Coding composition and a method of recognizing components thereof

FIELD: securities protection.

SUBSTANCE: invention relates to physicochemical protection of securities against falsifications. Coding composition contains one or several code-recognizing compounds, near IR region fluorescent agent, and IR-active compounds containing hydrogen-unbound or weakly bound X-H bonds (X = )-, N-, and ≡C-). Additionally included are IR-active compounds of general formula R1-C≡C-R2 (R1 and R2 are metal or halogen atoms). Method of invention resides in a single or multiple application(s) of one or several coding compositions onto object either avoiding spatial overlapping of compositions or in the form of compositions intersecting in different sequences of streaks, which sequences differ from each other in their code-recognizing components. Recognition of mutually masked code-recognizing and IR-active components is achieved either by way of varying wavelength in excitation spectra or varying intensity and shape of spectra in near IR fluorescence region. Sequence of applied streaks is determined from conformity of code-recognition spectra in higher monomolecular layer (or several monolayers) of composition in a streak intersection point to spectra of individual streaks.

EFFECT: increased information capacity of protection system due to increased diversity of differentiated components.

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The invention relates to the field of physico-chemical protection against counterfeiting of securities (banknotes, cheques, promissory notes, stock certificates and the like), print production (passports, licenses, certificates, tickets, cards and the like), valuable documents, manuscripts, works of art, packaged goods, jewelry, etc. as elements of protection are commonly used special image, label, tracers or special coding system ("Tagi" - "shortcuts" from the English word Tag label or passport of objects).

Divided into three levels of analysis or verification of security features:

I. non-destructive rapid diagnosis in the field by unskilled user visually and/or using low-detecting devices;

II. analysis (diagnosis, identification) with the possible application of a complex of partially destructive methods in the laboratory using standard equipment (spectrometers, etc. and with qualified personnel;

III. analysis (diagnosis, identification) in laboratory developers-producers with the use of special equipment or standard using a specific "know-how". The competition developers of security systems with clandestine laboratories level II requires the development of such high-tech t is hnology, to prevent the manufacturing of fakes or imitations of security features that are indistinguishable from the originals at level I.

Typical security features visual (or with the help of a magnifying glass) of the definition are, for example, a holographic image, colored micro-fiber or colored multilayer microparticles - microtag. The latter is interesting because it allows due to variations of the color layer and their sequence to encode information about a large number of objects, that represent the coding composition. The protection elements based on the effects of physico-chemical nature, are photo - and thermochromic paint, optically variable multilayer coating. This category includes many traditional elements of protection, based on the color of luminescence in the UV rays. The relative novelty among them is the introduction of fluorescent compounds in the form of paper impregnation or lamination coating to prevent photocopies of the document by creating interference (blowout).

In view of the obvious conveniences disadvantages of systems of visual authentication is the need for constant retraining users, as well as the unreliability of quantitative comparisons of features and their reproducibility. There is an increasing need for production machinace emich protection systems for automation of processes of recognition, for example, for machines of sorters and counters of banknotes, securities, and for other purposes.

Known optical machine-readable security system. In the patent [Stenzel on G., Lehle E. Paper secured against forgery and device for checking the attached to that particular of such papers. US Patent No. 4146792, Mar. 27 1979] system disclosed optical protection paper on the basis of injecting labels, fluorescent in the visible, ultraviolet and infrared ranges, and the reader, containing the source, filters and detectors. A more advanced method of protection is described in the patent [Schvoerer, M., Ney C. Procede de marquage d'objets par microcristaux a effet de memoire et marqueurs pour sa mise en oeuvre. European Patent No. 0282428 B1, 1992], which uses complicated effects, such as thermoluminescence, when the appearance and disappearance of luminescence is observed in the process of increasing the temperature of the sample. Such complications can be classified as known from the literature magnetoterapia effects on photoluminescence [Mil, Elefantis. The study of the magnetic and spin effects in molecular crystals and polymers. Information Bulletin of Russian Foundation for basic research, Vol.3, No. 3, s, 1995], when the magnetic field changes are observed and the intensity of the luminescence labels. This system attractive and to create a coding compositions differing in the relative magnitude of the effects in different spectral regions vidimos is - near infrared range, however, their disadvantage due to the low specificity of the spectra is the unreliability of differentiation of various compounds in the presence of background noise, distorting the relative magnitude of the effect.

In the above systems are non-destructive electron spectroscopy (reflection fluorescence), which are characterized by high sensitivity and high intrinsic width of the bands, which allows the use of low-detecting devices low spectral resolution. However, in contrast to the methods of vibrational spectroscopy, which is a classic tool of the chemical identification of compounds, the common disadvantage of the methods of electron spectroscopy is the low selectivity and specificity, which allows us to produce counterfeits or imitations of security features that are not visible to the detectors at level I.

Counterparts.

