RU2450358C1 - Method for protection from forgery and checking authenticity of articles - Google Patents

Abstract

FIELD: information technology.

SUBSTANCE: in the method, a means of protection is formed on an article with possibility of checking its presence or authenticity; parameters of information features is detected in response to external action with comparison of the detected features with standard features. The physical inspection method used is Raman spectroscopy; the means of protection - label - is the article itself, packaging or an area on the article or its packaging, on which chemical substances, whose chemical composition varies over time, are deposited or incorporated. During inspection, Raman spectra and fluorescence spectra of molecules of the chemical substances are picked up when said spectra are excited in the label by the monochromatic source of a Raman spectrometer. Alteration or replacement of the protected article is indicated by change in composition and concentration of the substances.

EFFECT: reduced cost of making labels while ensuring high degree of security.

21 cl, 5 dwg

Description

The invention relates to information storage means designed to protect against counterfeiting of securities, labels, containers and packaging, liquids and other similar products of mass production, controlled with the help of special devices during random control checks of the turnover of products, as well as retail chains and end consumers .

Modern practice of the use of protective technologies conditionally distinguishes three main forms of protection: declared, certified and hidden. Each of these main groups of protective technologies is designed and operates at a certain level of control by the consumer, manufacturer and relevant government agencies. Declared protection implies the availability of the information necessary for the consumer to decide on the authenticity of a product. Such informational support, for example, is advertising. Among other very obvious methods of open identification of goods, high-tech demetallized holograms on transparent bases can be distinguished. The use of open forms of protection against fraud and illegal trade requires constant and extensive advertising support and legislative support. Certified means of marking goods is a complex of hidden and visible technical measures of protection against falsification, the application technology and method of control of which are known only to the manufacturer of the product and / or the owner of the trademark. The presence and description of such protective measures, such as the method of their identification, may be a trade secret of the manufacturer (owner of the trademark) or partially disclosed to them in the certificate of security of the product. These methods primarily include various printing technologies (watermark, microtext, thermo- and photochromic additives in dyes), special types of paper materials for labels, hidden methods of labeling products. Hidden methods of entering and reading information embedded in visible protective technologies are also used - microtext in holograms, hidden barcode, special printing methods. These types of protection, as a rule, are monitored with the help of special devices during random control checks of the turnover of products.

For physical and chemical protection against securities counterfeiting (RU 2254354 C1, 06/20/2005), both single and multiple application of one or more coding compositions in composition without overlapping them in space, or in the form of strokes intersecting in different sequences, is used. Why use two or more compositions in intersecting strokes that differ by Raman scattering (Raman scattering) of the active components. Recognition of mutually masked Raman and IR active components is carried out by near-infrared Raman spectroscopy by changing the excitation wavelength of the spectra or by varying the intensity and shape of the near infrared fluorescence spectra. This method increases the information capacity of the protection system by increasing the variety of differentiable components. However, the disadvantage of this method is the narrow scope, namely the protection of documents on a paper basis.

Improving the effectiveness of securities protection (RU 2160928 C2, 20.12.2000), including using signs with a low and high level of protection, is carried out by introducing into the banknote a substrate having a security sign in or on one area of the substrate. Each feature with a high degree of protection is represented by a homogeneous mixture of at least two components exhibiting different detectable specific characteristics. This method is also intended to protect only valuable paper media.

The prior art system for marking a hydrocarbon fluid flowing from a source to a destination (RU 2302000 C2, 06.27.2007) contains a sensor for determining the properties of a fluid, a marker flow regulator for letting a predetermined amount of the marker into the fluid from the marker source. The fluid property is selected from the group consisting of temperature, flow, viscosity, density and concentration. A processor is connected to the sensor and to the regulator, which determines a predetermined amount of an input marker (in a particular case, diluted) in accordance with the property of the fluid and a given concentration of the marker in the fluid and controls the marker regulator. The invention allows the identification of oil, gasoline, kerosene, various types of fuel to assess the preservation of the original quality (dilution, counterfeiting), spill or leak of liquid hydrocarbons from pipelines, tankers or storage facilities. The disadvantage of this system is the large time required to implement this method.

