WO2011078675A1 - Security feature - Google Patents
Security feature Download PDFInfo
- Publication number
- WO2011078675A1 WO2011078675A1 PCT/NL2010/050885 NL2010050885W WO2011078675A1 WO 2011078675 A1 WO2011078675 A1 WO 2011078675A1 NL 2010050885 W NL2010050885 W NL 2010050885W WO 2011078675 A1 WO2011078675 A1 WO 2011078675A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- use according
- support structure
- security feature
- security
- functional group
- Prior art date
Links
- 125000000524 functional group Chemical group 0.000 claims abstract description 64
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 238000000862 absorption spectrum Methods 0.000 claims abstract description 5
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 5
- 230000005291 magnetic effect Effects 0.000 claims abstract description 5
- 238000004020 luminiscence type Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 10
- 230000008863 intramolecular interaction Effects 0.000 claims description 9
- 238000000295 emission spectrum Methods 0.000 claims description 7
- 230000005281 excited state Effects 0.000 claims description 5
- 108090000765 processed proteins & peptides Proteins 0.000 claims description 5
- 230000001419 dependent effect Effects 0.000 claims description 4
- 150000007523 nucleic acids Chemical group 0.000 claims description 3
- 239000002773 nucleotide Substances 0.000 claims description 3
- 125000003729 nucleotide group Chemical group 0.000 claims description 3
- 102000004196 processed proteins & peptides Human genes 0.000 claims description 3
- 108090000623 proteins and genes Chemical group 0.000 claims description 3
- 102000004169 proteins and genes Human genes 0.000 claims description 3
- 230000003098 cholesteric effect Effects 0.000 claims description 2
- 238000000695 excitation spectrum Methods 0.000 claims description 2
- 238000000504 luminescence detection Methods 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000012736 aqueous medium Substances 0.000 claims 1
- 239000002609 medium Substances 0.000 claims 1
- 230000001953 sensory effect Effects 0.000 claims 1
- 229920000642 polymer Polymers 0.000 description 20
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 12
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 229960000956 coumarin Drugs 0.000 description 6
- 235000001671 coumarin Nutrition 0.000 description 6
- 239000000976 ink Substances 0.000 description 6
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000002983 circular dichroism Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 4
- 150000001413 amino acids Chemical class 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 239000011888 foil Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 description 3
- 235000001014 amino acid Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000005670 electromagnetic radiation Effects 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 230000005389 magnetism Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000441 polyisocyanide Polymers 0.000 description 3
- 150000004032 porphyrins Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- IVRMZWNICZWHMI-UHFFFAOYSA-N azide group Chemical group [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 description 2
- 238000000978 circular dichroism spectroscopy Methods 0.000 description 2
- -1 coumarin Natural products 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- HCUYBXPSSCRKRF-UHFFFAOYSA-N diphosgene Chemical compound ClC(=O)OC(Cl)(Cl)Cl HCUYBXPSSCRKRF-UHFFFAOYSA-N 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- KJOLVZJFMDVPGB-UHFFFAOYSA-N perylenediimide Chemical compound C=12C3=CC=C(C(NC4=O)=O)C2=C4C=CC=1C1=CC=C2C(=O)NC(=O)C4=CC=C3C1=C42 KJOLVZJFMDVPGB-UHFFFAOYSA-N 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000021317 sensory perception Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- RWQNBRDOKXIBIV-UHFFFAOYSA-N thymine Chemical compound CC1=CNC(=O)NC1=O RWQNBRDOKXIBIV-UHFFFAOYSA-N 0.000 description 2
- GFFGJBXGBJISGV-UHFFFAOYSA-N Adenine Chemical compound NC1=NC=NC2=C1N=CN2 GFFGJBXGBJISGV-UHFFFAOYSA-N 0.000 description 1
- 229930024421 Adenine Natural products 0.000 description 1
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical compound [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 1
- 108010016626 Dipeptides Proteins 0.000 description 1
- 241000854350 Enicospilus group Species 0.000 description 1
- 238000006736 Huisgen cycloaddition reaction Methods 0.000 description 1
- 241000826860 Trapezium Species 0.000 description 1
- NPRDEIDCAUHOJU-UHFFFAOYSA-N [Pt].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Pt].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NPRDEIDCAUHOJU-UHFFFAOYSA-N 0.000 description 1
- 229960000643 adenine Drugs 0.000 description 1
- 125000003295 alanine group Chemical group N[C@@H](C)C(=O)* 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 125000002355 alkine group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000001540 azides Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000001142 circular dichroism spectrum Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000010908 decantation Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- IHFKUSHEZIZSDN-UHFFFAOYSA-N formamide;perylene Chemical compound NC=O.C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 IHFKUSHEZIZSDN-UHFFFAOYSA-N 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002073 nanorod Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000005298 paramagnetic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 235000018102 proteins Nutrition 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000000707 stereoselective effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- FAGLEPBREOXSAC-UHFFFAOYSA-N tert-butyl isocyanide Chemical compound CC(C)(C)[N+]#[C-] FAGLEPBREOXSAC-UHFFFAOYSA-N 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 229940113082 thymine Drugs 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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
- B42D25/30—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
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
-
- B42D2033/20—
-
- B42D2035/24—
-
- 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
- B42D25/391—Special inks absorbing or reflecting polarised light
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1044—Heterocyclic compounds characterised by ligands containing two nitrogen atoms as heteroatoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1088—Heterocyclic compounds characterised by ligands containing oxygen as the only heteroatom
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/14—Macromolecular compounds
Definitions
- the invention relates inter alia to the use of a certain type of security feature, the security feature itself, an article provided with a security feature and a method of authenticating an article provided with a security feature.
- a security feature in articles like paper including synthetic "paper” predominantly prepared from plastic, and documents produced therefrom like banknotes and the like is known in the art.
- the protection hereinafter named security feature, can be incorporated into the substrate during production.
- a watermark is the most familiar example of a security feature incorporated during production.
- Luminescent fibres and security threads in banknotes are generally known to the general public.
- one or more security features can be added to said substrate , e.g. with the aid of a special printing technique or by applying an optically active element like a hologram or kinegram. In such a situation the nature of the substrate is less significant. In both cases, i.e. during use of either normal paper or security paper as substrate a document comprising one or more security features is obtained.
- Security paper is distinguished from paper protected in a different manner because of the fact that a security feature is incorporated in the paper mass during production.
- security features suited for this purpose comprise inter alia also an optically active structure/print that shows an angularly dependent image/colour like a holographic structure at the front surface of EURO banknotes or an angularly dependent colour at the back thereof. For example, touching by the fingers and/or nails allows sensing a "ridged structure" in the striated rectangular trapezium left above the printed architectonic structure at the front of a EURO banknote.
- a subsequent step in detecting a security feature is using simple and cheap aids like an UV lamp, polarisator, conductivity measuring device and the like.
- This kind of aids is used e.g. during checking the genuineness of a banknote upon payment at a cash deck in a store.
- These security features that can be detected by means of simple aids are also called second line features.
- security features are present in banknotes, the existence of which is only known to the competent authorities or persons like commercial banks and/or central banks, and for which specific and sometimes complicated detection equipment is required in order to determine the presence thereof. Then there is talk of third and fourth line features.
- a fifth level used by e.g. forensic experts, as has been described in EP 1 902 855 A2.
- a transponder is used more and more in order to ensure the genuineness of a document, in particular identity documents.
- the transponder is incorporated in the document and comprises inter alia data of the legitimate owner.
- Sometimes the use of a transponder is problematic, e.g. in banknotes. This is caused by the costs and vulnerability in view of the usual way of handling these articles.
