Luminescent ink for cryptographic protection of documents and articles from falsification, methods for application thereof and methods of verifying said articles

FIELD: chemistry.

SUBSTANCE: luminescent protective ink contains a solvent and semiconductor nanocrystals dispersed in an organosilicon compound, consisting of successively arranged: semiconductor nucleus 1, first 2 and second 3 semiconductor layers and an outer 4 layer, the material of which is selected from an organosilicon polymer from a series which includes poly(aminoethyl)trimethoxysilane, poly(methacryl)triethoxysilane, poly(methyl) triethoxysilane, poly(mercaptoethyl) triethoxysilane, methyl-phenyl polysiloxane, polyethoxysilane. The semiconductor nanocrystals emit a fluorescent signal in a fluorescence wavelength range of 400-3000 nm under the effect of a visible or UV light source; the relative fluorescence quantum efficiency is at least 80%.

EFFECT: making a protective mark from luminescent protective ink, through which an article can be verified using simple means, providing further protection for twenty years.

13 cl, 4 dwg, 7 ex

 

The invention relates to compositions for coating, namely, printing inks containing fluorescent protective ink for encryption of documents and products from counterfeiting, to methods of their application, as well as to methods of control of authenticity of documents and products that bear such fluorescent ink.

The present invention can be used in making and handling protected against forgery of documents and articles having at least one characteristic of the authentication performed using visible and/or invisible protective labels, and methods of control of authenticity of documents and articles having a protective label from the claimed fluorescent ink containing fluorescent semiconductor nanocrystals (colloidal quantum dots).

One way of obtaining colloidal quantum dots included in a fluorescent ink, a method of colloidal synthesis of high-boiling organic solvent. To the peculiarities of colloidal quantum dots can be attributed to the fact that they consist of semiconductor nano crystal (core)coated with one or more crystalline semiconductor membrane and the outer organic layer of adsorbed surfactants.

In contrast to epitaxial kVA the starting point and most traditional organic and inorganic phosphors colloidal quantum dots possess a set of unique physical and chemical properties, including photostability, as well as the possibility of excitation of a mixture of quantum dots with different wavelength emission by a single radiation source. This makes it possible to obtain various fluorescent compounds for hidden protection (encryption) of falsification of documents and products.

The invention relates to fluorescent security ink containing semiconductor nanocrystals, for encryption of documents and products from fakes. We offer fluorescent ink can be used in making and handling protected against counterfeiting of banknotes, excise stamps, credit and other securities, including shares, bonds, certificates, bills, insurance policies, certificates, forms, notary, passports, identity cards, travel documents, lottery tickets and other securities, as well as plastic cards, driver's licenses, stamps and seals, intellectual property, including trademarks and service marks. Fluorescent ink can be used for marking and protecting of packaging products in various spheres of material production, including pharmaceutical, food, chemical industry and mechanical engineering. In addition, these inks can be used for marking jewelry and the products, Museum exhibits, as well as any other things that represent any material value.

The invention also relates to a method of applying a fluorescent protective ink on the documents and articles. Documents and articles intended application of fluorescent protective ink, can be made of any material, including paper, cardboard or wood; metal, including foil; synthetic polymers, including polyethylene, polypropylene, polycarbonate and other plastics; glass; natural fibers including cotton, silk, wool, hemp, synthetic fibers, laminated or of composite materials.

The present invention also includes several methods to control the authenticity of documents and articles having a protective mark on the basis of the claimed fluorescent ink containing semiconductor nanocrystals.

To implement the above methods of control of authenticity of documents and products, they must have at least one sign of authenticity, made using visible and/or invisible protective label. Protective label may be made in the form of guilloche elements or tangling grids, and/or micrographics, and/or microtext, and/or any other images or text, and/or protective fibers, Nansen the x on the surface of a document or article to any of the existing methods of printing, including printing (high, book) or deep, or flat, or digital or offset printing, or stencil, or iris printing, lithography, flexography, helloservant, metallographical, silk-screen printing, personalisation (the printing of variable data), or other method of applying paint or polymer compositions, printing inks or paints, inks for writing utensils (pen, ballpoint, liquid, gel pens and markers), seals and stamps, sealing wax (mastic) for seals. While the composition of such protective label should include fluorescent protective ink containing semiconductor nanocrystals.

Control of authenticity of documents and articles having a protective mark on the basis of the proposed fluorescent ink is performed with the use of sources of ultraviolet and/or visible light with further identification by visual or machine-definitions and mappings registered informative features with informative signs described in the reference document under visual definition, or existing in the database when the machine definition.

For media protective label stored and/or operated under optimal conditions of temperature and humidity conditions (temperature from + 10°C to + 30°C; humidity from to 60%; weakened luminous flux under natural light or low light with artificial lighting) additional protection is guaranteed for twenty years or more (OST 55.6.-85 "paper Documents. The rules state storage. Technical requirements". - M., 1985).

For media protective label stored and/or operated in severe conditions of temperature and humidity (temperature of -60°C to + 70°C (Pets short term exposure (less than 1 minute) to + 250°C); humidity is over 65%; bright sunlight) additional protection is guaranteed for 20 years or more when used for the manufacture of protective labels, fluorescent ink, containing in its composition as a solid dispersion medium silicone compound.

