JPH0368610A - Shape memory polymer material - Google Patents
Shape memory polymer materialInfo
- Publication number
- JPH0368610A JPH0368610A JP20514889A JP20514889A JPH0368610A JP H0368610 A JPH0368610 A JP H0368610A JP 20514889 A JP20514889 A JP 20514889A JP 20514889 A JP20514889 A JP 20514889A JP H0368610 A JPH0368610 A JP H0368610A
- Authority
- JP
- Japan
- Prior art keywords
- polymer
- shape
- polymer material
- materials
- shape memory
- 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 11
- 229920000431 shape-memory polymer Polymers 0.000 title abstract description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 27
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000178 monomer Substances 0.000 claims abstract description 15
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims description 22
- 239000000126 substance Substances 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 abstract description 12
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 abstract description 5
- 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
- 239000004793 Polystyrene Substances 0.000 abstract 1
- 229920002223 polystyrene Polymers 0.000 abstract 1
- 230000002787 reinforcement Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- -1 Softener Substances 0.000 description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 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 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
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-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
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 2
- 239000012778 molding material Substances 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- SUTQSIHGGHVXFK-UHFFFAOYSA-N 1,2,2-trifluoroethenylbenzene Chemical compound FC(F)=C(F)C1=CC=CC=C1 SUTQSIHGGHVXFK-UHFFFAOYSA-N 0.000 description 1
- 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 1
- CISIJYCKDJSTMX-UHFFFAOYSA-N 2,2-dichloroethenylbenzene Chemical compound ClC(Cl)=CC1=CC=CC=C1 CISIJYCKDJSTMX-UHFFFAOYSA-N 0.000 description 1
- JKNCOURZONDCGV-UHFFFAOYSA-N 2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound CN(C)CCOC(=O)C(C)=C JKNCOURZONDCGV-UHFFFAOYSA-N 0.000 description 1
- BHUGZIJOVAVBOQ-UHFFFAOYSA-N 2-(propylazaniumyl)acetate Chemical compound CCCNCC(O)=O BHUGZIJOVAVBOQ-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-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
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-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
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 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
- 230000002547 anomalous effect Effects 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- HOFRKADNFWPMNX-UHFFFAOYSA-N butan-1-ol;2-methylprop-2-enoic acid Chemical compound CCCCO.CC(=C)C(O)=O.CC(=C)C(O)=O HOFRKADNFWPMNX-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000006364 carbonyl oxy methylene group Chemical group [H]C([H])([*:2])OC([*:1])=O 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000013329 compounding Methods 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
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002648 laminated material Substances 0.000 description 1
- 239000007788 liquid 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
- 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
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 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
- 239000005060 rubber Substances 0.000 description 1
- 239000003566 sealing material Substances 0.000 description 1
- 239000011359 shock absorbing material Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
- Graft Or Block Polymers (AREA)
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、本来の目的とするＩｎ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 by heating operation etc. after installation or assembly, etc., to perform the original purpose of In, or to restore 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ては例えば、ノルボ
ルネン系ポリマー成形体（！Ｉｌ！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（ｖＦ開昭５９−
１１３１５号）等が知られている。Conventionally, regarding shape memory molded bodies, for example, norbornene polymer molded bodies (!Il! 1985-53528
), copolymer molded products of conjugated dienes or epoxy group-containing compounds, etc., and aromatic vinyl, unsaturated nitriles, acrylic esters, etc. (Japanese Patent Application Laid-Open No. 60-28433), or crosslinked molded products using polycaprolactone ( vF Kaisho 59-
No. 11315) etc. are known.
又、融点４０〜１００℃の結晶性ジエン系重合体を主成
分とする組成物からの架橋成形体（特開昭６２−１９２
４４０号）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マー（特
開昭６３−１７９９５５号）等も公知である。In addition, a crosslinked molded product made from a composition mainly composed of a crystalline diene polymer having a melting point of 40 to 100°C
440) and a blend polymer of a styrene-butadiene block copolymer and transpolyimbrene (Japanese Unexamined Patent Publication No. 179955/1983) are also known.
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.
（発明が解決し上うとする課題）
本発明の目的は加工性、透明性、耐熱性、耐候性、耐薬
品性、耐油性、耐溶剤性、耐水性、攬水祝油性、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。(Problems 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 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）
本発明はスチレン系ポリマーをアクリル系モノマーに接
触せしめ、次いでこれを重合に付し、又は更にｒＰＮ化
して得られる高分子物質より形成されたことをａ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 polymeric substance obtained by bringing a styrene polymer into contact with an acrylic monomer, then subjecting it to polymerization, or further converting it into rPN. The invention relates to 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
した後特定の温度下にで変形を与えても、再度特定の温
度に加熱することにより変形は自ｅｈ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！−求される分野での種々の
利用が可能である。Even if the material of the present invention is deformed at a specific temperature after being molded into the shape required for actual use, the deformation is self-removed by heating it again to the specific temperature and the original shape is removed. This function is possible because it can be restored to a similar shape! - It can be used in various fields.
