silicone rubber was diluted with 30% by weight toluene and applied to the aluminum deposited PET surface. The thickness was 20 m.

Comparative example 1

Unlike example 1, comparative example 1 includes an aluminum layer in contact with the silicone rubber of the intermediate layer 4.

Comparative example 2

Unlike example 2, comparative example 2 includes an aluminum layer in contact with the silicone rubber of the intermediate layer 4.

Comparative example 3

Unlike example 3, comparative example 3 includes an aluminum layer in contact with the silicone rubber of the intermediate layer 4.

Comparative example 4

Unlike example 4, comparative example 4 includes an aluminum layer in contact with the silicone rubber of the intermediate layer 4.

Comparative example 5

Unlike example 5, comparative example 5 includes an aluminum layer in contact with the silicone rubber of the intermediate layer 4.

Comparative example 6

Unlike example 3, comparative example 6 includes an insulating layer 5 made of polyethylene. The polyethylene does not have any aromatic hydrocarbons in its linear chain.

Comparative example 7

Unlike examples 6 and 7, comparative example 7 includes an insulator layer 5 made of KE-1950-50 as a silicone rubber.

Table 1 shows the results obtained by performing the evaluation described below on each of the elements 1 manufactured as described above. For "evaluation 1: initial failure rate ", the results listed in table 1 show only one failure in example 1 among examples 1 to 7. There were many failures in all the test pieces of comparative examples 2 to 7.

For "evaluation 2: durability performance "all examples 1 to 7 passed 10000 rounds of testing. None of the test pieces of comparative examples 2 to 7 passed 10000 rounds of the test.

For "evaluation 4: rubber elasticity property "the elastic modulus is 5.4 or more, initial failure does not occur, and the durability property is high. By making the insulating layer have an elastic modulus as high as or higher than 6 times that of the intermediate layer, cracking can be prevented.

For the evaluation shown in table 1, an element 1 having the configuration shown in fig. 1 was manufactured by applying a 20m silicone rubber layer onto the PET surface of 210297mm (a4) aluminum deposited PET film, sintering the resulting film for surface modification, and placing a 210297mm (a4) aluminum deposited PET film on the silicone rubber.

(evaluation 1): initial failure rate

With respect to the intermediate layer 4 (e.g., silicone rubber), the initial failure rate indicates the failure rate in the surface treatment and the electrode material. With respect to the insulating layer 5 (silicone rubber), the initial failure rate indicates the failure rate under the surface treatment condition. The initial failure rate indicates an initial rate of occurrence of a short circuit between the upper electrode and the lower electrode. The total number of samples was 50.

(evaluation 2): bending durability performance

Fig. 5 is a diagram showing an example of a pre-bending state in the operation of the bending tester for durability evaluation. As shown in fig. 5, in order to measure the bending durability performance of the element 1 formed in a cell shape, a 90 ° bending test was performed by using a mesa durability tester TCDM111LH (manufactured by Yuasa systems limited).

10 samples of element 1 were stacked between R30 clamps and connected in series. The samples were subjected to 10000 rounds of durability testing with 10 cycles per minute and p-p voltage values were measured. The samples were made into vertically long films.

The number of times the p-p voltage value decreases by 10% from the initial value is recorded in the number field.

(evaluation 3): electron Spin Resonance (ESR) measurement

Fig. 6 is a graph showing an example of ESR measurement of the intermediate layer 4. A material evaluation test was performed on the intermediate layer 4 by using a silicone rubber layer electron spin resonance spectrometer ESR (manufactured by JOEL ltd). In fig. 6, the broken line represents the measured T1 in the case where the ambient temperature is room temperature, and the solid line represents the measured T2 in the case where the ambient temperature is-150 ℃.

Electron spin resonance is typically shown in g-values as a function of the magnetic field strength on the horizontal axis and the waveform of the first derivative of the absorption spectrum on the vertical axis. The g value is a value inherent to each ESR signal, and is determined by the frequency (v) of the microwave applied to the sample and the intensity (H) of the resonance magnetic field. The ESR signal and lattice defects were identified by using the g value.

The ESR signal is used to observe a resonance phenomenon due to absorption of microwaves (electromagnetic waves having a frequency of about 9.4GHz and about 3cm: X band) caused by spin transition of unpaired electrons. Detection of the ESR signal means that unpaired electrons are present in the sample. In other words, the detection of a peak in the measurement waveform having a g value on the horizontal axis means the detection of unpaired electrons.

Fig. 6 shows the ESR signal of the intermediate layer 4 described in example 3.

How to read fig. 6 will be described in more detail. Isotropic materials are known to exhibit ESR signal strength that is substantially symmetric about the inversion point. In contrast, the waveforms T1 and T2 shown in fig. 6 are asymmetric about the inversion point Q. This indicates that the intermediate layer 4 has an anisotropic structure.

Shown as peak g of ESR signals measured at T1 and T2_AAnd g_BIn full agreement with the measurements of E 'center g | (═ 2.0014) and E' center g | (═ 2.0004) obtained from defects in the quartz glass.

This agreement is considered to indicate that the surface treatment causes defects of oxygen O in the silicone rubber, and that unpaired electrons are present at the defect sites.

The detection of two peaks at the center g | of E' in a typical quartz glass structure indicates that there is anisotropy in the depth direction of the sample, i.e., in the thickness direction of the intermediate layer 4.

Therefore, measurement T1 of intermediate layer 4 according to the present embodiment has two peaks between the g values of 2.004 and 1.998, which are considered to indicate that anisotropy exists in the thickness direction of intermediate layer 4.

