CN107561863B - 正型感光性树脂组成物及其应用 - Google Patents
正型感光性树脂组成物及其应用 Download PDFInfo
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- CN107561863B CN107561863B CN201710480604.4A CN201710480604A CN107561863B CN 107561863 B CN107561863 B CN 107561863B CN 201710480604 A CN201710480604 A CN 201710480604A CN 107561863 B CN107561863 B CN 107561863B
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Abstract
本发明是有关一种正型感光性树脂组成物及由该正型感光性树脂组成物所形成的保护膜,其用于形成TFT基板用平坦化膜、层间绝缘膜或光波导路的芯材或包覆材,所述保护膜具有绝缘性佳的特性。所述正型感光性树脂组成物包含碱可溶性树脂(A)、邻萘醌二叠氮磺酸酯(B)、选自由热酸发生剂及热碱发生剂所组成的群组的至少一种的化合物(C)、环状硅氧烷化合物(D)以及溶剂(E)。
Description
技术领域
本发明是有关于一种适用于液晶显示元件、有机EL显示元件等的TFT基板用平坦化膜、层间绝缘膜或光波导路的芯材或包覆材的正型感光性树脂组成物,及由其形成的保护膜、及具有所述保护膜的元件。其中,特别是提供一种曝光、显影后形成绝缘性佳的保护膜用正型感光性树脂组成物。
背景技术
近年来,在液晶显示器或有机电激发光显示器等领域中,为了可提高清晰度和分辨率,一般是经由增加显示装置的开口率而达成(如日本特许第2933879号公报所公开)。通过于透明的TFT基板用平坦化膜上形成一保护膜,使像素电极与数据线重叠,是与现有技术相比可提高开口率的方法。
TFT基板用平坦化膜的材料必须具有高耐热性、高透明性、低诱电性,因此本行业通常使用醌二叠氮化合物和酚醛树脂的组合(如日本特开平第7-98502号公报所公开)或醌二叠氮化合物和丙烯酸类树脂的组合(如日本特开平第10-153854及特开2001-281853号公报所公开),然而前述材料的耐热性并不理想,再者,当将基板进行高温处理时,亦产生固化膜黄化而造成透明度低下的问题。
尽管已针对前述所需特性提出种种用于制作保护膜的正型感光性树脂组成物,然该等材料的绝缘性要求亦无法令本行业所接收。
因此,目前本行业仍需开发出一种绝缘性佳的正型感光性树脂组成物,以利于液晶显示元件、有机显示元件的发展。
发明内容
本发明利用提供特殊环状硅氧烷化合物的成分,而得到绝缘性佳的正型感光性树脂组成物。
因此,本发明提供一种正型感光性树脂组成物,其包含:
碱可溶性树脂(A);
邻萘醌二叠氮磺酸酯(B);
化合物(C),其是选自由热酸发生剂及热碱发生剂所组成的群组;
式(1)所示结构的环状硅氧烷化合物(D);及
溶剂(E);
式(1)中:
R19及R20表示具有脂环式环氧基(alicyclic epoxy group)的一价基团或烷基,其中,t个R19及t个R20中,至少有一个是为具有脂环式环氧基(alicyclic epoxy group)的一价基团;及
t表示3以上的整数;
其中,所述R19及R20可为相同或不同,多个R19及多个R20可为相同或不同。
本发明亦提供一种于一基板上形成薄膜的方法,其包含使用前述的正型感光性树脂组成物施予所述基板上。
本发明又提供一种基板上的薄膜,其是由前述的方法所制得。
本发明再提供一种装置,其包含前述的薄膜。
具体实施方式
本发明提供一种正型感光性树脂组成物,其包含:
碱可溶性树脂(A);
邻萘醌二叠氮磺酸酯(B);
化合物(C),其是选自由热酸发生剂及热碱发生剂所组成的群组;
式(1)所示结构的环状硅氧烷化合物(D);及
溶剂(E);
式(1)中:
R19及R20表示具有脂环式环氧基(alicyclic epoxy group)的一价基团或烷基,其中,所述t个R19及t个R20中,至少有一个是为具有脂环式环氧基(alicyclic epoxy group)的一价基团;及
t表示3以上的整数;
其中,所述R19及R20可为相同或不同,所述多个R19及所述多个R20可为相同或不同。
以下将详细说明用于本发明的正型感光性树脂组成物的各个成分。
本发明的碱可溶性树脂(A)是指可溶于碱性水溶液中的树脂,其构造并无特别限制。较佳地,碱可溶性树脂(A)可为具有羧酸基的树脂或苯酚-酚醛清漆(phenol-novolac)树脂等。更佳地,碱可溶性树脂(A)可由一混合物于适当的聚合起始剂存在下所共聚合而得。
所述混合物可包含不饱和羧酸或不饱和羧酸酐化合物(a1)、具有环氧基的不饱和化合物(a2)及/或其他不饱和化合物(a3)。
所述不饱和羧酸或不饱和羧酸酐化合物(a1)可为包含羧酸基或羧酸酐结构,以及用以聚合键结的不饱和键的化合物。所述不饱和羧酸或不饱和羧酸酐化合物(a1)的结构并无特别限制,且所述不饱和羧酸或不饱和羧酸酐化合物(a1)可包含但不限于不饱和单羧酸化合物、不饱和二羧酸化合物、不饱和酸酐化合物、多环型不饱和羧酸化合物、多环型不饱和二羧酸化合物或多环型不饱和酸酐化合物等。
前述不饱和单羧酸化合物的具体例可包含但不限于(甲基)丙烯酸、丁烯酸、α-氯丙烯酸、乙基丙烯酸、肉桂酸、2-(甲基)丙烯酰乙氧基丁二酸酯[2-(meth)acryloyloxyethyl succinate monoester]、2-(甲基)丙烯酰乙氧基六氢化苯二甲酸酯、2-(甲基)丙烯酰乙氧基苯二甲酸酯或omega-羧基聚己内酯多元醇单丙烯酸酯(其可为东亚合成制造的商品,且其型号为ARONIX M-5300)等。
前述不饱和二羧酸化合物的具体例可包含但不限于马来酸、富马酸、甲基富马酸、衣康酸或柠康酸等。
前述的不饱和酸酐化合物可为所述不饱和二羧酸化合物的酸酐化合物。
前述多环型不饱和羧酸化合物的具体例可包含但不限于5-羧基双环[2.2.1]庚-2-烯、5-羧基-5-甲基双环[2.2.1]庚-2-烯、5-羧基-5-乙基双环[2.2.1]庚-2-烯、5-羧基-6-甲基双环[2.2.1]庚-2-烯或5-羧基-6-乙基双环[2.2.1]庚-2-烯。
前述多环型不饱和二羧酸化合物的具体例可包含但不限于5,6-二羧酸二环[2.2.1]庚-2-烯。
前述多环型不饱和酸酐化合物可为所述多环型不饱和二羧酸化合物的酸酐化合物。
前述不饱和羧酸或不饱和羧酸酐化合物(a1)可单独一种使用或混合多种使用。
较佳地,所述不饱和羧酸或不饱和羧酸酐化合物(a1)的具体例可为丙烯酸、甲基丙烯酸、马来酸酐、2-甲基丙烯酰乙氧基丁二酸酯或2-甲基丙烯酰基乙氧基六氢化苯二甲酸。
基于不饱和羧酸或不饱和羧酸酐化合物(a1),以及后述具有环氧基的不饱和化合物(a2)与其他不饱和化合物(a3)的总使用量为100重量份,所述不饱和羧酸或不饱和羧酸酐化合物(a1)的使用量可为10重量份至30重量份,较佳为10重量份至25重量份,且更佳可为15重量份至25重量份。
所述具有环氧基的不饱和化合物(a2)可包含具有环氧基的(甲基)丙烯酸酯化合物、具有环氧基的α-烷基丙烯酸酯化合物或环氧丙醚化合物等。
前述具有环氧基的(甲基)丙烯酸酯化合物的具体可包含但不限于(甲基)丙烯酸环氧丙酯、(甲基)丙烯酸2-甲基环氧丙酯、(甲基)丙烯酸3,4-环氧丁酯、(甲基)丙烯酸6,7-环氧庚酯、(甲基)丙烯酸3,4-环氧环己酯或(甲基)丙烯酸3,4-环氧环己基甲酯等。
前述具有环氧基的α-烷基丙烯酸酯化合物的具体例可包含但不限于α-乙基丙烯酸环氧丙酯、α-正丙基丙烯酸环氧丙酯、α-正丁基丙烯酸环氧丙酯或α-乙基丙烯酸6,7-环氧庚酯等。
前述环氧丙醚化合物的具体例可包含但不限于邻-乙烯基苯甲基环氧丙醚(o-vinylbenzylglycidylether)、间-乙烯基苯甲基环氧丙醚(m-vinylbenzylglycidylether)或对-乙烯基苯甲基环氧丙醚(p-vinylbenzylglycidylether)等。
前述具有环氧基的不饱和化合物(a2)可单独一种使用或混合多种使用。
较佳地,所述具有环氧基的不饱和化合物(a2)的具体例可为甲基丙烯酸环氧丙酯、(甲基)丙烯酸3,4-环氧环己基甲酯、甲基丙烯酸6,7-环氧庚酯、邻-乙烯基苯甲基环氧丙醚、间-乙烯基苯甲基环氧丙醚或对-乙烯基苯甲基环氧丙醚。
