marking an item or substrate, method of providing a marking an item or substrate and item or substra

专利摘要:
MARKING AN ITEM OR SUBSTRATE, METHOD OF PROVISING A MARKING OF AN ITEM OR SUBSTRATE AND ITEM OR A SUBSTRATE. The present invention relates to the marking of an item or a substrate, which is based on the marking of a precursor composition of chiral nematic liquid crystal (also called cholesteric). Before curing the chiral liquid crystal precursor composition in the chiral liquid crystal state, at least one optical property exhibited by the composition is modified by means of two different types of modifying agents, in at least one area of the product or substrate
公开号:BR112013029939B1
申请号:R112013029939-8
申请日:2012-05-24
公开日:2021-02-02
发明作者:Thomas Tiller；Olivier Rozumek；Tristan JAUZEIN；Andrea Callegari；Frédéric Gremaud；Brahim KERKAR
申请人:Sicpa Holding Sa；
IPC主号:

专利说明:

BACKGROUND OF THE INVENTION 1) Field of the present invention
[001] The present invention relates to the marking of an item or a substrate, which is based on the marking of a precursor composition of chiral nematic liquid crystal (also called cholesteric). Before curing the chiral liquid crystal precursor composition in the chiral liquid crystal state, at least one optical property exhibited by the composition is modified by means of two different types of modifying agents, in at least one area of the product or substrate . 2) Discussion of Background Information
[002] Counterfeiting is no longer a regional problem, but a worldwide problem that has an impact not only on manufacturers, but also on the consumer. Counterfeiting is a significant problem with goods such as clothes and watches, but it becomes even more serious when it affects medicines and drugs. Every year thousands of people around the world die from counterfeit drugs. Counterfeiting also has an impact on government revenues as it affects the collection of taxes for, for example, cigarettes and alcohol, due to the existence of a black market, where it is impossible to control and track counterfeiting (smuggled goods). , embezzled, etc.) with invalid tax stamps.
[003] Many solutions have been proposed to make counterfeiting impossible or at least very difficult and / or expensive, for example, RFID solutions as well as the use of invisible inks.
[004] More recently, a security feature has emerged and is used to authenticate a genuine product, such as a medicine and to prevent counterfeiting. This technology is based on optically variable inks. Its principle is based on the observable color difference of a marking made with optically variable inks when a package, security document, etc. taking the marking is seen from different angles ("the color depends on the viewing angle").
[005] Optically variable inks provide first-line recognition, not only by one person, but also facilitate machine readability. Many patents describe this type of security products, their composition and their application. An example of the various types of optically variable inks is the class of compounds called cholesteric liquid crystals. When illuminated with white light, the cholesteric liquid crystal structure reflects light of a certain color that depends on the material in question and generally varies according to the viewing angle and temperature. The cholesteric material itself is colorless and the color observed is the result of a physical reflection effect on the cholesteric helical structure that is adopted through the precursor composition of chiral liquid crystal at a given temperature. See, for example, JL Fergason, Molecular Crystals, vol. 1, pp 293 to 307 (1966), the entire description of which is incorporated into the present invention by reference to this document.
[006] EP-A-1 381 520 and EP-A-1 681 586, the entire descriptions of which are incorporated herein by reference, describe a birefringent mark and a method of applying it, in the form of a liquid crystal layer having a non-uniform pattern of regions of different thickness. The applied liquid crystal coating or layer can provide an image hidden on a reflective substrate to which the image is invisible when viewed under unpolarized light, but made visible under polarized light, or with the help of a polarizing filter.
[007] US Patent No. 5,678,863, the entire description of which is incorporated into the present invention by reference, describes the means for identifying documents of value that include a paper or a region of the polymer, the said region having a transparent and translucent characteristic. A liquid crystal material is applied to the region to produce an optical effect, which is different when viewed and transmitted to reflected light. The liquid crystal material is in a liquid state at room temperature and must be placed in a medium containing such as microcapsules, in order to be suitable for use in a printing process, such as engraving, roller, spray or inkjet. Printing.
[008] The ordered liquid crystalline state depends on the presence of a chiral contaminant. Nematic liquid crystals without chiral contaminants show a molecular arrangement that is characterized by its birefringence. Nematic polymers are known from, for example, EP-A-0 216 712, EP-A-0 847 432, and US Patent No. 6,589,445, the full descriptions of which are incorporated into the present invention by means of reference.
[009] As mentioned above, the liquid crystal-based security feature provides first-rate recognition by the consumer and also by merchants and producers of goods and articles. As with many other security features that are used in the market, there is always a temptation for counterfeiters to reproduce these security features and thereby mislead consumers and retailers. In view of the foregoing, there remains a need to improve the safety of liquid crystal polymer materials based on liquid crystal precursors.
[0010] One possibility of increasing the level of a security chiral liquid crystal polymer film appears to be overlapping a code in the form of a pattern, the indicia, a barcode, etc., on the polymer film of liquid crystal. However, there is always a risk that a counterfeiter tamper with the code manually and apply it to the liquid crystal polymer film.
[0011] A second possibility to overcome this problem is to introduce the code inside the liquid crystal polymer film. For example, US Patent No. 6,207,240, the entire description of which is incorporated into the present invention by reference, describes the effect of a coating of a cholesteric liquid crystal polymer (CLCP) with color dependent on the viewing angle whose reflection also includes the type of absorption of pigments that have a specific absorption color. A marking, such as a symbol or text, is generated on the CLCP coating by means of laser irradiation. Laser radiation carbonizes the CLCP material in the irradiated area. As a result, the color of the substrate on which CLCP is coated, or the color of the absorption pigments incorporated in the CLCP, becomes visible in the irradiated area. However, the method requires high-powered lasers to carbonize the material and make the marks visible.
[0012] Another possibility is described in U.S. 2006/0257633 A1, the entire description of which is incorporated into the present invention by reference, which is used not only for liquid crystal polymers, but for polymers in general. The method consists of applying a substance that permeates a predetermined region on the surface of the polymer substrate and brings a supercritical fluid in contact with the surface of the polymer substrate to which the permeating substance has been applied for the purpose to cause the permeating substance to permeate on the polymer substrate. The method makes it possible to selectively (partially) modify a portion of the polymer surface. However, for industrial processes where a high marking speed for a large number of items is required, the method is complex and expensive to implement.
[0013] One of the disadvantages of the methods mentioned above, is the lack of ability to modify the chiral liquid crystal polymer layer in a controlled and selective way, to create a marking or coding that is difficult, if not impossible, strong and reliable. , to reproduce and is also compatible with a production line (processes to manufacture items such as passports, packaging, etc.). SUMMARY OF THE PRESENT INVENTION
[0014] The present invention relates to the marking of an item or on a substrate. The marking comprises a layer (continuous or discontinuous) or a pattern of a chiral liquid crystal polymer composition that exhibits an initial set of optical properties and is made by curing a chiral liquid crystal precursor composition in a chiral liquid crystal state . The layer or pattern comprises 3)) one or more first areas showing a defined first modification of optical properties, which is different from the first set of optical properties and can be obtained by contacting the chiral liquid crystal precursor composition in one or more more first areas with a first modification agent; 4)) one or more second areas exhibiting a second set of modified optical properties that is different from the first set of optical properties and different from the first modified set of optical properties and can be obtained by contacting the precursor composition of chiral liquid crystal in one or more of the second areas with a second modifying agent that is of a different type than the first modifying agent.
[0015] In one aspect of the marking, at least one of the one or more first areas can be partially or completely overlapped by means of at least a second area and / or at least one of the one or more of the second areas can be partially or completely overlapping through at least one first area.
[0016] In another aspect of the marking, at least one of the one or more first areas cannot be overlapped by means of any second area and / or at least one of the one or more of the second areas cannot be overlapped by means of any first area.
[0017] In yet another aspect of the marking of the present invention, the first and second modified sets of optical properties may be different with respect to at least one light property that is reflected by means of the chiral liquid crystal polymer composition. For example, at least one property can be selected from one or more of the spectrum, the polarization, and Àmax of the reflected light.
[0018] In yet another aspect of the marking, the initial and the first and second sets of modified optical properties can comprise at least one property that is indicative of an optically anisotropic state of the chiral liquid crystal polymer composition.
[0019] In another aspect, the chiral liquid crystal precursor composition may comprise (i) one or more nematic compounds A, (ii) one or more contaminating chiral compounds B, which are capable of giving rise to a cholesteric state of the composition precursor of chiral liquid crystal, and (iii) at least one salt that changes from a maximum wavelength of the selective reflection band (Àmax) displayed by means of the polymer composition compared to a maximum wavelength of the selective reflection (Àmax) displayed by means of a polymer composition that does not contain at least one salt.
[0020] In one aspect, the one or more nematic compounds A, as well as one or more chiral contaminating compounds B can comprise at least one compound comprising at least one polymerizable group. The at least one polymerizable group can comprise, for example, an unsaturated carbon-carbon bond, such as a group of the general formula H2C = CH-C (O) -.
[0021] In another aspect, one or more of the nematic compounds A and all of one or more contaminating chiral compounds B may comprise at least one polymerizable group.
[0022] In yet another aspect, the chiral liquid crystal precursor composition may comprise at least one contaminating chiral compound B of formula (I):
wherein: R1, R2, R3, R4, R5, R6, R7 and R8 each, independently, denote C1-C6 alkyl and C1-C6 alkoxy; A1 and A2 each, independently, denotes a group of formula (i) to (iii): (i) - [(CH2) yO] zC (O) -CH = CH2; (ii) -C (O) -D1-O - [(CH2) yO] zC (O) -CH = CH2; (iii) -C (O) -D2-O - [(CH2) yO] zC (O) -CH = CH2; Di indicates a group with the formula (Ra), z
D2 indicates a group with the formula mz
m) n, o, p, q, r, s, t each denote independently 0, 1 or 2; y indicates 0, 1, 2, 3, 4, 5, or 6; z is equal to 0, if y is equal to 0 and z is equal to 1, if y is equal to 1 to 6.
[0023] In another aspect, at least one salt can be selected from metal salts and ammonium salts. For example, at least one salt may comprise at least one of lithium perchlorate, lithium nitrate, tetrafluorborate, lithium bromide, lithium chloride, tetrabutylammonium perchlorate, tetrabutylammonium chloride, tetrabutylammonium tetrafluorohydrate, tetrabutylammonium bromide, tetrabutylammonium bromide sodium, sodium chloride and sodium nitrate. In another aspect, at least one salt may comprise lithium perchlorate.
[0024] In another aspect of the marking of the present invention, the precursor chiral liquid crystal composition may be in an initial optically anisotropic state and one or more first areas of the initial optically anisotropic state may be changed to a first optically modified anisotropic state, and in one or more of the second areas of the initial optically anisotropic state it can be changed to a second optically modified anisotropic state or converted to an optically isotropic state.
[0025] In another aspect, the chiral liquid crystal precursor composition can be in an initial chiral liquid crystal state and one or more of the first chiral areas, the initial liquid crystal state can be changed to a first chiral liquid crystal state modified by means of the first modifying agent, and, from one or more domains of the second chiral liquid crystal initial state can be changed to a second chiral liquid crystal state or modified can be changed to a non-chiral liquid crystal state by means of of the second modification agent.
[0026] In yet another aspect of the marking of the present invention, the first modifying agent can be solid and / or semi-solid and the second modifying agent can be fluid and / or the first modifying agent can be practically unable to penetrate the composition chiral liquid crystal precursor and the second modifying agent can penetrate, at least partially, the precursor composition. A semi-solid is capable of supporting its own weight and maintaining its shape, despite having the ability to flow under pressure, for example.
[0027] In another aspect, the first modifying agent may be, or may comprise, a resin that is made from one or more polymerizable monomers. In addition, at least one of the one or more polymerizable monomers may comprise at least two unsaturated carbon-carbon bonds and / or may comprise at least one heteroatom selected from O, N and S. at least one of the one or more polymerizable monomers may comprise at least one group of the general formula H2C = CH-C (O) -or H2C = C (CH3) -C (O) -. In another aspect, the resin can comprise a radiation cured resin such as a UV cured resin and / or the resin can comprise a dry aqueous resin.
[0028] In another aspect, the second modifying agent can be selected from fluid and one or more of (a) a modifying composition comprising at least one compound selected from ketones having from 3 to about 6 carbon atoms, alkyl esters and dialkylamides of carboxylic acids comprising a total of 2 to about 6 carbon atoms, dialkyl sulfoxides containing a total of from 2 to about 4 carbon atoms, and optionally substituted nitrobenzene, (b ) a composition comprising the modification of at least one chiral liquid crystal precursor composition and (c) a composition comprising the modification of at least one contaminating chiral composition.
[0029] In yet another aspect of the marking of the present invention, the first modifying agent can be selected from a cured and / or dried resin solid or semisolid made from one or more polymerizable monomers, and both the first agent of modification as the second modifying agent can change an initial maximum wavelength of the selective reflection band (Àmax) displayed by means of the chiral liquid crystal precursor composition in the liquid crystal state.
[0030] In a still further aspect, the first modifying agent and the second modifying agent can act from opposite sides of the layer or the pattern of the chiral liquid crystal precursor composition. For example, the first modifying agent can be disposed between the substrate and the standard layer or in one or more of the first regions and the second modifying agent can act from the opposite side of the substrate, in one or more of the second areas .
[0031] In another aspect of the marking, the one or more first areas and / or one or more of the second areas can be in the form of at least one of an image, a photo, a logo, the signs and a pattern representing a code selected from one or more of a one-dimensional bar code, a stacked one-dimensional bar code, a two-dimensional bar code, a three-dimensional bar code, a point cloud, a network of lines and a data matrix and / or at least a part of the layer or the pattern can be in the form of at least one of an image, a photo, a logo, the signs and a pattern representing a code selected from one or more of a code one-dimensional bars, a stacked one-dimensional bar code, a two-dimensional bar code, a three-dimensional bar code, a data matrix.
