CN101652800B - Safety and/or valuable document having a photonic crystal - Google Patents
Safety and/or valuable document having a photonic crystal Download PDFInfo
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- CN101652800B CN101652800B CN2008800043902A CN200880004390A CN101652800B CN 101652800 B CN101652800 B CN 101652800B CN 2008800043902 A CN2008800043902 A CN 2008800043902A CN 200880004390 A CN200880004390 A CN 200880004390A CN 101652800 B CN101652800 B CN 101652800B
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- photonic crystal
- luminescent substance
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/20—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose
- B42D25/29—Securities; Bank notes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B42—BOOKBINDING; ALBUMS; FILES; SPECIAL PRINTED MATTER
- B42D—BOOKS; BOOK COVERS; LOOSE LEAVES; PRINTED MATTER CHARACTERISED BY IDENTIFICATION OR SECURITY FEATURES; PRINTED MATTER OF SPECIAL FORMAT OR STYLE NOT OTHERWISE PROVIDED FOR; DEVICES FOR USE THEREWITH AND NOT OTHERWISE PROVIDED FOR; MOVABLE-STRIP WRITING OR READING APPARATUS
- B42D25/00—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof
- B42D25/30—Identification or security features, e.g. for preventing forgery
- B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
- B42D25/378—Special inks
- B42D25/387—Special inks absorbing or reflecting ultraviolet light
Abstract
The invention relates to a safety and/or valuable document having a safety element, wherein the safety element has a photonic crystal arranged on a substrate in relation to an orientation defined on a surface of the substrate, and a luminescent substance. It is characterized in that an emission wavelength lambda of the luminescent substance, and a grid constant of the photonic crystal are aligned with each other and specified according to the formula lambda = m * 2 * d, wherein d is a distance between two lattice planes of the photonic crystal, and m is a positive integer.
Description
Technical field
The present invention relates to a kind of safety and/or value document with safety element, wherein safety element contains and is arranged in suprabasil photonic crystal and a kind of luminescent substance, and substrate has the sensing about the substrate surface definition.The invention still further relates to a kind of method of safety and/or value document and method of a kind of authenticating security and/or value document made.
Background technology
In valency printing and security printing are arranged always with the color of optically-variable as good security feature just can test simply because these colors need not the technology aid.By putting into practice as can be known for example color of these optically-variables of banknote and file.Although these colors are difficult to copy, yet as often very hurry in the check of cashier, therefore can only observe the existence of change color.Based on most color and pigment, for example have these effects and liquid crystal or thin slice that can be commercial, it is known that printing is forged, and distinguishes to some extent with original colour switching look although printing is forged obviously, the certain None-identified of the layman who lacks experience is true and false.
The security system that another kind is widely known by the people comprises the use of luminescent substance.In most of files of valency printing and security printing are arranged, cold light is arranged, because cold light can't copy with simple instrument (printer, duplicating machine), and only need the UV light source just can test.Defective is that most people is only done quick test with color impression, therefore luminously can for example imitate with marking pen in the part.In contrast, accurate study needs expensive spectrometer, can distinguish different emission wavelengths with it.Although realized thus a kind of simple and reliable machine check MACH CHK, the expense of instrument aspect is huge, thereby high cost.
By document WO 2006/045567 A2 as can be known a kind of this paper start safety and/or the value document of described structure.At this, use a kind of layer as photonic crystal, described layer by have ball that single mode diameter closely distributes in other words spheroid consist of, wherein spheroid consists of spherical close packing, namely consists of crystal structure.Therefore the diameter of ball concerning the various compositions of visible light, is shown with different conditioned reflexes by Bragg's law on the various crystal faces of crystal in this scope at 50-500nm.Obtain thus a kind of color effect of optically-variable, namely observe in their situation from the viewing angle that changes in other words in deflection safety and/or value document.According to this prior art, safety and/or value document can additionally contain luminescent substance.The diameter of spheroid is selected like this, makes it possible to access desired optically variable effects, and is totally independent of possible luminous.
For example in citing document WO 03/025035 A2, US 4,391,928, EP 0 441 559B1 and EP 0 955 323 B1, put down in writing the scheme of suitable manufacturing photonic crystal.
Luminous Shu Tongchang does not have directivity characteristics, because launching centre is in the inner static orientation of coating, printing ink or analog.By other technical field for example laser diode techniques cause luminous layer structure along certain space direction reflection or the thickness that strengthens forward to produce the luminous of orientation by having with its layer as can be known.Because production cost is too high, this structure is not to be applicable to very much valency printing and security printing.
Summary of the invention
Therefore technical matters to be solved by this invention is, a kind of safety element is provided, even it can also can obtain check with minimum aid at an easy rate when observation and comparison is hurry, and reliability is improved.
For solving this technical problem, the instruction that the present invention provides is that the emission wavelength lambda of luminescent substance and the grating constant of photonic crystal are coordinated with each other and predetermined by following formula:
lambda＝m＊2＊d，
Wherein, d is two interplanar distances of photonic crystal, and m is positive integer.
In other words, consist of the particulate of photonic crystal in view of diameter and arrangement and the coordination of transmitted wave appearance, so that luminous intensity is different under different viewing angles.
By the present invention, the reliable of luminous safe element there has been considerable improvement with simply checking.Because the reviewer only need make safety and/or value document be subject to a kind of irradiation of stimulated luminescence, the for example irradiation of UV, and check i) whether observe luminous, and ii) if whether this luminous intensity changes when safety and/or value document tilt.Only when meeting above-mentioned two standards, it is genuine that safety and/or value document just are considered to.No longer can copy with simple instrument by luminous safe element of the present invention.
