JP2000144545A - Piezoelectric material and its production - Google Patents
Piezoelectric material and its productionInfo
- Publication number
- JP2000144545A JP2000144545A JP23623099A JP23623099A JP2000144545A JP 2000144545 A JP2000144545 A JP 2000144545A JP 23623099 A JP23623099 A JP 23623099A JP 23623099 A JP23623099 A JP 23623099A JP 2000144545 A JP2000144545 A JP 2000144545A
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- JP
- Japan
- Prior art keywords
- piezoelectric
- piezoelectric material
- molded product
- fiber
- axial direction
- 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.)
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- Materials For Medical Uses (AREA)
- Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、圧電性高分子より
成る繊維状物、或いは成型であり、これの長軸方向に力
（運動）が作用したときに圧電効果が生じることに特徴
を有するもので、特に、外科用補綴材あるいは補強材、
圧電素子等の電気材料分野等に用いて好適なものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fibrous material or a molding made of a piezoelectric polymer, characterized in that a piezoelectric effect is generated when a force (movement) acts on the fibrous material in the longitudinal direction. In particular, surgical prostheses or reinforcements,
It is suitable for use in the field of electric materials such as piezoelectric elements.
【０００２】[0002]
【従来の技術】従来、圧電性高分子の研究は多くなさ
れ、これに関連する特許も多く出願されている。例え
ば、特公昭６１−３４２７８号公報には全芳香族ポリア
ミドフィルムを素材とした耐熱性に優れた高分子圧電性
フィルムに関する技術が開示され、また、特公昭６２−
１７８０１号公報においては、ポリフッ化ビニリデン系
フィルムを素材とした圧電性、焦電性高分子フィルムの
製造方法が、更に、特開平５−１５２６３８号公報には
ポリ乳酸を原料とし、押し出し成形やプレス成形した
後、さらに一軸延伸することにより、圧電性を付与する
技術が開示される。2. Description of the Related Art Hitherto, a great deal of research has been conducted on piezoelectric polymers, and many patents related thereto have been filed. For example, Japanese Patent Publication No. 61-34278 discloses a technique relating to a polymer piezoelectric film having excellent heat resistance using a wholly aromatic polyamide film as a material.
Japanese Patent No. 17801 discloses a method for producing a piezoelectric or pyroelectric polymer film using a polyvinylidene fluoride film as a material. Further, Japanese Patent Application Laid-Open No. 5-152538 discloses an extrusion molding or pressing method using polylactic acid as a raw material. A technique of imparting piezoelectricity by further uniaxially stretching after molding is disclosed.
【０００３】一方、電気刺激による人体組織、とくに硬
組織の成長促進効果は古くから知られている（I.Yasud
a,J.Jpn.Orthop.Assoc.,29,351(1955)）。また、ポリ乳
酸の骨成長促進に関しても筏らが報告している（Y.Ikad
a et al. J. Biomed. Mater.Res.,30,553(1996)）。さ
らに、ポリ乳酸の圧電性を利用して医用材料に応用した
特許としては特開平６−１４２１８２および特開平６−
１４２１８４がある。これらの研究から圧電性高分子は
生体組織の運動により圧電効果が生じ、生体組織の成長
促進を促すことが期待される。ポリ乳酸フィルムは一軸
延伸することによりｄ１４なる圧電率テンソルを有する
ことが知られている。つまり、延伸軸に対してずり変形
が加わると軸方向に分極が生じる。従って、繊維やロッ
ドのような成形物にこれらの軸方向の運動に応力が加わ
ると予測される形状の場合には圧電効果は小さいと考え
られる。On the other hand, the effect of promoting the growth of human tissues, particularly hard tissues, by electrical stimulation has been known for a long time (I. Yasud).
a, J. Jpn. Orthop. Assoc., 29, 351 (1955)). Raft et al. Also reported that polylactic acid promotes bone growth (Y. Ikad
a et al. J. Biomed. Mater. Res., 30, 553 (1996)). Further, patents which apply to medical materials utilizing the piezoelectricity of polylactic acid include JP-A-6-142182 and JP-A-6-142182.
