WO2006045567A2 - Utilisation de corps moules constitues de particules a noyau et enveloppe - Google Patents

Utilisation de corps moules constitues de particules a noyau et enveloppe Download PDF

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Publication number
WO2006045567A2
WO2006045567A2 PCT/EP2005/011380 EP2005011380W WO2006045567A2 WO 2006045567 A2 WO2006045567 A2 WO 2006045567A2 EP 2005011380 W EP2005011380 W EP 2005011380W WO 2006045567 A2 WO2006045567 A2 WO 2006045567A2
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WO
WIPO (PCT)
Prior art keywords
core
use according
shell particles
shell
security
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Application number
PCT/EP2005/011380
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German (de)
English (en)
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WO2006045567A3 (fr
Inventor
Holger Winkler
Matthias Kuntz
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Merck Patent Gmbh
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Publication of WO2006045567A2 publication Critical patent/WO2006045567A2/fr
Publication of WO2006045567A3 publication Critical patent/WO2006045567A3/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
    • B42D25/29—Securities; Bank notes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
    • B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
    • B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
    • B42D2035/24—

Definitions

  • the present invention relates to the use of moldings of core-shell particles for the production of optically variable security elements for security products, wherein the security elements simultaneously have another detectable security feature.
  • Security products such as banknotes, checks, credit cards, shares, passports, identity documents, driver's licenses, entrance tickets, tokens and the like have been equipped with various security features for many years, which are intended to complicate the counterfeiting of these products.
  • security products are equipped with different security elements that belong to different security levels. It is of great advantage if one and the same security element simultaneously belongs to several security levels or has several different detectable security features. This is the case, for example, if the security element has a plurality of mutually different optically perceptible security features or an optically perceptible and at least one further security feature perceptible only with auxiliary means. In the latter case, this is a combination of an open and a hidden security feature. It is particularly desirable if such a security element having a plurality of security features can be produced in a simple, preferably single, method step.
  • Colored safety elements are frequently used to produce the open, ie without or only with minor aids visible, security features.
  • optically variable security features have established themselves. Change this with changing illumination and / or viewing angle their visual appearance. Examples include holograms or security features that change their color and / or their brightness impression angle dependent.
  • optically variable security features are achieved by depositing multiple layers, each having different refractive indices, on suitable substrate surfaces, or by incorporating optically variable pigments into suitable support materials or by coating compositions comprising optically variable pigments on substrate surfaces receive.
  • US Pat. No. 4,434,010 discloses optically variable pigments which can be used in coating compositions for producing counterfeit-proof optically variable color effects. These pigments consist of several layers with different refractive indices and are produced in an elaborate and costly evaporation process. Due to their metal core they are only available opaque. A common use with optically invisible security features has not been described. In addition, the existing metal layers and the opacity of the pigments would severely affect the co-application of various visible and invisible security features.
  • US Pat. No. 5,424,119 describes a polymeric molded body which contains oriented multi-layer pigments which can have optically variable properties and can be used in security products to produce counterfeiting effects.
  • optically variable pigments to produce optically variable effects in security products generally has the disadvantage that the particulate structure of the pigments always makes visible visible and thus certain gloss and glitter effects can not be prevented.
  • the optical properties of the pigments are limited by interference, diffraction and reflection phenomena at the number of highly limited interfaces of the various layers of the pigments and the material selection for the layers is limited. If, at the same time, other particulate materials are to be used to produce optically invisible security features, the effect of the particles being often too great on one another or the particulate loading of coatings or polymeric layers becomes too great, so that mechanical stability problems arise.
  • Shaped bodies of core-shell particles which may have optical effects, including optically variable effects, are known.
  • EP 0 955 323 A1 describes core / shell particles whose core and shell materials can form a two-phase system, and which are characterized in that the shell material is filmable, the core is substantially dimensionally stable under the conditions of filming of the shell the core is not or only slightly swellable by the shell material, the cores one have monodisperse size distribution and there is a difference in the refractive indices of the core material and the shell material.
  • a dispersion can be prepared which is dried on a suitable substrate to form a film.
  • This movie can be one with the lighting and / or
  • molded articles of core-shell particles whose shell forms a matrix and whose core is substantially solid and has a substantially monodisperse size distribution, wherein differences in the refractive indices of the core material and the cladding material, are advantageous for the production can be used by security features that are optically variable and have at least one other detectable security feature.
  • such moldings can be used for the production of
  • the present invention is therefore the use of a shaped body of core-shell particles whose shell forms a matrix and the core is substantially solid and a substantially having monodisperse size distribution, wherein there is a difference between the refractive indices of the core material and the cladding material, for producing a security element which is optically variable and has at least one further detectable security feature.
  • the invention furthermore relates to the use of a molding described above, which is obtainable by a process in which a) the core-shell particles are heated to a temperature at which the shell is free-flowing, b) the flowable core-shell particles Particles from a) are oriented to a regular structure and c) the regular structure is solidified.
  • Another object of the present invention is the use of the shaped body described above for the production ofbut ⁇ elements for security products.
  • An additional object of the present invention is the use of the molding described above for the production of
  • optically variable security elements which are made using shaped bodies of core-shell particles whose shell forms a matrix and whose core is essentially solid and has a substantially monodisperse size distribution, wherein a difference between the refractive indices of the
  • Core material and the cladding material is made, produced and the have at least one further detectable security feature, another object of the present invention.
  • Optically variable security elements in the sense of the present invention are those which, under different illumination and / or viewing angles, have a different visually discernible color or color
  • the security elements show non-copyable color and gloss impressions, which are clearly visible to the naked eye.
  • the security elements preferably have three optically clearly distinguishable discrete colors under at least two different illumination or viewing angles at least two and at most four, but preferably at two different illumination or viewing angles two or three different illumination or viewing angles. This feature makes it easier for the viewer to recognize the security element as such and, at the same time, makes it more difficult to copy the feature, as color flop effects can not be copied and reproduced in the commercially available color copiers.
  • Security elements which have a color gradient when tilted over different illumination and / or viewing angles can likewise be used, since even such diffuse color changes can be easily detected by the human eye.
  • the other detectable security features are optical, machine or haptic detectable security features.
  • optically detectable security features are those that are visually perceptible with little or no tools, but are different from the optically variable color and / or Hell ⁇ gkeitseindruck. However, it is not excluded that such optically detectable
  • Security features are also machine-evaluable and thus can be detected by machine. These are additional visible ones Information such as printed characters, symbols or microtext, in particular, the additional optically detectable security feature but a laser mark.
