CN111394002A - 一种含二氧化硅空心球的透明显示膜及其制备方法和应用 - Google Patents
一种含二氧化硅空心球的透明显示膜及其制备方法和应用 Download PDFInfo
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- CN111394002A CN111394002A CN202010252770.0A CN202010252770A CN111394002A CN 111394002 A CN111394002 A CN 111394002A CN 202010252770 A CN202010252770 A CN 202010252770A CN 111394002 A CN111394002 A CN 111394002A
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Abstract
本发明提供了一种含二氧化硅空心球的透明显示膜及其制备方法和应用,属于投影用膜技术领域。本发明的透明显示膜包括依次层叠的投影显示层、基材层、胶粘剂层和离型材料层;所述投影显示层包括纳米磁性二氧化硅空心球。本发明在投影显示层中加入纳米磁性二氧化硅空心球,纳米二氧化硅空心球粒径分布均一、具有超高的比表面积、较窄的孔径分布和大孔容积,当光投射到投影显示层时,光的传播路径变长,光的保留时间也延长,有效提高了光的利用率和透光率,从而增强光学成像能力和投影显示效果。
Description
技术领域
本发明涉及投影膜技术领域,特别涉及一种含二氧化硅空心球的透明显示膜及其制备方法和应用。
背景技术
目前市场上的透明显示技术主要有:全息显示、TOLED(穿透式有机发光设备)、反射式显示器和透明LCD(Liquid Crystal Display,液晶显示器)。采用传统平板显示存在的问题有体积大、热量大、投射不清晰等问题,而且造价高昂,这限制了这项技术的应用。
投影显示膜(又可称为投影显示薄膜),是目前新型投影成像薄膜,它本身具有高的可见光透过性,其可贴附在透明玻璃上使用。一般地,这些投影显示膜中含有一些纳米扩散性粒子,如金刚石粒子、氧化铝粒子等,当投影仪照射在投影显示膜上时,粒子进行扩散,从而使得投影显示膜上可以成像。投影显示膜可以应用在如会议室、家庭影院、展会、展馆、科技展示、旅游景点以及室内或户外广告等多个领域。
现有技术对投影显示膜的研究,主要针对膜的雾度、透过率、成像亮度等方面。例如采用两种或两种以上折射率不同、粒径不同的材料粒子构成混合物,利用薄膜中不同折射率和不同粒径粒子的散射来实现成像;又如中国专利102449508A公开了通过限定透明膜的设计结构中存在多个互联空隙,互联空隙的体积不小于20%,从而使光线在空隙中反复进行漫反射,从而提高透明膜的性能。但上述技术方案制备得到的透明显示膜的投影显示效果并不好。
发明内容
本发明的目的在于提供一种含二氧化硅空心球的透明显示膜及其制备方法和应用。本发明通过在投影显示层中加入纳米磁性二氧化硅空心球,增强了透明膜的投影显示效果。
本发明提供了一种透明显示膜,包括依次层叠的投影显示层、基材层、胶粘剂层和离型材料层;所述投影显示层包括纳米磁性二氧化硅空心球。
优选地,所述纳米磁性二氧化硅空心球由包括以下步骤的方法制备得到:
将油性四氧化三铁和溶剂混合,得到分散混合液;
将所述分散混合液、曲拉通X-100、正己醇和水混合,得到分散复合液;
将所述分散复合液与硅源和浓氨水混合,常温下反应,得到纳米磁性二氧化硅;
将所述纳米磁性二氧化硅进行酸处理,得到所述纳米磁性二氧化硅空心球。
优选地,所述硅源为正硅酸四乙酯;所述浓氨水的质量百分浓度为20~25%。
