JP7207302B2 - Polysaccharide composition for producing piezoelectric film having d14 piezoelectric constant and method for producing piezoelectric film having d14 piezoelectric constant - Google Patents
Polysaccharide composition for producing piezoelectric film having d14 piezoelectric constant and method for producing piezoelectric film having d14 piezoelectric constant Download PDFInfo
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- JP7207302B2 JP7207302B2 JP2019526937A JP2019526937A JP7207302B2 JP 7207302 B2 JP7207302 B2 JP 7207302B2 JP 2019526937 A JP2019526937 A JP 2019526937A JP 2019526937 A JP2019526937 A JP 2019526937A JP 7207302 B2 JP7207302 B2 JP 7207302B2
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
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Classifications
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/704—Piezoelectric or electrostrictive devices based on piezoelectric or electrostrictive films or coatings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C41/00—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor
- B29C41/02—Shaping by coating a mould, core or other substrate, i.e. by depositing material and stripping-off the shaped article; Apparatus therefor for making articles of definite length, i.e. discrete articles
- B29C41/12—Spreading-out the material on a substrate, e.g. on the surface of a liquid
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L1/00—Compositions of cellulose, modified cellulose or cellulose derivatives
- C08L1/08—Cellulose derivatives
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/01—Manufacture or treatment
- H10N30/09—Forming piezoelectric or electrostrictive materials
- H10N30/098—Forming organic materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N30/00—Piezoelectric or electrostrictive devices
- H10N30/80—Constructional details
- H10N30/85—Piezoelectric or electrostrictive active materials
- H10N30/857—Macromolecular compositions
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- Medicinal Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Moulding By Coating Moulds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
本発明は多糖類を用いたｄ１４圧電定数を有する圧電フィルムの製造技術に関する。 The present invention relates to a technique for producing a piezoelectric film having a d14 piezoelectric constant using polysaccharides.
加圧等の形状変化によって電荷を発生する材料を圧電体と言い、各種センサーやアクチュエーターに幅広く応用されている。従来より圧電体としてはＰＺＴ（チタン酸ジルコン酸鉛）を始めとしたセラミックが利用されていたが、鉛を含有すること、高温焼成が必要なこと、可とう性を持たないこと、大面積化できないことなどに課題があった。このため、近年、ポリフッ化ビニリデン（ＰＶＤＦ）、ポリフッ化ビニリデン三フッ化エチレン共重合体（Ｐ（ＶＤＦ／ＴｒＦＥ））などの高分子圧電材料（特許文献１～３等）、圧電材料ではないが加圧によって電荷を発生するエレクトレット（特許文献４等）等の各種材料が提案されている。これらは、従来のセラミック圧電体では実現することができない大面積化や可とう性といった特徴を生かした用途で応用が期待されている。 Piezoelectric material is a material that generates electric charge when its shape is changed by pressurization, etc., and is widely used in various sensors and actuators. Conventionally, ceramics such as PZT (lead zirconate titanate) have been used as piezoelectric materials. I had a problem with what I couldn't do. For this reason, in recent years, polymer piezoelectric materials such as polyvinylidene fluoride (PVDF) and polyvinylidene fluoride trifluoride copolymer (P(VDF/TrFE)) (Patent Documents 1 to 3, etc.), and although not piezoelectric materials, Various materials have been proposed, such as electrets (Patent Document 4, etc.), which generate electric charges when pressurized. These are expected to be applied in applications that take advantage of their characteristics such as large area and flexibility, which cannot be realized with conventional ceramic piezoelectric materials.
しかしながら、これらの高分子圧電材料およびエレクトレットは温度変化に依る電荷発生（これを、焦電効果という）を伴うために、例えば、タッチセンサーなどに使用した場合は体温による焦電効果で発生する信号と、加圧による圧電効果で発生する信号とが混在してしまい、純粋に加圧を測定することが困難であるという問題がある。また、製造方法に関しても、専用の装置を用いた延伸と分極、或いは、分極が必要であり、そのためにコストが高くなるという問題があった。 However, these polymer piezoelectric materials and electrets are accompanied by charge generation due to temperature changes (this is called pyroelectric effect). , and a signal generated by the piezoelectric effect due to pressurization are mixed, and it is difficult to purely measure the pressurization. Further, regarding the production method, stretching and polarization using a dedicated device, or polarization is required, which raises the problem of high cost.
一方、ポリ乳酸、ポリアミノ酸、セルロースのような光学活性を有する高分子を配向させて分子対称性をD∞対称とすると、ずり方向の力による電荷を発生する圧電体である、ｄ１４圧電定数を有する圧電体（以下、「ｄ１４圧電体」とも略称する）になることが知られている（特許文献５、６、非特許文献１、２、３、４参照）。ｄ１４圧電体は分極を持たないために焦電効果を有さず、タッチセンサーなど温度が変化する用途でも純粋な加圧を測定できるという利点がある。 On the other hand, when optically active polymers such as polylactic acid, polyamino acid, and cellulose are oriented and the molecular symmetry is D∞ symmetry, the d14 piezoelectric constant, which is a piezoelectric material that generates charges due to the force in the shear direction, is It is known that a piezoelectric body (hereinafter also abbreviated as "d14 piezoelectric body") having a Since the d14 piezoelectric material has no polarization, it has no pyroelectric effect, and has the advantage of being able to measure pure pressure even in applications where the temperature changes, such as touch sensors.
しかしながら、特許文献５、６、非特許文献１、２に記載されている、ポリ乳酸、ポリアミノ酸、又はセルロースからなるｄ１４圧電体は、これらの高分子の未延伸のフィルムを一軸方向に延伸して主鎖を配向させることで得られている。これらの製造法では延伸中にフィルムが破断するリスクがあり、さらに延伸後にフィルムの幅（一軸方向と直交する方向の幅）が狭まるなどの問題がある。 However, the d14 piezoelectric material made of polylactic acid, polyamino acid, or cellulose described in Patent Documents 5 and 6 and Non-Patent Documents 1 and 2 stretches unstretched films of these polymers in a uniaxial direction. It is obtained by orienting the main chain with In these production methods, there is a risk that the film will be broken during stretching, and furthermore, there are problems such as the width of the film (the width in the direction orthogonal to the uniaxial direction) being narrowed after stretching.
上記の事情に鑑み、本発明が解決しょうとする課題は、未延伸のフィルムでありながら、高いｄ１４圧電定数を有する高分子圧電フィルムの製造を可能にする樹脂組成物および該樹脂組成物を用いたｄ１４圧電定数を有する圧電フィルムの製造方法を提供することにある。 In view of the above circumstances, the problem to be solved by the present invention is to provide a resin composition that enables the production of a polymer piezoelectric film having a high d14 piezoelectric constant even though it is an unstretched film, and to use the resin composition. The object of the present invention is to provide a method for manufacturing a piezoelectric film having a low d14 piezoelectric constant.
本発明者は、上記の課題を解決するために鋭意検討した結果、光学活性を有する高分子であるセルロース等の多糖類を液状媒体とともに複屈折を有する比較的高粘度の液状組成物に調製すると、該液状組成物を塗工、乾燥して得られるフィルムは、高いｄ１４圧電定数を有する圧電フィルムとなることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a relatively high-viscosity liquid composition having birefringence and a polysaccharide such as cellulose, which is an optically active polymer, is prepared together with a liquid medium. , the inventors have found that the film obtained by coating and drying the liquid composition is a piezoelectric film having a high d14 piezoelectric constant, and have completed the present invention.
すなわち、本発明は以下の通りである。
［１］ 多糖類および液状媒体を含み、複屈折を有する、多糖類組成物であって、ｄ１４圧電定数の最高値が１ｐＣ／Ｎ以上の圧電フィルムの製造に用いられる多糖類組成物。
［２］ 液状媒体が、沸点４０℃以上、２５０℃以下の液状媒体を１種以上含む、上記［１］記載の多糖類組成物。
［３］ 液状媒体が、沸点４０℃以上、２１０℃以下の液状媒体を１種以上含む、上記［１］記載の多糖類組成物。
［４］ 液状媒体が、メタノール、エタノール、水、１，４－ジオキサン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、γ－ブチロラクトン、ベンジルアルコール、１，２－ジクロロエタン、ジクロロメタン、クロロホルム、トリフルオロ酢酸からなる群から選択される１種以上である、上記［１］記載の多糖類組成物。
［５］ 多糖類のＧＰＣ法による数平均分子量が１０，０００以上である、上記［１］～［４］のいずれか１つに記載の多糖類組成物。
［６］ 多糖類がセルロースまたはその誘導体を含む、上記［１］～［５］のいずれか１つに記載の多糖類組成物。
［７］ 多糖類がセルロース誘導体を含み、該セルロース誘導体がメチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、モノアセチルセルロース、ジアセチルセルロース、トリアセチルセルロース、カルボキシメチルセルロースからなる群から選択される１種または２種以上である、上記［１］～［５］のいずれか１つに記載の多糖類組成物。
［８］ 多糖類がキサンタンを含む、上記［１］～［５］のいずれか１つに記載の多糖類組成物。
［９］ 多糖類組成物の固形分量が２０重量％以上である、上記［１］～［８］のいずれか１つに記載の多糖類組成物。
［１０］ 多糖類組成物の２５℃における粘度が５，０００ｍＰａ・ｓ以上である、上記［１］～［９］のいずれか１つに記載の多糖類組成物。
［１１］ 多糖類組成物の２５℃における粘度が５０，０００ｍＰａ・ｓ以上である、上記［１］～［９］のいずれか１つに記載の多糖類組成物。
［１２］ 多糖類および液状媒体を含み、複屈折を有する多糖類組成物を支持体上に塗工する第１工程、および該第１工程で得られた多糖類組成物層を乾燥してフィルムとする第２工程を含む、ｄ１４圧電定数の最高値が１ｐＣ／Ｎ以上の圧電フィルムの製造方法。
［１３］ 第２工程は磁場を作用させておらず、かつ、第２工程後に、フィルムの延伸工程を含まない、上記［１２］記載の方法。
［１４］ 液状媒体が沸点４０℃以上、２５０℃以下の液状媒体を１種以上含む、上記［１２］または［１３］記載の方法。
［１５］ 液状媒体が沸点４０℃以上、２１０℃以下の液状媒体を１種以上含む、上記［１２］または［１３］記載の方法。
［１６］ 液状媒体が、メタノール、エタノール、水、１，４－ジオキサン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、γ－ブチロラクトン、ベンジルアルコール、１，２－ジクロロエタン、ジクロロメタン、クロロホルム、トリフルオロ酢酸からなる群から選択される１種以上である、上記［１２］または［１３］記載の方法。
［１７］ 多糖類のＧＰＣ法による数平均分子量が１０，０００以上である、上記［１２］～［１６］のいずれか１つに記載の方法。
［１８］ 多糖類がセルロースまたはその誘導体を含む、上記［１２］～［１６］のいずれか１つに記載の方法。
［１９］ 多糖類がセルロース誘導体であり、該セルロース誘導体が、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、モノアセチルセルロース、ジアセチルセルロース、トリアセチルセルロース、カルボキシメチルセルロースからなる群から選択される１種または２種以上である、上記［１２］～［１７］のいずれか１つに記載の方法。
［２０］ 多糖類がキサンタンを含む、上記［１２］～［１７］のいずれか１つに記載の方法。
［２１］ 第１工程において、多糖類組成物の塗り厚が５００μｍ以下となるように多糖類組成物を塗工する、上記［１２］～［２０］のいずれか１つに記載の方法。
［２２］ 多糖類組成物の固形分量が２０重量％以上である、上記［１２］～［２１］のいずれか１つに記載の方法。
［２３］ 多糖類組成物の２５℃における粘度が５，０００ｍＰａ・ｓ以上である、上記［１２］～［２２］のいずれか１つに記載の方法。
［２４］ 多糖類組成物の２５℃における粘度が５０，０００ｍＰａ・ｓ以上である、上記［１２］～［２２］のいずれか１つに記載の方法。
［２５］ 第２工程が多糖類組成物層を３００℃以下の温度で乾燥することを含む上記［１２］～［２４］のいずれか１つに記載の方法。That is, the present invention is as follows.
