CN108291139A - 安全颜料、发光聚合物树脂及其制造方法 - Google Patents
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Abstract
本发明涉及用于安全应用的颜料颗粒，其包括热固性材料基质和嵌入其中并且由热塑性聚合物组成的多个核颗粒，其中特征物质溶解于所述核颗粒中并且所述特征物质为有机或金属有机物质。本发明还涉及通过如下制造安全颜料例如发光印刷颜料的方法：将其中发光体以溶解的形式存在的热塑性聚合物颗粒引入热固性材料基质中。
Description
本发明涉及安全颜料、特别地基于发光聚合物树脂的安全颜料及其制造方法。
本发明特别地涉及用于制造安全颜料如发光印刷颜料的方法，其借助于将其中在各自的情况下发光体以溶解形式存在的热塑性聚合物颗粒引入到热固性材料基质中。通过热塑性聚合物颗粒中发光体的分子分布，可大大降低达到一定亮度所需的染料量。随后引入到热固性材料基质中保护染料另外地免受被溶解聚合物的溶剂以及含水酸和碱侵蚀(袭击)。
文献US 5795379 A描述了将发光染料引入到固体树脂中。该文献仅涉及使用多异氰酸酯作为热固性材料基质及其制造方法。该文献中没有提到引入溶解在第二聚合物中的染料。针对含水的酸和碱仅实现不足的保护；此外，为了实现大的亮度需要大量的发光体。
文献DE 10 2006 008 245 A1描述了用一种(一个)有机或无机壳或用多种(多个)有机或无机壳直接包封有机发光物质以提高包封染料的耐光性。在该情况下，包封引入的染料的聚合物充当保护免受光作用的壳。
相反，在本发明中，发光染料以溶解的形式存在于聚合物中，因此大大降低了实现一定的亮度所需的染料量。通过另外引入到热固性材料基质中，实现了对特征物质的针对被溶剂以及含水酸和碱化学侵蚀的补充保护。在该情况下，热固性材料基质不充当单个核-壳颗粒的典型壳，而是充当包围多个核的油灰(Kitt)。这提供制造技术上的优势，例如可研磨性而不损失补充的保护性效果。
文献EP 1 208 382 B1描述了将多种离散的墨颗粒如聚苯乙烯的荧光微珠嵌入基质中，随后将其用充当扩散阻挡物的紧密的壳包封。同样在该现有技术中，染料的包封被用作针对水性的外部影响的保护。这种解决方案在技术上很复杂并且对于大批量生产而言可扩展性差，因为例如在研磨微囊化的颗粒时，壳被破坏且因此其保护性效果丧失。
专利EP 0 226 367 B1描述了荧光缩合聚合物颗粒与多种聚合物附聚以形成大的附聚颗粒。这种方法在技术上很复杂，因为难以在缩合聚合物内以足够细分布的形式溶解荧光物质。
根据本发明，通过使用热塑性材料而绕过了该问题。此外，疏水性热塑性材料提供更好的针对含水酸和碱的保护。
本发明的目的是提供相对于现有技术而言改善的发光印刷颜料。此外，本发明的目的是提供相对于现有技术而言改善的制造发光印刷颜料的方法。
这些目的通过独立权利要求中限定的特征的组合实现。本发明的扩展为从属权利要求的主题。
发明内容
项1.(第一方面)用于安全应用的颜料颗粒，包括：
-热固性材料基质，和
-多个嵌入其中的热塑性聚合物的核颗粒，其具有溶解在核颗粒中的特征物质，其中特征物质为有机或金属有机物质。
项2.(优选的)根据项1的颜料颗粒，其中特征物质为荧光或磷光或光致变色或热致变色的特征物质或者UV或IR或VIS吸收染料。
项3.(优选的)根据项1或2的颜料颗粒，其中荧光或磷光特征物质在UV光谱范围内是可激发的并且在可见光谱范围内发射。
项4.(优选的)根据项1-3之一的颜料颗粒，其中荧光或磷光特征物质在UV光谱范围内或在可见光谱范围内是可激发的并且在IR光谱范围内发射。
项5.(优选的)根据项1-4之一的颜料颗粒，其中形成能量转移体系的两种不同的发光染料以溶解的形式存在于核中，其中激发后的第一染料将其激发能部分或完全地转移至第二染料。
项6.(优选的)根据项1-5之一的颜料颗粒，其中热塑性聚合物选自聚苯乙烯(PS)、聚丙烯酸酯、聚乙烯(PE)、聚丙烯(PP)、聚碳酸酯(PC)、聚酰胺(PA)、聚氨酯(PU)、聚脲(PH)、聚对苯二甲酸乙二醇酯(PET)或其它聚酯，优选地选自聚苯乙烯(PS)或者选自以下之一：聚丙烯酸酯聚甲基丙烯酸甲酯(PMMA)、聚乙酸乙烯酯(PVAC)、聚氯乙烯(PVC)、聚丙烯腈(PAN)，特别优选地选自聚苯乙烯(PS)或聚甲基丙烯酸甲酯(PMMA)。
项7.(优选的)根据项1-6之一的颜料颗粒，其中热塑性聚合物的链长在1,000-1,000,000g/mol、特别地50,000-250,000g/mol的范围内。
项8.(优选的)根据项1-7之一的颜料颗粒，其中热固性材料基质包括加聚物、优选地不同的单胺、二胺或三胺与三聚体型异氰酸酯单体、特别优选地异佛尔酮二异氰酸酯的异氰脲酸酯三聚体的混合物。
项9.(优选的)根据项1-8之一的颜料颗粒，其中热塑性核颗粒以在0.1和25重量％之间、特别地3-20重量％的浓度存在于热固性材料基质中。
项10.(优选的)根据项1-9之一的颜料颗粒，根据测试方法A5、优选地A30，其对甲苯、乙酸乙酯、盐酸(5％)、氢氧化钠溶液(2％)和次氯酸钠溶液(5％活性氯)是稳定的，其中测试之后保留的特征强度高于初始强度的80％。