Methods of vibrational IR and Raman spectroscopy when using the detecting device is higher spectral resolution allow you to create a more perfect system of protection due to the presence in their spectra of a significant number of specific narrow bands having the character of "fingerprint" of connections. However, IR spectroscopy absorption requires sample preparation and the sample is destroyed. To implement nerazrushai is the reflection methods have been recently developed special lenses for IR microscopes [Akhmetov. Device for measuring spectra of diffuse reflection. USSR author's certificate No. 1637520, November 22, 1990, D.W.Sting, ATR objective and method for sample analyzation using an ATR crystal, USA Patent No. 5093580, March 3, 1992], however, the cost of such devices is high and, moreover, on a number of technical reasons they cannot be used as the detecting device level I. "Achilles heel" non-destructive method nonresonant RAMAN spectroscopy in the visible range due to the weakness of this effect (˜10-8) is the impurity fluorescence (quantum yield ˜10-3÷10-5)that overlaps the Raman spectra of most of the objects used in everyday life. The development of semiconductor technology has allowed us to create laser sources and detectors near infrared range, where the background, as it turned out, weakened more significantly than the intensity of the CU. Non-destructive systematic study of common materials by the method of Fourier-transform RAMAN spectroscopy in the near infrared range showed that more than 80% of the samples suitable for analysis (e.g. polymers, Raman spectra are often obscured by fluorescence [Agbenyega J.K., Ellis, G., P.J. Hendra Raman spectra of polymers. J.Wiley & Sons, 1997, 120 pp, A.H. Kuptsov, Zhizhin G.N. Handbook of fourier transform raman and infrared spectra of polymers. Elsevier Science, Amsterdam, Netherlands, 1998, 570 pp, Merchants AH, Zhizhin G.N. Fourier-transform Raman and Fourier transform infrared spectra of polymers. M.: FIZMATLIT, 2001, 657 S.]). Note that for increased what I noise immunity traditional electron-spectral protection systems was recently proposed patent [Albert C., Closs F., J. Kipper, Kurtz W, Beck K.H., R. Griebel Use of a liquid containing IR dyes as printing ink. USA Patent No. 5282894, 1994], revealing the composition of the dyes near infrared range. Appeared mass spectrometers suitable for analysis not only at the level II, but also relatively inexpensive mobile devices red-near infrared range (from 630 to 1700 nm) with semiconductor lasers and CCD or rulers for level I. we will Specify that this category of devices include spectral devices low resolution with a resolution of less than 0.5×103(or a resolution of more than 15-20 cm-1), whereas the devices of high resolution are provided >5×104(or with a resolution of less than 0.1 cm-1), in the interval - medium resolution. Standard serial devices last two categories refer to level II.

Most attractive for protection systems are resonance RAMAN spectroscopy or using the so-called CU-active (having several orders of magnitude more intense CU) materials. So in the patent [Macpherson I.A., Fraser I.F., White P.C., C.H. Munro, W.E. Smith Pigment compositions. USA Patent No. 5718754, 1998] proposed a system based on the composition of various azo-, azo-marinovich and floor and cyclic chromophores, readable by the method of resonant Raman (RR) visible range. It is known that adsorbed on the surfaces of some m is for metal (silver, gold, copper and some other) or hydrosols molecules of many substances find Reinforced the Surface of the CU strip (UPCR or SERS), particularly intense in the case of resonant excitation of the adsorbate (UPRR or SERRS). This phenomenon has been used in some elements of protection on the basis of compositions containing WPCR-active aggregates connections on the sols of metals [Macpherson I.A., Fraser I.F., Wilson S.K., White P.C., Munro S., Smith, W.E. Pigment compositions. USA Patent No. 5853464. 1998]. Although familiar with the technology UPCR (UPRR) presents a myriad of problems associated with the reproducibility of this effect and its reliability. Recently in the patent [Kazmaier P.M.. Buncel E.S., Herbert F. Method for document marking and recognition. USA Patent No. 5935755, 1999] proposed the use of combinations of a significant number of conditionally CU-active nizkomolekulyarnykh connections, groups, chromophores, etc. as tags. Dedicated Convention CU-active compounds included in the long list of patent related to the fact that in reality the majority of these compounds have a relatively low degree of superiority in the scattering cross-sections compared with conventional compounds, in the best case, the corresponding intensity RRC dyes.

Progress in the development of a photoconductive optical nonlinear materials for modern electronics has led to the emergence of polymeric materials having extremely online is Sinoe CU. This primarily refers to polymers of class polydiacetylene -[=CR-≡C-CR'=]n(PDA), especially in samples that form the so-called "stack" of polymer chains and having a crystalline structure. Synthesis of CU-active monomers RC≡-≡CR' described in [Yee L, Carbazolyl diacetylenic compounds. USA Patent No. 4125534, Nov.11, 1978]. The intensity of the bands KR skeleton polymer chains by two orders of magnitude superior to the intensity of the resonant Raman bands at side chains and groups of these polymers, as well as the characteristic intensities of the bands RRC dyes.

Similar to a patent [Bralchley R" Nugeni N.O., L.S. Ellis Ink Composition and Components Thereof. USA Patent No. 5324567, Jun. 28, 1994], which describes the use of some crystalline PDA as a label (not coding compositions) security printing inks. This recognition of PDA was suggested by recording Raman spectra in the region of the triple bands relations, where the most intensive band PDA, in comparison with the RAMAN spectrum of the reference sample under the same conditions.

A similar example of a highly RAMAN active materials other class can serve nicolerichie TRANS-polyene, such as polyacetylene [-CH=CH-]n(PA), the synthesis of which is described in [Kobrynski V.M. high-Molecular compounds, ser. In, 1994, 36, No. 5, s-894]. The properties of the composition nizkodefektnoj TRANS-nano-PA, stabilized transparent is Oh polymeric matrix of polyvinyl butyral, described in [Kobrynski V.M. Raman scattering composition of the highly organized TRANS-nano-polyacetylene. Reports of Physical Chemistry, C, 1998, SS-298, V.M.Kobryanskii, A.H.Kuptsov, D.Y.Paraschuk, A.N.Shchegolikhin, N.N.Melnik. Raman spectroscopy in nanopolyacetylene. In: Raman spectroscopy and light scattering technologies in material sciences, Proc. SPEE No. 4098, 2000. (4098-29)] (quantum yield higher than the matrix material by 4-5 orders of magnitude, i.e. about 10-3).

