TWI836005B - Piezoelectric sensor and method of manufacturing piezoelectric sensor - Google Patents

Abstract

An objective of the present invention is to provide a piezoelectric sensor that exhibits a high output voltage even during long-term use.

One embodiment of the present invention relates to a piezoelectric sensor and a method of manufacturing the piezoelectric sensor, the piezoelectric sensor including a metal layer, a piezoelectric layer, and a conductive coating layer in this order, wherein the ratio of the bending rigidity of the metal layer to the bending rigidity of the conductive coating layer is 10 to 100.

Description

壓電感測器及壓電感測器的製造方法 Piezo-inductor sensor and method for manufacturing the same

本發明的一實施型態係關於壓電感測器及壓電感測器的製造方法。 An embodiment of the present invention relates to a piezoelectric sensor and a manufacturing method of the piezoelectric sensor.

壓電感測器(踏墊(mat)感測器)常用於檢測人或物品的出入等。 Piezoelectric inductors (mat sensors) are often used to detect the entry and exit of people or objects.

如此的壓電感測器，在專利文獻1中揭示一種壓電感測器，其係在壓電片的一面疊合由鋁箔構成的訊號(signal)電極，在另一面疊合由鋁箔構成的接地極而成者。 Such a piezoelectric inductor is disclosed in Patent Document 1, which is formed by stacking a signal electrode made of aluminum foil on one side of a piezoelectric sheet and a ground electrode made of aluminum foil on the other side.

還有專利文獻2中揭示一種壓電感測器，其係在壓電層的兩側設置包含彈性體(elastomer)及導電材之電極層而成者。 Patent document 2 also discloses a piezoelectric inductor, which is formed by setting electrode layers including an elastomer and a conductive material on both sides of a piezoelectric layer.

[先前技術文獻] [Prior technical literature]

〔專利文獻〕 [Patent document]

[專利文獻1]日本特開2017-179126號公報 [Patent Document 1] Japanese Patent Publication No. 2017-179126

[專利文獻2]WO 2017/010135號 [Patent Document 2] WO 2017/010135

本發明者經過確認後發現：如前述專利文獻所揭示的以往壓電感測器若長期間使用，就會有輸出電壓降低，且依情況有時會有輸出電壓降低到無法再作為壓電感測器使用的程度之情形。 After confirmation, the inventor found that if the conventional piezoelectric sensor disclosed in the aforementioned patent document is used for a long time, the output voltage will decrease, and depending on the situation, the output voltage may decrease to the point that it can no longer be used as a piezoelectric sensor. The degree of use of the detector.

如上述，輸出電壓降低，就會無法與雜訊相區別，容易發生錯誤檢測，而必須常常更換壓電感測器。 As mentioned above, if the output voltage decreases, it will be unable to distinguish it from noise, and erroneous detection will easily occur, and the piezoelectric sensor must be replaced frequently.

本發明的一實施型態係提供一種即使長期使用亦會顯示高輸出電壓的壓電感測器。 An embodiment of the present invention provides a piezoelectric sensor that exhibits a high output voltage even after long-term use.

在如此的狀況下，本發明者為了解決前述課題而專心致志進行探討之結果發現：根據下述構成例即可解決前述課題。 Under such circumstances, the inventors of the present invention conducted intensive studies to solve the above-mentioned problems and found that the above-mentioned problems can be solved according to the following configuration example.

本發明的構成例係如以下所述： The composition examples of the present invention are as follows:

〔1〕壓電感測器，係依序包含金屬層、壓電層及導電性塗膜層，其中， [1] A piezoelectric sensor includes a metal layer, a piezoelectric layer and a conductive coating layer in sequence, where,

前述金屬層的彎曲剛性與前述導電性塗膜層的彎曲剛性之比為10至100。 The ratio of the bending rigidity of the aforementioned metal layer to the bending rigidity of the aforementioned conductive coating layer is 10 to 100.

〔2〕上述〔1〕所述之壓電感測器，其中，前述導電性塗膜層係包含導電性填料(filler)及黏結劑(binder)之層。 [2] The piezoelectric inductor described in [1] above, wherein the conductive coating layer comprises a layer of conductive filler and binder.

〔3〕上述〔1〕或〔2〕所述之壓電感測器，其中，前述壓電層係包含有機聚合物之不織布或織布，而該有機聚合物不具有起因於分子及結晶構造的偶極(dipole)。 [3] The piezoelectric inductor described in [1] or [2] above, wherein the piezoelectric layer is a non-woven fabric or a woven fabric comprising an organic polymer, and the organic polymer does not have a dipole arising from the molecular and crystal structure.

〔4〕上述〔3〕所述之壓電感測器，其中，前述有機聚合物為聚四氟乙烯。 [4] The piezoelectric inductor described in [3] above, wherein the organic polymer is polytetrafluoroethylene.

〔5〕上述〔3〕或〔4〕所述之壓電感測器，其中，構成前述不織布或織布之纖維的平均纖維徑為0.05至50μm。 [5] The piezoelectric inductor described in [3] or [4] above, wherein the average fiber diameter of the fiber constituting the nonwoven fabric or woven fabric is 0.05 to 50 μm.

〔6〕上述〔3〕至〔5〕中任一項所述之壓電感測器，其中，構成前述不織布或織布之纖維的纖維徑變動係數為0.7以下。 [6] A piezoelectric inductor as described in any one of [3] to [5] above, wherein the fiber diameter variation coefficient of the fiber constituting the nonwoven fabric or woven fabric is less than 0.7.

〔7〕上述〔1〕至〔6〕中任一項所述之壓電感測器，其中，前述壓電層的孔隙率為0.1至70體積%。 [7] The piezoelectric sensor according to any one of the above [1] to [6], wherein the piezoelectric layer has a porosity of 0.1 to 70% by volume.

〔8〕一種依序包含金屬層、壓電層及導電性塗膜層之壓電感測器的製造方法，其包含：在壓電層塗裝包含導電性填料及黏結劑之組成物，然後使該塗裝的組成物乾燥或硬化之步驟。 [8] A method for manufacturing a piezoelectric inductor comprising a metal layer, a piezoelectric layer and a conductive coating layer in sequence, comprising: coating the piezoelectric layer with a composition comprising a conductive filler and a binder, and then drying or curing the coated composition.

根據本發明的一實施型態，即使初期及長期使用，皆可得到顯示高輸出電壓的壓電感測器，可得到具有長期可靠性，具體而言係即使長期使用，也能夠容易地判別檢測對象的壓力與雜訊，鮮少會錯誤檢測之壓電感測器。 According to an embodiment of the present invention, it is possible to obtain a piezoelectric sensor that exhibits a high output voltage even in the initial stage and in long-term use, and has long-term reliability. Specifically, it is possible to easily identify and detect even in long-term use. The piezoelectric sensor rarely detects the pressure and noise of the object incorrectly.

《壓電感測器》 《Piezo-inductor detector》

本發明的一實施型態之壓電感測器(以下稱為「本感測器」)，係依序包含金屬層、壓電層及導電性塗膜層，其中，前述金屬層的彎曲剛性與前述導電性塗膜層的彎曲剛性之比(金屬層的彎曲剛性/導電性塗膜層的彎曲剛性)為10至100。 A piezoelectric inductor of an embodiment of the present invention (hereinafter referred to as "the present sensor") comprises a metal layer, a piezoelectric layer and a conductive coating layer in sequence, wherein the ratio of the bending rigidity of the metal layer to the bending rigidity of the conductive coating layer (bending rigidity of the metal layer/bending rigidity of the conductive coating layer) is 10 to 100.

本感測器因為使用金屬層及導電性塗膜層，所以會成為如前述的彎曲剛性之比，由於包夾壓電層之層具有如此的彎曲剛性之比，因此即使初期及長期使用，皆可得到顯示高輸出電壓的壓電感測器，可得到具有長期可靠性，具體而言係即使長期使用，也能夠容易地判別檢測對象的壓力與雜訊，鮮少會錯誤檢測之壓電感測器。 Because this sensor uses a metal layer and a conductive coating layer, it will have the bending stiffness ratio as mentioned above. Since the layer sandwiching the piezoelectric layer has such a bending stiffness ratio, it will be stable even in the initial and long-term use. A piezoelectric sensor showing a high output voltage can be obtained, and a piezoelectric sensor with long-term reliability can be obtained. Specifically, a piezoelectric inductor can easily determine the pressure and noise of the detection target and rarely detect errors even if it is used for a long time. detector.

本發明中，所謂的「長期使用」，係指例如：如下述實施例按壓本感測器1000次以上之情況。 In the present invention, the so-called "long-term use" refers to, for example, pressing the sensor more than 1,000 times as in the following embodiment.

本感測器會產生如此的效果原因為何雖然還不清楚，但可想成是因為本感測器受到按壓時壓電層的上表面側與下表面側的變形量出現差異，因而本感測器會顯示高輸出電壓，以及可想成是由於可抑制壓電層的塑性變形，因而本感測器在長時間顯示出高輸出電壓。 Although it is not clear why this sensor produces such an effect, it is thought that when this sensor is pressed, the deformation amount of the upper surface and the lower surface of the piezoelectric layer differs, so this sensor displays a high output voltage, and it is thought that the plastic deformation of the piezoelectric layer can be suppressed, so this sensor displays a high output voltage for a long time.

從即使初期及長期使用時均顯示更高輸出電壓的感測器之點來看，前述的彎曲剛性之比係在10以上100以下，較佳者為20以上，更佳者為30以上，較佳者為70以下，更佳者為60以下，特佳者為50以下。 From the point of view of the sensor showing a higher output voltage even in the initial and long-term use, the aforementioned bending stiffness ratio is 10 or more and 100 or less, preferably 20 or more, still more preferably 30 or more, and preferably The best one is below 70, the best one is below 60, and the very best one is below 50.

該彎曲剛性之比，具體上係可用下述實施例中揭示的方法測定。 The ratio of bending rigidity can be measured specifically by the method disclosed in the following examples.

本感測器以配置成壓力係施加於前述金屬層側而使用者為佳。如此使用本感測器，可更加抑制壓電層的塑性變形，因此即使經過更長時間亦可容易地得到顯示高輸出電壓的感測器。 The sensor is preferably configured so that pressure is applied to the side of the metal layer. By using this sensor in this way, the plastic deformation of the piezoelectric layer can be further suppressed, so that a sensor showing a high output voltage can be easily obtained even after a longer period of time.

本感測器並無特別限制於包含有金屬層、壓電層及導電性塗膜層，亦可視需要而在該等層之間等含有接著層等習知層，但較佳的是在壓電層的最大面的一側具有金屬層，在壓電層的最大面的另一側具有導電性塗膜層，更佳的是金屬層直接接於壓電層的最大面的一側，導電性塗膜層直接接於壓電層的最大面的另一側。換言之，與壓電層的最大面相隣的兩個層的彎曲剛性之比以在前述範圍內為佳。 The sensor is not particularly limited to include a metal layer, a piezoelectric layer and a conductive coating layer. It may also contain conventional layers such as adhesive layers between these layers if necessary, but it is better to One side of the largest surface of the electrical layer has a metal layer, and the other side of the largest surface of the piezoelectric layer has a conductive coating layer. More preferably, the metal layer is directly connected to one side of the largest surface of the piezoelectric layer to conduct electricity. The flexible coating layer is directly connected to the other side of the largest surface of the piezoelectric layer. In other words, the ratio of the bending rigidities of the two layers adjacent to the largest surface of the piezoelectric layer is preferably within the aforementioned range.