142184. From these studies, it is expected that the piezoelectric polymer generates a piezoelectric effect due to the movement of the living tissue, and promotes the growth of the living tissue. Polylactic acid films are known to have piezoelectric tensor composed d 14 by uniaxial stretching. That is, when shear deformation is applied to the stretching axis, polarization occurs in the axial direction. Therefore, it is considered that the piezoelectric effect is small in the case where a shape such as a fiber or a rod is expected to be subjected to stress in the movement in the axial direction.
【０００４】[0004]
【発明が解決しようとする課題】圧電性高分子を原料と
した繊維およびロッド等の成形物、ならびにそれらを加
工した織物、編物においては、付加される力は繊維軸方
向、あるいは繊維軸と直角方向が多い。通常、圧電性高
分子を用いてこのような繊維、あるいはロッド等を作製
しても上述したように、例えば延伸は繊維軸方向に沿っ
て行われるので、このような繊維軸方向にかかる力によ
っての圧電効果は小さく、また、繊維軸と直角方向の力
に関して圧電効果は０と考えられる。本発明は、圧電性
高分子を原料とした繊維状物および成形物、ならびにそ
れらを加工した織物、編物に繊維軸と平行あるいは直角
の力（運動）が働いた場合に圧電効果が大きく生じる繊
維あるいは成形物を提供するものである。In the case of molded articles such as fibers and rods made of a piezoelectric polymer as a raw material, and woven or knitted articles obtained by processing them, the applied force is in the direction of the fiber axis or at right angles to the fiber axis. There are many directions. Usually, even if such a fiber or a rod is manufactured using a piezoelectric polymer, as described above, for example, stretching is performed along the fiber axis direction. Is small, and the piezoelectric effect is considered to be zero with respect to the force in the direction perpendicular to the fiber axis. The present invention relates to a fibrous material and a molded product made of a piezoelectric polymer as a raw material, and a fiber that produces a large piezoelectric effect when a force (movement) parallel or perpendicular to the fiber axis acts on a woven or knitted fabric obtained by processing the fibrous or molded product. Alternatively, a molded product is provided.
【０００５】[0005]
【課題を解決するための手段】しかるに、本発明は、圧
電性高分子からなる繊維状物、または成形物であり、こ
れの軸方向に付加される張力によって圧電性を発生させ
るために、かかる張力の付加方向と異なる方向に捩りを
加えて構成したことを特徴とする圧電材、張力の付加方
向と異なる方向に結晶軸を構成した圧電材、捩り方向が
同一方向にまたは、反対方向と交互に、もしくは方向が
アトランダム加えられて成る圧電材、軸方向に対し、１
０〜６０°の捩りを加えて構成した圧電材、圧電性高分
子がポリ乳酸である圧電材、外科用補綴材あるいは補強
材として使用される圧電材、繊維状物、または成形物が
配向したものである圧電材、結晶軸方向が結晶あるいは
軸方向と一致している繊維状物、または成形物を捩るこ
とによって結晶軸方向が繊維あるいは成形物の長軸方向
と異なるよう構成する圧電材の製造法、非結晶状態の繊
維状物あるいは成形物をそのまま、若しくは延伸しなが
ら捩ることを特徴とする圧電材の製造法、捩りを同一方
向または、反対方向と交互に、もしくは方向がアトラン
ダムなるよう加えることに特徴を有するものである。SUMMARY OF THE INVENTION The present invention is directed to a fibrous or molded article made of a piezoelectric polymer, which is used to generate piezoelectricity by a tension applied in the axial direction. Piezoelectric material characterized by being twisted in a direction different from the direction in which the tension is applied, piezoelectric material having a crystal axis formed in a direction different from the direction in which the tension is applied, and the torsional direction is alternately in the same direction or in the opposite direction Or a piezoelectric material in which the directions are added at random
A piezoelectric material formed by applying a twist of 0 to 60 °, a piezoelectric material in which the piezoelectric polymer is polylactic acid, a piezoelectric material used as a surgical prosthesis or reinforcing material, a fibrous material, or a molded product is oriented. A piezoelectric material, a fibrous material whose crystal axis direction coincides with the crystal or axial direction, or a piezoelectric material whose crystal axis direction is different from that of the fiber or molded product by twisting the molded product Manufacturing method, a method for manufacturing a piezoelectric material characterized by twisting a fibrous material or molded product in an amorphous state as it is or while stretching, twisting in the same direction or alternately with the opposite direction, or the direction becomes at random. It has a characteristic in that it is added.
