DE102005045642B4 - Inorganic marker particles based on natural microorganisms for the identification of products for their proof of originality and method of production - Google Patents

Abstract

Inorganic marker particles based on natural microorganisms with a specific surface and characteristics specificity for the detectable labeling of products with known original information for their proof of originality,
marked by
an embodiment of the marking particles as biomineralized shell structures of biological microorganisms of a biomineralizing organism group with a specific individuality of the optical appearance of the three-dimensional shell structure selectively selected according to the criterion of a highly complex original information
Selecting one or more rare biomineralizing organism groups whose biological microorganisms produce biomineralized shell structures, from a particular sediment or field sample or a technically modified culture according to the criterion of highly complex original information of the biomineralized shell structure,
• Obtaining the biomineralized shell structure of the selected group of organisms and
• technical preparation of the biomineralized shell structures in terms of purity, size and surface technical preparation of the biomineralized shell structures by cleaning, mixing, sieving or crushing and / or by etching or ...

Description

The This invention relates to inorganic marking particles the basis of natural microorganisms with a specific individuality regarding surface and Characteristics for the detectable labeling of products with a well-known original information for their proof of originality and to a process for the preparation and use of such Marking particles.

Valuable, high-priced or highly taxed products such. Eg banknotes, Shares and certificates, but also so-called "label products" such as cosmetics, sound carriers, clothing, Shoes, handbags, watches and alcohol or tobacco are often faked. To EU data trade in counterfeit goods, illegal overproduction, parallel and Re-imports already account for 10% of world trade, causing international damage from 200-300 Equals billions of euros. The companies involved must be next to Sales losses in addition Image damage and at worst even product liability processes for counterfeit products to accept. Another current problem besides the product imitation is the product theft, especially of high-quality vehicles. The known in vehicles security features, such as The serial number engraved in the vehicle frame can be light be removed so that a unique identification on retrieval stolen vehicle is often difficult. The theft of a However, clearly identifiable vehicle is at considerable risk connected and therefore will be left rather.

aim A product security against imitation and theft is through appropriate individual, highly unique features on the product guarantee, that this is clearly recognizable as an original. For this purpose a distinction is made between public visible features (eg holograms) and non-public ones Features that are available with either a publicly available special reader (eg UV lamps for the detection of security fibers in banknotes) or only with hard-to-find devices (such as For example, electron microscopes) become visible. A row of different technical solutions for product protection is out known in the art.

State of the art

In the DE 198 09 085 A1 is described as a visually verifiable security feature a textile-like line structure of elaborately structured colored, coated or multi-component filaments. With the help of braiding the filament surface structure can be realized directly on products. In addition to threads, pigments, ie color particles, are often used for product protection. Diffractive effect pigments are for example from DE 10 2004 055 291 A1 known. In this case, colored platelet effect pigments with several layers, some of which contain colorants and some groove and lattice structures, are used. Optically detectable color effects can be detected directly and angle-dependent. Fundamentals about the use of multilayer interference pigments, including their calcination for protection against destruction, is the DE 100 51 062 A1 refer to.

Characteristic synthetic DNA sequences are used in an ink according to the JP 2002-167530 admixed. The DNA sequences contain user-specific data. By completing a strand of DNA on the product with the complementary DNA strand in a reading pen, detectable light is emitted. Biological safety pigments, in particular using bacteriorhodopsin (crystalline retinal protein from halobacteria) were reported by the Institute of Physical Chemistry of the Philips University of Marburg (see press release on Biotechnica 2003, available on the Internet at www.uni-marburg.de/zv/). news / archive / press03 / 02-10-03.html, as of 17.08.2005). The photochromic retinal protein shows a characteristic light-induced and reversible color change between violet and yellow. Radio frequency identifiable security features are described in the article "Creo and XINK Laboratories Announce World's First Security Ink for High Volume Flexographic RFID Antenna Production" (available on the Internet at http://www.creo.com/global/about_creo/news/2005/050526y .htm, as of 09.08.2005).

Nanoparticles with three-dimensional periodic structures on the model of opal-like structures, resulting in identifiable periodicities in the optical wavelength range are, for example, from US 2001/0019037 A1 or the US 6,261,469 B1 known. Color coded marking particles with multiple color layers are used in the DE 102 36 409 A1 disclosed. The use of water-soluble nanocrystals for product protection is known from US Pat US 2004/02030170 A1 known. Fluorescent nanocrystals are used in the US 6,576,155 B1 , polarizing, cholesteric nanocrystals in the JP 2003-073600 disclosed. The spectral encoding of ink by admixture of fluorescent semiconducting nanocrystals as quantum dots is described in US Pat US 2004/0262400 A1 described. The use of magnetic nanoparticles is described in an article written on 04.11.2003 by wissenschaft.de (available at http://www.wissenschaft.de/wissen/news/dru cken / 231687.html, as of 27.07.2005). The construction of nanoparticles with fluorescent or phosphorescent properties in a security printing fluid is described in US Pat WO 03/052025 A1 , a printing process using this security printing fluid in the WO 03/051643 A1 disclosed by the company NanoSolutions.

