Visual angle-depending color-shift pigment, method of manufacturing such pigments, employment of these pigments in applications associated with protection, composition of coating containing these pigments, and detection device

FIELD: protection coatings.

SUBSTANCE: invention aims at protecting bank notes and security papers against counterfeiting. Optically changing pigment contains interferential multilayer structure including light-transmitting dielectric layer having at least one luminescent material. Dielectric layer is selected from of rare-earth metal, bismuth, and principal group III element trifluorides; of principal group II element difluorides; mixtures thereof; organic or organometallic compounds. Luminescent material should be selected from organic or organometallic compounds containing transition or rare-earth metal ions. Above-defined structure may contain one or more semitransparent, partly reflecting layers, one or more nontransparent, fully reflecting layers, and one or more conducting layers. Pigment is prepared by a method including physical or chemical precipitation of the dielectric layer.

EFFECT: preserved proper properties of color shift, increased reliability of protection, and ensured identification simplicity at relatively low cost.

30 cl, 1 tbl, 9 ex

 

The present invention relates to pigments having a color shift depending on angle of view, the production method of the above-mentioned pigments, said pigments in applications related to security, the composition of the coating and granular material containing the above-mentioned pigments, and a detecting device for excitation and read-mentioned pigments.

Pigments having a color shift depending on angle of view, the so-called optically variable pigments, since 1987, has proven itself as an effective device of copy protection used on the banknotes and security documents. Currently, much of the paper money printed throughout the world, used optically variable device, copy protection, and among the latter recognized as the dominant optically variable ink (marketed under the trademark (OVI™)).

Shift colors depending on the angle of view cannot be reproduced using a color copying machines. Currently, the market offers many different types of materials optically changeable pigments (IPRs), and they are all based on thin-film interference structures. However, hue, color shift and color of structures depend on the material, to the th are layers, the sequence and number of layers, layer thickness, and the features used for their manufacturing process.

Very bright colors obtained using the IPR of the first type produced by physical vapour deposition, for example, in accordance with U.S. patent№№4705300, 4705356, 4721217, 4779898, 4930866, 5084351, and related subsequent patents. This IUP is made in the form of the foot thin film deposited from the vapor phase of the Fabry - Perot cavities. The described sequence of layers a simple three-layer and dual three-layer structure of metal - insulator - metal". The middle layer of metal can be implemented as an opaque totally reflecting layer to obtain the maximum reflectance of the incident light. The upper layer (s) of the metal must be partially transparent (transparent), so the light can get into the cavity Fabry - Perot and leaving it.

Incident light falling on flocculent particle optically variable pigment mentioned type metal - insulator - metal", it is partially reflected in the top layer of metal. The remainder of the light passes through the dielectric and is reflected in the lower metal layer. Both the reflected part of the incident light, in the end, recombinants and interfere with each other. Depending on the thickness of the dielectric layer and the wavelength of the incident light, it turns out constructive (reinforcing) or destructive (weakening) interference. If the incident light is white, some light components having specific wavelengths are reflected, whereas the other components having other wavelengths are not reflected. This allows the spectral selection, and consequently the appearance of colors.

It should be noted that the difference between the paths of the reflected upper layer and reflected by the lower layer part of the light depends on the angle of incidence, and therefore there is obtained interference.

The second type of IPRs, produced in accordance with European patent No. 708154, German patent No. 19525503 and U.S. patent No. 5624468, 5401306, 4978394, 4344987 and related subsequent patents based on the use of flocculent particles of aluminum having a coating. Method of chemical vapour deposition (CVD) or deposition from liquid phases of different chemical methods, mechanical tapered aluminum particles cover the dielectric layer and the subsequent metal layer or the second dielectric layer. The result in the form of interference colors is due to the same effect, which is described above. This type of IPRs cheaper to manufacture than the first type, but it also gives less vivid colors and less dependent on angle color shift than the first type.

Even the Dean, the third type of IPRs based on liquid-crystal pigments. Such pigments are produced, for example, in accordance with European patent No. 601483, 686674 and related, based on the polymerized phases of cholesteric liquid crystal (LCD). Phase cholesteric LCD demonstrate helical arrangement of molecules, resulting in periodic variation in the refractive index of the material along the perpendicular to the surface direction. This, in turn, affects the light scattering and/or transmission of light, which are similar to the effects of interference foot Fabry-Perot. Due to the spiral arrangement of the phases of cholesteric LCD, the light of one circular polarization is mainly reflected, while the component with the other circular polarization is predominantly transmitted and must be absorbed by the dark background. This type of IUP gives less vibrant colors than IPRs based on the metal reflector. However, he has excellent properties of color shift due to the very small refractive index of the organic material.

The fourth type of IPRs based on coated flaky particles of mica, are described in U.S. patents№№3874890, 3926659, 4086100, 4323554, 4565581, 4744832, 4867793, 5302199, 5350448, 5693134 and related. The coating is a material with a higher refractive index, for example, TiO3, caused by deposition from the liquid phase by various chemical methods or by way of CVD and acting as a partially reflecting surface on both sides of flocculent particles of mica. Mica plays the role of the dielectric. Using this type of IPRs, which is also known as "iridescently pigment receive only a pale color and subtle properties of the color shift.

The fifth type of IPRs is fully polymeric multilayer reflective and/or light-absorbing foil in accordance with U.S. patent No. 3711176 (see, for example, W.J. Schrenk et al. "Critical Reviews of Optical Science and Technology", CR39, 1997, cc.35-49). This foil is also interference device, which shows the properties of the spectral reflection and transmission, depending on the angle, and can be used to obtain the fifth type of optically variable pigment.

Large quantities of optically variable pigments receive for decorative purposes (paints, varnishes, etc. for cars), and therefore they are in the form of paints and aerosols - are available to the public. Protective potential signs of optically variable ink on the notes is significantly reduced, if you cannot distinguish between "protective IPR" from "decorative IPRs". In this regard, it should be noted that a counterfeiter could reproduce banknotes on svetooperatorom device and make defects in the matter of optically variable characteristics with the help industrial supply paints or sprays.

