CN112110848A - 一种新的二芳酰基咔唑化合物及其作为增感剂的应用 - Google Patents

一种新的二芳酰基咔唑化合物及其作为增感剂的应用 Download PDF

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CN112110848A
CN112110848A CN202010565795.6A CN202010565795A CN112110848A CN 112110848 A CN112110848 A CN 112110848A CN 202010565795 A CN202010565795 A CN 202010565795A CN 112110848 A CN112110848 A CN 112110848A
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赵文超
李家齐
麻忠利
王辰龙
王永林
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Insight High Technology Jiangsu Co ltd
Insight High Technology Beijing Co Ltd
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Insight High Technology Jiangsu Co ltd
Insight High Technology Beijing Co Ltd
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Abstract

本发明提供一种新的二芳酰基咔唑化合物，其与咔唑基肟酯光引发剂一起使用在光刻胶组合物中显示了显著的协同引发作用，当二芳酰基咔唑化合物与咔唑基肟酯光引发剂的摩尔比在0.1‑1.4之间显示了最佳的增感效果。

Description

一种新的二芳酰基咔唑化合物及其作为增感剂的应用
技术领域：
本发明属于有机化学及光固化技术领域，具体涉及一种新的二芳酰基咔唑化合物，其作为高活性增感剂与咔唑基肟酯一起构成光引发剂组合物，应用在光固化组合物中，尤其是用于制造光刻胶，显示出高感度特性。
背景技术：
光固化技术自70年代出现后得到了广泛应用，例如在涂料、印刷油墨、电子器件制造领域普遍采用了UV光固化技术，其中，影响固化效率的关键因素是光引发剂及与之配合使用的助引发剂成分，例如增感剂。咔唑基肟酯是肟酯类光引发剂中的重要一类，由于其具有相对较高的感度被本领域的技术人员所熟知和研究及使用，如专利公开号或公告号为CN1922142A(三菱化学)、CN100528838C(02)、CN101528694A(831)、CN101528693A、CN101508744A(304)、CN103153952A(03)、CN103492948A、CN107793502A的专利申请文件公开了具有各种不同取代基的咔唑基肟酯化合物，用在彩色滤光片、黑色矩阵、光间隔物、液晶分割取向等材料或器件方面。为提高色彩饱和度或遮盖力的需要，光固化配方中的颜料含量越来越高，尤其是高颜料含量的黑色光刻胶，固化过程中的光能利用率也因颜料的吸收而变小，需要开发有更高感度的光引发剂或光引发剂组合物，对现有光引发剂的增感也是提高感度的方法之一。现有技术中描述的增感剂如专利CN100528838C中公开的有二苯甲酮及其衍生物、硫杂蒽酮及其衍生物、蒽醌及其衍生物、香豆素衍生物、樟脑醌、吩噻嗪及其衍生物、3-(芳酰基亚甲基)噻唑啉、绕丹宁及其衍生物、曙红、罗丹明、吖啶、花青素、部花青染料、叔胺化合物；其中优选了二苯甲酮及其衍生物、硫杂蒽酮及其衍生物、蒽醌及其衍生物、香豆素衍生物。实验证明，这些增感剂在与咔唑基肟酯的混合使用时，并没有表现出令人满意的增感效果，有的化合物因含有酚羟基或苯胺基基团例如曙红、花青素、吩噻嗪而使光固化组合物配方光固化效率降低；在优选的四类化合物中，虽然它们自身也是光引发剂，但与咔唑基肟酯化合物比，光引发效率要低许多，与咔唑基肟酯混合使用时也没有表现出协同增感作用。所以实际上现有技术中并没有较理想的增感剂。
但是技术人员对提高曝光感度、解像力、热稳定性等性能的追求永远没有止境，现有产品和配方技术不断面临着新的挑战。
发明内容
