CN1081984C - 聚合物片材、保密票据制品和制备光学制品的方法 - Google Patents
聚合物片材、保密票据制品和制备光学制品的方法 Download PDFInfo
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Abstract
聚合物片材(11),该片材包括具有平行的第一表面(12)、第二表面(13)的第一层聚合物材料和置于第一层聚合物材料层中的多个多层薄膜薄片(16),所说的薄片具有平行的第一表面(17)、第二表面(18)和一个宽度,一个厚度,并具有宽度相对于厚度至少为2∶1的纵横比,所说的薄片加以取向,结果这些薄片位于该薄片的第一和第二平行表面基本上平行于第一层聚合物材料层的第一、第二平行表面的平面内。
Description
本发明涉及一种在其中放置有取向薄片的聚合物片材的多层干涉薄膜,一种使用这种薄膜的制品和一种方法。
专利No.5,135,812中公开了各种光学可变的多层干涉薄膜薄片,以及这些薄片如何加入油墨和油漆中。有必要寻找这些薄片的更多用途以拓宽其应用范围,例如,在塑料中封铸这些薄片,特别是用挤塑、共挤塑和铸塑的塑料片材来封塑。
总的来说,本发明的目的是提供一种挤塑或铸塑的并在其中有取向的多层干涉薄膜薄片的塑料片材,以及提供一种使用这些薄片的产品和一种方法。
本发明的另一目的是提供一种上述能挤塑或铸塑的塑料片材。
本发明的另一目的是提供一种上述薄片是双轴取向的塑料片材。
本发明的另一目的是提供一种上述的其中薄片是光学可变的塑料片材。
本发明的另一目的是提供一种上述能用常用的共挤塑生产线制备的塑料片材。
本发明的另一目的是提供一种上述的能涂覆到塑料基料上作为一种基材的塑料片材,在该塑料片材和该塑料基料之间粘合较弱。
本发明的另一目的是提供一种上述的具有可以是白色或彩色塑料基材的塑料片材。
本发明的另一目的是提供一种上述的其中具有一层或多层薄片的塑料片材。
本发明的另一目的是提供一种上述的其中不同层的薄片可以是不同颜色的塑料片材。
本发明的另一目的是提供一种上述的其中薄片在一层中随色移是光学可变的塑料片材,该层的色移与其他层的色移不同。
本发明的另一目的是提供一种上述的其中可向光学可变的薄片中加入另外的着色剂以改变光移或调整生成的颜色。
本发明的另一目的是提供一种上述的能易于掺入其他产品的塑料片材。
本发明的另一目的是提供一种上述的能切成窄条并组成线用于如钞票的证卷纸中的塑料片材。
本发明的另一目的是提供一种上述的其中该片材中只有相对少量的薄片但仍能达到所希望的光学效果的塑料片材。
本发明的另一目的是提供一种上述的具有光滑外表面的塑料片材。
本发明的另一目的是提供一种制备具有上述特征塑料片材的方法,其中在膜光学产品中使用机械流动来引起颜料薄片的层流取向。
本发明的另一目的是提供一种上述的稳定该塑料片材中薄片颜色特性的方法。
本发明的另外一些目的和特征体现在下面的对优选的实施方案和附图的详细介绍中。
图1是聚合物片材横切面局部等比例视图,该聚合物片材在其中含有本发明取向的多层干涉薄膜薄片。
图2是载于一塑料基材上的本发明共挤塑聚合物片材的剖视图。
图3是在塑料基材的相对两侧的两层上具有薄片的本发明共挤塑聚合物片材的剖视图。
图4是其中具有本发明薄片的基材的聚合物片材的剖视图,该片材的每侧都放置有可以是透明的或用颜色着色的塑料层。
图5是一种聚合物片材的剖视图,该聚合物片材具有厚的透明聚合物基层,在此上面是含有光学可变薄片及另外一些如染料、颜料、铝片等附加材料的聚合物材料薄层,以及一层透明的覆盖清漆。
图6是其中嵌入用本发明聚合物片材制成的线的钞票的平面视图,在该钞票的一面可看见此聚合物线。
图7是沿图6线7-7剖开的剖视图。
图8是类似于图7的视图,但显示该线织入钞票的方式以便在钞票的两侧都能看见此线。
图9是含有本发明聚合物片材的证卷文件(securrty document)剖视的部分等比例视图。
总的来说,本发明的聚合物片材包括具有第一和第二平行表面的一层聚合物材料层。在聚合物材料层内放置多个多层干涉薄膜片。该薄片具有第一和第二隔开的平行表面,并具有纵横比(宽度相对于厚度)至少为2∶1的宽度和厚度。该薄片位于该薄片的第一和第二表面基本上平行于聚合物材料层的第一和第二表面的平面内。
