CN104880856B - 一种彩色光阻剂及其应用、彩膜基板、液晶显示器 - Google Patents
一种彩色光阻剂及其应用、彩膜基板、液晶显示器 Download PDFInfo
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- CN104880856B CN104880856B CN201510354655.3A CN201510354655A CN104880856B CN 104880856 B CN104880856 B CN 104880856B CN 201510354655 A CN201510354655 A CN 201510354655A CN 104880856 B CN104880856 B CN 104880856B
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- UFHILTCGAOPTOV-UHFFFAOYSA-N tetrakis(ethenyl)silane Chemical compound C=C[Si](C=C)(C=C)C=C UFHILTCGAOPTOV-UHFFFAOYSA-N 0.000 description 1
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Classifications
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Abstract
本发明公开了一种彩色光阻剂及其应用、彩膜基板、液晶显示器,属于光敏材料领域。该彩色光阻剂包括光引发剂和量子点,该光引发剂为不含富电子基团的第一光引发剂和/或含有富电子基团的第二光引发剂;第二光引发剂包括共轭结构,且所述共轭结构由所述富电子基团与所述富电子基团的相邻基团构成。本发明实施例提供的彩色光阻剂中包含了正常发光的量子点,利用该彩色光阻剂制备得到的彩膜基板将具有高色域,能够有效改善液晶显示器的画质。
Description
技术领域
本发明涉及光敏材料领域,特别涉及一种彩色光阻剂及其应用、彩膜基板、液晶显示器。
背景技术
量子点(quantumdots,QDs)是一种由半导体材料制成的,稳定直径在2‐20nm的纳米粒子,一般呈球形或类球形。量子点是是纳米尺度上原子和分子的集合体,其既可由一种半导体材料组成(例如由IIB、VIA族元素CdS、CdSe、CdTe、ZnSe等,或者由IIIA、VA族元素InP、InAs等组成),也可以由两种或两种以上的半导体材料组成。作为一种新颖的半导体纳米材料,量子点具有激发光谱宽且连续分布、发射光谱窄而对称、颜色可调、光化学稳定性高、荧光寿命长等优点,广泛用于荧光标记、液晶显示器中背光模组的膜材等领域。
彩膜基板(Color Filter,CF)是液晶显示器中液晶显示面板的重要构成部分,其一般包括透明基板以及设置在透明基板上的黑矩阵层和彩色滤光层。其中彩色滤光层主要由彩色光阻剂制备得到,彩色光阻剂的主要成分包括:碱溶性树脂、感光树脂、颜料、光引发剂、溶剂等。然而,研究发现,利用感光树脂和颜料制备得到的彩色滤光层色域较窄,易导致彩膜基板出现溢色现象。基于量子点作为液晶显示器中背光组件的膜材,具有提高色域,改善液晶显示器画质的特点,发明人提出将量子点作为彩膜基板中彩色滤光层的感光材料,以提高色域。
在实现本发明的过程中,发明人发现现有技术至少存在以下问题:
当量子点和光引发剂混合时,会发生荧光淬灭现象。
发明内容
本发明实施例所要解决的技术问题在于,提供了一种包含量子点且量子点能够正常发光的彩色光阻剂及其应用、彩膜基板、液晶显示器。具体技术方案如下:
第一方面,本发明实施例提供了一种彩色光阻剂,包括光引发剂和量子点,所述光引发剂为不含富电子基团的第一光引发剂和/或含有富电子基团的第二光引发剂;
所述第二光引发剂包括共轭结构,且所述共轭结构由所述富电子基团与所述富电子基团的相邻基团构成。
作为优选,所述第二光引发剂中,富电子基团的个数为1个或者2个。
具体地,作为优选,所述第二光引发剂为全共轭型分子结构。
具体地,作为优选,所述第二光引发剂中,所述富电子基团与所述富电子基团的相邻基团共平面。
具体地,作为优选,所述第二光引发剂中,所有的原子均共平面。
具体地,作为优选,所述第二光引发剂为1‐[4‐(苯硫基)苯基]‐1,2‐辛烷二酮2‐(O‐苯甲酰肟)、1‐[9‐乙基‐6‐(2‐甲基苯甲酰基)‐9H‐咔唑‐3‐基]乙酮1‐(O‐乙酰肟)或过氧化二苯甲酰。
具体地,所述第一光引发剂选自二苯甲酮,4‐苯基二苯甲酮,4‐甲基二苯甲酮中的至少一种。
具体地,作为优选,所述彩色光阻剂包括以下重量百分含量的组分:所述量子点1‐20%、所述光引发剂1‐3%、交联剂1‐15%、碱溶性树脂5‐40%、余量为溶剂。
具体地,作为优选,所述交联剂选自乙烯系不饱和单体和/或丙烯系不饱和单体。
具体地,作为优选,所述碱溶性树脂为(甲基)丙烯酸共聚树脂和/或酯化的苯乙烯/马来酸酐共聚树脂。
具体地,作为优选,所述溶剂为丙二醇甲醚醋酸酯。
进一步地,作为优选,所述彩色光阻剂还包括1‐3%的助剂,所述助剂选自稳定剂、流平剂、消泡剂、防缩孔剂、附着力促进剂以及表面爽滑剂中的至少一种。
第二方面,本发明实施例提供了上述任意一种彩色光阻剂在制备液晶显示器用彩膜基板中的应用。
第三方面,本发明实施例提供了一种彩膜基板,该彩膜基板利用上述的任意一种彩色光阻剂制备得到。
第四方面,本发明实施例提供了一种液晶显示器,该液晶显示器包括上述的彩膜基板。
本发明实施例提供的技术方案带来的有益效果是:
本发明实施例提供的彩色光阻剂,包括光引发剂和量子点,当光引发剂不含富电子基团时,将不会有富电子转移到量子点的空穴轨道上,保证量子点不会发光淬灭。当光引发剂含有富电子基团时,通过使富电子基团与其相邻基团构成共轭结构,使富电子在其本身结构上发生电子云离域,提高其稳定性,而不会转移到量子点的空穴轨道上,进而保证量子点不会荧光淬灭,使其正常发光。如此以来,所得到的彩色光阻剂中包含了正常发光的量子点,利用该彩色光阻剂制备得到的彩膜基板将具有高色域,能够有效改善液晶显示器的画质。
附图说明
为了更清楚地说明本发明实施例中的技术方案,下面将对实施例描述中所需要使用的附图作简单地介绍,显而易见地,下面描述中的附图仅仅是本发明的一些实施例,对于本领域普通技术人员来讲,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1是本发明实施例5提供的自量子点与光引发剂混合形成彩色光阻剂开始直至随着对该彩色光阻剂曝光处理时间的延长,实施例1、3和4以及对比例提供的彩色光阻剂中量子点的荧光强度变化示意图。
具体实施方式
除非另有定义,本发明实施例所用的所有技术术语均具有与本领域技术人员通常理解的相同的含义。为使本发明的目的、技术方案和优点更加清楚,下面将结合附图对本发明实施方式作进一步地详细描述。
发明人研究发现,在制备含有量子点的彩色光阻剂时,如若所使用的光引发剂含有富电子时,该富足的电子将转移到量子点的空穴轨道上,即富电子将被量子点的表面陷阱捕获,使得正常的光致电子e‐和光致空穴h+的复合受阻,从而造成量子点发光淬灭。基于此,提供一种不含富电子的光引发剂或者其中富电子尽可能少且该尽可能少的富电子十分稳定的光引发剂十分必要。
第一方面,本发明实施例提供了一种彩色光阻剂,包括光引发剂和量子点,所述光引发剂为不含富电子基团的第一光引发剂和/或含有富电子基团的第二光引发剂;其中,第二光引发剂包括共轭结构,且该共轭结构由富电子基团与富电子基团的相邻基团构成。
