201105766 六、發明說明： 【發明所屬之技術領域】 本發明關係到可經由加熱而活化之膠帶，其在高溫下 具有非常低之流動性，並且在黏貼可撓性印刷電路板方 面，尤其在製造電子元件方面具有高度之交聯速度。 【先前技術】 具有可撓性之電子印刷電路板（“ Flexible Printed Circuit Boards” ，FPCBs;亦被稱之爲可撓性印刷電路板）在 今曰被使用在許多電子之設備中，諸如手機、收音機、電 腦、印表機以及許多其他之設備中。該等具有可撓性之電 子印刷電路板係由數層有裝設（尤其是有蝕刻）電子迴路之 可擦性銅層覆被薄板（“Flexible Copper Clad Laminates”， FCCL;亦被稱之爲銅層覆被薄板）所組成，其等於彼此之間 相互被黏貼。FCCL亦常被使用於電子之設備中。可撓性銅 層覆被薄板係由銅層及一層高熔點且具有阻抗能力之熱塑 性之塑膠，大多數之情況爲聚醯亞胺，較罕見者爲聚酯類， 諸如聚對苯二甲酸乙二酯（PET)或聚萘二甲酸乙二酯（PEN) 或液晶聚合物（LCP)，以及有些部分在其等之間還有一層黏 膠層等之層體所構成。 於製備FPCB或是以強化材料，即所謂之硬化劑強化 FCCL時，經常會使用到要求特別高之膠帶。一方面，在製 備可撓性銅層覆被薄板（FCCL)時，將銅層與聚醯亞胺層彼 此相互黏貼，此步驟通常係以丙烯酸黏膠組成物所完成； 另一方面，FPCB之各層FCCL彼此間亦相互黏貼，於該種 201105766 情況下’大多數之情形是聚醯亞胺層黏貼在聚醯亞胺層上 或是聚醯亞胺層黏貼在銅層上。除此之外，FCCL或完成之 FPCB還被黏貼在其他之基板（硬化材料，即所謂之「硬化 劑」）上以將該薄板做某種程度之硬化。可作爲強化材料使 用者例如有硬性玻璃纖維-環氧-板（FR-4)、聚醯亞胺、聚 酯、鋼及鋁。例如如果要在可撓性印刷電路板上裝設電子 元件’諸如晶片或類似之元件時及/或其等之使用係在於安 定時，則此尤其會引人關注。 對於用在該種黏貼上之膠帶有著非常高之要求。因爲 必須要達到非常高之黏貼功效、耐熱及耐化學藥品，所以 —般會使用可經由加熱而活化之膠帶，其等被使用於高溫 之下。此等膠帶於高溫之負載下在進行FPCB之黏貼時， 其經常在180°C之溫度下進行，而不會釋出揮發性之組成成 分。爲達到高度之內聚力，該等膠帶應於前述溫度之負載 下進行交聯網絡化反應。於進行黏貼之時要施予高壓以達 到良好之浸潤效果，此種黏貼大多數之情形係以熱壓方式 進行。有關於膠帶方面’以下之情況是有必要的，即膠帶 在高溫下僅能有非常低之流動性，以使其不會從黏接點處 被擠出。此可經由高黏稠度未經交聯網絡化之膠帶或經由 快速之交聯網絡化反應所達成。此外，該等膠帶接著還必 須耐得住焊浴之高溫，亦即是必須要經得住短時間非常高 溫之負載’例如288 °C。同時，於此經過黏貼之元件中不可 有氣泡產生。 基於此項理由，故使用純質之熱塑性塑膠是沒有意義 -4- 201105766 的，雖然該等塑膠非常容易熔化而且提供該待黏貼之基板 良好之浸潤結果，以及造成在數秒之內非常快速地發揮黏 貼之功效。但是在另一方面，該等熱塑性之塑膠於高溫下 質地相當的軟，所以該等塑膠在施壓之下進行黏貼時，傾 向於從黏接點處被擠壓出來。所以亦耐不住焊浴之高溫。 通常被作爲可交聯網絡化之膠帶使用者有環氧樹脂或 酚醛樹脂，其等和有些特定之固化劑反應並形成聚合物之 網絡物。 由可撓性體和環氧樹脂爲基礎所組成之黏膠組成物經 吊反應進f了地非吊緩慢’以致於黏貼之過程需進行相當長 之時間，並使得費用因此向上攀升。爲迴避此問題，於是 添加不同之加速劑，其等使得交聯網絡化之反應明顯增快。 而此等加速劑之缺點係爲經由環氧化物進行交聯網絡 化之膠帶，尤其是該等經過加速之系統，甚至已經於室溫 下或稍微升高之溫度下即開始發生交聯網絡化反應。 尤其是當調整高反應速度以縮短製備所需之時間時， 儲存之安定性經常會降低。大多數作爲此種應用之市售產 品因此必須被保存在5 °C下，以使其甚至能夠儲存足夠長 久之時間。 酚醛樹脂可被分成兩種類型，其中一種爲可溶酚醛樹 脂，其等於合成時形成於過量之甲醛之下，以及另一種爲 酚醛清漆，其等生成於少量之甲醛下。 可溶酚醛樹脂於高熱之下或是經由加入酸之下自發地 與自身分子產生交聯網絡化反應並釋出水分子，而酚醛清 201105766 漆則僅在分子之間相互反應，當甲醛分解劑作爲交聯網絡 劑作用時。當其等進行交聯網絡化反應時，不會分解生成 水。 如果希望使用一無氣泡產生之方法時，則通常要捨棄 使用酚醛樹脂。其中一個原因是可溶酚醛樹脂於反應時分 解所產生之水分可被預期產生氣泡，另外一個原因是於使 用酚醛清漆時需要用到交聯網絡劑，其於反應時可至少分 解產生甲醛，經常，如於六亞甲基四胺之情形中，還可分 解產生氨分子。此兩種氣態物質同樣可導致氣泡之形成。 交聯網絡劑樹脂主要被使用於組構物品時之黏貼上， 並且於固化之後形成非常易碎之黏膠組成物，其雖然有高 度之黏合強度，但卻幾乎不具可撓性。 對於在可撓性印刷電路板之使用上，提升可撓性是必 要之手段。一方面是黏貼時要有膠帶之幫助，其於理想之 情況下被捲成一紙捲狀物體，另一方面是其與可撓性印刷 電路板有關，其等亦必須被彎折，在以筆記型電腦中之印 刷電路板之實施例上即可看得很清楚，於筆記型電腦中可 開合之螢幕係透過可撓性印刷電路板與其他之開關相連 接。 使此等反應樹脂黏膠產生可撓性在兩種類型之黏膠上 是可行的。其中一種係爲以彈性體鏈產生可撓性之環氧樹 脂，其等經由非常短鏈之彈性體卻僅獲致有限度之可撓 性。另外一種可能性係經由添加彈性體，其被添加至黏膠 組成物中，以達到可撓性之產生。因爲該等彈性體在化學 201105766 上無法發生交聯網絡化反應，故僅有此類之彈性體可被使 用，其等於高溫之下仍然具有高度之黏稠性，因爲該黏膠 組成物否則在壓擠時會從黏接點處被擠出來。 由於該等膠帶於大多數之情況下係由溶液製備而成， 因此常常有困難發現彈性體，其等一方面具有足夠之鏈長 以致不會在高溫下流動，另一方面還要可溶解於或可均散 於常見之溶劑中。 利用熱熔法進行之製備工作對於形成交聯網絡之系統 而言要做到簡直是非常之困難，因爲必須要避免於製備之 過程中過早發生交聯網絡化反應。 於此特別適合使用丁腈橡膠，其等可溶解於特定之溶 劑中，或可經由均散法轉變成一可塗抹之懸浮溶液，但是 在高溫下卻僅會有限度地流動。 例如從DE 44 27 802 A得悉由丁腈橡膠及酚醛樹脂製 成之膠帶。此類膠帶被使用於黏貼智慧卡中之晶片模組。 於EP 1 6 1 5 97 8 A中同樣描述到使用於智慧卡之膠 帶。於此亦稱之爲酚醛清漆樹脂。黏貼智慧卡中之晶片模 組之應用在對於膠帶之要求上然而卻完全不同於可撓性印 刷電路板之黏貼。例如智慧卡不必通過焊浴高溫之試驗， 此外於黏貼中所產生之少數氣泡亦不會構成問題，只要氣 泡不會對於黏貼之功效產生不良之影響，因爲氣泡無法被 察覺。將EP 1 6 1 5 97 8 A之教示移轉至可撓性印刷電路板 範疇內之黏貼上因此似乎是不可能的。 【發明內容】 201105766 本發明之目的因此在於提供用於黏貼可撓性印刷電路 板之膠帶，經由該膠帶之使用可完全或至少部分避開目前 技術水準之缺點。 較偏好爲應該要將於熱壓時從黏接點處擠出之黏膠薄 膜減至最低。此外，有利者是於熱壓時或是於緊接其後之 擠壓時不要有氣泡形成，又有利者是室溫下之儲存安定性 應該要保證一年以上。儘管有長時間之儲存安定性，但仍 希望有儘可能快速之反應以增加該方法之速度。 【實施方式】 此目的之完成係經由膠帶之使用，正如其在主要申請 項中在特徵上更清楚之描述。附屬項之內容係爲本發明內 容有利之延伸及一經由使用而取得之黏合複合體。 因此，本發明之內容係使用可經由加熱而活化之膠帶 於黏貼電子元件及印刷電路板，該膠帶包含有黏膠組成 物，其係由至少下列成分所組成： a. 至少一種丙烯腈-丁二烯-共聚合物， b. 至少一種酚醛清漆樹脂，及 c. 一種甲醛釋出劑作爲固化劑 有利者爲’該黏膠組成物中丙烯腈-丁二烯·共聚合物 與酚醛清漆樹脂之含量比介在於3: 7至8: 2之範圍內， 所以較偏好之情況係丙烯腈-丁二烯-共聚合物以重量比爲 30至80個重量百分比及酚醛清漆樹脂以重量比爲20至70 個重量百分比之形式存在’其中組成成分a與b相加之結 果爲100個重量百分。 201105766 酚醛清漆樹脂尤其能夠於高溫下在固化劑之幫助下以 化學反應方式進行交聯網絡化反應。此交聯網絡化反應， 根據本發明，尤其僅經由酚醛清漆樹脂與固化劑在加熱之 下所進行之化學反應及/或經由固化劑與酚醛清漆樹脂和 聚合物基質於加熱下所進行之反應所完成。 可經由加熱而活化之黏膠組成物，因此被理解爲一種 聚合物組成物，其在加入熱能之下發生交聯網絡化反應， 並因此形成足以黏貼之黏合強度（充分之黏著力，充分之內 聚力）》此聚合物組成物同時於室溫下可不具有、或具有微 弱或強烈之觸摸黏性（接觸黏性，黏性）。 熱交聯網絡化反應之活化溫度明顯高於室溫之上，通 常介於至少1 oo°c或更高之溫度。熱交聯網絡化反應較偏好 之活化溫度，尤其爲保證具有必要之黏合強度，介於至少 120°c，尤其介於140°C和220°C之間。 用於根據本發明所使用膠帶之黏膠組成物可被限縮在 前述a.至c.之組成成分上，但於需要時亦可含有其他之組 成成分。 一般性之表述語「膠帶」於本發明之含意中包括所有 扁平之構造體，例如於二維空間伸展之薄片或薄片之片 段，在長度上做延伸，同時在寬度上做限制之帶狀物，帶 狀物之片段，空白片及類似之構造體。 理想情況下，酚醛清漆樹脂與固化劑（甲醛釋出劑）所 使用之含量比爲50: 1至5: 1個重量百分比（酚醛清漆樹 脂：固化劑），較偏好20 : 1至7 : 1 Gew.-%個重量百分比。 201105766 令人意外者是，於本發明中顯現於使用酚醛清漆樹脂 時，雖然出現酚醛清漆樹脂所預期之分解產物，例如甲醛 或氨（請參閱上文），但是在黏接點處卻沒有氣泡之形成。 於本發明中顯現根據本發明所使用之黏膠組成物係可 經由加熱而被活化，在加熱之下發生交聯網絡化反應並且 在加熱之下於接受黏貼之基板上呈現良好之流動性，於聚 醯亞胺上呈現良好之黏合性，對於溫度短暫之安定性爲至 少288°C以及於未發生交聯網絡化反應之狀態下可溶解或 懸浮在有機溶劑中。 根據本發明所使用之黏膠組成物因此相當適合用於完 成上述之目的。 根據本發明，尤其所有之丙烯腈·丁二烯橡膠，其所含 有之丙烯腈從15至55個重量百分比者，皆可被作爲丙烯 腈-丁二烯-共聚合物使用，於本案中丙烯腈-丁二烯-共聚合 物亦被稱之爲丙烯腈-丁二烯橡膠、腈-丁二烯橡膠或被簡 短稱之爲丁二腈橡膠。同樣，亦可使用由丙烯腈-丁二烯與 異戊二烯組成之共聚合物。於此共聚合物中，以1，2-銜接 之丁二烯之比例是不固定的。前述之聚合物可以不同之程 度被水化；甚至於完全被水化之聚合物，其雙鍵比例在1 % 以下者，亦是可以利用的。 丙烯腈·丁二烯橡膠係於高溫下或低溫下聚合而成。 可由購買所取得者有此類之系統，商品名稱例如有Εηι Chem 公司之 EuropreneTM，Bayer 公司之 Krynac TM 及 Perbunan TM或Zoen公司之Nipol及Breon，可購買得到經 -10- 201105766 水化之系統例如有Zoen公司之Zetpol或是Lanxess公司 之Therban，其等具不同之水化程度。上述之產品係作爲 根據本發明可有利被使用之系統之實施例。 於本發明中顯示丙烯腈含量較高之丁二腈橡膠有較佳 之黏合功效。對於強力之黏貼同樣有利者係高分子量，其 中必須要注意者是該聚合物還可被製備成溶液或懸浮液。 丁二腈橡膠可溶解或懸浮於短鏈之醇類及酮類中，例 如乙醇或丁酮。其中較偏好者爲丁酮，因爲其餘之組成成 分，尤其是酚醛清漆樹脂可更有效地被溶解於丁酮中。 酚醛清漆樹脂係可溶解、可熔化、不會自動固化以及 具儲存安定性之酚醛樹脂。其等係由甲醛和過量之酚在大 多數情況爲酸性固化劑之存在下經由縮合反應製備而成。 將其等經交聯網絡化反應製成硬質塑膠之鑄造元件係 在分解時釋出甲醛之固化劑*例如六亞甲基四胺（Urotropin) 之幫助下所進行。 由於空間位阻因素，交聯網絡化反應在對位上進行之 速度比在鄰位上快速。因此，在特別快速之交聯網絡化反 應方面較偏好使用酚醛清漆樹脂，其含有彼此以鄰位銜接 之酚單元。 於根據本發明有利於使用之酚醛清漆樹脂方面之實施 例例如有Sumitomo Bakelite之產品Durez及/或塑膠工程公 司之產品Plenco。 可考慮作爲固化劑者有各種甲醛釋出劑，例如六亞甲 基四胺（Hexa，HMTA，Urotropin)及/或各種甲醇胺衍生物， -11- 201105766 例如三甲醇基三聚氰胺或六甲醇基三聚氰胺。 由固化劑與酚醛清漆樹脂所進行之化學交聯網絡化反 應可於黏貼薄膜內達到非常大之強度。甚至對於聚醯亞胺 之黏合強度亦非常高。 爲增加黏著力，可於有利之方法中添加可與彈性體互 容之黏膠樹脂（「增黏劑」）。 可於根據本發明可經由加熱而活化之黏膠組合物中使 用之增黏劑例如有未經水化、經部分水化或完全水化之樹 脂，其係以松脂及松脂衍生物爲基礎結構，二環戊二烯之 水化聚合物，未經水化、經部分水化、經選擇或完全水化 之碳水化合物樹脂，其以c5·、C5/C9-或c9-單體流爲基礎 結構，聚萜烯樹脂，其以-璇烯及/或 ·蒎烯及/或-檸 檬烯爲基礎結構，較受偏好之純質c8-及C9-芳香烴化合物 之水化聚合物。上述之黏膠樹脂可以單獨亦可以混合物之 方式被使用。有利之作法是可添加增黏劑至20個重量百分 比，其係以所混合之黏膠組成物爲依據。 此外，還可使用少量之環氧樹脂。爲保持儲之存安定 性，環氧樹脂之含量較偏好不超過10個重量百分比。 環氧樹脂被理解爲單體化合物及寡聚合化合物，其中 每分子含有一個以上之環氧化物終端基。該等樹脂可爲縮 水甘油酯或表氯醇與雙酚A或雙酚F或與由此二者組成之 混合物形成之反應產物。