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WO2013011949A1 - Matériau électret thermorésistant et microphone à condensateur - Google Patents

Matériau électret thermorésistant et microphone à condensateur Download PDF

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Publication number
WO2013011949A1
WO2013011949A1 PCT/JP2012/067953 JP2012067953W WO2013011949A1 WO 2013011949 A1 WO2013011949 A1 WO 2013011949A1 JP 2012067953 W JP2012067953 W JP 2012067953W WO 2013011949 A1 WO2013011949 A1 WO 2013011949A1
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Prior art keywords
electret
resin layer
heat
base resin
layer
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PCT/JP2012/067953
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English (en)
Japanese (ja)
Inventor
伴幸 白川
博幸 長尾
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三菱樹脂株式会社
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Publication of WO2013011949A1 publication Critical patent/WO2013011949A1/fr

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    • H—ELECTRICITY
    • H04—ELECTRIC COMMUNICATION TECHNIQUE
    • H04R—LOUDSPEAKERS, MICROPHONES, GRAMOPHONE PICK-UPS OR LIKE ACOUSTIC ELECTROMECHANICAL TRANSDUCERS; DEAF-AID SETS; PUBLIC ADDRESS SYSTEMS
    • H04R19/00—Electrostatic transducers
    • H04R19/01—Electrostatic transducers characterised by the use of electrets
    • H04R19/016—Electrostatic transducers characterised by the use of electrets for microphones
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
    • H01G7/02—Electrets, i.e. having a permanently-polarised dielectric
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G7/00—Capacitors in which the capacitance is varied by non-mechanical means; Processes of their manufacture
    • H01G7/02—Electrets, i.e. having a permanently-polarised dielectric
    • H01G7/021—Electrets, i.e. having a permanently-polarised dielectric having an organic dielectric
    • H01G7/023—Electrets, i.e. having a permanently-polarised dielectric having an organic dielectric of macromolecular compounds

Definitions

  • the present invention relates to a heat-resistant electret material capable of exhibiting high interlayer adhesion and charge retention characteristics even when high-heat-resistant polytetrafluoroethylene (PTFE) is used as the fluororesin of the electret layer, and the heat-resistant electret
  • PTFE polytetrafluoroethylene
  • the present invention relates to a condenser-type microphone using a material.
  • An electret condenser microphone is known as one type of microphone.
  • Electret type condenser microphones are relatively easy to miniaturize, but when they are used in mobile phones that have been further thinned in recent years, in addition to miniaturization, they are thinned. It is desirable to do. Further, as a characteristic of the condenser microphone using the electret material, the sensitivity is improved when the thickness of the electret layer (insulating resin layer) is reduced.
  • Electrets are ferroelectric materials, which have the property that they accumulate charge semi-permanently (charge electrets) or have semi-permanent electrical polarity due to oriented dipoles (dipole electrets).
  • charge electrets charge semi-permanently
  • dipole electrets semi-permanent electrical polarity due to oriented dipoles
  • the electret is incorporated for the purpose of converting acoustic energy into a corresponding electrical signal by a potential difference displacement that occurs when either the electret fixed electrode or the counter electrode is vibrated by sound waves.
  • a fluororesin having a larger charge amount than other resins is used.
  • fluororesins tetrafluoroethylene-hexafluoropropylene copolymer (FEP) is known to have little charge decay, and FEP fused to a metal plate is a condenser for microphones that is an electronic component.
  • FEP tetrafluoroethylene-hexafluoropropylene copolymer
  • the electrets based on fluorine-containing polymers are generally charged by, for example, negative corona discharge in air.
  • solder that has been conventionally used for joining electronic components is required to be lead-free, that is, joined with solder that does not contain lead.
  • solder containing no lead has a higher melting point than conventional solder, and the soldering temperature needs to be 20 to 30 ° C. higher than conventional solder. Therefore, FEP is used for the insulating resin layer of the electret fixed electrode. If this is the case, there has been a problem that the FEP melts due to the soldering temperature, making it impossible to obtain good charging characteristics.
  • a resin material for the electret fixed electrode a material having heat resistance with respect to the soldering temperature of lead-free solder and excellent charging characteristics is required.
