CN103135353B - 树脂组成物、液晶显示装置、彩色滤光片及其制造方法 - Google Patents
树脂组成物、液晶显示装置、彩色滤光片及其制造方法 Download PDFInfo
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- CN103135353B CN103135353B CN201210513203.1A CN201210513203A CN103135353B CN 103135353 B CN103135353 B CN 103135353B CN 201210513203 A CN201210513203 A CN 201210513203A CN 103135353 B CN103135353 B CN 103135353B
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- photosensitive resin
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 40
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 11
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
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- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Landscapes
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- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Silicon Polymers (AREA)
Abstract
本发明提供一种感光性树脂组成物、彩色滤光片、制造方法及液晶显示装置,该感光性树脂组成物包括:碱可溶性树脂、含乙烯性不饱和基的化合物、光起始剂、有机溶剂、颜料及染料。该感光性树脂组成物具有显影后所形成的图案边缘平滑性佳及所制得的液晶显示装置的对比佳的优点。
Description
技术领域
本发明是有关一种液晶显示器的彩色滤光片用蓝色感光性树脂组成物。特别是有关一种显影后所形成的图案边缘平滑性佳及所制得的液晶显示装置的对比佳的彩色滤光片用蓝色感光性树脂组成物。
背景技术
在彩色滤光片制造过程中,感光性树脂的使用为一重要步骤。现有制造彩色滤光片的方法是将感光性树脂组成物形成于透明基板上,经由预烤(prebake)将组成物干燥,并进一步进行曝光及显影及后烤(postbake)等步骤,而得到各色的像素与遮光层。如日本特许公开第平2-144502及平3-53201号揭示制造各色像素的方法,日本特许公开第平6-35188号揭示使用包含黑色材料的光聚合性组成物制造黑色矩阵的方法。
近年来,液晶显示装置由于其轻、薄、省电等特性,使液晶显示器在各式电子用品上迅速的发展,例如电视。然而在此应用领域中,一般而言皆有高对比的要求。为了提升液晶显示装置高对比的特性,业界曾开发可提升彩色滤光片的对比度的感光树脂组合物,例如日本公开特许第2001-033616号所揭示者,其使用特定颜料C.I.Pigment Red 122的彩色滤光片用蓝色感光性树脂组成物。但以上述的技术所制得的液晶显示装置已无法满足现今业界对液晶显示器的对比日益升高的需求。
再者,现今液晶显示器的演进,皆朝向高解析度的方向,其中重要的改善方案即为增加像素的精细度,欲得高精细度的像素,则其像素图案的边缘须力求平滑性。然而,此等习知的感光性树脂当应用于制造滤光片时,涂布于例如透明导电薄膜(如氧化铟锡ITO蒸镀膜,IZO等)的无机膜或氮化硅及氧化硅薄膜上时,具有边缘平滑性不佳的缺点,此缺点会在像素层上造成裂痕或断层的现象发生。
因此,如何同时提升像素图案边缘的平滑性及液晶显示装置的对比,以达到目前业界的要求,为本发明所属技术领域中努力研究的目标。
发明内容
本发明利用提供特殊碱可溶性树脂的成分,而得到一显影后所形成的图案边缘平滑性佳及所制得的液晶显示装置的对比佳的彩色滤光片用感光性树脂组成物。
因此,本发明是有关一种感光性树脂组成物,其包含:
碱可溶性树脂(A);
含乙烯性不饱和基的化合物(B);
光起始剂(C);
有机溶剂(D);
颜料(E);及
染料(F);
其中,该碱可溶性树脂(A)包含聚硅氧烷聚合物(A-1),该聚硅氧烷聚合物(A-1)是由下列结构式(1)所表示的硅烷化合物经加水分解及缩合反应而得;
Si(Ra)z(ORb)4-z 结构式(1)
其中:
Ra表示至少一个为含有羧酸酐取代基的烷基,其他Ra是独立选自由氢原子、碳数1至10的烷基、碳数2至10的烯基及碳数6至15的芳基所组成的群;
Rb是独立选自由氢原子、碳数1至6的烷基、碳数1至6的酰基及碳数6至15的芳基;及
z表示1至3的整数。
本发明亦提供一种彩色滤光片的制造方法,其使用前述的感光性树脂组成物形成一像素层。
本发明又提供一种彩色滤光片,其是由前述的方法所制得。
本发明再提供一种液晶显示装置,包含前述的彩色滤光片。
本发明的感光性树脂组成物具有显影后所形成的图案边缘平滑性佳及所制得的液晶显示装置的对比佳的优点。
附图说明
图1为本发明一较佳实施例的彩色液晶显示器示意图。
图2为感光性树脂层对比测定状态(一)的示意图。
图3为感光性树脂层对比测定状态(二)的示意图。
图4为感光性树脂图案的边缘侧面状态(一)的示意图。
图5为感光性树脂图案的边缘侧面状态(二)的示意图。
图6为感光性树脂图案的边缘侧面状态(三)的示意图。
附图标号:
1感光性树脂层
2偏光板
3偏光板
4光源
5辉度计
10液晶显示装置
11彩色滤光片
12液晶
13第一基板
14第二基板
15配向层
16偏光板
20背光单元
171感光树脂层
172感光树脂层
173感光树脂层
具体实施方式
发明详细说明
本发明提供一种感光性树脂组成物,其包含:
碱可溶性树脂(A);
含乙烯性不饱和基的化合物(B);
光起始剂(C);
有机溶剂(D);
颜料(E);及
染料(F)。
根据本发明的该碱可溶性树脂(A)包含聚硅氧烷聚合物(A-1)。该聚硅氧烷聚合物(A-1)的构造并无特别限制,于本发明的一较佳具体例中,该聚硅氧烷聚合物(A-1)可使用硅烷化合物及/或聚硅氧烷加水分解及缩合而制得,较佳地,该缩合为部份缩合。
于本发明的一较佳具体例中,该硅烷化合物包含但不限于下列结构式(1)所示的结构:
Si(Ra)z(ORb)4-z 结构式(1)
其中:
Ra表示至少一个为含有羧酸酐取代基的烷基,其他Ra是独立选自由氢原子、碳数1至10的烷基、碳数2至10的烯基及碳数6至15的芳基所组成的群,复数的Ra可相同亦可不同;
Rb是独立选自由氢原子、碳数1至6的烷基、碳数1至6的酰基及碳数6至15的芳基所组成的群,复数的Rb可相同或相异;及
