CN1125172A - 荧光制品 - Google Patents

荧光制品 Download PDF

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CN1125172A
CN1125172A CN95117297A CN95117297A CN1125172A CN 1125172 A CN1125172 A CN 1125172A CN 95117297 A CN95117297 A CN 95117297A CN 95117297 A CN95117297 A CN 95117297A CN 1125172 A CN1125172 A CN 1125172A
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fluorescent
fluorescence coating
layer
reflecting layer
transparent resin
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米谷隆行
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YKK Corp
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Abstract

本发明公开了一种荧光制品(10，10a，10b)，它具有依次覆盖在反射层(3，3a)上的一层荧光层(2，2a)，和透明树脂层(1)。它采用SrAl2O4作为荧光颜料，将其引入荧光层(2，2a)中，采用不含紫外光吸收剂的透明树脂作为透明树脂层(1)。另外，为了便于使用，在反射层(3)中与该荧光层(2)接触的表面相对的表面上依次覆盖一层粘接层(4)和一层释放层(5)。

Description

荧光制品
本发明涉及一种荧光制品，特别是涉及一种能吸收及积聚光，而且当放于黑暗地方时能发射光的荧光制品。
至今，人们已经认识到ZnS∶Cu，(Ca，Sr)S∶Bi等荧光颜料(长余辉荧光体)，而且ZnS∶Cu荧光体已广泛用作发光涂料。
这些荧光颜料具有通过吸收光，如日光或荧光(积聚光)而激发自身的性能，并且当放于黑暗地方时发射光。由于这些荧光颜料能多次重复吸收—积聚—发射光的循环，它们在许多用途中得到了运用，例如用作标志及信号以防止灾祸及保证安全，汽车及建筑物中的各种引导信号，诸如领带别针和耳环那样的饰物，表中的刻度，诸如鱼漂和诱饵那样的钓鱼制品。
用于一般目的的领域时，这些荧光颜料通常被制成荧光板，其原因在于操作起来比较方便。
至今，这类荧光板已被设计成多种形式。通常采用ZnS∶Cu作为这些常规荧光板的荧光颜料。日本专利申请公开(早期公开)52—49245公开了一种可以印刷的封条或板，它是通过在一透明薄膜基体上形成一种在其中引入荧光粉(ZnS∶Cu)的发光层，而后在其上覆盖一层粘接层和一层释放层而形成的，在该发光层的上表面上可以粘有也可以不粘任何布、纸或薄膜层。
但是通常用于上述常规荧光板中的荧光颜料ZnS∶Cu有一个缺点，它会由于紫外光线而分解，由此而使积聚光和发射光的特性逐渐变次。
为了消除这些缺点，日本专利公开2—3704公开了一种方法，该方法包括将荧光颜料的细小颗粒包封在一种保护层中，该保护层由透明且能吸收紫外光的合成树脂制成，而日本专利申请公开60—135246公开了一种方法，它包括用一种含有紫外光吸收剂的透明合成树脂层涂覆含有荧光颜料的发光层。
此外，由该荧光颜料ZnS∶Cu发射的光缺少使视觉在整个夜晚均能感受的亮度。因此，当用于发光手表的刻度中时，需要将这种颜料与一种放射性物质结合起来使用，这样就可以通过该放射性物质的辐射而将其激发，并且使它能长时间发光。
