EP2409849A1 - Combination of a luminescent material with a hologram - Google Patents
Combination of a luminescent material with a hologram Download PDFInfo
- Publication number
- EP2409849A1 EP2409849A1 EP10170447A EP10170447A EP2409849A1 EP 2409849 A1 EP2409849 A1 EP 2409849A1 EP 10170447 A EP10170447 A EP 10170447A EP 10170447 A EP10170447 A EP 10170447A EP 2409849 A1 EP2409849 A1 EP 2409849A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- luminescent substance
- radiation
- volume hologram
- oxide
- radiation source
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
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- 229910001618 alkaline earth metal fluoride Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- GCTPMLUUWLLESL-UHFFFAOYSA-N benzyl prop-2-enoate Chemical compound C=CC(=O)OCC1=CC=CC=C1 GCTPMLUUWLLESL-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- DJUWPHRCMMMSCV-UHFFFAOYSA-N bis(7-oxabicyclo[4.1.0]heptan-4-ylmethyl) hexanedioate Chemical compound C1CC2OC2CC1COC(=O)CCCCC(=O)OCC1CC2OC2CC1 DJUWPHRCMMMSCV-UHFFFAOYSA-N 0.000 description 1
- KBWLNCUTNDKMPN-UHFFFAOYSA-N bis(oxiran-2-ylmethyl) hexanedioate Chemical compound C1OC1COC(=O)CCCCC(=O)OCC1CO1 KBWLNCUTNDKMPN-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000298 carbocyanine Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002872 contrast media Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- BOTLEXFFFSMRLQ-UHFFFAOYSA-N cyclopentyloxycyclopentane Chemical compound C1CCCC1OC1CCCC1 BOTLEXFFFSMRLQ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- 239000012955 diaryliodonium Chemical class 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 150000002012 dioxanes Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- ZINJLDJMHCUBIP-UHFFFAOYSA-N ethametsulfuron-methyl Chemical compound CCOC1=NC(NC)=NC(NC(=O)NS(=O)(=O)C=2C(=CC=CC=2)C(=O)OC)=N1 ZINJLDJMHCUBIP-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000009969 flowable effect Effects 0.000 description 1
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- BNRNAKTVFSZAFA-UHFFFAOYSA-N hydrindane Chemical compound C1CCCC2CCCC21 BNRNAKTVFSZAFA-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002601 lanthanoid compounds Chemical class 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- KHARCSTZAGNHOT-UHFFFAOYSA-L naphthalene-2,3-dicarboxylate Chemical compound C1=CC=C2C=C(C([O-])=O)C(C(=O)[O-])=CC2=C1 KHARCSTZAGNHOT-UHFFFAOYSA-L 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- WRAQQYDMVSCOTE-UHFFFAOYSA-N phenyl prop-2-enoate Chemical compound C=CC(=O)OC1=CC=CC=C1 WRAQQYDMVSCOTE-UHFFFAOYSA-N 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-M phthalate(1-) Chemical compound OC(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-M 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- GEKRJZFHLJNDQM-UHFFFAOYSA-N s-(naphthalen-1-ylmethyl) prop-2-enethioate Chemical compound C1=CC=C2C(CSC(=O)C=C)=CC=CC2=C1 GEKRJZFHLJNDQM-UHFFFAOYSA-N 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- WLOQLWBIJZDHET-UHFFFAOYSA-N triphenylsulfonium Chemical class C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 WLOQLWBIJZDHET-UHFFFAOYSA-N 0.000 description 1
- WUKMCKCDYKBLBG-UHFFFAOYSA-N tris(4-methoxyphenyl)sulfanium Chemical compound C1=CC(OC)=CC=C1[S+](C=1C=CC(OC)=CC=1)C1=CC=C(OC)C=C1 WUKMCKCDYKBLBG-UHFFFAOYSA-N 0.000 description 1
- QKFJVDSYTSWPII-UHFFFAOYSA-N tris(4-methylphenyl)sulfanium Chemical compound C1=CC(C)=CC=C1[S+](C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 QKFJVDSYTSWPII-UHFFFAOYSA-N 0.000 description 1
- 125000002221 trityl group Chemical group [H]C1=C([H])C([H])=C([H])C([H])=C1C([*])(C1=C(C(=C(C(=C1[H])[H])[H])[H])[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/14—Security printing
- B41M3/144—Security printing using fluorescent, luminescent or iridescent effects
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/40—Agents facilitating proof of genuineness or preventing fraudulent alteration, e.g. for security paper
- D21H21/44—Latent security elements, i.e. detectable or becoming apparent only by use of special verification or tampering devices or methods
- D21H21/48—Elements suited for physical verification, e.g. by irradiation
-
- G—PHYSICS
- G07—CHECKING-DEVICES
- G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
- G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
- G07D7/003—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using security elements
- G07D7/0032—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using security elements using holograms
-
- G—PHYSICS
- G07—CHECKING-DEVICES
- G07D—HANDLING OF COINS OR VALUABLE PAPERS, e.g. TESTING, SORTING BY DENOMINATIONS, COUNTING, DISPENSING, CHANGING OR DEPOSITING
- G07D7/00—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency
- G07D7/06—Testing specially adapted to determine the identity or genuineness of valuable papers or for segregating those which are unacceptable, e.g. banknotes that are alien to a currency using wave or particle radiation
- G07D7/12—Visible light, infrared or ultraviolet radiation
- G07D7/1205—Testing spectral properties
Definitions
- the invention relates to a composition for marking articles comprising a luminescent substance based on oxides, oxide sulfides and / or oxide fluorides of lanthanide ions and a holographic support for recording or reconstruction of a volume hologram.
- the luminescent substance has a characteristic emission spectrum and can be used in combination with the volume hologram for authentication and / or identification of products such as substances or mixtures of substances.
- a subject of the invention is a composition for marking articles, comprising (i) a luminescent substance comprising (a) an IR-stimulable component comprising at least one oxide, oxide sulfide or oxide fluoride of lanthanide ions, and (b) optionally one by UV Radiation excitable component and (ii) a holographic support for recording or reconstruction of a volume hologram.
- a luminescent substance comprising (a) an IR-stimulable component comprising at least one oxide, oxide sulfide or oxide fluoride of lanthanide ions, and (b) optionally one by UV Radiation excitable component and (ii) a holographic support for recording or reconstruction of a volume hologram.
- the possibilities for marking objects e.g. Construction or spare parts of electronic equipment, machinery, vehicles, aircraft, etc., packaging or containers, e.g. of pharmaceutical products, fashion items, documents, banknotes, etc. significantly improved.
- the possibility of information storage is also significantly increased.
- the composition according to the invention can be used to label Products in different ways.
- the luminescent substance can be introduced into the holographic carrier, it being possible for particles of the luminescent substance to be dispersed in the entire region of the carrier, in a part thereof or in individual layers thereof.
- the luminescent substance can also be arranged as a layer on one or both surfaces of the carrier.
- the luminescent substance is present separately from the carrier, so that luminescent substance and holographic carrier can be present in or on different regions of the product to be marked, wherein these two regions can be adjacent or separate from one another.
- Component (i) of the composition is a luminescent substance comprising (a) an IR-stimulable component comprising at least one oxide, oxide sulfide or oxide fluoride of lanthanide ions, and (b) optionally a UV-excitable component.
- Lanthanoid compounds for use as anti-Stokes luminescent substances are, for example, in WO 00/60527 .
- WO 2008/000461 as well as in the U.S. Patents 6,802,992 and 6 686 074 described, the contents of which are hereby incorporated by reference.
- These lanthanoid oxide sulfides can be used to label substances or mixtures of substances.
- Component (i) is an IR-radiation excitable component comprising an oxide, oxide sulfide or oxide fluoride of lanthanide ions.
- Component (b) is a UV-activatable component, which is conveniently an inorganic compound inert under ambient conditions, for example an optionally doped aluminate, which absorbs in the UV wavelength range and is characteristic of the compound Luminescence radiation, eg fluorescence radiation, emitted.
- Such compositions are the subject of the German patent application DE 10 2010 028 818.7 , the contents of which are expressly referred to.
- Component (a) is preferably a luminescent substance with "upconverter” and / or “anti-Stokes” properties.
- component (a) comprises an oxide, oxide or oxyfluoride of yttrium and an oxide, oxide or oxide fluoride of at least one, at least two or at least three further elements selected from lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium , Dysprosium, holmium, erbium, thulium, ytterbium and lutetium, and optionally at least one dopant selected from oxides and / or fluorides of main or subgroup elements.
- component (a) is a luminescent substance as in WO 2008/000461 described.
- the oxide, oxide sulfide or oxide fluoride of yttrium is preferably present in a proportion of ⁇ 85 mol% ⁇ 90 mol%, ⁇ 92 mol%, ⁇ 94 mol% or ⁇ 96 mol% , Further oxides, oxide sulfides or oxide fluorides are preferably present in a proportion of in each case up to 5 mol%, up to 3.5 mol% or up to 2 mol% based on the entire component (a).
- the further oxides, oxide sulfides or oxide fluorides are preferably selected from the oxides, oxide sulfides or oxide fluorides of erbium, ytterbium and of at least one further element, in particular of lutetium, gadolinium, holmium, thulium, dysprosium and / or europium.
- the oxides, oxide sulfides or oxide fluorides of erbium and ytterbium are preferably present in a proportion of 0.5-2 mol%, particularly preferably 1-2 mol% based on the total component (a).
- the further oxides, oxide sulfides or oxide fluorides are preferably used in minor proportions of, for example, 0.1-1 mol%, particularly preferably 0.1-0.5 mol%, based on the total component (a).
- component (a) of the luminescent substance besides the oxide, oxide sulfide or oxide fluoride of yttrium may contain oxides, oxide sulfides or oxide fluorides of 1, 2, 3, 4, 5, 6, 7 or even more other elements.
- Component (a) of the luminescent substance additionally additionally contains at least one dopant selected from oxides and / or fluorides of main or subgroup elements.
- the dopants are preferably present in a proportion of up to 5 mol%, more preferably of up to 2 mol%, even more preferably of up to 1 mol%, even more preferably of 0.05-1 mol% and most preferably from 0.1 to 0.2 mol% based on the entire component (a).
- a preferred dopant is a fluoride which may be exemplified by an alkaline earth metal fluoride or alkali metal fluoride, e.g. as potassium fluoride, can be used.
- the fluoride is preferably present in a proportion of 0.1-0.2 mol% based on the entire component (a).
- dopants are alkaline earth metals and / or subgroup elements which are in the form of cations which are twice or more positively charged, preferably in the form of oxides and / or fluorides.
- Particularly preferred dopants are calcium, zinc and / or titanium, for example in the form of the oxides calcium oxide, zinc oxide or titanium dioxide.
- the cationic dopants are preferably present in a proportion of 0.1-0.2 mol%, based on the total component (a).
- the IR-excitable component (a) of the luminescent substance (i) is characterized on the one hand by a high luminescence intensity and on the other hand by emission lines or peaks which are characteristic of the presence and the proportions of the individual fractions.
