JPH0696642B2 - Shape memory rubber elastic body and method of using the same - Google Patents
Shape memory rubber elastic body and method of using the sameInfo
- Publication number
- JPH0696642B2 JPH0696642B2 JP60227537A JP22753785A JPH0696642B2 JP H0696642 B2 JPH0696642 B2 JP H0696642B2 JP 60227537 A JP60227537 A JP 60227537A JP 22753785 A JP22753785 A JP 22753785A JP H0696642 B2 JPH0696642 B2 JP H0696642B2
- Authority
- JP
- Japan
- Prior art keywords
- elastic body
- rubber
- shape memory
- rubber elastic
- crystallinity
- 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 - Lifetime
Links
- 229920001971 elastomer Polymers 0.000 title claims description 64
- 239000005060 rubber Substances 0.000 title claims description 64
- 238000000034 method Methods 0.000 title claims description 5
- 229920000642 polymer Polymers 0.000 claims description 36
- 238000002425 crystallisation Methods 0.000 claims description 23
- 230000008025 crystallization Effects 0.000 claims description 23
- 230000009477 glass transition Effects 0.000 claims description 22
- 238000002844 melting Methods 0.000 claims description 20
- 230000008018 melting Effects 0.000 claims description 20
- 238000013329 compounding Methods 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 229920001084 poly(chloroprene) Polymers 0.000 claims description 13
- 239000002994 raw material Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 230000020169 heat generation Effects 0.000 claims description 5
- 244000043261 Hevea brasiliensis Species 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 244000001591 balata Species 0.000 claims description 2
- 235000016302 balata Nutrition 0.000 claims description 2
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical compound CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920003049 isoprene rubber Polymers 0.000 claims description 2
- 229920003052 natural elastomer Polymers 0.000 claims description 2
- 229920001194 natural rubber Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 239000005077 polysulfide Substances 0.000 claims description 2
- 229920001021 polysulfide Polymers 0.000 claims description 2
- 150000008117 polysulfides Polymers 0.000 claims description 2
- 238000004073 vulcanization Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000003566 sealing material Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000001125 extrusion Methods 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 230000005653 Brownian motion process Effects 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005537 brownian motion Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001739 density measurement Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000008393 encapsulating agent Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000010077 mastication Methods 0.000 description 1
- 230000018984 mastication Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000565 sealant Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001285 shape-memory alloy Inorganic materials 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000004636 vulcanized rubber Substances 0.000 description 1
Landscapes
- Processes Of Treating Macromolecular Substances (AREA)
- Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
【産業上の利用分野】 本発明は常温で変形を固定でき、融点以上に昇温させる
と加硫成形時の形状に復元させることのできる形状記憶
性ゴム弾性体及びその使用方法に関するに関するもので
ある。 その主な利用分野は封止材、防振ゴム部材、ギブスなど
の医療用部材、フックなどの建築用固定材、玩具用部材
等であり、使用に際して弾性を適当に維持しながら、加
温により容易に成形体の当初の形状に復元して目的を達
する分野に用いられるものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a shape memory rubber elastic body which can fix deformation at room temperature and can be restored to the shape at the time of vulcanization molding when heated above a melting point, and a method of using the same. is there. Its main fields of application are encapsulating materials, anti-vibration rubber materials, medical materials such as casts, architectural fixing materials such as hooks, toy materials, etc. It is used in a field where the object can be easily restored to the original shape and the purpose is reached.
熱的変化に対して生じる収縮とか他の形状への変形を利
用する技術は、プラスチックの分野において、例えば架
橋ポリオレフィンチューブを冷延伸させて変形固定し、
加熱して原形に復元させる熱収縮性チューブが知られて
いる。また、形状記憶弾性体として、ガラス転移温度が
10℃以上で分子量が100万以上のノルボルネン系ポリマ
ー（特開昭59−53528号）とか、ガラス転移温度が室温
以上の硬質樹脂状合成付加重合体（特開昭60−28433
号）が提案されている。In the field of plastics, for example, cross-linked polyolefin tubes are cold-stretched and deformed and fixed in the field of plastics, such as shrinkage caused by thermal change and deformation into other shapes.
A heat-shrinkable tube that is heated to restore the original shape is known. Further, as a shape memory elastic body, the glass transition temperature is
Norbornene-based polymers having a molecular weight of 1,000,000 or more at 10 ° C or higher (JP-A-59-53528), or hard resinous synthetic addition polymers having a glass transition temperature of room temperature or higher (JP-A-60-28433).
No.) is proposed.
しかし、ガラス転移温度が室温（23℃）以上の形状記憶
弾性体は、ガラス転移温度以下の温度で弾性が失われ、
弾性が要求される前記封止材等に適していない。また脆
化破損を伴うため大きな変形で固定できず、高温でなけ
れば原形に復元できない難点がある。However, a shape memory elastic body having a glass transition temperature of room temperature (23 ° C.) or higher loses elasticity at a temperature lower than the glass transition temperature,
It is not suitable for the encapsulant and the like that require elasticity. In addition, since it is accompanied by brittle fracture, it cannot be fixed with a large deformation, and it cannot be restored to its original shape unless it is at a high temperature.
