CN106142890B - Gas modulation lights Security element - Google Patents
Gas modulation lights Security element Download PDFInfo
- Publication number
- CN106142890B CN106142890B CN201610712780.1A CN201610712780A CN106142890B CN 106142890 B CN106142890 B CN 106142890B CN 201610712780 A CN201610712780 A CN 201610712780A CN 106142890 B CN106142890 B CN 106142890B
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- CN
- China
- Prior art keywords
- gas
- luminescent material
- security element
- luminescent
- false proof
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims description 9
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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
-
- 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
-
- 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
-
- 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
Landscapes
- Investigating Or Analysing Materials By The Use Of Chemical Reactions (AREA)
Abstract
The present invention relates to anti-counterfeit field, is related to a kind of luminous Security element of gas modulation.Specifically, the present invention relates to a kind of Security element, it includes false proof region, the first luminescent material and the second luminescent material are contained in the false proof region, and first luminescent material includes first gas modulation luminescent material, and second luminescent material includes the particle with stratum nucleare and gas-barrier layer, wherein, the stratum nucleare includes second gas modulation luminescent material, also, the stratum nucleare is coated by gas-barrier layer.The invention further relates to the method for making the Security element, include the anti-fake product of the Security element, the method for identifying the Security element or anti-fake product, ink comprising first luminescent material and/or the second luminescent material, and the purposes of first luminescent material and the second luminescent material in Security element is prepared.
Description
Technical field
The present invention relates to anti-counterfeit field, and in particular to a kind of Security element, the method for making the Security element, comprising
The anti-fake product of the Security element, the method for identifying the Security element or anti-fake product, comprising the first luminescent material and/
Or second luminescent material ink, and the purposes of the first luminescent material and the second luminescent material in Security element is prepared.
Background technology
For the purpose for preventing from palming off and forging, valuables are often matched somebody with somebody such as license, marketable securities and best brand of product
Security element is equipped with, to be tested to the authenticity of the valuables, while prevents unwarranted duplication.
Fluorescent material can be excited by the electromagnetic wave (such as ultraviolet light) of certain wavelength, so as to launch visible ray.Fluorescence
This feature of matter has been applied in Security element.Because the fluorescence detection device for being equipped with ultraviolet source is cheap, and
The method for detecting fluorescent characteristics is simple, quick and easy, is easy to be grasped and utilized by sales counter employee and ordinary populace, therefore,
Fluorescent characteristics is widely used as a kind of simple, reliable anti-counterfeiting characteristic in many national marketable securities.
But application of the fluorescent material on marketable securities alreadys exceed 50 years, moreover, common fluorescent class material exists
What in the market was easily commercially available, that give fraud molecule opportunity, and it can utilize the fluorescent material being conveniently easy to get to prepare
Into fluorescent ink, faked by the small mode of printing of offset printing or other costs.For current present situation, it is necessary to further
Existing Security element is improved, so that it is more difficult to replicate.
The luminescent spectrum and/or luminescent lifetime of gas modulation luminescent material can occur with the change of gaseous environment
Change, it is thus possible to be detected by instrument and/or visually observe the Security element comprising gas modulation luminescent material in difference
Luminosity (such as luminous intensity or glow color) in gaseous environment, to judge the true and false of Security element.
The content of the invention
In the present invention, unless otherwise stated, Science and Technology noun used herein has art technology
The implication that personnel are generally understood that.Also, involved laboratory operation step is to be widely used in corresponding field herein
Conventional steps.Meanwhile for a better understanding of the present invention, the definition and explanation of relational language is provided below.
As used in this article, term " luminescent material " refer to can by photon, charged particle, electric field or ionization spoke
That penetrates etc. is excited, and excitation energy is changed into the material of light radiation (such as fluorescence and/or phosphorescence).
As used in this article, term " gas modulation luminescent material " refers to that luminescent spectrum and/or luminescent lifetime can be with
The luminescent material the change of gaseous environment and changed.The change of the luminescent spectrum, including but not limited to feature peak intensity
Change (such as enhancing or decrease), change (such as red shift or blue shift), the change of characteristic peak number of characteristic peak wavelength of degree
The change (such as being changed into phosphorescence from fluorescence) of (such as increasing or decreasing) and characteristic peak species.In addition, some gas modulation hairs
The color of luminescent material can change with the change of gaseous environment.
The gas modulation luminescent material includes but is not limited to：The bipyridyl complex of ruthenium, the o-phenanthroline of ruthenium coordinate
Thing, the metalloporphyrin complex of palladium, the metalloporphyrin complex of platinum, the phthalocyanine complex of palladium, the phthalocyanine complex of platinum, the naphthalene phthalocyanine of palladium are matched somebody with somebody
Compound, the naphthalocyanine of platinum, decacyclene, fullerene, tetraiodofluorescein B, perylene, single ligand-complexes, the copper of copper
Multiple ligand complex, halo boron difluoride methylphenyl diketone class complex, the 9,10- diethyls optionally substituted by hexyl phenothiazine
Tetraphenyl ethylene, boron difluoride aminomethyl phenyl PLA, the iodo of methoxy substitution of alkenyl anthracene, propoxyl group or carbazyl substitution
Boron difluoride phenyl anthryl propanedione gathers newborn ester, rare earth metal complex, the intercalation of fluorescent whitening agent 357 or 85 and enters hydrotalcite
The fluorescent material and distyry-biphenyls material that interlayer is formed.
As used in this article, term " gaseous environment " includes but is not limited to vacuum, inert gas (such as helium or argon
Gas) atmosphere, steam atmosphere, oxygen atmosphere, nitrogen atmosphere, carbon dioxide atmosphere, organic solvent (such as ethyl acetate or four
Chlorination carbon) atmosphere, halogen atmosphere (such as iodine vapor), and the mixed-gas atmosphere being made up of multiple gases simple substance, for example, by
Mixed-gas atmosphere, air atmosphere or the characteristics of contaminated respiratory droplets gas atmosphere of oxygen and nitrogen composition.
, it is necessary to make Security element produce the specific change of luminosity with the change of gaseous environment in some occasions,
To produce more complicated antifalse effect.The present inventor is lighted gas modulation by in-depth study and performing creative labour
Material is coated, and is coordinated with uncoated gas modulation luminescent material, for manufacturing Security element, so that of the invention
Security element there is special antifalse effect, thus complete the present invention.
In one aspect, the invention provides a kind of Security element, it includes false proof region, and the false proof region is contained
First luminescent material and the second luminescent material, first luminescent material include first gas modulation luminescent material, described second
Luminescent material includes the particle with stratum nucleare and gas-barrier layer, wherein, the stratum nucleare includes the luminous material of second gas modulation
Material, also, the stratum nucleare is coated by gas-barrier layer.
In one embodiment of the invention, first luminescent material includes the luminous material of at least one gas modulation
Material.
In one embodiment of the invention, second luminescent material includes the luminous material of at least one gas modulation
Material.
In one embodiment of the invention, first luminescent material, first gas modulation luminescent material, second
Luminescent material and/or second gas modulation luminescent material have different luminescent spectrums in different gaseous environments.
In one embodiment of the invention, first luminescent material or first gas modulation luminescent material are the
There is the first luminescent spectrum in one gaseous environment, and there is the second luminescent spectrum in second gas environment, first hair
Light spectrum and the second luminescent spectrum are different, for example, the peak intensity that takes on a different character, characteristic peak wavelength, characteristic peak number and/or
Characteristic peak species.