Method of protection against forgery on the basis of introducing coding compositions using highly RAMAN active materials of classes polydiacetylene (PDA), monomers of diacetylene (MDA), the polyene or polyacetylenes SCHA), diamond films and their verification by the method of RAMAN spectroscopy in the near infrared range (see Fig.1) published by us in [Merchants AH Methods of vibrational spectroscopy in the task of identification of materials and technologies. Abstract. discos. academic stepdeck. physics-math. Sciences, M., 2000]. Later there was an application for a U.S. patent [A.N.Schegolikhin, O.L.Lazareva, V.P.Melnikov, V.Y.Ozeretski, L.D.Small. Raman-active taggants and their recognition. Pub. No: US2002/0025490 A1, 2002], which is adopted for the prototype.

The prototype.

Coding composition in the form of liquid or solid formulations based on one or more RAMAN active compounds from a number of monomers and polymers acetylenes and diacetylene, including thermochromic, linear polyins, TRANS-polyacetylenes, polyene, squarenew, cyanacrylate, polyimines, polyazines, poly(atinine is)aryleno, poly(ethynylene)heteroarenes, fullerenes and tubulanus, and fluorescently-active phosphors on up-conversion, and the method of applying the coding composition and identification of its components, including the application (implementation) on the object in the form of liquid or solid compositions and detection method nonresonant RAMAN spectroscopy in the near infrared range.

The disadvantages of the prototype.

1). The General feature of the vibrational spectra of most compounds is the presence of the most intense bands in the range from 400 to 3600 cm-1and almost empty area in the middle of the range from 1800 to 2800 cm-1(the so-called region triple bonds). This area is one third the area of measurement, and its "emptiness" is a disadvantage from the point of view of the density distribution of information along the axis of vibration frequencies. While lying in this range characteristic bands of vibrations of acetylene groups are the most intense in the spectra of CU-active components and not overlapping strips of substrates that are not in this range, but on the other hand, can easily give the chemical nature of the component compositions and contribute to their forgery.

2). In the prototype is asserted by the provision that the nonresonance condition register CR is more preferable in comparison with their conventional counterparts resonance methods CU - point the of view of quantitative analysis in the decision of problems of identification. This statement is true only partly appropriate. First, the item is inappropriate due to the fact that both patents counterparts, and in practice the initial task at level I is a rapid authentication (or fraud detection) - diagnostic, not identification task. Here it may be sufficient and qualitative analysis. And on the contrary - the need to use at this stage of non-destructive analyses of quantitative methods for the differentiation of coding compositions is a disadvantage rather than an advantage. Identification, in practice, forensic identification in order to identify and evidence is level II in forensic science or forensic laboratories (or in clandestine laboratories for the manufacture of fakes or imitations), which, along with non-destructive accepted and successfully used informative methods with partial destruction of samples. Secondly, the secondary absorption spontaneous CU quanta in less than RRC quanta, but still has a place on the impurities or operational pollution. Thirdly, differences in the integral intensity of the fluorescent background of the measured samples affect the temperature of the cooled semiconductor detectors near infrared range, respectively, of the spectrum the response capacity and therefore, the accuracy of quantitative measurements of spontaneous CU. So in real terms spontaneous CU, as well as the RRC has its limitations as a quantitative method. Thus, the purpose of the invention, namely the expansion of diversity coding compositions and their differentiation to diagnose at level I, more than would fit in with the desire to conditions when there is no absorption in the region of the excitation frequency KR (when operating in real conditions almost impossible), and the creation of a system based on a qualitative or semi-quantitative level of the ratio of the intensities of nearby bands differentiation.

3). To solve the identification problems (which were discussed in the application prototype) unsuitable, unstable in time components, such as, for example, monomers of diacetylenes (including irreversible thermochromic). Over time, they are in the process of solid-phase polymerization is transferred to another declared as separate components in the form.

4). The application indicates that the CU-active components (listed grade 12), respectively, and compositions on their basis are characterized by the presence of bands in the range 2300-1900 cm-1and can give visible in the total spectra the contributions of the individual components, with up to six components simultaneously, Thu is shown a concrete example. Moreover, it is proposed to use up to 9 CU-active and one luminescense connection listed two types of so-called "phosphors for up-conversion". Will primetim that only 9 classes of compounds of the above 12 contain a triple bond and really give a contribution in this range. In addition, not any combination of even 6 components out of 9 classes of compounds give spectral discernible pattern. In fact, this interval 400 cm-1filled unevenly and it is divided into several clusters. For example, the low-frequency bands are characterized by Organoelement acetylene group (IU -≡CR) with maxima at about 1950-1920 cm-1and most of the high-frequency - band maxima of the monomers of diacetylene General formula (RC≡-≡CR'), which lie in a narrow region 2270-2255 cm-1. The polymers of formula (=RC-C≡C-CR'=R C≡C-CR=) or (=RC-C≡C-CR'=RC≡C-CR'=) give bands in the area 2120-2080 cm-1Strip two components are distinguishable if their maxima are located at a distance greater than half-widths of the bands of the components, and the characteristic half-width averages about 30 cm-1. Although the width of one of the strips overtones of polyacetylene at 2150 cm-1approximately 80 cm-1For this reason, the representatives of one class declared in cha what totem interval 2300-1900 cm -1difficult to distinguish from each other (as in the "fingerprint" give interference bands of the substrate and other components of the composition). Note that when these half-widths of the bands can without much damage for the separation of components to reduce the spectral resolution of 4-7 cm-1up to 15-20 cm-1Thus, the number of reliably distinguishable combinations in the prototype is rather limited, and the possibility of increasing the information capacity of the system, a lot depends on the spectral resolution of the instruments.