Farther state of the art in the company prospectus "Trusted Products - Marken- and product protection "version 1.3d of the company mut GmbH, Wedel (available on the Internet under http://www.mut-gmbh.de/de/projects/image_processing/elemente/20040701163430.html) Stand 26.07.05) and the newsletter "News @ mut" 1/2004 (article "Trusted Products prevents counterfeiting" by Heino Prüß, in the internet available at www.mut-gmbh.de/en/company/press_releases/20040423120737/200404231207 37.pdf, Stand 25.08.05). In the aforementioned publications become forgery-proof Nanoparticles described as a tracer (marker) in a product introduced or with commercial Inkjet printers can be applied. The marking particles are very small and bare Eye not visible. They reflect a specific spectrum, so they only become visible when illuminated with special UV light. The surface and The properties of the marking particles can be for each customer and for each batch individually created. The individuality manifests itself in that the marking particles only when irradiated with light a very specific wavelength become visible and one for these marking particles give off characteristic spectrum. The individual surfaces and enable properties thus the identification by the so-called "spectral Fingerprint". Furthermore, the marking particles are inorganic. That's why they react not with the product material. They are heat resistant and resist acids and alkalis. It can be a very secure two-stage security system from nanoparticles and cryptography (encrypted information) applied become. A possible third stage represents the production as needed. Each order the customer is registered. You will only get such an amount of tag particles assigned as for the product batch needed becomes. The individually changed Properties of each batch are stored in a database. Special spectral detection systems for marker recognition will be also offered. The partner of the company courage in the field of marking particles is the company NanoSolutions, Hamburg.

Out the last mentioned publications is in connection with the two above - cited documents the Fa. NanoSolutions recognizable that the individual design of the surface the marking particle excluding the generation of different Spectra (reflection spectrum and with light excitability also emission spectrum) serves. Also appreciated in the two US papers above Marking particles with the three-dimensional periodic structures Following the example of opal structures work in this sense. By the generation of certain periodic structures of the tag particles Special reflection spectra are generated. Same goes for the above appreciated in the DE-writings colored platelet-shaped effect pigments, which in a layer groove and grid structures to produce have special reflection spectra by optical refraction. The marking particles used for product protection from the prior art With an individually structured surface, only the Generation of characteristic spectra, which with appropriate optical Suggestion are detectable. The preparation of such marking particles with reliable reproducible spectral properties is correspondingly expensive. The individual change the labeling particle for batch labeling requires extensive accompanying testing and control measures to ensure a reliably detectable To cause spectral change. Continue to be in principle special lighting equipment needed to the specific spectrum to stimulate. To prove the spectrum then turn completely special detection devices needed. These are each on Marking particles with changed To adapt spectra.

One Reworking the marking particles is expensive, but in the achievement of identical security features thoroughly feasible. The Security features to be protected But products should be impossible or just to me extreme effort to copy, but a relative allow easy identification. Although the development of new Characteristics driven by new, purely technical possibilities As a rule, these are also possible counterfeit documents Available.

Furthermore, the use of microscopic biogenic structures for the identification of the origin of objects is known from the prior art. Fibers, sediment particles or even diatoms (diatoms) are used. Since the composition of the diatom community is often highly specific for certain waters and for specific periods of time, there are examples where the diatoms are used in forensics, for example, to isolate the place where a victim has drowned. The respective identifiable diatom community is then located in the lung tissue of the dead. Similarly, diatoms are used in archeology to analyze the origin of ceramics. Find Cups of special species in clay matrix, its origin can be determined very accurately. Deposited silica shells are also referred to as "kieselguhr", but kieselguhr always includes a complex mixture of the shell structures of various diatoms that have settled at the point of origin and other elements, such as sand (see the publication "The Diatom Applications for the Environmental and Earth Sciences ", edited by EF Stoermer et al., Cambridge University Press 1999, pp. 389-418).

