JPS5839395B2 - Manufacturing method of linear piezoelectric material - Google Patents
Manufacturing method of linear piezoelectric materialInfo
- Publication number
- JPS5839395B2 JPS5839395B2 JP52103234A JP10323477A JPS5839395B2 JP S5839395 B2 JPS5839395 B2 JP S5839395B2 JP 52103234 A JP52103234 A JP 52103234A JP 10323477 A JP10323477 A JP 10323477A JP S5839395 B2 JPS5839395 B2 JP S5839395B2
- Authority
- JP
- Japan
- Prior art keywords
- piezoelectric material
- solution
- linear
- piezoelectric
- linear piezoelectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000463 material Substances 0.000 title claims description 44
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 229920000620 organic polymer Polymers 0.000 claims description 4
- 239000002861 polymer material Substances 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- ZGEYCCHDTIDZAE-BYPYZUCNSA-N L-glutamic acid 5-methyl ester Chemical compound COC(=O)CC[C@H](N)C(O)=O ZGEYCCHDTIDZAE-BYPYZUCNSA-N 0.000 claims 1
- 108700024573 poly-gamma-benzyl-L-glutamate Proteins 0.000 claims 1
- 239000004020 conductor Substances 0.000 description 7
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 4
- 229920000835 poly(gamma-benzyl-L-glutamate) polymer Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000005452 bending Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920001184 polypeptide Polymers 0.000 description 3
- 102000004196 processed proteins & peptides Human genes 0.000 description 3
- 108090000765 processed proteins & peptides Proteins 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- GQYHUHYESMUTHG-UHFFFAOYSA-N lithium niobate Chemical compound [Li+].[O-][Nb](=O)=O GQYHUHYESMUTHG-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002643 polyglutamic acid Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229920005613 synthetic organic polymer Polymers 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Electrophonic Musical Instruments (AREA)
Description
【発明の詳細な説明】
本発明は自由に屈曲することの可能な可撓性線状圧電材
料の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method of manufacturing a flexible linear piezoelectric material that can be bent freely.
従来、圧電性を示す材料として、水晶及びリチユムナイ
オベート等の結晶そして更にはチタン酸バリウム及びチ
タン・ジルコン酸鉛等の強誘電体セラミック等は圧電特
性の良いものとして知られており、振動子及び発火素子
等多くの分野で利用されている。Conventionally, as materials exhibiting piezoelectricity, crystals such as quartz and lithium niobate, as well as ferroelectric ceramics such as barium titanate and titanium/lead zirconate, are known to have good piezoelectric properties, and are known to have good piezoelectric properties. It is used in many fields such as children and ignition devices.
しかし、これらの材料はいずれも高脆材料であり、機械
的衝撃力に対して弱く割れ易い欠点を有していた。However, all of these materials are highly brittle and have the disadvantage of being weak against mechanical impact and easily cracking.
そのため、大きな曲率で曲げることはもちろん、細い線
状にすることも極めて困難であり、形状的に又使用形態
的に多くの制限があった。Therefore, it is extremely difficult not only to bend it with a large curvature, but also to form it into a thin line, and there are many limitations in terms of shape and usage.
一方、合成有機高分子圧電材料として知られているポリ
フッ化ビニリデン（以下ＰＶＦ２と略称する）を用いた
圧電材料は、薄い大面積に成形し得、可撓性を有する圧
電材料であり、使用形態自由度が大きい材料である。On the other hand, a piezoelectric material using polyvinylidene fluoride (hereinafter abbreviated as PVF2), which is known as a synthetic organic polymer piezoelectric material, can be formed into a thin large area and has flexibility. It is a material with a large degree of freedom.
しかしながら、とのＰＶＦ２圧電材料は、ＰＶＦ２を延
伸処理することにより結晶形を■型に変え主鎖を平面ジ
グザグ構造として配向することが圧電性を大きくするた
めの重要な要素となっており、プレス成形等の溶結成形
で自由な形状にすることは不可能であった。However, for the PVF2 piezoelectric material, the important factor for increasing piezoelectricity is changing the crystal shape to a ■ shape by stretching PVF2 and orienting the main chain as a planar zigzag structure. It was impossible to create a free shape by welding such as molding.
これに対して、ポリーｒ−メチルーＬ−グルタメート（
以下ＰＭＬＧと略称する）等の合成ポリペプチド系の圧
電材料は、溶液中から結晶化する場合に溶液の流れ方向
に分子鎖が配向することが知られており、これによって
可撓性を有する圧電材料が製作できる。In contrast, poly r-methyl-L-glutamate (
It is known that when synthetic polypeptide-based piezoelectric materials such as PMLG (hereinafter abbreviated as PMLG) are crystallized from a solution, the molecular chains are oriented in the flow direction of the solution. Materials can be produced.