项11.(优选的)根据项1-10之一的颜料颗粒，根据测试方法A5，其对丙酮是稳定的，其中测试之后保留的特征强度高于初始强度的80％。
项12.(第二方面)用于制造用于安全应用的颜料颗粒的方法，所述颜料颗粒包括热固性材料基质和多个嵌入其中的具有溶解在核颗粒中的特征物质的热塑性聚合物的核颗粒，其中特征物质为有机物质或金属有机络合物，所述方法具有如下的步骤：
a)将有机或金属有机特征物质溶解于热塑性聚合物中以用此方式提供具有溶解于其中的特征物质的热塑性颗粒的步骤；和
b)将步骤a)中获得的具有溶解于其中的特征物质的热塑性颗粒引入热固性材料基质中的步骤，
c)将步骤b)中获得的产物研磨成颜料颗粒的步骤。
项13.(优选的)根据项12的方法，其中步骤a)包括如下分步骤：
a1)将热塑性聚合物和有机或金属有机特征物质溶解在有机溶剂中，
a2)使用表面活性剂将步骤a1)的溶液分散在含水介质中；
a3)除去有机溶剂；
a4)分离核颗粒；
并且其中在步骤b)中，核颗粒的嵌入优选地通过核颗粒与加聚物的单体一起的捏合或挤出过程进行；
并且其中在步骤c)中，颜料颗粒的研磨进行至小于25μm、优选地小于12μm、特别优选地小于6μm的粒度(d99)。
项14.(第三方面)墨浓缩物(浓色体)，其包括根据项1-11之一的颜料颗粒，特别地以超过40％(重量百分数)的颜料颗粒的浓度。
项15.(第四方面)用于胶版印刷、丝网印刷或钢凹版印刷的印刷墨，其包括根据项1-11之一的颜料颗粒，优选地以1-40％(重量百分数)、特别优选地1-20％重量百分数的颜料颗粒的浓度。
项16.(第五方面)有价文件，其包括根据项1-11之一的安全颜料。
发明详述
本发明涉及将发光染料引入到固体树脂中的从文献US5795379A中已知的方法的有利发展。在根据本发明的方法中，发光染料或特征物质不是直接与树脂组分挤出的，而是在上游的步骤中溶解在热塑性聚合物的小球(或颗粒)中。溶解在聚合物中的染料的浓度在此优选在0.01％至15％的范围内。通过所述上游的方法步骤，与直接挤出到树脂中的有机染料相比，可以显著更低的有机发光物质的量例如10％-60％实现相同的最终产品的亮度。
本发明明确地不涉及具有限定的均匀几何形状的核-壳颗粒。
根据本发明的产品的另一优点在于：溶解在聚合物中的有机染料针对含水酸和碱的的稳定化。与文献EP 1 208 382 B1中描述的颜料相反，用包封的缩合树脂完全不间断地包封聚合物在此并不是决定性的。含有发光染料或特征物质的聚合物(例如PMMA)由于其与水溶液的不良润湿性而充当针对含水酸和碱的阻挡物，因此减少溶解的不稳定的染料与酸和碱之间的接触。
将稳定的聚合物球嵌入树脂中进一步容许借助于研磨容易地调节对于相应印刷工艺有利的颜料粒度，这导致生产工艺的简单和成本有效的可扩展性(可缩放性)。
此外，不同颜色的球的嵌入容许通过加色(additive color)混合而以简单的方式调节所需的发光色调。根据优选实施方式，将不同的染料一起引入到聚合物中以通过加色混合来调节所需的发光色调。
根据本发明的制造方法具有两个步骤。在第一制造步骤中，将发光有机物质或特征物质溶解在热塑性聚合物中。为此目的，将聚合物(例如聚甲基丙烯酸甲酯或聚苯乙烯)与发光物质或另外的特征物质一起溶解在合适的有机溶剂(例如二氯甲烷)中。为了将具有溶解的染料或特征物质的聚合物转换回到固体形式，可选择多种合成形式。优选地，借助于表面活性剂(例如十二烷基硫酸钠)将聚合物溶液分散在水中，并且通过简单的蒸发从混合物除去溶剂。另一可能性是使聚合物(包括溶解的染料/特征物质)在二乙醚中沉淀，随后研磨至所需的粒度(特别地在冷却下进行)。聚合物颗粒的优选粒度(d99)为小于7μm、特别优选地小于3μm。
热塑性核由热塑性聚合物、优选地热塑性的非交联聚合物组成。根据优选实施方式，核材料的聚合物由聚合的乙烯衍生物组成、进一步优选地由以下组成：聚苯乙烯(PS)或聚丙烯酸酯(其中优选地聚甲基丙烯酸甲酯(PMMA))、聚乙酸乙烯酯(PVAC)、聚氯乙烯(PVC)、聚丙烯腈(PAN)或者包含前述聚合物的一种或多种的共聚物如丙烯腈-丁二烯-苯乙烯共聚物(ABS)。根据另一优选实施方式，乙烯衍生物为聚乙烯(PE)、聚丙烯(PP)或由脂族碳链构建的其它聚合物。根据另一优选实施方式，核材料的聚合物由聚碳酸酯(PC)、聚酰胺(PA)或聚酯如聚对苯二甲酸乙二醇酯(PET)组成。
核材料的聚合物的链长优选在1,000-1,000,000g/mol的范围内、特别优选地在50,000-250,000g/mol的范围内。
在第一合成步骤结束之后，将根据以上描述制造的聚合物颗粒在第二制造步骤中作为发光物质引入到热固性材料基质中。为此目的，可将聚合物颗粒与所用的树脂类型(例如聚氨酯树脂或聚脲树脂)的原材料一起挤出或捏合。聚合物颗粒在混合物中的优选浓度在0.1％至25％的范围内、特别优选地在3％至20％(即重量百分数)的范围内。在挤出或捏合过程结束后，将得到的包含聚合物颗粒的树脂研磨成树脂粉末，其中可鉴于所需的印刷工艺而调节粒度。