本発明においてスチレン系ポリマーとしては通常公知の
ものを全て用いることができるが、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、ジクロロ
スチレン、トリフルオロスチレン等の単独重合体及びこ
れらとメチルメタクリレート、アクリロニトリル、ブタ
ジェン等との共重合体などが挙げられる。In the present invention, all commonly known styrenic polymers can be used, but specific examples include homopolymers of styrene, a-methylstyrene, methylstyrene, dichlorostyrene, trifluorostyrene, and methyl methacrylate. , acrylonitrile, a copolymer with butadiene, and the like.
又、本発明においてアクリル系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（ＥＭＡ）、ノタクリル酸ブチル（ＢＭ
ＡＬ ２−ヒトミキシエチルメタクリレート（ＨＥＭ
Ａ）、３−（トリメトキシシリル）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（＋）ｈｅｎｙｌ −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−ヒトａキシ
−３−７タクリロキシ）プロピルグリシン（ＮＰＧ−Ｇ
ＭＡ）、エチレングリコールジメタクリレート（ＥＤＭ
Ａ。Further, in the present invention, the acrylic monomer is not limited in type, but mono- or polyfunctional ones are included, and preferably, for example, methyl methacrylate (MMA), ethyl methacrylate (EMA), butyl notacrylate (BM
AL 2-human mixethyl methacrylate (HEM
A), 3-(trimethoxysilyl)propyl methacrylate (MSPM), 2-(phenylphosphoryl)ethyl methacrylate (+)henyl-P), 2-hydroxy-3-(β-7toxy)propyl methacrylate (HNPM) , N-phenyl-N-(2-human axy-3-7tacryloxy)propylglycine (NPG-G
MA), ethylene glycol dimethacrylate (EDM
A.
又はＩＧ）、ジエチレングリコールジメタクリレート（
ＤｉＥＤＭＡ）、トリエチレングリコールジメタクリレ
ート（ＴｒｉＥＤＭＡ）、】、４−ブタンジオールノメ
タクリレー ）（１，４−ＢｕＤＭＡ）、１．３−ブタ
ンジオールジメタクリレー）（１，３ＢｕＤＭＡ）、２
，２−ビス（４−（２−ヒドロキシ−３−７タクリロキ
シプロボキシ）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（ＢＰＤＭＡ）、２．２−ビス（４−７タクリロキシ
エトキシフエニル〉フロパン（Ｂｉｓ−ＭＥＰＰ）、２
，２−ビス（４−７タクリロキシボリエトキシフエニル
）プロパン（Ｂｉｓ−ＭＰＥＰＰ）、ジ（メタクリロキ
シエチル）トリフチルヘキサメチレンノウレタン（Ｕｒ
）ＭＡ）、）リメチロールプロパントリノタクリレート
（Ｔ Ｍ Ｐ Ｔ ）、ＣＩ＋、＝Ｃ（ＣＬ）ＣＯＯＣ
Ｉ（２ＣＦ３ （３ＦＭＡ）、ＣＨ２＝Ｃ（ＣＨ，）
ＣＯＯＣ１１２ＣＦ、ＣＦ、 （５ＦＭＡ）、ＣＩＩ
ｚ＝Ｃ（ＣＩｌ＊）ＣＯＯＣＨ２（ＣＦｚ）ｚｃＦｓ
（７ＦＭＡ）、ＣＨ２＝Ｃ（ＣＨ３）Ｃ００ＣＲ，（
ＣＦ２）、ＣＦ２Ｏ（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。or IG), diethylene glycol dimethacrylate (
DiEDMA), triethylene glycol dimethacrylate (TriEDMA), ], 4-butanediolmethacrylate) (1,4-BuDMA), 1,3-butanediol dimethacrylate) (1,3BuDMA), 2
,2-bis(4-(2-hydroxy-3-7tacryloxyproboxy)phenyl)propane (Bis GMA)
, 2,2-bis(4-methacryloxyphenyl)propane (BPDMA), 2,2-bis(4-7tacryloxyethoxyphenyl)furopane (Bis-MEPP), 2
, 2-bis(4-7tacryloxyboriethoxyphenyl)propane (Bis-MPEPP), di(methacryloxyethyl)triphthylhexamethyleneurethane (Ur
) MA), ) Limethylolpropane trinotacrylate (T M P T ), CI+, =C(CL)COOC
I(2CF3 (3FMA), CH2=C(CH,)
COOC112CF, CF, (5FMA), CII
z=C(CIl*)COOCH2(CFz)zcFs
(7FMA), CH2=C(CH3)C00CR, (
CF2), CF2O (8FMA), their corresponding 7 acrylates, and a-fluoroacrylates.