可使用者還有環氧化物酚醛清漆 樹脂’其係由表氯醇與酚和甲醛之反應產物相互反應而製 得。 -12- 201105766 可使用者甚至含數個環氧終端基之單體化合物，其被 作爲環氧樹脂之稀釋劑使用。同樣還可使用經過改變可撓 性之環氧樹脂。 有利於使用之環氧樹脂之實施例例如有Ciba Geigy之 Araldite™ 60 10' CY-281™' ECN™1 273 ' ECN™1280' MY 720 ' RD-2，Dow Chemicals 之 DERTM331、7 3 2、7 36、DEN™4 32 > Shell Chemicals 之 EponTM812、825、826、828、830 等，同 樣爲 Shell Chemicals 之 HPTtm1071、1079，Bakelite 股份有 限公司之 BakeliteTMEPR 161、166、172、191、194 等。 有利於使用之商業脂肪烴環氧樹脂例如有二氧化乙烯 基環己烷，如 Union Carbide 公司之 ERL-4206、4221、4201、 4289 或 0400 · 有利於使用之經可撓性處理之環氧樹脂可向No ve〇n 公司購買取得，其商品名爲Hycar。 有利於使用之環氧化物稀釋劑，其係含數個環氧終端 基之單體化合物，例如有 Bakelite股份有限公司之 BakeliteTM EPD KR、EPD Z8、EPD HD、EPD WF 等，或 UCCP 公司之 PolypoxTM R9、R12、R15、R19、R20 等。 可依選擇被使用之其他添加劑有： -一級抗氧化劑，例如具空間位阻之酚類 -二級抗氧化劑，例如亞磷酸鹽或硫醚 -其他之抗老化劑，例如具空間位阻之胺類 -製程安定劑，例如C-自由基捕捉劑 -抗光劑，例如UV·吸收劑 -13- 201105766 -加工輔助劑 -塡充劑，例如二氧化矽、玻璃（經過硏磨或以球珠之 形式），氧化鋁、氧化鋅、二氧化鈦、碳黑、金屬粉末等 -色素及顏料及光學增亮劑 -於需要時具較偏好之可撓性性質之其他聚合物。 上述以及於需要時之其他添加劑，尤其是當經由添加 該等添加劑係要調整該黏膠組成物有關特定使用用途之性 質時，才可單獨或彼此互相組合使用。 使用增塑劑亦可增加已被交聯網絡化之黏膠組成物之 可撓性。可被作爲增塑劑使用者有低分子之聚異戊二烯、 聚丁二烯、聚異丁烯或聚乙二醇及聚丙二醇。 由於丁二腈橡膠即使於高溫下不具太低之黏稠性，因 此在進行黏貼及熱壓時不會發生黏膠組成物從黏接點處被 擠出之情形。於此過程中，酚醛清漆樹脂及，於需要時， 聚合物基質和固化劑進行交聯網絡化反應，結果形成一個 三維空間之網絡化結構。 於製備膠帶時，將黏膠組成物之成分溶解或懸浮尤其 於一適當之溶劑，例如丁酮中，接著將其塗被在一可撓性 之基片上，其附有一層脫離層（例如一層防黏紙或一層防黏 膜），然後加以乾燥，所以黏膠可容易地再度從該基片上移 除。在經過適當之調製之後即可於室溫下製備空白片、紙 捲狀物體或其他之膜製品。適當之膜製品然後尤其在高溫 下被黏貼在接受黏貼之基片上，例如在聚醯亞胺上。 然而亦可將黏膠組成物直接塗被在聚醯亞胺載體上。 -14- 201105766 此種黏膠薄膜然後尤其可被用於覆蓋FPCB之銅電路路徑 上。 在這方面之使用上，根據本發明所使用之膠帶爲達到 更佳之易處理性，其可附加上一層覆蓋材料（剝離襯墊，防 黏襯墊），例如覆蓋經矽化之隔離紙、經矽化之聚合物薄膜 (例如經矽化之PET-薄膜）或類似之物品。 黏貼之動作沒有必要以單一步驟之方式進行，而是可 以首先將膠帶附在兩片基片中之其中一片上，其方法是以 中等之溫度將其黏貼。直到與第二片基片進行熱壓時，酚 醛清漆樹脂才會非常良好或部分被固化，且此黏膠薄膜達 到高度之黏合強度。 酚醛清漆樹脂和固化劑尤其在覆膜溫度時應該還未進 行化學反應，而是在進行熱黏貼時才彼此相互反應。 根據本發明之膠帶於所謂之快壓處理法中（QPP ;目前 技術水準；熱壓法例如於180°C及15巴下進行2分鐘；緊 接著進行烘箱存放例如於150°C下進行30分鐘至1小時） 以及於熱壓法中（HP ;熱壓法例如於180°C及15巴下進行 30分鐘）要呈現明顯之優點，方法是於明顯改善之條件下 (處理之時間縮短）皆可達到至少等量之黏貼產物，例如在 快壓處理法中針對於可比較之結果可捨棄其後進行之烘箱 存放步驟或是將熱處理步驟中壓擠時間減少至1分鐘（於保 留後續進行之烘箱存放時）；於熱壓法中’針對於可比較之 結果可將熱壓步驟同樣減少至1分鐘（分別在保留其餘上述 實施例値之參數下）。 -15- 201105766 以本文中所提出之膠帶可極佳地將經過蝕刻及/或未 經蝕刻之可撓性印刷電路板彼此之間相互黏貼（其中可將 聚醯亞胺黏貼在聚醯亞胺上或亦可將聚醯亞胺黏貼在銅 上：於此可將兩塊印刷電路板彼此黏貼，但亦可將兩塊以 上之印刷電路板彼此黏貼在一起，所以由是方式製備成多 印刷電路板複合體）；此外，還可極佳地將經過蝕刻及/或 未經蝕刻之可撓性印刷電路板以整個表面或部分表面之方 式黏貼在強化材料（硬化劑）之上或是以部分表面之方式與 強化材料（硬化劑）相黏貼（其中尤其可將聚醯亞胺黏貼在硬 化劑材質上，但亦可將銅層黏貼在該硬化劑之材質上）。 所有之黏貼主要係以熱壓法所完成，較偏好由快壓處 理法及/或熱壓處理法（請參閱上文）所完成。 因此本發明之內容又關及於一黏合複合體，其組成包 括至少兩塊經過黏貼之可撓性印刷電路板及一根據本發明 所述之膠帶，尤其是可經由加熱而活化之膠帶，正如其於 根據申請專利範圍其中任一項針對於使用之內容所述；進 一步被黏貼如上文中所述。因此本發明之內容又關及於一 黏合複合體，其組成包括至少一塊可撓性印刷電路板或一 黏合複合體，其組成包括至少兩塊可撓性印刷電路板於一 塊強化材料上以及一根據本發明所述之膠帶，正如其於根 據申請專利範圍其中任一項針對於使用之內容所述；進一 步被黏貼如上文中所述。 實施例 下文中將依據數個實施例對本發明做更詳細之說明， -16- 201105766 然而該等實施例並不會以任何方式對本發明造成限縮。 實施例1 將100等份.之Breon N41H80 (Zeon公司之丁二腈橡 膠，含41%之丙稀腈）及100等份之0\^62 12687 (511111丨1;〇111〇-Bakelite公司之酚醛清漆樹脂，已含7.4%六亞甲基四胺） 置入一均散機中並製備成30%之丁酮懸浮溶液。均散所需 之時間爲20小時。接著從溶液中將該可經由加熱而活化之 黏膠塗抹在一經過矽化之PET-薄膜（「防黏襯墊」）之上， 然後於100 °C下將其乾燥，結果形成一厚度爲25微米之黏 膠層。 實施例2 根據如實施例1相同之方法製備一黏膠組成物，其係 由100等份之Breon N41H80、50等份（以固體物質爲依據） 之樹脂Durez 37087 (爲Durez 1 2687 丁酮溶液之一種55% 之溶液，不含固化劑）及7等份之六亞甲基四胺。 實施例3 於此不使用實施例1中之丁二腈橡膠，而使用Lanxess 公司所生產之一種經水化之丁二腈橡膠Therban 4369 (係經 部分水化之丁二腈橡膠，含43 %之丙烯腈.）。 比較性實施例V 4 根據如實施例1相同之方法製備一黏膠組成物，於其 中將1/2之酚醛清漆樹脂以Bakelite公司之可溶性酚醛樹 脂9610LW取代。 比較性實施例V5 -17· 201105766 使用如實施例1中相同之原料，但是於100等份之丁 二腈橡膠中添加入300等份之酚醛清漆樹脂。 比較性實施例V6、V7及V8 接下來之比較性實施例使用三種商用產品於所述之應 用上。 V6: Sony 公司之 Sony 3410 (丁二腈橡膠（70% 丁二烯 / 30% 丙烯腈）-環氧樹脂-組成物， 1 : 1，於防黏襯墊上） V7: Sony公司之Sony 3450 (聚丙烯酸正丁酯；聚丙烯腈； 聚丙烯酸乙酯；環氧化物組成 物，2: 1: 4: 2，於防黏襯墊 上） V8 : DuPont公司之Pyralux LF 100 (於防黏襯墊上經改質之 丙烯酸黏膠組成物；彈 性體組成成分：82%之丙 烯酸正-丁酯，12%之丙 烯腈，6%之丙烯酸；樹 脂組成成分：酚甲醛樹 脂（酚醛清漆樹脂））201105766 VI. Description of the Invention: [Technical Field] The present invention relates to a tape that can be activated by heating, which has very low fluidity at high temperatures, and is particularly suitable for bonding flexible printed circuit boards, especially in manufacturing The electronic component has a high degree of crosslinking speed. [Prior Art] Flexible Printed Circuit Boards (FPCBs; also known as flexible printed circuit boards) are used today in many electronic devices, such as cell phones. Radio, computer, printer and many other devices. The flexible electronic printed circuit boards are made of several layers of (especially etched) electronic circuits of a rubbed copper layer coated sheet ("Flexible Copper Clad Laminates", FCCL; also known as The copper layer is composed of a thin plate) which is equal to each other being adhered to each other. FCCL is also commonly used in electronic devices. The flexible copper layer is coated with a copper layer and a thermoplastic resin having a high melting point and resistance. Most of the cases are polyimine, and the rarer one is polyester, such as polyethylene terephthalate. Diester (PET) or polyethylene naphthalate (PEN) or liquid crystal polymer (LCP), and some parts of it are also composed of a layer of adhesive layer and the like. When preparing FPCB or reinforcing FCCL with a reinforcing material called so-called hardener, it is often used to require particularly high-adhesive tape. On the one hand, in the preparation of a flexible copper layer coated sheet (FCCL), the copper layer and the polyimide layer are adhered to each other, this step is usually done with an acrylic adhesive composition; on the other hand, FPCB The layers of FCCL are also adhered to each other. In the case of 201105766, in most cases, the polyimide layer is adhered to the polyimide layer or the polyimide layer is adhered to the copper layer. In addition, the FCCL or the finished FPCB is also adhered to other substrates (hardened materials, so-called "hardeners") to harden the sheet to some extent. The reinforcing material can be used, for example, as a rigid glass fiber-epoxy-plate (FR-4), polyimide, polyester, steel, and aluminum. This is particularly interesting, for example, if electronic components such as wafers or the like are to be mounted on a flexible printed circuit board and/or the like is used for safety. There is a very high requirement for the tape