Method and set of printing inks for marking and identification of articles

FIELD: marking and identification of protected articles, such as bank-notes, service papers, labels, foil, fiber, card or industrial products.

SUBSTANCE: proposed printing ink contains dyes or pigments of expanded or hyperchromatic color space which is not reproduced by means of standard 4-color reproducing equipment. Identification of marking includes mathematical conversion of non-processed spectral information into statically independent hyperchromatic coordinates and comparison of selected hyperchromatic coordinates with respective standard magnitudes. Specification gives also description of printing inks and method of marking and identification of articles.

EFFECT: enhanced efficiency.

25 cl, 6 dwg, 2 tbl, 4 ex

 

The technical field to which the invention relates.

The present invention relates to the protection of documents and products, that is, banknotes, securities, documents of identification, ID cards, tickets, labels, protective films, protective threads and the like, the identification of which can be easily implemented using a stationary or portable electronic equipment such as receivers exchange (ATMs), technological devices, the device checks the tickets, the manual identification and others, and to methods of obtaining and identifying such security documents by the use of dyes or pigments having specific spectral characteristics of absorption.

The increasing availability of high-quality desktop hardware for color printing and reproduction, such as computer printers, color printing, color scanning and color copying equipment, to the public, poses additional problems of security documents. In particular, the currently adopted security settings do not provide sufficient protection against fraud in the receivers of ATMs, which are used to identify solely electronic means.

The level of technology

Known security settings that are appropriate to identify the purpose electronic means, described, for example, in documents EP-IN-0053124 and ER-IN-0053 183, ER-IN-0053125 and ER-IN-0024053. EP-IN-340898 or ER-IN-537431. These parameters are based on luminescence, magnetic properties or absorption of electromagnetic radiation in the invisible region of the spectrum. However, the application of some of these physical effects associated with disadvantages. For example, in the case of luminescence intensity of the measured radiation is generally low, therefore, requires a very complex technology, including shielding from ambient radiation and other effects of potential disturbances. Magnetic properties are less suitable as protection parameter, as in this case usually requires mechanical contact between the bill and the magnetic sensor (reading head). This is the main source of errors caused by jamming of crumpled banknotes in the reader.

Noteworthy is the lack of "classic" security settings banknotes based on UV or IR radiation, such that disclosed in document EP-B-0024053 consists in the fact that they used a single connection-absorber as a masking element protection outside the visible region of the spectrum. The presence of a masking element of protection can be identified using publicly available CCD cameras (e.g., door cameras, with sensibility is Yu in the wavelength range from 300 to 1100 nm) and public generic UV and IR filters, sold in photoshop. In addition, the generic compounds that absorb UV and IR radiation, are used in many areas of modern technology, namely in certain electrophotographic the developers, and thus, they are also available for sale.

Disclosure of inventions

Therefore, the aim of the present invention is to protect products against counterfeiting, which overcome the above-described shortcomings of the prior art and which permits easy identification of the specified products, through such devices as receivers exchange, ticket validators, etc.

The problem is solved, in particular, by using inks for printing and/or set of printing inks and their use for marking and/or identification of the product as set forth in the independent claims.

The present invention is based on the selection of dyes or pigments, which may not properly perceived by the human eye, in particular on the selection of such a set of printing inks or pigments that make up a color set, which is not fully perceived by the human eye.

The perception of color by the human eye based on the signals only three receptors of different types: one for the long-wave region (600 nm, red), one for the intermediate region (550 nm, green), and Odie is for the short wavelength region (450 nm, blue) spectrum. In addition to these receptors also have a receptor common white light having a maximum sensitivity at about 550 nm. The curves of the relative sensitivity of these three receptors, which correspond to the curves of the spectral absorption of the respective photopigments eyes, determined experimentally, and they are known as Functions of matching color and is established by the International Commission on illumination (CIE). These functions form the basis of all technology color man. It is noteworthy that every visible color can be expressed using this system CIE-XYZ, using three primary color coordinates: X (red), Y (green) and Z (blue); limiting the human perception of color only the three-dimensional color space. It should be noted that in the human eye there is no perception of light in the ultraviolet (UV, wavelength less than 400 nm) and infrared (IR, wavelength greater than 700 nm) bands of the electromagnetic spectrum.

In the past, considerable efforts were focused on the development and selection of dyes, pigments and other devices, in order to reproduce colors the most "naturally", in accordance with properties of the human eye. Modern technology of color reproduction based on a narrow selection of this item is suitable pigments for printing, careful selection of phosphors for cathode ray tubes and improved optical filter apparatus for color photography and scanning elements.

However, the color in the field of use for protection has a completely different purpose. Necessary objects should not be depicted in the "true" color, but much more often the color is purely functional load, for example, it is necessary to distinguish different designations within the series of exchange.

To counter current trends overall availability and even more perfect equipment for color reproduction, currency, valuable documents and other items, the reproduction of which is undesirable in the present invention describes a new method of marking and/or identification on the basis of the selected dyes or pigments. The present invention is based on the deliberate destruction of the primary colors of the three-dimensional color space CIE-XYZ. Marking valuable document or article according to the invention includes (i) the visible colors that are not used in conventional color reproduction or printing, (ii) sinks in a narrow band spectrum, which provide only pastel shadow color, and (iii) the invisible "colors", which correspond to the absorption outside the visible region of the electromagnetic spectrum (from 400 to 700 nm), Il is in the ultraviolet (wavelength less than 400 nm) and infrared (wavelength greater than 700 nm) range.

Thus, the present invention relates to ink for printing, which includes at least one dye or pigment having at least one absorption maximum in the visible region of the electromagnetic spectrum, which differs significantly from the absorption maxima of the basic color system of the CIE-XYZ, and at least one other dye or pigment having an absorption band in the visible region of the electromagnetic spectrum, with specified band width at half intensity narrower than 2400 cm-1preferably narrower than 2000 cm-1and most preferably narrower than 1500 cm-1and at least one other dye or pigment having at least one absorption maximum in the ultraviolet or infrared region, preferably in the near infrared region of the electromagnetic spectrum.

