TWI756679B - 一種改性馬來醯亞胺化合物及其製備方法及應用 - Google Patents
一種改性馬來醯亞胺化合物及其製備方法及應用 Download PDFInfo
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- TWI756679B TWI756679B TW109114940A TW109114940A TWI756679B TW I756679 B TWI756679 B TW I756679B TW 109114940 A TW109114940 A TW 109114940A TW 109114940 A TW109114940 A TW 109114940A TW I756679 B TWI756679 B TW I756679B
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Abstract
本發明係關於一種改性馬來醯亞胺化合物及其製備方法及應用,前述改性馬來醯亞胺化合物由化合物(A)或者含胺基矽烷的有機金屬鹽,以及含有至少兩個馬來醯亞胺基團的化合物(B)製備。本發明將含有至少兩個馬來醯亞胺基團的化合物(B)與含胺基的矽烷化合物(A)或者含胺基矽烷的有機金屬鹽進行預聚,得到一種含矽烷的改性馬來醯亞胺化合物,將其用於複合材料的樹脂組成物時,其具有與低極性樹脂更好的相容性,並在半固化片的烘乾過程中避免矽烷偶聯劑的揮發,並能降低雙馬來醯亞胺與其他樹脂之間反應性,使樹脂組成物的固化應力降低,增加樹脂組成物對增強材料或導電層之間的黏合力,並保持低介電損耗及高耐熱性。
Description
本發明涉及印刷電路技術領域,尤其涉及一種改性馬來醯亞胺化合物及其製備方法及應用。
隨著電子電氣行業的進步和終端電子的迅猛發展,電子線路基板的發展方向為輕薄化、高性能化、高可靠性以及環保等。馬來醯亞胺樹脂作為一種熱固性聚醯亞胺樹脂,在力學性能、電性能、耐熱性和耐溶劑性能方面均有著卓越的表現。在電子電路基板中,雙馬來醯亞胺樹脂或多馬來醯亞胺樹脂目前已在封裝基板領域有了大量的應用。但目前存在的問題之一為馬來醯亞胺樹脂在黏合力方面一直表現不足,因此,一般將其與黏結性較好的環氧樹脂、酚醛樹脂和氰酸酯樹脂進行組合使用,但是將雙馬來醯亞胺與極性較低樹脂進行組合時,其黏結性表現仍很差。
CN106700549A公開了一種改性雙馬來醯亞胺樹脂、增強層壓板及其製備方法,雙馬來醯亞胺樹脂經氰酸酯樹脂、橡膠、雙氰胺、二氧化矽改性得到改性雙馬來醯亞胺樹脂,以改性雙馬來醯亞胺樹脂為膠黏劑,以玻璃纖維為基材,經過浸塗上膠、膠布乾燥、層壓製備得到增強層壓板。該發明的優點是,提供了一種能夠滿足工業生產要求的改性雙馬
來醯亞胺樹脂以這種改性雙馬來醯亞胺樹脂與玻璃纖維製備的增強層壓板,不僅具有良好的耐熱性能,其力學性能也得到了顯著的提高,綜合性能優良,可應用於電氣絕緣、航空航天等領域。但是該發明中,得到的層壓板仍會存在介電常數和介電損耗較高的問題。
CN105295048A公開了一種高耐熱性液體改性雙馬來醯亞胺樹脂及其製備方法,將3-胺基苯並環丁烯與雙馬來醯亞胺單體經邁克爾加成熔融共聚形成預聚體,降溫後添加活性稀釋劑保溫,冷卻後加入溶有催化劑的溶液,混合均勻,真空蒸除溶解催化劑的溶劑,得到高耐熱性液態改性雙馬來醯亞胺樹脂。該發明提供的樹脂體系常溫下呈現流動液態,是雙馬樹脂領域不多見的品種,表現出良好的加工工藝性,適合目前多種複合材料成型工藝,不僅可用作高級覆銅板的基礎樹脂,而且還可以用於航空航天、交通運輸等領域的先進複合材料或耐高溫膠黏劑等。但是該發明的雙馬來醯亞胺樹脂與低極性樹脂組成的組成物與銅箔、玻璃纖維布等材料的黏結性較差,製備得到的層壓板的剝離強度低。
