TWI429723B - 電子部件用液狀接著劑及接著膠帶 - Google Patents

電子部件用液狀接著劑及接著膠帶 Download PDF

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Publication number
TWI429723B
TWI429723B TW100110045A TW100110045A TWI429723B TW I429723 B TWI429723 B TW I429723B TW 100110045 A TW100110045 A TW 100110045A TW 100110045 A TW100110045 A TW 100110045A TW I429723 B TWI429723 B TW I429723B
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Taiwan
Prior art keywords
component
liquid adhesive
adhesive
mass
compound represented
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TW100110045A
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English (en)
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TW201202370A (en
Inventor
Yuki Shimizu
Tatsuru Iwabuchi
Jun Tochihira
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Tomoegawa Co Ltd
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Publication of TW201202370A publication Critical patent/TW201202370A/zh
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Publication of TWI429723B publication Critical patent/TWI429723B/zh

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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01LSEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
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    • H01L24/26Layer connectors, e.g. plate connectors, solder or adhesive layers; Manufacturing methods related thereto
    • H01L24/28Structure, shape, material or disposition of the layer connectors prior to the connecting process
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    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09J109/02Copolymers with acrylonitrile
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Description

電子部件用液狀接著劑及接著膠帶
本發明係關於一種電子部件用液狀接著劑及接著膠帶,係用於構成半導體裝置的引線框架週邊之構件間,例如,引線接腳(lead pin)、半導體晶片搭載用基板、散熱板、半導體晶片本身等之接著用。
本案係主張以2010年3月25日於日本申請之日本特願2010-069063號為基礎之優先權,而於此引用其內容。
以往,於樹脂密封型半導體所使用的接著膠帶,係有引線框架固定用膠帶、TAB膠帶等。
例如,引線框架固定用接著膠帶,係藉由將引線框架的引線接腳固定,而作為有益於提升引線框架本身及半導體組裝步驟全體之生產成品率及生產性所使用。
此固定用接著膠帶,通常於引線框架製造廠貼附在引線框架上後,出貨至半導體製造廠,於半導體製造廠搭載IC後,以樹脂密封。
因此,引線框架固定用接著膠帶,除了必須有半導體等級的一般信賴性及貼附時的作業性外,亦要求貼附後立即之充分的室溫接著力、可承受於半導體裝置組裝步驟的充分的耐熱性等。
以往,作為用於此種用途的接著膠帶,例如,聚醯亞胺膜等承載膜上,塗佈聚丙烯腈、聚丙烯酸酯或是丙烯腈-丁二烯共聚物等合成橡膠系樹脂等單獨,或是經其他樹脂改質者,或者是與其他樹脂混合之接著劑,而作為B階段(B-Stage)使用者。
