CN116194284A - 阻气膜和波长转换片 - Google Patents
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- CN116194284A CN116194284A CN202180063792.5A CN202180063792A CN116194284A CN 116194284 A CN116194284 A CN 116194284A CN 202180063792 A CN202180063792 A CN 202180063792A CN 116194284 A CN116194284 A CN 116194284A
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Abstract
本公开的一个方面涉及的阻气膜具有依次层叠基材、第1AlOx蒸镀层、阻气性中间层、第2AlOx蒸镀层、以及阻气性被覆层而成的结构,第1AlOx蒸镀层和第2AlOx蒸镀层的厚度均为15nm以下,阻气性中间层和阻气性被覆层的厚度均为200~400nm,阻气性被覆层的根据纳米压痕法测定的复合弹性模量在测定温度25℃下为7~11GPa、在测定温度60℃下为5~8GPa。
Description
技术领域
本公开涉及阻气膜和波长转换片。
背景技术
在有机EL显示器或使用了量子点的QD液晶显示器等显示装置和太阳能电池等中,为了防止因水蒸气或氧等引起的品质劣化,使用了阻气膜(参照专利文献1~3)。
现有技术文献
专利文献
专利文献1:日本特开2016-6789号公报
专利文献2:日本特开2010-272761号公报
专利文献3:日本特开2018-13724号公报
发明内容
本发明所要解决的课题
用于上述用途的阻气膜不仅要求阻气性,还要求透明性。例如,在QD液晶显示器中,在用于将蓝色LED转换为白色的波长转换层中使用量子点(QD),但是量子点容易劣化,因此以覆盖波长转换层的两面的方式层叠阻气膜。在这种情况下,根据阻气膜的透明性、特别是泛黄(yellowness)的强度而转换的发光颜色发生变化,因此要求阻气膜减少泛黄。此外,在用于上述用途的阻气膜中,从提高透明性和抑制颜色不均等的观点来看,要求抑制褶皱,外观良好。
本公开是鉴于上述情况而完成的,其目的在于提供水蒸气阻隔性优异、能够减少泛黄、能够抑制褶皱的产生的阻气膜、以及使用了该阻气膜的波长转换片。
用于解决课题的手段
为了实现上述目的,本公开提供了一种阻气膜,具有依次层叠基材、第1AlOx蒸镀层、阻气性中间层、第2AlOx蒸镀层、以及阻气性被覆层而成的结构,上述第1AlOx蒸镀层和上述第2AlOx蒸镀层的厚度均为15nm以下,上述阻气性中间层和上述阻气性被覆层的厚度均为200~400nm,上述阻气性被覆层的根据纳米压痕法测定的复合弹性模量在测定温度25℃下为7~11GPa、在测定温度60℃下为5~8GPa。
根据上述阻气膜,通过具有上述层叠结构、各层的厚度在上述范围内、并且阻气性被覆层满足上述复合弹性模量的条件,可以得到优异的氧/水蒸气阻隔性、并且能够减少泛黄,能够抑制褶皱的产生。另外,通过使第1和第2AlOx蒸镀层的厚度为15nm以下、并且使阻气性中间层和阻气性被覆层的厚度为200~400nm,特别是在波长转换片的转换效率方面的影响大的蓝色LED的波长区域(300~400nm)中,可以减少阻气性中间层和阻气性被覆层与第1和第2AlOx蒸镀层之间的界面处的反射和干涉。此外,通过分别分开设置第1AlOx蒸镀层和第2AlOx蒸镀层、以及阻气性中间层和阻气性被覆层,可以使各层的厚度变薄,能够抑制褶皱和裂纹的产生,并且能够确保赋予阻气性的层的总厚度,因而能够得到良好的阻气性。另外,通过使阻气性被覆层的复合弹性模量在上述范围内,可以兼具对氧/水蒸气的阻气性和基材因热处理等而变形时的变形耐性。
在上述阻气膜中,优选的是,上述阻气性被覆层的根据纳米压痕法测定的硬度在测定温度25℃下为1.15~1.70GPa、在测定温度60℃下为0.85~1.30GPa。通过使阻气性被覆层满足上述硬度的条件,可以得到更优异的氧/水蒸气阻隔性,并且能够进一步减少泛黄,能够进一步抑制褶皱的产生。
