JPH0368611A - Shape memory polymer material - Google Patents
Shape memory polymer materialInfo
- Publication number
- JPH0368611A JPH0368611A JP20514989A JP20514989A JPH0368611A JP H0368611 A JPH0368611 A JP H0368611A JP 20514989 A JP20514989 A JP 20514989A JP 20514989 A JP20514989 A JP 20514989A JP H0368611 A JPH0368611 A JP H0368611A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- shape
- polymer material
- shape memory
- materials
- 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.)
- Pending
Links
- 239000002861 polymer material Substances 0.000 title abstract description 13
- 229920000431 shape-memory polymer Polymers 0.000 title abstract description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 22
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 abstract description 18
- 238000000034 method Methods 0.000 abstract description 12
- 239000000178 monomer Substances 0.000 abstract description 11
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 abstract description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract description 2
- 239000000049 pigment Substances 0.000 abstract description 2
- 239000004014 plasticizer Substances 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- 230000002787 reinforcement Effects 0.000 abstract 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 6
- -1 acrylic ester Chemical class 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XFCMNSHQOZQILR-UHFFFAOYSA-N 2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOC(=O)C(C)=C XFCMNSHQOZQILR-UHFFFAOYSA-N 0.000 description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000001294 propane Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- VDYWHVQKENANGY-UHFFFAOYSA-N 1,3-Butyleneglycol dimethacrylate Chemical compound CC(=C)C(=O)OC(C)CCOC(=O)C(C)=C VDYWHVQKENANGY-UHFFFAOYSA-N 0.000 description 2
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000009434 installation Methods 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 2
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- MKGVDTBQOGHJLF-UHFFFAOYSA-N (2-hydroxy-3-naphthalen-2-yloxypropyl) 2-methylprop-2-enoate Chemical compound C1=CC=CC2=CC(OCC(O)COC(=O)C(=C)C)=CC=C21 MKGVDTBQOGHJLF-UHFFFAOYSA-N 0.000 description 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- BHUGZIJOVAVBOQ-UHFFFAOYSA-N 2-(propylazaniumyl)acetate Chemical compound CCCNCC(O)=O BHUGZIJOVAVBOQ-UHFFFAOYSA-N 0.000 description 1
- UEKHZPDUBLCUHN-UHFFFAOYSA-N 2-[[3,5,5-trimethyl-6-[2-(2-methylprop-2-enoyloxy)ethoxycarbonylamino]hexyl]carbamoyloxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(=O)NCCC(C)CC(C)(C)CNC(=O)OCCOC(=O)C(C)=C UEKHZPDUBLCUHN-UHFFFAOYSA-N 0.000 description 1
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- GLUKIOBQQKVZGW-UHFFFAOYSA-N CC(=C)C(=O)OCC=P(=O)C1=CC=CC=C1 Chemical compound CC(=C)C(=O)OCC=P(=O)C1=CC=CC=C1 GLUKIOBQQKVZGW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000003484 crystal nucleating agent Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- UJKWLAZYSLJTKA-UHFFFAOYSA-N edma Chemical compound O1CCOC2=CC(CC(C)NC)=CC=C21 UJKWLAZYSLJTKA-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000007334 memory performance Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920001610 polycaprolactone Polymers 0.000 description 1
- 239000004632 polycaprolactone Substances 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 230000001012 protector Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000011359 shock absorbing material Substances 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Abstract
Description
【発明の詳細な説明】 （産業上の利用分野） 本発明は形状記憶性高分子材料に関する。[Detailed description of the invention] (Industrial application field) The present invention relates to shape memory polymeric materials.