附图中的图1更详细介绍了塑料或聚合物片材11,该片材11具有上下平面隔开的平行表面12和13。可通过铸塑和挤塑制备该聚合物片材11。同样,如下文所述,可通过共挤塑膜制备片材11,在该共挤塑膜中片材11形成数层中的一层。
形成片材11的薄膜的厚度应该至少是多层干涉薄膜片的厚度的两倍,该薄膜片一般具有大约1微米的厚度,以便该片材11具有大约两倍薄片的厚度,或者换句话说,如果该薄片的厚度为1微米时,片材11的厚度为2微米。
关于本发明,可以使用各种聚合物,例如可使用水性聚合物,聚乙烯醇、聚乙酸乙烯酯、聚乙烯吡咯烷酮、聚(乙氧基乙烯)、聚(甲氧基乙烯)、聚(丙烯酸)、聚(丙烯酰胺)、聚(氧乙烯)、聚(马来酐)、羟乙基纤维素、乙酸纤维素和如阿拉伯树胶和果胶的聚(糖化物)。如果采用有机溶剂基的话,几乎任何可溶的聚合物体系都可使用。这包括上述所列的水性聚合物的例子,还包括另外一些聚合物,聚(缩醛类)、如聚乙烯醇缩丁醛;聚(乙烯卤化物类)、如聚氯乙烯、聚1,2-二氯乙烯;聚(二烯类),如聚丁二烯;聚烯烃,如聚乙烯;聚(丙烯酸酯类),如聚丙烯酸甲酯;聚(甲基丙烯酸酯类),如聚甲基丙烯酸甲酯;聚(碳酸酯类),如聚(氧羰基氧己亚甲基);聚(酯类),如聚对苯二甲酸乙二醇酯;聚(氨酯类);聚(硅氧烷类);聚(硫化物类);聚(砜类);聚(乙烯腈类);聚(丙烯腈类);聚(苯乙烯);聚(亚苯基类),如聚(2,5-二羟基-1,4-亚苯基乙烯;聚(酰胺类);天然橡胶类;甲醛树脂类以及列于Po1ymerHandbook(第二版,J.Brandrup E.H.Emmergut,eds.,John Wi1ey和Sons,NY,1975,IV-242页)上的其他聚合物。
多个多层干涉薄膜薄片16置于片材11的上下表面12和13之间。薄片16具有平行的上表面17和下表面18,并具有一个沿着表面17、18最大的尺寸或宽度和在垂直于17、18表面方向上所测得的一个厚度,使得该薄片宽度相对于厚度的纵横比至少为2∶1。这些薄片可以是单色、也可以是光学可变的。这些薄片可根据专利No.5,135,812的内容来制备。光学可变的颜料可通过如专利No.5,135,812所述的所有的绝缘薄膜层或金属绝缘层来制备。
形成光学可变薄片的金属绝缘多层干涉薄膜涂层可以呈不透明的金属层形式,该金属层具有在第一和第二表面的每一面上低折射率的绝缘层和n/k之比近于1的吸收层的第一和第二表面,其中n是折射率,k是吸收常数。低折射率材料可是氟化镁,同时该吸收层是铬。该厚的基本上不透明的金属层可由铝构成。
待加入待制备的聚合物片材中的颜料片16可加入到干燥的聚合物中,并在加入挤塑料斗喂料系统之前与聚合物立即混合。颜料薄片的量可按所希望的比例加入,并且相对于该聚合物的重量可在大于30%到小于0.1%的范围内变化。将该混合有颜料薄片的聚合物加热至完全融化为一体。其中含有颜料薄片的熔融聚合物通过一个模头挤塑到一冷却的流延鼓里,这样该熔融的聚合物迅速骤冷形成无定形膜。一般该熔融的聚合物在20秒内从大约275℃的熔融温度冷却到120℃以下。
然后为了使该聚合物单轴取向,通过加热该膜到它的拉伸温度(大约90℃)并在两组夹辊间拉伸该膜来进行正向拉伸,在这两组夹辊中第二组比第一组转速快,造成该膜在一个方面上的拉伸并使得在该膜内分子链沿着拉伸方向排列,而引起该膜的单轴取向。在该膜单轴取向后,通过一个横向拉伸以形成双轴取向或垂直于单轴取向方向上的取向。在常用的拉幅机(未示出)上进行该横向拉伸,该拉幅机预热该膜至80-90℃,并通过夹住该膜的两边在100-120℃范围内拉伸,此时该膜在拉幅机上向前拉伸。当完成该横向拉伸后,该双轴取向膜通过一个常用的温度在200-230℃范围内的结晶炉(未示出),首先造成该膜更大程度的的结晶,分子链有规律地堆集在一起并引起密度增加;其次引起该无定形区域的松弛并作为应力消除区域;再其次引起该结晶区域在该膜的平面外解取向。这些变化提供了该膜可识别的特征。应变松弛和结晶使膜具有很好的尺寸稳定性。