[0032] In another aspect, the article or substrate may be or may comprise at least one of a label, packaging, cartridge, container or capsule containing foodstuffs, pharmaceuticals, nutraceuticals, or drinks, a bank note, a credit card, a stamp, a tax stamp, anti-counterfeiting stamp, a security document, a passport, an identity card, a driver's license, an access card, a transport ticket, a ticket from the event, a voucher, a transfer ink film, the reflective film, an aluminum foil, and a commercial merchandise.
[0033] The present invention also relates to a method of providing an item or substrate marking, as well as a product or substrate produced by this method. The method comprises: n) the application on a surface of an article or substrate, which brings about a first modifying agent in one or more first areas, a curable chiral liquid crystal precursor composition that assumes an initial chiral liquid crystal state , when heated, in such a way that the composition comprises at least a part of one or more first areas, the first modifying agent being able to modify the initial chiral liquid crystal state of the composition; o) heating the applied composition to bring it to a first modified chiral liquid crystal state in which one or more first areas and the initial chiral liquid crystal state in all other areas, if any, of the applied composition; p) applying to one or more of the second areas of the applied composition at least a second modifying agent, which is of a different type than the first modifying agent and (1) is capable of locally modifying the first chiral liquid crystal state initial and / or modified provided by b), or (2) is able to locally modify the initial and / or modified chiral liquid crystal states provided by b) by heating the composition; q) in the case of (2), heating the composition of at least one or more of the second areas and r) curing / polymerizing the entire, thus, chiral liquid precursor composition modified to produce a crystal polymer marking liquid on the article or substrate.
[0034] In one aspect of the method, at least one of the one or more first areas can be partially or completely overlapped by means of at least a second area and / or at least one of the one or more of the second areas can be partially or completely overlapping through at least one first area.
[0035] In another aspect of the method, at least one of the one or more first areas cannot be overlapped by means of any second area and / or at least one of the one or more of the second areas cannot be overlapped by means of any first area.
[0036] In yet another aspect of the marking of the present invention, the initial sets and the modified first and second sets of optical properties may be different with respect to at least one light property that is reflected by means of the polymer composition of chiral liquid crystal. For example, at least one property can be selected from one or more of the spectrum, the polarization, and Tmax of the reflected light.
[0037] In yet another aspect of the method, the initial sets and the modified first and second sets of optical properties can comprise at least one property that is indicative of an optically anisotropic state of the chiral liquid crystal polymer composition and / or it is indicative of the conversion from an optically anisotropic state to an optically isotropic state of the composition.
[0038] In another aspect, the chiral liquid crystal precursor composition may comprise (i) one or more nematic compounds A, (ii) one or more chiral contaminating compounds B, which are capable of giving rise to a cholesteric state of the precursor composition of the chiral liquid crystal, and (iii) at least one salt that changes from a maximum wavelength of the selective reflection band (Àmax) displayed through the composition of the polymer compared to a maximum wavelength of the selective reflection band ( Àmax) displayed by means of a polymer composition that does not contain at least one salt.
[0039] In one aspect, the one or more nematic compounds A, as well as one or more chiral contaminating compounds B can comprise at least one compound comprising at least one polymerizable group. The at least one polymerizable group can comprise, for example, an unsaturated carbon-carbon bond, such as a group of the general formula H2C = CH-C (O) -.
[0040] In another aspect, one or more of the nematic compounds A and all one or more chiral contaminating compounds B may comprise at least one polymerizable group.
[0041] In yet another aspect, the chiral liquid crystal precursor composition may comprise at least one contaminating chiral compound B of formula (I):
wherein: R1, R2, R3, R4, R5, R6, R7 and R8 each, independently, denote C1-C6 alkyl and C1-C6 alkoxy; A1 and A2 each, independently, denotes a group of formula (i) to (iii): (i) - [(CH2) yO] zC (O) -CH = CH2; (ii) -C (O) -D1-O - [(CH2) yO] zC (O) -CH = CH2; (iii) -C (O) -D2-O - [(CH2) yO] zC (O) -CH = CH2; Di denotes a formula group
D2 denotes a formula group
m, n, o, p, q, r, s, et each, independently, denotes 0, 1, or 2; y denotes 0, 1, 2, 3, 4, 5, or 6; z equals 0 if y equals 0 and z equals 1 if y equals 1 to 6.
[0042] In another aspect, at least one salt can be selected from metal salts and ammonium salts. For example, at least one salt may comprise at least one of lithium perchlorate, lithium nitrate, tetrafluorborate, lithium bromide, lithium chloride, tetrabutylammonium perchlorate, tetrabutylammonium chloride, tetrabutylammonium tetrafluorohydrate, tetrabutylammonium bromide, tetrabutylammonium bromide sodium, sodium chloride and sodium nitrate. In another aspect, at least one lithium perchlorate salt may comprise and / or lithium bromide.
[0043] In another aspect of the method of the present invention, the precursor chiral liquid crystal composition may be in an initial optically anisotropic state and in one or more domains of the first initial anisotropic optically state may have changed to a first optically anisotropic state modified, and in one or more of the second areas of the initial optically anisotropic state it may have changed to a second optically modified anisotropic state or converted to an optically isotropic state (depending on the nature of the second modifying agent, as described below).
[0044] In yet another aspect of the method of the present invention, the first modifying agent can be solid or semi-solid and the second modifying agent can be fluid and / or the first modifying agent can be practically unable to penetrate the precursor composition of chiral liquid crystal and the second modifying agent at least partially penetrate the chiral liquid crystal precursor composition.
[0045] In another aspect, the first modifying agent may be, or may comprise, a resin that is made from one or more polymerizable monomers. In addition, at least one of the one or more polymerizable monomers may comprise at least two unsaturated carbon-carbon bonds and / or may comprise at least one heteroatom selected from O, N and S. at least one of the one or more polymerizable monomers may comprise at least one group of the general formula H2C = CH-C (O) -or H2C = C (CH3) -C (O) -. In another aspect, the resin can comprise a radiation cured resin such as a UV cured resin and / or the resin can comprise a dry aqueous resin.
[0046] In another aspect, the second modifying agent can be selected from fluid and one or more of (a) a modifying composition comprising at least one compound selected from ketones having from 3 to about 6 carbon atoms, alkyl esters and dialkylamides of carboxylic acids comprising a total of 2 to about 6 carbon atoms, dialkyl sulfoxides containing a total of from 2 to about 4 carbon atoms, and optionally substituted nitrobenzene, (b ) a composition comprising the modification of at least one chiral liquid crystal precursor composition and (c) a composition comprising the modification of at least one contaminating chiral composition.
[0047] In yet another aspect of the method of the present invention, the first modifying agent can be selected from a solid or semi-solid of the cured or dry resin made from one or more polymerizable monomers, and both the first modifying agent how much the second modifying agent can change an initial maximum wavelength of the selective reflection band (Àmax) displayed by means of the chiral liquid crystal precursor composition in the liquid crystal state.
[0048] In yet another aspect of the method, step b) and / or step d) may comprise heating the chiral liquid crystal precursor composition to a temperature of about 55 ° C to about 150 ° C.
[0049] In another aspect, the chiral liquid crystal precursor composition can be applied to at least one coating by spraying, blade coating, roller coating, canvas coating, curtain coating, printmaking, flexography, screen printing, pad printing, continuous jet ink printing, jet ink printing with drop-on demand, and valve jet printing and / or the precursor chiral liquid crystal composition can be applied in the form of at least , one of a layer (continuous or discontinuous), an image, a photo, a logo, the signs and a pattern representing a code selected from one or more of a one-dimensional barcode, a stacked one-dimensional barcode, a code two-dimensional bar code, a three-dimensional bar code, a point cloud, a network of lines and a data matrix.
[0050] In another aspect of the method of the present invention, the first modifying agent may have been provided on the article or substrate in the first one or more areas of at least one coating by spraying, coating with a blade, roller coating, cover coating, curtain coating, gravure printing, flexography, printing, dry offset printing, typography, screen printing, pad printing, printing, drop-on demand jet ink printing, and continuous ink jet printing , valve jet and / or the first modifying agent can be present in the product or substrate, with one or more first areas in the form of at least one of an image, a photo, a logo, the signs and a pattern representing a code selected from one or more of the one-dimensional barcode, a stacked one-dimensional barcode, a two-dimensional barcode, a three-dimensional barcode, a point cloud , a network of lines and a data matrix.
[0051] In yet another aspect, the second modifying agent can be applied in one or more areas of, at least according to one of the printing, drop-on demand continuous jet ink printing, jet ink printing, coating by spraying, and valve jet printing and / or the second modifying agent can be applied to one or more of the second areas, in the form of at least one of an image, a photo, a logo, the indications and a pattern representing a code selected from one or more of a one-dimensional barcode, a stacked one-dimensional barcode, a two-dimensional barcode, a three-dimensional barcode, a point cloud, a network of lines and a data matrix.
[0052] In yet another aspect, the article or substrate may be or may comprise at least one of a label, packaging, cartridge, container or capsule containing food, beverages, nutraceuticals or pharmaceuticals, a banknote, a credit card, a stamp, a tax stamp, anti-counterfeiting stamp, a security document, a passport, an identity card, a driver's license, an access card, a transport ticket, a ticket from the event, a voucher, a transfer ink film, a reflective film, an aluminum foil, and commercial merchandise. BRIEF DESCRIPTION OF THE DRAWINGS
[0053] The present invention is further described in the following detailed description, with reference to a plurality of drawings by way of non-limiting examples of the exemplary embodiments of the present invention, and in which: - Fig. 1 is a schematic illustrating the procedures described in Examples 1 and 2; and - Figs. 2 and 3 show the different patterns that are obtained by providing the first and second areas of the substrate in different ways. DETAILED DESCRIPTION OF THE PRESENT INVENTION
[0054] The data presented in the present invention are by way of example and for the purpose of illustrative discussion of the modalities only, and are presented in order to provide what is believed to be the most useful and easily understood description of the principles and conceptual aspects of the present invention. In this regard, no attempt is made to show structural details of the present invention in more detail than is necessary for a fundamental understanding of the present invention, the description made with the drawings making it evident to those skilled in the art how the various forms of the present invention can be realized in practice.
[0055] The substrate or product for use in the present invention is not particularly limited and can be of several types. The substrate or product may, for example, consist (essentially) of, or comprise one or more of a metal (for example, in the form of a container, such as a canister of a capsule or a closed cartridge, for carrying out of various articles, such as, for example, nutraceuticals, pharmaceuticals, beverages or food products), a fabric, a coating, glass (for example, in the form of a container such as a bottle for making various articles, such as, for example, nutraceuticals, pharmaceuticals, beverages or food products), cardboard (for example, in the form of packaging), paper, and a polymeric material such as, for example, PET (polyethylene terephthalate) or polyethylene (for example, in the form of a container, or as a part of a security document). It is noted that these substrate materials are given for exemplary purposes only, without restricting the scope of the present invention. In general, any product or substrate (which may not necessarily be flat and may be irregular), the surface of which is not soluble, or only slightly soluble in solvent (s) used in the liquid chiral liquid crystal polymer composition is a precursor to a suitable substrate for the purposes of the present invention.
[0056] The substrate may advantageously have a dark or black surface or background, at least in the areas where the precursor chiral liquid crystal composition is to be applied. Without wishing to be linked to any theory, it is speculated that, in the case of a dark or black background, the light transmitted by the cholesteric liquid crystal material is largely absorbed by the background, through which any residual backscattering of the background does not disturb the perception of the background itself. reflection on the cholesteric liquid crystal material with the naked eye. In contrast, on a substrate with a white backlight surface or the reflection color of the cholesteric liquid crystal material is less visible when compared to a black or dark background, due to the strong backscattering from the background. However, even if a white background light or a cholesteric liquid crystal material can be recognized with the help of a circular polarizing filter, because it selectively reflects only one of the two possible circular polarized light components, according to the its chiral helical structure. In addition, even with a clear or white base it is possible to measure the optical properties of the chiral liquid crystal polymer such as, for example, Àmax with physical media. The substrate according to the present invention can further comprise additional security elements, such as organic and / or inorganic pigments, dyes, flakes, optically variable elements, magnetic pigments, etc.
[0057] The marking of the present invention comprises a layer (continuous or batch) or a pattern of a chiral cured liquid crystal precursor composition in a chiral liquid crystal state (= chiral liquid crystal polymer composition) which has a first set optical properties. The layer or pattern optionally comprises (and preferably), in addition to one or more areas that have the initial set of optical properties (i.e., where no modifying agent has been applied), (1) one or more first areas (for example, one, two, three, four, five, six, ten, fifteen, or first twenty areas, in a case of a data matrix this could be 256 areas when making a 16 * 16 matrix data), which have a first modified set of optical properties that is different from the first set of optical properties and can be obtained by contacting the chiral liquid crystal precursor composition in an uncured state, with one or more first areas with a first modification and (2) one or more of the second areas (for example, one, two, three, four, five, six, ten, fifteen, twenty or second areas, in the case of a data matrix this could be 256 areas over make a matrix of data 16 * 16), which present a second c modified set of optical properties which is different from the first set of optical properties and different from the first modified set of optical properties and can be obtained by contacting the chiral liquid crystal precursor composition in an uncured state, in one or more of the second areas with a second modifying agent that is of a different type than the first modifying agent. In this regard, it is to be appreciated that, for the first and second modified sets of optical properties to be different, it is sufficient that these sets are different with respect to at least and only one optical property. In other words, the first and second modified sets of optical properties can comprise identical optical properties while (at least) an optical property constituted therein is different.
[0058] The layer or pattern may comprise more than two different areas (that is, in addition to one or more of the first regions, the one or more of the second areas and, optionally, one or more areas that have the initial set optical properties) where the initial set of optical properties has been modified by more than two different modifying agents, provided that there are at least two domains in which two different types of modifying agents have been changed separately or together from the first set of optical properties. For example, the layer may comprise three, four, five, etc. different areas in which three, four, five, etc. of the different modifying agents have changed the initial set of optical properties to result in three, four, five, etc. of the modified sets optical properties. Following the use of only two modifiers, and in particular, two modifiers of a different type, it will be discussed frequently because of simplicity. It is to be appreciated, however, that the present invention is not limited to the use of only two modifying agents of different types, and is also not limited to the use of only one modifying agent of a given type. For the sake of example, three modifiers of different types can be used, or a first modifier and a second different modifier can be used.
