201132728 六、發明說明： 【發明所屬之技術領域】 著方法，更詳言之，在2個元 聚合物鏈之元件的方法，以及 本發明係關於元件之接 件的各自表面上接著經接枝 利用該方法所獲得的聚合物複合體。姓必丨及丄々 m 口體。特別係本發明係關於 將表面形成含多價陽離子之接枝 伐杈鰱的兀件、及表面形成含 多價陰離子之接枝鏈的元件，予以接著之方法。 【先前技術】 在電子或住宅建材的領域中，相關「接著」的要求性 能與利㈣境6呈高度化。例如就MEMSUICR0 ELECTR0 MECH臟AL SYSTEM，微機電系統） 的高機能化、多機能化、積體化，便要求各元件的=置 薄層化。因而，經高度控制的超薄膜接著技術開發便屬當 務之急。 β 已知有薄型接著層係將依蘭米爾-布洛吉特法 (Ungmuir-Blodegett ’簡稱LB)所製作的丙烯醯胺製高分 子奈米片（nanosheet)當作接著層，並利用無電解鍍便可製 作銅佈線（非專利文獻！）。但是，相關奈米水準厚度的接 者層幾乎尚未獲知。又’ 一般相關高分子界面的接著、剥 離、濕潤、吸附/脫附的機制、動態界面能量等非平衡現象， 就配合用途與規格的材料開發係屬非常重要，然而尚有頗 多不明確處，迫切渴求能解開迷惑。 1 9 91年有開發出使用高分子電解質的水溶液，製作薄 201132728 膜的「交又吸附法」（專利文獻n(非專利文獻2)(非專利 文獻^)。在該報告以後，不僅褐限於高分子電解質，就連 口中性尚分子、奈米粒子、膠質、蛋白質黏土化合物等亦 可展開相關交又吸附法」的特徵在於能依奈米水準進 订膜厚控制，且所構成物質的自由度、可利用結合的自由 度等。又，有使用為細胞或蛋白質對生化材料表面的吸附 性控制之表面設計技術（非專利文獻4)。 若將屬於高分子電解質的多價陽離子與多價陰離子相 混合’便利用強靜電相互作用使二者相吸附而形成聚離子 混合物。所以，若使經塗佈多價陽離子的基材表面、與經 塗佈多價陰離子的基材表面進行接觸，二者便可輕易地接 著（非專利文獻5)(非專利文獻6)(非專利文獻7)(非專利 文獻8)。但是，依照基材的種類，會有因水或濕氣的影響 而導致塗佈膜從基材表面上剝離，因而無法獲得充 著性能。 例如在受損傷的皮膚等處交錯積層著多價陽離子與多 價陰離子，而形成接著性優異之薄膜的技術，已知有如齐 米端帶(adhesive bandage)。但是，成為對象的：材僅; 定於與生化膜、蛋白等高分子電解質間之親和性較、 料而已’頗難廣範圍展開於工學材料領域。 即，即便使用高分子電解質的情況，因為基材與 層並未牢固地結合，因而會有容易剝離的問 » 彳卩1】如M e π h 4便有嘗試利用使用表面電漿聚合的方法，進行聚八， 膜間之接著，但因為係依照、使用光或熱的自由=聚== 4 201132728 行元件製造，因而接枝鏈的分子量與分子量分佈、或膜厚 的控制便不足，導致會含有低分子量聚合物成分、在剝離 時於聚合物界面處出現遭破壞等情況（專利文獻2非專利 文獻9)(非專利文獻1 〇)(非專利文獻丨丨）（非專利文獻 12 )(非專利文獻13)(非專利文獻丨4)(非專利文獻丨5)(非 專利文獻16)。 先行技術文獻 非專利文獻 非專利文獻 1 : Miyashita et al.，POLYMER PREP. JAPAN 54(1) 2005 非專利文獻 2: Decheretal.，Science, 277, 1232 (1997) 非專利文獻 3: Decher et al. , multilayer thin films sequenc i a 1 assembly of nanocomposite materials, wiley-vch, weinheim, (2003) 非專利文獻 4: A. SCHNEIDER etal. Langmuir, (2005) 非專利文獻 5 : Huck et al. , Langmuir 2008，24 11253-11260 非專利文獻 6 : Huck et al. Langmuir 2007，23, 3314-3321 非專利文獻 7 : Klok et al.，Macromolecules 2007, 40， 168-177 非專利文獻 8 : Fukuda et al_，Polymer Preprints,201132728 VI. Description of the invention: [Technical field to which the invention pertains] The method, more particularly, the method of the element of the two-dimensional polymer chain, and the respective surfaces of the connector of the invention relating to the element are subsequently grafted The polymer composite obtained by this method. The surname must be 丨 and 丄々 m mouth. In particular, the present invention relates to a method of forming a crucible containing a polyvalent cation grafted on a surface, and forming a graft chain containing a polyvalent anion on the surface, followed by a method. [Prior Art] In the field of electronic or residential building materials, the demand performance of the "continuation" is highly advanced. For example, in the case of MEMSUICR0 ELECTR0 MECH dirty AL SYSTEM, MEMS, high-performance, multi-functionalization, and integration, it is required to thin the layers of each component. Therefore, the development of highly controlled ultra-thin films followed by technology is a priority. β is known as a thin-type adhesive layer. A acrylamide-made nanosheet made of Ungmuir-Blodegett (LB) is used as an adhesive layer and uses electroless Copper wiring can be made by plating (non-patent literature!). However, the connector layer of the relevant nano level thickness is hardly known. In addition, the non-equilibrium phenomena such as the adhesion, peeling, wetting, adsorption/desorption, and dynamic interface energy of the general polymer interface are very important for the material development of the application and specifications. However, there are still many unclear points. I am eager to solve my confusion. In the year of 1991, the company developed the "adsorption and adsorption method" for the thin film of 201132728 (patent document n (Non-Patent Document 2) (Non-Patent Document 2). After the report, not only the brown is limited. Polymer electrolytes, which can be linked to neutral, molecular, nanoparticle, colloidal, protein clay compounds, etc., can also be developed by the method of binding the thickness of the film, and the freedom of the constituent materials. Degree, degree of freedom of use, etc. Further, there is a surface design technique using adsorption control of the surface of a biochemical material by a cell or a protein (Non-Patent Document 4). If a multivalent cation belonging to a polymer electrolyte is multivalent The anionic phase is mixed to facilitate the adsorption of the two phases by a strong electrostatic interaction to form a polyionic mixture. Therefore, if the surface of the substrate coated with the polyvalent cation is brought into contact with the surface of the substrate coated with the polyvalent anion, Both of them can be easily followed (Non-Patent Document 5) (Non-Patent Document 6) (Non-Patent Document 7) (Non-Patent Document 8). However, depending on the type of the substrate, there may be a cause. The coating film is peeled off from the surface of the substrate by the influence of water or moisture, and thus the charging performance cannot be obtained. For example, polyvalent cations and polyvalent anions are interleaved at the damaged skin or the like to form an excellent adhesion. The technique of the film is known as an adhesive bandage. However, it is only a target; the affinity for a polymer electrolyte such as a biofilm or a protein is relatively high, and it is difficult to expand. In the field of engineering materials, that is, even in the case of using a polymer electrolyte, since the substrate and the layer are not firmly bonded, there is a problem that the film is easily peeled off, such as M e π h 4 The method of surface plasma polymerization is carried out by argon, and the film is followed by a film, but the molecular weight and molecular weight distribution of the graft chain or the film thickness are determined by the use of light or heat free = poly == 201132728. The control is insufficient, and the low-molecular-weight polymer component may be contained, and the polymer interface may be damaged at the time of peeling (Patent Document 2 Non-Patent Document 9) (Non-Patent Document 1) Patent Document 丨丨) (Non-Patent Document 12) (Non-Patent Document 13) (Non-Patent Document 丨 4) (Non-Patent Document 丨 5) (Non-Patent Document 16). Prior Art Document Non-Patent Document Non-Patent Document 1: Miyashita Et al., POLYMER PREP. JAPAN 54(1) 2005 Non-Patent Document 2: Decher et al., Science, 277, 1232 (1997) Non-Patent Document 3: Decher et al., multilayer thin films sequenc ia 1 assembly of nanocomposite materials, Wiley-vch, Weinheim, (2003) Non-Patent Document 4: A. SCHNEIDER etal. Langmuir, (2005) Non-Patent Document 5: Huck et al., Langmuir 2008, 24 11253-11260 Non-Patent Document 6: Huck et al. Langmuir 2007, 23, 3314-3321 Non-Patent Document 7: Klok et al., Macromolecules 2007, 40, 168-177 Non-Patent Document 8: Fukuda et al_, Polymer Preprints,
Japan, 58(2), 3607-3608 (2009) 5 201132728 非專利文獻 9: K. G. Neoh etal.，Macromolecules， 30, 3354-3362 (1997) 非專利文獻 10 : K. G. Neoh et al.，Journal of Polymer Science ： Part A : Polymer Chemistry， 36, 357-366 (1998) 非專利文獻 11 : K. G. Neoh et al.，Langmuir, 14 921-927 (1998) 非專利文獻 12: K. G. Neoh et al.，Polymer, 39, 2429-2436 (1997) 非專利文獻 13 : K. G. Neoh et al· , Journal of Polymer Science ： Part A · Polymer Chemistry, 36, 31 07-3114 (1998) 非專利文獻 14 : K. G. Neoh et al.，Journal of Applied Polymer Science, 70, 19 77-1983 (1998) 非專利文獻 15: K. G. Neoh etal.，European Polymer Journal, 35, 1279-1288 (1999) 非專利文獻 1 6 : K. G. Neoh et al.，International Journal of Adhesion & Adhesives, 19, 359-365 (1999) 專利文獻1 :美國專利52081 1 1號 專利文獻2 :美國專利公報5, 755, 91 3、台灣國立科學 技術研究所、May 26，1998 【發明内容】 本發明者發現藉由使用在接著表面形成含有電解質構 6 201132728 、八互異極丨生之向分子接枝鏈層的2個元件，便可解決 上述問題。本發明所定義的「高分子接枝層」係指高分子 鏈末端或面分子鏈其中—部分利用共價鍵而與基材表面呈 固定化形成的奈米等級薄膜。因❿，高分子接枝層不會有 因利用洛劑進行洗淨、#因輕度摩擦而造成從基材表面上 卿㈣形。因而，本案發明目的在於提供：+會有在一 般接著法中’構成問題的在被接著體表面上發生接著層凝 聚破壞與殘膠等情形’在被黏體剝離時不會使被黏體遭損 傷可重複進订接著與剥離的極薄接著層、及含有接著層 的複合體。 s (發明所欲解決之課題） 即，發現組合經在基材上導入含有具正電荷多價陽離 子或兩性離子高分子接枝鏈的元件、與經在基材上導入含 有具負電荷多價陰離子或兩性離子高分子接枝鏈的元件， 而形成的新穎接著元件，具有強力的接著性能。例如含有 具正電荷多價陽離子的高分子接枝鏈係係有如含銨基物 (非專利文獻5)。具有含負電荷多價陰離子的高分子接枝 鏈係有如含磺酸基物（非專利文獻6)、具羧基物（非專利文 獻7)(非專利文獻8)等，就含兩性離子的高分子接枝鏈係 有如羰甜菜驗、磷酸甜菜驗、磺甜菜驗等。 項 根據此項發現而完成的本發明主 旨係包括有下述事 子或 (1) 一種元件之接著方法，係將表面已形成含多價陽離 兩性離子接枝鏈的第一元件、與表面已形成含夕 夕1貝陰 7 201132728 離子或兩性離子接枝鏈的第二元件，使該接枝鏈彼此間呈 相對面地進行接著。 (2) 如（1)所記載的方法，其中，使在上述第一元件與 上述第二元件之間介存著水才施行接著。 (3) 如（1)或（2)所記載的方法，其中，上述含多價陽離 子的接枝鏈係選自具吼啶鏽基或銨基的接枝鏈；上述含多 價陰離子的接枝鏈係選自具羧基、磺酸基、硫酸基、或磷 酸基的接賴；上料兩性料的高分子接枝鏈係選自具 羰甜菜撿、磷酸甜菜驗、磺甜菜撿等的接枝鏈。 (4) 如（1 M3)項中任一項所記載的方法，其中，上述 第-元件與上述第：元件係切、高分子、纖維素、金屬 或無機材料形成。 (5)如（1)〜（4)項中任一項所記載的方法，其中，上对 含多價陽離子或兩性離子的接枝鏈'及上述含多價陰離号 或兩性離子的接枝鏈，係分別經由共價鍵固定於上述第一 元件及上述第二元件上。 ⑻-種接著方法，係將元件進行暫時性接著的方法 將表面形成含多價陽離子或兩性離子接枝鏈的第—元件、 與表面形成含多價陰離子或兩性離子接枝鍵的第二元件， 使該接枝鏈彼此間呈相對面且介存著水進行接著，然後， 利用加熱或鹽溶液而予以剝離。 (7 ) ' 一種接者方法，係將矣ΛΡι JH/ J·、a a 係將表面形成含多價陽離子或兩姓 離子接枝鍵的第一 7L ^ Λ' ^ 肖表面形成含多價陰離子或兩姓 離子接枝鍵的第二元件，使兮技姑放〜 使該接枝鏈彼此間呈相對面且 8 201132728 加熱、或鹽溶液而予 對面並介存著水進行 存著水進行接著，然後，利用脫水、 以剝離後，再使該接枝鏈彼此間呈相 接著。 (8)—種聚合物複合體， 兩性離子接枝鏈的第一元件 兩性離子接枝鏈的第二元件 進行接著。 發明效果 係將表面形成含多價陽離子或 、與表面形成含多價陰離子或 ’使該接枝鏈彼此間呈相對面 根據本發明，提供將表面形成含多價陽離子之接枝鍵 的第-7L件、與表面形成含多價陰離子之接枝鏈的第二元 件進行接著的技術。即，本案發明係因為僅具相互不同極 性的物質才有接著性，目而可僅將料元件、部位進行選 擇性接著。 再者，根據本發明’因為在未使用接著劑與有機溶劑 、’月况下’將極少的水滴夾入接著界面，在將上述第一元 ::與上！第二元件進行接著，因而可提供不會污染周圍環 兄對環境的負荷極小之技術。 【貫施方式】 以下’針對本發明包括其最佳形態在内進行更具體的 ㈣本發明的接著方法係將表面形成含多價陽離子之接 二元M —元件、與表面形成含多價陰離子之接枝鏈的第 件，使該接枝鏈彼此間呈相對面進行接著。 201132728 本案發明所使用上述含聚陽離子的接枝鏈、及上述含 多價陰離子的接枝鏈，係主鏈或側鏈含有具互異極性官能 基的高分子。又，接枝鏈並不僅局限於由單一單體構成者， 亦可由2種以上的單體構成。 上述多價陰離子可使用一般具有諸如磺酸、硫酸、羧 酸、磷酸等可帶負電荷之官能基者，例如：聚磺酸苯乙烯、 聚乙烯硫酸、葡聚糖硫酸、軟骨膠硫酸、聚（3一甲基丙烯醯 基丙基鱗酸）、聚（甲基丙烯酸募聚乙二醇鱗酸）、玻尿酸、 聚丙烯酸、聚曱基丙烯酸、聚順丁烯二酸、聚反丁烯二酸、 聚（2-丙烯醯胺-2-曱基-1-丙烷磺酸）等’較佳係聚（募聚甲 基丙烯酸-3-磺丙醋）（PSPM)、聚甲基丙烯酸鈉鹽（pMANa) 等。 上述多價陽離子係可使用一般具有諸如吡啶鏽基、銨 基、四級銨基、胺基等可帶正荷電之官能基者，例如：聚 伸乙亞胺、聚烯丙胺鹽酸鹽、 聚二烯丙基氣化二甲銨、聚 乙稀口比咬、聚（N-甲基-2-乙稀。比咬）' 聚（N_甲基_4_乙稀吼 啶）、聚離胺酸、聚苯乙烯亞甲基二乙基甲胺、聚（甲基丙 烯酸二甲胺基乙酯）' 聚(2-曱基丙烯醯氧乙基碘化二甲銨) 等，較佳係聚（2-甲基丙烯醯氧乙基碘化二甲銨）（pMTAC) 等。 上述多價陰離子與上述多價陽離子的組合，較佳係有 如屬於多價陰離子的PSPM、與屬於多價陽離子的pMTAC之 組合等。 一端係利用共價 上述多價陽離子及上述多價陰離子的 10 201132728 鍵而分別與上述第一元件及上述第二元件呈固定化（接 枝）。 具體而言，將元件表面利用諸如··诎£(2_溴_2_曱基丙 炔醯氧基己基三乙氧基矽烷）、[或2-溴-2-甲基丙炔醯氧 基己基三甲氧基矽烷（BHM)、或2-溴-2-曱基-丙炔醯氧基 十一烷基膦酸（BUP)或卜（2’，2，，6，，6，-四曱基哌啶—！、氡 基）2苯基-乙膦酸等]等表面起始劑施行處理，而在元件 表面上將成為聚合開始起點的位點（site)利用共價鍵固定 化，藉由以該位點為起點的表面開始聚合法使多價陽離子 或多價陰離子進行成長，便可獲得在表面上牢固地接合著 含多價陽離子之接枝鏈或含多價陰離子之接枝鏈的元件。 所以’本案發明中’上述含多價陰離子的接枝鏈末端、及 上述含多價陽離子的接枝鏈末端係經由表面起始劑，並利 用共價鍵而與元件表面相結合，目而上述第一元件及上述 第二元件便可不致剝離地牢固固I若使依此獲得具有多 價陽離子接枝層的第_元件、與具多價陰離子接枝層的第 -兀件相貼合’在二接枝層間便會有強靜電相互作用，並 :此為主要原@，使元件彼此間相接著。所以，本質的接 者層係向分子電解f接枝層。且本發明卜因為該接枝 層與元件係利用共價鍵^化，目而發揮非常高的接著能 力。習知技術較錯積層法情況，接著層係由多價陽離子 與多價陰離子呈交錯積層的高分子電解質積層m，但因為 該積層膜與屬於被接著體的元件表面並非進行化學鍵社， 因而會有接著層容易從元件上㈣，'經剝離的接著：便 11 201132728 無法再利用等問題。 利用表面開始聚合法所形成之上述含多價陽離子的接 枝鏈、及上述含多價陰離子的接 範圍。 表面已形成上述含多價陽離子接枝鏈的上述第一元 件、與表面已形成上述含多價陰離子接枝鍵的上述第二元 件，係在二者間經由極少量的水進行接著而牢固地結合。 本案發明中，表面已形成上述含多價陽離子接技鏈的 上述第-几件、與表面已形成上述含多價陰離子接枝鍵的 上述第一疋件，在介存水進行接著後，藉由利用加敎、或 鹽溶液施行處理便可剝離。本案發明係利用加 溶液施行處理而進行剝離，蕤在丨私 现& 适仃利離，藉此在剝離時便可在不會引發 聚合物鏈遭破壞的情況下進行剝離。 本案發明中，經剝離的μ .贫 _ , 剌離的上述第一兀件與上述第二元件 係爾後使介存著水便可進行再接著。 再者，本案發明的上述第一元件及上述第二元件之材 質’係在利用上述表面處理劑便可導入聚合開始位點的前 提下，其餘並無特別的限制，較佳係例如：金屬基板、石夕 基板、石英基板、氟系聚合物、聚乙稀、聚丙烯、纖維素 專。該等的形狀亦無特別的限制，對諸如平面、球面、柱 狀表面、中空管内壁等任一表面均可適用。又’該等的表 面亦可為凹凸。 實施例 以下，針對本發明更進一步根據詳細的實施例進行說 12 201132728 明，惟本案發明並不僅侷限於此。 (實施例1-1) 在</) 1 6mm玻璃管中，依序添加BHE固定化石夕基板 (10x40mm2)、CuBr( 0. 025mmol)、CuBr2( 0. 00 5nimol)、4, 4’ _ 二曱基-2, 2’ -聯吡啶（0· 050mmol)、經調製為1. 82M的 SPMK(甲基丙烯酸-3-磺丙基鉀鹽）甲醇水溶液 6. OmL(MeOH/H2〇 = 5/2 ’ v/v)，施行冷凍脫氣，在 25°C 下進 行1 5小時反應，便在矽基板上形成屬於多價陰離子的 PSPMK聚合物之接枝鏈。反應溶液係呈紅色，且始終均勻。 所獲得PSPMK基板在使用索氏萃取器利用水施行洗淨，經 乾燥後，利用橢圓偏光儀確認到膜厚約22Onm。 (實施例1-2) 在φ 16mm玻璃管中，依序添加BHE固定化矽基板 (10x40mm2)、CuBr(0. 〇25mmol)、CuBr2( 0. 005mmol)、4, 4- 二曱基-2, 2’ _聯吡啶（〇. 〇5〇mm〇i)、異丙醇（3mL)、水 (5. OmL)、80%MTAC(2-甲基丙烯醯氧乙基氯化二曱銨）水溶 液3.0mL、2-溴化異丁酸乙酯（0.025mm〇1)，施行冷凍脫氣’ 在25°C下騎15 *時反應，便在石夕基板上形成屬於多價 陽離子的MTAC聚合物（PMTAC)之接枝鏈。反應溶液係呈紅 色，且始終均勻。所獲得PMTAC基板在使用索氏萃取器利 用水施行洗淨，經乾燥後’利用橢圓偏光儀確認到 130nm 。 (實施例1 - 3) 針對已形成PMTAC(含多價陽離子之接枝鍵）的第 13 201132728 件、與已形成PSPM(含多價陰離子之接枝鏈）的第二元件彼 此間之接著特性’利用拉伸試驗進行評估。在丨〇x4〇mm2的 PSPM與PMTAC基板上滴下5 // L水，並將基板端1 〇mm部分 相貼合（接觸面積=lcm2)。在此處放置5〇〇g(4. 9N)的錘，於 室溫下放置1小時後，使用拉伸試驗機（島津製EZ_Graph) 評估接著強度。測力器係使用5 0 N規格，上下方向的拉伸 速度係設為lmm/min。樣品的設置方法係如第1圖所示， 截氣閥（air check)部分由Kimwipe(精密科學擦拭紙）覆 蓋’並將石夕基板固定化。若將由測力器所檢測出的力（N) 格式化為實測接著面積每1 c m2之力的剪切力，並進行求 取’則PSPMK與PMTAC的組合係38N。 (實施例1-4) 在Φ 1 6mm玻璃管中’依序添加BHE固定化矽基板 (10x40x0.5mm3)、CuBr(0.025mmol)、4,4’-:f*-2,2’-Japan, 58(2), 3607-3608 (2009) 5 201132728 Non-Patent Document 9: KG Neoh et al., Macromolecules, 30, 3354-3362 (1997) Non-Patent Document 10: KG Neoh et al., Journal of Polymer Science : Part A : Polymer Chemistry, 36, 357-366 (1998) Non-Patent Document 11: KG Neoh et al., Langmuir, 14 921-927 (1998) Non-Patent Document 12: KG Neoh et al., Polymer, 39, 2429-2436 (1997) Non-Patent Document 13: KG Neoh et al., Journal of Polymer Science: Part A · Polymer Chemistry, 36, 31 07-3114 (1998) Non-Patent Document 14: KG Neoh et al., Journal of Applied Polymer Science, 70, 19 77-1983 (1998) Non-Patent Document 15: KG Neoh et al., European Polymer Journal, 35, 1279-1288 (1999) Non-Patent Document 16: KG Neoh et al., International Journal of Adhesion & Adhesives, 19, 359-365 (1999) Patent Document 1: US Patent 5,201,81, 1 Patent Document 2: US Patent Publication 5, 755, 91 3. National Institute of Science and Technology, Taiwan, May 26, 1998 [Invention Content] The inventors found that by using Surface configuration is formed contains an electrolyte 6201132728, Shu eight mutually different poles of the two elements green graft chain molecular layer, the above problems can be solved. The "polymer graft layer" as defined in the present invention refers to a nano-scale film in which a polymer chain terminal or a surface molecular chain is partially formed by immobilization with a surface of a substrate by a covalent bond. Because of the enthalpy, the polymer graft layer is not washed by the use of the agent, and the shape of the substrate is caused by slight friction. Therefore, the object of the present invention is to provide that: + there will be a problem in which the adhesion of the adhesive layer on the surface of the adherend occurs on the surface of the adherend, and the residual adhesive does not cause the adherend to be peeled off when the adherend is peeled off. The damage can be repeatedly ordered followed by peeling of the extremely thin back layer, and the composite containing the adhesive layer. s (the subject to be solved by the invention) That is, it is found that the combination introduces a component containing a positively charged polyvalent cation or a zwitterionic polymer graft chain onto a substrate, and introduces a negatively charged multivalent value on the substrate. The anionic or zwitterionic polymer grafts the elements of the chain, while forming a novel follower element with strong adhesion properties. For example, a polymer graft chain system containing a positively-charged polyvalent cation is, for example, an ammonium-containing compound (Non-Patent Document 5). The polymer graft chain having a negatively-charged polyvalent anion has a high concentration of zwitterion such as a sulfonic acid group-containing material (Non-Patent Document 6) and a carboxyl group (Non-Patent Document 7) (Non-Patent Document 8). The molecular graft chain system is, for example, a carbonyl beet test, a phosphoric acid beet test, a sulphur beet test, and the like. The subject matter of the present invention, which is accomplished in accordance with the present findings, includes the following or (1) an elemental method of forming a first element having a multivalent cationized zwitterionic graft chain, and a surface A second element comprising an ion or a zwitterionic graft chain has been formed which is followed by a face-to-face relationship with each other. (2) The method according to (1), wherein the water is interposed between the first element and the second element. (3) The method according to (1) or (2), wherein the polyvalent cation-containing graft chain is selected from the group consisting of a graft chains having an acridine rust group or an ammonium group; The branch chain is selected from the group consisting of a carboxyl group, a sulfonic acid group, a sulfate group or a phosphoric acid group; the polymer graft chain of the feeding material is selected from the group consisting of carbonyl beet mash, phosphoric acid beet test, and sulfone beet mash. Branch chain. (4) The method according to any one of (1), wherein the first element and the element are cut, a polymer, a cellulose, a metal or an inorganic material. (5) The method according to any one of (1) to (4), wherein the graft chain containing a polyvalent cation or a zwitterion and the above-mentioned multivalent anion or zwitterion are bonded The branches are respectively fixed to the first element and the second element via a covalent bond. (8) A method of subsequently attaching a component to a surface comprising a polyvalent cation or a zwitterionic graft chain, and a second component comprising a polyvalent anion or a zwitterionic