发明人合成出如式Ⅰ和式Ⅱ所示的一类新的二芳酰基咔唑化合物，意外发现，它们在与咔唑基肟酯例如
Figure BDA0002547783850000011
OXE 03按特定比例一起使用时可以起到显著的增感作用，增感效率显著高于现有技术所公开的那些化合物，由此提出一种含有上述二芳酰基咔唑化合物和咔唑基肟酯的光引发剂组合物及该光引发剂组合物在光固化组合物中的应用，特别是在光刻胶中的应用。
第一方面，提供一种二芳酰基咔唑化合物，结构如式Ⅰ或式Ⅱ所示，
Figure BDA0002547783850000021
其中，
R1，R8，R11，R18各自独立地是H，卤素原子，C1-C8烷基，C1-C8烷氧基，CN；
R2，R3，R4，R5，R6，R7，R12，R13，R14，R15，R16，R17各自独立地是H，F，Cl，COOR20，C1-C12直链或支链烷基，C1-C12直链或支链烷氧基，其中所述C1-C12直链或支链烷基未经取代或经一个或多个以下基团取代：苯基、C3-C6环烷基、C3-C6杂环基、F、Cl、COOR21、OR21、SR21、PO(OCnH2n+1)2、Si(CnH2n+1)3，n为1-4的整数；
条件是，每个苯甲酰基的苯环上至少有一个取代基是氟原子或含有氟代烷基的基团；R9，R19各自独立地是C1-C12直链或支链烷基，C2-C12烯基，C3-C12烯基烷基，其中的碳原子上的氢未经取代或经一个或多个以下基团取代：苯基、C3-C6环烷基、C3-C6杂环基、卤素、COOR20、OR20、SR20、PO(OCnH2n+1)2、Si(CnH2n+1)3，n为1-4的整数；或者C3-C12烯基烷基被一个或多个O、S、SO、SO2、CO、COO间隔；
或R9，R19各自独立地是C3-C12烷基，其烷基链经一个或多个O、S、SO、SO2、CO间隔；
或R9，R19各自独立地是苯基，苯基未经取代或经一个或多个C1-C8烷基、卤素原子、OR20、SR20、COR20、CN、COOH取代；
或R9可与取代基R1一起，或R9可与取代基R8一起构成C4-C6杂环结构；
或R19可与取代基R11一起，或R19可与取代基R18一起构成C4-C6杂环结构；
R20是C1-C12烷基或苯基，其未经取代或经一个或多个以下基团取代：苯基、C3-C6环烷基、C3-C6杂环基、F、Cl、OR21、SR21；
R21是C1-C12烷基。
优选地，式Ⅰ所示的化合物选自如式Ⅰ-A和式Ⅰ-B所示化合物；式Ⅱ所示的化合物选自如Ⅱ-A和Ⅱ-B所示化合物：
Figure BDA0002547783850000022
Figure BDA0002547783850000031
其中，
R2，R3，R4，R5，R6，R7，R12，R13，R14，R15，R16，R17各自独立地是H，F，Cl，COOR20，C1-C12直链或支链烷基，C1-C12直链或支链烷氧基，其中C1-C12直链或支链烷基未经取代或经一个或多个以下基团取代：苯基、C3-C6环烷基、C3-C6杂环基、F、Cl、COOR21、OR21、SR21、PO(OCnH2n+1)2、Si(CnH2n+1)3，n为1-4的整数；
条件是，每个苯甲酰基的苯环上至少有一个取代基是氟原子或含有氟代烷基的基团；
R9，R19的定义如上所述。
Y1，Y2各自独立地是C2-C8直链或支链烷基，链可以被O、S、NR21或羰基插入，或碳上的氢被OH、卤素原子取代。
优选地，式Ⅰ-A和Ⅰ-B所示的二芳酰基咔唑化合物的实例有：
Figure BDA0002547783850000032
Figure BDA0002547783850000041
第二方面，提供式Ⅰ或式Ⅱ所示的二芳酰基咔唑化合物的制备方法：以式Ⅲ-A或式Ⅲ-B所示的化合物为原料，与对应的酰基化试剂如取代芳酰氯或酸酐经一步或两步傅克酰基化反应得到对称或不对称的二芳酰基化合物；如任一芳基上含有羧基或含有具有再被取代活性的卤素原子时，可再与R20OH醇类化合物进行酯化反应或者醚化反应，得到式Ⅰ或式Ⅱ所示的二芳酰基咔唑化合物。
Figure BDA0002547783850000042
其中的R1，R8，R9，R11，R18，R19定义如上所述。
第三方面，本发明还提供了一种光引发剂组合物，包含至少一种上述二芳酰基咔唑化合物和至少一种咔唑基肟酯光引发剂，其中所述咔唑基肟酯光引发剂是指至少一个肟酯基团
Figure BDA0002547783850000043
