Product authentication method

FIELD: product authentication.

SUBSTANCE: system has at least one material, providing transformation with frequency increase, as protective marking and one authenticating apparatus, which has one source of electromagnetic radiation with one previously selected wave length and one second electromagnetic radiation source with one second previously selected wave length, which are different from each other and are selected in such a way, that they cause emission by material, providing for transformation with frequency increase, of electromagnetic radiation after combined irradiation by emission with first and second wave lengths, and emitted electromagnetic radiation has radiation with one additional third wave length, specific for return of one electron from activation ion energy level to level, at which electron is excited by combined emission with first and second wave lengths.

EFFECT: higher efficiency.

6 cl, 2 dwg

 

The present invention relates to an improved system protection products and improved method of authentication protected products, as stated in the restrictive parts of the independent claims.

Containing compositions of coating materials that transform with increasing frequency, in particular input as pigments in the composition of the coatings, are well known and described for applications related to the protection of documents in several publications (see, for example, GB 2258659, GB 2258660, Martindill in Polymers Paint Color Journal, 8, 1996.

Luminescent materials can absorb some of the energy acting on them, and then emit this absorbed energy in the form of electromagnetic radiation. Electromagnetic materials, ensuring the transformation with decreasing frequency, absorb electromagnetic radiation at a higher frequency (shorter wavelength) and re-emit it at a lower frequency (longer wavelength). Fluorescent materials that transform with increasing frequency, absorb electromagnetic radiation at the lower frequency and re-emit it at a higher frequency. Electroluminescent materials are used for marking and coding products for mass production, high-quality products known what's trademark as well as the protected documents. In some cases, a fluorescent material that transform with increasing frequency, add as a hidden "labels" in the composition is transparent or colored coating or ink for printing, which is (are) applied to products of well-known brands in the form of bar codes, logos, companies, labels, etc. This provides further recognition of the genuine product in the process of taking action against poddelyvali and industrial piracy.

The light emitted by the luminescent material is in the state of excitation of atoms or molecules. Accompanied by the emission decay in the excited state of atoms or molecules is the time constant of the decay, which depends on the material and may be in the range of values of the lifetime from less than 10-9seconds to several hours. This means that between excitation and emission light has a certain period of time. Most fluorescent materials or materials that transform with increasing frequency, suitable for the creation of machine-readable codes. Reading machine is a prerequisite for the application of materials that transform with increasing frequency, in the production of massovogo production, because this feature is widely used in automation, automatic sorting, when the control process of the parties, authentication products, quality and packaging. Of course, the ability to read machine is also used in the application of the protective measures to be undertaken in order to identify fakes and fraud, i.e. with the so-called machine verification (authentication).

Materials that transform with increasing frequency, are inorganic and consist essentially of a crystal lattice in which the ions of rare-earth metals are present as activators and sensitizers. The characteristics of the excitation and emission materials that transform with increasing frequency, are the essential characteristics of the rare earth metals. Their respective processes of optical absorption and emission are due to electron transitions within not completely filled 4f shell of the ion rare earth metal. This electron shell is well protected against chemical environment of the atom, so that changes in the crystal lattice, temperature, etc. are in this shell only limited impact. Therefore, ions of rare-earth metals have optical absorption in a narrow Polo is e and emission spectra, largely independent of the nature of the crystal lattice. Narrow discrete strip and the weak interaction with the crystal lattice usually lead to high color saturation when luminescence and a high quantum yield when luminescence.

Activators of luminescence in the form of ions of rare earth metals have an excited state with a relatively large time existence and specific electronic structure. This allows for sequential transfer of two or more photons in a single center luminescence and accumulate them in it. Thus, facilitated the transition of an electron to a level with more energy than one, which corresponds to the energy of the arriving photons. When this electron returns from his level with more energy in the ground state, the emitted photon having approximately the sum of the accumulated energies of the photons that are in the excited state. Thus, it is possible to convert, for example, infrared (IR) radiation into visible light. The halides of alkali and alkaline earth metals, and halides, oxychloride and oxysulfate yttrium, lanthanum and gadolinium principally used as a material of the host, whereas ions of Er3+But3+and Tm3+serve as activators. In addition, ions of ITE the Biya (3+) and/or other ions may be present in the crystal lattice as a sensitizer to increase the quantum yield.

Materials that transform with increasing frequency which is sufficiently stable for their introduction into the environment of the media, are widely described in the literature on qualitative and quantitative characteristics of the gratings hosts, processes, rare earth activators, modes of excitation and detection. Therefore, paddlewheel can have access to materials that transform with increasing frequency, and the published technology, so they have a possible opportunity to mimic the protective marking; thus, aspects of the protection of the products are no longer supported.

Security products described in patents GB 2258659, GB 2258660 contain protective marking-based materials that transform with increasing frequency-dependent absorption of two or more photons with the same wavelength. This requires active ions, which have energy levels, separated from each other at almost regular intervals, i.e. at such intervals, at least the distance between the primary state and the first excited state of the ion of the rare earth metal is essentially equal to the energy distance between the first and second excited state. This requirement approximately satisfy only the ions of Er3+But 3+and Tm3+and it represents the main constraint on expansion of assortment of manufactured products containing materials that transform with increasing frequency.