graft bond to the surface. The graft chains are placed opposite each other with water interposed therebetween, and then peeled off by heating or a salt solution. (7) 'A method of pick-up, which is to form a polyvalent anion or a first 7L ^ Λ ' ^ surface of a surface containing a multivalent cation or a double grafted ionic bond by 矣ΛΡι JH/J·, aa The second element of the ionic grafting bond of the two surnames is such that the grafting chains are placed opposite each other and the heat is applied to the opposite side and the salt solution is applied to the opposite side and the water is deposited to carry the water. Then, after dehydration and peeling, the graft chains are brought into contact with each other. (8) A polymer composite, the first element of the zwitterionic graft chain is followed by a second element of the zwitterionic graft chain. The effect of the invention is that the surface forms a multivalent cation or forms a polyvalent anion with the surface or 'the opposite side of the graft chain. According to the invention, the first step of forming a graft bond containing a polyvalent cation on the surface is provided. A 7L piece, a second element that forms a graft chain containing a polyvalent anion on the surface, is followed by a technique. Namely, in the case of the present invention, since only substances having mutually different polarities are attached, it is possible to selectively select only the material elements and the portions. Further, according to the present invention, since the extremely small water droplets are sandwiched into the subsequent interface without using an adhesive and an organic solvent, the above first element :: and above! The second component is then carried out, thus providing a technique that does not contaminate the surrounding environment with minimal load on the environment. [Complex mode] The following is a more specific method for the present invention including its optimum form. (IV) The subsequent method of the present invention forms a binary M-member containing a multivalent cation on the surface and forms a polyvalent anion with the surface. The first member of the graft chain is such that the graft chains are followed by opposite faces. In the invention of the present invention, the polycation-containing graft chain and the polyvalent anion-containing graft chain are used, and the main chain or the side chain contains a polymer having mutually different polar functional groups. Further, the graft chain is not limited to being composed of a single monomer, and may be composed of two or more kinds of monomers. The above polyvalent anion can be used generally having a negatively chargeable functional group such as a sulfonic acid, sulfuric acid, a carboxylic acid, a phosphoric acid, etc., for example, polysulfonic acid styrene, polyvinyl sulfuric acid, dextran sulfuric acid, cartilage sulfate, poly (3-methacryl decyl propyl tartaric acid), poly(methacrylic acid condensed polyethylene glycol squaraine), hyaluronic acid, polyacrylic acid, polyacrylic acid, polymaleic acid, polybutene Acid, poly(2-propenylamine-2-mercapto-1-propanesulfonic acid), etc. 'preferably poly (poly methacrylic acid-3-sulfoacetic acid) (PSPM), sodium polymethacrylate (pMANa) and so on. The above polyvalent cations may be those having a positively charged functional group such as a pyridine rust group, an ammonium group, a quaternary ammonium group, an amine group, etc., for example, a polyethylenimine, a polyallylamine hydrochloride, a poly Diallyl gasification of dimethylammonium, polyethylene, bite, poly(N-methyl-2-ethylene. Specific bite) 'poly(N_methyl_4_ethene acridine), poly(iso) Amine acid, polystyrene methylene diethylethylamine, poly(dimethylaminoethyl methacrylate) 'poly(2-mercapto propylene oxyethyl iodide), etc. Poly(2-methylpropenyloxyethyl iodide) (pMTAC) and the like. The combination of the polyvalent anion and the above polyvalent cation is preferably a combination of a PSPM belonging to a polyvalent anion, a pMTAC belonging to a polyvalent cation, or the like. One end is immobilized (joined) with the first element and the second element by a covalently bonded polyvalent cation and a 10 201132728 bond of the polyvalent anion. Specifically, the surface of the element is utilized, for example, (2_bromo-2-propenylpropynyloxyhexyltriethoxydecane), or 2-bromo-2-methylpropynyloxy Hexyltrimethoxydecane (BHM), or 2-bromo-2-indolyl-propynyloxyundecylphosphonic acid (BUP) or Bu (2',2,6,6,-tetraindole) A surface initiator such as piperidine-!, fluorenyl 2 phenyl-ethylphosphonic acid or the like is treated, and a site which becomes a starting point of polymerization on the surface of the element is immobilized by a covalent bond. When a polyvalent cation or a polyvalent anion is grown by a polymerization starting method starting from the site, a graft chain containing a polyvalent cation or a graft chain containing a polyvalent anion can be firmly bonded on the surface. Components. Therefore, in the invention of the present invention, the polyvalent anion-containing graft chain terminal and the polyvalent cation-containing graft chain terminal are bonded to the surface of the device by a covalent bond via a surface initiator. The first element and the second element can be firmly solidified without peeling off. If the first element having the multivalent cation graft layer is obtained thereby, the first element is bonded to the first member having the polyvalent anion graft layer. There is a strong electrostatic interaction between the two graft layers, and this is the main original @, which causes the components to follow each other. Therefore, the essential layer of the layer is to electro-flate the graft layer to the molecule. Further, in the present invention, since the graft layer and the element system are covalently bonded, a very high bonding ability is exhibited. In the case of the conventional technique, the layer is a polymer electrolyte layer m in which a multivalent cation and a polyvalent anion are alternately laminated, but since the laminated film and the surface of the element belonging to the adherend are not chemically bonded, There is a problem that the adhesive layer is easily removed from the component (4), and the peeling is followed: 11 201132728 can not be reused. The graft chain containing the polyvalent cation formed by the surface initiation polymerization method and the above-mentioned range containing the polyvalent anion are used. The first element having the above-mentioned multivalent cation graft chain formed on the surface and the second element having the above-mentioned polyvalent anion graft bond formed on the surface are firmly adhered to each other via a very small amount of water. Combine. In the invention of the present invention, the first member of the polyvalent cation-containing chain is formed on the surface, and the first member having the polyvalent anion-grafted bond formed on the surface is formed on the surface, and the carrier water is followed by It can be peeled off by treatment with twisting or salt solution. The invention of the present invention is peeled off by the treatment with a solution, and is detached, so that it can be peeled off without causing damage to the polymer chain at the time of peeling. In the invention of the present invention, the peeled μ, lean, and the first member are separated from the second member, and then the water is allowed to be deposited. Furthermore, the material of the first element and the second element of the present invention is not limited to the premise that the surface treatment agent can be introduced into the polymerization start site, and is preferably, for example, a metal substrate. , Shixi substrate, quartz substrate, fluorine polymer, polyethylene, polypropylene, cellulose. These shapes are also not particularly limited, and are applicable to any surface such as a flat surface, a spherical surface, a cylindrical surface, and an inner wall of a hollow tube. Also, these surfaces may be irregular. EXAMPLES Hereinafter, the present invention will be further described based on the detailed examples. The invention is not limited thereto. (Example 1-1) In a </) 16 mm glass tube, a BHE-immobilized Fossil substrate (10 x 40 mm 2 ), CuBr (0.025 mmol), CuBr 2 (0.000 5 nimol), 4, 4' _ were sequentially added. OmL (MeOH/H2〇= 5) Dimethyl-2, 2'-bipyridyl (0. 