[0059] In the marking of the present invention, there may also be at least a first area that is not overlapped by a second area and / or there may be at least a second area that is not overlapped by a first area. In addition, there can be at least one first area that is completely or partially overlapped by a second area and / or there can be at least a second area that is completely or partially overlapped by a first area. This includes the case where a first area is larger than the second area and completely includes / covers the second area and the case where a second area is larger than the first area and completely encompasses / covers the first area (as shown in Fig. . two). This also includes the case where a first area and a second area are the same size and completely coincident. The complete or partial overlap of a first area and a second area would result in a third area, that is, the overlap area, giving rise to a third modified set of optical properties (due to the combined action of the first and second modification). Of course, if more than two modifying agents are used, the largest possible number of areas with different sets of optical properties increases exponentially, thus further increasing the difficulty of falsifying the marking of the present invention. Merely by way of example, with three different modifying agents, there may be one or more areas in which only the first modification has been employed, one or more areas in which only the second modifying agent has been employed, one or more areas in which that only the third modifying agent was employed, from one or more domains in which both the first modifying agent and the second modifying agent were employed, one or more areas in which both the first modifying agent and the third, one modifying agent or more areas in which both the second modifying agent and the third modifying agent were used, and one or more domains in which all three modifying agents were employed. It is furthermore to be appreciated that, although the marking of the present invention will generally comprise at least one surface showing the first set of optical properties (i.e., without modification by any modifying agent), the presence of an area correspondent is not required. For example, the present invention also contemplates a marking in which the entire area occupied by the chiral liquid crystal precursor composition in the chiral liquid crystal state is occupied (and modified) by means of the first modifying agent and in which a second ( or more) area of the chiral liquid crystal precursor composition (but not the same entire area) are further modified by means of the second modifying agent (thereby giving rise to a label having one or more first areas that have undergone only the first modifying agent , the remainder being one or more areas modified by third parties, both the first modification agent and the second modification agent).
[0060] The first and second modifying agents for use in the present invention are of a different type. Merely as an example, modifying agents are of a different type, if they differ in consistency (for example, solids and / or semi-solids in one case and fluids (for example, liquid) in the other case) and / or that are different in their chemical nature (for example, a case in monomeric and polymeric, in the other case, essentially or organic, in an essentially inorganic case and in the other case) and / or if they change / alter an optical property of the composition through a different mechanism and / or if the different optical properties of the composition are altered / modified and / or, if they are able to penetrate, at least partially the precursor composition of unpolymerized chiral liquid crystal in one case and are substantially unable to penetrate the precursor non-polymerized chiral liquid crystal composition in the other case.
[0061] The initial set and the first and second (and optionally third, fourth, etc.) modified sets of optical marking properties of the present invention may differ by at least one property of the light radiation that is reflected by means of the polymer composition of chiral liquid crystal in a chiral liquid crystal state. For example, at least one property can be the spectrum (for example, in the visible, infrared and / or UV range), polarization, or Àmax (for example, in the visible, infrared and / or UV range) of reflected light . Àmax can, for example, be measured using a spectral analysis device, which measures the reflectance of a sample in the near-infrared-UV-visible range of the spectrum, such as the LabSpec Pro device by Boulder's Analitical Spectral Devices Inc., Colorado.
[0062] In another aspect of the marking, the initial set and the first and second (and optionally third, fourth, etc.) modified sets of optical properties may comprise at least one property that is indicative of an optically anisotropic or optically isotropic state of the liquid crystal polymer composition. An example of a corresponding property is the reflection of circular polarized light. In this regard, see the explanations provided, for example in Y. Jiang et al., "New approaches to pigment in optically variable safety inks, including polarization of liquid crystal cholesteric polymers (CLC)", Counterfeit and Safety Dissolution Techniques IV, SPIE 4677, 2002, the entire description of which is incorporated into the present invention by reference.
[0063] A chiral liquid crystal precursor composition that can be used to mark the present invention and can be applied (e.g., deposited) on at least part of at least one surface of the substrate (and, in a preferred embodiment) , over at least a part of the first modifying agent provided on at least one surface of the substrate) preferably comprises a mixture of (i) one or more nematic compounds and (ii) one or more cholesteric B compounds (i.e. contaminating chiral) (including cholesterol), which are capable of giving rise to a cholesteric state of the composition. The stage of the cholesteric state obtained depends on the relative proportion of the cholesteric and nematic compounds and the helical torsion energy of the cholesteric compound (s). Typically, the (total) concentration of one or more nematic compounds A in a precursor composition of a chiral liquid crystal for use in the present invention will be about four to about fifty times the (total) concentration of one or more cholesteric compounds B Often, a chiral liquid crystal precursor composition with a high concentration of cholesteric compounds is not desirable (although possible in many cases), because one or more of the cholesteric compounds tend to crystallize, making it impossible to obtain the desired liquid crystal state. having specific optical properties.
[0064] The nematic A compounds that are suitable for use in the precursor chiral liquid crystal composition are known in the art, when used alone (i.e., without cholesteric compounds) they combine with each other in a characteristic state through their birefringence. Non-limiting examples of nematic compounds A that are suitable for use in the present invention are described in, for example, WO 93/22397, WO 95/22586, EP-B-0 847 432, US Patent No. 6,589,445, US 2007 / 0224341 A1 and JP 2009-300662 A. The full descriptions of these documents are incorporated into the present invention by reference.
[0065] A preferred class of nematic compounds for use in the present invention comprises one or more (for example, 1, 2 or 3) polymerizable groups, identical or different from each other, by means of the molecule. Examples of polymerizable groups include groups that are capable of being part of a polymerization by means of free radicals and, in particular, groups containing a carbon-carbon double or triple bond, such as, for example, an acrylate unit, a radical vinyl or an acetylene radical. Particularly preferred as polymerizable groups are acrylate groups.
The nematic compounds for use in the present invention can also comprise one or more (for example, 1, 2, 3, 4, 5 or 6) aromatic groups, optionally substituted, preferably phenyl groups. Examples of the optional substituents on the aromatic groups include those shown in the present invention as examples of substituent groups on the phenyl rings of the contaminating chiral compounds of formula (I), such as, for example, (C1-C6) and / or (C1- C6) alkoxy groups.
[0067] Examples of groups that may optionally be present to link polymerizable groups and aryl groups (e.g., phenyl), in nematic compounds A include those that are exemplified in the present invention for the contaminating B chiral compounds of formula ( I) (including those of formula (IA) and formula (IB) described below). For example, nematic compounds A may comprise one or more groups of general formulas (i) to (iii) which are indicated above as meant for A1 and A2 in formula (I) (and formulas (IA) and (IB)), typically attached to the optionally substituted phenyl groups. Specific non-limiting examples of nematic compounds that are suitable for use in the present invention include: bis [4 - ({[4- (acrylaloxy) butoxy] carbonyl} oxy) benzoate] of 2-methoxybenzene-1,4-diyl; 4 - {[4 - ({[4- (acryl-oxy) butoxy] carbonyl} oxy) -2-methylbenzoate - {[4 - ({[4- (acryloxy) butoxy] carbonyl} oxy) benzoyl] oxide} -2- methoxyphenyl; bis [4 - ({[4- (acryloxy) butoxy] carbonyl} oxy) -2-methyl-benzoate] of 2-methoxybenzene-1,4-diyl; bis [4 - ({[4- (acryloxy) butoxy] carbonyl} oxy) -2-methyl-benzoate] of 2-methylbenzene-1,4-diyl; 4 - {[4- (acryl-oxy) butoxy] carbonyl} oxy) -3-methoxybenzoate 4 - {[4 - ({[4- (acryloxy) butoxy] carbonyl} oxy) benzoyl] oxy} -2- methylphenyl; bis [4 - ({[4- (acryloxy) butoxy] carbonyl} oxy) benzoate] of 2-methylbenzene-1,4-diyl; bis [4 - ({[4- (acryloxy) butoxy] carbonyl} oxy) -3-methoxy-benzoate] of 2-methylbenzene-1,4-diyl; 4 - {[4- (acryloxy) butoxy] carbonyl} oxy) -3,5-dimethoxybenzoate 4 - {[4 - ({[4- (acrylailoxy) butoxy] carbonyl} oxy) -3-methoxybenzoyl] oxy} -2-methylphenyl; bis [4 - ({[4- (acryloxy) butoxy] carbonyl} oxy) -3,5-dimethoxy-benzoate] of 2-methylbenzene-1,4-diyl; and 2-methoxybenzene-1,4-diyl [4 - ({[4- (acryloxy) butoxy] carbonyl} oxy) -3,5-di-methoxy-benzoate]; as well as 4 - {{4- (acryloxy) butoxy] carbonyl} oxy) -3,5-dimethoxybenzoate of 4 - {[4 - ({[4- (acryloxy) butoxy] carbonyl} oxy) -3- methoxybenzoyl] oxy} -2-methoxyphenyl. 4 - ({4- [4- (acryloxy) butoxy] benzoyl} oxy) 4- [4- (acryloxy) butoxy] -2-methylbenzoate) - 3-methylphenyl; 4- [4- (acryloxy) butoxy] -3-methylbenzoate 4 - ({4- [4- (acryloxy) butoxy] benzoyl} oxy) - 3-methylphenyl; bis {4- [4- (acryloxy) butoxy] -2-methylbenzoate} of 2-methylbenzene-1,4-diyl; 4- [4- (acryloxy) -butoxy] -2,5-dimethylbenzoate 4 - ({4- [4- (acryloxy) butoxy] -2-methylbenzoyl} oxy) -3-methylphenyl; 2-methylbenzene-4- [4- (4- (acryloxy) butoxy] -2,5-dimethylbenzoate} bis {4- [4- (acryloxy) butoxy] benzoate} of 2-methylbenzene- 1,4-diyl; 4- [4- (acryloxy) butoxy] -2,5-dimethylbenzoate 4 - ({4- [4- (acryloxy) butoxy] -3,5-dimethylbenzoyl} oxy) -3-methylphenyl; 2-methylbenzene-1,4-diyl bis {4- [4- (acryloxy) butoxy] -3,5-dimethylbenzoate}; bis {4- [4- (acryloxy) butoxy] -3,5-dimethylbenzoate} of 2-methoxybenzene-1,4-diyl; 4- [4- (acryloxy) -butoxy] -3,5-dimethylbenzoate 4 - ({4- [4- (acryloxy) butoxy] -3-methylbenzoyl} oxy) -2-methoxyphenyl; bis {4- [4- (acryloxy) butoxy] -3-methylbenzoate2-methoxybenzene-1,4-diyl} de; 4- [4- (acryloxy) -butoxy] -3-methylbenzoate of 4 - ({4- [4- (acryloxy) butoxy] benzoyl} oxy) -3-methoxyphenyl; 4- [4- (acryloxy) -butoxy] -2,5-dimethylbenzoate 4 - ({4- [4- (acryloxy) butoxy] benzoyl} oxy) -3-methoxyphenyl; bis {4- [4- (acryloxy) butoxy] -2-methoxybenzoate} of 2-methoxybenzene-1,4-diyl; bis {4- [4- (acryloxy) butoxy] -3,5-dimethoxybenzoate} of 2-methoxybenzene-1,4-diyl; bis {4- [4- (acryloxy) butoxy] -3-methoxybenzoate} of 2-methoxybenzene-1,4-diyl; bis {4- [4- (acryloxy) butoxy] benzoate} of 2-ethoxybenzene-1,4-diyl; bis {4- [4- (acryloxy) butoxy] -2-methylbenzoate} of 2-ethoxybenzene-1,4-diyl; bis {4- [4- (acryloxy) butoxy] benzoate} of 2- (propan-2-yloxy) benzene-1,4-diyl; 4 - ({4- [4- (acryloxy) butoxy] butoxy] benzoyl} oxy) -2- (propan-2-yloxy) phenyl 4- [4- (acryl-oxy) butoxy] -2-methylbenzoate; bis {4- [4- (acryloxy) butoxy] -2-methylbenzoate} of 2- (propan-2-yloxy) benzene-1,4-diyl; bis {4- [4- (acryloxy) butoxy] -2,5-dimethyl-benzoate} of 2- (propan-2-yloxy) benzene-1,4-diyl; bis {4- [4- (acryloxy) butoxy] -3,5-dimethyl-benzoate} of 2- (propan-2-yloxy) benzene-1,4-diyl; and 2- (propan-2-yloxy) benzene-1,4-diyl bis {4- [4- (acryloxy) butoxy] -3,5-dimethoxy-benzoate}.
[0068] One or more cholesteric B compounds (i.e., chiral contaminants) for use in the present invention preferably comprise at least one polymerizable group.
[0069] As noted above, suitable examples of one or more chiral contaminating compounds B include tose of formula (I):
wherein: R1, R2, R3, R4, R5, R6, R7 and R8 each, independently, denote C1-C6 alkyl and C1-C6 alkoxy; A1 and A2 each, independently, denotes a group of formula (i) to (iii): (i) - [(CH2) yO] zC (O) -CH = CH2; (ii) -C (O) -Di-O - [(CH2) yO] zC (O) -CH = CH2; (iii) -C (O) -D2-O - [(CH2) yO] zC (O) -CH = CH2; Di denotes a group of formula (Rs) qz
(iv) denotes a formula group
m, n, o, p, q, r, s, et each, independently, denotes 0, 1, or 2; y denotes 0, 1, 2, 3, 4, 5, or 6; z equals 0 if y equals 0 and z equals 1 if y equals 1 to 6.
