CN104903976B - 保护膜 - Google Patents

保护膜 Download PDF

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CN104903976B
CN104903976B CN201480004098.6A CN201480004098A CN104903976B CN 104903976 B CN104903976 B CN 104903976B CN 201480004098 A CN201480004098 A CN 201480004098A CN 104903976 B CN104903976 B CN 104903976B
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diaphragm
weight
diaphragm described
parts
polysiloxane
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CN104903976A (zh
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李熙济
金贤哲
朴容秀
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LG Corp
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LG Chemical Co Ltd
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Abstract

本申请涉及一种保护膜,包括所述保护膜的导电层压体,以及包括所述保护膜的偏光板。本申请提供了一种保护膜,所述保护膜能够由于其剥离强度被控制为低的而易于移除,具有优异的聚合稳定性和适用期,并可防止由于添加剂而导致的所述添加剂转移至粘附物的问题。

Description

保护膜
技术领域
本发明涉及一种保护膜,包括所述保护膜的导电层压体,以及包括所述保护膜的偏光板。
背景技术
本发明涉及一种保护膜。所述保护膜可以应用于导电层压体或偏光板。
透明电极用于多种领域中,例如各种显示设备、光电转换器(如太阳能电池等)、触摸板等的电极,且通过在透明基板(如玻璃、透明膜等)上形成透明导电薄层来制造。所述导电薄层需要保护膜在工艺中防止对所述薄层的损害(如污染、刮擦等)。
此外,所述偏光板也需要所述保护膜在由所述偏光板制造为LCD组件的过程期间保护所述偏光板以防外部的碰撞或摩擦,以及污染。
需要上述保护膜具有起初将所述保护膜固定于粘附物的程度的压敏粘合性,以及在工艺完成之后允许将所述保护膜从所述粘附物剥离而不会损伤所述粘附物的低剥离强度。此外,所述保护膜中包含的压敏粘合剂需要聚合稳定性和足够的适用期。有一种形成大量的交联以实现低剥离强度的方法,但是上述方法可导致聚合稳定性或适用期等降低的问题。此外,当向所述保护膜引入添加剂时,剥离是容易的,但可能产生所述添加剂迁移至所述粘附物的问题,从而导致了光学物理性能等的下降。
作为在先专利的专利文件1提出了一种用于防止对所述导电薄层的损害(如污染、刮擦等)的保护膜。
[技术文献]
[专利文件]
(专利文件1)日本专利申请第4342775号。
发明内容
[技术问题]