本发明实施例提供了一种彩色光阻剂,包括光引发剂和量子点,当光引发剂不含富电子基团时,将不会有富电子转移到量子点的空穴轨道上,保证量子点不会发光淬灭。当光引发剂含有富电子基团时,通过使富电子基团与其相邻基团构成共轭结构,使富电子在其本身结构上发生电子云离域,提高其稳定性,而不会转移到量子点的空穴轨道上,进而保证量子点不会发光淬灭,使其正常发光。如此以来,所得到的彩色光阻剂中包含了正常发光的量子点,利用该彩色光阻剂制备得到的彩膜基板将具有高色域,能够有效改善液晶显示器画质。
其中,第一光引发剂可以为本领域常见的不含有富电子或富电子基团的光引发剂。具体地,该第一光引发剂可以为二苯甲酮,4‐苯基二苯甲酮,4‐甲基二苯甲酮等。
作为优选,第二光引发剂中,富电子基团的个数为1个或者2个。本发明实施例通过将第二光引发剂中富电子基团的个数进行如上限定,以保证第二光引发剂中含有尽可能少的富电子,进而降低彩色光阻剂中量子点发光淬灭的几率。
作为优选,该第二光引发剂为全共轭型分子结构。本发明实施例通过将第二光引发剂限定为全共轭型分子结构,能够保证富电子在其本身结构上发生更好的电子云离域,富电子将更加稳定,而不会转移到量子点的空穴轨道上,从而保证量子点不会发光淬灭,使量子点正常发光。
进一步地,该第二光引发剂中,富电子基团与富电子基团的相邻基团共平面,优选第二光引发剂中所有的原子均共平面。本发明实施例通过对第二光引发剂进行如上限定,能够使富电子的离域性更好,其将不会转移到量子点的空穴轨道上,保证量子点不会发光淬灭,使量子点正常发光。
可以理解的是,第二光引发剂可以为本领域常见的具有如上限定结构的光引发剂。基于低成本及耐用度考虑,该第二光引发剂为1‐[4‐(苯硫基)苯基]‐1,2‐辛烷二酮2‐(O‐苯甲酰肟)、1‐[9‐乙基‐6‐(2‐甲基苯甲酰基)‐9H‐咔唑‐3‐基]乙酮1‐(O‐乙酰肟)或过氧化二苯甲酰,优选为1‐[9‐乙基‐6‐(2‐甲基苯甲酰基)‐9H‐咔唑‐3‐基]乙酮1‐(O‐乙酰肟)或过氧化二苯甲酰,更优选为1‐[9‐乙基‐6‐(2‐甲基苯甲酰基)‐9H‐咔唑‐3‐基]乙酮1‐(O‐乙酰肟)。其中,这三种第二光引发剂的具体信息如表1所示:
表1
具体地,光引发剂1‐[9‐乙基‐6‐(2‐甲基苯甲酰基)‐9H‐咔唑‐3‐基]乙酮1‐(O‐乙酰肟)具有如表1所示的分子结构,其虽然也含有N富电子基团,但是由于N富电子基团与其相邻的基团构成了共轭结构,N的富电子在其本身结构上将发生电子云离域,其不会向量子点发生电荷转移,从而使量子点正常发光。
而光引发剂1‐[4‐(苯硫基)苯基]‐1,2‐辛烷二酮2‐(O‐苯甲酰肟)具有如表1所示的分子结构,其中也有N富电子基团,且N富电子基团与其相邻的基团构成了共轭结构,但是由于N=旁边的长的烷基链使得分子不是共平面结构,导致N富电子的离域不如光引发剂1‐[9‐乙基‐6‐(2‐甲基苯甲酰基)‐9H‐咔唑‐3‐基]乙酮1‐(O‐乙酰肟)中N富电子的离域性能好,会有部分电子转移,导致部分量子点发光淬灭。当然,在特定情况下,发生部分荧光淬灭的量子点也可继续用于制备彩色光阻剂。
具体地,本发明实施例提供的彩色光阻剂中,量子点选自红光量子点、蓝光量子点、绿光量子点中的至少一种。举例来说,量子点可以为Si量子点、Ge量子点、InAs量子点、GaSb量子点、GaN量子点、ZnTe量子点、CdSe量子点、CdTe量子点、ZnSe量子点、CdS量子点、ZnO量子点、SiGe量子点或者它们的组合或者它们的核壳结构。一般情况下,本发明实施例所用的量子点的粒径约为2‐20nm,优选10‐20nm。可以理解的是,通过调节量子点的尺寸可以实现量子点的荧光峰位可调。
