WO2010020407A2

WO2010020407A2 - Method for recognising concealed markings, in particular for exposing pirated products or imitation goods

Info

Publication number: WO2010020407A2
Application number: PCT/EP2009/006014
Authority: WO
Inventors: Tanja Bendele
Original assignee: Bendele, Thomas
Priority date: 2008-08-19
Filing date: 2009-08-19
Publication date: 2010-02-25
Also published as: WO2010020407A3

Abstract

The invention relates to a method for recognising concealed markings on an object, said markings being applied to, fixed on and/or inserted into components and/or covers and/or accompanying documents of original products and can be made visible by means of an X-ray source and/or a THz-source by means of an imaging method.

Description

Method for detecting hidden markings, in particular for detecting product piracy or counterfeit products

The invention relates to a method for detecting hidden markings, which are mounted on, on and / or in components and / or sheaths and / or accompanying documents of original products and made visible by means of an X-ray source and / or THz source by means of imaging methods can be.

Task is the development of a method for combating product piracy, in particular a process that recognizes and / or can distinguish counterfeit medicines and counterfeit branded products. The process will be based on a combination of nondestructive analysis methods, whereby the distinction of the original counterfeit products will be made quickly, safely and reliably by detecting a hidden mark in the products. The process would make a successful counterfeit expensive enough to make counterfeiting unprofitable at best. Another important aspect of this procedure is to ensure the health of the European population with authorized pharmaceutical products and to detect unauthorized, potentially dangerous counterfeit medicines.

Currently, there is no non-destructive automated method of analyzing medicines for detecting counterfeit medicines. Over 50% of WHO's uncovered drugs contained no active ingredient, 19% the wrong dosage and 16% a wrong drug. Already 30% of the counterfeits are uncovered in industrialized countries. In Europe, the percentage of discovered counterfeit medicines is 1%. The number of unreported cases can be much higher due to sophisticated counterfeiting. Exactly these "good" counterfeits should be detected reliably with the developed procedure. The damage to the pharmaceutical industry can hardly be quantified and is estimated at 17 to 25 billion dollars.

So far, security technology in the area of civilian goods transport has been designed specifically to avert terrorist attacks. Here, the imaging search focuses on particular materials and shapes, i. on weapons and explosives. These methods are currently not suitable for detecting product piracy. Particularly in the pharmaceutical sector, the risks to the population due to uncontrolled import are more fake

1

BESTATIGUNGSKOPIE Medicines unmistakable. The usual imaging technique is based on x-ray scanning. There is no nondestructive and automated investigation of drugs to detect counterfeit medicines. All known tests relate to the inspection or test procedures in which the products are destroyed. The previous labeling is obvious and not forgery-proof. Therefore, the number of unrecognized, sophisticated counterfeits is estimated very high. The associated economic damage to industry and endangering the health of the population is a serious problem.

Currently, it is not possible to detect drug counterfeiting by a simple, fast and non-destructive process. Sophisticated drug counterfeiting currently remains undetected. So far, complex analysis methods, such as HPLC or dissolution tests have to be done in order to detect these counterfeits. The resulting damage to the pharmaceutical industry is estimated at $ 17 to $ 25 billion. In order to better enforce intellectual property rights, such as patent and trademark rights, the development of a non-destructive and discrete process is indispensable. This allows the consistent application of the Law on Improving the Enforcement of Intellectual Property (Directive 2004/48 / EC) and the EC Border Surveying Regulation (EC) No 1383/2003 on customs action against goods suspected of infringing certain intellectual property rights ,

The goal is:

1) Development of a non-destructive analytical method based on existing safety systems and supplementing them to detect counterfeit product piracy, especially counterfeit medicines.

2) the prevention of health risks to European and international populations arising from sophisticated counterfeiting of medicines and ensuring the supply of the population with authorized medicines;

3) the avoidance of economic damage by the industry through the infringement of intellectual property rights and

4) the improvement of the applicability of the Law on Improving the Enforcement of Intellectual Property (Directive 2004/48 / EC (29.04.2004, OJ EU No. L 195 p.16), the Border Seizure Regulation EC No. 1383/2003 Customs actions against goods suspected of infringing certain intellectual property rights. With successful implementation of the process and the associated overall concept, an internationally operating company should develop to avert product piracy and counterfeiting of medicines.