5). Among the above General formula structures with acetylene groups and substitutions about them missing the simplest structure of R1With≡R2where R1,2- metal or halogen. While the value of doubly these types of patterns consists, first, in their most low non-overlapping frequency range relative to the rest of acetylene-containing structures, including type Me-≡CR, where R is an organic radical, but not metal or halogen, and secondly, due to the symmetry of the structure with a multiple bond and heavy atoms, it is particularly active in the KYRGYZ Republic. Many recent experimental evidence rules can be found in the book [Merchants AH, Zhizhin G.N. Fourier-transform Raman and Fourier transform infrared spectra of polymers. M.: FIZMATLIT, 2001, 657 S.].

The technical objectives of the infusion is his invention are:

1. a significant increase in the information capacity of the protection system (increasing diversity differentiable components) without any noticeable appreciation of the detecting devices level I and the cost of manufacture of the compositions;

2. the complexity decoding of security elements using standard equipment level II;

3. a new way of encoding and reading information detecting device level I based on the determination of the sequence of applying overlapping strokes;

4. a new method of non-destructive diagnostics of faux finishing and rigging precious stones in jewelry without removing them from the frames using the detecting device level I.

The technical result is achieved by the fact that

1. In coding composition comprising one or more RAMAN active compounds from a number of squarenew, cyanacrylate, monomers and polymers acetylenes and diacetylene, including thermochromic, linear polyins, polyimines, polyazines, poly(ethynylene)aryleno, poly(ethynylene)heteroarenes, TRANS-polyacetylenes, polyene, fullerenes, tubulanus and fluorescently-active phosphors on up-conversion, add the fluorophores near infrared range, including giving the band RRC spectrum, and IR-active compounds containing hydrogen-unrelated, or loosely tie the nnye X-H bond X=O-, N-, ≡ - giving in a blank area of the Raman spectra from 1800 to 2800 cm-1negativeone strip secondary absorption near-IR fluorescence overtones X-H stretching vibrations, mutually masquerading with stripes CU-active compounds, with the number of CU-active compounds optionally include compounds of the form R1-C≡C-R2where R1,2- metal or halogen.

The proposed coding composition is explained as follows.

Fluorescently-active phosphors for up-conversion or, as they are often called in the literature, anti-Stokes phosphors - oxides or halides activated rare earth elements can be respectively represented by the General formula

R2(1-x)D2xO3-zSzor R(1-x)DxHal,

where R is rare earth elements such as yttrium, cerium, lanthanum, erbium, gadolinium, D is an element from the group comprising neodymium, erbium, yttrium, cerium, lutetium, ytterbium, holmium, thulium, samarium, europium, Hal is halogen such as chlorine, fluorine, bromine, iodine, x is a number less than 1, z is 0 or 1.

The fluorophores near IR-range - organic, metal-organic or inorganic dyes or pigments, fluorescing in the near infrared range. Typical examples of organic and metal-organic compounds - free or metal-containing phthalocyanines, Naftal cyanine, acid blue-black dyes, Nickel-dithiolene complexes and the like, Inorganic iron oxide pigments, chromium dioxide, lead chromate, etc.

In compounds of the form R1-C≡C-R2where R1,2- metal or halogen, for metals are for example, sodium, potassium, lithium, and the halogen is iodine, bromine, chlorine, fluorine.

2. The method of recognizing the components of the coding composition, comprising applying to the object and/or embed in its scope and recognition by the method of RAMAN spectroscopy in the near infrared range, in which the application of the coding composition according to claim 1 without overlapping it touches on the object, either in the form of intersecting in various sequences of strokes, which use two or more compositions in an intersecting strokes, varying only CU (RRC)- active components, with recognition in each coding composition according to claim 1 by the method of RAMAN spectroscopy in the near infrared range are mutually masked RAMAN and IR active components are carried out either by changing the wavelength of the excitation spectra in the range 970-1200 nm, or variations in the intensity and shape of the spectra near IR fluorescence components due to their properties of thermoluminescence, optical properties or magnetodynamic effects, photo and thermochromism, pH, piezo and solvatochromism, effects, Wuxi the foster KR (UPCR) and suppression of fluorescence when applied on the surface composition of colloidal silver either gold or copper, and the determination of the sequence of drawing the strokes coding compositions produced based on UPCR spectra of the top monomolecular layer or a few monolayers of the composition at the point of intersection of the strokes UPCR spectra of individual strokes.

The introduction of the coding composition in the object can be either in liquid or pasty state or in the process of its manufacture prior to joining the state of cure.

Coding composition according to claim 1 is applied on the verge of a precious stone, including jewelry, in the process of non-destructive and non-sample preparation in the field of diagnostics falsification of natural stones synthetic strip IR absorption overtones valence HE is wavering.

The technical result is also achieved by the fact that the monomers of diacetylenes, with time passing in polymeric form, are used as indicators of time of application of the composition, and not as an identifying components, as proposed in the prototype. For example, if the composition of the paste (ink) for handles, it becomes possible according to the degree of conversion of the polymer to confirm or refute the date of signing of documents.

The following examples show the basic provisions set forth in the technical is Eskom solution.

Example 1.