直接或通过一个羰基连接在N-取代咔唑母体结构上；其中R22为C1-C12烷基，其未经取代或经一个或多个以下基团取代：卤素原子、OR24、SR24、C3-C8环烷基、苯基、C4-C20杂芳基、COOR24；或R22为C6-C20芳基或C4-C20杂芳基，其各自未经取代或经一个或多个以下基团取代：卤素原子、C1-C20烷基、被一个或多个氟原子取代的C1-C8烷基、CN、OR24、SR24、NR25R26；或R22为C6-C20芳酰基，C4-C20杂芳酰基；R23选自C1-C12烷基，C6-C20芳基，C1-C4烷氧基；R24为H，C1-C8烷基，任意被一个或多个C3-C8杂环基、F、乙酰氧基取代的C1-C8烷基，苯基，C1-C20烷基苯基；R25，R26各自为C1-C4烷基，经OR24取代的C2-C4烷基，
或NR25R26为环状结构
Figure BDA0002547783850000051
所述咔唑母体结构选自咔唑、苯并咔唑、二苯并咔唑，母体结构上氢原子除被上述肟酯基团或连接着肟酯基团的羰基取代基外，还可以被以下一个或多个基团取代：C1-C20烷基，卤素，NO2，CN，OR27，C6-C20芳酰基，C4-C20杂芳酰基，4,5-二苯基咪唑-2基，母体结构上的取代基在空间上相邻时可以构成新的五元到七元环状结构；其中的C1-C20烷基未经取代或被以下一个或多个基团取代：卤素、C3-C8环烷基、C3-C8杂环烷基、苯基、COOR27、OR27、PO(OCnH2n+1)2、Si(CnH2n+1)3，n为1-4的整数，或者碳原子数大于3时被一个或多个氧原子插入；R27为C1-C8烷基，被C3-C8杂环烷基取代的C1-C8烷基；C6-C20芳酰基，C4-C20杂芳酰基中的芳基或杂芳基未经取代或被以下一个或多个基团取代：卤素原子，CN，
Figure BDA0002547783850000052
R24’，OR24’，SR24’，NR25’R26’，COOR24’，R24’SO2；R22’，R23’，R24’，NR25’R26’的定义与对应的R22，R23，R24，NR25R26相同。
优选地，所述咔唑基肟酯光引发剂选自以下化合物或者它们的任意混合物：
Figure BDA0002547783850000053
Figure BDA0002547783850000061
Figure BDA0002547783850000071
咔唑基肟酯的制备方法之一是以相应的酰基咔唑母体化合物为原料，经过肟化、酯化得到咔唑基肟酯，与此有关的现有技术很多可以参考，例如CN103153952A。
优选地，光引发剂组合物的制备方法包括：取一种增感剂化合物例如式Ⅰ-1化合物0.1摩尔量，取一种咔唑基肟酯例如式IV-22化合物0.1摩尔量，混合均匀即得到光引发剂组合物。或者在光固化组合物制备中直接将一种或多种增感剂化合物和一种或多种咔唑基肟酯与其他组分混合，但增感剂的合计摩尔量与咔唑基肟酯的合计摩尔量之比不大于2:1，优选0.1：1～1.4：1，更优选为0.22:1～1.16:1。
第四方面，本发明还提供一种光固化组合物，含有：
a.光引发剂组合物，含有至少一种式Ⅰ、式ⅡA和ⅡB所示的增感剂和至少一种式IV1-IV37所示的咔唑基肟酯化合物；可选地，组分a的质量占配方全部固体质量的比例为1-10％，优选1-8％。
b.至少一种可自由基聚合的化合物，可选地，所述可自由基聚合的化合物选自丙烯酸酯类化合物，甲基丙烯酸酯类化合物、含有丙烯酸酯基团或甲基丙烯酸酯基团的树脂或它们的任意混合物。
可自由基聚合的化合物中，低分子量的化合物实例有丙烯酸烷基酯、丙烯酸环烷基酯、丙烯酸羟基烷基酯、二烷基氨基烷基丙烯酸酯、甲基丙烯酸烷基酯、甲基丙烯酸环烷基酯、甲基丙烯酸羟基烷基酯、二烷基氨基烷基甲基丙烯酸酯，例如丙烯酸甲酯、丙烯酸丁酯、丙烯酸环己酯、丙烯酸2-羟乙酯、丙烯酸异冰片酯、甲基丙烯酸乙酯、聚硅氧烷丙烯酸酯；其他实例有丙烯腈、乙酸乙烯酯、乙烯基醚、苯乙烯、N-乙烯基吡咯烷酮。含有两个或更多双键的化合物实例有乙二醇、聚乙二醇、丙二醇、新戊二醇、1,6-己二醇的二丙烯酸酯，三羟基甲烷三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯、丙烯酸乙烯酯、疫氰脲酸三烯丙酯等。较高分子量的双键化合物实例有通称为低聚物的一大类物质，例如丙烯酸化的环氧树脂、丙烯酸化的聚酯树脂不饱和聚酯树脂、丙烯酸化的聚醚树脂、丙烯酸化的聚氨酯树脂，一般分子量在500-3000。