The proposed group of inventions provides additional protection and the ability to assess the authenticity of the media protective label. In addition, these methods of control of authenticity of documents with security label with the claimed fluorescent ink containing semiconductor nanocrystals can be used as one of the measures to combat counterfeiting of documents and products in all fields, including criminology for disclosure on a budget is the investigation of crimes.

The prior art solutions, in which for the protection of documents and products from fakes used luminescent materials containing semiconductor quantum dots. Thus, in patent US 7811470 B1, C09K 11/02, publ. 12.10.2010, describes a method for coloring water-based, containing semiconductor nanocrystals, and the use of this dye in the ink composition for coating on metal, glass, plastic film, textiles, wood, concrete and other materials, as well as in the ink composition for flexographic printing or screen printing. Fluorescent signal from the dye water-based can be detected (stored) after prolonged (up to ninety days) exposure to sunlight. However, this solution cannot be used in full for the protection of documents and products from imitations for a longer time, for example, more than one year due to degradation in the harsh environment of nanocrystals contained in the dye.

The prior art method of obtaining a semiconductor quantum dots and fluorescent material containing semiconductor quantum dots, which can be used, for example, as a fluorescent marker (EN 2381304 C1, C30B 7/00, C09K 11/02, publ. 10.02.2010). As a result of this synthesis is accomplished colloid is haunted quantum dots, which belong to I or type II: core/external organic and/or organosilicon polymer layer or the core/first semiconductor sheath/outer organic and/or organosilicon polymer layer, respectively.

The presence of the semiconductor shell for type II quantum dots provides an increase in the quantum yield of fluorescence and the increase in the photostability of quantum dots to external influences. This ensures the preservation of the fluorescent signal of quantum dots in a long time, at least 70% of the original.

The presence of external organic layer in the first and second types allows colloidal quantum dots to form a disperse system (sols) in different liquid and solid media.

The disadvantages include the inability of use of colloidal quantum dots as a protective labels in the products, for example, in money bills, the service life exceeding one year, due to degradation in the harsh conditions of the surrounding environment of quantum dots (nanocrystals), which leads to loss of the protective properties of banknotes and the impossibility of establishing the authenticity of banknotes. In addition, the material is not high enough relative quantum yield.

The closest analogue (prototype) proposed technical the RCM decision on the totality of the claimed features is the invention, disclosed in international publication WO 2007/137292 A1, C09K 11/00, publ. 19.11.2007. The paper describes a fluorescent ink, which include one or more types of quantum dots. Each type of quantum dots may have a wavelength of fluorescence from 400 nm to 2500 nm, the total geometric size of quantum dots does not exceed 20 nm and quantum yield of fluorescence does not exceed 60%. Fluorescent inks are composed of quantum dots of one or more types of solvent, co-solvent, surface-active substances (surfactants), acidity regulators, and viscosity, antiseptic substances and preservatives.

In the selected prototype quantum dots containing semiconductor core of the CdS have a maximum wavelength of fluorescence in the range from 400 nm to 560 nm; from CdSe - from 490 nm to 620 nm; CdTe - from 620 nm to 680 nm; from PbS - from 800 nm to 2300 nm; from PbSe - 1200 nm up to 2500 nm; from CuInGaS from 600 nm to 680 nm; from InGaP - from 600 nm to 700 nm; from ZnCuInGaS from 500 nm to 620 nm; from CuInGaSe from 700 nm to 1000 nm.

Known fluorescent ink can be part of typographical or automotive paints, and also in the paste composition for marking. While the photostability of luminescent ink is stored for six months or more, but not more than one year.

The disadvantages include the preservation of photostability for small promesed the time (up to one year). Therefore, the service life of products using such quantum dots, will not exceed one year. In addition, in the known material used quantum dots that have restrictions on the brightness of the fluorescence (relative quantum yield of 60%), resulting in the need to add them in ink in larger quantities.

The aim of the present invention is to provide a fluorescent protective ink included in the visible and/or invisible protective labels that can be printed on various types of surfaces. Fluorescent protective ink under the action of optimal and/or harsh environmental conditions can maintain the specified properties for twenty years or more.

The aim of the present invention is a method for assessing the authenticity of the media protective label simple technical means under control of authenticity of documents and products.

An additional objective of the present invention is the reduction of the processes of production and circulation of documents and products by reducing the cost of the protective label.

The technical result consists in obtaining fluorescent protective ink that emits a fluorescent signal that is stable for twenty years or more, has a high intensity emissions (in units of the medium relative quantum yield of fluorescence - 80% and above) under the action of a source of visible (400-700 nm) or ultraviolet (300-400 nm) radiation in the claimed range of wavelengths of fluorescence from 400 nm to 3000 nm.

The problem is solved and the technical result is achieved by the fact that the fluorescent protective ink includes a solvent and a polymer matrix in which is dispersed semiconductor nanocrystals consisting of consecutive: a semiconductor core of the first semiconductor layer, second semiconductor layer and the silicone polymer layer. When this semiconductor nanocrystals emit a fluorescent signal in the wavelength range of fluorescence from 400 to 3000 nm under the action of the light source of visible or ultraviolet range, and the relative quantum yield of fluorescence is not less than 80%.

