The present application claims the benefit of the earlier filing date of 11 008 765.7 filed in the European Patent Office on Nov. 3, 2011, the entire content of which application is incorporated herein by reference.
The present application relates to a hologram as well as a device comprising such a hologram.
Holograms have become widely used to determine whether or not sovereign documents such as banknotes, passports, ID cards and other personalized documents as well as credit cards are genuine of fake. Further, holograms are used to secure brand products from counterfeit. Examples for holograms comprise emboss type holograms in which an interference film is unevenly formed as is, for example, described in US 2002/0191234. Further examples comprise volume type holograms, in which the refractive index of an interference film is spatially modulated. Furthermore, holographic sensors are known in which a volume hologram interacts with an external stimulus so that the appearance thereof is changed, as is, for example, described in WO 2010/094948.
Generally, electronic equipment is made to be used within specific environmental conditions. For example, mobile phones should be used within a specific temperature range and they should not be subject to water contact which can occur in events of rain or during a machine washing program. Cardiac pacemakers should not be used in strong magnetic fields and watches should not be used for diving to specific depths of the sea. When an electronic equipment has been used under these conditions, it may fail and the user may demand repair or replacement under the guarantee of the electronic equipment. Nevertheless, the warranty conditions do not apply if the electronic equipment has been used under conditions which are not covered by the warranty. In order to proove whether a specific electronic equipment has been used under damaging conditions or not it has become practice to attach various types of sensor labels on the electronic equipment. For example, it is common practice to provide mobile electronic equipment such as mobile phones, MP3 players and others with water-contact identification labels in order to provide evidence in case the mobile electronic equipment has been brought into contact with water, as is, for example, described in US 2007/0207295, U.S. Pat. No. 7,772,215, and U.S. Pat. No. 7,744,997.
It is an object of the present invention to provide an improved hologram as well as a device comprising such a hologram.
According to the present invention, the above objects are solved by the claimed matter according to the independent claims.
The accompanying drawings are included to provide a further understanding of embodiments of the invention and are incorporated in and constitute a part of this specification. The drawings illustrate the embodiments of the present invention and together with the description serve to explain the principles. Other embodiments of the invention and many of the intended advantages will be readily appreciated, as they become better understood by reference to the following detailed description. The elements of the drawings are not necessarily to scale relative to each other. Like reference numbers designate corresponding similar parts.
In the following detailed description reference is made to the accompanying drawings, which form a part hereof and in which are illustrated by way of illustration specific embodiments in which the invention may be practiced. In this regard, directional terminology such as “top”, “bottom”, “front”, “back”, “leading”, “trailing” etc. is used with reference to the orientation of the Figures being described. Since components of embodiments of the invention can be positioned in a number of different orientations, the directional terminology is used for purposes of illustration and is in no way limiting. It is to be understood that other embodiments may be utilized and structural or logical changes may be made without departing from the scope defined by the claims.
The holographic layer 14 may comprise a volume hologram, for example a transmission or a reflection hologram. Specific types of holograms are Lippmann holograms, Denisjuk holograms, RGB holograms, rainbow hologram, computer-generated or digital holograms. Generally, the holographic layer is a photosensitive material, in which due to irradiation with electromagnetic radiation a modulation of the refractive index takes place. Examples of photosensitive material are given in U.S. Pat. No. 7,824,822, U.S. Pat. No. 7,521,155, U.S. Pat. No. 5,702,846, and U.S. Pat. No. 5,453,340. The holographic layer may comprise a photosensitive composition such as (a) one or more free-radically polymerizable compounds, (b) one or more free-radical polymerization initiators, (c) one or more cationically polymerizable compounds other than (a), (d) one or more initiators for cationic polymerization and (e) optionally further components.
