CN1346857A - 可发光的涂层组合物 - Google Patents
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Abstract
本发明涉及一种可发光的涂层组合物。特别是本发明涉及一种由粘合剂和可发光纤维组成的涂层组合物,以及这类涂层组合物的应用,特别是用于物体的标记。
Description
发明领域
本发明涉及一种可发光的涂层组合物。特别是本发明涉及一种由粘合剂和可发光纤维组成的涂层组合物,以及这类涂层组合物的应用,特别是用于物体的标记。
背景技术
术语“发光”意指气体、液体或固体在合适的能量输入后所产生的光发射,其发射的光可在可见光范围、UV-范围、红外范围和/或光谱范围。发光的表现形式有两种,即荧光和磷光。其详情可参阅Rmpp化学大全,第10版中词目“发光”“荧光”和“磷光”以及其中的参考文献。
其中均匀加入有发光染料或颜料的涂层是商业上惯用的。带有发荧光颜料的粘合剂用于标记的光学探测。但是这类涂层不在安全标记方面使用,因为其非特异性。而且在纸涂层和织物涂层的情况下,由于其中主要包含的荧光增亮剂(OBA)使图像模糊。此外,在这种情况下所使用的荧光染料的量也较大。
由德国公开文件19510468和19549374中已知一种在日光下能持久发荧光的透明薄膜,其通过在发荧光的薄膜中于整个薄膜上以均匀分布较大量的颜料可产生荧光效果。在德国实用新型文件9117086和欧洲专利0594765中描述了一种类似的由透明的薄膜材料构成的持久发荧光粘贴膜,该膜材料中加有较大量的均匀分布的发荧光的染料。
但是,前述的薄膜不适于安全标记,而是用于产生光学效果,优选用于广告目的,因为这种薄膜产生持久的用肉眼就可识别的发光。此外,需要大量的颜料以产生在整个薄膜上均匀分布的发光效果。
发明内容
本发明的目的是提一种可标记物体的系统。可充分利用一定量的物质来发光。特别是该系统能起安全功能或识别功能。
本发明的目的是提一种涂层组合物,它含有至少一种有机粘合剂和可发光纤维,并且该发光纤维是由含至少一种在其中均匀分布有可发光染料或颜料的形成纤维的材料组成。
本发明的涂层组合物可用于识别各类物体,其中,本发明的涂层组合物涂敷于该物体的表面。
有机粘合剂可包括各类粘合剂。但是该有机粘合剂必须选择这一类,即发光颜料或发光染料不受侵蚀,并不被纤维所溶解。另外,还要适于涂层组合物中所含的物质,特别是适于在涂层组合物中可能含有的溶剂。合适的有机粘合剂的例子是各类漆,特别是清漆。该有机粘合剂还涉及纸涂刷物质或薄膜涂刷物质。此外,有机粘合剂还涉及各类胶。所考虑的胶的例子是粘合胶,如基于溶剂的粘合胶、基于分散剂的粘合胶或熔化粘合胶。在本发明的涂层组合物中使用的有机粘合剂特别是透明的或基本透明的有机粘合剂。但是,也可采用半透明至不透明的粘合剂,特别是当涂敷薄的涂层组合物和纤维由涂层上“露出”时。
本发明所用的发光纤维是已知的(参看德国公开件19539315和19802588以及USA-专利5674437),并可从市售得到。这类纤维的制造商是Honeywell公司、Speciality Chemieals公司、早期的Riedel-de-Haen公司,该公司以Markennamen Lumilux牌号销售各种发光纤维,并且在纤维中分布的可发光的颜料根据不同分子发射不同波长的光(例如Lumilux蓝MF-P 831/22/3-LT型、Lumilux红MF-P-870/LT类、Lumilux黄MF-P 833/22/3-LT)。