另外，本感測器可具有以往的壓電感測器所具有的習知層，例如絶緣層、前述金屬層及導電性塗膜層以外的電極層等，以及，可具有從本感測器取電之構件等。 In addition, the present sensor may have conventional layers that are present in conventional piezoelectric sensors, such as insulating layers, electrode layers other than the aforementioned metal layers and conductive coating layers, and may have layers from the present sensor. Components for taking electricity, etc.

製造本感測器之方法，只要可得到依序包含金屬層、壓電層及導電性塗膜層之積層體即可，並無特別限制，例如，可將下述導電性塗料等塗裝於絶緣層等的絶緣體，然後將所得到的帶有導電性塗膜層之絶緣體以導電性塗膜層成為壓電層側的方式疊合，或者將下述導電性塗料等塗裝於支撐體，然後將從所得到的帶有導電性塗膜層之支撐體剝離的導電性塗膜層與壓電層疊合，但從可得到有良好的製造容易性，且在初期及長期使用時都顯示高輸出電壓之感測器，可容易地得到有良好的長期可靠性之感測器等之點來看，以下述的本製造方法為佳。 The method of manufacturing this sensor is not particularly limited as long as a laminate including a metal layer, a piezoelectric layer, and a conductive coating layer in this order can be obtained. For example, the following conductive coatings can be coated on An insulator such as an insulating layer, and then the obtained insulator with a conductive coating layer is laminated so that the conductive coating layer becomes the piezoelectric layer side, or the following conductive paint, etc. is applied to the support body, and then the conductive coating layer peeled off from the obtained support with the conductive coating layer and the piezoelectric layer are laminated, but it can be obtained with good ease of manufacturing and is stable both in the initial stage and in long-term use. In view of the fact that a sensor showing a high output voltage can be easily obtained and a sensor with good long-term reliability can be easily obtained, the following manufacturing method is preferable.

在使用如前述帶有導電性塗膜層之絶緣體的情況，在前述彎曲剛性之比的計算時並不考慮該絶緣體。 When using an insulator with a conductive coating layer as described above, the insulator is not considered in the calculation of the aforementioned bending stiffness ratio.

本感測器係檢測壓力之感測器，適合用於踏墊感測器、衝撃感測器、脈波等生物感測器、落座感測器等。 This sensor is a pressure sensor, suitable for use in foot pad sensors, impact sensors, pulse wave and other biosensors, seat sensors, etc.

<金屬層> <Metal layer>

前述金屬層並無特別限制，可採用以往壓電感測器中使用的電極。 The aforementioned metal layer is not particularly limited, and electrodes used in conventional piezoelectric sensors can be used.

前述金屬層的形狀、大小等，只要依據所希望的用途適當地選擇即可，並無特別限制。 The shape, size, etc. of the aforementioned metal layer can be appropriately selected according to the desired use and there is no particular limitation.

構成前述金屬層之金屬並無特別限制，可為例如：鋰、鈹、鎂、鈣、鍶、鋇、硼、鋁、鎵、銦、銻、錫、銀、金、銅、鎳、鈀、鉑、鉻、鉬、鎢、錳、鈷、上列金屬的合金。其中特別適合者係例如鋁、銅、銀、鎳。 The metal constituting the aforementioned metal layer is not particularly limited and may be, for example: lithium, beryllium, magnesium, calcium, strontium, barium, boron, aluminum, gallium, indium, antimony, tin, silver, gold, copper, nickel, palladium, platinum , chromium, molybdenum, tungsten, manganese, cobalt, alloys of the above metals. Particularly suitable among these are, for example, aluminum, copper, silver, nickel.

前述金屬層從本感測器的製造容易性、可容易地得到彎曲剛性之比在前述範圍內的感測器等之點來看，以採用市售的金屬板(箔)為佳。 The metal layer is preferably a commercially available metal plate (foil) from the viewpoint of ease of manufacturing of the sensor and the ease of obtaining a sensor with a bending rigidity ratio within the above range.

從即使初期及長期使用時皆可得到顯示高輸出電壓的感測器等之點來看，前述金屬層的彎曲剛性之值較佳者為10GPa以上，更佳者為40GPa以上，又更佳者為50GPa以上，較佳者為300GPa以下，更佳者為200GPa以下。 From the viewpoint of obtaining a sensor showing a high output voltage even during initial and long-term use, the bending rigidity value of the metal layer is preferably 10 GPa or more, more preferably 40 GPa or more, and still more preferably It is 50 GPa or more, preferably it is 300 GPa or less, and more preferably it is 200 GPa or less.

前述金屬層的厚度並無特別限制，可為與以往的電極一樣的厚度，但以能夠讓彎曲剛性在前述範圍之厚度為佳，從可容易地製造所 希望的感測器等之點來看，較佳者為0.001mm以上，更佳者為0.01mm以上，較佳者為1mm以下，更佳者為0.1mm以下。 The thickness of the metal layer is not particularly limited and can be the same as that of conventional electrodes. However, a thickness that can keep the bending rigidity within the aforementioned range is preferred, so that the entire metal layer can be easily manufactured. From the perspective of desired sensors, the preferred ones are 0.001mm or more, the more preferred ones are 0.01mm or less, the preferred ones are 1mm or less, and the more preferred ones are 0.1mm or less.

<導電性塗膜層> <Conductive coating layer>

前述導電性塗膜層只要是由導電性塗料形成之具有導電性的層即可而無特別限制，但通常是要發揮作為電極的機能之層。該導電性塗料並無特別限制，可採用習知塗料，且以包含導電性填料及黏結劑之導電性塗料為佳。 The conductive coating layer is not particularly limited as long as it is a conductive layer formed of a conductive coating, but it is usually a layer that functions as an electrode. The conductive coating is not particularly limited, and conventional coatings can be used, and conductive coatings containing conductive fillers and binders are preferred.

本發明中，所謂的「導電性」，係指具有低於1×10^-3Ω．cm之比電阻。該比電阻可用數位萬用電表(digital multimeter)測出電阻，然後利用下述式計算。 In the present invention, the so-called "conductivity" refers to a specific resistance lower than 1×10 ^-3 Ω. cm. The specific resistance can be measured by a digital multimeter and then calculated using the following formula.

比電阻(Ω．cm)=R×S/l 〔R：數位萬用電表測出的電阻值，S：由導電性塗料形成的層的截面積，l：電極間距離〕 Specific resistance (Ω.cm) = R×S/l 〔R: resistance value measured by digital multimeter, S: cross-sectional area of the layer formed by the conductive coating, l: distance between electrodes〕

前述導電性填料並無特別限制，可採用習知填料。 The aforementioned conductive filler is not particularly limited, and conventional fillers can be used.

前述導電性塗料中含有的導電性填料可為1種，亦可為形狀、大小、材質等不相同之2種以上。 The conductive filler contained in the conductive paint may be one type, or two or more types having different shapes, sizes, materials, etc.

前述導電性填料的材質，只要是具有導電性之材質即可並無特別限制，可為例如銅、銀、金、錫、鉍、鋅、銦、鎳、鈀等金屬、包含此等金屬之合金、碳黑、石墨，其中尤以銅、銀、碳黑為佳。 The material of the conductive filler is not particularly limited as long as it is conductive. It can be metals such as copper, silver, gold, tin, bismuth, zinc, indium, nickel, palladium, alloys containing these metals, carbon black, and graphite, among which copper, silver, and carbon black are particularly preferred.

前述導電性填料亦可為藉由在某種材料的表面進行前述金屬或合金等的鍍覆(plating)等而得到之填料。 The conductive filler may be a filler obtained by plating the metal, alloy, etc. on the surface of a certain material.

前述導電性填料的形狀亦無特別限制，可為例如塊狀、球狀、薄片狀、針狀、纖維狀、樹枝(dendrite)狀、線圈(coil)狀。 The shape of the conductive filler is not particularly limited, and may be, for example, block, spherical, flake, needle, fiber, dendrite, or coil.

前述導電性填料之以雷射繞射散射法(Microtrac法)測出的中值粒徑(Median diameter)(D50)，從可得到塗裝性良好的塗料，可容易地得到導電性良好的層等之點來看，以在5至30μm為佳。 The median diameter (D50) of the conductive filler measured by the Microtrac method is preferably between 5 and 30 μm, from the perspective of obtaining a coating with good coating properties and easily obtaining a layer with good conductivity.

從可容易地得到導電性良好的層之點來看，相對於前述導電性塗料的固形分100質量%，前述導電性填料的含量以60質量%以上為佳，更佳者為65質量%以上，以在95質量%以下為佳，更佳者為93質量%以下。 From the point of view of being able to easily obtain a layer with good conductivity, the content of the conductive filler is preferably 60% by mass or more, more preferably 65% by mass or more, and preferably 95% by mass or less, and more preferably 93% by mass or less, relative to 100% by mass of the solid content of the conductive coating.

前述黏結劑雖無特別限制，但以能夠保持前述導電性填料者為佳。 Although the aforementioned binder is not particularly limited, it is preferably one that can retain the aforementioned conductive filler.

前述導電性塗料中含有的黏結劑可為1種亦可為2種以上。 The binder contained in the conductive coating may be one or more than one.

前述黏結劑並無特別限制，可為例如：聚酯樹脂、丙烯酸樹脂、丁醛樹脂、熱塑性醯亞胺樹脂等熱可塑性樹脂；雙酚A型、雙酚F型、酚醛(novolak)型等環氧樹脂、液狀環氧化合物等環氧化合物、不飽和聚酯樹脂等聚酯樹脂、聚胺酯樹脂、可溶酚醛(resol)型、酚醛(novolak)型等酚樹脂、醯亞胺樹脂等熱硬化性樹脂；苯乙烯系彈性體、烯烴系彈性體、聚酯系彈性體、聚胺酯系彈性體、聚醯胺系彈性體、矽膠系彈性體等彈性體。 The aforementioned adhesive is not particularly limited, and may be, for example: thermoplastic resins such as polyester resins, acrylic resins, butyral resins, and thermoplastic imide resins; epoxy resins such as bisphenol A type, bisphenol F type, and novolak type, epoxy compounds such as liquid epoxy compounds, polyester resins such as unsaturated polyester resins, polyurethane resins, phenolic resins such as resol type and novolak type, thermosetting resins such as imide resins; elastomers such as styrene elastomers, olefin elastomers, polyester elastomers, polyurethane elastomers, polyamide elastomers, and silicone elastomers.

從可充分保持導電性填料，可容易地得到形狀保持性及導電性良好的層等之點來看，相對於前述導電性填料100質量份，前述黏結 劑的含量以在5質量份以上為佳，更佳者為7質量份以上，以在35質量份以下為佳，更佳者為20質量份以下。 From the viewpoint that the conductive filler can be fully retained and a layer with good shape retention and conductivity can be easily obtained, the above-mentioned bonding is The content of the agent is preferably not less than 5 parts by mass, more preferably not less than 7 parts by mass, preferably not more than 35 parts by mass, and more preferably not more than 20 parts by mass.

