TW201623317A - 經有機矽改質之光起始劑及含彼之光可固化黏著劑組合物 - Google Patents
經有機矽改質之光起始劑及含彼之光可固化黏著劑組合物 Download PDFInfo
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- TW201623317A TW201623317A TW104128497A TW104128497A TW201623317A TW 201623317 A TW201623317 A TW 201623317A TW 104128497 A TW104128497 A TW 104128497A TW 104128497 A TW104128497 A TW 104128497A TW 201623317 A TW201623317 A TW 201623317A
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- ISXOBTBCNRIIQO-UHFFFAOYSA-N tetrahydrothiophene 1-oxide Chemical compound O=S1CCCC1 ISXOBTBCNRIIQO-UHFFFAOYSA-N 0.000 description 1
- 125000002813 thiocarbonyl group Chemical group *C(*)=S 0.000 description 1
- 125000005152 trihalomethanesulfonyl group Chemical group 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
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Abstract
本發明揭示一種經有機矽改質之光起始劑,其由通式(I)表示:
□其中,R1及R2各自獨立地選自由C1-C20烷基、C2-C8烯基、C5-C8環烷基、芳基C1-C3烷基組成之群;R3、R4、R5、R6及R7中之一者為SIL1-X,且其餘各者各自獨立地選自由氫、C1-C20烷基、C2-C8烯基、C5-C8環烷基、芳基C1-C3烷基及鹵素組成之群;X為直接鍵或C1-C12伸烷基;且SIL1及SIL2各自獨立地由式-SiR8R9R10或式(R'SiO3/2)a(R"2SiO2/2)b(R'''3SiO1/2)c表示,其中R8、R9及R10各自獨立地選自由C1-C20烷基、C2-C8烯基、C5-C8環烷基、芳基及芳基C1-C3烷基組成之群,R'、R"及R'''各自獨立地選自由C1-C20烷基、C2-C8烯基、C5-C8環
烷基及苯基C1-C3烷基組成之群,且a、b及c為滿足以下條件之數值:a□0,b□0,c>0,a比c之比率為0至100,且b比c之比率為0至100。
Description
本發明係關於一種經有機矽改質之光起始劑及一種包含彼之光可固化黏著劑組合物。
用於光學透明顯示應用之黏著劑,例如塗覆或層壓於電子總成中之透明顯示基板上之黏著劑,必須具有UV輻射抗性、耐熱性、耐水解性、抗黃化及低混濁度之特性。另外,在暴露於電磁輻射下,起始光可固化黏著劑組合物中之光可固化反應之光起始劑應與組合物中之其他組分具有良好相容性,且具有足夠的活性以起始自由基聚合。當前,聚矽氧聚合物,諸如有機聚矽氧烷,廣泛用作光可固化黏著劑組合物之一部分。然而,市售光起始劑與聚矽氧系統不充分地相容或互溶。另外,許多市售光起始劑在自由基光固化反應期間或之後並不穩定,且導致固化黏著劑之諸如尤其在光學透明顯示應用中不可接受的混濁度及黃度之問題。
US 4,273,907 A揭示一種經有機聚矽氧烷改質之安息香類光起始劑。關於實際應用,必須提及,該等安息香衍生物在環境溫度下僅可儲存有限時間。當暴露於熱及/或UV輻射時,該等衍生物傾向於黃化。
US 4,536,265 A揭示一種經矽氧烷改質之苯乙酮類光起始劑。該苯乙酮類光起始劑亦具有黃化之傾向,且因此不適用於光學透明顯示應用。
US 5,776,658 A揭示一種經矽氧烷改質之光起始劑及感光性混合物。其係由安息香或α-羥基-烷基苯酮與乙烯基三甲氧基矽烷在RuH2(CO)(PPh3)3作為催化劑存在下製備。據報導光起始劑及感光性混合物具有水解穩定性。然而,Ru催化劑昂貴,且乙烯基矽氧烷將鄰位上之芳核烷化成羰基。對位未經佔據,且當暴露於UV輻射時可氧化,導致黃化。
EP 1072326 A2揭示一種含有矽氧烷之α-羥基-烷基苯酮型光起始劑。該專利申請案中報導之光起始劑具有苯基醚結構。該結構在UV輻射及熱條件下不穩定。在嚴苛條件下醚鍵將降解成酚結構,且酚結構將最終轉化成具有深色且對於用於光學透明顯示應用不可接受之類醌。
因此,本發明之目標為開發可克服至少一個此等難題之經有機矽改質之光起始劑。此等問題藉由所揭示之光起始劑解決。
