EP3049253A2 - Value document and method for verification of the presence thereof - Google Patents
Value document and method for verification of the presence thereofInfo
- Publication number
- EP3049253A2 EP3049253A2 EP14777522.5A EP14777522A EP3049253A2 EP 3049253 A2 EP3049253 A2 EP 3049253A2 EP 14777522 A EP14777522 A EP 14777522A EP 3049253 A2 EP3049253 A2 EP 3049253A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- substance
- luminescent
- detectable
- spectroscopic method
- homogeneous phase
- 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.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 32
- 238000012795 verification Methods 0.000 title 1
- 239000000126 substance Substances 0.000 claims abstract description 225
- 238000004611 spectroscopical analysis Methods 0.000 claims abstract description 89
- 238000005259 measurement Methods 0.000 claims abstract description 57
- 238000011156 evaluation Methods 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims description 95
- 230000005855 radiation Effects 0.000 claims description 22
- 238000005481 NMR spectroscopy Methods 0.000 claims description 21
- 230000005670 electromagnetic radiation Effects 0.000 claims description 18
- 238000000804 electron spin resonance spectroscopy Methods 0.000 claims description 18
- 238000001069 Raman spectroscopy Methods 0.000 claims description 14
- 238000003876 NQR spectroscopy Methods 0.000 claims description 11
- 238000010521 absorption reaction Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 7
- 238000012937 correction Methods 0.000 claims description 6
- 239000002105 nanoparticle Substances 0.000 claims description 6
- 239000007771 core particle Substances 0.000 claims description 3
- 239000010420 shell particle Substances 0.000 claims description 3
- 230000000712 assembly Effects 0.000 claims description 2
- 238000000429 assembly Methods 0.000 claims description 2
- 239000000758 substrate Substances 0.000 description 28
- 239000007787 solid Substances 0.000 description 24
- 239000013543 active substance Substances 0.000 description 17
- 238000004416 surface enhanced Raman spectroscopy Methods 0.000 description 15
- 238000009826 distribution Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 238000004020 luminiscence type Methods 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 5
- 230000002776 aggregation Effects 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229920001131 Pulp (paper) Polymers 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 239000011258 core-shell material Substances 0.000 description 4
- 238000005314 correlation function Methods 0.000 description 4
- 239000000049 pigment Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229910052566 spinel group Inorganic materials 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- HICARRDFVOAELS-UHFFFAOYSA-N O(Cl)Cl.[Y] Chemical compound O(Cl)Cl.[Y] HICARRDFVOAELS-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- PSNPEOOEWZZFPJ-UHFFFAOYSA-N alumane;yttrium Chemical compound [AlH3].[Y] PSNPEOOEWZZFPJ-UHFFFAOYSA-N 0.000 description 2
- -1 apatites Chemical class 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 229910003480 inorganic solid Inorganic materials 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- UBXAKNTVXQMEAG-UHFFFAOYSA-L strontium sulfate Chemical compound [Sr+2].[O-]S([O-])(=O)=O UBXAKNTVXQMEAG-UHFFFAOYSA-L 0.000 description 2
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 2
- 238000004415 surface enhanced infrared absorption spectroscopy Methods 0.000 description 2
- RLQWHDODQVOVKU-UHFFFAOYSA-N tetrapotassium;silicate Chemical compound [K+].[K+].[K+].[K+].[O-][Si]([O-])([O-])[O-] RLQWHDODQVOVKU-UHFFFAOYSA-N 0.000 description 2
- 238000000772 tip-enhanced Raman spectroscopy Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical group C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- DJHGAFSJWGLOIV-UHFFFAOYSA-K Arsenate3- Chemical class [O-][As]([O-])([O-])=O DJHGAFSJWGLOIV-UHFFFAOYSA-K 0.000 description 1
- 235000003197 Byrsonima crassifolia Nutrition 0.000 description 1
- 240000001546 Byrsonima crassifolia Species 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 238000003646 Spearman's rank correlation coefficient Methods 0.000 description 1
- 238000002872 Statistical quality control Methods 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 229910000611 Zinc aluminium Inorganic materials 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- JEROREPODAPBAY-UHFFFAOYSA-N [La].ClOCl Chemical compound [La].ClOCl JEROREPODAPBAY-UHFFFAOYSA-N 0.000 description 1
- MCVAAHQLXUXWLC-UHFFFAOYSA-N [O-2].[O-2].[S-2].[Gd+3].[Gd+3] Chemical compound [O-2].[O-2].[S-2].[Gd+3].[Gd+3] MCVAAHQLXUXWLC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052650 alkali feldspar Inorganic materials 0.000 description 1
- HXFVOUUOTHJFPX-UHFFFAOYSA-N alumane;zinc Chemical compound [AlH3].[Zn] HXFVOUUOTHJFPX-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- WAKZZMMCDILMEF-UHFFFAOYSA-H barium(2+);diphosphate Chemical compound [Ba+2].[Ba+2].[Ba+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O WAKZZMMCDILMEF-UHFFFAOYSA-H 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910052810 boron oxide Inorganic materials 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 150000004770 chalcogenides Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 description 1
