TW202031785A - 補強用樹脂組成物、電子零件、電子零件之製造方法、安裝結構體及安裝結構體之製造方法 - Google Patents

補強用樹脂組成物、電子零件、電子零件之製造方法、安裝結構體及安裝結構體之製造方法 Download PDF

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TW202031785A
TW202031785A TW108143756A TW108143756A TW202031785A TW 202031785 A TW202031785 A TW 202031785A TW 108143756 A TW108143756 A TW 108143756A TW 108143756 A TW108143756 A TW 108143756A TW 202031785 A TW202031785 A TW 202031785A
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resin composition
conductor
bump
electronic component
resin
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TW108143756A
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山津繁
鈴木康寬
日野裕久
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日商松下知識產權經營股份有限公司
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Publication of TW202031785A publication Critical patent/TW202031785A/zh

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    • 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
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Abstract

本發明提供一種不易在凸塊與導體之間發生導通不良且容易覆蓋導體與凸塊之接合處的補強用樹脂組成物。補強用熱硬化性樹脂組成物包含環氧樹脂(A)、酚樹脂(B)及苯并
Figure 108143756-A0304-12-0059-1

Description

補強用樹脂組成物、電子零件、電子零件之製造方法、安裝結構體及安裝結構體之製造方法
本揭示一般涉及一種補強用樹脂組成物、電子零件、電子零件之製造方法、安裝結構體及安裝結構體之製造方法。本揭示詳細而言是涉及一種補強用樹脂組成物、包含補強用樹脂組成物之硬化物的電子零件及其製造方法、包含補強用樹脂組成物之硬化物的安裝結構體及其製造方法。
將半導體晶片安裝於電路基板時，係將焊料製凸塊與電路基板所具備之導體進行電連接。在連接凸塊與導體時，有時會以樹脂組成物之硬化物覆蓋凸塊與導體的接合處來補強。譬如，於凸塊與導體之間配置樹脂組成物並予以加熱，藉此使凸塊與導體連接的同時，可以樹脂組成物之硬化物覆蓋接合處。專利文獻1(日本專利申請案公開2010-254895號公報)中揭示了一種可用於補強接合處的樹脂組成物一例。 在連接凸塊與導體時，有時會在凸塊與導體之間發生導通不良。尤其，加熱時的溫度一高，就容易發生導通不良。
本揭示目的在於提供一種不易在凸塊與導體之間發生導通不良且容易覆蓋導體與凸塊之接合處的補強用樹脂組成物。
本揭示一態樣之補強用樹脂組成物包含環氧樹脂(A)、酚樹脂(B)及苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)。
本揭示一態樣之電子零件具備：電子零件本體；導體，係形成於前述電子零件本體之表面上；焊料製凸塊，係配置在前述導體上且與前述導體電連接；及補強部。前述補強部為上述補強用樹脂組成物之硬化物，且覆蓋前述導體與前述凸塊之接合處。
本揭示一態樣之電子零件之製造方法係以上述補強用樹脂組成物覆蓋前述導體與前述凸塊之接合處後，使前述補強用樹脂組成物硬化。
本揭示一態樣之安裝結構體具備：具備第1導體之電路基板、具備第2導體之電子零件、焊料製凸塊及補強部。前述凸塊中介於前述第1導體與前述第2導體之間，且將前述第1導體與前述第2導體電連接。前述補強部為上述補強用樹脂組成物之硬化物，且覆蓋前述第1導體與前述凸塊之接合處、及前述第2導體與前述凸塊之接合處中之至少一者。
本揭示一態樣之安裝結構體之製造方法係以上述補強用樹脂組成物覆蓋前述第1導體與前述凸塊之接合處、及前述第2導體與前述凸塊之接合處中之至少一者後，使前述補強用樹脂組成物硬化。
1.概要 本揭示一實施形態之補強用樹脂組成物(以下亦稱樹脂組成物(X))包含環氧樹脂(A)、酚樹脂(B)及苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)。