一個態樣揭示一種經有機矽改質之光起始劑,其由下式(I)表示:
其中,R1及R2各自獨立地選自由C1-C20烷基、C2-C8烯基、C5-C8環烷基、芳基C1-C3烷基組成之群;R3、R4、R5、R6及R7中之一者為SIL1-X,且其餘各者各自獨立地
選自由氫、C1-C20烷基、C2-C8烯基、C5-C8環烷基、芳基C1-C3烷基及鹵素組成之群;X為直接鍵或C1-C12伸烷基;且SIL1及SIL2各自獨立地由式-SiR8R9R10或式(R'SiO3/2)a(R"2SiO2/2)b(R'''3SiO1/2)c表示,其中R8、R9及R10各自獨立地選自由C1-C20烷基、C2-C8烯基、C5-C8環烷基、芳基及芳基C1-C3烷基組成之群,R'、R"及R'''各自獨立地選自由C1-C20烷基、C2-C8烯基、C5-C8環烷基及苯基C1-C3烷基組成之群,且a、b及c為滿足以下條件之數值:a0,b0,c>0,a比c之比率為0至100,且b比c之比率為0至100。
另一態樣揭示一種光可固化組合物,其包含上文所定義之經有機矽改質之光起始劑。
另一態樣揭示上文所定義之光可固化組合物之用途,其用於黏結或層壓各種基板,且尤其用於光學組件之總成中,或用於在光學透明基板之間或在光學透明基板與不透明基板之間黏結或層壓。
另一態樣揭示一種經塗佈基板,其用上文所定義之光可固化組合物在至少一個表面上塗佈。
另一態樣揭示上文所定義之光可固化組合物之固化反應產物。
主題之其他特徵及態樣更詳細地闡述於下文中。
一般熟習此項技術者應理解,本論述僅為對例示性實施例之描述,且不意欲為限制本發明之更廣泛的態樣。
在一個態樣中,本發明通常針對一種經有機矽改質之光起始
劑,其由通式(I)表示:
R1及R2各自獨立地選自由C1-C20烷基、C2-C8烯基、C5-C8環烷基、芳基C1-C3烷基組成之群。
R3、R4、R5、R6及R7中之一者為SIL1-X,且其餘各者各自獨立地選自由氫、C1-C20烷基、C2-C8烯基、C5-C8環烷基、芳基C1-C3烷基及鹵素組成之群。
X為直接鍵或C1-C12伸烷基。
SIL1及SIL2各自獨立地由式-SiR8R9R10或式(R'SiO3/2)a(R"2SiO2/2)b(R'''3SiO1/2)c表示。
R8、R9及R10各自獨立地選自由C1-C20烷基、C2-C8烯基、C5-C8環烷基、芳基及芳基C1-C3烷基組成之群。
R'、R"及R'''各自獨立地選自由C1-C20烷基、C2-C8烯基、C5-C8環烷基及苯基C1-C3烷基組成之群。
a、b及c為滿足以下條件之數值:a0,b0,c>0,a比c之比率為0至100,且b比c之比率為0至100。
如本文中所使用,C1-C20烷基係指直鏈或分支鏈部分,其在該部分中之碳原子之間僅含有單鍵且包括例如C1-C18、C1-C12、C1-C10、C1-C8、C1-C6或C1-C4烷基。其實例為甲基、乙基、丙基、異丙基、正丁基、第二丁基、異丁基、第三丁基、戊基、己基、庚基、2,4,4-三甲基戊基、2-乙基己基、辛基、壬基、癸基、十一烷基、十二烷基、十六烷基、十八烷基及二十烷基。
如本文中所使用,鹵素係指氟、氯、溴或碘,例如氟、氯或溴,尤其氯或氟。
如本文中所使用,C1-C12伸烷基係指二價繫鏈基團(tethering group),其形成鍵以經由其末端碳原子連接分子片段,且包括例如亞甲基(-CH2-)、伸乙基(-CH2CH2-)、伸正丙基(-CH2CH2CH2-)、伸異丙基、伸正丁基、伸第二丁基、伸異丁基、伸第三丁基、伸戊基、伸己基、伸庚基、伸辛基、伸壬基、伸癸基、伸十一烷基或伸十二烷基。
如本文中所使用,C5-C8環烷基係指含有至少一個環之直鏈或分支鏈烷基,例如環戊基、甲基環戊基、環己基、甲基-或二甲基-環己基或環辛基,尤其環戊基及環己基。
如本文中所使用,C2-C8烯基係指單不飽和或多不飽和且直鏈或分支鏈烯基,且為例如C2-C6烯基或C2-C4烯基。其實例為烯丙基、甲基烯丙基、1,1-二甲基烯丙基、1-丁烯基、2-丁烯基、1,3-戊二烯基、1-己烯基及1-辛烯基,尤其烯丙基。R1及R2作為C2-C8烯基為例如C2-C6烯基,尤其C2-C4烯基。
如本文中所使用,芳基係指具有6至20個碳原子之不飽和芳族碳環基,其具有單環(例如苯基)或多個縮合(稠合)環,其中至少一個環為芳族(例如,萘基、二羥菲基、茀基或蒽基)。較佳之芳基包括苯基、萘基及其類似基團。如本文中所使用,芳基C1-C3烷基係指例如苯甲基、苯乙基、α-甲基苯甲基或α,α-二甲基苯甲基,尤其苯甲基。
以上基團可進一步經取代或不經取代。當經取代時,基團上之氫原子由取代基置換,該(等)取代基為一或多個獨立地選自以下各者之基團:烷基、烯基、炔基、環烷基、環烯基、環炔基、芳基、雜芳基、雜脂環基、芳烷基、雜芳烷基、(雜脂環基)烷基、羥基、受保護羥基、烷氧基、芳氧基、醯基、酯基、巰基、烷基硫基、芳基硫基、氰基、鹵素、羰基、硫羰基、O-胺甲醯基、N-胺甲醯基、O-胺硫甲醯基、N-胺硫甲醯基、C-醯胺基、N-醯胺基、S-磺醯胺基、N-磺醯胺基、C-羧基、受保護C-羧基、O-羧基、異氰酸基、氰硫基、異氰硫