從塗裝性等之點來看，前述導電性塗料以含有1種或2種以上的溶劑為佳，該溶劑並無特別限制，可為例如：甲醇、乙醇、異丙醇、丁基卡必醇(butyl carbitol)、丁氧基乙醇(butyl cellosolve)、丙二醇甲醚(propylene glycol monomethyl ether)等醇系溶劑；甲苯、二甲苯等芳香族系溶劑、甲基異丁酮(methyl isobutyl ketone)等酮系溶劑；醋酸甲酯、醋酸乙酯、丁基卡必醇醋酸酯(butyl carbitol acetate)等酯系溶劑。 From the perspective of coating properties, the conductive coating preferably contains one or more solvents. The solvent is not particularly limited and may be, for example, alcohol solvents such as methanol, ethanol, isopropyl alcohol, butyl carbitol, butyl cellosolve, propylene glycol monomethyl ether, etc.; aromatic solvents such as toluene and xylene; ketone solvents such as methyl isobutyl ketone; ester solvents such as methyl acetate, ethyl acetate, butyl carbitol acetate, etc.

前述導電性塗料中，除了前述成分以外，還可視需要在不損及本發明的效果之範圍內再含有以往習知添加劑。 In addition to the aforementioned components, the aforementioned conductive coating may also contain conventionally known additives as needed within the scope that does not impair the effects of the present invention.

如此添加劑可列舉例如：棕櫚酸(palmitic acid)、硬脂酸(stearic acid)等飽和脂肪酸；亞麻酸(linolenic acid)、亞油酸(linoleic acid)、油酸(oleic acid)等不飽和脂肪酸；該等酸的金屬鹽(金屬之例：鈉、鉀)；乳酸、酒石酸等具有羥基之有機酸；烷基磺酸系、烷基苯磺酸等之具有磺酸基之有機酸；金屬螯合形成劑；用來使硬化性樹脂硬化之硬化劑；分散劑；成膜助劑；表面調整劑；塑化劑；抗老化劑；顏料。 Examples of such additives include: saturated fatty acids such as palmitic acid and stearic acid; unsaturated fatty acids such as linolenic acid, linoleic acid, and oleic acid; metal salts of these acids (metallic examples: sodium and potassium); organic acids with hydroxyl groups such as lactic acid and tartaric acid; organic acids with sulfonic groups such as alkylsulfonic acid series and alkylbenzenesulfonic acid; metal chelating agents; hardeners for hardening hardening resins; dispersants; film-forming aids; surface conditioners; plasticizers; anti-aging agents; and pigments.

該等添加劑分別可為1種、或2種以上。 These additives may be one or more than one.

從初期及長期使用時可容易地得到顯示高輸出電壓的感測器等之點來看，前述導電性塗膜層的彎曲剛性之值以在0.1GPa以上為佳，更佳者為0.4GPa以上，特佳者為0.5GPa以上，以在30GPa以下為佳，更佳者為20GPa以下，特佳者為10GPa以下。 From the point of view that a sensor showing a high output voltage can be easily obtained during initial and long-term use, the bending rigidity value of the conductive coating layer is preferably above 0.1 GPa, more preferably above 0.4 GPa, and particularly preferably above 0.5 GPa, and preferably below 30 GPa, more preferably below 20 GPa, and particularly preferably below 10 GPa.

前述導電性塗膜層的厚度並無特別限制，可為與以往的電極一樣的厚度，但以能夠讓彎曲剛性在前述範圍之厚度為佳，從可容易地製造所希望的感測器等之點來看，較佳者為1至1000μm，更佳者為1至100μm。 The thickness of the conductive coating layer is not particularly limited and can be the same as that of conventional electrodes. However, a thickness that can keep the bending rigidity within the aforementioned range is preferred so that the desired sensor can be easily manufactured. From a certain point of view, the preferred range is 1 to 1000 μm, and the more preferred range is 1 to 100 μm.

另外，在壓電層為多孔質層，且將導電性塗料塗裝於如此多孔質層之情況，在該多孔質層的內部亦有形成導電性塗料的乾燥體或硬化體之情形，但在此情況，前述導電性塗膜層的厚度也是指從多孔質層的表面算起的厚度。 In addition, when the piezoelectric layer is a porous layer and the conductive coating is applied to such a porous layer, a dried body or a hardened body of the conductive coating may be formed inside the porous layer. However, in this case, the thickness of the conductive coating layer also refers to the thickness measured from the surface of the porous layer.

<壓電層> <Piezoelectric layer>

前述壓電層並無特別限制，可使用以往習知壓電片等，例如：壓電性樹脂層；多孔質層；由水晶、鈦酸鋇、鋯鈦酸鉛(lead zirconate titanate)等無機壓電材料所構成之層。 The aforementioned piezoelectric layer is not particularly limited, and conventional piezoelectric sheets can be used, such as: piezoelectric resin layer; porous layer; inorganic piezoelectric layer made of crystal, barium titanate, lead zirconate titanate, etc. A layer made of electrical materials.

前述壓電層可為單晶(monomorph)型、雙晶(bimorph)型或積層型的任一者。 The piezoelectric layer may be any of a monomorph type, a bimorph type, or a multilayer type.

另外，前述壓電層的形狀及大小等也無特別限制，可依據所希望的用途等而適當地選擇。 In addition, the shape and size of the aforementioned piezoelectric layer are not particularly limited and can be appropriately selected according to the desired use, etc.

前述壓電層的厚度可依據所要使用的用途而適當地選擇，但通常在10μm以上，較佳者為50μm以上，通常在1mm以下，較佳者為500μm以下。 The thickness of the piezoelectric layer can be appropriately selected according to the intended use, but is usually above 10 μm, preferably above 50 μm, and usually below 1 mm, preferably below 500 μm.

作為前述壓電層，以多孔質層為佳，含有樹脂成分的多孔質片更佳。該多孔質片的具體例可列舉如：多孔質有機聚合物片、包含有機聚合物之不織布或織布。 As the aforementioned piezoelectric layer, a porous layer is preferred, and a porous sheet containing a resin component is more preferred. Specific examples of the porous sheet include: a porous organic polymer sheet, a nonwoven fabric or a woven fabric containing an organic polymer.

其中，從可長期維持耐久性、變形性能等之點來看，尤以包含有機聚合物之不織布或織布為佳，更佳者為使有機聚合物附著於絶緣性不織布或織布而構成者、由包含有機聚合物之纖維所構成的不織布或織布，從可更容易地得到不是藉由壓電層的伸縮而是藉由外部施加的壓力而生電，且經過長期間亦會顯示高輸出電壓的感測器等之點來看，尤以包含有機聚合物之玻璃布或玻璃不織布為特佳。 Among these, nonwoven fabrics or woven fabrics containing organic polymers are particularly preferred from the viewpoint of maintaining durability, deformation properties, etc. for a long period of time, and even more preferred ones are those in which organic polymers are attached to insulating nonwoven fabrics or woven fabrics. Non-woven fabrics or woven fabrics composed of fibers containing organic polymers can more easily generate electricity not by expansion and contraction of the piezoelectric layer but by externally applied pressure, and can also show high performance over a long period of time. From the perspective of output voltage sensors, glass cloth or glass non-woven fabric containing organic polymers is particularly suitable.

從可容易地得到電荷保持性高的壓電層等之點來看，前述多孔質層的孔隙率較佳者為0.1體積%以上，更佳者為1體積%以上，又更佳者為2體積%以上，較佳者為70體積%以下，更佳者為60體積%以下，又更佳者為50體積%以下。 From the viewpoint of easily obtaining a piezoelectric layer with high charge retention properties, the porosity of the porous layer is preferably 0.1 volume % or more, more preferably 1 volume % or more, and still more preferably 2 Volume % or more, preferably 70 volume % or less, more preferably 60 volume % or less, still more preferably 50 volume % or less.

該孔隙率可用下述實施例中揭示的方法測定，另外，由有機聚合物所構成的多孔質層的孔隙率可用以下的方法計算。 The porosity can be measured by the method disclosed in the following examples. In addition, the porosity of the porous layer composed of the organic polymer can be calculated by the following method.

孔隙率=(有機聚合物的真密度-多孔質層的表觀密度)×100/有機聚合物的真密度 Porosity = (true density of organic polymer - apparent density of porous layer) × 100 / true density of organic polymer

其中，表觀密度係採用以多孔質層的質量及表觀體積所計算而得之值。 Among them, the apparent density is the value calculated using the mass and apparent volume of the porous layer.

前述有機聚合物中，從得到電荷保持量高，壓電特性良好的壓電層等之點來看，在不會損及本發明的效果之範圍內可含有1種或2種以上的無機填料。從可得到具有更高壓電率的壓電層等之點來看，該無機 填料以具有比聚合物高的電容率之填料為佳，例如以相對電容率ε在10至10000之無機填料為佳。無機填料的具體例可列舉如：氧化鈦、氧化鋁、鈦酸鋇、鋯鈦酸鉛、氧化鋯、氧化鈰、氧化鎳、氧化錫。 The aforementioned organic polymer may contain one or more inorganic fillers within the range that does not impair the effect of the present invention, from the viewpoint of obtaining a piezoelectric layer with high charge retention and good piezoelectric properties. From the viewpoint of obtaining a piezoelectric layer with a higher piezoelectric constant, the inorganic filler is preferably a filler with a higher capacitance than the polymer, for example, an inorganic filler with a relative capacitance ε of 10 to 10000. Specific examples of inorganic fillers include titanium oxide, aluminum oxide, barium titanate, lead zirconium titanate, zirconium oxide, barium oxide, nickel oxide, and tin oxide.