used on this type of adhesive. Since it is necessary to achieve very high adhesion, heat resistance and chemical resistance, it is common to use a tape that can be activated by heating, which is used under high temperature. These tapes are often subjected to FPCB adhesion under high temperature loads, often at a temperature of 180 ° C without releasing volatile constituents. In order to achieve a high degree of cohesion, the tapes should be crosslinked and networked under the load of the aforementioned temperature. High pressure is applied at the time of adhesion to achieve a good wetting effect, and most of the adhesion is carried out by hot pressing. Regarding the tape, it is necessary that the tape has only a very low fluidity at high temperatures so that it does not be squeezed out from the bonding points. This can be achieved via a tape of high viscosity uncrosslinked networked or via a rapid cross-linking network reaction. In addition, the tapes must then withstand the high temperatures of the solder bath, i.e., must withstand a very high temperature load for a short period of time, e.g., 288 °C. At the same time, no bubbles can be generated in the pasted components. For this reason, the use of pure thermoplastics is meaningless -4- 201105766, although these plastics are very easy to melt and provide good wetting results for the substrate to be pasted, and cause very fast play in seconds. The effect of pasting. On the other hand, however, these thermoplastic plastics are relatively soft at high temperatures, so when the plastics are applied under pressure, they tend to be squeezed out from the bonding points. Therefore, it can not withstand the high temperature of the solder bath. Tape users who are commonly used as crosslinkable networked have epoxy or phenolic resins that react with certain specific curing agents to form a network of polymers. The adhesive composition composed of the flexible body and the epoxy resin is suspended and moved slowly, so that the process of sticking takes a relatively long time, and the cost is thus increased. In order to avoid this problem, different accelerators were added, and the reaction of the cross-linking network was significantly increased. The disadvantages of these accelerators are the tapes that are crosslinked and networked via epoxides, especially in such accelerated systems, which have even begun to crosslink network at room temperature or slightly elevated temperatures. reaction. Especially when adjusting the high reaction rate to shorten the time required for preparation, the stability of storage is often lowered. Most commercially available products for this application must therefore be stored at 5 °C so that they can even be stored for long enough. The phenolic resin can be classified into two types, one of which is a resol phenolic resin which is equal to that formed under excess formaldehyde during synthesis, and the other which is a novolac lacquer which is formed under a small amount of formaldehyde. Resole phenolic resin spontaneously reacts with its own molecules to generate cross-linking network reaction and release water molecules under the action of adding acid, while phenolic acid 201105766 lacquer reacts only between molecules, when formaldehyde decomposition agent acts as When the cross-linking agent acts. When they are subjected to a cross-linking network reaction, water is not decomposed. If it is desired to use a bubble-free method, the phenolic resin is usually discarded. One of the reasons is that the water produced by the decomposition of the resol resin during the reaction can be expected to generate bubbles. Another reason is that the use of a novolac network is required when using a novolac, which can at least decompose to produce formaldehyde during the reaction, often In the case of hexamethylenetetramine, it is also decomposed to produce an ammonia molecule. These two gaseous substances can also cause the formation of bubbles. The crosslinked network agent resin is mainly used for the adhesion of the structural article, and after curing, forms a very brittle adhesive composition which, although having a high adhesive strength, is hardly flexible. For flexibility in the use of flexible printed circuit boards, it is necessary to increase flexibility. On the one hand, it is necessary to have the help of tape when pasting, which is ideally rolled into a roll of paper, and on the other hand it is related to the flexible printed circuit board, and the like must also be bent, taking notes The embodiment of the printed circuit board in the computer can be seen clearly. The screen that can be opened and closed in the notebook computer is connected to other switches through the flexible printed circuit board. It is feasible to make these reactive resin adhesives flexible on both types of adhesives. One of these is the production of a flexible epoxy resin with an elastomer chain which, through a very short chain elastomer, yields only a limited degree of flexibility. Another possibility is through the addition of an elastomer which is added to the adhesive composition to achieve flexibility. Since these elastomers are unable to crosslink network reaction on Chemistry 201105766, only such elastomers can be used, which is still highly viscous at high temperatures because the adhesive composition is otherwise under pressure. When squeezed, it will be squeezed out from the joint. Since these tapes are prepared from solutions in most cases, it is often difficult to find elastomers which, on the one hand, have sufficient chain length so as not to flow at high temperatures, and on the other hand are soluble in Or they can be dispersed in common solvents. The preparation by the hot melt method is extremely difficult for a system for forming a crosslinked network because it is necessary to avoid premature cross-linking