そこで、本発明者らは、常温でゴム弾性を有したゴム成
形体に前記のような形状記憶性を与えるべく種々検討し
て本発明の完成に至ったのである。その特徴とする点
は、結晶化度20％以上のクロロプレンゴムを主原料ポリ
マーとし、又はこれに結晶性ポリマーを配合し、更に配
合剤を配合して得られた結晶性ポリマー組成物を架橋し
て得られるガラス転移温度が−10℃以下、融点が35〜90
℃、結晶化度が10〜50％である形状記憶性ゴム弾性体で
ある。 ガラス転移点と結晶化及び融点については、周知である
が、本願発明の説明の必要上からその違いを明確にして
おく。ガラス転移とは、高温から温度を降下させた時、
総ての高分子物質に急激に起こる変化で、この温度以下
では硬化脆化を生じる。ガラス転移点（Tg）以下では、
ゴムらしい物性を示すために必要な分子鎖のセグメント
のミクロブラウン運動が停止すると考えられている。こ
れに対し、結晶化は適当な低温に暴露するとき多くのゴ
ムに生じる現象で、硬度やモジュラスの増大を伴なう。
ガラス転移との大きな違いは、硬くはなるが必ずしも脆
くはなく、ゴムらしい弾性を保持している点にある。結
晶化は比較的広い温度範囲で生じるが、それ以上の温度
では結晶が存在しない温度をその物質の融点（Tm）とい
う。融点（Tm）は、低分子物質では一義的に決定される
が、ゴム材料のような高分子材料ではTgよりは求め易い
が明確に求めるのは困難であるとされている。ゴムが加
工されたり、使用される際は、溶媒が存在しない固体又
は流動状態で、この時の基本特性として、ガラス転移点
と融点は重要である。本発明においても、これらの点が
重要性を有しており、前記のように規定されている。 原料ポリマーは結晶化度20％以上のクロロプレンゴムが
好ましい。また、ゴム加硫物は配合剤やドーピング等に
より導電性を有したものであると、通電発熱により原形
に復元できる。 クロロプレンゴムは重合温度を変えることにより、トラ
ンス−1,4結合、シス−1,4結合、1,2−結合、3,4−結合
とミクロ構造を異にする。重合温度が高いとトランス結
合が減少するのである。また、重合温度を変えることに
より、結晶化度を変化する。重合温度が高いほど結晶の
融点が低くなり、常温での結晶化度は小さくなる。結晶
化度は周知のように密度測定により求められ、それによ
ると、重合温度とポリマーの25℃における結晶化度の関
係は第１表の通りである。 以上から明らかなように、重合温度が低いとトランス結
合が増加し、その規則性から結晶化し易くなるのであ
る。 結晶化の速度はポリマーの種類、温度条件等によって決
まるが、例えば、接着剤としてのみ使用されている結晶
性クロロプレンゴムの結晶化速度（t0.5）は，−５℃に
おいて概ね15分であり、20〜25％の結晶化度を示すので
都合が良い。このような特性を示す結晶性クロロプレン
ゴムとしては、従来は接着剤として専ら使用されていた
電気化学工業（株）製の製品名デンカクロロプレンＡ−
90,A−100,A−120等が好適に使用される。 上記の結晶性ブレンド物の前記他のポリマーは、結晶化
が室温域で生じる1,2ブタジエンゴム、トランス−1,4イ
ソプレンゴム、ガタパッチャ又はバラタ天然ゴム、多硫
化ゴムの中から選ばれた１又は２以上のポリマーであ
る。ブタジエン共重合体のうち、SBR、NBRは結晶化を起
こさないゴムとして知られているが、SBRは高ブタジエ
ン共重合物になると結晶化を起こすので、前記結晶化度
の範囲内に収めて使用することもできる。 これらの結晶性ポリマーは単独で用いることもできる
が、要求されるゴムの性能を得るために他のポリマーと
のブレンド、他の可塑剤を始めとする配合剤を配合して
用いることができる。通電によって発熱させて元の形状
に復元させる手法により、封止接続等の目的を達成する
場合には、例えば、グラファイトやカーボン等の導電性
配合剤の添加やドーピング等により導電性処理を行なう
ことができる。 これにより得られた形状記憶性ゴム弾性体は、通電によ
り除晶するに充分な発熱を生ずる程度の通電性を有する
もので、当該ゴム弾性体の融点以上の温度で変形させ、
次いで当該弾性体の融点以下の温度で変形を固定し、使
用に際しては、当該弾性体の通電による発熱により形状
を原形に復する。Therefore, the present inventors have conducted various studies to give the above-mentioned shape memory property to the rubber molded body having rubber elasticity at room temperature, and completed the present invention. The characteristic point is that chloroprene rubber having a crystallinity of 20% or more is used as a main raw material polymer, or a crystalline polymer is blended with this, and a crystalline polymer composition obtained by blending a compounding agent is crosslinked. Glass transition temperature obtained by -10 ℃ or less, melting point 35 ~ 90
A shape memory rubber elastic body having a degree of crystallinity of 10 to 50% at ℃. The glass transition point, crystallization, and melting point are well known, but the differences will be clarified for the purpose of explaining the present invention. The glass transition is when the temperature is lowered from a high temperature,
This is a rapid change in all polymer substances, and causes hardening embrittlement below this temperature. Below the glass transition point (Tg),
It is considered that the micro Brownian motion of the segment of the molecular chain necessary for exhibiting rubber-like properties is stopped. On the other hand, crystallization is a phenomenon that occurs in many rubbers when exposed to an appropriate low temperature, and is accompanied by an increase in hardness and modulus.