From the publication "Diatomeen" of the Microbiological Association Munich eV by Dr. J. Henkel, 2005 (available on the Internet under the web address http://www.mikroskopie-muenchen.de/diatomeen.html, as of 28.07.2005) It is also known to use diatomaceous earth as an abrasive, for the filtration of beer and wine, and as a substrate for cosmetics.Also, kieselguhr was also needed for the production of dynamite to make the explosive explosive oil transportable in diatomaceous earth This publication also mentions that diatoms have extremely fine structures in their shell construction that can not yet be mimicked in terms of fineness and regularity even by today's advanced nanotechnology.Therefore, the shells of certain types of diatoms serve as test objects for the resolving power or the performance of microscope objectives is it from the US 2005/0025680 A1 It is known to prepare mesoporous silica particles and to use them for example as an ink absorbent in an inkjet printer paper. The document clearly shows how complex the manufacturing process is. In this case, no emphasis is placed on a high degree of reproduction due to the applications of the particles produced, but rather attempts to produce a specific diameter.

In the WO 87/06383 A1 the use of spores of bacteria or fungi as well as viruses for anti-counterfeiting is described. However, their envelope structures are not used as detection features, but their inherent genetic information. The detection of this information is extremely time-consuming and costly and reserved for authorized personnel only.

In the US 3,861,886 A from which the invention proceeds as the closest prior art, the marking of liquids, such as petroleum, is described for their origin, for example with glass microparticles as inorganic marking particles. The glass microparticles have various detectable properties in terms of size and shape. Microparticles with a size of between 10 nm and 500 μm are used. The skeletons of marine creatures can also be used, as they have distinctive shapes and therefore a specific individuality in terms of surface and properties. Thus, inorganic microparticles based on natural microorganisms are used for the detectable labeling of products with known original information for their proof of originality. The shape of these bio-microparticles carries thereby a source information that is not detected directly, but indirectly with special methods that map the properties of a totality of particles in the form of spectra or patterns. However, the microparticles used are not absolutely unique in their design and thus relatively easy to relate, so that they can only be used as non-public features. However, due to their secret arrangement and their elaborate detection, they can only be detected by authorized specialist personnel.

task

outgoing from the nearest State of the art regarding the known marking particles with individually structured surface for imitation protection the task for see the present invention therein, inorganic tag particles based on natural Microorganisms of the type described above are available which are technically processed in a special way and in a simpler way Way are directly optically detectable. There should be a great variability in the characteristic surface structuring to disposal Although reliable reproducible, but is safe from unauthorized imitation. A manufacturing process should ensure these criteria but still be relatively easy in its course. In the application The label particles are designed to be easy to identify and flexible be usable. The solution according to the invention for this task is different from the claims To take categories. Advantageous developments are each in the subclaims shown and explained in more detail below in connection with the invention.

• • Auswählen einer oder mehrerer seltener biomineralisierender Organismengruppen, deren biologische Mikroorganismen biomineralisierte Schalenstrukturen erzeugen, aus einem speziellem Sediment oder Freilandprobe oder einer technisch modifizierten Kultur nach dem Kriterium einer hochkomplexen originalen Information der biomineralisierten Schalenstruktur,
• • Gewinnen der biomineralisierten Schalenstruktur der ausgesuchten Organismengruppe und
• • technisches Aufbereiten der biomineralisierten Schalenstrukturen hinsichtlich Reinheit, Größe und Oberfläche erfolgende technische Aufbereitung der biomineralisierten Schalenstrukturen durch Reinigen, Mischen, Aussieben oder Zerkleinern und/oder durch Ätzen oder Beschichten einer oder mehrerer gewonnener biomineralisierter Schalenstrukturen,

wobei ein solches komplexes Erscheinungsbildes der dreidimensionalen Schalenstrukturen der Markierungspartikel durch die technische Aufbereitung der biomineralisierten Schalenstrukturen hergestellt wird, dass eine direkte Nachweisbarkeit der an einem Produkt applizierten Markierungspartikel durch eine optische Betrachtung möglich ist.The marking particles according to the invention are characterized by a formation of the marking particles as biomineralized shell structures of biological microorganisms of a biomineralizing organism group with a specific individuality of the optical appearance of the three-dimensional shell structure specifically selected on the criterion of a highly complex original information. The marking particles according to the invention can be prepared by

• • selecting one or more rare biomineralizing groups of organisms whose biolo microorganisms produce biomineralized shell structures, from a special sediment or field sample or a technically modified culture according to the criterion of highly complex original information of the biomineralized shell structure,
• • Obtaining the biomineralized shell structure of the selected group of organisms and
• Technical preparation of the biomineralized shell structures with regard to purity, size and surface technical preparation of the biomineralized shell structures by cleaning, mixing, screening or crushing and / or by etching or coating one or more recovered biomineralized shell structures,

wherein such a complex appearance of the three-dimensional shell structures of the marking particles is produced by the technical preparation of the biomineralized shell structures, that a direct detectability of the applied on a product marker particles by optical observation is possible.