The understanding of utilization of the present invention is that photonic crystal also can be used for making unoriented luminous radiation own to obtain the anisotropy distribution of intensity in Space Angle by refraction.
What be called as safety and/or value document for example is: I.D., travelling passport, ID card, pass, visa, duty stamp, ticket, driving license, running car card, banknote, check, stamp, credit card, any chip card and adhesive label (for example being used for product protection).These safety and/or value document have overlayer transparent on substrate, printed layers and the optics usually.Substrate is a kind of supporting structure, and the printed layers that contains information, image, pattern and analog is laid in the substrate.The specialized material of all paperys and/or plastics matter all is suitable as the material of substrate.
Safety element is the structural unit that comprises at least one security feature.Safety element can be a kind of can be for example to be connected bonding absolute construction unit with safety and/or value document, but safety element also can be the indivisible ingredient of safety and/or value document.The former example is exactly the visa that can be attached on safety and/or the value document.An example that is used for the latter is the integrated planar structure that for example is laminated in bank note or the voucher.The latter also comprises and is placed in suprabasil layer or coating.
Security feature is a kind of structure, the expense that it can improve with (relatively simply copying) or even produce without permission, reproduce, juggle things or change.Security feature in framework of the present invention by photonic crystal with luminescent substance is compound consists of.Compound concept is a kind of coupling of optics at this, is accompanied by the mutual coordination of interplanar distance and emission wavelength.
Luminous refer to the especially electromagnetic radiation in IR, visible light or UV scope relax towards emission the process that the lower state of energy relaxes towards electronic ground state usually from excited state in atom or molecular electronic system.At this, by exciting before electric energy or electromotive force (electroluminescence), electronics bombardment (cathodeluminescence), photon bombardment (photoluminescence), heat effect (thermoluminescence) or friction (triboluminescence) realization.In framework of the present invention, be preferably photoluminescence.Luminous phosphorescence and (light-) fluorescence of especially comprising.
Fluorescence be to active electronic state deactivating aspect the radiation, wherein, for example the transformation to ground state is (spinerlaubt) that allows spin from the active state to the low-energy state.The residence time at active state is about 10 usually
-8S, that is the emission of fluorescence directly stops after the energy that is used for exciting is introduced end.In contrast, phosphorescence be in mutual anabolic process to active state forbid spinning deactivate.Therefore relaxation is faint and slow.The residence time of active state be several milliseconds until several hours, and the corresponding emission that can observe muchly fluorescence.
The emission wavelength of luminescent substance is distinctive to the material of usefulness, and by active state and low energy electrons state for example the energy difference between the ground state determine.At this, the interior maximum emission intensity of emission spectrum is called as emission wavelength.
Luminescent substance contain can be luminous atom, molecule or particulate.Luminescent substance can be used to provide illuminant colour or luminous printing ink, it contains other composition commonly used of color or printing ink, such as bonding agent, bleeding agent, antistaling agent, biocide, surfactant, buffer substance, solvent (water and/or organic solvent), filling agent, pigment, effect pigment, antifoaming agent, antisettling agent, UV stabilizing agent etc.For a person skilled in the art, the printing ink color matching that is applicable to different printing technique is open by prior art, and the luminescent substance that uses by the present invention substitutes conventional dyes or pigment or sneaked into as the additional of conventional dyes or pigment.
When radiation wavelength during less than emission wavelength, radiation is used for activating luminous in function usually.Yet when relevant luminescent substance can carry out so-called upper transfer process (Up-ConversionProzessen), there is the radiation of higher wavelength also to work.
Crystal face is spatially by Miller indices h, k and l definition.Spacing d is defined herein as interplanar parallel to each other that is has the interplanar minor increment of identical Miller indices.
Spherical close packing is corresponding to fcc (face-centred cubic, face centered cubic, cube spherical close packing) or hcc hcp (close-packed hexagonal lattice, the hexagonal dense accumulation) lattice in other words.Grating constant a at this is:
a＝2
0.5＊D
Wherein, D is the diameter of ball or spheroid, and this diameter provides as the spacing of adjacent ball centre point.
Press Bragg's law, conditioned reflex is:
lambda＝m＊2＊d
D is the spacing of crystal face, and m is positive integer (rank), especially is 1,2,3,4,5,6,7,8,9 or 10.Next use m=1 (the 1st rank) to calculate.
The relation of d and a is as follows:
d＝a/(h
2+k
2+l
2)
0.5
The pass of emission wavelength lambda and sphere diameter D is:
D＝[(h
2+k
2+l
2)/8]
0.5＊lambda
Or represent (h at n
2+ k
2+ l
2) situation under
D＝(n/8)0.5＊lambda
Diameter D represents the mean diameter (or average headway of spheroid adjacent one another are) of spheroid, and it is defined as the maximal value of the linear criterion Density Distribution that is number relevant (single mode).This Density Distribution is passed through
q
r(x)＝dQ
r/dx
Draw, wherein q
rDensity Distribution, Q
r(x) distribution is summed up in the accumulation that relates to number, and dx is the diameter differential.
In framework of the present invention, Density Distribution should be tight as far as possible, thereby produce high-visible and reproducible angular relationship when observing.Preferably, when (mostly similar to Gaussian distribution) Density Distribution is a peaked half in density, have less than (on average) diameter D 10%, preferably less than diameter D 5%, ideally less than 2% the width of diameter D.