Examples of suitable free-radically polymerizable compounds (a) are acrylic-based monomers, styrene-based monomers and/or vinyl-based monomers. Specific monomers are acrylamide, methacrylamide, phenyl acrylate, 2 phenoxyethyl acrylate, mono(acryloyloxyethyl) naphthalenedicarboxylate, methylphenoxyethyl acrylate, nonylphenoxyethyl acrylate, acryloyloxyethyl hydrogenphthalate, phenoxy polyethylene glycol acrylate, 2,4,6 tribromophenyl acrylate, mono(2-methacryloyloxyethyl) diphenate, benzyl acrylate, 2,3-dibromophenyl acrylate, 2 hydroxy-3 phenoxypropyl acrylate, 2 naphthyl acrylate, N vinylcarbazole, 2 (9 carbazolyl)ethyl acrylate, triphenylmethyl triacrylate, 2-(tricyclo[5.2.1.02,6]dibromodecylthio)-ethyl acrylate, S (1 naphthylmethyl) thioacrylate, dicyclopentanyl acrylate, methylenebisacrylamide, polyethylene glycol diacrylate, trimethylpropane triacrylate, pentaerythritol acrylate, 2 acryloyloxy-ethyl 3-acryloyloxypropyl 2-hydroxydiphenate, 2 acryloyloxyethyl 3-acryloyloxypropyl 2-hydroxy-2,3-naphthalenedicarboxylate, 2- acryloyloxyethyl 3 acryloyloxypropyl 2-hydroxy-4,5-phenanthrenedi-carboxylate, dibromoneopentyl glycol diacrylate, dipentaerythritol hexaacrylate, 1,3-bis[2-acryloyloxy-3-(2,4,6-tribromophenoxy)propoxy]benzene, diethylene dithioglycol diacrylate, 2,2-bis(4-acryloyloxyethoxy-phenyl)propane, bis (4-acryloyloxydiethoxyphenyl)-methane, bis (4-acryloyloxyethoxy-3,5-dibromophenyl)-methane, 2,2-bis (4-acryoyloxyethoxyphenyl)propane, 2,2-bis (4-acryloyloxyethoxy-3,5-dibromophenyl)propane, bis(4-acryoyloxyethoxyphenyl) sulphone, bis(4-acryloyloxydiethoxyphenyl) sulphone, bis(4-acryloyloxypropoxy-phenyl) sulphone, bis(4-acryoyloxyethoxy-3,5-dibromo-phenyl) sulphone, styrene and 2-bromostyrene. It will be appreciated that it is also possible to use mixtures of a plurality of the compounds mentioned.
The initiators used for a free-radical polymerization (b) may be any desired free-radical-generating substances, for instance organic dyes with polymer salts, for example cyanines or salts of diphenyl-iodonium and diaryliodonium. Specific examples are anhydro-3,3′-dicarboxymethyl-9-ethyl-2,2′-thiacarbo-cyanine betaine, anhydro-3-carboxymethyl-3′,9-diethyl-2,2′-thiacarbocyanine betaine, 3,3′,9-triethyl-2,2′-thiacarbocyanine iodide, 3,9-diethyl-3′-carboxymethyl-2,2′-thiacarbocyanine iodide and 3,3′,9-triethyl-2,2′-(4,5,4′,5′,-dibenzo)thiacarbocyanine iodide, 2-[3-(3-ethyl-2-benzothiazolidene)-1-propenyl]-6-[2-(3-(3-ethyl-2-benzothiazolidene)ethylideneimino]-3-ethyl-1,3,5-thiadiazolium iodide, 2-[[3-allyl-4-oxo-5-(3-n propyl-5,6-dimethyl-2-benzothiazolidene)ethylidene-thiazolidene]methyl]3-ethyl-4,5-diphenylthiazolinium iodide, 1,1′,3,3,3′,3′-hexamethyl-2,2′-indon-tri-carbo-cyanine iodide, 3,3′-diethyl-2,2′-thiatricarbocyanine perchlorate, anhydro-1-ethyl-4-methoxy-3′-carboxy-methyl-5′-chloro-2,2′-quinothiacyanine betaine, anhydro-5,5′-diphenyl-9-ethyl-3,3′-disulphopropyloxa-carbocyanine hydroxide triethylamine salt. Specific examples of iodonium salts, for example halides, tetra-fluoro-borates or hexafluorophosphates, are diphenyliodonium, 4,4′-dichlorodiphenyliodonium, (4-methoxyphenyl)phenyl-iodonium, (4-octyloxyphenyl)phenyliodonium, 4,4′-dimethoxydiphenyliodonium, 4,4′-di-tert-butyldiphenyl-iodonium and 3,3′-dinitrodiphenyliodonium salts. It will be appreciated that it is also possible to use mixtures of a plurality of the compounds mentioned.