- Component (a) of the luminescent substance (i) can, as in WO 2008/000461 described produced.
- dopants for example of polyvalent cations and / or fluoride, causes drastic changes in the position and / or intensity of individual emission wavelengths. Furthermore, a strong increase in the total luminescence intensity is also found. It is believed that in addition to the two-photon absorption known in anti-Stokes materials, three-photon absorption also takes place.
- Component (b) of the luminescent substance (i) is a component which can be excited by UV radiation and emits a characteristic luminescence radiation after excitation. It is preferably an aluminate which is optionally doped with transition metal and / or lanthanide ions.
- Component (b) preferably contains an aluminate of alkaline earth metal ions, transition metal ions and / or lanthanide ions, preferably an aluminate of barium or magnesium or an aluminate of yttrium, optionally doped with Eu, Mn, Th and / or Cr ions.
- the location and / or intensity of the emission wavelengths can be varied.
- the UV sensitivity is increased.
- the dopant of component (b) is favorably present in a proportion of up to 10 mol%, up to 5 mol% or up to 1 mol% based on the entire component (b).
- the component (b) is favorably present in a total proportion of 1-30%, 5-20% or 8-12% based on the total weight of the components (a) and (b).
- the components (a) and / or (b) are present in the luminescent substance (i), preferably in crystalline form. Furthermore, it is preferred that the individual components consist of a single phase, for example a crystalline phase, which can be determined by X-ray diffractometric methods.
- the component (a) is particularly preferably in hexagonal crystalline form. If appropriate, the individual components (a) and / or (b) may also each consist of a mixture of a plurality of luminescent substances.
- the luminescent substance is usually present in the form of particles, the mean particle size being ⁇ 5 nm, in particular ⁇ 1 nm.
- the particle size is preferably in the range of 10 nm-100 ⁇ m, preferably 50 nm-50 ⁇ m, and particularly preferably about 100 nm-10 ⁇ m.
- the components (a) and (b) are preferably present in the luminescent substance (i) in a substantially homogeneous distribution, e.g. as a homogeneous distribution of particles, in particular of crystalline particles as described above before.
- This homogeneous distribution can be achieved by co-grinding the components in conventional milling equipment, e.g. Ball mills, can be achieved.
- Component (ii) of the agent according to the invention is a carrier for receiving or reconstructing a volume hologram.
- the carrier is a common carrier for volume holograms, eg a holographic film.
- the carrier may be a transparent or opaque carrier.
- the support may be of any size, eg from 1 mm 2 to 10 cm 2 . A usual size is about 15 x 20 mm.
- the shape of the carrier can be arbitrary, for example, round, rectangular, oval or irregular.
- the hologram may be a transmission or reflection (transmitted light) hologram. Specific types of holograms are Denisjuk holograms, RGB holograms, rainbow holograms, and computer-generated or digital holograms.
- the hologram contains stored data, information or interference patterns, for example in the form of one-dimensional or multidimensional barcodes, images, alphanumeric Characters, digital data bits or combinations thereof. The data may be stored in visible or invisible form.
- volume holograms The recording of volume holograms is performed by irradiating a photosensitive composition with coherent light at a reference wavelength or a reference wavelength combination.
- the reference wavelength is, for example, in the range of 100-1000 nm.
- Preferred materials for generating volume holograms are photosensitive compositions comprising polymerizable materials.
- the hologram can be recorded by an individualized irradiation, so that each individual hologram contains individual information.
- Preferred photosensitive compositions are in US 5,453,340 described, the disclosure of which is incorporated herein by reference.
- the photosensitive composition comprises (ii): (a) one or more radical polymerizable compounds, (b) one or more radical polymerization initiators, (c) one or more cationically polymerizable compounds other than (a), (d) one or several initiators for a cationic polymerization and (e) optionally further components.
- Suitable 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, (acryloxyethyl) naphthalenedicarboxylate monoester, methylphenoxyethyl acrylate, nonylphenoxyethyl acrylate, ⁇ -acryloxyetyl hydrogenphthalate, phenoxypolyethylene glycol acrylate, 2,4,6-tribromophenyl acrylate, (2-methacryloxyethyl) diphenate monoester, benzyl acrylate, 2 , 3-Dibromophenyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-naphthyl acrylate, N-vinylcarbazole, 2- (9-carbazole) ethyl acrylate, triphen
- any radical-generating substances such as organic dyes with polymer salts, eg, cyanines or salts of diphenyliodonium and diaryliodonium, can be used.
- organic dyes with polymer salts eg, cyanines or salts of diphenyliodonium and diaryliodonium
- cyanines or salts of diphenyliodonium and diaryliodonium can be used.
- Specific examples are anhydro-3,3'-dicarboxymethyl-9-ethyl-2,2'-thiacarbocyanine 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-trieth
- Component (c) of the photosensitive composition (ii) is one or more cationically polymerizable compounds.
- examples are glycidyl-based compounds, epoxides or vinyl-based compounds.
- Specific monomers are Diglycerolpolyglycidylether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluorisopropyl) cyclohexane, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, pt-Butylphenyldiglycidylether, diglycidyl adipate, diglycidyl o-phthalate, dibromophenyl
- Component (d) of the photosensitive composition (ii) is an initiator of cationic polymerization.
- compounds which produce Br Zernstedt or Lewis acids after decomposition for example Diaryliodoniumsalze, Triarylsulfonsalze, Eisenallensalze and the like.
- diaryliodonium salts are tetrafluoroborates, hexafluorophosphates, Hexafluoroarsenates and hexafluoroantimonates of iodonium compounds.
- triarylsulfone salts are tetrafluoroborates, hexafluorophosphates, hexafluoroarsenates and hexafluoroantimonates of sulfonium or triphenylsulfonium compounds such as 4-tert-butyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, tris (4-methoxyphenyl) sulfonium, 4-thiophenyltriphenylsulfonium. Combinations of several of the compounds mentioned are suitable.
- the photosensitive composition may optionally contain organic solvents, e.g. Ketones, esters, ethers, dioxanes, hydrocarbons such as cyclohexane, halogenated hydrocarbons, aromatics, alcohols or mixtures of one or more such solvents.
- organic solvents e.g. Ketones, esters, ethers, dioxanes, hydrocarbons such as cyclohexane, halogenated hydrocarbons, aromatics, alcohols or mixtures of one or more such solvents.
- Solventless photopolymer compositions can also be used.
- Further possible additives are binders, thermopolymerization inhibitors, silane coupling agents, plasticizers, dyes and / or copolymers.
- the recording and reconstruction of a volume hologram from a photosensitive composition can be carried out by known methods using coherent light radiation, eg laser light, such as in US 5,453,340 described, done. Other methods for producing holograms are in US 2009/286165 A described. The disclosure of this document is expressly incorporated by reference.
- the combination of luminescent substance and holographic support can be used for authentication or identification, for example as security marking of objects, eg substances or mixtures of substances. In this way, the authenticity of products or documents can be determined.
- the holographic support is usually mounted on a surface of the object to be marked. This can be done, for example, by using adhesive material. Alternatively, however, the holographic support can also be incorporated into the surface of the article to be coated.
- the Luminescent substance can be introduced into the carrier and / or be present as a layer on the upper and / or lower surface of the carrier, for example in an adhesive material used for binding the carrier to the article.
- the luminescent substance can also be applied separately from the carrier in or on the object. In this case, the luminescent substance and the carrier may be present side by side, for example in adjoining relation, or on different, spatially separated regions of the article.
- the data or information present in the luminescent substance and in the hologram can be correlated with one another.
- the data may also be associated with an external data carrier, e.g. an optical disc, a FLASH memory or an RFID.
- the luminescent substance can be introduced into or applied to any solid and / or liquid substances or substance mixtures.
- the luminescent substance can be applied to carrier substances, such as paints, toners, inks, paints, etc., or into products, such as plastics, metals, glass, silicones, paper, rubber, medicaments, etc.
- carriers substances such as paints, toners, inks, paints, etc.
- products such as plastics, metals, glass, silicones, paper, rubber, medicaments, etc.
- objects can be provided with a coating of the luminescent substance on its surface or parts thereof which have a layer thickness of, for example, 1-10 ⁇ m, preferably 1-5 ⁇ m.
- the luminescent substance is added to the product or a portion of the product in an amount of 20-2000 ppm, preferably 50-200 ppm.
- the luminescent substance according to the invention is suitable for use in biological systems, eg cell cultures, samples from body fluids or tissue sections or as a contrast agent.
- the luminescent substance can be coupled in nano- or microparticulate form to biological detection reagents.
- the surfaces of particles of the luminescent substance may be modified with deodetomines or other adhesive substances to provide the suspending properties, for example, in organic liquids such as oils, gasolines, liquefied gases etc., in aqueous fluids such as body fluids, in aqueous-organic fluid systems and flowable powders such as toners.
- the smaller the particles the lower their tendency to sedimentation.
- intensive grinding for example, the particle size can be reduced so far, for example to ⁇ 100 nm, that a stable suspension of the particles in liquids is achieved even without the addition of adhesive substances.
- An anti-counterfeiting of the marking is given by the fact that the emission lines characteristic of the respective luminescent substance represent a cryptographic key which can be compared to a detector adapted to the respective substance, i. the castle can be detected.
- the combination of the holographic support with the luminescent substance represents a further significant improvement in the anti-counterfeiting security of the marking.
- the luminescent substance preferably contains two components which can be excited to luminescence by radiation in different wavelength ranges.
- component (a) can be excited to luminescence with IR radiation in the range of 850-1500 nm, in particular of 920-1000 nm, and / or component (b) with UV radiation in the range of 350-420 nm, especially from 380-410 nm, are excited to luminescence.
- the presence of the luminescent substance in an article is detected by irradiation with two wavelengths.
- a first wavelength in the infrared range in particular with IR monochromatic laser light or with an IR light emitting diode with wavelengths between about 850 nm and 1500 nm, preferably between about 920 nm and 1000 nm, more preferably between about 950 nm and 1000 nm, most preferably between 920 nm and 985 nm, wherein component (a) is excited and the resulting emission radiation approximately in the range between 300 nm and 1700 nm, in particular between 350 nm and 1000 nm is detected.
- the irradiation of component (a) is preferably carried out with a power of 1-200 mW, in particular 10-80 mW.
- a second wavelength in the UV range in particular with UV monochromatic laser light or with a UV light emitting diode with wavelengths between about 350 nm and 450 nm, preferably between about 380 nm and 400 nm is used, wherein the Component (b) excited and the emission radiation by eg Fluorescence is detected in the range between 300 nm and 1700 nm, in particular between 350 nm and 1000 nm.
- the irradiation of component (b) is preferably carried out with a power of 2-50 mW, in particular 5-30 mW.
- the components (a) and (b) of the luminescent substance are separately excited to luminescence by irradiation with a wavelength in the IR range and by irradiation with a wavelength in the UV range, and the emission radiation of components (a) and ( b) is detected separately.
- the excitation of component (a) and component (b) may be sequential, i. take place at different times, preferably first the component (a) and then the component (b) is excited.
