201035276 六、發明說明： 【韻'明戶斤屬之^技^标>#貝;^】 發明領域 本發明係有關於一種用於各向異性導電膜之組成物。 更特別地，本發明係有關於一種藉由弓丨入聚酯聚矽氧烷共 聚物而不僅展現改良之起始黏著性且即使於高溫度/濕度 及熱衝擊條件下之長期操作後亦展現改良之黏著性及高可 靠度之用於各向異性導電膜之組成物，及—自此組成物製 造之各向異性導電膜。 I：先前技術1 相關技術說明 -般，各向異性㈣膜係減間分散導電顆粒之於膜 上之黏著劑。各向異性導電膜已被廣泛用以提供電組件間 (諸如’-LCD面板及-捲帶式載體封裝（亦稱為‘嘗，)間或 -印刷電路板及TCP間等）之連接。再者，各㈣性導麵 具有作為用於COG安裝、CQF安㈣之連接之材料之具吸 引力之注意。 各向異性導電膜-般係由一結合劑組份、一可固化組 份，及導電顆粒組成。依據可固化組份之_，各向異性 導電膜破分類為(i)環氧型各向異性導電膜，其使用一由以 環氧為主或以盼為主之樹脂及固化劑組成之可固化组份， 及⑻一曱細烯_旨齡向異性導頓，其❹一由（甲 基）丙稀酸絲料及單體及自由基起始·成之可固化 組份。 3 201035276 於環氧型各向異性導電膜(i)，環氧樹脂包含於固化後 形成一極堅固網絡結構之芳香族苯環，因此，證明良好之 可靠度。但是，因為環氧型各向異性導電膜需具有多數個 芳香族苯環，其不易調整於高溫度及壓力時之樹脂流動 性，且大量氣泡於連接期間產生，因此，降低膜之黏著。 再者，導電顆粒未被充份置於欲被彼此連接之電路間。再 者，環氧型各向異性導電膜之形成需極高反應溫度及長反 應期，因此，使其難以達成方法控制及維護連接裝置。 另一方面，丙烯酸型各向異性導電膜(ii)能經由快速之 基固化反應於數秒内快速固化，且可顯著降低黏著時間， 因此，顯著促進最終各向異性導電膜之生產速度。但是， 一般用於膜形成及流動性調整之具有低玻璃轉移溫度之聚 合物樹脂造成於電路間之呈連接狀態之各向異性導電膜之 重複收縮及膨脹，因此，使長期可靠度惡化。相反地，於 膜形成使用具高玻璃轉移溫度之聚合物樹脂會導致流動性 調整困難，因此，造成起始物理性質惡化，諸如，連接失 敗、低黏著性等。於其間反應速率被降低以保證導電顆粒 及電路間之連接之情況’由於結合劑組份及可固化組份間 之流變特徵而發生流動困難，因此’大量氣泡產生且長期 可靠度未被保證。相反地，於其間反應速率增加之情況， 導電顆粒及電路間之足夠接觸未被獲得，因此，良好之連 接可靠度不能被確保。 為解決相關技藝之此等問題，本發明提供一種用於各 向異性導電膜之組成物’其包含聚酯-聚矽氧烷共聚物作為 201035276 口劑組份，以具有良好流動性及提供高的起始黏著性， 同時藉由避免於各種應用之剝離而確保連接阻抗之高可靠 度及維持起始外觀，即使於高溫度/濕度及熱衝擊之條件下 長期操作後。 【韻^明内容^】 發明概要 本發明一方面係提供一種用於各向異性導電膜之組成 0 物。此組成物包含：一接合劑；一可固化組份；及導電顆 粒。接合劑包含(al)以化學式1表示之聚酯-聚矽氧烷共聚 物： hr (A)aB， 其中，“a”係1或更大之整數，（A)係一具有 H-[0-(CRl2)n-CO-]m-X-R2-之結構之聚酯單元，且B係一具有 結構之聚矽氧 烧單元， Q 其中，於(A)，X係氧或NRX(RX表示一具有1至20個碳原 子之單價之經取代或未經取代之烴基，其中，個別之碳原 子可以氧原子、氫，或-SiR’2-R2-NR’取代，其中，R，係彼此 相同或相異，JL表示一單價之經取代或未經取代之烴基， 且R2表示一具有1至40個碳原子之二價之經取代或未經取 代之烴基，其中，個別之碳原子可以氧原子取代），R1表示 氫或一單價之經取代或未經取代之烴基，且係彼此相同或 相異，R2表示一具有1至40個碳原子之之二價之經取代或未 經取代之烴基，其中’個別之碳原子可以氧原子取代，η係 5 201035276 從3至10之整數，且m係從丨至仞㈨之整數；且 其中，於(B)，R3係彼此相同或相異，且表示一具有^ 至2〇個碳原子之經取代或未縣代之脂族飽和或不飽和之 線性、環狀或分支之烴或烴氧基，或—具有6錢個碳原子 之經取代絲娜代之料独或㈣频氧基，Μ係彼 此相同或相異’且麵-具有丨至職碳原子之經取代或未 經取代之麟飽和之線性、環狀或分支之烴或烴氧基或 -具有6至2G個碳原子之經取代或未縣代之料族煙或 芳香族烴氧基’ p係0至3_之整數，_至5〇之整數，喺 〇或更大之整數，且t係1或更大之整數。 接合劑可包含(al)聚醋-聚矽氧烷共聚物，及(a2)至少一 選自丙烯腈樹脂、苯乙稀_丙稀腈樹脂、甲基丙稀酸甲醋_ 烯本乙細樹月曰、丁一燦樹脂、丙烯酸樹脂、胺基甲酸 酯樹脂、環氧樹脂、苯氧樹脂、聚醯胺樹脂、烯烴樹脂、 夕酮樹月日、5^乙稀醇縮丁酸樹脂、聚乙稀醇縮甲链樹脂， 及聚酯樹脂所組成族群之基質樹脂。 基貝樹脂（a2)可具有約1,000〜1，000,000之重量平均分 子量。 可口化組伤可為（甲基）丙烯酸酯自由基可固化材料或 環氧樹脂。 ^電顆粒可包含選自包含Au、Ag、Ni、Cu，及Pb之金 屬顆粒，顆粒；以金屬塗覆之聚合物樹賴粒；及於以 金屬塗覆之聚合物樹脂顆粒之表面上之經表面絕緣處理之 顆粒所組成族群之至少一者。 201035276 叙成物可進一步包含添加劑’諸如，偶合劑、填料、 曰―幻、聚合反應抑制劑、抗氧化劑、熱穩定劑、固化加 速劑等。 於—實施例，用於各向異性導電膜之組成物可包含： (a)接合劑；（bl)(甲基）丙烯酸酯自由基可固化材料；（cl)自 由基起始劑；及(d)導電顆粒。接合劑(a)以固體含量而言可 約5至約75重量％之聚酯-聚石夕氧烧共聚物（al)，其係以 0 1〇0重量％之接合劑為基準。 用於各向異性導電膜之組成物可包含：（a)l〇〇重量份之 , 接合劑；（bl)約1〇〇至約3〇〇重量份之（曱基）丙烯酸酯自由基 — 可固化材料；（cl)約5至約15重量份之自由基起始劑；及(d) 約10至約40重量份之導電顆粒。 (甲基）丙烯酸酯自由基可固化材料可包含（曱基）丙烯 酸酯單體、（甲基）丙烯酸酯寡聚物，或其等之混合物。 (甲基）丙烯酸酯單體可包含含羥基基團之（曱基）丙稀 〇 酸8旨、匸㈣線性烷基（曱基）丙烯酸酯、Cl_2()分支烷基（甲基) 丙烯酸酯、C6_20芳基（甲基）丙烯酸酯、c62〇芳基烷基（曱基) 丙烯酸酯、（：6_2〇環烷基（甲基）丙烯酸酯、多環狀（甲基）丙烯 酸酯、雜環狀（甲基）丙烯酸酯、含醚基團之烷基（曱基）丙烯 酸酯、含環氧基團之烷基（曱基）丙烯酸酯、含芳氧基基團之 (甲基）丙烯酸酯、炫撐基二醇（甲基）丙稀酸酯、雙紛-A二（甲 基）丙烯酸酯、以芴為主之（甲基）丙烯酸酯等。 (甲基）丙烯酸酯募聚物可包含以胺基甲酸酯為主之（甲 基）丙稀酸酯、以環氧為主之（甲基）丙埽酸酯、以聚酯為主 7 201035276 之（曱基）丙烯酸酯、以氟為主之（甲基）丙稀酸酯、以芴為主 之（甲基）丙烯酸酯、以矽為主之（甲基）丙烯酸酯、以磷酸為 主之（曱基）丙烯酸酯、以馬來醯亞胺改質之（甲基）丙烯酸 酯、丙烯酸酯（曱基丙烯酸酯）等。（甲基）丙烯酸酯寡聚物可 具有約1,000〜1,000,000之重量平均分子量。 自由基起始劑可為選自光可聚合之起始劑及熱固化起 始劑所組成族群之至少一者。 用於各向異性導電膜之組成物可進一步以固體含量而 言包含約3至8重量份之偶合劑，其係以100重量份之接合劑 為基準。 於另一實施例’用於各向異性導電膜之組成物可包 含.（a)接合劑；（b2)環氧樹脂；（c2)固化劑；（d)導電顆粒； (e)偶合劑，及(f)填料’其中’接合劑⑷以固體含量而言包 含約3至細重量％之聚§旨·料氧料聚物⑻，其係以 100重量％之接合劑為基準。 用於各向異性導電臈之組成物可包含：⑻約100重量份 之接合劑Ub2)約25至約60重量份之環氧樹脂；㈣約5至 約20重量份之固化劑；⑷約5至約μ重量份之導電顆粒；⑹ 約1至約8重量份之偶合劑；及_1〇至約灣量份之填料。 環氧樹脂可包含選自雙盼型、_清漆型、縮水甘油 基型、脂族’及脂觀魏樹脂缝成族敎環氧單體、 環氧寡聚物，及環氧聚合物之一或多者。 固化劑可為選自㈣酐為主^份、㈣ 份 '以㈣為主之組份、以肼為主之級份，及以陽離子為 201035276 主之組份所組成族群之至少一者。 依據另一方面，提供一種自前述用於各向異性導電膜 之組成物製造之各向異性導電膜。 【實施方式3 實施例之詳細說明 本發明之一方面係有關於一種用於各向異性導電膜之 組成物。此用於各向異性導電膜之組成物包含：一接合劑、 ^ 一可固化組份，及導電顆粒，其中，接合劑包含聚酯-聚矽 氧烷共聚物。 • 於一實施例’此組成物係自由基可固化型式，其使用 (曱基）丙烯酸酯自由基可固化材料作為可固化組份。 於另一實施例，此組成物係環氧型式，其使用環氧樹 脂作為可固化組份。 依據本發明之用於各向異性導電膜之組成物之組份將 更詳細說明。 q (a)接合劑 接合劑包含(al)聚酯-聚矽氧烷共聚物，及(a2)至少一基 質樹脂。 於一實施例，當（甲基）丙烯酸酯自由基可固化材料被作 為可固化組份，，接合劑包含約5至約75重量％之聚酯-聚矽 氧烷共聚物（al)及約25至約95重量％之基質樹脂(a2)。於此 範圍内，用於各向異性導電膜之組成物可提供良好之起始 黏著性及可罪度，同時藉由避免剝離而確保連接阻抗之高 可靠度及維持起始外觀’即使於高溫度/濕度及熱衝擊之條 9 201035276 件下長期操作後。 於另一實施例，當環氧樹脂被作為可固化組份，接合 劑包含約3至約60重量％之聚酯_聚矽氧烷共聚物（al)及約 40至約97重量％之基質樹脂(a2)。於此範圍内，用於各向異 性導電膜之組成物可提供良好起始黏著性及可靠度，同時 藉由避免刺離而確保連接阻抗之高可靠度及維持起始外 觀’即使於高溫度/濕度及熱衝擊條件下長期操作後。 (al)聚酯-聚矽氧烷共聚物 聚酯-聚矽氧烧共聚物(al)可以下列化學式丨表示： (A)aB， 其中，“a”係1或更大之整數，（A)係一具有 H-[0-(CRl2)n-C0-]m-X-R2-之結構之聚酯單元，且b係一具有 (R^SiO^p^R^SiOmWOmHUOmSiR42；^之結構之聚石夕氧 燒單元， 其中，於(A)，X係氧或NRX(RX表示一具有丨至20個碳原 子之單價之經取代或未經取代之烴基，其中，個別之峻原 子可以氧原子、氫，或-SiRirR2-NR'取代，其中，r’係彼此 相同或相異’且表示一單價之經取代或未經取代之烴基， 且R2表示一具有1至40個碳原子之二價之經取代或未經取 代之烴基，其中’個別之碳原子可以氧原子取代），Ri表示 氫或一單價之經取代或未經取代之烴基，且係彼此相同或 相異，R2表示一具有1至40個破原子之之二價之經取代或未 經取代之烴基，其中，個別之碳原子可以氧原子取代，η係 從3至10之整數，且m係從1至1000之整數；且 10 201035276 其中，於(B)，R3係彼此相同或相異，且表示一具有1 至20個碳原子之經取代或未經取代之脂族飽和或不飽和之 線性、環狀或分支之烴或烴氧基，或一具有6至20個碳原子 之經取代或未經取代之芳香族烴或芳香族烴氧基，R4係彼 此相同或相異’且表示一具有1至20個碳原子之經取代或未 經取代之脂族飽和之線性、環狀或分支之烴或烴氧基，或 一具有6至20個碳原子之經取代或未經取代之芳香族烴或 芳香族烴氧基’ P係〇至3000之整數，q係〇至5〇之整數，以系 〇 〇或更大之整數，且t係1或更大之整數。 組成物之聚S旨-聚石夕氧院共聚物（al)經由調整聚合化程 度及聚石夕氧烧與聚醋之含量比例而顯現數個較佳性質。與 、 一簡單混合物相比，聚矽氧烷及聚酯間之化學接合提供聚 醋-聚矽氧烷共聚物(al)較佳物理性質。再者，聚自旨_聚石夕氧 烧共聚物（al)顯現無渗出之效果。 聚石夕氧烧易顯示對基本材料之高親和力且展現與其它 Q 有機化合物之低相容性。但是，聚酯與聚矽氧烷之共聚合 導致諸如可溶性、流動性、與和種物件之黏著性、耐熱性、 耐衝擊性、耐候性、塗覆性質等之整體性質之改良。 聚酯-聚矽氧烷共聚物可依其一主要組份而定具有各 種物理性質。當共聚物之主要組份係聚酿時，共聚物改良 耐濕性/防火性、耐候性、抗磨損效果、抗黏性、防滑性等， 如此，共聚物可作為各向異性導電膜及表面塗覆材料各種 塗覆組成物之接合劑或添加劑。 當共聚物之主要組份係聚石夕氧烧時，共聚物改良電及 201035276 機械性質，如此，共聚物可用於各向異性導電膜，及電及 電子組件、層合電路板、複合材料、漆料、黏著劑、結構 材料、耐腐蝕材料等。 再者’組成物之聚酯-聚矽氧烷共聚物(al)可改良包含 於接合劑内之各種熱固性及/或熱塑性樹脂之性質。可添加 聚酯-聚矽氧烷共聚物(al)之熱固性樹脂之例子包含：環氧 樹脂、聚胺基甲酸酯、聚尿素、聚醯胺、不飽和聚酯樹脂、 聚酯-聚醚共聚物、聚醯亞胺、黑色素樹脂、酚樹脂、二烯 丙基酞酸酯樹脂，及其等之衍生物。可添加聚酯-聚矽氧烷 共聚物(al)之熱塑性樹脂之例子包含：聚丙烯腈、聚曱基丙 烯腈、聚丙烯酸甲酯、聚丙烯醯胺、聚甲基丙烯酸酯、聚 甲基丙烯酸酯，及其它丙烯酸酯、聚笨乙烯、聚酯、聚醯 胺、聚酯醯胺、聚胺基甲酸酯、聚氣乙烯、聚碳酸酯、聚 縮醛、聚偏二氣乙烯' 聚乙烯醇及纖維素衍生物。 於一實施例，當（甲基）丙烯酸酯自由基可固化材料被作 為可固化組份，接合劑以固體含量而言可包含約5至約75重 量％之聚酯-聚矽氧烷共聚物（al)，其係以接合劑之100重量 %為基準。於此範圍内，膜組成物改良膜之可靠度且不會 使其外觀惡化。 於另一實施例，當環氧樹脂作為可固化組份，接合劑 以固體含量而言可包含約3至約60重量％之聚酯-聚矽氧烷 共聚物（al)，其係以1〇〇重量％之接合劑為基準。於此範圍 内，膜組成物改良膜之可靠度’且不會使其外觀惡化。 (a2)基質樹脂 12 201035276 基質樹脂(a2)構成作為形成各向異性導電膜之義質之 接合劑組份，且可為選自典型之熱固性/熱塑性樹月^至少 一者。 基質樹脂之例子可不受限地包含丙稀猜樹脂、笨 丙稀腈樹脂、甲基丙埽酸甲酿_ 丁二參苯乙稀樹脂'丁二稀 樹脂、丙烯酸樹脂、胺基甲_樹脂、環氧樹脂、笨縫 樹脂·聚醯胺樹脂、稀煙樹脂、石夕鋼樹脂、聚乙缚醇縮二 〇 _脂、聚乙烯醇縮甲酸樹脂，及聚酉旨樹脂。此等樹脂可 單獨或其以二或更多之組合物使用。較佳地，聚乙歸醇缩 . 谓樹脂、聚乙烯醇縮甲醛樹脂、聚醋樹脂、酚樹脂、環 、 氧糾脂、笨氧樹脂，及丙烯酸樹脂可被使用。 當（曱基）丙稀酸酿自由基可固化材料被作為可固化組 伤，丙稀腈樹脂、苯乙晞-丙烯腈樹脂、甲基丙歸酸甲醋_ 丁二烯-苯乙稀樹脂、丁二稀樹脂、丙稀酸樹脂、胺基甲酸 酯樹脂、聚醯胺樹脂、烯烴樹脂、矽酮樹脂、聚乙烯醇縮 〇 丁醛樹脂、聚乙烯醇縮甲醛樹脂，及聚酯樹脂可作為基質 樹脂(a2)。 當環氧樹脂被作為可固化組份，環氧樹脂、笨氧樹脂， 及甲基丙烯酸甲酯-丁二烯_苯乙烯樹脂可作為基質樹脂 (a2)。 於一實施例’基質樹脂可具有約10004 000 000之重 篁平均分子量。若基質樹脂之重量平均分子量少於1〇〇〇 , 膜之形成由於過度黏著性質（其不利於膜形成）而未令人滿 意地達成。用者，若基質樹脂之重量平均分子量超過 13 201035276 1,000,000,基質樹脂與參與固化反應之（曱基）丙稀酸酯寡聚 物及單體之相容性降低，因此，於製備組成物液體混合物 期間造成相分離。 特別地，苯乙烯-丙烯腈樹脂證明較佳可靠度。苯乙烯 -丙烯腈樹脂之例子包含苯乙烯-丙烯腈(SAN)共聚物、苯乙 烯-丙烯腈-丙烯酸酯(ASA)共聚物等。 若大量之具有高玻璃轉移溫度之熱塑性樹脂被用於促 進可靠度之目的，熱塑性樹脂提供一硬化結構，其於固化 後使此膜變硬及脆。因此，當此膜接受連續外部應力，此 應力未於此膜解除’因此，造成破裂或此膜物理性質惡化。 因此，此問題可藉由添加一具有低玻璃轉移溫度及展 現橡膠特性之樹脂解決。作為具有此一低玻璃轉移溫度及 展現橡膠特性之樹脂，聚合物樹脂可被使用，諸如，丙烯 腈樹脂、曱基丙烯酸酯-丁二烯-苯乙烯樹脂、丁二烯樹脂、 丙烯酸樹脂、胺基甲酸酯樹脂等。但是，當使用具有此一 低玻璃轉移溫度及展現橡膠特性之樹脂，此樹脂造成各向 異性導制於高溫及高濕度條件下膨脹，因此，造成此膜 之可靠度惡化。因此’樹脂之添加量被保持儘量低。特別 地’一核殼型結構之聚合物共聚物樹脂可被使用，其間， 核係由具有橡膠相及較低麵轉移溫度之聚合物樹脂组 成，諸如，丁二烯’且殼係由具有較高_轉移溫度之聚 合物樹脂組成，諸如’丙埽酸樹脂或苯乙浠樹脂，因此， 解決各向異性導電膜之應力解除及有關於可靠度之膨脹之 問題。核型結構之聚合物共聚物樹脂之例子包含G· C。·， 14 201035276201035276 VI. Description of the invention: [Rhyme 'Ming 斤 斤 ^ ^ ^ ^ ^ 贝 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ More particularly, the present invention relates to a polyester polyoxyalkylene copolymer by bowing to exhibit not only improved initial adhesion but also long-term operation even under high temperature/humidity and thermal shock conditions. A modified adhesive and a highly reliable composition for an anisotropic conductive film, and an anisotropic conductive film produced from the composition. I: Prior Art 1 Description of the Related Art Generally, an anisotropic (tetra) film system is an adhesive for dispersing conductive particles on a film. Anisotropic conductive films have been widely used to provide connections between electrical components such as '-LCD panels and-tape carrier packages (also referred to as "tastes" or between printed circuit boards and TCP, etc.). Furthermore, each (four) guiding surface has the attractiveness as an attractive material for the COG mounting and the connection of the CQF (4). The anisotropic conductive film is generally composed of a binder component, a curable component, and conductive particles. According to the curable component, the anisotropic conductive film is classified into (i) an epoxy type anisotropic conductive film, which is composed of an epoxy-based or expectant-based resin and a curing agent. The solidified component, and (8) a fine olefin, an age-oriented heterosexual lead, which is a curable component starting from a (meth)acrylic acid filament and a monomer and a radical. 