050 mmol), SPMK (-3-sulfopropyl methacrylate) aqueous methanol solution prepared to 1.82 M. /2 'v/v), subjected to freeze degassing, and reacted at 25 ° C for 15 hours to form a graft chain of a PSPMK polymer belonging to a polyvalent anion on the ruthenium substrate. The reaction solution is red in color and is always uniform. The obtained PSPMK substrate was washed with water using a Soxhlet extractor, and after drying, the film thickness was confirmed to be about 22 nm by an ellipsometer. (Example 1-2) In a φ 16 mm glass tube, a BHE-immobilized ruthenium substrate (10×40 mm 2 ), CuBr (0. 〇 25 mmol), CuBr 2 (0.05 mmol), and 4, 4-dimercapto-2 were sequentially added. , 2'-bipyridyl (〇. 〇5〇mm〇i), isopropanol (3mL), water (5.0mL), 80% MTAC (2-methacryloyloxyethylammonium chloride) Aqueous solution 3.0 mL, 2-ethyl bromide isobutyrate (0.025 mm 〇 1), subjected to freeze degassing 'At the time of riding at 15 ° C at 15 °, the MTAC polymerization belonging to the multivalent cation was formed on the Shixi substrate. The graft chain of the substance (PMTAC). The reaction solution was red and always uniform. The obtained PMTAC substrate was washed with water using a Soxhlet extractor, and after drying, it was confirmed to be 130 nm by an ellipsometer. (Examples 1 - 3) The subsequent characteristics of the second element which has formed PMTAC (graft bond containing polyvalent cation) and the second element which has formed PSPM (graft chain containing polyvalent anion) 'Evaluate using the tensile test. 5 / 8 L of water was dropped on the PSPM and PMTAC substrate of 丨〇 x 4 〇 mm 2 , and the 1 〇 mm portion of the substrate end was attached (contact area = lcm 2 ). A 5 〇〇g (4.9 N) hammer was placed here, and after standing at room temperature for 1 hour, the strength was evaluated using a tensile tester (EZ_Graph, Shimadzu). The force measuring device uses the 50 N specification, and the tensile speed in the up and down direction is set to 1 mm/min. The sample was set up as shown in Fig. 1, and the air check portion was covered with Kimwipe (precision scientific wiping paper) and the Shishi substrate was fixed. If the force (N) detected by the dynamometer is formatted as the shear force of the force per 1 c m2 of the area, and the calculation is performed, then the combination of PSPMK and PMTAC is 38N. (Example 1-4) A BHE-immobilized ruthenium substrate (10x40x0.5mm3), CuBr (0.025mmol), 4,4'-:f*-2,2'- was sequentially added in a Φ 16 mm glass tube.
聯0比咬（〇. 〇50mmol )、異丙醇（3mL)、水（5.0mL)、80%MTAC 水溶液3. OmL，施行冷凍脫氣，在30°C下進行24小時反應。 所獲得基板在使用索氏萃取器利用水施行洗淨，並使乾 燥°利用橢圓偏光儀確認到PMTAC接枝鏈的膜厚約21 〇nm。 (實施例1-5) 針對依照實施例1-1已形成PSPMK(含多價陰離子之接 枝鏈）的第一元件、與依照實施例卜2已形成PMTAC(含多 價陽離子之接枝鏈）的第二元件間之接著特性，利用拉伸試 驗進行評估。在10x40mm2的PSPMK與PMTAC基板上滴下2 " l 水’並將基板端l〇min部分相貼合（接觸面積=lcm2)(第2 14 201132728 圖）。在此處放置500g(4.9N)的錘，於室溫下放置1小時 後，使用拉伸試驗機（島津製EZ-Graph)評估接著強度。測 力器係使用1 〇 〇 N規格’上下方向的拉伸速度係設為 lmm/min。樣品的設置方法係如第3圖所示，在二接著元件 的各自另一端貼附銘板（10x25x0.3mm3)，在將其固定於拉 伸試驗機的截氣閥上。若將由測力器所檢測出的力（N)格式 化為實測接著面積每1 cm2之力的剪切力，並進行求取，則 PSPMK與PMTAC的組合係84N。 (實施例1 - 6) 若將依照實施例1-1所調製得PSPMK接枝化矽基板（第 1元件）、與依照實施例1-4所調製得PMTAC接枝化矽基板 (第2元件）相貼合，則接著面積每1 cm2的剪切力係8 〇. 〇n。 此處在已剝離的元件上滴下2 # L水，並再度將基板端10mm 部分相貼合，結果二元件會接著，從拉伸試驗所求得每丨cm2 的剪切力係76.0N。此項結果顯示接枝化基板係可進行再 接著。 (實施例2) 在Φ 1 6mm玻璃管中，依序添加BHE固定化矽基板 (10x40mm2)' CuBr(0. 025mmol)、CuBr2(〇. 〇〇5mmol)、4, 4,- 二曱基-2, 2’ -聯吡啶（〇. 〇50mmol)、經調製為〇. 5M的曱基 丙烯酸鈉鹽（MANa)水溶液6.0roL(PH = 8.5)，施行冷;東脫氣， 在25C下進行3小時反應，便在矽基板上形成屬於多價陰 離子的MANa聚合物（PMANa)之接枝鏈。反應溶液係呈紅 色，且始終均勻。所獲得聚合物基板在使用索氏萃取器利 15 201132728 用水施行洗淨’經乾燥後’利用橢圓偏光儀確認到膜厚約 150nm。 與實施例1-2同樣的，製成有形成pMTAC(含多價陽離 子之接枝鍵）的第一元件。The mixture was subjected to freeze degassing at 30 ° C for 24 hours. The mixture was dehydrated and degassed by an amount of 3.0 mM (50 mL), isopropyl alcohol (3 mL), water (5.0 mL), and 80% aqueous solution of MTAC. The obtained substrate was washed with water using a Soxhlet extractor, and the dryness was confirmed by an ellipsometer to a film thickness of the PMTAC graft chain of about 21 〇 nm. (Example 1-5) For the first element in which PSPMK (graft chain containing polyvalent anion) was formed according to Example 1-1, and PMTAC (graft chain containing multivalent cation) was formed according to Example 2 The subsequent properties between the second components were evaluated using a tensile test. 2 "water' was dropped on the 10x40 mm2 PSPMK and PMTAC substrate and the substrate end l〇min portion was bonded (contact area = lcm2) (Fig. 2 14 201132728). A 500 g (4.9 N) hammer was placed here, and after standing at room temperature for 1 hour, the strength of the joint was evaluated using a tensile tester (EZ-Graph, Shimadzu). The dynamometer uses a 1 〇 〇 N specification. The tensile speed in the up and down direction is set to lmm/min. The sample was set up as shown in Fig. 3, and a nameplate (10x25x0.3mm3) was attached to the other end of each of the two subsequent members, and was fixed to the shutoff valve of the tensile tester. If the force (N) detected by the dynamometer is formatted into the shear force of the force per 1 cm2 of the measured area, the combination of PSPMK and PMTAC is 84N. (Examples 1 - 6) The PSPMK grafted ruthenium substrate (first element) prepared in accordance with Example 1-1 and the PMTAC grafted ruthenium substrate prepared according to Example 1-4 (second element) When the film is attached, the shear force per 1 cm2 of the area is 8 〇. 〇n. Here, 2 # L of water was dropped on the peeled member, and the 10 mm portion of the substrate end was again bonded. As a result, the second component was followed by a tensile force of 76.0 N per cm 2 from the tensile test. This result shows that the grafted substrate can be further processed. (Example 2) In a Φ 16 mm glass tube, a BHE-immobilized ruthenium substrate (10×40 mm 2 ) 'CuBr (0.025 mmol), CuBr 2 (〇. 〇〇 5 mmol), 4, 4,-dimercapto- 2, 2'-bipyridyl (〇. 〇 50 mmol), prepared as 〇. 5M aqueous solution of sodium methacrylate (MANa) 6.0roL (pH = 8.5), cold; east degassed, carried out at 25C 3 In the hourly reaction, a graft chain of a Mana polymer (PMANa) belonging to a polyvalent anion is formed on the ruthenium substrate. The reaction solution was red and always uniform. The obtained polymer substrate was washed with water using a Soxhlet extractor 15 201132728. After drying, the film thickness was confirmed to be about 150 nm by an ellipsometer. In the same manner as in Example 1-2, a first member which formed pMTAC (a graft bond containing a polyvalent cation) was prepared.
在10x40mm2的PMANa基板與PMTAC基板上滴下5//L 水，並將基板端l〇mm部分相貼合（接觸面積=lcm2) ^在此 處放置500g(4. 9N)的錘，於室溫下放置】小時後，使用拉 伸試驗機（島津製EZ-Graph)評估接著強度。測力器係使用 50N規格上下方向的拉伸速度係設為1 mm/m i n。若將由測 力器所檢測出的力（N)格式化為實測接著面積每lcm2之力 的剪切力，並進行求取，則⑽人以與pMTAC的組合係25N。 (實施例3) 與實施例1-1 ' 1-2同樣的在1〇x4〇mm2矽基板上形成 PSPMK與PMTAC ’並依照實施例卜5的順序，將矽基板端 lOnm2(接觸面積=lcm2)予以接著而形成複合體。 在上述複合體的單邊端垂吊著l〇〇g的錘，並利用夾具 抓住另-端且上舉，利用在大氣中呈垂直垂吊而確認到二 矽基板並沒有剝離。 在垂直地垂吊10 〇g錘(體積13cm”狀態下，將上述複 合體浸潰於脫離子水中（第4圖）。㈣，即便放置約⑷、 時，但一元件仍不會剝離。 在垂直地垂吊100§錘狀態下，將上述複合體浸潰於 〇.5M氣化鈉水溶液(第4圖）。然後，即便放置約【小時， 確認到單邊的元件出現自然剝離並掉落情形。 16 201132728 再者’由本案發明所形成的複合體確認到即便浸潰於 0. 5M食鹽水中仍可剝離。 再者’將經剝離的基板利用脫離子水施行洗淨，再依 照實施例1 -6的順序將該基板施行貼合，二者便會再度接 著。此時的接著面積每lcm2之剪切力係24N。此現象顯示 藉由分開使用水與食鹽水，便能可逆地重複進行接著與剝 離。 (實施例4-1) 在φ 18mm玻璃管中，依序添加BHM固定化玻璃基板 (10x40xlmm3)、BHM 固定化矽基板（10x40x0· 5mm3)、 CuBr2=(0.025mmol) 、 4,4’ -二曱基-2,2’ -聯吡咬 (0. 0 50mmol)、經調製為l 40M的SPMK之曱醇水溶液 6. OmL(MeOH/H2〇 = 5/2，v/v)，利用氬氣施行數分鐘的發泡 後’添加抗壞血酸（〇· 030mmol)，並於25。(：下攪拌15小時， 藉此便在玻璃及矽基板上形成PSPMK之接枝鏈。反應溶液 係呈紅色’且始终均勻。所獲得基板在使用索氏萃取器利 用水施行洗淨，浸潰於乙二醇中數分鐘後，再度利用水洗 淨並乾燥。利用分光橢圓偏光儀確認到矽基板上生成膜厚 約1 35nm的PSPMK接枝層。 (實施例4-2) 在φΐ 6mm玻璃管中，依序添加聚（偏氟乙烯_co-三氣 乙烯）薄膜（10x40x0. 〇1_3)與 BHM固定石夕基板 (10x40x0.5mm3)、CuBr=(0.030mmol)、4,4’-:f*_2,2’- 聯D比啶（0. 06 0mmo I)、經調製為1. 40Μ的SPMK之甲醇水溶 17 201132728 液6. OmL(MeOH/H2〇=5/2，v/v)，重複施行3次冷凍脫氣而 去除溶存氧之後’於氬氣流下，依25。(：進行3小時反應。 所獲得薄膜及基板在使用索氏萃取器利用水施行洗淨，浸 潰於乙二醇中數分鐘後’再度利用水洗淨並乾燥。利用分 光橢圓偏光儀確認到矽基板上生成膜厚約145ηιη的pspMK 接枝層。 (實施例4_3) 在<;〇 16mm玻璃管中’依序添加聚（偏氟乙烯-c〇_三氟 乙烯）薄膜（10x40x0. 01mm3)與 BHM固定石夕基板 (10x40x0. 5mm3)、CuBr=(0. 027mmol)、4, 4’ -二曱基-2, 2,- 聯0比0定（0. 05 6mmol )、異丙醇（3mL)、水（5.0mL)、80%MTAC 水溶液3· OmL ’施行冷凍脫氣，在30°C下進行16小時反應。 所獲得薄膜與矽基板在使用索氏萃取器利用水施行洗淨， 經乾燥後。利用橢圓偏光儀確認到矽基板上生成膜厚約 280nm的PMTAC接枝層。 (實施例4 - 4) 在φ 16mm玻璃管中’添加BUP固定化不銹鋼基板 (SUS304 製、10x40xlmm3) ' BHE 固定化石夕基板 (10x40x0.5mm3)、曱基丙烯酸曱酯（MMA，48.、 CuBr(0.025mmol) 、 (-)- 金 雀花驗 (sparteine)(0.0510mmol) 、 2-漠化異丁 酸乙醋 (0.025 mmol)、茴香醚（lmL)’重複施行3次冷床脫氣後， 於7 5 °C下進行4小時反應。