TWI415879B - 熱硬化性聚醯亞胺矽樹脂組成物 - Google Patents
熱硬化性聚醯亞胺矽樹脂組成物 Download PDFInfo
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- TWI415879B TWI415879B TW097133799A TW97133799A TWI415879B TW I415879 B TWI415879 B TW I415879B TW 097133799 A TW097133799 A TW 097133799A TW 97133799 A TW97133799 A TW 97133799A TW I415879 B TWI415879 B TW I415879B
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- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- ZJCFFCAWTLMEAE-UHFFFAOYSA-N ethyl hexyl carbonate Chemical compound [CH2]COC(=O)OCCCCCC ZJCFFCAWTLMEAE-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
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- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 229920001601 polyetherimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- WYVAMUWZEOHJOQ-UHFFFAOYSA-N propionic anhydride Chemical compound CCC(=O)OC(=O)CC WYVAMUWZEOHJOQ-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000004060 quinone imines Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
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Description
本發明是有關於一種熱硬化性聚醯亞胺矽樹脂組成物,詳細而言,關於一種含有自由基聚合性基團的聚醯亞胺矽系組成物,該組成物藉由與預定硬化劑組合,在較以往低的溫度下且短時間進行硬化,提供耐熱性、機械強度、可撓性、耐溶劑性以及與各種基材的黏合性優異的硬化覆膜。
聚醯亞胺樹脂(polyimide resin)的耐熱性高、電絕緣性優異,因此廣泛用作印刷電路基板、耐熱性黏合膠帶、電氣零件、半導體材料的保護膜、層間絕緣膜等。但聚醯亞胺樹脂僅溶於有限的溶劑,使得有時作業性差。因此,採用以下方法:於基材上塗佈較易溶於各種有機溶劑的聚醯胺酸,藉由高溫處理進行脫水環化而得到聚醯亞胺樹脂的方法。然而,在該方法中,必需進行高溫且長時間的加熱,因此容易引起基材的熱劣化。另一方面,若加熱不充分,則聚醯胺酸殘留在所得樹脂的結構中,導致耐濕性、耐腐蝕性等下降。
因此,已知於基材上塗佈可溶於有機溶劑的聚醯亞胺樹脂的溶液來代替聚醯胺酸,之後藉由加熱使溶劑揮散,形成聚醯亞胺樹脂覆膜的方法(例如日本專利特開平2-36232號公報)。但是,使用上述可溶於有機溶劑的聚醯亞胺樹脂得到的樹脂覆膜的耐溶劑性差。因此,有人提案
了一種可溶於有機溶劑且具有聚合性側鏈的加熱硬化型聚醯亞胺矽(例如日本專利特開平2-147630號公報、日本專利特開平7-268098號公報)。日本專利特開平2-147630號公報所記載的樹脂能夠利用熱的方法、光的方法中的任一種方法進行硬化。日本專利特開平7-268098號公報所記載的樹脂與有機氫矽氧烷進行氫甲矽烷基化反應而硬化,但硬化需要5個小時。
