CN1139628C - 使用位阻胺光稳定剂在聚氯乙烯制品中稳定荧光染料 - Google Patents

使用位阻胺光稳定剂在聚氯乙烯制品中稳定荧光染料 Download PDF

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CN1139628C
CN1139628C CNB988108895A CN98810889A CN1139628C CN 1139628 C CN1139628 C CN 1139628C CN B988108895 A CNB988108895 A CN B988108895A CN 98810889 A CN98810889 A CN 98810889A CN 1139628 C CN1139628 C CN 1139628C
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hindered amine
polyvinyl chloride
amine light
fluorescence
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K・M・怀特
K·M·怀特
帕维尔卡
L·A·帕维尔卡
莱特利
V·L·莱特利
科德尔
J·C·科德尔
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Abstract

一种荧光性能的耐久色彩的制品，它包括基本无溶剂的聚氯乙烯基质；噻吨荧光染料；和分子量小于约1000g/mol的仲或叔位阻胺光稳定剂。本发明的优点在于它提供的挠性聚氯乙烯薄膜表现出耐久的荧光色彩。

Description

使用位阻胺光稳定剂 在聚氯乙烯制品中稳定荧光染料
技术领域
本发明涉及聚氯乙烯制品，通过使用所选的位阻胺光稳定剂，该制品具有耐久的荧光色彩。
背景技术
长期置于阳光照射下，含着色剂的制品会褪色。例如，将制品在室外放置一个夏季后，在秋季到来时它们通常会失去原来的色彩。尽管这种褪色会发生在常规的着色剂和荧光着色剂中，但是荧光着色剂的褪色尤其严重。
置于日常阳光辐照中的荧光色彩制品的寿命通常为数个月，而使用常规着色剂的制品的寿命可达数年。尽管荧光着色剂的稳定性较差，但是由于其会提高制品的能见度而频繁使用。与常规着色剂不同，荧光着色剂可例如吸收非可见区的光线(如紫外光)，并将其以可见光谱的形式再发射。这种固有的性能使荧光制品在着色制品及其周围环境之间形成增加的可见反差。
逆向反射领域的研究人员尝试了使用各种方法来稳定含荧光着色剂的的聚合物制品。例如，Burns等在美国专利5,605,761中报道了使用位阻胺光稳定剂(HALS)来保持聚碳酸酯聚合物基质中含荧光染料的制品的耐久性。该文献还公开了所述荧光染料可以是噻吨、苝酰亚胺或硫靛染料，HALS可以是2，2，6，6-四烷基哌啶族化合物。尽管这些制品在保持荧光色彩稳定性方面相当有用，但是由于聚碳酸酯聚合物基质固有的刚性使之不是很柔软。
他人，例如Pavelka等在美国专利5,387,458中尝试使用能阻挡340-400nm范围的紫外光(UV)辐照的紫外光掩蔽层来保持荧光色彩。荧光色彩置于与掩蔽层相分离的层中。尽管由于荧光色彩的稳定性而使这些制品高度受益，但是它要求具有两层单独的层会提高结构的成本。另外，掩蔽层不能减少由于染料吸收可见光造成的荧光染料的分解。
聚氯乙烯(PVC)薄膜由于其挠性并可从市场上获得而适用于许多用途。在聚氯乙烯制品中通常使用UV吸收稳定剂使聚合物基质光稳定。参见例如Marice McMurrer，Update：UV Stabilizers，PLASTICS COMPOUNDING 40(Jan/Feb.1985)。但是UV稳定剂不能有效地稳定在基质中的荧光染料。
尽管目前广泛使用含荧光染料的PVC薄膜，但是它们具有很差的色彩保持性。造成褪色的因素包括在PVC基质中缺乏染料稳定性、染料迁移和由树脂提供的抗光致降解的保护性很小。