A known method of storing and encoding information (US 2011049239 A1, 03.03.2011), which uses a mixture of metal nanoclusters with dyes and other Raman-active substances. The method of reading and decoding stored information is carried out by measuring the Raman spectra. For the code, many points or markers are used, each of which consists of a mixture of two or more Raman-active substances deposited in different proportions on the object. The amount of substance in the mixture and the relative amount of each substance in the mixture is encoded by each point that carries information. By scanning a sequence of points on an object, information stored in a sequence can be read and decoded. The disadvantage of this method is the lack of changes in coding information under the influence of various chemical and physical factors, allowing to judge the proper storage, transportation and preservation of the original quality.

The closest analogue to the claimed method is a method of protection against counterfeiting and authentication of products (RU 2379757 C1, 01/20/2010), which includes the formation on the product of a protective agent of a given structure, configured to control the presence and authenticity of the said means by a physical analysis method, detecting certain parameters informative features in the response of the protective agent to the aforementioned external effect, followed by automatic comparison of the registered signs with the reference values by means of the detection means. The disadvantage of this method is the lack of changes in coding information under the influence of various chemical and physical factors, allowing to judge the proper storage, transportation and preservation of the original quality.

The present invention is to develop a method of protection against counterfeiting and authenticity control of both valuable products and any consumer goods with a high degree of protection, as well as fluids (for example, oil, gasoline, kerosene).

The technical results of the present invention are to reduce the cost of manufacturing protective labels for both valuable products and consumer goods while providing a high degree of protection against counterfeiting, as well as the possibility of storing extended information about this product, such as storage conditions, the ability to date the product and check for expiration expiration date.

A method of protecting against counterfeiting and authenticity control of products includes forming a protective structure of a predetermined structure on the product, configured to control the presence and authenticity of the said means by a physical analysis method, detecting the parameters of certain informative features in the response of the protective agent to the aforementioned external effect, followed by automatic comparison of the registered signs with reference values stored in the memory of the detection means. Raman spectroscopy is used as a physical method, the product itself, the packaging or a portion of the product or its packaging, on which chemical substances are applied or applied as a label, are used as a protective agent, and the presence and authenticity of the protective agent is controlled by recording Raman spectra and fluorescence spectra of chemical molecules in the form of a label during the excitation of these spectra in a tested protective agent by a source of monochromatic radiation of frames Anovsky spectrometer and comparing them with the reference ones. In this case, the label contains a chemical additive in which substances are used whose chemical composition changes over time and / or under a certain type of exposure. In the event of a change in the composition and concentration of the chemicals included in the specified label, it is concluded that the product to be protected has been changed or has been replaced.

In a preferred embodiment, the change in label is caused by dilution of the product to be protected.

In a preferred embodiment, several chemicals are used in the chemical label additive with different times of composition change and / or subject to change under different types of exposure.

In a preferred embodiment, the exposure is light, and / or temperature, and / or moisture, and / or heating, and / or radiation.

In a preferred embodiment, one of the substances included in the label is sulfur-containing, for example mercaptan.

In a preferred embodiment, the label is a one-, two- and three-dimensional image, and / or a one-dimensional or two-dimensional barcode (similar to, for example, a linear barcode or matrix barcode, such as a QR code, Aztec Code, etc.). Individual elements of the image may have different chemical composition, and the reading of such a label is carried out by measuring the spectra of one or more image elements. The relative position of the image elements and / or the application of overlapping image elements are part of the chemical passport of authenticity of the product.

In a preferred embodiment, to increase the sensitivity of Raman spectroscopy, its modifications are used: surface-enhanced Raman scattering, giant Raman scattering, resonant Raman scattering or stimulated Raman scattering.

In a preferred embodiment, when measuring the fluorescence spectrum and Raman spectra of light molecules of the chemical substances of the label, the sample or sample of the product is placed on a reinforcing substrate containing structures that enhance Raman scattering, or mixed with a preparation containing metal nanoparticles.

In a preferred embodiment, the Raman enhancing structure is a nanoparticle powder or a special SERS substrate embedded in the label.

In a preferred embodiment, one of the components of the reinforcing structure is silver.

In a preferred embodiment, the label contains one substance having high adhesion to the reinforcing structure.