  • PTFE polytetrafluoroethylene
  • PTFE is preferable as a resin material for electret fixed electrodes because it has a large amount of charge and little charge decay, and since it has a higher melting point than FEP, it is also heat resistant to the soldering temperature of lead-free solder
  • the PTFE film has a problem that it is difficult to adhere to a metal substrate.
  • an adhesive layer made of a thermoplastic resin other than PTFE is provided between the metal substrate and the PTFE film.
  • the adhesive layer when the adhesive layer is provided, the sensitivity as a fixed electrode may be impaired, and there is a problem that charging characteristics are deteriorated (charging attenuation is increased) by using a thermoplastic resin other than PTFE. Further, in order to improve the adhesion to a metal substrate with a PTFE film alone without providing an adhesive layer, it must be heat-sealed at a temperature greatly exceeding the melting point of PTFE (about 327 ° C.). When fused at a high temperature, there is a problem in that the charge decay increases.
  • Japanese Patent Application Laid-Open No. 2002-125297 describes an electret laminate in which a single thermoplastic resin film is adhered to the surface of a metal plate, but only an example using an FEP film as the thermoplastic resin film is disclosed. However, it is not clear how the PTFE film is adhered to the surface of the metal plate.
  • Japanese Patent No. 3692090 describes a multi-layer electret material in which an FEP film and a PTFE film are sequentially melt bonded on a metal plate. In this electret material, charge retention is achieved by laminating a fluororesin layer. There are disadvantages that are impaired. In addition, when FEP is used for the adhesive layer, the adhesive layer cannot be obtained unless the adhesive layer is thick, and the adhesive layer becomes thick. Has the disadvantage of not being suitable.
  • Japanese Patent Application Laid-Open No. 2010-279024 discloses a method of adding electric conductivity by adding carbon to a base resin layer provided between a metal substrate and an electret layer to enhance charge retention. ing.
  • this method has a problem that the interlaminar adhesion between the metal substrate and the base resin layer is reduced due to the low metal affinity of carbon itself, and the interlaminar adhesion between the base resin layer and the electret layer is insufficient. is there.
  • JP 2002-125297 A Japanese Patent No. 3692090 JP 2010-279024 A
  • the present invention solves such problems of the prior art, and has a large charge holding power and low charge attenuation, and further from a metal substrate and a fluororesin, particularly polytetrafluoroethylene (PTFE). It is an object of the present invention to provide a heat-resistant electret material having excellent adhesiveness with an electret layer.
  • PTFE polytetrafluoroethylene
  • the present inventor made a base resin within a range that does not impair the charge retention characteristics of silicon (Si), a silicon compound, or a mixture thereof having high metal affinity as an electret material. It was found that the interlayer adhesion of the metal substrate / underlying resin layer / electret layer can be improved by introducing it into the layer.
  • the present invention has been achieved on the basis of such knowledge, and the gist thereof is as follows.
  • An electret layer made of a fluororesin is formed on a metal base material through a base resin layer containing a fluororesin, silicon, a silicon compound, or a mixture thereof, and conductive carbon. Characteristic heat-resistant electret material.
  • the thickness of the metal substrate is 10 to 500 ⁇ m
  • the thickness of the base resin layer is 1 to 50 ⁇ m
  • the thickness of the electret layer is 8 to 50 ⁇ m.
  • the proportion of silicon element in the total 100 mol% of fluorine element, silicon element and carbon element contained in the base resin layer is 1 to 50 mol%, A heat-resistant electret material having a ratio of 5 to 10 mol%.
  • the ratio of silicon element and carbon element contained in the base resin layer is smaller than the ratio of carbon element on the metal substrate side, and on the electret layer side.
  • the metal base plate is made of stainless steel, aluminum, brass, iron, or an oxide thereof, and an alloy containing one or more of them. Or nickel, gold, silver, copper, tin, zinc, and platinum on the surface of a thin metal plate made of stainless steel, aluminum, brass, iron, or an oxide thereof, and an alloy containing one or more of these.
  • a heat-resistant electret material comprising a thin metal plate coated with at least one conductive metal selected from the group consisting of:
  • the volume resistance value of the surface of the base resin layer on the electret layer side is 10 10 ⁇ ⁇ m to 10 13 ⁇ ⁇ m, and the volume of the electret layer A heat-resistant electret material having a resistance value of 10 15 ⁇ ⁇ m or more.