技术文献提出分子结构中带有氨基的HALS与PVC不相容。例如，T.Hjertberg和E.M.Sorvik在DERGADATION AND STABILISATION OF PVC，E.D.Owen(出版商)21，69(1984)的Thermal Degradation of PVC中提到在高温下胺会引发PVC脱氯化氢，导致PVC基质降解。另外，基于仲或叔哌啶基胺的HALS是高碱性化合物。例如在水中测定时，与pkb为4.7的氨相比，2，2，6，6-四甲基哌啶的pkb为2.9。参见Can Zhang等的 位阻胺光稳定剂：暴露于酸的 影响，Volume 24 of JOURNAL OF POLYMER SCIENCE：PART C：POLYMER LETTERS453，453(1986)。由于其碱性，在挥发性酸(如盐酸(HCL))的存在下HALS会形成盐。盐酸是由“光引发的PVC薄膜的老化”导致的降解和氧化反应形成的。参见Martinez等的Prediction of Photoageing of Plasticized PVC FilmsContaining UV-Stabilisers，Volume 54 of POLYMER DEGRADATION ANDSTABILITY 49，49(1996)。碱性HALS的存在加上容易获得的HCl来源造成能降解PVC基质的酸碱反应。
由于PVC薄膜的挠性性能以及在许多制品中需要使用荧光着色剂，因此需要一种兼顾这些性能的耐久的着色制品。
发明的概述
本发明首次通过加入特殊类型的HALS来稳定一类荧光染料，提供一种着色制品，它在无溶剂的PVC主体基质中表现出耐久的荧光性能。与HALS与PVC不相容的已知报道相反，本发明发现在PVC主体基质中HALS和荧光染料的新组合表现出优良的着色的荧光制品的稳定化作用。由于PVC主体基质具有良好的机械和热性能，因此本发明制品适合于许多用途，包括，但不限于在衣物、交通控制标记和器件(如缠绕的标记)、背包和水中飘浮的安全器械。
简单地说，本发明制品表现出耐久的色彩和荧光性能，它包括(a)含有基本无溶剂的聚氯乙烯树脂的聚合物基质；(b)噻吨荧光染料；和(c)位阻胺光稳定剂，所述光稳定剂包括至少一个仲胺或叔胺基团，并且分子量小于约1000g/mol。可将这些组分混合成混合物，随后由混合物制成制品而制得本发明制品。
由于加工基本无溶剂的聚氯乙烯树脂需要将树脂置于高温中，因此不能预料可得到耐久的荧光色彩制品。如上所述，在高温下胺会引发聚氯乙烯脱氯化氢，导致聚氯乙烯基质降解。尽管存在这种概念，但是本发明制品具有令人惊奇的耐久性。因此，结合使用基本无溶剂的聚氯乙烯和HALS得到的结果是本领域在形成耐久的荧光色彩PVC制品方面所从未提到的。
本发明的优点在于它表现出耐久的色彩性能和荧光，无需使用保护外层。但是如有必要，可使用保护外层进一步增加本发明制品的耐久性。即使置于直射的阳光下，本发明制品保持色彩的时间和产生荧光的时间通常均比预计的时间更长久。因此，本发明制品是与逆向反射元件一起使用的良好的候选材料。
本发明另一个优点在于可在无溶剂体系中加工聚合物、染料和HALS，它不仅基本消除了溶剂向大气中的散发，而且通过不使用溶剂而降低了制品的制造成本。
附图简述
下面将结合附图进一步说明本发明，附图中；
图1是本发明逆向反射制品10的剖面图；
图2是本发明另一个实例的逆向反射制品20的剖面图；
图3是本发明另一个实例的逆向反射制品30的剖面图；
图4是本发明另一个实例的逆向反射制品50的剖面图；
图5是本发明另一个实例的逆向反射制品70的剖面图。
这些附图是示意性的而非成比例的，仅用于说明而非限定。
定义
在本文中，术语：
“着色剂”指用于使制品具有色调和色度的颜料、染料或其它物质；
“常规着色剂”指置于可见光和/或紫外光下，不会明显产生荧光并且用目测未表现出荧光性能的着色剂；
“立方角薄膜”指一个表面突出有立方角元件的单层逆向反射薄膜；
“立方角片材”指含有立方角元件的多层逆向反射片；
“耐久的”指经过照射而天候老化后具有增强的色彩和荧光保持性；
“嵌入透镜”逆向反射基片包括(a)具有间隔层的单层微球和(b)与微球背面光学相连的一层反射层以及嵌有微球前表面的一层粘合剂层；
“包封透镜”的逆向反射基片包括(a)一层单层微球和与微球背面相连的一层反射层，以及(b)放置在微球形成单元正面的一层覆盖层；
“露出透镜”逆向反射基片包括一层单层微球和与嵌入在粘合剂层中的微球背面相连的一层反射层；
“位阻胺光稳定剂”指用于光稳定荧光染料的添加剂，该稳定剂至少具有一个仲胺或叔胺基团；