In addition, the present invention relates to a set of printing inks containing at least two inks for printing, which is defined above. In particular the present invention discloses the use of "hyperchromic color system", incorporated into the appropriate set of dyes or pigments and/or appropriate set of printing inks and containing at least three, preferably at least 4 basic colors, which are chosen in such manner and on the Ohm, to have at least one maximum absorption, which is significantly different from the absorption maxima of the basic color system of the CIE-XYZ (which include additive primary colors - red, green, blue, or subtractive basic colors - yellow, purple, and blue, respectively). Moreover, the color system according to the invention may include components that selectively absorb in the UV, visible and IR spectral regions, which embodies the appropriate dyes or pigments. In addition, the system may include components, selectively reflective in the UV, visible and IR spectral regions, which embodies the appropriate pigments. Preferably visible dyes or pigments are chosen so that they had the spectral maxima of the transmission or reflection that differs from the highs of the CIE-XYZ, located at 450 nm (blue), 550 nm (green) and 600 nm (red). Preferably the color system according to the invention includes at least one dye or pigment absorbing in the UV or IR regions of the electromagnetic spectrum; more preferably color system includes at least two dye or pigment absorbing in the infrared region of the electromagnetic spectrum.

In the context of the present invention are of particular interest KRA is Italy or pigments, absorption in a narrow region of the spectrum, as they allow you to enter more spectral species within the given available range of the spectrum (such as the range from 300 to 1100 nm). In the visible range of the spectrum preferred dyes or pigments are significantly more narrow absorption bands compared with the color matching Function of the CIE-XYZ for the eyes. Then you can even block the visible region of the spectrum more than these three dyes or pigments, and thus creates a hyperchromic visible color space.

Features matching color for eyes have the following remarkable properties:

The maximum sensitivityHalf-band
Blue absorber445 nm (22500 cm-1)55 nm (2800 cm1)
Green absorber555 nm (18000 cm-1)110 nm (3600 cm-1)
Red absorber595 nm ( 16800 cm-1)85 nm (2400 cm-1)

The first of these figures relate to the wavelength (in nm); the second digit refers to the energy (in cm-1respectively.

Conversion factors 1000 cm-1corresponds to 10000/LW.

Width Pelosi cm -1corresponds to 10000 current/LW2

(DV - wavelength in nm; GSR - band width in nm).

Significantly more narrow absorption bands compared with those specified in the Function of matching color should mean in the context of the present invention, the absorption band having a width (width at half intensity) narrower than 2400 cm-1. In particular, the dye or pigment according to the invention preferably have a width less than 2000 cm-1more preferably, the width of the strip is less than 1500 cm-1. However, the bandwidth of the specified dye or pigment must be greater than 100 cm-1except in very escapology absorbers on the basis of rare earth elements.

In addition, interest narrowband dyes or pigments that absorb in the ultraviolet (300-400 nm) and in the infrared region, in particular in the range of wavelengths from 700 to 1100 nm, which can be detected using available industrial devices with silicon photodetectors, such as photodiodes, CMOS and CCD cameras. The use of a pair of compounds which absorb in a narrow band in the IR range of wavelengths allows you to make graphics "multivitamin" design protection, containing one or more invisible "infrared dyes". In a specific embodiment, which may be used three infrared pigment, absorbing in the range respectively from 700 to 800 nm, 800 to 900 nm and from 900 to 1000 nm, in order to print trichrome image in the infrared region of the electromagnetic spectrum, which is invisible to the naked human eye. This image can be masked by printing with consistent imposition of one or more visible colors, transparent to IR. Then trichrome image in the infrared region can be visualized or examined using the appropriate e "IR color camera and a visual color display.

Dyes or pigments, which can be used according to the present invention can typically be selected from among molecular organic compounds, polymeric organic compounds or inorganic compounds. In the framework of the present invention, the main element is to "dye" hyperchromic color system, embodied the relevant individual chemical compound which may have one or more absorption bands in the spectral range from 300 to 1100 nm. Thus, hyperchromic color system that includes at least three, preferably at least 4 basic colors, embodied paint to print or a set of printing inks containing, IU the greater extent, three, preferably at least 4 different chromophore compounds, that is, absorption spectra which differ significantly from others in the wavelength range from 300 to 1100 nm. The term "substantially different" according to the invention means that the ratio of the statistical correlation of the two spectra, represented by two vectors s1 and s2, which is expressed by the normalized scalar product (s1·s2)/([s1]·[s2]), should not exceed 0,95. In terms of the vectors s1 and s2" are explained below.

Thus, not all dyes or pigments are very different in color, for example, hyperchromic color system may include two different yellow, two different blue and two red dye or pigment in different ratios. Photocopieuse device will reproduce these colors, using only yellow, only blue, and the only red dye. Corresponding to the detecting device, in contrast, will be designed for two different yellow, two different blue and two red source, and thus has the ability to easily distinguish between the original and the copy.

The dyes and pigments used in the embodiment of the method and obtain inks for printing or covering compositions according to the invention can be found in the ranks classes of compounds. In the preferred embodiment, they can be selected from the group consisting of cyanine (polymethine) and related chromophores type Tianyou; quinones and related chromophores type quinones; porphyrins, phthalocyanines and related macrocyclic chromophores, as well as heterosomata polycyclic chromophores. In the context of the present invention, the term "chromophore" means "generating color" chemical group that absorbs radiation in the region of wavelengths from about 300 to 2500 nm. The chromophore may be molecular or polymeric structure; in addition, it can contain chemical deputies of all types and/or may be attached or grafted to the polymer chain.

Cyanine (polymethine) dyes known in the art and are used as photographic sensitizers (D.M.Sturmer, The Chemistry of Heterocyclic Compounds, vol.30, John Wiley, NY, 1977, pp.441-587; Eastman Kodak). In a more modern use of stable representatives of compounds of this class, selected from coumarins and rodinov, are also used as laser dyes (J.B.Marling, J.H.Hawley, E.M.Listen, W.B.Grant, Applied Optics, 13 (10), 2317 (1974)).

