WO2021020427A1 - Film de conversion d'énergie, élément de conversion d'énergie et procédé de production d'un film de conversion d'énergie - Google Patents

Film de conversion d'énergie, élément de conversion d'énergie et procédé de production d'un film de conversion d'énergie Download PDF

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WO2021020427A1
WO2021020427A1 PCT/JP2020/028997 JP2020028997W WO2021020427A1 WO 2021020427 A1 WO2021020427 A1 WO 2021020427A1 JP 2020028997 W JP2020028997 W JP 2020028997W WO 2021020427 A1 WO2021020427 A1 WO 2021020427A1
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Prior art keywords
energy conversion
film
porous resin
treatment
conversion film
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PCT/JP2020/028997
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English (en)
Japanese (ja)
Inventor
小池　弘
亮太 遠山
祐太郎 菅俣
誠一郎 飯田
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株式会社ユポ・コーポレーション
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Priority to JP2021535379A priority Critical patent/JP7203979B2/ja
Publication of WO2021020427A1 publication Critical patent/WO2021020427A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/32—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed at least two layers being foamed and next to each other
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof

Definitions

  • the present invention relates to an energy conversion film, an energy conversion element, and a method for manufacturing an energy conversion film.
  • a porous resin film having piezoelectricity has been used as an energy conversion film that converts mechanical energy into electrical energy.
  • a dielectric film in which a plastic film having air bubbles inside is pulled two-dimensionally and the surface thereof is coated with a conductive layer is applied to a microphone or the like (see Patent Document 1).
  • an anchor agent may be applied after the surface of the porous resin film is oxidized.
  • a method of providing electrodes on the porous resin film without using adhesives, anchors, etc. is studied. It had been. However, it has been difficult to maintain high adhesion between the electrode, which is usually made of metal, and the resin film for a long period of time.
  • An object of the present invention is to suppress a decrease in adhesion between an electrode and a porous resin film over time.
  • the present invention has been completed by finding that the above problems can be solved. That is, the present invention is as follows.
  • An energy conversion film which is a porous resin film and whose at least one surface satisfies the following formulas (1) and (2).
  • (1) 0.8 ⁇ S1 / S0 ⁇ 1.0 (2) 2.0 ⁇ S0
  • S0 represents the oxygen atom concentration (atm%) before the cleaning treatment (A) is performed.
  • S1 represents the oxygen atom concentration (atm%) after the cleaning treatment (A) is performed.
  • the oxygen atom concentration is the ratio of the number of oxygen atoms to the total number of oxygen atoms, carbon atoms and nitrogen atoms measured by XPS (X-ray electron photospectroscopy) (oxygen atom number / (oxygen atom number + carbon atom number +). The number of nitrogen atoms)).
  • the cleaning treatment (A) refers to a cleaning treatment with distilled water.
  • the porous resin film contains a polyolefin resin.
  • the porous resin film has 100 holes / mm 2 or more having a height in the thickness direction of 3 to 30 ⁇ m and a diameter in the plane direction of 50 to 500 ⁇ m.
  • the energy conversion film according to the above [1] or [2].
  • the porous resin film has a multilayer structure including at least one porous resin layer, and the surface of the outermost layer satisfies the above formulas (1) and (2).
  • the energy conversion film according to any one of the above [1] to [3].
  • S0 represents the oxygen atom concentration (atm%) before the cleaning treatment (A) is performed.
  • S1 represents the oxygen atom concentration (atm%) after the cleaning treatment (A) is performed.
  • the oxygen atom concentration is the ratio of the number of oxygen atoms to the total number of oxygen atoms, carbon atoms and nitrogen atoms measured by XPS (X-ray electron photospectroscopy) (oxygen atom number / (oxygen atom number + carbon atom number +). The number of nitrogen atoms)).
  • the cleaning treatment (A) refers to a cleaning treatment with distilled water. ]
  • the oxidation treatment is a dielectric barrier discharge treatment.
  • the washing treatment (B) includes a treatment of washing with water or an aqueous solution having a pH of 5 to 11.
  • the energy conversion film, the energy conversion element, and the method for producing the energy conversion film of the present invention will be described in detail, but the description of the constituent requirements described below is an example (typical example) as one embodiment of the present invention. Yes, it is not specified in these contents. Further, the dimensional ratio of the drawings is not limited to the ratio shown.
  • (meth) acrylic indicates both acrylic and methacrylic.
  • the energy conversion film of the present invention is a porous resin film, and at least one surface satisfies the following formulas (1) and (2).
  • (1) 0.8 ⁇ S1 / S0 ⁇ 1.0 (2) 2.0 ⁇ S0
  • S0 represents the oxygen atom concentration (atm%) before the cleaning treatment (A) is performed.
  • S1 represents the oxygen atom concentration (atm%) after the cleaning treatment (A) is performed.
  • the oxygen atom concentration is the ratio of the number of oxygen atoms to the total number of oxygen atoms, carbon atoms and nitrogen atoms measured by X-ray Photoelectron Spectroscopy (XPS) (oxygen atom number / (oxygen atom number /). Number + number of carbon atoms + number of nitrogen atoms)).
  • the cleaning treatment (A) refers to a cleaning treatment with distilled water. ]
  • the oxygen atom concentrations S0 and S1 measured by the XPS can be obtained from the ratio of the values obtained by multiplying the respective peak intensity areas of O1s, C1s and the like by the relative sensitivity of each peak. (See, for example, Yoshito Ikada, "Basics and Applications of Polymer Surfaces (1),” Kagaku-Dojin, 1986, Chapter 4).
  • the surface satisfying the formula (2) has a high oxygen atom concentration and high adhesion to the electrode. Further, the surface satisfying the formula (1) has a small change rate of oxygen atom concentration of 0.8 or more and 1.0 or less before and after the cleaning treatment (A), that is, exists on the surface of the porous resin film, and is present on the surface. The amount of the low molecular weight acidic compound that is not bound is small, and high adhesion to the electrode described later is maintained. Therefore, it is possible to provide an energy conversion film that suppresses a decrease in the adhesion between the porous resin film and the electrode with time and exhibits stable energy conversion performance for a long period of time.
  • the "cleaning treatment (A)” is an operation for measuring the amount of oxygen atom-containing foreign matter present on the surface of the porous resin film.
  • the "distilled water” used in the cleaning treatment (A) is water having a conductivity of 1.0 ⁇ S / cm or less at 25 ° C. and containing almost no impurities. Examples of the production method include a method of distilling ion-exchanged water with a distiller, and distillation may be repeated a plurality of times in order to increase the purity.
  • distilled water a commercially available product can be used, and examples thereof include distilled water for injection of Otsuka (trade name, Otsuka Pharmaceutical Co., Ltd.), distilled water (trade name, Wako Pure Chemical Industries, Ltd.) and the like.
  • the surfaces satisfying the formulas (1) and (2) can be formed by subjecting the film surface to an oxidation treatment and then a cleaning treatment (B) in the manufacturing process of the porous resin film.
  • the "cleaning treatment (B)” is a treatment in the manufacturing process of the porous resin film, and is different from the above-mentioned “cleaning treatment (A)". The details will be described later.
  • the adhesion to the electrode on the film surface is enhanced by the oxidation treatment, and the electrode can be provided on the porous resin film without the adhesive layer, the anchor layer, etc. It was found that the adhesion decreased with the passage of time.
  • the present inventors consider that foreign substances such as low molecular weight acidic compounds produced by the oxidation treatment intervene between the film surface and the electrode to reduce the adhesion, and the oxidation treatment is performed. After that, it was found that the adhesion between the porous resin film and the electrode can be maintained for a long period of time by further performing the cleaning treatment (B) to remove the foreign matter. It can be evaluated that the smaller the ratio of oxygen atom concentration (S1 / S0) before and after the cleaning treatment (A), the larger the ratio of foreign substances generated in the oxidation treatment.
  • the energy conversion film of the present invention is a porous resin film having a large number of pores inside.
  • An energy conversion film having an electro-mechanical energy conversion performance can be obtained by subjecting the porous resin film to an electretization treatment in which an electric charge is injected.
  • the electrical-mechanical energy conversion performance includes not only the ability to convert mechanical energy (kinetic energy) into electrical energy, but also the ability to convert electrical energy into mechanical energy (kinetic energy).
  • the energy conversion film of the present invention may be a porous resin film before the electretization treatment or a porous resin film after the electretization treatment.
  • the porous resin film after the electretization treatment is a film into which charges are intentionally injected, and has a large amount of electric charges as compared with those before the electretization treatment.
  • the porous resin film according to the present invention is a layer containing at least one porous resin layer, and the porous resin layer is obtained by film-molding a resin composition containing a thermoplastic resin.
  • the porous resin film may have a single-layer structure containing only the porous resin layer described below, or may have a multilayer structure having at least one of the porous resin layers. In the case of a single-layer structure, at least one of the surfaces on both sides of the porous resin layer satisfies the formulas (1) and (2). In the case of a multi-layer structure, the surface of at least one of the outermost layers on both sides satisfies the formulas (1) and (2).