在使樹脂組成物(X)之溫度上升以使其熱硬化時，在樹脂組成物(X)之熱硬化反應開始前，容易降低樹脂組成物(X)之黏度，即使溫度上升，也可輕易維持低黏度的狀態。即，可輕易提高樹脂組成物(X)之黏度開始增加的溫度。
並且，在使樹脂組成物(X)之溫度上升以使其熱硬化時，在樹脂組成物(X)之硬化反應開始後容易急遽發生硬化反應，而容易使黏度急遽增加。
所以，在樹脂組成物(X)之硬化反應開始前，使焊料製凸塊熔融，較容易連接導體與凸塊。接著，可在以樹脂組成物(X)覆蓋導體與凸塊之接合處的狀態下，使樹脂組成物(X)急遽硬化而輕易提高製造效率。所以，即使在凸塊為SAC焊料等熔點高的焊料製、加熱溫度高的情況下，也不容易在導體與凸塊之間發生導通不良。
2.詳細 以下，詳細說明本實施形態之樹脂組成物(X)、電子零件100(參照圖2)、電子零件100之製造方法(參照圖3A~圖3C)、安裝結構體1(參照圖4A~圖4C)及安裝結構體1之製造方法(參照圖5A~圖5C)。
2-1.樹脂組成物(X) 本實施形態之樹脂組成物(X)如上述包含環氧樹脂(A)、酚樹脂(B)及苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)。並且，樹脂組成物(X)宜包含活性劑(D)。以下說明環氧樹脂(A)、酚樹脂(B)、苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)及活性劑(D)之詳細內容。
(1)環氧樹脂(A) 環氧樹脂(A)係具有環氧基之化合物，具有經加熱而硬化之性質。所以，環氧樹脂(A)可賦予樹脂組成物(X)熱硬化性。
環氧樹脂(A)宜在常溫下為液態。此時，在樹脂組成物(X)中可輕易地使環氧樹脂(A)與其他成分混合。另，在常溫下為液態意指在大氣壓力下、且周圍溫度為5℃以上且28℃以下(尤其是20℃前後)之狀態下具有流動性。為了使環氧樹脂(A)在常溫下為液態，可使環氧樹脂(A)僅包含在常溫下為液態之成分，可使環氧樹脂(A)包含在常溫下為液態之成分與在常溫下非液態之成分，或可藉由反應性稀釋劑、溶劑等使環氧樹脂(A)在常溫下成為液態。
環氧樹脂(A)宜包含一分子內具有二個以上環氧基之液態環氧樹脂(A1)。環氧樹脂(A1)可包含譬如選自於由環氧丙基醚型環氧樹脂、環氧丙基胺型環氧樹脂、環氧丙基酯型環氧樹脂及烯烴氧化型(脂環式)環氧樹脂所構成群組中之一種以上成分。
環氧樹脂(A1)可包含譬如選自於由雙酚A型環氧樹脂、雙酚F型環氧樹脂等雙酚型環氧樹脂、加氫雙酚A型環氧樹脂、加氫雙酚F型環氧樹脂等加氫雙酚型環氧樹脂、聯苯型環氧樹脂、含萘環之環氧樹脂、脂環式環氧樹脂、二環戊二烯型環氧樹脂、苯酚酚醛型環氧樹脂、甲酚酚醛型環氧樹脂、三苯甲烷型環氧樹脂、脂肪族系環氧樹脂及三聚異氰酸三環氧丙基酯所構成群組中之一種以上成分。
環氧樹脂(A1)尤宜包含雙酚型環氧樹脂及加氫雙酚型環氧樹脂中之一者或兩者。此時，容易使樹脂組成物(X)低黏度化，且容易提升樹脂組成物(X)之硬化物的物性。
環氧樹脂(A1)亦可使用市售物。市售物可舉如雙酚A型環氧樹脂(Mitsubishi Chemical Co.製：型號jER828)及雙酚F型環氧樹脂(Mitsubishi Chemical Co.製：型號jER806)等。
環氧樹脂(A)可僅包含環氧樹脂(A1)，亦可包含環氧樹脂(A1)與環氧樹脂(A1)以外之環氧樹脂。
(2)酚樹脂(B) 酚樹脂(B)係具有酚性羥基之化合物。該酚性羥基可與環氧樹脂(A)之環氧基行反應。
酚樹脂(B)尤宜於一分子中具有二個以上酚性羥基。一分子中具有二個以上酚性羥基之酚樹脂(B)可舉如雙酚A、苯酚酚醛、甲酚酚醛等多官能酚類。酚樹脂(B)可包含該等成分中之一種以上。酚樹脂(B)亦可為市售物。市售物之酚樹脂可舉如苯酚甲醛酚醛樹脂(明和化成(股)製：型號MEH-8000H)、苯酚酚醛樹脂(明和化成(股)製：型號HF-1M)、苯酚芳烷基樹脂(明和化成(股)製：型號MEH-7800)、聯苯芳烷基樹脂(明和化成(股)製：型號MEH-7851SS)等。
酚樹脂(B)尤宜包含羥基當量為70g/eq以上且150g/eq以下之苯酚酚醛樹脂(B1)。此時，可提升酚樹脂(B)對環氧樹脂(A)之溶解性。另，在本說明書中，羥基當量意指根據JIS K 0070之中和滴定法所測得之數值。
苯酚酚醛樹脂(B1)尤宜為液態。即，酚樹脂(B)宜包含一分子中具有二個以上酚性羥基、羥基當量為70g/eq以上且150g/eq以下且為液態的苯酚酚醛樹脂(B1)。此時，可提升樹脂組成物(X)之濡溼性。所述苯酚酚醛樹脂(B1)之市售物可舉如苯酚甲醛酚醛樹脂(明和化成(股)製：型號MEH-8000H)。
酚樹脂(B)可僅包含苯酚酚醛樹脂(B1)，亦可包含苯酚酚醛樹脂(B1)與苯酚酚醛樹脂(B1)以外之酚樹脂。
(3)苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C) 苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)係包含二氫苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
