TWI500688B - 半導體密封用環氧樹脂組成物,半導體裝置及離型劑 - Google Patents
半導體密封用環氧樹脂組成物,半導體裝置及離型劑 Download PDFInfo
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- TWI500688B TWI500688B TW099135421A TW99135421A TWI500688B TW I500688 B TWI500688 B TW I500688B TW 099135421 A TW099135421 A TW 099135421A TW 99135421 A TW99135421 A TW 99135421A TW I500688 B TWI500688 B TW I500688B
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- epoxy resin
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Classifications
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- 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
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Description
本發明係關於半導體密封用環氧樹脂組成物、半導體裝置及離型劑。
半導體封裝組裝步驟中,藉由在半導體晶片的鋁電極與內引腳之間,將金線施行熱壓接而進行電氣式耦接的手法儼然是目前的主流。又,近年隨電子機器的小型化、輕量化、高性能化之市場動向,電子零件的高積體化、多針腳化正逐年進展。因而,便要求較先前更為複雜的焊接搭線步驟,當使用銅製引線框架的情況,因在長時間曝露於200~250℃高溫狀態下,因而銅表面的氧化便會更加進行。
在此種狀況下,即便習知對未氧化銅表面的接著性屬優異之半導體密封材,對表面狀態不同的氧化銅,多數情況係接著性較差,在樹脂密封後的脫模時或迴焊時會發生導致剝離的問題。
為抑制剝離用的內插品與密封材樹脂間之接著性,因為係屬與對模具的離型性呈相反之指標,因而若提升接著性則離型性便會變差,會有成形性降低的問題。就因電子零件的高積體化所造成的銅框架氧化問題,在以前為能兼顧接著性與離型性,便有提案將氧化聚乙烯蠟、及α-烯烴與順丁烯二酸的共聚合體之半酯化物,當作離型劑用的手法(例如參照專利文獻1、2)。根據該項手法,雖對未氧化銅的接著性與離型性均優異,但因為併用氧化聚乙烯蠟,因而會有密封樹脂對被氧化銅框架的接著力降低之問題。又,若α-烯烴部分係碳原子25個份以下的較短共聚合體離型劑(例如參照專利文獻3),會有連續成形性(通風孔阻塞等的離型性)差的問題。
專利文獻1:日本專利第3975386號公報
專利文獻2:日本專利第4010176號公報
專利文獻3:日本專利特公昭61-52862號公報
本發明係有鑑於該狀況而完成,在於提供對氧化銅的接著性呈良好,且離型性、連續成形性亦均優異的半導體密封用環氧樹脂組成物、及具備有由其施行密封之元件的半導體裝置及離型劑。
發明者等為解決上述問題而經深入鑽研,結果發現藉由在半導體密封用環氧樹脂組成物中使用特定離型劑,便可達成上述目的,遂完成本發明。
即,本發明係如下。
[1]一種半導體密封用環氧樹脂組成物,係含有:
(A)環氧樹脂、
(B)硬化劑、
(C)無機填充材、及離型劑;其中,上述離型劑係含有(D)將碳數28~60的α-烯烴與順丁烯二酸酐之共聚合體,利用碳數10~25的長鏈脂肪族醇進行酯化之化合物。
[2]如[1]所記載的半導體密封用環氧樹脂組成物,係更進一步含有下述一般式(I)所示矽氧烷加成聚合體改質物:
(式中,R1
~R2
係選自氫原子、碳數1~55的取代或非取代烴基、伸烷氧基環氧丙基醚基、及環氧烷基中,全部可為相同亦可為不同。R3
~R4
係選自氫原子、碳數1~10的取代或非取代烴基、胺基、羧基、環氧丙基醚基、及烷羧酸-4,4'-(1-甲基亞乙基)雙酚二環氧丙基醚基中,全部可為相同亦可為不同。n係指1~100的整數)。
[3]如[1]或[2]所記載的半導體密封用環氧樹脂組成物,其中,上述(D)將碳數28~60的α-烯烴與順丁烯二酸酐的共聚合體,利用碳數10~25的長鏈脂肪族醇進行酯化之化合物的含有量,係相對於上述離型劑總量100質量%,為55質量%以上且100質量%以下。
[4]如[2]所記載的半導體密封用環氧樹脂組成物,其中,上述矽氧烷加成聚合體改質物的含有量,係相對於上述半導體密封用環氧樹脂組成物總量100質量%,為0.1質量%以上且2質量%以下。
[5]如[1]至[4]項中任一項所記載的半導體密封用環氧樹脂組成物,其中,上述(A)環氧樹脂係含有從聯苯型環氧樹脂、對二甲苯型環氧樹脂、及具聯伸苯骨架之酚芳烷基型環氧樹脂所構成群組中選擇至少一種。
[6]如[1]至[5]項中任一項所記載的半導體密封用環氧樹脂組成物,係在設有含銅之引線框架的半導體裝置中,使用於半導體元件的密封。
[7]一種半導體裝置,係利用[1]至[6]項中任一項所記載之半導體密封用環氧樹脂組成物的硬化物,將半導體元件施行密封。
[8]一種離型劑,係含有(D)將碳數28~60的α-烯烴與順丁烯二酸酐的共聚合體,利用碳數10~25的長鏈脂肪族醇進行酯化之化合物。
[9]如[8]所記載的離型劑,係使用於半導體密封用環氧樹脂組成物。
[10]如[9]所記載的離型劑,其中,上述半導體密封用環氧樹脂組成物係在設有含銅之引線框架的半導體裝置中,使用於半導體元件的密封。
本發明的半導體密封用環氧樹脂組成物,係對氧化銅的接著性、及成形時的離型性與連續成形性均優異,且若使用該半導體密封用環氧樹脂組成物,將諸如IC、LSI等電子零件施行密封,便可獲得可靠度優異的半導體裝置。
