CN110561872B - 一种结构稳定的复合结构生色材料及其制备方法 - Google Patents
一种结构稳定的复合结构生色材料及其制备方法 Download PDFInfo
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Abstract
本发明涉及一种结构稳定的复合结构生色材料及其制备方法,属于新材料制备领域。一种结构稳定的复合结构生色材料,所述材料由透明热塑性聚合物与结构生色材料逐层叠加后使聚合物四周边缘热粘结成一整体所得,所述材料的上表面层和下表面层均为热塑性聚合物。本发明所述成型复合结构具有相对明显的结构色,良好的机械强度,克服了结构生色材料结构稳定性差的缺点,本方法操作简便,成本低廉,可以大面积应用,还可以方便实现图案化,适用于日用品、包装、装饰等领域。
Description
技术领域
本发明涉及一种结构稳定的复合结构生色材料及其制备方法,属于新材料制备领域。
背景技术
化学染色污染是工业污染的主要来源。染整过程可能产生大量污染废水和有毒物质,严重影响生态环境。同时,由于环境因素的影响,这种化学色可能逐渐退色或消失。
值得注意的是,结构色被认为是另一种可选的着色途径,它来自可见光与微观物理结构的相互作用。结构色分为彩虹色和非彩虹色,其中光子晶体是一种具有光子带隙特性的周期性有序电介质结构,当其光子带隙位于可见波长范围内时,光子晶体可以呈现出彩虹色。而非彩虹色可以通过具有特征尺寸为可见光波长量级的非晶光子结构展现,其微观结构单元呈短程有序、长程无序排列。但是目前人工构建的结构生色材料,胶体微球阵列无外加保护,结构稳定性差,限制了其广泛的应用。因此,结构稳定的结构生色材料的研究具有重要的意义。
发明内容
本发明的目的是提供一种结构稳定的复合结构生色材料及其制备方法。
一种结构稳定的复合结构生色材料,所述材料由透明热塑性聚合物与结构生色材料逐层叠加后使聚合物四周边缘热粘结成一整体所得,所述材料的上表面层和下表面层均为热塑性聚合物。
本发明所述结构稳定的复合结构生色材料由聚合物与结构生色材料由下至上逐层叠加而成。该结构将结构生色材料固定在两侧的连续的聚合物层间,结构稳定。
进一步地,本发明所述复合结构生色材料的层数可根据所需颜色、图案等效果需求进行选择和组合,原则上无特殊限制。本发明所述复合结构生色材料由聚合物层与结构色层叠加获得,至少3层,即两层聚合物层夹着中间结构色层。叠加时向上按次序结构色层与聚合物层叠加,保证各结构色层被两层聚合物层夹着。
进一步地,优选所述复合结构生色材料的总层数为3~15层。
本发明所述结构稳定的复合结构生色材料中,所述结构生色材料为微纳球构成的层膜,所述层膜由微纳球有序或无序堆叠构成。微纳球在两侧的聚合物层间进行排列、堆叠,形成单层排列或多层堆叠的结构。所述排列和堆叠可为有序或无序。
本发明所述结构稳定的复合结构生色材料中,所述结构生色材料包括微纳球,还可包括粘结剂和/或黑色色素。其中,微纳球可以与粘结剂共组装来进一步增强结构稳定性;添加黑色色素来进一步增强结构色的饱和度。
优选地,当结构生色材料中包含粘结剂时,粘结剂与微纳球乳液的质量比为0%~20%。
优选地,所述粘结剂为多巴胺及其衍生物、阿拉伯树胶、天然树胶、天然橡胶、聚氨酯类、聚脲类、聚丙烯酸酯类、酚醛树脂类、环氧树脂类、聚乙烯醇类中的一种或几种。
本发明所述结构稳定的复合结构生色材料中,所述微纳球为无机物微球或耐热的有机物微球。
本发明所述耐热的有机物微球为玻璃化温度高于热塑性聚合物玻璃化温度的有机物微球。
