CN109321157B - 光学膜用粘合剂组合物、光学膜用粘合剂层、带粘合剂层的光学膜和图像显示装置 - Google Patents
光学膜用粘合剂组合物、光学膜用粘合剂层、带粘合剂层的光学膜和图像显示装置 Download PDFInfo
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- MEJYOZOPFBOWNM-UHFFFAOYSA-N triethyl(heptyl)azanium Chemical compound CCCCCCC[N+](CC)(CC)CC MEJYOZOPFBOWNM-UHFFFAOYSA-N 0.000 description 1
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Abstract
一种光学膜用粘合剂组合物,其含有(甲基)丙烯酸系聚合物(A)、以及相对于所述(甲基)丙烯酸系聚合物(A)100重量份为0.01~3重量份的交联剂(B),所述(甲基)丙烯酸系聚合物(A)含有(甲基)丙烯酸烷基酯(a1)70重量%以上、含芳环的(甲基)丙烯酸酯(a2)3~25重量%、含酰胺基单体(a3)0.1~8重量%、含羧基单体(a4)0.01~2重量%和含羟基单体(a5)0.01~3重量%作为单体单元,所述(甲基)丙烯酸系聚合物(A)的重均分子量Mw为100万~250万且Mw/数均分子量Mn满足1.8以上且10以下。该粘合剂组合物能够形成对于玻璃和透明导电层可满足不产生发泡、剥离或加湿白浊的耐久性且可抑制因漏光导致的显示不均而且耐金属腐蚀性也优异的粘合剂层。
Description
相关申请
本申请是分案申请,其母案申请的申请号:201580017716.5(PCT/JP2015/060049),申请日:2015.03.31,优先权日:2014.03.31,发明名称:光学膜用粘合剂组合物、光学膜用粘合剂层、带粘合剂层的光学膜和图像显示装置。
技术领域
本发明涉及光学膜用粘合剂组合物和利用该粘合剂组合物在光学膜的至少单面形成有粘合剂层的带粘合剂层的光学膜。此外,本发明涉及使用上述带粘合剂层的光学膜的液晶显示装置、有机EL显示装置、PDP等图像显示装置。作为上述光学膜,可以使用偏振膜、相位差膜、光学补偿膜、增亮膜以及层叠有这些膜的光学膜。
背景技术
液晶显示装置等从其图像形成方式出发必须在液晶盒的两侧设置偏振元件,一般而言贴合有偏振膜。另外在液晶面板中,除了偏振膜以外,为了提高显示器的显示品质而开始使用各种各样的光学元件。例如使用作为防着色的相位差膜、用于改善液晶显示器的视场角的视场角放大膜、以及用于提高显示器的对比度的增亮膜等。这些膜统称为光学膜。
在将上述光学膜等光学部件贴合于液晶盒时,通常使用粘合剂。另外,光学膜与液晶盒的粘接或者光学膜间的粘接中,通常为了降低光的损失,各材料使用粘合剂进行密合。这种情况下,具有使光学膜固定时不需要干燥工序等的优点,因而对于粘合剂而言,通常使用在光学膜的单侧预先作为粘合剂层而设置有粘合剂的带粘合剂层的光学膜。带粘合剂层的光学膜的粘合剂层上通常贴附有脱模膜。
作为对上述粘合剂层要求的必要特性,要求将带粘合剂层的光学膜贴合于液晶面板的玻璃基板时的耐久性,例如在作为环境促进试验而通常进行的利用加热和加湿等的耐久试验中,要求不发生起因于粘合剂层的剥离、浮起等不良情况。
另外,光学膜(例如偏振板)具有通过加热处理而收缩的倾向。由于偏振板的收缩,形成粘合剂层的基础聚合物发生取向而产生相位差,其成为因漏光导致的显示不均的问题。因此,对于上述粘合剂层要求抑制显示不均。
提出了上述带粘合剂层的光学膜的形成粘合剂层的各种粘合剂组合物(例如专利文献1至3)。
另一方面,液晶显示装置的制造时,将上述带粘合剂层的偏振膜贴附于液晶盒时,从带粘合剂层的偏振膜的粘合剂层剥离脱模膜,而由于该脱模膜的剥离而产生静电。如此产生的静电对液晶显示装置内部的液晶的取向造成影响,招致不良。另外,在液晶显示装置的使用时有时产生因静电导致的显示不均。静电的产生例如能够通过在偏振膜的外表面形成抗静电层来进行抑制,为了在静电产生的本源的位置抑制产生,对粘合剂层赋予抗静电功能是有效的。
作为对粘合剂层赋予抗静电功能的手段,例如提出了在形成粘合剂层的粘合剂中配合离子性化合物(专利文献4至5)。专利文献4中记载了将包含咪唑鎓阳离子和无机阴离子的离子性固体配合进用于偏振膜的丙烯酸系粘合剂,专利文献5中记载了将由含有季氮原子的碳数6~50的阳离子与含氟原子的阴离子构成的鎓盐等在常温为液体的有机熔融盐配合进用于偏振膜的丙烯酸系粘合剂。
现有技术文献
专利文献
专利文献1:日本特开2012-158702号公报
专利文献2:日本特开2009-215528号公报
专利文献3:日本特开2009-242767号公报
专利文献4:日本特开2009-251281公报
专利文献5:国际公开2007/034533号小册子
发明内容
发明要解决的问题
液晶显示装置的使用时有时发生因静电导致的显示不均,因此在液晶面板的玻璃基板上有时形成透明导电层(例如含有氧化锡的氧化铟:ITO层)。另外,上述透明导电层除了因静电导致的显示不均的对策以外,将液晶显示装置用于触控面板的情况下,作为将液晶盒内的驱动电场和触控面板切断的屏蔽电极发挥功能。在该构成的液晶显示装置中,带粘合剂层的光学膜的粘合剂层直接贴合于上述ITO层。因此,对于上述粘合剂层,不仅要求对玻璃基板的密合性,还要求对ITO层的密合性。一般而言,与玻璃板相比,ITO层与粘合剂层的密合性更差,耐久性常成为问题。以将上述带粘合剂层的光学膜贴合于玻璃基板的状态置于60℃95%RH等高温高湿条件下后,若恢复至常温,则明显发生粘合剂层产生白浊的现象(加湿白浊)。若加湿白浊产生,则成为显示器的可视性下降的原因。
另外,上述粘合剂层与液晶面板的ITO层、迂回布线的铜等金属直接接触。因此,根据上述粘合剂层的组成,有可能腐蚀ITO层、金属。另外,若发生腐蚀,则有ITO层、迂回布线的电阻值上升的问题。
专利文献1中提出了相对于包含含芳环单体和含酰胺基单体的丙烯酸系聚合物100重量份配合异氰酸酯系交联剂4~20重量份的粘合剂组合物。然而,专利文献1中作为形成丙烯酸系聚合物的单体不含有含羟基单体,因此丙烯酸系聚合物与异氰酸酯系交联剂不能直接反应,从而发生相分离,由此有粘合剂容易发生白浊的倾向,是不优选的。另外,专利文献1的粘合剂组合物由于交联剂的比例多,因此有在耐久性试验中容易产生剥离的倾向。
另外,在专利文献2、3中提出了含有(甲基)丙烯酸聚合物以及交联剂的粘合剂组合物,该(甲基)丙烯酸聚合物含有含芳环的(甲基)丙烯酸酯、含氨基的(甲基)丙烯酸酯。然而,由专利文献2、3的粘合剂组合物形成的粘合剂层对ITO层的密合性差,不能满足耐久性。需要说明的是,在专利文献2的比较例中,公开了使用含酰胺基单体代替含氨基的(甲基)丙烯酸酯,如专利文献2、3的各表2的结果所示的那样,在使用含酰胺基单体的情况下,不能满足耐久性。
另一方面,如专利文献4、5所述,通过在形成粘合剂层的粘合剂中配合离子性化合物可以赋予抗静电功能。此外,液晶显示装置设想在各种各样的温湿度环境下使用,因此要求即便温度、湿度变化而表面电阻值也不变化、可长期赋予稳定的抗静电功能的粘合剂。近年来,与触控面板层叠的液晶显示装置、在液晶面板的玻璃基板上直接成膜ITO层等传感器电极的所谓On Cell触控面板型的液晶显示装置正在增加。这种情况下,可知若粘合剂层的表面电阻过低,则发生触控面板的灵敏度下降的问题。为了兼顾静电不均的防止和触控面板的灵敏度下降,需要将表面电阻控制在比以往更窄的范围内,因此要求比以前更稳定的抗静电功能。
专利文献4中提出了利用包含咪唑鎓阳离子、无机阴离子和离子性固体的丙烯酸系粘合剂形成长期赋予稳定的抗静电功能的粘合剂层。然而,专利文献4的粘合剂层的对ITO层的在加湿条件下的密合性不充分。另外,专利文献5中提出了包含常温下为液体的有机熔融盐的丙烯酸系粘合剂。然而,专利文献5所述的丙烯酸系粘合剂的有机熔融盐的分散性差,由该粘合剂形成的粘合剂层的抗静电功能的稳定性不充分。
本发明的目的在于提供光学膜用粘合剂组合物,该光学膜用粘合剂组合物能够形成对于玻璃和透明导电层均可满足不产生发泡、剥离或加湿白浊的耐久性且可抑制因漏光导致的显示不均而且耐金属腐蚀性也优异的粘合剂层。
另外,本发明的目的在于提供光学膜用粘合剂组合物,所述光学膜用粘合剂组合物能够形成对于玻璃和透明导电层均可满足不产生发泡、剥离或加湿白浊的耐久性且可抑制因漏光导致的显示不均而且耐金属腐蚀性也优异且可赋予稳定的抗静电功能的粘合剂层。
另外,本发明的目的在于提供具有利用上述光学膜用粘合剂组合物形成的粘合剂层的带粘合剂层的光学膜,以及提供使用了上述带粘合剂层的光学膜的图像显示装置。
用于解决问题的手段
本发明人为了解决上述课题而反复进行深入研究,结果发现下述光学膜用粘合剂组合物,从而完成了本发明。
即,本发明涉及:
一种光学膜用粘合剂组合物,其特征在于,含有(甲基)丙烯酸系聚合物(A)、以及相对于所述(甲基)丙烯酸系聚合物(A)100重量份为0.01~3重量份的交联剂(B),
所述(甲基)丙烯酸系聚合物(A)含有
(甲基)丙烯酸烷基酯(a1)70重量%以上、
含芳环的(甲基)丙烯酸酯(a2)3~25重量%、
含酰胺基单体(a3)0.1~8重量%、
含羧基单体(a4)0.01~2重量%、和
含羟基单体(a5)0.01~3重量%作为单体单元,
所述(甲基)丙烯酸系聚合物(A)的重均分子量Mw为100万~250万且Mw/数均分子量Mn满足1.8以上且10以下。
在上述光学膜用粘合剂组合物中,上述含酰胺基单体(a3)优选为含N-乙烯基的内酰胺系单体。
在上述光学膜用粘合剂组合物中,上述含羟基单体(a5)优选为(甲基)丙烯酸4-羟基丁酯。