前述有機聚合物並無特別限制，可可列舉例如：聚四氟乙烯聚合物(PTFE)、四氟乙烯與全氟烷基乙烯基醚之共聚物(PFA)、四氟乙烯與六氟丙烯之共聚物(FEP)、聚氯三氟乙烯(PCTFE)、四氟乙烯與乙烯之共聚物(ETFE)、聚偏二氟乙烯(PVdF)、聚氟乙烯(PVF)、四氟乙烯與六氟丙烯與偏二氟乙烯的共聚物(THV)等含氟系樹脂；聚丙烯、聚乙烯等聚烯烴系樹脂；聚苯乙烯、聚(甲基)丙烯酸酯、聚丙烯腈、聚氯乙烯，聚偏二氯乙烯等乙烯系聚合物；聚對苯二甲酸乙二酯、聚對苯二甲酸丁二酯、聚萘二甲酸乙二酯、聚乳酸、聚羥基烷酸酯、聚丁二酸丁二酯、聚琥珀酸乙二酯、聚琥珀酸己二酸乙烯酯(polyethylene succinate adipate)等聚酯系聚合物；尼龍6、尼龍66、尼龍11、尼龍12等聚醯胺系樹脂；聚芳醯胺等芳香族聚醯胺系樹脂；聚醯亞胺、聚醯胺醯亞胺、聚醚醯亞胺、雙馬來醯亞胺等亞胺系樹脂；聚碳酸酯、聚環烯烴類等工程塑膠類等熱塑性樹脂；不飽和聚酯、乙烯基酯樹脂、鄰苯二甲酸二烯丙酯樹脂、環氧樹脂、酚系樹脂、聚胺酯、矽系樹脂、醇酸樹脂、呋喃樹脂、雙環戊二烯樹脂、丙烯酸樹脂、碳酸烯丙酯樹脂等熱硬化性樹脂；聚矽氧樹脂。 The aforementioned organic polymer is not particularly limited, and examples thereof include: fluorine-containing resins such as polytetrafluoroethylene polymer (PTFE), copolymers of tetrafluoroethylene and perfluoroalkyl vinyl ether (PFA), copolymers of tetrafluoroethylene and hexafluoropropylene (FEP), polychlorotrifluoroethylene (PCTFE), copolymers of tetrafluoroethylene and ethylene (ETFE), polyvinylidene fluoride (PVdF), polyvinyl fluoride (PVF), copolymers of tetrafluoroethylene, hexafluoropropylene and vinylidene fluoride (THV); polyolefin resins such as polypropylene and polyethylene; vinyl polymers such as polystyrene, poly(meth)acrylate, polyacrylonitrile, polyvinyl chloride, and polyvinylidene chloride; polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polylactic acid, polyhydroxyalkanoate, polybutylene succinate, polyethylene succinate, and polyvinyl adipate (polyethylene succinate). Polyester polymers such as adipate; polyamide resins such as nylon 6, nylon 66, nylon 11, and nylon 12; aromatic polyamide resins such as polyarylamide; imide resins such as polyimide, polyamide imide, polyether imide, and dimaleimide; industrial polyester resins such as polycarbonate and polycycloolefins Thermoplastic resins such as process plastics; thermosetting resins such as unsaturated polyester, vinyl ester resin, diallyl phthalate resin, epoxy resin, phenolic resin, polyurethane, silicone resin, alkyd resin, furan resin, dicyclopentadiene resin, acrylic resin, allyl carbonate resin; polysilicone resin.

作為前述有機聚合物，體積電阻率係以1.0×10¹³Ω．cm以上之聚合物為佳，例如，聚醯胺系樹脂、芳香族聚醯胺系樹脂、聚烯烴系樹脂、聚酯系樹脂、聚丙烯腈、酚系樹脂、含氟系樹脂、醯亞胺系樹脂。 As the aforementioned organic polymer, a polymer having a volume resistivity of 1.0×10 ¹³ Ω·cm or more is preferred, for example, polyamide resins, aromatic polyamide resins, polyolefin resins, polyester resins, polyacrylonitrile, phenol resins, fluorine-containing resins, and imide resins.

其中，從耐熱性、耐候性良好等之點來看，係以不具有起因於分子及結晶構造的偶極之有機聚合物為佳。如此的聚合物可列舉例如：聚烯烴系樹脂(例：聚乙烯、聚丙烯、乙烯丙烯樹脂)、聚酯系樹脂(例：聚對苯二甲酸乙二酯)、聚胺酯樹脂、聚苯乙烯樹脂、聚矽氧樹脂等非氟系樹脂、以及聚四氟乙烯(PTFE)、四氟乙烯-全氟烷基乙烯基醚共聚物(PFA)、四氟乙烯-六氟丙烯共聚物(FEP)等含氟系樹脂。 Among them, organic polymers that do not have dipoles derived from molecules and crystal structures are preferred from the viewpoint of good heat resistance and weather resistance. Examples of such polymers include polyolefin resins (eg polyethylene, polypropylene, ethylene propylene resin), polyester resins (eg polyethylene terephthalate), polyurethane resins, and polystyrene resins. , non-fluorine resins such as polysilicone resin, and polytetrafluoroethylene (PTFE), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), etc. Fluorine-containing resin.

其中，從耐熱性及耐候性等之觀點來看，以可連續使用的溫度高，玻璃轉移點並不在本感測器的使用溫度範圍內之聚合物為佳。可連續使用的溫度可用UL746B(UL規格)所記載的連續使用溫度試驗測定，以在50℃以上為佳，以80℃以上更佳。另外，從耐濕性的觀點來看，以具有撥水性之聚合物為佳。 Among them, from the viewpoint of heat resistance and weather resistance, polymers that can be used continuously at a high temperature and whose glass transition point is not within the operating temperature range of this sensor are preferred. The temperature that can be used continuously can be measured by the continuous use temperature test described in UL746B (UL standard). It is preferably above 50°C, and more preferably above 80°C. In addition, from the viewpoint of moisture resistance, a polymer having water repellency is preferred.

作為具有此等特性之聚合物，以聚烯烴系樹脂、含氟系樹脂為佳，尤其，從即使在高溫下亦可得到壓電特性不易降低，可正確地檢測壓力之感測器等之點來看，以含氟系樹脂為更佳，以PTFE為特佳。尤其，在採用PTFE作為前述聚合物時，可得到耐熱性、壓力檢測能力及耐久性之平衡優異的感測器。 As polymers having such properties, polyolefin resins and fluorine-containing resins are preferred. In particular, fluorine-containing resins are preferred, and PTFE is particularly preferred, from the perspective that the piezoelectric properties are not easily reduced even at high temperatures, and a sensor that can accurately detect pressure can be obtained. In particular, when PTFE is used as the aforementioned polymer, a sensor with an excellent balance of heat resistance, pressure detection capability, and durability can be obtained.

當前述壓電層係由壓電材料以外的材料所構成的層時，例如前述多孔質層之情況，以經過極化處理之層為佳。藉由施加極化處理，可將電荷注入該層。多孔質層之情況，注入的電荷會集中在存在於多孔質層內的孔隙內而誘發極化。內部極化後之層，可藉由在層的厚度方向施加壓縮負載，而通過層的正面與背面將電荷取出。亦即，會對外部負載(電路)產生電荷移動而得到電動勢。 When the aforementioned piezoelectric layer is a layer composed of materials other than piezoelectric materials, such as the aforementioned porous layer, it is preferably a layer that has been polarized. By applying polarization, charges can be injected into the layer. In the case of a porous layer, the injected charges will be concentrated in the pores existing in the porous layer to induce polarization. The layer after internal polarization can be charged through the front and back surfaces of the layer by applying a compressive load in the thickness direction of the layer. That is, charge transfer will be generated to the external load (circuit) to obtain an electromotive force.

〔多孔質有機聚合物片〕 [Porous organic polymer sheet]

作為前述多孔質有機聚合物片，較佳者係由可保持電荷之有機聚合物所構成之片。作為如此的多孔質有機聚合物片，可列舉例如：由有機聚合物所構成之片狀的發泡體、由有機聚合物所構成之延伸多孔質膜、含有基質樹脂(有機聚合物)及電荷誘發性中空粒子(在中空粒子的表面的至少一部分附著有導電性物質之粒子)之多孔質有機聚合物片、以利用超臨界二氧化碳等萃取劑去除分散於有機聚合物中之相分離劑來形成孔隙之方法所形成之片。 As the porous organic polymer sheet, a sheet composed of an organic polymer capable of retaining electric charges is preferred. Examples of such porous organic polymer sheets include sheet-shaped foams made of organic polymers, extended porous films made of organic polymers, matrix resins (organic polymers) and charges. Porous organic polymer sheets of induced hollow particles (particles with a conductive substance attached to at least part of the surface of the hollow particles) are formed by removing a phase separation agent dispersed in the organic polymer using an extraction agent such as supercritical carbon dioxide A sheet formed by the method of pores.

〔包含有機聚合物之不織布或織布〕 [Nonwoven or woven fabrics containing organic polymers]

包含有機聚合物之不織布或織布，具體上係可列舉如：使有機聚合物附著於絶緣性不織布或織布而成者、由包含有機聚合物之纖維所構成之不織布或織布等。其中，從更加發揮前述效果等之點來看，以使有機聚合物附著於絶緣性不織布或織布而成者為佳。 Nonwoven fabrics or woven fabrics containing organic polymers include, for example, those formed by attaching organic polymers to insulating nonwoven fabrics or woven fabrics, and nonwoven fabrics or woven fabrics composed of fibers containing organic polymers. Among them, those formed by attaching organic polymers to insulating nonwoven fabrics or woven fabrics are preferred from the viewpoint of further exerting the aforementioned effects.

前述不織布可採用以濕式造紙方式、水軋(water punch)方式、化學黏合(chemical bond)方式、熱熔黏合(thermal bond)方式、紡黏(spun bond)方式、針軋(needle punch)方式、針腳式接合(stitch-bond)方式等各種製法製得的不織布，但從耐熱性、機械特性、耐溶劑性之點來看，較佳者為以利用自熔融纖維進行的熱熔黏合方式或紡黏方式製成之不織布。 The aforementioned nonwoven fabric can be made by various methods such as wet papermaking, water punching, chemical bonding, thermal bonding, spun bonding, needle punching, stitch-bonding, etc. However, in terms of heat resistance, mechanical properties, and solvent resistance, the best nonwoven fabric is made by thermal bonding or spun bonding using self-melting fibers.

構成前述織布之纖維(絲線)，可採用單絲(monofilamen)、複絲(multifilament)、短纖(staple)之任一者。編織法亦無特別限制，可列舉如：平織、斜紋織(twill)、緞織、雙層織、圓筒織等。在織構成方面，織紗組織、紗線支數、紗線密度並無特別限制。 The fibers (threads) constituting the aforementioned woven fabric may be monofilament, multifilament, or staple. The weaving method is not particularly limited, and examples include plain weave, twill weave, satin weave, double-layer weave, cylinder weave, etc. In terms of weaving composition, there are no special restrictions on the weaving yarn structure, yarn count, and yarn density.

構成前述不織布或織布之纖維的平均纖維徑，較佳者為0.05μm以上，更佳者為0.1μm以上，又更佳者為0.3μm以上，較佳者為50μm以下，更佳者為20μm以下，又更佳者為10μm以下。 The average fiber diameter of the fibers constituting the aforementioned nonwoven fabric or woven fabric is preferably 0.05 μm or more, more preferably 0.1 μm or more, still more preferably 0.3 μm or more, preferably 50 μm or less, and still more preferably 20 μm. below, and more preferably below 10 μm.

平均纖維徑在前述範圍內時，因為可形成顯示高柔軟性的不織布或織布、由於纖維表面積變大而可形成充分的保持電荷的空間、即使在形成薄的不織布或織布之情況也可提高纖維的分布均勻性之點故而較佳。 When the average fiber diameter is within the above range, it is possible to form a nonwoven fabric or woven fabric showing high flexibility, and the fiber surface area is increased to form a sufficient space for holding charges, even when a thin nonwoven fabric or woven fabric is formed. It is better because it improves the uniformity of fiber distribution.

構成前述不織布或織布之纖維的平均纖維徑，可藉由適當地選擇形成纖維的條件而調整，例如在以靜電紡絲(electrospinning)法製造時，係有：在靜電紡絲之際，降低濕度、減小噴嘴口徑、加大施加電壓、或加大電壓密度，可使所得到的纖維的平均纖維徑減小之傾向。 The average fiber diameter of the fibers constituting the aforementioned non-woven fabric or woven fabric can be adjusted by appropriately selecting the conditions for forming the fibers. For example, when manufacturing by electrospinning (electrospinning) method, the following is: During electrospinning, the average fiber diameter is reduced. Humidity, reducing the nozzle diameter, increasing the applied voltage, or increasing the voltage density tend to reduce the average fiber diameter of the obtained fibers.