- the reconstruction of the image produced by the holographic support may be carried out in a conventional manner by irradiation e.g. with a wavelength identical to the reference wave used to record the hologram.
- This wavelength can be in the range between 100-1000 nm and especially between 220-600 nm, e.g. at 266 nm, 405 nm or 530 nm.
- the wavelength may be identical to or different from a wavelength used to excite the luminescent substance.
- the Emission radiation of the luminescent substance are detected digitally together with the signal derived from the holographic carrier.
- digitized signals of the components (a) and (b) of the luminescent substance and of the hologram originating signals or parts of these signals (eg signals of individual peaks) can be converted by cryptographic measures using appropriate algorithms into a new signal.
- the data density can be increased by a factor of up to about 10 6 or more.
- the radiation sources are preferably each laser.
- the readout system preferably further contains a contact sensor, for example an optical contact sensor, which controls the radiation sources, so that activation of the radiation source takes place only when the readout system contacts a sample to be determined.
- a contact sensor for example an optical contact sensor, which controls the radiation sources, so that activation of the radiation source takes place only when the readout system contacts a sample to be determined.
- the irradiation of the product containing the luminescent substance by the readout system can be carried out directly with an optical waveguide or another optically relevant transfer medium, eg a solid optical body, a fluid, gas, etc.
- the detection can be done visually or by means of detectors.
- optical waveguides whose heads are ground as a converging lens, so that incident light (IR or UV light) and light emitted by the luminescent substance (specific emission spectrum) form a unit and can be focused at the same point.
- incident light IR or UV light
- light emitted by the luminescent substance specifically emission spectrum
- An advantage of this is that no mechanical misalignment between receiver and transmitter can take place.
- the attenuation factor of the optical fiber e.g. made of glass or plastic, may vary, the transition from the optical components (radiation source or detection element) to the optical waveguide being mounted with little covision.
- the length of the optical fiber may vary and is typically between 1 cm and 50 cm.
- the readout system further includes one or more optical detection elements which are used for the selective detection of the authenticity of the luminescent substance, e.g. in terms of wavelength and / or intensity, and the hologram are provided.
- the detection elements may be, for example, diodes, photoelements or electronic detectors.
- detector matrices are used with a plurality of detectors preferably set differently, e.g. Diodes, photoelements or CCD matrices.
- the detectors of the detector array may be equipped with a spectrometer and / or optical filters, e.g. Bandpass filters, combined.
- the readout system may also include a programmable electronic unit that enables digital evaluation and conditioning of the measurement signal.
- the readout system of the present invention is desirably used in conjunction with a combination of luminescent composition and volume hologram as previously described.
- step (b) first the irradiation in the IR range and then the irradiation in the UV range.
- step (d) comprises digital processing of the measurement signal or parts thereof.
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Abstract
Description
Die Erfindung betrifft eine Zusammensetzung zur Markierung von Erzeugnissen, umfassend einen Lumineszenzstoff, basierend auf Oxiden, Oxidsulfiden und/oder Oxidfluoriden von Lanthanoidionen und einen holografischen Träger zur Aufnahme oder Rekonstruktion eines Volumenhologramms. Der Lumineszenzstoff weist ein charakteristisches Emissionsspektrum auf und kann in Kombination mit dem Volumenhologramm zur Authentifizierung und/oder Identifizierung von Erzeugnissen wie etwa Stoffen oder Stoffgemischen eingesetzt werden.The invention relates to a composition for marking articles comprising a luminescent substance based on oxides, oxide sulfides and / or oxide fluorides of lanthanide ions and a holographic support for recording or reconstruction of a volume hologram. The luminescent substance has a characteristic emission spectrum and can be used in combination with the volume hologram for authentication and / or identification of products such as substances or mixtures of substances.
Ein Gegenstand der Erfindung ist eine Zusammensetzung zur Markierung von Erzeugnissen, umfassend (i) einen Lumineszenzstoff, enthaltend (a) eine durch IR-Strahlung anregbare Komponente, umfassend zumindest ein Oxid, Oxidsulfid oder Oxidfluorid von Lanthanoidionen, und (b) gegebenenfalls eine durch UV-Strahlung anregbare Komponente und (ii) einen holografischen Träger zur Aufnahme oder Rekonstruktion eines Volumenhologramms.A subject of the invention is a composition for marking articles, comprising (i) a luminescent substance comprising (a) an IR-stimulable component comprising at least one oxide, oxide sulfide or oxide fluoride of lanthanide ions, and (b) optionally one by UV Radiation excitable component and (ii) a holographic support for recording or reconstruction of a volume hologram.
Durch Verwendung der Kombination eines Lumineszenzstoffes und eines holografischen Trägers werden die Möglichkeiten zur Markierung von Gegenständen, z.B. Bau- oder Ersatzteilen von elektronischen Geräten, Maschinen, Fahrzeugen, Flugzeugen etc., Verpackungen oder Behältern, z.B. von pharmazeutischen Produkten, Modeartikeln, Dokumenten, Banknoten etc. erheblich verbessert. Durch eine gleichzeitige Authentifizierung des Lumineszenzstoffes und des Hologramms wird zudem die Möglichkeit der Informationsspeicherung deutlich vergrößert.By using the combination of a luminescent substance and a holographic support, the possibilities for marking objects, e.g. Construction or spare parts of electronic equipment, machinery, vehicles, aircraft, etc., packaging or containers, e.g. of pharmaceutical products, fashion items, documents, banknotes, etc. significantly improved. By simultaneously authenticating the luminescent substance and the hologram, the possibility of information storage is also significantly increased.
Die erfindungsgemäße Zusammensetzung kann zur Markierung von Erzeugnissen auf unterschiedliche Art und Weise eingesetzt werden. So kann z.B. der Lumineszenzstoff in den holografischen Träger eingebracht sein, wobei Partikel des Lumineszenzstoffes im gesamten Bereich des Trägers, in einem Teil davon oder in einzelnen Schichten davon dispergiert sein können. Darüber hinaus kann der Lumineszenzstoff auch als Schicht auf einer oder beiden Oberflächen des Trägers angeordnet sein. Noch eine weitere Möglichkeit besteht darin, dass der Lumineszenzstoff separat vom Träger vorliegt, so dass Lumineszenzstoff und holografischer Träger in oder auf verschiedenen Bereichen des zu markierenden Erzeugnisses vorliegen können, wobei diese beiden Bereiche benachbart oder voneinander getrennt sein können.The composition according to the invention can be used to label Products in different ways. Thus, for example, the luminescent substance can be introduced into the holographic carrier, it being possible for particles of the luminescent substance to be dispersed in the entire region of the carrier, in a part thereof or in individual layers thereof. In addition, the luminescent substance can also be arranged as a layer on one or both surfaces of the carrier. Yet another possibility is that the luminescent substance is present separately from the carrier, so that luminescent substance and holographic carrier can be present in or on different regions of the product to be marked, wherein these two regions can be adjacent or separate from one another.
Komponente (i) der Zusammensetzung ist ein Lumineszenzstoff enthaltend (a) eine durch IR-Strahlung anregbare Komponente, umfassend zumindest ein Oxid, Oxidsulfid oder Oxidfluorid von Lanthanoidionen, und (b) gegebenenfalls eine durch UV-Strahlung anregbare Komponente.Component (i) of the composition is a luminescent substance comprising (a) an IR-stimulable component comprising at least one oxide, oxide sulfide or oxide fluoride of lanthanide ions, and (b) optionally a UV-excitable component.
Lanthanoidverbindungen zur Verwendung als Antistokes-Lumineszenzstoffen sind beispielsweise in
Bevorzugt ist die Verwendung von Lumineszenzstoffen (i), die zwei in verschiedenen Wellenlängenbereichen anregbare Komponenten (a) und (b) enthalten. Komponente (a) ist eine durch IR-Strahlung anregbare Komponente, umfassend ein Oxid, Oxidsulfid oder Oxidfluorid von Lanthanoidionen. Komponente (b) ist eine durch UV-Strahlung anregbare Komponente, bei der es sich günstigerweise um eine unter Umgebungsbedingungen inerte anorganische Verbindung, z.B. ein gegebenenfalls dotiertes Aluminat, handelt, das im UV-Wellenlängenbereich absorbiert und eine für die Verbindung charakteristische Lumineszenzstrahlung, z.B. Fluoreszenzstrahlung, emittiert. Derartige Zusammensetzungen sind Gegenstand der deutschen Patentanmeldung
Komponente (a) ist vorzugsweise ein Lumineszenzstoff mit "Upconverter"-und/oder "Antistokes"-Eigenschaften. Vorzugsweise enthält die Komponente (a) ein Oxid, Oxidsulfid oder Oxidfluorid von Yttrium und ein Oxid, Oxidsulfid oder Oxidfluorid von mindestens einem, mindestens zwei oder mindestens drei weiteren Elementen ausgewählt aus Lanthan, Cer, Praseodym, Neodym, Samarium, Europium, Gadolinium, Terbium, Dysprosium, Holmium, Erbium, Thulium, Ytterbium und Lutetium sowie gegebenenfalls mindestens einen Dotierstoff, ausgewählt aus Oxiden und/oder Fluoriden von Haupt- oder Nebengruppenelementen. Beispielsweise handelt es sich bei Komponente (a) um einen Lumineszenzstoff wie in
In der gesamten Komponente (a) liegt das Oxid, Oxidsulfid oder Oxidfluorid von Yttrium vorzugsweise in einem Anteil von ≥ 85 mol-% ≥ 90 mol-%, ≥ 92 mol-%, ≥ 94 mol-% oder ≥ 96 mol-% vor. Weitere Oxide, Oxidsulfide oder Oxidfluoride liegen vorzugsweise in einem Anteil von jeweils bis zu 5 mol-%, bis zu 3,5 mol-% oder bis zu 2 mol-% bezogen auf die gesamte Komponente (a) vor. Vorzugsweise sind die weiteren Oxide, Oxidsulfide oder Oxidfluoride ausgewählt aus den Oxiden, Oxidsulfiden oder Oxidfluoriden von Erbium, Ytterbium und von mindestens einem weiteren Element, insbesondere von Lutetium, Gadolinium, Holmium, Thulium, Dysprosium und/oder Europium. Die Oxide, Oxidsulfide oder Oxidfluoride von Erbium und Ytterbium liegen vorzugsweise in einem Anteil von jeweils 0,5-2 mol-%, besonders bevorzugt von 1-2 mol-% bezogen auf die gesamte Komponente (a) vor. Die weiteren Oxide, Oxidsulfide oder Oxidfluoride werden vorzugsweise in geringeren Anteilen von beispielsweise 0,1-1 mol-%, besonders bevorzugt 0,1-0,5 mol-% bezogen auf die gesamte Komponente (a) verwendet.In the entire component (a), the oxide, oxide sulfide or oxide fluoride of yttrium is preferably present in a proportion of ≥85 mol% ≥90 mol%, ≥92 mol%, ≥94 mol% or ≥96 mol% , Further oxides, oxide sulfides or oxide fluorides are preferably present in a proportion of in each case up to 5 mol%, up to 3.5 mol% or up to 2 mol% based on the entire component (a). The further oxides, oxide sulfides or oxide fluorides are preferably selected from the oxides, oxide sulfides or oxide fluorides of erbium, ytterbium and of at least one further element, in particular of lutetium, gadolinium, holmium, thulium, dysprosium and / or europium. The oxides, oxide sulfides or oxide fluorides of erbium and ytterbium are preferably present in a proportion of 0.5-2 mol%, particularly preferably 1-2 mol% based on the total component (a). The further oxides, oxide sulfides or oxide fluorides are preferably used in minor proportions of, for example, 0.1-1 mol%, particularly preferably 0.1-0.5 mol%, based on the total component (a).
