CN102205761A - Anti-counterfeit security file and detection method thereof - Google Patents
Anti-counterfeit security file and detection method thereof Download PDFInfo
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- CN102205761A CN102205761A CN2011100759899A CN201110075989A CN102205761A CN 102205761 A CN102205761 A CN 102205761A CN 2011100759899 A CN2011100759899 A CN 2011100759899A CN 201110075989 A CN201110075989 A CN 201110075989A CN 102205761 A CN102205761 A CN 102205761A
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Abstract
The invention discloses a security file with an optical response function, containing a combination anti-counterfeit material of one or more rare earth compounds. The security file can emit infrared light after being subjected to ultraviolet excitation. The invention also discloses a method for detecting whether an anti-counterfeit characteristic exists or not in the file. The anti-counterfeit security file provided by the invention has the advantages that the material with the anti-counterfeit characteristic is not easy to copy; a specific detection device is needed for detecting the anti-counterfeit characteristic; and the anti-counterfeit concealment is strong and the like.
Description
Technical field
The invention belongs to field of anti-counterfeit technology, relate in particular to the secure file that contains the optic response anti-fake material and the detection method of secure file authenticity.
Background technology
Optic response feature anti-fake material is the false proof composition of well-known banknote, marketable securities and the protection of other secure files.This feature anti-fake material can be imprinted on the secure file by printing ink, also can be placed in the secure file substrate or the form by pad pasting, safety line or label is attached on the secure file.
Under ultraviolet light or infrared ray excited condition, the optic response feature all has description at the anti-fake material of visible light in a large amount of patents, as: patent HU200302789A2 discloses a kind of anti-forgery ink, comprised two kinds of optic response feature anti-fake materials in the printing ink: a kind of is the material of ultraviolet excitation, VISIBLE LIGHT EMISSION, and another kind is a material infrared ray excited, VISIBLE LIGHT EMISSION.Patent CN101195757A has announced a kind of preparation method of red up-conversion phosphor.Patent CN101168667A has announced the preparation method of green emitting phosphor that the fluorescence detector of available 365 nm of a kind of while and 254 nm detects.Patent CN101168664A provides a kind of manufacture method of blue colour fluorescent powder.Patent CN1415694 has announced a kind of preparation method who mixes the red fluorescence powder of europium, and the excitation wavelength of this fluorescent material is 254nm.At the existing optic response feature anti-fake material that on secure file, uses in a large number, patent CN2726032Y also discloses a kind of portable double wave anti-counterfeiting detection device, shines according to two kinds of fluorescent tubes of 365nm and 253.7nm and contains different fluorescent materials and produce the different colours fluorescence and come the true and false of secure file is differentiated.Patent CN1397795 has announced a kind of detection method and device of infrared up-conversion material, can directly handle and detect the visible light that excites of a plurality of different-wavebands to infrared up-conversion material and coding etc. thereof in the secure file.
Above material can detect by general on the market anti-counterfeiting detection device or under excitation source irradiation, just can be used as judgement with people's eyes, has the advantages that anti-fake material is imitated easily, anti-counterfeiting characteristic detects easily and false proof disguise is not strong.
Summary of the invention
At the deficiency that prior art exists, the object of the present invention is to provide the secure file of optic response feature anti-fake material;
Two of another object of the present invention is to provide the detection method at this secure file.
The object of the invention is achieved through the following technical solutions:
A kind of secure file, be that optic response feature anti-fake material is added in the secure file, specifically make up by following any one or more than one mode and finish: (1) directly is added into the papery secure file that makes in the paper pulp with this optic response feature anti-fake material particle in paper-making process; (2) this optic response feature anti-fake material particle is mixed with corresponding plastic master batch, after the technology such as fusion, film forming, the plastic basis material file of making; (3) with this optic response feature anti-fake material particle with is connected accordingly the material mixing after, prepare printing ink, republish to the base material of papery or plastic base by printing ink and to make corresponding secure file, mode of printing can be existing known any printing or coating methods such as offset printing, carved gravure, protruding seal, serigraphy, ink-jet, gentle version.When (4) making the secure file base material, this optic response feature anti-fake material is added in the needed base material functional coat.
Described optic response feature anti-fake material is specially the combination of one or more rare earth compounds, and its optic response mainly is under ultraviolet excitation, the result of rare earth element ion or the transition between different energy levels of atom 4f layer electronics; Its excitation wavelength is at ultraviolet band, and emission wavelength is at infrared band, and preferred excitation wavelength is the medium wave ultraviolet band of 280-350nm, and emission wavelength is the near infrared band of 800-1200nm.Rare earth element in the rare earth compound is a kind of element among Er, Nd, Pr, Ho, Yb and the Tm or the combination of more than one elements.
