EP1348575A1 - Sicherheitspapier und andere Sicherheitsartikel - Google Patents
Sicherheitspapier und andere Sicherheitsartikel Download PDFInfo
- Publication number
- EP1348575A1 EP1348575A1 EP02007000A EP02007000A EP1348575A1 EP 1348575 A1 EP1348575 A1 EP 1348575A1 EP 02007000 A EP02007000 A EP 02007000A EP 02007000 A EP02007000 A EP 02007000A EP 1348575 A1 EP1348575 A1 EP 1348575A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- absorber
- latent
- photoluminescent
- security
- preferentially
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000006096 absorbing agent Substances 0.000 claims abstract description 197
- 239000000203 mixture Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims description 39
- 238000006243 chemical reaction Methods 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 26
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 claims description 16
- 239000011159 matrix material Substances 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 10
- 239000003086 colorant Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 5
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 230000003595 spectral effect Effects 0.000 claims description 5
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims description 4
- 238000007641 inkjet printing Methods 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 235000019422 polyvinyl alcohol Nutrition 0.000 claims description 4
- 238000007650 screen-printing Methods 0.000 claims description 4
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims description 4
- FJGQBLRYBUAASW-UHFFFAOYSA-N 2-(benzotriazol-2-yl)phenol Chemical class OC1=CC=CC=C1N1N=C2C=CC=CC2=N1 FJGQBLRYBUAASW-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 229920010126 Linear Low Density Polyethylene (LLDPE) Polymers 0.000 claims description 2
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007648 laser printing Methods 0.000 claims description 2
- 238000012856 packing Methods 0.000 claims description 2
- 229920002959 polymer blend Polymers 0.000 claims description 2
- 239000004814 polyurethane Substances 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 238000012795 verification Methods 0.000 claims 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 abstract description 20
- 150000001875 compounds Chemical class 0.000 abstract description 12
- 239000000758 substrate Substances 0.000 abstract description 10
- 239000010410 layer Substances 0.000 description 65
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 16
- 239000002253 acid Substances 0.000 description 13
- 238000005424 photoluminescence Methods 0.000 description 12
- 230000005855 radiation Effects 0.000 description 11
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 10
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000012800 visualization Methods 0.000 description 7
- ISUMUAKOGDLTCO-UHFFFAOYSA-N 2-hydroxy-5-methylbenzotriazole Chemical compound C1=C(C)C=CC2=NN(O)N=C21 ISUMUAKOGDLTCO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 239000012965 benzophenone Substances 0.000 description 6
- 150000008366 benzophenones Chemical class 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 5
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000002378 acidificating effect Effects 0.000 description 4
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 230000000977 initiatory effect Effects 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 229920000092 linear low density polyethylene Polymers 0.000 description 4
- 239000004707 linear low-density polyethylene Substances 0.000 description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- 239000003223 protective agent Substances 0.000 description 4
- 238000012216 screening Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000012258 stirred mixture Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- OJLABXSUFRIXFL-UHFFFAOYSA-N (2-benzoylphenyl)-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C(=O)C1=CC=CC=C1 OJLABXSUFRIXFL-UHFFFAOYSA-N 0.000 description 3
- 239000012963 UV stabilizer Substances 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 3
- 230000003292 diminished effect Effects 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- YHCGGLXPGFJNCO-UHFFFAOYSA-N 2-(2H-benzotriazol-4-yl)phenol Chemical compound OC1=CC=CC=C1C1=CC=CC2=C1N=NN2 YHCGGLXPGFJNCO-UHFFFAOYSA-N 0.000 description 2
- DXPQDAHFCMBFMM-UHFFFAOYSA-N 2-benzoylbenzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 DXPQDAHFCMBFMM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001015 X-ray lithography Methods 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical class OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001565 benzotriazoles Chemical class 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 239000012230 colorless oil Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000010511 deprotection reaction Methods 0.000 description 2
- 238000000609 electron-beam lithography Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- NRZYYKACXDZFRF-UHFFFAOYSA-N tert-butyl carbamate Chemical compound CC(C)(C)OC(N)=O.CC(C)(C)OC(N)=O NRZYYKACXDZFRF-UHFFFAOYSA-N 0.000 description 2
- RUPAXCPQAAOIPB-UHFFFAOYSA-N tert-butyl formate Chemical group CC(C)(C)OC=O RUPAXCPQAAOIPB-UHFFFAOYSA-N 0.000 description 2
- 125000005931 tert-butyloxycarbonyl group Chemical group [H]C([H])([H])C(OC(*)=O)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- 150000003918 triazines Chemical class 0.000 description 2
- 238000002211 ultraviolet spectrum Methods 0.000 description 2
- 238000001429 visible spectrum Methods 0.000 description 2
- IEDOIPXWIBKTOF-UHFFFAOYSA-N (5-methylbenzotriazol-2-yl)-phenylmethanone Chemical group N1=C2C=C(C)C=CC2=NN1C(=O)C1=CC=CC=C1 IEDOIPXWIBKTOF-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical class OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- IOHPVZBSOKLVMN-UHFFFAOYSA-N 2-(2-phenylethyl)benzoic acid Chemical compound OC(=O)C1=CC=CC=C1CCC1=CC=CC=C1 IOHPVZBSOKLVMN-UHFFFAOYSA-N 0.000 description 1
- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 1