The project is highly interdisciplinary and requires a high degree of scientific expertise in the field of solid-state analysis, especially in the field of pharmaceuticals. Mandatory is the combination of solid-chemical, pharmaceutical, patent and analytical competences. It can be tested by means of terahertz spectroscopy (THz, new solid-state analytical method, pGe laser). The combination of classical solid-state analysis with THz allows purposeful approaches to detecting sophisticated counterfeit drugs. Based on many years of experience of the project partners, there is an interdisciplinary expertise to develop concrete combinations of analytical tools and procedures that distinguish authorized drugs reliably and non-destructively from counterfeit medicines. Due to the nondestructive and automated examination, this can be done discretely and quickly.

Terahertz radiation is electromagnetic radiation in the frequency range between 0.1 and 10 THz. Many compounds, materials or composite materials exhibit characteristic signatures in their absorption spectra in this spectral range. THz radiation is characterized by a high permeability. A preferred THz method is Time Domain Spectroscopy (THZ-TDS). Broadband electromagnetic THz radiation is generated by ultrashort femtosecond laser implants (fs). The laser radiation is divided into pumping and scanning beam. The pump beam is focused on a THz emitter. Such generated THz radiation is specifically broken and absorbed after impact with a sample, here original product or copycat product. The specific refraction and absorption also occurs at the intrinsic label and / or the additional label provided. The continuous or reflected portion of the THz radiation is directed to a detector and superimposed there with the fs scanning beam. With the help of the THz radiation a good spatial, ie three-dimensional resolution of the spectrum can be obtained. The spatial resolution is limited by the respectively used THz radiation and apparatus-specific parameters. In addition to the spatial resolution, a determination of the layer thickness is possible. If labels below the dissolution limit are used in the process, they can be read at least where there is an increased concentration. This can be done in certain "accumulations" occur, which can then be detected in the spectrum as inhomogeneity.

The core of the project is a procedure for the detection of product piracy with a focus on counterfeit medicines. Based on existing methods, such as in the area of airport security, the aim is to develop a non-public, forgery-proof labeling and / or marking procedure and to achieve this until the first market maturity. The period of time to reach the set goals is estimated to be two and a half years, with many of the planned work being carried out not consecutively but in parallel. The future customers come from the area of the entire pharmaceutical industry in accordance with the set focus. The expansion to any manufacturer of branded products, chemicals and mechanical engineering and establishment of a company is planned.

Evaluation of materials eligible for use as markers / markers in the applied methods (X-ray scanning, terahertz spectroscopy). Suitable markers or markers are metals, salts of metals, metal complexes, pigments based on metal complexes and / or metal salts, silicon oxides such as SiO 2, silicates, aluminates and other materials, substances and / or compounds which are known to the person skilled in the art and strongly absorbing or X-ray-deflecting. Alternatively or additionally, THz radiation absorbing and / or reflecting materials, substances and / or compounds, as well as composite materials are used. The reflective, absorbing or distracting properties of these can be further adjusted by the choice of their habitus or morphology.

A label may additionally be applied or incorporated into a material, or may be intrinsically present on or in the material. According to the invention intrinsically present markings of the original products are recognized by the method. These intrinsically present markings can preferably be present for process-related / manufacturing reasons. Examples of these are pigments in coatings or inks that are present on an envelope (outer packaging and / or blister), an information carrier (patient information, instructions for use, guarantee). By means of the method according to the invention, these intrinsically present markings can be recognized. If the producer of the copycat products does not know the exact composition of these coatings or colors, then the original product of copycat products can be distinguished by these intrinsic markers. A particular advantage of the method according to the invention is the three-dimensional recognition of these markings in original products, in particular in larger compilations or arrangements of the original products, ie if, for example, 5x5x10 original products (number of products in height x width x depth) are arranged. An x, y, z representation / coordinate system of an imaging process can be used to determine whether the number of markings and their spatial arrangement correspond to those of the original products. If marks are missing at certain positions (x, y, z coordinates), the product localized there is identified as a copycat product. A mark may also be provided in the coating or paint of a two-dimensional barcode. In addition, the mark may also be provided in a hole in aluminum blister or metal-containing components, preferably the hole or generally a marking is in each case less than 0.5 μm to 1 Angstrom, particularly preferably 100 nm to 1 Angstrom, particularly preferably 10 nm to 1 Angstrom ,

For example, an original drug package from a reimport with a mimic blister may have been provided with drug-containing tablets. This combination can be revealed with the method according to the invention, since the blister and, if appropriate, the active ingredient-containing tablet does not have the intrinsic or additionally attached marking of the original product. The markings are applied, for example, visually or by means of UV-visible marking on, in and / or on a product, for example a blister, a cardboard box or a leaflet, this being possible by means of a customary imprint. This text or barcode can be applied alone on a blister or product, better at the same time on the box, instructions for use, Belgleitdokumenten, outer packaging or, in the drug formulation, etc., thus increasing the possibility of detecting counterfeit products, for example, if an outer packaging was stolen from the original manufacturer and should come with another blister in the normal drug distribution route. Such a combination can be recognized immediately with the method according to the invention and be withdrawn from the drug distribution route.