The major difference from the glass transition is that it is hard but not necessarily brittle, and retains elasticity like rubber. Crystallization occurs in a relatively wide temperature range, but the temperature above which crystals do not exist is called the melting point (Tm) of the substance. The melting point (Tm) is uniquely determined for a low molecular weight substance, but it is said that it is easier to obtain a melting point (Tm) than a Tg for a polymer material such as a rubber material, but it is difficult to obtain the melting point clearly. When the rubber is processed or used, the glass transition point and the melting point are important as basic properties at this time in a solid state or a fluid state in which a solvent does not exist. Also in the present invention, these points are important and are defined as described above. The raw material polymer is preferably chloroprene rubber having a crystallinity of 20% or more. If the rubber vulcanizate has electrical conductivity due to compounding agents, doping, etc., the rubber vulcanizate can be restored to its original shape by heat generation by energization. Chloroprene rubber has different microstructures such as trans-1,4 bond, cis-1,4 bond, 1,2-bond and 3,4-bond by changing the polymerization temperature. Higher polymerization temperatures reduce trans coupling. Further, the crystallinity is changed by changing the polymerization temperature. The higher the polymerization temperature, the lower the melting point of the crystal and the lower the crystallinity at room temperature. The crystallinity is determined by density measurement as is well known, and according to it, the relationship between the polymerization temperature and the crystallinity of the polymer at 25 ° C. is as shown in Table 1. As is clear from the above, when the polymerization temperature is low, trans bonds increase, and the regularity facilitates crystallization. The rate of crystallization depends on the type of polymer, temperature conditions, etc. For example, the crystallization rate (t0.5) of crystalline chloroprene rubber used only as an adhesive is about 15 minutes at -5 ° C. , Which is convenient because it shows a crystallinity of 20 to 25%. As the crystalline chloroprene rubber exhibiting such characteristics, a product name Denkachloroprene A- manufactured by Denki Kagaku Kogyo Co., Ltd., which has been conventionally exclusively used as an adhesive, is used.
90, A-100, A-120 and the like are preferably used. The other polymer of the above crystalline blend is selected from 1,2 butadiene rubber, trans-1,4 isoprene rubber, gutter patcher or balata natural rubber, polysulfide rubber, where crystallization occurs at room temperature. Or two or more polymers. Among butadiene copolymers, SBR and NBR are known as rubbers that do not crystallize, but SBR causes crystallization when it becomes a high butadiene copolymer, so use it within the above range of crystallinity. You can also do it. These crystalline polymers can be used alone, but in order to obtain the required rubber performance, they can be blended with other polymers and compounded with other plasticizers and other compounding agents. When achieving the purpose of sealing connection, etc. by the method of generating heat by energization and restoring the original shape, for example, conduct conductive treatment by adding or doping a conductive compounding agent such as graphite or carbon. You can The shape-memory rubber elastic body thus obtained has electric conductivity such that sufficient heat is generated to remove crystals by energization, and is deformed at a temperature equal to or higher than the melting point of the rubber elastic body.
Then, the deformation is fixed at a temperature equal to or lower than the melting point of the elastic body, and when used, the shape is restored to the original shape by heat generation due to the energization of the elastic body.
上記のような結晶化度20％以上のクロロプレンゴムを主
原料ポリマーとし、又はこれに結晶性ポリマーを配合
し、更に配合剤を配合して得られた結晶性ポリマー組成
物を架橋して得られるガラス転移温度が−10℃以下、融
点が35〜90℃、結晶化度が10〜50％である結晶性ポリマ
ー又はポリマーブレンド物のゴム加硫物は、通常のゴム
の加硫成形により所定の形状に成形され、ガラス転移点
以上の温度で結晶化により変形を固定することができ、
常温で弾性を有しており、再度融点以上に加熱すること
により元の所定の形状に復元する。 本願形状記憶性ゴム弾性体の ガラス転移温度（以下Tgと記す）を−10℃以下とした
ことにより、 室温以上では硬化脆化し、本願発明の効果を奏し得な
い。Tgが下がるに従って、ゴムらしさ（柔軟性）が向上
するが、本願発明のゴム弾性体の性能を発現するのは−
10℃以下である。Tgは基本となる結晶性ポリマーの性質
及び配合によって定まるが、Tgが−10℃以下であれば弾
性（柔軟性）を損わない。 融点（以下Tmと記す）を５℃〜90℃とした。 融点は基本となる結晶性ポリマーの性質及び配合によっ
て定まる。Tmが35℃以下では夏期等の高温（30℃以上）
において除晶し、容易に除晶して形状が原形に復し、使
用に適しない。この最低温度が35℃である。Tmが上昇す
るに従って、結晶化速度が早まり容易に結晶化して変形
が固定しやすくなる。 しかし、Tmが90℃以上になるとゴム弾性体の固定時の剛
性も上昇し樹脂ライクになる。また、容易に変形が復元
しにくくなる。この臨界温度が90℃である。 結晶化度（以下Crと記す）が10〜50％である。 Crは基本となる結晶性ポリマーの性質及び配合によって