基于前述不饱和羧酸或不饱和羧酸酐化合物(a1)与所述具有环氧基的不饱和化合物(a2),以及其他不饱和化合物(a3)的总使用量为100重量份,所述具有环氧基的不饱和化合物(a2)的使用量可为25重量份至45重量份,较佳为25重量份至40重量份,且更佳可为30重量份至40重量份。
所述其他不饱和化合物(a3)可为(甲基)丙烯酸烷基酯、(甲基)丙烯酸脂环族酯、(甲基)丙烯酸芳基酯、不饱和二羧酸二酯、(甲基)丙烯酸羟烷酯、(甲基)丙烯酸酯的聚醚、芳香乙烯化合物,或者前述化合物以外的其他不饱和化合物。
前述(甲基)丙烯酸烷基酯的具体例可包含但不限于(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丙酯、(甲基)丙烯酸异丙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸异丁酯、(甲基)丙烯酸二级丁酯或(甲基)丙烯酸三级丁酯等。
前述(甲基)丙烯酸脂环族酯的具体例可包含但不限于(甲基)丙烯酸环己酯、(甲基)丙烯酸-2-甲基环己酯、三环[5.2.1.02,6]癸-8-基(甲基)丙烯酸酯[亦可称之为(甲基)丙烯酸双环戊酯]、(甲基)丙烯酸二环戊氧基乙酯、(甲基)丙烯酸异冰片酯或(甲基)丙烯酸四氢呋喃酯等。
前述(甲基)丙烯酸芳基酯的具体例可包含但不限于(甲基)丙烯酸苯基酯或甲基丙烯酸苯甲酯等。
前述不饱和二羧酸二酯的具体例可包含但不限于马来酸二乙酯、富马酸二乙酯或衣康酸二乙酯等。
前述(甲基)丙烯酸羟烷酯的具体例可包含但不限于(甲基)丙烯酸-2-羟基乙酯或(甲基)丙烯酸-2-羟基丙酯等。
前述(甲基)丙烯酸酯的聚醚的具体例可包含但不限于聚乙二醇单(甲基)丙烯酸酯或聚丙二醇单(甲基)丙烯酸酯等。
前述芳香乙烯化合物的具体例可包含但不限于苯乙烯、α-甲基苯乙烯、间-甲基苯乙烯,对-甲基苯乙烯或对-甲氧基苯乙烯等。
前述化合物以外的其他不饱和化合物的具体例可包含但不限于丙烯腈、甲基丙烯腈、氯乙烯、偏二氯乙烯、丙烯酰胺、甲基丙烯酰胺、乙烯乙酯、1,3-丁二烯、异戊二烯、2,3-二甲基1,3-丁二烯、N-环己基马来酰亚胺、N-苯基马来酰亚胺、N-苄基马来酰亚胺、N-丁二酰亚胺基-3-马来酰亚胺苯甲酸酯、N-丁二酰亚胺基-4-马来酰亚胺丁酸酯、N-丁二酰亚胺基-6-马来酰亚胺己酸酯、N-丁二酰亚胺基-3-马来酰亚胺丙酸酯或N-(9-吖啶基)马来酰亚胺等。
所述其他不饱和化合物可单独一种使用或混合多种使用。
前述其他不饱和化合物(a3)的具体例较佳可为(甲基)丙烯酸甲酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸三级丁酯、(甲基)丙烯酸苯甲酯、(甲基)丙烯酸双环戊酯、(甲基)丙烯酸二环戊氧基乙酯、苯乙烯或对-甲氧基苯乙烯。
基于前述不饱和羧酸或不饱和羧酸酐化合物(a1)与具有环氧基的不饱和化合物(a2),以及所述其他不饱和化合物(a3)的总使用量为100重量份,所述其他不饱和化合物(a3)的使用量可为25重量份至65重量份,较佳为35重量份至65重量份,且更佳为35重量份至55重量份。
本发明的碱可溶性树脂(A)在制造时所使用的溶剂可为醇类、醚类、二醇醚、乙二醇烷基醚乙酸醋酸酯、二乙二醇、二丙二醇、丙二醇单烷基醚、丙二醇烷基醚乙酸醋酸酯、丙二醇烷基醚丙酸酯、芳香烃、酮类或酯类等。
前述醇类溶剂的具体例可包含甲醇、乙醇、苯甲醇、2-苯乙醇或3-苯基-1-丙醇等。
前述醚类溶剂的具体例可包含四氢呋喃等。
前述二醇醚的具体例可包含乙二醇单丙醚、乙二醇单甲醚或乙二醇单乙醚等。
前述乙二醇烷基醚醋酸酯的具体例可包含乙二醇丁醚醋酸酯、乙二醇乙醚醋酸酯或乙二醇甲醚醋酸酯等。
前述二乙二醇的具体例可包含二乙二醇单甲醚、二乙二醇单乙醚、二乙二醇单丁醚、二乙二醇二甲醚、二乙二醇二乙醚或二乙二醇甲乙醚等。
前述二丙二醇的具体例可包含二丙二醇单甲醚、二丙二醇单乙醚、二丙二醇二甲醚、二丙二醇二乙醚或二丙二醇甲乙醚等。
前述丙二醇单烷基醚的具体例可包含丙二醇单甲醚、丙二醇单乙醚、丙二醇单丙醚或丙二醇单丁醚等。
前述丙二醇烷基醚醋酸酯的具体例可包含丙二醇甲醚醋酸酯、丙二醇乙醚醋酸酯、丙二醇丙醚醋酸酯或丙二醇丁醚醋酸酯等。
前述丙二醇烷基醚丙酸酯的具体例可包含丙二醇甲醚丙酸酯、丙二醇乙醚丙酸酯、丙二醇丙醚丙酸酯或丙二醇丁醚丙酸酯等。
前述芳香烃的具体例可包含甲苯或二甲苯等。
前述酮类的具体例可包含甲乙酮、环己酮或二丙酮醇等。
前述酯类的具体例可包含乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、2-羟基丙酸乙酯、2-羟基-2-甲基丙酸甲酯、2-羟基-2-甲基丙酸乙酯、羟乙酸甲酯、羟乙酸乙酯、羟乙酸丁酯、乳酸甲酯、乳酸丙酯、乳酸丁酯、3-羟基丙酸甲酯、3-羟基丙酸乙酯、3-羟基丙酸丙酯、3-羟基丙酸丁酯、2-羟基-3-甲基丁酸甲酯、甲氧基乙酸甲酯、甲氧基乙酸乙酯、甲氧基乙酸丁酯、乙氧基乙酸甲酯、乙氧基乙酸乙酯、乙氧基乙酸丙酯、乙氧基乙酸丁酯、丙氧基乙酸甲酯、丙氧基乙酸乙酯、丙氧基乙酸丙酯、丙氧基乙酸丁酯、丁氧基乙酸甲酯、丁氧基乙酸乙酯、丁氧基乙酸丙酯、丁氧基乙酸丁酯、3-甲氧基丁基乙酸酯、2-甲氧基丙酸甲酯、2-甲氧基丙酸乙酯、2-甲氧基丙酸丙酯、2-甲氧基丙酸丁酯、2-乙氧基丙酸甲酯、2-乙氧基丙酸乙酯、2-乙氧基丙酸丙酯、2-乙氧基丙酸丁酯、2-丁氧基丙酸甲酯、2-丁氧基丙酸甲酯、2-丁氧基丙酸乙酯、2-丁氧基丙酸丙酯、2-丁氧基丙酸丁酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-甲氧基丙酸丙酯、3-甲氧基丙酸丁酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、3-乙氧基丙酸丙酯、3-乙氧基丙酸丁酯、3-丙氧基丙酸甲酯、3-丙氧基丙酸乙酯、3-丙氧基丙酸丙酯、3-丙氧基丙酸丁酯、3-丁氧基丙酸甲酯、3-丁氧基丙酸乙酯、3-丁氧基丙酸丙酯或3-丁氧基丙酸丁酯等。
所述溶剂可单独一种使用或混合多种使用。
较佳地,前述溶剂的具体例可为二乙二醇二甲醚或丙二醇甲醚醋酸酯。
前述聚合起始剂的具体例可为偶氮化合物或过氧化物等。
所述偶氮化合物的具体例可包含但不限于2,2′-偶氮二异丁腈、2,2′-偶氮二(2,4-二甲基戊腈)、2,2′-偶氮二(4-甲氧基-2,4-二甲基戊腈)、2,2′-偶氮二(2-甲基丁腈)、4,4′-偶氮二(4-氰基戊酸)或2,2′-偶氮二(二甲基-2-甲基丙酸酯)等。
所述过氧化物的具体例可包含但不限于过氧化二苯甲酰、过氧化二月桂酰(dilauroyl peroxide)、第三丁基过氧化新戊酸酯(tert-butyl peroxypivalate)、1,1-二(第三丁基过氧化)环己烷[1,1-di(tert-butylperoxy)cyclohexane]或过氧化氢等。
所述聚合起始剂可单独一种使用或混合多种使用。
本发明的邻萘醌二叠氮磺酸酯(B)包含具有如下式(2)所示的结构的邻萘醌二叠氮磺酸酯(B-1)。其次,所述邻萘醌二叠氮磺酸酯(B)可选择性地包含其他邻萘醌二叠氮磺酸酯(B-2)。
所述邻萘醌二叠氮磺酸酯(B-1)具有如下式(2)所示的结构:
于式(2)中,R1分别独立地代表氢原子、经取代或未取代的烷基、芳香基或烯基。R2分别独立地代表氢原子或具有醌二叠氮结构的官能基。a、b、d及e分别代表大于或等于0的整数,且f及g的总和为大于或等于1的整数。当a、b、d及e的总和大于1时,多个R1分别可为相同或不同;当f及g的总和大于1时,多个R2的至少一个具有醌二叠氮结构的官能基。
所述具有式(2)所示的结构的邻萘醌二叠氮磺酸酯(B-1)可利用具有羟基的茀化合物来合成,或者通过芴酮与苯酚、邻苯二酚或邻苯三酚于硫代乙酸及酸性触煤的存在下进行反应制得。
所述具有式(2)所示的结构的邻萘醌二叠氮磺酸酯(B-1)是可为完全酯化或部分酯化的酯化物,较佳是由邻萘醌二叠氮磺酸或其盐类与具有羟基的茀化合物反应所制得,更佳是由邻萘醌二叠氮磺酸或其盐类与具有多元羟基的茀化合物反应所制得。
前述具有羟基的茀化合物的具体例可包含JFE化学株式会社制造的产品,且其型号为BPF(如下式(I-1)所示)或BCF(如下式(I-2)所示);本州化学株式会社制造的产品,且其型号为BisP-FL(如下式(I-1)所示);或者如下式(I-3)至式(I-5)所示的化合物:
所述邻萘醌二叠氮磺酸可包含但不限于邻萘醌二叠氮-4-磺酸、邻萘醌二叠氮-5-磺酸或邻萘醌二叠氮-6-磺酸等。所述邻萘醌二叠氮磺酸的盐类可包含但不限于邻萘醌二叠氮磺酸卤盐,具体例可包含邻萘醌二叠氮-4-磺酸氯或邻萘醌二叠氮-5-磺酸氯。
所述邻萘醌二叠氮磺酸酯(B-1)的使用量没有特别的限制,基于所述碱可溶性树脂(A)的使用量为100重量份,所述具有式(2)所示结构的邻萘醌二叠氮磺酸酯(B-1)的使用量为5重量份至50重量份,较佳为7重量份至45重量份,且更佳为10重量份至40重量份。
当使用所述具有式(2)所示结构的邻萘醌二叠氮磺酸酯(B-1)时,可进一步改善所述正型感光性树脂组成物的绝缘性。
所述邻萘醌二叠氮磺酸酯(B)可选择性地具有其他邻萘醌二叠氮磺酸酯(B-2)。
在本发明的一实施例中,所述邻萘醌二叠氮磺酸酯(B-2)是可为完全酯化或部分酯化的酯化物。所述邻萘醌二叠氮磺酸酯(B-2)较佳是由邻萘醌二叠氮磺酸或其盐类与羟基化合物反应所制得,更佳是由邻萘醌二叠氮磺酸或其盐类与多元羟基化合物反应所制得。
所述邻萘醌二叠氮磺酸可包含但不限于邻萘醌二叠氮-4-磺酸、邻萘醌二叠氮-5-磺酸或邻萘醌二叠氮-6-磺酸等。所述邻萘醌二叠氮磺酸的盐类可包含但不限于邻萘醌二叠氮磺酸卤盐。
所述羟基化合物可包含但不限于羟基二苯甲酮类化合物、羟基芳基类化合物、(羟基苯基)烃类化合物或其他芳香族羟基类化合物。所述羟基化合物可单独一种或混合多种使用。
前述的羟基二苯甲酮类化合物可包含但不限于2,3,4-三羟基二苯甲酮、2,4,4′-三羟基二苯甲酮、2,4,6-三羟基二苯甲酮、2,3,4,4′-四羟基二苯甲酮、2,4,2′,4′-四羟基二苯甲酮、2,4,6,3′,4′-五羟基二苯甲酮、2,3,4,2′,4′-五羟基二苯甲酮、2,3,4,2′,5′-五羟基二苯甲酮、2,4,5,3′,5′-五羟基二苯甲酮或2,3,4,3′,4′,5′-六羟基二苯甲酮等。
前述的羟基芳基类化合物可具有如下式(II-1)所示的结构:
于式(II-1)中,Z1至Z3表示氢原子或碳数为1至6的烷基;Z4至Z9表示氢原子、卤素原子、碳数为1至6的烷基、碳数为1至6的烷氧基(alkoxy)、碳数为1至6的脂烯基(alkenyl),或者环烷基(cycloalkyl);Z10及Z11表示氢原子、卤素原子及碳数为1至6的烷基;j、k及m表示1至3的整数;h表示0或1。
如式(II-1)所示的羟基芳基类化合物可包含但不限于三(4-羟基苯基)甲烷、双(4-羟基-3,5-二甲基苯基)-4-羟基苯基甲烷、双(4-羟基-3,5-二甲基苯基)-3-羟基苯基甲烷、双(4-羟基-3,5-二甲基苯基)-2-羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-4-羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-3-羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-2-羟基苯基甲烷、双(4-羟基-3,5-二甲基苯基)-3,4-二羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-3,4-二羟基苯基甲烷、双(4-羟基-3,5-二甲基苯基)-2,4-二羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-2,4-二羟基苯基甲烷、双(4-羟基苯基)-3-甲氧基-4-羟基苯基甲烷、双(3-环己基-4-羟基苯基)-3-羟基苯基甲烷、双(3-环己基-4-羟基苯基)-2-羟基苯基甲烷、双(3-环己基-4-羟基苯基)-4-羟基苯基甲烷、双(3-环己基-4-羟基-6-甲基苯基)-2-羟基苯基甲烷、双(3-环己基-4-羟基-6-甲基苯基)-3-羟基苯基甲烷、双(3-环己基-4-羟基-6-甲基苯基)-4-羟基苯基甲烷、双(3-环己基-4-羟基-6-甲基苯基)-3,4-二羟基苯基甲烷、双(3-环己基-6-羟基苯基)-3-羟基苯基甲烷、双(3-环己基-6-羟基苯基)-4-羟基苯基甲烷、双(3-环己基-6-羟基苯基)-2-羟基苯基甲烷、双(3-环己基-6-羟基-4-甲基苯基)-2-羟基苯基甲烷、双(3-环己基-6-羟基-4-甲基苯基)-4-羟基苯基甲烷、双(3-环己基-6-羟基-4-甲基苯基)-3,4-二羟基苯基甲烷、1-[1-(4-羟基苯基)异丙基]-4-[1,1-双(4-羟基苯基)乙基]苯、1-[1-(3-甲基-4-羟基苯基)异丙基]-4-[1,1-双(3-甲基-4-羟基苯基)乙基]苯或4,4′-[1-[4[-1-(4-羟基苯基)-1-甲基乙基]苯基]亚乙基]双酚等。
前述的(羟基苯基)烃类化合物可具有如下式(II-2)所示的结构:
于式(II-2)中,Z12及Z13表示氢原子或碳数为1至6的烷基,且p及q表示1至3的整数。
如式(II-2)所示的(羟基苯基)烃类化合物可包含但不限于2-(2,3,4-三羟基苯基)-2-(2′,3′,4′-三羟基苯基)丙烷、2-(2,4-二羟基苯基)-2-(2′,4′-二羟基苯基)丙烷、2-(4-羟基苯基)-2-(4′-羟基苯基)丙烷、双(2,3,4-三羟基苯基)甲烷或双(2,4-二羟基苯基)甲烷等。
前述的其他芳香族羟基类化合物可包含但不限于苯酚、对-甲氧基苯酚、二甲基苯酚、对苯二酚、双酚A、萘酚、邻苯二酚、1,2,3-苯三酚甲醚、1,2,3-苯三酚-1,3-二甲基醚、3,4,5-三羟基苯甲酸,或者部分酯化或部分醚化的3,4,5-三羟基苯甲酸等。
上述的羟基化合物较佳是选自于1-[1-(4-羟基苯基)异丙基]-4-[1,1-双(4-羟基苯基)乙基]苯、2,3,4-三羟基二苯甲酮、2,3,4,4′-四羟基二苯甲酮或上述材料的任意组合。
所述邻萘醌二叠氮磺酸或其盐类与羟基化合物的反应通常在二氧杂环己烷(dioxane)、N-吡咯烷酮(N-pyrrolidone)或乙酰胺(acetamide)等有机溶媒中进行。前述的反应更佳是添加三乙醇胺、碱金属碳酸盐或碱金属碳酸氢盐等碱性缩合剂。
所述邻萘醌二叠氮磺酸酯(B)的酯化度较佳在50%以上,亦即以所述羟基化合物中的羟基总量为100摩尔百分比计,所述羟基化合物中有50摩尔百分比以上的羟基与邻萘醌二叠氮磺酸或其盐类进行酯化反应。所述邻萘醌二叠氮磺酸酯(B)的酯化度更佳在60%以上。
基于所述碱可溶性树脂(A)的使用量为100重量份,所述邻萘醌二叠氮磺酸酯(B)的使用量可为5重量份至60重量份,较佳为7重量份至55重量份,且更佳为10重量份至50重量份。
根据本发明的所述化合物(C),是选自由热酸发生剂及热碱发生剂所组成的群组,且上述热酸产生剂或热碱发生剂可单独使用或混合多种而使用。
根据本发明的所述热酸发生剂包含离子性热酸发生剂及非离子性热酸发生剂。
所述离子性热酸发生剂较佳是不含有重金属或卤素离子。
所述离子性热酸发生剂的具体例为锍盐:如三苯基锍、1-二甲硫基萘、1-二甲硫基-4-羟基萘、1-二甲硫基-4,7-二羟基萘、4-羟基苯基二甲基锍、苄基-4-羟基苯基甲基锍、2-甲基苄基-4-羟基苯基甲基锍、2-甲基苄基-4-乙酰基苯基甲基锍、2-甲基苄基-4-苯甲酰基苯基甲基锍等的甲磺酸盐、三氟甲磺酸、樟脑磺酸、对甲苯磺酸、六氟膦酸盐、市售的苄基锍盐如SI-60、SI-80、SI-100、SI-110、SI-145、SI-150、SI-80L、SI-100L、SI-110L、SI-145L、SI-150L、SI-160L、SI-180L(均为三新化学工业(股)制)。
所述非离子性热酸产生剂例如,含卤素化合物、重氮甲烷化合物、砜化合物、磺酸酯化合物、羧酸酯化合物、磷酸酯化合物、磺酰亚胺化合物、磺化苯并三唑类化合物等。
所述含卤素化合物如卤代基团的烃化合物、卤代基的杂环化合物及其类似物,较佳为1,1-双(4-氯苯基)-2,2,2-三氯乙烷、2-苯基-4,6-双(三氯甲基)-s-三嗪、2-萘基-4,6-双(三氯甲基)-s-三嗪。
所述重氮甲烷化合物如双(三氟甲基磺酰基)重氮甲烷、双(环己基磺酰基)重氮甲烷、双(苯基磺酰基)重氮甲烷、双(对甲苯基)重氮甲烷、双(2,4-二甲苯磺酰基)重氮甲烷、双(对氯苯基)重氮甲烷、甲基磺酰基-对甲苯磺酰基重氮甲烷、环己基磺酰基(1,1-二甲基乙基磺酰)重氮甲烷、双(1,1-二甲基乙基磺酰)重氮甲烷、苯基磺酰基(苯甲酰基)重氮甲烷。