但是，放射性物质的缺点在于它在操作安全性方面受到严格的限制并且在废料处理时会使成本加大。
人们最近开发出了一种SrAl2O4荧光体，它是一种没有用通常广泛采用的荧光颜料ZnS∶Cu时所遇到的这类缺陷的荧光颜料(第248届荧光学会演讲，1993年11月26日召开，于PhysicalProperties Research Institute，Tokyo University)。
荧光颜料SrAl2O4具有作为荧光颜料的杰出的基础性能，举例来说，它具有出众的特点，如具有接近人类视觉光谱的发射光谱(峰值波长为520nm)，并且具有较宽的激发光谱，对于在短波长区域内的紫外光具有较高的激发效率。此外，它还显示出极高的余辉亮度，大约是常用的ZnS∶Cu的5—10倍高，而余辉衰减逐渐进行。
但是，该荧光颜料SrAl2O4的缺点在于与常规颜料ZnS∶Cu相比，它需要较长的时间来激发以达到饱和的余辉亮度。而且由于SrAl2O4易受水和湿气的侵害，采用这种颜料的夹层要为耐水性付出代价。
本发明的目的在于提供一种有效利用上述由作为荧光颜料的SrAl2O4所显示的杰出特点，最大限度消除其缺陷，达到快速激发并且生产高亮度持久余辉的荧光制品。
本发明的另一目的在于提供一种荧光制品，该制品除了具有上述荧光性能以外还具有杰出的耐光性，耐水性和耐热性，同时具有易于使用的板状形状。
为了达到上述目的，根据本发明，提供了一种荧光制品，该制品具有一层荧光层和一层透明树脂层，它们依次覆盖在一层反射层上，该荧光层含有作为荧光颜料而引入其中的SrAl2O4，而该透明树脂层是由不含紫外光吸收剂的透明树脂制成的。
根据本发明的一个优选方案，它提供了一种荧光板，即一种为了便于以自粘板形式使用的荧光制品，该板具有一层粘接层和一层释放层，它们依次覆盖在上述反射层与该荧光层接触的表面相对的表面上。
从下面结合附图的描述中，本发明的其它目的、特点及优点将变得显而易见。
图1是表示本发明的荧光制品的基础层状结构的横截面图；
图2是表示图1中所示的荧光制品的一个改进型例子的横截面图；
图3是表示本发明另一个荧光制品例子的层状结构的横截面图。
如上所述，用于本发明的荧光颜料SrAl2O4具有优异的性能，如产生极高的亮度，具有较长的余辉时间，也就是说，当它在吸收和积聚光(激发)之后在黑暗地方放光时它能持续长时间放光。但它有一个缺点，与常规广泛使用的荧光颜料ZnS∶Cu相比需要较长的时间激发并且耐水性较次。
本发明的荧光制品通过在含有荧光颜料SrAl2O4的荧光层的正面表面上覆盖不含紫外光吸收剂的透明树脂层并且在其反面表面上覆盖反射层来保护耐水性较差的荧光层使其免遭湿气和水的侵害，同时通过使表面保护透明树脂层不含有紫外光吸收剂而使入射光完全通过该透明树脂层并吸收在该荧光层中，而且使曾逃逸吸收的光线被位于反面表面的反射层反射并被该荧光层再次吸收，结果使得施加的光线有效地被该荧光层吸收并缩短了激发时间。
由于采取了上述层状结构，本发明的荧光制品获得了快速激发并显示出以高亮度长时间发光的杰出的功能和效果。
下面将参照在附图中所示的实施方案和一个操作例子对本发明作更进一步的描述。
图1表示本发明的荧光制品10的基础层状结构。在图1中，数字1代表透明树脂层，2代表荧光层，3代表反射层。
与常规保护层不同的是，该透明树脂层1应采用不含紫外光吸收剂的透明树脂。包含在该荧光层2中的荧光颜料SrAl2O4与常规广泛使用的颜料ZnS∶Cu不一样，它很少由于紫外光而变次，并且受紫外光(200—450nm)的激发。通过提高透明树脂层1对紫外光的透过率，荧光层2的荧光特性得以改善。当透明树脂层1的透明度不好时，其透光性就较次，且不可避免地会阻碍荧光层的光发射。
另外，荧光颜料SrAl2O4变次的主要因素在于水和湿气的作用。因此，关于作为保护膜的透明树脂层1的功能，必须选择在耐水性方面特别好的树脂作为透明树脂层1。当该荧光制品是用于汽车中时，由于汽车内的温度在夏季可能达到80℃，因此，该荧光制品有时需要采用耐热的树脂。