在上述阻气膜中,优选的是,对上述基材的上述第1AlOx蒸镀层侧的表面进行等离子体处理。通过使用对第1AlOx蒸镀层侧的表面进行了等离子体处理的基材,可以提高基材与第1AlOx蒸镀层的密合性,从而能够抑制这些层间的剥离。另外,通过使用对第1AlOx蒸镀层侧表面进行了等离子体处理的基材,可以通过等离子体处理提高层间的密合性,而不用形成锚固涂层等之类的用于提高密合性的层,因此与设置锚固涂层等的情况相比,可以提高光透过性。
在上述阻气膜中,优选的是,上述阻气性被覆层是使用含有选自由含羟基高分子化合物、金属醇盐、硅烷偶联剂以及它们的水解产物组成的组中的至少1种的阻气性被覆层形成用组合物而形成的层。通过使阻气性被覆层形成用组合物含有上述成分,容易将阻气性被覆层的复合弹性模量和硬度控制在上述范围内,并且能够得到更优异的氧/水蒸气阻隔性。另外,在上述成分当中,在并用含羟基高分子化合物和金属醇盐的水解产物的情况下,在含羟基高分子化合物的羟基与金属醇盐的水解产物的羟基之间形成强的氢键,表现出更高的阻气性。
本公开还提供一种波长转换片,具备:荧光体层和配置在上述荧光体层的至少一个面上的本公开的阻气膜。
本发明的效果
根据本公开,可以提供水蒸气阻隔性优异、能够减少泛黄、能够抑制褶皱的产生的阻气膜、以及使用了该阻气膜的波长转换片。
附图说明
[图1]是示出阻气膜的一个实施方式的示意性剖面图。
[图2]是示出波长转换片的一个实施方式的示意性剖面图。
具体实施方式
以下,参照附图对本公开的实施方式进行详细地说明。需要说明的是,在附图中,对相同或相等的要素标注相同的符号,并且省略重复的说明。
[阻气膜]
图1是示出本公开的阻气膜的一个实施方式的示意性剖面图。本实施方式涉及的阻气膜100具备:基材11、设置在基材11上的第1AlOx蒸镀层13、设置在第1AlOx蒸镀层13上的阻气性中间层14、设置在阻气性中间层14上的第2AlOx蒸镀层23、以及设置在第2AlOx蒸镀层23上的阻气性被覆层24。阻气膜100具备:由第1AlOx蒸镀层13和阻气性中间层14构成的第1阻隔层15、和由第2AlOx蒸镀层23和阻气性被覆层24构成的第2阻隔层25。
(基材11)
基材11优选为高分子膜。作为高分子膜的材质,例如可以列举出:聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯及聚萘二甲酸乙二醇酯等聚酯;尼龙等聚酰胺;聚丙烯和环烯烃等聚烯烃;聚碳酸酯;以及三乙酰纤维素等,但是不限于这些。高分子膜优选为聚酯膜、聚酰胺膜或聚烯烃膜,更优选为聚酯膜或聚酰胺膜,进一步优选为聚对苯二甲酸乙二醇酯膜。从透明性、加工适应性以及密合性的观点来看,优选为聚对苯二甲酸乙二醇酯膜。另外,从透明性和阻气性的观点来看,聚对苯二甲酸乙二醇酯膜优选为双轴拉伸聚对苯二甲酸乙二醇酯膜。
根据需要,基材11可以包含防静电剂、紫外线吸收剂、增塑剂以及润滑剂等添加剂。另外,也可以在基材11的第1AlOx蒸镀层13侧的表面11a上设置锚固涂层。锚固涂层例如可以通过使用选自聚酯树脂、异氰酸酯树脂、氨基甲酸酯树脂、丙烯酸树脂、聚乙烯醇树脂、乙烯乙烯醇树脂、乙烯基改性树脂、环氧树脂、含噁唑啉基的树脂、改性苯乙烯树脂、改性有机硅树脂或烷基钛酸酯等中的树脂来形成。锚固涂层可以通过单独使用上述树脂、或者使用组合两种以上上述树脂而成的复合树脂来形成。锚固涂层的厚度例如为0.001μm以上2μm以下。特别是,通过设置为在基材11成膜时串联(in-line)形成锚固涂层并拉伸而得到的带有锚固涂层(易粘接层)的基材膜,能够使锚固涂层的厚度非常薄(例如0.02μm以下),因此可以减少锚固涂层中的能量损耗。
另外,也可以对基材11的第1AlOx蒸镀层13侧的表面11a实施电晕处理、火焰处理以及等离子体处理等表面处理。特别是,通过在表面处理后的面上直接设置AlOx蒸镀层13,与设置锚固涂层等的情况相比,锚固涂层等中没有能量损耗,因此能够提高光透过性。作为等离子体处理,优选以下的反应性离子蚀刻处理。
基材11可以具备通过对其表面11a进行反应性离子蚀刻(以下也称为“RIE”)处理而形成的改性处理层。改性处理层是指通过对基材11的表面附近进行RIE处理而改性为层状的形态的部位。
RIE处理利用等离子体。通过等离子体中产生的自由基或离子,可以获得对基材11表面赋予官能团的化学效果。另外,通过离子蚀刻除去表面杂质,而且还可以获得使表面粗糙度增大的物理效果。因此,通过利用RIE处理表现出上述化学效果和上述物理效果的改性处理层,基材11与第1AlOx蒸镀层13之间的密合性提高,即使在高温高湿环境下,基材11与第1AlOx蒸镀层13之间也难以产生剥离。