The present invention is to overcome the disadvantages of the prior art.

In particular, the present invention is to develop new and improved items for security systems products.

An additional object of the invention is to improve the protective marking of products based on the materials that transform with increasing frequency.

According to another objective of the invention, the proposed composition and process of making new and unusual materials that transform with increasing frequency.

According to another objective of the invention, an improved method of authentication protected products.

These problems are solved with the help of distinctive features stated in the independent claims.

In particular, they are solved using advanced system protection products containing at least one material that transform with increasing frequency which contains at least one ion activator having discrete energy levels as, at least part of the protective marking, and at least one authenticating apparatus. This device contains at least one source of electromagnetic radiation with at least one first pre-selected wavelength and at least one second source of electromagnetic radiation with at least one second pre-selected wavelength, and the first and second wavelengths are different from each other and selected in such a way that cause the emission of electromagnetic material that transform with increasing frequency, electromagnetic radiation after combined irradiation with at least first and second wavelengths. The emitted electromagnetic radiation includes radiation with at least one additional third wavelength, which is specific for a refund, at least one electron from energy level ion activator on the level at which an electron is excited by the combined radiation from the at least first and second wavelengths.

Additional third wavelength different from the first and second wavelengths.

The term "system protection product" means a collection of some compounds with inherent properties, and the corresponding authenticating the devices, the one or sensing and/or detecting device, which is performed with the measurement and/or analysis and/or quantitative evaluation of the mentioned inherent properties using electronic and/or mechanical devices.

The term "protected product" shall mean the product contains material that transform with increasing frequency, at least one ion activator having discrete energy levels, as a protective marking, and which emits radiation after the combined excitation radiation with at least two wavelengths different from each other.

Protective marking can be incorporated into the coating composition, in particular in the form of ink for printing, and applied as a layer on the protected product. In another specific embodiment, the protective marking embedded in the material forming the protected product, for example in the paper, forming a banknote. Protective marking can also be applied on and/or embedded in another protective marking, such as a hologram.

The improved system according to the present invention extends the protection of the products. The use of materials that transform with increasing frequency, for protective marking no longer limited to those materials that have energy levels that are nearly identical inter is the al is exactly the same length from each other, and give the opportunity to use them in accordance with the invention is a random rare earth activator, because it has an intermediate state excitation with sufficient lifetime and grille-master, resistant to the environment. Thus, the group of ions of rare earth metals as activators significantly expanded.

Authenticating the device contains two or more sources of electromagnetic radiation, and the first source emits radiation with a first pre-selected wavelength, and the second source emits radiation with a second pre-selected wavelength. Additional sources can emit radiation with additional wavelengths. These sources can be combined into the same physical device. In a preferred embodiment, the source or sources of electromagnetic radiation is or are the laser or lasers or contain lasers. In fluorescent material, where the first energy level between the primary state and the first excited state of the ion activator is different from the second energy level between the first and second excited state, the radiation with said first wavelength corresponding to the Planck law ΔE=hv mentioned first energy level is, can only increase the population of activator ions in the first excited state. Simultaneous irradiation with a radiation source with the second wavelength corresponding to the second energy level, can further increase the population of ions in the first excited state up to the second excited state with higher energy. The resulting population of ions in the second excited state is roughly proportional to the product of the intensities of radiation from both the aforementioned first and second light sources. Electron is transferred from the core to the first excited state due to radiation from the first pre-selected wavelength, and passes from the first excited state second excited state due to radiation from the second pre-selected wavelength. You can choose to create a situation in which the electron moves in the excited state, in which energy is even greater if, in addition to subject material that transform with increasing frequency, the exposure to radiation of the appropriate wavelength. Mandatory pre-condition is that at least the radiation energy from the first and second wavelengths must create the possibility of electron transfer. When the electron returns to the showing or any state with more energy in any state with lower energy, is accompanied by the emission of electromagnetic radiation with a specific third pre-selected wavelength.

In another specific embodiment, the electron moves from the ground state to first excited state by radiation from the first pre-selected wavelength, and then gets back in the "intermediate" state of lower energy than the first excited state but not identical by the energy of the basic state, and then moves from this "intermediate" state to the second excited state by radiation from the second pre-selected wavelength. Thus, the excitation to the second state or States in which more energy can be considered joint excitation caused, at least two light sources of limited spectrum.

In the context of the present invention authenticating the device is portable or stationary. The laser or lasers can emit radiation with a pre-selected wavelengths in a continuous mode. In a preferred specific embodiment, the laser emits radiation in a pulsed mode in which the pulses have a peak power required to make detectable emission from a material that provides conversion for what achenium frequency. The laser preferably has a peak power equal to or greater than 1 W, and in an even more preferred embodiment is approximately 10 watts. In the specific case of a portable apparatus, the pulse repetition frequency and pulse width of the laser is chosen so that the average laser power is sufficiently low and therefore does not harm the eyes. The average laser power is preferably equal to or less than 5 mW, more preferably equal to or less than 1 mW, and still more preferably equal to or less than 0.5 mW. To satisfy the constraint on the average power applied to avoid the risk of damage to the eyes, and the pulse duration, characteristic of the laser pulses, equal to or less than 10 μs, preferably equal to or less than 1 μs, and more preferably equal to or less than 100 NS. For the same reason, the pulse repetition frequency equal to or less than 10 kHz, preferably equal to or less than 1 kHz, and still more preferably equal to or less than 100 Hz. When authenticating apparatus contains more than one laser, especially when the authentication apparatus is a portable, all lasers operate in pulsed mode and therefore satisfy the above constraints. All lasers are preferably lasers, compatible with equipment class 1.