【０００６】[0006]
【発明の実施の形態】本発明に用いる圧電性高分子は延
伸可能なものであり、また、延伸時あるいは延伸後に熱
あるいは液体で膨潤させる等の手段により捩り変形を与
え、これをそのまま固定することが可能であればその素
材は問わない。例えば、そのような素材としてポリフッ
化ビニリデン系高分子、ポリ乳酸系高分子が例示でき
る。特に、体内埋入用の医用材料として用いる場合には
ポリ乳酸系高分子が好適である。かかるポリ乳酸は光学
活性を有するＬ体であっても、Ｄ体であっても構わな
い。また、重合体が結晶を有するのであればモノマーで
ある乳酸がＬ体およびＤ体の共重合体であっても構わな
い。分子量に関しても特に限定されるものではなく、実
際上、使用条件に合致しておれば低分子量でもよい。ま
た、ねじることが可能であれば高分子量のものでも差し
支えない。繊維状物および成形物はある一定値以下の直
径であれば繊維として、それを上回るサイズであれば成
形物として定義することができるが、捩り変形を生じさ
せることが可能であればそのサイズに限定はない。実際
上は織物で使用される５μｍのものから数ｃｍのものま
で例示できる。また、その断面形状は円形であっても方
形であっても構わない。BEST MODE FOR CARRYING OUT THE INVENTION The piezoelectric polymer used in the present invention is stretchable, and is subjected to torsional deformation by means of swelling with heat or liquid during or after stretching, and is fixed as it is. The material does not matter as long as it is possible. For example, examples of such a material include a polyvinylidene fluoride polymer and a polylactic acid polymer. In particular, when used as a medical material for implantation into the body, a polylactic acid-based polymer is suitable. Such polylactic acid may be an optically active L-form or a D-form. In addition, as long as the polymer has crystals, lactic acid as a monomer may be a copolymer of L-form and D-form. The molecular weight is not particularly limited, and may be a low molecular weight as long as it meets the conditions of use. In addition, as long as it can be twisted, a high molecular weight compound may be used. A fibrous material and a molded product can be defined as a fiber if the diameter is less than a certain value, and a molded product if the diameter is larger than the fiber. There is no limitation. Practically, it can be exemplified from those of 5 μm used in textiles to those of several cm. The cross-sectional shape may be circular or square.
【０００７】かかる素材に圧電性を付与するための方法
としては対象物に対し捩れ加える方法が例示できる。か
かる条件については、使用する圧電性高分子によって異
り、またその条件によっても結晶化度や結晶形態が変化
することも考えられるが、特に、捩り加工後の結晶軸が
繊維軸と異なっていれば目的を達する。その意味におい
て、素材とする繊維、成形物は延伸され、分子配向した
ものであることが好ましく、また、その捩り角度につい
ては軸に対し５〜７５°好ましくは１０〜６０°の範囲
にあることが望ましい。かかる加工は、例えば走行する
対象物に対し連続的に行っても、また、定サイズに寸断
された素材に対しバッチ式で行っても良い。その際の条
件としては、加工素材に塑性変形を生じさせる足る温度
を加え、捩った後これを固定するために冷却することが
好ましい。以下、具体的にその方法について例示した図
面をもとに説明する。As a method for imparting piezoelectricity to such a material, a method of twisting an object can be exemplified. Such conditions differ depending on the piezoelectric polymer used, and it is conceivable that the degree of crystallinity and crystal morphology also change depending on the conditions.In particular, the crystal axis after twisting is different from the fiber axis. If you reach your goal. In that sense, it is preferable that the fiber and the molded product are stretched and molecularly oriented, and that the torsion angle is in the range of 5 to 75 °, preferably 10 to 60 ° with respect to the axis. Is desirable. Such processing may be performed continuously, for example, on a running object, or may be performed batch-wise on a material cut to a fixed size. As a condition at that time, it is preferable to apply a temperature sufficient to cause plastic deformation of the work material, twist the material, and then cool the material to fix it. Hereinafter, the method will be described specifically with reference to the drawings.