对基材11的RIE处理可以使用作为RIE方式的等离子体处理装置的公知装置来实施。作为该等离子体处理装置,优选卷取式的串联(in-line)等离子体处理装置。作为卷取式的串联等离子体处理装置,可以使用平面型等离子体处理装置、空心阳极型等离子体处理装置等。
对基材11的厚度没有特别地限定,优选为3μm以上100μm以下、更优选为5μm以上50μm以下。当该厚度为3μm以上时,容易进行加工,当其为100μm以下时,可以使阻气膜的总厚度变薄。
(第1AlOx蒸镀层13和第2AlOx蒸镀层23)
在本实施方式中,第1AlOx蒸镀层13通过蒸镀而形成在基材11上。另外,第2AlOx蒸镀层23通过蒸镀而形成在阻气性中间层14上。第1AlOx蒸镀层13和第2AlOx蒸镀层23是包含AlOx(氧化铝)的层。AlOx的透明性高,容易减少泛黄,因此优选。这里,从容易得到良好的阻气性、且容易减少泛黄的观点来看,x的值优选为0.01~2.00、更优选为1.00~1.90。第1AlOx蒸镀层13和第2AlOx蒸镀层23可以是相同的构成、也可以是不同的构成。
作为形成第1AlOx蒸镀层13和第2AlOx蒸镀层23时的蒸镀法,例如可以使用电阻加热式真空蒸镀法、EB(Electron Beam,电子束)加热式真空蒸镀法、感应加热式真空蒸镀法等。
第1AlOx蒸镀层13和第2AlOx蒸镀层23的膜厚均为15nm以下,优选为13nm以下。通过将该膜厚设为上述上限值以下,可以提高阻气膜的透明性,从而可以减少泛黄。另一方面,第1AlOx蒸镀层13和第2AlOx蒸镀层23的膜厚均优选为5nm以上、更优选为8nm以上。通过将该膜厚设为上述下限值以上,可以得到更良好的阻气性。
(阻气性中间层14和阻气性被覆层24)
在本实施方式中,阻气性中间层14和阻气性被覆层24是为了防止后续工序中的二次的各种损伤并且赋予高阻气性而设置的。阻气性中间层14和阻气性被覆层24可以是相同的构成、也可以是不同的构成。
阻气性中间层14和阻气性被覆层24优选是使用含有选自由含羟基高分子化合物、金属醇盐、硅烷偶联剂以及它们的水解产物组成的组中的至少1种的组合物而形成的层。具有该构成的阻气性中间层14和阻气性被覆层24可以通过使用以含有选自由含羟基高分子化合物、金属醇盐、硅烷偶联剂以及它们的水解产物组成的组中的至少1种的水溶液或水/醇混合溶液为主剂的组合物(以下,也称为涂布剂)来形成。从进一步提高阻气性的观点来看,涂布剂优选至少含有硅烷偶联剂或其水解产物;更优选含有选自由含羟基高分子化合物、金属醇盐以及它们的水解产物组成的组中的至少1种、以及硅烷偶联剂或其水解产物;进一步优选含有含羟基高分子化合物或其水解产物、金属醇盐或其水解产物、以及硅烷偶联剂或其水解产物。涂布剂例如可以通过以下方式制备:在将作为水溶性高分子的含羟基高分子化合物溶解于水系(水或者水/醇混合)溶剂而成的溶液中,将金属醇盐和硅烷偶联剂直接混合,或者将预先进行水解等处理后的物质混合。
对用于形成阻气性中间层14和阻气性被覆层24的涂布剂中所含的各成分进行详细的说明。作为涂布剂中所使用的含羟基高分子化合物,可以列举出聚乙烯醇、聚乙烯吡咯烷酮、淀粉、甲基纤维素、羧甲基纤维素、海藻酸钠等。这些当中,当在阻气性中间层14和阻气性被覆层24的涂布剂中使用聚乙烯醇(以下简称为PVA)的情况下,阻气性特别优异,因此优选。
从得到优异的阻气性的观点来看,阻气性中间层14和阻气性被覆层24优选由含有选自由下述通式(1)所表示的金属醇盐及其水解产物组成的组中的至少1种的组合物来形成。
M(OR1)m(R2)n-m···(1)
在上述通式(1)中,R1和R2均独立地为碳原子数为1~8的1价有机基团,优选为甲基、乙基等烷基。M表示Si、Ti、Al、Zr等n价的金属原子。m是1~n的整数。需要说明的是,在存在多个R1或R2的情况下,R1彼此之间或R2彼此之间可以相同、也可以不同。
作为金属醇盐,具体而言,可以列举出四乙氧基硅烷[Si(OC2H5)4]、三异丙氧基铝[Al(O-2’-C3H7)3]等。四乙氧基硅烷和三异丙氧基铝水解后在水系的溶剂中相对稳定,因此优选。
作为硅烷偶联剂,可以列举出由下述通式(2)所表示的化合物。通过使用由下述通式(2)所表示的硅烷偶联剂,可以进一步提高阻气膜的耐水性、耐热性
Si(OR11)p(R12)3-pR13···(2)