In a preferred embodiment, the substances that make up the label are applied to the product as part of a paint coating.

In a preferred embodiment, the substances that make up the label are included in the packaging or packaging of the product.

In a preferred embodiment, the label may contain one or more elements intended for orientation, positioning and analysis of the position of the label in the device. These elements are detected and read by detecting fluorescence and Raman scattering.

In a preferred embodiment, when comparing the fluorescence and Raman spectra of the light of the tested protective agent with the reference ones, the positions, intensities and shape of the spectral lines are taken into account; the ratio of the intensities of the lines of substances that make up the label or lines belonging to one substance from the composition of the label with each other; the ratio of the intensities of the lines of the substances of the label and the spectral lines of the substances that make up the protected product; the dependence of the spectra on the length and power of the exciting radiation, the observation angle, and temperature; the duration and nature of the afterglow.

The invention is illustrated by drawings.

Figure 1 is a block diagram of a Raman spectrometer used for registration and identification of protective labels on products.

Figure 2 represents the background Raman spectrum of the light of the product (which is used as ethyl alcohol) without a protective label.

Figure 3 is a Raman spectrum of a protective label ethanol (rhodamin 6g).

Figure 4 represents a spectrum of ethyl alcohol with a protective label, diluted with counterfeit in a ratio of 1: 1.

Figure 5 represents a spectrum of ethyl alcohol with a protective label, diluted with counterfeit in a ratio of 1: 3.

The method of protection against counterfeiting and authentication of products is as follows.

A series of spots are applied to the product, for example, to a self-adhesive label for alcoholic beverages, or to the material from which the container is made, each of which contains a substance or mixture of substances that have bright lines in the Raman spectrum. Substances can be applied both separately and as part of a paint coating.

In some cases, substances can be introduced directly into the composition of the protected product. The low detection limit of Raman spectroscopy allows the use of low concentrations of substances that do not lead to a deterioration in consumer qualities of the product.

At the first stage of the implementation of the method of protection and counterfeiting and authenticating the products, the background spectrum of the product section or its packaging, on which it is planned to place a protective label, is measured, after which the range of radiation energies of Raman scattering and fluorescence with a minimum background level is determined. Depending on the required degree of protection of the product, the number of chemicals introduced into the additive is selected, which have a set of bright lines in the Raman spectrum of light in the energy region with a minimum background level, and their concentration is set. The formed composition of the additive is applied to the product or its packaging or introduced into the composition of the product. After registering the fluorescence spectrum and the Raman spectrum of the light applied to the product protective labels, their characteristics are entered into the memory of the computer included in the spectrometer kit.

The presence and authenticity of the protective agent is controlled by a Raman spectrometer.

The device is a simple Raman spectrometer shown in figure 1,

where 1 is a semiconductor laser as a source of monochromatic radiation,

2 - interference narrow-band filter that cuts off the side radiation of the laser "laser line filter",

3 - dichroic mirror,

4 - high aperture lens,

5 - interference filter that transmits long-wave radiation and reflects the radiation of the exciting laser "long-pass filter" or a filter that cuts the radiation of the laser "notch filter",

6 - lens (lens system) that collects a signal on a pinhole or entrance slit of a monochromator,

7 - pinhole or entrance slit of the monochromator,

8 - monochromator,

9 - a photosensitive detector (CCD, CMOS, a line of photodiodes, etc.) connected to a miniature computer built into the device or to an external information processing module,

10 - embedded computer or external processing module.

A Raman spectrometer works as follows: the radiation of a semiconductor laser (1) passes through a narrow-band filter (2) and falls on a dichroic mirror (3).

The boundary wavelength of the dichroic mirror is selected so that the laser radiation is almost completely reflected by the mirror, and radiation with a longer wavelength passes through it without reflection. Thus, the laser beam, reflected from the dichroic mirror, falls on the lens (4). In the focal plane of the lens is placed the product, packaging, or a portion of the product or its packaging onto which chemicals are applied or applied in the form of a label.

The point at which the exciting radiation is collected is simultaneously the source of the Raman signal. Thus, the signal source is automatically in the focus of the lens.

