CN1100807C - 含有聚酯型聚氨酯粘结剂层的逆向反射制品 - Google Patents

含有聚酯型聚氨酯粘结剂层的逆向反射制品 Download PDF

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CN1100807C
CN1100807C CN96196872A CN96196872A CN1100807C CN 1100807 C CN1100807 C CN 1100807C CN 96196872 A CN96196872 A CN 96196872A CN 96196872 A CN96196872 A CN 96196872A CN 1100807 C CN1100807 C CN 1100807C
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M·D·克兰德尔
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Abstract

逆向反射制品(10)包括部分埋在粘结剂层(14)中的逆向反射元件(12)。所述的粘结剂层(14)含有聚酯型聚氨酯聚合物。所述的聚氨酯聚合物是(i)含有芳环并具有至少两个与芳环非共轭键合的异氰酸酯基的聚酯多元醇与(ii)多异氰酸酯的反应产物。使用这种粘结剂层的逆向反射制品在严苛的工业洗涤条件下具有极好的洗涤耐久性。

Description

含有聚酯型聚氨酯粘结剂层的逆向反射制品
本发明涉及含有聚氨酯粘结剂层的逆向反射制品。所述的聚氨酯是聚酯多元醇与多异氰酸酯的反应产物。所述的多异氰酸酯至少含有两个与至少一个芳环非共轭键合的异氰酸酯基。本发明也涉及带有这种逆向反射制品的服装制品。
逆向反射制品能将入射光反射回光源。这种独特的性能有利于逆向反射制品广泛使用在服装上。
在车辆交通附近工作或锻炼的人员必须明显可见，以免被过往车辆撞到。逆向反射制品通过逆向反射车辆前灯发出的光线而在夜间为驾驶员指明人员的存在。从车辆前灯发出的光线照到穿着者衣服上的逆向反射制品，并向车辆反射，以使驾驶员能发觉人员的存在。由逆向反射制品显示的明亮人影为驾驶员保留了更多的反应时间。
由于逆向反射制品常用于衣服，所以它们必须能耐洗涤条件--否则，这些制品在反复洗涤后不能继续起到安全作用。逆向反射领域中的研究人员发觉到了这个问题，所以他们一直在寻求开发一种耐洗逆向反射制品，以使逆向反射衣服在多次穿着和洗涤后仍能使穿着者明显可见。
研究人员也意识到需要开发特别适用于常在恶劣环境中穿着的衣服制品。这类衣服的实例包括救火队员外套和建筑工人安全防护衣。因为这些衣服常在苛刻的条件下使用，所以它们可能变得很脏，因此需要在工业洗涤条件下进行洗涤。所述工业洗涤条件一般包括高达40-90℃(105-190°F)的温度和10-12.5的pH值。
已用在衣服上的某些耐洗逆向反射制品包括透明微球暴露层、聚合物粘结剂层和镜面反射层。透明微球部分埋人聚合物粘结剂层中，镜面反射层位于微球埋入部分的下面。因为微球是暴露的，即没有被透光聚合物层覆盖，所以该制品常称为“暴露型透镜逆向反射制品”。照到逆向反射制品前表面的光线进入透明微球，透明微球改变了光线的方向，使其照到下面的镜面反射层，镜面反射层将其反射，使其重新进入微球，微球再次改变其方向，但这次是返回光源的方向。
在一次开发在工业洗涤条件下耐洗的暴露型透镜逆向反射制品的成功尝试中，Wu Shgong Li在美国专利5,200,262中将单层涂有金属的微球部分埋在粘结剂层中。该粘结剂层含有柔性聚合物和一种或多种异氰酸酯官能的硅烷偶联剂。所述的柔性聚合物含有可异氰酸酯固化的聚酯和一种或两种聚氨酯组分。
在另一次成功的尝试中，Li使用由电子束可固化的聚合物和一般一种或多种交联剂及硅烷偶联剂制得的粘结剂层(参照美国专利5,283,101)。电子束可固化的聚合物包括氯磺化聚乙烯、至少约含有70％重量聚乙烯的乙烯共聚物(如乙烯-乙酸乙烯酯、乙烯-丙烯酸酯和乙烯-丙烯酸共聚物)和聚(乙烯-共-丙烯-共-二烯)聚合物。微球被埋在固化的粘结剂层中。镜面反射金属层位于微球埋入部分上。
在另一方法中，Michael Crandall等揭示通过使含有芳族双螯合基团的化合物与反射金属层化学结合，制造耐洗的逆向反射制品。在一个实施方案中，该化合物被置于聚合物粘结剂层中。该粘结剂层较好含有交联的或有效交联的弹性体。交联的聚合物包括聚烯烃、聚酯、聚氨酯、聚环氧化物和天然或合成橡胶。这种产品揭示在美国专利5,474,827中。
本发明提供一种在工业洗涤条件下非常耐洗的新型逆向反射制品。该新型制品包括一层至少部分埋在粘结剂层中的逆向反射元件，所述的粘结剂层含有聚氨酯聚合物，所述的聚氨酯聚合物是(i)聚酯多元醇与(ii)多异氰酸酯的反应产物，所述的多异氰酸酯至少含有两个与至少一个芳环非共轭键合的异氰酸酯基。
在另一方面，本发明提供一种将逆向反射制品转移到服装和衣服制品上的方法，以使本发明的逆向反射制品置于它的外表面。
本发明与已知逆向反射制品的不同之处在于：粘结剂层含有由聚酯多元醇和多异氰酸酯制得的聚氨酯聚合物。所述的多异氰酸酯至少含有两个与至少一个芳环非共轭键合的异氰酸酯基。