  • silicon (Si) having a high metal affinity, a silicon compound, or a mixture thereof (hereinafter sometimes referred to as “Si component”) into the base resin layer
  • Si component silicon
  • Interlayer adhesion of the metal substrate / underlying resin layer / electret layer can be enhanced. That is, as is clear from the periodic table of elements, silicon is a substance that is closer to metal than carbon and has a higher metal affinity, and also has a higher affinity for fluorine (fluoride ions). Therefore, by including such a Si component in the base resin layer, the interlayer adhesion between the base resin layer and the metal base material can be improved. As a result, the interlayer of the metal base material / base resin layer / electret layer can be improved. It becomes possible to realize a heat-resistant electret material having excellent adhesion.
  • the electret layer fluorine resin is preferable as a resin material for the electret fixed electrode because it has a large charge amount and little charge attenuation, and further has a higher melting point than FEP.
  • PTFE thermoplastic urethane resin
  • the electret layer fluorine resin is preferable as a resin material for the electret fixed electrode because it has a large charge amount and little charge attenuation, and further has a higher melting point than FEP.
  • FIG. It is a graph which shows the displacement of the mol% of the silicon element and carbon element in the thickness direction of the base resin layer of the sample of Example 2. It is a graph which shows the displacement of the volume resistance value in the thickness direction of a base resin layer.
  • FIG. 1 is a cross-sectional view showing an example of an embodiment of the heat-resistant electret material of the present invention, wherein 1 is a metal substrate, 2 is a base resin layer, and 3 is an electret layer.
  • the metal substrate used in the present invention is a thin metal plate made of stainless steel, aluminum, titanium, brass, copper, iron, or an oxide thereof, and an alloy containing one or more of these, or stainless steel, aluminum, It is selected from nickel, gold, silver, copper, tin, zinc, and platinum on the surface of a thin metal plate made of titanium, brass, copper, iron, oxides thereof, or an alloy containing one or more of these. It is preferably a thin metal plate coated (plated or vapor-deposited) with at least one conductive metal.
  • the thickness of the metal substrate is not particularly limited in terms of charge retention, but is usually 10 to 500 ⁇ m, and is 50 to 200 ⁇ m from the viewpoint of workability and the recent demand for smaller and lighter electronic devices.
  • charge retention usually 10 to 500 ⁇ m, and is 50 to 200 ⁇ m from the viewpoint of workability and the recent demand for smaller and lighter electronic devices.
  • the volume resistance value in the temperature range of 10 ° C. to 350 ° C. of the metal substrate used in the present invention is more than 60 ⁇ 10 ⁇ 8 ⁇ ⁇ m and less than 100 ⁇ 10 ⁇ 8 ⁇ ⁇ m. preferable.
  • the volume resistivity of the metal substrate is equal to or less than 60 ⁇ 10 -8 ⁇ ⁇ m is not preferable because can not retain the charge long stably holding the electret layer, 100 ⁇ 10 -8 ⁇ ⁇ In the case of m or more, the absolute amount of charges that can be held in the electret layer is reduced, which is not preferable.
  • the fluororesin used in the base resin layer and electret layer of the present invention may be either heat-meltable or non-heat-meltable, and is an unsaturated fluorinated hydrocarbon, unsaturated fluorinated chlorinated hydrocarbon, ether
  • examples thereof include polymers or copolymers such as group-containing unsaturated fluorinated hydrocarbons, or copolymers of these unsaturated fluorinated hydrocarbons with ethylene.
  • these can also be used independently and can also be used as 2 or more types of mixtures.
  • a tetrafluoroethylene polymer a copolymer of tetrafluoroethylene and less than 2% by mass of a copolymerizable fluorine-containing monomer (modified PTFE), tetrafluoroethylene / perfluoro ( Alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (CTFE), polyvinylidene fluoride ( PVDF), tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer, polyvinylidene fluoride, and chlorotrifluoroethylene / ethylene copolymer are preferable.
  • PTFE tetrafluoroethylene polymer
  • PVDF polyvinyliden
  • Ruoroechiren polymer polytetrafluoroethylene
  • / or tetrafluoroethylene and copolymers of copolymerizable fluorinated monomers of less than 2 wt% modified PTFE
  • a treatment for increasing the crystallinity may be added after the electret layer is formed.
  • the method for increasing the crystallinity of the PTFE resin layer is not particularly limited, and examples thereof include rolling, annealing, electron beam irradiation, and the like.