In one embodiment of the invention, the of first luminescent material or first gas modulation luminescent material
One luminescent spectrum and the second luminescent spectrum have different number of characteristic peak.For example, first luminescent material is iodo difluoro
Change boron aminomethyl phenyl propanedione.Iodo boron difluoride aminomethyl phenyl propanedione is under ultraviolet excitation, aerial luminous light
Spectral curve and luminescent spectrum curve in nitrogen are respectively as shown Fig. 1 (1) and Fig. 1 (2).It can be seen that in sky
In gas, there is emission peak near 510nm in iodo boron difluoride aminomethyl phenyl propanedione, in nitrogen, near 510nm
Emission peak outside, there is another emission peak near 575nm in iodo boron difluoride aminomethyl phenyl propanedione.
In one embodiment of the invention, the of first luminescent material or first gas modulation luminescent material
One luminescent spectrum and the second luminescent spectrum have equal number of characteristic peak, also, the intensity at least one character pair peak is not
Together.For example, first luminescent material is three (2,2 '-bipyridyl) ruthenous chloride (II) (Ru (bpy)3C12)。Ru(bpy)3C12Under ultraviolet excitation, there is an emission peak respectively in air atmosphere and in nitrogen atmosphere, be respectively positioned on 605nm
Near.Ru(bpy)3C12Luminescent spectrum curve in air atmosphere and in nitrogen atmosphere is respectively such as the curve 1 and song in Fig. 2
Shown in line 2.It can be seen that Ru (bpy)3C12Intensity of the emission peak in nitrogen atmosphere it is substantially stronger than aerial
Spend stronger.
In one embodiment of the invention, first luminescent material or first gas modulation luminescent material are the
There is different luminescent lifetimes in one gaseous environment and second gas environment.
In one embodiment of the invention, first luminescent material or first gas modulation luminescent material are the
There is different luminescent spectrums and different luminescent lifetimes in one gaseous environment and second gas environment.For example, first hair
Luminescent material coordinates composition granule for a kind of multiple ligand of copper.The molecular formula of the multiple ligand complex of the copper is Cu (phen) (POP)
BF4(phen is o-phenanthroline, and POP is double (2- diphenylphosphinophenyls) ethers).The synthesis of the multiple ligand complex of the copper
See, for example, J.Am.Chem.Soc.2002,124,6.The multiple ligand complex of the copper can be launched under the exciting of ultraviolet light
Fluorescence.In oxygen atmosphere, fluorescent quenching can occur for the multiple ligand complex of the copper, cause luminous intensity and luminescent lifetime
Reduction.
In one embodiment of the invention, first luminescent material or first gas modulation luminescent material are the
There is different glow colors in one gaseous environment and second gas environment.For example, first luminescent material is iodo difluoro
Change boron aminomethyl phenyl propanedione particle.Iodo boron difluoride aminomethyl phenyl propanedione launches blue-green fluorescent in air atmosphere,
In nitrogen atmosphere in addition to launching blue-green fluorescent, while launch yellow phosphorescence so that the glow color of material is yellowish green
Color.
In one embodiment of the invention, the first gas modulation luminescent material is selected from transient metal complex
(such as the bipyridyl complex of ruthenium, the phenanthroline complexes of ruthenium, the metalloporphyrin complex of palladium, the metalloporphyrin complex of platinum, palladium
Phthalocyanine complex, the phthalocyanine complex of platinum, the naphthalocyanine of palladium, the naphthalocyanine of platinum, single part of copper coordinate
The multiple ligand complex of thing, copper), decacyclene, fullerene, tetraiodofluorescein B, perylene, halo boron difluoride phenylpropyl alcohol two
Ketone complex, the four benzene second optionally substituted by 9,10- divinyl anthracene that hexyl phenothiazine substitutes, propoxyl group or carbazyl
Alkene, the boron difluoride aminomethyl phenyl PLA of methoxy substitution, iodo boron difluoride phenyl anthryl propanedione gather newborn ester, rare earth
Metal complex, the intercalation of fluorescent whitening agent 357 or 85 enter fluorescent material, the distyry-biphenyls that hydrotalcite layers are formed
Material.
In one embodiment of the invention, the bipyridyl that the first gas modulation luminescent material is selected from ruthenium coordinates
Thing (such as three (2,2 '-bipyridyl) ruthenous chlorides (II)), the phenanthroline complexes of ruthenium, the metalloporphyrin complex of platinum, copper
Multiple ligand complex, halo boron difluoride methylphenyl diketone class complex (such as iodo boron difluoride aminomethyl phenyl propanedione).
In one embodiment of the invention, second luminescent material or second gas modulation luminescent material are the
There is the first luminescent spectrum in one gaseous environment, and there is the second luminescent spectrum in second gas environment, first hair
Light spectrum and the second luminescent spectrum are different, for example, the peak intensity that takes on a different character, characteristic peak wavelength, characteristic peak number and/or
Characteristic peak species.
In one embodiment of the invention, the of second luminescent material or second gas modulation luminescent material
One luminescent spectrum and the second luminescent spectrum have different number of characteristic peak.For example, the second gas modulation luminescent material bag
The aminomethyl phenyl propanedione of boron difluoride containing iodo.Iodo boron difluoride aminomethyl phenyl propanedione is under ultraviolet excitation, in air
In luminescent spectrum curve and luminescent spectrum curve in nitrogen respectively as shown Fig. 1 (1) and Fig. 1 (2).Can be with from figure
Find out, in atmosphere, there is emission peak near 510nm in iodo boron difluoride aminomethyl phenyl propanedione, in nitrogen, except
Outside emission peak near 510nm, there is another transmitting near 575nm in iodo boron difluoride aminomethyl phenyl propanedione
Peak.
In one embodiment of the invention, the of second luminescent material or second gas modulation luminescent material
One luminescent spectrum and the second luminescent spectrum have equal number of characteristic peak, also, the intensity at least one character pair peak is not
Together.For example, the second gas modulation luminescent material includes three (2,2 '-bipyridyl) ruthenous chloride (II) (Ru (bpy)3C12)。Ru(bpy)3C12Under ultraviolet excitation, there is an emission peak respectively in air atmosphere and in nitrogen atmosphere,
It is respectively positioned near 605nm.Ru(bpy)3C12Luminescent spectrum curve in air atmosphere and in nitrogen atmosphere is respectively as in Fig. 2
Curve 1 and curve 2 shown in.It can be seen that Ru (bpy)3C12Intensity of the emission peak in nitrogen atmosphere substantially compare
Aerial intensity is stronger.
In one embodiment of the invention, second luminescent material or second gas modulation luminescent material are the
There is different luminescent lifetimes in one gaseous environment and second gas environment.
In one embodiment of the invention, second luminescent material or second gas modulation luminescent material are the
There is different luminescent spectrums and different luminescent lifetimes in one gaseous environment and second gas environment.For example, second gas
Body modulation luminescent material includes a kind of multiple ligand complex of copper, and its molecular formula is Cu (phen) (POP) BF4(phen is adjacent luxuriant and rich with fragrance
Quinoline is coughed up, POP is double (2- diphenylphosphinophenyls) ethers).The synthesis of the multiple ligand complex of the copper see, for example,
J.Am.Chem.Soc.2002,124,6.The multiple ligand complex of the copper can launch fluorescence under the exciting of ultraviolet light.In oxygen
In gas atmosphere, fluorescent quenching can occur for the multiple ligand complex of the copper, cause the reduction of luminous intensity and luminescent lifetime.