另外，前述平均纖維徑係：以掃描式電子顯微鏡(SEM)觀察(倍率：10000倍)測定對象的纖維(群)，從得到的SEM影像隨機選擇20根纖維，量測各纖維的纖維徑(長徑)，根據該量測結果而算出的平均值。 In addition, the aforementioned average fiber diameter is the average value calculated based on the measurement results of observing the target fiber (group) with a scanning electron microscope (SEM) (magnification: 10,000 times), randomly selecting 20 fibers from the obtained SEM image, measuring the fiber diameter (long diameter) of each fiber.

構成前述不織布或織布之纖維的利用下述式計算的纖維徑變動係數，較佳者為0.7以下，更佳者為0.01以上0.5以下。當纖維徑變動係數在前述範圍內，纖維的纖維徑就會均勻，使用該纖維而得到的不織布或織布就會具有更高的孔隙率，因此可得到電荷保持性高的不織布或織布，故而較佳。 The fiber diameter variation coefficient of the fiber constituting the aforementioned nonwoven fabric or woven fabric calculated by the following formula is preferably 0.7 or less, and more preferably 0.01 or more and 0.5 or less. When the fiber diameter variation coefficient is within the aforementioned range, the fiber diameter of the fiber will be uniform, and the nonwoven fabric or woven fabric obtained using the fiber will have a higher porosity, so a nonwoven fabric or woven fabric with high charge retention can be obtained, which is preferred.

纖維徑變動係數=標準偏差/平均纖維徑(所謂的「標準偏差」，係前述20根纖維的纖維徑的標準偏差。) Fiber diameter variation coefficient = standard deviation/average fiber diameter (The so-called "standard deviation" is the standard deviation of the fiber diameters of the aforementioned 20 fibers.)

構成前述不織布或織布之纖維的纖維長，較佳者為0.1mm以上，更佳者為0.5mm以上，又更佳者為1mm以上，較佳者為1000mm以下，更佳者為100mm以下，又更佳者為50mm以下。 The fiber length of the fiber constituting the aforementioned nonwoven fabric or woven fabric is preferably 0.1 mm or more, more preferably 0.5 mm or more, and even more preferably 1 mm or more, and preferably 1000 mm or less, more preferably 100 mm or less, and even more preferably 50 mm or less.

前述不織布及織布的基重(單位面積重量)，較佳者為100g/m²以下，更佳者為0.1至50g/m²，又更佳者為0.1至20g/m²。 The basis weight (weight per unit area) of the nonwoven fabric and the woven fabric is preferably 100 g/m ² or less, more preferably 0.1 to 50 g/m ² , and even more preferably 0.1 to 20 g/m ² .

前述基重由於加長紡絲時間、增加紡絲噴嘴數等原因而有增大之傾向。 The aforementioned basis weight tends to increase due to reasons such as extending the spinning time and increasing the number of spinning nozzles.

前述不織布及織布係將前述纖維堆積成或製織成片狀而成者，如此不織布及織布可為由單層所構成者、或由材質及纖維徑不同的2層以上所構成者之其中任一者。 The aforementioned nonwoven fabric and woven fabric are formed by piling or weaving the aforementioned fibers into a sheet shape. Such nonwoven fabric and woven fabric may be composed of a single layer or composed of two or more layers of different materials and fiber diameters.

‧使有機聚合物附著於絶緣性不織布或織布而成者 ‧Organic polymers attached to insulating nonwoven fabrics or woven fabrics

使有機聚合物附著於絶緣性不織布或織布而成者(以下稱為「有機聚合物附著體」)中之有機聚合物的存在處並無特別限制，可為附著於構成絶緣性不織布或織布之纖維，亦可為存在於絶緣性不織布或織布中的空隙，但較佳者為被覆於構成絶緣性不織布或織布之纖維。 The location of the organic polymer in the body formed by attaching the organic polymer to the insulating nonwoven fabric or woven fabric (hereinafter referred to as the "organic polymer attached body") is not particularly limited. It may be attached to the fibers constituting the insulating nonwoven fabric or woven fabric, or may exist in the gaps in the insulating nonwoven fabric or woven fabric. However, it is preferably coated on the fibers constituting the insulating nonwoven fabric or woven fabric.

前述絶緣性不織布或織布可為有機材料製的不織布或織布，亦可為無機材料製的不織布或織布，但從更加發揮前述效果等之點來看，較佳者為無機材料製的不織布或織布。 The aforementioned insulating nonwoven or woven fabric may be a nonwoven or woven fabric made of an organic material or a nonwoven or woven fabric made of an inorganic material, but from the perspective of better exerting the aforementioned effects, a nonwoven or woven fabric made of an inorganic material is preferred.

該有機材料可列舉例如與前述有機聚合物一樣之聚合物。 Examples of the organic material include the same polymers as the above-mentioned organic polymers.

該無機材料可列舉例如：玻璃纖維、岩絨、碳纖維、氧化鋁纖維、矽灰石或鈦酸鉀等陶瓷纖維。其中，尤以玻璃纖維及/或陶瓷纖維為佳。 The inorganic material may include, for example, glass fiber, rock wool, carbon fiber, alumina fiber, wollastonite or ceramic fibers such as potassium titanate. Among them, glass fiber and/or ceramic fiber are particularly preferred.

從帶電特性等之點來看，絶緣性不織布或織布可為帶正電，亦可為帶負電。 From the perspective of charging characteristics, insulating nonwovens or woven fabrics can be positively charged or negatively charged.

另外，絶緣性不織布或織布與附著的有機聚合物，其帶電傾向可大致相同，亦可相異，但以在帶電列上相距較遠的材料的組合為佳。當絶緣性不織布或織布採用玻璃織布時，可容易地得到顯示高壓電常數，且可保持高壓電率之壓電層，故而較佳。 In addition, the charging tendency of the insulating nonwoven or woven fabric and the attached organic polymer can be roughly the same or different, but the combination of materials that are far apart in the charging series is preferred. When the insulating nonwoven or woven fabric uses glass fabric, it is easy to obtain a piezoelectric layer that shows a high piezoelectric constant and can maintain a high piezoelectric rate, so it is better.

使附著於前述絶緣性不織布或織布之有機聚合物，從帶電特性的觀點來看，可為容易帶負電者，亦可為容易帶正電者。絶緣性不織布或織布如由玻璃纖維所構成時，該有機聚合物以相較於玻璃纖維而言帶電列較位於負側之樹脂，例如以含氟系樹脂為佳。 The organic polymer attached to the insulating nonwoven fabric or woven fabric may be easily charged negatively or positively charged from the viewpoint of charging characteristics. When the insulating non-woven fabric or woven fabric is made of glass fiber, the organic polymer is preferably a resin whose electrified column is on the negative side compared to the glass fiber, such as a fluorine-containing resin.

又，使附著於前述絶緣性不織布或織布之有機聚合物，從耐熱特性的觀點來看，以熔融溫度高，且熱分解開始溫度高之樹脂為佳，例如，以含氟系樹脂、醯亞胺系樹脂為佳，在與玻璃織布或不織布組合時，以含氟樹脂，尤其是PTFE為佳。採用如此含氟系樹脂或醯亞胺系樹脂時，所得到的壓電層的耐熱性及耐候性優異，尤其是在70℃以上的高溫之壓電特性的經時安定性為優異，故而更佳。 In addition, the organic polymer attached to the insulating non-woven fabric or woven fabric is preferably a resin with a high melting temperature and a high thermal decomposition start temperature from the viewpoint of heat resistance properties. For example, fluorine-containing resin, fluorine-containing resin, etc. Imine-based resin is preferred, and when combined with glass woven fabric or non-woven fabric, fluorine-containing resin, especially PTFE, is preferred. When such a fluorine-containing resin or an amide-based resin is used, the obtained piezoelectric layer has excellent heat resistance and weather resistance, and especially has excellent stability over time of the piezoelectric characteristics at high temperatures of 70° C. or higher, so it is more suitable. good.

前述有機聚合物附著體的製造方法並無特別限制，但從製造容易性等之點來看，以將絶緣性不織布或織布浸漬於有機聚合物(包含有機聚合物之液體)中，然後將絶緣性不織布或織布取出，再使之乾燥或硬化之方法為佳。 There is no particular limitation on the method for manufacturing the aforementioned organic polymer attachment, but from the perspective of ease of manufacturing, it is preferred to immerse the insulating nonwoven fabric or woven fabric in an organic polymer (a liquid containing an organic polymer), then take out the insulating nonwoven fabric or woven fabric, and then dry or harden it.

前述有機聚合物附著體中之有機聚合物的含量，從更容易得到顯示更高輸出電壓的感測器等之點來看，較佳者為10質量%以上，更佳者為30質量%以上，較佳者為90質量%以下，更佳者為80質量%以下。 The content of the organic polymer in the aforementioned organic polymer attachment is preferably 10% by mass or more, more preferably 30% by mass or more, preferably 90% by mass or less, and more preferably 80% by mass or less, from the point of view of making it easier to obtain a sensor that exhibits a higher output voltage.

該含量可從例如：在氮氣等惰性氣體環境下，以有機聚合物的分解開始溫度以上，構成絶緣性不織布或織布之材料的軟化溫度以下左右的溫度進行加熱之時的加熱前後的質量變化而算出。 This content can range from, for example, the mass change before and after heating when heating is performed in an inert gas environment such as nitrogen at a temperature above the decomposition start temperature of the organic polymer and below the softening temperature of the material constituting the insulating nonwoven fabric or woven fabric. And figure it out.

‧由含有有機聚合物之纖維所構成之不織布或織布 ‧Non-woven fabrics or woven fabrics composed of fibers containing organic polymers

該纖維係以例如靜電紡絲法、熔融紡絲法、熔融靜電紡絲法、紡黏法(熔吹法)、濕式法、水刺(spunlace)法製造，但以特別是靜電紡絲法得到的纖維的纖維徑較小，用如此纖維形成的不織布或織布的孔隙率高且比表面積高，因此可得到具有高壓電性之不織布或織布。 The fiber is produced by, for example, electrospinning, melt spinning, melt electrospinning, spunbonding (melt blowing), wet spinning, or spunlace. However, the fiber diameter of the fiber obtained by electrospinning is particularly small, and the nonwoven or woven fabric formed by such fiber has a high porosity and a high specific surface area, so a nonwoven or woven fabric with high piezoelectricity can be obtained.

在採用靜電紡絲法形成包含有機聚合物的纖維時，係使用例如包含前述有機聚合物及視需要的溶劑之紡絲液。 When using electrostatic spinning to form fibers containing an organic polymer, a spinning solution containing the aforementioned organic polymer and, if necessary, a solvent is used.

前述紡絲液中含有的有機聚合物的比率，例如為5質量%以上，較佳者為10質量%以上，例如為100質量%以下，較佳者為80質量%以下，更佳者為70質量%以下。 The ratio of the organic polymer contained in the spinning solution is, for example, 5% by mass or more, preferably 10% by mass or more, for example, 100% by mass or less, preferably 80% by mass or less, and more preferably 70% by mass. mass% or less.

