TW200817489A - Heat-activable adhesive tape particularly for bonding electronic components and conductor tracks - Google Patents
Heat-activable adhesive tape particularly for bonding electronic components and conductor tracks Download PDFInfo
- Publication number
- TW200817489A TW200817489A TW096130652A TW96130652A TW200817489A TW 200817489 A TW200817489 A TW 200817489A TW 096130652 A TW096130652 A TW 096130652A TW 96130652 A TW96130652 A TW 96130652A TW 200817489 A TW200817489 A TW 200817489A
- Authority
- TW
- Taiwan
- Prior art keywords
- adhesive tape
- heat
- activatable adhesive
- acid
- rti
- Prior art date
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- 239000002390 adhesive tape Substances 0.000 title claims abstract description 15
- 239000004020 conductor Substances 0.000 title abstract description 8
- 239000000853 adhesive Substances 0.000 claims abstract description 32
- 230000001070 adhesive effect Effects 0.000 claims abstract description 31
- 229920001400 block copolymer Polymers 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 239000003822 epoxy resin Substances 0.000 claims description 24
- 229920000647 polyepoxide Polymers 0.000 claims description 24
- 229920001971 elastomer Polymers 0.000 claims description 20
- 239000000806 elastomer Substances 0.000 claims description 20
- 150000008064 anhydrides Chemical class 0.000 claims description 12
- 239000002738 chelating agent Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 229920005989 resin Polymers 0.000 claims description 10
- 239000011347 resin Substances 0.000 claims description 10
- -1 accelerators Substances 0.000 claims description 9
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- 229920000642 polymer Polymers 0.000 claims description 8
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- 125000003700 epoxy group Chemical group 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229920002554 vinyl polymer Polymers 0.000 claims description 6