  • a method of slow cooling after heat treatment using an oven or a heating furnace is the simplest and most common.
  • Japanese Patent Application Laid-Open No. 2007-039672 There is a method by EB (electron beam) irradiation described in the publication.
  • the crystallinity of the PTFE layer is preferably in the range of 20 to 80%. If the degree of crystallinity is less than 20%, the charge retention becomes worse, whereas if it exceeds 80%, the elasticity of the material decreases and becomes hard and brittle, so various post-processing (bending, cutting, punching, punching, etc.) sexuality gets worse.
  • Examples of the conductive carbon used in the base resin layer of the present invention include carbon black (Ketjen Black EC, furnace black, channel black, acetylene black, etc.), black pearl, carbon nanofiber, carbon nanotube, carbon nanohorn, and carbon nanoballoon. , Graphene, fullerene, and the like can be used. These may be used alone or in combination of two or more.
  • Si component material As a material for introducing the Si component into the base resin layer (hereinafter sometimes referred to as “Si component material”), a siloxane bond (—O—Si—O—) is formed in the coating film by heat curing.
  • a silane coupling agent such as triethylsilanol, an alkoxysilane, a silicone, a metal alkoxide, an organic siloxane, an aqueous silicate solution, or the like used in Examples described later can be used.
  • silane coupling agent triethylsilanol, hydrolyzable organosilane, vinyl silane, methacryl silane, epoxy silane, amino silane, isocyanate silane and the like can be used.
  • alkoxysilane represented by the formula (1) when n is 0, that is, Si (OR 2 ) 4 is referred to as tetrafunctional alkoxysilane, and when n is 1, that is, R 1 (Si). (OR 2 ) 3 is a trifunctional alkoxysilane, and n is 2, that is, R 1 2 (Si) (OR 2 ) 2 is a bifunctional alkoxysilane, and n is 3, that is, R 1 3 ( Si) (OR 2 ) is a monofunctional alkoxysilane.
  • trifunctional alkoxysilanes include trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, propyltrimethoxysilane, propyltriethoxysilane, Examples include isobutyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, and allyltriethoxysilane.
  • the bifunctional alkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldimethoxysilane, and diphenyldiethoxysilane.
  • tetramethoxysilane, tetraethoxysilane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane and the like are particularly preferable.
  • silicone polyether-modified silicone, epoxy-modified silicone, amino-modified silicone, and the like can be used in addition to straight silicon having only a methyl group or phenyl group as a substituent.
  • metal alkoxide tetraethyl titanate, tetraethyl zirconate, aluminum isopropionate, or the like can be used.
  • organic siloxane polydimethylsiloxane, polymethylvinylsiloxane, or the like can be used.
  • silicate of the silicate aqueous solution atrium silicate, potassium silicate, hafnium silicate, or the like can be used.
  • the above Si component materials may be used alone or in any combination of two or more at any ratio.
  • the base resin layer of the heat-resistant electret material of the present invention is a base resin layer forming coating solution containing fluororesin, Si component material and conductive carbon, bar coating, spray coating, dip coating, spin coating, roller coating, impregnation coating. , Electrostatic coating, curtain flow coating (screen coating), gravure coating, die coating, slide coating, wire bar coating, knife coating, spin flow coating, etc. And can be obtained by drying and / or baking at a temperature of about room temperature to about 400 ° C. for 5 to 60 minutes. It can also be obtained by screen printing, gravure printing, or a method of laminating (thermocompression bonding) a previously prepared base resin layer film. In the case of the coating (coating) method, the heat-resistant electret material can be made thinner and thinner than the film laminating method.
  • the coating solution for forming the base resin layer can contain a binder resin, and the mass ratio of the binder resin to the fluororesin is preferably 5 to 50:95 to 50.
  • a binder resin for example, a resin having heat resistance equivalent to that of a fluororesin, that is, a thermal decomposition starting temperature of 300 ° C. or more and having adhesion to a metal substrate is preferable.
  • Particularly suitable as such a binder resin are polyimide resin (PI), polyamideimide resin (PAI), polyphenylene sulfide resin (PPS), polyethersulfone resin (PES), polyetheretherketone (PEEK), polyether. Imide (PEI), polybenzimidazole (PBI), epoxy resin, or a mixture thereof. More preferably, it is PAI.