- MTRJKZUDDJZTLA-UHFFFAOYSA-N iron yttrium Chemical compound [Fe].[Y] MTRJKZUDDJZTLA-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000012067 mathematical method Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 238000002094 microwave spectroscopy Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- GFKJCVBFQRKZCJ-UHFFFAOYSA-N oxygen(2-);yttrium(3+);trisulfide Chemical compound [O-2].[O-2].[O-2].[S-2].[S-2].[S-2].[Y+3].[Y+3].[Y+3].[Y+3] GFKJCVBFQRKZCJ-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229910052655 plagioclase feldspar Inorganic materials 0.000 description 1
- 229920000015 polydiacetylene Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000007619 statistical method Methods 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- JOPDZQBPOWAEHC-UHFFFAOYSA-H tristrontium;diphosphate Chemical compound [Sr+2].[Sr+2].[Sr+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JOPDZQBPOWAEHC-UHFFFAOYSA-H 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 1
- 238000002460 vibrational spectroscopy Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
- 229910000164 yttrium(III) phosphate Inorganic materials 0.000 description 1
- UXBZSSBXGPYSIL-UHFFFAOYSA-K yttrium(iii) phosphate Chemical compound [Y+3].[O-]P([O-])([O-])=O UXBZSSBXGPYSIL-UHFFFAOYSA-K 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
- G07D7/20—Testing patterns thereon
- G07D7/202—Testing patterns thereon using pattern matching
- G07D7/2041—Matching statistical distributions, e.g. of particle sizes orientations
-
- 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
- B42D25/30—Identification or security features, e.g. for preventing forgery
-
- 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
-
- 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
-
- 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
Definitions
- the invention relates to a value document such as a banknote and a method for checking the presence thereof.
- the authenticity assurance of value documents by means of luminescent substances has long been known. Preference is given to using rare earth-doped host lattices, wherein the absorption and emission ranges can be varied within a wide range by suitable tuning of rare earth metal and host lattice.
- the use of magnetic and electrically conductive materials for authenticity assurance is known per se. Magnetism, electrical conductivity and luminescence emission are mechanically detectable by commercially available measuring devices, and luminescence is also visual in sufficient intensity when emitted in the visible range.
- Value document comprising particulate agglomerates, each containing at least two different (especially solid) homogeneous phases, wherein the first homogeneous phase based on a first non-luminescent, detectable by a spectroscopic method substance and the second homogeneous phase based on a second non-luminescent, detectable by a spectroscopic method substance.
- the spectroscopic method on which the first spectral method is based and the second measurement signal, caused by the second substance, which is the basis of the spectroscopic method. Intensity are available, there is a statistical correlation between the first measurement signal intensities and the second measurement signal intensities.
- non-luminescent substance of the first (especially solid) homogeneous phase and the non-luminescent substance of the second (especially solid) homogeneous phase of the following five types of substances, namely a means Nuclear magnetic resonance spectroscopy detectable substance, a substance detectable by means of electron spin resonance spectroscopy, a substance detectable by means of nuclear quadrupole resonance spectroscopy, a substance detectable by means of SER (Surface Enhanced Raman) spectroscopy and a
- non-luminescent substance of the first homogeneous phase and the non-luminescent substance of the first homogeneous phase luminescent substance of the second homogeneous phase from the following five types of substance, namely a substance detectable by nuclear magnetic resonance spectroscopy, a substance detectable by electron spin resonance spectroscopy, a substance detectable by nuclear quadrupole resonance spectroscopy, a substance detectable by means of SER (Surface Enhanced Raman) spectroscopy and a by means of SEIRA ( Surface Enhanced Infrared Absorption Spectroscopy detectable material, with the proviso that the nature of the non-luminescent material of the first homogeneous phase is different than the type of non-luminescent substance of the second homogeneous phase.
- SER Surface Enhanced Raman
- a preferred combination is particle agglomerates having a first homogeneous phase detectable by SER spectroscopy and a second homogeneous phase detectable by SER spectroscopy, the exciting electromagnetic radiation of the spectroscopic method being infrared radiation.
- Another preferred combination is encapsulated particle agglomerates having a first homogeneous phase detectable by SER spectroscopy and a second homogeneous phase detectable by SER spectroscopy, the exciting electromagnetic radiation of the spectroscopic method being infrared radiation.