Component (c) of the photosensitive composition is one or more cationically polymerizable compounds. Examples are glycidyl-based compounds, epoxides or vinyl-based compounds. Specific monomers are diglycerol polyglycidyl ether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluoroisopropyl)cyclohexane, sorbitol polyglycidyl ether, trimethylolpropane poly-glycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, p-t-butyl-phenyl diglycidyl ether, diglycidyl adipate, diglycidyl o-phthalate, dibromophenyl glycidyl ether, dibromo-neopentyl glycol, glycol diglycidyl ether, 1,6-di-methylolperfluorohexane glycidyl ether, 1,2,7,8-di-epoxyoctane, 4,4′-bis (2,3-epoxypropoxyperfluoro-iso-propyl)diphenyl ether, 3,4-epoxycyclohexylmethyl 3′,4′-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyl-oxirane, 1,2,5,6-diepoxy-4,7-methaneperhydroindene, 2-(3,4-epoxycyclohexyl)-3′,4′-epoxy-1,3-dioxane-5-spiro-cyclohexane, 1,2 ethylenedioxybis(3,4-epoxycyclohexyl-methane), 4′,5′-epoxy-2′-methylcyclohexylmethyl 4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol bis (3,4-epoxycyclohexanecarboxylate), bis(3,4-epoxy-cyclohexylmethyl) adipate, di-2,3-epoxycyclopentyl ether, vinyl 2-chloroethyl ether, vinyl n-butyl ether, triethylene glycol divinyl ether, 1,4-cyclohexane-dimethanol divinyl ether, trimethylolethane trivinyl ether or vinyl glycidyl ether. It is also possible to use combinations of the abovementioned compounds.
Component (d) of the photosensitive composition is an initiator for a cationic polymerization. Suitable compounds here are those which, after decomposition, generate Bronsted or Lewis acids, for example diaryl-iodonium salts, triarylsulphonium salts, iron-allene salts and the like. Examples of diaryliodonium salts are tetrafluoroborates, hexafluorophosphates, hexafluoroarsenates and hexafluoroantimonates of iodonium compounds. Examples of triarylsulphonium salts are tetrafluoroborates, hexafluorophosphates, hexafluoroarsenates and hexafluoroantimonates of sulphonium or triphenylsulphonium compounds, for instance 4-tert-butyltriphenylsulphonium, tris(4-methylphenyl)sulphonium, tris (4-methoxyphenyl) sulphonium, 4-thiophenyltriphenyl-sulphonium. Combinations of a plurality of the compounds mentioned are also suitable.
The photosensitive composition may optionally comprise organic solvents, for example ketones, esters, ethers, dioxanes, hydrocarbons, for instance cyclohexane, halo-hydrocarbons, aromatics, alcohols or mixtures of one or more such solvents. It is also possible to use solvent-free photopolymer compositions. Further possible additives are binders, thermal polymerization inhibitors, silane coupling agents, plasticizers, dyes and/or copolymers. Further examples comprise lithium niobate, barium titanate, and gallium arsenide. Typical layer thicknesses of holographic material are 10 nm to 1 mm, specifically 100 nm to 100 μm, more specifically 1 μm to 50 μm. For example, a holographic layer may comprise a photopolymer in which upon irradiation with light, monomer particles are polymerized in the exposed portion. As the monomer particles are further polymerized, they move to the exposed portion. Thereby, the concentration of monomer particles varies by location. As a result, refractive index modulation occurs. Thereafter, when ultraviolet light or visible light is irradiated on the entire surface of the photopolymer, the monomer particles are completely polymerized. Thereby, a kind of “fixation step” takes place. Since the refractive index of the optical cured photopolymer varies with incident light, interference fringes (brightness and darkness) that occurred due to interference between reference and object illumination light can be recorded as changes of refractive index.
As has been explained above, the functional layer 17, 27 shown in
In the context of the present specification the term “water” comprises pure water, water with arbitrary additives as well as aqueous solutions. Specific examples comprise seawater or any kind of water that is present in a common environment. For example, upon contact with water, the functional layer 17, 27 may change its appearance, for example, it may become opaque. As a further example, the layer may change its color, for example, when the temperature exceeds a specific temperature range. For example, a color change may take place at a temperature of more than 60° C. or below −10° C., or when a portable hard disc has dropped onto a hard surface. Further, the functional layer 17, 27 may change its color, when being exposed to a strong magnetic field or when specific time from application to the substrate has been exceeded. Further, the layer may change its appearance after a contact with specific chemicals, for example when chemicals such as acid, alkylene, solvents are dispersed in air. Further, the functional layer may also change its appearance when a crash has taken place, for example, when the device has fallen to earth. Additionally, the functional layer may change its appearance, when a specific mechanical force has been applied, for example, when a watch has been used for diving to a specific depth of the sea.