基板係使用索氏萃取器利用甲 苯施行洗淨，再使真空乾燥。利用橢圓偏光儀確認到矽基 18 201132728 板上生成膜厚約30ηιη的PMMA接枝薄膜。 將所獲得不銹鋼及石夕基板再度放入史16min玻璃管中， 並在其中添加〇1^1"(0.022111111〇1)、4,4，-二甲基-2,2，-聯。比 咬（〇.〇42mmol)、MTAC(12_ 2minol)、2-溴化異丁 酸乙酿 (〇_〇llmmol)、異丙醇（〇.23mL)、2,2,2,2-三氟乙醇 (4. 6mL)，經施行3次冷凍脫氣後’依6(TC進行88小時反 應。所獲得基板在使用索氏萃取器利用水施行洗淨，經乾 燥後’利用橢圓偏光儀確認到形成膜厚約5〇nm之由 PMMA~b-PMTAC構成的嵌段共聚物接枝層。 (實施例4-5) 針對已形成接枝鏈的元件彼此間之接著特性，依照實 施例1-5的順序利用拉伸試驗進行評估。若將依實施例4-1 所調製得PSPMK接枝化玻璃基板、與依實施例卜2所調製 得PMTAC接枝化矽基板相貼合’則接著面積每丨cm2的剪切 力係10. 3N。 再者’若將依實施例4-1所調製得PSPMK接枝化玻璃 基板、與依實施例4-3所調製得pMTAC接枝化聚（偏氟乙烯 c〇-二氟乙烯）薄膜相貼合，則接著面積每lcm2的剪切力 係25. 1N。若將依實施例4-2所調製得PSPMK接枝化聚（偏 氟乙烯-co-三氟乙烯）薄膜、與依實施例卜2所調製得 PMTAC接枝化矽基板相貼合，則接著面積每lcm2的剪切力 係 34. 7N。 若將依實施例1-1所調製得PSPMK接枝化矽基板、與 依實施例4-3所調製得PMTAC接枝化聚（偏氟乙烯三氟乙烯） 19 201132728 薄膜相貼合，則接著面積每lcm2的剪切力係12. 3N。 若將依實施例1-1所調製得PSPMK接枝化矽基板、與 依實施例4-4所調製得PMMA-b-PMTAC接枝化不銹鋼基板相 貼合’則接著面積每1 cm2的剪切力係1 〇 . 7N。 由上述得知’此手法可將諸如玻璃、氟系薄膜、石夕、 不錢鋼等異種材質的基板進行接著。 (實施例5-1) 針對依實施例1-1形成PSPMK(含多價陰離子之接枝鏈） 的第一元件、與依實施例1-2形成PMTAC(含多價陽離子之 接枝鏈）的第二元件間之接著特性，利用拉伸試驗進行評 估。在10x40mm2的PSPMK與PMTAC基板上滴下2// L水， 並使基板端5mm部分相貼合（接觸面積=0 5cm2)。在此處放 置500g(4.9N)的錘，於室溫下放置}小時後，使用拉伸試 驗機（島津製EZ-Graph)評估接著強度。測力器係使用 1 000N規格，上下方向的拉伸速度係設為lmm/min。試料係 如第3圖所示，在二接著元件的另一端貼附不銹鋼板 (1 0x25x0. 3mm3)，並將其固定於拉伸試驗機的截氣閥上。 :¾將由測力器所檢測出的力（N)格式化為實測接著面積每 lcm2之力的剪切力，並進行求取，則pspMK與pMTAC的組 合係1 51N。 (實施例5-2) 利用分光橢圓偏光儀（Five Lab製MASS-102)求取實施 例5-1所使用剝離前後的毛刷膜厚。光源係使用由氙弧光 燈所產生的白色雷射（波長380-9〇〇nm)，依入射角度7〇。 20 201132728 進行測定。發現PMTAC毛刷的膜厚會從11 〇nm稍微降低至 95mn ° PSPMK毛刷則保持ΐ65ηπι狀態，並無發現有變化。 任一者均未出現因剝離而導致其中一毛刷薄膜從基板上消 失情形’並無明顯的膜厚變化，因此顯示依拉伸試驗所進 行的剝離係發生於二毛刷界面處。 (實施例5-3) 針對貫施例5-1所使用剝離前後的元件表面，利用X 光光電子能譜分析法（XPS)進行分析的光譜，如第5圖所 不。xps 測定係使用 ULVAC_PHI 製 XPS APEX，並在 ixi〇-6pa 條件下，依150W照射A1-K α單色χ射線，且檢測基板的 45。方向光電子。相關MTAC毛刷，在剝離前後的元素組成 幾乎無變化，任—者均等同從MTAG的分子構造所求得元素 組成（C/〇/n/C1=67/17/8/8)。另一方面，在 pspMK 毛刷經 剝離後的表面上’除源自SPMK的碳、氧、硫、鉀之外，尚 新出現氮與氯的尖峰。此現象可認為係在剝離時，其中一 部分PMTAC分子被脫離，並移動 所致。 移動至咖毛刷表面的緣故 (實施例5-4) 在依實施例5-1剝離的元件 ,..千上滴下2//L的水，並再度 使基板端5mm部分相貼合，社罢_ _ 、’°果一 7L件會再度接著，由 伸試驗所求得每W㈣切力係π肩。 將該剝㈣元件利用同樣的操作進行貼合，結果二= 會再度接者。此時每lcm2的剪 造成剝離、以及因重複施行再二30肩。若因剪切而 導致接著強度降低， 21 201132728 但毛刷會殘存於a件上，顯示接技化基板可進行再接著。. (實施例5-5) 在依實施例5-1所調製得複合體的單邊端垂直垂吊 l〇〇g的錘（體積13cm3)，並浸潰於脫離子水中（第3圖）。 然後，即使放置約24小時，二元件仍不會剝離。 。 在垂直地垂吊l〇0g錘狀態下，將上述複合體浸潰於 0. 5M氣化鈉水溶液（第4圖）。然後，即便放置約i小時，、 確認到單邊的元件出現自然剝離並掉落情形。 (實施例5-6) 在此將㈣離的元件利用脫離子水施行洗淨並自然乾 燥後’滴τ 2 # L的水，再使基板端5min部分相貼合，結果 二元件會再度接著。從拉伸試驗所求得每lcm2的剪切力°係 104N。 (實施例5-7) 利用原子力顯微鏡（AFM)觀察依實施例5_6所剝離的 元件表面（第6圖）。懸臂係使用彈力常數42Nnfl的氮化矽 製PPP-NGHR-2〇(NAN〇SENSORS公司製），依照仙邮製 AgiieM 5000的AC模式（相當於輕拍式），依掃描速度 lOvms-1在大氣中於室溫下進行觀察。1〇"mxl(^m平方的 均方根粗糙度（RMS)係當PMTAC毛刷的情況，在接著前係 1. 6nm，而經在氣化鈉水溶液中剝離後則為丨· 8nm。又，psp服 毛刷表面係接著前為2· Onm ’而剝離後則為2. 4nm，任一毛 刷表面並沒有因接著剝離而造成表面粗縫度極端增大情 形。 22 201132728 (實施例5-8) 在依實施例5-1所調製得複合體的單邊端，垂直垂吊 100g的錘（體積13cm3)，並浸潰於〇· 5M氣化鈉水溶液中（第 4圖）。經約1小時後，單邊的元件出現自然剝離並掉落後， 將元件利用脫離子水施行洗淨並自然乾燥，經依基板端 夾入2 # L水的狀態進行貼合，二元件會再度接著。經重複 在此氣化鈉水溶液中的剝離與洗淨、以及利用脫離子水施 行的接著合計2次後，施行拉伸試驗，結果每丨cm2的剪切 力係92N。此現象顯示藉由分開使用水與食鹽水便能可 逆地重複進行接著與剝離。 (實施例6) 在依實施例2所調製得10x4〇inm2的pMANa基板、與 PMTAC基板上，滴下2以L的水，依照實施例5-1的方法使 二基板端5ιηιπ部分相貼合，使用拉伸試驗機（島津製 EZ-Graph)進行接著強度的評估。測力器係使用1〇〇〇N規 才σ上下方向的拉伸速度係設為1 mm/mi η。若將由測力器 所檢測出的力（Ν)格式化為實測接著面積每lcm2之力的剪 切力’並進行求取’ PMANa與PMTAC的組合係108N。 (實施例7 -1) 使用依實施例4-1所調製得SPMK接枝化玻璃基板、與 依實施例1-2所調製得PMTAC接枝化矽基板，依照實施例 5-1的方法使二者相接著。接著面積每lcm2的剪切力係 86N ° (實施例7-2) 23 201132728 使依如實施例1 -3在玻璃基板上所調製pMTAC毛刷、 以及依實施例1-1所調製得SPMK接枝化矽基板，依照實施 例5-1的方法使二者相接著。接著面積每lcm2的剪切力係 107N。 (實施例7-3) 使依實施例4-1所調製得SPMK接枝化玻璃基板、與依 實施例7-2所調製得PMTAC毛刷，依照實施例5]的方法 使二者相接著。接著面積每lcm2的剪切力係99N。 (實施例8-1)(兩性離子毛刷彼此間的接著：磺甜菜驗例） 在Ρ 16ππη玻璃管中，依序添加BHE固定化矽基板 (10x40x0. 5ιιππ3) 、CuBr(0.025mmol) 、2,2’_ 聯吡啶 (0· 05 0mmol)、3-(N-2 -甲基丙烯醯氧乙基_NN_二甲基）氨 化丙烷磺酸酯（MAPS、5_ 9mmol)、曱醇（2· 〇mL)、水（2. OmL)， 施行冷凍脫氣，再於3 0。(：進行6小時反應。所獲得基板在 使用索氏萃取器利用TFE施行洗淨，並乾燥。利用橢圓偏 光儀確認到PM APS接枝鏈的膜厚約1 〇〇 nm。 (實施例8-2) 針對已形成PMAPS接枝鏈的元件彼此間之接著特性， 利用拉伸試驗進行評估。在1〇><4〇|1]|1]2的pMAps基板上放入 64 C熱水’並使基板端5mm部分相貼合（接觸面積 =0.5(：111)。在此處放置5〇〇§(4.91〇的錘，於熱水中靜置1.5 小時後’經去除水份，再於室溫大氣中放置2小時。在拉 伸試驗機（島津製EZ-Graph)上安裝lkN規格的測力器，並 依lmm/min的拉伸速度評估接著強度。 24 201132728 若將由測力器所檢測出的力（N)格式化為實測接著面 積每lcm2之力的剪切力，並進行求取，pMAps彼此間的組 合係154N。 (實施例8 - 2) 另一方面’在大氣中室溫（25t:)下，於PMAps基板上 滴下2 // L的水，並使基板端5 _部分相貼合，即便載置 500g(4.9N)的錘，並於室溫下放置2小時，但2片pMAps 基板彼此間仍接著。但是，從拉伸試驗所獲得剪切接著力， 經換算為每1 cm2係〇. 5N。 (實施例9-1)(針對耐熱性） 在依實施例1-1所獲得PSPMK毛刷基板上滴下2 # L的 水，使依實施例卜2所獲得PMTAC毛刷基板的端5_部分 相貼合，載置50Og的錘，經於室溫下靜置2小時，而使二 基板接著。將其懸吊於恆溫烤箱内，並垂直垂吊i 〇〇g的 錘。即使在150t下經過6小時，接著面仍未剝離地保持 著錘。 (比較例1) 依與實施例卜2同樣的，在矽基板上形成pMTAC接枝 鏈。利用橢圓偏光儀確認到膜厚約6〇nm。 針對已开> 成PMTAC(含多價陽離子之接枝鏈）的第一元 件彼此間之接著特性，利用拉伸試驗進行評估。在丨〇x4〇mm2 的PMTAC基板上滴下5 /z L的水，並使基板端1〇mm部分相 貼合（接觸面積=lcm2)。在此處放置5〇〇g(4.9N)的錘，於室 溫下放置1小時後，使用拉伸試驗機（島津製EZ_Graph)評 201132728 估接著強度。測力器係使用5ON規格，上下方向的拉伸速 度係設為lmm/min。樣品的設置方法係如第1圖所示。 若將由測力器所檢測出的力（N )格式化為實測接著面 積每lcm2之力的剪切力，並進行求取，pMTAC彼此間的組 合係1. 7N。 (比較例2) 在φ 1 6mm玻璃管中，依序添加BHE固定化石夕基板 (10x40mm2) 、 CuBr(0. 〇25mmol) 、 （_)金雀花驗 (0. 050mmol) '茴香驗（imL)、甲基丙稀酸曱醋（·α、 58. 2mmol)、2-溴化異丁酸乙酯（〇· 〇25mmol)，施行冷埭脫 氣’再於60C進行24小時反應，便在碎基板上形成mma 聚合物的聚曱基丙烯酸甲酯（PMMA)接枝鏈。反應溶液係呈 黃色，且始終均勻。所獲得PMMA接枝基板在使用索氏萃取 器利用曱苯施行洗淨，並乾燥。利用橢圓偏光儀確認到膜 厚約10 0 n m。 針對已形成PMMA接枝鍵的第一元件彼此間之接著特 性’利用拉伸試驗進行評估，在10x4〇mm2的PMMA基板上 滴下5 # L的水’使基板端1 〇min部分相貼合（接觸面積 -lcm)。在此處放置5〇〇g(4.9N)的錘，於室溫下放置1小 時後，使用拉伸試驗機（島津製EZ — Graph)評估接著強度。 測力器係使用50N規格，上下方向的拉伸速度係設為 lmm/min。樣品的設置方法係如第1圖所示。 PMMA彼此間的組合係當為求取將由測力器所檢測出的 力（N) ’從實測接著面積格式化為每lcm2力的剪切力，而 26 201132728 裝設於拉伸試驗機之際，僅因些微的碰撞便發生剝離，因 而無法測定剪切力。 (比較例3) 在P 16mm玻璃管中，依序添加HE固定化矽基板 (10x40mm ) CuBr(0. 025mmol) (-)金雀花驗 (0· 05 0_〇1)、茴香醚（lmL)、丙烯酸己酯（34. 2随〇1)、2_ 溴化異丁酸乙酯（〇. 〇25mmo 1)，施行冷凍脫氣，再於8〇艺 進行15小時反應。反應溶液呈紅色，且始終均勻。所獲得 聚（丙烯酸己酯）（PHA)基板在使用索氏萃取器利用甲苯施 行洗淨’經乾燥後’利用橢圓偏光儀確認到膜厚約65nm。 針對已形成中性接枝鏈的第一元件彼此間之接著特 性，利用拉伸試驗進行評估。在10x40mm2的pHA接枝基板 上滴下5 " L的水，並使基板端1 〇mm部分相貼合（接觸面積 = lcm2)。在此處放置500g(4.9N)的錘，於室溫下放置i小 時後，使用拉伸試驗機（島津製EZ-Graph)評估接著強度。 測力器係使用50N規格，上下方向的拉伸速度係設為 lmm/min。樣品的設置方法係如第1圖所示。 PHA接枝基板彼此間的組合係當為求取將由測力器所 檢測出的力（N)’從實測接著面積格式化為每lcm2力的剪 切力，而裝設於拉伸試驗機之際，僅因些微的碰撞便發生 剝離，因而無法測定剪切力。 (比較例4 ) 依與實施例1-2同樣的，在矽基板上形成pMTAC接枝 鏈。利用橢圓偏光儀確認到膜厚約60nm。 27 201132728 針對已形成PMTAC(含多價陽離子之接枝鏈）的第一元 件彼此間之接著特性，利用拉伸試驗進行評估。在1〇x4〇mm2 的PMTAC基板上滴下2/zL的水，並使基板端1〇mm部分相 貼合（接觸面積=lcm2)。在此處放置5〇〇g(4 9N)的錘，於室 溫下放置1小時後，使用拉伸試驗機（島津製EZ_Graph)評 估接著強度。測力器係使用1〇ΟΝ規格，上下方向的拉伸速 度係設為lmm/min。樣品的設置方法係如第3圖所示，在 二接著元件的另一端貼附鋁板（10x25x〇. 3mm3)，並將其固 定於拉伸試驗機的截氣閥上。 若將由測力器所檢測出的力（N)格式化為實測接著面 積每lcm2之力的剪切力，並進行求取，pMTAC彼此間的組 合係2. 7N。 (比較例5) 在P 16mm玻璃管中’依序添加BHE固定化矽基板 (10x40mra2) ' CuBr(0. 025mmo 1) > (-)金雀花驗 (〇· 050mmol)、茴香醚（imL)、甲基丙烯酸甲酯（MMA、 58. 2mmol) ' 2-溴化異丁酸乙酯（〇. 〇25mmol)，施行冷康脫 氣’再於60°C進行24小時反應’便在矽基板上形成MMA 聚合物的聚甲基丙烯酸甲酯（PMMA)接枝鏈。反應溶液係呈 黃色’且始終均勻。所獲得p_A接枝基板在使用索氏萃取 器利用曱苯施行洗淨，經乾燥後’利用橢圓偏光儀確認到 膜厚約1 OOnm。 針對已形成PMMA接枝鍵的第一元件彼此間之接著特 性，利用拉伸試驗進行評估。在10x40mm2的PMMA基板上 28 201132728 滴下2 v L的水，並使基板端} 〇mm部分相貼合（接觸面積 -lcm)。在此處放置500g(4.9N)的錘，於室溫下放置1小 時後，使用拉伸試驗機（島津製EZ-Graph)評估接著強度。 測力器係使用100N規格，上下方向的拉伸速度係設為 1 mm/mi η。樣品的設置方法係如第3圖所示，在二接著元件 的另一端貼附銘板（10x25x0_3mm3)，並將其固定於拉伸試 驗機的截氣閥上。 PMMA彼此間的組合係當為求取將由測力器所檢測出的 力（N) ’從貫測接著面積格式化為每丨cm2力的剪切力，而 裝設於拉伸試驗機之際，僅因些微的碰撞便發生剝離，因 而無法測定剪切力。 (比較例6) 在P 1 6mm玻璃管中，依序添加BHE固定化矽基板 (10x40mm2) 、 CuBr(0. 025mmol) > (_)金雀花撿 (0. 〇50mmol)、茴香醚（imL)、丙烯酸己酯（34. 2mm〇1)、2_ 溴化異丁酸乙酯（〇· 〇25mmol)，施行冷凍脫氣，再於8〇<t 進行15小時反應。反應浴液係呈紅色，且始終均勻。所獲 得聚（丙烯酸己酯）（PHA)基板在使用索氏萃取器利用曱苯 施行洗淨，經乾燥後，利用橢圓偏光儀確認到膜厚約65nm。 針對已形成中性接枝鏈的第一元件彼此間之接著特 I1 生利用拉伸试驗進行評估。在1 〇x40mm2的PHA接枝基板 上滴下2 μ L的水’並使基板端1 〇min部分相貼合（接觸面積 -lcm)。在此處放置5〇〇g(4.9N)的錘，於室溫下放置丄小 時後’使用拉伸試驗機（島津製EZ-Graph)評估接著強度。 29 201132728 測力器係使用100N規格，上下方向的拉伸速度係設為 1 mm/m i η。樣品的設置方法係如第3圖所示，在二接著元件 的另一端貼附鋁板（10x25x0, 3咖，並將其固定於拉伸試 驗機的截氣閥上。 ΡΗΑ接枝基板彼此間的組合係當為求取將由測力器所 檢測出的力（Ν)，從實測接著面積格式化為每力的剪 切力’而裝設於拉伸試驗機之際，僅因些微的碰撞便發生 剝離，因而無法測定剪切力。 【圖式簡單說明】 強度而使用的拉伸 第1圖係本案實施例中為評估接著 試驗機概略圖。