上述交联剂(B)优选含有选自异氰酸酯系化合物和过氧化物中的至少1种。上述异氰酸酯系化合物优选含有脂肪族多异氰酸酯系化合物。
上述光学膜用粘合剂组合物可以还含有硅烷偶联剂(C)。作为上述硅烷偶联剂(C),优选在1分子内具有2个以上的烷氧基甲硅烷基的硅烷偶联剂。另外,作为上述硅烷偶联剂(C),优选在分子内具有环氧基的硅烷偶联剂。上述硅烷偶联剂(C)相对于上述(甲基)丙烯酸系聚合物(A)100重量份优选含有0.001~5重量份。
上述光学膜用粘合剂组合物可以还含有离子性化合物(D)。上述离子性化合物(D)优选为碱金属盐和/或有机阳离子-阴离子盐。另外,上述离子性化合物(D)优选包含含氟基的阴离子。上述离子性化合物(D)相对于上述(甲基)丙烯酸系聚合物(A)100重量份优选含有0.05~10重量份。
上述光学膜用粘合剂组合物可以还含有具有反应性甲硅烷基的聚醚化合物(E)。具有上述反应性甲硅烷基的聚醚化合物(E)相对于上述(甲基)丙烯酸系聚合物(A)100重量份优选含有0.001~10重量份。
另外,本发明涉及一种光学膜用粘合剂层,其特征在于,由上述光学膜用粘合剂组合物形成。
另外,本发明涉及一种带粘合剂层的光学膜,其特征在于,在光学膜的至少一侧形成有上述光学膜用粘合剂层。
另外,本发明涉及一种图像显示装置,其特征在于,使用至少一张上述带粘合剂层的光学膜。
发明的效果
本发明的光学膜用粘合剂组合物含有以规定量的单体单元的比例含有含芳环的(甲基)丙烯酸酯(a2)、含酰胺基单体(a3)、含羧基单体(a4)和含羟基单体(a5)且具有特定的重均分子量和分子量分布的(甲基)丙烯酸系聚合物(A)作为基础聚合物。具有由含有该特定组成的(甲基)丙烯酸系聚合物(A)和规定量的交联剂(B)的光学膜用粘合剂组合物所得到的粘合剂层的带粘合剂层的光学膜对于玻璃和透明导电层(ITO层等)而言,不产生加湿白浊的耐久性均良好,均能够在贴附于液晶盒等的状态下抑制剥离、浮起等的产生。
一般而言,对ITO层等透明导电层的耐久性也容易受到ITO层的组成的影响,并且观察到与高锡比率的结晶性ITO层相比,低锡比率的非晶性ITO层的耐久性更差的倾向。由光学膜用粘合剂组合物得到的粘合剂层对于非晶性ITO层也能够实现稳定的耐久性。另外,具有本发明的粘合剂层的带粘合剂层的光学膜的对透明导电层的耐金属腐蚀性也优异。
另外,将使用带粘合剂层的偏振板等带粘合剂层的光学膜的液晶显示装置等图像显示装置置于加热、加湿条件下时,在液晶面板等的周边部产生周边不均、角不均之类因(拔白)所导致的显示不均,有时产生显示不良,本发明的粘合剂光学膜的粘合剂层由于使用了上述光学膜用粘合剂组合物,因而能够抑制显示屏幕的周边部分的漏光所导致的显示不均。
另外,对于本发明的光学膜用粘合剂组合物,可以通过配合离子性化合物(D)来赋予抗静电功能。本发明的光学膜用粘合剂组合物含有上述该特定组成的(甲基)丙烯酸系聚合物(A)和规定量的交联剂(B),因此在配合有离子性化合物(D)的情况下,能够形成可赋予稳定的抗静电功能的粘合剂层。另外,本发明的光学膜用粘合剂组合物具有良好的返工性,通过配合具有反应性甲硅烷基的聚醚化合物(E),能够进一步提高返工性。
具体实施方式
本发明的光学膜用粘合剂组合物包含(甲基)丙烯酸系聚合物(A)作为基础聚合物。(甲基)丙烯酸系聚合物(A)中,作为单体单元,通常含有(甲基)丙烯酸烷基酯作为主要成分。需要说明的是,(甲基)丙烯酸酯是指丙烯酸酯和/或甲基丙烯酸酯,是与本发明的(甲基)同样的意思。
作为构成(甲基)丙烯酸系聚合物(A)的主骨架的(甲基)丙烯酸烷基酯,可以例示直链状或支链状的烷基的碳数1~18的(甲基)丙烯酸烷基酯。例如,上述烷基可以例示:甲基、乙基、丙基、异丙基、丁基、异丁基、戊基、己基、环己基、庚基、2-乙基己基、异辛基、壬基、癸基、异癸基、十二烷基、异肉豆蔻基、月桂基、十三烷基、十五烷基、十六烷基、十七烷基、十八烷基等。这些可以单独使用也可以组合使用。这些烷基的平均碳数优选为3~9。
(甲基)丙烯酸系聚合物(A)中使用含芳环的(甲基)丙烯酸酯(a2)。含芳环的(甲基)丙烯酸酯(a2)是在其结构中具有芳环结构且包含(甲基)丙烯酰基的化合物。作为芳环,可以举出苯环、萘环或联苯环。含芳环的(甲基)丙烯酸酯(a2)能够满足耐久性(尤其对透明导电层的耐久性)且改善因周边部的拔白导致的显示不均。
作为含芳环的(甲基)丙烯酸酯(a2)的具体例,例如可以举出:(甲基)丙烯酸苄酯、(甲基)丙烯酸苯酯、邻苯基苯酚(甲基)丙烯酸酯、苯氧基(甲基)丙烯酸酯、(甲基)丙烯酸苯氧基乙酯、(甲基)丙烯酸苯氧基丙酯、苯氧基二乙二醇(甲基)丙烯酸酯、环氧乙烷改性壬基苯酚(甲基)丙烯酸酯、环氧乙烷改性甲酚(甲基)丙烯酸酯、苯酚环氧乙烷改性(甲基)丙烯酸酯、(甲基)丙烯酸2-羟基-3-苯氧基丙酯、(甲基)丙烯酸甲氧基苄酯、(甲基)丙烯酸氯苄酯、(甲基)丙烯酸甲苯基酯、聚苯乙烯基(甲基)丙烯酸酯等具有苯环的(甲基)丙烯酸酯;羟乙基化β-萘酚丙烯酸酯、(甲基)丙烯酸2-萘并乙酯、丙烯酸2-萘氧基乙酯、(甲基)丙烯酸2-(4-甲氧基-1-萘氧基)乙酯等具有萘环的(甲基)丙烯酸酯;(甲基)丙烯酸联苯酯等具有联苯环的(甲基)丙烯酸酯。
作为上述含芳环的(甲基)丙烯酸酯(a2),从粘合特性、耐久性的方面出发,优选(甲基)丙烯酸苄酯、(甲基)丙烯酸苯氧基乙酯,特别优选(甲基)丙烯酸苯氧基乙酯。
含酰胺基单体(a3)是在其结构中包含酰胺基且包含(甲基)丙烯酰基、乙烯基等聚合性不饱和双键的化合物。作为含酰胺基单体(a3)的具体例,可以举出(甲基)丙烯酰胺、N,N-二甲基(甲基)丙烯酰胺、N,N-二乙基(甲基)丙烯酰胺、N-异丙基丙烯酰胺、N-甲基(甲基)丙烯酰胺、N-丁基(甲基)丙烯酰胺、N-己基(甲基)丙烯酰胺、N-羟甲基(甲基)丙烯酰胺、N-羟甲基-N-丙烷(甲基)丙烯酰胺、氨基甲基(甲基)丙烯酰胺、氨基乙基(甲基)丙烯酰胺、巯基甲基(甲基)丙烯酰胺、巯基乙基(甲基)丙烯酰胺等丙烯酰胺系单体;N-(甲基)丙烯酰吗啉、N-(甲基)丙烯酰哌啶、N-(甲基)丙烯酰吡咯烷等N-丙烯酰杂环单体;N-乙烯基吡咯烷酮、N-乙烯基-ε-己内酰胺等含N-乙烯基的内酰胺系单体等。含酰胺基单体(a3)在满足耐久性的方面是优选的,在含酰胺基单体(a3)之中,尤其含N-乙烯基的内酰胺系单体满足对透明导电层的耐久性而优选。
含羧基单体(a4)是在其结构中包含羧基且包含(甲基)丙烯酰基、乙烯基等聚合性不饱和双键的化合物。作为含羧基单体(a4)的具体例,例如可以举出(甲基)丙烯酸、(甲基)丙烯酸羧乙酯、(甲基)丙烯酸羧戊酯、衣康酸、马来酸、富马酸、丁烯酸等。上述含羧基单体(a4)之中,从共聚性、价格和粘合特性的观点出发,优选丙烯酸。
含羟基单体(a5)是在其结构中具有羟基且包含(甲基)丙烯酰基、乙烯基等聚合性不饱和双键的化合物。作为含羟基单体(a5)的具体例,例如可以举出:(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸3-羟基丙酯、(甲基)丙烯酸4-羟基丁酯、(甲基)丙烯酸6-羟基己酯、(甲基)丙烯酸8-羟基辛酯、(甲基)丙烯酸10-羟基癸酯、(甲基)丙烯酸12-羟基月桂酯等(甲基)丙烯酸羟烷基酯、丙烯酸(4-羟甲基环己基)甲酯等。上述含羟基单体(a5)之中,从耐久性的方面出发,优选(甲基)丙烯酸2-羟基乙酯、(甲基)丙烯酸4-羟基丁酯,特别优选(甲基)丙烯酸4-羟基丁酯。
这些共聚单体在粘合剂组合物含有交联剂的情况下形成与交联剂的反应点。含羧基单体(a4)、含羟基单体(a5)富有与分子间交联剂的反应性,因此优选用于提高所得粘合剂层的凝聚性、耐热性。另外,含羧基单体(a4)在兼顾耐久性和返工性的方面是优选的,含羟基单体(a5)在返工性的方面是优选的。
(甲基)丙烯酸系聚合物(A)在全部构成单体(100重量%)的重量比率中包含规定量的上述各单体作为单体单元。(甲基)丙烯酸烷基酯(a1)的重量比率可以设定作为(甲基)丙烯酸烷基酯(a1)以外的单体的余量,具体来说,为70重量%以上。(甲基)丙烯酸烷基酯(a1)的重量比率可以在70~96.88重量%的范围内进行调整。将(甲基)丙烯酸烷基酯(a1)的重量比率设为上述范围在确保粘接性方面是优选的。
含芳环的(甲基)丙烯酸酯(a2)的重量比率为3~25重量%,优选为8~22重量%,更优选为12~18重量%。含芳环的(甲基)丙烯酸酯(a2)的重量比率小于3重量%时,不能充分抑制显示不均。另一方面,若大于25重量%,则对显示不均的抑制反而不充分,耐久性也下降。
含酰胺基单体(a3)的重量比率为0.1~8重量%,优选为0.3~5重量%,更优选为0.3~4重量%,进一步优选为0.7~2.5重量%。含酰胺基单体(a3)的重量比率小于1重量%时,特别是不能满足对透明导电层的耐久性。另一方面,若大于8重量%则耐久性下降,另外从返工性的方面出发也不优选。
含羧基单体(a4)的重量比率为0.01~2重量%,优选为0.05~1.5重量%,进一步优选为0.1~1重量%,最优选为0.1~0.5重量%。含羧基单体(a4)的重量比率小于0.01重量%时,不能满足耐久性。另一方面,大于2重量%的情况下,不能满足耐金属腐蚀性,另外从返工性的方面出发也不优选。
含羟基单体(a5)的重量比率为0.01~3重量%,优选为0.1~2重量%,进一步优选为0.2~2重量%。含羟基单体(a5)的重量比率小于0.01重量%时,粘合剂层变得交联不足,不能满足耐久性、粘合特性。另一方面,大于3重量%的情况下,则不能满足耐久性。
上述(甲基)丙烯酸系聚合物(A)中除了上述单体单元以外并不特别需要含有其它单体单元,但是以粘接性、耐热性的改善为目的,可以通过共聚导入1种以上的具有(甲基)丙烯酰基或乙烯基等具有不饱和双键的聚合性的官能团的共聚单体。
