TWI820025B - 硬化性組成物、硬化物、半導體密封材料及印刷配線基板 - Google Patents
硬化性組成物、硬化物、半導體密封材料及印刷配線基板 Download PDFInfo
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- TWI820025B TWI820025B TW107117764A TW107117764A TWI820025B TW I820025 B TWI820025 B TW I820025B TW 107117764 A TW107117764 A TW 107117764A TW 107117764 A TW107117764 A TW 107117764A TW I820025 B TWI820025 B TW I820025B
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- Prior art keywords
- active ester
- compound
- curable composition
- ester compound
- dihydroxynaphthalene
- Prior art date
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Abstract
本發明之目的在於提供一種硬化物於高溫條件下之彈性模數低之活性酯化合物、含有其之硬化性組成物、其硬化物、半導體密封材料及印刷配線基板,而提供一種為二羥基萘化合物(a1)與芳香族單羧酸或其酸鹵化物(acid halide)(a2)之二酯化物的活性酯化合物、含有其之硬化性組成物、其硬化物、半導體密封材料及印刷配線基板。上述活性酯化合物具有其硬化物於高溫條件下之彈性模數低之特徵。
Description
本發明係關於一種高溫條件下之彈性模數低之活性酯化合物、含有其之硬化性組成物、其硬化物、半導體密封材料及印刷配線基板。
於半導體或多層印刷基板等所使用之絕緣材料之技術領域中,伴隨著各種電子構件之薄型化或小型化,要求開發出匹配該等市場動向之新穎樹脂材料。作為對半導體密封材料所要求之性能,為了提高回流焊性而要求高溫條件下之彈性模數低。此外,硬化物之耐熱性或耐吸濕性當然重要,作為訊號之高速化及高頻化對策,重要的是硬化物之介電常數及介電損耗正切值低,就高溫條件下之可靠性而言,重要的是玻璃轉移溫度(Tg)等物性不會變化,作為伴隨著薄型化之翹曲或變形對策,硬化收縮率或線膨脹係數低等亦較重要。
作為硬化物之耐熱性或介電特性等優異之樹脂材料,已知有使用異酞酸二(1-萘基酯)作為環氧樹脂之硬化劑之技術(參照下述專利文獻1)。專利文獻1所記載之環氧樹脂組成物藉由使用異酞酸二(α-萘基酯)作為環氧樹脂硬化劑,而與使用苯酚酚醛清漆樹脂之類的習知型環氧樹脂硬化劑之情形相比,硬化物之介電常數或介電損耗正切之值確實較低,但硬化物於高溫條件下之彈性模數並未滿足近年來所要求之等級。又,由於熔融黏度高,故而於半導
體密封材料等要求熔融黏度低之用途中使用存在限制。
[先前技術文獻]
[專利文獻]
[專利文獻1]日本特開2003-82063號公報
因此,本發明所欲解決之課題在於提供一種高溫條件下之彈性模數低之活性酯化合物、含有其之硬化性組成物、其硬化物、半導體密封材料及印刷配線基板。
本發明人等為了解決上述課題經潛心研究後,結果發現為二羥基萘化合物與芳香族單羧酸或其酸鹵化物(acid halide)之二酯化物的活性酯化合物不僅硬化物於高溫條件下之彈性模數低,而且熔融黏度亦低,從而完成本發明。
即,本發明係關於一種活性酯化合物,其係二羥基萘化合物(a1)與芳香族單羧酸或其酸鹵化物(a2)之二酯化物。