3 201035276 In the epoxy anisotropic conductive film (i), the epoxy resin contains an aromatic benzene ring which forms a very strong network structure after curing, thus demonstrating good reliability. However, since the epoxy type anisotropic conductive film is required to have a plurality of aromatic benzene rings, it is difficult to adjust the resin fluidity at a high temperature and pressure, and a large number of bubbles are generated during the joining, thereby lowering the adhesion of the film. Furthermore, the conductive particles are not sufficiently placed between the circuits to be connected to each other. Further, the formation of the epoxy-type anisotropic conductive film requires extremely high reaction temperature and long reaction period, so that it is difficult to achieve method control and maintenance of the connection device. On the other hand, the acrylic type anisotropic conductive film (ii) can be rapidly cured in a few seconds via a rapid radical curing reaction, and the adhesion time can be remarkably lowered, thereby significantly promoting the production speed of the final anisotropic conductive film. However, the polymer resin having a low glass transition temperature generally used for film formation and fluidity adjustment causes repeated shrinkage and expansion of the anisotropic conductive film in a connected state between circuits, thereby deteriorating long-term reliability. Conversely, the use of a polymer resin having a high glass transition temperature in film formation causes difficulty in adjustment of fluidity, thus causing deterioration of initial physical properties such as connection failure, low adhesion, and the like. During this time, the reaction rate is lowered to ensure the connection between the conductive particles and the circuit. 'Because of the rheological characteristics between the binder component and the curable component, flow becomes difficult. Therefore, a large amount of bubbles are generated and long-term reliability is not guaranteed. . On the contrary, in the case where the reaction rate is increased, sufficient contact between the conductive particles and the circuit is not obtained, and therefore, good connection reliability cannot be ensured. In order to solve such problems of the related art, the present invention provides a composition for an anisotropic conductive film which comprises a polyester-polyoxyalkylene copolymer as a 201035276 oral component for good fluidity and high supply. The initial adhesion, while ensuring high reliability of the connection resistance and maintaining the initial appearance by avoiding peeling off in various applications, even after long-term operation under conditions of high temperature/humidity and thermal shock. [Rhyme content] Summary of the Invention In one aspect, the present invention provides a composition for an anisotropic conductive film. The composition comprises: a bonding agent; a curable component; and conductive particles. The bonding agent comprises (al) a polyester-polyoxyalkylene copolymer represented by Chemical Formula 1: hr (A) aB, wherein "a" is an integer of 1 or more, and (A) is one having H-[0 - (CRl2)n-CO-]mX-R2-structured polyester unit, and B is a structured polyoxo-oxygen unit, Q wherein, in (A), X-based oxygen or NRX (RX represents a a substituted or unsubstituted hydrocarbon group having a monovalent number of 1 to 20 carbon atoms, wherein the individual carbon atoms may be substituted with an oxygen atom, hydrogen, or -SiR'2-R2-NR', wherein R is the same as each other Or different, JL represents a monovalent substituted or unsubstituted hydrocarbon group, and R2 represents a divalent substituted or unsubstituted hydrocarbon group having 1 to 40 carbon atoms, wherein the individual carbon atoms can be oxygenated Atom substituted), R1 represents hydrogen or a monovalent substituted or unsubstituted hydrocarbon group and is the same or different from each other, and R2 represents a divalent substituted or unsubstituted one having 1 to 40 carbon atoms. a hydrocarbon group in which 'an individual carbon atom may be substituted with an oxygen atom, η system 5 201035276 is an integer from 3 to 10, and m is an integer from 丨 to 仞 (9); In (B), R3 is the same or different from each other and represents a linear, cyclic or branched hydrocarbon or hydrocarbon oxygen having a saturated or unsaturated aliphatic or unsaturated group having from 2 to 2 carbon atoms. a group, or a substituted sina or a (d) oxy group having 6 carbon atoms, which are the same or different from each other and have a substituted or unsubstituted carbon atom. Linear, cyclic or branched hydrocarbon or alkoxy group saturated with lin or - substituted or unsubstituted generation of a group of 6 or 2G carbon atoms or an aromatic hydrocarbon oxy 'p system 0 to 3 _ integer , an integer from _ to 5 喺〇, 喺〇 or a larger integer, and t is an integer of 1 or greater. The bonding agent may comprise (al) a polyacetamide-polyoxyalkylene copolymer, and (a2) at least one selected from the group consisting of acrylonitrile resin, styrene-acrylonitrile resin, methyl acetonate methyl vinegar Shuyue, Ding Yican resin, acrylic resin, urethane resin, epoxy resin, phenoxy resin, polyamide resin, olefin resin, ketene tree, 5^ ethyl alcohol butyrate resin A matrix resin of a group consisting of a polyethylene glycol chain-strand resin and a polyester resin. The base resin (a2) may have a weight average molecular weight of about 1,000 to 1,000,000. The palatable group injury can be a (meth) acrylate radical curable material or an epoxy resin. The electro-particles may comprise metal particles selected from the group consisting of Au, Ag, Ni, Cu, and Pb, particles; polymer-coated granules coated with metal; and on the surface of the polymer-coated resin particles coated with metal At least one of the group consisting of particles subjected to surface insulation treatment. The 201035276 composition may further comprise additives such as coupling agents, fillers, fluorene, polymerization inhibitors, antioxidants, heat stabilizers, curing accelerators, and the like. In the embodiment, the composition for the anisotropic conductive film may comprise: (a) a bonding agent; (bl) a (meth) acrylate radical curable material; (cl) a radical initiator; d) Conductive particles. The bonding agent (a) may be from about 5 to about 75% by weight, based on the solid content, of the polyester-polyoxanthene oxide copolymer (al) based on 0.1% by weight of the bonding agent. The composition for the anisotropic conductive film may comprise: (a) a part by weight of a bonding agent; (bl) from about 1 Torr to about 3 parts by weight of a (fluorenyl) acrylate radical - a curable material; (cl) from about 5 to about 15 parts by weight of a radical initiator; and (d) from about 10 to about 40 parts by weight of conductive particles. The (meth) acrylate radical curable material may comprise a (fluorenyl) acrylate monomer, a (meth) acrylate oligomer, or a mixture thereof. The (meth) acrylate monomer may comprise a hydroxyl group-containing (fluorenyl) acrylic acid, a ruthenium (tetra) linear alkyl (fluorenyl) acrylate, a Cl 2 () branched alkyl (meth) acrylate. , C6_20 aryl (meth) acrylate, c62 aryl aryl alkyl (fluorenyl) acrylate, (: 6 2 〇 cycloalkyl (meth) acrylate, polycyclic (meth) acrylate, heterocyclic (meth) acrylate, alkyl group (alkyl) acrylate containing ether group, alkyl (indenyl) acrylate containing epoxy group, (meth) acrylate containing aryloxy group , stilbene diol (meth) acrylate, bis-A bis (meth) acrylate, bismuth-based (meth) acrylate, etc. (meth) acrylate polymer Containing a urethane-based (meth) acrylate, an epoxy-based (meth) acrylate, a polyester-based 7 201035276 (mercapto) acrylate, Fluorine-based (meth) acrylate, bismuth-based (meth) acrylate, bismuth-based (meth) acrylate, phosphoric acid-based (Mercapto) acrylate, (meth) acrylate modified with maleimide, acrylate (methacrylate), etc. The (meth) acrylate oligomer may have a weight average of about 1,000 to 1,000,000. The radical initiator may be at least one selected from the group consisting of a photopolymerizable initiator and a heat curing initiator. The composition for the anisotropic conductive film may further comprise a solid content. About 3 to 8 parts by