JP2022550652A - 電場法を用いた形態可変型マイクロパターン化高分子触覚素材の製造方法 - Google Patents
電場法を用いた形態可変型マイクロパターン化高分子触覚素材の製造方法 Download PDFInfo
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Abstract
Description
2. 大韓民国公開特許第10-2017-0032625号公報
2. D.Liu et al.,Angew.Chem.2014,1236,4630-4634
3. D.Liu et al.Proc.Nat.Acad.Sci.2015 112(13)、3880-3885
4. W.FENG et al.Adv.Func.Mater.2019,1901681
1.パターン化された電極基板の作製
電場ベースの液晶配向プラットホームのために、パターン化された電極基板を作った。リフト-オフ(Lift-off)工程法を用いてガラス基板にITOパターンを具現した。一番目のITOガラス基板は、10μm幅と10μm間隔の縞パターンを有し、二番目のITOガラス基板は、10μm幅と30μm間隔の縞パターンを有する。
ガラスITO電極パターン基板をアセトン(acetone,SAMCHUN chemical)、エタノール(ethyl alcohol,SAMCHUN chemical)、3次蒸留水(18.3MΩ/cm,Human Corp.)を順次に用いて洗浄した。液晶単量体分子の垂直配向誘導のためにイミド系高分子のうち、疏分子性高分子(molecular-phobic polyimide)溶液を基板上にスピンコートし、90℃及び200℃でそれぞれソフトベーキング(soft baking)及びハードベーキング(hard baking)で硬化させ、疏分子性高分子膜を得た。
一定の間隔をあけて電場を印加する電極セルを作製するために、2枚の基板を使用し、両基板の間に5μmビーズ(bead)を配置して合わせた。UV硬化用糊(glue)を用いてビーズと混合した後、光硬化によって両基板を接着させた。特に、パターン化された基板を90゜の角度で交差して接合し、周期的な格子電極構造を作製した。合計2種のパターン化された電極基板を用いて3種の電極セルを作製した。
実施例で用いられる混合物は、2個のアクリル基が付着した4-(3-アクリロイルオキシプロピルオキシ)ベンゾ酸2-フェニル-1,4-フェニレンエステル(4-(3-acryloyloxypropyloxy)-benzoic acid 2-methyl-1,4-phenylene ester,69wt%)、1個のアクリル基が付着した4-メトキシベンゾ酸4-(6-アクリロイルオキシ-ヘキシルオキシ)フェニルエステル(4-methoxybenzoic acid 4-(6-acryloyloxy-hexyloxy)phenyl ester,30wt%)、光開始剤である2,2-ジメトキシ-2-フェニル-アセトフェノン(2,2-dimethoxy-2-phenyl-acetophenone,1wt%)で構成された混合物を使用し、上の混合物は冷却過程で順に等方相、ネマチック相を有する。等方相からネマチック相への転移温度は、約87℃である。上の混合物を等方相状態でサンドウィッチセル内に注入し、毛細管力によって注入した。その後、ネマチック相となる75℃まで温度を下げて維持した。
交流電場を用いて順次にトップ-ダウン(top-down)方法で電場を印加した。パターン1はf=100kHz、V0=10V、パターン2はf=100kHz、V0=15V、パターン3はf=100kHz、V0=30Vにおいて最も規則的なマイクロ構造体が形成された。その後、電場と温度を維持した状態でUV照射によって光硬化を行った。50~100mWの強度で20分以上照射して完全に硬化させ、高分子薄膜を作製した。
温度調節装置(hearting stage,LINKAM)を用いて等方相温度から冷却させながら、ネマチック液晶相で電場を印加することによって現れる光学テクスチャーを、偏光顕微鏡(LV100-POL,Nikon)で観察した。また、高分子薄膜を作製した後、一方のガラス基板を除去した後、常温で薄膜の光学テクスチャーを観察し、それを図2及び図3に示した。
一方のガラス基板を除去した高分子薄膜コーティング基板を使用し、温度調節装置(hearting stage,LINKAM)を用いて常温から昇温及び冷却をしながら表面形状を変化させた。この時、現れる表面形状イメージと表面粗度グラフを表面分析機(surface profiler,msurf)で観察し、図4及び図5に示した。
図6の(a)は、温度による液晶ネットワーク高分子薄膜の摩擦係数を観察した実験設計図である。図6の(b)は、比較群として微細パターン無しで液晶単位体がいずれも垂直配列を維持したまま電極文様の表面構造だけを有している高分子薄膜と平らなガラス間の摩擦係数を温度によって観察したグラフである。このとき、ガラス転移温度以上の温度で高分子薄膜の粘弾性が急に減少して摩擦係数も大きい減少を示した後、それ以上の温度では類似の値を維持した。
Claims (17)
- 次の段階を含む形態可変型マイクロパターン化高分子薄膜の製造方法:
(a)パターン化された電極基板の上部に高分子配向膜を形成させる段階;
(b)前記高分子配向膜が形成されており、パターン化された電極基板2個を、一定の間隔をあけて交差するように結合させ、サンドウィッチ電極セルを作製する段階;
(c)前記サンドウィッチ電極セルの両基板の間に液晶有機高分子混合物を注入する段階;及び
(d)前記液晶有機高分子混合物が注入されているサンドウィッチ電極セルに電場を印加した状態で光硬化を行い、マイクロパターン化高分子薄膜を製造する段階。 - 前記(a)段階のパターン化された電極基板は、縞パターンを有する電極基板であることを特徴とする、請求項1に記載の形態可変型マイクロパターン化高分子薄膜の製造方法。
