CN102365387B - 气体屏蔽膜、包含它的电子器件、气体屏蔽袋、以及气体屏蔽膜的制造方法 - Google Patents
气体屏蔽膜、包含它的电子器件、气体屏蔽袋、以及气体屏蔽膜的制造方法 Download PDFInfo
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Abstract
本发明提供一种气体屏蔽膜,与塑料薄膜(1)的各主面接触的气体屏蔽层(2)是利用催化CVD得到的SiCNFH层,满足0.01<I(SiH)/I(SiN)<0.05、0.00<I(CH)/I(SiN)<0.07、0.04<I(NH)/I(SiN)<0.08、以及0.05<I(CF)/I(SiN)<0.3的条件,或者是SiOCNH层,满足0.1<I(SiH)/I(NH)<0.9、0.0<I(CH)/I(NH)<0.3、8<I(SiN)/I(NH)<20、以及2<I(SiO2)/I(NH)<8的条件,或者是SiCNH层,满足0.01<I(SiH)/I(SiN)<0.05、0.00<I(CH)/I(SiN)<0.07、以及0.04<I(NH)/I(SiN)<0.08的条件。这里,I表示有关附记在其后的括号内的原子键的傅立叶变换红外分光光谱的峰强度。
Description
技术领域
本发明涉及为了保护各种物品以实现对其特性的维持而防止不希望的气体侵入的气体屏蔽膜、利用它的物品、以及该气体屏蔽膜的制造方法。
背景技术
食品、医药品、触摸面板、有机EL(电致发光)元件、无机EL元件、太阳能电池、电子纸等物品会因大气中的水蒸气或氧而变质、劣化,损害其作为商品的价值。所以,要利用不会使大气中的水分或氧透过的具有所谓的气体屏蔽特性的膜来包装或密封。
但是,对于用于如上所述的各种物品的特性维持及保护的气体屏蔽膜所要求的屏蔽特性的程度随着这些物品的种类而不同。例如,作为用于有机EL元件的气体屏蔽膜,要求非常高的屏蔽特性。但是,与之相比,在用于食品或医药品等的保护的气体屏蔽膜中,即使不具有那样高的屏蔽特性也可以利用。
另一方面,有机EL显示元件作为自发光型的显示器受到关注,然而有机发光层、电子输送层、空穴输送层等有机分子层具有与大气中的水蒸气或氧反应而劣化的致命的弱点。
所以,在现实状况下,通过在基本上不会透过水蒸气和氧的玻璃基板上形成有机EL元件,继而将该有机EL元件用金属的密封罐或玻璃覆盖来实现长寿命化。
该情况下,密封罐或密封用玻璃的成本就成为问题。作为其解决对策,需要有不是利用密封罐或密封用玻璃而是利用薄膜来形成气体屏蔽层的技术,即所谓的薄膜密封技术。
另外,如果从作为将来的商品所被期待的柔软并且轻质的显示元件的技术性观点考虑,则希望开发出不使用玻璃基板而在塑料薄膜上形成有机EL层的显示元件。
为此,就需要不会使对于有机EL层来说有害的水蒸气或氧等气体透过的气体屏蔽膜、和保护形成于其上的有机EL元件的薄膜密封技术。
所以,作为用于开发柔性有机EL元件的技术性课题,第一,需要形成与塑料薄膜密合的高屏蔽性的薄膜的技术,第二,需要借助用于保护对气体、热、等离子体等耐受性弱而易于受到损伤的有机EL层的气体屏蔽膜的薄膜密封技术。
作为意图解决这些问题的尝试,在专利文献1的日本特表2002-532850号公报中,公开了屏蔽膜的形成方法的一例。该专利文献1中公开的方法中,利用聚合物层与无机材料层的层叠结构制作屏蔽膜。该聚合物层是利用单体(典型的情况是含有丙烯酸酯的单体系)的蒸镀和其后的借助紫外线照射的光聚合来形成的。另外,作为无机材料层,利用溅射等形成二氧化硅、氧化铝、氧化钛、氧化铟、氧化锡、氮化铝、或氮化硅等的层。此外,可以认为,聚合物层主要用于有机EL元件的平坦化或填充无机材料层的缺陷,无机材料层显示出屏蔽性。