本发明人发现，这种粘结剂层可提供具有极好耐洗性的逆向反射制品。本发明的逆向反射制品在工业条件下反复洗涤后仍能保留较大百分数的初始逆向反射性。改进的洗涤性能可能归功于粘结剂层的柔软性和水解稳定性。据认为，这些因素有助于将逆向反射元件牢固地固定在粘结剂层中，并在使用金属反射层时抑制了逆向反射元件的氧化。氧化的金属不能有效地逆向反射光线。
附图中：
图1是本发明逆向反射制品10的截面图；
图2表示含有本发明逆向反射制品10的转移制品(transfer article)30；
图3表明带有本发明逆向反射制品10的衣服制品40；
图4是本发明逆向反射制品的工业洗涤性能的示意图。
图1-3是理想化的，并未按尺寸进行绘制。
图1中表示的逆向反射制品10包括部分埋在粘结剂层14中的逆向反射元件12。逆向反射元件12包括微球形光学元件16和镜面反射层18。微球16和镜面反射层18将大部分入射光反射到光源。照到逆向反射制品前表面19上的光线通过微球16，并被反射层18所反射，再次进入微球，微球中光线方向又被改变到向光源反射的方向。所示的织物20粘接在粘结剂层14的对面，以提高制品的结构整体性。逆向反射制品10可用于构成部分衣服制品的基材(未画出)上。
粘结剂层含有聚氨酯聚合物，它是是(i)聚酯多元醇与(ii)多异氰酸酯的反应产物，所述的多异氰酸酯至少含有两个与至少一个芳环非共轭键合的异氰酸酯基。该聚氨酯聚合物含有氨酯基，-NHCOO-，但也可含有其它基团，如脲基。当二胺链增长剂用于下述反应混合物中时，可在聚合物中产生脲基。
该聚氨酯聚合物较好由聚酯多元醇、多异氰酸酯和链增长剂混合物的一步法反应制得。在一步法，聚合在单个反应中进行，这与包括额外步骤的预聚法(先形成预聚物，然后与链增长剂反应)相反。为了加速形成聚合物，也可将催化剂加入到反应混合物中。
聚酯多元醇的官能度约高达8，但较好是2-4。聚酯多元醇较好是二元醇、三元醇或两者的混合物。聚酯多元醇可用如下通式表示：
Figure C9619687200061
式中R是含有3-12个碳原子的脂族基团，R1是含有高达14个碳原子的脂族或芳族基团。聚酯多元醇的数均分子量较好为500-5000，更好为750-4000，最好为1000-3000。聚酯多元醇的酸值较好不大于1.0，更好不大于0.7。酸值可按ASTMD4662-93进行测量。
聚酯多元醇可由三种反应物：芳香酸、脂肪酸和二元醇制得。两种酸较好按1∶1的摩尔比使用。芳香酸的重量百分数较好约为15-40％，更好为20-35％。脂肪酸的重量百分数较好约为20-45％，更好为25-40％。二元醇按适于与酸反应的量使用，它的链长为3-12个碳原子，更好为4-8个碳原子。
芳香酸可以是间苯二甲酸之类的二元酸，脂肪酸可以是壬二酸之类的二元酸。芳族二元酸一般含有单个芳环(5-6个碳原子)，但也可含有2-3个芳环(10或14个环原子)。脂族二元酸一般含有4-10个碳原子，较好含有6-8个碳原子。
用于制备聚酯多元醇的二元醇可含有约3-12个碳原子，例如是1，6-己二醇、1，4-丁二醇、2-甲基-1，3-丙二醇、新戊二醇或环己烷二甲醇。
市售聚酯多元醇的实例是购自Ruco Polymer Corporation of Hicksville，NewYork的RucoflexTM S-1035-55。据称，这种聚酯多元醇含有约40％重量的1，6-己二醇、约28％重量的间苯二甲酸和约32％重量的壬二酸。其它可用的市售聚酯多元醇包括：购自Miles，Inc.，Pittsburgh，Pennsylvania的DesmophenTM多元醇、购自Inolex Chemical Co.，Philadelphia，Pennsylvania的LexorezTM多元醇和购自Witco Corporation，New York，New York的FormezTM多元醇。
本发明中所用的多异氰酸酯至少含有两个与至少一个芳环非共轭键合的异氰酸酯基。每个异氰酸酯基与所连芳环间一般有1-20个碳原子，较好有1-2个碳原子。两个异氰酸酯基较好在六元芳环的1，3位上连接到每个芳环上。多异氰酸酯的实例包括：
Figure C9619687200071
间-四甲基二甲苯二异氰酸酯(TMXDI)；
Figure C9619687200072
二甲苯二异氰酸酯；聚异氰酸(二甲基间-异丙烯基苄)酯；
(由(异氰酸(二甲基间-异丙烯基苄)酯通过双键的反应形成)式中x是2-20的整数；和聚(酚-甲醛)N-(亚烷基异氰酸根合氨基甲酸酯)；式中R是含有1-20个碳原子的脂族基，x与上述定义相同。
芳族多异氰酸酯的其它实例包括甲苯二异氰酸酯(TDI)、二(4-苯基)甲烷异氰酸酯(也称作二苯甲烷二异氰酸酯或MDI)和多亚苯基多亚甲基异氰酸酯(PMDI)。这些多异氰酸酯具有与芳环共轭键合的异氰酸酯基，但它们可与上述芳族多异氰酸酯结合使用。也可使用上述多异氰酸酯的混合物、低聚物和聚合物，而且如果有一个以上异氰酸酯官能团，这些混合物、低聚物和聚合物，就认为是本发明中所用的术语所指的多异氰酸酯。
合适的市售多异氰酸酯的实例包括TMXDI(Cytec Industries，West Patterson，New Jersey)；Mondur CB-75(Miles Inc.，Pittsburgh，Pennsylvania)；和DesmodurW(Miles Inc.，Pittsburgh，Pennsylvania)。