（従来の技術）
高分子化合物の成形体において、その形状のままでは装
着や組立て、搬送時の作業が困難な場合に、−時的に作
業の際の取扱いが容易となる様に変形し、装着や組立て
等が終了した後で加熱操作等により所定の形状に回復さ
せ、本末の目的とする働きをさせること又は変形した成
形体を元の状態に回復させること自体に主点を置いた用
途等に適した材料、即ち形状記憶性成形体について従来
から種々検討がなされている。(Prior art) When it is difficult to attach, assemble, or transport a molded article of a polymer compound in its original shape, it is sometimes deformed to make it easier to handle during the operation. Applications that focus on restoring a predetermined shape through heating operations, etc. after installation or assembly, etc., to perform the intended function, or restoring a deformed molded product to its original state. Various studies have been made on materials suitable for such purposes, that is, shape-memory molded bodies.
従来から、形状記憶性成形体についでは例えば、ノルボ
ルネン系ポリマー威形体（特開昭５９−５３５２８号）
、共役ジエン又はエポキシ基含有化合物等と芳香族ビニ
ル、不飽和ニトリル又はアクリル酸エステル等との共重
合体成形体（特開昭６０−２８４３３号）或いはポリカ
プロラクトンを用いた架橋成形体（特開昭５９−１１３
１５号）等が知られている。Conventionally, regarding shape memory molded bodies, for example, norbornene-based polymer shaped bodies (Japanese Patent Application Laid-open No. 59-53528) have been used.
, a copolymer molded product of a conjugated diene or an epoxy group-containing compound, etc., and an aromatic vinyl, an unsaturated nitrile, or an acrylic ester (JP-A-60-28433), or a cross-linked molded product using polycaprolactone (JP-A-60-28433) Showa 59-113
No. 15) etc. are known.
又、融点４０〜１００℃の結晶性ジエン系重合体を主成
分とする岨戊物からの架橋成形体（特開昭６２−１９２
４４０％ ）や、スチレン−ブタジェンブロック共重合
体とトランスポリインブレン等とのブレンドポリｖ−（
ｍｍＷ８６３−１７９９５５号＞Ｗ＆公知ｔ’アル。In addition, a crosslinked molded product made from a molded product containing a crystalline diene polymer having a melting point of 40 to 100°C as a main component (Japanese Patent Application Laid-Open No. 62-192
440%), blended polyv-(
mmW863-179955>W & known t'al.
しかし、これらは加工性が良くない、透明性に劣る、又
は、形状を回復させるのに時間がかかる、高温を要する
などいずれも一長一短があった。However, these materials all have advantages and disadvantages, such as poor workability, poor transparency, time required to recover shape, and high temperature requirements.
（発明が解決しようとする課ＩＩ）
本発明の目的は加工性、透明性、耐熱性、耐候性、ｉ薬
品性、耐油性、耐溶剤性、耐水性、攬水攬油性、耐摩耗
性、不燃性などに優れると共に、形状記憶性能において
も前記従来技術の短所を改善するもので、加熱により、
短時間に高い回復率で復元できる優れた形状記憶性高分
子材料を提供することにある。(Issue II to be solved by the invention) The objects of the present invention are processability, transparency, heat resistance, weather resistance, chemical resistance, oil resistance, solvent resistance, water resistance, water and oil repellency, abrasion resistance, In addition to being excellent in nonflammability, it also improves the disadvantages of the conventional technology in terms of shape memory performance, and by heating,
The object of the present invention is to provide an excellent shape memory polymer material that can be restored in a short period of time with a high recovery rate.
（課題を解決するための手段）
本発明はアクリル系ポリマーをスチレン系モノマーに接
触せしめ、次いでこれを重合に付し、又は更にＩＰＮ化
して得られる高分子物質より形成されたことを特徴とす
る形状記憶性高分子材料に係る。(Means for Solving the Problems) The present invention is characterized in that it is formed from a polymer material obtained by bringing an acrylic polymer into contact with a styrene monomer, then subjecting it to polymerization, or further converting it into IPN. Concerning shape memory polymer materials.
本発明の前記材料は一旦実際の使用に必要な形状に成形
したａＷ定の温度下にて変形を与えても、再度特定の温
度に加熱することにより変形は自動的に除去され当初の
形状又はそれに近い形状に回復させることができること
から、このような機能が要求される分野での種々の利用
が可能である。Once the material of the present invention is molded into the shape required for actual use, even if it is deformed at a constant temperature, the deformation is automatically removed by heating it to a specific temperature again, and the original shape or Since it can be restored to a shape similar to that, it can be used in various fields where such functions are required.
