CN103875026B - Verify method and apparatus and the application of this device of the secure file with the security feature that form is fluorescent printing element - Google Patents
Verify method and apparatus and the application of this device of the secure file with the security feature that form is fluorescent printing element Download PDFInfo
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- CN103875026B CN103875026B CN201280043461.6A CN201280043461A CN103875026B CN 103875026 B CN103875026 B CN 103875026B CN 201280043461 A CN201280043461 A CN 201280043461A CN 103875026 B CN103875026 B CN 103875026B
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- G—PHYSICS
- G07—CHECKING-DEVICES
- G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
- G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
- G07D7/06—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using wave or particle radiation
- G07D7/12—Visible light, infrared or ultraviolet radiation
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- G—PHYSICS
- G07—CHECKING-DEVICES
- G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
- G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
- G07D7/06—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using wave or particle radiation
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Abstract
Description
本发明涉及一种用于验证带有形式为至少一个荧光的印刷元件的安全特征的安全文件的方法和装置以及相应装置的应用。这种方法尤其可以通过智能手机执行或者这种装置可以是智能手机的集成部件。The invention relates to a method and a device for authenticating a security document with a security feature in the form of at least one fluorescent printing element and to the use of the corresponding device. In particular, the method can be carried out by a smartphone or the device can be an integrated part of the smartphone.
很早就由现有技术已知带有形式为发光物质的安全特征的安全文件,由此使得该安全文件能防伪或可验证。安全文件根据本发明尤其是其中存在防伪的需求的钞票、旅行护照、身份证、驾照、票或类似的文件或物体。Security documents with security features in the form of luminescent substances are already known from the prior art, thereby rendering the security document counterfeit-proof or verifiable. Security documents according to the invention are in particular banknotes, travel passports, identity cards, driver's licenses, tickets or similar documents or objects in which there is a need for security against counterfeiting.
EP1673231B1描述了一种有价文件,带有具有用于检查有价文件的至少两种不同的特征材料的有价文件基体。至少一种特征材料通过一种发光材料或发光材料的混合物形成。特征材料能够用可见的或红外的辐射照射,其中在红外的频谱范围内出现发射。基于检测到的发射进行真实性的检查。EP1673231B1 describes a value document with a value document substrate having at least two different characteristic materials for checking the value document. At least one feature material is formed by a luminescent material or a mixture of luminescent materials. Characteristic materials can be irradiated with visible or infrared radiation, with emissions occurring in the infrared spectral range. A plausibility check is performed based on the detected emissions.
EP0977670B1揭示了一种印刷的有价文件,带有形式为基于掺杂稀土金属的基质晶格的发光物质的真实性特征。基质晶格几乎在整个可见的频谱范围内吸收,使得所有的线在发光物质的可见的频谱范围内被压制。发光物质的激发区域与强光源,如卤素灯、闪光灯等的照射区域重合。然而也可以通过来自可见范围的光激发。EP0977670B1 discloses a printed value document with an authenticity feature in the form of a luminescent substance based on a matrix lattice doped with rare earth metals. The matrix lattice absorbs almost in the entire visible spectral range, so that all lines are suppressed in the visible spectral range of the luminescent substance. The excited region of the luminescent substance coincides with the irradiated region of a strong light source, such as a halogen lamp or a flash lamp. However, excitation by light from the visible range is also possible.
EP0991522B1包括一种带有发光物质的有价文件,其具有大体上位于红外-频谱范围内的发射频谱,当所述发光物质以不改变所述文件的最大的量混入到所述有价文件中时,所述发光物质只有在高的测量技术方面的开销的情况下才能通过常用的检测器查证。提供基于掺杂钬的基质晶格的材料作为恰当的物质。EP0991522B1 comprises a value document with a luminescent substance having an emission spectrum substantially in the infrared-spectral range, when the luminescent substance is mixed into the value document in a maximum amount that does not alter the document At this time, the luminescent substances can only be detected by conventional detectors with high measurement-technical outlay. Materials based on holmium-doped host lattices are provided as suitable substances.
