TWI801565B - 樹脂組成物、疊層體、附樹脂組成物層之半導體晶圓、附樹脂組成物層之半導體搭載用基板、以及半導體裝置 - Google Patents

樹脂組成物、疊層體、附樹脂組成物層之半導體晶圓、附樹脂組成物層之半導體搭載用基板、以及半導體裝置 Download PDF

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TWI801565B
TWI801565B TW108114230A TW108114230A TWI801565B TW I801565 B TWI801565 B TW I801565B TW 108114230 A TW108114230 A TW 108114230A TW 108114230 A TW108114230 A TW 108114230A TW I801565 B TWI801565 B TW I801565B
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resin composition
bis
mass
flux
parts
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TW108114230A
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TW202003756A (zh
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岡庭正志
瀧口武紀
東口鑛平
木田剛
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日商三菱瓦斯化學股份有限公司
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Abstract

本發明提供一種樹脂組成物,兼顧優良的助熔劑活性及高絕緣可靠性,有良好的保存安定性,且作為疊層體時有作業性良好的可撓性。本發明之樹脂組成物,含有:螯合助熔劑(A)、熱自由基聚合起始劑(B)、及自由基聚合性化合物(C)。

Description

樹脂組成物、疊層體、附樹脂組成物層之半導體晶圓、附樹脂組成物層之半導體搭載用基板、以及半導體裝置
本發明係關於樹脂組成物、使用了樹脂組成物之疊層體、附樹脂組成物層之半導體晶圓、附樹脂組成物層之半導體搭載用基板、及半導體裝置。詳言之,本發明係關於就黏接劑用途而言為有用的樹脂組成物。
近年來伴隨半導體裝置的小型化及高性能化,作為將半導體晶片(以下有時簡稱「晶片」)搭載於半導體搭載用基板(以下有時簡稱「基板」)的方法,倒裝晶片(flipchip)安裝受人注目。倒裝晶片安裝,一般而言,係將晶片與基板予以接合後,在晶片與基板之間隙內填充底層填充材並使其硬化之工法。但是伴隨半導體裝置之小型化、高性能化,排列在晶片的電極的窄節距化、電極間的窄間距化越來越進展,因底層填充材的填充的長時間化導致作業性惡化、未填充等填充不良發生會成為問題。針對此點,有人研究對於晶片或基板供給預塗底層 填充材(preapplied underfill material)後,同時進行晶片與基板之接合及底層填充材之填充的工法。
晶片與基板之接合係介隔易氧化的金屬例如:焊料、銅進行時,為了將成為妨礙接合之原因的氧化膜從接合部除去並獲得良好的金屬接合,有時會在預塗底層填充材中添加來自羧酸等的助熔劑成分。
來自羧酸等的助熔劑成分,於半導體封裝體安裝後仍會存在,會使得已硬化的底層填充材料中之焊料、銅之相互連接腐蝕並使其劣化,或是促進焊料、銅的離子化,進而有因此遷移造成接合部間的填充不良的顧慮。
專利文獻1記載含有具三
Figure 108114230-A0305-02-0004-29
骨架之酚醛樹脂(phenolic resin)的薄膜狀黏接劑。三
Figure 108114230-A0305-02-0004-30
因為會和銅離子、從焊料產生的錫離子等金屬離子形成錯合物,故藉由有該骨架之樹脂進入黏接劑會發揮能夠抑制由於金屬離子的遷移導致電性不良的好處。
專利文獻2記載含有熱硬化性樹脂與螯合助熔劑之樹脂組成物。藉由使用螯合助熔劑,螯合助熔劑會捕捉硬化物中之金屬離子,藉此抑制由於金屬離子的遷移導致的電性不良,能形成有可靠性的接合。
專利文獻3記載使用自由基聚合性單體與熱自由基起始劑獲得之預塗底層填充材。藉由使用熱自由基起始劑,樹脂組成物之硬化時間不會花費長時間。
〔先前技術文獻〕 〔專利文獻〕
〔專利文獻1〕 日本特開2011-052109號公報
〔專利文獻2〕 日本特表2005-501725號公報
〔專利文獻3〕 日本特表2015-503220號公報
但是專利文獻1因在黏接劑中不含助熔劑成分,在接合時無法去除接合部之氧化膜,無法獲得良好的金屬接合。
又,專利文獻2記載含有螯合助熔劑與環氧樹脂之樹脂組成物,會有在比起倒裝晶片安裝時之接合溫度更為低溫,環氧樹脂會和螯合助熔劑擁有之苯酚性羥基進行反應,無法獲得良好的接合的缺點。
專利文獻3因不含助熔劑成分,無法去除接合部的氧化膜,無法獲得良好的金屬接合。故在使用底層填充材前需要預先去除接合部之金屬氧化膜的步驟,作業步驟會複雜化。
本發明有鑑於如此的課題,提供一種樹脂組成物,兼顧為了去除氧化膜而獲得金屬接合之充分的優良的助熔劑活性、及高絕緣可靠性,有良好的保存安定性,進而有使用於作為疊層體時作業性良好的可撓性。
本案發明人等為了解決前述問題而努力研究,結果發現含有螯合助熔劑(A)、熱自由基聚合起始劑(B)、及自由基聚合性化合物(C)的樹脂組成物能夠解決前述課題,乃完成本發明。
亦即,本發明包含下列內容。
〔1〕一種樹脂組成物,含有螯合助熔劑(A)、熱自由基聚合起始劑(B)、及自由基聚合性化合物(C)。
〔2〕如〔1〕之樹脂組成物,其中,該螯合助熔劑(A)之熔點為235℃以下。
〔3〕如〔1〕或〔2〕之樹脂組成物,其中,該螯合助熔劑(A)之分子量為150以上500以下。
〔4〕如〔1〕~〔3〕中任一項之樹脂組成物,其中,使用該螯合助熔劑(A)於下列焊料潤濕性試驗中獲得之焊球之接觸角未達1.20弳;焊料潤濕性試驗:於厚度12μm之銅箔之光澤面塗佈該螯合助熔劑,在該螯合助熔劑上放置直徑0.5mm的焊球,之後於保持在235℃的熱板上加熱1分鐘,使焊料熔融後,於室溫冷卻;冷卻後測定在該銅箔上擴開的焊球的半徑(a)及焊球的高度(b),並依下式算出接觸角;焊球之接觸角=2arctan{(b)/(a)}。
〔5〕如〔1〕~〔4〕中任一項之樹脂組成物,其中,該螯合助熔劑(A)含有下式(1)表示之化合物及/或下式(2)表示之亞胺化合物;【化1】
Figure 108114230-A0305-02-0007-1
式中,Q為伸芳基、伸烷基、伸烯基、環伸烷基、環伸烯基、伸雜環基、或伸雜芳基,R1及R2各自獨立地為氫原子、甲基、乙基、丙基、丁基、戊基、或己基,R3及R4各自獨立地為烷基、環烷基、芳基、雜芳基、或雜環基,鍵結於伸芳基、伸烷基、伸烯基、環伸烷基、環伸烯基、伸雜環基、伸雜芳基、烷基、環烷基、芳基、及雜芳基之氫原子,也可取代為羥基或巰基;
Figure 108114230-A0305-02-0007-2
式中,R5為氫原子、甲基、乙基、丙基、丁基、戊基、或己基,R6及R7各自獨立地為烷基、環烷基、芳基、雜芳基、或雜環基,針對烷基、環烷基、芳基、雜芳基、及雜環基,鍵結於基之氫原子也可取代為羥基或巰基。
〔6〕如〔5〕之樹脂組成物,其中,該式(1)表示之亞胺化合物中之R3及R4為2-羥基苯基。
〔7〕如〔1〕~〔6〕中任一項之樹脂組成物,其中,該螯合助熔劑(A)含有選自由N,N’-雙(亞柳基)-1,2-丙烷二胺、N,N’-雙(亞柳基)乙二胺、N,N’-雙(亞柳基)-1,3-丙烷二胺、及N,N’-雙(亞柳基)-1,2-苯二胺構成之群組中之至少一種。
〔8〕如〔1〕~〔7〕中任一項之樹脂組成物,其中,該螯合助熔劑(A)含有N,N’-雙(亞柳基)-1,2-丙烷二胺及/或N,N’-雙(亞柳基)-1,3-丙烷二胺。
〔9〕如〔1〕~〔8〕中任一項之樹脂組成物,其中,該熱自由基聚合起始劑(B)為有機過氧化物。
〔10〕如〔9〕之樹脂組成物,其中,該熱自由基聚合起始劑(B)之10小時半衰期溫度為100℃以上。
〔11〕如〔9〕或〔10〕之樹脂組成物,其中,該熱自由基聚合起始劑(B)為二烷基過氧化物及/或過氧化氫。
〔12〕如〔9〕~〔11〕中任一項之樹脂組成物,其中,該熱自由基聚合起始劑(B)含有選自由二異丙苯過氧化物、二(2-第三丁基過氧化異丙基)苯、二第三丁基過氧化物、1,1,3,3-四甲基丁基過氧化氫、2,5-二甲基-2,5-二(第三丁基過氧化過氧化過氧化)己-3-炔、2,5-二甲基-2,5-二(第三丁基過氧化過氧化過氧化)己烷、二第三己基過氧化物、第三丁基異丙苯過氧化物、二第三戊基過氧化物、第三戊基過氧化氫、第三丁基過氧化氫、異丙苯過氧化氫、二異丙基苯過氧化氫、及對薄荷烷過氧化物構成之群組中之至少一種。
〔13〕如〔9〕~〔12〕中任一項之樹脂組成物,其中,該熱自由基聚合起始劑(B)含有選自由二異丙苯過氧化物、異丙苯過氧化氫、二異丙基苯過氧化氫、二(2-第三丁基過氧化異丙基)苯、及對薄荷烷過氧化物構成之群組中之至少一種。