本発明においでアクリル系ポリマーとしては通常公知の
ものを用いることができ、例えば下記アクリルモノマー
の単独又は共重合体を用いることができる。In the present invention, commonly known acrylic polymers can be used, such as single or copolymers of the following acrylic monomers.
アクリルモノマーとしては種類は制限されないが、単ま
たは多官能性のものが含まれ、好ましくは、例えばメタ
クリル酸メチル（ＭＭＡ）、メタクリル酸エチル（ＥＭ
Ａ）、メタクリル酸ブチル（ＢＭＡ）、２−ヒドロキシ
エチルメタクリレート（ＨＥＭＡ）、３−（）リメトキ
シシリル）プロピルメタクリレート（ＭＳＰＭ）、２−
（フェニルホスホリル）エチルメタクリレート（ｐｈｅ
ｎｙｌ Ｐ ）、２−ヒドロキシ−３−（β−す７ト
キシ）プロピルメタクリレート（ＨＮＰＭ）、Ｎ−フェ
ニル−Ｎ−（２−ヒドロキシ−３−メタクリロキシ）プ
ロピルグリシン（Ｎ Ｐ Ｃ−Ｇ Ｍ Ａ ）、エチレ
ングリコールジメタクリレート（ＥＤＭＡ、又はＩＧ）
、ジエチレングリコールジメタクリレート（ＤｉＥＤＭ
Ａ）、トリエチレングリコールジメタクリレート（Ｔ
ｒｉＥＤＭＡ）、１，４−プタンジオールジメタクリレ
ー）（１，４ＢｕＤＭＡ）、１，３−ブタンジオールジ
メタクリレート（１，３−ＢｕＤＭＡ）、２，２−ビス
〔４−（２−ヒドロキシ−３−メタクリロキシプロポキ
シ）フェニル〕プロパン（Ｂｉｓ−ＧＭＡ）、２，２−
ビス（４−メタクリロキシフェニル）プロパン（ＢＰＤ
ＭＡ）、２，２−ビス（４−）！クリロキシエトキシフ
ェニル）プロパン（Ｂｉｓ−ＭＥＰＰ）、２，２−ビス
（４−メタクリロキシポリエトキシフェニル）プロパン
（Ｂｉｓ−ＭＰＥＰＰ）、ジ（メタクリロキシエチル）
トリノチルヘキサメチレンジウレタン（ＵＤＭＡ）、）
リノチロールプロパントリノタクリレート（ＴＭＰＴ）
、
Ｃ１１□＝Ｃ（ＣＩｌ、）ＣＯＯＣ１１２ＣＦ３ （
３ＦＭＡ）、ＣＨ，＝Ｃ（ＣＨ３）Ｃ００ＣＨ２ＣＦ、
ＣＦｆｆ （５ＦＭＡ）、Ｃｌ２＝Ｃ（ＣＨｊ）ＣＯ
ＯＣＨ，（ＣＦ２）２ＣＦ３ （７ＦＭＡ）、ＣＨｚ
＝Ｃ（Ｃ１１＊）ＣＯＯＣｌ１２（ＣＦｉ）３ｃＦＪ
（８ＦＭＡ）、これらの対応する各７クリレート、各
ａ−フルオロアクリレートを例示することができる。The type of acrylic monomer is not limited, but mono- or polyfunctional ones are included, and preferably, for example, methyl methacrylate (MMA), ethyl methacrylate (EM
A), butyl methacrylate (BMA), 2-hydroxyethyl methacrylate (HEMA), 3-()rimethoxysilyl)propyl methacrylate (MSPM), 2-
(phenylphosphoryl)ethyl methacrylate (phe
nyl P ), 2-hydroxy-3-(β-7toxy)propyl methacrylate (HNPM), N-phenyl-N-(2-hydroxy-3-methacryloxy)propylglycine (N P C-G MA ), Ethylene glycol dimethacrylate (EDMA, or IG)
, diethylene glycol dimethacrylate (DiEDM
A), triethylene glycol dimethacrylate (T
riEDDMA), 1,4-butanediol dimethacrylate (1,4BuDMA), 1,3-butanediol dimethacrylate (1,3-BuDMA), 2,2-bis[4-(2-hydroxy-3- Methacryloxypropoxy)phenyl]propane (Bis-GMA), 2,2-
Bis(4-methacryloxyphenyl)propane (BPD
MA), 2,2-bis(4-)! Chryloxyethoxyphenyl)propane (Bis-MEPP), 2,2-bis(4-methacryloxypolyethoxyphenyl)propane (Bis-MPEPP), di(methacryloxyethyl)