- Another preferred combination is particle agglomerates having a first homogeneous phase detectable by SER spectroscopy and a second homogeneous phase detectable by SEIRA spectroscopy, the exciting electromagnetic radiation of the spectroscopic method being infrared radiation.
- particle agglomerates with a first homogeneous phase which can be detected by means of SER spectroscopy
- a second homogeneous phase which can be detected by nuclear magnetic resonance spectroscopy or by electron spin resonance spectroscopy or by nuclear quadrupole resonance spectroscopy.
- the exciting radiation is infrared radiation
- the exciting radiation in the radio wavelength range in the case of nuclear magnetic resonance spectroscopy or nuclear quadrupole resonance spectroscopy the exciting radiation in the radio wavelength range
- electron spin resonance spectroscopy the exciting radiation in the radio to microwave wavelength range.
- a statistical correlation function with respect to the measured values obtained is calculated and their amount compared with a threshold value.
- a correlation function normalized in magnitude to a value range of 0 to 1 an existing statistical correlation and thus authenticity is recognized if the amount is> 0.3, preferably> 0.5, and particularly preferably> 0.7.
- the procedure for assessing the authenticity of a value document can be as follows: In a first step, the measurement data for the non-luminescent substances, which are the basis of the respective spectroscopic method, are used obtained first measurement signal intensities and second measurement signal intensities. In a second step, the measurement data are normalized. In a third step, a transformation of the coordinate axes takes place, preferably a rotation through 45 ° in order to minimize the scattering of the data points along a coordinate axis. In a fourth step, the quantiles are determined in the direction of the two new coordinate axes, preferably the quartiles, and set their distances or differences in relation to each other. By comparing this ratio with previously determined threshold values, the authenticity of the value document is determined.
- the measured values of locations in the immediate vicinity of the measured values below the specific threshold value are also not used for the authenticity determination.
- Documents of value within the scope of the invention are items such as banknotes, checks, stocks, tokens, identity cards, passports, credit cards, documents and other documents, labels, seals, and items to be protected, such as CDs, packaging and the like.
- the preferred application is banknotes, which are based in particular on a paper substrate.
- Luminescent substances are used as standard for securing banknotes. In the case of a luminescent authentication feature, e.g. is introduced at various locations in the paper of a banknote, the luminescence signals of the feature at the various locations naturally subject to certain fluctuations.
- NMR nuclear magnetic resonance
- ESR Electron spin resonance spectroscopy
- the microwave spectroscopy is based on an exciting electromagnetic radiation having a wavelength in a range of 1 mm to 10 cm.
- the sub-millimeter wave spectroscopy is based on an exciting electromagnetic radiation having a wavelength in the range of 100 ⁇ to 1 mm (also known as terahertz radiation).
- the vibrational spectroscopy in particular Raman spectroscopy, more particularly the SER (Surface Enhanced Raman) spectroscopy or the SERR (Surface Enhanced Resonant Raman) spectroscopy, is based on exciting electromagnetic radiation having a wavelength in the range from 200 nm to 3 ⁇ , preferably in a range of 780 nm to 3 ⁇ , ie near infrared radiation.
- Infrared spectroscopy in particular SEIRA (Surface Enhanced Infrared Absorption), is based on an exciting wavelength in the range from 800 nm to 1 mm, preferably 3 ⁇ m to 1 mm, ie medium and far infrared radiation.
- SEIRA Surface Enhanced Infrared Absorption
- the present invention is based on the finding that a specific generation of mixed, particulate agglomerates of a first non-luminescent substance on the one hand and a second non-luminescent substance on the other hand, each of which can be detected spectroscopically, the effect of a statistical correlation of the intensity fluctuations Measurement signal intensities of both substances result.
- Non-correlating authenticity features are in particular the mixtures of two different non-luminescent, spectroscopically detectable substances, which are each untreated and powdery.
- it is the basic principle of the present invention that two or more substances with different measurable properties are combined in a single particle.
- the relative intensities of the measurement signals are coupled to one another, so that security features based on such particles can be distinguished, for example, from a simple mixture of the individual particles of the two or more substances.
- the use of the above effect leads to an increase in the protection against counterfeiting, because non-correlating feature signals can be recognized as "spurious.”
- the number of possible codings can be increased.
- the two individual non-luminescent feature substances A and B and a luminescent or non-luminescent feature substance C contains, by means of a targeted particulate agglomeration of respectively two or three of the feature substances, the four distinguishable variants (A + B), C / A, (B + C) / ( A + C), B / (A + B + C) are generated, with the signals of the substances within a bracket correlating with each other.