As the polymer matrix use the organosilicon compounds that can be selected from the group consisting of silicones, including silicone fluids, silicone elastomers, silicone resins, silanes or siloxanes.

In an advantageous embodiment of the semiconductor core is composed of a semiconductor material selected from the group of: ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, PbS, PbSe, PbTe, InP, InAs, CuInS2, CuInSe2, AgInS2, AgInSe2the first semiconductor layer which consists of a semiconductor material, selected from the group of: ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, PbS, PbSe, PbTe, InP, InAs, and the second semiconductor layer comprises a semiconductor material selected from the group of: ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, PbS, PbSe, PbTe, InP, InAs.

The presence of the first semiconductor membrane in semiconductor nanocrystals allows to eliminate the defects in the crystal lattice of the semiconductor cores, which increases the brightness of the luminescence under the action of the light source of visible or ultraviolet range, while the relative quantum yield of fluorescence increases and is not less than 80%.

The presence of the second semiconductor shell in semiconductor nanocrystals provides protection for the core and the first semiconductor membrane from exposure to the environment, which in turn ensures the stability of the fluorescent signal emitted by the fluorescent ink, for twenty years or more.

External covalently linked silicone polymer layer consists of a silicone polymer material chosen from the group: allyltriethoxysilane, (aminoalkyl)trialconsistent, (mercaptoethyl)trialconsistent, (alkylaryl)trialconsistent, tetraalkoxysilane, polysiloxanes.

The external organosilicon polymer layer as the second semiconductor shell provides additional protection from exposure to the environment. However, its main role is involved in the formation of colloidal solutions (sols), which are applied on various types of surfaces in the form of visible and/or invisible protective label.

It was established experimentally that the semiconductor nanocrystals have a hydrodynamic diameter in the sols of not more than 100 nm. The diameter of the semiconductor core is not more than 40 nm, and the thickness of each of the semiconductor layers is not more than 10 nm.

In addition, the fluorescent ink may contain a mixture of different semiconductor nanocrystals.

The solvent can be used in standard solvents. In the preferred embodiment, this may be water or alcohol, for example ethanol, propanol, isopropanol, butanol or a combination thereof. In addition, the solvent may be used saturated and unsaturated, or aromatic liquid hydrocarbons. In an advantageous embodiment, it is hexane, heptane, octane, nonan or their combination, as well as toluene, xylene or a combination thereof.

The composition of the fluorescent protective ink can optionally include surfactants selected from the group: polyethylene glycol, polypropyleneglycol, though, tetraethoxysilane, tetrahydrofuran, diethyleneoxide.

The composition of the fluorescent protective the ink can also include acrylic or polyurethane varnish.

Due to the unique combination of features belonging semiconductor nanocrystals included in the fluorescent ink which emits a fluorescent signal that is stable for twenty years or more, and has a high intensity emission is possible using the inventive fluorescent ink composition of the visible and/or invisible protective label by applying a product that can have any geometric shape and may be made of any known materials.

Also the problem is solved and the technical result is achieved in that in the method of controlling the authenticity of the product containing the protective label, use visualization protective label under the influence of a light source of visible or ultraviolet range, with subsequent visual identification received informative features, which include color hue and brightness, by comparison with informative signs described in the reference document and/or presents a reference mark and/or color of satin flowers, and the comparison of obtained and described informative features. Based on this comparison one can make a conclusion about the authenticity of the product. Moreover, as the protective label use visible and/or invisible protective the th tag-based fluorescent ink, above.

Also the problem is solved and the technical result is achieved in that in the method of controlling the authenticity of the product containing the protective label use reading fluorescent signal, comparing the received data with the existing database of signals, analysis of the obtained data comparison and subsequent results on the indicator and/or the display device on the basis of which one can make a conclusion about the authenticity of the product, and as a protective label use visible and/or invisible protective label-based fluorescent ink described above.

Fluorescent protective ink containing semiconductor nanocrystals dispersed in a polymeric matrix, and a solvent. The semiconductor nanocrystals used the nanocrystals is related to the third type: "core/first semiconductor shell/second semiconductor shell/outer silicone layer. Hereinafter use the following notation semiconductor nanocrystals type III: core/first semiconductor shell/second semiconductor shell/outer silicone layer. For example, CdSe/CdS/ZnS/tetraethoxysilane.

The claimed group of inventions is illustrated by drawings, on which:

Figure 1 - schematic image is laid on the semiconductor nanocrystals, members of the fluorescent protective ink;

Figure 2 fluorescence spectra of semiconductor nanocrystals;

Figure 3 is a graph of luminescence intensity (registration signal at 620 nm) fluorescent ink deposited on a silicon wafer with semiconductor nanocrystals structure of CdSe/CdS/ZnS/polymethylsiloxanes upon irradiation with a blue led (450 nm, 12 W) within 6,000 hours at a temperature of 30-50°C;

4 is a fluorescence spectrum of the fluorescent ink on the basis of a mixture of 4 kinds of semiconductor nanocrystals.

Figure 1 shows the structure of the semiconductor nanocrystals included in the fluorescent protective ink. Semiconductor nanocrystals are composed of a semiconductor core 1, the first semiconductor layer 2, the second semiconductor layer 3, the outer silicone polymer layer 4.