作为这样的共聚单体的具体例,可以举出:马来酸酐、衣康酸酐等含酸酐基单体;丙烯酸的己内酯加成物;烯丙基磺酸、2-(甲基)丙烯酰胺-2-甲基丙磺酸、(甲基)丙烯酰胺丙磺酸、(甲基)丙烯酸磺酸丙酯等含磺酸基单体;2-羟基乙基丙烯酰磷酸酯等含磷酸基单体等。
另外,也可以举出(甲基)丙烯酸氨基乙酯、(甲基)丙烯酸N,N-二甲氨基乙酯、(甲基)丙烯酸叔丁基氨基乙酯等(甲基)丙烯酸烷氨基烷基酯;(甲基)丙烯酸甲氧基乙酯、(甲基)丙烯酸乙氧基乙酯等(甲基)丙烯酸烷氧基烷基酯;N-(甲基)丙烯酰氧基亚甲基琥珀酰亚胺、N-(甲基)丙烯酰-6-氧基六亚甲基琥珀酰亚胺、N-(甲基)丙烯酰-8-氧基八亚甲基琥珀酰亚胺等琥珀酰亚胺系单体;N-环己基马来酰亚胺、N-异丙基马来酰亚胺、N-月桂基马来酰亚胺、N-苯基马来酰亚胺等马来酰亚胺系单体;N-甲基衣康酰亚胺、N-乙基衣康酰亚胺、N-丁基衣康酰亚胺、N-辛基衣康酰亚胺、N-2-乙基己基衣康酰亚胺、N-环己基衣康酰亚胺、N-月桂基衣康酰亚胺等衣康酰亚胺系单体等作为改性目标的单体例。
此外,作为改性单体,也可以使用乙酸乙烯酯、丙酸乙烯酯等乙烯基系单体;丙烯腈、甲基丙烯腈等氰基丙烯酸酯系单体;(甲基)丙烯酸缩水甘油酯等含环氧基的(甲基)丙烯酸酯;聚乙二醇(甲基)丙烯酸酯、聚丙二醇(甲基)丙烯酸酯、甲氧基乙二醇(甲基)丙烯酸酯、甲氧基聚丙二醇(甲基)丙烯酸酯等二醇系(甲基)丙烯酸酯;(甲基)丙烯酸四氢糠醇酯、氟(甲基)丙烯酸酯、硅酮(甲基)丙烯酸酯、2-甲氧基丙烯酸乙酯等(甲基)丙烯酸酯单体等。此外,可以举出异戊二烯、丁二烯、异丁烯、乙烯基醚等。
此外,作为上述以外的可共聚的单体,可以举出含有硅原子的硅烷系单体等。作为硅烷系单体,例如可以举出:3-丙烯酰氧基丙基三乙氧基硅烷、乙烯基三甲氧基硅烷、乙烯基三乙氧基硅烷、4-乙烯基丁基三甲氧基硅烷、4-乙烯基丁基三乙氧基硅烷、8-乙烯基辛基三甲氧基硅烷、8-乙烯基辛基三乙氧基硅烷、10-甲基丙烯酰氧基癸基三甲氧基硅烷、10-丙烯酰氧基癸基三甲氧基硅烷、10-甲基丙烯酰氧基癸基三乙氧基硅烷、10-丙烯酰氧基癸基三乙氧基硅烷等。
另外,作为共聚单体,也可以使用三丙二醇二(甲基)丙烯酸酯、四乙二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、双酚A二缩水甘油醚二(甲基)丙烯酸酯、新戊二醇二(甲基)丙烯酸酯、三羟甲基丙烷三(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、二季戊四醇五(甲基)丙烯酸酯、二季戊四醇六(甲基)丙烯酸酯、己内酯改性二季戊四醇六(甲基)丙烯酸酯等(甲基)丙烯酸与多元醇的酯化物等具有2个以上的(甲基)丙烯酰基、乙烯基等不饱和双键的多官能性单体;在聚酯、环氧、氨基甲酸酯等骨架上作为与单体成分同样的官能团加成(甲基)丙烯酰基、乙烯基等不饱和双键2个以上而成的聚酯(甲基)丙烯酸酯、环氧(甲基)丙烯酸酯、氨基甲酸酯(甲基)丙烯酸酯等。
(甲基)丙烯酸系聚合物(A)中的上述共聚单体的比例在上述(甲基)丙烯酸系聚合物(A)的全部构成单体(100重量%)的重量比率中为0~10%左右、更优选为0~7%左右、进一步优选为0~5%左右。
本发明的(甲基)丙烯酸系聚合物(A)通常使用重均分子量为100万~250万的(甲基)丙烯酸系聚合物。如果考虑耐久性、尤其耐热性,则优选重均分子量为120万~200万。若重均分子量小于100万,则从耐热性的方面考虑是不优选的。另外,若重均分子量大于250万,则有粘合剂容易变硬的倾向,容易产生剥离。另外,表示分子量分布的重均分子量(Mw)/数均分子量(Mn)为1.8以上且10以下,优选为1.8~7,更优选为1.8~5。分子量分布(Mw/Mn)超过10时,从耐久性的方面考虑是不优选的。需要说明的是,重均分子量、分子量分布(Mw/Mn)通过GPC(凝胶渗透色谱)进行测定,根据利用聚苯乙烯换算算出的值求出。
这种(甲基)丙烯酸系聚合物(A)的制造可以适当选择溶液聚合、本体聚合、乳液聚合、各种自由基聚合等公知的制造方法。另外,所得的(甲基)丙烯酸系聚合物(A)可以是无规共聚物、嵌段共聚物、接枝共聚物等中的任意种。
需要说明的是,在溶液聚合中,作为聚合溶剂,例如可以使用乙酸乙酯、甲苯等。作为具体的溶液聚合例,反应在氮等惰性气体气流下加入聚合引发剂并通常在50~70℃左右、5~30小时左右的反应条件下进行。
对于用于自由基聚合的聚合引发剂、链转移剂、乳化剂等没有特别限定,可以适当选择使用。需要说明的是,(甲基)丙烯酸系聚合物(A)的重均分子量能够通过聚合引发剂、链转移剂的使用量、反应条件进行控制,根据他们的种类适当调整其使用量。
作为聚合引发剂,可列举例如:2,2’-偶氮二异丁腈、2,2’-偶氮双(2-脒基丙烷)二盐酸盐、2,2’-偶氮双[2-(5-甲基-2-咪唑啉-2-基)丙烷]二盐酸盐、2,2’-偶氮双(2-甲基丙脒)二硫酸盐、2,2’-偶氮双(N,N’-二亚甲基异丁基脒)、2,2’-偶氮双[N-(2-羧基乙基)-2-甲基丙脒]水合物(和光纯药公司制、VA-057)等偶氮系引发剂、过硫酸钾、过硫酸铵等过硫酸盐、过氧化二碳酸二(2-乙基己基)酯、过氧化二碳酸二(4-叔丁基环己基)酯、过氧化二碳酸二仲丁酯、过氧化新癸酸叔丁酯、过氧化特戊酸叔己酯、过氧化新戊酸叔丁酯、二过氧化月桂酰、二正辛酰基过氧化物、过氧化-2-乙基己酸1,1,3,3-四甲基丁酯、二(4-甲基苯甲酰基)过氧化物、二过氧化苯甲酰、过氧化异丁酸叔丁酯、1,1-二(叔己基过氧化)环己烷、叔丁基过氧化氢、过氧化氢等过氧化物系引发剂、过硫酸盐与亚硫酸氢钠的组合、过氧化物与抗坏血酸钠的组合等将过氧化物与还原剂组合的氧化还原系引发剂等,但不限于此。
上述聚合引发剂可以单独使用,另外也可以混合使用2种以上,整体上的含量相对于单体100重量份优选为0.005~1重量份左右,更优选为0.02~0.5重量份左右。
需要说明的是,使用例如2,2’-偶氮二异丁腈作为聚合引发剂来制造上述重均分子量的(甲基)丙烯酸系聚合物(A)时,聚合引发剂的使用量相对于单体成分的总量100重量份优选为0.06~0.2重量份左右,更优选为0.08~0.175重量份左右。
作为链转移剂,例如可以举出月桂基硫醇、缩水甘油基硫醇、巯基乙酸、2-巯基乙醇、巯基乙酸、巯基乙酸2-乙基己酯、2,3-二巯基-1-丙醇等。链转移剂可以单独使用,另外也可以混合使用2种以上,整体上的含量相对于单体成分的总量100重量份为0.1重量份左右以下。
另外,作为进行乳液聚合时使用的乳化剂,例如可以举出:十二烷基硫酸钠、十二烷基硫酸铵、十二烷基苯磺酸钠、聚氧乙烯烷基醚硫酸铵、聚氧乙烯烷基苯基醚硫酸钠等阴离子系乳化剂、聚氧乙烯烷基醚、聚氧乙烯烷基苯基醚、聚氧乙烯脂肪酸酯、聚氧乙烯-聚氧丙烯嵌段聚合物等非离子系乳化剂等。这些的乳化剂可以单独使用也可以并用2种以上。
此外,作为反应性乳化剂,作为导入有丙烯基、烯丙醚基等自由基聚合性官能团的乳化剂,具体来说,例如有アクア口ンHS-10、HS-20、KH-10、BC-05、BC-10、BC-20(以上均为第一工业制药公司制)、アデ力リアソ一プSE10N(旭电化工公司制)等。反应性乳化剂在聚合后被带入聚合物链,因此耐水性变好从而优选反应性乳化剂。乳化剂的使用量相对于单体成分的总量100重量份为0.3~5重量份,从聚合稳定性、机械的稳定性出发更优选0.5~1重量份。
本发明的粘合剂组合物含有交联剂(B)。作为交联剂(B),可以使用有机系交联剂、多官能性金属螯合物。作为有机系交联剂,可以举出异氰酸酯系交联剂、过氧化物系交联剂、环氧系交联剂、亚胺系交联剂等。多官能性金属螯合物是多价金属与有机化合物共价键合或配位键合的物质。作为多价金属原子,可以举出Al、Cr、Zr、Co、Cu、Fe、Ni、V、Zn、In、Ca、Mg、Mn、Y、Ce、Sr、Ba、Mo、La、Sn、Ti等。作为进行共价键合或配位键合的有机化合物中的原子,可以举出氧原子等,作为有机化合物,可以举出烷基酯、醇化合物、羧酸化合物、醚化合物、酮化合物等。
作为交联剂(B),优选异氰酸酯系交联剂和/或过氧化物系交联剂。
作为异氰酸酯系交联剂(B),可以使用至少具有2个异氰酸酯基的化合物。例如,可以使用通常可用于氨基甲酸酯化反应的公知的脂肪族多异氰酸酯、脂环族多异氰酸酯、芳香族多异氰酸酯等。
作为脂肪族多异氰酸酯,例如可以举出:三亚甲基二异氰酸酯、四亚甲基二异氰酸酯、六亚甲基二异氰酸酯、五亚甲基二异氰酸酯、1,2-丙烯二异氰酸酯、1,3-亚丁基二异氰酸酯、十二亚甲基二异氰酸酯、2,4,4-三甲基六亚甲基二异氰酸酯等。
作为脂环族异氰酸酯,例如可以举出:1,3-环戊烯二异氰酸酯、1,3-环己烷二异氰酸酯、1,4-环己烷二异氰酸酯、异佛尔酮二异氰酸酯、氢化二苯基甲烷二异氰酸酯、氢化苯二亚甲基二异氰酸酯、氢化甲苯二异氰酸酯、氢化四甲基苯二甲基二异氰酸酯等。
作为芳香族二异氰酸酯,例如可以举出:苯二异氰酸酯、2,4-亚甲苯基二异氰酸酯、2,6-亚甲苯基二异氰酸酯、2,2’-二苯基甲烷二异氰酸酯、4,4’-二苯基甲烷二异氰酸酯、4,4’-甲苯胺二异氰酸酯、4,4’-二苯基醚二异氰酸酯、4,4’-二苯基二异氰酸酯、1,5-萘二异氰酸酯、苯二亚甲基二异氰酸酯等。
另外,作为异氰酸酯系交联剂(B),可以举出上述二异氰酸酯的低聚物(二聚物、三聚物、五聚物等)、与三羟甲基丙烷等多元醇反应的氨基甲酸酯改性物、脲改性物、缩二脲改性物、脲基甲酸酯改性物、异氰脲酸酯改性物、碳二亚胺改性物等。
作为异氰酸酯系交联剂(B)的市售品,例如可以举出:商品名“ミリ才ネ一トMT”“ミリ才ネ一トMTL”“ミリ才ネ一トMR-200”“ミリ才ネ一トMR-400”“コロネートL”“コロネートHL”“コロネートHX”[以上日本聚氨酯工业公司制];商品名“TAKENATE D-110N”“TAKENATE D-120N”“TAKENATE D-140N”“TAKENATE D-160N”“TAKENATE D-165N”“TAKENATE D-170HN”“TAKENATE D-178N”“TAKENATE 500”“TAKENATE 600”[以上为三井化学公司制];等。这些化合物可以单独使用,另外也可以混合使用2种以上。