上述目的、以及其他目的、特徵及優點,利用以下所述較佳實施形態、及其所附示的以下圖式便可更加明瞭。
本發明的半導體密封用環氧樹脂組成物,較佳係含有:(A)環氧樹脂、(B)硬化劑、(C)無機填充材、及離型劑。該離型劑較佳係含有:(D)將碳數28~60的α-烯烴與順丁烯二酸酐的共聚合體,利用碳數10~25的長鏈脂肪族醇進行酯化之化合物。
以下,針對各成分進行詳述。
本發明所使用的(A)環氧樹脂,係在半導體密封用環氧樹脂組成物中一般所使用者的前提下,其餘並無特別的限制,可舉例如將諸如酚酚醛型環氧樹脂、鄰甲酚酚醛型環氧樹脂等酚、甲酚、二甲酚、間苯二酚、兒茶酚、雙酚A、雙酚F等酚類及/或α-萘酚、β-萘酚、二羥基萘等萘酚類,與諸如甲醛、乙醛、丙醛、苯甲醛、水楊醛等具醛基的化合物,在酸性觸媒下進行縮合或共縮合而獲得的酚醛樹脂,經施行環氧化者;或者例如由使諸如雙酚A、雙酚F、雙酚S、雙酚A/D等二環氧丙基醚、屬於烷基取代或非取代雙酚之二環氧丙基醚的聯苯型環氧樹脂、酚類及/或萘酚類,與二甲氧基對二甲苯或雙(甲氧基甲基)聯苯所合成的酚芳烷基樹脂之環氧化物、茋型環氧樹脂、氫醌型環氧樹脂;或者由酞酸、二聚酸等多元酸與表氯醇的反應所獲得環氧丙基酯型環氧樹脂;或者由二胺基二苯基甲烷、異三聚氰酸等多元胺、與表氯醇的反應而獲得的環氧丙基胺型環氧樹脂;雙環戊二烯與酚類之共縮合樹脂之屬於環氧化物的雙環戊二烯型環氧樹脂;具萘環的環氧樹脂、三酚甲烷型環氧樹脂、三羥甲基丙烷型環氧樹脂、萜烯改質環氧樹脂、將烯烴鍵結利用過醋酸等過酸進行氧化而獲得的線狀脂肪族環氧樹脂、脂環族環氧樹脂、以及將該等環氧樹脂利用諸如聚矽氧、丙烯腈、丁二烯、戊二烯系橡膠、聚醯胺系樹脂等進行改質的環氧樹脂等等,該等係可單獨使用、亦可組合使用2種以上。
該等之中,就從對氧化銅的接著性觀點,較佳係下述一般式(II)所示聯苯型環氧樹脂、下述一般式(III)所示對二甲苯型環氧樹脂、及下述一般式(IV)所示具聯伸苯骨架之酚芳烷基型環氧樹脂。
(一般式(II)中,R1
~R4
係選自氫原子、及碳數1~10之取代或非取代的一價烴基中,全部可為相同亦可為不同。n係0~3的整數)。
(一般式(III)中,R係選自氫原子、及碳數1~10之取代或非取代的一價烴基中,n係0~20的整數)。
(一般式(IV)中,R5
~R13
係選自氫原子、及碳數1~10之取代或非取代的一價烴基中,全部可為相同亦可為不同。n係0~3的整數)。
上述一般式(II)中的R1
~R4
係選自氫原子、甲基、乙基、丙基、丁基、異丙基、異丁基等碳數1~10的烷基、以及甲氧基、乙氧基、丙氧基、丁氧基等碳數1~10的烷氧基、以及苯基、甲苯基、二甲苯基等碳數6~10的芳香基、以及苄基、苯乙基等碳數6~10的芳烷基等之中,其中較佳為氫原子或甲基。上述一般式(II)所示聯苯型環氧樹脂係可舉例如:以4,4'-雙(2,3-環氧丙氧基)聯苯或4,4'-雙(2,3-環氧丙氧基)-3,3',5,5'-四甲基聯苯為主成分的環氧樹脂;使表氯醇與4,4'-雙酚或4,4'-(3,3',5,5'-四甲基)雙酚進行反應,而獲得的環氧樹脂等,其中較佳為以4,4'-雙(2,3-環氧丙氧基)-3,3',5,5'-四甲基聯苯為主成分的環氧樹脂,就市售物可取得例如:YX-4000K、YX-4000H(Japan Epoxy Resins股份有限公司製商品名)等。當使用該聯苯型環氧樹脂時,會提升對氧化銅的接著性。其調配量在為能發揮其性能的前提下,相對於環氧樹脂全量,較佳為20質量%以上、更佳為30質量%以上、特佳為50質量%以上。
上述一般式(III)中的R係選自氫原子、甲基、乙基、丙基、丁基、異丙基、異丁基等碳數1~10的烷基、以及甲氧基、乙氧基、丙氧基、丁氧基等碳數1~10的烷氧基、以及苯基、甲苯基、二甲苯基等碳數6~10的芳香基、以及苄基、苯乙基等碳數6~10的芳烷基等之中,其中較佳為氫原子或甲基。上述一般式(III)所示對二甲苯型環氧樹脂更佳係以n=0為主成分的環氧樹脂,就市售物可取得例如NC2000(日本化藥股份有限公司製商品名)等。當使用該對二甲苯型環氧樹脂時,其調配量在為能發揮其性能的前提下,相對於環氧樹脂全量,較佳係設為10質量%以上、更佳係設為20質量%以上。
上述一般式(IV)中的R5
~R13
係選自氫原子、以及甲基、乙基、丙基、丁基、異丙基、異丁基等碳數1~10的烷基、以及甲氧基、乙氧基、丙氧基、丁氧基等碳數1~10的烷氧基、以及苯基、甲苯基、二甲苯基等碳數6~10的芳香基、以及苄基、苯乙基等碳數6~10的芳烷基等之中,其中,較佳為氫原子或甲基。上述一般式(IV)所示具聯伸苯骨架之酚芳烷基型環氧樹脂,較佳係以n=0為主成分的環氧樹脂,就市售物係可取得例如NC-3000L(日本化藥股份有限公司製商品名)等。當使用該具聯伸苯骨架之酚芳烷基型環氧樹脂時,其調配量在為能發揮其性能的前提下,相對於環氧樹脂全量,較佳係設為10質量%以上、更佳係設為20質量%以上。
上述一般式(II)所示聯苯型環氧樹脂、上述一般式(III)所示對二甲苯型環氧樹脂、及上述一般式(IV)所示具聯伸苯骨架之酚芳烷基型環氧樹脂,分別係可單獨使用、亦可併用2種以上。當併用2種以上的情況,該等的調配量係相對於(A)環氧樹脂全量,合計較佳係設為50質量%以上、更佳係設為70質量%以上。
本發明的(A)環氧樹脂含有量,相對於半導體密封用環氧樹脂組成物總量100質量%,雖無特別的限定,但較佳係0.8質量%以上且12質量%以下,更佳係1.5質量%以上且10質量%以下。
本發明所使用的(B)硬化劑係在屬於半導體密封用環氧樹脂組成物中一般使用者的前提下,其餘並無特別的限制,可例如酚樹脂。此種酚樹脂系硬化劑係一分子內具有2個以上酚性羥基的單體、寡聚物、聚合物全部,就其分子量、分子構造並無特別的限定,可舉例如:使酚酚醛樹脂、甲酚酚醛樹脂等酚、甲酚、間苯二酚、兒茶酚、雙酚A、雙酚F、苯基酚、胺基酚等酚類及/或α-萘酚、β-萘酚、二羥基萘等萘酚類,與甲醛等具醛基的化合物,在酸性觸媒下進行縮合或共縮合而獲得的樹脂;由酚類及/或萘酚類、與二甲氧基對二甲苯或雙(甲氧基甲基)聯苯所合成的酚芳烷基樹脂等,該等係可單獨使用、亦可組合使用2種以上。