优选地,所述酸处理的酸为50~60wt%的稀硝酸;所述酸处理的温度为50~80℃,时间为6~12h。
优选地,所述基材层包括聚对苯二甲酸乙二醇酯薄膜、聚乙烯薄膜、聚氯乙烯薄膜或玻璃材料。
优选地,所述投影显示层包括以下重量百分含量的组分:
纳米磁性二氧化硅空心球 10~20%;
热塑性树脂 55%~75%;
散射粒子材料 1%~10%;
无机纳米黑色颜料 1‰~5‰;
分散剂 0.1%~6.3%;
固化剂 0.1%~10%。
优选地,所述散射粒子材料包括三氧化二铝、氧化锌、氧化锆、二氧化钛和有机玻璃粒子中的一种或几种。
优选地,所述热塑性树脂包括丙烯酸类树脂、聚酯树脂、聚烯烃树脂、纤维素树脂、乙烯基树脂和聚碳酸酯树脂中的一种或几种。
本发明还提供了上述所述透明显示膜的制备方法,包括以下步骤:
将纳米磁性二氧化硅空心球形成浆料后涂布在基材层的一侧表面,固化成型,形成投影显示层;
在所述基材层的另一侧表面涂覆胶黏剂,形成胶粘剂层;
将所述离型材料层与胶粘剂层复合,收卷后制得所述透明显示膜。
本发明还提供了上述所述透明显示膜在投射系统中的应用。
本发明提供了一种透明显示膜,包括依次层叠的投影显示层、基材层、胶粘剂层和离型材料层;所述投影显示层包括纳米磁性二氧化硅空心球。本发明在投影显示层中加入纳米磁性二氧化硅空心球,纳米二氧化硅空心球粒径分布均一、具有超高的比表面积、较窄的孔径分布和大孔容积,当光投射到投影显示层时,光的传播路径变长,光的保留时间也延长,有效提高光的利用率和透光率,从而增强光学成像能力和投影显示效果。
实施例的结果表明,本发明提供的透明显示膜透光率可达90~95%,光通量可达1195~1262lm。
具体实施方式
本发明提供了一种透明显示膜,包括依次层叠的投影显示层、基材层、胶粘剂层和离型材料层;所述投影显示层包括纳米磁性二氧化硅空心球。
在本发明中,所述纳米磁性二氧化硅空心球优选由包括以下步骤的方法制备得到:
将油性四氧化三铁和溶剂混合,得到分散混合液;
将所述分散混合液、曲拉通X-100、正己醇和水混合,得到分散复合液;
将所述分散复合液与硅源和浓氨水,常温下反应,得到纳米磁性二氧化硅;
将所述纳米磁性二氧化硅进行酸处理,得到所述纳米磁性二氧化硅空心球。
本发明将油性四氧化三铁和溶剂混合,得到分散混合液;
在本发明中,所述油性四氧化三铁的粒径为优选为10~20nm,更优选为15nm;所述溶剂优选为环己烷,所述油性四氧化三铁在所述溶剂中的浓度优选为100~500mg/L,更优选为200~400mg/L,最优选为250~300mg/L。本发明对所述油性四氧化三铁和溶剂的来源没有特殊的限定,采用本领域技术人员熟知或市售产品即可。
在本发明中,所述混合优选为超声混合,所述超声混合的时间优选为0.5h~2h。
本发明将所述分散混合液、曲拉通X-100、正己醇和水混合,得到分散复合液;
在本发明中,所述曲拉通X-100、正己醇和水的体积比优选为1~10∶1~10∶1~5,更优选为6∶6∶1;所述油性四氧化三铁与曲拉通X-100的用量比优选为2~6mg∶1~4mL,更优选为5mg∶3mL。本发明对所述曲拉通X-100、正己醇的来源没有特殊的限定,采用本领域技术人员熟知或市售产品即可。
在本发明中,所述混合优选为超声混合,所述超声混合的时间优选为1h~3h。
本发明将所述分散复合液与硅源和浓氨水混合,常温下反应,得到纳米磁性二氧化硅。
在本发明中,所述硅源优选为正硅酸四乙酯,所述浓氨水的质量百分浓度优选为20~25%;所述油性四氧化三铁与硅源的用量比优选为0.5~2mg∶35~50μL,更优选为1mg∶40μL;所述浓氨水与硅源的体积比优选为5~8∶2~5,更优选为7∶4;所述常温下反应的时间优选为24小时以上。本发明对所述硅源和浓氨水的来源没有特殊的限定,采用本领域技术人员熟知或市售产品即可。