Due to the technical preparation of the selected shell structures, a unique individualization takes place in the invention. The shell structures themselves or the organisms producing them can be technically processed or modified. The technical preparation of the shell structures is preferably carried out by cleaning and screening to remove unwanted foreign bodies and shell structures, mixing to bring together different shell structures or crushing to divide larger shell structures into concise fragments. This technical preparation makes the natural shell structures usable for the marking particles and adapted to the particular application. Furthermore, etching or coating of the biomineralized shell structures can take place. If, for example, SiO ₂ · nH ₂ O (silicate) is etched with hydrofluoric acid HF (alkaline pH values approx.> 8.5), this results in a loss of mass of the particles, as a result of which a change in the structure and a reduction in the sedimentation rate are achieved. CaCO ₃ particles (calcite) can be appropriately etched by acidic pH values. Coating, for example with Au, C or Pt, can be done, for example, by sputtering or vapor deposition, thereby achieving a change in the conductivity and solution properties of the mineralized shell structures. Furthermore, a spectral surface modification can be achieved by coating.

in the Contrary to purely technically generated marking particles point the technically modified biogenic marker particles after the Invention based on fractal and three-dimensional Based on a much higher structural complexity. The Selection of a mineral material as a basis for marking particles guaranteed about that In addition, extensive protection against thermal, chemical and microbial destruction at of manufacture and in use. The biogenic marker particles are over it In addition, inert and burden neither the product nor the surrounding Environment or the users. Furthermore, they own because of their mineralized shell construction basically a very high mechanical Stability.

With The invention relates to technically processed, unique biogenic Structures for the technical individualization of imitation and theft to be protected Products, resulting in a significantly increased counterfeiting and theft protection results. This will be very individual marking particles Their basic individuality is offered firstly by a rare one Occurrence of the mineralized shell structures producing biological microorganisms in nature and secondly by their special technical treatment in terms of purity, size and surface is justified. In doing so, the biomineralized shell structures pass through them Connection of species-specific biological structures with a technical preparation unique information in robust biogenic Microstructures available. Any usable shell structure suitable for use as a tag particle selected according to the criterion of highly complex original information is already unmistakable in its original geometry. by virtue of morphological features can the shell structures clearly one of the very many types of organisms assigned and thus systematized. By this kind specificity of the shell structures is their independent high reproducibility, but only under the supervision of a highly specialized Specialist, sure assured. additionally the technical preparation changes the individuality of the marking particles further improved. Here, purity is a criterion. At the marked Product occurring foreign particles or other shell structures, the not correspond to the original information, indicate a falsification of the product. The size of the shell structures is also adjustable by selection or crushing. Farther can on the surface the marking particles different coatings, for example reflective, fluorescent or phosphorescent colors, for further Individualization be appropriate.

Preference may also be given to predetermined mixtures of the processed biomineralized shell structures of different biological microorganisms. Any number of highly specific mixtures can be prepared and both uniform marking particles and multiforme marking particles are provided. All marking particles are unmistakable on their own geometry alone. However, a mixture of different manifestations, which, however, still clearly differs from natural mixtures, increases the protection against counterfeiting according to the number of components in the mixture many times over.

Prefers it is the marking particles according to the invention biomineralized shell structures of diatoms, radiolarians, Synurophycae, coccolithophores or Magnetospirillum spp. when biomineralizing organism groups. In this case, the particle size of the marking particles depending on application and verification requirements (public / non-public Characteristics recognizable with / without aids) preferably between 30 nm and 2 mm. It can the smaller and smallest marking particles than dry or dissolved powder be applied on or in the product. The larger and largest marking particles, on the other hand, can placed as single marks on exposed parts of the product become. A combination of both is also possible. Because of the big diversity in recent and fossil species (about 100,000 species) as well as genetically modifiable crops Diatoms and the other biomineralized organisms a very big reservoir at possible, distinctive shell structures.