〔14〕如〔1〕~〔13〕中任一項之樹脂組成物,其中,該自由基聚合性化合物(C)係含有選自由馬來醯亞胺基、(甲基)丙烯醯基、丙烯基、及乙烯基構成之群組中之至少一種之官能基的化合物。
〔15〕如〔14〕之樹脂組成物,其中,該自由基聚合性化合物(C)係含有馬來醯亞胺基之化合物。
〔16〕如〔14〕或〔15〕之樹脂組成物,其中,該自由基聚合性化合物(C)含有選自由2,2-雙{4-(4-馬來醯亞胺苯氧基)苯基}丙烷、1,2-雙(馬來醯亞胺)乙 烷、1,4-雙(馬來醯亞胺)丁烷、1,6-雙(馬來醯亞胺)己烷、N,N’-1,3-伸苯基二馬來醯亞胺、N,N’-1,4-伸苯基二馬來醯亞胺、N-苯基馬來醯亞胺、下式(3)表示之馬來醯亞胺化合物、下式(4)表示之馬來醯亞胺化合物、及下式(5)表示之馬來醯亞胺化合物構成之群組中之至少一種;
Figure 108114230-A0305-02-0009-3
式(3)中,R8各自獨立地表示氫原子或甲基,n1表示1以上之整數;
Figure 108114230-A0305-02-0009-4
式(4)中,n2之平均值為1以上30以下;
Figure 108114230-A0305-02-0009-5
式(5)中,R9及R10各自獨立地表示氫原子、甲基或乙基,R11各自獨立地表示氫原子或甲基。
〔17〕如〔14〕~〔16〕中任一項之樹脂組成物,其中,該自由基聚合性化合物(C)含有選自由該2,2’-雙{4-(4-馬來醯亞胺苯氧基)苯基}丙烷、該式(3)表示之馬來醯亞胺化合物、該式(4)表示之馬來醯亞胺化合物、及該式(5)表示之馬來醯亞胺化合物構成之群組中之至少一種之馬來醯亞胺化合物。
〔18〕如〔1〕~〔17〕中任一項之樹脂組成物,其中,該樹脂組成物中之該螯合助熔劑(A)之含量相對於該自由基聚合性化合物(C)之合計量100質量份為5質量份以上50質量份以下。
〔19〕如〔1〕~〔18〕中任一項之樹脂組成物,其中,該樹脂組成物中之該熱自由基聚合起始劑(B)之含量相對於該自由基聚合性化合物(C)之合計量100質量份為0.005質量份以上5質量份以下。
〔20〕如〔1〕~〔19〕中任一項之樹脂組成物,更含有無機填充材(D)。
〔21〕如〔20〕之樹脂組成物,其中,該無機填充材(D)具有電絕緣性。
〔22〕如〔20〕或〔21〕之樹脂組成物,其中,該無機填充材(D)含有選自由二氧化矽、氫氧化鋁、氧化鋁、軟水鋁石、氮化硼、氮化鋁、氧化鎂、及氫氧化鎂構成之群組中之至少1種。
〔23〕如〔20〕~〔22〕中任一項之樹脂組成物,其中,該無機填充材(D)之平均粒徑為3μm以下。
〔24〕如〔20〕~〔23〕中任一項之樹脂組成物,其中,該樹脂組成物中之該無機填充材(D)之含量相對於該自由基聚合性化合物(C)之合計量100質量份為300質量份以下。
〔25〕如〔1〕~〔24〕中任一項之樹脂組成物,更含有可撓性賦予成分(E)。
〔26〕如〔25〕之樹脂組成物,其中,該可撓性賦予成分(E)含有熱塑性之高分子化合物,該高分子化合物之重量平均分子量為1,000以上1,000,000以下。
〔27〕如〔25〕或〔26〕之樹脂組成物,其中,該可撓性賦予成分(E)為(甲基)丙烯酸基寡聚物及/或(甲基)丙烯酸基聚合物。
〔28〕如〔1〕~〔27〕中任一項之樹脂組成物,係用於預塗式底層填充材。
〔29〕一種疊層體,具備:支持基材;及疊層在該支持基材上之含有如〔1〕~〔28〕中任一項之樹脂組成物之層。
〔30〕一種附樹脂組成物層之半導體晶圓,具備半導體晶圓及疊層在該半導體晶圓之如〔29〕之疊層體;該含有樹脂組成物之層疊層於該半導體晶圓。
〔31〕一種附樹脂組成物層之半導體搭載用基板,具備:半導體搭載用基板,及疊層於該半導體搭載用基板之如〔29〕之疊層體,該含有樹脂組成物之層疊層於該半導體搭載用基板。
〔32〕一種半導體裝置,具備:如〔30〕之附樹脂組成物層之半導體晶圓,及/或如〔31〕之附樹脂組成物層之半導體搭載用基板。
依照本發明,可獲得兼顧優良的助熔劑活性及高絕緣可靠性,有良好的保存安定性,且作為疊層體使用時有良好作業性之可撓性的樹脂組成物。又,藉 由將樹脂組成物塗佈在支持基材上,能夠提供有助熔劑活性、絕緣可靠性、及保存安定性優異之樹脂組成物層之疊層體。
以下針對本實施方式(以下簡稱「本實施形態」)詳細說明。又,以下之本實施形態係為了說明本發明之例示,本發明不只限於本實施形態。
本說明書中,「(甲基)丙烯醯基」係指「丙烯醯基」及和其對應之「甲基丙烯醯基」兩者。「(甲基)丙烯酸基」係指「丙烯酸基」及和其對應之「甲基丙烯酸基」兩者。「(甲基)丙烯酸酯」係指「丙烯酸酯」及和其對應之「甲基丙烯酸酯」兩者。
本實施形態之一態樣之樹脂組成物,含有螯合助熔劑(A)、熱自由基聚合起始劑(B)、及自由基聚合性化合物(C)。本實施形態之樹脂組成物,作為預塗底層填充材有用。
本實施形態之其他態樣之樹脂組成物,除了前述各成分,更含有無機填充材(D)。
本實施形態之其他態樣之樹脂組成物,除了前述各成分,更含有可撓性賦予成分(E)。
本實施形態之其他態樣,也提供使用本實施形態之樹脂組成物獲得之疊層體(以下也稱為「樹脂疊層體」)、使用疊層體製作之附樹脂組成物層之半導體晶 圓、使用疊層體製作之附樹脂組成物層之半導體搭載用基板、及使用本實施形態之樹脂組成物製作之半導體裝置。
〔I.樹脂組成物〕
本實施形態之樹脂組成物,含有螯合助熔劑(A)、熱自由基聚合起始劑(B)、及自由基聚合性化合物(C)。本實施形態之樹脂組成物,作為晶片之倒裝晶片安裝中使用之黏接劑有用。本實施形態之樹脂組成物亦可更含有無機填充材(D)及/或可撓性賦予成分(E)。
〔I-1.螯合助熔劑(A)〕
藉由使用本實施形態之螯合助熔劑(A),相較於習知之羧酸系之助熔劑成分,可達成弱酸化,能期待絕緣可靠性更好。
本實施形態之螯合助熔劑(A),考量在倒裝晶片安裝中,於焊料之熔點以下提高助熔劑之運動性而展現為了充分去除金屬氧化膜之助熔劑活性之觀點,例如:焊料種類為錫-銀合金時,螯合助熔劑在單體狀態之熔點宜為235℃以下較佳,180℃以下更佳。下限不特別限定,為-50℃。
又,本實施形態之螯合助熔劑(A),因為需防止在倒裝晶片安裝時展現助熔劑活性前便揮發,亦即防止在去除接合部之氧化膜前螯合助熔劑(A)揮發掉,分子量為150以上較佳,200以上更佳。又,本實施形態之螯合助熔劑(A),在樹脂組成物之中有高運動性,所以考量獲得充分的助熔劑活性之觀點,分子量500以下較佳,400以下更佳。
本實施形態之螯合助熔劑(A),考量倒裝晶片安裝時連接端子間可良好的接合的觀點,使用螯合助熔劑單體在下列焊料潤濕性試驗獲得之焊球之接觸角宜微達1.20弳較佳,未達1.10弳更佳。又,針對具體的試驗方法,如實施例記載。
(焊料潤濕性試驗)
在厚度12μm的銅箔之光澤面塗佈前述螯合助熔劑,在前述螯合助熔劑上放置直徑0.5mm的焊球。之後於保持在235℃的熱板上加熱1分鐘,使焊料熔融後,於室溫冷卻。冷卻後,測定在前述銅箔上擴開的焊球的半徑(a)及焊球的高度(b),並依下式算出接觸角。
焊球之接觸角=2arctan{(b)/(a)}
本實施形態之螯合助熔劑(A),只要是作為金屬離子捕捉劑作用的助熔劑即可,不特別限定,宜為下式(1)及/或下式(2)表示之亞胺化合物較佳。藉由使用如此的亞胺化合物,能夠有效率地捕捉銅離子等金屬離子,可期待抑制由於遷移之誘發導致填充不良等的效果。
Figure 108114230-A0305-02-0014-6
Figure 108114230-A0305-02-0015-7
式(1)表示之亞胺化合物中,Q為伸芳基、伸烷基、伸烯基、環伸烷基、環伸烯基、伸雜環基、或伸雜芳基,R1及R2各自獨立地為氫原子、甲基、乙基、丙基、丁基、戊基、或己基,R3及R4各自獨立地為烷基、環烷基、芳基、雜芳基、或雜環基。鍵結於伸芳基、伸烷基、伸烯基、環伸烷基、環伸烯基、伸雜環基、伸雜芳基、烷基、環烷基、芳基、及雜芳基之氫原子也可取代為羥基或巰基。
伸芳基不特別限定,例如:伸苯基(鄰伸苯基、間伸苯基、對伸苯基)、伸聯苯基、伸萘基、聯伸萘基、伸蒽基、及伸菲基。
伸烷基不特別限定,例如:亞甲基、伸乙基、三亞甲基、四亞甲基、五亞甲基、六亞甲基、七亞甲基、八亞甲基、九亞甲基、十亞甲基、十一亞甲基、十二亞甲基、十三亞甲基、十四亞甲基、十五亞甲基、及十六亞甲基之直鏈狀伸烷基;甲基伸乙基、甲基伸丙基、乙基伸乙基、1,2-二甲基伸乙基、1,1-二甲基伸乙基、1-乙基伸丙基、2-乙基伸丙基、1,2-二甲基伸丙基、2,2-二甲基伸丙基、1-丙基伸丙基、2-丙基伸丙基、1-甲基-1-乙基伸丙基、1-甲基-2-乙基-伸丙基、1-乙基-2-甲基-伸丙基、2-甲基-2-乙基-伸丙基、1-甲基伸丁基、2-甲基伸丁基、3-甲基伸丁基、2-乙基伸丁基、甲基伸戊基、乙基伸戊基、甲基伸己基、甲基伸庚基、甲基伸辛基、甲基伸壬基、甲基伸癸基、甲基伸十一烷基、甲基伸十二烷基、甲基伸十四烷基、及甲基伸十八烷基之分支鏈狀伸烷基。
伸烯基不特別限定,例如:伸乙烯基、1-甲基伸乙烯基、伸丙烯基、1-伸丁烯基、2-伸丁烯基、1-伸戊烯基、及2-伸戊烯基。
環伸烷基不特別限定,例如:伸環丙基、伸環丁基、伸環戊基、伸環己基、伸環庚基、伸環辛基、伸環己基、1,2-伸環己基雙(亞甲基)、1,3-伸環己基雙(亞甲基)、及1,4-伸環己基雙(亞甲基)。
伸環烯基不特別限定,例如:伸環丙烯基、伸環丁烯基、伸環戊烯基、伸環己烯基、及伸環辛烯基。