z表示1至3的整数。
根据本发明的结构式(1)化合物中,较佳地,Ra表示至少一个为含有琥珀酸酐(succinic acid anhydride)取代基的烷基。于本发明的具体例中,含有羧酸酐取代基的烷基为甲基、乙基、正丙基、异丙基、正丁基、叔丁基、正己基、正癸基。另一方面,非含有羧酸酐取代基的烷基的其他Ra中的烯基及芳基依所欲的性质,可不含取代基或包含取代基。于本发明的具体例中,非含有羧酸酐取代基的烷基的其他Ra中,碳数1至10的烷基为甲基、乙基、正丙基、异丙基、正丁基、叔丁基、正己基、正癸基、三氟甲基、2,2,2-三氟乙基、3,3,3-三氟丙基、3-胺丙基、3-巯丙基和3-异氰酸丙基;碳数2至10的烯基为乙烯基、3-烯丙氧丙基和3-甲基烯丙氧丙基;碳数6至15的芳基为苯基、甲苯基、p-羟基苯基、1-(p-羟基苯基)乙基、2-(p-羟基苯基)乙基、4-羟基-5-(p-羟基苯基羰氧基)戊基和萘基。
根据本发明的结构式(1)化合物中,Rb是独立选自由氢原子、碳数1至6的烷基、碳数1至6的酰基及碳数6至15的芳基所组成的群。复数的Rb可相同或相异。Rb中的烷基、酰基及芳基依所欲的性质,可不含取代基或包含取代基。于本发明的具体例,Rb中碳数1至6的烷基为甲基、乙基、正丙基、异丙基及正丁基;碳数1至6的酰基为乙酰基;碳数6至15的芳基为苯基。
根据本发明的结构式(1)化合物中,z表示1至3的整数;当z为1时,表示包含三官能性的硅烷;当z为2时,表示包含二官能性的硅烷;当z为3时,表示包含单官能性的硅烷。
于本发明的较佳具体例中,结构式(1)化合物中含有羧酸酐取代基的硅烷化合物包含但不限于,(i)三官能性硅烷:2-丁二酸酐乙基三甲氧基硅烷、3-丁二酸酐丙基三苯氧基硅烷、由信越化学所制造的市售品(3-丁二酸酐丙基三甲氧基硅烷,商品名X-12-967)、由WACKER公司所制造的市售品(3-丁二酸酐丙基三乙氧基硅烷,商品名GF-20)、3-戊二酸酐丙基三甲氧基硅烷(3-trimethoxysilylpropyl glutaric anhydride,简称TMSG)、3-戊二酸酐丙基三乙氧基硅烷、3-戊二酸酐丙基三苯氧基硅烷等;(ii)二官能性硅烷:二(丁二酸酐丙基)二正丁氧基硅烷、二(丁二酸酐乙基)二甲氧基硅烷等;(iii)单官能性硅烷:三(丁二酸酐丙基)苯氧基硅烷、二(丁二酸酐乙基)甲基甲氧基硅烷等。上述的各种硅烷化合物可单独一种使用或混合多种使用。
于本发明的另一较佳具体例中,该硅烷化合物包含但不限于下列结构式(2)所示的结构:
Si(Ri)y(ORj)4-y 结构式(2)
其中:
Ri表示选自由氢原子、碳数1至10的烷基、碳数2至10的烯基及碳数6至15的芳基所组成的群,其中碳数1至10的烷基不含有羧酸酐取代基,及复数的Ri可相同亦可不同。
Rj是独立选自由氢原子、碳数1至6的烷基、碳数1至6的酰基及碳数6至15的芳基所组成的群,复数的Rj可相同或相异;及
y表示1至3的整数。
结构式(2)化合物中未含有羧酸酐取代基的硅烷化合物包含但不限于,(i)四官能性硅烷:四甲氧基硅烷、四乙氧基硅烷、四乙酰氧基硅烷[tetraacetoxysilane]、四苯氧基硅烷等;(ii)三官能性硅烷:甲基三甲氧基硅烷[methyltrimethoxysilane简称MTMS]、甲基三乙氧基硅烷、甲基三异丙氧基硅烷、甲基三正丁氧基硅烷、乙基三甲氧基硅烷、乙基三乙氧基硅烷、乙基三异丙氧基硅烷、乙基三正丁氧基硅烷、正丙基三甲氧基硅烷、正丙基三乙氧基硅烷、正丁基三甲氧基硅烷、正丁基三乙氧基硅烷、正己基三甲氧基硅烷、正己基三乙氧基硅烷、癸基三甲氧基硅烷、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、3-丙烯酰氧基丙基三乙氧基硅烷、3-甲基丙烯酰氧基丙基三甲氧基硅烷、3-甲基丙烯酰氧基丙基三乙氧基硅烷、苯基三甲氧基硅烷[phenyltrimethoxysilane简称PTMS]、苯基三乙氧基硅烷[phenyltriethoxysilane简称PTES]、对-羟基苯基三甲氧基硅烷、1-(对-羟基苯基)乙基三甲氧基硅烷、2-(对-羟基苯基)乙基三甲氧基硅烷、4-羟基-5-(对-羟基苯基羰氧基)戊基三甲氧基硅烷、三氟甲基三甲氧基硅烷、三氟甲基三乙氧基硅烷、3,3,3-三氟丙基三甲氧基硅烷、3-胺丙基三甲氧基硅烷、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-环氧丙氧基丙基三乙氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷、3-巯丙基三甲氧基硅烷、2-环氧丙烷基丁氧基丙基三苯氧基硅烷、由东亚合成所制造的市售品(2-环氧丙烷基丁氧基丙基三甲氧基硅烷,商品名TMSOX;2-环氧丙烷基丁氧基丙基三乙氧基硅烷,商品名TESOX);(iii)二官能性硅烷:二甲基二甲氧基硅烷[dimethyldimethoxysilane簡稱DMDMS]、二甲基二乙氧基硅烷、二甲基二乙醯氧基硅烷、二正丁基二甲氧基硅烷、二苯基二甲氧基硅烷、二異丙氧基-二(2-環氧丙烷基丁氧基丙基)硅烷[diisopropoxy-di(2-oxetanylbutoxy propyl)silane简称DIDOS]、二(3-環氧丙烷基戊基)二甲氧基硅烷;(iv)單官能性硅烷:三甲基甲氧基硅烷、三正丁基乙氧基硅烷、3-環氧丙氧基二甲基甲氧基硅烷、3-環氧丙氧基二甲基乙氧基硅烷、二(2-環氧丙烷基丁氧基戊基)2-環氧丙烷基戊基乙氧基硅烷、三(2-環氧丙烷基戊基)甲氧基硅烷等。上述的各种硅烷化合物可单独一种使用或混合多种使用。
于本发明的一具体例中,当进行如结构式(1)化合物的共聚合反应时,化合物(1)所含的羧酸酐将自行开环,使其具有亲水性的羧酸根。上述所获得的聚硅氧烷聚合物(A-1),对碱性显影液有较佳的显影性。其中聚合反应的温度是为可使羧酸酐充分开环者,较佳是于高于100C反应30分钟。
根据本发明,当进行羧酸酐开环反应时,羧酸酐开环量相对聚硅氧烷聚合物(A-1)中的硅原子并不受限制,较佳是大于10mol%。当羧酸根少于10mol%时,聚硅氧烷聚合物(A-1)的亲水性则不足。因此,当所涂布而成的图案于碱性显影液中显影时,将造成低感光性与显影性不佳。羧酸根的含量可如但不限于下述方法测定。
首先,将1重量%苯标准品及聚硅氧烷聚合物(A-1)混合,以进行元素分析及1H-NMR测定,并于元素分析中计算苯莫耳数对Si原子的莫耳数。并以1H-NMR测定(使用1H-NMR:CDCl3溶剂)羧酸的峰面积及苯的峰面积,相对聚硅氧烷聚合物(A-1)中的硅原子的羧酸酐开环量可藉由苯莫耳数而计算得。
本发明中,前述聚硅氧烷包含但不限于由下式(3)所示的聚硅氧烷:结构式(3)
其中:
Rc、Rd、Re及Rf是分别选自由氢原子、碳数1至10的烷基、碳数2至6的烯基及碳数6至15的芳基所组成的群;其中该烷基、烯基或芳基较佳是含有取代基;