- the particulate agglomerates according to the invention each contain at least two different solid homogeneous phases, the first solid homogeneous phase being based on a first non-luminescent substance which can be detected by a spectroscopic method (also referred to herein as the "first non-luminescent feature substance") and the second solid homogeneous phase on a second non-luminescent, by means of
- the exciting electromagnetic radiation of the spectroscopic method may have a wavelength in a range from 200 nm to 100 m, preferably 780 nm to 100 m.
- the particulate agglomerates are non-planar or platelet-like, but three-dimensionally expanded, in particular spherical or globular (for example elliptical) or fractal. This provides a direct analysis of the different solid homogeneous phases with simple methods such as e.g. complicated by light microscopy.
- non-luminescent feature substance means that the spectroscopically detectable feature substance is not a luminescent pigment, as is typically used in the prior art for securing banknotes and other value documents.
- the adhesion of the two substances, in the form of solid homogeneous phases, must be sufficiently strong that no separation of the two substances takes place during storage and processing, at least not in a degree disturbing the production of safety features.
- the particulate agglomerates according to the invention may in particular be core / shell particles, particle agglomerates, encapsulated particle agglomerates or particles enveloped by nanoparticles. Particle agglomerates and encapsulated particle agglomerates are particularly preferred.
- the shell or capsule may be on an inorganic or organic based material (eg inorganic oxide or organic polymer). A shell of inorganic oxides, eg S1O2, is preferred.
- the agglomerates are preferably prepared by a special process in which the different security features (that is, the different non-luminescent substances) are mixed in a salt-containing aqueous solution at low shear forces and then an aqueous silicate solution is metered in.
- the silicate solution is neutralized by a likewise added or already contained in the aqueous salt solution acid source and connects by the resulting S1O2 the individual particles of security features to solid agglomerates.
- an agglomerate may comprise single particles of two or more security features (luminescent or non-luminescent) and, in addition, individual particles of one or more inactive materials which themselves are not security features.
- the non-luminescent substance which can be detected by means of a specific spectroscopic method of the first and second solid homogeneous phase of the particulate agglomerate is preferably one by means of nuclear magnetic resonance spectroscopy (NMR), nuclear quadrupole resonance spectroscopy (NQR), electron spin resonance spectroscopy (ESR), SER (Surface Enhanced Raman) spectroscopy or SEIRA (Surface Enhanced Infrared Absorption) spectroscopy of detectable matter.
- NMR nuclear magnetic resonance spectroscopy
- NQR nuclear quadrupole resonance spectroscopy
- ESR electron spin resonance spectroscopy
- SEIRA Surface Enhanced Raman Absorption
- the abbreviation SER is understood to mean the surface-enhanced Raman scattering.
- SEIRA means surface-enhanced infrared absorption.
- the non-luminescent substance detectable by NMR spectroscopy will hereinafter also be referred to as "NMR-active substance” or “NMR-tag”.
- the non-luminescent substance that can be detected by means of ESR spectroscopy is also referred to below as “ESR-active substance” or “ESR-tag”.
- the non-luminescent substance detectable by NQR spectroscopy will hereinafter also be referred to as "NQR-active substance” or “NQR-tag”.
- the non-luminescent substance detectable by SER spectroscopy will hereinafter also be referred to as "SERS active substance” or "SERS tag”.
- the non-luminescent substance of the first solid homogeneous phase and the non-luminescent substance of the second solid homogeneous phase can be detected in particular by the following five types of substance, namely a substance detectable by nuclear magnetic resonance spectroscopy, a substance detectable by means of electron spin resonance spectroscopy, a nuclear quadrupole resonance nance spectroscopy detectable substance, a substance detectable by means of SER (Surf ace Enhanced Raman) spectroscopy and a substance detectable by means of SEIRA (Surface Enhanced Infrared Absorption) spectroscopy, with the proviso that the type of non-luminescent substance is the first solid homogeneous phase with the type of non-luminescent substance of the second solid homogeneous phase is identical.
- SER Surface Enhanced Infrared Absorption
- the two non-luminescent substances must differ with regard to the signal position of the measurement signal.
- the non-luminescent substance of the first solid homogeneous phase and the non-luminescent substance of the second solid homogeneous phase are of the following five types of substances, namely a substance detectable by nuclear magnetic resonance spectroscopy, a substance detectable by means of electron spin resonance spectroscopy Core- quadrupole resonance spectroscopy detectable substance, a means
- SER Surface Enhanced Raman
- SEIRA Surface Enhanced Infrared Absorption
- the particulate agglomerate may be e.g. to combine NMR tags and SERS tags in the form of a particle agglomerate. If a simple mixture of NMR tags and SERS tags were introduced into the (paper) substrate of a value document, both types of particles could be randomly distributed in the substrate. In such a random distribution, there is no correlation between the measured NMR signals and the measured SERS signals. If, on the other hand, an agglomerate of both particle types is introduced into the substrate of a value document, the two signals correlate with one another. Sites with relatively high NMR signals also show increased SERS signals, sites with relatively low NMR signals also show reduced SERS signals.