有关本发明,业已发现就该膜中的颜料薄片16的取向而言,该膜的双轴取向有着另外的优点。已发现当膜正通过正向拉伸时,具有第一表面17和第二表面18的、垂直于拉伸方向放置的该颜料薄片可能被翻倒,结果它们的第一表面17和第二表面18位于平行于该膜第一和第二表面的平面内。类似地,当该膜通过横向拉伸时,表面位于垂直于横向拉伸方向的方向上的颜料薄片16可能被翻倒,结果它们的第一表面17和第二表面18也位于平行于该膜11的第一和第二表面的平面内。
膜11的这种双轴取向的结果示于图1,其中如图1的剖视图所示的膜11的横切面,该颜料薄片16位于平行于该膜表面12和13的平面内。同样,观察也示于图1纵向方向的剖视图,该薄片16也位于平行于该膜表面12和13的平面内。
已发现在膜的双轴取向过程中这种机械运动引起前述膜中颜料薄片的适当排列,结果该薄片放于该膜的表面之下以提供一个具有光滑的第一表面12和第二表面13的膜,这一点很重要。这种在双轴取向过程中的机械运动也是所希望的,因为该熔融聚合物仍然是粘稠的,以致于在成膜过程中,在没用前述的机械拉伸的情况下,该薄片很难置于该粘稠的物质中。还发现当制备的膜越薄时,所有的或几乎所有的薄片16适当取向的可能性越大。作为例子,膜11具有2-5微米的厚度,而该颜料片具有1-2微米的厚度。
经过结晶炉的膜11可被冷却,然后可通过裁边和裁成同样合适的尺寸来切成所希望的宽度,例如1-3毫米宽度。下文结合本文所公开发明的其他实施方案介绍图1所示膜的应用。
当希望给聚合物片材11提供另外的载体时,可用基材或基材层21来形成图2所示的复合结构22。该基材或基材层21具有隔开的平行上表面26和下表面27。该基材层21可以由任何合成的、成膜的聚合物材料构成。适合的聚合物材料包括热塑性材料。
基材层21可以如膜11一样的方式进行双轴取向,首先在正向上拉伸然后横向拉伸以产生连续的双轴拉伸。
应该懂得在本发明中,通过挤塑一种热塑性聚合物管、接着骤冷、再加热,然后通过内部气压膨胀来引起在一个方向上的横向取向,并产生相反方向的轴向取向,这样来实现同步双轴取向。可通过以一定的速度拉伸该聚合物管子来完成同步双轴取向,该速度可引起在与由气体膨胀引起的取向的第一方向的垂直的轴向取向。
也应该懂得在本发明中,通过多孔模头的独立模孔同时共挤塑各自的成膜层,然后将仍然是熔融的各层结合,或优选通过一个单一的共挤塑料道,其中各自聚合物的熔融流首先在一个通向模头集流腔的料道里汇合在一起,然后在层流条件下不混合从模口共挤塑来形成复合片材,通过这样基本上可同时形成第二层11和基材21,然后可拉伸该共挤塑的片材以同时在两层的正向上使分子取向,接着横向拉伸以产生两层的双轴取向并据此引起第二层11的部分结晶。在这些情况下,可优选在尺寸限制情况下,在高于第二层聚合物的结晶熔化温度热定形和使该膜冷却以确保该第二层聚合物仍保持基本的无定形。由一层聚酯基材层和一层冷却的聚酯第二层构成的聚合物膜一般是在200-250℃的温度范围内进行热定形。由于第二层11的无定形,基本上消除了或至少显著减少了取向过程中颜料薄片周围的空隙以提高该膜的光学性能。于是,如图2所示,含有多层干涉薄膜薄片的第二层11置于一个表面上,例如置于基材21的上表面或第一表面26。采用这种两层排列,可提供一层相对厚的21层和一层很薄的11层,含有多层干涉薄膜薄片的这薄层或第二层充分利用这些薄片,因为这些薄片是这层中昂贵的组份。于是,通过具有二或三层随机分散的薄片(在实行中)以得到具有很薄层的连续涂层,因此使用少量的材料同时仍提供了所希望的颜色饱和度,这样就有可能获得几乎完全的颜色饱和度。
关于提供图1中所示的聚合物片材11,还应懂得除前文介绍的挤塑制备外,还可通过铸塑,例如通过常用缝式流铸机制备。在铸塑中,如同挤塑,可引入多层干涉薄膜薄片并和溶有聚合物的溶液混合,然后通过缝式流铸机。该铸塑过程也可引起薄片16的取向,结果薄片16水平放置或位于平行于片材11的上表面12和下表面13的平面内。