Porphyrins and related compounds can be considered as macrocyclic cyanine structure and the conformational rigidity due to its own cyclic structure, including the availability of the m a coordinating metal ion, such as Mg2+and others. In the long-wavelength absorption band of porphyrins is very sharp, and they represent an almost perfect example of the dye according to the invention with a narrow absorption band. The chlorophyll-a absorption band at 660 nm, the extinction coefficient ε=85000) is a dye of this class (.Sauer et al., J.Am.Chem. Soc. 88 (1966), 2681-88). Because porphyrins and related compounds is quite difficult to synthesize, their industrial application is limited to compounds of natural origin.

Phthalocyanines and related compounds represent "industrial version of the porphyrins. They usually absorb in the wavelength region of the visible spectrum, and the width of the absorption band depends strongly on the packing of the crystal structure (aggregation). Usually a narrow absorption band is observed in dilute solution of such dyes and certain pigments in the solid state, in particular, if there is no stacking of the chromophore groups of the pigment. Class phthalocyanines generally also includes analogs with a greater degree of coupling, such as naphthalocyanine, which absorb in the far IR region, as well as heterosomata analogues phthalocyanines; a common item that defines this class of compounds is that they are all made from aromatic the RTO-dicarboxylic acids or their derivatives.

Quinone dyes known in the art and are used in dyeing and in related areas (for example, Indigo dyes, antrahinonovye dyes, etc.). Along the quinone skeleton can be electronegative groups or atoms, in order to strengthen the intensity of the absorption band or in order to shift the absorption band in the longwave region of the spectrum. For some of the dyes of this class, especially those in which no group NH or HE observed a narrow absorption band. Examples of such dyes are N,N'-dialkylanilines, N,N'-alkylenediamine and others.

Heterosomata polycyclic hydrocarbon dyes are rigid planar molecular structure, similar to the graphite lattice, which contain respective deputies. Examples of such dyes are perylenediimide, chinagreen, dioxazine and others.

An important aspect in the development of pigments that absorb in the narrow region of the spectrum, is to prevent aggregation of the individual molecules of the coloring matter; this tendency is inherent in the majority of organic polycyclic compounds, and she is greatly enhanced if possible formation of hydrogen bonds. In most cases, aggregation leads to broadening of the spectral bands n the absorption; thus, in the framework of the present invention aggregation is an undesirable phenomenon. To solve aggregation there are different ways:

- the use of the coloring matter molecules that do not form these aggregates, ashiraya absorption band,

- the use of the coloring matter molecules, which are soluble in inert compound polymer carrier; received significantly shredded polymers, dyed, can be used as a pigment for printing,

- the use of the coloring matter molecules that are capable of copolymerizate in a given polymer matrix, for example, polystyrene, or which can be inoculated to an existing polymer; received significantly shredded polymers, dyed, can be used as a pigment for printing or as laterala Supplement.

A significant number of dyes or pigments suitable for carrying out the invention, already described in the literature. However, usually commercially available dyes are specially designed to match the color functions for broad lines of the human eye. For this reason, the majority of known compounds or compositions that absorb in the narrow area, do not apply in the industry as dyes or pigments, or because of "missing the I in them saturated color, which is perceived by the human eye, or because of a change in color depending on the light ("true color"). This is also true for industrial dyes or pigments that absorb in the infrared region, which are intended for use in optical recording materials that require a fairly broad absorption band.

The lack of industrial market for most of the dyes or pigments used in the framework of the present invention, increase protection for the described method and its embodiments. When using non-industrial dyes or pigments in the field of protection of printed products require their specialized production and the result is effective control of source material; these very important requirements guarantee the security of the document.

Preferred dyes according to the present invention shown in figure 2. On figa depicted hexadeca-(3-ethoxy-1-thiophenolate)phthalocyanine-zinc(II)absorbing in the region of 780 nm. On figb depicted DECA-(3-ethoxy-1-thiophenolate)hexa-(3-methyl-1-thiophenolate)phthalocyanine-zinc(II)absorbing in the region of 850 nm. The formula on figb given for industrial product and represents a statistical average of a distribution of substituents.

In t is hnologie identification, presented in the invention, the intensity values of spectral reflectance for the identified document is not used directly as such, but rather are associated with the composition of the dye and/or pigment on paper, in order to give the system a high degree of stability in the practical application.

In the following it is assumed that the document is subjected to identification by assessing its characteristics of light reflection. However, the method and device can be used with the necessary changes, as well as with the identification document according to its characteristics of light transmittance, such those used in some types of vending machines for the sale of goods. In the case of reflection using traditional pigments mixing subtractive colour observed in the reflection color is due to the spectral absorption of the pigment, since the incident light first passes through the pigment, is reflected back from the white background and passes a second time through the pigment. The overall effect is a simple doubling of the visible color saturation compared with the corresponding transmission case.

To estimate values of optical density OD=lg(I0/IRefor OD=lg(I0/ICR), not the values themselves intensity of the reflected or missed with the ETA. At a given wavelength λ the optical density is proportional to the concentration of the pigment, the layer thickness d and the value of the specific absorption pigment ε(λ)

OD(λ)=·d·ε(λ) (law Bera).

In hyperchromic color system select the base color is free, provided that the specified base color has different absorption spectra or reflection, such as defined above. The correlation between the measured absorption spectrum or reflection S(λ) and the corresponding "hyperconcave coordinates" x1, x2, X3, x4, ... in the selected hyperchromic color system, which denote the concentration or "optical density" of an individual chromophore compounds can be installed using linear algebra. Derived "hyperconcave coordinates" allow remarkable set of statistically independent values for each dye or pigment hyperchromic color system, if the dyes or pigments set have overlapping absorption spectra. This method will be described in the following using the well-known formalism of matrix algebra.