5 / / L water was dropped on the 10 x 40 mm 2 PMANa substrate and the PMTAC substrate, and the substrate end l〇 mm portion was attached (contact area = 1 cm 2 ) ^ 500 g (4.9 N) of the hammer was placed here at room temperature After placing for an hour, the strength was evaluated using a tensile tester (EZ-Graph, Shimadzu). The force measuring device is set to a tensile speed of 1 mm/m i n using the 50N gauge in the up and down direction. If the force (N) detected by the dynamometer is formatted as the shear force of the force of the measured area per 1 cm 2 of the area, and (10), the combination with the pMTAC is 25N. (Example 3) PSKPM and PMTAC ' were formed on a 1 〇 x 4 〇 mm 2 矽 substrate in the same manner as in Example 1-1 '1-2, and the ruthenium substrate end lOnm2 (contact area = 1 cm 2 ) was obtained in the order of Example 5 ) is then followed to form a composite. A hammer of l〇〇g was hung on one side of the above-mentioned composite body, and the other end was lifted by a jig, and it was confirmed that the second substrate was not peeled off by hanging vertically in the atmosphere. The vertical composite was immersed in a 10 〇g hammer (volume 13 cm), and the composite was immersed in deionized water (Fig. 4). (4) Even if about (4) was placed, one component would not peel off. Vertically hang the 100 § hammer, the above composite was immersed in a 〇.5M vaporized sodium aqueous solution (Fig. 4). Then, even if it was placed for about [hours, it was confirmed that the unilateral component naturally peeled off and fell. 16 201132728 Further, the composite formed by the invention of the present invention was confirmed to be peelable even when immersed in 0.5 M saline. Further, the peeled substrate was washed with deionized water, and then according to the examples. The substrate is bonded in the order of 1 -6, and the two are followed again. The shearing force per 1 cm 2 of the subsequent area is 24 N. This phenomenon shows that it can be reversibly repeated by using water and saline separately. (Example 4-1) A BHM-immobilized glass substrate (10×40×1 mm 3 ), a BHM-immobilized ruthenium substrate (10×40×0·5 mm 3 ), CuBr 2=(0.025 mmol), and 4 were sequentially added to a φ 18 mm glass tube. , 4'-dimercapto-2,2'-bipyridyl (0. 0 50mmol O. </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> </ RTI> <RTIgt; And at 25: (: stirring for 15 hours, thereby forming a graft chain of PSPMK on the glass and tantalum substrate. The reaction solution is red' and always uniform. The obtained substrate is washed with water using a Soxhlet extractor. After being immersed in ethylene glycol for several minutes, it was washed again with water and dried. It was confirmed by a spectroscopic ellipsometer that a PSPMK graft layer having a film thickness of about 1 35 nm was formed on the ruthenium substrate. (Example 4-2) In a φΐ 6mm glass tube, a poly(vinylidene fluoride-co-triethylene) film (10x40x0. 〇1_3) and a BHM fixed slab substrate (10x40x0.5mm3), CuBr=(0.030mmol), 4, were sequentially added. 4'-:f*_2,2'-linked D-pyridinium (0. 06 0mmo I), prepared as 1.40Μ of SPMK in methanol water soluble 17 201132728 liquid 6. OmL (MeOH/H2〇=5/2, v/v), repeated three times of degassing to remove dissolved oxygen, 'under argon flow, according to 25 (: 3 hours of reaction. The obtained film and substrate are using Soxhlet extractor The mixture was washed with water, and after being immersed in ethylene glycol for several minutes, it was washed again with water and dried. It was confirmed by a spectroscopic ellipsometer that a pspMK graft layer having a film thickness of about 145 η was formed on the ruthenium substrate. (Example 4_3) In the <;〇16mm glass tube, sequentially add poly(vinylidene fluoride-c〇-trifluoroethylene) film (10x40x0. 01mm3) and BHM fixed Shishi substrate (10x40x0. 5mm3), CuBr=(0. 027mmol) ), 4, 4'-dimercapto-2, 2,- 0 to 0 (0. 05 6mmol), isopropanol (3mL), water (5.0mL), 80% MTAC aqueous solution 3·OmL 'Execution The mixture was degassed by freezing and subjected to a reaction at 30 ° C for 16 hours. The obtained film and the ruthenium substrate were washed with water using a Soxhlet extractor and dried. It was confirmed by an ellipsometer that a PMTAC graft layer having a film thickness of about 280 nm was formed on the ruthenium substrate. (Examples 4 - 4) 'BUP-immobilized stainless steel substrate (made of SUS304, 10x40xlmm3) 'BHE fixed fossil substrate (10x40x0.5mm3), decyl methacrylate (MMA, 48., CuBr) in φ 16mm glass tube (0.025mmol), (-)- sparteine (0.0510mmol), 2-divinated isobutyric acid vinegar (0.025 mmol), anisole (lmL)' repeated 3 times of degassing of the cold bed The reaction was carried out for 4 hours at 75 ° C. The substrate was washed with toluene using a Soxhlet extractor and dried under vacuum. It was confirmed by ellipsometry that the PMMA of the film thickness of about 30 ηηη was formed on the 矽 18 201132728 plate. Branch film. The obtained stainless steel and Shixi substrate were placed again in a 16-minute glass tube, and 〇1^1"(0.022111111〇1), 4,4,-dimethyl-2,2,-linked was added thereto. Specific bite (〇.〇42mmol), MTAC (12_ 2minol), 2-brominated isobutyric acid ethyl (〇_〇llmmol), isopropanol (〇.23mL), 2,2,2,2-three Fluoroethanol (4.6 mL) was subjected to 3 freezes and degassing, followed by 6 (TC for 88 hours. The obtained substrate was washed with water using a Soxhlet extractor, dried) It was confirmed by an ellipsometer that a block copolymer graft layer composed of PMMA~b-PMTAC having a film thickness of about 5 Å was formed. (Example 4-5) Adhesive properties of elements which have formed a graft chain with each other The evaluation was carried out by the tensile test in the order of Examples 1-5. The PSPKK grafted glass substrate prepared in accordance with Example 4-1 and the PMTAC grafted ruthenium substrate prepared in accordance with Example 2 were obtained. The bonding force of the area of each of the cm2 is 10.3 N. Further, if the PSPMK grafted glass substrate prepared in accordance with Example 4-1, and the pMTAC prepared according to Example 4-3, The grafting force of the grafted poly(vinylidene fluoride c〇-difluoroethylene) film is 25.1N. The grafting of PSPMK prepared according to Example 4-2 is carried out. 7N。 If the film is bonded to the PMTAC grafted ruthenium substrate prepared according to the embodiment 2, the shear force of the area per 1 cm 2 is 34.7 N. The PSPMK grafted ruthenium substrate prepared in Example 1-1 and the PMTAC grafted poly(vinylidene fluoride trifluoroethylene) prepared according to Example 4-3 19 2011327 28 The film is bonded, and then the shear force per area of 1 cm 2 is 12.3 N. If the PSPMK grafted to the ruthenium substrate prepared according to Example 1-1, and the PMMA-modified according to Example 4-4 The bonding force of the b-PMTAC grafted stainless steel substrate is then 1 〇. 7N per 1 cm 2 of the shearing force. It is known from the above that this method can be followed by a substrate of a different material such as glass, fluorine-based film, Shixia, and Coin Steel. (Example 5-1) A first element for forming PSPMK (graft chain containing a polyvalent anion) according to Example 1-1, and a PMTAC (graft chain containing a polyvalent cation) were formed according to Example 1-2. The subsequent properties between the second components were evaluated using a tensile test. 2 / / L of water was dropped on a 10 x 40 mm 2 PSPKK and PMTAC substrate, and the 5 mm portion of the substrate end was attached (contact area = 5 cm 2 ). A 500 g (4.9 N) hammer was placed here, and after standing at room temperature for 1 hour, the strength of the joint was evaluated using a tensile tester (EZ-Graph, Shimadzu). The force measuring device uses the 1 000 N specification and the tensile speed in the up and down direction is set to 1 mm/min. The sample was attached to a stainless steel plate (10x25x0. 3mm3) at the other end of the second component as shown in Fig. 3, and was fixed to the air shutoff valve of the tensile tester. :3⁄4 The force (N) detected by the force gauge is formatted as the shear force of the force per 1 cm 2 of the measured area, and the combination of pspMK and pMTAC is 1 51N. (Example 5-2) The thickness of the brush before and after peeling used in Example 5-1 was determined by a spectroscopic ellipsometer (MASS-102 manufactured by Five Lab). The light source uses a white laser (wavelength 380-9 〇〇 nm) produced by a xenon arc lamp at an incident angle of 7 〇. 20 201132728 The measurement was carried out. It was found that the film thickness of the PMTAC brush was slightly lowered from 11 〇 nm to 95 mn. The PSPMK brush was maintained at ΐ65 ηπι state, and no change was found. Either one of the cases where one of the brush films disappeared from the substrate due to peeling did not show a significant change in film thickness, so that the peeling performed by the tensile test occurred at the interface of the two-brush. (Example 5-3) The spectrum of the surface of the element before and after peeling used in Example 5-1 was analyzed by X-ray photoelectron spectroscopy (XPS), as shown in Fig. 5. The xps measurement was performed using a ULVAC_PHI XPS APEX, and under the condition of ixi〇-6pa, the A1-Kα monochromatic ray was irradiated at 150 W, and the substrate 45 was detected. Directional optoelectronics. The relevant MTAC brush has almost no change in the elemental composition before