  • the latter can be obtained in a molded body which contains at least one core and / or cladding material suitable for laser marking, which contains suitable additives or which, in addition to the core-shell particles, at least one further material suitable for laser marking contains, is described with a laser beam.
  • the shaped body according to the invention contains at least one material with luminescent, magnetic, electrically conductive, thermoelectric or piezoelectric properties, which may be particulate and embedded in the molded body. Suitable materials are described below.
  • Haptic detectable security features are those that can be detected by the human sense of touch. This does not exclude that they can also be detected mechanically by means of suitable equipment.
  • Haptically detectable security features are obtainable via the incorporation of suitable materials into the molding in the sense of the invention or via a subsequent mechanical treatment of the molding, for example by using temperature and pressure.
  • suitable materials and methods are described below.
  • moldings of core-shell particles are used, the shell forms a matrix and the core is substantially solid and has a substantially monodisperse size distribution, with differences in the refractive indices of Kemmaterials and the
  • Sheath material exist.
  • the moldings described therein are films which are produced on a suitable substrate and consist predominantly of core / shell particles whose cores are substantially dimensionally stable under the conditions of filming of the shell and whose shell material is filmable, so that in the case of Softening of the shell material to a viscoelastic or liquid state, the cores of the core / shell particles can form at least domains of regular arrangement, which are then solidified by drying the film. Subsequently, the film is released from the substrate.
  • the filmed shell material then forms depending on its proportion in ⁇ er ⁇ core / shell particles either a continuous, all spaces between the Kempumblen filling phase, or it forms adhesive points only in the region of the contact points of the core particles, through which the regular arrangement is fixed.
  • the regularly arranged, substantially spherical or globular cores have a monodisperse size distribution and form a diffraction grating, which causes I nterferenzerscheinept.
  • EP 0 955323 A1 has a large number of, in particular, polymeric materials to choose from. These are going to be there the filmability of the shell material and / or selected according to the difference in the refractive indices of the core and the cladding material.
  • polymers are now selected as core material or as sheath material or as core and sheath material Laser marking are suitable.
  • the core material or jacket material is polystyrene or a styrene copolymer.
  • the shaped bodies can be provided with sufficient mechanical strength with a further optically detectable security feature.
  • the shaped bodies are additionally printed by means of known techniques with signs or symbols or provided with or microtexts.
  • the method for producing the moldings according to EP 0 955 323 A1 leads to the generation of domains having a regular structure of the cores, it is possible for the cores to have a uniform structure over the entire length spatial extension of the formed bodies (films) can not be guaranteed. As a result, there may be local differences in the optically variable behavior of the formed films, which are not always desirable. In addition, possibly incorporated into the moldings particulate additives could interfere with the formed domains with regular core structure sensitive, which can lead to further irregularities and thus attenuated optically variable color effects.
  • shaped articles in the context of the present invention are those shaped articles which correspond in their composition to the shaped articles described in International Patent Application WO 03/025035 A2.
  • the shaped body is preferably a film, a film or a layer which is preferably firmly joined to at least one further layer of another flat material which determines the mechanical properties of the composite (composite material).
  • composite material composite material
  • Corresponding materials are described in the German patent application DE 10227 071 A1. The content of both patent applications expressly also belongs to the content of the present application.
  • the cores of the core-shell particles used in the present invention may be made of a variety of materials as long as there is a difference between the refractive indices of the core material and the cladding material and the cores remain substantially solid under the processing conditions. This is achieved by using materials which either do not flow or become fluid at a temperature above the flow temperature of the jacket material.
  • polymeric materials with a correspondingly high glass transition temperature (T 9 ) or inorganic core materials are selected.
  • the cores of the core-shell particles are made of an organic polymeric material, which is in particular crosslinked, or contain this predominantly.
  • Polymers and / or copolymers that may or may not be included in the core material are high molecular compounds that either do not or become fluid at a temperature above the flow temperature of the shell material. This means that the cores produced from them are essentially solid.
  • Suitable polymers are both polymers and copolymers of polymerizable unsaturated monomers and polycondensates and copolycondensates of monomers having at least two reactive groups, such as.
  • As high molecular weight aliphatic, aliphatic / aromatic or wholly aromatic polyester polyamides, polycarbonates, polyureas and polyurethanes, but also aminoplast and phenoplast resins, such as.
  • epoxy resins which are also suitable as core material
  • epoxy prepolymers for example by reaction of bisphenol A or other bisphenols, resorcinol,
  • Hydroquinone, hexanediol, or other aromatic or aliphatic di- or polyols, or phenol-formaldehyde condensates, or mixtures thereof are obtained with each other with epichlorohydrin, or other di- or polyepoxides, mixed with other compounds capable of condensation directly or in solution and cured ,
  • the polymers of the core material are expediently cross-linked (co) polymers, since these usually show their glass transition only at high temperatures.
  • These crosslinked polymers can either already during the polymerization or polycondensation or Co polymerization or
  • Copolycondensation be crosslinked, or they can be completed the actual (co) polymerization or (co) polycondensation have been postcrosslinked in a separate process step.
  • the monodisperse cores are obtained from organic polymeric materials by emulsion polymerization.
  • auxiliaries and additives used for example polymerization initiators, dispersing aids, emulsifiers, crosslinkers and the like, reference is expressly made to the corresponding statements in EP 0 955 323 A1 and in WO 03/025035 A2.
  • the core consists predominantly of an inorganic material, preferably a metal or semimetal or a metal chalcogenide or metal pnictide.
  • chalcogenides are those compounds in which an element of the 16th group of the peroxide system is the electronegative binding partner; pnictides are those in which an element of the 15th group of the periodic table is the electronegative binding partner.
  • Preferred cores consist of metal chalcogenides, preferably metal oxides, or metal pnictides, preferably nitrides or phosphides.
  • Metal in terms of these terms are all elements that can occur as electropositive partner in comparison to the counterions, such as the classical metals of the subgroups, or the main group metals of the first and second main group, as well as all elements of the third main group, as well as silicon, Germanium, tin, lead, phosphorus, arsenic, antimony and bismuth.
  • the preferred metal chalcogenides and metal pnictides include, in particular, silicon dioxide, aluminum oxide, gallium nitride, boron nitride and aluminum nitride, and also silicon and phosphorus nitride.
  • starting materials for the production of the core-shell particles are preferably monodisperse cores of silicon dioxide, which can be obtained, for example, by the process described in US Pat. No. 4,911,903.
  • the cores are thereby produced by hydrolytic polycondensation of tetraalkoxysilanes in an aqueous-ammoniacal medium, initially producing a sol of primary particles and then bringing the resulting SiO 2 particles to the desired particle size by continuous, controlled metered addition of tetraalkoxysilane.