专利文献1的屏蔽膜的问题是,为了获得高屏蔽性,必须反复进行多次聚合物层与无机材料层的层叠,从而形成10微米左右的合计厚度。另外,为了制造该屏蔽膜,需要像真空蒸镀、光聚合、以及溅射那样各种处理过程和装置,因此制造设备复杂化,成本升高。此外,聚合物层自身基本上没有屏蔽性,另外,无机材料层自身一般是多孔的或多晶粒子状,因此很难充分地防止来自有机EL元件的、尤其是来自侧面的水蒸气或氧的侵入。
所以,专利文献2的日本特开2008-155585号公报公开了在塑料薄膜的至少一个主面上包含依次层叠的第一、第二、以及第三有机·无机复合层的气体屏蔽膜,这些有机·无机复合层都含有特意地导入的碳、硅、氮以及氢。在该情况下,利用等离子体CVD(化学气相淀积)形成的第一和第三有机·无机复合层与利用等离子体CVD或Cat-CVD(催化CVD)形成的第二有机·无机复合层相比,具有更大的碳组成比。另外,在第二有机·无机复合层中,与第一和第三有机·无机复合层相比,将硅与氮的合计组成比设定得更大。
而且,有机·无机复合材料是指有机材料与无机材料的组合,然而与以往所知的复合物(composite)材料之类的单纯的混合物不同,其混合为纳米量级或分子量级的材料被特称为有机·无机复合材料(例如参照专利文献3的日本特开2005-179693号公报)。
专利文献1:日本特表2002-532850号公报
专利文献2:日本特开2008-155585号公报
专利文献3:日本特开2005-179693号公报
专利文献2中公开的气体屏蔽膜与专利文献1中公开的屏蔽膜相比,只要包含相当少的层叠数的气体屏蔽层就可以发挥优异的气体屏蔽性。另外,专利文献2中公开的气体屏蔽膜与专利文献1中公开的屏蔽膜相比,可以简便地并且低成本地制作。
但是,在气体屏蔽膜的技术领域中,希望进一步提高气体屏蔽膜的屏蔽性和进一步实现其制造的简便化和低成本化。
发明内容
所以,本发明的目的在于,与专利文献2中公开的气体屏蔽膜相比,实现屏蔽性的进一步的提高、以及制造的进一步的简便化和低成本化。
本发明的气体屏蔽膜的特征在于,包含与塑料薄膜的两个主面分别接触的气体屏蔽层,该气体屏蔽层是利用Cat-CVD堆积的SiCNFH层、SiOCNH层以及SiCNH层的任意一种,SiCNFH层满足0.01<I(SiH)/I(SiN)<0.05、0.00<I(CH)/I(SiN)<0.07、0.04<I(NH)/I(SiN)<0.08、以及0.05<I(CF)/I(SiN)<0.3的条件,SiOCNH层满足0.1<I(SiH)/I(NH)<0.9、0.0<I(CH)/I(NH)<0.3、8<I(SiN)/I(NH)<20、以及2<I(SiO2)/I(NH)<8的条件,此外,SiCNH层满足0.01<I(SiH)/I(SiN)<0.05、0.00<I(CH)/I(SiN)<0.07、以及0.04<I(NH)/I(SiN)<0.08的条件,这里,I表示有关附记在其后的括号内的原子键的傅立叶变换红外分光(以下记作FTIR)光谱的峰强度。
而且,优选SiCNFH层满足0.01<I(SiH)/I(SiN)<0.03、0.00<I(CH)/I(SiN)<0.02、0.05<I(NH)/I(SiN)<0.08、以及0.05<I(CF)/I(SiN)<0.25的条件,SiOCNH层满足0.1<I(SiH)/I(NH)<0.5、0.0<I(CH)/I(NH)<0.2、10<I(SiN)/I(NH)<20、以及2<I(SiO2)/I(NH)<5的条件,此外,SiCNH层满足0.01<I(SiH)/I(SiN)<0.03、0.00<I(CH)/I(SiN)<0.02、以及0.05<I(NH)/I(SiN)<0.08的条件。