根据优选实施方式，将加聚物用于制造用热塑性核处理的热固性材料基质。在此，优选地，在工业捏合机中将三聚体型异氰酸酯单体、优选地异佛尔酮二异氰酸酯的异氰脲酸酯三聚体与不同的单胺、二胺或三胺的混合物加热至150℃-250℃、优选地180℃并且在该过程中捏合直至硬化。
根据另一优选实施方式，为了制造用热塑性核处理的热固性材料基质，在5℃-250℃的范围内的温度下在螺杆挤出机中以升高温度曲线将三聚体型异氰酸酯单体、优选地异佛尔酮二异氰酸酯的异氰脲酸酯三聚体与不同的单胺、二胺或三胺的混合物挤出。
在挤出过程或捏合过程结束之后，将所得到的包含特征物质的树脂粉末研磨至对应于相应应用的粒度。例如，对于在胶版印刷应用中的使用，颜料优选地具有<12μm的粒度(d99)。对于在丝网印刷应用中的使用，颜料优选地具有<25μm的粒度(d99)。对于在钢凹版印刷应用中的使用，颜料优选地具有<6μm的粒度(d99)。
根据优选实施方式，颜料具有小于6μm的粒度(d99)。
作为特征物质，可溶解在非极性有机溶剂中的有机或金属有机分子是特别合适的。无机颜料颗粒或量子点等的引入在技术上是困难的(例如，在核聚合物中不溶解，可能附聚)并且不提供根据本发明的所有优点(例如提高的每单位所使用的发光体量的亮度)，并且出于该原因而不为优选的。
根据优选实施方式，特征物质是发光染料。根据优选实施方式，发光染料是荧光染料。根据另一优选实施方式，发光染料是磷光染料。根据另一优选实施方式，发光染料是在UV范围内可激发的发光染料，其在可见光谱范围内发射。根据另一优选实施方式，所述发光染料是在可见光谱范围内可激发的发光染料，其在可见光谱范围内发射。根据另一优选实施方式，发光染料是在红外范围内发射的发光染料。染料可为纯有机分子和金属有机络合物两者。
根据优选实施方式，将两种或更多种荧光或磷光发光染料混合以产生能量转移体系或FRET体系，其中激发后的第一发光染料可将其激发能部分或完全地递送至第二发光染料。在这种FRET体系的情况下，所涉及的发光染料之一优选地在UV范围内可激发并在可见光谱范围内发射，而另一种发光染料在可见光谱范围内可激发并在可见光谱范围内发射。
可UV激发或在可见光谱范围内可激发并且在可见光谱范围内发射的发光染料的物质类别的实例为纯有机发光染料和发光金属络合物。可能的染料类别是例如二芳基多烯、二芳基乙烯、芳基乙炔、唑、吡唑、吲哚、蒽酮、醌、菁(Cyanine)、罗丹明、嗪、吩嗪、噻嗪、吩噻嗪、苝、涤纶、香豆素、苯并嗪酮或苯并噻嗪酮以及稀土金属络合物如β-二酮酸稀土金属络合物或吡啶二羧酸(Dipicolinat)稀土金属络合物，在本文中优选地中性带电(带电为中性)的稀土金属络合物。其它类别的有机发光染料也可使用。
在红外范围内发射的合适的发光染料的实例是有机荧光染料或发光金属络合物，例如IR-1048、Cy7或Nd(TTA)3(三-噻吩甲酰三氟丙酮钕)。
FRET体系的实例是例如黄-绿色可激发的荧光染料和黄-绿色发射的荧光染料的混合物，如2,9-双(2,6-二异丙基苯基)蒽[2,1,9-def:6,5,10-d'e'f']二异喹啉-1,3,8,10(2H,9H)-四酮(C48H42N2O4，具有橙色发光发射的绿色可激发的苝染料，在下文中称为“F-橙”)与N-(2-(4-氧代-4H-苯并[d][1,3]嗪-2-基)苯基)萘-2-磺酰胺(C24H16N2O4S，具有绿色发光发射的可UV激发的发光染料，在下文中称为“F-绿”)以1:15的重量比的混合物。
FRET体系还可用于读取发光颜料中的鉴证组分。因此，受体染料不仅可通过供体染料的能量转移来激发，而且受体染料的直接激发可导致其发光。例如，一方面F-橙和F-绿的混合物可在UV-A范围内例如在365nm处激发(F-绿的激发，随后能量转移到F-橙)。另一方面，对于鉴证测试，F-橙也可直接被激发，例如通过波长525nm的光。因此，受体物质的直接激发可用于将FRET体系与其它染料体系区分开来，并且提供例如可在实验室中或通过传感器自动地分析的另外的安全级别。
根据优选实施方式，发光染料因此含有能量转移体系(FRET体系)、优选地作为供体的UV-可激发的发光染料和作为受体的在可见范围内可激发的发光染料的FRET体系。受体优选为苝染料。受体优选地用作鉴定标记物。
优选地，特征物质是红外吸收剂。特别优选地，红外吸收剂在可见光谱范围内没有或仅有很少的吸收。根据优选实施方式，吸收剂是窄带的(例如具有小于200nm的FWHM(“半峰全宽”))或尖锐带的(例如具有小于30nm的FWHM)，并因此在窄的光谱范围内吸收。根据另一优选实施方式，吸收剂以宽带方式吸收(例如，具有大于200nm的FWHM)。根据优选实施方式，红外吸收剂的吸收最大值在700nm-900nm的范围内，优选在700nm-800nm的范围内，因此适合于经由用于钞票的标准红外传感器被读取。根据另一优选实施方式，红外吸收剂的吸收最大值高于900nm、进一步优选地高于950nm、特别优选地在1,000nm-1,100nm的范围内，并且因此不被用于钞票的标准红外传感器检测到，然而可通过用于钞票的特殊红外传感器检测。