If substitute spheroid, use other particle type body, such as thin layer platelet or thin bar, so from above-mentioned meaning, compact Size Distribution no less important.Then use average equivalent diameter
Substitute mean diameter D, this equivalence diameter calculates from associated shape according to the geometrical rule of definition and draws.But in this case, the distribution of aspect ratios of corresponding compactness (different how much extensions of particulate) is also very important.
Usually stipulate that in framework of the present invention photonic crystal does not have complete band gap for emission wavelength.Have the up to now only in theory supposition of photonic crystal of complete band gap, it is characterized in that light can not propagated towards any one direction in space.When photonic crystal had incomplete band gap, as employed in the framework of the present invention, light only can be propagated towards certain direction in space so.
Luminescent substance can be launched in IR, visible light or UV in principle.Preferred emission is carried out in visible light, because at this moment just finished check to safety and/or value document by simple visual check.
Luminescent substance can comprise luminescent dye and/or luminous pigment.
Luminescent dye can be chosen from " potpourris of organic fluorescent dye, naphthalimide, cumarin, xanthene, thioxanthene, naphthalene lactim, azlactone, methine, oxazines, thiazine and different two or more these class materials ".Luminous pigment can be from " ZnS:Ag, Zn-silicate, SiC, ZnS, CdS (activating with Cu or Mn), ZnS/CdS:Ag, ZnS:Cu, Al, Y
2O
2S:Eu, Y
2O
3: Eu, YVO
4: Eu, Zn
2SiO
4: Mn, CaVVO
4, (Zn, Mg) F
2: Mn, MgSiO
3: Mn, ZnO:Zn, Gd
2O
2S:Tb, Y
2O
2S:Tb, La
2O
2S:Tb, BaFCl:Eu, LaOBr:Tb, Mg-tungstate radicle, (Zn, Be)-silicate: Mn, Cd-borate: Mn, Ca
10(PO
4)
6F, Cl:Sb, Mn, (SrMg)
2P
2O
7: Eu, Sr
2P
2O
7: Sn, Sr
4Al
14O
25: Eu, Y
2SiO
5: Ce, Tb, Y (P, V) O
4: Eu, BaMg
2Al
10O
27: Eu, MaAl
11O
19: Ce, the potpourri of Tb and different two or more these class materials " in choose.At this, ": " is front to be host lattice, is doped chemical after ": ".
Preferably, luminescent substance is a kind of fluorescent dye of choosing from " potpourris of organic fluorescent dye, naphthalimide, cumarin, xanthene, thioxanthene, naphthalene lactim, azlactone, methine, oxazines, thiazine and different two or more these class materials ".Other suitable and preferred fluorescent dye is only such as list of references: " FluorescentDyes (fluorescent dye) " of Schwander etc., be stated from Ullmann ' s Encyclopedia of IndustrialChemistry (chemical encyclopedia of Ullmann), Wiley-VCH Verlag GmbH ﹠amp; Co.KGaA, 2002; WO 03/052025A; WO 02/053677A; EP 0147252 A; GB 2,258, and 659; And the Xerox Discloser Journal (Xerox's invention magazine) of F.M.Winnik etc., Vol.17, No.3,1992,161-162 page or leaf.
In framework of the present invention, also can advantageously use two or more different luminescent substances, wherein, different luminescent substances has different emission wavelengths.Different emission referred to herein as the wavelength difference that is at least 3nm, 5nm, 10nm, 20nm or 30nm in visible light.Produce different angles based on different emission wavelengths, luminous different colours is observed with high especially or low especially intensity respectively under these angles.High strength refers to the maximum intensity of observing with regard to emission wavelength.Low-intensity refers to the intensity that relative high strength diminishes, and for example diminishes at least 5%, 10%, 20%, 30%, 50% or 80%.When inclination safety and/or value document, produce thus luminous coloration.
Photonic crystal is that fcc or the hcc lattice of a consists of by grating constant advantageously, wherein d=a/n
0.5, n=1 to 20, especially n=1 to 5, n represents (h
2+ k
2+ l
2), h, k and l are as Miller indices.The particulate of lattice-site or photonic crystal can have arbitrary shape in principle, for example as thin layer platelet or thin bar.But preferably, lattice-site or particulate design become spheroid.
Particularly preferably be, spheroid is core-shell particulate, and they are arranged in the spherical close packing.The mean diameter to be set of spheroid depends on the emission wavelength of the luminescent substance that uses at this.Therefore when luminescent substance was launched in IR scope (780-3000nm), the mean diameter of spheroid was in the 270-5000nm scope, especially in the 270-2500nm scope.When luminescent substance was launched in visible-range (380-780nm), the mean diameter of spheroid was in the 135-1200nm scope, especially in the 135-600nm scope.When luminescent substance was launched in UV scope (100-380nm), the mean diameter of spheroid was in the 35-600nm scope, especially in the 35-300nm scope.
Photonic crystal can for example be made under pressure by depositing mutually by self-organization from liquid, just looks like to be such in ink-jet printing process.For example, from SiO
2Solution manufacture of intraocular opaline is by fully open.