EP0053183B1揭示了一种有价证券,具有形式为发光和吸收的物质的真实性特征,所述物质可通过不可见的和/或可见的光激发并且仅在不可见的光学频谱范围内发光。EP0053183B1 discloses a document of value which has an authenticity feature in the form of a luminescent and absorbing substance which is excitable by invisible and/or visible light and which emits light only in the invisible optical spectral range.
此外还应参考EP0052624B1、EP0053124B1、EP0053148B1、EP0975468B1和EP0975469B1,其中同样描述了带有发光的真实性特征的有价文件。发光材料的激发既可以在可见的频谱范围也可以在不可见的频谱范围中进行。作为附加的安全因素要指出的是,在可见的范围内应当尽可能不出现发射。Reference should also be made to EP0052624B1, EP0053124B1, EP0053148B1, EP0975468B1 and EP0975469B1, which likewise describe documents of value with luminous authenticity features. The excitation of the phosphor can take place both in the visible and in the invisible spectral range. As an additional safety factor, it should be noted that as far as possible no emissions should occur in the visible range.
为了验证安全文件通常需要专门的检测装置,这些检测装置大多数静止地运行并且仅提供给有限的用户群。此外,在一段时间以来一直追求为移动应用提供检测器。In order to verify security documents, special testing devices are often required, most of these testing devices are inactive and are only available to a limited group of users. Furthermore, providing detectors for mobile applications has been pursued for some time.
WO2006/056268A1和DE102004056007A1包含了一种移动的验证装置,用于检查旅行证件的真实性。验证装置包括用于识别合法用户的识别装置、用于基于识别装置的信号开启验证装置的开启装置、用于读取包含在旅行证件的页面上的图像或字母数字的信息的光学读取单元、用于根据预给定的算法处理由光学的读取单元提供的信号的数据处理装置、用于显示读取的数据以及验证结果的显示单元以及用于将读取的数据或验证结果加密传输到中央站的通信单元。按照一种优选的实施形式,移动电话可以用作图形显示单元、数据处理单元和通信单元。例如采用摄像头作为光学的读取单元,其优选具有包括可调制的、尤其是可脉冲的光源,如LED或激光二极管的照明装置。通过使用这种照明系统可以激发包含在印刷油墨的颜料中的安全元件,并且在此获得的信号同样被用于检查真实性。WO2006/056268A1 and DE102004056007A1 contain a mobile authentication device for checking the authenticity of travel documents. The authentication means comprises identification means for identifying the legitimate user, opening means for opening the authentication means based on a signal of the identification means, an optical reading unit for reading the image or alphanumeric information contained on the pages of the travel document, A data processing device for processing the signals provided by the optical reading unit according to a predetermined algorithm, a display unit for displaying the read data and verification results and for encrypted transmission of the read data or verification results to Communication unit of the central station. According to a preferred embodiment, the mobile telephone can be used as graphics display unit, data processing unit and communication unit. For example, a camera is used as the optical reading unit, which preferably has an illumination device with a modulatable, in particular pulsed, light source, such as an LED or a laser diode. Security elements contained in the pigments of the printing ink can be excited by using such an illumination system, and the signals obtained here are likewise used for authenticity checks.
在CN1462010A中记载了一种借助于移动电话识别伪造的钞票的系统。钞票借助于红外条形码加密。条形码被记录在中央计算机-数据库中。在钞票进入流通之后,可以借助于通过恰当的软件实现的、移动电话的钞票识别功能检查钞票的真实性。为此通过移动无线连接访问中央数据库。A system for identifying counterfeit banknotes by means of a mobile phone is described in CN1462010A. Banknotes are encrypted with the help of infrared barcodes. The barcodes are recorded in a central computer-database. After the banknotes have been put into circulation, the authenticity of the banknotes can be checked by means of the banknote recognition function of the mobile phone implemented by suitable software. For this purpose the central database is accessed via a mobile wireless connection.