- 150000008065 acid anhydrides Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 125000003118 aryl group Chemical group 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229920006132 styrene block copolymer Polymers 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 238000012661 block copolymerization Methods 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
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- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
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- 230000004048 modification Effects 0.000 claims 1
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- 101001045744 Sus scrofa Hepatocyte nuclear factor 1-beta Proteins 0.000 description 20
- 238000004132 cross linking Methods 0.000 description 14
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- 239000000758 substrate Substances 0.000 description 10
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- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
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- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
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- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J7/00—Adhesives in the form of films or foils
- C09J7/10—Adhesives in the form of films or foils without carriers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/12—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives
- C08J5/124—Bonding of a preformed macromolecular material to the same or other solid material such as metal, glass, leather, e.g. using adhesives using adhesives based on a macromolecular component
- C08J5/128—Adhesives without diluent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/105—Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/11—Compounds containing metals of Groups 4 to 10 or of Groups 14 to 16 of the Periodic Table
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
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Description
200817489 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種在高溫具低流動性之熱可活化黏著 劑’其特別適合黏著撓性印刷導體軌道（撓性印刷電路板 FPCB 卜 【先前技術】 如今撓性印刷電路板常用於多種電子裝置，例如手 機、收音機、電腦、印表機等。其乃由銅層及高熔融抗性 熱塑性塑料（大多數爲聚醯亞胺，少數爲聚酯）所構成。此 等FPCB往往是由具特殊規格之膠帶所製得。一方面，爲 製得FPCB，銅箔須黏著於聚醯亞胺板；另方面，個別的 FPCB亦須互相黏著，在此場合下，聚醯亞胺黏著聚醯亞 胺。除此等應用外，FPCB亦黏著其他基材。 用於此等黏著任務之膠帶必須具有特殊規格。因爲必 須具備高黏著性能，所用膠帶通常爲在高溫加工之熱可活 化膠帶。此等膠帶在高溫（往往是約200°C之高溫）黏著 FPCB時，必須不會釋出揮發性成分。爲獲得高度內聚力’ 膠帶必須能在加熱時交聯。在黏合操作時之高壓，使得膠 帶在高溫之流動性須低。亦即未交聯膠帶之黏度須高’或 須快速交聯。此外，膠帶亦必須能耐軟焊料浴（soldei： bath)，換句話說，膠帶必須能短暫耐28 8°C之高溫。 爲此理由，採用純熱塑性樹脂並不合理，儘管它易熔’ 能確保黏合基材之潤溼，並可在數秒內快速黏合。然而在 高溫下，它太軟以致於在黏合過程中加壓會擠出黏合線 200817489 外。再者，它也不能耐軟焊料浴。 就可交聯膠帶而言，通常採用環氧樹脂或酚醛樹脂’ 其可和特殊硬化劑反應而得聚合物網狀結構。在本特殊場 合下，不能採用酚醛樹脂，因在交聯硬化過程中會釋出脫 除產物，而在硬化過程或最後在軟焊料浴導致起泡。 環氧樹脂主要用於結構黏合，經合適交聯劑固化後， 產生非常脆的黏著劑，其雖有高黏合強度，但實質上無可 撓性。 可撓性的提升乃應用於FPCB不可或缺的。一方面， 黏合乃利用理想上成卷之膠帶；另方面，導體軌道須爲撓 性，可彎曲，例如膝上型個人電腦之導體軌道即須爲撓性， 其可折疊式螢幕乃利用FPCB連接其他電路。 可用兩種方法使環氧樹脂黏著劑可撓化。首先，已知 利用彈性體鏈可使環氧樹脂可撓化，但由於彈性體鏈很 短，故可撓化程度有限。獲得可撓性之另外方案是在黏著 劑中加入彈性體。此案之缺點是彈性體未化學交聯，亦即 只有在高溫仍保持高黏度之彈性體才能使用。 因膠帶通常乃由溶液製得，往往不易尋求同時具備在 高溫不流動的足夠長的鏈及能溶解於溶液中之足夠短的鏈 之彈性體。 雖然可利用熱熔膠操作（hotmelt operation)，但在交聯 系統中頗爲困難，因必須在生產過程中防止太早的交聯。 在FPCB製造及加工領域之許多應用中，膠帶乃自通 常用於保護膠帶之離型介質取出，然後貼到欲黏合之基材 -6- 200817489 上。在此場合下，於操作前往往已模切之膠帶必須確保在 剝開離型介質時，或貼合到基材時不會變形。因爲剝開離 型介質時須施一點力量，膠帶的彈性模數必須足夠大，才 不會受力而產生任何延伸或其他變形。既然所用之產物須 儘可能的薄，就不易在膠帶中添加載體；事實上，一般而 言，膠帶只合一層黏著劑。因此，該黏著劑必須具足夠高 的彈性模數，而不會延伸。 美國專利第5,369，167A號有提及基於酸酐改質之嵌段 f ~ 共聚物及環氧樹脂之黏著劑；以及此複合配方之製法。此 外，須用交聯劑使環氧樹脂進行交聯。但該專利中，並未 提到膠帶。 類似的黏著劑於日本專利第5 7/ 1 493 69 A1亦有記載。 其環氧樹脂亦需要硬化劑。其中並未揭示膠帶 歐洲專利第1，3 11，5 59A2號記載著利用螯合劑使順丁 烯二酸酐改質之嵌段共聚物交聯，其中提到嵌段共聚物混 合物之內聚力有提升。儘管在高溫有螯合劑和環氧樹脂交 ί 聯，但未提及熱活化膠帶之製法。 此外，螯合劑與例如酸改質之丙烯酸酯黏著劑交聯記 載於例如美國專利第 4,005,247A號或美國專利第 3,7 69,254A 號。 德國專利第1 0-2004-03 1 - 1 88A1號揭示黏合電子元件 及可撓性導體軌道之膠帶，乃由至少一種酸改質或酸酐改 質之乙烯基芳基嵌段共聚物及環氧樹脂。但其中未提及金 屬螯合劑。 -7- 200817489 德國專利第 1 0-2004-007-25 8A1號揭示的用於黏著性 條狀片之黏著劑包含下列組成： -酸改質或酸酐改質之乙烯基芳基嵌段共聚物， -如下式所示之金屬螯合劑： (Rl〇)nM(XR2Y)m 式中Μ乃選自週期表主族元素第二、三、四、五週期 之金屬或過渡金屬；