伸雜環基不特別限定,例如:四氫呋喃-2,5-二基、
Figure 108114230-A0305-02-0016-31
啉-2,3-二基、哌喃-2,4-二基、1,4-二
Figure 108114230-A0305-02-0016-32
烷-2,3-二基、1,3-二
Figure 108114230-A0305-02-0016-33
烷-2,4-二基、哌啶-2,4-二基、哌啶-1,4-二基、吡咯啶-1,3-二基、
Figure 108114230-A0305-02-0016-34
啉-2,4-二基、及哌
Figure 108114230-A0305-02-0016-35
-1,4-二基。
伸雜芳基不特別限定,係前述伸芳基之碳原子中之一者以上之碳原子取代成如氧原子、硫原子、氮原子、磷原子之雜原子而得之基。具體而言,可列舉菲、吡咯、吡
Figure 108114230-A0305-02-0016-36
、吡啶、嘧啶、吲哚啉、異吲哚啉、喹啉、異喹啉、喹
Figure 108114230-A0305-02-0016-37
啉、咔唑、苯基咔唑、菲啶、吖啶、呋喃、苯并呋喃、異苯并呋喃、二苯并呋喃、苯基二苯并呋喃、二苯基二苯并呋喃、噻吩、苯基噻吩、二苯基噻吩、苯并噻吩、二苯并噻吩、苯基苯并噻吩、二苯基苯并噻吩、苯基二苯并噻吩、及苯并噻唑為2價基者。
烷基不特別限定,例如:甲基、乙基、正丙基、異丙基、正丁基、2-丁基、異丁基、第三丁基、正戊基、2-戊基、第三戊基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、正己基、2-己基、3-己基、2-甲基戊基、3-甲基戊基、4-甲基戊基、及2-甲基戊烷-3-基。
環烷基不特別限定,例如:環丙基、環丁基、環戊基、及環己基。
芳基不特別限定,例如:苯基、萘基、蒽基、菲基、及聯苯基。
雜芳基不特別限定,可列舉2-側氧基吡咯烷基、哌啶基、哌
Figure 108114230-A0305-02-0017-38
基、
Figure 108114230-A0305-02-0017-39
啉代基、四氫呋喃基、四氫哌喃基、四氫噻吩基、全氫萘基、吡咯基、呋喃基、噻吩基、吡啶基、嘧啶基、吡
Figure 108114230-A0305-02-0017-41
基、嗒
Figure 108114230-A0305-02-0017-42
基、吡唑基、咪唑基、
Figure 108114230-A0305-02-0017-43
唑基、噻唑基、吲哚基、苯并呋喃基、苯并噻吩基、喹啉基、異喹啉基、喹喔啉基、呔
Figure 108114230-A0305-02-0017-44
基、喹唑啉基(quinazolyl)、
Figure 108114230-A0305-02-0017-45
啶基、
Figure 108114230-A0305-02-0017-46
啉基、苯并咪唑基、苯并
Figure 108114230-A0305-02-0017-47
唑基、苯并噻唑基、及四氫萘基。
式(2)表示之亞胺化合物中,R5為氫原子、甲基、乙基、丙基、丁基、戊基、或己基,R6及R7各自獨立地為烷基、環烷基、芳基、雜芳基、或雜環基。鍵結於烷基、環烷基、芳基、雜芳基、及雜環基之氫原子也可取代為羥基或巰基。針對烷基、環烷基、芳基、雜芳基、及雜環基,同前所述。
式(1)表示之亞胺化合物中,考量展現優良的助熔劑活性,以良好效率捕捉金屬離子之觀點,R3及R4宜為2-羥基苯基較佳。
式(1)表示之亞胺化合物,考量在倒裝晶片安裝中,於焊料之熔點以下提高助熔劑之運動性而展現為了充分去除金屬氧化膜之助熔劑活性之觀點,例如:N,N’-雙(亞柳基)-1,2-丙烷二胺、N,N’-雙(亞柳基)乙二胺、N,N’-雙(亞柳基)-1,3-丙烷二胺、及N,N’-雙(亞柳基)-1,2-苯二胺較佳,考量兼顧安裝時展現優異之助熔劑活性、及抑制安裝時之揮發成分之觀點,例如:N,N’-雙(亞柳基)-1,2-丙烷二胺及/或N,N’-雙(亞柳基)-1,3-丙烷二胺更佳。
該等螯合助熔劑可單獨使用1種或組合使用2種以上。
螯合助熔劑(A)也可使用市售品。
本實施形態之樹脂組成物中之螯合助熔劑(A)之含量不特別限定,考量兼顧樹脂組成物之助熔劑活性、及清漆及樹脂組成物之保存安定性之觀點,相對於後述自由基聚合性化合物(C)之合計量100質量份,為5質量份以上50質量份以下較佳,考量確保在室溫之清漆之保存安定性之觀點,為10質量份以上35質量份以下更佳。
〔I-2.熱自由基聚合起始劑(B)〕
本實施形態之熱自由基聚合起始劑(B),只要是會促進自由基聚合性化合物(C)之自由基聚合反應者即不特別限定,可使用公知品。其中,考量清漆及樹脂組成物之保存安定性、及倒裝晶片安裝中之溫度範圍之觀點,有機過氧化物較佳。
有機過氧化物,例如:二醯基過氧化物、過氧化二碳酸酯、過氧化酯、過氧化縮酮、二烷基過氧化物、及過氧化氫。
二醯基過氧化物,例如:二異丁醯基過氧化物、二(3,5,5-三甲基己醯基)過氧化物、二過氧化月桂醯、二琥珀酸過氧化物、二(3-甲基苯甲醯基)過氧化物、苯甲醯基(3-甲基苯甲醯基)過氧化物、二過氧化苯甲醯。
過氧化碳酸酯,例如:過氧化二碳酸二正丙酯、過氧化二碳酸二異丙酯、過氧化二碳酸二(4-第三丁基環己基)酯、過氧化二碳酸二(2-乙基己基)酯、過氧化二碳酸二第二丁基酯。
過氧化酯,例如:過氧化新癸酸異丙苯酯、過氧化新癸酸1,1,3,3-四甲基丁酯、過氧化新癸酸第三己酯、過氧化新癸酸第三丁酯、過氧化三甲基乙酸第三己酯、過氧化三甲基乙酸第三丁酯、過氧化-2-乙基己酸1,1,3,3-四甲基丁酯、2,5-二甲基-2,5-二(2-乙基己醯基過氧化)己烷、過氧化-2-乙基己酸第三己酯、過氧化-2-乙基己酸第三丁酯、過氧化異丙基單碳酸第三己酯、過氧化-3,5,5-三甲基己酸第三丁酯、過氧化月桂酸第三丁酯、過氧化異丙基單碳酸第三丁酯、過氧化-2-乙基己基單碳酸第三丁酯、過氧化苯甲酸第三己酯、2,5-二甲基-2,5-二(苯甲醯基過氧化)己烷、過氧化乙酸第三丁酯、過氧化-3-甲基苯甲酸第三丁酯、過氧化苯甲酸第三丁酯。
過氧化縮酮,例如:1,1-二(第三己基過氧化)環己烷、1,1-二(第三丁基過氧化)環己烷、2,2-二(第三丁基過氧化)丁烷、正丁基-4,4-二-(第三丁基過氧化)三甲基乙酸酯、2,2-二(4,4-二-(第三丁基過氧化)環己基)丙烷。
二烷基過氧化物,例如:二(2-第三丁基過氧化異丙基)苯、二異丙苯過氧化物、2,5-二甲基-2,5-二(第三丁基過氧化)己烷、第三丁基異丙苯過氧化物、二第 三己基過氧化物、二第三丁基過氧化物、二第三戊基過氧化物、2,5-二甲基-2,5-二(第三丁基過氧化)己-3-炔。
過氧化氫,例如:對薄荷烷過氧化氫、二異丙基苯過氧化氫、1,1,3,3-四甲基丁基過氧化氫、異丙苯過氧化氫、第三丁基過氧化氫、第三戊基過氧化氫。
本實施形態之熱自由基聚合起始劑(B),考量即使將樹脂組成物溶解或分散在有機溶劑而得的清漆予以乾燥後,樹脂組成物中之熱自由基聚合起始劑(B)仍有良好反應性之觀點,10小時半衰期溫度為100℃以上較佳,110℃以上更佳。上限不特別限定,例如:250℃。10小時半衰期溫度,係指溶於溶劑(例如:苯)時之熱自由基聚合起始劑之濃度減少到初始值之一半為止的時間(半衰期)成為10小時的溫度。10小時半衰期溫度例如可依下列方式測定。首先,將熱自由基聚合起始劑溶於苯,獲得濃度0.1mol/L之溶液。將此溶液封入到預先已將內部空氣取代為氮氣的玻璃管內。然後,將玻璃管浸於已設在預定溫度的恆溫槽,以使熱自由基聚合起始劑熱分解。在此,若令分解速度常數為k、時間為t、熱自由基聚合起始劑之初始濃度為[PO]0、時間t後之熱自由基聚合起始劑之濃度為[PO]t,成立kt=ln[PO]0/[PO]t之關係。若將時間t與ln[PO]0/[PO]t之關係作圖,從其斜率可求分解速度常數k。半衰期時間t1/2成立[PO]0/[PO]t=2的關係,故可由t1/2=ln2/k的關係式,來求得於某溫度之半衰期時間t1/2。針對多個溫度求半衰期時間t1/2,並將lnt1/2與1/T之關係作圖,可藉此得到10小時半衰期溫度。T係絕對溫度(單位:K)。又,也可利用熱自由基聚合起始劑之製造公司出版的型錄、技術資料記載的10小時半衰期溫度的數據。
就熱自由基聚合起始劑(B)而言,考量使樹脂組成物溶解或分散於有機溶劑而得的清漆予以乾燥後有更良好反應性之觀點,宜為二烷基過氧化物及/或過氧化氫較佳。
其中,考量溶劑溶解性之觀點,為二異丙苯過氧化物、二(2-第三丁基過氧化異丙基)苯、二第三丁基過氧化物、1,1,3,3-四甲基丁基過氧化氫、2,5-二甲基-2,5-二(第三丁基過氧化)己-3-炔、2,5-二甲基-2,5-二(第三丁基過氧化)己烷、二第三己基過氧化物、第三丁基異丙苯過氧化物、二第三戊基過氧化物、第三戊基過氧化氫、第三丁基過氧化氫、異丙苯過氧化氫、二異丙基苯過氧化氫、及對薄荷烷過氧化物更佳,考量能理想地抑制清漆乾燥時及安裝時之揮發成分的觀點,為二異丙苯過氧化物、異丙苯過氧化氫、二異丙基苯過氧化氫、二(2-第三丁基過氧化異丙基)苯、及對薄荷烷過氧化氫又更佳。