The core 1 may consist of a semiconductor material selected from the group of: ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, PbS, PbSe, PbTe, A1N, A1P, AlAs, AlSb, GaN, GaP, GaAs, GaSb, InN, InSb, InP, InAs, CuInGaS2, CuInGaSe2, CuInS2, CuInSe2, AgInS2, AgInSe2, AuGaTe2that is cited as an example, but not limiting the present invention.

Layer 2 may consist of a semiconductor material selected from the group of: ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, InP, InAs, InN, InSb, HgSe, HgTe, GaN, GaP, GaAs, GaSb, PbS, PbSe, PbTe, CuInGaS2, CuInGaSe2, AgInS2, AgInSe2, AuGaTe2, ZnCuInS2that is cited as an example, but not limiting the present invention.

The layer 3 may consist of a semiconductor material selected from the group of: ZnS, ZnSe, ZnTe, CdS, CdSe, CdTe, PbS, PbSe, PbTe, InP, InAs, which is cited as an example, but not limiting the present invention.

The layer 4 may consist of a silicone polymer material chosen from the group: allyltriethoxysilane, (aminoalkyl)trialconsistent, (mercaptoethyl)trialconsistent, (alkylaryl)trialconsistent, tetraalkoxysilane, polysiloxanes.

Changing the colloidal synthesis of (time, temperature, solvent composition), the qualitative and quantitative composition of the semiconductor material in the core, the composition of the semiconductor materials in the layers, the composition of the outer silicon layer can be obtained semiconductor nanocrystals and, accordingly, the fluorescent ink containing the semiconductor nanocrystals, with the given values of the fluorescent signal, which will last a long time under different environmental conditions.

Under the fluorescent signal should be understood detected informative signs, which, depending on the method of control will be divided into PR the signs visual and machine definitions. Signs of a visual determination applies, for example, the colour of the fluorescence label. Signs of a machine definition include, for example, defined sets of peaks with different wavelength fluorescence and the ratio of intensities of emission at several wavelengths.

Fluorescent ink containing semiconductor nanocrystals can have a certain maximum and minimum value of the wavelength of the maximum peak fluorescence. Listed below the maximum value of the wavelength of the peak maxima of the fluorescence of semiconductor cores are evidence that fluorescent inks emit a fluorescent signal in the present wavelength range 400-3000 nm, but are not limited to all possible combinations of semiconductor nanocrystals and sets of peaks with different wavelength fluorescence used to obtain mono - or multivariate (multi-color) fluorescent signal (Figure 2, Figure 4).

In particular, semiconductor nanocrystals containing semiconductor core of the CdS have a maximum value of the wavelength of the peak maxima of fluorescence in the range from 390 nm to 490 nm; a semiconductor core of CdSe from 470 nm to 690 nm; semiconductor CdTe core - from 550 nm to 700 nm; a semiconductor core of InP from 500 nm to 590 nm; a semiconductor core of CunS 2from 600 nm to 850 nm; a semiconductor core of the PbS from 800 nm to 2300 nm; a semiconductor core of the PbSe - 1000 nm to 2500 nm; semiconductor PbTe core - from 1200 nm to 3000 nm.

In an advantageous embodiment, when along with photostability it is desirable to obtain the relative quantum yield of fluorescence above 80%, while the cost of the protective label should be significantly lower analogues, it is possible to use semiconductor nanocrystals structure of CdSe/CdS/ZnS/polymethylsiloxanes. The maximum value of the wavelength of the peak maxima of fluorescence for a given type of semiconductor nanocrystals are in the range of from 500 nm to 700 nm, and the hydrodynamic diameter of the colloidal solution is not more than 40 nm.

If you want to get the maximum value of the wavelength range from 400 to 500 nm, while the use of semiconductor nanocrystals structure of the CdS/CdTe/ZnS/polymethylsiloxanes, which have maximum values of the wavelengths of fluorescence in the desired range, while the hydrodynamic diameter of the colloidal solution is not more than 30 nm.

Semiconductor nanocrystals structure of InAs/CdSe/ZnSe/methyl-phenyl of polysiloxan have a maximum wavelength of fluorescence in the range from 700 to 1600 nm hydrodynamic diameter of the colloidal solution is not more than 100 nm.

If you want to get maximum value DL is n waves in the range from 1600 to 3000 nm, the use of semiconductor nanocrystals structure of PbTe/PbS/ZnS/the phenyl polysiloxane, which have maximum values of the wavelengths of fluorescence in the desired range, while the hydrodynamic diameter of the colloidal solution is not more than 100 nm.

Preferential the embodiments of the present invention shown in examples 1-7.

Example 1. Fluorescent ink contained semiconductor nanocrystals structure of ZnSe/ZNS/CdS/poly(aminoethyl)trimethoxysilane, dispersed in a two-component silicone elastomer on the basis of a platinum catalyst (Dow Corning ® QP1). The solvent used was ethanol. Fluorescence spectrum of the ink containing nanocrystals ZnSe/ZnS/CdS, shown in figure 2 (pos.5). The size of the nanocrystals was 20 nm. The wavelength of maximum fluorescence was 400 nm.