另外,塑料薄膜优选为具有120℃以上的玻璃化温度或200℃以上的熔点、或者200℃以上的液晶化温度的耐热性的塑料薄膜。此外,塑料薄膜优选被进行了表面平坦化处理。
在气体屏蔽膜中,还优选在气体屏蔽层上附加地包含导电层。
通过将本发明的气体屏蔽膜作为保护层含有,就可以改善各种电子器件的耐久性。这些电子器件可以是触摸面板、有机EL器件、无机EL器件、薄膜太阳能电池、以及电子纸的任意一种。另外,使用本发明的气体屏蔽膜形成的气体屏蔽袋可以维持各种物品的特性,延长该物品的保存期间。
在制造本发明的气体屏蔽膜的方法中,可以利用使用选自有机硅烷化合物、有机氨基硅化合物、氨、氟碳、氧、以及氢中的原材料的Cat-CVD,简便并且低成本地形成气体屏蔽层。
根据本发明,通过与塑料薄膜的两个主面分别接触地利用Cat-CVD设置特定的有机·无机复合层的气体屏蔽层,就可以提供与先行技术相比能够实现屏蔽性的提高以及制造的简便化和低成本化的气体屏蔽膜。
另外,通过利用此种气体屏蔽膜,可以防止各种电子器件的特性劣化,还可以提供能够保护各种物品的气体屏蔽性的袋子。
附图说明
图1是表示本发明的一个实施方式的气体屏蔽膜的示意性剖面图。
图2是表示能够形成有机·无机复合层的Cat-CVD成膜装置的一例的示意性框图。
图3是表示在与本发明密切相关的参考例1的气体屏蔽膜中测定出的WVTR(水蒸气透过率)的时间依赖性的曲线图。
图4是表示在本发明的实施例1中堆积的SiCNFH层的FTIR的一例的曲线图。
图5是表示在实施例1中对Cat-CVD的灯丝温度进行各种改变而堆积的SiCNFH层中有关各种原子键的FTIR的吸收光谱的峰强度比的曲线图。
图6是针对图5所示的SiCNFH层表示CF原子键相对于SiN原子键的FTIR的吸收光谱强度比的曲线图。
图7是表示在本发明的实施例2中堆积的SiOCNH层的FTIR的一例的曲线图。
图8是表示在本发明的实施例3中堆积的SiCNH层的FTIR的一例的曲线图。
具体实施方式
图1以示意性剖面图表示出本发明的一个实施方式的气体屏蔽膜。该气体屏蔽膜中,在塑料薄膜1的两个主面上分别设有由特定的有机·无机复合层构成的气体屏蔽层2。
该特定的有机·无机复合层是利用Cat-CVD堆积的SiCNFH层、SiOCNH层以及SiCNH层中的任意一种,SiCNFH层满足0.01<I(SiH)/I(SiN)<0.05、0.00<I(CH)/I(SiN)<0.07、0.04<I(NH)/I(SiN)<0.08、以及0.05<I(CF)/I(SiN)<0.3的条件,SiOCNH层满足0.1<I(SiH)/I(NH)<0.9、0.0<I(CH)/I(NH)<0.3、8<I(SiN)/I(NH)<20、以及2<I(SiO2)/I(NH)<8的条件,此外,SiCNH层满足0.01<I(SiH)/I(SiN)<0.05、0.00<I(CH)/I(SiN)<0.07、以及0.04<I(NH)/I(SiN)<0.08的条件,这里,I表示有关附记在其后的括号内的原子键的FTIR光谱的峰强度。
而且,对于FTIR的光谱峰的波数位置,在SiN键中处于约870cm-1,在SiH键中处于约2170cm-1,在CH键中处于约2920cm-1,在NH键中处于约3380cm-1,在CF键中处于约1170cm-1,此外,在SiO2键中处于约1150cm-1,强度I是以吸收光学密度光谱的峰强度评价的。
