TW202142632A - 導電性組成物及使用其之屏蔽封裝體之製造方法 - Google Patents
導電性組成物及使用其之屏蔽封裝體之製造方法 Download PDFInfo
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Abstract
本發明係提供一種可藉由噴塗形成對100MHz~40GHz之電磁波具有良好的屏蔽性、且與封裝體之密著性及雷射標記辨識性良好的屏蔽層的導電性組成物、及使用該導電性組成物的屏蔽封裝體之製造方法。
一種導電性組成物,至少含有:(A)重量平均分子量為1000以上且40萬以下之(甲基)丙烯酸系樹脂;(B)於分子內具有環氧丙基及/或(甲基)丙烯醯基之單體;(C)平均粒徑為10nm~700nm之粒狀樹脂成分;(D)平均粒徑為10~500nm之導電性填料;(E)平均粒徑為1~50μm之鱗片狀導電性填料;(F)自由基聚合引發劑;(G)環氧樹脂硬化劑;且於包含上述丙烯酸系樹脂(A)、上述單體(B)及上述粒狀樹脂成分(C)之樹脂成分中,上述粒狀樹脂成分(C)之含有比率為3~27質量%;上述導電性填料(D)與上述導電性填料(E)之合計含量相對於上述樹脂成分100質量份為2000~12000質量份;上述自由基聚合引發劑(F)之含量相對於上述樹脂成分100質量份為0.5~40質量份;上述環氧樹脂硬化劑(G)之含量相對於前述樹脂成分100質量份為0.5~40質量份。
Description
本發明係關於導電性組成物及使用其之屏蔽封裝體之製造方法。
背景技術
於輔助汽車之駕駛操作之先進駕駛輔助系統(ADAS)中,就像人類行動一樣,藉由高精度地進行「認知」、「判斷」、「操作」而實現安全的行駛。其中,在如同人類的眼睛般進行「認知」之感測器、具體而言進行前方監視或周邊監視之感測器方面,採用了使用高頻範圍電磁波的毫米波雷達的感測器,其使用量正在增加。又,伴隨著第五代移動通信系統(5G)的普及,在行動電話或平板電腦等中高頻範圍電磁波的利用亦正在增加。
伴隨著利用此種高頻範圍電磁波的增加,恐有電子零件因為高頻範圍電磁波而產生錯誤動作之虞,故要求可形成對高頻範圍電磁波、例如100MHz~40GHz之電磁波具有屏蔽性的屏蔽層的導電性組成物。
又,於塗佈導電性組成物之封裝體之表面,會有將序號或型號等雷射標記之情形。因此,為了可利用條碼讀取器等隔著屏蔽層讀取已施於封裝體表面的雷射標記,屏蔽層需要由薄膜形成。另一方面,若屏蔽層越薄,屏蔽性有越差的傾向,故要求可形成兼具對高頻範圍電磁波的屏蔽性與雷射標記辨識性的屏蔽層的導電性組成物。
於專利文獻1中記載有一種導電性樹脂組成物,其係可利用噴塗形成對10MHz~1000MHz之電磁波具有良好屏蔽性的屏蔽層的導電性組成物,且所獲得的屏蔽層與封裝體之密著性良好。
然而,於專利文獻1中並未就兼具對超過1000MHz之高頻範圍電磁波的屏蔽性與雷射標記辨識性有所記載。進而,就屏蔽層與封裝體之密著性方面,市場的需求正在提高,要求進一步改善。
先行技術文獻
專利文獻
[專利文獻1] 國際公開2019/009124號公報
發明概要
發明欲解決之課題
本發明係鑑於上述而完成者,其目的在於提供一種導電性組成物,係可利用噴塗形成對100MHz~40GHz之電磁波具有良好屏蔽性的屏蔽層者,且獲得之屏蔽層與封裝體之密著性及雷射標記辨識性良好。又,本發明之目的在於提供一種可容易地形成上述屏蔽層的屏蔽封裝體之製造方法。
用以解決課題之手段
本發明之導電性組成物至少含有:(A)重量平均分子量為1000以上且40萬以下之(甲基)丙烯酸系樹脂;(B)於分子內具有環氧丙基及/或(甲基)丙烯醯基之單體;(C)平均粒徑為10nm~700nm之粒狀樹脂成分;(D)平均粒徑為10~500nm之導電性填料;(E)平均粒徑為1~50μm之鱗片狀導電性填料;(F)自由基聚合引發劑;(G)環氧樹脂硬化劑;且於包含上述丙烯酸系樹脂(A)、上述單體(B)及上述粒狀樹脂成分(C)之樹脂成分中,上述粒狀樹脂成分(C)之含有比率為3~27質量%;上述導電性填料(D)與上述導電性填料(E)之合計含量相對於上述樹脂成分100質量份為2000~12000質量份;上述自由基聚合引發劑(F)之含量相對於上述樹脂成分100質量份為0.5~40質量份;上述環氧樹脂硬化劑(G)之含量相對於上述樹脂成分100質量份為0.5~40質量份。
上述環氧樹脂硬化劑(G)可為選自於由酚系硬化劑、咪唑系硬化劑、胺系硬化劑及陽離子系硬化劑所構成群組中之至少一種。
上述粒狀樹脂成分(C)可為選自於由聚丁二烯橡膠、聚矽氧及苯乙烯丁烯橡膠所構成群組中之至少一種。
上述鱗片狀導電性填料(E)之縱橫比可為5~20。
上述單體(B)可為於分子內具有環氧丙基及(甲基)丙烯醯基者。
上述導電性填料(D)與上述導電性填料(E)之含有比率((D):(E))可為以質量比計為5:1~1:10。