weight of the coupling agent based on 100 parts by weight of the bonding agent. In another embodiment, the composition for the anisotropic conductive film may comprise (a) a bonding agent; (b2) Epoxy resin; (c2) curing agent; (d) conductive particles; (e) coupling agent, and (f) filler 'wherein the bonding agent (4) contains about 3 to 3% by weight in terms of solid content. The oxygenate polymer (8) is based on 100% by weight of the bonding agent. The composition for anisotropic conductive crucible may comprise: (8) about 100 parts by weight of the bonding agent Ub2) from about 25 to about 60 parts by weight. Epoxy resin; (iv) from about 5 to about 20 parts by weight of curing agent; (4) from about 5 to about μ parts by weight Conductive particles; about 1 to about 8 parts by weight of the coupling agent ⑹; Wan and _1〇 to about an amount of filler parts. The epoxy resin may comprise one selected from the group consisting of a double-presence type, a varnish type, a glycidyl type, an aliphatic 'and a lipid-wetting resin, a bismuth epoxy monomer, an epoxy oligomer, and an epoxy polymer. Or more. The curing agent may be at least one selected from the group consisting of (four) anhydrides, (four) parts, (four)-based components, cesium-based fractions, and cations, 201035276 main components. According to another aspect, there is provided an anisotropic conductive film produced from the foregoing composition for an anisotropic conductive film. [Embodiment 3] DETAILED DESCRIPTION OF THE EMBODIMENTS One aspect of the invention relates to a composition for an anisotropic conductive film. The composition for an anisotropic conductive film comprises: a bonding agent, a curable component, and conductive particles, wherein the bonding agent comprises a polyester-polyoxyalkylene copolymer. • In one embodiment, the composition is a free-radically curable version using a (mercapto) acrylate radical curable material as the curable component. In another embodiment, the composition is an epoxy type which uses an epoxy resin as the curable component. The components for the composition of the anisotropic conductive film according to the present invention will be described in more detail. q (a) bonding agent The bonding agent comprises (al) a polyester-polyoxyalkylene copolymer, and (a2) at least one matrix resin. In one embodiment, when the (meth) acrylate radical curable material is used as the curable component, the binder comprises from about 5 to about 75% by weight of the polyester-polyoxyalkylene copolymer (al) and about 25 to about 95% by weight of the matrix resin (a2). Within this range, the composition for the anisotropic conductive film can provide good initial adhesion and sin, while ensuring high reliability of the connection resistance and maintaining the initial appearance by avoiding peeling, even at high Temperature/humidity and thermal shock strips 9 201035276 After long-term operation. In another embodiment, when the epoxy resin is used as the curable component, the bonding agent comprises from about 3 to about 60% by weight of the polyester-polyoxyalkylene copolymer (al) and from about 40 to about 97% by weight of the substrate. Resin (a2). Within this range, the composition for the anisotropic conductive film can provide good initial adhesion and reliability while ensuring high reliability of the connection resistance and maintaining the initial appearance by avoiding puncturing, even at high temperatures. / After long-term operation under humidity and thermal shock conditions. (al) Polyester-polyoxyalkylene copolymer The polyester-polyoxyalkylene oxide copolymer (al) may be represented by the following chemical formula: (A) aB, wherein "a" is an integer of 1 or more, (A Is a polyester unit having the structure of H-[0-(CRl2)n-C0-]mX-R2-, and b is a polylith having the structure of (R^SiO^p^R^SiOmWOmHUOmSiR42; An oxygen-burning unit, wherein, in (A), X-based oxygen or NRX (RX represents a monovalent substituted or unsubstituted hydrocarbon group having from 丨 to 20 carbon atoms, wherein the individual atom may be an oxygen atom, Hydrogen, or -SiRirR2-NR', wherein r' is the same or different from each other and represents a monovalent substituted or unsubstituted hydrocarbon group, and R2 represents a divalent having from 1 to 40 carbon atoms. a substituted or unsubstituted hydrocarbon group in which 'an individual carbon atom may be substituted with an oxygen atom), and Ri represents hydrogen or a monovalent substituted or unsubstituted hydrocarbon group which are the same or different from each other, and R 2 represents a one having 1 a divalent, substituted or unsubstituted hydrocarbon group of up to 40 atomic atoms, wherein the individual carbon atoms may be substituted with an oxygen atom, and the η system is an integer from 3 to 10, and m is an integer from 1 to 1000; and 10 201035276 wherein, in (B), R3 are the same or different from each other and represent a substituted or unsubstituted aliphatic saturated or unsubstituted having 1 to 20 carbon atoms a saturated linear, cyclic or branched hydrocarbon or alkoxy group, or a substituted or unsubstituted aromatic hydrocarbon or aromatic hydrocarbonoxy group having 6 to 20 carbon atoms, R4 being identical or different from each other' And represents a substituted or unsubstituted aliphatic saturated linear, cyclic or branched hydrocarbon or alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted having 6 to 20 carbon atoms The substituted aromatic hydrocarbon or aromatic hydrocarbonoxy 'P is 整数 to an integer of 3,000, q is 〇 to an integer of 5 ,, to an integer of 〇〇 or greater, and t is an integer of 1 or more. The composition of the poly(S)-polysocene copolymer (al) exhibits several preferred properties by adjusting the degree of polymerization and the ratio of polyoxo-oxygen to polyglycol. Compared with a simple mixture, The chemical bonding between the decane and the polyester provides the preferred physical properties of the polyacetal-polyoxyalkylene copolymer (al). The purpose of the poly-stone oxy-coal copolymer (al) is to show no oozing effect. The polyoxo oxy- oxime easily shows high affinity to the basic material and exhibits low compatibility with other Q organic compounds. However, polyester and The copolymerization of polyoxyalkylene leads to an improvement in the overall properties such as solubility, fluidity, adhesion to articles, heat resistance, impact resistance, weather resistance, coating properties, etc. Polyester-polysiloxane copolymerization The material may have various physical properties depending on one of its main components. When the main component of the copolymer is brewed, the copolymer improves moisture resistance/fire resistance, weather resistance, abrasion resistance, anti-stick property, and slip resistance. Alternatively, the copolymer can be used as a binder or additive for various coating compositions of anisotropic conductive films and surface coating materials. When the main component of the copolymer is agglomerated, the copolymer improves the electrical properties and the mechanical properties of 201035276. Thus, the copolymer can be used for anisotropic conductive films, and electrical and electronic components, laminated circuit boards, composite materials, Paints, adhesives, structural materials, corrosion resistant materials, etc. Further, the polyester-polyoxyalkylene copolymer (al) of the composition can improve the properties of various thermosetting and/or thermoplastic resins contained in the bonding agent. Examples of the thermosetting resin to which the polyester-polyoxyalkylene copolymer (al) may be added include: epoxy resin, polyurethane, polyurea, polyamine, unsaturated polyester resin, polyester-polyether Copolymers, polyimine, melanin resins, phenol resins, diallyl phthalate resins, and derivatives thereof. Examples of the thermoplastic resin to which the polyester-polyoxyalkylene copolymer (al) may be added include polyacrylonitrile, polydecyl acrylonitrile, polymethyl acrylate, polyacrylamide, polymethacrylate, polymethyl Acrylate, and other acrylates, polystyrene, polyester, polyamide, polyester decylamine, polyurethane, polyethylene, polycarbonate, polyacetal, polyvinylidene dioxide Vinyl alcohol and cellulose derivatives. In one embodiment, when the (meth) acrylate radical curable material is used as the curable component, the binder may comprise from about 5 to about 75% by weight of the