基于上述,本发明实施例提供了一种具有优选组成及配比的彩色光阻剂,该彩色光阻剂包括以下重量百分含量的组分:上述的量子点1‐20%、上述的光引发剂1‐3%、交联剂1‐15%、碱溶性树脂5‐40%、余量为溶剂。通过将上述各组分混合均匀即可得到本发明实施例期望的彩色光阻剂。
本发明实施例提供的彩色光阻剂,通过上述各组分之间的协同复配作用,在紫外光条件下,光引发剂吸收光能后能够产生自由基,引发交联剂发生交联固化反应,形成致密且稳定的彩膜。而量子点在均匀分布在该彩膜中形成发光活性点,并在光照作用下发射荧光。可见,通过在彩色光阻剂中添加量子点,能够有效提高所形成的高聚物薄膜的色域,并同时具有激发光谱宽且连续分布、发射光谱窄而对称、颜色可调、光化学稳定性高、荧光寿命长等优点。
具体地,本发明实施例中所用的交联剂选自乙烯系不饱和单体和/或丙烯系不饱和单体。作为优选,该乙烯系不饱和单体和/或丙烯系不饱和单体的官能度大于等于1。
本发明实施例所用的交联剂在紫外光条件下,可以被自由基引发聚合,发生光交联固化反应形成高聚物,进而形成致密的彩膜。为了提高该交联剂的交联性能,该乙烯系不饱和单体、丙烯系不饱和单体均具有如下结构单元:
其中,R为氢或甲基;
R1为苯基、羟基苯基、甲基苯基、乙基苯基、萘基或腈基;
R2、R3均为具有1‐8个碳原子的烷基、具有1‐8个碳原子的羟烷基、二烷基胺烷基、苯基、苄基或月桂酯基,其中,所述二烷基胺烷基中的烷基包括1‐8个碳原子数;
R4为具有3‐8个碳原子的烷基。
举例来说,本发明实施例中所用的交联剂可以选自以下物质中的至少一种:(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸丙酯、(甲基)丙烯酸丁酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸月桂酯、甲基丙烯酸缩水甘油酯、单(甲基)丙烯酸聚乙二醇酯等单官能(甲基)丙烯酸酯类;1,3‐丁二醇二(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、甘油二(甲基)丙烯酸酯、三丙二醇二丙烯酸酯,己二醇丙烯酸二酯、聚乙二醇200二(甲基)丙烯酸酯、聚乙二醇400二(甲基)丙烯酸酯、聚乙二醇600二(甲基)丙烯酸酯等二官能(甲基)丙烯酸酯类;甘油三(甲基)丙烯酸酯、季戊四醇单羟基三(甲基)丙烯酸酯、三羟甲基丙烷三(甲基)丙烯酸酯、乙氧化三羟甲基丙烷三(甲基)丙烯酸酯等三官能(甲基)丙烯酸酯类;季戊四醇四丙烯酸酯等四官能(甲基)丙烯酸酯类;二季戊四醇单羟基五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯等高官能(甲基)丙烯酸酯类;苯乙烯、羟苯乙烯、α‐甲基苯乙烯、乙烯基甲苯、乙烯基萘、乙烯基二甲苯、二乙烯基苯、二乙烯基甲苯、二乙烯基萘、二乙烯基吡啶、二乙烯基硅烷、三乙烯基硅烷、二甲基二乙烯基硅烷、二乙烯基甲基硅烷、甲基三乙烯基硅烷、二乙烯基苯基硅烷、三乙烯基苯基硅烷、三乙烯基硅烷、四乙烯基硅烷、聚(甲基乙烯基硅氧烷)、聚(乙烯基氢硅氧烷)等,但不限以上种类。
具体地,该碱溶性树脂为(甲基)丙烯酸共聚树脂和/或酯化的苯乙烯/马来酸酐共聚树脂。
为了能在后续显影过程中使用碱性显影液将未固化的彩膜清洗下来,达到显影的目的。本发明实施例使用具有羧酸基团的碱溶性树脂,从而使该羧酸基团在显影过程中与碱液反应,生成水溶性的盐,使碱溶性树脂溶解于碱性显影液(例如KOH、NaHCO3、Na2CO3、TMAH(四甲基氢氧化铵)等)中。基于此,本发明实施例使用(甲基)丙烯酸共聚树脂和/或酯化的苯乙烯/马来酸酐共聚树脂作为碱溶性树脂。更具体地,该(甲基)丙烯酸共聚树脂可以由乙烯系不饱和单体和/或丙烯系不饱和单体与(甲基)丙烯酸进行共聚合反应得到。其中,(甲基)丙烯酸共聚树脂的重均分子量为10000‐200000,优选50000‐150000;由于碱溶性树脂含有适当的酸值,可以保证在显影过程中有足够的羧酸基团和碱液反应,使未紫外固化的彩膜能被显影液清洗下来,达到显影的目的。基于此,本发明实施例将(甲基)丙烯酸共聚树脂的酸值控制在50‐250,优选100‐200。