and after the stripping, and all of them are equivalent to the elemental composition obtained from the molecular structure of MTAG (C/〇/n/C1=67/17/8/8). On the other hand, in addition to the carbon, oxygen, sulfur, and potassium derived from SPMK, the peak of nitrogen and chlorine is newly formed on the surface of the pspMK brush after peeling off. This phenomenon can be considered to be caused by the fact that some of the PMTAC molecules are detached and moved during peeling. Moving to the surface of the coffee brush (Example 5-4) In the element peeled off according to Example 5-1, 2//L of water was dripped on the surface, and the 5 mm portion of the substrate end was again bonded. Stop _ _, '° fruit a 7L piece will be followed again, from the extension test to find each W (four) shear force π shoulder. The stripping (four) component is bonded by the same operation, and the result is that the second= will be re-connected. At this time, the shearing per lcm2 caused peeling, and two or more shoulders were repeatedly applied. If the strength is lowered due to shearing, 21 201132728, but the brush will remain on the a piece, indicating that the technical substrate can be followed. (Example 5-5) A hammer (volume 13 cm 3 ) of l〇〇g was vertically suspended at one end of the composite prepared in accordance with Example 5-1, and impregnated in deionized water (Fig. 3). . Then, even if left for about 24 hours, the two components will not peel off. . 5微米化化钠水溶液(第4图) The above composite was immersed in a 0.5 M gasified sodium aqueous solution (Fig. 4). Then, even if it is left for about i hours, it is confirmed that the unilateral element is naturally peeled off and dropped. (Example 5-6) Here, the (4)-off element is washed with deionized water and naturally dried, and then the water of the τ 2 2 L is dripped, and then the 5 min portion of the substrate is bonded to each other, and the second component is again followed. . A shear force of 104 N per 1 cm 2 was obtained from the tensile test. (Example 5-7) The surface of the element peeled off according to Example 5-6 was observed by an atomic force microscope (AFM) (Fig. 6). The cantilever system is made of PPP-NGHR-2〇 (manufactured by NAN〇SENSORS Co., Ltd.) with a linear constant of 42Nnfl, according to the AC mode of the Agiie M 5000 (equivalent to the tapping type), at a scanning speed of lOvms-1 in the atmosphere. The observation was carried out at room temperature. 1〇"mxl(^m square root mean square roughness (RMS) is the case of the PMTAC brush, which is 1. 6 nm before the stripping, and 丨·8 nm after stripping in the vaporized sodium aqueous solution. Moreover, the surface of the PSP clothing brush is 2·Onm′ before peeling and 2. 4 nm after peeling, and the surface of any brush is not extremely increased due to peeling. 22 201132728 (Example) 5-8) A 100 g hammer (volume 13 cm 3 ) was vertically suspended at one end of the composite prepared in Example 5-1, and immersed in an aqueous solution of 〇·5M vaporized sodium (Fig. 4). After about 1 hour, the unilateral components are naturally peeled off and fall behind. The components are washed with deionized water and dried naturally. After being sandwiched by 2 # L water according to the substrate end, the two components will be attached. Further, after the peeling and washing in the vaporized sodium aqueous solution and the subsequent use of the deionized water were repeated twice, a tensile test was performed, and as a result, the shear force per cm 2 was 92 N. This phenomenon was revealed. By using water and saline separately, it is possible to reversibly repeat and peel off. (Example 6) The pMANa substrate of 10×4〇inm2 prepared in Example 2 and the water of 2 L were dropped on the PMTAC substrate, and the two substrate ends were bonded together according to the method of Example 5-1, and a tensile tester was used. EZ-Graph) was used to evaluate the strength of the joint. The force measuring device used the 1〇〇〇N gauge to set the tensile speed in the up-and-down direction to 1 mm/mi η. If the force is detected by the dynamometer (Ν) formatted to measure the shear force of the force of the area per 1 cm 2 and to obtain the combination of PMANa and PMTAC 108N. (Example 7 -1) SPMK was prepared by using Example 4-1. The branched glass substrate and the PMTAC grafted ruthenium substrate prepared in accordance with Example 1-2 were followed by the method according to Example 5-1. The shear force per area of 1 cm 2 was 86 N ° (Example) 7-2) 23 201132728 The pMTAC brush prepared on the glass substrate according to Example 1-3, and the SPMK grafted ruthenium substrate prepared in accordance with Example 1-1 were subjected to the method of Example 5-1. The two were followed by a shear force of 107 N per 1 cm 2 of the area. (Example 7-3) SPMK grafted according to Example 4-1 was grafted. The glass substrate and the PMTAC brush prepared in accordance with Example 7-2 were followed by the method of Example 5. The shearing force per area of 1 cm 2 was 99 N. (Example 8-1) The zwitterionic brush is followed by each other: sulfone beet test) In the Ρ 16ππη glass tube, BHE immobilized ruthenium substrate (10x40x0. 5ιιππ3), CuBr (0.025mmol), 2,2'_bipyridine (0) are sequentially added. · 05 0mmol), 3-(N-2 -methacryloyloxyethyl_NN_dimethyl)ammonium propane sulfonate (MAPS, 5-9 mmol), decyl alcohol (2·〇mL), water ( 2. OmL), freeze degassing, and then 30. (: The reaction was carried out for 6 hours. The obtained substrate was washed with TFE using a Soxhlet extractor, and dried. The film thickness of the PM APS graft chain was confirmed to be about 1 〇〇 nm by an ellipsometer. (Example 8 - 2) Evaluation of the adhesion characteristics of the elements which have formed the PMAPS graft chain by the tensile test. Place 64 C hot water on the pMAps substrate of 1〇><4〇|1]|1]2 'And make the 5mm part of the substrate end fit (contact area = 0.5 (: 111). Place 5 § § (4.91 锤 hammer, let stand for 1.5 hours in hot water) after removing water, then Place it in the atmosphere at room temperature for 2 hours. Install a lkN-size force gauge on a tensile tester (EZ-Graph, Shimadzu), and evaluate the strength according to the tensile speed of 1 mm/min. 24 201132728 If it is to be operated by a dynamometer The detected force (N) is formatted as a shear force for measuring the force of the area per 1 cm 2 and is determined, and the combination of pMAps with each other is 154 N. (Examples 8 - 2) On the other hand, 'in the atmosphere At room temperature (25t:), 2 / 2 L of water was dropped on the PMAPS substrate, and the 5 _ part of the substrate was bonded, even if 500 g (4.9 N) was placed. The hammer was placed at room temperature for 2 hours, but the two pMAps substrates were followed by each other. However, the shearing force obtained from the tensile test was converted to 1 cm 2 〇 5 N. (Example 9 - 1) (for heat resistance) 2# L of water was dropped on the PSPMK brush substrate obtained in Example 1-1, and the end 5_ portion of the PMTAC brush substrate obtained in Example 2 was attached. Put a 50Og hammer and let it stand at room temperature for 2 hours to bring the two substrates together. Suspend it in a constant temperature oven and hang the hammer of i 〇〇g vertically. Even after 6 hours at 150t, then The surface was held without a peeling. (Comparative Example 1) A pMTAC graft chain was formed on a ruthenium substrate in the same manner as in Example 2. The film thickness was confirmed to be about 6 〇 nm by an ellipsometer. The subsequent characteristics of the first elements of the PMTAC (graft chain containing polyvalent cations) are evaluated by a tensile test. 5 / z L of water is dropped on the 丨〇x4〇mm2 PMTAC substrate, and The 1 mm portion of the substrate end is attached (contact area = 1 cm 2 ). Place a 5 〇〇 g (4.9 N) hammer here and place it at room temperature for 1 hour. After that, the tensile strength was evaluated using a tensile tester (Shimadzu EZ_Graph) 201132728. The force gauge was used in the 5ON specification, and the tensile speed in the up and down direction was set to 1 mm/min. The sample setting method is shown in Fig. 1. 7N。 The force of the force measured by the dynamometer (N) is measured as the force of the force of the area of the force per lcm2, and the pMTAC is 1. 7N. (Comparative Example 2) BHE-immobilized fossil substrate (10x40 mm2), CuBr (0. 