trinotylhexamethylene diurethane (UDMA), )
Linotyrolpropane trinotacrylate (TMPT)
, C11□=C(CIl,)COOC112CF3 (
3FMA), CH,=C(CH3)C00CH2CF,
CFff (5FMA), Cl2=C(CHj)CO
OCH, (CF2)2CF3 (7FMA), Chz
=C(C11*)COOCl12(CFi)3cFJ
(8FMA), each of these corresponding 7 acrylates, and each a-fluoroacrylate can be exemplified.
又、スチレン系モノマーとしては通常公知のものは全て
用いることができ、具体例としてはスチレン、ａ−メチ
ルスチレン、メチルスチレン、ククロロスチレン等の単
独或いはこれらと７クリロニトリル、フタジエン、エチ
レングリコールジノタフリレー）（ＩＧ）、１−．４−
ブタンジオールジメタクリレート（１，４ＢｕＤＭＡ）
、ジエチレングリコールジメタクリレート（ＤｉＥＤＭ
Ａ）、トリエチレングリコールジメタクリレー）（Ｔｒ
ｉＥＤＭＡ）、１．３−ブタンジオールジメタクリレー
ト（ｈ３−ＢｕＤＭＡ）、２，２−ビス（４−（２−ヒ
ドロキシ−３−メタクリロキシプロポキシ）フェニル〕
プロパン（Ｂｉｓ−ＧＭＡ）、トリノチロールプロパン
トリノタクリレート（ＴＭＰＴ）等との混合物などが挙
げられる。Furthermore, as the styrene monomer, all commonly known styrene monomers can be used, and specific examples include styrene, a-methylstyrene, methylstyrene, dichlorostyrene, etc. alone or in combination with 7-crylonitrile, phthadiene, ethylene glycoldinol, etc. Tough Relay) (IG), 1-. 4-
Butanediol dimethacrylate (1,4BuDMA)
, diethylene glycol dimethacrylate (DiEDM
A), triethylene glycol dimethacrylate) (Tr
iEDMA), 1,3-butanediol dimethacrylate (h3-BuDMA), 2,2-bis(4-(2-hydroxy-3-methacryloxypropoxy)phenyl)
Examples include mixtures with propane (Bis-GMA), trinotylolpropane trinotacrylate (TMPT), and the like.
本発明においては上記アクリル系ポリマーをスチレン系
モノマーに接触せしめ、次いでこれを重合に付すること
により高分子物質を得るが、その際アクリル系ポリマー
にスチレン系モノマーを接触させると、通常前者が後者
中で溶解又は膨潤し、もしくは後者が前者中に含浸する
などの態様を呈する。又、重合方法としでは、スチレン
系モノマーの公知の重合方法が採用できるが、光重合、
熱重合が好ましい。In the present invention, a polymer substance is obtained by bringing the acrylic polymer into contact with a styrene monomer and then subjecting it to polymerization. At this time, when the acrylic polymer is brought into contact with a styrene monomer, the former usually The latter dissolves or swells in the former, or the latter impregnates the former. In addition, as a polymerization method, a known polymerization method for styrene monomers can be adopted, but photopolymerization,
Thermal polymerization is preferred.