- FRSMLANYBOTORN-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)phenol Chemical compound OC1=CC=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 FRSMLANYBOTORN-UHFFFAOYSA-N 0.000 description 1
- JEQDLQXVZAUQIT-UHFFFAOYSA-N 2-[(2-hydroxyphenyl)diazenyl]-3-phenylphenol Chemical compound Oc1ccccc1N=Nc1c(O)cccc1-c1ccccc1 JEQDLQXVZAUQIT-UHFFFAOYSA-N 0.000 description 1
- ZCILGMFPJBRCNO-UHFFFAOYSA-N 4-phenyl-2H-benzotriazol-5-ol Chemical class OC1=CC=C2NN=NC2=C1C1=CC=CC=C1 ZCILGMFPJBRCNO-UHFFFAOYSA-N 0.000 description 1
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical class OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 description 1
- WDMFHQNUSVLQMS-UHFFFAOYSA-N 5-(3,3-dimethyl-2-bicyclo[2.2.1]heptanylidene)pent-3-en-2-one Chemical compound C1CC2C(C)(C)C(=CC=CC(=O)C)C1C2 WDMFHQNUSVLQMS-UHFFFAOYSA-N 0.000 description 1
- UWSMKYBKUPAEJQ-UHFFFAOYSA-N 5-Chloro-2-(3,5-di-tert-butyl-2-hydroxyphenyl)-2H-benzotriazole Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O UWSMKYBKUPAEJQ-UHFFFAOYSA-N 0.000 description 1
- AIXZBGVLNVRQSS-UHFFFAOYSA-N 5-tert-butyl-2-[5-(5-tert-butyl-1,3-benzoxazol-2-yl)thiophen-2-yl]-1,3-benzoxazole Chemical compound CC(C)(C)C1=CC=C2OC(C3=CC=C(S3)C=3OC4=CC=C(C=C4N=3)C(C)(C)C)=NC2=C1 AIXZBGVLNVRQSS-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- 208000028006 Corneal injury Diseases 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 150000008360 acrylonitriles Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 125000000751 azo group Chemical class [*]N=N[*] 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229940092714 benzenesulfonic acid Drugs 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- CSKNSYBAZOQPLR-UHFFFAOYSA-N benzenesulfonyl chloride Chemical compound ClS(=O)(=O)C1=CC=CC=C1 CSKNSYBAZOQPLR-UHFFFAOYSA-N 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 1
- 150000001788 chalcone derivatives Chemical class 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- MGHPNCMVUAKAIE-UHFFFAOYSA-N diphenylmethanamine Chemical class C=1C=CC=CC=1C(N)C1=CC=CC=C1 MGHPNCMVUAKAIE-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- IAJNXBNRYMEYAZ-UHFFFAOYSA-N ethyl 2-cyano-3,3-diphenylprop-2-enoate Chemical compound C=1C=CC=CC=1C(=C(C#N)C(=O)OCC)C1=CC=CC=C1 IAJNXBNRYMEYAZ-UHFFFAOYSA-N 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000011346 highly viscous material Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000002186 photoactivation Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 125000006239 protecting group Chemical group 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229940058287 salicylic acid derivative anticestodals Drugs 0.000 description 1
- 150000003872 salicylic acid derivatives Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
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
- B42D25/21—Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof characterised by a particular use or purpose for multiple purposes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/14—Security printing
- B41M3/142—Security printing using chemical colour-formers or chemical reactions, e.g. leuco-dye/acid, photochromes
-
- 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
-
- 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
- B42D25/36—Identification or security features, e.g. for preventing forgery comprising special materials
- B42D25/378—Special inks
- B42D25/382—Special inks absorbing or reflecting infrared light
-
- 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
Definitions
- the present invention relates to a security item, as well as to a method for producing such security item. More specifically, it relates to a security item that can be imprinted with specific information. It generally applies to articles whose counterfeiting is to be made difficult or impossible and/or whose authenticity and/or validity is to be identified.
- security features are contained in or applied on the substrate - usually paper or plastic - of the document and hamper the unauthorized reproduction of the document. They can usually not individually be imprinted with specific information. Such information is - as for example on a passport - imprinted on the substrate of the document, but not within a security feature. While such security features can efficiently hamper unauthorized reproduction of such a substrate, they can, however, not prevent that the information on such an authentic document is altered, e.g. the name of a passport holder or the date of birth on a driver license is changed.
- Such efforts include, e.g., inkjet-printing of a halftone shadow-image of the passport holder's photograph over the entire document or laminating of the document with a protective layer that can not be removed without destroying document and/or protective layer.
- security features that can be imprinted with specific information, e.g. the passport holder's name or photograph offer an enhanced level of security when compared with security articles of prior art.
- British Patent Specification GB 1123274 discloses an identification document having embedded therein superposed layers of a fluorescent material and an ultraviolet screening agent.
- the layer of ultraviolet screening agent has a code formed therein so that when the document is illuminated with ultraviolet radiation, the code can be seen.
- the code is invisible in light containing only small amounts of ultraviolet radiation (e.g. daylight).
- United States Patent Specification US 5,005,873 discloses an article for identification having embedded therein superposed layers of at least two different fluorescent materials and, in one preferred embodiment, visual identification data is provided by a pattern of a UV absorbing agent.
- British Patent Specification GB 2300596 discloses a security feature comprising a transparent or translucent substrate and two fluorescent components and a UV light absorber preferably incorporated in a layer between each of the fluorescent components, thus providing a composite which has different appearance in reflected and transmitted UV light.