第五方面，本发明还提供一种油墨或涂料，除含有上述光固化组合物外，还可根据油墨颜色，印刷用途等性能要求添加其他必要成分。该油墨或涂料可以用于图案印刷，3D打印、PCB阻焊层，液体或干膜抗蚀材料，基材保护涂层等。
第六方面，本发明还提供一种粘合剂，除含有上述光固化组合物外，还可根据粘合剂的性能要求添加其他必要成分。该粘合剂可以用于粘合玻璃、塑料、金属构件等，也可用于液晶显示面板周边与电子元器件UV密封胶，光学膜与电子线路板UV胶粘剂。
除此处举例外，本领域技术人员很容易根据现有技术和光固化组合物的用途需要添加其它必要成分，例如稳定剂、表面活性剂、流平剂、分散剂。
第七方面，本发明还提供一种光刻胶，含有：
a.至少一种上述光引发剂组合物，可选地，其质量占配方全部固体质量的比例为0.2-10％，优选1-8％；
b.至少一种可自由基聚合的化合物，例如多官能丙烯酸酯单体；
c.碱溶性树脂；
d.颜料；
e.溶剂。
组分b中的多官能丙烯酸酯的实例有二季戊四醇六丙烯酸酯，季戊四醇丙烯酸酯；c组分c碱溶性树脂的实例是具有羧酸基团的聚丙烯酸酯，例如甲基丙烯酸、衣康酸、马来酸等与常见单体按需要比例进行共聚得到的共聚物，常见单体例如丙烯酸甲酯、甲基丙烯酸丁酯、丙烯酸苄酯、丙烯酸羟乙酯、苯乙烯、丁二烯、马来酸酐等；共聚物的实例优选为甲基丙烯酸甲酯和甲基丙烯酸共聚物、甲基丙烯酸苄酯和甲基丙烯酸共聚物、甲基丙烯酸甲酯和甲基丙烯酸丁酯及甲基丙烯酸与苯乙烯共聚物。
组分d的颜料实例如C.I.颜料红177、C.I.颜料绿7、C.I.颜料蓝15:6、溶剂蓝25、炭黑、钛黑、C.I.颜料黑1。
有关组分b，组分c，组分d和组分e的现有文献很多例如CN103153952A，本领域技术人员可以根据需要选择。
除组分a作为光引发剂外，还可以加入其它现有商品化或现有技术中已有的光引发剂或助引发剂，只要有利于光固化组合物尤其是光刻胶的性能。例如Omnirad BDK、Omnirad 369、Omnirad 379、Omnirad 389、Omnirad TPO、Omnirad 819、Omnirad ITX、Omnirad DETX、Omnirad 784。Omnirad为IGM树脂公司商品。
除上述组分外，还可添加其他树脂的实例有聚甲基丙烯酸烷基酯、乙基纤维素、羧甲基纤维素、线型酚醛树脂、聚乙烯醇缩丁醛、聚醋酸乙烯酯、聚酯、聚酰亚胺。
第八方面，提供一种黑色光刻胶，当上述光刻胶中颜料是经良好分散的黑色颜料例如碳黑或钛黑时，就成为一种黑色光刻胶。用黑色光刻胶可以制造黑色矩阵、单元间隔(Cell gap)的间隔物、微透镜。
第九方面，使用本发明的光刻胶和/或黑色光刻胶为原料经由彩色滤光片的加工过程可以得到彩色滤光片器件，是彩色显示屏的重要部件。
使用含有本发明的光引发剂组合物的任一材料例如油墨、涂料、粘合剂、光刻胶、黑色光刻胶作为原料，经必要工序加工得到的任何物品例如彩色滤光片、彩色显示屏。
第十方面，使用本发明的二芳酰基咔唑衍生物及光引发剂组合物为配方组分，经加工制成的各类元器件密封胶、光学膜制成品，包括阴性钝化膜、光固化光敏性表面涂层、隔绝膜、偏光片涂层等制成品。
具体实施方式
以下实施例和对比例能更详细地阐述本发明。
光源设备：
365nm LED面光源，蓝天特灯发展有限公司；
测试设备：
体视显微镜，COVS-50G，广州市明美光电技术有限公司，线宽单位为um。
实验材料：
式Ⅰ-1化合物：来自化合物制备例1；
式Ⅱ-2化合物：来自化合物制备例2；
Omnirad DETX：IGM树脂公司光引发剂产品；
Esacure 3644：IGM树脂公司光引发剂产品；
Omnirad EMK：IGM树脂公司光引发剂产品；
OXE 02：式IV-1化合物，BASF公司光引发剂产品；
OXE 03：式IV-22化合物，BASF公司光引发剂产品；
NCI 831：式IV-9化合物，日本ADEKA株式会社产品；
PBG 304：式IV-2化合物，常州强力电子新材料股份有限公司产品；
Photomer 6010：脂肪族聚氨酯三丙烯酸酯，IGM树脂公司产品；
DPHA：二季戊四醇五、六丙烯酸酯，天津天骄化工有限公司产品；
HPMA：聚马来酸，美国阿拉丁工业公司产品。
化合物制备例二芳酰基咔唑化合物的制备
制备例1 9-乙基-3,6-二[4-(2,2,3,3-四氟丙氧基)苯甲酰基]咔唑的制备(式Ⅰ-1化合物)的制备