“聚合物基质”指主要的聚合物材料，其中能容纳荧光染料和位阻胺光稳定剂；
“仲胺基团”指含有氮(N)和一个与氮原子相连的氢(H)原子的基团；
“叔胺基团”指含有氮(N)并且氮原子上不连接有氢原子(H)的基团；
“基本无溶剂的聚氯乙烯树脂”指不使用溶剂就可进行挤出或压延加工的聚合的聚氯乙烯树脂；
“噻吨荧光染料”指具有噻吨单元作为分子结构一部分的荧光染料；
“天候老化”指将制品放置在天然或人造环境中，包括例如加热、光照、水汽腐蚀和紫外光照射。
说明性实例的详细描述
本发明将基本无溶剂的聚氯乙烯主体基质与荧光染料和位阻胺光稳定剂结合在一起，形成耐久的着色荧光制品。
图1是本发明立方角基逆向反射制品10。制品10(常称为“立方角薄膜”)包括许多立方角元件12和基体层14。在图中未表示的有荧光染料和位阻胺光稳定剂。光线通过正面或第一主表面15进入立方角薄膜10。该光线随后穿过基体层14，照射立方角元件12的平面11，并沿箭头18所指的入射方向回射。
图2是本发明立方角基逆向反射制品20。制品20包括放置在立方角薄膜21的正面或第一主表面25上的主体层26。立方角薄膜21包括许多立方角元件22并可任选地包括基体层24。在一个较好的实例中，主体层26包括基本无溶剂的聚氯乙烯基质、荧光染料和位阻胺光稳定剂(图中均未表示)，并且该层是制品20的最外层。基体层24和主体层26的区别在于它是直接位于立方角元件底部的材料层。如有必要，基体层24(如有的话)和/或立方角元件22可包括基本无溶剂的聚氯乙烯基质、荧光染料和位阻胺光稳定剂。
图3是本发明微球基逆向反射制品30。制品30包括置于嵌入透镜逆向反射基片31的正面或第一主表面35上的主体层36。嵌入透镜片材的一个说明性例子可参见美国专利4,505,967(Bailey)。基片31包括带有间隔层34并嵌入粘合剂层33中的单层微球、镜面反射层38和任选的粘合剂层40。光线通过正面41入射逆向反射制品30。光线随后透过主体层36和粘合剂层33，射入微球32，穿过间隔层34照射镜面反射层38，并沿箭头37所示的入射方向回射。
逆向反射基片还可以是露出透镜的或包封透镜的，这些片材的例子可分别参见美国专利5,316,838(Crandall)和4,025,159(McGrath)。在一个较好的实例中，主体层36包括基本无染料的聚氯乙烯基质、荧光染料和位阻胺光稳定剂。
尽管不是必需的，但是本发明制品可任选地包括含有或不含有紫外光吸收剂的保护外层。该外层最好对可见光是基本透明的，并包括能屏蔽大部分入射的紫外光的手段。图4表示具有立方角薄膜51的逆向反射实例50。主体层56位于立方角薄膜51的正面或主表面55上。放置在主体层56的第一侧57上的是外层58。在一个较好的实例中，主体层56包括基本无溶剂的聚氯乙烯基质、荧光染料和位阻胺光稳定剂。外层58较好与主体层56共延伸，以提供最大的保护。
用于本发明的聚合物基质含有基本无溶剂的聚氯乙烯作为主体基质。该聚合物基质无需掺混其它聚合物(如丙烯酸聚合物)以获得良好的耐久性，因此可主要由无溶剂的聚氯乙烯组成。可向基质中加入增塑剂以获得所需的物理性能，如挠性。适用的增塑剂的说明性例子包括邻苯二甲酸二2-乙基己酯(它以DOP的商品名购自Aristech Chemical Corp)和邻苯二甲酸二异壬酯(它以JAYFLEX DINP的商品名购自Exxon Corp.)。可加入UV吸收剂(如羟基二苯酮)以稳定PVC，防止紫外光降解。可作为加工助剂加入的其它添加剂包括填料、热稳定剂和润滑剂。
增塑的PVC的优点在于它具有优良的挠性，从而适用于从织物至具有复合曲线的各种基材，例如交通隔离墩(barrel)。本发明制品具有足够的挠性，能在室温下缠卷在直径为3mm的芯轴上而不开裂。增塑的PVC还能容易地通过粘合方法或机械方法附着在基材上。一种说明性的机械方法包括将本发明产品缝纫在织物基材上。
可如下制得基本无溶剂的PVC薄膜：将混有荧光染料和HALS的PVC树脂挤出或压延成名义厚度约为0.025-3.2mm(0.001-0.125英寸)，较好约0.076-0.5mm(0.003-0.02英寸)的薄膜或立方角薄膜。后一种范围是较好的原因在于它更适用于逆向反射片。薄膜厚度可随具体用途不同而不同。例如，如果用途需要较高的耐久性，则通常约0.75mm(0.030英寸)级别的较厚的薄膜更适用。PVC薄膜或立方角薄膜的厚度对加入薄膜中的荧光染料和位阻胺光稳定剂的用量具有影响。