- United States Patent Specification US 5,360,235 discloses an optical marking system with coating materials transparent in daylight and having the property of absorbing ultraviolet light, applied to a portion of a surface which is a good ultraviolet reflector. This object appears unmarked when observed by the naked eye, but when observed through a device, the different UV absorbing/reflecting markings become apparent.
- the ultraviolet absorbing material is a ultraviolet absorbing benzophenone.
- This object is achieved by providing at least one security element having at least one segment comprising at least one latent UV or IR absorber.
- said latent absorber can be converted into an actual absorber (alternatively referred to as "the latent absorber's active form” or "the absorber” in the following). Since both the latent absorber and the liberated absorber itself are preferentially colorless and transparent throughout the visible spectrum, information imprinted within a substrate containing said absorbers is invisible to the naked eye. Moreover, the information is also invisible under UV or IR irradiation.
- a chemical, thermal or lithographic process e.g. photo-lithography, electron beam lithography, X ray lithography, spatially resolved heat- or micro wave treatment
- the latent absorber's active form or "the absorber” in the following. Since both the latent absorber and the liberated absorber itself are preferentially colorless and transparent throughout the visible spectrum, information imprinted within a substrate containing said absorbers is invisible to the naked eye. Moreover, the information is also invisible under UV or IR irradiation.
- the imprinted data becomes apparent as a shadow image on the photoluminescent screen, since, in the areas where the latent absorber has been converted to the absorber, the light is being absorbed and does not reach the photoluminescent device.
- a screen has to be used which allows the conversion of infrared radiation into the visible range.
- the latent absorber is a latent UV absorber allowing for a much easier detection, as a corresponding photoluminescent device simply has to convert ultraviolet irradiation into the visible range.
- the security element is in a form selected from the group consisting of fibres, threats, strips, films, sheets, layers, tapes, plates, discs, chips and/or combinations thereof.
- the actual security element can have a multitude of forms.
- the at least one latent absorber is applied to or embedded in a matrix.
- this matrix is transparent for wavelengths in the visible region and/or in the spectral region which can potentially be absorbed by the latent absorber, i.e. by the latent absorbers active form.
- the matrix is made of a polymer or a polymer blend, wherein preferentially the polymer is chosen from the group consisting of polyethylene (PE), in particular linear low-density polyethylene (LLDPE) or ultra-high molecular weight polyethylene (UHMW-PE), polypropylene (PP), polyethyleneterephthalate (PET), polycarbonate (PC), polyvinylalcohol (PVA1), polyvinylchloride (PVC), polyurethane (PU) and mixtures thereof.
- PE polyethylene
- LLDPE linear low-density polyethylene
- UHMW-PE ultra-high molecular weight polyethylene
- PP polypropylene
- PET polyethyleneterephthalate
- PC polycarbonate
- PVA1 polyvinylalcohol
- PVC polyvinylchloride
- PU polyurethane
- the latent absorber can be a mixture of different components, e.g. a mixture of a potentially absorbing molecule which has been chemically modified in such way as not to absorb in the UV or IR range, with another molecule capable of setting free a chemical species initiating the conversion of the potentially absorbing molecule to the latent absorbers active form by e.g. removing a particular protective group.
- the latent absorber is non-photoluminescent and colourless. If however the latent absorber is photoluminescent, there is no need for a particular photoluminescent screen to detect regions where the latent absorber has been converted to its active form since the latent absorber at the same time takes over the detection function. Such a compound therefore might, after conversion to the active form, by absorbing, directly convert the irradiated light in the UV/IR range, which is invisible to the naked eye, into visible light. Clearly, an additional photoluminescent screen can still be employed.
- the latent absorber is a latent UV absorber and the latent UV absorber is at least partially converted to its absorbing form, wherein preferentially the absorbing form is present in a spatially resolved manner.
- At least one security element comprises at least one photoluminescent substance, which may preferentially be embedded in a matrix as mentioned above or which may even more preferentially be present in a separate layer.
- the provision of actual detection means within the security item facilitates detection of the imprinted information substantially. In such a case, no separate photoluminescent screen is necessary. Irradiation with e.g. appropriate UV light directly makes the imprinted information visible to the naked eye, as irradiation not absorbed by the converted latent absorber will be converted into the visible range by the photoluminescent substance.
- a number of photoluminescent substances showing different colours in fluorescence can be employed, wherein preferentially different colours are arranged in a spatially resolved manner and/or in different layers. It is for example possible to provide particular regions like stripes of particular colour, thus increasing the inherent security of the feature and the attractive character of it.
- a particularly interesting embodiment of the present invention is characterised in that there is at least one layer comprising latent UV absorber sandwiched between two layers comprising photoluminescent substance.
- the two photoluminescent layers show different colours in fluorescence.
- a latent image imprinted in the layer comprising the latent absorber will show up in a different colour depending on the side of the laminate from which observation occurs.
- Another particularly interesting embodiment of the present invention is characterised in that there is at least two layers comprising latent UV absorber which is at least partially converted to its absorbing form in a spatially resolved manner, wherein between these two layers there is at least one layer comprising the photoluminescent substance, and wherein preferentially the information contained in the spatial arrangement of the absorbing form is different in the two layers.
- Such an arrangement of layers within one laminate allows to provide for an essentially transparent feature and which, if irradiated with UV or IR, displays different information depending on the side of observation.
- a laminate of at least three layers comprising latent UV absorber at least partially converted to its absorbing form in a spatially resolved manner in that between the at least three layers there are layers comprising the photoluminescent substance, wherein preferentially the photoluminescent layers show different colours in fluorescence, and wherein even more preferentially the information contained in the spatial arrangement of the absorbing form is different in each of the layers comprising latent UV absorber.