CN101824148A公開了一種含八乙烯基籠型倍半矽氧烷的雙馬來醯亞胺-三嗪樹脂及其製備方法。按重量計,在120~140℃下,將100份雙馬來醯亞胺緩慢加入到O,O'-二烯丙基雙酚A中,得到預聚體I;緩慢地將1894份八乙烯基籠型倍半矽氧烷加入到120~140℃的預聚體I中,得到預聚體II;稱取215~280份的氰酸酯,緩慢加入到預聚體II中,升溫至140~160℃,再保溫攪拌1~2小時,得到一種含八乙烯基籠型倍半矽氧烷的雙馬來醯亞胺-三嗪樹脂。製得的樹脂可作為電子訊息領域製備高性能覆銅板等的基礎材料。但是該樹脂的黏結性較差,製備得到的覆銅板
的剝離強度較低。
因此,本領域亟待開發一種新型的馬來醯亞胺化合物,改善與低極性樹脂組合的黏結性能,且得到低介電和高耐熱的層壓板。
本發明的目的之一在於提供改性馬來醯亞胺化合物,改善與低極性樹脂組合的黏結性能,進而製備得到高剝離強度、低介電和高耐熱性的層壓板。
為達此目的,本發明採用以下技術手段:
本發明提供一種改性馬來醯亞胺化合物,所述改性馬來醯亞胺化合物由化合物(A)或者含胺基矽烷的有機金屬鹽,以及含有至少兩個馬來醯亞胺基團的化合物(B)製備,所述化合物(A)的分子結構如下:
所述R1、R2和R3各自獨立地選自C1~C6(例如C1、C2、C3、C4、C5或C6)烷基;
所述m為0或1。
本發明將含有至少兩個馬來醯亞胺基團的化合物(B)與含胺基的矽烷化合物(A)或者含胺基矽烷的有機金屬鹽進行加熱反應,得到一種含矽烷的改性馬來醯亞胺化合物。將其用於複合材料的樹脂組成物時,其具有與低極性樹脂更好的相容性,並在半固化片的烘乾過程中避免矽烷偶聯劑的揮發,並能降低雙馬來醯亞胺與其他樹脂之間反應性,使樹脂組成物的固化應力降低,增加樹脂組成物對增強材料或導電層之間的黏合力,並保持低介電損耗和高耐熱性。
本發明中,化合物(A)或者胺基矽烷的有機金屬鹽的N原子與化合物(B)中羰基鄰位連接,示例性地可以形成如下結構的改性馬來醯亞胺化合物:
上述結構僅為了表述化合物(A)或胺基矽烷的有機金屬鹽和化合物(B)反應後的連接方式,並不限於上述結構,根據原料結構的不同,得到的改性馬來醯亞胺化合物的結構也會有所不同。
理想地,所述化合物(A)具有如下式I至式III所示的結構中的任意一種:
所述R1、R2、R3、Y1、Y2和Y3均具有與前文相同的選擇範圍。
理想地,所述R1、R2和R3各自獨立地選自CH3、C2H5或C3H7中的任意一種。
理想地,所述Y1和Y2各自獨立地選自
本發明理想化合物(A)中包含上述連接基團,這些連接基團能夠延長鏈長度,避免樹脂固化後的交聯結構對矽氧烷的影響,能夠進一步提升樹脂的黏結性能,另外這些結構的主鏈具有更高的剛性,有利於高耐熱性。
理想地,所述化合物(B)具有如下式IV或式V所示的結構:
所述R、R4~R11各自獨立地選自-H、C1~C15(例如C1、C2、C3、C4、C5、C6、C7、C8、C9、C10、C11、C12、C13、C14等)烷基、、或中的任意一種,理想-H、-CH3、-C2H5、-
C3H7、-C4H9、-C5H11、-C8H17、-C15H31、、或中的任意一種;
所述n為1~10的整數,例如2、3、4、5、6、7、8、9等。
本發明的目的之二在於提供一種目的之一所述的改性馬來醯亞胺化合物的製備方法,所述製備方法包括:化合物(A)或者含胺基矽烷的有機金屬鹽與含有至少兩個馬來醯亞胺基團的化合物(B)進行加熱反應,得到所述改性馬來醯亞胺化合物。
理想地,所述加熱反應的溫度為100~200℃,理想110℃、120℃、130℃、136℃、141℃、145℃、151℃、156℃、160℃、165℃和170℃。
理想地,所述加熱反應的時間為1~30小時,理想2小時、3小時、4小時、5小時、6小時、7小時、8小時、10小時、12小時、16小時、21小時、28小時。