1a.制备9-乙基-3,6-二(4-氟苯甲酰基)咔唑
将N-乙基咔唑19.5g，加入250ml二氯乙烷中溶解，再加入34g三氯化铝，保持0～-5℃，向溶液中滴加对氟苯甲酰氯40g，然后保持反应液0-5℃反应15小时。将反应液分批加入0℃的100ml10％HCl溶液中，加完搅拌30min。静置30分钟后分液，二氯乙烷相用50ml 2％氢氧化钠溶液洗涤30min，分出二氯乙烷相。减压蒸馏二氯乙烷溶液并回收二氯乙烷，剩余物中加入80ml乙酸乙酯结晶，得产物30.5g，白色粉末含量98.5％，收率69.5％。
1b.制备9-乙基-3,6-二[4-(2,2,3,3-四氟丙氧基)苯甲酰基]咔唑
将步骤1a制备的9-乙基-3,6-二(4-氟苯甲酰基)咔唑30g，2,2,3,3-四氟丙醇25g，氢氧化钠8g，溶入200ml吡啶中，70℃反应18h。减压蒸馏，蒸出吡啶及多余的2,2,3,3-四氟丙醇。剩余物中加入100ml水，250ml二氯乙烷，搅拌1h。分离水相，二氯乙烷溶液用100ml水洗涤2次。减压蒸馏回收二氯乙烷，在剩余物中加入150ml乙酸乙酯和2g活性炭，加热回流1小时，过滤活性炭，滤液被减压蒸馏去除约100ml乙酸乙酯后，降温结晶，过滤后干燥滤饼得27.8g，浅黄色粉末，含量98.5％，收率61.4％。经1H-NMR(CDCl3)证实该结构，δ[ppm]:1.512(t,3H)，4.425-4.483(m,6H)，5.949-6.277(m,2H)，7.016-7.045(m,4H)，7.496-7.517(d,2H)，7.844-7.868(d,4H)，7.990-8.011(d,2H)，8.534(s,2H)。
制备例2 11-(2-乙基己基)-5,8二[4-(2,2,3,3-四氟丙氧基)苯甲酰基]-11H-苯并[a]咔唑(式Ⅱ-2化合物)的制备
2a.制备11-(2-乙基己基)-5,8二(4-氟苯甲酰基)-11H-苯并[a]咔唑
在50ml单口瓶中加入B03D 2.0g,加入二氯乙烷20ml溶解，加入氯化锌0.2g，邻氟苯甲酰氯2.3g，80℃搅拌反应10小时。降温后反应液用20ml水洗涤两次，将二氯乙烷溶液减压浓缩至干，得到棕色粘稠状物4.0g，不经纯化用于2b的反应中。
2b.制备11-(2-乙基己基)-5,8二[4-(2,2,3,3-四氟丙氧基)苯甲酰基]-11H-苯并[a]咔唑
将步骤2a的产物11-(2-乙基己基)-5,8二(4-氟苯甲酰基)-11H-苯并[a]咔唑4.0g用吡啶20ml溶解在50ml单口瓶中，再加入四氟丙醇2.2g，氢氧化钠1.2g，升温至80℃搅拌5小时。将反应液滴加到100ml水中，然后用100ml二氯乙烷搅拌1h后静置分层。分出的二氯乙烷溶液被减压浓缩至干，得到咖啡色固体4.7g。此固体用20ml乙酸乙酯和20ml乙醇混合溶剂加热溶解，加入0.25g活性炭回流1小时，热过滤，滤液降温后析出黄色结晶，干燥后称重2.5g，两步反应合计收率51.3％，含量98.51％。经1H-NMR(CDCl3)证实该结构，δ[ppm]:0.754-0.789(m,6H)，1.126-1.328(m,8H)，2.113(s,1H)，4.369-4.452(t,2H)，4.513-4.599(t,2H)，4.928(m,2H)，4.994-5.342(m,1H)，5.537-5.885(m,1H)，7.251-7.272(m,4H)，7.430-7.455(d,1H)，7.566-7.811(m,6H)，7.950-7.979(d,1H)，8.430(s,1H)，8.571(s,1H)，8.668-8.695(d,1H)，8.736-8.764(d,1H)。
光引发剂组合物制备
组合物制备例1：
取式Ⅱ-2所示化合物12g、OXE-02 28g放入研钵中研磨混合，得到40g组合物，酰基咔唑化合物与咔唑基肟酯光引发剂的摩尔比为0.22。
组合物制备例2：
取式Ⅰ-1所示化合物12g、OXE-02 28g放入研钵中研磨混合，得到40g组合物，酰基咔唑化合物与咔唑基肟酯光引发剂的摩尔比为0.27。
组合物制备例3：
取式Ⅰ-1所示化合物12g、OXE-03 12g放入研钵中研磨混合，得到24g组合物，酰基咔唑化合物物与咔唑基肟酯光引发剂的摩尔比为1.16。
组合物制备例4：
取式Ⅱ-2所示化合物12g、OXE-03 28g放入研钵中研磨混合，得到40g组合物，酰基咔唑化合物与咔唑基肟酯光引发剂的摩尔比为0.41。