According to this method, a standard absorption spectrum of S(λ) dye or pigment is expressed by the vector s=(s1, s2, s3, ... sn), where s1, s2, s3 , ... snrepresent the measured values of the spectral absorption (optical density OD=lg(I0/IRef), as defined in the prior art) at n different wavelengths λ1that λ2that λ3, ... λn. These wavelengths can be selected in this invention freely, but they must be associated with the use of dyes or pigments to provide excellent discrimination of the various components of hyperchromic color system.

In addition, hyperchromic color system will include m different dyes, and the value m is smaller, usually half or less than n, the number of measured intensity values for different Dean waves of light. Thus, there are m of these vectors s, representing the spectra of absorption or reflection of dyes or pigments. These m vectors s are arranged in a rectangular matrix containing m columns by n elements each. Any linear combination of the dyes within the selected hyperchromic color system will lead to the spectrum of absorption or reflection of y=(y1,2,3,n)that can be expressed using matrix equations

And·x=y

where a means the specified matrix size (n x m); x is a vector of m linear factors corresponding to wipe the color coordinates, and we mean the vector obtained n values of the spectral absorption or reflection.

On the other hand, knowing the matrix a, we can Express the measured absorption spectrum or reflection N1 in units hypercity coordinates x, using the classical formula of "least squares" linear algebra

x=(A'·A)-1·'·N1,

in which A' denotes the transposed matrix a and (A'·A)-1means converts the matrix. The adequacy of the compliance of this approximation can be estimated using statistical criteria such as the sum of squared deviations (y-Y1)'·(u-U1), or other criteria known from the prior art. Such criteria can be used as an additional means of identification.

Preferably the adequacy of compliance appreciate the balance, or the number R, which is defined as R={(U1-u)'·(U1-u)}/[(N1)'·(U1)], where y=And·x represents a calculated theoretical spectrum corresponding to hypercity coordinates x, and N1 denotes the spectrum of the sample measured during the test. The value of R is zero for a perfect match (y=Y1) and R is equal to 1 if there is no match (y=0). In addition, this number R is relatively insensitive to random fluctuations (statistical noise)affecting the measured spectrum N1, but very sensitive to sist the automatic bias that is, the presence of incorrect or additional, unexpected dye or pigment in the cover composition.

In addition, the same purpose can be used with other similar algorithms of linear algebra. Noteworthy is the decomposition algorithm for special values (SVD), which refers to the problem of solving equations and the method of "least squares".

The above means that there is a (m x n) matrix M, in which the measured spectrum refers to hypercity coordinates x of the corresponding color space, using a simple mathematical transformation

x=M·.

This matrix M=(A'·A)-1·And' can be calculated from the absorption spectra of base colors hyperchromic color system.

The above-mentioned dyes or pigments hyperchromic color system introduced in the ink for printing, or in the covering composition, or in a set of printing inks or coating compositions used according to the present invention, in the method of marking a product, such as a banknote, a document, ticket, label, foil, thread, card or industrial goods, which includes a stage ensure marking of the specified products, such as indexes or schema defined by the consumer, which is applied by using at least one of the inks for printing or covering composition, or set of printing inks or coating compositions, which are defined above.

In addition, these dyes or pigments are incorporated in the ink for printing or covering composition, or in a set of printing inks or coating compositions and applied to the product used according to the present invention, in the method of product identification, such as a banknote, a document, a ticket, a foil, a thread, a label, card or industrial goods, which includes the following stages:

a) measuring the optical spectrum of absorption, reflection or transmission for the specified product, labeled as described above, in the ultraviolet and/or visible and/or infrared range of the electromagnetic spectrum;

b) comparison of the spectrum and/or received the information with a corresponding range of authentic products and/or received the information.

Stages of marking and identification of this method can be carried out together or separately from each other, by one or by different operators in the same place or in different places using either the same or different devices.

Paint or cover composition used to perform the labeling, can be selected from the group pasty inks, such as inks for metallography, letterpress and ofsatellite; from the group of liquid inks, such as inks for screen printing, yliopistokatu and inks for gravure printing, or from a group of colors for drop on demand and continuous inkjet printing. In addition, the cover composition used to perform marking, contain toners for electrostatic (dry) or electrophoretic (wet) process printing.

Application schema defined by the consumer, by using printing inks or set of printing inks containing the dye for each of the selected basic colors generalized hyperchromic color space. In addition, individual-based paint may contain more than one dye or pigment that embody these basic colors.

Spectra of printed circuits can be registered, as is known from the prior art, using any combination of a broadband source, emitting light, and many narrowband sensitive photodetectors; the combination of broadband sensitive photodetector and multiple narrowband sources emitting light, or a combination of a broadband source, emitting light, and a dispersive or diffractive spectrophotometric device. In addition, there may be used a combination of multiple narrow-band light source, the Cove, emitting light, such as LEDs, and sensitive broadband imaging devices such as CMOS and CCD cameras, for the implementation of spectral or hyperspectral image printed circuit.

Phase extraction and matching hypercity coordinates, and not the rough data of the spectra of absorption, reflection or transmission, provides the advantage of stability. It is noteworthy that hyperchromic color space can be selected in such a way as to contain the first pigments decorative purposes together with the second pigments to provide protection where pigments for decorative and security purposes have overlapping absorption spectra. In this case, it would be very difficult to identify the presence and quantity of the protective pigment in the marking without converting spectral information in a statistically independent quantities hypercity coordinates.

How to protect a document in accordance with the present invention and obtained protective documents or products are very well adapted for machine identification, which is used in the receivers of ATMs, automatic cash machines, high-speed sorting machines, devices, checking tickets, etc. Machine identification, of course, limited to the verification of such a characteristic is of cteristic protection detection which is really quick and do not require direct contact between the document and the reader because of the danger of obstruction promotion (jamming). Therefore, when the machine identification optical methods are preferred among other methods. Thanks to the use of selective absorption, not available emission light that is reflected from the document, more than enough to provide very fast measurement cycle and thus for the identification device with high speed.