迄今,上述类型的纤维仅在制造形成纤维的材料如纸或织物的过程中以如下形式引入;在造纸过程中该纤维加到纸浆中,在织物生产中,该纤维加到用于纺织成纤维的原料中。这就产生较大的配料。发光纤维在该类产品中仅作难以伪造的安全标记之用,例如在纸币中。这些纤维的基质是丝、纤维素、乙酸纤维素、聚酰胺、聚酯;它们以有机或无机发光染料引入(参看德国公开件19539315和19802588以及USA-专利5674437)。但在现有技术中,这类纤维不用于制备功能涂层中。
本发明使用的发光纤维是现有技术已知的。例如可参阅德国公开件19530315和19802588以及USA-专利5674437。
可发光纤维的制备通常是按如下进行的,将可发光染料加到形成纤维的材料中或加到其溶液中,并由这些物料纺织成纤维。再一种可能是使纤维或形成纤维的材料与可发光染料的溶液或分散体接触(例如通过喷洒、浸入、浸渍等),并干燥所得的纤维。
在本发明的涂层组合物中可发光纤维的用量和纤维的性质,特别是纤维的长度和厚度以及纤维材料和染料的种类是如此确定的,即不干扰涂敷工艺。另外,必须能达到标记功能。
通常,本发明的涂层组合物含发光纤维的量按100重量份涂层组合物计为0.0001-10重量份,特别是0.001-7.5重量份,优选0.001-5重量份。本发明使用的发光纤维的长度可在宽的范围内变化,通常为0.05-10mm,特别是0.1-5mm。所有发光纤维的厚度可在宽范围内变化,通常为1-1000μm,特别是10-100μm。
形成纤维的材料可包括所有已知的形成纤维的材料,只要它与本发明的涂层组合物相容。适用的形成纤维的材料的实例为丝、纤维素、乙酸纤维素、聚酰胺、聚酯、聚丙烯酸酯、聚烯烃、聚氨酯、棉花以及上述材料的混合物。所用的纤维包含可发光染料或可发光颜料,其量按纤维重量计通常是大于5重量%至到50重量%,特别是7-40重量%,优选10-20重量%。
可发光染料或可发光颜料可是无机的或有机的。特别是可发光染料或可发光颜料至少是部分在用紫外线辐照时应产生发光效果。该发光效果可基于荧光或磷光。
根据本发明的实施方案,可发光染料或可发光颜料可选择这一类,即在紫外线辐照下可发射可见光范围和/或红外线范围的光。特别是该可发光染料或可发光颜料要如此选择,即在紫外线辐照下至少发射可见光范围的光。该可发光颜料的实例可为无机发光物质。对此其实例为碱土金属、副族元素或稀土的磷酸盐、钨酸盐、氧化物、硅酸盐和铝酸盐以及碱金属、碱土金属的卤化物,它们以一种或多种活化剂如Mn2+、Mn4+、Sb3+、Sn2+、Pb2+、Cu+、Ag+、稀土掺杂。另一些实例为硫化锌、硫化锌镉、碱土金属铝酸盐、碱土金属硫化物和碱土金属硅酸盐以及其混合物,总是以至少一种过渡金属元素和/或镧素元素掺杂。还有一些实例可参阅德国公开件19539315和19802588以及USA-专利5674437。
但是,可发光染料或可发光颜料也可以是有机发光物质。其实例为可发光的,特别是可发荧光的碳环或杂环的芳香族系列如可发光的,特别是可发荧光的苯衍生物、吖啶衍生物、呫吨衍生物、噻吨衍生物、芘衍生物、茋衍生物、香豆素衍生物和吡唑啉衍生物以及上述化合物的混合物。
可发光染料或可发光颜料通常是一种荧光物质(荧光染料)。但是,根据本发明,可发光染料或可发光颜料还可是荧光团,它首先通过化学反应,例如酶催化或不催化,转变成可发荧光的化学化合物。在本发明范围内使用的术语“可发光染料”或“可发光颜料”意指既是可发光染料(颜料)本身,也可是适合的前体,该前体通过化学反应转变成可发光染料(颜料)。
按照本发明的一种特殊实施方案,可在涂层组合物中相互组合不同的纤维,在纤维中涂敷有不同的可发光的染料或颜料,在用适合能量激发后发射出不同波长或光谱颜色的光。