前述聚合物可單獨使用1種，亦可使用2種以上。 The above-mentioned polymers may be used alone or in combination of two or more.

前述溶劑只要是可使前述聚合物溶解或分散者即可而無特別限制，可為例如水、二甲基乙醯胺、二甲基甲醯胺、四氫呋喃、甲基吡咯啶酮、二甲苯、丙酮、三氯甲烷、乙苯、環己烷、苯、環丁碸、甲醇、 乙醇、酚、吡啶、碳酸伸丙酯、乙腈、三氯乙烷、六氟異丙醇、二***。此等溶劑可使用1種，亦可使用2種以上。 The aforementioned solvent is not particularly limited as long as it can dissolve or disperse the aforementioned polymer, and may be, for example, water, dimethylacetamide, dimethylformamide, tetrahydrofuran, methylpyrrolidone, xylene, acetone, chloroform, ethylbenzene, cyclohexane, benzene, cyclobutane, methanol, ethanol, phenol, pyridine, propylene carbonate, acetonitrile, trichloroethane, hexafluoroisopropanol, diethyl ether. One or more of these solvents may be used.

紡絲液中的前述溶劑的含量，例如為0質量%以上，較佳者為10質量%以上，更佳者為20質量%以上，例如為90質量%以下，較佳者為80質量%以下。 The content of the aforementioned solvent in the spinning solution is, for example, 0% by mass or more, preferably 10% by mass or more, more preferably 20% by mass or more, for example, 90% by mass or less, preferably 80% by mass or less.

前述紡絲液除了前述有機聚合物以外，另可含有無機填料、界面活性劑、分散劑、電荷調整劑、機能性粒子、接著劑、黏度調整劑、纖維形成劑等添加劑。此等添加劑可單獨使用1種，亦可使用2種以上。 In addition to the aforementioned organic polymer, the aforementioned spinning liquid may also contain additives such as inorganic fillers, surfactants, dispersants, charge modifiers, functional particles, adhesives, viscosity modifiers, and fiber forming agents. These additives may be used alone or in combination of two or more.

在前述紡絲液中，若前述有機聚合物在前述溶劑中的溶解度低(例如有機聚合物為PTFE，溶劑為水之情況)，從在紡絲時使有機聚合物保持纖維形狀等之點來看，以含有1種或2種以上的纖維形成劑為佳。 In the aforementioned spinning solution, if the solubility of the aforementioned organic polymer in the aforementioned solvent is low (for example, the organic polymer is PTFE and the solvent is water), it is preferred to contain one or more fiber-forming agents from the viewpoint of keeping the organic polymer in a fiber shape during spinning.

作為前述纖維形成劑，以在溶劑中具有高溶解度的有機聚合物為佳，可列舉例如：聚環氧乙烷、聚乙二醇、聚葡萄糖、藻酸、殼聚糖(chitosan)、澱粉、聚乙烯吡咯啶酮、聚丙烯酸、聚甲基丙烯酸、聚丙烯醯胺、纖維素、聚乙烯醇。 As the aforementioned fiber forming agent, organic polymers with high solubility in the solvent are preferred, and examples thereof include: polyethylene oxide, polyethylene glycol, polydextrose, alginic acid, chitosan, starch, polyvinyl pyrrolidone, polyacrylic acid, polymethacrylic acid, polyacrylamide, cellulose, and polyvinyl alcohol.

使用前述纖維形成劑時，雖取決於溶劑的黏度、在溶劑中的溶解度，但紡絲液中的前述纖維形成劑的含量例如為0.1質量%以上，較佳者為1質量%以上，例如為15質量%以下，較佳者為10質量%以下。 When using the aforementioned fiber-forming agent, although it depends on the viscosity of the solvent and the solubility in the solvent, the content of the aforementioned fiber-forming agent in the spinning solution is, for example, 0.1 mass% or more, preferably 1 mass% or more, for example 15% by mass or less, preferably 10% by mass or less.

前述紡絲液可用習知方法將前述有機聚合物、溶劑及視需要而添加的添加劑相混合來製造。 The aforementioned spinning liquid can be produced by mixing the aforementioned organic polymer, solvent and additives added as needed using a known method.

前述有機聚合物為PTFE時，前述紡絲液的較佳例可列舉以下的紡絲液(1)。 When the organic polymer is PTFE, preferred examples of the spinning liquid include the following spinning liquid (1).

紡絲液(1)：含有30質量%以上，70質量%以下，較佳者為35質量%以上，較佳者為60質量%以下的PTFE，含有0.1質量%以上，10質量%以下，較佳者為1質量%以上，較佳者為7質量%以下的纖維形成劑，及含有合計100質量%之剩餘質量%的溶劑之紡絲液 Spinning liquid (1): containing 30% by mass or more and 70% by mass or less, preferably 35% by mass or more and 60% by mass or less of PTFE, 0.1% by mass or more and 10% by mass or less, preferably 1% by mass or more and 7% by mass or less of a fiber forming agent, and a total of 100% by mass of a residual solvent.

進行靜電紡絲時的施加電壓，較佳者為1kV以上，更佳者為5kV以上，又更佳者為10kV以上，較佳者為100kV以下，更佳者為50kV以下，又更佳者為40kV以下。 The applied voltage during electrospinning is preferably 1 kV or more, more preferably 5 kV or more, still more preferably 10 kV or more, more preferably 100 kV or less, more preferably 50 kV or less, and still more preferably Below 40kV.

靜電紡絲中使用的紡絲噴嘴的前端徑(外徑)，較佳者為0.1mm以上，更佳者為0.2mm以上，較佳者為2.0mm以下，更佳者為1.6mm以下。 The tip diameter (outer diameter) of the spinning nozzle used in electrospinning is preferably 0.1 mm or more, more preferably 0.2 mm or more, preferably 2.0 mm or less, and more preferably 1.6 mm or less.

更具體地說，例如在使用前述紡絲液(1)時，前述施加電壓較佳者為10至50kV，更佳者為10至40kV，前述紡絲噴嘴的前端徑(外徑)較佳者為0.3至1.6mm。 More specifically, for example, when using the spinning solution (1), the applied voltage is preferably 10 to 50 kV, and more preferably 10 to 40 kV, and the front end diameter (outer diameter) of the spinning nozzle is preferably 10 to 50 kV. is 0.3 to 1.6mm.

在使用前述纖維形成不織布時，具體而言，係例如：可同時進行採用靜電紡絲法來製造前述纖維之步驟、及將前述纖維堆積成片狀而形成不織布之步驟，或者在進行製造出前述纖維之步驟之後，才進行以濕式法等將前述纖維堆積成片狀而形成不織布之步驟。 When the aforementioned fibers are used to form a nonwoven fabric, specifically, for example, the steps of manufacturing the aforementioned fibers by electrostatic spinning and stacking the aforementioned fibers into a sheet to form a nonwoven fabric can be performed simultaneously, or after the step of manufacturing the aforementioned fibers is performed, the step of stacking the aforementioned fibers into a sheet to form a nonwoven fabric by a wet method or the like is performed.

以前述濕式法來形成不織布之方法，可列舉例如：使用含有前述纖維之水分散液，使前述纖維堆積(集積)在例如紗網(mesh)上使之成形(造紙)成片狀之方法。 An example of a method of forming a nonwoven fabric by the wet method is a method of using an aqueous dispersion containing the fibers, depositing (accumulating) the fibers on, for example, a mesh (mesh), and forming (making paper) into a sheet. .

此濕式法中之纖維的使用量，相對於前述水分散液全量，較佳者為0.1至10質量%，更佳者為0.1至5質量%。在此範圍內使用纖維時，可在使纖維堆積之步驟中有效率地活用水，而且，纖維的分散狀態會變好，可得到均勻的濕式不織布。 The amount of fiber used in this wet method is preferably 0.1 to 10% by mass, and more preferably 0.1 to 5% by mass, relative to the total amount of the aforementioned aqueous dispersion. When the fiber is used within this range, water can be used efficiently in the step of stacking the fiber, and the dispersion state of the fiber will be improved, so that a uniform wet nonwoven fabric can be obtained.

前述水分散液中，為了使分散狀態良好，可添加由陽離子型、陰離子型、非離子型等界面活性劑等所構成之分散劑或油劑，以及抑制氣泡發生之消泡劑等各1種或2種以上。 To the aqueous dispersion, in order to achieve a good dispersion state, a dispersant or oil agent composed of a cationic, anionic, nonionic surfactant, etc., and a defoaming agent that suppresses the generation of bubbles can be added. Or 2 or more types.

在使用前述纖維來形成織布時，可用包含製造前述纖維的步驟、及將所得到的纖維織成片狀而形成織布的步驟之方法來製造。 When the aforementioned fiber is used to form a woven fabric, it can be produced by a method including a step of producing the aforementioned fiber and a step of weaving the obtained fiber into a sheet shape to form the woven fabric.

將纖維織成片狀之方法，可採用習知紡織方法，可列舉如：噴水式織機(water jet loom)、噴氣式織機(air jet loom)、劍桅式織機(rapier loom)等方法。 The fiber can be woven into a sheet by conventional weaving methods, such as water jet loom, air jet loom, rapier loom, etc.

前述有機聚合物為PTFE時，以在形成不織布或織布之後，進行加熱處理為佳。該加熱處理係對所得的不織布或織布進行一般常為200至390℃之30至300分鐘的熱處理而進行。藉由此加熱處理，可將殘留於不織布或織布之前述溶劑及纖維形成劑等去除。 When the aforementioned organic polymer is PTFE, it is preferred to perform a heat treatment after forming a nonwoven fabric or a woven fabric. The heat treatment is performed by subjecting the obtained nonwoven fabric or woven fabric to a heat treatment at a temperature of generally 200 to 390°C for 30 to 300 minutes. By this heat treatment, the aforementioned solvent and fiber forming agent remaining in the nonwoven fabric or the woven fabric can be removed.

舉例來具體說明前述不織布的製造方法包含有以靜電紡絲法來製造由PTFE所構成的纖維之步驟的情況。由PTFE纖維所構成的不織布的製造方法，可採用習知製造方法，可列舉例如日本特表2012-515850號公報中記載的以下的方法，亦即包含下列步驟之方法： A specific example will be given of a case where the manufacturing method of the nonwoven fabric includes a step of manufacturing fibers made of PTFE by an electrospinning method. The nonwoven fabric composed of PTFE fibers can be manufactured using conventional manufacturing methods. For example, the following method is described in Japanese Patent Publication No. 2012-515850, that is, a method including the following steps:

提供含有PTFE、纖維形成劑及溶劑，且至少具有50,000cP的黏度的紡絲液之步驟； A step of providing a spinning solution containing PTFE, a fiber former and a solvent and having a viscosity of at least 50,000 cP;

將紡絲液利用噴嘴進行紡絲且利用靜電牽引使之纖維化之步驟； The step of spinning the spinning liquid using a nozzle and fiberizing it using electrostatic attraction;

將前述纖維收集在收集器(例：收線捲軸)之上，形成前驅物之步驟； The step of collecting the aforementioned fibers on a collector (e.g., a take-up reel) to form a precursor;

對前述前驅物進行焙燒將前述溶劑及前述纖維形成劑去除而形成由PTFE纖維構成的不織布之步驟。 The step of baking the aforementioned precursor to remove the aforementioned solvent and the aforementioned fiber forming agent to form a non-woven fabric composed of PTFE fibers.