有用链增长剂包括二元醇和二胺，如1，4-丁二醇、1，6-环己烷二甲醇、1，6-己二醇、2-甲基-1，3-丙二醇、双酚A、分子量为100-500的聚环氧烷烃多元醇和4，4′-亚甲基二(2-氯苯胺)。链增长剂也可包括三元醇，如甘油、三羟甲基丙烷等。优选的链增长剂是1，4-丁二醇。
反应混合物中异氰酸酯基与羟基的比率较好为0.9-1.2，更好为1-1.1。异氰酸酯基与羟基之比仅包括多异氰酸酯上的异氰酸酯基，但聚酯多元醇和链增长剂上的羟基都用于计算羟基数。链增长剂与聚酯多元醇的重量比(weight percent)约为0.5-5，更好为0.7-4，最好为0.9-3。
催化剂一般用在反应混合物中。多异氰酸酯与含活性氢化合物反应的催化剂在本领域中是众所周知的，例如参见美国专利4,495,061。优选的催化剂包括有机金属化合物和胺。有机金属化合物可以是有机锡化合物，如二甲基二月桂酸锡、二丁基二月桂酸锡、二丁基二硫醇锡、二甲基二巯基乙酸锡和二辛基二巯基乙酸锡。胺催化剂较好是叔胺，如三亚乙基二胺、B，B″-二吗啉代乙醚和三(二甲氨乙基)苯酚。反应混合物中催化剂的用量为0.05-0.30％重量，较好为0.06-0.20％重量，更好为0.07-0.15％重量。
除了上述组分外，反应混合物还可含有其它添加剂，如增附剂。增附剂的实例包括异氰酸酯官能的硅烷、胺官能的硅烷、巯基官能的硅烷和缩水甘油基官能的硅烷。其它增附剂包括有机官能的铬化合物、有机官能的钛和诸如1994年3月23日提交和题目为“逆向反射制品及其制造方法”的美国专利申请08/216,404(现为美国专利5,474,827)中揭示的螯合剂。上述的专利参考结合于本发明。
另外，粘结剂层可含有着色剂(如颜料、染料和金属片)、填料、稳定剂(如热稳定剂和抗氧化剂(如受阻酚)和光稳定剂(如受阻胺或紫外稳定剂))、阻燃剂、流动改性剂(如碳氟化合物或硅氧烷之类的表面活性剂)、增塑剂和弹性体。选择这些添加剂时应当小心，因为其中某些添加剂可能会损害耐洗涤性。例如，大量的阻燃剂(如蜜胺焦磷酸盐)可能在洗涤后对制品的逆向反射性能产生不利影响。对具有铝逆向反射层的制品优选的着色剂包括黑色染料，如金属偶氮染料。
粘结剂层一般是厚度约为1-250微米的连续、不透液体的聚合物片状层。它的厚度较好为50-150微米。小于50微米的厚度可能太薄，结果不能粘附到基材和光学元件上。超过150微米的厚度可能不必要地使制品发硬，而且增加了成本。
如上所述，光学元件由粘结剂层支承，以改变光线的方向。光学元件可以是微球，但为了最均匀和有效地进行逆向反射，光学元件较好是基本上为球形的微球。所述的微球较好是基本上透明的，从而减少光线的吸收，将大多数的入射光线逆向反射。“透明”一词是指能透过光线。微球通常是基本上无色的，但也可用某些其它方式着色。微球可以用玻璃、非玻璃陶瓷或合成树脂制成。一般来说，玻璃微球和非玻璃陶瓷是优选的，因为它们比由合成树脂制成的微球更硬更耐用。可用于本发明中的微球的实例揭示在如下美国专利中：1,175,224、2,461,011、2,726,161、2,842,446、2,853,393、2,870,030、2,939,797、2,965,921、2,992,122、3,468,681、3,946,130、4,192,576、4,367,919、4,564,556、4,758,469、4,772,511和4,931,414。这些专利中揭示的内容参考结合于本发明中。
微球的平均直径一般为约30-200微米。直径小于这个范围的微球可能提供较低的逆向反射性，直径超过这个范围的微球可能为逆向反射制品带来不合需要的粗糙结构，或可能不合需要地降低逆向反射制品的柔软性。用于本发明中的微球的折射率约为1.7-2.0，一般认为该范围对暴露型透镜逆向反射制品有用。
如上述所述，本发明中所用的光学元件可具有位于光学元件埋入部分下面的金属反射层，以提供许多逆向反射元件。金属反射层较好置于光学元件的埋入部或后部。本发明中所用的“金属反射层”一词是指含有纯或合金型元素金属的层，该层能反射光线，较好镜面反射光线。该金属可以是由真空淀积法、汽相淀积法、化学淀积法或非电镀法产生的连续镀层。金属层应厚得足以反射入射光。金属反射层的厚度一般约为50-150纳米。
许多金属可用于制备镜面反射金属层。这些金属包括元素铝、银、铬、镍、镁等。因为铝和银能提供良好的逆向反射亮度，所以它们是优选的。当使用铝时，某些金属可能是金属氧化物和/或氢氧化物形式。虽然银镀层的反射色比铝镀层更明亮，但铝镀层一般是优选的，因为当粘附于玻璃光学元件时铝镀层能提供更好的耐洗涤性。
介质镜可代替金属反射层用作镜面反射层。介质镜可类似于美国专利3,700,305和4,763,985(Bingham)中揭示的已知介质镜。这两个专利中揭示的内容参考结合于本发明中。