network reaction during the preparation process. It is particularly suitable to use nitrile rubber which can be dissolved in a specific solvent or can be converted into a smearable suspension solution by a homogenous method, but only flows at a high temperature. Tapes made of nitrile rubber and phenolic resins are known, for example, from DE 44 27 802 A. This type of tape is used to attach a wafer module to a smart card. The tape used for smart cards is also described in EP 1 6 1 5 97 8 A. Also referred to herein as novolac resin. The application of the wafer module in the smart card is applied to the tape but is completely different from the adhesion of the flexible printed circuit board. For example, the smart card does not have to pass the high temperature test of the solder bath, and the small number of bubbles generated in the paste does not pose a problem as long as the bubble does not adversely affect the effect of the paste because the bubble cannot be detected. It seems impossible to transfer the teaching of EP 1 6 1 5 97 8 A to the adhesive in the category of flexible printed circuit boards. SUMMARY OF THE INVENTION 201105766 The object of the present invention is therefore to provide an adhesive tape for adhering a flexible printed circuit board, by which the disadvantages of the state of the art can be completely or at least partially avoided. It is preferred to minimize the amount of adhesive film that should be extruded from the bonding point during hot pressing. In addition, it is advantageous that no bubbles are formed during hot pressing or immediately after extrusion, and it is advantageous that the storage stability at room temperature should be guaranteed for more than one year. Despite the long-term storage stability, it is desirable to have the fastest possible response to increase the speed of the process. [Embodiment] The completion of this object is via the use of a tape as it is described more clearly in the main application. The contents of the sub-items are an advantageous extension of the content of the invention and a bonded composite obtained through use. Accordingly, the present invention is directed to an electronic component and a printed circuit board using an adhesive tape that is activated by heating, the tape comprising a viscose composition comprising at least the following components: a. at least one acrylonitrile-butyl a diene-copolymer, b. at least one novolac resin, and c. a formaldehyde releasing agent as a curing agent is advantageously an 'acrylonitrile-butadiene·copolymer and novolak resin in the adhesive composition The content ratio is in the range of 3:7 to 8:2, so the preferred ratio is acrylonitrile-butadiene-copolymer in a weight ratio of 30 to 80% by weight and the novolac resin in weight ratio. In the form of 20 to 70 weight percent, 'the composition a and b are added together and the result is 100 weight percent. 201105766 The novolac resin is especially capable of cross-linking network reaction in a chemical reaction mode with the aid of a curing agent at a high temperature. This cross-linking network reaction, according to the invention, in particular only via a chemical reaction of the novolac resin with the curing agent under heating and/or via a curing agent with a novolac resin and a polymer matrix under heating Completed. A viscose composition that can be activated by heating, and thus is understood to be a polymer composition that undergoes a cross-linking network reaction under the addition of thermal energy, and thus forms an adhesive strength sufficient for adhesion (sufficient adhesion, sufficient) Cohesive force) This polymer composition may have no or weak touch adhesiveness (contact viscosity, viscosity) at room temperature. The activation temperature of the thermal crosslinking network reaction is significantly higher than above room temperature, usually at a temperature of at least 1 oo ° C or higher. The thermal cross-linking network reaction is preferred to the activation temperature, especially to ensure the necessary bond strength, between at least 120 ° C, especially between 140 ° C and 220 ° C. The adhesive composition for the tape used in accordance with the present invention may be limited to the components of the aforementioned a. to c., but may also contain other constituent components as needed. The general expression "tape" in the meaning of the present invention includes all flat structures, such as fragments of sheets or sheets that are stretched in two dimensions, extending in length while limiting the width of the ribbon. , fragments of ribbons, blank sheets and similar structures. Ideally, the ratio of the novolac resin to the curing agent (formaldehyde eliminator) is from 50:1 to 5:1 by weight (novolac resin: curing agent), preferring 20:1 to 7:1 Gew.-% by weight. 201105766 Surprisingly, in the present invention, when a novolak resin is used, although a decomposition product expected from a novolak resin such as formaldehyde or ammonia (see above) appears, there is no bubble at the bonding point. Formation. It is apparent in the present invention that the adhesive composition used in accordance with the present invention can be activated by heating, undergoes a cross-linking network reaction under heating, and exhibits good fluidity on a substrate that is subjected to adhesion under heating, It exhibits good adhesion to polyamidiamine, is stable to a temperature of at least 288 ° C and can be dissolved or suspended in an organic solvent in the absence of cross-linking network reaction. The adhesive composition used in accordance with the present invention is therefore quite suitable for accomplishing the above purposes. According to the present invention, especially all of the acrylonitrile butadiene rubber, which contains from 15 to 55 weight percent of acrylonitrile, can be used