所述砜化合物如β-酮砜化合物、β-磺酰基化合物、二芳基砜化合物等;较佳为4-三苯甲酰甲基砜、三甲苯基苯甲酰甲基砜、双(苯基磺酰基)甲烷、4-氯苯基-4-甲基苯基砜。
所述磺酸酯化合物,如烷基磺酸酯、卤代烷基磺酸酯、芳基磺酸酯、亚胺基磺酸酯;较佳为苯偶姻甲苯磺酸酯(benzoin tosylate)、焦棓酚甲磺酸酯、硝基苄基-9,10-二乙氧基蒽-2-磺酸酯、2,6-二硝基苯磺酸钠及市售亚胺基磺酸酯,例如PAI-101、PAI-106(绿化学株式会社制造)、CGI-1311(Ciba Specialty Chemicals公司制造)。
所述羧酸酯化合物如羧酸邻硝基苄基酯及其类似物。
所述磺酰亚胺化合物如N-(三氟甲基磺酰氧基)琥珀酰亚胺(商品名SI-105,绿化学株式会社制造)、N-(樟脑磺酰氧基)琥珀酰亚胺(商品名SI-106,绿化学株式会社制造)、N-(4-甲基苯磺酰氧基)琥珀酰亚胺(商品名SI-101,绿化学株式会社制造)、N-(2-三氟甲基苯磺酰氧基)琥珀酰亚胺、N-(4-氟苯基磺酰氧基)琥珀酰亚胺、N-(三氟甲基磺酰氧基)邻苯二甲酰亚胺、N-(樟脑磺酰基)邻苯二甲酰亚胺、N-(2-三氟甲基苯磺酰氧基)邻苯二甲酰亚胺、N-(2-氟苯基磺酰氧基)邻苯二甲酰亚胺、N-(三氟甲基磺酰氧基)二苯基马来酰亚胺(商品名PI-105,绿化学株式会社制造)、N-(樟脑磺酰氧基)二苯基马来酰亚胺、4-(甲基苯磺酰氧基)二苯基马来酰亚胺、N-(2-三氟甲基苯磺酰氧基)二苯基马来酰亚胺、N-(4-氟苯基磺酰氧基)二苯基马来酰亚胺、N-(4-氟苯基磺酰氧基)二苯基马来酰亚胺、N-(苯基磺酰氧基)双环[2.2.2.1]庚-5-烯-2,3-二羧酰亚胺(商品名NDI-100,绿化学株式会社制造)、N-(4-甲基苯磺酰氧基)双环[2.2.1]庚-5-烯-2,3-二羧酰亚胺(商品名NDI-101,绿化学株式会社制造)、N-(三氟甲磺酰氧基)双环[2.2.1]庚-5-烯-2,3-二羧酰亚胺(商品名NDI-105,绿化学株式会社制造)、N-(九氟丁磺酰氧基)双环[2.2.1]庚-5-烯-二酰亚胺(商品名NDI-109,绿化学株式会社制造)、N-(樟脑磺酰氧基)双环[2.2.1]庚-5-烯-二酰亚胺(商品名NDI-106,绿化学株式会社制造)、N-(樟脑磺酰基)-7-氧杂二环[2.2.1]庚-5-烯-2,3-二羧酰亚胺、N-(三氟甲基磺酰氧基)-7-氧杂二环[2.2.1]庚-5-烯-2,3-二羧酰亚胺、N-(4-甲基苯磺酰氧基)双环[2.2.1]庚-5-烯-2,3-二羧酰亚胺、N-(4-甲基苯磺酰氧基)-7-氧杂二环[2.2.1]庚-5-烯-2,3-二羧酰亚胺、N-(2-三氟甲基苯磺酰氧基)双环[2.2.1]庚-5-烯-2,3-二羧酰亚胺、N-(2-三氟甲基苯磺酰氧基)-7-氧杂双环[2.2.2.1]庚-5-烯-2,3-二羧酰亚胺、N-(4-氟苯基磺酰氧基)双环[2.2.1]庚-5-烯-2,3-二羧酰亚胺、N-(4-氟苯基磺酰基)-7-氧杂二环[2.2.1]庚-5-烯-2,3-二羧酰亚胺、N-(三氟甲基磺酰氧基)双环[2.2.1]庚烷-5,6-氧基-2,3-二羧酰亚胺、N-(樟脑磺酰氧基)双环[2.2.1]庚烷-5,6-氧基-2,3-二羧酰亚胺N-(4-甲基苯磺酰氧基)双环[2.2.1]庚烷-5,6-氧基-2,3-二羧酰亚胺、N-(2-三氟甲基苯磺酰氧基)二环[2.2.2.1]庚烷-5,6-氧基-2,3-二羧酰亚胺、N-(4-氟苯基磺酰氧基)双环[2.2.1]庚烷-5,6-氧基-2,3-二羧酸酰亚胺、N-(三氟甲基磺酰氧基)萘基二羧酰亚胺(商品名NAI-105,绿化学株式会社制造)、N-(樟脑磺酰氧基)萘二酰亚胺(商品名NAI-106,绿化学株式会社制造)、N-(4-甲基苯磺酰氧基)萘基二羧酰亚胺(商品名NAI-101,绿化学株式会社制造)、N-(苯基磺酰氧基)萘基二羧酰亚胺(商品名NAI-100,绿化学株式会社制造)、N-(2-三氟甲基苯磺酰氧基)萘基二羧酰亚胺、N-(4-氟苯基磺酰氧基)萘基二羧酰亚胺、N-(五氟乙基磺酰氧基)萘基二羧酰亚胺、N-(七氟丙基磺酰氧基)萘基二羧酰亚胺、N-(九氟丁基磺酰氧基)萘基二羧酰亚胺(商品名NAI-109,绿化学株式会社制造)、N-(乙基磺酰氧基)萘基二羧酰亚胺、N-(丙基磺酰氧基)萘基二羧酰亚胺、N-(丁基磺酰氧基)萘基二羧酰亚胺(商品名NAI-1004,绿化学株式会社制造)、N-(戊基磺酰氧基)萘基二羧酰亚胺、N-(己基磺酰氧基)萘基二羧酰亚胺、N-(庚基磺酰氧基)萘基二羧酰亚胺、N-(辛基磺酰氧基)萘基二羧酰亚胺、N-(壬基磺酰氧基)萘二酰亚胺。
其他热酸发生剂如1-(4-正丁氧基-1-萘基)四氢噻吩鎓三氟甲烷磺酸酯(1-(4-n-butoxy-1-naphthalenyl)tetrahydrothiophenium trifluoromethanesulfonate)、1-(4,7-二正丁氧基-1-萘基)四氢噻吩鎓三氟甲烷磺酸酯(1-(4,7-dibutoxy-1-naphthalenyl)tetrahydrothiophenium trifluoromethanesulfonate)的四氢噻吩盐。
根据本发明的所述热碱发生剂的具体例为过渡金属络合物类、酰基肟类。所述过渡金属络合物类如溴基十五烷铵高氯酸钴、溴基十五烷甲胺高氯酸钴、溴基十五烷丙胺高氯酸钴、六铵高氯酸钴、六甲胺高氯酸钴、六溴丙胺高氯酸钴及其类似物。
所述酰基肟如丙酰乙酰氧丁基肟、丙酰二苯甲酮肟、丙酰丙酮肟、丁酰苯乙酮肟、丁酰二苯甲酮肟、丁酰丙酮肟、己二酰苯乙酮肟、己二酰二苯甲酮肟、己二酰丙酮肟、丙烯酰苯乙酮肟、丙烯酰基二苯甲酮肟、丙烯酰基丙酮肟等。
另一方面,根据本发明的所述热碱产生剂较佳是包含下列式(3)所示的化合物或其盐类衍生物及/或下列式(4)所示的化合物及/或下列式(5)所示的化合物:
其中:
r表示2至6的整数;及
R31、R32各自独立表示氢原子、碳数1至8的烷基、碳数1至6的可具有取代基的羟烷基、或碳数2至12的二烷基胺基。
较佳地,r表示3至5的整数。
于本发明的具体例中,R31、R32为各自独立表示的氢原子;碳数1至8的烷基,可例如但不限于:甲基、乙基、异丙基、正丁基、叔丁基或正己基等;碳数1至6的可具有取代基的羟烷基,可例如但不限于:烃甲基、2-羟乙基、2-羟丙基、2-羟基异丙基、3-羟基-叔丁基或6-羟基己基等;或碳数2至12的二烷基胺基,可例如但不限于:二甲基胺基、甲基乙基胺基、二乙基胺基、二异丙基胺基、叔丁基甲基胺基或二正己基胺基等。
所述式(3)所示的化合物或其盐类衍生物的较佳具体例为1,5-二氮杂双环[4.3.0]壬-5-烯(DBN)、1,5-二氮杂双环[4.4.0]癸-5-烯、1,8-二氮杂双环[5.4.0]十一碳-7-烯(DBU)、5-羟基丙基-1,8-二氮杂双环[5.4.0]十一碳-7-烯或5-二丁基胺基-1,8-二氮杂双环[5.4.0]十一碳-7-烯、或Aporo公司的制品:SA810、SA831、SA841、SA851、5002;更佳为DBN、SA851或5002。
其中:
R33、R34、R35及R36各自独立表示氢原子、碳数1至8的可具有取代基的烷基、碳数3至8的可具有取代基的环烷基、碳数1至8的可具有取代基的烷氧基、碳数2至8的可具有取代基的烯基、碳数2至8的可具有取代基的炔基、可具有取代基的芳基或可具有取代基的杂环基;
R37及R38各自独立表示氢原子、碳数1至8的可具有取代基的烷基、碳数3至8的可具有取代基的环烷基、碳数1至8的可具有取代基的烷氧基、碳数2至8的可具有取代基的烯基、碳数2至8的可具有取代基的炔基、可具有取代基的芳基或可具有取代基的杂环基、或彼此结合形成可具有取代基的单环、或彼此结合形成可具有取代基的多环;
R39表示碳数1至12的可具有取代基的烷基、碳数3至12的可具有取代基的环烷基、碳数2至12的可具有取代基的烯基、碳数2至12的可具有取代基的炔基、可具有碳数为1至3的烷基取代基的芳基、可具有碳数为1至3的烷基取代基的芳烷基或可具有取代基的杂环基,但R39的碳原子总数为12以下。
其中:
R33、R34、R35及R36、R37及R38的定义如式(4)所示;
R40表示碳数1至12的可具有取代基的亚烷基、碳数3至12的可具有取代基的亚环烷基、碳数2至12的可具有取代基的亚烯基、碳数2至12的可具有取代基的亚炔基、可具有碳数为1至3的烷基取代基的亚芳基、可具有碳数为1至3的烷基取代基的亚芳烷基或可具有取代基的杂环基,但R40的碳原子总数为12以下。
