CN1040694C - 柔性立方角逆向反光薄片 - Google Patents

柔性立方角逆向反光薄片 Download PDF

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CN1040694C
CN1040694C CN94193853A CN94193853A CN1040694C CN 1040694 C CN1040694 C CN 1040694C CN 94193853 A CN94193853 A CN 94193853A CN 94193853 A CN94193853 A CN 94193853A CN 1040694 C CN1040694 C CN 1040694C
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K·L·史密斯
T·J·黄
J·C·科德尔
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Abstract

反光物(10)包括主体部分(14)和从主体部分(14)背面突出的多重立方角单元(12)。主体部分(14)包括弹性模量小于7×108帕斯卡的透光聚合材料的主体层(18)。立方角单元(12)包括弹性模量大于16×108帕斯卡的透光聚合材料。这种结构的反光物易于弯曲，同时保持良好反光性能。

Description

柔性立方角逆向反光薄片
本发明涉及柔性立方角反光薄片，更具体地涉及立方角单元采用高弹性模量聚合物以及主体部分采用低弹性模量聚合物的柔性立方角逆向反光薄片。
逆向反光薄片(以下简称“反光薄片”)具有使入射光按原方向返回的能力。这种独特能力使反光薄片广泛地用于各种物体。反光薄片常常用于扁平而不可弯曲的物体，例如路牌和路障；然而，经常会出现需要将薄片用于不规则或者弯曲表面的情况。例如，将反光薄片粘附于卡车尾部的旁边，这要求薄片越过沟槽和耸出铆钉，或者将薄片粘附到诸如道路工安全防护衣等的弯曲基材上。在基材表面是不规则的或弯曲情况下，就要求反光薄片具有优良整合性(conformability)和弯曲性，但是不能损害逆向反光性能。
主要有两类逆向反光薄片：球状薄片和立方角薄片。球状薄片利用许多玻璃或陶瓷微球来反射入射光。微球相互之间被分隔开，因此不会明显地赋于薄片被弯曲的性能。另一方面，典型立方角薄片利用许多刚性并交联的立方角元件反射入射光。在弯曲过程中，立方角元件形状可能会变形，导致逆向反光性下降。因此，立方角薄片的结构在使薄片被整合或弯曲并且仍保持令人满意的反光性程度方面存在限度。许多研究者为了试图扩大或消除这些限度，已经采用许多不同途径制造在被弯曲或整合后有良好逆向反光性的立方角薄片。下述专利披露了这些不同方法的例子，美国专利3,684,348，3,924,929，3,992,080，4,555,161，4,576,850，4,668,558，4,582,885，5,177,304，5,189,553和英国专利GB2,245,219A。
美国专利3,684,348披露了一种反光薄片，这种薄片具有突出于主体部分的多重立方角结构。立方角结构和主体部分分别由基本透明的合成塑性树脂所形成，相互粘合形成复合结构。据披露，为了便于安装并且能适应各种构型的表面，该主体部分可弯曲。
美国专利3,924,929披露了一种立方角反光薄片，它包括多重三棱形反光单元，这些单元被交联隔膜分隔成小单元。可以将多重反光薄片单元粘合到可弯曲的背衬，如聚酯或聚氯乙烯网。反光薄片单元固定在背衬上的方式使得这种可弯曲物体能沿两条相邻边缘的任一方向卷起来或者折叠起来。
美国专利3,992,080披露的反光薄片在伸展开时具有良好反光性。这种薄片包括第一条透明弯曲合成树脂带，它具有位于薄片一个表面上的多重立方角结构。在松驰状态下，立方角结构被粘合于长度略短于第一条带的第二柔性背衬材料上。第一条带与带有立方角结构的第二条带相粘合，立方角结构靠近第二条带。这种复合反光薄片材料有褶裥，因此能够在支撑物表面上伸展开，这时消除了褶裥情况。据披露，这种结构可使薄片伸展开，同时避免了立方角结构的变形。
美国专利4,555,161披露了一种反光薄片，这种薄片的柔性高因此可适应多种用途。这种反光薄片包括由柔性合成可塑性片材构成的基片，扩张长度相同的柔性透明合成塑料的覆盖片，在基片和覆盖片之间的多重反光薄膜片。这种薄膜片按照预先确定方式排列，在薄膜片之间及四周区域，基片和覆盖片彼此粘合在一起，提供了一种多重不连续的单元，薄膜片就位于这种单元中。各薄膜片的一部分限定出将反光性赋予薄片的多重微型立方角结构。
