TWI478961B - 具有醇羥基之新穎聚醯亞胺矽氧及其製法 - Google Patents
具有醇羥基之新穎聚醯亞胺矽氧及其製法 Download PDFInfo
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- TWI478961B TWI478961B TW099133308A TW99133308A TWI478961B TW I478961 B TWI478961 B TW I478961B TW 099133308 A TW099133308 A TW 099133308A TW 99133308 A TW99133308 A TW 99133308A TW I478961 B TWI478961 B TW I478961B
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- hydroxyl group
- divalent organic
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims description 61
- 230000001476 alcoholic effect Effects 0.000 title claims description 33
- 238000000034 method Methods 0.000 title claims description 5
- 125000000962 organic group Chemical group 0.000 claims description 63
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 31
- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 150000002923 oximes Chemical class 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 13
- 150000008065 acid anhydrides Chemical class 0.000 claims description 13
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- 150000004985 diamines Chemical class 0.000 claims description 12
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- 125000000217 alkyl group Chemical group 0.000 claims description 9
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- 150000008064 anhydrides Chemical class 0.000 claims description 7
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 6
- 230000018044 dehydration Effects 0.000 claims description 4
- 238000006297 dehydration reaction Methods 0.000 claims description 4
- 150000002466 imines Chemical class 0.000 claims description 4
- 238000007363 ring formation reaction Methods 0.000 claims description 4
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- 125000001183 hydrocarbyl group Chemical group 0.000 claims 3