本发明旨在一种保护膜,包括所述保护膜的导电层压体,以及包括所述保护膜的偏光板,并提供保护膜,所述保护膜具有控制为低的剥离强度,因而有助于保护膜的移除,并且所述保护膜具有优异的聚合稳定性和适用期,可以防止由于添加剂而导致的所述添加剂转移至粘附物的问题。
[技术方案]
根据本发明的一个方面,提供了一种保护膜。所述保护膜可应用于导电层压体,并可用于防止在导电层压体的制造过程中对导电层的损害(如污染、刮擦等)。此外,本发明的一个实施方式的保护膜可应用于偏光板,并可在由所述偏光板制造为LCD组件的过程期间保护所述偏光板以防外部的碰撞或摩擦,以及污染。
一种示例性的保护膜包括含有压敏粘合剂基础树脂的压敏粘合剂层。所述压敏粘合剂基础树脂可包含聚有机硅氧烷作为聚合单元。即可将所述聚有机硅氧烷引入所述树脂中作为聚合单元。
在本发明的一个实施方式中,所述聚有机硅氧烷的聚合单元可衍生自以下式1的化合物。作为本说明书中所用的“衍生自”,例如,可指的是,在聚有机硅氧烷的聚合单元形成聚合物之前,聚有机硅氧烷可由能够成为聚合物的单元的具体化合物形成。
[式1]
在式1中,n可以是0-1500范围内的整数。在本发明的实施方式中,n可以是5-1300、10-1000、15-800、20-500、25-400、30-300、35-200或40-180范围内的整数。当控制所述聚有机硅氧烷的链长时,所述聚有机硅氧烷可适当包含于所述压敏粘合剂基础树脂中作为聚合单元,从而可获得适于所述保护膜的低剥离强度和聚合稳定性。此外,R可代表相同或不相同的组分,且可分别代表氢、烷基、烷氧基、烯基或炔基。在以上描述中,例如,R可为含有1至30个碳原子的烷基,更具体地,为甲基、乙基或丙基。
除非另有规定,本说明书中所用术语“烷基”可指的是具有1至20个碳原子、1至16个碳原子、1至12个碳原子、1至8个碳原子或1至4个碳原子的直链或支链烷基,或具有3至20个碳原子、3至16个碳原子或4至12个碳原子的环烷基。所述烷基可以任意地被一个或多个取代基所取代。
除非另有规定,本说明书中所用术语“烷氧基”可指的是具有1至8个碳原子或1至4个碳原子的烷氧基。所述烷氧基可具有直链、支链或环形。此外,所述烷氧基可以任意地被一个或多个取代基所取代。
此外,除非另有规定,本说明书中所用的“烯基”可指的是具有2至20个碳原子、2至16个碳原子、2至12个碳原子、2至8个碳原子或2至4个碳原子的烯基。所述烯基可具有直链、支链或环形。此外,所述烯基可以任意地由一个或多个取代基所取代。
此外,除非另有规定,本说明书中所用的“炔基”可指的是具有2至20个碳原子、2至16个碳原子、2至12个碳原子、2至8个碳原子或2至4个碳原子的炔基。
此外,式1的P可以是可聚合官能团。即可通过所述可聚合官能团将所述聚有机硅氧烷引入所述树脂中。此外,可不需特别限定地采用能够被聚合的任意官能团作为所述可聚合官能团,例如,所述可聚合官能团可以是烯基、环氧基、氰基、羧基、丙烯酰基、甲基丙烯酰基、丙烯酰氧基或甲基丙烯酰氧基。
此外,在本发明的一个实施方式中,所述可聚合官能团可仅与聚有机硅氧烷链的一端结合。即可将可聚合官能团形成于两端的聚有机硅氧烷排除在式1的化合物之外。在以上描述中,当可聚合双键存在于两端时,在聚合期间进行交联,从而可能形成在溶剂中不溶的沉淀,或者可能会难以从反应器收集树脂。即交联可在涂布后熟化的条件下形成,且可不在制备树脂的工艺中形成。
合成所述聚有机硅氧烷的方法不作特别的限定,例如,可包括:通过氢化硅烷化使具有可与所述压敏粘合剂基础树脂交联的官能团的乙烯化合物与具有SiH基的硅酮树脂反应,从而将可聚合官能团引入所述硅酮树脂的方法;硅氧烷化合物与具有可聚合官能团的硅氧烷化合物的缩合反应的方法,等等。