Example 2. Fluorescent ink contained semiconductor nanocrystals structure InP/CdSe/ZnS/poly(methacrylate)triethoxysilane dispersed in polydimethylsiloxane. The solvent used was toluene. Fluorescence spectrum of the ink containing nanocrystals InP/CdSe/ZnS, shown in figure 2 (pos.6). The size of the nanocrystals was 24 nm. The wavelength of maximum fluorescence of 525 nm.

Example 3. Fluorescent ink contained semiconductor nanocrystals structure of CdSe/CdS/ZnS/poly(methyl)triethoxy is Ilan, dispersed in polydimethylsiloxane. As a surfactant was used though. As the lacquer was used acrylic lacquer. The solvent used was a mixture of toluene and xylene. Fluorescence spectrum of the ink containing nanocrystals of CdSe/CdS/ZnS, shown in figure 2 (pos.7). The size of the nanocrystals was 7 nm. The wavelength of maximum fluorescence was 550 nm.

Example 4. Fluorescent ink contained semiconductor nanocrystals patterns CuInS2/ZnSe/ZnS /poly(mercaptoethyl)trimethoxysilane dispersed in vinylpolysiloxane resin. The solvent used was hexane. Fluorescence spectrum of the ink containing nanocrystals CuInS2/ZnSe/ZnS, shown in figure 2 (pos.8). The size of the nanocrystals was 25 nm. The wavelength of maximum fluorescence was 680 nm.

Example 5. Fluorescent ink contained semiconductor nanocrystals structure of InAs/CdSe/ZnSe/methyl-phenyl of polysiloxane dispersed in polydimethylsiloxane. The solvent used was toluene. Fluorescence spectrum of the ink containing nanocrystals InAs/CdSe/ZnSe shown in figure 2 (pos.9). The size of the nanocrystals was 35 nm. The wavelength of maximum fluorescence amounted to 1300 nm.

Example 6. Fluorescent ink contained semiconductor nanocrystallisation PbSe/CdSe/ZnS/politician, dispersed in polymethylsiloxane 200. The solvent used was ethanol. Fluorescence spectrum of the ink containing nanocrystals PbSe/CdSe/ZnS, shown in figure 2 (pos.10). The size of the nanocrystals was 40 nm. The wavelength of maximum fluorescence was 2000 nm.

Example 7. Fluorescent ink contained semiconductor nanocrystals structure of PbTe/PbS/ZnS/politician dispersed in polymethylsiloxane 200. The solvent used was water. The size of the nanocrystals was 70 nm. The wavelength of maximum fluorescence amounted to 3000 nm (not shown in the figure).

Example 7. Fluorescent ink contained a mixture of 4 different semiconductor nanocrystals, dispergirovannoyj in the polymer matrix is a polydimethylsiloxane. The solvent used was toluene. Figure 4 shows the spectrum of the fluorescent ink containing a mixture of four different semiconductor nanocrystals: CdS/CdTe/ZnS/poly(methyl)triethoxysilane (size 5 nm, the wavelength of maximum fluorescence - 430 nm); CdS/CdTe/ZnS/poly(methyl)triethoxysilane (size 9 nm, the wavelength of maximum fluorescence - 490 nm); CdSe/CdS/ZnS/poly(methyl)triethoxysilane (size 7 nm, the wavelength of maximum fluorescence at 550 nm); CdSe/CdS/ZnS/poly(methyl)triethoxysilane (size 15 nm, the wavelength of maximum fluorescence at 610 nm).

In all these examples, the SRO is service fluorescent ink 20 years or more, and quantum yield of the luminescence of semiconductor nanocrystals in the ink composition, more than 80%.

Previously on documents and/or products that you want to protect against forgery, applied luminescent ink containing semiconductor nanocrystals. Fluorescent ink can be used as an independent protective label (such as fluorescent markers), and be part of a more complex security labels.

Method of monitoring the authenticity of the products having the protective label from the claimed fluorescent ink, perform one of two possible options.

The first option is to render the protective label under the influence of the light source. As a protective label use visible eye label based fluorescent ink described above. Visualization of the protective label is realized under the action of visible or ultraviolet light. Next, conduct a visual identification of the received informative features, which include color hue and brightness, by comparison with informative signs described in the reference document and/or presents a reference mark and/or color of atlases colors such as Pantone). After mapping obtained and described informative features make the convicts who tell about genuine or falsified documents, or products.

The second option is to read the fluorescent signal of the spectrometer or device based on a set of bandpass filters, comparing the received data with the existing database of signals. The device should detect the fluorescent signal by recording and analyzing the fluorescence spectrum of the protective label. In one implementation read from the device the signal is stored and analyzed by the microcontroller. The microcontroller calculates the wavelengths of the peaks, their relative intensity, determines the characteristic properties of the obtained spectrum and compares the data with data codes stored in memory. The result of the analysis and the comparison is displayed on the indicator and/or the display device in the form specified informational messages, which allows to make a conclusion about the authenticity or forgery of documents or products.

In the stability of the fluorescent signal emitted by the fluorescent protective ink for a long time, is accomplished through a comprehensive technical result, namely that the claimed fluorescent ink can be used in making and handling protected against forgery of documents and products made from natural, synthetic and composite materials having at least one sign of genuine leather, the particular made using visible and/or invisible protective label with subsequent identification by visual or machine definition.