Authenticating apparatus also contains Opticheskie elements for directing and/or focusing the laser beam on the material, providing a transform with increasing frequency, or to create a parallel beam of light. In addition, the apparatus may include an optoelectronic detection device. Authenticating the device can be connected to the chip of a computer or microcontroller, evaluation and processing data about emission.

Irradiation using at least first and second pre-selected wavelengths can occur exactly at the same time or with a time delay relative to each other. The delay time must be selected within a range of times of existence of the relevant excited States.

In the context of the present invention, the term "electromagnetic radiation" includes radiation (as stimulating and emitted with wavelengths in the range from 1 nm to 1 mm, But for the most part of the exciting radiation and the greater part of the emitted radiation is radiation with wavelengths in the range from 100 nm to 10 μm; thus it covers invisible ultraviolet (UV) and infrared electromagnetic radiation.

Additional emitted radiation with a specific pre-selected third wavelength, which is used for the detection occurs in the range 150 - 2500 nm. In a preferred specific embodiment assests is of additional emitted radiation with a specific pre-selected third wavelength, which discovers, is visible to the naked human eye and is in the range of 400-600 nm. In an alternative embodiment, the pre-selected third wavelength is detected by the silicon detector.

In another specific embodiment, the present invention specific third wavelength, which is used to detect material that transform with increasing frequency, is invisible to the naked human eye zone of the spectrum and is preferably in the range 180-400 nm.

In yet another specific embodiment of the present invention the emitted radiation with a specific wavelength, which is used to detect material that transform with increasing frequency, is invisible to the naked human eye and is preferably in the range 700-2500 nm, more preferably in the range of 1100-2500 nm.

In an additional specific embodiment of the invention the radiation with specific third wavelength is machine-detectable and machine-readable. The sensitivity of the human eye is about 1 LM/m2for receptors colors and 0.01 LM/m2for receptors of white light. In this context, the term "detection is mine" means, that radiation can be detected using a suitable optoelectronic detecting device. Optoelectronic detection is possible up to the level of counting single photons, then, to the level of 10-14 LM/m2. In the case of electronic or optoelectronic detection does not require the excitation of the material that transform with increasing frequency, continuous beam with the first and second pre-selected wavelengths. You can find reaction already at the single pulse excitation with both wavelengths. This is possible because usually supplied electronic detecting devices are fast enough to detect the emitted radiation having a specific wavelength, even if they operate on pulses in the microsecond or shorter time scale. "Inertia" of the human eye causes the visual detection of events occurring in less than 1/10 second. Consequently, it is possible to develop optoelectronic detecting device that works in completely hidden mode, even in the presence of conventional materials that transform with increasing frequency which themselves must have a clearly visible reaction. Covert detection increases the potential protection in a way consistent with the present invention./p>

Materials that transform with increasing frequency, with ions of rare earth activators that have roughly the same energy levels between the primary state and the first few excited States, are well known in the Annex of the protection. In addition to these ions present invention emphasizes the possibility of using ions of rare earth activators having different energy levels between their various States, to transform with increasing frequency in relation to the phosphors of other species that are used in the application associated with protection.

Material that transform with increasing frequency, can be crystalline component selected from the group consisting of pure or mixed halides lantanides, alkaline and alkaline earth elements, as well as pure or mixed oxyhalogenation yttrium, lanthanum and gadolinium and oxysulfides yttrium, lanthanum and gadolinium as a matrix-host with embedded ions of rare earth metals as activators and chosen as sensitizers.

Material that transform with increasing frequency, is preferably a pigment with a particle size in the range of 0.1-50 μm, more preferably in the range of 1-20 μm, and even Bo which it preferably 3-10 μm.

In a preferred specific embodiment of the present invention, the pigment is introduced into the system protection products, contains ceramic particles.

Ceramic substances are composite solids formed by the regulated castelvania glass. They can be produced by heating a suitable glass precursor with providing partial crystallization of the glass composition. Thus, glass-ceramic materials contain some amount of crystalline phase embedded in the glass phase.

The crystalline phase of the glass-ceramic substance preferably is a fluorescent material. It is of particular interest and have a particular value for fluorescent materials, which are unstable in normal environment and which are due to the presence of this phase can be protected from the negative effects of oxygen, moisture, etc. Matrix glass protects the crystals from dissolving in an aggressive environment and provides an introduction into the composition of the coating, etc. Therefore, new types of fluorescent materials is possible in this way to adapt the application to print.

