Title of Invention	A LUMINESCENT SUBSTANCE, SECURITY PAPER, SECURITY ELEMENT, VALUE DOCUMENT AND A METHOD OF PRODUCING A VALUE DOCUMENT"
Abstract	The invention relates to a printed value document having at least one luminescent substance.

Full Text

Value document [001] This invention relates to a luminescent substance, a value document, a secu-rity element and a security paper having at least one luminescent substance as an authenticity feature. The invention also relates to different methods for checking the authenticity of such value document, security element or securi-ty paper, and to methods for production thereof. [002] Security paper will hereinafter be understood to be paper that is e.g. already equipped with security elements, such as a watermark, security thread, holo-gram patch, etc., but is not yet fit for circulation and is an intermediate prod-uct in production of the value document. Value document will refer to the product fit for circulation. [003] The designation "value document" will refer in the context of the invention to bank notes, checks, shares, tokens, identity cards, credit cards, passports and other documents as well as labels, seals, packages or other elements for product protection. [004] The protection of value documents against forgery by means of luminescent substances has been known for some time. EP 0 052 624 B2 uses for exam-ple luminescent substances based on host lattices doped with rare earth met-als. [005] Preferably, substances are used in which either the absorption or the emis-sion is outside the visible spectral range. [006] If the emissions are at wavelengths between approx. 400 run and approx. 700 nm, the luminescent substances are detectable with the eye upon suitable ex-citation. For some applications this is desired, e.g. in authenticity testing by illumination with UV light. For other applications, however, it is of advan-tage if the emission is outside the visible spectral range, since special detec-tors are then necessary for detecting the substances. -2- [007] However, luminescent substances with characteristic properties that are suit-able for protecting value documents and in particular for automatic authen-ticity recognition are restricted in number. Most inorganic and organic lumi-nescent substances have uncharacteristic, wide spectra, insufficient emission intensity and are moreover often commercially available. This impedes their identification and makes it impracticable to use several of said substances si-multaneously. [008] Starting out from this prior art, the invention is based on the problem of in-creasing the number of luminescent substances suitable as authenticity fea-tures for value documents and providing in particular value documents and security papers having authenticity features in the form of luminescent sub-stances that differ from value documents and security papers having hitherto known luminescent substances by a characteristically altered excitation and/or emission spectrum. [009] The solution to this problem can be found in the independent claims. Devel-. opments are the subject matter of the subclaims. [0010] According to the invention, at least one luminescent substance is used for protection. Preferably, its emission spectrum is in the visible or infrared spectral range (VIS, IR), Particularly preferably, the luminescent substance emits in the near infrared (N1R). The excitation is preferably also effected in the near infrared. [0011] Depending on the inventive luminescent substance used, the emission band can follow the Stokes or anti-Stokes rule or quasi-resonance can be ob-served. [0012] The substances suitable for the inventive authenticity protection are lumines-cent substances with the general formula XZO4 where -3- X stands for Sca Yb Lac Ced Pre Ndf Smg Euh GdI Tbk Dy1 Hom Ern Tmo Ybp Luq Sb(III)r Bis Crt Mn(III)u Fe(III)v [Baw Mn(II)x Fe(II)y Caz Sn(II)a Srß Co? Nid CUe]3/2 [Na?, Kx?]3/2 [U(IV)µPbp Ths]3/4 U(IV) f/3 and Z stands for Nbza Tazb Vzc Pzd [Tize Zrzf Sn(IV)zg]5/4 Wzh5/6 Fe(III)zi5/3 and a+b+c+d+e+f+g+h+i+k+l+m+n+o+p+q+r+s+t+u+v+ 3/2(w + x + y + z + a +ß +? + d +e) + 3(? + ?) + 3/4(µ + p+s) + f/2 = 1, and a, b, c, d, e, f, g, h, i, k, 1, m, n, o, p, q, r, s, t, u, v, w, x, y, z, a, ß, ?, d, e, ?, ?,µ, p, s, and f each range from 0 to 1, and za + zb + zc + zd + 