• • Auswählen einer oder mehrerer seltener biomineralisierender Organismengruppen, deren biologische Mikroorganismen biomineralisierte Schalenstrukturen erzeugen, aus einem speziellem Sediment oder Freilandprobe oder einer technisch modifizierten Kultur nach dem Kriterium einer hochkomplexen originalen Information der biomineralisierten Schalenstruktur,
• • Gewinnen der biomineralisierten Schalenstruktur der ausgesuchten Organismengruppe und
• • technisches Aufbereiten der biomineralisierten Schalenstrukturen durch reinigen, Mischen, Aussieben oder Zerkleinern und/oder durch Ätzen oder Beschichten einer oder mehrerer gewonnener biomineralisierter Schalenstrukturen.

The production processes for producing the marking particles based on natural microorganisms according to the invention can vary, are highly efficient, relatively inexpensive and ensure uniqueness and perfect reproducibility. Highly specialized manufacturing expertise is required to provide additional reliable protection against counterfeiting. A preferred method of producing the marking particles according to the invention is characterized by

• Selecting one or more rare biomineralizing organism groups whose biological microorganisms produce biomineralized shell structures, from a particular sediment or field sample or a technically modified culture according to the criterion of highly complex original information of the biomineralized shell structure,
• • Obtaining the biomineralized shell structure of the selected group of organisms and
• • technical preparation of the biomineralized shell structures by cleaning, mixing, screening or crushing and / or by etching or coating one or more recovered biomineralized shell structures.

By selecting one or more rare biomineralizing groups of organisms may be uniform Labeling particles with identical appearance or multiforme Marker particles with a mixed appearance, next to the specific individuality every single shell structure in itself even the mixed Composition of different shell structures another Security feature is produced.

Already The selection and procurement of suitable microorganisms can be designed in this way be that for it a copycat practically impossible is to get them too. Preferably, a selection a rare biomineralizing group of organisms from Antarctic Species, species from isolated lakes on islands or from remote mountain lakes respectively. So can very rare (special fossil deposits) or hard to reach deposits (Deep sea or remote ecosystems, about isolated lakes in northern Canada). scientific Although institutes and collections hold a large number of cultivated ones and fossil biomineralized unicellular organisms. Still, it is for scientific Purposes often very difficult, certain species even in small quantities to procure and / or to cultivate. The selection for further processing to marking particles will be quite difficult on such focus on procuring species.

Next the direct procurement of suitable microorganisms can this also be obtained by cultivation. A cultivation of live For example, taken and isolated microalgae species requires a high level of very special knowledge that requires a biological education. For the isolation, determination, cultivation and modification of biomineralized Structures are needed very specialized skills that from counterfeiters are much harder to provide than simple technical expertise.

• • geringes Verändern der Konzentration der in der Kultur zu Verfügung stehenden Nährstoffe (z. B. Silikat bei Kieselalgen)
• • erzwungenes Fusionieren der Zellen zwischen unterschiedlichen Arten von biologischen Mikroorganismen in einer biomineralisierenden Organismengruppe,
• • Einbringen von artfremden Substanzen oder Elementkonzentrationen und/oder
• • gentechnisches Verändern, wie z. B. gezieltes Mutieren zur Erzeugung von knock-out-Mutanten.

The highly specialized individuality of the microparticles used can be achieved in their extraction by culturing by a technical modification of the cultivation conditions of the shell structure-producing microorganisms, so that already systematically altered shell structures are produced. The modified microparticles can then be processed further technically. In the technical modification, it may be preferable to act

• • little change in the concentration of nutrients available in the culture (eg silicate in diatoms)
• Forced fusion of cells between different types of biological microorganisms in a biomineralizing organ nismengruppe,
• • introduction of alien substances or element concentrations and / or
• • genetically modified, such. B. targeted mutation to generate knock-out mutants.

To the Area of cultivation thus, for example, selection, mutations, cell fusion. By certain changes the culture conditions, the type-specific morphology, for example modified by diatoms. This is the case with diatoms low silicate concentrations and the addition of germanium on strong the appearance of the bowls. Targeted mutations (knock-out mutants) can also to a systematic change of the shell structures to lead. Likewise forced cell fusion between different species of a genus usually lead to structures that do not exist in nature. Different type Substances or elemental concentrations (for example germanium, fluorescent dyes, silicate or strontium, magnesium) may be used during the Growth into the biomineralized structures. For this Modifications require highly specialized knowledge.

The The aforementioned method steps can preferably also be combined so that a variable combination of the various selection and modification options is reached. The combination can only be one single biomineralizing organism group or a mixture of several be related to biomineralizing organisms groups. For every special Application then becomes several types of biomineralized shell structures mixed in a specific, unique ratio. It should each introduced a modified structure for high security applications be, there not to exclude is that the structures in the academic field of interest electron microscopy to be examined. this could conversely, as part of a cooperation for the regular monitoring of certain Products are used. After all can for further security increase still a changing use of the various combination options done so a very big Variety of different, but always clearly identifiable Marking particles can be produced. One to the respective Needs adapted, regular change The composition of the marking particles ensures that an imitation through procurement and production of the relevant or similar Organisms not feasible in time is.