基、硝基、矽基、次磺醯基、亞磺醯基、磺醯基、鹵烷基、鹵烷氧基、三鹵甲磺醯基、三鹵甲磺醯胺基及胺基,包括經單取代胺基及經二取代胺基,及其受保護衍生物。在芳基經取代之情況下,芳基上之取代基可形成稠合至芳基之非芳族環,其包括環烷基、環烯基、環炔基及雜環基。
如本文中所使用,(R'SiO3/2)a(R"2SiO2/2)b(R'''3SiO1/2)c之結構可參考含於矽氧烷結構中之某些單元來識別。此等單元已命名為M、D及T單元,其分別表示具有經驗式R'SiO3/2、R"2SiO2/2及R'''3SiO1/2之單元,其中R'、R"及R'''中之每一者表示如上文所定義之單價取代基。字母名稱M、D、T分別係指單元為單官能、雙官能或三官能之事實。M、D及T之單元以隨機或嵌段方式排列。舉例而言,M、D及T之單元之嵌段可彼此跟隨,但個別單元亦可以隨機分佈方式鍵聯,此視製備期間所使用之矽氧烷而定。
在一個實施例中,R1及R2各自獨立地選自由C1-C20烷基、C2-C8烯基、C5-C8環烷基、芳基、芳基C1-C3烷基組成之群。在一個特定實施例中,R1及R2為C1-C8烷基,尤其C1-C6烷基,較佳C1-C4烷基,諸如甲基、乙基、正丙基、異丙基、正丁基、異丁基或第三丁基,尤其甲基。
在另一實施例中,R5為SIL1-X,且R3、R4、R6及R7中之每一者為氫或C1-C8烷基,較佳氫、甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、己基或辛基,尤其氫。
在另一實施例中,SIL1及/或SIL2為由式SiR8R9R10表示之矽基,其中R8、R9及R10各自獨立地選自由C1-C20烷基、C2-C8烯基、C5-C8環烷基、芳基及芳基C1-C3烷基組成之群。在一個特定實施例中,R8、R9及R10各自獨立地為C1-C8烷基,尤其C1-C6烷基,較佳C1-C4烷基,諸如甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基或苯
基或苯甲基,尤其甲基或苯甲基。較佳地,SIL1及/或SIL2係選自由三甲基矽基(TMS)、二甲基苯基矽基、二甲基苯乙基矽基及三正丙基矽基組成之群。在一個特定實施例中,R8、R9及R10各自獨立地為甲基,且SIL1及/或SIL2對應於三甲基矽基(TMS)。在另一特定實施例中,R8及R9各自獨立地為甲基,R10為苯基,且因此SIL1及/或SIL2對應於二甲基苯基矽基。在又一特定實施例中,R8及R9各自獨立地為甲基,R10為苯乙基,且因此SIL1及/或SIL2對應於二甲基苯乙基矽基。在又一特定實施例中,R8、R9及R10為正丙基,且因此SIL1對應於三正丙基矽基。
在另一實施例中,SIL1及/或SIL2各自獨立地為由通式(R'SiO3/2)a(R"2SiO2/2)b(R'''3SiO1/2)c表示之矽氧基,其中R'、R"及R'''各自獨立地選自由以下各者組成之群:C1-C20烷基、C2-C8烯基、C5-C8環烷基及苯基C1-C3烷基,尤其C1-C8烷基,較佳C1-C6烷基,更佳C1-C4烷基,諸如甲基、乙基、正丙基或正丁基,尤其甲基;a、b及c為滿足以下條件之數值:a0,較佳0a5000,更佳0a1000;b0,較佳0b10000,更佳0b1000;c>0,較佳1c5000,更佳1c1000;a比c之比率為0至100,較佳0至50,更佳0至30;且b比c之比率為0至100,較佳0至80,更佳0至60。在一個特定實施例中,R'、R"及R'''各自為甲基,且a=0,b=1且c=2,且因此矽氧基對應於1,1,1,3,5,5,5-七甲基三矽氧基。在另一特定實施例中,R'、R"及R'''各自為甲基,且a=0,b=1且c=3,且因此矽氧基對應於1,1,1,5,5,5,7,7,7-九甲基四矽氧基。
在另一實施例中,鍵聯基團X為直接鍵或C1-C12伸烷基,尤其C1-C8伸烷基,較佳C1-C6伸烷基,更佳C1-C4伸烷基,諸如亞甲基、伸乙基、伸正丙基、伸異丙基、伸正丁基、伸異丁基或伸第三丁基,尤其直接鍵、亞甲基、伸乙基或伸正丙基。
尤其較佳為以下化合物:-式(1)之化合物,其中R1及R2為甲基,R5為SIL1-X-,其中SIL1為三甲基矽基且X為直接鍵,R3、R4、R6及R7為氫,且SIL2為1,1,1,3,5,5,5-七甲基三矽氧基;-式(1)之化合物,其中R1及R2為甲基,R5為SIL1-X-,其中SIL1為1,1,1,3,5,5,5-七甲基三矽氧基且X為伸乙基,R3、R4、R6及R7為氫,且SIL2為1,1,1,3,5,5,5-七甲基三矽氧基;-式(1)之化合物,其中R1及R2為甲基,R5為SIL1-X-,其中SIL1為1,1,1,3,5,5,5-七甲基三矽氧基且X為伸正丙基,R3、R4、R6及R7為氫,X為正丙基,且SIL2為1,1,1,3,5,5,5-七甲基三矽氧基;-式(1)之化