TWI801488B - 樹脂組成物及其硬化物、電子零件用接著劑、半導體裝置,以及電子零件 - Google Patents
樹脂組成物及其硬化物、電子零件用接著劑、半導體裝置,以及電子零件 Download PDFInfo
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Abstract
本發明之目的在於提供硬化後,對於落下時之衝擊的抗性優異,耐溶劑性亦優異之樹脂組成物及其硬化物、包含該樹脂組成物之電子零件用接著劑、包含該樹脂組成物之硬化物的半導體裝置、以及電子零件。
該樹脂組成物之特徵係包含(A)氫化雙酚A型環氧樹脂、(B)多官能硫醇樹脂及(C)硬化觸媒,硬化物之50℃下之彈性模數為0.5GPa以上。較好為(B)成分包含甘脲化合物之樹脂組成物。
Description
本發明有關樹脂組成物及其硬化物、電子零件用接著劑、半導體裝置,以及電子零件。尤其有關適於電子零件用接著劑之樹脂組成物、包含該樹脂組成物之硬化物的半導體裝置,以及電子零件。
目前使用之行動終端等中內置有電子零件。對於該行動終端等有多種要求耐落下衝擊性(以下係對於落下時之衝擊的抗性)之用途。因此,對於電子零件之接著等所使用之樹脂組成物要求該等抗性。
另一方面,對於電子零件之接著等使用之樹脂組成物亦要求於製造步驟中,可耐受用以去除焊料助焊劑及灰塵等之洗淨步驟,亦即要求耐溶劑性。
過去以來,為了改善樹脂組成物對於落下時之衝擊的抗性,已知有利用硬化物之低玻璃轉移溫度化(低Tg化)之低彈性率化之方法(例如專利文獻1之第0009、0077、0079~0081段落)。以該方法,使樹脂之硬化物之交聯密度變低,而容易膨潤。因此,有使耐溶劑性變差的問題。然而,使硬化物高玻璃轉移溫度化(高Tg化)時,有使對於落下時之衝擊抗性劣化之問題。因此,不適於使用作為電子零件(例如音圈馬達(VCM、相機之對焦等所使用)或影像感測器模組等)用之接著劑。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2012-188628號公報
[發明欲解決之課題]
本發明係鑒於上述問題點而完成者。目的在於提供硬化後,對於落下時之衝擊的抗性優異,耐溶劑性亦優異之樹脂組成物及其硬化物、包含該樹脂組成物之電子零件用接著劑、包含該樹脂組成物之硬化物的半導體裝置、以及電子零件。
[用以解決課題之手段]
本發明人等為解決上述問題而進行檢討,發現包含(A)特定構造之環氧樹脂、(B)硫醇系硬化劑及(C)硬化觸媒之樹脂組成物可兼具對於落下時之衝擊的抗性與耐溶劑性兩者。
本發明有關藉由具有下述構成而解決了上述問題之樹脂組成物、電子零件用接著劑、半導體裝置以及電子零件。
[1] 一種樹脂組成物,其特徵係包含
(A)氫化雙酚A型環氧樹脂、
(B)多官能硫醇樹脂、及
(C)硬化觸媒,
硬化物之50℃下之彈性模數為0.5GPa以上。
[2] 如上述[1]之樹脂組成物,其中進而於20℃以上且未達50℃下之彈性模數為0.5GPa以上。
[3] 如上述[1]或[2]之樹脂組成物,其中硬化物之玻璃轉移溫度超過50℃。
[4] 如上述[1]至[3]中任一項之樹脂組成物,其中(B)成分包含分子中不具有酯鍵之多官能硫醇樹脂。
[5] 如上述[1]至[4]中任一項之樹脂組成物,其中(B)成分包含甘脲化合物。
[6] 如上述[5]之樹脂組成物,其中(B)成分之甘脲化合物相對於(B)成分100質量份為40~100質量份。
[7] 如上述[1]至[6]中任一項之樹脂組成物,其中進而包含氧化矽填料。
[8] 一種電子零件用接著劑,其包含如上述[1]至[7]中任一項之樹脂組成物。
[9] 一種如上述[1]至[7]中任一項之樹脂組成物的硬化物。
[10] 一種半導體裝置,其包含如上述[9]之硬化物。
[11] 一種電子零件,其包含如上述[9]之硬化物或如上述[10]之半導體裝置。
[發明效果]