  • monodisperse SiO 2 cores having mean particle diameters of between 0.05 and 10 ⁇ m can be produced with a standard deviation of 5%.
  • preferred starting materials are SiO 2 nuclei which are coated with (semi-) metals or non-absorbing metal oxides in the visible range, for example TiO 2 , ZrO 2 , ZnO 2 , SnO 2 or Al 2O 3.
  • metal oxides coated with Si ⁇ 2 -Keme example, in US 5,846,310, DE 19842 134 and DE 199 29 109 described in more detail.
  • monodisperse cores of non-absorbing metal oxides such as TiO 2 , ZrO 2 , ZnO 2 , SnO 2 or Al 2 O 3 or metal oxide mixtures. Their preparation is described for example in EP 0 644 914. Furthermore, the process according to EP 0 216 278 for the production of monodisperse SiO 2 cores is readily transferable to other oxides with the same result.
  • Particles are also suitable monodisperse cores of polymers containingtik ⁇ closed particles, which consist for example of metal oxides.
  • Such materials are offered, for example, by the company micro capseries- undmaschines GmbH in Rostock. According to customer requirements, microencapsulations based on polyesters, polyamides and natural and modified carbohydrates are manufactured.
  • monodisperse cores of metal oxides which are coated with organic materials for example silanes.
  • the monodisperse cores are dispersed in alcohols and modified with common organoalkoxysilanes.
  • the silanization of spherical oxide particles is also described in DE 43 16 814.
  • the size and particle size distribution of the cores can be adjusted particularly well if the cores predominantly or exclusively consist of organic polymers and / or copolymers.
  • the cores are predominantly a single polymer or copolymer.
  • the jacket material In order to be able to produce suitable moldings from the core-shell particles, it is important that the jacket material can be made into a film. It must therefore be able to be heated to a temperature at which the jacket is flowable.
  • the shell is softened, visco-elastic plasticized or liquefied.
  • the jacket material has a flow temperature which is significantly lower than the flow temperature of the core material.
  • Polymers that meet the specifications for a jacket material are also in the Gru ppen the polymers and copolymers of polymerizable unsaturated monomers, as well as the polycondensates and copolycondensates of monomers having at least two reactive groups, such as.
  • the high molecular weight aliphatic, aliphatic / aromatic or wholly aromatic polyester and polyamides are also in the Gru ppen the polymers and copolymers of polymerizable unsaturated monomers, as well as the polycondensates and copolycondensates of monomers having at least two reactive groups, such as.
  • the high molecular weight aliphatic, aliphatic / aromatic or wholly aromatic polyester and polyamides are also in the Gru ppen the polymers and copolymers of polymerizable unsaturated monomers, as well as the polycondensates and copolycondensates of monomers having at least two reactive groups, such as.
  • selected components from all groups of organic film formers are suitable for their preparation.
  • Some other examples may illustrate the wide range of polymers suitable for the manufacture of the sheath.
  • polymers such as polyethylene, polypropylene, polyethylene oxide, polyacrylates, polymethacrylates, polybutadiene, polymethyl methacrylate, polytetrafluoroethylene, polyoxymethylene, polyesters, polyamides, polyepoxide, polyurethane, rubber, polyacrylonitrile and polyisoprene are suitable.
  • the jacket is to be comparatively high-refractive, for example, polymers with preferably aromatic basic structure such as polystyrene, polystyrene copolymers such as, for example, are suitable for the jacket.
  • polymers with preferably aromatic basic structure such as polystyrene, polystyrene copolymers such as, for example, are suitable for the jacket.
  • SAN aromatisctvaliphatician polyesters and polyamides, aromatic polysulfones and polyketones, polyvinyl chloride, polyvinylidene chloride, as well as suitable Selection of a high-index core material also polyacrylonitrile or polyurethane.
  • Core-shell particles which have been bonded to the core via an intermediate layer have proven to be particularly suitable for the production of the moldings used according to the invention.
  • the intermediate layer in a preferred embodiment of the invention is a layer of crosslinked or at least partially crosslinked polymers.
  • the crosslinking of the intermediate layer via free radicals, for example induced by UV irradiation, or preferably via di- or oligofunctional monomers take place.
  • Preferred intermediate layers of this embodiment contain from 0.01 to 100% by weight, particularly preferably from 0.25 to 10% by weight, of di- or oligofunctional monomers.
  • Preferred di- or oligofunctional Ivlonomere are in particular isoprene and allyl methacrylate (ALMA).
  • Such an intermediate layer of crosslinked or at least partially crosslinked polymers preferably has a thickness in the range of less than 1 nm to 20 nm. If the intermediate layer thickens, the refractive index of this layer is chosen such that it either the refractive index of Kemmaterials or the refractive index of Sheath material corresponds.
  • copolymers are used as interlayer, which, as described above, contain a crosslinkable monomer, so it presents the expert any problems, corresponding copolymerizable
  • Suitable monomers For example, corresponding copolymerizable monomers can be selected from a so-called Qe scheme (see Textbooks of Macromolecular Chemistry).
  • corresponding copolymerizable monomers can be selected from a so-called Qe scheme (see Textbooks of Macromolecular Chemistry).
  • preferably monomers such as methyl methacrylate and methyl acrylate may be polymerized. 11380
  • the shell polymers are grafted onto the core directly via a corresponding functionalization of the core.
  • the surface functionalization of the core forms the above-mentioned intermediate layer.
  • the type of surface functionalization depends mainly on the material of the core. Silica surfaces can be suitably modified, for example, with silanes bearing corresponding reactive end groups, such as epoxy functions or free double bonds.
  • Other surface functionalizations for example for metal oxides, can be carried out using titanates or organoaluminum compounds which each contain organic side chains with corresponding functions.
  • For polymeric cores it is possible, for example, to use a styrene functionalized on aromatic compounds, such as bromostyrene. This functionalization can then be used to achieve the growth of the sheath polymers.
  • the intermediate layer can also bring about adhesion of the jacket to the core via ionic interactions or complex bonds.
  • the jacket of these core-shell particles consists of essentially unvarnished organic polymers, which are preferably grafted onto the core via an at least partially crosslinked intermediate layer.
  • the jacket substantially determines the material properties and processing conditions of the core-shell particles, those skilled in the art will select the jacket material according to common considerations in polymer technology.
