Films with variable angle of view made from crystalline colloidal alloys. RU patent 2504804.

FIELD: physics.

SUBSTANCE: radiation diffracting film has a viewing surface and an ordered periodic array of particles embedded in the material of the array. The array of particles has a crystalline structure, having (i) a plurality of first crystal planes of said particles that diffract infrared radiation, where said first crystal planes are parallel to said viewing plane; and (ii) a plurality of second crystal planes of said particles that diffract visible radiation. When the film is turned about an axis perpendicular to the viewing surface and at a constant viewing angle of said film, visible radiation with the same wavelength is reflected from the second crystal planes with intervals equal to about 60°.

EFFECT: designing a film for authenticating or identifying an object.

23 cl, 5 dwg

The technical field

This invention relates to a film materials, radiation, and more specifically, to the periodic arrays held in the composition of the matrix particles that visible and infrared radiation.

The level of technology

radiation materials on the basis of crystal colloidal arrays are used variety of purposes. Crystalline colloidal array (KCM) is a three-dimensional sorted array of monodisperse colloidal particles. The particles are usually consist of polymer, such as polystyrene. Such colloidal dispersion of particles may with the formation of ordered arrays (crystal structures), characterized by periods of a crystal lattice which are comparable with the wavelength of ultraviolet, visible or infrared radiation. These crystalline structure used to filter the narrow lanes of selected wavelengths from a wide range of incident radiation while obstructed radiation related areas of wavelengths. Alternatively KCM produced to radiation in order to use them as dyes, markers, optical switches, optical switches and sensors.

Many of these devices get in the way dispergirovanija particles in the liquid environment, after which the particles as an ordered array. Position of particles in an array can be fixed in the result of mutual polymerization particles or as a result of the introduction of solvent, which provides swelling and fixation of particles with each other.

Other KCM receive from the dispersion equally charged monodisperse particles in the medium. Dispersion is applied on the substrate, and that the media is evaporated to receive the ordered periodic array of particles. Array fix the place of drawing of the array cover of the cure polymer, such as acrylic polymer polyurethane, alkyd polymer, polyester complex, polymer, polysulphide or polymer. Methods of obtaining such KCM described in U.S. patent №6894086, is incorporated by reference. Alternatively particles can have the structure of the «core-shell», where the kernel receive materials, such as those described above for unitary particles, and shell are obtained from the same polymers, which are used in the material kernel, although some arrays particles with the structure of the «core-shell» polymer shell differs from the core material. These particles with the structure of the «core-shell», and methods for their production are described, for example, the publication of the patent application, US no 2007/0100026, incorporated herein by reference.

In such arrays unitary particles or particles «core-shell structure radiation in accordance with the law Bragg, where the radiation corresponding to the terms of the Bragg, is reflected, while the neighboring spectral region, do not meet the conditions of Bragg, skipped through the device. Wavelength of the reflected radiation is partly determined by the effective refractive index of the array and the distance between the particles in the array.

Disclosure of the invention

The present invention includes radiation film with surface observations, and at least part of the surface observation is located in the plane of observation. The film includes an ordered periodic array of particles, included in the matrix material, and an array of particles has a crystal structure, where the crystal structure has (i) a set of the first planes in the crystal of particles infrared radiation, and (ii) the set of second planes in the crystal of particles visible radiation.

In addition, the present invention is enabled method for obtaining optically variable device to fight counterfeiting, including obtaining of dispersion of monodisperse particles; infliction of dispersion of particles on a substrate so that the particles as an ordered periodic array, which radiation; drawing on an array of particles cover from the composition of the matrix; and the fixation with coating array of particles for reception of a film, including the crystal structure, where the particles are of such dimensions that the crystalline structure has (i) a set of the first planes crystal from particles that infrared radiation, and (ii) the set of second planes in the crystal of particles visible radiation.

Brief description of drawings

Figure 1 is a perspective view for radiation material according to the present invention, showing the first set of planes particles;

Figure 2 represents another view for radiation material, shown in figure 1, showing yet another set of planes particles;

Figure 3 is a top view for radiation material, shown in figure 1, showing the additional sets of planes particles;

Figure 4 represents another variant of the invention, includes two films radiation material according to the present invention; and

Figure 5 represents another variant of the invention, includes three films radiation material according to the present invention.

Realization of the invention

For the purposes of onward detailed description of the invention must understand that the invention can be implemented in different variations and alternative sequences stages except when clearly indicated otherwise. In addition, all the numbers, expressing, for example, the quantity of ingredients used in the description of the invention and claims to be understood as in all cases, modified the term «approximately», except working examples or cases where expressly stated otherwise. Accordingly, except as expressly otherwise stated, all numerical parameters shown in the following is a description of the invention and applied the formula of the invention, are approximate values that may vary depending on the desired properties obtained during the implementation of the present invention. And furthermore, without trying to limit the application of the doctrine of equivalents to the volume of the claims of the invention formula, each numerical parameter should be seen at least in light of the number of significant digits, and considering the use of conventional methods of rounding. Despite the fact that the numerical ranges and options that set the scope of the invention, are approximate values, numerical values provided in the specific examples, presented in the most accurately. However, any numerical value in its very nature contains certain errors, inevitably resulting from the availability of standard deviation detected in the measurements of this value in the corresponding tests.

In addition, you must understand that any numerical range, referred to herein, is intended to include all subnets, concluded within its limits. For example, the range of 1 to 10» is intended to enable all subnets from (and including) the specified minimum value of 1 up to the maximum value of 10, that is, including the minimum value greater or equal to 1, and the maximum value equal or less than 10.

In this application, the use of the singular includes the use of the plural, and the plural number covers a single number, unless otherwise stated specifically. In addition, in this application, the use of «or» means «and/or», unless otherwise stated specifically, even though in certain cases «and/or» used explicitly.

The term «polymer» is deemed to include , copolymer of. The term «metal» includes metals, oxides of metals and metalloids. The term «apply» and related terms (such as the introduction) is related to the penetration of a liquid phase.