本發明進而係關於一種硬化性組成物,其含有上述活性酯化合物及硬化劑。
本發明進而係關於一種硬化物,其係上述硬化性組成物之硬化物。
本發明進而係關於一種半導體密封材料,其係使用上述硬化性組成物而成。
本發明進而係關於一種印刷配線基板,其係使用上述硬化性組
成物而成。
根據本發明,可提供一種硬化物於高溫條件下之彈性模數低之活性酯化合物、含有其之硬化性組成物、其硬化物、半導體密封材料及印刷配線基板。
圖1係實施例1中所獲得之活性酯化合物(1)之GPC線圖。
以下,對本發明詳細地進行說明。
本發明之活性酯化合物係二羥基萘化合物(a1)與芳香族單羧酸或其酸鹵化物(a2)之二酯化物。
上述二羥基萘化合物(a1)例如可列舉:二羥基萘、或於二羥基萘之芳香環上具有1個或多個取代基之二羥基萘化合物。上述取代基例如可列舉:脂肪族烴基、烷氧基、鹵素原子、芳基、芳烷基等。上述脂肪族烴基可為直鏈型及支鏈型之任一種,結構中亦可具有不飽和鍵。具體而言,可列舉:甲基、乙基、丙基、丁基、戊基、己基等烷基;環己基等環烷基;乙烯基、烯丙基、炔丙基等含不飽和鍵之基等。上述烷氧基可列舉:甲氧基、乙氧基、丙氧基、丁氧基等。上述鹵素原子可列舉:氟原子、氯原子、溴原子等。上述芳基可列舉:苯基、萘基、蒽基、及於該等之芳香核上取代有上述脂肪族烴基或烷氧基、鹵素原子等之結構部位等。上述芳烷基可列舉:苄基、苯基乙基、萘基甲基、萘基乙基、及於該等之芳香核上取代有上述烷基或烷氧基、鹵素原子
等之結構部位等。又,上述二羥基萘化合物(a1)中之兩個羥基之取代位置並無特別限定。作為一例,可列舉:1,2-二羥基萘、1,3-二羥基萘、1,4-二羥基萘、1,5-二羥基萘、1,6-二羥基萘、1,8-二羥基萘、2,3-二羥基萘、2,6-二羥基萘、2,7-二羥基萘、3,4-二羥基萘等。上述二羥基萘化合物(a1)可單獨地使用1種,亦可併用2種以上。
上述二羥基萘化合物(a1)之中,就成為硬化物於高溫條件下之彈性模數低,且硬化性等亦優異之活性酯化合物之方面而言,較佳為1,6-二羥基萘化合物或2,7-二羥基萘化合物。
上述芳香族單羧酸或其酸鹵化物(a2)可列舉:苯羧酸、萘羧酸、於該等之芳香核上具有1個或多個脂肪族烴基、烷氧基、鹵素原子、芳基、芳烷基等取代基之化合物、及該等之酸鹵化物等。該等可單獨地使用1種,亦可併用2種以上。其中,就成為硬化物於高溫條件下之彈性模數低,且硬化性等亦優異之活性酯化合物之方面而言,較佳為苯羧酸或其鹵化物。因此,作為本發明之活性酯化合物之更佳結構,可列舉下述結構式(1)所表示者。
(式中,R1分別獨立地為脂肪族烴基、烷氧基、鹵素原子、芳基、芳烷基之任一者,可鍵結於形成萘環之任一碳原子;R2分別獨立地為脂肪族烴基、烷氧基、鹵素原子、芳基、芳烷基之任一者,可鍵結於形成苯環之任一碳原子;m為0或1~6之整數,n為0或1~5之整數)
上述二羥基萘化合物(a1)與芳香族單羧酸或其酸鹵化物(a2)之反應,例如可藉由在鹼觸媒之存在下於40~65℃左右之溫度條件下進行加熱攪拌之方法進行。反應亦可視需要於有機溶劑中進行。又,亦可於反應結束後,視需要藉由水洗或再沈澱等對反應產物進行精製。
上述鹼觸媒例如可列舉:氫氧化鈉、氫氧化鉀、三乙胺、吡啶等。該等可分別單獨地使用,亦可併用2種以上。又,亦可以3.0~30%左右之水溶液之形式使用。其中,較佳為觸媒能力高之氫氧化鈉或氫氧化鉀。
上述有機溶劑例如可列舉:丙酮、甲基乙基酮、甲基異丁基酮、環己酮等酮溶劑;乙酸乙酯、乙酸丁酯、乙酸賽璐蘇(cellosolve acetate)、丙二醇一甲醚乙酸酯、卡必醇乙酸酯等乙酸酯溶劑;賽璐蘇、丁基卡必醇等卡必醇溶劑;甲苯、二甲苯等芳香族烴溶劑;二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮等。該等可分別單獨地使用,亦可以2種以上之混合溶劑之形式使用。