Particularly preferably be, core-shell particulate has the core of being made by the organic or inorganic Sandwich materials and the shell of being made by polymerization organic shell material, and wherein sheathing material can flow when temperature raises, and Sandwich materials then can't flow when temperature raises.Background is, be to form photonic crystal, this essential periodicity long-range structure for example spherical close packing must in the direction of definition, make.If have this core-capsomeric filling agent or emulsion or suspending liquid when temperature raises, to suffer pressure, when particulate can move mutually, impel particulate to arrange and the location towards the spherical close packing on the substrate surface at the shearing that produces between particulate so.Flowable shell has been simplified particulate this ordering campaign relative to each other under the pressure and temperature condition, and has produced and have fabulous long-range order (Fernordnung) and single-orientated photonic crystal in substrate.Specifically, also there are various operational feasibilities at this.
The inorganic sandwich material can be chosen from " metal, semimetal, metal chalcogenide especially metal oxide, metal pnictide especially the potpourri of metal nitride or metal phosphide and different two or more these class materials ", wherein, metal can be made of the element of first three main group of the periodic table of elements or be made of the metallic element of subgroup, and wherein semimetal can comprise Si, Ge, As, Sb and Bi, particularly from " SiO
2, TiO
2, ZrO
2, SnO
2And Al
2O
3" in choose.
Organic Sandwich materials preferably can be from " aliphatic series; the polyester of aliphatic series/aromatic or all aromatic; polyamide; polycarbonate; polyureas; polyurethane, amino resin, bakelite resin is formaldehyde for example, the melamine condensate thing of urea or phenol, epoxide resin, acrylate such as methyl methacrylate, butyl methacrylate, isopropyl methacrylate, polystyrene, PVC, polyacrylonitrile, random or the segmented copolymer of one or more these class homopolymer, and two or more different these class homopolymer or the potpourri of multipolymer " in choose.
Sheathing material can be preferably from " aliphatic series; the polyester of aliphatic series/aromatic or all aromatic; polyamide; polycarbonate; polyureas; polyurethane, amino resin, bakelite resin, formaldehyde for example, the melamine condensate thing of urea or phenol, epoxide resin, polyepoxide, polymethacrylate such as polymethylmethacrylate, poly-n-butyl methacrylate, the polyacrylic acid isopropyl ester, polystyrene, PVC, polyacrylonitrile, tygon, polypropylene, polyethylene oxide, polybutadiene, teflon, polyoxymethylene, natural rubber, polyisoprene, random or the segmented copolymer of one or more these class homopolymer, and two or more different these class homopolymer or the potpourri of multipolymer " in choose.
Suitable is, Sandwich materials is compared sheathing material and had higher glass temperature, because under the temperature that is between the glass temperature of material, only sheathing material can flow, and Sandwich materials can't flow.Sandwich materials can for example have and is higher than 60 ℃ and preferably is higher than 80 ℃ of glass temperatures that most preferably are higher than 90 ℃, and sheathing material for example can have in 40-90 ℃ of scope the especially glass temperature between 60-80 ℃.For example when organic polymer during as Sandwich materials, recommend this glass temperature range.Alternatively, for example in the situation of using the inorganic sandwich material, the glass temperature of Sandwich materials is higher than 300 ℃, and the glass temperature of sheathing material is for example also very high in the situation that is polycarbonate so, for example 80-250 ℃, especially in 120 to 200 ℃ scope.
When making photonic crystal, consist of matrix and spheroid or core implantation (with fixing) sheathing material in this matrix and should have the refractive index (being also referred to as refractive index) that is different from the Sandwich materials refractive index.Different refractive indexes referred to herein as, and difference is at least 0.001, better at least 0.01, advantageously at least 0.1.The technician is not difficult to select applicable material from aforementioned material for Sandwich materials and sheathing material in view of the difference of refractive index.Here, Sandwich materials also or sheathing material have respectively higher refractive index.
The weight ratio of Sandwich materials and sheathing material is between 2: 1 to 1: 5, especially between 3: 2 to 1: 3.All be in the situation of polymeric material at bi-material, this ratio preferably can be greater than 2: 3.
Between core-capsomeric core and shell, articulamentum can be set.Crosslinked or partial cross-linked organic polymer is applicable to this.Alternatively, function also can be brought into play for connecting or adhere to sheathing material in professional mode in the surface of core.
Be suitable for generating the core of photonic crystal-capsomeric Production Example and be explained as starting in the described prior art at this paper, equally also put down in writing other modification and the details of Sandwich materials, sheathing material, articulamentum etc.At this point at length with reference to prior art.
Photonic crystal can be designed to thin layer, layer or film used according to the present invention.Correspondingly, they can be applied in the substrate with common cladding process or adhesion medium.The indivisible ingredient that they can configuration file at this point is for example under the situation of card structure.
Can consist of visible pattern by photonic crystal of the present invention, for example the profile of object or person thing or letter and/or digital character string.Bar code also can be used as pattern.Then carry out coating or correspondingly intercept film with corresponding typography.Certainly, photonic crystal also can macroscopically isotropic ground that is pattern-free ground formation.
There are different possibilities in the layout of luminescent substance.Luminescent substance can be arranged in the particulate of photonic crystal.In core-capsomeric situation, can be arranged in core-capsomeric Sandwich materials and/or the sheathing material.For this reason, in the situation of organic Sandwich materials, associated materials solidify or polymerization before preferably mix equably with luminescent substance in the production run at particulate.Can produce luminous doping in the situation of inorganic sandwich material, for example mix rare earth element, it is loaded in the host lattice of Sandwich materials.Then can generate a kind of photonic crystal of not sneaking into luminous particle, avoid reliably thus the formation of photonic crystal because existing gapped luminous particle to be obstructed.