理想地,所述加熱反應在冷凝回流的條件下進行。
理想地,所述加熱反應在攪拌下進行。
理想地,所述化合物(A)或者含胺基矽烷的有機金屬鹽與化合物(B)的莫耳比為10:90~80:20,例如10:90、15:85、20:80、24:76、30:70、40:60、50:50、60:40、70:30、80:20等。為了使化合物(A)與化合物(B)能夠充分的發生反應,進一步理想地,莫耳比為30:70~50:50,例如30:70、35:65、38:62、40:60、45:55、50:50等。
理想地,所述加熱反應中加入促進劑。
理想地,所述促進劑的用量為化合物(B)質量的0.01~10%,例如0.1%、0.5%、1%、1.5%、2%、2.5%、3%、3.5%、4%、4.5%、5%、5.5%、6%、6.5%、7%、7.5%、8%、8.5%、9%、9.5%等。
理想地,所述促進劑包括過氧化二枯基、叔丁基過氧化枯基、過氧化二叔丁基、過氧化異丙基碳酸叔丁酯、2,5-二甲基-2,5-二叔丁基枯基過氧基己炔-3、2,5-二甲基2,5-二叔丁基過氧化己烷、過氧化對孟烷、1,1-雙(叔戊基過氧)環己烷、過氧化氫二異丙基苯、過氧化苯甲醯、過氧化苯甲醯衍生物、乙醯丙酮的金屬鹽、環烷酸的金屬鹽、五氧化釩、胺類化合物、季銨鹽、咪唑、三苯基膦或三苯基膦衍生物中的任意一種或至少兩種組合。
理想地,所述加熱反應中加入溶劑。
理想地,所述溶劑的用量為化合物(B)質量的10~500%,例如50%、100%、150%、200%、250%、300%、350%、400%、450%、480%等,理想50~400%;
理想地,所述溶劑包括甲苯、二甲苯、環己烷、四氫呋喃、N,N-二甲基甲醯胺(DMF)或丁酮中的任意一種或至少兩種組合。
本發明的目的之三在於提供一種樹脂組成物,所述樹脂組成物中含有目的之一所述的改性馬來醯亞胺化合物。
本發明的目的之四在於提供一種預浸片,所述預浸片包括增強材料及通過含浸乾燥後附著其上的目的之三所述的樹脂組成物。
理想地,所述增強材料包括玻璃纖維布。
本發明的目的之五在於提供一種絕緣板,所述絕緣板包括至少一張目的之四所述的預浸片。
本發明的目的之六在於提供一種覆金屬箔層壓板,所述覆金屬箔層壓板包括至少一張目的之四所述的預浸片以及覆於疊合後的預浸片一側或兩側的金屬箔。
本發明的目的之七在於提供一種印刷電路板,所述印刷電路板包括至少一張目的之四所述的預浸片,或至少一張目的之五所述的絕緣板,或至少一張目的之六所述的覆金屬箔層壓板。
相對於先前技術,本發明具有以下功效:
本發明將含有至少兩個馬來醯亞胺基團的化合物(B)與含胺基的矽烷化合物(A)或者含胺基矽烷的有機金屬鹽進行加熱反應,得到一種含矽烷的改性馬來醯亞胺化合物。將其用於複合材料的樹脂組成物時,其具有與低極性樹脂更好的相容性,並在半固化片的烘乾過程中避免矽烷偶聯
劑的揮發,並能降低雙馬來醯亞胺與其他樹脂之間反應性,使樹脂組成物的固化應力降低,增加樹脂組成物對增強材料或導電層之間的黏合力,並保持低介電損耗和高耐熱性。
下面通過具體實施方式來進一步說明本發明的技術手段。所屬技術領域中具有通常知識者應該明瞭,所述實施例僅僅是幫助理解本發明,不應視為對本發明的具體限制。
下文所涉及到的化合物的詳細訊息如下:
KBM-602:N-2-(β-胺乙基)-3-γ-胺丙基甲基二甲氧基矽烷,日本信越;
KBM-603:N-2-(胺乙基)-3-胺丙基三甲氧基矽烷,日本信越;
KBM-903:3-胺丙基三甲氧基矽烷,日本信越;
KBE-903:3-胺丙基三乙氧基矽烷,日本信越;
1,2-乙二胺,N,N'-雙苄基-N-[3-(三甲氧基矽烷)丙基]-鹽酸鹽,CAS:145151-33-3,試劑,市售;
KBM-403:3-縮水基甘油醚氧基丙基甲基三甲氧基矽烷,日本信越;