依據本發明[1],可提供硬化後對於落下時之衝擊的抗性優異且耐溶劑性亦優異之樹脂組成物。依據本發明[8],可提供硬化後對於落下時之衝擊的抗性優異且耐溶劑性亦優異之電子零件用接著劑。
依據本發明[9],可提供耐落下衝擊性優異且耐溶劑性亦優異之樹脂組成物的硬化物。
依據本發明[10],可提供包含對於落下時之衝擊的抗性優異且耐溶劑性亦優異之樹脂組成物的硬化物之信賴性高的半導體裝置。依據本發明[11],可提供包含對於落下時之衝擊的抗性優異且耐溶劑性亦優異之樹脂組成物的硬化物之信賴性高的電子零件。
本發明之樹脂組成物(以下簡稱為樹脂組成物)之特徵係包含(A)氫化雙酚A型環氧樹脂、(B)多官能硫醇樹脂及(C)硬化觸媒,硬化物之50℃下之彈性模數為0.5GPa以上。
(A)成分之氫化雙酚A型環氧樹脂對樹脂組成物賦予硬化性、耐熱性、接著性、耐落下衝擊性、耐溶劑性等。又,氫化雙酚A亦稱為氫化雙酚A(HBPA)或2,2’-雙(4-羥基環己基)丙烷。(A)成分有時含有單官能體或二聚物作為雜質。相對於樹脂組成物中之環氧樹脂100質量份,(A)成分較好包含65質量份以上。又,更好包含70質量份以上。進而較好包含75質量份以上。(A)含量較少時,對於落下時之衝擊的抗性容易劣化。作為(A)成分之市售品舉例為三菱化學製氫化雙酚A型環氧樹脂(品名:YX8000、YX8034、YX8040)、共榮社化學製氫化雙酚A型環氧樹脂(品名:EPOLIGHT 4000)、新日本理化製氫化雙酚A型環氧樹脂(品名:RIKARESIN)等。(A)成分可單獨使用該等市售品,亦可併用兩種以上。
(B)成分之多官能硫醇樹脂對樹脂組成物賦予彈性、耐濕性。(B)成分若為2官能以上,則未特別限定,但基於耐濕性之觀點,較好為分子內不具有酯鍵之構造。(B)成分包含甘脲化合物時,由於分子骨架剛直且可提高彈性率,故而更好。作為甘脲化合物,舉例為以通式(1)表示者:
(式中,R1
及R2
分別獨立為氫、碳數1~10之烷基、或苯基,n為0~10之整數)。又,更好為化學式(2)或化學式(3)表示者:
又,作為分子中不具有酯鍵之多官能硫醇樹脂舉例為通式(4)表示者:
(式中,R3
、R4
、R5
及R6
分別獨立為氫或Cn
H2n
SH(n為2~6),且R3
、R4
、R5
及R6
之至少一個為Cn
H2n
SH(n為2~6))。通式(4)之硫醇化合物,基於硬化性之觀點,較好n為2~4。且基於硬化物物性與硬化速度之均衡觀點,更好係n為3之巰丙基。
作為(B)成分之市售品舉例為四國化成工業製硫醇甘脲衍生物(品名:TS-G(相當於化學式(2),硫醇當量:100g/eq)、C3 TS-G(相當於化學式(3),硫醇當量:114g/eq))、或SC有機化學製硫醇化合物(品名:PEPT(相當於化學式(4),硫醇當量:124g/eq))。(B)成分可單獨使用該等市售品,亦可併用兩種以上。
且,作為(B)成分,甘脲化合物相對於(B)成分100質量份,為40~100質量份時,就樹脂組成物之硬化後彈性模數之觀點而言較佳。且更好為50~100質量份。又更好為60~100質量份。
(C)硬化觸媒對樹脂組成物賦予硬化性。(C)成分若為一般硬化觸媒,則未特別限定,舉例為例如膦系、胺系等。
作為膦系硬化觸媒,舉例為三苯膦、三丁膦、三(對-甲基苯基)膦、三(壬基苯基)膦等。胺系硬化觸媒包含咪唑系硬化觸媒。作為胺系硬化觸媒舉例為2,4-二胺基-6-[2’-甲基咪唑基-(1’)]乙基-s-三嗪等之三嗪化合物、1,8-二氮雜雙環[5,4,0]十一碳烯-7(DBU)、1,4-二氮雜雙環[2.2.2]辛烷(DABCO)、三伸乙二胺、苄基二甲基胺、三乙醇胺等之三級胺化合物。且,作為咪唑硬化觸媒,舉例為2-甲基咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑等之咪唑化合物。基於於低溫快速硬化之觀點,較好為2-甲基咪唑或1,4-二氮雜雙環[2.2.2]辛烷(DABCO)。