作为异氰酸酯系交联剂(B),优选脂肪族多异氰酸酯及作为其改性物的脂肪族多异氰酸酯系化合物。脂肪族多异氰酸酯系化合物与其它异氰酸酯系交联剂相比,交联结构富于柔软性,容易缓和与光学膜的膨胀/收缩相伴的应力,在耐久性试验中不容易产生剥离。作为脂肪族多异氰酸酯系化合物,特别优选六亚甲基二异氰酸酯及其改性物。
作为过氧化物,只要是通过加热或光照射产生自由基活性物种而使粘合剂组合物的基础聚合物的交联推进的物质就能够适当地使用,考虑到作业性和稳定性,优选使用1分钟半衰期温度为80℃~160℃的过氧化物,更优选使用1分钟半衰期温度为90℃~140℃的过氧化物。
作为可使用的过氧化物,例如可以举出:过氧化二碳酸二(2-乙基己基)酯(1分钟半衰期温度:90.6℃)、过氧化二碳酸二(4-叔丁基环己基)酯(1分钟半衰期温度:92.1℃)、过氧化二碳酸二仲丁酯(1分钟半衰期温度:92.4℃)、过氧化新癸酸叔丁酯(1分钟半衰期温度:103.5℃)、过氧化特戊酸叔己酯(1分钟半衰期温度:109.1℃)、过氧化新戊酸叔丁酯(1分钟半衰期温度:110.3℃)、二过氧化月桂酰(1分钟半衰期温度:116.4℃)、二正辛酰基过氧化物(1分钟半衰期温度:117.4℃)、过氧化-2-乙基己酸1,1,3,3-四甲基丁酯(1分钟半衰期温度:124.3℃)、二(4-甲基苯甲酰基)过氧化物(1分钟半衰期温度:128.2℃)、二过氧化苯甲酰(1分钟半衰期温度:130.0℃)、过氧化异丁酸叔丁酯(1分钟半衰期温度:136.1℃)、1,1-二(叔己基过氧化)环己烷(1分钟半衰期温度:149.2℃)等。其中,尤其从交联反应效率优异出发,优选使用过氧化二碳酸二(4-叔丁基环己基)酯(1分钟半衰期温度:92.1℃)、二过氧化月桂酰(1分钟半衰期温度:116.4℃)、二过氧化苯甲酰(1分钟半衰期温度:130.0℃)等。
需要说明的是,过氧化物的半衰期是表示过氧化物的分解速度的指标,是指过氧化物的残留量达到一半为止的时间。关于用于以任意的时间得到半衰期的的分解温度、任意的温度下的半衰期时间,在制造商目录等中有记载,例如记载于日本油脂株式会社的“有机过氧化物目录第9版(2003年5月)”等。
交联剂(B)的使用量相对于(甲基)丙烯酸系聚合物(A)100重量份优选为0.01~3重量份,更优选为0.02~2重量份,进一步优选为0.03~1重量份。需要说明的是,交联剂(B)不足0.01重量份时,粘合剂层变得交联不足,有不能满足耐久性、粘合特性的风险,另一方面,若大于3重量份,则可观察到粘合剂层变得过硬而耐久性下降的倾向。
上述异氰酸酯系交联剂可以单独使用1种,另外也可以混合使用2种以上,整体上的含量为相对于上述(甲基)丙烯酸系聚合物(A)100重量份优选含有0.01~2重量份的上述异氰酸酯系交联剂,更优选含有0.02~2重量份,进一步优选含有0.05~1.5重量份。可以考虑凝聚力、耐久性试验中的剥离的阻止等而适当含有。
上述过氧化物可以单独使用1种,另外也可以混合使用2种以上,整体上的含量为相对于上述(甲基)丙烯酸系聚合物(A)100重量份含有上述过氧化物0.01~2重量份,优选含有0.04~1.5重量份,更优选含有0.05~1重量份。为了调整加工性、返工性、交联稳定性、剥离性等,在该范围内适当选择。
需要说明的是,作为反应处理后的残留的过氧化物分解量的测定方法,例如可以通过HPLC(高效液相色谱)进行测定。
更具体而言,例如可以将反应处理后的粘合剂组合物每次取出约0.2g,浸渍于乙酸乙酯10mL,用振荡机在25℃下、120rpm下进行3小时振荡萃取后,在室温静置3天。接着,加入乙腈10mL,在25℃下、120rpm下振荡30分种,将利用膜过滤器(0.45μm)进行过滤得到的萃取液约10μL注入HPLC进行分析,作为反应处理后的过氧化物量。
本发明的粘合剂组合物中可以含有硅烷偶联剂(C)。通过使用硅烷偶联剂(C),可以提高耐久性。作为硅烷偶联剂,具体来说例如可以举出:3-缩水甘油醚氧基丙基三甲氧基硅烷、3-缩水甘油醚氧基丙基三乙氧基硅烷、3-环氧丙氧基丙基甲基二乙氧基硅烷、2-(3,4-环氧环己基)乙基三甲氧基硅烷等含环氧基的硅烷偶联剂、3-氨基丙基三甲氧基硅烷、N-2-(氨基乙基)-3-氨基丙基甲基二甲氧基硅烷、3-三乙氧基甲硅烷基-N-(1,3-二甲基亚丁基)丙胺、N-苯基-γ-氨基丙基三甲氧基硅烷等含氨基的硅烷偶联剂、3-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等含(甲基)丙烯酰基的硅烷偶联剂、3-异氰酸酯丙基三乙氧基硅烷等含异氰酸酯基的硅烷偶联剂等。作为上述例示的硅烷偶联剂,优选含环氧基的硅烷偶联剂。
另外,作为硅烷偶联剂(C),也可以使用在分子内具有多个烷氧基甲硅烷基的硅烷偶联剂。具体来说,例如可以举出信越化学公司制X-41-1053、X-41-1059A、X-41-1056、X-41-1805、X-41-1818、X-41-1810、X-40-2651等。这些在分子内具有多个烷氧基甲硅烷基的硅烷偶联剂不容易挥发,由于具有多个烷氧基甲硅烷基因而对提高耐久性有效,是优选的。特别是,带粘合剂层的光学膜的被粘物是与玻璃相比烷氧基甲硅烷基难以反应的透明导电层(例如ITO等)的情况下,耐久性是适宜的。另外,在分子内具有多个烷氧基甲硅烷基的硅烷偶联剂优选在分子内具有环氧基,进一步优选在分子内具有多个环氧基。在分子内具有多个烷氧基甲硅烷基且具有环氧基的硅烷偶联剂在被粘物为透明导电层(例如ITO等)的情况下也有耐久性良好的倾向。作为在分子内具有多个烷氧基甲硅烷基且具有环氧基的硅烷偶联剂的具体例,可以举出信越化学公司制X-41-1053、X-41-1059A、X-41-1056,特别优选环氧基含量多的信越化学公司制X-41-1056。
上述硅烷偶联剂(C)可以单独使用,另外也可以混合使用2种以上,整体上的含量相对于上述(甲基)丙烯酸系聚合物(A)100重量份优选为0.001~5重量份的上述硅烷偶联剂,更优选0.01~1重量份,进一步优选0.02~1重量份,更进一步优选0.05~0.6重量份。这是提高耐久性、适度地保持对玻璃和透明导电层的粘接力的量。
本发明的粘合剂组合物可以含有离子性化合物(D)。作为离子性化合物(D),可以优选地使用碱金属盐和/或有机阳离子-阴离子盐。碱金属盐可以使用碱金属的有机盐和无机盐。需要说明的是,本发明中所称的“有机阳离子-阴离子盐”表示其阳离子部由有机物构成的有机盐,阴离子部可以为有机物也可以为无机物。“有机阳离子-阴离子盐”也被称作离子液体、离子性固体。
<碱金属盐>
作为构成碱金属盐的阳离子部的碱金属离子,可以举出锂、钠、钾各离子。这些碱金属离子之中优选锂离子。
碱金属盐的阴离子部可以由有机物构成,也可以由无机物构成。作为构成有机盐的阴离子部,例如可以举出CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)3C-、C4F9SO3 -、C3F7COO-、(CF3SO2)(CF3CO)N-、-O3S(CF2)3SO3 -、PF6 -、CO3 2-、由下述通式(1)至(4)表示的阴离子部等。
(1):(CnF2n+1SO2)2N-(其中,n为1~10的整数)、
(2):CF2(CmF2mSO2)2N-(其中,m为1~10的整数)、
(3):-O3S(CF2)lSO3 -(其中,l为1~10的整数)、
(4):(CpF2p+1SO2)N-(CqF2q+1SO2)(其中,p、q为1~10的整数)。尤其包含氟原子的阴离子部由于可得到离子解离性好的离子化合物因而优选使用。作为构成无机盐的阴离子部,可以使用Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、ClO4 -、NO3 -、AsF6 -、SbF6 -、NbF6 -、TaF6 -、(CN)2N-等。作为阴离子部,优选(CF3SO2)2N-、(C2F5SO2)2N-等由上述通式(1)表示的(全氟烷基磺酰基)酰亚胺,特别优选由(CF3SO2)2N-表示的(三氟甲磺酰基)酰亚胺。
作为碱金属的有机盐,具体来说,可以举出乙酸钠、海藻酸钠、木质素磺酸钠、甲苯磺酸钠、LiCF3SO3、Li(CF3SO2)2N、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(C4F9SO2)2N、Li(CF3SO2)3C、KO3S(CF2)3SO3K、LiO3S(CF2)3SO3K等,这些之中优选LiCF3SO3、Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(C4F9SO2)2N、Li(CF3SO2)3C等,更优选Li(CF3SO2)2N、Li(C2F5SO2)2N、Li(C4F9SO2)2N等含氟的锂酰亚胺盐,特别优选(全氟烷基磺酰基)酰亚胺锂盐。
另外,作为碱金属的无机盐,可以举出高氯酸锂、碘化锂。
<有机阳离子-阴离子盐>
在本发明中使用的有机阳离子-阴离子盐由阳离子成分和阴离子成分构成,上述阳离子成分包含有机物。作为阳离子成分,具体来说,可以举出吡啶鎓阳离子、哌啶鎓阳离子、吡咯烷鎓阳离子、具有吡咯啉骨架的阳离子、具有吡咯骨架的阳离子、咪唑鎓阳离子、四氢嘧啶鎓阳离子、二氢嘧啶鎓阳离子、吡唑鎓阳离子、噻唑鎓阳离子、四烷基铵阳离子、三烷基锍阳离子、四烷基鏻阳离子等。