Beispielsweise kann die Komponente (a) des Lumineszenzstoffes neben dem Oxid, Oxidsulfid oder Oxidfluorid von Yttrium Oxide, Oxidsulfide oder Oxidfluoride von 1, 2, 3, 4, 5, 6, 7 oder noch mehr weiteren Elementen enthalten.For example, component (a) of the luminescent substance besides the oxide, oxide sulfide or oxide fluoride of yttrium may contain oxides, oxide sulfides or oxide fluorides of 1, 2, 3, 4, 5, 6, 7 or even more other elements.
Komponente (a) des Lumineszenzstoffes enthält zusätzlich zusätzlich mindestens einen Dotierstoff ausgewählt aus Oxiden und/oder Fluoriden von Haupt- oder Nebengruppenelementen. Die Dotierstoffe liegen vorzugsweise in einem Anteil jeweils bis zu 5 mol-%, besonders bevorzugt von jeweils bis zu 2 mol-%, noch mehr bevorzugt von jeweils bis zu 1 mol-%, noch mehr bevorzugt von 0,05-1 mol-% und am meisten bevorzugt von 0,1-0,2 mol-% bezogen auf die gesamte Komponente (a) vor.Component (a) of the luminescent substance additionally additionally contains at least one dopant selected from oxides and / or fluorides of main or subgroup elements. The dopants are preferably present in a proportion of up to 5 mol%, more preferably of up to 2 mol%, even more preferably of up to 1 mol%, even more preferably of 0.05-1 mol% and most preferably from 0.1 to 0.2 mol% based on the entire component (a).
Ein bevorzugter Dotierstoff ist ein Fluorid, das beispielsweise als ein Erdalkalimetallfluorid oder als Alkalimetallfluorid, z.B. als Kaliumfluorid, eingesetzt werden kann. Das Fluorid liegt vorzugsweise in einem Anteil 0,1-0,2 mol-% bezogen auf die gesamte Komponente (a) vor.A preferred dopant is a fluoride which may be exemplified by an alkaline earth metal fluoride or alkali metal fluoride, e.g. as potassium fluoride, can be used. The fluoride is preferably present in a proportion of 0.1-0.2 mol% based on the entire component (a).
Weitere bevorzugte Dotierstoffe sind Erdalkalimetalle und/oder Nebengruppenelemente, die als zweifach oder noch höher positiv geladene Kationen, vorzugsweise in Form von Oxiden und/oder Fluoriden vorliegen. Besonders bevorzugte Dotierstoffe sind Calcium, Zink und/oder Titan, beispielsweise in Form der Oxide Calciumoxid, Zinkoxid bzw. Titandioxid. Die kationischen Dotierstoffe liegen vorzugsweise in einem Anteil von jeweils 0,1-0,2 mol-% bezogen auf die gesamte Komponente (a) vor.Further preferred dopants are alkaline earth metals and / or subgroup elements which are in the form of cations which are twice or more positively charged, preferably in the form of oxides and / or fluorides. Particularly preferred dopants are calcium, zinc and / or titanium, for example in the form of the oxides calcium oxide, zinc oxide or titanium dioxide. The cationic dopants are preferably present in a proportion of 0.1-0.2 mol%, based on the total component (a).
Die IR-anregbare Komponente (a) des Lumineszenzstoffes (i) zeichnet sich einerseits durch eine hohe Lumineszenzintensität und andererseits durch Emissionslinien bzw. -peaks aus, die für das Vorhandenseins und die Anteile der einzelnen Anteile charakteristisch sind. So können durch spezifische Kombinationen von Oxiden, Oxidsulfiden oder Oxidfluoriden mit Dotierstoffen eine praktisch unbegrenzte Zahl verschiedener Emissionsspektren erzeugt werden.The IR-excitable component (a) of the luminescent substance (i) is characterized on the one hand by a high luminescence intensity and on the other hand by emission lines or peaks which are characteristic of the presence and the proportions of the individual fractions. Thus, by specific combinations of oxides, oxide sulfides or oxide fluorides with dopants, a virtually unlimited number of different emission spectra can be generated become.
Komponente (a) des Lumineszenzstoffes (i) kann wie in
Komponente (b) des Lumineszenzstoffes (i) ist eine durch UV-Strahlung anregbare Komponente, die nach Anregung eine charakteristische Lumineszenzstrahlung emittiert. Es handelt sich dabei vorzugsweise um ein Aluminat, das gegebenenfalls mit Übergangsmetall- und/oder Lanthanoidionen dotiert ist. Vorzugsweise enthält Komponente (b) ein Aluminat von Erdalkalimetallionen, Übergangsmetallionen und/oder Lanthanoidionen, vorzugsweise ein Aluminat von Barium oder Magnesium oder ein Aluminat von Yttrium, gegebenenfalls dotiert mit Eu-, Mn-, Th-und/oder Cr-lonen. Durch Einstellung der Stöchiometrie von Erdalkalimetall-, Übergangsmetall- und/oder Lanthanoidionen im Aluminat kann die Lage und/oder Intensität der Emissionswellenlängen variiert werden. Durch Dotierung mit Übergangsmetall- und/oder Lanthanoidionen wird die UV-Sensibilität gesteigert. Der Dotierstoff der Komponente (b) liegt günstigerweise in einem Anteil von bis zu 10 mol-%, bis zu 5 mol-% oder bis zu 1 mol-% bezogen auf die gesamte Komponente (b) vor.Component (b) of the luminescent substance (i) is a component which can be excited by UV radiation and emits a characteristic luminescence radiation after excitation. It is preferably an aluminate which is optionally doped with transition metal and / or lanthanide ions. Component (b) preferably contains an aluminate of alkaline earth metal ions, transition metal ions and / or lanthanide ions, preferably an aluminate of barium or magnesium or an aluminate of yttrium, optionally doped with Eu, Mn, Th and / or Cr ions. By adjusting the stoichiometry of alkaline earth metal, transition metal and / or lanthanide ions in the aluminate, the location and / or intensity of the emission wavelengths can be varied. By doping with transition metal and / or lanthanide ions, the UV sensitivity is increased. The dopant of component (b) is favorably present in a proportion of up to 10 mol%, up to 5 mol% or up to 1 mol% based on the entire component (b).
Die Komponente (b) liegt günstigerweise in einem Gesamtanteil von 1-30 %, 5-20 % oder 8-12 % bezogen auf das Gesamtgewicht der Komponenten (a) und (b) vor.The component (b) is favorably present in a total proportion of 1-30%, 5-20% or 8-12% based on the total weight of the components (a) and (b).
Die Komponenten (a) und/oder (b) liegen im Lumineszenzstoff (i) vorzugsweise in kristalliner Form vor. Weiterhin ist bevorzugt, dass die einzelnen Komponenten aus einer einzigen Phase, beispielsweise einer kristallinen Phase bestehen, die durch röntgendiffraktometrische Methoden bestimmt werden kann. Besonders bevorzugt liegt die Komponente (a) in hexagonal kristalliner Form vor. Gegebenenfalls können die einzelnen Komponenten (a) und/oder (b) auch jeweils aus einer Mischung mehrerer Lumineszenzstoffe bestehen.The components (a) and / or (b) are present in the luminescent substance (i), preferably in crystalline form. Furthermore, it is preferred that the individual components consist of a single phase, for example a crystalline phase, which can be determined by X-ray diffractometric methods. The component (a) is particularly preferably in hexagonal crystalline form. If appropriate, the individual components (a) and / or (b) may also each consist of a mixture of a plurality of luminescent substances.
Der Lumineszenzstoff liegt üblicherweise in Form von Partikeln vor, wobei die mittlere Partikelgröße ≥ 5 nm, insbesondere ≥ 1 nm ist. Vorzugsweise liegt die Partikelgröße im Bereich von 10 nm-100 µm, vorzugsweise von 50 nm-50 µm und besonders bevorzugt von etwa 100 nm-10 µm.The luminescent substance is usually present in the form of particles, the mean particle size being ≥ 5 nm, in particular ≥ 1 nm. The particle size is preferably in the range of 10 nm-100 μm, preferably 50 nm-50 μm, and particularly preferably about 100 nm-10 μm.
Die Komponenten (a) und (b) liegen im Lumineszenzstoff (i) vorzugsweise in einer im wesentlichen homogenen Verteilung, z.B. als homogene Verteilung von Partikeln, insbesondere von kristallinen Partikeln wie zuvor beschrieben, vor. Diese homogene Verteilung kann durch gemeinsames Mahlen der Komponenten in üblichen Mahlvorrichtungen, z.B. Kugelmühlen, erreicht werden.The components (a) and (b) are preferably present in the luminescent substance (i) in a substantially homogeneous distribution, e.g. as a homogeneous distribution of particles, in particular of crystalline particles as described above before. This homogeneous distribution can be achieved by co-grinding the components in conventional milling equipment, e.g. Ball mills, can be achieved.
Komponente (ii) des erfindungsgemäßen Mittels ist ein Träger zur Aufnahme oder Rekonstruktion eines Volumenhologramms. Der Träger ist ein üblicher Träger für Volumenhologramme, z.B. ein holografischer Film. Der Träger kann ein transparenter oder undurchsichtiger Träger sein. Der Träger kann eine beliebige Größe, z.B. von 1 mm2 bis zu 10 cm2 aufweisen. Eine übliche Größe ist etwa 15 x 20 mm. Die Form des Trägers kann beliebig, z.B. rund, rechteckig, oval oder unregelmäßig sein.Component (ii) of the agent according to the invention is a carrier for receiving or reconstructing a volume hologram. The carrier is a common carrier for volume holograms, eg a holographic film. The carrier may be a transparent or opaque carrier. The support may be of any size, eg from 1 mm 2 to 10 cm 2 . A usual size is about 15 x 20 mm. The shape of the carrier can be arbitrary, for example, round, rectangular, oval or irregular.