A particular application of the invention provided with the invention special, based on the shell structures of natural organisms Labeling particle provides a direct detectability of the applied Marking particles in the form of technically processed biomineralized Shell structures on the product by a visual inspection of the complex appearance of the three-dimensional shell structures the marking particle. additionally spectrally Components are therefore not necessarily required for verification. The marking particles according to the invention or their complex three-dimensional appearances can through easy viewing - depending on size even with the bare one Eye - and compare reliably recognized with the familiar model in their specific individuality become.

Generally can be applied the marking particles according to the invention for tampering protection of finished products by incorporation or application (for example in or on packaging, banknotes or security-related documents, such as securities, shares, secret documents, identity cards or tickets) or by mixing in as an ingredient (for example, cosmetics, Cigarettes, medicines). These may be the starting materials for example, banknotes, varnishes, printing inks, adhesives, Plastics or writing inks act. As an application method for the Marking particles are, for example, all printing methods, Painting process, papermaking process, plastic manufacturing process or emulsion method. It is important in the application the marking particle on or in the product on the marking particles exerted To know the pressure to make the marking particles their physical Select properties accordingly. The marking particles can in printing inks for the different printing processes are incorporated. flexo inks, Gravure and screen printing processes are not critical. Optionally occurring Problems can be met with a careful Selection of the size of the marking particles be countered (Inkjettinte particle size up to about 0.6 microns up to 1 mm for the other printing methods).

The marking particles according to the invention can be positioned as a public feature (for example as a hologram). The detection with the naked eye is readily possible with marking particles having a size in the range from 1 mm to 2 mm. From a size of about 100 microns, the shell structures can be detected, for example, with a thread counter (10x magnification) or magnifying glass. Depending on the design of the nanoparticles, for example equipment with a fluorescent color, it is also possible to observe them in special light, for example in UV light with a publicly available special reader (for example a banknote validator). Positioning as a non-public feature is also possible. The auxiliary means of proof are then correspondingly more complex and difficult to obtain in the public. This may be, for example, a light microscope, a scanning or transmission electron microscope or an apparatus for electron holography in the detection of magnetic marking particles. To further improve anti-imitation protection, the marker particles of the invention may be combined with cryptographic features. These are, for example, the application of the marking particles in certain patterns, for example barcode patterns. Furthermore, the optical and haptic properties of the printed surfaces can be demonstrably changed by admixing larger amounts of the marking particles in printing inks.

By Deposit of the original information regarding the geometric shape or shapes of the tag particles (eg, photo) can be made by comparison a clear identification of the labeling particles or the Mixture of it done. Here, the deposit in special Databases are made available to the respective auditor of originality. But it can also be done in-situ deposit directly on the product, for quick and easy access to the original information to reach. This can be, for example, the incorporation the geometric shape of the marking particle or particles in the product to be protected act as a watermark.

Farther can The marking particles are applied to a product against theft to protect, since the product can be clearly identified by the marking particles is and remains. This can be a secure transfer deposition of Labeling particles take place in the product. For example, uniforme or multiform biogenic marker particles according to the invention, which are photographed and documented in a database, interchangeable in a clear plastic badge or other carrier material integrated and visible (eg sealed in the windscreen) or invisibly attached to a number on vehicles become. Other applications of the marking particles, such as directly in the window glass or in the vehicle paint, are also possible. There the procurement of the technically manipulated marking particles extremely difficult and also every single shell structure, similar to a fingerprint, already has an individual pattern, there is no way copy the tag particles in any way. This applies, unlike similar, Chip- or hologram-based systems, also for the manufacturer of the plaques. Thus, you can z. B. vehicles are very safe individualized. In addition, needs there are no aids except possibly a medium magnification (10-20 ×) and the query of a database, to unambiguously identify a stolen vehicle

embodiments

forms of training the marking particles according to the invention and their production process explained in more detail with reference to the schematic figures. Showing:

1A ... 1G various biomineralized shell structures of the prior art,

2 a mixture of biomineralized shell structures,

3 an application of the marking particles to a product to be protected and

4 SEM images of marking particles in a printing varnish.

The 1A shows various biomineralized shell structures of diatoms as drawings by Ernst Haeckel. The book "Art Forms of Nature" by Ernst Haeckel, reprinted in 1998 of the first edition in 1904, Prestel Verlag, further color plates on biomineralized shell structures other organisms are taken.Diatoms are complex, highly porous silicate shells of different sizes in the range of 2-2000 microns There are also many rare species (fossil species, freshwater species) that are abundant in deposits as diatomite or kieselguhr in very different grades and, when processed into tag particles, the smaller species (Minidiscus, Cyclotella) are predominantly for inkjet Printing, medium (3-10 μm) types for offset, rotogravure and flexo printing and large to very large types (from 10 μm for example Thalassiosira, Coscinodiscus) preferably for offset printing, screen printing or steel engraving.