本发明将所述纳米磁性二氧化硅进行酸处理,得到所述纳米磁性二氧化硅空心球。
在本发明中,所述酸处理的酸优选为50~60wt%的稀硝酸;所述酸处理的温度优选为50~80℃,时间优选为6~12h。在本发明中,所述酸处理的目的是去除部分四氧化三铁,得到纳米磁性二氧化硅空心球。
在本发明中,所述投影显示层优选包括以下重量百分含量的组分:
纳米磁性二氧化硅空心球 10~20%;热塑性树脂 55%~75%;散射粒子材料1%~10%;无机纳米黑色颜料 1‰~5‰;分散剂 0.1%~6.3%;固化剂 0.1%~10%;所述投影显示层的厚度优选为10~40μm,更优选为20~30μm。
在本发明中,所述纳米磁性二氧化硅空心球的重量百分含量优选为10%~20%,更优选为13%~18%。
在本发明中,所述热塑性树脂的重量百分含量优选为55%~75%,更优选为60%~70%;所述热塑性树脂优选包括丙烯酸类树脂、聚酯树脂、聚烯烃树脂、纤维素树脂、乙烯基树脂和聚碳酸酯树脂中的一种或几种;更优选为聚甲基丙烯酸甲酯树脂、聚对苯二甲酸乙二酯树脂、聚萘二甲酸树脂、聚丙烯树脂、环烯烃聚合物树脂、乙酸丙酸纤维素树脂、聚乙烯醇缩丁醛树脂、聚碳酸酯树脂和聚苯乙烯树脂中的一种或几种;本发明对所述热塑性树脂的来源没有特殊的限定,采用本领域技术人员熟知的或市售产品即可。
在本发明中,散射粒子材料的重量百分含量优选为1%~10%,更优选为4%~6%;所述散射粒子材料优选包括三氧化二铝、氧化锌、氧化锆、二氧化钛和有机玻璃粒子中的一种或几种;所述氧化锆优选为二氧化锆;所述有机玻璃粒子优选为聚甲基丙烯酸甲酯粒子;本发明对所述三氧化二铝、氧化锌、氧化锆、二氧化钛和有机玻璃粒子的混合比例没有特殊的要求,采用任意比例混合即可;在本发明中,所述散射粒子材料的粒径为优选为1nm~20μm,更优选为100nm~10μm;本发明对所述散射粒子材料的来源没有特殊的限定,采用本领域技术人员熟知的或市售产品即可。
在本发明中,所述无机纳米黑色颜料的重量百分含量优选为1‰~5‰,更优选为2‰~4‰,最优选为3‰;所述无机纳米黑色颜料优选包括炭黑、骨黑和铁黑中的一种或几种;所述无机纳米黑色颜料的粒径优选为25nm~700nm,更优选为100~500nm;本发明对所述无机纳米黑颜料的来源没有特殊的限定,采用本领域技术人员熟知的或市售产品即可。
在本发明中,所述分散剂的重量百分含量优选为0.1%~6.3%,更优选为2%~4%,最优选为3%;所述分散剂优选包括Disperbyk-162、Disperbyk-163、Disperbyk-168、Solsperse-5000、Solsperse-12000、Solsperse-22000、Solsperse-24000、Solsperse-32000、Solsperse-32500、Solsperse-6000、Solsperse-39000、Dispers-710、Dispers-685、Dispers-652、Dispers-655、EFKA Additives-4030和EFKA Additives-4330中的一种或几种,所述Disperbyk-162、Disperbyk-163、Disperbyk-168优选来自毕克化学公司;所述Solsperse-5000、Solsperse-12000、Solsperse-22000、Solsperse-24000、Solsperse-32000、Solsperse-32500、3Solsperse-6000、Solsperse-39000优选来自路博润公司;所述Dispers-710、Dispers-685、Dispers-652、Dispers-655优选来自德固萨公司;所述EFKAAdditives-4030、EFKA Additives-4330优选来自埃夫卡公司。