在本发明的实施方式中,所述聚有机硅氧烷可具有,例如,3000-20000g/mol、3500-18000g/mol、4000-16000g/mol或4500-14000g/mol的官能团当量作为如上所述的一端。当所述官能团当量小于3000g/mol时,则在将要获得的压敏粘合剂基础树脂聚合时不能将所述聚有机硅氧烷充足地引入所述压敏粘合剂基础树脂,且粘附物可能被污染或者剥离性能可能不会充分展现出来。此外,当所述官能团当量大于20000g/mol时,则可能不会获得足够的粘着力,且交联可在聚合期间进行,从而可能形成在溶剂中不溶的沉淀,或者可能会难以从反应器收集所述树脂。
此外,所述聚有机硅氧烷的重均分子量不作特别的限定,且可优选在300-100000的范围内。当所述分子量在300以下时,将要获得的压敏粘合剂基础树脂的耐热性可能会不足,且当所述分子量在100000以上时,所述聚有机硅氧烷可能会难以与所述压敏粘合剂基础树脂混合。在本发明的实施方式中,所述分子量,例如,可在400-50000、400-30000或500-20000的范围内。此外,所述聚有机硅氧烷可在25℃下具有30-500mm2/s(平方毫米/秒)、40-400mm2/s、50-300mm2/s或200-550mm2/s的粘度。所述分子量或粘度可能随所述聚有机硅氧烷的链长而不同,且当控制所述聚有机硅氧烷的链长在上述范围内时,所述聚有机硅氧烷可适当包含于所述压敏粘合剂基础树脂中作为聚合单元,从而可获得适于所述保护膜的低剥离强度和聚合稳定性。
如上所述,所述保护膜额外包含于导电膜中以防止在所述导电膜的制造过程中对所述薄层的污染、刮擦等,且需要上述保护膜有低剥离强度以使得可在所述工艺结束之后将所述保护膜剥离而不会损伤所述导电薄层。通常地,已采用基于硅酮或氟的添加剂来释放以实现上述低剥离强度。然而,当采用所述基于硅酮或氟的添加剂时,在剥离时会发生所述添加剂转移至基板,剥离可能不会彻底地进行,从而所述导电膜的光学物理性能明显下降。如上所述,在根据本发明的一个实施方式的保护膜中,采用了包含引入了所述聚有机硅氧烷链的压敏粘合剂基础树脂的压敏粘合剂层,从而可容易地释放所述膜。此外,由于硅酮化合物包含于所述压敏粘合剂基础树脂中作为聚合单元,且所述硅酮化合物并不用作所述添加剂,故可防止由于所述添加剂的迁移而导致的降低所述粘附物的光学物理性能的问题。
在以上描述中,聚有机硅氧烷不作特别的限定,只要聚有机硅氧烷可被引入所述压敏粘合剂基础树脂即可。如上所述,所述聚有机硅氧烷可通过衍生自式1的化合物的聚有机硅氧烷来满足。上述聚有机硅氧烷可为市售的且可包括,例如,X-24-8201、X-22-174DX、X-22-2426、X-22-2404、X-22-164A、X-22-164C(信越化学株式会社(Shin-Etsu ChemicalCo.,Ltd.)制造),BY16-152D、BY16-152、BY16-152C(道康宁东丽株式会社(Dow CorningToray Co.,Ltd.)),以及FM-0711、FM-0721、FM-0725(CHISSO株式会社(ChissoCorporation)),等等。
在本发明的实施方式中,所述压敏粘合剂基础树脂可包含(甲基)丙烯酸酯单体作为聚合单元。本发明的一个实施方式的压敏粘合剂基础树脂可包含80-99.8重量份、82-99.5重量份、84-99重量份、86-97重量份或87-95重量份的(甲基)丙烯酸酯单体,以及0.1-10重量份、0.1-8重量份、0.1-7重量份、0.1-6重量份、0.1-5重量份、0.1-3重量份或0.1-1.5重量份的聚有机硅氧烷作为聚合单元。本申请中所用单位“重量份”可指的是重量比。当将所述单体之间的重量比按照以上所述调节时,可有效保持所述压敏粘合剂层的物理性能,如起始粘着力、耐久性、剥离强度等。