The present invention includes radiation material that radiation in the visible and/or invisible part of the electromagnetic spectrum, and the ways of its receipt. The material includes an ordered periodic array of particles, included in the polymer matrix. Array includes multiple layers of particles and satisfies the law Bragg in the form of:

mλ=2ndsinθ,

where m is an integer number n is the effective refractive index of the array, d is the distance between the layers of particles, and λ represents the wavelength of the radiation reflected from a plane or a layer of particles angle θ. In accordance with the use of this document «one» wavelength diffracted radiation includes band of the electromagnetic radiation spectrum in a neighborhood of a given wavelength. For example, the reference wavelength of 600 nanometers (nm) may include the range from 595 to 605 nm. Reflected radiation can enter the visible part of the spectrum or the invisible part of the spectrum (infrared or ultraviolet radiation). In accordance with the use of this document, if it will be said that the periodic array of particles radiation by law Bragg or reflects radiation in accordance with the law Bragg, it is assumed that at least some portion of the incident radiation crystal structure of the array, thereby, generating some portion recognised in accordance with the law Bragg radiation.

Material radiation, in General includes periodic array of organic particles held in the organic matrix. Parallel layers or planes formed by periodic array of particles, interacting with the incident radiation in accordance with the law Bragg. Wavelength diffraction of light at a given angle is proportional to the distance between the planes Bragg, educated periodic array of particles, which is proportional to the diameter of the particles for the close-Packed spheres. Wavelength diffraction also depends on the effective refractive index of the material. The effective refractive index of the material, radiation, is well approximated as value of the refractive index materials radiation material, including particles and the matrix material surrounding particles. The intensity of the diffracted radiation depends on the spread of the refractive index of the material, radiation, which is determined by the composition of the particles and the matrix. The intensity of diffraction affects also the number of layers formed by an array of particles and the matrix, and the difference between the refractive indices of the alternating layers. A greater number of particle layers creates a more significant intensity of diffraction. The greater the intensity of diffraction also creates a big difference between the refractive indices of the alternating layers. The big difference between the refractive indices of the alternating layers can be achieved by using particles and the matrix, with a relatively large difference in their respective indices of refraction. Alternatively, change the layer structure and increase the difference between the refractive indices of the layers can aimed expansion of particles and/or the matrix.

radiation material according to the present invention includes an array of particles, recorded in a matrix, as described above, and it is produced in the form of a film that may be or may not be self-sustaining. The film includes surface observations, which at least partially located in the plane and does not protected during use, such as in the case of the product. To describe the relationship between the particles in the figures 1-5 demonstrated only particles of the film. However, you must understand that arrays of particles of the present invention are recorded in the composition of the matrix, as described above. For example, type of surface includes the composition of the matrix, which is not demonstrated in the drawings. In line with this, a reference to an array of particles of the present invention can be attributed to the film of the present invention, involving both the array and the composition of the matrix.

How can you tell when referring to figures 1 and 2, array 2 of the present invention includes many particles 4, arranged in the form of a periodic structure, called this document a crystalline structure. Crystal structure includes many of the first planes in the crystal L of particles 4, which generally are parallel to the plane of the surface observation 6. The first plane of the crystal L represent the position of 111 cubic (FCC) of the crystal. (As noted above, surface observations 6 also includes the composition of the matrix, which is not shown). The first plane of the crystal L incident radiation (for example, falling rays I 1 and 2 ) in accordance with the law Bragg receiving the reflected radiation, which is shown reflected beams R 1 and R 2 . As demonstrated in figure 1, the diffracted radiation is in the sense that the length of the waves diffracted radiation varies depending on viewing angle vertically. Viewing angle vertical is the angle of the incident light also makes with the plane of the surface observation 6. Figure 1 shows two falling beam radiation I 1 and 2 , colliding with an array of 2 two different angles, the angle of the incident beam I 1 forms with surface observations of 6 is smaller than the angle with the surface observation 6 forms the incident beam 12. The corresponding reflected radiation (ray R 1 ), which is reflected from the first planes in the crystal L in accordance with the law Bragg, being caused by the incident radiation I 1 forms smaller angle with the surface observation 6 than the reflected beam, R 2 , obtained from the incident radiation I 2 .

As indicated in figure 2, the crystal structure of the array 2 in the film sets and many in the General case, the second parallel planes in the crystal P (such as a plane 220 in the crystal HCC), passing through the centres of particles is 4, the second plane of the crystal R are perpendicular to the surface observation 6 and the first planes of the crystal L. Incident radiation, with an array of 2 at small angles of the incident radiation, as shown incident beam I 3 , by law Bragg. Similarly radiation incident at small angles, at small angles is reflected from the planes R, as shown by the reflected beam R 4 . Under a small angle of the incident and reflected light means the value, less than about 30 degrees from the surface observation 6.

According to one embodiment of the particle 4 shall be of such dimensions that the wavelength of the radiation reflected from the first planes in the crystal L, is in the infrared part of the electromagnetic spectrum, while the wavelength of the radiation reflected from the second planes in the crystal R, is in the visible part of the electromagnetic spectrum. The wavelengths of reflected radiation is determined, at least partially, corresponding distances between sets of planes L and R. In accordance with the law Bragg more interplanar distance (corresponding to the variable «d») leads to higher wavelength of the reflected radiation, for example, in the infrared part of the electromagnetic spectrum. To select the wavelength of the radiation reflected from the first planes in the crystal L, and wavelengths of the radiation reflected from the second planes in the crystal R, you can control the size of the particles 4, the wavelength of the radiation reflected from the second planes in the crystal P is smaller than the wavelength of the radiation reflected from the first planes in the crystal L. How can you tell when referring as an example to figures 1 and 2, radiation wavelength R 3 is smaller than the wavelengths of radiation R 1 and R 2 .