polyester-polyoxyalkylene copolymer in terms of solid content. (al), based on 100% by weight of the bonding agent. Within this range, the film composition improves the reliability of the film without deteriorating its appearance. In another embodiment, when the epoxy resin is used as the curable component, the binder may comprise from about 3 to about 60% by weight of the polyester-polyoxyalkylene copolymer (al) in terms of solid content, which is 1 The binder of % by weight is based on the binder. Within this range, the film composition improves the reliability of the film' without deteriorating its appearance. (a2) Matrix resin 12 201035276 The matrix resin (a2) constitutes a binder component as a substance for forming an anisotropic conductive film, and may be at least one selected from the group consisting of typical thermosetting/thermoplastic trees. Examples of the matrix resin may include, without limitation, propylene guess resin, acrylonitrile resin, methyl propyl phthalate, styrene diphenyl styrene resin, butyl diene resin, acrylic resin, amine methyl resin, Epoxy resin, stupid resin, polyamide resin, dilute smoke resin, Shishi steel resin, polyglycol condensate, fat, polyvinyl carboxylic acid resin, and polyphthalic acid resin. These resins may be used singly or in combination of two or more. Preferably, the polyethylene resin is a resin, a polyvinyl formal resin, a polyester resin, a phenol resin, a ring, an oxygen-correcting resin, an epoxy resin, and an acrylic resin. When the (mercapto) acrylic acid free radical curable material is used as a curable group, acrylonitrile resin, styrene-acrylonitrile resin, methyl propyl acetate _ butadiene-styrene resin , butyl dilute resin, acrylic resin, urethane resin, polyamide resin, olefin resin, fluorenone resin, polyvinyl butyral resin, polyvinyl formal resin, and polyester resin It can be used as a matrix resin (a2). When an epoxy resin is used as the curable component, an epoxy resin, an epoxy resin, and a methyl methacrylate-butadiene-styrene resin can be used as the matrix resin (a2). In one embodiment, the matrix resin can have a weight average molecular weight of about 10004 000 000. If the weight average molecular weight of the matrix resin is less than 1 Å, the formation of the film is not satisfactorily achieved due to the excessive adhesion property which is disadvantageous to film formation. If the weight average molecular weight of the matrix resin exceeds 13 201035276 1,000,000, the compatibility of the matrix resin with the (mercapto) acrylate oligomer and monomer involved in the curing reaction is lowered, thereby preparing a liquid mixture of the composition. Phase separation occurs during the period. In particular, styrene-acrylonitrile resins demonstrate better reliability. Examples of the styrene-acrylonitrile resin include a styrene-acrylonitrile (SAN) copolymer, a styrene-acrylonitrile-acrylate (ASA) copolymer, and the like. If a large amount of thermoplastic resin having a high glass transition temperature is used for the purpose of promoting reliability, the thermoplastic resin provides a hardened structure which makes the film hard and brittle after curing. Therefore, when the film receives a continuous external stress, the stress is not released from the film. Therefore, cracking or deterioration of the physical properties of the film is caused. Therefore, this problem can be solved by adding a resin having a low glass transition temperature and exhibiting rubber properties. As the resin having such a low glass transition temperature and exhibiting rubber characteristics, a polymer resin such as an acrylonitrile resin, a methacrylate-butadiene-styrene resin, a butadiene resin, an acrylic resin, an amine can be used. Carbamate resin and the like. However, when a resin having such a low glass transition temperature and exhibiting rubber properties is used, the resin causes the anisotropy to be expanded under high temperature and high humidity conditions, thereby deteriorating the reliability of the film. Therefore, the amount of resin added is kept as low as possible. In particular, a polymer core copolymer resin having a core-shell structure may be used, in which the core system is composed of a polymer resin having a rubber phase and a lower surface transfer temperature, such as butadiene' The high-transfer temperature polymer resin composition, such as 'propionic acid resin or styrene resin, therefore solves the problem of stress relief of the anisotropic conductive film and expansion of reliability. An example of a polymer copolymer resin having a core structure includes G·C. ·, 14 201035276
Ltd.生產之 AC 系列、Resinous Kasei Co·，Ltd.生產之Rkb 系 列等。在此，RKB系列係其間一由甲基丙烯酸甲酯丁二烯 -苯乙烯等組成之核殼共聚物樹脂分散於環氧樹脂之產物。 基質樹脂(a2)可以約5至約50重量％之量使用，其係以 1〇〇重量％之組成物為基準。於此範圍内，各向異性導電膜 不會遭受膜性質、外觀，及連接阻抗惡化。 b)可固化組份 由基可固化材料或⑽)The AC series manufactured by Ltd., the Rkb series manufactured by Resinous Kasei Co., Ltd., and the like. Here, the RKB series is a product in which a core-shell copolymer resin composed of methyl methacrylate butadiene-styrene or the like is dispersed in an epoxy resin. The matrix resin (a2) may be used in an amount of from about 5 to about 50% by weight based on 1% by weight of the composition. Within this range, the anisotropic conductive film does not suffer from film properties, appearance, and deterioration of connection resistance. b) curable component from base curable material or (10))
於本發明’（M)(甲基）丙烯酸酯自 環氧樹脂可作為可固化組份。 M)自由基可固化材料 自由基可固化材料可為（甲基）丙烯酸酯寡聚物、（甲某) 丙烯酸酯單體，或其等之混合物。 土 (甲基）丙烯酸酯自由基可固化材料(bl)以固體含量而 言可以約100至約300重量份之量使用，其係以1〇〇重量广之 接合劑為基準。於此範圍内，組成物提供良好外觀及固化 性質，及以與物件之接觸、可靠度，及膜性暂 非又夂膜㈣而t㈣較 佳性。 (bll)(甲基）丙烯酸酯寡聚物 一或多種選自此項技藝已知之任何適合（甲基）丙稀酸 酯募聚物族群之寡聚物可作為（曱基）丙烯酸酯募聚物。較佳 地’（甲基）丙烯酸酯募聚物可為以胺基曱酸酯為主之（曱某) 丙烯S文酯、以環氧為主之（甲基）丙烯酸酯、以聚鲳為主之（曱 基）丙烯酸酯、以氟為主之（甲基）丙烯酸酯、以 ，主之（甲 土）丙烯酸酯、以矽為主之（甲基）丙烯酸酯、以磷酸為主之 15 201035276 (甲基）丙烯酸酯、以馬來醯亞胺為主之（曱基）丙烯酸酯、丙 烯酸酯（甲基丙烯酸酯）等，其具有約1，〇〇〇〜1,000,〇〇〇範圍之 重量平均分子量。此等化合物可單獨或以其二或更多者之 組合物使用。 特別地，以胺基甲酸酯為主之（甲基）丙烯酸酯可具有自 多元醇，諸如，聚酯多元醇、聚醚多元醇、聚碳酸酯多元 醇、聚己内酯多元醇、四氫°夫喃-環氧丙烧開環共聚物、聚 丁二醇、聚二甲基矽氧烷二醇、乙二醇、丙二醇、1,4-丁二 醇、1,5-戊二醇、1,6-己二醇、新戊二醇、1,4-環己烷二甲 醇、雙酚A '氫化雙酚A等；及異氰酸酯化合物，諸如，2,4-甲苯二異氰酸酯、1,3-二甲苯二異氰酸酯、1,4-二甲苯二異 氰酸酯、1，5-萘二異氰酸酯、1,6-己烷二異氰酸酯、異佛爾 酮二異氰酸酯等合成之此分子之中間結構。 以環氧為主之（曱基）丙烯酸酯可具有包含一 2-溴氫 醌、間苯二酚、鄰苯二酚、雙酚(雙酚A、雙酚F、雙酚AD、 雙酚S等）、4,4’-二羥基聯笨、雙(4-羥基苯基)醚等之主幹， 及一或更多之取代基，諸如，烷基基團、芳基基團、曱基 醇基團、環狀脂族基團、鹵素（四溴雙酚A)等，之此分子之 中間結構。 此外，（曱基）丙烯酸酯寡聚物可含有至少二馬來醯亞胺 基團，且不受限地包含1-曱基-2,4-雙馬來醯亞胺苯、NW-間-苯撐基雙馬來醯亞胺、Ν,Ν'-對-苯撐基雙馬來醯亞胺、 NW-間-曱苯撐基雙馬來醯亞胺、Ν,ΝΓ-4,4-聯苯撐基雙馬來 醯亞胺、NW-4,4-(3,3^二曱基-聯苯撐基）雙馬來醯亞胺、 16 201035276 Ν，Ν’·4,4-(3,3’-二甲基二笨基甲烷）雙馬來醯亞胺、 N,N -4,4-(3,3 -—乙基二苯基甲炫)雙馬來醯亞胺、ν，ν，-4,4_ 二苯基甲烷雙馬來醯亞胺、Ν，Ν，_4,4_二苯基丙烷雙馬來醯 亞胺、Ν，Ν-4,4-二笨基醚雙馬來醯亞胺、 砜雙馬來醯亞胺、2,2_雙[4_(4_馬來醯亞胺基笨氧基）苯基] 丙烷' 2,2-雙[3-s-丁基_4_(4_馬來醯亞胺基笨氧基）苯基]丙 烷、U-雙[4-(4-馬來醯亞胺基苯氧基）苯基]癸烷、4 4，亞環 己基雙[Η4-馬來醯亞胺基苯氧基)_2環己基苯及2,2林 [4-(4-馬來醯亞胺基笨氧基）苯基]六氟丙烷。此等化合物可 單獨或以其二或更多者之組合物使用。 於Λ施例’（甲基）丙稀酸酯寡聚物可包含以下列化學 式2表示之自芴衍生物獲得之以芴為主之（甲基）丙烯酸酯：The '(M)(meth)acrylate self-epoxy resin of the present invention can be used as a curable component. M) Radical Curable Material The radical curable material may be a (meth) acrylate oligomer, a (meth) acrylate monomer, or a mixture thereof. The soil (meth) acrylate radical curable material (b1) may be used in an amount of from about 100 to about 300 parts by weight based on the total weight of the binder. Within this range, the composition provides good appearance and curing properties, and is in contact with the article, reliability, and film properties are not good for the film (4) and t (four). (bll) (meth)acrylate oligomers One or more oligomers selected from any suitable (meth) acrylate ester polymer group known in the art can be used as (mercapto) acrylates to condense Things. Preferably, the '(meth)acrylate convergent polymer is an amino phthalate-based bismuth acrylate, an epoxy-based (meth) acrylate, and a polyfluorene. The main (mercapto) acrylate, fluorine-based (meth) acrylate, the main (methane) acrylate, bismuth-based (meth) acrylate, phosphoric acid-based 15 201035276 (meth) acrylate, maleic imine-based (fluorenyl) acrylate, acrylate (methacrylate), etc., having a range of about 1, 〇〇〇 to 1,000, 〇〇〇 Weight average molecular weight. These compounds may be used singly or in combination of two or more thereof. In particular, the urethane-based (meth) acrylate may have a self-polyol such as a polyester polyol, a polyether polyol, a polycarbonate polyol, a polycaprolactone polyol, or four. Hydrogen-propanol-glycidyl open-loop copolymer, polytetramethylene