图2以示意性框图来图解可以形成如上所述的有机·无机复合层的Cat-CVD成膜装置的一例。该成膜装置具备反应容器11,其具有气体导入口11a和排气口11b。在反应容器11内,设有加热灯丝12和用于支承与之面对的基体或基板(塑料薄膜等)13的支承台14。此外,灯丝12与反应容器11外的电源15连接。从图2中可以清楚地看到,在该加热合成中,可以利用极为简略且低成本的成膜装置来形成各种有机·无机复合膜。而且,加热灯丝12例如由Ta、W等高熔点金属形成,在塑料薄膜基板上的成膜中,为了抑制由来自加热灯丝的辐射热造成的塑料薄膜的热变形,通常被加热到1100℃到1300℃左右。
本发明的作为特定的有机·无机复合层的SiCNFH层、SiOCNH层、以及SiCNH层可以利用此种Cat-CVD理想地堆积。在该Cat-CVD中,可以优选利用选自有机硅烷化合物、有机氨基硅化合物、氨、氟碳、氧、以及氢中的原料气体。
实施例
下面,将连同与本发明密切相关的参考例的气体屏蔽膜一起,对本发明的各种实施例的气体屏蔽膜进行说明。
(参考例1)
首先,作为与本发明密切相关的参考例1,本发明人研究了仅在基底的塑料薄膜的一个主面上形成作为有机·无机复合层的SiCNFH层的单层的气体屏蔽膜的屏蔽特性。
在本参考例1中,在由PEN(聚萘二甲酸乙二醇酯)构成的厚200μm的塑料薄膜上,利用Cat-CVD法形成了设定厚度为1000nm的单层的SiCNFH层。在利用该Cat-CVD形成SiCNFH层时,将单甲基硅烷(以下简称为“1MS”)/H2/N2/NH3/C4F8以5/200/200/200/20(sccm)的流量比导入成膜装置内。
对如此得到的SiCNFH层中所含的各种原子键利用FTIR进行了研究,其结果是,观测到SiN、CF、SiH、CH、NH等原子键,确认是有机·无机复合层。
在本参考例1中,利用Lyssy公司的气体透过率测定装置测定了仅在PEN薄膜的一个主面上具有单层的SiCNFH层的气体屏蔽膜的屏蔽特性。更具体来说,在水蒸气透过率(也称作WVTR)的测定中,使用了Lyssy公司的屏蔽测定仪L80-5000(JIS-K7129-A法)。
图3是表示在参考例1的气体屏蔽膜中测定出的WVTR的时间依赖性的曲线图。即,图3的曲线图的横轴表示时间(hr),纵轴表示WVTR(g/m2/day)。这里,g/m2/day表示每一天透过气体屏蔽膜的每1m2的面积的水蒸气的质量。而且,Lyssy公司的屏蔽测试仪L80-5000的测定的下限极限值是0.001(g/m2/day),很难测定比该值更低的WVTR。
在图3的WVTR试验中,水蒸气是从基底的PEN薄膜侧提供的。从图3的曲线图中可以清楚地看到,在仅在PEN薄膜的一面具有单层的SiCNFH屏蔽层的参考例1的气体屏蔽膜中,从试验开始到约25小时(约1天)维持大约小于0.02(g/m2/day)的WVTR,然而在其后直到约50小时(约2天)WVTR增大到约0.075(g/m2/day)后就平稳化,直至约60小时(约2.5天),在经过该约2.5天后WVTR急剧地增大而无法起到作为气体屏蔽膜的作用。
本发明人对此种气体屏蔽膜的劣化的现象进行了详细研究。其结果是,发现气体屏蔽膜的劣化是由如下原因引起的,即,随着时间经过,基底的PEN薄膜吸收水分子,此后由所吸收的水分子使得特别是PEN薄膜与气体屏蔽层的界面劣化。
(实施例1)
本发明的实施例1的气体屏蔽膜如图1所示,在作为基底的塑料薄膜1的两个主面上具有单层的气体屏蔽层2。具体来说,在本实施例1中,在PEN薄膜的两面的任意一侧都利用与参考例1的情况类似的Cat-CVD形成单层的SiCNFH屏蔽层。但是,本实施例1中,通过将Cat-CVD的原料气体流量比的1MS/H2/NH3/C4F8以5/200/200/200/20(sccm)为基本进行各种变更,并且使灯丝温度也进行各种变化,而制作出多个气体屏蔽膜。