在上述通式(2)中,R11表示甲基、乙基等烷基,R12表示被烷基、芳烷基、芳基、烯基、丙烯酰氧基取代的烷基、或者被甲基丙烯酰氧基取代的烷基等1价有机基团,R13表示1价的有机官能团,p表示1~3的整数。需要说明的是,在存在多个R11或R12的情况下,R11彼此之间或R12彼此之间可以相同、也可以不同。作为由R13所表示的1价的有机官能团,可以列举出含有缩水甘油氧基、环氧基、巯基、羟基、氨基、被卤素原子取代的烷基、或异氰酸酯基的1价的有机官能团。
作为硅烷偶联剂,具体而言,可以列举出:乙烯基三甲氧基硅烷、γ-氯丙基甲基二甲氧基硅烷、γ-氯丙基三甲氧基硅烷、3-环氧丙氧基丙基甲基二甲氧基硅烷、3-环氧丙氧基丙基三甲氧基硅烷、3-环氧丙氧基丙基甲基二乙氧基硅烷、3-环氧丙氧基丙基甲基三乙氧基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-甲基丙烯酰氧基丙基甲基二甲氧基硅烷等硅烷偶联剂等。
另外,硅烷偶联剂可以是由上述通式(2)所表示的化合物聚合而成的多聚体。作为多聚体,优选三聚体、更优选1,3,5-三(3-三烷氧基甲硅烷基烷基)异氰脲酸酯。这是3-异氰酸酯基烷基烷氧基硅烷的缩聚物。已知的是,在该1,3,5-三(3-三烷氧基甲硅烷基烷基)异氰脲酸酯中,异氰酸基部分没有化学反应性,但是因脲酸基部分的极性而确保了反应性。已知的是,通常,与3-异氰酸酯基烷基烷氧基硅烷同样地添加到粘接剂等中,以作为粘接性提高剂。因此,通过将1,3,5-三(3-三烷氧基甲硅烷基烷基)异氰脲酸酯添加到含羟基高分子化合物中,可以因氢键而提高阻气性中间层14和阻气性被覆层24的耐水性。3-异氰酸酯基烷基烷氧基硅烷的反应性高、液体稳定性低,与此相对,1,3,5-三(3-三烷氧基甲硅烷基烷基)异氰脲酸酯因脲酸基部分的极性而不具有水溶性,但是容易在水系溶液中分散,从而可以稳定地保持液体粘度。另外,3-异氰酸酯基烷基烷氧基硅烷与1,3,5-三(3-三烷氧基甲硅烷基烷基)异氰脲酸酯的耐水性能相同。
1,3,5-三(3-三烷氧基甲硅烷基烷基)异氰脲酸酯可以通过3-异氰酸酯基丙基烷氧基硅烷的热缩合来制造,有时也含有原料3-异氰酸酯基丙基烷氧基硅烷,但是没有特别的问题。更优选为1,3,5-三(3-三烷氧基甲硅烷基丙基)异氰脲酸酯、进一步优选为1,3,5-三(3-三甲氧基甲硅烷基丙基)异氰脲酸酯。该甲氧基的水解速度快,并且能够相对廉价地得到含丙基的物质,因此1,3,5-三(3-三甲氧基甲硅烷基丙基)异氰脲酸酯在实用上是有利的。
另外,在不损害阻气性的范围内,根据需要,涂布剂中还可以添加异氰酸酯化合物、或分散剂、稳定剂、粘度调节剂等公知的添加剂。
用于形成阻气性中间层14和阻气性被覆层24的涂布剂例如可以通过浸渍法、辊涂法、凹版涂布法、逆转凹版涂布法、气刀涂布法、逗号涂布法、模涂法、丝网印刷法、喷涂法、凹版胶印法等进行涂布。涂布该涂布剂而成的涂膜例如可以通过热风干燥法、热辊干燥法、高频照射法、红外线照射法、UV照射法或它们的组合来进行干燥。
使上述涂膜干燥时的温度例如可以设为温度50~150℃、优选设为温度70~100℃。通过将干燥时的温度设在上述范围内,可以进一步抑制在第1AlOx蒸镀层13和第2AlOx蒸镀层23、阻气性中间层14和阻气性被覆层24中产生裂纹,从而能够表现出优异的阻气性。
阻气性中间层14和阻气性被覆层24的厚度以固化后的膜厚计均为200~400nm、优选为230~380nm、更优选为250~350nm。通过将该膜厚设为上述上限值以下,可以提高阻气膜的透明性、可以减少泛黄,同时能够抑制在阻气性中间层14和阻气性被覆层24中产生褶皱。另一方面,通过将该膜厚设为上述下限值以上,可以得到良好的阻气性。
阻气性中间层14和阻气性被覆层24的合计厚度优选为400~800nm、更优选为450~600nm。另外,阻气性中间层14的厚度与阻气性被覆层24的厚度也可以不同。阻气性中间层14的厚度相对于阻气性被覆层24的厚度的比(阻气性中间层14的厚度/阻气性被覆层24的厚度)可以为1.0~2.0、也可以超过1.0且为2.0以下、也可以为1.1~1.5。通过使阻气性被覆层24的厚度与阻气性中间层14的厚度相同或更薄,容易进一步抑制褶皱的产生,并且容易使阻气性被覆层24变得更硬。