【０００８】図１には本発明に係る圧電材を連続的に製
造する装置を例示する。同図において、１は加撚のため
の回転を与える駆動装置、２は糸管、３は乾熱槽、４は
ローラー槽、５は巻取機であり、駆動装置１の回転を受
けてこれに連結された糸管２より繰り出される糸に一定
の回転を与えて捩り、これを乾熱槽３、ローラ槽４を経
て巻取機５に巻き取られる過程において固定する。な
お、かかる加工に供される糸は延伸されたものであって
も、未延伸のものであっても良い。一方、他の方法とし
て、紡糸、延伸を連続的に行い、これを巻き取る過程で
図１のような回転を与え、その後熱セットして固定する
方法も例示できる。また、成形物においては一端を固定
し、他端よりトルクを加えたり、或いは押出し成形、延
伸装置を用い、成形物を押出す際に回転を与えることに
よっても加工を行うことができる。図３および図４に
は、本発明における捩り方法の他の例を示す。かかる方
法は同一方向に回転する１対のローラ（Ａ）、（Ｂ）を
並設し、被加工物を該ローラでニップしてx方向に進行
させるに際し、ローラ（Ｂ）をy方向に往復動させるこ
とによって図５で示すように異なる方向の捩りが交互に
繰り返される例を示す。かかる構成によると、捩り方向
が切り変わる境界部で電位差が生じ易い特徴がある。な
お、かかる交互の捩りのピッチ、周期は任意に設定すれ
ばよい。以下に実施例を挙げて説明する。FIG. 1 illustrates an apparatus for continuously producing a piezoelectric material according to the present invention. In the figure, reference numeral 1 denotes a driving device for imparting rotation for twisting, 2 denotes a yarn tube, 3 denotes a dry heat tank, 4 denotes a roller bath, and 5 denotes a winding machine. The yarn unwound from the yarn tube 2 connected to the torsion tube is given a certain rotation and twisted, and is fixed in the process of being wound up by the winder 5 through the dry heat tank 3 and the roller tank 4. The yarn to be subjected to such processing may be drawn or undrawn. On the other hand, as another method, there can be exemplified a method in which spinning and drawing are continuously performed, a rotation as shown in FIG. Further, the molded product can be processed by fixing one end and applying a torque from the other end, or by using an extrusion molding or stretching device and applying rotation when extruding the molded product. 3 and 4 show another example of the twisting method according to the present invention. In this method, a pair of rollers (A) and (B) rotating in the same direction are arranged side by side, and when the workpiece is nipped by the rollers and advanced in the x direction, the roller (B) reciprocates in the y direction. 5 shows an example in which twisting in different directions is alternately repeated as shown in FIG. According to such a configuration, there is a characteristic that a potential difference is easily generated at a boundary portion where the twist direction changes. The pitch and cycle of such alternate torsion may be set arbitrarily. An example will be described below.