5/4 (ze + zf + zg) + 5/6zh + 5/3zi = 1, and za, zb, zc, zd, ze, zf, zg, zh and zi each range from 0 to 1. [0013] The symbols listed for X and Z correspond to the symbols in the periodic system of the elements, O stands for oxygen. [0014] The X elements Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Sb, Bi, and Cr have the oxidation state 3 here. [0015] The X elements Ba, Ca, Sn, Sr, Co, Ni and Cu have the oxidation state 2 here. [0016] The X elements Na and K have the oxidation state 1 here. [0017] The X elements Mn and Fe have the oxidation state 2 and/or 3 here. [0018] The X elements Pb and Th have the oxidation state 4 here. [0019] The X element U has the oxidation states 4 and/or 6 here. [0020] The Z elements Nb, Ta, V and P have the oxidation state 5 here. -4- [0021] The Z elements Ti, Zr and Sn have the oxidation state 4 here. [0022] The Z element W has the oxidation state 6 here. [0023] The Z element Fe has the oxidation state 3 here. [0024] It is of course possible to replace individual X and/or Z elements by further elements, such as indium (In), aluminum (Al), magnesium (Mg) and chromi-um (Cr), as long as the stoichiometric ratios are taken into account and the . crystal lattice allows. In particular, dopings with chromium and aluminum or with magnesium and aluminum are preferred. [0025] In a preferred embodiment, the X element present is at least La or Y or both, i.e. it holds that b?0 and/or c?0 in the general formula. All other X ele-ments or only selected ones thereof can of course also be present additional-ly. In particular, k ? 0 and/or o ? 0 holds here. [0026] In a further preferred embodiment, X stands for Yb Lac and b + c = 1 and 0 [0027] It is further preferred that X stands for La or for Y, i.e. that only one X ele-ment is present in the general formula. [0028] In another preferred embodiment, X stands for Yb Lac Pre Ndf Dyl, Hom Ern Ybp Crt Mn(III)u Fe(III)v [Mn(II)x Fe(II)y Co? Nid Cue]3/2 and it holds that b + c + e + f+l + m + n + p + t+u + v + 3/2(x + y + ? + d + e) = 1, and b, c, e, f, 1, m, n, p, t, u, v, x, y, ?,d,e each range from 0 to 1. [0029] Further it is preferred if the inventive luminescent substance contains at least one, at least two or at least three rare earth elements as X elements, i.e. that c ?0 and/or d ? 0 and/or e? 0 and/or f ? 0 and/or g? 0 and/or h ?0 and/or i ?0 and/or k? 0 and/or 1? 0 and/or m? 0 and/or n ? 0 and/or o ?0 and/or p?0 and/or q ? 0. -5- [0030] In particular, the rare earth elements are selected from the group of Ho, Er, Yb and Nd, i.e. f ? 0 and/or m ? 0 and/or n ? 0 and/or p ? 0. Particularly preferably, Y is also present in the presence of Ho, Er, Yb and/or Nd. [0031] If at least two rare earth elements are present, these are particularly prefer-ably the combinations Er and Yb with n ? 0 and p ? 0, Nd and Yb with f? 0 and p?0 or Er and Nd with n?0 and f ? 0. [0032] If Ho, Er or Yb is present according to the general formula, i.e. if m ? 0 or n ?0 or p?0, then Pr, Dy, Nd, Cr, Mn, Fe, Co, Ni and/or Cu are preferably also present, so that it holds that e ?0 and/or 1?0 and/or f?0 and/or t ? 0 and/or u ? 0 and/or v ? 0 and/or x ? 0 and/or y ? 0 and/or ? ? 0 and/or d? 0 and/or e ? 0. [0033] If Nd is present according to the general formula, i.e. if f ? 0, then Pr, Dy, Cr, Mn, Fe, Co, Ni and/or Cu are preferably also present, so that it holds that e ? 0 and/or 1 ? 0 and/or t ? 0 and/or u ? 0 and/or v ?0 and/or x ? 0 and/or y ? 0 and/or ? ? 0 and/or d?0 and/or e ?0. [0034] In a further preferred embodiment, X stands for Yb Lac Pre Ndf Ern Ybp Fe(III)v, and b + c + e + f+n + p + v=l,and b, c, e, f, n, p and v each range from 0 to 1. [0035] Further preferably, X stands for Yb Ybp Pre, b + e + p=l,b, e and p each range from 0 to 1, it preferably holding that 0 [0036] Further preferably, X stands for Yb Ndf Fe(III)v, b + f+v=l,b,f and v each range from 0 to 1, it preferably holding that 0 [0037] Further preferably, X stands for Yb Ern, b + n = 1, b and n each range from 0 to 1, it preferably holding that 0 -6- [0038] Further preferably, X stands for Yb Ndf Ern, b + f+n=l,b, f and n each range from 0 to 1, it preferably holding that 0 [0039] Further preferably, X stands for Yb Ybp Ndf, b + p + f = 1, b, p and f each range from 0 to 1, it preferably holding that 0 [0040] Further preferably, X stands for Yb Ndf, b + f = 1, b and f each range from 0 to 1, it preferably holding that 0 [0041] Further preferably, X stands for Yb Ybp, b + p = 1, b and p each range from 0 to 1, it preferably holding that 0 [0042] Further preferably, X stands for Y. [0043] In a further preferred embodiment, the Z element present is at least Ta, Nb, P, Ti or W. At least all five elements can also be present. Thus it holds that za ? 