本発明者等はこの点に着目し、このような可撓性を有す
る圧電材料から線状圧電材料を製作することにつき検討
を重ねた結果本発明を完成したものである。The present inventors paid attention to this point and completed the present invention as a result of repeated studies on manufacturing a linear piezoelectric material from such a flexible piezoelectric material.
すなわち本発明の目的は、自由に屈曲することの可能な
可撓性線状圧電材料の製造方法を提供することである。That is, an object of the present invention is to provide a method for manufacturing a flexible linear piezoelectric material that can be freely bent.
本発明につき概説すれば、本発明の線状圧電材料の製造
方法は導電性を有する線状材料の表面に、溶液中より成
膜するときに溶液の流れ方向に分子鎖が配向する性質を
有する有機高分子材料を含む溶液を塗布し、該塗布溶液
に一定の流れ方向を付与しながら溶媒を除去して圧電材
料層を形成することを特徴とするものである。To summarize the present invention, the method for producing a linear piezoelectric material of the present invention has the property that when a film is formed from a solution on the surface of a conductive linear material, molecular chains are oriented in the flow direction of the solution. The method is characterized in that a solution containing an organic polymeric material is applied, and the solvent is removed while imparting a certain flow direction to the applied solution to form a piezoelectric material layer.
本発明における圧電材料の一例であるポリーγ−ベンジ
ルーＬ−グルタメート（以下ＰＢＬＧと略称する）は、
生体高分子の分野でも良く研究されている合成ポリペプ
チドの１種であり、溶液中から結晶化する場合に溶液の
流れ方向に分子鎖が配向する。Poly γ-benzy-L-glutamate (hereinafter abbreviated as PBLG), which is an example of the piezoelectric material in the present invention, is
It is a type of synthetic polypeptide that has been well studied in the field of biopolymers, and when crystallized from a solution, its molecular chains are oriented in the direction of flow of the solution.
本発明等は、ＰＢＬＧをジオキサンに溶解して粘調な溶
液をつくり、この溶液を斜めに立てかけたガラヌ板等の
平滑な面に沿って流し、これをジオキサンが完全に蒸発
して高分子固体が得られる１でスパチュラを用いて流れ
方向に沿ってならした。In the present invention, PBLG is dissolved in dioxane to create a viscous solution, and this solution is poured along a smooth surface such as a Galanu board placed diagonally, and the dioxane is completely evaporated to form a polymer solid. 1 was obtained, and was smoothed along the flow direction using a spatula.
このようにして得られたフィルムの両面にアルミニウム
蒸着膜を形成し、流れの方向に対して４５°の角度方向
に引張り振動応力を加え圧電性を測定すると、圧電率ｄ
２５＝ １．４Ｘ １０−１２Ｃ／Ｎの値が得られた。An aluminum vapor-deposited film is formed on both sides of the film thus obtained, and the piezoelectricity is measured by applying tensile vibration stress at an angle of 45° to the direction of flow.
A value of 25=1.4X 10-12C/N was obtained.
この圧電材料は、薄い高分子フィルムであり、引張り強
度及び耐折疲労強度に優れた高分子圧電材料であり、２
００°Ｃを越える温度１で溶結せず、又分解も非常に遅
い材料であることが認められた。This piezoelectric material is a thin polymer film, and is a polymer piezoelectric material with excellent tensile strength and bending fatigue strength.
It was found that the material does not weld at temperatures exceeding 00°C and decomposes very slowly.
同様な手法によりつくったＰＭＬＧにおいては、圧電率
ｄ２． ＝ ２．ＯＸ １０−１２Ｃホの値が得られた
。In PMLG made by a similar method, piezoelectric constant d2. = 2. A value of OX 10-12C was obtained.
この結果から、これらの高分子圧電材料は、溶液中より
成膜するときに溶液の流れの方向に分子配列をそろえる
性質を有しており、これに機械的応力を加えることによ
りその配向度が向上する特性をもっていることがわかる
。These results show that these polymeric piezoelectric materials have the property of aligning their molecules in the direction of the flow of the solution when they are formed into a film from a solution, and that the degree of orientation can be changed by applying mechanical stress to this material. It can be seen that it has improved properties.
又この高分子圧電材料に、分子配列にズリ応力が加えら
れるように力を加えた場合には、応力と垂直方向に電荷
が発生するような圧電性を示すことが認められた。Furthermore, when a force was applied to this polymeric piezoelectric material so as to apply shear stress to the molecular arrangement, it was observed that it exhibited piezoelectricity in which an electric charge was generated in a direction perpendicular to the stress.