作為(C)成分之市售品舉例為「AMICURE PN-23」(味之素精密科技(股)商品名)、「AMICURE PN-40」(味之素精密科技(股)商品名)、「AMICURE PN-50」(味之素精密科技(股)商品名)、「HARDNER X-3661S」(ACR(股),商品名)、「HARDNER X-3670S」(ACR(股),商品名)、「NOVACURE HX-3742」(旭化成(股),商品名)、「NOVACURE HX-3721」(旭化成(股),商品名)、「NOVACURE HXA9322HP」(旭化成(股),商品名)、「NOVACURE HXA3922HP」(旭化成(股),商品名)、「NOVACURE HXA3932HP」(旭化成(股),商品名)、「NOVACURE HXA5945HP」(旭化成(股),商品名)、「NOVACURE HXA9382HP」(旭化成(股),商品名)、「FUJICURE FXR1121」(T&K TOKA(股),商品名)、「FUJICURE FXE-1000」(T&K TOKA(股),商品名)、「FUJICURE FXR-1030」(T&K TOKA(股),商品名)等,但未限定於該等。(C)成分可單獨使用該等市售品,亦可併用兩種以上。作為(C)成分,基於使用期限、硬化性之觀點,較好為潛在性硬化觸媒。
(A)成分相對於樹脂組成物100質量份,為10~70質量份時,基於樹脂組成物兼具對於落下時之衝擊的抗性與黏度之觀點係較好。且,更好為20~60質量份。又更好為30~60質量份。
(B)成分之硫醇當量,對於全部環氧基1當量,較好為0.5~2.5當量。且更好為0.5~2.0。又更好為0.5~1.5。特佳為0.8~1.2。藉由將(B)成分之硫醇當量與全部環氧基當量設為上述範圍內(亦即樹脂組成物中之硫醇基總數與全部環氧基之總數為上述範圍內),可防止硬化後之樹脂組成物硬度不足及韌性不足。
(C)成分相對於包含(A)成分之全部環氧樹脂及(B)成分之合計100質量份,較好含有0.1~10質量份,更好為0.3~10質量份,又更好為0.5~10質量份。若為0.1質量份以上,則反應性良好。若為5質量份以下,則耐熱性良好,進而增黏倍率安定。又,(C)成分有時以分散於環氧樹脂之分散液形態提供。使用此等形態之(C)成分時,應注意需將使其分散之環氧樹脂量自(C)成分去除。
樹脂組成物進而包含(D)無機填料時,由於防止垂流而較佳,適合作為分散用。作為(D)成分,基於作業性之觀點,較好為球狀。(D)成分較好為氧化矽或氧化鋁。
作為氧化矽粉末舉例為熔融氧化矽、普通矽石、球狀氧化矽、破碎氧化矽、結晶性氧化矽、非晶質氧化矽等。
(D)成分之平均粒徑並未特別限定,但較好為0.1~15μm。此係基於(D)成分對於樹脂組成物中之分散性及樹脂組成物之低黏度化之觀點。未達0.1μm時,樹脂組成物之黏度上升,有樹脂組成物之作業性劣化之虞。超過15μm時,有(D)成分難以於樹脂組成物中均一分散之虞。作為市售之氧化矽粉末(氧化矽填料),舉例為ADMATECHS製氧化矽(製品名:SO-E2,平均粒徑:0.5 μm)、龍森製氧化矽(製品名:MP-8FS,平均粒徑:0.7 μm)、DENKA製氧化矽(品名:FB-5D,平均粒徑:5μm)等。(D)成分可單獨使用該等市售品,亦可併用兩種以上。
基於進一步高彈性率化提高耐溶劑性之觀點,(D)成分相對於樹脂組成物100質量份,較好為0~40質量份。多於40質量份時,由於相對地樹脂成分減少,故有耐落下衝擊性劣化之虞。
於不損及本發明目的之範圍內,樹脂組成物中可進而根據需要調配安定化劑(例如有機酸、硼酸酯、金屬螯合劑)、碳黑、鈦黑、矽烷偶合劑、離子捕捉劑、調平劑、抗氧化劑、消泡劑、搖變劑、其他添加劑等。又樹脂組成物中亦可調配黏度調整劑、難燃劑或溶劑等。