〇25 mmol), (_) gorse test (0. 050 mmol) 'fennel test (imL) was sequentially added to a φ 16 mm glass tube. ), methyl acetonate vinegar (·α, 58.2 mmol), 2-ethyl bromide isobutyrate (〇·〇 25 mmol), subjected to cold degassing and then reacted at 60 C for 24 hours, A polymethyl methacrylate (PMMA) graft chain of mma polymer is formed on the crushed substrate. The reaction solution is yellow and is always uniform. The obtained PMMA graft substrate was washed with a benzene by a Soxhlet extractor and dried. The film thickness was confirmed to be about 10 0 n m using an ellipsometer. The adhesion characteristics of the first members having formed the PMMA graft bond to each other were evaluated by a tensile test, and 5 # L of water was dropped on a 10×4 mm 2 PMMA substrate to make the substrate end 1 〇 min portion fit ( Contact area - lcm). A 5 〇〇g (4.9 N) hammer was placed here, and after standing at room temperature for 1 hour, the strength was evaluated using a tensile tester (Shimadzu EZ-Graph). The force gauge is 50N, and the vertical speed is set to lmm/min. The method of setting the sample is shown in Figure 1. The combination of PMMA with each other is to determine the force (N) detected by the dynamometer from the measured joint area to the shear force per lcm2 force, and 26 201132728 is installed on the tensile test machine. The peeling occurs only due to a slight collision, and thus the shear force cannot be measured. (Comparative Example 3) In a P 16 mm glass tube, a HE-immobilized ruthenium substrate (10×40 mm) CuBr (0.225 mmol) (-) ginseng flower (0·05 0_〇1), anisole (lmL) was sequentially added. ), hexyl acrylate (34.2 with 〇1), 2_ethyl isobutyrate bromide (〇. 25mmo 1), subjected to freeze degassing, and then reacted for 15 hours at 8 〇. The reaction solution is red in color and is always uniform. The obtained poly(hexyl acrylate) (PHA) substrate was subjected to washing with toluene using a Soxhlet extractor, and dried to confirm a film thickness of about 65 nm by an ellipsometer. The evaluation of the tensile properties was carried out for the adhesion characteristics of the first members which had formed the neutral graft chain to each other. 5 " L of water was dropped on a 10 x 40 mm2 pHA grafted substrate, and the 1 〇mm portion of the substrate end was attached (contact area = lcm2). A 500 g (4.9 N) hammer was placed here, and after standing for one hour at room temperature, the strength of the joint was evaluated using a tensile tester (EZ-Graph, Shimadzu). The force gauge is 50N, and the vertical speed is set to lmm/min. The method of setting the sample is shown in Figure 1. The combination of the PHA graft substrates is set in a tensile tester in order to determine the force (N)' detected by the force measuring device from the measured contact area to a shear force per cm 2 force. At the same time, peeling occurs only due to a slight collision, and thus the shear force cannot be measured. (Comparative Example 4) A pMTAC graft chain was formed on a ruthenium substrate in the same manner as in Example 1-2. The film thickness was confirmed to be about 60 nm by an ellipsometer. 27 201132728 The evaluation of the tensile properties of the first elements of the formed PMTAC (graft chains containing polyvalent cations) was carried out using a tensile test. 2/zL of water was dropped on a 1 〇 x 4 〇 mm 2 PMTAC substrate, and the 1 〇 mm portion of the substrate end was bonded (contact area = 1 cm 2 ). A 5 〇〇g (49 N) hammer was placed here, and after standing at room temperature for 1 hour, the subsequent strength was evaluated using a tensile tester (EZ-Graph, Shimadzu). The dynamometer is 1 〇ΟΝ in size and the up and down stretching speed is set to 1 mm/min. The sample was set up as shown in Fig. 3, and an aluminum plate (10x25x〇. 3mm3) was attached to the other end of the second member and fixed to the shutoff valve of the tensile tester. 7N。 The force of the force measured by the dynamometer (N) is measured to the shear force of the force of the force of each of the thickness of 1 cm2, and the combination of pMTAC is 2. 7N. (Comparative Example 5) In a P 16 mm glass tube, 'BHE-immobilized ruthenium substrate (10x40 mra2) 'CuBr (0. 025 mmo 1) > (-) gorse test (〇·050 mmol), anisole (imL) Methyl methacrylate (MMA, 58.2 mmol) '2-ethyl bromide isobutyrate (〇. 〇 25 mmol), subjected to cold degassing 'reaction at 60 ° C for 24 hours' A polymethyl methacrylate (PMMA) graft chain of MMA polymer is formed on the substrate. The reaction solution was yellow' and was always homogeneous. The obtained p_A grafted substrate was washed with benzene by a Soxhlet extractor, and after drying, the film thickness was confirmed to be about 100 nm by an ellipsometer. The evaluation of the tensile properties was carried out for the adhesion characteristics of the first members which have formed the PMMA graft bond to each other. On a 10x40mm2 PMMA substrate 28 201132728 Drop 2 v L of water and make the substrate end 〇mm part fit (contact area -lcm). A 500 g (4.9 N) hammer was placed here, and after standing at room temperature for 1 hour, the strength of the joint was evaluated using a tensile tester (EZ-Graph, Shimadzu). The force measuring device is 100N gauge, and the tensile speed in the up and down direction is set to 1 mm/mi η. The sample was set up as shown in Figure 3. A nameplate (10x25x0_3mm3) was attached to the other end of the second component and attached to the air bleed valve of the tensile tester. The combination of PMMAs is used to determine the force (N) detected by the dynamometer from the measured area to the shear force per cm2 of force, and is installed on the tensile testing machine. The peeling occurs only due to a slight collision, and thus the shear force cannot be measured. (Comparative Example 6) In a P 1 6 mm glass tube, a BHE-immobilized ruthenium substrate (10×40 mm 2 ), CuBr (0.025 mmol) > (_) gorse (0. 〇 50 mmol), anisole ( imL), hexyl acrylate (34.2 mm 〇 1), 2 _ ethyl isobuty bromide (〇·〇 25 mmol), subjected to freeze degassing, and further reacted at 8 Torr for 15 hours. The reaction bath is red and always uniform. The obtained poly(hexyl acrylate) (PHA) substrate was washed with benzene by a Soxhlet extractor, and after drying, the film thickness was confirmed to be about 65 nm by an ellipsometer. The first element which has formed a neutral graft chain is evaluated by a tensile test. 2 μL of water was dropped on a PMA grafted substrate of 1 〇 x 40 mm 2 and the 1 〇 min portion of the substrate was bonded (contact area - lcm). A 5 〇〇g (4.9 N) hammer was placed here, and after standing for a small time at room temperature, the subsequent strength was evaluated using a tensile tester (EZ-Graph, Shimadzu). 29 201132728 The dynamometer uses the 100N specification and the tensile speed in the up and down direction is set to 1 mm/m i η. The sample was set up as shown in Fig. 3, and an aluminum plate (10x25x0, 3 coffee) was attached to the other end of the second component and fixed on the gas shutoff valve of the tensile tester. The combination system is installed on the tensile testing machine when the force (Ν) detected by the force measuring device is determined from the measured contact area, and only a slight collision occurs. The peeling occurred and the shearing force could not be measured. [Simplified illustration of the drawing] Tensile drawing used for the strength is an outline of the evaluation test machine in the present embodiment.
第2圖係本案實施例中元件 第3圖係為評估接著強度 之接著方法的概略圓。 而使用的拉伸試驗機概略 為評估朝接著部位平行方向施加靜冇重昧的 保持力之試驗裝置概略I h重時的 第5圖係為觀察剝離前後的元件表面 電子能譜分析面，而利用X光光 施行評估時的測定結果圖。 圖係為觀察已剝離的元件表面， 微鏡(則)進行觀察時的照片。 j用原子力顯 【主要元件符號說明】 無 30Fig. 2 is an element in the embodiment of the present invention. Fig. 3 is a schematic circle for evaluating the subsequent strength of the subsequent strength. The tensile tester used is a test apparatus for estimating the holding force of the static weight in the parallel direction of the subsequent portion. The fifth figure when the weight is I h is the observation surface of the element surface before and after the peeling, and A measurement result chart when evaluation is performed by X-ray light. The figure is a photograph when observing the surface of the peeled component and observing the micromirror (then). j uses atomic force display [Main component symbol description] None 30