根据优选实施方式，UV吸收剂的吸收最大值或强吸收带在315nm至380nm的UV-A范围内、特别优选在350nm至380nm的范围内。根据另一优选实施方式，UV吸收剂的吸收最大值或强吸收带在200nm至315nm、进一步优选地220nm至290nm、特别优选地240nm至270nm的UV-B/C范围内。
合适的红外吸收剂例如可从Fujifilm Imaging Colorants公司(例如CCK-55)、BASF公司(例如Lumogen IR-Absorber)或以商标名Epolight从Epolin公司商购获得。例如，Epolight 4101在739nm处以窄带方式吸收并且当以稀释形式引入聚合物中时不显示可察觉的固有颜色。同样，例如Epolight 4831在1,000nm处以窄带方式吸收，并且当以稀释形式引入聚合物中时不显示可察觉的固有颜色。
合适的UV吸收剂可例如以商标名Tinuvin和Chimassorb得自BASF公司。例如，Tinuvin 326在360nm处具有强吸收带并且Chimassorb 81在330nm处具有强吸收带。
根据优选实施方式，特征物质为可转换(可切换)的染料。优选地，它是热致变色或光致变色染料。根据优选实施方式，可转换染料是光致变色化合物。优选地，这是可在第一可见状态和第二可见或不可见状态之间转换的光致变色化合物。在一个方向上的转换(切换)操作优选通过用UV光照射来进行，而切换回是通过自身(热)或通过用可见光照射来进行的。
根据优选实施方式，光致变色染料也是发光染料。在此，染料的两种转换状态或仅一种转换状态可为能发光的。多种转换状态可具有相同的发光性质(例如，在相同波长下的发射)或不同的发光性质(例如转换操作之后发射波长的变化)。
根据优选实施方式，由转换操作产生的吸收带或发射带、特别地所产生的吸收带在可见光谱范围内。
根据另一优选实施方式，由转换操作产生的吸收带或发射带在红外范围内、例如在700nm-900nm的范围内。
合适的热致变色染料的实例是例如(a)在温度变化时通过结构变化改变其颜色的有机分子，如9,9'-二亚呫吨(9,9'-Bixanthyliden)和10,10'-二亚蒽酮(10,10'-Bianthronylidene；(b)无色母体染料(例如螺内酯、螺吡喃)和可逆质子供体(例如双酚A、1,2,3-三唑)和相变材料(例如石蜡)的组合，其在温度变化时通过无色母体染料的质子化/去质子化而改变颜色；(c)以温度依赖性方式改变其颜色强度的染料或金属络合物，例如在铕络合物的情况下的温度猝灭；和(d)具有不同温度行为的多种染料的组合(例如铽和铕络合物的混合物，如文献EP 0 256 922 B1中所述，其可以温度依赖性方式发红(红光)或发绿(绿光)。
在此，(a)和(d)由于明显的颜色变化而为优选的，而(b)由于复杂性和难以实施而为不那么优选的。
合适的光致变色染料的实例是例如螺吡喃、芪/氮杂芪、三芳基甲烷、硝酮、俘精酸酐、萘并吡喃、螺嗪、醌和二芳基乙烯。二芳基乙烯由于其高的光稳定性而为优选的。例如，以开环结构形式的二芳基乙烯BTF6(＝1,2-双(2-甲基-1-苯并噻吩-3-基)全氟环戊烯)在200nm至300nm处的UV范围内吸收并且在可见光谱范围内没有可察觉的吸收带，因此是无色的。然而，在用波长254nm的UV光照射之后，它转变成在530nm处的可见光谱范围内具有吸收带、因此有色的闭环结构。在用波长315nm的UV光激发时，闭合和开环结构两者都在450nm处发射，因此同时给出发光染料。
通过等待(热)或用可见光(例如波长400nm的光)照射，闭环结构可返回到开环结构。
此外，可通过不同特征物质的有针对性的组合(或联合包封)来制备更复杂的编码，并制备同时适合于不同机器可读的验证方法的特征颗粒。
除了特征物质之外，可将另外的添加剂添加至聚合物颗粒。
根据优选实施方式，将所谓的增塑剂如己二酸二乙基己酯、邻苯二甲酸二丁酯或邻苯二甲酸二异壬酯添加至聚合物颗粒。作为物质类别，这里可使用邻苯二甲酸的二酯、己二酸的二酯和癸二酸与链较长的单醇(2-乙基己醇、异壬醇、癸醇、脂肪醇、苯甲醇、乙二醇醚)的二酯，柠檬酸的三酯，链较长的脂族醇的磷酸酯，脂族醇的二苯甲酸酯，脂肪酸与脂族醇的酯，聚乙二醇醚的二酯，树脂酸与链较长的脂族醇的酯，基于环氧化脂肪酸酯或环氧化油的增塑剂，碳增塑剂和氯化石蜡。以此方式，可调节聚合物核的机械性质。特别地，可增加用于某些特征物质的核材料的接受性(吸收性)。
优选地，相对于核材料的质量，添加0.1-5重量％、进一步优选地0.2-2重量％、特别优选地0.3-0.6重量％的增塑剂。
根据另一优选实施方式，将UV吸收剂添加至核材料。以此方式，例如特征物质的耐光性可被改善。添加的UV吸收剂优选地在200nm-350nm的波长范围内吸收。合适的UV吸收剂可例如以商标名Tinuvin和Chimassorb(例如Chimassorb 81)商购自BASF公司。
根据另一优选实施方式，将染料添加至核材料。以此方式，例如可调节胶囊的固有着色(例如红色或蓝色)。同样，可使用染料来调制特征物质的激发或发射光谱。