适用于本发明的荧光染料是噻吨族化合物。可使用单种染料或组合使用多种染料。适用于本发明的说明性的市售噻吨荧光染料包括HOSTASOLRED GG、HOSTASOLYELLOW 3G、DAY-GLOD-304和DAY-GLOD-315。
一种适用的橙色荧光染料是14H-蒽[2，1，9-mna]噻吨-14-酮，它以C.I.溶剂橙64(HOSTASOLRED GG)的商品名购自Hoescht Celanese，它具有下列化学结构：
一种适用的黄色荧光染料是N-十八烷基-苯并[k.l]噻吨-3，4-二羧酰亚胺，它以C.I.溶剂黄98(HOSTASOLYELLOW 3G)的商品名购自HoeschtCelanese，它具有下列化学结构：
Figure C9881088900092
另一种适用的黄色荧光染料是DAY-GLOD-304，它是购自Day-Glo ColorCorp.，Cleveland，Ohio的噻吨化合物。另一种适用的橙色荧光染料是DAY-GLOD-315，它也是购自Day-Glo Color Corp.的噻吨化合物。
本发明薄膜中通常含有高达2重量％，较好约0.01-1.0重量％的染料。该重量百分数是按本发明薄膜总重量计算的。本发明可适用在该范围以外的染料加入量以获得所需的色彩。例如，如果将染料加入较厚的薄膜中，较少的染料加入量就可获得相同的视觉效果。与含有较少相同染料的制品相比，含有较大染料量的制品一般具有较亮的荧光和更深的色彩。但是，具有高染料含量的制品会表现出自身淬灭现象，该现象是染料分子吸收附近的染料分子发出的能量而产生的。这种自身淬灭会导致荧光亮度不合需求地下降。
具有过量染料的制品会变得不透明，可能是因为部分过量的染料不溶解于聚合物基质中造成的。对于要求本发明制品能透光的用途，例如要求逆向反射的用途，本领域的普通技术人员应注意选择合适的染料含量，从而使基本所有染料均溶解在聚合物基质中。对于无需透光的用途，例如装饰用途，染料的含量是不重要的，因为透明度不成问题。
可向本发明中加入其它染料和颜料(无论是荧光的还是非荧光的)以调节制品的色彩和外观。但是应注意选择染料和颜料及其用量，从而对制品中荧光染料的性能不造成明显影响。如果本发明制品中包括逆向反射元件，则染料和颜料不应不合需求地影响制品的透明度。如果本发明制品的透明度下降，则会不合需求地降低其逆向反射性能。
如上所述，许多技术文献指出位阻胺光稳定剂(HALS)的氨基与聚氯乙烯不相容。因此使用某些HALS来光稳定本发明荧光色彩的PVC制品是令人惊奇的。
不想受理论的束缚，但相信本发明将所选的HALS、基本无溶剂的聚氯乙烯主体基质和所选的荧光染料组合在一起阻止了目前仍不明原因的降解和/或染料与聚氯乙烯之间的反应。如我们所知，本发明的优点是通过将本文所述的基本无溶剂的聚氯乙烯基质、噻吨荧光染料和位阻胺光稳定剂结合在一起而获得的。
通常，本发明制品中含有高达约2重量％，较好约0.05-1.0重量％的HALS。HALS的重量百分数是按照本发明薄膜的总重量计算的。
适用于本发明的说明性市售HALS包括TINUVIN770、TINUVIN144和SANDUVORPR-31。
一种化学式为癸二酸二-(2，2，6，6-四甲基-4-哌啶基)酯、分子量约为480g/mol并且含有仲胺基团的HALS可以TINUVIN770的商品名购自Ciba-Geigy Corp.，并具有下列化学结构：
Figure C9881088900111
该HALS具有两个仲胺基团，该基团中氮原子与两个碳原子和一个氢原子相连。
一种化学式为2-正丁基-2-(3，5-二叔丁基-4-羟基苄基)丙二酸二-(1，2，2，6，6-五甲基-4-哌啶基)酯(分子量为685g/mol)并含有叔胺的HALS可以TINUVIN144的商品名购自Ciba-Geigy Corp.，它具有下列化学结构：
一种化学结构为[(4-甲氧基苯基)亚甲基]丙二酸二(1，2，2，6，6-五甲基-4-哌啶基)酯、分子量约为529g/mol并含有叔胺的HALS以SANDUVORPR-31的商品名购自Clariant Corp.，它具有下列化学结构；
TINUVIN144和SANDUVORPR-31各自具有两个叔胺基团，其中氮原子与三个碳原子相连。
