CN1057042C - 显色虹彩薄膜及其制备方法 - Google Patents

显色虹彩薄膜及其制备方法 Download PDF

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CN1057042C
CN1057042C CN95104909A CN95104909A CN1057042C CN 1057042 C CN1057042 C CN 1057042C CN 95104909 A CN95104909 A CN 95104909A CN 95104909 A CN95104909 A CN 95104909A CN 1057042 C CN1057042 C CN 1057042C
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雷马克里斯那S·谢帝
斯克特A·库柏
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Abstract

公开了包括至少10层基本平行薄膜层的热塑性树脂薄膜，其中连接的相邻层具有折射率至少相差约0.03的透明热塑性树脂材料，此薄膜包含足够量的可溶于薄膜层的热塑性树脂材料的透明染料，其中加入染料的层加强或改善了薄膜的反射和透过色彩中至少一种外观色彩。

Description

显色虹彩薄膜及其制备方法
本发明涉及多层共挤出光反射薄膜，该薄膜具有光干涉引起的窄反射带。当反射带出现在可见波长范围内时，薄膜为虹彩的。同样，当反射带落在可见波长范围之外时，薄膜要么反射紫外光，要么反射红外光。这种多层薄膜及其制备方法在现有技术中是公知的，如在美国专利US3565985，3759657，3773882和3801429和其它专利中都已公开。
这种多层薄膜包括透明热塑性树脂材料的多个基本平行的层，其中连接的相邻层具有折射率至少相差约0.03的不同树脂材料。此薄膜至少包含10层，更常见地，包含至少35层，优选至少包含70层。
薄膜各层都很薄，通常为约30至500nm，优选约50-400nm，这样在从很多界面反射的光波中造成相干涉。依据层的厚度和聚合物的折射率，一个主要的波长带被反射，而余下的光透过薄膜，反射波长与一对薄膜层的光厚度之和成比例。
反射光的多少和色彩强度取决于两个折射率之间的差别、层的光厚度的比例、层数和厚度均匀性。若折射率相同，则自两层界面之间完全无反射，对于多层虹彩薄膜，连接的相邻层的折射率至少相差0.03，优选至少相差0.06或更多。对于第一级反射，当层的光厚度相等时，反射光最强，尽管当两光厚度的比落入5∶95和95∶5之间可得到合适的强反射光。少于10层时可获得明显的色彩反射。然而，要达到最大的色彩强度，需要具有35至1000层或甚至更多层。高色彩强度与相对窄的反射带和在其峰位时具有强反射光相关。应当认识到，虽然为方便起见，这里使用了术语“色彩强度”，但是同样的考虑适用于紫外和红外范围内看不见的反射。
这种多层薄膜可用骤冷辊流延工艺制备，此工艺中使用单集料管平薄膜模头和与之配合的供料头，该供料头从两个或多个挤出机的每一个中收集熔体并将其排列成需要的层型。供料头已经在美国专利US3565985和3773882中公开，此供料头可用于形成两组分(即：ABAB…)交替的层；三组分(例如ABCABCA…或ACBACBC…)交替层或更多组分交替层。很窄的多层流流过单集料管平膜模头，在模中各层同时在模的宽度方向展宽并变到与最终模出口厚度一样薄。层数及层的厚度分布可通过插入不同供料头模加以改变。通常，最外层或片材各边上的层要比其它层厚。这种厚的表皮层可由构成光学芯组分中的一种组成；可以是与用于带来需要的机械、热密封或其它性能不同的聚合物；也可以是这些聚合物的结合。
虹彩薄膜方面最近的一些进展公开于美国再公告专利US31780；4937134；和5089318中。美国再公告专利31780公开了使用热塑性对苯二酸酯聚酯或共聚酯树脂作为体系的高折射率组分。弹性体干涉薄膜的形成公开于美国专利US4937134中，其中所有的树脂材料为特定热塑性聚氨酯、聚酯嵌段酰胺或柔性共聚酯。美国专利5089318公开了包括至少大体相互平行的10层膜的多层反光透明热塑性树脂薄膜，其中连接的相邻层具有折射率至少相差约0.03的不同透明热塑性树脂材料，并且树脂材料中至少一种为工程热塑性弹性体树脂。