  • the porous resin film is preferably a stretched film further containing a pore-forming agent because it is easy to form the desired pores.
  • the shape and size of the pores in the porous resin film may be appropriately set according to the required performance and the like, and are not particularly limited. It is considered that different charges are held in pairs on the opposite inner surfaces of the individual pores inside the porous resin film, as in the case of a single-plate capacitor. Therefore, in order to accumulate electric charges inside like a single plate type capacitor, it is preferable that the pores of the porous resin film have an area and a height of a certain value or more. If the area of the pores is a certain amount or more, a sufficient capacitance can be obtained and an electret having excellent performance can be easily obtained.
  • the "area” of the pores means the maximum value of the pore area in the cross section parallel to the surface of the porous resin layer.
  • the “height” of the pores means the maximum value of the pore diameter in the thickness direction of the porous resin layer. From these points, it can be said that the larger the size (area) of the individual pores inside the porous resin film, the more effective the function, but the discharge (short circuit) generated by the communication between the adjacent pores is reduced and accumulated. From the viewpoint of increasing the electric charge, the size of the pores is preferably not more than a certain value. Further, when the height (distance) of the pores is equal to or less than a certain value, the electric charge is easily polarized and an electret having excellent charge stability is easily obtained.
  • the porous resin film preferably has a specific amount of pores of a specific size effective for accumulating electric charges.
  • the height of the film in the thickness direction is 3 to 30 ⁇ m
  • the diameter of the film in the surface direction is 50 to 50. It is preferable to have 100 / mm 2 or more of pores having a size of 500 ⁇ m, more preferably 150 / mm 2 or more, further preferably 200 / mm 2 or more, and particularly preferably 300 / mm 2 or more.
  • the porous resin film has a height of 3 to 30 ⁇ m in the thickness direction of the film and a diameter of the film in the surface direction.
  • pores is 50 ⁇ 500 [mu] m, preferably has 3,000 / mm 2 or less, and more preferably has 2,500 / mm 2 or less, further preferably has 2,000 / mm 2 or less, It is particularly preferable to have 1,500 pieces / mm 2 or less.
  • the charge storage capacity tends to improve and the energy conversion efficiency tends to improve.
  • the number of holes of the specific size is smaller, it is possible to prevent the adjacent holes from communicating with each other and causing a discharge (short circuit) between the adjacent holes.
  • Insufficient compression recovery of the porous resin film causes adverse effects such as a decrease in the restoration rate while the film is repeatedly compressed and restored. Therefore, when a porous resin film, that is, an energy conversion film is used as an energy conversion element such as a piezoelectric element, the product life may be shortened. In consideration of these balances, it is preferable to adjust the size of the pores in the porous resin film within the above range.
  • the porosity of the porous resin film may be appropriately set according to the required performance and the like, and is not particularly limited, but is preferably 20 to 80%. Such a vacancy rate correlates with the number of valid vacancy described above.
  • the porosity of the porous resin film means the ratio (volume fraction) of the volume occupied by the pores in the film to the total volume of the film.
  • the pore ratio of the porous resin film is equal to the ratio of the area occupied by the pores (area ratio) in the cross section of the film in the thickness direction on the premise that the pores are uniformly distributed throughout the film.
  • the porosity of the porous resin film in the present invention is calculated by observing the cross section of the material in the thickness direction with a scanning electron microscope, capturing the observation image into an image analyzer, and analyzing the observation area. It can be obtained as the area ratio of the pores on the cross section.
  • a sample for cross-section observation is prepared from the porous resin film by a method such as a gallium focused ion beam so that the pores are not crushed. The cross-sectional observation of this sample is performed at an appropriate magnification (for example, 2000 times, etc.) using a scanning electron microscope (manufactured by JEOL Ltd., trade name: JSM-6490) or the like.
  • the ratio (area ratio) of the area occupied by the pores in the sample cross section was calculated. This can be used as the porosity.
  • the porosity of the porous resin film is preferably 20% or more, preferably 25% or more, from the viewpoint of ensuring the charge storage capacity by providing a large number of pores having a size suitable for accumulating charges inside the film. % Or more, more preferably 30% or more, and particularly preferably 35% or more.
  • the pore ratio of the porous resin film is determined. It is preferably 80% or less, more preferably 70% or less, further preferably 60% or less, and particularly preferably 55% or less.
  • the porous resin layer contains a thermoplastic resin, but it is preferable to contain a pore-forming agent from the viewpoint of pore-forming property, and from the viewpoint of improving chargeability and heat resistance. , It is preferable to contain metal soap.
  • Thermoplastic resin is a matrix resin having a porous resin layer, and imparts a piezoelectric effect and compression recovery.
  • an insulating polymer material that does not easily conduct electricity can be preferably used.
  • thermoplastic resins examples include polyolefin resins such as polyethylene resins, polypropylene resins, polybutenes, and 4-methyl-1-pentene (co) polymers; Ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, metal salt (ionomer) of ethylene- (meth) acrylic acid copolymer, ethylene- (meth) acrylic acid alkyl ester copolymer (alkyl) The number of carbon atoms in the group is preferably 1 to 8), a functional group-containing olefin resin such as maleic acid-modified polyethylene or maleic acid-modified polypropylene; Polyester-based resins such as aromatic polyesters (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.) or aliphatic polyesters (polybutylene succinate, polylactic acid, etc.); Polyamide-based resins such as nylon-6, nylon-6,6,
  • polyethylene resin examples include low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, low crystalline or amorphous ethylene / ⁇ -olefin copolymer, or ethylene-cyclic olefin copolymer. Coalescence and the like can be mentioned.
  • polypropylene-based resins include crystalline polypropylene, low-crystalline polypropylene, amorphous polypropylene, propylene / ethylene copolymer (random copolymer or block copolymer), propylene / ⁇ -olefin copolymer, or propylene. -Ethylene / ⁇ -olefin copolymer, etc.) and the like.
  • the ⁇ -olefin is not particularly limited as long as it can be copolymerized with ethylene and propylene.
  • ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1 -Heptene, 1-octene, etc. can be mentioned.
  • thermoplastic resins polyolefin-based resins or functional group-containing olefin-based resins having excellent insulating properties and processability are preferable.
  • thermoplastic resin one type may be selected from the above-mentioned thermoplastic resins and used alone, or two or more types may be selected and used in combination.
  • polypropylene resins are particularly preferable from the viewpoints of insulation, processability, water resistance, chemical resistance, cost and the like.
  • the polypropylene-based resin preferably contains a resin having a melting point lower than that of the propylene homopolymer in an amount of 2 to 25% by mass based on the total amount of the thermoplastic resin.
  • a resin having a low melting point include polyethylene-based resins, and among them, high-density, medium-density, or low-density polyethylene is preferable.
  • the content (content rate) of the thermoplastic resin in the porous resin layer is not particularly limited, and for example, as a matrix resin of the porous resin layer, communication between the pores is formed while forming a sufficient pore interface in the same layer. It may be appropriately set from the viewpoint of suppressing the above and ensuring the mechanical strength of the porous resin film.
  • the thermoplastic resin is preferably contained in an amount of 50% by mass or more, more preferably 60% by mass or more, further preferably 65% by mass or more, and 70% by mass. It is particularly preferable to contain more than mass%.
  • the thermoplastic resin is preferably contained in an amount of 98% by mass or less, more preferably 97% by mass or less, further preferably 96% by mass or less, and particularly preferably 85% by mass or less.
  • Pore-forming agent examples include a foaming agent and a filler, and examples of the filler include an inorganic filler and an organic filler.
  • a foaming agent for example, a resin composition containing a thermoplastic resin constituting a porous resin layer and a pyrolytic foaming agent is melt-kneaded, and then extruded into a film to be foamable.
  • a porous resin layer can be obtained by obtaining a resin film and heating it to a temperature equal to or higher than the decomposition temperature of a thermally decomposable foaming agent to foam it.
  • a filler When a filler is used as the pore-forming agent, stretching of the film (layer) containing the filler facilitates the formation of a large number of pores inside the film with the filler as the starting point (nucleus). It is possible to control the size or frequency of the pores by controlling the content or stretching conditions of the filler, and the size (height) of the pores by controlling the particle size or stretching conditions of the filler. And diameter) can be controlled. Further, since the filler can function as a support in the pores even after the pores are formed, the pores are not easily crushed. In the obtained electret, sufficient compression recovery is likely to be exhibited even if a compressive force is repeatedly applied, and further stabilization of piezoelectric performance (pillar effect) can be expected.
  • the content of the filler in the porous resin layer is preferably 2% by mass or more, more preferably 4% by mass or more, further preferably 10% by mass or more, and 14% by mass from the viewpoint of forming sufficient pores. % Or more is particularly preferable.
  • the content is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, 25. Mass% or less is particularly preferable.
  • the content of the filler is equal to or higher than the lower limit of the above-mentioned preferable range, it is easy to obtain pores of a size suitable for accumulating a sufficient number of charges in the stretching step described later, and desired piezoelectric performance can be obtained. Easy to get.