本實施形態之熱自由基聚合起始劑(B)也可使用市售品,例如:日本油脂(股)公司製之PERBUTYL H、PERISOBUTYL H、PEROCTA H、PERCUMYL P、PERMENTA H(以上為過氧化氫)、PERHEXYNE 25B、PERBUTYL D、PERBUTYL C、PERHEXA 25B、PERHEXYL D、PERCUMYL D、PERBUTYL P(以上為二烷基過氧化物)、PERHEXA V、PERHEXA 22(以上為過氧化縮酮)、PERBUTYL Z、及PERBUTYL A(以上為過氧化酯);ARKEMA Yoshitomi(股)製之LUPEROX TAH、LUPEROX TBH(以上為過氧化氫)、及LUPEROX DTA(以上為二烷基過氧化物)。
該等熱自由基聚合起始劑(B)可單獨使用1種或組合使用2種以上。
本實施形態之樹脂組成物中之熱自由基聚合起始劑(B)之含量不特別限定,考量對於自由基聚合性化合物(C)賦予充分的硬化性的觀點,相對於自由基聚合性化合物(C)之合計量100質量份為0.005質量份以上5質量份以下較佳,考量抑制揮發成分並抑制硬化中之孔隙之觀點,為0.05質量份以上3質量份以下更佳。
〔I-3.自由基聚合性化合物(C)〕
本實施形態之自由基聚合性化合物(C),只要是會因自由基聚合反應而進行聚合之化合物即無特殊限制。其中,宜為含有選自由馬來醯亞胺基、(甲基)丙烯醯基、丙烯基、及乙烯基構成之群組中之至少一種官能基之化合物較佳,考量絕緣可靠性、及耐熱性之觀點,含有馬來醯亞胺基之化合物更理想。
作為含有馬來醯亞胺基之化合物,只要是在分子中有1個以上之馬來醯亞胺基之化合物即無特殊限制。例如:N-苯基馬來醯亞胺、N-羥基苯基馬來醯亞胺、雙(4-馬來醯亞胺苯基)甲烷、4,4-二苯基甲烷雙馬來醯亞胺、雙(3,5-二甲基-4-馬來醯亞胺苯基)甲烷、雙(3-乙基-5-甲基-4-馬來醯亞胺苯基)甲烷、雙(3,5-二乙基-4-馬來醯亞胺苯基)甲烷、苯基甲烷馬來醯亞胺、鄰伸苯基雙馬來醯亞胺、間伸苯基雙馬來醯亞胺、對伸苯基雙馬來醯亞胺、鄰伸苯基雙檸康醯亞胺、間伸苯基雙檸康醯亞胺、對伸苯基雙檸康醯亞胺、2,2-雙(4-(4-馬來醯亞胺苯氧基)-苯基)丙烷、3,3-二甲基-5,5-二乙基-4,4-二苯基甲烷雙馬來醯亞胺、4-甲基-1,3-伸苯基雙馬來醯亞胺、1,6-雙馬來醯亞胺-(2,2,4-三甲基)己烷、4,4-二苯醚雙馬來醯亞胺、4,4-二苯基碸雙馬來醯亞胺、1,3-雙(3-馬來醯亞胺苯氧基)苯、1,3-雙(4-馬來醯亞胺苯氧基)苯、4,4-二苯基甲烷雙檸康醯亞胺、2,2-雙[4-(4-檸康醯亞胺苯氧基)苯基〕丙烷、雙(3,5-二甲基-4-檸康醯亞胺苯基)甲烷、雙(3-乙基-5-甲基-4-檸康醯亞胺苯基)甲烷、雙(3,5-二乙基-4-檸康醯亞胺苯基)甲烷、聚苯基甲烷馬來醯亞 胺、酚醛清漆型馬來醯亞胺化合物、聯苯芳烷基型馬來醯亞胺化合物、2,2-雙{4-(4-馬來醯亞胺苯氧基)苯基}丙烷、1,2-雙(馬來醯亞胺)乙烷、1,4-雙(馬來醯亞胺)丁烷、1,6-雙(馬來醯亞胺)己烷、N,N’-1,3-伸苯基二馬來醯亞胺、N,N’-1,4-伸苯基二馬來醯亞胺、N-苯基馬來醯亞胺、下式(3)表示之馬來醯亞胺化合物、下式(4)表示之馬來醯亞胺化合物、及下式(5)表示之馬來醯亞胺化合物。該等含有馬來醯亞胺基之化合物可單獨使用1種或組合使用2種以上。其中,考量對於有機溶劑之溶解性之觀點,宜為2,2-雙{4-(4-馬來醯亞胺苯氧基)苯基}丙烷、下式(3)表示之馬來醯亞胺化合物、下式(4)表示之馬來醯亞胺化合物、及下式(5)表示之馬來醯亞胺化合物較佳。
又,也能以將此等馬來醯亞胺化合物予以聚合而獲得之預聚物、或將馬來醯亞胺化合物與胺化合物等其他化合物聚合而獲得之預聚物等的形式摻合,該等化合物可單獨使用1種或組合使用2種以上。
Figure 108114230-A0305-02-0023-8
式(3)中,R8各自獨立地表示氫原子或甲基。又,式(3)中,n1表示1以上之整數,n1之上限值通常為10,考量對有機溶劑之溶解性之觀點,為7較佳。
又,式(3)也可為n1不同的化合物之混合物。
Figure 108114230-A0305-02-0024-9
式(4)中,n2之平均值為7以上30以下之範圍。
又,式(4)也可為n2不同的化合物之混合物。
Figure 108114230-A0305-02-0024-10
式(5)中,R9、及R10各自獨立地表示氫原子、甲基或乙基。
式(5)中,R11各自獨立地表示氫原子或甲基。
又,就本實施形態中之自由基聚合性化合物(C)而言,考量對於有機溶劑之溶解性、及確保可撓性之觀點,宜含有前述式(4)表示之馬來醯亞胺化合物且併用選自由2,2-雙{4-(4-馬來醯亞胺苯氧基)苯基}丙烷、前述式(3)表示之馬來醯亞胺化合物、及前述式(5)表示之馬來醯亞胺化合物構成之群組中之至少1種以上之馬來醯亞胺化合物更佳。
含有馬來醯亞胺基之化合物也可使用市售品,例如:大和化成工業(股)製BMI-2300(前述式(3)中之R8皆為氫原子,且n1為1以上3以下之馬來醯亞胺化合物);KI化成(股)製BMI-70(前述式(5)中之R9為甲基、R10為乙基、R11為氫原子之馬來醯亞胺化合物、雙(3-乙基-5-甲基-4-馬來醯亞胺苯基)甲烷)、BMI-80(2,2-雙{4-(4-馬來醯亞胺苯氧基)苯基}丙烷)、BMI-1000P(前述式(4)中之n2為14(平均值)之馬來醯亞胺化合物)、BMI-650P(前述式(4)中之n2為9(平均值)之馬來醯亞胺化合物)。
就含有(甲基)丙烯醯基之化合物而言,只要是在分子中有1個以上之(甲基)丙烯醯基之化合物即無特殊限制。例如:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸異丙酯、(甲基)丙烯酸異丁酯、二(甲基)丙烯酸乙二醇酯、二(甲基)丙烯酸二乙二醇酯、三羥甲基丙烷三(甲基)丙烯酸酯、四羥甲基甲烷四(甲基)丙烯酸酯、2-羥基-1,3-二(甲基)丙烯醯氧基丙烷、2,2-雙[4-((甲基)丙烯醯氧基甲氧基)苯基]丙烷、2,2-雙[4-((甲基)丙烯醯氧基聚乙氧基)苯基]丙烷、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸三環癸酯、參((甲基)丙烯醯氧乙基)異氰尿酸酯、及胺甲酸酯(甲基)丙烯酸酯,可使用1種或適當混用2種以上。
作為含有丙烯基之化合物,只要是在分子中有1個以上之丙烯基之化合物即無特殊限制。例如:丙烯基苯、丙烯基萘、丙烯基蒽、丙烯基苯酚、鄰丙烯基苯氧基苯之一官能丙烯基化合物;雙丙烯基苯醚、2,2-雙[4-(鄰丙烯基苯氧基)苯基]丙烷、雙[4-(鄰丙烯基苯氧基)苯基]醚、雙[4-(鄰丙烯基苯氧基)苯基]碸、4,4’-雙(鄰丙烯基苯氧基)二苯基酮、2,2-雙[4-(鄰丙烯基苯氧基)苯基]壬烷、2,2-雙[3-第三丁基-4-(鄰丙烯基苯氧基)苯基]丙烷、2,2-雙[3-第二丁基-4-(鄰丙烯基苯氧基)苯基]丙烷、1,1-雙[4-(鄰丙烯基苯氧基)苯基]癸烷、1,1-雙[2-甲基-4-(鄰丙烯基苯 氧基)-5-第三丁基苯基]-2-甲基丙烷、4,4’-環亞己基-雙[1-(鄰丙烯基苯氧基)-2-(1,1-二甲基乙基)苯]、4,4’-亞甲基-雙[1-(鄰丙烯基苯氧基)-2,6-雙(1,1-二甲基乙基)苯]、4,4’-亞甲基-雙[1-(鄰丙烯基苯氧基)-2,6-二-第二丁基苯]、4,4’-環亞己基-雙[1-(鄰丙烯基苯氧基)-2-環己基苯]、4,4’-亞甲基-雙[1-(鄰丙烯基苯氧基)-2-壬基苯]、4,4’-(1-甲基亞乙基)-雙[1-(鄰丙烯基苯氧基)-2,6-雙(1,1-二甲基乙基)苯、4,4’-(2-乙基亞己基)-雙[1-(鄰丙烯基苯氧基)-苯]、4,4’-(1-甲基亞庚基)-雙[1-(鄰丙烯基苯氧基)-苯]、4,4’-環亞己基-雙[1-(鄰丙烯基苯氧基)-3-甲基苯]、2,2-雙[4-(鄰丙烯基苯氧基)苯基]-丙烷、2,2-雙[4-(鄰丙烯基苯氧基)苯基]-六氟丙烷、2,2-雙[3-甲基-4-(鄰丙烯基苯氧基)苯基]-丙烷、2,2-雙[3-甲基-4-(鄰丙烯基苯氧基)苯基]-六氟丙烷、2,2-雙[3,5-二甲基-4-(鄰丙烯基苯氧基)苯基]-丙烷、2,2-雙[3,5-二甲基-4-(鄰丙烯基苯氧基)苯基]-六氟丙烷、2,2-雙[3-乙基-4-(鄰丙烯基苯氧基)苯基]-丙烷、2,2-雙[3-乙基-4-(鄰丙烯基苯氧基)苯基]-六氟丙烷、雙[3-甲基-(鄰丙烯基苯氧基)苯基]-甲烷、雙[3,5-二甲基-(鄰丙烯基苯氧基)苯基]-甲烷、雙[3-乙基-(鄰丙烯基苯氧基)苯基]-甲烷、3,8-雙[4-(鄰丙烯基苯氧基)苯基]-三環-[5,2,1,02.6]癸烷、4,8-雙[4-(鄰丙烯基苯氧基)苯基]-三環-[5,2,1,02.6]癸烷、3,9-雙[4-(鄰丙烯基苯氧基)苯基]-三環-[5,2,1,02.6]癸烷、4,9-雙[4-(鄰丙烯基苯氧基)苯基]-三環-[5,2,1,02.6]癸烷、1,8-雙[4-(鄰丙烯基苯氧基)苯基]-薄荷烷、1,8-雙[3-甲基-4-(鄰丙烯基苯氧基)苯基]-薄荷烷、1,8-雙[3,5-二甲基-4-(鄰丙烯基苯氧基)苯基]-薄荷烷,可使用1種或將2種以上適當混用。
作為含有乙烯基之化合物,只要是分子中有1個以上之乙烯基之化合物即無特殊限制。例如:乙基乙烯醚、丙基乙烯醚、羥基乙基乙烯醚、乙二醇二乙烯醚、有乙烯基之2官能性伸苯醚寡聚物之乙烯醚類,可使用1種或將2種以上適當混用。