CN101252612A揭示了一种移动电话,带有用于检查钞票真实性的系统。该系统包括设置在移动电话上的CCD-摄像机以及光源,所述光源设置在与CCD-摄像机相同的侧面上。光源优选包括红外线光源以及紫外线光源。系统还可以具有红外线滤波器和紫外线滤波器,所述红外线滤波器和紫外线滤波器可以借助于转送机构移动到所述红外线光源或紫外线光源。通过所述的系统,在移动电话中通常使用的CCD-摄像头可以检测钞票的安全特征。所述方案的缺点在于,需要在移动电话上进行额外的修改,如设置光源。CN101252612A discloses a mobile phone with a system for checking the authenticity of banknotes. The system comprises a CCD camera arranged on the mobile phone and a light source which is arranged on the same side as the CCD camera. The light source preferably includes an infrared light source and an ultraviolet light source. The system may also have an infrared filter and an ultraviolet filter which can be moved to the infrared light source or the ultraviolet light source by means of a transfer mechanism. With the described system, a CCD-camera commonly used in mobile phones can detect security features of banknotes. The disadvantage of this solution is that additional modifications are required on the mobile phone, such as setting the light source.
由US2006/0279732A1公开了带有集成式光谱学的传感器的移动电话。光谱学的传感器包括光源和照片传感器其中,移动电话已经存在的闪光灯和CMOS/CCD-图像-传感器被用作光源和照片传感器。借助于移动电话应当进行物体,如钞票、珠宝等的真实性检查。然而没有详细描述所使用的辐射的波长范围。A mobile phone with an integrated spectroscopic sensor is known from US 2006/0279732 A1. Spectroscopic sensors include light sources and photo sensors, wherein flashlights and CMOS/CCD image sensors already present in mobile phones are used as light sources and photo sensors. Authenticity checks of objects, such as banknotes, jewellery, etc., are to be carried out by means of a mobile phone. The wavelength range of the radiation used is however not described in detail.
US2005/0100204A1揭示了用于检测荧光的颗粒以检查文件的真实性的方法和装置。该装置包括带有集成式的光源和照片传感器的移动电话。US2005/0100204A1 discloses a method and a device for detecting fluorescent particles to check the authenticity of documents. The device includes a mobile phone with an integrated light source and photo sensor.
US2010/144387A1揭示了一种多功能的便携式电子装置,带有集成的验证功能。该装置例如可以是移动电话或者PDA。为了验证如钞票的有价文件,例如通过来自装置的光源的红光或蓝紫色的光激发相应的区域。由此导致的发射可以通过肉眼评估并且还借助于摄像机模块检测。借助于中央处理单元与给定的数据进行比较。验证结果在显示单元被输出。US2010/144387A1 discloses a multifunctional portable electronic device with an integrated authentication function. The device can be, for example, a mobile phone or a PDA. For authenticating documents of value such as banknotes, the corresponding regions are excited, for example, by red or violet light from a light source of the device. The resulting emission can be evaluated visually and also detected by means of a camera module. A comparison is made with the given data by means of the central processing unit. The verification result is output on the display unit.
EP1986162A1描述了一种用于真实性检查的装置和方法,其中,包括真实性特征的目标区域被用可见的或不可见的光激发,并且借助于照片传感器检测处于可见或不可见的频谱范围内的发射。EP1986162A1 describes a device and a method for authenticity checking, wherein a target area comprising an authenticity feature is excited with visible or invisible light and is detected by means of a photo sensor in the visible or invisible spectral range launch.
EP1672668A1研究了荧光的安全特征,其在可见的频谱范围内发光。为了激发,可以使用带有LED阵列的照明单元,该照明单元可以在不同频谱范围内发光。EP1672668A1 studies the security features of fluorescence, which emits light in the visible spectral range. For excitation, a lighting unit with an array of LEDs can be used, which can emit light in different spectral ranges.