glycol, polydimethyloxanediol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol 1,6-hexanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, bisphenol A 'hydrogenated bisphenol A, etc.; and an isocyanate compound such as 2,4-toluene diisocyanate, 1, Intermediate structure of this molecule synthesized by 3-xylene diisocyanate, 1,4-dimethylbenzene diisocyanate, 1,5-naphthalene diisocyanate, 1,6-hexane diisocyanate, isophorone diisocyanate or the like. The epoxy-based (fluorenyl) acrylate may have a 2-bromohydroquinone, resorcinol, catechol, bisphenol (bisphenol A, bisphenol F, bisphenol AD, bisphenol S). Or the like, 4,4'-dihydroxy phenyl, bis(4-hydroxyphenyl) ether or the like, and one or more substituents such as an alkyl group, an aryl group, a mercapto alcohol a group, a cyclic aliphatic group, a halogen (tetrabromobisphenol A), etc., the intermediate structure of this molecule. Further, the (fluorenyl) acrylate oligomer may contain at least a dimaleimide group, and includes, without limitation, 1-mercapto-2,4-bismaleimide benzene, NW-inter- Benzene-based bismaleimide, hydrazine, Ν'-p-phenylene bismaleimide, NW-m-p-phenylene bismaleimide, hydrazine, ΝΓ-4,4- Biphenylene bismaleimide, NW-4,4-(3,3^didecyl-biphenylene) bismaleimide, 16 201035276 Ν,Ν'·4,4-( 3,3'-Dimethyldipyridylmethane)Bismaleimide, N,N-4,4-(3,3--ethyldiphenylmethano)Bismaleimide, ν ,ν,-4,4_ diphenylmethane bismaleimide, anthracene, anthracene, _4,4_diphenylpropane, bismaleimide, anthracene, anthracene-4,4-diphenyl ether Maleidin, sulfone, bismaleimide, 2,2_bis[4_(4_maleimido)oxy]phenyl]propane' 2,2-bis[3-s-butyl Base_4_(4_maleimidophenyloxy)phenyl]propane, U-bis[4-(4-maleimidophenoxy)phenyl]decane, 4 4, Cyclohexyl bis[Η4-maleimidophenoxy)_2cyclohexylbenzene and 2,2 lin [4-(4-maleimido)oxy]phenyl]hexa Fluoropropane. These compounds can be used singly or in combination of two or more thereof. The (meth) acrylate oligomer may contain a fluorene-based (meth) acrylate obtained from the hydrazine derivative represented by the following Chemical Formula 2:
〇 其中，R獨立地表示—烷基基團、一烷氧基基團、一 芳基基團，或一環烷基基團，之整數，且nS2~52 整數。 以苟為主之（甲基）丙烯醆酯之例子包含以芴為主之環 氧（曱基）丙烯酸酯寡聚物、芴胺基甲酸酯（甲基）丙烯酸酯寡 聚物等。 特別地，以努為主之環氧（甲基）丙烯酸酯寡聚物可藉由 於5 0 ~ 12 0 °C於一溶劑内使芴化合物與縮水甘油基（甲基）丙 烯酸酯反應5至30小時而獲得。芴胺基甲酸酯（甲基）丙烯酸 17 201035276 酯寡聚物可藉由於酯中使苟二醇衍生物與二異氰酸酯及羥 基（甲基）丙烯酸酯反應而獲得。溶劑之例子可包含烷撐基單 烷基醚乙酸酯，諸如，甲基溶纖劑乙酸酯、丙二醇單甲基 醚乙酸酯、3-甲氧基丁基_1_乙酸酯等、曱基乙基酮、甲基 戊基酮等。 使用一或多種之以芴為主之（曱基）丙烯酸酯寡聚物作 為（曱基）丙烯酸酯募聚物可藉由芴結構之較佳絕緣性質使 短路達最小且確保低起始連接阻抗及高可靠度，因此，改 良最終產物之生產力及可靠度。 (Μ2)(甲基）丙稀酸酯單體 (甲基）丙烯酸酯單體於此組成物帶作為一反應性稀釋 劑。 (甲基）丙烯酸酯單體可為選自此項技藝已知之任何適 合（甲基）丙烯酸酯單體之至少一者。 (曱基）丙稀酸酯單體之例子可不受限地包含含經基基 團之（曱基）丙烯酸酯、C^o線性烷基（甲基）丙烯酸酯、C^o 分支烧基（甲基）丙稀酸5旨、C6-20芳基（甲基）丙歸酸S旨、 芳基烷基（甲基）丙烯酸酯、含C6_20環烷基之（曱基）丙烯酸 酯、多環狀（曱基）丙烯酸酯、雜環狀（甲基）丙烯酸酯、含醚 基團之（曱基）丙烯酸酯、含環氧基困之（曱基）丙稀酸酯、含 芳氧基團之（曱基）丙稀酸酯、烷撐基二醇（甲基）丙烯酸酯、 雙酚-A二（甲基）丙烯酸酯、以芴為主之（曱基）丙稀酸酯、酸 碟氧基乙基（甲基）丙細酸醋荨。此等化合物可單獨或以其二 或更多者之組合物使用。 18 201035276 特別地，（甲基）丙烯酸酯單體之例子可包含1，6-己二醇 單（甲基）丙烯酸酯、2-羥基乙基（甲基）丙烯酸酯、2-羥基丙 基（甲基）丙姊酸Sb、2-輕基丁基（甲基）丙稀酸g旨、2-經基-3_ 苯氧基丙基（甲基）丙烯酸酯、1，4-丁二醇（甲基）丙烯酸酯、 2-羥基烷基（甲基）丙烯醯基磷酸酯、4-羥基環己基（甲基）丙 烯酸酯、新戊二醇單（甲基）丙烯酸酯、三甲基醇乙烷二（甲 基）丙烯酸酯、三甲基醇丙炫二（曱基）丙烯酸酯、季戊四醇 三（曱基）丙烯酸酯、二季戊四醇五（曱基）丙稀酸酯、季戊四 醇六（甲基）丙烯酸酯、二季戊四醇六（曱基）丙烯酸酯、甘油 二（曱基）丙烯酸酯、t-氫糠基（甲基）丙烯酸酯、異癸基（甲基） 丙烯酸酯' 2-(2-乙氧基乙氧基）乙基（甲基）丙烯酸酯、硬脂 基（甲基）丙姊酸醋、月桂基（甲基）丙稀酸酿、2-苯氧基乙基 (曱基）丙烯酸酯、異冰片基（甲基）丙烯酸酯、十三烷基（甲基） 丙烯酸酯、乙氧基化壬基酚（甲基）丙烯酸酯、乙二醇二（曱 基）丙烯酸酯、二甘醇二（曱基）丙烯酸酯、三甘醇二（甲基) 丙烯酸酯、t-乙二醇二（曱基）丙烯酸酯、聚乙二酵二（甲基) 丙烯酸酯、1，3-丁二醇二（甲基）丙烯酸酯、三丙甘醇二（甲基) 丙烯酸酯、乙氧基化雙酚·Α二（甲基）丙烯酸酯、環己烷二甲 醇二（曱基）丙烯酸酯、苯氧基-t-二醇二（甲基)丙烯酸酯、2_ 曱基丙浠醯氧基乙基磷酸酯、二曱基醇三環癸烷二（甲基) 丙烯酸酯、三甲基醇丙烷苯甲酸酯丙烯酸酯、以芴為主之 (曱基）丙烯酸酯、酸磷氧基乙基（甲基）丙烯酸酯等。此等化 合物可單獨或以其二或更多者之組合物使用。 作為（甲基）丙烯酸酯單體，以化學式2表示之具一场主 19 201035276 幹之以芴為主之基）丙烯酸酯單體可被使用。以芴為主之 (甲基）丙烯酸酯單體之例子包含此項技藝已知之以芴為主 之環氧（甲基）丙烯酸酯單體、以芴為主之胺基甲酸酯（甲美) 丙烯酸酯單體等。以芴為主之（甲基）丙烯酸酯單體一 得之例子係Osaka Gas Co.，Ltd.(日本）之BPEFA。 b2)環氧樹脂 環氧樹脂可包含選自雙酚型、酚醛清漆型、縮水甘、由 基型、脂族及脂環狀環氧樹脂所組成族群之環氧單體、产 氧寡聚物’及環氧聚合物之—或多者。環氧樹脂可選自二 項技藝已知之任何適合環氧樹脂，只要其包含 ^雙盼型、祕清漆型、縮水甘油基型、脂族、脂環^ 環氧樹脂等之分子結構之接合結構。 較佳地，於室溫係固體之環氧樹脂可與可添加 環乳樹脂之於室溫係液體之環氧樹脂使用。於室溫係 之％乳樹脂之例子衫限地包㈣料漆環氧樹脂 _清漆魏_旨、於請料二 甲盼 之雙，氧樹二： 二:':=限地包一_-其等 r氧環氧樹脂之例子不受限地包含二聚物酸改質之 質之環氧樹脂等。 妝土甲w曰改 除前述典型環氧樹脂外， 脂，其可藉㈣ 使用主之環氧樹 %刀子、、-。構之較佳絕緣性質使短路達最小且 20 201035276 ^低起始ί接阻抗及高可靠度，因此，改良最終產物之 力及可靠度。以苟為主之環氧之基本結構係以化學式2 表示。 %氧樹脂(b2)以固體冬旦工 ^ 口騷3里而言可以約25至約60重量份 之篁使用，其係以100重量份之接合劑為基準。於此範圍 内，組成物提供良好之顿及連接阻抗，且㈣較佳之可 靠度及膜性質。 可購知之壤氧樹脂之例子不受限地包含D E R _ 3 3【（陶氏Wherein R independently represents an alkyl group, an alkoxy group, an aryl group, or a cycloalkyl group, an integer, and an integer of nS2~52. Examples of the (meth) propylene oxime ester which is mainly ruthenium include an oxime-based oxime (meth) acrylate oligomer, a glutamate (meth) acrylate oligomer, and the like. In particular, the epoxy-based (meth) acrylate oligomer can be reacted with glycidyl (meth) acrylate by 5 to 30 ° C in a solvent in a solvent Obtained in hours. Amide (meth)acrylic acid 17 201035276 The ester oligomer can be obtained by reacting a decanediol derivative with a diisocyanate and a hydroxy (meth) acrylate in an ester. Examples of the solvent may include an alkylene monoalkyl ether acetate such as methyl cellosolve acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl_1_acetate, or the like. , mercapto ethyl ketone, methyl amyl ketone and the like. The use of one or more ruthenium-based (fluorenyl) acrylate oligomers as (mercapto) acrylate rallies minimizes short circuits and ensures low initial connection resistance by the preferred insulating properties of the ruthenium structure And high reliability, thus improving the productivity and reliability of the final product. (Μ2) (Methyl) acrylate monomer The (meth) acrylate monomer is used as a reactive diluent in this composition. The (meth) acrylate monomer can be at least one selected from any suitable (meth) acrylate monomer known in the art. Examples of the (mercapto) acrylate monomer may include, without limitation, a mercapto group-containing (fluorenyl) acrylate, a C^o linear alkyl (meth) acrylate, and a C^o branched alkyl group ( Methyl)acrylic acid 5, C6-20 aryl (meth)propionic acid S, arylalkyl (meth) acrylate, C6-20 cycloalkyl (fluorenyl) acrylate, polycyclic (mercapto) acrylate, heterocyclic (meth) acrylate, ether group-containing (fluorenyl) acrylate, epoxy group-containing (mercapto) acrylate, aryloxy group (mercapto) acrylate, alkylene glycol (meth) acrylate, bisphenol-A di(meth) acrylate, hydrazine-based (fluorenyl) acrylate, acid dish Oxyethyl (meth)propionate vinegar. These compounds may be used singly or in combination of two or more thereof. 18 201035276 In particular, examples of the (meth) acrylate monomer may include 1,6-hexanediol mono(meth)acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl ( Methyl)propionic acid Sb, 2-light butyl butyl (meth) acrylate, 2-carbyl-3 phenoxypropyl (meth) acrylate, 1,4-butane diol ( Methyl) acrylate, 2-hydroxyalkyl (meth) propylene decyl phosphate, 4-hydroxycyclohexyl (meth) acrylate, neopentyl glycol mono (meth) acrylate, trimethyl alcohol B Alkane di(meth)acrylate, trimethylol propionate (mercapto) acrylate, pentaerythritol tris(decyl) acrylate, dipentaerythritol penta(indenyl) acrylate, pentaerythritol hexa(methyl) Acrylate, dipentaerythritol hexa(meth) acrylate, glycerol di(decyl) acrylate, t-hydroindenyl (meth) acrylate, isodecyl (meth) acrylate ' 2- (2-B Oxyethoxyethyl)ethyl (meth) acrylate, stearyl (meth) propionate vinegar, lauryl (methyl) acrylic acid, 2-benzene Ethyl ethyl (fluorenyl) acrylate, isobornyl (meth) acrylate, tridecyl (meth) acrylate, ethoxylated nonyl phenol (meth) acrylate, ethylene glycol bis ( Mercapto) acrylate, diethylene glycol bis(indenyl) acrylate, triethylene glycol di(meth) acrylate, t-ethylene glycol di(decyl) acrylate, polyethylene diacetate di(methyl) Acrylate, 1,3-butanediol di(meth)acrylate, tripropylene glycol di(meth)acrylate, ethoxylated bisphenol·quinone di(meth)acrylate, cyclohexane Methanol bis(indenyl) acrylate, phenoxy-t-diol di(meth) acrylate, 2-mercaptopropoxy Ethyl phosphate, dinonyl alcohol tricyclodecane di (methyl) Acrylate, trimethylolpropane benzoate acrylate, fluorene-based (fluorenyl) acrylate, acid phosphorus oxyethyl (meth) acrylate, and the like. These compounds may be used singly or in combination of two or more thereof. As the (meth) acrylate monomer, an acrylate monomer represented by Chemical Formula 2, which is represented by Chemical Formula 2, can be used. Examples of the bismuth-based (meth) acrylate monomer include an oxime-based epoxy (meth) acrylate monomer known as ruthenium, and a ruthenium-based urethane (Kami ) Acrylate monomer and the like. An example of a bismuth-based (meth) acrylate monomer is BPEFA of Osaka Gas Co., Ltd. (Japan). B2) The epoxy resin epoxy resin may comprise an epoxy monomer selected from the group consisting of a bisphenol type, a novolac type, a glycidyl group, a group consisting of a base type, an aliphatic group and an aliphatic epoxy group, and an oxygen generating oligomer. 