其中,就從低黏度化、低吸濕性的觀點,較佳係具下述一般式(V)所示聯伸苯骨架的酚芳烷基樹脂。
(一般式(V)中,R14
~R22
係選自氫原子、及碳數1~10之取代或非取代的一價烴基中,全部可為相同亦可為不同。n係0~10的整數)。
上述式(V)中的R14
~R22
係全部可為相同亦可為不同,選自氫原子、甲基、乙基、丙基、丁基、異丙基、異丁基等碳數1~10的烷基、以及甲氧基、乙氧基、丙氧基、丁氧基等碳數1~10的烷氧基、以及苯基、甲苯基、二甲苯基等碳數6~10的芳香基、以及苄基、苯乙基等碳數6~10的芳烷基等碳數1~10之取代或非取代的一元烴基之中,較佳為氫原子及甲基。上述一般式(V)所示具聯伸苯骨架之酚芳烷基樹脂,可例如R14
~R22
全部均為氫原子的化合物等,其中,就從熔融黏度的觀點,較佳為含有n為1以上之縮合體達50質量%以上的縮合體混合物。此種化合物就市售物係可取得如MEH-7851SS(明和化成股份有限公司製商品名)。當使用該具有聯伸苯骨架之酚芳烷基樹脂時,就其調配量係為能發揮其性能,相對於(B)硬化劑全量,較佳設為50質量%以上、更佳設為70質量%以上。
本發明硬化劑(B)的含有量並無特別的限定,相對於半導體密封用環氧樹脂組成物總量100質量%,較佳設為0.8質量%以上且12質量%以下、更佳設為1.5質量%以上且10質量%以下。
(A)環氧樹脂與(B)硬化劑的當量比[即,(A)環氧樹脂中的環氧基數/(B)硬化劑中的羥基數之比]並無特別的限制,為將各未反應分抑制為較少,較佳係設定於0.5~2範圍內,更佳係設為0.6~1.5。為能獲得成形性、耐迴焊性均優異的半導體密封用環氧樹脂組成物,更佳係設定於0.8~1.2範圍內。
本發明的半導體密封用環氧樹脂組成物亦可更進一步含有(E)硬化促進劑。(E)硬化促進劑係在半導體密封用環氧樹脂組成物中一般所使用者的前提下,其餘並無特別的限制,可舉例如:1,8-二氮雜雙環(5,4,0)十一碳烯-7、1,5-二氮雜雙環(4,3,0)壬烯、5,6-二丁胺基-1,8-二氮雜雙環(5,4,0)十一碳烯-7等環脒化合物;苄基二甲胺、三乙醇胺、二甲胺基乙醇、參(二甲胺基甲基)酚等三級胺化合物及該等的衍生物;2-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑等咪唑化合物及該等的衍生物;三丁膦、甲基二苯膦、三苯膦、參(4-甲基苯基)膦、二苯膦、苯膦等有機膦;以及由在該等有機膦中加成諸如1,4-苯醌、2,5-甲醌、1,4-萘醌、2,3-二甲基苯醌、2,6-二甲基苯醌、2,3-二甲氧基-5-甲基-1,4-苯醌、2,3-二甲氧基-1,4-苯醌、苯基-1,4-苯醌等醌化合物、或雙酚A、雙酚F、雙酚S、酚樹脂等具π鍵的化合物而構成,具有分子內極化的化合物等有機磷化合物;四苯鏻四苯基硼酸鹽、三苯膦四苯基硼酸鹽等四苯硼酸鹽及該等的衍生物等等,該等係可單獨使用、亦可組合使用2種以上。其中,就從成形性的觀點,較佳為有機磷化合物,更佳為有機膦、及有機膦與醌化合物的加成物,特佳為三苯膦、以及三苯膦、參(4-甲基苯基)膦、參(4-甲氧基苯基)膦等第三膦、與對苯醌、1,4-萘醌等醌化合物的加成物。
(E)硬化促進劑的調配量係在屬於能達成硬化促進效果之量的前提下,其餘並無特別的限制,相對於(A)環氧樹脂總量100質量%,較佳為0.1~10質量%、更佳為1~5質量%。若未滿下限值,則會有短時間的硬化性劣化之傾向,反之,若超過上限值,則硬化速度過於快速,會有因未填充等而導致較難獲得良好成形品的傾向。
本發明所使用的(C)無機填充劑,係屬於為求吸濕性、降低線膨脹係數、提升熱傳導性、以及提升強度,而調配於成形材料中者,可舉例如:熔融二氧化矽、結晶二氧化矽、氧化鋁、鋯、矽酸鈣、碳酸鈣、鈦酸鉀、碳化矽、氮化矽、氮化鋁、氮化硼、氧化鈹、二氧化鋯、鋯、鎂橄欖石、皂石、尖晶石、高鋁紅柱石、二氧化鈦等的粉體、或者經將該等施行球形化的磨球、玻璃纖維等。此外,具難燃效果的無機填充劑係可舉例如:氫氧化鋁、氫氧化鎂、硼酸鋅、鉬酸鋅等。該等無機填充劑係可單獨使用、亦可組合使用2種以上。上述(C)無機填充劑中,就從降低線膨脹係數的觀點較佳為熔融二氧化矽,而就從高熱傳導性的觀點較佳為氧化鋁,而填充劑形狀係就從成形時的流動性及模具磨損性之觀點,較佳為球形。
(C)無機填充劑的調配量係就從成形性、吸濕性、降低線膨脹係數、及提升強度的觀點,相對於半導體密封用環氧樹脂組成物總量100質量%,較佳為80質量%以上、更佳為82~96質量%範圍、特佳為86~92質量%。若未滿下限值,則會有可靠度降低的傾向,反之,若超過上限值,則會有成形性降低的傾向。
在本發明所使用的離型劑中,含有:(D)將碳數28~60的α-烯烴與順丁烯二酸酐的共聚合體,利用碳數10~25的長鏈脂肪族醇進行酯化之化合物(以下亦稱「(D)化合物」)。該(D)化合物係有效於提高在(A)環氧樹脂中的分散性、提升對氧化銅的接著力與離型性。
(D)化合物中所使用碳數28~60的α-烯烴並無特別的限制,可舉例如:1-廿八碳烯、1-卅碳烯、1-卅一碳烯、1-卅二碳烯、1-卅三碳烯、1-卅四碳烯、1-卅五碳烯、1-卅六碳烯、1-四十碳烯、1-四十一碳烯(1-hentetracontyne)、1-四十二碳烯、1-四十三碳烯、1-四十四碳烯、1-五十碳烯、1-五十一碳烯、1-五十二碳烯(1-dopentacontyne)、1-五十三碳烯、1-五十五碳烯、1-六十碳烯等直鏈型α-烯烴;3-甲基-1-卅碳烯、3,4-二甲基-卅碳烯、3-甲基-1-四十碳烯、3,4-二甲基-四十碳烯等分支型α-烯烴等等,該等係可單獨使用、亦可組合使用2種以上。
(D)化合物中所使用α-烯烴的碳數,若未滿下限值,則連續成形性(離型性)會變差,反之,若超過上限值,則對氧化銅的接著性會降低。