本発明においては上記スチレン系ポリマーをアクリル系
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、その際スチレン系ポリマー
にアクリル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ｌｌ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、重合方法としては、アクリ
ル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 styrene polymer into contact with an acrylic monomer and then subjecting it to polymerization. At this time, when the styrene polymer is brought into contact with an acrylic monomer, the former usually The latter is dissolved or wetted in the former, or the latter is impregnated in the former. As the polymerization method, any known polymerization method for acrylic monomers can be employed, but photopolymerization and thermal polymerization are 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４０〜１００℃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 heating polymerization, for example, by heating at a temperature of about 40 to 100 degrees Celsius, or by photopolymerization, for example, by irradiating 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ては上記の高分子物
質をＩ Ｐ Ｎ （Ｉ ｎｔｅｒ−ｐｅｎｅＬｒａｔｉ
ｎｇＰ ｏｌｙ＊ｅｒ Ｎ ｅＬｗｏｒｋ）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ｆｉ（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イルム化しておき、これ
にゲスト高分子を形成するモノマーを気相状態で注入す
るか、前記モノマーを含む溶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より重
合又は架橋させるものである。第二の方法は、通常のＴ
ＰＮ形戒と同じく、高分子物質を適当な溶媒に溶解させ
ておき、これにデ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、必要に応じて加熱処理等を
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 used as an IPN (Inter-peneLrati)
ngPoly*erNeLwork) is also included. ■PNization is a polymer that is originally formed by mixing two types of chain polymers in liquid fi (a solution is also possible), crosslinking either or both of them, and intertwining their molecular chains with each other. When this method is utilized in the present invention, several anomalous methods are used. For example, in the first method, a polymer substance is made into a film in advance, and a monomer that forms a guest polymer is injected into the film in a gas phase, or the film is immersed in a solution containing the monomer, and then the monomer is injected into the film. After that, it is polymerized or crosslinked by heating or light irradiation. The second method is the normal T
Similar to the PN type precept, this method involves dissolving a polymeric substance in a suitable solvent, reacting the mixture with a dest component, casting the solution into a film, and subjecting it to heat treatment, etc., if necessary. Other methods can also be used.
ＩＰＮ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
上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で
後架備する方法等が挙げられる。尚、本発明のアクリル
系モノマーを重合させて得られるポリマーとスチレン系
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 IPN formation, it is necessary to perform crosslinking, and the method for this is, for example, using a styrene polymer that has been crosslinked in advance by a conventional method, using a difunctional or higher functional acrylic monomer, A method of obtaining a crosslinked polymer by polymerization, or post-crosslinking the obtained uncrosslinked polymer using a radical source such as an organic peroxide, radiation, an ionic compound, an ion source, etc. in a method suitable for the polymer, etc. can be mentioned. In addition, a polymer blend of a polymer obtained by polymerizing the acrylic monomer of the present invention and a styrene 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、耐薬品性、耐油性、耐溶剤性、耐水性、
祝水祝油性、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 substance used in the present invention has processability, transparency, heat resistance, weather resistance, chemical resistance, oil resistance, solvent resistance, water resistance,
It has excellent oil 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より塗料化
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！ＨＩ＃等のゴム、プラスチック配合剤を
配合してもよい。The polymeric material of the present invention can be produced by molding the polymeric substance obtained above into a desired shape by extrusion molding, injection molding, compression molding, etc., or by dissolving or dispersing it in an appropriate solvent and making it into a paint. After making it into a form, it is used for the purpose described below. At that time, fillers, reinforcing agents,
Softener, plasticizer, compatibilizer, crystal nucleating agent, anti-aging agent, antioxidant, anti-ozonant, ultraviolet absorber, pigment, dye, tackifier! Rubber and plastic compounding agents such as HI# may also be blended.
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＄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、変形
温度が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 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; deformation temperature When 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がラス
転移点以上の温度下″Ｃｈ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 Las transition point.