樹脂組成物可藉由將例如(A)成分~(C)成分及其他添加劑等同時或分別於根據需要下邊加以加熱處理邊攪拌、熔融、混合、分散而獲得。作為該等混合、攪拌、分散等之裝置並未特別限制,但可使用具備攪拌、加熱裝置之擂潰機、亨歇爾混合機、3輥研磨機、球磨機、行星式混合機、珠磨機等。又,該等裝置可適當組合使用。
如此所得之樹脂組成物為熱硬化性。樹脂組成物之熱硬化較好於60~90℃進行30~120分鐘。
本發明之樹脂組成物的硬化物於50℃下之彈性模數為0.5GPa以上。如以往,於將硬化物之玻璃轉移溫度設為室溫以下,降低室溫下之彈性模數而實現耐落下衝擊性之提高時,若進一步使溫度降低至比玻璃轉移溫度低,則會使彈性模數顯著上升,使對於落下時之衝擊的抗性劣化。本發明之樹脂組成物之硬化物係玻璃轉移溫度超過50℃者。因此,即使於室溫下,進一步降低溫度,由於彈性模數之變化較小,進而因使用(A)成分,故對於落下時之衝擊的抗性優異。又,於電子零件之洗淨步驟,大多使用超音波洗淨。因此,於超音波洗淨會有發生熱,而使所使用的溶劑溫度上升至50℃附近的情況。因此,樹脂組成物之硬化物於50℃下之彈性模數未達0.5GPa時,會使耐溶劑性劣化。如此,於20℃以上且未達50℃下之彈性模數非0.5GPa以上時,耐溶劑性容易劣化,但本發明之樹脂組成物之硬化物係玻璃轉移溫度超過50℃者。亦即於20℃以上且未達50℃下之彈性模數為0.5GPa以上。因此,耐溶劑性不會劣化。本發明之樹脂組成物之硬化物於50℃下之彈性模數更好為0.8GPa以上。又更好為1GPa以上。特佳為1.5 GPa以上。且樹脂組成物之硬化物於50℃下之彈性模數上限較好為6GPa以下。且更好為5GPa以下。又更好為4GPa以下。
[電子零件用接著劑]
本發明之電子零件用接著劑包含上述樹脂組成物。
(樹脂組成物之硬化物)
本發明之樹脂組成物之硬化物係上述樹脂組成物之硬化物。
[半導體裝置、電子零件]
本發明之半導體裝置由於包含上述樹脂組成物之硬化物,故對於落下時之衝擊的抗性優異。且信賴性高。
本發明之電子零件由於包含上述硬化物或上述之半導體裝置,故對於落下時之衝擊的抗性優異,且信賴性高。
[實施例]
以下,針對本發明藉由實施例加以說明,但本發明並非限定於此。又,以下實施例中,份、%只要未特別說明,則表示質量份、質量%。
(A)成分之氫化雙酚A型環氧樹脂使用三菱化學製氫化雙酚A型環氧樹脂(品名:YX8000,環氧當量:205g/eq),(A’)成分之氫化雙酚A型環氧樹脂使用三菱化學製雙酚A型環氧樹脂(品名828EL,環氧當量:173g/eq),(A’)成分之矽氧烷骨架環氧樹脂使用Momentive Performance Materials Inc.製矽氧烷骨架環氧樹脂(品名:TSL9906,環氧當量:181g/eq),(B)成分之(B-1)C3 TS-G使用四國化成工業製甘脲衍生物(品名:C3 TS-G,硫醇當量:114g/ eq),(B-2)PEPT使用SC有機化學製硫醇化合物(品名:PEPT,硫醇當量:124g/eq),(B-3)PEMP使用SC有機化學製季戊四醇肆(3-巰基丙酸酯)(商品名:PEMP,硫醇當量:128g/eq),(C)成分之(C-1)硬化觸媒使用T&K TOKA製硬化觸媒(品名:FXR1211),(C-2)硬化觸媒使用旭化成製硬化觸媒(品名:HXA3922),(D)成分之氧化矽使用ADMATECHS製氧化矽(品名:SO-E2,平均粒徑:0.5 μm),矽烷偶合劑使用信越化學工業製3-縮水甘油氧基丙基三甲氧基矽烷(品名:KBM-403)。
[實施例1~8、比較例1~3]
以表1、2所示之調配混合原料後,於室溫使用3輥混合機予以分散。藉此製作實施例1~8、比較例1~3之樹脂組成物。
(對於落下時之衝擊的抗性測定)
<<耐落下衝擊試驗之測定所用之構件>>
・構件1:SUS基板
・構件2:Ni包覆塊,尺寸:寬:9mm×長:9mm×厚:4mm
<<耐落下衝擊試驗之測定方法>>
(i)於SUS基板上,塗佈所調製之樹脂組成物(試料)作為接著劑。塗佈樣品尺寸為寬:9mm×長:9mm×厚:0.3 mm。