除有机粘合剂和可发光的纤维外,本发明的涂层组合物还可含有通常的各类助剂、加工助剂或添加剂。但是,该助剂、加工助剂或添加剂必须如此选择,即发光颜料或发光染料不受侵蚀或不被纤维所溶解。合适的助剂、加工助剂或添加剂的实例是填料、抗氧化剂、抗老化剂、抗UV-辐照助剂、流动性调制助剂、溶剂和分散剂、乳化剂或颜料。
按本发明的一种特殊实施方案,本发明的涂层组合物可含有一种选择性的UV-抗老化助剂,它吸收日光的短波长部分。由此纤维的耐用性或可发光性可保持较长时间。
本发明的目的还提供一种通过在塑料、纸、硬纸板、纸板盒、织物或金属表面涂敷本发明的涂层组合物来制备可发光涂层的方法。在表面上的涂层厚通常达到0.1-1000μm,特别是1-500μm。该该敷过程如此制定,即根据本发明涂层组合物的组成,特别是本发明所采用的发光纤维的量、长度和强度、该过程不会受纤维存在的干扰。对这里所涉及的层厚,即0.1-1000μm,特别是1-500μm,可采用的优选方法如刮刀涂布、辊式涂布、喷涂或浇涂。
由此,产生例如下述的新的应用可能性:
该涂层组合物特别用于在物体表面上制备可发光涂层。用该涂层组合物可涂敷几乎任意类型的表面,如塑料、纸、硬板纸、纸板盒、织物或金属表面。
发光涂层组合物的涂敷可用于标记物体,即施加识别功能或安全功能。如果将纤维加到粘合剂中,则与透明薄膜组合就可用作有价值文件的层压薄膜;该层压薄膜可使小批量和最小批量的经济生产成为可能。小的张贴品在与易撕开的安全薄膜组合的情况下例如可用作安全标签。
与所述涂层组合物相结合,不同的颜色组合,即纤维与不同的发光颜料组合使在UV-当下可呈对应关系。以这种方法,能容易明确识不同标记的物体。此外,可发光涂层组合物还可用于产生光学效果。如果将发光纤维加到漆中,在与合适光源相配合下可达到广告或产品设计的有趣发光效果。
本发明的涂层组合物特别可用于涂敷各类条形材料如金属薄膜或塑料薄膜,特别是标签薄膜或自粘性标签薄膜、粘合带、纸、硬纸板、纸板盒、织物或纤维物质。塑料薄膜可包括透明的和不透明的有色薄膜。
按照一种特别的实施方案,本发明的涂层组合物可用于制备标签薄膜。
标签薄膜通常由在其一面上涂有粘合层的原来的薄膜层组成,该层上覆盖以可撕去的保护纸,如硅化的纸或涂膜的纸;需要时,在背对粘合层的薄膜层上还可用印漆涂敷,以达较好的可印刷性。
作为粘合层,可采用由粘合剂、发光纤维和还可有通常的添加剂组成的涂层组合物;由此薄膜可制备标签或张贴品(标记),其粘合层具有安全功能。
此外,还有一种可能性,即采用由漆如印漆、发光纤维和还可有通常的添加物组成的本发明的涂层组合物涂刷标签的背对粘合层的薄膜面;由这种薄膜制备标签或张贴品(标记),其漆层具有安全功能。该漆可包括印漆,它使标签薄膜具有印刷可能性或改进其印刷可能性。当然,在标签薄膜的情况下,不仅粘合层,还有可存在的漆层均可由本发明的涂层组合物制备。
本发明的优点在于,其上涂敷有发光染料的发光纤维,与用发光染料颗粒本身均相染色相比能有局部浓度的发射强度,因此产生改进的可识别性。这就允许使用总计少得多的颜料浓度或染料浓度。换句话说,通过在纤维材料上涂敷染色剂颜料,还可在使用较少的涂层组合物的情况下达到高的局部染色剂,因此能达到良好的可探测性,即有利的信号/噪声-比。
通过不同发光颜色的纤维的混合和通过纤维的不同混合比可得到几乎无限的各种编码容限。
在涂层组合物中引入纤维,并接着涂敷例如纸、织物、薄膜或其它物体的优点在于可有许多通用的可能性。特别是经济性地进行小批量生产。在以粘合剂或漆的形式使用本发明的涂层组合物作为涂层时,产生了附加的安全功能。