- a separation of the two substances is to be prevented.
- a simple mixture of strongly different particles such as NMR tags of size 5 to 10 ⁇ and SERS tags of size 100 nm
- a different installation behavior takes place in a paper substrate. These include enrichment at different locations (eg at the paper fiber surface or in fiber spaces due to different surface charge of the particles), a different dispersion behavior (eg clumping of the SERS tags in water), different reactions.
- Tention properties eg different strong retention assets in the paper web of a paper machine
- a mechanical segregation eg size separation by shaking movements during transport of a container with pul verförmigen feature substances.
- microscope setup is meant that the measuring device used for the investigation, for example by a high spatial resolution in the measuring field, is able to check individual or only a few particles with regard to the property to be measured.
- ESR-active substances as a security feature inter alia for banknotes is known in the art (see for example US 4,376,264 A, US 5,149,946 A and DE 195 18 086 A).
- EP 0 775 324 B1 describes the use of substances as a security feature which are excited by resonance in the high-frequency range without additional applied electrical or magnetic fields ("zero field"), in particular NQR-active substances in EP 2 505 619 A1.
- the encapsulation of luminescent substances in a polymer or siliceous shell or the like is e.g. from WO 2011/066948 AI, US 2003/0132538 AI and WO 2005/113705 AI known.
- the four distinguishable variants (A + B), C / A, (B + C) / (A + C), B / (A + B + C) are generated, with the signals of the substances within a bracket correlating with each other.
- the luminescent Substance can be excited in particular by radiation in the infrared and / or visible and / or ultraviolet range for luminescence emission, preferably phosphorescence emission.
- the luminescent substance may be a substance emitting in the visible or in the non-visible spectral range (eg in the UV or NIR range). Luminescent substances that emit in the NIR range are preferred (the abbreviation NIR stands for near infrared).
- the luminescent material may be based on a matrix-forming inorganic solid doped with one or more rare earth metals or transition metals.
- the luminescent substance is also referred to hereinafter as "luminophore particle.”
- Suitable inorganic solids which are suitable for forming a matrix are, for example:
- Oxides especially 3- and 4-valent oxides such.
- titanium oxide alumina, iron oxide, boron oxide, yttrium oxide, cerium oxide, zirconium oxide, bismuth oxide, and more complex oxides such.
- B. grenade including u. A. e.g. Yttrium iron garnets, yttrium aluminum garnets, gadolinium gallium garnets;
- Perovskites including u.A. Yttrium aluminum perovskite, lanthanum gallium perovskite; Spinels, including u. A. zinc-aluminum spinels, magnesium-aluminum spinels, manganese-iron spinels; or mixed oxides, e.g. ITO (Indium Tin Oxide);
- Oxyhalides and oxychalcogenides in particular oxychlorides such.
- Sulfides and other chalcogenides e.g. Zinc sulfide, cadmium sulfide, zinc selenide, cadmium selenide;
- Sulfates in particular barium sulfate and strontium sulfate
- Phosphates in particular barium phosphate, strontium phosphate, calcium phosphate, yttrium phosphate, lanthanum phosphate, as well as more complex phosphate-based compounds such as apatites, among others.
- Silicates and aluminosilicates especially zeolites, e.g. Zeolite A, zeolite Y; zeolite-related compounds such as e.g. sodalites; Feldspats such. Alkali feldspar, plagioclase;
- inorganic classes of compounds such as e.g. Vanadates, germanates, arsenates, niobates, tantalates.
- Another picture results from the combination of two different feature substances, e.g. a first non-luminescent feature substance and a second non-luminescent feature substance, to a particulate agglomerate (see Figure 1).
- a particulate agglomerate obtained by agglomerating a mixture of feature substances "A" and "B” would combine both types of feature substances.
- FIG. 2 schematically compares the measurement signal intensities of the feature substances "A” and “B” at four locations of a paper substrate, wherein the densely dotted areas symbolize high signal intensities and the less dense areas less signal intensities.
- Feature substances "A” and “B”, each having a high measurement signal intensity are used in low amount. This results in some areas giving a high "Signal A” and some areas having a high “Signal B”. There is no relationship between the two signals, i. no statistical correlation.