在本发明中,所述固化剂的重量百分含量优选为0.1%~10%,更优选为2%~8%,最优选为4%~6%;所述固化剂优选为热塑性固化剂或紫外固化剂,所述固化剂优选包括IRGACURE127、IRGACURE184、IRGACURE2959、IRGACURE651、IRGACURE369、IRGACURE907、IRGACURE 1300、IRGACURE819、IRGACURE784、DarocurITX、Darocur4265或Lucerin TPO。在本发明中,所述固化剂的来源优选自美国汽巴公司。
本发明对所述投影显示层的制备方法没有特殊的限定,将各组分混合均匀后使用即可;具体的如:将所述热塑性树脂、散射粒子材料、无机纳米黑色颜料、分散剂和固化剂混合均匀,得到混合物;在所述纳米磁性二氧化硅空心球表面包覆所述混合物,固化,得到所述投影显示层。
在本发明中,所述基材层优选包括聚对苯二甲酸乙二醇酯薄膜、聚乙烯薄膜、聚氯乙烯薄膜或玻璃材料;所述基材层的厚度优选为20~100μm,更优选为50~70μm。本发明对所述基材层的来源没有特殊的限定,采用本领域技术人员熟知的或市售产品即可。
在本发明中,所述胶粘剂层优选包括丙烯酸酯胶粘剂、聚氨酯胶粘剂或有机硅胶粘剂;所述胶黏剂层的厚度优选为10~50μm,更优选为20~30μm。本发明对所述胶黏剂层的来源没有特殊的限定,采用本领域技术人员熟知的或市售产品即可。
在本发明中,所述离型材料层优选包括PE离型膜、PC离型膜、PS隔离膜、PMMA离型膜、BOPP离型膜、PE剥离膜、塑料薄膜、TPX离型膜、PVC剥离膜或离型纸,所述离型材料层的厚度优选为0.5~150μm,更优选为20~120μm。在本发明中,所述离型材料层的主要作用为隔离、填充、保护和易于剥离。本发明对所述离型材料层的来源没有特殊的限定,采用本领域技术人员熟知的或市售产品即可。
本发明还提供了上述透明显示膜的制备方法,包括以下步骤:
将纳米磁性二氧化硅空心球形成浆料后涂布在基材层的一侧表面,固化成型,形成投影显示层;
在所述基材层的另一侧表面涂覆胶黏剂,形成胶粘剂层;
将所述离型材料层与胶粘剂层复合,收卷后制得所述透明显示膜。
本发明还提供了所述透明显示膜在投射系统中的应用。
为了进一步说明本发明,下面结合实施例对本发明提供的透明显示膜及其制备方法和应用进行详细地描述,但不能将它们理解为对本发明保护范围的限定。
实施例1
称取10mg油性四氧化三铁,分散于40mL环己烷中,超声1h后,加入6mL曲拉通X-100,6mL正己醇,1mL水,常温超声1h,随后缓慢加入400μL正硅酸四乙酯,超声1.5h后,加入0.8mL浓氨水,常温反应24h之后,在10000转/分钟的转速下离心分离收集,然后在60℃下加入1mL硝酸,加热反应8.5h,离心收集,得到纳米磁性二氧化硅空心球。
将以下重量百分含量的组分:纳米磁性二氧化硅空心球 15%;聚甲基丙烯酸甲酯树脂 71.7%;三氧化二铝 5%;炭黑 3‰;Disperbyk-162 3%;IRGACURE127 5%均匀混合,搅拌并静置后,制备得到25μm的投影显示层;
将所述投影显示层涂布在聚对苯二甲酸乙二醇酯薄膜(50μm)的一侧表面,固化成型;
在所述聚对苯二甲酸乙二醇酯薄膜的另一侧表面涂覆丙烯酸酯胶粘剂(30μm);
将所述PE离型膜(60μm)与丙烯酸酯胶粘剂复合;
收卷后制得所述透明显示膜。
实施例2
称取20mg油性四氧化三铁,分散于85mL环己烷中,超声1.5h后,加入15mL曲拉通X-100,15mL正己醇,12mL水,常温超声1.2h,随后缓慢加入800μL正硅酸四乙酯,超声1.5h后,加入0.8mL浓氨水,常温反应24h之后,在10000转/分钟的转速下离心分离收集,然后在60℃下加入1.5mL硝酸,加热反应8.5h,离心收集,得到纳米磁性二氧化硅空心球。