In one embodiment of the invention, second luminescent material or second gas modulation luminescent material are the
There is different glow colors in one gaseous environment and second gas environment.For example, the second gas modulation luminescent material bag
The aminomethyl phenyl propanedione particle of boron difluoride containing iodo.Iodo boron difluoride aminomethyl phenyl propanedione is launched in air atmosphere
Blue-green fluorescent, in nitrogen atmosphere in addition to launching blue-green fluorescent, while launch yellow phosphorescence so that material lights
Color is yellow green.
In one embodiment of the invention, the second gas modulation luminescent material is selected from transient metal complex
(such as the bipyridyl complex of ruthenium, the phenanthroline complexes of ruthenium, the metalloporphyrin complex of palladium, the metalloporphyrin complex of platinum, palladium
Phthalocyanine complex, the phthalocyanine complex of platinum, the naphthalocyanine of palladium, the naphthalocyanine of platinum, single part of copper coordinate
The multiple ligand complex of thing, copper), decacyclene, fullerene, tetraiodofluorescein B, perylene, halo boron difluoride phenylpropyl alcohol two
Ketone complex, the four benzene second optionally substituted by 9,10- divinyl anthracene that hexyl phenothiazine substitutes, propoxyl group or carbazyl
Alkene, the boron difluoride aminomethyl phenyl PLA of methoxy substitution, iodo boron difluoride phenyl anthryl propanedione gather newborn ester, rare earth
Metal complex, the intercalation of fluorescent whitening agent 357 or 85 enter fluorescent material, the distyry-biphenyls that hydrotalcite layers are formed
Material.
In one embodiment of the invention, the bipyridyl that the second gas modulation luminescent material is selected from ruthenium coordinates
Thing (such as three (2,2 '-bipyridyl) ruthenous chlorides (II)), the phenanthroline complexes of ruthenium, the metalloporphyrin complex of platinum, copper
Multiple ligand complex, halo boron difluoride methylphenyl diketone class complex (such as iodo boron difluoride aminomethyl phenyl propanedione).
In certain embodiments of the invention, the first gas modulation luminescent material and second gas modulation are luminous
Material is different.In such embodiment, the first luminescent material and the second luminescent material contain different gas modulation hairs
Luminescent material.
In one embodiment of the invention, the of first luminescent material or first gas modulation luminescent material
One luminescent spectrum and the second luminescent spectrum have different number of characteristic peak；Second luminescent material or second gas modulation
The first luminescent spectrum and the second luminescent spectrum of luminescent material have equal number of characteristic peak, also, at least one corresponding special
The intensity for levying peak is different.For example, the first gas modulation luminescent material is iodo boron difluoride aminomethyl phenyl propanedione；Institute
It is Ru (bpy) to state second gas modulation luminescent material3C12。
In one embodiment of the invention, the of first luminescent material or first gas modulation luminescent material
One luminescent spectrum and the second luminescent spectrum have equal number of characteristic peak, also, the intensity at least one character pair peak is not
Together；Also, the first luminescent spectrum and the second luminescent spectrum of second luminescent material or second gas modulation luminescent material have
There is different number of characteristic peak.For example, the first gas modulation luminescent material is Ru (bpy)3C12；The second gas is adjusted
Luminescent material processed is iodo boron difluoride aminomethyl phenyl propanedione.
In certain embodiments of the invention, the first gas modulation luminescent material and second gas modulation are luminous
Material is identical.In such embodiment, the first luminescent material and the second luminescent material contain identical gas modulation hair
Luminescent material, wherein, the first luminescent material includes the uncoated gas modulation luminescent material, and the second luminescent material bag
Containing the gas modulation luminescent material coated by gas-barrier layer.By being coated to gas modulation luminescent material,
So that the sensitivity that the luminosity of the gas modulation luminescent material after cladding changes to gaseous environment reduces, and thus, cladding
Gas modulation afterwards is luminous to show the luminosity different from uncoated gas modulation luminescent material.That is, first
Although luminescent material and the second luminescent material include identical gas modulation luminescent material, there is different luminosities.
In certain embodiments, the gas modulation luminescent material is in second gas environment (such as air atmosphere or oxygen
Gas atmosphere) in luminous intensity be weaker than the luminous intensity in first gas environment (such as nitrogen atmosphere).Such gas modulation
Luminescent material with gas-barrier layer after being coated, its hair in second gas environment (such as air atmosphere or oxygen atmosphere)
Luminous intensity is also weaker than the luminous intensity in first gas environment (such as nitrogen atmosphere).However, due to gas-barrier layer
In the presence of the decrease amplitude of luminous intensity of the coated gas modulation luminescent material in second gas environment is less than without bag
The gas modulation luminescent material covered.
In one embodiment of the invention, it is (such as poly- to be selected from high-molecular compound for the material of the gas-barrier layer
Dimethyl siloxane, polyethylene, polypropylene, polyisoprene, polystyrene, makrolon, polyvinyl acetate, polyethylene
Alcohol, polyvinyl chloride, polyvinylidene chloride, polytetrafluoroethylene (PTFE), polyacrylonitrile, natural rubber, nylon-6, ethyl cellulose, poly- first
Base ethyl acrylate) and silica.
In one embodiment of the invention, the gas-barrier layer completely or partially blocking oxygen can ooze
Thoroughly.
In certain embodiments of the invention, gas barrier layer material to the barrier property of oxygen mainly by material pair
The infiltration coefficient P of oxygen is determined, also, infiltration coefficient P can be calculated by below equation：
P=S × D；
Wherein, S represents the solubility factor of oxygen in the material, and D represents the diffusion coefficient of oxygen in the material.
In one embodiment of the invention, the material of the gas-barrier layer has low oxygen permeability coefficient (example
Such as it is less than 1, less than 0.1 or less than 0.01).Such gas-barrier layer has high barrier property, such as polyethylene to oxygen
Alcohol barrier layer or polyacrylonitrile barrier layer.
In one embodiment of the invention, the material of the gas-barrier layer has high oxygen permeability coefficient (example
Such as it is higher than 1, higher than 10 or higher than 100).Such gas-barrier layer has low barrier property, such as silica to oxygen
Barrier layer or ethyl cellulose barrier layer.
In the present invention, it is that those skilled in the art are known with the method for gas-barrier layer cladding gas modulation luminescent material
's.For example, Anal.Chem.2001 can be used, the method described in 73,4988 prepares the gas through gas-barrier layer cladding and adjusted
Luminescent material processed.Or the particle of coated silica is prepared as seed according to the method in above-mentioned document, and it is laggard
One step absorption other materials (such as polyvinyl alcohol), obtains the second luminescent material.
In a preferred embodiment, by selecting the species of gas-barrier layer, the second luminescent material can be caused
Intensity ratio in two kinds of specific gaseous environments is a particular value.
For example, second luminescent material is three (2,2 '-bipyridyl) ruthenous chlorides (II) of polyvinyl alcohol cladding
Grain.Second luminescent material is a particular value in the intensity ratio of first gas environment and second gas environment.