Described rare earth compound is one or more the combination in rare earth organic complex or the rare earth inorganic compound.The part of rare earth organic complex is a beta-diketon, aromatic cycle compound, heterocyclic compound, the combination of one or more parts in neutral ligand or the macrocyclic ligand.Beta-diketon is that substituting group is straight chained alkyl, cycloalkyl and derivative thereof, aromatic alkyl and derivative thereof, fragrant heterocycle and derivative thereof etc.; Aromatic cycle compound is aromatic carboxylic acids, condensed-nuclei aromatics and derivative thereof; Heterocyclic compound is bipyridyl and derivative, Phen and derivative thereof, oxine and indoles and derivative thereof etc.; Neutral ligand is triphen phosphine oxide and derivative, dialkyl sulphoxide, pyridine nitric oxide and derivative thereof etc.; Macrocyclic ligand is big acyclic polyether, encircles many ketone, porphyrin and replacement porphyrin, phthalocyanine and substituted phthalocyanine, conjugated polyene compound, polyamide and replace polyamide and polyether-ketone etc. greatly.
Described rare earth inorganic compound is one or more combination of compounds in rare earth oxide, oxyhalide, oxysulfide, fluoride, aluminate, tungstates, phosphate, titanate, molybdate or the vanadate.
Described optic response feature anti-fake material is stimulated back stocks displacement greater than 500nm.The average grain diameter of optic response feature anti-fake material is less than 100 microns particle, preferably less than 30 microns particle, and the particle that best is less than 10 microns.
Among the present invention, detect the method for this secure file, can form by the following step:
A) launch the optical signalling that one or more specific wavelengths are arranged to the secure file that contains optic response feature anti-fake material, being preferably wave-length coverage is the medium ultraviolet light of 280-350nm;
B) detect the optical detector signal of launching, preferred wavelength range is the infrared light of 800-1200nm;
C), and calculate the result according to detected position and the strength difference of transmitting;
D) carry out whether having in the file judgement of described anti-fake material according to the calculated signals result.
The wider wave more than 2 can be accepted in the source of accepting of the optical detector signal that detection is launched from described secure file, between the preferred 800-1200nm.
Fig. 1 is that a typical case detects this secure file device, concrete grammar is: emission light 2 scioptics 3 that ultraviolet source 1 sends are concentrated, shine then on the pattern 6 that contains this optic response feature anti-fake material in the secure file 5, send characteristic optical signal 4, the characteristic optical signal, is responded to by induction installation 10 behind the conduction of optical fiber 8 and the filter plate 9 through slit 7, induced signal can be differentiated by output device 12 after oversampling circuit 11 is changed.
Optic response feature anti-fake material in the secure file of the present invention is to be made by one or more rare earth compounds, its excitation wavelength is at ultraviolet band, emission wavelength is at infrared band, advantage such as have that anti-fake material is not easy to copy, anti-counterfeiting characteristic needs the particular detection device to detect and false proof disguise is strong.
Description of drawings
Fig. 1 is for detecting the checkout gear structural representation of secure file of the present invention.
The number in the figure explanation
1-ultraviolet source 2-emission light 3-lens 4-characteristic optical signal
5-secure file 6-contains the pattern 7-slit of optic response feature anti-fake material
8-optical fiber 9-filter plate 10-induction installation 11-circuit 12-output device
The specific embodiment
Below by specific embodiment, further specify the present invention and how to realize.
The preparation of optic response feature anti-fake material
With ammonium vanadate 100 minutes, 4 parts of gadolinium oxides, 30 parts of yittrium oxide, after 6 parts of mixing of ytterbium oxide, through ball milling 1 hour, 700 degree high-temperature calcinations 2 hours, cooling discharging is after pulverize, and average grain diameter reaches 10 microns.The ultraviolet excitation of material rice in 325 can be launched the infrared light of 990nm.
The preparation of optic response feature anti-fake material
With 30 parts of yittrium oxide, after 6 parts of mixing of neodymia, through ball milling 1 hour, 1200 degree high-temperature calcinations 2 hours, cooling discharging is after pulverize, and average grain diameter reaches 10 microns.The ultraviolet excitation of material rice in 315 can be launched the infrared light of 1030nm.