本發明之屏蔽封裝體之製造方法,係製造藉由屏蔽層被覆封裝體而成之屏蔽封裝體,該封裝體係於基板上搭載有電子零件且該電子零件已藉密封材所密封者;上述屏蔽封裝體之製造方法至少具有以下步驟:於基板上搭載複數個電子零件,且於該基板上填充密封材並使之硬化,藉此將上述電子零件密封之步驟;於上述複數個電子零件間切削密封材,形成槽部,藉由該等槽部使基板上之各電子零件之封裝體個別化之步驟;於上述經個別化之封裝體之表面,藉由噴霧塗佈上述導電性組成物之步驟;將於上述封裝體之表面塗佈有導電性組成物之基板加熱,使上述導電性組成物硬化,藉此形成屏蔽層之步驟;及沿著上述槽部將上述基板切斷,藉此獲得單片化之屏蔽封裝體之步驟。
發明效果
根據本發明之導電性組成物,可藉由噴塗法形成均勻厚度之塗膜,且獲得之塗膜可保護封裝體,避免100MHz~40GHz之電磁波。然後,藉由將本發明之導電性組成物噴塗於封裝體表面,可容易地形成屏蔽性優異、且與封裝體之密著性及雷射標記辨識性優異之屏蔽層。
又,根據本發明之屏蔽封裝體之製造方法,不使用大型裝置就能有效率地製造上述屏蔽性、與封裝體之密著性優異的屏蔽封裝體。
用以實施發明之形態
本發明之導電性組成物如上所述至少含有:(A)重量平均分子量為1000以上且40萬以下之(甲基)丙烯酸系樹脂;(B)於分子內具有環氧丙基及/或(甲基)丙烯醯基之單體;(C)平均粒徑為10nm~700nm之粒狀樹脂成分;(D)平均粒徑為10~500nm之導電性填料;(E)平均粒徑為1~50μm之鱗片狀導電性填料;(F)自由基聚合引發劑;(G)環氧樹脂硬化劑;且於包含上述丙烯酸系樹脂(A)、上述單體(B)及上述粒狀樹脂成分(C)之樹脂成分中,上述粒狀樹脂成分(C)之含有比率為3~27質量%;上述導電性填料(D)與上述導電性填料(E)之合計含量相對於上述樹脂成分100質量份為2000~12000質量份;上述自由基聚合引發劑(F)之含量相對於上述樹脂成分100質量份為0.5~40質量份;上述環氧樹脂硬化劑(G)之含量相對於上述樹脂成分100質量份為0.5~40質量份。
該導電性組成物之用途並無特別限定,但適合使用在利用噴塗等霧狀地噴射於單片化前之封裝體或經單片化之封裝體的表面形成屏蔽層,獲得屏蔽封裝體。
上述(甲基)丙烯酸系樹脂(A)係至少包含丙烯酸酯及/或甲基丙烯酸酯作為構成單體的聚合物,並無特別限定,但例如可使用含有選自於由下列所構成群組中之至少一種作為構成單體的聚合物:丙烯酸甲酯、丙烯酸乙酯、丙烯酸丙酯、丙烯酸正丁酯、甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丙酯及甲基丙烯酸正丁酯。關於構成單體,於不違反本發明目的之範圍內亦可包含丙烯酸酯或甲基丙烯酸酯以外的構成單體。含有二種以上單體時,可為交替共聚物、亦可為無規共聚物、亦可為嵌段共聚物、亦可為接枝共聚物。此處,所謂「(甲基)丙烯酸系樹脂」係「丙烯酸系樹脂」及「甲基丙烯酸系樹脂」的總稱。
上述(甲基)丙烯酸系樹脂(A)的重量平均分子量係1000以上、宜為5000以上、較佳為7000以上、更佳為10000以上。又,為40萬以下、宜為20萬以下、較佳為15萬以下、更佳為5萬以下。重量平均分子量為1000以上時,導電性組成物之黏度易成為適合噴塗的黏性,易獲得導電性填料優異的分散性。又,重量平均分子量為40萬以下時,導電性提高,易獲得優異的屏蔽性。
再者,於本說明書中,所謂「重量平均分子量」可藉由凝膠滲透層析法(GPC)進行測定,為使用四氫呋喃作為流動相,使用換算成聚苯乙烯之校準曲線算出之值。
關於此種(甲基)丙烯酸系樹脂,例如可使用日本特開2016-155920號公報、日本特開2015-59196號公報、日本特開2016-196606號公報、WO2016/132814之燒成糊料用共聚物等。又,亦可使用市售的丙烯酸系樹脂,例如可使用共榮公司化學(股)製「KC-1100」或「KC-1700P」。
(甲基)丙烯酸系樹脂(A)之含量於樹脂成分中宜為1~70質量%、較佳為10~65質量%、更佳為15~60質量%。
上述單體(B)為於分子內具有環氧丙基及/或(甲基)丙烯醯基之化合物,較佳為於分子內具有環氧丙基及(甲基)丙烯醯基之化合物。再者,於本說明書中,「單體(B)」係亦包含低聚物或分子量小於1000之預聚物者。
上述單體(B)具有環氧丙基時,環氧丙基當量並無特別限定,但宜為100~300g/eq、較佳為150~250g/eq。又,上述單體(B)具有(甲基)丙烯醯基時,(甲基)丙烯醯基當量並無特別限定,但宜為100~300g/eq、較佳為150~250g/eq。再者,該環氧丙基當量及(甲基)丙烯醯基當量為理論值,但視情況亦可為以公知方法求出者。
關於具有環氧丙基之化合物並無特別限定,例如可列舉:乙基環氧丙基醚、丁基環氧丙基醚、三級丁基環氧丙基醚、烯丙基環氧丙基醚、芐基環氧丙基醚、環氧丙基苯基醚、雙酚A、二環氧丙基醚等環氧丙基化合物等。
關於具有(甲基)丙烯醯基之化合物,只要為具有丙烯醯基或甲基丙烯醯基之化合物即可,並無特別限定,例如可列舉:丙烯酸異戊酯、新戊二醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、二-三羥甲基丙烷四丙烯酸酯、2-羥基-3-丙烯醯氧基丙基甲基丙烯酸酯、乙二醇二甲基丙烯酸酯及二乙二醇二甲基丙烯酸酯等。