Use in the situation of polymeric material in core-capsomeric sandwich zone and/or shell zone, each polymkeric substance contains luminous monomer component, that is to say regular, static, block ground or as side chain (graft copolymer).In the situation of cross-linked polymer, crosslinking medium also can be luminous.At last, luminescent substance can be covalently, ion ground or be connected on the polymer chain synthetically.
Luminescent substance also can be arranged between the particulate of photonic crystal lattice certainly.In the situation of using pigment, recommend the diameter D of pigment particle
pWith the diameter D of the particulate of photonic crystal lattice (or
) ratio D
p/ D (or D
p/
) be less than 0.5, preferably less than 0.1, most preferably less than 0.02.Pigment particle can be arranged between the particulate of photonic crystal or the spheroid and in fact can not cause damage to particulate or spheroid when printing.When luminescent substance was luminescent dye, they can freely be distributed between the particulate of photonic crystal lattice and arrangement that can the stray light sublattice.In both cases, the manufacturing of photonic crystal is by with the mixing and next realize to the formation of the long-range order of crystal of the particulate of photonic crystal and luminescent substance, just as described above.A kind of flexible program to this is that luminescent substance for example passes through successively adsorption precipitation on the surface of photonic crystal particulate.Realize a kind of uniform growth at the particulate of photonic crystal thus, the result obtains compact Density Distribution.At this advantageously, the particulate of photonic crystal and luminescent substance can be selected and change independently of one another, and this is so that become easy with the adaptive of the different product that valency printing and security printing are arranged.
Scheme as an alternative, photonic crystal also can be provided with luminescent substance below.Therefore for example the available pigment that contains luminescent substance or printing ink carry out coating to substrate and for example print.Then photonic crystal is coated to for example on the coating as film under the simplest situation.This flexible program is the simplest with regard to method and technology, and also allows for example to be variety classes or the safety of value and/or value document is revised luminescent substance/photonic crystal in simple mode system.
At last, can be in photonic crystal and/or contain in the layer of luminescent substance and settle extraly non-luminous colorant, such as dyestuff or pigment.For this reason, can consider that all are general in safety and/or value document field, well known to a person skilled in the art colorant.Equally, legal property material commonly used can be set in other layer of photonic crystal or safety and/or value document.
The invention still further relates in addition a kind of for the manufacture of the method by safety of the present invention and/or value document or safety element, wherein, substrate on the surface or part surface be provided with coating, coating contains the particulate of the photonic crystal that will form, and this coating is compressed under the effect in heat and pressure, the luminescent layer that wherein will contain alternatively luminescent substance before the fine-grained coating of tool is applied in the substrate, and/or wherein particulate contain luminescent substance or mix therewith.In the form of implementation of this manufacture method, realized the formation of photonic crystal with compression.
Preferably be 60-260 ℃ in temperature and especially carry out heat effect in 70-190 ℃ the scope, the duration is 0.5-7200S, preferably at 0.5-3600S, most preferably is 1-10S.Compression can realize with the pressure in the scope of the preferred 1-20bar of 1-100bar.Compression is finished by pressing especially lamination usually.Use the inorganic sandwich material and with and the glass temperature polymkeric substance higher than sheathing material situation about being connected under, for example between 80 to-250 ℃, heat effect occurs under corresponding higher temperature, for example between 140-250 ℃.
On with the coating of photonic crystal particulate, isolation and/or protective seam can be set.Protective seam can be in heat effect and pressure-acting process with substrate, according to circumstances with luminescent layer and be with fine-grained coating welding or be laminated into laminated composite.Protective seam should be transparent with regard to emission wavelength lambda.
Different from preceding method is, also can make thus by safety of the present invention and/or value document, that is, the photonic crystal of completed especially form of film (thickness is for example at 0.1-500 μ m) is applied in the substrate and by bonding or by stacked and is attached thereto.Wherein, luminescent substance is also Already in the photonic crystal.Certainly also can arrange in advance at this and to have for example substrate of printed layers of independent coating that contains luminescent substance.
The invention still further relates in addition a kind of safety and/or value document, it obtains by method of the present invention by aforementioned.
The present invention relates to a kind of check at last by the method for safety of the present invention and/or value document or safety element, wherein for example get off to activate luminescent substance to be used for the emission luminous radiation by being exposed to the UV radiation, wherein rely on the intensity of determining luminous radiation relevant for the angle on safety and/or value document surface, and wherein the fixed angular relationship of luminous radiation and predetermined angular relationship are compared.If can't determine any angular relationship, or fixed angular relationship is inconsistent with predetermined angular relationship, is not by safety of the present invention and/or value document so just, thereby copies.If fixed angular relationship is consistent with the angular relationship of being scheduled to, safety and/or value document are exactly by of the present invention so, thereby are genuine.Under the simplest situation, thisly determine to finish by visual check.But also can determine angular relationship with machine.Under the situation of different luminescent substances, thisly to determine to implement for emission wavelength separately, different angular relationships provides different emission wavelengths.
Description of drawings
Hereinafter explain in detail the present invention by only being implemented the example shown in the form.
Example 1: by the different structure form of safety of the present invention and/or value document;
Example 2: the angular relationship of the fluorescence of object in the example 1.
Embodiment
Fig. 1 shows the xsect by the different modification of safety of the present invention and/or value document.