所述式(4)及(5)所示的化合物的较佳具体例为如{[(2-硝基苄基)氧基]羰基}甲基胺、{[(2-硝基苄基)氧基]羰基}丙基胺、{[(2-硝基苄基)氧基]羰基}己基胺、{[(2-硝基苄基)氧基]羰基}环己胺、{[(2-硝基苄基)氧基]羰基}苯胺、{[(2-硝基苄基)氧基]羰基}哌啶、双{[(2-硝基苄基)氧基]羰基}己二胺、双{[(2-硝基苄基)氧基]羰基}苯二胺、双{[(2-硝基苄基)氧基]羰基}甲苯二胺、双{[(2-硝基苄基)氧基]羰基}-二胺基二苯基甲烷、双{[(2-硝基苄基)氧基]羰基}哌嗪、{[(2,6-二硝基苄基)氧基]羰基}-甲胺、{[(2、6-二硝基苄基)氧基]羰基}丙基胺、{[(2,6-二硝基苄基)氧基]羰基}己基胺、{[(2,6-二硝基苄基)氧基]羰基}环己胺、{[(2、6-二硝基苄基)氧基]羰基}苯胺、{[(2,6-二硝基苄基)氧基]羰基}哌啶、双{[(2,6-二硝基苄基)氧基]羰基}己二胺、双{[(2,6-二硝基苄基)氧基]羰基}苯二胺、双{[(2,6-二硝基苄基)氧基]羰基}甲苯二胺、双{[(2,6-二硝基苄基)氧基]羰基}二胺基二苯基甲烷、双-{[(2,6-二硝基苄基)氧基]羰基}哌嗪等的邻硝基苄基胺基甲酸酯类;如{[(α,α-二甲基-3,5-二甲氧基苄基)氧基]羰基}甲基胺、{[(α,α-二甲基-3,5-二甲氧基苄基)氧基]羰基}丙基胺、{[(α,α-二甲基-3,5-二甲氧基苄基)氧基]羰基}己基胺、{[(α,α-二甲基-3,5-二甲氧基苄基)氧基]羰基}环己基胺、{[(α,α-二甲基-3,5-二甲氧基苄基)氧基]羰基}苯胺、{[(α,α-二甲基-3,5-二甲氧基苄基)氧基]羰基}哌啶、双{[(α,α-二甲基-3,5-二甲氧基苄基)氧基]羰基}己二胺、双{[(α,α-二甲基-3,5-二甲氧基苄基)氧基]羰基}苯二胺、双{[(α,α-二甲基-3,5-二甲氧基苄基)氧基]羰基}甲苯二胺、双{[(α,α-二甲基-3,5-二甲氧基苄基)氧基]羰基}二胺基二苯基甲烷、双{[(α,α-二甲基-3,5-二甲氧基苄基)氧基]羰基}哌嗪等的α,α-二甲基-3,5-二甲氧基苄基胺基甲酸酯类;及如N-(异丙氧基羰基)-2,6-二甲基哌啶、N-(异丙氧基羰基)-2,2,6,6-四甲基哌啶、N-(异丙氧基羰基)二异丙基胺、N-(异丙氧基羰基)吡咯烷、N-(异丙氧基羰基)-2,5-二甲基吡咯烷、N-(异丙氧基羰基)氮杂环丁烷、N-(1-乙基丙氧基羰基)-2,6-二甲基哌啶、N-(1-乙基丙氧基羰基)-2,2,6,6-四甲基哌啶、N-(1-乙基丙氧基羰基)二异丙胺、N-(1-乙基丙氧基羰基)吡咯烷、N-(1-乙基丙氧基羰基)-2,5-二甲基吡咯烷、N-(1-乙基丙氧基羰基)-氮杂环丁烷、N-(1-丙基丁氧基羰基)-2,6-二甲基哌啶、N-(1-丙基丁氧基羰基)-2,2,6,6-四甲基哌啶、N-(1-丙基丁氧基羰基)二异丙基胺、N-(1-丙基丁氧基羰基)吡咯烷、N-(1-丙基丁氧基羰基)-2,5-二甲基吡咯烷、N-(1-丙基丁氧基羰基)-氮杂环丁烷、N-(环戊氧基羰基)-2,6-二甲基哌啶、N-(环戊氧基羰基)-2,2,6,6-四甲基哌啶、N-(环戊氧基羰基)二异丙胺、N-(环戊氧基羰基)吡咯烷、N-(环戊氧基羰基)-2,5-二甲基吡咯烷、N-(环戊氧基羰基)-氮杂环丁烷、N-(环己基羰基)-2,6-二甲基哌啶、N-(环己基羰基)-2,2,6,6-四甲基哌啶、N-(环己基羰基)二异丙胺、N-(环己基羰基)吡咯烷、N-(环己基羰基)-2,5-二甲基吡咯烷、N-(环己基羰基)-氮杂环丁烷、N-(叔丁氧基羰基)-2,6-二甲基哌啶、N-(叔丁氧基羰基)-2,2,6,6-四甲基哌啶、N-(叔丁氧基羰基)二异丙胺、N-(叔丁氧基羰基)吡咯烷、N-(叔丁氧基羰基)-2,5-二甲基吡咯烷、N-(叔丁氧基羰基)-氮杂环丁烷、N-(苄氧基羰基)-2,6-二甲基哌啶、N-(苄氧基羰基)-2,2,6,6-四甲基哌啶、N-(苄氧基羰基)二异丙胺、N-(苄氧基羰基)吡咯烷、N-(苄氧基羰基)-2,5-二甲基吡咯烷、N-(苄氧基羰基)-氮杂环丁烷或1,4-双(N,N′-二异丙基胺基羰基氧基)环己烷;更佳为N-(异丙氧基羰基)-2,6-二甲基哌啶、N-(1-乙基丙氧基羰基)二异丙胺、N-(环戊氧基羰基)-2,6-二甲基哌啶、N-(苄氧基羰基)吡咯烷或1,4-双(N,N′-二异丙基胺基羰基氧基)环己烷等的其他化合物。
其他热碱发生剂如2-硝基苄基环己基胺基甲酸酯(2-nitrobenzylcyclohexylcarbamate)或O-胺基甲酰基羟胺酰胺(O-carbamoylhydroxyamines amide)。
于本发明的具体例中,基于所述碱可溶性树脂(A)的使用量为100重量份,所述化合物(C)的使用量为0.3至3重量份;较佳为0.4至2.5重量份,更佳为0.5至2重量份。若未使用所述化合物(C)时,则所述正型感光性树脂组成物会有绝缘性不佳的问题。
根据本发明的式(1)所示结构的环状硅氧烷化合物(D),所述式(1)如下所示:
其中:
R19及R20表示具有脂环式环氧基(alicyclic epoxy group)的一价基团或烷基,其中,所述t个R19及t个R20中,至少有一个是为具有脂环式环氧基(alicyclic epoxy group)的一价基团;及
t表示3以上的整数,较佳为3至6的整数;
其中,所述R19及R20可为相同或不同,所述多个R19及所述多个R20可为相同或不同。
所述环状硅氧烷化合物(D)包含但不限于2,4-二[2-(3-{氧杂双环[4.1.0]庚基})乙基]-2,4,6,6,8,8-六甲基-环四硅氧烷硅氧烷、4,8-二[2-(3-{氧杂双环[4.1.0]庚基})乙基]-2,2,4,6,6,8-六甲基-环四硅氧烷、2,4-二[2-(3-{氧杂双环[4.1.0]庚基})乙基]-6,8-二丙基-2,4,6,8-四甲基-环四硅氧烷、4,8-二[2-(3-{氧杂双环[4.1.0]庚基})乙基]-2,6-二丙基-2,4,6,8-四甲基-环四硅氧烷、2,4,8-三[2-(3-{氧杂双环[4.1.0]庚基})乙基]-2,4,6,6,8-五甲基-环四硅氧烷、2,4,8-二[2-(3-{氧杂双环[4.1.0]庚基})乙基]-6-丙基-2,4,6,8-四甲基-环四硅氧烷、2,4,6,8-四[2-(3-{氧杂双环[4.1.0]庚基})乙基]-2,4,6,8-四甲基-环四硅氧烷、具有脂环式环氧基的倍半硅氧烷(silsesquioxane)等。
具体而言,作为上述的式(1)所示结构的环状硅氧烷化合物(D)的具体例,如下所示。
所述式(1)所示结构的环状硅氧烷化合物(D)可单独一种或或混合两种以上使用。
基于所述碱可溶性树脂(A)的使用量为100重量份,所述式(1)所示结构的环状硅氧烷化合物(D)的使用量为3重量份至30重量份,较佳为4重量份至25重量份,且更佳可为5重量份至20重量份。
当未使用所述式(1)所示结构的环状硅氧烷化合物(D)时,则所述正型感光性树脂组成物会有绝缘性不佳的问题。
本发明的溶剂(E)以可与其他有机成分完全溶解,且其挥发性必须高到在常压下只需少许热量便可使其从分散液中蒸发者为宜。因此,常压下沸点低于150℃的溶剂最常被使用。
本发明适用的溶剂(E)可包含苯、甲苯或二甲苯等的芳香族溶剂;甲醇或乙醇等的醇类溶剂;乙二醇单丙醚、二乙二醇二甲醚、四氢呋喃、乙二醇单甲醚、乙二醇单乙醚、二乙二醇甲醚、二乙二醇乙醚或二乙二醇丁醚等的醚类溶剂;乙二醇甲醚醋酸酯、乙二醇乙醚醋酸酯、丙二醇甲醚醋酸酯、丙二醇乙醚醋酸酯、丙二醇丙醚醋酸酯或3-乙氧基丙酸乙酯等的酯类溶剂;甲乙酮或丙酮等的酮类溶剂。
较佳地,所述溶剂(E)可为二乙二醇二甲醚、丙二醇甲醚醋酸酯或3-乙氧基丙酸乙酯的单独一种或并用两种。
基于所述碱可溶性树脂(A)的使用量为100重量份,所述溶剂(E)的使用量为100重量份至1000重量份,较佳为120重量份至800重量份,且更佳可为150重量份至600重量份。
根据本发明的树脂组成物可选择性地进一步添加添加剂(F),具体而言,添加剂(F)例如是增感剂(sensitizer)、密着助剂(adhesion auxiliary agent)、界面活性剂(surfactant)、溶解促进剂(solubility promoter)、消泡剂(defoamer)或其组合。