在本发明的实施方式中,所述(甲基)丙烯酸酯单体可以是(甲基)丙烯酸烷基酯。例如,所述(甲基)丙烯酸酯单体可以是选自(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)丙烯酸叔丁酯、(甲基)丙烯酸仲丁酯、(甲基)丙烯酸戊酯、(甲基)丙烯酸2-乙基己基酯、(甲基)丙烯酸2-乙基丁基酯、(甲基)丙烯酸正辛酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸异壬酯、(甲基)丙烯酸月桂酯和(甲基)丙烯酸十四烷基酯中的一种或多种,但并不仅限于此。
此外,本发明的一个实施方式的压敏粘合剂基础树脂可进一步包含衍生自具有可交联官能团的可共聚单体的聚合单元。在本发明的实施方式中,所述具有可交联官能团的可共聚单体可以是选自含羟基的共聚单体、含羧基的共聚单体和含氮的共聚单体中的一种或多种。在以上描述中,相对于100重量份的所述压敏粘合剂基础树脂,所述具有可交联官能团的可共聚单体可以以0.01-14重量份、0.5-14重量份、1-13重量份、2-12重量份、3-11重量份、3-9重量份或3-8重量份被包含。当将所述具有可交联官能团的可共聚单体调节为上述范围内时,可确保所述基础树脂的储存稳定性。更具体地,采用形成大量交联的方法来实现适于所述保护膜的低剥离强度,且可将含可交联官能团的单体用于上述方法。然而,当在所述树脂中所述含可交联官能团的单体以14重量份以上被包含以实现低剥离强度时,可降低所述基础树脂的储存稳定性和聚合稳定性。
在本发明的实施方式中,所述压敏粘合剂层可进一步包含能够交联所述压敏粘合剂基础树脂的多官能交联剂。所述多官能交联剂的实例可包括:基于异氰酸酯的化合物、基于环氧化物的化合物、基于氮丙啶的化合物、基于金属螯合物的化合物等,且考虑到所述树脂中包含的可交联官能团的类型,可适当选取其一种类型或两种或更多种类型。所述异氰酸酯化合物的实例可包括二异氰酸酯、二甲苯二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯、异佛尔酮二异氰酸酯、四甲基二甲苯二异氰酸酯、萘二异氰酸酯等,或者上述中的一种或多种基于异氰酸酯的化合物与多元醇的加成反应产物。所述多元醇的实例可包括三羟甲基丙烷等。此外,所述环氧化合物的实例可包括乙二醇二缩水甘油醚、三缩水甘油醚、三羟甲基丙烷三缩水甘油醚、N,N,N',N'-四缩水甘油基乙二胺、丙三醇二缩水甘油基醚等的一种类型或两种或更多种类型,以及氮丙啶化合物的实例可包括N,N'-甲苯-2,4-二(1-氮丙啶甲酰胺)、N,N'-二苯基甲烷-4,4'-二(1-氮丙啶甲酰胺)、三亚乙基三聚氰胺、二间苯二甲酰-1-(2-甲基氮丙啶)、三-1-氮丙啶基氧化膦等的一种类型或两种或更多种类型。此外,所述金属螯合物的实例可包括将多价金属(如Al、Fe、Zn、Sn、Ti、Sb、Mg或V)与乙酰丙酮或乙酰乙酸乙酯配位而制得的化合物。
在本发明的实施方式中,所述多官能交联剂可以是脂族线性多价NCO与脂族环形多价NCO的混合物。例如,所述脂族线性多价NCO可以是六亚甲基二异氰酸酯,而所述脂族环形多价NCO可以是异佛尔酮二异氰酸酯。可将所述脂族线性多价NCO与所述脂族环形多价NCO以6:4至9:1范围内的比例混合以形成混合物,且NCO可在所述混合物中以8-20wt%被包含。此外,在本说明书中,所述NCO可指的是异氰酸酯基团。