[1] A polysaccharide composition containing a polysaccharide and a liquid medium and having birefringence, the polysaccharide composition being used for producing a piezoelectric film having a maximum d14 piezoelectric constant of 1 pC/N or more.
[2] The polysaccharide composition according to [1] above, wherein the liquid medium contains one or more liquid media having a boiling point of 40°C or higher and 250°C or lower.
[3] The polysaccharide composition according to [1] above, wherein the liquid medium contains one or more liquid media having a boiling point of 40°C or higher and 210°C or lower.
[4] The liquid medium is methanol, ethanol, water, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, benzyl alcohol, 1,2-dichloroethane, dichloromethane, chloroform, The polysaccharide composition according to [1] above, which is one or more selected from the group consisting of trifluoroacetic acid.
[5] The polysaccharide composition according to any one of [1] to [4] above, wherein the polysaccharide has a number average molecular weight of 10,000 or more according to the GPC method.
[6] The polysaccharide composition according to any one of [1] to [5] above, wherein the polysaccharide contains cellulose or a derivative thereof.
[7] The polysaccharide contains a cellulose derivative, and the cellulose derivative is selected from the group consisting of methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, monoacetylcellulose, diacetylcellulose, triacetylcellulose, and carboxymethylcellulose. The polysaccharide composition according to any one of [1] to [5] above, which is one or more.
[8] The polysaccharide composition according to any one of [1] to [5] above, wherein the polysaccharide contains xanthan.
[9] The polysaccharide composition according to any one of [1] to [8] above, wherein the polysaccharide composition has a solid content of 20% by weight or more.
[10] The polysaccharide composition according to any one of [1] to [9] above, wherein the polysaccharide composition has a viscosity of 5,000 mPa·s or more at 25°C.
[11] The polysaccharide composition according to any one of [1] to [9] above, wherein the polysaccharide composition has a viscosity of 50,000 mPa·s or more at 25°C.
[12] A first step of coating a polysaccharide composition containing a polysaccharide and a liquid medium and having birefringence on a support, and drying the polysaccharide composition layer obtained in the first step to obtain a film A method for producing a piezoelectric film having a maximum d14 piezoelectric constant of 1 pC/N or more, comprising a second step of:
[13] The method according to [12] above, wherein the second step does not apply a magnetic field and does not include a film stretching step after the second step.
[14] The method according to the above [12] or [13], wherein the liquid medium contains one or more liquid media having a boiling point of 40°C or higher and 250°C or lower.
[15] The method according to the above [12] or [13], wherein the liquid medium contains one or more liquid media having a boiling point of 40°C or higher and 210°C or lower.
[16] The liquid medium is methanol, ethanol, water, 1,4-dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, benzyl alcohol, 1,2-dichloroethane, dichloromethane, chloroform, The method according to the above [12] or [13], which is one or more selected from the group consisting of trifluoroacetic acid.
[17] The method according to any one of [12] to [16] above, wherein the polysaccharide has a number average molecular weight of 10,000 or more by GPC method.
[18] The method according to any one of [12] to [16] above, wherein the polysaccharide comprises cellulose or a derivative thereof.
[19] The polysaccharide is a cellulose derivative, and the cellulose derivative is selected from the group consisting of methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, monoacetylcellulose, diacetylcellulose, triacetylcellulose, and carboxymethylcellulose. The method according to any one of [12] to [17] above, which is one or more than one.
[20] The method according to any one of [12] to [17] above, wherein the polysaccharide contains xanthan.
[21] The method according to any one of [12] to [20] above, wherein in the first step, the polysaccharide composition is applied so that the coating thickness of the polysaccharide composition is 500 μm or less.
[22] The method according to any one of [12] to [21] above, wherein the polysaccharide composition has a solid content of 20% by weight or more.
[23] The method according to any one of [12] to [22] above, wherein the polysaccharide composition has a viscosity at 25°C of 5,000 mPa·s or more.
[24] The method according to any one of [12] to [22] above, wherein the polysaccharide composition has a viscosity of 50,000 mPa·s or more at 25°C.
[25] The method according to any one of [12] to [24] above, wherein the second step comprises drying the polysaccharide composition layer at a temperature of 300° C. or less.
［２６］ 上記［１２］～［２５］のいずれか１つの方法で製造されたｄ１４圧電定数の最高値が１ｐＣ／Ｎ以上の圧電フィルムの片面または両面に電極が形成されており、前記電極に配線が接続されていることを特徴とする、センサーまたはアクチュエーター。
［２７］ 被検査物に貼付して使用され、被検査物の曲げや歪みを検知する、上記［２６］に記載のセンサーまたはアクチュエーター。
［２８］ 圧電体として、上記［１２］～［２５］のいずれか１つの方法で製造されたｄ１４圧電定数の最高値が１ｐＣ／Ｎ以上の圧電フィルムを具備する、モノモルフ、バイモルフ、片持ち梁構造からなる群から選択される構造のセンサーまたはアクチュエーター。[26] Electrodes are formed on one or both sides of a piezoelectric film having a maximum d14 piezoelectric constant of 1 pC/N or more produced by the method of any one of [12] to [25] above, and A sensor or actuator characterized by a wire connection.
[27] The sensor or actuator according to [26] above, which is attached to an object to be inspected and detects bending or strain of the object to be inspected.
[28] A monomorph, bimorph, or cantilever comprising, as a piezoelectric body, a piezoelectric film having a maximum d14 piezoelectric constant of 1 pC/N or more, manufactured by any one of the methods of [12] to [25] above. A sensor or actuator of structure selected from the group consisting of structures.
本発明の多糖類組成物によれば、ｄ１４圧電定数が大きく、しかも、その製造過程におけるフィルムに破断が生じるリスクがなく、かつ圧電特性発現後も広い幅のフィルムを得ることができる。このため、意図した設計幅の圧電フィルムを製造することができ、無機圧電体にはなく、有機圧電体オリジナルの特徴である、大面積化をより簡便に実現することができる。 According to the polysaccharide composition of the present invention, it is possible to obtain a film having a large d14 piezoelectric constant, no risk of breakage in the film during its production process, and a wide width even after the development of piezoelectric properties. Therefore, it is possible to manufacture a piezoelectric film having an intended design width, and it is possible to more easily achieve a large area, which is a feature of the original organic piezoelectric material, which is not found in inorganic piezoelectric materials.
また、従来の圧電フィルムを使用したセンサーは、フィルムを延伸して得られた圧電フィルムに電極を形成してセンサーとしていたが、本発明の多糖類組成物を使用すれば、例えば、金属箔等の導電体を支持体として、これに塗工、乾燥することで、圧電フィルムの製造と同時に電極として前記金属箔等の導電体を備えるセンサーを作製することができる。このため、従来では考えられなかったプロセスによってセンサーを作製することができる。 Further, conventional sensors using a piezoelectric film are formed by forming electrodes on the piezoelectric film obtained by stretching the film. By using the conductor of (1) as a support, coating and drying on this, a sensor having the conductor such as the metal foil as an electrode can be produced at the same time as the piezoelectric film is produced. For this reason, the sensor can be produced by a process that has not been conceived in the past.
以下、本発明をその好適な実施形態を示してより詳しく説明する。 Hereinafter, the present invention will be described in more detail by showing its preferred embodiments.
本発明でいう「ｄ１４圧電定数」とは、圧電テンソルの一つであり、ずり応力を印加したときに発生する電荷の量から求められる。単位ずり応力あたりの発生電荷量がｄ１４圧電定数となる。また、「ｄ１４圧電定数の最高値」とは、ずり応力をかける方向を変えて測定した場合に得られるｄ１４圧電定数のうちの最高値を意味するものとし、例えば、フィルムに対するずり応力をかける方向を１０°毎（好ましくは５°毎、より好ましくは１°毎）変更して測定することで決定することができる。ここでいう「ずり応力をかける方向」とはフィルムの主面内に描かれる、主面の中心を通る仮想直線の方向であり、例えば、「１０°毎変更する」とは、フィルムの主面の中心を軸として回転角が１０°相違する仮想直線を放射状に設定することを意味する。 The "d14 piezoelectric constant" referred to in the present invention is one of piezoelectric tensors, and is obtained from the amount of charge generated when shear stress is applied. The amount of charge generated per unit shear stress is the d14 piezoelectric constant. In addition, the "maximum value of the d14 piezoelectric constant" means the maximum value of the d14 piezoelectric constant obtained when the measurement is performed while changing the direction in which the shear stress is applied. can be determined by changing every 10° (preferably every 5°, more preferably every 1°) and measuring. The "direction in which shear stress is applied" as used herein is the direction of an imaginary straight line drawn in the main surface of the film and passing through the center of the main surface. This means radially setting imaginary straight lines having rotation angles different from each other by 10° around the center of .
なお、ｄ１４圧電定数を有するフィルム（以下、「ｄ１４圧電体フィルム」ともいう。）は、理論上、フィルムを構成する分子の配向方向に対して交差角度が４５°となる方向からフィルムに周期的な引張り応力を加えて圧電定数を測定する場合に最大の値が出る。従って、分子の配向方向に対する交差角が４５°となる方向からずり応力を加えて発生する電荷の量を測定することでｄ１４圧電定数の最高値を決定することができる。 In theory, a film having a d14 piezoelectric constant (hereinafter also referred to as a “d14 piezoelectric film”) has a periodicity of The maximum value is obtained when the piezoelectric constant is measured by applying a large tensile stress. Therefore, the maximum value of the d14 piezoelectric constant can be determined by measuring the amount of charge generated by applying shear stress from the direction in which the crossing angle with respect to the orientation direction of the molecules is 45°.