(D)化合物中所使用碳數10~25的一元醇並無特別的限制,可舉例如:癸醇、十一烷醇、月桂醇、十三烷醇、肉荳蔻醇、十五烷醇、鯨蠟醇、十七烷醇、硬脂醇、十九烷醇、二十烷醇等直鏈型或分支型脂肪族飽和醇;己烯醇、2-己烯-1-醇、1-己烯-3-醇、戊烯醇、2-甲基-1-戊烯醇等直鏈型或分支型脂肪族不飽和醇;環戊醇、環己醇等脂環式醇;苄醇、桂皮醇等芳香族醇;糠醇等雜環式醇等等,該等係可單獨使用、亦可組合使用2種以上。較佳為碳數10~22的直鏈型醇、更佳為碳數15~20的直鏈型脂肪族飽和醇。
(D)化合物中所使用一元醇的碳數,若未滿下限值,則連續成形性(離型性)會變差,反之,若超過上限值,則對氧化銅的接著性會降低。
本發明的(D)化合物中,碳數28~60的α-烯烴與順丁烯二酸酐的共聚物並無特別的限制,可舉例如:下述一般式(VI)所示化合物、下述一般式(VII)所示化合物等,就市售物係可取得將例如:1-廿八碳烯、1-卅碳烯、1-四十碳烯、1-五十碳烯、1-六十碳烯(1-hexacontyne)等使用為原料的Diacarna(註冊商標)30(三菱化學股份有限公司製商品名)。
上述一般式(VI)及(VII)中,R係碳數26~56的一元脂肪族烴基,n係1以上的整數。m係α-烯烴與順丁烯二酸酐的共聚合比,並無特別的限制,當將α-烯烴設為X莫耳、將順丁烯二酸酐設為Y莫耳時,X/Y(即,m)較佳係1/2~10/1、更佳係大致等莫耳程度的1/1前後。
碳數28~60的α-烯烴、與順丁烯二酸酐的共聚物之製造方法,並無特別的限制,可使用例如使原材料進行反應等一般的共聚合方法。在反應中,亦可使用能將α-烯烴與順丁烯二酸酐予以溶解的有機溶劑等。有機溶劑並無特別的限制,較佳為甲苯,亦可使用例如芳香族系溶劑、醚系溶劑、鹵系溶劑等。反應溫度係依照所使用有機溶劑的種類而有所差異,就從反應性、生產性的觀點,較佳設為50~200℃、更佳設為100~150℃。反應時間係在能獲得共聚物的前提下,其餘並無特別的限制,就從生產性的觀點,較佳設為1~30小時、更佳設為2~15小時、特佳設為4~10小時。待反應結束後,視需要可在加熱減壓下等情況下,將未反應成分、溶劑等予以除去。其條件,就溫度較佳係設為100~220℃、更佳設為120~180℃,就壓力較佳係設為13.3×103
Pa以下、更佳設為8×103
Pa以下,就時間較佳係設為0.5~10小時。又,在反應中,視需要亦可添加偶氮雙異丁腈(AIBN)、過氧化苯甲醯(BPO)等自由基聚合系起始劑。
將碳數28~60的α-烯烴與順丁烯二酸酐的共聚物,利用碳數10~25的一元醇進行酯化之方法,並無特別的限制,可例如在共聚物中使一元醇進行加成反應等一般的手法。碳數28~60的α-烯烴與順丁烯二酸酐的共聚物、及一元醇的反應莫耳比,並無特別的限制,可任意設定,但因為藉由調整該反應莫耳比,便可控制親水性的程度,因而最好配合目標的密封用成形材料再適當設定。在反應中,亦可使用能溶解α-烯烴與順丁烯二酸酐的有機溶劑等。有機溶劑並無特別的限制,較佳為甲苯,亦可使用例如芳香族系溶劑、醚系溶劑、鹵系溶劑等。反應溫度係依照所使用有機溶劑的種類而有所差異,但就從反應性、生產性的觀點,較佳設為50~200℃、更佳設為100~150℃。反應時間係在能獲得共聚物的前提下,其餘並無特別的限制,但就從生產性的觀點,較佳設為1~30小時、更佳設為2~15小時、特佳設為4~10小時。待反應結束後,視需要可在加熱減壓下等情況下,將未反應成分、溶劑等予以除去。此條件,就溫度較佳設為100~220℃、更佳係設為120~180℃,就壓力較佳係設為13.3×103
Pa以下、更佳係設為8×103
Pa以下,就時間較佳係設為0.5~10小時。又,在反應中,視需要亦可添加例如乙基胺、N,N-二甲胺基吡啶等胺系觸媒、硫酸、對甲苯磺酸等酸觸媒等等反應觸媒。
(D)化合物可舉例如:在結構式中含有將選自下式(a)或(b)所示二酯、及式(c)~(f)所示單酯中1種以上,當作重複單元的化合物等,亦可含有式(g)或(h)所示非酯。此種化合物係有如:(1)主鏈骨架單獨由(a)~(f)中任1種構成者;(2)無規含有(a)~(f)中任2種以上者、或規則性含有者、或嵌段狀含有者;(3)無規含有(a)~(f)中任1種或2種以上與(g)及/或(h)者、或規則性含有者、或嵌段狀含有者等,該等係可單獨使用、亦可組合使用2種以上。又,尚可為例如:(4)無規含有(g)及(h)者、或規則性含有者、或嵌段狀含有者、及/或(5)含有分別單獨由(g)或(h)構成者。(D)成分的酯化率係就從離型性及接著性的觀點,較佳設為20莫耳%以上,(D)化合物較佳係式(c)~(f)所示單酯中任1種或2種以上合計含有20莫耳%以上的化合物,更佳係含有30莫耳%以上的化合物。
上式(a)~(h)中,R1
係碳數26~56的一價脂肪族烴基;R2
係碳數10~25的一價烴基。m係α-烯烴(X)與順丁烯二酸酐(Y)的共聚合莫耳比X/Y,較佳為1/2~10/1、更佳為1/1左右。
(D)化合物的數量平均分子量係在重複單元達1以上的前提下,其餘並無特別的限制,不管哪一分子量區域,均可實現對氧化銅良好的接著性與離型性,但數量平均分子量最好為2000~10000。
(D)化合物中,雖即使未反應α-烯烴含有0~33質量%,連續成形性及對氧化銅的接著性仍不會有變化,但若含有量超過上限值,則成形品表面髒污(封裝髒污)情形會有趨於明顯的傾向。
(D)化合物的調配量並無特別的限制,相對於(A)環氧樹脂總量100質量%,較佳設為0.5~10質量%、更佳設為1~5質量%。若調配量未滿下限值,則會有離型性降低的傾向,若超過上限值,便會有對氧化銅的接著性嫌不足傾向。
本發明的半導體密封用環氧樹脂組成物中,在不致損及當作離型劑時能達成本發明效果的範圍內,尚可將例如:棕櫚蠟、褐煤酸、硬脂酸、高級脂肪酸、高級脂肪酸金屬鹽、褐煤酸酯等酯系蠟、或聚乙烯、或聚烯烴系蠟等習知公知離型劑,與(D)化合物併用。