[0070] In one aspect, one or more contaminating chiral compounds B may comprise one or more isomanide derivatives of formula (IA):
wherein: R1, R2, R3, R4, R5, R6, R7 and R8 each, independently, denote C1-C6 alkyl and C1-C6 alkoxy; A1 and A2 each, independently, denotes a group of formula (i) to (iii): (i) - [(CH2) yO] zC (O) -CH = CH2; (ii) -C (O) -Di-O - [(CH2) yO] zC (O) -CH = CH2; (iii) -C (O) -D2-O - [(CH2) yO] zC (O) -CH = CH2; Di denotes a formula group
D2 denotes a formula group
m, n, o, p, q, r, s, et each, independently, denotes 0, i, or 2; y denotes 0, i, 2, 3, 4, 5, or 6; z equal 0 if y equal 0 ez equal i if y equal ia 6.
[007i] In an embodiment of the compounds of formula (IA) (and of the compounds of formula (I)), Ri, R2, R3, R4, R5, R6, R7 and R8 each, independently, denotes Ci- C6 alkyl. In an alternative embodiment, Ri, R2, R3, R4, R5, R6, R7 and R8 in formula (IA) (and in formula (I)) each, independently, denotes Ci-C6 alkoxy.
[0072] In another embodiment of the compounds of formula (I) and formula (IA), Ai and A2 each, independently, denotes a group of formula - [(CH2) yO] zC (O) -CH = CH2; R1, R2, R3 and R4 each, independently, denote C1 -C6 alkyl; in, n, o, p each, independently, denotes 0, i, or 2. In yet another modality, Ai and A2 in formula (I) and formula (IA) each, independently, denotes a group of the formula - [(CH2) yO] zC (O) -CH = CH2; R1, R2, R3 and R4 each, independently, denote C1 -C6 alkoxy; and m, n, o, and p each, independently, denotes 0, i, or 2.
[0073] In another embodiment of the compounds of formula (IA) (and of formula (I)), A1 and A2 each, independently, denotes a group of formula -C (O) -Di-O- [ (CH2) yO] zC (O) -CH = CH2 and / or of formula - C (O) -D2-O - [(CH2) yO] zC (O) -CH = CH2; and RI, R2, R3, R4, R5, Re, R7 and R8 each, independently, denote C 1 -C 6 alkyl. In an alternative modality, Ai and A2 in formula (IA) (and in formula (I)) each, independently, denotes a group of formula -C (O) -Di-O - [(CH2) yO] zC (O) - CH = CH2 and / or a group of formula -C (O) -D2-O - [(CH2) yO] zC (O) -CH = CH2; and Ri, R2, R3, R4, R5, Re, R7 and R8 each, independently, of Ci-Ce alkoxy note.
[0074] In another aspect, one or more contaminating chiral compounds B can comprise one or more isosorbide derivatives represented by the formula (IB):
where: Ri, R2, R3, R4, R5, Re, R7 and R8 each, independently, denote Ci-Ce alkyl and Ci-Ce alkoxy; Ai and A2 each, independently, denotes a group of formula (i) to (iii): (i) - [(CH2) yO] zC (O) -CH = CH2; (ii) -C (O) -Di-O - [(CH2) yO] zC (O) -CH = CH2; (iii) -C (O) -D2-O - [(CH2) yO] zC (O) -CH = CH2; Di denotes a group of formula (R5) M
D2 denotes a group of formula (R7),
m, n, o, p, q, r, s, et each, independently, denotes 0, 1, or 2; y denotes 0, 1, 2, 3, 4, 5, or 6; z equals 0 if y equals 0 and z equals 1 if y equals 1 to 6.
[0075] In an embodiment of the compounds of formula (IB), R1, R2, R3, R4, R5, R6, R7 and R8 each, independently, denotes C1-C6 alkyl. In an alternative embodiment, R1, R2, R3, R4, R5, R6, R7 and R8 in formula (IB) each, independently, denote C1-C6 alkoxy.
[0076] In another embodiment of the compounds of formula (IB), A1 and A2 each, independently, denotes a group of formula - [(CH2) y-O] z-C (O) -CH = CH2; R1, R2, R3 and R4 each, independently, denote C1-C6 alkyl; in, n, o, p each, independently, denotes 0, i, or 2. In yet another modality, Ai and A2 in formula (IB) each, independently, denotes a group of formula - [(CH2) yO] zC (O) -CH = CH2; R1, R2, R3 and R4 each, independently, denote C1 -C6 alkoxy; and m, n, o, and p each, independently, denotes 0, i, or 2.
[0077] In another embodiment of the compounds of formula (IB), Ai and A2 each, independently, denotes a group of formula -C (O) -Di-O - [(CH2) yO] zC (O ) -CH = CH2 and / or of the formula -C (O) -D2-O - [(CH2) y-O] zC (O) -CH = CH2; and R1, R2, R3, R4, R5, R6, R7 and R8 each, independently, denote C1 -C6 alkyl. In an alternative modality, Ai and A2 in the formula (IB) each, independently, denotes a group of the formula -C (O) -Di-O - [(CH2) yO] zC (O) -CH = CH2 and / or a group of formula - C (O) -D2-O - [(CH2) yO] zC (O) -CH = CH2; and Ri, R2, R3, R4, R5, Re, R7 and R8 each, independently, denote C 1 -C 6 alkoxy.
[0078] In a preferred embodiment, the alkyl and alkoxy groups of Ri, R2, R3, R4, R5, Re, R7 and R8 in formulas (I), (IA) and (IB) can comprise 3, 4, 6 or 7 carbon atoms and in particular, 4 or 6 carbon atoms.
[0079] Examples of alkyl groups comprising 3 or 4 carbon atoms include isopropyl and butyl. Examples of the alkyl groups comprising 6 or 7 carbon atoms include hexyl, 2-methylpentyl, 3-methylpentyl, 2,2-dimethylpentyl, and 2,3-dimethylpentyl.
[0080] Examples of alkoxy groups comprising 3 or 4 carbon atoms include isopropoxy, but-1-oxy, but-2-oxy, and tert-butoxy. Examples of alkoxy groups comprising 6 or 7 carbon atoms include hex-1-oxy, hex-2-oxy, hex-3-oxy, 2-methylpent-1-oxy, 2-methylpent-2-oxy, 2-methylpent -3-oxy, 2-methylpent-4-oxy, 4-methylpent-1-oxy, 3-methylpent-1-oxy, 3-methylpent-2-oxy, 3-methylpent-3-oxy, 2,2-dimethylpent -1-oxy, 2,2-dimethylpent-3-oxy, 2,2-dimethylpent-4-oxy, 4,4-dimethylpent-1-oxy, 2,3-dimethylpent-1-oxy, 2,3-dimethylpent -2-oxy, 2,3-dimethylpent-3-oxy, 2,3-dimethylpent-4-oxy, and 3,4-dimethylpent-1-oxy.
[0081] Specific non-limiting examples of the contaminating chiral compounds B of formula (I) for use in the present invention include: bis (4- (4- (acryloxy)) -3-methoxybenzoyl-oxy) -3-methoxybenzoate) of (3R, 3aR, 6R, 6aR) -hexahydrofuro [3,2-b] furan-3,6-diyl; 4- (4- (acryloxy) benzoyloxy) -3-methoxy-benzoate from (3R, 3aR, 6R, 6aR) -6- (4- (4- (acryloxy) -3-methoxybenzoyloxy) -3-methoxybenzoyloxy) -hexa -hydrofuro [3,2-b] -furan-3-yl; bis (4- (4 (acryloxy) benzoyloxy) -benzoate) of (3R, 3aR, 6R, 6aR) -hexahydrofuro [3,2-b] furan-3,6-diyl; bis (4- (4- (acryloxy) butoxy) -benzoate) of (3R, 3aR, 6R, 6aR) -hexahydrofuro [3,2-b] furan-3,6-diyl; (3R, 3aR, 6R, 6aR) -hexahydrofuro [3,2-b] furan-3,6-diyl bis (4- (acryloxy) -2-methyl-benzoate); bis (4- (4- (acryloxy) benzoyloxy) -3-methoxybenzoate) from (3R, 3aR, 6S, 6aR) -hexahydrofuro [3,2-b] furan-3,6-diyl; bis (4- (4- (acryloxy) -3-methoxy-benzoyloxy) benzoate) of (3R, 3aR, 6R, 6aR) -hexa-hydrofuro [3,2-b] furan-3,6-diyl; bis (4- (4 (acryloxy) benzoyloxy) -3-methoxybenzoate) from (3R, 3aR, 6R, 6aR) -hexahydrofuro [3,2-b] furan-3,6-diyl; 2-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloxy) - benzoyl] oxy} -3-methoxybenzoyl) -1 , 4: 3,6-dianhydro-D-mannitol; 2,5-bis-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-methoxybenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloxy) -2-methylbenzoyl] oxy} -2-methoxybenzoyl) -1.4: 3,6-dianhydro-D-mannitol; 2-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloyloxy) -3-methylbenzoyl] oxide} -2-methoxybenzoyl) -1.4: 3,6-dianhydro-D-mannitol; 2-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloyloxy) -3-methylbenzoyl] oxide} -2-methoxybenzoyl) -1.4: 3,6-dianhydro-D-mannitol; 2-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloxy) -2,5- dimethylbenzoyl] oxide} -2- methoxybenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2-O- (4 - {[4- (acryloxy) -2,5-dimethylbenzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloxy) -3-methylbenzoyl] oxy} -2-methoxybenzoyl) -1,4: 3,6-dianhydro-D-mannitol 2-O- (4 - {[4- (acrylaloxy) -2-methoxy-5-methylbenzoyl] oxy} -2-methoxybenzoyl ) -5-O- (4 - {[4- (acryloxy)) -3-methylbenzoyl] oxy} -2-methoxybenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2-O- (4 - {[4- (acryloxy) -2-methoxybenzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloyloxy) -3-methylbenzoyl] oxide} -2-methoxybenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2-O- (4 - {[4- (acryloxy) -2-methoxybenzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloxy) -3-methoxybenzoyl] oxide} -2-methoxybenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2-O- (4 - {[4- (acryloxy) -2-methoxybenzoyl] oxy} benzoyl) -5-O- (4 - {[4- (acryloxy)) -3- methoxybenzoyl] oxy} benzoyl) -1, 4: 3,6-dianhydro-D-mannitol; 2,5-bis-O- (4 - {[4- (acryloxy) benzoyl] oxy} -3-methoxybenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2-O- (4 - {[4- (acryloxy) -2-methoxybenzoyl] oxy} -2,5-dimethylbenzoyl) -5-O- (4 - {[4- (acryloyloxy) -3-methoxybenzoyl] oxy} -3-methylbenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2-O- (4 - {[4- (acryloxy) -2-methoxybenzoyl] oxy} -2-methylbenzoyl) -5-O- (4 - {[4- (acryloyloxy) -3-methoxybenzoyl] oxide} -3-methylbenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2-O- (4 - {[4- (acryloxy) -2-methoxy-5-methylbenzoyl] oxy} -2-methylbenzoyl) -5-O- (4 - {[4- (acryloxy) -5-methoxy- 2-methylbenzoyl] oxy} -3-methylbenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-ethoxybenzoyl) -5-O- (4 - {[4- (acryloxy)) -3-ethoxybenzoyl] oxy} benzoyl) - 1,4: 3,6-dianhydro-D-mannitol; 2-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-ethoxy-5-methylbenzoyl) -5-O- (4 - {[4- (acryloyloxy) - 3-ethoxybenzoyl] oxy} benzoyl ) -1,4: 3,6-dianhydro-D-mannitol; 2-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-ethoxy-5-methylbenzoyl) -5-O- (4 - {[4- (acryloxy)) - 5-ethoxy-2-methylbenzoyl ] oxy} benzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2-O- (4 - {[4- (acryloxy)) -3-ethoxybenzoyl] oxy} benzoyl) -5-O- (4 - {[4- (acryloxy) -2-methylbenzoyl] oxy} -2-ethoxybenzoyl) -1.4: 3,6-dianhydro-D-mannitol; 2-O- (4 - {[4- (acryloxy) -2,5-dimethylbenzoyl] oxy} -2-ethoxybenzoyl) -5-O- (4 - {[4- (acryloxy) -2-methylbenzoyl] oxy} -2-ethoxybenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2,5-bis-O- (4 - {[4- (acryloxy) -2,5-dimethylbenzoyl] oxy} -2-ethoxybenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2,5-bis-O- (4 - {[4- (acryloxy) -2-ethoxybenzoyl] oxy} -2-ethoxybenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2,5-bis-O- (4 - {[4- (acryloxy) -2-methoxybenzoyl] oxy} -2-ethoxybenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2,5-bis-O- (4 - {[4- (acryloxy) -2-ethoxybenzoyl] oxy} -2-methoxybenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2,5-bis-O- (4 - {[4- (acryloxy) -2-ethoxybenzoyl] oxy} -3-methylbenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2,5-bis-O- (4 - {[4- (acryloxy) -2-ethoxybenzoyl] oxy} -3-methoxybenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2,5-bis-O- (4 - {[4- (acrylaloxy) -3-methoxybenzoyl] oxy} -3-methoxybenzoyl) -1,4: 3,6-dianhydro-D-mannitol; 2,5-bis-O- (4 - {[4- (acrylaloxy) -3-methoxybenzoyl] oxy} -3-methoxybenzoyl) -1,4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloxy) - benzoyl] oxy} -3-methoxybenzoyl) -1 , 4: 3,6-dianhydro-D-glucitol; 2,5-bis-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-methoxybenzoyl) -1,4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloxy) -2-methylbenzoyl] oxy} -2-methoxybenzoyl) -1.4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloyloxy) -3-methylbenzoyl] oxide} -2-methoxybenzoyl) -1.4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloyloxy) -3-methylbenzoyl] oxide} -2-methoxybenzoyl) -1.4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloxy) -2,5- dimethylbenzoyl] oxide} -2- methoxybenzoyl) -1,4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) -2,5-dimethylbenzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloxy) -3-methylbenzoyl] oxy} -2-methoxybenzoyl) -1,4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) -2-methoxy-5-methylbenzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloxy) -3-methylbenzoyl] oxy} -2-methoxybenzoyl) -1,4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) -2-methoxybenzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloxy) -3-methylbenzoyl] oxy} -2 -methoxybenzoyl) -1,4: 3,6-dianhydro-D-glucitol; 2,5-bis-O- (4 - {[4- (acryloxy) benzoyl] oxy} -3-methoxybenzoyl) -1,4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) -2-methoxybenzoyl] oxy} -2-methoxybenzoyl) -5-O- (4 - {[4- (acryloxy) -3-methoxybenzoyl] oxide} -2 -methoxybenzoyl) -1,4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) -2-methoxybenzoyl] oxy} benzoyl) -5-O- (4 - {[4- (acryloxy)) -3- methoxybenzoyl] oxy} benzoyl) -1, 4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) -2-methoxybenzoyl] oxy} -2,5-dimethylbenzoyl) -5-O- (4 - {[4- (acryloxy) -3-methoxybenzoyl] oxide} -3-methylbenzoyl) -1,4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) -2-methoxybenzoyl] oxy} -2-methylbenzoyl) -5-O- (4 - {[4- (acryloxy) -3-methoxybenzoyl] oxy} -3 -methylbenzoyl) -1,4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) -2-methoxy-5-methylbenzoyl] oxy} -2-methylbenzoyl) -5-O- (4 - {[4- (acryloxy) -5-methoxy- 2-methylbenzoyl] oxy} -3-methylbenzoyl) -1,4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-ethoxybenzoyl) -5-O- (4 - {[4- (acryloyloxy) -3- ethoxybenzoyl] oxy} benzoyl) -1, 4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-ethoxy-5-methylbenzoyl) -5-O- (4 - {[4- (acryloyloxy) - 3-ethoxybenzoyl] oxy} benzoyl ) -1,4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) benzoyl] oxy} -2-ethoxy-5-methylbenzoyl) -5-O- (4 - {[4- (acryloxy)) - 5-ethoxy-2-methylbenzoyl ] oxy} benzoyl) -1,4: 3,6-dianhydro-D-glucitol 2-O- (4 - {[4- (acrylaloxy) -3-ethoxybenzoyl] oxy} benzoyl) -5-O- ( 4 - {[4- (acryloxy) -2-methylbenzoyl] oxy} -2-ethoxybenzoyl) -1,4: 3,6-dianhydro-D-glucitol; 2-O- (4 - {[4- (acryloxy) -2,5-dimethylbenzoyl] oxy} -2-ethoxybenzoyl) -5-O- (4 - {[4- (acryloxy) -2-methylbenzoyl] oxy} -2-ethoxybenzoyl) -1,4: 3,6-dianhydro-D-glucitol 2,5-bis-O- (4 - {[4- (acrylaloxy) -2,5-dimethylbenzoyl] oxide} -2 -ethoxybenzoyl) -1,4: 3,6-dianhydro-D-glucitol; 2,5-bis-O- (4 - {[4- (acryloxy) -2-ethoxybenzoyl] oxy} -2-ethoxybenzoyl) -1,4: 3,6-dianhydro-D-glucitol; 2,5-bis-O- (4 - {[4- (acryloxy) -2-methoxybenzoyl] oxy} -2-ethoxybenzoyl) -1,4: 3,6-dianhydro-D-glucitol; 2,5-bis-O- (4 - {[4- (acryloxy) -2-ethoxybenzoyl] oxy} -2-methoxybenzoyl) -1,4: 3,6-dianhydro-D-glucitol; 2,5-bis-O- (4 - {[4- (acryloxy) -2-ethoxybenzoyl] oxy} -3-methylbenzoyl) -1,4: 3,6-dianhydro-D-glucitol; and 2,5-bis-O- (4 - {[4- (acryloxy) -2-ethoxybenzoyl] oxy} -3-methoxybenzoyl) -1,4: 3,6-dian-hydro-D-glucitol.
