CN103265829A - 用于低折射层的含有含氟化合物的涂覆组合物、抗反射膜、偏光片与图像显示装置 - Google Patents

用于低折射层的含有含氟化合物的涂覆组合物、抗反射膜、偏光片与图像显示装置 Download PDF

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CN103265829A
CN103265829A CN2012104360613A CN201210436061A CN103265829A CN 103265829 A CN103265829 A CN 103265829A CN 2012104360613 A CN2012104360613 A CN 2012104360613A CN 201210436061 A CN201210436061 A CN 201210436061A CN 103265829 A CN103265829 A CN 103265829A
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孙晟豪
金润凤
张元硕
赵容均
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Abstract

本发明提供用于低折射层的含有下面化学式1的含氟化合物的涂覆组合物、使用该组合物的抗反射膜,以及含有该抗反射膜的偏光片与图像显示装置,其中下述化学式1的含氟化合物具有低的折光率1.28-1.40,从而能够容易地调节抗反射膜的折光率,并且有效地用作抗反射膜的涂层材料,该反射膜具有优异的机械性能例如耐久性等。[化学式1]

Description

用于低折射层的含有含氟化合物的涂覆组合物、抗反射膜、偏光片与图像显示装置
相关申请的交叉引用 
本申请根据美国法典第35章第119条(35U.S.C.§119),要求于2011年11月4日在韩国知识产权局递交的韩国专利申请No.10-2011-0114392的优先权,该申请的内容以参阅的方式全文并入本文中。 
技术领域
本申请涉及用于低折射层的含有下面化学式1的含氟化合物的涂覆组合物、使用该组合物的抗反射膜,以及含有该抗反射膜的偏光片与图像显示装置,其中下述化学式1的含氟化合物具有低的折光率1.28-1.40,从而能够容易地调节抗反射膜的折光率,并且有效地用作抗反射膜的涂层材料,该反射膜具有优异的机械性能例如耐久性等; 
[化学式1] 
Figure BDA00002357736600011
背景技术
现代人已接触到各种显示器例如显像管,诸如监视器的阴极射线管(CRT)、电视的彩色显像管(CPT),薄膜晶体管液晶显示器(TFT-LCD)偏光片、等离子显示板(PDP)滤光器、RPTS滤光器、移动电话的液晶、手表、照片和相框。在这些显示器暴露在光线例如自然光的情况下,反射光可能造成眼睛疲劳或头痛,眼睛可能无法清楚地聚焦于在显示屏上显示的图像,使得对比度可能会变差。为了解决这些问题,人们已经开展了形成抗反射膜的技术研究,采用形成在基底上的折射率低 于基底的折射率的膜的方法以减少反射。为了得到这样的抗反射功能,该抗反射膜具有如下结构,其中在玻璃、塑料膜上涂覆含有在其中应用了硬涂覆溶液的硬涂覆层、含有在其中应用了折光率为1.6或更高的涂覆溶液的高折射层,以及含有在其中应用了低折光率1.3-1.5的涂覆溶液的低折射层。近来,为了减少复杂的工艺,抗反射膜的结构已被改变为双层结构,其中低折射层被直接应用于硬涂覆层。除了低折光率外,该低折射层应具有诸如高可见光透光度、耐久性、抗污染、机械强度等物理性能。此外,同时,该低折射层应容易通过大规模涂覆方法,诸如卷筒涂覆法、凹版涂覆法、坡流涂覆法、喷涂法、丝网印刷法等进行涂覆,并且容易通过连续的固化方法例如紫外线固化法进行固化。 