在所述压敏粘合剂层中,相对于100重量份的所述压敏粘合剂基础树脂,所述多官能交联剂可以以0.01-20重量份、0.1-18重量份、0.5-15重量份、1.5-10重量份、2-8重量份、2.5-5重量份或2.5-4重量份被包含。为了实现适于所述保护膜的低剥离强度,采用了形成大量交联的方法,需要使用过量的交联剂。然而,当使用所述过量的交联剂时,可产生增大所述压敏粘合剂层的涂布溶液的适用期的问题。当将根据本发明的一个实施方式的压敏粘合剂层中的多功能交联剂的含量限定为20重量份以下、14重量份以下或者10重量份以下时,可改善所述压敏粘合剂层的适用期。
此外,根据本发明的一个实施方式的压敏粘合剂层可进一步包含固化延迟剂。所述固化延迟剂的实例可包括以下一种或多种:β-酮酯,如乙酰乙酸甲酯、乙酰乙酸乙酯、乙酰乙酸辛酯、乙酰乙酸油烯基酯(oleyl acetoacetate)、乙酰乙酸月桂酯、乙酰乙酸硬脂酰酯等;或者β-二酮,如乙酰丙酮、2,4-己二酮、苯甲酰丙酮等。
根据本发明的一个实施方式的压敏粘合剂层,除了上述组分之外,还可进一步包含一种类型或两种或更多种类型的添加剂,如硅烷偶联剂、增粘剂、环氧树脂、紫外光稳定剂、着色剂、增强剂、填料、消泡剂、表面活性剂、催化剂或增塑剂。
在本发明的实施方式中,所述保护膜可进一步包含基底层,且可在所述基底层的一侧上形成所述压敏粘合剂层。所述基底层可包含基于聚酯的聚合物、基于聚烯烃的聚合物、基于降冰片烯的聚合物、单组份聚合物(如聚碳酸酯、聚醚砜、聚芳酯等)、共聚聚合物或者基于环氧化物的聚合物。所述基底层的厚度不作特别的限定,但通常在约20-300μm的范围内,且优选在30-200μm的范围内。
在本发明的实施方式中,形成本发明的实施方式的压敏粘合剂层的压敏粘合剂基础树脂可通过与上述多官能交联剂混合来固化。此外,所述压敏粘合剂基础树脂,到所述树脂的粘度增长至在制备完成时所述树脂的起始粘度的二倍以上为止,在使所述树脂与交联剂混合之后,恰好需要5小时以上。更具体地,上述时间可在5-100小时、10-100小时、15-100小时或20-100小时的范围内。当所述压敏粘合剂层的粘度增长至所述起始粘度的二倍以上时,进一步的涂布过程是不可能的,从而所述需要的时间可在本说明书中定义为适用期。本发明的一个实施方式的保护膜可充分确保如上所述的适用期,从而可有效进行所述制造过程。
根据本发明的另一个方面,提供了一种导电层压体。一种示例性导电层压体可进一步包含上述的保护膜。在本发明的实施方式中,所述导电层压体可进一步包括具有至少一个导电层的导电膜,以及粘附于所述导电膜的一侧的所述保护膜。
本发明的实施方式的导电膜不作特别的限定,只要其包含至少一层所述导电层即可。形成所述导电层的材料的实例可包括:金属,如金、银、铂、钯、铜、铝、镍、铬、钛、铁、钴、锡和它们两种以上的合金;金属氧化物,包括氧化铟、氧化锡、氧化钛、氧化镉或它们两种类型以上的混合物;以及包含碘化铜等的其它金属氧化物。所述导电层可以是晶体层,或者非结晶层。在本发明的实施方式中,可优选采用氧化铟锡(ITO)来形成所述导电层,但并不仅限于此。此外,考虑到连续膜的形成的可能性、导电性、透明度等,如上所述的导电层的厚度可调节为约10-300nm,且优选约10-200nm。