Can see substrate 1 by Fig. 1 a, substrate 1 can be single or multiple lift.Printed layers 2 directly is placed in this substrate, and wherein printed layers 2 contains two kinds of equally distributed different fluorescent materials.The emission wavelength of the first fluorescent material is 500nm, and the emission wavelength of the second fluorescent material is 707nm.Next be the photonic crystal 3 that is designed to film according to sequence.This photonic crystal 3 is by consisting of by the described core of document WO 2003/025035 A2-shell particulate.The particulate mean diameter that described core-shell particulate has is 354nm.Protective seam 4 to visible transparent is close on the photonic crystal 3, and protective seam 4 itself can be single or multiple lift.Also can arrange the middle layer of single or multiple lift between printed layers 2 and photonic crystal 3, this is in the drawings for succinct former thereby do not illustrate.Substrate 1 and printed layers 2, photonic crystal 3 and protective seam 4 interconnect by stacked, and integrant layer group.
In the flexible program of Fig. 1 b, used identical fluorescent material, but fluorescent material is arranged in the photonic crystal 3.Can cancel printed layers 2 thus.Fluorescent material is absorbed or is adsorbed on core-capsomeric surface, and evenly distributes.
At the diameter of the particulate of emission wavelength and photonic crystal 3 and finally also obtain universal time coordinated with grating constant a and the interplanar crystal spacing d of photonic crystal 3, the result is, at the surface normal of comparatively safe and/or value document during into about 45 °, red (707nm) is launched with maximum intensity, yet when 0 ° and 90 °, intensity weakens greatly, usually at below 90% of maximum intensity.In contrast, green (500nm) only be observed under 45 ° for maximum intensity 10% or less, yet when 0 ° and 90 °, reach maximum intensity.
By Fig. 2 a this point as can be known, wherein this relates to the projection of hemisphere on the surface normal direction of safety and/or value document shown in the perspective in Fig. 2 b.When regional G is shown in green in the situation of about 90 ° and 0 °, can see that regional R takes on a red color in about 45 ° situation.
Claims (42)
1. safety and/or value document with safety element, wherein said safety element comprise and are arranged in suprabasil photonic crystal and luminescent substance, and described substrate has the orientation about the surface definition of described substrate,
It is characterized in that,
The emission wavelength lambda of described luminescent substance and the grating constant of described photonic crystal are coordinated with each other and predetermined by following formula, namely
lambda＝m＊2＊d，
Wherein d is two interplanar distances of described photonic crystal, and m is positive integer.
2. by safety claimed in claim 1 and/or value document, wherein, described luminescent substance is launched in IR, visible light or UV.
3. by claim 1 or 2 described safety and/or value documents, wherein, described luminescent substance comprises luminescent dye and/or luminous pigment.
4. by safety claimed in claim 3 and/or value document, wherein, described luminescent dye from " potpourris of organic fluorescent dye, naphthalimide, cumarin, xanthene, thioxanthene, naphthalene lactim, azlactone, methine dyes, oxazine, thiazine and different two or more these class materials ", choose and/or luminous pigment from " ZnS:Ag, Zn-silicate, SiC, ZnS, CdS; with Cu or Mn activation, ZnS/CdS:Ag, ZnS:Cu, Al, Y
2O
2S:Eu, Y
2O
3: Eu, YVO
4: Eu, Zn
2SiO
4: Mn, CaVVO
4, (Zn, Mg) F
2: Mn, MgSiO
3: Mn, ZnO:Zn, Gd
2O
2S:Tb, Y
2O
2S:Tb, La
2O
2S:Tb, BaFCl:Eu, LaOBr:Tb, Mg-tungstate radicle, (Zn, Be)-silicate: Mn, Cd-borate: Mn, Ca
10(PO
4)
6F, Cl:Sb, Mn, (SrMg)
2P
2O
7: Eu, Sr
2P
2O
7: Sn, Sr
4Al
14O
25: Eu, Y
2SiO
5: Ce, Tb, Y (P, V) O
4: Eu, BaMg
2Al
10O
27: Eu, MaAl
11O
19: Ce, the potpourri of Tb and different two or more these class materials " in choose.
5. by safety claimed in claim 1 and/or value document, wherein, described luminescent substance is fluorescent dye, and this fluorescent dye is chosen from " potpourris of organic fluorescent pigment, naphthalimide, cumarin, xanthene, thioxanthene, naphthalene lactim, azlactone, methine dyes, oxazine, thiazine and different two or more these class materials ".
6. by safety claimed in claim 1 and/or value document, wherein, described photonic crystal is that fcc or the hcc lattice of a consists of by grating constant, and d=a/n
0.5, n=1 to 20, wherein n representative (h
2+ k
2+ l
2), h, k and l are as Miller indices.
7. by safety claimed in claim 6 and/or value document, wherein n=1 to 5.
8. by safety claimed in claim 1 and/or value document, wherein, the lattice-site of described photonic crystal consists of by spheroid or its central point.
9. by safety claimed in claim 8 and/or value document, wherein, described spheroid is core-shell particulate, and they are arranged in the spherical close packing.
10. by safety claimed in claim 9 and/or value document, wherein, when described luminescent substance was launched in IR (780-3000nm), the mean diameter of described spheroid was in the scope of 270-5000nm.
11. by safety claimed in claim 10 and/or value document, wherein, the mean diameter of described spheroid is in the 270-2500nm scope.
12. by safety claimed in claim 9 and/or value document, wherein, when described luminescent substance was launched in visible light (380-780nm), the mean diameter of described spheroid was in the scope of 135-1200nm.
13. by the described safety of claim 12 and/or value document, wherein, the mean diameter of described spheroid is in the scope of 135-600nm.