- a laminate like this particular information imprinted on particular layers will appear in different colours and different superposition is depending on the side from which observation occurs.
- Such a laminate shows an extremely high security with respect to falsification or counterfeiting.
- the security level can be increased even more by providing at least one photoluminescent substance within or on the security item which is oriented in or on a substrate such that it exhibits polarised emission and/or absorption.
- the visibility of the information will thus depend on the angle of the polarisation of the irradiated light and/or on the angle of a polarizing filter which is used for detection: In particular if the direction of polarisation of the irradiated light or of the polarizing filter for detection is rotated continuously, a bright/dark effect can be observed with the imprinted information.
- the photoluminescent substance can have polarizing properties, but it is also possible to provide a latent absorber which exhibits polarised absorption in its absorbing form, and in case of a latent absorber which is photoluminescent or in the case of an absorber which is photoluminescent, exhibits polarised absorption and/or emission. Moreover, if photolytical conversion of the latent absorber to the absorber is employed, this conversion can be carried out employing polarized radiation, thus leading to preferential conversion of molecules oriented essentially parallel to the optical axis of the radiation, similarly resulting in polarized absorption.
- the latent absorber is a latent UV absorber and is a derivative of 2-2-hydroxyphenylbenzotriazole, 2-hydroxybenzophenone, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-phenol, or azobenzene, or a mixture thereof.
- a still further preferred embodiment of the present invention is characterised in that the security item is an object whose counterfeiting is to be made difficult or impossible and/or whose authenticity and/or validity is to be identified and/or the purpose of which is to have information contained therein in the form of areas essentially containing latent absorber and areas essentially containing absorber in a spatially resolved manner, wherein preferentially the security item is selected from the group of banknotes, checks, stocks and bonds, securities, identification cards, passports, drivers licences, admission tickets, stamps, bankcards, credit cards, packing material.
- the present invention additionally relates to a method of producing security items as described above, characterised in that an object is provided with a security element which contains at least one segment comprising at least one latent UV or IR absorber.
- the latent absorber is a latent UV absorber and the latent UV absorber is at least partially converted to its absorbing form by means of a chemical or photochemical process, if needed assisted or followed by heat treatment, wherein preferentially the conversion is carried out in a spatially resolved manner.
- various processes are possible, e.g. a photographic process, a lithographic process, a screen printing process, an inkjet printing process or a laser printing process. Further preferred embodiments of the method according to the present invention are given in the dependent claims.
- the present invention provides an article containing a latent UV absorber.
- a latent UV absorber Upon appropriate treatment, e.g. in a lithographic process (photo-lithography, electron beam lithography, X ray lithography, spatially resolved heat- or micro wave treatment), said latent UV absorber can be converted into an actual UV absorber in a spatially resolved manner. Since both the latent UV absorber and the liberated UV absorber itself are essentially colorless and transparent throughout the visible spectrum, information imprinted within a substrate containing said absorbers is invisible to the naked eye. Moreover, the information is also invisible under UV irradiation.
- the imprinted information becomes apparent as a shadow image on the photoluminescent screen, since, in the areas where the latent absorber has been converted to the UV absorber, the UV light is being absorbed and does not reach the photoluminescent device.
- Fig. 1 shows such an article I containing latent UV absorber 1 dispersed in a matrix 2.
- the latent UV absorber (given as empty circles) has not been converted to the actual absorber yet.
- Fig. 2 shows the actual conversion process, i.e. the selective, spatially resolved conversion of a latent UV absorber 1 to a UV absorber 6 by exposure to UV light of appropriate wavelength 3 through a photomask II, which photomask comprises the information that shall be imprinted.
- Converted latent UV absorber is given by circles with a cross.
- Fig. 3 shows an article IV according to the present invention comprising latent UV absorber 1 and UV absorber 6 in a spatially resolved manner thus providing a latent, invisible pattern formed by zones V of latent UV absorber 1 and zones VI containing UV absorber 6.
- Fig. 4 shows the visualization of a latent pattern contained in article IV according to Fig. 3 by irradiation of a photoluminescent screen VII containing photoluminescent species 8 through said article with UV light 7 of appropriate wavelength for stimulation of photoluminescence in VII.
- Zones IX in VII adjacent to zones VI in IV containing UV absorber 6 appear dark, while zones VIII in VII adjacent to zones V in IV containing latent UV absorber 1 show photoluminescence 9.
- both the latent UV absorber and a photoluminescent substance within the same layer or in a printing ink.
- the photoluminescence intensity will be strongly diminished, due to extinction of the excerted UV radiation and/or due to energy transfer processes from the photoluminescent compound to the UV absorber.
- the photoluminescent substance is provided in a separate layer, since better contrast between areas of latent and activated UV absorber can be achieved in that way.
- energy transfer processes either hopping or Förster-type
- Latent UV absorbers such as the ones disclosed herein allow for a multitude of different, personalizable security elements.
- two separate photoluminescent screens which contain photoluminescent dyes which fluoresce in .different colors can be employed instead of the single photoluminescent layer.
- Such a device would, if irradiated with UV light, show one image in one color on one side of the security element, and a different image in a different color on the other side of the element.
- the two photoluminescent layers can additionally be separated by a supplementary UV absorbing layer which prevents undesired excitation of the layer not facing the UV light source. It is also possible to have this middle layer made from a layer containing latent UV absorber and thus providing an additional information layer. In such manner, multitudes of different combinations are feasible.