本発明は、上記のような溶液中より成膜するときに溶液
の流れ方向に分子鎖が配向する性質を有する有機高分子
材料の特性を利用して、導電性線状材料の表面に高分子
圧電材料の層を形成した線状圧電材料であるが、その製
造に当っては、前記有機高分子材料を溶剤に溶解し、２
５重量％程度に濃縮した溶液中に導電性線状材料を浸清
し、該溶液に一定の流れ方向を与えるために例えば垂直
方向に引上げて乾燥する。The present invention utilizes the property of organic polymer materials, which have the property that molecular chains are oriented in the flow direction of the solution when a film is formed from a solution as described above, to deposit polymer molecules on the surface of a conductive linear material. This is a linear piezoelectric material in which a layer of piezoelectric material is formed, but in manufacturing it, the organic polymer material is dissolved in a solvent, and 2
A conductive linear material is immersed in a solution concentrated to about 5% by weight, and then pulled up and dried, for example, vertically, in order to give the solution a constant flow direction.
ＰＢＬＧ及びＰＭＬＧは一度乾燥状態にすることにより
ジオキサンには不溶の高分子固体となるので、上記の操
作を繰返すことにより塗膜の厚さを０．３ ｍｍ程度１
でとすることができる。Once PBLG and PMLG are dried, they become polymer solids that are insoluble in dioxane, so by repeating the above operation, the thickness of the coating film can be reduced to about 0.3 mm.
It can be done.
溶液濃度を大きくすることにより塗布回数を減すること
はできるが、溶液濃度の高い状態の塗布では圧電性が充
分に発揮されない。Although the number of applications can be reduced by increasing the solution concentration, the piezoelectricity cannot be sufficiently exhibited if the solution is applied at a high concentration.
このようにして作成した線状圧電材料の表面にアルミニ
ウム等の金属の層をスパッタリング等により形成し表面
（対向）電極を設けることにより圧電出力を取り出すこ
とができる。Piezoelectric output can be extracted by forming a layer of metal such as aluminum by sputtering or the like on the surface of the linear piezoelectric material created in this way and providing a surface (counter) electrode.
本発明にむける圧電材料としては、前記の性質を有する
有機高分子材料であれば使用可能であるが、特にポリペ
プチド系のような合成蛋白質例えばＰＢＬＧ及びＰＭＬ
Ｇ等が適当である。As the piezoelectric material for the present invention, any organic polymeric material having the above-mentioned properties can be used, but in particular, synthetic proteins such as polypeptides, such as PBLG and PML, can be used.
G etc. are suitable.
又、中心導電体としＱ上銅線の他に、リン青銅（，５Ｂ
ＳＳ扛）線バネ材料、ピアノ線のような金属材料更には
炭素繊維等、導電性物質であればこれらを電極として使
用可能であり、又絶縁゛；イ物質の表面を導体化したも
のも適用することができる。In addition, in addition to the copper wire on Q as the center conductor, phosphor bronze (,5B
Conductive materials such as SS wire spring materials, metal materials such as piano wire, and even carbon fiber can be used as electrodes, and insulating materials whose surfaces are made conductive can also be used. can do.
又、表面電極としては、Ａ１等の金属導電材料をスパッ
タリングにより形成したもの、導電性塗料を塗布したも
の、金属を無電解メッキしたもの等を使用することがで
きる。Further, as the surface electrode, those formed by sputtering a metal conductive material such as A1, those coated with conductive paint, those plated with metal electrolessly, etc. can be used.
この表面電極は利用方法によっては必要としない。This surface electrode may not be necessary depending on the usage.
次に本発明を実施例により説明するが、本発明はこれら
によりなんら限定されるものではない。EXAMPLES Next, the present invention will be explained with reference to Examples, but the present invention is not limited to these in any way.
実施例 １
中心に直径０．５ｍｍの銅網を用い、その表面に厚さ０
．３ｍｍのポリーγ−メチルーＬ−グルタメート（ＰＭ
ＬＧ）圧電体層を形成した。Example 1 A copper net with a diameter of 0.5 mm is used at the center, and a thickness of 0 on the surface is used.
．． 3 mm polygamma-methyl-L-glutamate (PM
LG) A piezoelectric layer was formed.