本発明において重合反応を加熱重合によるときは例えば
約４０〜１００℃の温度で、約１０〜１５０分程度加熱
することにより、又、光重合によるときは例えば可視光
線、紫外線を照射して数分〜数十分重合するのが好まし
い。In the present invention, when the polymerization reaction is carried out by heat polymerization, for example, by heating at a temperature of about 40 to 100°C for about 10 to 150 minutes, or when carried out by photopolymerization, for example, by irradiating with visible light or ultraviolet light for several minutes. It is preferable to polymerize for several tens of minutes.
本発明の形状記憶性高分子材料としでは上記の高分子物
質をＩ Ｐ Ｎ （Ｉ ｎｔｅｒ −ｐｅｎｅｔｒａｔ
ｉｎｇｐ ０１ｙＨｅｒＮ ｅｔｗｏｒｋ）化したもの
も包含する。■ＰＮ化は本来２種の鎖状のポリマーを液
体状態（溶液でも可〉で混合し、両方又はいずれか一方
を架橋させ、互いに分子鎖を絡み合わせた形で形成され
るポリマーである０本方法を本発明に利用する場合、幾
つかの変則的方法が用いられる。即ち、例えば第一の方
法は、予め高分子物質をフィルム化しておき、これにゲ
スト高分子を形成するモノマーをス相状態で注入するか
、前記モノマーを含むｆ＃液に前記フィルムを浸漬し、
注入し、しかる後、加熱又は光照射等の操作に上り重合
又は架橋させるものである。第二の方法は、通常のＪＰ
Ｎ形威形成じく、高分子物質を適当な溶媒に溶解させて
おき、これにゲスト成分を混合反応させ、その溶液をキ
ャストしてフィルム化し、必要に応じで加熱処理等を行
う方法である。その他の方法も使用することができる。As the shape memory polymer material of the present invention, the above polymer substance is
ingp01yHerNetwork) is also included. ■PNization is originally a polymer formed by mixing two types of chain polymers in a liquid state (a solution is also possible), crosslinking both or one of them, and intertwining the molecular chains with each other. When the method is utilized in the present invention, several irregular methods are used.For example, the first method is to form a polymer material into a film in advance, and then steam-phase the monomer that will form the guest polymer onto this film. or immersing the film in an f# solution containing the monomer,
It is injected and then subjected to operations such as heating or light irradiation to polymerize or crosslink. The second method is normal JP
This is a method in which a polymer substance is dissolved in an appropriate solvent, a guest component is mixed and reacted with the N-form, and the solution is cast to form a film, which is then subjected to heat treatment, etc., if necessary. . Other methods can also be used.
ＪＰＮ化を進めるためには架橋を行う必要があるが・そ
の方法としては例えばスチレン系ポリマーを予め常法に
より架橋したものを使用する、前記アクリル系モノマー
として２官能以上のものを用いて、重合によって架橋化
ポリマーを得る、或いは得られた未架橋重合体を有機パ
ーオキサイド、放射線、イオン性化合物などのラジカル
源、イオン源などによって、その重合体に適した方法″
ｃｔ＆架橋する方法等が挙げられる。尚、本発明のスチ
レン系モ／マーを重合させて得られるポリマーとアクリ
ル系ポリマーのポリマーブレンドを本発明の形状記憶性
高分子材料として用いることもできる。In order to proceed with JPN conversion, it is necessary to perform crosslinking, but the method for this is, for example, using a styrene polymer that has been crosslinked in advance by a conventional method, or using a difunctional or higher functional acrylic monomer as the acrylic monomer. to obtain a crosslinked polymer, or the obtained uncrosslinked polymer to a radical source such as an organic peroxide, radiation, an ionic compound, an ion source, etc., using a method suitable for the polymer.
Examples include a method of ct & crosslinking. In addition, a polymer blend of a polymer obtained by polymerizing the styrenic mo/mer of the present invention and an acrylic polymer can also be used as the shape memory polymer material of the present invention.