DDM:二胺基二苯甲烷,印度阿圖;
DDS:二胺基二苯碸,印度阿圖;
CAS:92-87-5,4,4'-二胺基聯苯,試劑,市售;
BMI-50P:多官能馬來醯亞胺樹脂,日本KI;
BMI-70:雙(3-乙基-5-甲基-4-馬來醯亞胺基苯)甲烷,日本KI;
BMI-80:2,2-二(4-(4-馬來醯亞胺苯氧基)苯基)丙烷,日本KI。
合成例1~6
合成例1~6提供種改性馬來醯亞胺化合物,製備步驟如下:
將含胺基的矽烷化合物(KBM-602,KBM-603,KBM-903,KBE-903)、含有至少兩個馬來醯亞胺基團的化合物(BMI-70,BMI-80,BMI-50P)、促進劑和溶劑加入具有冷凝回流、攪拌和加熱的反應容器中,加熱攪拌回流後,蒸出反應物中的溶劑,冷卻至常溫,得到改性馬來醯亞胺化合物P1~P6。
合成例1~6的原料組成、反應時間和反應溫度詳見表1。
表1中,──代表不添加對應物質。
合成例7~10
本合成例提供一種改性馬來醯亞胺化合物P7~P10,其製備方法如下:
將KBM-403、二胺化合物(DDM、DDS或4,4'-二胺基聯苯)和DMF加入具有冷凝回流,攪拌和加熱的反應容器中,加熱至160℃攪拌回流2小時,然後加入含有兩個以上馬來醯亞胺基團的化合物(BMI-70或BMI-50P),加熱攪拌回流後,蒸出反應物中的溶劑,冷卻至常溫,得到改性馬來醯亞胺化合物P7~10。
合成例7~10的原料組成、反應時間和反應溫度詳見表2。
表2中,──代表不添加對應物質。
對比合成例1
按照專利申請CN101775139A的實施例1製備得到的改性雙馬來醯亞胺樹脂(D1),具體步驟如下:
將100份雙馬來醯亞胺、50份二烯丙基苯基化合物、12份γ胺丙基三乙氧基矽烷及0.50~1.50份水在室溫下混合在溫度為40℃的條件下反應
60分鐘;再升溫至150 C,預聚反應120分鐘後,得到一種改性雙馬來醯亞胺樹脂D1。
實施例1~10、對比例1~2
實施例1~10、對比例1~2分別提供一種樹脂膠液及層壓板,具體製備過程如下:
(1)樹脂膠液的製備:
先將改性馬來醯亞胺化合物(P1~P10、D1中的一種)或未改性的馬來醯亞胺化合物在DMF中溶解,然後與配方中的其他組分混合均勻,即得到樹脂膠液;具體配方詳見表3;
(2)層壓板的製備:
取型號為2116的玻璃纖維布均勻浸漬上述樹脂膠液,在鼓風烘箱中於155℃烘烤5min製得預浸片,將6張上述預浸片重疊,上下覆35μm反轉銅箔,於真空熱壓機中在3MPa壓力和220℃溫度下壓製90min得到層壓板。
性能測試:
(1)玻璃化轉變溫度Tg:使用動態熱機械分析(DMA)測試,參考IPC-TM-6502.4.24所規定的DMA測試方法。
(2)熱分解溫度(Td):使用熱失重分析(TGA)測試,參考標準IPC-TM-650 2.4.24.6。
(3)剝離強度(PS):指在室溫下將每毫米銅箔剝離覆銅板所需的拉力。
(4)介電常數(Dk)和介電損耗因數(Df):使用平板電
容法測定,參考標準IPC-TM-650 2.4.24。
(5)阻燃:按照UL94“50W(20mm)垂直燃燒試驗:V-0、V-1和V-2”測試方法測試,認定V-0為阻燃。
(6)熱膨脹係數和50~260℃熱膨脹比例:測試採用靜態熱分析儀(TMA)測試,測試參考標準IPC-TM-650 2.4.24。
(7)熱應力:將帶銅的層壓板漂浮在熔融狀態的錫液表面,溫度288℃,以分層或氣泡的時間作為測試結果。
上述測試結果詳見表3。
表3中各組分的詳細訊息如下:
OPE-2St:三菱瓦斯,雙端烯烴官能化聚苯醚;
B-1000:日本曹達,聚丁二烯樹脂;
Ricon257:美國克雷威勒,丁二烯-苯乙烯-二乙烯基苯枝化三元共聚物;
A1536:美國科騰,SEBS樹脂;