- the term "pure substance agglomerate” is understood to mean an agglomerate which has only particles of a single particle type.
- Particulate agglomerates obtainable from particles "A” and particles "B” are used.
- the starting materials A and B may each have a high or a low intensity. This results in areas with increased “signal A” and at the same time increased “signal B” and areas with low “signal A” and at the same time low “signal B”. In other words, there is a statistical correlation between the two signals.
- the relationship between "Signal A” and “Signal B” shown on the right in Figure 2 is not necessarily directly proportional.
- the particulate agglomerates are ideally, but not necessarily, comprised of 50% Particles A and 50% Particles B. It is possible that a production method results in particulate agglomerates having a random internal distribution of feature substances A and B.
- agglomerate compositions can be formed which on average consist of ten feature substance particles and contain agglomerates with a composition "5A + 5B", but also "3A + 7B” and "7A + 3B” etc.
- a particularly strong signal of substance "A” is measured, but the signal of substance "B” is not significantly increased, but this is statistically unlikely Local depletion or agglomeration of the agglomerates is likely to cause a degree of depletion of the signals of "A" and "B.”
- the signals correlate with each other.
- the dot distribution shown in FIG. 4 would ideally represent a line. Due to the statistical composition of the agglomerates, this behavior is often not present in reality, because for such behavior all agglomerates would have to have a fixed ratio of eg exactly 50% "A” content and exactly 50% "B” content. In practice, however, the generation of such systems or their approximation to this state is possible, for example by (1) an electrostatic preference for heterogeneous agglomeration, or (2) a massive increase in the number of particles per agglomerate, or (3) by use of nanoparticles, or (4) through controlled assembly of core-shell systems of defined sizes.
- the ratio of the intensities between "A” and "B" at arbitrary locations of the sheet is within a very narrow range of values, which is a property advantageous for authentication and also allows discrimination of correlating and non-correlating systems.
- the correlation can be detected at the microscopic level, ie for individual particles. For this purpose, a single agglomerate or a group of agglomerates is examined and it is checked whether they respectively show the properties of the individual substances "A" and "B" used for the construction of the agglomerates.
- Ranking Perform the calculations not on the original values, but on the ranking indices.
- Spearman Rank Correlation Coefficient Bravais-Pearson correlation coefficient above applied to rank order indices.
- Kendall's Tau Examines how often all pairs of data points maintain order.
- the above correlation function can be calculated with respect to the measured values obtained and their amount compared with a threshold value.
- an existing statistical correlation and thus authenticity is recognized if the amount is> 0.3, preferably> 0.5, and particularly preferably> 0.7.
- Example 2 Method with several steps, with the aim of evaluating the length-to-width ratio of the point clouds obtained from the measured data (see FIG. 5). To minimize the influence of "outliers", In each case, the 25% of the highest and lowest signal values were ignored. Correlating point clouds are elongated and have a pronounced length-to-width ratio; in uncorrelated point clouds, their length and width are about the same.
- the following procedure can be used for evaluating the authenticity of a value document:
- the measurement data of the two spectroscopic methods (which are possibly identical) are obtained.
- the measured data are normalized.
- a transformation of the coordinate axes takes place, preferably a rotation through 45 ° in order to minimize the scattering of the data points along a coordinate axis.
- the quantiles are determined in the direction of the two new coordinate axes, preferably the quartiles, and set their distances or differences in relation to each other. By comparing this ratio with previously determined threshold values, the authenticity of the value document is determined.
- the value document according to the invention can additionally have a print, a watermark and / or a security element based on a security patch or a security strip.
- additional security elements are factors which interfere with the correct evaluation of the statistical correlation or cause an additional correlation effect which is not caused by the particular structure of the particulate agglomerate according to the invention.
- FIG. 6 shows a comparison between the measurement signals of two non-correlating feature substances in an unprinted paper substrate and after overprinting with a striped pattern.
- overprinting e.g. by absorbing the radiation used for the excitation, which lowers the signal intensity of the two features used.
- attenuation of the signal occurs at the overprinted points, causing a spatial correlation of the signal intensities of both feature substances.
- This results in a similar effect as achieved by the use of particulate agglomerates according to the invention. Consequently, a clear distinction between "normal", i.e. non-inventive, features and features according to the invention is made more difficult, and therefore, by way of example, two ways are listed below which eliminate or reduce such undesired correlation effects caused by overprinting or the like:
- an additional at a certain emission wavelength luminescent or separately with the detectable component introduced into the value document of the spectroscopic method, which is non-correlating (correction component).
- a suitable, third non-correlating component and normalizing by its signal intensity for example, all of the disturbing effects described above disappear.