Many luminescent materials-owners of interest with photophysical point of view, Vlada, for example, water-soluble to some or major extent, such as fluorides, chlorides or bromides of the elements of the group of lanthanides. This solubility is due to the relatively weak electrostatic forces in the crystal lattice, associated with ions of valence minus one. For the same reason and/or because of the presence of heavy ions, these materials are characterized only by the modes of low-frequency vibrations (phonon modes) of their crystal lattices. The absence of high-frequency modes of oscillation results in a significantly increased time of the existence of excited States and quantum outputs with luminescence. The reason for this is that the probability of withdrawal of the vibrational excitation of the ion activator initiated electronically, is low, if the energy gap to the next, the underlying electronic level is much higher than the highest energy mode oscillations (energy phonons) of the crystal lattice. The energy transfer into the crystal lattice becomes negligible in such cases. Thus, it would be highly desirable materials-owners with low energy phonons, and is especially true in the field of phosphors that provide conversion with increasing frequency and in which a long excited state is of necessary to achieve high quantum yields. Unfortunately, the solubility and sensitivity to humidity of the halides of the lanthanides and related materials up to the present time hindered relevant technical applications.

The crystalline component of the glass-ceramic material preferably has an energy of phonons, not exceeding 580 cm-1preferably not exceeding 400 cm-1and even more preferably not exceeding 350 cm-1. These values are typical for solids with relatively low energy phonons, which are particularly suitable as hosts luminescence, as they provide emission from excited energy levels, which otherwise would have been possible in solids with high energy phonons, such as oxides, etc.

As mentioned above, the phonons is the lattice vibrations in the material. The corresponding energy of the phonons associated with the dependence of the Planck ΔE=hv, with its characteristic connection frequency ν band maximum of the measured absorption additives for removal of metal impurities (DUMP). If Horny ion rare earth element has the possibility of switching between two selected energy levels, corresponding to a value only slightly greater than the energy of the phonons of the lattice material master, this energy is becoming the public will quickly diffuse into the crystal lattice without emission of electromagnetic radiation (transition, not accompanied by radiation). In the lattice-owner with significantly lower energy phonons the same transition to mostly be accompanied by radiation. In intermediate cases, both processes, i.e. castelvania, accompanied by radiation and not accompanied by radiation, will be complemented by each other.

In the case of ion Pr3+levelCG4ion Pr3+only 3000 cm-1exceeds the level of3F4. This matrix oxide Si-Oh, which is praseodymium glass, only small fluctuations (1100 cm-1) phonons are required for bridging this gap. Thus, any excited electron located at the level of1G4will quickly return to the level of3F4phonons, exciting the crystal lattice, while the electromagnetic radiation of the appropriate wavelength will not. In the matrix LaF3,alloy Pr3+,the energy of the phonons is 350 cm-1and ion transfer Pr3+with level1G4at the level3F4occurs with radiation. In addition, the existence of the state of1G4greatly increased.

Since the energy of the phonons regulate by means of the radiation intensity in the band, and the mass of the ions forming the crystal lattice, heavy element is with weak ties will represent materials with minimal energy phonons. Glass containing fluoride heavy metals, such as, for example, ZBLAN (53ZrF4·20BaF2·4LaF3AlF3·20NaF), have a half inherent silicates, the maximum energy of the phonons and therefore take twice as phonons, than you need to suppress the level1G4ion Pr3+. The ZBLAN glass, forming the well-known lattice-owner in the application associated with lasers and fiber optics, can also be used as the glass component of the glass-ceramic composite materials of the present invention.

Ceramic material is preferably transparent to electromagnetic radiation in the range 400-750 nm, i.e. in the visible range of the electromagnetic spectrum. The transparency of the glass-ceramic material is determined by the average size of the embedded crystals and/or the difference between the refractive indices of the crystals and the matrix glass.

In a preferred specific embodiment, the average crystal size not greater than 40 nm.

In an additional preferred specific embodiment, the average distance from one crystal to another crystal, introduced in the matrix glass, may not exceed 50 nm, preferably not less than 40 nm. In addition to transparency another aspect, the associated ograniczeniami, imposed on the size of the crystals is to protect the crystals of the matrix glass. These crystals are the owners of properties that transform with increasing frequency, with low resistance to environmental influences and are not physically or chemically resistant organic resins, humidity, etc. can effectively protect the matrix glass having such chemical and physical resistance. Even the grinding of ceramic materials to the desired particle size surprisingly does not have a negative impact on properties that transform with increasing frequency, inherent in these glass-ceramic materials. The crystals are sufficiently protected by the matrix glass, when such a crystal is sufficiently small.

In a preferred specific embodiment, at least one crystal embedded in a matrix of glass, contains the active ion.

In the context of the present invention, active and/or sensitizing ions present at least in one of the crystals in the matrix glass, are ions of rare earth metals having a suitable electronic structure, particularly suitable are ions of rare earth elements selected from the group consisting of Pr3+Nd3+Sm3+Eu+ , Tb3+, Dy3+, Ho3+Er3+Tm3+and Yb3+.

