CN114515682A - 一种柔性透明超低水汽透过率阻隔膜及其制备方法 - Google Patents
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Abstract
本发明提供一种柔性透明超低水汽透过率阻隔膜及其制备方法,涉及柔性薄膜领域,包括自下而上依次复合的有机柔性衬底、一层或多层具有褶皱形貌的隔水隔氧薄膜、有机层,所述隔水隔氧薄膜由有机聚合物层、无机氧化物层自下而上复合而成。本柔性透明超低水汽透过率阻隔膜在有机柔性衬底上依次叠加具有“褶皱”形貌的有机聚合物层和无机氧化物层的隔水隔氧薄膜。利用有机聚合物层和无机氧化物层之间的热膨胀系数不同的原理在产生独特的“褶皱”形貌同时生成表面十分均匀致密的无机物层,从而实现对水汽氧气的阻隔,最终实现可见光透过率(380至800nm)大于85%和水汽透过率(WVTR)在38℃,90%RH条件下低于5×10‑6g/m2/天。
Description
技术领域
本发明涉及柔性薄膜技术领域,具体为一种柔性透明超低水汽透过率阻隔膜及其制备方法。
背景技术
随着如有机电致发光二极管(OLED)、有机薄膜太阳能电池(OPVs)和量子点电致发光二极管(QLED)等柔性电子器件的兴起,起水氧阻隔作用的柔性电子器件阻隔膜技术也提出了新的要求。从原先LCD液晶显示器要求的低于10-2g/m2/天的透水率,到柔性太阳能电池要求的低于10-4g/m2/天的透水率,再到现如今QLED显示器要求的低于10-6g/m2/天的透水率,柔性分装需要不断跟进。
在传统的多层有机/无机叠层阻隔膜技术中,有机层添加一方面可以减少由于单层无机氧化物厚度的增加所造成的针孔和裂纹,同时延长气体的渗透路径,从而使阻隔性能得到提高;有机层添加另一个作用是起“平坦化”的作用,即降低基材表面的粗糙度,使无机氧化物镀层与之更好的结合。但是“平坦化”后再沉积的无机氧化物表面通常存在较大的应力,从而无法得到均匀且致密阻隔层,导致了水汽氧气更容易通过薄膜缺陷透过薄膜。
因此,针对目前现有技术的不足,提供一种通过利用有机层与无机层热膨胀系数不同的原理,在无机氧化物层引入“褶皱”结构,从而获得了极其均匀致密的阻隔层,实现了WVTR一个以上数量级地降低。从而提供了大规模生产超低水汽透过率阻隔膜的新思路。
发明内容
(一)解决的技术问题
针对现有技术的不足,本发明提供了一种柔性透明超低水汽透过率阻隔膜及其制备方法,解决了上述背景技术中提出的问题。
(二)技术方案
为实现以上目的,本发明通过以下技术方案予以实现:一种柔性透明超低水汽透过率阻隔膜,包括自下而上依次复合的有机柔性衬底、一层或多层具有褶皱形貌的隔水隔氧薄膜、有机层,所述隔水隔氧薄膜由有机聚合物层、无机氧化物层自下而上复合而成。
优选的,所述阻隔膜的总体厚度小于150μm,所述阻隔膜除去有机柔性衬底的总厚度小与50μm。
优选的,所述有机柔性衬底为二甲酸乙二醇酯薄膜(PET)、聚萘二甲酸乙二醇酯薄膜(PEN)、聚丙烯薄膜(BOPP、OPP)、聚乙烯薄膜(PE)、聚酰亚胺薄膜(PI膜)、聚碳酸酯薄膜(PC)中的一种。
优选的,所述有机柔性衬底的厚度在10至125μm的范围内。
优选的,所述有机聚合物层和有机层为UV胶、有机改性陶瓷、有机/无机杂化聚合物、PDMS、甲基聚硅氧烷树脂、环氧基硅烷、丙烯酸复合粘合剂、聚氨酯胶粘剂中的一种或多种。
优选的,所述有机聚合物层和有机层的厚度在1至5μm之间。
优选的,所述无机氧化物层为Al2O3-ZnO(AZO)、In2O3-ZnO(IZO)、In2O3-SnO2(ITO)、Al2O3、ZnO、SiO2、AlN、Si3N4、Nb2O5中的一种或多种。