- An object of the invention is to reduce or avoid one or more of the disadvantages of the state of the art mentioned above, and/or to offer a useful alternative.
- the invention aims at providing a security feature and its use, which feature allows different security features/securing properties to be positioned with respect to one another on molecular scale.
- a further object is to provide a compound as security feature having a specific mutual molecular orientation of the active (to be detected) group or groups.
- Yet an other object is to establish an efficient and/or specific intramolecular interaction between different active groups or compounds, such as for example between luminescent compounds.
- Still another object is to provide a compound wherein functional groups having different properties are combined into one macromolecule.
- Still another object is the provision of a security feature that can unite all security levels varying from the first visible level to the machine readable signals for the benefit of the forensic level within a molecule.
- a security feature according to claim 1 In the context of the invention the following expressions are used.
- a functional group is a compound that is present at the polyisocyano support structure, preferably polyisocyanopeptide support structure, having a visibly perceptible property and/or a measurable property. Properties are exemplified by among others colour, luminescence, (para)magnetism and electric conductivity. Functional groups of a biological kind can also be used such as for example, nucleic acid fragments, proteins, peptides or nucleotides.
- the expression support structure is used in the context of the present invention to denote a polyisocyano support structure as well as a polyisocyanopeptide support structure.
- a reactive group is a group at the polyisocyano support structure or the peptide part or at the functional group, which allows coupling a functional group to the support structure, e.g. a polyisocyano mono and/or dipeptide support structure.
- Acetylene and azide groups are examples of such reactive groups.
- Luminescence is understood to mean emitting electromagnetic radiation after excitation. This expressions comprises both fluorescence and phosphorescence.
- Lifetime of the excited state is understood to mean the average lifetime of the excited state. This lifetime is inversely proportional to the rate of decay of the excited state.
- the security feature according to the invention comprises a support structure (hereinafter sometimes referred to as the polymer), i.e. a polyisocyano support structure, preferably a chiral polyisocyanopeptide structure, which functions as a carrier for coupling one or more functional groups of the same or different nature and thus having separately visual perceptible or detectable properties or not.
- a support structure hereinafter sometimes referred to as the polymer
- a polyisocyano support structure preferably a chiral polyisocyanopeptide structure
- Many functional groups can be coupled to one and the same polymer molecule. Because functional groups are present at the chiral carrier in a spatially very specific configuration with respect to one another, very specific and unique intramolecular interactions are possible between the various functional groups that have been coupled and/or the chiral support structure. This results in a response of the security feature to e.g.
- the support structure can be functionalized with only one kind of functional group.
- Different functional groups can also be present attached to one and the same polymeric molecule, thereby causing the functionalized polymer to show a combination of totally different properties such as for example luminescence and (para)magnetism, a colour and conductivity or different colours in the visible region and absorption in the near infrared range.
- the support structure has a helical configuration the skeleton structure will show a CD (circular dichroism) signal, which is detectable by CD spectroscopy, in addition to all signals derived from the functional groups.
- CD circular dichroism
- the signal of a functional group can be polarized by the chirality of the skeleton structure like polarized luminescence.
- the polyisocyano support structure advantageously the
- polyisocyanopeptide support structure provided with at least one functional group shows circularly polarised luminescence, in particular circularly polarised fluorescence.
- This characteristic may be derived from the support structure, e.g. the helix configuration, one or more functional groups or combination thereof.
- This kind of security feature can be detected by an appropiate fluorometer under electromagnetic radiation, e.g. UV illumination, using one or more circularly polarising filters (polarisers).
- polarisers filters
- the functionalized polymer is provided also with hydrophilic groups, for example ethylene glycol or cellulose side groups. This allows using the functionalized compounds directly in the (paper) manufacturing process. If the functionalized compound is to be incorporated in a plastic, a more apolar character is required. This can be set by means of apolar side chains and/or additional groups, which are to be attached. From such a plastic a foil can be produced, which then can be used as a socalled foil strip, a patch or a thread in or on the paper. This foil can also be further processed, so that it also attains other properties caused by this specific further processing step. Security fibers having a number of properties can also be manufactured from plastic comprising
- these fibers can be processed e.g. into the paper mass.
- the dissolution behaviour adjusted by means of suitable functional groups is also important, when the compounds are to be used in inks or pigments as security features.
- a further advantage of the functionalized support structure is that the whole molecule is organic, which is an advantage for application in security inks.
- the polyisocyano support structure can be prepared by means of Ni(ll) catalyzed
- polyisocyanopeptides The presence of peptide side chains achieves a more stable helix having a larger rigidity because of the H bridge interactions between the peptide side chains.
- the preparation of polyisocyanopeptides is described, e.g. in Cornelissen, J. J. L. M.; Graswinckel, W. S.;
- diagram 1 shows a large number of synthesized polymers based on isocyanopeptide in view of rather simple amino acids like alanine, glycine, serine and histidine.
- reactive groups in particular an acetylene group or an azide group are described in Schwartz, E.; Kitto, H. J.; de Gelder, R.; Nolte, R. J. M.; Rowan, A. E.;
- the functional groups can be selected from the group comprising luminescent
- chromophores compounds having (para)magnetic or electromagnetic properties, compounds having an absorption spectrum in the UV range and/or the visible range and/or the IR or near IR range, compounds showing electrical conductivity (optionally via mutual orientation), biochemical compounds, compounds affording a liquid crystal behaviour to the security feature and combinations thereof.
- the functional group is a luminescent chromophore.
- Thiophene, coumarin, perylene and porphyrin can be mentioned as examples. See Kitto, H. J.; Schwartz, E.;
- the chromophore coupled to the support structure exhibits luminescence characteristics through intramolecular interaction of the coupled groups, which characteristics differ from the luminescence characteristics of the same but uncoupled groups.
- the emission spectra and/or the lifetime of the exited state of luminescence as a result of the intramolecular interactions between at least one type of functional groups differ from the emission spectra and/or the lifetime of the excited state of the monomeric units of the respective type of functional groups.
- At least two different kinds of luminescent chromophores are coupled to the polyisocyano(peptide) support structure, wherein the emission spectrum of one kind of luminescent chromophore overlaps with the excitation spectrum of the other kind of luminescent chromophore.
- Examples of such a combination are platinum-porphyrin with perylene, and coumarin and perylene. Kitto et al., supra.
- a paragmagnetic functionality is coupled to the support structure like e.g. a porphyrin , such as is described for a polyisocyanopeptide support structure by Witte, P. A. J.; Castriciano, M.; Cornelissen, J. J. L. M.; Scolaro, L. M.; Nolte, R. J. M.;
- Perylene diimide
- a group for an electrical conductive functionalized polymer See Schwartz, E.; Palermo, V.; Finlayson, C. E.; Huang, Y.-S.; Otten, M. B. J.;
- At least one functional group is a biochemical compound, for example selected from the group of nucleic acid fragments, protein structures, peptides and smaller biochemical compounds like for example the nucleotides thymine and adenine such as described in Otten, M. B. J. PhD thesis:
- the security feature exhibits the behaviour of a liquid crystal, such as nematic or cholesteric behaviour. See Metselaar, G. A.; Wezenberg, S. J.; Cornelissen, J. J. L. M.; Nolte, R. M.; Rowan, A. E. Lyotropic liquid-crystalline behavior of polyisocyanodipeptides. J. Polym. Sci., Part A: Polym. Chem. 2007, 45, (6), 981 -988.
- the security feature has a solubility, which is adapted to the matrix wherein it is incorporated or processed.
- a group offering hydrophilic behaviour is an alcohol such as ethylene glycol.