近年來,正在開發並製造如第1圖至第3圖所示之構造的樹脂密封型半導體裝置(半導體封裝體)。
第1圖之樹脂密封型半導體裝置,係具有將引線接腳3與底板2係以接著層6連接,半導體晶片1係搭載於底板2上,而與半導體晶片1與引線接腳3之間的接合線4一同藉由樹脂5密封之構造。
此外,第2圖的裝置係具有將引線接腳3與半導體晶片1以接著層6固定,而與接合線4一同藉由樹脂5密封之構造。
第3圖的裝置,係具有晶片墊7上搭載半導體晶片1,電極8藉由接著層6固定,且於半導體晶片1與電極8之間,以及電極8與引線接腳3之間分別以接合線4連結,而此等係藉由樹脂5密封之構造。
作為第1圖至第3圖所示之構造的樹脂密封型半導體裝置之接著層,已知有可在較低溫接著、硬化,而具有充分之耐熱信及信賴性等之接著劑(例如,參照專利文獻1)。
而且,信賴性意指即使在後述之遷移(migration)試驗(PCBT: Pressure Cooker Biased Test)的條件下,亦不會引起電流的漏電或短路。
然而,對於此種接著劑,已尋求更加提升其抗遷移性。
抗遷移性意指於遷移試驗中,不引起短路、無樹突(dendrite)成長。
[專利文獻]
[專利文獻1]日本特開平09-176593號公報
本發明係有鑑於以上之問題點而完成者,其目的在於提供一種電子部件用液狀接著劑及接著膠帶,係可在低溫接著、硬化,具有充分之耐熱性及信賴性,且抗遷移性優良。
本發明係藉由下述之技術性構造,而可解決上述課題。
(1)一種電子部件用液狀接著劑,係於有機溶劑中溶解有:成分(a)丙烯腈-丁二烯共聚物、成分(b)酚樹脂、及成分(c)含有兩個以上馬來醯亞胺基之化合物,而前述成分(c)係包含之後所述的式(1)所示之化合物,以及(2)所示之化合物者。
(2)如第1項所述之電子部件用液狀接著劑,其中,前述成分(a)之慕尼黏度(Mooney viscosity)係50至90M1+4 100℃者。
(3)如第1項所述之電子部件用液狀接著劑,其中,前述成分(a)係具有羧基之丙烯腈-丁二烯共聚物者。
(4)如第1項所述之電子部件用液狀接著劑,其中,前述成分(b)係包含可溶酚醛型(resol-type)烷基酚的酚樹脂者。
(5)如第1項所述之電子部件用液狀接著劑,其中,前述成分(b)係併用可溶酚醛型酚樹脂與酚醛清漆型(novolac-type)酚樹脂者。
(6)如第1項所述之電子部件用液狀接著劑,其中,前述成分(c)之式(1)及(2)所示化合物的質量比係3:3至3:45者。
(7)如第1項所述之電子部件用液狀接著劑,其中,相對於成分(a)100質量份,成分(b)、成分(c)的合計含量係10至900質量份,且成分(b)、成分(c)的合計含量中,成分(b)的質量比例係10至90質量%者。
(8)如第1項所述之電子部件用液狀接著劑,其中,復含有成分(d)二胺化合物者。
(9)如第8項所述之電子部件用液狀接著劑,其中,前述成分(d)係後述的式(3)所示之化合物者。
(10)如第8項所述之電子部件用液狀接著劑,其中,前述成分(d)係後述的下式(4)所示之化合物,且重量平均分子量為200至7,000者。
(11)如第1項所述之電子部件用液狀接著劑,其中,包含佔全部固體成分4至40質量%之粒徑1μm以下的填料者。
(12)一種接著膠帶,其係於耐熱性膜的至少一面塗佈第1項所述之電子部件用液狀接著劑並加以乾燥而形成有接著層者。
(13)如第12項所述之接著膠帶,其中,耐熱性膜係聚醯亞胺膜者。
(14)一種接著膠帶,其係於剝離性膜之至少一面塗佈第1項所述之電子部件用液狀接著劑並加以乾燥而形成有接著層者。
藉由本發明,可提供可在低溫接著、硬化,具有充分之耐熱性及信賴性,且抗遷移性優良的電子部件用液狀接著劑及接著膠帶。
換言之,本發明之電子部件用液狀接著劑,係可在低溫接著或硬化,具有充分之耐熱性及信賴性,且抗遷移性優良,故使用本發明之接著膠帶,適合使用例如作為引線框架固定用膠帶、TAB膠帶等,於構成半導體裝置的引線框架週邊的構件間,例如,引線接腳、半導體晶片搭載用基板、散熱板、半導體晶片本身等的接著。
以下,對本發明進行詳細說明。
首先,說明電子部件用液狀接著劑之較佳例。但本發明不侷限於此等範例所述者。
本發明之電子部件用液狀接著劑,係於有機溶劑中溶解有:成分(a)丙烯腈-丁二烯共聚物、成分(b)酚樹脂、及成分(c)含有兩個以上馬來醯亞胺基之化合物,而前述成分(c)係包含下式(1)所示以及(2)所示之化合物。
以下對各成分進行說明。
成分(a):
作為成分(a)之丙烯腈-丁二烯共聚物,係可全部使用公知者,而以具有羥基之丙烯腈-丁二烯共聚物為佳。
其理由係因為加熱時的溶融黏度變高而熱安定性提升,與其他樹脂的相容性上升而絕緣性安定,樹脂的張力強度上升之故。
具有羧基之丙烯腈-丁二烯共聚物中的羧基當量,係以1000至20000為佳。
並且,羧基當量係以數目平均分子量所計算之值。
此外,當慕尼黏度為50至90M1+4 (100℃)者為佳。
其原因係因為當慕尼黏度在上述範圍內時,則熱安定性變好、耐熱性提升之故。
此外,因溶劑溶解性的提升、溶融黏度降低,而作為接著劑使用時,其作業性及接著性良好因而較佳。
慕尼黏度若低於上述範圍之下限,則樹脂的耐熱性降低,變得無法得到半導體組裝步驟所必須的耐熱性。此外,若接著劑的B階段之溶融黏度降低,則對引線框架之加工時的接著劑的流出增加,而使得加工性降低,故為不佳。另一方面,慕尼黏度若超過上述範圍之上限,則接著劑難以溶融,流動性降低,引線框架的貼附性降低。此外,對溶劑的溶解性降低,製成接著劑之作業性降低,故為不佳。