關於上述二羥基萘化合物(a1)與芳香族單羧酸或其酸鹵化物(a2)之反應比例,就以高產率獲得目標之活性酯化合物之方面而言,較佳為相對於上述二羥基萘化合物(a1)所具有之羥基之合計1莫耳,上述芳香族單羧酸或其酸鹵化物(a2)成為0.95~1.05莫耳的比例。
上述活性酯化合物之熔融黏度較佳為依據ASTM D4287,利用ICI黏度計所測得之150℃之值為0.01~50dPa‧s之範圍,尤佳為0.01~5dPa‧s之範圍。
本發明之硬化性組成物亦可將上述本發明之活性酯化合物與其他活性酯化合物一併含有。作為上述其他活性酯化合物,可列舉:於分子結構中具有1個酚性羥基之化合物與芳香族多羧酸或其酸鹵化物之酯化物;多羥基苯與芳香族單羧酸或其酸鹵化物之酯化物;於分子結構中具有1個酚性羥基之
化合物、芳香族多羧酸或其酸鹵化物及於分子結構中具有2個以上之酚性羥基之化合物之酯化物;芳香族多羧酸或其酸鹵化物、於分子結構中具有2個以上之酚性羥基之化合物及芳香族單羧酸或其酸鹵化物之酯化物等。
於使用上述其他活性酯化合物之情形時,就充分發揮本發明所起到之效果之方面而言,本發明之活性酯化合物相對於本發明之活性酯化合物與其他活性酯化合物之合計之比例,較佳為80質量%以上,更佳為90質量%以上。又,本發明之活性酯化合物與其他活性酯化合物之調配物之熔融黏度較佳為0.01~50dPa‧s之範圍,尤佳為0.01~5dPa‧s之範圍。調配物之熔融黏度係依據ASTM D4287,利用ICI黏度計所測得之於150℃之值。
本發明之硬化性組成物含有上述之活性酯化合物及硬化劑。上述硬化劑只要為可與上述活性酯化合物反應之化合物即可,並無特別限定,可應用各種化合物。作為硬化劑之一例,例如可列舉環氧樹脂。
上述環氧樹脂例如可列舉:苯酚酚醛清漆型環氧樹脂、甲酚酚醛清漆型環氧樹脂、萘酚酚醛清漆型環氧樹脂、雙酚酚醛清漆型環氧樹脂、聯苯酚酚醛清漆型環氧樹脂、雙酚型環氧樹脂、聯苯型環氧樹脂、三苯酚甲烷型環氧樹脂、四苯酚乙烷型環氧樹脂、二環戊二烯-苯酚加成反應型環氧樹脂、苯酚芳烷基型環氧樹脂、萘酚芳烷基型環氧樹脂等。
於本發明之硬化性組成物中,上述活性酯化合物與硬化劑之調配比例並無特別限定,可視所需之硬化物性能等適當進行調整。作為將環氧樹脂用作硬化劑之情形之調配之一例,較佳為相對於硬化性組成物中之環氧基之合計1莫耳,上述活性酯化合物中之官能基之合計成為0.7~1.5莫耳的比例。
本發明之硬化性組成物亦可進而含有其他樹脂成分。其他樹脂成分例如可列舉:二胺基二苯基甲烷、二伸乙基三胺、三伸乙基四胺、二胺基二苯基碸、異佛爾酮二胺、咪唑、BF3-胺錯合物、胍衍生物等胺化合物;二氰
二胺(dicyandiamide)、由次亞麻油酸之二聚物與乙二胺合成之聚醯胺樹脂等醯胺化合物;鄰苯二甲酸酐、偏苯三甲酸酐(trimellitic anhydride)、焦蜜石酸二酐、順丁烯二酸酐、四氫鄰苯二甲酸酐、甲基四氫鄰苯二甲酸酐、甲基耐地酸酐(methylnadic acid anhydride)、六氫鄰苯二甲酸酐、甲基六氫鄰苯二甲酸酐等酸酐;氰酸酯樹脂;雙馬來亞醯胺樹脂;苯并樹脂;苯乙烯-順丁烯二酸酐樹脂;以二烯丙基雙酚或三聚異氰酸三烯丙酯(triallyl isocyanurate)為代表之含烯丙基之樹脂;多磷酸酯或磷酸酯-碳酸酯共聚物等。該等可分別單獨地使用,亦可併用2種以上。該等其他樹脂成分之調配比例並無特別限定,可視所需之硬化物性能等適當進行調整。
本發明之硬化性組成物亦可視需要含有硬化促進劑、阻燃劑、無機質填充材、矽烷偶合劑、脫模劑、顏料、乳化劑等各種添加劑。