For example, second luminescent material is three (2,2 '-bipyridyl) ruthenous chlorides (II) of coated with silica
Grain.Second luminescent material is a particular value in the intensity ratio of first gas environment and second gas environment.
In a preferred embodiment, the gas-barrier layer is more than 50% to the transmitance of electromagnetic wave, such as greatly
In 55%, more than 60%, more than 70%, more than 80% or more than 90%, preferably greater than 80%, more preferably greater than 90%.
In one embodiment of the invention, first luminescent material and the second luminescent material are positioned at described false proof
In the same false proof region of element.
In one embodiment of the invention, first luminescent material and the second luminescent material are positioned at described false proof
In the different false proof regions of element.
In a preferred embodiment, first luminescent material and the second luminescent material are respectively present in described
In the first false proof region and the second false proof region of Security element；Also, in the case where exciting light irradiation, the first false proof region is
Intensity ratio in one gaseous environment and second gas environment is the first particular value, and the second false proof region is in the first gas
Intensity ratio in body environment and second gas environment is the second particular value, wherein, the first particular value be different from (such as
Below or above) the second particular value.
In a preferred embodiment, first particular value is more than 1, and second particular value is less than 1.
In a preferred embodiment, first particular value is more than 1, and second particular value is equal to 1.
In a preferred embodiment, first particular value be more than 1, second particular value be more than 1 and
In the first particular value.
In a preferred embodiment, first particular value is equal to 1, and second particular value is more than 1.
In a preferred embodiment, first particular value is equal to 1, and second particular value is less than 1.
In a preferred embodiment, first particular value is less than 1, and second particular value is more than 1.
In a preferred embodiment, first particular value is less than 1, and second particular value is equal to 1.
In a preferred embodiment, first particular value be less than 1, second particular value be less than 1 and
In the first particular value.
In a preferred embodiment, first luminescent material and the second luminescent material are respectively present in described
In the first false proof region and the second false proof region of Security element；Also, in the case where exciting light irradiation, the first false proof region is
The ratio between luminescent lifetime in one gaseous environment and second gas environment is the first particular value, and the second false proof region is in the first gas
The ratio between luminescent lifetime in body environment and second gas environment is the second particular value, wherein, the first particular value be different from (such as
Below or above) the second particular value.
In a preferred embodiment, first particular value is more than 1, and second particular value is less than 1.
In a preferred embodiment, first particular value is more than 1, and second particular value is equal to 1.
In a preferred embodiment, first particular value be more than 1, second particular value be more than 1 and
In the first particular value.
In a preferred embodiment, first particular value is equal to 1, and second particular value is more than 1.
In a preferred embodiment, first particular value is equal to 1, and second particular value is less than 1.
In a preferred embodiment, first particular value is less than 1, and second particular value is more than 1.
In a preferred embodiment, first particular value is less than 1, and second particular value is equal to 1.
In a preferred embodiment, first particular value be less than 1, second particular value be less than 1 and
In the first particular value.
In a preferred embodiment, first luminescent material and the second luminescent material are respectively present in described
In the first false proof region and the second false proof region of Security element, also, in the case where exciting light irradiation, in first gas environment,
First false proof region and the second false proof region have identical luminous intensity, in second gas environment, the first false proof region and
Second false proof region has different luminous intensities.
For example, first luminescent material is the phenanthroline complexes of ruthenium, its molecular formula is Ru (phen)3Cl2(phen
For o-phenanthroline), it is present in the first false proof region of Security element；Second luminescent material is to have coated polypropylene
The phenanthroline complexes of the ruthenium of nitrile gas-barrier layer, it is present in the second false proof region of Security element.Exciting
Under light irradiation, in first gas environment, such as in nitrogen atmosphere, the first false proof region and the second false proof region have identical
Luminous intensity, in second gas environment, such as in air atmosphere, the luminous intensity in the first false proof region is weaker than the second false proof area
Domain.The Ru (phen)3Cl2Can be by commercially available.
In a preferred embodiment, first luminescent material and the second luminescent material are respectively present in described
In the first false proof region and the second false proof region of Security element, also, in the case where exciting light irradiation, in first gas environment,
First false proof region and the second false proof region have different luminous intensities, in second gas environment, the first false proof region and
Second false proof region has identical luminous intensity.
For example, first luminescent material is the metalloporphyrin complex of platinum, its molecular formula is PtOEP, (OEP is porphyrin), its
It is present in the first false proof region of Security element；Second luminescent material is to have coated ethyl cellulose gas-barrier layer
The platinum metalloporphyrin complex, it is present in the second false proof region of Security element.Under ultraviolet light, first
In gaseous environment, such as the nitrogen oxygen mixed gas containing 5% oxygen, the luminous intensity in the first false proof region is less than the second false proof area
Domain, in second gas environment, such as in oxygen atmosphere, the first false proof region and the second false proof region it is luminous complete by oxygen
Quenching, luminous intensity is zero.The metalloporphyrin complex of the platinum can be by commercially available.
In a preferred embodiment, first luminescent material and the second luminescent material are respectively present in described
In the first false proof region and the second false proof region of Security element, also, in the case where exciting light irradiation, in first gas environment,
First false proof region and the second false proof region have identical luminous intensity and identical luminescent lifetime, in second gas environment
In, the first false proof region and the second false proof region have different luminous intensities and different luminescent lifetimes.
For example, first luminescent material is a kind of multiple ligand complex of copper, its molecular formula is Cu (phen) (POP)
BF4(phen is o-phenanthroline, and POP is double (2- diphenylphosphinophenyls) ethers).The synthesis ginseng of the multiple ligand complex of the copper
See J.Am.Chem.Soc.2002,124,6).The multiple ligand complex of the copper can launch fluorescence under the exciting of ultraviolet light.
In oxygen atmosphere, fluorescent quenching can occur for the multiple ligand complex of the copper, cause luminous intensity to reduce.Second luminous material
Expect to coordinate composition granule to have coated the multiple ligand of the copper of the gas-barrier layer of high obstructing performance (such as polyvinyl alcohol).Institute
The first luminescent material is stated to be present in the first false proof region；Second luminescent material is present in the second false proof region.
First gas environment, such as in nitrogen atmosphere, excite under light irradiation, the first false proof region and the second false proof region have identical
Luminous intensity and identical luminescent lifetime；In second gas environment, such as in oxygen atmosphere, excite under light irradiation, first is anti-
The luminous intensity and luminescent lifetime in pseudo- region are less than the second false proof region.
In a preferred embodiment, first luminescent material and the second luminescent material are respectively present in described
In the first false proof region and the second false proof region of Security element, also, in the case where exciting light irradiation, in first gas environment,
First false proof region and the second false proof region have identical glow color, in second gas environment, the first false proof region and
Second false proof region has different glow colors.
For example, first luminescent material is iodo boron difluoride aminomethyl phenyl propanedione particle.Iodo boron difluoride first
Base phenylpropanedione particle launches blue-green fluorescent in air atmosphere, in nitrogen atmosphere in addition to launching blue-green fluorescent,
Launch yellow phosphorescence simultaneously.Second luminescent material is gas-barrier layer (such as the polyvinyl alcohol gas for having coated high obstructing performance
Barrier layer) iodo boron difluoride aminomethyl phenyl propanedione particle.First luminescent material is present in the first false proof region
In, second luminescent material is present in the second false proof region.In the case where exciting light irradiation, in first gas environment, such as nitrogen
In gas atmosphere, the first false proof region and the second false proof region have identical glow color, are all yellow green；In second gas
In environment, such as air atmosphere, the first false proof region and the second false proof region have different glow colors, the first false proof area
The glow color in domain is blue-green, and the glow color in the second false proof region is yellow green.