環之化合物。苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)依原材料之種類而具有各種結構。苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)譬如可由各種苯酚、胺及甲醛等合成。
二氫苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
環於化學上相當穩定，所以在常態下不會進行苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)之聚合反應。但，藉由將苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)加熱至約170℃以上，二氫苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
環會開環而生成具有由酚性羥基與鹼性胺基構成之二胺基二苯基結構的聚苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物。藉由該開環形成之二胺基二苯基結構中存在的鹼性胺基可作為環氧樹脂(A)與酚樹脂(B)之反應的硬化促進劑，促進在高溫下之反應。具體上，可促進在比SAC焊料之熔點更高之溫度下的反應。所以，可於焊料開始熔融後，加速樹脂組成物(X)之硬化反應。並且，二氫苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
環在達170℃之前不會開環，所以環氧樹脂(A)與酚樹脂(B)不會進行反應，而可至焊料熔融為止前抑制樹脂組成物(X)硬化。而且，在二氫苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
環開環後，酚樹脂(B)之酚性羥基會自聚合而不產生副產物、或與環氧樹脂(A)等行反應。如此一來，於焊料熔融後，藉由二氫苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
環之開環，樹脂組成物(X)會急速反應。
苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)宜包含分子內具有多個
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
環之多價
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C1)。多價
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C1)可藉由與環氧樹脂(A)之反應而輕易形成三維交聯結構。所以，苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)包含多價
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C1)時，相較於不包含多價
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C1)之情況，較可增大樹脂組成物(X)之硬化物的玻璃轉移溫度(Tg)。
多價
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C1)亦可使用市售物。苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C1)之代表市售物一例可舉：P-d型苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物：苯酚、二胺基二苯甲烷與甲醛之聚合物(四國化成工業(股)製)。P-d型苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物譬如具有如下述之結構。
[化學式1]
Figure 02_image001
(式中，R表示氫或烯丙基；烯丙基可為拉電子基，亦可為推電子基)。
多價
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C1)的代表市售物一例可舉：F-a型苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物：雙酚F、苯胺與甲醛之聚合物(四國化成工業(股)製)。F-a型苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物具有如下述之結構。
[化學式2]
Figure 02_image003
(4)活性劑(D) 樹脂組成物(X)如上述宜包含活性劑(D)。活性劑(D)具有去除金屬氧化膜之功能，所以藉由樹脂組成物(X)包含活性劑(D)，可賦予樹脂組成物(X)熔劑作用。另，熔劑作用意指去除要塗佈焊料糊之金屬表面所生氧化皮膜的還原作用，及使熔融焊料之表面張力降低以促進焊料對接合金屬表面之濡溼性的作用。