使用介质镜时，微球一般具有折射率n2，并在上面涂覆一层折射率为n1的透明材料。折射率为n1的透明材料对面与折射率为n3的材料接触。折射率n2和n3至少为0.1，较好至少为0.3，比n1更高或更低。透明材料层的光学厚度一般相当于波长范围为380-1000纳米的光线的约1/4波长的奇数倍(即1，3，5，7.....)。因此，n2＞n1＜n3或n2＜n1＞n3，而且透明层两侧材料的折射率可能比n1都更高或都更低。当n1比n2和n3高时，n1较好为1.7-4.9，n2和n3较好为1.2-1.7。相反，当n1比n2和n3低时，n1较好为1.2-1.7，n2和n3较好为1.7-4.9。
介质镜较好含有连接排列(contiguous array)材料，至少一种是层形的，具有交替次序的折射率。在一个优选的实施方案中，连续排列具有2到7层，较好3到5层，并邻接于球形透镜元件。所有层较好是透光材料，而且是清澈或基本上无色的，以减少光线吸收和最大程度地显示下面的着色粘结剂层。介质镜可提供非常好的逆向反射性，虽然它一般不如金属反射层那样有效。
在所需折射率范围内能用于提供透明材料的许多化合物的实例是：高折射率材料，如CdS、CeO2、CsI、GaAs、Ge、InAs、InP、InSb、ZrO2、Bi2O3、ZnSe、ZnS、WO3、PbS、PbSe、PbTe、RbI、Si、Ta2O5、Te、TiO3；低折射率材料，如Al2O3、AlF3、CaF2、CeF3、LiF、MgF2、NaCle、Na3AlF6、ThOf2、全氟丙烯与偏二氟乙烯的弹体共聚物(折射率为＞＞1.38)等。其它的材料记载在Thin Film Phenomena，K.L.Chopra，750页，McGraw-Hill BookCompany，New York，(1969)。优选的连续(succeeding)层含有冰晶石(Na3AlF6)和硫化锌。
逆向反射制品10可通过先形成图2所示的制品30而制成。制品30一般称为转移制品(transfer article)。为了制造转移制品30，将大量逆向反射元件12部分埋在粘结剂层14中。这可以按所需的临时排列将透明微球16排列在载体织物(carrier web)32上而办到。微球16较好尽可能紧密地填充在载体32上，可以用常规的方法(如印刷法、筛选法、串联法)或用热压辊(hot can roll)进行排列。载体织物32可包括纸片36上的可加热软化聚合物层34。对于载体织物32有用的聚合物层34的实例包括聚氯乙烯；聚烯烃，如聚乙烯、聚丙烯和聚丁烯；和聚酯等。就将微球涂布在载体织物上的进一步讨论，请参阅美国专利4,763,985、5,128,804和5,200,262中。这些专利揭示的内容参考结合于本发明中。
聚合物层34按所需的排列将微球16固定。部分取决于载体织物32和微球16的特性，可能需要通过涂布选择的脱模剂或增附剂对载体32和/或微球16进行处理(condition)，以获得所需的载体脱模性能。
然后将反射层18涂布到微球突起一侧的载体织物32上。通过控制微球16埋在载体织物中的深度，可部分控制由反射层18覆盖的微球部分所表示的逆向反射元件12的大小。形成逆向反射元件12后，可在镜面反射层上形成粘结剂层14，以制造制品30。
将反应物混合在一起，然后迅速将其涂覆在反射层18上，可在反射层18上形成粘结剂层14。一般将涂层加热到25-150℃，以提高反应速率。较好将涂覆的混合物加热到35-120℃，更好加热到40-110℃。加热步骤能形成弹性良好的聚氨酯粘结剂层，从而使制品具有很好的耐洗涤性。为了形成粘合剂层，可在反射层上形成其它聚氨酯聚合物层。另外，在聚合物完全反应前，将织物20放在涂覆的混合物上，可将其粘附在粘结剂层上。形成粘结剂层后，可将载体32与转移制品30分离，从而可使逆向反射制品32用于所需的目的。
本发明的逆向反射制品可用缝纫之类的机械方法结合在基材上。然而在某些应用中，需要用粘合剂层(未画出)将制品固定在基材上，可带或不带织物层20。粘合剂层可以是压敏粘合剂、加热活化粘合剂或紫外辐射活化粘合剂。带逆向反射制品的基材可放在衣服制品的外表面，从而按通常方法穿在人身上时可显露逆向反射制品。该基材例如可以是含有棉、毛、亚麻、尼龙、聚烯烃、聚酯、纤维素、人造丝、聚氨酯、乙烯基树脂、丙烯酸类树脂、橡胶、斯潘德克斯(spandex)等的编织物、针织物或非织造织物，或者它可由皮革或纸制成。
图3表示带有长条形片或带状逆向反射制品42的安全马甲。安全马甲通常由筑路工人穿着，以提高对过往驾驶人员的可见度。这种马甲常与污垢和灰尘接触。因此，这种逆向反射制品必须能耐严厉的洗涤条件，这样马甲能重复使用多次。本发明的逆向反射片能进行这种清洗。
虽然选用安全马甲40进行说明，但本发明的衣服制品可制成各种形式。本发明中所用的“衣服制品”一词是指已裁制成人类可穿戴的可洗涤服装。可显示本发明逆向反射制品的衣服制品的其它实例包括衬衫、汗衫、夹克衫(如消防队员夹克衫)、外套、裤子、鞋子、袜子、手套、腰带、帽子、西服、连体式服装、手提包、背包等。
                          实施例
如下测试方法用在实施例中。
                       工业洗涤过程