作为阴离子成分,例如可使用Cl-、Br-、I-、AlCl4 -、Al2Cl7 -、BF4 -、PF6 -、ClO4 -、NO3 -、CH3COO-、CF3COO-、CH3SO3 -、CF3SO3 -、(CF3SO2)3C-、AsF6 -、SbF6 -、NbF6 -、TaF6 -、(CN)2N-、C4F9SO3 -、C3F7COO-、((CF3SO2)(CF3CO)N-、-O3S(CF2)3SO3 -、下述通式(1)至(4)所示的阴离子成分等。
(1):(CnF2n+1SO2)2N-(其中,n为1~10的整数)、
(2):CF2(CmF2mSO2)2N-(其中,m为1~10的整数)、
(3):-O3S(CF2)lSO3 -(其中,l为1~10的整数)、
(4):(CpF2p+1SO2)N-(CqF2q+1SO2)(其中,p、q为1~10的整数)。其中,尤其包含氟原子的阴离子成分由于可得到离子解离性良好的离子化合物而优选使用。
作为有机阳离子-阴离子盐的具体例,可以从包含上述阳离子成分和阴离子成分的组合的化合物适当选择使用。
例如,1-丁基吡啶鎓四氟硼酸盐、1-丁基吡啶鎓六氟磷酸盐、1-丁基-3-甲基吡啶鎓四氟硼酸盐、1-丁基-3-甲基吡啶鎓三氟甲磺酸盐、1-丁基-3-甲基吡啶鎓双(三氟甲磺酰基)酰亚胺、1-丁基-3-甲基吡啶鎓双(五氟乙磺酰基)酰亚胺、1-己基吡啶鎓四氟硼酸盐、2-甲基-1-吡咯啉四氟硼酸盐、1-乙基-2-苯基吲哚四氟硼酸盐、1,2-二甲基吲哚四氟硼酸盐、1-乙基咔唑四氟硼酸盐、1-乙基-3-甲基咪唑鎓四氟硼酸盐、1-乙基-3-甲基咪唑鎓乙酸酯、1-乙基-3-甲基咪唑鎓三氟乙酸酯、1-乙基-3-甲基咪唑鎓七氟丁酸盐、1-乙基-3-甲基咪唑鎓三氟甲磺酸盐、1-乙基-3-甲基咪唑鎓全氟丁磺酸盐、1-乙基-3-甲基咪唑鎓二氰胺、1-乙基-3-甲基咪唑鎓双(三氟甲磺酰基)酰亚胺、1-乙基-3-甲基咪唑鎓双(五氟乙磺酰基)酰亚胺、1-乙基-3-甲基咪唑鎓三(三氟甲磺酰基)甲基化物、1-丁基-3-甲基咪唑鎓四氟硼酸盐、1-丁基-3-甲基吡咯烷鎓六氟磷酸盐、1-丁基-3-甲基咪唑鎓三氟乙酸酯、1-丁基-3-甲基咪唑鎓七氟丁酸盐、1-丁基-3-甲基咪唑鎓三氟甲磺酸盐、1-丁基-3-甲基咪唑鎓全氟丁磺酸盐、1-丁基-3-甲基咪唑鎓双(三氟甲磺酰基)酰亚胺、1-己基-3-甲基咪唑鎓溴盐、1-己基-3-甲基咪唑鎓氯盐、1-己基-3-甲基咪唑鎓四氟硼酸盐、1-己基-3-甲基吡咯烷鎓六氟磷酸盐、1-己基-3-甲基咪唑鎓三氟甲磺酸盐、1-辛基-3-甲基咪唑鎓四氟硼酸盐、1-辛基-3-甲基吡咯烷鎓六氟磷酸盐、1-己基-2,3-二甲基咪唑鎓四氟硼酸盐、1,2-二甲基-3-丙基咪唑鎓双(三氟甲磺酰基)酰亚胺、1-甲基吡唑鎓四氟硼酸盐、3-甲基吡唑鎓四氟硼酸盐、四己基铵双(三氟甲磺酰基)酰亚胺、二烯丙基二甲基铵四氟硼酸盐、二烯丙基二甲基铵三氟甲磺酸盐、二烯丙基二甲基铵双(三氟甲磺酰基)酰亚胺、二烯丙基二甲基铵双(五氟乙磺酰基)酰亚胺、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)铵四氟硼酸盐、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)铵三氟甲磺酸盐、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)铵双(三氟甲磺酰基)酰亚胺、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)铵双(五氟乙磺酰基)酰亚胺、缩水甘油基三甲基铵三氟甲磺酸盐、缩水甘油基三甲基铵双(三氟甲磺酰基)酰亚胺、缩水甘油基三甲基铵双(五氟乙磺酰基)酰亚胺、1-丁基吡啶鎓(三氟甲磺酰基)三氟乙酰胺、1-丁基-3-甲基吡啶鎓(三氟甲磺酰基)三氟乙酰胺、1-乙基-3-甲基咪唑鎓(三氟甲磺酰基)三氟乙酰胺、N,N-二乙基-N-甲基-N-(2-甲氧基乙基)铵(三氟甲磺酰基)三氟乙酰胺、二烯丙基二甲基铵(三氟甲磺酰基)三氟乙酰胺、缩水甘油基三甲基铵(三氟甲磺酰基)三氟乙酰胺、N,N-二甲基-N-乙基-N-丙基铵双(三氟甲磺酰基)酰亚胺、N,N-二甲基-N-乙基-N-丁基铵双(三氟甲磺酰基)酰亚胺、N,N-二甲基-N-乙基-N-戊基铵双(三氟甲磺酰基)酰亚胺、N,N-二甲基-N-乙基-N-己基铵双(三氟甲磺酰基)酰亚胺、N,N-二甲基-N-乙基-N-庚基铵双(三氟甲磺酰基)酰亚胺、N,N-二甲基-N-乙基-N-壬基铵双(三氟甲磺酰基)酰亚胺、N,N-二甲基-N,N-二丙基铵双(三氟甲磺酰基)酰亚胺、N,N-二甲基-N-丙基-N-丁基铵双(三氟甲磺酰基)酰亚胺、N,N-二甲基-N-丙基-N-戊基铵双(三氟甲磺酰基)酰亚胺、N,N-二甲基-N-丙基-N-己基铵双(三氟甲磺酰基)酰亚胺、N,N-二甲基-N-丙基-N-庚基铵双(三氟甲磺酰基)酰亚胺、N,N-二甲基-N-丁基-N-己基铵双(三氟甲磺酰基)酰亚胺、N,N-二甲基-N-丁基-N-庚基铵双(三氟甲磺酰基)酰亚胺、N,N-二甲基-N-戊基-N-己基铵双(三氟甲磺酰基)酰亚胺、N,N-二甲基-N,N-二己基铵双(三氟甲磺酰基)酰亚胺、三甲基庚基铵双(三氟甲磺酰基)酰亚胺、N,N-二乙基-N-甲基-N-丙基铵双(三氟甲磺酰基)酰亚胺、N,N-二乙基-N-甲基-N-戊基铵双(三氟甲磺酰基)酰亚胺、N,N-二乙基-N-甲基-N-庚基铵双(三氟甲磺酰基)酰亚胺、N,N-二乙基-N-丙基-N-戊基铵双(三氟甲磺酰基)酰亚胺、三乙基丙基铵双(三氟甲磺酰基)酰亚胺、三乙基戊基铵双(三氟甲磺酰基)酰亚胺、三乙基庚基铵双(三氟甲磺酰基)酰亚胺、N,N-二丙基-N-甲基-N-乙基铵双(三氟甲磺酰基)酰亚胺、N,N-二丙基-N-甲基-N-戊基铵双(三氟甲磺酰基)酰亚胺、N,N-二丙基-N-丁基-N-己基铵双(三氟甲磺酰基)酰亚胺、N,N-二丙基-N,N-二己基铵双(三氟甲磺酰基)酰亚胺、N,N-二丁基-N-甲基-N-戊基铵双(三氟甲磺酰基)酰亚胺、N,N-二丁基-N-甲基-N-己基铵双(三氟甲磺酰基)酰亚胺、三辛基甲基铵双(三氟甲磺酰基)酰亚胺、N-甲基-N-乙基-N-丙基-N-戊基铵双(三氟甲磺酰基)酰亚胺、1-丁基-3-甲基吡啶-1-鎓三氟甲烷磺酸盐等。作为这些的市售品,例如可以使用“CIL-314”(JapanCarlit Co制)、“ILA2-1”(广荣化学社制)等。
另外,例如可以举出四甲基铵双(三氟甲磺酰基)酰亚胺、三甲基乙基铵双(三氟甲磺酰基)酰亚胺、三甲基丁基铵双(三氟甲磺酰基)酰亚胺、三甲基戊基铵双(三氟甲磺酰基)酰亚胺、三甲基庚基铵双(三氟甲磺酰基)酰亚胺、三甲基辛基铵双(三氟甲磺酰基)酰亚胺、四乙基铵双(三氟甲磺酰基)酰亚胺、三乙基丁基铵双(三氟甲磺酰基)酰亚胺、四丁基铵双(三氟甲磺酰基)酰亚胺、四己基铵双(三氟甲磺酰基)酰亚胺等。
另外,例如可以举出:1-二甲基吡咯烷鎓双(三氟甲磺酰基)酰亚胺、1-甲基-1-乙基吡咯烷鎓双(三氟甲磺酰基)酰亚胺、1-甲基-1-丙基吡咯烷鎓双(三氟甲磺酰基)酰亚胺、1-甲基-1-丁基吡咯烷鎓双(三氟甲磺酰基)酰亚胺、1-甲基-1-戊基吡咯烷鎓双(三氟甲磺酰基)酰亚胺、1-甲基-1-己基吡咯烷鎓双(三氟甲磺酰基)酰亚胺、1-甲基-1-庚基吡咯烷鎓双(三氟甲磺酰基)酰亚胺、1-乙基-1-丙基吡咯烷鎓双(三氟甲磺酰基)酰亚胺、1-乙基-1-丁基吡咯烷鎓双(三氟甲磺酰基)酰亚胺、1-乙基-1-戊基吡咯烷鎓双(三氟甲磺酰基)酰亚胺、1-乙基-1-己基吡咯烷鎓双(三氟甲磺酰基)酰亚胺、1-乙基-1-庚基吡咯烷鎓双(三氟甲磺酰基)酰亚胺、1,1-二丙基吡咯烷鎓双(三氟甲磺酰基)酰亚胺、1-丙基-1-丁基吡咯烷鎓双(三氟甲磺酰基)酰亚胺、1,1-二丁基吡咯烷鎓双(三氟甲磺酰基)酰亚胺、1-丙基哌啶鎓双(三氟甲磺酰基)酰亚胺、1-戊基哌啶鎓双(三氟甲磺酰基)酰亚胺、1,1-二甲基哌啶鎓双(三氟甲磺酰基)酰亚胺、1-甲基-1-乙基哌啶鎓双(三氟甲磺酰基)酰亚胺、1-甲基-1-丙基哌啶鎓双(三氟甲磺酰基)酰亚胺、1-甲基-1-丁基哌啶鎓双(三氟甲磺酰基)酰亚胺、1-甲基-1-戊基哌啶鎓双(三氟甲磺酰基)酰亚胺、1-甲基-1-己基哌啶鎓双(三氟甲磺酰基)酰亚胺、1-甲基-1-庚基哌啶鎓双(三氟甲磺酰基)酰亚胺、1-乙基-1-丙基哌啶鎓双(三氟甲磺酰基)酰亚胺、1-乙基-1-丁基哌啶鎓双(三氟甲磺酰基)酰亚胺、1-乙基-1-戊基哌啶鎓双(三氟甲磺酰基)酰亚胺、1-乙基-1-己基哌啶鎓双(三氟甲磺酰基)酰亚胺、1-乙基-1-庚基哌啶鎓双(三氟甲磺酰基)酰亚胺、1,1-二丙基哌啶鎓双(三氟甲磺酰基)酰亚胺、1-丙基-1-丁基哌啶鎓双(三氟甲磺酰基)酰亚胺、1,1-二丁基哌啶鎓双(三氟甲磺酰基)酰亚胺、1,1-二甲基吡咯烷鎓双(五氟乙磺酰基)酰亚胺、1-甲基-1-乙基吡咯烷鎓双(五氟乙磺酰基)酰亚胺、1-甲基-1-丙基吡咯烷鎓双(五氟乙磺酰基)酰亚胺、1-甲基-1-丁基吡咯烷鎓双(五氟乙磺酰基)酰亚胺、1-甲基-1-戊基吡咯烷鎓双(五氟乙磺酰基)酰亚胺、1-甲基-1-己基吡咯烷鎓双(五氟乙磺酰基)酰亚胺、1-甲基-1-庚基吡咯烷鎓双(五氟乙磺酰基)酰亚胺、1-乙基-1-丙基吡咯烷鎓双(五氟乙磺酰基)酰亚胺、1-乙基-1-丁基吡咯烷鎓双(五氟乙磺酰基)酰亚胺、1-乙基-1-戊基吡咯烷鎓双(五氟乙磺酰基)酰亚胺、1-乙基-1-己基吡咯烷鎓双(五氟乙磺酰基)酰亚胺、1-乙基-1-庚基吡咯烷鎓双(五氟乙磺酰基)酰亚胺、1,1-二丙基吡咯烷鎓双(五氟乙磺酰基)酰亚胺、1-丙基-1-丁基吡咯烷鎓双(五氟乙磺酰基)酰亚胺、1,1-二丁基吡咯烷鎓双(五氟乙磺酰基)酰亚胺、1-丙基哌啶鎓双(五氟乙磺酰基)酰亚胺、1-戊基哌啶鎓双(五氟乙磺酰基)酰亚胺、1,1-二甲基哌啶鎓双(五氟乙磺酰基)酰亚胺、1-甲基-1-乙基哌啶鎓双(五氟乙磺酰基)酰亚胺、1-甲基-1-丙基哌啶鎓双(五氟乙磺酰基)酰亚胺、1-甲基-1-丁基哌啶鎓双(五氟乙磺酰基)酰亚胺、1-甲基-1-戊基哌啶鎓双(五氟乙磺酰基)酰亚胺、1-甲基-1-己基哌啶鎓双(五氟乙磺酰基)酰亚胺、1-甲基-1庚基哌啶鎓双(五氟乙磺酰基)酰亚胺、1-乙基-1-丙基哌啶鎓双(五氟乙磺酰基)酰亚胺、1-乙基-1-庚基哌啶鎓双(五氟乙磺酰基)酰亚胺,1-乙基-1-戊基哌啶鎓双(五氟乙磺酰基)酰亚胺、1-乙基-1-己基哌啶鎓双(五氟乙磺酰基)酰亚胺、1-乙基-1-庚基哌啶鎓双(五氟乙磺酰基)酰亚胺、1-丙基-1-丁基哌啶鎓双(五氟乙磺酰基)酰亚胺、1,1-二丙基哌啶鎓双(五氟乙磺酰基)酰亚胺、1,1-二丁基哌啶鎓双(五氟乙磺酰基)酰亚胺等。