Shows that in a blank area of the CU can be very intense bands due to secondary absorption overtones X-H stretching vibrations that exceed the intensity of the CU strips of the same compounds. When the excitation of KR on line 1064 nm Nd:YAG laser in the near infrared range of samples of kaolinite along with the spectra of CU and fluorescence observed bands of the secondary absorption of the impurity fluorescence (after the primary, causing the fluorescence), which can be seen from figure 2. In the IR spectra of the near and middle range of kaolinite-aluminum hydrosilicate (on the left in figure 2) are observed very intense bands of stretching vibrations are not associated hydrogen bond Oh-groups about 3621, 3653, 3670, 3695 cm-1and their overtones about 7066, 7112, 7140, 7170 cm-1. All spectra were obtained on a FTIR spectrometer (Bruker (Germany) model IFS 66 Raman module FRA106. Strip overtones reproduce the characteristic contour of the fundamental tone and quite intense. Figure 2 on the right band bands with downward-highs of about 2328, 2282, 2254, 2224 cm-1corresponds to the difference between the wave number of the incident Nd:YAG na3epa, 9394 cm-1and wave numbers of the bands around 7066, 7112, 7140, 7170 cm-1and plays the loop that confirms their identity lanes secondary absorption fluorescence IR overtones. While their intensity is Yunosti far exceeds the intensity of all bands of CU kaolinite. The intensity of the overtones are usually several orders of magnitude weaker than the fundamental tone, but very IR-active stretching vibrations of H-H-bonds are characterized by amplitude and strongly anharmonicity movements of the proton and have the most intense overtones. In addition, excited in the solid sample fluorescence in the diffuse scattering in the volume leads to an increase in the degree of absorption.

Example 2.

The demonstration that the relative intensity of the bands overtones in the recorded spectra is associated with the intensity of fluorescence varies proportionally with it, but not CU, shown in Fig. 3. Spectra obtained upon excitation at line 1064 nm Nd:YAG laser Fourier IFS66 spectrometer module FRA106. Sample # 1 - industrial design of prefabricated talc (magnesium hydrosilicate) in the surfactant micelles used in paint and varnish materials. Sample # 2: a mixture of sample No. 1 - 99 concerns and industrial semi-finished iron oxide pigment - 1 concerns prepared using ball mills. Source components obtained on a paint and varnish company Yaroslavl. The addition of the fluorophore increases the intensity of fluorescence in the near infrared range (upper spectrum in figure 3). Facing down the absorption bands correspond to overtones of the valence HE oscillations talc (stronger about 2212 and less about 2244 cm-1distinctive in appearance is eat, what is observed in the IR spectrum of talc is more intense near 3676 and less about 3692 cm-1). In the spectrum of sample No. 1, the relative intensity of overtones weaker intensities of the bands CU talc, whereas in the spectrum of sample # 2 they are far superior to the CR intensity and increase in proportion to the intensity of the fluorescence.

Example 3.

Demonstration of reciprocal compensation and dropout in the middle infrared bands of CU-active components and the IR-active components is shown in figure 4. The sample of industrial semi-finished product of kaolinite in the surfactant micelles for paint materials mixed with mills with monomer diacetylene (1,6-bis((4-carbonyl)-phenoxy)hexa-2,4-Dien)-(Ethylenediamine) in the ratio 3:5, then the last by solid state reaction depolimerization in PDA at a temperature of 215°C for 6 hours. Spectrum obtained by excitation at line 1064 nm using Fourier IFS66 spectrometer module FRA106. Overlapping bands with maxima, facing up (which corresponds to the CU MDA about 2260 cm-1and CU ICP approximately 2115 cm-1) and down (IR absorption overtones νHEkaolinite), as can be seen from figure 4 in comparison with Fig.2, complicates the decoding of the structural-group composition using standard equipment. Indeed, the maximum CR of about 2115 cm-1looks to the to the minimum between the downward-IR-bands, and the strip is about 2260 cm-1no noticeable between the bands of infrared absorption. Note that the masking narrow fluorescent stripes of phosphors on up-conversion of about 2700-3100 cm-1can be achieved at the expense of components that absorb in the range of about 200 cm-1slightly higher 3150 cm-1IR spectrum (frequency overtones usually slightly below twice the magnitude of the fundamental tone).

Example 4.

Variation in the intensity of fluorescent background (significant reduction contributions) to decrypt the RRC-active components of the coding composition is shown in figure 5 on the example of industrial organic dye blue-black acid obtained from NIOPIK. The dye due to the long-wavelength absorption gives fluorescence in the near infrared range, and weak bands RRC-spectrum (upper spectrum in figure 5). The sample was a 20% aqueous solution of the dye (ink)printed on a sheet of white paper (and implemented in the scope of the paper). Raman spectra were recorded after drying ink. The relative weakening of its fluorescence when adsorbed on the surface of colloidal silver and simultaneously strengthen the contribution RRC dye is achieved due to the effect UPRR (bottom spectrum), by adding successively 2 microdrops approximately 5 μl of commercially available ready water dissolve the s polylysine at a concentration of 0.01% and colloidal silver at a concentration of 0.15% directly to the site with dried ink. Using the same concentrations of colloids with other metals - gold, copper - achieved several smaller values of amplification of the Raman spectra, respectively, and the relative weakening of the background. Spectra UPRR on the surfaces of colloidal particles of various metals do not have stripes of colloids and presents only reinforced bands of the dye, so that the differences are only related to the total intensity of all bands of the dye as a whole and the contribution of fluorescent background (for this reason UPRR spectra of other metals not shown). However, the gold colloids are more stable over time, are stored for a long time and do not require freshly prepared solutions. Spectra were recorded upon excitation at line 685 nm diode laser using a Raman spectrometer FORAM685-2 by FOSTER and FREEMAN (England). Set for deposition of droplets and the solutions obtained from the firm FOSTER & FREEMAN. It should be noted that the addition of fresh solutions of colloidal silver guarantees the availability of intensive effect of UPCR unlike similar systems, immediately entered into the composition, as proposed in patent [Macpherson I.A., Fraser I.F., Wilson S.K., White P.C., C.H. Munro, W.E. Smith Pigment compositions. USA Patent No. 5853464. 1998].