- luminescent substances which have particularly small or ideally no spatially dependent fluctuations in the luminescence intensity in an unmodified paper substrate, ie would have a spatially homogeneous luminous intensity without additional influences. Applied to the example shown in FIG. 6, this would mean that the periodic weakening due to the overprinted fringe pattern influences the third component in addition to the first two feature substances.
- the output states of all other components can be recalculated, thus eliminating all correlation effects that affect all three components equally, depending on the application case overprinting and thickness differences in the Substrate, but has no effect on correlation effects that affect only certain components.In this way, the agglomeration-based correlation effects according to the invention are not affected.
- Correction Method 2 When the introduction of the above-mentioned third component is e.g. For cost reasons undesirable, other methods can be used depending on the application. If the measurement signal intensity is in an unmodified paper substrate, e.g. usually above a certain level
- Threshold value and will only become effective through overprinting effects or thickness changes. Changes in the paper substrate, etc. brought below this threshold, corresponding data points can be eliminated from the analysis. This method is particularly useful in cases of abrupt and sharp intensity changes, such as overprinting with sharply defined lines and areas, but less for gradual gradations of color with a smooth transition or filigree patterns. If the measured regions are locally close to one another, it is advantageous to likewise eliminate all adjacent measuring points when the threshold value is undershot at a measuring point (see FIG. 7). This excludes partially overprinted measuring ranges at the boundary of an overprinted area, even if their intensities are above the threshold value due to the only incomplete overpressure.
- FIG. 7 shows how overprinted measuring ranges are excluded below an intensity threshold value (designated by crosses in the figure). Subsequently, the adjacent areas are also excluded.
- particulate agglomerates according to the invention are described below in connection with FIG. 8 on the basis of preferred embodiments.
- a number of preparation processes are suitable for producing the particulate agglomerates according to the invention starting from a first non-luminescent feature substance and a second non-luminescent feature substance (and optionally one or more further luminescent or non-luminescent feature substances).
- the previously isolated particles are caused to assemble into a larger unit.
- the way The larger unit obtained is then fixed so that the particles can no longer separate from each other during use as a security feature. It is crucial that the larger units contain as much as possible equal parts of both (or of the three or more) feature substances, with most production methods a random statistical mixture of the particles is obtained.
- the agglomerates contain only one particle type. This can e.g. then take place if the different feature substances are not thoroughly mixed before the assembly process, or if the combination of similar substances is favored by surface effects or the like. In the normal case, or if the synthesis procedures are carried out correctly, however, such effects are negligible.
- the particle size (D99) of the agglomerates is therefore preferably in the range from 1 to 100 ⁇ m, particularly preferably from 5 to 30 ⁇ m, very particularly preferably from 10 to 20 ⁇ m.
- macroscopic carrier bodies in which the different feature substances are incorporated for example planchettes or mottled fibers, can be used instead of the described particle agglomerates.
- These carrier bodies can then have sizes in excess of 100 ⁇ in individual or all room dimensions, eg have sizes in the millimeter range.
- the particles from which the agglomerate is composed should be significantly smaller than the agglomerate, since with decreasing size a higher number of particles per agglomerate can be incorporated.
- a higher number of incorporated particles increases the likelihood of a "suitable distribution" of both types of particles in the agglomerate, meaning the following relationship: If the starting material were so large that only three particles of substances A and B could form an agglomerate, Without exceeding the maximum agglomerate size, the combinations ⁇ '/, ⁇ ' /, ⁇ '/, ⁇ ' would be conceivable, but such a composition would be completely unsuitable for the use according to the invention, since 25% of the agglomerates would consist only of one single substance (AAA or BBB) and thus produce no correlation, the other 75% would consist of one-third of one substance and two-thirds of the second substance, and would thus produce only poor correlation values.
- luminescent feature substances show a significant loss of intensity, which is mostly due to the enlargement of the surface, since here energy can be dissipated without radiation to surface defects. Certain non-luminescent feature substances also adversely react to significantly increased particle surfaces. Too large a grain size, however, leads to the problems described above in the preparation of suitable agglomerates.
- small to medium size particles e.g. with a grain size between 1 and 5 ⁇ used.
- the ratio of the two substances A and B, from which the agglomerates are prepared is ideally 1: 1, if both substances have the same intensity and grain size.
- an adaptation of this ratio may be advantageous. It may also be necessary under certain circumstances to adjust the quantitative ratio in order, for example, to generate a specific desired mean intensity ratio of both signals in the end product.
- the units referred to as "agglomerates” are according to one variant a disordered pile of adhering particles which have been fixed or permanently "stuck together" (see FIGS. 8 a and b). This can be done, for example, by cladding with a polymer or silica layer (see, for example, WO 2006/072380 A2), or by linking the particle surfaces to one another via chemical groups, etc. Such agglomerates are technically relatively easy to produce and are therefore preferred.