美国专利4,576,850，4,582,855和4,668,558披露的反光立方角薄膜具有良好柔性和尺寸稳定性。这种反光薄膜由(1)和(2)构成的交联聚合物组成，(1)是许多含有一个或多个碳环和/或杂环基团的一价或多价部分的硬链段，(2)是许多一价或多价部分的软链段。硬链段部分的主转化温度超过250K，软链段部分的玻璃化温度低于250K，并且平均分子量为约500-5,000。
美国专利5,117,304披露了一种基于光学透明的脂肪族聚氨酯聚合物的柔性反光薄片。这种反光薄片包括在界接区(land)和位于该区上的单元列。反光单元中使用一种脂肪聚氨酯聚合物，该聚合物具有许多结构式为C(O)N(H)-C6H10-N(H)C(O)的硬链段，由此使薄片具备柔性。
美国专利5,189,553披露了适应弯曲应用的反光立方角薄片。该薄片具有为在薄片弯曲时的伸展所设计的外表面，以及为在薄片弯曲时的压缩所设计的内表面。相对于外表面和内表面之间为薄片中性弯曲区域(neutral bending access region)，使薄片弯曲时存在一种基本上不存在应力和形变的中性弯曲区。该薄片也具有许多反射立方角单元，有意使其表面靠近中性弯曲区。据披露，对于特定曲率半径而言，这种薄片提高了反光特性。
英国专利申请GB2,245,219A披露了一种柔性反光薄片材料，它具有由透明合成树脂构成的相对柔性的主体组件。这种柔性主体组件具有第一个面和第二个面，其中第一个面是平面，第二个面具有位于其上的紧密间隔的反光微棱镜。主体组件从第一个面到微球底部的厚度是5.08到25.4微米。微棱镜高度25.4到254微米。粘合涂料位于第二个面上的某些微棱镜上，而柔性背衬组件延伸于第二个面上，用粘合涂料将背衬粘合到微棱镜。
尽管上述专利披露了柔性反光立方角薄片的许多不同结构，某些披露的结构在构造时较为复杂。另外的结构，尽管与典型的反光薄片相比不太复杂，但要采用较昂贵聚合物材料，或者在高度弯曲或变形时只能提供有限的反光性，或者根本没有告诉人们在薄片被弯曲或变形后是任何实现良好反光性。
本发明提供了制备一种柔性立方角反光薄片的新型途径。与某些已有技术中的柔性立方角反光薄片相比，本发明薄片结构较简单，而且这种薄片能异乎寻常地进行弯曲和整合同时保留高度反光性。而且，这种薄片是由相对价廉聚合物制成。扼要地讲，本发明立方角反光薄片含有：主体部分，它包括由弹性模量低于7×108帕斯卡(pascals)的透光聚合材料构成的主体层；以及，从主体部分的第一侧面突出的许多立方角单元，这种立方角单元含有弹性模量超过16×108帕斯卡的透光聚合材料。
本发明与已知的立方角反光薄片的不同之处在于，立方角单元由高弹性模量聚合材料制成，主体部分由低弹性模量聚合材料制成。术语“弹性模量”指用静态标量法A按ASTM D 882-756测定的弹性模量，条件为5吋初始夹具间隔，1吋样品宽度，夹具间隔速率按每分钟1吋。
如上所述，薄片立方体部分和主体部分采用不同聚合物的反光薄片是人们已知的，举例来讲可参见美国专利5,117,304和英国专利3,684,384；然而，据认为，并无专利披露过将高弹性模量立方体和低弹性模量主体层结合在一起。这种结合具有明显优越性，因为这种薄片可以被充分弯曲而基本上不会造成反光性的损失。由本发明薄片的柔性足够强，使得可用常规的压敏粘合剂将薄片粘合剂到高整合性的表面(如突出铆钉上)。在弯曲时，立方角单元具有出色的尺寸稳定性，因此整合时具有良好反光性能。可在高温下保持这种尺寸稳定性和良好反光性能。
在本发明的附图以及详尽叙述中，更全面地阐述本发明的上述优点及其它优点，其中相同编号表示类似部件。然而，应该认识到，这些描述和附图仅用于阐述目的，并不用于限定本发明范围。
图1是本发明立方角反光薄片10的剖面图。
图2是图1的立方角反光薄片10的背视图。
在叙述本发明的较佳实施例时，采用专门术语以便表达清晰。然而，本发明并不限定于所选择的专门术语，应理解，所选用的每个术语代表相类似的所有技术对应词。