Ri乃烷基或芳基； η 乃零或更大之整數； X及γ乃氧或氮，其均可利用雙鍵連接r2 ; R2乃連接X及Y之伸烷基，其可爲分枝的，或在鏈中 含氧或其他雜原子； m乃至少1之整數。 -增黏樹脂。 黏著性片條（adhesive sheet strip)可藉由在黏合線 (bondline)方向進行延展性拉伸而分離。 其中並未提及添加含環氧化物之化合物。 【發明內容】 有鑑於此，本發明之目的在提供一種熱可活化膠帶， 其受熱會交聯，加熱時黏度低，對聚醯亞胺之黏著性佳， 在未交聯狀態可溶於有機溶劑，且在室溫有高彈性模數。 令人驚奇的是利用申請專利範圍獨AL項所述之膠帶即 可實現此目的。申請專利範圍附屬項提供本發明標的物之 有利發展及可能的應用。 200817489 特別適合黏合電子元件和導體軌道之熱活化性黏著劑 至少包含 a) 酸改質或酸酐改質之乙烯基芳族嵌段共聚物， b) 含環氧基化合物， c) 金屬螯合劑。 在本發明中所言之”膠帶”包含所有片狀結構，例如 二維延展的片或片材、寬度有限而長度伸長之帶、帶材、 模切材等。 < 所用之黏著劑較佳爲嵌段共聚物，其包含較佳爲苯乙 烯之乙烯基芳族嵌段（A嵌段），及主要由較佳爲丁二烯及異 戊間二烯之1,3-二烯聚合而得之嵌段（B嵌段）。依本發明， 均聚物及共聚物嵌段均可使用。所得嵌段共聚物可含相同 或不同嵌段B，其可部分、選擇性或完全地氫化。嵌段共 聚物可呈線型A-B-A結構。亦可採用輻射構型之嵌段共聚 物、星形及線形多嵌段共聚物。其他可存、在的成分尙包含 A-B二嵌段共聚物。依本發明，乙烯基芳族化合物和'異丁 U 烯之嵌段共聚物亦可用。所有前述聚合物可單獨使用或互 相混合使用。 至少一些所用的嵌段共聚物必須經酸改質或酸酐改 質，改質操作主要是利用不飽和單羧酸及多羧酸或酸酐的 自由基插枝共聚合：例如富馬酸、衣康酸、檸康酸、丙烯 酸、馬來酐、衣康酐、檸康酐，較佳爲馬來酐。酸或酸酐 之用量較佳爲佔嵌段共聚物重量的0.5至4重量％。 可採用市售之嵌段共聚物，例如Shell之KratonTMFG1901 -9- 200817489 及 KratonTMFG19 24或 Asahi之 TuftecTMM1913及 TuftecTMM 1 943。 一般的瞭解，環氧樹脂爲每分子具一個以上環氧基之 單體或寡聚物。其可爲縮水甘油酯或表氯醇和雙酚A或雙 酚F或此兩者之混合物之反應產物。同樣適用的有環氧酚 醛樹脂，其乃酚及甲醛之反應產物再和表氯醇進行反應而 得。亦可採用具兩個或以上環氧末端基之單體化合物做爲 環氧樹脂之稀釋劑。亦可用彈性改質之環氧樹脂或環氧 改質之彈性體，例如環氧化苯乙烯嵌段共聚物（如Daicel 公司之 Epofriend) 〇 環氧樹脂例如有Ciba Geigy公司之AralditeTM6010、 CY-281TM、ECNTM 1 27 3、ECNTM 1280、MY720、RD-2; Dow 化 學公司之 DERTM33 1、73 2、7 36、DENTM432 ; Shell 化學公司 之 EponTM812、825、826、828、830 等及 HPTtm1071、1079; Bakelite 公司之 B akeli te™EPR 1 6 1 ' 166、172、191、194 等。 市售脂族環氧樹脂例如二氧化乙烯環己烷（如Union Carbide 公司之 ERL-4206、422 1、420 1、429 8 或 0400) 〇 彈性化彈性體可得自如Nov eon公司之Hy car。 環氧稀釋劑（含兩個或以上環氧基之單體）例如Bakelite 公司之 BakeliteTMEPD KR、EPD Z8、EPD HD、EPD WF 等或 UCCP 公司之 PolypoxTMR9、R12、R15、R19、R20 等。 雖然如前述，不一定要加交聯劑，但是仍可再加硬化 劑。在此所用的硬化劑必須只是具酸基或酸酐基之物質， 因主要用於環氧交聯反應之胺及胍和酸酐反應，而减少反 應基之數目。 -10- 200817489 除了已經談到之酸改質酸酐改質之乙烯基芳基嵌段共 聚物，亦可再加酸或酸酐以獲得較高的交聯度，故進一步 改善內聚力。在此情況下，如美國專利第3,970,608A號所 述，可用單體酸酐及酸，酸改質或酸酐改質之聚合物，以 及酸酐共聚物，如聚乙烯甲醚-馬來酐共聚物’例如是ISP 公司之 GantrezTM。 金屬螯合劑中之金屬可爲週期表主族元素第二、三、 四及五週期之金屬及過渡金屬。特別合適的是鋁、錫、鈦、 f 銷、給、飢、銳、絡、鑑、鐵、姑及姉。特佳爲銘及欽。 各種金屬螯合劑可用於螯合交聯，並可用下式表示： (Rl〇)nM(XR2Y)m 式中 Μ係如前述之金屬，