In addition to functionality, selection criteria include toxicity as well as environmental and economic aspects. Measurements are made using terahertz spectroscopy, radiation in the frequency range between micro and infrared waves, such as between 1011 and 1013 Hz (reference is made in full to the disclosure "terahertz rays bring insight, Chem. Unserer Zeit, 2005 39, 279-281). or conventional Röntgenscannem performed, especially as they are used to screen baggage at airports. An inventive X-ray scanner works with X-ray brake radiation, also called white X-ray radiation. The products are provided between the X-ray source and a detector for measurement. The scanner and labeling strategies were tested on the basis of a selection of practical product examples from the pharmaceutical sector, such as folding boxes, blisters and leaflets. These include positive and negative tests, blank tests and the use of statistical test methods.

Strengthen:

- Combating the increasing counterfeiting of medicines and thus ensuring the supply of authorized safe medicines to the European population, combating product piracy in general, protecting intangible assets, in particular protecting research-intensive products. The innovative technical process improves the fight against product piracy. It can be used to detect counterfeit medicines as well as branded products. The analysis procedure is non-destructive and automatic. Original products can be quickly and reliably distinguished from copies. It is based on the discovery of secret information of the products, which only the manufacturer knows. This is groundbreaking on a global scale. This innovative technical process will allow research-based companies worldwide to better protect their products from piracy because it operates discreetly. Even contract manufacturers should not be able to determine the secret markings. Currently, the tests are based on visual inspection, or testing, where the products must be destroyed. The process will also be modified so that it can be used at airports to combat terrorism. The detection should be done automatically by trained security personnel. Ensuring the health care of the European population with approved pharmaceutical products through the detection of counterfeit medicines is guaranteed. In this way, considerable damage to the health of the population and financial damage can be averted from the European economy. The safeguarding and enforcement of Intellectual Property Rights of the knowledge-based European economy will be significantly improved.

The invention relates to a method for the detection of original products and imitation products, wherein the original product has at least one mark, preferably, the original product has a plurality of markings, this can be 1 to 10,000 marks, which are not obvious as a marker is, and by means of X-rays and / or radiation in the THz range or by the combination of both methods is recognizable. The marker (s) is / are preferably present in the product intrinsically or inherently or technically intrinsically. The advantage is that the manufacturer does not have to modify his processes and there is no need for a separate marking. The products only have to be examined very carefully and then preferably form the master or the master template. The marking is preferably always identical in all batches in all markings and over a plurality of batches at least some of the markings are identical.

Original products are understood to be products that are protected by a property right or trademark and in particular have at least one marking. As an original product but other products can be considered. As an imitation product, all products are considered that copy or imitate the original products. In particular, imitation products are also understood as those products which are manufactured or distributed without the consent of the owner of the property rights. In doing so, the distribution can be territorially different with and without the consent of the holder of the IPR. With the method according to the invention, the unlawful distribution of the legitimate distribution of the products can be revealed. As an original product in the context of the invention, the product as such but also the product together with its outer packaging, outer packaging, accompanying letter, accompanying documents, instructions for use. At and / or in all these components, the markings may be appropriate to be visualized by means of an x-ray source and / or a terahertz radiation source and at least one imaging method. The method preferably works with an original product which has at least one marking which, in particular in the UV and / or VIS range, is not visible as a marking and can be recognized by means of X-radiation and / or radiation in the THz range. X-ray scanners and / or computer tomographs and / or a THz spectrometer are preferably used for the method.

By definition, the label may be an intrinsic and / or additional label present in the original product. An intrinsic marker thus inherently exhibits the original product without being extra attached. Such a mark may be the commonly used printing ink with which a blister, informational material or wrapper is usually printed. This ink may differ from that of imitation products, because it has a different chemical composition. It will be understood by those skilled in the art that these intrinsic labels can thus be any suitable inherent parameter of original and mimetic products.