接下來,上述共聚物的丙烯腈含有率較佳為5至50質量%,更佳為10至40質量%。
丙烯腈含有率若於上述範圍內,則耐熱性、溶劑溶解性係於合適地範圍,其絕緣性安定而信賴性提升故為佳。
若低於上述範圍之下限,則樹脂的耐熱性降低,變得無法得到半導體組裝步驟所必須的耐熱性,因而不佳。另一方面,若超過上述範圍之上限,則對溶劑的溶解性降低(製成接著劑之作業性降低),因而不佳。此外,抗遷移性亦降低。
成分(b):
作為成分(b)之酚樹脂,係可使用公知者,就可使接著溫度、接著劑的硬化溫度低溫化,以及可得到充分的接著力方面而言,係以包含可溶酚醛型烷基酚的酚樹脂為佳。
此外,更佳為併用可溶酚醛型的酚及酚醛清漆型的酚。
並且,可溶酚醛型酚樹脂與酚醛清漆型酚樹脂之質量比係以100:5至100:100者為佳,以100:10至100:50者為更佳。
其原因係因為併用可溶酚醛型的酚及酚醛清漆型的酚可抑制抑制表面的黏性,而可抑制引線框架加工時的搬運不良之故。
此外,因酚醛清漆型酚樹脂之單獨的硬化性不良,若相對於可溶酚醛型酚,酚醛清漆型酚樹脂的質量比過剩,則接著劑的硬化性降低而抗遷移性降低,因而不佳。
具體而言,可列舉如可溶酚醛型之對-第三丁基酚與酚醛清漆型之鄰-第三丁基酚。
成分(c):
作為成分(c)之含有兩個以上馬來醯亞胺基之化合物,係必須併用上述式(1)及(2)所示之化合物者。
其原因係因為可使接著溫度、接著劑的硬化溫度低溫化,此外,可得到高接著力。另外,藉由併用提升熱安定性、提升於熱溫時的接著性;並且,提升與其他樹脂的相溶性,抗遷移性優良之故。
而且,上述式(1)及(2)所示化合物之質量比,係以3:3至3:45者為佳,以3:3.9至3:19.5者為較佳,以1:3至1:7者為更佳。
本發明之電子部件用液狀接著劑,以復含有成分(d):二胺化合物者為佳,而成分(d)係含有下式(3)或(4)所示之化合物者為更佳。
H2 N-R1 -NH2  (3)
(式中,R1 表示2價的芳香族基)
(式中,R2 表示伸丙基或是苯氧基亞甲基,n表示0至7之整數)
其原因係因為藉由將馬來醯亞胺基作為硬化劑使用,可調整硬化溫度之故。
作為上述式(3)所示之化合物,可列舉例如接下來所述者。本發明不限定於前述之2價的芳香族基。2價的芳香族基意指包含芳香族基的2價基,亦可因應所須而選擇任何一種基。例如,不限定數量的苯基,此外必要時可具有取代基。3,3’-二胺基聯苯、3,4’-二胺基聯苯、4,4’-二胺基聯苯、3,3’-二胺基二苯基甲烷、3,4’-二胺基二苯基甲烷、4,4’-二胺基二苯基甲烷、2,2-(3,3’-二胺基二苯基)丙烷、2,2-(3,4’-二胺基二苯基)丙烷、2,2-(4,4’-二胺基二苯基)丙烷、2,2-(3,3’-二胺基二苯基)六氟丙烷、2,2-(3,4’-二胺基二苯基)六氟丙烷、2,2-(4,4’-二胺基二苯基)六氟丙烷、3,3’-氧基二苯胺、3,4’-氧基二苯胺、4,4’-氧基二苯胺、3,3’-二胺基二苯硫醚、3,4’-二胺基二苯硫醚、4,4’-二胺基二苯硫醚、3,3’-二胺基二苯碸、3,4’-二胺基二苯碸、4,4’-二胺基二苯碸、1,3-雙[1-(3-胺基苯基)-1-甲基乙基]苯、1,3-雙[1-(4-胺基苯基)-1-甲基乙基]苯、1,4-雙[1-(3-胺基苯基)-1-甲基乙基]苯、1,3-雙(3-胺基苯氧基)苯、1,3-雙(4-胺基苯氧基)苯、1,4-雙(3-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、3,3’-雙(3-胺基苯氧基)二苯基醚、3,3’-雙(4-胺基苯氧基)二苯基醚、3,4’-雙(3-胺基苯氧基)二苯基醚、3,4’-雙(4-胺基苯氧基)二苯基醚、4,4’-雙(3-胺基苯氧基)二苯基醚、4,4’-雙(4-胺基苯氧基)二苯基醚、1,4-雙[1-(4-胺基苯基)-1-甲基乙基-雙(3-胺基苯氧基)聯苯、3,3’-雙(4-胺基苯氧基)聯苯、3,4’-雙(3-胺基苯氧基)聯苯、3,4’-雙(4-胺基苯氧基)聯苯、4,4’-雙(3-胺基苯氧基)聯苯、4,4’-雙(4-胺基苯氧基)聯苯、雙[4-(3-胺基苯氧基)苯基]碸、雙[4-(4-胺基苯氧基)苯基]碸、2,2-雙[3-(3-胺基苯氧基)苯基]丙烷、2,2-雙[3-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(3-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[3-(3-胺基苯氧基)苯基]六氟丙烷、2,2-雙[3-(4-胺基苯氧基)苯基]六氟丙烷、2,2-雙[4-(3-胺基苯氧基)苯基]六氟丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、9,9-雙(3-胺基苯基)茀、9,9-雙(4-胺基苯基)茀等。
上述式(4)所示之化合物,重量平均分子量係以200至7,000為佳。
其原因係因容易溶解於溶劑中而為容易處理者。
作為上述式(4)所示之化合物,可列舉例如,雙(3-胺基丙基)四甲基二矽氧烷、胺基丙基末端的二甲基矽氧烷4聚體、或是8聚體、雙(3-胺基苯氧基甲基)四甲基二矽氧烷等,亦可將此等混用。