一般に、ｄ１４圧電体フィルムにおけるフィルムを構成する分子の配向方向は、フィルムを力学的に延伸した方向やフィルムに外部からかけた電磁場の方向など、ｄ１４圧電体フィルムの製造方法から特定することができる。通常、フィルムを力学的に延伸してｄ１４圧電体フィルムを製造した場合はフィルムの延伸方向が配向方向とされ、フィルムに外部から電磁場をかけてｄ１４圧電体フィルムを製造した場合は電磁場の方向あるいは電磁場の方向に対する垂直方向が配向方向とされる。本発明においては、フィルム製造時の多糖類組成物の塗工方向が配向方向であると特定した。なお、製法が分からないｄ１４圧電体フィルムの場合、偏光顕微鏡、Ｘ線結晶回折、ＩＲ２色比などの分析から分子の向きを実際に確認して配向方向を決定することができる。この場合、フィルム中の個々の分子の向きを確認して、同一方向を向いている分子の数が最も多い分子群を構成する分子の向きが配向方向と定められるが、このようにして定められた配向方向は、例えば、ｄ１４圧電体フィルムがフィルムを力学的に延伸することで製造されたものである場合は、通常、フィルムの延伸方向と一致し、ｄ１４圧電体フィルムがフィルムに電磁場をかけて製造されたものである場合は、通常、電磁場の方向と一致する。本発明において、多糖類組成物の塗工、乾燥により得られるｄ１４圧電体フィルムも、偏光顕微鏡、Ｘ線結晶回折、ＩＲ２色比などの分析から分子の向き、すなわち、多糖類分子の主鎖の向きを実際に確認して配向方向を決定すれば、その配向方向は、通常、多糖類組成物の塗工方向と一致する。 In general, the orientation direction of the molecules constituting the film in the d14 piezoelectric film can be specified from the manufacturing method of the d14 piezoelectric film, such as the direction in which the film is dynamically stretched and the direction of the electromagnetic field applied to the film from the outside. . Normally, when a d14 piezoelectric film is produced by mechanically stretching a film, the stretching direction of the film is taken as the orientation direction, and when an electromagnetic field is applied to the film from the outside to produce a d14 piezoelectric film, the direction of the electromagnetic field or The orientation direction is the direction perpendicular to the direction of the electromagnetic field. In the present invention, the coating direction of the polysaccharide composition during film production is specified as the alignment direction. In the case of a d14 piezoelectric film whose production method is unknown, the orientation direction can be determined by actually confirming the orientation of the molecules through analysis such as polarizing microscope, X-ray crystal diffraction, and IR dichroic ratio. In this case, the orientation of the individual molecules in the film is confirmed, and the orientation of the molecules constituting the molecular group with the largest number of molecules facing the same direction is determined as the alignment direction. For example, when the d14 piezoelectric film is produced by mechanically stretching the film, the orientation direction usually coincides with the stretching direction of the film, and the d14 piezoelectric film applies an electromagnetic field to the film. If it was manufactured by a In the present invention, the d14 piezoelectric film obtained by coating and drying the polysaccharide composition is also analyzed by polarizing microscope, X-ray crystal diffraction, IR dichroic ratio, etc. If the alignment direction is determined by actually confirming the orientation, the alignment direction usually coincides with the coating direction of the polysaccharide composition.
本発明におけるｄ１４圧電フィルムにおいて、「ｄ１４圧電定数の最高値」は、１ｐＣ／Ｎ以上が好ましく、２ｐＣ／Ｎ以上がより好ましく、３ｐＣ／Ｎ以上がさらに好ましい。圧電定数は高ければ高いほど好ましく、上限値には特に制限はないが、好ましくは４０ｐＣ／Ｎ以下である。 In the d14 piezoelectric film of the present invention, the "maximum value of the d14 piezoelectric constant" is preferably 1 pC/N or more, more preferably 2 pC/N or more, and even more preferably 3 pC/N or more. The higher the piezoelectric constant, the better, and the upper limit is not particularly limited, but is preferably 40 pC/N or less.
本発明では、従来のフィルムの延伸という手法を用いることなく、多糖類および液状媒体を含み多糖類組成物を支持体上に塗工する第１工程および該第１工程で得られた多糖類組成物層を乾燥してフィルムとする第２工程を含む方法によって、ｄ１４圧電定数の最高値が１ｐＣ／Ｎ以上のｄ１４圧電フィルムを製造する。これは、多糖類が、支持体上に塗工するという操作のみで高度に配向し得、加熱を含む乾燥工程を経てもなお塗工後の配向状態を保持することを見出したことによる。すなわち、本発明では、フィルムを延伸する、あるいは、電磁場を用いて配向させることなく、多糖類分子が高度に配向して、ｄ１４圧電定数の最高値が１ｐＣ／Ｎ以上のｄ１４圧電フィルムを製造することに成功した。このため、本発明の多糖類組成物から製造されるｄ１４圧電フィルムは、未延伸フィルムでありながら、ｄ１４圧電定数の最高値が、１ｐＣ／Ｎ以上である。 In the present invention, the first step of coating a polysaccharide composition containing a polysaccharide and a liquid medium on a support without using the conventional method of stretching a film, and the polysaccharide composition obtained in the first step A d14 piezoelectric film having a maximum d14 piezoelectric constant of 1 pC/N or more is produced by a method comprising a second step of drying the layer to form a film. This is due to the discovery that polysaccharides can be highly oriented simply by coating them on a support and retain the oriented state after coating even after a drying step including heating. That is, in the present invention, a d14 piezoelectric film having a maximum d14 piezoelectric constant of 1 pC/N or more is produced by highly orienting polysaccharide molecules without stretching the film or using an electromagnetic field for orientation. succeeded in Therefore, the d14 piezoelectric film produced from the polysaccharide composition of the present invention has a maximum d14 piezoelectric constant of 1 pC/N or more even though it is an unstretched film.
なお、「塗工」とは、多糖類および液状媒体を含む多糖類組成物を支持体表面に塗り広げることであり、支持体表面と平行な方向にせん断が作用する。「塗工」と「延伸」はいずれも厚みを持った形状の樹脂を厚みの薄いフィルム状に成形するために用いられる手法で、広義には「延伸」に「塗工」も含まれると解釈し得る。従って、本明細書でいう「延伸」とは、液状媒体を含まない状態の樹脂に於いて加熱等を用いて弾性率を下げて引張あるいはプレス等を用いて、厚みの薄いフィルム状に成形することと定義し、「塗工」とは樹脂に液状媒体を含ませることで流動性を持たせて、その流動状態でせん断の力を加えることで、厚みの薄いフィルム状に成形し、その後に液状媒体を除去することと定義する。 The term "coating" means spreading a polysaccharide composition containing a polysaccharide and a liquid medium on the surface of a support, and shear acts in a direction parallel to the surface of the support. Both "coating" and "stretching" are methods used to form a thick resin into a thin film. In a broad sense, "stretching" is interpreted to include "coating" can. Therefore, the term "stretching" as used in this specification means that the elastic modulus of a resin that does not contain a liquid medium is lowered by heating or the like, and the resin is then stretched or pressed to form a thin film. "Coating" means adding fluidity to the resin by including a liquid medium, and applying a shearing force in the fluidized state to form a thin film, and then Defined as removing the liquid medium.
本発明において、多糖類組成物は複屈折を持つことと高い粘度を持つことが必要である。多糖類組成物が複屈折を持つとは、すなわち多糖類組成物中の多糖類分子が液状でありながら何らかの規則配列を持つことと同義である。多糖類は剛直な分子構造を有するため液状媒体に溶解させるとある程度の濃度（曇点）以上で複屈折を示す。多糖類組成物が複屈折を持つ場合は、塗工という操作により多糖類分子が高度に配向するが、複屈折を持たない場合は塗工によるせん断力程度では多糖類分子がd１４圧電定数を持つレベルで高度に配向することはない。また、多糖類組成物の粘度が低い場合、塗工により多糖類分子の高度な配向が実現したとしても、乾燥中に、多糖類組成物層中の多糖類分子が等方的な状態に戻るのに対し、多糖類組成物の粘度が高い場合は加熱を含む乾燥工程を経てもなお多糖類組成物層中の多糖類分子は塗工後の高度な配向状態を保持する。複屈折を持つ多糖類組成物の２５℃における粘度は、５，０００ｍＰａ・ｓ以上が好ましく、２０，０００ｍＰａ・ｓ以上がさらに好ましく、５０，０００ｍＰａ・ｓ以上がより好ましい。 In the present invention, the polysaccharide composition is required to have birefringence and high viscosity. That a polysaccharide composition has birefringence means that the polysaccharide molecules in the polysaccharide composition have some regular arrangement while being in a liquid state. Since polysaccharides have a rigid molecular structure, they exhibit birefringence above a certain concentration (cloud point) when dissolved in a liquid medium. When the polysaccharide composition has birefringence, the polysaccharide molecules are highly oriented by the operation of coating, but when the polysaccharide composition does not have birefringence, the polysaccharide molecules have a d14 piezoelectric constant with a shear force due to coating. It is not highly oriented at level. Further, when the viscosity of the polysaccharide composition is low, even if the polysaccharide molecules are highly oriented by coating, the polysaccharide molecules in the polysaccharide composition layer return to an isotropic state during drying. On the other hand, when the viscosity of the polysaccharide composition is high, the polysaccharide molecules in the polysaccharide composition layer maintain a highly oriented state after coating even after a drying step including heating. The viscosity of the polysaccharide composition having birefringence at 25° C. is preferably 5,000 mPa·s or more, more preferably 20,000 mPa·s or more, and even more preferably 50,000 mPa·s or more.
＜多糖類組成物＞
本発明の多糖類組成物は、多糖類および液状媒体を少なくとも含む。
［（Ａ）多糖類］
本発明において使用する多糖類（以下、「Ａ成分」ともいう）は、アルドヘキソース、アロース、アルトロース、グルコース、マンノース、グロース、イドース、ガラクトース、タロース、リブロース、キシルロース、リボース、アラビノース、キシロース、リキソース、デオキシリボース、プシコース、フルクトース、ソルボース、タガトース、フコース、フクロース、ラムノース等の単糖およびその誘導体からなる群から選択される１種類以上を単量体単位とするポリマー（すなわち、多糖類）であればよい。なお、多糖類の「誘導体」としては、天然の状態で誘導体化されて得られるものと多糖あるいはその誘導体として取り出した後にさらに有機合成反応を用いて誘導体化されているものが存在するが、いずれを用いてもよい。天然の状態で誘導体化されて得られるものの例としては、キサンタン、アルギン酸等が挙げられる。一方、有機合成反応を用いて誘導体化されているものの例としては、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、モノアセチルセルロース、ジアセチルセルロース、トリアセチルセルロース、カルボキシメチルセルロース等のセルロース誘導体、ヒドロキシプロピルキサンタンガム、カルボキシル化プルラン等の非セルロースの誘導体が挙げられる。また、上記に挙げるセルロース誘導体がイソシアネートを用いたウレタン化、エポキシドを用いたヒドロキシアルキル化、酸塩化物等を用いたエステル化、アクリルニトリルを用いたシアノエチル化等で誘導体化されたものも本発明でいう「セルロース誘導体」に含まれる。<Polysaccharide composition>
A polysaccharide composition of the present invention comprises at least a polysaccharide and a liquid medium.