作为用于抗反射的具有低折光率的基于氟的材料,日本公开专利公报No.1998-182745公开了通过聚合含有多功能的(multi-functional)含氟的(甲基)丙烯酸酯的单体组合物制得的具有低折光率的基于氟的材料。然而,对于含有氟烷基的丙烯酸酯,当氟的含量下降时,折光率可能下降,当氟的含量增高时,透明度可能变差。 
如上所述,相关现有技术中已经检验了作为用于低折射层的抗反射材料的多种基于氟的涂覆溶液组合物。然而,现有技术中仍需要具有低的折光率足以获得抗反射效果和使用单涂层来抵抗刮痕的机械强度的材料,以及使用该材料的涂覆方法。 
发明概述 
本发明的一个实施方案涉及提供一种用于低折射层的含有含氟化合物的涂覆组合物,该组合物作为一种具有低折光率的材料,足以获得抗反射的效果以及强的机械强度以使用单涂层来对抗刮痕,本发明的实施方案还涉及使用该组合物的抗反射膜以及含有该抗反射膜的偏光片和图像显示装置。 
在一个通常的方面,本发明提供用于低折射层的含有下面化学式 1的含氟化合物的涂覆组合物、使用该组合物的抗反射膜,以及含有该抗反射膜的偏光片与图像显示装置,其中下述化学式1的含氟化合物具有低的折光率1.28-1.40,从而能够容易地调节抗反射膜的折光率,并且有效地用作抗反射膜的涂层材料,该反射膜具有优异的机械性能例如耐久性等。 
[化学式1] 
Figure BDA00002357736600031
在化学式1中, 
R1-R4各自独立地为氢、(C1-C20)烷基、或(C6-C20)芳基,且R1和R2不同时为氢; 
m和n各自独立地为2-10的整数,A、B、D和E各自独立地为氢、氟或(C1-C4)烷基,前提是氟的含量占A、B、D和E的总原子含量的50%或更多,并且 
R1-R4的烷基和芳基可进一步被氟取代。 
化学式1的含氟化合物的折光率为1.28-1.40,优选低的折光率1.28-1.35,从而能够容易地调节抗反射膜的折光率,并且有效地用作抗反射膜的涂层材料,该反射膜具有优异的机械性能例如耐久性等。 
化学式1的含氟化合物的实例包括但不限于下面的化合物: 
Figure BDA00002357736600041
化学式1的含氟化合物通过使化学式2的氟化二烷基硅烷化合物、化学式3-1的酰氯化合物以及化学式3-2的酰氯化合物在脱氯化氢试剂存在下相互反应而制备。 
[化学式1] 
Figure BDA00002357736600042
[化学式2] 
Figure BDA00002357736600043
[化学式3-1] 
Figure BDA00002357736600044
[化学式3-2] 
Figure BDA00002357736600045
在这些化学式中,R1、R2、m、n、A、B、D和E各自具有与化学式1中相同的定义。 
在该方法中用作无水溶剂的有乙醚、四氢呋喃、二氯甲烷等,并且基于化学式2的氟化二烷基硅烷化合物,脱氯化氢试剂的用量为2.0-2.5当量。此外,用作脱氯化氢试剂的有吡啶、三乙胺等。反应温度可根据使用的溶剂而改变,但通常为0-25℃。反应时间可根据反应温度和所用溶剂而改变,但通常可为30分钟至6小时,优选2小时或更短。 
化学式2的氟化二烷基硅烷化合物通过两种方法制备:一种方法是通过使用镁作为催化剂在-78℃至25℃的温度下,使下面化学式4的硅烷化合物、化学式5-1的氟化溴代醇(bromoalcohol)化合物以及化学式5-2的氟化溴代醇(bromoalcohol)化合物与格氏试剂(Grignard reagent)反应;另一种方法是在(C1-C10)烷基锂存在下,在-78℃至25℃的温度下使化学式4的硅烷化合物、化学式5-1的氟化溴代醇化合物以及化学式5-2的氟化溴代醇化合物与阴离子试剂反应。 