液狀接著劑的調配比例,相對於成分(a)100質量份,以成分(b)、成分(c)的合計含量為10至900質量份為佳。以合計含量為20至800質量份為較佳,以合計含量為50至400質量份更佳,以合計含量為100至400質量份為特佳。
若成分(b)、成分(c)的合計含量於上述範圍內,則於經塗佈而硬化後,接著層的耐熱性,特別是提升Tg、楊氏模數(Young’s modulus),而適於目的之用途。
此外,將接著層硬化至B階段時,接著層本身不脆化而作業性為良好,與載體之耐熱性膜的密著性亦趨於良好。
此時,就作業性、硬化樹脂的特性方面而言,成分(b)、成分(c)的合計含量中成分(b)的質量比例係以10至90質量%為佳,以20至53質量%者為更佳。
此外,成分(c)與成分(d)的調配比例,相對於成分(c)之馬來醯亞胺基1莫耳當量,成分(d)的胺基,其範圍設定為0.01至2.0莫耳當量為佳,0.1至1.0莫耳當量為更佳。
當成分(d)之胺基當量於上述範圍內,將接著層硬化至B階段時,接著層本身不脆化而作業性為良好,與載體之耐熱性膜的密著性亦為良好。
此外,因混合時不會膠化,故可調整接著劑。
成分(a)、成分(b)、成分(c)、以及成分(d)的混合,係於溶解此等之溶媒中進行。
溶媒係可因應所須而選擇,可列舉例如N-甲基-2-吡咯烷酮、N,N-二甲基乙醯胺、N,N-二甲基甲醯胺、二甲亞碸、環丁碸(sulfolane)、六甲基膦酸三胺、1,3-二甲基-2-咪唑啶、已烷、苯、甲苯、二甲苯、甲基乙基酮、丙酮、二乙基醚、四氫呋喃、二烷、1,2-二甲氧基乙烷、二乙二醇二甲基醚、甲賽璐蘇(methyl cellosolve)、乙酸賽路蘇、甲醇、乙醇、丙醇、異丙醇、乙酸甲酯、乙酸乙酯、乙腈、氯化甲烷、氯仿、四氯化碳、氯苯、二氯苯、二氯乙烷、三氯乙烷等。自此等中,可適當選擇使用可溶解各成份之種類與量。
關於液狀接著劑,可為了促進上述成份(a)等、以及成份(b)等的加成反應,而因應所須添加反應促進劑。反應促進劑可列舉例如二氮雜雙環辛烷(diazabicyclooctane)、或者是過氧化甲基乙基酮、過氧化環己烷、過氧化3,3,5-三甲基環己酮、過氧化甲基環己酮、過氧化乙醯乙酸甲酯、過氧化乙醯丙酮、1,1-雙(過氧化第三丁基)-3,3,5三甲基己烷、1,1-雙(過氧化第三丁基)-環己烷、2,2-雙(過氧化第三丁基)-辛烷、正丁基-4,4-雙(過氧化第三丁基)戊酸酯、2,2-雙(過氧化第三丁基)丁烷、氫過氧化第三丁基(tert-butyl hydroperoxide)、氫過氧化茴香烴(cumene hydroperoxide)、二-氫過氧化異丙苯、氫過氧化對-甲烷、二氫過氧化2,5-二甲基己烷-2,5-、氫過氧化1,1,3,3-四甲基丁基、過氧化二-第三丁基、過氧化第三丁基異丙苯基(cumyl)、過氧化二-異丙苯基、a,a’-雙(過氧化第三丁基-間-異丙基)苯、2,5-二甲基-2,5-二(過氧化第三丁基)己烷、2,5-二甲基-2,5-二(過氧化第三丁基)己炔、過氧化乙醯、過氧化異丁基、過氧化辛醯、過氧化癸醯、過氧化苯甲醯、過氧化十二醯、過氧化3,5,5-三甲基己醯、過氧化丁二酸、過氧化2,4-二氯苯甲醯、過氧化間-甲苯甲醯基、過氧化二碳酸二-異丙酯、過氧化二碳酸二-2-乙基己酯、過氧化二碳酸二-正-丙酯、過氧化二碳酸雙-(4-第三丁基環己基)酯、過氧化二碳酸二-十四醯酯、過氧化二碳酸二-2-乙氧基乙酯、過氧化二碳酸二-甲氧基異丙酯、過氧化二碳酸二(3-甲基-3-甲氧基丁基)酯、過氧化二碳酸二-丙烯酯、過氧化乙酸第三丁酯、過氧化異丁酸第三丁酯、過氧化三甲基乙酸第三丁酯、過氧化新癸酸第三丁酯、過氧化新癸酸異丙苯酯、第三丁基過氧化-2-乙基己酯、第三丁基過氧化-3,5,5-三甲基己酯、過氧化十二酸第三丁酯、過氧化安息香酸第三丁酯、過氧化異酞酸二-第三丁酯、2,5-二甲基-2,5-二(過氧化苯甲醯)已烷、過氧化順丁烯二酸第三丁酯、第三丁基過氧化異丙基碳酸酯(t-butyl peroxy isopropylcarbonate)、過氧化辛酸異丙苯酯、過氧化新癸酸第三己酯、過氧化三甲基乙酸第三己酯、過氧化新己酸第三丁酯、過氧化乙醯環己基磺醯基、過氧化丙烯基碳酸第三丁酯等有機過氧化物;1,2-二甲基咪唑、1-甲基-2-乙基咪唑、2-甲基咪唑、2-乙基-4-甲基咪唑、2-十一基咪唑、2-十七基咪唑、2-苯基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-苄基-2-苯基咪唑‧偏苯三甲酸鹽、1-苄基-2-乙基咪唑、1-苄基-2-乙基-5-甲基咪唑、2-乙基咪唑、2-異丙基咪唑、2-苯基-4-苄基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-十一基咪唑、1-氰基乙基-2-異丙基咪唑、1-氰基乙基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑鎓偏苯三甲酸酯、1-氰基乙基-2-苯基咪唑鎓偏苯三甲酸酯、2,4-二胺-6-[2’-甲基咪唑基-(1’)]-乙基-s-三、2,4-二胺-6-[2’-乙基-4-甲基咪唑基-(1’)]-乙基-s-三、2,4-二胺-6-[2’-十一基咪唑基-(1’)]-乙基-s-三、2-