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

In particular, the challenge is to develop any type of optically variable pigments (IPRs), which have, in addition to shift colors depending on the angle of view, additional signs, the consequence of which is a reaction to external energy.

An additional challenge is to develop protective IPR"substantially different from "decorative IPRs" and thus keeping the correct properties of the color shift.

An additional challenge is to develop protective IPRs with means for simply and reliably to distinguish it, in particular, from decorative IPRs.

An additional challenge is to develop the IPR, which can be identified using simple devices, and machine-identifiable at low and high speed.

An additional challenge is to develop methods for the production of protective IPRs, in particular, by using the same equipment and process used for the production of decorative IPRs, without a substantial increase in production costs.

These challenges are due to the presence of the proposed invention features, Pref is given in the independent claims.

In particular, these tasks are solved by using pigments containing interference structure, at least two thin film layers of different materials, and the above-mentioned pigments have a color shift depending on angle of view, and at least one of these layers contains at least one luminescent material.

In the first specific embodiment, the IPR has a structure containing at least one light-absorbing dielectric layer with a first and a second surface essentially parallel to each other, and at least one semi-transparent partially reflecting layer located on each of the aforementioned first and said second surfaces of the dielectric layer, and the fluorescent material contains at least one of the dielectric layers.

In the second specific embodiment, the IPR has the structure that contains the opaque totally reflecting layer, having a first and a second surface essentially parallel to each other, and at least one sequence that is located at least on one of the mentioned first and second surfaces of the opaque totally reflecting layer, with the said sequence contains at least one dielectric layer and at least one translucent is, a partially reflective layer, and a dielectric layer mentioned sequence is adjacent to the fully reflective layer, luminescent material contains at least one of the dielectric layers.

Partially reflecting and partially transmitting the upper layer has a thickness in the range of 5-25 nm. Semi-transparent partially reflecting layer is preferably selected from metals, metal oxides or sulfides of metals such as aluminum, chromium, MoS2, Fe2O3.

The dielectric layer consists of a material with low refractive index having a refractive index of not more than 1,50, provided that this material does not contain a fluorescent material. This material is preferably selected from MgS2, SiO2, AlF3. The use of dielectrics with a low refractive index leads to a major shift in color depending on the angle. The thickness of the dielectric depends on the desired color IPRs; it is about 200-600 nm. For example, the IPR-shift color from gold to green with a layer MgF2the thickness of 440 nm, and the IPR with a color shift from green to blue has a thickness of 385 nm.

Opaque totally reflecting layer selected from metals or alloys of metals such as aluminum, silver, copper, cobalt and Nickel, alloys of aluminum.

Most preferred is al mine with reflection coefficient, close to 99% in all interest area of the spectrum. Fully reflecting layer has a thickness in the range of 50-150 nm.

The pigments of the latter type may have a structure of Cr/MgF2/Al/ MgF2/Cr to get the same properties of reflection for both sides. The Central layer of aluminum acts as a full reflector. In the context of the present invention, it is sufficient to consider half of this structure IPRs, i.e. stop Cr/MgF2/Al.

In the context of the present invention, the terms "partially reflecting", "transparent", "opaque", "fully reflect", "the dielectric (dielectric)", "hue", "color", "color", etc. refer to those parts of the electromagnetic spectrum, which play an important role in people's lives.

Definitions of terms and expressions used throughout this application, is given in accordance with Römpp Chemie Lexikon, ed. J. Falbe, M. Regitz, 9th edition, Georg Thieme, Stuttgart New York, 1992.

These pigments consist of flocculent particles, which have a length of about 20-30 μm and a thickness of about 1 μm.

In yet another specific embodiment of the invention, ions of luminescent material embedded in the dielectric coating on the flaky aluminum particles to obtain IPRs above-mentioned second type. Mentioned dielectric coating can also be applied in any way x the chemical deposition from the vapor phase, using a reactor with a fluidized bed, or alternatively, a wet chemical methods known in the technical literature.

It is noteworthy that the properties of color shift in these types of IPRs are associated with implemented by the difference of the paths inside the dielectric orthogonal falling and grazing incidence. An incident beam dirrahiuma according to the law of Snell's law, n1·sin(α)=n2·sin(β), where n2and n1the respective refractive indices of the materials 1 and 2, and α and β - corresponding angles between the ray and the normal to the surface. Under the assumption that n1=1 (for air), the condition incidence angle (α=90°) is described in the form sin(β)=1/n2. Then the maximum length L of the path of light inside the dielectric, expressed through the optical thickness d, can be represented in the following form L = d/sqrt[1-(1/n22)]. The following table 1 illustrates this dependence for example a few typical materials, if available, are listed packing density, R).

The dielectric layer helplearn particles IPRs may contain at least one ion fluorescent material. Specific interest in the purposes of the present invention trivalent ions of some transition e is the elements, such as chromium (Cr3+), iron (Fe3+), etc. Specifically preferred are ions of rare earth elements. Preferred ions of rare earth elements selected from the group consisting of yttrium (Y3+), praseodymium (Pr3+), neodymium (Nd3+), samarium (Sm3+), europium (Eu3+), terbium (Tb3+), dysprosium (Dy3+), holmium (But3+), erbium (Er3+), thulium (Tm3+) and ytterbium (Yb3+).

The practical implementation of such alloying using as dielectric MgS2is quite complicated, because ion of Mg2+has a relatively small radius (72 nm) ion compared with the radii (86-102 nm) trivalent ions of rare earth elements, and the necessary charge compensation. Although co-evaporation MgF2with trivalent fluorides of rare earth elements, it is chemically doped materials, narrow grille-master MgF2can't take the strain, make voluminous doping ions, which would, among other deficiencies, leads to the formation of clusters. Klastirovannye excited ions, rare earth elements are subjected to rapid deactivation without radiation, so no luminescence is not observed.