WO2008/113963A1揭示了一种用于真实性检查的可移动的装置,带有两个相对布置的LED,所述LED发出可见光,该可见光借助于菲涅耳透鏡聚焦并且照射在一组安全元件上。借助于图像传感器检测由安全元件发出的光线并且由处理器继续处理。发出的光线处于可见的频谱范围内。检查的结果被光学或声学地信号表示。WO 2008/113963 A1 discloses a mobile device for authenticity checks with two oppositely arranged LEDs emitting visible light which is focused by means of a Fresnel lens and illuminates a set of security elements . The light emitted by the security element is detected by means of an image sensor and further processed by a processor. The emitted light is in the visible spectrum. The result of the inspection is signaled optically or acoustically.
WO2010/100378A2记载了一种用于光学分析物体或文件上的物质的方法。以可见的光线照射物体或文件,以激发物质,该物质接着发出可见光。为了使不能在可见光中检测到的独特的有色辐射可见,采用相应的滤光元件。WO 2010/100378 A2 describes a method for the optical analysis of substances on objects or documents. Shining an object or document with visible light to excite a substance that then emits visible light. Corresponding filter elements are used in order to visualize unique colored radiation that cannot be detected in visible light.
本发明所要解决的技术问题在于提供一种用于验证安全文件的装置、该装置的应用和方法。按本发明的装置的特点应当尤其是,该装置由简单的、可普遍获取的部件构成并且相比传统使用的验证装置廉价地实现。尤其追求这样地构造用于验证这种安全文件的装置和方法,使得所述装置和方法可以轻易地集成到移动电话、智能电话和类似的装置中。The technical problem to be solved by the present invention is to provide a device for verifying security documents, an application and a method of the device. In particular, the device according to the invention should be characterized in that it consists of simple, widely available components and is realized at a lower cost than conventionally used verification devices. In particular, it is desirable to design devices and methods for authenticating such security documents in such a way that they can be easily integrated into mobile phones, smartphones and similar devices.
按权利要求1所述的、用于验证安全文件的方法用于解决按本发明的技术问题。按权利要求4所述的、用于验证安全文件的装置也用于解决按本发明的技术问题。最后,本发明给出了一种按权利要求7所述的、这种用于验证安全文件的装置的应用。The method for verifying security documents according to claim 1 serves to solve the technical problem according to the invention. A device for verifying security documents according to claim 4 also serves to solve the problem according to the invention. Finally, the invention provides a use of such a device for authenticating security documents according to claim 7 .
按本发明的、用于验证安全文件的方法包括下述步骤:首先借助于在可见的频谱范围内发光的光源激发设置在安全文件的检查区域中的颜料状的荧光印刷元件。如尤其是在现代移动电话中应用的那样,优选使用用作闪光灯或拍照灯的LED-灯作为光源。然而,激发也可以通过连续的光源,如通过氖管、卤素辐射器或LED-照明装置实现。激发同样也可以通过自然的太阳光实现。为了激发优选使用的荧光印刷元件,通常蓝色的光就足够。由于激发从荧光的印刷元件发射光线。通过照片传感器检测颜料状的荧光印刷元件的发射并且接着评估。通过专门的应用程序进行评估,该应用程序也考虑不同的光源。照片传感器优选是移动电话的图像传感器,而应用程序可以作为所谓的APP安装在智能手机上。The method according to the invention for authenticating a security document comprises the steps of first exciting a pigment-like fluorescent printing element arranged in the inspection region of the security document by means of a light source which emits light in the visible spectral range. As is used in particular in modern mobile phones, LED lamps, which are used as flashlights or camera lights, are preferably used as light sources. However, excitation can also be effected by continuous light sources, for example by neon tubes, halogen radiators or LED lighting. Excitation can also be achieved by natural sunlight. In order to excite the preferably used fluorescent printing elements, blue light is usually sufficient. Light is emitted from the fluorescent printing element due to excitation. The emission of the pigmented fluorescent printing element is detected by a photo sensor and then evaluated. The evaluation is carried out by means of a dedicated application which also takes into account different light sources. The photo sensor is preferably the image sensor of the mobile phone, while the application program can be installed on the smartphone as a so-called APP.