上述硬化促進劑例如可列舉:磷系化合物、三級胺、咪唑化合物、吡啶化合物、有機酸金屬鹽、路易斯酸、胺錯鹽等。其中,就硬化性、耐熱性、電特性、耐濕可靠性等優異之方面而言,磷系化合物中較佳為三苯基膦,三級胺中較佳為1,8-二氮雜雙環-[5.4.0]-十一烯(DBU),咪唑化合物中較佳為2-乙基-4-甲基咪唑,吡啶化合物中較佳為4-二甲胺基吡啶。
上述阻燃劑例如可列舉:紅磷、磷酸一銨、磷酸二銨、磷酸三銨、多磷酸銨等磷酸銨、磷醯胺等無機磷化合物;磷酸酯化合物、膦酸化合物、次膦酸(phosphinic acid)化合物、氧化膦(phosphine oxide)化合物、磷烷(phosphorane)化合物、有機系含氮磷化合物、9,10-二氫-9-氧雜-10-磷雜菲-10-氧化物、10-(2,5-二羥基苯基)-10H-9-氧雜-10-磷雜菲-10-氧化物、10-(2,7-二羥基萘基)-10H-9-氧雜-10-磷雜菲-10-氧化物等環狀有機磷化合物,及使其與環氧樹脂或酚樹脂等化合物反應所得之衍生物等有機磷化合物;三化合物、三聚氰酸(cyanuric acid)化合物、異三聚氰酸化合物、啡噻等氮系阻燃劑;
聚矽氧油、聚矽氧橡膠、聚矽氧樹脂等聚矽氧系阻燃劑;金屬氫氧化物、金屬氧化物、金屬碳酸鹽化合物、金屬粉、硼化合物、低熔點玻璃等無機阻燃劑等。於使用該等阻燃劑之情形時,較佳為硬化性組成物中0.1~20質量%之範圍。
上述無機質填充材係例如於將本發明之硬化性組成物用於半導體密封材料用途之情形時等進行調配。上述無機質填充材例如可列舉:熔融二氧化矽、結晶二氧化矽、氧化鋁、氮化矽、氫氧化鋁等。其中,就能夠更多地調配無機質填充材之方面而言,較佳為上述熔融二氧化矽。上述熔融二氧化矽可使用破碎狀、球狀之任一種,為了提高熔融二氧化矽之調配量,且抑制硬化性組成物之熔融黏度之上升,較佳為主要使用球狀者。為了進一步提高球狀二氧化矽之調配量,較佳適當地調整球狀二氧化矽之粒度分佈。其填充率較佳為以硬化性組成物100質量份中0.5~95質量份之範圍進行調配。
此外,於將本發明之硬化性組成物用於導電膏等用途之情形時,可使用銀粉或銅粉等導電性填充劑。
如以上所詳細說明,本發明之活性酯化合物及含有其之硬化性組成物具有硬化物於高溫條件下之彈性模數低之特徵。此外,對樹脂材料所要求之其他一般要求性能亦充分高,如向通用有機溶劑之溶解性或耐熱性、耐吸水性、低硬化收縮性、介電特性等亦優異且熔融黏度低等。因此,除印刷配線基板或半導體密封材料、抗蝕劑材料等電子材料用途以外,亦可廣泛地應用於塗料或接著劑、成型品等用途。
於將本發明之硬化性組成物用於印刷配線基板用途或增層接著膜用途之情形時,一般較佳為調配有機溶劑並進行稀釋而使用。上述有機溶劑可列舉:甲基乙基酮、丙酮、二甲基甲醯胺、甲基異丁基酮、甲氧基丙醇、環己酮、甲基賽璐蘇、乙基二乙二醇乙酸酯、丙二醇一甲醚乙酸酯等。有機溶劑
之種類或調配量可視硬化性組成物之使用環境而適當調整,例如於印刷配線板用途中,較佳為甲基乙基酮、丙酮、二甲基甲醯胺等沸點為160℃以下之極性溶劑,較佳為以非揮發分成為40~80質量%之比例使用。於增層接著膜用途中,較佳為使用丙酮、甲基乙基酮、環己酮等酮溶劑;乙酸乙酯、乙酸丁酯、乙酸賽璐蘇、丙二醇一甲醚乙酸酯、卡必醇乙酸酯等乙酸酯溶劑;賽璐蘇、丁基卡必醇等卡必醇溶劑;甲苯、二甲苯等芳香族烴溶劑;二甲基甲醯胺、二甲基乙醯胺、N-甲基吡咯啶酮等,較佳為以非揮發分成為30~60質量%之比例使用。
又,使用本發明之硬化性組成物製造印刷配線基板之方法例如可列舉如下方法:將硬化性組成物含浸於補強基材中,使之硬化而獲得預浸體,將其與銅箔重疊,進行加熱壓接。上述補強基材可列舉:紙、玻璃布、玻璃不織布、聚芳醯胺(aramid)紙、聚芳醯胺布、玻璃氈、玻璃粗紗布等。硬化性組成物之含浸量並無特別限定,通常較佳以預浸體中之樹脂成分成為20~60質量%之方式進行製備。