涂层组合物中的纤维量以及纤维的尺寸是如此限定的,即在日光下用肉眼观察时不可识别或几乎不可识别,例如在透明的涂层组合物情况下,在涂层中的纤维可作为细小的浑浊被察觉。相反,在通过合适的光源如UV-灯激发时,由于高的局部染色剂浓度,纤维的发光已可用肉眼识别,只要使用了这类在激发后至少部分能发射可见光波长范围的染色剂。
通过选定发光物质,安全功能几乎可任意控制。如果选用在以合适能量的光激发后仅在红外光谱范围发射的发光物质颜料,则可得到附加的安全功能,因为该辐射不能为肉眼所看到,仅能用合适的方法如红外光谱法来探测。
实施例
将以下列实施例阐明本发明,但决不限制本发明。
实施例1
在100份含聚丙烯酸酯粘合剂的乙酸乙酯的溶液(固体含量:30%)中均匀混入0.01份市售的在UV-辐照下发光的Lumilux红MF-P 870/LT型纤维(Honeywell公司,Speciality Chemicals,以前的Riedel-de-Haёn)。然后用刮刀在PVC-薄膜上涂上该粘合剂,其层厚为200μm,并用热空气干燥。干燥的粘合剂层(60μm)再用硅化纸覆盖。该粘性薄膜经裁剪或冲压加工后,得到自粘性标签或粘贴条,在UV光辐照下,其粘合剂层显示在所加纤维范围内的红荧光。在日光下用肉眼观察时,该纤维是不可识别的。相反,在UV-灯下,该发光现象就可内肉眼观察到。
实施例2
在100份含聚丙烯酯粘合剂的乙酸乙酯的溶液(固体含量:30%)中均匀混入各种市售的在UV-辐照下发光的纤维的混合物,即0.005份Lumilux红MF-P 870/LT光纤维、0.004份Lumilux蓝MF-P 871/LT型发光纤维和0.002份Lumilux绿MF-P877/LT型发光纤维。然后用刮刀在透明的聚酯薄膜上涂上该粘合剂,其层厚为60μm,并用热空气干燥。干燥的粘合剂层(20μm)再用硅化纸覆盖。该粘性薄膜经加工后得到自粘性层压膜,其在UV-光辐射下,按照纤维红、蓝或绿在所加纤维范围内局部显示出彩色的荧光。在日光下肉眼观察时,该纤维是不可识别的。相反,在UV-灯下该发光现象就可用肉眼清楚地看到。
实施例3
在100份含聚丙酯粘合剂的含水分散液(固体含量:50%)中均匀混入各种市售的在UV-辐照下发光的纤维的混合物,即0.005份Lumilux红MF-P870/LT型发光纤维、0.004份Lumilux蓝MF-P871/LT型发光纤维和0.002份Lumilux绿MF-P877/LT型发光纤维。然后用印花辊筒在硅纸上涂上该粘合剂,其层厚为40μm,并用热空气干燥。干燥的粘合剂层(20μm)再用纸覆盖以致粘合剂层转移到纸上。该粘性纸膜经加工后得到自粘性标签,其在UV-光辐射下,局部显示纤维纤维范围的彩色荧光(红、蓝或绿)。在日光下用肉眼观察时,该纤维是不可识别的。相反,在UV-灯下该发光现象就可用肉眼清楚地看到。
实施例4
在100份聚酯漆中,均匀混入各种市售的在UV-辐照下发光的纤维,即0.007份Lumilux红MF-P870/LT型发光纤维、0.003份Lumilux绿MF-P 877/LT型发光纤维。在各种表面上以薄层(20μm)涂敷该漆,干燥后用UV-光辐照其局部显示在所加纤维范围内的红的或绿的荧光。在日光下用肉眼观察时,该纤维是不可识别的。相反,在UV-炮下该发光现象就可用肉眼清楚地看到。
Claims (19)
1.一种涂层组合物,它含至少一种有机粘合剂和纤维,该纤维包括至少一种在其中分布有可发光染料或颜料的形成纤维的材料。
2.权利要求1的涂层组合物,其特征在于,有机粘合剂选自漆,特别是清漆、纸涂刷物质或薄膜涂刷物质、胶如粘合胶;特别是基于溶剂的粘合胶和基于分散剂的粘合胶或熔化粘合胶、以及上述粘合剂的混合物。
3.权利要求1或2的涂层组合物,其特征在于,有机粘合剂是透明的或基本上透明的或是不透明的或基本上不透明的。