as an acrylonitrile-butadiene-copolymer, in the present case, propylene. The nitrile-butadiene-copolymer is also known as acrylonitrile-butadiene rubber, nitrile-butadiene rubber or simply referred to as succinonitrile rubber. Also, a copolymer composed of acrylonitrile-butadiene and isoprene may also be used. In this copolymer, the ratio of 1,2-bonded butadiene is not fixed. The aforementioned polymers may be hydrated to varying degrees; even those which are completely hydrated may have a double bond ratio of less than 1%. The acrylonitrile-butadiene rubber is polymerized at a high temperature or at a low temperature. The system can be purchased by the purchaser, such as EuropreneTM from ιηι Chem, KrynacTM and PerbunanTM from Bayer or Nipol and Breon from Zoen, which can be purchased, for example, by -10- 201105766 hydration system. There are Zetpol from Zoen or Therban from Lanxess, which have different degrees of hydration. The above products are examples of systems that can be advantageously used in accordance with the present invention. The succinonitrile rubber having a higher acrylonitrile content in the present invention has a better bonding effect. It is also advantageous for a strong adhesive to be a high molecular weight, and it must be noted that the polymer can also be prepared as a solution or suspension. The succinonitrile rubber can be dissolved or suspended in short-chain alcohols and ketones such as ethanol or methyl ethyl ketone. The preferred one is methyl ethyl ketone because the remaining constituent components, especially the novolak resin, can be more effectively dissolved in methyl ethyl ketone. The novolak resin is a phenolic resin which is soluble, meltable, does not cure automatically, and has storage stability. These are prepared by condensation reaction of formaldehyde and excess phenol in the presence of an acidic curing agent in most cases. Casting elements which are subjected to cross-linking network reaction to form a rigid plastic are carried out with the aid of a curing agent* which releases formaldehyde upon decomposition, such as hexamethylenetetramine (Urotropin). Due to steric hindrance, the cross-linking network reaction is faster in the alignment than in the adjacent position. Therefore, it is preferred to use a novolak resin which contains phenol units which are ortho-positioned to each other in a particularly fast cross-linking network reaction. Examples of the novolak resin which is advantageously used according to the present invention are, for example, the product of Sumitomo Bakelite, Durez, and/or the product of plastic engineering company Plenco. As a curing agent, various formaldehyde releasing agents such as hexamethylenetetramine (Hexa, HMTA, Urotropin) and/or various methanolamine derivatives, -11-201105766, such as trimethylol melamine or hexamethyl melamine, may be considered. . The chemical crosslinking network reaction by the curing agent and the novolak resin can achieve very high strength in the adhesive film. Even the adhesion strength to polyimine is very high. In order to increase the adhesion, a viscose resin ("tackifier") which is compatible with the elastomer can be added in an advantageous manner. A tackifier which can be used in a viscose composition which can be activated by heating according to the invention, for example, a resin which has not been hydrated, partially hydrated or completely hydrated, which is based on turpentine and rosin derivatives. a hydrated polymer of dicyclopentadiene, a carbohydrate resin that has not been hydrated, partially hydrated, selected or fully hydrated, based on a c5·, C5/C9- or c9- monomer stream Structure, polyterpene resin, which is based on -decene and / or decene and / or - limonene, is more preferred than the hydrated polymer of the preferred pure c8- and C9-aromatic hydrocarbon compounds. The above-mentioned viscose resin can be used singly or in a mixture. Advantageously, a tackifier can be added to 20 weight percent based on the mixed adhesive composition. In addition, a small amount of epoxy resin can be used. In order to maintain the stability of the storage, the content of the epoxy resin is preferably no more than 10% by weight. Epoxy resins are understood to be monomeric compounds and oligomeric compounds in which more than one epoxide end group is present per molecule. These resins may be the reaction product of glycidyl ester or epichlorohydrin with bisphenol A or bisphenol F or a mixture of the two. The user also has an epoxy phenol novolak resin which is obtained by reacting epichlorohydrin with a reaction product of phenol and formaldehyde. -12- 201105766 It is possible to use even a monomer compound containing several epoxy terminal groups, which is used as a diluent for epoxy resins. Epoxy resins with varying flexibility can also be used. Examples of epoxy resins which are advantageous for use are, for example, Ciba Geigy's AralditeTM 60 10' CY-281TM' ECNTM1 273 ' ECNTM1280' MY 720 ' RD-2, owTM 331 of Dow Chemicals, 7 3 2. 