s为介于1至1000间的整数;较佳地,s为介于3至300间的整数;更佳地,s为介于5至200间的整数。
当s为自2至1000的整数时,每个Rc为相同或不同,且每个Rd为相同或不同。较佳地,烷基例如但不限于甲基、乙基、正丙基等;烯基例如但不限于乙烯基、丙烯酰氧基丙基、甲基丙烯酰氧基丙基等;芳基例如但不限于苯基、甲苯基、萘基等。
Rg及Rh是分别选自由氢原子、碳数1至6的烷基、碳数1至6的酰基及碳数6至15的芳基所组成的群;其中该烷基、酰基或芳基较佳是含有取代基。较佳地,烷基例如但不限于甲基、乙基、正丙基、异丙基、正丁基等;酰基例如但不限于乙酰基。芳基例如但不限于苯基。
于本发明的较佳具体例中,该聚硅氧烷包含但不限于1,1,3,3-四甲基-1,3-二甲氧基二硅氧烷、1,1,3,3-四甲基-1,3-二乙氧基二硅氧烷、1,1,3,3-四乙基-1,3-二乙氧基二硅氧烷、Gelest公司制硅烷醇末端聚硅氧烷的市售品[商品名如DM-S12(分子量400~700)、DMS-S15(分子量1500~2000)、DMS-S21(分子量4200)、DMS-S27(分子量18000)、DMS-S31(分子量26000)、DMS-S32(分子量36000)、DMS-S33(分子量43500)、DMS-S35(分子量49000)、DMS-S38(分子量58000)、DMS-S42(分子量77000)、PDS-9931(分子量1000~1400)等]等。上述各种聚硅氧烷可单独一种使用或混合多种使用。
当该硅烷化合物与聚硅氧烷混合使用时,其混合比率并无特别限制。较佳地,该硅烷化合物与聚硅氧烷的Si原子莫耳数比是介于100:0.01~50:50之间。
于本发明的在一较佳具体例中,该聚硅氧烷(A-1)除了可由上述的硅烷化合物及/或聚硅氧烷进行加水分解及部分缩合而制得外,亦可混合二氧化硅(silicon dioxide)粒子进行共聚合反应。该二氧化硅的平均粒径并无特别的限制,其平均粒径是介于2nm至250nm之间。较佳地,其平均粒径是介于5nm至200nm之间。更佳地,其平均粒径是介于10nm至100nm之间。
该二氧化硅粒子可例如由触媒化成公司所制造的市售品[商品名如OSCAR 1132(粒径12nm;分散剂为甲醇)、OSCAR 1332(粒径12nm;分散剂为正丙醇)、OSCAR 105(粒径60nm;分散剂为γ-丁内酯)、OSCAR 106(粒径120nm;分散剂为二丙酮醇)等]、由扶桑化学公司所制造的市售品[商品名如Quartron PL-1-IPA(粒径13nm;分散剂为异丙酮)、Quartron PL-1-TOL(粒径13nm;分散剂为甲苯)、Quartron PL-2L-PGME(粒径18nm;分散剂为丙二醇单甲醚)、Quartron PL-2L-MEK(粒径18nm;分散剂为甲乙酮)等]、由日产化学公司所制造的市售品[商品名如IPA-ST(粒径12nm;分散剂为异丙醇)、EG-ST(粒径12nm;分散剂为乙二醇)、IPA-ST-L(粒径45nm;分散剂为异丙醇)、IPA-ST-ZL(粒径100nm;分散剂为异丙醇)等]。上述各种二氧化硅粒子可单独一种使用或混合多种使用。
该二氧化硅粒子与该硅烷化合物及/或聚硅氧烷混合时,并无使用量的限制。较佳地,该二氧化硅粒子的Si原子莫耳数与该聚硅氧烷聚合物(A-1)的Si原子莫耳数比为1%~50%之间。
根据本发明的聚硅氧烷聚合物(A-1)可由但不限于硅烷化合物及/或聚硅氧烷、二氧化硅粒子等混合物经加水分解及缩合反应而得;较佳地,由结构式(1)或结构式(2)所表示的硅烷化合物经加水分解及缩合反应而得,较佳是将反应物加入如水的溶剂中,并添加催化剂,及加热搅拌。水解反应的副产物(醇类,例如甲醇)及缩合反应的副产物(水)视需要可于搅拌中经由蒸馏去除。
根据本发明,制造聚硅氧烷聚合物(A-1)的反应溶剂并无特殊限制,例如可使用下文中所述的有机溶剂(D)。溶剂的使用量可为相对于全体有机硅烷量的10至1000重量%;较佳为100重量%。当使用水为水解反应的溶剂时,较佳是相对于1mol的水解量,添加0.5至2mol的水。
根据本发明,制造聚硅氧烷聚合物(A-1)时所视需要添加的催化剂并无特殊限制,较佳是使用酸性催化剂或碱性催化剂。酸性催化剂例如:盐酸、硝酸、硫酸、氟酸、草酸、磷酸、醋酸、三氟乙酸、甲酸、多价羧酸及其酸酐。碱性催化剂例如:三乙胺、三丙胺、三正丁胺、三戊胺、三己胺、三庚胺、三辛胺、二乙胺、三乙醇胺、二乙醇胺、氢氧化钠、氢氧化钾水合物、含胺基化合物。催化剂的使用量可为基于全体有机硅烷量为100重量%,较佳为0.01至10重量%。
于本发明的一较佳具体例中副产物的醇、水及催化剂在水解反应及缩合反应后,并不存于聚硅氧烷聚合物(A-1)溶液中,俾利涂布性及储存的稳定性。可视需要进行去除步骤。根据本发明的去除步骤并无特殊限制,较佳地,去除醇类或水的方法,是将聚硅氧烷聚合物(A-1)溶液以适当的疏水性溶剂稀释后,利用水清洗数次并蒸发;去除催化剂的方法,可独立使用离子交换树脂程序或加上前述的水清洗步骤。
本发明的其中一技术特征在于使用经羧酸酐取代的聚硅氧烷聚合物(A-1),其可大幅提升感光性树脂制成滤光片的对比及密着性。相反地,未使用羧酸酐改质的聚硅氧烷聚合物(A-1)时,所制得的彩色滤光片具有对比及密着性不佳的缺点。
本发明的聚硅氧烷聚合物(A-1)使用量较佳基于碱可溶性树脂(A)使用量100重量份,该聚硅氧烷聚合物(A-1)的使用量介于5至70重量份;更佳介于8至65重量份;尤佳介于10至60重量份。则当应用此感光性树脂组成物于制造滤光片时,具有较佳的对比性及密着性。
于本发明的一较佳具体例中,该碱可溶性树脂(A)进一步包含一丙烯酸系树脂(A-2)。于本发明的一较佳具体例中,丙烯酸系树脂(A-2)是由含一个或一个以上的羧酸基的乙烯性不饱和单体,以及其他可共聚合的乙烯性不饱和单体共聚合而得。以100重量份计,该丙烯酸系树脂(A-2)是由50至95重量份的含一个或一个以上羧酸基的乙烯性不饱和单体和5至50重量份的乙烯性不饱和单体共聚合而得。
前述该含羧酸基的乙烯性不饱和单体是选自丙烯酸、甲基丙烯酸、丁烯酸、α-氯丙烯酸、乙基丙烯酸、肉桂酸、2-丙烯酰乙氧基丁二酸酯、2-甲基丙烯酰乙氧基丁二酸酯及2-异丁烯酰乙氧基丁二酸酯等的不饱和一元羧酸类;马来酸、马来酸酐、富马酸、衣康酸、衣康酸酐、柠康酸及柠康酸酐等,不饱和二元羧酸(酐)类;三价以上的不饱和多元羧酸(酐)类;较佳地,该含羧酸基的乙烯性不饱和单体是选自丙烯酸、甲基丙烯酸、2-丙烯酰乙氧基丁二酸酯、2-甲基丙烯酰乙氧基丁二酸酯及2-异丁烯酰乙氧基丁二酸酯;更佳地,该羧酸基的乙烯性不饱和单体是选自2-丙烯酰乙氧基丁二酸酯、2-甲基丙烯酰乙氧基丁二酸酯、2-异丁烯酰乙氧基丁二酸酯,可以提高颜料分散性、增进显影速度以及减少残渣发生。