在本发明的实施方式中,所述导电层可通过锚定层或介电层形成于塑料基底膜上。所述锚定层或介电层可起到增强所述导电层与所述基底膜之间的粘附力,并改善抗刮擦性或抗弯折性的作用。如上所述的锚定层或介电层可采用无机物质(如SiO2、MgF2、Al2O3等)、有机物质(如丙烯酸树脂、氨基甲酸酯树脂、三聚氰胺树脂、醇酸树脂、基于硅氧烷的聚合物等)或者它们两种类型以上的混合物而通过真空沉积法、溅射法、离子电镀法或涂布法来形成。所述锚定层或介电层可形成为具有约100nm以下,特别地,15-100nm,更特别地,20-60nm的厚度。
在本发明的实施方式中,可在其上形成了所述导电层的基底或基板上进行适当的粘合处理,如电晕放电处理、紫外照射处理、等离子体处理、溅射蚀刻处理等。
所述导电膜可进一步包括显露所述导电层的透明基底。作为所述透明基底,特别地,优选采用具有优异透明度或耐热性的透明基底。如上所述的有机聚合物的实例可包括单组份聚合物,如基于聚酯的聚合物(如聚对苯二甲酸乙二醇酯),基于聚烯烃的聚合物,基于降冰片烯的聚合物,聚碳酸酯,聚醚砜或聚芳酯,共聚聚合物,或者基于环氧化物的聚合物,等等。所述透明基底的实例可优选包含上述有机聚合物的膜状形态的产品、片状形态的产品和其他模塑产品。
在本发明的实施方式中,所述导电膜的结构不作特别的限定,且可包括硬涂层、所述透明基底层和所述导电层。此外,所述保护膜上的压敏粘合剂层可位于所述导电膜的硬涂层上。
根据本发明的另一个方面,提供了一种偏光板。一种示例性的偏光板可包括上述的保护膜。在本发明的实施方式中,所述偏光板可包括至少一个偏光片,以及粘附于所述偏光片的一侧的所述保护膜。所述具有保护膜的偏光板可适用于所有常规液晶显示设备,且所述液晶面板的类型不作特别的限定。例如,可形成包括所述保护膜粘合于液晶单元的任一侧或两侧的液晶面板的液晶显示设备。
[有益效果]
根据本发明的实施方式的保护膜具有控制为低的的剥离强度,从而所述保护膜的移除是容易的,所述保护膜具有优异的聚合稳定性和适用期,并可防止由于添加剂而导致的所述添加剂转移至粘附物的问题。
具体实施方式
下文中,本发明将结合根据本发明的实施方式的实施例和未根据本发明的实施方式的对比实施例(但并不仅限于以下实施例)进行详细描述。
实施例1
压敏粘合剂层的制备
在乙酸乙酯中,将丙烯酸-2-乙基己基酯(2-EHA)、作为反应性聚有机硅氧烷的X-22-2426(信越化学株式会社)和丙烯酸-2-羟乙基酯(2-HEA)以89:1:10(2-EHA:X-22-2426:2-HEA)的重量比共聚,从而获得了基于丙烯酸的共聚物溶液。
接着,相对于100重量份的基于丙烯酸的共聚物(固体部分),将7.5重量份的HMDI/IPDI(=8/2重量比(NCO%:16wt%),其为基于异氰酸酯的交联剂)、7重量份的作为固化延迟剂的乙酰丙酮和0.01重量份的作为催化剂的二月桂酸二丁基锡混合,从而获得了压敏粘合剂组合物。
保护膜的制备
将所述压敏粘合剂组合物涂布于A4300PET(Toyobo株式会社(Toyobo Co.,Ltd.))(厚度:100μm)的一侧上,干燥,从而形成了具有20μm厚度的透明压敏粘合剂层。将所述涂布于A4300PET的一侧上的透明压敏粘合剂层在干燥和覆盖剥离膜之后,立即在40℃下熟化4天。
导电层压体的制备
将制得的保护膜粘附于作为ITO膜的L2CC5(LG化学株式会社)的一侧。将所述保护膜层压以使得所述保护膜的压敏粘合剂层接触所述ITO膜的硬涂层。
实施例2
除了采用X-22-174DX(信越化学株式会社)作为聚有机硅氧烷来替代X-22-2426(信越化学株式会社)之外,以与实施例1相同的方式制备所述保护膜和导电层压体。
实施例3