- apolar functional groups can be used to facilitate incorporating the security feature in a plastic.
- security feature is preferred in articles selected from the group comprising security paper, value paper, security documents, identity documents, value documents, vouchers, tickets, labels, prescription forms, certificates and packages.
- the invention relates to an article, preferably selected from the group comprising security paper, value paper, security documents, identity documents, value documents, vouchers, tickets, labels, prescription forms, certificates and packages, the article comprising at least one security feature comprising a polyisocyano support structure having at least one functional group, preferably a polyisocyanopeptide structure.
- the invention relates to a security feature comprising a polyisocyano support structure having at least one functional group, preferably a
- the invention also relates to a method of authenticating articles provided with a security feature according to the invention, wherein a property dependent from the functional group and/or from the polyisocyano support is determined, for example via sensory perception, and preferably a machine detectable, more preferably measurable property.
- a property dependent from the functional group and/or from the polyisocyano support is determined, for example via sensory perception, and preferably a machine detectable, more preferably measurable property.
- the method according to the invention uses polarised luminescence spectroscopy to detect circularly polarised luminescence.
- chirality of a polyisocyano support structure preferably a polyisocyanopeptide support structure provided with at least one functional group is determined.
- E.g CD spectroscopy is preferably used to determine circular dichroism.
- Fig. 1 is a diagram of a configuration of a polyisocyanopeptide support structure having reactive groups
- Fig. 2 a) - e) are diagrams presenting different possibilities of functionalizing the
- Fig. 3 a) - d) are diagrams of a polyisocyanopeptide support structure functionalized with a chromophore and associated spectra;
- Fig. 4 a) - c) are diagrams of a polyisocyanopeptide support structure functionalized with two chromophores and associated spectra.
- Fig. 1 a diagrammatic representation of the structure of a base molecule is shown. It consists of polymerized isocyanide provided with alanine side chains. By means of the side chains of the amino acids beta type H bridge interactions cause a stabilized structure of the helix, of which the helix can be laevorotary or dextrorotary depending on the stereospecific configuration of the amino acid side chains.
- the base structure exhibits a large stability, wherein the length can vary from about 100 nm to about 20 ⁇ .
- the terminal amino acid comprises a reactive group indicated by X, with which the functional groups can be attached to the polyisocyano support structure.
- Fig. 2 diagrammatically illustrates the flexibility of the polyisocyanopeptide support structure in view of obtaining a functionalized polymer.
- the functional group itself comprises a reactive group, which is able to react with the reactive group X.
- Fig. 2a a schematic example is presented, wherein a polyisocyanopeptide is functionalized with one kind of functional group, indicated here as A.
- Fig. 2b provides an example of a polyisocyanopeptide that comprises differing functional groups, indicated here as group A and group B, and that are distributed in blocks.
- Fig. 2c provides a diagrammatic example of a polyisocyanopeptide, to which two functional groups, i.e. group A and group B are attached at random.
- Fig. 2d represents a polyisocyanopeptide having functional groups A and B in an alternating order.
- Fig. 2e shows an example of a support molecule functionalized with groups A and B, to which a hydrophilic additional group indicated by a grey circle has been coupled at several positions, thereby allowing the molecule to dissolve in an aqueous environment.
- Fig. 3 shows a diagrammatic example of a molecule that comprises one luminescent chromophore as a functional group, i.e. perylene-diimide (A).
- the occupation level of the functional group is 100 % in this example (see Fig. 2a).
- De spectral data of this compound and those of the non-coupled units are shown in Figs. 3b - 3d.
- the black lines indicate the functionalized molecule (the polymer) in this figure; the grey lines the non-coupled units (monomers).
- the isocyanide monomer (138 mg, 0.194 mmol) was dissolved in CHCI 3 . 1/1000 equiv. of nickel (1 mL of a 0.19 mM solution of Ni(CI0 4 ) 2 in EtOH/CHCI 3 ) was added to the stirred solution. After 1 h. the isocyanide was consumed completely. The polymer was concentrated to about 10 mL and precipitated in 100 mL of methanol/water (1 :1 v/v) under vigorous stirring. Then the solid was collected by centrifugation and subsequent decantation of the solvent. The solid was again dissolved in chloroform (5 mL) and precipitated in about 60 mL methanol. The solid polymer was again collected.
- Fig. 4 a diagrammatic example shows a molecule that has been functionalized with two different chromophores, i.e. perylene diimide (black, Fig. 4a) (A) and coumarin (grey in Fig. 4a) (B).
- Fig. 4a diagram representing the functionalized polymer the occupation of the polymer is 50% A and B respectively and is at random;
- Fig. 4b comprises the UV visible absorption spectrum and the emission spectrum of the assembling monomeric units. In both the UV visible absorption spectrum and the fluorescence spectrum of the functionalized molecule the presence of both chromophores, i.e.
- the occupation (degree) of the polymer is mentioned, that is to say that a certain percentage of all terminal amino acids is occupied with a functionality.
- a difference in percentage directly effects the intensity of the signal and the degree of the intramolecular interactions.
Abstract
The invention relates to the use of a polyisocyano support structure provided with at least one functional group as a security feature, preferably a polyisocyanopeptide support structure, in particular in an article selected from the group comprising security paper, value paper, security documents, identity documents, value documents, vouchers, tickets, labels, prescription forms, certificates and packages. Examples of functional groups comprise luminescent chromophores, compounds having (para)magnetic properties, compounds having an absorption spectrum in the UV range and/or the visible range and/or the IR range or near IR range, compounds showing electrical conductivity, optionally via mutual orientation, biochemical compounds, compounds affording a liquid crystal behaviour to the security feature and combinations thereof.
Description
SECURITY FEATURE
The invention relates inter alia to the use of a certain type of security feature, the security feature itself, an article provided with a security feature and a method of authenticating an article provided with a security feature. The application of a security feature in articles like paper including synthetic "paper" predominantly prepared from plastic, and documents produced therefrom like banknotes and the like is known in the art. For securing this kind of paper and documents produced thereof many securing methods and materials are known in order to prevent easy counterfeiting. The protection, hereinafter named security feature, can be incorporated into the substrate during production. In case of a paper substrate a security paper is obtained. A watermark is the most familiar example of a security feature incorporated during production. Luminescent fibres and security threads in banknotes are generally known to the general public. Also after producing a substrate like paper one or more security features can be added to said substrate , e.g. with the aid of a special printing technique or by applying an optically active element like a hologram or kinegram. In such a situation the nature of the substrate is less significant. In both cases, i.e. during use of either normal paper or security paper as substrate a document comprising one or more security features is obtained.
Security paper is distinguished from paper protected in a different manner because of the fact that a security feature is incorporated in the paper mass during production.
The general public relies on sensory perception in order to recognize the genuineness (authenticating) of an article like a security document or value document, e.g. viewing with the eyes and sensing with the fingers often in order to determine the presence of a security feature and/or its position. In addition to the security threads and watermarks mentioned above security features suited for this purpose comprise inter alia also an optically active structure/print that shows an angularly dependent image/colour like a holographic structure at the front surface of EURO banknotes or an angularly dependent colour at the back thereof. For example, touching by the fingers and/or nails allows sensing a "ridged structure" in the striated rectangular trapezium left above the printed architectonic structure at the front of a EURO banknote.