其它可共聚合的乙烯性不饱和单体的具体例如:苯乙烯、α-甲基苯乙烯、乙烯基甲苯、对氯苯乙烯、甲氧基苯乙烯等的芳香族乙烯基化合物;N-苯基马来酰亚胺、N-邻-羟基苯基马来酰亚胺、N-间-羟基苯基马来酰亚胺、N-对-羟基苯基马来酰亚胺、N-邻-甲基苯基马来酰亚胺、N-间-甲基苯基马来酰亚胺、N-对-甲基苯基马来酰亚胺、N-邻-甲氧基苯基马来酰亚胺、N-间-甲氧基苯基马来酰亚胺、N-对-甲氧基苯基马来酰亚胺、N-环己基马来酰亚胺等马来酰亚胺类;丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丙酯、甲基丙烯酸正丙酯、丙烯酸异丙酯、甲基丙烯酸异丙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸异丁酯、甲基丙烯酸异丁酯、丙烯酸第二丁酯、甲基丙烯酸第二丁酯、丙烯酸第三丁酯、甲基丙烯酸第三丁酯、丙烯酸2-羟基乙酯、甲基丙烯酸2-羟基乙酯、丙烯酸2-羟基丙酯、甲基丙烯酸2-羟基丙酯、丙烯酸3-羟基丙酯、甲基丙烯酸3-羟基丙酯、丙烯酸2-羟基丁酯、甲基丙烯酸2-羟基丁酯、丙烯酸3-羟基丁酯、甲基丙烯酸3-羟基丁酯、丙烯酸4-羟基丁酯、甲基丙烯酸4-羟基丁酯、丙烯酸烯丙酯、甲基丙烯酸烯丙酯、丙烯酸苯甲酯、甲基丙烯酸苯甲酯、丙烯酸苯酯、甲基丙烯酸苯酯、丙烯酸三乙二醇甲氧酯、甲基丙烯酸三乙二醇甲氧酯、甲基丙烯酸十二烷基酯、甲基丙烯酸十四烷基酯、甲基丙烯酸十六烷基酯、甲基丙烯酸十八烷基酯、甲基丙烯酸二十烷基酯、甲基丙烯酸二十二烷基酯、丙烯酸双环戊烯基氧化乙酯等的不饱和羧酸酯类;丙烯酸N,N-二甲基胺基乙酯、甲基丙烯酸N,N-二甲基胺基乙酯、丙烯酸N,N-二乙基胺基丙酯、甲基丙烯酸N,N-二甲基胺基丙酯、丙烯酸N,N-二丁基胺基丙酯、甲基丙烯酸N,异-丁基胺基乙酯;丙烯酸环氧丙基酯、甲基丙烯酸环氧丙基酯等不饱和羧酸环氧丙基酯类;乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯等的羧酸乙烯酯类;乙烯基甲醚、乙烯基乙醚、烯丙基环氧丙基醚、甲代烯丙基环氧丙基醚等不饱和醚类;丙烯腈、甲基丙烯腈、α-氯丙烯腈、氰化亚乙烯等的氰化乙烯基化合物;丙烯酰胺、甲基丙烯酰胺、α-氯丙烯酰胺、N-羟乙基丙烯酰胺、N-羟乙基甲基丙烯酰胺等的不饱和酰胺;1,3-丁二烯、异戊烯、氯化丁二烯等的脂肪族共轭二烯类。
较佳地,该共聚合的乙烯性不饱和单体是选自苯乙烯、N-苯基马来酰亚胺、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸2-羟基乙酯、甲基丙烯酸2-羟基乙酯、丙烯酸苯甲酯、甲基丙烯酸苯甲酯、丙烯酸、甲基丙烯酸、2-丙烯酰乙氧基丁二酸酯、丙烯酸双环戊烯基氧化乙酯、2-甲基丙烯酰乙氧基丁二酸酯及2-异丁烯酰乙氧基丁二酸酯,更佳地,该共聚合的乙烯性不饱和单体是选自2-丙烯酰乙氧基丁二酸酯、2-甲基丙烯酰乙氧基丁二酸酯及2-异丁烯酰乙氧基丁二酸酯等的含羧酸基乙烯性不饱和单体,可以提高颜料分散性、增进显影速度以及减少残渣发生,且该些可共聚合的乙烯性不饱和单体可单独一种或混合复数种使用。
此外,于制备本发明丙烯酸系树脂(A-2)所使用的溶剂为选自乙二醇甲醚、乙二醇乙醚、二甘醇甲醚、二甘醇乙醚、二甘醇正丙醚、二甘醇正丁醚、三甘醇甲醚、三甘醇乙醚、丙二醇甲醚、丙二醇乙醚、一缩二丙二醇甲醚、一缩二丙二醇乙醚、一缩二丙二醇正丙醚、一缩二丙二醇正丁醚、二缩三丙二醇甲醚、二缩三丙二醇乙醚等的(聚)亚烷基二醇单烷醚类;乙二醇甲醚醋酸酯、乙二醇乙醚醋酸酯、丙二醇甲醚醋酸酯、丙二醇乙醚醋酸酯等(聚)亚烷基二醇单烷醚醋酸酯类;二甘醇二甲醚、二甘醇甲乙醚、二甘醇二乙醚、四氢呋喃等其他醚类;甲乙烷酮、环己酮、2-庚酮、3-庚酮等酮类;2-羟基丙酸甲酯、2-羟基丙酸乙酯等乳酸烷酯类;2-羟基-2-甲基丙酸甲酯、2-羟基-2-甲基丙酸乙酯、3-甲氧基丙酸甲酯、3-甲氧基丙酸乙酯、3-乙氧基丙酸甲酯、3-乙氧基丙酸乙酯、乙氧基乙酸乙酯、羟基乙酸乙酯、2-羟基-3-甲基丁酸甲酯、3-甲基-3-甲氧基丁基乙酸酯、3-甲基-3-甲氧基丁基丙酸酯、乙酸乙酯、乙酸正丙酯、乙酸异丙酯、乙酸正丁酯、乙酸异丁酯、乙酸正戊酯、乙酸异戊酯、丙酸正丁酯、丁酸乙酯、丁酸正丙酯、丁酸异丙酯、丁酸正丁酯、丙酮酸甲酯、丙酮酸乙酯、丙酮酸正丙酯、乙酰乙酸甲酯、乙酰乙酸乙酯、2-氧基丁酸乙酯等其他酯类;甲苯、二甲苯等芳香族碳氢化合物类;N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺等羧酸酰胺类等,较佳地,该溶剂是选自丙二醇甲醚醋酸酯、3-乙氧基丙酸乙酯,且前述溶剂可单独一种或混合复数种使用。
此外,要再说明的是,该丙烯酸系树脂(A-2)制备时所使用的起始剂,一般为自由基型聚合起始剂,具体例如:2,2′-偶氮双异丁腈、2,2′-偶氮双(2,4-二甲基戊腈)、2,2′-偶氮双(4-甲氧基-2,4-二甲基戊腈)、2,2′-偶氮双-2-甲基丁腈等偶氮(azo)化合物、过氧化二苯甲酰等过氧化合物。
较佳地,基于碱可溶性树脂(A)使用量100重量份,该丙烯酸系树脂(A-2)的使用量为30至95重量份;更佳介于35至92重量份,尤佳介于40至90重量份。则当应用此感光性树脂组成物于制造滤光片时,具有较佳的显影性。
根据本发明的含乙烯性不饱和基的化合物(B)是指具有至少一个乙烯性不饱和基的不饱和化合物。于本发明的具体例中,具有一个乙烯性不饱和基化合物为:丙烯酰胺、(甲基)丙烯酰吗啉、(甲基)丙烯酸-7-氨基-3,7-二甲基辛酯、异丁氧基甲基(甲基)丙烯酰胺、(甲基)丙烯酸异冰片基氧乙酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸-2-乙基己酯、乙基二甘醇(甲基)丙烯酸酯、第三辛基(甲基)丙烯酰胺、二丙酮(甲基)丙烯酰胺、(甲基)丙烯酸二甲氨基酯、(甲基)丙烯酸十二烷基酯、(甲基)丙烯酸二环戊烯氧基乙酯、(甲基)丙烯酸二环戊烯酯、N,N-二甲基(甲基)丙烯酰胺、(甲基)丙烯酸四氯苯酯、(甲基)丙烯酸-2-四氯苯氧基乙酯、(甲基)丙烯酸四氢糠酯、(甲基)丙烯酸四溴苯酯、(甲基)丙烯酸-2-四溴苯氧基乙酯、(甲基)丙烯酸-2-三氯苯氧基乙酯、(甲基)丙烯酸三溴苯酯、(甲基)丙烯酸-2-三溴苯氧基乙酯、(甲基)丙烯酸-2-羟乙酯、(甲基)丙烯酸-2-羟丙酯、乙烯基己内酰胺、N-乙烯基皮酪烷酮、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸五氯苯酯、(甲基)丙烯酸五溴苯酯、聚单(甲基)丙烯酸乙二醇酯、聚单(甲基)丙烯酸丙二醇酯、(甲基)丙烯酸冰片酯等。