除了以94:1:5(2-EHA:X-22-2426:2-HEA)的重量比采用丙烯酸-2-乙基己基酯、作为反应性聚有机硅氧烷的X-22-2426(信越化学株式会社)和丙烯酸-2-羟乙基酯来制备共聚物,以及相对于100重量份的所述共聚物,采用3.8重量份的HMDI/IPDI(=8/2重量比(NCO%:16wt%),其为基于异氰酸酯的交联剂)之外,以与实施例1相同的方式制备了所述保护膜和导电层压体。
实施例4
除了以94.5:0.5:5(2-EHA:X-22-2426:2-HEA)的比例采用丙烯酸-2-乙基己基酯、作为反应性聚有机硅氧烷的X-22-2426(信越化学株式会社)和丙烯酸-2-羟乙基酯来制备共聚物,以及相对于100重量份的所述共聚物,采用3.8重量份的HMDI/IPDI(=8/2重量比(NCO%:16wt%),其为基于异氰酸酯的交联剂)之外,以与实施例1相同的方式制备了所述保护膜和导电层压体。
对比实施例1
除了在不添加聚有机硅氧烷的情况下以85:15(2-EHA:2-HEA)的比例采用丙烯酸-2-乙基己基酯和丙烯酸-2-羟乙基酯来制备共聚物,以及相对于100重量份的所述共聚物,采用11.7重量份的HMDI/IPDI(=8/2重量比(NCO%:16wt%),其为基于异氰酸酯的交联剂)之外,以与实施例1相同的方式制备了所述保护膜和导电层压体。
对比实施例2
除了在不添加聚有机硅氧烷的情况下以95:5(2-EHA:2-HEA)的比例采用丙烯酸-2-乙基己基酯和丙烯酸-2-羟乙基酯来制备共聚物,以及相对于100重量份的所述共聚物,采用3.8重量份的HMDI/IPDI(=8/2重量比(NCO%:16wt%),其为基于异氰酸酯的交联剂)之外,以与实施例1相同的方式制备了所述保护膜和导电层压体。
对比实施例3
除了以90:10(2-EHA:2-HEA)的比例采用丙烯酸-2-乙基己基酯和丙烯酸-2-羟乙基酯作为树脂来制备共聚物,相对于100重量份的所述共聚物,添加0.1重量份不具有可聚合官能团的BYK-377作为聚有机硅氧烷,以及相对于100重量份的所述共聚物,采用7.5重量份的HMDI/IPDI(=8/2重量比(NCO%:16wt%),其为基于异氰酸酯的交联剂)之外,以与实施例1相同的方式制备了所述保护膜和导电层压体。
实验实施例1:剥离强度
将实施例和对比实施例中熟化(固化)的保护膜的压敏粘合剂层粘附于所述ITO膜的硬涂层,150℃下在其上热处理1小时,然后在室温条件下,采用高速剥离测试仪(CBT-4720,忠北技术株式会社(Chung-buk Tech)制造)以180°剥离角度和20m/min剥离速度测量剥离强度(宽度:1英寸)。
实验实施例2:适用期
采用旋转粘度计(LVDV-II pro,布洛克菲尔德工程实验室公司(BrookfieldEngineering Laboratories,Inc.)制造)在#63轴、温度25℃的条件,并在50rpm的速率下,测量实施例和对比实施例中制备的压敏粘合剂组合物的粘度。将所述共聚物和所述交联剂刚刚混合好的组合物的粘度假设为起始粘度,测量到所述粘度相比于所述起始粘度增长二倍以上为止所需时间的变化,并将其定义为适用期。
实验实施例3:雾度
将所述保护膜从实施例和对比实施例中制备的导电层压体剥离,然后采用雾度测量仪(HM-150)测量所述导电层压体的雾度。
[表1]
适用期(hr) 剥离强度(gf/in) 雾度(%)
实施例1 12 19 0.82
实施例2 11 21 0.89
实施例3 75 86 0.84
实施例4 74 91 0.81
对比实施例1 2 25 0.89
对比实施例2 74 154 0.88
对比实施例3 10 25 2.1