增感剂的种类并无特别的限制。增感剂较佳为使用含有酚式羟基(phenolichydroxy)的化合物,例如是:
(1)三苯酚型化合物(trisphenol type compound):如三(4-羟基苯基)甲烷、双(4-羟基-3-甲基苯基)-2-羟基苯基甲烷、双(4-羟基-2,3,5-三甲基苯基)-2-羟基苯基甲烷、双(4-羟基-3,5-二甲基苯基)-4-羟基苯基甲烷、双(4-羟基-3,5-二甲基苯基)-3-羟基苯基甲烷、双(4-羟基-3,5-甲基苯基)-2-羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-4-羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-3-羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-2-羟基苯基甲烷、双(4-羟基-3,5-二甲基苯基)-3,4-二羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-3,4-二羟基苯基甲烷、双(4-羟基-2,5-二甲基苯基)-2,4-二羟基苯基甲烷、双(4-羟基苯基)-3-甲氧基-4-羟基苯基甲烷、双(5-环己基-4-羟基-2-甲基苯基)-4-羟基苯基甲烷、双(5-环己基-4-羟基-2-甲基苯基)-3-羟基苯基甲烷、双(5-环己基-4-羟基-2-甲基苯基)-2-羟基苯基甲烷或双(5-环己基-4-羟基-2-甲基苯基)-3,4-二羟基苯基甲烷等;
(2)双苯酚型化合物(bisphenol type compound):如双(2,3,4-三羟基苯基)甲烷、双(2,4-二羟基苯基)甲烷、2,3,4-三羟基苯基-4′-羟基苯基甲烷、2-(2,3,4-三羟基苯基)-2-(2′,3′,4′-三羟基苯基)丙烷、2-(2,4-二羟基苯基)-2-(2′,4′-二羟基苯基)丙烷、2-(4-羟基苯基)-2-(4′-羟基苯基)丙烷、2-(3-氟基-4-羟基苯基)-2-(3′-氟基-4′-羟基苯基)丙烷、2-(2,4-二羟基苯基)-2-(4′-羟基苯基)丙烷、2-(2,3,4-三羟基苯基)-2-(4′-羟基苯基)丙烷或2-(2,3,4-三羟基苯基)-2-(4′-羟基-3′,5′-二甲基苯基)丙烷等;
(3)多核分枝型化合物(polynuclear branched compound):如1-[1-(4-羟基苯基)异丙基]-4-[1,1-双(4-羟基苯基)乙基]苯或1-[1-(3-甲基-4-羟基苯基)异丙基]-4-[1,1-双(3-甲基-4-羟基苯基)乙基]苯等;
(4)缩合型苯酚化合物(condensation type phenol compound):如1,1-双(4-羟基苯基)环己烷等;
(5)多羟基二苯甲酮类(polyhydroxy benzophenone):如2,3,4-三羟基二苯甲酮、2,4,4′-三羟基二苯甲酮、2,4,6-三羟基二苯甲酮、2,3,4-三羟基-2′-甲基二苯甲酮、2,3,4,4′-四羟基二苯甲酮、2,4,2′,4′-四羟基二苯甲酮、2,4,6,3′,4′-五羟基二苯甲酮、2,3,4,2′,4′-五羟基二苯甲酮、2,3,4,2′,5′-五羟基二苯甲酮、2,4,6,3′,4′,5′-六羟基二苯甲酮或2,3,4,3′,4′,5′-六羟基二苯甲酮等;或
(6)上述各种类含有酚式羟基的化合物的组合。
基于所述碱可溶性树脂(A)的使用量为100重量份,所述增感剂的使用量为5至50重量份;较佳为8重量份至40重量份;且更佳为10重量份至35重量份。
密着助剂例如是三聚氰胺(melamine)化合物及硅烷系化合物等。密着助剂的作用在于增加由正型感光性树脂组成物所形成的保护膜与被保护的元件的间的密着性。
三聚氰胺的市售品例如是由三井化学制造的商品名为Cymel-300或Cymel-303等;或者由三和化学制造的商品名为MW-30MH、MW-30、MS-11、MS-001、MX-750或MX-706等。
当使用三聚氰胺化合物做为密着助剂时基于所述碱可溶性树脂(A)的使用量为100重量份,所述三聚氰胺化合物的使用量为0重量份至20重量份;较佳为0.5重量份至18重量份;且更佳为1.0重量份至15重量份。
硅烷系化合物例如是乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、3-丙烯酰氧基丙基三甲氧基硅烷、乙烯基三(2-甲氧基乙氧基)硅烷、氮-(2-胺基乙基)-3-胺基丙基甲基二甲氧基硅烷、氮-(2-胺基乙基)-3-胺基丙基三甲氧基硅烷、3-胺丙基三乙氧基硅烷、3-环氧丙氧基丙基三甲氧基硅烷、3-环氧丙氧基丙基二甲基甲氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷、3-氯丙基甲基二甲氧基硅烷、3-氯丙基三甲氧基硅烷、3-甲基丙烯氧基丙基三甲氧基硅烷、3-巯丙基三甲氧基硅烷或由信越化学公司制造的市售品(商品名如KBM403)等。
当使用硅烷系化合物作为密着助剂时,基于所述碱可溶性树脂(A)的使用量为100重量份,所述硅烷系化合物的使用量为0重量份至2重量份;较佳为0.05重量份至1重量份;且更佳为0.1重量份至0.8重量份。
界面活性剂例如是阴离子系界面活性剂、阳离子系界面活性剂、非离子系界面活性剂、两性界面活性剂、聚硅氧烷系界面活性剂、氟系界面活性剂或其组合。
界面活性剂的实例包括(1)聚环氧乙烷烷基醚类(polyoxyethylene alkylethers):聚环氧乙烷十二烷基醚等;(2)聚环氧乙烷烷基苯基醚类(polyoxyethylenephenyl ethers):聚环氧乙烷辛基苯基醚、聚环氧乙烷壬基苯基醚等;(3)聚乙二醇二酯类(polyethylene glycol diesters):聚乙二醇二月桂酸酯、聚乙二醇二硬酸酯等;(4)山梨糖醇酐脂肪酸酯类(sorbitan fatty acid esters);以及(5)经脂肪酸改质的聚酯类(fatty acid modified poly esters);及(6)经三级胺改质的聚胺基甲酸酯类(tertiaryamine modified polyurethanes)等。界面活性剂的市售商品例如是KP(由信越化学工业制造)、SF-8427(由道康宁东丽聚硅氧股份有限公司(Dow Corning Toray Silicone Co.,Ltd.)制造)、Polyfiow(由共荣社油脂化学工业制造)、F-Top(由得克姆股份有限公司制造(Tochem Products Co.,Ltd.)制造)、Megaface(由大日本印墨化学工业(DIC)制造)、Fluorade(由住友3M股份有限公司(Sumitomo 3M Ltd.)制造)、Surflon(由旭硝子制造)、SINOPOL E8008(由中日合成化学制造)、F-475(由大日本印墨化学工业制造)或其组合。
基于所述碱可溶性树脂(A)的使用量为100重量份,所述界面活性剂的使用量为0.5重量份至50重量份;较佳为1重量份至40重量份;且更佳为3至30重量份。
消泡剂的实例包括Surfynol MD-20、Surfynol MD-30、EnviroGem AD01、EnviroGem AE01、EnviroGem AE02、Surfynol DF 110D、Surfynol 104E、Surfynol 420、Surfynol DF37、Surfynol DF58、Surfynol DF66、Surfynol DF70以及Surfynol DF210(由气体产品(Air products)制造)等。
基于所述碱可溶性树脂(A)的使用量为100重量份,所述消泡剂的使用量为1重量份至10重量份;较佳为2重量份至9重量份;且更佳为3重量份至8重量份。
溶解促进剂的实例包括氮-羟基二羧基酰亚胺化合物(N-hydroxydicarboxylicimide)以及含酚式羟基的化合物。
基于所述碱可溶性树脂(A)的使用量为100重量份,所述溶解促进剂的使用量为1重量份至20重量份;较佳为2重量份至15重量份;且更佳为3重量份至10重量份。
根据本发明的正型感光性树脂组成物例如是以下列方式来制备:将碱可溶性树脂(A)、邻萘醌二叠氮磺酸酯(B)、化合物(C)、环状硅氧烷化合物(D)以及溶剂(E)放置于搅拌器中搅拌,使其均匀混合成溶液状态,必要时,可添加添加剂(F)。