优选的,所述无机氧化物层的厚度在10至500nm之间。
一种柔性透明超低水汽透过率阻隔膜的制备方法,包括以下步骤:
步骤一:清洗有机柔性衬底,优选将直径为10cm的有机柔性衬底利用去离子水、无水乙醇和丙酮超声清洗;
步骤二:在由步骤一得到的有机柔性衬底上利用旋涂、喷涂、刮涂或浸涂的方式涂敷一层1至5μm的有机聚合物层,并用紫外光或者热固化2至8分钟;
步骤三:将由步骤二得到的有机聚合物层与机柔性衬底组成的复合膜置于磁控真空腔体中预热,基底温度提高到60至90℃预热30min;然后在10至1000W射频功率,纯Ar流量5至100SCCM,工作压力0.17至1Pa下用平面靶材在上述有机聚合物层上通过磁控溅射沉积厚度为10至500nm的无机氧化物层,无机氧化物层与有机聚合物层之间形成具有褶皱形貌的隔水隔氧薄膜;
步骤四:重复上述步骤二至步骤四,制备2至5个隔水隔氧薄膜;
步骤五:在最上层的隔水隔氧薄膜上利用旋涂、浸涂或者喷涂等方式涂敷一层1至5μm的有机层并固化2至8分钟;
步骤六:用兰光公司C390H水汽透过率测试仪与岛津公司UV-3600紫外-可见-近红外分光光度计测试上述阻隔膜的阻隔性能与光透性能。
(三)有益效果
本发明提供了一种柔性透明超低水汽透过率阻隔膜及其制备方法。具备以下有益效果:
1、该柔性透明超低水汽透过率阻隔膜及其制备方法,本柔性超低水汽透过率阻隔膜在有机柔性衬底上依次叠加具有“褶皱”形貌的有机聚合物层和无机氧化物层的隔水隔氧薄膜。利用有机聚合物层和无机氧化物层之间的热膨胀系数不同的原理在产生独特的“褶皱”形貌同时生成表面十分均匀致密的无机物层,从而实现对水汽氧气的阻隔,最终实现可见光范围透光率高于85%和水汽透过率(WVTR)低于5×10-6g/m2/day。
附图说明
图1为本发明的制备过程示意图;
图2为本发明的阻隔膜示意图;
图3为本发明实施例3中未旋涂顶层有机层时的扫描电镜图。
图2中:1有机柔性衬底、2有机聚合物层、3无机氧化物层、4有机层。
具体实施方式
本发明实施例提供一种柔性透明超低水汽透过率阻隔膜,如图2所示,包括自下而上依次复合的有机柔性衬底1、一层或多层具有褶皱形貌的隔水隔氧薄膜、有机层4,隔水隔氧薄膜由有机聚合物层2、无机氧化物层3自下而上复合而成。
阻隔膜的总体厚度小于150μm,阻隔膜除去有机柔性衬底1的总厚度小与50μm。有机柔性衬底1为二甲酸乙二醇酯薄膜(PET)、聚萘二甲酸乙二醇酯薄膜(PEN)、聚丙烯薄膜(BOPP、OPP)、聚乙烯薄膜(PE)、聚酰亚胺薄膜(PI膜)、聚碳酸酯薄膜(PC)中的一种。有机柔性衬底1的厚度在10至125μm的范围内。
有机聚合物层2和有机层4为UV胶、有机改性陶瓷、有机/无机杂化聚合物、PDMS、甲基聚硅氧烷树脂、环氧基硅烷、丙烯酸复合粘合剂、聚氨酯胶粘剂中的一种或多种。有机聚合物层2和有机层4的厚度在1μm至5μm之间。
无机氧化物层3为Al2O3-ZnO(AZO)、In2O3-ZnO(IZO)、In2O3-SnO2(ITO)、Al2O3、ZnO、SiO2、AlN、Si3N4、Nb2O5中的一种或多种。无机氧化物层3的厚度在10至500nm之间。
如图1所示,一种柔性透明超低水汽透过率阻隔膜的制备方法,包括以下步骤:
步骤一:利用去离子水、丙酮和乙醇清洗有机柔性衬底1;
步骤二:在由步骤一得到的有机柔性衬底1上利用旋涂、喷涂、刮涂或浸涂的方式涂敷一层1至5μm的有机聚合物层2,并用紫外光或者热固化2至8分钟;