[0082] The one or more contaminating chiral compounds B will generally be present in a total concentration comprised between about 0.1% to about 30%, by weight, for example, from about 0.1% to about from 25%, or from about 0.1% to about 20% by weight, based on the total weight of the composition. For example, in the case of jet ink printing, the best results will often be obtained in concentrations of 3% to 10% by weight, for example, between 5% and 8% by weight, based on the total weight of the composition. The one or more nematotic compounds A will often be present in a concentration of about 30% to about 50% by weight, based on the total weight of the composition.
[0083] Especially in cases where the first modification agent is able to change the position of a selective reflection band displayed by means of a precursor composition of a chiral liquid crystal containing salt of an additional component of the precursor composition of chiral liquid crystal for use in the present invention is a salt and, in particular, a salt that is capable of changing the position of the selective reflection band displayed by means of the cured chiral liquid crystal precursor composition (in the liquid crystal state chiral), compared to the position of the selective reflection band displayed through the cured composition without the salt. In this regard, the explanations in US Provisional Patent Applications No. 61/420, 580 and 61/420, 582, both filed December 7, 2010, the full descriptions of which are expressly incorporated into the present invention by reference, may be referred to. With regard to the selective reflection band displayed by means of a chiral liquid crystal polymer composition the explanations in US Patent No. 7,742,136 or US 2010/0025641, the full descriptions of which are expressly incorporated into the present invention by reference, can, for example, be referred to.
[0084] The extent to which the position of the selective reflection band displayed by a given cured chiral liquid crystal precursor composition can be altered by the presence of a salt depends on several factors, such as, inter alia, the salt cation, the anion of salt, and salt concentration, per gram of dry extract. It is generally preferred that a salt be present in a given chiral liquid crystal precursor composition to a concentration that displaces the position of the selective reflection band displayed by means of a cured chiral liquid crystal precursor composition by means of at least about 5 nm, for example, by means of at least about 10 nm, at least about 20 nm, at least about 30 nm, at least about 40 nm, or at least about 50 nm. Suitable (total) salt concentrations are often within the range of about 0.01% to about 10% by weight, for example, from about 0.1% to about 5% by weight, with based on the content of the solid chiral liquid crystal precursor composition. Salt concentrations above the indicated ranges are often difficult to achieve due to the limited solubility of the salt in the precursor chiral liquid crystal composition.
[0085] Non-limiting examples of suitable salts include salts which comprise a metal cation (metals of the main group, transition metals, lanthanides and atinides). For example, the metal can be an alkali or alkaline earth metal, such as, for example, Li, Na. Li salts are particularly preferred. Other non-limiting examples of suitable salts include quaternary ammonium salts such as tetraalkylammonium salts. Examples of suitable anions include "normal" ions such as, for example, halide (eg, fluoride, chloride, bromide, iodide), perchlorate, nitrate, nitrite, sulfate, sulfonate, sodium sulfite, carbonate, bicarbonate nate, cyanide, cyanate and thiocyanate, as well as complex ions, such as, for example, tetrafluorborate. Specific but non-limiting examples of suitable salts include lithium perchlorate, lithium nitrate, tetrafluorborate, lithium bromide, lithium chloride, tetrabutylammonium perchlorate, tetrabutylammonium chloride, tetrabutylammonium tetrafluorohydrate, tetrabutylammonium bromide, carbonate, carbonate sodium and sodium nitrate. Of course, mixtures of two or more salts (for example, two, three, four or more salts) can be used as well. If two or more salts are present, they may or may not comprise the same cation and / or the same anion. In another aspect, at least one salt may comprise lithium perchlorate and / or lithium bromide.
[0086] A non-limiting example of a first modifying agent for use in the present invention includes a substance, and in particular, a resin that is capable of changing the position of the selective reflection band displayed by means of a composition cured chiral liquid crystal precursor that contains a salt that is able to change the position of the selective reflection band displayed by means of the cured chiral liquid crystal precursor composition (in the chiral liquid crystal state), compared to the position of the cured liquid crystal selective reflection displayed through the cured composition without the salt. Such resin will hereinafter be referred to as "modifying resin." In this regard, the detailed explanations in U.S. Provisional Patent Application No. 61/420, 580 and 61/420, 582, may be referred to again.
[0087] The modifying resin for use as a first modifying agent in the present invention will generally be disposed between the substrate and the chiral liquid crystal precursor composition (and in direct contact with the latter). A modifying resin for use in the present invention is not particularly limited as long as it is capable of altering at least one optical property which is exhibited by the precursor composition of cured chiral liquid crystal on the substrate of a remarkable way. In this regard, it is preferred that the modifying resin at least be able to change the position of the selective reflection band as represented by Àmax and, in particular, to be able to displace Àmax by at least about 5 nm, by example, by means of at least about 10 nm, at least about 20 nm, at least about 30 nm, at least about 40 nm, or at least about 50 nm. This ability depends on several factors, such as, inter alia, the components of the chiral liquid crystal precursor composition, for example, the salt (s) and the chiral contaminant (s) formed therein, and the presence (or absence) of functional groups on the modifying resin (and therefore on its surface).
[0088] Examples of modifying resins that are suitable for use as a first modifying agent in the present invention include those made from one or more (e.g., one, two, three or four) polymerizable monomers that include one or more ( for example, one, two or three) heteroatoms selected from, for example, o, N, or S. In this respect, it is to be appreciated that polymerizable monomers are not limited to those that are polymerizable by radical polymerization free. On the contrary, these monomers include, for example, monomers that are polymerizable by means of cationic and / or anionic polymerization and / or by means of polycondensation. Thus, examples of resins that are suitable for the purposes of the present invention include organic resins, such as polyacrylates, polymethacrylates, polyvinylethers, polyvinylesters, polyesters, polyethers, polyamides, polyurethanes, polycarbonates, polysulfones, phenolic resins, epoxy resins non-limiting, and the mixed forms of these resins. Mixed inorganic / organic resins, such as silicones (eg, polyorganosiloxanes) are suitable as well. A specific type of resin that can be used in the present invention are aqueous resins, such as, for example, polyamide resins (for example, CAS 175893-71-7, CAS 303013-12-9, CAS 393802-62-5 , CAS 122380-38-5, CAS 9003-39-8).
[0089] Non-limiting examples of modifying resins for use as the first modifying agent in the present invention further include those which are made from one or more monomers selected from polyether acrylates, modified polyether acrylates (such as, for example) , polyester modified with amine acrylates), polyester acrylates, modified polyester acrylates (such as, for example, amine modified polyester acrylates), tetrafunctional polyester acrylates, hexafunctional polyester acrylates, bifunctional aromatic urethane acrylates , bifunctional aliphatic urethane acrylates, trifunctional aliphatic urethane acrylates, hexafunctional aliphatic urethane acrylates, aliphatic urethane monoacrylates, diacrylates, epoxy Bisphenol A acrylates, epoxy modified acrylates (epoxy modified acrylates, epoxy modified acrylates, epoxy modified acrylates, such as, for example, modified epoxy fatty acid acrylates), acrylic oligomers, hydrocarbon oligomer acrylate, ethoxylated phenol acrylates, polyethylene glycol diacrylates, propoxylated neopentylglycol diacrylates, diacrylated bisphenol A, dipropylene glycol diacrylates derivatives, dipropylene glycol diacrylates, polyethylene diacrylates, polypropylene diacrylates, polypropylene diacrylates, polypropylene diacrylates, polyethylene diacrylates, polypropylene diacrylates, polypropylene diacrylates. - ditrimethylol propane acrylates, dipentaerythritol hexacrylates, mixtures of tripentaerythritol, dipropylene glycol diacrylates and tetra-acrylates, hexanediol diacrylates, ethoxylated trimethylalpropane triacrylates, and a tripropylene dihydrate that is more than one or more dihydroglycyl compounds with a different tripropylene glycol. of the monomers above).
[0090] It is to be appreciated that a modifying resin for use in the present invention does not have to be completely cured (polymerized) or dried before being brought into contact with a chiral liquid crystal precursor composition, as long as it is capable resist components and, in particular, the solvent that may be (and usually will be) present in the precursor chiral liquid crystal (uncured) composition (for example, that the to any significant extent). The curing of a modifying resin only partially cured can be completed, for example, in conjunction with the curing of the precursor chiral liquid crystal (for example, by means of UV radiation).
[0091] One of the advantages of the present invention over the existing prior art (as illustrated in, for example, WO 2001/024106, WO 2008/127950, the complete descriptions of which are incorporated into the present invention by reference) , is the ability to create a perfect record without using masking techniques. By perfect registration means the possibility of having in a very few steps and / or process (s) of steps of a single layer of liquid crystal polymer, in which two or more areas with different simultaneously changing color and / or properties Different positions of the selective reflection band are present, and these areas can be perfectly adjacent without even a gap or an overlap between them. This advantage results from the fact that the chiral liquid crystal precursor composition is applied in a single step, and its properties are modified locally by means of the modifying resin. To achieve a similar result without the instant method, two or more chiral liquid crystal precursor compositions would have to be applied in successive steps with excessively high precision so that they would cover adjacent regions, without gaps or overlaps. The present method allows for the simple creation of a logo, coding marking, barcode, pattern, a data matrix, etc., which contains different information and / or color at the same time. The possibilities offered by the present method include the use of mixtures of modifying resins (for example, mixtures of two, three, four or more, modifying resins), both in the form of cured physical mixtures of two or more modifying resins and in the form of two or more different ones by modifying the resins that are (separately) present at different locations on the substrate surface.
[0092] Alternatively, or in addition, two or more different liquid precursor compositions of chiral crystals that differ, for example, in the concentration of salt (s) contained in them and / or differ in that they contain different salts and from there they can also be used. This in itself gives rise to a large number of possible combinations of chiral liquid crystal precursor compositions and modifying resins that can be present on the surface of a single substrate. This high number of possible combinations allows, among others, the possibility of creating a specific code, and / or the marking, which is difficult to falsify, because whoever wants to reproduce would have to know the exact composition of the precursor compositions of liquid crystals chiral, the type, quantity, and concentration of salt (s) contained therein and the nature of the modifying resin (s). An already large number of possible combinations can be further (and significantly) increased by using more than a second modifying agent in combination with one or more (or each) of the precursor composition (s) combinations chiral liquid crystal (s) and modifying agent (s). The incorporation of additional specific security elements, such as, for example, near-infrared, infrared and / or UV security elements, pigments, magnetic particles, in at least two different ranges of size, such as, for example, "normal" size and nanoscale pigments (known exclusively to the manufacturer of the marking) in the precursor composition of chiral liquid crystal and / or in the modification of resin, makes counterfeiting even more difficult. Accordingly, the present invention also contemplates and encompasses the use of chiral liquid crystal precursor compositions and modifying resins that include such specific additional security elements.