In a preferred specific embodiment of the present invention a ceramic material is akceptowalny glass-ceramic material. Oxychoride have low energy phonon matrix of fluoride, as well as durability and low mechanical properties of oxide glasses. Oxide glass will determine the mechanical and physical properties of the composite material, while the optical properties of the active ion will be governed embedded fluoride crystalline phase.

The preferred matrix acceptedno glass consisting essentially of glass NAS (Na2O·Al2OSiO2). NAS as glass host exhibits favorable properties in connection with the melting and molding, good transparency and excellent durability. The content of SiO2in the molar composition of the glass is preferably from 30 mol.% to 90 mol.%, more preferably from 50 mol.% up to 80 mol.%. The higher the content of SiO2in the glass, the higher the viscosity, which they have, and the easier of them can be molded in large blocks. However, the preservation of fluorine is less than the glasses that have the content of SiO2approaching the lower limit. SiO2you can replace, for example, GeO and Al2About3you can replace Ga2About3. The content of the alkali metal (in the form of Na2O) can be fully or partially replaced by other alkaline or alkaline earth metals, and a mixture of alkali or alkaline earth metals, for example, in the form of HLW. In the glass NAS you can add many other components to modify and bring to a desired value of the refractive index, expansion, durability, density and color of the matrix glass.

The crystalline phase in oksihlorid preferably contains LaF3. Glass-ceramic materials containing LaF3can be obtained through heat treatment, representing a vacation glass NAS enriched in Al2About3before saturation LaF3. Solubility LaF3is determined by the content of Al2About3in the glass. Content LaF3that is significantly below the limit of solubility, leading to persistent glasses, which do not form a glass-ceramic material by heat treatment. Therefore, the content of the LaF3in the glass it is necessary to maintain the level within ±15%, preferably 10% of the limit of solubility LaF3. In case of replacement of the content of alkali metal compositions based on alkali-earth metals solubility LaF3increases. Therefore, the number of LaF3should have taken ivalsa. Glass-ceramic material containing LaF3shows chemical resistance, which in many aspects is more preferable than the previously used ceramic materials, for example glass-ceramic materials containing ZBLAN.

Crystalline phase LaF3provides separation of any rare earth element. Therefore, by replacing part or all of the contents La3+ions of other rare earth elements, you can get a huge set of luminescent materials that transform with increasing and decreasing frequency, with a very unusual electronic structure, responsive to excitation radiation and still have not found wide application in the known phosphors for protection of documents and products. Thus, the use of luminescent ceramic materials in combination with two - or multiphoton excitation, corresponding to an improved system protection products according to the present invention significantly expands the palette of possible luminescence in the conversion mode with increasing frequency.

In a preferred specific embodiment, akceptowalny ceramic material is transparent and colorless to the human eye.

Ensuring proper microstructure, it is possible to reach p is srcnode acceptedno ceramic material, which is equivalent to the transparency of the best optical glass. In General, the microstructure of the glass containing LaF3. depends on the heat treatment temperature. In the case of heat treatment at 750°C for 4 hours becomes visible large number of relatively small (approximately 7 mm) crystals LaF3. The higher the temperature, the larger crystallites grow. At 800°With the average crystal size is 20 nm (the longest axis?), and at 825°With observed average crystallite size of more than 30 nm. Because one factor affecting transparency, are the appropriate size of crystallites, a ceramic material, which is formed at 750°C for 4 hours, proved to be the most transparent of all. Even with the increase of crystallite size due to heat treatment at temperatures up to 775°transparency remained higher than that of the raw material. Transparency is measured as a function of the excitation, which is the amount of total losses for the effects of scattering and absorption. At a temperature of 850°akceptowalny ceramic material becomes opaque.

Glass-ceramic materials subjected to a vacation, you can grind with obtaining pigment. The optimal particle size for most applications, print related, is 3-10 μm. After NR is the implementation of such particles transparent acceptedno ceramic material in a clear floor or media ink can be applied on substrate invisible product code. Because you can develop oxytorinae ceramic pigments with the properties of the emission, which do not contribute to the response to the excitation radiation with the commonly used wavelengths, a potential forger becomes very difficult to localize and identify the markings or repair technical parameters of pigment.

An additional part of the present invention is an improved method of authentication protected products, including the stages at which

a) choose at least one material that transform with increasing frequency, with the electronic structure containing discrete energy levels;

b) choose tools emission of electromagnetic radiation with at least one first pre-selected wavelength and at least one second pre-selected wavelength, and, optionally, with other wavelengths, with at least first and second wavelengths are different from each other;

C) subjecting the material that transform with increasing frequency selected at step a), the radiation exposure with at least first and second selectable wavelengths defined at step b), in which the first wavelength contributes to the transition, at least, real the electron from the first energy level, at least one second energy level at which energy is greater than the first level and the second wavelength promotes the transition of an electron from the second energy level to at least one third energy level and the third energy level, the energy is greater than the second energy level;

g) optional subject material that transform with increasing frequency, the influence of radiation with at least one additional wavelength, which promotes the transition of an electron to the energy levels at which energy is greater than the third level;

d) record the emission spectrum resulting from the decay of excited States of the material that transform with increasing frequency;

e) analyze the emission spectrum for the presence of at least one wavelength that is specific to the collapse transition, at least one electron with at least the third energy level, or level with more energy.