在本实施方式中,阻气性被覆层24的根据纳米压痕法测定的复合弹性模量在测定温度25℃下为7~11GPa、在测定温度60℃下为5~8GPa。另外,优选的是,阻气性被覆层24的根据纳米压痕法测定的硬度在测定温度25℃下为1.15~1.70GPa、在测定温度60℃下为0.85~1.30GPa。阻气性被覆层24的复合弹性模量和硬度可以通过上述涂布剂的组成(特别是硅烷偶联剂的量)、或根据形成层时的加热温度控制交联密度等来进行调整。
在本说明书中,阻气性被覆层24的上述复合弹性模量和硬度表示根据纳米压痕法算出的复合弹性模量和硬度。纳米压痕法是指对目标测定对象进行准静态压入试验,以获得试样的机械特性的测定法。复合弹性模量和硬度例如可以通过以下的装置进行测定。
测定装置使用了安装有作为转换器的nanoDMA III transducer(商品名)的Bruker Japan K.K.制造的Hysitron TI-Premier(商品名)。压头使用了前端开口角为142.3°的Berkovich型金刚石加热用压头TI-0283(商品名)。测定温度使用Bruker JapanK.K.制造的加热台xSol 400(商品名)来进行控制。温度控制时的升温速度设为20℃/分钟,在加热台达到所期望的温度后,保持10分钟后实施测定。另外,预先对作为标准试样的熔融石英进行试验,并且对接触深度与接触投影面积的关系进行校正。关于纳米压痕法的测定条件,通过准静态试验以30nm/秒的压入速度压入至深度30nm后,在最大深度保持1秒,然后以30nm/秒的速度卸荷。通过分析60~95%区域的卸荷曲线相对于卸荷时的最大载荷的结果,根据Oliver-Pharr法计算复合弹性模量和硬度。
阻气性被覆层24的根据纳米压痕法测定的复合弹性模量在测定温度25℃下为7~11GPa、优选为7.5~10.5GPa。另外,阻气性被覆层24的根据纳米压痕法测定的复合弹性模量在测定温度60℃下为5~8GPa、优选为5.5~7.5GPa。通过使该复合弹性模量为上述上限值以下,能够抑制在阻气性被覆层24中产生褶皱,通过使其为上述下限值以上,能够得到良好的阻气性。
阻气性被覆层24的根据纳米压痕法测定的硬度在测定温度25℃下优选为1.15~1.70GPa、更优选为1.20~1.65GPa。另外,阻气性被覆层24的根据纳米压痕法测定的硬度在测定温度60℃下优选为0.85~1.30GPa、更优选为0.90~1.30GPa。通过使该硬度为上述上限值以下,能够进一步抑制在阻气性被覆层24中产生褶皱,通过使其为上述下限值以上,能够得到更良好的阻气性。
以上,对本公开的阻气膜的优选的一个实施方式进行了说明,但是本公开的阻气膜不限于上述实施方式。阻气膜可以在基材11与第1AlOx蒸镀层13之间、第1AlOx蒸镀层13与阻气性中间层14之间、阻气性中间层14与第2AlOx蒸镀层23之间、以及第2AlOx蒸镀层23与阻气性被覆层24之间的任一者中具备也可以不具备其他层。在不具备其他层的情况下,上述各层分别接触。另外,除了第1阻隔层15和第2阻隔层25以外,阻气膜还可以进一步具备其他阻隔层。但是,当阻隔层的层叠数增加时,透明性容易降低,并且随着形成层时的加热次数的增加,阻气膜容易产生褶皱和卷曲。因此,阻气膜优选仅具备第1阻隔层15和第2阻隔层25作为阻隔层。另外,阻气膜还可以具备以下的哑光层。
(哑光层)
为了发挥1个以上的光学功能和防静电功能,在阻气膜的最表面设置哑光层。例如,在阻气膜用于在波长转换片中保护荧光体层的情况下,哑光层设置在阻气膜的与荧光体层侧相反一侧的表面上。这里,作为光学功能,没有特别地限定,可以列举出:防止干涉条纹(云纹)功能、防止反射功能、扩散功能等。这些当中,哑光层优选至少具有防止干涉条纹功能作为光学功能。在本实施方式中,对哑光层至少具有防止干涉条纹功能的情况进行说明。
哑光层可以含有粘合剂树脂和微粒而构成。并且,也可以通过以使得微粒的一部分从哑光层的表面露出来的方式将微粒埋入粘合剂树脂中,从而在哑光层的表面产生微细的凹凸。通过在阻气膜的表面设置这样的哑光层,能够更充分地防止牛顿环等干涉条纹的产生,结果,能够得到高效率且高精细、长寿命的波长转换片。