再者,(D)化合物的含有量,相對於離型劑總量100質量%,雖無特別的限定,但最好設為55質量%以上且100質量%以下。藉由設為此種範圍,便可實現對氧化銅良好的接著性與離型性。
本發明所用的矽氧烷加成聚合體改質物,係下述一般式(I)所示,將二甲基矽氧烷的甲基取代基其中一部分,利用諸如烷基、環氧基、羧基、及胺基等取代基進行取代的改質聚矽氧油,因為與樹脂間之親和性優異,因而可獲得耐焊錫應力性、與流動性均良好的半導體密封用環氧樹脂組成物。又,具有使離型劑分散於樹脂中的效果,亦可期待不會使接著性降低、以及提高離型效果的效果。上述矽氧烷加成聚合體改質物係1種或2種以上混合,相對於半導體密封用環氧樹脂組成物全體,可使用0.1~2質量%。但,當矽氧烷加成聚合體改質物超過上限值時,容易發生表面污染情形,會有樹脂滲出變長的可能性,反之,當使用未滿下限值時,並無法獲得充分低的彈性模數、及離型劑的分散性。
(一般式(I)中,R1
~R2
係選自氫原子、碳數1~55的取代或非取代烴基、伸烷氧基環氧丙基醚基、及環氧烷基中,全部可為相同亦可為不同。R3
~R4
係選自氫原子、碳數1~10的取代或非取代烴基、胺基、羧基、環氧丙基醚基、及烷羧酸-4,4'-(1-甲基亞乙基)雙酚二環氧丙基醚基中,全部可為相同亦可為不同。n係1~100的整數)。
本發明的半導體密封用環氧樹脂組成物中,就從提升IC等半導體元件的耐濕性、高溫放置特性之觀點,亦可添加陰離子交換體。陰離子交換體並無特別的限制,可使用習知公知物,例如:水滑石、或選自銻、鉍、鋯、鈦、錫、鎂、鋁中之元素的含氫氧化物等,該等係可單獨使用、亦可組合使用2種以上。其中,較佳為下述一般式(VIII)所示水滑石、及鉍的含氫氧化物。
Mg1-x
Alx
(OH)2
(CO3
)x/2
‧mH2
O (VIII)
(0<X≦0.5,m係正整數)
陰離子交換體的調配量係在能捕捉諸如鹵離子等離子性雜質的足夠量前提下,其餘並無特別的限制,相對於(A)環氧樹脂總量100質量%,較佳為0.1~30質量%、更佳為1~10質量%、特佳為2~5質量%。若調配量未滿下限值,則會有離子性雜質的捕捉嫌不足傾向,反之,若超過上限值時,相較於調配量在此以下的情況下,效果並無太大差異,因而不利經濟效益。
本發明的半導體密封用環氧樹脂組成物中,為能提高樹脂成分與無機填充劑間之接著性,視需要可添加例如環氧矽烷、硫醇基矽烷、胺基矽烷、烷基矽烷、脲矽烷、乙烯基矽烷等各種矽烷系化合物、或鈦系化合物、鋁螯合類、鋁/鋯系化合物等公知偶合劑。若例示該等,可舉例如:乙烯基三乙氧基矽烷、乙烯基參(β-甲氧基乙氧基)矽烷、γ-甲基丙烯醯氧基丙基三甲氧基矽烷、β-(3,4-環氧環己基)乙基三甲氧基矽烷、γ-環氧丙氧基丙基三甲氧基矽烷、γ-環氧丙氧基丙基甲基二甲氧基矽烷、γ-環氧丙氧基丙基三乙氧基矽烷、乙烯基三乙醯氧基矽烷、γ-硫醇基丙基三甲氧基矽烷、γ-硫醇基丙基甲基二甲氧基矽烷、γ-硫醇基丙基三乙氧基矽烷、γ-胺基丙基三甲氧基矽烷、γ-胺基丙基甲基二甲氧基矽烷、γ-胺基丙基三乙氧基矽烷、γ-苯胺基丙基三甲氧基矽烷、γ-苯胺基丙基甲基二甲氧基矽烷、N-β-(胺基乙基)-γ-胺基丙基三甲氧基矽烷、γ-(β-胺基乙基)胺基丙基二甲氧基甲基矽烷、N-(三甲氧基矽烷基丙基)乙二胺、N-(二甲氧基甲基矽烷基異丙基)乙二胺、N-β-(N-乙烯基苄基胺基乙基)-γ-胺基丙基三甲氧基矽烷、γ-氯化丙基三甲氧基矽烷、六甲基二矽烷、乙烯基三甲氧基矽烷等矽烷系偶合劑;三異硬脂醯基鈦酸異丙酯、參(二辛基焦磷酸酯)鈦酸異丙酯、三(N-胺基乙基-胺基乙基)鈦酸異丙酯、四辛基雙(二(十三烷基)磷酸酯)鈦酸酯、四(2,2-二烯丙氧基甲基-1-丁基)雙(二(十三烷基))磷酸鈦酸酯、雙(二辛基焦磷酸酯)氧基醋酸鈦酸鹽、雙(二辛基焦磷酸酯)伸乙基鈦酸鹽、三辛醯基鈦酸異丙酯、二甲基丙烯基異硬脂醯基鈦酸異丙酯、三(十二烷基)苯磺醯基鈦酸異丙酯、異硬脂醯基二丙烯基鈦酸異丙酯、三(二辛基磷酸酯)鈦酸異丙酯、三異丙苯基苯基鈦酸異丙酯、四異丙基雙(二辛基磷酸酯)鈦酸酯等鈦酸酯系偶合劑等,該等係可單獨使用、亦可組合使用2種以上。
上述偶合劑的調配量,係相對於(C)無機填充劑總量100質量%,較佳為0.05~5質量%、更佳為0.1~2.5質量%。若未滿下限值,則會有耐濕性降低傾向,反之,若超過上限值,便會有封裝的成形性降低傾向。
再者,本發明的半導體密封用環氧樹脂組成物中,視需要尚可調配入其他添加劑,例如:溴化環氧樹脂、三氧化銻、四氧化銻、五氧化銻等,含有鹵原子、銻原子、氮原子或磷原子的公知有機或無機化合物;金屬氫氧化物等難燃劑;碳黑、有機染料、有機顏料、氧化鈦、鉛丹、氧化鐵紅等著色劑;咪唑、三唑、四唑、三等、及該等的衍生物;鄰胺基苯甲酸、沒食子酸、丙二酸、蘋果酸、順丁烯二酸、胺基酚、喹啉等及該等的衍生物;脂肪族酸醯胺化合物、二硫代胺基甲酸鹽(dithiocarbamate)、噻二唑衍生物等接著促進劑等等。
本發明的半導體密封用環氧樹脂組成物係在能將各種原材料均勻分散混合的前提下,可使用任何手法進行調製,一般的手法係有如:將既定調配量的原材料利用混合機等進行充分混合後,再利用諸如軋輪機、捏合機、擠出機等進行熔融混練後,再施行冷卻、粉碎的方法。若依照配合成形條件的尺寸與質量進行打錠化便可輕易使用。
再者,本發明的半導體密封用環氧樹脂組成物,亦可溶解於各種有機溶劑中,經形成液狀半導體密封用環氧樹脂組成物之後才使用,亦可將該液狀半導體密封用環氧樹脂組成物薄薄地塗佈於板或薄膜上,再依樹脂的硬化反應不致進行的條件使有機溶劑揮散後,使用依此所獲得的薄片或薄膜狀半導體密封用環氧樹脂組成物。