缩合到树脂中的聚合物颗粒不一定必须是球形的。鉴于用发光有机染料处理的聚合物结构，也可使用片状或未限定的颗粒形状。
根据优选实施方式，将染料挤出在聚合物组合物中并且随后研磨至所需粒度，优选在0.05μm-100μm的范围内。
根据本发明，将特征物质(例如荧光物质、金属有机或有机IR或UV吸收剂、光致变色物质)、特别地发光物质以溶解的形式存在于其中的热塑性核引入到热固性材料基质中。以此方式，尤其实现以下优点：
-通过热塑性材料(例如PMMA)使发光物质对含水的酸和碱稳定化；
-为此，对于酸/碱稳定化无需封闭的外壳；
-可研磨性和因此的简单和成本较低的制造工艺直至工业规模的可扩展性；
-通过将荧光物质物理溶解在热塑性材料中而实现较高的发光效率；以此方式这导致减少的材料使用和降低的成本；
-通过极性热固性材料基质对表面的改性导致改善的在印刷油墨中的引入。
安全颜料优选地用于制造有价文件。这优选地通过以印刷油墨印刷、特别地用于胶版印刷、丝网印刷或钢凹版印刷进行。代替将颜料直接引入到印刷漆和/或印刷墨中,也可首先由颜料制造墨浓缩物。所述墨浓缩物例如具有50％的颜料含量并且可稍后被引入到印刷漆或印刷墨中。这具有应用技术优势，例如较快速的引入或在引入期间避免灰尘。
替代地，也可将安全颜料引入到聚合物组合物中，优选地以制备母料或制造有价文件基材、安全箔、斑纹纤维或安全线。例如，这可通过挤出进行。
在下文中将参照实施方式更详细地描述本发明。
实施例1：绿色荧光颜料
将50g具有100,000g/mol的平均分子量的PMMA球与5g N-(2-(4-氧代-4H-苯并[d][1,3]嗪-2-基)苯基)萘-2-磺酰胺(C24H16N2O4S)一起溶解于1升二氯甲烷中。将该混合物与5升1％十二烷基硫酸钠水溶液一起置于反应器中并用均化器分散5分钟。随后，在搅拌的同时在500毫巴下蒸发二氯甲烷。在除去二氯甲烷后，剩余的水相包含约55g具有约2μm平均粒度的PMMA球，其包含溶解的染料1(在下文中称为“PMMA 1”)。使用超速离心机，在各情况下用1升水将颗粒洗涤三次并且随后在60℃下干燥。
在实验室捏合机中将如下组分在180℃下捏合直至固化：
79.63g异佛尔酮二异氰酸酯的异氰脲酸酯三聚体
22.46g苯甲酰胺
2.00g脲
14.12g三聚氰胺
10g PMMA 1。将获得的颗粒研磨成11μm的粒度(d99)。这得到0.72％的染料在颜料中的质量比例。
用三辊研磨机将所得颜料以15％的浓度引入胶版漆(Sicpa Holding SA)中并且在胶版印刷中以2g/m2印样重量印样。获得在365nm激发光下发绿色荧光的印样。
印样显示高的对有机溶剂以及含水的酸和碱的稳定性，而纯染料的印样是不耐受的。
实施例2：红色荧光颜料
将50g具有100,000g/mol的平均分子量的PMMA球与3g Eu(TTA)3(TPPO)2(TTA＝噻吩甲酰三氟丙酮；TPPO＝三苯基氧化膦)一起溶解于1升二氯甲烷中。将该混合物与5升1％十二烷基硫酸钠水溶液一起置于反应器中并用均化器分散5分钟。随后，在搅拌的同时在500毫巴下蒸发二氯甲烷。在除去二氯甲烷后，剩余的水相包含约53g具有约2μm平均粒度的PMMA球，其包含溶解的染料2(在下文中称为“PMMA 2”)。使用超速离心机，在各情况下用1升水将颗粒洗涤三次并且随后在60℃下干燥。
在实验室捏合机中将以下组分在180℃下捏合直至固化：
79.63g异佛尔酮二异氰酸酯的异氰脲酸酯三聚体
31.72g对甲苯磺酰胺
2.00g脲
14.12g三聚氰胺
10g PMMA 2。将获得的颗粒研磨成11μm的粒度(d99)。用三辊研磨机将所得颜料以15％的浓度引入胶版漆(hubergroup Deutschland GmbH)中并且在胶版印刷中以2g/m2印样重量印样。获得在365nm激发光下发红色荧光的印样。
印样显示高的对有机溶剂以及含水的酸和碱的稳定性，而纯染料的印样是不耐受的。
实施例3(对比例)
在实验室捏合机中将以下组分在180℃下捏合直至固化：
79.63g异佛尔酮二异氰酸酯的异氰脲酸酯三聚体
31.72g对甲苯磺酰胺
2.00g脲
14.12g三聚氰胺
9g N-(2-(4-氧代-4H-苯并[d][1,3]嗪-2-基)苯基)萘-2-磺酰胺(C24H16N2O4S)。将获得的颗粒研磨成11μm的粒度d99。这得到6.6％的染料在颜料中的质量比例。
用三辊研磨机将所得颜料以15％的浓度引入胶版漆(Sicpa Holding SA)中并且在胶版印刷中以2g/m2印样重量印样。
实施例4：黄色荧光颜料
将50g具有120,000g/mol的平均分子量的PMMA球与3g N-(2-(4-氧代-4H-苯并[d][1,3]嗪-2-基)苯基)萘-2-磺酰胺(C24H16N2O4S)(＝染料1)和2g Eu(TTA)3(TPPO)2(TTA＝噻吩甲酰三氟丙酮；TPPO＝三苯基氧化膦)(＝染料2)一起溶解于1升二氯甲烷中。将该混合物与5升1％十二烷基硫酸钠水溶液一起置于反应器中并用均化器分散5分钟。随后，在搅拌的同时在500毫巴下蒸发二氯甲烷。在除去二氯甲烷后，剩余的水相包含约55g具有约2μm平均粒度的PMMA球，其包含溶解的染料1和染料2(在下文中称为“PMMA 1-2”)。使用超速离心机，在各情况下用1升水将颗粒洗涤三次并且随后在60℃下干燥。