Ri係烷基或芳基，如甲基、乙基、丁基、異丙基或苄基， n係零或更大整數， X及Υ係氧或氮，其均可利用雙鍵連接R2 ’ R2係連接X及Y之伸烷基，其可呈分枝狀，或在鏈中 含氧或其他雜原子， m係整數，但至少爲1。 較佳之螯合配位基乃由下列化合物反應而得··三乙醇 胺、2,4-戊二酮、2-乙基-1，3-己二醇或乳酸。特佳之交聯劑 爲乙醯丙酮酸鋁及乙醯丙酮酸鈦。 所選酸及/或酸酐基對乙醯丙酮基的比必須約相同’以 便獲得最適交聯，經發現交聯劑少許過量是正面的。雖然 -11- 200817489 爲得適當的交聯，酐基及乙醯丙酮基中之任一基均不可有 5倍的莫耳過量，但是此兩基的比是可變化的。 環氧樹脂和彈性體之化學交聯可在黏著性薄膜中產生 很高的強度。其對聚醯亞胺的黏合強度亦明確地很高。 爲提升黏著性，亦可添加能和嵌段共聚物中彈性體鏈 段相容的增黏劑。 可用於本發明壓敏性黏著劑之增黏劑例如基於松香或 松香衍生物之未氫化、部分氫化或完全氫化之樹脂，二環 〇 戊二烯的氫化聚合物，基於C5、c5/c9或C9單體流之未氫 化、部分氫化、選擇性或完全氫化之樹脂，基於α -蒎烯及 /或/3 -蒎烯及/或（5 -寧烯之聚萜烯樹脂，和較佳爲純C8及 C9芳族的氫化聚合物。前述之增黏劑樹脂可單獨或混合使 用。 其他適用之添加劑典型上包含： -主抗氧化劑，如位阻酚 -次級抗氧化劑，如亞磷酸酯或硫醚 U -製程安定劑，如c-自由基補獲劑 -光安定劑，如紫外線吸收劑或位阻胺 -加工助劑 -末端嵌段補強樹脂 -塡充料，如二氧化矽、玻璃（經硏磨的或顆粒）、氧化 鋁、氧化鋅、碳酸鈣、二氧化鈦、碳黑、金屬粉末等 -顏料、染料及光學增亮劑 -必要時，其他聚合物，較佳爲本質爲彈性體者。 -12- 200817489 本發明系統的優點是很低之軟化溫度，其乃來自嵌段 共聚物末端嵌段中的聚苯乙烯之軟化點。因在交聯反應過 程中，彈性體引入聚合物網絡，在典型上用於黏合FPCB 之高溫（高至200°C)下，此反應很快，在黏合線上沒有黏著 劑滲出之現象。藉由添加所謂的催速劑可進一步提升反應 速度。 可用的促進劑例如： -三級胺，例如苄二甲胺、二甲胺甲酚、三（二甲胺甲 ( 基）酚 -三鹵化硼-胺錯合物 -被取代之咪唑 -三苯膦 理想上酸改質及/或酸酐改質之彈性體和環氧樹脂之 用量比例乃使環氧基和酐基之莫耳分率正好相等。若只用 稍微改質之彈性體及具低環氧化物當量的低分子量環氧樹 脂’則結果只得很少量-低於10重量％之環氧樹脂，百分率 I# 係所用之環氧樹脂的對改質苯乙烯嵌段共聚物而言。 雖然爲得足夠的交聯，酐基和環氧基均不可大於4倍 的莫耳過量，但是此兩基的比例可在廣範圍內變化。 爲製造膠帶，黏著性成分較佳爲溶於合適溶劑，例如 甲苯或萘70/90及丙酮之混合物；並使溶液塗於附有離型 層（如離型紙或離型薄膜）之撓性基板上；乾燥塗層，使得 組成物又能容易自基板再次移除。經合適的加工、模切， 乃在室溫製得輥狀或其他形狀產物。然後較佳爲在高溫將 -13· 200817489 對應形狀黏著於欲黏合之基板（如聚醯亞胺）上。 亦可直接將黏著劑塗在聚醯亞胺基板上。然後此種黏 著劑片可用於罩蓋FPCB中之銅導體軌道。 不一定須在單一製程中完成貼合操作。膠帶可先以熱 層合黏附於兩基板之一。在實際上和第二基板（第二聚醯亞 胺片或銅箔）熱黏合操作中，樹脂接著完全或部分硬化，並 使黏合線獲得高黏合強度。 所混合的環氧樹脂較佳在層合溫度時應先不進行任何 ( 化學反應，而是在熱貼合時與酸或酸酐反應。 本發明黏著劑之優點是彈性體事實上和樹脂化學結 合；不必在環氧樹脂中加入硬化劑，因爲彈性體本身即硬 化劑。 由於製程中乾燥操作產生和金屬螯合物之交聯，所以 本發明黏著劑明顯硬化，彈性模數也提高。 令人驚奇的是儘管在室溫交聯，通常在高於150°C之 熱活化會在彈性體之酸基及酐基和金屬螯合物之間導至改 I 質彈性體和環氧樹脂交聯，產生高度內聚力及高黏合強 度。金屬螯合物並不會妨害第二階段之交聯。 【實施方式】 玆以非限制本發明範圍之實施例進一步說明本發明。 〔貫施例一〕 在甲苯中溶解92.5克KratonTMFG1901(馬來酐改質之苯 乙烯-乙烯/丁烯-苯乙烯嵌段共聚物，其中具30重量％聚苯 乙烯嵌段及約2重量％馬來酐）、7.5克BakeliteTMEPR191(環 -14- 200817489 氧樹脂）及2克乙醯丙酮酸鋁之混合物，並將所得溶液塗於 1.5克/米3矽酮化離型紙上，在1 10°C乾燥塗層15分鐘。 黏著層厚度爲25微米。 〔實施例二〕 在甲苯中溶解 87·4·克 KratonTMFG1901 、2.6 克 3&1^1^674?11161(環氧樹脂）、10克尺62&川6了41100((£&5111^11) 公司之氫化烴樹脂，軟化點約100°C)及1.5克乙醯丙酮酸鋁 之混合物，並將所得溶液塗於1.5克/米3矽酮化離型紙上， ^ 在110°c乾燥塗層15分鐘。