[化学式2] 
Figure BDA00002357736600051
[化学式4] 
[化学式5-1] 
Figure BDA00002357736600053
[化学式5-2] 
在这些化学式中,R1、R2、m、n、A、B、D和E各自具有与化学式1中相同的定义。 
在该方法中,使用单独的溶剂例如乙醚、四氢呋喃、己烷、庚烷等以及至少两种溶剂互相混合的混合溶剂作为无水溶剂。基于化学式4的硅烷化合物,镁通常的用量为2.0-2.1当量。作为烷基锂有机金属试剂的有正丁基锂、仲丁基锂、叔丁基锂等。通常,基于化学式4的硅烷化合物,烷基锂有机金属试剂的用量为2.0-2.1当量。反应温度可根据所用溶剂而改变,但通常为-78℃至25℃。优选地,氯代锂取代反应在-78℃下进行,化学式5-1和5-2的氟化溴代醇化合物在-10℃至25℃下反应。反应时间可根据反应温度和所用溶剂而改变,但通常为30分钟至6小时,优选2小时或更短。 
化学式1的含氟化合物的含量为用于低折射层的涂覆组合物的总固体含量的1-50wt%(重量百分比)。在含量低于1wt%的情况中,难以获得抗反射效果,在含量高于50wt%的情况中,难以获得机械性能。因此,优选保持该含量范围。 
按照本发明示例性的实施方案,用于低折射层的涂覆组合物可包含化学式1的含氟化合物、具有丙烯酸不饱和基团的化合物、低折光率的颗粒和溶剂。 
更具体地,所述用于低折射层的涂覆组合物包含化学式1的含氟化合物、具有丙烯酸不饱和基团的化合物、低折光率的颗粒和溶剂,具有3-8wt%的固体含量,其中所述固体可含有1-50wt%的化学式1的含氟化合物,5-40wt%的具有丙烯酸不饱和基团的化合物以及1-60wt%的低折光率的颗粒。 
在用于低折射层的涂覆组合物的固体含量低于3wt%的情况下,固化过程可能消耗长时间且经济效益可能降低,在固体含量高于8 wt%的情况下,涂覆溶液的粘度增加,这样可能难以进行薄膜涂覆并且涂覆膜的平面化程度可能变差。具有丙烯酸不饱和基团的化合物用于提高固化层的固化程度。本文中,在该具有丙烯酸不饱和基团的化合物含量低于用于低折射层的涂覆组合物的固体含量的5wt%的情况下,固化该低折射层表面时可能存在问题,在含量高于40wt%的情况下,该低折射层的折光率升高,这样抗反射效果可能变差。具有丙烯酸不饱和基团的化合物可为(甲基)丙烯酸酯,在本发明中,(甲基)丙烯酸酯是指丙烯酸酯或甲基丙烯酸酯。(甲基)丙烯酸酯的具体实例包括乙基(甲基)丙烯酸酯、乙基己基(甲基)丙烯酸酯、三羟甲基三(甲基)丙烯酸酯、己二醇(甲基)丙烯酸酯、三丙二醇二(甲基)丙烯酸酯、二甘醇二(甲基)丙烯酸酯、季戊四醇三(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯等。 
作为低折射的颗粒,可使用LiF、MgF、3NaF、AlF、Na3AlF6或具有真空区的中空二氧化硅。使用低折射的颗粒来降低折光率以提高抗反射特性和抗刮痕,所述颗粒可具有1nm-100nm的颗粒尺寸。在颗粒尺寸小于1nm的情况下,凝结(coagulation)现象可能增多,在颗粒尺寸大于100nm的情况下,由于白化现象,透明度可能降低。该低折射颗粒的含量可占用于低折射层的涂覆组合物的总固体含量的1-60wt%。当该低折射的颗粒的含量小于1wt%时,通过提高夹层粘附强度来提高抗刮痕的效果及抗反射的效果可能减弱,当该含量高于60wt%时,可见光透光率可能与所用颗粒的量成比例的略微降低。因此,可优选维持该含量范围。 