0 and/or zb ? 0 and/or zd ? 0 and/or ze ? 0 and/or zh ? 0. [0044] Further preferably, the Z elements present are only elements selected from the group of Ta, Nb and P. Thus Z stands for Nbza TaZb Pzd, za + zb + zd = 1, and za, zb and zd each range from 0 to 1, it preferably holding that 0 [0045] Further preferably, Z stands for Nbza Tazb, za + zb = 1, and za and zb each range from 0 to 1, it preferably holding that 0 [0046] Compounds with the following formulae are also preferred: Yb Lac Nbzn Tazb O4, where b + c=1,za + zb=1, and b, c, za and zb each range from 0 to 1. Yb Ybp NbO4, where b and p range from 0 to 1, b + p = 1. Particularly preferably it holds that p> 0.5. -7- Yb Ybp Ndf NbO4, where b, p and f each range from 0 to 1, and b + p + f =1. [0047] Particularly preferred compounds are YNbO4; YbNdfNbO4with b + f=l and 0 Yb Ndf NbO4: (Cr, Al) with 0 Yb Ybp Prc NbO4 with b + e + p = 1 and 0 [0048] It preferably holds for all compounds in which Y and Yb are present that the' proportion of Yb is greater than the proportion of Y. [0049] The positions and forms (intensity, width, etc.) of the excitation and/or emis-sion bands are dependent on the quantity ratios of the elements involved, the type of elements and the type and quantity of the dopants. [0050] For protection of value documents it is possible to use both broadband and narrowband luminescence, but for reasons of selectivity the narrowband lu-minescence is preferred. [0051] One normally speaks of narrowband emission when the bands occurring in the emission spectrum show an average half-value width of less than 50 nm. However, this does not mean that bands having a half-value width outside this range do not also solve the inventive problem. [0052] Variation and combination of the inventive luminescent substances open up numerous possibilities for influencing the excitation and emission spectra of -8- the inventive luminescent substances and thus producing a multiplicity of se-curity features. Besides the evaluation of the excitation and/or emission spec-tra, the lifetime of luminescence or decay time can likewise be used for dis-tinction. Evaluation can take account of not only the wavelengths of the exci-tation or emission lines but also their number and/or form and/or intensities, so that any desired coding can be represented. [0053] Likewise it is possible to obtain an energy transfer between like and/or un-like elements in certain inventive luminescent substances, i.e. produce a quasi-resonance, and to use it for identification. [0054] If the value document is marked, not with one, but with several, of the inven-tive luminescent substances, the number of distinguishable combinations can be increased further. If different mixing ratios are moreover distinguished from each other, the number of combinations can be increased again. Mark-ing can be done either at different places on the value document or at the same place. If the luminescent substance is applied or incorporated at differ-ent places on the value document, it is possible to produce a spatial code, in the simplest case e.g. a bar code. [0055] Further, the falsification security of the value document can be increased if the special selected luminescent substance e.g. in a value document is linked with other information of the value document, permitting a check by means of a suitable algorithm. The value document can of course have further addi-tional authenticity features, such as classic fluorescence and/or magnetism, besides the inventive luminescent substance. [0056] The luminescent substances can be incorporated into the value document in a great variety of ways according to the invention. For example, the lumines- cent substances can be incorporated into a printing ink. It is also possible to admix the luminescent substance to the paper pulp or plastic mass during production of a value document based on paper or plastic. The luminescent