In a preferred embodiment, first luminescent material and the second luminescent material are respectively present in described
In the first false proof region and the second false proof region of Security element, also, in the case where exciting light irradiation, in first gas environment,
First false proof region and the second false proof region have different glow colors, in second gas environment, the first false proof region and
Second false proof region has identical glow color.
For example, first luminescent material is iodo boron difluoride aminomethyl phenyl propanedione particle, the second luminescent material is
The iodo boron difluoride aminomethyl phenyl of the gas-barrier layer (such as ethyl cellulose gas-barrier layer) of low barrier energy is coated
Propanedione particle.First luminescent material is present in the first false proof region, and it is anti-that second luminescent material is present in second
In pseudo- region.In the case where exciting light irradiation, in first gas environment, such as oxygen and nitrogen containing 10% (volume fraction) oxygen
Mixed-gas atmosphere in, the glow color in the first false proof region is blue-green, and the glow color in the second false proof region is green
Color.In second gas environment, such as in oxygen atmosphere, the glow color in the first false proof region and the second false proof region is all indigo plant
Green.
In one embodiment of the invention, gas modulation of the invention lights Security element including at least the first hair
Luminescent material, the second luminescent material and the 3rd luminescent material, wherein, it is luminous that first luminescent material includes first gas modulation
Material；Second luminescent material is the particle with stratum nucleare and gas-barrier layer 1, and the stratum nucleare includes the second luminescent material,
Also, the stratum nucleare is coated by gas-barrier layer 1；3rd luminescent material is with stratum nucleare and gas-barrier layer 2
Particle, the stratum nucleare includes the 3rd luminescent material, also, the stratum nucleare is coated by gas-barrier layer 2.
In certain embodiments of the invention, the first gas modulation luminescent material, the luminous material of second gas modulation
Two or three in material and third gas modulation luminescent material are identicals.
In certain embodiments of the invention, the first gas modulation luminescent material, the luminous material of second gas modulation
Material and third gas modulation luminescent material are identicals.
In a preferred embodiment, first luminescent material, the second luminescent material and the 3rd luminescent material point
It is not present in the first false proof region, the second false proof region and the 3rd false proof region of the Security element.Exciting light irradiation
Under, intensity ratio of the first false proof region in first gas environment and second gas environment is the first particular value, second
False proof region is the second particular value in the intensity ratio in first gas environment and second gas environment, and the 3rd is false proof
Intensity ratio of the region in first gas environment and second gas environment is the 3rd particular value.First particular value,
At least two in second particular value and the 3rd particular value differ.
In a preferred embodiment, first luminescent material, the second luminescent material and the 3rd luminescent material point
It is not present in the first false proof region, the second false proof region and the 3rd false proof region of the Security element.Exciting light irradiation
Under, the ratio between the luminescent lifetime of the first false proof region in first gas environment and second gas environment is the first particular value, second
False proof region is the second particular value in the ratio between luminescent lifetime in first gas environment and second gas environment, and the 3rd is false proof
The ratio between the luminescent lifetime of region in first gas environment and second gas environment is the 3rd particular value.First particular value,
At least two in second particular value and the 3rd particular value differ.
In the embodiment above, first particular value, the second particular value and the 3rd particular value form one group of coding.
When differentiating the true and false of the Security element, by judging whether the coding is identical with preset value, to judge the Security element
The true and false.
In a preferred embodiment, the gas-barrier layer 1 is less than gas-barrier layer to the barrier property of oxygen
2, for example, the gas-barrier layer 1 is silica barrier layer, the gas-barrier layer 2 is polyvinyl alcohol barrier layer.
In a preferred embodiment, in the case where exciting light irradiation, in first gas environment, such as in nitrogen atmosphere,
Three false proof regions have identical luminous intensity, in second gas environment, such as in oxygen atmosphere, the first false proof region tool
There is the luminous intensity lower than the second false proof region, the second light-emitting zone has the luminous intensity lower than the 3rd false proof region.
In the present invention, it is preferred to the false proof region is letter, numeral, word, bar code, Quick Response Code or pattern；
Or collectively constitute letter, numeral, word, bar by multiple false proof regions (such as the first false proof region and second false proof region)
Shape code, Quick Response Code or pattern.
In a preferred embodiment, in the case where exciting light irradiation, in first gas environment, it is observed that anti-
Occur letter, numeral, word, bar code, Quick Response Code and/or pattern on pseudo- element, and in second gas environment, Wu Faguan
Observe the letter, numeral, word, bar code, Quick Response Code and/or pattern.
In a preferred embodiment, in the case where exciting light irradiation, in first gas environment, go out on Security element
Existing letter, numeral, word, bar code, Quick Response Code and/or pattern, and the letter, numeral, word, bar code, Quick Response Code
And/or specific color is presented in pattern, and in second gas environment, the letter, numeral, word, bar code, Quick Response Code
And/or pattern shows different colors.
In embodiments of the invention, it is preferable that in the second gas environment residing for the Security element, oxygen
Content is higher than first gas environment.In a preferred embodiment, the first gas environment is not oxygenous gas
Environment.In a preferred embodiment, the second gas environment is air atmosphere or oxygen atmosphere.
In the present invention, it is preferred to the Security element be ink layer, it is safety line, pad pasting, labeling, joint strip, trade mark, anti-
Pseudo- fiber, label or packaging material.
On the other hand, present invention also offers the first luminescent material as defined above and the second luminescent material to prepare
Purposes in Security element.
In one embodiment of the invention, the Security element be ink layer, safety line, pad pasting, labeling, joint strip,
Trade mark, anti-false fiber, label or packaging material.
In one embodiment of the invention, first luminescent material and the second luminescent material are with the shape of composition
Formula is applied.
In one embodiment of the invention, first luminescent material and the second luminescent material are by separate administration.
On the other hand, present invention also offers a kind of method for making Security element, including the use of as defined above
One luminescent material and the second luminescent material.
In a preferred embodiment, first luminescent material and the second luminescent material are present in ink, and
Security element is formed by way of printing.Preferably, the ink is selected from offset ink, letterpress printing ink, base gravure ink, soft
Printing ink and silk-screen ink.
In one embodiment of the invention, first luminescent material and/or the second luminescent material are present in fiber
In, such as be present in the different zones of fiber, Security element is formed by way of spinning.
In one embodiment of the invention, first luminescent material and the second luminescent material are with the shape of composition
Formula is applied.
In one embodiment of the invention, first luminescent material and the second luminescent material are by separate administration.
On the other hand, the invention provides a kind of ink, it contains the first luminescent material as defined above and/or
Two luminescent materials.
In one embodiment of the invention, the ink is selected from offset ink, letterpress printing ink, base gravure ink, flexo
Ink and silk-screen ink.
In one embodiment of the invention, the ink be used to manufacture Security element.
On the other hand, the invention provides a kind of anti-fake product, comprising of the present invention anti-in the anti-fake product
Pseudo- element.
In a preferred embodiment, described Security element is with pad pasting, labeling, joint strip, label, trade mark, safety
The form of line or packaging material is arranged on the anti-fake product.