關於具有環氧丙基及(甲基)丙烯醯基之化合物,例如可列舉:丙烯酸環氧丙基醚、甲基丙烯酸環氧丙基醚、4-羥丁基丙烯酸酯環氧丙基醚、雙酚A二環氧丙基醚丙烯酸加成物、苯基環氧丙基醚丙烯酸酯六亞甲基二異氰酸酯胺基甲酸酯預聚物等。
此等單體(B)可單獨使用一種,亦可併用二種以上。於導電性組成物使用丙烯酸系樹脂時,有加熱硬化後之屏蔽層與封裝體之密著性變差之傾向,但藉由併用上述單體(B),即使為高度添加上述導電性填料(D)及上述導電性填料(E)之情形,仍可獲得屏蔽層與封裝體之優異密著性。
上述單體(B)之含量於樹脂成分中宜為5~80質量%、較佳為10~50質量%、更佳為15~40質量%。
關於粒狀樹脂成分(C)只要平均粒徑為10nm~700nm,並無特別限定,但例如可列舉由聚丁二烯橡膠、聚矽氧及苯乙烯丁烯橡膠等構成者。由提高分散性之觀點,粒狀樹脂成分(C)亦可作為預先分散於液狀硬化性樹脂之母料,添加於導電性組成物中。關於液狀硬化性樹脂,宜為環氧樹脂,具體而言可列舉:雙酚A型環氧樹脂、雙酚F型環氧樹脂、苯酚酚醛型環氧樹脂、雙酚A酚醛型環氧樹脂、溴化環氧樹脂、環氧丙基胺型環氧樹脂等。液狀硬化性樹脂之環氧丙基當量並無特別限定,但宜為80~400g/eq、較佳為100~300g/eq。再者,該環氧丙基當量為理論值,但視情況亦可為以公知方法求出者。
於此,本說明書中,所謂「平均粒徑」係指利用雷射繞射散射法測得的以個數為基準的平均粒徑D50(中值粒徑)。
粒狀樹脂成分(C)之含量只要於樹脂成分中為3~27質量%,則並無特別限定,但宜為5~16.5質量%。粒狀樹脂成分(C)之含量為3質量%以上時,分散於導電性組成物中之粒狀樹脂成分(C)可吸收燒成時因導電性填料燒結而於屏蔽層內產生的應力,藉此容易獲得優異的密著性,在粒狀樹脂成分(C)之含量為27質量%以下時,可無損導電性,容易獲得優異的屏蔽性。
含有上述液狀硬化性樹脂時,其含量並無特別限定,但於樹脂成分中宜為6~55質量%、較佳為10~35質量%。
關於平均粒徑為10~500nm之導電性填料(D)並無特別限定,但宜為銅奈米粒子、銀奈米粒子、金奈米粒子。藉由導電性填料(D)之平均粒徑為10~500nm,由於可填充微米尺寸之導電性填料彼此的間隙,故容易大量添加導電性填料,可提高對100MHz~40GHz之電磁波的屏蔽性。
導電性填料(D)之含量並無特別限定,但宜相對於樹脂成分100質量份為400~10000質量份、較佳為2000~7000質量份、更佳為2200~7000質量份、尤佳為2500~6000質量份。若含量為400質量份以上,屏蔽層之導電性為良好,即使基於雷射標記辨識性之觀點而減薄塗佈膜厚,仍容易獲得優異的屏蔽性,若含量為10000質量份以下,則屏蔽層與封裝體之密著性、尤其是後述角摩耗試驗中亦容易獲得優異的密著性,容易使硬化後之導電性組成物之物性變為良好。
關於平均粒徑為1~50μm之鱗片狀導電性填料(E)並無特別限定,但較佳為銅粉、銀粉、金粉、銀被覆銅粉或銀被覆銅合金粉,由降低成本之觀點,更佳為銅粉、銀被覆銅粉或銀被覆銅合金粉。若導電性填料(E)之平均粒徑為1μm以上,導電性填料(E)之分散性為良好,可防止凝集,且容易被氧化,若為平均粒徑為50μm以下,封裝體與接地電路之連接性與雷射標記辨識性良好。
銀被覆銅粉係具有銅粉、與被覆該銅粉粒子之至少一部分的銀層或含銀層者,銀被覆銅合金粉係具有銅合金粉、與被覆該銅合金粒子之至少一部分的銀層或含銀層者。銅合金粒子例如鎳含量為0.5~20質量%、且鋅含量為1~20質量%、剩餘部分由銅構成,剩餘部分的銅亦可包含不可避免的雜質。藉由如此使用具有銀被覆層的銅合金粒子,可獲得屏蔽性及耐變色性優異的屏蔽封裝體。
鱗片狀導電性填料(E)之振實密度宜為4.0~6.5g/cm3
。若振實密度於上述範圍內,屏蔽層的導電性更為良好。
又,鱗片狀導電性填料(E)之縱橫比宜為5~20。若縱橫比於上述範圍內,屏蔽層的導電性更為良好。
導電性填料(E)之含量並無特別限定,但相對於樹脂成分100質量份,宜為400~10000質量份、較佳為1500~8000質量份、更佳為2000~7000質量份、尤佳為2500~6000質量份。若含量為400質量份以上,屏蔽層之導電性變得良好,容易獲得對100MHz~40GHz之電磁波優異的屏蔽性,若含量為10000質量份以下,屏蔽層與封裝體之密著性及硬化後之導電性組成物之物性容易變得良好,於利用後述切割機進行切斷時屏蔽層不易產生缺損。
上述導電性填料(D)與上述導電性填料(E)之合計含量係相對於樹脂成分100質量份為2000~12000質量份、宜為3000~12000質量份、較佳為5000~11000質量份、更佳為5500~10000質量份。藉由含量為2000質量份以上,即使基於雷射標記辨識性之觀點而減薄塗佈膜厚,仍容易獲得優異的屏蔽性,藉由含量為12000質量份以下,則容易獲得屏蔽層與封裝體之優異的密著性。
導電性填料(D)與導電性填料(E)之含有比率(導電性填料(D):導電性填料(E))並無特別限定,但宜以質量比計為5:1~1:10。
關於自由基聚合引發劑(F)並無特別限定,例如可使用藉由加熱而使自由基聚合開始之熱聚合引發劑、或藉由能量線照射而使自由基聚合開始之能量線聚合引發劑。