本實施形態中之樹脂組成物不特別限定,考量良好的助熔劑活性、及確保薄膜之強度之觀點,自由基聚合性化合物(C)之合計量相對於螯合助熔劑(A)20質量份宜為50質量份以上200質量份以下較佳,考量獲得良好的薄膜形成性之觀點,宜為80質量份以上150質量份以下更佳。
其中,含有馬來醯亞胺基之化合物宜為自由基聚合性化合物(C)之中之50~100%較佳。
含有馬來醯亞胺基之化合物,考量以充分的均衡性具有優良的助熔劑活性、優良的可撓性、及低熱膨脹率之觀點,相對於自由基聚合性化合物(C)之全體量100質量份,宜含有前述式(3)表示之馬來醯亞胺基化合物5質量份以上50質量份以下較佳,含有前述式(4)表示之馬來醯亞胺基化合物5質量份以上70質量份以下較佳,含有前述式(5)表示之馬來醯亞胺化合物5質量份以上50質量份以下較佳,含有2,2-雙{4-(4-馬來醯亞胺苯氧基)苯基}丙烷5質量份以上50質量份以下較佳。
〔I-4.無機填充材(D)〕
本實施形態中,為了使耐燃性更好、熱傳導率更好、及熱膨脹率減小,可以含有無機填充材(D)。無機填充材(D)之種類不特別限定,例如:熔融二氧化矽等二氧化矽;軟水鋁石、氫氧化鋁、及氧化鋁等鋁化合物;氧化鎂、及氫氧化鎂等鎂化合物;碳酸鈣等鈣化合物;氧化鉬、及鉬酸鋅等鉬化合物;天然滑石、及煅燒滑石等滑石;雲母;短纖維狀玻璃、球狀玻璃、及微粉末玻璃(例如:E玻璃、T玻璃、D玻璃)等玻璃。該等無機填充材(D)可單獨使用1種或組合使用2種以上。
該等之中,考量樹脂組成物之耐燃性更好、及熱膨脹率減小之觀點,無機填充材(D)宜為二氧化矽較理想,其中,熔融二氧化矽更理想。熔融二氧化矽,例如:電化(股)製之SFP-120MC、Admatechs(股)製之SC1050、SC2050、SE1030、SE1050、SE2050。又,使用在底層填充材用途時,使用低α射線等級之二氧化矽較理想,例如:Admatechs(股)製之SV-EM1、SX-EM1。
無機填充材(D)之平均粒徑不特別限定,當本實施形態之樹脂組成物係作為預塗底層填充材使用時,考量因應排列在晶片之電極之窄節距化、電極間之窄間距化之觀點,為3μm以下較理想,電極間之節距成為60μm以下之情形,更宜為1μm以下。
又,本說明書中,無機填充材(D)之「平均粒徑」係指無機填充材(D)之中位徑。在此,中位徑係指,當以某粒徑作為基準,將粉體的粒度分布分為2個部分時,粒徑較大側之粒子之個數、或質量、與粒徑較小側之個數、或質量,分別各佔全部粉體之50%的粒徑。無機填充材(D)之平均粒徑(中位徑),可利用濕式雷射繞射散射法測定。
本實施形態中,使用無機填充材(D)時之含量,考量樹脂組成物之耐燃性更好、及熱膨脹率減小、且確保預塗底層填充材接合時之流動性之觀點,相對於樹脂組成物中之自由基聚合性化合物(C)之合計量100質量份宜設為300質量份以下較佳,200質量份以下更佳。又,無機填充材(D)之含量,相對於前述含量100質量份為10質量份以上較佳,50質量份以上更理想。又,併用2種以上之無機填充材(D)時,該等合計量宜符合前述含量之範圍較佳。
〔I-5.可撓性賦予成分(E)〕
本實施形態中之可撓性賦予成分(E)無特殊限制,例如:聚醯亞胺、聚醯胺醯亞胺、聚苯乙烯、聚烯烴、苯乙烯-丁二烯橡膠(SBR)、異戊二烯橡膠(IR)、丁二烯橡膠(BR)、丙烯腈丁二烯橡膠(NBR)、聚胺甲酸酯、聚丙烯、(甲基)丙烯酸基寡聚物、(甲基)丙烯酸基聚合物、聚矽氧樹脂、及苯氧基樹脂之類之熱塑性高分子化合物。該等可撓性賦予成分(E)可單獨使用1種或組合使用2種以上。
該等之中,考量對於製造樹脂組成物時使用之有機溶劑之溶解性、和馬來醯亞胺化合物的相容性、樹脂組成物之熔融黏度之控制性、及可撓性賦予之觀點,可撓性賦予成分(E)宜為選自由(甲基)丙烯酸基寡聚物、及(甲基)丙烯酸基聚合物構成之群組中之至少1種較佳。(甲基)丙烯酸基寡聚物、及(甲基)丙烯酸基聚合物,例如:東亞合成(股)之「ARUFON」系列、綜研化學(股)之「ACTFLOW」系列、根上工業(股)之「PARACRON」系列、可樂麗(股)之「KURARITY」系列。
可撓性賦予成分(E)之分子量不限定,考量對於樹脂組成物賦予可撓性之觀點,重量平均分子量為1,000以上較佳,考量硬化物之柔軟性、及賦予良好的靭性之觀點,2,000以上更佳。又,作為預塗底層填充材使用時,為了不使樹脂組成物卡在金屬接合部內,能獲得更良好且安定形狀之接合,宜控制樹脂組成物之熔融黏度為低且確保接合時之樹脂組成物之流動性較佳。考量如此的觀點,可撓性賦予成分(E)之重量平均分子量為1,000,000以下較佳,800,000以下更佳,100,000以下又更佳,考量溶劑溶解性之觀點,10,000以下更為理想。藉由使用有此理想範圍之重量平均分子量之可撓性賦予成分(E),能夠兼顧樹脂組成物之可撓性、及作為預塗底層填充材使用時之接合性。
本實施形態中,使用可撓性賦予成分(E)時之含量,考量熔融黏度之控制性之觀點,相對於樹脂組成物中之前述自由基聚合性化合物(C)之合計量100質量份設為100質量份以下較佳,50質量份以下更佳,30質量份以下更理想。又,可撓性賦予成分(E)在樹脂組成物中之含量,考量能更有效且確實發揮使用可撓性賦予成分(E)所獲致之作用效果之觀點,相對於樹脂組成物中之前述自由基聚合性化合物(C)之合計量100質量份設為1質量份以上較佳,5質量份以上更佳。又,併用2種以上之可撓性賦予成分(E)時,該等之合計量宜為前述含量之範圍內較佳。
〔I-6.其他成分〕
本實施形態之樹脂組成物中,除了螯合助熔劑(A)、熱自由基聚合起始劑(B)、自由基聚合性化合物(C)、無機填充材(D)、及可撓性賦予成分(E)以外,也可更含有1種或2種以上之其他成分。
例如:本實施形態之樹脂組成物中,為了吸濕耐熱性更好、及提升和晶片樹脂組成物間之黏接性之目的,也可含有矽烷偶聯劑。矽烷偶聯劑,只要是一般係使用在無機物之表面處理且和螯合助熔劑(A)之反應性低的矽烷偶聯劑即不限定。例如:乙烯基矽烷系矽烷偶聯劑(例如γ-甲基丙烯醯氧基丙基三甲氧基矽烷)、苯胺基矽烷系矽烷偶聯劑(例如N-苯基-3-胺基丙基三乙氧基矽烷)、苯基矽烷系矽烷偶聯劑、咪唑矽烷系矽烷偶聯劑。該等矽烷偶聯劑可單獨使用1種或組合使用2種以上。
使用矽烷偶聯劑時,其添加量不限定。惟,考量吸濕耐熱性更好、及倒裝晶片安裝時之揮發量減少之觀點,其含量相對於樹脂組成物中之前述自由基聚合性化合物(C)之合計量100質量份為0.05質量份以上20質量份以下較佳,0.1質量 份以上15質量份以下更佳。又,併用2種以上之矽烷偶聯劑時,該等之合計量為前述含量之範圍內較佳。
本實施形態之樹脂組成物中,為了使疊層體之製造性更好等目的,也可含有濕潤分散劑。濕潤分散劑只要是一般在塗料等使用之濕潤分散劑即不限定。例如:BYK Chemie Japan(股)製之Disperbyk-110、同-111、同-180、同-161、BYK-W996、同-W9010、同-W903。該等濕潤分散劑可單獨使用1種或組合使用2種以上。
使用濕潤分散劑時,在樹脂組成物中之含量不限定,但考量疊層體之製造性更好之觀點,相對於自由基聚合性化合物(C)100質量份,濕潤分散劑之比率為0.1質量份以上5質量份以下較佳,0.5質量份以上3質量份以下更佳。又,併用2種以上之濕潤分散劑時,該等合計量為前述含量之範圍內較佳。
本實施形態之樹脂組成物中,為了黏接性賦予等目的,也可含有苯并
Figure 108114230-A0305-02-0031-48
化合物。就苯并
Figure 108114230-A0305-02-0031-49
化合物而言,只要是就因熱而進行開環聚合之化合物而公知且是一般使用者則無特殊限制。例如:下式(6)、下式(7)、及下式(8)表示之化合物。
Figure 108114230-A0305-02-0031-11
式(6)表示之化合物中,R11各自獨立地表示氫原子、芳基、芳烷基、烯丙基、烷基或環烷基,R12各自獨立地表示氫原子、芳基、芳烷基、烯丙基、烷基或環烷基,X1表示伸烷基、下式(9)表示之基、式「-SO2-」表示之基、式「-CO-」表示之基、氧原子或單鍵。
芳基不特別限定,例如:苯基、萘基、蒽基、菲基、及聯苯基。
芳烷基不特別限定,例如:苄基、及苯乙基。
烷基不特別限定,例如:甲基、乙基、正丙基、異丙基、正丁基、2-丁基、異丁基、第三丁基、正戊基、2-戊基、第三戊基、2-甲基丁基、3-甲基丁基、2,2-二甲基丙基、正己基、2-己基、3-己基、2-甲基戊基、3-甲基戊基、4-甲基戊基、及2-甲基戊烷-3-基。
環烷基不特別限定,例如:環丙基、環丁基、環戊基、及環己基。
伸烷基不特別限定,例如:亞甲基、伸乙基、三亞甲基、四亞甲基、五亞甲基、六亞甲基、七亞甲基、八亞甲基、九亞甲基、十亞甲基、十一亞甲基、十二亞甲基、十三亞甲基、十四亞甲基、十五亞甲基、及十六亞甲基之直鏈狀伸烷基;甲基伸乙基、甲基伸丙基、乙基伸乙基、1,2-二甲基伸乙基、1,1-二甲基伸乙基、1-乙基伸丙基、2-乙基伸丙基、1,2-二甲基伸丙基、2,2-二甲基伸丙基、1-丙基伸丙基、2-丙基伸丙基、1-甲基-1-乙基伸丙基、1-甲基-2-乙基-伸丙基、1-乙基-2-甲基-伸丙基、2-甲基-2-乙基-伸丙基、1-甲基伸丁基、2-甲基伸丁基、3-甲基伸丁基、2-乙基伸丁基、甲基伸戊基、乙基伸戊基、甲基伸己基、甲基伸 庚基、甲基伸辛基、甲基伸壬基、甲基伸癸基、甲基伸十一烷基、甲基伸十二烷基、甲基伸十四烷基、及甲基伸十八烷基之分支鏈狀伸烷基。