The specific position of the functional layer 17, 27 depends on the function thereof. The functional layer 17, 27 may be disposed between the holographic layer 14, 24 and the substrate 10, 20 or may be disposed over the holographic layer 14, 24. For example, the functional layer may be a water contact indicator. In this case the functional layer 17, 27 may be disposed over the cover layer 18. Alternatively, the cover layer 18 may be replaced by the functional layer 17, 27. For example, the functional layer may comprise a combination of BaSO4, TiO2, cellulose and an indicator dye. Upon contact with water, the indicator dye will change its color so that it can be demonstrated that the holographic layer has been exposed to water. As a further example, the functional layer 17, 27 may comprise a water contact indicator including a coated or printed layer comprising a water soluble polymer which is encapsulated in a highly cross-linked matrix. Upon exposure to water the water soluble polymers swells or expands, however its complete dissolution is hindered by the encapsulating cross-linked matrix. Due to the binary phase aspect of the water impregnated layer an opacity results. The opacity is sufficient to block light when a selective visual or scanning reading of the hologram is performed. Furthermore, if the functional layer 17, 27 is printed, the image of the print can only be visually detected after exposure to water. Such a type of sensor is reliable and functions as a single layer that can easily be integrated into a holographic layer stack. The degree of swelling of the polymer and degree of cross-linking of the encapsulation can be tuned so that the opacity is specific to certain illumination wavelength. For example, blue and green light having a longer wavelength can be selectively blocked, whereas shorter wavelengths light such as red light can remain unaffected. This aspect may be useful in color change detection in full-color holograms.
Furthermore, the functional layer 17, 27 may detect temperature changes or changes in pH when using layers including a material that may be subject to an azo-coupling reaction. For example, the following materials may be employed, and the following reaction may take place upon a temperature change or a change in pH:
Further examples of the functional layer may comprise coupling reagents with specific color change chemistry and dependency on temperature, pH and light exposure. The nature of the polymer and/or formulation uses support the azo-dye coupling reagents can also influence the final color change and, more importantly, the rate of the color change. In this way, a graduated change can be detected directly corresponding to the extent of exposure to the stimuli. For example, polymers or additives that serve as acid generators or scavengers are particularly useful to regulate color changes.
As a further example, the functional layer 17, 27 may detect a strong magnetic field. In this case, for example, the functional layer may comprise a metal-based pigment or a pigment with a sufficient electric conductivity such as carbon black. The functional layer 17, 27 further comprises a gel-like coated or printed layer which serves as a carrier. The pigments are mobile within the carrier layer. Accordingly, a strong magnetic field serves to elevate the pigment to the uppermost surface of the sensor layer, whereby a reading or detection is enabled. In other words, when being exposed to a strong magnetic field, the functional layer 17, 27 having this construction will change its optical properties.
As a further example, the functional layer 17, 27 may be configured to detect exposure to heat. In this case, for example, the functional layer 17 may be implemented as a black film, for example, as a shrinking foil comprising voids. For example, the functional layer 17 may replace the black film 12 shown in
Further embodiments and modifications of the described hologram are easily conceiveable to the person skilled in the art.
According to a further embodiment, the functional layer 17, 27 may be attached to the holographic layer stack in such a manner that any kind of manipulation or replacement of this function layer will destroy the hologram. For example, the functional layer 17, 27 may be attached to the holographic layer 14, 24 by a strong adhesive so that it can not be removed from the holographic layer without damaging it. As a consequence, a manipulation of the functional layer such as replacing a colored functional layer by an uncolored one, is prevented.
According to a further embodiment, the functional layer 17, 27 may comprise more than one sub-layers. For example, the functional layer 17, 27 may comprise two sub-layers that react with each other when being exposed to the environmental influence to change the optical appearance thereof.
As is clearly to be understood, the holographic layer stack may as well comprise more than one functional layer. For example, the holographic layer stack may comprise a plurality of functional layers each reacting upon a different external stimulus. The hologram comprising the functional layer adds a further functionality to the security and/or functional label, and can be easily integrated into the layer stack. Hence, this hologram can save significant cost in manufacturing because one integrated label delivers security and functionality.
While embodiments of the invention have been described above, it is obvious that further embodiments may be implemented. For example, further embodiments may comprise any subcombination of features recited in the claims or any subcombination of elements described in the examples given above. Accordingly, this spirit and scope of the appended claims should not be limited to the description of the embodiments contained herein.
Number | Date | Country | Kind |
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11008765.7 | Nov 2011 | EP | regional |