Although the first and second pre-selected wavelengths have to choose so that they differed from each other, additional wavelengths may be the same as the first and/or second wavelength, or can be completely different.

An alternative way of authenticating the protected product VK is uchet stages, which

a) choose at least one material that transform with increasing frequency, with the electronic structure containing discrete energy levels;

b) choose at least one source of electromagnetic radiation which emits a beam with wavelengths that are in pre-selected range of frequencies containing at least one first wavelength, facilitating the transition of at least one electron in the material that transform with increasing frequency selected at step a), the first energy level to at least one second energy level at which energy is greater than the first level, and at least one second wavelength in facilitating the transition electrons from the second energy level to at least one third energy level at which energy more, and at the second energy level, while the first and second wavelengths are different from each other;

C) subjecting the material that transform with increasing frequency selected at step a), the impact of the beam with wavelengths defined at step b);

d) measure the absorption spectrum of the material that transform with increasing frequency;

d) analyze the mentioned absorption spectrum completely and/or substantially absorbed by the I pre-selected wavelength, which is not the first wavelength, in particular the second wavelength.

In this method, the radiation is also emitted by the material that transform with increasing frequency. However, the mode detection based on measurement of the emitted radiation, and the measurement of the absorption characteristics. Absorption lines are observed at the wavelengths corresponding to the spectral transitions from the occupied levels of the excited States to the unoccupied levels of the excited States with higher energy.

Another alternative way of authenticating the protected product includes the steps in which

a) choose at least one luminescent material having electron structure containing discrete energy levels;

b) choose at least one source of electromagnetic radiation emitting at least one first wavelength, facilitating the transition of a significant part of the material in the first or corresponding higher energy excited state, and at least one second wavelength that is substantially different from the first wavelength corresponding to the spectral absorption of the material in the first or corresponding higher energy excited state;

C) subjecting the material selected in step (a), the impact of the source of electromagnetic radiation,in particular at the stage b);

g) registering the absorption of light by the material at the second wavelength;

d) analyze the absorption of light registered in step g), in the presence or absence of the above material.

When all the authentication methods of the protected product that transform with increasing frequency selected at step a)constitutes at least part of the protective marking applied and/or embedded into the protected product.

Part of the present invention is also protective marking providing the emission of electromagnetic radiation with a certain wavelength as a feature of authentication, and the emission of electromagnetic radiation is realized in the form of emission of antistokovskogo material in the excitation antistokovskogo material by electromagnetic radiation with at least two different wavelengths.

In an additional specific embodiment, the protective marking is part of the protected product.

1 schematically shows the system of protection of products embodying including material that transform with increasing frequency, and the authentication apparatus containing two sources of electromagnetic radiation and detecting device.

Figure 2 presents the energy UB is neither and optical transitions in materials, providing a conversion frequency: a) material with ravnovesie energy levels suitable for excitation at one wavelength (prior art), and b) material with energy levels arranged in different periods, requiring excitation at multiple wavelengths, at least two wavelengths.

Figure 1 shows the authentication apparatus 1, which is part of system protection products according to the present invention. There are two laser diode 2 and 3, which is arranged to emit radiation having two different wavelengths λ1and λ2. Their light is directed to the optical system 4 by means of two dichroic mirrors 5 and 6, and then focuses on the marking 7 containing material that provides conversion with increasing wavelength. Marking 7 deposited on the surface 7a. The signal response of the marking 7 is focused by the optical system 4 and passes the dichroic mirrors 5 and 6, going through the filter 10 to the photodetector 8. This particular implementation with two excitation sources provides an efficient signal conversion with increasing frequency from antistatisch materials that are not equally spaced from each other energy levels in their electronic structure. Scheme microcontro the Lera 9 is connected to the power source 12 and activates the pulsed laser diodes 2 and 3 with appropriate temporal sequence of excitation. Diagram of the controller 9 also receives the output signal from the photodetector 8 to evaluate the signal response on transform with increasing frequency. The purpose of the filter 10 is to select a suitable wavelength of the signal response. It is possible to provide a display 11 for displaying the result of the authentication operation.

Figure 2 is conventionally shown two structural diagram of energy levels of electrons encountered in materials that transform with increasing frequency, on the basis of ions of rare earth metals.

In figure 2,and shows a diagram of energy levels for a material having approximately evenly spaced from each other energy levels. These materials are suitable for excitation of the single wavelength. In the above example, ytterbium (3+), for example, in the form of Y202S:Er,Yb, acts as an ion sensitizer, and erbium (3+) - ion activator. When it is exposed to IR radiation with a wavelength of 980 nm, ytterbium ion moves from the ground state (2F7/2in the first excited state (2F5/2). The energy of the excited Yb3+then passed Jonah Er3+and facilitating its transition from the ground state (4I15/2in the first excited state (4I11/2). Due to further exposure of the excited ion Ef3+infrared) is rising with the wavelength of 980 nm he can go to the second excited state ( 4F7/2with more energy. This is the second excited state decays without radiation and the transition occurs in the state of4S3/2, which has a longer time existence, and which, in turn, is the decay transition ion Er3+in the main condition (4I15/2) emitting green light having a wavelength of 550 nm.