本发明所述结构稳定的复合结构生色材料中,所述微纳球为实心或空心微纳球。
本发明所述结构稳定的复合结构生色材料中,所述微纳球的直径为10~1000nm。
优选地,所述结构生色材料为微纳球构成的层膜,由微纳球有序或无序堆叠构成;所述微纳球为无机物微球或耐热的有机物微球,所述微纳球的直径为10~1000nm,所述微纳球为实心或空心微纳球。
进一步地,所述微纳球为无机物微球为二氧化硅微球,二氧化钛微球,氧化锌微球,氧化铝微球,二氧化锆微球,五氧化二钒微球。
进一步地,所述耐热的有机物微球为交联的聚合物微球或含硫树脂微球。
更进一步地,本发明所述微纳球为双酚甲醛树脂微球。
上述无机物微球和耐热的有机物微球均可按现有技术公开的方法制得。
进一步地,所述热塑性聚合物为聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、聚甲醛,聚碳酸酯,聚酰胺、丙烯酸类塑料、线性聚烯烃及其共聚物、聚砜、聚苯醚,聚氨酯、聚四氟乙烯、聚对苯二甲酸乙二醇酯中的一种。
上述线性聚烯烃指聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、丙烯酸类塑料外的其他线性聚烯烃。
更进一步地,本发明所述热塑性聚合物为聚氯乙烯(PVC)膜,热塑性聚氨酯(TPU)膜。
本发明的另一目的是提供上述结构稳定的复合结构生色材料的制备方法。
本发明提供两种可选的技术方案用于制备上述结构稳定的结构生色材料。
一个技术方案为:一种结构稳定的结构生色材料的制备方法,包括下述工艺步骤:
将固含量为5%~30%的微纳球的乳液在一透明热塑性聚合物层上进行有序或无序组装,形成结构色层;将所得的涂覆有结构色层的热塑性聚合物层上覆盖另一层透明的热塑性聚合物层,通过热压使其两层热塑性聚合物层四周边缘贴合,并粘结成一个整体,得到结构稳定的结构生色材料单元;通过热压使所得结构生色材料单元的热塑性聚合物层的四周边缘及相接触的两层聚合物层贴合并粘结成整体。
另一技术方案为:一种结构稳定的结构生色材料的制备方法,包括下述工艺步骤:将固含量为5%~30%的微纳球的乳液在一透明的热塑性聚合物层上进行有序或无序组装,形成结构色层;将所得的涂覆有结构色层的热塑性聚合物层上覆盖另一层透明的热塑性聚合物层,重复上述操作,直至获得目标层数,通过热压使所有热塑性聚合物层四周边缘贴合并粘结成整体;也可以分步热压直至获得目标层数。
上述两种制备方法的技术方案中,所述结构色层的制备过程中,微纳球与粘合结剂共组装,粘结剂为多巴胺及其衍生物、阿拉伯树胶、天然树胶、天然橡胶、聚氨酯类、聚脲类、聚丙烯酸酯类、酚醛树脂类、环氧树脂类、聚乙烯醇类中的一种或几种,粘结剂与微纳球乳液的质量比为0%~20%。
上述两种制备方法的技术方案中,在热塑性聚合物层上有序组装微纳球的方法为加热组装法,沉积法,刮涂法,旋涂法;在热塑性聚合物层上无序组装微纳球的方法为滴涂法,喷涂法,打印法。
上述两种制备方法的技术方案中,所述通过热压使两层热塑性聚合物层贴合并粘结成整体的设备为热压设备,热压的温度为80~250℃,压力为4~16kN。
本发明的有益效果为:热塑性材料是日常生活中应用最广泛的聚合物之一,并且具有加工方便、综合性能好的优点。商品化热塑性材料与结构色相结合是一种新型、经济、环保的策略,该成型复合结构具有相对明显的结构色,良好的机械强度,克服了结构生色材料结构稳定性差的缺点,本方法操作简便,成本低廉,可以大面积应用,还可以方便实现图案化,适用于日用品、包装、装饰等领域。
附图说明