碱溶性树脂制备
在1L将甲基丙烯酸苄酯18g、甲基丙烯酸6g、甲基丙烯酸羟乙酯6g、偶氮二异丁腈1.5g、十二硫醇0.6g、甲苯200ml放入恒压滴液漏斗，在500ml四口瓶中放入100ml甲苯，氮气置换，升温至80℃，滴加漏斗中溶液，反应6h后降温滤出，得到24g白色碱溶性树脂。
光刻胶组合物实施例及对比例
按表1～4中所述各组分配制各实施例及对比例。引发剂和增感剂可使用组合物制备例中的组合物或按表中比例混合在溶解于PMA中，再将组合物溶液与黑色色浆按比例混合。将各组分混合均匀后，使用10μm线棒在载玻片上涂膜，90℃烘箱烘干5min，使用365nm光源配合120μm掩膜板进行固化，使用1％NaOH溶液25℃进行显影，并用纯净水浸泡清洗10s，90℃烘箱烘干30min后测量显影图像线宽，线宽单位为μm。
表1
Figure BDA0002547783850000111
表2
Figure BDA0002547783850000112
表3
Figure BDA0002547783850000113
表4
对比例10 对比例11 对比例12
Omnirad DETX 0.024 0 0
ESacure 3644 0 0.024 0
Omnirad EMK 0 0 0.024
OXE 02 0.056 0.056 0.056
PMA 2 2 2
黑色色浆 4.5 4.5 4.5
增感剂/引发剂摩尔比 0.79 0.25 0.65
表1、表2及表4中实施例及对比例经过涂布、固化、显影、测量，数据如表5、表6、表7、表8所示，结果显示：在使用Ⅰ-1作为增感剂搭配多种不同咔唑基肟酯，其使用比例在本发明要求的范围内的实施例显影效果明显好于未使用增感剂、单独使用增感剂或增感剂用量在本发明要求范围值以外的对比例，特别是对比例2的结果表明，式Ⅰ-1所示化合物单独不能形成显影图案，几乎没有引发聚合的作用。对比表4配方和表8数据显示，使用Ⅰ-1作为增感剂其增感效果明显优于硫杂蒽酮、香豆素、四乙基米氏酮，后三者的显影线宽甚至小于单用肟酯对比例1配方。
表3中实施例及对比例经过涂布、固化、显影、测量，数据如表7所示，结果显示：在使用Ⅱ-2作为增感剂搭配多种不同咔唑基肟酯，其使用比例在本发明要求的范围内的实施例显影效果明显好于未使用增感剂、单独使用增感剂或增感剂用量在本发明要求范围值以外的对比例，特别是对比例9的结果表明，式Ⅱ-2所示化合物单独使用不能形成显影图案，几乎没有引发聚合的作用。对比表4配方和表8数据显示，使用Ⅱ-2作为增感剂的增感效果显著高于硫杂蒽酮、香豆素、四乙基米氏酮。
表5
Figure BDA0002547783850000121
表6
实施例5 实施例6 对比例6 对比例7
显影点/s 32 25 30 22
显影线宽 163.0 130.0 138.0 115.0
表7
实施例7 实施例8 实施例9 对比例1 对比例5 对比例8 对比例9
显影点/s 34 30 21 20 35 22 20
显影线宽 143.2 133.6 126.0 119.6 131.5 110.2 0
表8
Figure BDA0002547783850000122
Figure BDA0002547783850000131
粘合剂实施例
按表9各组分配制各实施例及对比例，将各组分混合均匀后，使用50μm线棒在载玻片上涂膜，使用365nm光源配合掩膜板进行固化，固化后测量膜重，然后在室温下的丙酮中浸泡36h后再次测量膜重，计算凝胶转化率。
表9
实施例10 实施例11 对比例13
Photomer 6010 5 5 5
HPMA 4.5 4.5 4.5
OXE 02 0 0 0.5
组合物制备例1 0.5 0 0
组合物制备例2 0 0.5 0
表9对比例与实施例测试数据如表10所示。由数据可见，实施例10和实施例11使用本发明提供的光固化组合物的粘合剂光照双键凝胶转化率明显高于单独使用肟酯光引发剂的对比例13。
表10
实施例10 实施例11 对比例13
凝胶转化率 92.5％ 92.7％ 85.2％
综上所述，本发明提供的新型二芳酰基咔唑化合物与咔唑基肟酯光引发剂一起使用在光刻胶组合物或粘合剂中显示了显著的增感作用，当二芳酰基咔唑化合物与咔唑基肟酯光引发剂的摩尔比在0.1-1.4之间显示出了最佳的增感效果。

Claims (20)

1.一种二芳酰基咔唑化合物，结构如式Ⅰ或式Ⅱ所示，
