TW202212316A - 用於低間隙底部填充應用之與助熔劑相容的環氧酚系黏著劑組合物 - Google Patents

用於低間隙底部填充應用之與助熔劑相容的環氧酚系黏著劑組合物 Download PDF

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Publication number
TW202212316A
TW202212316A TW110111505A TW110111505A TW202212316A TW 202212316 A TW202212316 A TW 202212316A TW 110111505 A TW110111505 A TW 110111505A TW 110111505 A TW110111505 A TW 110111505A TW 202212316 A TW202212316 A TW 202212316A
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Taiwan
Prior art keywords
cycloaliphatic
flux
compatible
adhesive
epoxy
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TW110111505A
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English (en)
Inventor
雷司米沙 Ｍ 斯利達
展航 楊
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德商漢高智慧財產控股公司
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Application filed by 德商漢高智慧財產控股公司 filed Critical 德商漢高智慧財產控股公司
Priority to JP2023560528A priority Critical patent/JP2024515506A/ja
Priority to KR1020237033261A priority patent/KR20230164059A/ko
Priority to PCT/US2021/045140 priority patent/WO2022211838A1/en
Publication of TW202212316A publication Critical patent/TW202212316A/zh
Priority to US18/372,206 priority patent/US20240010890A1/en

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    • C09J163/10—Epoxy resins modified by unsaturated compounds
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/732—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids of unsaturated hydroxy carboxylic acids
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    • C07C69/76—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring
    • C07C69/84—Esters of carboxylic acids having a carboxyl group bound to a carbon atom of a six-membered aromatic ring of monocyclic hydroxy carboxylic acids, the hydroxy groups and the carboxyl groups of which are bound to carbon atoms of a six-membered aromatic ring
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C08G59/5046—Amines heterocyclic