可不受限制地使用任何有机溶剂,只要该溶剂适于溶解所述固体成分。例如,可使用醇类、醋酸酯类、酮类或芳香溶剂。更具体地,可使用甲醇、乙醇、异丙醇、丁醇、2-甲氧基乙醇、2-乙氧基乙醇、2-丁氧基乙醇、2-异丙基乙醇、乙酸甲酯、乙酸乙酯、乙酸丁酯、甲 乙酮、甲基异丁基酮、环己烷、环己酮、甲苯、二甲苯或苯等,以及可将其中至少两种混合应用。可加入溶剂使得用于低折射层的涂覆组合物的固体含量为3-8wt%。在固体含量小于3wt%的情况下,固化过程可能需要长时间,这样经济效益可能降低,在固体含量大于8wt%的情况下,涂覆溶液的粘度增加,这样薄膜涂覆可能变得困难并且涂覆膜的平面化可能变差。 
本发明的用于低折射层的涂覆组合物还可包括光引发剂,其中该光引发剂是紫外线可降解化合物,例如α-氨基苯乙酮、1-羟基环己基苯基酮、苄基二甲基缩酮、羟基二甲基苯乙酮、安息香、安息香甲醚、安息香乙醚、安息香异丙醚、安息香丁醚等,而且基于100重量份的化学式1的含氟化合物,该光引发剂的含量可为1-20重量份。在光引发剂的含量低于1重量份的情况下,该较低涂覆组合物可能不会固化,在含量高于20重量份的情况下,由于涂覆组合物的过度固化,在低折射层中可能产生裂缝,这样抗裂痕与抗磨损性可能变差。 
此外,本发明的用于低折射层的涂覆组合物还可包括需要的添加剂,只要该添加剂是现有技术中常规使用的,任何添加剂都可应用而不受限制。例如,可使用光刺激剂、抗氧化剂、UV吸收剂、UV稳定剂、热稳定剂、热聚合抑制剂、均化剂、表面活性剂、润滑剂等。此外,添加剂的含量可在使涂覆组合物的性能不会变差的范围内。 
在另一个通常的方面,本发明提供由用于低折射层的含氟化合物的涂覆组合物制备的抗反射膜。该抗反射膜通过已知方法,采用用于低折射层的含氟化合物的涂覆组合物制备。 
在所述抗反射膜中,依次形成于透明基底上的硬涂覆层和低折射层可通过应用适于硬涂覆层的组合物以及本发明的适于较低折射层的涂覆组合物以合适的方法来形成,所述方法例如模具涂覆方法、气刀涂覆方法、逆转辊涂布方法、喷射涂布方法、叶片涂覆方法、铸造方法、凹版涂布和旋转涂布方法等。 
该抗反射膜可包括使用适于低折射层的涂覆组合物形成的低折射层,其具有这样的结构,在该结构中,低折射层独立地涂覆于透明基底上,或者硬涂覆层和低折射层顺序地涂覆在透明基底上。作为透明基底,只要该膜是透明的塑料膜,可使用任何膜,可优选使用聚对苯二甲酸乙二醇酯膜或三乙酸纤维素膜。该透明基底膜可具有8-300μm的厚度,优选40-100μm。形成于透明基底上的低折射层的折光率在25℃可为1.28-1.40。当低折射层的折光率低于该范围时,抗反射效果可能降低,当低折射层的折光率高于该范围时,预定的颜色可能被反射光增强。除了优异的抗反射特性外,上述制备的抗反射膜具有优异的抗刮痕和粘附特性。 
在另一个通常的方面,提供含有该抗反射膜的偏光片。该偏光片不作具体限制,可使用多种偏光片。例如,作为偏光片,可以是通过使亲水的聚合物膜(例如聚乙烯醇膜、乙烯-醋酸乙烯酯共聚物部分皂化膜(saponificated film)等)吸收碘或双色材料(例如双色染料)经单轴拉伸获得的膜,以及多烯定向膜例如聚乙烯醇的脱水材料或聚氯乙烯的脱氯化氢材料。在这些偏光片中,可优选由聚乙烯醇膜和诸如碘等的双色材料构成的偏光片。偏光片的厚度不作具体限制,通常可为约5-80μm。 
在另一个通常的方面,本发明提供包括该抗反射膜或在显示器上表面形成的偏光片的图像显示装置。例如,将本发明形成的具有抗反射膜的偏光片嵌入显示装置中,这样可制得多种具有优异可视性的显示装置。而且,本发明的抗反射膜可附于显示装置的窗口上。本发明的抗反射膜可优选应用于反射型液晶显示器(LCD)、穿透式LCD、半穿透式LCD或具有不同驱动方案的LCD,这些方案诸如扭曲向列型(TN)模式、超扭曲向列型(STN)模式、分支编码本(OCB)模式、混合对准向列(HAN)模式、垂直对齐(VA)模式、内启动开关(IPS)模式等。此外,本发明的抗反射膜可用于不同的显示装置,例如等离子显示器、 场发射显示器、有机电致发光(EL)显示器、无机EL显示器、电子纸等。 