作为透明树脂层1的材料，可以考虑上述各种因素而选择一种特别适用的树脂，作为该材料的具体例子，可以提出聚碳酸酯，丙烯酸树脂，聚氯乙烯及聚酯。
荧光层2是含有荧光颜料SrAl2O4的一层，它具有可以通过吸收光，如日光或荧光(积聚光)而激发并且当置于黑暗地方时会发光的特性。它构成了荧光制品10的主要一层。
荧光层2的形成过程按下列方式进行：将主要由SrAl2O4组成的荧光颜料分散在通过将树脂溶解在溶剂中而制成的清漆中，从而制成一种油墨，并且利用一种合适的手段，如丝网印刷术将该油墨印刷或施加到基体(透明树脂层1或反射层3)的表面上。荧光层中的SrAl2O4的含量可以设定在占最终形成的薄膜的重量的70—85％范围内。如果该含量低于70％重量，则发出的光亮度不足。反过来说，如果该含量超过85％重量，则在油墨制备过程中就很难将荧光颜料引入清漆中。一般说来，考虑到由于薄膜形成之后干燥(如由于溶剂的挥发)而引起的重量损失，油墨中SrAl2O4的含量在40—60％重量范围内是合适的。
用来制备清漆的树脂的例子可以包括上面例举的用来制备透明树脂层的那些树脂。考虑到耐热性，用作清漆的优选的树脂是丙烯酸树脂，氯乙烯—丙烯酸树脂(共聚物)等。利用丝网印刷可以获得较好的印刷。
反射层3是用来改善发光的荧光层2的亮度的层。它位于荧光层2的反面表面上并且可以实现将该荧光层吸收过的已逃逸的光反射并且使该反射光被荧光层再次吸收的功能以及保护该荧光层2使之免受湿气和水的侵害的功能。
反射层3的形成过程是通过制备含有白色颜料，如氧化钛(钛白)的板、油墨或涂覆材料并且通过粘接、印刷或施加将其覆盖在荧光层的反面表面上而实现的。在优选的实施方案中，最好使加入荧光层2和反射层3中的颜料不同而加入其中的其它成分则相同，以确保在该荧光层和反射层之间实现紧密、快速的粘接。
上述透明树脂层1，荧光层2和反射层3的总厚度在70—600μm范围内是合适的，优选的是在160—600μm范围内。如果总厚度低于70μm，则该荧光层太薄以致于不容易获得如本发明所期望的快速激发、高亮度及长余辉的荧光制品，而且该透明树脂层同样也会过分薄以致于不能达到对荧光层提供完全满意的保护的目的。因此，任何偏离上述范围的总厚度均是无益的。
总厚度不低于160μm的板或夹层物具有合适的柔软性，从而使其在粘接到物体表面上时具有不容易破裂的优点，或者在粘接结合之后不容易起皱。该总厚度使该荧光层获得足够的厚度，从而使该荧光制品具有足够的所期望的荧光性能。由于它还使该透明树脂层获得足够的厚度，该透明树脂层对荧光层提供彻底的保护并且具有较高的耐水性及耐热性。因此，该板可有利地用作为汽车中的粘接板。
但是，如果总厚度超过600μm，则该板将过分厚且刚硬，不具有柔软性，结果将产生不容易粘接到弯曲表面上的缺点并且在粘接之后容易与表面分离。另外，该板在通过切割形成合适的形状时容易产生裂纹或断开。
当透明树脂层、荧光层和反射层的总厚度在160—600μm范围内时，由这些层组成的板既不会太薄也不会太厚，而具有合适的厚度，并且具有容易切割的优点。当总厚度在70—160μm范围内时则可以将该荧光夹层物作为封条，而总厚度在160—600μm范围内时则可以将其作为板。这种分类是出于方便的目的，它并非是对由本发明所提出的荧光制品的基本要求。用于本发明的术语“板”应作广义理解，包括封条在内。
现在将对该夹层物的备层的厚度进行描述。首先，透明树脂层1的厚度在10—400μm范围内是合适的。优选的是100—400μm。如果该厚度低于10μm，该透明树脂层由于过低的厚度而不能令人满意地起到保护层的作用而且很容易受到外部的影响(水、热等的作用)。当向外部影响暴露时，透明树脂层1在使荧光层保持其荧光特性方面将会遇到困难。因此，本发明的目的将不容易实现。