[0093] It is also to be appreciated that the present invention is not limited to the visible range of the electromagnetic spectrum. For example, a modifying resin for use in the present invention can support all or part of the selective reflection band displayed by means of a chiral liquid crystal precursor composition cured from the IR range to the visible range, or from the visible range to the UV range, or from the IV range to the UV range, and vice versa, for example, from visible UV.
The chiral liquid crystal precursor composition and the composition for making the modifying resin or other modifying agent can first be applied to the surface of the substrate or product by any suitable method such as, for example, spray coating , blade coating, coating roll, screen coating, curtain coating, gravure printing, flexography, printing, dry offset printing, typography, screen printing, pad printing and inkjet offset printing (for example, jet ink printing, printing of drop-on demand jet ink, valve jet printing). In one of the embodiments of the present invention, the application (for example, deposition) of a composition to make the layer or pattern and / or a composition to cause the modifying resin to be carried out with a printing technique, such as, for example, example, jet ink printing (continuous, demand drop-on, etc.), flexography, pad printing, rotogravure, screen printing, etc. Of course, other printing techniques known to those skilled in the printing technique can also be used. In one of the preferred embodiments of the present invention, flexographic printing is used both for the application of the modifying resin and for the application of the chiral liquid crystal precursor composition. In another preferred embodiment of the present invention, jet ink printing techniques are used both for the application of the modifying resin and for the application of the chiral liquid crystal precursor composition. It is also contemplated that two different techniques can be used, respectively, to apply the modifying resin and the chiral liquid crystal precursor composition. Industrial jet ink printers, commonly used for numbering, coding and marking conditioned and printed lines, are particularly suitable. Preferred jet ink printers include single nozzle continuous jet ink printers (also called raster or multi-level printers) and drop-on demand jet ink printers, especially valve jet printers. The thickness of the liquid crystal polymer composition applied, after curing, according to the application techniques described above, will generally be at least about 1 µm, for example, at least about 2 mM, or at least about 3 µm or at least about 4 mm, and will generally be no more than about 20 µm, for example, no more than about 15 µm, and no more than about 10 µm, or not more than about 6 mM. The thickness of the modification resin applied, after curing, according to the application techniques described above will generally be at least about 1 µm, for example, at least about 2 mM or at least about 3 mM, or at least about 5 æm, but it will generally be no more than about 10 æm.
[0095] In particular, if a composition for use in the present invention (i.e., a composition for making a chiral liquid crystal precursor or a composition for making a modifying resin), it should be applied by means of printing techniques , set forth above, the composition will generally be comprised of a solvent to adjust its viscosity to a value that is suitable for the application of the technique employed (printing). Typical values for the flexographic printing viscosity of the composition used in the present invention are in the range of about 10 seconds to about 120 seconds, preferably 10 to 100 seconds, more preferably 10 to 60 seconds, even more preferably 10 40 seconds, using, for example, a DIN Number 4 cup, at 25 ° C. Suitable solvents are known to those skilled in the art. Non-limiting examples of these include low polar and aprotic low viscosity organic solvents, such as, for example, methyl ethyl ketone (MEK), acetone, cyclohexanone, ethyl acetate, ethyl 3-ethoxypropionate and the mixtures of two or more of the same.
[0096] Furthermore, in particular if a composition for use in the present invention (i.e., a composition for making a chiral liquid crystal precursor or a composition for making a modifying resin) is to be applied by means of jet ink printing (continuous), the composition will generally also be understood by means of at least one conductivity agent known to those skilled in the art.
[0097] If a chiral liquid crystal precursor composition and / or a composition for making a modifying resin for use in the present invention is to be cured / polymerized by means of UV radiation, the composition will also comprise at least one photoinitiator. Non-limiting examples of the various suitable photoinitiators include α-hydroxy ketones, such as 1-hydroxy-cyclohexyl-phenyl-ketone and a mixture (for example, about 1: 1) of 1-hydroxy-cyclohexyl-phenyl- ketone and one or more of the benzophenones, 2-hydroxy-2-methyl-1-phenyl-1-propanone, and 2-hydroxy-1- [4- (2-hydroxyethoxy) phenyl] -2-methyl-1-propanone; phenylglyoxylates such as methylbenzoylformate and the mixture of 2- [2-oxo-phenyl-acetoxy-2-ethoxy] -ethyl ester of oxy-phenyl-acetic acid and 2- [2-hydroxy-ethoxy] -ethyl ester of oxy-phenyl acid - acetic; benzildimethyl ketals, such as alpha, alpha-dimethoxy-alpha-phenylacetophenone; α-aminoketones, such as 2-benzyl-2- (dimethylamino) -1- [4- (4-morpholinyl) phenyl] -1-butanone and 2-methyl-1- [4- (methylthio) phenyl] -2- (4-morpholinyl) - 1-propanone, with the aforementioned photoinitiators, the composition may also include coinitiators such as phosphine and phosphine oxide derivatives, such as diphenyl (2,4,6-trimethylbenzoyl oxide) - phosphine, phenyl-bis (2,4,6-trimethylbenzoyl) supplied by Ciba, and also thioxanthone derivatives such as Speedcure ITX (CAS 142770-42-1), Speedcure DETX (CAS 82799-448), Speedcure CPTX (CAS 5495- 84-1-2 or CAS 83846-86-0) provided by Lambson.
[0098] If a composition for use in the present invention (i.e., a composition for making a chiral liquid crystal precursor or a composition for making a modifying resin), it must be cured by means of a method that is different from irradiation with UV light, such as, for example, by means of high energy particles, X-rays, gamma rays (for example, electron beams), etc., the use of a photoinitiator can, of course, be waived.
[0099] It may also be possible or desirable to cure, in a particular way, the composition to make a thermally modifying resin. In this case, the composition will normally contain at least one thermal polymerization initiator, such as, for example, a peroxide or an azo compound. Other examples of thermal polymerization initiators are well known to those skilled in the art.
A chiral liquid crystal precursor composition and a composition for providing a modifying resin for use in the present invention can also comprise a variety of other optional components that are suitable and / or desirable to achieve a certain desired property of the composition and in In general, it can comprise all components / substances that do not adversely affect a necessary property of the composition in a significant way. Non-limiting examples of such optional components are resins, silane compounds, adhesion promoters, sensitizers for photoinitators (if present), etc. For example, especially a chiral liquid crystal pre-cursor composition for use in the present invention can comprise one or more silane compounds. Non-limiting examples of suitable silane compounds include optionally polymerizable silanes, such as those of the formula R1R2R3-Si-R4 wherein R1, R2 and R3 independently represent alkoxy and alkoxyalkoxy having a total of from 1 to about 6 atoms carbon and R4 represents vinyl, allyl, (C1-10) alkyl, (meth) acryloxy-alkyl (C1-6) alkyl, and glycidyloxy (C1-6) alkyl, such as, for example, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris ( 2-methoxyethoxy) silane, 3-methacryloxypropyl-trimethoxysilane, Octiltriethoxysilane, and 3- glycidyloxypropyl triethoxysilane from the Dynasilan ® family provided by Evonik.
[00101] The concentration of one or more silane compounds, if present, in the chiral liquid crystal precursor composition will generally be from about 0.5% to about 5% by weight, based on the total weight of the composition.
[00102] In order to enhance the security of the marking according to the present invention, a composition for making a modifying resin and / or a composition for making a chiral liquid crystal precursor for use in the present invention it can also comprise one or more pigments and / or dyes that absorb in the visible or invisible region of the electromagnetic spectrum and / or one or more pigments and / or dyes, which are luminescent and / or one or more magnetic particles and / or one or more pigments, in different size ranges (for example, "normal" size and nanoscale pigments). Non-limiting examples of suitable pigments and / or dyes that absorb in the visible or invisible region of the electromagnetic spectrum include phthalocyanine derivatives. Non-limiting examples of suitable luminescent pigments and / or dyes include lanthanide derivatives. Non-limiting examples of suitable magnetic pigments include transition metal oxide particles, such as iron and chromium oxides. The presence of pigment (s) and / or dye (s) will promote and reinforce the security of marking against counterfeiting.
[00103] After the application of the precursor chiral liquid crystal composition in the form of a layer or pattern on the surface of the substrate or product carrying the one or more first modifying agents in one or more first areas, the composition can be brought to a chiral liquid crystal state displaying the initial configuration of optical properties (and the first modified set of optical properties in one or more first areas). For this purpose, the chiral liquid crystal pre-cursor composition is heated, in which the solvent contained in the composition, if present, is evaporated and the promotion of the desired chiral liquid crystal state occurs. The temperature used to evaporate the solvent and to promote the formation of the liquid crystal state depends on the components of the chiral liquid crystal precursor composition and will, in many cases, vary from about 55 ° C to about 150 ° C, for example , between about 55 ° C to about 100 ° C, preferably between about 60 ° C to about 100 ° C. Examples of suitable heating sources include conventional heating means, such as a hot plate, an oven, a flow of hot air and, in particular, radiation sources, such as, for example, an IR lamp. The required heating time depends on several factors, such as, for example, the components of the chiral liquid crystal precursor composition, the type of heating device and the intensity of the heating (output energy of the heating device). In many cases, a warm-up time of about 0.1 s, about 0.5 s, or about 1 second to about 30 seconds, such as, for example, no more than about 20 seconds , no more than about 10 seconds, or no more than about 5 seconds will be sufficient.
[00104] After the formation of the chiral liquid crystal state, the second modifying agent (s) can be applied on one or more of the second areas of the composition in the initial state chiral liquid crystal (and, optionally, also in one or more of the first areas or parts of it). The second modifying agent is able to change the initial chiral liquid crystal state (optionally after heating, depending on the type of the second modifying agent) and the first modified chiral liquid crystal state (if applied to a first area or part of the same). The second modifying agent can be applied to the step where the chiral liquid crystal precursor composition is still in a heated state (for example, immediately after the heating operation is completed) or can be applied after the chiral liquid crystal precursor composition has cooled to at least some extent (for example, it is substantially at room temperature). If desired, the cooling of the chiral liquid crystal precursor composition can be accelerated by means known to those skilled in the art, such as, for example, by blowing ambient air over the previously heated composition. Applying the second modifying agent to the chiral liquid crystal precursor composition in a chilled state can improve the resolution of the label. On the other hand, the application of the second modifying agent immediately after the completion of the heating operation may be desirable, if the whole process of making the marking is being carried out in the simplest and fastest way possible.
[00105] The second modifying agent for use in the present invention will not extract any of the compounds that form the initial or first modified chiral liquid crystal state, nor will it modify the chemical structure of these compounds to any significant degree (and, preferably not at all). Without wishing to be linked to any theory, it is speculated that at least some of the second modifying agents that can be employed will initiate a very localized and controlled chiral reorganization of the liquid crystal state.
[00106] In the marking according to the present invention, the second modifying agent normally, depending on its nature, modifies the initial (unmodified) chiral liquid crystal state (and, if applied in one of the first or more domains) or parts, also the first modified chiral liquid crystal state) from an anisotropic (or predominantly substantially) state that is characterized by specific optical properties for: (i) the isotropic liquid crystal state (predominantly or substantially) where the colors of the displacement properties of the chiral liquid crystal state are substantially absent and / or are not detectable to the naked eye (as predicted by, for example, a kind of modifying agent I set out below), or ( ii) a modified (second) chiral liquid crystal state that exhibits a second set of modified optical properties with at least one optical property, which is different from one corresponding optical property of the initial chiral liquid crystal state (as predicted, for example, in the modifying agents of species II or III set out below).
[00107] The second modifying agent may, for example, be a "species I" modifying agent. A modifying agent of species I will normally be constituted by one or more aprotic organic compounds which are liquid at room temperature and, preferably, have a relatively high dipole moment and a relatively high dielectric constant. Non-limiting examples of these include ketones having from 3 to about 6 carbon atoms, alkyl esters and dialkylamides of carboxylic acids comprising a total of 2 to about 6 carbon atoms, dialkyl sulfoxides containing a total of from 2 to about 4 carbon atoms, and, optionally substituted nitrobenzene (for example, substituted with alkyl), such as, for example, dimethyl ketone, methyl ethyl ketone, ethyl acetate, dimethylformamide, dimethyl sulfoxide, nitrobenzene, nitrotoluene, and mixtures of two or more of them. Preferred compounds for use in or as a species I modifying agent include acetone, methyl ethyl ketone and ethyl acetate.
A species modifying agent I for use in the present invention may further comprise one or more viscosity-adjusting resins. Of course, the resin (s) must be compatible with the technical application (for example, printing) that is to be used. Non-limiting examples of resins that may be suitable, depending on the particular circumstances, include polyester resins, such as, for example, DYNAPOL ® L 1203, L 205, L 206, L 208, L 210, L 411, L 651, L658 , L 850, L 912, L 952, LH 530, LH 538, LH 727, LH 744, LH 773, LH 775, LH 818, LH 820, LH 822, LH 912, LH 952, LH 530, LH 538, LH 727, LH 744, LH 773, LH 775, LH 818, LH 820, LH 822, LH 823, LH 826, LH 828, LH 830, LH 831, LH 832, LH 833, LH 838, LH898, LH 908, LS436 , LS615, P1500, S1218, S1227, S1247, S1249, S1252, S1272, S1401, S1402, S1426, S1450, S1510, S1606, S1611, S243, S320, S341, S361, S394 and S EP1408 from Evonik. Other suitable resins known to those skilled in the art can also be used. In a preferred embodiment, one or more are selected from DYNAPOL ® resins L 1203, L 205, L 206, L 208, L 210, L 411, L 651, L658, L 850, L 912, L 952, 530 LH , LH 538, LH 727, LH 744 from Evonik. A typical range for the concentration of one or more resins is from about 3% to about 15% by weight, based on the total weight of type I modifying agent.
