CN1894314A - 用于制备可用于阻断近红外光透射的聚合物薄膜的方法 - Google Patents

用于制备可用于阻断近红外光透射的聚合物薄膜的方法 Download PDF

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CN1894314A
CN1894314A CNA2004800374729A CN200480037472A CN1894314A CN 1894314 A CN1894314 A CN 1894314A CN A2004800374729 A CNA2004800374729 A CN A2004800374729A CN 200480037472 A CN200480037472 A CN 200480037472A CN 1894314 A CN1894314 A CN 1894314A
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R·A·福吉尔
R·A·海斯
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EIDP Inc
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Abstract

本发明是红外线(IR)阻断涂层和将IR阻断涂层施加到聚合物表面上的方法。所述方法包括以下步骤：将IR阻断材料分散在包含溶解的聚合物的溶剂混合物中，和使用标准印刷方法涂覆本体聚合物、优选片材或者薄膜的表面的至少一部分。本发明还提供了安全玻璃层压材料，其聚合物夹层具有改进的对玻璃的粘合性以及光阻断性质。

Description

用于制备可用于阻断近红外光透射的聚合物薄膜的方法
技术领域
本发明涉及可用于阻断红外(IR)和/或近红外(NIR)光的薄膜。本发明具体地涉及在其至少一部分表面上具有IR和/或NIR-阻断涂层的聚合物以及制备该聚合物的方法。
背景技术
对控制汽车和建筑物中的日照得热量存在不断增强的兴趣。已经提出了各种涂覆的玻璃用以降低通过窗口的日照得热量。然而，这些涂层通常是银或者其他金属化合物薄膜，通常也阻断电动能量。这种作用使各种现代必需品例如移动电话、全球定位卫星(GPS)单元以及收费道路上的自动收费器无法工作。然而，已经证明，当阻断粒子彼此良好分离时，电动能量能够通过处理的窗口。
包含分散的阻断粒子和配置在玻璃或者其他基材上的涂层是众所周知的。参考例如U.S.5,518,810；U.S.6,579,608；和U.S.6,506,487。这些粒子可以包括紫外线吸收化合物，可见着色颜料，NIR(热)吸收化合物，或者这些物质的任何组合。然而，本领域中已知的能量阻断涂层通常具有差的对某些聚合物表面的粘合性，特别是聚乙烯醇缩丁醛(PVB)。对于保证层压安全玻璃具有适合的功能，聚合物夹层和能量阻断涂层和玻璃两者之间的良好的粘合性是必要的。粘合性过低可以导致安全玻璃层压材料的脱落，而粘合性过高可以导致冲击破坏。
发明内容
在一个方面，本发明是一种聚合物，该聚合物具有至少部分地被涂层覆盖的表面，所述涂层包含红外线阻断粒子，其中所述聚合物是薄膜或者片材的形式。
在另一个方面，本发明是一种组合物，其是包含在二甲基甲酰胺(DMF)中的氧化铟锡(ITO)和聚乙烯醇缩丁醛的分散体。
在另一个方面，本发明是制备聚合物薄膜或者片材的方法，该聚合物薄膜或者片材具有至少一个至少部分地被涂层覆盖的表面，该涂层包含红外线阻断粒子。IR阻断涂层通过包括以下步骤的方法施加：(1)将IR阻断粒子分散在PVB和二甲基甲酰胺(DMF)的混合物中，获得IR阻断油墨；(2)将IR阻断油墨印刷到聚合物表面的至少一部分上。