已需要将色彩包括在这些虹彩薄膜中以使其外表增加新的内容。这些色彩可加强或改变虹彩薄膜的反射或透过色彩。此外，在随观察角度改变虹彩的同时，非虹彩保持不变，因此可观察到的色彩将会基于虹彩和非虹彩组分的结合显著改变。不幸的是，将非虹彩色加入虹彩薄膜中证明难以掌握。在讨论塑料颜料时，将染料和颜料区别开很重要。在主要加工条件下，颜料实质上不溶于塑料，而染料是可溶的。
试图加入各种颜料，珠光和非珠光的都达不到满意的结果。现在确信，造成这样差结果的原因为如下之一个或多个因素：对于第一级最亮的色彩，位于薄膜光芯的薄膜层厚度通常为约0.03至0.2微米，而颜料颗粒大小通常约0.3微米左右。这就意味着颜料颗粒大于薄膜层厚度，因此使用这些颜粒破坏了两层之间的界面，结果造成虹彩和光散射损失。使用颗粒小于光芯层厚度的颜料会使薄膜加工过程中产生附聚和聚集，从而导致形成颗粒尺寸大于光芯层厚度的彩色体。在那些不发生这种聚集的场合中，会遇到两种相同不理想结果中的一种。要么颜料的浓度不够，达不到明显效果；要么当加入颜料的浓度对于最终薄膜的外观足以产生明显效果时，树脂性能被改变的程度较大，以致不能生产共挤出薄膜。已通过将颜料加入薄膜的表层进行了克服此问题的尝试，其中薄膜表层的厚度通常为3至7微米，并包括了薄膜总厚度的20至25％。这里同样为达到虹彩色的给定浓度，最好加入不多的颜料而能发挥最大的作用，这样薄膜看起来没有加颜料，当超过此浓度时，发现加入量对树脂而言太多，以至树脂不能延伸及流延成薄膜。
现在已经发现，若将具有某种特性的透明染料加入各层的树脂材料中，上述问题可以解决。
本发明涉及一种改进的具有色彩的多层反光薄膜，更特别涉及包括至少10层基本平行薄膜层的透明热塑性树脂薄膜，其中连接的相邻层具有折射率至少相差约0.03的不同透明热塑性树脂材料，涉及含有足量透明染料(此染料溶于薄膜层的热塑性树脂材料中)的薄膜中，加染料的层增强或改善了薄膜的反射和/或透过色彩中的至少一种外观色彩。
根据本发明，先有技术中的虹彩薄膜通过向其中加入特定染料进行改进。
本发明可用于迄今存在的所有多层薄膜。这些薄膜包括多层基本平行的透明热塑性树脂材料层，其中连接的相邻层具有折射率至少相差约0.03，优选相差0.06的不同树脂材料。这些薄膜至少包含10层，或一般至少包含35层，优选包含至少70层。薄膜各层都很薄，通常约30至500nm，优选约50至400nm。
多层薄膜通常由骤冷辊工艺制备，其中，用供料头收集从两个或多个挤出机出来的热塑性树脂熔体，并将其排列成需要的层型。很窄的多层流流过一单集料管平膜模头，使所有层同时在模的宽度方向延伸并变到最终模出口厚度。层数及层的厚度分布可通过使用不同的供料头模进行改变。通常，最外层或片材的每一侧的薄膜层比其它层更厚，这样形成相对厚的表层，用于形成表层树脂材料可以为构成光芯组分中的一种，或与用于使其具有需要的机械、热密封或其它性能的不同聚合物，或这些聚合物的组合。
根据本发明，将着色剂加入其中一种或多种树脂材料中，加入量要足以使薄膜反射色彩中的至少一种，或薄膜透过色中的至少一种，或两者(相对于不用着色剂时存在的相同性质)都能增强或改变。着色剂可以加入全部光芯层中或绝大部分光芯层中和/或所有或并非所有表层中。加入着色剂的层数及每层中着色剂的浓度随所需的色彩效果而变化。
为在本发明可使用，着色剂必须具有三个特点。首先，它必须透明，即基本不影响无着色剂的薄膜的虹彩性，换言之，薄膜的虹彩外观无明显变化。第二，着色剂必须溶于所加入的热塑性树脂材料中。这就意味着颜料类着色剂不能用。第三，着色剂在用于形成薄膜的加工条件下必须稳定。稳定性不仅指染料的色彩，还指染料在形成薄膜过程中承受的温度下，必须不迁移并且不挥发，其中温度通常高达约300℃。一般在约200～260℃之间。
可用于本发明的染料中，令人特别感兴趣的是那些溶于脂肪族或芳香族化合物中的染料，通常，偶氮染料，蒽醌染料、吡唑啉酮衍生物和吡啶酮染料适用于本发明。还有各种可加入塑料中的荧光染料也适用于本发明。
虽然前述染料属于优选中的，但容易想到，其它染料只要具有前面提到的三个性质，也可以使用。还会想到在光芯的各层中可以包含不同染料，因为染料(此染料溶于薄膜层其中一层的热塑性树脂材料中)当加入相邻连接层的树脂材料中时，可能缺少其中一种或多种所需的性质。
某一特定的染料是否满足三个必要条件，可很容易用一个简短的试验方法测定，即将染料和树脂材料混合并观察得到的性能。其中染料和热塑性树脂材料混合的方法不属于本发明的一部分，任何常规方法都可以使用。