substances can likewise be provided on or in a plastic supporting material, which for example can in turn be at least partly embedded in the paper pulp. -9- The supporting material, which is based on a suitable polymer, such as PMMA, and in which the inventive luminescent substance is embedded, can have the form of a security thread, a mottling fiber or a planchet. Likewise, for product protection the luminescent substance can be e.g. incorporated di-rectly into the material of the object to be protected, e.g. in housings and plastic bottles. [0057] However, the plastic or paper supporting material can also be fastened to any other desired object e.g. for product protection. In this case the supporting material preferably has the form of a label. If the supporting material is part of the product to be protected, as is the case e.g. with tear threads, any other design is of course also possible. In certain application cases it can be expe-dient to provide the luminescent substance as an invisible coating on the val-ue document. It can be present here all over or also in the form of certain pat-terns, such as stripes, lines, circles, or also in the form of alphanumeric char-acters. To ensure the invisibility of the luminescent substance, it is possible according to the invention to use either a colorless luminescent substance in the printing ink or coating lacquer, or a colored luminescent substance in such a low concentration that the transparency of the coating is just given. Alternatively or in addition, the supporting material can also already be suit-ably colored, so that colored luminescent substances are not perceived due to their inherent color. [0058] The inventive luminescent substances are normally processed in the form of pigments. For better processing or to increase their stability, the pigments can in particular be present as individually encapsulated pigment particles or be covered with an inorganic or organic coating. For example, the individual pigment particles are surrounded by a silicate cover and can thus be more easily dispersed in media. Likewise, different pigment particles of a combi-nation can be encapsulated jointly, e.g. in fibers, threads, silicate covers. It is thus e.g. no longer possible to change the "code" of the combination subse-quently. "Encapsulation" refers here to complete encasing of the pigment -10- particles, while "coating" also refers to partial encasing or coating of the pig-ment particles. [0059] The inventive luminescent substances are characterized in particular by their high intensity in the emission spectrum and the simple production. Further-more, the inventive luminescent substances have the advantage that the loca-tion of the emission bands is already influenced by simple variation in the el-ementary composition, thereby providing a multiplicity of distinguishable feature substances. [0060] In the following, some examples of the inventive luminescent substance will be explained in more detail. [0061] For preparation, the initial substances in oxidic form or substances that can be converted to oxides are mixed in a suitable ratio, then annealed, crushed, washed (e.g. with water), dried and ground. Example 1: Y0.1 Yb0..9TaO4 [0062] 539.46 g of Ta2O5, 27.57 g of Y2O3, 432.97 g of Yb2O3 and 500.00 g of Na2-SO4 (ultrapure, anhydrous) as a fluxing agent are intimately intermixed in a paddle mixer. The mix is poured into a crucible and annealed at 1150°C for 6 to 24 hours. The material cooled for 1 to 2 days after the oven is switched off is liberated from the sulfate by washing, and ground with a common pin mill to fineness that permits homogeneous and invisible incorporation into paper or printing inks. [0063] The thus produced compound has the totals formula Y0.1Yb0.9TaO4. Example 2: Y2.4Yb0..3Nd0. 