The marking which can be recognized by means of the method is preferably carried out by substances and / or compounds which deflect the X-ray radiation more strongly than the material surrounding the marking. An example is a metal-containing ink, ink on a cardboard box, a tantalum-containing ink on a SmPC. Nor can the marking be nearly transparent to the X-radiation and / or the terahertz radiation. A mark can also be based on being nearly transparent to X-rays and being visible to and strongly absorbed by terahertz radiation.

The marking is preferably carried out by metals, semimetals, rare earth metals, such as those of the main groups and subgroups of the Periodic Table of the Elements (PSE) IIa, MIb, IVb, Vb, VIb, VIIb, VIIIb, Ib, IIb, IIIa, Va, VIa and / or VIIa, in particular the marking is carried out by its salts, complexes, pigments or composite materials comprising at least one of said metals or elements. Particular preference is given to their salts, complexes, pigments comprising tantalum and / or samarium but also to silicon oxides, such as siloxanes and / or SiO 2 -based or aluminum-containing paper coatings, papers or boards or paints modified therewith.

The labeling is preferably carried out by tantalum and / or samarium or rare earth metals, salts, complexes or other compounds containing these metals. According to the method, the marking is effected by substances and / or compounds which absorb more strongly in the THz spectral range than the material surrounding the marking. Examples thereof are metals, siloxanes, SiO 2 -containing compounds, aluminum-containing compounds, glass and / or silicates on and / or in paper, cardboard, plastics, in particular PE, PP; Hydrocarbons, paraffins, ceramics etc.

Preferably, the label consists of a chemical element, such as preferably a semi-metal or metal such as silicon, tantalum, neodymium, cerium, lanthanum, gadolinium and / or samarium or a rare earth metal.

Alternatively or additionally, the label may be an inorganic and / or organic polymeric compound, preferably with a semimetal and / or Metal such as silicon, tantalum, neodymium, cerium, lanthanum, gadolinium and / or samarium or rare earth metals functionalized. Preference is given to silanes, silicones which can be crosslinked by condensation and are then a marking of the original product, in particular they are functionalized with at least one selenide metal.

The invention also provides the use of an X-ray scanner and / or computed tomography for spatial recognition and / or two-dimensional recognition (sectional planes that can be assembled) and optionally pictorial representation of markers, in particular intrinsic and / or additional markers, in original products and imitation products, in particular to identify the original products and counterfeit products and discover the counterfeit products as such. The invention also relates to the combined use of THz spectroscopy and X-ray scanners for the detection of original products and imitation products, wherein the original product has at least one label. The X-ray scanner is preferably suitable for measuring markings three-dimensionally and displaying them three-dimensionally or in sectional planes via an imaging method. The X-ray scanner preferably operates with X-ray brake radiation, in particular a tungsten or else a copper anode or a correspondingly different metal. The choice of anode material depends on the design of the X-ray scanner or the capacity, if an entire container with products is to be measured particularly hard X-radiation is needed.

The invention also provides a method for detecting original products and copycat products, comprising the steps of a) providing the original products and / or copycat products, optionally in a spatial arrangement of at least two of the products along at least one of the axes x, y and z (axis) , in particular with an aforementioned marking according to claims 1 to 24, b) detecting the position of the marking in the product and optionally spatially in the arrangement, in particular detecting the x, y, z coordinates in space, by means of X-radiation and / or radiation in THz range or by the combination of both methods, c) analyzing the positions of the markers in the products, d) determining the position of the original products and / or the imitation products, optionally in the arrangement. In the method according to the invention, an X-ray scanner which determines the markings two-dimensionally and / or three-dimensionally is preferably used. Particularly preferred is an X-ray scanner operating with X-ray brake radiation. As anode material in general, all suitable materials known to those skilled in consideration. These may be in particular tungsten, copper and other common metals or possibly also alloys.

Original product, characterized in that it comprises a drug comprising an envelope (outer packaging, blister or the like), an active ingredient-containing formulation and is protected in particular by protective rights. An imitation product, is in particular characterized in that it visually resembles the original product and manufactured without the consent of the owner and / or placed on the market is possibly only with the consent of the owner in certain countries may be spent and imported into an unauthorized country ,

According to the invention, paper, plastics, paraffins, hydrocarbons, certain ceramics or, in particular, generally materials which are based primarily on intermolecular van der Waals interactions or weak intermolecular interactions, and / or in particular a density of less than 1 g / cm ³ or 1 kg / have m ³ as transparent in the THz spectral range. In general, all substances, compounds or phases of substances or compounds are suitable as label (A) whose phase has denser and / or stronger interactions than a second (B) less dense phase of substances and / or compounds and / or with weaker interactions , Examples of (B) Overpacks such as plastics, paper, paperboard such as PE blisters, cardboard boxes, examples of (A) are metals, glass, pigments, etc.