Measurement T2 shows a peak g of the ESR signal between g values of 2.070 and 2.001_C。

Typically, low temperature measurements at-150 ℃ reduce the effects of thermal movement and relaxation time of electrons. This increases the sensitivity of the ESR signal and makes it difficult to observe the measurement of the ESR signal in a room temperature environment.

Peak g in measurement T2 not detected in measurement T1_CAre believed to represent peroxide radicals.

In other words, according to the intermediate layer 4 of the present embodiment, "there is at least one peak between g values of 2.04 to 1.98 when measured by using an electron spin resonance spectrometer". This signal is manifested by unpaired electrons that are particularly likely to retain charge, and can sustain a large amount of power generation.

Similarly to the intermediate layer 4, the insulating layer 5 also "has at least one peak between g values of 2.04 to 1.98" when measured by using an electron spin resonance spectrometer. This signal is manifested by unpaired electrons that are particularly likely to retain charge, and can sustain a large amount of power generation.

It is evident from the measurement T2 that the intermediate layer 4 "according to this example has at least one peak between g values of 2.070 to 2.001" when measured using an electron spin resonance spectrometer at-150 ℃. This signal is manifested by unpaired electrons that are particularly likely to retain charge, and can sustain a large amount of power generation.

Based on the foregoing measurements, the samples in table 1 that showed as many or more than 80% negative peaks as the spectrum of measurement T2 according to example 3 were labeled with a, around 30% with B, and no peak with C.

The same measurements were again made on the samples of example 3 at least six months after the surface modification treatment and were found to show similar spectra. That is, the unpaired electronic structure according to the present invention is stably held in the intermediate layer 4.

Table 2 shows measurement of ESR signals when surface-treating silicone rubber and PET by corona discharge, ultraviolet irradiation and electron beam irradiation.

TABLE 2

The measurement samples listed are formed by forming the intermediate layer 4 on the second electrode 3 and then performing a corresponding surface treatment. The measurement sample is obtained by releasing the respective intermediate layer 4. The PET part of the second electrode 3 remaining after releasing the intermediate layer 4 was used as a measurement sample, in which aluminum was dissolved out from the intermediate layer 4 with dilute hydrochloric acid.

ESR signals are classified as follows:

none: indistinguishable from background noise;

tracking: there is a significant signal but difficult to quantify compared to background noise;

low: a clearly quantifiable signal; and

high: there is a signal that is one or more digits higher than the low signal.

(evaluation 4): elastic property of rubber

The rubber elasticity properties of the element 1 were measured by using an instrument described below. Rubber elasticity refers to the entropy elasticity exhibited by a polymer that includes crosslinking points.

First, method 1 for evaluating the elastic modulus will be described.

Method for evaluating elastic modulus 1

The rubber elasticity evaluation test was conducted by using a compression tester (Strograp VE5D (manufactured by Toyo Seiki Seisaku-sho Co., Ltd.)) under the following conditions:

the load range is as follows: 50N;

the load range is as follows: 100, respectively;

testing speed: 500 mm/min;

chuck distance: 60 mm;

measuring the temperature: room temperature @ B3-110

Sample preparation: punching with a No. 6 dumbbell-shaped cutter, wherein the width is 4 mm; and

specification length: 20mm

Next, method 2 for evaluating the elastic modulus will be described.

Method for evaluating elastic modulus 2

The rubber elasticity evaluation test was performed by considering the poisson's ratio of the indenter and the poisson's ratio of the material based on the Martens hardness (ISO 14577). Specifically, the intermediate layer 4 having a thickness of 100m or less was measured by the technique for evaluating an elastic modulus according to method 2.

As described above, according to the present embodiment, at least one insulating layer 5 is located between the pair of electrodes 2 and 3 of the element 1. Even if the intermediate layer 4 having a low tear strength is thinly formed for the purpose such as improved power generation performance, providing the insulator layer 5 in contact with the intermediate layer 4 can reduce the initial failure rate during manufacturing and improve durability.

Since a thinner dielectric can be manufactured, a small-sized high-output power generation device can be provided by caulking a large number of dielectrics.

Although the preferred embodiments of the present invention have been described, the present invention is not limited to such specific embodiments. Unless otherwise indicated in the foregoing description, various modifications and changes may be made without departing from the spirit of the invention as set forth in the claims.

For example, the element described in the foregoing embodiment is not limited to the power generating element, but may be used as a sensor as a detecting element for detecting contact in the form of an electric signal. The element may also be used as other element for converting an external force into electrical energy.

The effects described in the embodiments of the present invention are merely examples of some of the most suitable effects of the present invention. Therefore, the effects of the present invention are not limited to the effects described in the embodiments of the present invention.

The above examples are illustrative and not limiting of the invention. Accordingly, many additional modifications and variations are possible in light of the above teaching. For example, at least one element of the various illustrative and exemplary embodiments herein may be combined with or substituted for one another within the scope of this disclosure and the appended claims. Further, features of the components of the embodiments, such as the number, position, and shape, are not limited to the embodiments, and thus may be preferably provided. It is, therefore, to be understood that within the scope of the appended claims, the disclosure of the present invention may be practiced otherwise than as specifically described herein.

Unless specifically identified as a performance order or clearly by context, the method steps, processes, or operations described herein are not to be construed as necessarily requiring their performance in the particular order discussed or illustrated. It should also be understood that additional or alternative steps may be employed.