4.权利要求1-3之一的涂层组合物,其特征在于,该涂层组合物含纤维量按100重量份的涂层组合物计为0.0001-10重量份,特别是0.001-7.5重量份,优选为0.001-5重量份。
5.权利要求1-4之一的涂层组合物,其特征在于,形成纤维的材料选自丝、纤维素、乙酸纤维素、聚酰胺、聚酯、聚丙烯酸酯、聚烯烃、聚氨酯和棉花以及其混合物。
6.权利要求1-5之一的涂层组合物,其特征在于,纤维的长度为0.05-10mm,特别是0.1-5mm,纤维的厚度变化范围为1-1000μm,特别是10-100μm。
7.权利要求1-6之一的涂层组合物,其特征在于,该纤维含可发光染料或可发光颜料的量按纤维重量计大于5重量%直到50重量%,特别是7-40重量%,优选为10-20重量%。
8.权利要求1-7之一的涂层组合物,其特征在于,可发光染料或可发光颜料是无机性质或有机性质的。
9.权利要求1-8之一的涂层组合物,其特征在于,该可发光染料或可发光颜料在紫外辐射的激发下,至少部分发出荧光效果,特别是发射可见光或/和红外光。
10.权利要求1-9之一的涂层组合物,其特征在于,该可发光染料或可发光颜料是无机发光物质,特别是选自硫化锌、硫化锌镉、碱土金属铝酸盐、碱土金属硫化物和碱土金属硅酸盐以及其混合物,总是以至少一种过渡金属元素和/或镧系元素掺杂。
11.权利要求1-9之一的涂层组合物,其特征在于,该可发光染料或可发光颜料是有机发光物质,特别是选自可发光的,特别是可发荧光的碳环或杂环的芳香族系列,特别是苯衍生物、吖啶衍生物、呫吨衍生物、噻吨衍生物、芘衍生物、茋衍生物、香豆素衍生物和吡唑啉衍生物以及上述化合物的混合物。
12.权利要求1-11之一的涂层组合物,其特征在于,该可发光染料或可发光颜料是荧光物质(荧光染料)或荧光团,该荧光团首先通过化学反应转变成可发荧光的化学化合物,并且该化学反应可经酶催化。
13.权利要求1-12之一的涂层组合物,其特征在于,该涂层组合物可含通常的各类助剂,加工助剂或添加剂如填料、抗氧化剂、抗老化剂、抗UV-辐照助剂、流动性调制助剂、溶剂和分散剂、乳化剂或颜料,而且抗UV-辐照的助剂优选是选择性的UV-抗老化助剂,它吸收日光的短波长部分。
14.权利要求1-13之一的涂层组合物在物体表明上形成可发光的涂层的应用,特别是用于物体的识别和/或产生光学效果。
15.权利要求14的应用,其特征在于,该表面由塑料、纸、硬板纸、纸板盒、织物或金属。
16.权利要求14或15的应用,其特征在于,该物体包括各类条形材料如金属薄膜或塑料薄膜,特别是标签薄膜或自粘性标签薄膜、粘合带、纸、硬板纸和纸板盒、织物、或纤维物质。
17.一种在塑料、纸、硬板纸、纸板盒、织物或金属上通过涂敷权利要求1-13之一的涂层组合物而制备可发光涂层的方法,其特征在于,在表面上涂敷的涂层组合物的层厚优选为0.1-1000μm,特别是1-500μm。
18.一种在其表面上涂敷有权利要求1-13之一的涂层组合物的物体,其特征在于,所涂敷的涂层组合物的层厚优选为0.1-1000μm,特别是1-500μm。
19.权利要求18的物体,其特征在于,流物体包括各类薄膜如金属薄膜或塑料薄膜,特别是标签薄膜,优选自粘性标签薄膜、各类粘合带、纸、硬板纸和纸板盒或纤维材料,特别包括粘贴标签,在这种情况下该粘贴层和/或可能有的漆层作为可发光的层形成。
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- 2001-09-08 AT AT01121522T patent/ATE346892T1/de not_active IP Right Cessation