    • C08G59/5053—Amines heterocyclic containing only nitrogen as a heteroatom
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Abstract

本發明提供可用作低間隙底部填充之與助熔劑相容的環氧酚黏著劑組合物及可用於其中之新穎酚類。該等與助熔劑相容的環氧酚黏著劑組合物包括環氧組分，其包括具有環脂肪族、脂環族或混合環脂肪族-芳香族主鏈之環氧化合物；多官能酚系組分及觸媒。該等與助熔劑相容的組合物可用作底部填充密封劑，其(1) 快速填充諸如倒裝晶片總成之半導體裝置中之底部填充空間，(2) 使該裝置能夠藉由短時間熱固化牢固地連接至電路板且具有良好生產力，及(3) 展現優良抗焊料回流性。

Description

用於低間隙底部填充應用之與助熔劑相容的環氧酚系黏著劑組合物
本發明係關於用於低間隙底部填充應用之與助熔劑相容環氧酚系黏著劑組合物及可用於其中之新穎酚類。
提供以下討論僅用以幫助讀者理解本揭示內容，且不允許描述或構成現有技術。
近年來，小型電子用具之流行使得半導體裝置之期望大小縮小。因此，晶片封裝之大小正實質上縮小至裸晶粒本身之大小。使新的封裝設計具有更多功能、更精細間距、低間隙、更薄封裝以及擴展的下游市場之趨勢不僅帶來更高可靠性要求，而且亦產生前幾代底部填充技術不存在之許多新挑戰。
將積體電路附接至有機基板板之倒裝晶片方法使用積體電路上之一系列金屬焊料凸塊，該等凸塊與板上之金屬結合位點形成互連。積體電路之作用側翻轉倒置以使積體電路上之凸塊與基板上之金屬結合位點接觸。使用有機焊接助熔劑以去除金屬氧化物並在總成在高於焊料之熔融溫度下加熱時促進焊料之潤濕。將積體電路附接至基板之此製程稱為回流焊接。助熔劑之目的係清潔金屬之表面以改良電連接。焊料或低熔點合金可包含基板上之金屬結合位點、積體電路上之凸塊或二者，此取決於所選之材料。高熔點合金亦可同樣存在於無鉛焊料中。類似地，主要出於對環境之關注，高熔點合金可存在於無鉛焊料中。
利用小間隙底部填充，助熔劑之殘餘物難以自窄間隙去除。因此，在焊料回流製程之後不自板去除助熔劑殘餘物之免清潔助熔劑係用於大多數倒裝晶片應用之助熔劑選擇。該等免清潔助熔劑可在晶片佈置之前分配至板上之金屬結合位點。為在回流製程之前維持晶片與板之對準，可將黏性助熔劑施加至晶片上之凸塊。將含有焊料凸塊之積體電路浸於助熔劑中達設定深度以將期望量之黏性助熔劑僅施加至凸塊之表面。然後將晶片對準並放置於基板上，以使得助熔劑塗佈之凸塊接觸基板上之適當金屬結合位點。黏性助熔劑經調配以獲得較高固體含量，此有助於在回流之前將晶片黏著至基板。因此，黏性助熔劑充當臨時膠水，以在將總成置於回流爐期間保持晶片之適當對準。常用黏性助熔劑係免清潔表面安裝製程中所用之焊料膏助熔劑媒劑。
儘管免清潔焊料膏助熔劑媒劑之調配物有所變化，但典型組合物含有50%松香、40%溶劑、5-8%增稠劑及2-5%助熔劑活化劑(例如，有機酸及胺)。儘管助熔劑之大多數溶劑在回流製程期間蒸發掉，但留下松香酯及焊料膏成分之其他非揮發性殘餘物。
在焊料回流以將積體電路附接至基板之後，倒裝晶片總成中之積體電路與有機基板之間之間隙藉由毛細管作用利用底部填充囊封劑或黏著劑進行填充。囊封劑之目的係減輕焊料互連上之熱機械應力，該等熱機械應力係由矽積體晶片(熱膨脹係數(CTE) = 2.5 ppm/℃)與有機基板(CTE = 15-20 ppm/℃)之間之熱膨脹係數差異引起。
倒裝晶片總成中所用之典型底部填充囊封劑係由環氧樹脂、固化劑及無機填充劑組成以在固化時獲得交聯熱固性聚合物。固化聚合物之性質(例如，CTE及彈性模數)有助於在使用期間減輕焊料接點上之熱機械應力，該熱機械應力係藉由熱循環測試進行測試。典型熱循環測試涉及在-55℃及125℃下倒裝晶片總成對兩種不同液體之重複暴露，其中在每一溫度下具有10分鐘停留時間。因此，底部填充囊封劑之總體目的係藉由減輕焊料接點上之熱機械應力增強倒裝晶片總成之操作壽命及可靠性。
若干製程及材料性質特徵決定底部填充囊封劑之材料選擇。首先，環氧底部填充囊封劑應在生產期間在晶片下快速流動。囊封劑之黏度、表面張力及粒徑分佈可經最佳化以在囊封步驟期間達成晶片下之高效流動。為進一步減少底部填充時間，基板可經加熱以降低未固化囊封劑之黏度並增強材料之流動速度。通常在分配囊封劑之前將基板板表面加熱至70℃，以達成此效應。其次，環氧底部填充囊封劑應相對較快地固化。典型底部填充囊封劑係經設計以在130-170℃之溫度下固化(即，形成不可逆地交聯結構)之環氧調配物。最後，環氧底部填充囊封劑應在熱循環測試期間牢固地黏附至晶片及基板二者。若環氧自晶片或基板表面脫落或分層，則將不能達成互連上之適當應力緩解。