步骤三:将由步骤二得到的有机聚合物层2与机柔性衬底1组成的复合膜置于磁控真空腔体中预热,基底温度提高到60至90℃预热30min;然后在10至1000W射频功率,纯Ar流量5至100SCCM,工作压力0.17至1Pa下用平面靶材在上述有机聚合物层2上通过磁控溅射沉积厚度为10至500nm的无机氧化物层3,无机氧化物层3与有机聚合物层2之间形成具有褶皱形貌的隔水隔氧薄膜;
步骤四:重复上述步骤二至步骤四,制备2至5个隔水隔氧薄膜;
步骤五:在最上层的隔水隔氧薄膜上利用旋涂、浸涂或者喷涂等方式涂敷一层1至5μm的有机层4并固化2至8分钟;
步骤六:用兰光公司C390H水汽透过率测试仪、钙测试系统与岛津公司UV-3600紫外-可见-近红外分光光度计测试上述阻隔膜的阻隔性能与光透性能。
本柔性超低水汽透过率阻隔膜在有机柔性衬底1上依次叠加具有“褶皱”形貌的有机聚合物层2和无机氧化物层3的隔水隔氧薄膜。利用有机聚合物层2和无机氧化物层3之间的热膨胀系数不同的原理在产生独特的“褶皱”形貌同时生成表面十分均匀致密的无机物层,从而实现对水汽氧气的阻隔,最终实现可见光透过率大于85%和水汽透过率(WVTR)低于5×10-6g/m2/天。
为了方便理解本发明,下面将结合实施例与附图对本发明进行更全面的描述。但具体实施例仅用于解释本发明,本发明并不局限于本文所述的实施例。
实施例1,将直径为10cm、厚度为100μm的PET用去离子水冲洗5min,并用无水乙醇浸泡5min,再利用丙酮进行超声清洗15min,最后在无水乙醇中超声清洗30min,烘干。接着利用旋涂机在PET衬底上旋涂1um的UV胶,利用紫外光照射2分钟固化。将带有有机层的PET置于磁控真空腔体中预热,基底温度提高到70℃预热30min。然后在100W射频功率,纯Ar流量5SCCM,工作压力0.17Pa下用平面靶材在衬底上通过磁控溅射沉积厚度为50nm的AZO薄膜,并与UV胶组成作为隔水隔氧薄膜。将上述PET衬底与隔水隔氧薄膜置于旋涂匀胶机。最后用兰光公司C390H型水汽透过率仪与岛津公司UV-3600紫外-可见-近红外分光光度计测试阻隔膜的阻隔性能与光透性能。
实施例2,将直径为10cm、厚度为100μm的PET用去离子水冲洗5min,并用无水乙醇浸泡5min,再利用丙酮进行超声清洗15min,最后在无水乙醇中超声清洗30min,烘干。接着利用旋涂机在PET衬底上旋涂1um的UV胶,利用紫外光照射2分钟固化。将带有有机层的PET置于磁控真空腔体中预热,基底温度提高到70℃预热30min。然后在100W射频功率,纯Ar流量5SCCM,工作压力0.17Pa下用平面靶材在衬底上通过磁控溅射沉积厚度为100nm的AZO薄膜,并与UV胶组成作为隔水隔氧薄膜。将上述PET衬底与隔水隔氧薄膜置于旋涂匀胶机。最后用钙测试系统与岛津公司UV-3600紫外-可见-近红外分光光度计测试阻隔膜的阻隔性能与光透性能。
实施例3,将直径为10cm、厚度为100μm的PET用去离子水冲洗5min,并用无水乙醇浸泡5min,再利用丙酮进行超声清洗15min,最后在无水乙醇中超声清洗30min,烘干。接着利用旋涂机在PET衬底上旋涂1um的UV胶,利用紫外光照射2分钟固化。将带有有机层的PET置于磁控真空腔体中预热,基底温度提高到70℃预热30min。然后在100W射频功率,纯Ar流量5SCCM,工作压力0.17Pa下用平面靶材在衬底上通过磁控溅射沉积厚度为150nm的AZO薄膜,并与UV胶组成作为隔水隔氧薄膜。最后用钙测试系统与岛津公司UV-3600紫外-可见-近红外分光光度计测试阻隔膜的阻隔性能与光透性能。