The dielectric layer containing the aforementioned fluorescent material selected from a group status is the present from diferido elements of the second main group or of zinc or cadmium, or mixtures thereof. In a preferred specific embodiment, use CaF2as a dielectric material, LEGIROVANNOGO trivalent rare earth elements, in particular lanthanides, because the radii of the ions of CA2+(100 nm) and Ln2+are comparable. However, it is necessary to compensate for the positive excess charge dopant containing Ln2+. Charge compensation can be either anionic, conducted by replacing the fluoride ion (F-, 133 PM) oxide ion (O-, 140 PM), or cationic carried out by replacement of calcium ion (CA2+, 100 PM) sodium ion (Na+, 102 PM). Anionic compensation easily be done by annealing the material in oxygen, but this is not practicable in the presence of heat-sensitive fabric substrate. Cationic compensation requires co-deposition using the same number of ions Ln2+and Na+when simultaneous careful regulation during the process of sputtering.

Dielectric materials, ensuring easy implementation of a fluorescent material, in particular, trivalent ions of rare earth elements, but without compensation charge, which are selected from the group consisting of triptolide rare earth elements, triptolide bismuth, or mixtures thereof, a complex of trivalent fluorides the ions of rare earth elements or bismuth and monovalent ions of alkali elements or divalent ions of alkaline earth or transition elements, in particular, zinc, and mixtures thereof. Specifically preferred are triptolide yttrium and, in particular ions aluminescent materials, i.e. YF3, LaF3, CeF3, GdF3, LuF3and BiF3or, alternatively, among them complex fluorides, for example, ALnF4, AeLn2F8, ALn2F10where a is a monovalent ion alkaline element, preferably selected from among Li+, Na+To+, AE - divalent ion, alkaline earth or transition element, preferably selected from among Mg2+, CA2+, Sr2+, Ba2+, Zn2+, Ln a is a trivalent rare earth element ion, preferably selected from among Y3+La3+CE3+, Gd3+or VA3+. In the context of the present invention, pure fluoride, or a mixture thereof is preferable mentioned complex fluorides, because the characteristics of the first evaporation are better regulated.

For the introduction of fluorescent material, in particular, trivalent ions of the transition elements, the dielectric materials are selected from the group consisting of triptolide elements of the third main group or bismuth, or trivalent ions of transition elements or their mixtures, complex fluorides of elements of the third main group or of bismuth ion alkaline element, ion deliciosamente the element or mixtures thereof. Specifically, are acceptable materials type EF3where E is ion Al3+, Ga3+In3+Bi3+or trivalent ion of a transition element, or Na3AlF6.

Fluoride materials are the preferred dielectrics-hosts-mentioned ions of luminescent materials. It is noteworthy that fluorides have the range of low-energy phonons, i.e. their absorption bands of infrared light (IR light) are located at the level of low energy. Under such circumstances, vibrational deactivation embedded excited ions fluorescent material rigidly suppressed, which leads to high yields of luminescence and long-excited States. In addition, the fluorides are quite unusual matrix-owner in case of an industrial supply of luminescent materials. This allows you to unlock the potential of the shielding capabilities of the present invention. For this reason, ions luminescent material embedded in the IPR, it is possible to distinguish, for example, in their particular time decay of the luminescence from the usual mixtures industrial supply luminescent materials and optically variable inks that are not protective.

In any case, IPRs, with the centers of luminescence that is embedded inside volume of the cavity Fabry - Perot can be distinguished from aluminescent the IPRs and added fluorescent material in their excitation spectrum, depending on the angle. Volumetric resonator based on IPRs has the ability the internal amplification of the intensity of the incident light for wavelengths corresponding to the minimum reflectivity of the resonator, i.e. satisfying the condition of the laser resonator, n·d=kλ/2. At these wavelengths, the cavity is preferably takes away energy from the environment, and the intensity of light inside the resonator is many times higher than the intensity of the outside of it. Thus, the fluorescent material inside the resonator will be stronger to get excited when the resonance condition in the resonator is performed than when this condition is not met. Due to the fact that the wavelength at the resonance in the cavity depends on the angle, the luminescence intensity obtained for different angles of the same excitation radiation will be different, and this makes it possible to determine that the luminescent material is located inside the resonator on the basis of IPRs, not outside of it.

The deposition of luminescent dielectric layer can be performed in the same way, which is used for the deposition of a layer of MgF2, MgF2it is possible to precipitate from the hot poluraspada by electron beam sputtering. Fluorides of rare earth elements are more or less compatible with MgF2the melting temperature and the characteristics of evaporated the Oia, therefore, they can be precipitated in the same manner. Alloying elements in fluoride, which is the matrix, can be added in advance; for example, 2% EuF3you can pre-fused with 98% LaF3for the formation of a homogeneous mixture, and this mixture can be used as a deposited material. In the following table 2 summarizes the melting and boiling points of some common dielectric materials used in the context of the present invention.

Physical and chemical properties, i.e. the preferred charge radii of ions and chemical affinity of the ions of yttrium and lanthanides are the same or very close, so in mixed triptolide all ions of the above-mentioned metals evaporate almost with the same speed in terms of electron-beam sputtering. This favorable condition for spraying mixed or alloyed materials. Lanthanum TRIFLUORIDE is practically preferred material in the material master for the purposes of the present invention, because all the other triptolide rare earth elements form extensive solid solutions with LaF3so after their crystallization does not occur clustering (grouping) of the ions, and can basically avoid suppression concentration at low concentrations of active IO is s.

For the realization of complex coding, matrix-owner of the same dielectric can implement more than one active ion fluorescent material. On the basis of this encoding can be implemented protective system, using a set of different matrices hosts and a set of different ions luminescent materials implemented in the above-mentioned matrix-owners. So you can get associated with a particular application, coded on luminescence, optically variable pigments.

The total number of ions matrix-owner, replaced by doping ions luminescent materials, typically 0.1-10%. Too high concentration of doping ions leads to samopodoben luminescence, whereas a too low concentration is difficult to detect and is not suitable for applications involving high-speed reading.

In an additional specific embodiment of the present invention, the aforementioned fluorescent material is an organic or ORGANOMETALLIC compound.