实施本发明时，提供了在高度弯曲条件下保持良好尺寸稳定性和高度反光性的立方角反光薄片。图1是本发明立方角反光薄片10的一个实例。立方角反光薄片10包括许多立方角单元12和主体部分14。主体部分14包括界接层(land layer)16和主体层18。主体层典型功能是保护薄片免受环境因素影响和/或对薄片提供重要的机械完整性。在一个较佳实施例中，主体层18是薄片10的前侧上的最外层。界接层16是与立方角单元底部最邻近相连的一层，这与主体层18不同，因此此处术语“接界层”指这样的一层。
立方角单元12从主体部分14的第一面即从后侧面20突出。立方角单元12含有弹性模量超过16×108帕斯卡，较佳地超过18×108帕斯卡，更佳地超过20×108帕斯卡的透光聚合材料；主体层18含有弹性模量低于7×108帕斯卡，较佳地低于5×108帕斯卡，更佳地低于3×108帕斯卡的透光聚合材料。
这样，立方角单元12所含的整合材料的弹性模量就比主体层聚合材料至少大9×108帕斯卡，而且可以比主体层聚合材料大11×108、13×108或甚至17×108帕斯卡。光从前表面21进入立方角薄片10。接着，光线穿过主体部分14，入射到立方角元件12的平面22，并按箭头23所示方向返回。
在较佳结构中，立方角单元12和界接层16由类似或相同种类的聚合物制成，而且界接层16的厚度被降至最小。典型地，界接层厚度为约0到150微米，更佳地约为1到100微米。典型地，主体层的厚度约为20-1000微米，更佳地为约50到250微米。尽管最好将界接层保持最低厚度，仍希望薄片10有某一界接层16，从而在界接层16和主体层18之间提供平界面。立方角的元件12典型高度范围约20到500微米，更典型范围为约60到180微米。尽管图1所示的本发明实施例仅有一个主体层18，主体部分14中有一个以上主体层18同样在本发明范围内。
图2是立方角单元12的背侧面。如图所示，立方角单元12按配对方式，在薄片的一个侧面排成一列。每个立方角单元12是带有三个露出平面22的三棱镜形。平面22基本上彼此相垂直(与房间的角落类似)，棱镜顶点与底部中心准垂直。典型地，在面22之间的角度对于一列中每个立方角单元都相同，该角约为90°。然而，众所周知该角度可偏离90°；参见，例如，Appledorn等的美国专利4,775,219。尽管每个立方角单元12的顶点可与立方角单元底部的中心垂直准直，参见例如美国专利3,684,348，但该顶点也可与底部中心呈倾斜，如美国专利4,588,258中所披露的那样。因此，本发明并不限于任何特定立方角几何形状，然而，在许多种已知立方角构型中(参见如美国专利4,938,563，4,775,219，4,243,618，4,202,600和3,712,706)，在美国专利4,588,258中报道的立方角薄片更合适，因为这种薄片在多视平面中可提供广角反光。
在立方角单元12的背面上可以加上一种特殊反射层，如金属涂层(未表示出)，以促进反光。可用熟知工艺涂上金属涂层，如蒸气沉积或化学沉积铝、银或镍之类的金属。可在立方角单元的背面上涂上底层(primer layer)以促进金属涂层的粘合。除了金属涂层之外或者作为金属涂层的代替层，可将密封膜施加到立方角单元的背面，例如美国专利4,025,159和5,117,304。密封膜在立方体的背面保留一个空气界面以便增加反光性。立方角单元的后面还可有背衬层或粘合层，以确保立方角反光薄片10牢固地粘附于底板上。
构成本发明反光薄片的聚合材料是透光的。这表明，在特定波长下该聚合物至少能透过70％入射光强度。更佳地，用于本发明反射薄片的聚合物透光性超过80％，最好超过90％。
在立方角单元中所用的聚合材料倾向用硬的刚性材料。聚合物材料可以是热塑性或交联树脂。这些聚合物弹性模量较佳地超过18×108帕斯卡，更佳地超过20×108帕斯卡。
当立方体中采用热塑性树脂时，玻璃化温度通常超过80℃，软化温度通常大于150℃。一般来讲，立方角层是无定形的或半晶体，聚合物的线性塑模收缩率通常低于1％。
立方角元件所用的热塑性聚合物实施例包括丙烯酸类聚合物，如聚甲基丙烯酸甲酯；聚碳酸酯；纤维素制品如纤维素醋酸酯，纤维素(醋酸酯加丁酸酯)，纤维素硝酸酯；环氧化物；聚酯，如聚对苯二酸丁二酯，聚对苯二酸乙二酯；含氟聚合物，如聚氯氟乙烯，聚偏氟乙烯；聚酰胺，如聚己内酰胺，聚氨基癸酸，聚(亚己基二胺-合-己酸)，聚酰胺-合-酰亚胺，聚酯-合-酰亚胺；聚醚酮；聚醚酰亚胺；聚烯烃，如聚甲基戊烯；聚苯基醚；聚苯硫；聚苯乙烯和聚苯乙烯共聚物如聚(苯乙烯-合-丙烯腈)，聚(苯乙烯-合-丙烯腈-合-丁二烯)；聚硫砜；硅酮改性聚合物(即含少量(低于10％重量)硅酮的聚合物)，如硅酮聚酰胺和硅酮聚碳酸酯；氟改性聚合物如全氟聚对苯二甲酸乙二酯；以及上述聚合物的混合物，如聚酯和聚碳酸酯混合物，含氟聚合物和丙烯酸类聚合物混合物。