  • the shaped bodies of core-shell particles are to be used to produce a security element which is optically variable and has at least one further optically detectable security feature, in particular a laser marking, it is a simple one T / EP2005 / 011380
  • Embodiment of the present invention it is possible to select the material for the cores and / or the jacket so that the shaped bodies are laser markable. This can be achieved without problems if polymers are selected as core material or as cladding material or as core and cladding material, which are suitable for laser marking. These are, in particular, polyethylene terephthalate, styrene copolymers, acrylonitrile-butadiene-styrene, polystyrene, polyphenyl ethers, polyphenylene sulfide, polyarylates, polyaryl sulfides, polyaryl sulfones or polyaryl ether ketones. Since there must be a difference in the refractive indices of core material and cladding material, it goes without saying that different materials are used for the core material and the cladding material.
  • the core material or the shell material is preferably made of polystyrene or a styrene Cop ⁇ lymer.
  • the core-shell particles have an average particle diameter in the range of about 50-500 nm.
  • particles in the range of 100-500 nm are used, and particularly preferably particles having a particle diameter of 150-400 nm, since with particles in this order of magnitude (depending on the achievable in the resulting crystal structure refractive index contrast) reflections of different wavelengths of visible light clearly Distinguish from each other and so particularly pronounced for optical effects in the visible range opalescence in a variety of colors occurs.
  • the cores of the core-shell particles have a substantially spherical, in particular spherical shape and have a substantially monodisperse size distribution, ie they are present in a very narrow particle size distribution.
  • the average particle diameter of the core particles is in the range of 30-400 nm, in particular in the range of 60-350 nm and particularly preferably in the range of 90-300 nm.
  • the particle diameter of the core particles is about 60 to about 80%, in particular from about 65 to about 75% of the total diameter of the core-shell particles.
  • the weight ratio of core to shell in the range of 2: 1 to 1: 5, preferably in the range of 3: 2 to 1: 3 and particularly preferably in the range of less than 1, 2: 1.
  • the weight ratio of core to shell is less than 1: 1, with a typical upper limit of shell ratio for a core to shell weight ratio of 2: 3.
  • the shaped bodies of core-shell particles are produced according to international patent application WO 03/025035, ie if the core-shell particles are exposed to a mechanical force in the production of the shaped bodies, three-dimensional shaped bodies having a focal arrangement of the cores are obtained which occurs over the entire spatial extent of the moldings.
  • This long-range arrangement corresponds to a dense spherical packing which is arranged in the form of a cubic-face-centered spherical packing, but which does not completely correspond to it due to the spaces filled by the casing material.
  • the cores regularly arranged in this way in the matrix form a diffraction grating, at which reflection, interference and scattering of irradiated light take place simultaneously and homogeneously over the entire spatial extent occupied by the shaped body.
  • the achievable visual appearance is significantly influenced by the middle
  • Inventive moldings preferably have a difference ⁇ n between the refractive indices of the core material and the cladding material of at least 0.01, and preferably of at least 0.1.
  • the material of the core may be higher refractive than the material of the shell or vice versa.
  • the material of the core is higher refractive than the material of the shell.
  • the intensity of the color effects occurring increases with the refractive index difference between the structure-forming cores and the matrix-forming outer shells of the particles.
  • a refractive index difference as possible is e.g. achieved when polystyrene (PS) is selected as Kempolymer and polyacrylate (PEA) as a sheath polymer.
  • PS polystyrene
  • PPA polyacrylate
  • systems with a lower refractive index difference are also of interest for use in security elements with a soft, optically variable effect, since they can be used to achieve slight color shimmer effects (pearlescent gloss).
  • the molded articles used in the present invention are prepared by heating the core-shell particles to a temperature at which the shell is flowable, the thus obtained flowable 11380
  • Core-Mantel-Partik ⁇ l are oriented to a regular structure and the regular structure is solidified.
  • the last-mentioned step generally takes place with cooling of the core-shell particles, evaporation of any solvent present and drying of the layer obtained.
  • the flowable core-shell particles are applied to a substrate, from which the dried shaped body obtained after solidification of the core-shell particles is removed again.
  • the core-shell particles are oriented to a regular structure by subjecting the flowable core-shell particles to a mechanical force.
  • This is preferably the action of shear forces which, for example, act on the still flowable core-shell particles during a pressing process, an extrusion process, a co-extrusion process or a spray-casting process.
  • the flowable core-shell particles do not have to be applied to a substrate and later removed from it as a film.
  • This type of orientation is expressly preferred because it allows the above-described regular arrangement of a quasi cubic-area-centered spherical packing for the core particles to be achieved.
  • due to the nature and intensity of the force an additional
  • the chain ends of the sheath polymers generally tend to assume a ball shape. If two particles come too close, the balls are compressed according to the model and repulsive forces are created. Since the mantle polymer chains of different particles also interact with each other, the polymer chains are stretched according to the model when two particles separate from each other. The tendency of the sheath polymer chains to assume a ball shape again results in a force that pulls the particles closer together again. After the model presentation, the far-reaching
  • At least one contrast material is incorporated in a shaped body which consists of core-shell particles, wherein the at least one contrast material is a soluble or insoluble colorant.
  • Soluble colorants are usually soluble, mostly organic, dyes of natural or synthetic origin and usually selected from the compound classes of carbonyl colorants such as quinones, indigoid colorants and quinacridones, cyanine colorants such as di- and triarylmethanes and quinone imines, azo colorants, azomethines and methines, isoindoline colorants, phthalocyanines and dioxazines are.
  • Insoluble colorants are organic or inorganic color pigments. These are preferably absorption pigments and in a variant of the invention particularly preferably black pigments.
  • contrast materials are usually inorganic or organic pigments, which may be of natural or synthetic origin.
  • pigments are understood to mean any solid substance which exhibits an optical effect in the visible wavelength range of the light or which has certain functional properties.
  • such substances are referred to as pigments which correspond to the definition of pigments according to DIN 55943 or DIN 55944.
  • a pigment is an inorganic or organic, colored or achromatic colorant practically insoluble in the application medium or a substance practically insoluble in the application medium, which has special properties, for example magnetic, electrical or electromagnetic properties.
  • absorption and gloss pigments can be used in accordance with the invention, it also being possible in particular to use interference pigments. It has been shown, however, that the use of absorption pigments is preferred, in particular for increasing the intensity of the optical effects.
  • color pigments means all pigments that give a different color than white or black, such as Heliogen TM Blue K 6850 (BASF, Cu phthalocyanine pigment), Heliogen TM Green K 8730 (BASF, Cu phthalocyanine pigment), Bayferrox TM 105 M (Bayer, iron oxide-based red pigment) or chrome oxide green GN-M (Fa Bayer, chromium oxide-based green pigment).