熱聚合引發劑並無特別限制,可適當使用先前使用的有機過氧化物系或偶氮系化合物。
關於有機過氧化物系聚合引發劑,例如可列舉:甲基乙基酮過氧化物、環己酮過氧化物、甲基環己酮過氧化物、甲基乙醯乙酸酯過氧化物、乙醯基乙酸酯過氧化物、1,1-雙(三級己基過氧)-3,3,5-三甲基環己烷、1,1-雙(三級己基過氧)-環己烷、1,1-雙(三級丁基過氧)-3,3,5-三甲基環己烷、1,1-雙(三級丁基過氧)-2-甲基環己烷、1,1-雙(三級丁基過氧)-環己烷、1,1-雙(三級丁基過氧)環十二烷、過氧化苯甲酸三級己酯、2,5-二甲基-2,5-雙(苯甲醯基過氧)己烷、三級丁基過氧烯丙基單碳酸酯、三級丁基三甲基矽基過氧化物、3,3',4,4'-四(三級丁基過氧羰基)二苯基酮、2,3-二甲基-2,3-二苯基丁烷等。
又,作為偶氮系聚合引發劑,例如可列舉:2-苯基偶氮-4-甲氧基-2,4-二甲基戊腈、1-[(1-氰基-1-甲基乙基)偶氮]甲醯胺、1,1'-偶氮雙(環己烷-1-甲腈)、2,2'-偶氮雙(2-甲基丁腈)、2,2'-偶氮雙異丁腈、2,2'-偶氮雙(2,4-二甲基戊腈)、2,2'-偶氮雙(2-甲基丙脒)二鹽酸鹽、2,2'-偶氮雙(2-甲基-N-苯基丙脒)二鹽酸鹽,2,2'-偶氮雙[N-(4-氯苯基)-2-甲基丙脒]二氫氯化物、2,2'-偶氮雙[N-(4-氫苯基)-2-甲基丙脒]二鹽酸鹽、2,2'-偶氮雙[2-甲基-N-(苯基甲基)丙脒]二鹽酸鹽、2,2'-偶氮雙(異丁酸)二甲酯。
上述熱聚合引發劑可單獨使用一種,亦可併用二種以上。
自由基聚合引發劑(F)之含量相對於樹脂成分100質量份為0.5~40質量份、宜為2~30質量份、較佳為5~20質量份。於自由基聚合引發劑之含量為上述範圍內時,導電性組成物之硬化足夠、屏蔽層與封裝體表面之密著性與屏蔽層之導電性變得良好,容易獲得屏蔽性優異的屏蔽層。又,藉由選擇自由基聚合引發劑的種類或量,可以做到因應縮短硬化時間或室溫下的長期保存穩定性等目的的使用。
環氧樹脂硬化劑(G)並無特別限定,例如可列舉:酚系硬化劑、咪唑系硬化劑、胺系硬化劑、陽離子系硬化劑等。此等可單獨使用一種,亦可併用二種以上。
關於酚系硬化劑,例如可列舉:酚醛苯酚、萘酚系化合物等。
關於咪唑系硬化劑,例如可列舉:咪唑、2-十一烷基咪唑、2-十七烷基咪唑、2-甲基咪唑、2-乙基咪唑、2-苯基咪唑、1-苄基-2-苯基咪唑、2-乙基-4-甲基-咪唑、1-氰乙基-2-十一烷基咪唑。
關於陽離子系硬化劑之例,可列舉以下列諸等為代表的鎓系化合物:三氟化硼的胺鹽、P-甲氧基苯重氮鎓六氟磷酸鹽、二苯基錪六氟磷酸鹽、三苯基鋶鹽、四正丁基鏻四苯硼酸鹽、四正丁基鏻-o, o-二乙基二硫代磷酸鹽。
環氧樹脂硬化劑(G)之含量相對於樹脂成分100質量份為0.5~40質量份、宜為1~20質量份、較佳為2~15質量份。硬化劑之含量為0.5質量份以上時,屏蔽層與封裝體表面之密著性優異,屏蔽層之導電性變得良好,容易獲得屏蔽性優異的屏蔽層,硬化劑之含量為40質量份以下時,容易獲得保存安定性優異的導電性組成物。
又,於無損發明目的之範圍內,於本發明之導電性組成物中亦可添加消泡劑、增稠劑、黏著劑、填充劑、阻燃劑、著色劑等周知的添加劑。
本發明之導電性組成物為了可利用噴霧將導電性組成物均勻地塗佈於封裝體表面,宜為相較於所謂的導電性糊料為更低的黏度。
本發明之導電性組成物的黏度宜根據用途或塗佈所使用的機器而適當調整,並無特別限定,但作為一般的標準如下所述。黏度的測定方法亦不限定,但若導電性樹脂組成物為低黏度,可以圓錐平板型旋轉黏度計(所謂錐板式黏度計)進行測定,若為高黏度,則可以單一圓筒形旋轉黏度計(所謂B型或BH型黏度計)進行測定。
以圓錐平板型旋轉黏度計進行測定時,使用布魯克菲爾德(BROOK FIELD)公司之錐板心軸CP40(錐板角度:0.8°、錐板半徑:24mm),以10rpm測得的黏度宜為10mPa・s以上、較佳為30mPa・s以上。若黏度為10mPa・s以上,可防止在塗佈面並非水平時滴液,容易無不均地形成導電性塗膜。再者,黏度在10mPa・s附近或比10mPa・s低時,為了獲得期望厚度的均一塗膜,有效的方法是進行所謂的重複塗佈,即反覆如下操作:每一次的塗佈量為少量來形成薄膜,並於薄膜上再形成薄膜。又,只要為可利用圓錐平板型旋轉黏度計測定的黏度,再高也沒有問題。
以單一圓筒形旋轉黏度計進行測定時,使用轉子No.2以10rpm測得的黏度宜為10dPa・s以下、較佳為5dPa・s以下。若為10dPa・s以下,可防止噴嘴阻塞,容易無不均地形成導電性塗膜。又,只要為可利用單一圓筒形旋轉黏度計測定的黏度,再低也沒有問題。
導電性組成物之黏度係根據樹脂成分之黏度或導電性填料之含量等而異,故為了使導電性組成物之黏度在上述範圍內,可使用溶劑。於本發明中可使用的溶劑並無特別限定,例如可列舉:丙二醇單甲醚、3-甲氧基-3-甲基-1-丁醇、3-甲氧基-3-甲基-1-丁基乙酸酯、丙酮、甲基乙基酮、苯乙酮、甲基賽璐蘇、甲基賽璐蘇乙酸酯、甲基卡必醇、二乙二醇二甲醚、四氫呋喃、乙酸甲酯、乙酸丁酯等。此等可單獨使用一種,亦可併用二種以上。