适合于形成立方角单元的其他材料是受到光辐照时，可通过自由基聚合机理而交联的活性树脂体系，光辐照实例有电子束、紫外光或可见光。另外，这些材料可用加热手段通过添加诸如过氧化苯甲酰的热引发剂而进行聚合。还可以采用辐射诱发的阳离子可聚合树脂。
适合于形成立方角单元的反应性树脂可以是光引发剂和至少一种含丙烯酸基团的化合物的混合物。更合适的是，树脂混合物含有双功能或多功能化合物，以便在辐照时确保形成交联聚合物网络结构。
可通过自由基机理聚合的树脂实例包括从环氧化物衍生的丙烯酸基树脂，聚酯，聚醚和氨基甲酸乙酯，烯键不饱和化合物，至少有一个侧丙烯酸酯基团的氨基塑料衍生物，至少有一个侧丙烯酸酯基团的异氰酸酯，除了丙烯酸酯环氧化物的环氧树脂，以及上述混合物和组合。本专利所用术语丙烯酸酯包括丙烯酸酯和甲基丙烯酸酯。Martens的美国专利4,576,850披露了可用于本发明立方角单元中的交联树脂例子。
烯键不饱和树脂包括单体及聚合物，它们含碳、氢和氧，此外还可含有氮、硫和卤素。氧或氮原子或者两种原子通常存在于醚，酯，氨基甲酸乙酯，酰胺和尿素基团中。烯键不饱和化合物分子量较合适的范围为低于4,000，较佳的是酯类化合物，它是由含脂肪族单羟基或脂肪族多羟基化合物和不饱和羧酸的反应形成的酯类。不饱和羧酸的例子有丙烯酸，甲基丙烯酸，衣康酸，巴豆酸，异巴豆酸，马来酸等。
下面列出具有丙烯酸和甲基丙烯酸基团的某些化合物实例。被列出化合物起说明作用，并不局限于这些化合物。
(1)单功能化合物：
丙烯酸乙酯，丙烯酸正丁酯，丙烯酸异丁酯，丙烯酸-2-乙基己酯，丙烯酸正己酯，丙烯酸正辛酯，丙烯酸异丙冰片酯，丙烯酸四氢呋糠酯，丙烯酸-2-苯甲氧乙酯，N，N-二甲基丙烯酰胺；
(2)双功能化合物；
1，4-丁二醇二丙烯酸酯，1，6-己二醇二丙烯酸酯，新戊二醇二丙烯酸酯，乙二醇二丙烯酸酯，三甘醇二丙烯酸酯，和四甘醇二丙烯酸酯；
(3)多功能化合物：
三羟甲基丙烯三丙烯酸酯，丙三醇三丙烯酸酯，戊赤藓醇三丙烯酸酯，戊赤藓醇四丙烯酸酯，和三(2-丙烯酰氧乙基)异氰尿酸酯。
其它烯键不饱和化合物和树脂的某些典型实例包括苯乙烯，二乙烯苯，乙烯甲苯，N-乙烯吡咯烷酮，N-乙烯基己内酰胺，一烯丙基、多烯丙基和多甲基烯丙基酯，如二烯丙基对苯二甲酸酯和二烯丙基己二酸酯，以及羧酸酰胺，如N，N-二烯丙基己二酰二胺。
可与丙烯酸化合物掺合的光聚合引发剂实例包括下述代表性的引发剂：苯偶酰，邻苯甲酸甲酯，苯偶姻，苯偶姻乙醚，苯偶姻异丙醚，苯偶姻异丁醚等，二苯甲酮/叔胺，乙酰苯(如2，2-乙氧基乙酰苯)，苯偶酰甲基酮缩醇，1-羟基环己基苯基酮，2-羟基-2-甲基-1-苯丙基-1-酮，1-(4-异丙基苯基)-2-羟基-2-甲基丙基-1-酮，2-苄基-2-N，N-二甲基氨基-1-(4-吗啡代苯基)-1-丁酮，2，4，6-三甲基苯甲酰基二苯基膦氧化物，2-甲基-1-4-(甲基硫代)苯基-2-吗啡基-1-丙酮等。这些化合物可单独使用或结合使用。
阳离子可聚合材料包括含环氧和乙烯醚功能基团的材料，但并不局限于这些材料。这些体系可用鎓盐引发剂进行光引发，如三芳基巯和二芳基碘鎓盐。
用于立方角单元的较佳聚合物包括聚碳酸酯，聚甲基丙烯酸甲酯，聚对苯二甲酸乙二醇酯和交联丙烯酸酯，例如多功能丙烯酸酯或环氧化物和掺有单功能和多功能单体的丙烯酸酯化的(acrylated)氨基甲醇乙酯。这些聚合物因下述一种或多种原因而被优选出：热稳定性，环境稳定性，透明性，从工具或塑模中极佳脱模性，和能够容纳反射涂层。
如上所述，界接层所用的聚合物材料可与立方角单元所用的聚合物相同，只要让界接层厚度保持最低厚度。界接层最好实际上是扁平的，以致于在立方体和主体层之间有较佳的界面。在立方体和界接层之间要避免孔洞和/或界面粗糙性，从而当光由此被反射时，反光薄片可呈现出最佳亮度。良好界面可防止反射光在传播中发生折射。在大多数情况下，界面层与立方角单元是一体化的。“一体化”指界接层和立方角由一种聚合材料形成，而并不是随后结合在一起的两种不同聚合层。立方角单元和界接层所用材料的折射指数与主体层材料的折射指数可不同。尽管希望界接层用类似于立方体材料所用的聚合物，界接层也可以用柔软聚合物制成，如在主体层中所用的柔软聚合物。