甲基咪唑鎓異三聚氰酸加成物、2-苯基咪唑鎓異三聚氰酸加成物、2,4-二胺-6-[2’-甲基咪唑基-(1’)]-乙基-s-三-異三聚氰酸加成物、2-苯基-4,5-二羥基甲基咪唑、2-苯基-4-苄基-5-羥基甲基咪唑、4,4’-亞甲基-雙-(2-乙基-5-甲基咪唑)、1-胺乙基-2-甲基咪唑、1-氰基乙基-2-苯基-4,5-二(氰基乙氧基甲基)咪唑、1-十二基-2-甲基-3-苄基咪唑鎓氯化物、2-甲基咪唑‧苯并三唑加成物、1-胺乙基-2-乙基咪唑、1-(氰基乙基胺乙基)-2-甲基咪唑、N,N’-[2-甲基咪唑基-(1)-乙基]-己二醯基二醯胺、N,N’-雙-(2-甲基咪唑基-1-乙基)尿素、N-(2-甲基咪唑基-1-乙基)尿素、N,N’-[2-甲基咪唑基-(1)-乙基]十二烷二醯二醯胺(dodecanedioyldiamide)、N,N’-[2-甲基咪唑基-(1)-乙基]二十烷二醯二醯胺、1-苄基-2-苯基咪唑‧鹽酸鹽等咪唑類;三苯基膦等反應促進劑。可單獨使用,亦可組合兩種以上使用。
此外,液狀接著劑為了使適用於接著膠帶時的貼附特性安定,可含有粒徑1μm以下的填料。
貼附特性的安定,係意指將接著膠帶熱壓接合於導線上時,防止接著劑因溶融而自膠帶端面溢出,且接著層保持適當的厚度而維持接著性。
填料的含有率,係設定為總固體成分之4至40質量%,而較佳係9至24質量%之範圍。
含有率若於上述範圍內,則貼附特性的安定化效果變大,另外,因接著膠帶的接著強度提升,積層等之加工性變得良好,故為佳。
作為填料,可使用例如氧化矽、石英粉、氧化鋁、碳酸鈣、氧化鎂、鑽石粉、雲母、氟樹脂、鋯石粉等。
此外,液狀接著劑,亦可因應所須,而於反應結束後,亦即在乾燥後將之取出,以有機溶劑、水、或者有機溶劑與水的混合物洗淨後,再次因應所須溶解於所選擇之有機溶劑而作為接著劑使用。
可用於洗淨的有機溶劑,可列舉例如丙酮、甲基乙基酮、己烷、苯、甲苯、二甲苯、甲醇、乙醇、丙醇、二乙醚、四氫呋喃、乙酸甲酯、乙酸乙酯、乙腈、二氯甲烷、氯仿、四氯化碳、氯苯、二氯苯、二氯乙烷、三氯乙烷等。
接下來,對本發明之接著膠帶進行說明。
本發明之接著膠帶,係於耐熱性膜或剝離性膜之至少一面塗佈上述電子部件用液狀接著劑,而經乾燥形成接著層者。
此時,塗佈厚度係5至100μm,而尤以為10至50μm之範圍者為佳。
作為耐熱性膜,可列舉例如聚醯亞胺、聚苯硫醚(polyphenylene sulfide)、聚醚、聚乙二醯脲(polyparabanic acid)、及聚乙烯對苯二甲酸酯(polyethylene terephthalate)等耐熱性樹脂膜;環氧樹脂-玻璃布、環氧樹脂-聚醯亞胺-玻璃布等複合耐熱膜,而特別以聚醯亞胺膜為佳。
耐熱性膜的厚度,係設定為7.5至130μm,以12.5至75μm之範圍為佳。耐熱性膜的形狀及尺寸係可因應所須而選擇。
若於上述範圍內,則接著膠帶之厚度足夠,沖壓作業變得容易。
作為剝離性膜,厚度係為1至200μm,而尤以10至100μm之範圍者為佳,作為暫時性載體之作用。剝離性膜的形狀及尺寸係可因應所須而選擇。可以使用的剝離性膜可列舉如聚丙烯膜、氟樹脂系膜、聚乙烯膜、聚乙烯對苯二甲酸酯膜、紙、以及視狀況而於此等以矽氧樹脂賦予剝離性者等。
此等之剝離性膜,90°剝離強度係以0.01至7.0g/cm之範圍為理想。
剝離強度若於上述範圍內,則搬運接著膠帶時,剝離性膜不會輕易自接著層剝離,且於使用時剝離性膜可自接著層完全剝離,作業性為良好。
而且,當耐熱性膜形成接著層時,亦可於接著層上再設置保護膜。
作為保護膜,亦可使用與上述剝離性膜相同者。
(實施例)
以下依據實施例對本發明進行詳細說明。
[實施例1] 成分(a):
丙烯腈-丁二烯共聚物(不含有羧基,慕尼黏度70M1+4 100℃,丙烯腈含有率27%)100質量份
成分(b):
對-第三丁基酚型可溶酚醛酚樹脂(商品名稱:「CKM-1282」,昭和高分子公司製造)50質量份
對-第三丁基酚與Bis-A之共聚型酚醛清漆酚樹脂(CKM-2400,昭和高分子公司製造)20質量份
成分(c):
市售之前述式(1)所示之化合物30質量份
市售之前述式(2)所示之化合物50質量份
成分(d):
1,3-雙(3-胺丙基)-1,1,3,3-四甲基二矽氧烷0.25質量份
將以上之成分添加於四氫呋喃中並充分混合、溶解,將固體成分比率調整成為30質量%,得到實施例1之電子部件用液狀接著劑。
而相對於馬來醯亞胺基1莫耳當量,胺基的莫耳當量係0.51。
[實施例2]
將成分(a)變更如下述。
成分(a):
羧基改質丁二烯-丙烯腈共聚物(羥基當量100,慕尼黏度60M1+4 100℃,丙烯腈含有率27%)100質量份
此外與實施例1以同樣方式進行處理,得到實施例2之電子部件用液狀接著劑。
[實施例3]
將成分(b)變更如下述。
成分(b):
對-第三丁基酚型可溶酚醛酚樹脂(商品名稱:「CKM-1282」,昭和高分子公司製造)70質量份
此外與實施例1以同樣方式進行處理,得到實施例3之電子部件用液狀接著劑。
[實施例4]
將成分(b)變更如下述。
成分(b):
對-第三丁基酚型可溶酚醛酚樹脂(商品名稱:「CKM-1282」,昭和高分子公司製造)50質量份
對-第三丁基酚與Bis-A之共聚型酚醛清漆酚樹脂(CKM-2400,昭和高分子公司製造)40質量份
此外與實施例1以同樣方式進行處理,得到實施例4之電子部件用液狀接著劑。