A subsequent step in detecting a security feature is using simple and cheap aids like an UV lamp, polarisator, conductivity measuring device and the like. This kind of aids is used e.g.
during checking the genuineness of a banknote upon payment at a cash deck in a store. These security features that can be detected by means of simple aids are also called second line features. Furthermore, security features are present in banknotes, the existence of which is only known to the competent authorities or persons like commercial banks and/or central banks, and for which specific and sometimes complicated detection equipment is required in order to determine the presence thereof. Then there is talk of third and fourth line features. Finally, there is a fifth level, used by e.g. forensic experts, as has been described in EP 1 902 855 A2.
A transponder is used more and more in order to ensure the genuineness of a document, in particular identity documents. The transponder is incorporated in the document and comprises inter alia data of the legitimate owner. Sometimes the use of a transponder is problematic, e.g. in banknotes. This is caused by the costs and vulnerability in view of the usual way of handling these articles.
Many security features starting from the second level are based on specific properties of chemical compounds. Some examples of patent documents describing certain properties of compounds for use in securing security documents and/or value documents comprise:
luminescence through excitation by electrical current (WO 2004 108426 A2) or by change of shape (WO 01 83237 A1 );
- magnetic behaviour (EP 1 646 057 A2, EP 1 646 056 A1 ); and
- electrical conductivity (US 2006 0075249 A1 ).
In the majority of luminescent features use is made of excitation by light. For the most part the luminescent properties are chosen in the visible or near IR range. Here compounds, materials and configurations are searched, which offer specific final luminescence properties and characteristics as is described for example in DE 10 2006 047 851 A1 , DE 10 2006 047 852 A1 , US 2007 0132984 A1 , US 2007 0187630 A1 and EP 1 801 759 A1
In addition to the paper itself, usually specific fibers, foils, security threads and inks are the direct carriers of the security features. Often in one and the same carrier such as e.g. a security thread, different security features are combined such as materials which show fluorescence and materials that show magnetism. Usually this means that a number of security features are present spatially distributed in/on the carrier. It is also possible to incorporate the security features in inks that are delivered subsequently onto the substrate.
If one applies inks having different security features in succession, it is difficult though possible to do so in register, so that multiple, different security features can be detected at one position. It is also possible to incorporate different security features in one and the same ink, thereby simplifying the application in register. Then it is desired that the nature of the compounds comprising the security features, allows forming a stable blend. Using different compounds as security features, of which the dissolution behaviour is less compatible, may interfere with the forming of a stable blend, even including the risk of separation during of after the application. In DE 2005 047 609 A1 it has been tried to solve the problem of application in register of different security features/properties by manufacturing particles having a core-shell structure, wherein the core possesses other properties than the shell.
An object of the invention is to reduce or avoid one or more of the disadvantages of the state of the art mentioned above, and/or to offer a useful alternative.
More particularly, the invention aims at providing a security feature and its use, which feature allows different security features/securing properties to be positioned with respect to one another on molecular scale.
A further object is to provide a compound as security feature having a specific mutual molecular orientation of the active (to be detected) group or groups.
Yet an other object is to establish an efficient and/or specific intramolecular interaction between different active groups or compounds, such as for example between luminescent compounds.
Still another object is to provide a compound wherein functional groups having different properties are combined into one macromolecule.
Still another object is the provision of a security feature that can unite all security levels varying from the first visible level to the machine readable signals for the benefit of the forensic level within a molecule. According to a first aspect of the invention one or more objects are achieved by the use of a security feature according to claim 1 .
In the context of the invention the following expressions are used.
A functional group is a compound that is present at the polyisocyano support structure, preferably polyisocyanopeptide support structure, having a visibly perceptible property and/or a measurable property. Properties are exemplified by among others colour, luminescence, (para)magnetism and electric conductivity. Functional groups of a biological kind can also be used such as for example, nucleic acid fragments, proteins, peptides or nucleotides. The expression support structure is used in the context of the present invention to denote a polyisocyano support structure as well as a polyisocyanopeptide support structure.
A reactive group is a group at the polyisocyano support structure or the peptide part or at the functional group, which allows coupling a functional group to the support structure, e.g. a polyisocyano mono and/or dipeptide support structure. Acetylene and azide groups are examples of such reactive groups.
Luminescence is understood to mean emitting electromagnetic radiation after excitation. This expressions comprises both fluorescence and phosphorescence.
Lifetime of the excited state is understood to mean the average lifetime of the excited state. This lifetime is inversely proportional to the rate of decay of the excited state.
The security feature according to the invention comprises a support structure (hereinafter sometimes referred to as the polymer), i.e. a polyisocyano support structure, preferably a chiral polyisocyanopeptide structure, which functions as a carrier for coupling one or more functional groups of the same or different nature and thus having separately visual perceptible or detectable properties or not. Many functional groups can be coupled to one and the same polymer molecule. Because functional groups are present at the chiral carrier in a spatially very specific configuration with respect to one another, very specific and unique intramolecular interactions are possible between the various functional groups that have been coupled and/or the chiral support structure. This results in a response of the security feature to e.g. electromagnetic irradiation that differs significantly from the response of a security feature, wherein the functional group as such, i.e. without the specific intramolecular interactions, is present.
It is also possible to couple many different types of functional groups having distinguished functionality to the same support structure, usually the same polymeric support molecule. This allows to give one and the same support structure after functionalizing several properties that can be separately perceived and/or detected like colour, luminescence; (para)magnetic behaviour and e.g. conductivity.
Furthermore, it also belongs to the possibilities to prepare blends of different kinds of functionalized support structures, which have an identical or very similar dissolution behaviour because the molecules possess a corresponding base structure and additionally can be provided with specific groups which effect the dissolution behaviour, thereby reducing the risk of undesired separation during application.
The support structure can be functionalized with only one kind of functional group. Different functional groups can also be present attached to one and the same polymeric molecule, thereby causing the functionalized polymer to show a combination of totally different properties such as for example luminescence and (para)magnetism, a colour and conductivity or different colours in the visible region and absorption in the near infrared range. Also there can be interactions between different kinds of functional groups thereby modifying the behaviour of functional groups with respect to detection with e.g.
electromagnetic radiation. Then a unique signal is to be detected, which cannot be reproduced by blending of the individual functional groups, because in such a case the unique spatial positions and thus the specific intramolecular interactions of the functional groups with respect to one another would be absent. Because the support structure has a helical configuration the skeleton structure will show a CD (circular dichroism) signal, which is detectable by CD spectroscopy, in addition to all signals derived from the functional groups. Furthermore the signal of a functional group can be polarized by the chirality of the skeleton structure like polarized luminescence. In a preferred embodiment the polyisocyano support structure, advantageously the
polyisocyanopeptide support structure, provided with at least one functional group shows circularly polarised luminescence, in particular circularly polarised fluorescence. This characteristic may be derived from the support structure, e.g. the helix configuration, one or more functional groups or combination thereof. This kind of security feature can be detected by an appropiate fluorometer under electromagnetic radiation, e.g. UV illumination, using one or more circularly polarising filters (polarisers).
Furthermore it is possible to adjust the solubility of the functionalized polymer by giving at least a part of the side chains of the polymer a character adapted to a desired
environment/solvent through additional groups. In order to establish a useful solubility in an aqueous environment the functionalized polymer is provided also with hydrophilic groups, for example ethylene glycol or cellulose side groups. This allows using the functionalized compounds directly in the (paper) manufacturing process. If the functionalized compound is to be incorporated in a plastic, a more apolar character is required. This can be set by means of apolar side chains and/or additional groups, which are to be attached. From such a plastic a foil can be produced, which then can be used as a socalled foil strip, a patch or a thread in or on the paper. This foil can also be further processed, so that it also attains other properties caused by this specific further processing step. Security fibers having a number of properties can also be manufactured from plastic comprising
functionalized compounds. Then these fibers can be processed e.g. into the paper mass.