使得薄片16的宽面侧放着的薄片16的运动通过三个方面的努力来实现。在溶剂铸塑膜中,重力对薄片16宽边朝下放起着很大的作用。该铸塑膜的干燥过程中所产生的表面张力增强了这种宽面朝下的趋势,该铸塑膜的干燥过程类似于前文所述的双轴拉伸。考虑表面张力的作用,当聚合物干燥和溶剂蒸发时,该聚合物趋于收缩并把该薄片拉平。铸塑过程中在流动方向上,该流动会引起该薄片沿流动方向取向,同时让该薄片在重力的作用下排列,结果这些薄片平放。如果该聚合物是热熔材料,接着存在于涂布缝口模头的剪切力引起该薄片平放。因此可发现这些薄片以与挤塑膜双轴拉伸十分相同的方式取向。
在图3所示的本发明的实施方案中,一层11层也可以在第二表面27上,从而使基材21的另一面上具有相同或不同的颜色效果。可使用本发明的多层干涉薄膜薄片来提供单色的颜料或光学可变的颜料。因此,在基材的两个相对面上的两个不同层11可具有不同的颜色或可具有相同或不同的光学可变特性。为了加强对颜色的感受,该基材21可配有黑色染料或另外可着色以达到不同的颜色效果。该基材也可以是白色。
图4示出了复合结构32,其中中心层11是载有薄片的层,两个外层21是透明的或是用颜色着色的以在11层的两个相对面上形成不同或相同的颜色效果。
图3和图4的复合结构可以前文所述的方法共挤塑。应懂得如果需要的话,可提供另外一些能以前文所述的方法同时共挤塑双轴拉伸的层。
本发明的聚合物片材复合材料的厚度可在12-500微米、3-175微米内变化,优选为3-30微米。作为例子,第二层11可占整个组合物厚度的1-50%,一般为1-20%。第二层优选具有最高为20微米的厚度,更优选为0.5-10微米。
适于用作11层颜料的多层干涉薄膜薄片包括多层光学涂层,一般为三层、五层和更多层以产生更强的分光效果。作为例子,五层光学可变的薄片在对称设计中是优选的,如专利No.5,135,812所述,这五层的构成是:首先是一层薄的半不透明金属层,接着依次是第一绝缘层,厚的金属反射层,第二层绝缘层和薄的半不透明第二层金属层。第一层半不透明金属层和绝缘层形成一个光学涂层的底部结构(substructure),该底部结构是第二层半不透明金属层和绝缘层的光学涂层底部结构的相反形式(inverted version)。每一层半不透明的薄金属层优选含有标称5纳米厚的铬层。每一层绝缘层是由如二氧化硅或氟化镁的绝缘材料形成,以在具体的设计波长中形成几个半波的光学厚度。厚的金属反射层可包括厚度为40或高于40纳米的铝层从而提供高不透明度和高反射性。另外,可使用象镍和不锈钢的材料来代替半不透明金属层中的铬。也可以使用折射率为1.65或更小的如氟化镁(1.38)和氧化铝(1.65)的无机材料,来代替绝缘层中折射率为1.46的二氧化硅。可以使用如金、铜或银以及钴-镍磁性合金的材料来代替金属反射层的铝。
可使用类似于五层结构设计的三层光学可变薄片,但可去掉第二层半不透明金属层和绝缘层的光学涂料基底结构。另外,可使用如U.S.专利5,278,590所述的三层光学设计作为该干涉薄片。
随着入射光角度的变化,优选的五层光学可变的薄片的实例呈现深绿和紫色色调。深绿的光学可变薄片对于二氧化硅层在约515纳米波长处含有多个半波。这样就产生了在515纳米处具有第六级反射最大值的光学可变薄片。在515纳米波长处具有60%或大于60%反射率的窄束反射脉冲结果是在附近波长处反射几乎为零。尽管在近红外区和短波长蓝色区域处产生第四和第八级反射最大值,但该薄片仍产生饱和的绿色。由于二氧化硅层低的折射率(1.46)和它的高序数,随着涂层观察角的变化产生了大量的色移。在观察角为45°时,第六级峰移(peak shifts)进入蓝色区域,并且第四级峰移缩减进入红色区域,在515纳米绿色区域剩下低反射。因此,当观察角增加时,该涂层的表观颜色从深绿变成紫色。
第二优选的五层光学可变的薄片包括在450纳米处具有多个半波的二氧化硅层。该涂层在光谱的红色部分有第四级反射峰,在光谱的蓝色部分有第6级反射峰,当从法线入射处观察时,该反射峰产生深紫色。当从大角处观察时,第四级峰移入绿区,并在蓝区和红区中反射较低。这就造成在大角观察时,该涂层的表观颜色从紫色变成绿色。