[(A) Polysaccharide]
Polysaccharides used in the present invention (hereinafter also referred to as "component A") include aldohexose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, ribulose, xylulose, ribose, arabinose, xylose, and lyxose. , deoxyribose, psicose, fructose, sorbose, tagatose, fucose, fuculose, rhamnose, etc., and derivatives thereof. Just do it. The "derivatives" of polysaccharides include those obtained by derivatization in a natural state and those obtained by further derivatization using an organic synthesis reaction after being extracted as a polysaccharide or a derivative thereof. may be used. Examples of those obtained by derivatization in a natural state include xanthan, alginic acid, and the like. On the other hand, examples of those derivatized using organic synthesis reactions include cellulose derivatives such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, monoacetylcellulose, diacetylcellulose, triacetylcellulose, and carboxymethylcellulose. , hydroxypropylxanthan gum, carboxylated pullulan and other non-cellulose derivatives. In addition, the above-mentioned cellulose derivatives derivatized by urethanization using isocyanate, hydroxyalkylation using epoxide, esterification using acid chloride or the like, cyanoethylation using acrylonitrile, etc. are also present. It is included in the "cellulose derivative".
グルコース、マンノース、ガラクトース、キシロース、フルクトースおよびその誘導体からなる群から選択される１種類以上を単量体単位とするポリマー（特に、グルコースおよびその誘導体からなる群から選択される１種類以上を単量体単位とするポリマー）は、多糖類組成物中での溶解性乃至分散性の点で好ましい。 A polymer whose monomer units are one or more selected from the group consisting of glucose, mannose, galactose, xylose, fructose and derivatives thereof (in particular, one or more monomers selected from the group consisting of glucose and derivatives thereof) A polymer used as a body unit) is preferable from the viewpoint of solubility or dispersibility in the polysaccharide composition.
ポリマー（多糖類）は、ホモポリマー、コポリマーのいずれであってもよい。好ましいホモポリマーの具体例としては、例えば、セルロース、プルラン、デキストラン等が挙げられる。中でもセルロースは価格や性能の面から好ましい。 A polymer (polysaccharide) may be either a homopolymer or a copolymer. Specific examples of preferred homopolymers include cellulose, pullulan, dextran, and the like. Among them, cellulose is preferable in terms of price and performance.
好ましいコポリマーの具体例としては、キサンタン、グアガム、アルギン酸等が挙げられる。また、化学修飾された多糖類もホモポリマーとコポリマーという分類ではコポリマーと言え、中でもセルロース誘導体は価格や性能の面から好ましい。 Specific examples of preferred copolymers include xanthan, guar gum, alginic acid, and the like. In addition, chemically modified polysaccharides can also be classified as copolymers in the classification of homopolymers and copolymers, and among them, cellulose derivatives are preferable in terms of cost and performance.
多糖類はセルロースなどのように（分岐鎖が無いと言う意味での）直鎖型のポリマーであってもよく、キサンタンなどのように分岐鎖のある分岐型のポリマーであっても良いが、価格や種類の豊富さという観点から直鎖型のポリマーが好ましい。 The polysaccharide may be a linear polymer (in the sense of having no branched chain) such as cellulose, or a branched polymer having a branched chain such as xanthan. Linear polymers are preferred from the viewpoint of price and variety.
本発明において、多糖類は１種または２種以上を使用できる。なかでも、セルロース、セルロース誘導体、キサンタンが好ましく、より好ましくは、セルロース誘導体、キサンタンであり、特に好ましくは、メチルセルロース、エチルセルロース、ヒドロキシエチルセルロース、ヒドロキシプロピルセルロース、ヒドロキシプロピルメチルセルロース、モノアセチルセルロース、ジアセチルセルロース、トリアセチルセルロース、カルボキシメチルセルロースからなる群から選択される１種または２種以上であり、最も好ましくは、ヒドロキシプロピルセルロース、エチルセルロース、トリアセチルセルロースである。 In the present invention, one or more polysaccharides can be used. Among them, cellulose, cellulose derivatives and xanthan are preferred, cellulose derivatives and xanthan are more preferred, and methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropylmethyl cellulose, monoacetyl cellulose, diacetyl cellulose and triacetyl cellulose are particularly preferred. One or more selected from the group consisting of acetyl cellulose and carboxymethyl cellulose, most preferably hydroxypropyl cellulose, ethyl cellulose and triacetyl cellulose.
本発明において、多糖類の分子量特性は特に制限はされないが、フィルムの破断伸度向上の観点から、数平均分子量が１０，０００以上であることが好ましく、３０，０００以上がより好ましい。また、多糖類組成物の取扱い性の観点から、数平均分子量が１，０００，０００以下であることが好ましく、８００，０００以下がより好ましい。ここでいう、数平均分子量は、ＧＰＣ法（ゲル浸透クロマトグラフィー）によって測定されるポリスチレン換算値である。 In the present invention, the molecular weight characteristics of the polysaccharide are not particularly limited, but from the viewpoint of improving the breaking elongation of the film, the number average molecular weight is preferably 10,000 or more, more preferably 30,000 or more. Moreover, from the viewpoint of the handleability of the polysaccharide composition, the number average molecular weight is preferably 1,000,000 or less, more preferably 800,000 or less. The number average molecular weight referred to here is a polystyrene equivalent value measured by the GPC method (gel permeation chromatography).
［（Ｂ）液状媒体］
本発明において使用する液状媒体（以下、「Ｂ成分」ともいう）とは、それを媒体としてＡ成分が溶解乃至分散状態を形成し得る、２５℃で液状の化合物であれば、特に制限なく使用できる。[(B) liquid medium]
The liquid medium used in the present invention (hereinafter also referred to as "B component") is a compound that is liquid at 25 ° C. and in which the A component can form a dissolved or dispersed state using it as a medium. can.
具対的には、水；クロロホルム、ジクロロメタン、塩化メチレン、トリクロロエチレン、二塩化エチレン、１，２－ジクロロエタン、テトラクロロエタン、クロロベンゼンなどのクロロ炭化水素系化合物；パーフルオロ－ｔｅｒｔ－ブタノール、ヘキサフルオロ－２－メチルイソプロパノール、１，１，１，３，３，３－ヘキサフルオロイソプロパノール、２，２，２－トリフルオロエタノール、ヘキサフルオロアセトン等のフッ素含有分岐アルコール系又はケトン系化合物；ホルムアミド、Ｎ－メチルピロリドン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、ピリジン、アセトニトリルなどの含窒素極性化合物；アセトン、メチルエチルケトン、ジエチルケトン、メチルイソブチルケトン、アセトフェノン、シクロヘキサノンなどのアルキルケトン系化合物；安息香酸メチル、安息香酸エーテル、安息香酸ブチルなどの安息香酸エステル系化合物；ベンゼン、トルエン、キシレン、トリメチルベンゼン、ソルベントナフサ、１－メチルナフタレン、２－メチルナフタレン、ナフタレンなどの芳香族炭化水素系化合物；ジエチレングリコールモノメチルエーテル、トリエチレングリコールモノメチルエーテル、トリエチレングリコールジメチルエーテル、プロピレングリコールモノメチルエーテルなどのグリコールエーテル系化合物；メチルセロソルブアセテート、メトキシプロピルアセテート、カルビトールアセテート、ブチルカルビトールアセテートなどのグリコールエステル系化合物；ジメチルエーテル、ジエチルエーテル、ジプロピルエーテル、テトラヒドロフラン、１，４－ジオキサン、１，３－ジオキソラン、メチルｔ－ブチルエーテル、石油エーテルなどのエーテル系化合物；ジメチルスルホキシド、ジメチルスルホンなどのスルホキシド・スルホン系化合物；γ－ブチロラクトン、γ－バレロラクトン、δ－バレロラクトン等のラクトン系化合物；メタノール、エタノール、プロパノール、ブタノール、ペンタノール、エチレングリコール、プロピレングリコール、クレゾール、ポリエチレングリコール、ベンジルアルコールなどのアルコール系化合物；ノルマルヘキサン、シクロヘキサン、ノルマルヘプタン、イソオクタン、ノルマルデカンなどの炭化水素系化合物；トリメチルアミン、トリエチルアミン、トリブチルアミン等のアミン系化合物；酢酸エチル、酢酸ブチル等のカルボン酸エステル系化合物；トリフルオロ酢酸、酢酸、ギ酸等のカルボン酸系化合物等が挙げられる。 Specifically, water; chlorohydrocarbon compounds such as chloroform, dichloromethane, methylene chloride, trichlorethylene, ethylene dichloride, 1,2-dichloroethane, tetrachloroethane, and chlorobenzene; perfluoro-tert-butanol, hexafluoro-2 - fluorine-containing branched alcoholic or ketone compounds such as methylisopropanol, 1,1,1,3,3,3-hexafluoroisopropanol, 2,2,2-trifluoroethanol, hexafluoroacetone; formamide, N-methyl nitrogen-containing polar compounds such as pyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, pyridine and acetonitrile; alkyl ketone compounds such as acetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone, acetophenone and cyclohexanone; methyl benzoate , benzoic acid ether, benzoic acid ester compounds such as butyl benzoate; aromatic hydrocarbon compounds such as benzene, toluene, xylene, trimethylbenzene, solvent naphtha, 1-methylnaphthalene, 2-methylnaphthalene, naphthalene; diethylene glycol monomethyl Glycol ether compounds such as ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, and propylene glycol monomethyl ether; glycol ester compounds such as methyl cellosolve acetate, methoxypropyl acetate, carbitol acetate, and butyl carbitol acetate; dimethyl ether, diethyl Ether compounds such as ether, dipropyl ether, tetrahydrofuran, 1,4-dioxane, 1,3-dioxolane, methyl t-butyl ether, and petroleum ether; sulfoxide/sulfone compounds such as dimethyl sulfoxide and dimethyl sulfone; γ-butyrolactone, Lactone compounds such as γ-valerolactone and δ-valerolactone; Alcohol compounds such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, cresol, polyethylene glycol, and benzyl alcohol; Normal hexane, cyclohexane, Hydrocarbon compounds such as normal heptane, isooctane and normal decane; amine compounds such as trimethylamine, triethylamine and tributylamine; carboxylic acid ester-based compounds; carboxylic acid-based compounds such as trifluoroacetic acid, acetic acid, and formic acid;
これらの中でも、Ａ成分との相溶性、および、支持体上の多糖類組成物層を乾燥してフィルムとする際の乾燥のしやすさ等の観点から、構成元素として、炭素および水素を含む化合物か、或いは、炭素および水素とともに酸素またはハロゲンを含む化合物であって、分子量が１０００以下の化合物から選択される１種以上であることが好ましい。また、かかる好適な化合物は、アルコール系化合物、水、エーテル系化合物、含窒素極性化合物、ラクトン系化合物、クロロ炭化水素系化合物、カルボン酸系化合物からなる群から選択される１種以上であることがより好ましい。さらにこれらの中でも、Ａ成分との相溶性、および、多糖類組成物層の乾燥過程での多糖類分子の配向状態の保持性の観点から、メタノール、エタノール、水、１，４－ジオキサン、Ｎ，Ｎ－ジメチルホルムアミド、Ｎ，Ｎ－ジメチルアセトアミド、γ－ブチロラクトン、ベンジルアルコール、１，２－ジクロロエタン、ジクロロメタン、クロロホルム、トリフルオロ酢酸からなる群から選択される１種以上が特に好ましい。 Among these, carbon and hydrogen are included as constituent elements from the viewpoints of compatibility with component A and ease of drying when the polysaccharide composition layer on the support is dried to form a film. It is preferably one or more compounds selected from compounds or compounds containing oxygen or halogen together with carbon and hydrogen and having a molecular weight of 1000 or less. In addition, such suitable compounds are one or more selected from the group consisting of alcohol compounds, water, ether compounds, nitrogen-containing polar compounds, lactone compounds, chlorohydrocarbon compounds, and carboxylic acid compounds. is more preferred. Furthermore, among these, methanol, ethanol, water, 1,4-dioxane, N , N-dimethylformamide, N,N-dimethylacetamide, γ-butyrolactone, benzyl alcohol, 1,2-dichloroethane, dichloromethane, chloroform and trifluoroacetic acid are particularly preferred.