另外,可以举出:使用三甲基锍阳离子、三乙基锍阳离子、三丁基锍阳离子、三己基锍阳离子、二乙基甲基锍阳离子、二丁基乙基锍阳离子、二甲基癸基锍阳离子、四甲基鏻阳离子、四乙基鏻阳离子、四丁基鏻阳离子、四己基鏻阳离子代替上述化合物的阳离子成分后的化合物等。
另外,可以举出:使用双(五氟磺酰基)酰亚胺、双(七氟丙磺酰基)酰亚胺、双(九氟丁磺酰基)酰亚胺、三氟甲磺酰基九氟丁磺酰亚胺、七氟丙磺酰基三氟甲磺酰亚胺、五氟乙磺酰基九氟丁磺酰亚胺、六氟环丙烷-1,3-双(磺酰基)酰亚胺阴离子等代替上述双(三氟甲磺酰基)酰亚胺后的化合物等。
另外,作为离子性化合物(D),在上述的碱金属盐、有机阳离子-阴离子盐以外,还可以举出氯化铵、氯化铝、氯化铜、氯化亚铁、氯化铁、硫酸铵等无机盐。这些离子性化合物(D)可以单独使用也可以并用多种。
本发明的粘合剂组合物中的离子性化合物(D)的比例相对于(甲基)丙烯酸系聚合物(A)100重量份优选为0.05~10重量份。上述离子性化合物(D)不足0.05重量份时,抗静电性能的提高效果有时不充分。上述离子性化合物(D)优选为0.1重量份以上,更优选为0.5重量份以上。另一方面,上述离子性化合物(D)若大于10重量份,则有时耐久性变得不充分。上述离子性化合物(D)优选为5重量份以下,更优选为3重量份以下,进一步优选为1重量份以下。上述离子性化合物(D)的比例可以采用上述上限值或下限值来设定优选的范围。
本发明的粘合剂组合物中可以配合具有反应性甲硅烷基的聚醚化合物(E)。聚醚化合物(E)从可以提高返工性的方面考虑是优选的。聚醚化合物(E)例如可以使用日本特开2010-275522号公报中公开的聚醚化合物。
具有反应性甲硅烷基的聚醚化合物(E)具有聚醚骨架且在至少1个的末端具有下述通式(1):-SiRaM3-a所示的反应性甲硅烷基。
(式中,R为具有或不具有取代基的碳数1~20的一价有机基,M为羟基或水解性基团,a为0~2的整数。其中,存在多个R时,多个R彼此可以相同也可以不同,存在多个M时,多个M彼此可以相同也可以不同。)
作为具有上述反应性甲硅烷基的聚醚化合物(E),可以举出通式(2):RaM3-aSi-X-Y-(AO)n-Z所示的化合物。
(式中,R为具有或不具有取代基的碳数1~20的一价有机基,M为羟基或水解性基团,a为0~2的整数。其中,存在多个R时,多个R彼此可以相同也可以不同,存在多个M时,多个M彼此可以相同也可以不同。AO表示直链或支链的碳数1~10的氧亚烷基,n为1~1700,表示氧亚烷基的平均加成摩尔数。X表示碳数1~20的直链或支链的亚烷基。Y表示醚键、酯键、氨酯键或碳酸酯键。
Z表示氢原子、一价的碳数1~10的烃基、
通式(2A):-Y1-X-SiRaM3-a所示的基团、
(式中,R、M、X与上述相同。Y1表示单键、-CO-键、-CONH-键或-COO-键)、或者通式(2B):-Q{-(OA)n-Y-X-SiRaM3-a}m所示的基团
(式中,R、M、X、Y与上述相同。OA与上述的AO相同,且n与上述相同。Q是2价以上的碳数1~10的烃基,m与该烃基的价数相同)。)。
作为具有反应性甲硅烷基的聚醚化合物(E)的具体例,例如可以举出Kaneka公司制的MS聚合物S203、S303、S810;SILYL EST250、EST280;SAT10、SAT200、SAT220、SAT350、SAT400、旭硝子公司制的EXCESTAR S2410、S2420或S3430等。
本发明的粘合剂组合物中的聚醚化合物(E)的比例相对于(甲基)丙烯酸系聚合物(A)100重量份优选为0.001~10重量份。上述聚醚化合物(E)不足0.001重量份时,返工性的提高效果有时不充分。上述聚醚化合物(E)优选为0.01重量份以上,更优选为0.1重量份以上。另一方面,上述聚醚化合物(E)若大于10重量份,则从耐久性的方面考虑是不优选的。上述聚醚化合物(E)优选为5重量份以下,更优选为2重量份以下。上述聚醚化合物(E)的比例可以采用上述上限值或下限值设定优选的范围。
此外,本发明的粘合剂组合物中可以含有其它公知的添加剂,例如可以根据所使用的用途适当添加聚丙二醇等聚亚烷基二醇的聚醚化合物、着色剂、颜料等粉体、染料、表面活性剂、增塑剂、增粘剂、表面润滑剂、流平剂、软化剂、抗氧化剂、抗老化剂、光稳定剂、紫外线吸收剂、阻聚剂、无机或有机的填充剂、金属粉、粒子状物、箔状物等。另外,在可控制的范围内可以采用加入有还原剂的氧化还原系。这些添加剂相对于(甲基)丙烯酸系聚合物(A)100重量份在优选为5重量份以下、更优选为3重量份以下、进一步优选为1重量份以下的范围中使用。
利用上述粘合剂组合物形成粘合剂层,在粘合剂层的形成时,优选对交联剂整体的添加量进行调整,并且充分考虑交联处理温度、交联处理时间的影响。
交联处理温度、交联处理时间可以根据所使用的交联剂进行调整。交联处理温度优选为170℃以下。
另外,该交联处理可以在粘合剂层的干燥工序时的温度下进行,可以在干燥工序后另行设置交联处理工序来进行。
另外,关于交联处理时间,可以考虑生产率、作业性进行设定,通常为0.2~20分钟左右,优选为0.5~10分钟左右。
本发明的带粘合剂层的光学膜等带粘合剂层的光学部件中利用上述粘合剂组合物在光学膜的至少单面形成有粘合剂层。
作为形成粘合剂层的方法,例如通过如下等方法进行制作:将上述粘合剂组合物涂布于经剥离处理的分离件等,干燥除去聚合溶剂等而形成粘合剂层后转印于光学膜的方法;或者,在光学膜上涂布上述粘合剂组合物,干燥除去聚合溶剂等而在光学膜上形成粘合剂层的方法。需要说明的是,在粘合剂的涂布时,可以适当新加入除聚合溶剂以外的一种以上的溶剂。
作为经剥离处理的分隔件,优选使用硅酮剥离衬材。在这种衬材上涂布本发明的粘接剂组合物并使之干燥而形成粘合剂层的工序中,作为使粘合剂干燥的方法,根据目的可以适当采用适当的方法。优选对上述涂布膜进行加热干燥的方法。加热干燥温度优选为40℃~200℃,进一步优选为50℃~180℃,特别优选为70℃~170℃。通过将加热温度设为上述的范围,可以得到具有优异粘合特性的粘合剂。
干燥时间可适当采用适当的时间。上述干燥时间优选为5秒~20分钟,进一步优选为5秒~10分钟,特别优选10秒~5分钟。
另外,可以在光学膜的表面形成投锚层或实施电晕处理、等离子体处理等各种易粘接处理后形成粘合剂层。另外,也可以对粘合剂层的表面进行易粘接处理。
作为粘合剂层的形成方法,可以使用各种方法。具体来说,例如可以举出:辊涂、辊舐涂布、凹版涂布、逆转式涂布、辊刷、喷涂、浸渍辊涂布、棒涂、刮刀涂布、气刀涂布、帘式涂布、唇口涂布、利用模涂机等的挤出涂布法等方法。
粘合剂层的厚度没有特别限制,例如为1~100μm左右。优选为2~50μm,更优选为2~40μm,进一步优选为5~35μm。
上述粘合剂层露出的情况下,可以在供于实用之前利用经剥离处理的片材(分隔件)保护粘合剂层。
作为分隔件的构成材料,例如可以列举:聚乙烯、聚丙烯、聚对苯二甲酸乙二酯、聚酯膜等塑料膜、纸、布、无纺布等多孔质材料、网、发泡片材、金属箔和这些层叠体等适当的薄片物等,从表面平滑性优异的方面出发,优选使用塑料膜。
作为该塑料膜,只要是可保护上述粘合剂层的膜就没有特别限定,例如可以举出:聚乙烯膜、聚丙烯膜、聚丁烯膜、聚丁二烯膜、聚甲基戊烯膜、聚氯乙烯膜、氯乙烯共聚物膜、聚对苯二甲酸乙二酯膜、聚对苯二甲酸丁二酯膜、聚氨酯膜、乙烯-乙酸乙烯酯共聚物膜等。
上述分隔件的厚度通常为5~200μm,优选为5~100μm左右。对于上述分隔件,也可以根据需要进行利用硅酮系、氟系、长链烷基系或脂肪酰胺系的脱模剂、二氧化硅粉等进行的脱模和防污处理;涂布型、混炼型、蒸镀型等抗静电处理。特别是,通过适当对上述分隔件的表面进行硅酮处理、长链烷基处理、氟处理等剥离处理,可以进一步提高从上述粘合剂层的剥离性。
需要说明的是,上述的带粘合剂层的光学膜的制作时使用的经剥离处理的片材可以直接用作带粘合剂层的光学膜的分隔件,可以进行工序面中的简化。
作为光学膜,使用液晶显示装置等图像显示装置的形成中所使用的光学膜,其种类没有特别限制。例如,作为光学膜可以举出偏振膜。偏振膜通常使用在偏振片的单面或双面具有透明保护膜的偏振膜。
偏振片没有特别限定,可以使用各种偏振片。作为偏振片,例如可以举出:使聚乙烯醇系膜、部分缩甲醛化聚乙烯醇系膜、乙烯-乙酸乙烯酯共聚物系部分皂化膜等亲水性高分子膜上吸附碘、二色性染料的二色性物质并进行单轴拉伸而成的偏振片、聚乙烯醇的脱水处理物、聚氯乙烯的脱盐酸处理物等多烯系取向膜等。这些之中,包含聚乙烯醇系膜和碘等二色性物质的偏振片是适合的。这些偏振片的厚度没有特别限制,一般而言为80μm左右以下。
将聚乙烯醇系膜用碘染色并进行单轴拉伸而成的偏振片例如可以如下制造:将聚乙烯醇系膜浸渍在碘的水溶液中由此进行染色,拉伸至原长的3~7倍,由此制造。根据需要,也可以浸渍于可包含硼酸、硫酸锌、氯化锌等的碘化钾等水溶液中。此时,可以根据需要在染色前将聚乙烯醇系膜浸渍于水来进行水洗。可以通过对聚乙烯醇系膜进行水洗由此清洗聚乙烯醇系膜表面的污渍、抗粘连剂,此外通过使聚乙烯醇系膜溶胀由此还具有防止染色的不均等不均匀的效果。拉伸可以在用碘染色后进行,也可以一边染色一边进行拉伸,另外也可以在进行拉伸后用碘进行染色。在硼酸、碘化钾等水溶液、水浴中也可以进行拉伸。