本発明で使用される高分子物質は、加工性、透明性、耐
熱性、耐候性、ｉｔ！品性、耐油性、耐溶剤性、耐水性
、祝水役油性、耐摩耗性、不燃性に優れると共に、形状
記憶性に優れる。The polymeric material used in the present invention has excellent processability, transparency, heat resistance, weather resistance, and IT! It has excellent properties, oil resistance, solvent resistance, water resistance, water resistance, abrasion resistance, nonflammability, and shape memory.
本発明の高分子材料は、上記で得られた高分子物質を例
えば押出成形、射出成形、圧縮成形等で所望の形に成形
又は適当な溶媒に溶解又は分散させることに上り塗料化
することによって所望の形態にした後、後述の用途に使
用される。その際に更に必要に応じて充填剤、補強剤、
軟化剤、可塑剤、相溶化剤、結晶核剤、老化防止剤、酸
化防止剤、オゾン劣化防止剤、紫外線吸収剤、顔料、染
料、粘着付与樹脂等のゴム、プラスチック配合剤を配合
してもよい。The polymer material of the present invention can be produced by molding the polymer substance obtained above into a desired shape, for example, by extrusion molding, injection molding, compression molding, etc., or by dissolving or dispersing it in an appropriate solvent, and then turning it into a paint. After forming into the desired form, it is used for the purposes described below. At that time, fillers, reinforcing agents,
Even if rubber and plastic compounding agents such as softeners, plasticizers, compatibilizers, crystal nucleating agents, anti-aging agents, antioxidants, anti-ozonants, ultraviolet absorbers, pigments, dyes, and tackifying resins are added. good.
本発明の高分子材料から得られる物品はその形状又は肉
厚に応じて素手、工兵或いは圧縮成形機等の装置を用い
て所望とする第２の形に変形されて用いられる。を形さ
せる際の温度は該高分子物品が容易に変形し、かつ変形
時に亀裂を生じさせない温度であればよい、−船釣には
高分子物質のガラス転移点以上の温度が好ましい、！！
形湿温度前記転移点以上である場合には変形後前記転移
点以下に急冷し、変形を固定することが好ましい。The article obtained from the polymeric material of the present invention is used after being transformed into a desired second shape using bare hands, an engineer, or a device such as a compression molding machine, depending on its shape or wall thickness. The temperature at which the polymeric article is shaped may be any temperature that allows the polymeric article to be easily deformed and does not cause cracks during deformation. - For boat fishing, a temperature higher than the glass transition point of the polymeric material is preferred! !
When the shape and humidity temperature is above the transition point, it is preferable to rapidly cool down to below the transition point after deformation to fix the deformation.
このようにして得られた形状記憶性高分子物品はガラス
転移点以上の温度下で容易に当初の形状にあるいはそれ
に近い形状に戻すことができる。The shape memory polymer article thus obtained can be easily returned to its original shape or a shape close to it at a temperature above the glass transition point.
通常高分子物質のガラス転移点以上（５０〜１００℃）
に加熱すればよく、それに上って変形は自動的に除去さ
れ、形状が回復する。Usually above the glass transition point of polymeric substances (50-100℃)
All you have to do is heat it up to that point, and the deformation will be automatically removed and the shape will be restored.
本発明の材料より得られる形状記憶性高分子物品は、−
旦変形させた該物品を所定の形状まで回復しうるので、
該物品の使用の際に、その形状のままでは装着や組立で
、搬送等が困難な場合に取り扱いが容易になる梯形状を
変え、装着や組立等が終了した後で加熱操作に上り所定
の形状に回復させ、本来の目的とする働きをさせるのに
、又変形した該物品を元の状態に回復させること自体に
主点を置いた用途に使用できる。具体的には前者では、
パイプや電線等の接合部の接合材やシール材、パイプや
棒状物体の内、外部ラミネート材、スプリント材、各種
固定材、衝撃吸収材等、後者では、玩具用部材、文具材
、教材、装飾品材等である。又、その他、医療用患部固
定材、スポーツ用プロテクター材、人形、造花、型取り
材及びかつら用頭部型取り材等にも使用することができ
る。The shape memory polymer article obtained from the material of the present invention is -
Since the article that has been deformed can be restored to a predetermined shape,
When using the product, if the shape is difficult to install or assemble, change the ladder shape to make it easier to handle, and after the installation or assembly is completed, heat it up and heat it to the specified temperature. It can be used to restore the shape and function as intended, and can be used for purposes that focus on restoring the deformed article to its original state. Specifically, in the former case,
Bonding materials and sealing materials for joints of pipes and electric wires, external laminate materials for pipes and rod-shaped objects, splint materials, various fixing materials, shock absorbing materials, etc. The latter include toy materials, stationery materials, teaching materials, and decorations. Materials, etc. In addition, it can also be used for medical fixation materials for affected areas, sports protector materials, dolls, artificial flowers, molding materials, head molding materials for wigs, etc.