3CaAlNb2O12 Component Quantity Substance Purity 1 359.660 g Y2O3 5N 2 78.46 g Yb2O3 4N 3 66.988 g Nd2O3 4N 4 74.431 g CaO reagent-g 5 67.662 g A12O3 4N -11- 6 352.80 g Nb2O5 4N 7 1000.00 g Na2SO4 (ultrapure) [0064] Components 1 to 7 are mixed intimately at high turbulence. The mix is poured into crucibles (sintered ceramics based on A12O3) and annealed at 1150°C between 6 to 24 hours. The material cooled over 1 to 2 days after the oven is switched off is washed free of sulfate (detection limit [0065] The thus produced compound has the totals formula Y24Yb0.3Nd0.3-CaAlNb2O12. Example 3: Y0.65Yb0.18Er0.17NbO4 Component Quantity Substance Purity 1 267.58 g Y2O3 5N 2 129.31 g Yb2O3 4N 3 118.543 g Er2O3 3N 4 484.57 g Nb2O5 4N 5 1000.00 g Na2SO4 (ultrapure) [0066] Components 1 to 5 are mixed intimately at high turbulence. The mix is poured into crucibles (sintered ceramics based on Al2O3) and annealed at 1150°C between 6 to 24 hours. The material cooled over 1 to 2 days after the oven is switched off is washed free of sulfate (detection limit [0067] The thus produced compound has the totals formula Y0.65Yb0.18Er0.17NbO4. Example 4: Y0. 4Yb0. 5Nd0.1NbO4 Component Quantity Substance purity 1 153.92 g Y2O3 5N -12- 2 335.77 g Yb2O3 4N 3 57.338 g Nd2O3 3N 4 452.970 g Nb2O5 4N 5 1000.00 g Na2SO4 (ultrapure) [0068] Components 1 to 5 are mixed intimately at high turbulence. The mix is poured into crucibles (sintered ceramics based on Al2O3) and annealed at 1150°C between 6 to 24 hours. The material cooled over 1 to 2 days after the oven is switched off is washed free of sulfate (detection limit [0069] The thus produced compound has the totals formula Y0.4Yb0.5Nd0.1NbO4. Example 5: Y0.099Yb0.9Pr0.001NbO4 Component Quantity Substance Purity 1 34.76 g Y2O3 5N 2 551.44 g Yb2O3 4N 3 0.51 R Pr6O11 4N 4 413.29 g Nb2O5 4N 5 1000.00 g Na2SO4 (ultrapure) [0070] Components 1 to 5 are mixed intimately at high turbulence. The mix is poured into crucibles (sintered ceramics based on Al2O3) and annealed at 1150°C between 6 to 24 hours. The material cooled over 1 to 2 days after the oven is switched off is washed free of sulfate (detection limit [0071] The thus produced compound has the totals formula Y0.099Yb0.9Pr0.001NbO4. -13- Example 6: Y0.967Eu0.033NbO4 Component Quantity Substance Purity 1 440.44 g Y2O3 5N 2 23.42 g Eu2O3 4N 3 536.14 g Nb2O5 4N 4 1000.00 g Na2SO4 (ultrapure) [0072] Components 1 to 4 are mixed intimately at high turbulence. The mix is poured into crucibles (sintered ceramics based on A12O3) and annealed at 1150°C between 6 to 24 hours. The material cooled over 1 to 2 days after the oven is switched off is washed free of sulfate (detection limit [0073] The thus produced compound has the totals formula Y0.967Eu0.033NbO4. Example 7: Y2.8Er0.2Nb0.60Fe4O12 Component Quantity Substance Purity 1 419.55 g Y2O3 5N 2 50.76 g Er2O3 4N 3 105.83 g Nb2O5 4N 4 423.86 g Fe2O3 Carbonyl iron 5 500.00 g Na2SO4 (ultrapure) [0074] Components 1 to 5 are mixed intimately at high turbulence. The mix is poured into crucibles (sintered ceramics based on A12O3) and annealed at 1150°C between 6 to 24 hours. The material cooled over 1 to 2 days after the . oven is switched off is washed free of sulfate (detection limit [0075] The thus produced compound has the totals formula Y2. 8Er0.2Nb0.60Fe4O12. -14- [0076] Further embodiments and advantages of the invention will be explained in the following with reference to the figure. The proportions shown in the fig-ure do not necessarily correspond to the relations existing in reality and serve mainly to improve clarity. [0077] Fig. 1 shows an inventive value document in cross section. [0078] Fig. 1 shows an embodiment of the inventive security element. The security element consists in this case of a label 2 composed of a paper or plastic layer 3, a transparent cover layer 4 and an adhesive layer 5. Said label 2 is con-nected via the adhesive layer 5 to any desired substrate 1. Said substrate 1 can be a value document, identity card, passport, certificate or the like, but also another object to be protected, such as a CD, package or the like. The luminescent substance 6 is contained within the volume of the layer 3 in this embodiment. [0079] Alternatively, the luminescent substance could also be contained in a print-ing ink (not shown) which is printed on one of the label layers, preferably on the surface of the layer 3. [0080] Instead of providing the luminescent substance in or on a supporting material which is then fastened to an object as a security element, it is also possible according to the invention to provide the luminescent substance directly in the value document to be protected or on the surface thereof in the form of a coating. - 15- - Claims 1. - A luminescent substance with the general formula XZO4 where X stands for Sca Yb Lac Ced Pre Ndf Smg Euh Gd, Tbk