- the particles can have a different structure without losing functionality (see FIGS. 8 c, d and e).
- alternative embodiments, such as ordered agglomerates or core-shell systems may have advantageous properties (eg, a controlled particle distribution). However, their synthesis is usually more complex.
- Figure 8 with respect to the particulate agglomerates, the following examples are shown:
- core-shell particles wherein the core is formed by a first feature substance and the shell is formed by a plurality of second feature substances;
- core-shell particles wherein the core is formed by a first feature substance and the continuous, homogeneous shell is formed from a second material;
- the particulate agglomerates used according to the invention can be incorporated in the value document itself, in particular in the paper substrate. Additionally or alternatively, the particulate agglomerates can be applied to the value document, for example printed on it.
- the value document substrate does not necessarily have to be a paper substrate, it could also be a plastic substrate or a substrate having both paper components and plastic components. The invention will be explained in more detail below with reference to exemplary embodiments.
- the Raman active material As the Raman active material, the polydiacetylene of Example 12 of the specification US 5,324,567 is used.
- the ESR-active substance used is a strontium titanate doped with 1000 ppm of manganese, as described in document US Pat. No. 4,376,264. Both substances are present as particles having average particle sizes in the range 1-5 ⁇ .
- the produced agglomerates are then added to the paper pulp during sheet production so that the agglomerates are contained in the resulting sheet in a mass fraction of 0.1% by weight.
- the intensity of the signal of the respective security features is determined (intensity of the Raman signal or intensity of the ESR signal).
- the measured signal intensities of the two different security features correlate with each other.
- the ESR-active substance used is a strontium titanate doped with 1000 ppm of chromium, as described in US Pat. No. 4,376,264.
- the intensity of the signal of the respective security features is determined (intensity of the ESR signal or intensity of the SERS signal).
- the measured signal intensities of the two different security features correlate with each other.
- a single particle analysis can be performed.
- the ESR properties of a single agglomerate in the sheet can be e.g. be examined with a suitable ESR microscope.
- the SERS properties of a single agglomerate can be studied, for example, by a suitable TERS (Tip-Enhanced Raman Spectroscopy) setup or a Raman microscope. Both the specific ESR properties and the specific SERS properties of the security features used as starting materials can be detected in the individual particles of the agglomerates produced.
- the first zero-field active substance a manganese ferrite is used, as described in Example 2 of the document WO 96/05522 A.
- the second zero-field active substance used is an isotopically labeled yttrium oxychloride.
- the use of isotope-labeled chlorine-containing substances as zero-field-active security features is described in general in document WO 03/014700 A2. Both substances have average particle sizes below 5 ⁇ . 16.5 g of the first zero-field active substance and 16.5 g of the second zero-active substance are dispersed in 245 g of water.
- the produced agglomerates are then added to the paper pulp during sheet production so that the agglomerates are contained in the resulting sheet in a mass fraction of 0.1 weight percent.
- the intensity of the respective NQR signal of the two safety features used as starting materials is determined at several different points on the sheet. The measured signal intensities of the two security features correlate with each other.
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CN111612965B (en) * | 2020-05-19 | 2022-04-01 | 武汉卓目科技有限公司 | Method, apparatus and device for denomination recognition using security thread magnetic encoding |
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NL8000734A (en) | 1980-02-06 | 1981-09-01 | Houtum & Palm Papierfab | IDENTIFIABLE PAPER BY PHYSICAL ROAD. |
ES8203280A1 (en) * | 1980-05-30 | 1982-04-01 | Gao Ges Automation Org | Paper security with authenticity mark of luminescent material and method for the authentication thereof. |
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-
2013
- 2013-09-27 DE DE102013016134.7A patent/DE102013016134A1/en active Pending
-
2014
- 2014-09-29 ES ES14777522.5T patent/ES2665152T3/en active Active
- 2014-09-29 US US15/023,597 patent/US9542788B2/en active Active
- 2014-09-29 WO PCT/EP2014/002643 patent/WO2015043761A2/en active Application Filing
- 2014-09-29 EP EP14777522.5A patent/EP3049253B1/en active Active
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DE102013016134A1 (en) | 2015-04-02 |
US9542788B2 (en) | 2017-01-10 |
US20160232735A1 (en) | 2016-08-11 |
EP3049253B1 (en) | 2018-02-21 |
WO2015043761A2 (en) | 2015-04-02 |
ES2665152T3 (en) | 2018-04-24 |
WO2015043761A3 (en) | 2015-06-25 |
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