本発明において、Ｂ成分は１種または２種以上を使用できるが、沸点が低すぎると安全性や塗工性の点で問題があり、沸点が高すぎると乾燥性や十分な圧電性が得られないという点で問題がある。従って、沸点４０℃以上２５０℃以下の液状媒体を１種以上含む態様が好ましく、沸点４０℃以上２１０℃以下の液状媒体を１種以上含む態様がより好ましい。また、液状媒体全体の５０～１００重量％が、沸点４０℃以上２５０℃以下の液状媒体であることが好ましく、沸点４０℃以上２１０℃以下の液状媒体であることが好ましい。 In the present invention, one or more types of component B can be used, but if the boiling point is too low, there are problems in terms of safety and coating properties, and if the boiling point is too high, drying properties and sufficient piezoelectricity can be obtained. The problem is that you can't Therefore, an embodiment containing one or more liquid media having a boiling point of 40° C. or more and 250° C. or less is preferable, and an embodiment containing one or more liquid media having a boiling point of 40° C. or more and 210° C. or less is more preferable. Further, 50 to 100% by weight of the entire liquid medium is preferably a liquid medium having a boiling point of 40°C or higher and 250°C or lower, more preferably a liquid medium having a boiling point of 40°C or higher and 210°C or lower.
Ａ成分とＢ成分の量比は特に限定はされないが、一般的には、Ａ成分とＢ成分の重量比（Ａ成分：Ｂ成分）が１：９～７：３であり、好ましくは２：８～６：４である。 The weight ratio of component A to component B is not particularly limited, but the weight ratio of component A to component B (component A:component B) is generally 1:9 to 7:3, preferably 2: 8-6:4.
［その他の成分］
多糖類組成物には、本発明の作用効果（すなわち、フィルムを構成する多糖類分子の配向）を大きく損なわない範囲内で、多糖類組成物の特性改善やフィルム特性の改善を目的としてＡ、Ｂ成分以外の配合成分をさらに含有させることができる。かかる任意の配合成分としては、例えば、無機フィラー、有機フィラー、顔料、結晶核剤、消泡剤、酸化防止剤、増粘剤などの各種添加剤、多糖類以外の高分子化合物が挙げられる。これらの任意の配合成分の添加量は、少な過ぎると添加の効果を損なうが、多くなると樹脂組成物の特性（複屈折や粘度等）やフィルムの特性（圧電等）を損なうおそれがある。このためＡ、Ｂ成分以外の任意の配合成分の含有量はＡ成分に対して通常５０重量％以下が好ましく、３０重量％以下がより好ましく、１０重量％以下がさらに好ましい。[Other ingredients]
In the polysaccharide composition, A, for the purpose of improving the characteristics of the polysaccharide composition and improving the film characteristics within a range that does not significantly impair the effects of the present invention (that is, the orientation of the polysaccharide molecules constituting the film). A compounding component other than the B component can be further contained. Examples of such optional ingredients include inorganic fillers, organic fillers, pigments, crystal nucleating agents, antifoaming agents, antioxidants, various additives such as thickeners, and polymeric compounds other than polysaccharides. If the amount of these optional compounding components added is too small, the effect of the addition is impaired, but if the amount is too large, the properties of the resin composition (birefringence, viscosity, etc.) and the properties of the film (piezoelectricity, etc.) may be impaired. Therefore, the content of optional ingredients other than components A and B is generally preferably 50% by weight or less, more preferably 30% by weight or less, and even more preferably 10% by weight or less, relative to component A.
多糖類組成物の形態は溶液でも分散液でもよいが、大きなｄ１４圧電定数の発現の観点から、多糖類組成物の形態は溶液であることが好ましい。多糖類組成物は複屈折を有する必要があるが、一般的に多糖類溶液が複屈折を持つ場合、多糖類分子が何らかの規則構造を取っているが溶液全体で見ると多糖類分子の向きは等方的な状態である。このため、せん断力が加わると溶液全体の多糖類分子の向きが揃った規則構造になりやすく、溶液全体の多糖類分子の主鎖が配向して、より大きなｄ１４圧電定数が得られやすい。複屈折を有しない場合はせん断力が加わっても複屈折を有する場合のようには高い配向が得られない。なお、多糖類組成物は、せん断時の多糖類分子の高い配向のために必ず高い粘度が必要である訳ではなく、前述のとおり、フィルムとする際の乾燥工程における塗工後の高度な配向状態を保持するためである。本発明において多糖類組成物が複屈折を有するとは、クロスニコルの状態の２枚の偏光板の間に多糖類組成物を静置して透過光で観察した場合に組成物全体が明るく、暗い部分を有しない場合をいう。 The form of the polysaccharide composition may be either a solution or a dispersion, but from the viewpoint of developing a large d14 piezoelectric constant, the form of the polysaccharide composition is preferably a solution. A polysaccharide composition must have birefringence. In general, when a polysaccharide solution has birefringence, the polysaccharide molecules have some regular structure, but the orientation of the polysaccharide molecules in the entire solution is It is an isotropic state. Therefore, when a shearing force is applied, the polysaccharide molecules in the entire solution tend to form an ordered structure in which the directions are aligned, and the main chains of the polysaccharide molecules in the entire solution are oriented, making it easier to obtain a larger d14 piezoelectric constant. If the film does not have birefringence, even if a shearing force is applied, a high degree of orientation cannot be obtained as in the case of having birefringence. It should be noted that the polysaccharide composition does not necessarily require a high viscosity for high orientation of the polysaccharide molecules during shearing, and as described above, a high degree of orientation after coating in the drying process when forming a film. This is to hold the state. In the present invention, the expression that the polysaccharide composition has birefringence means that when the polysaccharide composition is placed between two polarizing plates in a crossed Nicol state and observed with transmitted light, the entire composition is bright and dark. It means the case of not having
また、特に制限はされないが、多糖類組成物は、複屈折や粘度の観点から、また、フィルムの膜厚確保の観点から、固形分量が１０重量％以上の組成物であることが好ましく、より好ましくは２０重量％以上、さらに一層好ましくは３０重量％以上である。 In addition, although not particularly limited, the polysaccharide composition is preferably a composition having a solid content of 10% by weight or more from the viewpoint of birefringence and viscosity and from the viewpoint of ensuring the film thickness. It is preferably 20% by weight or more, and even more preferably 30% by weight or more.
多糖類組成物は、公知の攪拌機や分散機を用いて調製することができる。すなわち、Ａ成分およびＢ成分を、これら以外の任意の配合成分を含有させる場合は該任意の配合成分とともに、公知の攪拌機や分散機により混合することで調製される。 A polysaccharide composition can be prepared using a known stirrer or disperser. That is, when the A component and the B component are mixed with any other optional compounding component, they are prepared by mixing them with a known stirrer or disperser.
攪拌機や分散機の例としては、ディゾルバー、プラネタリミキサー、ロールミル、サンドミル、ボールミル、ビーズミル、ホモジナイザー、高圧ホモジナイザー、アジホモミキサー、自転・公転ミキサーなどが挙げられる。 Examples of stirrers and dispersers include dissolvers, planetary mixers, roll mills, sand mills, ball mills, bead mills, homogenizers, high-pressure homogenizers, ajihomomixers, and rotation/revolution mixers.
混合温度は特に限定されず、非加熱で混合しても、加熱下で混合してもよいが、加熱する場合、室温～１５０℃程度が好ましい。また、混合時間も特に限定はされないが、例えば、自転・公転ミキサーを用いて混合する場合、混合時間は１０分～１時間程度が好ましい。 The mixing temperature is not particularly limited, and the mixture may be mixed without heating or with heating. The mixing time is also not particularly limited, but for example, when mixing using a rotation/revolution mixer, the mixing time is preferably about 10 minutes to 1 hour.
＜圧電フィルムの製造方法＞
［多糖類組成物の調製］
支持体上に塗工する塗工液として、上記の多糖類組成物を調製する。<Method for manufacturing piezoelectric film>
[Preparation of polysaccharide composition]
The above polysaccharide composition is prepared as a coating solution to be applied onto a support.
［多糖類組成物の塗工、乾燥］
多糖類組成物を支持体上に塗工し（第１工程）、得られた多糖類組成物層を乾燥する（第２工程）ことで、多糖類を含むフィルム（未延伸フィルム）が得られる。第１工程での多糖類組成物の塗工方法は、多糖類組成物に一方向にせん断力が作用し流動性をもつ樹脂組成物がフィルム状に変形、加工すれば良く、具体的な塗工手法としてはバーコート、カンマコート、ダイコート、スロットダイコート、ブレードコート、グラビアコート、グラビアオフセット印刷など公知の塗工方法が挙げられる。塗工に当たってコーターが動いても、支持体が動いても、両方動いても良い。塗工は、一方向にせん断力が作用していれば良く、バーコートなどのように支持体に対して所定の一方向に向けて多糖類組成物が塗り進められていても良く、ダイコートなどのようにせん断力が働いた多糖類組成物が支持体上にキャストされても良い。この所定の一方向に向けて多糖類組成物にせん断力が作用していく方向が多糖類分子の配向方向（すなわち、多糖類分子の主鎖の配向方向）になる。なお、「塗工方向」とは、この所定の一方向に向けて多糖類組成物にせん断が作用している方向のことである。[Coating and drying of polysaccharide composition]
A polysaccharide-containing film (unstretched film) is obtained by coating a polysaccharide composition on a support (first step) and drying the obtained polysaccharide composition layer (second step). . The method of coating the polysaccharide composition in the first step may be performed by applying a shear force to the polysaccharide composition in one direction and deforming and processing the fluid resin composition into a film. Examples of the method include known coating methods such as bar coating, comma coating, die coating, slot die coating, blade coating, gravure coating, and gravure offset printing. During coating, the coater may move, the support may move, or both may move. Coating may be performed by applying a shearing force in one direction, and the polysaccharide composition may be applied in one predetermined direction to the support such as bar coating, such as die coating. A polysaccharide composition subjected to a shear force such as may be cast onto a support. The direction in which the shearing force acts on the polysaccharide composition in this predetermined direction is the orientation direction of the polysaccharide molecules (that is, the orientation direction of the main chains of the polysaccharide molecules). The "coating direction" is the direction in which the polysaccharide composition is sheared in this one predetermined direction.