- FIG. 5 shows a laminate XII of two articles IV according to Fig. 3 with a photoluminescent middle layer VII containing photoluminescent species 8. Again, absorbing parts are indicated by circles with crosses.
- Fig. 6 shows an article XII according to Fig. 5 under UV irradiation 7 viewed in reflection from above.
- the pattern 'A' imprinted in layer X is visualized on VII. Regions where there is actual absorber (circles with crosses) will appear dark as no irradiated UV will reach the photoluminescent layer VII in these regions.
- Fig. 7 shows an article according to Fig. 5 under UV irradiation 7 viewed in reflection from below.
- the latent pattern 'B' imprinted in layer XI is visualized on VII. Depending on the side of observation there will therefore be a different pattern visible.
- Fig. 8 shows an article according to Fig. 5 under UV irradiation 7 viewed in transmission with irradiation from above and observation from below.
- the latent pattern 'A' imprinted in layer X is visualized on VII, while the pattern 'B' will not be visible as behind there is no photoluminescent element which might visualise whether UV irradiation has been absorbed or not.
- Fig. 9 shows an article according to Fig. 5 under UV irradiation 7 viewed in transmission with irradiation from below and observation from above.
- the latent pattern 'B' imprinted in layer XI is visualized on VII.
- Figures 5 to 9 therefore show that a sophisticated security feature can be obtained by a simple three layer laminate, where depending on the mode of observation (reflection, transmission) and depending on their side of observation (below, above), different patterns will appear in the visible range.
- the actual conversion of the latent UV absorber to the actual UV absorber can either be carried out prior or after the actual lamination process of this three-layer laminate.
- selective imprinting takes place on one of the layers, namely the wanted one.
- imprinting takes place from the side where the layer to be imprinted is located, thus it is e.g.
- Fig. 10 shows an even more sophisticated article according to the invention consisting of a laminate of three layers according to Fig. 3, whereas layer X contains a latent pattern 'A', layer XI contains a latent pattern 'B' and the layer XVII contains a latent pattern 'C'.
- Layer X and layer XI are separated by a photoluminescent screen VII exhibiting one particular photoluminescence color, layer XI and layer XVII are separated by a photoluminescent screen XVIII also exhibiting one particular photoluminescence color which may or may not be equal to the one of the photoluminescent screen VII.
- Layer XI may or may not contain a latent pattern.
- An article for identification as disclosed in the present patent application can be incorporated in a document as 'blank', e.g. without imprinted information.
- the information can later be imprinted in the article on demand.
- the batch size is not crucial. It is as well possible to imprint a single, unique piece of information such as the name of a passport holder in such an article as well as it is possible to imprint the date of issue in a series of stock certificates.
- the imprinting can be carried out by various techniques as mentioned above, particularly advantageous combinations might be imprinting by using an inkjet printer with particular inks to introduce the agent for the conversion and to subsequently pass the substrate through a heating device such as a laminator in order to actually initiate the chemical reaction for the conversion of the latent UV absorber to the actual UV absorber.
- a heating device such as a laminator
- Another possibility would be to use a laser printer which already uses a combination of irradiated light and heat for the imprinting process. Slight modification of such a laser printer to irradiate in a spectral region capable of initiating the conversion process might be necessary for the use of a laser printer for conversion.
- EP0952467A1 discloses a composition containing latent UV absorbers for forming ocular devices.
- the compositions may be used to conveniently and efficiently produce ocular devices through UV initiated, free radical polymerisation.
- the latent absorber contained in the composition does not interfere with the UV initiation process but can - after the polymerisation step - be converted into the active UV absorber thus providing protection from harmful UV radiation potentially causing corneal damage.
- EP 0097841A1 discloses a composition containing latent ester UV stabilizers for polycarbonate resins, permitting the cure of the resin by UV irradiation without interference by the latent UV stabilizer. Conversion of the latent stabilizer to the activate UV absorber provides a UV stabilizer for the polycarbonate.
- the latent UV absorbers employed in these documents of prior art are used in a completely different field of application, i.e. not in the field of security features.
- the conversion to the active UV absorber does not occur photochemically and not in a spatially resolved manner.
- the latent absorbers disclosed therein liberate as active UV absorber derivatives of benzophenone, which have, much in contrast to the preferred compounds disclosed in the present patent application, a comparably low extinction in the desired UV regime.
- these latent UV absorbers and their application can not - in any way - be compared to the latent UV absorbers and the field of application of the present invention, they shall be mentioned at this point with reference to the state of the art in the field of latent UV absorbers.
- the invention provides latent UV absorbers for use in articles for identification and/or information storage and methods of their production.
- UV absorber is meant a compound or composition capable of absorbing or screening out UV radiation.
- the absorption properties of the UV absorber may or may not arise from internal conversion processes, such as - for example - excited state intramolecular proton transfer. Preferentially, it does arise from internal conversion processes.
- latent UV absorber is meant a compound or composition capable of liberating a UV absorber. With respect to the liberated UV absorber, the latent UV absorber's absorption is strongly diminished or is only present to a minimal extent or is essentially shifted out of the range of the original absorption spectrum of the UV absorber.
- Figure 14 shows an illustrative example. Figure 14 shows UV spectra of a latent UV absorber (2-2-benzoyl-5-methylphenylbenzotriazole, thin, solid line) and its corresponding UV absorber (2-2-hydroxy-5-methylbenzotriazole, thick solid line). It additionally shows the emission spectrum of an ordinary 'blacklight'-UV lamp (dotted line).