活性劑(D)宜包含熔點為130℃以上且220℃以下之有機酸(D1)及熔點為130℃以上且220℃以下之胺(D2)中之至少一者。此時，可藉由活性劑(D)使環氧樹脂(A)之硬化反應不易被促進。而且，即使使用熔點為200℃附近或200℃以上的焊料，依舊可在使焊料熔融之前去除焊料的氧化皮膜。又，在焊料熔融前有機酸(D1)或胺(D2)便會熔融，而可在焊料熔融前將樹脂組成物(X)行低黏度化，從而可提升樹脂組成物(X)之濡溼性。
有機酸(D1)譬如可包含選自於由松香成分材料、己二酸、戊二酸、琥珀酸、丙二酸、檸檬酸、辛二酸(cork acid)、癸二酸及庚二酸所構成群組中之一種以上。有機酸(D1)尤宜包含琥珀酸(熔點186℃)、己二酸(熔點152℃)、辛二酸(熔點142℃)、癸二酸(熔點133℃)。
胺(D2)只要是可作為熔劑使用之胺即無特別限定，譬如可包含選自於由各種胺鹽、三乙醇胺(TEA)及胍所構成群組中之一種以上。
活性劑(D)亦可包含有機酸(D1)及胺(D2)以外之成分。活性劑(D)既可包含熔點低於130℃之有機酸或胺，亦可包含熔點超過220℃之有機酸或胺。
(5)其他成分(E) 樹脂組成物(X)亦可包含環氧樹脂(A)、酚樹脂(B)、苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)及活性劑(D)以外之成分(E)。成分(E)可包含譬如松香等成分改質劑、填料、觸變性賦予劑等。
(6)各成分之含有比率 在樹脂組成物(X)中，相對於環氧樹脂(A)、酚樹脂(B)、苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)及活性劑(D)之合計，環氧樹脂(A)之比率宜為20重量%以上且60重量%以下。
並且在樹脂組成物(X)中，相對於環氧樹脂(A)、酚樹脂(B)、苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)及活性劑(D)之合計，酚樹脂(B)之比率宜為10重量%以上且40重量%以下。
又在樹脂組成物(X)中，相對於環氧樹脂(A)、酚樹脂(B)、苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)及活性劑(D)之合計，苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)之比率宜為5重量%以上且30重量%以下。
並且在樹脂組成物(X)中，相對於環氧樹脂(A)、酚樹脂(B)、苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)及活性劑(D)之合計，活性劑(D)之比率宜為3重量%以上且40重量%以下。
在樹脂組成物(X)中，藉由環氧樹脂(A)、酚樹脂(B)、苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)及活性劑(D)之比率滿足上述條件，可降低樹脂組成物(X)之硬化物的玻璃轉移溫度的同時，可提升樹脂組成物(X)之硬化物的彈性模數。所以，可提升以樹脂組成物(X)之硬化物覆蓋焊料周圍所得之補強效果。
尤其，相對於環氧樹脂(A)、酚樹脂(B)、苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)及活性劑(D)之合計，環氧樹脂(A)之比率宜為60重量%以下。此時，可使樹脂組成物(X)迅速硬化，並可抑制樹脂組成物(X)之硬化變慢。
尤其，相對於環氧樹脂(A)、酚樹脂(B)、苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)及活性劑(D)之合計，苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)之比率宜為30重量%以下。此時，可抑制於樹脂組成物(X)之硬化物產生孔隙(氣泡)。
2-2.使用樹脂組成物(X)來補強導體與凸塊之接合處 以下，說明使用樹脂組成物(X)來製造用以補強導體與焊料製凸塊之接合處之補強部的方法。
於導體上配置焊料製凸塊，使該凸塊熔融而可將導體與凸塊進行電連接。以樹脂組成物(X)之硬化物覆蓋該導體與凸塊之接合處，可補強導體與凸塊之接合處。譬如，當在導體與凸塊之間配置有樹脂組成物(X)的狀態下將凸塊及樹脂組成物(X)加熱，樹脂組成物(X)會因樹脂組成物(X)之黏度下降而流動，隨此凸塊便會接觸導體。在樹脂組成物維持流動性的狀態下，凸塊會熔融而熔接於導體。藉由樹脂組成物(X)覆蓋導體與凸塊之接合處，並在該狀態下硬化來製作補強部。藉此，可將導體與凸塊電連接，且以樹脂組成物(X)之硬化物的補強部覆蓋導體與凸塊之接合處而達成補強。為了使凸塊熔融，凸塊及樹脂組成物(X)會被加熱至比焊料熔點更高的溫度為止。
於圖1之圖表顯示將導體與凸塊電連接且製作補強部時之加熱溫度的曲線及樹脂組成物(X)之黏度變化之例。在圖1之圖表中，實線表示加熱溫度，虛線表示樹脂組成物(X)之黏度。圖中之T3(℃)為凸塊之熔點，T1(℃)及T2(℃)為滿足室溫＜T1＜T2＜T3之關係的特定溫度。