在另一个方面，本发明是制备聚合物薄膜或者片材的方法，该聚合物薄膜或者片材具有至少一个至少部分地被涂层覆盖的表面，所述涂层包含红外线阻断粒子，其中IR阻断涂层包含分散在PVB中的IR阻断粒子，该方法包括以下步骤：使IR阻断粒子、二甲基甲酰胺(DMF)和PVB的混合物通过研磨装置，以分散IR阻断粒子而获得IR阻断油墨；和将所述油墨印刷到聚合物薄膜或者片材的表面上。
在另一个方面，本发明是层压材料，其包含聚合物薄膜或者片材，其中所述薄膜或者片材包含至少一个至少部分地被IR阻断涂层覆盖的表面，所述涂层包含IR阻断粒子和PVB。
在另一个方面，本发明是层压材料，其包含至少两个聚合物薄膜或者片材的层，所述两个层的至少一个具有至少一个至少部分地被IR阻断涂层覆盖的表面，所述涂层包含IR阻断粒子和PVB。
附图描述
图1是一系列具有PVB片材的玻璃层压材料的光透射光谱的图形，所述片材是未涂覆的或者用能量阻断涂料涂覆的。
发明的详细说明
本文的定义适用于在本说明书中使用的术语，除非在特定的情况下另外限定。
正如在此使用的，就包含一种或多种聚合物的液体而言的术语“溶液”指其中至少一种溶质是聚合物的液体，虽然可溶性聚合物及其他物质，包括其他的聚合物，也可以以未溶解的形式存在于所述液体中。
正如在此使用的，术语“分散体”和“悬浮体”是可互换的，并且指包含颗粒物质的液体。分散体可以是就沉淀、絮凝、离浆等等而言稳定的、不稳定的或者部分稳定的。
正如在此使用的，术语“能量阻断”和“IR阻断”指降低能量传输的性质，或者特别地降低红外线能量传输的性质。阻断可以通过任何机理实现，例如吸收、反射等等。
正如在此使用的，术语“红外”包括近红外。
术语“有限量”和“有限值”指不等于零的量。
术语“大约”指量、尺寸、配方、参数及其他数量和特征不是和不必是精确的，而是依照要求可以是近似的和/或较大的或者较小的，反映出公差、换算系数、舍入、测量误差等等，以及本领域技术人员已知的其他因素。通常，量、尺寸、配方、参数或者其他数量或者特征是“大约”或者“近似的”，无论是否这样明确地说明。
在一个实施方案中，本发明是聚合物，在其表面的至少一部分上配置了红外线阻断材料的涂层，所述红外线阻断材料已经被预先分散在聚合物基质中。适用于本发明的聚合物是也适用于具有玻璃的层压材料的那些，并且优选可用于建筑或者汽车玻璃窗。例如，适合的聚合物是在光谱可见区中透光的那些。更具体地，适合的聚合物包括，非限制地，聚酯；聚氨酯；聚氯乙烯；聚缩醛；聚乙烯醇缩丁醛(PVB)；以及从乙烯与烯属不饱和羧酸和/或其衍生物的共聚获得的酸共聚物和共聚物离聚物。优选所述聚合物是聚乙烯醇缩丁醛。
所述聚合物可以通过常规方法成型为薄膜或者片材，例如通过各种常规的挤出方法，包括，非限制地，流延薄膜挤出方法或者吹塑薄膜挤出方法。
所述聚合物在其表面的至少一个上至少部分地被包含红外线阻断材料的涂层覆盖。所述红外线阻断材料可以是任何阻碍红外线光透射、优选特别是近红外光透射的材料。这类材料是已知的并且可以被认为是常规的。这类材料包括，例如，氧化铟锡(ITO)、氧化锑锡(ATO)、六溴化镧和铁氧化物。优选IR阻断材料是颗粒形式。通常所述粒子具有超细的粒子尺寸，使得层压材料的透明度不被不利地影响。优选本发明的IR阻断粒子包括ATO或者ITO。更优选，IR阻断粒子包括ITO。
本领域技术人员，根据例如和物理性能(例如涂层的雾度，或者涂覆的表面对层压材料中的另一种表面的粘合性)保持平衡的所希望的透射比水平，能够确定IR阻断粒子在IR阻断涂层中的适当的水平。然而，优选地，IR阻断材料以有限的量存在于涂层中，该量基于分散体(即IR阻断材料、DMF和聚合物)的总重量为最多大约30wt％，更优选大约10重量％到大约20wt％，并且更优选大约15重量％。
本发明中，IR阻断粒子作为小的粒子在基质中的分散体涂覆到聚合物的表面，所述基质包含有机溶剂例如二甲基甲酰胺(DMF)和聚合物粘合剂。优选地，聚合物粘合剂被溶解在有机溶剂中。优选地，聚合物粘合剂与被涂覆的聚合物是相同的或者相容的。“相容的”是指聚合物粘合剂强烈地粘附于被涂覆的聚合物的表面。聚合物粘合剂起到促进所述粒子粘合到聚合物表面的作用，并且改进涂覆的聚合物对层压材料中的邻接层的粘合性。