In a preferred embodiment, described anti-fake product be banknote, security (such as stock), bill (such as
Check, admission ticket or ticket), commodity sign, commodity packaging, documentary evidence (such as certificate, identity card or passport) or antifake certificate
Block (such as credit card or bank book).
Another further aspect, the invention provides a kind of method for differentiating Security element or anti-fake product as described above, it is wrapped
Include following steps：
Step 1：Exciting light is acted on into Security element, observes the color in false proof region in Security element, or detection is prevented
The luminescent spectrum and/or luminescent lifetime in false proof region in pseudo- element；
Step 2：Change the gaseous environment residing for Security element, above-mentioned exciting light is acted on into the Security element, observe
The color in the false proof region, or the luminescent spectrum and/or luminescent lifetime in the detection false proof region；
Step 3：Color, luminescent spectrum and/or the luminescent lifetime in the false proof region are before and after contrast gaseous environment changes
No generation is expected to be changed, to determine the true and false of Security element or anti-fake product.
The beneficial effect of invention
In the present invention, by the Surface coating gas-barrier layer of the gas modulation luminescent material in routine, cladding can be made
The sensitivity that material for gaseous environment afterwards changes reduces, also, by adjusting the species of gas-barrier layer, can be to bag
The change of luminosity of the material under gas with various environment after covering is regulated and controled, and then can be realized in specific gas
In environment, gas modulation luminescent material produces the different changes of luminosity.
In the present invention, the gas modulation luminescent material of routine and the gas modulation luminescent material after cladding are used cooperatively
In Security element so that the luminosity of Security element produces specific change with the change of gaseous environment, generates more
Add complicated and unique antifalse effect.
Embodiment of the present invention is described in detail below in conjunction with drawings and examples, still, art technology
Personnel will be understood that drawings below and embodiment are merely to illustrate the present invention, rather than the restriction to the scope of the present invention.According to
The following detailed description of accompanying drawing and preferred embodiment, various purposes of the invention and favourable aspect are for people in the art
It will be apparent for member.
Brief description of the drawings
Fig. 1 is under ultraviolet excitation, and luminescent spectrum of the iodo boron difluoride aminomethyl phenyl propanedione in air atmosphere is bent
Line (1), and the luminescent spectrum curve (2) in nitrogen atmosphere.It can be seen that in atmosphere, iodo boron difluoride first
There is emission peak near 510nm in base phenylpropanedione, in nitrogen, in addition to the emission peak near 510nm, and iodo difluoro
Change boron aminomethyl phenyl propanedione and occur another emission peak near 575nm.
Fig. 2 is the Ru (bpy) of uncoated gas-barrier layer under ultraviolet excitation3C12Particle is luminous in air atmosphere
The curve of spectrum (curve 1) and the luminescent spectrum curve (curve 2) in nitrogen atmosphere, it is Ru (bpy) at 605nm3C12Transmitting
Peak.It can be seen that in nitrogen atmosphere, the transmitting peak intensity at 605nm is substantially than aerial transmitting peak intensity
It is stronger.
Fig. 3 is the Ru (bpy) for having coated polyvinyl alcohol gas-barrier layer3C12Luminescent spectrum of the particle in air atmosphere
Curve (curve 1) and the luminescent spectrum curve (curve 2) in nitrogen atmosphere, it is Ru (bpy) at 605nm3C12Emission peak.
It can be seen that the Ru (bpy) of polyvinyl alcohol gas-barrier layer is coated3C12Particle is in nitrogen atmosphere and air gas
Luminescent spectrum curve in atmosphere is close, illustrates that gas-barrier layer can reduce Ru (bpy)3C12Luminosity to gaseous environment
The sensitiveness of change.
Fig. 4 is the printed patterns schematic diagram of Security element 1 in embodiment 3 and 4, and a regions is utilize ink A printings in figure
Obtained pattern, b regions are to print obtained pattern using ink B.Excited using the ultraviolet light of 365nm wavelength, in sky
In gas, red fluorescence is launched in two regions (as shown in figure (1))；In nitrogen, the luminous intensity in a regions substantially increases, b
Region luminous intensity not change (as figure (2) shown in).
Fig. 5 is the printed patterns schematic diagram of Security element 2 in embodiment 6 and 7, and a regions is utilize ink A printings in figure
Obtained pattern, b regions are to print obtained pattern using ink B.Excited using the ultraviolet light of 365nm wavelength, in sky
In gas, blue-green fluorescent is launched in two regions (as shown in figure (1))；In nitrogen, a regions send yellow-green fluorescence, b areas
Still launch blue-green fluorescent in domain (as shown in figure (2)).
Embodiment
It is illustrative to embodiment of the present invention below in conjunction with embodiment, but those skilled in the art
It will be understood that the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Do not noted in embodiment
Bright actual conditions person, the condition suggested according to normal condition or manufacturer are carried out.Material therefor or the unreceipted production firm of equipment
Person, being can be by the conventional products of acquisition purchased in market.
The Ru (bpy) of the coating polyvinyl alcohol gas-barrier layer of embodiment 13C12Particle preparation
Reagent：Ru(bpy)3C12To be commercially available；The Ru (bpy) of coated silica gas-barrier layer3C12Particle is joined
It is prepared by the method for examining document Anal.Chem.2001,73,4988；Other reagents are commercially available conventional products.
Preparation process：Polyvinyl alcohol is dissolved in the water first and is prepared into the aqueous solution, then by the Ru of coated silica
(bpy)3C12Particle is scattered in polyvinyl alcohol water solution, polyvinyl alcohol is fully adsorbed in particle surface, and finally centrifugation is dry
It is dry.
The Ru (bpy) of the coating polyvinyl alcohol gas-barrier layer of embodiment 23C12Particle detection
Use fiber spectrometer detection Ru (bpy)3C12And the Ru (bpy) of polyvinyl alcohol gas-barrier layer is coated3C12The luminescent spectrum curve of particle.
Fig. 2 is the Ru (bpy) of uncoated gas-barrier layer3C12Luminescent spectrum curve (curve 1) in air atmosphere and
Luminescent spectrum curve (curve 2) in nitrogen atmosphere.It is Ru (bpy) at 605nm3C12Emission peak, it is in nitrogen atmosphere
Intensity be 1.95 times of the intensity in air atmosphere.
Fig. 3 is the Ru (bpy) for having coated polyvinyl alcohol gas-barrier layer3C12Luminescent spectrum of the particle in air atmosphere
Curve (curve 1) and the luminescent spectrum curve (curve 2) in nitrogen atmosphere.It can be seen that polyvinyl alcohol is coated
The Ru (bpy) of gas-barrier layer3C12Particle is close with the luminescent spectrum curve in air atmosphere in nitrogen atmosphere, illustrates gas
Body barrier layer can reduce Ru (bpy)3C12The sensitiveness that changes to gaseous environment of luminosity.
The preparation of the Security element 1 of embodiment 3
Take 10mg Ru (bpy)3C12As the first luminescent material, it is dissolved in 30mL chloroforms, is prepared into solution.Take
Silicone oil 10g, is added in solution, stirring, makes it be completely dissolved to form solution A.Solution A is evenly laid out in clean quartz
Glass surface, solvent chloroform is volatilized completely, form sticky grease.2g silicon dioxide powders are taken, are mixed with grease
Close, make silica dispersed in grease, form sticky ink A.