In an additional specific embodiment of the present invention, the dielectric layer comprises two or more sublayers, and the fluorescent material contains at least one of the sublayers. These sublayers are dielektricheskii and layers. The sublayer that contains a fluorescent material, hereinafter referred to as the first sublayer. The first sublayer adjacent at least one of the first or second surfaces of the opaque totally reflecting layer, and at least a second sublayer consists of a material having a refractive index equal to or less than a 1.50, in particular from MgF2and AlF3.

Dielectric-based MgF2conventional IPRs of the first type may be completely or partially replaced by one of the doped dielectric materials, such as yttrium fluoride and/or lanthanide. For example, if the entire layer MgF3substituted LnF3(Ln=Y, La, Lu...) this will lead to greater refractive index, with a concomitant reduced color shift depending on angle. To save the properties of the color shift in the IPR, in accordance with the present invention it is preferable that only a portion of the dielectric layer was replaced LnF3. As the inner layer on top of the Central reflector of aluminium, the preferred doped LnF3. In particular, favorable conditions for the preservation of the properties of color shift in IPRs are obtained if the thickness of the layer doped with a fluorescent material is selected less than 10% of the total thickness of the dielectric.

Although the properties of the color shift in the IPR is not affected posledovatelno the b layer MgF 2and LnF3(in both cases, the longest possible optical path inside the dielectric layer is set by the ratio L=(L1+L2)={d1/sqrt[1-(1/n12)]}+{d2/sqrt[1-(1/n22)]}, where d1and d2denote the thickness of the respective layers, a n1and n2the respective refractive indices). The location at which the layer doped LnF3closer to the aluminium reflector, allows to isolate it with a layer of MgF2from the upper contact of the chrome coating. It should be noted that chromium is a known suppressor of some centers of luminescence.

To compensate for the possible reduction of shift colors depending on the angle, which is caused by the presence of a layer LnF3in accordance with the invention, it is possible to replace part of the MgF2dielectric layer AlF3. AlF3has a smaller refractive index (n=1,23)than MgF2and therefore can easily compensate for the introduction of the equivalent layer LaF3(n=1.55V).

In another specific embodiment of the invention, the structure of the IPR contains at least one light-absorbing dielectric layer with the first and second surfaces and at least one semi-transparent partially reflecting layer of a material with a higher refractive index having a refractive index, p is at least 2.00 and located, at least one of the first and second surfaces of the dielectric material, and fluorescent material contained in the material with higher refractive index. In particular, to obtain IPRs above the fourth type ions luminescent material embedded in an inorganic coating of flaky particles of mica having a large refractive index. Mentioned inorganic coating can be applied either by chemical deposition from the vapor phase, i.e. with the use of a reactor with a fluidized bed, or alternatively, deposition from liquid phases of different chemical methods, which are described in the technical literature. In this particular embodiment, the luminescence centers are not located inside the optical resonator on the basis of IPRs, and therefore is not observed characteristics of excitation depending on the angle.

In an additional specific embodiment of the present invention, the structure of the IPR contains opaque totally reflecting layer, preferably, flocculent particles of aluminum, with the first and second surfaces and at least one semi-transparent partially reflecting layer of a material with a higher refractive index having a refractive index of at least 2.00 and is the th, at least one of the first and second surfaces of the dielectric material, and fluorescent material contained in the material with higher refractive index.

Preferred materials with a large refractive index consist of Fe2O3and TiO2.

The invention is in no way limited to the IPR organic type. In an additional specific embodiment, its implementation, the dielectric layer consists of organic or ORGANOMETALLIC polymer.

Manufacturer of fully polymeric cocodimama film and a bright shiny pigments in principle described in the document WO 99/36478. This optically variable device based on the foot alternating layers of polymer of high and low refractive indices. For example, the foot of 209 alternating layers of polyethylene-2,6-naphthalate (PAN) and polymethylmethacrylate (PMMA) is produced by co-extrusion to obtain optically variable polymer foil, which carries out a color shift from blue to red during transmission and from yellow to greenish reflection in the range of angles of incidence from direct to acute. Other polymers, such as polyethylene terephthalate (PET), polybutylene terephthalate (pbtf was honored with), can be used in the manufacture of such polymer stop, which can also contain more than two different types is of polimerov.

A huge variety of organic and ORGANOMETALLIC luminescent materials can be embedded in the plastic material by diffusion or by dissolving in the molten state. In particular, it is proved that the polymethylmethacrylate (PMMA) is a suitable matrix for some very light fluorescent materials. In a preferred specific embodiment of the invention, derivatives of perylene, such as diimide N,N'-bis(2,6-bis-aminobutiramida)-phenyl-perylenetetracarboxylic acid (perilipin"), embedded in PMMA, can with advantage be used for the manufacture of a fluorescent dye having a fluorescent response of a material with good long-term stability.

This PMMA doped luminescent "paraliminal", used along with a PEN, instead of the undoped PMMA as described in example 1 of WO 99/36478, for the manufacture of multilayer optically variable foil, which has the additional properties of fluorescence (perilipin: the last maximum absorption at 520 nm; emission maximum is at 555 nm). Thus obtained optically variable foil then crushed, getting bright shiny pigment. Such fluorescent optically variable foil or pigment can be distinguished by the angular dependence of its (his) spectra excited is I and the radiation from the luminescent material, which are just outside the optically variable foot.

In accordance with the document WO 99/36478, optically variable plastic feet can perform as an optical filter, having a well-defined and dependent on the angle of filtering characteristics. In such an implementation, the luminescence is chosen so that it is excited and is visible only under properly defined angles.

Fluorescent paint may be present or at least in one of the two layers of polymeric multilayer foot, or at least one component of a pigment, or even in all its components or layers. As is obvious to experts in the field of technology, of course, possible to use other types of fluorescent materials that differ from the "Prelimina", and other types of polymers.

Such polymers can be rolled out with obtaining very thin foils, the thickness is about 5 μm. Numerous foil can be ekstradiroval together ("co-extrusion"), so that the diameter of individual component foil procures a thickness of about 200-600 nm, which is preferable for the effects of optical interference. Organic or ORGANOMETALLIC compounds can either be added to the polymer before manufacture of the foil, or - alternatively - appreciated by the VAT component in foil before co-extrusion. The printing process can also be used for the implementation of a special pattern (characters) in the luminescent element. Fluorescent ink printed on the surface, will migrate in the polymer under the influence of heat during subsequent processing stages. After co-extrusion, the obtained multi-layer plastic foil can be cut with obtaining the pigment, preferably in cryogenic conditions.