于本发明的具体例中,具有2个或2个以上乙烯性不饱和基的不饱和化合物为:乙二醇二(甲基)丙烯酸酯、二(甲基)丙烯酸二环戊烯酯、三甘醇二丙烯酸酯、四甘醇二(甲基)丙烯酸酯、三(2-羟乙基)异氰酸酯二(甲基)丙烯酸酯、三(2-羟乙基)异氰酸酯三(甲基)丙烯酸酯、己内酯改质的三(2-羟乙基)异氰酸酯三(甲基)丙烯酸酯、三(甲基)丙烯酸三羟甲基丙酯、环氧乙烷(以下简称EO)改质的三(甲基)丙烯酸三羟甲基丙酯、环氧丙烷(以下简称PO)改质的三(甲基)丙烯酸三羟甲基丙酯、三甘醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、季戊四醇四(甲基)丙烯酸酯、聚酯二(甲基)丙烯酸酯、聚乙二醇二(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇四(甲基)丙烯酸酯、己内酯改质的二季戊四醇六(甲基)丙烯酸酯、己内酯改质的二季戊四醇五(甲基)丙烯酸酯、四(甲基)丙烯酸二三羟甲基丙酯、EO改质的双酚A二(甲基)丙烯酸酯、PO改质的双酚A二(甲基)丙烯酸酯、EO改质的氢化双酚A二(甲基)丙烯酸酯、PO改质的氢化双酚A二(甲基)丙烯酸酯、PO改质的甘油三丙酸酯、EO改质的双酚F二(甲基)丙烯酸酯、酚醛聚缩水甘油醚(甲基)丙烯酸酯等。
较佳地,该含乙烯性不饱和基的化合物(B)为三丙烯酸三羟甲基丙酯、EO改质的三丙烯酸三羟甲基丙酯、PO改质的三丙烯酸三羟甲基丙酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯、二季戊四醇五丙烯酸酯、二季戊四醇四丙烯酸酯、己内酯改质的二季戊四醇六丙烯酸酯、四丙烯酸二三羟甲基丙酯、PO改质的甘油三丙酸酯,该等含乙烯性不饱和基的化合物(B)可单独一种或混合复数种使用。
根据本发明的含乙烯性不饱和基的化合物(B)使用量较佳地,基于碱可溶性树脂(A)使用量100重量份,该含乙烯性不饱和基的化合物(B)的使用量重量份为该碱可溶性树脂(A)重量份的0.1至5倍(10至500重量份),更佳地,该含乙烯性不饱和基的化合物(B)的使用量重量份为该碱可溶性树脂(A)重量份的0.3至4倍(30至400重量份),尤佳地,该含乙烯性不饱和基的化合物(B)的使用量重量份为该碱可溶性树脂(A)重量份的0.5至3倍(50至300重量份)。
根据本发明的光起始剂(C)为本发明所属技术领域中具通常知识者可选用者,例如可选自含有O-酰基肟(oxime)系光起始剂、三氮杂苯(triazine)类光起始剂、苯乙烷酮(acetophenone)类化合物、二咪唑类化合物(biimidazole),或二苯甲酮(benzophenone)类化合物。
较佳地,以碱可溶性树脂(A)使用量为100重量份计,该光起始剂(C)的使用量重量份为2至200重量份;更佳地,该光起始剂(C)的使用量重量份为5至180重量份;尤佳地,该光起始剂(C)的使用量重量份10至150重量份。
于本发明的具体例中,O-酰基肟系光起始剂为:1-[4-(苯基硫代)苯基]-庚烷-1,2-二酮2-(O-苯酰基肟)、1-[4-(苯基硫代)苯基]-辛烷-1,2-二酮2-(O-苯酰基肟、1-[4-(苯酰基)苯基]-庚烷-1,2-二酮2-(O-苯酰基肟)、1-[9-乙基-6-(2-甲基苯酰基)-9H-咔唑-3-取代基]-乙烷酮1-(O-乙酰基肟)、1-[9-乙基-6-(3-甲基苯酰基)-9H-咔唑-3-取代基]-乙烷酮1-(O-乙酰基肟)、1-[9-乙基-6-苯酰基-9H-咔唑-3-取代基]-乙烷酮1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-4-四氢呋喃基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-4-四氢吡喃基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-5-四氢呋喃基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-5-四氢吡喃基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-4-四氢呋喃基甲氧基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-4-四氢吡喃基甲氧基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-5-四氢呋喃基甲氧基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-5-四氢吡喃基甲氧基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二氧杂戊环基)苯酰基}-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二氧杂戊环基)甲氧基苯酰基}-9H-咔唑-3-取代基]-1-(O-乙酰基肟)等。
于本发明的具体例中,三氮杂苯(triazine)类光起始剂为:2,4-双(三氯甲基)-6-对-甲氧基苯乙烯基-s-三氮杂苯[2,4-Bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine]、2,4-双(三氯甲基)-6-(1-对-二甲基胺基苯基-1,3-丁二烯基)-s-三氮杂苯[2,4-Bis(trichloromethyl)-6-(1-p-dimethylaminophenyl-1,3-butadienyl)-s-triazine]、2-三氯甲基-4-胺基-6-对-甲氧基苯乙烯基-s-三氮杂苯[2-trichloromethyl-4-amino-6-(p-methoxy)styryl-s-triazine]等。
于本发明的具体例中,苯乙烷酮类(acetophenone)光起始剂为:对二甲胺苯乙烷酮、α,α′-二甲氧基氧化偶氮苯乙烷酮、2,2′-二甲基-2-苯基苯乙烷酮、对-甲氧基苯乙烷酮、2-甲基-1-(4-甲基硫代苯基)-2-吗啉代-1-丙酮、2-苄基-2-N,N-二甲胺-1-(4-吗啉代苯基)-1-丁酮。
于本发明的具体例中,二咪唑类(biimidazole)化合物光起始剂为:2,2′-双(邻-氯苯基)-4,4′,5,5′-四苯基二咪唑、2,2′-双(邻-氟苯基)-4,4′,5,5′-四苯基二咪唑、2,2′-双(邻-甲基苯基)-4,4′,5,5′-四苯基二咪唑、2,2′-双(邻-甲氧基苯基)-4,4′,5,5′-四苯基二咪唑、2,2′-双(邻-乙基苯基)-4,4′,5,5′-四苯基二咪唑、2,2′-双(对-甲氧基苯基)-4,4′,5,5′-四苯基二咪唑、2,2′-双(2,2′,4,4′-四甲氧基苯基)-4,4′,5,5′-四苯基二咪唑、2,2′-双(2-氯苯基)-4,4′,5,5′-四苯基二咪唑、2,2′-双(2,4-二氯苯基)-4,4′,5,5′-四苯基二咪唑等。
于本发明的具体例中,二苯甲酮类(benzophenone)化合物光起始剂为:噻吨酮、2,4-二乙基噻吨酮、噻吨酮-4-砜、二苯甲酮、4,4′-双(二甲胺)二苯甲酮、4,4′-双(二乙胺)二苯甲酮等。