图4是表示本实施例1中堆积的SiCNFH层的FTIR的一例的曲线图。即,该曲线图的横轴表示波数(cm-1),纵轴表示吸收强度。如该曲线图中所示,观察到基于SiN键、CF键、SiH键、CH键、NH键等的吸收峰,可知作为有机·无机复合层形成SiCNFH层。
图5和图6表示在使Cat-CVD中的灯丝温度进行各种变化而堆积的SiCNFH层中有关各种原子键的FTIR的吸收光谱强度比。即,这些曲线图的横轴表示灯丝温度,纵轴表示吸收光谱的峰强度比。
图5的曲线图中,圆圈标记、三角标记、以及倒三角标记分别表示SiH键、CH键、以及NH键的吸收强度相对于SiN键的吸收强度的比率。另外,图6的曲线图的圆圈标记表示CF键的吸收强度相对于SiN键的吸收强度的比率。
在图5和图6的曲线图中,SiCNFH层满足0.01<I(SiH)/I(SiN)<0.05、0.00<I(CH)/I(SiN)<0.07、0.04<I(NH)/I(SiN)<0.08、以及0.05<I(CF)/I(SiN)<0.3的条件。而且,如前所述,I表示有关附记在其后的括号内的原子键的FTIR光谱的峰强度。
在PEN薄膜的两面形成满足此种实施例1的吸收光谱强度比的条件的单层的SiCNFH屏蔽层的情况下,与上述的参考例1的情况不同,即使在WVTR试验中经过约3天以后,也完全观察不到屏蔽特性的急剧的劣化。
另外,气体屏蔽膜的屏蔽特性可以通过控制原料气体的流量比、灯丝温度、薄膜基板温度等来调整,在本实施例1中特性特别良好的气体屏蔽膜在WVTR试验中即使经过3天后也没有显现出测定值,即具有小于0.001(g/m2/day)的优异的屏蔽特性。
在显示如此优异的屏蔽特性的气体屏蔽膜中分析了SiCNFH屏蔽层的FTIR光谱的峰强度比,其结果是,满足0.01<I(SiH)/I(SiN)<0.03、0.00<I(CH)/I(SiN)<0.02、0.05<I(NH)/I(SiN)<0.08、以及0.05<I(CF)/I(SiN)<0.25的条件。
(实施例2)
在本发明的实施例2的气体屏蔽膜中,也与实施例1的情况类似,在PEN薄膜的两面形成单层的气体屏蔽层。但是,在本实施例2中,作为单层的气体屏蔽层利用Cat-CVD形成SiOCNH层。
本实施例2中,通过将Cat-CVD的原料气体流量比以1MS/NH3/H2/N2=5/200/200/200(sccm)以及O2/Ar(含有10%的O2的O2/Ar混合气体)=20(sccm)为基本进行各种变更,并且还对灯丝温度进行各种改变,而制作出多个气体屏蔽膜。
与图5类似的图7是表示在本实施例2中堆积的SiOCNH层的FTIR的一例的曲线图。即,该曲线图的横轴表示波数(cm-1),纵轴表示吸收强度。如该曲线图中所示,观察到基于SiN键、SiO2键、SiH键、CH键、NH键等的吸收峰,可知作为有机·无机复合层形成SiOCNH层。
与图5的情况相同,在本实施例2中,也在对Cat-CVD中的灯丝温度进行各种改变而堆积的SiOCNH层中,测定出有关各种原子键的FTIR的吸收光谱强度比。其结果是,本实施例2的SiOCNH层满足0.1<I(SiH)/I(NH)<0.9、0.0<I(CH)/I(NH)<0.3、8<I(SiN)/I(NH)<20、以及2<I(SiO2)/I(NH)<8的条件。
在PEN薄膜的两面形成满足此种本实施例2的吸收光谱强度比的条件的单层的SiOCNH屏蔽层的情况下,也与上述的参考例1的情况不同,即使在WVTR试验中经过大约3天以后,也完全没有观察到屏蔽特性的急剧的劣化。