  • the content of the filler is not more than the upper limit of the above-mentioned preferable range, the decrease in film strength due to excessive pore formation is likely to be suppressed. In the obtained energy conversion film, sufficient compression recovery is likely to be exhibited even if a compressive force is repeatedly applied, and it can be expected that the piezoelectric performance will be stable.
  • the foaming agent can be used alone, the inorganic filler can be used alone, the organic filler can be used alone, or a combination of two or more of the foaming agent, the inorganic filler, and the organic filler can be used.
  • the content ratio of each is not particularly limited.
  • the content ratio of the inorganic filler can be 10 to 99% by mass, 20 to 90% by mass, or 30 to 80% by mass with respect to the total amount of the pore forming agent. Good.
  • Foaming Agent examples include thermal decomposition type foaming agents as described above. Specifically, for example, azodicarbonamide, benzenesulfonylhydrazide, dinitrosopentamethylenetetramine, toluenesulfonylhydrazide, 4,4- Examples thereof include oxybis (benzenesulfonyl hydrazide).
  • the content of the foaming agent in the porous resin layer is preferably 1% by mass or more, more preferably 3% by mass or more, still more preferably 5% by mass or more, from the viewpoint of forming sufficient pores.
  • the content is preferably 25% by mass or less, more preferably 20% by mass or less, and further preferably 15% by mass or less.
  • the inorganic filler is preferable because a large number of products having different particle sizes are commercially available at low cost.
  • the inorganic fillers include heavy calcium carbonate, light calcium carbonate, calcined clay, silica, diatomaceous earth, white clay, talc, titanium oxide, barium sulfate, alumina, zeolite, mica, sericite, bentonite, etc. Examples thereof include sepiolite, vermiculite, dolomite, wallastonite, glass fiber and the like, but the present invention is not particularly limited thereto.
  • heavy calcium carbonate, light calcium carbonate or titanium oxide is preferable, and heavy calcium carbonate is more preferable, from the viewpoint of pore forming property and cost.
  • These inorganic fillers can be used alone or in combination of two or more.
  • Organic Filler is available as spherical particles having a uniform particle size, and the pores formed in the porous resin layer also tend to have a uniform size and shape.
  • the organic filler it is preferable to select resin particles of a type different from that of the thermoplastic resin which is the main component of the porous resin layer.
  • the thermoplastic resin is a polyolefin-based resin
  • preferable organic fillers include resin particles that are incompatible with polyolefin and do not have fluidity during kneading and stretching molding of the polyolefin-based resin.
  • Specific examples thereof include crosslinked acrylic resin, crosslinked methacrylic resin, crosslinked styrene resin, and crosslinked urethane resin, but the present invention is not particularly limited thereto.
  • the resin particles made of these crosslinked resins are available as spherical particles having a uniform particle size in advance, and are particularly preferably used because the size of the pores can be easily adjusted.
  • the organic filler is incompatible with the thermoplastic resin, which is the main component of the porous resin layer, but is melt-kneaded together with the thermoplastic resin to form a sea-island structure, and the organic filler, which is an island, is empty during stretch molding. It may become the core of the hole and form the desired hole.
  • the thermoplastic resin is a polyolefin resin
  • specific examples of such an organic filler include polyethylene terephthalate, polybutylene terephthalate, polycarbonate, nylon-6, nylon-6,6, cyclic olefin polymer, and polystyrene.
  • a polymer such as polymethacrylate, which has a melting point higher than the melting point of the polyolefin resin (for example, 170 to 300 ° C.) or a glass transition temperature (for example, 170 to 280 ° C.) and is a matrix resin by melt-kneading.
  • a polymer such as polymethacrylate, which has a melting point higher than the melting point of the polyolefin resin (for example, 170 to 300 ° C.) or a glass transition temperature (for example, 170 to 280 ° C.) and is a matrix resin by melt-kneading.
  • examples thereof include resin particles that can be finely dispersed in the based resin.
  • the organic filler may be used alone or in combination of two or more.
  • the volume average particle size of the inorganic filler or organic filler (median diameter (D 50 ) measured by a particle size distribution meter by laser diffraction) is appropriately selected in consideration of forming pores of a size suitable for accumulating electric charges.
  • the volume average particle size of the inorganic filler is preferably 3 ⁇ m or more, more preferably 4 ⁇ m or more, and 5 ⁇ m or more. It is more preferable to have.
  • the volume average particle size of the inorganic filler is preferably 30 ⁇ m or less, more preferably 20 ⁇ m or less, and further preferably 15 ⁇ m or less.
  • the inorganic filler and the organic filler When the inorganic filler and the organic filler are used in combination, the inorganic filler and the organic filler having individual particle sizes within the same volume average particle size may be used in combination, or the inorganic filler and the organic filler are mixed. Those having the same volume average particle size as the state measured by a particle size distribution meter by laser diffraction may be used.
  • the porous resin layer preferably contains a metal soap from the viewpoint of further enhancing the charge retention performance of the energy conversion film and suppressing the deterioration of the piezoelectric performance even when stored or used in a high temperature environment.
  • the metal soap used in the present invention the metal soap which is melted and uniformly dispersed in the thermoplastic resin at the kneading stage of the raw material and which is solid at the environmental temperature after the formation of the porous resin layer has high charge retention performance. Easy to exert and preferable. Therefore, assuming that the melting point of the thermoplastic resin is Tm (° C.), the melting point of the metal soap is preferably in the range of 50 to (Tm + 50) ° C., and more preferably in the range of 70 to (Tm + 40) ° C. It is preferably in the range of 100 to (Tm + 30) ° C., more preferably in the range of 100 to (Tm + 30) ° C.
  • thermoplastic resin when a polypropylene resin (melting point 160 to 170 ° C.) is used as the thermoplastic resin, it is preferable to use a metal soap having a melting point of 50 to 220 ° C., and it is preferable to use a metal soap having a melting point of 70 to 210 ° C. It is more preferable to use a metal soap having a melting point of 100 to 200 ° C.
  • the metal soap Since the metal soap has a melting point in the above temperature range, it melts and uniformly disperses in the thermoplastic resin during layer molding of the porous resin layer, and maintains its dispersed state in the thermoplastic resin after layer molding. It solidifies as it is and becomes difficult to flow. At the time of electretization treatment, the metal soap is oriented by the dipoles in the molecule, and it is presumed that the orientation of the metal soap enhances the charge retention performance.
  • the metal soap is preferably a metal salt of a fatty acid, and more preferably a metal salt of a higher fatty acid.
  • fatty acids include saturated fatty acids, unsaturated fatty acids and structural isomers thereof.
  • the number of carbon atoms per fatty acid molecule is usually 5 to 30, preferably 6 to 28 carbon atoms, more preferably 8 to 24 carbon atoms, and further preferably 10 to 20 carbon atoms.
  • metal salts of saturated fatty acids are preferable because they tend to have a high melting point and a porous resin film having excellent heat resistance.
  • the metal element of the metal soap is not particularly limited as long as it is a metal that forms a stable salt with a fatty acid.
  • sodium (Group 1), magnesium (Group 2), calcium (Group 2), barium (Group 2), zinc (Group 12) and aluminum (Group 12) At least one of Group 13) is more preferred.
  • at least one of calcium, zinc and aluminum is particularly preferable from the viewpoint of safety, calcium or aluminum is particularly preferable, and aluminum is most preferable from the viewpoint of further enhancing the charge retention performance.
  • the metal soap may be a basic salt.
  • the most preferably used metal soap is a saturated higher fatty acid aluminum salt.
  • the saturated higher fatty acid aluminum salt include dihydroxyaluminum octadecanoate, hydroxyaluminum dioctadecanoate, aluminum trioctadecanoate, dihydroxyaluminum dodecanoate, hydroxyaluminum didodecanoate, aluminum tridodecanoate, dihydroxyaluminum 2-ethylhexanoate, and di-2. Examples thereof include hydroxyaluminum ethylhexanate and aluminum tri-2-ethylhexanoate.
  • the above-mentioned metal soaps are generally used in the plastic industry as various additives (for example, stabilizers, lubricants, filler dispersants, anti-shear agents, fluidity improvers, nucleating agents or anti-blocking agents). ing.
  • the metal soap in the porous resin film is added to enhance the chargeability of the film, and is added as a functional agent for suppressing the deterioration of the piezoelectric performance especially in a high temperature environment. Therefore, from the viewpoint of suppressing the deterioration of the piezoelectric performance of the energy conversion element, the amount of metal is relatively larger than the blending amount (for example, 0.01% by mass) when used as the above-mentioned general various additives. It is preferable to add soap.
  • the content of the metal soap in the porous resin layer is 0.02% by mass with respect to 100% by mass of the composition composed of the thermoplastic resin and the metal soap constituting the porous resin layer from the viewpoint of charge retention ability. % Or more is preferable, 0.03% by mass or more is more preferable, 0.05% by mass or more is further preferable, 0.1% by mass or more is particularly preferable, and 0.2% by mass or more is most preferable.
  • the metal soap is made up of 100% by mass of the composition composed of the thermoplastic resin constituting the porous resin layer and the metal soap. On the other hand, it is preferably 20% by mass or less, more preferably 10% by mass or less, further preferably 5% by mass or less, particularly preferably 3% by mass or less, and most preferably 0.7% by mass or less.