更に他の機能材、圧電体、導電性高分子材料などと複合
化することにより、温度センサーとしてら使用すること
ができる。Furthermore, by combining it with other functional materials, piezoelectric materials, conductive polymer materials, etc., it can be used as a temperature sensor.
（実 施 例） 以下に実施例を挙げて説明する。(Example) Examples will be described below.
実施例１
スチレンモノマー（Ｓｔ）９ｇ及び５ＦＭＡ １ｇ１
：Ｎして、それぞれ０，５ｗｔ％のカン７アーキ／ン（
ＣＱ）及びノメチルアミノエチルメタクリレート（ＤＭ
ＡＥＭＡ）を溶解し、更にこれにポリメタクリル酸エチ
ル（ＰＥＭＡ）２０．を溶解し均一化した後、可視光を
照射して光重合した。得られた高分子物質のビッカース
硬度は７．０５）ＩＶ（２５℃）であった。Example 1 Styrene monomer (St) 9g and 5FMA 1g1
:N, respectively 0.5wt% Kan7 Arch/N (
CQ) and nomethylaminoethyl methacrylate (DM
Polyethyl methacrylate (PEMA) 20. After dissolving and homogenizing, visible light was irradiated to photopolymerize. The Vickers hardness of the obtained polymeric material was 7.05) IV (25°C).
得られた高分子材料を５０Ｘ５Ｘ１ｍ−の長方形サンプ
ルに成形し、これを９５℃のＷ；Ｉ浴中で延伸し、氷水
中で固定後、これを再び９５℃の湯浴中に一定時間浸漬
し、各時間における回復率を求めた。下記に結果を示す
。The obtained polymeric material was formed into a rectangular sample measuring 50 x 5 x 1 m, which was stretched in a W; , the recovery rate at each time was determined. The results are shown below.
Ｌ艷４捻吐 −一匪艷４法吐−
ｉｌ Ｌ４５Ｌ
６０ ９６ ９６ ９８
大施例２
Ｓｔ ９ｇ及び５ＦＭＡ １ｇの代りに、５ｔ１５
１１及びエチレングリフールジメタクリレー）（ＩＧ）
５ｇを使用した他は実施例１と同様にして重合を行った
。得られた高分子材料のビッカース硬度は９．４５ＨＶ
（２５℃）であった。L45L 60 96 96 98 Large example 2 St 9g and 5FMA 5t15 instead of 1g
11 and ethyleneglyfur dimethacrylate) (IG)
Polymerization was carried out in the same manner as in Example 1 except that 5 g was used. The Vickers hardness of the obtained polymer material is 9.45HV
(25°C).
得られた高分子材料を６Ｉｌｌ−φ×５曽曽の円柱状サ
ンプルに成形し、これを９５℃の湯浴中で圧縮し、氷水
中で固定後、これを再び９５℃の湯浴中に一定時間浸漬
し、各時間における回復率を求めた。下記に結果を示す
。The obtained polymeric material was molded into a cylindrical sample of 6 Ill-φ x 5 Soso, compressed in a 95°C water bath, fixed in ice water, and then placed in a 95°C water bath again. It was immersed for a certain period of time, and the recovery rate at each time was determined. The results are shown below.