Embodiment 3
The preparation of optic response feature anti-fake material
The KOH of 6mmol hexafluoroacetylacetone (H-HFA) and 6mmol is added in the mixed solution that the water of the ethanol that contains 50mL and 50mL makes, then in this mixed solution, add 0.5mmolErCl successively
36H
20,1.5mmolYbCl
36H
2O and 4mmol triphenylphosphine oxide (TPPO), and then with this mixed solution standing over night at room temperature, dry out solvent, washing, and crystallization finally obtains material Er in ethanolic solution
1/3Yb
2/3(HFA)
3(TPPO)
2, this material can send the infrared light of 1000nm behind the burst of ultraviolel of 335nm.
Embodiment 4
The preparation of optic response feature anti-fake material
With 3mmol2-acetyl group acenaphthenyl-4-Trifluoromethyl-1,3-diketone and 1mmol Phen are dissolved in absolute ethyl alcohol, stir down in wherein dripping 1mmolErCl
3, regulate pH value to 7.0～8.0 to wherein adding the NaOH aqueous solution then, mixture is warming up to 60 ℃ and stirred 2 hours, is chilled to room temperature, the sedimentation and filtration that obtains, successively with ethanol and distilled water washing, 105 ℃ of dry down products that get.This material can be launched the infrared light of 1200nm behind the ultraviolet excitation of 325nm.
Embodiment 5
The preparation of optic response feature anti-fake material
With 3mmol2-acetyl group acenaphthenyl-4-methyl isophthalic acid, 3-diketone and 1mmol Phen are dissolved in absolute ethyl alcohol, stir down in wherein dripping 1mmolNdCl
3, regulate pH value to 7.0～8.0 to wherein adding the NaOH aqueous solution then, mixture is warming up to 65 ℃ and stirred 3 hours, is chilled to room temperature, the sedimentation and filtration that obtains, successively with ethanol and distilled water washing, 110 ℃ of dry down products that get.This material can be launched the infrared light of 1064nm behind the ultraviolet excitation of 325nm.
Embodiment 6
The preparation of optic response feature anti-fake material
With 6mmol2-acetyl group acenaphthenyl-4-methyl isophthalic acid, 3-diketone and 2mmol Phen are dissolved in anhydrous normal butyl alcohol, to wherein slowly adding 2mmolHoCl
3, regulate pH value to 7.0～8.0 with the 5%NaOH aqueous solution, mixture is warming up to 65 ℃ and stirred 3 hours, is chilled to room temperature, the sedimentation and filtration that obtains, successively with ethanol and distilled water washing, 110 ℃ of dry down products that get.This material can be launched the infrared light of 2000nm behind the ultraviolet excitation of 325nm.
Embodiment 7
The preparation of optic response feature anti-fake material
With 3mmol2-acetyl group naphthyl-4-seven fluoropropyls-1,3-diketone and 2mmol triphen phosphine oxide are dissolved in anhydrous isopropyl alcohol, and stirring at room adds 1mmolDyCl in batches
3, regulate pH value to 7.0～8.0 with the 5%KOH aqueous solution, mixture is warming up to 65 ℃ and stirred 1.5 hours, is chilled to room temperature, the sedimentation and filtration that obtains, successively with ethanol and distilled water washing, 110 ℃ of dry down products that get.This material can be launched the infrared light of 1330nm behind the ultraviolet excitation of 335nm.
Embodiment 8
The preparation of optic response feature anti-fake material
Under the room temperature, add 3mmol2-acetyl group anthryl-4-Trifluoromethyl-1 in the absolute ethyl alcohol successively, 3-diketone and 2mmol methyl-sulfoxide are opened and are stirred, in wherein slowly adding 1mmolYbCl
3, regulate pH value to 7.0～8.0 with the NaOH aqueous solution, mixture is warming up to 70 ℃ and stirred 3 hours, is chilled to room temperature, the sedimentation and filtration that obtains, successively with absolute ethyl alcohol and distilled water washing, 105 ℃ of dry down products that get.This material can be launched the infrared light of 980nm behind the ultraviolet excitation of 335nm.
Embodiment 9
The preparation of optic response feature anti-fake material
Room temperature, with 10mmol2-acetyl thiophene base-4-Trifluoromethyl-1,3-diketone and 7mmol8-oxyquinoline are dissolved in anhydrous normal propyl alcohol under the nitrogen protection, stir down in wherein dripping 3mmolTmCl
3, regulate pH value to 7.0～8.0 to wherein adding the KOH aqueous solution then, mixture is warming up to 65 ℃ and stirred 2 hours, is chilled to room temperature, the sedimentation and filtration that obtains, successively with absolute ethyl alcohol and distilled water washing, 100～110 ℃ of dry down products that get.This material can be launched the infrared light of 1480nm behind the ultraviolet excitation of 325nm.