在该评估中可以与安全文件的、没有设置荧光的印刷元件的其余表面(比较区域)进行比较或者与未激发的荧光印刷元件的图像拍摄进行比较。比较数据通常存储在数据库中,该数据库例如存放在移动电话中或者可在线获取。然而也可以在方法过程中产生比较所需的数据,方式是借助于激发的光源照亮安全文件的比较区域并且检测比较区域的发射。备选地,也可以在未激发的状态检测荧光的印刷元件并且用于比较。In this evaluation, a comparison can be made with the remaining surface of the security document (comparison area) of the printing element not provided with fluorescence or with an image recording of an unexcited fluorescent printing element. The comparison data are usually stored in a database, for example stored in a mobile phone or available online. However, the data required for the comparison can also be generated during the method by illuminating the comparison region of the security document with an excited light source and detecting the emission of the comparison region. Alternatively, fluorescent printing elements can also be detected in the unexcited state and used for comparison.
在最后的方法步骤中进行验证结果的输出,优选输出到移动电话的显示屏上。在需要时,该验证结果可以由移动电话传输到远方的接收者。In a final method step, the verification result is output, preferably on a display of the mobile phone. The verification result can be transmitted by the mobile phone to a remote recipient when required.
借助于按本发明的方法验证的安全文件具有形式为至少一个颜料状的荧光印刷元件的安全特征,其在电磁辐射的第一波长范围内可激发,以便发射第二波长范围中的电磁辐射,其中,第一和第二波长范围处于可见的频谱范围内。The security document authenticated by means of the method according to the invention has a security feature in the form of at least one pigment-like fluorescent printing element which is excitable in a first wavelength range of electromagnetic radiation in order to emit electromagnetic radiation in a second wavelength range, Wherein, the first and the second wavelength range are in the visible spectral range.
特别优选的是,使用变化形式的细颗粒的、无机LED-转换发光材料作为荧光的印刷元件,其加入到印刷颜料、印刷油墨或印泥中。在制造LED时使用的转换发光材料属于这一组,以便为了产生白光将半导体在蓝色区域中的发射的至少一部分转换到另一颜色区域中。Particular preference is given to using modified forms of fine-grained, inorganic LED-converting phosphors as fluorescent printing elements which are added to printing pigments, printing inks or printing pads. The conversion phosphors used in the production of LEDs belong to this group in order to convert at least part of the emission of the semiconductor in the blue region into another color region for the generation of white light.
按本发明的装置包括可自由编程的移动电话,带有用于发射可见频谱范围内的光线的光源和用于拍摄或测量可见频谱范围内的光线的照片传感器。这样配置可自由编程的移动电话,使得该移动电话能够将通过照片传感器拍摄或测量的由颜料状的荧光印刷元件发射的辐射与预定的数据进行比较并且可以信号化表示一致或偏差,以验证检查的安全文件的安全特征。The device according to the invention comprises a freely programmable mobile phone with a light source for emitting light in the visible spectral range and a photo sensor for recording or measuring light in the visible spectral range. The freely programmable mobile phone is configured in such a way that it is able to compare the radiation emitted by the pigment-like fluorescent printing element, taken or measured by a photo sensor, with predetermined data and can signal a coincidence or deviation to verify the inspection The security features of the security file.
按本发明的验证装置的一个重要优点在于,仅需要一个相应配置的移动电话。因此为安全文件的真实性检验提供了一种简单并且廉价的方案。验证装置可以提供给较广泛的用户群,其能够与地点无关地进行安全文件的检查。An important advantage of the authentication device according to the invention is that only one correspondingly equipped mobile phone is required. A simple and inexpensive solution is thus provided for the authenticity check of security documents. The verification device can be made available to a wider user group, which enables location-independent checking of security documents.