NQ1025J:無機填料NQ1025J球型熔融二氧化矽,D50=3.0μm,江蘇聯瑞新材料股份有限公司;
Bt-93W:美國雅寶,十溴二苯乙撐,阻燃劑;
OP935:美國克萊恩,含磷阻燃劑;
DCP:過氧化二異丙苯,引發劑。
──代表不添加對應物質。
由表3可知,本發明提供的改性馬來醯亞胺化合物與低極性樹脂組合後,具有較強的黏結性能,製備得到的層壓板具有較高的剝離強度,同時具有良好的介電性能和耐熱性能,其中,剝離強度為大於0.8N/mm,1GHz介電常數小於3.8,1GHz介電損耗因數小於0.002,玻璃化
轉變溫度大於190℃,熱分解溫度大於400℃,50~260℃熱膨脹比例小於2%,熱應力均大於60min。
對比例1沒有將含有胺基的矽烷化合物與馬來醯亞胺進行預聚,而是分別加入至樹脂膠液中,最終得到的層壓板的剝離強度較高,Tg和Td較低,Dk和Df較高,熱膨脹係數和膨脹比例較大,耐熱性能明顯下降。這是由於,在膠液固化的過程中,含有胺基的矽烷化合物快速揮發,而且雙馬來醯亞胺與烯烴樹脂的固化反應較快,進而使上述性能降低。
對比例2中所使用的改性馬來醯亞胺化合物的製備原料中還包括二烯丙基苯基化合物,與實施例相比,其介電性能明顯降低,介電常數和介電損耗明顯偏高,這是由於二烯丙基苯基化合物與雙馬來醯亞胺的反應比較複雜,對介電性能造成了不利影響。
本發明通過上述實施例來說明本發明的詳細方法,但本發明並不局限於上述詳細方法,即不意味著本發明必須依賴上述詳細方法才能實施。所屬技術領域中具有通常知識者應該明瞭,對本發明的任何改進,對本發明產品各原料的均等替換及輔助成分的添加、具體方式的選擇等,均落在本發明的保護範圍和公開範圍之內。
Claims (14)
- 如申請專利範圍第1或2項所記載之改性馬來醯亞胺化合物,其中,前述R1、R2及R3各自獨立地選自CH3、C2H5或C3H7所成群中的任意一種。
- 一種改性馬來醯亞胺化合物的製備方法,其係製備如申請專利範圍第1至4項中任一項所記載之改性馬來醯亞胺化合物,其特徵係:前述製備方法包含:化合物(A)或者含胺基矽烷的有機金屬鹽與含有至少兩個馬來醯亞胺基團的化合物(B)進行加熱反應,得到前述改性馬來醯亞胺化合物。
- 如申請專利範圍第5項所記載之製備方法,其中,前述加熱反應的溫度為100至200℃;前述加熱反應的時間為1至30小時;前述加熱反應在冷凝回流的條件下進行;前述加熱反應在攪拌下進行。
- 如申請專利範圍第5或6項所記載之製備方法,其中,前述化合物(A)或者含胺基矽烷的有機金屬鹽與化合物(B)的莫耳比為10:90至80:20。
- 如申請專利範圍第5或6項所記載之製備方法,其中,前述加熱反應中加入促進劑,前述促進劑的用量為化合物(B)質量的0.01至10%。
- 如申請專利範圍第5或6項所記載之製備方法,其中,前述加熱反應中加入溶劑,前述溶劑的用量為化合物(B)質量的10至500%。
- 一種樹脂組成物,其特徵係:前述樹脂組成物中含有申請專利範圍第1至4中任一項所記載之改性馬來醯亞胺化合物。
- 一種預浸片,其特徵係:前述預浸片包含增強材料及通過含浸乾燥後附著其上的申請專利範圍第10項所記載之樹脂組成物。
- 一種絕緣板,其特徵係:前述絕緣板包含至少一張申請專利範圍第11項所記載之預浸片。
- 一種覆金屬箔層壓板,其特徵係:前述覆金屬箔層壓板包含至少一張申請專利範圍第11項所記載之預浸片以及覆於疊合後的預浸片一側或兩側的金屬箔。
- 一種印刷電路板,其特徵係:前述印刷電路板包含至少一張申請專利範圍第11項所記載之預浸片,或至少一張申請專利範圍第12項所記載之絕緣板,或至少一張申請專利範圍第13項所記載之覆金屬箔層壓板。
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