- 239000000243 solution Substances 0.000 description 28
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- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
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Description
本發明關於一種具有一級羥基之新穎聚醯亞胺,其由於其耐熱性、耐化學藥品性、絕緣性能及可撓性而適用於半導體裝置之保護絕緣膜、多層印刷電路板之絕緣膜、焊料保護膜及覆蓋膜等;及用於製造該聚醯亞胺之方法。
至今,已經有人以各種方法硏究並提出具有酚羥基之聚醯亞胺類(參見,專利文件1、2、3及4)。再者,也曾有人提出具有環氧基或不飽和烴基及二級醇羥基之聚醯亞胺(參見,專利文件5)。再者,已經有人提出具有富於反應性之一級醇羥基的聚醯亞胺(參見,專利文件6)。
專利文件1:JP-A-6-200216
專利文件2:日本專利案第3329677號
專利文件3:JP-A-2004-51794
專利文件4:JP-A-2007-217490
專利文件5:JP-A-2001-335619
專利文件6:JP-A-2006-131892
然而,尚未硏發出使用經酸酐改質之聚矽氧之具有富於反應性之一級醇羥基的聚醯亞胺矽氧。
由於上述情況而完成本發明並提供使用經酸酐改質之聚矽氧之具有一級醇羥基的新穎聚醯亞胺矽氧,及用於製造該聚醯亞胺矽氧之方法。
換言之,本發明提供下列項目1至8。
1.一種具有一級醇羥基之聚醯亞胺矽氧,其係藉由下列通式(1)表示:
其中k及m各自為正整數,其中k及m滿足0.01k/(k+m)<1之關係;X為下列通式(2)所示之四價有機基團;
其中R1
各自獨立地為具有1至8個碳原子之單價烴基,R2
各自獨立地為三價有機基團,及n為平均1至120之數值;Y各自為二價有機基團且其至少一部分係由下列通式(3)表示:
其中A各自為選自下列基團之二價有機基團:
其可互為相同或不同,B及C各自為具有1至4個碳原子之烷基或氫原子,其可互為相同或不同,a為0或1,b為0或1,c為0至10之整數,及R3
各自為選自含有酚羥基或醇羥基之有機基團的單價基團,其中R3
之至少一者為含有一級醇羥基之有機基團;及W為X以外的四價有機基團。
2.如第1項之聚醯亞胺矽氧,其係下列通式(1-1)所示之聚醯亞胺矽氧:
其中X及W與上文相同;Y1
各自為通式(3)所示之二價有機基團且Y2
各自為通式(3)所示之基團以外的二價有機基團;及p及r各自為正整數,且q及s各自為0或正整數,其中p、q、r及s滿足p+q=k及r+s=m的關係(其中k及m與上文相同)。
3.如第1或2項之聚醯亞胺矽氧,其中在該通式(3)中,R3
之至少一者為選自-OH、-OCH2
CH(OH)CH2
OH及-OCH(CH2
OH)CH2
OH之單價基團。
4.如第1至3項中任一項之聚醯亞胺矽氧,其中在該通式(1)中,W為下式所示之四價有機基團之一:
5.如第1至4項中任一項之聚醯亞胺矽氧,其具有20至200 KOH mg/g之OH值。
6.如第2至5項中任一項之聚醯亞胺矽氧,其中Y2
為至少一選自下列者下列通式(4)所示之二價有機基團:
其中D各自獨立地為任何下列二價有機基團:-CH2
-,-O-,-SO2
-,-CONH-,e及f各自獨立地為0或1且g為0或1;及下列通式(5)所示之二價有機基團
其中R4
各自獨立地為具有1至8個碳原子之單價烴基且h為1至80之整數。
7.如第1至6項中任一項之聚醯亞胺矽氧,其末端具有酚基、硫醇基或羧基。
8.一種具有一級醇羥基之聚醯亞胺矽氧之製法,該聚醯亞胺矽氧係藉由下列通式(1)表示:
其中k及m各自為正整數,其中k及m滿足0.01k/(k+m)<1之關係,X為下列通式(2)所示之四價有機基團,
其中R1
各自獨立地為具有1至8個碳原子之單價烴基,R2
各自獨立地為三價有機基團,及n為平均1至120之數值,Y各自為二價有機基團且其至少一部分係由下列通式(3)表示:
其中A各自為選自下列基團之二價有機基團:-CH2
-,-O-,-SO2