As demonstrated in figure 3, the array 2 can be viewed from many directions. How can you tell when applying to lines A-F, with the surface observation 6 in the array is located 2 many sets of second-planes of the crystal R. for Example, the incident radiation, with an array of 2 in the direction from line A to line D, by law Bragg and reflects from the second planes in the crystal R between lines A and D. The incident radiation, with an array of 2 in the direction from line to line E, by law Bragg and reflects from the second planes in the crystal R between lines A and E. Another set of second-planes of the crystal R between the lines Cyr similarly radiation incident in the direction from line C to line F. The same phenomenon occurs for the second planes in the crystal R between lines A and D while observing in the direction of the D-link for the second planes in the crystal R between the lines b and E, with supervision in the direction from line to line E and for the second planes in the crystal R between the lines C and F The observation in the direction of the line F to the line C. Each of these areas of surveillance and sets of second-planes of the crystal R separated from each other at approximately 60 degrees. The layout of the six sets of second-planes of the crystal " R " is the sign of the crystal structure of the array 2. Therefore, the Bragg diffraction at small angles in the array 2 takes place approximately 60-degree intervals. In the case of planes R visible radiation, it can detect in the form of Ohr Hozer, the observed with a 60-degree intervals, or visible to 30 degrees and invisible to 30 degrees. Thus, the rotation of the array 2, as it is indicated by a double arrow Z, around the axis perpendicular to the plane of the surface observation 6, (or when traveling in the direction of observation of the user in relation to it) visible radiation is observed to be fired and for every 30 degrees of rotation.

Visible radiation can represent the emergence of a color shift, or may be in the form of images. For example, visible radiation, reflected the second crystal planes R, can be in the green of the visible spectrum, so that when aligning the second planes in the crystal-R in the field of view • user and the rotation of the film in relation to the user in the plane of the film green colour disappears, and the film looks dark, that is, no visible radiation is not reflected. In another embodiment reflected visible radiation from the second planes in the crystal P may be in the form of images, which disappears when the rotation of the film. Methods of obtaining the image in the array are described below.

In yet another variant of the implementation of the present invention includes a multi-layer film 102, including at least two arrays 20, 120 (figure 4 and 5). Arrays 20 and 120 radiation at least in the set of relevant second planes in the crystal P 1 and P 2 . The second plane of the crystal P 1 and P 2 can be offset each other, as shown in figure 4, so that when the rotation of multilayer film 102, as described above, visible radiation reflected from the second planes in the crystal P 1 and P 2 alternating manner. The length of the waves diffracted radiation reflected from the second planes in the crystal P 1 and P 2 , may be identical to each other or different from each other. For example, the second plane of the crystal P 1 in the array 20 may reflect a solid color (green), while the second plane of the crystal P 2 in the array 120 can reflect the image. The rotation of the film 102 may lead to a striped reflection from the second planes in the crystal P 1 and P 2 , so that will be alternating way to appear green color and image. Figure 5 demonstrates the multi-layer foil 202, including three arrays, 2, 20 and 120. Arrays 2, 20 and 120 can be obtained in a wide range of configurations. For example, an array of 2 may reflect the visible radiation from the first planes in the crystal L, an array of 20 may reflect visible light (color or image) from the second planes in the crystal P 1 , and the array of 120 can reflect visible light (color or image) from the second planes in the crystal P 2 . Arrays 20 and 120 reflect their planes in the crystal L infrared radiation. The relative locations of arrays 20 and 120 (figures 4 and 5) may be adjusted to reflect the second planes in the crystal P 1 and P 2 are not in the phase of each other or would have had the same direction, or overlap each other. In addition, to achieve the desired effect in color, the effect on the image, infrared reflectance or their combinations in multi-layer foil can be included multiple arrays. You must understand that, in accordance with the present invention may be obtained many variations of multilayer films.

Particles

Suitable materials for particles include polystyrene, polyurethane, acrylic polymers, alkyd polymers, polyester complex, polymers, polysulphides, polymers-polymers, made from polymers and inorganic materials such as metal oxides (e.g., aluminium oxide, silicon dioxide or titanium dioxide) or semiconductors (for example, cadmium selenide), or composites of these materials.

In one embodiment particles have in the General case of a unitary structure. In accordance with the use of this document «unitary structure» denotes the sign of particles, each of which has in the General case of uniform structure in the absence of components, although its composition may vary by volume unitary particles thus, as it can occur in in her solvent or matrix. In the alternative, the particles can have the structure of the «core-shell», where the kernel receive from a composition different from the composition of the shell. Suitable composition engine particles include organic polymers such as polystyrene, polyurethane, acrylic polymers, alkyd polymers, polyester complex, polymers, polysulphides, polymers or polymers produced from polymers and inorganic materials such as metal oxides (e.g., aluminium oxide, silicon dioxide or titanium dioxide) or semiconductors (for example, cadmium selenide). Suitable composition shell include organic polymers (for example, polystyrene, polyurethane, acrylic polymers, alkyd polymers, polyester complex, polymers, polysulphides, polymers or polymers produced from polymers), the composition of the shell particles differs from the matrix material for a specific array of particles possessing the structure of the «core-shell». Membrane material can be in the sense that the material of the shell is located in the environment of the nucleus of each particle without the formation of a film of a material of the shell, so that the particles having the structure of «core-shell», remain in the polymer matrix in the form of discrete particles. As such the array consists of at least three General areas: namely, matrix, shell particle and the nucleus of the particles. Alternatively, the membrane material can be film-forming, so that the material of the shell formed a film around the nucleus. Material kernel and the shell material are characterized by different indexes of refraction. In addition to this, the index of refraction of the shell may vary depending on the thickness of the shell in the form of the gradient of the refractive index on the thickness of the shell. The gradient of the refractive index can be a result of the presence of the gradient of the composition of a material of the shell on thickness of the shell.