  • the black pigments are again preferred among the absorption pigments.
  • pigmentary carbon black eg the carbon black product line from Degussa (in particular Purex TM LS 35 or Corax TM N 115 or Flammruss TM 101)
  • iron oxide black e.g the carbon black product line from Degussa (in particular Purex TM LS 35 or Corax TM N 115 or Flammruss TM 101)
  • iron oxide black e.g the carbon black product line from Degussa (in particular Purex TM LS 35 or Corax TM N 115 or Flammruss TM 101)
  • iron oxide black e.g the carbon black product line from Degussa (in particular Purex TM LS 35 or Corax TM N 115 or Flammruss TM 101)
  • iron oxide black e.g the carbon black product line from Degussa (in particular Purex TM LS 35 or Corax TM N 115 or Flammruss TM 101)
  • iron oxide black
  • Manganese black as well as cobalt black and antimony black are examples of manganese black as well as cobalt black and antimony black.
  • Black mica grades can also be used advantageously as black pigment (for example Iriodin TM 600, Merck, iron oxide-coated mica).
  • the average particle diameter of the particulate contrast materials is in the range of about 1 nm to about 35 microns. Such particles only interact locally with the grating formed from the cores. Electron micrographs prove that the embedded particles do not or only slightly disturb the lattice of core particles. In this case, the particle size of the contrast materials, which are often also platelet-shaped pigments, means the respectively greatest extent of the particles. If platelet-shaped pigments have a thickness in the range of the particle size of the cores or even below it, this does not disturb the lattice orders according to available investigations. It has also been shown that the
  • both spherical and platelet-shaped and needle-shaped contrast materials can be incorporated.
  • the average particle diameter of the at least one contrast material is at least twice as large as the mean particle diameter of the cores, wherein the average particle diameter of the at least one contrast material is preferably at least four times as large as the average particle diameter. diameter of the nuclei, since then the observable interactions are even lower.
  • a reasonable upper limit of the particle size of the contrast materials results from the limit at which the individual particles themselves become visible or impair the mechanical properties of the shaped body due to their particle size. The determination of this upper limit presents no difficulty for the skilled person.
  • contrast material Of importance to the desired effect is also the amount of contrast material used. It has been found that effects are usually observed when at least 0.05% by weight of contrast material, based on the weight of the molding, is used. It is particularly preferred if the molding body contains at least 0.2% by weight and particularly preferably at least 1% by weight of contrast material, since these increased contents of contrast material generally also lead to more intensive effects.
  • the shaped body contains not more than 12% by weight and preferably not more than 5% by weight of contrast material.
  • the incorporated contrast materials cause an increase in brilliance, contrast and depth of the observed optically variable color effects in the moldings according to the invention.
  • many of these contrast materials are also capable of absorbing laser beams, causing the can be laser marked with the addition of the contrast materials.
  • Laser-sensitive contrast materials are, for example, various fillers, inorganic pigments including electrically conductive pigments and / or effect pigments such as, for example, interference pigments, in particular pearlescent pigments.
  • Suitable effect pigments are, for example, all known gloss pigments (metal and pearlescent pigments), as described, for example, in US Pat. B. from the companies Engelhard Corp., Eckart-Werke and Merck KGaA.
  • Suitable electrically conductive pigments are, for. As the marketed under the trade name Minatec® pigments Merck KGaA.
  • Other suitable laser-sensitive pigments are the oxides, hydroxides, sulfides, sulfates and phosphates of metals, such as. As copper, bismuth, tin, zinc, silver, antimony, manganese, iron, nickel or chromium, which are often inorganic color pigments.
  • contrast materials are selected from the materials described above, moldings are obtained which are also laser-markable, even if the core and cladding materials are not selected from the abovementioned materials suitable for laser marking.
  • laser-sensitive contrast materials can themselves be used as core particles, for example in the form of the previously described SiO 2 spheres.
  • the shaped bodies or the security elements produced therefrom are marked with high-energy radiation in the wavelength range from 157 to 10600 nm, in particular in the range from 300 to 10600 nm.
  • the energy densities of the lasers used are generally in the range from 0.3 mJ / cm 2 to 50 mJ / cm 2 , preferably in the range from 0.3 mJ / cm 2 to 10 mJ / cm 2 .
  • nanoparticles are incorporated in the matrix phase (in the shell) of the shaped bodies in addition to the cores of the core-shell particles.
  • Preferred materials are inorganic nanoparticles, in particular nanoparticles of metals or of Il-Vl or III-V semiconductors or of materials which influence the magnetic / electrical (electronic) properties of the materials.
  • preferred nanoparticles are noble metals, such as silver, gold and platinum, semiconductors or insulators, such as zinc and cadmium chalcogenides, oxides, such as hematite, magnetite or perovskites, or metal pnictides, eg. B. gallium nitride or mixed phases of these materials. These nanoparticles are used in average particle sizes of 1 nm to 50 nm.
  • the moldings for the use according to the invention may additionally or alternatively contain other materials, namely mechanically detectable constituents. This does not exclude that certain contrast materials and nanoparticles due to their special properties (magnetic, electrically conductive, special shape or even colored) are also mechanically detectable with suitable equipment.
  • Machine-detectable components in the sense of the present invention are substances with luminescent, electrically conductive, magnetic, thermoelectric or piezoelectric properties.
  • Formkörpem of core-shell particles for Verwen ⁇ tion according to the invention are present.
  • Luminescent compounds are understood as meaning substances which emit mechanically measurable and optionally visible radiation by excitation in the visible wavelength range, in the IR or in the UV wavelength range of the light, by electron beams or by X-rays. These also include substances which emit radiation by excitation in the electromagnetic field, the so-called electroluminescent substances which, if appropriate, additionally luminesce by excitation in the UV or IR wavelength range. Suitable for this purpose are all known particulate and soluble substances having the abovementioned properties.
  • the particulate substances are in a suitable particle size, ie with an average particle size of from about 0.001 to about 35 .mu.m, preferably from 0.005 to 20 .mu.m and particularly preferably from 0.01 to 1 .mu.m before.
  • particulate substances need not necessarily be present in pure form, but may as well be microencapsulated particles and impregnated with luminescent substances, doped or coated
  • Support materials include. For this reason, luminescent substances can be incorporated both into the core particles (or as core particles) and into the matrix (shell) of the shaped bodies of core-shell particles n. This applies to both soluble and particulate luminescent materials. It goes without saying that the particle size of the particulate luminescent substances in the cores must not exceed the mean particle diameter of the cores.