1. Fluorescent protective ink containing a solvent and semiconductor nanocrystals dispersed in the silicone compound as a polymeric matrix consisting of consecutive: a semiconductor core, the first and second semiconductor layers, characterized in that the core material of the nanocrystals selected from the group comprising ZnS, CdSe, PbSe, InP, InAs, CuInS2; the material of the first semiconductor layer selected from the group comprising: ZnS, ZnSe, CdS, CdSe, PbS; the material of the second semiconductor layer selected from the group comprising: ZnS, ZnSe, CdS; these nanocrystals include the outer layer, the material of which is selected from a silicone polymer, from a range that includes poly(aminoethyl)trimethoxysilane, poly(methacrylate)triethoxysilane, poly(methyl)triethoxysilane, poly(mercaptoethyl)trimethoxysilane, methyl-phenyl of polysiloxan, politician; and the material of the polymer matrix is selected from a range that includes silicone elastomer, polydimethylsiloxane, polymethylsiloxane, vinylpolysiloxane resin; semiconductor nanocrystals emit a fluorescent signal in the wavelength range of fluorescence from 400 to 3000 nm is the od action of a light source of visible or ultraviolet range, the relative quantum yield of fluorescence is not less than 80%.

2. Fluorescent ink according to claim 1, characterized in that the solvent used water.

3. Fluorescent ink according to claim 1, characterized in that the solvent is chosen from the group consisting of ethanol, propanol, isopropanol, butanol, or a combination of both.

4. Fluorescent ink according to claim 1, characterized in that the solvent is chosen from the group consisting of hexane, heptane, octane, nonan or a combination of both.

5. Fluorescent ink according to claim 1, characterized in that the solvent is chosen from the group consisting of toluene, xylene, or a combination of both.

6. Fluorescent ink according to claim 1, characterized in that the composition may include a mixture of different semiconductor nanocrystals.

7. Fluorescent ink according to claim 1, characterized in that the semiconductor nanocrystals have a hydrodynamic diameter in the sols of not more than 100 nm.

8. Fluorescent ink according to claim 1, characterized in that the diameter of the semiconductor core is not more than 40 nm.

9. Fluorescent ink according to claim 1, characterized in that the composition can optionally include surfactants selected from the group: polyethylene glycol, polypropyleneglycol, though, tetraethoxysilane, tetrahydrofuran, diethyleneoxide.

10. Fluorescent ink according to claim 1 characterized in, the composition can optionally include acrylic or polyurethane varnishes.

11. The method of applying a fluorescent protective ink products, characterized in that these products cause the fluorescent ink according to claims 1-10.

12. Method of monitoring the authenticity of the product containing the protective label, including the visualization of the protective label under the influence of a light source of visible or ultraviolet range, with subsequent visual identification received informative features, which include color hue and brightness, by comparison with informative signs described in the reference document and/or presents a reference mark and/or color of satin flowers, the comparison of the received and informative features described on the basis of which one can make a conclusion about the authenticity of the product, characterized in that the protective label use visible and/or invisible protective label-based fluorescent ink according to claims 1-10.

13. Method of monitoring the authenticity of the product containing the protective label, including the reading of the fluorescence signal, comparing the received data with the existing database of signals, analysis of the obtained data comparison and subsequent results on the indicator and/or the display device, on the basis of which they make Zack is Uchenie about the authenticity of the product, characterized in that the protective label use visible and/or invisible protective label on the basis of the fluorescent ink according to claims 1-10.



 

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21 cl, 16 dwg

FIELD: textiles; paper.

SUBSTANCE: invention relates to a means of protection on a paper base, and also to the method of manufacturing this means of protection and to protected documents, which have, at least one such means of protection, built in them and/or on them. Means of protection on or in such a document, like a paper with protection from forgery, which has a paper base, possessing tensile strength while wet and opposite flat surfaces. In this case the base has the symbols printed on only one side, where the symbols are visible from the printed side and from the opposite surface of the base.

EFFECT: increase in the degree of protection of documents from forgery, with easier verification of their authenticity at the same time.

21 cl, 2 dwg

FIELD: textile, paper.

SUBSTANCE: cardboard is used in products which originality should be confirmed. Cardboard contains filamentary matrix with two surfaces. Back surface of filamentary matrix includes layer of surface sizing compound containing marking agent in the form of particles less than 50 mcm in size. For cardboard production filamentary matrix is used, which surface is sized from at least one side representing back side of cardboard. Marking agent in the form of particles of less than 50 mcm size is introduced into sizing compound and marking agent particles are fixed on cardboard. Filamentary matrix is subject to surface sizing in pot or in film and sizing press or by means of doctoring device.

EFFECT: reduction of marking agent particles consumption by 80-90% and improvement of products quality.

34 cl, 1 dwg, 2 ex

FIELD: chemistry.

SUBSTANCE: disclosed is a yellow afterglow material having the chemical formula aY2O3·bAl2O3·cSiO2:mCe·nB·xNa·yP, where a. b. c. m, n. x and y are coefficients, where a is not less than 1 but not greater than 2, b not less than 2 but not greater than 3, c is not less than 0.001 but not greater than 1, m is not less than 0.0001 but not greater than 0.6, n is not less than 0.0001 but not greater than 0.5, x is not less than 0.0001 but not greater than 0.2, and y is not less than 0.0001 but not greater than 0.5, wherein Y, Al and Si are basic elements and Ce, B, Na and P are activators. Also disclosed is a method of producing the disclosed material and a light-emitting diode device using said material.