本领域技术人员可以理解的是,本发明实施例所使用的溶剂为本领域现有技术,通过使用溶剂将其他各成分溶解并混合均匀,使得所制备的彩膜达到理想的粘度,利于喷涂、辊涂或丝印到透明基板上。举例来说,该溶剂可选自如下物质中的至少一种:乙二醇单甲醚醋酸酯、乙二醇单乙醚醋酸酯、乙二醇单丁醚醋酸酯、二乙二醇单甲醚醋酸酯、乙二醇单乙醚醋酸酯、乙二醇单丁醚醋酸酯、丙二醇单甲醚醋酸酯、丙二醇单乙醚醋酸酯或丙二醇单丁醚醋酸酯、醋酸乙酯、醋酸丁酯等酯类溶剂;乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、二乙二醇单甲醚、乙二醇单乙醚、乙二醇单丁醚、丙二醇单甲醚、二丙二醇单甲醚等醚类溶剂;正丙醇、异丙醇、正丁醇、异丁醇等醇类溶剂;丁酮、环己酮、异佛尔酮等酮类溶剂;甲苯、二甲苯等芳香溶剂;石脑油、氧化石脑油、溶剂石脑油等石油系溶剂。优选丙二醇单甲醚醋酸酯、乙二醇单乙醚醋酸酯、丁酮、二丙二醇单甲醚,但不限以上化合物。进一步优选为丙二醇甲醚醋酸酯。
进一步地,为了提高所制备的彩膜的综合性能,本发明实施例中,彩色光阻剂还包括1‐3%的助剂,其中该助剂选自稳定剂、流平剂、消泡剂、防缩孔剂、附着力促进剂以及表面爽滑剂中的至少一种,从而使所制备的彩膜更加致密、光滑、附着力更高。
第二方面,本发明实施例提供了上述的彩色光阻剂在制备液晶显示器用彩膜基板中的应用。
通过使用本发明实施例提供的彩色光阻剂制备液晶显示器用彩膜基板,所得到的彩膜基板色域更高,利于提高液晶显示器的画质。可以理解的是,使用彩色光阻剂制备彩膜基板,更具体为制备彩色光滤层对于本领域技术人员来说是一种常用的现有技术。
举例来说,可以采用如下方法利用彩色光阻剂制备彩色光滤层:
步骤101、使用旋涂法对本发明实施例提供的彩色光阻剂进行成膜处理,形成厚度为2‐10um的液膜。举例来说,该液膜的厚度可以为2‐5μm、4‐7μm、6‐9μm、5.5μm、6.5μm、7.5μm、8.5μm、9.5μm等。
步骤102、采用紫外光对步骤101形成的液膜进行曝光处理,得到固化的彩膜。其中,所采用的紫外光的波长可以为365nm、曝光能量可以为50‐500MJ/cm2,优选100MJ/cm2。
步骤103、利用碱性显影液对步骤102得到的固化彩膜进行显影处理,以去除其中的碱溶性树脂,得到图案化的彩膜。其中,碱性显影液优选氢氧化钾溶液,显影时间可以为30‐100s,优选50s。
步骤104、对步骤103得到的图案化的彩膜进行水洗,然后进行烘干处理。其中烘干处理过程中,烘干温度可以为100‐250℃,优选150℃;烘干时间可以为20‐60分钟,优选30分钟。
第三方面,本发明实施例提供了一种彩膜基板,该彩膜基板采用本发明实施例提供的上述彩色光阻剂制备得到。
本发明实施例提供的彩膜基板,由于使用了含有量子点的彩色光阻剂,具有高色域的特点,其用于液晶显示器中更利于提高液晶显示器的画质。
可以理解的是,本发明实施例提供的彩膜基板
第四方面,本发明实施例提供了一种液晶显示器,该液晶显示器包括本发明实施例提供的上述彩膜基板。可以理解的是,使用彩膜基板制备液晶显示器是本领域常用的现有技术,本发明实施例在此不对其作具体地限定。
以下将通过具体实施例进一步地描述本发明。