主体层是由易弯曲、卷曲、挠曲、整合或伸展的低弹性模量聚合物构成。弹性模量较适宜的是低于5×108帕斯卡，更合适的是低于3×108帕斯卡。一般来讲，主体层聚合物玻璃化温度低于50℃。较佳地，这种聚合物能在立方体上所处温度条件下保持其物理上完整性。这种聚合物的Vicate软化温度超过50℃是有利的。较佳地，这种聚合物线性模塑收缩率低于1％。用于主体层中的较佳聚合材料应耐紫外光辐照降解，以便可将这种反光薄片户外长期应用。主体层所用的聚合物的实例包括：
氟代聚合物，例如聚氯三氟乙烯，如Kel-F800TM，明尼苏达州圣保罗的3M产品；聚(四氟乙烯-合-六氟丙烯)，如Exac FEPTM(可购自马萨诸塞州Brampton的Norton Performance)；聚(四氟乙烯-合-全氟烷基乙烯醚)，如Exac，PEATM(NortonPrformance)；聚(偏氟乙烯-合-六氟丙烯)，如Kynar Flex-2800TM(可购自由宾夕法尼亚州Philadelphia的Pennwalt Corpa-tion)。
离子型乙烯共聚物如钠盐或锌离子的聚(乙烯-合-甲基丙烯酸)盐，如Surlyn-8920TM和Surlyn-9910TM(可购自特拉华州Wilmington的E.I.duPont Nemours)。
低密度聚乙烯类如低密度聚乙烯，线性低密度聚乙烯，和极低密度聚乙烯；
增塑的乙烯基卤代聚合物，如增塑聚氯乙烯；
聚乙烯共聚物包括：酸性功能聚合物，如聚(乙烯-合-丙烯酸)和聚(乙烯-合-甲基丙烯酸)，聚(乙烯-合-马来酸)，和聚(乙烯-合-富马酸)；丙烯酸功能聚合物，如聚(乙烯-合-烷基丙烯酸酯)，其中烷基是甲基，乙基，丙基，丁基等，或者CH3(CH2)n-，其中n是0-12，和聚(乙烯-合-乙烯乙酸酯)；和
脂肪族和芳香族聚氨酯由下述单体(1)-(3)衍生出：(1)二异氰酸酯，如二环己基甲烷-4，4′-二异氰酸酯，异佛尔酮二异氰酸酯，1，6-亚己基二异氰酸酯，环己基二异氰酸酯，二苯基甲烷二异氰酸酯，和这些二异氰酸酯的组合，(2)聚二醇，如聚戊二烯亚戊基己二酸乙二醇，聚四亚甲基醚乙二醇，聚乙二醇，聚乙酸内酯二醇，聚-1，2-丁烯氧化物乙二醇，以及这些聚二醇的组合，和(3)链补充剂，丁二醇或己二醇。商品聚氨酯包括：PN-04或3429(新罕布什尔州Seabrook的Morton International Inc.)或X-4107(俄亥俄州Cleveland的B.F.Goodrich Company)。
上述聚合物的组合也可用于主体部分的主体层中。用于主体层的较佳聚合物包括：含有羧基基团或羧酸酯单元的乙烯共聚物，如聚(乙烯-合-丙烯酸)，聚(乙烯-合-甲基丙烯酸)，聚(乙烯-合-乙烯醋酸酯)；离子交联乙烯共聚物；增塑聚氯乙烯；和脂肪族氨基甲酸乙酯。由于下述一种或多种原因而优选这些聚合物：合适机械性能，对界接层的良好粘合，透明性和环境稳定性。
在一个实例中，其中含有聚碳酸酯立方角单元和/或聚碳酸酯界接层，和一个含有聚乙烯共聚物(例如聚(乙烯-合-(甲基)丙烯酸)，聚(乙烯-合-乙烯乙酸酯)或聚(乙烯-合-丙烯酸酯))的主体层，在主体层和界接层之间或主体层和立方角单元之间加上薄连接层(未表示出)可改善这些层之间界面粘合。可在主体层被层压于界接层上或压在立方角单元上之前，将连接层施涂在主体层上，可以以薄涂层形式，利用下述化合物进行施涂：如有机溶液中脂肪族聚氨酯，例如PermuthaneTM U26-248溶液，(马萨诸塞州Peabod的Permuthane Company的商品)；Q-thaneTMQC-4820(新罕布什州Seabrook的K.J.Quin and Co.，Inc.)；脂肪族聚氨酯水溶性分散体，如NeoRezTM R-940，R-9409，R-960，R-962，R-967和R-972(马萨诸塞州Wilmington的ICI Resins US的商品)；丙烯酸聚合物水溶性分散体，如NeoCrylTM A-601，A-612，A-614，A-621和A-6092(马萨诸塞州Wilmington的ICI ResinsUS)；或者丙烯酸烷基酯和脂肪族氨基甲酸乙酯共聚物水溶性分散体，如NeoPaoTM，R-9000(萨诸塞州Wilmington的ICI ResinsUS)。此外，可用诸如电晕式等离子体处理的放电法进一步改善连接层与主体层或者连接层与界接层或与立方角单元的粘合情况。