In one embodiment kernel particles receive as a result of emulsion polymerization of monomers predecessors kernel in the presence of surface-active substances, resulting in the dispersion of nuclei. Surfactants, suitable for use in the dispersion of particles of organic polymer, include, but are not limited to: sodium, 1--2- sodium (commercially available under the name Sipomer COPS-I from the company Rhodia Corporation), and sodium. Particularly suitable for surface-active substances are those which have minimal soluble in dispersant fluid (such as water) of dispersion of particles. The dispersion of particles nuclei add monomers shell together with surface-active agent ( above) so that the monomers shell on particles of nuclei. Particles with a structure of «core-shell», clear of dispersion by methods such as ultrafiltration, dialysis or ion exchange, removing unwanted materials such as unreacted monomer, small polymers, water, initiator of the surface-active agent, unrelated salt and crushed (agglomerated particles), to obtain of charged particles with the structure of the «core-shell». When cleaning the charged particles particularly suitable for use is ultrafiltration. In case of finding in the dispersion together with particles of other materials such as salt or by-products, the repulsive force between charged particles can be loosened; therefore, the dispersion of particles clear to the substantive content only charged particles, which then will be easy to repel each other and form the substrate of an ordered array, as described below.

In yet another embodiment particles with a unitary structure of the obtained dispersion monomers together with initiators in the solution to obtain a unitary particles, as described above in relation to the production of nuclei particles possessing the structure of the «core-shell». The variance of the unitary particles cleaned in such a way as it was described above to obtain the dispersion only charged unitary particles, which then form the substrate of an ordered array, as described below.

An array of particles

After removing excess of materials raw materials, by-products, the solvent and the like electrostatic repulsion of charged particles leads to particles in the form of an ordered array. Purified dispersion of particles is applied to the substrate and dried. The dispersion of the particles deposited on the substrate may contain 10-70% (vol.) charged particles, or 30-65% (vol.) charged particles. Dispersion can be applied to the substrate by dipping, spraying, brush application, coating cushion, curtain coating, coating douche or spin pack coating to obtain the desired thickness. Wet coating can have a thickness of 4-50 microns, such as 20 microns. After drying, the material contains essentially the only particles that in array form Bragg and, accordingly, radiation.

Dried array of particles (unitary or with the structure of the «core-shell») on a substrate is fixed in the polymer matrix by mapping the array of coating particles of the fluid composition of the matrix, which includes the monomers or other materials-predecessors of polymers, as described in U.S. patent №6894086 (included in this document by reference), the interpenetration array of particles and composition of the matrix. Material composition of the matrix can be applied as a coating on the dried up an array of particles by dipping, spraying, brush application, coating roller coating using engraved cylinder, curtain coating, coating douche, spin pack coating or coating. Under the coating, meaning that cures the composition of the matrix covers at least essentially the entire array and at least partially fills the gaps between the particles.

Material of the matrix may represent an organic polymer, such as polystyrene, polyurethane, acrylic polymers, alkyd polymers, polyester complex, polymers, polymers and/or polymers produced from polymer. In one embodiment, the implementation of the matrix material is a soluble in water or hydrophilic acrylic polymer. In one embodiment, the implementation of the matrix material is a soluble in water or hydrophilic acrylic polymer. Monomers, suitable for use in obtaining soluble in water or hydrophilic matrix, include, but are not limited to: , polyethylene glycol (600), polyethylene glycol (400), polyethylene glycol (200) and acrylic acid, followed by curing the composition of the matrix to produce organic matrix. Other monomers, suitable for use in obtaining soluble in water or hydrophilic polymer matrix may include polyethylene glycol (1000), (350), (350), (550), (550), bisphenol A, 2-(2-), acrylamide, , , polyethylene glycol (600), polyethylene glycol (400), bisphenol A, and .

As detailed below, an array of particles, included in the matrix can be obtained on the substrate, which performs the function of temporary supports, or on a substrate, which is a desirable version of the end-use of material, radiation. Under the temporary support means that the substrate is used to facilitate radiation material according to the present invention, which later it is removed in the form of a self-sustaining, such as, for example, the self-sustaining film, or in the form of crushed dispersed material. After this film material, radiation or particles of the material, radiation, can be plotted on a different removed or added to the composition (such as the composition of the coating) for own final intended use. The final variant of use and the final form of the material, radiation, limit those described in this document.

In the case of multilayer films (for example, films 102 and 202) several films, including the appropriate arrays (for example, arrays 20 and 120)recorded in the relevant matrices, get together and laminate by thermal bonding or foil connection with each other by means of glue. Multilayer films may be or may not be self-sustaining.

In one embodiment radiation material according to the present invention is a and essentially solid. The term « means that material, radiation, does not contain material, such as water, and how is a hydrogel and not formed from hydrogel. In certain embodiments of the implementation of the radiation material according to the present invention essentially includes only particles and the matrix for the possible existence of a certain amount of residual solvent and, thus, essentially is hard. Volumetric ratio between the particles and the matrix material, radiation, is typically in the range from approximately 25:75 to approximately 80:20.

Image in material, radiation, can be obtained using actinic radiation, as described below. In one embodiment, the implementation of an array of particles include matrix thus, as a result of the preliminary aggregation equally charged particles in the form of periodic array on the substrate and application of an array of particles coverage of composition of the matrix. On a periodic array of particle coating can be applied as a result of composition of the matrix on the array by spray, brush application, coating roller coating using engraved cylinder, curtain coating, coating douche, spin pack coating or coating (as described in U.S. patent №6894086) or by introducing an array of particles in the composition of the coating to the substrate.

In yet another variant of the implementation of the first part of the array, which has a coating of matrix expose actinic radiation curing matrix in part, influenced by. The remaining to the exposed section of change to create an array indignation and prevent radiation rest of it. Indignation for the orderly periodic array of particles can be created using various methods, including, for example, drawing on the array solvent, which at least partially dissolves particles, overheating exposed parts for the destruction of particles or mechanical destruction of particles.