通过洗涤和干燥一片带有逆向反射制品的织物来评估耐洗涤性。洗涤和干燥的复合顺序被称作一个循环。试样用购自Pellerin Milnor Corp.的30015M4G型Milnor System 7洗衣机进行洗涤，选择用于严重污染的有色织物的程序7。该织物是100％棉巾，逆向反射制品用缝制法固定在织物上。在洗衣机中加入足够片数(约80片)的织物(约45厘米×75厘米)，使负载达28磅。其中包括1-4片带有几个(一般为5个)尺寸为5×15厘米的本发明逆向反射制品的织物。所用的洗涤剂是30克FACTORTM洗涤剂(购自Diversey Fabrilife Chemicals，Inc.，Cincinnati，Ohio，按重量计它含有约40％焦磷酸四钠、30％壬基苯氧基聚氧乙烯乙醇、20％碳酸钠和10％无定形二氧化硅)和60克ORTHOSILTM(购自Elf Atochem NorthAmerica，Philadelphia，Pennsylvania的pH助洗剂，含有约40％重量的NaOH和60％重量的偏硅酸钠)。程序7中按如下步骤完成循环中的洗涤部分。
操作                             时间(分)
洗涤(suds)                        10
清洗(flush)                       2
清洗                              7
清洗                              7
清洗                              2
热水漂洗(rinse)                   2
冷热水混合漂洗                    2
冷水漂洗                          4
甩干                              6
                           合计41(51：20*)*总时间(分)，包括大致的装入时间。
在洗涤步骤中，在搅拌下将热水(68升74℃)和洗涤剂加入洗衣机的洗涤桶中。在清洗步骤中，在排干了含有洗涤剂的废水后，将等量的新鲜热水(68升74℃)加入到洗涤桶中。
漂洗步骤基本上与清洗步骤相同，所不同的是水更冷一些。在第一次漂洗时，水温约为74℃；在第二次漂洗(冷热水混合漂洗)时，水温约为约为46℃；最后冷水漂洗时，水温约为18℃。在清洗和漂洗过程中搅动洗涤桶。在甩干步骤中，洗衣机进行高速旋转，从所洗试样中除去水。在洗涤后但在测试逆向反射性之前，将试样放在MaytagTM家用干燥器中按常规设定(on regular setting)干燥30分钟，完成一个工业洗涤工艺循环。在指定的循环数后，测试每个试样中部的逆向反射亮度。
                          逆向反射性试验
按标准化试验ASTM E 810-93b测量逆向反射系数RA。测试的结果表示为初始逆向反射亮度的百分数，其中RA按烛光/勒克斯·米2(cd.lx-1.m-2)。ASTM E810-93b中所用的入射角为-4度，观察角为0.2度。进一步参考“ASTM E 810-93b”是指入射角和观察角如上句规定的ASTM E 810-93b。
                            术语汇编
RucoflexTM S-1035-55，购自Ruco Polymer Corp.的聚酯多元醇。
BDO：1，4-丁二醇
Silane A 1310：购自OS Specialties，Inc.，Danbury，Connecticut的γ-异氰酸酯基丙基三乙氧基硅烷
TMXDI：购自Cytec Industries，West Patterson，New Jersey的四甲基二甲苯二异氰酸酯
MondurTM CB-75：购自Miles Inc.，Pittsburgh，Pennsylvania的基于甲苯二异氰酸酯的多异氰酸酯
FomrezTM SUL-3：购自Witco Corp.，New York New York的二丁基二乙酸锡
NCO：异氰酸酯
DesmodurTM N-100：购自Miles的1，6-己烷二异氰酸酯的缩二脲
JeffamineTM D-2000：购自Huntsman Chemical Corp.，Salt Lake City，Utah的分子量为2000的二胺
DesmophenTM XP-7053：购自Miles的脂环族二胺(当量＝277)
DBTDL：二丁基二月桂酸锡
                      实施例1
在玻璃微球的突起部分汽相淀积镜面反射的铝层，形成单层逆向反射元件。玻璃微球的平均直径为40-90微米，并部分和暂时埋入载体片材中。所述的载体片材包括重叠在聚乙烯层上的纸，微球埋入聚乙烯层中。将支承涂铝微球的载体片材用作涂覆微球粘结组合物的基底。所述的粘结组合物含有：
30.0克RucoflexTM S-1035-55
0.30克1，4-丁二醇
1.20克OSi-Silane A-1310
3.96克Cytec-TMXDI
1.85克Miles-MondurTM CB-75，三官能芳族异氰酸酯
0.05克Witco-FomrezTM SUL-3，催化剂
按上述次序将各反应物称入一个烧瓶中，进行聚氨酯生成反应。室温下用手混合反应物，并迅速将其涂覆在铝汽相涂覆层上，厚度为4密耳。将涂层放在66℃(150°F)烘箱中30秒钟，然后粘贴上100％聚酯织物。再将所得的逆向反射制品放在110℃(230°F)烘箱中10分钟。加热产生位于汽相涂覆微球和织物间的弹性热固性聚酯聚氨酯粘结剂层。