  • the binder resin may be dissolved in the liquid medium or may be uniformly dispersed in the liquid medium as fine particles.
  • Liquid media that can be used include water, polar organic solvents, non-polar organic solvents, and mixtures thereof. When water is used as the liquid medium, it is preferable to add a surfactant to the liquid medium in order to reduce the surface tension of the liquid medium and improve the dispersibility of the binder resin and fluororesin powder.
  • the binder resin is PI, PAI, PES, or the like and is relatively easily dissolved in an organic solvent such as N-methylpyrrolidone or a mixture of N-methylpyrrolidone and diacetone alcohol or xylene
  • the binder resin It is preferable to use by dissolving in a liquid medium.
  • water containing a surfactant is used as the liquid medium, and the binder resin is used in the liquid medium. It is preferable to uniformly disperse and use.
  • the thickness of the base resin layer thus obtained is not particularly limited, but is preferably 1 to 50 ⁇ m. Thickness of the base resin layer that has conductivity and contributes to interlayer adhesion is desirable from the viewpoint of charge retention and interlayer adhesion. However, even if it is too large, the interlayer adhesion is caused by cohesive peeling in the layer. Sex is reduced. In general, a charge retention rate of 80% or more is sufficient when a heat-resistant electret material is used as a condenser microphone. Therefore, the film thickness of the base resin layer is particularly preferably in the range of 3 to 30 ⁇ m. A range of 5 to 20 ⁇ m is more preferable.
  • the volume resistance value of the surface of the base resin layer on the electret layer side in the temperature range of 10 ° C. to 350 ° C. is preferably 10 10 to 10 13 ⁇ ⁇ m. If the volume resistance value of the surface of the base resin layer on the electret layer side is too small, it is not preferable because the charge retained in the electret layer cannot be stably maintained for a long time, and if it is too large, it is retained in the electret layer. This is not preferable because the absolute amount of charge that can be generated is reduced.
  • the base resin layer has a feature that the volume resistance value sequentially increases from the metal substrate side to the electret layer side in the thickness direction, and the volume resistance value at the thickness 1/2 of the base resin layer is 10 It is larger than 9 ⁇ ⁇ m and not more than 10 12 ⁇ ⁇ m, and the volume resistance value on the surface of the base resin layer on the electret layer side is not less than 10 10 ⁇ ⁇ m, more preferably not less than 10 11 ⁇ ⁇ m and not more than 10 13 ⁇ ⁇ m. It becomes.
  • the proportion of conductive carbon (carbon element) contained in the base resin layer is a metal group as will be described later. This is thought to be due to the fact that the proportion of insulating silicon element decreases with increasing from the material side to the electret layer side.
  • the base resin layer of the heat-resistant electret material of the present invention has an elemental analysis for obtaining a good balance between the improvement in interlayer adhesion due to the inclusion of the Si component and the improvement in conductivity due to the inclusion of conductive carbon.
  • the ratio of silicon element to the total of 100 mol% of fluorine element, silicon element and carbon element contained in the base resin layer determined by 1 is 1 to 5 mol%, and the ratio of carbon element is 5 to 10 mol%. Is preferred. If the ratio of silicon element is less than this range, the effect of improving interlayer adhesion by introducing the Si component into the base resin layer cannot be sufficiently obtained, and if it is too high, the conductivity of the base resin layer is lowered. As a result, the charge retention characteristics deteriorate.
  • the ratio of the carbon element corresponds to the total of the carbon element derived from the fluororesin and the carbon element derived from the conductive carbon and the carbon element derived from other carbon-containing components such as the binder resin in the base resin layer.
  • this ratio is too less than the above range, the conductivity of the base resin layer is insufficient, not only the charge retention characteristics are lowered, but also the flexibility is impaired, due to shear stress at the time of bending and punching, Problems such as film breakage (chips) and cracks occur. If the amount is too large, the heat resistance at high temperatures during soldering is reduced.
  • the base resin layer of the heat-resistant electret material of the present invention is such that the ratio of silicon element and carbon element contained is smaller than the ratio of carbon element on the metal substrate side, and the electret layer On the side, the proportion of silicon element is higher than the proportion of carbon element.
  • the component gradient occurs in the process of volatilization of the solvent due to the specific gravity difference between the carbon element and the silicon element, so that more carbon elements gather than the silicon element on the metal substrate side, And since there is a tendency that more silicon element collects than carbon element on the electret layer side, adhesion between the base resin layer and the electret layer can be improved, and conductivity can be imparted to the base resin layer. It is thought that it will become.