如果透明树脂层的厚度不低于100μm，该板将获得足以避免在通过粘接用于物体表面时受到损坏如破裂及起皱的柔软性，保护荧光层免受损坏，(如由于变曲)，以及显示出特别好的保护功能以抵抗外部影响。但是如果该透明树脂层的厚度超过400μm，则该板将变得如此刚硬以致于使柔软性下降，并且在粘接到弯曲表面上时会产生困难，粘接后容易与表面剥离，而且在切割时容易发生裂纹或断裂。过大的厚度还会使荧光层发出的光的亮度下降。
荧光层2的厚度在50—200μm范围内是合适的，如果该厚度低于50μm，则本发明的荧光制品将不能充分显示出所期望的效果，即快速激发，高亮度和长余辉。
亮度和余辉时间在该厚度增加时成比例增加，但是如果该厚度超过200μm，由于在诸如快速激发、亮度或余辉性能等特性方面没有产生相应的改进，则过量的厚度是不经济的。
最后，反射层3的厚度不在10μm以下是合适的。如果它低于10μm，则反射层3就会产生使部分光透过去的缺点，不能起到作为该反射层主要目的的反射光的作用，并且使快速激发变得困难。
顺便说一句，该反射层的厚度只需在该反射层像所期望的那样显示出反射光的作用的范围内即可。对该厚度没有设定上限。考虑到诸如在前面所提到的难以粘接到弯曲表面上以及在通过切割形成板的过程中会发生裂纹的问题，可以对该厚度进行适当设定以适合特定的用途。
图2表示图1所示出的荧光制品的基础层状结构的一个改进型例子。
在图2所示的荧光制品10a中，荧光层2a完全被反射层3a覆盖并且紧密封闭于反射层3a和透明树脂层1之间。利用该结构，荧光层2a与湿气及水完全隔开，荧光制品10a的耐水性得到进一步改进。
图3表示出于使用方便目的而以自粘板形式形成的荧光制品10b，即所述的通过在反射层3的反面表面上依次覆盖粘接层4和释放层5而制成的荧光板或标鉴。在该结构的其它部分，该荧光制品10b与图1所示的荧光制品相同。
当试图将荧光制品10b用于温度相当高的条件下，如在汽车内时，应选择一种在耐热性方面特别好的压敏粘接剂(如以编号“500”出售的Nitto Electric Industrial Co.，Ltd的产品)并将其用作粘接层4。释放层可以是任何一种熟知的、可以从市场买到的释放纸。
由于本发明的荧光制品使用SrAl2O4作为荧光颜料并采用如上所述在含有SrAl2O4的荧光层的正面表面上有一层不含有紫外光吸收剂的透明树脂层和在其反面表面上有一层反射层的层状结构，它保护了耐水性不好的荧光层使之免受湿气和水的侵害，并且使之充分显示出荧光效果，同时使该荧光层有效地吸收入射光，进行快速激发，并且长时间以高亮度产生余辉。因此，它可以有效且恒定地重复吸收—积聚(激发)—发出光的循环，并且可以广泛用于需要在黑暗地方发出光的运用中。当所述的荧光板是通过依次在反射层的反面表面上覆盖粘接层和释放层而形成时，由于它仅通过分离该释放层就可以将它很容易地粘接到给定的支撑体(成品或其一部分)的表面上，因此它使用很方便。
另外，由于采用SrAl2O4作荧光颜料，所制成的荧光制品很少由于紫外光而退化，因而可以用于室外，其稳定性得到了改善。由于这种荧光制品不含放射性物质，它不会对人体产生负作用，不会对荧光表面的范围产生限制。
现在，我们将在下文中对体现本发明的制造例子进行描述。实施例
在厚度为300μm的聚碳酸酯的透明树脂板上，利用丝网印刷术以不同的最终厚度(50—200μm)施加通过将清漆和50％重量的SrAl2O4捏混而产生的油墨，该清漆含有溶解在丁基纤维素溶剂中的氯乙烯—丙烯酸树脂，然后将其干燥以形成一层荧光层。
而后，在上面所形成的荧光层上，施加通过将含有氯乙烯—丙烯酸树脂(在丁基纤维素溶剂中)的相同的清漆与21％重量氧化钛混合而产生的油墨并干燥，从而形成厚度为14μm的反射层。随后，在所形成的反射层上，施加一种压敏粘接剂(由Toyo InkMfg.Co制造，以产品编号“DF2700 M12—X”出售)，并将一种释放纸粘到它上面，从而获得层状结构如图3所示的荧光板。