制造方法
可使用挤出或压延法制备本发明薄膜。尽管这两种方法均适用于制备基本平坦的薄膜，但是它们具有不同的加工方法。挤出包括在压力下加工粘性的熔体，将其以连续的料流压过一个成形模头，形成薄膜。压延使用熔融的粘性物质，将其加入连续的共旋转的平行辊对之间形成薄膜。挤出的优点在于如果要制备立方角薄膜时，可直接将离开挤出机的原料夹至具有立方角凹陷的模具中。另一方面，压延的优点在于使用这种方法能经济地制得挠性的PVC薄膜。
具有耐久的色彩和荧光性能的制品的制造方法包括：(a)将基本无溶剂的聚氯乙烯树脂、噻吨荧光染料和位阻胺光稳定剂混合成混合物，所述稳定剂至少包括一个仲胺或叔胺基团，分子量小于1000g/mol；和(b)由该混合物形成制品。
在挤出加工中，一般先将聚合物树脂/染料/HALS混合物搅拌混合在一起。聚合物树脂通常是小颗粒状的。在加热和螺杆旋转作用下，将混合物加入挤出机，混合物被混合并转变成粘性的熔体。通常使用具有多个加热区的挤出机。应选择挤出温度使组分熔融，但温度不应太高以防其降解。当使用上述荧光染料和HALS时，合适的挤出温度约为175-205℃。离开挤出模头的熔体通常与铬合金辊或抛光的铸塑辊接触，形成基本平坦的薄膜。
如有必要，可使离开挤出模头的熔体与其中具有立方角凹陷的模具或器具接触。当将熔体夹入模具中以后，形成的立方角薄膜较好具有最薄的基体层和许多立方角元件，这些立方角元件的底部平面与所述基体层相邻。例如可参见美国专利5,450,235(Smith等)和国际专利公开WO 95/11464(Benson等)描述的立方角片材的制造方法。挤出是制造本发明立方角薄膜的最好方法。
立方角元件可任选地蒸气涂覆金属层，如蒸气涂覆铝或银以提高逆向反射性能。但是，蒸气涂覆立方角元件会使发出荧光的立方角薄膜具有灰色的外观，这种外观对于某些用途是不合需求的。
在压延加工中，将聚氯乙烯树脂(通常是粉末状的)、荧光染料和位阻胺光稳定剂加入混合单元中深度混合。可加入其它添加剂(如增塑剂、UV吸收剂、热稳定剂、填料和润滑剂以获得所需的物理性能)和/或加工助剂。通常混合单元带有长条刀片并带有夹套以便加热或冷却。在混合过程中，PVC粉末吸收添加剂(包括染料和HALS)形成粉末混合物。经过强烈混合后，通常将粉末冷却并加至筛网除去金属，因为如果存在金属颗粒，它会损害压延辊的表面。通常将过筛的粉末混合物加入持续混合的熔融单元，使混合物形成熔融的粘性物质，该物质就是要加入压延辊的原料。可以加热通常配置有四根辊的压延辊。在制造本发明制品时，将压延辊加热至其表面温度约为170-180℃(340-355°F)。辊的配置也是重要的因素。将粘性的熔融原料加入压延机，形成的薄膜或片材的厚度由最后辊之间的间隙所控制。
尽管这种次序通常用于压延加工，但是根据所需的最终产物可进行多种变化。由于经济效益而使压延成为本发明较好的方法。
本领域已知在高温下胺会引发PVC脱氯化氢，但是本发明发现如本文实施例所述在高达205℃(255°F)的温度下通过压延或挤出制得的PVC制品是耐久的。
无论通过挤出还是通过压延制得的基本平坦的薄膜均可层压在现成的逆向反射基片(如立方角基或微球基片材)上。通常，将薄膜层压在逆向反射基片的正面或第一主表面上，制得新的本发明逆向反射制品。例如，如图2所示，将通常是基本平坦的薄膜的主体层26层压在立方角薄膜21的正面或第一主表面上，形成本发明逆向反射制品20。同样，在图3中，将基本平坦的薄膜的主体层36层压在微球基逆向反射基片31的正面或第一主表面35上，形成本发明逆向反射制品30。
在一个较好的实例中，本发明薄膜用作辐照固化立方角元件的载体。这些立方角元件所包括的活性树脂能通过光化辐照(例如电子束、紫外光或可见光)利用自由基聚合机理进行交联。美国专利5,450,235(Smith等)和国际申请公开WO 95/11464给出了这些活性树脂的例子。活性树脂较好在本发明薄膜上原位固化。图5给出了本发明立方角基逆向反射制品70，它是1995年4月27日公开的名为“超挠性逆向反射立方角复合片材及其制造方法”的国际专利公开WO/11464的原理制得的。图5的实例被设计成高挠性的逆向反射片材，适合于贴合褶皱的和/或柔软的表面。