Substrate

The substrate can be a flexible material, such as metal sheet or foil (for example, aluminum foil, paper or film (or list) of a composite polyester or poly (ethylene terephthalate) (PET), or rigid material such as glass or plastic. The term «flexible» refers to the possibility of backing the impact of mechanical stresses, such as at bending, tensile, compression, and so forth, without any significant irreversible changes. One of the suitable for use microporous substrates is sheet. Some examples of microporous sheets are described in the patents of USA №№4833172; 4861644 and 6114023, which are incorporated herein by reference. Commercially available Millipore plates are sold under the designation Teslin® in PPG Industries, Inc.. Other suitable for use flexible substrates include natural leather, synthetic leather, finished with natural skin with synthetic leather, suede, vinyl nylon, foam (foam EVA), thermoplastic urethane (TPU), the chamber filled with liquid, polyolefins and polyolefin mixture, polyvinylacetate and its copolymers, polyvinylchloride and its copolymers, urethane elastomers, synthetic textile and natural textiles.

In certain embodiments of the implementation of flexible substrates are compressible substrates. The term «compressible substrate», and similar terms refer to substrates, able to be subjected to deformation of compression and restore essentially the same form immediately after the termination of exposure deformation of compression. The term «deformation of compression» refers to mechanical stress, which reduces the volume of the substrate at least temporarily at least in one direction. As noted above, the composite material of the present invention may be applied to compressible substrate. The term «compressible substrate», and similar terms refer to substrates, able to be subjected to deformation of compression and restore essentially the same form immediately after the termination of exposure deformation of compression. The term «deformation of compression», and similar terms refer to mechanical stress, which reduces the volume of the substrate at least temporarily at least in one direction. Compressible substrate is that which, for example, is characterized by relative compression, equal to 50% and more, such as 70%, 75% or 80% or more. Specific examples of compressible substrates include those that involve the foam and polymer chamber filled with air, fluid and/or plasma. «Foam» can be plastic or natural material, including foam with open-cell foam and/or foam with closed pores. «The foam with open pores» indicates that the foam includes many interrelated air cavities; «closed cell foam» indicates that the foam includes discrete closed pores. Examples of foams include, but are not limited to: , polyvinylacetate and/or his copolymers, polyvinylchloride and/or his copolymers, (met), , foams, thermoplastic and polyolefin foams and polyolefin mixture. Polyolefin foams include, but are not limited to: , penopolietilenovye sleeping and («EVA») foams. «EVA foam can include foam with open-cell foam and/or foam with closed pores. EVA foam may include flat sheets or plates or molded foams EVA, such as the spaces between the lining and sole shoes. Different types of EVA foam can be characterised by different types of porosity of the surface. Molded EVA foam can be tightly Packed surface or crust, while the flat sheets or plates can have a porous surface.

Composite material can be applied to the product in different ways. In one embodiment composite material was obtained on the substrate, and are removed from the substrate and crushed to obtain dispersed forms, such as the form of flakes. Crushed composite material can be included as a Supplement in the composition of coating for the product. Beneficial could be minimizing the turbidity of the composition of coating, containing crushed composite material. Reduced turbidity can be achieved by decreasing the difference in refractive index between the matrix and the particles of the composite material. However, reduction of the difference of refraction in the General case leads to a decrease in the intensity of the broken radiation. Therefore, in the case of the desirability of minimum turbidity and reduce the difference in the refractive indices of intensity can be saved as a result of increasing the thickness of the composite material that is due to the increase in the number of particle layers in the array, in comparison with what is in place for the material of which the refractive index of the matrix and particles differ from each other to a greater extent.

In one embodiment, the composition of the coating includes «hard surface», such as in the case of alkoxide. can be further incorporated into and/or put into a reaction with other connections and/or polymers, known state of the art. Particularly suitable for use are the compositions containing siloxanes, formed as the result, at least partial hydrolysis , such as the one described by the above formula. Examples of suitable compounds and methods of their production are described in U.S. patents№№6355189; 6264859; 6469119; 6180248; 5916686; 5401579; 4799963; 5344712; 4731264; 4753827; 4754012; 4814017; 5115023; 5035745; 5231156; 5199979; and 6106605, which are incorporated herein by reference.

In certain embodiments of the implementation of the includes a combination of [(C 1-C 3 )alkyl]three(C 1-C 4 ) monomer and Tetra(C 1-C 6 ) monomer. [(C 1-C 3 )alkyl]three(1-4 ) monomers, suitable for use in the coating compositions of the present invention comprise , a-, a-, b-, b-, a-, a-, b-, b-, gamma , their hydrolysates and/or blends of such monomers. Suitable tetrakis(1-C 6 ) that can be used in combination with [(C 1-C 3 )alkyl]three(C 1-C 4 )alkoxysilane in coating compositions of the present invention, include, for example, materials, such as , tetraethoxysilane, , , , and their mixtures.

In certain embodiments of the implementation of the [(C 1-C 3 )alkyl]three(1-4 ) and tetrakis(1-C 6 ) monomers used in the coating compositions of the present invention are present with the mass ratio between [(C 1-C 3 )alkyl]three(1-4 )alkoxysilane and Tetra(C 1-C 6 )alkoxysilane in the range from 0.5:1 to 100:1, such as from 0.75:1 to 50:1, and in some cases from 1:1 up to 5:1. In certain embodiments of the implementation of the at least partially hydrolyzed to its Association with other components of the composition of coating, such as prisoners in polymer particles, lend colour. Such reaction of hydrolysis is described in U.S. patent №6355189, in column 3, in lines 7 to 28, the quoted part of which is incorporated herein by reference. In certain embodiments of the implementation of the water in the quantity necessary for hydrolysis alkoxide (). For example, the specific options for implementing water is present in a quantity equal to at least 1.5 moles of water per mol alkoxide. In certain embodiments implement appropriate can be atmospheric moisture in the case of the sufficiency of such.

In certain embodiments of implementation for catalysis reaction of hydrolysis and condensation serves catalyst. In certain embodiments of the implementation of the catalyst is an acidic material and/or material, different from the acidic material which generates acid when exposed to actinic radiation. In certain embodiments of the implementation of the acidic material chosen from the organic acids, inorganic acids or their mixture. examples of such materials include acetic, formic, , , nitric, hloristovodorodnuyu, phosphoric, hydrofluoric, sulfuric acid, or mixtures thereof.