将以下重量百分含量的组分:纳米磁性二氧化硅空心球 10%;聚对苯二甲酸乙二酯树脂 74.2%;氧化锆 8%;骨黑 5‰;Solsperse-5000 6.3%;IRGACURE651 1%均匀混合,搅拌并静置后,制备得到20μm的投影显示层;
将所述投影显示层涂布在乙烯薄膜(20μm)的一侧表面,固化成型;
在所述乙烯薄膜的另一侧表面涂覆聚氨酯胶粘剂(50μm);
将所述PC离型膜(60μm)与聚氨酯胶粘剂复合;
收卷后制得所述透明显示膜。
实施例3
称取15mg油性四氧化三铁,分散于55mL环己烷中,超声1h后,加入8mL曲拉通X-100,8mL正己醇,6mL水,常温超声1h,随后缓慢加入600μL正硅酸四乙酯,超声1.5h后,加入0.8mL浓氨水,常温反应24h之后,在10000转/分钟的转速下离心分离收集,然后在70℃下加入1mL硝酸,加热反应9h,离心收集,得到纳米磁性二氧化硅空心球。
将以下重量百分含量的组分:纳米磁性二氧化硅空心球 20%;聚萘二甲酸树脂73.6%;二氧化钛 6%;铁黑 2‰;Solsperse-22000 0.1%;DarocurITX 0.1%均匀混合,搅拌并静置后,制备得到35μm的投影显示层;
将所述投影显示层涂布在聚氯乙烯薄膜(80μm)的一侧表面,固化成型;
在所述聚氯乙烯薄膜的另一侧表面涂覆有机硅胶粘剂(35μm);
将所述TPX离型膜(60μm)与有机硅胶粘剂复合;
收卷后制得所述透明显示膜。
实施例4
称取8mg油性四氧化三铁,分散于40mL环己烷中,超声0.5h后,加入5mL曲拉通X-100,5mL正己醇,1mL水,常温超声1h,随后缓慢加入350μL正硅酸四乙酯,超声1.5h后,加入0.8mL浓氨水,常温反应24h之后,在10000转/分钟的转速下离心分离收集,然后在65℃下加入0.9mL硝酸,加热反应8h,离心收集,得到纳米磁性二氧化硅空心球。
将以下重量百分含量的组分:纳米磁性二氧化硅空心球 16%;环烯烃聚合物树脂59.6%;氧化锌 9%;炭黑 4‰;EFKA Additives-4030 6%;DarocurITX 9%均匀混合,搅拌并静置后,制备得到15μm的投影显示层;
将所述投影显示层涂布在玻璃材料(80μm)的一侧表面,固化成型;
在所述玻璃材料的另一侧表面涂覆丙烯酸酯胶粘剂(15μm);
将所述PE离型膜(60μm)与丙烯酸酯胶粘剂复合;
收卷后制得所述透明显示膜。
实施例5
称取6mg油性四氧化三铁,分散于40mL环己烷中,超声1h后,加入5mL曲拉通X-100,5mL正己醇,0.8mL水,常温超声1.2h,随后缓慢加入250μL正硅酸四乙酯,超声1.2h后,加入0.8mL浓氨水,常温反应24h之后,在10000转/分钟的转速下离心分离收集,然后在62℃下加入0.8mL硝酸,加热反应8h,离心收集,得到纳米磁性二氧化硅空心球。
将以下重量百分含量的组分:纳米磁性二氧化硅空心球 12%;乙酸丙酸纤维素树脂 65.9%;聚甲基丙烯酸甲酯粒子 10%;骨黑 1‰;Dispers-685 6%;Darocur4265 6%均匀混合,搅拌并静置后,制备得到50μm的投影显示层;
将所述投影显示层涂布在聚氯乙烯薄膜(30μm)的一侧表面,固化成型;
在所述聚氯乙烯薄膜的另一侧表面涂覆丙烯酸酯胶粘剂(30μm);
将所述PE离型膜(60μm)与丙烯酸酯胶粘剂复合;
收卷后制得所述透明显示膜。
对比例1
将以下重量百分含量的组分:聚甲基丙烯酸甲酯树脂86.7%;三氧化二铝5%;炭黑3‰;Disperbyk-162 3%;IRGACURE127 5%均匀混合,搅拌并静置后,制备得到25μm的投影显示层;