Brief description of drawings

Next, this invention will be further explained by using drawings and examples. These drawings and the examples do not limit the scope of the present invention.

1 shows a diagram of an embodiment of an extended color space according to the present invention, illustrating the use of dyes or pigments with narrow absorption band inside and outside the visible range of the spectrum.

Figure 2 shows the formulas of the two compounds which absorb in the infrared region, which are used in the framework of the present invention.

Figure 3 shows the spectral characteristics of the reflection element of the image printed by the ink of example 1.

Figure 4 shows the spectral characteristics of tragerelement image, printed ink of example 2.

Figure 5 shows the spectral characteristics of the reflection element of the image printed by the ink of example 3.

Figure 6 shows the spectral characteristics of the reflection element of the image printed by the ink of example 4.

Detailed description of the invention

In the first schematic example shown in figure 1, extended hyperchromic color space is formed from ten dyes or pigments with narrow absorption band, which is indicated by numbers from 1 to 10. They have absorption bands with maxima within the spectral range from 300 to 1100 nm (wavelengths). Dye 1 has a maximum absorption in the UV region (350 nm). Dyes 2, 3, 4 and 5 have absorption maxima in the visible region (425, 500, 575, 650 nm) and dyes 6, 7, 8, 9 and 10 have absorption maxima in the infrared region (725, 800, 875, 950 and 1025 nm, wavelengths). In particular, the visible area of the overlapped four dyes instead of three, corresponding to the receptors of the human eye. It is essential that the visible dyes 3 and 4 are chosen so that they had absorption maxima around 500 nm, falling into the region between the blue (450 nm) and green (550 nm), 575 nm, respectively, falling into the region between the blue (450 nm), green (550 nm) and red (600 nm) of the photoreceptors of the human eye. Colors such as these, if they socatots the pure blue (425 nm) and pure red (650 nm) dye, it will be impossible to reproduce using standard trichrome technology of flowers, because the four limiting conditions cannot display the three variables.

Now, the product is marked with the use of inks for printing or set of printing inks containing one or more dyes or pigments that absorb in the narrow band. Colour information is available for the specified products according to the invention effectively is selected from desaturating set, although people can see and describe the color only in the framework of three-dimensional perception of color. Thus, the impression of the human eye is about the color of the protected product corresponds to the projection of the real color information for the specified products on the three-dimensional system of color perception. This projection is carried out in the light of the source of radiation used for inspection of the document. Change quality to a specified source of radiation may lead to a different projection, and therefore to a different perception of color. Use in coatings dyes or pigments that absorb in the narrow band of the visible spectrum, invariably leads to a change of colors depending on the light ("true color").

When the specified product, such as a banknote or document that is reproduced using a color copier or scanner is, the spectral information of the document in the visible region is distributed via channels through the respective optical filters in three basic colors - red, green, and blue. The common projection of the color information contained in the specified document in the three color channels, by using ordinary light of a copier or scanner. When scanned color information in the following is reproduced by printing instead of the original dyes that absorb in the narrow band of the spectrum, on paper deposited standard dyes or pigments, the corresponding three-dimensional perception of color by the human eye. The resulting play will look almost the same, when considered in the same light that was used when scanning of the original. However, the copy may look quite different when seen in a different light, different from that used when scanning of the original.

In particular, the optical characteristics outside of the visible range, i.e. the elements that are located in the UV (UV dye 1), and signs located in the infrared region (IR dyes from 6 to 10) are not reproduced in the normal reproduction equipment, and thus, these features are absent on the copy. Visible signs due to the dyes 2-5, will play the us, but with distortion. The "color difference" between the original and its falsification can be detected by the human eye by comparing both under razlichnimi at least two visible light sources, and in the full range from UV to IR spectrum using photodetectors or spectroscopic devices.

In the subsequent receipt and application of a set of printing inks according to the present invention are exemplified by three different types of formulations of paint.

Recipe 1. The kit printed metallographic paints with five colors

Product fitting Tung oil and phenolic resin modified maleic acid, in a high-boiling mineral oil PKWF 28/31)35%
Highly polymerized oil alkyd resin7,5%
Alkylphenol resin, modified raw Tung oil in the solvent for paints 27/2916%
Polyethylene wax1,5%
Calcium carbonate30,3%
Dyes and pigments4,5%
Paint thinner 27/29 (Shell Industrial Chemicals)5%
Octoate cobalt (11% metal)0,1%
Octoate manganese (10% metal) 0,1%

Dyes and pigments

Paint 1: peak absorption at 470 nm
Acridine Orange Base (company Aldrich)1,0%
Calcium carbonate3,5%
Paint 2: peak absorption at 850 nm
DECA-(3-ethoxy-1-thiophenolate)hexa-(3-methyl-1-thiophenolate)phthalocyanine-zinc (II) (company Avecia)4,0%
Calcium carbonate0,5%
Paint 3: peak absorption at 380 nm
Tinuvin 1130 (firm Ciba)4,5%
Calcium carbonate-
Paint 4: peak absorption at 980 nm
Longwave absorber in the near IR region (Avecia)3,0%
Calcium carbonate1,5%
Paint 5: absorption peaks at 620 and 780 nm
X-form pigment of copper phthalocyanine1,8%
Calcium carbonate2,7%

These components are mixed together and the mixture is homogenized by twice about what Askania through a three-roll mill.

Recipe 2. The kit UV-drying printing inks for dry offset printing with three colors

Epoxyacrylate oligomer39%
Trimethylolpropane monomer31%
Genorad 16 (firm Rahn)1%
Talc2%
Dyes and pigments4,5%
Calcium carbonate10,5%
Aerosil 200 (Degussa-Huels)4%
Irgacure 500 (CIBA)6%
Genocure EPD (Rahn)2%

Dyes and pigments

Paint 1: peak absorption at 550 nm
Rhodamine B (Aldrich)1,5%
Calcium carbonate3,0%
Paint 2: peak absorption at 780 nm
Octabrominated copper(II)4,5%
Calcium carbonate-
Paint 3: peak absorption at 890 nm
Hexadeca-(3-ethoxy-1-thiophenolate)phthalocyanine-zinc(II) (Avecia)2,7%
Calcium carbonate1,8%

These components are mixed together and the mixture is homogenized by lucrative passing through the three-roll mill.