因此,本發明之目的在於提供一種在較低溫度下且短時間硬化的聚醯亞胺矽樹脂組成物。
本發明人等進行了各種研究,結果發現:藉由將含有自由基聚合性基團的聚醯亞胺矽樹脂與特定的硬化劑組合,能夠達到上述目的。即,本發明關於一種熱硬化性聚醯亞胺矽樹脂組成物,其中包括:100重量份的含有結合在矽原子上的自由基聚合性基團的聚醯亞胺矽樹脂、0.1~20重量份的過氧碳酸酯硬化劑以及溶劑,其中熱硬化性聚醯亞胺矽樹脂組成物中的樹脂成分是由聚醯亞胺矽樹脂組成。
本發明之組成物為與各種有機溶劑相溶的溶液狀,操作性優異。另外,本發明之組成物藉由低溫且短時間的熱處理可以形成硬化覆膜。所得硬化覆膜的耐熱性、機械強度、耐溶劑性以及與各種基材的密合性優異。
為讓本發明之上述和其他目的、特徵和優點能更明顯易懂,下文特舉較佳實施例,並配合所附圖式,作詳細說
明如下。
本發明之樹脂組成物,其聚醯亞胺矽樹脂中的矽原子上結合的自由基聚合性基團在過氧碳酸酯的存在下硬化。藉此可以達成低溫下的快速硬化。作為上述自由基聚合性基團,可以列舉出:乙烯基、丙烯基、(甲基)丙烯醯氧丙基、(甲基)丙烯醯氧乙基、(甲基)丙烯醯氧甲基、苯乙烯基等。上述基團中,從容易獲取原料的角度考慮,較佳的是乙烯基。只要是聚醯亞胺矽樹脂的矽部分,則上述自由基聚合性基團可以存在於端部、中央部等任一部位。
本發明中使用的過氧碳酸酯可以列舉出:第三級丁基過氧異丙基碳酸酯、第三級丁基過氧2-乙基己基碳酸酯、第三級戊基過氧2-乙基己基碳酸酯等單過氧碳酸酯;二(2-乙基己基)過氧二碳酸酯、1,6-雙(第三級丁基過氧羰氧基)己烷、雙(4-第三級丁基環己基)過氧二碳酸酯、二(2-乙氧基乙基)過氧二碳酸酯、二(正丙基)過氧二碳酸酯、二異丙基過氧二碳酸酯等。其中,較佳的是第三級丁基過氧2-乙基己基碳酸酯、第三級戊基過氧2-乙基己基碳酸酯、1,6-雙(第三級丁基過氧羰氧基)己烷、雙(4-第三級丁基環己基)過氧二碳酸酯。上述過氧碳酸酯與本發明中的聚醯亞胺樹脂具有良好的相溶性,達到低溫下的快速硬化。
相對於100重量份的聚醯亞胺矽樹脂,過氧碳酸酯的量為0.1~20重量份,較佳的是1~10重量份。若過氧碳酸酯的添加量超過上述上限值,則本發明之組成物的保存
穩定性及硬化物的耐高溫高濕性趨於下降。而當過氧碳酸酯的添加量少於上述下限值時,硬化物的耐溶劑性差。
作為本發明之組成物中的溶劑,只要是能夠溶解聚醯亞胺矽樹脂和過氧碳酸酯的溶劑即可。適合的溶劑的例子可以列舉出:四氫呋喃、茴香醚等醚類;環己酮、2-丁酮、甲基異丁基酮、2-庚酮、2-辛酮、苯乙酮等酮系溶劑;乙酸丁酯、苯甲酸甲酯、γ-丁內酯等酯系溶劑;丁基溶纖劑醋酸酯、丙二醇單甲醚乙酸酯等溶纖劑系溶劑;N,N-二甲基甲醯胺、N,N-二甲基乙醯胺、N-甲基-2-吡咯烷酮等醯胺系溶劑以及甲苯、二甲苯等芳香族烴類系溶劑,較佳的是酮系溶劑、酯系溶劑以及溶纖劑系溶劑。上述溶劑可以單獨使用,也可以是兩種或兩種以上組合使用。上述溶劑的量,較佳的是,依賴於樹脂的溶解性、塗佈時的作業性、所需覆膜的厚度等而適當調節,通常在聚醯亞胺樹脂濃度為1~50重量百分比(wt%)的範圍內使用。或者,在保存組成物時先製成較高的樹脂濃度,使用時可以稀釋成所需濃度。
較佳的是,聚醯亞胺矽樹脂包含下述式(1)所示的兩種重複單元。
上式為一種組成式。即,k和m表示包括A的重複單元與包括B的重複單元的含有比例。k為0≦k≦1、m為
0<m≦1的數,k+m=1。如以下所說明,B為矽殘基,含有自由基聚合性基團。各構成單元可以隨機結合。
式(1)中的X為下述四價基團中的任一種。
式(1)中的A為下述式(2)表示的二價基團。
上述式(2)中,D彼此獨立地表示下述二價有機基團中的任一種。e、f、g為0或1。
-CH2-、-O-、-SO2-、-CONH-、、、
作為式(2)所表示的基團,可以列舉出下述基團。
式(1)中,B以下述式(3)來表示。