As a catalyst hydrolysis and condensation coating compositions of the present invention can be used any material which generates acid when exposed to actinic radiation, such as a Lewis acid and/or acid Б. examples of compounds, acid generating include salt and salt, aromatic salt, salt, o-nitrobenzaldehyde, polymers described in U.S. patent №3991033, esters described in U.S. patent №3849137, , their polyesters and derivatives, have entered end groups described in U.S. patent №4086210, esters or aromatic sulfonic acids, alcohols having group in the position of alpha or beta relative to the group of ester sulfonic acids, N- aromatic amide or , aromatic , and resins having in chains groups, such as those described in U.S. patent №4368253. Examples of these acid catalysts, activated radiation, are also described in U.S. patent №5451345.

In certain embodiments of the implementation of the connection, the generating acid, is a cationic , such as salt. examples of such materials include salt and salts, which are available commercially under the name SarCat® CD-1012 and CD-1011 of the company Sartomer Company. Other suitable salts are described in U.S. patent №5639802, in a fragment from column 8, line 59 to speakers 10, line 46. Examples of such onievyh salts include tetrafluoroborate 4,4'-, phenyl-4-, , [4-[(2-)oxy] phenyl] and their mixtures.

The quantity of catalyst used in coating compositions of the present invention, can vary widely and depends on the specific materials used are. All you need is the amount needed for catalysis and/or initiation of the reaction of hydrolysis and condensation, e.g. catalysing number. In certain embodiments of the implementation of the acidic material and/or material that generates acid can be used in the range from 0.01 to 5% in mass) in calculating the cumulative mass of the composition.

radiation material obtained in accordance with the invention may be used in marking devices, including in the case of valuable documents, products of industrial production and packaging and identification documents, in particular, to devices for fighting counterfeiting. Examples of valuable documents include currency, credit cards, certificates of conformity, collectibles and trading cards, written documents, security documents or registration documents (for example, truck), self-adhesive labels conformity tickets (for example, tickets, events or punitive coupons for violation of Parking rules), tax stamps, coins, stamps, cheques and payment orders, printed materials, lottery tickets, tokens and/or tags, documents of strict accountability (for example, the testimony), key-cards, keys, tracking devices and support and elements as part of the barcode. Products of industrial production and packaging of the products of industrial production can include details of the aircraft, vehicle components, such as the ID number of transport funds, pharmaceuticals and personal care products, media, clothing and footwear, and electronics, batteries, ophthalmic devices, alcohol, food, printing inks and printing consumables, stationery, luxury goods, such as suitcases and handbags, sporting goods, software and software packing, seals from tampering, arts and crafts (including original works of art), construction materials, military equipment, toys, fuel, industrial equipment, biological materials and living goods, jewelry, books, Antiques, safety devices (e.g. fire extinguishers and filtration devices), carpets and other items of furniture, chemical reagents, medical devices, paints and coatings and the window and transparencies. Examples of identity documents, which may contain composite obtained in accordance with the present invention, include driver's licenses, ID cards (government, corporate, and educational), passport, visas, certificates of marriage, medical identification bracelets and diplomas. These examples are not intended to limit the scope of the invention and represent only a selection of devices that may contain radiation material according to the present invention. Such options are not intended for use restrictions.

radiation material according to the present invention can be used to certify the authenticity of the product thus, as in the case authenticate the document or devices, or of identifying the origin of the product industrial production. The document, such as card-pass, which contains radiation material according to the present invention, he would be considered authentic, if a product containing material, radiation, would have its properties, such as of certain wavelengths of radiation with a particular level of intensity. «Card-pass» includes documents or device, that confirm the identity of the owner thereof or allow access to an object, such as in the form of a token. Card-pass may identify the owner of the card (for example, card or passport), or it can perform the function of a document or device, that indicate the permission of their owner to the custodial facility. For example, the card is a pass that looks genuine, can be tested for properties radiation. Counterfeit card-pass could not demonstrate this property. Similarly, consumers of the product (such as the pharmaceutical product, as proposed in the package with optically variable device to fight counterfeiting according to the present invention can put the packaging tested for its authenticity as a result of tests on her diffraction properties. Packaging that does not give an adequate response, would be considered counterfeit, while packaging that really has this property would be considered genuine. Other consumer goods may also include radiation materials according to the present invention thus, as on the housing product industrial production (e.g. electronic device) or on the surface of an item of clothing (for example, footwear).

Material radiation, may additionally be at least partially covered composition of the coating in a multilayer structure. In one embodiment of the composite material is applied above the composition of the coating in the form of «solid cover». In yet another variant of the implementation of the composite material is applied antiglare coating, such as in the case of laminated package. Antiglare coating may be obtained from a dielectric material; for example, metal oxides, such as Zr 2 SnO 4 , In 2 SO 4 , SnO 2 , TiO 2 , In 2 O 3 , ZnO, Si 3 N 4 and/or Bi 2 O 3 , deposited by sputtering.

The following examples are provided to demonstrate the General principles of the invention. Presented concrete examples should not be considered as a limitation of the present invention. Unless otherwise stated, all the parts are common parts.

Example 1. infrared radiation particles, having the structure of «core-shell»

Dispersion of particles possessing structure « kernel/styrene-methyl- shell», in the water received by the following method.

Sodium bicarbonate from the company Aldrich Chemical Company, Inc. (2 g) mixed with 2400 g deionized water and added in a 4-quart reaction chamber, equipped with a thermocouple, a solar cover, a mixer, and reflux condenser inlet of nitrogen. Through a mixture for 25 minutes while stirring blew nitrogen, and then over it formed a nitrogen atmosphere. The mixture while stirring was added Aerosol MA80-I (5.0 g) from the company Cytec Industries, Inc. and 3.0 g Brij 35 ( ether (23)from Aldrich Chemical Company, Inc., 1.2 g sodium (CLO) and 150 g of ethylene, styrene monomer (500 g), all received from the company Aldrich Chemical Company, Inc.. the Mixture was heated to approximately 65 C when using casing. The mixture while stirring was added sodium persulphate from the company Aldrich Chemical Company, Inc. (6,0 g 200 g deionized water). With stirring temperature for up to 2.5 hours to withstand approximately 65 degrees C. for 40 minutes stirred, and after that was added to the reaction tank mixture of water (300 g), Brij 35 (3.0 g), styrene (68 g), methyl methacrylate (102 g), (15 g) and CLOS (0.8 g), reagents available in the company Aldrich Chemical Company, Inc.. the Temperature of the mixture for about 3.5 hours kept equal to 65 degrees C. Obtained in the result of the polymer dispersion was filtered through bag filter.