定まる。結晶化度20％以上のクロロプレンゴムを主原料
ポリマーに使用した結晶性ポリマー組成物の架橋後のも
ののCrが10〜50％となるのは、その他に配合されること
のある他の結晶性ポリマー、配合剤、加硫系、加硫条件
等によりCrが変化するからである。他の結晶化度の低い
ポリマーの添加や可塑剤、配合剤の過度の添加によって
結晶化度は低下する。反対に、結晶化度の高いポリマー
の添加や加硫系、加硫条件による適正な架橋によって結
晶化度は上昇する。これらは配合ごと加硫系、加硫条件
ごとに決定される量である。もっとも、この結晶化度
は、圧縮、伸長等の外力、冷却速度、結晶化温度等によ
って変化するため、本件発明では、100℃で結晶を除晶
後、０℃で急冷して密度法にて測定した。Crが10％以下
の物質は自然界に数多く存在し、この程度の結晶化度で
は本願発明の作用は奏し得ない。少なくともCrは10％以
上である。Crが上昇するに従って当該ゴム弾性体は結晶
化度が上昇し、変形が強固に固定できるようになる。し
かし、50％以上となると、容易に結晶が除晶し得なくな
る。また、樹脂状となりゴムらしさを失ってしまう。 以上の〜に記載した、これらTg,Tm,Crは独立した物
理量ではなく、一方の変更によって他方が変動する密接
な関係を有し、ポリマー及び配合によって変化するが、
上記限定された数値範囲とした時に、好適に本願発明の
作用効果を発現する。 以下実施例によって本発明を詳細に説明する。A chloroprene rubber having a crystallinity of 20% or more as described above is used as a main raw material polymer, or a crystalline polymer is blended with the chloroprene rubber, and a crystalline polymer composition obtained by blending a compounding agent is cross-linked. A rubber vulcanizate of a crystalline polymer or a polymer blend having a glass transition temperature of −10 ° C. or lower, a melting point of 35 to 90 ° C., and a crystallinity of 10 to 50% can be obtained by vulcanizing and molding a usual rubber to a predetermined degree. Shaped, the deformation can be fixed by crystallization at a temperature above the glass transition point,
It has elasticity at room temperature and is restored to its original predetermined shape by heating again above its melting point. By setting the glass transition temperature (hereinafter referred to as Tg) of the shape-memory rubber elastic body of the present application to −10 ° C. or lower, curing embrittlement occurs at room temperature or higher, and the effect of the present invention cannot be obtained. As Tg decreases, rubber-likeness (flexibility) improves, but the performance of the rubber elastic body of the present invention is expressed by −
It is below 10 ℃. Tg is determined by the properties and blending of the basic crystalline polymer, but elasticity (flexibility) is not impaired if Tg is -10 ° C or lower. The melting point (hereinafter referred to as Tm) was set to 5 ° C to 90 ° C. The melting point is determined by the nature and formulation of the underlying crystalline polymer. When Tm is 35 ° C or lower, high temperature during summer (30 ° C or higher)
It is not suitable for use because it is crystallized in (1) and crystallized easily and the shape returns to its original shape. This minimum temperature is 35 ° C. As the Tm increases, the crystallization speed increases, and the crystallization easily occurs and the deformation tends to be fixed. However, when the Tm is 90 ° C or higher, the rigidity when fixing the rubber elastic body also increases and becomes resin-like. In addition, it becomes difficult for the deformation to be restored easily. This critical temperature is 90 ° C. The crystallinity (hereinafter referred to as Cr) is 10 to 50%. Cr is determined by the nature and formulation of the underlying crystalline polymer. Cr of 10 to 50% after cross-linking of a crystalline polymer composition using a chloroprene rubber having a crystallinity of 20% or more as a main raw material polymer is other crystalline polymer that may be blended with other. This is because Cr changes depending on the compounding agent, the vulcanization system, the vulcanization conditions and the like. The crystallinity is lowered by the addition of another polymer having a low crystallinity or the excessive addition of a plasticizer or a compounding agent. On the contrary, the crystallinity is increased by the addition of a polymer having a high crystallinity and proper crosslinking depending on the vulcanization system and vulcanization conditions. These are amounts that are determined for each vulcanization system and each vulcanization condition. However, since this crystallinity changes depending on external force such as compression and extension, cooling rate, crystallization temperature, etc., in the present invention, the crystal is decrystallized at 100 ° C. and then rapidly cooled at 0 ° C. by the density method. It was measured. A large number of substances having Cr of 10% or less exist in nature, and the crystallinity of this level cannot exert the effect of the present invention. At least Cr is 10% or more. As Cr increases, the degree of crystallinity of the rubber elastic body increases, and the deformation can be firmly fixed. However, if it exceeds 50%, the crystals cannot be easily removed. In addition, it becomes resinous and loses its rubberiness. As described in the above, these Tg, Tm, and Cr are not independent physical quantities, but have a close relationship in which one changes and the other fluctuates.