Figure 108114230-A0305-02-0033-12
式(7)表示之化合物中,R13各自獨立地表示氫原子、芳基、芳烷基、烯丙基、烷基或環烷基,R14各自獨立地表示氫原子、芳基、芳烷基、烯丙基、烷基或環烷基,X2表示伸烷基、下式(9)表示之基、式「-SO2-」表示之基、式「-CO-」表示之基、氧原子或單鍵。
針對芳基、芳烷基、烷基、環烷基、及伸烷基,同前所述。
Figure 108114230-A0305-02-0033-13
式(8)表示之化合物中,R15各自獨立地表示氫原子、芳基、芳烷基、烯丙基、烷基或環烷基,R16各自獨立地表示氫原子、芳基、芳烷基、烯丙基、烷基或環烷基,X3表示伸烷基、下式(9)表示之基、式「-SO2-」表示之基、式「-CO-」表示之基、氧原子或單鍵。
針對芳基、芳烷基、烷基、環烷基、及伸烷基同前所述。
Figure 108114230-A0305-02-0034-14
式(9)表示之化合物中,Y為伸烷基或有芳香族環之碳數6以上30以下之烴基,n3表示1以上之整數。
針對伸烷基,同前所述。
作為有芳香族環之碳數6以上30以下之烴基,不特別限定,例如:從苯、聯苯、萘、蒽、茀、菲、苯并二茚(indacene)、聯三苯、乙烯合萘、萉(phenalene)之有芳香族性之化合物之核取走2個氫原子而得的2價基。
具體例可列舉下式(10)表示之化合物、下式(11)表示之化合物、下式(12)表示之化合物、下式(13)表示之化合物、下式(14)表示之化合物、下式(15)表示之 化合物、及下式(16)表示之化合物。該等苯并
Figure 108114230-A0305-02-0035-50
化合物可單獨使用1種或組合使用2種以上。
Figure 108114230-A0305-02-0035-15
Figure 108114230-A0305-02-0035-16
Figure 108114230-A0305-02-0035-17
Figure 108114230-A0305-02-0036-18
Figure 108114230-A0305-02-0036-19
Figure 108114230-A0305-02-0036-20
Figure 108114230-A0305-02-0037-21
本實施形態中,使用苯并
Figure 108114230-A0305-02-0037-51
時之含量不限定,但就確保和晶片之充分的黏接性之觀點,相對於自由基聚合性化合物(C)之合計量100質量份,含有苯并
Figure 108114230-A0305-02-0037-52
Figure 108114230-A0305-02-0037-53
化合物5質量份以上60質量份以下較佳,25質量份以上45質量份以下更佳。又,併用2種以上之苯并
Figure 108114230-A0305-02-0037-54
化合物時,該等合計量宜為前述含量之範圍內較佳。
本實施形態之樹脂組成物中,在無損所期待特性之範圍內,也可因應各種目的含有各種添加劑。添加劑,例如:紫外線吸收劑、抗氧化劑、螢光增白劑、染料、顏料、增黏劑、潤滑劑、消泡劑、塗平劑、光澤劑、及阻燃劑。該等添加劑可單獨使用1種或組合使用2種以上。
本實施形態之樹脂組成物中,其他添加劑之含量不特別限定,通常相對於樹脂組成物中之前述自由基聚合性化合物(C)之合計量100質量份各為0.01質量份以上10質量份以下。
本實施形態之樹脂組成物,係藉由將螯合助熔劑(A)、熱自由基聚合起始劑(B)、自由基聚合性化合物(C)、無機填充材(D)、可撓性賦予成分(E)、及其他成 分混合以製備。視需要,也可製成該等成分溶解或分散於有機溶劑而得之清漆之形態。本實施形態之樹脂組成物之清漆,適合使用於作為製作下列本實施形態之疊層體時之清漆。有機溶劑能理想地使前述成分分別溶解或分散,且只要是無損本實施形態之樹脂組成物所期待效果則不限定。有機溶劑,例如:甲醇、乙醇、及丙醇等醇類;丙酮、甲乙酮、及甲基異丁基酮等酮類;二甲基乙醯胺、及二甲基甲醯胺等醯胺類;甲苯、及二甲苯等芳香族烴類。該等有機溶劑可單獨使用1種或組合使用2種以上。
本實施形態之樹脂組成物,助熔劑活性、可撓性、及絕緣可靠性優異。又,藉由將樹脂組成物塗佈在支持基材上,能夠提供有助熔劑活性優異之樹脂層之疊層體。就本實施形態之樹脂組成物以疊層體之形態使用之預塗底層填充材而言,助熔劑活性、可撓性、及絕緣可靠性優異,此外倒裝晶片安裝時之接合性、吸濕耐熱性及和晶片之黏接性亦優良等其他理想的效果也能發揮。如此,本實施形態之樹脂組成物有各種優良的特徵,且特別是能以高水平兼顧助熔劑活性、可撓性及絕緣可靠性,故作為底層填充材極有用。
〔II.疊層體、使用疊層體製作之附樹脂組成物層之半導體晶圓、使用疊層體製作之附樹脂組成物層之基板及半導體裝置〕
本實施形態之疊層體、附樹脂組成物層之半導體晶圓、附樹脂組成物層之基板及半導體裝置,皆使用前述本實施形態之樹脂組成物形成。
〔II-1.疊層體〕
本實施形態之疊層體,係前述本實施形態之樹脂組成物附著於支持基材而得。支持基材不特別定,可使用高分子薄膜。高分子薄膜之材質,例如含有選 自由聚氯乙烯、聚偏二氯乙烯、聚丁烯、聚丁二烯、聚胺甲酸酯、乙烯-氧化乙烯基共聚物、聚對苯二甲酸乙二醇酯、聚萘二甲酸乙二醇酯及聚對苯二甲酸丁二醇酯之聚酯、聚乙烯、聚丙烯、乙烯-丙烯共聚物、聚甲基戊烯、聚醯亞胺及聚醯胺構成之群組中之至少1種以上之樹脂之薄膜、及在該等薄膜之表面塗佈了脫模劑之脫模薄膜,該等之中,尤其聚酯、聚醯亞胺、聚醯胺較理想,其中係屬於聚酯之1種的聚對苯二甲酸乙二醇酯尤佳。
本實施形態之支持基材之厚度不限定,考量疊層體之製造性,例如樹脂組成物塗佈於支持基材時塗佈厚度之安定性之觀點,宜為10μm以上100μm以下較佳。又,考量疊層體之運送性之觀點,10μm以上100μm以下較佳。又,就其厚度之下限而言,考量確保製造疊層體時之產率之觀點,又更佳為12μm以上,尤佳為25μm以上,特佳為30μm以上。又,又其厚度之上限而言,考量支持基材最終而言不作為半導體裝置之構成構件而存在而是在步驟中途被剝離,故就疊層體之製造成本之觀點,宜為80μm以下較佳,50mm以下又更佳。
在前述支持基材上形成由本實施形態之樹脂組成物構成之層(以下也簡稱「樹脂組成物層」)而製造本實施形態之疊層體之方法,並不限定,例如將本實施形態之樹脂組成物溶解或分散於有機溶劑而得的清漆塗佈在前述支持基材之表面,於加熱及/或減壓下乾燥,去除溶劑而使本實施形態之樹脂組成物固化,形成樹脂組成物層之方法等。乾燥條件不特別限定,係乾燥成使有機溶劑相對於樹脂組成物層之含有比率成為相對於樹脂組成物層之總量(100質量%)為通常10質量%以下,較佳為5質量%以下。達成乾燥之條件,取決於清漆中之有機溶劑之種類與摻合量而異,例如:相對於含有螯合助熔劑(A)、熱自由基聚合起始劑(B)及自由基聚合性化合物(C)之樹脂組成物之合計量100質量份,含有30質量 份以上60質量份以下之甲乙酮之清漆的情形,乾燥的指標為在1大氣壓下以90℃以上160℃以下之加熱條件下乾燥約1分鐘以上10分鐘以下。尤其針對加熱溫度,需注意熱自由基聚合起始劑(B)由於氧導致失活、揮發。若加熱本實施形態之清漆,則熱自由基聚合起始劑(B)之分解會進行,且產生的活性自由基會因氣體環境中之氧而失活、或熱自由基聚合起始劑、其分解物揮發,因而使得貢獻於自由基聚合性化合物(C)之聚合之自由基數減少,有倒裝晶片安裝時樹脂組成物之硬化反應不進行的顧慮。所以,本實施形態之樹脂組成物適合使用在清漆之乾燥溫度以上之溫度範圍有10小時半衰期溫度之熱自由基聚合起始劑(B)。本實施形態之疊層體中,樹脂組成物層之厚度不限定,但考量樹脂組成物層乾燥時更良好地去除溶劑等輕揮發成分的觀點、及能更有效且確實發揮作為疊層體之功能之觀點,5μm以上500μm以下之範圍為宜。
〔II-2.使用疊層體製作之附樹脂組成物層之半導體晶圓、使用疊層體製作之附樹脂組成物層之基板〕
本實施形態之附樹脂組成物層之半導體晶圓,係由前述本實施形態之疊層體與半導體晶圓形成,本實施形態之附樹脂組成物層之基板,係由前述本實施形態之疊層體與基板形成。
製作本實施形態之附樹脂組成物層之半導體晶圓之方法不限定,例如可藉由將半導體晶圓之已形成電極之面亦即實施和基板之接合之面,和本實施形態之疊層體之樹脂組成物層以面對的方式貼合以獲得。又,製作本實施形態之附樹脂組成物層之基板之方法不限定,例如:可藉由將基板之晶片搭載側之面與本實施形態之疊層體之本實施形態之樹脂組成物層以面對的方式貼合以獲得。
本實施形態之疊層體貼合於半導體晶圓或基板之方法不特別限定,可理想地使用真空加壓式層合機。於此情形,介隔橡膠等彈性體對於本實施形態之疊層體加壓並貼合之方法較佳。層合條件只要是該業界一般使用的條件即不特別限定,例如於10℃以上140℃以下之溫度、1kgf/cm2以上11kgf/cm2以下之範圍之接觸壓力、及20hPa以下之氣體環境減壓下進行。層合步驟之後,也可利用以金屬板進行熱壓製,使已貼合之疊層體平滑化。前述層合步驟及平滑化步驟,可利用市售的真空加壓式層合機連續進行。貼在半導體晶圓或基板的疊層體,最晚在晶片之倒裝晶片安裝前皆實施支持基材之除去。
〔II-3.半導體裝置〕