[實施例5]
將成分(c)變更如下述。
成分(c):
市售之前述式(1)所示之化合物15質量份
市售之前述式(2)所示之化合物65質量份
此外與實施例1以同樣方式進行處理,得到實施例5之電子部件用液狀接著劑。
[實施例6]
將成分(d)變更如下述。
成分(d):
此外與實施例1以同樣方式進行處理,得到實施例6之電子部件用液狀接著劑。
[實施例7]
將成分(b)及成分(c)變更如下述。
成分(b):
對-第三丁基酚型可溶酚醛酚樹脂(商品名稱:「CKM-1282」,昭和高分子公司製造)16.6質量份
對-第三丁基酚與Bis-A之共聚型酚醛清漆酚樹脂(CKM-2400,昭和高分子公司製造)6.7質量份
成分(c):
市售之前述式(1)所示之化合物10質量份
市售之前述式(2)所示之化合物16.7質量份
此外與實施例1以同樣方式進行處理,得到實施例7之電子部件用液狀接著劑。
[實施例8]
將成分(b)及成分(c)變更如下述。
成分(b):
對-第三丁基酚型可溶酚醛酚樹脂(商品名稱:「CKM-1282」,昭和高分子公司製造)33.3質量份
對-第三丁基酚與Bis-A之共聚型酚醛清漆酚樹脂(CKM-2400,昭和高分子公司製造)13.4質量份
成分(c):
市售之前述式(1)所示之化合物20質量份
市售之前述式(2)所示之化合物33.3質量份
此外與實施例1以同樣方式進行處理,得到實施例8之電子部件用液狀接著劑。
[實施例9]
將成分(b)及成分(c)變更如下述。
成分(b):
對-第三丁基酚型可溶酚醛酚樹脂(商品名稱:「CKM-1282」,昭和高分子公司製造)133.3質量份
對-第三丁基酚與Bis-A之共聚型酚醛清漆酚樹脂(CKM-2400,昭和高分子公司製造)53.4質量份
成分(c):
市售之前述式(1)所示之化合物80質量份
市售之前述式(2)所示之化合物133.3質量份
此外與實施例1以同樣方式進行處理,得到實施例9之電子部件用液狀接著劑。
[實施例10]
將成分(b)及成分(c)變更如下述。
成分(b):
對-第三丁基酚型可溶酚醛酚樹脂(商品名稱:「CKM-1282」,昭和高分子公司製造)266.6質量份
對-第三丁基酚與Bis-A之共聚型酚醛清漆酚樹脂(CKM-2400,昭和高分子公司製造)106.7質量份
成分(c):
市售之前述式(1)所示之化合物160質量份
市售之前述式(2)所示之化合物266.7質量份
此外與實施例1以同樣方式進行處理,得到實施例10之電子部件用液狀接著劑。
[實施例11]
將成分(b)及成分(c)變更如下述。
成分(b):
對-第三丁基酚型可溶酚醛酚樹脂(商品名稱:「CKM-1282」,昭和高分子公司製造)85.7質量份
對-第三丁基酚與Bis-A之共聚型酚醛清漆酚樹脂(CKM-2400,昭和高分子公司製造)34.3質量份
成分(c):
市售之前述式(1)所示之化合物11.2質量份
市售之前述式(2)所示之化合物18.8質量份
此外與實施例1以同樣方式進行處理,得到實施例11之電子部件用液狀接著劑。
[實施例12]
將成分(b)及成分(c)變更如下述。
成分(b):
對-第三丁基酚型可溶酚醛酚樹脂(商品名稱:「CKM-1282」,昭和高分子公司製造)32.1質量份
對-第三丁基酚與Bis-A之共聚型酚醛清漆酚樹脂(CKM-2400,昭和高分子公司製造)12.9質量份
成分(c):
市售之前述式(1)所示之化合物39.4質量份
市售之前述式(2)所示之化合物65.6質量份
此外與實施例1以同樣方式進行處理,得到實施例12之電子部件用液狀接著劑。
[實施例13]
將成分(b)及成分(c)變更如下述。
成分(b):
對-第三丁基酚型可溶酚醛酚樹脂(商品名稱:「CKM-1282」,昭和高分子公司製造)21.4質量份
對-第三丁基酚與Bis-A之共聚型酚醛清漆酚樹脂(CKM-2400,昭和高分子公司製造)8.6質量份
成分(c):
市售之前述式(1)所示之化合物45質量份
市售之前述式(2)所示之化合物75質量份
此外與實施例1以同樣方式進行處理,得到實施例13之電子部件用液狀接著劑。
[實施例14]
將成分(b)及成分(c)變更如下述。
成分(b):
對-第三丁基酚型可溶酚醛酚樹脂(商品名稱:「CKM-1282」,昭和高分子公司製造)10.7質量份
對-第三丁基酚與Bis-A之共聚型酚醛清漆酚樹脂(CKM-2400,昭和高分子公司製造)4.3質量份
成分(c):
市售之前述式(1)所示之化合物50.6質量份
市售之前述式(2)所示之化合物84.4質量份
此外與實施例1以同樣方式進行處理,得到實施例14之電子部件用液狀接著劑。
[實施例15]
將成分(c)變更如下述。
成分(c):
市售之前述式(1)所示之化合物5質量份
市售之前述式(2)所示之化合物75質量份
此外與實施例1以同樣方式進行處理,得到實施例15之電子部件用液狀接著劑。
[實施例16]
將成分(c)變更如下述。
成分(c):
市售之前述式(1)所示之化合物10質量份
市售之前述式(2)所示之化合物70質量份
此外與實施例1以同樣方式進行處理,得到實施例16之電子部件用液狀接著劑。
[實施例17]
將成分(c)變更如下述。
成分(c):
市售之前述式(1)所示之化合物20質量份
市售之前述式(2)所示之化合物60質量份