When the above numerical range is limited, the effects of the present invention are suitably exhibited. The present invention will be described in detail below with reference to examples.
【実施例１】 第２表に示した配合のＡ〜Ｈの実施例及び比較例の各ゴ
ム原料を通常の素練り、 混練り作業により均等に混合分散させた後、175℃、13
分間加硫成形してシート状加硫ゴムとした。 このゴム弾性体の物性を測定した結果を第３表に示し
た。結晶性クロロプレンゴムを用いた本発明の形状記憶
性ゴム弾性体は、低結晶性のクロロプレンゴムとほぼ同
等の耐熱性（120℃）を示している。また、圧縮永久歪
み（120℃）も同等の値を示している。引張り強さと引
裂き強さは、後者より優れるが結晶時と除晶時で物性が
大きく異なる。 硬さ（JISスプリングＡ）は、除晶時には約50〜60であ
るが、結晶化により硬さが約20〜30上昇する。ところ
が、反撥弾性は若干低下するもののなお40％以上の値を
保持している。 ゲーマンねじり試験（結晶化→除晶）の結果 この試験は既知トルクのワイヤーで各温度においてゴム
試験片を捩り、その捩れ角からスティフネスを知るため
のもので、広くゴム材料の耐寒性を評価するのに使用さ
れている。第１図に試験結果を図示した。見掛のガラス
転移温度（Tg）は図中の曲線の直線部分を温度軸に外挿
することにより求められる。耐寒性はこのガラス転移点
及び比モジュラスを示す温度で評価される。すなわち、
室温時剛さの２倍に剛くなる温度T5を示す温度付近まで
は室温時剛さを維持し、ゴム状弾性体とみなすことがで
きる。同じく５倍のT5,同10倍のT10の温度付近はわずか
な温度範囲で剛さが著しく変化し、皮革状態の範囲であ
り、T100では硬化が著しく見掛のガラス転移温度とみな
されている。但し、本明細書においてはT50をガラス転
移点（Tg）と評価している。図中において、結晶時の曲
線が高温において除晶時の曲線と交わる点Ａをそのゴム
の融点（Tm）とみなすことができる。 第１図から得られる知見から重要なことは、結晶時と除
晶時とにおいて、捩れ角（剛性率）は大きく変化する
が、ガラス転移点は大きく変化しないことである。ま
た、結晶時、除晶時のいずれもガラス転移温度以下に曝
すことにより瞬時にガラス転移を生ずるが、温度を如何
に下げようとも、結晶化は瞬時には進行しないことであ
る。このことからも、これらの現象は一般にいわれてい
るように全く異なる機構により生ずることが立証され
る。 上記諸物性は配合により、さまざまに変更できることが
第３表よりわかる。配合により大きく性能が変わるの
で、種々の目的に合わせて自由に設計することが可能で
ある。 以下図面によって、本発明の形状記憶性ゴム弾性体の復
元のようすを示す。 第２図（ａ）は実施例１の配合Ａで得られた短冊状の形
状記憶性ゴム弾性体（１）をぜんまい状に捲回し、０℃
で２時間放置して形状を固定したものである。この状態
でこの形状記憶性ゴム弾性体（１）は弾性を有している
ので指で解いても捲回状態に戻る。次に（ｂ）に示した
ように70℃の湯が入っているビーカー（２）中に入れる
と、瞬時に（ｃ）のように元の平坦な短冊状になり、形
状記憶が立証されたのである。Example 1 Each rubber raw material of the examples A to H of the formulations shown in Table 2 and the comparative examples was subjected to ordinary mastication, After uniformly mixing and dispersing by kneading work, 175 ℃, 13
It was vulcanized and molded for minutes to obtain a sheet-shaped vulcanized rubber. The results of measuring the physical properties of this rubber elastic body are shown in Table 3. The shape memory rubber elastic body of the present invention using the crystalline chloroprene rubber exhibits heat resistance (120 ° C.) almost equal to that of the low crystalline chloroprene rubber. The compression set (120 ° C) also shows the same value. The tensile strength and tear strength are superior to those of the latter, but the physical properties differ greatly between crystallization and decrystallization. The hardness (JIS spring A) is about 50 to 60 at the time of crystallization, but the hardness increases by about 20 to 30 due to crystallization. However, although the impact resilience is slightly reduced, it still holds a value of 40% or more. Results of Gehman torsion test (crystallization → decrystallization) This test is to twist a rubber test piece at each temperature with a wire of known torque and to know the stiffness from the twist angle, and widely evaluate the cold resistance of rubber materials. Used to The test results are shown in FIG. The apparent glass transition temperature (Tg) can be obtained by extrapolating the straight line portion of the curve in the figure to the temperature axis. Cold resistance is evaluated by the glass transition temperature and the temperature at which the specific modulus is exhibited. That is,
To near the temperature which indicates the temperature T 5 made stiff twice the room temperature TokiTsuyoshi is maintains the room temperature TokiTsuyoshi is, it can be regarded as a rubber-like elastic body. Similarly, in the vicinity of the temperatures of 5 times T 5 and 10 times T 10 , the rigidity changes remarkably in a slight temperature range and is in the leather state range, and in T 100 , curing is considered to be an apparent glass transition temperature. Has been done. However, in the present specification, T 50 is evaluated as the glass transition point (Tg). In the figure, the point A where the curve during crystallization intersects with the curve during crystallization at high temperature can be regarded as the melting point (Tm) of the rubber. What is important from the knowledge obtained from FIG. 1 is that the twist angle (rigidity) greatly changes between crystallization and decrystallization, but the glass transition point does not change significantly. Further, both during crystallization and during crystallization, the glass transition occurs instantly when exposed to the glass transition temperature or lower, but no matter how the temperature is lowered, the crystallization does not proceed instantaneously. This also proves that these phenomena are caused by completely different mechanisms as is generally said. It is understood from Table 3 that the above physical properties can be variously changed depending on the composition. Since the performance greatly changes depending on the composition, it can be freely designed for various purposes. The following will show how the shape-memory rubber elastic body of the present invention is restored with reference to the drawings. FIG. 2 (a) shows that the strip-shaped shape memory rubber elastic body (1) obtained by the compounding A of Example 1 is wound into a mainspring, and the temperature is 0 ° C.