如圖1所示，首先將加熱溫度從室溫上升至T1(℃)為止。接著，一邊放慢加熱溫度之升溫速度，並同時使加熱溫度上升至T2(℃)為止。再來，一邊提高升溫速度一邊使加熱溫度升溫至比T3(℃)更高的溫度(峰值溫度)為止。接著將加熱溫度下降至室溫為止。
凸塊之熔點T3(℃)依構成凸塊之焊料組成而定，當焊料為Sn-Ag-Cu(SAC)系焊料時，T3(℃)譬如為217以上且230℃以下。T1(℃)宜規定在樹脂組成物(X)開始熔融之溫度附近。T1(℃)並無特別限定，譬如為140℃以上且160℃以下。T2(℃)宜規定在高於T1(℃)、且比樹脂組成物(X)開始硬化之溫度更低的溫度。T2並無特別限定，譬如為160℃以上且200℃以下。峰值溫度宜規定在高於T3(℃)、且比樹脂組成物(X)開始硬化之溫度更高的溫度。峰值溫度並無特別限定，譬如為232℃以上且255℃以下。加熱溫度從室溫上升至T1(℃)為止時的加熱溫度之升溫速度並無特別限定，譬如為5℃/秒以下。加熱溫度從T1(℃)上升至T2(℃)為止之所需時間並無特別限定，譬如為60秒以上且100秒以下。加熱溫度從T2(℃)上升至峰值溫度(℃)為止時的升溫速度譬如為4℃/秒以下。加熱溫度為T3(℃)以上之時間並無特別限定，譬如為30秒以上且90秒以下。
如圖1所示，從T1(℃)附近開始，樹脂組成物(X)之黏度下降並開始流動。所以，藉由控制從室溫至T1(℃)為止之加熱溫度的升溫速度，可控制從加熱開始至樹脂組成物(X)開始流動之前的時間。
如圖1所示，即使使加熱溫度從T1(℃)上升至T2(℃)，樹脂組成物(X)依舊維持低黏度。所以，藉由控制從T1(℃)至T2(℃)為止之升溫速度，可控制樹脂組成物(X)維持流動性的時間。藉此，可使樹脂組成物(X)充分流動而抑制於補強部產生孔隙的情況。
如圖1所示，加熱溫度若從T2(℃)往峰值溫度攀升，即使加熱溫度超過T3(℃)，短時間內樹脂組成物(X)之黏度也不易提高，樹脂組成物(X)仍維持具有流動性之狀態，接著黏度才會急遽增加。即，即使加熱溫度超過焊料之熔點，在短時間內樹脂組成物(X)仍易維持具有流動性的狀態。所以，藉由樹脂組成物(X)流動，凸塊容易與導體接觸，且凸塊容易與導體熔融接合。且，已熔融之凸塊的自對準效果不容易受樹脂組成物(X)阻礙。並且，當樹脂組成物(X)包含活性劑(D)時，加熱溫度從T2(℃)上升至T3(℃)期間，可藉由活性劑(D)之熔劑作用迅速去除焊料之氧化皮膜。因此，可將導體與焊料良好連接，而可更抑制導通不良的發生。
接下來，在樹脂組成物(X)覆蓋導體與焊料之接合處的狀態下進行硬化，來製造用以覆蓋導體與焊料之接合處的補強部。如圖1所示，即使加熱溫度從峰值溫度往室溫下降，樹脂組成物(X)之黏度依舊會持續增加。所以，可在導體與焊料之接合處被樹脂組成物(X)覆蓋之狀態下，使該樹脂組成物(X)迅速硬化。
樹脂組成物(X)之所以能實現所述黏度行為，吾人認為是因為樹脂組成物(X)包含環氧樹脂(A)、酚樹脂(B)、苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)及活性劑(D)的緣故。
具體上，吾人認為在樹脂組成物(X)熔融時，即使加熱溫度從T1(℃)往T2(℃)攀升，黏度也不易增加是因為苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)熔融後樹脂組成物(X)才熔融所致。而且，吾人認為即使加熱溫度達T3(℃)，樹脂組成物(X)的黏度也沒有立即提高而是過一段時間後黏度才急遽增加，是因為苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)之開環反應在170℃以上之高溫下才產生所致。
並且，當樹脂組成物(X)包含活性劑(D)時，因活性劑(D)包含有機酸(D1)及胺(D2)中之至少一者，而可利用活性劑(D)使環氧樹脂(A)之硬化反應不易被促進。藉此還能在加熱溫度達T3(℃)之前易將樹脂組成物(X)之黏度維持地較低。
又，吾人認為即使加熱溫度從峰值溫度往室溫下降，樹脂組成物(X)依舊迅速硬化，不僅是因為苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)的自聚合反應，還有苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物(C)與環氧樹脂(A)反應而形成三維交聯結構所致。因此，可提升樹脂組成物(X)之硬化物的玻璃轉移溫度(Tg)。
所以，只要將樹脂組成物(X)應用於圖2所示之電子零件100，便可製造覆蓋電子零件本體200所具備之導體210與凸塊32之接合處20的補強部4。
並且，只要將樹脂組成物(X)應用於圖4A所示安裝結構體1，便可在連接電路基板2之第1導體21與凸塊32時製造覆蓋第1導體21與凸塊32之接合處20的補強部4。
本實施形態之樹脂組成物(X)亦可於導體與凸塊經電連接後，用來製造覆蓋導體與凸塊之接合處的補強部。
2-3.電子零件及其製造方法 以下說明應用了樹脂組成物(X)之電子零件100之構成及其製造方法。
(1)電子零件之構成 參照圖2說明本實施形態之電子零件100。另，以下所示電子零件100之構成僅為一例，電子零件100之構成不受以下內容限定。