合物,其中R1及R2為甲基,R5為SIL1-X-,其中SIL1為1,1,1,5,5,5,7,7,7-九甲基四矽氧基且X為伸乙基,R3、R4、R6及R7為氫,且SIL2為1,1,1,3,5,5,5,7,7,7-九甲基四矽氧基;-式(1)之化合物,其中R1及R2為甲基,R5為SIL1-X-,其中SIL1為二甲基苯基矽烷且X為伸乙基,R3、R4、R6及R7為氫,且SIL2為二甲基苯基矽烷;-式(1)之化合物,其中R1及R2為甲基,R5為SIL1-X-,其中SIL1為二甲基苯甲基矽烷且X為伸乙基,R3、R4、R6及R7為氫,且SIL2為二甲基苯甲基矽烷;-式(1)之化合物,其中R1及R2為甲基,R5為SIL1-X-,其中SIL1為三正丙基矽烷且X為伸乙基,R3、R4、R6及R7為氫,且SIL2為三正丙基矽烷;以下特定化合物作為經有機矽改質之光起始劑亦特別受關注:
所揭示之經有機矽改質之光起始劑可藉由熟習此項技術者已知之方法製備。典型地,製備方法包括三個步驟:如實例中所展示之親核取代反應或矽氫化反應步驟、親核加成反應步驟及脫氫反應步驟。適合方法為例如PCT/CN2012/085935所揭示。
另一態樣係針對一種光可固化組合物,其包含如上文所定義之
經有機矽改質之光起始劑。詳言之,光可固化組合物包含:(A)至少一種烯系不飽和自由基光可聚合化合物;及(B)至少一種上文所定義之經有機矽改質之光起始劑。
組分(A)可含有一或多個烯烴雙鍵。對組分(A)不存在限制,且組分(A)及其他視情況選用之組分或添加劑之實例可見於例如明確地以引用之方式併入本文中之US 6376568 B1中。在一個實施例中,組分(A)可為至少一種光可聚合有機聚矽氧烷或聚矽氧樹脂,較佳(甲基)丙烯醯氧基矽氧烷。組合物中所用的上文所定義之經有機矽改質之光起始劑的量不受限,但按該組合物之總重量計在例如0.1至30重量%、較佳0.2至15重量%範圍內。
另一態樣係關於上文所定義之光可固化組合物之用途。光可固化組合物具有極佳混濁度及黃度,且因此適用於黏結或層壓各種基板,且尤其用於光學組件之總成中,或用於在光學透明基板之間或光學透明基板與不透明基板之間黏結或層壓。
參考以下實例可更佳地理解本發明。
Et2O:乙基醚
n-BuLi:正丁基鋰
TMSCl:氯化三甲基矽烷
THF:四氫呋喃
TLC:薄層層析法
TMS:三甲基矽基
(TMSO)2MeSiH:1,1,1,3,5,5,5-七甲基三矽氧烷
根據如下文所展示之流程1來合成光起始劑PI-1。在配備有溫度計、冷卻裝置及滴液漏斗之500mL燒瓶中,在-78℃下,用n-BuLi(41.7mL,2.4M於THF中)處理含有1,4-二溴苯(23.6g,100mmol)之200ml Et2O,且接著在-78℃下,用TMSCl(5.2mL,40mmol)來淬滅反應物,且獲得呈油狀之IM-1(22g,96%產率)。在含有SOCl2(14.3g,120mmol)之120mL甲苯及120mL THF存在下,在-15℃至-5℃下,使2-羥基-2-甲基丙酸(10.41g,100mmol)與吡咯啶(28.4g,400mmol)偶合6小時,且獲得11g 70%產率之B-1。
在配備有溫度計、冷卻裝置及滴液漏斗之100mL燒瓶中,將11g B-1添加至THF 2mL及甲苯12mL之溶劑混合物中。藉由真空/N2淨化對溶液進行脫氣。將混合物冷卻至-35至-30℃,且歷經0.5小時緩慢添加n-BuLi(2.4M於己烷中,2mL,4.8mol),保持溫度低於-30℃。在配備有溫度計、冷卻裝置及滴液漏斗之另一100mL燒瓶中,將(4-溴苯基)三甲基矽烷(1.0g,4.8mmol)溶解於THF 2mL及甲苯12mL之溶劑混合物中,且冷卻至-35℃。亦對溶液進行徹底脫氣。將n-BuLi(2.4M於己烷中,2mL,4.8mol)緩慢地添加至冷溶液中,保持溫度低於-30℃。經由導管歷經30分鐘時間段,將醯胺烷氧化物溶液轉化成芳基鋰漿液。使所得溶液歷經1小時升溫至-15℃,且接著歷經1小時時間段升溫至-5℃。使混合物在-5℃下老化直至如藉由TLC所測定反應完成。藉由2N鹽酸水溶液以劇烈攪拌淬滅反應。此得到0.620g(61%)呈無色油狀之IM-2。亦達成按比例增加,且獲得總計24g IM-2。
隨後,在60℃下將1,1,1,3,5,5,5-七甲基三矽氧烷(0.485g,2.18mmol)及B(C6F5)3(1.7mg,0.0033mmol)添加至IM-2(0.90g,2.18mmol)中,持續30分鐘。接著再攪拌混合物30分鐘。在矽膠管柱上藉由管柱層析法純化反應混合物,且獲得1.0g PI-1。按比例增加以得
到總計4.9g PI-1。
根據如下文所展示之流程2合成光起始劑PI-2。將含有1-溴-4-乙烯基苯(183mg,1mmol)、甲苯(10mL)、1,1,1,3,5,5,5-七甲基三矽氧烷(445mg,2mmol)及1,3-二乙烯基-1,1,3,3-四甲基二矽氧烷鉑(0)錯合物之二甲苯(2重量% Pt,20μL)饋入50mL舒倫克管(Schlenk tube)中,接著將混合物加熱至110℃後持續2天,管柱層析法展現複雜化合物,其於TLC板上僅展示一斑點。接著處理大量的IM-3 1-溴-4-乙烯基苯(18.3g)。產物未經進一步純化即用於下一步驟。