7 36, DENTM4 32 > Shell Chemicals' EponTM 812, 825, 826, 828, 830, etc., are also Shell Chemicals' HPTtm 1071, 1079, Bakelite Co., Ltd. BakeliteTM EPR 161, 166, 172, 191, 194, and the like. Commercially available aliphatic hydrocarbon epoxy resins which are advantageous for use are, for example, vinyl epoxide such as ERL-4206, 4221, 4201, 4289 or 0400 from Union Carbide Co., Ltd. Available from No ve〇n, the trade name is Hycar. An epoxide thinner that is advantageous for use as a monomeric compound containing several epoxy terminal groups, such as BakeliteTM EPD KR, EPD Z8, EPD HD, EPD WF, etc. from Bakelite, Inc., or PolypoxTM from UCCP R9, R12, R15, R19, R20, etc. Other additives which may be used depending on the choice are: - primary antioxidants such as sterically hindered phenols - secondary antioxidants such as phosphites or thioethers - other anti-aging agents such as sterically hindered amines Class-process stabilizers, such as C-radical scavengers - light stabilizers, such as UV·absorbers-13-201105766 - processing aids - chelating agents, such as cerium oxide, glass (either honed or by beads) In the form of aluminum oxide, zinc oxide, titanium dioxide, carbon black, metal powders, etc. - pigments and pigments and optical brighteners - other polymers having preferred flexibility properties when desired. The above and other additives as needed, especially when the additives are to be adjusted for the particular use of the properties by the addition of such additives, can be used alone or in combination with one another. The use of plasticizers also increases the flexibility of the adhesive composition that has been crosslinked and networked. As a plasticizer, users can have low molecular weight polyisoprene, polybutadiene, polyisobutylene or polyethylene glycol and polypropylene glycol. Since the succinonitrile rubber does not have too low a viscosity even at a high temperature, the adhesive composition is not extruded from the bonding point during the bonding and hot pressing. In this process, the novolac resin and, if necessary, the polymer matrix and the curing agent undergo a cross-linking network reaction, resulting in a networked structure in three dimensions. In preparing the tape, the components of the adhesive composition are dissolved or suspended, especially in a suitable solvent, such as methyl ethyl ketone, which is then coated onto a flexible substrate with a release layer (eg, a layer) The release paper or a layer of anti-adhesive film is then dried, so the adhesive can be easily removed from the substrate again. Blank sheets, paper rolls or other film articles can be prepared at room temperature after appropriate preparation. The appropriate film product is then adhered, particularly at elevated temperatures, to the substrate to which the adhesive is applied, such as on polyimide. However, the adhesive composition can also be applied directly onto the polyimide. -14- 201105766 This type of adhesive film can then be used especially to cover the copper circuit path of the FPCB. In this aspect of use, the tape used in accordance with the present invention achieves better handleability, which can be attached with a cover material (release liner, release liner), for example, covered with deuterated release paper, deuterated A polymeric film (eg, a deuterated PET-film) or the like. The action of the pasting does not have to be carried out in a single step, but the tape can first be attached to one of the two substrates by adhering it at a moderate temperature. The phenol novolak resin is cured very well or partially until hot pressing with the second substrate, and the adhesive film achieves a high degree of bonding strength. The novolac resin and the curing agent should not have undergone a chemical reaction especially at the film temperature, but react with each other even when the heat is applied. The tape according to the invention is in a so-called fast-pressing process (QPP; current state of the art; hot pressing, for example at 180 ° C and 15 bar for 2 minutes; followed by oven storage, for example at 150 ° C for 30 minutes Up to 1 hour) and in the hot pressing method (HP; hot pressing method, for example, 30 minutes at 180 ° C and 15 bar), there are obvious advantages, under the conditions of obvious improvement (shortening of processing time) At least an equal amount of the adhesive product can be achieved, for example, in the rapid pressure treatment, the oven storage step can be discarded for the comparable results or the pressing time in the heat treatment step can be reduced to 1 minute (after the retention is continued) When the oven is stored), the hot pressing step can be reduced to 1 minute for the comparable results in the hot pressing method (under the parameters of the remaining examples above, respectively). -15- 201105766 The etched and/or unetched flexible printed circuit boards are excellently adhered to each other with the tape proposed in the paper (wherein the polyimide can be adhered to the polyimide) The polyimide may be adhered to the copper: the two printed circuit boards may be adhered to each other, but two or more printed circuit boards may be adhered to each other, so that the printing is prepared by multi-printing. a circuit board composite); in addition, the etched and/or unetched flexible printed circuit board can be excellently adhered to the reinforcing material (hardener) as a whole surface or a part of the surface or Part of the surface is adhered to the reinforcing material (hardener) (in particular, the polyimide may be adhered to the hardener material, but the copper layer may be adhered to the material of the hardener). All pastes are mainly done by hot pressing, preferring to be done by rapid pressure treatment and/or hot pressing (see above). Therefore, the present invention relates to an adhesive composite comprising at least two pasted flexible printed circuit boards and a tape according to the invention, in particular a tape which can be activated by heating, as It is described in the context of any of the scope of the patent application; it is further pasted as described above. Therefore, the present invention relates to an adhesive composite comprising at least one flexible printed circuit board or a bonded composite comprising at least two flexible printed circuit boards on a reinforcing material and a The tape according to the invention is as described for the use in accordance with any of the scope of the patent application; further pasted as described above. EXAMPLES Hereinafter, the present invention will be described in more detail based on a number of examples, and the examples are not intended to limit the invention in any way. Example 