Recipe 3. Part of a set of printing inks for gravure printing with 4 colors

Ethanol32%
The ethyl acetate45,3%
Dicyclohexyltin (Unimoll 66, supplied by Bayer)4,5%
Resin modified with fumaric acid (Rokramar 7200, supplied by the firm of Robert Kraemer GmbH&Co)3%
Polyvinyl butyral resin (Pioloform BN18, supplied by the company Wacker)12%
Dyes and pigments3,2%

Dyes and pigments

Paint 1: peak absorption at 550 nm
Rhodamine In the basis (company Aldrich)0,4%
The ethyl acetate2,8%
Paint 2: absorption peaks at 610 and 680 nm
Luxol fast blue MSN (Aldrich)3,2%
The ethyl acetate-
Paint 3: peak absorption at 440 nm
Macroflex Yellow 6G (Bayer)1,0%
The ethyl acetate2,2%
Paint 4: peak on the underlining at 800 nm
IR-absorbing dye RSOS (firm Honeywell)1,0%
The ethyl acetate2,2%

Resin is dispersed with a solvent for 15 minutes, using laboratory equipment for dispersion. Then add dyes and recipes additionally dispersed for 15 minutes. The viscosity of the resulting formulation is brought to a value you want to print (test with a Cup of 15-25" DIN4, depending on the application), using a mixture of ethyl acetate/ethanol (1:1).

To illustrate the reflectivity, which can be obtained using a set of printing inks in accordance with this embodiment of formulations were prepared with four sample for printing.

Example 1. Ink for gravure printing, obtained by mixing ink 1 and ink 2 recipe 1 (see above) in the ratio of 1:1 and printed on paper at a density of 8 g/m2. Reflection spectrum is shown in figure 3.

Example 2. Ink for gravure printing, obtained by mixing paint 3 paint 4 paint 5 formulation 1 (see above) in the ratio 1:1:1 and printed on paper at a density of 8 g/m2. Reflection spectrum is shown in figure 4.

Example 3. UV-drying paint for dry offset printing obtained by mixing dye 1, dye 2 and dye 3 recipes 2 (see the e) in the ratio 1:1:1 and printed on paper at a density of 1 g/m 2. Reflection spectrum is shown in figure 5.

Example 4. Ink for gravure printing, obtained by mixing paint 1 paint 2 paint 3 paint-and 4 formulation 3 (see above) in the ratio 1:1:1:1 and applied manually on the paper roller at a thickness of 4 μm (theoretical wet film). Reflection spectrum is shown in Fig.6.

Now the way o ' hypercity coordinate" additionally illustrated using a schematic diagram of a working example, which is shown below in table 1. The reader has 12 spectral bands with centers at wavelengths 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900 and 950 nm, respectively. In addition, can be selected other numbers of channels at different wavelengths. These channels can even be arranged irregularly, and "channel" may include more than one wavelength or spectral band.

Hyperchromic color space that contains 6 basic colors, embodied with the use of dyes or pigments having 6 significantly different spectra. These dyes or pigments give feedback optical density Spectrum 1 Spectrum 2 Spectrum 3 Spectrum 4 Spectrum 5 Spectrum and 6, respectively, in the specified reading device; the combination of these variables is the matrix a, which represents the mathematical basis hyperchromic color space.

Ismaren the th unknown range "Range" can be expressed using hypercity coordinates x hyperchromic color space by calculating the works

x=(A'·A)-1·'·y.

In the running example, we obtained the following values of the color coordinates (CCRD) y in units of six basic colors: 0,35, 0,10, 0,00, 0,40, 0,00, 0,15. This is an exact linear combination, which is used to build values in this schematic the working example.

In addition, this example illustrates various matrix algorithm, in particular the matrix

M=(A'·A)-1·And,

which is used to convert the measured spectrum from the color coordinates of x in accordance with the formula x=M*y. For this system the basic colors and this type of reader, the matrix M must be calculated only once and can then be stored in the reader as part of the identification algorithm. It can be interpreted as a kind of key that allows you to extract the corresponding color coordinates from more abundant spectral information.

In the schematic working example of identifying and taking into account table 2 below, it is assumed that hypercity system is covered by a six dyes or pigments having spectra (Range 1 - Range 6)forming the matrix A. it is Assumed that the reflection intensity can be measured for 12 strips lighting with centers at wavelengths 400, 450, 500, 550, 600, 650, 700, 750, 800, 850, 900 and 950 nm.

The first metering the config vector Range N1" is made, assuming the concentration ratios for the six basic colors, equal 0,35, 0,10, 0,00, 0,40, 0,00, 0,15, and calculate the corresponding theoretical values of optical density of reflection for 12 strips lighting. After converting the vector Range N1" in hyperconcave coordinates, CCRD1, concentration ratios are well reproduced with the remainder value R=0,000045, i.e. close to zero.

Now for the simulation of practical application in the vector Range N1" perturbation is introduced by adding a random signal of moderate amplitude, which leads to the "measured" vector "Spectrum U2". After transformation of this vector in hyperconcave coordinates, CCRD2, their values are moderately deviate from the values for the original but they are reproduced in the main lines. The remainder value R=0,015 is acceptable; this indicates that the spectrum reflection Spectrum U2" is still within a certain hyperchromic color space this application, and therefore may be perceived as identical, but with some "contamination".