'and epoxy polymers - or more. The epoxy resin may be selected from any suitable epoxy resin known in the art as long as it comprises a molecular structure of a double-presence type, a secret varnish type, a glycidyl type, an aliphatic group, an alicyclic epoxy resin, or the like. . Preferably, the epoxy resin which is solid at room temperature can be used together with an epoxy resin which can be added to the room temperature liquid of the ring-shaped latex resin. Example of a % of milk resin at room temperature (4) paint epoxy resin _ varnish Wei _ purpose, in the request of dimethyl hope double, oxygen tree two: two: ': = limited land package _- Examples of the epoxy resin such as the epoxy resin include a dimer acid-modified epoxy resin. In addition to the above-mentioned typical epoxy resin, the grease can be used (4) to use the main epoxy tree, knives, and -. The preferred insulating properties of the structure minimize the short circuit and 20 201035276 ^ low initial impedance and high reliability, thus improving the strength and reliability of the final product. The basic structure of the epoxy-based epoxy is represented by Chemical Formula 2. The % oxy-resin (b2) may be used in an amount of from about 25 to about 60 parts by weight, based on 100 parts by weight of the binder, in terms of solids. Within this range, the composition provides good resistance and connection resistance, and (iv) better reliability and film properties. Examples of commercially available oxy-resin include, without limitation, D E R _ 3 3 [(Dow
^ib#) ' YDCN-500-80P (Kukdo Chemical) ' YDCN-500-90P (Kukdo Chemical)、YP_5〇 (T〇ht〇 Chemical)、pKFE (InChemRez)等。 cl)自由基起始劑 自由基起始劑（cl)係用於其間可固化組份係自由基可 固化材料之情況。自由基起始劑(cl)可包含光可聚合之起始 劑、熱固化起始劑’及其等之組合物。 自由基起始劑(cl)可為以過氧化物為主或以偶氮為主 之起始劑。以過氧化物為主之起始劑之例子不受限地包含 第三丁基過氧月桂酸酯、l，l，3,3-t-甲基丁基過氧-2-乙基己 酸酯、2,5-二曱基-2,5-二(2-乙基己醯基過氧）己烷、1-環己 基-1-甲基乙基過氧-2-乙基己酸醋、2,5-二曱基-2,5-二（間-曱苯醯基過氧）己烷、第三丁基過氧異丙基單碳酸酯、第三 丁基過氧-2-乙基己基單碳酸酯、第三己基過氧苯甲酸酯、 第三丁基過氧乙酸酯、二異丙苯基過氧化物、2,5-二曱基 -2,5-二（第三丁基過氧）己烷、第三丁基異丙苯基過氧化物、 21 201035276 第三己基過氧新癸酸醋、第三己基過氧-2-乙基己酸醋、第 三丁基過氧-2-2-乙基己酸醋 '第三丁基過氧異丁酸醋、u_ 雙（第三丁基過氧)環己烧、第三己基過氧異丙基單碳酸酯、 第三丁基過氧-3,5,5_三甲基己酸g旨、第三丁基過氧新戍酸 醋、異丙苯基過氧新癸酸醋、二異丙基苯過氧化氣、異丙 苯過氧化氫、異丁基過氧化物、2,4_二氯苯甲醯基過氧化 物、3,5,5-二甲基己醯基過氧化物、辛醯基過氧化物、月桂 醯基過氧化物、月桂基過氧化物、硬脂醯基過氧化物、琥 觸氧化物、苯m基過氧化物、3,5,5.三甲基己酿基魏 化物、苯甲醯基過氧甲苯、U，3,3_四甲基丁基過氧新癸酸 酯、1-環己基-1-甲基乙基過氧新癸酸酯、二正丙基過氧二 碳酸酯 '二異丙基過氧二碳酸酯、雙(4_第三丁基環己美） 過氧二碳酸酯、二-2-乙氧基甲氧基過氧二碳酸酯、二(2_^ 基己基過氧)二碳酸酯、二甲氧基丁基過氧二碳醆酯、二(3 甲基-3-甲氧基丁基過氧）二碳酸酯、匕卜雙（第二 —'已暴過 氧)-3,3,5-三曱基環己烷、1,1-雙（第三己基過氧)環己烷、1 1 雙（第三丁基過氧)-3,3,5-三甲基環己烷、U_(第二 ’斤 一1 j基過氧） 環十二烷、2,2-雙（第三丁基過氧)癸烷、第三丁其= 土〜甲基石夕 烷基過氧化物、雙（第三丁基)二曱基矽烷基過氧化物、第一 丁基三稀丙基石夕炫基過氧化物、雙（第三丁基）二稀内美 基過氧化物、三（第二丁基)稀丙基石夕烧基過氧化物等， 氣為主之起始劑之例子不受限地包含2,2f-偶fj 双·笑曱氧基 -2,4-二甲基戊腈）、二曱基-2,2'-偶氮雙(2-甲基丙酸购）、2 = 偶氮雙(N-環己基-2-甲基丙醯胺）、2,2-偶氮雙(2 4 _ ’ ，H~〜甲基戊 22 201035276 腈）2,2 -偶it雙(2_曱基丁腈）、Μ,偶氮雙[N_(2_丙稀基)_2_ :基丙酿胺]' 2,2,_偶氮雙(N-丁基-2-甲基丙醯胺）、2,2。偶 亂雙[N-(2-丙稀基)_2_甲基丙醯胺]、u，_偶氮雙(環己炫小 甲，）、Η(氰基-1-曱基己基)偶說]曱醯胺等。此等化合物 母者係單獨或其以—或更多者之組合物使用。 自由基起始劑(c2)以固體含量而言可以約5至約15重量 伤之里使用，其係以湖重量份之接合劑為基準。若自由基 起始劑之量少於5重量份，固化反應未被充份實施 ，因此， 使卜觀及可#度惡化。若自由基起始劑之量超過Μ重量 份’可能由於剩餘之基而有於耐腐似可靠度惡化之問題。 c2)固化劑 固化劑（c2)係用於其間可固化組份係環氧樹脂之情 況。固化劑(C2)可選自此項技藝已知之任何適合之環氧固化 型式之熱固化劑。固化劑(c 2)之例子可不受限地包含以酸酐 為主之組份、以胺為主之組份、以喃唾為主之組份、以肼 為主之組份，及以陽離子為主之組份。此等組份可單獨或 以其二或更多者之組合物使用。 以陽離子為主之組份可較佳地被使用，且包含，例如， 銨/銻六氟化物。 固化劑（c2)以固體而言可以約5至約20重量份之量使 用’其係以100重量份之接合劑為基準。若固化劑之量少於 5重量份，固化反應未被充份實施，因此，使外觀及可靠度 惡化。若固化劑之量超過約20重量份’可能由於剩餘固化 劑而有穩定性及可靠度惡化之問題。 23 201035276 d)導電顆粒 組成物之導電顆粒可作為填料以賦予組成物導電性 質。 導電顆粒可選自此項技藝已知之任何適合導電顆粒。 導電顆粒之例子可不受限地包含包含Au、Ag、Ni、Cu、 Sn、Ti及Pb之金屬顆粒；碳顆粒；以金屬塗覆之聚合物樹 脂顆粒；及於以金屬塗覆之聚合物樹脂顆粒之表面上之經 表面絕緣處理之顆粒。此等顆粒可單獨或以其二或更多者 之組合物使用。 石炭顆粒之例子可包含碳黑、石墨、活性破、碳鬚晶、 富勒烯、碳奈米管等。 聚合物樹脂之例子不受限地包含聚乙烯、聚丙烯、聚 酯、聚苯乙烯、聚乙烯醇等。 用於塗覆聚合物樹脂之金屬之例子可不受限地包含 Au、Ag、Ni 等。 導電顆粒之尺寸可依據依應用之電路間距而定之用途 而選擇，且係於約2至約30 μηι之範圍。 當組成物係自由基可固化型式，導電顆粒以固體含量 而言可以約10至約40重量份之量使用，其係以100重量份之 接合劑為基準。若導電顆粒之量少於約1〇重量份，連接失 敗會於連接期間於端子間未對準時由於連接區域減少而發 生，且若導電顆粒之量超過約40重量份，差的絕緣會發生。 當組成物係環氧固化型，導電顆粒以固體含量而言可 以約5至約25重量份之量使用，其係以100重量份之接合劑 24 201035276 為基準。於此範圍内，會不具有連接及絕緣失敗。 e) 偶合劑 〃偶口劑(e)可為至少一選自乙稀基三氯石夕院、乙稀基三 氧土石夕燒、3·環^丙氧基丙基三甲氧基石夕&、3-甲基丙稀 氧基丙基三甲氧基石夕院、2_胺基乙基冬胺基丙基甲基二甲 乳基石夕燒、3_脲基丙基三乙氧基石夕烧等之石夕烧偶合劑。 、、田、、且成物係基固化型式，偶合劑（e)以固體含量而言可 ◎ X約1〇或更少之重量份，且較佳係約3至約8重量份，之量 使用’其係以100重量份之接合劑為基準。 。田、、且成物係ί衣氧固化型式，固化劑⑷以固體含量而言 , 可以約1至約8重量份之量使用，其係以100重量份之接合劑 ' 為基準。 f) 填料 填料(f)可被包含於環氧固化型式組成物内。於此組成 物’填料(f)以固體含量而言可以約20至約50重量份之量使 Q 用，其係以100重量份之接合劑為基準。 特別地’填料可包含具有約5〜2〇nm尺寸之疏水性奈米 夕石顆粒。疏水性奈米石夕石顆粒可接受使用有機石夕烧之表 面處理。可購得之填料之例子不受限地包含Aer〇sil R-972、Ae⑽U R-搬、Ae⑽u R舰—R 8i2、A應u R-8200等。 填料(f)於接合及固化方法期間可提供適合流動性及一 膜固化結構，因此，藉由抑制高溫時之膨脹確保較佳之起 始黏著性及低連接阻抗。 25 201035276 於一實施例，用於各向異性導電膜之組成物可進一步 包含添加劑，諸如，增黏劑、聚合反應抑制劑、抗氧化劑、 熱穩定劑、固化加速劑等，以對此組成物提供另外物理性 質，且不會使基礎性質惡化。添加劑可單獨或以其二或更 多者之組合物使用。於此組成物，添加劑以固體含量而言 可以約0. 1至約5重量份之量使用，其係以100重量份之接合 劑為基準。 聚合反應抑制劑之例子可包含選自氳醌、氫醌單甲基 醚、對-苯醌、吩噻肼，及其等之混合物之至少一者。抗氧 化劑可包含酚或羥基肉桂酸酯化合物。抗氧化劑之例子可 包含四-(甲撐基-(3,5-二第三丁基-4-氫肉桂酸酯）曱烷、3,5-雙（1,1-二甲基乙基）-4-羥基苯丙酸硫醇二-2,1-乙烷二基 酯、十八烷基3,5-二第三丁基-4-羥基氫肉桂酸酯（可購自 (：化3(：〇.,1^1.)、2,6-二小對-甲基酚等。 固化加速劑可包含至少一選自固體之以咪唑為主之加 速劑，及固體及液體之以胺為主之固化加速劑等之加速 劑。需注意添加劑不限於此間揭露者。 依據本發明之另一方面，提供一種由如上所述之用於 各向異性導電膜之組成物形成之各向異性導電膜。製造此 各向異性導電膜之方法不限於特定方法。於一實施例，一 或多種選自構成接合劑之基質樹脂之樹脂溶於有機溶劑形 成一第一溶液，其與聚酯-聚矽氧烷共聚物、可固化組份及 導電顆粒以不被粉碎之速率攪拌一預定時間以形成一第二 溶液，其被塗敷於一離型膜至約10至約50 μιη之厚度，且乾 26 201035276 燥一預定時間以使有機溶劑蒸發，因此，形成一單層之各 向異性導電膜。在此，有機溶劑可選自此項技藝已知之任 何適合溶劑。上述方法可重複多次以形成一多層之各向異 性導電膜。 其次，本發明將參考合成實施例及其它實施例更詳細 地說明。需注意此等實施例僅作為例示而提供，且不限制 本發明之範圍。 實施例 〇 ^ 用於下列實施例及比較例之組份係如下： (a)接合劑 Μ , (al)聚酯-聚矽氧烷共聚物（Coentec GP 140 & Shin-Etsu KP-550P) (a2)基質樹脂 (a21)30重量％之溶於甲苯/甲基乙基酮共沸溶劑内之以 腈丁二稀橡膠(NBR)為主之樹脂(N-21，Nippon Zeon) (a22)25重量％之溶於甲基乙基酮内之以丙烯基為主之^ib#) 'YDCN-500-80P (Kukdo Chemical) 'YDCN-500-90P (Kukdo Chemical), YP_5〇 (T〇ht〇 Chemical), pKFE (InChemRez), and the like. Cl) Free radical initiator The radical initiator (cl) is used in the case where the curable component is a radical curable material. The radical initiator (cl) may comprise a photopolymerizable initiator, a heat curing initiator, and the like. The radical initiator (cl) may be a peroxide-based or azo-based initiator. Examples of peroxide-based initiators include, without limitation, tert-butylperoxylaurate, 1,1,3,3-t-methylbutylperoxy-2-ethylhexanoic acid. Ester, 2,5-dimercapto-2,5-di(2-ethylhexylperoxy)hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoic acid vinegar , 2,5-dimercapto-2,5-di(m-nonylphenyloxyperoxy)hexane, tert-butylperoxyisopropylmonocarbonate, tert-butylperoxy-2-ethyl Hexyl monocarbonate, third hexyl peroxybenzoate, tert-butyl peroxyacetate, dicumyl peroxide, 2,5-dimercapto-2,5-di (p. Tributyl peroxy) hexane, tert-butyl cumyl peroxide, 21 201035276 third hexyl peroxy neodecanoic acid vinegar, third hexyl peroxy-2-ethylhexanoic acid vinegar, third butyl Base peroxy-2-2-ethylhexanoic acid vinegar 't-butylperoxy isobutyric acid vinegar, u_bis(t-butylperoxy)cyclohexane, third hexylperoxyisopropyl monocarbonate , tert-butylperoxy-3,5,5-trimethylhexanoic acid g, t-butyl peroxy neodecanoic acid vinegar, cumyl peroxy neodecanoic acid vinegar, diisopropylbenzene Oxidation gas, cumene peroxygen Hydrogen, isobutyl peroxide, 2,4-dichlorobenzhydryl peroxide, 3,5,5-dimethylhexyl peroxide, octyl peroxide, lauryl peroxide , lauryl peroxide, stearyl peroxide, sulphate oxide, benzene m-based peroxide, 3,5,5. trimethylhexanyl-based, benzylidene-based peroxytoluene, U,3,3_tetramethylbutyl peroxy neodecanoate, 1-cyclohexyl-1-methylethyl peroxy neodecanoate, di-n-propyl peroxydicarbonate 'diisopropyl Peroxydicarbonate, bis(4_t-butylcyclohexyl)peroxydicarbonate, di-2-ethoxymethoxy peroxydicarbonate, bis(2-ylhexylperoxy)di Carbonate, dimethoxybutyl peroxydicarbonate, bis(3methyl-3-methoxybutylperoxy)dicarbonate, bismuth (secondary - 'over-oxygenated)- 3,3,5-trimethylcyclohexane, 1,1-bis(trihexylperoxy)cyclohexane, 1 1 bis(t-butylperoxy)-3,3,5-trimethyl Cyclohexane, U_(second' jin-1 y1 peroxy) cyclododecane, 2,2-bis(t-butylperoxy)decane, third butyl group = soil ~methyl sulphite Base , bis(tert-butyl)didecylfluorenyl peroxide, first butyltrisulphate, bis(t-butyl) dicarbemic peroxide, three (Second butyl), propyl sulfanyl peroxide, etc., examples of gas-based initiators include, without limitation, 2,2f-even fj bis-rhodium oxy-2,4-dimethyl