在实验室捏合机中将以下组分在180℃下捏合直至固化：
71.8g异佛尔酮二异氰酸酯
34.8g对甲苯磺酰胺
20.09g三聚氰胺
10g PMMA 1-2。将获得的颗粒研磨成11μm的粒度(d99)。用三辊研磨机将所得颜料以15％的浓度引入基于水的丝网印刷墨(KG)中并且在丝网印刷中以6g/m2印样重量印样。获得通过以365nm的激发发黄色荧光的印样。
印样显示高的对有机溶剂以及含水的酸和碱的稳定性，而纯染料的印样是不耐受的。
实施例5：黄色荧光颜料
将25g具有80,000g/mol的平均分子量的PMMA球与2g N-(2-(4-氧代-4H-苯并[d][1,3]嗪-2-基)苯基)萘-2-磺酰胺(C24H16N2O4S)(＝染料1)一起溶解于0.5升二氯甲烷中。将该混合物与2.5升1％十二烷基硫酸钠水溶液一起置于反应器中并用均化器分散5分钟。随后，在搅拌的同时在500毫巴下蒸发二氯甲烷。
在第二反应器中，将25g具有100,000g/mol的平均分子量的PMMA球与2g Eu(TTA)3(TPPO)2(TTA＝噻吩甲酰三氟丙酮；TPPO＝三苯基氧化膦)(＝染料2)一起溶解于0.5升二氯甲烷中。将该混合物与2.5升1％十二烷基硫酸钠水溶液一起置于反应器中并用均化器分散5分钟。随后，在搅拌的同时在500毫巴下蒸发二氯甲烷。
在除去二氯甲烷后，剩余的水相各自包含约25g具有约2μm平均粒度的PMMA球，其包含溶解的染料1或溶解的染料2(在下文中称为“PMMA1b”和“PMMA 2b”)。使用超速离心机，在各情况下用1升水将颗粒洗涤三次并且随后在60℃下干燥。
在实验室捏合机中将以下组分在180℃下捏合直至固化：
71.8g异佛尔酮二异氰酸酯
22.46g苯甲酰胺
20.09g三聚氰胺
5g PMMA 1b
5g PMMA 2b。将获得的颗粒研磨成11μm的粒度(d99)。用三辊研磨机将所得颜料以15％的浓度引入基于水的丝网印刷墨(KG)中并且在丝网印刷中以6g/m2印样重量印样。获得通过以365nm的激发发黄色荧光的印样。
印样显示高的对有机溶剂以及含水的酸和碱的稳定性，而纯染料的印样是不耐受的。
实施例6：实施例1和3(对比例)的强度和稳定性测量
对在限定的测量几何结构下产生的印样进行强度测量。作为测量装置，荧光光谱仪Perkin-Elmer LS50B用于此目的。
在对比例3中，已使用超过8倍的染料量。然而，所获得的发光强度不高于实施例1中的发光强度。
通过将来自实施例1的印样和来自对比例3的印样浸入1摩尔浓度氢氧化钠溶液中10分钟来测试针对碱的稳定性。随后的强度测量再次在限定的测量几何结构下进行。测量装置Perkin-Elmer LS50B也用于此目的。
| 样品 | 在碱稳定性测试之后的保留强度 |
| 实施例1 | 78％ |
| 对比例3 | 12％ |
实施例7：IR吸收颜料
将25g具有80,000g/mol的平均分子量的PMMA球与1g IR吸收剂CKK-55(FujifilmImaging Colorants)和0.25g邻苯二甲酸二丁酯一起溶解于0.5升二氯甲烷中。将该混合物与2.5升1％十二烷基硫酸钠水溶液一起置于反应器中并用均化器分散5分钟。随后，在搅拌的同时在500毫巴下蒸发二氯甲烷。
在除去二氯甲烷后，剩余的水相包含约26g具有约2μm平均粒度的PMMA球，其包含溶解的IR吸收剂CKK-55(在下文中称为“PMMA CCK-55”)。使用超速离心机，在各情况下用1升水将颗粒洗涤三次并且然后在60℃下干燥。
在实验室捏合机中将以下组分在180℃下捏合直至固化：
71.8g异佛尔酮二异氰酸酯
22.7g苯甲酰胺
20.09g三聚氰胺
10g PMMA CKK-55。将获得的颗粒研磨成11μm的粒度(d99)。用三辊研磨机将所得颜料以15％的浓度引入胶版漆(Sicpa Holding SA)中并且在胶版印刷中以2g/m2印样重量印样。印样显示在850nm处的NIR范围内的吸收带。
印样显示高的对有机溶剂以及含水的酸和碱的稳定性，而纯吸收剂的印样是不耐受的。
实施例8：光致变色颜料
将50g具有110,000g/mol的平均分子量的PMMA球与和1.65g顺式-1,2-二氰基-1,2-双(2,4,5-三甲基-3-噻吩基)乙烯(C18H18N2S2)一起溶解于1升二氯甲烷中。将该混合物与5升1.5％十二烷基硫酸钠水溶液一起置于反应器中并用均化器分散5分钟。随后，在搅拌的同时在750毫巴下蒸发二氯甲烷。在除去二氯甲烷后，剩余的水相包含约51g具有约2μm平均粒度的PMMA球，其包含溶解的光致变色染料(在下文中称为“PMMA DBP”)。使用超速离心机，在各情况下用1升水将颗粒洗涤三次并且然后在60℃下干燥。
在实验室捏合机中将以下组分在140℃下捏合直至固化：
73.1g异佛尔酮二异氰酸酯
20.47g苯甲酰胺
21.29g三聚氰胺