Dyl, Hom Ern Timo Ybp Luq Sb (III)r Bis Crt Mn(III)u Fe(III)v [Baw Mn(II)x Fe(II)y Caz Sn(II)a Srß Co? Nid Cue]3/2 [Na?, K?]3 [U(IV)µ, Pbp Ths]3/4 U(VI)f/2 and Z stands for Nbzn Taz b Vzc Pzd [Tize Zrzf Sn(IV)zg]5/4 Wzh5/6 Fe(III)Zl5/3 and a + b + c + d + e + f+g + h+i+k + l + m + n + o + p + q + r + s + t+u + v + 3/2 (w + x + y + 2 + a+ß +? + d+e) + 3(? +?) + 3/4(µ + p + s) + f/2 = 1, and a, b, c, d, e, f, g, h, i, k, 1, m, n, o, p, q, r, s, t, u, v, w, x, y, z, a, ß, ?, d, e, ?, ?, µ, p, s and f each range from 0 to 1, and za + zb + zc + zd + 5/4 (ze + zf + zg) + 5/6zh + 5/3zi = 1, and za, zb, zc, zd, ze, zf, zg, zh and zi each range from 0 to 1. (I) 2. A luminescent substance according to claim 1, wherein b? 0 and/or c? 0 and/or k?0and/oro?O. 3. A luminescent substance according to claim 1 or 2, wherein b + c = 1 and 0 1 and0 4. A luminescent substance according to at least one of claims 1 to 3, wherein c = 1 orb=l. 5. A luminescent substance according to claim 1 or 2, wherein - 16- X stands for Yb Lac Prc Ndf Dyl Hom Ern Ybp Crt Mn(III)u Fe(III)v [Mn(II)x Fe(II)y Co? Nid Cue]3/2, and b + c + e + f+l + m + n + p + t+u + v + 3/2(x + y + ? + d + e) = 1, and b, c, e, f, 1, m, n, p, t, u, v, x, y, ?, d, e each range from 0 to 1. 6. A luminescent substance according to at least one of claims 1 to 5, wherein c? 0 and/or d ? 0 and/or e? 0 and/or f ? 0 and /or g ? 0 and/or h?0 and/or i ? 0 and/or k ? 0 and/or 1? 0 and/or m? 0 and/or n? 0 and/or o? 0 and/or p ? 0 and/or q? 0. 7. A luminescent substance according to at least one of claims 1, 2, 5 and 6, wherein m? 0 and/or n? 0 and/or f?0 and/or p? 0. 8. A luminescent substance according to at least one of claims 1, 2, 5 to 7, wherein (n ? 0 and p ? 0) or (f? 0 and p ? 0) or (n? 0 and f ? 0). 9. A luminescent substance according to at least one of claims 1, 2, 5 to 8, wherein if m ? 0 or n ? 0 or p ? 0, then it holds that e ? 0 and/or I ? 0 and/or f ? 0 and/or t ? 0 and/or u? 0 and/or v? 0 and/or x ? 0 and/or y ? 0 and/or ? ? 0 and/or d? 0 and/or e ? 0. 10. A luminescent substance according to at least one of claims 1, 2, 5 to 8, wherein if f? 0, then it holds that e ? 0 and/or 1? 0 and/or t ? 0 and/or u ? 0 and/or v ? 0 and/or x ? 0 and/or y ? 0 and/or ? ? 0 and/or d ?0 and/or e ? 0. 11. A luminescent substance according to at least one of claims 1, 2, 5 to 10, wherein X stands for Yb Lac Pre Ndf Ern Ybp Fe(III)v, and b + c + e + f+n + p + v= 1, and b, c, e, f, n, p and v each range from 0 to 1. 12. A luminescent substance according to at least one of claims 1, 2, 5, 6, 7, 9 to 11, wherein X stands for Yb Ybp Pre, b + e + p = 1, and b, e and p each range from 0 to 1, it preferably holding that 0 -17- 13. A luminescent substance according to at least one of claims 1, 2, 5, 6, 9 to 11, wherein X stands for Yb Ndf Fe(III)v, b + v + f = 1, and b, f and v each range from 0 to 1, it preferably holding that 0 14. A luminescent substance according to at least one of claims 1, 2, 5, 6, 9 to 11, wherein X stands for Yb Ern, b + n = 1, and b and n each range from 0 to 1, it preferably holding that 0 15. A luminescent substance according to at least one of claims 1, 2, 5 to 11, wherein X stands for Yb Ndf Ern, b + f + n = 1, and b, f and n each range from 0 to 1, it preferably holding that 0 16. A luminescent substance according to at least one of claims 1, 2, 5, 6, 7, 9 to 11, wherein X stands for Yb Ybp Ndf, b + p + f= 1, and b, p and f each range from 0 to 1, it preferably holding that 0 17. A luminescent substance according to at least one of claims 1, 2, 5, 6, 9 to 11 and 15, wherein X stands for Yb Ndf, b + f = 1, and b and f each range from 0 to 1, it preferably holding that 0 18. A luminescent substance according to at least one of claims 1, 2, 5, 6, 9, 11 and 16, wherein X stands for Yb Ybp, b + p = 1, and b and p each range from 0 to 1, it preferably holding that 0 19. A luminescent substance according to at least one of claims 1, 2, 4, 5, 11 to 18, wherein X stands for Y. 20. A luminescent substance according to at least one of claims 1 to 19, wherein the luminescent substance is additionally doped, preferably with Al and/or Mg and/or Cr. 21. A luminescent substance according to at least one of claims 1 to 20, wherein the luminescent substance is additionally doped with (Al and Mg) or (aluminum and Cr). -18- 22. A luminescent substance according to at least one of claims 1 to 21, wherein za ^ 0 and/or zb ? 