本发明亦提供一种于一基板上形成薄膜的方法,其包含使用前述的正型感光性树脂组成物施予所述基板上。
本发明又提供一种基板上的薄膜,其是由前述的方法所制得。
根据本发明的所述薄膜,其较佳是为液晶显示元件或有机电激发光显示器中TFT基板用的平坦化膜、层间绝缘膜或光波导路的芯材或包覆材的保护膜。
本发明再提供一种装置,其包含前述的薄膜。
以下将详细描述保护膜的形成方法,其依序包括:使用正型感光性树脂组成物来形成预烤涂膜、对预烤涂膜进行图案化曝光、通过碱显影移除曝光区域以形成图案;以及进行后烤处理以形成保护膜。
形成预烤涂膜
通过回转涂布、流延涂布或辊式涂布等涂布方式,在被保护的元件(以下称为基材)上涂布溶液状态的正型感光性树脂组成物,以形成涂膜。
基材可以是用于液晶显示装置的无碱玻璃、钠钙玻璃、硬质玻璃(派勒斯玻璃)、石英玻璃、附着有透明导电膜的此等玻璃,或是用于光电变换装置(如固体摄影装置)的基材(如:硅基材)。
形成涂膜的后,以减压干燥方式去除正型感光性树脂组成物的大部分有机溶剂,然后以预烤(pre-bake)方式将残余的有机溶剂完全去除,使其形成预烤涂膜。
上述减压干燥及预烤的操作条件可依各成分的种类、配合比率而异。一般而言,减压干燥乃在0托(torr)至200托的压力下进行1秒钟至60秒钟,并且预烤乃在70℃至110℃温度下进行1分钟至15分钟。
图案化曝光
以具有特定图案的光罩对上述预烤涂膜进行曝光。在曝光过程中所使用的光线,以g线、h线或i线等紫外线为佳,并且用来提供紫外线的设备可为(超)高压水银灯或金属卤素灯。
显影
将经曝光的预烤涂膜浸渍于温度介于23±2℃的显影液中,进行约15秒至5分钟的显影,以去除经曝光的预烤涂膜的不需要的部分,亦即经曝光的区域溶解于显影液中,未经曝光的区域则保留,由此可在基材上形成具有预定图案的保护膜的半成品。显影液的具体例包括但不限于氢氧化钠、氢氧化钾、碳酸钠、碳酸氢钠、碳酸钾、碳酸氢钾、硅酸钠、甲基硅酸钠(sodium methylsilicate)、氨水、乙胺、二乙胺、二甲基乙醇胺、氢氧化四甲铵(THAM)、氢氧化四乙铵、胆碱、吡咯、呱啶或1,8-二氮杂双环[5.4.0]-7-十一烯等碱性化合物。
值得一提的是,显影液的浓度太高会使得特定图案损毁或造成特定图案的解析度变差;浓度太低会造成显影不良,导致特定图案无法成型或者曝光部分的组成物残留。因此,浓度的多少会影响后续正型感光性树脂组成物经曝光后的特定图案的形成。显影液的浓度范围较佳为0.001wt%至10wt%;更佳为0.005wt%至5wt%;再更佳为0.01wt%至1wt%。本发明的实施例是使用2.38wt%的氢氧化四甲铵的显影液。值得一提的是,即使使用浓度更低的显影液,本发明正型感光性树脂组成物也能形成良好的微细化图案。
后烤处理
用水清洗基材(其中基材上有预定图案的保护膜的半成品),以清除上述经曝光的预烤涂膜的不需要的部分。然后,用压缩空气或压缩氮气干燥上述具有预定图案的保护膜的半成品。最后以加热板或烘箱等加热装置对上述具有预定图案的保护膜的半成品进行后烤(post-bake)处理。加热温度设定在100℃至250℃之间,使用加热板时的加热时间为1分钟至60分钟,使用烘箱时的加热时间则为5分钟至90分钟。由此,可使上述具有预定图案的保护膜的半成品的图案固定,以形成保护膜。
通过以下列实施例予以详细说明本发明,并不意味本发明仅局限于此等实施例所公开的内容。
碱可溶性树脂(A)的合成
<合成例A-1>
在一容积1000毫升的四颈锥瓶上设置氮气入口、搅拌器、加热器、冷凝管及温度计。导入氮气后,添加20重量份的甲基丙烯酸(以下简称为MAA)、35重量份的甲基丙烯酸环氧丙酯(以下简称为GMA)、30重量份的甲基丙烯酸双环戊酯(以下简称为FA-513M)、15重量份的苯乙烯(以下简称为SM)、5重量份的2,2′-偶氮双(2,4-二甲基戊腈)(以下简称为ADVN)及300重量份的二乙二醇二甲醚(以下简称为Diglyme)至反应瓶中。接着,缓慢搅拌上述成分,并将溶液加热至70℃。进行聚缩合反应4小时后,将溶剂脱挥,即可制得合成例A-1的碱可溶性树脂(A-1)。
<合成例A-2至合成例A-5>
合成例A-2至合成例A-5是以与合成例A-1相同的步骤来制备,并且其不同处在于合成例A-2至合成例A-5是改变碱可溶性树脂中原料的种类与使用量及其聚合条件,且其配方及聚合条件如表1所示,在此不另赘述。
PGMEA 丙二醇甲醚醋酸酯 propylene glycol monomethyl ether acetate
AMBN 2,2′-偶氮二-2-甲基丁腈 2,2′-azobis-2-methyl butyronitrile
ADVN 2,2′-偶氮二(2,4-二甲基戊腈) 2,2′-Azobis(2,4-dimethylvaleronitrile)
具有式(2)所示结构的邻萘醌二叠氮磺酸酯化合物(B-1)的合成
<合成例B-1-1>
于干燥的氮气环境中,将0.1摩尔前述式(I-1)所示具有羟基的茀化合物及0.13摩尔的邻萘醌二叠氮-5-磺酸氯加至450g的γ-丁内酯中。
然后,将0.14摩尔的三乙胺溶解于50g的1,4-二恶烷中,以配置成一混合溶液。将所述混合溶液滴加至前述的γ-丁内酯溶液中,并避免溶液的温度超过35℃。
于30℃搅拌2小时后,过滤沉淀析出的三乙胺盐,并将滤液倒入水中。
然后,过滤收集沉淀物,并利用真空干燥机烘干沉淀物,即可制得具有如下式(I-1-1)所示结构的合成例B-1-1且其酯化率为65%:
<合成例B-1-2>
于干燥的氮气环境中,将0.1摩尔前述式(I-2)所示具有羟基的茀化合物及0.14摩尔的邻萘醌二叠氮-5-磺酸氯加至450g的γ-丁内酯中。
然后,将0.154摩尔的三乙胺溶解于50g的1,4-二恶烷中,以配置成一混合溶液。将所述混合溶液滴加至前述的γ-丁内酯溶液中,并避免溶液的温度超过35℃。
于30℃搅拌2小时后,过滤沉淀析出的三乙胺盐,并将滤液倒入水中。
然后,过滤收集沉淀物,并利用真空干燥机烘干沉淀物,即可制得具有如下式(I-2-1)所示的结构的合成例B-1-2且其酯化率为70%:
<合成例B-1-3>
于干燥的氮气环境中,将0.1摩尔前述式(I-3)所示具有羟基的茀化合物及0.26摩尔的邻萘醌二叠氮-5-磺酸氯加至450g的γ-丁内酯中。
然后,将0.28摩尔的三乙胺溶解于50g的1,4-二恶烷中,以配置成一混合溶液。将所述混合溶液滴加至前述的γ-丁内酯溶液中,并避免溶液的温度超过35℃。
于30℃搅拌2小时后,过滤沉淀析出的三乙胺盐,并将滤液倒入水中。
然后,过滤收集沉淀物,并利用真空干燥机烘干沉淀物,即可制得具有如下式(I-3-1)所示的结构的合成例B-1-3,且其酯化率为65%:
<合成例B-1-4>
于干燥的氮气环境中,将0.1摩尔前述式(I-3)所示具有羟基的茀化合物及0.28摩尔的邻萘醌二叠氮-5-磺酸氯加至450g的γ-丁内酯中。
然后,将0.33摩尔的三乙胺溶解于50g的1,4-二恶烷中,以配置成一混合溶液。将所述混合溶液滴加至前述的γ-丁内酯溶液中,并避免溶液的温度超过35℃。
于30℃搅拌2小时后,过滤沉淀析出的三乙胺盐,并将滤液倒入水中。
然后,过滤收集沉淀物,并利用真空干燥机烘干沉淀物,即可制得具有如下式(I-4-1)所示的结构的合成例B-1-4且其酯化率为70%:
正型感光性树脂组成物的制备
<实施例1>
使用前述合成例A-1所制得的碱可溶性树脂(A-1)100重量份、5重量份的前述合成例B-1-1所制得的邻奈醌二叠氮磺酸酯(B-1-1)、0.5重量份的NDI-105(以下简称C-1)、3重量份的表2中D-1所示的结构及1重量份的SF-8427(以下简称F-1)加入溶剂丙二醇甲醚醋酸酯(以下简称E-1)100重量份后,以摇动式搅拌器,加以溶解混合,即可调制而得正型感光性树脂组成物,所述正型感光性树脂组成物以下记的各测定评价方式进行评价,所得结果如表2所示。
<实施例2至实施例10>
实施例2至实施例10的正型感光性树脂组成物是以与实施例1相同的步骤分别制备,并且其不同处在于:改变成分的种类及其使用量,如表2所示。将实施例2至10所制得的正型感光性树脂组成物以后述评价方式进行评价,其结果如表2所示。
<比较例1至比较例3>
比较例1至比较例3的正型感光性树脂组成物是以与实施例1相同的步骤分别制备,并且其不同处在于:改变成分的种类及其使用量,如表2所示。将比较例1至比较例3所制得的正型感光性树脂组成物以后述评价方式进行评价,其结果如表2所示。