The shape was fixed by leaving it for 2 hours. In this state, since the shape memory rubber elastic body (1) has elasticity, it returns to the wound state even if it is unwound with a finger. Then, as shown in (b), when placed in a beaker (2) containing 70 ° C hot water, the original flat strip was instantly formed as shown in (c), demonstrating shape memory. Of.
【実施例２】 本発明の形状記憶性ゴム弾性体に導電性を付与させて、
形状記憶合金と同様な通電発熱による復元が可能かどう
かのテストをするために、積層成形と二重押出成形によ
る二種類の通電発熱実験を行なった。 本実施例に使用した配合を第４表に、ゴムの物性を第５
表に示した。導電性を持たせたゴム（Ｋ）も非導電性の
ゴム（Ｊ）もいずれも耐熱性（120℃）、耐油性（＃１
油120℃）を有している。 −積層成形− 第３図（ａ）は実施例１の配合Ａによって得られた形状
記憶性ゴム弾性体（１）のシート２枚の間に、実施例２
の配合Ｋによって得られた導電性の形状記憶性ゴム弾性
体（３）を両端に電極（４）（４）を取付けてサンドイ
ッチ状に挟んでいる様子を示している。これらは積層圧
着し175℃で10分間一体成形した。次にこれを（ｂ）の
ように湾曲させて、室温で24時間放置した。放置後の積
層形状記憶性ゴム弾性体は伸張しても直ちに図のように
戻る。更に、この形状記憶性ゴム弾性体に24V、４分間
通電したところ、昇温して元の偏平なシート状に復元し
た。 −二重押出成形− 第４表に示した非導電性ゴム（Ｊ）と導電性ゴム（Ｋ）
を調製し、これを第４図（ａ）のように内層が導電性ゴ
ム（Ｋ）で外層が非導電性ゴム（Ｊ）となるよう二重押
出し成形し、蒸気圧8kg/cm2×15分で蒸気加硫を行なっ
た。この棒状形状記憶性ゴム弾性体（５）を第４図
（ｂ）のように湾曲させて、０℃、２時間放置し、変形
を固定した。この弾性体は両端から引いて伸しても、放
すと直ちに図のような湾曲形状に戻る。ところが、端部
の電極により通電（24V,2分）して、70℃以上になると
除晶してほぼ（ａ）の形状の元の棒状に復元した。 第５図は本発明品を封止材（８）として使用している様
子を示している。第５図（ａ）にみられるような封止材
（８）を1/2に圧縮して（ｂ）のような封止材とし、フ
ランジのような当接部材（６）（６）間に生じた隙間
（７）部分へ挿入し、90℃に加熱した。加熱によって直
ちに（ａ）に示したような形状に復元しようとして、
（ｃ）にみられるように隙間の完全な封止が可能であっ
た。Example 2 By imparting conductivity to the shape memory rubber elastic body of the present invention,
In order to test whether or not it is possible to restore by the same heat generation as the shape memory alloy, two kinds of heat generation experiments were conducted by lamination molding and double extrusion molding. The composition used in this example is shown in Table 4, and the physical properties of rubber are shown in Table 5.
Shown in the table. Both conductive rubber (K) and non-conductive rubber (J) have heat resistance (120 ° C) and oil resistance (# 1).
Oil 120 ° C). -Layered Molding- FIG. 3 (a) shows Example 2 between two sheets of the shape memory rubber elastic body (1) obtained by the compounding A of Example 1.