The dissolution behaviour adjusted by means of suitable functional groups is also important, when the compounds are to be used in inks or pigments as security features.
A further advantage of the functionalized support structure is that the whole molecule is organic, which is an advantage for application in security inks.
The polyisocyano support structure can be prepared by means of Ni(ll) catalyzed
polymerization starting from an isocyano monomer, like tert-butyl isocyanide. The bulky alkyl groups effect stabilization of the helix thus formed. Functionalized polyisocyanides offering a detectable paramagnetic signal are described, e.g. in Vlietstra, E. J.; Nolte, R. J. M.;
Zwikker, J. W.; Drenth, W.; Meijer, E. W., Synthesis and magnetic properties of a rigid high- spin density polymer with piperidine-N-oxyl pending groups, Macromolecules, 1990, 23, (4), 946-948 and Abdelkader, M.; Drenth, W.; Meijer, E. W., Synthesis and characterization of a stable poly(iminomethylene) with pendant phenoxyl radicals, Chem. Mater. 1991 , 3, (4), 598- 602.
The presence of peptide side chains achieves a more stable helix having a larger rigidity because of the H bridge interactions between the peptide side chains. The preparation of polyisocyanopeptides is described, e.g. in Cornelissen, J. J. L. M.; Graswinckel, W. S.;
Adams, P. J. H. M.; Nachtegaal, G. H.; Kentgens, A. P. M.; Sommerdijk, N. A. J. M.; Nolte, R. J. M. Synthesis and characterization of polyisocyanides derived from alanine and glycine dipeptides. J. Polym. Sci., Part A: Polym. Chem. 2001 , 39, (24), 4255-4264, Cornelissen, J.
J. L. M.; Donners, J. J. J. M.; de Gelder, R.; Graswinckel, W. S.; Metselaar, G. A.; Rowan, A. E.; Sommerdijk, N. A.; Nolte, R. J. M. beta -Helical polymers from isocyanopeptides. Science 2001 , 293, (5530), 676-680 en de thesis "Polymerization of Isocyanopeptides" van
Metselaar, G.A., 2006 (ISBN 90-9020135-1 ). In Cornelissen, J. J. L. M. Hierarchical transfer of stereochemical information in synthetic macromolecules, Pure Appl. Chem., 2002, 74, (11), 2021 -2030 diagram 1 shows a large number of synthesized polymers based on isocyanopeptide in view of rather simple amino acids like alanine, glycine, serine and histidine. Examples of reactive groups, in particular an acetylene group or an azide group are described in Schwartz, E.; Kitto, H. J.; de Gelder, R.; Nolte, R. J. M.; Rowan, A. E.;
Cornelissen, J. J. L. M. Synthesis, characterisation and chiroptical properties of 'click'able polyisocyanopeptides. J. Mater. Chem. 2007, 17, (19), 1876-1884, and Schwartz, E.; Koepf, M.; Kitto, H. J.; Espelt, M.; Nebot-Carda, V. J.; De Gelder, R.; Nolte, R. J. M.; Cornelissen, J. J. L. M.; Rowan, A. E. Water soluble azido polyisocyanopeptides as functional-sheet mimics. J. Polym. Sci., Part A: Polym. Chem. 2009, 47, 4150-4164 respectively.
Coupling a functional group via a reactive group to the polyisocyanopeptide support structure is described, e.g. in Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B. A stepwise Huisgen cycloaddition process: Copper (I) -catalyzed regioselective "ligation" of azides and terminal alkynes. Angew. Chem., Int. Ed. 2002, 41 , (14), 2596-2599.
The functional groups can be selected from the group comprising luminescent
chromophores, compounds having (para)magnetic or electromagnetic properties, compounds having an absorption spectrum in the UV range and/or the visible range and/or the IR or near IR range, compounds showing electrical conductivity (optionally via mutual orientation), biochemical compounds, compounds affording a liquid crystal behaviour to the security feature and combinations thereof. In an embodiment the functional group is a luminescent chromophore. Thiophene, coumarin, perylene and porphyrin can be mentioned as examples. See Kitto, H. J.; Schwartz, E.;
Nijemeisland, M.; Koepf, M.; Cornelissen, J.; Rowan, A. E.; Nolte, R. J. M., Post- modification of helical dipeptido polyisocyanides using the 'click' reaction. J. Mater. Chem. 2008, 18, (46), 5615-5624.
In a particular embodiment the chromophore coupled to the support structure exhibits luminescence characteristics through intramolecular interaction of the coupled groups, which characteristics differ from the luminescence characteristics of the same but uncoupled groups. In a further embodiment thereof the emission spectra and/or the lifetime of the exited state of luminescence as a result of the intramolecular interactions between at least one type of functional groups differ from the emission spectra and/or the lifetime of the excited state of the monomeric units of the respective type of functional groups.
According to a particularly preferred embodiment at least two different kinds of luminescent chromophores are coupled to the polyisocyano(peptide) support structure, wherein the emission spectrum of one kind of luminescent chromophore overlaps with the excitation spectrum of the other kind of luminescent chromophore. Examples of such a combination are platinum-porphyrin with perylene, and coumarin and perylene. Kitto et al., supra. In a particular embodiment a paragmagnetic functionality is coupled to the support structure like e.g. a porphyrin , such as is described for a polyisocyanopeptide support structure by Witte, P. A. J.; Castriciano, M.; Cornelissen, J. J. L. M.; Scolaro, L. M.; Nolte, R. J. M.;
Rowan, A. E. Helical polymer-anchored porphyrin nanorods. Chem. Eur. J. 2003, 9, (8), 1775-1781 , comprising a metal ion having unpaired spin, which is incorporated therein. See also Vlietstra, supra and Abdelkader, supra.
In a particular embodiment at least two different functional groups having different electromagnetic properties are bonded to the support structure. Perylene (diimide) is an example of a group for an electrical conductive functionalized polymer. See Schwartz, E.; Palermo, V.; Finlayson, C. E.; Huang, Y.-S.; Otten, M. B. J.;
Liscio, A.; Trapani, S.; Gonzalez-Valls, I.; Brocorens, P.; Cornelissen, J. J. L. M.; Peneva, K.;
Mullen, K.; Spano, F.; Yartsev, A.; Westenhoff, S.; Friend, R. H.; Beljonne, D.; Nolte, R. J.
M.; Samori, P.; Rowan, A. E. 'Helter Skelter-like' Perylene Polyisocyanopeptides. Chem. Eur. J. 2009, 15, 2536-2547.
In a further embodiment of the use according to the invention at least one functional group is a biochemical compound, for example selected from the group of nucleic acid fragments, protein structures, peptides and smaller biochemical compounds like for example the nucleotides thymine and adenine such as described in Otten, M. B. J. PhD thesis:
Functionalized Polyisocyanides. Radboud University, Nijmegen, Netherlands, ISBN: 978-90- 9024890-5.
According to yet another embodiment the security feature exhibits the behaviour of a liquid crystal, such as nematic or cholesteric behaviour. See Metselaar, G. A.; Wezenberg, S. J.; Cornelissen, J. J. L. M.; Nolte, R. M.; Rowan, A. E. Lyotropic liquid-crystalline behavior of polyisocyanodipeptides. J. Polym. Sci., Part A: Polym. Chem. 2007, 45, (6), 981 -988.
According to a particular embodiment the security feature has a solubility, which is adapted to the matrix wherein it is incorporated or processed. An example of a group offering hydrophilic behaviour is an alcohol such as ethylene glycol. As described above, apolar functional groups can be used to facilitate incorporating the security feature in a plastic.