-,-CONH-,其可互為相同或不同,B及C各自為具有1至4個碳原子之烷基或氫原子,其可互為相同或不同,a為0或1,b為0或1,c為0至10之整數,及R3
各自為選自含有酚羥基或醇羥基之有機基團的單價基團,其中R3
之至少一者為含有一級醇羥基之有機基團;及W為X以外的四價有機基團,該方法包含:使具有酚羥基之二胺與經酸酐改質之聚矽氧、酸酐及,必要的話,沒有酚羥基和羧基之二胺反應以獲得聚醯胺酸;接著對該聚醯胺酸進行脫水閉環反應以獲得下列通式(6)所示之具有酚羥基之聚醯亞胺:
其中X、W、k及m與上文相同;及Z各自為二價有機基團且其至少一部分為下列通式(7)所示之二價有機基團:
其中A各自為選自下列基團之二價有機基團:-CH2
-,-O-,-SO2
-,-CONH-,其可互為相同或不同,B及C各自為具有1至4個碳原子之烷基或氫原子,其可互為相同或不同,a為0或1,b為0或1,c為0至10之整數,以及隨後使該聚醯亞胺與縮水甘油反應,並另外任意與酸酐反應。
本發明之聚醯亞胺矽氧係有優異反應性且也有優異之對基材之黏著力及耐化學藥品性。此外,該聚醯亞胺矽氧提供具有可撓性及低應力性質之固化產物。因此,本發明之聚醯亞胺矽氧係適當作為供電氣和電子部件及半導體裝置等用之保護膜。
本發明之聚醯亞胺矽氧係藉由下列通式(1)表示。
在本發明之聚醯亞胺矽氧中,X具有下列通式(2)所示之結構。本發明之聚醯亞胺矽氧係藉由併入此單元變成可撓性。
在該式(2)中,R1
各自獨立地為具有1至8個碳原子之單價烴基,及其實例包括烷基如甲基、乙基、丙基、丁基、戊基及己基;環烷基如環戊基及環己基;芳基如苯基;芳烷基如苯甲基及苯乙基;及烯基如乙烯基、烯丙基、丙烯基、異丙烯基及丁烯基。從原料易取得性之觀點來看,較佳為甲基、乙基、苯基及乙烯基。
在該式(2)中,R2
各自獨立地為三價有機基團,較佳為具有2至10個碳原子之三價有機基團。其實例包括可藉由自烷基丁二酸酐類如丙基丁二酸酐;降莰烯二羧酸酐;丙基納迪克酸酐(propylnadic anhydride);及苯二甲酸酐移除羧或羧酸酐基所形成之殘基。較佳為來自降莰酸酐及聚丁二酸酐之殘基。再者,在該式(2)中,n為1至120之整數,較佳3至80,且更佳5至50。
關於X,可述及下列結構。
在上述結構中,n1
及n2
各自為0或1或更大之整數並滿足n1
+n2
=n之關係。再者,n3
及n4
各自為0或1或更大之整數並滿足n3
+n4
=n之關係。再者,n5
及n6
各自為0或1或更大之整數並滿足n5
+n6
=n之關係。
關於X,更明確地說,可述及下列結構。
上述X可衍生自經改質之聚矽氧,該聚矽氧係藉由使上述具有不飽和基團之酸酐如丁二酸酐、降莰烯二羧酸酐、丙基納迪克酸酐或苯二甲酸酐與有機氫聚矽氧烷反應獲得。依據該有機氫聚矽氧烷中之眾多矽氧烷單元的分佈,也能分配所得之經酸酐改質之聚矽氧烷的眾多矽氧烷單元。因此,該式(2)中之n表示其平均值。
通式(1)中的Y各自為具有一級醇羥基的二價有機基團且其至少一部分係由下列通式(3)表示。
在該式(3)中,A各自獨立地為選自下列基團之二價有機基團:-CH2
-,-O-,-SO2
-,-CONH-,在該式(3)中,a為0或1,b為0或1,c為0至10之整數,且c較佳為1至10之整數。
在該式(3)中,B及C各自為具有1至4個碳原子之烷基或氫原子並可互為相同或不同。其實例包括甲基、乙基、丙基、丁基及氫原子。這些當中,從原料之易取得性的觀點來看,較佳為甲基及氫原子。
在上述式(3)中,R3
各自為選自含有酚羥基或醇羥基之有機基團的單價基團,且R3
之至少一者為含有一級醇羥基之有機基團。明確地說,可述及-OH、-OCH2
CH(OH)CH2
OH及-OCH(CH2
OH)CH2
OH。
關於該式(3)所示之基團,可述及下列基團。
另一個部分之Y可為上述通式(3)所示之基團以外的二價有機基團。也就是說,本發明之聚醯亞胺矽氧較佳為下列通式(1-1)所示之聚醯亞胺矽氧。
在該式(1-1)中,X及W與上文相同。
Y1
各自為上述通式(3)所示之二價有機基團且Y2
各自為上述通式(3)所示之基團以外的二價有機基團,p及r各自為正整數,且q及s各自為0或正整數,其中p、q、r及s滿足p+q=k及r+s=m的關係(其中k及m與上文相同)。
Y2
各自為上述通式(3)所示之基團以外的二價有機基團,即,沒有一級醇羥基之二價有機基團。明確地說,Y2