在配備有溫度計、冷卻裝置及滴液漏斗之100mL燒瓶中,將B-1(654mg,4.2mg)添加至THF 2mL及甲苯12mL之溶劑混合物中。藉由真空/N2淨化對溶液進行脫氣。將混合物冷卻至-35至-30℃,且歷經0.5小時緩慢添加n-BuLi(1.6M於己烷中,2.63mL,4.2mol),保持溫度低於-30℃。在配備有溫度計、冷卻裝置及滴液漏斗之另一100mL
燒瓶中,將IM-3(1.18g,5mmol)溶解於甲苯12ml及THF 2mL中且冷卻至-30℃。亦對溶液進行徹底脫氣。歷經2小時將n-BuLi(1.6M於己烷中,3.12mL,5mol)緩慢添加至冷溶液中以形成白色漿液,保持溫度低於-30℃。歷經30分鐘時間段將醯胺烷氧化物溶液轉化成芳基鋰漿液。使所得溶液歷經1小時將升溫至-15℃,且接著歷經1小時時間段升溫至-5℃。使混合物在-5℃下老化直至如藉由TLC所測定反應完成。在劇烈攪拌下藉由導入冰冷2N鹽酸水溶液中來淬滅反應物。此得到0.9g呈油狀之粗製IM-4。按比例增加以獲得8.1g IM-4。
在下一步驟中,在60℃下將1,1,1,3,5,5,5-七甲基三矽氧烷(0.485g,2.18mmol)及B(C6F5)3(1.7mg,0.0033mmol)添加至IM-4(0.90g,2.18mmol)中,持續30分鐘。接著再攪拌混合物30分鐘。在矽膠管柱上藉由管柱層析法純化反應混合物以得到1.0g PI-2。按比例增加以得到總計4.9g PI-2。1H NMR(400MHz,CDCl3):0.01(m,6H),0.1(m,36H),0.82(m,2H),1.58(m,6H),2.65(m,2H),7.03-7.45(m,2H),8.12(m,2H)。
根據如下文所展示之流程3合成光起始劑PI-3。在第一步驟中,將含有1-烯丙基-4-溴苯(7.5g,38mmol)、甲苯(100mL)、1,1,1,3,5,5,5-七甲基三矽氧烷(12.6g,57mmol)及1,3-二乙烯基-1,1,3,3,-四甲基二矽氧烷鉑(0)錯合物之二甲苯(2重量% Pt,750μL)饋入250mL舒倫克管中,接著將混合物加熱至110℃後持續16小時。產物IM-6未經進一步純化即用於下一步驟。
在配備有溫度計、冷卻裝置及滴液漏斗之100mL燒瓶中,將B-1(1.95g,12.4mg)添加至THF 2mL及甲苯12mL之溶劑混合物中。藉由真空/N2淨化對溶液進行脫氣。將混合物冷卻至-35至-30℃,且歷經0.5小時緩慢添加n-BuLi(2.5M於己烷中,5.0mL,12.4mol),保持溫度低於-30℃。在配備有溫度計、冷卻裝置及滴液漏斗之另一100mL燒瓶中,將IM-5(5.2g,12.4mmol)溶解於甲苯12ml及THF 2mL中且冷卻至-30℃。亦對溶液進行徹底脫氣。歷經2小時將n-BuLi(2.5M
於己烷中,5.0mL,12.4mol)緩慢添加至冷溶液中以形成白色漿液,保持溫度低於-30℃。歷經30分鐘時間段將醯胺烷氧化物溶液轉化成芳基鋰漿液。使所得溶液歷經1小時升溫至-15℃,且接著歷經1小時時間段升溫至-5℃。使混合物在-5℃下老化直至如藉由TLC所測定反應完成。在劇烈攪拌下藉由逐滴添入冰冷2N鹽酸水溶液中來淬滅反應物。此得到900mg呈油狀之粗製IM-6。
在下一步驟中,在60℃下將1,1,1,3,5,5,5-七甲基三矽氧烷(0.485g,2.18mmol)及B(C6F5)3(1.7mg,0.0033mmol)添加至IM-6(0.90g,2.18mmol)中,持續30分鐘。接著再攪拌混合物30分鐘。在矽膠管柱上藉由管柱層析法純化反應混合物,且獲得1.0g PI-3。按比例增加以得到總計4.9g PI-3。1H NMR(400MHz,CDCl3):0.01(s,6H),0.09(s,36H),0.49(t,J=9.0Hz,2H),1.61(s,6H),1.64(m,2H),2.67(t,J=7.5Hz,2H),7.21(d,J=9.0Hz,2H),8.16(d,J=9.0Hz,2H)。
PI-2(E1)用以評估光起始、UV抗性、抗黃化及抗混濁特性。第一比較實例為Darocur® 1173(CE1),當需要UV塗層即使在長期暴露於日光後亦僅展現最小黃化時,尤其推薦其。第二比較實例為IM-4(CE2),其為僅在苯基中經單取代之聚矽氧。第三比較實例為PI-0(CE3),其為在α-羥基-烷基苯酮之羥基中經單取代之聚矽氧。用於評估之光起始劑結構展示如下:
在評估中,將光起始劑均勻地混合於丙烯酸酯聚矽氧基質(15MDMA:60DMA=4:1)中且分別暴露於UV輻射。每次用於光可固化組合物中之光起始劑之量按黏著劑組合物之總重量計為1.6重量%。