  • luminescent substances besides all kinds of organic luminescent substances, the following compounds can be mentioned here: Ag-doped zinc sulfide ZnS: Ag, zinc silicate, SiC, ZnS, CdS activated with Cu or IvIn, ZnS / CdS: Ag; ZnS: Cu, Al; Y 2 O 2 SiEu; Y 2 O 3 : Eu; YVO 4 : Eu; Zn 2 SiO 4 : Mn;
  • Substances with electrically conductive properties are usually particulate and consist of or contain electrically conductive substances.
  • pigments which have at least one electrically conductive layer on a substrate which is selected from the group consisting of TiO 2 , synthetic or natural mica, other layer silicates, glass, SiO 2 and / or Al 2 O 3 .
  • the substrates mentioned are platelet-shaped.
  • Pigments consisting of an electrically conductive material are also suitable.
  • the electrically conductive layer or the electrically conductive material comprises one or more conductive doped metal oxides, such as For example, tin oxide, zinc oxide, indium oxide or titanium oxide, which are doped with gallium, aluminum, indium, thallium, germanium, tin, phosphorus, arsenic, antimony, selenium, tellurium and / or fluorine.
  • conductive doped metal oxides such as For example, tin oxide, zinc oxide, indium oxide or titanium oxide, which are doped with gallium, aluminum, indium, thallium, germanium, tin, phosphorus, arsenic, antimony, selenium, tellurium and / or fluorine.
  • the above conductive pigments may have one or more further layers above and / or below the conductive layer. These layers may contain metal oxides, metal oxide hydrates, metal suboxides, metal fluorides, metal nitrides, metal oxynitrides or mixtures of these materials.
  • the color properties of the conductive pigments can be adapted to the requirements of the user, in particular if the additional layers are located below the conductive layer.
  • the conductivity can be tailored to the requirements of the application.
  • a particularly preferred material for an electrically conductive pigment is a mica coated with at least one electrically conductive metal oxide layer. Particularly preferred here is a
  • Such pigments are commercially available under the name Minatec® from Merck KGaA.
  • electrically conductive particles from other manufacturers are also suitable.
  • the electrically conductive particles have average particle sizes of from about 0.001 to about 35 .mu.m, preferably from 0.005 to 20 .mu.m and particularly preferably from 0.10 to 10 .mu.m. In this case, a narrow particle size distribution is preferred.
  • substances with magnetic properties are usually particulate.
  • all particles which consist of magnetizable materials or contain magnetizable materials as core, coating or doping are suitable for this purpose.
  • all known materials such as magnetizable metals, magnetizable metal alloys or metal oxides and oxide hydrates, such as ⁇ -Fe 2 O 3 or FeOOH, can be used as the magnetizable materials.
  • Their applicability is limited only by the average particle size which is in the range from about 0.01 to about 35 ⁇ m, preferably from 0.03 to 30 ⁇ m U and particularly preferably from 0.04 to 20 ⁇ m.
  • the magnetic properties of the particles must be so strong that they can be determined by machine. Their shape is not essential, especially needle-shaped magnetic particles can be incorporated. As with luminescent substances, magnetic particles whose mean particle diameters do not exceed the average particle diameter of the cores of the core-shell particles can be incorporated not only into the matrix but also into the cores of the core-shell particles. This is particularly possible when an organic polymer is used as the core material.
  • thermoelectric and piezoelectric materials can be incorporated into the moldings of core-shell particles.
  • thermoelectric materials thereby substances with high electrical, but low thermal conductivity are used, such as nanostructures of heavy elements such as cesium bismuth tellurides, lead tellurides, lead selenium selenides, bismuth tellurides, Antimon ⁇ Telluride etc.
  • piezoelectric material are preferably quartz used particles which generate an electrical voltage during deformation or cause a Defor ⁇ mation when applying an electrical voltage, which can lead to color changes in the molding of core-shell particles. These materials have average particle sizes of about 0.001 to about
  • the machine-readable constituents mentioned here can be present individually or mixed with one another in the shaped bodies of core-shell particles according to the present invention.
  • Such forms of coding are already known per se and include, for example, differently colored luminescent particles in defined relation to one another, which can clearly identify a specific product or even a specific batch of a product.
  • Jacket materials may well include various machine-readable materials of the same or different types.
  • the concentration of the machine-readable constituents in the shaped body is determined by the degree of its machine detectability and by the application properties in the core or shell material of the shaped bodies.
  • the machine-readable constituents are present in an amount of from 0.01 to 12% by weight, preferably in an amount of from 0.05 to 10% by weight and more preferably from 0.1 to less than 5% by weight, in each case on the weight of the molding, in this before.
  • the mold body for use according to the invention has a machine-detectable component in addition to the optically variable coloration and is also laser-markable due to the selection of the core and / or cladding material.
  • security elements are available which are optically variable and may additionally contain both a further optically detectable security feature and a machine-detectable security feature.
  • the additional optically detectable constituent leads to a visible effect, which can be reliably recognized by the inexperienced observer without further aids.
  • the additional optically detectable effect can in any case also consist solely or additionally of printed characters or symbols or of visible microtexts applied in the customary manner.
  • these molded articles can be provided with a high-low structure by pressing, embossing, stamping and other similar methods without losing the optically variable coloring of the molded articles as a whole.
  • the moldings are heated locally or over the entire surface until a flowability of at least parts of the matrix is reached (partial melt).
  • C are generally sufficient temperatures of about 5O 0 C to about 220 0th
  • the moldings are provided at pressures of about 100 bar to about 600 bar with a high-low structure and then allowed to cool. During cooling, the pre-created high-low structure manifests.
  • Shaped bodies which, in addition to the optically variable coloring, also have a high-low structure, can thus be used without difficulty for producing security elements which are optically variable and at the same time have a haptically detectable security feature, since regardless of their shape and depth, as a rule can be detected by the human sense of touch. This does not rule out that these high-low structures can also be detected by machine.
  • the shaped bodies can only be provided with a high-low structure if the shaped body is already present as a security element in or on a product to be protected, for example in order to prevent the high-low Structure is damaged when incorporating the security element into the product to be protected. If suitable protective measures are taken, the high-low structure can also be applied in advance to the shaped body.
  • optically variable properties of the moldings used according to the invention are clearly different from the optically variable properties of security elements which are different when thin film sequences are used Refractive indices or can be produced using optically variable pigments.
  • the nuclei in the moldings used according to the invention form a spatial diffraction grating, which has many individual diffraction centers horizontally and vertically, at which incident light is scattered, reflected and transmitted, and where it therefore becomes considerable Interference phenomena comes, which can not be imitated especially with optically variable pigments.