8.5g PMMA DBP。将获得的颗粒研磨成11μm的粒度(d99)。用三辊研磨机将所得颜料以15％的浓度引入胶版漆(Sicpa Holding SA)中并且在胶版印刷中以2g/m2印样重量印样。获得无色的印样，其在以330nm照射下显示淡红色印记。该颜色印记通过轻微加热或通过以(例如波长520nm的)可见光照射而消失。
印样显示高的对有机溶剂以及含水的酸和碱的稳定性，而纯染料的印样是不耐受的。
实施例9：具有UV吸收剂和固有颜色的颜料
将50g具有100,000g/mol的平均分子量的PMMA球与1.5g蓝色颜料"苏丹蓝II"(1,4-双(丁基氨基)蒽醌，C22H26N2O2)和1g UV吸收剂2-羟基-4-(辛氧基)二苯甲酮(CH3(CH2)7OC6H3(OH)COC6H5)一起溶于1升二氯甲烷中。将该混合物与5升1％十二烷基硫酸钠水溶液一起置于反应器中并用均化器分散5分钟。随后，在搅拌的同时在750毫巴下蒸发二氯甲烷。在除去二氯甲烷后，剩余的水相包含约51g具有约2μm平均粒度的PMMA球，其包含溶解的蓝色染料和UV吸收剂(在下文中称为“PMMA SBUV”)。使用超速离心机，在各情况下用1升水将颗粒洗涤三次并且然后在60℃下干燥。
在实验室捏合机中将以下组分在140℃下捏合直至固化：
73.1g异佛尔酮二异氰酸酯
20.47g苯甲酰胺
21.29g三聚氰胺
8.5g PMMA SBUV。将获得的颗粒研磨成11μm的粒度(d99)。用三辊研磨机将所得颜料以15％的浓度引入胶版漆(Sicpa Holding SA)中并且在胶版印刷中以2g/m2印样重量印样。获得呈蓝色并且另外在280-350nm的范围内具有吸收带的印样。
印样显示高的对有机溶剂以及含水的酸和碱的稳定性，而纯吸收剂的印样是不耐受的。
Claims (16)
1.用于安全应用的颜料颗粒，包括：
-热固性材料基质，和
-多个嵌入其中的热塑性聚合物的核颗粒，其具有溶解在核颗粒中的特征物质，其中特征物质为有机或金属有机物质。
2.根据权利要求1的颜料颗粒，其中特征物质为荧光或磷光或光致变色或热致变色的特征物质或者UV或IR或VIS吸收染料。
3.根据权利要求1或2的颜料颗粒，其中荧光或磷光特征物质在UV光谱范围内是可激发的并且在可见光谱范围内发射。
4.根据权利要求1-3之一的颜料颗粒，其中荧光或磷光特征物质在UV光谱范围内或在可见光谱范围内是可激发的并且在IR光谱范围内发射。
5.根据权利要求1-4之一的颜料颗粒，其中形成能量转移体系的两种不同的发光染料以溶解的形式存在于核颗粒中，其中第一染料在激发后将其激发能部分或完全地转移至第二染料。
6.根据权利要求1-5之一的颜料颗粒，其中热塑性聚合物选自聚苯乙烯(PS)、聚丙烯酸酯、聚乙烯(PE)、聚丙烯(PP)、聚碳酸酯(PC)、聚酰胺(PA)、聚氨酯(PU)、聚脲(PH)、聚对苯二甲酸乙二醇酯(PET)或其它聚酯，优选地选自聚苯乙烯(PS)或者选自以下之一：聚丙烯酸酯聚甲基丙烯酸甲酯(PMMA)、聚乙酸乙烯酯(PVAC)、聚氯乙烯(PVC)、聚丙烯腈(PAN)，特别优选地选自聚苯乙烯(PS)或聚甲基丙烯酸甲酯(PMMA)。
7.根据权利要求1-6之一的颜料颗粒，其中热塑性聚合物的链长在1,000-1,000,000g/mol、特别地50,000-250,000g/mol的范围内。
8.根据权利要求1-7之一的颜料颗粒，其中热固性材料基质包括加聚物、优选地不同的单胺、二胺或三胺与三聚体型异氰酸酯单体、特别优选地异佛尔酮二异氰酸酯的异氰脲酸酯三聚体的混合物。
9.根据权利要求1-8之一的颜料颗粒，其中热塑性核颗粒以在0.1和25重量％之间、特别地3-20重量％的浓度存在于热固性材料基质中。
10.根据权利要求1-9之一的颜料颗粒，根据测试方法A5、优选地A30，其对甲苯、乙酸乙酯、盐酸(5％)、氢氧化钠溶液(2％)和次氯酸钠溶液(5％活性氯)是稳定的，其中测试之后保留的特征强度高于初始强度的80％。
11.根据权利要求1-10之一的颜料颗粒，根据测试方法A5，其对丙酮是稳定的，其中测试之后保留的特征强度高于初始强度的80％。
12.用于制造根据权利要求1的用于安全应用的颜料颗粒的方法，包括如下的步骤：
a)将有机或金属有机特征物质溶解于热塑性聚合物中以用此方式提供具有溶解于其中的特征物质的热塑性颗粒的步骤；和
b)将步骤a)中获得的具有溶解于其中的特征物质的热塑性颗粒引入热固性材料基质中的步骤，
c)将步骤b)中获得的产物研磨成颜料颗粒的步骤。
13.根据权利要求12的方法，其中步骤a)包括如下分步骤：
a1)将热塑性聚合物和有机或金属有机特征物质溶解在有机溶剂中，
a2)使用表面活性剂将步骤a1)的溶液分散在含水介质中；
a3)除去有机溶剂；
a4)分离核颗粒；
并且其中在步骤b)中，核颗粒的嵌入优选地通过核颗粒与加聚物的单体一起的捏合或挤出过程进行；
并且其中在步骤c)中，颜料颗粒的研磨进行至小于25μm、优选地小于12μm、特别优选地小于6μm的粒度(d99)。
14.墨浓缩物，其包括根据权利要求1-11之一的颜料颗粒，特别地以超过40％(重量百分数)的颜料颗粒的浓度。