Modeling rigging in the vector Range N1" introduced substantial modification in one single point (700 nm, the number allocated)to obtain the "measured" vector "Range F3". Retrieved hyperconcave coordinates, CCRD3 amazingly well reproduce the coordinate values for the original; however, the high value ostad is R=0,212 clearly indicates, a sample having a reflection spectrum Spectrum U3" is beyond a certain hyperchromic color space this application, and therefore should be rejected as a forgery!

Thus, when the test document will be rejected if the conversion of the measured spectrum of the optical reflection density in hyperconcave coordinates corresponding hyperchromic system gives a remainder value R above 0.10 or if one of the received hypercity coordinate is outside its original "given" values, that is, outside a corresponding predetermined range of deviation of the concentration. This phase extraction and matching hypercity coordinates and magnitudes of the remainder R, and not by comparing the raw spectral parameters of absorption, reflection or transmission, provides the advantage of reliability and feasibility of almost 100%rejection fakes; all of which can be implemented on low-cost, universal, non-contact, optical equipment identification, working with high speed, in combination with printed on the document security features, based on material specific to the consumer.

Table 1
Schematic working example op is adelene hypercity coordinate
Entered spectra of (A):
Range of 1Range 2Range 3Range 4Range 5Range 6
400 nm0,2000,0000,0001,2002,0000,050
450 nm1,0000,0500,0001,0001,8000,100
500 nm0,2000,3000,0500,5001,5000,200
550 nm0,0501,2000,2000,2001,0000,500
600 nm0,0000,2000,5000,0500,5000,100
650 nm0,0000,0501,500.0,0500,1000,000
700 nm0,0000,0000,5000,2000,0000,000
750 nm0,0000,0000,2001,0000,0500,000
800 nm0,0000,0000,0500,300 0,2000,000
850 nm0,0000,0000,0000,050to 0.9000,050
900 nm0,0000,0000,0000,0000,2000,200
950 nm0,0000,0000,0000,0000,1001,100

The measured spectrum (in)

Range
400 nm0,560
450 nm0,770
500 nm0,330
550 nm0,300
600 nmto 0.060
650 nm0,030
700 nm0,080
750 nm0,400
800 nm0,120
850 nm0,030
900 nm0,030
950 nm0,170

The matrix a'·And

2
123456
11,0830,1700,0201,3502,5500,175
0,1701,5750,4300,4531,8450,685
30,0200,4302,835to 0.4800,6950,160
41,3500,453to 0.4803,8685,3350,368
52,5501,8450,6955,33511,6521,325
60,1750,6850,1600,3681,3251,565

The matrix (A'·A)-1

123456
12,1340,2970,077-0,194-0,4340,037
20,2971,028-0,1080,210-0,286-0,280
30,077-0,1080,378-0,0810,0140,007
4-0,1940,210-0,0810,803-0,3600,054
5-0,434-0,2860,014-0,360,399 -0,081
60,037-0,2800,0070,054-0,0810,813

1. The ink for printing, which comprises a) at least one dye or pigment having at least one absorption maximum in the visible region of the electromagnetic spectrum, which differs significantly from the absorption maxima of the basic color system of the CIE-XYZ, and b) at least one other dye or pigment having an absorption band in the visible region of the electromagnetic spectrum, with specified band width at half intensity already 2400 cm-1, preferably 2000 cm-1and most preferably 1500 cm-1and

C) at least one other dye or pigment having at least one absorption maximum in the ultraviolet or infrared region, preferably in the near infrared region of the electromagnetic spectrum.

2. The ink for printing according to claim 1, containing at least three, preferably at least four different dye or pigment having the absorption spectra, which differ significantly among themselves.

3. The ink for printing according to any one of claims 1 or 2, containing the th, at least two, preferably at least three different dye or pigment having at least one absorption maximum in the infrared region, preferably in the near infrared region of the electromagnetic spectrum.

4. The ink for printing according to claim 1, containing at least four different dye or pigment having at least one absorption maximum in the visible region of the electromagnetic spectrum.

5. The ink for printing according to claim 1, additionally containing a reflective pigment.

6. A set of printing inks containing at least two inks for printing according to claim 1.

7. A set of printing inks according to claim 6, containing at least three, preferably at least four different inks for printing according to any one of claims 1 to 5, with each ink contains a dye or pigment, which differ from dyes or pigments in different colors for printing.

8. A set of printing inks according to claim 7, in which various dyes or pigments have at least one absorption maximum in the visible region of the electromagnetic spectrum.

9. A set of printing inks according to claim 6, in which at least one ink for printing, preferably at least two and more preferably at least three inks for printing contain dye or pigment, which have, at least, one of the N. the maximum absorption in the ultraviolet or infrared region, preferably in the near infrared region of the electromagnetic spectrum.

10. A set of printing inks according to claim 6, in which at least one ink for printing contains reflective pigment.

11. A method of marking a product, such as a banknote, a document, ticket, label, foil, thread, card or industrial goods, which includes a stage ensure marking of the specified product, which is applied by using at least one ink for printing according to any one of claims 1 to 5, or a set of printing inks according to any one of p-10, or by using at least one covering compositions containing at least one ink for printing according to any one of claims 1 to 5, or a set of printing inks according to any one of PP-10.

12. The method according to claim 11, in which at least one covering composition selected from the group consisting of paste paints, including paints for metallography, letterpress and offset printing; from the group consisting of liquid inks, such as inks for screen printing, yliopistokatu and inks for gravure printing, from the group consisting of toners for electrostatic or electrophoretic printing, or from the group consisting of inks for inkjet printing, which include paint to drip on demand ink jet printing and continuous inkjet printing the tee.

13. The method of product identification, such as a banknote, a document, a ticket, a foil, a thread, a label, card or industrial goods, which includes stages:

a) measured spectrum of absorption, reflection or transmission of the specified product, labeled by the method according to any of § § 11 or 12, in the ultraviolet and/or visible and/or infrared range of the electromagnetic spectrum;

b) mapping the spectrum measured at the stage a)and/or received the information with a corresponding range of authentic products and/or received the information.