電子零件100並無特別限定，譬如為表面安裝型半導體晶片。半導體晶片並無特別限定，譬如為BGA(Ball Grid Array：球柵陣列)、WLP(Wafer Level Package：晶圓級封裝)等。
電子零件100具備電子零件本體200、導體210、焊料製凸塊30與補強部4。
導體210係形成於電子零件本體200之表面，所以導體210在電子零件本本體200之表面上露出在外部。電子零件100為WLP時，電子零件本體200譬如包含設有重配線層之矽基板，導體210譬如為已與重配線層電連接之導柱(pillar)。電子零件100為BGA時，電子零件本體200譬如為以密封樹脂密封經安裝於基板上之晶粒而構成的封包，導體210譬如為已與晶粒電連接之電極墊。電子零件本體200之結構不限於前述，只要是因應電子零件100之種類的適當結構即可。
凸塊30係配置於導體210上且與導體210電連接。所以，於凸塊30與導體210之間形成有接合處20。凸塊30並無特別限定，譬如可為SAC焊料製，亦可為錫銅系(Sn-Bi系)焊料製。Sn-Bi系焊料除Sn及Bi外，亦可含有選自於由Ag、Ni、Fe、Ge、Cu及In所構成群組中之至少1種材料。為了提升Sn-Bi系焊料之機械性能，Sn-Bi系焊料宜包含選自於由Ag、Ni、Fe及Ge所構成群組中之至少一種材料。
補強部4為樹脂組成物(X)之硬化物。在電子零件100中，補強部4覆蓋著凸塊30與導體210之接合處20。即，在電子零件100中，凸塊30與導體210之接合處20被樹脂組成物(X)之硬化物所覆蓋。所以，可藉由補強部4來補強凸塊30與導體210之接合處20，提升電子零件100之連接可靠性。
(2)電子零件之製造方法 以下將一邊參照圖3A~圖3C，一邊說明電子零件100之製造方法。
首先，準備具備導體210之電子零件本體200，並將樹脂組成物(X)配置成覆蓋導體210(參照圖3A)。配置樹脂組成物(X)之方法並無特別限定，譬如可藉由噴墨法等印刷法、轉印等方法進行。
接下來，將凸塊30配置於導體210之上方，以使凸塊30與樹脂組成物(X)相接(參照圖3B)。凸塊30譬如可使用焊球。
接著，在圖3B所示狀態下加熱凸塊30及樹脂組成物(X)。加熱方法並無特別限定，譬如可採用利用回焊爐進行之加熱。此時，譬如可依圖1所示之回焊曲線，來加熱凸塊30及樹脂組成物(X)。
如同上述「2-2.使用樹脂組成物(X)來補強導體與凸塊之接合處」項目中所記載，在凸塊30熔融之前，樹脂組成物(X)係維持低黏度。且，即使凸塊30開始熔融，樹脂組成物(X)之黏度也不會立刻提高，過一段時間後黏度才急遽增加。所以，可以樹脂組成物(X)覆蓋導體210與凸塊30之接合處20後，再使樹脂組成物(X)硬化。藉此可使導體210與凸塊30良好連接。因此可抑制導體210與凸塊30之導通不良。並且可以樹脂組成物(X)之硬化物覆蓋導體210與凸塊30之接合處20。所以可補強導體210與凸塊30之接合處20。
2-4.安裝結構體及其製造方法 (1)安裝結構體 參照圖4A~圖4C來說明本實施形態之安裝結構體1。另，以下所示安裝結構體1之構成僅為一例，安裝結構體1之構成不受以下內容限定。
安裝結構體1具備電路基板2、電子零件3、凸塊32與補強部4。
電路基板2譬如為母基板、封裝基板或中介層(interposer)基板。譬如，電路基材2為玻璃環氧製、聚醯亞胺製、聚酯製、陶瓷製等之絕緣基板。於電路基板2之表面上形成有第1導體21。所以，電路基板2具備第1導體21。第1導體21並無特別限定，譬如為導體配線。
電子零件3譬如為半導體晶片，較具體而言，譬如為BGA(ball grid array)、LGA(land grid array：平面柵陣列)或CSP(chip size package：晶粒尺寸封裝)等倒裝晶片型晶片。電子零件3亦可為PoP(Package-on-Package：層疊式封裝)型晶片。於電子零件3之表面上形成有第2導體31。所以，電子零件3具備第2導體31。第2導體31並無特別限定，譬如為電極墊。
凸塊32中介於電路基板2之第1導體21與電子零件3之第2導體31之間。凸塊32係和第1導體21與第2導體31相互電連接。凸塊32並無特別限定，譬如可為SAC焊料製，亦可為錫銅系(Sn-Bi系)焊料製。
補強部4為樹脂組成物(X)之硬化物。在安裝結構體1中，補強部4覆蓋著凸塊32與第1導體21之接合處20。即，在安裝結構體1中，凸塊32與第1導體21之接合處20被樹脂組成物(X)之硬化物所覆蓋。所以，可藉由補強部4來補強凸塊32與第1導體21之接合處20，提升安裝結構體1之連接可靠性。
在圖4A所示之安裝結構體1中，補強部4覆蓋著電路基板2之第1導體21與凸塊32之接合處20，惟不受此限。
譬如，亦可如圖4B所示之安裝結構體1，電子零件3之第2導體31與凸塊32之接合處20被補強部4所覆蓋。
並且，譬如亦可如圖4C所示之安裝結構體1，電路基板2之第1導體21與凸塊32之接合處20被補強部4覆蓋，且電子零件3之第2導體31與凸塊32之接合處20被補強部4所覆蓋。