                      实施例2-8
除了按表1改变反应物和条件以外，按上述方法制备实施例2-15。用量用克表示。
                         表1
 实施例 Rucoflex-TMS-1035-55 1，4-丁二醇 SilaneA-1310 CytecTMTMXDI DesmodurTMCB-75 FomrezTMSUL-3 二丁基二月桂酸锡 JeffamineD-2000  DesmodurTMN-100 DesmophenTMXP-7053
  1   30.0  0.30  1.20  3.96    1.85  0.05
 2a   30.0  0.30  1.20  3.49    3.09  0.05
 3b   30.0  0.30  1.20  3.03    4.31  0.05
 4c   30.0  0.30  1.20  2.33    6.16  0.05
 5d   30.0  0.30  1.20  4.67  0.08
 6e   30.0  0.30  1.20  3.49  0.05     1.82
 7f   30.0  1.20  3.16    2.80  0.05    0.90
 8g   30.0  1.20  2.91    2.57  0.05  0.30
a按实施例1所述的方法进行，所不同的是涂层在66℃(150°F)烘箱中放置120秒钟，然后在104℃(220°F)烘箱中放置30秒钟。贴上聚酯织物后，将制品在104℃(220°F)烘箱中放置10分钟。
b按实施例1所述的方法进行。
c按实施例1所述的方法进行。
d按实施例1所述的方法进行，所不同的是在将织物层压到试样上之前，让涂层在室温下放置2分钟，然后在66℃烘箱中放置2分钟，在104℃烘箱中放置2.5分钟。
e按实施例1所述的方法进行，所不同的是涂层在66℃烘箱中放置45秒钟。贴上聚酯织物后，将制品放在104℃烘箱中10分钟。
f按实施例1所述的方法进行。
g按实施例1所述的方法进行。
主要反应组分及其相互比率和用量概括在表2中。
                                         表2
实施例   NCO(1)    NCO(2)    比率(1)∶(2) 链增长剂  链增长剂用量*   NCO/OH比率   催化剂
    1  TMXDI   CB-75  85∶15   BDO     1.0     1.05   SUL-3
    2  TMXDI   CB-75  75∶25   BDO     1.0     1.05   SUL-3
    3  TMXDI   CB-75  65∶35   BDO     1.0     1.05   SUL-3
    4  TMXDI   CB-75  50∶50   BDO     1.0     1.05   SUL-3
    5  TMXDI   BDO     1.0     1.05   DBTDL
    6  TMXDI   N-100  75∶25   BDO     1.0     1.05   SUL-3
    7  TMXDI   CB-75  75∶25   XP7053     3.0     1.05   SUL-3
    8  TMXDI   CB-75  75∶25   D-2000     1.0     1.05   SUL-3
*链增长剂的用量单位是相对于多元醇的％重量。
按工业洗涤方法对试样进行洗涤，并按ASTM E-810-93b测试逆向反射亮度系数RA。保留的逆向反射亮度％确定为初始逆向反射亮度的％。RA结果记载在如下表3中，保留的逆向反射亮度记载在如下表4中。
                                                      表3
                                                      R A 值
  循环   实施例1   实施例2   实施例3   实施例4   实施例5   实施例6   实施例7   实施例8
    0     438     624     608     650     392     681     616     634
    1     396     551     567     571     330     560     540     545
    2     383     527     503     474     375     489     517     512
    3     380     496     453     415     380     413     484     479
    4     364     470     419     367     372     365     472     462
    5     359     448     391     328     355     335     455     445