免清潔助熔劑殘餘物與環氧底部填充囊封劑之間之相互作用對於達成最大黏著及期望倒裝晶片可靠性甚為重要。作為黏性助熔劑用於倒裝晶片製程之典型焊料膏助熔劑組合物含有松香或類似樹脂。在將積體電路回流焊接至基板之後，松香之殘餘物及助熔劑之非揮發性有機成分留在基板上。儘管該等免清潔殘餘物就其腐蝕性而言對總成係良好的，但已知該等殘餘物造成空洞及焊料擠壓，此不利地影響裝置之黏著及電完整性。此結果可由於底部填充囊封劑之差黏著而導致晶片表面之早期分層。囊封劑自晶片之此脫層可使用掃描聲學顯微鏡(SAM)檢測及量測，此允許檢測晶片表面與環氧底部填充之間空隙之存在。
因此，助熔劑與底部填充囊封劑之相容性係底流製程性能之重要準則。
在經受重複焊料回流條件時顯示穩定Tg且具有低吸濕性之與助熔劑相容的底部填充黏著劑將係高度期望的。維持穩定Tg對於在較高溫度下之良好黏著甚為重要。
本揭示內容提供可用作底部填充密封劑之與助熔劑相容的組合物，其(1) 快速填充半導體裝置(例如，倒裝晶片總成)中之底部填充空間，(2) 使裝置能夠藉由短時間熱固化牢固地連接至電路板且具有良好生產力，及(3) 展現優良熱循環性質。組合物包含環氧樹脂組分、酚系組分及觸媒。本揭示內容亦提供可用於組合物中之新穎酚類。
使用本揭示內容之組合物，半導體裝置(例如，倒裝晶片總成)可(1) 由於經改良之固化速度及延長之可用工作壽命而快速組裝且沒有生產線停機時間，以及(2)藉由組合物之短時間熱固化牢固地連接至電路板，其中所得安裝結構展現優良熱衝擊性質或熱循環性質。
因此，本揭示內容提供通常用於低間隙底部填充應用之與助熔劑相容的環氧酚黏著劑組合物。組合物包括： 環氧組分，其包含具有環脂肪族、脂環族或混合環脂肪族-芳香族、脂環族-芳香族主鏈之環氧化合物； 酚系組分，例如，多官能酚；及 觸媒。
環氧組分可為具有環脂肪族、脂環族、混合環脂肪族-芳香族或脂環族-芳香族主鏈之環氧化合物。
酚系組分可係例如由一般結構I、II、III及/或IV代表之多官能酚：
Figure 02_image001
Figure 02_image003
其中X係單環、二環或多環結構，其為視情況具有脂肪族側鏈之環脂肪族、脂環族或混合環脂肪族-芳香族，且酯基團之氧可直接連接至環或脂肪族側鏈； X 1係視情況包含雜原子O或S之伸烷基或具支鏈伸烷基； R 3係H、烷基或環烷基； L 1及L 2獨立地選自共價鍵、視情況包含雜原子O或S之伸烷基、具支鏈伸烷基及伸環烷基； R 1及R 2係H、甲基或OH，前提條件係在每一環中R 1或R 2中之至少一者係OH；且 結構I、II、III及IV中存在之酯基團可為一級或二級酯基團。 或者，酚組分可選自結構V、VI及/或VII：
Figure 02_image005
其中R係脂肪族、環脂肪族、脂環族、混合芳香族-環脂肪族或聚合物主鏈；另外，在結構V及VII中，R可為稠合環； R 1及R 2係H、烷基或OH，前提條件係R 1或R 2中之至少一者係OH； L選自共價鍵、視情況具有雜原子O或S之伸烷基、伸環烷基及具支鏈伸烷基；L亦可含有酯或碳酸酯鍵聯； n=1-10；且 連接至結構V中之酚環的稠合環係可選的且在存在時可為芳香族、環脂肪族、脂環族或雜環。
觸媒可選自咪唑、經取代咪唑、潛在性咪唑、經囊封咪唑、酚官能化咪唑及萘酚官能化咪唑、以及脒及胍型觸媒或酚官能化咪唑觸媒。
本揭示內容之益處及優點自以下實施方式將變得更顯而易見。
如所提及，本揭示內容提供可用於低間隙底部填充應用之與助熔劑相容的環氧酚黏著劑組合物。組合物寬泛地包含環氧組分、酚系組分及觸媒。
環氧組分可選自具有環脂肪族、脂環族、混合環脂肪族-芳香族或混合脂環族-芳香族主鏈之環氧化合物。 特別有用之環氧樹脂係下文式中所示之EP4088S、Eponex1510、HP7200、Hyloxy改質劑107及其混合物，但亦可使用具有環脂肪族、混合環脂肪族-芳香族主鏈及/或芳香族主鏈之其他樹脂。實例包括由Sugai Chemical Industry共用之單官能及雙官能十氫萘縮水甘油基醚、基於環脂肪族主鏈(例如，金剛烷環結構)之單及多官能縮水甘油基醚，包括單及多官能十氫萘縮水甘油基醚、單及多官能DCPD縮水甘油基醚、氫化雙酚A之二縮水甘油醚、單及多官能金剛烷基縮水甘油基醚、環脂肪族縮水甘油基酯、環狀單烯及多烯之單及多官能環氧化物及其混合物。