表2
B-1-1 合成例B-1-1
B-1-2 合成例B-1-2
B-1-3 合成例B-1-3
B-1-4 合成例B-1-4
B-2-1 1-[1-(4-羟基苯基)异丙基]-4-[1,1-双(4-羟基苯基)乙基]苯与邻萘醌二叠氮-5-磺酸所形成的邻萘醌二叠氮磺酸酯
B-2-2 2,3,4-三羟基二苯甲酮与邻萘醌二叠氮-5-磺酸所形成的邻萘醌二叠氮磺酸酯
B-2-3 2,3,4,4′-四羟基二苯甲酮与邻萘醌二叠氮-5-磺酸所形成的邻萘醌二叠氮磺酸酯
C-1 NDI-105(绿化学株式会社制造)
C-2 SI-105(绿化学株式会社制造)
C-3 PAI-106(绿化学株式会社制造)
C-4 SI-100(三新化学制)
C-5 SI-150(三新化学制)
C-6 {[(2-硝基苄基)氧基]羰基}甲基胺
C-7 {[(α,α-二甲基-3,5-二甲氧基苄基)氧基]羰基}己基胺
C-8 丙酰二苯甲酮肟
C-10 N-(异丙氧基羰基)-2,6-二甲基哌啶
E-1 丙二醇甲醚醋酸酯
E-2 二乙二醇二甲醚
E-3 3-乙氧基丙酸乙酯
F-1 SF-8427
F-2 3-环氧丙氧基丙基三甲氧基硅烷(KBM403,信越化学制)
评价方式
<绝缘性>
将正型感光性树脂组成物以旋转涂布的方式涂布在SUS基板上,得到厚度约2μm的预涂膜,接着以110℃预烤2分钟后,在曝光机(AG500-4N;M&R Nano Technology制)以能量为200J/cm2的紫外光照射预涂膜,接着,再以曝光机直接照射显影后的涂膜,其能量为300mJ/cm2,最后,以230℃后烤60分钟,即可获得SUS基板上的绝缘膜。利用蒸镀法于所述绝缘膜上形成Pt/Pd电极图案而制作成测定用样品,接着,使用Precision LCR meter(Yokogawa Hewlett Packard″HP4284A″)于10kHz的频率下,通过CV法测得介电常数。
◎:介电常数≤3.3
○:3.3<介电常数≤3.6
△:3.6<介电常数≤3.9
×:介电常数>3.9
上述实施例仅为说明本发明的原理及其功效,而非限制本发明。所属技术领域技术人员对上述实施例所做的修改及变化仍不违背本发明的精神。
Claims (10)
2.根据权利要求1所述的正型感光性树脂组成物,其中,所述碱可溶性树脂(A)是由不饱和羧酸或不饱和羧酸酐化合物(a1)、含环氧基的不饱和化合物(a2)及其他不饱和化合物(a3)所共聚合而得。
3.根据权利要求1所述的正型感光性树脂组成物,其中,基于所述碱可溶性树脂(A)的使用量为100重量份,所述邻萘醌二叠氮磺酸酯(B)的使用量为5至60重量份;所述化合物(C)的使用量为0.3至3重量份;所述环状硅氧烷化合物(D)的使用量为3至30重量份;及所述溶剂(E)的使用量为100至1000重量份。
5.根据权利要求4所述的正型感光性树脂组成物,其中,基于所述碱可溶性树脂(A)的使用量为100重量份,所述式(2)所示结构的邻萘醌二叠氮磺酸酯化合物(B-1)的使用量为5至50重量份。
6.根据权利要求1所述的正型感光性树脂组成物,其中,所述热酸发生剂是选自由锍盐、含卤素化合物、重氮甲烷化合物、砜化合物、磺酸酯化合物、羧酸酯化合物、磷酸酯化合物、磺酰亚胺化合物、磺化苯并三唑类化合物及其组合所组成的群组。
7. 根据权利要求1所述的正型感光性树脂组成物,其中,所述热碱发生剂是选自由过渡金属络合物类、酰基肟类、下列式(3)所示结构的化合物或其盐类衍生物、下列式(4)所示结构的化合物、下列式(5)所示结构的化合物及其组合所组成的群组:
其中:
m表示2至6的整数;及
R31、R32各自独立地表示氢原子、碳数1至8的烷基、碳数1至6的可具有取代基的羟烷基或碳数2至12的二烷基胺基;
其中:
R33、R34、R35及R36各自独立地表示氢原子、碳数1至8的可具有取代基的烷基、碳数3至8的可具有取代基的环烷基、碳数1至8的可具有取代基的烷氧基、碳数2至8的可具有取代基的烯基、碳数2至8的可具有取代基的炔基、可具有取代基的芳基或可具有取代基的杂环基;
R37及R38各自独立地表示氢原子、碳数1至8的可具有取代基的烷基、碳数3至8的可具有取代基的环烷基、碳数1至8的可具有取代基的烷氧基、碳数2至8的可具有取代基的烯基、碳数2至8的可具有取代基的炔基、可具有取代基的芳基或可具有取代基的杂环基、或彼此结合形成可具有取代基的单环;或彼此结合形成可具有取代基的多环;及
R39表示碳数1至12的可具有取代基的烷基、碳数3至12的可具有取代基的环烷基、碳数2至12的可具有取代基的烯基、碳数2至12的可具有取代基的炔基、可具有碳数为1至3的烷基取代基的芳基、可具有碳数为1至3的烷基取代基的芳烷基或可具有取代基的杂环基,但R39的碳原子总数为12以下;
其中:
R33、R34、R35及R36、R37及R38的定义如式(4)所示;及
R40表示碳数1至12的可具有取代基的亚烷基、碳数3至12的可具有取代基的亚环烷基、碳数2至12的可具有取代基的亚烯基、碳数2至12的可具有取代基的亚炔基、可具有碳数为1至3的烷基取代基的亚芳基、可具有碳数为1至3的烷基取代基的亚芳烷基或可具有取代基的杂环基,但R40的碳原子总数为12以下。
8.一种于一基板上形成薄膜的方法,其包含使用如权利要求1-7任一项所述的正型感光性树脂组成物施予所述基板上。
9.一种基板上的薄膜,其是由权利要求8所述的方法所制得。
10.根据权利要求9所述的薄膜,其是为液晶显示元件或有机电激发光显示器中薄膜电晶体基板用的平坦化膜、层间绝缘膜或光波导路的芯材或包覆材的保护膜。
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CN101443704A (zh) * | 2006-05-16 | 2009-05-27 | 日产化学工业株式会社 | 正型感光性树脂组合物以及由其得到的多孔膜 |
JP2011227291A (ja) * | 2010-04-20 | 2011-11-10 | Adeka Corp | ポジ型感光性組成物及び永久レジスト |
CN102566279A (zh) * | 2010-11-25 | 2012-07-11 | 株式会社艾迪科 | 正型感光性树脂组合物及永久抗蚀剂 |
CN103781814A (zh) * | 2011-10-25 | 2014-05-07 | 株式会社艾迪科 | 光固化性树脂组合物以及新型硅氧烷化合物 |
JP2015069172A (ja) * | 2013-09-30 | 2015-04-13 | Jsr株式会社 | 感放射線性樹脂組成物、硬化膜、その形成方法、半導体素子及び表示素子 |
CN104950580A (zh) * | 2014-03-28 | 2015-09-30 | 奇美实业股份有限公司 | 感光性聚硅氧烷组合物及其应用 |
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CN101443704A (zh) * | 2006-05-16 | 2009-05-27 | 日产化学工业株式会社 | 正型感光性树脂组合物以及由其得到的多孔膜 |
JP2011227291A (ja) * | 2010-04-20 | 2011-11-10 | Adeka Corp | ポジ型感光性組成物及び永久レジスト |
CN102566279A (zh) * | 2010-11-25 | 2012-07-11 | 株式会社艾迪科 | 正型感光性树脂组合物及永久抗蚀剂 |
CN103781814A (zh) * | 2011-10-25 | 2014-05-07 | 株式会社艾迪科 | 光固化性树脂组合物以及新型硅氧烷化合物 |
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CN105637008A (zh) * | 2013-10-16 | 2016-06-01 | 日本化药株式会社 | 固化性树脂组合物及其固化物 |
CN104950580A (zh) * | 2014-03-28 | 2015-09-30 | 奇美实业股份有限公司 | 感光性聚硅氧烷组合物及其应用 |
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