0 and/or ze ? 0 and/or zh ? 0. 23. A luminescent substance according to at least one of claims 1 to 22, wherein Z stands for Nbzn Tazb Pzd, za + zb + zd = 1, and za, zb and zd each range from 0 to 1, it preferably holding that 0 24. A luminescent substance according to at least one of claims 1 to 23, wherein Z stands for Nbzn Tazb, za + zb = 1, and za and zb each range from 0 to 1, it prefer- ably holding that 0 25. A luminescent substance according to at least one of claims 1 to 24, wherein Z stands for Nb with za = 1 or Ta with zb = 1 or P with zd = 1. 26. A security element comprising a luminescent substance according to at least one of claims 1 to 25. 27. A security element according to claim 26, wherein the security element has the form of a strip or band. 28. A security element according to claim 26 or 27, wherein the element is formed as a security thread, planchet or mottling fiber. 29. A security element according to claim 26, characterized in that the security ele ment is formed as a label. 30. A security element according to at least one of claims 26 to 29, characterized in that the at least one luminescent substance is embedded into a supporting material of the security element or applied to the supporting material. 31. A security paper comprising a luminescent substance according to at least one of claims 1 to 25. 32. A value document comprising a luminescent substance according to at least one of claims 1 to 25. -19- 33. A value document according to claim 32, wherein the value document consists of paper or plastic. 34. A value document according to claim 32 or 33, wherein the luminescent sub- stance is incorporated into the volume of the value document or present in a layer applied to the value document. 35. A value document according to at least one of claims 32 to 34, wherein the lumi- nescent substance is provided as an invisible coating at least partly covering the surface of the value document. 36. A value document according to at least one of claims 32 to 35, wherein the lumi- nescent substance is admixed, to a printing ink. 37. A value document according to at least one of claims 32 to 36, wherein the coat- ing has the form of one or more strips. 38. A value document according to at least one of claims 32 to 37, wherein the lumi- nescent substance is present as pigment particles. 39. A method for producing a value document according to at least one of claims 32 to 38, characterized in that the luminescent substance is added to a printing ink. 40. A method for producing a value document according to at least one of claims 32 to 38, characterized in that the luminescent substance is applied by a coating pro- cess. 41. A method for producing a value document according to at least one of claims 32 to 38, characterized in that the luminescent substance is incorporated into the vol- ume of the value document. 42. A method for producing a value document according to at least one of claims 32 to 38, characterized in that the luminescent substance is supplied to the value document by accordingly prepared mottling fibers. -20- 43. A method for producing a value document according to at least one of claims 32 to 38, characterized in that the luminescent substance is supplied to the value document by an accordingly prepared security thread. 44. A test method for checking the authenticity of a value document according to at least one of claims 32 to 38 or of a security element according to at least one of claims 26 to 30, characterized in that the wavelengths and/or number and/or the form and/or the intensities of the emission lines and/or the excitation bands of the luminescent substances are evaluated. 45. A test method for checking the authenticity of a value document or security ele- ment according to claim 44, characterized in that the emission lines and/or excita- tion bands represent a coding. 46. A test method for checking the authenticity of a value document according to at least one of claims 32 to 38 or of a security element according to at least one of claims 26 to 30, characterized in that the lifetimes of luminescence of the lumi- nescent substances are evaluated. The invention relates to a printed value document having at least one luminescent substance.