The preparation of optic response feature anti-fake material
With 3mmol2-acetyl group naphthyl-4-perfluor certain herbaceous plants with big flowers alkyl-1,3-diketone and 1mmol4,5-diaza fluorenes-9-ketone is dissolved in anhydrous tetrafluoro normal propyl alcohol, stirs down in wherein dripping 1mmolNdCl
3, regulate pH value to 7.0～8.0 to wherein adding the KOH aqueous solution then, mixture is warming up to 75 ℃ and stirred 2.5 hours, is chilled to room temperature, the sedimentation and filtration that obtains, washs with absolute ethyl alcohol and distilled water successively, dry under 100～120 ℃ product.This material can be launched the infrared light of 1064nm behind the ultraviolet excitation of 345nm.
The preparation method of papery optic response feature secure file
With embodiment 1 gained anti-fake material particle in paper-making process in being added into through the slurry after concentrating, account for paper pulp weight 3%.The papery secure file of the corresponding size that makes after passing through and copy paper, top sizing, press polish, cutting.
The preparation method of plastic base optic response feature secure file
In the plastics extrusion, embodiment 1 false proof particle is added in the plastic master batch with 3% the ratio of adding, through after fusion, the granulation again by being molded into corresponding plastic basis material, make the plastic safety file of corresponding size after cutting.
Embodiment 13
The engraving intaglio printing ink of optic response feature anti-fake material
Make the black engraving intaglio printing ink according to above-mentioned prescription with conventional printing ink manufacturing process.
Embodiment 14
The silk-screen ink of optic response feature anti-fake material
Make the pearly-lustre screen printing ink according to above-mentioned prescription with conventional printing ink manufacturing process.
Embodiment 15
The making of optic response feature secure file
The engraving intaglio printing ink of the embodiment 13 prepared a kind of optic response feature anti-fake materials mode with carved gravure is printed on the plain paper, obtains having the printing figure message of at least 10 micron thickness.The secure file that contains these picture and text is through ultraviolet excitation, and the infrared light of 1000nm can be launched in the picture and text position, and detected next by detector shown in Figure 1.
Embodiment 16
The detection method of optic response feature security document
Contain optic response feature anti-fake material pattern part in the optic response feature secure file that embodiment 15 is made and place under the checkout gear of Fig. 1, can determine the true and false of this secure file by the detection that its feature is transmitted.Ultraviolet source among Fig. 1 be emission wavelength at the LED of 325nm ultraviolet emission pipe, induction installation is infrared photodiode, specifically responding to wave-length coverage is 880-1050nm.
Claims (11)
1. secure file with optic response feature anti-fake material, it is characterized in that: optic response feature anti-fake material is added in the secure file, makes up by following any one or more than one mode and finish: (1) directly is added into the papery secure file that makes in the paper pulp with optic response feature anti-fake material particle in paper-making process; (2) with optic response feature anti-fake material particle and corresponding plastic master batch through mixing, after the fusion, film-forming process, making the plastic basis material secure file; (3) with this optic response feature anti-fake material particle with is connected accordingly the material mixing after, prepare printing ink, republish to the base material of papery or plastic base by printing ink and make corresponding secure file; When (4) making the secure file base material, this optic response feature anti-fake material is added in the needed base material functional coat; Described optic response feature anti-fake material be excitation wavelength at ultraviolet band, emission wavelength is at the rare earth compound of infrared band.
2. a kind of secure file with optic response feature anti-fake material according to claim 1 is characterized in that: the rare earth element in the described rare earth compound is a kind of element among Er, Nd, Pr, Ho, Yb and the Tm or the combination of more than one elements.
3. a kind of secure file with optic response feature anti-fake material according to claim 1 is characterized in that: described rare earth compound is one or more the combination in rare earth organic complex or the rare earth inorganic compound.
4. a kind of secure file according to claim 3 with optic response feature anti-fake material, it is characterized in that: the part of described rare earth organic complex is a beta-diketon, aromatic cycle compound, heterocyclic compound, the combination of one or more parts in neutral ligand or the macrocyclic ligand.