此外,在本实施例2中,也可以通过控制原料气体的流量比、灯丝温度、薄膜基板温度等来调整气体屏蔽膜的屏蔽特性,特别在特性良好的气体屏蔽膜中,即使在WVTR试验中经过3天后也没有显现出测定值,即,具有小于0.001(g/m2/day)的优异的屏蔽特性。
在显示如此优异的屏蔽特性的气体屏蔽膜中分析了SiOCNH屏蔽层的FTIR光谱的峰强度比,其结果是,满足0.1<I(SiH)/I(NH)<0.5、0.0<I(CH)/I(NH)<0.2、10<I(SiN)/I(NH)<20、以及2<I(SiO2)/I(NH)<5的条件。
(实施例3)
在本发明的实施例3的气体屏蔽膜中,也与实施例1的情况类似,在PEN薄膜的两面形成单层的气体屏蔽层。但是,在本实施例3中,作为单层的气体屏蔽层利用Cat-CVD形成SiCNH层。
本实施例3中,通过将Cat-CVD的原料气体流量比以1MS/NH3/H2/N2=5/200/200/200(sccm)为基本进行各种变更,并且还对灯丝温度进行各种改变,而制作出多个气体屏蔽膜。
与图5类似的图8是表示在本实施例3中堆积的SiCNH层的FTIR的一例的曲线图。即,该曲线图的横轴表示波数(cm-1),纵轴表示吸收强度。如该曲线图中所示,观察到基于SiN键、CN键、SiH键、CH键、NH键等的吸收峰,可知作为有机·无机复合层形成SiCNH层。
与图5的情况相同,在本实施例3中,也在对Cat-CVD中的灯丝温度进行各种改变而堆积的SiCNH层中,测定出有关各种原子键的FTIR的吸收光谱强度比。其结果是,本实施例3的SiCNH层满足0.01<I(SiH)/I(SiN)<0.05、0.0<I(CH)/I(SiN)<0.07、0.04<I(NH)/I(SiN)<0.08的条件。
在PEN薄膜的两面形成满足此种本实施例3的吸收光谱强度比的条件的单层的SiCNH屏蔽层的情况下,也与上述的参考例1的情况不同,即使在WVTR试验中经过大约3天以后,也完全没有观察到屏蔽特性的急剧的劣化。
此外,在本实施例3中,也可以通过控制原料气体的流量比、灯丝温度、薄膜基板温度等来调整气体屏蔽膜的屏蔽特性,在特性特别良好的气体屏蔽膜中,即使在WVTR试验中经过3天后也没有得到作为测定检测极限的0.001(g/m2/day)的数据,即具有小于0.001(g/m2/day)的优异的屏蔽特性。
对显示如此优异的屏蔽特性的气体屏蔽膜中的SiCNH屏蔽层的FTIR光谱的峰强度比进行了分析,其结果是,满足0.01<I(SiH)/I(SiN)<0.03、0.00<I(CH)/I(SiN)<0.02、以及0.05<I(NH)/I(SiN)<0.08的条件。
(变形例)
在上述的实施例中,以在塑料薄膜的两面形成相同种类的气体屏蔽层的情况作为例示进行了说明。但是,堆积在塑料薄膜的两面的气体屏蔽层不需要是相同的种类。即,也可以在塑料薄膜的一个主面上堆积选自SiCNFH层、SiOCNH层、以及SiCNH层中的屏蔽层,在其另一个主面上堆积与在其一个主面上选择的种类不同的SiCNFH层、SiOCNH层、以及SiCNH层的任意一种。
例如,对于在PEN薄膜的一个主面上形成SiCNFH层并且在另一个主面上形成SiOCNH层的气体屏蔽膜的样品的一例进行了WVTR测定,其结果是,即使经过6天后,也没有得到作为检测极限的0.001(g/m2/day)的数据,可知其WVTR小于0.001(g/m2/day)。
但是,在用于柔性有机EL元件中的气体屏蔽膜的情况下,要求1μg/m2/day左右的极高的水蒸气屏蔽性。该情况下,可以通过在塑料薄膜的两面上,分别利用Cat-CVD形成SiCNFH层、SiOCNH层、以及SiCNH层当中相互不同的种类的2层以上,来明显地提高该有机EL元件的寿命和可靠性。