    6     356     434     358     297     361     304     435     427
    7     357     412     338     271     353     276     430     416
    8     348     391     316     251     355     260     411     402
    9     340     379     294     223     340     246     405     392
    10     336     358     278     209     343     230     392     383
    11     327     351     255     333     224     382     365
    12     332     335     245     334     210     376     368
    13     316     321     233     340     198     367     362
    14     321     310     223     326     190     367     359
    15     313     297     213     324     178     346     328
    16     304     288     201     320     170     338     324
    17     304     274     198     317     162     328     316
    18     298     258     192     320     158     322     302
    19     293     243     180     316     150     314     290
    20     287     227     172     302     144     302     284
    21     291     296     301     280
    22     284     292     292     274
    23     264     296     275     258
    24     268     290     274     250
    25     264     285     267     246
                                             表4
                                          亮度保留率(％)
  循环号#   实施例1   实施例2   实施例3   实施例4    实施例5   实施例6   实施例7   实施例8
    0    100.0   100.0   100.0   100.0    100.0   100.0    100.0   100.0
    1    90.4   88.3   93.3   87.8    84.2   82.2    87.7   86.0
    2    87.4   84.5   82.7   72.9    95.7   7.18    83.9   80.8
    3    86.8   79.5   74.5   63.8    96.9   60.6    78.6   75.6
    4    83.1   75.3   68.9   56.5    94.9   53.6    76.6   72.9
    5    82.0   71.8   64.3   50.5    90.6   49.2    73.9   70.2
    6    81.3   69.6   58.9   45.7    92.1   44.6    70.6   67.4
    7    81.5   66.7   55.6   41.7    90.1   40.5    69.8   65.6
    8    79.5   62.7   52.0   38.6    90.6   38.2    66.7   63.4
    9    77.6   60.7   48.4   34.3    86.7   36.1    65.7   61.8
    10    76.7   57.4   45.7   32.2    87.5   33.8    63.6   60.4
    11    74.7   56.3   41.9    84.9   32.9    62.0   57.6
    12    75.8   53.7   40.3    85.2   30.8    61.0   58.0
    13    72.1   51.4   38.3    86.7   29.1    59.6   57.1