The polymeric materials preferably should be soluble in the polymer substrate or mixed with it, to avoid turning it into an opaque due to the presence of a second phase having a different refractive index. The goals set by the invention, can achieve a molecular or polymeric luminescent materials. You can also use colloidal luminescent materials of organic, ORGANOMETALLIC or inorganic nature, provided that the size of the particles does not exceed 50 nm.

In another specific embodiment, the structure of IPRs based on polymerized phases of cholesteric liquid crystal (LCD). The luminescent material may be part of a phase molecular liquid crystal, i.e. it can be covalently associated with a cholesteric liquid crystal, or may be implemented in a variety of "guest - host" phase liquid crysta is La and is bound by the van der Waals forces.

In an additional specific embodiment of the present invention, the IPR shows the electroluminescence.

In a preferred specific embodiment of the present invention, the structure contains the opaque totally reflecting layer, having a first and a second surface essentially parallel to each other, and at least one sequence that is located at least on one of the mentioned first and second surfaces of the opaque totally reflecting layer, with the said sequence contains at least one electrically conductive layer, having a greater work function of at least one dielectric layer and at least one semi-transparent partially reflecting layer, and the conductive layer, having a large work function, the aforementioned sequence is adjacent to the fully reflective layer, luminescent material contains at least one of the dielectric layers.

In the art known electroluminescent devices, in particular organic electroluminescent devices (organic light-emitting diodes, Aside), which are described, for example, in U.S. patents№№ 3995299, 4164431, 4539507, 4720432, 4679292, 5736754, 5759709, 5817431 in many other patent publications.

The device is based on Osipov is accordance with known prior art thin-film stop, containing at least three different layers: the first electrically conductive layer, characterized by a first function more electrical work, for example, indium oxide-tin (Reis), followed by a dielectric layer, characterized by a light-emitting ability, such as polyparaphenylene (PPV), followed by the second conductive layer characterized by a second function less electrical work, for example, an alloy of magnesium and silver. If your device applied electric potential, so that the positive pole of the power source connected to the first conducting layer, having a greater electrical output operation, and the negative pole of the power source connected to the second conducting layer having a low electrical output operation, the charge carriers in the form of holes and electrons instantly injections specified in the dielectric layer through the above first and second conductive layer, respectively. These charge carriers in the form of holes and electrons eventually recombine within the mentioned dielectric layer, creating excited States of the molecules and causing a corresponding emission of light (electroluminescence).

More complex devices based on Osipov in accordance with the prior art contain two dielectric layers, the first one is that is a polymer with a hole (p-) conductivity, such as polyvinylcarbazole, and the second is a polymer with e (n) conductivity, such as polythiophene, and mentioned dielectric layers enclosed between these two conductive layers, so that the polymer with p-conductivity is turned to the conductive layer having the function of most electrical work, polymer with n-conductivity is turned to the conductive layer having the function of a smaller electrical work. In this case, one of the two polymer layers must also be a light emitter.

In other devices, the polymer dielectric layer is not involved in the emission of light, but instead a thin layer of highly efficient light-emitting paints, such as porphyrin compound is introduced between the polymer layers with p - and n-conductivity to perform the function of light emission.

In some devices, as materials with p - and n-conductivity are molecular compounds, such as triarylamine or naftopererobniy (the NWF), respectively, oligo(hexa)tifany or hydrochinon aluminum (Alq).

According to the existing prior art, Aside made for lighting or display and have to obtain the maximum amount of emitted light. For these reasons, the dielectric layer, and at least one of the above electro is rovodnik layers are made so optically transparent, to the extent possible.

According to the present invention, an organic light-emitting device is arranged so that it can simultaneously show an optical flexibility and light emission upon excitation current. To obtain optical variability, a dielectric layer or a combination of the dielectric layers is chosen so as to provide a total thickness in the range between 200 nm and 800 nm. The rear electrode of the device is fully reflective layer and the front electrode of the device is partially reflecting and/or partially transmitting layer, so that together with the dielectric layer they form a resonator Fabry - Perot known from other optically variable devices described in the technical literature. Partially reflecting and/or partially transmitting layer preferably has a reflection coefficient close to that of 0.38, which will lead to almost the same intensity of the beam reflected from the front electrode and the transmitted beam reflected from the back of the electrode beam and the transmitted beam.

Fully reflective electrode may be a layer of aluminum, covered with a thin layer of indium oxide-tin (Reis), as an electrode having a large work function (injection hole). Partially reflecting and/or partially transmitting electrode can be a thin (3-4 nm) layer of chromium that plays a role is lectrode, having a small work function (injection of electrons). The dielectric can be made of polyparaphenylene (PPV) as a light-emitting material. Specialists in the art will easily be able to conclude that other combinations of suitable materials based on existing descriptions of the production technology Osipov.

According to the invention, the same multilayer stop thus combines the functions of the electroluminescent device (Aside) and optically variable devices (BARS). This is achieved through a combination of a dielectric layer or multilayer films with the properties of light emission, and mentioned dielectric layer or multi-layer film has a suitable thickness to ensure the effects of optical interference between the first and second surfaces, the first and second at least partially reflective electrodes are located on said first and second surfaces, respectively, mentioned dielectric layer or multilayer film, so that the said first and second electrodes have the properties of injection of carriers, respectively, in the form of holes and electrons.

Considering the description of the proposed technical solutions together with descriptions of the known technical solutions technology Osipov, a specialist in this field of technology is key will be able to realize numerous alternative specific embodiments of optically variable device based on Osipov (acid-BARS). The specialist will also be able to use inorganic, light-emitting dielectric, as described in previously published literature electroluminescent devices. Or specialist will be able to choose to use a combination of organic and inorganic materials for the manufacture of dielectric, a light-emitting layer.