作为粘合剂树脂,没有特别地限定,可以使用光学透明性优异的树脂。更具体而言,例如可以使用聚酯系树脂、丙烯酸系树脂、丙烯酸氨基甲酸酯系树脂、聚酯丙烯酸酯系树脂、聚氨酯丙烯酸酯系树脂、氨基甲酸酯系树脂、环氧系树脂、聚碳酸酯系树脂、聚酰胺系树脂、聚酰亚胺系树脂、三聚氰胺系树脂、酚醛系树脂等热塑性树脂、热固性树脂、电离放射线固化性树脂等。另外,除了有机树脂以外,还可以使用二氧化硅粘合剂。这些当中,从材料的广泛性来看,优选使用丙烯酸系树脂、氨基甲酸酯系树脂;从耐光性和光学特性优异的观点来看,更优选使用丙烯酸系树脂。这些不仅可以使用1种,也可以多种组合使用。
作为微粒,没有特别地限定,例如可以使用二氧化硅、粘土、滑石、碳酸钙、硫酸钙、硫酸钡、氧化钛、氧化铝等无机微粒;以及其他的苯乙烯树脂、氨基甲酸酯树脂、有机硅树脂、丙烯酸树脂、聚酰胺树脂等有机微粒。这些当中,作为微粒,使用由二氧化硅、丙烯酸树脂、氨基甲酸酯树脂、聚酰胺树脂等构成的折射率为1.40~1.55的微粒在透过率方面是优选的。折射率低的微粒价格高,另一方面,折射率过高的微粒倾向于损害透过率。这些不仅可以使用1种,也可以多种组合使用。
微粒的平均粒径优选为0.1~30μm、更优选为0.5~10μm。当微粒的平均粒径为0.1μm以上时,倾向于得到优异的防止干涉条纹功能,当其为30μm以下时,倾向于进一步提高透明性。
以哑光层总量为基准,哑光层中的微粒的含量优选为0.5~30质量%、更优选为3~10质量%。当微粒的含量为0.5质量%以上时,倾向于进一步提高光扩散功能和防止干涉条纹的产生的效果,当其为30质量%以下时,不会使亮度降低。
哑光层可以通过涂布包含上述粘合剂树脂和微粒的涂布液并使其干燥固化来形成。作为涂布方法,可以列举出利用凹版涂布机、浸涂机、逆转涂布机、线棒涂布机以及模涂机等的涂布方法。
哑光层的厚度优选为0.1~20μm、更优选为0.3~10μm。通过使哑光层的厚度为0.1μm以上,容易得到均匀的膜,倾向于容易充分地得到光学功能。另一方面,通过使哑光层的厚度为20μm以下,在哑光层中使用微粒的情况下,微粒向哑光层的表面露出,倾向于容易获得赋予凹凸的效果。
具有以上说明的构成的本实施方式的阻气膜可以用于需要与氧或水蒸气的透过有关的阻气性的用途。本实施方式的阻气膜例如对于食品及药品等的包装材料、使用量子点的QD液晶显示器等液晶显示器的背光用的波长转换片、有机电致发光(有机EL)显示器的密封部件、有机EL照明的波长转换片、以及太阳能电池的保护片等是有用的,特别适合用于液晶显示器的背光用的波长转换片。
[波长转换片]
图2是示出本公开的波长转换片的一个实施方式的示意性剖面图。图2所示的波长转换片包含量子点等荧光体,例如,可以用于作为LED波长转换用的背光单元。
图2所示的波长转换片200示意性地构成为具备:包含荧光体的荧光体层(波长转换层)7、和分别设置在荧光体层7的一个面7a侧和另一个面7b侧的阻气膜100、100。由此,成为在阻气膜100、100之间包裹(即,密封)有荧光体层7的结构。这里,由于需要对荧光体层7赋予阻气性,因此优选设置为利用一对阻气膜100、100夹持荧光体层7而成的结构。以下,对构成波长转换片200的各层进行详细地说明。
(阻气膜)
作为阻气膜100、100,可以使用图1所示的阻气膜100。在波长转换片200中,配置在荧光体层7的一个面7a侧的阻气膜100与配置在另一个面7b侧的阻气膜100可以相同、也可以不同。
阻气膜100、100可以如图2所示的那样以使得阻气性被覆层24与荧光体层7相对的方式配置,也可以以使得基材11与荧光体层7相对的方式配置。从进一步抑制由氧和水蒸气引起的荧光体层7的劣化的观点来看,阻气膜100、100优选以使得阻气性被覆层24与荧光体层7相对的方式配置。阻气性被覆层24与荧光体层7也可以直接接触。另外,为了提高阻气性被覆层24与荧光体层7的密合性,也可以在阻气性被覆层24上设置底漆层。阻气膜100也可以利用粘接剂与其他膜(例如聚对苯二甲酸乙二醇酯膜)粘贴而用作层压膜。另外,阻气膜100也可以层叠2层以上使用。
(荧光体层)
荧光体层7是包含密封树脂9和荧光体8的厚度为数十~数百μm的薄膜。作为密封树脂9,例如可以使用感光性树脂或热固性树脂。在密封树脂9的内部,荧光体8以混合1种以上的状态而被密封。在将荧光体层7和一对阻气膜100、100层叠时,密封树脂9将它们接合起来,并且发挥填埋它们之间的空隙的作用。另外,荧光体层7也可以是将仅密封有1种荧光体8的荧光体层层叠两层以上而成的结构。对于在这些1层或两层以上的荧光体层中所使用的两种以上的荧光体8而言,选择激发波长相同的荧光体。该激发波长基于由LED光源射出的光的波长来选择。两种以上的荧光体8的荧光色相互不同。在使用蓝色LED(峰值波长450nm)作为LED光源并且使用2种荧光体8的情况下,各荧光色优选为红色、绿色。各荧光的波长及由LED光源射出的光的波长基于滤色片的分光特性来选择。关于荧光的峰值波长,例如,红色为650nm,绿色为550nm。