另外作为偏振片,可以使用厚度为10μm以下的薄型的偏振片。从薄型化的观点出发而言,该厚度优选为1~7μm。这种薄型的偏振片由于厚度不均少、可视性优异并且尺寸变化少,因此耐久性优异、以及作为偏振膜的厚度也可薄型化,这点是优选的。
作为薄型的偏振片,典型地可列举:日本特开昭51-069644号公报、日本特开2000-338329号公报、WO2010/100917号小册子、PCT/JP2010/001460的说明书或日本特愿2010-269002号说明书、日本特愿2010-263692号说明书中记载的薄型偏振膜。这些薄型偏振膜可以通过包含如下工序的制法得到:将聚乙烯醇系树脂(以下也称作PVA系树脂)层和拉伸用树脂基材在层叠体的状态下进行拉伸的工序;和进行染色的工序。根据该制法,即便PVA系树脂层薄,通过被拉伸用树脂基材支撑,也能够在没有因拉伸所致的破裂等不良情况的情况下进行拉伸。
作为上述薄型偏振膜,从在包含在层叠体的状态下进行拉伸的工序和进行染色的工序的制法之中也能够高倍率拉伸且能够提高偏振性能的方面考虑,优选利用WO2010/100917号小册子、PCT/JP2010/001460的说明书、日本特愿2010-269002号说明书或日本特愿2010-263692号说明书所述的包含在硼酸水溶液中进行拉伸的工序的制法所得到的薄型偏振膜,特别优选利用日本特愿2010-269002号说明书、日本特愿2010-263692号说明书所述的包含在硼酸水溶液中进行拉伸前进行辅助性的空中拉伸的工序的制法所得到的薄型偏振膜。
作为构成透明保护膜的材料,例如可以使用透明性、机械强度、热稳定性、水分屏蔽性、各向同性等优异的热塑性树脂。作为这种热塑性树脂的具体例,可以举出三乙酸纤维素等纤维素树脂、聚酯树脂、聚醚砜树脂、聚砜树脂、聚碳酸酯树脂、聚酰胺树脂、聚酰亚胺树脂、聚烯烃树脂、(甲基)丙烯酸系树脂、环状聚烯烃树脂(降冰片烯系树脂)、聚芳酯树脂、聚苯乙烯树脂、聚乙烯醇树脂和这些的混合物。需要说明的是,在偏振片的单侧利用粘接剂层贴合透明保护膜,在另一单侧,可以使用(甲基)丙烯酸、氨基甲酸酯系、丙烯酸系氨基甲酸酯系、环氧系、硅酮系等热固性树脂或紫外线固化型树脂作为透明保护膜。透明保护膜中可以包含1种以上的可选的适当添加剂。作为添加剂,例如可以举出:紫外线吸收剂、抗氧化剂、润滑剂、增塑剂、脱模剂、抗着色剂、阻燃剂、核剂、抗静电剂、颜料、着色剂等。透明保护膜中的上述热塑性树脂的含量优选为50~100重量%、更优选为50~99重量%、进一步优选为60~98重量%、特别优选为70~97重量%。透明保护膜中的上述热塑性树脂的含量为50重量%以下的情况下,有可能不能充分表现热塑性树脂原本具有的高透明性等。
如果上述偏振片和透明保护膜的贴合中使用的粘接剂为光学透明,则没有特别限制,可以使用水系、溶剂系、热熔胶系、自由基固化型、阳离子固化型的各种形态的粘接剂,水系粘接剂或自由基固化型粘接剂是适宜的。
另外,作为光学膜,例如可以举出:反射板、半透板、相位差膜(包含1/2、1/4等波片)、视觉补偿膜、增亮膜等有时在液晶显示装置等的形成中所使用的形成光学层的光学膜。这些可以单独用作光学膜,此外在实用时也可以在上述偏振膜上层叠1层或2层以上使用。
在偏振膜上层叠有上述光学层的光学膜可以利用液晶显示装置等的制造过程中依次分别层叠的方式进行形成,但预先层叠形成光学膜的方式有品质的稳定性、组装作业等优异且可改善液晶显示装置等制造工序的优点。层叠可以使用粘合层等适当的粘接方式。在上述的偏振膜与其它光学层的粘接时,它们的光学轴可以根据作为目标的相位差特性等设为适当的配置角度。
本发明的带粘合剂层的光学膜可以优选地用于液晶显示装置等各种图像显示装置的形成等。液晶显示装置的形成可以依据以往进行。即,液晶显示装置通常适当装配液晶盒等显示面板与带粘合剂层的光学膜和根据需要的照明系统等构成部件,并组装驱动电路等由此形成,在本发明中,除了使用本发明的带粘合剂层的光学膜以外没有特别限定,可以依据以往。液晶盒例如也可以使用TN型、STN型、π型、VA型、IPS型等任意类型等的液晶盒。
可以形成在液晶盒等显示面板的单侧或两侧配置有带粘合剂层的光学膜的液晶显示装置、照明系统使用背光或反射板的液晶显示装置等适当的液晶显示装置。此时,本发明的带粘合剂层的光学膜可以在液晶盒等显示面板的单侧或两侧设置。在两侧设置光学膜时,它们可以相同也可以不同。此外,在液晶显示装置的形成时,例如可以在适当的位置配置1层或2层以上的扩散层、防眩层、防反射膜、保护板、棱镜阵列、棱镜阵列片、光扩散片、背光等适当部件。
实施例
以下,通过实施例具体说明本发明,本发明不限于这些实施例。需要说明的是,各例中的份和%均为重量基准。以下,没有特别规定的室温放置条件全部为23℃65%RH。
<(甲基)丙烯酸系聚合物(A)的重均分子量的测定>
(甲基)丙烯酸系聚合物(A)的重均分子量(Mw)通过GPC(凝胶渗透色谱)进行测定。对于Mw/Mn,也同样进行测定。
·分析装置:东曹公司制、HLC-8120GPC
·柱:东曹公司制、G7000HXL+GMHXL+GMHXL
·柱尺寸:各计90cm
·柱温度:40℃
·流量:0.8mL/min
·注入量:100μL
·洗脱液:四氢呋喃
·检测器:差示折射计(RI)
·标准试料:聚苯乙烯
<偏振膜的制造>
将厚度80μm的聚乙烯醇膜一边在30℃、0.3%浓度的碘溶液中进行1分钟染色,一边在速度比不同的辊间拉伸至3倍。之后,一边在60℃、包含4%浓度的硼酸、10%浓度的碘化钾的水溶液中浸渍0.5分钟一边拉伸至综合拉伸倍率为6倍。接着,通过在30℃、包含1.5%浓度的碘化钾的水溶液中浸渍10秒钟进行清洗后,在50℃进行4分钟干燥,得到了厚度30μm的偏振片。利用聚乙烯醇系粘接剂在该偏振片的双面贴合经皂化处理的厚度80μm的三乙酸纤维素膜从而制造偏振膜。
实施例1
(丙烯酸系聚合物(A1)的制备)
在具有搅拌叶片、温度计、氮气导入管、冷却器的四口烧瓶中投入含有丙烯酸丁酯74.8份、苯氧基丙烯酸乙酯23份、N-乙烯基-2-吡咯烷酮1.5份、丙烯酸0.3份、丙烯酸4-羟基丁酯0.4份的单体混合物。此外,相对于上述单体混合物(固体成分)100份,将作为聚合引发剂的2,2’-偶氮二异丁腈0.1份与乙酸乙酯100份一起投入,一边缓慢搅拌一边导入氮气进行氮置换后,将烧瓶内的液温保持在55℃附近进行8小时聚合反应,制备了重均分子量(Mw)160万、Mw/Mn=3.7的丙烯酸系聚合物(A1)的溶液。
(粘合剂组合物的制备)
相对于在制造例1中得到的丙烯酸系聚合物(A1)的溶液的固体成分100份,配合异氰酸酯交联剂(三井化学公司制的TAKENATE D160N、三羟甲基丙烷六亚甲基二异氰酸酯)0.1份、过氧化苯甲酰(日本油脂公司制的ナイパ一BMT)0.3份和γ-缩水甘油醚氧基丙基甲氧基硅烷(信越化学工业社制:KBM-403)0.2份,制备了丙烯酸系粘合剂组合物的溶液。
(带粘合剂层的偏振膜的制作)
接着,将上述丙烯酸系粘合剂组合物的溶液在经硅酮系剥离剂处理的聚对苯二甲酸乙二酯膜(分隔膜:三菱化学聚酯膜株式会社制,MRF38)的单面上涂布使得干燥后的粘合剂层的厚度为23μm,在155℃进行1分钟干燥,在分隔膜的表面形成了粘合剂层。接着,在上述中制造的偏振膜上转印形成在分隔膜上的粘合剂层,制作了带粘合剂层的偏振膜。
实施例2~29、比较例1~13
在实施例1中,如表1所示那样,改变丙烯酸系聚合物(A)的制备中使用单体的种类、其使用比例,另外控制制造条件,制备了表1所述的聚合物性状(重均分子量,Mw/Mn)的丙烯酸系聚合物的溶液。
另外,对于所得到的各丙烯酸系聚合物的溶液,除了如表1所示那样改变交联剂(B)的种类或其使用量、硅烷偶联剂(C)的种类或使用量(或不使用)以外,与实施例1同样地进行,制备了丙烯酸系粘合剂组合物的溶液。另外,使用该丙烯酸系粘合剂组合物的溶液与实施例1同样地制作了带粘合剂层的偏振板。需要说明的是,在实施例24至26、28和比较例5中,制备了以表1所示的比例配合有离子性化合物(D)的丙烯酸系聚合物的溶液,在实施例27中,制备了以表1所示的比例配合有具有反应性甲硅烷基的聚醚化合物(E)的丙烯酸系聚合物的溶液。
对于上述实施例和比较例中得到的带粘合剂层的偏振膜进行了以下的评价。评价结果示于表2中。需要说明的是,表面电阻值的测定仅对于实施例24至26、28和比较例5中得到的带粘合剂层的偏振膜进行。
<利用玻璃时的耐久性试验>
将带粘合剂层的偏振膜切断为37英寸尺寸后作为样品。使用层压机将该样品贴合于厚度0.7mm的无碱玻璃(康宁公司制,EG-XG)。接着,在50℃、0.5MPa进行15分钟高压釜处理,使上述样品完全与无丙烯酸系玻璃密合。对于实施了该处理的样品,在80℃、85℃、90℃(其中90℃仅针对实施例3、23、25、28、29和比较例4、5)的各气氛下实施500小时处理后(加热试验),另外,在60℃/90%RH、60℃/95%RH的各气氛下实施500小时处理后(加湿试验),另外,以1小时将85℃和-40℃的环境循环1次的条件实施了300个循环后(热冲击试验),由下述基准目视评价偏振板和玻璃之间的外观。
(评价基准)
◎:完全没有发泡、剥离等外观上的变化。
○:虽然轻微,但是在端部存在剥离或发泡,实用上没有问题。
△:在端部存在剥离或发泡,只要不是特别的用途,就实用上没有问题。
×:在端部存在显著剥离,实用上存在问题。
<利用ITO玻璃时的耐久性试验>