黏著層厚度爲25微米。 〔比較例三〕 在甲苯中溶解92.5克KratonTMFG1901(馬來酐改質之苯 乙烯-乙烯/丁烯-苯乙烯嵌段共聚物，其中具30重量％聚苯 乙烯嵌段及約 2 重量％馬來酐）及 7.5 克 BakeliteTMEPR191(環氧樹脂）之混合物，並將所得溶液塗於 1.5克/米3矽酮化離型紙上，在ll〇°C乾燥塗層15分鐘。 黏著層厚度爲25微米。 (j F_?CB和所得膠帶之黏合 利用實施例1至3所得膠帶各黏合兩片FPCB。爲此目 的，在100°C將膠帶層合於聚醯亞胺/銅箔FPCB層合板中 之聚醯亞胺片上。然後將另一 FPCB之聚醯亞胺片黏合於 膠帶，並將整個組合放入可加熱之Biirkle壓機中，於180°C 加壓1.3MPa經歷30分鐘。 亂試方法 前面實施例所得黏著劑板係以下列測試方法測其性質： -15- 200817489 FPCB之T-剝雛試驗 利用拉力試驗機（Z wick公司製），以180°角及50毫米/ 分鐘之速率剝離前面製程所得之FPCB/膠帶/FPCB之複合 體，測量所需的力量（牛頓/厘米）。在20°C及50%相對溼度 下，進行測試。每一測試値均測定三次。 在5%伸長率之力i 因爲如此高可撓性薄材料往往不易測定其彈性模數， 所以改測在5 %伸長率之力量。其藉由自黏著條衝切1厘米 寬及10厘米長黏著劑；並夾於拉力試驗機，以300毫米/ 分鐘之速率拉伸該條，記錄在5 %伸長率之力量。結果以牛 頓/厘米記錄。 軟焊料浴耐性 將前面製程黏合所得FPCB複合體放入溫度爲288°C之 軟焊料浴10秒。若不會產生氣泡引起FPCB中聚醯亞胺層 膨脹，則表示本黏合能耐軟焊料浴。然而即使略有氣泡產 生，均列爲失敗。 溫度安定性 彷照前面所述T-剝離試驗，依據上述所揭示之方式所 製得之FPCB複合體之一端被懸吊起來，而另一端吊著500 克之重物。在7〇°C做靜態剝離試驗。測量單位時間靜態剝 離之距離（毫米/小時）。 試驗結果 爲評估前述諸例的黏著劑，先做T -剝離試驗。結果列 於表1中。 -16- 200817489 表1 T-剝離試驗（牛頓/厘米） 實施例 1 8.6 實施例 2 14.8 實施例 3 9.7 由此可知實施例 1及實施例 3均同樣可得高黏著強
度。 膠帶之溫度安定性可用靜態剝離試驗評估’結果列於 表2中。 表2 70°C靜態T-剝離試驗（毫米/小時） 實施例1 4 實施例2 11
實施例 3 - 實施例1及3並無大差異；只是實施例2採用樹脂摻 混料，剝離略多。在5 %伸長率下的拉力列於表3。 表3 在5%伸長率下的拉力（牛頓/厘米） 實施例1 1.4 實施例2 1.2 實施例3 0.6 -17- 200817489 以螯合劑交聯明顯提升拉伸膠帶所需的力量 此三例均通過金屬熔化液測試。 【圖式簡單說明】 Μ 〇 y \ \Ν 【元件符號說明】 無。
Claims (1)
- 200817489 十、申請專利範圍： 1. 一種熱可活化膠帶，其特別適用於黏合電子元件及電 路，其中黏著劑至少包含下列成分： a) 酸改質或酸酐改質之乙烯基芳基嵌段共聚物， b) 含環氧基之化合物， c) 金屬螯合劑。 2 ·如申請專利範圍第1項所述之熱可活化膠帶’其中乙嫌 基芳基嵌段共聚物爲苯乙烯嵌段共聚物。 Η 3·如申請專利範圍第1或2項所述之熱可活化膠帶，其中 含環氧基之化合物爲環氧樹脂及/或環氧化聚合物。 4 ·如申請專利範圍第1至3項任一項所述之熱可活化膠 帶，其中環氧基和彈性體之酸基及/或酸酐基於150°C以 上之溫度進行交聯。 5 ·如前述申請專利範圍任一項所述之熱可活化膠帶，其中 金屬螯合劑可用下式表示： (RlO)nM(XR2Y)m V 式中 Μ係週期表主族元素第二、三、四或五週期之金屬或過渡金屬， R!係烷基或芳基，如甲基、乙基、丁基、異丙基或节基， η係零或較大整數， · X及Υ係氧或氮，其均可利用雙鍵連接R2， R2係連接X及Y之伸烷基，其可呈分枝狀，或在鏈中含 氧或其他雜原子， m係整數，但至少爲1。 -19- 200817489 6 ·如目丨j述申請專利範圍任一項所述之熱可活化膠帶，其中 金屬螯合劑係乙醯丙酮酸鋁或乙醯丙酮酸鈦。 7 ·如目ij述申請專利範圍任一項所述之熱可活化膠帶，其中 膠帶包含其他酸酐、其他彈性體、增黏樹脂、催速劑、 染料、碳黑及/或金屬粉末。 8 ·如則述申請專利範圍任一項所述之熱可活化膠帶，其中 環氧樹脂分率不大於酸改質及/或酸酐改質之彈性體重 量之10 %，較佳爲5重量％。 广 9. 一種以黏著劑黏合塑膠元件之方法，其中採用如前述申 g靑專利範圍中至少一項之熱可活化膠帶，其乃至少由酸 改質及/或酸酐改質之乙烯基芳基嵌段共聚物及環氧樹 脂組成的。 10·—種如前述申請專利範圍中至少一項之熱可活化膠帶 的用法，其係用於黏合塑膠元件。 11 · 一種如前述申請專利範圍中至少一項之熱可活化膠帶 / 的用法，其係用於黏合電子元件及/或撓性印刷電路板 C / (FPCB)。 1 2 · —種如前述申請專利範圍中至少一項之熱可活化膠帶 的用法，其係用於黏合聚醯亞胺。 -20- 200817489 七、指定代表圖： (一） 本案指定代表圖為：無。 (二) 本代表圖之元件符號簡單說明： Ληπΐ 無 八、本案若有化學式時，請揭示最能顯示發明特徵的化學式： 無-4-