Figure 02_image007
酚系組分可為多官能酚且可選自其式在下文給出之彼等：
Figure 02_image009
該等多官能酚類(即，酚類1-4)係新穎的且形成本揭示內容之另一態樣。
除以上新穎酚類以外，可使用某些已知脂環族酚類作為組合物之酚系組分。適宜酚類係由DIC International Chemicals以商標名Phenolite TM酚清漆型酚醛樹脂出售。尤其適宜之已知酚類係DCPD酚醛清漆及甲酚酚醛清漆。亦有用者係雙酚A清漆型酚醛樹脂、苯酚清漆型酚醛樹脂、三嗪清漆型酚醛樹脂、二烯丙基雙酚A、二羥基萘(所有異構物)、2-烯丙基苯基清漆型酚醛樹脂、二羥基二苯甲酮(所有異構物)、三羥基二苯甲酮(所有異構物)、Rezicure 3000、雙(4-羥基苯基)硫醚及雙(4-羥基苯基)碸。
酚系組分亦可為由一般結構I、II、III及/或IV代表之多官能酚：
Figure 02_image011
Figure 02_image013
其中X係單環、二環或多環結構，其為視情況具有脂肪族側鏈之環脂肪族或脂環族；且酯基團之氧直接連接至該環或側鏈； X 1係視情況包含雜原子O或S之伸烷基或具支鏈伸烷基； R 3係H、烷基或環烷基； L 1及L 2獨立地選自共價鍵、視情況包含雜原子O或S之伸烷基、具支鏈伸烷基及伸環烷基； R 1及R 2獨立地係H、甲基或OH，前提條件係在每一環中R 1或R 2中之至少一者係OH；且 結構I、II、III及IV中存在之酯官能性可為一級或二級酯基團。
與助熔劑相容的環氧酚黏著劑化合物中所用之酚可選自結構V、VI及/或VII之化合物：
Figure 02_image015
其中R係脂肪族、環脂肪族、脂環族、混合芳香族-環脂肪族或聚合物主鏈；另外，在結構V及VII中，R可為稠合環； R 1及R 2係H、烷基或OH，前提條件係R 1或R 2中之至少一者係OH； L選自共價鍵、視情況具有雜原子O或S之伸烷基、伸環烷基及具支鏈伸烷基；L亦可含有酯或碳酸酯鍵聯； n=1-10；且 連接至結構V中之酚環的稠合環係可選的且在存在時可為芳香族、環脂肪族、脂環族或雜環。
以上醯亞胺或鄰苯二甲醯亞胺官能酚類可藉由脂肪族、脂環族、芳香族、芳烷基胺利用單或多官能酸酐亞胺化來獲得。酸酐可選自甲基六氫鄰苯二甲酸酐、納迪克酸酐(nadic anhydride)(甲基-5-降莰烯-2,3-二甲酸酐；「MNA」)或5-降莰烯-2,3-二甲酸酐、六氫-4-甲基鄰苯二甲酸酐(MHHPA)、甲基四氫鄰苯二甲酸酐(MTHPA)、甲基環己烯-1,2-二甲酸酐、甲基二環[2.2.1]庚烷-2,3-二甲酸酐、二環[2.2.1]庚烷-2,3-二甲酸酐、(2-十二烯-1-基)琥珀酸酐、戊二酸酐、檸康酸酐、甲基琥珀酸酐、2,2-二甲基琥珀酸酐、2,2-二甲基戊二酸酐、3-甲基戊二酸酐、3,3-四亞甲基戊二酸酐、3,3-二甲基戊二酸酐、羥基鄰苯二甲酸酐之若干異構物或其混合物。
可用於亞胺化反應之多官能酸酐包括聚丙烯-接枝-馬來酸酐、聚乙烯-接枝-馬來酸酐、丁二烯-馬來酸酐共聚物、苯乙烯-馬來酸酐共聚物及其他共聚物及馬來酸酐、衣康酸酐及檸康酸酐之三元共聚物。
可用於亞胺化反應之胺及胺官能酚類包括(但不限於)胺基酚之若干異構物、兒茶酚胺、胺基萘酚、二聚體二胺、TCD-二胺(3(4),8(9)-雙(胺基甲基)-三環癸烷)、環己胺、脂肪族、環脂肪族及脂環族一級二胺。
環氧酚黏著劑組合物可進一步包含馬來醯亞胺樹脂，其可為雙馬來醯亞胺、多官能馬來醯亞胺或下文表示之結構VIII及IX之酚官能馬來醯亞胺。
Figure 02_image017
其中L選自共價鍵、視情況具有雜原子O或S之伸烷基、伸環烷基及具支鏈伸烷基；L亦可含有酯或碳酸酯鍵聯；且 結構VIII中之稠合環係可選的且當存在時其係芳香族、環脂肪族、脂環族或雜環。
馬來醯亞胺樹脂可藉由單或多官能一級胺與馬來酸酐之亞胺化反應獲得或可藉由單或多官能脂肪族、環脂肪族、脂環族或芳烷基醇與6-馬來醯亞胺基己酸之費歇爾酯化(Fisher esterification)獲得。酚官能馬來醯亞胺亦可藉由胺基酚類之若干異構物、胺基萘酚類、兒茶酚胺或側鏈胺官能酚類與馬來酸酐之亞胺化反應獲得。