较佳地,该光起始剂为1-[4-(苯基硫代)苯基]-辛烷-1,2-二酮2-(O-苯酰基肟)、1-[9-乙基-6-(2-甲基苯酰基)-9H-咔唑-3-取代基]-乙烷酮1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-(2-甲基-4-四氢呋喃甲氧基苯酰基)-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、乙烷酮-1-[9-乙基-6-{2-甲基-4-(2,2-二甲基-1,3-二氧杂戊环基)甲氧基苯酰基}-9H-咔唑-3-取代基]-1-(O-乙酰基肟)、2,4-双(三氯甲基)-6-对-甲氧基苯乙烯基-s-三氮杂苯[2,4-Bis(trichloromethyl)-6-(p-methoxy)styryl-s-triazine]、2-苄基-2-N,N-二甲胺-1-(4-吗福啉代苯基)-1-丁酮、2,2′-双(2,4-二氯苯基)-4,4′,5,5′-四苯基二咪唑、4,4′-双(二乙胺)二苯甲酮等。
较佳地,根据本发明的感光性树脂组成物,在不影响物性范围内,可依需要进一步添加前述光起始剂以外的起始剂,例如:α-二酮(α-diketone)类化合物、酮醇(acyloin)类化合物、酮醇醚(acyloin ether)类化合物、酰膦氧化物(acylphosphineoxide)类化合物、醌(quinone)类化合物、含卤素类化合物、过氧化物。
于本发明的具体例中,α-二酮类化合物的具体例如:苯偶酰(benzil)、乙酰基(acetyl)等;酮醇类化合物的具体例如:二苯乙醇酮(benzoin)等;酮醇醚类化合物的具体例如:二苯乙醇酮甲醚(benzoin methylether)、二苯乙醇酮乙醚(benzoin ethylether)、二苯乙醇酮异丙醚(benzoin isopropyl ether)等;酰膦氧化物类化合物的具体例如:2,4,6-三甲基苯酰二苯基膦氧化物(2,4,6-trimethyl-benzoyl diphenylphosphineoxide)、双-(2,6-二甲氧基苯酰)-2,4,4-三甲基苯基膦氧化物[bis-(2,6-dimethoxy-benzoyl)-2,4,4-trimethylbenzylphosphineoxide]等;醌类化合物的具体例如:蒽醌(anthraquinone)、1,4-萘醌(1,4-naphthoquinone)等;含卤素类化合物的具体例如:苯酰甲基氯(phenacylchloride)、三溴甲基苯砜(tribromomethyl phenylsulfone)、三(三氯甲基)-s-三氮杂苯[tris(trichloromethyl)-s-triazine]等;过氧化物的具体例如:二-第三丁基过氧化物(di-tertbutylperoxide)等,前述的起始剂依需要可单独一种或混合复数种使用。本发明的有机溶剂(D)为本发明所属技术领域中具通常知识者可选用者,该有机溶剂(D)的选择上,需可溶解碱可溶性树脂(A)、含乙烯性不饱和基的化合物(B)及光起始剂(C),且不与该等成份相互反应,并具有适当的挥发性者。
较佳地,根据本发明的有机溶剂(D)使用量基于碱可溶性树脂(A)使用量100重量份,有机溶剂(D)的的使用量为500至5,000重量份;更佳为800至4,500重量份;尤佳为1,000至4,000重量份。
于本发明的具体例中,上述有机溶剂(D)可选自前述丙烯系树脂(A-2)聚合过程中所使用的溶剂,在此不赘述,较佳为丙二醇甲醚醋酸酯或3-乙氧基丙酸乙酯。该等有机溶剂(D)可单独一种或混合复数种使用。
根据本发明的颜料(E)主体为蓝色颜料(E-1),本发明所属技术领域中具通常知识者可选用合宜的蓝色颜料(E-1),于本发明的具体例中,蓝色颜料(E-1)为C.I.颜料蓝15:1、15:2、15:3、15:4、15:6、21、22、60、64。
较佳地,根据本发明的颜料(E)进一步包含紫色颜料(E-2),本发明所属技术领域中具通常知识者可选用合宜的紫色颜料(E-2),于本发明的具体例中,紫色颜料(E-2)为C.I.颜料紫19、23、29、32、33、36、37、38、40、50。
根据本发明的颜料(E)及染料(F)的使用量,较佳地,基于颜料(E)及染料(F)的合计使用量100重量%,该颜料(E)的使用量为50至99.5重量%;更佳为55至99.0重量%;尤佳为60至98.0重量%。
本发明中,当未使用颜料(E)时,所制得的彩色滤光片会有后烤色差过大的问题发生。
本发明的染料(F)可搭配颜料(E)使用,本发明所属技术领域中具通常知识者可选择特定光谱的染料(F),于本发明的具体例中,该染料(F)为偶氮染料、偶氮金属错合物染料、蒽醌染料、靛蓝染料、硫靛染料、酞菁染料、二苯甲烷染料、三苯甲烷染料、呫吨染料、噻嗪染料、阳离子染料、菁染料、硝基染料、喹啉染料、萘醌染料、恶嗪染料等。
于本发明的较佳具体例中,根据本发明的染料(F)为C.I.溶剂红2、C.I.溶剂红24、C.I.溶剂红27、C.I.溶剂红49、C.I.溶剂红52、C.I.溶剂红57、C.I.溶剂红89、C.I.溶剂红111、C.I.溶剂红114、C.I.溶剂红119、C.I.溶剂红124、C.I.溶剂红135、C.I.溶剂红136、C.I.溶剂红137、C.I.溶剂红138、C.I.溶剂红139、C.I.溶剂红143、C.I.溶剂红144、C.I.溶剂红145、C.I.溶剂红146、C.I.溶剂红147、C.I.溶剂红148、C.I.溶剂红149、C.I.溶剂红150、C.I.溶剂红151、C.I.溶剂红152、C.I.溶剂红155、C.I.溶剂红156、C.I.溶剂红162、C.I.溶剂红168、C.I.溶剂红169、C.I.溶剂红170、C.I.溶剂红171、C.I.溶剂红172、C.I.溶剂红177、C.I.溶剂红178、C.I.溶剂红179、C.I.溶剂红181、C.I.溶剂红190、C.I.溶剂红191、C.I.溶剂红194、C.I.溶剂红199、C.I.溶剂红200、C.I.溶剂红201、C.I.溶剂红299、C.I.直接红2、C.I.直接红81、C.I.酸性红1、C.I.酸性红14、C.I.酸性红27、C.I.酸性红52、C.I.酸性红87、C.I.酸性红88、C.I.酸性红289、C.I.碱性红1、C.I.媒介红3、C.I.冰染红21、C.I.还原红1、C.I.还原红2、C.I.还原红15、C.I.还原红23、C.I.还原红41、C.I.还原红47、C.I.分散红1、C.I.分散红11、C.I.分散红15、C.I.分散红22、C.I.分散红60、C.I.分散红92、C.I.分散红146、C.I.分散红191、C.I.分散红283、C.I.分散红288、C.I.活性红12。上述个各染料可依所需的性质单独或混合使用。
本发明中,当未使用染料(F)时,所制得的彩色滤光片会有对比不佳且显影后所形成的图案边缘平滑性的问题发生。
较佳地,本发明的颜料(E)及染料(F)使用量基于颜料(E)及染料(F)的合计使用量100重量%,该染料(F)的使用量介于0.5至50重量%;更佳介于1.0至45重量%;尤佳介于2.0至40重量%。