15MDMA為藉由在正丁基二甲基矽醇鋰存在下,使經矽烷醇封端之聚二甲基矽氧烷(來自AB Specialty Silicones之Andisil MOH 1000)與甲基丙烯醯氧基丙基三甲氧基矽烷(來自Gelest Inc.之Gelest SIA 200.0)反應來製備的丙烯酸酯聚矽氧。
60DMA為藉由在正丁基二甲基矽醇鋰存在下,使經矽烷醇封端之聚二甲基矽氧烷(來自AB Specialty Silicones之Andisil OH 50,000)與甲基丙烯醯氧基丙基三甲氧基矽烷(來自Gelest Inc.之Gelest SIA
200.0)反應來製備的丙烯酸酯聚矽氧。
15MDMA及60DMA之合成製備之細節為熟習此項技術者所已知,且揭示於例如US 5663269之實例3中。
接著將光起始劑及聚合物之每次所得混合物置放於2個具有750微米氣隙之玻璃層之間,以提供750微米厚的光起始劑及聚合物之層,且接著使用具有H燈泡之Fusion System UV室(製造商:Loctite;型號:UVALOC 1000)在180mW/cm2下進行UV照射30秒以引起固化。固化後,立即藉由購自Datacolor Corporation之Datacolor 650設備根據ASTM D1003量測樣品之透射率、混濁度及b*值(黃度),且結果展示於表1中。固化後,與包含其他比較光起始劑之組合物相比,包含PI-2之組合物展示較低混濁度及低b*值。另外,使固化樣品在QUV測試機器(購自Q-Lab之UVA-340)中老化400小時。用於老化之波長範圍為295nm至365nm,且發射主峰在340nm下。再次量測樣品之透射率、混濁度及b*值(黃度),且結果展示於表1中。
熟習此項技術者熟知混濁度值指示樣品是否透明,且透明度隨混濁度值降低而增加。另外,b*值指示固化樣品之黃度,且黃度之趨勢隨b*值降低而減小。
自表1可看出,包含光起始劑PI-2之組合物E1在透射率、混濁度及b*值方面展現極佳特性,且極適用於光學透明應用。
與其他樣品相比,藉由比較光起始劑Darocur®1173起始之老化
比較樣品CE1在透射率、混濁度值及b*值方面展現較差特性。藉由比較光起始劑PI-0起始之老化比較樣品CE2在透射率及混濁度值方面展現良好特性,但指示老化產物之黃度的其b*值顯著較大。藉由比較光起始劑IM-4起始之老化比較樣品CE3在透射率及b*值方面具有良好特性,但其渾濁度*值相當大。僅藉由本發明光起始劑PI-2起始之老化樣品在透射率、混濁度值及b*值方面展現極佳效能組合。
儘管不希望受以下理論束縛,但假定藉由CE1-3中之光起始劑起始之老化實例的增加之透射率、混濁度值及b*值由在固化及老化過程期間光起始劑之降解及具有低分子量之化合物之生成所引起。出人意料地,本發明人發現,藉由使用所揭示之經有機矽改質之光起始劑,可防止在固化產物固化及老化期間存在具有低分子量之化合物,這歸因於此等光起始劑之獨特結構及設計。
在不偏離本發明之精神及範疇之情況下,本發明之此等及其他修改及變化可由一般熟習此項技術者實踐。另外,應理解,各種實施例之態樣可全部或部分互換。此外,一般熟習此項技術者將瞭解,前述實施方式僅以實例說明之,且不意欲限制本發明,因此進一步描述於該等隨附申請專利範圍中。
Claims (21)
- 一種經有機矽改質之光起始劑,其由通式(I)表示:
- 如請求項1之經有機矽改質之光起始劑,其中R1及R2為C1-C4烷基,較佳甲基、乙基、正丙基、異丙基、正丁基、異丁基或第三丁基,尤其甲基。
- 如請求項1或2之經有機矽改質之光起始劑,其中R5表示SIL1-X-,且R3、R4、R6及R7各自獨立地選自由氫、C1-C4烷基及苯基C1-C3 烷基組成之群,較佳選自氫、甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、己基或辛基,尤其氫。
- 如請求項1或2之經有機矽改質之光起始劑,其中SIL1及/或SIL2由式-SiR8R9R10表示,其中R8、R9及R10各自獨立地選自由C1-C4烷基、苯基及苯基C1-C3烷基組成之群,較佳選自甲基、乙基、正丙基、異丙基、正丁基、異丁基、第三丁基、苯基、苯甲基及苯乙基。
- 如請求項4之經有機矽改質之光起始劑,其中SIL1及/或SIL2係選自由三甲基矽基、二甲基苯基矽基、二甲基苯乙基矽基及三正丙基矽基組成之群。
- 如請求項1或2之經有機矽改質之光起始劑,其中SIL1及/或SIL2由式(R'SiO3/2)a(R"2SiO2/2)b(R'''3SiO1/2)c表示,其中R'、R"及R'''為甲基,a=0,b=1,c=2,且SIL1及/或SIL2對應於1,1,1,3,5,5,5-七甲基三矽氧烷。
- 如請求項1或2之經有機矽改質之光起始劑,其中SIL1及/或SIL2由式(R'SiO3/2)a(R"2SiO2/2)b(R'''3SiO1/2)c表示,其中R'、R"及R'''為甲基,a=0,b=1,c=3,且SIL1及/或SIL2對應於1,1,1,5,5,5,7,7,7-九甲基四矽氧基。