(ii)於塗佈之試料上載置Ni包覆塊,作為試驗片。
(iii)將試驗片投入加熱至80℃之烘箱中,使試料加熱硬化30分鐘。
(iv)將試料加熱硬化後,自烘箱取出試驗片,於室溫使用落下衝擊試驗機(日立技術服務公司製),將Ni包覆塊自SUS板剝離之高度設為落下高度。落下高度係自200mm開始,每次升高100mm高度直至500mm。500mm以上則逐次升高50mm高度,進行試驗。又落下次數係對每高度進行5次,若未剝離則以下一高度進行試驗。結果示於表1、2。耐落下衝擊性之高度較好為450mm,更好為600mm以上。
(彈性模數之測定)
於不鏽鋼板(SUS-304製,平滑板:40mm×60mm×0.3 mm)上,以硬化時之膜厚成為500±100μm之方式塗佈樹脂組成物形成塗膜。之後,於80℃放置1小時使之硬化。將該塗膜自不鏽鋼板剝離後,以切割器切取為特定尺寸(5 mm×40mm)。又,切口以砂紙修飾為平滑。該塗膜依據JIS C6481使用精工儀器公司製之動態熱機械測定(DMA),利用拉伸法於頻率10Hz進行測定。表1、2中顯示50℃之儲存彈性模數。表1、2中雖未記載,但實施例1~6之彈性模數即使於0℃仍未大幅變化。且,藉由DMA測定所得之損失彈性模數/儲存彈性模數之最大值的溫度設為玻璃轉移溫度,結果所有實施例中玻璃轉移溫度均超過50℃。另一方面,比較例3之彈性模數,於設為0℃時,彈性率變高。圖1中顯示實施例6、7及比較例3之DMA圖譜。
(耐溶劑性之評價)
(i)於LCP基板上,塗佈所調製之樹脂組成物(試料)作為接著劑。塗佈尺寸為2φmm。
(ii)於塗佈之試料上,載置3.2mm×1.6mm×0.45mm厚之氧化鋁片,作為試驗片。
(iii)將試驗片投入加熱至80℃之烘箱中,使試料加熱硬化30分鐘。
(iv)試驗片於二醇醚系溶劑中於50℃含浸30分鐘後,自溶劑取出試驗片以純水進行清洗。隨後,將經清洗之試驗片於80℃乾燥1小時。
(v)經乾燥之試驗片於室溫測定剪切強度。60N以上為合格。
如表1、2所知,使用包含(A)~(C)成分之樹脂組成物的所有實施例1~8,彈性模數均為0.5GPa以上,且耐落下衝擊性之值亦良好。彈性模數為0.5GPa以上的實施例中,進行耐溶劑性試驗之實施例2、6及7於耐溶劑性之評價中剪切強度均為100N以上,如表3所示,可確認耐溶劑性之評價結果為良好。相對於此,不包含(A)成分之比較例1,耐落下衝擊性差。50℃之彈性模數過低之比較例2,雖包含(A)成分,但由於彈性模數低,故耐溶劑性差。不包含(A)成分之比較例3,由於彈性模數低,故耐溶劑性差。
本發明之樹脂組成物由於硬化後之耐落下衝擊性優異,耐溶劑性亦優異,故非常有用。包含該樹脂組成物之硬化物的半導體裝置、電子零件對於落下時之衝擊的抗性優異,為高信賴性。
圖1係實施例6、7及比較例3之DMA圖譜。
Claims (10)
- 一種樹脂組成物,其係包含(A)氫化雙酚A型環氧樹脂、(B)多官能硫醇樹脂、及(C)硬化觸媒,且前述樹脂組成物的硬化物之50℃下之彈性模數為0.5GPa以上,相對於樹脂組成物100質量份,含有30~60質量份的前述(A)成分,前述(B)成分包含甘脲化合物。
- 如請求項1之樹脂組成物,其中進而於20℃以上且未達50℃下之彈性模數為0.5GPa以上。
- 如請求項1或2之樹脂組成物,其中硬化物之玻璃轉移溫度超過50℃。
- 如請求項1或2之樹脂組成物,其中(B)成分之甘脲化合物相對於(B)成分100質量份為40~100質量份。
- 如請求項1或2之樹脂組成物,其中進而包含氧化矽填料。
- 一種電子零件用接著劑,其包含如請求項1至6中任一項之樹脂組成物。
- 一種如請求項1至6中任一項之樹脂組成物的硬化物。
- 一種半導體裝置,其包含如請求項8之硬化物。
- 一種電子零件,其包含如請求項8之硬化物或如請求項9之半導體裝置。
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