  • the porous resin layer can contain additives such as a dispersant, a heat stabilizer (antioxidant), and a light stabilizer, if necessary.
  • the content of the dispersant in the porous resin layer is preferably 0.01% by mass or more from the viewpoint of improving the dispersibility of the pore-forming agent and suppressing the generation of coarse pores or communication pores. 03% by mass or more is more preferable, and 0.05% by mass or more is further preferable. On the other hand, from the viewpoint of moldability and charge retention of the porous resin layer, the content is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less.
  • dispersant examples include, but are not limited to, dispersants such as fatty acids, glycerin fatty acids, polyglycerin fatty acid esters, sorbitan fatty acid esters, silane coupling agents, poly (meth) acrylic acid or salts thereof.
  • the content of the heat stabilizer in the porous resin layer is usually 0.001 to 1% by mass.
  • the heat stabilizer include, but are not limited to, steric hindrance phenol-based, phosphorus-based, amine-based and other heat stabilizers.
  • the melting point of the heat stabilizer is preferably high from the viewpoint of charge retention performance, but from the viewpoint of uniformly dispersing the heat stabilizer in the porous resin layer, the melting point of the heat stabilizer is preferably low. Therefore, it is preferable that the melting point of the heat stabilizer has a melting point in the same temperature range as that of metal soap.
  • the content of the light stabilizer in the porous resin layer is usually 0.001 to 1% by mass.
  • the light stabilizer include, but are not limited to, sterically hindered amine-based, benzotriazole-based, and benzophenone-based light stabilizers.
  • the energy conversion film may have a single-layer structure consisting of only a porous resin layer having the above composition, or may have a multilayer structure having at least one porous resin layer.
  • the porous resin film preferably has a multi-layered structure having at least a core layer and a skin layer, and preferably has a three-layer structure of a skin layer / core layer / skin layer. More preferred.
  • the surface of the outermost layer satisfies the formulas (1) and (2).
  • the surface of the outermost skin layer satisfies the formulas (1) and (2).
  • the multi-layered energy conversion film is more preferably provided with a skin layer made of a stretched resin film on at least one surface of the core layer made of the porous resin film described above, and on both sides of the core layer made of the porous resin film described above. It is more preferable to provide a skin layer made of a stretched resin film.
  • FIG. 1 shows a configuration example of an energy conversion film 1 having a multilayer structure as an embodiment of the present invention.
  • the energy conversion film 1 includes a core layer 2 and a skin layer 3 provided on one surface of the core layer 2.
  • the energy conversion film 1 may also include a skin layer 4 on the other surface of the core layer 2, if necessary.
  • the adhesion to the electrodes provided on the respective surfaces 3a and 4a is improved.
  • the multilayer structure of the core layer and the skin layer can be formed by using the above-mentioned porous resin layer as the core layer and providing the skin layer on the surface of the core layer.
  • the skin layer is preferably laminated on at least one surface of the core layer (porous resin layer), and more preferably laminated on both sides of the core layer.
  • the surface of the core layer By covering the surface of the core layer with the skin layer, it is possible to prevent the electric charges stored inside through the pores in the core layer from being discharged to the atmosphere.
  • the surface strength of the film can be improved, and by smoothing the surface, the adhesiveness with the electrode is likely to be improved.
  • the skin layer is preferably a resin film containing a thermoplastic resin.
  • the skin layer may be a porous resin film like the core layer.
  • the thermoplastic resin constituting the skin layer for example, the resin listed as the thermoplastic resin of the porous resin film can be selected and used.
  • the skin layer may or may not contain metal soap like the core layer. From the viewpoint of using the skin layer as a protective layer for the core layer, it is preferable that the skin layer does not contain metal soap. When the skin layer contains metal soap, it is preferable that the content thereof is lower than that of the core layer.
  • the skin layer has a composition that makes it more difficult to form pores than the core layer, or that the pore ratio is lower than that of the core layer.
  • the formation of such a skin layer is a method of reducing the content of the pore-forming agent from that of the core layer, and the volume average particle diameter of the pore-forming agent used for the skin layer of the pore-forming agent used for the core layer. This can be achieved by a method of making the particle size smaller than the volume average particle size, or a method of forming a core layer by biaxial stretching and forming a skin layer by uniaxial stretching to make a difference in stretching ratio between the two.
  • the skin layer preferably contains a filler.
  • An undulating structure can be formed on the surface of the skin layer by the filler, and an anchoring effect that enhances the adhesion to the electrodes can be obtained.
  • the dielectric constant of the skin layer can be improved and the electrical characteristics of the core layer can be modified.
  • the filler for the skin layer the fillers listed in the above-mentioned porous resin layer can be used.
  • the filler of the skin layer may be the same type as the pore-forming agent of the porous resin film, or may be different types. Among the pore-forming agents, the inorganic filler is preferable because it is easy to obtain an anchoring effect.
  • the skin layer When the pore forming agent is contained in the skin layer, it is preferable to use the same dispersant as the dispersant used for the porous resin film. From the viewpoint of improving the physical strength of the skin layer and improving the durability of the core layer, it is preferable that the skin layer does not contain a pore-forming agent.
  • the skin layer is preferably a stretched film.
  • the uniformity of the thickness (film thickness) of the skin layer and the uniformity of electrical characteristics such as dielectric strength can be improved. If the thickness of the skin layer is highly uniform, local discharge concentration in the thin part of the skin layer is unlikely to occur during charge injection using a high voltage, so high voltage application for effective charge injection is applied. Easy to do.
  • the skin layer may have a single layer structure or a multi-layer structure having two or more layers.
  • a multi-layer structure by changing the type and content of the thermoplastic resin, pore-forming agent, and dispersant used for each layer, it is possible to design a multi-layer porous resin film with higher charge retention performance. It will be easy.
  • the types, contents, thicknesses, etc. of the components constituting each skin layer may be the same or different.
  • the thickness of the core layer is preferably 10 ⁇ m or more, more preferably 20 ⁇ m or more, further preferably 30 ⁇ m or more, and particularly preferably 40 ⁇ m or more.
  • the thickness of the core layer is preferably 500 ⁇ m or less, more preferably 300 ⁇ m or less, further preferably 150 ⁇ m or less, and particularly preferably 120 ⁇ m or less.
  • the thickness of the skin layer is not particularly limited, but is preferably 0.1 ⁇ m or more, more preferably 0.3 ⁇ m or more, further preferably 0.5 ⁇ m or more, and 0.7 ⁇ m or more. Is particularly preferable. When it is 0.1 ⁇ m or more, the thickness of the skin layer can be easily made uniform, the charge injection amount can be made uniform, and the dielectric strength can be easily improved. On the other hand, the thickness of the skin layer is preferably 100 ⁇ m or less, more preferably 50 ⁇ m or less, further preferably 30 ⁇ m or less, and particularly preferably 10 ⁇ m or less. When the thickness of the skin layer is 100 ⁇ m or less, when the electric charge is injected into the porous resin film having a multilayer structure, the electric charge can easily reach the core layer inside the film.
  • the skin layer is preferably thinner than the core layer. Since the skin layer is a layer that is relatively less likely to be elastically deformed in the thickness direction than the core layer, by suppressing the thickness of the skin layer, the compressive elastic modulus of the porous resin film or the like does not decrease, and the energy conversion efficiency is improved. It will be easier to maintain.
  • the ratio of the thickness of the core layer to the thickness of the skin layer is preferably 1.1 to 1000, more preferably 2 to 300, and preferably 5 to 150. More preferably, it is particularly preferably 10 to 50. The same ratio when there are a plurality of skin layers is calculated using the total thickness of each layer.
  • the thickness of the single-layer structure porous resin film can be in the same range as the core layer.
  • the film thickness is a value obtained by measuring the total film thickness using a thickness gauge based on JIS K7130: 1999 “Plastic-Film and Sheet-Thickness Measuring Method”.
  • the thickness of each layer constituting the multi-layered film is measured as follows. The sample to be measured is cooled to a temperature of ⁇ 60 ° C. or lower with liquid nitrogen, and a razor blade is applied at a right angle to the sample placed on the glass plate to cut the sample to prepare a sample for cross-sectional measurement.
  • the cross-sectional observation of the obtained sample is performed with a scanning electron microscope, the boundary line of each layer is discriminated from the pore shape and the appearance of the composition, and the ratio of each layer thickness obtained from the observation image to the total thickness of the film is determined.
  • the thickness of each layer is calculated by multiplying the total thickness of the film obtained by using a thickness gauge by the above ratio of the thickness of each layer.
  • the energy conversion film is preferably insulating, and the surface resistivity of at least one surface is preferably 1 ⁇ 10 13 ⁇ / ⁇ or more, and more preferably 5 ⁇ 10 13 ⁇ / ⁇ or more.
  • the surface resistivity of at least one surface of the energy conversion film is preferably 9 ⁇ 10 17 ⁇ / ⁇ or less, and more preferably 5 ⁇ 10 16 ⁇ / ⁇ or less.