可使用各種觸媒，其中包括咪唑、經取代咪唑、潛在性咪唑、經囊封咪唑、酚官能化咪唑及萘酚官能化咪唑。已發現咪唑觸媒Technicure EMI-24CN係特別期望之固化劑。例如，在4%濃度下，具有此觸媒之環氧酚黏著劑組合物顯示Tg與其他性能性質之優良平衡。可使用自Evonik Corporation獲得以商標名Curezol出售之潛在性咪唑、來自A&C catalysts之經囊封咪唑及酚或萘酚官能化咪唑(例如，Aradur 3123)。較佳觸媒包括Technicure EMI 24-CN、Curezol 2-PHZ-S、Curezol 2-PZ、Curezol 2PZ-吖嗪、Aardur 3123及胺及多胺官能咪唑。
環氧組分對酚系組分之比率可為1:1至1:0.05。該比率較佳為1: 0.2，且更佳1: 0.1。環氧組分及酚系組分之組合通常構成黏著劑組合物之約50%，其餘者係選自固化劑、加速劑、觸媒、流動改質劑、填充劑、黏著促進劑及觸變劑。
在某些實施例中，黏著劑組合物可進一步包含一或多種流動添加劑、黏著促進劑、導電性添加劑、流變改質劑或諸如此類，以及其任兩種或更多種之混合物。視需要，組合物中可含有各種添加劑，例如有機或無機填充劑、觸變劑、矽烷偶合劑、稀釋劑、改質劑、著色劑(例如，顏料及染料)、表面活性劑、防腐劑、穩定劑、塑化劑、潤滑劑、消泡劑、整平劑及諸如此類；然而，並不限於該等。具體而言，組合物較佳包含選自由有機或無機填充劑、觸變劑及矽烷偶合劑組成之群之添加劑。該等添加劑可以總組合物之約0.1重量%至約50重量%、更佳總組合物之約2重量%至約10重量%之量存在。
觸變劑可包括(但不限於)滑石、發煙二氧化矽、經表面處理之超細碳酸鈣、氧化鋁細粒、片狀氧化鋁；層狀化合物(例如蒙脫石)、針狀化合物(例如硼酸鋁晶須)及諸如此類。在該等中，滑石、發煙二氧化矽及細氧化鋁係特別期望的。該等試劑可以重量計以總組合物之約1%至約50%、更佳約1%至約30%之量存在。
矽烷偶合劑可包括(但不限於) γ-胺基丙基三乙氧基矽烷、γ-巰基丙基三甲氧基矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、γ-縮水甘油氧基丙基三甲氧基矽烷及諸如此類。
如本文所用，「流動添加劑」係指矽聚合物、丙烯酸乙酯/丙烯酸2-乙基己基酯共聚物、酮肟磷酸酯之烷醇銨鹽及諸如此類，以及其組合。該等添加劑中之一些係自商業來源(例如，BYK及Evonik Corporation)購得。
本揭示內容提供以下非限制性及非詳盡性實例。 實例
在酚環氧調配物中篩選若干咪唑觸媒，如表1中所示。所測試之一些調配物顯示當使用適宜咪唑加速劑時具有較高Tg。液體咪唑觸媒(Technicure EMI-24CN)似乎在降低固化溫度方面表現最佳。此觸媒之低黏度係額外優點。 表 1 ： 酚固化環氧系統之初始調配物篩選
調配物 組分 DSC 峰值溫度 Tg
F1 BPF DGE、1,1,1(參羥基苯基)乙烷、curezol 2PZ (6%) 125℃ 132℃
F2 BPF DGE、1,1,1(參羥基苯基)乙烷、1-(2-氰基乙基)-2-苯基咪唑(Technicure EMI-24CN)  (5%) 125℃ 115℃
F3 830CRP、GY 9820、1,1,1(參羥基苯基)乙烷、curezol 2PHZ-S (5%) 160℃ 138℃
F4 830CRP、GY 9820、1,1,1(參羥基苯基)乙烷、curezol 2PZ (5%) 130℃ 126℃
F5 830CRP、GY 9820、1,1,1(參羥基苯基)乙烷、curezol 2PZ吖嗪(5%) 130℃ 143℃
已發現，具有環脂肪族主鏈之環氧樹脂顯示良好的助熔劑相容性。以純淨形式針對助熔劑相容性進行篩選之一些環氧樹脂包括EP4088S、Eponex1510、HP7200L、Hyloxy改質劑107及上述之混合物。所有該等環氧樹脂均具有環脂肪族或混合環脂肪族-芳香族主鏈。助熔劑相容性研究係使用含有約5%助熔劑之環氧樹脂並將混合物加熱至約80℃達約30分鐘並將混合物高速混合來實施。將其冷卻至室溫並儲存後，其產生澄清混合物而無任何混濁。
對於酚系組分，製得含有環脂肪族或脂肪族主鏈之若干多官能酚類，如以下實例中所述。 實例 1 ：四官能酚 1 之合成
Figure 02_image019
在配備有熱電偶、機械攪拌器及冷凝器之1L 3頸燒瓶中放置於甲苯600mL中之4,8-雙(羥基甲基)三環[5.2.1.0 2,6]癸烷(49.2g, 250mmol)、雙酚酸(143.5g, 500mmol)、PTSA (3g, 1.5%)。將混合物與水共沸蒸餾攪拌12h。冷卻至環境溫度後，將甲苯傾倒出並將剩餘固體溶解於1 L乙酸乙酯中。將溶液用水洗滌一次，用碳酸氫鈉水溶液洗滌兩次並用水洗滌一次。溶液經無水Na 2SO 4乾燥後，使用旋轉蒸發器在減壓下蒸發溶劑。在高真空下在80℃下若干小時以去除最後痕量之溶劑，以獲得呈紫色固體之酚1 (152g, 83%)。 實例 2 ：四官能酚 2 之合成