Figure FDA0002547783840000011
其中，
R1，R8，R11，R18各自独立地是H，卤素原子，C1-C8烷基，C1-C8烷氧基，CN；
R2，R3，R4，R5，R6，R7，R12，R13，R14，R15，R16，R17各自独立地是H，F，Cl，COOR20，C1-C12直链或支链烷基，C1-C12直链或支链烷氧基，其中烷基未经取代或经1个或多个基团取代：苯基、C3-C6环烷基、F、Cl、COOR21、OR21、SR21、PO(OCH2n+1)2、Si(CnH2n+1)3，n为1-4的整数；
条件是，每个苯甲酰基的苯环上至少有一个取代基是氟原子或含有氟代烷基的基团；
R9，R19各自独立地是C1-C12直链或支链烷基，C2-C12烯基，C3-C12烯基烷基，其中的碳原子上的氢未经取代或经1个或多个一下基团取代：苯基、C5-C6环烷基、C3-C6杂环基、卤素、COOR20、OR20、SR20、PO(OCnH2n+1)2、Si(CnH2n+1)3，n为1-4的整数；或者C3-C12烯基烷基被一个或多个O，S，SO、SO2、CO、COO间隔；
或R9，R19各自独立地是C3-C12烷基，链中经一个或多个O，S，SO、SO2、CO间隔；
或R9，R19各自独立地是苯基，苯基未经取代或经一个或多个C1-C8烷基、卤素原子、OR20、SR20、COR20、CN、COOH；
或R9可与取代基R1一起，或R9可与取代基R8一起构成C4-C6杂环结构；
或R19可与取代基R11一起，或R19可与取代基R18一起构成C4-C6杂环结构；
R20是C1-C12烷基或苯基，其未经取代或经1个或多个基团取代：苯基、C3-C6环烷基、F、Cl、OR21、SR21；
R21是C1-C12烷基。
2.根据权利要求1的二芳酰基咔唑化合物，其中式Ⅰ选自如式Ⅰ-A和式Ⅰ-B所示化合物；式Ⅱ选自如式Ⅱ-A和式Ⅱ-B所示化合物：
Figure FDA0002547783840000012
Figure FDA0002547783840000021
其中，
R2，R3，R4，R5，R6，R7，R12，R13，R14，R15，R16，R17各自独立地是H，F，Cl，COOR20，C1-C12直链或支链烷基，C1-C12直链或支链烷氧基，其中烷基未经取代或经1个或多个基团取代：苯基、C3-C6环烷基、C3-C6杂环基、F、Cl、COOR21、OR21、SR21、PO(OCH2n+1)2、Si(CnH2n+1)3，n为1-4的整数；
条件是，每个苯甲酰基的苯环上至少有一个取代基是氟原子或含有氟代烷基的基团；
R9，R19各自独立地是C1-C12直链或支链烷基，C2-C12烯基，C3-C12烯基烷基，其中的碳原子上的氢未经取代或经1个或多个一下基团取代：苯基、C5-C6环烷基、C3-C6杂环基、卤素、COOR20、OR20、SR20、PO(OCnH2n+1)2、Si(CnH2n+1)3，n为1-4的整数；或者C3-C12烯基烷基被一个或多个O，S，SO、SO2、CO、COO间隔；
或R9，R19各自独立地是C3-C12烷基，链中经一个或多个O，S，SO、SO2、CO间隔；
或R9，R19各自独立地是苯基，苯基未经取代或经一个或多个C1-C8烷基、卤素原子、OR20、SR20、COR20、CN、COOH；
R20是C1-C12烷基，其未经取代或经1个或多个基团取代：苯基、C3-C6环烷基、C3-C6杂环基、F、Cl、OR21、SR21；
R21是C1-C12烷基；
Y1，Y2各自独立地是C2-C8直链或支链烷基，链可以被O，S，NR21或羰基插入，或碳上的氢被OH，卤素原子取代。
3.根据权利要求1的二芳酰基咔唑化合物，选自以下化合物之一或者它们的任意混合物：
Figure FDA0002547783840000022
Figure FDA0002547783840000031
4.一种权利要求1中二芳酰基咔唑化合物的制备方法，其特征是：以式Ⅲ-A或式Ⅲ-B为原料，用对应的取代芳酰氯或酸酐经一步或两步付克酰基化反应得到对称或不对称的二芳酰基化合物；如任一芳基上含有羧基或含有具有再被取代活性的卤素原子时，再与R20OH醇类化合物进行酯化反应或者醚化反应，得到二芳酰基咔唑化合物式Ⅰ或式Ⅱ。
Figure FDA0002547783840000041
5.一种光引发剂组合物，含有至少一种权利要求1的二芳酰基咔唑化合物和至少一种咔唑基肟酯光引发剂，其中咔唑基肟酯光引发剂是指至少一个肟酯基团