According to one embodiment variant, the method uses as marker in the THz range a material, in particular a substance and / or compound, with intermolecular hydrogen bonds, which is solid or pasty, especially at 20 ° C. Preference is given to materials, substances or compounds having strong hydrogen bonds, such as OH..O, NH ... O, OH... N, CF... HC, C-Cl... H hydrogen bonds, but also salts particularly suitable as well as other known to the expert intermolecular and / or intramolecular hydrogen bonds. These markers can also be materials such as resins, which cure only at elevated temperatures and then are fixed at 20 ⁰ C. The marking preferably comprises at least one metal, metal salt, metal complex, metal oxide, pigment, composite material, ceramic and / or clay or a mixture of at least two of the materials mentioned. The marking may in particular comprise at least one SiO 2, silicate, silicon-containing compound, aluminum, tantalum, thallium and / or samarium or a compound containing these metals.

Particularly preferably, the marking comprises at least one material, in particular a substance and / or compound, such as at least one metal-containing compound which absorbs in the region of the radiation maximum of the X-ray radiation source. Preferably, the marking is on and / or in the product (original product), optionally at least on and / or in an envelope, on and / or in an information material and / or on and / or in another component of the repackaged product and / or on and / or in the accompanying documents. Particularly preferably, a plurality of markings are provided on all components or components of the original product to allow maximum distinctness of the original product and the counterfeit.

According to the invention, the original product is provided with markings on and / or in the envelope, i. Outer packaging, such as cardboard boxes, on the information material, i. Instructions for use or patient information, and on and / or in another envelope, such as the blister, i. one or more components of the blister, such as an aluminum layer, PE packaging or other plastic attached or embedded in the plastic. According to one embodiment of the invention, a drug, for example, all its sheaths (outer packaging and blister) and / or information materials are provided with markings. Preferably, these markers are incorporated in a coating, such as the printing ink or another coating, or else in a wrapping material. A marking is considered embedded if, for example, it has been incorporated into the PE in a polymeric material, such as PE of the blister, during its production. It may also be incorporated in paper, cardboard or other natural or synthetic polymer or composite material. Thus, according to a preferred alternative of the method according to the invention or the use of an original product, preferably pharmaceuticals, on several components such as at least one envelope and information materials markings. The markings are arranged so that an always identical original product three-dimensionally a defined pattern or motif in a scan with at least one X-ray beam and / or at least one THz beam after detection and

Conversion generated in an imaging process. Even more preferred is a method in which a two-dimensional, preferably a three-dimensional detection of the markings by means of X-ray and / or THz radiation not only an original product, but a defined two- or three-dimensional compilation of at least two original products, in particular a variety of these original products, the three-dimensional have a defined arrangement. Such an arrangement can have, for example, 5 × 5 × 10 packs (250 packs arranged in three dimensions) (height × depth × width), for example drug packs. If every pack including wrapping (outer packaging, blister) and information material has at least three intrinsic markings, 250 x 3 markers must exist in three dimensions, via their x, y, z coordinates, using 100% original products using X-ray scanners and / or THz spectrometers be recognized. The assignment or adjustment is done by imaging and a master showing the markers with their x, y, z coordinates. This three-dimensional arrangement of original products would then have three spatially defined markings per original product, so that 3 times 5 × 5 × 10 spatially defined markings are detected in space. In the absence of a mark in an original product, for example, the blister is not marked, this would be detected. Such a measurement result of the method according to the invention would reveal the replacement of a blister in an original envelope, here outer packaging. By means of this measuring method, it would thus be possible to reveal wrappings, in particular pharmaceutical cardboard boxes filled with copying blister packs and / or copying information material.