この線状圧電材料は、ポリーγ−メ羊ルーＬ−グルタメ
ートの１０％ジオキサン溶液を２５％濃度に濃縮し、こ
の溶液中に直径０．５ｍｍの銅線を浸清し、垂直方向に
３ｃｍ／分の速度で引き上げ、高さ２．５ ｍ ｔで上
げその状態で乾燥して作成した。This linear piezoelectric material was prepared by concentrating a 10% dioxane solution of poly-gamma-L-glutamate to a concentration of 25%, immersing a copper wire with a diameter of 0.5 mm in this solution, and immersing it in a vertical direction of 3 cm/3 cm. The specimen was lifted at a speed of 2.5 m, raised to a height of 2.5 m t, and dried in that state.
この操作を繰り返して塗膜の厚さを０．３ｍｍとするこ
とができた。This operation was repeated until the thickness of the coating film was 0.3 mm.
この線状圧電材料の表面にスパッタリングによりＭ層を
形成し表面電極を形成した。An M layer was formed on the surface of this linear piezoelectric material by sputtering to form a surface electrode.
この線状圧電材料１０ｃｍを切り取り、中心導電体と表
面電極間の電圧を、この線状圧電材料に曲げ応力を加え
て測定した結果、曲げ応力を加えたとき、数１０ｍｙの
パルス状の電圧が観測された。A 10cm piece of this linear piezoelectric material was cut out, and the voltage between the center conductor and the surface electrode was measured by applying bending stress to this linear piezoelectric material. When bending stress was applied, a pulse-like voltage of several 10 my was observed. Observed.
以上説明したように、本発明により製造された線状圧電
材料は中心導電体に可撓性を有する圧電材料の層が被覆
され、中心導電体に圧電出力が発生する構造とした圧電
材料であり、この線の振動によっても中心導電体に圧電
出力が得られる材料であるため、各種音響機器用の振動
弦等として用いれば、弦の振動を他の変換素子を用いる
ことなしに電気信号に変換することができ、
この形態の
圧電素子の利用分野は極めて広いものである。As explained above, the linear piezoelectric material manufactured according to the present invention is a piezoelectric material having a structure in which a center conductor is coated with a layer of a flexible piezoelectric material, and a piezoelectric output is generated in the center conductor. Since this material can generate piezoelectric output in the center conductor even by the vibration of this wire, if it is used as a vibrating string for various audio equipment, the vibration of the string can be converted into an electrical signal without using any other conversion element. This type of piezoelectric element can be used in an extremely wide range of fields.
Claims (1)
するときに溶液の流れ方向に分子鎖が配向する性質を有
する有機高分子材料を含む溶液を塗布し、該塗布溶液に
一定の流れ方向を付与しながら溶媒を除去して圧電材料
層を形成することを特徴とする線状圧電材料の製造方法
。 ２ 有機高分子材料がポリーγ−メチルーＬ−グルタメ
ート又はポリーγ−ベンジルーＬ−グルタメートである
特許請求の範囲１項記載の線状圧電材料の製造方法。[Scope of Claims] 1. Applying a solution containing an organic polymer material having a property that molecular chains are oriented in the flow direction of the solution when forming a film from the solution onto the surface of a conductive linear material, A method for producing a linear piezoelectric material, which comprises forming a piezoelectric material layer by removing a solvent while imparting a constant flow direction to the coating solution. 2. The method for producing a linear piezoelectric material according to claim 1, wherein the organic polymer material is poly γ-methyl-L-glutamate or poly γ-benzyl-L-glutamate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52103234A JPS5839395B2 (en) | 1977-08-30 | 1977-08-30 | Manufacturing method of linear piezoelectric material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP52103234A JPS5839395B2 (en) | 1977-08-30 | 1977-08-30 | Manufacturing method of linear piezoelectric material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5437300A JPS5437300A (en) | 1979-03-19 |
| JPS5839395B2 true JPS5839395B2 (en) | 1983-08-30 |
Family
ID=14348754
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP52103234A Expired JPS5839395B2 (en) | 1977-08-30 | 1977-08-30 | Manufacturing method of linear piezoelectric material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5839395B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63990U (en) * | 1986-06-23 | 1988-01-06 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5032597A (en) * | 1973-07-25 | 1975-03-29 | ||
| JPS5284498A (en) * | 1975-12-29 | 1977-07-14 | Mitsubishi Petrochemical Co | Piezooelectric material |
-
1977
- 1977-08-30 JP JP52103234A patent/JPS5839395B2/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5032597A (en) * | 1973-07-25 | 1975-03-29 | ||
| JPS5284498A (en) * | 1975-12-29 | 1977-07-14 | Mitsubishi Petrochemical Co | Piezooelectric material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63990U (en) * | 1986-06-23 | 1988-01-06 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5437300A (en) | 1979-03-19 |
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