The present application relates to a hologram as well as to a method of forming 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 or 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. In order to improve security, it is an important issue to protect the holograms themselves from making copies thereof.
It is an object of the present invention to provide an improved hologram as well as a method of forming a hologram having improved properties.
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 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.
For example, generally a volume or Lippmann type hologram may be manufactured by a content production step in which first an image to be shown in the hologram is formed by, for example, capturing images, converting the image into computer graphic images and editing the obtained images. Thereafter, a hologram master is produced so that a plurality of holograms may be manufactured by a simple copying step. For manufacturing a hologram master, interference fringes of object illumination light of an image and reference light are successively recorded in a holographic layer using production laser light. For example, a wavelength of 100 to 1000 nm, specifically 200 to 900 nm and more specifically 300 to 800 nm and further 400 to 700 nm may be used as production laser light. For copying the master, a further holographic layer is brought into contact with the master and copying laser light is irradiated thereto. The copying laser light can be identical with the production laser light or of a different spectrum. The laser light reflected by the hologram and the (reference) laser light interfere with each other to form interference fringes in the holographic layer. Thereby, the hologram is copied. 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-acryloyl-oxydiethoxyphenyl) 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′-indotricarbo-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-fluoroborates or hexafluorophosphates, are diphenyliodonium, 4,4′-dichlorodiphenyliodonium, (4-methoxyphenyl)phenyliodonium, (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-epoxypropoxyperfluoroiso-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 Brønsted or Lewis acids, for example diaryl-iodonium salts, triarylsulphonium salts, iron-allene salts and the like. Examples of diaryliodonium salts are tetrafluoroborates, hexafluorophosphates, hexa-fluoroarsenates and hexafluoroantimonates of iodonium compounds. Examples of triarylsulphonium salts are tetrafluoroborates, hexafluorophosphates, hexafluoro-arsenates 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.
A compound which may comprise an oxide, oxide sulphate or oxide fluoride of an alkali, earth alkali or transition element, lanthanide oxide, lanthanide oxide sulphate or lanthanide oxide fluoride. Optionally, the compound may comprise at least one further element selected from the group consisting of yttrium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Optionally, the compound may further comprise at least one dopant selected from oxides and/or fluorides of main group or transition group elements. As has been mentioned above, the second wavelength may be different from the first wavelength. Accordingly, so-called stokes or anti-stokes luminescent substances comprising lanthanoid compounds may be used. Examples thereof are described in WO 00/60527, WO 2008/000461, U.S. Pat. No. 6,802,992 and U.S. Pat. No. 6,686,074.
The luminescent material is incorporated before or after the step of developing the photopolymer. Accordingly, the photoluminescent material is disposed adjacent to one or both of the surfaces of the holographic layer. Thereafter, the holographic layer is further processed by applying the further layers by generally known processes. Then, the sheet-like layer stack will be cut into pieces to isolate the single holographic labels.
As has become apparent from
According to a further modification, the hologram may be manufactured utilizing more than one wavelength of the irradiating laser light. This kind of holograms sometimes is referred to RGB holograms (in the case of three manufacturing wavelengths) or rainbow holograms (in the case of a plurality of manufacturing wavelengths). In this case, a plurality of luminescent materials, each absorbing a specific wavelength of the manufacturing wavelengths may be selected and incorporated into the hologram, for example, the holographic layer or any other layer of the hologram layer stack. As a further option, a luminescent material absorbing a plurality of manufacturing wavelengths can be selected and incorporated into the hologram.
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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11 005 309.7 | Jun 2011 | EP | regional |