在以下具体实施例中,所涉及的操作未注明条件者,均按照常规条件或者制造商建议的条件进行。所用原料未注明生产厂商及规格者均为可以通过市购获得的常规产品。
实施例1
本实施例提供了一种彩色光阻剂,包括以下质量百分含量的组分:量子点5%、光引发剂1%、交联剂4%、碱溶性树脂20%、余量为溶剂。
其中,量子点为球形CdTe量子点,平均粒径为10nm;光引发剂为1‐[4‐(苯硫基)苯基]‐1,2‐辛烷二酮2‐(O‐苯甲酰肟);交联剂为(甲基)丙烯酸甲酯;碱溶性树脂为丙烯酸共聚树脂(该丙烯酸共聚树脂由质量分数分别为20%的丙烯酸以及80%的甲基丙烯酸甲酯共聚合形成,重均分子量为100,000(Mw),分子量分布指数为1.93,酸值为180mgKOH/g);溶剂为乙二醇单乙醚醋酸酯。
实施例2
本实施例提供了一种彩色光阻剂,包括以下质量百分含量的组分:量子点10%、光引发剂2%、交联剂5%、碱溶性树脂30%、余量为溶剂。
其中,量子点为球形CdS量子点,平均粒径为10nm;光引发剂为二苯甲酮;交联剂为(甲基)丙烯酸乙酯;该碱溶性树脂为10重量份的丙烯酸共聚树脂(该丙烯酸共聚树脂由质量分数分别为10%的丙烯酸、50%的甲基丙烯酸甲酯以及40%的丙烯酸辛酯共聚合形成,重均分子量为50,000(Mw),分子量分布指数为2.10,酸值为100mgKOH/g)以及30重量份的仲丁醇酯化的苯乙烯马来酸酐的共聚物(重均分子量为60,000,酸值为150mgKOH/g);溶剂为丙二醇甲醚醋酸酯。
实施例3
本实施例提供了一种彩色光阻剂,包括以下质量百分含量的组分:量子点20%、光引发剂3%、交联剂5%、碱溶性树脂40%、余量为溶剂。
其中,量子点为球形SiGe量子点,平均粒径为15nm;光引发剂为过氧化二苯甲酰;交联剂为(甲基)丙烯酸丙酯;该碱溶性树脂为仲丁醇酯化的苯乙烯马来酸酐的共聚树脂(重均分子量为30,000(Mw),分子量分布指数为2.03,酸值为170mgKOH/g);溶剂为二丙二醇单甲醚。
实施例4
本实施例提供了一种彩色光阻剂,包括以下质量百分含量的组分:量子点15%、光引发剂2.5%、交联剂4.5%、碱溶性树脂25%、余量为溶剂。
其中,量子点为球形CdSe量子点,平均粒径为8nm;光引发剂为1‐[9‐乙基‐6‐(2‐甲基苯甲酰基)‐9H‐咔唑‐3‐基]乙酮1‐(O‐乙酰肟);交联剂为1,3‐丁二醇二(甲基)丙烯酸酯;该碱溶性树脂为碱溶性树脂为30重量份的丙烯酸共聚树脂(该丙烯酸共聚树脂由20%的丙烯酸以及80%的甲基丙烯酸甲酯共聚合形成,重均分子量为100,000(Mw),分子量分布指数为1.93,酸值为180mgKOH/g)以及20重量份的仲丁醇酯化的苯乙烯马来酸酐的共聚物(重均分子量为24,000,酸值为150);溶剂为丙二醇甲醚醋酸酯。
对比例
本对比实施例提供了一种彩色光阻剂,包括以下质量百分含量的组分:量子点15%、光引发剂2.5%、交联剂4.5%、碱溶性树脂25%、余量为溶剂。
其中,量子点为球形CdSe量子点,平均粒径为8nm;光引发剂为2‐苄基‐2‐二甲基氨基‐1‐(4‐吗啉苯基)丁酮;交联剂为1,3‐丁二醇二(甲基)丙烯酸酯;该碱溶性树脂为碱溶性树脂为30重量份的丙烯酸共聚树脂(该丙烯酸共聚树脂由20%的丙烯酸以及80%的甲基丙烯酸甲酯共聚合形成,重均分子量为100,000(Mw),分子量分布指数为1.93,酸值为180mgKOH/g)以及20重量份的仲丁醇酯化的苯乙烯马来酸酐的共聚物(重均分子量为24,000,酸值为150);溶剂为丙二醇甲醚醋酸酯。
其中,2‐苄基‐2‐二甲基氨基‐1‐(4‐吗啉苯基)丁酮的商品名为369,CAS号为119313‐12‐1,分子结构如下所示:
实施例5
本实施例分别采用实施例1‐4以及对比例提供的彩色光阻剂制备彩膜基板中的彩色光滤层,方法如下:
步骤a、使用旋涂法对上述各实施例提供的彩色光阻剂进行成膜处理,形成厚度为5um的液膜。
步骤b、采用紫外光对步骤a形成的液膜进行曝光处理,得到固化的彩膜。其中,所采用的紫外光的波长可以为365nm、曝光能量为100MJ/cm2。
步骤c、利用碱性显影液对步骤b得到的固化彩膜进行显影处理,以去除其中的碱溶性树脂,得到图案化的彩膜。其中,碱性显影液为氢氧化钾溶液,显影时间为50s。
步骤d、对步骤c得到的图案化的彩膜进行水洗,然后进行烘干处理。其中烘干处理过程中,烘干温度为150℃;烘干时间为30分钟。
对实施例1‐4以及对比例提供的彩色光阻剂中量子点的荧光强度进行了观察,具体地,在配制各彩色光阻剂的过程中,当量子点与光引发剂混合时观察量子点的荧光强度;然后,在对各彩色光阻剂曝光后3秒观察其中所含量子点的荧光强度,量子点荧光强度的变化结果分别如表2和图1所示:
表2
由表2可知,当实施例1‐4提供的彩色光阻剂中量子点与光引发剂混合后,量子点的荧光强度基本没有变化,且在彩色光阻剂曝光3秒后,仅仅实施例1中的量子点略有变暗,即实施例1中的量子点出现了部分发光淬灭,不过仍然可用于制备彩膜基板。而实施例2‐4中的量子点在彩色光阻剂曝光3秒后,量子点的强度没有发生变化,即这些量子点没有出现发光淬灭,能有效用于制备高色域的彩膜基板。而对比例提供的彩色光阻剂中量子点在与光引发剂混合后,量子点的荧光强度略有变暗,并在彩色光阻剂曝光3秒后,其中的量子点出现了显著的发光淬灭现象,将无法用于制备彩膜基板。
同样地如图1所示,自量子点与光引发剂混合形成彩色光阻剂开始,然后随着对该彩色光阻剂进行曝光处理时间的延长,实施例1、3、4中的量子点的荧光强度在初始下降约20%左右后均变得稳定,其中,当光引发剂为1‐[9‐乙基‐6‐(2‐甲基苯甲酰基)‐9H‐咔唑‐3‐基]乙酮1‐(O‐乙酰肟)时,量子点的荧光强度下降水平最低,且量子点的发光性能最优;而当光引发剂为2‐苄基‐2‐二甲基氨基‐1‐(4‐吗啉苯基)丁酮时,量子点的荧光强度下降水平最高,最后直至完全淬灭。
综上所述,本发明实施例1‐4提供的光引发剂均不会使量子点发生较严重的发光淬灭现象,当将其与量子点混合后制备得到的彩色光阻剂均能够用于制备高色域的彩膜基板。
实施例6
本实施例分别利用实施例1‐4以及对比例提供的彩色光阻剂制备液晶显示器,所制备的液晶显示器均包括背光源和液晶显示面板。其中,液晶显示面板包括彩膜基板,而彩膜基板包括透明基板以及设置在透明基板上的黑矩阵层和彩色滤光层。具体地,该彩色滤光层分别由实施例1‐4以及对比例提供的彩色光阻剂制备得到。然后对上述各液晶显示器的色域性能进行了测试,测试结果如表3所示:
表3
由表3可知,利用本发明实施例提供的彩色光阻剂制备得到的液晶显示器具有高色域,该高色域能有效改善液晶显示器的画质,利于提高用户的使用舒适度。
以上所述仅为本发明的较佳实施例,并不用以限制本发明的保护范围,凡在本发明的精神和原则之内,所作的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (13)
1.一种彩色光阻剂,包括光引发剂和量子点,所述光引发剂为不含富电子基团的第一光引发剂和/或含有富电子基团的第二光引发剂;
所述第二光引发剂包括共轭结构,且所述共轭结构由所述富电子基团与所述富电子基团的相邻基团构成;
所述第一光引发剂选自4‐苯基二苯甲酮或4‐甲基二苯甲酮;
所述彩色光阻剂包括以下重量百分含量的组分:所述量子点1‐20%、所述光引发剂1‐3%、交联剂1‐15%、碱溶性树脂5‐40%、余量为溶剂。
2.根据权利要求1所述的彩色光阻剂,其特征在于,所述第二光引发剂中,富电子基团的个数为1个或者2个。
3.根据权利要求2所述的彩色光阻剂,其特征在于,所述第二光引发剂为全共轭型分子结构。