The uncovering of copycat products in original envelopes has hitherto not been automated with other prior art methods. According to a particularly preferred embodiment of the method according to the invention or else the use according to the invention, at least a two-dimensional, automated examination of the original products and copycat products of potentially present metals, metal layers or other THz-impermeable materials can take place with the aid of the THz radiation. By means of X-radiation, preferably whole containers, cardboard boxes or pallets can be scanned three-dimensionally and the markings can be displayed in three dimensions, for example via x, y, z coordinates, by means of an imaging method. In the absence of markings in the x, y, z coordinate system, it can be concluded that there is a copycat product. Currently used methods are based on the scanning of individually scanned products, a measurement in a three-dimensional compilation or arrangement is not yet possible. An example of such a known method is the 2D barcode which can be detected on each individual package (1 x1 x1, ie a package or at most a two-dimensional arrangement of packaging, such as 1 x5x5 (H x T x B) Laser must be scanned.

According to one embodiment variant, the method by means of THz and / or an X-ray source and using at least one detector allows readout of the markings in order to provide individualized information on this product. In particular, the method can be used to individualise individual products, individual batches or product series. The individualized information may preferably be visualized by means of an imaging process. According to a further embodiment, the read-out individualized information of a product can be compared via a computer-aided system with master information stored for the original product. It is particularly preferred that the computerized system makes a classification of the scanned products in suspected cases of counterfeiting and highly likely original product.

According to a further embodiment, the method can make counterfeit medicines of authorized drugs within the meaning of the German Medicines Act (AMG) or a comparable national, regional and / or international pharmaceutical law distinguishable by a separate non-obvious marking attached only to the original manufacturer or his authorized contract manufacturer will, read out. With particular preference, the method makes it possible to differentiate non-destructive pharmaceutical counterfeiting of original medicines, in particular of approved medicaments within the meaning of the Medicines Act (AMG) or a comparable national, regional and / or international pharmaceutical law. Non-destructive within the meaning of the invention means that the method allows a classification in suspected cases of counterfeiting of the drug and original product, in particular authorized drug. The cases of suspicion can then be investigated in individual cases with other methods without destruction or by means of solution-based analytical methods. These are XRPD, IR, NIR, CP-MAS, THz ₁ Raman, GC-MS, MS, TOF-SIM, X-ray fluorescence, or solvent-based assays such as HPLC; GC, release tests or other analytical methods known to those skilled in the art.

It is preferred after the first classification of a product, in particular Drug as a suspected case first applied a non-destructive analytical method.

According to a further preferred embodiment, the markers comprise reflective materials, in particular X-rays or THz radiation-reflecting materials. With respect to the THz radiations, the reflective material may have a geometric arrangement that leads to the retroreflection of the THz radiation. These may be, for example, molded plastic particles in spherical or prismatic shape with reflective coated inner surfaces. An object of the invention is also a marking for the recognition of original products and imitation products, according to the method described above. According to two alternative embodiments, the marking may comprise a reflective material and / or a THz radiation substantially absorbing material or a THz radiation substantially impermeable material.

The marker according to the invention may additionally contain encrypted information. A marking according to the invention comprises at least one substance and / or compound which deflects the X-radiation more strongly than the material surrounding the marking. In particular, the marking has a substantially defined density. Preferably, the label is not crystalline, in particular, the label is amorphous. Particularly preferably, the label is a constituent of a coating, in particular a pigment or a modified pigment, preferably a molecule in the form of a metal complex. Likewise, the marking may essentially comprise a chemical element and / or a molecular material, in particular an organic-inorganic, preferably molecular, polymeric material whose absorption edge lies just below the characteristic wavelength of the X-ray radiation source.

The invention also relates to an article, in particular original product, more preferably pharmaceuticals comprising at least one envelope and an active ingredient formulation and optionally an information carrier comprising at least one marker, in particular as defined above or according to one of claims 1 to 32. The article may also be a consumer product such as glasses, pens, scientific articles, scientific equipment, clothing, luggage, bag, satchel, or any other suitable article, especially fashion articles. The embodiments serve to illustrate the general method principle, they are not intended to limit the invention thereto.

EXAMPLES

THz Spectroscopy: Radiation source of THz TD spectrometer (titanium-sapphire (Ti: Sa) Femtosecond laser (fs laser) from KMLabs Inc. pumped at 532 nm Verdi laser (from Coherent) The fs laser emits pulses at 800 nm, fwhm = 25 fs, repetition rate = 80 MHz, average power = 600 mW Details can be found in the following literature, the entire disclosure of which is the subject of this invention (CA Schmuttenmaer, Chem. Rev. 104, 1759 (2004)).

Experiments 1 to 3: Using THz, a coating based on siloxanes and nanoscale SiO2 particles could be visualized on a paper and a PE film, as well as on a PP layer. In the THz spectrum, the areas of the coating can be easily distinguished from areas of the uncoated paper, PEs and PPs.