  • the content of the Si component material in the above-described coating resin for forming the base resin layer is based on the fluororesin in the coating solution for forming the base resin layer.
  • 1.0 to 115.0 mass%, particularly 1.1 to 111.0 mass% is preferable.
  • the conductive carbon content is preferably 10.0 to 20.0% by mass, particularly 11.0 to 15.0% by mass, based on the fluororesin in the base resin layer forming coating solution.
  • the electret layer of the heat-resistant electret material of the present invention is a fluororesin-containing electret layer-forming coating solution prepared in the same manner as the base resin layer-forming coating solution except that it does not contain conductive carbon and Si component materials. And can be formed on the base resin layer in the same manner as the base resin layer.
  • the above base resin layer-forming coating solution is applied onto a metal substrate and the temperature is about 100 to 200 ° C. for about 1 to 10 minutes. Then, the electret layer forming coating solution is applied onto the dried coating film, dried at about 100 to 200 ° C. for about 1 to 10 minutes, and finally heated and fired at about 350 to 450 ° C. for about 1 to 10 minutes.
  • the base resin layer and the electret layer are preferably laminated on the metal substrate.
  • the thickness of the electret layer thus obtained is not particularly limited, but is preferably 8 to 50 ⁇ m, particularly preferably 15 to 45 ⁇ m.
  • the volume resistance value of the electret layer in the temperature range of 10 ° C. to 350 ° C. is preferably 10 15 ⁇ ⁇ m or more. When the volume resistance value of the electret layer is less than 10 15 ⁇ ⁇ m, the absolute amount of charges held in the electret layer is reduced, and the long-term holding stability of the held charges is also deteriorated. Absent.
  • the heat-resistant electret material of the present invention preferably has a metal substrate thickness of 50 to 500 ⁇ m, more preferably 80 to 300 ⁇ m, a base resin layer thickness of 1 to 50 ⁇ m, more preferably 2 to 20 ⁇ m, and an electret layer thickness.
  • the volume resistance value in the temperature range from 350 ° C.
  • a laminated member satisfying 100 ⁇ 10 ⁇ 8 ⁇ ⁇ m, 10 10 ⁇ ⁇ m ⁇ B ⁇ 10 13 ⁇ ⁇ m, and C ⁇ 10 15 ⁇ ⁇ m is preferable.
  • the heat-resistant electret material of the present invention is a conductive metal substrate and electret layer containing a fluororesin, an Si component and conductive carbon between a metal thin plate base material and a fluororesin layer which is an electret layer.
  • Such a heat-resistant electret material according to the present invention can be manufactured by only a wet process, not a dry process that requires a high level of dustproof equipment, so that the electret material can be provided at a low cost. Moreover, since the heat-resistant electret material of the present invention is a thin-film electret material with high charge retention, the members (earphones, headphones, microphones, etc.) that use this material can be made more compact.
  • a liquid A consisting of 0.5% by mass of 2-mass% 2- (diethylamino) ethanol was prepared.
  • a solution prepared by adjusting triethylsilanol (silane coupling agent) manufactured by Tokyo Chemical Industry Co., Ltd. with distilled water to 10% by mass is liquid B.
  • a liquid and B liquid were mixed by the compounding quantity shown in Table 1, and it was set as the coating liquid for base resin layer formation.
  • Table 1 the ratio of carbon black to the PTFE in the prepared coating solution for forming the base resin layer and the ratio of pure triethylsilanol are shown together.
  • a coating solution for forming an electret layer consisting of 0.3% by mass of 5-trimethylbenzene was prepared.
  • the laminated member is subjected to a charging process by performing a corona discharge of -1,000 V using a high voltage power source amplification / control device (MODEL610-C manufactured by Trek Japan Co., Ltd.) in the atmosphere of normal temperature and normal pressure.
  • a high voltage power source amplification / control device MODEL610-C manufactured by Trek Japan Co., Ltd.
  • samples of electret materials were produced.
  • the thickness of the base resin layer of each sample is 5 ⁇ m, and the thickness of the electret layer is 25 ⁇ m.