可将着色剂、紫外吸收剂、光稳定剂、自由基消除剂或抗氧剂、加工助剂如抗粘结剂、脱模剂、润滑剂及其它添加剂添加到主体部分或立方角单元。当然，选择的特定着色剂取决于薄片所需的颜色。典型的着色剂添加量为约0.01到0.5％(重量)。典型的紫外线吸收剂添加量为约0.5到2.0％(重量)。紫外吸收剂实例包括苯并三唑的衍生物，如TinuvinTM 327，328，900，1130，Tinuvin-PTM(纽约州Ardsley的Ciba-Geigy Corporation商品)；二苯甲酮的化学衍生物，如UvinulTM-M40，408，D-50(新泽西州Clifton的BASF Cor-poration商品)；SyntaseTM230，800，1200(宾夕法尼亚州Pitts-burgh的Neville-Organics，Inc.商品)；或者二苯基丙烯酸酯化学衍生物，如UvinulTM-N35，539，(新泽西州Clifton的BASF Cor-poration.商品)。可使用的光稳定剂包括受阻胺类，其典型含量为约0.5到2.0％(重量)。受阻胺光稳定剂实例包括TinuvinTM-144，292，622，770和ChimassorbTM-944(都是纽约州Ardsley的Ciba-Geigy Corp.商品)。自由基清除剂或抗氧剂典型用量约0.01-0.5％(重量)。合适的抗氧剂包括受阻酚醛树脂，如IrganoxTM-1010，1076，1035或MD-1024，或IrgafosTM-168(纽约州Ardsley的Ciba-Geigy Corp.商品)。为了改善树脂加工性，可添加少量其它加工助剂，通常其含量占聚合物树脂量1％以下。可用的加工助剂包括脂肪族酯类，或者脂肪族酰胺(可购自康尼狄克州Norwalk的Glyco Inc.)，硬脂酸金属盐(可购自新泽西州Hoboken的HenkelCorp.)或者Wax ETM(新泽西州Somerville的Hoechst CelaneseCorporation商品)。
本发明立方角反光薄片可按下述步骤制作，(a)用弹性模量大于16×108帕斯卡的透光材料形成多重立方角单元；和(b)将主体层与多重立方角单元固定，其中的主体层含有弹性模量低于7×108帕斯卡的透光材料。可以按照制作立方角薄片的许多已知(或今后发现的)方法实施步骤(a)和(b)，例如可参阅美国专利3,689,346、3,811,983、4,332,847和4,601,861，不同之处在于，用高弹性模量聚合物来形成立方角单元，用低弹性模量聚合物形成主体层。可将主体层直接固定到立方角单元的基部，或者通过界接层将主体层固定到立方角单元。如上所述，最好使界接层保持最低厚度，而且界接层最好由高弹性模量聚合物制成。
下述实施例将进一步说明本发明特点和优点。然而，应清楚地认识到，尽管这些实施例用于阐述说明，但是本发明范围并不受特定的组分和用量以及其它条件的过份限制。
实施例实施例1(对比例1)
将熔融聚碳酸酯树脂(MakrolonTM，2407，由宾夕法尼亚州Pittsburgh的Mobay Corporation供应的商品)浇注到带有微立方棱镜凹口的加热微结构镍具上，凹口深度约86微米(0.0034时)。配对立方角单元的光轴与主槽口倾斜4.31度，用这种配对立方角单元形成微立方凹口，在Szczech的美国专利5,138,488中有一般性叙述。镍具厚度508微米(0.020吋)，加热镍具到215.6℃(420°F)。为了复制微立方凹口，将温度287.8℃(550F)的熔融聚碳酸酯注入到镍具上，压力约1.03×107-1.38×107帕斯卡(1500-2000psi)，时间约0.7秒。在填充立方凹口同时，在镍具上的连续界接层处沉积额外的聚碳酸酯，它的厚度约51微米(0.002吋)。事先挤压出的厚43微米(0.0017吋)、冲击改性过的连续聚甲基丙烯酸甲酯主体层膜(Plexiglass 60％VO-45和40％DR-1000，由宾夕法尼亚州Philadelphia的Rohm and Haas Company供应商品)再层压到连续性聚碳酸酯界接层上，表面温度约190.6℃(375°F)。带有层压的聚碳酸酯和聚(甲基丙烯酸甲酯)主体层的刀具再于室温空气下冷却18秒钟至温度71.1-87.8℃(160-190°F)，让层压材料固化。再从微结构刀具取下层压样品。实施例2