Figure 02_image021
在配備有熱電偶、機械攪拌器及冷凝器之1L 3頸燒瓶中放置於甲苯400mL中之3-甲基-1,5-戊二醇(8.94g, 75mmol)、雙酚酸(43.11g, 150mmol)、PTSA (1.1g, 2.2%)。將混合物與水共沸蒸餾攪拌12h。冷卻至環境溫度後，將甲苯傾倒出並將所得固體溶解於600 mL乙酸乙酯中。將溶液用水洗滌一次，用碳酸氫鈉水溶液洗滌兩次並用水洗滌一次。溶液經無水Na 2SO 4乾燥後，使用旋轉蒸發器在減壓下蒸發溶劑。在高真空下在80℃下若干小時以去除最後痕量之溶劑，以獲得呈紫色固體之酚2 (38g, 88%)。 實例 3 ：雙官能酚 3 之合成
Figure 02_image023
在配備有熱電偶、機械攪拌器及冷凝器之1L 3頸燒瓶中放置於甲苯600mL中之4,8-雙(羥基甲基)三環[5.2.1.0 2,6]癸烷(54.4g, 277mmol)、4-羥基苯甲酸(76.55g, 554mmol)、PTSA (2.6g, 2%)。將混合物與水共沸蒸餾攪拌12h。冷卻至環境溫度後，將甲苯傾倒出並將所得固體溶解於1 L乙酸乙酯中。溶液用水洗滌一次，用碳酸氫鈉水溶液洗滌兩次並用水洗滌一次。溶液經無水Na 2SO 4乾燥後，使用旋轉蒸發器在減壓下蒸發溶劑。在高真空下在80℃下若干小時以去除最後痕量之溶劑，以獲得呈紫色固體之酚3 (95g, 77%)。 實例 4 ：四官能酚 4 之合成
Figure 02_image025
在配備有熱電偶、機械攪拌器及冷凝器之1L 3頸燒瓶中放置於甲苯600mL中之4,8-雙(羥基甲基)三環[5.2.1.0 2,6]癸烷(35g, 177mmol)、3,4-二羥基苯基乙酸(59.96g，356 mmol)、PTSA (1.9g, 2%)。將混合物與水共沸蒸餾攪拌48h。冷卻至環境溫度後，將甲苯傾倒出並將剩餘固體溶解於1 L乙酸乙酯中。將溶液用水洗滌一次，用碳酸氫鈉水溶液洗滌兩次並用水洗滌一次。溶液經無水Na 2SO 4乾燥後，使用旋轉蒸發器在減壓下蒸發溶劑。在高真空下在80℃下若干小時以去除最後痕量之溶劑以獲得呈褐色固體之酚4 (79g, 82%)。
製作若干未填充環氧酚調配物並進行篩選，如下表2所示。 表 2 ： 未填充環氧酚系調配物
調配物 1 183C (g) 2 180C (g) 3 180D (g) 4 178B (g) 5 178F (g) 6 178D (g)
EPN 9820    5.73 5.44 3.28 2.66 1.68
EP4088S 3.73 1.99 1.89 3.28 3.04 1.93
BPA DGE    3.14 2.98         
HP7200L 2.32               
MY 0510 5.13    3.24 7.56 5.48 3.46
Hyloxy改質劑107    1.47            
o,o’-二烯丙基雙酚A          1.414 0.56 0.707
TD2131 1.13 2.0 1.9         
實例1之酚 1             0.56   
Technicure EMI-24CN 0.492 0.57 0.62 0.62 0.49 0.311
DSC峰值溫度(℃) 140℃ 138℃ NA 136℃ 137℃ 140℃
Tg (℃) 154℃ 115℃ 155℃ 150℃ 144℃ 134℃
上表2顯示若干環氧酚系未填充調配物及其固化及Tg概況。咪唑觸媒之量在所有該等調配物中保持恆定在4 wt%。發現使用Hyloxy改質劑107有益於降低黏度。然而，此環脂肪族環氧不利地影響Tg。使用四官能酚1與使用二烯丙基雙酚A之調配物相比似乎顯著增加Tg (表2中之調配物5對6)。
由於環脂肪族環氧樹脂以純淨形式顯示良好助熔劑相容性，因此將若干經填充調配物與其他環氧樹脂摻和以獲得Tg、黏度與助熔劑相容性之平衡。開發至少部分地含有具有環脂肪族主鏈之環氧樹脂之若干環氧酚系調配物以改良助熔劑相容性。與未填充調配物相比，當使用二氧化矽作為填充劑時，經填充調配物與等效的未填充調配物相比顯示Tg顯著降低。為獲得在120-140℃範圍內之Tg，可藉由添加具有環脂肪族-脂肪族主鏈之多官能酚類對調配物進行改質，以製得表3中所示之調配物。 表 3 ： 使用與助熔劑相容的環氧樹脂之環氧酚系經填充調配物