实施例4,将直径为10cm、厚度为100μm的PET用去离子水冲洗5min,并用无水乙醇浸泡5min,再利用丙酮进行超声清洗15min,最后在无水乙醇中超声清洗30min,烘干。接着利用旋涂机在PET衬底上旋涂1um的UV胶,利用紫外光照射2分钟固化。将带有有机层的PET置于磁控真空腔体中预热,基底温度提高到70℃预热30min。然后在100W射频功率,纯Ar流量5SCCM,工作压力0.17Pa下用平面靶材在衬底上通过磁控溅射沉积厚度为150nm的AZO薄膜,并与UV胶组成作为隔水隔氧薄膜。根据上述步骤再制备一层隔水隔氧薄膜。最后用钙测试系统与岛津公司UV-3600紫外-可见-近红外分光光度计测试阻隔膜的阻隔性能与光透性能。
实施例5,将直径为10cm、厚度为100μm的PET用去离子水冲洗5min,并用无水乙醇浸泡5min,再利用丙酮进行超声清洗15min,最后在无水乙醇中超声清洗30min,烘干。接着利用旋涂机在PET衬底上旋涂1um的UV胶,利用紫外光照射2分钟固化。将带有有机层的PET置于磁控真空腔体中预热,基底温度提高到70℃预热30min。然后在100W射频功率,纯Ar流量5SCCM,工作压力0.17Pa下用平面靶材在衬底上通过磁控溅射沉积厚度为150nm的AZO薄膜,并与UV胶组成作为隔水隔氧薄膜。根据上述步骤再制备一层隔水隔氧薄膜,将上述PET衬底与两层隔水隔氧薄膜置于旋涂匀胶机,再旋涂一层UV胶,利用紫外光照射,8分钟后彻底固化。最后用钙测试系统与岛津公司UV-3600紫外-可见-近红外分光光度计测试阻隔膜的阻隔性能与光透性能。
实施例6,将直径为10cm、厚度为100μm的PET用去离子水冲洗5min,并用无水乙醇浸泡5min,再利用丙酮进行超声清洗15min,最后在无水乙醇中超声清洗30min,烘干。接着利用旋涂机在PET衬底上旋涂1um的UV胶,利用紫外光照射2分钟固化。将带有有机层的PET置于磁控真空腔体中预热,基底温度提高到70℃预热30min。然后在100W射频功率,纯Ar流量5SCCM,工作压力0.17Pa下用平面靶材在衬底上通过磁控溅射沉积厚度为100nm的AZO薄膜,并与UV胶组成作为隔水隔氧薄膜。根据上述步骤再制备两层隔水隔氧薄膜,将上述PET衬底与三层隔水隔氧薄膜置于旋涂匀胶机,再旋涂一层UV胶,利用紫外光照射,8分钟后彻底固化。最后用钙测试系统与岛津公司UV-3600紫外-可见-近红外分光光度计测试阻隔膜的阻隔性能与光透性能。
实施例7,将直径为10cm、厚度为100μm的PET用去离子水冲洗5min,并用无水乙醇浸泡5min,再利用丙酮进行超声清洗15min,最后在无水乙醇中超声清洗30min,烘干。接着利用旋涂机在PET衬底上旋涂1um的UV胶,利用紫外光照射2分钟固化。将带有有机层的PET置于磁控真空腔体中预热,基底温度提高到70℃预热30min。然后在100W射频功率,纯Ar流量5SCCM,工作压力0.17Pa下用平面靶材在衬底上通过磁控溅射沉积厚度为100nm的AZO薄膜,并与UV胶组成作为隔水隔氧薄膜。根据上述步骤再制备五层隔水隔氧薄膜,将上述PET衬底与六层隔水隔氧薄膜置于旋涂匀胶机,再旋涂一层UV胶,利用紫外光照射,8分钟后彻底固化。最后用钙测试系统与岛津公司UV-3600紫外-可见-近红外分光光度计测试阻隔膜的阻隔性能与光透性能。