In figure 2,b shows a diagram of the energy levels of the material that transform with increasing frequency, with neravnodushiya apart the levels present in the marking 7, shown in figure 1. Such materials require two excitation wavelengths or more, and use a combination of two or more lasers. As the example shows a diagram of the energy levels and the two-step conversion mechanism of the ion Pr3+in acceptedno glass-ceramic material. Matrix electroluminescent material-owner LaF3Pr presents in the form of a crystalline component considered a ceramic material. Irradiation of this material IR-radiation with a first pre-selected wavelength (1014 nm) promotes the transition of ions Pf3+from the ground stateCH4in the excited state1G4. This last condition is no longer possible to reach any other what about the excited state when exposed to radiation with a wavelength of 1014 nm. However, additional material irradiation radiation with the second wavelength (850 nm) promotes the transition of some of the excited ions of Pr3+from the state of1G4in the excited state3P2with more energy. Then decay without emission transition in the state of3Paboutwhich, in turn, is the collapse of the energy transition in the state of3H5and emission of visible radiation having a wavelength of 530 nm. After that there is a return from a state of3H5in the basic state3H4no radiation.

When the lasers operate in pulsed mode, there must be pulsed excitation of the material that transform with increasing frequency, compliance with appropriate spatial-temporal compliance during the life time of a population of ions in the first excited state. The same thing happens when you have to reach excited States with even more energy by irradiation of radiation with additional wavelengths. However, in some cases, it may be useful time delay in the range from 0.1 μs to 1000 μs between pulses of different wavelengths to ensure impacts on material specific internal energy transfer processes, resulting in what is the appearance of a population (ions) in a desired excited state. As such, the internal energy transfer processes are specific for each material, the excitation pulses of two or more wavelengths allows you to find the path of development and identification of more specific detectable luminescent materials.

1. Advanced system protection products containing at least one material that provides the conversion of the frequency of radiation during irradiation of the material by electromagnetic radiation, which contains at least one ion activator having discrete energy levels, as at least part of the protective marking and one authenticating apparatus, characterized in that the authenticating apparatus contains at least one source of electromagnetic radiation with at least one first pre-selected wavelength and at least one second source of electromagnetic radiation with at least one second pre-selected wavelength, and the first and second wavelengths are different from each other and selected in such a way that cause the emission of a material that transform with increasing frequency, electromagnetic radiation after combined irradiation with at least first and second wavelengths and emitted electromagnetic radiation is tion contains radiation, at least one additional third wavelength-specific return at least one electron from energy level ion activator to the level at which an electron is excited by the combined radiation from the at least first and at least second wavelengths.

2. System protection products according to claim 1, characterized in that the first and second sources of electromagnetic radiation include one laser.

3. System protection products according to claim 2, characterized in that the laser operates in pulsed mode.

4. System protection products according to claim 1, wherein authenticating the device contains at least one optoelectronic detecting device.

5. System protection products according to one of claims 1 to 4, characterized in that the authenticating apparatus further comprises optical elements for directing and/or focusing the laser beam on the material that transform with increasing frequency.

6. System protection products according to claim 1, characterized in that the additional third wavelength is in the range of 150 nm and 3000 nm.

7. System protection products according to claim 6, characterized in that the additional third wavelength is in the range of 400 nm and 700 nm.

8. System protection products according to claim 6, characterized in that the additional third wavelength on titsa in the range of 180 nm and 400 nm.

9. System protection products according to claim 6, characterized in that the additional third wavelength is in the range of 700 nm and 2700 nm, preferably in the range of 1100 nm and 2500 nm.

10. System protection products according to claim 1, characterized in that the material that transform with increasing frequency, is machine-readable.

11. System protection products according to claim 1, characterized in that the material that transform with increasing frequency, contains at least one crystalline component selected from the group consisting of pure or mixed halides of the lanthanides, alkali and alkaline earth metals, as well as pure or mixed oxyhalogenation yttrium, lanthanum and gadolinium and oxysulfides yttrium, lanthanum and gadolinium as a matrix-host with embedded ions of rare earth elements as activators, and optionally, as sensitizers.

12. System protection products according to claim 1, characterized in that the material that transform with increasing frequency, contains ceramic particles.

13. System protection products according to claim 1, characterized in that the material that transform with increasing frequency, is a pigment with a particle size in the range between 0.1 μm and 50 μm, preferably in the range of values between 1 μm and 20 μm, and Adebola preferably between 3 μm and 10 μm.

14. System protection products by item 12, characterized in that the crystalline component of the glass-ceramic material has tenovuo energy not exceeding 580 cm-1preferably not exceeding 400 cm-1and even more preferably not exceeding 350 cm-1.

15. System protection products indicated in paragraph 12, wherein the glass-ceramic composite material is preferably transparent to electromagnetic radiation in the range between 400 nm and 750 nm.