- the latent UV absorber can be converted to the UV absorber by, e.g. photocleavage or deprotection upon exposure to acidic, basic of oxidizing species. These species are preferentially photochemically released and the deprotection of the latent UV absorber can occur at elevated temperatures.
- Figure 13 shows an example of such an acid-labile latent UV absorber (see discussion further below).
- the latent UV absorber may or may not be photoluminescent and may or may not be colorless. Preferentially, it is non-photoluminescent and colorless.
- the UV absorber may or may not be photoluminescent and may or may not be colorless. Preferentially, it is non-photoluminescent and colorless.
- UV radiation is meant any radiation within a portion of the electromagnetic spectrum in the wavelength regime ranging from 180-500 nm.
- protecting agent any compound or composition that reacts with the UV absorber so as to render the UV absorber substantially less effectively absorbing in the range of the original absorption spectrum of the UV absorber.
- useful absorbers include, without limitation, benzophenones, benzotriazoles, triazines, substituted acrylonitriles, salicylic acid derivatives, benzoic acid derivatives, cinnamic acid derivatives, chalcone derivatives, nickel complexes, azo derivatives and mixtures and/or covalently bond combinations thereof. They can alternatively be bound to polymers, occur as polymer side groups or be part of the polymer backbone. Such compounds are disclosed in, e.g., US Patents US 3,391,110, US 5,098,445, US 4,963,160, US 3,391,110 and US 3,162,676.
- benzophenones include, without limitation, 2-hydroxy benzophenones such as 2-hydroxy benzophenone, 2-hydroxy-4-(octyloxy)benzophenone, 2-hydroxy-4-acryloxy alkoxy benzophenones, 2,4-dihydroxy benzophenones, and the like, and mixtures thereof.
- benzotriazoles include, without limitation, 2-2-hydroxyphenylbenzotriazole, 2-2-hydroxy-5-methylphenylbenzotriazole, 2-2-benzotriazol-2-yl)-p-cresol, 2,4-di- tert -butyl-6-(5-chlorobenzotriazol-2-yl)phenol, 2-(2-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, and the like, and mixtures thereof.
- triazines include, without limitation, 2-2-hydroxy-4,6-triphenyl-1,2,3-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxy-phenol and the like, and mixtures thereof.
- Additional absorbers useful in the invention are azo-dyes, polymethines, and the like, and mixtures thereof.
- Preferred UV absorbers are hydroxyphenylbenzotriazoles, hydroxybenzophenones and hydroxyphenyltriazines.
- a wide range of such UV absorbers is commercially available, e.g. from Ciba speciality chemicals under the trade names Chimassorb and Tinuvin.
- the latent absorber undergoes regeneration or restoration of its absorbtion characteristics.
- the conditions for regeneration will depend on the protecting agent and absorber used. For example, in cases where the hydroxy group of a 2-hydroxy phenylbenzotriazole or a 2-hydroxy benzophenone is esterified with benzoic acid or a benzoic acid derivative, regeneration may be carried out by irradiation with high energy UV light, typically in the range of 220-400 nm, preferentially in the range of 220-340 nm, and even more preferentially within a narrow interval centered around 254 nm (see Fig. 11).
- PAG's for the conversion process might be of advantage in particular in case the security item is to be used under daylight conditions (e.g. for banknotes), as the irradiation-frequency for the initiation of the PAG can be shifted well out of the spectral region of the sun thus avoiding undesired conversion of the latent UV absorber contained in the security feature during use.
- a possible irradiation frequency well out of the spectral region of the sun would for example be 254 nm.
- Even more advantageous are systems where increased temperatures are required to convert the latent UV absorber to the UV absorber in the presence of a preferentially photochemically generated acid. In such systems, the latent UV absorber is not converted to the UV absorber, even if some acid is unwantedly liberated during use, e.g. due to exposure to sunlight.
- regeneration may be carried out by a mild oxidizing agent. Said oxidizing agent may be photochemically released.
- An example of a class of latent UV absorbers are esters of 2-hydroxy-5-methylbenzotriazole. They can be obtained by reacting the hydroxy group of 2-hydroxy-5-methylbenzotriazole with a compound or composition such as acid chlorides.
- An example of a latent UV absorber is 2-benzoyl-5-methylbenzotriazole, which can be obtained by reacting 2-hydroxy-5-methylbenzotriazole with benzoyl chloride in the presence of pyridine.
- the benzoyl ester group of this substance can be cleaved photochemically, thus returning 2-hydroxy-5-methylbenzotriazole. This reaction is shown in Fig. 12.
- esterification of 2-hydroxy-5-methylbenzotriazole can be carried out using di- tert -butyl dicarbamate as protecting agent.
- the tertiary butoxycarbonyl group of the obtained, latent UV absorber can be removed by acidic species, thus returning 2-hydroxy-5-methylbenzotriazole. This reaction is shown in Fig. 13.
- PAG's photo acid generators
- PAG's include benzenesulfonic acid derivatives, arylmethylsulfones, benzenesulfonates, thriphenylsulphoniumtriflates, thriphenylsulphoniumhexafluoro-antimonates, etc.
- a protective ester group of a latent UV absorber can be saponified by a basic species, again returning the UV absorber.
- the basic species is preferentially photochemically released.
- Compounds which liberate bases upon irradiation are generally known as photo base generators (PBG's).