[00109] Type I modifying agents may further comprise one or more conductivity agents, such as, for example, salts that are sufficient to impart conductivity to the species of modifying agent I in order to allow its use in combination with a printer, such as, for example, a continuous inkjet printer. Examples of suitable conductivity agents include those described above, as examples of conductivity agents for use in the chiral liquid crystal precursor composition of the present invention, such as, for example, tetrabutyl ammonium nitrate, ammonium perchlorate of tetrabutyl, tetrabutylammonium hexafluorphosphate, potassium hexafluorphosphate, potassium thiocyanate, lithium perchlorate and other conductivity agents known in the art.
[00110] When modifying agents of species I comprise a solvent or a mixture of solvent, after evaporation of the solvent, the initial chiral liquid crystal state (and also the first modified chiral liquid crystal state, if applicable) will go locally (in one or more second areas) to change from a state (predominantly or substantially) optically anisotropic to a state (predominantly or almost) optically isotropic.
[00111] The second modifying agent can also be a "species II" modifying agent, that is, a (second) precursor chiral liquid crystal composition. The chiral liquid precursor composition for the application of one or more of the second areas of the chiral liquid precursor composition may be the same as or different from the base of the chiral liquid precursor composition to be modified. In addition, everything defined above in relation to the base of the chiral liquid crystal precursor composition (eg components, application methods, etc.) applies equally, without exception, and also to the precursor liquid crystal composition chiral, in the present invention, as a second modifying agent (type II modifying agent). For example, as in the case of the chiral liquid crystal precursor composition of one or more chiral contaminating compounds B will generally be present in the modifying agent of species II, in a total concentration comprised between about 0.1% to about 30% by weight, for example, from about 0.1% to about 25%, or from about 0.1% to about 20% by weight, based on the total weight of the species modifying agent II . In addition, one or more nematic compounds A will often be present in the species modifying agent II in a concentration of about 30% to about 50% by weight, based on the total weight of the species modifying agent II.
[00112] If the species modifying agent II is different from the base of the chiral liquid crystal precursor composition to be modified one or more differences may be related, for example, one or more of compounds A and B and / or one its salt, as described in paragraph [0109] that are present in these compositions and / or for the concentrations of one or more of the same compounds. For example, one or the only difference between these compositions may be that one or more (or all) of the contaminating chiral compounds B are present in the species modifying agent II at a concentration / concentrations that are / are different from those of the corresponding concentration / concentrations in the base composition. In addition, one or the only difference between these compositions, which may be one or more contaminating chiral compounds B in the basic composition are of formula (I) above and / or related to formulas and at least one of the one or more compounds Chiral contaminants B in the species modifying agent II is different from formula (I) and / or related formulas. For example, at least one of the one or more chiral contaminating compounds B in the species II modifying agent can be an isosorbide or isomanide derivative as described in, for example, EP-B-0 847 432, GB- A-2 330 139, and US Patent No. 6,589,445, the complete descriptions of which are incorporated into the present invention by reference.
[00113] It is to be appreciated in the present invention that if the modifying agent of species II is different from the composition of the chiral-based liquid crystal precursor, it can also be applied to one or more surface areas of the substrate or product that do not have the base composition (but can optionally carry a first modifying agent). In this way, a greater variability in the marking of the present invention can be created, that is, one or more areas with a species modifying agent II in a chiral liquid crystal state (obtained after renewed heating) and / or one or more areas with a species II modifying agent, whose chiral liquid crystal state (formed after heating) is modified by the first modifying agent.
[00114] After the application (for example, deposition) of the species modifying agent II to one or more of the second areas of the composition of the chiral precursor liquid crystal base in the liquid crystal state, the system is brought to a second state of chiral liquid crystal modified in order to obtain the second modified set of optical properties in one or more second areas. For this purpose, at least one or more of the second areas is heated, in which the solvent contained in the species II modifying agent, if present, is evaporated and the promotion of the desired second modified chiral liquid crystal state in one or more second areas are slow to happen. The temperature used to evaporate the solvent and to promote the formation of the second modified liquid crystal chiral state depends on the components of the species modifying agent II and will appear, in many cases, ranging from about 55 ° C to about 150 ° C , for example, from about 55 ° C to about 100 ° C, preferably between about 60 ° C to about 100 ° C. Examples of suitable heating sources include conventional heating means and, in particular, radiation sources, such as, for example, an IR lamp.
[00115] It is to be understood here that, in the case of the use of a species II, that is, modifying agent, a (second) pre-cursory composition of chiral liquid crystal, such as a second modifying agent of the marking according with the present invention is not identical or similar to a simple overlap of two layers of liquid chiral nematic. This is a significant difference from the prior art. In particular, when the base chiral liquid crystal precursor composition is deposited on a substrate and brought to the initial chiral liquid crystal state, this state is characterized by means of step p1. Likewise, when the second chiral liquid crystal precursor composition (species modifying agent II) is deposited on one or more of the second areas of the base composition and brought to the second modified chiral liquid crystal state in the second modified state is characterized by a step p2 (which can be the same or different from p1). In this regard, it is noted that the product obtained after cure / polymerization in the process of the present invention is not a superposition of a first chiral liquid crystal state that has a p1 step and a second chiral liquid crystal state that has a p2 field. On the contrary, the loading area of a second chiral liquid crystal precursor composition, once brought into the second modified chiral liquid crystal state, has a step p2 ', which is different from p1 and p2, but is somewhat dependent on the nature of p1.
[00116] In yet another embodiment of the present invention, the second modifying agent can be a "species III" modifying agent, i.e., a contaminating chiral composition. The contaminating chiral composition preferably comprises one or more (e.g., one, two, three or four) chiral contaminating compounds C of formula (I) defined above and / or related to the formulas. In a more preferred embodiment, the contaminating chiral composition comprises at least one contaminating chiral C compound and at least one other contaminating chiral compound that is different from a compound of formula (I) and the related formulas. The at least one contaminating chiral compound D can be selected, for example, from the derivatives of isosorbides and isomanides which are described in, for example, EP-B-0 847 432, GB-A-2 330 139 , and US Patent No. 6,589,445, the complete descriptions of which are incorporated into the present invention by reference.
[00117] As chiral contaminating C compounds, which are, preferably, present in the contaminating chiral composition (species modifying agent III) the chiral B contaminating compounds defined above can, for example, be used. In this way, everything that is defined above with respect to compounds B and applies equally, without exception, also to compounds of C. Furthermore, it is to be appreciated that the contaminating chiral compound (or the only one) that is present in the contaminating chiral composition it can be identical to one (or the only) contaminating chiral B compound that is present in the chiral liquid crystal precursor composition.
[00118] The contaminating chiral composition will normally consist of one or more chiral contaminating compounds in a total concentration ranging from about 0.1% to about 30% by weight, for example, from about 0.1 % to about 25%, or from about 0.1% to about 20%, by weight, based on the total weight of the composition. Often, the total concentration will be 3% to 10% by weight, for example, between 5% and 8% by weight, based on the total weight of the chiral liquid crystal precursor composition.
[00119] Additional information regarding species modifying agents I, II III can be found in U.S. patent application Nos. 12/783, 068, 12/783, 078, 12/783, 081 and 12/783, 088, all filed on May 19, 2010, all descriptions of which are expressly incorporated into the present invention by reference.
[00120] In particular, if the contaminating chiral composition is to be applied using the printing techniques defined above, for example, through inkjet printing, the composition will usually comprise a solvent to adjust its viscosity to a value that is suitable for the application (printing) technique employed. Typical viscosity values for inkjet printing inks are in the range of about 4 to about 30 mPa.s at 25 ° C. Suitable solvents are known to those skilled in the art. Non-limiting examples of these include low-viscosity, low-polar and aprotic organic solvents, such as, for example, methyl ethyl ketone (MEK), acetone, ethyl acetate, 3-ethoxypropionate acetate, toluene and mixtures two or more of them. Other suitable components necessary for the printing techniques used in the context of the present invention may also be present (resins, salts, etc.), and are known to those skilled in the art. For example, the contaminating chiral composition may comprise one or more conductivity agents, such as, for example, salts that are sufficient to impart conductivity to the contaminating chiral composition to allow its use in combination with a printer , such as, for example, a continuous ink jet printer. Examples of suitable conductivity agents include those that are described above, as examples of conductivity agents for use in the chiral liquid crystal precursor composition of the present invention, such as, for example, tetrabutyl ammonium nitrate, tetrabutyl ammonium perchlorate, tetrabutylammonium hexafluorphosphate, potassium hexafluorphosphate, potassium thiocyanate, lithium perchlorate and other conductivity agents known in the art.
[00121] After applying the contaminating chiral composition to one or more of the second areas of the chiral liquid crystal precursor composition in the initial state of chiral liquid crystals that exhibit the initial set of optical properties (and, optionally, also with one or more first domains or parts thereof), one or more of the second areas are brought into the second modified chiral liquid crystal state with the second modified set of optical properties. For that purpose, at least one or more of the second areas over which the contaminating chiral composition that has been applied is heated, in which the solvent contained in the composition, if present, is evaporated and the promotion of the second modified liquid crystal state desired chiral occurs. The temperature used to evaporate the solvent and to promote the formation of the second chiral modified liquid crystal state depends, for example, on the components of the contaminating chiral composition and will appear, in many cases, ranging from about 55 ° C to about 150 ° C, for example, between about 55 ° C to about 100 ° C, preferably between about 60 ° C to about 100 ° C. Examples of suitable heating sources include conventional heating means and, in particular, radiation sources, such as, for example, an IR lamp.
[00122] In the marking according to the present invention, the deposition of one or more of the second modifying agents (species modifying agent I and / or II, species modifying agent and / or species modifying agent III) it can be carried out in one or more of the second areas of the chiral liquid crystal precursor composition in the initial chiral liquid crystal state (in which the second areas can include or be one or more of the first domains or parts thereof, in which the composition is the first exclusively modified chiral liquid crystal state), preferably with a printing technique and, in particular, a selected printing technique, printing inkjet, continuous drop jet on-demand inkjet printing and coating by spraying. The advantage, in particular, in comparison with the prior art using laser or partially polymerized or polymerized liquid crystal extraction agents is the speed and ease of forming the marking, which is generated in almost real time. Another advantage of using the printing techniques above is the precision and stability of the marking created within the chiral liquid crystal state. Another advantage of using this printing technique is the almost limitless marking possibilities that can be created, varying in almost real time. In a preferred embodiment, inkjet techniques are used to modify the application of the composition. Industrial jet ink printers, commonly used for numbering and coding and marking conditioned lines and printers, are particularly suitable. Preferred jet inkjet printers are single continuous nozzle inkjet printers (also called raster or multi-level printers) and drop-on demand inkjet printers, especially valve jet printers.
[00123] In order to improve the resolution of the applied marking it will often be advantageous if immediately after the application of a second modifying agent in one or more of the second areas of the precursor composition of chiral liquid crystal a current of air is applied that passes over the surface of the chiral liquid crystal precursor composition, preferably (substantially) parallel thereto. The air flow can be generated by any means, for example, with an industrial air dryer. The air flow will preferably not be intense and / or high speed. The air temperature will generally be ambient (for example, around 20 ° C), but it can also be slightly higher or lower, for example, up to about 60 ° C, up to about 40 ° C, or up to about 30 ° C . The phrase "immediately after the application of a second modifying agent" is understood to mean, without delay, for example, within a period of no more than about 10 seconds, for example, no more than about 5 seconds, no more than about 3 seconds, no more than about 2 seconds, or no more than about 1 second after the completion of the application of the second modifying agent.
[00124] The area of the chiral liquid crystal precursor composition applied to which each of the first and second (additional) and any modifying agents is generally applied will be about 0.1% to about 99.9% of the total area of the chiral liquid applied to the precursor crystal composition. The area will often be at least about 1%, for example, at least about 5% or at least about 10% and not more than about 99%, for example, not more than about 95% or no higher than about 90% of the total area of the applied chiral liquid crystal precursor composition.
[00125] As in the case of the first modifying agent, it is evidently possible to use more than one second modifying agent (for example, two, three or more of the second different modifying agents), and to apply them. them simultaneously and / or successively in the applied chiral liquid crystal precursor composition (for example, in areas other than the applied chiral liquid crystal precursor composition). Merely by way of example, the different second modifying agents may comprise modifying agents of two different species III, or may be constituted by means of a species modifying agent I, a species modifying agent II and a modifying agent of species III, or can comprise two different agents of modification of species II and modifiers of species I, etc. It is also possible, for example, to apply a first and second modifying agent to later apply a second different modifying agent in at least part of the area where the initially first modifying agent was applied (and, optionally, also in one or more regions where the first second modifying agent was not applied). In this regard, it is to be appreciated though that, especially in cases where both species I modifying agents are used, a species modifying agent II and / or a species modifying agent III are employed, it may be desirable , for reasons of convenience, carry out the heating that is necessary for a species II or species III modifying agent also in the case of species I modifying agent. In other words, although it is not necessary, heat is (again) possible of the chiral liquid crystal precursor composition, after application of the modifying agent I species (and, optionally, the passage of air over the surface of the chiral liquid crystal precursor composition) to further modify the chiral liquid crystal state and / or removal of any residual solvent that was present in the modifying agents of species I. However, in most cases, a heating operation (additional), after the application of the species of a Modification people I will not be necessary. If used, the temperature used for this heating operation (optional) will, in many cases, be from about 55 ° C to about 150 ° C, for example, between about 55 ° C to about 100 ° C, or between about 60 ° C to about 100 ° C. Examples of suitable heating sources include conventional heating means and, in particular, radiation sources, such as, for example, an IR lamp.