較佳為至少一個選自下列通式(4)所示之二價有機基團及下列通式(5)所示之二價有機基團。
該式(4)如下。
在上式中,D各自獨立地為與上述所界定之A相同的二價有機基團。此外,e及f各自獨立地為0或1且g為0或1。
關於該式(4),可述及下列基團。
該式(5)如下。
在該式(5)中,R4
各自獨立地為具有1至8個碳原子之單價烴基,且其實例包括甲基、乙基、丙基、丁基、己基、環己基及苯基。這些當中,從原料之可取得性的觀點來看,特佳為甲基及苯基。
在該式(5)中,h為1至80之整數,較佳1至20之整數。
在該式(1)中,W可為任何習知之多種不同基團,只要其係上述X以外之四價有機基團並可例示下列基團。
具有上述各結構之聚醯亞胺矽氧具有較佳5,000至200,000之分子量(數量平均分子量),特佳8,000至100,000。當其分子量太小時,由該聚醯亞胺矽氧樹脂所獲得之膜的強度有時候會變低。另一方面,當其分子量太大時,該聚醯亞胺矽氧樹脂具有對溶劑差之相容性且在一些案例中處理能力將降低。
再者,含有X之重複單元的數目k為正整數且較佳為1至500,更佳3至300。含有W之重複單元的數目m為正整數且較佳為1至500,更佳3至300。
再者,k之比例,即,k/(k+m)滿足0.01k/(k+m)<1之關係。較佳地,該比例為0.1或更高且小於約1,更佳0.2或更高且小於0.95或更低,且特佳0.5或更高或0.9或更低。當該比例為低於0.01時,將難以達成足夠之可撓性。
本發明之聚醯亞胺矽氧較佳具有依據JIS K0070為20至200 KOH mg/g之OH值,特別是30至150 KOH mg/g。當該OH值落於該範圍以內時,在將該聚醯亞胺矽氧應用於後述應用之案例中,將獲得具有特別優良之性質者。
為了製造本發明之聚醯亞胺矽氧,先使具有酚羥基之二胺、經酸酐改質之聚矽氧、酸酐及,必要的話,沒有酚羥基和羧基之二胺反應以獲得聚醯胺酸。
該具有酚羥基之二胺的實例包括具有酚基之二胺類,如3,3’-二胺基-4,4’-二羥基聯苯、2,2’-二胺基-4,4’-二羥基聯苯、2,2-雙(4-胺基-3-羥苯基)丙烷、2,2-雙(3-胺基-4-羥苯基)丙烷、9,9-雙(3-胺基-4-羥苯基)茀、2,2’-亞甲基雙[6-(4-胺基-3,5-二甲基苯甲基)-4-甲基]酚、3,3’-二胺基-4,4’-二羥基二苯醚及2,2-雙(3-胺基-4-羥苯基)六氟丙烷。
關於該經酸酐改質之聚矽氧,可述及,例如,下列化合物。
在上式中,n為1至120之整數,較佳3至80之整數,且更佳5至50之整數。此外,n5
及n6
各自為0或1或更大之整數並滿足n5
+n6
=n。
該聚醯胺酸聚合時所用之酸酐的實例包括3,3’,4,4’-二苯碸四羧酸二酐、3,3’,4,4’-聯苯基四羧酸二酐、2,3’,3,4’-聯苯基四羧酸二酐、5-(2,5-二氧四氫-3-呋喃基)-3-甲基-3-環己烯-1,2-二羧酸酐、4-(2,5-二氧四氫呋喃-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’-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-三甲氧基苯基)丙烷、1,3-四甲基二矽氧烷雙鄰-苯二甲酸二酐及4,4’-氧二鄰-苯二甲酸二酐。
該沒有酚羥基和羧基之二胺的實例包括4,4’-二胺基苯甲醯胺苯、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-苯二異亞丙基)二苯胺、4,4’-(間-苯二異亞丙基)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)聯苯及9,9-雙(4-胺苯基)茀。
在該聚醯胺酸之合成中,該二胺組分對該酸二酐組分之比例係適當地仰賴該聚醯亞胺等之分子量的調整決定且通常為以莫耳比計在0.95至1.05之範圍中,較佳0.98至1.02。關此,為了於該聚醯亞胺矽氧末端引入反應性官能基,可加入胺基醇、胺基硫醇、官能性酸酐如偏苯三甲酸酐及胺化合物。在此案例中彼等加入之量較佳為以該酸二酐組分或該二胺組分為基準20莫耳%或更低。