此外與實施例1以同樣方式進行處理,得到實施例17之電子部件用液狀接著劑。
[實施例18]
將成分(c)變更如下述。
成分(c):
市售之前述式(1)所示之化合物40質量份
市售之前述式(2)所示之化合物40質量份
此外與實施例1以同樣方式進行處理,得到實施例18之電子部件用液狀接著劑。
[比較例1]
將成分(c)變更如下述。
成分(c):
市售之前述式(1)所示之化合物80質量份
此外與實施例1以同樣方式進行處理,得到不含式(2)所示化合物之比較例1的電子部件用液狀接著劑。
[比較例2]
將成分(c)變更如下述。
成分(c):
市售之前述式(2)所示之化合物80質量份
此外與實施例1以同樣方式進行處理,得到不含式(1)所示化合物之比較例2的電子部件用液狀接著劑。
實施例及比較例的主要條件如表1所示。
將前述實施例1至18及比較例1、2之電子部件用液狀接著劑以使乾燥後的接著層之厚度為20μm的方式塗佈於聚醯亞胺膜之兩面,於熱風循環型乾燥機中以160℃乾燥5分鐘,製作使用實施例1至18及比較例1、2的接著劑之接著膠帶。
接下來,使用採用了實施例1至18及比較例1、2的接著劑之接著膠帶,可用於如第1圖所示之半導體封裝體,而將與底板貼合的引線框架以下述流程組裝。
接著膠帶的沖壓:藉由模具將接著膠帶沖壓為環狀。
接著膠帶的暫時接著:將底板置於加熱板上,將經沖壓為環狀之膠帶以金屬桿壓附而暫時接著。
而暫時性接著的條件為140℃/2秒/4Kgf/cm2
引線框架的組裝:將上述步驟之暫時接著有接著膠帶的底板,與引線框架(Cu材質)本體的位置重疊,於加熱之加熱板上加熱加壓,使引線框架(Cu材質)與底板藉由接著膠帶而貼合。
而貼合的條件為140℃/2秒/4Kgf/cm2
接著膠帶固化(curing):放入經氮氣置換的熱風循環型爐內,使其熱硬化。
而熱硬化的條件為200℃/1小時。
接下來,使用所製作之與底板貼合的引線框架(Cu材質),以下述流程組裝半導體封裝體。
晶粒接著(die bonding):使用晶粒接著用銀膠,將半導體晶片接著於與底板貼合的引線框架的底板部份,以150℃ 2小時使其硬化。
打線(wire bonding):藉由打線,以金線將半導體晶片上的結合線與引線接腳的內部引線端部的鍍銀部分進行配線。
鑄型(molding):以環氧系鑄型劑進行轉移鑄型。
完成步驟:實施復位、沖壓、外引線部份的鍍覆等步驟,完成封裝。
[評估] [低溫接著、硬化]
對於實施例1至18及比較例1、2的接著膠帶,進行是否可容易且迅速地接著於被附著體(亦即底板或者是引線接腳)之評估。
具體而言,在100℃、140℃或者180℃將接著膠帶貼合(貼附)於銅板後,測定寬10mm的膠帶於室溫之90°剝離強度(接著力)。
結果表示於表2。
接下來,將接著力為4.2 N/cm以上作為可接著,以下述基準進行[低溫接著、硬化]的評估。
◎:可在100℃接著。實用上屬優良者。
○:可在140℃接著。實用上無問題者。
△:可在180℃接著。可實用者。
×:無法在180℃接著。實用上有問題者。
低溫接著、硬化的評估結果表示於表5。
[耐熱性]
以如下述之孔洞、剪力接著力為基準進行評估。
(孔洞)
當接著劑硬化時,藉由顯微鏡以視覺判定接著劑內產生的孔洞是否成為實用上有問題的程度。
具體而言,在140℃將接著膠帶貼合(貼附)於銅板後,保管於30℃/70%RH溼度調節72小時,作為試驗用樣品。
接下來,將試驗用樣品置於160℃的加熱器組件上1分鐘,藉由顯微鏡以視覺判定膠帶與銅板間的孔洞的狀態。
[剪力接著力] [製作試驗體]
將裁切為寬5mm×長度75mm的接著膠帶,在140℃貼合(貼附)於20mm×20mm的銅板的端部(一片之中央部份)。
貼附面積為25mm2 (5mm×5mm尺寸),未黏著於銅材之膠帶長度為70mm。
[剪力接著強度測定]
將上述試驗體固定於160℃的加熱器組件上後,將膠帶未黏著於銅板的部分連接於萬能拉伸試驗機,測定剪力接著強度。
測定時,銅板-拉伸試驗機的夾具間隔距離為50mm,拉伸速度為50mm/分。
並且,為使測定溫度安定化,將試驗體固定於加熱器組件上,經五秒後開始測定。
結果表示於表3。
接下來,以下述基準進行[耐熱性]的評估。
◎:無孔洞,且剪力接著強度40N/cm2 以上(於實用上完全無問題)。
○:無孔洞,且剪力接著強度20N/cm2 以上且未達40N/cm2 (於實用上無問題)。
△:無孔洞,且剪力接著強度未達20N/cm2 (於實用上無問題)。
×:有孔洞,且剪力接著強度未達20N/cm2 (於實用上有問題)。
耐熱性的評估結果表示於表5。
[引線接腳的尺寸安定性]
使接著劑硬化時,依據引線接腳的位置偏移是否達到實用上有問題的程度而進行評估。
具體而言,使用模具將接著膠帶沖壓為外尺寸22mm×內尺寸20mm之正方形(環狀)後,以熱加壓而貼附於評價用引線框架(QFP208接腳)之指定位置。
熱加壓條件,係壓力5Kgf/cm2 、壓合時間0.3秒。壓合溫度為120至140℃(將引線接腳上之接著劑厚度成為15至18μm的溫度視為可貼合之溫度)。
並且,經使用之引線框架的接腳間距為168μm。
[引線接腳之位置偏移的測定]
於膠帶剛貼附後及於熱風循環型爐200℃/1小時處理後,以顯微鏡測定引線框架的接腳間距。
壓合溫度與測定結果表示於表4。
接下來,以下述基準進行[引線接腳的尺寸安定性]的評估。