智能手机属于可自由编程的移动电话,其可以通过附加的程序(所谓的App)由用户单独加装新的功能。验证所需的光源以及照片传感器是按标准存在于智能手机中,因此不必改变现有的硬件。智能手机通常具有LED-光源,用于实现闪光或照明功能。借助于这种所谓的LED-闪光可以对用作安全特征的荧光印刷元件进行激发。智能手机-照片传感器,例如CCD-传感器、CMOS-传感器或者Foveon-传感器配备有10ms至50ms范围内的快门系统,尤其是33ms范围内的、波长范围在约360nm至1100nm的快门系统。这种照片传感器通常构造有RGB-虑色器和IR-阻隔滤波器,因为该照片传感器直至约1100nm都是敏感的并且尤其在780nm至1100nm的不可见的范围内具有高度的敏感性。Smartphones are freely programmable mobile phones, which can be individually equipped with new functions by the user via additional programs (so-called apps). The light source and photo sensor required for verification are present in the smartphone as standard, so no changes to existing hardware are necessary. Smartphones often have LED-light sources for flash or lighting functions. With the aid of such so-called LED flashes, fluorescent printing elements used as security features can be excited. Smartphone photo sensors, such as CCD-sensors, CMOS-sensors or Foveon-sensors, are equipped with shutter systems in the range of 10 ms to 50 ms, especially in the range of 33 ms, in the wavelength range from about 360 nm to 1100 nm. Such photo sensors are usually designed with RGB color filters and IR blocking filters, since they are sensitive up to approximately 1100 nm and have a high sensitivity especially in the invisible range of 780 nm to 1100 nm.
本发明的一个重要的优点在于,通过用作安全特征的荧光印刷元件实现在可见的频谱范围内的发射。因为这种发射处于可见的频谱范围内,所以这种发射能够在低耗费并且没有专门的检测器的情况下被检测,例如通过智能手机的彩色图像传感器检测。在由现有技术已知的方案中,替代前述方案通常通过使用的发光材料导致不可见的范围中的发射,该发射的检测明显更耗费。An important advantage of the invention is that the emission in the visible spectral range is achieved by means of the fluorescent printing element used as a security feature. Since this emission is in the visible spectral range, it can be detected with low outlay and without special detectors, for example by a color image sensor of a smartphone. In the solutions known from the prior art, the alternatives to the above usually result in emissions in the invisible range due to the luminescent materials used, the detection of which is significantly more complex.
按照一种有利的实施形式,用于激发荧光的印刷元件的第一波长范围在380nm到500nm之间。第一波长范围的平均波长优选在可见的频谱范围内,其中,其同样优选在380nm至500nm之间的波长范围内。对于一些实施形式,在420nm至470nm之间的平均波长或者在450nm至470nm之间的平均波长被证明是有利的。According to an advantageous embodiment, the first wavelength range for exciting the fluorescent printing element is between 380 nm and 500 nm. The average wavelength of the first wavelength range is preferably in the visible spectral range, wherein it is likewise preferably in the wavelength range between 380 nm and 500 nm. For some embodiments, an average wavelength between 420 nm and 470 nm or between 450 nm and 470 nm has proven to be advantageous.
荧光的印刷元件在第二波长范围内发光,其波长优选在可见的频谱范围内。第二波长范围的波长或平均波长优选在490nm到780nm之间或者在550nm到780nm之间的可见的频谱范围内。The fluorescent printing element emits light in the second wavelength range, preferably in the visible spectral range. The wavelength or mean wavelength of the second wavelength range is preferably in the visible spectral range between 490 nm and 780 nm or between 550 nm and 780 nm.
安全特征通常通过印刷技术施加到安全文件上或者集成在安全文件中。所使用的印刷颜料、印刷油墨或印泥优选具有聚合的粘结剂基质,在该粘结剂基质中均匀地分散有荧光的印刷元件。印刷颜料、印刷油墨或印泥借助于恰当的涂覆方法,如凹雕印刷、凹版印刷、胶印印刷、苯胺印刷、丝网印刷、喷墨印刷、转印印刷、再转印印刷、激光-转印-印刷、柔性印刷或者编号装置施加在安全文件上或者通过印刷内层和接下来的层压集成在安全文件中。The security features are usually applied to the security document by printing techniques or integrated in the security document. The printing pigments, printing inks or ink pads used preferably have a polymeric binder matrix in which the fluorescent printing elements are dispersed homogeneously. Printing pigments, printing inks or ink pads by means of suitable application methods, such as intaglio printing, gravure printing, offset printing, flexographic printing, screen printing, inkjet printing, transfer printing, retransfer printing, laser-transfer printing - Printing, flexographic printing or numbering means applied on the security document or integrated in the security document by printing the inner layer and subsequent lamination.