Acid-BARS according to the invention can be used as such in the form of optically variable light-emitting foil. This foil can be applied to paper money, documents, articles, etc. by means of hot or cold stamping, etc. as a protective element. You can provide for electrical connection of the electrodes to test the light emitting ability of the applied protective foil.

Alternatively, acid-BARS according to the invention can grind with getting helplearn of the pigment particles and to use in the composition of the paint or coating for printing with the print characters on the protected documents or products, or for coating articles. In this case, it is possible to provide the control equipment that emits electrons for excitation of flocculent particles electroluminescent IPRs in the composition of the paint or coating for printing to identify the protective trait. At first, cell battery (included) the container level, mentioned encoded luminescence, optically variable pigment can be identified with the naked eye, watching it shift color depending on the angle. At more advanced level, for example, at points of sale through vending machines, you can use simple tools, such as lamp UV light or small photovoltaic device detection of luminescence, for improved verification of identity. To check the luminescence of individual flocculent particles of the pigment can also use the magnifier, which increases 50-100 times that works with long-wave ultraviolet light. And finally, at the level of Central banks, it is possible to realize a quantitative description of the properties of the color shift, but also a quantitative assessment of the glow IPRs within the parameters of wavelength, intensity and decay time. In addition, fluorescent IPRs according to the present invention is suitable for high-speed detection is carried out at ATMs.

EXAMPLES

Now the invention will be illustrated in the following examples.

1. IUP with a shift in color from gold to green and green luminescence color

To prepare the sodium-compensated phosphor CaF2:Tb,Na by fusing together MESI of calcium fluoride (92 mass parts), fluoride, terbium (6,7 mass parts) and sodium fluoride (1,3 mass parts) at 1500°C.

By means of physical vapour deposition (DGAP) laid siege to the substrate a sequence of 5 layers with the following content:

chrome metal, with a thickness of 4 nm;

CaF2:Tb,Na (2,5% TbF3in CaF2), of a thickness of 480 nm;

metal aluminium, of a thickness of 40 nm;

CaF2:Tb,Na (2,5% TbF3in CaF2), of a thickness of 480 nm;

chrome metal, with a thickness of 4 nm.

The total optical path when the orthogonal drop: 600 nm (n=1,25).

Luminescence of terbium activated long-wave ultraviolet light (UV light).

2. IUP with a shift from gold to green and red luminescence

By DGAP besieged on a substrate a sequence of 7 layers with the following content:

chrome metal, with a thickness of 4 nm;

MgF2thickness 208 nm;

LaF3:Eu (1% EuF3in LaF3), of a thickness of 205 nm;

metal aluminium, of a thickness of 40 nm;

LaF3:Eu (1% EuF3in LaF3), of a thickness of 205 nm;

MgF2thickness 208 nm;

chrome metal, with a thickness of 4 nm.

The total optical path when the orthogonal fall: 605 nm.

Luminescence of europium-activated long-wave UV-light.

3. Compensated by the shift of the colour of IUP with a shift in color from gold to green and Lumine what Cinzia in the infrared region

By DGAP besieged on a substrate a sequence of 7 layers with the following content:

chrome metal, with a thickness of 4 nm;

AlF3thickness of 240 nm;

LaF3:Nd (3% NdF3in LaF3), of a thickness of 200 nm;

metal aluminium, of a thickness of 40 nm;

LaF3:Nd (3% NdF3in LaF3), of a thickness of 200 nm;

AlF3thickness of 240 nm;

chrome metal, with a thickness of 4 nm.

The total optical path when the orthogonal fall: 605 nm.

Luminescence of neodymium is activated by long-wavelength UV light or, alternatively, the selected wavelengths of the Nd absorption in the visible or near IR region.

4. Compensated by the shift of the colour of IUP with a shift in color from gold to green and luminescence in the infrared region

By DGAP besieged on a substrate a sequence of 7 layers with the following content:

chrome metal, with a thickness of 4 nm;

MgF2thickness of 395 nm;

LaF3:Yb (5% YbF3in LaF3), of a thickness of 40 nm;

metal aluminium, of a thickness of 40 nm;

LaF3:Yb (5% YbF3in LaF3), of a thickness of 40 nm;

MgF2thickness of 395 nm;

chrome metal, with a thickness of 4 nm.

The total optical path when the orthogonal fall: 607 nm.

Luminescence of ytterbium activated infrared radiation (IR radiation) with a wavelength of 950 nm is observed in the spectra the General range 980-1000 nm.

5. Encoded luminescence IUP with a color shift from green to blue

By DGAP besieged on a substrate a sequence of 7 layers with the following content:

chrome metal, with a thickness of 5 nm;

MgF2thickness of 200 nm;

LaF3:Pr,Tb,Tm (1% PrF3+0,5% TbF3+0,5 TmF3in LaF3), the thickness of 166 nm;

metal aluminium, of a thickness of 40 nm;

LaF3:Pr,Tb,Tm (1% PrF3+ 0,5% TbF3+ 0,5 TmF3in LaF3), the thickness of 166 nm;

MgF2thickness of 200 nm;

chrome metal, with a thickness of 5 nm.

The total optical path when the orthogonal fall: 535 nm.

Luminescence of ytterbium activated long-wave UV-light.

6. Luminous, optically variable IPRs based on mica that transform with increasing frequency

Luminescent oxide, Vanadate or oxysulfide film can be obtained on glass substrates by chemical vapour deposition (CVD) using the method and device according to U.S. patent No. 3894164. This method can be adapted to the coating of the particles in the reactor with a fluidized bed.