【０００９】[0009]
【実施例１】分子量が３０万のポリＬ乳酸を原料とし、
２３５度の温度で紡糸機より押出し、水冷による冷却
後、１３０℃の乾熱槽にて９倍に延伸し、直径０．３ｍ
ｍの繊維糸を得た。これを８０℃のシリコーンオイル中
で１５ｃｍ当り２０回転／ｍｉｎの回転速度で９０回ね
じった。（６００ｔ／ｍ（長さ１ｍ当たりのネジリ数に
相当））。走査電子顕微鏡観察からねじり角度は約３０
度であった。前記において得たねじり加工前とねじり加
工後の繊維の圧電性を測定した。測定方法は図２に概略
図を示す、アクチュエーター（ソレノイド）６、試料は
さみ治具（可動側）９、試料はさみ治具（固定側）１
０、電極１１、ロックインアンプ１２より成る装置に白
金コート部分８を設けた試料７を装着し、測定した。測
定繊維長は６ｃｍ、この試験繊維の両端２ｃｍに通電の
ため白金コートを行ったものを用いた。ロックインアン
プ１２から出力された正弦波に従ってアクチュエーター
６が往復運動し、試験繊維に繰り返し張力がかかるよう
になっており、静止時の抵抗値は１０ＭΩ以上で測定不
可能であった。また、静止時の電圧は０．０１〜０．０
２ｍＶであった。測定結果を表１に示す。なお、対照区
は捩り加工前のものである。Example 1 Poly L-lactic acid having a molecular weight of 300,000 was used as a raw material,
It was extruded from a spinning machine at a temperature of 235 ° C, cooled by water cooling, stretched 9 times in a 130 ° C dry heat tank, and had a diameter of 0.3 m.
m of fiber yarn was obtained. This was twisted 90 times in silicone oil at 80 ° C. at a rotation speed of 20 revolutions / min per 15 cm. (600 t / m (corresponding to the number of twists per 1 m length)). The torsion angle was about 30 from scanning electron microscope observation.
Degree. The piezoelectricity of the fibers obtained before and after the twisting was measured. The measuring method is schematically shown in FIG. 2.
A sample 7 provided with a platinum-coated portion 8 was attached to an apparatus consisting of a 0, an electrode 11, and a lock-in amplifier 12, and measurement was performed. The measurement fiber length was 6 cm, and the test fiber was formed by applying platinum coating to both ends 2 cm for energization. The actuator 6 reciprocated in accordance with the sine wave output from the lock-in amplifier 12, and the test fiber was repeatedly subjected to tension. The voltage at rest is 0.01 to 0.0.
It was 2 mV. Table 1 shows the measurement results. In addition, a control section is a thing before twist processing.
【００１０】[0010]
【表１】 [Table 1]
【００１１】測定結果からも明らかに繊維をねじること
によって白金コートした電極間で大きな起電力が生じて
いることがわかる。これに対し、対照区のものは起電力
が生じているが微弱である。これは上述した特開平６−
１４２１８４に記述されているように理想的に結晶相に
平行な力が加わっていないためであると考えられる。From the measurement results, it is apparent that a large electromotive force is generated between the platinum-coated electrodes by twisting the fiber. On the other hand, in the control group, the electromotive force is generated, but is weak. This is described in Japanese Patent Laid-Open No.
This is probably because a force parallel to the crystal phase is not ideally applied as described in 142184.
【００１２】[0012]
【発明の効果】本発明は、圧電性高分子を原料とした繊
維およびロッド、ならびにそれらを加工した織物、編物
であり、繊維軸と平行あるいは直角の力が働いた場合に
圧電効果が大きく生じる繊維あるいは成形物を提供する
ものであり、具体的には圧電性高分子を原料とした繊維
あるいは成形物を軸方向と結晶軸方向を異なるようにし
て達成したものでものである。その効果の一例として、
外科用補綴、補強材としてこの繊維からなる織物を使用
すると繊維軸方向の張力によって圧電効果が生じ、骨や
軟部組織の再生を促すこと可能とし、更に、２次元、３
次元の繊維製品に加工することが可能であるから当該用
途のみでなく、電気部品等、多くの産業分野への適用も
可能なものである。Industrial Applicability The present invention relates to fibers and rods made of a piezoelectric polymer as raw materials, and woven or knitted fabrics obtained by processing them, and a large piezoelectric effect is produced when a force parallel or perpendicular to the fiber axis is applied. The present invention provides a fiber or a molded product, specifically, a fiber or a molded product obtained by using a piezoelectric polymer as a raw material by setting the axial direction and the crystal axis direction to be different from each other. As an example of the effect,
The use of a woven fabric made of this fiber as a surgical prosthesis or a reinforcing material generates a piezoelectric effect due to the tension in the fiber axis direction, thereby enabling the regeneration of bone and soft tissue to be promoted.