溶劑之含量宜根據導電性組成物之用途或塗佈所使用的機器等而適當調整。因此,雖然根據樹脂成分的黏度及導電性填料的含量等而異,但以標準而言,溶劑之含量是相對於導電性組成物的含有成分(溶劑除外)的合計量而為10~60質量%左右。
藉由本發明之導電性組成物獲得之屏蔽層,與利用銅箔等形成之接地電路的密著性優異。具體而言,由於從屏蔽封裝體之一部分露出的接地電路的銅箔與屏蔽層之密著性為良好,故於屏蔽封裝體表面塗佈導電性組成物形成屏蔽層後,將封裝體切斷而單片化時,可防止因切斷時的衝擊而使屏蔽層從接地電路剝離。
藉由本發明導電性組成物所形成的塗膜被使用作為屏蔽層時,由獲得對100MHz~40GHz之電磁波優異的屏蔽性的觀點,比電阻宜為5.0×10-5
Ω・cm以下。
接著,利用圖式來說明關於用以使用本發明之導電性組成物來獲得屏蔽封裝體之方法的一實施形態。
首先,如圖1(a)所示,準備於基板1搭載複數個電子零件(IC等)2、且於此等複數個電子零件2間設置有接地電路圖案(銅箔)3者。
接著,如同圖(b)所示,於此等電子零件2及接地電路圖案3上填充密封材4並使之硬化,而將電子零件2密封。
然後,於同圖(c)中如箭頭所示,於複數個電子零件2間切削密封材4,形成槽部,藉由此等槽部使基板1的各電子零件的封裝體個別化。符號A表示分別經個別化之封裝體。接地電路之至少一部分從構成槽的壁面露出,槽底部並未完全地貫通基板。
另一方面,將特定量的上述樹脂成分、導電性填料及硬化劑與視需要而使用之溶劑混合,準備導電性組成物。
接著,藉由周知的噴槍等霧狀地噴射導電性組成物,均勻地塗佈於封裝體表面。此時的噴射壓力或噴射流量、噴槍的噴射口與封裝體表面的距離可視需要適當設定。
接著,將塗佈有導電性組成物的封裝體加熱,使溶劑充分地乾燥後,進一步加熱使導電性組成物充分地硬化,如同圖(d)所示,於封裝體表面使屏蔽層(導電性塗膜)5形成。此時的加熱條件可適當設定。圖2係顯示此狀態下基板的俯視圖。符號B1
、B2
、…B9
係分別表示單片化前之屏蔽封裝體,符號11~19係分別表示此等屏蔽封裝體間的槽。
接著,如於圖1(e)中箭頭所示,藉由切割機等沿著單片化前之封裝體的槽的底部將基板切斷,獲得經單片化之封裝體B。
藉此獲得的經單片化之封裝體B,由於在封裝體表面(上表面部、側表面部、及上表面部與側表面部的交界的角部)均形成有均勻的屏蔽層,故可獲得良好的屏蔽效果。且由於屏蔽層與封裝體表面及接地電路的密著性優異,故可防止因藉由切割器等將封裝體單片化時的衝擊,而使屏蔽層從封裝體表面或接地電路剝離。
符號說明
A:於基板上經個別化之封裝體
B:經單片化之屏蔽封裝體
B1
,B2
,B9
:單片化前之屏蔽封裝體
C:晶片樣品
1:基板
2:電子零件
3:接地電路圖案(銅箔)
4:密封材
5:屏蔽層(導電性塗膜)
11~19:槽
21~26:電路
27,28:電路端部
29:屏蔽層(導電性塗膜)
30:基板
31:電極墊
32:導電性組成物之硬化物
40:電磁波屏蔽效果測定裝置
41,41’:同軸波導管轉接器
42:樣品保持件
43:測定樣品
[實施例]
以下,根據實施例詳細地說明本發明之內容,但本發明並不限定於以下實施例。又,於以下,除非另有說明,「份」或「%」為質量基準。
[實施例、比較例]
相對於以下所示之(甲基)丙烯酸系樹脂、單體及母料之合計量100質量份,以表1所記載之比率摻配導電性填料、自由基聚合引發劑、環氧樹脂硬化劑及溶劑,進行混合,得到導電性組成物。使用的各成分的細節如下。
(甲基)丙烯酸系樹脂1:分子量=17000
(甲基)丙烯酸系樹脂2:分子量=100000、共榮公司化學(股)製「KC-1700P」
(甲基)丙烯酸系樹脂3:分子量=130000、共榮公司化學(股)製「KC-1100」
單體1:4-丙烯酸羥丁酯環氧丙基醚
母料1:使由平均粒徑100nm之聚丁二烯橡膠構成之粒狀樹脂成分分散於雙酚A型環氧樹脂中而成之母料、粒狀樹脂成分之含量為30質量%
母料2:使由平均粒徑100nm之聚矽氧構成之粒狀樹脂成分分散於雙酚F型環氧樹脂中而成之母料、粒狀樹脂成分之含量為25質量%
導電性填料1:銀粒子(平均粒徑=150nm)
導電性填料2:銀被覆銅合金粉(平均粒徑=5μm、小片狀、縱橫比=2~10、振實密度=5.8g/cm3
)
導電性填料3:銀被覆銅合金粉(平均粒徑=70μm、小片狀、縱橫比=2~10、振實密度=5.5g/cm3
)
自由基聚合引發劑:2,2’-偶氮雙(異丁酸)二甲酯
環氧樹脂硬化劑:四國化成工業股份有限公司製「2E4MZ(2-乙基-4-甲基咪唑)」
溶劑:甲基乙基酮(MEK)
如下所述進行上述實施例及比較例之導電性組成物之評價。將結果顯示於表1。
・雷射標記辨識性
使用Esi公司製之綠光飛秒加工機「Lode Stone」以如下所示之雷射標記條件於塑模樹脂上實施雷射標記(資料矩陣碼:17字元)。接著,使用噴塗裝置(Nordson Asymtek製「SL-940E」)將導電性組成物以如下噴塗條件噴塗於塑模樹脂上後,於100℃下加熱10分鐘、之後於150℃下加熱50分鐘,使之硬化,形成厚度6μm之塗佈膜。使用以下設定條件的條碼讀取器(Honey well公司製「條碼讀取器 Xenon 1902」、附件:AR-01),進行從塗佈膜之上能否讀取已施於塑模樹脂上之雷射標記的試驗。可讀取者為雷射標記辨識性優異,為「○」,不能讀取者為雷射標記辨識性差,為「╳」。