EFFECT: making alternating current light-emitting diodes from luminescent materials.

10 cl, 6 dwg, 4 tbl, 14 ex

FIELD: metallurgy.

SUBSTANCE: composition for marking of metal products produced by powder metallurgy method includes not more than 50% of wt % of luminophor and 50 wt % and more of binding-lubricating agent being fatty acid derivatives or powders of synthetic wax and/or paraffin. Marking of metal products by this composition consists in mixing of alloy metal powder with marking composition, which consists of at least one inorganic agent with property to provide luminescence at irradiation and binding-lubricating agent with subsequent pressing of obtained mixture and its sintering at temperature not exceeding 900°C.

EFFECT: possibility of products marking during their production by powder metallurgy method, simplifying marking technology and providing safety.

15 cl, 1 dwg, 8 ex

FIELD: chemistry.

SUBSTANCE: invention relates to light-converting coating material for greenhouses and a composition for producing said material and can be used in agriculture and plant growing to grow plants in protected ground. The light-converting coating material consists of an optically transparent base and a light-converting composition which is deposited on the base and consists of a polymer matrix and a phosphor. The phosphor is semiconductor nanocrystals which are made of a semiconductor core and at least one semiconductor cladding such that the particle size of the nanocrystals in the light-converting composition ranges from 1 nm to 100 nm.

EFFECT: present invention considerably increases crop yield by converting part of UV radiation into the orange-red spectral range.

17 cl, 3 dwg, 2 tbl, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to novel complexes of rare-earth elements, which can be used as active layers of organic light-emitting diodes, optical-electronic devices as well as fluorescent labels and markers. Disclosed is a luminescent complex of rare-earth elements of formula [Ln(L1)3L2] (I), where Ln is an ion of a trivalent rare-earth element, L1 is a diketonate ligand - a derivative of 3-polyfluoroalkyl-1-pyrazolyl-1,3-propanediol of formula (II), where RF is CH2F, CHF2, CF3, fluorinated alkyl, cycloalkyl or aryl, L2 is an auxiliary bidentate N, P or O-containing ligand. A method of producing compound (I) is also disclosed.

EFFECT: invention enables to obtain novel compounds (I) with high luminescence intensity compared to their non-fluorinated counterparts, and also enables to vary in a wide range such process parameters of compounds (I) as thermal stability, film-forming capacity, solubility and volatility in a vacuum, which are necessary for use in optical-electronic devices.

2 cl, 3 dwg, 12 ex

FIELD: physics.

SUBSTANCE: invention relates to a method of predicting photostability of colloidal semiconductor quantum dots with a nucleus-shell structure in an oxygen-containing medium, involving measuring kinetics of a photoluminescent signal of quantum dots for the tested and reference batches, determining for said batches values of a parameter which characterises the rate of decay of the photoluminescent signal over time. The rate is characterised by that quantum dots are pre-deposited on the surface of a solid substrate, and said measurement is carried out in a gaseous medium containing ozone with fixed concentration. Further, a higher level of photostability of the tested batch relative the reference batch is predicted with the ratio of values of said parameter corresponding to decrease in the rate of decay of the photoluminescent signal for the tested batch relative the reference batch and vice versa.

EFFECT: use of the present method does not require use special expensive microscopic equipment, powerful photoexcitation sources, additional photoexcitation sources and liquid or toxic chemicals.

3 cl, 1 dwg

Luminous body // 2445340

FIELD: physics.

SUBSTANCE: inorganic composition for producing electroluminescent material contains the following, pts.wt: 80-95 semiconductor compound consisting of group II and group VI elements; 0.001-3 iridium source or a combination of an iridium source and at least one source of metal other than iridium; 3-9 activator. To obtain electroluminescent material, the inorganic composition is subjected to an explosion using a propellant and/or blasting explosive in a sealed vessel followed by thermal treatment. The obtained electroluminescent material is used as a light-emitting layer between electrodes of an inorganic electroluminescent device whose brightness when excited with direct current is equal to or higher than 10000 cd/m2.

EFFECT: invention not only increases brightness but also prolongs the service life of the light-emitter.

12 cl, 5 dwg, 2 tbl, 3 ex

FIELD: chemistry.

SUBSTANCE: nanocomposite has a thermoplastic copolymer as a polymer matrix. At the step of preparing a composition or moulding the article, nanosized silicon is added to the copolymer as a light-converging component in amount of 0.001-1.5 wt % with particle size 1-5 nm, said component containing silicon dioxide in the surface layer of the core.

EFFECT: invention enables to form a nanocomposite having bright and sustained photoluminescence in the range from 750 to 500 nm, which is retained at high temperatures.

4 dwg, 5 ex

FIELD: physics.