因此,用于本发明的在聚合物膜中的第二层或11层含有的光学可变的薄片一般呈现两种截然不同的颜色,当从垂直于薄片表面的方向上观察时呈一种颜色,当从与该薄片表面呈大角(如45°)处观察时呈另外一种颜色。因为使用了至少一层具有低折射率(优选为1.65和更低)的绝缘层,所以获得了这种奇迹般的色移。
适于用作本发明聚合物膜的第二层或11层的薄片具有0.5-200微米的粒径,优选为1-20微米,该“粒径”是指薄片最大宽度的尺寸。该薄片的平均粒径,即最大宽度优选为1-20微米。
该光学可变薄片的纵横比(指最大宽度与厚度之比)适当地大于2∶1,优选为5-10∶1。
为了获得本发明优良的特性,位于11层中的光学可变薄片的浓度,相对于11层中聚合物的重量而言,适当的为1-50%(重量),优选为2-30%(重量)。
关于本发明,业已发现最好在相对高的温度下烘烤该颜料薄片,例如在250℃或更高温度下烘烤2-4个小时以使该颜料片更耐用。虽然还不完全明白其反应机理,但据信在空气或氧气中高温烘烤可提高这些薄片的耐用性。实质上,在聚合物薄膜的挤塑和双轴取向过程中,把该颜料薄片置于聚合物膜上也能获得同样的效果,因为也使用了高温。
虽然在本发明中介绍过在挤塑聚合物材料之前把这些颜料薄片加入到聚合物材料中,但应该懂得如果需要的话,薄片16可在单体转移过程中加入或加入到高压釜中。然而已发现优选在聚酯合成的酯化反应阶段把这些薄片以乙二醇分散液形式加入。另外,在挤塑之前,可把该颜料薄片直接加入聚合物片中。因此,这些薄片可以干粉形式加入聚合物中,再从此熔融挤塑。
本发明中制备的膜的各层可含有在制备聚合物膜中通常使用的任何添加剂。因此,如果合适的话,可把如染料、颜料、润滑剂、抗氧剂、防粘剂、表面活性剂、紫外线稳定剂、粘度改善剂和分散稳定剂加入到第一层和/或第二层中。具体地讲,为了产生具有其他色移效果的其他颜色,该光学可变薄片的分光效果可与加入到第二层的聚合物材料中的匹配或对比染料颜料和/或颜料结合起来。透明的颜料和染料可用来遮挡不希望的颜色,如专利No.5,135,812所述。
应该懂得这里所公开的复合结构也可以由密封在本身上的材料构成,另外也可以提供其他层来实现密封。还应该懂得,本发明制备的聚合物薄膜可在一面或两面上涂覆一层或多层另外的涂层,如油墨、清漆和/或金属层以形成一个层压或复合材料,该材料和其组分材料相比具有改良的性能,如抗静电性、增加粘合性或脱模性(release)。
双轴取向一般可通过适当量的正向和横向拉伸进行来制备所需厚度的膜。作为实例,一个膜在正方向上被拉伸原尺寸的3.6倍,在侧方向或横向被拉伸原尺寸的4.2倍。该膜组合物在约225℃温度下、展幅炉中、尺寸限制的条件下最后进行热定形。
根据前述本发明制备的并在其中具有取向的多层干涉薄膜薄片的双轴取向聚合物膜光学制品可用于许多种不同的产品中。可得到特别新颖的和称心的颜色效果,这可用于各种装饰目的。当该薄片呈光学可变颜料的形式时,它们在为证卷文件提供安全性能方面特别有用,该证卷文件如钞票、证书、信用卡,安全型身份文件如驾驶执照等。为了减少对这种膜的大量需求,可把少量的这种聚合物膜加入到证卷文件中。它们也可以加入到可能被仿造物品的标签或包装中。证卷文件中存在甚至少量的该聚合物片材也可能使一个人,如在街上的一个人通过观察是否存在一个色移就很容易辨别真品和伪造品。
由于这里采用了复杂的工艺,如果仿造者可能复制这些多层干涉薄层薄片,也是很复杂的,因而提供了安全性。另外,它需要大量的基建投资将薄片加入双轴取向聚合物薄膜中来创造所希望的光学效果。此外,该证卷文件不能在彩色复印机上复印,因为该光学可变特性不能通过彩色复印机复制。
图5是另外一个复合聚合物片材结构34,其中该聚合物结构具有一个有上表面37和下表面38的基材36。和前述实施例中的基材相比,基材36可相对厚一些,例如为5密耳到3/8英寸,并可以是透明的。在37面上的中心层11可以是前述的类型,并可以为含有前述光学可变薄片16的聚合物材料薄层形成。除了该光学可变薄片外,11层可搀有其他材料,如染料、颜料和铝片等。这些染料、颜料和类似物可用于现有技术中熟练人员所公知的各种目的。例如,它们可以用来遮挡各个角度不希望的颜色。它们也可以用来消除一个颜色。在11层上面可有一个覆盖层39,该覆盖层39可由相对较硬的材料如清漆制成。如图5所示,这种复合结构34可用于许多应用中,如用于地板或其它装饰效果。