<雷射標記條件>
雷射圖案:點
雷射標記深度:最大40μm
雷射標記直徑:40μm
雷射標記間隔:10μm
雷射聚焦之Z方向偏移值:0.0mm
功率:0.3W
雷射脈衝間之距離:1.89μm
照射速度:188.5mm/s
頻率:100KHz
重複數:2
<噴塗條件>
主空氣:1.0psi
輔助空氣:6psi
噴頭速度:400mm/s
噴嘴尺寸:30G
塗佈對象物表面之溫度:25℃
從塗佈對象物表面到噴嘴的距離:約1.5cm
<條碼讀取器之設定條件>
瞄準(照準功能):關
列印設定:1或2
讀取對象:資料 矩陣
・導電性塗膜之導電性(比電阻)
以比電阻來評價從實施例1之導電性組成物獲得之導電性塗膜之導電性。具體而言,如圖4所示,於間隔了60mm的兩端設置有以銅箔形成之電極墊31的玻璃環氧基板30上,將設置了寬度5mm狹縫的厚度55μm聚醯亞胺膜,以狹縫端部與兩端電極墊31重疊之方式予以黏貼遮蔽。於其上,使用噴塗裝置(Nordson Asymtek製「SL-940E」)以如下的噴塗條件噴塗已於各實施例及比較例獲得的導電性組成物。
<噴塗條件>
主空氣:2.8psi
輔助空氣:5psi
噴頭間距:3.0mm
噴頭速度:450mm/s
噴嘴尺寸:30G
塗佈對象物表面之溫度:25℃
從塗佈對象物表面到噴嘴的距離:約1.5cm
接著,藉由於100℃下加熱10分鐘、然後於150℃下加熱60分鐘使之硬化,將聚醯亞胺膜剝離,獲得形成為長度70mm、寬度5mm、厚度約6μm之硬化物32將兩端電極墊31間連接的基板30。使用測試儀對該硬化物樣品測定電極墊間的電阻值(Ω),由截面積(S、cm2
)與長度(L、cm)藉由下式(1)計算比電阻(Ω・cm)。
樣品的截面積、長度及比電阻,係於三片玻璃環氧基板分別形成5根硬化物樣品,合計共形成15根,求得其平均值。又,若比電阻為5×10-5
Ω・cm以下,屏蔽性為良好,適合用作屏蔽層。
又,關於其他實施例及比較例亦以相同方式測定比電阻。
・導電性組成物之密著性(角摩耗試驗)
關於IC封裝體之模型,使用由玻璃環氧製基材(FR-5)與塑模樹脂形成,且如圖3所示,於內層具有由厚度35μm銅箔與通孔鍍敷所形成之電路21~26的晶片樣品C(1.0cm×1.0cm、厚度1.3mm)。電路21、22、23為連續的一個電路的一部分,電路24、25、26為另一個連續的一個電路的一部分,但電路21~23與電路24~26不連接。電路22、25分別於箭頭位置具有銅箔從晶片樣品之下部局部露出的焊墊部分,電路21、26分別具有從晶片樣品之兩端面露出的電路端部27、28。
以如下噴塗條件藉由噴塗將導電性組成物塗佈於上述晶片樣品C的表面,於100℃下加熱10分鐘、之後於150℃下加熱50分鐘,藉此而使之硬化,形成膜厚約6μm之屏蔽層(導電性塗膜)29。
<噴塗條件>
主空氣:2.8psi
輔助空氣:5psi
噴頭間距:3.0mm
噴頭速度:450mm/s
噴嘴尺寸:30G
塗佈對象物表面之溫度:25℃
從塗佈對象物表面到噴嘴的距離:約1.5cm
然後,於厚度0.5mm、寬度15mm之金屬刮刀被覆AS ONE(股)製「乳膠製手套(Clean Knoll Nitrile Gloves)」,以700g壓力摩擦晶片樣品C之角部來回3次,觀察導電性塗膜是否剝離。未觀察到剝離者為密著性優異,為「○」,確認有少許剝離者為密著性差,為「╳」。
・導電性組成物之密著性(焊料浸漬前後的比較)
基於JIS K 5600-5-6:1999(交叉切割法)評價屏蔽層與封裝體表面或與接地電路的密著性。
具體而言,準備覆銅積層板用於評價與接地電路之密著性,準備用於評價與封裝體表面之密著性之塑模樹脂。分別以形成寬度5cm、長度10cm之開口部之方式以聚醯亞胺膠帶進行遮蔽,使用噴塗裝置SL-940E(Nordson Asymtek製)按以下噴塗條件噴塗導電性組成物後,於150℃下加熱60分鐘,藉此使之硬化,將聚醯亞胺膠帶剝離,形成厚度約6μm之塗膜。於形成有塗膜的銅箔及塑模樹脂上進行交叉切割試驗。交叉切割試驗係針對回焊前者、進行過3次於最高溫度260℃下進行10秒鐘回焊處理者實施。
<噴塗條件>
主空氣:2.8psi
輔助空氣:5psi
噴頭間距:3.0mm
噴頭速度:450mm/s
噴嘴尺寸:30G
塗佈對象物表面之溫度:25℃
從塗佈對象物表面到噴嘴的距離:約1.5cm
密著性的評價以如下基準進行,若為1以上,判斷為密著性優異。
0:切口邊緣非常光滑、任何網格眼都沒有剝落。
1:在切口交叉處發生塗膜的小剝離。於交叉切割部分受到影響者明顯不超過5%。
2:塗膜沿著切口邊緣及/或交叉處剝離。於交叉切割部分受到影響者明顯超過5%但不超過15%。
3:塗膜沿著切口邊緣部分地或全面地產生大的剝離、及/或網格的各個部分部分地或全面地剝離。於交叉切割部分受到影響者明顯超過15%但不超過35%。
4:塗膜沿著切口邊緣部分地或全面地產生大的剝離、及/或幾處網格部分地或全面地剝離。於交叉切割部分受到影響者明顯不超過35%。