Use of the security feature is preferred in articles selected from the group comprising security paper, value paper, security documents, identity documents, value documents, vouchers, tickets, labels, prescription forms, certificates and packages.
According to a subsequent aspect the invention relates to an article, preferably selected from the group comprising security paper, value paper, security documents, identity documents, value documents, vouchers, tickets, labels, prescription forms, certificates and packages, the article comprising at least one security feature comprising a polyisocyano support structure having at least one functional group, preferably a polyisocyanopeptide structure.
According to yet another aspect the invention relates to a security feature comprising a polyisocyano support structure having at least one functional group, preferably a
polyisocyanopeptide structure. If the support structure itself has a characteristic which can be used for securing an article, then the support structure only may also be used as a security feature. E.g. the polyisocyanopeptide showing circularly dichroism due to its helical configuration is a useful security feature. According to yet another aspect the invention also relates to a method of authenticating articles provided with a security feature according to the invention, wherein a property dependent from the functional group and/or from the polyisocyano support is determined, for example via sensory perception, and preferably a machine detectable, more preferably measurable property. Advantageously the method according to the invention uses polarised luminescence spectroscopy to detect circularly polarised luminescence. In a particular embodiment thereof additionally the chirality of a polyisocyano support structure, preferably
a polyisocyanopeptide support structure provided with at least one functional group is determined. E.g CD spectroscopy is preferably used to determine circular dichroism.
The preferred embodiments of the use of a security feature according to the first aspect of the invention, which have been described above, are applicable to these aspects of the invention in a similar way.
The invention will be illustrated by means of the attached drawing, wherein:
Fig. 1 is a diagram of a configuration of a polyisocyanopeptide support structure having reactive groups;
Fig. 2 a) - e) are diagrams presenting different possibilities of functionalizing the
polyisocyanopeptide support structure;
Fig. 3 a) - d) are diagrams of a polyisocyanopeptide support structure functionalized with a chromophore and associated spectra; and
Fig. 4 a) - c) are diagrams of a polyisocyanopeptide support structure functionalized with two chromophores and associated spectra.
In Fig. 1 a diagrammatic representation of the structure of a base molecule is shown. It consists of polymerized isocyanide provided with alanine side chains. By means of the side chains of the amino acids beta type H bridge interactions cause a stabilized structure of the helix, of which the helix can be laevorotary or dextrorotary depending on the stereospecific configuration of the amino acid side chains. The base structure exhibits a large stability, wherein the length can vary from about 100 nm to about 20 μηη. These values correspond to a molecular mass of 6.105 to 1 .10s grmol"1 (Cornelissen, J.J.L.M.; Donners, J.J.J.M., ; de Gelder, R.; Graswinckel, W.S. ; Metselaar, G.A. ; Rowan, A.E.; Sommerdijk , N.A.J. M.; Nolte, R.J.M., Science 2001 , 293 (5530), 676-680). The terminal amino acid comprises a reactive group indicated by X, with which the functional groups can be attached to the polyisocyano support structure. Another method of preparing a polymer having functional groups is modifying the functional group in such a way that the functionalized polymer is derived therefrom through
polymerization.
Fig. 2 diagrammatically illustrates the flexibility of the polyisocyanopeptide support structure in view of obtaining a functionalized polymer. The functional group itself comprises a reactive group, which is able to react with the reactive group X.
In Fig. 2a a schematic example is presented, wherein a polyisocyanopeptide is functionalized with one kind of functional group, indicated here as A.
Fig. 2b provides an example of a polyisocyanopeptide that comprises differing functional groups, indicated here as group A and group B, and that are distributed in blocks.
Fig. 2c provides a diagrammatic example of a polyisocyanopeptide, to which two functional groups, i.e. group A and group B are attached at random. Fig. 2d represents a polyisocyanopeptide having functional groups A and B in an alternating order.
Fig. 2e shows an example of a support molecule functionalized with groups A and B, to which a hydrophilic additional group indicated by a grey circle has been coupled at several positions, thereby allowing the molecule to dissolve in an aqueous environment.
In Fig. 2 only two different kinds of functional groups are shown, but it will be clear that many more different groups may be present. Fig. 3 shows a diagrammatic example of a molecule that comprises one luminescent chromophore as a functional group, i.e. perylene-diimide (A). The occupation level of the functional group is 100 % in this example (see Fig. 2a). De spectral data of this compound and those of the non-coupled units are shown in Figs. 3b - 3d. The black lines indicate the functionalized molecule (the polymer) in this figure; the grey lines the non-coupled units (monomers).
It is immediately evident that the spectral properties of the functionalized polymer differ from those of the assembling monomeric parts. Especially the differences in UV visible absorption (Fig. 3b), in emission (Fig. 3c) and in circular dichroism (CD, Fig. 3d) are striking. In the UV vis region it is clear that the spectrum of the polymer is broadened and shifted to longer wavelengths with respect to the non-coupled units. This is also reflected in the fluorescence- emission spectrum, where the spectrum of the polymer is shifted even tens of nanometers and moreover has a different intensity. A clear signal can be recognized in the perylene chromophore region of the CD spectrum in contrast to the non-coupled units where this signal is absent in this area.
The polymer shown in Fig. 3 was prepared as follows. /V-methylmorpholine (NMM) (76 μΙ, 0.69 mmol, 2.5 equiv.) and perylene formamide (200 mg, 0.27 mmol) were dissolved in 50 mL CH2CI2 under Schlenk conditions. The resulting solution was cooled to -30°C using acetone/C02. Stepwise (3 portions ) a total amount of 180 μΙ_ NMM (1 .64 mmol, 6 equiv) and 39 μΙ diphosgene (0.32 mmol, 1.2 equiv.) were added. TLC was used to watch the reaction progress. First, 2.5 equiv. of NMM were added followed by dropwise addition in 10 minutes of 0.5 equiv. of diphosgene in CH2CI2 (3 mL). The temperature was maintained at -30°C during the addition. The same amounts were added a second time. The remaining amounts were needed to complete the reaction. The temperature of the reaction mixture was adjusted to 0°C. Under vigorous stirring the reaction mixture was added to 100 mL of an ice- cold saturated aqueous sodium bicarbonate solution. 100 mL of CHCI3 was added. The organic layer was separated and washed with an aqueous 10% (w/w) sodium carbonate solution. After in vacuo evaporation of the solvent a red solid was obtained. The solid was purified by column chromatography. The yield was 171 mg (88%) of the isocyanide monomer. The isocyanide monomer (138 mg, 0.194 mmol) was dissolved in CHCI3. 1/1000 equiv. of nickel (1 mL of a 0.19 mM solution of Ni(CI04)2 in EtOH/CHCI3) was added to the stirred solution. After 1 h. the isocyanide was consumed completely. The polymer was concentrated to about 10 mL and precipitated in 100 mL of methanol/water (1 :1 v/v) under vigorous stirring. Then the solid was collected by centrifugation and subsequent decantation of the solvent. The solid was again dissolved in chloroform (5 mL) and precipitated in about 60 mL methanol. The solid polymer was again collected. This purifying step was repeated until no monomer emission was observed. Finally the red solid was dried in vacuo. The yield was 135 mg (98%). In Fig. 4 a diagrammatic example shows a molecule that has been functionalized with two different chromophores, i.e. perylene diimide (black, Fig. 4a) (A) and coumarin (grey in Fig. 4a) (B). Fig. 4a diagram representing the functionalized polymer, the occupation of the polymer is 50% A and B respectively and is at random; Fig. 4b comprises the UV visible absorption spectrum and the emission spectrum of the assembling monomeric units. In both the UV visible absorption spectrum and the fluorescence spectrum of the functionalized molecule the presence of both chromophores, i.e. perylene (450-600 nm) and coumarin (300-400 nm) can be seen. Comparing the fluorescence spectrum of the molecule that has been functionalized with both perylene and coumarin (Fig. 4c; grey lines) with the fluorescence spectrum of a molecule that has been functionalized with coumarin only (like diagrammatically shown in Fig. 2a) (Fig. 4c; black line) reveals that in the first case the
fluorescence of the coumarin is shifted clearly towards shorter wavelengths and thus there is a specific interaction between these chromophores.