另外,在希望具有难以将气体屏蔽膜的表面污染的性质或疏水性的情况下,气体屏蔽膜的最外层优选为含有氟的SiCNFH层。另一方面,在希望气体屏蔽膜的表面具有与粘接剂等的良好的接合性的情况下,其最外层优选为SiOCNH层或SiCNH层。特别是,在气体屏蔽膜上形成透明氧化物导电膜的情况下,优选作为其最外层形成可以获得与氧化物层的良好的接合性的SiOCNH层。
此外,在上述的实施例中作为用作基底的塑料薄膜,例示出使用PEN薄膜的情况。但是,可以用作基底的塑料薄膜并不限于PEN,当然也可以使用PET(聚对苯二甲酸乙二醇酯)、PI(聚酰亚胺)、氟树脂、PC(聚碳酸酯)、PAR(多芳基化合物)、PES(聚醚砜)、耐热液晶薄膜等其他各种塑料薄膜。虽然在Cat-CVD中能够利用灯丝的热辐射而使基底薄膜的温度上升,然而由于在该基底薄膜的支承台中附加有冷却装置,因此塑料薄膜只要具有120℃以上的玻璃化温度或200℃以上的熔点、或者200℃以上的液晶化温度的耐热性就已足够。
但是,作为基底的塑料薄膜的表面最好尽可能平坦或平滑。这是因为,在塑料薄膜的表面粗糙度大的情况下,在其表面粗糙的突起部或凹部中屏蔽层的覆盖不足或产生针孔,进而以这些局部的缺陷为起点,气体屏蔽膜的屏蔽特性明显地降低。所以,在作为基底的塑料薄膜的表面粗糙度大的情况下,优选利用等离子体CVD等对其表面进行平滑化处理,或涂覆附加的平滑化层。而且,上述的实施例中所用的PEN薄膜具有10nm以下的表面粗糙度(Ra值)。
(应用例)
如上述的背景技术中所说明的那样,气体屏蔽膜可以作为用于食品、医药品、触摸面板、有机EL(电致发光)元件、无机EL元件、太阳能电池、电子纸等各种物品的保护层理想地使用。
首先,在用于保护食品、医药品、电子部件、以及其他物品的袋子中,可以利用本发明的气体屏蔽膜。即,可以通过在2片屏蔽特性在长时间内不会劣化的本发明的气体屏蔽膜之间夹持应当保护的物品,将这些薄膜的周围用粘接剂密封,来形成保护袋。此时,也优选向保护袋内封入密封气体,或封入脱氧剂。
另外,通过在本发明的气体屏蔽膜的至少一个主面上形成导电层,可以形成具有高气体屏蔽特性和其耐久性的电极膜。作为此种导电层,当然可以利用蒸镀等来赋予金属层。另外,也可以在气体屏蔽膜上,形成透明导电性氧化物层。像这样具有透明导电性氧化物层的气体屏蔽膜可以发挥各种电子式显示元件等的电极层和气体屏蔽层两种功能,因此具有出色的有用性。即,此种气体屏蔽膜例如可以在触摸面板中作为具有优异的气体屏蔽特性的电极层来利用。
另外,对于本领域技术人员来说,显而易见,如上所述地可以长时间维持极高的屏蔽特性的本发明的气体屏蔽膜也可以理想地应用于要求长时间维持高度的气体屏蔽特性的、特别是有机EL元件、以及无机EL元件、太阳能电池、电子纸等电子器件中。该情况下,通过将本发明的气体屏蔽膜作为基板利用,还可以提供柔性的有机EL元件、无机EL元件、薄膜太阳能电池、电子纸等。
工业上的可利用性
如上所述,根据本发明,通过与塑料薄膜的两个主面分别接触地设置特定的有机·无机复合层的气体屏蔽层,可以提供与先行技术相比能够实现气体屏蔽性的提高及制造的简化和低成本化的气体屏蔽膜。
另外,通过利用此种气体屏蔽膜,还可以提供能够防止各种电子器件的特性劣化、能够保护各种物品的气体屏蔽性的袋子。
符号说明
1塑料薄膜,2由利用Cat-CVD堆积的有机·无机复合层构成的气体屏蔽层,11反应容器,11a气体导入口,11b排气口,12加热灯丝,13基体或基板(塑料薄膜),14支承台
Claims (9)