5:連分類4都不能分類的剝離程度之任一種。
又,使用圖5所示之系統對實施例1之導電性組成物評價對18~40GHz之電磁波的屏蔽性。具體而言,使用噴塗裝置SL-940E(Nordson Asymtek製)將導電性組成物以如下噴塗條件噴塗於厚度約25μm之聚醯亞胺膜上後,於100℃下加熱10分鐘、之後於150℃下加熱50分鐘,藉此使之硬化,形成厚度約6μm之塗膜,配合測定探頭進行裁斷,作為測定樣品43。
<噴塗條件>
主空氣:2.8psi
輔助空氣:5psi
噴頭間距:3.0mm
噴頭速度:450mm/s
噴嘴尺寸:30G
塗佈對象物表面之溫度:25℃
從塗佈對象物表面到噴嘴的距離:約1.5cm
就獲得之測定樣品43以如下測定條件利用波導管法進行十次測定,藉由測得之衰減量的平均值評價屏蔽性。
<測定條件>
資料點:201
中間頻率:100Hz
圖5所示之系統由電磁波屏蔽效果測定裝置40、傳送接收電磁波之同軸波導管轉接器41、41’、及固定測定樣品之樣品保持件42構成。
傳送之電磁波為18~26.5GHz時,使用Keysight Technologies公司製的網路分析儀「E8361A」作為電磁波屏蔽效果測定裝置40,使用Keysight Technologies公司製的「K-281C」作為同軸波導管轉接器41、41’,使用厚度3mm的EM Labs股份有限公司製的樣品保持件「WR-42」作為樣品保持件42。
又,傳送之電磁波為26.5~40GHz時,使用Keysight Technologies公司製的網路分析儀「E8361A」作為電磁波屏蔽效果測定裝置40,使用Keysight Technologies公司製的「R-281A」作為同軸波導管轉接器41、41’,使用厚度3mm的EM Labs股份有限公司製的樣品保持件「WR-28」作為樣品保持件42。
同軸波導管轉接器41、41’係相對向地設置,於同軸波導管轉接器41、41’之間配置有樣品保持件42,該樣品保持件42固定有測定樣品43。
於波導管法中,首先將從電磁波屏蔽效果測定裝置40輸出的信號輸入至傳送側的同軸波導管轉接器41。然後,將於接收側的同軸波導管轉接器41’接收到的信號利用電磁波屏蔽效果測定裝置40測定信號位準。再者,電磁波屏蔽效果測定裝置40係以在樣品保持件42未設置測定樣品43之狀態作為基準,輸出在樣品保持件42設置測定樣品43時的衰減量。
衰減量為80dB以上者,評價為屏蔽效果優異。
由表1所示之結果確認:由各實施例之導電性組成物獲得之塗膜均具有良好的導電性。又,如圖6、7所示,確認衰減量為80dB以上且對18~40GHz之電磁波的屏蔽性優異。再者,由於電磁波之頻率越低,穿透性越低,故若對18GHz以上電磁波具有優異的屏蔽性,可說對小於18GHz之電磁波的屏蔽性亦優異。因此,確認對100MHz~40GHz頻帶之電磁波具有優異的屏蔽性。又,確認屏蔽層與封裝體表面或與接地電路之密著性或雷射標記辨識性均為良好。
由表2所示之結果可知,比較例1(相當於專利文獻1記載的導電性樹脂組成物)為不含有粒狀樹脂成分之例,比較例2為粒狀樹脂成分之含量小於下限值之例,角摩耗試驗並不佳。
比較例3為粒狀樹脂成分之含量超過上限值之例,比電阻較高、不能獲得期望的屏蔽性。
比較例4為環氧樹脂硬化劑之含量小於下限值之例,角摩耗試驗並不佳。
比較例5為平均粒徑為1~50μm之導電性填料之形狀不是鱗片狀之例,無法形成均勻的導電性塗膜。
A:於基板上經個別化之封裝體
B:經單片化之屏蔽封裝體
B1
,B2
,B9
:單片化前之屏蔽封裝體
C:晶片樣品
1:基板
2:電子零件
3:接地電路圖案(銅箔)
4:密封材
5:屏蔽層(導電性塗膜)
11~19:槽
21~26:電路
27,28:電路端部
29:屏蔽層(導電性塗膜)
30:基板
31:電極墊
32:導電性組成物之硬化物
40:電磁波屏蔽效果測定裝置
41,41’:同軸波導管轉接器
42:樣品保持件
43:測定樣品
圖1係顯示屏蔽封裝體之製造方法之一實施形態的示意剖面圖。
圖2係顯示個別化前之屏蔽封裝體之一例的俯視圖。
圖3係顯示用於評價導電性塗膜之密著性(角摩耗試驗)的晶片樣品的示意剖面圖。
圖4係顯示用於評價導電性塗膜之導電性的形成有硬化物樣品的基板的俯視圖。
圖5係顯示於波導管法中使用之系統的構造圖。
圖6係顯示對18~26.5GHz之電磁波的屏蔽性的曲線圖。
圖7係顯示對26.5~40GHz之電磁波的屏蔽性的曲線圖。
A:於基板上經個別化之封裝體
B:經單片化之屏蔽封裝體
1:基板
2:電子零件
3:接地電路圖案(銅箔)
4:密封材
5:屏蔽層(導電性塗膜)
Claims (7)
- 一種導電性組成物,至少含有: (A)重量平均分子量為1000以上且40萬以下之(甲基)丙烯酸系樹脂; (B)於分子內具有環氧丙基及/或(甲基)丙烯醯基之單體; (C)平均粒徑為10nm~700nm之粒狀樹脂成分; (D)平均粒徑為10~500nm之導電性填料; (E)平均粒徑為1~50μm之鱗片狀導電性填料; (F)自由基聚合引發劑; (G)環氧樹脂硬化劑;且 於包含前述丙烯酸系樹脂(A)、前述單體(B)及前述粒狀樹脂成分(C)之樹脂成分中,前述粒狀樹脂成分(C)之含有比率為3~27質量%; 前述導電性填料(D)與前述導電性填料(E)之合計含量相對於前述樹脂成分100質量份為2000~12000質量份; 前述自由基聚合引發劑(F)之含量相對於前述樹脂成分100質量份為0.5~40質量份; 前述環氧樹脂硬化劑(G)之含量相對於前述樹脂成分100質量份為0.5~40質量份。