Example 5.

When applying two or more compositions may additional hidden coded based on the method of determining the sequence is Yesenia overlapping strokes. For example, intersecting guilloche patterns of different colors are often used as copy-protection securities. The sequence of application of the signature and seal to documents, Zapiski text also raises questions about the sequence of applying overlapping strokes. Twenty years ago in the journal of the American Academy of forensic Sciences [Taylor L.R. Intersecting Lines as a Means of Fraud Detection. // Journal of Forensic Sciences. - 1984, v.29, n.1, p.92-98] describes how to establish their sequence. Since then, he has appeared various modifications and approaches, but the consistency of the two strokes of the same color and similar composition (e.g., two paste black or both the same blue shades) is still a problem. We have developed an approach based on the analysis and comparison of the spectra of the individual lines and their intersection with the method of spectroscopy CU, especially effective with UPCR (see Fig.6). This technology allows to obtain high quality spectra of the top monolayers of the material of the letter at the expense of gain applied in a certain way at the analyzed point colloidal silver. The use of such a solution in the literature (including patent) is not described. Meanwhile, using two pens with ink (paste) of the same composition, one of which sod is RIT CU-active component (or both)of the different and technology UPCR (UPRR) you can create secure documents with binary coding information based on a series of overlapping strokes. This example demonstrates the ability to determine the sequence of crossed lines two songs of blue with different WPCR-active fluorophores near infrared range in weight concentrations of about 15% in the form of pastes for ballpoint pens on the basis of phenol-formaldehyde resins. In the first composition - standard pasta for ballpoint pens domestic production (NIOPIK) used WPCR-active component - phtalocyanine dye. The second pasta Italian production for ballpoint pens Corvina - dye type of fat-soluble violet Methyl Violet. Figure 6 shows the intersection of the strokes of these two compositions (UPRR spectra, respectively b and C of figure 6) in two different sequences of their application (UPRR spectra in the centers of the intersection zone touches - a and d), and the second stroke is applied after the complete drying of the first. According UPRR spectra of the top monolayer of the composition at the point of intersection of strokes spectra of individual strokes shows how the composition was applied later. No other method of traditionally used in forensic laboratories to achieve bezoshibochnogo the reading sequence of intersections in such a case is impossible.

Advantages simultaneously with CU-active components of the coding composition the use of additional types of fluorescent and infrared-active components:

- Standard excitation at 1064 nm (or non-standard in the range of 970 - 1205 nm) bands additional components fall into the above an empty area of the Raman spectra that first, can significantly increase the information capacity Raman spectra bands of the IR-active vibrations, Smoking or weak in CR, and secondly, the overlapping and mutually disguise band components of the coding composition based on acetylene groups, bands triple ties and other vibrational bands in this range.

- Characteristic, diverse in shape, narrow and intense bands of the secondary absorption overtones hydrogen-disjoint valence X-N oscillations, especially O-H vibrations, can be used as components of the coding composition, which are not observed with conventional excitation in the visible range. Free from hydrogen bonds X-H-group (X=O-, N-, ≡O-, S-, S-) is analytically very convenient, as they are narrow, intense, no overlap and lie on the high-frequency edge of the IR spectra (they lie in the range from 2500 to 3750 cm-1but the most convenient are the first three that lie in the interval 3300-3750 cm-1see the wasps ν OHfigure 2). Strip the first three types of links do not occur in the vibrational spectra of typical substrates (except for those containing fillers of the type of kaolinite and talc) as paper, polymers, metals, since X-H-bonds are present in the hydrogen-bound form, which leads to a significant (depending on the strength of H-bonds on hundreds and even thousands of cm-1) the decrease in the frequency of the oscillations and the broadening.

- The distance between the maxima of the bands overtones and their half-width is slightly higher than the fundamental tone, which facilitates spectral hardware requirements for authorizing force. To demonstrate the range of the valence HE oscillations in figure 2 below, along with bands of kaolinite shows the spectrum of gibbsite - aluminium hydroxide, which, incidentally, are the most intense in the spectrum of this mineral. In a great variety of bands HE's the only groups only in the infrared spectra of minerals you will find in the book [Plyusnina I.I. Infrared spectra of minerals. From MSU, 1977].

Way cheaper components of the protection system as a whole on the basis of achieved benefits:

1. Coding composition. As its components are only the most CU-active ingredients listed in the prototype and is not introduced into the composition at the same time up to 9 of these components, each of which is subject to the full high cost, and limited to a maximum of 6 different classes with well separated peaks. Set CU-active components expands relatively cheaper IR dyes in one of the following number: phthalocyanines, naphthalocyanines, Nickel-dithiolene complexes, amine compounds, aromatic amines, marinovich and other dyes, as well as relatively inexpensive IR-active compounds with H-H-bonds.

2. The detecting device can be reduced by lowering the requirements, for example, in resolution because of the differentiation of heterogeneous components coding composition does not require a standard resolution of 4-7 cm-1(as mentioned in the prototype), but rather and 20 cm-1that for the same range of registration on the matrix or line allows more than three-fold to reduce the number of pixels of the detector and it is essential to win money (detectors - the most expensive part of the instrument). The spectral range of the detecting device in comparison with a standard range of recording the Raman spectra from 100 to 3500 cm-1can be narrowed down to the range from 1300 to 3100 cm-1. In Fourier spectrometers can triple to reduce the stroke length of the moving mirror. But adding a table with controlled heating or solenoid with a magnetic field will not lead to notable Doroga the s of the detecting system.