通常高分子物質のがラス転移点以上（５０〜１００℃）
に加熱すればよく、それによって変形は自動的に除去さ
れ、形状が回復する。Normally, polymeric substances have a lath transition point or higher (50 to 100℃)
The deformation is automatically removed and the shape is 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て
、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より所定
の形状に回復させ、本末のａ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 it is difficult to attach, assemble, or transport the product in its original shape, change the ladder shape to make it easier to handle, and then heat it to the desired shape after the product has been installed or assembled. It can be used for purposes such as restoring a 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＃！能材、圧電体、導電性？に分子材料などと
複合化することにより、温度センサーとしても使用する
ことができる。Yet another #! Powerful materials, piezoelectric materials, conductivity? By combining it with molecular materials, it can also 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
スチレンポリマー ５重量部をｎ−ブチルメタクリレ−
）（ｎ−ＢｕＭＡ）５重量部に溶解し、下記の方法で光
重合を行い、重合硬化物を得た。Ｎち、モノマーに対し
てそれぞれ０，５ｗｔ％のカン７アーキノン（ＣＱ）、
クメチルアミノエチルメタクリレー）（ＤＭＡＥＭＡ）
を添加、室温下で可視光を１゜分照射して重合を行った
。得られた高分子材料のビッカース硬度は５．６７ＨＶ
（２５℃）であった。Example 1 5 parts by weight of styrene polymer was added to n-butyl methacrylate.
) (n-BuMA) was dissolved in 5 parts by weight, and photopolymerization was performed in the following manner to obtain a polymerized and cured product. N, 0.5 wt% of can-7-archynone (CQ) based on the monomer, respectively;
(DMAEMA)
was added, and polymerization was carried out by irradiating visible light for 1° at room temperature. The Vickers hardness of the obtained polymer material was 5.67HV
(25°C).
得られた高分子材料を５０Ｘ Ｓ Ｘ １ ｍ−の長方
形サンプルに成形し、これを９５℃の湯浴中で延伸し、
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 of 50×S×1 m−, which was stretched in a water bath at 95°C.
After fixing in ice water, this was again immersed in a 95°C water bath for a certain period of time, and the recovery rate at each time was determined. The results are shown below.
４褒」側Ｓユ −一量Ｅ」側左上−
り丞 ＬＬ Ｌ４
２５ ９０ ９０ ９０
８０ ９４ ９４ ９４実施例
２
ｎ ＢｕＭＡ ５重量部の代りに、メチルノタクリ
レート（ＭＭＡ）４重ｉｔｓ及び１，４−ブタンノオー
ルジメタクリレート（１，４−ＢｕＤＭＡ）１重量部を
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１２．９ＨＶ（２５
℃）であった。Example 2 n Instead of 5 parts by weight of BuMA, 4 parts of methylnotacrylate (MMA) and 1, Polymerization was carried out in the same manner as in Example 1, except that 1 part by weight of 4-butanol dimethacrylate (1,4-BuDMA) was used. The Vickers hardness of the obtained polymer material was 12.9HV (25
℃).
得られた高分子材料を実施例１と同様の条件で形状記憶
試験を行った。結果を下記に示す。The obtained polymer material was subjected to a shape memory test under the same conditions as in Example 1. The results are shown below.
Ｌ漣」へ５１ ■ ０ （以 上） ダイキン工業株式会社51 to L Ren ■ 0 (that's all) Daikin Industries, Ltd.
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 by being formed from a polymeric substance obtained by bringing a styrene-based polymer into contact with an acrylic monomer and then subjecting it to polymerization or further converting it into IPN.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20514889A JPH0368610A (en) | 1989-08-08 | 1989-08-08 | Shape memory polymer material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP20514889A JPH0368610A (en) | 1989-08-08 | 1989-08-08 | Shape memory polymer material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0368610A true JPH0368610A (en) | 1991-03-25 |
Family
ID=16502217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP20514889A Pending JPH0368610A (en) | 1989-08-08 | 1989-08-08 | Shape memory polymer material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0368610A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1818161A1 (en) * | 2006-02-10 | 2007-08-15 | Mnemoscience GmbH | Shape memory polymers and shape memory polymer compositions responsive towards two different stimuli |
| 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 JP20514889A patent/JPH0368610A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1818161A1 (en) * | 2006-02-10 | 2007-08-15 | Mnemoscience GmbH | Shape memory polymers and shape memory polymer compositions responsive towards two different stimuli |
| WO2007090685A1 (en) * | 2006-02-10 | 2007-08-16 | Mnemoscience Gmbh | Shape memory polymers and shape memory polymer compositions responsive towards two different stimuli |
| 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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