5. a kind of secure file with optic response feature anti-fake material according to claim 4 is characterized in that: described beta-diketon is that substituting group is a kind of in straight chained alkyl, cycloalkyl and derivative thereof, aromatic alkyl and derivative thereof or fragrant heterocycle and the derivative thereof; Described aromatic cycle compound is aromatic carboxylic acids or condensed-nuclei aromatics and derivative thereof; Described heterocyclic compound is a kind of in bipyridyl and derivative, Phen and derivative thereof, oxine or indoles and the derivative thereof; Described neutral ligand is a kind of in triphen phosphine oxide and derivative, dialkyl sulphoxide or pyridine nitric oxide and the derivative thereof; Described macrocyclic ligand is big acyclic polyether, encircles many ketone, porphyrin and replacement porphyrin, phthalocyanine and substituted phthalocyanine, conjugated polyene compound, polyamide and replace a kind of in polyamide or the polyether-ketone greatly.
6. a kind of secure file with optic response feature anti-fake material according to claim 3 is characterized in that: described rare earth inorganic compound is one or more combination of compounds in rare earth oxide, oxyhalide, oxysulfide, fluoride, aluminate, tungstates, phosphate, titanate, molybdate or the vanadate.
7. a kind of secure file with optic response feature anti-fake material according to claim 1 is characterized in that: described optic response feature anti-fake material is stimulated back stocks displacement greater than 500nm.
8. a kind of secure file according to claim 1 with optic response feature anti-fake material, it is characterized in that: the excitation wavelength of the anti-fake material of described optic response feature is the medium wave ultraviolet band of 280-350nm, and emission wavelength is the near infrared band of 800-1200nm.
9. a kind of secure file with optic response feature anti-fake material according to claim 1 is characterized in that: the mode of printing of printing ink is a kind of in offset printing, carved gravure, protruding seal, serigraphy, ink-jet, flexographic printing, rotogravure or the coating method.
10. test right requires among the 1-9 method of secure file arbitrarily, and it is as follows to detect step:
A) launch the optical signalling that one or more specific wavelengths are arranged to the secure file that contains optic response feature anti-fake material, preferred wavelength range is the medium ultraviolet light of 280-350nm;
B) detect the optical detector signal of launching from secure file, preferred wavelength range is the infrared light of 800-1200nm;
C), and calculate the result according to detected position and the strength difference of transmitting;
D) carry out whether having in the file judgement of described anti-fake material according to the calculated signals result.
11. method according to claim 10 is characterized in that: detection can be accepted two above wider wave from the source of accepting of the optical detector signal that described secure file is launched, between the preferred 800-1200nm.
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| CN2011100759899A CN102205761A (en) | 2011-03-28 | 2011-03-28 | Anti-counterfeit security file and detection method thereof |
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| CN2011100759899A CN102205761A (en) | 2011-03-28 | 2011-03-28 | Anti-counterfeit security file and detection method thereof |
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| CN2011100759899A Pending CN102205761A (en) | 2011-03-28 | 2011-03-28 | Anti-counterfeit security file and detection method thereof |
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| CN102909988A (en) * | 2012-10-31 | 2013-02-06 | 中国人民银行印制科学技术研究所 | Valuable document and identification method thereof |
| CN103882774A (en) * | 2014-04-09 | 2014-06-25 | 亚太森博（山东）浆纸有限公司 | Anti-counterfeit white cardboard |
| CN104914094A (en) * | 2010-02-04 | 2015-09-16 | 光谱***公司 | Gas activated changes to ligth absorption and emission characteristics for security articles |
| CN105355136A (en) * | 2015-09-06 | 2016-02-24 | 深圳市天兴诚科技有限公司 | Anti-counterfeiting method |
| CN105398253A (en) * | 2015-09-06 | 2016-03-16 | 深圳市天兴诚科技有限公司 | Anti-counterfeiting material and preparation method thereof |
| CN105469698A (en) * | 2015-12-05 | 2016-04-06 | 深圳市天兴诚科技有限公司 | Anti-counterfeiting method |
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| WO2021013448A1 (en) * | 2019-07-19 | 2021-01-28 | Bundesdruckerei Gmbh | Security feature for a security document or value document, comprising at least one luminescent substance that can be excited in the ultraviolet spectral range and emits in the infrared spectral range |
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| CN104914094A (en) * | 2010-02-04 | 2015-09-16 | 光谱***公司 | Gas activated changes to ligth absorption and emission characteristics for security articles |
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| CN105398253A (en) * | 2015-09-06 | 2016-03-16 | 深圳市天兴诚科技有限公司 | Anti-counterfeiting material and preparation method thereof |
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| CN106400596A (en) * | 2016-10-27 | 2017-02-15 | 西安西正印制有限公司 | Durable anti-fake rice paper and manufacturing technique thereof |
| CN106638149A (en) * | 2016-10-27 | 2017-05-10 | 西安西正印制有限公司 | Chinese art paper with anti-counterfeiting function and preparation process of Chinese art paper |
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Application publication date: 20111005 |