具体实施方式
在下面的实施例以及对比例中,将详细描述本发明的效果。提供下面的实施例用于说明的目的,而不用来限制本发明的范围。 
[制备例1]含氟化合物的制备 
本发明的不同含氟化合物通过下面的第一和第二反应过程制备。 
<第一反应过程> 
在5L反应瓶中注入四氢呋喃(THF),冷却至-78℃。然后将下表1中描述的5mol硅烷化合物(反应剂I)、5mol镁屑以及5mol氟化溴代醇化合物(反应剂II)依次放入反应瓶中,搅拌10min,然后将该混合物搅拌1.5小时,同时使温度缓慢升高至室温。搅拌完成后,通过将500g氢氯酸(HCl)溶解于1L水中然后将该溶解物质加入到反应瓶中终止反应,然后静置20min。当生成物分散入水中,THF层变得透明,在THF层完全蒸发后,通过柱层析分离和纯化产物即氟化二羟基硅烷化合物。下表1显示了每个制得的化合物的收率(56.6-66.7%)和1H NMR。 
[表1] 
Figure BDA00002357736600101
<第二反应过程> 
在3L反应瓶中,注入二氯甲烷(MC),然后在室温下加入下表2中描述的3mol酰氯化合物(反应物III)以及3mol在第一反应过程中获得的物质,然后加入11mol三乙胺与上述混合物反应1h。当反应完成时,加水然后将生成物静置20min。当该生成物分散入水中,MC层变得透明,在MC层完全蒸发后,通过柱层析分离和纯化产物即氟化二烷基二丙烯酸硅烷化合物。收率为70.3-90.5%,各制得化合物的收率以及 1H NMR如下表2所示。各化合物的折光率通过使用589nm的D-光钨丝灯作为光源,经折射计(型号名称:2T,日本ATAGO ABBE)检测。各化合物的折光率为1.28-1.40,如表3所示。 
[表2] 
Figure BDA00002357736600121
[表3] 
Figure BDA00002357736600131
[实施例1]用于低折射层的涂覆溶液的制备 
将3g的含氟化合物(6)以及2.5g二季戊四醇六丙烯酸酯(NK化学公司,A-DPH)与224g的甲基异丁基酮(MIBK)混合,完全溶解,然后与6g中空的二氧化硅(JGCCC)混合。随后加入0.3g的α-氨基苯乙酮(BASF,Irgacure 907)作为光引发剂,由此制备用于低折射层的涂覆溶液。 
Figure BDA00002357736600132
[实施例2]用于低折射层的涂覆溶液的制备 
除了使用含氟化合物(4)以外,通过与实施例1相同的方法制备用于低折射层的涂覆溶液。 
[实施例3]用于低折射层的涂覆溶液的制备 
除了使用含氟化合物(7)以外,通过与实施例1相同的方法制备用于低折射层的涂覆溶液。 
Figure BDA00002357736600141
[实施例4]用于低折射层的涂覆溶液的制备 
除了使用含氟化合物(2)以外,通过与实施例1相同的方法制备用于低折射层的涂覆溶液。 
Figure BDA00002357736600142
[实施例5]抗反射膜的制作 
在将硬涂覆层和低折射层层压在厚度为80μm的透明三乙酸纤维素(TAC)膜表面的过程中,使用线锭将实施例1制备的用于低折射层的涂覆溶液以及硬涂覆溶液(Kyoeisha,HX-610UV)分别调整至120nm和5μm。在层压每一层后,通过独立的干燥和固化过程制作抗反射膜。干燥在90℃下进行1分钟,UV固化使用高压汞灯(120W/cm)进行10秒钟。 
[实施例6]抗反射膜的制作 
除了使用实施例2中制备的涂覆溶液以外,通过与实施例5相同的方法制备抗反射膜。 
[实施例7]抗反射膜的制作 