- 如請求項1或2之經有機矽改質之光起始劑,其中X為直接鍵或C1-C3伸烷基,較佳直接鍵、亞甲基、伸乙基或伸正丙基。
- 如請求項1或2之經有機矽改質之光起始劑,其中R1及R2為甲基,R5為SIL1-X-,其中SIL1為三甲基矽基且X為直接鍵,R3、R4、R6及R7為氫,且SIL2為1,1,1,3,5,5,5-七甲基三矽氧基。
- 如請求項1或2之經有機矽改質之光起始劑,其中R1及R2為甲基,R5為SIL1-X-,其中SIL1為1,1,1,3,5,5,5-七甲基三矽氧基且X為伸乙基,R3、R4、R6及R7為氫,且SIL2為1,1,1,3,5,5,5-七甲基三矽 氧基。
- 如請求項1或2之經有機矽改質之光起始劑,其中R1及R2為甲基,R5為SIL1-X-,其中SIL1為1,1,1,3,5,5,5-七甲基三矽氧基且X為伸正丙基,R3、R4、R6及R7為氫,X為正丙基,且SIL2為1,1,1,3,5,5,5-七甲基三矽氧基。
- 如請求項1或2之經有機矽改質之光起始劑,其中R1及R2為甲基,R5為SIL1-X-,其中SIL1為1,1,1,5,5,5,7,7,7-九甲基四矽氧基且X為伸乙基,R3、R4、R6及R7為氫,且SIL2為1,1,1,5,5,5,7,7,7-九甲基四矽氧基。
- 如請求項1或2之經有機矽改質之光起始劑,其中R1及R2為甲基,R5為SIL1-X-,其中SIL1為二甲基苯基矽烷且X為伸乙基,R3、R4、R6及R7為氫,且SIL2為二甲基苯基矽烷。
- 如請求項1或2之經有機矽改質之光起始劑,其中R1及R2為甲基,R5為SIL1-X-,其中SIL1為二甲基苯甲基矽烷且X為伸乙基,R3、R4、R6及R7為氫,且SIL2為二甲基苯甲基矽烷。
- 如請求項1或2之經有機矽改質之光起始劑,其中R1及R2為甲基,R5為SIL1-X-,其中SIL1為三正丙基矽烷且X為伸乙基,R3、R4、R6及R7為氫,且SIL2為三正丙基矽烷。
- 一種經有機矽改質之光起始劑,其選自由以下各者組成之群:
- 一種光可固化組合物,其包含如請求項1至16中任一項之經有機矽改質之光起始劑。
- 如請求項17之光可固化組合物,其中該經有機矽改質之光起始劑之量按該組合物之總量計為0.5重量%至5重量%,較佳1重量%至3重量%,更佳1.5重量%至2重量%。
- 一種如請求項17或18之光可固化組合物之用途,其用於黏結或層壓各種基板,且尤其用於光學組件之總成中,或用於在光學透明基板之間或光學透明基板與不透明基板之間黏結或層壓。
- 一種經塗佈基板,其用如請求項17或18之光可固化組合物在至 少一個表面上塗佈。
- 一種如請求項17之光可固化組合物之固化反應產物。
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US4273907A (en) | 1979-07-18 | 1981-06-16 | Shin-Etsu Chemical Co., Ltd. | Benzoin-bonded organopolysiloxanes and method for the preparation thereof |
DE3107087A1 (de) | 1980-02-29 | 1981-12-24 | CIBA-GEIGY AG, 4002 Basel | "photopolymerisierbare gemische und verfahren zur photopolymerisation von kationisch polymerisierbaren verbindungen" |
JPS57207622A (en) | 1981-06-18 | 1982-12-20 | Toray Silicone Co Ltd | Photopolymerization sensitizer and its preparation |
US4477326A (en) * | 1983-06-20 | 1984-10-16 | Loctite Corporation | Polyphotoinitiators and compositions thereof |
US4534838A (en) * | 1984-04-16 | 1985-08-13 | Loctite Corporation | Siloxane polyphotoinitiators of the substituted acetophenone type |
US4536265A (en) | 1984-04-19 | 1985-08-20 | Loctite Corporation | Siloxane polyphotoinitiators of the substituted acetophenone type |