The 1B shows a historical Diatomeen Kreispräparat of the company Watson & Sons, London. The diatom range is 2 mm in diameter. The 1C shows individual biomineralized shell structures of radiolarians in detail. Radiolarians are complex, porous silicate shells that only occur and thrive in saltwater. Their size ranges from 30 μm to several 100 μm. There are hardly any deposits, but an occurrence in deep-sea sediments is relatively common, so that the heavy procurement represents an additional safety feature. The 1D shows single biomineralized shell structures of coccolithophores. Coccolithophorides are generally platelet-shaped calcite marine organisms with a size between 5-15 μm. Coccolithophorids are easy to cultivate. The 1E and 1F show microscope images of Synurophycae ( 1E Synura uvella (Stone em Koskikov); 1F Mallomonas duerrschmidtiae (Siver, Hamer & Kling)). These are usually flat and diamond-shaped silicate shells of freshwater organisms, which are constructed like silicate diatoms but have smaller dimensions (1-2 μm). Of the 1G Microscope images of chain-forming structures of Magnetospirillum magnetotacticum (magnetotactic bacteria) can be seen. These are well culturable, tiny magnetite particles (about 30-100 nm), whose specific arrangement can be achieved by applying a magnetic field during production or application.

All in the 1A to F shown biomineralized shell structures of the prior art are suitable for the production of marking particles according to the invention and can be used after appropriate technical preparation as marking particles, for example in printing inks, but also directly in the material of the product to be created or in adhesives for application to the finished product become.

In the 2 a micrograph of a mixture of two different label particles is shown. These are the elliptical shells of Fragilariopsis kerguelensis with size dimensions between 30 and 70 μm. The needle-shaped shells of Thalassiotrix antarctica are up to 1 mm long. Depending on the application, they can also be screened out of the mixture. This mixture of diatoms comes from an Antarctic sediment, which lies in 5000 m water depth, between 1.5 and 3 m thick and about 120 000 years old, whereby it is only available to very specific facilities and people, which in turn is a safety feature ,

• 1. Die Steuerbanderole von Zigarettenschachteln wird mit einer Sicherheitsfarbe zusätzlich bedruckt, die Markierungspartikel in Form von dreizackigen Schalenstrukturen der Größe 800 nm mit integrierter Tetraederstruktur enthält, die zusätzlich mit einer fluoreszierenden Farbe beschichtet wurden (oder in die eine fluoreszierenden Farbe während der Aufzucht eingeschleust wurde), siehe unterer Teil der Steuerbanderole in 3 (schematische Darstellung mit Maßstabsverzerrung). Durch Prüfen unter der UV-Lampe werden diese feinen Strukturen dann sichtbar. Mit Hilfe einfacher Mittel wie einer 10fachen Lupe kann die Struktur bereits deutlicher erkannt werden. Das für den Originalitätsvergleich erforderliche Abbild der originalen Information kann beispielsweise als Wasserzeichen im Druckbild der Steuerbanderole mitgedruckt werden, siehe oberer Teil der Steuerbanderole in 3.
• 2. Ein Plattenlabellogo, das auf Musik-CDs aufgedruckt wird, enthält biogene Markierungspartikel. Wenn der Verdacht besteht, dass es sich um bei den im Handel befindlichen Tonträgern um Fälschungen handelt, kann mit Hilfe einer elektronenmikroskopischen Untersuchung und einem anschließenden Originalitätsvergleich schnell und zuverlässig festgestellt werden, ob es sich tatsächlich um Plagiate handelt oder nicht.
• 3. In teurer Kosmetik wie beispielsweise Cremes oder Parfums werden biogene Markierungspartikel bis zu einem bestimmten Anteil – bis zu dem sie das Aussehen, die Konsistenz oder Funktion des Produktes nicht beeinflussen – direkt eingebracht. Hier kann eine Prüfung auf Echtheit ebenfalls mit dem Mikroskop erfolgen.