第二个样品按实施例1所述步骤制备，不同之处是主体层是事先挤压出的厚79微米(O.0031吋)的连续性聚(乙烯-合-丙烯酸)膜(PrimacorTM 3440，材料由Dow Chemical Company，Midland，Michigan提供)。为了促进该膜粘合到聚碳酸酯表面，涂上脂肪族聚氨基甲酸乙酯底层。底层(Q-ThaneTM QC-4820，由新罕布什州Seabrook的K.J.Quinn and Co.，Inc.提供)以溶剂形式进行涂布，形成最终干厚度约2.5微米(0.0001吋)的底层。实施例3
第三个样品按实施例1所述步骤制备，不同之处是主体层是事先挤压出的厚71微米(0.0028吋)的聚氨基甲酸乙酯主体层(MorthaneTMPNO3，由新罕布什Seabrook的Morton International提供)。
表1列出了实试例1-3估价的层压样品的主体层材料的弹性模量。按照ASTM D882-75b用Sintech 1静态称量恒速握力间隔试验机测弹性模量，试验机是由明尼苏达州Eden Prairie的MTSSystems Corp.生产。所有样品的立方体和界接层所用的聚碳酸酯弹性模量是20.0×108帕斯卡(29.1×104psi)。
表1
实施例 主体层材料 弹性模量
    123 聚甲基丙烯酸甲酯聚(乙烯-合-丙烯酸)脂肪族聚氨基甲酸乙酯 24.4×108帕斯卡(35.4×104psi)1.24×108帕斯卡(1.80×104psi)0.34×108帕斯卡(0.50×104psi)
实施例1-3样品的表观弯曲模量用TaberTM V-5刚性试验机测试，该仪器由纽约州North Tonawanda的Taber InstrumentCorp制造。按照ASTM D747-84a进行计算。表2列出其结果。
实施例1-3样品还试验了弯曲到曲率半径9.52微米(0.375吋)引起的光程差(OPD)。采用相移Twyman-Green干涉仪(亚利桑那州Tucson的WYKO Corporation制造)在波长633纳米处测量OPD。OPD提供了波阵面被立方角单元反射时，表征波阵面畸变的手段。光学畸变的增加意味着反射光的分散或直接转变成傅立叶光学(fourier optics)发散曲线(divergence profile)(例如，参见″TheNew Physical Optics Notebook：Tutorials in Fourier Optics″，Reynolds，DeVelis，Parrent，and Thompson，SPIE Press 1989)。对于给定形变，使OPD波阵面畸变降低的样品或结构是优选的。
在代表三种实施例的样品中选出三种立方角单元。在沿与主槽相平行的轴进行弯曲之前和之后，测量三种立方角中每一种的OPD与波长数的关系。再微分OPD结果，得到仅与三种立方角中每一例的弯曲相关的OPD，平均差分结果，得到与每种样品弯曲相关最终平均OPD。采用OPD的峰谷比(P-V)和均方根(RMS)来表征波阵面畸变。表2列出P-V和RMS OPD。
表2
实施例 表观弯曲模量   P-V OPDa   RMS OPDa
    1  8.62×108帕斯卡(1.25×105psi)     1.12 0.27
    2  1.73×108帕斯卡(0.25×105psi)     0.72 0.14
    3  1.24×108帕斯卡(0.18×105psi)     0.67 0.12
a.与弯曲至曲率半径9.52微米(0.375吋)相关的OPD变化。
表2数据说明，采用较低模量主体层薄膜和高弹性立方角材料可得到柔性很强的层状材料。令人惊奇的是，与高模量主体层的常规层状物相比较，对于给定的畸变，所得到的易弯曲层状物的其光学性能降低程度小得多。
在本发明主旨和范畴之内，可对本发明作各种修改和改动。因此，应当认识到，本发明并不局限于上述说明，本发明受下述权利要求的限制条件及任何对等条件的限制。

Claims (15)

1.一种逆向反光薄片，它含有：
(a)具有第一和第二主表面的主体部分，该主体部分包括一含有聚合材料的主体层，该主体层让光线通过第一或第二主表面进入该层并穿过该层从另一主表面离开；和
(b)从主体部分的第二主表面突出的立方角单元，使通过第二主表面离开主体部分的光线进入立方角单元，并在立方角单元中被反射，重新进入主体部分；
其特征在于，主体层的弹性模量低于7×108帕斯卡，而且立方角单元含有一聚合材料，该聚合材料的弹性模量比主体层大从而使逆向反光薄片被弯曲时不会造成逆向反光性的显著损失。