利用依照本發明所獲得半導體密封用環氧樹脂組成物,將元件施行密封而獲得的半導體裝置,係有如:在銅引線框架的支撐構件上,搭載諸如:半導體晶片、電晶體、二極體、閘流體等主動元件、或諸如電容器、電阻體、線圈等被動元件等等元件,再將必要的部分利用本發明半導體密封用環氧樹脂組成物施行密封之半導體裝置等。此種半導體裝置係有如:在銅引線框架上固定著半導體元件,再將焊接墊等元件端子部與引線部,利用焊接搭線或凸塊進行耦接後,再使用本發明半導體密封用環氧樹脂組成物利用轉印成形等進行密封而構成,例如:DIP(Dual Inline Package)、PLCC(Plastic Leaded Chip Carrier)、QFP(Quad Flat Package)、SOP(Small Outline Package)、SOJ(Small Outline J-lead package)、TSOP(Thin Small Outline Package)、TQFP(Thin Quad Flat Package)等一般的樹脂密封型IC。
圖1所示係相關使用本發明半導體密封用環氧樹脂組成物的半導體裝置一例之截面構造圖。在晶片焊墊3上隔著黏晶材硬化體2積層著2層的半導體元件1並固定。半導體元件1的電極焊墊與銅引線框架5之間利用金線4耦接。半導體元件1係利用密封用樹脂組成物的硬化體6而密封。銅引線框架5較佳係半導體裝置技術領域中,一般所使用的通用含銅之引線框架。該含銅之引線框架係在含銅的前提下,其餘並無特別的限定,較佳係至少表面含銅的引線框架、或銅合金的引線框架、或由銅構成的引線框架等。
使用本發明半導體密封用環氧樹脂組成物,將元件施行密封的方法,最一般係低壓轉印成形法,但亦可使用射出成形法、壓縮成形法等。當半導體密封用環氧樹脂組成物在常溫下呈液狀或糊膏狀時,便可例如點膠方式、注模方式、印刷方式等。
再者,不僅將元件直接施行樹脂密封的一般密封方法,尚有例如半導體密封用環氧樹脂組成物不會直接接觸到元件形態的中空封裝方式,亦可適用為中空封裝用的半導體密封用環氧樹脂組成物。
再者,本發明的半導體密封用環氧樹脂組成物係對氧化銅的接著性、離型性、連續成形性等均優異,若使用該半導體密封用環氧樹脂組成物,將諸如IC、LSI等電子零件施行密封,便可獲得可靠度優異的半導體裝置。
以下,針對本發明舉實施例進行詳細說明,惟本發明並不僅侷限於該等。
合成例1:將碳數28~60的α-烯烴與順丁烯二酸酐之共聚物,利用碳數18的一元醇施行酯化的化合物(D)之合成
將1-廿八碳烯、1-卅碳烯、1-四十碳烯、1-五十碳烯、1-六十碳烯等的混合物、與順丁烯二酸酐的共聚物(三菱化學股份有限公司製、商品名Diacarna(註冊商標)30)300g、及硬脂醇140g,溶解於甲苯500ml中,經依110℃進行8小時反應後,一邊階段性升溫至160℃,一邊將甲苯除去,在減壓下,依160℃進行6小時反應,而將未反應成分除去,便獲得目標單酯化率100莫耳%的化合物1(489g)。分子量係經以四氫呋喃為溶析液,且利用聚苯乙烯換算的凝膠滲透色層分析儀進行測定,結果為數量平均分子量(Mn)=4100、分子量分佈(Mw/Mn)=3.52,未反應的硬脂醇殘留量係佔化合物1全體的1%以下。
將上述化合物1(100g)溶解於丙酮400ml中,再添加正己烷300ml。過濾所析出的沉澱物,經乾燥,便獲得化合物1的高分子量體70g。分子量係經以四氫呋喃為溶析液,且利用聚苯乙烯換算的凝膠滲透色層分析儀進行測定,結果為數量平均分子量(Mn)=5600、分子量分佈(Mw/Mn)=1.82。且,從上清液中將溶劑餾除,經乾燥,便獲得化合物1的低分子量體20g。分子量係經以四氫呋喃為溶析液,且利用聚苯乙烯換算的凝膠滲透色層分析儀進行測定,結果為數量平均分子量(Mn)=2400、分子量分佈(Mw/Mn)=2.21。
合成例2:將碳數28~60的α-烯烴與順丁烯二酸酐之共聚物,利用碳數12的一元醇進行酯化之化合物(D)的合成
除取代硬脂醇,改為添加1-十二碳醇97g之外,其餘均依照合成例1所記載的方法,獲得單酯化率100莫耳%的化合物2(385g)。分子量係經以四氫呋喃為溶析液,且利用聚苯乙烯換算的凝膠滲透色層分析儀進行測定,結果為數量平均分子量(Mn)=3800、分子量分佈(Mw/Mn)=3.81,未反應的1-十二碳醇殘留量係佔化合物2全體的1%以下。
合成例3:將碳數28~60的α-烯烴與順丁烯二酸酐之共聚物,利用碳數22的一元醇進行酯化之化合物(D)的合成
除取代硬脂醇,改為添加廿二烷醇(花王股份有限公司製、商品名KALCOL220-80)170g之外,其餘均依照合成例1所記載的方法,獲得單酯化率100莫耳%的化合物3(458g)。分子量係經以四氫呋喃為溶析,且利用聚苯乙烯換算的凝膠滲透色層分析儀進行測定,結果為數量平均分子量(Mn)=4400、分子量分佈(Mw/Mn)=3.55,未反應的廿二烷醇殘留量係佔化合物3全體的1%以下。
合成例4:將碳數20~24的α-烯烴與順丁烯二酸酐之共聚物,利用碳數18的一元醇進行酯化之化合物的合成
將1-廿碳烯、1-廿二碳烯、及1-廿四碳烯的混合物(出光興產股份有限公司製、商品名LINEALENE 2024)180g、與順丁烯二酸酐58g,溶解於甲苯500ml中,一邊依110℃進行加熱,一邊每隔20分鐘將BPO(0.16g)分開3次添加。待BPO添加結束後,將反應溶液再依110℃加熱7小時。在該共聚物的甲苯溶液中添加硬脂醇162g,經依110℃進行8小時反應後,一邊階段性升溫至160℃,一邊將甲苯除去,在減壓下依160℃進行6小時反應,而將未反應成分除去,便獲得目標單酯化率100莫耳%的化合物4(380g)。分子量係經以四氫呋喃為溶析液,且利用聚苯乙烯換算的凝膠滲透色層分析儀進行測定,結果為數量平均分子量(Mn)=9800、分子量分佈(Mw/Mn)=2.63,未反應的硬脂醇殘留量係佔化合物4全體的1%以下。
合成例5:將碳數28~60的α-烯烴與順丁烯二酸酐的共聚物,利用碳數8的一元醇進行酯化之化合物的合成
除取代硬脂醇,改為添加1-辛醇68g之外,其餘均依照合成例1所記載的方法,獲得單酯化率100莫耳%的化合物5(340g)。分子量係經以四氫呋喃為溶析液,且利用聚苯乙烯換算的凝膠滲透色層分析儀進行測定,結果為數量平均分子量(Mn)=3700、分子量分佈(Mw/Mn)=3.80,未反應的1-辛醇殘留量係佔化合物5全體的1%以下。