在对比实施例1和2中,未将聚有机硅氧烷链引入所述压敏粘合剂层,因而得到了不充足的适用期或测得了高剥离强度。对比实施例3中,由于包含聚有机硅氧烷作为添加剂,结果造成了剥离所述保护膜之后所述添加剂转移至所述ITO,从而降低了光学物理性能。

Claims (18)

1.一种保护膜,其包括压敏粘合剂层,所述压敏粘合剂层包含压敏粘合剂基础树脂,
其中,所述压敏粘合剂基础树脂包含作为聚合单元的聚有机硅氧烷、作为聚合单元的(甲基)丙烯酸酯单体以及作为聚合单元的具有可交联官能团的可共聚单体,
其中,所述聚有机硅氧烷的聚合单元衍生自以下式1的化合物:
[式1]
其中,在式1中,n为0-1500范围内的整数,R代表相同或不相同的组分,且分别代表氢、烷基、烷氧基或炔基,以及P为可聚合官能团,
其中,所述聚有机硅氧烷具有3000-20000g/mol的官能团当量。
2.权利要求1所述的保护膜,其中,所述聚有机硅氧烷具有300-100000的重均分子量。
3.权利要求1所述的保护膜,其中,所述可聚合官能团包括烯基、环氧基、氰基、羧基、丙烯酰基、甲基丙烯酰基、丙烯酰氧基或甲基丙烯酰氧基。
4.权利要求1所述的保护膜,其中,所述压敏粘合剂基础树脂包含衍生自80-99.8重量份的所述(甲基)丙烯酸酯单体和0.1-10重量份的聚有机硅氧烷的聚合单元。
5.权利要求1所述的保护膜,其中,所述具有可交联官能团的可共聚单体为选自含羟基的共聚单体、含羧基的共聚单体和含氮的共聚单体中的一种或多种。
6.权利要求1所述的保护膜,其中,相对于100重量份的所述压敏粘合剂基础树脂,所述具有可交联官能团的可共聚单体以0.01-14重量份被包含。
7.权利要求1所述的保护膜,其中,所述压敏粘合剂层进一步包含交联所述压敏粘合剂基础树脂的多官能交联剂。
8.权利要求7所述的保护膜,其中,所述多官能交联剂为选自基于异氰酸酯的化合物、基于环氧化物的化合物、基于氮丙啶的化合物和基于金属螯合物的化合物中的一种或多种。
9.权利要求7所述的保护膜,其中,所述多官能交联剂为脂族线性多价NCO与脂族环形多价NCO的混合物。
10.权利要求7所述的保护膜,其中,在所述压敏粘合剂层中,相对于100重量份的所述压敏粘合剂基础树脂,所述多官能交联剂以0.01-20重量份被包含。
11.权利要求1所述的保护膜,其中,所述压敏粘合剂层进一步包含固化延迟剂。
12.权利要求11所述的保护膜,其中,所述固化延迟剂为选自乙酰乙酸甲酯、乙酰乙酸乙酯、乙酰乙酸辛酯、乙酰乙酸油烯基酯、乙酰乙酸月桂酯、乙酰乙酸硬脂酰酯、乙酰丙酮、2,4-己二酮或苯甲酰丙酮中的一种或多种。
13.权利要求1所述的保护膜,其进一步包括基底层,其中,所述压敏粘合剂层形成于所述基底层的一侧上。
14.权利要求13所述的保护膜,其中,所述基底层包含:聚碳酸酯,聚醚砜或聚芳酯。
15.权利要求13所述的保护膜,其中,所述基底层包含:基于聚酯的聚合物,基于聚烯烃的聚合物或基于降冰片烯的聚合物,或基于环氧化物的聚合物。
16.权利要求1所述的保护膜,其中,所述压敏粘合剂基础树脂为如下树脂:所述树脂,到所述树脂的粘度与刚刚制得的树脂的起始粘度相比增长至二倍以上为止,在使树脂与交联剂混合之后,紧接着需要5小时以上。
17.一种导电层压体,其包括:
具有至少一个导电层的导电膜;以及
粘附于所述导电膜的一侧的权利要求1所述的保护膜。
18.一种偏光板,其包括:
至少一个偏光片;以及
粘附于所述偏光片的一侧的权利要求1所述的保护膜。
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