15.用于胶版印刷、丝网印刷或钢凹版印刷的印刷墨，其包括根据权利要求1-11之一的颜料颗粒，优选地以1-40％(重量百分数)、特别优选地1-20％重量百分数的颜料颗粒的浓度。
16.有价文件，其包括根据权利要求1-11之一的安全颜料。
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| DE102015014526.6 | 2015-11-11 | ||
| DE102015014526.6A DE102015014526A1 (de) | 2015-11-11 | 2015-11-11 | Sicherheitspigment, lumineszierendes Polymerharz und Verfahren zum Herstellen desselben |
| PCT/EP2016/001864 WO2017080655A1 (de) | 2015-11-11 | 2016-11-09 | Sicherheitspigment, lumineszierendes polymerharz und verfahren zum herstellen desselben |
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| CN110846909A (zh) * | 2018-07-20 | 2020-02-28 | 宁波凯丽安科技股份有限公司 | 一种发红光的光致变色染料 |
| CN112011177A (zh) * | 2019-05-30 | 2020-12-01 | 金旸（厦门）新材料科技有限公司 | 一种pa/pmma复合材料和制备原料及其制备方法和应用 |
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| EP3842253B1 (en) | 2019-12-23 | 2024-03-20 | HID Global CID SAS | Uv curable and heat sealable ink |
| WO2022112459A1 (en) * | 2020-11-30 | 2022-06-02 | Merck Patent Gmbh | Light emitting polymer material particle |
| EP4052920A1 (en) * | 2021-03-01 | 2022-09-07 | Gleitsmann Security Inks GmbH | A method for continuously or semi-continuously numbering of banknotes using laser writing |
| CN115691854B (zh) * | 2022-10-11 | 2024-06-07 | 长春理工大学 | 磁光各向异性导电赝三色旗型纳米带阵列及其制备技术 |
| DE102023101913A1 (de) | 2023-01-26 | 2024-08-01 | Giesecke+Devrient Currency Technology Gmbh | Datenträger mit maschinenlesbarem Sicherheitsmerkmal, Herstellungsverfahren und Echtheitsüberprüfungsverfahren |
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- 2016-11-09 WO PCT/EP2016/001864 patent/WO2017080655A1/de active Application Filing
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| EP3374464B1 (de) | 2021-05-19 |
| US20180320015A1 (en) | 2018-11-08 |
| CA3004124A1 (en) | 2017-05-18 |
| WO2017080655A1 (de) | 2017-05-18 |
| EP3374464A1 (de) | 2018-09-19 |
| DE102015014526A1 (de) | 2017-05-11 |
| MX2018005804A (es) | 2018-08-01 |
| ES2882108T3 (es) | 2021-12-01 |
| CN108291139B (zh) | 2021-03-09 |
| HUE055337T2 (hu) | 2021-11-29 |
| CA3004124C (en) | 2022-03-15 |
| US10995231B2 (en) | 2021-05-04 |
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