式(3)中,R1彼此獨立地表示碳原子數為1~8的一價烴基,可以列舉如:甲基、乙基、丙基、丁基、戊基、己基等烷基;環戊基、環己基等環烷基;苯基等芳基;苄基、苯乙基等芳烷基等。從容易獲取原料的角度考慮,較佳的是甲基、乙基、苯基。R2為上述自由基聚合性基團。
a為0~100的整數,較佳的是3~70的整數。b為1~100的整數,較佳的是3~70的整數,更佳的是5~50的整數。
式(1)的聚醯亞胺樹脂,其聚苯乙烯換算的重量平均分子量為5000~150000,較佳的是8000~100000。分子量小於上述下限值的聚醯亞胺樹脂,所得覆膜的強度低。而分
子量超過上述上限值的聚醯亞胺樹脂缺乏對溶劑的相溶性,難以操作。
聚醯亞胺矽樹脂可以利用習知的方法來製備。首先,向溶劑中加入用於衍生X的酸二酐、用於衍生A的二胺以及用於衍生B的二胺基聚矽氧烷,使之在低溫下、即20℃~50℃左右反應,製造聚醯亞胺樹脂的前驅體聚醯胺酸。接下來,將所得聚醯胺酸溶液較佳的是升溫至80℃~200℃,特別佳的是升溫至140℃~180℃,使聚醯胺酸的醯胺進行脫水閉環反應,從而得到聚醯亞胺矽樹脂的溶液。將該溶液投入到水、甲醇、乙醇、乙腈等溶劑中,使反應產物沉澱,並乾燥該沉澱物,從而可以得到聚醯亞胺矽樹脂。
其中,相對於四羧酸二酐,二胺以及二胺基聚矽氧烷的總計比例以莫耳比計算,較佳的是0.95~1.05,特別佳的是0.98~1.02的範圍。另外,作為製造聚醯亞胺矽樹脂時所使用的溶劑,可以列舉出:N-甲基-2-吡咯烷酮、環己酮、γ-丁內酯、N,N-二甲基乙醯胺等。另外,藉由並用甲苯、二甲苯等芳香族烴類,也可以容易地利用共沸除去醯亞胺化時生成的水。上述溶劑可以單獨使用一種,也可以是兩種或兩種以上組合使用。
需要說明的是,為了調整聚醯亞胺矽樹脂的分子量,也可以添加鄰苯二甲酸酐、苯胺等一官能基原料。此時,相對於聚醯亞胺矽樹脂,上述一官能基原料的添加量較佳的是小於等於10莫耳百分比。
另外,在醯亞胺化過程中,可以採用藉由添加脫水劑及醯亞胺化催化劑,並根據需要加熱至50℃左右而進行醯亞胺化的方法。在上述方法中,作為脫水劑,例如可以使用乙酸酐、丙酸酐、三氟乙酸酐等酸酐。相對於1莫耳的二胺,脫水劑的使用量較佳的是1~10莫耳。作為醯亞胺化催化劑,例如可以使用吡啶、三甲基吡啶、二甲基吡啶、三乙胺等第三級胺。相對於1莫耳所使用的脫水劑,醯亞胺化催化劑的使用量較佳的是0.5~10莫耳。
在使用二胺以及四羧酸二酐中的至少一種的多種情況下,對反應方法沒有特別限定,例如有:預先將全部原料混合後使之共縮聚的方法、或者一邊使所使用的兩種或兩種以上的二胺或四羧酸二酐個別地進行反應一邊依序添加的方法等。
作為用於衍生X的酸二酐,可以列舉出:3,3’,4,4’-二苯基碸四羧酸二酐、3,3’,4,4’-聯苯四羧酸二酐、2,3’,3,4’-聯苯四羧酸二酐、5-(2,5-二氧代四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、4-(2,5-二氧代四氫呋喃-3-基)-1,2,3,4-四氫萘-1,2-二羧酸酐、1,2,3,4-丁烷四羧酸二酐、3,3’,4,4’-二苯甲酮四羧酸二酐、4,4’-六氟亞丙基雙鄰苯二甲酸二酐、2,2’-雙(對-偏苯三甲氧苯基(p-trimethoxyphenyl))丙烷、1,3-四甲基二矽氧烷雙鄰苯二甲酸二酐、4,4’-氧基二鄰苯二甲酸二酐。
作為用於衍生A的二胺,可以列舉出:4,4’-二胺基苯甲醯苯胺、4,4’-二胺基二苯醚、3,4’-二胺基二苯醚、4,4’-
二胺基二苯碸、3,3’-二甲基-4,4’-二胺基聯苯、4,4’-(對亞苯基二異亞丙基)二苯胺、4,4’-(間亞苯基二異亞丙基)二苯胺、1,3-雙(4-胺基苯氧基)苯、1,4-雙(4-胺基苯氧基)苯、1,3-雙(3-胺基苯氧基)苯、2,2-雙[4-(4-胺基苯氧基)苯基]丙烷、2,2-雙[4-(4-胺基苯氧基)苯基]六氟丙烷、雙[4-(4-胺基苯氧基)苯基]碸、雙[4-(3-胺基苯氧基)苯基]碸、4,4’-雙(4-胺基苯氧基)聯苯、9,9’-雙(4-胺基苯基)芴等。