又，在如圖4A及圖4C所示之安裝結構體1中鄰接之第1導體21的間隔小(窄間隔)、或如在圖4B及圖4C所示之安裝結構體1中鄰接之第2導體31的間隔小的情況下，鄰接之補強部4亦可彼此相互連接而成一體化。並且，在圖4A~圖4C所示之安裝結構體1中，鄰接之所有補強部4亦可相互連接在一起。即，電路基板2之表面可被補強部4所覆蓋，電子零件3之表面亦可被補強部4所覆蓋。
並且在圖4C所示之安裝結構體1中，覆蓋第1導體21與凸塊32之接合處20的補強部4可與覆蓋第2導體31與凸塊32之接合處20的補強部4相互連接而成一體化。惟，在構成凸塊32之焊料的熔點以上之溫度下進行多次加熱時(譬如，回焊步驟或修復步驟等)，於焊料再次熔融時內壓會上升而可能產生焊料溢料(solder flash)。所以，覆蓋第1導體21與凸塊32之接合處20的補強部4與覆蓋第2導體31與凸塊32之接合處20的補強部4未一體化較佳。
(2)安裝結構體之製造方法 以下，參照圖5A~圖5C說明圖4A所示之安裝結構體1之製造方法。
首先，準備具備第1導體21之電路基板2，並將樹脂組成物(X)配置成覆蓋第1導體21(參照圖5A)。配置樹脂組成物(X)之方法並無特別限定，譬如可藉由印刷、轉印、塗佈等方法進行。
接下來，準備具備第2導體31之電子零件3。第2導體31上設置有凸塊32，且第2導體31與凸塊32為電連接狀態。將該電子零件3以凸塊32與樹脂組成物(X)接觸的方式配置於電路基板2之上(參照圖5B)。
接著，在圖5B所示狀態下加熱凸塊32及樹脂組成物(X)。加熱方法並無特別限定，譬如可採用利用回焊爐進行之加熱。此時，譬如可依圖1所示之回焊曲線，來加熱凸塊32及樹脂組成物(X)。
如同上述「2-2.使用樹脂組成物(X)來補強導體與凸塊之接合處」項目中所記載，在凸塊32熔融之前，樹脂組成物(X)係維持低黏度。且，即使凸塊32開始熔融，樹脂組成物(X)之黏度也不會立刻提高，過一段時間後黏度才急遽增加。所以，可以樹脂組成物(X)覆蓋第1導體21與凸塊32之接合處20後，再使樹脂組成物(X)硬化。藉此可使第1導體21與凸塊32良好連接，而可抑制第1導體21與凸塊32之導通不良。並且可以樹脂組成物(X)之硬化物覆蓋第1導體21與凸塊32之接合處20。所以可補強導體21與凸塊32之接合處20。
另，在上述安裝結構體1之製造方法中，於第2導體31上設有凸塊32，惟不受此限。譬如，亦可於第1導體21上設有凸塊32。此時，可將樹脂組成物(X)配置成覆蓋第2導體31，並在連接第2導體31與凸塊32時，以樹脂組成物(X)覆蓋第2導體31與凸塊32之接合處20後，再使樹脂組成物(X)硬化。屆時，可如圖4B所示之安裝結構體1，藉由補強部4補強第2導體31與凸塊32之接合處20。 實施例
1.調製樹脂組成物 以表1及表2所示比率將表1及表2中所示成分混合而獲得樹脂組成物。另，表1中所示成分詳細如下。 ・EPICLON835LV：在25℃下為液態之雙酚F型環氧樹脂，環氧當量160~170，在25℃下之黏度2000~2500mPa・s，DIC股份公司製，品名EPICLON835LV。 ・MEH8000H：在25℃下為液態之酚樹脂，25℃之黏度1500~3500mPa・s，明和化成股份公司製，型號MEH-8000H。 ・P-d：p-d型苯并
Figure 108143756-A0304-12-0059-1
Figure 108143756-A0304-12-0000-4
化合物，四國化成股份公司製。 ・2P4MHZ：2-苯基-4-羥甲基-5-甲基咪唑，型號2P4MHZ-PW，四國化成工業股份公司製。 ・己二酸：己二酸，熔點152~155℃，東京化成工業股份公司製。 ・琥珀酸：琥珀酸，熔點185~189℃，東京化成工業股份公司製。 ・TEA：三乙醇胺，熔點199℃，東京化成工業股份公司製。 ・胍：胍鹽酸鹽，熔點185~189℃，東京化成工業股份公司製。
2.評估 (1)硬化性 測定實施例1~10及比較例1~6之樹脂組成物在240℃下之凝膠時間。凝膠時間之測定係使用TA Instruments公司製流變計(DISCOVERY HR-2)。另，凝膠時間係至樹脂組成物(X)之儲存彈性模數與損耗模數成一致為止之時間。接著，以下述基準評估樹脂組成物之凝膠時間。將其結果列於下述表1及表2。 ・A：120秒以上且低於600秒(硬化性特別良好) ・B：60秒以上且低於120秒(硬化性良好) ・C：低於60秒或在600秒以上(具有硬化性)
(2)濡溼性 使用實施例1~10及比較例1~6之樹脂組成物，於銅製板上形成厚度0.1mm之膜。將熔點222℃之SAC305焊料成形為直徑0.35mm之球狀後，將該SAC305焊料置於膜上。接著，依每一膜及SAC305焊料將板在240℃下加熱3分鐘後，冷卻至室溫。接著確認SAC305焊料之俯視直徑(D)及高度尺寸(H)，並根據該結果求出以{(D-H)/D}×100(%)之算式算出之值。以該值作為濡溼性之指標。依以下基準評估該值。將其結果列於下述表1及表2。 ・A：55%以上(對焊料之濡溼性特別良好)。 ・B：40%以上且小於55%(對焊料之濡溼性良好)。 ・C：小於40%(對焊料具有濡溼性)。