1.一种气体屏蔽膜,其特征在于,具有与塑料薄膜(1)的两个主面分别接触的气体屏蔽层(2),
所述气体屏蔽层是利用Cat-CVD堆积的SiCNFH层、SiOCNH层以及SiCNH层中的任意一种,
所述SiCNFH层满足0.01<I(SiH)/I(SiN)<0.05、0.00<I(CH)/I(SiN)<0.07、0.04<I(NH)/I(SiN)<0.08、以及0.05<I(CF)/I(SiN)<0.3的条件,
所述SiOCNH层满足0.1<I(SiH)/I(NH)<0.9、0.0<I(CH)/I(NH)<0.3、8<I(SiN)/I(NH)<20、以及2<I(SiO2)/I(NH)<8的条件,
此外,所述SiCNH层满足0.01<I(SiH)/I(SiN)<0.05、0.00<I(CH)/I(SiN)<0.07、以及0.04<I(NH)/I(SiN)<0.08的条件,
这里,I表示有关附记在其后的括号内的原子键的傅立叶变换红外分光光谱的峰强度,
而且,对于傅立叶变换红外分光的光谱峰的波数位置,在SiN键中处于870cm-1,在SiH键中处于2170cm-1,在CH键中处于2920cm-1,在NH键中处于3380cm-1,在CF键中处于1170cm-1,此外,在SiO2键中处于1150cm-1。
2.根据权利要求1所述的气体屏蔽膜,其特征在于,所述SiCNFH层满足0.01<I(SiH)/I(SiN)<0.03、0.00<I(CH)/I(SiN)<0.02、0.05<I(NH)/I(SiN)<0.08、以及0.05<I(CF)/I(SiN)<0.25的条件,
所述SiOCNH层满足0.1<I(SiH)/I(NH)<0.5、0.0<I(CH)/I(NH)<0.2、10<I(SiN)/I(NH)<20、以及2<I(SiO2)/I(NH)<5的条件,
此外,所述SiCNH层满足0.01<I(SiH)/I(SiN)<0.03、0.00<I(CH)/I(SiN)<0.02、以及0.05<I(NH)/I(SiN)<0.08的条件。
3.根据权利要求1所述的气体屏蔽膜,其特征在于,在与所述塑料薄膜接触的气体屏蔽层上层叠有所述SiCNFH层、所述SiOCNH层、以及所述SiCNH层中的任意一种附加的气体屏蔽层,与所述塑料薄膜接触的气体屏蔽层与所述附加的气体屏蔽层是彼此不同种类的层。
4.根据权利要求1所述的气体屏蔽膜,其特征在于,所述塑料薄膜是具有120℃以上的玻璃化温度或200℃以上的熔点、或者200℃以上的液晶化温度的耐热性的塑料薄膜。
5.根据权利要求1所述的气体屏蔽膜,其特征在于,所述塑料薄膜被进行了表面平坦化处理。
6.根据权利要求1所述的气体屏蔽膜,其特征在于,在所述气体屏蔽膜的至少一个面上还附加地包含导电层。
7.一种电子器件,其特征在于,作为保护层包含权利要求1所述的气体屏蔽膜。
8.根据权利要求7所述的电子器件,其特征在于,所述电子器件是触摸面板、有机EL器件、无机EL器件、太阳能电池以及电子纸的任意一种。
9.一种气体屏蔽袋,其特征在于,以权利要求1所述的气体屏蔽膜形成。
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KR102282214B1 (ko) | 2014-08-01 | 2021-07-26 | 삼성전자주식회사 | 가스 배리어성 점착 시트의 점착층용 조성물, 상기 조성물로부터 제조되는 가스 배리어성 점착 시트, 상기 가스 배리어성 점착 시트가 구비된 광학시트 |
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