14. by safety claimed in claim 9 and/or value document, wherein, when described luminescent substance was launched in UV (100-380nm), the mean diameter of described spheroid was in the scope of 35-600nm.
15. by the described safety of claim 14 and/or value document, wherein, the mean diameter of described spheroid is in the scope of 35-300nm.
16. by safety claimed in claim 9 and/or value document, wherein, described core-shell particulate has the core of being made by the Sandwich materials of organic or inorganic and the shell of being made by the organic sheathing material of polymerization, wherein, Sandwich materials is compared sheathing material and is had higher glass temperature, under the temperature that is between the glass temperature of described material, only sheathing material can flow, and Sandwich materials can't flow.
17. by the described safety of claim 16 and/or value document, wherein, inorganic Sandwich materials is chosen from " metal, semimetal, metal chalcogenide, metal oxide, metal pnictide, metal nitride or metal phosphide and their potpourri ", wherein, metal can be made of the element of first three main group of the periodic table of elements or be made of the metallic element of subgroup, and wherein semimetal comprises Si, Ge, As, Sb and Bi.
18. by the described safety of claim 17 and/or value document, wherein, inorganic Sandwich materials is from " SiO
2, TiO
2, ZrO
2, SnO
2And Al
2O
3" in choose.
19. by one of claim 16 to 18 described safety and/or value document, wherein, described Sandwich materials has the glass temperature that is in greater than in 60 ℃ the scope.
20. by the described safety of claim 19 and/or value document, wherein, described Sandwich materials has the glass temperature that is in greater than in 80 ℃ the scope.
21. by the described safety of claim 19 and/or value document, wherein, described Sandwich materials has the glass temperature that is in greater than in 90 ℃ the scope.
22. by safety claimed in claim 1 and/or value document, wherein, described luminescent substance is arranged in the described photonic crystal.
23. by the described safety of claim 22 and/or value document, wherein, described luminescent substance is arranged in the particulate of described photonic crystal.
24. by claim 22 or 23 described safety and/or value documents, wherein, described luminescent substance is arranged between the particulate of described photonic crystal.
25. by safety claimed in claim 1 and/or value document, wherein, described photonic crystal below is provided with luminescent substance.
26. by the described safety of claim 19 and/or value document, wherein, described Sandwich materials has and is higher than 300 ℃ glass temperature.
27. by the described safety of claim 22 and/or value document, wherein, described luminescent substance is arranged in described core-capsomeric Sandwich materials and/or the sheathing material.
28. one kind for the manufacture of the method by safety claimed in claim 1 and/or value document or safety element, wherein, substrate on the surface or part surface be provided with coating, described coating contains the particulate of photonic crystal, and described coating is compressed under the effect in heat and pressure, the luminescent layer that wherein will contain luminescent substance is applied in the substrate, and/or wherein the particulate of photonic crystal comprise luminescent substance or mix therewith.
29. by the described method of claim 28, wherein, the temperature of heat effect utilization in 60-180 ℃ scope carried out, the duration is 0.5-7200S.
30. by the described method of claim 29, wherein, the temperature of heat effect utilization in 70-130 ℃ scope carried out.
31. by the described method of claim 29, wherein, the duration is 0.5-3600S.
32. by the described method of claim 29, wherein, the duration is 1-10S.
33. by claim 28 or 29 described methods, wherein, compression utilizes the pressure of 1-100bar to carry out.
34. by the described method of claim 33, wherein, compression utilizes the pressure of 1-20bar to carry out.
35. by the described method of claim 33, wherein, compression is finished by pressing.
36. by the described method of claim 33, wherein, compression is finished by lamination.
37. by the described method of claim 28, wherein, at the coating with photonic crystal particulate isolation and/or protective seam are set.
38. by the described method of claim 37, wherein, described protective seam between the action period of heat and pressure with described substrate, with luminescent layer and with the coating welding of photonic crystal particulate or be laminated into laminated composite.
39. by the described method of claim 38, wherein, described protective seam is transparent with regard to emission wavelength lambda.
40. by safety and/or value document or the safety element that obtains by the described method of claim 28.
41. be I.D., travelling passport, ID card, the pass, visa, duty stamp, ticket, driving license, running car card, banknote, check, stamp, credit card, chip card or adhesive label in form of implementation by claim 1 or 40 described safety and/or value document.