虹彩薄膜的性质在于对于给定的反射色彩薄膜具有唯一的透过色彩。例如，对红反射色具有兰透过色；对于绿反射色，具有粉红透过色；对于兰反射色，具有黄透过色，等等。加入透明染料将或增强和/或改变反射和/或透过色。红色染料将增强反射红色的虹彩薄膜中的红色，并且将透过的兰色变为紫红色或洋红色(依红色染料的浓度而定)。同样，红色染料将兰色反射虹彩薄膜中的兰色变成紫红色或洋红色，并将透过的黄色变为橙色。使用各种染料的不同组合，同样也会发生虹彩薄膜反射或透过色的变化。不同的着色剂可用于虹彩薄膜的不同组分中，结果与组合染料相似。虹彩薄膜中的一组分使用红色而另一组分使用黄色将会产生与使用橙色相似的效果。
热塑性树脂中可加入的染料量仅受热塑性树脂材料中能溶解的量及在主要加工条件下可以加工而不产生迁移或挥发的限制。热塑性树脂中加入的染料的量取决于所需的效果。非常低的染料浓度会导致虹彩薄膜出现浅色光或青色(Pastel)强光。高染料浓度又会导致对于最终虹彩薄膜染料的影响太强。
为了说明本发明，下面给出了一些实施例，但应明了这些实施例不是用于限制本发明的。除非另外说明，本说明书和权利要求中的所有温度都为摄氏度，所有份数和百分数都按重量计。
                      实施例1
将对苯二甲酸乙二醇酯热塑性聚酯(PET)从一挤出机中，聚甲基丙烯酸甲酯(PMMA)从另一挤出机中加入供料头中，形成115层光芯层，并通过第三个挤出机将第二表层聚对苯二甲酸丁二醇酯加到每个表面，形成0.75密耳(19微米)厚的虹彩薄膜。此薄膜为明亮虹彩的，从反射的垂直倾角方向看基本为红色，从透过的垂直倾角方向看为兰色。
重复上述步骤，不同的是将红色吡啶酮染料以浓度约0.7％加入PMMA中，这种染料是透明的，溶于PMMA中，在加工条件下稳定(在260℃下薄膜加工过程中承受最大温度时不迁移、不挥发)。得到的薄膜光彩夺目，通过红色染料增强了红反射色，兰透过色变为紫色，薄膜呈红色调。
                    实施例2
制备与实施例1的光芯中具有相同聚合物的多层结构，不同的是光芯有229层，通过第三个挤出机加入的两个外表层为聚对苯二甲酸乙二醇酯(PET)。得到的薄膜厚度为1.40密耳(35.5微米)，其虹彩色比实施例1中的强，这是因为光芯中的层数增加了。红色染料的加入导致红反射色加强，兰透过色变为紫红色。
                       实施例3-6
重复实施例1，改变之处如下：
实施例 总层数    高折射率聚合物   低折射率取合物 表层聚合物
    3   117       PET     PMMA   PET W/红色
    4   117    PET W/红色     PMMA      PBT
    5   231       PET     PMMA   PBT W/红色
    6   231    PET W/红色     PMMA      PBT
                  实施例7-30
重复上述6个实施例中具有不同厚度的薄膜，得到下列垂直倾角方向的反射色：兰/紫、兰/绿、红/绿和红/黄。
                  实施例31-60
用兰色蒽醌染料按浓度约0.4％重复实施例1至24。
                   实施例61-90
用绿色蒽醌染料和黄色吡唑啉酮染料的组合以浓度约为0.15％重复实施例1-24。
                   实施例91-92
用黄色吡唑啉酮染料以浓度为0.6％重复实施例1和2。得到的虹彩薄膜从反射的垂直倾角方向看为红色和黄色。
                  实施例93
用黑色铬复合染料以浓度6％重复实施例2，得到的虹彩薄膜从反射的垂直倾角方向看为红色和黄色。
本发明中可进行各种替换和变化而不超出本发明的实质和保护范围。上述实施例表示可用PBT、PET和PMMA进行组合，及将染料加入其中薄膜某一组分中制备薄膜。染料可加入能用于制备虹彩薄膜的任何热塑性树脂材料中，只要所使用的染料满足三个必要条件。染料也可以加入虹彩薄膜的不只一层中，还可以在虹彩薄膜的所有层中都包含染料。此外还要注意，虽然本发明公开的是生产流延型平膜，也可以用成管的(吹膜)方法制备闪光薄膜。因此，这里公开的各种具体方案仅起到说明的目的，而不是用于限制本发明。