本发明在证卷文件41中采用本发明的聚合物膜的实施方式的实例示于图6。在图6中,证卷文件为片状材料的形式,如钞票,由厚度为2-3密耳,具有第一和第二表面42和43的纸制成,表面42和43相互隔开,并与线46平行,线46至少部分地埋入票据纸中。线46横向延伸通过该票据邻近的一侧,如图6所示,而该线的彼此隔开的部分46a暴露于一表面或上表面42,紧接的部分46b则埋入票据纸中,如图7所示。另外,如图8所示,线46可以埋入钞票纸中使彼此隔开的部分46a可从表面42观看到,紧接的部分46b埋入票据纸中,并且另外的彼此隔开的部分46c可从钞票的另一面43看到。
线46可由双轴取向的聚合片材11或上述的流延膜来制得。将片材11切成适当的宽度,如1.3-3密耳宽,0.5密耳厚可得到用作线46的细长条。该线可以具有长方形的截面。根据本发明,该线可以装入钞票中,如图6所示,以从钞票的一面消除一种颜色或提供一种颜色或一种光学可变效果。如果如图7所示装入钞票中,该线部分可以票据两面看到,钞票的两个相对面可获得两种不同的颜色效果或光学可变效果。例如,一面具有由黄变绿的色移,而另一面具有由绿变蓝的色移。另外,一面可以只是金属反射物,如在这里加入了铝片,而另一面有光学可变效果。
应该懂得除了本发明聚合物膜线外,还可把少部分本发明聚合物膜加入证卷文件中以由此形成一个整体。因此,可在信用卡、过境通行证(transit passes)或其他重要文件中使用少部分该聚合物膜。
图9表示了一份证卷文件的例子,这里所示的文件可以是适当大小的California驾驶执照51的形式,以便它易放入常用的钱夹里,如2"×31/4"。它有一个由前述类型的适当塑料制成的相对硬的基材52。它可有一个适当的厚度,如2-10密耳。它有两个隔开的平行上表面53和下表面54。一层适当材料(如纸)层56通过加热加压和使用粘合剂(未示出)层压在53面上。根据该证卷文件的应用情况,56层可载有图片或照片57和印刷信息58,如图8所示。该照片,例如可是彩色照片,印刷的信息可以是不同的颜色。在这种应用情况下,56层可以是不透明的。然而,应该懂得,如果需要,层56可由半透明材料制成。
可通过使用透明的粘合剂(未示出)和适当的加热和加压把本发明的聚合物层61层压粘合到层56上,来制成该证卷文件。该聚合物片材含有前述类型的多层干涉薄膜薄片62。作为例子,在这个应用中该聚合物片材61可相对薄,如2-3微米。薄片的浓度可相对低,如在前文所定的低范围内,结果该聚合物片材61是半透明的,以便人眼可观察到片材56上的信息,如照片57和印刷的信息58。在这个应用中的薄片62可以光学可变型的来提供一个相对低的颜色浓度,这里对人眼仍存在一个色移,从而为证卷文件51提供了另外一级安全保护。
总之,有关本发明,通过把多层干涉薄膜薄片加入聚合物膜中,可以最大化该光学薄片的光学效果并最小化所需薄片的量。这一点是很重要的,因为相对于聚合物膜的成本而言,该颜料薄片是相对昂贵的。理论上,具有互相接触的薄片的单层平面薄片可达到最佳光学效果,以便实际上是单层并最少使用该薄片。实事上,这种薄片的最佳排列是很难达到的,因为该聚合物片材具有第三维尺寸,因此这些薄片不可能位于任何单一平面上。在薄片之间还有一些交错或空隙。然而,通过如前文所述的薄片在聚合物片材中的取向,达到了这些薄片的最佳光学性能。通过在挤塑过程中采用高于约250℃的相对高温,降低了该熔融聚合物的粘度。这就使这些薄片更容易以前文所述希望的方式取向。另外,通过挤塑,然后拉伸该聚合物薄膜以使该膜很薄,可使这些薄片最佳分配。通过使用黑色或深色背景,观察者观察到比用白色背景更亮的光学效果。在共挤塑层使用染料,仍可获得不同的光学效果。本发明中经铸塑或挤塑制备的聚合物片材是很稳定并耐用的。
Claims (34)
1、一种聚合物片材,该聚合物片材包括具有平行的第一和第二表面的第一层聚合物材料和置于第一层聚合物材料层中的许多多层干涉薄膜薄片,所说的薄片具有平行的第一和第二表面,有一个宽度和一个厚度,并且宽度相对于厚度的纵横比至少为2∶1,所说的薄片取向使得这些薄片位于这些薄片的第一和第二平行表面基本上平行于第一层聚合物材料的第一和第二平行表面的平面内。