Figure FDA0002547783840000042
直接或通过一个羰基连接在N-取代咔唑母体结构上；其中R22为C1-C12烷基，其未经取代或被1个或多个以下基团取代：卤素原子、OR24、SR24、C3-C8环烷基、苯基、C4-C20杂芳基、COOR24、；或R22为C6-C20芳基或C4-C20杂芳基，其各自未经取代或经一个或多个以下基团取代：卤素原子、C1-C20烷基、被一个或多个氟原子取代的C1-C8烷基、CN、OR24、SR24、NR25R26；或R22为C6-C20芳酰基，C4-C20杂芳酰基；R23选自C1-C12烷基，C6-C20芳基，C1-C4烷氧基；R24为H，C1-C8烷基，任意被一个或多个C3-C8杂环基、F、乙酰氧基取代的C1-C8烷基，苯基，C1-C20烷基苯基；R25，R26各自为C1-C4烷基，经OR24取代的C2-C4烷基，或NR25R26为环状结构
Figure FDA0002547783840000043
咔唑基的母体结构选自咔唑、苯并咔唑、二苯并咔唑，母体结构上氢原子除被上述肟酯基团或连接着肟酯基团的羰基取代基外，还可以被以下一个或多个基团取代：C1-C20烷基，卤素，NO2，CN，OR27，C6-C20芳酰基，C4-C20杂芳酰基，4,5-二苯基咪唑-2基，母体结构上的取代基在空间上相邻时可以构成新的五元到七元环状结构；其中的C1-C20烷基未经取代或被以下一个或多个基团取代：卤素、C3-C8环烷基、C3-C8杂环基、苯基、COOR27、OR27、PO(OCnH2n+1)2、Si(CnH2n+1)3，n为1-4的整数，或者碳原子数大于3时被一个或多个氧原子插入；R27为C1-C8烷基，被C3-C8杂环烷基取代的C1-C8烷基；C6-C20芳酰基，C4-C20杂芳酰基中的芳基或杂芳基未经取代或被以下一个或多个基团取代：卤素原子，CN，
Figure FDA0002547783840000044
R24’，OR24’，SR24’，NR25’R26’，COOR24’，R24’SO2；R22’，R23’，R24’，NR25’R26’的定义与对应的R22，R23，R24，NR25R26相同。
6.根据权利要求5的光引发剂组合物，其中咔唑基肟酯光引发剂选自以下商品或化合物或者它们的任意混合物：
Figure FDA0002547783840000051
Figure FDA0002547783840000061
Figure FDA0002547783840000071
Figure FDA0002547783840000081
7.根据权利要求5的光引发剂组合物，其中权利要求1的二芳酰基咔唑化合物与咔唑基肟酯光引发剂的摩尔比为0.1:1～1.4:1。
8.一种光固化组合物，含有
a.至少一种权利要求5的光引发剂组合物
b.至少一种可自由基聚合的化合物。
9.根据权利要求8的光固化组合物，其中可自由基聚合的化合物选自丙烯酸酯类化合物、甲基丙烯酸酯类化合物，含有丙烯酸酯或甲基丙烯酸酯基团的树脂或它们的任意混合物。
10.根据权利要求8的光固化组合物，其中a组分在全部固体份中的质量占比为1-10％。
11.一种含有权利要求8-10的光固化组合物的油墨。
12.一种含有权利要求8-10的光固化组合物的涂料。
13.一种含有权利要求8-10的光固化组合物的粘合剂。
14.一种光刻胶，含有：
a.至少一种权利要求5的光引发剂组合物，
b.多官能丙烯酸酯单体，
c.碱溶性树脂，
d.颜料，
e.溶剂。
15.一种黑色光刻胶，根据权利要求14的光刻胶，其中颜料是经良好分散的碳黑或钛黑。
16.一种黑色矩阵，其特征为使用权利要求15的黑色光刻胶制造。
17.一种光间隔物，其特征为使用权利要求15的黑色光刻胶制造。
18.一种彩色滤光片器件，使用权利要求14和15的光刻胶为光刻胶原料经由滤光片的加工过程得到的滤光片器件。
19.一种物品，使用权利要求11-15的任一材料作为原料，经涂布，光固化及其他必要工序加工得到的。
20.根据权利要求19所述的物品，使用本发明的二芳酰基咔唑衍生物及光引发剂组合物为配方组分，经加工制成的各类光学膜制成品，包括阴性钝化膜、光固化光敏性表面涂层、隔绝膜、偏光片涂层等制成品。
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