如图5所示，逆向反射制品70包括包括许多基本独立的立方角元件72和具有两个主表面71和73的主体层76，立方角元件由第一主表面73突出并具有零至最小的基体。因此，本实例基本无基体层并且立方角元件的正表面75并列在表面73上。在一个较好的实例中，主体层76包括基本无溶剂的聚氯乙烯基质、荧光染料和位阻胺光稳定剂(图中均未表示)，它是制品70的最外层。
实施例
下列实施例用于说明本发明不同实例和细节。尽管这些实施例用于该目的，但是其所使用的具体组分和用量以及其它条件和细节不对本发明范围构成限制。除非另有说明，否则所有的百分数均为重量百分数。
加速天候老化
为了以加速的方式模拟在室外阳光下的暴露，根据ASTM G-26 B型，方法A所述的方法对某些试样进行辐照以加速天候老化。光源为6500W水冷氙弧灯，具有硼硅酸盐内部和外部过滤器。光源发出的光密度约为0.55W/m2。天候老化方法包括在约63℃的黑板温度(如试验方法所述)下放置102分钟，随后用去离子水喷雾的同时对试样照射18分钟。
紫外-可见(UV-Vis)吸收光谱法
在天候老化前后用UV-Vis光谱法测定主要染料的吸收带(456nm)来测定试样中荧光染料的保持量。UV-Vis分光光度计的一个说明性例子是UV2101-PC型Shimadzu分光光度计。
根据比尔定律，吸光度下降意味着染料浓度下降。“染料保持百分数”是由经天候老化试样的峰值吸光度与原来未经天候老化的峰值吸光度的比例算得的。
在实施例中使用下列简称：简称            含义PVC              聚氯乙烯主体基质T-770            位阻胺光稳定剂TINUVIN770癸二酸二-(2，2，6，6-四甲基-4-哌啶
             基)酯，分子量约480g/mol，购自Ciba-Geigy Corp.，Hawthorne，NYT-144            位阻胺光稳定剂TINUVIN144 2-正丁基-2-(3，5-二叔丁基-4-羟苄
             基)丙二酸二-(1，2，2，6，6-五甲基-4-哌啶基)酯，分子量约
             685g/mol，购自Ciba-Geigy Corp.PR-31            位阻胺光稳定剂[(4-甲氧基苯基)-亚甲基]丙二酸二-(1，2，2，6，6-五
             甲基-4-哌啶基)酯，分子量约529g/mol，购自Clariant Corp.，
             Charlotte，NCT-622     位阻胺光稳定剂TINUVIN622琥珀酸二甲酯与4-羟基-2，2，6，6-四
      甲基-1-哌啶乙醇的共聚物，分子量(Mn)约大于2500g/mol，购自
      Ciba-Geigy Corp.C-944     位阻胺光稳定剂CHIMASORB944FL聚[6-[(1，1，3，3-四甲基丁基)氨
      基]-s-三嗪-2，4-二基][2，2，6，6-四甲基-4-哌啶基亚氨基]六亚甲基
      [(2，2，6，6-四甲基-4-哌啶基)亚氨基]，分子量(Mn)约大于
      2500g/mol，购自Ciba-Geigy Corp.T-440     位阻胺光稳定剂TINUVIN440，低分子量乙酰化的位阻胺，分子量
      约435g/mol，购自Ciba-Geigy Corp.C-3346    位阻胺光稳定剂CYASORB3346，低聚的位阻胺，分子量(Mn)约大于
      1600g/mol，购自American Cyanamid Corp.SO63      噻吨黄色荧光染料HOSTASOLRED GG，14H-蒽[2，1，9]噻吨-14-酮，
      购自Hoechst Celanese，Charlotte，NCSY98      噻吨橙色荧光染料HOSTASOLYELLOW 3G，N-十八烷基苯并[k，l]噻
      吨-3，4-二羧酰亚胺，购自Hoechst Celanese，Charlotte，NCD-304     噻吨黄色荧光染料DAy-GlO304，购自Day-Glo Color Corp.，