1 100 parts aliquot of Breon N41H80 (Zeon succinonitrile rubber, containing 41% acrylonitrile) and 100 aliquots of 0\^62 12687 (511111丨1; 〇111〇-Bakelite Company) The novolak resin, which already contained 7.4% hexamethylenetetramine), was placed in a homodisperser and prepared into a 30% methyl ethyl ketone suspension solution. The time required for the dispersion is 20 hours. The heat-activated adhesive is then applied from a solution onto a deuterated PET film ("anti-stick liner") and then dried at 100 ° C to form a thickness of 25 Micron adhesive layer. Example 2 A viscose composition was prepared according to the same procedure as in Example 1 except that 100 parts aliquots of Breon N41H80, 50 aliquots (based on solid matter) of the resin Durez 37087 (Durez 1 2687 butanone solution) A 55% solution containing no curing agent) and 7 parts of hexamethylenetetramine. Example 3 The succinonitrile rubber of Example 1 was not used here, and a hydrated succinonitrile rubber Therban 4369 (a partially hydrated succinonitrile rubber containing 43%) produced by Lanxess Co., Ltd. was used. Acrylonitrile.). Comparative Example V 4 A viscose composition was prepared according to the same procedure as in Example 1, in which 1/2 of the novolac resin was replaced with Bakelite's soluble phenolic resin 9610 LW. Comparative Example V5 -17·201105766 The same raw materials as in Example 1 were used, but 300 aliquots of novolac resin were added to 100 parts aliquot of succinonitrile rubber. Comparative Examples V6, V7 and V8 The following comparative examples used three commercial products for the applications described. V6: Sony's Sony 3410 (succinonitrile rubber (70% butadiene / 30% acrylonitrile) - epoxy resin composition, 1 : 1, on the release liner) V7: Sony's Sony 3450 (Polybutyl acrylate; polyacrylonitrile; polyethyl acrylate; epoxide composition, 2: 1: 4: 2, on release liner) V8: DuPont Pyralux LF 100 (for anti-adhesive liner) The modified acrylic adhesive composition on the mat; elastomer composition: 82% n-butyl acrylate, 12% acrylonitrile, 6% acrylic; resin composition: phenol formaldehyde resin (novolac resin)
以製備之膠帶黏貼FCCL 將FCCL (可撓性銅層覆被薄板）Pyralux LF9110R [層體 排列順序（銅 305公克/平方公尺）+ (25微米丙烯酸黏膠組 成物）+ (25微米聚醯亞胺層；Kapton®)]分別以依據實施例 1至5製成之膠帶黏貼在一由FR-4 (「硬化劑」：大約10 -18- 201105766 公分X 2.5公分）組成之強化薄片上。 於黏貼時，將膠帶於100 °C下黏貼在由聚醯亞胺/銅薄 膜組成之FCCL-層之聚醯亞胺薄膜上，並將防黏襯墊移 除’其中該膠帶比接受黏貼之FCCL稍微短些，以便於稍 後有位置可抓住。接著將此由FCCL及黏膠組成之複合體 於100°C下黏貼在由FR-4組成之硬化薄片上，並且將此整 個複合體置入一可加熱之 Biirklepresse熱壓機中，並於 180°C 及1.3 MPa之壓力下擠壓（「熱擠壓」）20分鐘。 於記錄反應曲線時，將擠壓時間從1分鐘至30分鐘做 變化調整。 測試方法 將依據上述實施例製備之黏膠薄膜依下列測試方法進 行其特性之硏究。 FCCL-硬化層-複合體之L型剝離試驗[IPC-TM-650編號 2.4.9] 利用Zwick公司生產之拉伸測試機，針對依據上述方 法所製備由FCCL及FR-4-硬化層組成之複合體以及針對由 購買取得之比較性實施例V6至V8，將和硬化層成90°角之 FCCL以50毫米/分鐘之速度抽離，並測量所需之施力（單 位：牛頓/公分）。對於經由製備而成之實施例及比較性實 施例1至3及V4、V5之測量係經過於23 °C及50%相對濕 度下之黏貼後進行。每個測量値皆以三重複方式測定之。 反應曲線 紀錄實施例1及2與比較性實施例V6、V7及V8之反 -19- 201105766 應曲線圖，針對此等反應曲線圖於如上文中所述之L型剝 離試驗中測量相關於擠壓時間（施於固化劑上之熱壓）之黏 合力。同時評量於焊浴試驗後氣泡生成之情況。 擠出反應 擠出反應係依照下列之方式進行測定。將膠帶如上所 述於100°C黏貼在FCCL上，並將防黏襯墊移除。接著在該 複合體上打三個直徑爲5毫米之小孔。然後再將此經鑿孔 之複合體黏貼在FR-4之材料上，並隨之將其擠壓（熱擠壓 法；以可加熱之BUrklepresse熱壓機於180°C下及4MPa之 壓力下熱壓20分鐘）。經過20分鐘之擠壓後，測量黏膠組 成物被擠入該等孔洞中有多遠之距離。分別測定各個小孔 最大可及範圍之平均値。 焊浴安定性 將依據上述方法黏合之FCCL-硬化層-複合物以FCCL 之面放置於28 8 °C高溫之焊浴上10秒鐘。黏合結果被評定 爲具焊浴安定性之條件是，如果在黏貼處沒有形成使FCCL 聚醯亞胺膨脹或是可被光學儀器偵測到之氣泡時。而該試 驗被評定爲不通過之情形是，如果已經有輕微之氣泡生成 出現時。 儲存安定性 本試驗被視爲通過之條件是，如果於規定之儲存條件 下經過以紙捲狀物體形式儲存之黏膠薄膜於儲存之後相較 於新鮮製成之黏膠薄膜可被確定黏合強度無顯著之滑落時 (以FCCL-硬化層-複合物，如上所示，進行L型剝離試驗測 -20- 201105766 量）。 結果： L型剝離試驗 爲判斷上述諸實施例於黏合方面之技術，首先進行L 型剝離試驗 表1 : L型剝離試驗 實施例 1 2 3 V4 V5 L型剝離試驗單位牛頓/公分 32.7 34.1 22.6 ——— 29.8 18.2 貫施例5因其顯現之僵硬性而無法被黏貼得很好，且其濕 潤接受黏貼物體之表面不足，因此造成較小之黏合力。 焊浴試驗 於實施例1至3及比較性實施例V4及V5等進行焊浴 試驗。其中實施例1、2及3通過該項試驗，反而兩個比較 性實施例卻在黏貼點處呈現許多氣泡，所以沒有通過該項 試驗。 時間性之反應/反應曲線 表2中示出「反應曲線」試驗之結果 表2:反應速度，與擠壓時間相關之黏合力 說明：[牛頓/公分]/ /起泡（bloating) -21- 201105766 (自5分鐘起，不再有任何實施例還有氣泡存在） 擠壓時間 實施例1 實施例2 實施例V6 實施例V7 實施例V8 1分鐘 28//kB 27//kB 18//kB 28//B 2.7//wMB 2分鐘 29//kB 28//kB 18//kB 29//wMB 3.9//wMB 5分鐘 29 28 19 30 6.4 10分鐘 29 28 23 30 15 30分鐘 30 29 25 30 19Adhesive tape is used to bond FCCL FCCL (flexible copper layer coated sheet) Pyralux LF9110R [Layer order (copper 305 g/m2) + (25 μm acrylic viscose composition) + (25 μm polypeptone) The imine layer; Kapton®) was respectively adhered to a reinforced sheet composed of FR-4 ("hardener": about 10 -18 to 201105766 cm X 2.5 cm) by a tape made according to Examples 1 to 5. When pasting, the tape is adhered to the FCCL-layer polyimide film composed of polyimide/copper film at 100 ° C, and the anti-adhesive liner is removed, wherein the tape is more adhesive than the adhesive. The FCCL is a bit shorter so that you can grab it later. The composite consisting of FCCL and viscose was then adhered to a hardened sheet consisting of FR-4 at 100 ° C, and the entire composite was placed in a heated Biirklepresse hot press at 180 Squeeze ("hot extrusion") for 20 minutes at a pressure of °C and 1.3 MPa. When the reaction curve is recorded, the extrusion time is adjusted from 1 minute to 30 minutes. Test Method The adhesive film prepared in accordance with the above examples was subjected to the study of its characteristics in accordance with the following test methods. FCCL-hardened layer-composite L-type peel test [IPC-TM-650 No. 2.4.9] Using a tensile tester manufactured by Zwick, for the composition of FCCL and FR-4-hardened layers prepared according to the above method The composite and the comparative examples V6 to V8 obtained from the purchase, the FCCL at a 90° angle to the hardened layer was withdrawn at a speed of 50 mm/min, and the required force was measured (unit: Newton/cm) . The measurement of the prepared examples and comparative examples 1 to 3 and V4, V5 was carried out after pasting at 23 ° C and 50% relative humidity. Each measurement enthalpy is measured in three replicates. The reaction curves are recorded in the inverse of Examples 1 and 2 and Comparative