[00126] In particular, when two or more different second modifying agents are being employed the printing process can be carried out with a multi-head system (with, for example, two, three, four, five or more heads) in which each one contains a different modifying agent head. An advantage of such a configuration is that, during the printing process, it is possible to obtain a sequential modification different from the initial chiral liquid crystal state and, therefore, a large number of unique markings. With the multi-head system, areas with different optical properties can also be obtained in the same marking, which constitute a single marking in itself (especially when it is in the form of a data matrix). Examples of such data arrays with several multicolor data arrays are described in, for example, WO 2008/127950 and WO 01/24106, the entire descriptions of which are incorporated herein by reference.
[00127] In order to enhance the security of the marking according to the present invention, the second modifying agent may further comprise one or more pigments and / or dyes which absorb in the visible or invisible region of the electromagnetic spectrum and / or may comprise additionally one or more pigments and / or dyes, which are luminescent. Non-limiting examples of suitable pigments and / or dyes that absorb in the visible or invisible region of the electromagnetic spectrum include phthalocyanine derivatives. Non-limiting examples of suitable luminescent pigments and / or dyes include lanthanide derivatives. The presence of pigment (s) and / or dye (s) will promote and reinforce the security of marking against counterfeiting. Of course, in addition to the components discussed above modifying the composition for use in the present invention can comprise any other component / substances that do not adversely affect the desired properties of the composition to significantly modify.
[00128] The marking according to the present invention is eventually obtained by curing and / or polymerizing the composition that has been modified locally (in one or more areas) through the action of the first and second agent of modification (and any additional modification agents, if employed). The fixation or hardening is preferably carried out by irradiation with UV light, which induces the polymerization of the polymerizable groups present in the precursor chiral liquid crystal composition (and, optionally, in the modifying agent (s) ).
[00129] Therefore, a whole process of placing a marking of the present invention can comprise the following steps (using a modifying agent of a first and a second modifying agent): - providing a functionalized substrate, which comprises a first agent modifying the surface of a substrate or an item; - curing and / or drying of the modifying resin applied at least partially, for example totally; - the application of a chiral liquid crystal precursor composition (containing the salt) over a portion of the substrate that has the modifying resin in it so that the chiral liquid precursor composition covers the modifying resin in the first one or more areas of the applied composition; - heating the precursor chiral liquid crystal composition applied to bring it to the chiral liquid crystal state; - applying a second modifying agent to one or more of the second areas of the chiral liquid crystal precursor composition in the chiral liquid crystal state; - heating the precursor chiral liquid crystal composition to which the second modifying agent was applied (by means of modifying agents of species II and species III); - curing / polymerizing the liquid crystal precursor composition in a chiral liquid crystal polymer state (and, optionally, completing the curing and / or drying of the modifying resin) to obtain the marking according to the present invention .
[00130] It should be noted in the present invention that no substantial cure / polymerization of the precursor chiral liquid crystal composition takes place until the end of the described production process.
[00131] By functionalized substrate is meant a substrate as described above, which comprises the first modifying agent according to the present invention (for example, at least one resin as described above cured and / or dry, see Fig. 1).
[00132] The following examples are intended to illustrate the present invention without restricting it. Example 1
[00133] A PET substrate (50 μm thickness) is functionalized with a UV-curable resin used as a first modifying agent. This first modifying agent is deposited on the substrate using a flexographic printing process, in one or more first areas and is cured with a UV dryer. The functionalized substrate is placed on a conveyor belt and passed under a first continuous inkjet nozzle (head 1; CIJ printer from Domino, UK; pressure jet 2500-3000 mbar; nozzle width 75 um), which contains a chiral liquid crystal precursor composition (see Composition 1 below). Head 1 applies a layer of composition 1 (thickness 5 μm) on the functionalized substrate. Subsequently, the substrate thus coated is heated with an IR lamp (IR strip, PCS Inc. & Research Inc., US; 15 cm long lamp; max 500 W) for about 1 second, in order to promote the state chiral liquid crystal composition 1. In this phase, the liquid crystal layer that is chiral, in the upper part of the functionalized substrate comprises one or more first areas that require a first defined modification of optical properties (located in the areas where the resin has been deposited) which is different from the initial set of optical properties obtained in the areas where Composition 1 is applied directly to the substrate, that is, in the absence of the first modifying agent. In a subsequent step, the substrate having the chiral liquid crystal layer on it is passed under a second continuous inkjet nozzle (Head 2), which is applied a second modifying agent (see Composition 2 below) at the top of the substrate in one or more regions where the first modifying agent was not applied. The resulting product is subjected to a current of ambient air. It is observed that in the area (s) where the second modifying agent was deposited a second set of modified optical properties appears. This second set is different from the first set of optical properties and from the first set of optical properties. The substrate with the three distinct areas (first and second initial areas,) is then cured, with a UV dryer (see above) to fix the liquid crystal and polymer state to obtain a marking according to the present invention. , which has at least three different sets of optical properties.
Example 2
[00134] Example 1 is repeated, but replacing Composition 2 with Composition 3 described below. In contrast to Example 1 after the application of composition 3, the resulting product is not only subjected to a flow of ambient air, but is also heated with an IR lamp for about 1 second in order to promote the crystal state chiral liquid of Composition 3.
[00135] The procedures set out in Examples 1 and 2 are illustrated in Fig. 1.
Examples 3 and 4
[00136] Examples 1 and 2 are repeated with the exception that Head 2 Composition 2 (Example 1) or Composition 3 (Example 2) is applied in one or more of the second areas, which overlap partially or totally, or are located within one or more first areas, to thereby create one or more areas that have a modified (third) set of optical properties that is different from that of the first and second initial sets of modified properties. The corresponding patterns (including those obtained according to Examples 1 and 2) are illustrated in Fig. 2. This allows, for example, to create a data matrix, which is the sum of points of different optical properties (for example , different colors) within a limited area, thereby increasing the level of safety (if, for example, the second modifying agent comprises a fluorescent dye.). In Fig. 3, a mark is shown in the form of a code generated from a data matrix as in the following example: the first modifying agent is in the form of a rectangle, in which it overlaps the crystal polymer layer liquid, which was further modified by means of the second modifying agent in the form of a data matrix.
[00137] It should be noted that the previous examples were presented for the purpose of explanation only and are in no way to be interpreted as limiting the present invention. Although the present invention has been described with reference to an exemplary embodiment, it is understood that the words that have been used in the present invention are words of description and illustration, rather than words of limitation. Changes may be made, within the scope of the appended claims, as presently indicated, with the changes, without departing from the scope and spirit of the present invention in its aspects. Although the present invention has been described with reference to particular means, materials and modalities, the present invention is not intended to be limited to the details described therein, instead the present invention extends to all functionally equivalent structures, methods and uses, such as are within the scope of the appended claims.

权利要求:
Claims (16)
[0001]
1. Marking of an item or substrate, where the marking comprises a layer or pattern of a chiral liquid crystal polymer composition that exhibits an initial set of optical properties and is made by curing a precursor liquid crystal composition chiral in a chiral liquid crystal state, and in which the layer or pattern comprises (1) one or more, first areas presenting a first modified set of optical properties, which is different from the first set of optical properties and can be obtained by contacting the chiral liquid crystal precursor composition in one or more first areas with a first modifying agent; (2) one or more, second areas showing a second modified set of optical properties that is different from the first set of optical properties and different from the first modified set of optical properties and can be obtained by contacting the precursor chiral liquid crystal composition in one or more of the second areas with a second modifying agent that is of a different type than the first modifying agent, characterized by the fact that the first modifying agent is disposed between the substrate and the layer or pattern in one or more areas, the second modifying agent acts from the side opposite the substrate in one or more areas, and in which at least one of the first or more areas is not overlapped by any second area and / or at least one of the one or more second areas is not overlapped by any first area.
[0002]
2. Marking according to claim 1, characterized by the fact that the first and second modified initial sets of optical properties differ in relation to at least one light property that is reflected by means of the chemical liquid crystal polymer composition ral.
[0003]
3. Marking according to claim 1 or 2, characterized by the fact that the chiral liquid crystal precursor composition comprises (i) one or more nematic compounds A, (ii) one or more contaminating chiral compounds B, which are capable of giving rise to a cholesteric state of the precursor chiral liquid crystal composition, and (iii) at least one salt that changes from a maximum wavelength of a selective reflection band (Àmax) displayed through the composition of the polymer compared to a maximum wavelength of a selective reflection band (Àmax) displayed by means of a polymer composition that does not contain at least one salt.
[0004]
4. Marking according to claim 3, characterized by the fact that the chiral liquid crystal precursor composition comprises at least one chiral contaminating compound B of formula (I):
[0005]
5. Marking according to claim 3 or 4, characterized by the fact that at least one salt is selected from metal salts and ammonium salts.
[0006]
6. Marking according to any one of claims 1 to 5, characterized by the fact that the chiral liquid crystal precursor composition is in an optically anisotropic state and in which one or more of the first regions of the optically anisotropic state is changed to a first optically modified anisotropic state, and / or one or more of the second areas of the optically anisotropic state is changed to a second optically modified anisotropic state or converted to an optically isotropic state.
[0007]
7. Marking according to any one of claims 1 to 6, characterized by the fact that the chiral liquid crystal precursor composition is in an initial chiral liquid crystal state and in which, in one or more of the first areas, the chiral liquid state initial chiral liquid crystal is changed to a first modified chiral liquid crystal state by means of the first modifying agent, and one or more areas of the second initial chiral liquid crystal state is changed to a second chiral liquid crystal state or modified and converted to a non-chiral liquid crystal state by means of the second modifying agent.
[0008]
8. Marking according to any one of claims 1 to 7, characterized in that the first modifying agent is solid or semi-solid and the second modifying agent is fluid.
[0009]
Marking according to any one of claims 1 to 8, characterized in that the first modifying agent is or comprises a resin made from one or more polymerizable monomers.
[0010]
10. Marking according to any one of claims 1 to 9, characterized in that the second modifying agent is fluid and selected from one or more of (a) a modifying composition comprising at least one compound selected from of ketoins having from 3 to 6 carbon atoms, alkyl esters and carboxylic acid dialkylamides comprising a total of 2 to 6 carbon atoms, dialkyl sulfoxides containing a total of 2 to 4 carbon atoms , and optionally substituted nitrobenzene; (b) a modifying composition comprising at least one chiral liquid crystal precursor composition, and (c) a modifying composition comprising at least one contaminating chiral composition.
[0011]
11. Marking according to claim 10, characterized by the fact that the first modifying agent is selected from cured and / or dry solid or semi-solid resins made from one or more polymerizable monomers, and in which both the first modifying agent and the second modifying agent alter an initial maximum wavelength of a selective reflection band (Àmax) displayed by the chiral liquid crystal precursor composition in the chiral liquid crystal state.
[0012]
12. Marking according to any one of claims 1 to 11, characterized by the fact that the one or more first areas and / or one or more second areas are in the form of at least one image, a photo, a logo , clues, and a pattern representing a code selected from one or more of a one-dimensional bar code, a stacked one-dimensional bar code, a two-dimensional bar code, a three-dimensional bar code, a point cloud , a network of lines and a data matrix.
[0013]
13. Marking according to any one of claims 1 to 12, characterized by the fact that the item or substrate is or comprises at least a label, package, cartridge, container or capsule containing foodstuffs , pharmaceuticals, nutraceuticals or beverages, a bank note, a credit card, a rubber stamp, a tax stamp, anti-counterfeiting stamp, a security document, a passport, an identity card, a driver's license, a card access, a transport ticket, an event ticket, a voucher, a transfer of film ink, a reflective film, an aluminum foil and commercial merchandise.
[0014]
14. Method for providing the marking of an item or substrate as defined in claim 1, the method comprising: a) applying to a surface of an article or substrate that carries a first modifying agent in one or more first areas of a composition curable chiral liquid crystal precursor that assumes an initial chiral liquid crystal state when heated, such that the composition includes at least a part of one or more first areas, the first modifying agent being able to modify a initial chiral liquid crystal of the composition; b) heating the applied composition to bring it to a first modified chiral liquid crystal state in one or more first areas and to the initial chiral liquid crystal state in all other areas, if any, of the applied composition; c) applying to one or more of the second areas of the applied composition, at least a second modifying agent which is of a different type than the first modifying agent and (1) is capable of locally modifying the modified chiral liquid crystal states initial and / or primary supplied by b), or (2) is capable of locally modifying the initial chiral states and / or the liquid crystal primaries provided by b) by heating the composition; d) in the case of (2), heating the composition of at least one or more of the second areas and e) curing the chiral liquid crystal precursor composition thus modified to produce a chiral liquid crystal polymer marking on the article or substrate, characterized by the fact that in said method the second modifying agent acts from the side opposite the substrate in one or more second areas, and in which at least one of the first or more areas is not overlapped by any second area and / or at least one of the one or more second areas is not overlapped by any first area.
[0015]
15. Method according to claim 14, characterized in that the chiral liquid crystal precursor composition comprises (i) one or more nematic compounds A; (ii) one or more contaminating chiral compounds B that are capable of giving rise to a cholesteric state of the precursor chiral liquid crystal composition, and (iii) at least one salt that changes from a maximum wavelength to a selective reflection band (Àmax) displayed through the composition in the chiral liquid crystal state compared to a maximum wavelength of a selective reflection band (Àmax) displayed through a composition in a chiral liquid crystal state that do not contain at least one salt.
[0016]
16. Method according to claim 14 or 15, characterized in that the second modifying agent is fluid and selected from one or more of (a) a modifying composition comprising at least one compound selected from ketones having 3 to 6 carbon atoms, alkyl esters and carboxylic acid dialkylamides comprising a total of 2 to 6 carbon atoms, dialkyl sulfoxides containing a total of from 2 to 4 atoms carbon, and optionally substituted nitrobenzene, (b) modifying a composition comprising at least one chiral liquid crystal precursor composition, and (c) a composition comprising modifying at least one contaminating chiral composition.

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法律状态:
2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-07-23| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-04-28| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-11-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-02-02| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 24/05/2012, OBSERVADAS AS CONDICOES LEGAIS. |

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