調配物 1(g) 178D 2(g) 178F 3(g) 180D 4(g) 180E 5(g) 183C 6(g) 183D
EPN 9820 10.06 10.04 16.21 12.95      
EP4088S 11.313 11.30 5.63 4.49 13.97 11.98
BPA DGE       8.89 7.1      
HP7200L             8.68 7.45
MY0510 20.531 20.51 9.662 17.0 19.24 23.065
四官能酚1    2.13            
酚-酚醛清漆TD2131       5.72 4.57 4.24 3.62
O,O’-二烯丙基雙酚A 4.23 2.13            
Technicure EMI-24CN 1.86 1.87 1.85 1.85 1.85 1.85
SE2050二氧化矽 50.0 50.0 49.975 49.975 49.975 49.975
KD1 1.0 1.0 1.0 1.0 1.0 1.0
W9010 0.5 0.5 0.5 0.5 0.5 0.50
Z6040 0.5 0.5 0.5 0.5 0.5 0.50
PC1344 0.05 0.05 0.05 0.05 0.05 0.05
                    
總計 100.0 100.0 100.0 100.0 100.0 100.0
表3之若干經填充調配物之Tg及黏度概況顯示於表4中。環氧酚系化學之一個顯著特徵係，即使DSC峰值溫度較低，在第二次DSC Tg上升後亦觀察到Tg之增加。此結果可能來自在第二次加熱期間之額外交聯。當裝置經受多個焊料回流條件時，增加之Tg可有益於裝置之可靠性。 表 4 ： 原型調配物之固化概況、黏度及 Tg
調配物 DSC 峰值固化溫度 ( ℃ ) 在 20 s -1 下之黏度 (cP) 25-260 ℃ DSC 斜升後之第一 Tg 25-260 ℃之第二次斜升後之第二 Tg
w/o 助熔劑 0 hr
1 160 3169 99 119
2 150 7377 113 128
3 139 48902 123 127
4 137 23291 141 143
5 138 16441 120 132
6 138 10972 126 143

Claims (17)

  1. 一種用於低間隙底部填充應用之與助熔劑相容的環氧酚黏著劑，其包含： 環氧組分，其包含具有環脂肪族、脂環族或混合環脂肪族-芳香族、脂環族-芳香族主鏈之環氧化合物； 多官能酚系組分；及 觸媒。
  2. 如請求項1之與助熔劑相容的環氧酚黏著劑，其中該環氧化合物係選自EP4088S、Eponex1510、HP7200L、Hyloxy改質劑107、單及多官能十氫萘縮水甘油基醚、單及多官能DCPD縮水甘油基醚、氫化雙酚A之二縮水甘油醚、單及多官能金剛烷基縮水甘油基醚、環脂肪族縮水甘油基酯、衍生自環脂肪族單胺及二胺之縮水甘油基化合物、環狀單烯及多烯之單及多官能環氧化物及其混合物。
  3. 如請求項1之與助熔劑相容的環氧酚黏著劑，其中該觸媒係選自咪唑、經取代咪唑、潛在性咪唑、經囊封咪唑、酚官能化咪唑及萘酚官能化咪唑。
  4. 如請求項3之與助熔劑相容的環氧酚黏著劑，其中該觸媒係選自Technicure EMI 24-CN、Curezol 2-PHZ-S、Curezol 2-PZ、Curezol 2PZ-吖嗪、Aardur 3123、Ajicure系列、Technicure系列、Resicure系列、Technirez系列及胺及多胺官能咪唑。
  5. 如請求項1之與助熔劑相容的環氧酚黏著劑，其中該係酚選自結構I、II、III及/或IV：
    Figure 03_image027
    其中X係單環、二環或多環結構，其係視情況具有脂肪族側鏈之環脂肪族或脂環族；酯基團之氧直接連接至該環或該脂肪族側鏈； X 1係視情況包含雜原子O或S之伸烷基或具支鏈伸烷基； R 3係H、烷基或環烷基； L 1及L 2獨立地選自共價鍵、視情況包含雜原子O或S之伸烷基、具支鏈伸烷基及伸環烷基； R 1及R 2獨立地係H、甲基或OH，前提條件係在每一環中R 1或R 2中之至少一者係OH；且 結構I、II、III及IV中存在之酯基團可為一級或二級酯基團。
  6. 如請求項1之與助熔劑相容的環氧酚黏著劑，其中該多官能酚系組分係選自以下酚系化合物：
    Figure 03_image029