In the abovementioned examples the occupation (degree) of the polymer is mentioned, that is to say that a certain percentage of all terminal amino acids is occupied with a functionality. One can select this percentage as desired upon synthesizing the compounds. A difference in percentage directly effects the intensity of the signal and the degree of the intramolecular interactions.
Claims
1 . Use of a polyisocyano support structure provided with at least one functional group as a security feature.
2. Use according to claim 1 , wherein the polyisocyano support structure is a
polyisocyanopeptide support structure.
3. Use according to claim 1 or 2, wherein the functional group has a sensory perceptible property and/or a physically detectable property.
4. Use according to claim 3, wherein the functional group is selected from the group comprising luminescent chromophores, compounds having (para)magnetic or
electromagnetic properties, compounds having an absorption spectrum in the UV range and/or the visible range and/or the IR range or near IR range, compounds showing electrical conductivity, biochemical compounds, compounds affording a liquid crystal behaviour to the security feature and combinations thereof.
5. Use according to claim 4, wherein the functional group is a luminescent
chromophore, which has luminescence characteristics through intramolecular interaction of the coupled groups, which characteristics differ from the luminescence characteristics of the same but non-coupled groups.
6. Use according to claim 5, wherein the emission spectra and/or the lifetime of the exited state of luminescence as a result of the intramolecular interactions between at least one type of functional groups differ from the emission spectra and/or the lifetime of the excited state of the monomeric units of the respective type of functional groups.
7. Use according to claim 4, wherin the functional group comprises at least two different kinds of luminescent chromophores, wherein the emission spectrum of one kind of luminescent chromophore overlaps with the excitation spectrum of the other kind of luminescent chromophore.
8. Use according to anyone of the preceding claims, wherein the polyisocyano support structure provided with at least one functional group shows circularly polarised
luminescence, in particular circularly polarised fluorescence.
9. Use according to anyone of the preceding claims, wherein a functional group emits in the visible region.
10. Use according to anyone of the preceding claims 1 -8, wherein a functional group 5 emits in the non-visible range.
1 1 . Use according to claim 4, wherein the support structure provided with functional groups shows electrical conductivity through the specific mutual orientation of the functional groups.
10
12. Use according to claim 4, wherein the biochemical compound is selected from the group of nucleic acid fragments, protein structures, peptides and nucleotides.
13. Use according to claim 4, wherein at least two different functional groups having 15 different electromagnetic properties are bonded to the support structure.
14. Use according to anyone of the preceding claims, wherein the security feature shows the behaviour of a liquid crystal.
20 15. Use according to claim 14, wherein the security feature shows a nematic behaviour.
16. Use according to claim 14, wherein the security feature show a cholesteric behaviour.
17. Use according to anyone of the preceding claims, wherein the support structure is 25 provided with an additional group for solubilising the security feature in an aqueous medium.
18. Use according to anyone of the preceding claims 1 -16, wherein the support structure is provided with an additional group for solubilising the security feature in an apolar medium.
30 19. Use according to anyone of the preceding claims, wherein the security feature is incorporated in an ink or pigment.
20. Use according to anyone of the preceding claims in articles selected from the group comprising security paper, value paper, security documents, identity documents, value
35 documents, vouchers, tickets, labels, prescription forms, certificates and packages.
21 . Article selected from the group comprising security paper, value paper, security documents, identity documents, value documents, vouchers, tickets, labels, prescription forms, certificates and packages, the article comprising at least one security feature comprising a polyisocyano support structure having at least one functional group, preferably
5 a polyisocyanopeptide structure.
22. Security feature comprising a polyisocyano support structure having at least one functional group, preferably a polyisocyanopeptide structure.
10 23. Security feature according to claim 22 showing circularly polarised luminescence, in particular circularly polarised fluorescence.
24. Method of authenticating articles provided with a security feature according to claim 21 , wherein a property dependent from the functional group and/or the polyisocyano support
15 structure is determined.
25. Method according to claim 24, wherein the chirality of a polyisocyanopeptide support structure provided with at least one functional group is determined.
20 26. Method according to claim 24 or 25 using polarised luminescence spectroscopy to detect circularly polarised luminescence, in particular circularly polarised fluorescence of the security feature.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP10807560A EP2516582A1 (en) | 2009-12-24 | 2010-12-23 | Security feature |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
NL2004018A NL2004018C2 (en) | 2009-12-24 | 2009-12-24 | SAFETY FEATURE. |
NL2004018 | 2009-12-24 |
Publications (1)
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WO2011078675A1 true WO2011078675A1 (en) | 2011-06-30 |
Family
ID=42537390
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/NL2010/050885 WO2011078675A1 (en) | 2009-12-24 | 2010-12-23 | Security feature |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2516582A1 (en) |
NL (1) | NL2004018C2 (en) |
WO (1) | WO2011078675A1 (en) |
Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001083237A1 (en) | 2000-05-03 | 2001-11-08 | Hologram Industries (S.A.) | Means for making a substrate secure |
WO2004108426A2 (en) | 2003-06-11 | 2004-12-16 | Bundesdruckerei Gmbh | Valuable document comprising a security element and method for producing said valuable document |
US20050042428A1 (en) * | 2003-08-22 | 2005-02-24 | Dean David M. | Methods for identity verification using transparent luminescent polymers |
US20050103424A1 (en) * | 2003-09-12 | 2005-05-19 | Nguyen My T. | Method for recording information in luminescent compositions and uses thereof in articles of manufacture |
US20060075249A1 (en) | 2004-10-04 | 2006-04-06 | Hayes Ralph E | Electromagnetic security device |