The polymer dispersion subjected ultrafiltration using a 4-inch (102 mm) casing equipped with membrane size 2,41 inches (61,2 mm), where both components are received in the company PTI Advanced Filtration, Inc., Oxnard, California, and pumped using a peristaltic pump with a flow rate is approximately equal to 170 ml / second. After removal 2882 g dispersion added water (2882 g). This currency was repeated several times until you replace the 7209 g on 7209 g deionized water. After this additional amount removed until reaching the level of solid substances in a mixture of equal 42,6 mass percent. Material with a device for spin pack coating from the company Frontier Industrial Technology, Inc., , Pennsylvania was deposited on a substrate made of polyethylene terephthalate (PET), which has a thickness of 2 mil (51 microns), and within 60 seconds dried at 180 degrees Fahrenheit (82,2 OC) to the thickness of the dry material is equal to approximately 10 microns. The resulting material radiation at 821 nm, as measured using a spectrophotometer Saga 500 from Varian, Inc.

Example 2. visible light particles, having the structure of «core-shell»

Dispersion of particles possessing structure «polystyrene- kernel/styrene-methyl--

shell, in the water received by the following method. 3.0 g of sodium bicarbonate from the company Aldrich Chemical Company, Inc. mixed with 4100 g deionized water and added to the 12-liter reaction chamber, equipped with a thermocouple, a solar cover, a mixer, and reflux condenser inlet of nitrogen. Through a mixture for 40 minutes while stirring blew nitrogen, and then over it formed a nitrogen atmosphere. The mixture while stirring was added Aerosol MA80-I (16.0 g 410 was deionized water) from the company Cytec Industries, Inc., styrene monomer (416,4 g) and 8.0 g Brij 35 ( ether (23)), where both components are received in the company Aldrich Chemical Company, Inc., followed by washing with the help of 48 g deionized water. Mixture for 30 minutes was heated to approximately 50 degrees when using casing. After that to a mix added 8.0 g from the company Aldrich Chemical Company, Inc.. Mixture was heated up to 60 C, and then added with stirring styrene monomer (940 g). The mixture while stirring was added sodium persulphate from the company Aldrich Chemical Company, Inc. (12 grams per 144 of deionized water). The temperature of the mixture within 90 minutes kept constant. With stirring to a mix added DVB from the company Aldrich Chemical Company, Inc. (100 g). Had adding 6.0 g Brij 35 100 g deionized water. After that the mixture while stirring was added sodium persulphate from the company Aldrich Chemical Company, Inc. (3.0 g 900 g deionized water). The reaction mixture while stirring was added mixture of styrene (150 g), methyl methacrylate (200 g), (35 g), all of which are available in the digging Aldrich Chemical Company, Inc.. The reaction mixture while stirring was added sodium (CLO) (4.5 g) followed by washing with the help of 100 g of deionized water. The temperature of the mixture for about 4 hours kept equal to 60°n Obtained in the result of the polymer dispersion was filtered through bag filter. After that is obtained as a result of the polymer dispersion subjected ultrafiltration using a 4-inch (102 mm) casing equipped with membrane size 2,41 inches (61,2 mm), where both components received from the company PTI Advanced Filtration, Inc., Oxnard, California, and pumped using a peristaltic pump with a flow rate is approximately equal to 170 ml / second. After removal of 3000 g dispersion added water (3022 g). This currency was repeated several times until you replace the 7997 g on 7997 g deionized water. After that I deleted the additional number of up to the level of solid substances in a mixture of equal 44,4 mass percent. Material with a device for spin pack coating was deposited on a substrate made of polyethylene terephthalate, having a thickness of two Mila (fifty one micron), and within one minute dried at 180 degrees Fahrenheit (82,2°C) to the thickness of dry porous material, equal to about 8 microns. The resulting material light 494 nm.

Example 3. The organic matrix

The organic composition, under the influence of ultraviolet radiation, received in accordance with the following methodology. Mixture diphenyl(2,4,6-)phosphine oxide/2-hydroxy-2- (0.2 g) with the composition of the 50/50 from the company Aldrich Chemical Company, Inc. with stirring was added to a mixture of 6 g (20) and 4 grams of 1,4-, where both components are received in the company Sartomer Company, Inc., Exton, Pennsylvania.

Example 4. The image of the variable angle of observation

Two drops of UV- compositions, obtained in example 3, placed on a black part of the card opacity of The Leneta Company, , new Jersey, which is slightly cleaned out with a very thin skins Scotch-Brite® (abrasive skin available in the company ZM Corp., Minneapolis, Minnesota). Material obtained in example 1, placed on the card facing down the opacity so that particles with structure « kernel/styrene-methyl- shell», would be in a besieged UV coating and substrate polyethylene terephthalate (PET) would be facing up. On top of a substrate of PET placed not having the cover sheet of the PET. The upper side of the PET use a roller to smudging and indentation of UV cure coatings example 3 in the gaps in the material of the case 1.

On top of a substrate of PET on the part of the map opacity containing a combination of materials from example 1 and example 3, placed the template with the image. Template included transparencies and opaque area. Sample under the action of UV radiation through the transparent parts of the template when using a mercury lamp 100 W. Template and substrate of the PET, including particles were removed from the map opacity and sample cleaned with isopropyl alcohol.

On the map opacity received a film that has the same structure that and transparent sections in the template. The resulting image when observed under the indirect angles to the surface revealed reflected the green color, which has been turned on and off during the rotation in the plane of the film surface. The image was almost colourless when viewing angle, normal to the surface, that is, when observing the observer plane surface at a right angle.