Documents:

03914-kolnp-2006 abstract.pdf

03914-kolnp-2006 claims.pdf

03914-kolnp-2006 correspondence others.pdf

03914-kolnp-2006 description(complete).pdf

03914-kolnp-2006 drawings.pdf

03914-kolnp-2006 form-1.pdf

03914-kolnp-2006 form-3.pdf

03914-kolnp-2006 form-5.pdf

03914-kolnp-2006 general power of authority.pdf

03914-kolnp-2006 international publication.pdf

03914-kolnp-2006 international search authority report.pdf

03914-kolnp-2006 pct others.pdf

03914-kolnp-2006 priority document.pdf

03914-kolnp-2006-assignment.pdf

03914-kolnp-2006-correspondence-1.1.pdf

03914-kolnp-2006-correspondence-1.2.pdf

03914-kolnp-2006-form-18.pdf

03914-kolnp-2006-form-3-1.1.pdf

3909-KOLNP-2012-(08-02-2013)-CORRESPONDENCE.pdf

3914-KOLNP-2006-(03-10-2012)-ABSTRACT.pdf

3914-KOLNP-2006-(03-10-2012)-ANNEXURE TO FORM 3.pdf

3914-KOLNP-2006-(03-10-2012)-CLAIMS.pdf

3914-KOLNP-2006-(03-10-2012)-CORRESPONDENCE.pdf

3914-KOLNP-2006-(03-10-2012)-DRAWINGS.pdf

3914-KOLNP-2006-(03-10-2012)-FORM-1.pdf

3914-KOLNP-2006-(03-10-2012)-FORM-13.pdf

3914-KOLNP-2006-(03-10-2012)-FORM-2.pdf

3914-KOLNP-2006-(03-10-2012)-OTHERS.pdf

3914-KOLNP-2006-(03-10-2012)-PA.pdf

3914-KOLNP-2006-(03-10-2012)-PETITION UNDER RULE 137.pdf

3914-KOLNP-2006-(07-05-2013)-ABSTRACT.pdf

3914-KOLNP-2006-(07-05-2013)-CLAIMS.pdf

3914-KOLNP-2006-(07-05-2013)-CORRESPONDENCE.pdf

3914-KOLNP-2006-(07-05-2013)-FORM 3.pdf

3914-KOLNP-2006-(07-05-2013)-OTHERS.pdf

3914-KOLNP-2006-(08-02-2013)-CORRESPONDENCE.pdf

3914-KOLNP-2006-(14-08-2012)-CORRESPONDENCE.pdf

3914-KOLNP-2006-(17-07-2012)-ENGLISH TRANSLATION OF PRIORITY DOCUMENTE.pdf

3914-KOLNP-2006-(17-07-2012)-EXAMINATION REPORT REPLY RECEIVED.pdf

3914-KOLNP-2006-(29-11-2013)-CORRESPONDENCE.pdf

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