該二胺與該酸二酐之反應通常在溶劑中進行。此溶劑可為能溶解聚醯亞胺之溶劑。該溶劑之具體實例包括醚類如四氫呋喃及苯甲醚;酮類如環己酮、2-丁酮、甲基異丁酮、2-庚酮、2-辛酮及苯乙酮;酯類如醋酸丁酯、苯甲酸甲酯及γ-丁內酯;纖維素類如丁基纖維素醋酸酯及丙二醇單甲醚醋酸酯;醯胺類如N,N-二甲基甲醯胺、N,N-二甲基乙醯胺及N-甲基-2-吡咯烷酮;及芳族烴類如甲苯及二甲苯。該溶劑較佳為酮、酯及纖維素,特佳γ-丁內酯、丙二醇單甲醚醋酸酯、N,N-二甲基乙醯胺或N-甲基-2-吡咯烷酮。這些溶劑之一種可單獨使用或可合併使用二或多種。通常,考量每1批之產率及溶解黏度等,調整該量以致於該聚醯亞胺之濃度變成10至40重量%。
接著,對上述獲得之聚醯胺酸施以脫水閉環反應以獲得通式(6)所示之具有酚羥基之聚醯亞胺,隨後使該聚醯亞胺與縮水甘油反應,並另外視需要與酸酐反應,藉以可獲得本發明之聚醯亞胺矽氧。
在該式(6)中,X、W、k及m與上文相同。
此外,Z各自為二價有機基團且其至少一部分為下列通式(7)所示之二價有機基團。
在該式(7)中,A、B、C、a、b及c與上文相同。
也就是說,關於該聚醯亞胺之合成,將上文所獲得之聚醯胺酸溶液加熱至通常80至200℃之溫度範圍,較佳140至180℃或將醋酸酐/吡啶混合溶液加至該聚醯胺酸溶液,並將所得之溶液加熱至約50℃藉以使該脫水之閉環反應能於該聚醯胺酸之醯胺部分處進行,藉以可獲得聚醯亞胺。
縮水甘油係以所需當量加至由此所獲得之分子中具有酚羥基之聚醯亞胺的有機溶劑溶液,該聚醯亞胺係由上述通式(6)表示,並整個加熱。因此,可獲得上述通式(1)所示之具有醇羥基的聚醯亞胺矽氧。儘管必須改變依據所引入之醇羥基的量作變化之縮水甘油的量,但是通常所變化之縮水甘油的量較佳為等於該酚羥基之0.3至3莫耳當量。反應溫度為40℃至180℃,較佳60至130℃。反應時間為數分鐘至12小時。再者,為加速該反應之目的,可添加觸媒如三乙胺。
再者,關於能在該縮水甘油反應之後任意反應之酸酐,可述及苯二甲酸酐、降莰烯二羧酐、環己基二羧酸酐、甲基環己基二羧酸酐及丁二酸酐等。
關於該酸酐之反應,藉由依所需之當量添加該酸酐及整個加熱,可獲得具有羧基且也具有醇羥基之目標聚醯亞胺矽氧。
由此所獲得之根據本發明的聚醯亞胺矽氧由於反應性等而為主要具有一級醇羥基之聚醯亞胺矽氧。此具有一級醇羥基之新穎的聚醯亞胺矽氧可用於半導體裝置之保護絕緣膜、多層印刷電路板之絕緣膜、焊料保護膜及覆蓋膜等,該等膜係有優異耐熱性、耐化學藥品性、絕緣性能及可撓性。
下文將引用合成實施例、實施例及比較例進一步詳細描述本發明,但是本發明並不限於下列實施例。
在裝備攪拌器、溫度計及氮取代裝置之燒瓶內填充31.0g(0.15 mol)之4,4’-氧二鄰-苯二甲酸二酐、155.1g(0.15 mol)之經酸酐改良的聚矽氧,其一般結構係由下式(8)表示,及600g之N-甲基-2-吡咯烷酮。接著,配合控制將91.5g(0.25 mol)之2,2-雙(4-胺基-3-羥苯基)六氟丙烷加至該燒瓶以致於該反應系統之溫度不超過50℃。其後,於室溫另攪拌該混合物10小時。接下來,將帶有蓄水器之迴流冷凝器安裝於該燒瓶,添加100g之二甲苯並將整個加熱至170℃。當維持於該溫度6小時時,獲得棕色溶液。
等由此所獲得之棕色溶液冷卻至室溫(25℃)之後,獲得具有酚羥基之聚醯亞胺溶液。接著,將23g之縮水甘油填至燒瓶中之聚醯亞胺溶液,接著於120℃加熱3小時。等該反應完成之後,將該溶液冷卻至室溫並將該反應溶液倒入甲醇中。接著,等所得之沉澱物過濾並乾燥之後,獲得具有一級醇羥基之目標聚醯亞胺。關於該聚合物之1
H-NMR(Lambda 300,由JEOL所製造)分析的結果,於10 ppm衍生自該酚羥基之峰減小且於4.6 ppm及4.8 ppm觀察到一級和二級醇羥基之峰,以致於發現到該聚合物為具有由下式所示之重複單元的結構之聚合物(參見第1圖)。關於凝膠滲透層析(GPC)之結果,該聚合物之數量平均分子量為39,000且依據JIS K0070之OH值為100 KOH mg/g。
在裝備攪拌器、溫度計及氮取代裝置之燒瓶內填充55.5g(0.125 mol)之4,4’-六氟亞丙基雙鄰-苯二甲酸二酐、137.0g(0.125 mol)之經酸酐改良的聚矽氧烷,其一般結構係由下式(9)表示,及800g之γ-丁內酯。接著,配合控制將91.5g(0.25 mol)之2,2-雙(4-胺基-3-羥苯基)六氟丙烷加至該燒瓶以致於該反應系統之溫度不超過50℃。其後,於室溫另攪拌該混合物10小時。接下來,將帶有蓄水器之迴流冷凝器安裝於該燒瓶,添加200g之二甲苯並將整個加熱至170℃。當維持於該溫度6小時時,獲得棕色溶液。