- 2001-09-08 DE DE50111530T patent/DE50111530D1/de not_active Expired - Fee Related
- 2001-09-08 EP EP20010121522 patent/EP1191076B1/de not_active Expired - Lifetime
- 2001-09-21 JP JP2001289790A patent/JP2002105409A/ja active Pending
- 2001-09-24 US US09/960,721 patent/US6673437B2/en not_active Expired - Fee Related
- 2001-09-25 CN CN01140895A patent/CN1346857A/zh active Pending
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CN102482538B (zh) * | 2009-09-08 | 2015-04-22 | 联邦印刷有限公司 | 具有固定在其上的混合纤维的塑料薄膜 |
CN102154824A (zh) * | 2011-02-14 | 2011-08-17 | 江南大学 | 在夜晚可以发光的功能性织物的制造方法 |
CN102154824B (zh) * | 2011-02-14 | 2012-07-11 | 江南大学 | 在夜晚可以发光的功能性织物的制造方法 |
CN105874109B (zh) * | 2013-11-14 | 2019-01-01 | 霍尼韦尔国际公司 | 发光纤维,包括该发光纤维的制品,和形成该发光纤维的方法 |
CN105874109A (zh) * | 2013-11-14 | 2016-08-17 | 霍尼韦尔国际公司 | 发光纤维,包括该发光纤维的制品,和形成该发光纤维的方法 |
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CN107406694B (zh) * | 2014-12-30 | 2020-06-26 | 莫门蒂夫性能材料股份有限公司 | 发光的有机硅涂料 |
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CN107236442B (zh) * | 2017-07-25 | 2019-04-30 | 滁州卷烟材料厂 | 一种荧光防伪铝箔纸 |
CN109836990A (zh) * | 2019-02-27 | 2019-06-04 | 吉林省铭嘉建筑材料有限公司 | 一种具有防伪功能的聚氨酯防水涂料及其制备方法 |
Also Published As
Publication number | Publication date |
---|---|
ATE346892T1 (de) | 2006-12-15 |
EP1191076B1 (de) | 2006-11-29 |
US6673437B2 (en) | 2004-01-06 |
DE10047677A1 (de) | 2002-04-25 |
JP2002105409A (ja) | 2002-04-10 |
DE50111530D1 (de) | 2007-01-11 |
US20020076550A1 (en) | 2002-06-20 |
EP1191076A1 (de) | 2002-03-27 |
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