4.根据权利要求1‐3任一项所述的彩色光阻剂,其特征在于,所述第二光引发剂中,所述富电子基团与所述富电子基团的相邻基团共平面。
5.根据权利要求4所述的彩色光阻剂,其特征在于,所述第二光引发剂中,所有的原子均共平面。
6.根据权利要求1所述的彩色光阻剂,其特征在于,所述第二光引发剂为1‐[4‐(苯硫基)苯基]‐1,2‐辛烷二酮2‐(O‐苯甲酰肟)、1‐[9‐乙基‐6‐(2‐甲基苯甲酰基)‐9H‐咔唑‐3‐基]乙酮1‐(O‐乙酰肟)或过氧化二苯甲酰。
7.根据权利要求1所述的彩色光阻剂,其特征在于,所述交联剂选自乙烯系不饱和单体和/或丙烯系不饱和单体。
8.根据权利要求7所述的彩色光阻剂,其特征在于,所述碱溶性树脂为(甲基)丙烯酸共聚树脂和/或酯化的苯乙烯/马来酸酐共聚树脂。
9.根据权利要求8所述的彩色光阻剂,其特征在于,所述溶剂为丙二醇甲醚醋酸酯。
10.根据权利要求7‐9任一项所述的彩色光阻剂,其特征在于,所述彩色光阻剂还包括1‐3%的助剂,所述助剂选自稳定剂、流平剂、消泡剂、防缩孔剂、附着力促进剂以及表面爽滑剂中的至少一种。
11.权利要求1‐10任一项所述的彩色光阻剂在制备液晶显示器用彩膜基板中的应用。
12.一种彩膜基板,利用权利要求1‐10任一项所述的彩色光阻剂制备得到。
13.一种液晶显示器,包括权利要求12所述的彩膜基板。
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US10983432B2 (en) * | 2015-08-24 | 2021-04-20 | Samsung Electronics Co., Ltd. | Photosensitive compositions, preparation methods thereof, quantum dot polymer composite prepared therefrom |
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CN106569389B (zh) * | 2015-10-12 | 2021-07-16 | 东友精细化工有限公司 | 自发光感光树脂组合物、滤色器和包括滤色器的显示设备 |
CN105353555B (zh) * | 2015-12-08 | 2018-08-14 | 深圳市华星光电技术有限公司 | 量子点彩膜基板的制作方法 |
KR102333141B1 (ko) * | 2016-02-22 | 2021-11-30 | 삼성디스플레이 주식회사 | 감광성 수지 조성물 및 이를 사용하여 제조된 색변환층을 포함하는 표시 장치 |
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CN106773276B (zh) * | 2017-03-28 | 2019-08-09 | 青岛海信电器股份有限公司 | 量子点彩色滤光片及制备方法、液晶面板、液晶显示设备 |
CN109021702A (zh) * | 2018-07-13 | 2018-12-18 | 苏州星烁纳米科技有限公司 | 量子点墨水以及量子点膜 |
CN109233804B (zh) * | 2018-09-05 | 2021-07-20 | 纳晶科技股份有限公司 | 量子点粉末及其制备方法、发光器件、量子点组合物、量子点膜及其制备方法 |
CN109298599B (zh) * | 2018-09-25 | 2022-09-16 | 苏州星烁纳米科技有限公司 | 光刻胶组合物、彩膜基板和显示装置 |
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