Take the Ru (bpy) of 10mg coating polyvinyl alcohol gas-barrier layers3C12Particle is scattered in as the second luminescent material
Solution is prepared into 30mL chloroforms.Silicone oil 10g is taken, is added in solution, stirs, makes it be completely dissolved to form solution B.
Solution B is evenly laid out in clean Quartz glass surfaces, solvent chloroform is volatilized completely, form sticky grease.
2g silicon dioxide powders are taken, are mixed with grease, make silica dispersed in grease, form sticky ink B.
Ink A and ink B are respectively printed at paper surface, obtain Security element 1, it has as shown in Figure 4 false proof
Region.In figure, a regions are to print obtained pattern using ink A, and b regions are to print obtained pattern using ink B.Will print
The false proof region made is fully dried, and detects its luminescent properties.
The detection of the Security element 1 of embodiment 4
With the false proof region of 365nm ultraviolet lights, transmitting light is collected by portable fiber-optic spectrometer, launches the number of light
Handled according to the analysis software (Spectra Suite) carried by spectrometer.As shown in figure 4, in atmosphere, a regions and
B launches red fluorescence in region.Pattern is positioned in quartz glass seals box, is passed through high pure nitrogen, is swashed with same light source
Hair, by portable fiber-optic spectrometer launch the collection and data processing of light.As a result show, compared with atmosphere, a
Luminous intensity of the region in nitrogen substantially increases, and luminous intensity of the b regions in nitrogen does not change.By than less
With the luminous intensity in each region in gaseous environment, the true and false of Security element can be effectively identified.
The preparation of the iodo boron difluoride aminomethyl phenyl propanedione particle of the coating polyvinyl alcohol gas-barrier layer of embodiment 5
Reagent：Iodo boron difluoride aminomethyl phenyl propanedione particle bibliography ACSNANO, 2010,4,4989 method
Prepare；The iodo boron difluoride aminomethyl phenyl propanedione particle bibliography Langmuir of coated silica, 2003,19,
It is prepared by 6693 method；Other reagents are conventional products purchased in market.
Preparation process：Polyvinyl alcohol is dissolved in the water first and is prepared into the aqueous solution, then by the iodine of coated silica
It is scattered in for boron difluoride aminomethyl phenyl propanedione particle in polyvinyl alcohol water solution, polyvinyl alcohol is fully adsorbed in particle
Surface, last centrifugal drying.
The preparation of the Security element 2 of embodiment 6
10mg iodo boron difluoride aminomethyl phenyl propanedione particles are taken to be dissolved in 30mL trichlorines as the first luminescent material
In methane, solution is prepared into.Silicone oil 10g is taken, is added in solution, stirs, makes it be completely dissolved to form solution A.Solution is equal
It is even to be laid in clean Quartz glass surfaces, solvent chloroform is volatilized completely, form sticky grease.Take 2g dioxies
SiClx powder, is mixed with grease, makes silica dispersed in grease, forms sticky ink A.
The iodo boron difluoride aminomethyl phenyl propanedione particle of 10mg coating polyvinyl alcohol gas-barrier layers is taken as second
Luminescent material, it is scattered in 30mL chloroforms and is prepared into solution.Silicone oil 10g is taken, is added in solution, stirs, makes its complete
Dissolving forms solution B.Solution B is evenly laid out in clean Quartz glass surfaces, solvent chloroform is volatilized completely, shape
Into sticky grease.2g silicon dioxide powders are taken, are mixed with grease, make silica dispersed in grease, shape
Into sticky ink B.
Ink A and ink B are respectively printed at paper surface, obtain Security element 2, it has as shown in Figure 5 false proof
Region.In figure, a regions are to print obtained pattern using ink A, and b regions are to print obtained pattern using ink B.Will print
The false proof region made is fully dried, and detects its luminescent properties.
The detection of the Security element 2 of embodiment 7
With the false proof region of 365nm ultraviolet lights, transmitting light is collected by portable fiber-optic spectrometer, launches the number of light
Handled according to the analysis software (Spectra Suite) carried by spectrometer.As shown in figure 5, in atmosphere, a regions and
B launches blue-green fluorescent in region.Pattern is positioned in quartz glass seals box, is passed through high pure nitrogen, with same light source
Excite, by portable fiber-optic spectrometer launch the collection and data processing of light.As a result show, a regions are in nitrogen
Launch yellow-green fluorescence, and blue-green fluorescent is still launched in b regions in nitrogen.By comparing gas with various environment Zhong Ge areas
The glow color in domain, it can effectively identify the true and false of Security element.
Although the embodiment of the present invention has obtained detailed description, it will be appreciated by those skilled in the art that：Root
According to disclosed all teachings, various modifications and changes can be carried out to details, and these change in the guarantor of the present invention
Within the scope of shield.The four corner of the present invention is provided by appended claims and its any equivalent.
Claims (95)
1. a kind of Security element, it includes false proof region, and the first luminescent material and the second luminescent material are contained in the false proof region,
First luminescent material includes first gas modulation luminescent material, and second luminescent material includes to be hindered with stratum nucleare and gas
The particle of interlayer, wherein, the stratum nucleare includes second gas modulation luminescent material, also, the stratum nucleare is by gas-barrier layer institute
Cladding.
2. Security element according to claim 1, wherein, first luminescent material is sent out comprising at least one gas modulation
Luminescent material.
3. Security element according to claim 1, wherein, second luminescent material is sent out comprising at least one gas modulation
Luminescent material.
4. Security element according to claim 1, wherein, first luminescent material, first gas modulation luminescent material,
Second luminescent material and/or second gas modulation luminescent material have different luminescent spectrums in different gaseous environments.
5. Security element according to claim 1, wherein, first luminescent material or first gas modulation luminescent material
There is the first luminescent spectrum in first gas environment, and there is the second luminescent spectrum in second gas environment, described
First luminescent spectrum of one luminescent material or first gas modulation luminescent material is different from the second luminescent spectrum.
6. Security element according to claim 5, wherein, first luminescent material or first gas modulation luminescent material
The first luminescent spectrum and the second luminescent spectrum take on a different character peak intensity, characteristic peak wavelength, characteristic peak number and/or spy
Levy peak species.
7. Security element according to claim 5, wherein, first luminescent material or first gas modulation luminescent material
The first luminescent spectrum and the second luminescent spectrum there is different number of characteristic peak.
8. Security element according to claim 5, wherein, first luminescent material or first gas modulation luminescent material
The first luminescent spectrum and the second luminescent spectrum there is equal number of characteristic peak, also, at least one character pair peak is strong
Degree is different.
9. Security element according to claim 5, wherein, first luminescent material or first gas modulation luminescent material
There is different luminescent lifetimes in first gas environment and second gas environment.
10. Security element according to claim 5, wherein, first luminescent material or the luminous material of first gas modulation
Material has different luminescent spectrums and different luminescent lifetimes in first gas environment and second gas environment.
11. Security element according to claim 5, wherein, first luminescent material or the luminous material of first gas modulation
Material has different glow colors in first gas environment and second gas environment.