3. The means of application to the substrate. In addition to the traditional use of the compositions in the composition of the printing ink that is limited by hardware capabilities or require any special tools for application to complex surfaces (e.g., for protection of works of art and so on), as well as perform this procedure by the consumer without the use of printing equipment, proposed the introduction of coding compositions and the composition of the pastes or inks for pens.

Thus, the advantages of the proposed technical solutions allow to reduce significantly the cost of encoding, protection and authentication of objects.

Example 6.

Portable RAMAN spectrometer and method for recognizing coding components of the compositions, the proposed method may have additional application - namely, for the diagnosis of falsification of a number of precious stones, such as emeralds. It is known that one way of differentiating natural gemstones from synthetic flux is analyzed for the presence (or absence) in the IR spectra of the valence bands HE oscillations. To obtain the IR spectra of good quality stone jewelry is required plane-parallel cutting and removing from the rim. Last, if it is undesirable, it is possible, but is, change the cut of the stone under convenience method is not possible. In addition, it is not always expert gemologist has at hand rather expensive and bulky IR spectrometer. However, when the excitation of the Raman spectra in the near infrared range at line 1064 nm Nd:YAG laser FTIR spectrometer (Bruker IFS66 (Germany) with the module FRA106 simultaneously with strips of CU in the blank areas are experiencing strip secondary absorption overtones bands νOH, which differ from natural synthetic flux stones, in this case emeralds (Fig.7).

The example shows how, with the composition containing the infrared dye to the adjacent or opposite face of the stone, inside where the laser hits, you can diagnose the presence or absence of a genetic type of stone is natural or synthetic flux. While the above bands can be detected with inexpensive portable RAMAN spectrometer.

1. Coding composition containing one or more RAMAN active compounds from a number of monomers and polymers acetylenes and diacetylene, including thermochromic, linear polyins, TRANS-polyacetylenes, polyene, squarenew, cyanacrylate, polyimines, polyazines, poly(ethynylene)aryleno, poly(ethynylene)heteroarenes, fullerenes and tubulanus, and fluorescenceactivated of phosphors on agriculture is nversio, characterized in that it added the fluorophores near infrared range, including giving the band RRC spectrum, and IR-active compounds containing hydrogen-unrelated or weakly related X-H bond, where X=O-, N-, ≡ - giving in a blank area of the Raman spectra from 1800 to 2800 cm-1negativeone strip secondary absorption near-IR fluorescence overtones X-H stretching vibrations, mutually masquerading with stripes CU-active compounds, with the number of CU-active compounds optionally include compounds of the form R1-C≡C-R2where R1,2- metal or halogen.

2. The method of recognizing the components of the coding composition, comprising applying to the object and/or embed in its scope and recognition by the method of RAMAN spectroscopy in the near infrared range, in which the application of the coding composition according to claim 1 without overlapping it touches on the object, either in the form of intersecting in various sequences of strokes, which use two or more compositions in an intersecting strokes, varying only CU (RRC)-active components, with recognition in each coding composition according to claim 1 by the method of RAMAN spectroscopy in the near infrared range are mutually masked RAMAN and IR active components are carried out either by changing the wavelength of the excitation spectra of the range 970-1200 nm, any variations in the intensity and shape of the spectra near IR fluorescence components due to their properties of thermoluminescence, optical properties or magnetodynamic effects, photo and thermochromism, pH, piezo and solvatochromism, gain effects of the KYRGYZ Republic (UPCR) and suppression of fluorescence when applied on the surface composition of colloidal silver, or gold, or copper, and the determination of the sequence of drawing the strokes coding compositions produced based on UPCR spectra of the top monomolecular layer or a few monolayers of the composition at the point of intersection of the strokes UPCR spectra of individual strokes.

3. The way to recognize the coding of the composition by the method of RAMAN spectroscopy in the near infrared range according to claim 2, characterized in that the coding composition according to claim 1 is applied on the verge of a precious stone, including jewelry, in the process of non-destructive and non-sample preparation in the field of diagnostics falsification of natural stones synthetic strip IR absorption overtones valence HE is wavering.



 

Same patents:

FIELD: estimation of authenticity of documents, excise brands, bank-notes and securities.

SUBSTANCE: proposed compound is prepared by mixing gadolinium oxysulfide activated by terbium and yttrium oxysulfide activated by ytterbium and erbium. Size of crystal particles of said luminophores does not exceed 1.5 mcm. Compound thus prepared is introduced into printing ink and is applied on surface to be marked by letterpress printing method in form of mark which is invisible at common lighting. Mark is visualized by infra-red light source and/or ultraviolet radiation thus causing its green glow. Document is subjected to identification for estimation of its authenticity of falsification. Marking retains preset properties for extended period of time at high temperatures, bright light and high moisture content.

EFFECT: enhanced efficiency of protection against falsification.

4 cl, 3 ex

FIELD: automated recognition of symbols.

SUBSTANCE: method includes following stages: tuning, forming symbols models, recognition, recording background model together with background of read image, separating model of registered background from elementary image of background, combining for each position of symbol of model of letters and/or digits with elementary displaying of appropriate background, forming of combined models, comparison of unknown symbols to combined models, recognition of each unknown symbol as appropriate symbol, combined model of which is combined with it best in accordance to "template comparison" technology.

EFFECT: higher efficiency.

10 cl, 10 dwg

FIELD: technologies for validating documents, etc.