SUBSTANCE: luminophore consists of crystal lattice of seed material with activating additives representing ions Eu2+, Tb3+ and/or Eu3+. Said seed material, when excited by high-energy excitation radiation, absorbs at least portion of said excitation radiation to, then, emit radiation with lower power. Note here that seed material lattice represents carbide-silicon nitride compounds not containing cerium as activating additive. Invention covers also luminophore with its seed material lattice represents compound with general formula Ln2Si4N6C, where Ln stands for element or mix of elements selected from group including yttrium, lanthanum, gadolinium and lutetium.

EFFECT: reduced tendency to luminescence quenching, higher temperature and chemical stability.

11 cl, 6 dwg, 4 ex

FIELD: chemistry.

SUBSTANCE: invention relates to scintillation materials, specifically to two-layer fibrous scintillators for detecting slow neutrons and suitable for making scintillation fibrous detectors for radiation environmental monitoring, for monitoring space and industrial neutron background, for making systems for monitoring nuclear fuel and articles made from fissile materials, as well as for making antiterrorist radiation monitoring systems. The method of making two-layer fibrous scintillator involves heating core and cladding material at 180-190°C, pressure 150-180 kg/cm2 and then moulding the two-layer structure of the fibre through extrusion at a rate of 1.0-1.5 m/h. The material of the core of the scintillator contains the following in wt %: silver chloride 5.0-10.0; silver bromide 87.5-85.0; silver iodide 0.5-1.0; thallium (I) iodide 7.0-4.0, and the cladding material of the scintillator contains the following in wt %: silver chloride 18.0-20.0; silver bromide 80.5-79.4; silver iodide 0.1-0.5; thallium (I) iodide 0.5-1.0. The invention enables to obtain a new generation of flexible long two-layer fibrous scintillators with fluorescence spectrum maximum between 600 nm and 800 nm.

EFFECT: two-layer fibre structure enables transmission of scintillation radiation with virtually no loss owing to the effect of total internal reflection of radiation in the core of the fibre at the core-cladding boundary surface.

3 ex

Valuable document // 2407771

FIELD: information technology.

SUBSTANCE: counterfeit protected paper, protective element or valuable document contains a luminophor of general formula XZO4, in which X denotes YbLacPreNdfErnYbpFe(III)v, where b + c + e + f + n + p + v=1, and each of indices b, c, e, f, n, p, v assumes a value between 0 and 1, where either n≠0 and p≠0, or f≠0 and p≠0, or n≠0and f≠0, Z denotes NbzaTazbPzd, where za + zb + zd = 1, and each of the indices za, zb and zd assumes a value between 0 and 1. The luminophor can be added to printing ink, can be deposited on a surface or entered into the volume of the valuable document and can be embedded into the composition of melange fibres, protective threads. The valuable document can be made from paper or a polymer, the protective element can be made in form of a strip, tape, thread, plate, melange fibre or label. To authenticate the document, duration of luminescence or wavelength and/or number and/or form and/or intensity of the line of the radiation emitted by the luminophors and/or the band exciting radiation is analysed. The lines of radiation emitted by the luminophors and/or bands of exciting radiation form a code.

EFFECT: increase in number of luminophors used during authentication.

48 cl, 1 dwg, 2 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: polymer composition contains a first basic polymer (A) containing at least a thermoplastic polymer; a second basic polymer (B) containing at least a thermoplastic polymer and which is incompatible with the first basic polymer (A); and an additive (C) containing at least a substance which is incompatible with any of the first basic polymer (A) and the second basic polymer (B). The additive (C) is a liquid or suspension at temperature lower than the pyrolysis temperature of the first basic polymer (A) and the pyrolysis temperature of the second basic polymer (B). Components (A), (B) and (C) are separated from each other by a phase, and boundary surfaces, each lying between two phases (A), (B) and (C), are in contact with each other, forming spatially continuous parallel boundary surfaces. A moulded product, for example, is a filter or a spacer for refrigerators or capacitors. The polymer composition is used to produce an adhesive, ink, paint, films and fibre for a powdered catalyst.

EFFECT: polymer composition and products therefrom quasi-stably contain a large amount of substance which is incompatible with a polymer matrix, therefore suitable for obtaining moulded articles and other products having various properties.

25 cl, 10 ex

FIELD: chemistry.

SUBSTANCE: water based flexographic contains biodegradable polyhydroxyalkanoate (PHA) consisting of monomers having the following formula: where n is an integer from 1 to 5, and R1 is selected from a group comprising hydrogen, alkyl from C1 to C20, and alkenyl from C1 to C20, and having molecular weight ranging from 500 to 5000000 g/mol, binder substance which is three-block amphiphilic compound having two hydrophobic terminal areas with linear and/or branched aliphatic chains CnH2n+2, n = 1-40, and one central hydrophilic area - polyethylene glycol and its derivatives; or having one central hydrophobic area with linear and/or branched aliphatic chains CnH2n+2, n = 1-40, and two hydrophilic terminal areas, a solvent, and a dye or pigment in amount sufficient for leaving a visible mark on a base. Concentration of PHA in the ink ranges from 20 to 80% (weight/volume), concentration of the binder ranges from 0.5 to 20% (weight/volume), concentration of the solvent ranges from 1 to 25% (weight/volume) and concentration of the dye or pigment ranges from 1 to 40% (weight/volume). Described also is a method of preparing water based flexographic ink and a printing composition which contains the said flexographic ink.

EFFECT: improved biodecomposition properties.

13 cl, 6 ex

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