於將本發明之硬化性組成物用於半導體密封材料用途之情形時,一般較佳為調配無機質填充材。半導體密封材料例如可使用擠出機、捏合機、輥等將調配物進行混合而製備。關於使用所獲得之半導體密封材料成型半導體封裝之方法,例如可列舉:使用澆鑄成型或轉移成形機、射出成型機等將該半導體密封材料進行成形,進而於50~200℃之溫度條件下進行2~10小時加熱之方法,藉由此種方法,可獲得作為成形物之半導體裝置。
[實施例]
繼而,藉由實施例、比較例對本發明具體地進行說明。實施例中之「份」及「%」之記載只要無特別說明,則為質量基準。
◆熔融黏度測定法
於本案實施例中,活性酯化合物之熔融黏度係依據ASTM D4287,利用ICI黏度計測定150℃之熔融黏度所得。
實施例1 活性酯化合物(1)之製造
於安裝有溫度計、滴液漏斗、冷凝管、分餾管、攪拌器之燒瓶中添加1,6-二羥基萘160g及甲苯1100g,一面對系統內於減壓下進行氮氣置換一面進行溶解。繼而,添加苯甲醯氯218g,一面對系統內於減壓下進行氮氣置換一面進行溶解。添加四丁基溴化銨0.6g,一面吹送氮氣,一面將系統內控制為60℃以下,歷時3小時滴加20%氫氧化鈉水溶液420g。滴加結束後,直接繼續攪拌1小時進行反應。反應結束後,靜置反應混合物,進行分液,去除水層。於殘留之有機層中添加水,進行約15分鐘攪拌混合後,靜置混合物,進行分液,去除水層。將該操作反覆進行至水層之pH值成為7後,利用傾析器脫水將水分及甲苯去除,獲得活性酯化合物(1)。活性酯化合物(1)之熔融黏度為0.11dPa‧s。
實施例2 活性酯化合物(2)之製造
於安裝有溫度計、滴液漏斗、冷凝管、分餾管、攪拌器之燒瓶中添加2,7-二羥基萘160g及甲苯1100g,一面對系統內於減壓下進行氮氣置換一面進行溶解。繼而,添加苯甲醯氯218g,一面對系統內於減壓下進行氮氣置換一面進行溶解。添加四丁基溴化銨0.6g,一面吹送氮氣,一面將系統內控制為60℃以下,歷時3小時滴加20%氫氧化鈉水溶液420g。滴加結束後,直接繼續攪拌1小時進行反應。反應結束後,靜置反應混合物,進行分液,去除水層。於殘留之有機層中添加水,進行約15分鐘攪拌混合後,靜置混合物,進行分液,去除水層。將該操作反覆進行至水層之pH值成為7後,利用傾析器脫水將水分及甲苯去除,獲得活性酯化合物(2)。活性酯化合物(2)之熔融黏度為0.07dPa‧s。
比較製造例1 活性酯化合物(1')之製造
於安裝有溫度計、滴液漏斗、冷凝管、分餾管、攪拌器之燒瓶中添加間苯
二甲醯氯202g及甲苯1250g,一面對系統內於減壓下進行氮氣置換一面進行溶解。繼而,添加1-萘酚288g,一面對系統內於減壓下進行氮氣置換一面進行溶解。添加四丁基溴化銨0.63g,一面吹送氮氣,一面將系統內控制為60℃以下,歷時3小時滴加20%氫氧化鈉水溶液420g。滴加結束後,直接繼續攪拌1小時進行反應。反應結束後,靜置反應混合物,進行分液,去除水層。於殘留之有機層中添加水,進行約15分鐘攪拌混合後,靜置混合物,進行分液,去除水層。將該操作反覆進行至水層之pH值成為7後,利用傾析器脫水將水分及甲苯去除,獲得活性酯化合物(1')。活性酯化合物(1')之熔融黏度為0.65dPa‧s。
實施例3、4及比較例1
以下述表1所示之比例調配各成分以製造硬化性組成物。使硬化性組成物流入至模框中,使用壓製機於175℃之溫度下進行10分鐘成型。自模框中取出成型物,於175℃之溫度下使之硬化5小時而獲得硬化物。對於硬化物,以下述要領進行評價試驗。將結果示於表1。