      Cleveland，OHD-315     噻吨橙色荧光染料DAY-GlO314，购自Day-Glo Color Corp.D-838     香豆素荧光POTOMACYELLOWTM D838染料，购自Day-Glo Color Corp.RED FB    蒽吡啶酮荧光红染料FLUORESCENT RED FBTM，购自Keystone Aniline
      Corp.，Chicago，ILRED 5B    硫靛荧光红染料HOSTASOL RED 5B C.I.(色彩指数)Vat Red 41，购
      自Hoechst Celanese
实施例1
如下制得厚度约0.089-0.11mm(0.0035-0.0045英寸)的聚氯乙烯薄膜：将PVC树脂(制剂S00354，含UV吸收剂购自Alpha Chemical and Plastics Corp.)与约0.2％SO63荧光染料和约0.5％T-770HALS混合在一起。将树脂/染料/HALS翻转混合。随后使用带有5个设定在约175℃、205℃、205℃、175℃和175℃的加热区并且薄膜模头设定在约180℃的单螺杆挤出机将该混合物挤出成基本平坦的薄膜。该挤出机是一种3/4英寸单螺杆Brabender挤出机，带有抛光的铬合金辊。
对试样进行100小时天候老化，结果列于表1和2。
实施例2和3以及比较例A-E均用实施例1的方法制得，但是如表1所述使用不同的HALS或不使用HALS。对试样进行100小时天候老化，结果列于表1。
                          表1
          含SO63荧光染料并带有各种HALS的PVC挤出薄膜
实施例     HALS  100小时天候老化后的染料保持百分数
1     T-770     55
2     T-144     66
3     PR-31     61
比较例A     T-622     9
比较例B     C-944     14
比较例C     T-440     11
比较例D     C-3346     15
比较例E     无     7
由表1结果可见，不含HALS的试样(比较例E)的性能最差，薄膜中几乎所有染料均被破坏。分子量超过1000g/mol的HALS(比较例A、B和D)在稳定荧光染料方面的表现很差。分子量为435g/mol的比较例C表现不佳，因为不含有至少一个仲胺或叔胺基团。
根据实施例1制得实施例4-6的试样，但是如表2所示使用不同的荧光染料。除非另有说明，否则对试样进行100小时加速的天候老化，结果列于表2。
根据实施例1制得比较例E-N的试样，但是如表2所示使用不同的荧光染料并使用或不使用HALS。除非另有说明，否则对试样进行100小时加速的天候老化，结果列于表2。
                    表2
    含各种荧光染料并含有或不含有HALS的PVC挤出薄膜
实施例   荧光染料   使用的HALS 染料保持百分数
1     SO63     T-770     55
4a     SY98     T-770     56
5     D-304     T-770     53
6a     D-315     T-770     39
比较例E     SO63     无     7
比较例Fa     SY98     无     37
比较例G     D-304     无     35
比较例Ha     D-315     无     17
比较例I     D-838     T-770     9
比较例J     RED FB     T-770     13
比较例b     RED 5B     T-770     5
比较例L     D-838     无     18
比较例M     RED FB     无     25
比较例Nb     RED 5B     无     3
a试样进行了200小时加速的天候老化
b试样进行了50小时加速的天候老化
如表2所示，含噻吨荧光染料和T-770 HALS的本发明试样(试样1、4、5和6)的性能要优于用相同T-770 HALS稳定的不含噻吨荧光染料的试样(比较例I、J和K)。含有噻吨荧光染料但不含HALS的试样(比较例E、F、G和H)所保持的染料量少于含有HALS的试样(实施例1、4、5和6)所保持的染料量。最后，将比较例I、J和K与比较例L、M和N相比较，表明即使使用HALS，不含噻吨荧光染料的试样不能保持其色彩。因此，在这种情况下，使用HALS(即使是较好的HALS)也是无效的。