16. System protection products by item 12, characterized in that the crystalline component of the glass-ceramic material has an average size equal to or less than 50 nm, preferably equal to or less than 40 nm.

17. System protection products by item 12, characterized in that the crystalline component of the glass-ceramic material contains at least one active ion to provide conversion properties of long-wavelength light in the short wavelength light.

18. System protection products 17, characterized in that the active ion and, optionally, sensitizing ion are ions of rare earth metals selected from the group consisting of Pr3+Nd3+Sm3+Eu3+, Tb3+, Dy3+, Ho3+Er3+Tm3+and Yb3+.

19. System protection products by item 12, characterized in that the ceramic mA what eriala is akceptowalny ceramic material.

20. System protection products according to claim 19, characterized in that the crystalline component of the glass-ceramic composite material contains LaF3.

21. System protection products according to claim 19, characterized in that the matrix glass mentioned glass-ceramic composite material consists essentially of Na2O-Al2O3-SiO2.

22. An improved authentication method protected products, including the stages at which (a) select at least one material that provides the conversion of the frequency of radiation during irradiation of the material by electromagnetic radiation contained in the protected product and having an electronic structure that contains discrete energy levels,

b) choose tools emission of electromagnetic radiation, at least one first pre-selected wavelength and at least one second pre-selected wavelength, and, optionally, with other wavelengths, with at least first and second wavelengths are different from each other,

C) subjecting the material that transform with increasing frequency selected in step (a), radiation exposure, at least first and second selectable wavelengths defined at step b), in which the first length in the us contributes to the transition, at least one electron from the first energy level, at least one second energy level at which energy is greater than the first level and the second wavelength promotes the transition of an electron from the second energy level, at least one third energy level and the third energy level, the energy is greater than the second energy level,

g) optionally, subjecting the material that transform with increasing frequency, the influence of radiation, at least one additional wavelength, which promotes the transition of an electron to the energy levels at which energy is greater than the third level,

d) record the emission spectrum resulting from the decay of excited States of the material that transform with increasing frequency,

e) authenticate the protected product through analysis of the emission spectrum obtained by irradiation of this material protected products that transform with increasing frequency, electromagnetic radiation, in the presence of at least one wavelength that is specific to the collapse transition, at least one electron, at least from the third energy level, or level with more energy.

23. Phase the bath authentication method of the protected product includes the steps which a) choose at least one material that provides the conversion of the frequency of radiation during irradiation of the material by electromagnetic radiation contained in the protected product with the electronic structure containing discrete energy levels,

b) choose at least one source of electromagnetic radiation which emits a beam with wavelengths that are in pre-selected range of frequencies containing at least one first wavelength, facilitating the transition of at least one electron in the material that transform with increasing frequency selected at step a), the first energy level, at least one second energy level at which energy is greater than the first level, and at least one second wavelength in facilitating the transition of an electron from the second energy level, at least one third energy level at which energy is greater than the second energy level, while the first and second wavelengths are different from each other,

C) subjecting the material that transform with increasing frequency selected at step a), the impact of the beam with wavelengths defined at step b),

d) measure the absorption spectrum of the material providing the conversion enhancement is m frequency

d) authenticate the protected product by analyzing the absorption spectrum obtained by irradiation of this material protected products that transform with increasing frequency, electromagnetic radiation, on the subject of full and/or substantial absorption pre-selected wavelength than the first wavelength, in particular the second wavelength.

24. An improved authentication method of the protected product includes the steps in which (a) select at least one luminescent material having electron structure containing discrete energy levels, which must be contained in the protected product;

b) choose at least one source of electromagnetic radiation emitting at least one first wavelength, facilitating the transition of a significant part of the material in the first or corresponding higher energy excited state, and at least one second wavelength that is substantially different from the first wavelength corresponding to the spectral absorption of the material in the first or corresponding higher energy excited state,

C) subjecting the material selected in step (a), the impact of the source of electromagnetic radiation, in particular at the stage b)

g) registering the absorption of light by the material at the second wavelength,

d) authenticate the protected product through analysis of registered light absorption at step g), in the presence or absence of material.

25. Protective marking providing the emission of electromagnetic radiation with a certain wavelength as a feature of authentication, and the emission of electromagnetic radiation is realized in the form of emission of antistokovskogo material by excitation last electromagnetic radiation of at least two different wavelengths.

26. The product having a protective marking that provide emission of electromagnetic radiation with a certain wavelength as a feature of authentication, and the emission of electromagnetic radiation is realized in the form of emission of antistokovskogo material by excitation last electromagnetic radiation of at least two different wavelengths.



 

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SUBSTANCE: system has at least one material, providing transformation with frequency increase, as protective marking and one authenticating apparatus, which has one source of electromagnetic radiation with one previously selected wave length and one second electromagnetic radiation source with one second previously selected wave length, which are different from each other and are selected in such a way, that they cause emission by material, providing for transformation with frequency increase, of electromagnetic radiation after combined irradiation by emission with first and second wave lengths, and emitted electromagnetic radiation has radiation with one additional third wave length, specific for return of one electron from activation ion energy level to level, at which electron is excited by combined emission with first and second wave lengths.

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