- 如請求項1之導電性組成物,其中前述環氧樹脂硬化劑(G)為選自於由酚系硬化劑、咪唑系硬化劑、胺系硬化劑及陽離子系硬化劑所構成群組中之至少一種。
- 如請求項1或2之導電性組成物,其中前述粒狀樹脂成分(C)為選自於由聚丁二烯橡膠、聚矽氧及苯乙烯丁烯橡膠所構成群組中之至少一種。
- 如請求項1至3中任一項之導電性組成物,其中前述鱗片狀導電性填料(E)之縱橫比為5~20。
- 如請求項1至4中任一項之導電性組成物,其中前述單體(B)為於分子內具有環氧丙基及(甲基)丙烯醯基者。
- 如請求項1至5中任一項之導電性組成物,其中前述導電性填料(D)與前述導電性填料(E)之含有比率((D):(E)),以質量比計為5:1~1:10。
- 一種屏蔽封裝體之製造方法,該屏蔽封裝體係藉由屏蔽層被覆封裝體而成,該封裝體係於基板上搭載有電子零件且該電子零件已藉密封材所密封者,前述屏蔽封裝體之製造方法至少具有以下步驟: 於基板上搭載複數個電子零件,且於該基板上填充密封材並使之硬化,藉此將前述電子零件密封之步驟; 於前述複數個電子零件間切削密封材,形成槽部,藉由該等槽部使基板上之各電子零件之封裝體個別化之步驟; 於前述經個別化之封裝體之表面,藉由噴霧塗佈如請求項1至6中任一項之導電性組成物之步驟; 將於前述封裝體之表面塗佈有導電性組成物之基板加熱,使前述導電性組成物硬化,藉此形成屏蔽層之步驟;及 沿著前述槽部將前述基板切斷,藉此獲得單片化之屏蔽封裝體之步驟。
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JP4019254B2 (ja) * | 2002-04-24 | 2007-12-12 | 信越化学工業株式会社 | 導電性樹脂組成物 |
JP5332464B2 (ja) * | 2008-09-30 | 2013-11-06 | 住友ベークライト株式会社 | 樹脂組成物および樹脂組成物を使用して作製した半導体装置 |
EP3650499B1 (en) * | 2017-07-07 | 2023-11-08 | Tatsuta Electric Wire & Cable Co., Ltd. | Electroconductive resin composition and method for manufacturing shielded package using same |
KR20190009124A (ko) | 2017-07-18 | 2019-01-28 | 세메스 주식회사 | 디스플레이 셀들을 검사하기 위한 장치 및 방법 |
KR102428873B1 (ko) * | 2017-10-13 | 2022-08-02 | 타츠타 전선 주식회사 | 차폐 패키지 |
-
2020
- 2020-12-29 TW TW109146715A patent/TWI833059B/zh active
-
2021
- 2021-01-15 JP JP2022518601A patent/JPWO2021220557A1/ja active Pending
- 2021-01-15 WO PCT/JP2021/001289 patent/WO2021220557A1/ja active Application Filing
- 2021-01-15 CN CN202180030027.3A patent/CN115397915A/zh active Pending
- 2021-01-15 US US17/916,681 patent/US20230151228A1/en active Pending
- 2021-01-15 KR KR1020227029422A patent/KR20230005118A/ko unknown
Also Published As
Publication number | Publication date |
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WO2021220557A1 (ja) | 2021-11-04 |
TWI833059B (zh) | 2024-02-21 |
CN115397915A (zh) | 2022-11-25 |
JPWO2021220557A1 (zh) | 2021-11-04 |
KR20230005118A (ko) | 2023-01-09 |
US20230151228A1 (en) | 2023-05-18 |
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