In the following, some embodiments for an application of the marking particles according to the invention are shown:

• 1. The tax stamp of cigarette packets is additionally printed with a security ink containing marking particles in the form of tri-layered shell structures of size 800 nm with an integrated tetrahedral structure additionally coated with a fluorescent paint (or into which a fluorescent dye has been introduced during rearing) , see the lower part of the tax stamp in 3 (schematic representation with scale distortion). By examining under the UV lamp these fine structures then become visible. With the help of simple means such as a 10x magnifying glass, the structure can already be recognized more clearly. The image of the original information required for the originality comparison can be printed, for example, as a watermark in the printed image of the tax stamp, see the upper part of the tax stamp in FIG 3 ,
• 2. A record label logo printed on music CDs contains biogenic marking particles. If it is suspected that the commercially available phonograms are counterfeits, it can be quickly and reliably determined with the help of an electron microscopic examination and a subsequent originality comparison, whether they are indeed plagiarized or not.
• 3. In expensive cosmetics such as creams or perfumes, biogenic marking particles are incorporated directly up to a certain level - up to which they do not affect the appearance, texture or function of the product. Here, a check for authenticity can also be done with the microscope.

Example of the technical implementation the use of biomineralized shell structures as a security feature:

The marking particles, for example diatoms, which are deliberately combined in a mixture, can be admixed with a printing lacquer (aqueous dispersion) in an amount of 0.05 to 5%. On a laboratory scale, about 0.001 g of marking particles (about 1%) of biomineralized shell structures from Costalite with a size of about 5 μm were stirred into about 2 g of pressure varnish. In a subsequent pressure test on a sample printing device about 0.2 g of the printing varnish were printed. In the analysis of any sample with the scanning electron microscope, the marking particles were clearly visible (see 4 ). The offset process is the most commonly used printing process. The design is arbitrary. The structure of the organisms used in each case can be printed as a background image, whereby the examiner knows how the structure has to look under the SEM.

Claims (8)

Inorganic marker particles based on natural microorganisms having a specific surface and properties specificity for the detectable labeling of products with known original information for their proof of originality, characterized by the formation of the marking particles as biomineralized shell structures of biological microorganisms of a biomineralizing organism group with one according to the criterion a high com plexen original information specifically selected specific individuality of the optical appearance of the three-dimensional shell structure, producible by • selecting one or more rare biomineralizing groups of organisms whose biological microorganisms produce biomineralized shell structures, from a special sediment or field sample or a technically modified culture according to the criterion of highly complex original information the biomineralized shell structure, obtaining the biomineralized shell structure of the selected group of organisms and technical preparation of the biomineralized shell structures with regard to purity, size and surface technical preparation of the biomineralized shell structures by cleaning, mixing, sieving or crushing and / or by etching or coating one or more recovered biomineralized shell structures, such a complex Ers The image of the three-dimensional shell structures of the marking particles is produced by the technical preparation of the biomineralized shell structures in such a way that a direct detectability of the marking particles applied to a product is possible by optical observation. Inorganic marker particles according to claim 1, characterized by a predetermined mixture of the recycled biomineralized shell structures of different biological Microorganisms. Inorganic marker particles according to claim 1 or 2, characterized by recycled biomineralized shell structures of diatoms, radiolarians, synurophycae, coccolithophores or magnetospirillum spp. as biomineralizing organism groups. Inorganic marker particles according to one of claims 1 to 3, characterized by a particle size between 30 nm and 2 mm. Process for the preparation of inorganic marking particles based on natural microorganisms with a specific individuality regarding surface and Characteristics for the detectable labeling of products with a well-known original information for their proof of originality according to one of the claims 1 to 4, marked by • Select one or more less frequently biomineralizing groups of organisms whose biological microorganisms produce biomineralized shell structures, from a special one Sediment or field trial or a technically modified culture according to the criterion of a highly complex original information of the biomineralized shell structure, • winning the biomineralized Peel structure of the selected organism group and • technical Preparing the biomineralized shell structures by cleaning, Mixing, sieving or crushing and / or by etching or coating one or more recovered biomineralized shell structures. Method according to claim 5, characterized by selecting one or several rare biomineralizing organisms Antarctic species, species from isolated lakes on islands or out remote mountain lakes. Method according to claim 5 or 6, marked by technical modification of a culture • low Change the concentration of nutrients available in the culture, • enforced Fusion of cells between different types of biological Microorganisms in a biomineralizing organism group, • Introduce of alien substances or element concentrations and / or • genetic engineering Change. Method according to one of claims 5 to 7, characterized by variably combining the various selection and technical treatment options within and between different microorganisms.