作為用於衍生B的二胺基聚矽氧烷,可以使用在上述式(3)的兩末端結合有胺基的二胺基聚矽氧烷。
藉由將如此操作而得到的聚醯亞胺矽樹脂和過氧碳酸酯以及溶劑利用混合器等的習知方法進行混合,可以得到本發明之組成物。上述組成物中,可以在不阻礙本發明之目的的範圍內添加慎用的添加劑、例如用於提高與基材的密合性的矽烷耦合劑。
當上述組成物中含有低沸點的溶劑時,於基材上塗佈上述組成物後,使該溶劑揮發,之後在約80℃~200℃的溫度下加熱0.5~2小時,可以除去溶劑,並且可以硬化。因此,上述組成物適合作為對耐熱性較低的基材或因熱而變質的材料施與覆膜的覆膜劑。並且,無需用於照射光的特別的裝置,簡便地得到固化覆膜,因此認為上述組成物有助於提高作業性以及節省資源。
以下,給出實施例來進一步說明本發明,但本發明並不限於這些實施例。
在具備攪拌機、溫度計及氮置換裝置的燒瓶內加入71.6g(0.2莫耳)的3,3’,4,4’-二苯基碸四羧酸二酐及350g的環己酮。然後,一邊進行調節使反應系統的溫度不超過50℃,一邊向上述燒瓶內滴加將87.6g(0.1莫耳)的下述式(4)表示的二胺基乙烯基矽氧烷和41.1g(0.1莫耳)的2,2-雙[4-(4-胺基苯氧基)苯基]丙烷溶解於100g的環己酮中的溶液。滴加結束後,再於室溫下攪拌10小時。接著,在上述燒瓶上安裝帶有水分收納器的回流冷凝器,之後加入50g的二甲苯,升溫至150℃,並保持該溫度6小時,得到黃褐色溶液。將如此操作而得到的溶液冷卻至室溫(25℃)後投入到甲醇中,乾燥所得的沉澱物,得到含有下述式(5-1)及(5-2)表示的重複單元的聚醯亞胺矽樹脂。
測定所得樹脂的紅外線吸收圖譜時,未出現來自未反應的聚醯胺酸的吸收,在1,780cm-1和1,720cm-1處確認到來自亞胺基的吸收。利用以四氫呋喃作為溶劑的凝膠滲透層析法(GPC)測定該樹脂的重量平均分子量(聚苯乙烯換算)時,其重量平均分子量為34000。將該樹脂作為聚醯亞胺矽樹脂(a)。
在具備攪拌機、溫度計及氮置換裝置的燒瓶內加入88.8g(0.2莫耳)的4,4’-六氟亞丙基雙鄰苯二甲酸二酐和550g的環己酮。然後,一邊進行調節使反應系統的溫度不超過50℃,一邊向上述燒瓶內滴加將192.2g(0.06莫耳)的下述式(6)表示的二胺基乙烯基矽氧烷及40.9g(0.14莫耳)的1,3-雙(3-胺基苯氧基)苯溶解於200g的環己酮中的溶液。滴加結束後,再於室溫下攪拌10小時。接著,在上述燒瓶上安裝帶有水分收納器的回流冷凝器,之後加入70g的二甲苯,升溫至150℃,並保持該溫度6小時,得到黃
褐色溶液。將如此操作而得到的溶液冷卻至室溫(25℃)後投入到甲醇中,乾燥所得的沉澱物,得到含有下述式(7-1)及(7-2)表示的重複單元的聚醯亞胺矽樹脂。
測定所得樹脂的紅外線吸收圖譜時,未出現來自未反應的聚醯胺酸的吸收,在1,780cm-1和1,720cm-1處確認到來自亞胺基的吸收。按照與合成例1相同之方式測定該樹脂的重量平均分子量時,其重量平均分子量為42000。將該樹脂作為聚醯亞胺矽樹脂(b)。
在具備攪拌機、溫度計及氮置換裝置的燒瓶內加入62.0g(0.2莫耳)的羥基二鄰苯二甲酸二酐和400g的正甲基-2-吡咯烷酮。然後,一邊進行調節使反應系統的溫度不超過50℃,一邊向上述燒瓶內滴加將102g(0.06莫耳)的下述式(8)表示的二胺基乙烯基矽氧烷和57.5g(0.14莫耳)
的2,2-雙[4-(4-胺基苯氧基)苯基]丙烷溶解於100g的環己酮中的溶液。滴加結束後,再於室溫下攪拌10小時。接著,在上述燒瓶上安裝帶有水分收納器的回流冷凝器,之後加入70g的二甲苯,升溫至150℃,並保持該溫度6小時,得到黃褐色溶液。將如此操作而得到的溶液冷卻至室溫(25℃)後投入到甲醇中,乾燥所得的沉澱物,得到下述式(9-1)及(9-2)表示的聚醯亞胺矽樹脂。