Got the suspension of the industrial supply of pigment based on mica particles that do not have coverage in the reactor with a fluidized bed heated to a temperature of 480-500°C. a Stream of gaseous argon carrier p is lowered at a rate of approximately 400 ml/min through evaporative furnace, heated to approximately 220°and containing a homogeneous mixture consisting of 92 mole percent of 2,2,6,6 tetramethyl-3,5-heptanedionato yttrium, 3 molar percent of 2,2,6,6 tetramethyl-3,5-heptanedionato erbium and 5 molar percent of 2,2,6,6 tetramethyl-3,5-heptanedionato ytterbium, and was introduced as the first of a reagent gas in a reactor with a fluidized bed. The gaseous mixture of argon (supplied with a speed of 500 ml/min) and gaseous hydrogen sulfide (supplied with the speed of 200 ml/min) was administered as a second gas reactant in said reactor with a fluidized bed. After deposition of the layer with a suitable thickness of the layer of luminescent material on the basis of Y2O2S:Er,Yb that transform with increasing frequency, on the surface of the flaky particles of mica, stopped the flow of the first gas-reagent and annealed pigment at 800°C.

Luminescent coating, having a large refractive index acts as a mirror component that the IPRs on both sides of the mica insulator. This type fluorescent IPRs does not demonstrate the characteristics of excitation depending on the angle.

7. Luminous, optically variable IPR-based flocculent particles of aluminum

Fluorescent films on glass substrates can be obtained by deposition from the liquid, that is, various wet chemical methods type "Sol gel in accordance with U.S. patent No. 4965091. A variant of this method can be used to coat the particles.

Received a suspension of one mass part of the industrial supply, raw pigment-based flocculent particles of aluminum (i.e. with the surface of the oxide without impurities) 5 mass parts of isopropyl alcohol. After adding 1 part of tetraethoxysilane and 0.1 part of a 10%aqueous solution of terbium nitrate in water, was added 1 part of 5%aqueous ammonia solution. The mixture was gradually heated to 80 °With stirring for 8 hours, cooled and filtered. The pigment coated was dried and annealed at 450 °C, after which the excited luminescence of terbium green when excited by long-wavelength UV light.

The second coating of metallic molybdenum was applied to the fluorescent coating in accordance with known methods, to create an optical cavity Fabry - Perot and due to this to get the effect of the color shift.

8. Luminous, optically variable organic pigment

Organic luminescent IPRs was prepared as follows.

As the fluorescent dye used N,N'-bis(2,5-decret-butylphenyl)-3-4-9-10-prerendered, this paint is known from the publications heliocentricism.

As the foil material used polietilene eftalit (PET), having the refractive index n=1,57. As the source materials used pre-prepared transparent Mylar foil having a thickness of 5 μm.

PETP-foil with a thickness of 5 μm was coated N,N'-bis(2,5-di-tert-butyl-phenyl)-3-4-9-10-presidentialbased hands it across a 0.1%solution of fluorescent dye in isopropyl alcohol. The foil with the same coating after drying was coated in vacuum aluminum, reaching a thickness of 40 nm on one side and 140 nm on the other side (which required multiple passes).

Then there was the Assembly of the five-layer composite foil containing:

the covering layer of the transparent PET film with a thickness of 20 microns;

the first layer is dried and aluminized Mylar film thickness of 5 μm with aluminum coating thickness of 140 nm, focused to the center of the Assembly, the middle layer of a transparent PET film with a thickness of 20 microns;

the second layer is dried and aluminized Mylar film thickness of 5 μm with aluminum coating thickness of 140 nm, focused to the center of the Assembly, cover with a layer of transparent PET film with a thickness of 20 μm.

This Assembly has a total thickness of 70 μm, and then unrolled (were subjected to co-extrusion) when the temperature of the rolls in the range between 100°120°to obtain the new total thickness of 5 μm. The total length of the foil as a result of this led is ilaci 14 times, and the corresponding thickness of the individual components decreased in 14 times. The finished multi-layer foil had the following structure:

PET (1,45 μm);

aluminum (3 nm);

PET with a fluorescent dye (350 nm);

aluminum (10 nm);

PET (1,45 μm);

aluminum (10 nm);

PET with a fluorescent dye (350 nm);

aluminum (3 nm);

PET (1,45 μm).

The total optical path between the outer and inner layer of aluminum, i.e. the optical length of the resonator Fabry - Perot, had in this case is n·d=550 nm, which gave IUP with a color shift from green to blue.

The intermediate and cover layers PETP fundamentally necessary to increase the overall thickness of the main foot that allows for the simultaneous extrusion into the desired size. In this case, it is also possible introduction of fluorescent material in the covering layers, and not in the dielectric layers of the Fabry - Perot. The advantages of the presence of the fluorescent material in the resonator, in particular, the ability of the machine to establish such a presence in relation to a simple mixture of normal IUP and fluorescent material, appear in connection with the marking "resonator".

9. Electroluminescent, optically variable organic pigment

Electroluminescent IPRs was prepared as follows.

On PET-foil substrate with motorstv the action of the released coating evaporated following sequence of layers:

1) chrome (3,5 nm) (the layer with the injection of electrons);

2) oligophenylenes (350 nm);

3) the indium oxide-tin (5 nm) (the layer with the injection of holes);

4) aluminum (40 nm) (counter-electrode);

5) the indium oxide-tin (5 nm) (the layer with the injection of holes);

6) oligophenylenes (350 nm);

7) chromium (3,5 nm) (the layer with the injection of electrons).

Layers of chromium, indium oxide-tin and aluminum was evaporated electron-beam method, and the layers of oligopyrimidine evaporated by thermospray.

Oligophenylenes received as samospaseniyu product of 1,4-dimethoxy-2,5-bis-chloromethyl-benzene by reaction with tert-butoxylated sodium in tetrahydrofuran, to yield the product, the average molecular weight of which was about 1000.

Thus obtained layer was separated from the substrate with water and crushed, getting the pigment. Thus obtained IUP had a color shift from green to blue, and showed the luminescence of yellow-green color when exposed to a negative corona discharge.

1. Pigment containing interference structure having at least two thin film layers of different materials, and the pigment has a color shift depending on angle of view, wherein the interference structure includes a light-absorbing dielectric layer containing, m is Nisha least one luminescent material.

2. The pigment according to claim 1, characterized in that its structure contains at least one light-absorbing dielectric layer with the first and second surfaces essentially parallel to each other, and at least one semi-transparent partially reflecting layer located on each of the aforementioned first and second surfaces of the dielectric layer, and the fluorescent material contains at least one of the dielectric layers.