合成例6:將碳數28~60的α-烯烴與順丁烯二酸酐的共聚物,利用碳數28的一元醇進行酯化之化合物(D)的合成
除取代硬脂醇,改為添加廿八烷醇[素材機能研究所股份有限公司製、商品名Policosanol(源自米糠)]214g之外,其餘均依照合成例1所記載的方法,獲得單酯化率100莫耳%的化合物6(506g)。分子量係經以四氫呋喃為溶析液,且利用聚苯乙烯換算的凝膠滲透色層分析儀進行測定,結果為數量平均分子量(Mn)=4800、分子量分佈(Mw/Mn)=3.91,未反應的廿八烷醇殘留量係佔化合物6全體的1%以下。
相關實施例1~10及比較例1~9所使用的成分,如下示。
環氧當量185、融點108℃的聯苯型環氧樹脂(Japan Epoxy 股份有限公司製、商品名EPIKOTE YX-4000K)、
環氧當量237、軟化點52℃的對二甲苯型環氧樹脂(日本化藥公司製、商品名NC2000)、
環氧當量273、軟化點52℃的具聯伸苯骨架之酚芳烷基型環氧樹脂(簡稱「聯苯芳烷基型環氧樹脂」)(日本化藥公司製、商品名NC-3000L)
羥基當量199、軟化點64℃的具聯伸苯骨架之酚芳烷基型酚樹脂(簡稱「聯苯芳烷基樹脂」)(明和化成股份有限公司製、商品名MEH-7851SS)
平均粒徑10.8μm、比表面積5.1m2
/g的球狀熔融二氧化矽(電氣化學工業股份有限公司製、商品名電化熔融二氧化矽(DF)球形粉末型式(等級FB-105))
依上述合成例所獲得化合物1~6,其他的離型劑係氧化聚乙烯蠟(Clariant公司製、商品名PED191)、褐煤酸系蠟(Clariant公司製、商品名Licowax E)、α-烯烴單體(Chevron Phillips Chemical Company製、商品名Alpha Olefin C30+)
三苯膦與對苯醌的加成物(北興化學股份有限公司製、商品名TPP-BQ)
矽氧烷加成聚合體改質物:將聚矽氧油A[將下式(IX)所示化合物(TORAY‧Dow Corning股份有限公司製、BY-750、分子量約1500)、與雙酚A型環氧樹脂(Japan Epoxy Resins股份有限公司製、JER(註冊商標)YL-6810(環氧當量172g/eq、融點45℃)12質量份,依140℃進行加溫熔融,再添加G1-1(6質量份)、三苯膦0.15質量份,再經依140℃施行30分鐘熔融混合而獲得的熔融反應物)
聚矽氧油B[下式(X)所示化合物;式(X)中,m、n、l、a及b係相同或不同的整數(TORAY‧Dow Corning股份有限公司製、商品名FZ-3730)]
偶合劑:γ-環氧丙氧基丙基三甲氧基矽烷(CHISSO股份有限公司製、商品名S510=GPS-M)
著色劑:碳黑(三菱化學股份有限公司製、商品名carbon#5)
將上述成分分別依表1及表2所示質量份進行調配,再依混練溫度100℃、混練時間30分鐘的條件進行雙軸混練,經冷卻後再粉碎,便製得半導體密封用環氧樹脂組成物。另,比較例4及5的化合物1及化合物4、與氧化聚乙烯蠟,係經與聯苯型環氧樹脂依170℃、6小時的條件施行預混練後才使用。
將所製得實施例及比較例的半導體密封用環氧樹脂組成物,依下述各試驗進行評估。評估結果如表3及表4所示。
將氧化銅基材、與經打錠化的半導體密封用環氧樹脂組成物,經依175℃、70kg/cm2
、2分鐘的條件施行一體成形,獲得切頭體狀成形品(上徑2mm×下徑3mm×厚3mm)後,再將所獲得各成形品的基材予以固定,從橫向按押半導體密封用環氧樹脂組成物的硬化部位,並測定其轉矩(N)。
離型時荷重評估用模具係轉印成形模,由上模、中模、下模構成。圖2所示係經成形後的中模平面概略圖。經成形後,附著於中模上的成形品形狀係直徑14.0mm、高1.5mm厚。圖2中,11係中模,12係殘料廢品,13係流道。14係成形品,15係通風孔。16係把手,17係推拉力計插入用孔。
使用圖2所示離型時荷重評估用模具,依模具溫度175℃、注入壓力6.9MPa、硬化時間1分鐘,將評估用材料施行轉印成形。經成形後,在中模11上所附著的圓形成形品14中,從中模上部的孔17碰抵推拉力計(參照圖3),測定當將成形品突出時所施加的荷重。接著,將評估用材料施行20射膠成形時,針對後半段10射膠的成形品施行測定,並將其平均值視為「離型荷重」且進行評估。
使用低壓轉印自動成形機(第一精工股份有限公司製、GP-ELF),依模具溫度175℃、注入壓力9.8MPa、硬化時間70秒,將80針腳方形扁平封裝(80pQFP;Cu製引線框架、封裝外寸:14mm×20mm×厚2mm、焊墊尺寸:6.5mm×6.5mm、晶片尺寸6.0mm×6.0mm×厚0.35mm),連續地施行密封成形直到400射膠為止。
通風孔阻塞係每隔50射膠便依目視觀察模具,確認有無通風孔阻塞,並依下述4階段進行評估。
A:直到400射膠為止均無問題
B:直到300射膠為止有發生通風孔阻塞
C:直到200射膠為止有發生通風孔阻塞
D:直到100射膠為止有發生通風孔阻塞
相關模具髒污,觀察400射膠的模具,並從澆口的髒污擴展程度,依下述5階段進行評估。
A:無髒污
B:髒污雖有擴展,在封裝表面的10面積%以下
C:髒污雖有擴展,在封裝表面的超過10面積%~20面積%以下
D:髒污雖有擴展,在封裝表面的超過20面積%~50面積%以下
E:髒污雖有擴展,在封裝表面的超過50面積%
相關封裝髒污,觀察400射膠的封裝,並從澆口的髒污擴展程度,依下述5階段進行評估。
A:無髒污
B:髒污雖有擴展,在封裝表面的10面積%以下
C:髒污雖有擴展,在封裝表面的超過10面積%~20面積%以下
D:髒污雖有擴展,在封裝表面的超過20面積%~50面積%以下
E:髒污雖有擴展,在封裝表面的超過50面積%