  • the surface resistivity By setting the surface resistivity to or less than the above upper limit value, it is possible to prevent the adhesion of foreign matter such as dust and dirt. In addition, it is easy to prevent the local discharge from being transmitted through the foreign matter during the electretization process and hindering the electretization process.
  • the surface resistivity of the film is measured under the conditions of a temperature of 23 ° C. and a relative humidity of 50% using a double ring method electrode according to JIS K6911: 1995 “General Test Method for Thermosetting Plastics”. It is a value calculated based on the following formula (3) from the surface resistivity measured in the above.
  • Kf RS ⁇ ⁇ ⁇ (D + d) / (Dd)
  • Kf Surface resistivity ( ⁇ / ⁇ ) RS: Surface resistance ( ⁇ ) ⁇ : Pi d: Outer diameter (cm) of the inner circle of the surface electrode
  • D Inner diameter (cm) of the annular electrode on the surface
  • the energy conversion film of the present invention can be produced by forming a porous resin film, oxidizing at least one surface of the porous resin film, and then performing a cleaning treatment (B). By subjecting the obtained energy conversion film to an electretization treatment, it is possible to provide an energy conversion film having energy conversion performance.
  • the resin composition containing the above raw materials may be melt-kneaded, extruded from a single die, and stretched if necessary.
  • each layer is laminated by a coextrusion method using a multi-layer die using a feed block or a multi-manifold, an extrusion lamination method using a plurality of dies, or the like.
  • the film can be produced.
  • a coextrusion method using a multi-layer die and an extrusion lamination method may be combined.
  • the porous resin film is preferably a stretched film stretched at least in the uniaxial direction. Stretching improves the uniformity of the thickness of the porous resin film and facilitates the formation of a large number of pores inside. Further, in the case of a multi-layered porous resin film having a core layer and a skin layer, it is preferable that the skin layer is laminated on the core layer and then stretched at least in the uniaxial direction. By laminating the skin layer on the core layer and then stretching the film, the uniformity of the film thickness is improved as compared with the case where the stretched films are laminated, and as a result, the electrical characteristics are improved.
  • the pores formed in the porous resin layer by stretching have a relatively large volume, a relatively large number of pores, and a shape independent of each other from the viewpoint of retaining electric charges.
  • the size of the pores tends to be larger when stretched in the biaxial direction than when stretched only in the uniaxial direction.
  • MD Machine Direction
  • TD Transverse Direction
  • the disk-shaped pores are stretched in the plane direction around the pore forming agent. Can be formed, so that positively and negatively polarized charges can be easily accumulated in the pores by electretization treatment, and the charge retention performance is improved. Therefore, the porous resin film is preferably a biaxially stretched film.
  • Stretching can be performed by various known methods. Specifically, a longitudinal stretching method using the difference in peripheral speed of the roll group, a transverse stretching method using a tenter oven, a sequential biaxial stretching method in which the longitudinal stretching and the transverse stretching are performed in the forward or reverse order, a rolling method, Examples include a simultaneous biaxial stretching method using a combination of a tenter oven and a linear motor, a simultaneous biaxial stretching method using a combination of a tenter oven and a pantograph, and the like. In addition, a simultaneous biaxial stretching method by the tubular method, which is a stretching method of an inflation film, can be mentioned.
  • the temperature during stretching is preferably 1 to 70 ° C. lower than the melting point of the crystal part of the main thermoplastic resin from the glass transition point of the main (mostly used in terms of mass ratio) thermoplastic resin used for the porous resin film. ..
  • the main thermoplastic resin is a propylene homopolymer (melting point 155 to 167 ° C.)
  • it is preferably in the range of 100 to 166 ° C.
  • high-density polyethylene melting point 121 to 136 ° C.
  • it is preferably in the range of 70 to 135 ° C.
  • the stretching efficiency of the layer having the largest set basis weight (usually the core layer) or the layer having the highest set porosity (usually the core layer) is taken into consideration.
  • the stretching temperature is determined by using thermoplastic resins having different melting points or glass transition points for the core layer and the skin layer, the porosity of each layer can be adjusted.
  • the draw ratio is not particularly limited, and may be appropriately determined in consideration of the draw characteristics of the thermoplastic resin used for the porous resin film, the desired porosity, and the like.
  • the draw ratio is preferably 1.2 times or more, more preferably 2 times or more when stretched in the uniaxial direction.
  • the draw ratio is preferably 12 times or less, more preferably 10 times or less.
  • the area stretching ratio (product of the longitudinal magnification and the horizontal magnification) is preferably 1.5 times or more, and more preferably 4 times or more.
  • the same area stretching ratio is preferably 60 times or less, more preferably 50 times or less.
  • the draw ratio is preferably 1.2 times or more, more preferably 2 times or more when stretching in the uniaxial direction.
  • the draw ratio is preferably 10 times or less, more preferably 5 times or less.
  • the area stretching ratio is preferably 1.5 times or more, more preferably 4 times or more.
  • the same area stretching ratio is preferably 20 times or less, more preferably 12 times or less.
  • the ratio of the longitudinal magnification to the lateral magnification is preferably 0.4 or more, more preferably 0.5 or more, and preferably 0.7 or more. It is more preferably 0.8 or more, and particularly preferably 0.8 or more.
  • the ratio of the vertical magnification to the horizontal magnification is preferably 2.5 or less, more preferably 2.0 or less, further preferably 1.5 or less, and 1.3 or less. Is particularly preferred.
  • the stretching speed is preferably 20 to 350 m / min from the viewpoint of stable stretch molding.
  • the oxidation treatment can be performed on one surface or both sides of the porous resin film.
  • the oxidation treatment is performed on the surface of the skin layer.
  • the oxidation treatment is not particularly limited as long as the surface of the object to be treated can be oxidized, and a known oxidation treatment can be used.
  • Specific examples of the oxidation treatment include dielectric barrier discharge treatment, frame treatment, ozone treatment and the like. Among them, a dielectric barrier discharge that can obtain a high treatment effect and cause less damage to the film is preferable as a film treatment method.
  • Dielectric barrier discharge is a discharge that occurs when at least one of a pair of parallel plate electrodes with a certain interval is covered with an insulator (dielectric) and a high voltage and high flow voltage is applied between the electrodes. is there.
  • This discharge causes a phenomenon in which a gas normally existing in an insulated space is ionized.
  • this ionized gas acts on a substance, its surface receives energy, the surface energy becomes high, and it becomes an activated state.
  • polar groups are generated on the surface, and wettability and adhesion are improved.
  • the dielectric barrier discharge is sometimes expressed as "atmospheric pressure plasma", "corona discharge", or the like.
  • the voltage applying means is usually configured by using a high-frequency transmitter that generates an AC voltage of a predetermined frequency f and a high-voltage transformer that boosts the magnitude of the AC voltage output from the high-frequency transmitter to a predetermined voltage.
  • a high frequency transmitter for example, a high frequency power supply (CT-0212) manufactured by Kasuga Electric Works Ltd. can be used.
  • CT-T02W transformer
  • the voltage applying means is usually configured by using a high-frequency transmitter that generates an AC voltage of a predetermined frequency f and a high-voltage transformer that boosts the magnitude of the AC voltage output from the high-frequency transmitter to a predetermined voltage.
  • CT-0212 high frequency power supply
  • CT-T02W transformer manufactured by Kasuga Electric Works Ltd.
  • the frequency f of the AC voltage output from the high frequency transmitter is preferably in the range of 10 to 200 kHz.
  • the frequency f of the AC voltage output from the high frequency transmitter is preferably in the range of 10 to 200 kHz.
  • uniform discharge is likely to occur (discharge is unlikely to be locally concentrated), which is preferable.
  • the frequency region of 200 kHz or less it is difficult to form a low-resistance discharge channel due to the residual ions generated by the staying of the ions generated by the discharge as they are, and the discharge is locally concentrated and uniform processing cannot be performed, resulting in a large current. Is preferable for safety because it is easy to avoid the flow of high heat and the generation of high heat.
  • the waveform of the AC voltage output from the high-frequency transmitter is not particularly limited as long as the frequency is in the above range of 10 to 200 kHz, and even if it is a sine wave, it is a square wave (including a pulse waveform). It may be.
  • the discharge amount is preferably 600 J / m 2 (10 W / min / m 2 ) or more, and more preferably 1,200 J / m 2 (20 W / min / m 2). ) That's it. Further, the discharge amount is preferably 12, 000J / m 2 (200W ⁇ min / m 2) or less, and more preferably not more than 10,800J / m 2 (180W ⁇ min / m 2).
  • the amount of discharge when the frame processing is performed is preferably 8,000 J / m 2 or more, and more preferably 20,000 J / m 2 or more.
  • the discharge amount is preferably 200,000 J / m 2 or less, and more preferably 100,000 J / m 2 or less.
  • the surface that has been oxidized is subjected to a cleaning treatment (B).