3. The pigment according to claim 1, characterized in that its structure contains the opaque totally reflecting layer, having a first and a second surface essentially parallel to each other, and at least one sequence, formed on at least one of the specified first and second surfaces of the opaque totally reflecting layer, with the specified sequence contains at least one dielectric layer and at least one semi-transparent partially reflecting layer, and the dielectric layer sequence is adjacent to the fully reflective layer, luminescent material contains at least one of the dielectric layers.

4. The pigment according to claim 1, characterized in that its structure contains the opaque totally reflecting layer having first and second is th surface, essentially parallel to each other, and at least one sequence that is located, at least one of the specified first and second surfaces of the opaque totally reflecting layer, with the said sequence contains at least one electrically conductive layer, having a greater work function of at least one dielectric layer and at least one semi-transparent partially reflecting layer, and an electrically conductive layer having a large work function, the specified sequence is adjacent to the fully reflective layer, luminescent material contains at least in one of the dielectric layers.

5. The pigment according to any one of claim 2 to 4, characterized in that at least one of the dielectric layers contains at least a first and a second sublayer, which is the dielectric layer, and the fluorescent material contains at least one of the sublayers.

6. The pigment under item 5, wherein the first sublayer is adjacent at least one of the first or second surfaces of the opaque totally reflecting layer and contains a fluorescent material, and at least a second sublayer made of a material having a refractive index equal to or less than a 1.50, in particular from MgF2and AlF3.

7. Pigmento to claim 1, wherein the structure includes at least one light-absorbing dielectric layer with the first and second surfaces and at least one semi-transparent partially reflecting layer of a material with a higher refractive index having a refractive index of at least 2.00 and located, at least one of the first and second surfaces of the dielectric material, and fluorescent material contained in the material with higher refractive index.

8. The pigment according to claim 1, characterized in that the structure contains at least one opaque totally reflecting layer having first and second surfaces, and at least one semi-transparent partially reflecting layer of a material with a higher refractive index having a refractive index of at least 2.00 and located, at least one of the first and second surfaces of the dielectric material, and fluorescent material contained in the material with higher refractive index.

9. The pigment according to claims 1 to 8, characterized in that at least one of the dielectric layers containing a specified fluorescent material selected from the group consisting of triptolide rare earth elements, triptolide bismuth, or mixtures thereof, complex fluorides trivalent ions redkozemelnye or bismuth and monovalent ions of alkali elements or divalent ions of alkaline earth or transition elements, in particular, zinc, and mixtures thereof.

10. The pigment according to claim 9, characterized in that the rare earth elements selected from the group consisting of yttrium and lanthanoids.

11. The pigment according to any one of claims 1 to 8, characterized in that at least one of the dielectric layers containing a specified fluorescent material selected from the group consisting of triptolide elements of the third main group or bismuth, or trivalent ion of a transition element or their mixtures, complex fluorides of elements of the third main group or of bismuth ion alkaline elements, alkaline earth ion of an element or zinc or mixtures thereof.

12. The pigment according to any one of claims 1 to 8, characterized in that at least one of the dielectric layers containing a specified fluorescent material selected from the group consisting of diferido elements of the second main group or of zinc, or cadmium, or mixtures thereof.

13. The pigment according to any one of claims 1 to 8, characterized in that at least one of the dielectric layers containing the aforementioned fluorescent material selected from the group consisting of organic or ORGANOMETALLIC compounds.

14. The pigment according to any one of claims 1 to 13, characterized in that the luminescent material is an ion of the transition element.

15. The pigment according to any one of claims 1 to 13, wherein the transition element is the nom rare earth element.

16. The pigment according to any one of claims 1 to 13, characterized in that the luminescent material is an organic or ORGANOMETALLIC compound.

17. The pigment according to claim 1, characterized in that at least two layers have the nature of the organic thermoplastic polymer and at least one of these layers contains a fluorescent material.

18. The pigment according to 17, characterized in that the luminescent material is selected from the group consisting of organic compounds, ORGANOMETALLIC compounds and ions of transition elements, in particular ions of rare earth elements.

19. The pigment according to any one of claims 1 to 18, characterized in that 0.1-10% dielectric material is replaced by a fluorescent material.

20. The pigment according to claim 1, characterized in that it contains liquid crystal, optically variable pigments, in particular, a polymer having a cholesteric phase liquid crystal.

21. The pigment according to any one of claims 1 to 18, designed for use as a security feature.

22. A method of obtaining a pigment according to any one of claims 1 to 16, comprising the step of deposition of at least one of the dielectric layers containing fluorescent material, by way of physical vapour deposition.

23. The method according to item 22, wherein using a physical deposition method of steam the basics, the selected method consisting of sputtering, magnetron sputtering, thermal evaporation, and evaporation using electron-beam processing.

24. A method of obtaining a pigment according to any one of claims 1 to 16, comprising the step of deposition of at least one of the dielectric layers containing fluorescent material, a method of chemical deposition from the vapor phase.

25. The method according to paragraph 24, wherein using the method of chemical deposition from the vapor phase, the selected method comprising thermoreactive deposition, reactive sputtering and coating in the fluidized bed.

26. A method of producing a pigment according to any one of claims 1 to 16, comprising the step of deposition from the liquid phase chemical method, at least one of the dielectric layers containing fluorescent material, in particular by the controlled hydrolysis of the precursor in solution.

27. A method of obtaining optically variable pigments in one of the 17 or 18, comprising the step of receiving at least one of the layers containing the aforementioned fluorescent material, by a method selected from extrusion and co-extrusion.

28. The composition of the coating, in particular an ink for printing containing pigment according to any one of claims 1 to 18.

29. The product, in particular the protected document is t, containing layer coating composition, particularly the inks for printing on p. 28.

30. Bulk material containing optically variable pigments according to any one of claims 1 to 18.



 

Same patents:

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41 cl, 2 tbl, 12 ex

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2 tbl

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EFFECT: the invention allows to simplify process and to upgrade parameters of the pigment.

2 cl, 1 tbl, 1 ex

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