It shows a state in which the conductive shape memory rubber elastic body (3) obtained by the compounding K of (3) is attached to both ends with electrodes (4) and (4) and sandwiched in a sandwich shape. These were laminated and pressure-bonded and integrally molded at 175 ° C. for 10 minutes. Then, this was curved as in (b) and left at room temperature for 24 hours. After being left standing, the laminated shape memory rubber elastic body immediately returns as illustrated even when stretched. Further, when a voltage of 24 V was applied to this shape memory rubber elastic body for 4 minutes, the temperature was raised and the original flat sheet was restored. -Double extrusion molding-Non-conductive rubber (J) and conductive rubber (K) shown in Table 4
As shown in Fig. 4 (a), double-extrusion molding was performed so that the inner layer was the conductive rubber (K) and the outer layer was the non-conductive rubber (J), and the vapor pressure was 8 kg / cm 2 × 15. Steam vulcanization was performed in minutes. This rod-shaped shape memory rubber elastic body (5) was curved as shown in FIG. 4 (b) and left at 0 ° C. for 2 hours to fix the deformation. Even if the elastic body is pulled from both ends and stretched, it immediately returns to the curved shape as shown when released. However, electricity was applied (24 V, 2 minutes) by the electrode at the end, and at 70 ° C. or higher, the crystals were crystallized and restored to the original rod shape of approximately (a). FIG. 5 shows how the product of the present invention is used as a sealing material (8). Between the contact members (6) and (6) such as flanges, the sealing material (8) as shown in FIG. 5 (a) is compressed to 1/2 to form the sealing material as shown in (b). It was inserted into the gap (7) created in the above and heated to 90 ° C. Immediately trying to restore the shape shown in (a) by heating,
It was possible to completely seal the gap as seen in (c).
本発明の形状記憶性ゴム弾性体は、下記のような特徴を
備えている。 大きな変形で固定出来る。 通常のゴム弾性体と全く同様に加工出来る。 常温（−10〜30℃）で変形が固定できる。 100℃以下（概ね35〜90℃）の低温で形状が復元出来
るので、現場施工も簡単である。 変形固定時も形状復元時も大きな強度を有する。変
形固定時も弾性を有している。 耐オゾン性に優れている。 導電性を与えれば外部から熱水、ヒーター等の加熱手
段によらず、通電によって原形に復元できる。 したがって、本発明の形状記憶性ゴム弾性体は、可逆性
フックなど建築用固定材、電気制御防振ゴム、形状記憶
ストッパーなど防振ゴム部材、人工筋肉、ギブスなど医
療用部材、封止材、自動車用衝撃吸収部材、玩具用部材
等さまざまな分野で広範囲な用途に用いることができ
る。The shape memory rubber elastic body of the present invention has the following features. Can be fixed with a large deformation. It can be processed exactly like an ordinary rubber elastic body. Deformation can be fixed at room temperature (-10 to 30 ℃). Since the shape can be restored at a low temperature of 100 ° C or less (generally 35 to 90 ° C), on-site construction is easy. It has great strength both when it is deformed and fixed and when it is restored to its original shape. It has elasticity even when it is deformed and fixed. Has excellent ozone resistance. If it is made electrically conductive, it can be restored to its original shape by energization regardless of external heating means such as hot water or a heater. Therefore, the shape memory rubber elastic body of the present invention is a building fixing material such as a reversible hook, an electric control anti-vibration rubber, an anti-vibration rubber member such as a shape memory stopper, an artificial muscle, a medical member such as a cast, a sealing material, It can be used for a wide range of applications in various fields such as automobile shock absorbing members and toy members.
【図面の簡単な説明】 第１図はゲーマンねじり試験結果を示すグラフである。
第２図（ａ）は本発明の形状記憶性ゴム弾性体をゼンマ
イ状に形状保持させた様子を示す斜視図、（ｂ）は湯中
へ投入している様子を示す斜視図、（ｃ）は復元の様子
を示す斜視図である。第３図（ａ）は形状記憶性ゴム弾
性体の積層体を作成している様子を示す斜視図であり、
（ｂ）は通電の様子を示す斜視図である。第４図（ａ）
は本発明品を用いた二重押出成形品の端面斜視図であ
り、（ｂ）は通電の様子を示す斜視図である。第５図
（ａ）、（ｂ）、（ｃ）は本発明の形状記憶性ゴム弾性
体を封止材として用いている様子を示す斜視図である。 （１）（３）（５）……形状記憶性ゴム弾性体、（２）
……ビーカー （４）……電極、（６）……当接部材 （７）……隙間、（８）……封止材 （Ｊ）……非導電性ゴム、（Ｋ）……導電性ゴムBRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a graph showing the results of the Gehman torsion test.
FIG. 2 (a) is a perspective view showing a shape-memory rubber elastic body of the present invention held in a spiral shape, (b) is a perspective view showing a state of being poured into hot water, and (c). [Fig. 3] is a perspective view showing a state of restoration. FIG. 3 (a) is a perspective view showing a state where a laminated body of shape memory rubber elastic body is formed,
(B) is a perspective view showing a state of energization. Figure 4 (a)
[FIG. 3] is a perspective view of an end surface of a double extrusion molded product using the product of the present invention, and (b) is a perspective view showing a state of energization. 5 (a), (b), and (c) are perspective views showing a state in which the shape memory rubber elastic body of the present invention is used as a sealing material. (1) (3) (5) ... Shape memory rubber elastic body, (2)
...... Beaker (4) ...... Electrode, (6) …… Abutting member (7) …… Gap, (8) …… Sealant (J) …… Non-conductive rubber, (K) …… Conductive Rubber
Claims (4)
原料ポリマーとし、又はこれに結晶性ポリマーを配合
し、更に配合剤を配合して得られた結晶性ポリマー組成
物を架橋して得られるガラス転移温度が−10℃以下、融
点が35〜90℃、結晶化度が10〜50％である形状記憶性ゴ
ム弾性体。A chloroprene rubber having a crystallinity of 20% or more is used as a main raw material polymer, or a crystalline polymer is added to the chloroprene rubber as a main raw material polymer, and a compounding agent is further added to obtain a crosslinked crystalline polymer composition. A shape memory rubber elastic body having a glass transition temperature of -10 ° C or lower, a melting point of 35 to 90 ° C, and a crystallinity of 10 to 50%.