实施例8,将直径为10cm、厚度为100μm的PET用去离子水冲洗5min,并用无水乙醇浸泡5min,再利用丙酮进行超声清洗15min,最后在无水乙醇中超声清洗30min,烘干。接着利用旋涂机在PET衬底上旋涂1um的UV胶,利用紫外光照射2分钟固化。将带有有机层的PET置于磁控真空腔体中预热,基底温度提高到70℃预热30min。然后在100W射频功率,纯Ar流量5SCCM,工作压力0.17Pa下用平面靶材在衬底上通过磁控溅射沉积厚度为100nm的SiO2薄膜,并与UV胶组成作为隔水隔氧薄膜。根据上述步骤再制备五层隔水隔氧薄膜,将上述PET衬底与六层隔水隔氧薄膜置于旋涂匀胶机,再旋涂一层UV胶,利用紫外光照射,8分钟后彻底固化。最后用钙测试系统与岛津公司UV-3600紫外-可见-近红外分光光度计测试阻隔膜的阻隔性能与光透性能。
以下为各实施例的WVTR与透光率的试验数据表:
尽管已经示出和描述了本发明的实施例,对于本领域的普通技术人员而言,可以理解在不脱离本发明的原理和精神的情况下可以对这些实施例进行多种变化、修改、替换和变型,本发明的范围由所附权利要求及其等同物限定。
Claims (7)
1.一种柔性透明超低水汽透过率阻隔膜的制备方法,其特征在于,包括以下步骤:
步骤一:利用去离子水、丙酮和乙醇清洗有机柔性衬底;
步骤二:在由步骤一得到的有机柔性衬底上利用旋涂、喷涂、刮涂或浸涂的方式涂敷一层1μm至5μm的有机聚合物层,并用紫外光2至20分钟或者或者在60至120℃热固化24至72h;
步骤三:将由步骤二得到的有机聚合物层与机柔性衬底组成的复合膜置于磁控真空腔体中预热,基底温度提高到60至90℃预热30min;然后在10至1000W射频功率,纯Ar流量5至100SCCM,工作压力0.17至1Pa下用平面靶材在上述有机聚合物层上通过磁控溅射沉积厚度为10至500nm的无机氧化物层,无机氧化物层与有机聚合物层之间形成具有褶皱形貌的隔水隔氧薄膜;
步骤四:重复上述步骤二至步骤四,制备2至5个隔水隔氧薄膜;
步骤五:在最上层的隔水隔氧薄膜上利用旋涂、浸涂或者喷涂等方式涂敷一层1至5μm的有机层并固化2至8分钟;
步骤六:用兰光公司C390H水汽透过率测试仪与岛津公司UV-3600紫外-可见-近红外分光光度计测试上述阻隔膜的阻隔性能与光透性能。
2.根据权利要求1所述的一种柔性透明超低水汽透过率阻隔膜的制备方法,其特征在于:所述有机柔性衬底为二甲酸乙二醇酯薄膜(PET)、聚萘二甲酸乙二醇酯薄膜(PEN)、聚丙烯薄膜(BOPP、OPP)、聚乙烯薄膜(PE)、聚酰亚胺薄膜(PI膜)、聚碳酸酯薄膜(PC)中的一种。
3.根据权利要求2所述的一种柔性透明超低水汽透过率阻隔膜的制备方法,其特征在于:所述有机柔性衬底的厚度在10至125μm的范围内。
4.根据权利要求1所述的一种柔性透明超低水汽透过率阻隔膜的制备方法,其特征在于:所述有机聚合物层和有机层为UV胶、有机改性陶瓷、有机/无机杂化聚合物、PDMS、甲基聚硅氧烷树脂、环氧基硅烷、丙烯酸复合粘合剂、聚氨酯胶粘剂中的一种或多种。
5.根据权利要求4所述的一种柔性透明超低水汽透过率阻隔膜的制备方法,其特征在于:所述有机聚合物层和有机层的厚度在1至5μm之间。
6.根据权利要求1所述的一种柔性透明超低水汽透过率阻隔膜的制备方法,其特征在于:所述无机氧化物层为Al2O3-ZnO(AZO)、In2O3-ZnO(IZO)、In2O3-SnO2(ITO)、Al2O3、ZnO、SiO2、AlN、Si3N4、Nb2O5中的一种或多种。
7.根据权利要求6所述的一种柔性透明超低水汽透过率阻隔膜的制备方法,其特征在于:所述无机氧化物层的厚度在10至500nm之间。
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