    14    73.3   49.7   36.7    83.2   27.9    59.6   56.6
    15    71.5   47.6   35.0    82.7   26.1    56.2   51.7
    16    69.4   46.2   33.1    81.6    54.9   51.1
    17    69.4   43.9   32.6    80.9    53.2   49.8
    18    68.0   41.3   31.6    81.6    52.3   47.6
    19    66.9   38.9   29.6    80.6    51.0   45.7
    20    65.5   36.4   28.3    77.0    49.0   44.8
    21    66.4    75.5    48.9   44.2
    22    64.8    74.5    47.4   43.2
    23    60.3    75.5    44.6   40.7
    24    61.2    74.0    44.5   39.4
    25    60.3    72.7    43.3   38.8
表3和表4中的数据表明本发明的试样具有极好的耐工业洗涤性。

Claims (15)

1.一种逆向反射制品，其特征在于它包括：
一层至少部分埋在粘结剂层中的逆向反射元件，所述的粘结剂层含有聚氨酯聚合物，所述的聚氨酯聚合物是(i)聚酯多元醇与(ii)多异氰酸酯的反应产物，所述的多异氰酸酯至少含有两个与至少一个芳环非共轭键合的异氰酸酯基。
2.如权利要求1所述的逆向反射制品，其特征在于所述的聚氨酯聚合物是由聚酯多元醇、链增长剂和多异氰酸酯的一步法反应制得。
3.如权利要求1或2所述的逆向反射制品，其特征在于所述的聚酯多元醇是芳香酸、脂肪酸和二元醇的反应产物。
4.如权利要求3所述的逆向反射制品，其特征在于在制备聚酯多元醇时，按1∶1的摩尔比使用芳香酸和脂肪酸，所述二元醇的链长为3-12个碳原子。
5.如权利要求3所述的逆向反射制品，其特征在于所述聚酯多元醇的数均分子量为500-5000。
6.如权利要求5所述的逆向反射制品，其特征在于所述聚酯多元醇的数均分子量为750-4000。
7.如权利要求6所述的逆向反射制品，其特征在于所述聚酯多元醇的数均分子量为1000-3000。
8.如权利要求1所述的逆向反射制品，其特征在于聚酯多元醇的酸值不大于1.0。
9.如权利要求8所述的逆向反射制品，其特征在于所述聚酯多元醇的酸值不大于0.7，聚酯多元醇的官能度为2-4，所述的聚酯多元醇是二元醇、三元醇或其混合物。
10.如权利要求1所述的逆向反射制品，其特征在于所述多异氰酸酯选自1，4-丁烷二异氰酸酯、二甲苯二异氰酸酯、聚异氰酸(二甲基间-异丙烯基苄)酯、聚(酚-甲醛)N-(亚烷基异氰酸根合氨基甲酸酯)及它们的混合物。
11.如权利要求3所述的逆向反射制品，其特征在于所述的聚氨酯聚合物由异氰酸酯与羟基之比为0.9-1.2，链增长剂与聚酯多元醇的重量比为0.5-5的反应混合物制得。
12.如权利要求1所述的逆向反射制品，其特征在于有两个与六元芳环非共轭键合的异氰酸酯基，芳环与异氰酸酯基间有1-2个碳原子。
13.如权利要求1所述的逆向反射制品，其特征在于链增长剂与聚酯多元醇的重量比为0.9-3，所述聚氨酯聚合物是热固性弹性体，所述的聚氨酯聚合物是在有机金属或胺催化剂的存在下制得，链增长剂是1，4-丁二醇，链增长剂与聚酯多元醇的重量比为0.5-5，聚氨酯聚合物是在二丁基二月桂酸锡催化剂的存在下制得，所述的反应混合物含有增附剂，粘结剂层的厚度为1-250微米，所述的逆向反射元件包括平均直径为30-200微米的透明微球，并在微球埋入部分之下设置铝或银反射层。
14.如权利要求1所述的逆向反射制品，其特征在于在10次工业洗涤循环后仍至少保留30％的初始逆向反射亮度。
15.一种服装制品，其特征在于它包括如权利要求1-14所述的逆向反射制品和形成服装制品部分外部的基材，所述的逆向反射制品被固定在所述的基材上。
CN96196872A 1995-09-15 1996-08-05 含有聚酯型聚氨酯粘结剂层的逆向反射制品 Expired - Fee Related CN1100807C (zh)

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CN1196067A (zh) 1998-10-14
EP0850259B1 (en) 1999-06-09
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JP3950941B2 (ja) 2007-08-01
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US5645938A (en) 1997-07-08

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