将所述投影显示层涂布在聚对苯二甲酸乙二醇酯薄膜(50μm)的一侧表面,固化成型;
在所述聚对苯二甲酸乙二醇酯薄膜的另一侧表面涂覆丙烯酸酯胶粘剂(30μm);
将所述PE离型膜(60μm)与丙烯酸酯胶粘剂复合;
收卷后制得所述透明显示膜。
对实施例1~5以及对比例1制得的透明显示膜应用到投射系统,进行透光率和光通量测定,结果如表1所示。
表1 实施例1~5以及对比例1制得的透明显示膜的测定结果
透光率(%) | 光通量(lm) | |
实施例1 | 95 | 1262 |
实施例2 | 94 | 1195 |
实施例3 | 90 | 1236 |
实施例4 | 93 | 1199 |
实施例5 | 92 | 1213 |
对比例1 | 85 | 986 |
由表1可以看出,未经加入纳米磁性二氧化硅空心球的透明显示膜透光率为85%,光通量为986lm,经加入纳米磁性二氧化硅空心球的透明显示膜的透光率可达90~95%,光通量可达1195~1262lm,说明经加入纳米磁性二氧化硅空心球后,可以提高投影显示效果。
以上所述仅是本发明的优选实施方式,并非对本发明作任何形式上的限制。应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以做出若干改进和润饰,这些改进和润饰也应视为本发明的保护范围。
Claims (10)
1.一种透明显示膜,其特征在于,包括依次层叠的投影显示层、基材层、胶粘剂层和离型材料层;所述投影显示层包括纳米磁性二氧化硅空心球。
2.根据权利要求1所述的透明显示膜,其特征在于,所述纳米磁性二氧化硅空心球由包括以下步骤的方法制备得到:
将油性四氧化三铁和溶剂混合,得到分散混合液;
将所述分散混合液、曲拉通X-100、正己醇和水混合,得到分散复合液;
将所述分散复合液与硅源和浓氨水混合,常温下反应,得到纳米磁性二氧化硅;
将所述纳米磁性二氧化硅进行酸处理,得到所述纳米磁性二氧化硅空心球。
3.根据权利要求2所述的透明显示膜,其特征在于,所述硅源为正硅酸四乙酯;所述浓氨水的质量百分浓度为20~25%。
4.根据权利要求2所述的透明显示膜,其特征在于,所述酸处理的酸为50~60wt%的稀硝酸;所述酸处理的温度为50~80℃,时间为6~12h。
5.根据权利要求1所述的投影显示膜,其特征在于:所述基材层包括聚对苯二甲酸乙二醇酯薄膜、聚乙烯薄膜、聚氯乙烯薄膜或玻璃材料。
6.根据权利要求1所述的透明显示膜,其特征在于,所述投影显示层包括以下重量百分含量的组分:
纳米磁性二氧化硅空心球10~20%;
热塑性树脂55%~75%;
散射粒子材料1%~10%;
无机纳米黑色颜料1‰~5‰;
分散剂0.1%~6.3%;
固化剂0.1%~10%。
7.根据权利要求6所述的透明显示膜,其特征在于:所述散射粒子材料包括三氧化二铝、氧化锌、氧化锆、二氧化钛和有机玻璃粒子中的一种或几种。
8.根据权利要求6所述的透明显示膜,其特征在于:所述热塑性树脂包括丙烯酸类树脂、聚酯树脂、聚烯烃树脂、纤维素树脂、乙烯基树脂和聚碳酸酯树脂中的一种或几种。
9.权利要求1~8任一项所述透明显示膜的制备方法,其特征在于,包括以下步骤:
将纳米磁性二氧化硅空心球形成浆料后涂布在基材层的一侧表面,固化成型,形成投影显示层;
在所述基材层的另一侧表面涂覆胶黏剂,形成胶粘剂层;
将所述离型材料层与胶粘剂层复合,收卷后制得所述透明显示膜。
10.权利要求1~8任一项所述的透明显示膜或权利要求9所述制备方法制得的透明显示膜在投射系统中的应用。
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