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| TWI493004B (zh) * | 2009-08-12 | 2015-07-21 | Tesa Se | 封裝電子零件之方法 |
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2006
- 2006-10-06 DE DE102006047738A patent/DE102006047738A1/de not_active Withdrawn
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- 2007-08-20 TW TW096130652A patent/TWI453266B/zh not_active IP Right Cessation
- 2007-09-24 KR KR1020097009340A patent/KR101496787B1/ko not_active Expired - Fee Related
- 2007-09-24 EP EP07820503A patent/EP2079815B1/de not_active Not-in-force
- 2007-09-24 DE DE502007005081T patent/DE502007005081D1/de active Active
- 2007-09-24 AT AT07820503T patent/ATE481459T1/de active
- 2007-09-24 US US12/440,276 patent/US9273231B2/en not_active Expired - Fee Related
- 2007-09-24 CN CNA2007800374281A patent/CN101522844A/zh active Pending
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- 2007-09-24 WO PCT/EP2007/060096 patent/WO2008043660A1/de not_active Ceased
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| TWI482831B (zh) * | 2009-08-12 | 2015-05-01 | Tesa Se | 封裝電子零件之方法 |
| TWI493004B (zh) * | 2009-08-12 | 2015-07-21 | Tesa Se | 封裝電子零件之方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2008043660A1 (de) | 2008-04-17 |
| KR20090088873A (ko) | 2009-08-20 |
| EP2079815A1 (de) | 2009-07-22 |
| DE102006047738A1 (de) | 2008-04-10 |
| TWI453266B (zh) | 2014-09-21 |
| US20100012271A1 (en) | 2010-01-21 |
| US9273231B2 (en) | 2016-03-01 |
| ATE481459T1 (de) | 2010-10-15 |
| KR101496787B1 (ko) | 2015-02-27 |
| CN101522844A (zh) | 2009-09-02 |
| EP2079815B1 (de) | 2010-09-15 |
| DE502007005081D1 (de) | 2010-10-28 |
| JP2010505978A (ja) | 2010-02-25 |
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