また、塗工（第１工程）と乾燥（第２工程）を一回行う、一回塗りでも良いし、塗工（第１工程）と乾燥（第２工程）を複数回繰り返す、重ね塗りを行っても良い。一回塗りの方がコスト的に優位だが、塗工における「塗り厚」が大きすぎると、多糖類組成物にせん断力が作用しにくくなり、多糖類分子が配向しにくくなる。このため、圧電フィルムの膜厚を厚くしたい場合は重ね塗りをするのが好ましい。 In addition, coating (first step) and drying (second step) may be performed once, coating may be performed once, and coating (first step) and drying (second step) may be repeated multiple times. you can go One-time coating is advantageous in terms of cost, but if the "coating thickness" in coating is too large, it becomes difficult for the shearing force to act on the polysaccharide composition, and the polysaccharide molecules become difficult to orient. Therefore, when it is desired to increase the film thickness of the piezoelectric film, it is preferable to apply multiple coatings.
多糖類組成物の塗工における「塗り厚」とは、塗工によりせん断がかかる時の多糖類組成物層の厚みである。このため、塗工方法にも依るが「塗り厚」は支持体とコーターの間の最短距離、あるいはコーターの隙間の距離である。例えば、支持体上にバーコートにより塗工を行う場合、支持体とバーの最短距離である。例えば、バーが丸みを帯びるなどしてバー全体の高さが均一でない場合、支持体とバーの最短距離は、バーの支持体に最近接する部分と支持体の間の距離を指す。ダイコーターのように多糖類組成物が隙間から放出される場合はこの隙間の距離を指す。塗り厚が大きいと多糖類組成物に作用するせん断力が小さくなり、かつ塗工から乾燥後までに塗工直後の配向状態が保持されにくい傾向となる。これは、多糖類組成物層の厚さが大きくなると単に多糖類組成物層が乾燥されにくくなるだけでなく、基材との界面の効果が相対的に少なくなり多糖類組成物層内の棒状の多糖類分子の運動性が上がるためと考えられる。従って、塗り厚は１０００μｍ以下が好ましく、５００μｍ以下がより好ましく、２００μｍ以下が特に好ましい。なお、塗り厚が小さすぎると、均一に塗工することが困難になることや、乾燥後のフィルムの絶縁不良などの不具合があるため、塗り厚は０．１μｍ以上が好ましく、１μｍ以上がより好ましい。 The “coating thickness” in coating of the polysaccharide composition is the thickness of the polysaccharide composition layer when shear is applied by coating. Therefore, although it depends on the coating method, the "coating thickness" is the shortest distance between the support and the coater, or the distance between the coaters. For example, when bar coating is performed on a support, it is the shortest distance between the support and the bar. For example, if the height of the entire bar is not uniform, such as when the bar is rounded, the shortest distance between the support and the bar refers to the distance between the portion of the bar closest to the support and the support. When the polysaccharide composition is released from a gap like a die coater, it refers to the distance of this gap. If the coating thickness is large, the shear force acting on the polysaccharide composition will be small, and the orientation state immediately after coating will tend to be difficult to maintain from coating to drying. This is because when the thickness of the polysaccharide composition layer increases, not only does the polysaccharide composition layer become more difficult to dry, but also the effect of the interface with the substrate is relatively reduced, resulting in a rod-like shape in the polysaccharide composition layer. This is thought to be because the mobility of the polysaccharide molecules in the Therefore, the coating thickness is preferably 1000 μm or less, more preferably 500 μm or less, and particularly preferably 200 μm or less. If the coating thickness is too small, it may be difficult to apply a uniform coating, and there may be problems such as poor insulation of the film after drying. preferable.
通常、「塗り厚」と乾燥して得られるフィルムの膜厚とは異なる。樹脂組成物に粘度があるため、塗工直後の樹脂組成物の膜厚は「塗り厚」の通りではなく薄くなる。「フィルムの膜厚」はさらに乾燥により、溶剤が抜けることによって膜減りしてさらに薄くなる。すなわち、乾燥して得られるフィルムの膜厚は「塗り厚」より小さい。このため、前述の通り塗り厚は薄い方が好ましいが、大きい膜厚のフィルムを得たい場合一回の塗工、乾燥によって得ることができない膜厚のフィルム（圧電フィルム）を得たいときは、５００μｍ以下の塗り厚にて、２回以上の重ね塗りをして、所望の厚さのフィルムを製造するのが好ましい。 Generally, the "coat thickness" is different from the thickness of the film obtained after drying. Since the resin composition has viscosity, the film thickness of the resin composition immediately after coating is not as described in the "coating thickness" but is thin. The "thickness of the film" becomes thinner as the film is further dried and the solvent is removed. That is, the film thickness obtained by drying is smaller than the "coating thickness". For this reason, as mentioned above, the thinner the coating thickness, the better. It is preferred to produce a film of desired thickness using two or more overcoatings with a coating thickness of 500 μm or less.
［塗工と延伸について］
塗工と延伸はいずれも厚みを持った形状の樹脂を厚みの薄いフィルム状に成形するために用いられる手法で、広義には「延伸」に「塗工」も含まれると解釈できる。本発明に於いて「延伸」は溶剤を含まない状態に於いて加熱等を用いて弾性率を下げて引張あるいはプレス等をもちいて、厚みの薄いフィルム状に成形する工程と定義する。一方、「塗工」は樹脂に溶剤を含ませることで流動性を持たせて、その流動状態でせん断の力を加えることで、厚みの薄いフィルム状に成型し、その後に溶剤を除去する工程と定義する。[About coating and stretching]
Both coating and stretching are methods used to form a thick resin into a thin film. In the present invention, "stretching" is defined as a step of forming a thin film by stretching or pressing after lowering the elastic modulus by heating in a solvent-free state. On the other hand, "coating" is a process in which a solvent is added to the resin to give it fluidity, and a shearing force is applied to the resin to form a thin film, after which the solvent is removed. defined as
多糖類組成物が塗工される支持体は、塗工におけるせん断力に耐え得る機械強度と乾燥に耐え得る耐熱性があれば良く、絶縁体であっても導電体であっても良い。絶縁体の場合は、ポリエチレンテレフタレート（ＰＥＴ）、ポリエチレンナフタレート、ポリイミド等のプラスチックが挙げられる。導電体の場合、銅箔、銅箔付きポリイミド、ＩＴＯガラス、金属を蒸着あるいはスパッタしたＰＥＴなどが挙げられる。 The support on which the polysaccharide composition is coated may be either an insulator or a conductor, as long as it has mechanical strength to withstand shearing force during coating and heat resistance to withstand drying. Insulators include plastics such as polyethylene terephthalate (PET), polyethylene naphthalate, and polyimide. In the case of conductors, copper foil, polyimide with copper foil, ITO glass, and PET obtained by depositing or sputtering metal can be used.
（乾燥方法）
支持体上に形成された多糖類組成物層の乾燥方法は、塗工後の多糖類組成物層における多糖類分子の配向状態を保持しつつ液状媒体を除去できる方法であればどんな方法でも良く、常温、常圧での乾燥（自然乾燥）でも良いし、加熱乾燥でも減圧乾燥でも良い。加熱乾燥の場合、バッチオーブン、熱風乾燥炉、ベルト式連続炉、遠赤外線乾燥炉など公知の加熱機器を用いることが出来る。(Drying method)
The method for drying the polysaccharide composition layer formed on the support may be any method as long as it can remove the liquid medium while maintaining the orientation of the polysaccharide molecules in the polysaccharide composition layer after coating. , drying at normal temperature and pressure (natural drying), heat drying, or reduced pressure drying may be used. In the case of heat drying, known heating equipment such as a batch oven, a hot air drying oven, a belt-type continuous oven, and a far-infrared drying oven can be used.
乾燥により液状の多糖類組成物が、固形分量９５重量％以上の固体のフィルムとなる。一般的には乾燥の条件は多糖類組成物のＢ成分の沸点、塗工の際の塗り厚、乾燥器内の風速と空気の循環量等により乾燥温度、乾燥時間等のパラメーターを調節する。本発明において乾燥の際に注意することは、乾燥時に塗工直後に実現されていた多糖類の高い配向状態が元に戻る場合があることである。乾燥条件の設定にはこの点に注意しながらパラメーターを選定する必要がある。乾燥工程での乾燥温度は一定でも良いし、１００℃で加熱後、１５０℃で加熱のような不連続に温度を変える態様でも良いし、１００℃から１５０℃へと徐々に昇温するような、連続的に温度を変える態様でも良い。乾燥温度はＢ成分の沸点、塗り厚、多糖類のガラス転移温度などにも依るが、多糖類の劣化防止の観点から３００℃以下が好ましく、２５０℃以下がより好ましく、２００℃以下がさらに好ましく、１８０℃以下が最も好ましい。 Upon drying, the liquid polysaccharide composition forms a solid film with a solids content of 95% by weight or more. In general, the drying conditions are adjusted by adjusting the boiling point of the B component of the polysaccharide composition, the coating thickness during coating, the wind speed and the amount of air circulation in the dryer, and other parameters such as drying temperature and drying time. In the present invention, it should be noted that the highly oriented state of the polysaccharides that was realized immediately after coating may be restored during drying. When setting drying conditions, it is necessary to select parameters while paying attention to this point. The drying temperature in the drying step may be constant, may be a mode in which the temperature is discontinuously changed such as heating at 100°C and then heating at 150°C, or may be such that the temperature is gradually increased from 100°C to 150°C. Alternatively, the temperature may be changed continuously. The drying temperature depends on the boiling point of component B, the coating thickness, the glass transition temperature of the polysaccharide, etc., but is preferably 300° C. or less, more preferably 250° C. or less, and even more preferably 200° C. or less from the viewpoint of preventing deterioration of the polysaccharide. , 180° C. or less is most preferred.
（アニール処理）
乾燥後の多糖類フィルムには適切な温度と時間のアニール処理を施しても良いし、しなくとも良い。(annealing treatment)
The polysaccharide film after drying may or may not be annealed at an appropriate temperature and time.