Das Hologramm kann ein Transmissions- oder Reflexions(Durchlicht)hologramm sein. Spezifische Typen von Hologrammen sind Denisjuk-Hologramme RGB-Hologramme, Regenbogenhologramme sowie computergenerierte oder digitale Hologramme. Das Hologramm enthält gespeicherte Daten, Informationen bzw. Interferenzmuster, z.B. in Form von ein- oder mehrdimensionalen Barcodes, Bildern, alphanumerischen Zeichen, digitalen Datenbits oder Kombinationen davon. Die Daten können in sichtbarer oder unsichtbarer Form gespeichert sein.The hologram may be a transmission or reflection (transmitted light) hologram. Specific types of holograms are Denisjuk holograms, RGB holograms, rainbow holograms, and computer-generated or digital holograms. The hologram contains stored data, information or interference patterns, for example in the form of one-dimensional or multidimensional barcodes, images, alphanumeric Characters, digital data bits or combinations thereof. The data may be stored in visible or invisible form.
Die Aufnahme von Volumenhologrammen erfolgt durch Bestrahlung einer photosensitiven Zusammensetzung mit kohärentem Licht bei einer Referenzwellenlänge oder einer Referenzwellenlängen-Kombination.Die Referenzwellenlänge liegt z.B. im Bereich von 100-1000 nm. Bevorzugte Materialien für die Erzeugung von Volumenhologramme sind photosensitive Zusammensetzungen umfassend polymerisierbare Materialien. Die Aufnahme des Hologramms kann gegebenenfalls durch eine individualisierte Bestrahlung erfolgen, so dass jedes einzelne Hologramm eine individuelle Information enthält. Bevorzugte photosensitive Zusammensetzungen sind in
In einer bevorzugten Ausführungsform umfasst die photosensitive Zusammensetzung (ii): (a) eine oder mehrere radikalische polymerisierbare Verbindungen, (b) einen oder mehrere radikalische Polymerisationsinitiatoren, (c) eine oder mehrere kationisch polymerisierbare Verbindungen verschieden von (a), (d) einen oder mehrere Initiatoren für eine kationische Polymerisation und (e) gegebenenfalls weitere Komponenten.In a preferred embodiment, the photosensitive composition comprises (ii): (a) one or more radical polymerizable compounds, (b) one or more radical polymerization initiators, (c) one or more cationically polymerizable compounds other than (a), (d) one or several initiators for a cationic polymerization and (e) optionally further components.
Beispiele für geeignete radikalisch polymerisierbare Verbindungen (a) sind Acryl-basierende Monomere, Styrol-basierende Monomere und/oder Vinyl-basierende Monomere. Spezifische Monomere sind Acrylamid, Methacrylamid, Phenylacrylat, 2-Phenoxyethylacrylat, (Acryloxyethyl) naphthalindicarboxylat-Monoester, Methylphenoxyethylacrylat, Nonylphenoxyethylacrylat, β-Acryloxyetylhydrogenphthalat, Phenoxypolyethylenglycolacrylat, 2,4,6-Tribromphenylacrylat, (2-Methacryloxyethyl) diphenat-Monoester, Benzylacrylat, 2,3-Dibromphenylacrylat, 2-Hydroxy-3-phenoxypropylacrylat, 2-Naphthylacrylat, N-Vinylcarbazol, 2-(9-Carbazol)ethylacrylat, Triphenylmethyltriacrylat, 2-(Tricyclo[5,2,10.-2.6] dibromdecylthio)ethylacrylat, S-(1-Naphthylmethyl)thioacrylat, Dicyclopentanylacrylat, Methylenbisacrylamid, Polyethylenglycoldiacrylat, Trimethylpropantriacrylat, Pentaerythritolacrylat, (2-Acryloxyethyl)(3-acryloxypropyl-2-hydroxy)diphenat, (2-Acryloxyethyl)(3-acryloxypropyl-2-hydroxy)2,3-naphthalindicarboxylat, (2-Acryloxyethyl)(3-acryloxypropyl-2-hydroxy)4,5-phenanthrendicarboxylat-Diester, Dibromneopentylglycoldiacrylat, Dipentaerythritolhexaacrylat, 1,3-Bis-[2-acryloxy-3-(2,4,6-tribrom-phenoxy)propoxy]benzol, Diethylendithioglycoldiacrylat, 2,2-Bis(4-acryloxy-ethoxyphenyl)propan, Bis(4-acryloxydiethoxyphenyl)methan, Bis(4-acryloxy-ethoxy-3,5-dibromphenyl)methan, 2,2-Bis(4-acryloxyethoxyphenyl)propan, 2,2-Bis(4-acryloxyethoxy-3,5-dibromophenyl)propan, Bis(4-acryloxyethoxy-phenyl)sulfon, Bis(4-acryloxydiethoxyphenyl)sulfon, Bis(4-acryloxypropoxy-phenyl)sulfon, Bis(4-acryloxyethoxy-3,5-dibromphenyl)sulfon, Styrol und 2-Bromstyrol. Selbstverständlich können auch Gemische von mehreren der genannten Verbindungen eingesetzt werden.Examples of suitable 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, (acryloxyethyl) naphthalenedicarboxylate monoester, methylphenoxyethyl acrylate, nonylphenoxyethyl acrylate, β-acryloxyetyl hydrogenphthalate, phenoxypolyethylene glycol acrylate, 2,4,6-tribromophenyl acrylate, (2-methacryloxyethyl) diphenate monoester, benzyl acrylate, 2 , 3-Dibromophenyl acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-naphthyl acrylate, N-vinylcarbazole, 2- (9-carbazole) ethyl acrylate, triphenylmethyl triacrylate, 2- (tricyclo [5,2,10.-2,6] dibromodecylthio) ethyl acrylate, S- (1-naphthylmethyl) thioacrylate, dicyclopentanyl acrylate, methylenebisacrylamide, polyethylene glycol diacrylate, trimethylpropane triacrylate, pentaerythritol acrylate, (2-acryloxyethyl) (3-acryloxypropyl-2-hydroxy) diphenate, (2-acryloxyethyl) (3-acryloxypropyl-2 -hydroxy) 2,3-naphthalenedicarboxylate, (2-acryloxyethyl) (3-acryloxypropyl-2-hydroxy) 4,5-phenanthrenedicarboxylate diester, dibromoneopentyl glycol diacrylate, dipentaerythritol hexaacrylate, 1,3-bis [2-acryloxy-3- (2 , 4,6-tribromo-phenoxy) propoxy] benzene, diethylene dithioglycol diacrylate, 2,2-bis (4-acryloxy-ethoxyphenyl) propane, bis (4-acryloxydiethoxyphenyl) methane, bis (4-acryloxy-ethoxy-3,5-dibromophenyl ) methane, 2,2-bis (4-acryloxyethoxyphenyl) propane, 2,2-bis (4-acryloxyethoxy-3,5-dibromophenyl) propane, bis (4-acryloxyethoxyphenyl) sulfone, bis (4-acryloxydiethoxyphenyl) sulfone , Bis (4-acryloxypropoxyphenyl) sulfone, bis (4-acryloxyethoxy-3,5-dibromophenyl) sulfone, styrene and 2-bromostyrene. Of course, mixtures of several of the compounds mentioned can be used.
Als Initiator für eine radikalische Polymerisation (b) können beliebige radikalgenerierende Substanzen wie etwa organische Farbstoffe mit Polymersalzen, z.B. Cyanine oder Salze von Diphenyliodonium und Diaryliodonium, verwendet werden. Spezifische Beispiele sind Anhydro-3,3'-dicarboxymethyl-9-ethyl-2,2'-thiacarbocyaninbetain, Anhydro-3-carboxymethyl-3',9-diethyl-2,2'-thiacarbocyaninbetain, 3,3',9-Triethyl-2,2'-thiacarbocyaniniodid, 3,9-Diethyl-3'-carboxymethyl-2,2'-thiacarbocyaniniodid und 3,3',9-Triethyl-2,2'-(4,5,4',5'-dibenzo)thiacarbocyanin iodid, 2-[3-(3-Ethyl-2-benzothiazoliden)-1-propenyl]-6-[2-(3-(3-ethyl-2-benzothiazoliden)ethyliden-imino]-3-ethyl-1,3,5-thiadiazoliumiodid, 2-[[3-Allyl-4-oxo-5-(3-n-propyl-5,6-dimethyl-2-benzothiazoliden)-ethyliden-thiazoliden]methyl]3-ethyl-4,5-diphenylthiazoliniumiodid, 1,1',3,3, 3',3'-Hexamethyl-2,2'-indotricarbocyaniniodid, 3,3'-Diethyl-2,2'-thiatricarbo-cyaninperchlorat, Anhydro-1-ethyl-4-methoxy-3'-carboxymethyl-5'-chlor-2,2'-quinothiacyaninbetain, Anhydro-5,5'-diphenyl-9-ethyl-3,3'-disulfopropyloxa-carbocyaninhydroxidtriethylaminsalz. Spezifische Beispiele für lodonium Salze, z.B. Halogenide, Tetrafluoroborate oder Hexafluorphosphate, sind Diphenyliodonium-, 4,4'-Dichlorodiphenyliodonium-, (4-Methoxyphenyl)phenyliodonium-, (4-Octyloxyphenyl)phenyliodonium-, 4,4'-Dimethoxydiphenyliodonium-, 4,4'-Ditertiär-butyldiphenyliodonium- und 3,3'-Dinitro-diphenyliodoniumsalze. Selbstverständlich können auch Gemische von mehreren der genannten Verbindungen eingesetzt werden.As the initiator for radical polymerization (b), any radical-generating substances such as organic dyes with polymer salts, eg, cyanines or salts of diphenyliodonium and diaryliodonium, can be used. Specific examples are anhydro-3,3'-dicarboxymethyl-9-ethyl-2,2'-thiacarbocyanine 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-benzothiazoliden) -1-propenyl] -6- [2- (3- (3-ethyl-2-benzothiazoliden) ethylidene-imino] -3 -ethyl-1,3,5-thiadiazolium iodide, 2 - [[3-allyl-4-oxo-5- (3-n-propyl-5,6-dimethyl-2-benzothiazolide) ethylidene-thiazolide] methyl] 3 -ethyl-4,5-diphenylthiazolinium iodide, 1,1 ', 3,3,3', 3'-hexamethyl-2,2'-indotricarbocyanine iodide, 3,3'-diethyl-2,2'-thiaryarbo-cyanine perchlorate, anhydro 1-ethyl-4-methoxy-3'-carboxymethyl-5'-chloro-2,2'-quinothiacyanine betaine, anhydro-5,5'-diphenyl-9-ethyl-3,3'-disulfopropyloxa-carbocyanine triethylamine salt Specific Examples for iodonium salts, for example halides, tetrafluoroborates or hexafluorophosphates, are diphenyliodonium, 4,4'-dichloro odiphenyliodonium-, (4-Methoxyphenyl) phenyliodonium, (4-octyloxyphenyl) phenyliodonium, 4,4'-dimethoxydiphenyliodonium, 4,4'-di-tertiary-butyldiphenyliodonium and 3,3'-dinitro-diphenyliodonium salts. Of course, mixtures of several of the compounds mentioned can be used.