EP1646056A1 (en) | 2004-10-09 | 2006-04-12 | European Central Bank | Security document on which data can be stored and method and apparatus for reading data from and writing data on the security document |
EP1646057A2 (en) | 2004-10-09 | 2006-04-12 | European Central Bank | Security document and method for identification and/or authentication of a security document |
DE102005047609A1 (en) | 2005-10-05 | 2007-04-12 | Giesecke & Devrient Gmbh | Assurance of authenticity of value documents by means of feature substances |
US20070132984A1 (en) | 2005-12-13 | 2007-06-14 | Ncr Corporation | Secure tag |
EP1801759A1 (en) | 2005-12-21 | 2007-06-27 | Banque De France | Method of securing documents, associated authenticating method and apparatus |
US20070187630A1 (en) | 2006-02-16 | 2007-08-16 | Ncr Corporation | Secure tag coding |
EP1902855A2 (en) | 2004-02-26 | 2008-03-26 | De Nederlandsche Bank N.V. | Multicoloured foil |
DE102006047851A1 (en) | 2006-10-10 | 2008-04-17 | Giesecke & Devrient Gmbh | Authenticity feature in the form of luminescent substances |
DE102006047852A1 (en) | 2006-10-10 | 2008-04-17 | Giesecke & Devrient Gmbh | Authenticity feature in the form of a luminescent substance |
-
2009
- 2009-12-24 NL NL2004018A patent/NL2004018C2/en not_active IP Right Cessation
-
2010
- 2010-12-23 EP EP10807560A patent/EP2516582A1/en not_active Withdrawn
- 2010-12-23 WO PCT/NL2010/050885 patent/WO2011078675A1/en active Application Filing
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001083237A1 (en) | 2000-05-03 | 2001-11-08 | Hologram Industries (S.A.) | Means for making a substrate secure |
WO2004108426A2 (en) | 2003-06-11 | 2004-12-16 | Bundesdruckerei Gmbh | Valuable document comprising a security element and method for producing said valuable document |
US20050042428A1 (en) * | 2003-08-22 | 2005-02-24 | Dean David M. | Methods for identity verification using transparent luminescent polymers |
US20050103424A1 (en) * | 2003-09-12 | 2005-05-19 | Nguyen My T. | Method for recording information in luminescent compositions and uses thereof in articles of manufacture |
EP1902855A2 (en) | 2004-02-26 | 2008-03-26 | De Nederlandsche Bank N.V. | Multicoloured foil |
US20060075249A1 (en) | 2004-10-04 | 2006-04-06 | Hayes Ralph E | Electromagnetic security device |
EP1646057A2 (en) | 2004-10-09 | 2006-04-12 | European Central Bank | Security document and method for identification and/or authentication of a security document |
EP1646056A1 (en) | 2004-10-09 | 2006-04-12 | European Central Bank | Security document on which data can be stored and method and apparatus for reading data from and writing data on the security document |
DE102005047609A1 (en) | 2005-10-05 | 2007-04-12 | Giesecke & Devrient Gmbh | Assurance of authenticity of value documents by means of feature substances |
US20070132984A1 (en) | 2005-12-13 | 2007-06-14 | Ncr Corporation | Secure tag |
EP1801759A1 (en) | 2005-12-21 | 2007-06-27 | Banque De France | Method of securing documents, associated authenticating method and apparatus |
US20070187630A1 (en) | 2006-02-16 | 2007-08-16 | Ncr Corporation | Secure tag coding |
DE102006047851A1 (en) | 2006-10-10 | 2008-04-17 | Giesecke & Devrient Gmbh | Authenticity feature in the form of luminescent substances |
DE102006047852A1 (en) | 2006-10-10 | 2008-04-17 | Giesecke & Devrient Gmbh | Authenticity feature in the form of a luminescent substance |
Non-Patent Citations (15)
Title |
---|
ABDELKADER, M.; DRENTH, W.; MEIJER, E. W.: "Synthesis and characterization of a stable poly(iminomethylene) with pendant phenoxyl radicals", CHEM. MATER., vol. 3, no. 4, 1991, pages 598 - 602 |
CORNELISSEN, J. J. L. M.: "Hierarchical transfer of stereochemical information in synthetic macromolecules", PURE APPL. CHEM., vol. 74, no. 11, 2002, pages 2021 - 2030 |
CORNELISSEN, J. J. L. M.; GRASWINCKEL, W. S.; ADAMS, P. J. H. M.; NACHTEGAAL, G. H.; KENTGENS, A. P. M.; SOMMERDIJK, N. A. J. M.;: "Synthesis and characterization of polyisocyanides derived from alanine and glycine dipeptides", J. POLYM. SCI., PART A: POLYM. CHEM., vol. 39, no. 24, 2001, pages 4255 - 4264 |
CORNELISSEN, J.J.L.M.; DONNERS, J.J.J.M.; DE GELDER, R.; GRASWINCKEL, W.S.; METSELAAR, G.A.; ROWAN, A.E.; SOMMERDIJK , N.A.J.M.; N, SCIENCE, vol. 293, no. 5530, 2001, pages 676 - 680 |
HEATHER J KITTO ET AL: "Post-modification of helical dipeptido polyisocyanides using the 'click' reaction", JOURNAL OF MATERIALS CHEMISTRY,, vol. 18, no. 46, 1 January 2008 (2008-01-01), pages 5615 - 5624, XP009126768 * |
KITTO, H. J.; SCHWARTZ, E.; NIJEMEISLAND, M.; KOEPF, M.; CORNELISSEN, J.; ROWAN, A. E.; NOLTE, R. J. M.: "Post- modification of helical dipeptido polyisocyanides using the 'click'reaction", J. MATER. CHEM., vol. 18, no. 46, 2008, pages 5615 - 5624, XP009126768, DOI: doi:10.1039/b811002f |
METSELAAR, G. A.; WEZENBERG, S. J.; CORNELISSEN, J. J. L. M.; NOLTE, R. M.; ROWAN, A. E.: "Lyotropic liquid-crystalline behavior of polyisocyanodipeptides", J. POLYM. SCI., PART A: POLYM. CHEM., vol. 45, no. 6, 2007, pages 981 - 988 |
OTTEN, M. B. J.: "PhD thesis: Functionalized Polyisocyanides", RADBOUD UNIVERSITY |
POLYMERIZATION OF ISOCYANOPEPTIDES"VAN METSELAAR, 2006 |
ROSTOVTSEV, V. V; GREEN, L. G.; FOKIN, V. V.; SHARPLESS, K. B.: "A stepwise Huisgen cycloaddition process: Copper(I)-catalyzed regioselective "ligation" of azides and terminal alkynes", ANGEW. CHEM., INT. ED., vol. 41, no. 14, 2002, pages 2596 - 2599, XP002524189, DOI: doi:10.1002/1521-3773(20020715)41:14<2596::AID-ANIE2596>3.0.CO;2-4 |
SCHWARTZ, E.; KITTO, H. J.; DE GELDER, R.; NOLTE, R. J. M.; ROWAN, A. E.; CORNELISSEN, J. J. L. M.: "Synthesis, characterisation and chiroptical properties of 'click'able polyisocyanopeptides", J. MATER. CHEM., vol. 17, no. 19, 2007, pages 1876 - 1884 |
SCHWARTZ, E.; KOEPF, M.; KITTO, H. J.; ESPELT, M.; NEBOT-CARDA, V. J.; DE GELDER, R.; NOLTE, R. J. M.; CORNELISSEN, J. J. L. M.; R: "Water soluble azido polyisocyanopeptides as functional {3-sheet mimics", J. POLYM. SCI., PART A: POLYM. CHEM., vol. 47, 2009, pages 4150 - 4164 |
SCHWARTZ, E.; PALERMO, V.; FINLAYSON, C. E.; HUANG, Y.-S.; OTTEN, M. B. J.; LISCIO, A.; TRAPANI, S.; GONZAIEZ-VAIIS, I.; BROCORENS: "Helter Skelter-like' Perylene Polyisocyanopeptides", CHEM. EUR. J., vol. 15, 2009, pages 2536 - 2547 |
VLIETSTRA, E. J.; NOLTE, R. J. M.; ZWIKKER, J. W.; DRENTH, W.; MEIJER, E. W.: "Synthesis and magnetic properties of a rigid high- spin density polymer with piperidine-N-oxyl pending groups", MACROMOLECULES, vol. 23, no. 4, 1990, pages 946 - 948 |
WITTE, P. A. J.; CASTRICIANO, M.; CORNELISSEN, J. J. L. M.; SCOLARO, L. M.; NOLTE, R. J. M.; ROWAN, A. E.: "Helical polymer-anchored porphyrin nanorods", CHEM. EUR. J., vol. 9, no. 8, 2003, pages 1775 - 1781 |
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EP2516582A1 (en) | 2012-10-31 |
NL2004018C2 (en) | 2011-06-27 |
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