Example 5. Laminated composite image of the variable angle of observation

Methodology study 4 was repeated two more times to get the two additional layers of film, which was applied on top of the material from example 4 (image 1).

In the first repeated technique used material from example 1 with a different pattern of that in the result of the rise to another image (image 2). Material featuring 2 was applied over the film from example 4 (image 1), shifted 90 degrees relative to the orientation film from example 4 (image 1).

In the second method of repeated material from example 2 was administered in material from the example 5 with the subsequent realization of the methods of example 4. The image on the resulting film formed with one another template structure, receiving the third layer (figure 3), which were placed over the film image 2. Composite with three layers in the result led to the obtaining of the plot composite image, which had copper-red color in the observation of the normal to the surface and green when observed under an angle to the surface, equal to 45 degrees or less, (picture 3). Composite image also included a plot of generated image (image 1). This image when observed under the indirect angles demonstrated reflected the green color, which was turned off during the rotation of the composite plane composite film. When the image 1 turned off, it became visible to other reflected green image (image 2). This has been observed every 30 degrees during the rotation of the composite image. On the merits in the case of visible image 1 image 2 was invisible. Similarly, in the case of visible image 2 invisible was a picture 1.

This multi-layer film demonstrated color (image), which in turn are included, and shut down during the rotation of the film in its own plane (picture 1 and picture 2), and other color (image), which you can see at observation angle of the observer.

Despite above preferred embodiments of the present invention can be made and obvious modification and amendment of this invention without deviating from the extent and nature of the present invention. The volume of the present invention is defined in the accompanying claims and its equivalents.

1. A diffracting wave radiation film having a surface observations, where at least part of the said surface observations is located in the plane of observation, including the ordered periodic array of particles, included in the matrix material, where an array of particles has a crystalline structure, and where the said crystal structure has (i) a set of the first planes in the crystal of the mentioned particles that infrared radiation, where referred to the first plane of the crystal parallel to the mentioned plane of observation; and (ii) the set of second planes in the crystal of the mentioned particles that visible radiation, and at the rotation of the film around the axis perpendicular to the surface observation and constant observation angle referred film visible light with the same length of a wave is reflected from the second planes in the crystal at intervals of approximately 60 degrees.

7. Film 6, in which referred crystal structure includes three sets of second planes in the crystal.

8. Film 6, in which at constant observation angle vertically to the plane of observation of the visible radiation with discrete provisions of visibility at the above-surface observations of the film.

9. Film according to claim 1, further comprising another one ordered periodic array of particles, included in the material of the matrix, the mentioned one more massive particles has a crystalline structure that has (i) another set of first planes in the crystal of the mentioned particles that infrared radiation, and (ii) another many second planes in the crystal of the mentioned particles that visible radiation.

10. Film on item 9, in which referred to the second plane of the crystal mentioned two arrays different wavelengths of radiation.

11. Film on item 9, in which referred to the second plane of the crystal mentioned two arrays radiation with the various provisions of visibility at the above-surface observations of the film.

12. Film according to claim 1 in which the particles contain polystyrene, polyurethane, acrylic polymer, alkyd polymer, polyester complex, polymer, polysulfide, polymer and/or polymer derived from polymer, and the matrix contains material selected from the group consisting of polyurethane, acrylic polymer alkidnogo polymer, polyester complex, polymer, , polymer and/or polymer, which derives from polymer.

13. The film section 12 of the matrix also contains inorganic material.

14. Film according to claim 1, which referred to the particles of organic polymer include a core surrounded by a shell, which has a composition different from the composition of referred kernel.

15. The film paragraph 14, in which the kernel particles contain polystyrene, polyurethane, acrylic polymer, alkyd polymer, polyester complex, polymer, polysulfide, polymer and/or polymer derived from polymer, and in which, and the matrix, and the shell contain polyurethane, acrylic polymer, alkyd polymer, polyester complex, polymer, polysulfide, polymer and/or polymer derived from polymer.

16. A product incorporating a substrate and device security, in which the said device security system includes the radiation film according to claim 1.

17. The product according to article 16, in which the product includes valuable document, the product of industrial production, packing products of industrial production and/or identity document.

18. The product according to paragraph 17, where sheet are produced separately from the product and cause the product.

19. The product according see item 18, in which the array has dispersible form for applying to the product.

20. A method of obtaining a device to fight counterfeiting, including: obtain the dispersion of monodisperse particles; infliction of dispersion of particles on a substrate so that the particles as an ordered periodic array, which radiation; drawing on an array of particles cover from the composition of the matrix; and the fixation with coating array of particles for reception of a film with surface observations, including crystal structure, where the particles are of such dimensions that the crystalline structure had (i) the set of the first planes in the crystal of particles infrared radiation, where the first mentioned parallel to the plane of the crystal referred to the plane of observation; and (ii) the set of second planes in the crystal of particles visible radiation, and at the rotation of the film around the axis perpendicular to the surface observation and constant observation angle referred film visible light with the same length of a wave is reflected from the second planes in the crystal at intervals of approximately 60 degrees.

21. The method according to claim 20 in which the particles are of such dimensions that the distance between the planes of the crystal in the crystal structure are any greater than the distance between the second crystal planes in the crystal structure.

22. The method according to item 21, in which the film has a surface observations, where at least part of the surface observation is located in the plane of observation, and where the first plane of the crystal are parallel to the plane of observation, and the second plane of the crystal are arranged at an angle to the plane of observation.

23. The method according to article 22, additionally including: acquisition of further dispersion of monodisperse particles; the application of different dispersion of particles on a substrate so that the particles as another orderly periodic array, which radiation; infliction to another array particles cover from the composition of the matrix; and fixation of another has the floor array of particles of obtaining another film, including other ordered periodic array of particles, included in the matrix material, where another array particles has a crystalline structure has (i) another set of first planes in the crystal of particles infrared radiation, and (ii) other set of second planes in the crystal of particles visible radiation; and folding of the films so that the second plane of the crystal two arrays were at an angle relative to each other.