Valeronitrile, dimercapto-2,2'-azobis(2-methylpropionic acid), 2 = azobis(N-cyclohexyl-2-methylpropanamide), 2,2 -Azobis(2 4 _ ' ,H~~methylpenta-22 201035276 nitrile) 2,2-octet bis(2_mercaptobutyronitrile), anthracene, azobis[N_(2-propyl) _2_ : propylamine] 2,2,-azobis(N-butyl-2-methylpropanamide), 2, 2. Occasionally double [N-(2-propionyl)_2-methylpropionamide], u, _ azobis(cyclohexyls), Η(cyano-1-indolyl) even ] guanamine and the like. The parent compounds of these compounds are used alone or in combination with - or more. The radical initiator (c2) may be used in an amount of from about 5 to about 15 parts by weight based on the solid content, based on the weight of the lake. If the amount of the radical initiator is less than 5 parts by weight, the curing reaction is not sufficiently carried out, so that the degree of deterioration and the degree of deterioration are deteriorated. If the amount of the radical initiator exceeds Μ by weight, there may be a problem that the corrosion resistance is deteriorated due to the remaining base. C2) Curing agent The curing agent (c2) is used for the case where the epoxy resin is a component. The curing agent (C2) may be selected from any suitable epoxy curing type of heat curing agent known in the art. Examples of the curing agent (c 2 ) may include, without limitation, an acid anhydride-based component, an amine-based component, a samarium-based component, a ruthenium-based component, and a cation. The main component. These components may be used singly or in combination of two or more thereof. A cation-based component can be preferably used, and includes, for example, ammonium/niobium hexafluoride. The curing agent (c2) may be used in an amount of from about 5 to about 20 parts by weight in terms of solids, based on 100 parts by weight of the bonding agent. If the amount of the curing agent is less than 5 parts by weight, the curing reaction is not sufficiently carried out, so that the appearance and reliability are deteriorated. If the amount of the curing agent exceeds about 20 parts by weight, there may be a problem of deterioration in stability and reliability due to the remaining curing agent. 23 201035276 d) Conductive particles The conductive particles of the composition act as a filler to impart conductivity to the composition. The electrically conductive particles can be selected from any suitable electrically conductive particles known in the art. Examples of the conductive particles may include, without limitation, metal particles containing Au, Ag, Ni, Cu, Sn, Ti, and Pb; carbon particles; polymer resin particles coated with metal; and polymer resins coated with metal Surface-treated particles on the surface of the particles. These particles may be used singly or in combination of two or more thereof. Examples of the charcoal particles may include carbon black, graphite, active broken, carbon whiskers, fullerenes, carbon nanotubes, and the like. Examples of the polymer resin include, without limitation, polyethylene, polypropylene, polyester, polystyrene, polyvinyl alcohol, and the like. Examples of the metal used for coating the polymer resin may include, without limitation, Au, Ag, Ni, and the like. The size of the conductive particles can be selected depending on the application depending on the circuit pitch of the application, and is in the range of about 2 to about 30 μm. When the composition is a radical curable type, the conductive particles may be used in an amount of from about 10 to about 40 parts by weight based on the solid content, based on 100 parts by weight of the binder. If the amount of the conductive particles is less than about 1 part by weight, the connection failure occurs due to a decrease in the connection area during misalignment between the terminals during the connection, and if the amount of the conductive particles exceeds about 40 parts by weight, poor insulation may occur. When the composition is epoxy-curable, the conductive particles may be used in an amount of from about 5 to about 25 parts by weight, based on 100 parts by weight of the bonding agent 24 201035276. Within this range, there will be no connection and insulation failure. e) coupling agent 〃 coupler (e) may be at least one selected from the group consisting of ethylene-triclosan, ethylene-trioxide, sulphur, and tris-propyloxypropyltrimethoxy sulphate & , 3-methylpropoxypropyltrimethoxy sylvestre, 2-aminoethylammonylpropylmethyl dimethyl milyl sulphate, 3- ureidopropyl triethoxy sulphur, etc. Shishi siu coupler. , the field, and the system based curing type, the coupling agent (e) may be in a solid content of about 10,000 or less by weight, and preferably from about 3 to about 8 parts by weight. The use is based on 100 parts by weight of the bonding agent. . The field, and the compound is an oxygen-cured type, and the curing agent (4) may be used in an amount of from about 1 to about 8 parts by weight, based on 100 parts by weight of the binder. f) Filler Filler (f) can be included in the epoxy cured version of the composition. The composition 'filler (f) may be used in an amount of from about 20 to about 50 parts by weight in terms of solid content, based on 100 parts by weight of the binder. In particular, the filler may comprise hydrophobic nano-stone particles having a size of about 5 to 2 〇 nm. Hydrophobic nano-stone particles can be treated with the surface treatment of organic stone. Examples of commercially available fillers include, without limitation, Aer〇sil R-972, Ae(10)U R-trans, Ae(10)u R-R 8i2, A should be u R-8200, and the like. The filler (f) provides suitable flowability and a film-cured structure during the bonding and curing process, thereby ensuring better initial adhesion and low connection resistance by suppressing expansion at high temperatures. 25 201035276 In one embodiment, the composition for an anisotropic conductive film may further contain an additive such as a tackifier, a polymerization inhibitor, an antioxidant, a heat stabilizer, a curing accelerator, etc. to the composition Provide additional physical properties without deteriorating the underlying properties. The additive may be used singly or in combination of two or more thereof. The composition may be used in an amount of from about 0.1 to about 5 parts by weight based on 100 parts by weight of the binder. Examples of the polymerization inhibitor may include at least one selected from the group consisting of hydrazine, hydroquinone monomethyl ether, p-benzoquinone, phenothiquinone, and the like. The antioxidant may comprise a phenol or a hydroxycinnamate compound. Examples of the antioxidant may include tetrakis-(methylidene-(3,5-di-t-butyl-4-hydrocinnamate) decane, 3,5-bis(1,1-dimethylethyl). 4-hydroxyphenylpropionic acid thiol di-2,1-ethanediester, octadecyl 3,5-di-t-butyl-4-hydroxyhydrocinnamate (available from (3) (: 〇., 1^1.), 2,6-di-p-methylphenol, etc. The curing accelerator may comprise at least one imidazole-based accelerator selected from solids, and amines as solid and liquid. An accelerator for a curing accelerator or the like as a main component. It is noted that the additive is not limited to the disclosed one. According to another aspect of the present invention, there is provided an anisotropy formed by the composition for an anisotropic conductive film as described above The conductive film. The method for producing the anisotropic conductive film is not limited to a specific method. In one embodiment, one or more resins selected from the matrix resin constituting the bonding agent are dissolved in an organic solvent to form a first solution, which is combined with a polyester- The polyoxyalkylene copolymer, the curable component and the electrically conductive particles are agitated at a rate not to be pulverized for a predetermined time to form a second solution which is applied to a release film to from about 10 to about 50. The thickness of μιη, and dry 26 201035276 is dried for a predetermined time to evaporate the organic solvent, thereby forming a single layer of an anisotropic conductive film. Here, the organic solvent may be selected from any suitable solvent known in the art. The invention may be repeated a plurality of times to form a multilayer anisotropic conductive film. Second, the present invention will be described in more detail with reference to the synthesis examples and other embodiments. It is to be noted that these embodiments are provided by way of illustration only and not limitation Scope of the Invention Example 用于 The components used in the following examples and comparative examples are as follows: (a) Adhesive Μ, (al) Polyester-polyoxyalkylene copolymer (Coentec GP 140 & Shin-Etsu KP-550P) (a2) 30% by weight of matrix resin (a21) Resin based on nitrile butadiene rubber (NBR) dissolved in toluene/methyl ethyl ketone azeotropic solvent (N-21, Nippon Zeon (a22) 25 wt% dissolved in methyl ethyl ketone based on propylene