优选地，所述聚合物粘合剂包括PVB。更优选地，聚合物粘合剂基本上由PVB组成。更优选地，聚合物粘合剂基本上由具有大约23％自由羟基的PVB组成。
根据希望的涂层性质，本领域技术人员能够确定聚合物粘合剂的适当水平。然而，优选地，聚合物粘合剂以有限的量存在，该量基于IR阻断粒子分散体的总重量为最多大约20重量％，更优选大约3到大约13重量％，并且更优选大约8重量％。值得注意的是包含大约8重量％的23％自由羟基PVB的涂层。
在另一个实施方案中，本发明是将IR阻断材料的分散体施加到聚合物材料的表面的至少一部分上的方法，其包括将所述分散体印刷到所述表面上的步骤。优选所述聚合物材料是薄膜或者片材的形式。优选所述印刷步骤是常规方法，例如苯胺印刷或者凹板印刷。所述方法可以包括以下步骤：使IR阻断粒子通过研磨或者磨碎装置，例如Eiger磨，以降低IR阻断材料的粒子尺寸，和/或将所述材料分散在有机溶剂或者聚合物基质中。因此，IR阻断材料可以以干燥的形式或者作为在有机溶剂中的分散体或者作为在聚合物基质中的分散体通过研磨装置。如此获得的分散的油墨可以被印刷到所述聚合物的至少一个表面的至少一部分上。优选油墨被直接印刷到聚合物表面上。涂覆的聚合物可以任选地通过本领域中已知的任何合适的方法干燥，例如通过施加热或者真空或者两者。
在另一个实施方案中，本发明是层压材料，其包括至少一种聚合物层，该聚合物层至少部分地被包含IR阻断材料的涂层覆盖。适合的和优选的聚合物层和IR阻断涂层如以上提出的。所述层压材料优选包含至少一片玻璃，但是作为玻璃的替代物可以在刚性的透明层中包括另一种材料。
在另一个实施方案中，本发明包括至少两个聚合物层的层压材料，其中至少一个聚合物层已经被至少部分地用包含IR阻断材料的涂层覆盖。同样，适合的和优选的聚合物层和IR阻断涂层如以上提出的。所述片材可以作为邻接和相邻层层压在一起，或者可以由其他的层压层分离。涂覆的聚合物可以包括相同的材料或者不同的材料，包括相同的或者不同的IR阻断材料。在优选的实施方案中，所述涂层或者多个涂层被配置在所述聚合物层的两个之间。更优选两个聚合物层是邻近的。在另一个优选的实施方案中，所述层压材料包括玻璃或者在刚性透明层中作为玻璃替代物的其他材料的至少一个外层。更优选，所述层压材料包括两个玻璃或者其他刚性透明材料的外层。
本发明层压材料中的聚合物的涂覆表面可以是离开层压材料外表面取向的，或者朝着层压材料外表面取向的，或者可以是层压材料的外表面。玻璃窗领域中的普通技术人员可以预见到各种层压材料结构。
实施例
仅仅为了说明性的目的给出实施例和对比实施例，不意欲以任何方式限制本发明的范围。
实施例1
将氧化铟锡(40gms)分散在300gms的6.4％ PVB在DMF中的溶液中。将所述分散体在Eiger磨中、在环境温度下研磨大约4小时，或者直到混合物呈现均匀的外观。然后使用轮转凹版印刷方法将分散体手工浸渍到3GO-基PVB(30密耳)片材上。网速度是50fpm。PVB片材使用最多四层ITO分散体印刷。在每次印刷过程之后从印刷的PVB片材上切割下试样。
将涂覆的PVB片材的试样层压在两层透明玻璃(厚度2.3mm)之间。通过测量雾度、pummeling和波长在275到2500纳米范围内的光的透射比，来对玻璃层压材料进行测试。
示于图1中的类似的实验的光透射比结果清楚地表明，在较长的波长、包括NIR波长下，当应用本发明的涂层时，光的透射比显著地降低。此外，使用提高的ITO水平透射比甚至进一步降低。
虽然以上描述了和特别地举例说明了本发明的某些优选实施方案，但不打算将本发明局限于这样的实施方案。在不背离以下权利要求中阐述的本发明的范围和精神下，可以作出各种修改。