实施例7
使用试验规模的压延方法如下制得聚氯乙烯薄膜：将PVC粉末与约0.2％SY98荧光染料和约0.5％T-770 HALS混合在一起。加入其它添加剂，如UV吸收剂、热稳定剂、增塑剂、润滑剂和填料作为加工助剂或帮助形成挠性的PVC薄膜。将混合物加入过滤器，除去金属(如果有的话)。随后将其连续混合成熔融的物质、研磨并加入全部加热至约177℃(350℃)的辊中，形成厚度约0.13-0.15mm(0.005-0.006英寸)厚的本发明薄膜。对试样进行400小时加速的天候老化试验，结果列于下表3。
比较例Q
根据实施例7制得压延的PVC薄膜，但是不向PVC粉末中加入HALS。对试样进行400小时加速的天候老化试验，结果列于下表3。
                         表3
             含SY98荧光染料的压延的PVC薄膜
实施例   HALS   荧光染料 染料保持百分数(400小时老化后)
7   T-770   SY98     76
比较例Q   无   SY98     1.3
由表3可见，含有荧光染料和HALS的本发明压延的PVC薄膜的性能明显优于不含HALS的试样。
对实施例4试样及其对照的比较例E试样进行400小时加速的天候老化，结果列于表4。
                           表4
                含SY98荧光染料的PVC挤出薄膜
实施例   HALS   荧光染料 染料保持百分数(400小时老化后)
4   T-770   SY98     29
比较例E   无   SY98     9
由表4可见，含有荧光染料和HALS的本发明PVC挤出薄膜的性能优于不含HALS的试样的性能。
本文所引用的所有参考文献在此均引为参考。

Claims (14)

1.一种表现出耐久的色彩和荧光性能的制品，它包括：
(a)含有基本无溶剂的聚氯乙烯树脂的聚合物基质；
(b)噻吨荧光染料；和
(c)位阻胺光稳定剂，所述光稳定剂包括至少一个仲胺或叔胺基团，并且分子量小于1000g/mol。
2.如权利要求1所述的制品，其特征在于所述聚合物基质还包括增塑的聚氯乙烯树脂。
3.如权利要求1或2所述的制品，其特征在于所述位阻胺光稳定剂选自癸二酸二-(2，2，6，6-四甲基-4-哌啶基)酯、2-正丁基-2-(3，5-二叔丁基-4-羟基苄基)丙二酸二-(1，2，2，6，6-五甲基-4-哌啶基)酯和[(4-甲氧基苯基)亚甲基]二(1，2，2，6，6-五甲基-4-哌啶基)酯中的至少一种。
4.如权利要求1或2所述的制品，其特征在于所述制品是逆向反射立方角薄膜。
5.如权利要求1或2所述的制品，其特征在于所述制品是下面放置有逆向反射基片的薄膜。
6.如权利要求5所述的片材，其特征在于所述逆向反射基片是立方角基片材或微球基片材。
7.如权利要求6所述的制品，它还包括保护外层。
8.具有耐久的色彩和荧光性能的制品的制造方法，它包括：
(a)将基本无溶剂的聚氯乙烯树脂、噻吨荧光染料和位阻胺光稳定剂混合成混合物，所述稳定剂至少包括一个仲胺或叔胺基团，分子量小于1000g/mol；和
(b)由该混合物形成制品。
9.如权利要求1所述的制品，其特征在于按制品总重量计，所述制品最多含有2重量％噻吨荧光染料。
10.如权利要求1所述的制品，其特征在于按制品总重量计，所述制品最多含有2重量％位阻胺光稳定剂。
11.如权利要求8所述的方法，其特征在于按制品总重量计，所述制品最多含有2重量％噻吨荧光染料。
12.如权利要求8所述的方法，其特征在于按制品总重量计，所述制品最多含有2重量％位阻胺光稳定剂。
13.一种表现出耐久的色彩和荧光性能的制品，所述制品包括：
(a)一层，包括(i)聚氯乙烯主体基质、(ii)包含至少一种仲胺或叔胺基团、分子量小于1000g/mol的位阻胺光稳定剂、和(iii)噻吨荧光染料的层；和
(b)保护层，它包含紫外光吸收剂，所述保护层置于(a)中所述的一层上。
14.如权利要求13所述的制品，其特征在于所述聚氯乙烯主体基质基本是无溶剂的。
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