Experiment 4: A strip of cardboard is prepared by means of a concentrated solution of nickel chloride in such a way that with the aid of these differently thick marking strips are applied at irregular intervals on the cardboard. The resulting pattern is comparable to that of a barcode. This prepared sample plate is positioned between a THz radiation source and a detector, as shown in the figure below, so that the sample plate is within the beam path. The pattern applied to the sample plate by the saline solution can thus be imaged and recognized by two-dimensional scanning of the pattern by the detector and subsequent imaging procedures.

X-ray scanner:

Experiment 5: A strip of cardboard is prepared by means of a concentrated solution of nickel chloride so as to be applied to the board at irregular intervals with the aid of these differently thick marking strips. The resulting pattern is comparable to that of a barcode. This prepared sample plate is positioned between an X-ray source and a camera so that the sample plate is within the beam path. The camera is provided with a fluorescent layer, so that an X-ray sensitive

Exposure of the film is possible. That through the saline on the sample plate applied pattern can be imaged and recognized as an absorption image on the film of the camera in this way with the X-ray source switched on and opened. The salt solution used is matched to the used, based on Cu radiation X-ray source. The absorption edge of the nickel is 1.4879 Å (Angstrom) just below the characteristic wavelength of the copper of 1.5406 Å (Angstroms) (Cu-Ka _1; (κ _a ι _P hai)).

Experiment 6: A drug carton with two blisters of 10 tablets and a leaflet was printed with a color containing nickel chloride in each case the letters XYZ. The X-ray source and the camera are positioned as in Experiment 5. Although they can not be imaged and recognized as XYZ as the absorption image on the film of the camera because of the parallel arrangement of the instructions for use, but at a specific location in the carton a typical for nickel chloride absorption can be detected. The letters on the cardboard can be recognized because of their arrangement in the absorption image.

Experiment 7: Experiment 6 is retrieved. Both the blister, a package leaflet and the cardboard are printed with the letter combination XYZ. The ink was mixed with ceria. The measurement is now done by means of an X-ray tomograph (CT). In the pictures, the marked patterns are clearly recognizable completely or at least as a stronger absorption.

Experiment 8: Experiment 7 We repeat with the change that this time titanium oxide was added to the ink for the pattern. The titanium oxide is well identified by the greater absorption in the visualization of the CT measurement.

Experiment 9: Experiment 7 We repeated with the change that time

Tungsten oxide was added to the ink for the pattern. The tungsten oxide is well identified by the greater absorption in the visualization of the CT measurement.

The figures show an arrangement of drug boxes 1 in Figure 1 with

Markings 2. In the figure 2 use information 3 are shown with marks 2.

Claims

claims

1. A method for the detection of original products and imitation products, characterized in that the original product has at least one mark which is not obvious as a marker, and by means of X-radiation and / or radiation in the THz range or by the combination of both methods is recognizable.

2. A method for the detection of original products and copycat products, characterized in that the original product has at least one intrinsic and / or additional label, which is not obvious as a marker, and by means of X-radiation and / or radiation in the THz range by the combination of both methods recognizable is.

3. The method according to claim 1 or 2, characterized in that the original product has at least one mark, which is not visible in particular in the UV / VIS as a marker, and by means of X-radiation and / or radiation in the THz range is recognizable.

4. The method according to any one of claims 1 to 3, characterized in that the method uses an X-ray scanner and / or computed tomography.

5. The method according to any one of claims 1 to 4, characterized in that the method uses a THz spectrometer.

6. The method according to any one of claims 1 to 5, characterized in that the marking is effected by substances and / or compounds which deflect the X-radiation stronger than the material surrounding the marking.

7. The method according to any one of claims 1 to 6, characterized in that the marking is carried out by metals, semi-metals, rare earth metals, such as those of the main and subgroups of the Periodic Table of the Elements (PSE) IIa, IHb, IVb, Vb, VIb, VIIb , VIIIb, Ib, IIb, purple, Va, Via and / or VIIa.

8. The method according to any one of claims 1 to 7, characterized in that the marking is effected by salts, complexes, pigments or composite materials.

9. The method according to any one of claims 1 to 8, characterized in that the marking is carried out by tantalum, neodymium, cerium, lanthanum, gadolinium and / or samarium or rare earth metals, alloys thereof, salts, complexes or other compounds containing these metals.