Claims (14)

1.一种聚合物，其具有至少部分地被涂层覆盖的表面，所述涂层包含红外线阻断粒子，其中所述聚合物是薄膜或者片材的形式。
2.权利要求1的聚合物，其中所述红外线阻断粒子包括选自以下的材料：氧化铟锡(ITO)、氧化锑锡(ATO)、六溴化镧和铁氧化物。
3.一种组合物，其是包含在二甲基甲酰胺(DMF)中的氧化铟锡(ITO)和聚乙烯醇缩丁醛的分散体。
4.权利要求3的组合物，其包含8重量％的23％自由羟基的聚乙烯醇缩丁醛。
5.一种制备聚合物薄膜或者片材的方法，所述聚合物薄膜或者片材具有至少一个至少部分地被红外线阻断涂层覆盖的表面，所述方法包括通过印刷将所述红外线阻断涂层施加到聚合物薄膜或者片材的步骤。
6.权利要求5的方法，其中所述红外线阻断涂层作为油墨施加，该油墨包含红外线阻断材料、聚乙烯醇缩丁醛和二甲基甲酰胺。
7.权利要求5的方法，其中红外线阻断涂层包含选自以下的红外线阻断材料：氧化铟锡(ITO)、氧化锑锡(ATO)、六溴化镧和铁氧化物。
8.一种制备聚合物薄膜或者片材的方法，该聚合物薄膜或者片材具有至少一个至少部分地被涂层覆盖的表面，所述涂层包含红外线阻断粒子，其中所述IR阻断涂层包含分散在PVB中的IR阻断粒子，所述方法包括以下步骤：使IR阻断粒子通过研磨装置，以分散IR阻断粒子，从而获得IR阻断油墨；和将所述油墨印刷到聚合物薄膜或者片材的表面上。
9.权利要求8的方法，其中使IR阻断粒子与二甲基甲酰胺、聚乙烯醇缩丁醛或者二甲基甲酰胺和聚乙烯醇缩丁醛两者一起通过所述研磨装置。
10.权利要求8的方法，其中所述IR阻断粒子包括选自以下的红外线阻断材料：氧化铟锡(ITO)、氧化锑锡(ATO)、六溴化镧和铁氧化物。
11.一种层压材料，其包含聚合物薄膜或者片材，其中所述薄膜或者片材包括至少一个至少部分地被IR阻断涂层覆盖的表面，所述IR阻断涂层包含IR阻断粒子和PVB。
12.权利要求11的层压材料，其中所述IR阻断粒子包括选自以下的红外线阻断材料：氧化铟锡(ITO)、氧化锑锡(ATO)、六溴化镧和铁氧化物。
13.一种层压材料，其包含至少两个聚合物薄膜或者片材层，所述两个层的至少一个具有至少一个至少部分地被IR阻断涂层覆盖的表面，所述IR阻断涂层包含IR阻断粒子和PVB。
14.权利要求13的层压材料，其中所述IR阻断粒子包括选自以下的红外线阻断材料：氧化铟锡(ITO)、氧化锑锡(ATO)、六溴化镧和铁氧化物。
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Open date: 20070110