除了使用实施例3中制备的涂覆溶液以外,通过与实施例5相同的方法制备抗反射膜。 
[实施例8]抗反射膜的制作 
除了使用实施例4中制备的涂覆溶液以外,通过与实施例5相同的方法制备抗反射膜。 
[实验例1] 
测量制得的抗反射膜的平均反射比、透光度以及雾度(haze),结果如表4所示。 
1)反射比估计:将涂覆膜的背面变黑后,使用固体Spec 3700分光光度计(Shimadzu公司)测量反射比以估计最小反射比的值。 
2)透光度和雾度估计:按照JIS K7105标准,使用HM-150(Murakami公司)测量涂覆层的透光度和雾度。 
[表4] 
如表4所示,令人欣喜的是使用实施例1-4的用于低折射层的涂覆溶液制备的抗反射膜的平均反射比为1.1-1.3%,具有优异的抗反射效果。此外,氟含量越高,雾度可能越大。然而,使用实施例1-4的用于低折射层的涂覆溶液制备的抗反射膜的显示了低的雾度0.3-0.4%。除了氟化合物的种类外,实施例1-4的用于低折射层的涂覆溶液具有相同组成。结果,令人欣喜的是,作为必要成分包含于用于低折射层的涂覆组合物内的具有特殊结构的含氟化合物,其通过使用例如中空的二氧化硅等低折射材料来辅助抗反射效果。 
如上所述,本发明的用于低折射层的涂覆组合物包括含氟化合物,该化合物具有优异的光学性能例如低至1.28-1.40的折光率以及优异的机械性能,能够容易地调节抗反射膜的折光率。此外,使用用于 低折光率层的涂覆组合物制作的抗反射膜可具有优异的光学和机械性能,例如低的反射比和优异的可见光透光率。 

Claims (13)

1.一种用于低折射层的涂覆组合物,其含有化学式1表示的含氟化合物
[化学式1]
Figure FDA00002357736500011
在化学式1中,
R1-R4各自独立地为氢、(C1-C20)烷基或(C6-C20)芳基,且R1和R2不同时为氢;
m和n各自独立地为2-10的整数;
A、B、D和E各自独立地为氢、氟或(C1-C4)烷基,前提是氟含量占A、B、D和E的总原子含量的50%或更多;以及
R1-R4的烷基和芳基可进一步被氟取代。
2.根据权利要求1所述的用于低折射层的涂覆组合物,其中化学式1的含氟化合物的含量占所述用于低折射层的涂覆组合物的总固体含量的1-50wt%。
3.根据权利要求1所述的用于低折射层的涂覆组合物,其中所述组合物含有化学式1的含氟化合物、具有丙烯酸不饱和基团的化合物、低折光率的颗粒、光引发剂和溶剂。
4.根据权利要求3所述的用于低折射层的涂覆组合物,其中所述具有丙烯酸不饱和基团的化合物的含量占所述用于低折射层的涂覆组合物的总固体含量的5-40wt%。
5.根据权利要求1所述的用于低折射层的涂覆组合物,其中所述化学式1的含氟化合物的折光率为1.28-1.40。
6.根据权利要求1所述的用于低折射层的涂覆组合物,其中所述化学式1的含氟化合物选自具有如下结构的化合物:
Figure FDA00002357736500021
7.根据权利要求1所述的用于低折射层的涂覆组合物,其中所述组合物的折光率为1.28-1.4。
8.一种抗反射膜,其含有由权利要求1-7中任一项所述的用于低折射层的涂覆组合物制成的低折射层。
9.根据权利要求8所述的抗反射膜,其中所述抗反射膜含有独立涂覆于透明基底上的低折射层。
10.根据权利要求8所述的抗反射膜,其中所述抗反射膜含有依次涂覆于透明基底上的硬涂覆层以及低折射层。
11.一种偏光片,其含有权利要求8所述的抗反射膜。
12.一种图像显示装置,其含有在其上表面形成的权利要求8所述的抗反射膜。
13.一种图像显示装置,其含有在其上表面形成的权利要求11所述的偏光片。
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