US4507187A (en) * | 1984-04-19 | 1985-03-26 | Loctite Corporation | Siloxane photoinitiators with aryoyl formate groups |
US4666953A (en) * | 1985-03-28 | 1987-05-19 | Loctite Corporation | Silicone polyphotoinitiators |
JPS62179506A (ja) * | 1986-01-27 | 1987-08-06 | ロクタイト.コ−ポレ−シヨン | ポリ光重合開始剤とその調製方法および該開始剤の性質を利用した硬化性組成物 |
JP2716509B2 (ja) * | 1989-03-01 | 1998-02-18 | 三菱化学株式会社 | ジチオカーバメート基含有ポリシロキサン |
DE4120418A1 (de) * | 1991-06-20 | 1992-12-24 | Wacker Chemie Gmbh | Haertbare organo(poly)siloxanmassen |
US5663269A (en) | 1992-03-31 | 1997-09-02 | Loctite Corporation | Organosiloxane fluids prepared using organo-lithium reagents |
DE4435487A1 (de) | 1994-10-04 | 1996-04-11 | Hoechst Ag | Mit Silikonen kompatible Photoinitiatoren und diese enthaltende lichtempfindliche Gemische |
JPH09183770A (ja) | 1995-10-31 | 1997-07-15 | Nippon Bayeragrochem Kk | 1−アジン−テトラゾリノン類及び除草剤 |
FR2750429B1 (fr) * | 1996-06-27 | 1998-08-07 | Essilor Int | Materiau a base de silicone reticule comportant un photoamorceur fixe, son procede de preparation, produit polymerique hydrophile obtenu a partir de ce materiau et son procede de preparation, et nouveaux photoamorceurs |
DE69817194D1 (de) * | 1997-09-11 | 2003-09-18 | Arch Spec Chem Inc | Eine negativ arbeitende fotoresistzusammensetzung auf basis von polyimid-vorläufern |
US6376568B1 (en) | 1999-07-29 | 2002-04-23 | Ciba Specialty Chemicals Corporation | Surface-active photoinitiators |
ATE483819T1 (de) * | 2002-03-06 | 2010-10-15 | Basf Se | Enzymatisches verfahren zur herstellung einer photoinitiatoren enthaltenden organosiliziumgruppe |
EP1523506B1 (en) | 2002-07-19 | 2012-09-12 | Basf Se | New difunctional photoinitiators |
WO2006107824A2 (en) * | 2005-04-01 | 2006-10-12 | Monsanto Technology Llc | Control of n-(phosphonomethyl) iminodiacetic acid conversion in manufacture of glyphosate |
JP4941657B2 (ja) * | 2007-04-06 | 2012-05-30 | 信越化学工業株式会社 | 有機ケイ素化合物及びその製造方法並びに光重合性組成物及び無機材料 |
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WO2014086000A1 (en) | 2012-12-05 | 2014-06-12 | Henkel (China) Company Limited | Silicone-compatible photoinitiators |
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