The lens uses high-aperture optics, which makes it possible to focus the laser radiation into a spot of the smallest possible size, as well as to collect the maximum amount of scattered radiation. The high aperture of the lens allows you to collect the signal from a large solid angle and thereby increase the sensitivity of the analyzer. The optical signal collimated by the lens is incident on a dichroic mirror. Since the wavelengths of the Stokes Raman lines are greater than the wavelength of the exciting laser and the boundary wavelength of the dichroic mirror, the signal of interest to us passes through the mirror with almost no reflection.

When measuring the Raman spectrum, it is necessary to clear the studied optical signal from the dominant Rayleigh scattering with a wavelength that matches the wavelength of the exciting laser.

In a Raman spectrometer, with which the proposed method is implemented, the signal is filtered twice: a dichroic mirror (3) and a long-wave filter (or Notch filter) (5). Moreover, the narrower the width of the transition section of the transmittance of the filter, the closer you can get closer to the laser line during measurements, and therefore more fully measure the Raman spectrum in the region of small Raman shifts.

The purified signal is focused on pinhole 7 by collimator 6. The pinhole is used for spatial filtering and to increase the spatial resolution of the spectrometer. The received light signal is sent to the slit of a monochromator (8) of a spectral analyzer (9) using an additional lens system or optical fiber tape. The spectra obtained at the photosensitive detector of the analyzer (9) are then converted to digital form and transmitted to a computer (10), where they are processed.

To obtain additional information about the substances that make up the label and the product to be protected (and therefore increase the level of protection or the amount of information stored in the label), the spectrometer can be improved:

1) the excitation circuit may include several lasers for taking spectra at different wavelengths of the exciting radiation;

2) the excitation circuit can include an optical shutter or a pulsed laser, and the registration circuit can be equipped with an optical shutter or electronics, which allows obtaining spectra with a time resolution. The afterglow pattern of certain substances is an important identification characteristic;

3) the scheme can be supplemented with optical elements for rotation and analysis of the polarization of light to measure the Raman spectra of light and fluorescence in different polarizations;

4) the measured signal can be modulated in one way or another (for example, by periodically modulating the power of the exciting radiation, its wavelength or polarization), then when using a demodulator in the registration circuit, the signal-to-noise ratio can be significantly improved;

5) the fluorescence signal is often many times higher than the Raman signal. This can lead to undesirable consequences when registering the spectrum with a photosensitive detector. So, for example, in the CCD, this leads to a scale in some pixels of the detector and “spreading” of the charge across the pixels of the detector. To reduce this effect, additional controllable shutters, shutters, apertures, and apertures can be provided in the spectrometer to prevent light from the bright spectral line from entering the detector. If necessary, they can be installed or removed using control electronics to remove all or part of the spectrum;

6) Raman spectrometer can be combined into one optical circuit with a conventional or fluorescence microscope. In this case, in addition to measuring the spectrum of Raman scattering and fluorescence of a substance, it becomes possible to observe the general image of an object at the focal point of a Raman microscope. Such an improvement can be extremely useful for aligning, positioning, and analyzing the orientation of the mark in the instrument.

In the chemical label can be used substances whose chemical composition changes over time. In the particular case, several substances with different times of composition change are used in the label. Change in label caused by dilution of the protected product.

In the event of a change in the composition and concentration of the substances that make up the specified label, it is concluded that the protected product has undergone a change or has been replaced.

The substances used in the label undergo a change under a certain type of exposure. The exposure is light, and / or temperature, and / or moisture, and / or heating, and / or radioactive radiation. The substances included in the label may be subject to change under various types of exposure.

In the present invention, the chemical label can be a one-, two- and three-dimensional image, and / or a one-dimensional or two-dimensional barcode (similar, for example, to a linear barcode, or matrix, such as a QR code, Aztec Code, etc.). In this case, individual image elements can have different chemical composition, and reading such a label is carried out by measuring the spectra of one or more image elements. The label may contain one or more elements intended for orientation, positioning and analysis of the position of the label in the device. The detection and manifestation of these elements can be made by the physical method of analysis, by detecting the parameters of certain informative features in the response of these elements to a certain external physical effect. In particular, they can consist of substances having bright and / or extremely characteristic lines in the fluorescence and Raman spectra of light. This will allow them to be easily and accurately identified and used to establish the position of the mark and when positioning it.