Examples V6, V7 and V8 - 201105766. The graphs for these reaction curves are related to the extrusion in the L-type peel test as described above. Adhesion of time (hot pressing applied to the curing agent). At the same time, the bubble formation after the solder bath test was evaluated. Extrusion reaction The extrusion reaction was carried out in the following manner. The tape was adhered to the FCCL at 100 ° C as described above, and the release liner was removed. Three small holes of 5 mm in diameter were then placed on the composite. The perforated composite is then adhered to the material of FR-4 and subsequently extruded (hot extrusion; with a heated BUrklepresse hot press at 180 ° C and a pressure of 4 MPa) Hot pressing for 20 minutes). After 20 minutes of extrusion, it was measured how far the adhesive composition was squeezed into the holes. The average enthalpy of the maximum reach of each well was determined. Solder bath stability The FCCL-hardened layer-composite bonded according to the above method was placed on a 28 ° C high temperature solder bath for 10 seconds on the surface of the FCCL. The adhesion result is evaluated as having the stability of the solder bath if there is no bubble formed at the adhesion to expand the FCCL polyimide or to be detected by the optical instrument. The case where the test is rated as not passing is if a slight bubble generation has occurred. Storage stability This test is considered to be a condition that if the adhesive film stored in the form of a roll of paper is stored under the specified storage conditions, the adhesive strength can be determined after storage compared to the freshly prepared adhesive film. When there is no significant slip (as shown in the FCCL-hardened layer-composite, as shown above, the L-type peel test is measured -20-201105766). Results: L-type peeling test In order to judge the techniques of the above-mentioned examples in terms of bonding, the L-type peeling test was first carried out. Table 1: L-type peeling test Example 1 2 3 V4 V5 L-type peeling test unit Newton/cm 32.7 34.1 22.6 — —— 29.8 18.2 Example 5 cannot be adhered very well due to its apparent stiffness, and its wetness accepts insufficient surface of the adherent object, thus causing less adhesion. Solder bath test Solder bath tests were carried out in Examples 1 to 3 and Comparative Examples V4 and V5. Among them, Examples 1, 2 and 3 passed the test, but the two comparative examples showed a lot of bubbles at the sticking point, so the test was not passed. Time-Reaction/Reaction Curve Table 2 shows the results of the “Reaction Curve” test. Table 2: Reaction speed, adhesion force related to extrusion time Description: [Newton/cm]//bloating-21- 201105766 (There are no more examples of bubbles present since 5 minutes) Extrusion time Example 1 Example 2 Example V6 Example V7 Example V8 1 minute 28//kB 27//kB 18//kB 28//B 2.7//wMB 2 minutes 29//kB 28//kB 18//kB 29//wMB 3.9//wMB 5 minutes 29 28 19 30 6.4 10 minutes 29 28 23 30 15 30 minutes 30 29 25 30 19
Darin bedeuten : kB :無氣泡產生；wMB :少數微氣泡；b :氣泡 於實施例1及2和數種商用產品之比較中呈現出實施 例1及2比比較性實施例V6及V8反應明顯更快速，甚至 於短暫之擠壓時間之後亦比V7產生明顯更少之氣泡。 擠出反應 表3示出「擠出反應」試驗之結果。 表3 :擠出反應 _ 實施例1 實施例2 實施例V6 實施例V7 實施例V8 擠出長度單位毫米 0.4 0.5 0.5 1.3 0.8 實施例V7及V8呈現比根據本發明實施例1及2明顯更強 之擠出結果。 儲存安定性 根據本發明之實施例於室溫（25 °C)及環境濕度下儲存 一年之後實施L型剝離試驗之結果維持表1中所示數値之 水準，而比較性實施例V6及V7於相同條件下之儲存後則 於L型剝離試驗中呈現施力/剝離數値下滑70%至90%。 -22- 201105766 實施例V6及V7必須被儲存在5 °C下，以將其特性幾 乎保留下來，而實施例1及2於室溫下至少呈現1年以上 之安定性》 結論 比較性實施例V4及V5於焊浴試驗中呈現不足之安定 性。比較性實施例V 5除此之外還無法被黏貼得夠好。比較 性實施例V6及V8於酚醛清漆樹脂和固化劑間之交聯網絡 化反應方面反應非常緩慢，而比較性實施例V7於擠壓時傾 向於產生無法容忍之氣泡。實施例V6及V7此外還無法被 儲存於室溫之下。 僅有根據本發明之實施例1、2及3通過所有之試驗。 本文中所述之膠帶極適合於根據本發明之使用，尤其 是完成根據本發明之目的。尤其根據本發明之黏膠組成物 係該等產品之平衡。 【圖式簡單說明】 無。 【主要元件符號說明】 無。 -23-Darin bedeuten: kB: no bubble generation; wMB: a few microbubbles; b: bubbles in the comparison of Examples 1 and 2 and several commercial products show that Examples 1 and 2 are significantly more reactive than Comparative Examples V6 and V8 Faster, even after a short squeeze time, produces significantly fewer bubbles than V7. Extrusion Reaction Table 3 shows the results of the "extrusion reaction" test. Table 3: Extrusion Reaction - Example 1 Example 2 Example V6 Example V7 Example V8 Extrusion Length Unit mm 0.4 0.5 0.5 1.3 0.8 Examples V7 and V8 are significantly stronger than Examples 1 and 2 according to the present invention. The result of the extrusion. Storage Stability The results of performing the L-type peel test after one year of storage at room temperature (25 ° C) and ambient humidity according to an embodiment of the present invention maintain the level shown in Table 1, while Comparative Example V6 and After storage of V7 under the same conditions, the force/peel number 値 decreased by 70% to 90% in the L-type peeling test. -22- 201105766 Examples V6 and V7 must be stored at 5 °C to retain their properties, while Examples 1 and 2 exhibit at least one year of stability at room temperature. Conclusion Comparative Example V4 and V5 exhibit insufficient stability in the solder bath test. Comparative Example V5 was not able to be adhered well enough. Comparative Examples V6 and V8 reacted very slowly in the cross-linking network reaction between the novolak resin and the curing agent, while Comparative Example V7 was inclined to produce intolerable bubbles upon extrusion. Examples V6 and V7 were not yet able to be stored at room temperature. Only all of the tests were carried out according to Examples 1, 2 and 3 of the present invention. The tapes described herein are highly suitable for use in accordance with the present invention, particularly in accordance with the purpose of the present invention. In particular, the adhesive composition according to the present invention is a balance of such products. [Simple description of the diagram] None. [Main component symbol description] None. -twenty three-