○:膠帶剛貼附之接腳間距,以及以熱風循環型爐處理200℃/1小時後之接腳間距,皆於168μm±10%以內。
△:膠帶剛貼附之接腳間距,以及以熱風循環型爐處理200℃/1小時後之接腳間距,皆超過168μm±10%而於168μm±15%以內。
×:膠帶剛貼附之接腳間距,以及以熱風循環型爐處理200℃/1小時後之接腳間距,皆為超過168μm±15%之值。
引線接腳的尺寸安定性的評估結果表示於表5。
[信賴性]
對如前述所得到之封裝體,進行PCBT試驗(Pressure Cooker Biased Test)。
條件係以施加100伏特、在130℃、2atm、85%RH實施,進行電氣信賴性試驗。
接下來,以下述基準進行[信賴性]的評估。
○:240小時中無短路。
×:240小時中有短路。
信賴性的評估結果表示於表5。
[抗遷移性]
於前述信賴性試驗之後,研磨封裝體使接著劑面露出,以顯微鏡觀察之。
接下來,以下述基準進行[抗遷移性]的評估。
◎:沒有確認到樹突,引線接腳亦無變色。
○:沒有確認到樹突,引線接腳有變色。
×:有樹突
抗遷移性的評估結果表示於表5。
[作業性]
組裝引線框架時之接著膠帶的貼附等,使用時之處理性(捲曲、搬移性)及接著膠帶的接著劑表面之黏性,係以下述基準進行[作業性]評估。
○:無黏性而非常利於進行作業
△:黏性少而利於進行作業
×:有黏性而不利於進行作業
評估結果表示於表5。
[評估結果]
如表5所示,實施例1至18的接著膠帶,全部為△以上而無實用上的問題。
特別是實施例5、實施例9、實施例16及實施例17,其低溫接著、硬化、耐熱性、抗遷移性優良。又以實施例2之低溫接著、硬化、耐熱性、抗遷移性為優良。
相對於此,比較例1的接著膠帶,於信賴性試驗有短路、抗遷移性有樹突,故有實用上的問題。
此外,比較例2的接著膠帶,關於耐熱性及引線接腳的尺寸安定性有實用上的問題。
(產業上之可利用性)
可提供一種可在低溫接著、硬化,具有充分之耐熱性及信賴性,且抗遷移性優良的電子部件用液狀接著劑及接著膠帶。
1‧‧‧半導體晶片
2‧‧‧底板
3‧‧‧引線接腳
4‧‧‧接合線
5‧‧‧樹脂
6‧‧‧接著層
7‧‧‧晶片墊
8‧‧‧電極
第1圖係使用本發明或以往之接著膠帶的樹脂密封型半導體裝置(半導體封裝體)的一例之剖面圖。
第2圖係使用本發明或以往之接著膠帶的樹脂密封型半導體裝置(半導體封裝體)的其他例之剖面圖。
第3圖係使用本發明或以往之接著膠帶的樹脂密封型半導體裝置(半導體封裝)的又一其他例之剖面圖。
1...半導體晶片
2...底板
3...引線接腳
4...接合線
5...樹脂
6...接著層

Claims (13)

  1. 一種電子部件用液狀接著劑,係於有機溶劑中溶解有:成份(a)丙烯腈-丁二烯共聚物、(b)酚樹脂、及(c)含有兩個以上馬來醯亞胺基之化合物,其中,前述成份(c)係包含下式(1)所示之化合物以及下式(2)所示之化合物者, 前述成份(c)之上式(1)及(2)所示化合物的質量比係3:3至3:45者。
  2. 如申請專利範圍第1項所述之電子部件用液狀接著劑,其中,前述成份(a)之慕尼黏度(Mooney viscosity)係50至90M1+4 100℃者。
  3. 如申請專利範圍第1項所述之電子部件用液狀接著劑,其中,前述成份(a)係具有羧基之丙烯腈-丁二烯共聚物者。
  4. 如申請專利範圍第1項所述之電子部件用液狀接著劑,其中,前述成份(b)係包含可溶酚醛型(resol-type)烷基酚的酚樹脂者。
  5. 如申請專利範圍第1項所述之電子部件用液狀接著劑,其中,前述成份(b)係併用可溶酚醛型(resol-type)酚樹脂與酚醛清漆型(novolac-type)酚樹脂者。
  6. 如申請專利範圍第1項所述之電子部件用液狀接著劑,其中,相對於成分(a)100質量份,成分(b)、成份(c)的總合係10至900質量份,且成分(b)、成份(c)的合計含量中,成分(b)的質量比例係10至90質量%者。
  7. 如申請專利範圍第1項所述之電子部件用液狀接著劑,其中,復含有成份(d)二胺化合物者。
  8. 如申請專利範圍第7項所述之電子部件用液狀接著劑,其中,前述成份(d)係下式(3)所示之化合物者,H2 N-R1 -NH2 (3)(式中,R1 表示2價的芳香族基)。
  9. 如申請專利範圍第7項所述之電子部件用液狀接著劑,其中,前述成份(d)係下式(4)所示之化合物,且重量平均分子量為200至7,000者, (式中,R2 表示丙烯基或苯氧基亞甲基,n為0至7的整數)。
  10. 如申請專利範圍第1項所述之電子部件用液狀接著劑,其中,包含佔全部固體成分4至40質量%之粒徑1 μm以下的填料者。
  11. 一種接著膠帶,其係至少於耐熱性膜的單面塗佈申請專利範圍第1項所述之電子部件用液狀接著劑並加以乾燥而形成有接著層者。
  12. 如申請專利範圍第11項所述之接著膠帶,其中,耐熱性膜係聚醯亞胺膜者。
  13. 一種接著膠帶,其係至少於剝離性膜之單面塗佈申請專利範圍第1項所述之電子部件用液狀接著劑並加以乾燥而形成有接著層者。
TW100110045A 2010-03-25 2011-03-24 電子部件用液狀接著劑及接著膠帶 TWI429723B (zh)

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