Since it is possible to process into a three-dimensional fiber product, it can be applied not only to the use but also to many industrial fields such as electric parts.
【図１】本発明圧電材の製造装置を例示した模式図。FIG. 1 is a schematic view illustrating a device for manufacturing a piezoelectric material of the present invention.
【図２】圧電効果の測定試験機を示す概略図。FIG. 2 is a schematic view showing a measuring machine for measuring the piezoelectric effect.
【図３】本発明圧電材の他の製造例を示す側面図。FIG. 3 is a side view showing another example of manufacturing the piezoelectric material of the present invention.
【図４】図３の斜視図。FIG. 4 is a perspective view of FIG. 3;
【図５】図３の方法によって得た本発明圧電材の模式
図。FIG. 5 is a schematic view of the piezoelectric material of the present invention obtained by the method of FIG.
１ 回転駆動装置 ２ 糸管 ３ 乾熱槽 ４ ローラー ５ 巻取機 ６ アクチュエーター（ソレノイド） ７ 圧電性測定試料 ８ 試料（７）の白金コート部分 ９ 試料はさみ治具（可動側） １０ 試料はさみ治具（固定側） １１ 電極 １２ ロックインアンプ DESCRIPTION OF SYMBOLS 1 Rotation drive device 2 Thread tube 3 Dry heat tank 4 Roller 5 Winder 6 Actuator (solenoid) 7 Piezoelectric measurement sample 8 Platinum coat part of sample (7) 9 Sample scissor jig (movable side) 10 Sample scissor jig (Fixed side) 11 electrodes 12 lock-in amplifier
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｈ０１Ｌ 41/22 Ｈ０１Ｌ 41/22 Ｚ Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat II (Reference) H01L 41/22 H01L 41/22 Z
Claims (10)
成形物であり、これの軸方向に付加される張力によって
圧電性を発生させるために、かかる張力の付加方向と異
なる方向に捩りを加えて構成したことを特徴とする圧電
材。1. A fibrous material or a molded product made of a piezoelectric polymer, and in order to generate piezoelectricity by a tension applied in an axial direction of the fibrous material, twist in a direction different from a direction in which the tension is applied. A piezoelectric material characterized by being additionally configured.
構成した請求項１記載の圧電材。2. The piezoelectric material according to claim 1, wherein the crystal axis is formed in a direction different from the direction in which the tension is applied.
と交互に、もしくは方向がアトランダム加えられて成る
請求項１または２項記載の圧電材。3. The piezoelectric material according to claim 1, wherein the torsion direction is the same, alternately with the opposite direction, or at random.
えて構成した請求項１〜３のいずれか１項記載の圧電
材。4. The piezoelectric material according to claim 1, wherein the piezoelectric material is twisted by 10 to 60 ° with respect to the axial direction.
〜４のいずれか１項記載の圧電材。5. The method according to claim 1, wherein the piezoelectric polymer is polylactic acid.
5. The piezoelectric material according to any one of items 4 to 4.
される請求項１~５のいずれか１項記載の圧電材。6. The piezoelectric material according to claim 1, which is used as a surgical prosthetic material or a reinforcing material.
である請求項１〜６のいずれか１項記載の圧電材。7. The piezoelectric material according to claim 1, wherein the fibrous material or the molded product is oriented.
している繊維状物、または成形物を捩ることによって結
晶軸方向が繊維あるいは成形物の長軸方向と異なるよう
構成する圧電材の製造法。8. Production of a piezoelectric material in which the crystal axis direction is different from the longitudinal direction of the fiber or molded product by twisting the molded product or the fibrous material whose crystal axis direction matches the axial direction. Law.
そのまま、若しくは延伸しながら捩ることを特徴とする
圧電材の製造法。9. A method for manufacturing a piezoelectric material, comprising twisting a non-crystalline fibrous material or molded product as it is or while stretching it.
互に、もしくは方向がアトランダムなるよう加えること
を特徴とする圧電材の製造法。10. A method for manufacturing a piezoelectric material, characterized in that torsion is applied in the same direction, alternately with the opposite direction, or at random.
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