リマーは結晶化が室温域で生じる1,2ブタジエンゴム、
トランス−1,4イソプレンゴム、ガタパッチャ又はバラ
タ天然ゴム、多硫化ゴムの中から選ばれた１又は２以上
のポリマーである特許請求の範囲第１項記載の形状記憶
性ゴム弾性体。2. The other crystalline polymer of the crystalline polymer composition is 1,2 butadiene rubber in which crystallization occurs at room temperature,
The shape memory rubber elastic body according to claim 1, which is one or more polymers selected from trans-1,4 isoprene rubber, gutter patcher or balata natural rubber, and polysulfide rubber.
ーピングにより導電性を付与した特許請求の範囲第１項
記載の形状記憶性ゴム弾性体。3. The shape memory rubber elastic body according to claim 1, wherein a conductive compounding agent is used as the compounding agent or conductivity is imparted by doping.
原料ポリマーとし、又はこれに結晶性ポリマーを配合
し、更に配合剤を配合して得られた結晶性ポリマー組成
物を架橋して得られるガラス転移温度が−10℃以下、融
点が35〜90℃、結晶化度が10〜50％である形状記憶性ゴ
ム弾性体であって、配合剤に導電性配合剤を用いるか、
又はドーピングにより導電性を付与した導電性を有する
形状記憶性ゴム弾性体を当該ゴム弾性体の融点以上の温
度で変形させ、次いで当該弾性体の融点以下の温度で変
形を固定し、使用に際しては、当該弾性体の通電による
発熱により形状を原形に復することを特徴とする形状記
憶性ゴム弾性体の使用方法。4. A crystalline polymer composition obtained by using a chloroprene rubber having a crystallinity of 20% or more as a main raw material polymer, or by blending a crystalline polymer therein, and further blending a compounding agent into the crystalline polymer composition. A shape memory rubber elastic body having a glass transition temperature of −10 ° C. or lower, a melting point of 35 to 90 ° C., and a crystallinity of 10 to 50%, wherein a conductive compounding agent is used as a compounding agent,
Alternatively, a conductive shape memory rubber elastic body having conductivity by doping is deformed at a temperature equal to or higher than the melting point of the rubber elastic body, and then the deformation is fixed at a temperature equal to or lower than the melting point of the elastic body. A method of using a shape-memory rubber elastic body, wherein the shape is restored to the original shape by heat generation due to the energization of the elastic body.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60227537A JPH0696642B2 (en) | 1985-10-12 | 1985-10-12 | Shape memory rubber elastic body and method of using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60227537A JPH0696642B2 (en) | 1985-10-12 | 1985-10-12 | Shape memory rubber elastic body and method of using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6286025A JPS6286025A (en) | 1987-04-20 |
| JPH0696642B2 true JPH0696642B2 (en) | 1994-11-30 |
Family
ID=16862455
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60227537A Expired - Lifetime JPH0696642B2 (en) | 1985-10-12 | 1985-10-12 | Shape memory rubber elastic body and method of using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0696642B2 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0323742A3 (en) * | 1987-12-28 | 1990-10-17 | Tonen Chemical Corporation | Polymer composition, its heat resistant, shape memory formed product and method of producing same |
| JPH0674311B2 (en) * | 1988-11-04 | 1994-09-21 | 三菱重工業株式会社 | Elastic memory polymer powder material and method of using the same |
| JPH031946U (en) * | 1989-05-30 | 1991-01-10 | ||
| SE9902131L (en) * | 1999-06-08 | 2000-12-09 | Nolato Silikonteknik Ab | Method and apparatus for producing an elastic member and component comprising such elastic member |
| US7938923B2 (en) * | 2004-06-04 | 2011-05-10 | Cornerstone Research Group, Inc. | Method of making and using shape memory polymer composite patches |
| CN101343385A (en) * | 2007-07-12 | 2009-01-14 | Nok株式会社 | Vibration damping rubber and engine fixing support |
| CN110435170B (en) * | 2019-08-12 | 2021-04-13 | 南京林业大学 | Modification method for improving shape memory performance of gutta percha |
| CN111330292B (en) * | 2020-03-09 | 2022-03-29 | 奥飞娱乐股份有限公司 | Deformation toy and gutta-percha deformation toy |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6028433A (en) * | 1983-07-26 | 1985-02-13 | Nippon Zeon Co Ltd | Shape-memory molded body and method for using the same |
-
1985
- 1985-10-12 JP JP60227537A patent/JPH0696642B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6286025A (en) | 1987-04-20 |
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