等由此所獲得之棕色溶液冷卻至室溫(25℃)之後,獲得具有酚羥基之聚醯亞胺溶液。接著,將18.3g之縮水甘油填至燒瓶中之聚醯亞胺溶液,接著於120℃加熱3小時。等該反應完成之後,將該溶液冷卻至室溫並將該反應溶液倒入甲醇中。接著,等所得之沉澱物過濾並乾燥之後,獲得具有一級醇羥基之目標聚醯亞胺。關於該聚合物之1
H-NMR分析的結果,於10 ppm衍生自該酚羥基之峰減小且於4.6 ppm及4.8 ppm觀察到一級和二級醇羥基之峰,以致於發現到該聚合物為具有由下式所示之重複單元的結構之聚合物(參見第2圖)。關於凝膠滲透層析(GPC)之結果,該聚合物之數量平均分子量為32,000且依據JIS K0070之OH值為100 KOH mg/g。
在裝備攪拌器、溫度計及氮取代裝置之燒瓶內填充31.0g(0.1 mol)之4,4’-氧二鄰-苯二甲酸二酐、184.2g(0.1 mol)之經酸酐改良的聚矽氧,其一般結構係由下式(10)表示,及800g之γ-丁內酯。接著,配合控制將36.6g(0.1 mol)之2,2-雙(4-胺基-3-羥苯基)六氟丙烷及23.4g(0.08 mol)之1,4-二胺基苯氧基苯加至該燒瓶以致於該反應系統之溫度不超過50℃。其後,添加4.4g(0.02 mol)之對-胺基酚並於室溫另攪拌該混合物10小時。接下來,將帶有蓄水器之迴流冷凝器安裝於該燒瓶,添加200g之二甲苯並將整個加熱至170℃。當維持於該溫度6小時時,獲得棕色溶液。
等由此所獲得之棕色溶液冷卻至室溫(25℃)之後,獲得具有酚羥基之聚醯亞胺溶液。接著,將16.5g之縮水甘油填至燒瓶中之聚醯亞胺溶液,接著於120℃加熱3小時。等該反應完成之後,將該溶液冷卻至室溫並將該反應溶液倒入甲醇中。接著,等所得之沉澱物過濾並乾燥之後,獲得具有一級醇羥基之目標聚醯亞胺。關於該聚合物之1
H-NMR分析的結果,於10 ppm衍生自該酚羥基之峰減小且於4.6 ppm及4.8 ppm觀察到一級和二級醇羥基之峰,以致於發現到該聚合物為具有由下式所示之重複單元的結構之聚合物(參見第3圖)。關於凝膠滲透層析(GPC)之結果,該聚合物之數量平均分子量為19,000且依據JIS K0070之OH值為39 KOH mg/g。
在裝備攪拌器、溫度計及氮取代裝置之燒瓶內填充31.0g(0.1 mol)之4,4’-氧二鄰-苯二甲酸二酐、164.4g(0.15 mol)之經酸酐改良的聚矽氧,其一般結構係由下式(9)表示,其係與實施例2所用之聚矽氧相同,及800g之γ-丁內酯。接著,配合控制將45.2g(0.175 mol)之2,2-雙(4-胺基-3-羥苯基)六氟丙烷及14.6g(0.05 mol)之1,4-二胺基苯氧基苯加至該燒瓶以致於該反應系統之溫度不超過50℃。其後,添加5.5g(0.025 mol)之對-胺基酚並於室溫另攪拌該混合物10小時。接下來,將帶有蓄水器之迴流冷凝器安裝於該燒瓶,添加200g之二甲苯並將整個加熱至170℃。當維持於該溫度6小時時,獲得棕色溶液。
等由此所獲得之棕色溶液冷卻至室溫(25℃)之後,獲得具有酚羥基之聚醯亞胺溶液。接著,將10.9g之縮水甘油填至燒瓶中之聚醯亞胺溶液,接著於120℃加熱3小時。等該反應完成之後,將該溶液冷卻至室溫並將該反應溶液倒入甲醇中。接著,等所得之沉澱物過濾並乾燥之後,獲得具有一級醇羥基之目標聚醯亞胺。關於該聚合物之1
H-NMR分析的結果,於10 ppm衍生自該酚羥基之峰減小且於4.6 ppm及4.8 ppm觀察到一級和二級醇羥基之峰,以致於發現到該聚合物為具有由下式所示之重複單元的結構之聚合物(參見第4圖)。關於凝膠滲透層析(GPC)之結果,該聚合物之數量平均分子量為22,000且依據JIS K0070之OH值為51 KOH mg/g。
儘管已經詳細並引用具體實例描述本發明,但是熟於此藝之士顯而易知可於其內完成多種不同變化及修飾而不會悖離其範疇。
本案係建基於2009年9月30日申請之日本專利案第2009-227159號,在此以引用的方式將其全文併入以供參考。