多糖類組成物の塗工、乾燥により形成される本発明のｄ１４圧電体フィルムは、支持体から分離しても良いし、支持体をそのまま電極、補強材などに用いて、電極付き圧電フィルムや補強材付き圧電フィルムとしても良い。このため、支持体には離型処理、防錆処理、密着向上処理などの表面処理が行われていても良く、未処理でも良い。 The d14 piezoelectric film of the present invention formed by coating and drying the polysaccharide composition may be separated from the support, or the support may be used as an electrode or a reinforcing material as it is to form a piezoelectric film with an electrode or the like. A piezoelectric film with reinforcing material may be used. Therefore, the support may be subjected to a surface treatment such as release treatment, rust prevention treatment, adhesion improvement treatment, or may be untreated.
本発明のｄ１４圧電フィルムの膜厚は、特に限定はされないが、フレキシブルな圧電体としての用途を考えると、１～５００μｍが好ましく、２～１００μｍがより好ましい。また、可とう性や後述する本発明の圧電フィルムを用いたセンサー全体の軽薄短小化の観点から、２０～８０μｍが特に好ましい。厚さが１μｍ未満では、十分に高い絶縁信頼性が得られない恐れがある。 The film thickness of the d14 piezoelectric film of the present invention is not particularly limited, but is preferably 1 to 500 μm, more preferably 2 to 100 μm, considering its use as a flexible piezoelectric body. Further, from the viewpoint of flexibility and miniaturization of the entire sensor using the piezoelectric film of the present invention, which will be described later, 20 to 80 μm is particularly preferable. If the thickness is less than 1 μm, it may not be possible to obtain sufficiently high insulation reliability.
本発明のｄ１４圧電フィルムをセンサーやアクチュエーターとして利用する際の好適なフィルムの形態としては、例えば、塗工、乾燥して得られたｄ１４圧電フィルム（多糖類を含むフィルム）から、フィルムの軸線（中心線）が、多糖類分子の配向方向に対して４５度の交差角度をなすように切り出されたフィルムが挙げられる。また、本発明のｄ１４圧電フィルムの平面形状は特に限定されず、例えば、正方形、矩形等である。 A preferred form of the film when using the d14 piezoelectric film of the present invention as a sensor or actuator is, for example, a d14 piezoelectric film (a film containing a polysaccharide) obtained by coating and drying, from which the axis of the film ( center line) is cut out so as to form an intersection angle of 45 degrees with respect to the orientation direction of the polysaccharide molecules. Moreover, the planar shape of the d14 piezoelectric film of the present invention is not particularly limited, and may be, for example, a square, a rectangle, or the like.
（電極）
本発明のｄ１４圧電フィルムをセンサーやアクチュエーターとして利用するためには、フィルムの対向した２面に電極を形成する必要がある。電極の厚さは１０ｎｍ～２５μｍ程度が好ましく、１００ｎｍ～１２．５μｍ程度がより好ましい。厚さが２５μｍを超えるとフィルムの変形を阻害し、１０ｎｍより薄いと電気伝導性やピンホールなどの問題が発生する。電極形成は蒸着、スパッタなどの既存の圧電フィルムで利用される公知の方法で形成することが出来る。また、電極あるいは電極形成した絶縁体を支持体にして、これに多糖類組成物の塗工、乾燥を行うことで、電極付きの圧電フィルムを効率良く製造することもできる。電極の素材は十分な電気伝導性が担保されるのであれば金、銀、銅、白金、ニッケル、錫、アルミニウムなどの金属でも良いし、ＩＴＯ、ＦＴＯなどの金属酸化物でも良いし、ポリチオフェン、ポリアニリンなどの有機導電材料でも良い。(electrode)
In order to use the d14 piezoelectric film of the present invention as a sensor or actuator, it is necessary to form electrodes on two opposite surfaces of the film. The thickness of the electrode is preferably about 10 nm to 25 μm, more preferably about 100 nm to 12.5 μm. If the thickness exceeds 25 μm, deformation of the film is inhibited, and if it is thinner than 10 nm, problems such as electrical conductivity and pinholes occur. Electrodes can be formed by known methods such as vapor deposition and sputtering, which are used for existing piezoelectric films. Alternatively, a piezoelectric film with electrodes can be produced efficiently by using an electrode or an insulator formed with electrodes as a support, coating the polysaccharide composition on the support, and drying the support. Materials for the electrodes may be metals such as gold, silver, copper, platinum, nickel, tin, and aluminum, metal oxides such as ITO and FTO, polythiophene, and the like, as long as sufficient electrical conductivity is ensured. An organic conductive material such as polyaniline may also be used.
［デバイス］
本発明のｄ１４圧電フィルムはその両面に電極を備えることによりセンサーやアクチュエーターとして利用できる。例えば、両面に電極が形成されたｄ１４圧電フィルムはそのまま歪みや引張りセンサーとして使用できる。また、電極が形成されたｄ１４圧電フィルムを被検査物に、貼りつけることで、被検査物の曲げや歪みを検知するセンサーとして使用できる。ここで、「被検査物」とは、例えば、人体、自動車、道路、橋梁等である。また、両面に電極が形成された圧電フィルムは、モノモルフ、バイモルフ、片持ち梁構造に用いられることで押圧、振動などを検知することが出来るセンサーやアクチュエーターとして利用することができる。電極が形成された本発明のｄ１４圧電フィルムと圧電性を有しない別のフィルム（例えば、ゴム製フィルム等）とを端面を合わせて互いの表面（圧電フィルムにおける電極表面と、圧電性を有しないフィルムの表面）が同一の平面を成すように接合することで引張りセンサーとして利用しても良い。[device]
The d14 piezoelectric film of the present invention can be used as a sensor or actuator by providing electrodes on both sides thereof. For example, a d14 piezoelectric film with electrodes formed on both sides can be used directly as a strain or tension sensor. Also, by attaching the d14 piezoelectric film on which electrodes are formed to an object to be inspected, it can be used as a sensor for detecting bending or distortion of the object to be inspected. Here, the "object to be inspected" is, for example, a human body, an automobile, a road, a bridge, or the like. A piezoelectric film having electrodes formed on both sides can be used as a sensor or actuator capable of detecting pressure, vibration, etc. by being used in a monomorph, bimorph, or cantilever structure. The d14 piezoelectric film of the present invention on which an electrode is formed and another non-piezoelectric film (for example, a rubber film) It may be used as a tension sensor by bonding so that the surfaces of the films form the same plane.
電極からの信号引出しの回路は既知の方法が利用できる。例えば、予め配線を具備させた電極と本発明のｄ１４圧電フィルムを接合する方法、両面に電極が形成された本発明のｄ１４圧電フィルムの電極にフレキシブルプリント基板などの配線を接合する方法などが挙げられる。 A known method can be used for a circuit for extracting signals from the electrodes. For example, a method of bonding an electrode having wiring in advance and the d14 piezoelectric film of the present invention, and a method of bonding wiring such as a flexible printed circuit board to the electrode of the d14 piezoelectric film of the present invention having electrodes formed on both sides thereof. be done.
両面に電極が形成された本発明のｄ１４圧電フィルムのさらに外側に電磁波シールド層を用いることができる。電磁波シールド層は銅やアルミの金属箔をそのまま用いる方法や、蒸着、スパッタなどで絶縁層や接着層上に形成する方法など既知の方法を用いることが出来る。電磁波シールド層はグラウンドと接続（アース）するのが好ましい。また、電磁波シールド層はｄ１４圧電フィルムに形成された電極の一方と接続しても良い。 An electromagnetic wave shielding layer can be used on the outer side of the d14 piezoelectric film of the present invention having electrodes formed on both sides. The electromagnetic wave shielding layer can be formed by a known method such as using a metal foil of copper or aluminum as it is, or forming it on an insulating layer or adhesive layer by vapor deposition, sputtering, or the like. The electromagnetic wave shield layer is preferably grounded (earthed). Also, the electromagnetic wave shield layer may be connected to one of the electrodes formed on the d14 piezoelectric film.
センサーに力学的負荷がかかって発生する信号（電荷）はチャージアンプなど既知の回路を用いて取り出すことが出来る。また、バンドパスフィルターなどを用いてノイズを除去したり、Ａ／Ｄ変換を用いて信号をデジタル変換することが出来る。 A signal (charge) generated by a mechanical load applied to the sensor can be extracted using a known circuit such as a charge amplifier. In addition, noise can be removed using a bandpass filter or the like, and a signal can be converted into a digital signal using A/D conversion.
本発明のセンサーは引張り、歪み、曲げ、振動、音波などを定量的に評価することが出来るので様々なものを測定することが可能である。例えば心拍や呼吸などの生体信号、橋や道路などのインフラの歪みや振動、自動車や飛行機などの機体の歪み、押圧や歪みを検知するパネルなどの新しいユーザーインターフェースなどに利用することができる。 Since the sensor of the present invention can quantitatively evaluate tension, strain, bending, vibration, sound waves, etc., it is possible to measure various things. For example, it can be used for biomedical signals such as heartbeat and respiration, distortion and vibration of infrastructure such as bridges and roads, distortion of aircraft such as automobiles and airplanes, and new user interfaces such as panels that detect pressure and distortion.
以下、実施例及び比較例により本発明をより具体的に説明するが、本発明は以下の実施例によって制限を受けるものではなく、上記・下記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。 Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited by the following examples, and can be appropriately modified within the scope of the above and the following. Of course, it is also possible to carry out the method using other methods, and all of them are included in the technical scope of the present invention.
まず、物性および特性の測定方法および評価方法（試験方法）について説明する。 First, methods for measuring and evaluating physical properties and characteristics (testing methods) will be described.
１．粘度測定
－測定装置－
ブルックフィールド社製のコーンプレート粘度計を使用した。
ＲＶＤＶ－II＋Ｐｒｏ
コーンスピンドル ＣＰＥ－５２
－測定方法－
ＪＩＳ Ｚ８８０３に準拠し、２５℃にて多糖類組成物の粘度を測定した。多糖類組成物を円すいと平円板の組み合わせから必要量（０．５ｍｌ）を測り取り、回転数０．２ｒｐｍにて粘度計を作動させた。測定開始から３０秒後の粘度値を採用した。1. Viscosity measurement -Measuring device-
A Brookfield Cone Plate Viscometer was used.
RVDV-II + Pro
cone spindle CPE-52
-Measuring method-
The viscosity of the polysaccharide composition was measured at 25°C according to JIS Z8803. A required amount (0.5 ml) of the polysaccharide composition was measured from a combination of a cone and a flat disc, and the viscometer was operated at a rotation speed of 0.2 rpm. The viscosity value 30 seconds after the start of measurement was adopted.
ポリヒドロキシ酸組成物の粘度測定も上記と同様にして行った。 The viscosity measurement of the polyhydroxy acid composition was also performed in the same manner as described above.