基于颜料(E)及染料(F)的合计使用量100重量份,当该染料(F)的使用量介于0.5至50重量份时,则所制得的彩色滤光片会有后烤色差较低、对比不佳且显影后所形成的图案边缘平滑性的问题较不易发生。
本发明的颜料(E)及染料(F)总使用量,较佳地,基于碱可溶性树脂(A)使用量100重量份,颜料(E)及染料(F)的总使用量为100至800重量份;更佳为120至700重量份;尤佳为150至600重量份。
较佳地,根据本发明的感光性树脂组成物可依所需的物性及化性进一步包含添加剂,此添加剂的选择为本发明所属技术领域中具通常知识者可决定者。于本发明的具体例中,该添加剂为填充剂、碱可溶性树脂(A)以外的高分子化合物、密着促进剂、抗氧化剂、紫外线吸收剂、防凝集剂。
于本发明较佳的具体例中,该填充剂为:玻璃、铝;碱可溶性树脂(A)以外的高分子化合物为聚乙烯醇、聚乙二醇单烷基醚、聚氟丙烯酸烷酯;密着促进剂为乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、乙烯基三(2-甲氧乙氧基)硅烷、N-(2-氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、N-(2-氨基乙基)-3-氨基丙基三甲氧基硅烷、3-氨基丙基三乙氧基硅烷、3-环氧丙醇丙基三甲氧基硅烷、3-环氧丙醇丙基甲基二甲氧基硅烷、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-硫醇基丙基三甲氧基硅烷;紫外线吸收剂为2,2-硫代双(4-甲基-6-第三丁基苯酚)、2,6-二-第三丁基苯酚等的抗氧化剂;2-(3-第三丁基-5-甲基-2-羟基苯基)-5-氯苯基迭氮、烷氧基苯酮;及防凝集剂为聚丙烯酸钠。
根据本发明的添加剂使用量为本发明所属技术领域中具通常知识者可决定者,较佳地,基于碱可溶性树脂(A)100重量份,该添加剂的使用量为0至10重量份;更佳为0至6重量份;尤佳为0至3重量份。
本发明亦提供一种彩色滤光片的制造方法,其是使用前述的感光性树脂组成物形成一像素层。
本发明又提供一种彩色滤光片,其是由前述的方法所制得。
将根据本发明的感光性树脂组成物应用于滤光片的制造方法是为本发明所属技术领域中具通常知识者可实施者,于本发明的具体例中,先将前述碱可溶性树脂(A)、含有乙烯性不饱和基的化合物(B)、光起始剂(C)、颜料(E)及染料(F)均匀分散于有机溶剂(D)中,形成一液态的蓝色感光性树脂组成物后,再藉由回转涂布、流延涂布、喷墨涂布(ink-jet)或辊式涂布等方式,将前述蓝色感光性组成物涂布在基板上。涂布后,先以减压干燥的方式,去除大部分的溶剂,再以预烤(prebake)方式将溶剂去除而形成一预烤涂膜。其中,减压干燥及预烤的条件,依各成份的种类,配合比率而异,通常,减压干燥乃在0至200mmHg的压力下进行1秒钟至60秒钟,而预烤乃在70至110℃温度下进行1分钟至15分钟。预烤后,该预烤涂膜于所指定的光罩(mask)下曝光,于23±2℃温度下浸渍于显影液15秒至5分钟进行显影,不要的部分除去而形成图案,之后以水洗净,再以压缩空气或压缩氮气将图案风干,风干后的具有光硬化涂膜层的基板,利用热板或烘箱等加热装置,在温度100至280℃下加热1至15分钟,将涂膜中的挥发性成分去除,并且使涂膜中未反应的乙烯性不饱和双键进行热硬化反应,即可制得蓝色滤光片片段,接着分别将绿色感光树脂组成物及红色感光树脂组成物以相同的制程方式再在预定的像素部上分别形成绿色滤光片片段,及红色滤光片片段即可得到一具有红、绿、蓝三色滤光片片段的彩色滤光片。
于本发明的较佳实施例中,前述制程曝光使用的光线为g线、h线、i线等的紫外线为佳,而紫外线装置为(超)高压水银灯及金属卤素灯;前述基板为:用于液晶显示装置等的无碱玻璃、钠钙玻璃、硬质玻璃(派勒斯玻璃)、石英玻璃及于此等玻璃上附着透明导电膜者,或用于固体摄影装置等的光电变换装置基板(如:硅基板)。此等基板一般是先形成隔离各像素着色层的黑色矩阵(black matrix)。
于本发明的较佳实施例中,显影液为: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、氨水、乙胺、二乙胺、二甲基乙醇胺、氢氧化四甲铵、氢氧化四乙铵、胆碱、吡咯、呱啶、1,8-二氮杂二环-(5,4,0)-7-十一烯等碱性化合物所构成的碱性水溶液,其浓度一般为0.001至10重量%;较佳为0.005至5重量%;更佳为0.01至1重量%。
本发明再提供一种液晶显示装置,其特征在于包含前述的彩色滤光片。
根据本发明的液晶显示装置通常包含于一彩色液晶显示装置,本发明的一具体例参看图1,此彩色液晶显示装置包含:一液晶显示装置10,及一背光单元20。
该液晶显示装置10包括一第一基板13、一与该第一基板13成一间隔设置的第二基板14、一与该第一基板13连接的彩色滤光片11、一夹置在该第一、二基板13、14之间的液晶12、分别形成在该彩色滤光片11及第二基板14表面的配向层15,及分别形成在第一、二基板13、14远离该液晶12的表面的偏光板16,其中,该第一基板13即为彩色滤光片(color filter,CF)侧基板,该第二基板14即为业界一般通称的薄膜电晶体(TFT)侧基板。
该背光单元20与该液晶显示装置10的第二基板14上的偏光板16连接,两者组合而制得彩色液晶显示装置。
根据本发明的液晶显示装置可应用TN(Twisted Nematic;扭曲向列)、STN(Super Twisted Nematic;超扭曲向列)、IPS(In-Plane switching;面内切换)、VA(Vertical Alignment;垂直配向)、OCB(Optically Compensated Birefringence;光学补偿弯曲)及强诱电性液晶等液晶。液晶显示装置的制作为本技术领域所周知且非为本发明的重点,因此不再多加赘述。
兹以下列实例予以详细说明本发明,唯并不意谓本发明仅局限于此等实例所揭示的内容。
聚硅氧烷聚合物(A-1)的合成例
将500毫升的三口烧瓶中加入如表1所示的硅烷化合物、溶剂及触媒,并在室温下搅拌超过30分钟。然后将烧瓶沉浸在40°C油浴中搅拌30分钟,再加热至115°C油浴超过30分钟。当加热开始1小时后,内部温度达到100°C,并继续加热搅拌120分钟(内部温度为100至110°C)。在反应过程中,共蒸馏出甲醇及水作为副产品。将二丙酮醇加入所制得的聚硅氧烷聚合物(A-1)的溶液中,而得到重量比43wt%的聚硅氧烷聚合物(A-1)溶液。进一步测定所制得的聚硅氧烷聚合物(A-1)的平均分子量(Mw)记载于表1。
表1:聚硅氧烷聚合物(A-1)的合成例的组成比例
丙烯酸系树脂(A-2)的合成例
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,并导入氮气且依表2所示用量加入进料组成物以及溶剂。其中,单体混合物的入料方式为连续添加。