接着,对荧光体8的粒子结构进行说明。作为荧光体8,优选使用颜色纯度高、能够期待亮度提高的量子点。作为量子点,例如可以列举出作为发光部的核由作为保护膜的壳被覆而成的物质。作为上述核,例如可以列举出硒化镉(CdSe)等,作为上述壳,例如可以列举出硫化锌(ZnS)等。CdSe粒子的表面缺陷被带隙大的ZnS所被覆,由此量子效率提高。另外,荧光体8也可以是核被第1壳和第2壳双重地被覆的结构。在这种情况下,核可以使用CdSe,第1壳可以使用硒化锌(ZnSe),第2壳可以使用ZnS。另外,作为除了量子点以外的荧光体8,也可以使用YAG:Ce等。
上述荧光体8的平均粒径优选为1~20nm。另外,荧光体层7的厚度优选为1~500μm。
以荧光体层7总量为基准,荧光体层7中的荧光体8的含量优选为1~20质量%、更优选为3~10质量%。
作为密封树脂9,例如可以使用热塑性树脂、热固性树脂、以及紫外线固化型树脂等。这些树脂可以单独地使用1种,也可以2种以上组合使用。
作为热塑性树脂,例如可以使用醋酸纤维素、硝酸纤维素、乙酸丁酸纤维素、乙基纤维素以及甲基纤维素等纤维素衍生物;乙酸乙烯酯及其共聚物、氯乙烯及其共聚物、以及偏二氯乙烯及其共聚物等乙烯基系树脂;聚乙烯醇缩甲醛及聚乙烯醇缩丁醛等缩醛树脂;丙烯酸树脂及其共聚物、甲基丙烯酸树脂及其共聚物等丙烯酸类树脂;聚苯乙烯树脂;聚酰胺树脂;线状聚酯树脂;氟树脂;以及聚碳酸酯树脂等。
作为热固性树脂,可以列举出酚醛树脂、尿素三聚氰胺树脂、聚酯树脂以及有机硅树脂等。
作为紫外线固化型树脂,可以列举出环氧丙烯酸酯、氨基甲酸酯丙烯酸酯、以及聚酯丙烯酸酯等光聚合性预聚物。另外,也可以将这些光聚合性预聚物作为主要成分,并使用单官能或多官能的单体作为稀释剂。
实施例
以下,列举实施例并对本公开进行具体地说明,但是本公开不限于这些。
[实施例1~6和比较例1~6]
<阻气膜的制作>
首先,作为基材,准备了厚度为12μm的双轴拉伸聚对苯二甲酸乙二醇酯膜。使用平面型等离子体处理装置,在基材的一个面上通过RIE处理在基材上形成改性处理层。接着,在改性处理层上形成第1AlOx蒸镀层。第1AlOx蒸镀层是通过在改性处理层上真空蒸镀氧化铝而形成的。具体而言,使用利用电子束加热方式的真空蒸镀装置,在向该装置中导入氧气的同时使金属铝蒸发。由此,形成了预定膜厚的第1AlOx蒸镀层。接着,依次形成阻气性中间层、第2AlOx蒸镀层、阻气性被覆层。第2AlOx蒸镀层通过与第1AlOx蒸镀层同样的方法形成。作为阻气性中间层和阻气性被覆层,根据各实施例和比较例使用了以下的涂层A和B。通过以上的方法,得到了具有依次层叠有基材/第1AlOx蒸镀层/阻气性中间层/第2AlOx蒸镀层/阻气性被覆层的结构的阻气膜。
(涂层A)
将下述所示的A液、B液及C液以A液/B液/C液=70/20/10(固体成分质量比)混合而成的溶液通过凹版涂布法进行涂布并使其干燥,形成了预定厚度的阻气性中间层或阻气性被覆层。
(涂层B)
将下述所示的A液和B液以A液/B液=70/30(固体成分质量比)混合而成的溶液通过凹版涂布法进行涂布并使其干燥,形成了预定厚度的阻气性中间层或阻气性被覆层。
A液:在17.9g的四乙氧基硅烷和10g的甲醇中加入72.1g的0.1N盐酸,搅拌30分钟使其水解而得的固体成分为5质量%(换算为SiO2)的水解溶液。
B液:含有5质量%的聚乙烯醇的水/甲醇=95/5(质量比)水溶液。
C液:用水/异丙醇的混合液(水:异丙醇的质量比为1:1)将1,3,5-三(3-三烷氧基甲硅烷基丙基)异氰脲酸酯稀释为固体成分为5质量%而得的水解溶液。
[实施例7]
作为基材,使用在厚度为12μm的双轴拉伸聚对苯二甲酸乙二醇酯膜的层叠阻隔层一侧的表面上层叠由脂肪族聚氨酯树脂构成的厚度为0.005μm的锚固涂层而构成的基材,不进行RIE处理,除此以外,与实施例1同样地得到了阻气膜。