  • the shaped bodies show a spatial optically variable overall impression which occurs over their entire extent and which does not reveal any particulate and in particular no glitter effects.
  • optically variable behavior can also be represented in the usual colorimetric measurements.
  • the usual goniometric measurements in the CIELAB system according to Hunter in the entire color range, on which an optically variable color behavior can be observed show considerably higher values for the color strength (chroma) in the moldings used according to the invention than obtainable with pigment coatings are that contain optically active pigments which are active in the same color space, ie have approximately the same color flop, for example from red to gold and green to blue-green.
  • the chroma values of the moldings used are often twice and sometimes a multiple of the chromium values obtainable with pigments.
  • optically variable behavior of the moldings used according to the invention can not be copied by the use of optically variable pigments. Differences in color behavior are not only visible, but the use of the shaped bodies in security elements can also be explicitly demonstrated by specific measurements of the colorimetry. This specific detectability of the material used plays a not to be underestimated role for the security against forgery of the optically variable behavior of the security elements produced with the Formkörpem.
  • Moldings easily, namely in particular on the adjustment of the distances of the core particles, the refractive index difference of core and Mantel ⁇ material, the nature and intensity of the force in the orienting orientation of the core particles and optionally the addition of contrast materials possible. In this way, security elements can be obtained, which can be tailored to the exact requirements of the respective user.
  • the security element thus produced (periodicity of the core particles, refractive index difference of nuclear and
  • Cladding material via a reflection spectrum, which is determined by irradiation of whiter light, for example with a white LED, and subsequent detection, for example with a diode array.
  • the moldings for use according to the invention are preferably in sheet form, for example as films or films, and consist of at least 60% by weight, preferably at least 80% by weight and in particular at least 95% by weight, of core-shell particles.
  • the moldings may additionally contain auxiliaries and additives. These are used to adjust the application and processing required and required performance characteristics.
  • auxiliaries and additives are antioxidants, UV stabilizers, biocides, plasticizers, film-forming aids, leveling agents, fillers, melt aids, Adhesive oil, release agents, application aids, mold release agents and viscosity modifiers, e.g. As thickeners or flow improvers.
  • the shaped bodies which essentially consist of core-shell particles
  • This further sheet-like material which is usually selected from the materials metal, glass, wood, polymers (plastics), paper or cardboard, then determines the mechanical properties of the resulting composite material significantly.
  • the other planar material is advantageously selected from the materials, paper, cardboard and polymers.
  • thermoplastics and rubber polymers are preferred.
  • thermoplastics used are those which are processable in the soft-elastic state, preferably at temperatures below 200 ° C.
  • thermoplastic polyolefins such as various polystyrene grades such as standard polystyrene, impact polystyrene, polystyrene foams or copolymers of styrene and other monomers such as acrylonitrile or acrylonitrile-butadiene or acrylonitrile-styrene-acrylic ester are used.
  • thermoplastic elastomers such as styrene-butadiene-styrene block polymers , thermoplastic elastomers of ethylene and propylene, thermoplastic
  • the rubber polymers for example, 1,4-polyisoprene, polychloroprene, polybutadiene, styrene-butadiene rubber, nitrile rubber, butyl rubber, ethylene-propylene rubber having ethylidene norbornene content and polyoctenamer are preferred.
  • the resulting composite materials combine the advantages of both layers, namely the optical and other previously described properties of the molded articles with the mechanical and processing properties of the further sheetlike material.
  • the composite material exhibits the high elasticity and tear strength of the rubber and the optical and otherwise detectable properties of the molded articles described above.
  • thermoplastic materials as a further sheet material, a mechanical hardness and scratch resistance can be achieved, which can not have the moldings alone.
  • the obtained composite materials can be subjected to a complete or large-scale hot working.
  • the other sheetlike material which essentially determines the mechanical properties of the composite, may contain various additives, in particular colorants and fillers, but also the previously mentioned other contrast materials, nanoparticles and mechanically detectable materials in suitable concentration ,
  • the production of the composite materials takes place in such a way that at least one shaped body, which consists essentially of core-shell particles, is firmly connected to at least one further sheet-like material.
  • This can preferably be achieved by mechanical action, preferably by uniaxial pressing and / or by heating, by adhesive bonding.
  • the composite materials are in the form of laminates of at least two layers, wherein a layer is formed by a molding described above.
  • a layer of a core-shell particle shaped body described above is located between two further sheetlike materials, which may have identical or different compositions.
  • Such composites can be produced, for example, by pouring and injecting, laminating or laminating the various materials.
  • composites are also suitable which contain the optically variable shaped bodies as the upper layer.
  • the shaped bodies from core-sheath particles in a translucent form, so that information which is located in deeper layers of the layer composite can still be seen through the layer consisting of the shaped body.
  • the shaped bodies described above, or else the composite materials can also be comminuted to pigments of suitable size by cutting or breaking and optionally by subsequent grinding (preferably at very low temperatures, for example after cooling in liquid nitrogen or dry ice) this form for the production of security elements according to, used in the present invention.
  • the particulate fragments (pigments) from the Formkörpem from core-shell particles all properties, which have already been extensively described in advance for the moldings themselves.
  • the pigments thus produced can then be used in coating compositions, such as paints and printing inks, as precursors in the form of
  • Pigment blends, IVIasterbatches, pastes, pastes, granules, pellets and the like can be used to prepare security elements according to the present invention.
  • the printing methods customary for the production of security elements are preferably used in order, for example, to apply printing inks to suitable carrier materials.
  • incorporation of the pigments into plastic compositions can take place.
  • security elements can be produced which are optically variable and have at least one further detectable security feature.
  • Security products within the meaning of the present invention are value documents such as banknotes, checks, credit cards, shares, passports, identity documents, driver's licenses, entrance tickets, tokens, labels, packaging materials, seals and the like, but also objects to be protected for everyday use, such as clothing , Shoes, household items, household electronic articles and the like, wherein the security element produced according to the invention is preferably mounted directly on these objects.
  • the security element produced according to the invention can be wholly or partially applied to the security products or introduced into them.
  • the above-described molded article or a composite material produced therewith is in the form of a planar structure, this material can be the However, the surface of the security element to be produced thereby or be incorporated into the security element, for example in the form of stripes, dots, lines, alphanumeric characters, pictorial representations, etc., but may also form the security element as such, which may also take different forms.
  • the latter is in turn attached to the surface of the security products to be protected or incorporated into these, but may also represent the security product itself to be protected.
  • the shaped article or the composite material produced therewith is in the form of pigments
  • security products are produced therefrom which preferably contain these pigments in the form of imprints (which may likewise be differently shaped) or which consist at least partly of plastics into which the Pigments are incorporated.