Komponente (c) der photosensitiven Zusammensetzung (ii) ist eine oder mehrere kationisch polymerisierbare Verbindungen. Beispiele sind Glycidylbasierende Verbindungen, Epoxide oder Vinyl-basierende Verbindungen. Spezifische Monomere sind Diglycerolpolyglycidylether, Pentaerythritolpolyglycidylether, 1,4-Bis(2,3-epoxypropoxyperfluorisopropyl)cyclohexan, Sorbitolpolyglycidylether, Trimethylolpropanpolyglycidylether, Resorcindiglycidylether, 1,6-Hexandioldiglycidylether, Polyethylenglycoldiglycidylether, Phenylglycidylether, p-t-Butylphenyldiglycidylether, Diglycidyladipat, Diglycidyl-o-phthalat, Dibromphenylglycidylether, Dibromneopentyl, Glycoldiglycidylether, 1,6-Dimethylolperfluorhexanglycidylether, 1,2,7,8-Diepoxyoctan, 4,4'-Bis(2,3-epoxypropoxyperfluorisopropyl)diphenylether, 3,4-Epoxycyclohexylmethyl-3',4'-epoxycyclohexancarboxylat, 3,4-Epoxycyclohexyloxiran, 1,2,5,6-Diepoxy-4,7-methanperhydroinden, 2-(3,4-Epoxycyclohexyl)-3',4'-epoxy-1,3-dioxan-5-spirocyclohexan, 1,2-Ethylen-dioxy-bis(3,4-epoxycyclohexylmethan), 4',5'-Epoxy-2'-methylcyclohexyl-methyl-4,5-epoxy-2-methylcyclohexancarboxylat, Ethylenglycol-bis(3,4-epoxycyclohexancarboxylat), Bis(3,4-epoxycyclohexylmethyl)adipat, Di-2,3-epoxycyclo-pentylether, Vinyl-2-chlorethylether, Vinyl-n-butylether, Triethylenglycoldivinylether, 1,4-Cyclohexandimethanoldivinylether, Trimethylolethantrivinylether oder Vinylglycidylether. Auch Kombinationen der oben genannten Verbindungen können eingesetzt werden.Component (c) of the photosensitive composition (ii) is one or more cationically polymerizable compounds. Examples are glycidyl-based compounds, epoxides or vinyl-based compounds. Specific monomers are Diglycerolpolyglycidylether, pentaerythritol polyglycidyl ether, 1,4-bis (2,3-epoxypropoxyperfluorisopropyl) cyclohexane, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, resorcinol diglycidyl ether, 1,6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, phenyl glycidyl ether, pt-Butylphenyldiglycidylether, diglycidyl adipate, diglycidyl o-phthalate, dibromophenyl , Dibromoneopentyl, glycol diglycidyl ether, 1,6-dimethylolperfluorohexane glycidyl ether, 1,2,7,8-diepoxyoctane, 4,4'-bis (2,3-epoxypropoxyperfluoroisopropyl) diphenyl ether, 3,4-epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 3,4-epoxycyclohexyloxirane, 1,2,5,6-diepoxy-4,7-methane perhydroindene, 2- (3,4-epoxycyclohexyl) -3 ', 4'-epoxy-1,3-dioxane-5-spirocyclohexane, 1,2-Ethylene-dioxy-bis (3,4-epoxycyclohexylmethane), 4 ', 5'-epoxy-2'-methylcyclohexyl-methyl-4,5-epoxy-2-methylcyclohexanecarboxylate, ethylene glycol bis (3,4- epoxycyclohexanecarboxylate), bis (3,4-epoxycyclohexylmethyl) adipate, di-2,3-epoxy cyclo-pentyl ether, vinyl 2-chloroethyl ether, vinyl n-butyl ether, triethylene glycol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, trimethylolethane trivinyl ether or vinyl glycidyl ether. Combinations of the above compounds can also be used.
Komponente (d) der photosensitiven Zusammensetzung (ii) ist ein Initiatior für eine kationische Polymerisation. Hier sind Verbindungen geeignet, die nach Zerfall Br∅nstedt- oder Lewis-Säuren erzeugen, z.B. Diaryliodoniumsalze, Triarylsulfonsalze, Eisenallensalze und ähnliche. Beispiele für Diaryliodoniumsalze sind Tetrafluorborate, Hexafluorphosphate, Hexafluorarsenate und Hexafluorantimonate von lodoniumverbindungen. Beispiele für Triarylsulfonsalze sind Tetrafluorborate, Hexafluorphosphate, Hexafluorarsenate und Hexafluorantimonate von Sulfonium- oder Triphenylsulfoniumverbindungen, wie etwa 4-tert-Butyltriphenylsulfonium, Tris(4-methylphenyl)sulfonium, Tris(4-methoxyphenyl)sulfonium, 4-Thiophenyltriphenylsulfonium. Auch Kombinationen von mehreren der genannten Verbindungen sind geeignet.Component (d) of the photosensitive composition (ii) is an initiator of cationic polymerization. Here are compounds which produce Br Zernstedt or Lewis acids after decomposition, for example Diaryliodoniumsalze, Triarylsulfonsalze, Eisenallensalze and the like. Examples of diaryliodonium salts are tetrafluoroborates, hexafluorophosphates, Hexafluoroarsenates and hexafluoroantimonates of iodonium compounds. Examples of triarylsulfone salts are tetrafluoroborates, hexafluorophosphates, hexafluoroarsenates and hexafluoroantimonates of sulfonium or triphenylsulfonium compounds such as 4-tert-butyltriphenylsulfonium, tris (4-methylphenyl) sulfonium, tris (4-methoxyphenyl) sulfonium, 4-thiophenyltriphenylsulfonium. Combinations of several of the compounds mentioned are suitable.
Die photosensitive Zusammensetzung kann gegebenenfalls organische Lösungsmittel, z.B. Ketone, Ester, Ether, Dioxane, Kohlenwasserstoffe wie etwa Cyclohexan, Halogenkohlenwasserstoffe, Aromate, Alkohole oder Gemische von einem oder mehreren solcher Lösungsmittel enthalten. Auch lösungsmittelfreie Photopolymerzusammensetzungen können verwendet werden. Weitere mögliche Additive sind Bindemittel, Thermopolymerisationsinhibitoren, Silankoppler, Plastifizierungsmittel, Farbstoffe und/oder Copolymere.The photosensitive composition may optionally contain organic solvents, e.g. Ketones, esters, ethers, dioxanes, hydrocarbons such as cyclohexane, halogenated hydrocarbons, aromatics, alcohols or mixtures of one or more such solvents. Solventless photopolymer compositions can also be used. Further possible additives are binders, thermopolymerization inhibitors, silane coupling agents, plasticizers, dyes and / or copolymers.
Die Aufnahme und Rekonstruktion eines Volumenhologramms aus einer photosensitiven Zusammensetzung kann nach bekannten Methoden unter Verwendung von kohärenter Lichtstrahlung, z.B. Laserlicht, wie z.B. in
Die Kombination aus Lumineszenzstoff und holografischem Träger kann zur Authentifizierung oder Identifizierung, beispielsweise als Sicherheitsmarkierung von Gegenständen, z.B. Stoffen oder Stoffgemischen, verwendet werden. Auf diese Weise kann die Echtheit von Produkten oder Dokumenten bestimmt werden. Der holografische Träger wird üblicherweise auf eine Oberfläche des zu markierenden Gegenstands angebracht. Dies kann z.B. durch Verwendung von Haftmaterial erfolgen. Alternativ kann der holografische Träger jedoch auch in die Oberfläche des zu beschichtenden Gegenstands eingearbeitet werden. Der Lumineszenzstoff kann in den Träger eingebracht sein und/oder als Schicht auf der oberen und/oder unteren Oberfläche des Trägers, z.B. in einem zur Bindung des Trägers an den Gegenstand verwendeten Haftmaterial, vorliegen. Alternativ bzw. zusätzlich kann der Lumineszenzstoff auch separat vom Träger in oder auf den Gegenstand aufgebracht sein. In diesem Fall können der Lumineszenzstoff und der Träger nebeneinander, z.B. in angrenzender Beziehung, oder auf verschiedenen, räumlich voneinander getrennten Bereichen des Gegenstands vorliegen.The combination of luminescent substance and holographic support can be used for authentication or identification, for example as security marking of objects, eg substances or mixtures of substances. In this way, the authenticity of products or documents can be determined. The holographic support is usually mounted on a surface of the object to be marked. This can be done, for example, by using adhesive material. Alternatively, however, the holographic support can also be incorporated into the surface of the article to be coated. Of the Luminescent substance can be introduced into the carrier and / or be present as a layer on the upper and / or lower surface of the carrier, for example in an adhesive material used for binding the carrier to the article. Alternatively or additionally, the luminescent substance can also be applied separately from the carrier in or on the object. In this case, the luminescent substance and the carrier may be present side by side, for example in adjoining relation, or on different, spatially separated regions of the article.
Die im Lumineszenzstoff und im Hologramm vorhandenen Daten bzw. Informationen können miteinander korreliert sein. Die Daten können auch mit einem externen Daten- bzw. Informationsträger in Verbindung stehen, z.B. einer optischen Disc, einem FLASH-Speicher oder einem RFID.The data or information present in the luminescent substance and in the hologram can be correlated with one another. The data may also be associated with an external data carrier, e.g. an optical disc, a FLASH memory or an RFID.
Der Lumineszenzstoff kann, da er chemisch inert ist, in beliebige feste und/oder flüssige Stoffe oder Stoffgemische eingebracht oder darauf aufgebracht werden. Beispielsweise kann der Lumineszenzstoff Trägersubstanzen, wie etwa Lacke, Toner, Tinten, Farben etc., oder in Produkte, wie Kunststoffe, Metalle, Glas, Silikone, Papier, Gummi, Medikamente etc., aufgebracht bzw. eingebracht werden. So können beispielsweise Gegenstände mit einer Auflage des Lumineszenzstoffes auf ihrer Oberfläche oder Teilen davon versehen werden, die eine Schichtdicke von beispielsweise 1-10 µm, bevorzugt 1-5 µm aufweisen. Vorzugsweise wird der Lumineszenzstoff dem Produkt oder einem Teil des Produkts in einem Anteil von 20-2000 ppm, vorzugsweise 50-200 ppm, hinzugesetzt. Auch zum Einsatz in biologischen Systemen, z.B. Zellkulturen, Proben aus Körperflüssigkeiten bzw. Gewebeschnitten oder als Kontrastmittel, ist der erfindungsgemäße Lumineszenzstoff geeignet. Dabei kann der Lumineszenzstoff in nano- oder mikropartikulärer Form an biologische Nachweisreagenzien gekoppelt werden. Weiterhin können die Oberflächen von Partikeln des Lumineszenzstoffes mit Deodetominen oder anderen Haftsubstanzen modifiziert werden, um die Suspendierungseigenschaften z.B. in organischen Flüssigkeiten wie etwa Ölen, Benzinen, Flüssiggasen etc., in wässrigen Flüssigkeiten wie etwa Körperflüssigkeiten, in wässrigorganischen Flüssigkeitssystemen und fließfähigen Pulvern wie etwa Tonern, zu verbessern. Je kleiner die Partikel sind, desto geringer ist ihre Neigung zur Sedimentation. Durch intensives Mahlen kann z.B. die Partikelgröße soweit, z.B. auf ≤ 100 nm verringert werden, dass auch ohne Zusatz von Haftsubstanzen eine stabile Suspension der Partikel in Flüssigkeiten erreicht wird.Since it is chemically inert, the luminescent substance can be introduced into or applied to any solid and / or liquid substances or substance mixtures. For example, the luminescent substance can be applied to carrier substances, such as paints, toners, inks, paints, etc., or into products, such as plastics, metals, glass, silicones, paper, rubber, medicaments, etc. Thus, for example, objects can be provided with a coating of the luminescent substance on its surface or parts thereof which have a layer thickness of, for example, 1-10 μm, preferably 1-5 μm. Preferably, the luminescent substance is added to the product or a portion of the product in an amount of 20-2000 ppm, preferably 50-200 ppm. Also for use in biological systems, eg cell cultures, samples from body fluids or tissue sections or as a contrast agent, the luminescent substance according to the invention is suitable. In this case, the luminescent substance can be coupled in nano- or microparticulate form to biological detection reagents. Furthermore, the surfaces of particles of the luminescent substance may be modified with deodetomines or other adhesive substances to provide the suspending properties, for example, in organic liquids such as oils, gasolines, liquefied gases etc., in aqueous fluids such as body fluids, in aqueous-organic fluid systems and flowable powders such as toners. The smaller the particles, the lower their tendency to sedimentation. By intensive grinding, for example, the particle size can be reduced so far, for example to ≦ 100 nm, that a stable suspension of the particles in liquids is achieved even without the addition of adhesive substances.