- PBG's photo base generators
- the above examples are particularly interesting in the scope of the invention because they allow for a spatially resolved conversion of the latent UV absorber by lithographic methods.
- Examples of PBG's are benzhydrylammonium salts.
- cleaving species in a spatially resolved manner by different than lithographic means, e.g. by inkjet printing, screen-printing, etc.
- While protection of the hydroxy group of a UV absorber is the most straight forward approach to obtain latent UV absorbers, it is alternatively feasible to reduce the C O group of certain of the absorbers, especially benzophenones, to the corresponding alcohol by a reducing agent such as aluminum triisopropoxide.
- the ketals may be formed from absorbers containing ketone carbonyls.
- the absorbance spectrum of certain absorbers can be shifted outside the usual absorbance regime by chemical alterations. For example, phenylazophenol and derivatives can be esterified to shift the absorption spectrum out of the original range.
- the invention consists of one substrate for an identification article comprising, consisting essentially of, or consisting of a composition comprising at least one latent UV absorber.
- the invention provides a latent UV absorber comprising, consisting essentially of or consisting of a UV absorber altered reversibly in such way that the absorption of said UV absorber is strongly diminished or shifted outside the original absorption spectrum of the UV absorber.
- a blend film containing 1% w/w of 2-2-benzoyl-5-methylbenzotriazole in LLDPE (Dowlex BG 2340, Dow Chemicals) was produced by dissolving 5 mg 2-2-benzoyl-5-methylbenzotriazole in 2 ml CH 2 Cl 2 and decorating 450 mg of LLDPE pellets with that solution. After evaporation of the solvent at ambient, the decorated pellets were pressed into a blend film at 180 °C in a hot press. The obtained blend film was cut into pieces. These pieces were mixed and processed into a film again. This process was repeated four times in order to obtain homogeneous distribution of the latent UV absorber within the polymer matrix.
- photomasks Two pieces of this film were irradiated through photomasks showing different black-and-white images with high energy UV light from a high-pressure Hg lamp (Philipps HPR 125 W) for 1 h.
- the photomasks were produced by printing the respective images on ordinary transparency sheets made of poly(ethyleneterephthalate) with an ordinary office-type laser printer.
- the selectively irradiated film pieces were laminated each onto one side of a photoluminescent film made of polypropylene containing 0.05% w/w of a fluorescent dye (Uvitex OB ONE, Ciba Speciality Chemicals).
- a fluorescent dye Uvitex OB ONE, Ciba Speciality Chemicals.
- a blend film containing 1% w/w of 2-2-benzoyl-5-methylbenzotriazole in LLDPE was produced according to Example 1.
- a 2 cm x 2 cm piece of this blend film was irradiated for 20 min with light (low pressure Hg UV lamp, center frequency 254 nm) through a photomask made of steel containing square holes with 200 micron diameter, arranged in a chessboard-like pattern. After this time, the film was visually still uniformly transparent and colorless. Investigation of the film on a photoluminescent background under UV irradiation clearly revealed the hidden chessboard pattern as shadow image on the photoluminescent background.
- the product was found to efficiently cleave at elevated temperatures in the presence of acids to quantitatively restore 2-2-hydroxy-5-methylbenzotriazole.
- the product was found to efficiently cleave under UV irradiation (low pressure Hg UV lamp, center frequency 254 nm) to quantitatively restore benzenesulfonic acid.
- UV irradiation low pressure Hg UV lamp, center frequency 254 nm
- the product is thus suitable as photo acid generator.
- a blend film containing 1% w/w of 2-2-benzoyl-5-methylbenzotriazole and 1% of 2-benzoyl-benzenesulfonate in LLDPE was produced according to Example 1.
- a 2 cm x 2 cm piece of this blend film was irradiated for 10 min with light from a 254 nm UV lamp through a photomask made from a poly(vinylalcohol) sheet with a black-and-white image printed thereon by aid of an ordinary office-type ink jet printer. Subsequently, the sample was baked for 10 min at 110 °C. After this time, the film was visually still uniformly transparent and colorless. Investigation of the film on a photoluminescent background clearly revealed the hidden image as shadow image on the photoluminescent background.