《壓電感測器的製造方法》 《Manufacturing method of piezoelectric inductor》

本發明的一實施型態之壓電感測器的製造方法(以下稱為「本製造方法」)係依序包含金屬層、壓電層及導電性塗膜層之壓電感測器(較佳者為前述本感測器)的製造方法，其包含：將前述導電性塗料塗裝於前述壓電層，然後使該塗裝的塗料乾燥或硬化的步驟。 A method of manufacturing a piezoelectric sensor (hereinafter referred to as the "manufacturing method") according to an embodiment of the present invention is a piezoelectric sensor (relatively referred to as a piezoelectric sensor) including a metal layer, a piezoelectric layer and a conductive coating layer in sequence. Preferably, the manufacturing method of the above-mentioned sensor) includes the steps of applying the conductive paint to the piezoelectric layer, and then drying or hardening the applied paint.

塗裝導電性塗料之方法並無特別限制，可毫無限制地使用習知方法，可列舉例如：無氣噴塗(airless spray)、空氣噴塗(air spray)、刷塗、輥塗等塗佈方法、將壓電層浸漬於導電性塗料中之方法。 There is no particular limitation on the method of applying the conductive coating, and known methods can be used without limitation, for example: airless spray, air spray, brush coating, roller coating, and the method of immersing the piezoelectric layer in the conductive coating.

在該塗裝時，以讓形成的壓電層的厚度在前述範圍內而進行塗裝為佳。 During the coating, it is preferred to coat the piezoelectric layer so that the thickness thereof is within the aforementioned range.

使前述塗料乾燥或硬化時的條件並無特別限制，只要依據所使用的黏結劑及溶劑等而適當地選擇即可，可在常溫下使之乾燥及/或硬化，亦可在加熱下使之乾燥及/或硬化。 The conditions for drying or hardening the aforementioned paint are not particularly limited, as long as they are properly selected according to the binder and solvent used, and they can be dried and/or hardened at room temperature or heated. Drying and/or hardening.

另外，前述乾燥或硬化亦可視需要而在減壓下進行，或在氮氣環境下等惰性氣體環境下進行。 In addition, the aforementioned drying or curing can also be carried out under reduced pressure, or in an inert gas environment such as a nitrogen environment, as needed.

在將前述金屬層與壓電層疊合時，可視需要而使用接著劑，亦可只是單純地使金屬箔等與壓電片等接觸而已。如為後者，亦可在如上述之接觸之後施加壓力。 When laminating the metal layer and the piezoelectric layer, an adhesive may be used if necessary, or the metal foil may be simply brought into contact with the piezoelectric sheet or the like. In the latter case, pressure may also be applied after contact as described above.

在將金屬層與壓電層疊合之前、或塗裝導電性塗料之前，較佳者為先利用電漿處理或電暈處理等習知方法對金屬層及壓電層的表面進行表面處理。 Before laminating the metal layer and the piezoelectric layer, or before applying the conductive coating, it is better to first perform surface treatment on the surface of the metal layer and the piezoelectric layer using known methods such as plasma treatment or corona treatment.

前述壓電層如為由壓電材料以外的材料構成的層，例如前述多孔質層之情況，較佳者為對該壓電層進行極化處理。藉由施加極化處理，可將電荷注入該層。 If the piezoelectric layer is a layer made of a material other than a piezoelectric material, for example, in the case of the porous layer, it is preferable to perform a polarization treatment on the piezoelectric layer. By applying a polarization treatment, charges can be injected into this layer.

前述極化處理之方法，可採用習知方法，並無特別限制，可列舉例如：直流電壓施加處理及交流電壓施加處理等電壓施加處理、電暈放電處理。 The aforementioned polarization treatment method can be a conventional method without particular limitation. Examples thereof include: voltage application treatment such as DC voltage application treatment and AC voltage application treatment, and corona discharge treatment.

例如，電暈放電處理係可使用由市售的高電壓電源及電極所構成的裝置而進行。 For example, corona discharge treatment can be performed using a device composed of a commercially available high-voltage power supply and electrodes.

放電條件只要依據所使用的壓電層的材料及厚度而適當地選擇即可，在例如壓電層為由PTFE所構成的多孔質層時，較佳的條件係可列舉如：高電壓電源的電壓為-0.1至-100kV，更佳者為-1至-20kV，電流為0.1mA以上，100mA以下，更佳者為1mA以上，80mA以下，電極間距離為0.1cm以上，100cm以下，更佳者為1cm以上，10cm以下，施加電壓為0.01MV/m以上，10.0MV/m以下，更佳者為0.5MV/m以上，2.0MV/m以下之條件。 The discharge conditions can be appropriately selected according to the material and thickness of the piezoelectric layer used. For example, when the piezoelectric layer is a porous layer composed of PTFE, the preferred conditions are as follows: the voltage of the high voltage power source is -0.1 to -100 kV, preferably -1 to -20 kV, the current is 0.1 mA or more and 100 mA or less, preferably 1 mA or more and 80 mA or less, the distance between electrodes is 0.1 cm or more and 100 cm or less, preferably 1 cm or more and 10 cm or less, and the applied voltage is 0.01 MV/m or more and 10.0 MV/m or less, preferably 0.5 MV/m or more and 2.0 MV/m or less.

前述極化處理，可為對壓電片等壓電層單體進行之極化處理，但較佳者為在形成前述導電性塗膜之後、在將壓電層與金屬層疊合之後、在形成依序包含金屬層、壓電層及導電性塗膜層的積層體之後、在使用多孔質層與絶緣層等以往習知層之積層體作為前述壓電層時之形成該積層體之後等進行極化處理。 The aforementioned polarization treatment may be carried out on a single piezoelectric layer such as a piezoelectric sheet, but preferably, after forming the aforementioned conductive coating film, after laminating the piezoelectric layer and the metal layer, and then forming After forming a laminate including a metal layer, a piezoelectric layer, and a conductive coating layer in this order, and after using a laminate of conventionally known layers such as a porous layer and an insulating layer as the piezoelectric layer, etc. Polarization treatment.

此可想成是因為可利用與壓電層疊合的層防止經極化處理而使得保持於壓電層之電荷在與外部環境電性連接之後衰減，而可得到更高靈敏度的壓電感測器之緣故，或可想成是因為會有可在壓電層及與該壓電層疊合的層之間形成可保持電荷之新的界面的傾向，而使所得到的壓電感測器中的壓電層的壓電率提高之緣故。 This is thought to be because the layer stacked with the piezoelectric layer can prevent the charge retained in the piezoelectric layer from decaying after being electrically connected to the external environment due to polarization treatment, thereby obtaining a piezoelectric inductor with higher sensitivity, or because there is a tendency to form a new interface that can retain charge between the piezoelectric layer and the layer stacked with the piezoelectric layer, thereby improving the piezoelectric constant of the piezoelectric layer in the obtained piezoelectric inductor.

[實施例] [Implementation example]

接著，呈示實施例來更詳細地說明本發明的一實施型態，不過本發明並不受該等實施例所限定。 Next, an embodiment is presented to illustrate an implementation form of the present invention in more detail, but the present invention is not limited to such embodiments.

〔實施例1〕 [Example 1]

在10cm見方的下述壓電片的一面側中央部的9cm見方的範圍，塗佈Plascoat股份有限公司製的Polycalm PCS-1201S(包含導電性填料及黏結劑)，在80℃下熟化30分鐘使之硬化而形成導電性塗膜(厚度：10μm)，以其作為訊號極。 Apply Polycalm PCS-1201S (containing conductive filler and binder) manufactured by Plascoat Co., Ltd. to a 9cm square area in the center of one side of the following piezoelectric sheet of 10cm square, and cure it at 80°C for 30 minutes. It is hardened to form a conductive coating film (thickness: 10μm), which is used as a signal electrode.

前述壓電片係如下述製作。 The aforementioned piezoelectric sheet is manufactured as follows.

將單纖維徑為5至8μm，纖維徑變動係數為0.3之玻璃纖維扎成束而形成纖維束(纖維束徑(長徑)：15μm)，用所得到的纖維束進行平織而作 成玻璃織布。將此玻璃織布浸漬於PTFE分散液中使PTFE粒子含浸於其中，製作成壓電片(厚度：100μm)。 Glass fibers with a single fiber diameter of 5 to 8 μm and a fiber diameter variation coefficient of 0.3 are bundled to form a fiber bundle (fiber bundle diameter (long diameter): 15 μm), and the obtained fiber bundle is woven flat to make a glass woven fabric. This glass woven fabric is immersed in a PTFE dispersion to impregnate PTFE particles therein, and a piezoelectric sheet (thickness: 100 μm) is made.

所得到的壓電片的基重為1.2g/m²。 The basis weight of the obtained piezoelectric sheet was 1.2 g/m ² .

從所得到的壓電片切取試驗片，在氮氣環境下，以400℃進行30分鐘的加熱，根據加熱前後的質量變化算出玻璃的質量及PTFE的質量，求出所得到的壓電片中的PTFE含有比率。該PTFE含有比率為35質量%。 A test piece was cut out from the obtained piezoelectric sheet and heated at 400°C for 30 minutes in a nitrogen atmosphere. The mass of the glass and the mass of PTFE were calculated from the mass changes before and after heating, and the mass of the obtained piezoelectric sheet was determined. PTFE content ratio. The PTFE content ratio is 35% by mass.

另外，從前述PTFE及玻璃的質量比及試驗片的質量實測值，算出假設沒有空隙之試驗片的理論體積，且藉由量測該試驗片的尺寸而算出試驗片的實測體積，利用下式而從理論體積與實測體積之差算出所得到的壓電片的孔隙率。該孔隙率為34體積%。 In addition, the theoretical volume of the test piece assuming no voids was calculated from the mass ratio of PTFE and glass and the measured mass of the test piece, and the measured volume of the test piece was calculated by measuring the size of the test piece. The porosity of the obtained piezoelectric sheet was calculated from the difference between the theoretical volume and the measured volume using the following formula. The porosity is 34% by volume.

孔隙率(體積%)=(1-(理論體積/實測體積))×100 Porosity (volume %) = (1-(theoretical volume/measured volume))×100

在壓電片之與導電性塗膜相反的一側面，設置9cm見方的鋁箔(厚度：18μm)作為接地極而形成壓電感測器。 On the side of the piezoelectric sheet opposite to the conductive coating, a 9 cm square aluminum foil (thickness: 18 μm) is placed as a ground electrode to form a piezoelectric inductor.

使用春日電機(股份有限公司)製的電暈放電裝置，以電極間距離12.5mm，電極間電壓-15kV，在室溫下進行3分鐘(在不發生過電流之條件下)，對所得到的壓電感測器進行電暈放電，完成前述壓電感測器的極化處理。 Using a corona discharge device manufactured by Kasuga Electric Co., Ltd., the obtained piezo-inductor was subjected to corona discharge at an inter-electrode distance of 12.5 mm and an inter-electrode voltage of -15 kV for 3 minutes at room temperature (without overcurrent), completing the polarization treatment of the aforementioned piezo-inductor.