Eine Fälschungssicherheit der Markierung ist dadurch gegeben, dass die für den jeweiligen Lumineszenzstoff charakteristischen Emissionslinien eine kryptografischen Schlüssel darstellen, die mit einem an den jeweiligen Stoff angepassten Detektor, d.h. dem Schloss, nachgewiesen werden können. Die Kombination des holografischen Trägers mit dem Lumineszenzstoff stellt eine weitere deutliche Verbesserung der Fälschungssicherheit der Markierung dar.An anti-counterfeiting of the marking is given by the fact that the emission lines characteristic of the respective luminescent substance represent a cryptographic key which can be compared to a detector adapted to the respective substance, i. the castle can be detected. The combination of the holographic support with the luminescent substance represents a further significant improvement in the anti-counterfeiting security of the marking.
Der Lumineszenzstoff enthält vorzugsweise zwei Komponenten, die durch Strahlung in unterschiedlichen Wellenlängenbereichen zur Lumineszenz angeregt werden können. Vorzugsweise kann die Komponente (a) mit IR-Strahlung im Bereich von 850-1500 nm, insbesondere von 920-1000 nm, zur Lumineszenz angeregt werden und/oder die Komponente (b) mit UV-Strahlung im Bereich von 350-420 nm, insbesondere von 380-410 nm, zur Lumineszenz angeregt werden.The luminescent substance preferably contains two components which can be excited to luminescence by radiation in different wavelength ranges. Preferably, component (a) can be excited to luminescence with IR radiation in the range of 850-1500 nm, in particular of 920-1000 nm, and / or component (b) with UV radiation in the range of 350-420 nm, especially from 380-410 nm, are excited to luminescence.
Der Nachweis des Vorhandenseins des Lumineszenzstoffes in einem Gegenstand erfolgt durch Bestrahlung mit zwei Wellenlängen. Zur Anregung der Komponente (a) wird eine erste Wellenlänge im Infrarotbereich, insbesondere mit IR-monokohärentem Laserlicht oder mit einer IR-Leuchtdiode mit Wellenlängen zwischen etwa 850 nm und 1500 nm, vorzugsweise zwischen etwa 920 nm und 1000 nm, besonders bevorzugt zwischen etwa 950 nm und 1000 nm, am meisten bevorzugt zwischen 920 nm und 985 nm verwendet, wobei die Komponente (a) angeregt und die resultierende Emissionsstrahlung etwa im Bereich zwischen 300 nm und 1700 nm, insbesondere zwischen 350 nm und 1000 nm nachgewiesen wird. Die Bestrahlung von Komponente (a) erfolgt vorzugsweise mit einer Leistung von 1-200 mW, insbesondere 10-80 mW.The presence of the luminescent substance in an article is detected by irradiation with two wavelengths. For excitation of component (a), a first wavelength in the infrared range, in particular with IR monochromatic laser light or with an IR light emitting diode with wavelengths between about 850 nm and 1500 nm, preferably between about 920 nm and 1000 nm, more preferably between about 950 nm and 1000 nm, most preferably between 920 nm and 985 nm, wherein component (a) is excited and the resulting emission radiation approximately in the range between 300 nm and 1700 nm, in particular between 350 nm and 1000 nm is detected. The irradiation of component (a) is preferably carried out with a power of 1-200 mW, in particular 10-80 mW.
Zur Anregung der Komponente (b) wird eine zweite Wellenlänge im UV-Bereich, insbesondere mit UV-monokohärentem Laserlicht oder mit einer UV-Leuchtdiode mit Wellenlängen zwischen etwa 350 nm und 450 nm, vorzugsweise zwischen etwa 380 nm und 400 nm verwendet, wobei die Komponente (b) angeregt und die Emissionsstrahlung durch z.B. Fluoreszenz etwa im Bereich zwischen 300 nm und 1700 nm, insbesondere zwischen 350 nm und 1000 nm nachgewiesen wird. Die Bestrahlung von Komponente (b) erfolgt vorzugsweise mit einer Leistung von 2-50 mW, insbesondere 5-30 mW.For excitation of component (b), a second wavelength in the UV range, in particular with UV monochromatic laser light or with a UV light emitting diode with wavelengths between about 350 nm and 450 nm, preferably between about 380 nm and 400 nm is used, wherein the Component (b) excited and the emission radiation by eg Fluorescence is detected in the range between 300 nm and 1700 nm, in particular between 350 nm and 1000 nm. The irradiation of component (b) is preferably carried out with a power of 2-50 mW, in particular 5-30 mW.
Bevorzugt ist, dass die Komponenten (a) und (b) des Lumineszenzstoffes durch Bestrahlung mit einer Wellenlänge im IR-Bereich und durch Bestrahlung mit einer Wellenlänge im UV-Bereich jeweils separat zur Lumineszenz angeregt werden und die Emissionsstrahlung der Komponenten (a) und (b) separat nachgewiesen wird. Hierzu kann die Anregung von Komponente (a) und Komponente (b) sequenziell, d.h. zu unterschiedlichen Zeiten erfolgen, wobei vorzugsweise zunächst die Komponente (a) und anschließend die Komponente (b) angeregt wird.It is preferred that the components (a) and (b) of the luminescent substance are separately excited to luminescence by irradiation with a wavelength in the IR range and by irradiation with a wavelength in the UV range, and the emission radiation of components (a) and ( b) is detected separately. To this end, the excitation of component (a) and component (b) may be sequential, i. take place at different times, preferably first the component (a) and then the component (b) is excited.
Die Rekonstruktion des vom holografischen Träger erzeugten Bildes kann auf übliche Weise durch Bestrahlung z.B. mit einer Wellenlänge erfolgen, die mit der zur Aufnahme des Hologramms verwendeten Referenzwelle identisch ist. Diese Wellenlänge kann im Bereich zwischen 100-1000 nm und insbesondere zwischen 220-600 nm, z.B. bei 266 nm, 405 nm oder 530 nm, liegen. Die Wellenlänge kann mit einer zur Anregung des Lumineszenzstoffes verwendeten Wellenlänge identisch oder davon verschieden sein.The reconstruction of the image produced by the holographic support may be carried out in a conventional manner by irradiation e.g. with a wavelength identical to the reference wave used to record the hologram. This wavelength can be in the range between 100-1000 nm and especially between 220-600 nm, e.g. at 266 nm, 405 nm or 530 nm. The wavelength may be identical to or different from a wavelength used to excite the luminescent substance.
In einer bevorzugten Ausführungsform der Erfindung kann die Emissionsstrahlung des Lumineszenzstoffes zusammen mit dem vom holografischen Träger stammenden Signal digital nachgewiesen werden. Dabei können digitalisierte Signale der von den Komponenten (a) und (b) des Lumineszenzstoffes sowie vom Hologramm stammenden Signale oder Teile dieser Signale (z.B. Signale einzelner Peaks) durch kryptografische Maßnahmen unter Anwendung geeigneter Algorithmen in ein neues Signal umgewandelt werden. Durch Kombination dieser von mehreren verschiedenen Komponenten stammenden Signale kann die Datendichte um einen Faktor von bis zu etwa 106 oder mehr erhöht werden.In a preferred embodiment of the invention, the Emission radiation of the luminescent substance are detected digitally together with the signal derived from the holographic carrier. In this case, digitized signals of the components (a) and (b) of the luminescent substance and of the hologram originating signals or parts of these signals (eg signals of individual peaks) can be converted by cryptographic measures using appropriate algorithms into a new signal. By combining these signals from several different components, the data density can be increased by a factor of up to about 10 6 or more.
Ein weiterer Gegenstand der Erfindung ist ein Auslesesystem zum Nachweis eines Lumineszenzstoffes und zur Aufnahme oder Rekonstruktion eines Volumenhologramms in oder auf einem Erzeugnis, enthaltend:
- (i) mindestens eine Strahlenquelle zur Anregung des Lumineszenzstoffes, vorzugsweise eine erste Strahlenquelle im IR-Bereich und eine zweite Strahlenquelle im UV-Bereich,
- (ii) gegebenenfalls eine Strahlenquelle zur Aufnahme oder Rekonstruktion des Volumenhologramms,
- (iii) gegebenenfalls einen Kontaktsensor zur Aktivierung der Strahlenquellen bei Kontakt des Auslesesystems mit dem Erzeugnis und
- (v) mindestens ein optisches Detektionselement für den Nachweis des Lumineszenzstoffes und des Volumenhologramms.
- (i) at least one radiation source for exciting the luminescent substance, preferably a first radiation source in the IR range and a second radiation source in the UV range,
- (ii) optionally a radiation source for recording or reconstruction of the volume hologram,
- (iii) optionally a contact sensor for activating the radiation sources upon contact of the readout system with the product and
- (V) at least one optical detection element for the detection of the luminescent substance and the volume hologram.
Die Strahlenquellen sind vorzugsweise jeweils Laser. Das Auslesesystem enthält vorzugsweise weiterhin einen Kontaktsensor, z.B. einen optischen Kontaktsensor, der die Strahlenquellen steuert, so dass eine Aktivierung der Strahlenquelle nur bei Kontakt des Auslesesystems mit einer zu bestimmenden Probe erfolgt. Die Bestrahlung des den Lumineszenzstoff enthaltenden Produkts durch das Auslesesystem kann direkt mit einem Lichtwellenleiter oder einem anderen optisch relevanten Transfermedium, z.B. einem optischen Feststoffkörper, einem Fluid, Gas etc., erfolgen. Die Detektion kann visuell oder mittels Detektoren erfolgen.The radiation sources are preferably each laser. The readout system preferably further contains a contact sensor, for example an optical contact sensor, which controls the radiation sources, so that activation of the radiation source takes place only when the readout system contacts a sample to be determined. The irradiation of the product containing the luminescent substance by the readout system can be carried out directly with an optical waveguide or another optically relevant transfer medium, eg a solid optical body, a fluid, gas, etc. The detection can be done visually or by means of detectors.