本實施形態之半導體裝置,具有本實施形態之附樹脂組成物層之半導體晶圓、及/或本實施形態之附樹脂組成物層之基板,係由本實施形態之樹脂組成物、晶片及基板等構成。製造本實施形態之半導體裝置之方法不限定,例如以切削的方式將本實施形態之附樹脂組成物層之半導體晶圓予以薄化並實施利用切割鋸所為之個片化,製成附樹脂組成物層之晶片,並將其搭載在基板之方法。又,本實施形態之附樹脂組成物層之基板中也可以搭載晶片。附樹脂組成物層之晶片搭載於基板之方法及半導體晶片搭載於附樹脂組成物層之基板之方法,可理想地使用因應熱壓接工法的倒裝晶片接合器。又,本實施形態中,係簡單說明晶片對於基板進行倒裝晶片安裝的情形,但也可將晶片進行倒裝晶片安裝且採用基板以外的對象作為採用本實施形態之樹脂組成物之對象。例如:本實施形態之樹脂組成物,也可使用在將晶片搭載於半導體晶圓上時之半導體晶圓與晶片之接合部、經由TSV(Through Silicon Via)而進行晶片間連接之晶片疊層體之各晶片間之接合部,皆能獲得本實施形態獲致之優越性。
〔實施例〕
以下揭示實施例及比較例並對本發明詳細說明,但本發明不限於該等實施例。
1.螯合助熔劑評價
(1)評價對象
為了評價螯合助熔劑單體的各特性,將以下4種螯合助熔劑作為評價對象,並揭示結果如表1。
(i)N,N’-雙(亞柳基)-1,2-丙烷二胺(熔點:45℃、分子量:282、東京化成工業(股)製)
(ii)N,N’-雙(亞柳基)乙二胺(熔點:126℃、分子量:268、東京化成工業(股)製)
(iii)N,N’-雙(亞柳基)-1,3-丙烷二胺(熔點:53℃、分子量:282、東京化成工業(股)製)
(iv)N,N’-雙(亞柳基)-1,2-苯二胺(熔點:164℃、分子量:316、東京化成工業(股)製)
(2)焊料潤濕性試驗
將(i)~(iv)之螯合助熔劑散布在厚度12μm之電解銅箔(3EC-III、三井金屬礦業(股)製)之光澤面,放置直徑0.5mm的焊球(ECO SOLDER BALL M705、Sn-3.0Ag-0.5Cu合金、千住金屬工業(股)製)。將其於保持在235℃的熱板上加熱1分鐘,於銅箔上使焊料熔融後,於室溫冷卻。藉由測定焊球之接觸角來得到焊球在銅箔上的潤濕擴開,以評價助熔劑活性。焊球之接觸角,係使用數位顯微鏡(KH-7700、HIROX(股)製),測定在銅箔上熔融而潤濕擴開的焊球的半徑(a)及 焊球的高度(b),依下式求算接觸角。又,焊球的半徑(a),係使用焊料熔融而潤濕擴開之範圍中的最大直徑的一半之值。又,焊球的高度(b),係使用從已熔融的焊料的頂點向銅箔面拉垂線的線段長度。
焊球之接觸角=2arctan{(b)/(a)}
焊球之接觸角未達1.20弳者記載為A,為1.20弳以上者記載為C。
Figure 108114230-A0305-02-0043-22
由表1可確認焊料潤濕性試驗中,(i)~(iv)皆為良好的結果。以下之實施例中,使用N,N’-雙(亞柳基)-1,2-丙烷二胺及N,N’-雙(亞柳基)-1,3-丙烷二胺作為螯合助熔劑。
2.樹脂組成物及疊層體之製作
(實施例1)
將作為螯合助熔劑(A)之N,N’-雙(亞柳基)-1,2-丙烷二胺(東京化成工業(股)製)之甲乙酮(以下有時簡稱「MEK」)溶液(按不揮發成分換算計,係20質量份)、作為熱自由基聚合起始劑(B)之二異丙苯過氧化物(KISHIDA化學(股)製、10小時半衰期溫度:116.4℃)0.5質量份、作為第1自由基聚合性化合物(C)之式(3)中之R8皆為氫原子且n1為1以上3以下之馬來醯亞胺化合物(BMI-2300、大和化成工業(股)製)之MEK溶液(按不揮發成分換算計,係8質量份)、作為第2自由基聚合性化合物(C)之馬來醯亞胺化合物(BMI-1000P、KI化成(股)製)之MEK溶液(按不揮發成分換算計,係25質量份)、作為第3自由基聚合性化合物(C)之雙(3-乙基-5-甲基-4-馬來醯亞胺苯基)甲烷(BMI-70、KI化成(股)製)之MEK溶液(按不揮發成分換算 計,係16質量份)、作為第4自由基聚合性化合物(C)之2,2-雙{4-(4-馬來醯亞胺苯氧基)苯基}丙烷(BMI-80、KI化成(股)製)之MEK溶液(按不揮發成分換算計,係16質量份)、作為第1無機填充材(D)之漿液二氧化矽(SV-EM1、固體成分65%、均粒徑:0.3μm、Admatechs(股)製)75質量份、作為第2無機填充材(D)之漿液二氧化矽(SX-EM1、固體成分65%、均粒徑:0.3μm、Admatechs(股)製)25質量份、作為可撓性賦予成分(E)之丙烯酸基聚合物(US-6170、東亞合成(股)製)10質量份、以及作為密合性賦予成分之苯并
Figure 108114230-A0305-02-0044-55
(Pd型苯并
Figure 108114230-A0305-02-0044-56
、四國化成工業(股)製)之MEK溶液(按不揮發成分換算計,係25質量份)予以混合,使用高速攪拌裝置攪拌30分鐘,獲得清漆。將此清漆塗佈在表面塗了脫模劑的厚度38μm的聚對苯二甲酸乙二醇酯薄膜(TR1-38、Unitika(股)製),於100℃進行5分鐘加熱乾燥,獲得本發明之樹脂組成物層之厚度為30μm之疊層體。
(實施例2)
將作為螯合助熔劑(A)之N,N’-雙(亞柳基)-1,3-丙烷二胺(東京化成工業(股)製)之MEK溶液變更為按不揮發成分換算計係20質量份,除此以外,和實施例1同樣進行,製備清漆,得到疊層體。
(實施例3)
使用二(2-第三丁基過氧化異丙基)苯(PERBUTYL P、日油(股)製、10小時半衰期溫度:119.2℃)作為熱自由基聚合起始劑(B),並變更其使用量為0.5質量份,除此以外和實施例1同樣進行,製備清漆,獲得疊層體。
(實施例4)
將作為螯合助熔劑(A)之N,N’-雙(亞柳基)-1,3-丙烷二胺(東京化成工業(股)製)之MEK溶液以按不揮發成分換算計20質量份使用,使用二(2-第三丁基過氧化異丙基)苯(PERBUTYL P、日油(股)製、10小時半衰期溫度:119.2℃)作為熱自由基聚合起始劑(B),並變更其使用量為0.5質量份,除此以外和實施例1同樣進行而製備清漆,獲得疊層體。
(實施例5)
使用N,N’-雙(亞柳基)-1,2-丙烷二胺(東京化成工業(股)製)之MEK溶液作為螯合助熔劑(A),並將其使用量變更為按不揮發成分換算計係60質量份,除此以外和實施例1同樣進行,製備成清漆,獲得疊層體。
(實施例6)
使用1,1-二(第三己基過氧化)環己烷(PERHEXA HC、日油(股)製、10小時半衰期溫度:87.1℃)作為熱自由基聚合起始劑(B),並變更其使用量為0.5質量份,除此以外和實施例1同樣進行,製備成清漆,獲得疊層體。
(比較例1)
不使用螯合助熔劑(A),除此以外和實施例3同樣進行,製備成清漆,獲得疊層體。
(比較例2)
不使用熱自由基聚合起始劑(B),並變更成使用2-苯基-4-甲基咪唑(東京化成工業(股)製)之MEK溶液(按不揮發成分換算計,係0.5質量份)作為硬化促進劑,除此以外和實施例1同樣進行,製備成清漆,獲得疊層體。
(比較例3)
將雙酚A型環氧化合物(EXA-850CRP、環氧基當量171g/eq.、DIC(股)製)之MEK溶液(按不揮發成分換算計係62質量份)、酚醛清漆型苯酚化合物(PHENOLITE KA-1163、羥基當量118g/eq.、DIC(股)製)之MEK溶液(按不揮發成分換算計係38質量份)、作為螯合助熔劑(A)之N,N’-雙(亞柳基)-1,2-丙烷二胺(東京化成工業(股)製)之MEK溶液(按不揮發成分換算計係20質量份)、作為硬化促進劑之2-苯基-4-甲基咪唑之MEK溶液(按不揮發成分換算計係0.1質量份)、作為無機填充材(D)之漿液二氧化矽(SC-1050MLQ、平均粒徑:0.3μm、按不揮發成分換算計係100質量份)、作為可撓性賦予成分(E)之丙烯酸基聚合物(US-6170、東亞合成(股)製)10質量份、以及作為密合性賦予成分之苯并
Figure 108114230-A0305-02-0046-57
(Pd型苯并
Figure 108114230-A0305-02-0046-58
、四國化成工業(股)製)之MEK溶液(按不揮發成分換算計係25質量份)予以混合,使用高速攪拌裝置攪拌30分鐘,獲得清漆。將此清漆塗佈在表面塗了脫模劑的厚度38μm的聚對苯二甲酸乙二醇酯薄膜(TR1-38),於100℃進行5分鐘加熱乾燥,獲得疊層體。
3.評價方法
(1)能否製作清漆
在實施例1~6及比較例1~3的清漆製作過程中,若未能確認到清漆之凝膠化、樹脂組成物成分之沉降等則評為A,若確認到清漆之凝膠化、樹脂組成物成分之沉降等則評為C。結果示於表2。
(2)清漆保存安定性
使用B型黏度計(東京計器(股)製)測定實施例1~6及比較例1~3獲得之清漆之黏度(c),於密閉容器內於室溫放置2週後,再度使用B型黏度計測定黏度(d)。依下式算出經2週間後之黏度之變化率,變化率未達20%時記載為AA,經2週間後之黏度之變化率為20%以上且未達40%時記載為A,經2週後之黏度之變化率為40%以上時記載為C。結果示於表2。
黏度之變化率={|(d)-(c)|/(c)}×100
(3)安裝試驗
將實施例1~6及比較例1~3獲得之疊層體切成8mm×8mm之正方形,並層合於評價用基板上後,使用倒裝晶片接合器(LFB-2301,新川(股)製),於台座溫度70℃、接合頭溫度300℃、負荷50N、時間8秒之條件,將半導體晶片進行壓接並實施安裝試驗。由安裝試驗樣本之剖面觀察,若確認半導體晶片側之Cu柱上之焊料與基板側之配線之間生成了合金則記載A,未確認到生成合金則記載C。結果示於表2。