為了從壓電感測器向經極化處理之壓電感測器提取電信號，使用銀漿將信號極與同軸電纜的芯線電連接，並且將銀漿用於接地極與同軸電纜的編織線電連接。 In order to extract electrical signals from the piezoelectric sensor to the polarized piezoelectric sensor, silver paste is used to electrically connect the signal electrode to the core wire of the coaxial cable, and silver paste is used to the ground electrode and the braided wire of the coaxial cable. Electrical connection.

所得到的壓電片之訊號極及接地極的彎曲剛性係以如下所述的方式測定。訊號極的彎曲剛性為2GPa，接地極的彎曲剛性為70GPa。 The bending rigidity of the signal electrode and ground electrode of the obtained piezoelectric sheet was measured as follows. The bending rigidity of the signal electrode is 2GPa, and the bending rigidity of the ground electrode is 70GPa.

<彎曲剛性> <Bending rigidity>

彎曲剛性係定義為材料的楊氏係數與斷面二次矩之積。斷面二次矩係以W×D³/12所示，W及D分別為材料的寬度及厚度。 Bending stiffness is defined as the product of the Young's modulus and the second moment of section of a material. The second moment of section is expressed as W×D ³ /12, where W and D are the width and thickness of the material, respectively.

訊號極的楊氏係數係依據下述方式測定：將Polycalm PCS-1201S塗佈在玻璃板上，在80℃下熟化30分鐘使之硬化後，藉由從玻璃板剝離，得到厚度10μm的塗膜，然後用所得到的塗膜按照JIS R 1602(3點彎曲法)進行靜力試驗而得出楊氏係數。 The Young's coefficient of the signal electrode is measured as follows: Polycalm PCS-1201S is coated on a glass plate, cured by aging at 80°C for 30 minutes, and then peeled off from the glass plate to obtain a coating film with a thickness of 10 μm. , and then use the obtained coating film to perform a static test in accordance with JIS R 1602 (3-point bending method) to obtain the Young's coefficient.

接地極的楊氏係數係使用前述疊合之前的鋁箔，按照JIS Z 2280(3點彎曲法)以測定靜態楊氏係數。 The Young's coefficient of the ground electrode was measured in accordance with JIS Z 2280 (3-point bending method) using the aluminum foil before lamination.

將已與前述同軸電纜連接之壓電感測器整個用PET製膠帶加以密封，再在其外側兩面積層導電性膠帶作為電磁屏蔽層。接著，使用銀膠將該電磁屏蔽層與前述同軸電纜的編包線予以電性連接。然後，用PET製膠帶將所得到的積層體密封，製成評價用感測器。 The piezoelectric inductor connected to the aforementioned coaxial cable is sealed with PET tape, and then conductive tape is layered on both sides of its outer side as an electromagnetic shielding layer. Then, the electromagnetic shielding layer is electrically connected to the braided wire of the aforementioned coaxial cable using silver glue. Then, the resulting laminate is sealed with PET tape to make an evaluation sensor.

<感測器之對於按壓的初期性能評價> <Evaluation of the initial performance of the sensor for pressure>

為了評定評價用感測器的初期性能如何，將製成的評價用感測器以訊號極在下側的方式放置在絶緣性的水平的台上，且將同軸電纜連接至示波器，按照JIS B 9717-1而進行輸出電壓的測定。在室溫下，對於如上述 配置的評價用感測器的上側中央，從鉛直方向用ψ80mm的不銹鋼製的壓頭以2mm/s的速度進行按壓，測出按壓時的輸出電壓。結果顯示於表1中。 In order to evaluate the initial performance of the evaluation sensor, the manufactured evaluation sensor was placed on an insulating horizontal table with the signal pole at the bottom, and the coaxial cable was connected to an oscilloscope to measure the output voltage according to JIS B 9717-1. At room temperature, the center of the upper side of the evaluation sensor configured as above was pressed at a speed of 2mm/s with a ψ80mm stainless steel pressure head from the lead vertical direction, and the output voltage during pressing was measured. The results are shown in Table 1.

<感測器承受反覆按壓的耐久性能評價> <Evaluation of the durability of the sensor under repeated pressure>

為了評定評價用感測器的耐久性的好壞，以與前述一樣的方法，在室溫下用ψ80mm的不銹鋼製的壓頭以500mm/s之速度從相對於鉛直方向傾斜14°之角度反覆地按壓與示波器連接的評價用感測器的上側中央，具體而言，係按壓10,000次、100,000次或1,000,000次時，測定各個輸出電壓。結果顯示於表1中。 In order to evaluate the durability of the evaluation sensor, in the same manner as described above, a ψ80mm stainless steel indenter was repeatedly tilted at an angle of 14° with respect to the vertical direction at a speed of 500mm/s at room temperature. The upper center of the evaluation sensor connected to the oscilloscope is pressed, specifically, 10,000 times, 100,000 times, or 1,000,000 times, and each output voltage is measured. The results are shown in Table 1.

〔比較例1〕 [Comparison Example 1]

除了使用與前述接地極相同的鋁箔替代前述導電性塗膜來作為訊號極之外，以與實施例1同樣的方法製作出評價用感測器，與實施例1同樣進行該感測器的性能評價。結果係顯示於表1中。 In addition to using the same aluminum foil as the ground electrode instead of the conductive coating as the signal electrode, the evaluation sensor was made in the same way as in Example 1, and the performance evaluation of the sensor was carried out in the same way as in Example 1. The results are shown in Table 1.

〔實施例2〕 [Example 2]

除了使用9cm見方的銅箔(厚度：35μm)替代實施例1中使用的接地極來作為接地極之外，與實施例1同樣，進行感測器承受反覆按壓的耐久性能評價。將按壓1000次時的輸出電壓在1500mV以上的情況評價為AA，將1000mV以上且未達1500mV之情況評價為BB，將300mV以上且未達1000mV之情況評價為CC，將未達300mV之情況評價為DD。結果顯示於表2中。 The durability of the sensor under repeated pressing was evaluated in the same manner as in Example 1, except that a 9 cm square copper foil (thickness: 35 μm) was used instead of the grounding electrode used in Example 1 as the grounding electrode. The output voltage above 1500 mV after 1000 pressings was evaluated as AA, above 1000 mV but below 1500 mV was evaluated as BB, above 300 mV but below 1000 mV was evaluated as CC, and below 300 mV was evaluated as DD. The results are shown in Table 2.

另外，與實施例1同樣測出的接地極的彎曲剛性為129GPa。 In addition, the bending rigidity of the ground electrode measured in the same manner as in Example 1 was 129 GPa.

〔實施例3〕 [Implementation Example 3]

除了使用9cm見方的鎳箔(厚度：30μm)替代實施例2中使用的接地極來作為接地極之外，與實施例2同樣，進行感測器承受反覆按壓的耐久性能評價。結果顯示於表2中。 The durability of the sensor under repeated pressing was evaluated in the same manner as in Example 2, except that a 9 cm square nickel foil (thickness: 30 μm) was used instead of the grounding electrode used in Example 2. The results are shown in Table 2.

另外，與實施例1同樣測定的接地極的彎曲剛性為198GPa。 In addition, the bending rigidity of the ground electrode measured in the same manner as in Example 1 was 198 GPa.

〔比較例2〕 [Comparison Example 2]

除了使用9cm見方的銅箔(厚度：35μm)替代實施例3中使用的訊號極作為訊號極之外，與實施例3同樣，進行感測器承受反覆按壓的耐久性能評價。結果顯示於表2中。 The durability of the sensor under repeated pressing was evaluated in the same manner as in Example 3, except that a 9 cm square copper foil (thickness: 35 μm) was used instead of the signal electrode used in Example 3. The results are shown in Table 2.

另外，與實施例1同樣進行測定所得到的訊號極的彎曲剛性為129GPa。此時的訊號極的楊氏係數係用疊合之前的銅箔，按照JIS Z 2280(三點彎曲法)測定靜態楊氏係數。 In addition, the bending rigidity of the signal pole obtained by measuring in the same manner as in Example 1 is 129 GPa. The Young's modulus of the signal pole at this time is the static Young's modulus measured according to JIS Z 2280 (three-point bending method) using the copper foil before stacking.

Claims (8)

一種壓電感測器，係依序包含金屬層、壓電層及導電性塗膜層，其中，前述金屬層的彎曲剛性與前述導電性塗膜層的彎曲剛性之比為10至100。 A piezoelectric sensor includes a metal layer, a piezoelectric layer and a conductive coating layer in sequence, wherein the ratio of the bending rigidity of the metal layer to the bending rigidity of the conductive coating layer is 10 to 100. 如申請專利範圍第1項所述之壓電感測器，其中，前述導電性塗膜層係包含導電性填料及黏結劑之層。 The piezoelectric inductor as described in Item 1 of the patent application, wherein the conductive coating layer is a layer containing conductive fillers and adhesives. 如申請專利範圍第1或2項所述之壓電感測器，其中，前述壓電層係包含有機聚合物之不織布或織布，而該有機聚合物不具有起因於分子及結晶構造的偶極。 A piezoelectric inductor as described in item 1 or 2 of the patent application, wherein the piezoelectric layer is a non-woven fabric or a woven fabric comprising an organic polymer, and the organic polymer does not have a dipole resulting from a molecular and crystal structure. 如申請專利範圍第3項所述之壓電感測器，其中，前述有機聚合物為聚四氟乙烯。 For the piezoelectric sensor described in item 3 of the patent application, the organic polymer is polytetrafluoroethylene. 如申請專利範圍第3項所述之壓電感測器，其中，構成前述不織布或織布之纖維的平均纖維徑為0.05至50μm。 The piezoelectric sensor as described in item 3 of the patent application, wherein the average fiber diameter of the fibers constituting the non-woven fabric or woven fabric is 0.05 to 50 μm. 如申請專利範圍第3項所述之壓電感測器，其中，構成前述不織布或織布之纖維的纖維徑變動係數為0.7以下。 The piezoelectric sensor described in claim 3, wherein the fiber diameter variation coefficient of the fibers constituting the non-woven fabric or woven fabric is 0.7 or less. 如申請專利範圍第1或2項所述之壓電感測器，其中，前述壓電層的孔隙率為0.1至70體積%。 For the piezoelectric sensor described in item 1 or 2 of the patent application, the porosity of the piezoelectric layer is 0.1 to 70% by volume. 一種申請專利範圍第1至7項中任一項所述之壓電感測器的製造方法，該壓電感測器係依序包含金屬層、壓電層及導電性塗膜層，且該製造方法包含：在壓電層塗裝包含導電性填料及黏結劑之組成物，然後使該塗裝的組成物乾燥或硬化之步驟。 A method for manufacturing a piezoelectric sensor as described in any one of items 1 to 7 of the patent application, the piezoelectric sensor sequentially includes a metal layer, a piezoelectric layer and a conductive coating layer, and the The manufacturing method includes the steps of coating a composition containing conductive filler and a binder on the piezoelectric layer, and then drying or hardening the coating composition.