Es können beispielsweise Lichtwellenleiter verwendet werden, deren Köpfe als Sammellinse geschliffen sind, so dass eingestrahltes Licht (IR- bzw. UV-Licht) und vom Lumineszenzstoff emittiertes Licht (spezifisches Emissionsspektrum) eine Einheit bilden und im gleichen Punkt fokussiert sein können. Ein Vorteil dabei ist, dass keine mechanische Dejustierung zwischen Empfänger und Sender erfolgen kann. Der Dämpfungsfaktor des Lichtwellenleiters, z.B. aus Glas oder Kunststoff, kann variieren, wobei der Übergang von den optischen Bauelementen (Strahlungsquelle bzw. Detektionselement) zum Lichtwellenleiter kovisionsarm angebracht ist. Die Länge des Lichtwellenleiters kann variieren und liegt typischerweise zwischen 1 cm und 50 cm.For example, it is possible to use optical waveguides whose heads are ground as a converging lens, so that incident light (IR or UV light) and light emitted by the luminescent substance (specific emission spectrum) form a unit and can be focused at the same point. An advantage of this is that no mechanical misalignment between receiver and transmitter can take place. The attenuation factor of the optical fiber, e.g. made of glass or plastic, may vary, the transition from the optical components (radiation source or detection element) to the optical waveguide being mounted with little covision. The length of the optical fiber may vary and is typically between 1 cm and 50 cm.
Das Auslesesystem enthält weiterhin ein oder mehrere optische Detektionselemente, die für den selektiven Nachweis der Authentizität des Lumineszenzstoffs, z.B. hinsichtlich der Wellenlänge und/oder Intensität, und des Hologramms vorgesehen sind. Die Detektionselemente können beispielsweise Dioden, Fotoelemente oder elektronische Detektoren sein. Vorzugsweise werden Detektormatrices mit mehreren, vorzugsweise unterschiedlich eingestellten Detektoren verwendet, z.B. Dioden, Fotoelemente oder CCD-Matrices. Die Detektoren bzw. einzelne Detektoren der Detektormatrix können mit einem Spektrometer und/oder optischen Filtern, z.B. Bandpassfiltern, kombiniert werden.The readout system further includes one or more optical detection elements which are used for the selective detection of the authenticity of the luminescent substance, e.g. in terms of wavelength and / or intensity, and the hologram are provided. The detection elements may be, for example, diodes, photoelements or electronic detectors. Preferably, detector matrices are used with a plurality of detectors preferably set differently, e.g. Diodes, photoelements or CCD matrices. The detectors of the detector array may be equipped with a spectrometer and / or optical filters, e.g. Bandpass filters, combined.
Das Auslesesystem kann außerdem gegebenenfalls eine programmierbare elektronische Einheit enthalten, die eine digitale Auswertung und Aufbereitung des Messsignals ermöglicht.Optionally, the readout system may also include a programmable electronic unit that enables digital evaluation and conditioning of the measurement signal.
Das erfindungsgemäße Auslesesystem wird günstigerweise in Verbindung mit einer wie zuvor beschriebenen Kombination aus lumineszenter Zusammensetzung und Volumenhologramm verwendet.The readout system of the present invention is desirably used in conjunction with a combination of luminescent composition and volume hologram as previously described.
Noch ein weiterer Gegenstand der Erfindung ist ein Verfahren zum kombinierten Nachweis der Authentizität eines Lumineszenzstoffes und eines Volumenhologramms in oder auf einem Erzeugnis, umfassend die Schritte:
- (a) Bereitstellen eines Erzeugnisses, das auf das Vorhandensein einer erfindungsgemäßen Zusammensetzung getestet werden soll,
- (b) Bestrahlen des Erzeugnisses mit mindestens einer Strahlenquelle zur Anregung des Lumineszenzstoffes, z.B. einer ersten Strahlungsquelle im IR-Bereich und einer zweiten Strahlungsquelle im UV-Bereich, um Emissionsstrahlung von IR- und UV-anregbaren Komponenten der Lumineszenzmarkierung zu erzeugen, und mindestens einer Strahlenquelle zur Rekonstruktion des Volumenhologramms,
- (c) separates Nachweisen der erzeugten Emissionsstrahlungen und
- (d) Bestimmen eines Messsignals aus den nachgewiesenen Emissionsstrahlungen oder eines daraus durch kryptografische Maßnahmen gewonnenen Signals und gegebenenfalls Vergleichen des Signals mit einem vorgegebenen Muster.
- (a) providing a product to be tested for the presence of a composition according to the invention,
- (B) irradiating the product with at least one radiation source for exciting the luminescent substance, for example a first radiation source in the IR range and a second radiation source in the UV range, to generate emission radiation of IR- and UV-excitable components of the luminescent marker, and at least one Radiation source for the reconstruction of the volume hologram,
- (c) separate verification of the emissions emitted and
- (D) determining a measurement signal from the detected emission radiation or a signal obtained therefrom by cryptographic measures and optionally comparing the signal with a predetermined pattern.
Vorzugsweise erfolgt in Schritt (b) zunächst die Bestrahlung im IR-Bereich und anschließend die Bestrahlung im UV-Bereich. Vorzugsweise umfasst Schritt (d) eine digitale Aufbereitung des Messsignals oder Teilen davon.Preferably, in step (b), first the irradiation in the IR range and then the irradiation in the UV range. Preferably, step (d) comprises digital processing of the measurement signal or parts thereof.
Claims (16)
dadurch gekennzeichnet,
dass
characterized,
that
dadurch gekennzeichnet,
dass die Komponente (a) des Lumineszenzstoffes (i) ein Oxid, Oxidsulfid oder Oxidfluorid von Yttrium und ein Oxid, Oxidsulfid oder Oxidfluorid von mindestens einem, mindestens zwei oder mindestens drei weiteren Elementen ausgewählt aus Lanthan, Cer, Praseodym, Neodym, Samarium, Europium, Gadolinium, Terbium, Dysprosium, Holmium, Erbium, Thulium, Ytterbium und Lutetium sowie gegebenenfalls mindestens einen Dotierstoff, ausgewählt aus Oxiden und/oder Fluoriden von Haupt- oder Nebengruppenelementen, enthält.A composition according to claim 1 or 2,
characterized,
that the component (a) of the luminescent substance (i) an oxide, oxide sulfide or oxide fluoride of yttrium, and an oxide, oxide sulfide or oxide fluoride of at least one, at least two or at least three further elements selected from lanthanum, cerium, praseodymium, neodymium, samarium, europium , Gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, and optionally at least one dopant selected from oxides and / or fluorides of main or subgroup elements.
dadurch gekennzeichnet,
dass die Komponente (b) des Lumineszenzstoffes (i) ein Aluminat, gegebenenfalls dotiert mit Übergangsmetall- und/oder Lanthanoidionen, enthält.A composition according to any one of claims 1 to 3,
characterized,
that component (b) of the luminescent substance (i) an aluminate, optionally doped with transition metal and / or lanthanide ions contains.
dadurch gekennzeichnet,
dass die Komponenten (a) und (b) des Lumineszenzstoffes (i) in Form von Partikeln, insbesondere mit einer mittleren Partikelgröße von 10 nm-100 µm vorliegen.Agent according to one of claims 1 to 4,
characterized,
that the components (a) and (b) the luminescent substance (i) in the form of particles, in particular having a mean particle size of 10 nm-100 microns are present.
dadurch gekennzeichnet,
dass die Komponente (a) des Lumineszenzstoffes (i) mit IR-Strahlung im Bereich von 850-1500 nm, insbesondere von 920-1000 nm, zur Lumineszenz angeregt werden und/oder
die Komponente (b) des Lumineszenzstoffes (i) mit UV-Strahlung im Bereich von 350-420 nm, insbesondere von 380-410 nm, zur Lumineszenz angeregt werden kann.A composition according to any one of claims 1 to 5,
characterized,
that the component (a) of the luminescent substance (i) with IR radiation in the range of 850-1500 nm, especially 920 to 1000 nm, are excited to luminescence and / or
the component (b) of the luminescent substance (i) can be excited to luminescence with UV radiation in the range of 350-420 nm, in particular of 380-410 nm.
dadurch gekennzeichnet,
dass der holografische Träger (ii) eine photosensitive Zusammensetzung zur Aufnahme eines Volumenhologramms umfasst, enthaltend:
characterized,
that the holographic support (ii) a photosensitive composition for recording a volume hologram, comprising:
eingebracht in oder aufgetragen auf ein Erzeugnis.Composition according to one of Claims 1 to 7,
incorporated in or applied to a product.
weiterhin umfassend den Nachweis der Authentizität des Lumineszenzstoffes und des Volumenhologramms.Use according to claim 9,
further comprising the detection of the authenticity of the luminescent substance and the volume hologram.
dadurch gekennzeichnet,
dass die Authentizität des Lumineszenzstoffes und des Volumenhologramms durch ein oder mehrere daran angepasste Auslesesysteme nachgewiesen werden.Use according to one of claims 9 or 10,
characterized,
that the authenticity of the luminescent substance and the volume hologram are detected by one or more readout systems adapted thereto.
dadurch gekennzeichnet,
dass das Detektionselement ein oder mehrere CCD-Module gekoppelt mit einem Spektrometer umfasst.Readout system according to claim 13,
characterized,
that the detection member comprises one or more modules coupled to a CCD spectrometer.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10170447A EP2409849A1 (en) | 2010-07-22 | 2010-07-22 | Combination of a luminescent material with a hologram |
| PCT/EP2011/062552 WO2012010665A2 (en) | 2010-07-22 | 2011-07-21 | Combination of a luminescence substance with a hologram |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP10170447A EP2409849A1 (en) | 2010-07-22 | 2010-07-22 | Combination of a luminescent material with a hologram |
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| Publication Number | Publication Date |
|---|---|
| EP2409849A1 true EP2409849A1 (en) | 2012-01-25 |
Family
ID=42598759
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP10170447A Withdrawn EP2409849A1 (en) | 2010-07-22 | 2010-07-22 | Combination of a luminescent material with a hologram |
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| Country | Link |
|---|---|
| EP (1) | EP2409849A1 (en) |
| WO (1) | WO2012010665A2 (en) |
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| CN105667111A (en) * | 2016-01-21 | 2016-06-15 | 张利平 | Variable pattern and character packaging box applying method |
| DE102017103780A1 (en) | 2017-02-23 | 2018-08-23 | Tailorlux Gmbh | Method for identifying a material or material mixture |
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Also Published As
| Publication number | Publication date |
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| WO2012010665A3 (en) | 2012-06-07 |
| WO2012010665A2 (en) | 2012-01-26 |
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