14. The method according to item 13, which is carried out using equipment such as a receiver exchange, the device checks the tickets, or the manual identification.

15. The method according to PP or 14, in which the range specified at the stage a), is measured as a vector of numerical values representing the absorption and/or reflection and/or transmission of specified markings at selected values of the wavelengths or in a selected number of areas of wavelengths.

16. The method according to PP or 14, in which stage b) is carried out by extracting statistically independent hypercity coordinate of the specified marking of the vector of numerical values measured at the stage a), and mapping at least one of these hypercity coordinate with the appropriate standard EIT is the group of genuine products, and output indicator of the identity of the mapping, using pre-established criteria for the decision.

17. The manner of identification of goods indicated in paragraph 13, in which the spectrum is recorded by use of a combination of a broadband source, emitting light, and many narrowband sensitive photodetectors; or using a combination of broadband sensitive photodetector and multiple narrowband sources emitting light; or using a combination of a broadband source, emitting light, and the dispersion or diffraction spectrometry device.

18. The manner of identification of goods indicated in paragraph 13, in which the spectrum is recorded by use of a combination of multiple narrowband sources emitting light, such as LEDs, and broadband sensitive imaging devices such as CMOS and CCD cameras, receiving the information of the spectral or hyperspectral image.

19. The method of identifying articles on article 16, which includes the statistically independent hyperconcave coordinates output from the measured spectrum using a mathematical algorithm of least squares.

20. The label, which includes at least one ink for printing according to any one of claims 1 to 5, and/or at least one set of PE is atnah ink according to any one of p-10.

21. The product, such as a banknote, a document, a ticket, a foil, a thread, a label, card or industrial goods, which includes at least one marking according to claim 20.

22. Using a combination of (a) at least one dye or pigment having at least one absorption maximum in the visible region of the electromagnetic spectrum, which differs significantly from the absorption maxima of the basic color system of the CIE-XYZ, and b) at least one other dye or pigment having an absorption band in the visible region of the electromagnetic spectrum, with specified band width at half intensity already 2400 cm-1, preferably 2000 cm-1and most preferably 1500 cm-1and C) at least one other dye or pigment having at least one absorption maximum in the ultraviolet or infrared region, preferably in the near infrared region of the electromagnetic spectrum, for marking and/or identification of the product, such as a banknote, a document, a ticket, a foil, a thread, a label, card or industrial goods.

23. The application of inks for printing according to any one of claims 1 to 5 for marking and/or identification of the product, such as a banknote, a document, a ticket, a foil, a thread, a label, card or industrial goods.

24. Application of a set of printing the ink according to any one of p-10 for marking and/or identification of the product, such as a banknote, a document, a ticket, a foil, a thread, a label, card or industrial goods.

25. The use of marking in claim 20 for product identification, such as a banknote, a document, a ticket, a foil, a thread, a label, card or industrial goods.



 

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FIELD: chemical industry; methods of production of the coatings with the strong adhesion.

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The invention relates to the printing industry, namely the production of printing inks for inkjet printers

The invention relates to ink for ink-jet printing, including personal printers

The invention relates to the technology of binders based Uralkalij products intended for use as paints and other coatings for the surface treatment and finishing of various materials based on paper (decorative, label paper, Wallpaper, securities and so on)

FIELD: polymer production.

SUBSTANCE: invention relates to production of polymeric binders for toner and can be used for copying appliances and printers. Process comprises separate preparation via emulsion polymerization of (i) low-molecule weight copolymer of styrene (α-methylstyrene), 2-ethylhexyl acrylate (or butyl acrylate) and methacrylic acid at monomer weight ratio (88-91.5):(8-11):(0.5-1.0) with intrinsic viscosity in toluene 0.08-1.2 dL/g and (ii) high-molecule weight copolymer of styrene (α-methylstyrene) and 2-ethylhexyl acrylate (or butyl acrylate) at monomer weight ratio (88-92):(8-12) with intrinsic viscosity in toluene 1.0-1.28 dL/g. In both cases, polymerization is carried out at 60-70% to monomer conversion close to 100%. Resulting latexes of low- and high-molecule weight copolymers are supplemented by stopper and antioxidant and then mixed with each other at "dry" weight ratio between 70:30 and 75:25 and coagulated intrinsic viscosity in toluene 1.0-1.28 dL/g. with electrolyte solutions to form polymer characterized by intrinsic viscosity in toluene 0.4-0.45 dL/g and polydispersity Mw/Mn, which ensures bimodal molecular weight distribution of copolymer. The latter has melting (spreading) point 125-137°C and softening temperature 70-75°C.

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2 cl, 1 tbl, 4 ex

FIELD: chemical industry; methods of production of the coatings with the strong adhesion.

SUBSTANCE: the invention is pertaining to the method of production of the coatings with the strong adhesion on the inorganic or organic substrate, which provides, that one inorganic or organic substrate is subjected to the treatment with the low-temperature plasma, the corona discharge or the treatment with the gaseous flame, at the normal atmospheric pressure deposit on the inorganic or organic substrate one or several photoinitiating agents or the mixtures of the at least one ethylene- unsaturated with the monomers and-or the oligomers containing at least one ethylene- unsaturated group, or the solutions, suspensions or emulsions of the above indicated substances using the suitable methods; the above indicated substances are not necessary subjected to drying and-or to the electromagnetic irradiation; and either on the preliminary so treated substrate deposit the composition including at least one ethylene- unsaturated monomer or the oligomer and the coating is subjected to hardening under action of the UF/ the visual rays emission or the electron beam; or on the substrate with such a preliminary coating made out of the photoinitiating agent they apply the printing ink coating and dry it. The method has the high efficiency and allows to produce the coating with the good adhesion and is suitable for to production of the products made out of the various plastics materials and-or metals or the glass types with the coatings having the good adhesion.

EFFECT: the invention ensures the high efficiency of the method, production of the highly adhesive coatings suitable for manufacture of the products made out of the various plastics materials, metals or the glass types.

18 cl, 19 ex

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