在上述<利用玻璃时的耐久性试验>中,在用作被粘物的无碱玻璃上形成结晶性ITO或非晶性ITO层后,作为<利用ITO玻璃时的耐久性试验>的被粘物。如上述那样,除了改变被粘物且在ITO层上贴合样品以外,以与上述<利用玻璃时的耐久性试验>同样的步骤实施了利用ITO玻璃时的耐久性试验。ITO层利用溅射形成。关于ITO的组成,结晶性ITO的Sn比率为10重量%,非晶性ITO的Sn比率为3重量%,样品的贴合前,各实施140℃×60分钟的加热工序。需要说明的是,ITO的Sn比率根据Sn原子的重量/(Sn原子的重量+In原子的重量)算出。
<耐金属腐蚀性>
将带粘合剂层的偏振膜切断为8mm×8mm后作为样品。将在膜表面形成有ITO层的导电性膜(商品名:ELECRYSTA(P400L)、日东电工株式会社制)切断为15mm×15mm,将该样品贴合至该导电性膜上的中央部后,在50℃、5atm进行15分钟高压釜处理后,作为耐腐蚀性的测定样品。使用后述的测定装置对所得到的测定用样品的电阻值进行测定,将其作为“初始电阻值”。
之后,将测定用样品投入60℃/90%RH的环境中500小时后,测定电阻值,作为“湿热后的电阻值”。需要说明的是,上述的电阻值使用Accent Optical Technologies公司制HL5500PC进行测定。根据如上所述进行测定的“初始电阻值”和“湿热后的电阻值”,利用下式算出“电阻值变化”。
<显示不均>
将带粘合剂层的偏振膜切断成纵420mm×横320mm的尺寸后作为样品,准备两块样品。将该样品用层压机贴合至厚度0.07mm的无碱玻璃板的双面使得形成正交尼科尔。接着,在50℃、5atm进行15分钟的高压釜处理后作为二次样品(初始)。接着,将二次样品在90℃的条件下进行了24小时的处理(加热后)。将初始和加热后的二次样品置于1万坎德拉的背光上,根据下述的基准目视评价漏光。
(评价基准)
◎:没有角不均的产生,实用上没有问题。
○:略微产生角不均,未表现在显示区域中,因而实用上没有问题。
△:角不均产生而略微表现在显示区域中,但实用上没有问题。
×:角不均产生而明显表现在显示区域中,实用上存在问题。
<导电性:表面电阻值(Ω/□)>
将带粘合剂层的偏振膜的分隔膜剥离后,测定了粘合剂表面的表面电阻值(初始)。另外,将带粘合剂层的偏振膜投入60℃/95%RH的环境中500小时后,在40℃进行1小时干燥,然后剥离分隔膜,然后测定了粘合剂表面的表面电阻值(湿热后)。测定使用MITSUBISHI CHEMICAL ANALYTECH公司制的MCP-HT450进行。
<加湿白浊>
将带粘合剂层的偏振膜切断为50mm×50mm的尺寸,贴合于玻璃。此外,将厚度25μm的PET膜(ダイアホイルT100-25B,三菱树脂公司制)切断为50mm×50mm的尺寸,贴合于偏振膜的上表面作为测定用样品。将测定用样品投入60℃/95%RH的环境中250小时后,在室温下取出,测定10分钟后的雾度值。雾度值使用村上色彩技术研究所公司制的雾度计HM150进行测定。
<返工性>
将带粘合剂层的偏振膜裁切成纵120mm×横25mm后作为样品。使用层压机将该样品贴附于厚度0.7mm的无碱玻璃板(康宁公司制,EG-XG),接着在50℃、5atm下进行15分钟高压釜处理使之完全密合后,测定了该样品的粘接力。对于粘接力而言,对于该样品,利用拉伸试验机(Autograph SHIMAZU AG-1 1OKN)在剥离角度90°、剥离速度300mm/min下对拉伸剥离时的粘接力(N/25mm、测定长度80mm)进行测定,由此求出粘接力。测定以1次/0.5s的间隔进行采样,将其平均值作为测定值。
表1
表1中,丙烯酸系聚合物(A)的制备中使用的单体表示
BA:丙烯酸丁酯、
PEA:丙烯酸苯氧基乙酯、
NVP:N-乙烯基-吡咯烷酮、
NVC:N-乙烯基-ε-己内酰胺、
AAM:丙烯酰胺、
AA:丙烯酸、
HBA:丙烯酸4-羟基丁酯、
HEA:丙烯酸2-羟基乙酯。
交联剂(B)中的“异氰酸酯系”的“D160N”表示三井化学公司制的TAKENATE D160N(三羟甲基丙烷的六亚甲基二异氰酸酯的加合物),“C/L”表示日本聚氨酯工业公司制的コロネ一トL(三羟甲基丙烷的甲苯二异氰酸酯的加合物)。
“过氧化物系”表示过氧化苯甲酰(日本油脂社制,ナイパ一BMT),
关于“硅烷偶联剂(C)”,表示
KBM403:信越化学工业株式会社制的KBM403、
X-41-1056:信越化学工业株式会社制的X-41-1056,
“离子性化合物(D)”表示
Li-TFSI:三菱材料公司制的双(三氟甲磺酰基)酰亚胺锂;
EMP-TFSI:三菱材料公司制的1-乙基-1-甲基吡咯烷鎓双(三氟甲磺酰基)酰亚胺。
“聚醚化合物(E)”表示Kaneka公司制的サイリルSAT10。
表2
Claims (17)
1.一种光学膜用粘合剂组合物,其特征在于,含有(甲基)丙烯酸系聚合物(A)、以及相对于所述(甲基)丙烯酸系聚合物(A)100重量份为0.01重量份~3重量份的交联剂(B),
所述(甲基)丙烯酸系聚合物(A)仅含有
(甲基)丙烯酸烷基酯(a1)70重量%以上、
含芳环的(甲基)丙烯酸酯(a2)3重量%~25重量%、
含酰胺基单体(a3)1重量%~8重量%、
含羧基单体(a4)0.01重量%~2重量%、和
含羟基单体(a5)0.01重量%~3重量%作为单体单元,
所述含酰胺基单体(a3)为(甲基)丙烯酰胺,
所述(甲基)丙烯酸系聚合物(A)的重均分子量Mw为100万~250万且Mw/数均分子量Mn满足1.8以上且10以下。
2.如权利要求1所述的光学膜用粘合剂组合物,其特征在于,
所述含羟基单体(a5)为(甲基)丙烯酸4-羟基丁酯。
3.如权利要求1所述的光学膜用粘合剂组合物,其特征在于,
所述交联剂(B)含有选自异氰酸酯系交联剂和过氧化物系交联剂中的至少1种。
4.如权利要求3所述的光学膜用粘合剂组合物,其特征在于,
所述异氰酸酯系交联剂含有脂肪族多异氰酸酯系化合物。
5.如权利要求1所述的光学膜用粘合剂组合物,其特征在于,还含有硅烷偶联剂(C)。
6.如权利要求5所述的光学膜用粘合剂组合物,其特征在于,
所述硅烷偶联剂(C)在1分子内具有2个以上的烷氧基甲硅烷基。
7.如权利要求5所述的光学膜用粘合剂组合物,其特征在于,
所述硅烷偶联剂(C)在分子内具有环氧基。
8.如权利要求5所述的光学膜用粘合剂组合物,其特征在于,
所述硅烷偶联剂(C)的含量相对于所述(甲基)丙烯酸系聚合物(A)100重量份为0.001重量份~5重量份。
9.如权利要求1所述的光学膜用粘合剂组合物,其特征在于,还含有离子性化合物(D)。
10.如权利要求9所述的光学膜用粘合剂组合物,其特征在于,
所述离子性化合物(D)为碱金属盐和/或有机阳离子-阴离子盐。
11.如权利要求10所述的光学膜用粘合剂组合物,其特征在于,
所述离子性化合物(D)含有含氟基的阴离子。
12.如权利要求9所述的光学膜用粘合剂组合物,其特征在于,
所述离子性化合物(D)的含量相对于所述(甲基)丙烯酸系聚合物(A)100重量份为0.05重量份~10重量份。
13.如权利要求1~12中任一项所述的光学膜用粘合剂组合物,其特征在于,
还含有具有反应性甲硅烷基的聚醚化合物(E)。
14.如权利要求13所述的光学膜用粘合剂组合物,其特征在于,
所述具有反应性甲硅烷基的聚醚化合物(E)的含量相对于所述(甲基)丙烯酸系聚合物(A)100重量份为0.001重量份~10重量份。
15.一种光学膜用粘合剂层,其特征在于,由权利要求1~14中任一项所述的光学膜用粘合剂组合物形成。
16.一种带粘合剂层的光学膜,其特征在于,
在光学膜的至少一侧形成有权利要求15所述的光学膜用粘合剂层。
17.一种图像显示装置,其特征在于,
使用了至少一张权利要求16所述的带粘合剂层的光学膜。
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CN107254269A (zh) | 2017-10-17 |
TW201945499A (zh) | 2019-12-01 |
TW201542736A (zh) | 2015-11-16 |
KR20220119189A (ko) | 2022-08-26 |
CN109321157A (zh) | 2019-02-12 |
WO2015152201A1 (ja) | 2015-10-08 |
TWI672347B (zh) | 2019-09-21 |
KR20160141750A (ko) | 2016-12-09 |
JP6106205B2 (ja) | 2017-03-29 |
US20170022396A1 (en) | 2017-01-26 |
JP2019059940A (ja) | 2019-04-18 |
JP2019056117A (ja) | 2019-04-11 |
CN109439237A (zh) | 2019-03-08 |
TWI747024B (zh) | 2021-11-21 |
CN109554143A (zh) | 2019-04-02 |
CN109439238A (zh) | 2019-03-08 |
JP6748692B2 (ja) | 2020-09-02 |
KR20220038509A (ko) | 2022-03-28 |
KR102584006B1 (ko) | 2023-10-04 |
JP6748693B2 (ja) | 2020-09-02 |
CN106133096A (zh) | 2016-11-16 |
JP2017119878A (ja) | 2017-07-06 |
JP2015199942A (ja) | 2015-11-12 |
JP2018131626A (ja) | 2018-08-23 |
KR102434581B1 (ko) | 2022-08-22 |
CN106133096B (zh) | 2018-11-13 |
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