2、权利要求1中的片材,该片材还具有粘合到所说的第一层上的第二层聚合物材料,所说的第二层聚合物材料作为基层,所说的第一层聚合物材料层作为第二层。
3、权利要求1中的片材,该片材是挤塑的。
4、权利要求1中的片材,该片材是铸塑的。
5、权利要求1中的片材,其中所说的薄片是双轴取向的。
6、权利要求2中的片材,其中所说的薄片是光学可变的。
7、权利要求2中的片材,其中所说的第二层是着色的。
8、权利要求2中的片材,其中所说的第一层是无定形的。
9、权利要求2中的片材,其中所说的基层和第二层是共挤塑的。
10、权利要求2中的聚合物片材,其中所说的基层是着色的。
11、权利要求8中的片材,其中所说的第二层基本是结晶的。
12、权利要求11中的片材,其中所说的第二层聚合物材料具有第一和第二平行表面,其中所说的第一层聚合物材料层置于第二层的第一表面上并且第三层聚合物材料粘结到第二层的第二表面上,所说的第三层聚合物材料具有在其上放置的许多的多层干涉薄膜薄片,在第三层中所说薄片被取向,结果这些薄片位于薄片的第一和第二平行表面平行于第三层的第一和第二平行表面的平面内。
13、权利要求9中的聚合物片材,其中所说的基层是结晶的,所说的第二层是无定形的。
14、权利要求13中的聚合物片材,其中基层和第二层均是双轴取向的。
15、一种保密票据制品,具有第一和第二表面的材料片材,载于该材料片材的光学物品,所说的光学物品包括一层具有第一和第二平行表面的聚合物材料层,置于该聚合物材料层中的多个取向的多层干涉薄膜薄片,所说的薄片具有第一和第二平行表面、一个宽度和厚度,并具有宽度相对厚度至少为2∶1的纵横比,薄片的第一和第二的平行表面平行于该聚合物材料层的第一和第二表面。
16、权利要求15中的制品,其中所说的聚合物材料层是双轴取向的,该薄片位于在双轴取向方向上的平面内,该薄片的第一和第二表面基本上平行于该材料层的第一和第二表面。
17、权利要求15中的制品,还具有另外一层聚合物材料,其粘接到所说的第一层聚合物材料上。
18、权利要求15中的制品,其中所说的薄片是光学可变的。
19、权利要求15中的制品,其中所说的物品呈细长带状,其中所说的带子至少部分埋在该材料片材中。
20、权利要求15的制品,还具有一片材,该片材载有一图像,该图像置于位于该光学物品之下的第一表面上,其中该光学物品是半透明以便通过该光学物品观察到该图像。
21、权利要求15的制品,其还具有至少一种填充剂,该填充剂以染料或颜料的形式加入到该聚合物材料中。
22、权利要求15中的制品,其中所说的聚合物材料是双轴取向聚合物层,或是铸塑层。
23、权利要求17中的制品,其中所说的另外一层聚合物材料层是彩色的。
24、权利要求19中的制品,其中所说的带子有区段部分,其中所说的部分通过保密票据制品的至少一面是露出可见的。
25、权利要求24中的制品,其中所说的带子具有另外一部分,其中所说的这一部分在该材料片材的另一面是露出可见的。
26、权利要求21中的制品,其中所说的染料和颜料被选来遮盖在各个角度不希望的颜色。
27、权利要求22中的制品,其中一种染料或颜料置于该聚合物材料中。
28、权利要求27中的制品,其中所说染料和颜料被选来遮盖在各个角度不希望的颜色。
29、一种制备一种光学制品的方法,该光学产品使用了多层干涉薄膜薄片,这些薄片具有第一、第二平行表面、一个宽度和一个厚度,并具有宽度相对于厚度至少为2∶1的纵横比,该方法包括将聚合物材料熔化;把薄片引入聚合物材料;把熔化的聚合物材料制成其中含有薄片的熔融的物质从而当该熔融的物质被制成了具有第一、第二平行表面的片材时,使这些薄片在该熔融的物质中取向,结果薄片的第一、第二表面位于平行于该片材第一、第二表面的平面内;冷却该片材,并使其固化制成片材。
30、权利要求29中的方法,包括加热已冷却的片材;在第一和第二方向上拉伸该片材,以引起该片材中的分子链的双轴取向,同时引起薄片的取向,使得这些薄片位于双轴取向方向的平面内;接着冷却该片材。