  • the cleaning solvent used in the cleaning treatment (B) is preferably water or an aqueous solution from the viewpoint of solubility of a low molecular weight acidic compound to be removed by cleaning, and for example, a cleaning treatment such as immersing in water or an aqueous solution is performed. Will be washed. In particular, it is preferable to wash with water or an aqueous solution having a pH of 5 to 11. By cleaning with a neutral, weakly basic or weakly acidic solvent, no acid or base remains on the surface of the porous resin film after cleaning, and the adhesion of the electrodes in the energy conversion element manufactured using this does not remain.
  • the liquid is absorbed by spraying or showering the liquid on both sides or at least the oxidized surface.
  • Various means such as passing over a sponge-like roll can be applied.
  • the method of immersing the film in a liquid is particularly preferable because the film surface can be kept uniformly wet by water or an aqueous solution.
  • a drying treatment may be performed.
  • the method of the drying treatment is not particularly limited, and known drying methods such as hot air drying and infrared drying can be used.
  • FIG. 2 shows an example of the manufacturing process of the energy conversion film 1. This manufacturing process is an example, and the process differs depending on the layer structure of the film, the number of stretched axes, and the like.
  • the energy conversion film 1 having a three-layer structure can be manufactured by three extruders 51 to 53.
  • the resin composition of each layer is melt-kneaded and extruded by three extruders 51 to 53, and the skin layer, the core layer, and the skin layer are laminated in this order in the intermediate runner 54 and co-extruded from the T die 55.
  • the co-extruded skin layer / core layer / skin layer laminated film is cooled by the cooling roll 56, stretched in the longitudinal direction (MD) by the stretching device 57, and then further laterally (TD) by the stretching device 58. It is stretched.
  • the surface of the stretched film is oxidized in the oxidation treatment device 59, and then passed through the water tank in the cleaning treatment device 60 to perform the oxidation treatment (B) on the surface of the stretched film.
  • the film dried in the drying device 61 is taken up by the take-up roll 62.
  • the pores inside the porous resin film can be further expanded by pressure treatment.
  • a porous resin film is placed in a pressure vessel, and the inside of the vessel is pressurized with a non-reactive gas to allow the non-reactive gas to permeate into the pores, and then the porous resin film is placed under non-pressurization. Do it by releasing it.
  • the non-reactive gas used include an inert gas such as argon and helium, nitrogen, carbon dioxide or a mixed gas thereof, air and the like.
  • an inert gas such as argon and helium, nitrogen, carbon dioxide or a mixed gas thereof, air and the like.
  • the processing pressure during the pressurization treatment is not particularly limited, but is preferably in the range of 0.2 to 10 MPa, more preferably 0.3 to 8 MPa, and even more preferably 0.4 to 6 MPa. When it is 0.2 MPa or more, the pressure is sufficient and a sufficient expansion effect can be easily obtained.
  • the treatment time of the pressurization treatment is not particularly limited, but is preferably in the range of 1 hour or more, more preferably 1 to 50 hours.
  • the treatment time is 1 hour or more, the pores can be sufficiently filled with the non-reactive gas.
  • the non-reactive gas is dissipated during the heat treatment described later, and a stable expansion effect is obtained. Tends to be difficult to obtain.
  • the take-up roll of the porous resin film When the take-up roll of the porous resin film is pressure-treated, it is desirable to take it together with a buffer sheet and then pressurize it so that the non-reactive gas easily permeates into the inside of the take-up roll.
  • the cushioning sheet include a foamed polystyrene sheet, a foamed polyethylene sheet, a foamed polypropylene sheet, a non-woven fabric, a woven fabric, a sheet having a communication gap such as paper, and the like.
  • the pressure-treated porous resin film is preferably heat-treated from the viewpoint of maintaining its expansion effect.
  • the porous resin film expands by performing a pressure treatment and releasing it under non-pressurization. However, if left as it is, the non-reactive gas that has permeated into the pores will gradually escape, and the porous resin film may return to its original thickness. Therefore, it is desirable to heat-treat the expanded porous resin film to promote the crystallization of the thermoplastic resin so that the expansion effect can be maintained even after the inside of the pores drops to atmospheric pressure.
  • the heat treatment can be performed within a temperature range equal to or higher than the glass transition point of the main thermoplastic resin of the porous resin film and lower than the melting point of the crystal part.
  • the main thermoplastic resin is a propylene homopolymer (melting point 155 to 167 ° C.)
  • it is in the range of 80 to 160 ° C.
  • a known method can be used as a heating method. Specific examples include, but are not limited to, hot air heating by hot air from a nozzle, radiant heating by an infrared heater, contact heating by a roll with a temperature control function, and the like.
  • non-contact heat treatment such as hot air heating or radiant heating tends to maintain a high expansion ratio. There is a tendency.
  • the electretization process is a process of injecting an electric charge into an energy conversion film.
  • the electretization process there are several processing methods. For example, there are known an electro-electret method in which both sides of a film are held by a conductor and a DC high voltage or a pulsed high voltage is applied, and a radio electret method in which the film is irradiated with ⁇ -rays or electron beams to form an electret. Is.
  • the electro-electret-forming method using DC high-voltage discharge has a small device and a small load on workers and the environment, and is suitable for electret-forming treatment of polymer materials such as porous resin films. It is preferable.
  • FIG. 3 shows an electretizing device by DC high voltage discharge as an example of the electretizing device.
  • an energy conversion film 1 is fixed between a needle-shaped electrode 11 and a ground electrode 12 connected to a DC high-voltage power supply 10 and a predetermined voltage is applied. By applying a voltage, the energy conversion film 1 can accumulate a large amount of electric charges inside the film.
  • the applied voltage during the electret formation is the film thickness, pore ratio, material of the thermoplastic resin or pore forming agent used, processing speed, shape and material, size of the electrode used, or the desired charge in the energy conversion film. It may be set appropriately in consideration of the amount and the like.
  • the applied voltage is not particularly limited, but is preferably 5 kV or higher, more preferably 6 kV or higher, and even more preferably 7 kV or higher. By setting the value to the above lower limit or more, a sufficient amount of electric charge can be injected, and the desired piezoelectric performance tends to be easily exhibited.
  • the applied voltage of the electret formation treatment is preferably 100 kV or less, more preferably 70 kV or less, and further preferably 50 kV or less.
  • the treatment temperature at the time of electrification treatment may be appropriately set and is not particularly limited, but it is preferably performed from the glass transition point or more of the main thermoplastic resin used for the energy conversion film to the melting point or less of the crystal part.
  • the treatment temperature is above the glass transition point, the molecular motion of the amorphous part of the thermoplastic resin is active and the molecular arrangement is suitable for the given charge, so that efficient electretization treatment is possible. ..
  • the energy conversion film contains metal soap
  • the treatment temperature is equal to or higher than the melting point of the metal soap, the metal soap molecules also form an arrangement suitable for the given electric charge, so that more efficient electrification treatment can be performed. It will be possible.
  • the processing temperature does not exceed the melting point of the main thermoplastic resin used for the energy conversion film. ..
  • an excessive charge may be injected into the energy conversion film intentionally or unintentionally.
  • the static elimination treatment a known method using a voltage application type static eliminator (ionizer), a self-discharge type static eliminator, or the like can be used.
  • the surface charge of the energy conversion film can be removed, but the charge accumulated inside the film, particularly in the pores of the core layer, cannot be completely removed. Therefore, the static elimination treatment does not significantly reduce the performance of the electret material. Therefore, it is possible to prevent the discharge phenomenon of the energy conversion film by performing such a static elimination treatment to remove the excess charge on the film surface.
  • the energy conversion element of the present invention includes the above-mentioned energy conversion film and electrodes provided on at least one surface of the energy conversion film.
  • the energy conversion element of the present invention inputs and outputs electric power or an electric signal, and from the viewpoint of more efficient input and output, it is usually preferable to provide a pair of electrodes on both sides of the energy conversion film. ..
  • FIG. 4 shows the configuration of the energy conversion element 5 including the energy conversion film 1 shown in FIG. 1 as an embodiment of the present invention.
  • the energy conversion element 5 includes an energy conversion film 1 and an electrode 6 on one surface thereof.
  • the energy conversion element 5 can include an electrode 7 on the other surface of the energy conversion film 1.
  • the pair of electrodes 6 and 7 are provided on the surface of the energy conversion film 1, that is, on the surface 3a of the skin layer 3 and the surface 4a of the skin layer 4.
  • the surfaces 3a and 4a satisfy the formulas (1) and (2).
  • the timing of installing the electrodes is not particularly limited, and may be, for example, before or after the electretization process. After the electretization process, it is possible to prevent a part of the injected charge from being dissipated through the electrodes during the electretization process. However, when a load such as heat is applied to the film during the subsequent electrode installation, a part of the injected charge is dissipated, and the piezoelectric performance may be slightly deteriorated. At present, judging from the performance of the energy conversion element finally obtained, it is preferable to provide an electrode in advance before the electretization treatment and then perform the above-mentioned electretization treatment.
  • Examples of the electrode include a thin film formed of a known conductive material such as metal particles, conductive metal oxide particles, carbon-based particles, or a conductive resin.
  • Examples of the electrode include a coating film obtained by printing or coating a conductive paint, a metal vapor deposition film, and the like.