如上面所述获得的荧光板确实显示出非常高亮度的发射光，并且产生很长时间的余辉。与不含反射层的荧光板相比，它们产生十分快速的激发。
尽管在本文中公开了一些特定的方案及制造例子，但本发明还可以以其它一些特定的形式体现出来，它们并不脱离本发明的精神或基本特征。所描述的方案和例子应作全面考虑，它们是用来说明的而不是限制性的，本发明的范围应由所附的权利要求书来限定，而不是由上面的描述来限定，因此，来自该权利要求书的等价涵义及范围内的所有改变均应包括在本发明中。

Claims (20)

1.一种荧光制品，它包括：一层反射层，覆盖在所述的反射层上的荧光层，以及覆盖在所述荧光层上的透明树脂层；所述的荧光层含有SrAl2O4作为荧光颜料，所述的透明树脂层是由不含紫外光吸收剂的透明树脂形成的。
2.根据权利要求1的荧光制品，其中所述的反射层、荧光层和透明树脂层的总厚度在70—600μm范围内。
3.根据权利要求1的荧光制品，其中所述的反射层的厚度不低于10μm，所述荧光层的厚度在50—200μm范围内，所述透明树脂层的厚度在10—400μm范围内。
4.根据权利要求1的荧光制品，其中所述反射层的厚度不低于10μm，所述荧光层的厚度在50—200μm范围内，所述的透明树脂层的厚度在100—400μm范围内。
5.根据权利要求1—4中任意一个的荧光制品，其中在所述荧光层中SrAl2O4的含量在70—85％重量范围内。
6.根据权利要求1—4中任意一个的荧光制品，其中所述的荧光层是由含有SrAl2O4的合成树脂制成的。
7.根据权利要求6的荧光制品，其中所述的反射层是由含有白色颜料的合成树脂制成的，所述的合成树脂基本上与用于荧光层中的相同。
8.根据权利要求1—4中任意一个的荧光制品，其中所述的反射层是含有白色颜料的合成树脂层。
9.根据权利要求1—4中任意一个的荧光制品，其中所述的荧光层完全被所述的反射层覆盖，并且紧密封闭在所述的反射层和所述的透明树脂层之间。
10.根据权利要求1—4中任意一个的荧光制品，它还包括一层粘接层和一层释放层，它们依次覆盖在所述的反射层中与荧光层接触的表面相对的表面上。
11.根据权利要求1—4中任意一个的荧光制品，其中所述的透明树脂层是由选自聚碳酸酯、丙烯酸树脂、聚氯乙烯和聚酯的一种形成的。
12.根据权利要求6的荧光制品，其中所述的合成树脂是选自丙烯酸树脂、聚氯乙烯、氯乙烯—丙烯酸树脂及其混合物中的一种。
13.根据权利要求8的荧光制品，其中所述的合成树脂是选自丙烯酸树脂、聚氯乙烯、氯乙烯—丙烯酸树脂及其混合物中的一种。
14.根据权利要求8的荧光制品，其中所述的白色颜料是钛白。
15.一种荧光板，它包括：
一种释放板，
覆盖在所述的释放板上的粘接层，
与所述的粘接层相粘接的反射层，该反射层是由含有白色颜料的合成树脂制成的，
覆盖在所述的反射层上的荧光层，该荧光层是由含有SrAl2O4的合成树脂制成的，以及
覆盖在所述的荧光层上的透明树脂层。
16.根据权利要求15的荧光板，其中所述的反射层的厚度不低于10μm，所述的荧光层的厚度在50—200μm之间，而所述的透明树脂层的厚度在10—400μm范围内。
17.根据权利要求15或16的荧光板，其中在所述的荧光层中的SrAl2O4的含量为70—85％重量之间。
18.根据权利要求15或16的荧光板，其中所述的透明树脂层是由选自聚碳酸酯、丙烯酸树脂、聚氯乙烯以及聚酯的一种制成的。
19.根据权利要求15或16的荧光板，其中所述的合成树脂是选自丙烯酸树脂、聚氯乙烯、氯乙烯—丙烯酸树脂及其混合物中的一种。
20.根据权利要求15或16的荧光板，其中所述的白色颜料是钛白。
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