    DCPD清漆型酚醛樹脂、甲酚清漆型酚醛樹脂、雙酚A清漆型酚醛樹脂、酚清漆型酚醛樹脂、三嗪清漆型酚醛樹脂、二烯丙基雙酚A、二羥基萘(所有異構物)、2-烯丙基苯基清漆型酚醛樹脂、二羥基二苯甲酮(所有異構物)、三羥基二苯甲酮(所有異構物)、Rezicure 3000、雙(4-羥基苯基)硫醚及雙(4-羥基苯基)碸。
  7. 如請求項1之與助熔劑相容的環氧酚黏著劑，其中該酚系組分係選自結構V、VI及/或VIII：
    Figure 03_image031
    其中R係脂肪族、環脂肪族、脂環族、混合芳香族-環脂肪族或聚合物主鏈；另外，在結構V及VII中，R可為稠合環； R 1及R 2係H、烷基或OH，前提條件係R 1或R 2中之至少一者係OH； L選自共價鍵、視情況具有雜原子O或S之伸烷基、伸環烷基及具支鏈伸烷基；L亦可含有酯或碳酸酯鍵聯； n=1-10；且 連接至結構V中之酚環的稠合環係可選的且在存在時可為芳香族、環脂肪族、脂環族或雜環。
  8. 如請求項1之與助熔劑相容的環氧酚黏著劑，其進一步包含馬來醯亞胺樹脂。
  9. 如請求項8之與助熔劑相容的環氧酚黏著劑，其中該馬來醯亞胺樹脂係結構VIII及IX之雙馬來醯亞胺、多官能馬來醯亞胺：
    Figure 03_image033
    其中L選自共價鍵、視情況具有雜原子O或S之伸烷基、伸環烷基及具支鏈伸烷基；L亦可含有酯或碳酸酯鍵聯；且 結構VIII中之稠合環係可選的且當存在時其係芳香族、環脂肪族、脂環族或雜環。
  10. 如請求項9之與助熔劑相容的環氧酚黏著劑，其中該雙馬來醯亞胺或多官能馬來醯亞胺係藉由單或多官能一級胺利用馬來酸酐亞胺化獲得或藉由單或多官能脂肪族、環脂肪族、脂環族或芳烷基醇利用6-馬來醯亞胺基己酸費歇爾酯化(Fisher esterification)來獲得。
  11. 如請求項1之與助熔劑相容的環氧酚黏著劑，其中該環氧樹脂對該酚之比率係1:1至1:0.05。
  12. 如請求項1之與助熔劑相容的環氧酚黏著劑，其進一步包含固化劑、加速劑、觸媒、流動改質劑、填充劑、黏著促進劑及觸變劑。
  13. 一種酚，其選自：
    Figure 03_image035
    。
  14. 一種酚，其選自結構I、II、III及IV中之一或多者：
    Figure 03_image037
    其中X係單環、二環或多環結構，其為視情況具有脂肪族側鏈之環脂肪族或脂環族；且酯基團之氧直接連接至該環或該脂肪族側鏈； X 1係視情況具有雜原子O或S之伸烷基或具支鏈伸烷基； R 3係H、烷基或環烷基； L 1及L 2獨立地選自共價鍵、視情況包含雜原子O或S之伸烷基、具支鏈伸烷基及伸環烷基； R 1及R 2獨立地係H、甲基或OH，前提條件係在每一環中R 1或R 2中之至少一者係OH；且 結構I、II、III及IV中存在之酯基團可為一級或二級酯基團。
  15. 一種酚，其選自結構V、VI及VII中之一或多者：
    Figure 03_image039
    其中R係脂肪族、環脂肪族、脂環族、混合芳香族-環脂肪族或聚合物主鏈；另外，在結構V及VII中，R可為稠合環； R 1及R 2係H、烷基或OH，前提條件係R 1或R 2中之至少一者係OH； n=1-10；且 連接至結構V中之酚環的稠合環係可選的且在存在時可為芳香族、環脂肪族、脂環族或雜環。
  16. 一種酚，其選自結構VIII及IX中之一或多者：
    Figure 03_image041
    其中L選自共價鍵、視情況具有雜原子O或S之伸烷基、伸環烷基及具支鏈伸烷基；L亦可含有酯或碳酸酯鍵聯；且 結構VIII中之稠合環係可選的且當存在時其係芳香族、環脂肪族、脂環族或雜環。
  17. 如請求項1之與助熔劑相容的環氧酚黏著劑，其中： 該環氧化合物選自EP4088S、Eponex1510、HP7200L、Hylox改質劑107及其混合物； 該多官能酚選自：
    Figure 03_image043
    ；且該觸媒係選自Technicure EMI 24-CN、Curezol 2-PHZ-S、Curezol 2-PZ、Curezol 2PZ-吖嗪及Aardur 3123。
TW110111505A 2020-06-01 2021-03-30 用於低間隙底部填充應用之與助熔劑相容的環氧酚系黏著劑組合物 TW202212316A (zh)

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