  • the conductive material examples include metal particles such as gold, silver, platinum, copper and silicon; tin-doped indium oxide (ITO), antimon-doped tin oxide (ATO), fluorine-doped tin oxide (FTO), aluminum-doped zinc oxide and the like.
  • Conductive metal oxide particles examples thereof include materials obtained by mixing carbon-based particles such as graphite, carbon black, Ketjen black, carbon nanofiller, or carbon nanotubes with a solution or dispersion of a binder resin component.
  • binder resin component examples include acrylic resin, urethane resin, ether resin, ester resin, epoxy resin, vinyl acetate resin, vinyl chloride resin, vinyl chloride-vinyl acetate copolymer, amide resin, and melamine resin.
  • examples thereof include a phenol resin, a vinyl alcohol resin, and a modified polyolefin resin.
  • the conductive material examples include a solution or dispersion of a conductive resin such as a polyaniline resin, a polypyrrole resin, or a polythiophene resin.
  • Examples of the printing method when the electrode is provided by printing using the ink of the conductive material include screen printing, flexo printing, gravure printing, inkjet printing, letterpress printing, offset printing and the like.
  • a coating device when an electrode is provided by coating using a paint of a conductive material for example, a die coater, a bar coater, a comma coater, a lip coater, a roll coater, a curtain coater, a gravure coater, a spray coater, and a blade.
  • Examples thereof include a coater, a reverse coater, and an air knife coater.
  • a metal such as aluminum, zinc, gold, silver, platinum, nickel is vaporized under reduced pressure and vapor-deposited on the surface of the energy conversion film, and a metal thin film formed directly on the surface is used, as well as polyethylene terephthalate.
  • a metal thin film formed by depositing a metal such as aluminum, zinc, gold, silver, platinum, or nickel on a carrier such as a (PET) film, and the metal thin film transferred to the surface of an energy conversion film is mentioned. Be done.
  • the electrode is a laminate in which an electrode such as a coating film of the conductive paint or a metal vapor deposition film is previously formed on a dielectric film such as a polyethylene terephthalate film or a polypropylene film, and an energy conversion film so that the electrode is on the outside. It may be provided by laminating. Examples of the bonding method include known methods such as dry laminating, wet laminating, and extruded laminating. In this case, the dielectric film is bonded to the surface of the energy conversion film, but the surfaces satisfying the formulas (1) and (2) have high adhesion to the derivative film, and the adhesion does not decrease with time. Therefore, the adhesion to the electrode does not decrease with time, and excellent energy conversion performance can be maintained for a long period of time.
  • the thickness of the electrode is not particularly limited, but is preferably 0.1 ⁇ m or more, more preferably 1 ⁇ m or more, and further preferably 5 ⁇ m or more.
  • the thickness of the electrode is preferably 200 ⁇ m or less, more preferably 50 ⁇ m or less, and further preferably 20 ⁇ m or less.
  • the surface resistivity of the electrode is preferably 1 ⁇ 10 -3 ⁇ / ⁇ or more, and preferably 1 ⁇ 10 -1 or more, for the purpose of easily inputting and outputting electric power.
  • an electrode of 1 ⁇ 10 -3 ⁇ / ⁇ or more is provided and the electrode is provided by coating, it is not necessary to provide the electrode thickly, and it is porous due to the heat of drying and sintering after coating. Deformation such as crushing of pores in the resin film and heat shrinkage of the porous resin film can be suppressed. Further, when the electrodes are provided by metal vapor deposition, it is possible to suppress film deformation due to the heat of the metal to be deposited.
  • the surface resistivity of the electrode is preferably 9 ⁇ 10 7 ⁇ / ⁇ or less, and more preferably 9 ⁇ 10 4 ⁇ / ⁇ or less.
  • the resistance value of the electrode is 9 ⁇ 10 7 ⁇ / ⁇ or less, the transmission efficiency of the electric signal is high, and the performance as a material for electric and electronic input / output devices tends to be improved.
  • the resistivity of the electrode surface is calculated by the following formula (4) from the resistivity value measured by the four-probe method according to JIS K7194: 1994 "Resistance test method by the four-probe method of conductive plastic". The value calculated based on this.
  • (4) Ke F ⁇ R Ke: Surface resistivity ( ⁇ / ⁇ )
  • F Correction coefficient (described in JIS K7194)
  • R Resistance value ( ⁇ )
  • the energy conversion film and the energy conversion element of the present invention use a porous resin film, the cost is relatively low, unlike semiconductor materials that have been widely used as materials for electric-mechanical energy conversion. For example, it is easy to increase the area of the film by about 10 to 50,000 cm 2 in a plan view.
  • the plan-viewing area thereof may be appropriately set in consideration of desired performance, physical restrictions on the installation location, etc., and is not particularly limited, but 20 to 20 to 30,000 cm 2 is preferable, and 50 to 25,000 cm 2 is more preferable.
  • the voltage generated by the impact is preferably 150 mV or more, more preferably 200 mV or more, still more preferably 300 mV or more, from the viewpoint of practical performance of the energy conversion element. It is particularly preferable that the voltage is 4000 mV or more.
  • the upper limit is not particularly limited, but is preferably 5000 mV or less, more preferably 3000 mV or less, further preferably 2000 mV or more, and particularly preferably 10000 mV or less.
  • the above generated voltage can be measured by a ball drop test. Specifically, an iron ball having a height of 8 mm in the vertical direction, a diameter of 9.5 mm, and a mass of 3.5 g is placed on an energy conversion element placed on a horizontal plane in an environment of a temperature of 23 ° C. and a relative humidity of 50%. The generated voltage generated by the impact when naturally dropped is measured 10 times, and the value obtained by calculating the average value of the generated voltage is defined as the generated voltage.
  • Table 1 shows the compositions of the resin compositions a and c.
  • the resin composition a for the skin layer and the resin composition c for the core layer were melt-kneaded by three extruders set at 230 ° C., respectively. Then, it was supplied to a feed block type multilayer die set at 250 ° C., laminated in the die in the order of a / c / a lamination, and extruded into a sheet. This was cooled to 60 ° C. by a cooling device to obtain a three-layer unstretched sheet.
  • the obtained unstretched sheet was heated to 135 ° C. using a heating roll and stretched 5 times in the vertical direction (MD direction) by utilizing the difference in peripheral speed of the roll group to obtain a uniaxially stretched sheet.
  • the obtained uniaxially stretched sheet is cooled to 60 ° C., reheated to 155 ° C. using an oven, stretched 9 times in the lateral direction (TD direction) using a tenter, and then further to 160 ° C. using an oven. It was heated and annealed to obtain a biaxially stretched sheet.
  • the obtained biaxially stretched sheet was cooled to 60 ° C., the ears were slit, and a porous resin film having a three-layer structure (number of stretched axes of each layer: biaxial / biaxial / biaxial, thickness of each layer: 1 ⁇ m / 68 ⁇ m / 1 ⁇ m, the thickness of the entire film: 70 ⁇ m) was obtained.
  • the surface resistivity of the obtained porous resin film was 10 14 ⁇ / ⁇ or more on both the front and back sides. Further, all of the porous resin films had pores inside, and the pore ratio of the entire film was 50%.
  • Table 2 shows the composition of the porous resin film.
  • the obtained porous resin film is cooled to a temperature of -60 ° C or less with liquid nitrogen, and a razor blade (manufactured by Chic Japan Co., Ltd., trade name: Proline blade) is applied to the sample placed on a glass plate.
  • a razor blade manufactured by Chic Japan Co., Ltd., trade name: Proline blade
  • the obtained sample was photographed using a scanning electron microscope (manufactured by JEOL Ltd., trade name: JSM-6490) at a magnification of 500 times, and the images were laminated so that the observation length was 1 mm wide.
  • the oxidized surface was subjected to a cleaning treatment (B) by passing a porous resin film through a water tank filled with water. Then, water was squeezed with a squeeze roll and dried with hot air at 70 ° C. to obtain an energy conversion film.
  • Example 2 Energy conversion of Example 2 in the same manner as in Example 1 except that the treatment condition of the oxidation treatment was set to nitrogen under atmospheric pressure and the output was changed to 150 (W ⁇ min / m 2 ). I got a film.
  • Comparative Example 1 An energy conversion film of Comparative Example 1 was obtained in the same manner as in Example 1 except that the washing treatment (B) and the drying treatment were not performed in Example 1.
  • ⁇ XPS measurement conditions The atomic concentration was measured by XPS under the following equipment and measurement conditions, and was obtained from the ratio of the values obtained by multiplying the peak intensity areas of O1s, C1s and N1s by the relative sensitivity of each peak.
  • a PET film with a thickness of 12 ⁇ m (trade name: E5200, manufactured by Toyobo Co., Ltd.) is subjected to a roll-to-roll vacuum vapor deposition apparatus so that the thickness of the vapor deposition film becomes 30 nm under vacuum conditions of 1 ⁇ 10 -2 Pa.
  • Aluminum was vapor-deposited on the surface to prepare a metal-deposited film having a surface resistance of 1 ⁇ / ⁇ .