Q 共聚物樹脂（KLS-1040, Fujikura Kasei Co. Ltd.) (a23)40重量％之溶於甲基乙基酮内之胺基甲酸酯樹脂 (KUB2001, Kangnam Chemical Co. Ltd.) (a24)30/30/40之重量比例之雙酚-A環氧樹脂/反應性環 氧稀釋劑/甲基丙烯酸甲酯-丁二烯-苯乙烯核殼共聚物之混 合物（RKB-2023, Reginous Kasei) (a25)30重量％之溶於甲苯内之以苯氧基為主之樹脂 (PKHH, Inchemrez Co. , Ltd. , USA) 27 201035276 (b)可固化組份 (bl)(曱基）丙烯酸酯自由基可固化枓料 (bi 1)胺基甲酸醋（甲基）丙烯酸嗤寡聚物（Miramer PU-330, Miwon Commercial) (b 12)3克之2-甲糧丙烯乳基乙基碌酸酷及ι〇克之季戊 四醇三-(甲基）丙烯酸酯之混合物 (b2)以環氧為主之樹脂 (b21)30重量％之溶於曱苯/曱基乙基酮共沸溶劑内之 環氧樹脂(JER-834, Japan Expoy Resin Co. Ltd ) (b22)30重量％之溶於甲苯/甲基乙基酮共沸溶劑内之 以芴為主之環氧樹脂（BPEFG, Osaka Gas Co.，Ltd.) (cl)熱固性自由基起始劑：苯甲醯基過氧化物 (c2)固化劑：芳香族銃六氟銻酸鹽（San aid SI-60L， Sanshin Chemical Co. , Ltd.) (d) 導電顆粒 (dl)具有5 μπι直徑之23GNR5· 0-MX(NCI製造） (d2)具有 5 μιη直徑之AULEB-004A(Sekisui Co. , Ltd.製 造） (e) 偶合劑：γ-環氧丙氧基丙基三甲氧基矽烧(kbm_4〇3, Shin-Etsu Chemical Co. , Ltd.) (f) 填料：接受以辛基矽烷表面處理之疏水性奈米矽石 顆粒（Aerosil R-805, Degussa) 實施例1-6 藉由混合第1表所示之組份而製備之每一組成物於室 28 201035276 溫(25°C)以300 rpm攪拌60分鐘。每一組成物係使用一塗膜 刮刀塗敷至一經矽離型劑處理之聚乙烯基底膜至20 μιη之 厚度。組成物於50°C乾燥10分鐘。 第1表 單位(克） 實施例 i Π 2 3 4 5 6 接合劑 (al) 1 10 20 1 10 20 (a21) 20 20 15 - - - (a22) 20 20 15 - - - (a23) 9 - - - - - (a24) - - - 25 25 25 (a25) - - - 19 10 - 可固化組份 (bll) 30 30 30 - - - (bl2) 13 13 13 - - - (b21) - - - 23 23 23 (b22) - - - 14 14 14 起始劑 (cl) 2 2 2 - - - (c2) 一 - - 3 3 3 導電顆粒 (dl) 5 5 5 - - - (d2) - - - 4 4 4 偶合劑 ⑹ 一 - - 1 1 1 填料 (f) - - - 10 10 10Q Copolymer Resin (KLS-1040, Fujikura Kasei Co. Ltd.) (a23) 40% by weight of urethane resin dissolved in methyl ethyl ketone (KUB2001, Kangnam Chemical Co. Ltd.) (a24 a mixture of bisphenol-A epoxy resin/reactive epoxy diluent/methyl methacrylate-butadiene-styrene core-shell copolymer in a weight ratio of 30/30/40 (RKB-2023, Reginous Kasei) (a25) 30% by weight of a phenoxy-based resin dissolved in toluene (PKHH, Inchemrez Co., Ltd., USA) 27 201035276 (b) Curable component (bl) (fluorenyl) acrylic acid Ester free radical curable pigment (bi 1) urethane methacrylate (Miramer PU-330, Miwon Commercial) (b 12) 3 g of 2-methyl propylene acrylate ethyl sulphonate A mixture of a fine and a gram of pentaerythritol tris-(meth) acrylate (b2) an epoxy resin-based resin (b21) 30% by weight of an epoxy resin dissolved in an azene/mercaptoethyl ketone azeotropic solvent Resin (JER-834, Japan Expoy Resin Co. Ltd) (b22) 30% by weight of ruthenium-based epoxy resin (BPEFG, Osaka Gas Co., dissolved in toluene/methyl ethyl ketone azeotropic solvent) Ltd.) (cl) Solid free radical initiator: benzylidene peroxide (c2) curing agent: aromatic hexafluoroantimonate (San aid SI-60L, Sanshin Chemical Co., Ltd.) (d) conductive particles ( Dl) 23GNR5·0-MX having a diameter of 5 μm (manufactured by NCI) (d2) AULEB-004A (manufactured by Sekisui Co., Ltd.) having a diameter of 5 μη (e) coupling agent: γ-glycidoxypropane (Trim_3〇3, Shin-Etsu Chemical Co., Ltd.) (f) Filler: accepting hydrophobic nano-fine particles treated with octyldecane (Aerosil R-805, Degussa) Examples 1-6 Each of the compositions prepared by mixing the components shown in Table 1 was stirred at room temperature for 28 minutes at room temperature of 20, 2010, and at 60 rpm for 60 minutes. Each of the compositions was applied to a polyethylene base film treated with a release agent to a thickness of 20 μm using a film doctor blade. The composition was dried at 50 ° C for 10 minutes. Table 1 (g) Example i Π 2 3 4 5 6 Adhesive (al) 1 10 20 1 10 20 (a21) 20 20 15 - - - (a22) 20 20 15 - - - (a23) 9 - - - - - (a24) - - - 25 25 25 (a25) - - - 19 10 - Curable component (bll) 30 30 30 - - - (bl2) 13 13 13 - - - (b21) - - - 23 23 23 (b22) - - - 14 14 14 Starting agent (cl) 2 2 2 - - - (c2) One - - 3 3 3 Conductive particles (dl) 5 5 5 - - - (d2) - - - 4 4 4 Coupler (6) One - - 1 1 1 Filler (f) - - - 10 10 10
比較例1~4 比較例係除第2表列示之組成物外藉由如上實施例相Comparative Examples 1 to 4 Comparative examples are the same as those listed in the second table by the above examples.
同方法獲得。 第2表 單位(克） 比較例 1 2 3 4 接合劑 (al) - 25 - 25 (a21) 20 15 - - (a22) 20 10 - - (a23) 10 - - - (a24) - - 25 20 (a25) - - 20 - 可固化組份 (bll) 30 30 - - (bl2) 13 13 - - (b21) - - 23 23 (b22) - - 14 14 起始劑 (cl) 2 2 - - (c2) - - 3 3 (dl) 5 5 - - 29 201035276 導電顆粒 (dl) 5 5 - _ 偶合劑 _ - - 4 4 填料 (f) - - 10 10 <各向異性導電膜之物理性質及可靠度之測試> 每一各向異性導電膜於室溫留置1小時，其後，於160 它及1秒之預壓縮條件下及180°C，5秒及3 MPa之主要壓縮 條件使用ITO(氧化銦錫）玻璃、COF及TCP(帶式載體封裝） 連接。七個樣品自每一各向異性導電膜獲得。然後，黏著 性及接觸接觸阻抗係使用此等樣品個別對於9〇。黏著 (ASTM D3330/D3330M-04)及4-探針方法（ASTM F43-64T) 作測試。再者，於高溫度/濕度之可靠度係藉由相同方法於 溫度85°C及85%之相對濕度持續丨〇〇〇小時之條件下測試 (ASTM D1H)。樣品之熱衝擊可靠度係藉由一4〇〇(：與8〇。c 間之振盪溫度持續1〇〇〇週期而評估(AStm D1183)。結果係 顯示於第3及4表。 第3表Obtained by the same method. Table 2 (g) Comparative Example 1 2 3 4 Adhesive (al) - 25 - 25 (a21) 20 15 - - (a22) 20 10 - - (a23) 10 - - - (a24) - - 25 20 (a25) - - 20 - Curable component (bll) 30 30 - - (bl2) 13 13 - - (b21) - - 23 23 (b22) - - 14 14 Starting agent (cl) 2 2 - - ( C2) - - 3 3 (dl) 5 5 - - 29 201035276 Conductive particles (dl) 5 5 - _ coupling agent _ - - 4 4 filler (f) - - 10 10 < physical properties of anisotropic conductive film and Reliability Test> Each anisotropic conductive film was left at room temperature for 1 hour, after which ITO was used under 160 pre-compression conditions and 1 second pre-compression conditions and 180 ° C, 5 seconds and 3 MPa main compression conditions. (Indium Tin Oxide) Glass, COF and TCP (Tape Carrier Package) connections. Seven samples were obtained from each anisotropic conductive film. Then, the adhesion and contact contact resistance were used individually for 9 〇. Adhesion (ASTM D3330/D3330M-04) and 4-probe method (ASTM F43-64T) were tested. Furthermore, the reliability at high temperature/humidity was tested by the same method at a temperature of 85 ° C and a relative humidity of 85% for a continuous hour (ASTM D1H). The thermal shock reliability of the sample was evaluated by an oscillation temperature of 8 〇〇 (: and 8 〇 c for 1 〇〇〇 period (AStm D1183). The results are shown in Tables 3 and 4. Table 3
ϋ 30 201035276 第4表 項目(Ω，Ohm) 起始黏著 性 高溫度/濕度可靠 度評估後之黏著 性 熱衝擊可靠度 評估後之黏著 性 實施例1 __1.30 3.85 3.95 實施例2 實施例3 0.77 2.97 2.89 1. 19 3. 31 3. 21 實施例4 1.21 3.91 3.98 實施例5 0. 77 2.98 2.91 實施例6 1.05 3.48 3.59 比較例1 2.56 5.21 5.46 比較例2 2.34 4.86 4.93 比較例3 2.19 6.44 5.80 比較例4 2. 11 5. 26 5. 47 如第3表所示，與比較例相比，實施例1至6於起始黏著 ^ 性及可靠度評估後之黏著性之項目展現較佳結果。再者， 如第4表所示，實施例丨至6展現比比較例更低之起始及於可 靠度評估後之阻抗。 雖然例示之實施例已被提供以例示本發明，其等僅係 用以例示，且各種改質及改變可由熟習此項技藝者於未偏 〇 離於所附申請專利範圍中所示之本發明之精神及範圍下為 之。再者，依據本發明之組成物包含所有之以化學式1表八 之聚酿-聚石夕氧院共聚物，且所附之申請專利範圍不限於此 化學式表示之種類，且包含與本發明之標的有關之所有改 質及改變。 【圖式簡單説明】 (無） 【主要元件符號說明】 (無） 31ϋ 30 201035276 Table 4 (Ω, Ohm) Adhesion after evaluation of adhesive thermal shock reliability after initial adhesion high temperature/humidity reliability Example 1 __1.30 3.85 3.95 Example 2 Example 3 0.77 2.97 2.89 1. 19 3. 31 3. 21 Example 4 1.21 3.91 3.98 Example 5 0. 77 2.98 2.91 Example 6 1.05 3.48 3.59 Comparative Example 1 2.56 5.21 5.46 Comparative Example 2 2.34 4.86 4.93 Comparative Example 3 2.19 6.44 5.80 Comparative Example 4 2. 11 5. 26 5. 47 As shown in Table 3, the adhesion properties of Examples 1 to 6 after initial adhesion and reliability evaluation showed better results than the comparative examples. . Further, as shown in the fourth table, the examples 丨 to 6 exhibited a lower starting point than the comparative example and an impedance after the reliability evaluation. The exemplified embodiments have been provided for exemplification of the present invention, and are intended to be illustrative only, and various modifications and changes can be made by those skilled in the art without departing from the scope of the appended claims. The spirit and scope of it. Furthermore, the composition according to the present invention comprises all of the poly-glycoside copolymers of the above formula 8 of the chemical formula 1, and the scope of the appended patent application is not limited to the type indicated by the chemical formula, and includes the invention. All changes and changes related to the subject matter. [Simple description of the diagram] (None) [Explanation of main component symbols] (None) 31