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Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02007000A EP1348575A1 (de) | 2002-03-27 | 2002-03-27 | Sicherheitspapier und andere Sicherheitsartikel |
PCT/EP2003/002905 WO2003080364A1 (en) | 2002-03-27 | 2003-03-20 | Security paper and other security items |
AU2003226672A AU2003226672A1 (en) | 2002-03-27 | 2003-03-20 | Security paper and other security items |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP02007000A EP1348575A1 (de) | 2002-03-27 | 2002-03-27 | Sicherheitspapier und andere Sicherheitsartikel |
Publications (1)
Publication Number | Publication Date |
---|---|
EP1348575A1 true EP1348575A1 (de) | 2003-10-01 |
Family
ID=27798814
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP02007000A Withdrawn EP1348575A1 (de) | 2002-03-27 | 2002-03-27 | Sicherheitspapier und andere Sicherheitsartikel |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP1348575A1 (de) |
AU (1) | AU2003226672A1 (de) |
WO (1) | WO2003080364A1 (de) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1995075A1 (de) * | 2007-05-24 | 2008-11-26 | Gemplus SA. | Datenträger mit gedruckten Kenndaten und fälschungssicheren Maßnahmen |
EP2233315A1 (de) | 2009-03-26 | 2010-09-29 | CSEM Centre Suisse d'Electronique et de Microtechnique SA - Recherche et Développement | Authentifizierungselement und System für verpackte Artikel und Verfahren zur Herstellung des Authentifizierungselements |
DE102011018852A1 (de) | 2011-04-27 | 2012-10-31 | Mitsubishi Hitec Paper Europe Gmbh | Wärmeempfindliches Aufzeichnungsmaterial mit Authentifikationsmerkmal |
KR20120140630A (ko) * | 2011-06-21 | 2012-12-31 | 제너럴 일렉트릭 캄파니 | 광학 데이터 저장 매체에 데이터를 기록하는 방법 및 광학 데이터 저장 매체 |
US9566813B2 (en) | 2006-12-18 | 2017-02-14 | Gemalto Oy | Data carrier with see-through window and method for producing it |
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GB1123274A (en) | 1966-04-27 | 1968-08-14 | Virginia Laminating Company | Identification document |
EP0097841A1 (de) | 1982-06-10 | 1984-01-11 | General Electric Company | Polycarbonatzusammensetzung welche einen Ester als latenten UV Stabilisator enthält |
US5005873A (en) | 1986-04-07 | 1991-04-09 | West Michael A | Marking of articles |
US5098445A (en) | 1989-03-14 | 1992-03-24 | Ciba-Geigy Corporation | Ultraviolet radiation absorbing agent for bonding to an ocular lens |
US5360235A (en) | 1969-11-01 | 1994-11-01 | The United States Of America As Represented By The Secretary Of The Navy | Secret optical marking |
GB2300596A (en) | 1995-05-10 | 1996-11-13 | Portals Ltd | Fluorescent security feature for cheques and banknotes |
EP0952467A1 (de) | 1998-04-20 | 1999-10-27 | JOHNSON & JOHNSON VISION PRODUCTS, INC. | Durch freie Radikale polymerisierende, latente UV-Absorber enthaltende okulare Vorrichtungen |
EP0982149A1 (de) * | 1998-08-28 | 2000-03-01 | Dai Nippon Printing Co., Ltd. | Übertragungsfolie zur Herstellung fluoreszierender latenter Bilder, Verfahren zu dessen Benutzung, sowie Sicherheitsmuster enthaltende Materialien |
WO2001042031A1 (en) * | 1999-12-10 | 2001-06-14 | Laser Lock Technologies, Inc. | Counterfeit detection system |
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- 2002-03-27 EP EP02007000A patent/EP1348575A1/de not_active Withdrawn
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- 2003-03-20 AU AU2003226672A patent/AU2003226672A1/en not_active Abandoned
- 2003-03-20 WO PCT/EP2003/002905 patent/WO2003080364A1/en not_active Application Discontinuation
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EP0982149A1 (de) * | 1998-08-28 | 2000-03-01 | Dai Nippon Printing Co., Ltd. | Übertragungsfolie zur Herstellung fluoreszierender latenter Bilder, Verfahren zu dessen Benutzung, sowie Sicherheitsmuster enthaltende Materialien |
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US9566813B2 (en) | 2006-12-18 | 2017-02-14 | Gemalto Oy | Data carrier with see-through window and method for producing it |
EP2114690B1 (de) * | 2006-12-18 | 2018-11-21 | Gemalto Oy | Datenträger mit sichtfenster und verfahren zu seiner herstellung |
EP1995075A1 (de) * | 2007-05-24 | 2008-11-26 | Gemplus SA. | Datenträger mit gedruckten Kenndaten und fälschungssicheren Maßnahmen |
WO2008142545A2 (en) * | 2007-05-24 | 2008-11-27 | Gemplus | Information medium with printed identification information and anti-forgery means |
WO2008142545A3 (en) * | 2007-05-24 | 2009-01-22 | Gemplus | Information medium with printed identification information and anti-forgery means |
EP2233315A1 (de) | 2009-03-26 | 2010-09-29 | CSEM Centre Suisse d'Electronique et de Microtechnique SA - Recherche et Développement | Authentifizierungselement und System für verpackte Artikel und Verfahren zur Herstellung des Authentifizierungselements |
EP2233314A1 (de) | 2009-03-26 | 2010-09-29 | CSEM Centre Suisse d'Electronique et de Microtechnique SA - Recherche et Développement | Authentifizierungselement und System für verpackte Artikel und Verfahren zur Herstellung des Authentifizierungselements |
DE102011018852A1 (de) | 2011-04-27 | 2012-10-31 | Mitsubishi Hitec Paper Europe Gmbh | Wärmeempfindliches Aufzeichnungsmaterial mit Authentifikationsmerkmal |
EP2517888A1 (de) | 2011-04-27 | 2012-10-31 | Mitsubishi HiTec Paper Europe GmbH | Wärmeempfindliches Aufzeichnungsmaterial mit Authentifikationsmerkmal |
EP2517889A1 (de) | 2011-04-27 | 2012-10-31 | Mitsubishi HiTec Paper Europe GmbH | Wärmeempfindliches Aufzeichnungsmaterial mit Authentifikationsmerkmal |
KR20120140630A (ko) * | 2011-06-21 | 2012-12-31 | 제너럴 일렉트릭 캄파니 | 광학 데이터 저장 매체에 데이터를 기록하는 방법 및 광학 데이터 저장 매체 |
US8475975B2 (en) * | 2011-06-21 | 2013-07-02 | General Electric Company | Method of recording data in an optical data storage medium and an optical data storage medium |
Also Published As
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AU2003226672A1 (en) | 2003-10-08 |
WO2003080364A1 (en) | 2003-10-02 |
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