８３ ４３ １００６７
５２ １００（以 上）83 43 10067
52 100 (or more)
Claims (1)
せしめ、次いでこれを重合に付し、又は更にＩＰＮ化し
て得られる高分子物質より形成されたことを特徴とする
形状記憶性高分子材料。(1) A shape-memory polymeric material, characterized in that it is formed from a polymeric substance obtained by bringing an acrylic polymer into contact with a styrene monomer and then subjecting it to polymerization or further converting it into IPN.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20514989A JPH0368611A (en) | 1989-08-08 | 1989-08-08 | Shape memory polymer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20514989A JPH0368611A (en) | 1989-08-08 | 1989-08-08 | Shape memory polymer material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0368611A true JPH0368611A (en) | 1991-03-25 |
Family
ID=16502234
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20514989A Pending JPH0368611A (en) | 1989-08-08 | 1989-08-08 | Shape memory polymer material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0368611A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999042528A2 (en) * | 1998-02-23 | 1999-08-26 | Mnemoscience Gmbh | Shape memory polymers |
| EP0789602A4 (en) * | 1994-10-03 | 1999-11-10 | Menlo Care Inc | Polymeric medical device systems having shape memory |
| WO2001091822A1 (en) * | 2000-05-31 | 2001-12-06 | Mnemoscience Gmbh | Shape memory thermoplastics and polymer networks for tissue engineering |
| US7217744B2 (en) | 2002-02-26 | 2007-05-15 | Mnemoscience Gmbh | Polymeric networks |
| JP2007191648A (en) * | 2006-01-20 | 2007-08-02 | Kyoto Institute Of Technology | Method for producing multi-phase polymer material and the multi-phase polymer material |
| EP2046408A1 (en) * | 2006-07-28 | 2009-04-15 | 3M Innovative Properties Company | Shape memory polymer articles with a microstructured surface |
| US7951319B2 (en) | 2006-07-28 | 2011-05-31 | 3M Innovative Properties Company | Methods for changing the shape of a surface of a shape memory polymer article |
-
1989
- 1989-08-08 JP JP20514989A patent/JPH0368611A/en active Pending
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0789602A4 (en) * | 1994-10-03 | 1999-11-10 | Menlo Care Inc | Polymeric medical device systems having shape memory |
| WO1999042528A2 (en) * | 1998-02-23 | 1999-08-26 | Mnemoscience Gmbh | Shape memory polymers |
| WO1999042528A3 (en) * | 1998-02-23 | 1999-11-04 | Mnemoscience Gmbh | Shape memory polymers |
| US6388043B1 (en) | 1998-02-23 | 2002-05-14 | Mnemoscience Gmbh | Shape memory polymers |
| US6720402B2 (en) | 1998-02-23 | 2004-04-13 | Mnemoscience Gmbh | Shape memory polymers |
| WO2001091822A1 (en) * | 2000-05-31 | 2001-12-06 | Mnemoscience Gmbh | Shape memory thermoplastics and polymer networks for tissue engineering |
| US7217744B2 (en) | 2002-02-26 | 2007-05-15 | Mnemoscience Gmbh | Polymeric networks |
| JP2007191648A (en) * | 2006-01-20 | 2007-08-02 | Kyoto Institute Of Technology | Method for producing multi-phase polymer material and the multi-phase polymer material |
| EP2046408A1 (en) * | 2006-07-28 | 2009-04-15 | 3M Innovative Properties Company | Shape memory polymer articles with a microstructured surface |
| EP2046408A4 (en) * | 2006-07-28 | 2009-08-19 | 3M Innovative Properties Co | Shape memory polymer articles with a microstructured surface |
| US7951319B2 (en) | 2006-07-28 | 2011-05-31 | 3M Innovative Properties Company | Methods for changing the shape of a surface of a shape memory polymer article |
| US10279069B2 (en) | 2006-07-28 | 2019-05-07 | 3M Innovative Properties Company | Shape memory polymer articles with a microstructured surface |
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