實施例1~5係對氧化銅的接著強度、離型性(離型荷重)均呈良好。矽氧烷加成聚合體改質物係含有聚矽氧油成分的實施例6及7,亦是對氧化銅的接著強度、離型性(離型荷重)均呈良好,且連續成形性(模具髒污)亦獲更進一步改善。(A)環氧樹脂係全量使用聯苯型環氧樹脂或具聯伸苯骨架之酚芳烷基型環氧樹脂(聯苯芳烷基型環氧樹脂),並含有聚矽氧油成分的實施例8及實施例9,亦是離型性(離型荷重)呈良好,對氧化銅的接著強度獲更進一步改善。α-烯烴單體在(D)化合物中含35質量%的實施例10,相較於比較例之下,對氧化銅的接著強度、離型性(離型荷重)均呈良好。比較例1~3的離型性(離型荷重)差。又,離型劑成分係併用氧化聚乙烯蠟的比較例4~5及比較例7,連續成形性(通風孔阻塞)並非良好,且對氧化銅的接著亦受相當抑制。又,該比較例5係相當於專利文獻1或2所記載的實施例1。含褐煤酸系離型劑的比較例8及9,對氧化銅的接著強度較弱,且離型性(離型荷重)亦差。
本申請案係以日本平成21年10月20日所提出申請的日本特許出願特願2009-241427、平成22年3月25日所提出申請的日本特許出願特願2010-070700、及平成22年4月27日所提出申請的日本特許出願特願2010-102429為基礎並主張優先權,並將其揭示全部融入於本案中。
1...半導體元件
2...黏晶材硬化體
3...晶片焊墊
4...金線
5...銅引線框架
6...硬化體
11...中模
12...殘料廢品
13...流道
14...成形品
15...通風孔
16...把手
17...推拉力計插入用孔
圖1為相關使用本發明半導體密封用環氧樹脂組成物的半導體裝置一例之截面構造圖。
圖2為本發明半導體密封用環氧樹脂組成物,經利用為評估離型時荷重用的評估用模具進行成形後,中模狀態的平面概略圖。
圖3為圖2所示中模的成形品附近之A部分截面構造概略圖。
1...半導體元件
2...黏晶材硬化體
3...晶片焊墊
4...金線
5...銅引線框架
6...硬化體
Claims (8)
- 一種半導體密封用環氧樹脂組成物,係在設有含銅之引線框架的半導體裝置中,使用於半導體元件的密封;其含有:(A)環氧樹脂、(B)硬化劑、(C)無機填充材及離型劑;上述離型劑係含有(D)將碳數28~60的α-烯烴與順丁烯二酸酐之共聚合體利用碳數10~25的長鏈脂肪族醇進行酯化之化合物。
- 如申請專利範圍第1項之半導體密封用環氧樹脂組成物,其中,係更進一步含有下述一般式(I)所示矽氧烷加成聚合體改質物:
- 如申請專利範圍第1項之半導體密封用環氧樹脂組成物,其中,上述(D)將碳數28~60的α-烯烴與順丁烯二酸酐的共聚合體利用碳數10~25的長鏈脂肪族醇進行酯化之化合物的含有量,係相對於上述離型劑總量100質量%,為55質量%以上且100質量%以下。
- 如申請專利範圍第2項之半導體密封用環氧樹脂組成物,其中,上述矽氧烷加成聚合體改質物的含有量,係相對於上述半導體密封用環氧樹脂組成物總量100質量%,為0.1質量%以上且2質量%以下。
- 如申請專利範圍第1項之半導體密封用環氧樹脂組成物,其中,上述(A)環氧樹脂係含有從聯苯型環氧樹脂、對二甲苯型環氧樹脂、及具聯伸苯骨架之酚芳烷基型環氧樹脂所構成群組中選擇之至少一種。
- 一種半導體裝置,係利用申請專利範圍第1至5項中任一項之半導體密封用環氧樹脂組成物的硬化物,將半導體元件施行密封。
- 一種離型劑,係在設有含銅之引線框架的半導體裝置中,使用於半導體元件的密封;其含有(D)將碳數28~60的α-烯烴與順丁烯二酸酐的共聚合體利用碳數10~25的長鏈 脂肪族醇進行酯化之化合物。
- 如申請專利範圍第7項之離型劑,係使用於半導體密封用環氧樹脂組成物。
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WO2014116996A1 (en) * | 2013-01-25 | 2014-07-31 | Washington State University Research Foundation | Derivatives of fatty esters, fatty acids and rosins |
JP2016023279A (ja) * | 2014-07-23 | 2016-02-08 | 住友ベークライト株式会社 | 封止用樹脂組成物、半導体装置および構造体 |
JP6922158B2 (ja) * | 2016-04-20 | 2021-08-18 | 住友ベークライト株式会社 | 熱硬化性樹脂組成物、樹脂封止基板、および電子装置 |
JP6688992B2 (ja) * | 2016-07-29 | 2020-04-28 | パナソニックIpマネジメント株式会社 | 封止用エポキシ樹脂組成物、硬化物、及び半導体装置 |
CN106608008B (zh) * | 2016-11-28 | 2018-11-23 | 西安空间无线电技术研究所 | 一种脱模剂及其制备方法和在环氧树脂灌封中的应用 |
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CN113614141B (zh) * | 2019-03-27 | 2024-02-20 | 住友电木株式会社 | 密封用树脂组合物和半导体装置 |
CN111261527B (zh) * | 2020-02-11 | 2021-10-01 | 深圳市法本电子有限公司 | 一种半导体封装构件及其制备方法 |
CN111619046A (zh) * | 2020-05-25 | 2020-09-04 | 余姚市远东化工有限公司 | 一种耐储存的脱模剂及其制备方法 |
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CN112759891A (zh) * | 2020-12-28 | 2021-05-07 | 广东盈骅新材料科技有限公司 | 环氧树脂组合物及含有其的透明复合材料、层压板 |
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