The relative position of the image elements may be part of a chemical passport of authenticity.

To increase the sensitivity of Raman spectroscopy, modifications are used: surface-enhanced Raman scattering, giant Raman scattering, resonant Raman scattering or stimulated Raman scattering. When measuring the fluorescence spectrum and Raman spectra of light molecules of chemical substances, tags, a sample or sample of the product is placed on a reinforcing substrate containing structures that enhance Raman scattering, or mixed with a preparation containing metal nanoparticles. The Raman scattering enhancing structure may be a powder or a special SERS substrate embedded in the label.

The substances that make up the label are applied to the product as part of a paint coating.

An unlimited number of variations of combinations of chemical points of their location, their concentrations and a low detection limit of Raman spectroscopy provide a high degree of protection against counterfeiting and a high level of control of the authenticity of products.

In a specific example of the method, ethanol was used as the protected product. Figure 2 shows in which energy ranges the spectrum of the protected product will give the smallest background signal. Any chemical substances whose Raman spectral lines are in this energy range can be introduced into the protective label, which allows spectral analysis with a low detection limit.

Figure 3 shows the spectrum of Raman scattering of ethyl alcohol with a protective label (rhodamin 6g), taken as the reference.

For comparison, figure 4 shows the spectrum of ethyl alcohol with a protective label, diluted with counterfeit in a ratio of 1: 1, and on

5 is a spectrum of ethyl alcohol with a protective label, diluted with counterfeit in a ratio of 1: 3. When comparing the spectra of Fig. 4 and Fig. 5 with the reference spectrum (Fig. 3), which is carried out programmatically in the computer of the spectrometer, the ratio of the intensities of the spectral lines of the components of the label to the intensities of the spectral lines of the protected product is taken into account. As a result of the comparison, it is found that in Fig. 4 the concentration of the components of the label (in this case, rhodamine-6g) is 2 times less than the reference, and in Fig. 5 4 times less than the reference, which allows us to conclude that the product was diluted.

The combination of the amount of chemical elements introduced into the additive and their concentration is a chemical passport of authenticity of the product. Any deviations from the characteristics of the passport indicate the falsification of the protective label. The performed experiments confirmed the effectiveness of the proposed method of protection and authentication of products, their packaging and labels.

In another embodiment of the method, a fluid is used as the product. The refinery produces several types of fuel: summer and winter diesel, gasolines of various degrees of purification or with different octane numbers. To protect its products, identify cases of substitution, the plant adds a small amount of the marking composition to the fuel shipped. Each grade of fuel is marked with its own unique label. If desired, the label may be unique for each batch of products shipped. Or a more complex system could be used. Part of the label encodes the type of fuel, the other encodes the batch number, or other information that needs to be "recorded." In addition, the label can have several parts of different levels of protection: low for consumers and higher for manufacturers and law enforcement officers (whose existence is not publicly disclosed). When checking gas stations owned by the refinery or its partners, the Raman / Raman spectra and the fluorescence of fuel samples from the dispensing columns of the gas station are measured. The measurement procedure takes tenths of a second. The measured spectrum is analyzed to determine the presence of labels and their concentrations. Lack of label means replacing the product. A change in label concentration indicates that the fuel has been diluted. The detection of labels of other types of fuel (say, cheaper) in the sample may also testify to the same. A similar check can be performed by the distributor or end user, using a portable device with a tag database loaded into it. The tag can be used in operational investigative measures to detect illegal fuel and gas extraction. By analyzing the insignificant traces of marks, it can be proved that a labeled batch of fuel was in this fuel storage some time ago. Thus, the chemical label provides evidence for security and law enforcement personnel. The use of chemical components in the label, which change with time or under the influence of a certain type of exposure, also allows us to analyze the storage conditions of products. During control, the concentrations of the remaining starting components of the label and reaction products are measured. Based on these measurements, a conclusion is drawn about the duration and intensity of certain influences.

In conclusion, we can say that the estimated cost of manufacturing a security label by the claimed method is about 0.01 rubles with a circulation of 100 thousand copies, which is three orders of magnitude lower than that of labels used in analogues.