图1(a)~(c)为实施例1所得的结构稳定的复合结构生色材料的照片;
图2为实施例1所得的结构稳定的复合结构生色材料c的截面扫描电镜图;
图3(a)和(b)为实施例2所得的结构稳定的复合结构生色材料手机壳的照片及弯曲照片;
图4为实施例3所得的结构稳定的复合结构生色材料照片。
图5为本发明所述结构稳定的复合结构生色材料的结构示意图。
具体实施方式
下述非限制性实施例可以使本领域的普通技术人员更全面地理解本发明,但不以任何方式限制本发明。
下述实施例中所述试验方法,如无特殊说明,均为常规方法;所述试剂和材料,如无特殊说明,均可从商业途径获得。
实施例1
1、通过喷涂法在镂空模具的遮盖下,分别喷涂固含量为10%的直径为283nm,239nm和197nm的双酚甲醛树脂微球乳液在PVC膜上无序组装制备三种颜色的非晶光子结构的图案。
2、热压设备预热至120℃,将涂覆有非晶光子结构图案的PVC膜上覆盖另一层PVC膜,通过热压使其两层PVC膜贴合并粘结成整体,压力为8kN,得到结构稳定的复合结构生色材料。
实施例2
1、分别将固含量为10%的直径为283,239和197nm的双酚甲醛树脂微球乳液按20:1的质量比与固含量为0.01g/ml的炭黑水溶液复配得混合乳液,通过喷涂法在镂空模具的遮盖下,分别喷涂3种双酚甲醛树脂微球混合乳液在TPU膜上无序组装制备非晶光子结构的图案。
3、热压设备预热至120℃,将涂覆有非晶光子结构图案的TPU膜上覆盖TPU手机壳,通过热压使其两层TPU膜贴合并粘结成整体,压力为8kN,得到结构稳定的复合结构生色材料手机壳。
实施例3
1、通过加热组装法,在加热板上放置一PVC膜,温度为60℃,将固含量为10%的直径为283nm的双酚甲醛树脂微球乳液在PVC膜上有序组装制备光子晶体。
2、热压设备预热至120℃,将涂覆有光子晶体层的PVC膜上覆盖另一层PVC膜,通过热压使其两层PVC膜贴合并粘结成整体,压力为8kN,得到结构稳定的复合结构生色材料。
实施例4
1、通过喷涂法在镂空模具的遮盖下,喷涂固含量为10%的二氧化硅微球乳液在PVC膜上无序组装制备非晶光子结构的图案。
2、热压设备预热至120℃,将涂覆有非晶光子结构图案的PVC膜上覆盖另一层PVC膜,通过热压使其两层PVC膜贴合并粘结成整体,压力为8kN,得到结构稳定的复合结构生色材料。
实施例5
1、通过滴涂法在镂空模具的遮盖下,滴涂固含量为10%的聚硫树脂微球乳液在TPU膜上无序组装制备非晶光子结构的图案。
2、热压设备预热至110℃,将涂覆有非晶光子结构图案的TPU膜上覆盖另一层TPU膜,通过热压使其两层TPU膜贴合并粘结成整体,压力为8kN,得到结构稳定的复合结构生色材料。
实施例6
1、通过刮涂法,在一PVC膜上将固含量为10%的二氧化钛微球乳液在PVC膜上有序组装制备光子晶体。
2、热压设备预热至120℃,将涂覆有光子晶体层的PVC膜上覆盖另一层PVC膜,通过热压使其两层PVC膜贴合并粘结成整体,压力为8kN,得到结构稳定的复合结构生色材料。
实施例7
1、通过旋涂法,在一TPU膜上将固含量为10%的氧化锌微球乳液在TPU膜上有序组装制备光子晶体。
2、热压设备预热至120℃,将涂覆有光子晶体层的TPU膜上覆盖另一层TPU膜,通过热压使其两层TPU膜贴合并粘结成整体,压力为8kN,得到结构稳定的复合结构生色材料。
实施例8
1、通过喷涂法,在一PVC膜上喷涂固含量为10%的直径为239nm的双酚甲醛树脂微球乳液无序组装制备非晶光子结构,将涂覆有非晶光子结构的PVC膜上覆盖另一层PVC膜。