42. one kind is used for check by the method for claim 1 or 40 or 41 described safety and/or value document or safety element, wherein the stimulated luminescence material is to be used for the emission luminous radiation, wherein rely on relevant for the angle on safety and/or value document surface and the intensity of luminous radiation is observed or determine, and the angular relationship of the luminous radiation that wherein will observe or determine compares with predetermined angular relationship.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102007007029A DE102007007029A1 (en) | 2007-02-08 | 2007-02-08 | Security and / or value document with photonic crystal |
| DE102007007029.4 | 2007-02-08 | ||
| PCT/DE2008/000228 WO2008095481A2 (en) | 2007-02-08 | 2008-02-06 | Safety and/or valuable document having a photonic crystal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101652800A CN101652800A (en) | 2010-02-17 |
| CN101652800B true CN101652800B (en) | 2013-02-06 |
Family
ID=39575538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008800043902A Active CN101652800B (en) | 2007-02-08 | 2008-02-06 | Safety and/or valuable document having a photonic crystal |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP2118855B1 (en) |
| CN (1) | CN101652800B (en) |
| AU (3) | AU2008213463A1 (en) |
| CA (1) | CA2677418C (en) |
| DE (1) | DE102007007029A1 (en) |
| WO (1) | WO2008095481A2 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007012042A1 (en) | 2007-03-13 | 2008-09-18 | Giesecke & Devrient Gmbh | security element |
| GB0720550D0 (en) | 2007-10-19 | 2007-11-28 | Rue De Int Ltd | Photonic crystal security device multiple optical effects |
| CA2656506A1 (en) * | 2009-02-27 | 2010-08-27 | Bank Of Canada | Security device |
| DE102011112696B4 (en) * | 2011-08-31 | 2016-02-18 | Martin-Luther-Universität Halle-Wittenberg | Solar cell with film for back contact, process for its preparation and use of a film as back contact |
| ES2632808T3 (en) * | 2014-09-04 | 2017-09-15 | Nicox Science Ireland | Carnosine compounds donors of nitric oxide |
| EP3109060B1 (en) | 2015-06-23 | 2018-08-15 | Hueck Folien Gesellschaft m.b.H. | Safety element and method for manufacturing a safety element |
| WO2020192579A1 (en) * | 2019-03-22 | 2020-10-01 | 苏州科技大学 | Anti-counterfeiting mark and anti-counterfeiting paper |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005077668A1 (en) * | 2004-02-16 | 2005-08-25 | Hueck Folien Ges.M.B.H. | Tamper-proof, color-shift security feature |
| CN1687306A (en) * | 2005-04-29 | 2005-10-26 | 中国科学院上海硅酸盐研究所 | Luminescent material converted in nano level with yttrium oxide as matrix and preparation method |
| WO2006045567A2 (en) * | 2004-10-25 | 2006-05-04 | Merck Patent Gmbh | Use of moulding bodies made of core-shell particles |
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| US4391928A (en) | 1981-09-04 | 1983-07-05 | Nl Industries, Inc. | Opacifying polymeric particle and uses |
| FR2554122B1 (en) | 1983-11-02 | 1987-03-20 | Rhone Poulenc Spec Chim | NOVEL COMPOSITION FOR MARKING DOCUMENTS AND METHOD FOR VERIFYING THE AUTHENTICITY OF SUCH DOCUMENTS |
| JP2790381B2 (en) | 1990-02-03 | 1998-08-27 | 三井化学株式会社 | Cored multilayer emulsion particles |
| GB2258659B (en) | 1991-08-14 | 1995-06-07 | De La Rue Thomas & Co Ltd | Luminescent materials and their use in security documents |
| DE19820302A1 (en) | 1998-05-04 | 2000-02-24 | Basf Ag | Core / shell particles, their manufacture and use |
| US6576155B1 (en) | 1998-11-10 | 2003-06-10 | Biocrystal, Ltd. | Fluorescent ink compositions comprising functionalized fluorescent nanocrystals |
| US7241502B2 (en) | 2001-09-14 | 2007-07-10 | Merck Patentgesellschaft | Moulded bodies consisting of core-shell particles |
| JP2005513198A (en) | 2001-12-18 | 2005-05-12 | ナノゾルティオンス ゲーエムベーハー | Security printing liquid and method using nanoparticles |
| DE10227071A1 (en) * | 2002-06-17 | 2003-12-24 | Merck Patent Gmbh | Composite material containing core-shell particles |
| GB0615921D0 (en) * | 2006-08-10 | 2006-09-20 | Rue De Int Ltd | Photonic crystal security device |
-
2007
- 2007-02-08 DE DE102007007029A patent/DE102007007029A1/en not_active Withdrawn
-
2008
- 2008-02-06 AU AU2008213463A patent/AU2008213463A1/en not_active Abandoned
- 2008-02-06 CN CN2008800043902A patent/CN101652800B/en active Active
- 2008-02-06 WO PCT/DE2008/000228 patent/WO2008095481A2/en active Application Filing
- 2008-02-06 CA CA2677418A patent/CA2677418C/en active Active
- 2008-02-06 EP EP08715461.3A patent/EP2118855B1/en active Active
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2014
- 2014-07-11 AU AU2014203815A patent/AU2014203815A1/en not_active Abandoned
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2016
- 2016-09-09 AU AU2016225899A patent/AU2016225899B2/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005077668A1 (en) * | 2004-02-16 | 2005-08-25 | Hueck Folien Ges.M.B.H. | Tamper-proof, color-shift security feature |
| WO2006045567A2 (en) * | 2004-10-25 | 2006-05-04 | Merck Patent Gmbh | Use of moulding bodies made of core-shell particles |
| CN1687306A (en) * | 2005-04-29 | 2005-10-26 | 中国科学院上海硅酸盐研究所 | Luminescent material converted in nano level with yttrium oxide as matrix and preparation method |
Also Published As
| Publication number | Publication date |
|---|---|
| DE102007007029A1 (en) | 2008-08-14 |
| WO2008095481A3 (en) | 2008-12-11 |
| EP2118855B1 (en) | 2020-09-23 |
| AU2008213463A1 (en) | 2008-08-14 |
| WO2008095481A2 (en) | 2008-08-14 |
| AU2014203815A1 (en) | 2014-07-31 |
| CN101652800A (en) | 2010-02-17 |
| AU2016225899B2 (en) | 2018-02-01 |
| CA2677418A1 (en) | 2008-08-14 |
| CA2677418C (en) | 2016-09-20 |
| AU2016225899A1 (en) | 2016-09-29 |
| EP2118855A2 (en) | 2009-11-18 |
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