2.如权利要求1所述的逆向反光薄片，其特征在于，该立方角单元含有弹性模量比主体层的弹性模量至少大9×108帕斯卡的聚合材料。
3.如权利要求2所述的逆向反光薄片，其特征在于，该立方角单元含有弹性模量比主体层的弹性模量至少大11×108帕斯卡的聚合材料。
4.如权利要求3所述的逆向反光薄片，其特征在于，该立方角单元含有弹性模量比主体层的弹性模量至少大13×108帕斯卡的聚合材料。
5.如权利要求1所述的逆向反光薄片，其特征在于，该立方角单元含有弹性模量高于16×108帕斯卡的透光聚合材料。
6.如权利要求1所述的逆向反光薄片，其特征在于，主体部分包括厚度0-150微米范围的界接层，它由弹性模量大于16×108帕斯卡的聚合材料构成。
7.如权利要求6所述的逆向反光薄片，其特征在于，界接层厚度范围1-100微米。
8.如权利要求6-7所述的逆向反光薄片，其特征在于，立方角单元和界接层由弹性模量大于18×108帕斯卡的聚合物构成。
9.如权利要求1所述的逆向反光薄片，其特征在于，主体层厚度约20-1000微米，立方角单元的高度约60-180微米。
10.如权利要求1所述的逆向反光薄片，其特征在于，立方角单元含有弹性模量大于18×108帕斯卡的透光聚合材料，主体层含有弹性模量低于5×108帕斯卡的透光聚合材料。
11.如权利要求1所述的逆向反光薄片，其特征在于，立方角单元含有弹性模量大于20×108帕斯卡的透光聚合材料，主体层含有弹性模量低于3×108帕斯卡的透光聚合材料。
12.如权利要求1所述的逆向反光薄片，其特征在于，主体层含有由选自下组的聚合物：聚(乙烯-合-丙烯酸)，聚(乙烯-合-甲基丙烯酸)，聚(乙烯-合-乙烯醋酸酯)，离子型乙烯共聚物，和脂肪族氨基甲酸乙酯；立方角单元含有选自下组的聚合物：聚碳酸酯，聚甲基丙烯酸甲酯，聚对苯二甲酸乙二醇酯，和交联丙烯酸酯。
13.如权利要求1所述的逆向反光薄片，其特征在于，主体层含有聚(乙烯-合-丙烯酸)或聚(乙烯-合-甲基丙烯酸)，和立方角单元含有聚碳酸酯。
14.制备逆向反光薄片的方法，其特征在于，该法包括：
(a)用弹性模量大于16×108帕斯卡的透光材料形成多重立方角单元；和
(b)将主体层固定到多重立方角单元，其中主体层含弹性模量低于7×108帕斯卡的透光材料。
15.如权利要求14所述的方法，其特征在于，还包括：
用弹性模量大于16×108帕斯卡的透光材料形成界接层；和
将界接层固定于立方角单元，使界接层位于立方角单元和主体层之间。
CN94193853A 1993-10-20 1994-10-20 柔性立方角逆向反光薄片 Expired - Lifetime CN1040694C (zh)

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AU7983494A (en) 1995-05-08
DK0724731T3 (da) 2000-04-17
ES2141264T3 (es) 2000-03-16
EP0724731A1 (en) 1996-08-07
US5988820A (en) 1999-11-23
DE69422823T2 (de) 2000-06-15
DE69422823D1 (de) 2000-03-02
ATE189316T1 (de) 2000-02-15
JP3623506B2 (ja) 2005-02-23
US20020126382A1 (en) 2002-09-12
US5450235A (en) 1995-09-12
US7568807B2 (en) 2009-08-04
CA2172636C (en) 2006-01-24
CA2172636A1 (en) 1995-04-27
US6350035B1 (en) 2002-02-26
US20070014011A1 (en) 2007-01-18
US7185993B2 (en) 2007-03-06
JPH09504622A (ja) 1997-05-06
CN1133635A (zh) 1996-10-16
EP0724731B1 (en) 2000-01-26
WO1995011466A1 (en) 1995-04-27

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