  • polyester adhesive trade name: ADCOTE AD502, manufactured by Toyo Morton, solid content concentration 50% by mass
  • polyisocyanate (trade name: CAT-10L, manufactured by Toyo Morton, solid content concentration 52.5% by mass).
  • ethyl acetate in a mass ratio of 15: 1.5: 25 to prepare an adhesive coating material.
  • the metal-deposited film is cut into a square of 100 mm in length and 100 mm in width, and an adhesive paint is applied to the surface on which the metal-deposited film is not deposited so that the amount of coating after drying is 2 g / m 2.
  • an adhesive layer was provided on one side of the metallized film.
  • the energy conversion film to be evaluated was cut into a square of 200 mm in length ⁇ 200 mm in width, and a metal-deposited film was formed on the central portion of the front surface and the back surface of the obtained cut film via an adhesive layer, and the vapor-deposited film was the outermost layer. I pasted it so that it would be.
  • the adhesive was cured in an oven at 40 ° C. for 24 hours to obtain an energy conversion film having electrodes on both sides.
  • a resin film having electrodes on both sides was installed on the ground electrode 12 board of the electret-making device shown in FIG. 3 so that the surface faces the main electrode side.
  • the distance between the needle-shaped electrodes was set to 10 mm
  • the distance between the needle-shaped electrode and the ground electrode was set to 10 mm.
  • An electret treatment was carried out by applying a DC voltage of ⁇ 10 KV to the needle-shaped electrode for 5 seconds.
  • the central portion of the energy conversion film of 200 mm ⁇ 200 mm was cut into a width of 20 mm using a cutter knife to obtain a strip-shaped energy conversion element having a width of 20 mm ⁇ a length of 200 mm (electrode size: 20 mm ⁇ 100 mm).
  • Friction treatment In order to evaluate the performance of the energy conversion element after deterioration due to normal use, friction treatment was performed prior to the subsequent evaluation.
  • the energy conversion elements obtained in Examples and Comparative Examples were sandwiched between PET films having a thickness of 50 ⁇ m, an additional load of 500 g was applied by a Gakushin tester, and a friction load of 43,200 reciprocations was applied at a speed of 30 reciprocations / min. ..
  • the generated voltage was measured in an environment of a temperature of 23 ° C. and a relative humidity of 50% using the ball drop test apparatus shown in FIG.
  • one end of the lead wires 17 and 18 is used for the electrodes on the front and back surfaces of the sample 20 (energy conversion element 5) having a length of 20 mm and a width of 200 mm using a conductive tape (trade name: AL-25BT, manufactured by Sumitomo 3M Ltd.).
  • the other ends of the lead wires 17 and 18 were connected to a high-speed recorder 19 (trade name: GR-7000, manufactured by Keyence).
  • the sample 20 was placed on the insulating sheet 15 (soft vinyl chloride sheet, thickness 1 mm) of the ball drop test apparatus shown in FIG. 5 with the surface facing up.
  • a glass plate 14 (thickness 8 mm) was placed on the upper surface of the sample 20, and an iron ball 16 having a diameter of 9.5 mm and a mass of 3.5 g was placed on the glass plate 14.
  • the iron ball 16 is naturally dropped onto the sample 20 from a height of 8 mm in the vertical direction from the glass plate 14, the voltage signal from the sample 20 is taken into the high-speed recorder 19, and the maximum voltage generated by the impact of the falling ball is measured 10 times. Then, the average value of the maximum voltage was defined as the generated voltage (mV).
  • Epoxy adhesive manufactured by Cemedine Co., Ltd., trade name: High Super 30, two-component mixed type
  • a PET film with a width of 20 mm and a length of 200 mm and a thickness of 50 ⁇ m is used as the energy conversion element.
  • a sample for measuring peel strength was prepared by pasting in the overlapping direction. After storing in a thermostatic chamber (temperature 23 ° C., relative humidity 50%) for 12 hours or more, the end of the energy conversion film and the end of the PET film were attached to the clamps of a tensile tester (AUTOGRAPH) manufactured by Shimadzu Corporation.
  • AUTOGRAPH tensile tester
  • the PET film was pulled at a tensile speed of 50 mm / min at an angle of 180 ° with respect to the energy conversion film, and the electrode portion (metal-deposited film) was peeled off from the energy conversion film.
  • the stress at the time of stability was measured by a load cell and used as the peeling force.
  • the peeling force is 200 g / cm or more or the energy conversion film is torn and the adhesion is very good.
  • the peeling force is 50 g / cm or more and less than 200 g / cm, and the adhesion is good.
  • the peeling force is 50 g / cm. Less than cm and poor adhesion
  • the energy conversion films of each Example and Comparative Example were stored at room temperature for one year from the production to obtain an energy conversion film after one year.
  • the energy conversion element was manufactured as described above using the energy conversion film after one year had passed, and was used as the energy conversion element one year after the manufacture.
  • the atomic concentration, the generated voltage, and the adhesion to the electrodes were evaluated for the energy conversion element one year after the production.
  • Table 3 shows the evaluation results immediately after production.
  • Table 4 shows the evaluation results one year after the production.
  • the energy conversion films of Examples 1 and 2 having surfaces satisfying the formulas (1) and (2) have adhesion to electrodes when used in an energy conversion element. Is high, and a sufficient generated voltage is obtained. This high electrode adhesion is maintained even after one year has passed from immediately after production, and the decrease in generated voltage is suppressed as compared with the comparative example.
  • the oxygen atom concentration on the surface was increased by the oxidation treatment and the formula (2) was satisfied, but the oxygen atom concentration was lowered after the cleaning treatment (A), and the formula (1) was changed. Not satisfied. Therefore, the adhesion of the electrodes is high immediately after production, and a sufficient generated voltage is obtained, but after one year, the adhesion of the electrodes is greatly reduced, and a sufficient generated voltage is not obtained.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

La présente invention supprime la détérioration dans le temps au niveau de l'adhésion entre une électrode et un film de résine poreuse.　Un film de conversion d'énergie qui est un film de résine poreuse ayant au moins une surface qui satisfait la formule (1) et la formule (2) décrites ci-dessous.　(1) 0,8 ≤ S1/S0 ≤ 1,0 (2) 2,0 ≤ S0 (dans les formules, S0 représente la concentration en atome d'oxygène (% atm) avant le traitement de nettoyage (A) ; et S1 représente la concentration en atome d'oxygène (% atm) après le traitement de nettoyage (A). La concentration en atome d'oxygène est le rapport du nombre d'atomes d'oxygène au nombre total d'atomes d'oxygène, d'atomes de carbone et d'atomes d'azote tel que déterminé par spectroscopie photoélectronique aux rayons X (XPS), à savoir (le nombre d'atomes d'oxygène)/((le nombre d'atomes d'oxygène) + (le nombre d'atomes de carbone) + (le nombre d'atomes d'azote)). Le traitement de nettoyage (A) est un traitement de nettoyage à l'aide d'eau distillée.)
PCT/JP2020/028997 2019-07-31 2020-07-29 Film de conversion d'énergie, élément de conversion d'énergie et procédé de production d'un film de conversion d'énergie WO2021020427A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04328135A (ja) * 1991-04-30 1992-11-17 Masuda Kenkyusho:Kk 樹脂成形品のコロナ放電処理方法および装置
JPH06336529A (ja) * 1993-05-28 1994-12-06 Nippon Paint Co Ltd コロナ放電処理方法
JP2011018897A (ja) * 2009-06-11 2011-01-27 Nitto Denko Corp 圧電・焦電素子用多孔質樹脂シート及びその製造方法
WO2011034186A1 (fr) * 2009-09-17 2011-03-24 株式会社ユポ・コーポレーション Film de conversion d'énergie
JP2013060530A (ja) * 2011-09-13 2013-04-04 Seiko Epson Corp 接合方法および接合体
WO2018143294A1 (fr) * 2017-02-01 2018-08-09 株式会社ユポ・コーポレーション Film de conversion d'énergie et élément de conversion d'énergie l'utilisant

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3571180B2 (ja) * 1997-06-06 2004-09-29 日本バイリーン株式会社 非導電性多孔質体の総表面の処理方法
JP4930913B2 (ja) * 2005-09-12 2012-05-16 東レバッテリーセパレータフィルム合同会社 多孔性素材のプラズマ処理方法及び処理装置

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04328135A (ja) * 1991-04-30 1992-11-17 Masuda Kenkyusho:Kk 樹脂成形品のコロナ放電処理方法および装置
JPH06336529A (ja) * 1993-05-28 1994-12-06 Nippon Paint Co Ltd コロナ放電処理方法
JP2011018897A (ja) * 2009-06-11 2011-01-27 Nitto Denko Corp 圧電・焦電素子用多孔質樹脂シート及びその製造方法
WO2011034186A1 (fr) * 2009-09-17 2011-03-24 株式会社ユポ・コーポレーション Film de conversion d'énergie
JP2013060530A (ja) * 2011-09-13 2013-04-04 Seiko Epson Corp 接合方法および接合体
WO2018143294A1 (fr) * 2017-02-01 2018-08-09 株式会社ユポ・コーポレーション Film de conversion d'énergie et élément de conversion d'énergie l'utilisant

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