２．多糖類組成物の複屈折の確認
ガラス板２枚に多糖類組成物を入れ、上下の偏光板がクロスニコルの状態で多糖類組成物（液状物）の複屈折の有無を調べた。全体やスライドの一部などを動かさずに静置した状態で視野が一様に明るい時を複屈折有り、暗い部分を有する時を複屈折無しと判断した。2. Confirmation of Birefringence of Polysaccharide Composition The polysaccharide composition was placed on two glass plates, and the presence or absence of birefringence of the polysaccharide composition (liquid) was examined with the upper and lower polarizing plates in crossed Nicol state. When the field of view was uniformly bright in a state where the whole or part of the slide was not moved, it was determined that there was birefringence, and when there was a dark portion, it was determined that there was no birefringence.
３．ｄ１４圧電定数（最高値）の測定
－測定サンプルの作成－
フィルムから、長手の軸線が、塗工方向に対して４５度の交差角度をなすように、２２（ｍｍ）×８（ｍｍ）のサイズの短形のフィルムを切り出した。そして、フィルムの両面の中央部に１１×５（ｍｍ）の電極を形成させた。電極は金スパッタで形成させた。金スパッタは真空デバイス社製のイオンスパッタ（ＭＳＰ－１Ｓ）を用いた。両面の電極の端にドーダイトＤ－３６２（藤倉化成社製）を用いてアルミ箔のリード線（５０×２（ｍｍ））を接着した。
－測定－
東洋精機社製のレオログラフソリッドＳ１に測定サンプルを固定し、周波数１０Ｈｚで２５℃にて、測定サンプルに印加されるせん断ひずみが０．１％～１％の範囲に収まるように、おおよそ２×１０６Ｎ／ｍ２～６×１０６Ｎ／ｍ２のせん断応力をフィルムの長手の軸線方向に印加し、リード線から電荷を測定し、該測定サンプルの複素圧電率ｄ１４の実数部を計算した。3. Measurement of d14 piezoelectric constant (maximum value) -Preparation of measurement sample-
A rectangular film with a size of 22 (mm) x 8 (mm) was cut from the film so that the longitudinal axis formed a crossing angle of 45 degrees with the coating direction. Electrodes of 11×5 (mm) were formed in the center of both surfaces of the film. Electrodes were formed by gold sputtering. Ion sputtering (MSP-1S) manufactured by Vacuum Device Co., Ltd. was used for gold sputtering. Aluminum foil lead wires (50×2 (mm)) were adhered to the ends of the electrodes on both sides using Dodite D-362 (manufactured by Fujikura Kasei Co., Ltd.).
-measurement-
The measurement sample is fixed to Rheolograph Solid S1 manufactured by Toyo Seiki Co., Ltd., and at a frequency of 10 Hz and 25 ° C., so that the shear strain applied to the measurement sample falls within the range of 0.1% to 1%. A shear stress of × 10 6 N/m 2 to 6 × 10 6 N/m 2 is applied in the longitudinal axis direction of the film, the charge is measured from the lead wire, and the real part of the complex piezoelectric constant d14 of the measurement sample is Calculated.
４．フィルムの膜厚
フィルムの膜厚はミツトヨ社製マイクロメーターを用いて塗膜１枚（約２５０平方センチメートル）につき１０点を測定し、１μｍまでを読み取り、その平均値を算出した。4. Film Thickness The thickness of the film was measured at 10 points per sheet (approximately 250 square centimeters) using a micrometer manufactured by Mitutoyo Co., Ltd., reading up to 1 μm, and calculating the average value.
５．使用材料
実施例および比較例で用いた材料は以下の通り。
・ヒドロキシプロピルセルロース：和光純薬工業株式会社製「ヒドロキシプロピルセルロース６.０～１０.０」（ＧＰＣによる数平均分子量：約１４００００）
註）「ヒドロキシプロピルセルロース６.０～１０.０」における「６．０～１０．０」は２重量％水溶液（２０℃）が６～１０ｍＰａ・ｓの粘度を持つことを意味する。5. Materials Used Materials used in Examples and Comparative Examples are as follows.
・ Hydroxypropyl cellulose: “Hydroxypropyl cellulose 6.0 to 10.0” manufactured by Wako Pure Chemical Industries, Ltd. (number average molecular weight by GPC: about 140000)
Note) "6.0 to 10.0" in "hydroxypropyl cellulose 6.0 to 10.0" means that a 2 wt% aqueous solution (20°C) has a viscosity of 6 to 10 mPa·s.
・エチルセルロース：和光純薬工業株式会社製「エチルセルロース（約４９％エトキシ）１００」
註）「エチルセルロース（約４９％エトキシ）１００」における「（約４９％エトキシ）」はセルロースの総ヒドロキシ基の４９モル％がエトキシ基に置換されていることを意味し、「１００」とはトルエン８０％／エタノール２０％の５重量％溶液（２５℃）が９０．０～１１０．０ｍＰａ・ｓの粘度を持つことを意味する。・ Ethyl cellulose: “Ethyl cellulose (about 49% ethoxy) 100” manufactured by Wako Pure Chemical Industries, Ltd.
Note) "(About 49% ethoxy)" in "Ethyl cellulose (about 49% ethoxy) 100" means that 49 mol% of the total hydroxyl groups of cellulose are substituted with ethoxy groups, and "100" means toluene It means that a 5 wt % solution of 80%/20% ethanol (25° C.) has a viscosity of 90.0-110.0 mPa·s.
・トリアセチルセルロース：和光純薬工業株式会社「三酢酸セルロース」 ・Triacetyl cellulose: Wako Pure Chemical Industries, Ltd. "Triacetate cellulose"
・ポリ乳酸：Aldrich社「Poly(L-lactide), inherent viscosity ～2.0 dl/g」
・γ－ブチルラクトン：純正化学株式会社 特級
・ジオキサン：純正化学株式会社「１，４－ジオキサン」特級
・トリフルオロ酢酸：東京化成工業株式会社 特級
・クロロホルム：純正化学株式会社 特級・ Polylactic acid: Aldrich "Poly (L-lactide), inherent viscosity ~ 2.0 dl / g"
・γ-Butyl lactone: Junsei Chemical Co., Ltd. special grade ・Dioxane: Junsei Chemical Co., Ltd. “1,4-dioxane” special grade ・Trifluoroacetic acid: Tokyo Chemical Industry Co., Ltd. special grade ・Chloroform: Junsei Chemical Co., Ltd. special grade
（実施例１）
下記の表１に示す配合でヒドロキシプロピルセルロース（Ａ成分）と１，４－ジオキサン（Ｂ成分）を容器に入れ、ヒドロキシプロピルセルロースが溶解するまで混合した。混合には、ＴＨＹＮＫＹ社製の自転・公転ミキサーである「あわとり錬太郎（ＡＲＥ－３１０）」を用いた。また、Ａ成分の溶解のために適宜８０℃未満の加熱を行った。多糖類組成物をスポイトで離型ＰＥＴに垂らし、ヨシミツ精機株式会社製のＹＢＡ型ベーカーアプリケーター（３型）を用いて多糖類組成物を離型ＰＥＴに塗工した。「塗り厚」は１２．５μｍに設定した。室温で３０分間乾燥させた後、さらに１５０℃にて１５分間乾燥し、十分に放冷した後で離型ＰＥＴから剥離してヒドロキシプロピルセルロース単体のフィルムを得た。(Example 1)
Hydroxypropyl cellulose (Component A) and 1,4-dioxane (Component B) were placed in a container according to the formulation shown in Table 1 below and mixed until the hydroxypropyl cellulose was dissolved. For mixing, a rotation/revolution mixer "Awatori Rentaro (ARE-310)" manufactured by THYNKY was used. In addition, heating at a temperature of less than 80° C. was appropriately performed for dissolving the A component. The polysaccharide composition was dropped on the release PET with a dropper, and the release PET was coated with the polysaccharide composition using a YBA baker applicator (type 3) manufactured by Yoshimitsu Seiki Co., Ltd. "Paint thickness" was set to 12.5 μm. After drying at room temperature for 30 minutes, it was further dried at 150° C. for 15 minutes, allowed to cool sufficiently, and then peeled from the release PET to obtain a film of hydroxypropyl cellulose alone.
（実施例２～５、比較例１、２）
表１に示す配合に変更した以外は実施例１と同様にして多糖類組成物またはポリヒドロキシ酸組成物を調製し、さらに表１に示す条件（塗り厚、塗り回数、乾燥条件）でフィルムを作製した。(Examples 2 to 5, Comparative Examples 1 and 2)
A polysaccharide composition or polyhydroxy acid composition was prepared in the same manner as in Example 1 except that the formulation was changed to that shown in Table 1, and a film was formed under the conditions shown in Table 1 (coating thickness, number of coatings, drying conditions). made.
実施例１～５、比較例１、２における上記の試験１～５での測定結果を表１に記載した。なお、表１中のＡ、Ｂ成分及びポリ乳酸の配合量、合計量の数値は「重量部」であり、固形分の数値は「重量％」である。また、圧電判定はｄ１４圧電定数の最高値が１ｐＣ／Ｎ以上が合格（○）、ｄ１４圧電定数の最高値が１ｐＣ／Ｎ未満が不合格（×）である。粘度測定限界は３２８,０００ｍＰａ・ｓである。 Table 1 shows the measurement results of the above Tests 1 to 5 in Examples 1 to 5 and Comparative Examples 1 and 2. In Table 1, the compounding amount and the total amount of components A, B and polylactic acid are "parts by weight", and the solid content is "% by weight". In addition, the piezoelectric judgment is pass (o) when the maximum value of the d14 piezoelectric constant is 1 pC/N or more, and fails (x) when the maximum value of the d14 piezoelectric constant is less than 1 pC/N. The viscosity measurement limit is 328,000 mPa·s.
本出願は、日本で出願された特願２０１７－１２５６６２（出願日：２０１７年６月２７日）を基礎としており、その内容は本明細書に全て包含される。 This application is based on Japanese Patent Application No. 2017-125662 (filing date: June 27, 2017) filed in Japan, the contents of which are all incorporated herein.
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| JP2011155574A (en) | 2010-01-28 | 2011-08-11 | Konica Minolta Medical & Graphic Inc | Laminated ultrasonic vibrator, ultrasonic probe using the same, and ultrasonic medical image diagnostic device |
| WO2012026494A1 (en) | 2010-08-25 | 2012-03-01 | 三井化学株式会社 | Macromolecular piezoelectric material and manufacturing method therefor |
| JP2014502416A (en) | 2010-09-27 | 2014-01-30 | タフツ ユニバーシティー／トラスティーズ オブ タフツ カレッジ | Silk-based piezoelectric material |
| JP2015189823A (en) | 2014-03-27 | 2015-11-02 | 三菱化学株式会社 | boron nitride sheet |
| JP2016112773A (en) | 2014-12-15 | 2016-06-23 | コニカミノルタ株式会社 | Polyarylate film and method for producing the same |
| WO2017061209A1 (en) | 2015-10-06 | 2017-04-13 | 三井化学株式会社 | Long, slab-shaped piezoelectric body and production method therefor, laminate and production method therefor, fabric, garment, and biological information acquisition device |
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