(4)安裝樣本外觀
使用光學顯微鏡從半導體晶片之正上方觀察安裝試驗後之樣本。若在半導體晶片之表面未確認到實施例1~6及比較例1~3獲得之樹脂組成物之附著則記載AA,若確認在半導體晶片之表面有少許實施例1~6及比較例1~3獲得之樹脂組成物之附著但認為在實際使用上對品質不造成影響則記載A,在半導體晶片之表面確認有實施例1~6及比較例1~3獲得之樹脂組成物之附著且是實際使用上無法容許者記載C。結果示於表2。
(5)可撓性
將實施例1~6及比較例1~3獲得之樹脂疊層體裁切成5cm×10cm的條狀後,於室溫以支持基材之聚對苯二甲酸乙二醇酯薄膜成為內側的方式捲繞在外徑為3cm的金屬管,保持5秒後捲回。重複此作業10次後,以目視確認本發明之樹脂組成物層有無龜裂,並實施可撓性之評價。完全沒發生龜裂者記載AA,發生少許龜裂但認為係實際使用上對於品質不造成影響者記載A,發生龜裂且是實際使用上不容許者記載C。結果示於表2。
(6)絕緣可靠性
以真空層合機在印刷配線基板之L/S=40μm/40μm之微細電路圖案上貼附實施例1~6及比較例1~3獲得之疊層體,並填埋微細配線間。使用烘箱,將前述製作之附疊層體之微細電路圖案基板於200℃加熱3小時,製成試驗樣本。針對獲得之試驗樣本,於溫度85℃、濕度60%之條件下進行168小時加濕熱處理作為前處理,將處理後之樣本流入設定最高溫度260℃之回流步驟3次。將前處理後之試驗樣本於溫度130℃、濕度85%、施加電壓5.0V之條件連續測定濕中絕緣電阻。針對評價基準,電阻值107Ω以下記載短路,直到短路之時間為300小時以上者記為A,未達300小時者記載為C。結果示於表2。
Figure 108114230-A0305-02-0048-23
本申請案係基於2018年4月26日提申的日本專利申請案(日本特願2018-84967),其內容在此援用作為參照。
〔產業利用性〕
本發明之樹脂組成物,如前所述,助熔劑活性、可撓性、及低熱膨脹性優異,且發揮各種效果,故能理想地作為樹脂組成物,尤其黏接劑用樹脂組成物使用。又,本發明之樹脂組成物作為預塗底層填充材料有用。本發明之樹脂組成物,因為助熔劑活性優異,在進行半導體晶片與基板之接合、半導體晶片與半導體晶圓之接合,進而半導體晶片與半導體晶片之接合時,可獲得良好的接合狀態,故極為有用。
Figure 108114230-A0101-11-0002-1

Claims (26)

  1. 一種樹脂組成物,含有螯合助熔劑(A)、熱自由基聚合起始劑(B)、及自由基聚合性化合物(C);該螯合助熔劑(A)含有下式(1)表示之化合物及/或下式(2)表示之亞胺化合物;該螯合助熔劑(A)之含量相對於該自由基聚合性化合物(C)之合計量100質量份,為10質量份以上50質量份以下;該自由基聚合性化合物(C)包含下式(4)表示之馬來醯亞胺化合物、以及選自由2,2-雙(4-(4-馬來醯亞胺苯氧基)苯基)丙烷、下式(3)表示之馬來醯亞胺化合物、及下式(5)表示之馬來醯亞胺化合物構成之群組中之至少1種以上之馬來醯亞胺化合物;
    Figure 108114230-A0305-02-0050-24
    式中,Q為伸芳基、伸烷基、伸烯基、環伸烷基、環伸烯基、伸雜環基、或伸雜芳基,R1及R2各自獨立地為氫原子、甲基、乙基、丙基、丁基、戊基、或己基,R3及R4為2-羥基苯基,鍵結於伸芳基、伸烷基、伸烯基、環伸烷基、環伸烯基、伸雜環基、及伸雜芳基之氫原子,也可取代為羥基或巰基;
    Figure 108114230-A0305-02-0050-25
    式中,R5為氫原子、甲基、乙基、丙基、丁基、戊基、或己基,R6及R7各自獨立地為烷基、環烷基、芳基、雜芳基、或雜環基,鍵結於烷基、環烷基、芳基、雜芳基、及雜環基之氫原子也可取代為羥基或巰基;
    Figure 108114230-A0305-02-0050-26
    式(3)中,R8各自獨立地表示氫原子或甲基,n1表示1以上之整數;
    Figure 108114230-A0305-02-0051-27
    式(4)中,n2之平均值為1以上30以下;
    Figure 108114230-A0305-02-0051-28
    式(5)中,R9及R10各自獨立地表示氫原子、甲基或乙基,R11各自獨立地表示氫原子或甲基。
  2. 如申請專利範圍第1項之樹脂組成物,其中,該螯合助熔劑(A)之熔點為235℃以下。
  3. 如申請專利範圍第1項之樹脂組成物,其中,該螯合助熔劑(A)之分子量為150以上500以下。
  4. 如申請專利範圍第1項之樹脂組成物,其中,使用該螯合助熔劑(A)於下列焊料潤濕性試驗中獲得之焊球之接觸角未達1.20弳;焊料潤濕性試驗:於厚度12μm之銅箔之光澤面塗佈該螯合助熔劑,在該螯合助熔劑上放置直徑0.5mm的焊球,之後於保持在235℃的熱板上加熱1分鐘,使焊料熔融後,於室溫冷卻;冷卻後測定在該銅箔上擴開的焊球的半徑(a)及焊球的高度(b),並依下式算出接觸角; 焊球之接觸角=2arctan{(b)/(a)}。
  5. 如申請專利範圍第1項之樹脂組成物,其中,該螯合助熔劑(A)含有選自由N,N’-雙(亞柳基)-1,2-丙烷二胺、N,N’-雙(亞柳基)乙二胺、N,N’-雙(亞柳基)-1,3-丙烷二胺、及N,N’-雙(亞柳基)-1,2-苯二胺構成之群組中之至少一種。
  6. 如申請專利範圍第1項之樹脂組成物,其中,該螯合助熔劑(A)含有N,N’-雙(亞柳基)-1,2-丙烷二胺及/或N,N’-雙(亞柳基)-1,3-丙烷二胺。
  7. 如申請專利範圍第1項之樹脂組成物,其中,該熱自由基聚合起始劑(B)為有機過氧化物。
  8. 如申請專利範圍第7項之樹脂組成物,其中,該熱自由基聚合起始劑(B)之10小時半衰期溫度為100℃以上。
  9. 如申請專利範圍第7項之樹脂組成物,其中,該熱自由基聚合起始劑(B)為二烷基過氧化物及/或過氧化氫。
  10. 如申請專利範圍第7項之樹脂組成物,其中,該熱自由基聚合起始劑(B)含有選自由二異丙苯過氧化物、二(2-第三丁基過氧化異丙基)苯、二第三丁基過氧化物、1,1,3,3-四甲基丁基過氧化氫、2,5-二甲基-2,5-二(第三丁基過氧化過氧化過氧化)己-3-炔、2,5-二甲基-2,5-二(第三丁基過氧化過氧化過氧化)己烷、二第三己基過氧化物、第三丁基異丙苯過氧化物、二第三戊基過氧化物、第三戊基過氧化 氫、第三丁基過氧化氫、異丙苯過氧化氫、二異丙基苯過氧化氫、及對薄荷烷過氧化物構成之群組中之至少一種。
  11. 如申請專利範圍第7項之樹脂組成物,其中,該熱自由基聚合起始劑(B)含有選自由二異丙苯過氧化物、異丙苯過氧化氫、二異丙基苯過氧化氫、二(2-第三丁基過氧化異丙基)苯、及對薄荷烷過氧化物構成之群組中之至少一種。
  12. 如申請專利範圍第1項之樹脂組成物,其中,該樹脂組成物中之該螯合助熔劑(A)之含量相對於該自由基聚合性化合物(C)之合計量100質量份為5質量份以上50質量份以下。
  13. 如申請專利範圍第1項之樹脂組成物,其中,該樹脂組成物中之該熱自由基聚合起始劑(B)之含量相對於該自由基聚合性化合物(C)之合計量100質量份為0.005質量份以上5質量份以下。
  14. 如申請專利範圍第1項之樹脂組成物,更含有無機填充材(D)。
  15. 如申請專利範圍第14項之樹脂組成物,其中,該無機填充材(D)具有電絕緣性。
  16. 如申請專利範圍第14項之樹脂組成物,其中,該無機填充材(D)含有選自由二氧化矽、氫氧化鋁、氧化鋁、軟水鋁石、氮化硼、氮化鋁、氧化鎂、及氫氧化鎂構成之群組中之至少1種。
  17. 如申請專利範圍第14項之樹脂組成物,其中,該無機填充材(D)之平均粒徑為3μm以下。
  18. 如申請專利範圍第14項之樹脂組成物,其中,該樹脂組成物中之該無機填充材(D)之含量相對於該自由基聚合性化合物(C)之合計量100質量份為300質量份以下。
  19. 如申請專利範圍第1項之樹脂組成物,更含有可撓性賦予成分(E)。
  20. 如申請專利範圍第19項之樹脂組成物,其中,該可撓性賦予成分(E)含有熱塑性之高分子化合物,該高分子化合物之重量平均分子量為1,000以上1,000,000以下。
  21. 如申請專利範圍第19項之樹脂組成物,其中,該可撓性賦予成分(E)為(甲基)丙烯酸基寡聚物及/或(甲基)丙烯酸基聚合物。
  22. 如申請專利範圍第1項之樹脂組成物,係用於預塗式底層填充材。
  23. 一種疊層體,具備:支持基材;及疊層在該支持基材上之含有如申請專利範圍第1項之樹脂組成物之層。
  24. 一種附樹脂組成物層之半導體晶圓,具備半導體晶圓及疊層在該半導體晶圓之如申請專利範圍第23項之疊層體;該含有樹脂組成物之層疊層於該半導體晶圓。
  25. 一種附樹脂組成物層之半導體搭載用基板,具備:半導體搭載用基板,及疊層於該半導體搭載用基板之如申請專利範圍第23項之疊層體,該含有樹脂組成物之層疊層於該半導體搭載用基板。
  26. 一種半導體裝置,具備:如申請專利範圍第24項之附樹脂組成物層之半導體晶圓,及/或如申請專利範圍第25項之附樹脂組成物層之半導體搭載用基板。
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