測定所得樹脂的紅外線吸收圖譜時,未出現來自未反應的聚醯胺酸的吸收,在1,780cm-1和1,720cm-1處確認到來自亞胺基的吸收。按照與合成例1相同之方式測定該樹脂的重量平均分子量時,其重量平均分子量為35000。將該樹脂作為聚醯亞胺矽樹脂(c)。
製備用於比較的不含自由基聚合性基團的聚醯亞胺矽樹脂。
在具備攪拌機、溫度計和氮置換裝置的燒瓶內加入71.6g(0.2莫耳)的3,3’4,4’-二苯基碸四羧酸二酐和350g的環己酮。然後,一邊進行調節使反應系統的溫度不超過50℃,一邊向上述燒瓶內滴加將84.0g(0.6莫耳)的下述式(10)表示的二胺基矽氧烷及50g(0.1莫耳)的2,2-雙[4-(4-胺基苯氧基)苯基]丙烷溶解於100g的環己酮中的溶液。滴加結束後,再於室溫下攪拌10小時。接著,在上述燒瓶上安裝帶有水分收納器的回流冷凝器,之後加入50g的二甲苯,升溫至150℃,並保持該溫度6小時,得到黃褐色溶液。將如此操作而得到的溶液冷卻至室溫(25℃)後投入到甲醇中,乾燥所得的沉澱物,得到含有下述式(11-1)及(11-2)表示的重複單元的聚醯亞胺矽樹脂。
測定所得樹脂的紅外線吸收圖譜時,未出現來自未反應的聚醯胺酸的吸收,在1,780cm-1和1,720cm-1處確認到
來自亞胺基的吸收。按照與合成例1相同之方式測定該樹脂的重量平均分子量時,其重量平均分子量為30000。將該樹脂作為聚醯亞胺矽樹脂(d)。
將表1所示的聚醯亞胺矽樹脂、硬化劑及溶劑按照表中所示的添加比例混合,製備樹脂組成物。需要說明的是,表1中的「份」均表示「重量份」。另外,表1中硬化劑一欄的記號分別表示下述硬化劑。
(I)第三級丁基過氧-2-乙基己基碳酸酯
(II)1,6-雙(第三級丁基過氧羰氧基)己烷
(III)第三級戊基過氧2-乙基己基碳酸酯
(IV)雙(4-第三級丁基環己基)過氧二碳酸酯
(V)1,1-雙(第三級丁基過氧)-3,3,5-三甲基環己烷
(VI)過氧化環己酮
(VII)苯甲醯過氧化物
(VIII)過氧化乙酸第三級丁酯
(IX)1,1,3,3-四甲基丁基氫過氧化物
於塗覆有氟樹脂的板上塗佈所得的各熱硬化性樹脂組成物,使乾燥後的厚度為約0.1mm,於80℃下加熱30分鐘,再於150℃下加熱1小時,形成聚醯亞胺樹脂硬化覆膜。將所得的硬化覆膜於常溫的N-甲基-2-吡咯烷酮(NMP)中浸漬30分鐘,之後目視觀察覆膜是否膨脹。結果如表2
所示。
於銅基板上塗佈樹脂組成物,於80℃下加熱30分鐘,再於表1所示的各最終硬化溫度下加熱1小時,形成硬化覆膜。利用方格剝離試驗(JISK5400)評價所得的帶有硬化覆膜的銅基板在150℃的乾燥機中放置360小時後的黏合性(作為「耐熱黏合性」)或在120℃、2氣壓的飽和水蒸氣中放置168小時後的黏合性(作為「高溫高濕黏合性」)。結果如表2所示。需要說明的是,表2中的數值(分子/分母)表示每100個分畫數(分母)中的未剝離的分畫數(分子)。即,100/100時表示完全沒有剝離,0/100時表示全部剝離。
將實施例2、4及比較例1的組成物分別於80℃下加熱30分鐘、再於150℃下加熱1小時,針對所得硬化物,依據JIS K7113測定拉伸率和拉伸強度。結果如表3所示。
由表2可知:與缺少硬化劑或自由基聚合性的比較例及含有其他過氧化物的參考例的組成物相比,包括含有自由基聚合性基團的聚醯亞胺矽和過氧碳酸酯的組成物的硬化性能明顯高,藉由在150℃~180℃左右的溫度下加熱數小時左右,形成耐溶劑性、耐熱性、機械特性優異的硬化
物。
本發明之組成物可用作電氣零件、半導體材料的保護膜、層間絕緣膜、黏合膠帶。特別適合施與耐熱性較低的基材或因熱而變質的材料。
雖然本發明已以較佳實施例揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作些許之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為准。
Claims (4)