(3)孔隙 由實施例1~10及比較例1~6之樹脂組成物製作硬化物。具體上，係於銅製板(2.5cm×2.5cm)上黏貼0.5mm厚之U字型矽橡膠並倒入樹脂組成物，從上蓋上載玻片(2.5cm×2.5cm厚度1mm)後以夾具固定以防樹脂組成物漏出。接著，將樹脂組成物在240℃之硬化爐中加熱20分鐘使其硬化，藉此製作出厚度0.5mm且大小2.0cm×2.0cm之硬化物。觀察該硬化物具有之孔隙(氣泡)，並按以下基準做評估。將其結果列於下述表1及表2。 ・A：孔隙數低於10個。 ・B：孔隙數為10個以上且低於30個。 ・C：孔隙數為30個以上。
(4)綜合評估 按以下基準評估上述硬化性、濡溼性及孔隙之評估結果。並將其結果列於下述表1及表2。 ・A：在硬化性、濡溼性及孔隙之評估中全部得A評價。 ・B：在硬化性、濡溼性及孔隙之評估中B評價為一個以上，無C評價。 ・C：在硬化性、濡溼性及孔隙之評估中C評價為一個以上。
[表1]
Figure 02_image005
[表2]
Figure 02_image007
1:安裝結構體 2:電路基板 3:電子零件 4:補強部 20:接合處 21:第1導體 30,32:凸塊 31:第2導體 100:電子零件 200:電子零件本體 210:導體
圖1係顯示將本揭示一實施形態之補強用樹脂組成物與焊料加熱時之回焊曲線一例的圖表。 圖2係顯示本揭示一實施形態之電子零件一例的概略截面圖。 圖3A~圖3C係顯示同上之電子零件之製造方法一例的概略截面圖。 圖4A~圖4C係顯示本揭示一實施形態之安裝結構體一例的概略截面圖。 圖5A~圖5C係顯示同上之安裝結構體之製造方法一例的概略截面圖。
4:補強部
20:接合處
30:凸塊
100:電子零件
200:電子零件本體
210:導體

Claims (10)

  1. 一種補強用樹脂組成物，包含： 環氧樹脂(A)、 酚樹脂(B)及 苯并
    Figure 108143756-A0304-12-0059-1
    Figure 108143756-A0304-12-0000-4
    化合物(C)。
  2. 如請求項1之補強用樹脂組成物，其更包含活性劑(D)。
  3. 如請求項2之補強用樹脂組成物，其中相對於前述環氧樹脂(A)、前述酚樹脂(B)、前述苯并
    Figure 108143756-A0304-12-0059-1
    Figure 108143756-A0304-12-0000-4
    化合物(C)及前述活性劑(D)之合計， 前述環氧樹脂(A)之比率為20重量%以上且60重量%以下， 前述酚樹脂(B)之比率為10重量%以上且40重量%以下， 前述苯并
    Figure 108143756-A0304-12-0059-1
    Figure 108143756-A0304-12-0000-4
    化合物(C)之比率為5重量%以上且30重量%以下， 前述活性劑(D)之比率為3重量%以上且40重量%以下。
  4. 如請求項2或3之補強用樹脂組成物，其中前述活性劑(D)包含熔點為130℃以上且220℃以下之有機酸(D1)及熔點為130℃以上且220℃以下之胺(D2)中之至少一者。
  5. 如請求項1或2之補強用樹脂組成物，其中前述酚樹脂(B)包含羥基當量為70g/eq以上且150g/eq以下之苯酚酚醛樹脂(B1)。
  6. 如請求項1或2之補強用樹脂組成物，其中前述苯并
    Figure 108143756-A0304-12-0059-1
    Figure 108143756-A0304-12-0000-4
    化合物(C)包含分子內具有多個
    Figure 108143756-A0304-12-0059-1
    Figure 108143756-A0304-12-0000-4
    環之多價
    Figure 108143756-A0304-12-0059-1
    Figure 108143756-A0304-12-0000-4
    化合物(C1)。
  7. 一種電子零件，具備： 電子零件本體； 導體，係形成在前述電子零件本體之表面上； 焊料製凸塊，係配置於前述導體上且與前述導體電連接；及 補強部，係如請求項1至6中任一項之補強用樹脂組成物的硬化物，且覆蓋前述導體與前述凸塊之接合處。
  8. 一種電子零件之製造方法，係如請求項7之電子零件之製造方法， 該方法係以如請求項1至6中任一項之補強用樹脂組成物覆蓋前述導體與前述凸塊之接合處後，使前述補強用樹脂組成物硬化。
  9. 一種安裝結構體，具備： 電路基板，其具備第1導體； 電子零件，其具備第2導體； 焊料製凸塊，其中介於前述第1導體與前述第2導體之間，且和前述第1導體與前述第2導體電連接；及 補強部，係如請求項1至6中任一項之補強用樹脂組成物的硬化物，且覆蓋前述第1導體與前述凸塊之接合處、及前述第2導體與前述凸塊之接合處中之至少一者。
  10. 一種安裝結構體之製造方法，係如請求項9之安裝結構體之製造方法， 該方法係以如請求項1至6中任一項之補強用樹脂組成物覆蓋前述第1導體與前述凸塊之接合處、及前述第2導體與前述凸塊之接合處中之至少一者後，使前述補強用樹脂組成物硬化。
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