10. The method according to any one of claims 1 to 9, characterized in that the marking is effected by substances and / or compounds which absorb stronger in the THz spectral range than the material surrounding the marking.

11. The method according to any one of claims 1 to 10, characterized in that the marking in the THz range based on a material having intermolecular hydrogen bonds, and in particular at 20 ⁰ C is solid or pasty.

12. The method according to any one of claims 1 to 1 1, characterized in that the marking comprises at least one metal, metal salt, metal complex, metal oxide, pigment, composite material, ceramic and / or clay or a mixture of at least two of said materials.

13. The method according to any one of claims 1 to 13, characterized in that the marking comprises at least one SiO ₂ , silicate, silicon-containing compound, aluminum-containing compounds, tantalum, thallium and / or samarium.

14. The method according to any one of claims 1 to 13, characterized in that the marking comprises at least one material and / or metal-containing compound which absorbs in the region of the radiation maximum of the X-ray source.

15. The method according to any one of claims 1 to 14, characterized in that the markings on and / or in the product, optionally at least on and / or in an enclosure, on and / or in an information material and / or on and / or in a further component of the repackaged product and / or on and / or provided in the accompanying documents.

16. The method according to any one of claims 1 to 15, characterized in that the means of THz and / or an X-ray source and using at least one detector read markers an individualized

Provide information about this product.

17. The method according to any one of claims 1 to 16, characterized in that the individualized information is visualized by means of an imaging method.

18. The method according to any one of claims 1 to 17, characterized in that the read out individualized information of a product are compared via a computer-aided system with stored for the original product master information.

19. The method according to any one of claims 1 to 18, characterized in that the process makes counterfeit medicines of approved drugs within the meaning of the Medicines Act (AMG) or a comparable national, regional and / or international pharmaceutical law distinguishable by the method.

20. The method according to any one of claims 1 to 18, characterized in that by the method non-destructive drug counterfeiting of original pharmaceuticals, in particular of approved drugs within the meaning of the Medicines Act (AMG) or a comparable national, regional and / or international pharmaceutical law, made distinguishable.

21. The method according to any one of claims 1 to 20, characterized in that the marking comprises a reflective material.

22. The method according to any one of claims 1 to 21, characterized in that the marking consists of a chemical element.

23. The method according to any one of claims 1 to 22, characterized in that the label is an inorganic and / or organic polymeric compound.

24. Use of an X-ray scanner, THz spectrometer and / or computed tomography for the two-dimensional and / or spatial detection and optionally visual representation of markings in original products and imitation products.

25. A method of detecting original products and counterfeit products comprising the steps a) providing the original products and / or copycat products, optionally in a spatial arrangement of at least two of the products along at least one of the axes x, y and z, in particular with an aforementioned marking according to claims 1 to 24, b) detecting the position of the marker in the product and optionally spatially in the arrangement, in particular the x, y, z coordinates in space, by means of X-radiation and / or radiation in the THz range or by the combination of both methods, c) analyzing the positions of the markers in the products, d ) Determining the position of the original products and / or the imitation products, if necessary in the order.

26. The method according to claim 25, characterized in that the X-radiation is that of an X-ray scanner, in particular an X-ray scanner designed for the three-dimensional determination of the markings, in particular an X-ray scanner operating with X-ray braking radiation.

27. Marking for recognizing original products and imitation products, according to one of claims 1 to 26.

28. A marking comprising at least one substance and / or compound which deflects the X-ray radiation more strongly than the material surrounding the marking and absorbs the THz radiation more strongly than the surrounding material.

29. A marker according to claim 27 or 28, characterized in that it comprises a reflective material.

Mark according to claim 27 or 28, characterized in that it substantially absorbs or is substantially impermeable to THz radiation.

31. A marker according to claim 27 or 28, characterized in that it scatters the X-radiation at least 30% more than that of the immediately surrounding material or the marking absorbs THz radiation 30% stronger than the immediate surrounding material, in particular each independently from 30 to 90%.

32. Marker according to claim 27 or 28, characterized in that it has substantially a narrowly defined density, which preferably deviates by at least plus / minus 5% from that of the material immediately surrounding it.

33. A marking according to claim 27 or 28, characterized in that it comprises essentially a chemical element and / or a molecular material whose absorption edge is just below the characteristic wavelength of the X-ray source.

32. Article, in particular original product, more preferably medicaments comprising at least one coating and an active ingredient-containing formulation and optionally an information carrier comprising at least one marker according to one of claims 1 to 32.