- 一種熱硬化性聚醯亞胺矽樹脂組成物,包括:一具有以下述式(1)表示的兩種重複單元,並以聚苯乙烯換算的重量平均分子量5,000~150,000的聚醯亞胺矽樹脂,100重量份;一過氧碳酸酯硬化劑,0.1~20重量份;以及一溶劑,其中該熱硬化性聚醯亞胺矽樹脂組成物中的樹脂成分是由該聚醯亞胺矽樹脂組成,
- 如申請專利範圍第1項所述之熱硬化性聚醯亞胺矽樹脂組成物,其中R2為乙烯基。
- 如申請專利範圍第1項所述之熱硬化性聚醯亞胺矽樹脂組成物,其中過氧碳酸酯硬化劑選自從第三級丁基過氧2-乙基己基碳酸酯、第三級戊基過氧2-乙基己基碳酸酯、1,6-雙(第三級丁基過氧羰氧基)己烷、雙(4-第三級丁基環己基)過氧二碳酸酯所組成的組群。
- 如申請專利範圍第1項所述之熱硬化性聚醯亞胺矽樹脂組成物,其中上述溶劑選自酮系溶劑、酯系溶劑以及溶纖劑系溶劑所組成的組群。
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CN109181526A (zh) * | 2018-07-19 | 2019-01-11 | 北京理工大学 | 基于聚硅氧烷共聚改性聚酰亚胺的柔性耐高温漆包线漆组合物及其制备方法 |
JP7024660B2 (ja) * | 2018-08-10 | 2022-02-24 | 信越化学工業株式会社 | 熱硬化性樹脂組成物及び半導体装置 |
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GB8431735D0 (en) * | 1984-12-15 | 1985-01-30 | Isothermic Eng & Research Ltd | Manufacture of casings for quilted articles |
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JP3974686B2 (ja) * | 1997-06-17 | 2007-09-12 | 東レ・ダウコーニング株式会社 | 有機樹脂改質剤および有機樹脂 |
US7141614B2 (en) | 2001-10-30 | 2006-11-28 | Kaneka Corporation | Photosensitive resin composition and photosensitive films and laminates made by using the same |
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JPH08218034A (ja) * | 1995-02-15 | 1996-08-27 | Nippon Steel Chem Co Ltd | ポリイミド系耐熱性コーティング剤組成物 |
JP2006269250A (ja) * | 2005-03-24 | 2006-10-05 | Shin Etsu Chem Co Ltd | 導電性膜形成用組成物、導電性膜の形成方法及び導電性膜 |
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EP2033985A2 (en) | 2009-03-11 |
EP2033985B1 (en) | 2017-04-12 |
EP2033985A3 (en) | 2009-10-07 |
KR20090025155A (ko) | 2009-03-10 |
JP2009062429A (ja) | 2009-03-26 |
TW200914500A (en) | 2009-04-01 |
US7981976B2 (en) | 2011-07-19 |
JP4590443B2 (ja) | 2010-12-01 |
KR101497704B1 (ko) | 2015-03-02 |
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