第1圖為實施例1之1
H-NMR圖。
第2圖為實施例2之1
H-NMR圖。
第3圖為實施例3之1
H-NMR圖。
第4圖為實施例4之1
H-NMR圖。
Claims (7)
- 一種具有一級醇羥基之聚醯亞胺矽氧,其係藉由下列通式(1)表示:
- 如申請專利範圍第1項之聚醯亞胺矽氧,其係下列通式(1-1)所示之聚醯亞胺矽氧:
- 如申請專利範圍第1或2項之聚醯亞胺矽氧,其中在該通式(3)中,R3 之至少一者為選自-OH、-OCH2 CH(OH)CH2 OH及-OCH(CH2 OH)CH2 OH之單價基團。
- 如申請專利範圍第1項之聚醯亞胺矽氧,其中在該通式(1)中,W為下式所示之四價有機基團之一:
- 如申請專利範圍第2項之聚醯亞胺矽氧,其中Y2 為至少一選自下列者下列通式(4)所示之二價有機基團:
- 如申請專利範圍第1項之聚醯亞胺矽氧,其末端具有酚基、硫醇基或羧基。
- 一種具有一級醇羥基之聚醯亞胺矽氧之製法,該聚醯亞胺矽氧係藉由下列通式(1)表示:
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EP (1) | EP2305736B1 (zh) |
JP (1) | JP5499312B2 (zh) |
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JP6810677B2 (ja) * | 2017-12-05 | 2021-01-06 | 信越化学工業株式会社 | 新規テトラカルボン酸二無水物、ポリイミド樹脂及びその製造方法、感光性樹脂組成物、パターン形成方法及び硬化被膜形成方法、層間絶縁膜、表面保護膜、電子部品 |
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US20060069227A1 (en) * | 2004-09-30 | 2006-03-30 | Shin-Etsu Chemical Co., Ltd. | Polyimide having an alcoholic hydroxyl group and a process for the preparation thereof |
TW200619271A (en) * | 2004-09-30 | 2006-06-16 | Shinetsu Chemical Co | The polyimide having alcoholic hydroxyl group and the manufacturing method of the same |
TW200804518A (en) * | 2006-06-06 | 2008-01-16 | Shinetsu Chemical Co | Polyimide silicone resin composition |
TW200804462A (en) * | 2006-02-15 | 2008-01-16 | Shinetsu Chemical Co | Polyimidesilicone resin and thermosetting composition comprising the same |
TW200914499A (en) * | 2007-08-22 | 2009-04-01 | Sony Chem & Inf Device Corp | Novel amide group-containing siloxane amine compound |
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JP3221756B2 (ja) | 1992-12-28 | 2001-10-22 | 新日鐵化学株式会社 | プリント基板用耐熱性接着剤フィルム及びその使用方法並びにこれを用いたプリント基板の製造方法 |
JP3329677B2 (ja) | 1997-01-10 | 2002-09-30 | 信越化学工業株式会社 | 熱硬化性樹脂組成物 |
JP2001335619A (ja) | 1999-12-28 | 2001-12-04 | Kanegafuchi Chem Ind Co Ltd | エポキシ変性ポリイミドおよび、これを用いた感光性組成物、カバーレイフィルム、ソルダーレジスト、プリント配線板 |