31、权利要求29中的方法,还包括共挤塑具有另外一层聚合物材料层的片材,使得这另外一层粘接到片材的第一表面上。
32、权利要求29中的方法,还包括一个步骤,该步骤包括将熔融物质成形在可剥离的基材上,拉伸该聚合物片材以使当聚合物固化时聚合物中的薄片取向;和从可剥离的基材上分离该固化的聚合物片材。
33、权利要求31中的方法,还包括把一种色料引入到该另外一层共挤塑材料层中的步骤。
34、权利要求31中的方法,还包括共挤塑另外一层聚合物材料的步骤,使得另一层粘接到该片材的第二表面上。
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1995
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- 1995-01-24 ES ES95908680T patent/ES2250968T3/es not_active Expired - Lifetime
- 1995-01-24 AT AT95908680T patent/ATE306389T1/de active
- 1995-01-24 DE DE69535073T patent/DE69535073T2/de not_active Expired - Lifetime
- 1995-01-24 CA CA002181588A patent/CA2181588C/en not_active Expired - Lifetime
- 1995-01-24 EP EP95908680A patent/EP0741639B1/en not_active Expired - Lifetime
- 1995-01-24 WO PCT/US1995/001014 patent/WO1995021057A1/en active IP Right Grant
- 1995-01-24 CN CN95191497A patent/CN1081984C/zh not_active Expired - Lifetime
- 1995-01-24 AU AU16910/95A patent/AU684146B2/en not_active Expired
- 1995-01-24 JP JP7520650A patent/JPH09508593A/ja active Pending
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Also Published As
Publication number | Publication date |
---|---|
HK1011640A1 (en) | 1999-07-16 |
DE69535073D1 (de) | 2006-08-03 |
WO1995021057A1 (en) | 1995-08-10 |
CN1140432A (zh) | 1997-01-15 |
ES2250968T3 (es) | 2006-04-16 |
EP0741639B1 (en) | 2005-10-12 |
EP0741639A4 (en) | 1998-01-28 |
EP0741639A1 (en) | 1996-11-13 |
ATE306389T1 (de) | 2005-10-15 |
DE69535073T2 (de) | 2006-12-14 |
CA2181588C (en) | 2007-03-27 |
US5424119A (en) | 1995-06-13 |
AU1691095A (en) | 1995-08-21 |
DK0741639T3 (da) | 2006-01-16 |
CA2181588A1 (en) | 1995-08-10 |
JPH09508593A (ja) | 1997-09-02 |
AU684146B2 (en) | 1997-12-04 |
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