- 前記(b)段階の高分子配向膜が形成されており、パターン化された電極基板は、異なる間隔の縞パターンを有する電極基板であることを特徴とする、請求項1に記載の形態可変型マイクロパターン化高分子薄膜の製造方法。
- 前記縞パターンにおいて、各縞の幅は5~20μmであり、縞間の間隔は5~40μmであることを特徴とする、請求項2に記載の形態可変型マイクロパターン化高分子薄膜の製造方法。
- 前記サンドウィッチ電極セルの厚さは、2~20μmであることを特徴とする、請求項1に記載の形態可変型マイクロパターン化高分子薄膜の製造方法。
- 前記液晶有機高分子混合物は、一つ以上のアクリル基が付着した液晶有機高分子、及び光開始剤を含有することを特徴とする、請求項1に記載の形態可変型マイクロパターン化高分子薄膜の製造方法。
- 前記液晶有機高分子は、4-(3-アクリロイルオキシプロピルオキシ)ベンゾ酸2-メチル-1,4-フェニレンエステル(4-(3-acryloyloxypropyloxy)-benzoic acid 2-methyl-1,4-phenylene ester)、)、4-シアノフェニル-4’-(6-アクリロイルオキシヘキシルオキシ)ベンゾエート(4-cyanophenyl-4’-(6-acryloyloxyhexyloxy)benzoate)、及び1,4-ビス-[4-(6-アクリロイルオキシヘキシルオキシ)ベンゾイルオキシ]-2-メチルベンゼン(1,4-bis-[4-(6-acryloyloxyhexyloxy)benzoyloxy]-2-methylbenzene)からなる群から一つ以上が選択されることを特徴とする、請求項6に記載の形態可変型マイクロパターン化高分子薄膜の製造方法。
- 前記光開始剤は、2,2-ジメトキシ-2-フェニル-1-アセトフェノン(2,2-dimethoxy-2-phenyl- acetophenone)、ビス(2,4,6-トリメチルベンゾイル)-フェニルホスフィンオキシド(bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide)、ビス(η-5,2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)-フェニル)チタニウム(Bis(η-5-2,4-cylcopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium)、及び2-ベンジル-2-ジメチルアミノ-1-(4-モルフォリノフェニル)-ブタノン-1(2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1)からなる群から一つ以上が選択されることを特徴とする、請求項6に記載の形態可変型マイクロパターン化高分子薄膜の製造方法。
- 前記(d)段階は、10~200mWの強度で1分~2時間UV照射することを特徴とする、請求項1に記載の形態可変型マイクロパターン化高分子薄膜の製造方法。
- 前記(a)段階は、前記パターン化された電極基板の上部にイミド系の疏分子性高分子溶液をコートし硬化させて高分子配向膜を形成させることを特徴とする、請求項1に記載の形態可変型マイクロパターン化高分子薄膜の製造方法。
- 前記硬化は、60~120℃の温度でのソフトベーキング(soft baking)、及び150~200℃温度でのハードベーキング(hard baking)を行うことを特徴とする、請求項10に記載の形態可変型マイクロパターン化高分子薄膜の製造方法。
- 前記液晶有機高分子を等方相温度で前記電極セルの両基板の間に注入した後、冷却させてネマチック液晶相の温度で電場を印加することを特徴とする、請求項1に記載の形態可変型マイクロパターン化高分子薄膜の製造方法。
- 前記電場は、交流電場であることを特徴とする、請求項1に記載の形態可変型マイクロパターン化高分子薄膜の製造方法。
- 前記電場は、80kHz~2MHzの電場周期と2~200Vの電圧であることを特徴とする、請求項1に記載の形態可変型マイクロパターン化高分子薄膜の製造方法。
- 前記形態可変型マイクロパターン化高分子薄膜は、触覚素材又はセンサー素材として使用することを特徴とする、請求項1に記載の形態可変型マイクロパターン化高分子薄膜の製造方法。
- 請求項1~15のいずれか一項に記載の方法によって製造され、電極の交差する部分に-1位相欠陥が形成されており、電極の垂直及び水平の間に+1の位相欠陥が形成されており、対角線中心に-1位相欠陥が形成されており、外部温度が増加するにつれて位相欠陥周囲の表面陥没変形が5~800nmまで増加して表面の粗さ又は摩擦力の変化が誘導されることを特徴とする、形態可変型マイクロパターン化高分子薄膜。
- 請求項1~15のいずれか一項に記載の方法によって製造され、電極の交差する部分に-1位相欠陥が形成されており、電極の垂直及び水平の間に+1の位相欠陥が形成されており、対角線中心に-1位相欠陥が形成されており、外部温度が増加するにつれて位相欠陥周囲の表面陥没変形が5~800nmまで増加して表面の粗さ又は摩擦力の変化が誘導され、前記液晶有機高分子は、4-(3-アクリロイルオキシプロピルオキシ)ベンゾ酸2-メチル-1,4-フェニレンエステル(4-(3-acryloyloxypropyloxy)-benzoic acid 2-methyl-1,4-phenylene ester)及び4-メトキシベンゾ酸4-(6-アクリロイルオキシ-ヘキシルオキシ)フェニルエステル(4-methoxybenzoic acid 4-(6-acryloyloxy-hexyloxy)phenyl ester)であることを特徴とする、形態可変型マイクロパターン化高分子触覚素材。
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