JP4120780B2 (ja) | 2002-07-19 | 2008-07-16 | 信越化学工業株式会社 | フェノール性水酸基を有するポリイミド樹脂の製造方法 |
JP4530284B2 (ja) * | 2004-10-07 | 2010-08-25 | 信越化学工業株式会社 | ポリイミド系光硬化性樹脂組成物並びにパターン形成方法及び基板保護用皮膜 |
JP2009020246A (ja) * | 2007-07-11 | 2009-01-29 | Toray Ind Inc | 感光性樹脂組成物、これを用いた絶縁性樹脂パターンの製造方法および有機電界発光素子 |
JP2009227159A (ja) | 2008-03-24 | 2009-10-08 | Mazda Motor Corp | 車両のデフレクタ装置 |
JP5206977B2 (ja) | 2009-03-12 | 2013-06-12 | 信越化学工業株式会社 | 新規ポリイミドシリコーン及びこれを含有する感光性樹脂組成物並びにパターン形成方法 |
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US20060069227A1 (en) * | 2004-09-30 | 2006-03-30 | Shin-Etsu Chemical Co., Ltd. | Polyimide having an alcoholic hydroxyl group and a process for the preparation thereof |
TW200619271A (en) * | 2004-09-30 | 2006-06-16 | Shinetsu Chemical Co | The polyimide having alcoholic hydroxyl group and the manufacturing method of the same |
TW200804462A (en) * | 2006-02-15 | 2008-01-16 | Shinetsu Chemical Co | Polyimidesilicone resin and thermosetting composition comprising the same |
TW200804518A (en) * | 2006-06-06 | 2008-01-16 | Shinetsu Chemical Co | Polyimide silicone resin composition |
TW200938590A (en) * | 2007-03-12 | 2009-09-16 | Sabic Innovative Plastics Ip | Polysiloxane/polyimide copolymer blends |
TW200914499A (en) * | 2007-08-22 | 2009-04-01 | Sony Chem & Inf Device Corp | Novel amide group-containing siloxane amine compound |
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KR20110035985A (ko) | 2011-04-06 |
US20110077374A1 (en) | 2011-03-31 |
KR101729780B1 (ko) | 2017-04-24 |
JP2011094131A (ja) | 2011-05-12 |
JP5499312B2 (ja) | 2014-05-21 |
EP2305736A1 (en) | 2011-04-06 |
EP2305736B1 (en) | 2013-04-03 |
US8487062B2 (en) | 2013-07-16 |
TW201130893A (en) | 2011-09-16 |
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