四颈锥瓶的内容物被搅拌时,油浴的温度被提升至100℃,然后依表2所示将聚合用起始剂2,2′-偶氮双-2-甲基丁腈(以下简称AMBN)4重量份溶于有机溶剂EEP中,并以五等份的重在一小时间隔添加在四颈锥瓶中。
聚合过程的反应温度维持100℃,聚合时间6小时。聚合完成后,将聚合产物自四颈锥瓶中取出,将溶剂脱挥,以得丙烯酸系树脂(A-2)。
表2:丙烯酸系树脂(A-2)的合成例的组成比例
感光性树脂组成物实施例
表3所示的各成分及使用量,以摇动式搅拌器,加以溶解混合,即可调制而得彩色滤光片用蓝色感光性树脂组成物。
评价方式
将感光性树脂组成物以旋转涂布的方式,涂布在100mm×100mm的玻璃基板上,先进行减压干燥,压力100mmHg、时间30秒钟,然后再进行预烤,温度80℃、时间2分钟,可形成一膜厚2.5μm的预烤涂膜。再以紫外光(曝光机Canon PLA-501F)100mJ/cm2的光量照射该预烤涂膜后,该预烤涂膜再浸渍于23℃的显影液1分钟,以纯水洗净。
其次,再以235℃后烤30分钟,即可在玻璃基板上形成一膜厚2.0μm的感光性树脂层。
(a)对比
由所得的感光性树脂层,以图2及图3所示的方法所测得的辉度计算对比;其中,将所得的感光性树脂层1置于两枚偏光板2、3之间,从光源4所照射出来的光依序透过偏光板2、感光性树脂层1、偏光板3,而最后透过偏光板3的辉度(cd/cm2)则以辉度计5(日本Topcon公司制,型号BM-5A)进行测量。
如图2所示,当偏光板3的偏光方向与偏光板2的偏光方向互相平行时,所测得的辉度为A(cd/cm2);另外,如图3所示,当偏光板3的偏光方向与偏光板2的偏光方向互相垂直时,所测得的辉度为B(cd/cm2);则对比度可藉由辉度A与辉度B的比值(辉度A/辉度B)而得,其评价标准如下。
○:(辉度A/辉度B)≧3500
△:3000≦(辉度A/辉度B)<3500
×:(辉度A/辉度B)<3000
(b)图案边缘平滑性
所得的感光性树脂层,以扫描式电子显微镜(SEM)观察,根据边缘侧面(edge profile)的形状以评价其平滑性
○:如图4所示,感光性树脂层171的边缘角(相对于基板14的侧壁角)为10°<θ1≦60°。
△:如图5所示,感光性树脂层172的边缘角(相对于基板14的侧壁角)为60°<θ2≦90°。
╳:如图6所示,感光性树脂层173的边缘角(相对于基板14的侧壁角)为θ3>90°。
(c)后烤色差
将感光性树脂组成物以旋转涂布的方式,涂布在100mm×100mm的玻璃基板上,先进行减压干燥,压力100mmHg、时间30秒钟,然后再进行预烤,温度80℃、时间2分钟,可形成一膜厚2.5μm的预烤涂膜。再以紫外光(曝光机Canon PLA-501F)100mJ/cm2的光量照射该预烤涂膜后,该预烤涂膜再浸渍于23℃的显影液1分钟,以纯水洗净,以色度计(大冢电子公司制,型号MCPD)测定其色度(L*,a*,b*)。
其次,再以235℃后烤30分钟,即可在玻璃基板上形成一膜厚2.0μm的感光性树脂层。再次测定其色度变化,并根据其色度变化ΔEab*以如下的基准评价:
ΔEab*={(ΔL)2+(Δa)2+(Δb)2}1/2
○:色度变化ΔEab*<3
△:3≦色度变化ΔEab*<6
×:色度变化ΔEab*≧6
(d)密着性
根据于JIS.K5400(1900)8.5密着性试验中,8.5.2的基盘目法测定,将后烤(postbake)后的镀膜以小刀割成100个基盘目,再以胶带沾粘后撕下,计算被撕下基盘目的数目,根据下列的基准评价。
○:0个以下。
△:0至10个。
×:10个以上。
表3:感光性树脂组成物实施例与比较例的组成比例及评价结果
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。本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。本发明的权利范围应如权利要求所列。
Claims (11)
1.一种感光性树脂组成物,其特征在于,所述的感光性树脂组成物包含:
碱可溶性树脂;
含乙烯性不饱和基的化合物;
光起始剂;
有机溶剂;
颜料;及
染料;
其中,所述碱可溶性树脂包含聚硅氧烷聚合物以及丙烯酸系树脂,所述聚硅氧烷聚合物是由结构式Si(Ra)z(ORb)4-z所表示的硅烷化合物经加水分解及缩合反应而得;
其中:
Ra表示至少一个为含有羧酸酐取代基的烷基,其他Ra是独立选自由氢原子、碳数1至10的烷基、碳数2至10的烯基及碳数6至15的芳基所组成的群;其中,所述碳数2至10的烯基为乙烯基、3-烯丙氧丙基或3-甲基烯丙氧丙基;所述碳数6至15的芳基为苯基、甲苯基、p-羟基苯基、1-(p-羟基苯基)乙基、2-(p-羟基苯基)乙基、4-羟基-5-(p-羟基苯基羰氧基)戊基或萘基;
Rb是独立选自由氢原子、碳数1至6的烷基、乙酰基及苯基所组成的群;z表示1至3的整数。
2.根据权利要求1所述的感光性树脂组成物,其特征在于,基于碱可溶性树脂使用量100重量份,所述聚硅氧烷聚合物的使用量介于5至70重量份。
3.根据权利要求1所述的感光性树脂组成物,其特征在于,基于碱可溶性树脂使用量100重量份,所述丙烯酸系树脂的使用量为30至95重量份。
4.根据权利要求1所述的感光性树脂组成物,其特征在于,基于碱可溶性树脂使用量100重量份,所述含乙烯性不饱和基的化合物的使用量介于10至500重量份;所述光起始剂的使用量介于2至200重量份;所述有机溶剂的使用量介于500至5,000重量份且所述颜料与染料的总使用量介于100至800重量份。
5.根据权利要求1所述的感光性树脂组成物,其特征在于,所述颜料含有一蓝色颜料。
6.根据权利要求1所述的感光性树脂组成物,其特征在于,所述颜料有一紫色颜料。
7.根据权利要求1所述的感光性树脂组成物,其特征在于,所述染料包含一红色染料。
8.根据权利要求1所述的感光性树脂组成物,其特征在于,基于颜料及染料的合计使用量100重量%,所述颜料的使用量介于50至99.5重量%,染料的使用量介于0.5至50重量%。
9.一种彩色滤光片的制造方法,其特征在于,使用根据权利要求1至8中任一权利要求所述的感光性树脂组成物形成一像素层。
10.一种彩色滤光片,其特征在于,由根据权利要求9的彩色滤光片的制造方法所制得。
11.一种液晶显示装置,其特征在于,所述的液晶显示装置包含根据权利要求10的彩色滤光片。
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CN101806999A (zh) * | 2009-02-13 | 2010-08-18 | 住友化学株式会社 | 着色感光性树脂组合物和滤色器 |
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CN103135353A (zh) | 2013-06-05 |
US20130142966A1 (en) | 2013-06-06 |
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