在各实施例和比较例中使用的涂层种类、形成阻气性中间层和阻气性被覆层时的干燥温度和时间、第1和第2AlOx蒸镀层(表中,将它们统称为“蒸镀层”)的厚度、以及阻气性中间层和阻气性被覆层(表中,将它们统称为“涂层”)的厚度如表1所示。需要说明的是,阻气性中间层和阻气性被覆层的加热干燥通过以下方式进行:将感温贴片(Heat Label)(MICRON Corp.制造)贴在干燥前的涂膜表面上,干燥后确认温度,以成为任意的温度、且以成为任意的干燥时间的方式调整烘箱温度和线速度。表1所示的干燥温度是上述感温贴片的温度。
[表1]
<复合弹性模量和硬度的测定>
在实施例和比较例中所得的阻气膜中,通过以下的方法测定阻气性被覆层的复合弹性模量和硬度。测定装置使用了安装有作为转换器的nanoDMA III transducer(商品名)的Bruker Japan K.K.制造的Hysitron TI-Premier(商品名)。压头使用了前端开口角为142.3°的Berkovich型金刚石加热用压头TI-0283(商品名)。测定温度使用Bruker JapanK.K.制造的加热台xSol 400(商品名)进行了控制。温度控制时的升温速度设为20℃/分钟,在加热台达到所期望的温度后,保持10分钟后实施测定。另外,对作为标准试样的熔融石英预先试验,并校正接触深度与接触投影面积的关系。关于纳米压痕法的测定条件,通过准静态试验以30nm/秒的压入速度压入至深度30nm后,在最大深度下保持1秒,然后以30nm/秒的速度卸荷。通过分析60~95%区域的卸荷曲线相对于卸荷时的最大载荷的结果,根据Oliver-Pharr法计算复合弹性模量和硬度。它们的结果如表2所示。
<b*的测定>
使用测色仪(Suga Test Instruments Co.,Ltd.制造、商品名:Colour Cute i),在测定条件:C光2度视野中测定实施例和比较例中所得的阻气膜的L*a*b*表色系中的色坐标b*。如果b*为0.5以下,则判断为泛黄减少。结果如表2所示。
<水蒸气透过度(WVTR)的测定>
实施例和比较例中所得的阻气膜的水蒸气透过度通过以下的方法进行测定。首先,利用丙烯酸氨基甲酸酯树脂粘接剂将25μm的聚对苯二甲酸乙二醇酯膜与实施例和比较例中所得的阻气膜的阻气性被覆层面粘贴在一起而制作了层压膜。通过使用水蒸气透过度测定装置(MOCON公司制造、商品名:PERMATRAN-W 3/34),在温度40℃、相对湿度90%的条件下测定该层压膜的水蒸气透过度。测定是对初期的层压膜和在温度60℃、相对湿度90%下保存1000小时后的层压膜进行的。测定方法根据JIS K-7126、B法(等压法),测定值以单位[g/m2·天]表示。需要说明的是,进行三次同样的测定,取其平均值。结果如表2所示。
<外观评价>
在实施例和比较例所得的阻气膜中,通过目视观察阻气性被覆层表面,基于以下的评价基准来评价外观。结果如表2所示。
A:几乎没有褶皱,整洁
B:虽然有一些褶皱,但较少且不明显
C:有许多深的褶皱,不良
[表2]
符号的说明
7…荧光体层、8…荧光体、9…密封树脂、11…基材、13…第1AlOx蒸镀层、14…阻气性中间层、15…第1阻隔层、23…第2AlOx蒸镀层、24…阻气性被覆层、25…第2阻隔层、100…阻气膜、200…波长转换片。
Claims (5)
1.一种阻气膜,具有依次层叠基材、第1AlOx蒸镀层、阻气性中间层、第2AlOx蒸镀层、以及阻气性被覆层而成的结构,
所述第1AlOx蒸镀层和所述第2AlOx蒸镀层的厚度均为15nm以下,
所述阻气性中间层和所述阻气性被覆层的厚度均为200~400nm,
所述阻气性被覆层的根据纳米压痕法测定的复合弹性模量在测定温度25℃下为7~11GPa、在测定温度60℃下为5~8GPa。
2.根据权利要求1所述的阻气膜,其中,
所述阻气性被覆层的根据纳米压痕法测定的硬度在测定温度25℃下为1.15~1.70GPa、在测定温度60℃下为0.85~1.30GPa。
3.根据权利要求1或2所述的阻气膜,其中,
对所述基材的所述第1AlOx蒸镀层侧的表面进行等离子体处理。
4.根据权利要求1至3中任一项所述的阻气膜,其中,
所述阻气性被覆层是使用含有选自由含羟基高分子化合物、金属醇盐、硅烷偶联剂以及它们的水解产物组成的组中的至少1种的阻气性被覆层形成用组合物而形成的层。
5.一种波长转换片,具备:荧光体层和配置在所述荧光体层的至少一个面上的权利要求1至4中任一项所述的阻气膜。
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