高溫條件下之儲存彈性模數之測定
自上述硬化物切出5mm×54mm×2.4mm尺寸之試片。針對試片,使用黏彈性測定裝置(Rheometric公司製造之「固體黏彈性測定裝置RSAII」),於矩形張力法、頻率1Hz、升溫溫度3℃/分鐘之條件測定260℃之儲存彈性模數。
高溫條件下之彎曲彈性模數及彎曲變形之測定
自上述硬化物切出25mm×70mm×2.4mm尺寸之試片。針對試片,使用萬能材料試驗機(英斯特朗公司製造之「5582型」),於試驗速度1.0mm/分鐘、試驗溫度260℃之條件下測定彎曲彈性模數及彎曲變形。
環氧樹脂(*1):甲酚酚醛清漆型環氧樹脂(DIC股份有限公司製造之「N-655-EXP-S」,環氧當量202g/當量)
Claims (5)
- 一種硬化性組成物,其含有活性酯化合物及硬化劑,該活性酯化合物係二羥基萘化合物(a1)與芳香族單羧酸或其酸鹵化物(acid halide)(a2)之二酯化物,且具有下述結構式(1)所表示之分子結構,
- 如請求項1所述之硬化性組成物,其中,該硬化劑為環氧樹脂。
- 一種硬化物,其係請求項2所述之硬化性組成物之硬化物。
- 一種半導體密封材料,其係使用請求項2所述之硬化性組成物而成。
- 一種印刷配線基板,其係使用請求項2所述之硬化性組成物而成。
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US8288591B2 (en) * | 2008-11-20 | 2012-10-16 | Designer Molecules, Inc. | Curing agents for epoxy resins |
US20130012620A1 (en) * | 2010-03-17 | 2013-01-10 | Designer Molecules, Inc. | Curing agents for epoxy resins |
CN102985485B (zh) | 2010-07-02 | 2014-09-03 | Dic株式会社 | 热固性树脂组合物、其固化物、活性酯树脂、半导体密封材料、预浸料、电路基板、及积层薄膜 |
JP5804991B2 (ja) | 2012-03-19 | 2015-11-04 | 富士フイルム株式会社 | 光反射フィルム、自動車用フロントガラス、建材用ガラス |
KR101350997B1 (ko) * | 2012-08-21 | 2014-01-14 | 주식회사 신아티앤씨 | 전기적 특성이 우수한 에폭시 화합물 및 그 제조방법 |
TWI572665B (zh) * | 2012-10-17 | 2017-03-01 | Dainippon Ink & Chemicals | 活性酯樹脂、環氧樹脂組成物、其硬化物、預浸體、 電路基板以及積層膜 |
CN103408510B (zh) * | 2013-07-26 | 2015-12-09 | 深圳先进技术研究院 | 含萘液晶环氧树脂化合物,其制备方法及组合物 |
JP6376395B2 (ja) * | 2014-12-05 | 2018-08-22 | Dic株式会社 | 活性エステル化合物、活性エステル樹脂、硬化性組成物、その硬化物、ビルドアップフィルム、半導体封止材料、プリプレグ、回路基板、及び活性エステル樹脂の製造方法 |
TWI685540B (zh) | 2014-12-15 | 2020-02-21 | 日商迪愛生股份有限公司 | 熱硬化性樹脂組成物、其硬化物、及用於其之活性酯樹脂 |
-
2018
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