  • FIG. 1 describes the angle-dependent colorimetric characterization of a shaped article according to the present invention, which has a color flop of red / orange over yellow / green to blue, with a device PE Lambda 900 with goniometer accessory
  • FIG. 2 describes the angle-dependent colorimetric characterization of an optically variable pigment on the black part of the color chart, which has a color flop from red / orange to yellow / green, with the same measuring instrument, for comparison

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Abstract

L'invention concerne l'utilisation de corps moulés constitués de particules à noyau et enveloppe pour produire des éléments de sécurité optiquement variables pour des produits de sécurité. Selon l'invention, les éléments de sécurité présentent simultanément un autre attribut de sécurité détectable, notamment un attribut de sécurité détectable de manière optique, mécanique ou haptique. L'invention concerne également des éléments de sécurité et des produits de sécurité fabriqués à partir de ces corps moulés.
PCT/EP2005/011380 2004-10-25 2005-10-24 Utilisation de corps moules constitues de particules a noyau et enveloppe WO2006045567A2 (fr)

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WO2008095481A2 (fr) * 2007-02-08 2008-08-14 Bundesdruckerei Gmbh Document de sécurité et/ou de valeur à cristal photonique
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WO2010091925A1 (fr) 2009-02-12 2010-08-19 Evonik Degussa Gmbh Cellule solaire de conversion de fluorescence et sa fabrication dans le procédé de coulée en plaques
WO2010118920A1 (fr) 2009-04-15 2010-10-21 Evonik Degussa Gmbh Cellule solaire à conversion de fluorescence-fabrication par moulage par injection
DE102009027431A1 (de) 2009-07-02 2011-01-05 Evonik Degussa Gmbh Fluoreszenzkonversionssolarzelle - Herstellung im Extrusionsverfahren oder im Coextrusionsverfahren
EP2284019A1 (fr) * 2009-06-22 2011-02-16 Polska Wytwornia Papierow Wartosciowych S.A. Papier sécurisé pour la gravure au laser, document sécurisé et procédé pour la fabrication de documents sécurisés
DE102010028186A1 (de) 2010-04-26 2011-10-27 Evonik Röhm Gmbh Fluoreszenzkonversionssolarzelle Lacke
DE102010028180A1 (de) 2010-04-26 2011-10-27 Evonik Röhm Gmbh Fluoreszenzkonversionssolarzelle - Herstellung im Extrusionslaminationsverfahren oder im Kleberlaminationsverfahren
WO2012013455A1 (fr) 2010-07-30 2012-02-02 Evonik Röhm Gmbh Pièce moulée en polyméthyl(meth)acrylate pour la conversion par fluorescence, leur fabrication par le procédé de coulée en plaque et leur utilisation dans des collecteurs solaires
EP2212121B1 (fr) 2007-10-19 2015-12-23 De La Rue International Limited Dispositif de sécurité à cristaux photoniques et procédé

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WO2007096291A1 (fr) * 2006-02-21 2007-08-30 Basf Se Utilisation de systèmes polymères colorés pour emballages
WO2008095481A2 (fr) * 2007-02-08 2008-08-14 Bundesdruckerei Gmbh Document de sécurité et/ou de valeur à cristal photonique
DE102007007029A1 (de) 2007-02-08 2008-08-14 Bundesdruckerei Gmbh Sicherheits- und/oder Wertdokument mit photonischem Kristall
WO2008095481A3 (fr) * 2007-02-08 2008-12-11 Bundesdruckerei Gmbh Document de sécurité et/ou de valeur à cristal photonique
CN101652800B (zh) * 2007-02-08 2013-02-06 联邦印刷厂有限公司 具有光子晶体的安全和/或有价文件
AU2016225899B2 (en) * 2007-02-08 2018-02-01 Bundesdruckerei Gmbh Safety and/or valuable document having a photonic crystal
WO2008141973A1 (fr) * 2007-05-18 2008-11-27 Unilever Plc Particules monodispersées
EP2212121B1 (fr) 2007-10-19 2015-12-23 De La Rue International Limited Dispositif de sécurité à cristaux photoniques et procédé
WO2010070678A1 (fr) * 2008-12-15 2010-06-24 Council Of Scientific & Industrial Research Produit optiquement variable à surface modifiée pour élément de sécurité
CN102282218A (zh) * 2008-12-15 2011-12-14 科学与工业研究委员会 用于防伪特征的表面修饰的光学可变产品
WO2010091925A1 (fr) 2009-02-12 2010-08-19 Evonik Degussa Gmbh Cellule solaire de conversion de fluorescence et sa fabrication dans le procédé de coulée en plaques
DE102009000813A1 (de) 2009-02-12 2010-08-19 Evonik Degussa Gmbh Fluoreszenzkonversionssolarzelle I Herstellung im Plattengußverfahren
DE102009002386A1 (de) 2009-04-15 2010-10-21 Evonik Degussa Gmbh Fluoreszenzkonversionssolarzelle - Herstellung im Spritzgussverfahren
WO2010118920A1 (fr) 2009-04-15 2010-10-21 Evonik Degussa Gmbh Cellule solaire à conversion de fluorescence-fabrication par moulage par injection
EP2284019A1 (fr) * 2009-06-22 2011-02-16 Polska Wytwornia Papierow Wartosciowych S.A. Papier sécurisé pour la gravure au laser, document sécurisé et procédé pour la fabrication de documents sécurisés
DE102009027431A1 (de) 2009-07-02 2011-01-05 Evonik Degussa Gmbh Fluoreszenzkonversionssolarzelle - Herstellung im Extrusionsverfahren oder im Coextrusionsverfahren
DE102010028180A1 (de) 2010-04-26 2011-10-27 Evonik Röhm Gmbh Fluoreszenzkonversionssolarzelle - Herstellung im Extrusionslaminationsverfahren oder im Kleberlaminationsverfahren
DE102010028186A1 (de) 2010-04-26 2011-10-27 Evonik Röhm Gmbh Fluoreszenzkonversionssolarzelle Lacke
DE102010038685A1 (de) 2010-07-30 2012-02-02 Evonik Röhm Gmbh Fluoreszenzkonversionssolarzelle Herstellung im Plattengußverfahren
WO2012013455A1 (fr) 2010-07-30 2012-02-02 Evonik Röhm Gmbh Pièce moulée en polyméthyl(meth)acrylate pour la conversion par fluorescence, leur fabrication par le procédé de coulée en plaque et leur utilisation dans des collecteurs solaires

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