Claims (21)

1. A method of protection against counterfeiting and authenticity control of a product, comprising forming a protective structure on a product of a predetermined structure, configured to control the presence and authenticity of the said tool by a physical analysis method, detecting the parameters of certain informative features in the response of the protective tool to the aforementioned external influence, followed by automatic comparison registered signs with reference values stored in the memory of the detection means, characterized in that Raman spectroscopy is used as a physical method, the product itself, the packaging or a portion of the product or its packaging, on which chemical substances are applied or applied as a label, are used as a protective agent, and the presence and authenticity of the protective agent is controlled by recording Raman spectra and fluorescence spectra of molecules of chemical substances labels in the process of excitation of these spectra in a tested protective agent by a source of monochromatic radiation of Raman spectrometer and comparing them with the reference ones, and the label contains a chemical additive that uses substances whose chemical composition changes over time and / or under a certain type of exposure, and in case of a change in the composition and concentration of chemicals included in the specified label , conclude that the protected product has undergone a change or has been replaced. 2. The method according to claim 1, characterized in that the change in label caused by dilution of the protected product. 3. The method according to claim 1, characterized in that in the chemical additive labels used several chemicals with different times of change in composition. 4. The method according to claim 1, characterized in that the exposure is light, and / or temperature, and / or moisture, and / or heating, and / or radioactive radiation. 5. The method according to claim 1, characterized in that in the chemical additive of the label several chemicals are used, subject to change with different types of exposure. 6. The method according to claim 1, characterized in that at least one of the substances included in the label is sulfur-containing. 7. The method according to claim 6, characterized in that at least one of the substances included in the label is a mercaptan. 8. The method according to claim 1, characterized in that the chemical label is a one-, two- and three-dimensional image and / or one-dimensional or two-dimensional barcode. 9. The method according to claim 8, characterized in that the individual image elements can have different chemical composition, and the reading of such a label is carried out by measuring the spectra of one or more image elements. 10. The method according to claim 8, characterized in that the relative position of the image elements is part of a chemical passport of authenticity of the product. 11. The method according to claim 8, characterized in that the order of applying the overlapping image elements is part of the chemical passport of authenticity of the product. 12. The method according to claim 1, characterized in that in order to increase the sensitivity of Raman spectroscopy, modifications are used: surface-enhanced Raman scattering, giant Raman scattering, resonant Raman scattering or stimulated Raman scattering. 13. The method according to p. 12, characterized in that when measuring the fluorescence spectrum and Raman spectra of light molecules of chemicals, the label of the product sample or sample is placed on a SERS-active reinforcing substrate containing structures that enhance Raman scattering, or mixed with a preparation containing SERS-active metal nanoparticles. 14. The method according to p. 12, characterized in that to enhance Raman scattering use a structure that is a powder of SERS-active nanoparticles or a special SERS-active substrate, embedded in the label. 15. The method according to item 13 or 14, characterized in that one of the components of the reinforcing structure is silver. 16. The method according to item 13 or 14, characterized in that the tag contains at least one substance having high adhesion to the reinforcing structure. 17. The method according to claim 1, characterized in that the chemicals that make up the label are applied to the product as part of a paint coating. 18. The method according to claim 1, characterized in that the chemicals that make up the label are introduced into the packaging or packaging of the product. 19. The method according to claim 8, characterized in that the label may contain one or more elements intended for orientation, positioning and analysis of the position of the label in the device, the detection and reading of which is carried out by a physical analysis method, by detecting the parameters of certain informative signs in the response of these elements on a certain external physical effect. 20. The method according to claim 19, characterized in that said elements are detected and read out by detecting fluorescence and Raman scattering. 21. The method according to claim 1, characterized in that when comparing the fluorescence and Raman spectra of the light of the tested protective agent with the reference, the positions, intensities and shape of the spectral lines are taken into account; the ratio of the intensities of the lines of the substances that make up the label, or lines belonging to one substance from the composition of the label, with each other; the ratio of the intensities of the lines of the substances of the label and the spectral lines of the substances that make up the protected product; the dependence of the spectra on the length and power of the exciting radiation, the observation angle, and temperature; the duration and nature of the afterglow.

Images