Claims (10)

1.一种透明热塑性树脂叠层薄膜，它包括很薄的、厚度约30至500nm的基本均匀的至少10层，所述层基本平行并且所述层的两个表面之一构成叠层薄膜的最外表面，连接的相邻层具有不同的透明热塑性树脂材料，连接的相邻层区别在于折射率至少相差约0.03，其特征在于此薄膜含有足够量的可溶于薄膜层的热塑性树脂材料中的稳定透明染料，其中加入染料的层，增强和改善了薄膜的反射和透过色彩中的至少一种外观色彩。
2.权利要求1的透明热塑性树脂叠层薄膜，其中叠层薄膜最外表面具有叠层表层，所述表层为一层厚度基本均匀的透明热塑性树脂材料层，每个表层厚度为薄膜和表层总厚度的至少5％。
3.权利要求2的透明热塑性树脂叠层薄膜，其中表层包括聚对苯二甲酸乙二醇酯或聚对苯二甲酸丁二醇酯。
4.权利要求1的透明热塑性树脂叠层薄膜，其中所述相邻树脂材料具有的折射率至少相差约0.06。
5.权利要求1的透明热塑性树脂叠层薄膜，其中一种热塑性树脂材料为聚对苯二甲酸乙二醇酯或聚甲基丙烯酸甲酯。
6.权利要求1的透明热塑性树脂叠层薄膜，其中染料存在于每种不同热塑性树脂材料中。
7.权利要求1的透明热塑性树脂叠层薄膜，其中染料并非存在于所有不同的透明热塑性材料中。
8.一种制备透明热塑性树脂叠层薄膜的方法，此薄膜包含很薄的厚度均匀的至少10层，所述层基本平行，连接的相邻层为折射率至少相差约0.03的不同透明热塑性树脂材料，通过将薄膜各层叠合，使连接的相邻层折射率至少相差0.03，其特征在于使用含可溶解的、稳定透明的稳定染料的透明热塑性树脂材料作为其中至少一层，染料的加入量要足以增强和改善叠层薄膜反射和/或透过色彩中的至少一种外观色彩。
9.权利要求8的方法，其中所有不同透明热塑性树脂材料包含溶解的透明染料。
10.权利要求8的方法，其中并非所有不同的透明热塑性树脂材料中都包含溶解的透明染料。
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DE69503181D1 (de) 1998-08-06
CA2148387C (en) 2002-03-26
EP0681910A1 (en) 1995-11-15
KR950031501A (ko) 1995-12-18
KR100347879B1 (ko) 2003-03-04
JPH0875920A (ja) 1996-03-22
CN1120997A (zh) 1996-04-24

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