按照一种有利的实施形式,颜料状的荧光印刷元件具有在1μm至20μm的d50颜料分布。d50-值是平均颜料大小的尺寸。d50表示50%的颜料小于给定的值。在另一种实施形式中,d50颜料分布在μm以下的范围中,尤其是在纳米级的范围内被证明是有利的。在此,d50颜料分布有利地在3nm至30nm的范围内或者在100nm至500nm的范围内。According to an advantageous embodiment, the pigmented fluorescent printing element has a d50 pigment distribution of 1 μm to 20 μm. The d50-value is a measure of the average pigment size. d50 indicates that 50% of the pigment is less than the given value. In another embodiment, it has proven to be advantageous for the d50 pigments to be distributed in the sub-μm range, in particular in the nanoscale range. Here, the d50 pigment distribution is advantageously in the range of 3 nm to 30 nm or in the range of 100 nm to 500 nm.
按照一种优选的实施形式,荧光的印刷元件通过发光材料形成,该发光材料从下面的组中选出:According to a preferred embodiment, the fluorescent printing element is formed by a luminescent material selected from the following group:
-掺杂铕的碱土金属正硅酸盐发光材料和掺杂铕的碱土金属硅酸盐发光材料;- Europium-doped alkaline earth metal orthosilicate luminescent materials and europium-doped alkaline earth metal silicate luminescent materials;
-氮化物的发光材料;- luminescent materials of nitrides;
-掺杂铈的稀土金属-铝-镓-石榴石-发光材料;- Rare earth metals doped with cerium-aluminum-gallium-garnet-luminescent materials;
-发红光的(Ca,Sr)S:Eu2+,和- red-emitting (Ca,Sr)S:Eu 2+ , and
-发绿光的SrGa2S4:Eu2+。- Green-emitting SrGa 2 S 4 :Eu 2+ .
掺杂铕的碱土金属正硅酸盐发光材料或掺杂铕的碱土金属硅酸盐发光材料优选按照一般化学式构造:Europium-doped alkaline earth metal orthosilicate phosphors or europium-doped alkaline earth metal silicate phosphors are preferably structured according to the general formula:
MII 2SiO4:Eu2+其中,MII=Ca,Sr,Ba和/或M II 2 SiO 4 :Eu 2+ where M II =Ca, Sr, Ba and/or
MII 3SiO5:Eu2+其中,MII=Sr,Ba。在Eu2+-激活的正硅酸盐在激发时根据具体的发光材料成分在蓝色频谱范围内宽频地以在500nm至620nm之间的发射波长最大值发光时,在黄色或桔黄色的频谱范围内在550nm至610nm之间发光的硅酸盐具有明显更小的半值宽度的发射频谱。M II 3 SiO 5 :Eu 2+ where M II =Sr, Ba. When excited, Eu 2+ -activated orthosilicates emit broad-band in the blue spectral range with an emission wavelength maximum between 500 nm and 620 nm, depending on the specific luminescent material composition, in the yellow or orange spectrum Silicates that emit in the range between 550 nm and 610 nm have an emission spectrum with a significantly smaller half-value width.
掺杂铈的稀土金属-铝/镓-石榴石-发光材料优选按照一般化学式构造:MIII 3(Al1-xGax)5O12:Ce3+其中,MIII=Y,Gd,Tb,Lu并且0≤x≤1。这种发光材料类的特征在于,通过改变稀土元素阳离子和Ce3+-含量以及通过在阴离子部分晶格中的置换,也就是通过镓-铝置换,发射波长能够在可见频谱的宽范围内也就是从500nm至600nm的范围内移动。The rare earth metal-aluminum/gallium-garnet phosphor doped with cerium is preferably structured according to the general chemical formula: M III 3 (Al 1-x Ga x ) 5 O 12 :Ce 3+ where M III =Y, Gd, Tb ,Lu and 0≤x≤1. This class of luminescent materials is characterized in that, by varying the cation and Ce3+-contents of the rare earth elements and by substitution in the anion partial lattice, that is to say by gallium-aluminum substitution, emission wavelengths can be obtained in a wide range of the visible spectrum, ie from Move within the range of 500nm to 600nm.