  • ⁇ Coating hardness> Each sample was evaluated for coating film hardness. The results are shown in Table 5. The hardness was measured on the surface of the electret layer based on JIS-K5400 using “553-M1” manufactured by Yasuda Seiki Co., Ltd. The value of the coating film hardness indicates that the coating film hardness is higher in the order of B ⁇ HB ⁇ F ⁇ B ⁇ H ⁇ 2H ⁇ .
  • the peeling failure rate is high, and when the thickness is 60 ⁇ m or more, cohesive peeling occurs in the layer and the peeling failure rate tends to increase. It is in. Accordingly, it can be seen that a thickness range of 1 to 50 ⁇ m is appropriate for the base resin layer.
  • the thickness of the electret layer is less than 5 ⁇ m, the charge retention performance is remarkably deteriorated. Energy is needed, material and energy are wasted. It is generally said that the thinner the electret layer is, the better the S / N ratio is.
  • the thickness range of the electret layer for which reduction in thickness and cost is required is 8 to It can be seen that 50 ⁇ m is suitable.
  • the etching conditions were 2 kV and 20 mA with Ar + , and the etching rate was 5.0 nm / min.
  • Mg—K ⁇ was used as the light source, and the measurement was performed under the conditions of an output of 8 kW ⁇ 30 mA and a degree of vacuum of 5 ⁇ 10 ⁇ 6 Pa. The results are shown in FIG. 5 (Example 1) and FIG. 6 (Example 2).

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Acoustics & Sound (AREA)
  • Signal Processing (AREA)
  • Electrostatic, Electromagnetic, Magneto- Strictive, And Variable-Resistance Transducers (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un matériau électret thermorésistant qui présente une grande capacité de rétention de la charge, une faible atténuation de la charge et une adhérence supérieure entre un substrat métallique et une couche d'électret formée à partir d'une résine fluorée, en particulier du polytétrafluoroéthylène (PTFE). Un matériau électret thermorésistant (10) comprend, sur un substrat métallique (1), un électret (3) formé à partir d'une résine fluorée, avec entre eux une couche de mise à la masse en résine (2) comprenant une résine fluorée, du silicium et/ou un composé de silicium, et du carbone conducteur. En introduisant du silicium hautement métallophile et/ou un composé de silicium hautement métallophile dans la couche de mise à la masse en résine en une proportion qui ne compromet pas ses caractéristiques de rétention de charge du matériau électret, il est possible d'améliorer l'adhérence entre le substrat métallique, la couche de mise à la masse en résine et la couche d'électret.
PCT/JP2012/067953 2011-07-15 2012-07-13 Matériau électret thermorésistant et microphone à condensateur WO2013011949A1 (fr)

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WO2018101359A1 (fr) * 2016-11-30 2018-06-07 株式会社ユポ・コーポレーション Élément piézoélectrique et instrument de musique

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JP6381390B2 (ja) * 2014-09-30 2018-08-29 株式会社アコー 音・振動検出センサ

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JP2005262497A (ja) * 2004-03-16 2005-09-29 Nippon Valqua Ind Ltd エレクトレット固定電極用積層板
WO2009128503A1 (fr) * 2008-04-17 2009-10-22 旭硝子株式会社 Électret et dispositif de conversion à induction électrostatique
JP2010279024A (ja) * 2009-04-27 2010-12-09 Nitto Denko Corp エレクトレット材および静電型音響変換器

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JP2005262497A (ja) * 2004-03-16 2005-09-29 Nippon Valqua Ind Ltd エレクトレット固定電極用積層板
WO2009128503A1 (fr) * 2008-04-17 2009-10-22 旭硝子株式会社 Électret et dispositif de conversion à induction électrostatique
JP2010279024A (ja) * 2009-04-27 2010-12-09 Nitto Denko Corp エレクトレット材および静電型音響変換器

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Publication number Priority date Publication date Assignee Title
WO2018101359A1 (fr) * 2016-11-30 2018-06-07 株式会社ユポ・コーポレーション Élément piézoélectrique et instrument de musique
CN109983593A (zh) * 2016-11-30 2019-07-05 优泊公司 压电元件及乐器
JPWO2018101359A1 (ja) * 2016-11-30 2019-10-24 株式会社ユポ・コーポレーション 圧電素子および楽器
US11176918B2 (en) 2016-11-30 2021-11-16 Yupo Corporation Piezoelectric element and musical instrument

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