SUBSTANCE: device has detector with electrodes, detector and signals processing device, during check an alternating electric field is formed, which excites electro-luminescent radiation. One detector detects electro-luminescent signal of validity mark and transforms it to electrical signal, one electrode is made flat or in form of electro-conductive covering of pressing roller, another - in form of electro-conductive film of pressing roller, or one electrode is made plated of transparent electro-conductive material or in form of round electrode in form of one or several wires, and other one - in form of electrode head.

EFFECT: higher efficiency.

3 cl, 12 dwg

FIELD: sorting of bank notes.

SUBSTANCE: the disadvantage of the known devices of the similar type consists in inconvenience of their use, since the possibility of free and easy access to the path of motion of the bank notes is not provided for the user because of a complicated mechanical construction of the transportation system. Owing to it, it is complicatedly enough to extract the bank notes, which because of malfunctions in the process of their transportation may block the transportation system. The invention makes it possible to eliminate the mentioned disadvantage due to the fact that the device for sorting of bank notes consists at least of three component, and at least of two separated from the external components.

EFFECT: a free and easy access to the transportation system is provided.

17 cl, 4 dwg

The invention relates to a method for ensuring the authenticity of the subject by applying to a photochromic ink

The invention relates to a latent raster printed image on a substrate, which shows, in particular, the multi-color reverse image under the influence of ultraviolet rays, and also to a method for producing such images

The invention relates to control of banknotes in a Bank sorting machines

Valuable document // 2232422
The invention relates to a valuable document, such as security, identity card, etc., equipped with at least one sign of authenticity in the form of material luminescing

The invention relates to the field of printing and can be used for production and protection against forgery of securities

The invention relates to a sensor with improved signal-to-noise ratio, intended for use as a discriminator for determining Svornosti sheets in cash and other devices when using sheets with a great variety of properties

FIELD: optical data carriers.

SUBSTANCE: device has cation dye or mixture of cation dyes with optical characteristics, changed by means of recording beam, an at least one substance with functions of damper and phenol or substituted phenol with one hydroxide group or more, while it additionally contains phenol or substituted phenol in form of phenolate ion, forming a portion of anions for dye cations, as a stabilizer. Data carrier can contain anionic metal-organic thyolene complex as damper, which forms other portion of anions for dye cations.

EFFECT: higher stability, higher durability, lower costs.

5 cl, 1 tbl, 3 ex

FIELD: color-forming compositions and recording material.

SUBSTANCE: claimed composition includes developer containing urea-urethane compound and colorless or light colored leuco dye. Recording material based on this composition also is proposed.

EFFECT: color-forming compositions with improved image conservation ability and increased image intensity.

21 cl, 14 tbl, 153 ex

The invention relates to a method for ensuring the authenticity of the subject by applying to a photochromic ink

The invention relates to the field of devices that change color under the influence of electric current, namely, the electrochromic device and method of its manufacture

The polarizer // 2199571
The invention relates to a light polarizers and can be used in flat panel LCD displays, lighting, optical modulators, matrix systems light modulation, etc
The invention relates to applied electrochemistry, specifically to the electrochromic composition and method of manufacturing devices on the basis of such composition

The invention relates to the field of organic chemistry, namely to new individual compounds of class imidazopyridines, method of production thereof, which exhibit fluorescent properties and can be used as starting products for the synthesis of new heterocyclic systems, as well as substances for sample labeling and additives for reflective paints

The invention relates to materials for the preparation of superfine,non-ferrous, thermostable polarizing coatings (PP), which can be used in optics for manufacturing a display device, the production of Polaroid film on a polymer basis, polarizing glass for construction and automotive industries

FIELD: color-forming compositions and recording material.

SUBSTANCE: claimed composition includes developer containing urea-urethane compound and colorless or light colored leuco dye. Recording material based on this composition also is proposed.

EFFECT: color-forming compositions with improved image conservation ability and increased image intensity.

21 cl, 14 tbl, 153 ex

FIELD: optical data carriers.

SUBSTANCE: device has cation dye or mixture of cation dyes with optical characteristics, changed by means of recording beam, an at least one substance with functions of damper and phenol or substituted phenol with one hydroxide group or more, while it additionally contains phenol or substituted phenol in form of phenolate ion, forming a portion of anions for dye cations, as a stabilizer. Data carrier can contain anionic metal-organic thyolene complex as damper, which forms other portion of anions for dye cations.

EFFECT: higher stability, higher durability, lower costs.

5 cl, 1 tbl, 3 ex

FIELD: securities protection.

SUBSTANCE: invention relates to physicochemical protection of securities against falsifications. Coding composition contains one or several code-recognizing compounds, near IR region fluorescent agent, and IR-active compounds containing hydrogen-unbound or weakly bound X-H bonds (X = )-, N-, and ≡C-). Additionally included are IR-active compounds of general formula R1-C≡C-R2 (R1 and R2 are metal or halogen atoms). Method of invention resides in a single or multiple application(s) of one or several coding compositions onto object either avoiding spatial overlapping of compositions or in the form of compositions intersecting in different sequences of streaks, which sequences differ from each other in their code-recognizing components. Recognition of mutually masked code-recognizing and IR-active components is achieved either by way of varying wavelength in excitation spectra or varying intensity and shape of spectra in near IR fluorescence region. Sequence of applied streaks is determined from conformity of code-recognition spectra in higher monomolecular layer (or several monolayers) of composition in a streak intersection point to spectra of individual streaks.

EFFECT: increased information capacity of protection system due to increased diversity of differentiated components.

3 cl, 7 dwg, 6 ex

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