发红光的(Ca,Sr)S:Eu2+和发绿光的硫代镓酸锶SrGa2S4:Eu2+具有在约650nm至约525nm范围内的λmax值。The red-emitting (Ca,Sr)S:Eu 2+ and the green-emitting strontium thiogallate SrGa 2 S 4 :Eu 2+ have lambda max values in the range of about 650 nm to about 525 nm.
尤其优选的是通过氮化物的发光材料形成荧光的印刷元件。该发光材料优选掺杂Eu2+或Ce3+作为激活剂。该发光材料的基质晶格优选通过M-Si-N结构的氮化硅酸盐、通过M-Si-O-N结构的硅基氧氮化物、通过M-Al-N结构的铝氮化物、通过M-Si-Al-N结构的硅铝氮化物或者通过M-Si-Al-O-N结构的硅铝氧氮化物构成。Particularly preferred are printed elements which are fluorescent by means of nitride phosphors. The luminescent material is preferably doped with Eu 2+ or Ce 3+ as activator. The host lattice of the luminescent material preferably passes through the nitrided silicate of the M-Si-N structure, the silicon-based oxynitride through the M-Si-ON structure, the aluminum nitride through the M-Al-N structure, through the M - Si-Al-N structure of Si-Al-Nitride or Si-Al-O-Nitride of M-Si-Al-ON structure.
特别优选的是,荧光的印刷元件由氮化物的发光材料构成,该发光材料具有M-Si-N、M-Si-O-N、M-Al-N、M-Si-Al-N或M-Si-Al-O-N结构的基质晶格并且掺杂Eu2+作为激活剂,或者具有M-Si-N、La-Si-N、M-Si-Al-N或M-Si-Al-O-N结构的基质晶格并且掺杂Ce3+作为激活剂。在此,M表示金属,该金属优选通过Ca,Sr和/或Ba构成。Particularly preferably, the fluorescent printing element consists of a nitride phosphor with M-Si-N, M-Si-ON, M-Al-N, M-Si-Al-N or M-Si - Al-ON structure host lattice and doped with Eu 2+ as activator, or with M-Si-N, La-Si-N, M-Si-Al-N or M-Si-Al-ON structure host lattice and doped with Ce3 + as activator. Here, M stands for a metal which is preferably formed by Ca, Sr and/or Ba.
在以下的表格1和2中归纳了掺杂Eu2+或Ce3+的氮化物发光材料的重要代表,并且说明了其表明特征的发射波长。Important representatives of Eu 2+ - or Ce 3+ -doped nitride phosphors are summarized in Tables 1 and 2 below and their characteristic emission wavelengths are indicated.
表1Table 1
表格2Form 2
在此示例性地列举的各种发光材料应当不表示限制。也可以采用其它恰当的发光材料,这些发光材料在激发之后在蓝色或可见的频谱范围内发射可见光,以及采用不同发光材料的混合物。此外,一种优选的实施形式在于,尤其是那些也被用于制造发白光的LED的转换发光材料以恰当的方式通过改变晶格成分、激活剂浓度和/或通过共掺杂其它不同特性的稀土金属离子改性并且以这种形式作为按本发明的荧光印刷元件使用。The various luminescent materials exemplarily listed here should not represent limitations. It is also possible to use other suitable phosphors which, after excitation, emit visible light in the blue or visible spectral range, as well as mixtures of different phosphors. Furthermore, a preferred embodiment consists in that, in particular, those conversion phosphors which are also used for producing white-emitting LEDs are suitably modified by changing the lattice composition, the activator concentration and/or by co-doping other different properties The rare earth metal ions are modified and used in this form as phosphor printing elements according to the invention.
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Granted publication date: 20161026 |