2、重复上述操作,形成5层的复合结构,其中结构生色材料分别在两侧的连续的聚合物层间。
3、热压设备预热至120℃,通过热压使所有PVC层四周边缘贴合并粘结成整体,压力为8kN,得到结构稳定的复合结构生色材料。
实施例9
1、通过打印法在PVC膜上打印固含量为10%的直径为230nm二氧化钛微球乳液,无序组装制备结构色图案。
2、热压设备预热至120℃,将打印有结构色图案的PVC膜上覆盖另一层PVC膜,通过热压使其两层PVC膜贴合并粘结成整体,压力为8kN,得到结构稳定的复合结构生色材料。
以上实例只是用于帮助更好的理解本发明的核心思想及技术方法,但不能以此限制本发明的保护范围。应当指出,对于该领域的普通技术人员,在依据本发明原理的基础上,还可以对本发明进行一定的改进与拓展,这些改进与拓展也在本发明权利要求的保护范围内;凡依据本发明精神实质所做的等效变换或修饰,都应涵盖在本发明的权利要求保护范围内。
Claims (7)
1.一种结构稳定的复合结构生色材料,其特征在于:所述材料由透明热塑性聚合物与结构生色材料逐层叠加后使聚合物四周边缘热粘结成一整体所得,所述材料的上表面层和下表面层均为热塑性聚合物,
所述复合结构生色材料的总层数为5~15层,
所述结构生色材料为微纳球构成的层膜,由微纳球有序或无序堆叠构成;所述微纳球为无机物微球或耐热的有机物微球,所述微纳球的直径为10~1000nm,所述微纳球为实心或空心微纳球,所述耐热的有机物微球为玻璃化温度高于热塑性聚合物玻璃化温度的有机物微球,
所述复合结构生色材料按下述方法制得:将固含量为5%~30%的微纳球的乳液在一透明的热塑性聚合物层上进行有序或无序组装,形成结构色层;将所得的涂覆有结构色层的热塑性聚合物层上覆盖另一层透明的热塑性聚合物层,重复上述操作,直至获得目标层数,通过热压使所有热塑性聚合物层四周边缘贴合并粘结成整体;也可以分步热压直至获得目标层数。
2.根据权利要求1所述的材料,其特征在于:所述无机物微球为二氧化硅微球,二氧化钛微球,氧化锌微球,氧化铝微球,二氧化锆微球,五氧化二钒微球;所述耐热的有机物微球为交联的聚合物微球或含硫树脂微球。
3.根据权利要求1所述的材料,其特征在于:所述热塑性聚合物为聚乙烯、聚丙烯、聚氯乙烯、聚苯乙烯、聚甲醛,聚碳酸酯,聚酰胺、丙烯酸类塑料、聚砜、聚苯醚,聚氨酯、聚四氟乙烯、聚对苯二甲酸乙二醇酯中的一种。
4.权利要求1~3任一项所述的结构稳定的复合结构生色材料的制备方法,其特征在于:包括下述工艺步骤:将固含量为5%~30%的微纳球的乳液在一透明的热塑性聚合物层上进行有序或无序组装,形成结构色层;将所得的涂覆有结构色层的热塑性聚合物层上覆盖另一层透明的热塑性聚合物层,重复上述操作,直至获得目标层数,通过热压使所有热塑性聚合物层四周边缘贴合并粘结成整体;也可以分步热压直至获得目标层数。
5.根据权利要求4所述的方法,其特征在于:所述结构色层的制备过程中,微纳球与粘合结剂共组装,粘结剂为多巴胺的衍生物、天然树胶、聚氨酯类、聚脲类、聚丙烯酸酯类、酚醛树脂类、环氧树脂类、聚乙烯醇类中的一种或几种,粘结剂与微纳球乳液的质量比为0%~20%。
6.根据权利要求4所述的方法,其特征在于:在热塑性聚合物层上有序组装微纳球的方法为加热组装法,沉积法,刮涂法,旋涂法;在热塑性聚合物层上无序组装微纳球的方法为滴涂法,喷涂法,打印法。
7.根据权利要求4所述的方法,其特征在于,所述热压的设备为热压设备,热压的温度为80~250℃,压力为4~16kN。
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