12. Security element according to claim 1, the first gas modulation luminescent material is selected from Transition metal complexes
Thing, decacyclene, fullerene, tetraiodofluorescein B, perylene, halo boron difluoride methylphenyl diketone class complex, optionally by hexyl
Tetraphenyl ethylene, the boron difluoride of methoxy substitution that 9,10- divinyl anthracene, propoxyl group or the carbazyl of phenthazine substitution substitute
Aminomethyl phenyl PLA, iodo boron difluoride phenyl anthryl propanedione gather newborn ester, rare earth metal complex, fluorescent whitening agent 357
Or 85 intercalation enter hydrotalcite layers formed fluorescent material, distyry-biphenyls material.
13. Security element according to claim 12, wherein, the bipyridyl that the transient metal complex is selected from ruthenium coordinates
Thing, the phenanthroline complexes of ruthenium, the metalloporphyrin complex of palladium, the metalloporphyrin complex of platinum, the phthalocyanine complex of palladium, the phthalocyanine of platinum are matched somebody with somebody
Compound, the naphthalocyanine of palladium, the naphthalocyanine of platinum, copper single ligand-complexes and copper multiple ligand complex.
14. Security element according to claim 12, wherein, the first gas modulation luminescent material is selected from the connection pyrrole of ruthenium
Pyridine complex, the phenanthroline complexes of ruthenium, the metalloporphyrin complex of platinum, the multiple ligand complex of copper, halo boron difluoride phenylpropyl alcohol
Diones complex.
15. Security element according to claim 14, wherein, the bipyridyl complex of the ruthenium for three (2,2 '-bipyridyl
Base) ruthenous chloride (II).
16. Security element according to claim 14, wherein, the halo boron difluoride methylphenyl diketone class complex is iodine
For boron difluoride aminomethyl phenyl propanedione.
17. Security element according to claim 1, second luminescent material or second gas modulation luminescent material are the
There is the first luminescent spectrum in one gaseous environment, and there is the second luminescent spectrum in second gas environment, second hair
First luminescent spectrum of luminescent material or second gas modulation luminescent material is different from the second luminescent spectrum.
18. Security element according to claim 17, wherein, second luminescent material or the luminous material of second gas modulation
Material the first luminescent spectrum and the second luminescent spectrum take on a different character peak intensity, characteristic peak wavelength, characteristic peak number and/or
Characteristic peak species.
19. Security element according to claim 17, wherein, second luminescent material or the luminous material of second gas modulation
The first luminescent spectrum and the second luminescent spectrum of material have different number of characteristic peak.
20. Security element according to claim 17, wherein, second luminescent material or the luminous material of second gas modulation
The first luminescent spectrum and the second luminescent spectrum of material have an equal number of characteristic peak, also, at least one character pair peak
Intensity is different.
21. Security element according to claim 17, wherein, second luminescent material or the luminous material of second gas modulation
Material has different luminescent lifetimes in first gas environment and second gas environment.
22. Security element according to claim 17, wherein, second luminescent material or the luminous material of second gas modulation
Material has different luminescent spectrums and different luminescent lifetimes in first gas environment and second gas environment.
23. Security element according to claim 17, wherein, second luminescent material or the luminous material of second gas modulation
Material has different glow colors in first gas environment and second gas environment.
24. Security element according to claim 1, the second gas modulation luminescent material is selected from Transition metal complexes
Thing, decacyclene, fullerene, tetraiodofluorescein B, perylene, halo boron difluoride methylphenyl diketone class complex, optionally by hexyl
Tetraphenyl ethylene, the boron difluoride of methoxy substitution that 9,10- divinyl anthracene, propoxyl group or the carbazyl of phenthazine substitution substitute
Aminomethyl phenyl PLA, iodo boron difluoride phenyl anthryl propanedione gather newborn ester, rare earth metal complex, fluorescent whitening agent 357
Or 85 intercalation enter hydrotalcite layers formed fluorescent material, distyry-biphenyls material.
25. Security element according to claim 24, wherein, the bipyridyl cooperation crossed metal complex and be selected from ruthenium
Thing, the phenanthroline complexes of ruthenium, the metalloporphyrin complex of palladium, the metalloporphyrin complex of platinum, the phthalocyanine complex of palladium, the phthalocyanine of platinum are matched somebody with somebody
Compound, the naphthalocyanine of palladium, the naphthalocyanine of platinum, copper single ligand-complexes and copper multiple ligand complex.
26. Security element according to claim 24, wherein, the second gas modulation luminescent material is selected from the connection pyrrole of ruthenium
Pyridine complex, the phenanthroline complexes of ruthenium, the metalloporphyrin complex of platinum, the multiple ligand complex of copper, halo boron difluoride phenylpropyl alcohol
Diones complex.
27. Security element according to claim 26, wherein, the bipyridyl complex of the ruthenium for three (2,2 '-bipyridyl
Base) ruthenous chloride (II).
28. Security element according to claim 26, wherein, the halo boron difluoride methylphenyl diketone class complex is iodine
For boron difluoride aminomethyl phenyl propanedione.
29. Security element according to claim 1, the first gas modulation luminescent material and second gas modulation are luminous
Material is different.
30. Security element according to claim 29, wherein, first luminescent material or the luminous material of first gas modulation
The first luminescent spectrum and the second luminescent spectrum of material have different number of characteristic peak；Second luminescent material or second gas
The first luminescent spectrum and the second luminescent spectrum for modulating luminescent material have equal number of characteristic peak, also, at least one right
Answer the intensity of characteristic peak different.
31. Security element according to claim 29, wherein, first luminescent material or the luminous material of first gas modulation
The first luminescent spectrum and the second luminescent spectrum of material have an equal number of characteristic peak, also, at least one character pair peak
Intensity is different；Also, the first luminescent spectrum and second of second luminescent material or second gas modulation luminescent material lights
Spectrum has different number of characteristic peak.
32. Security element according to claim 1, the first gas modulation luminescent material and second gas modulation are luminous
Material is identical gas modulation luminescent material.
33. Security element according to claim 32, wherein, the gas modulation luminescent material is in second gas environment
Luminous intensity be weaker than the luminous intensity in first gas environment.
34. Security element according to claim 33, wherein, the second gas environment is air atmosphere or oxygen gas
Atmosphere.
35. Security element according to claim 33, wherein, the first gas environment is nitrogen atmosphere.
36. Security element according to claim 1, the material of the gas-barrier layer is selected from high-molecular compound and dioxy
SiClx.
37. Security element according to claim 36, wherein, the high-molecular compound be selected from dimethyl silicone polymer,
It is polyethylene, polypropylene, polyisoprene, polystyrene, makrolon, polyvinyl acetate, polyvinyl alcohol, polyvinyl chloride, poly-
Vinylidene chloride, polytetrafluoroethylene (PTFE), polyacrylonitrile, natural rubber, nylon-6, ethyl cellulose and polyethyl methacrylate.
38. Security element according to claim 36, wherein, the gas-barrier layer can completely or partially obstruct oxygen
The infiltration of gas.
39. Security element according to claim 36, wherein, the gas-barrier layer is more than to the transmitance of electromagnetic wave
50%.
40. the Security element according to claim 39, wherein, the gas-barrier layer is more than to the transmitance of electromagnetic wave
55%.
41. the Security element according to claim 39, wherein, the gas-barrier layer is more than to the transmitance of electromagnetic wave
60%.
42. the Security element according to claim 39, wherein, the gas-barrier layer is more than to the transmitance of electromagnetic wave
70%.
43. the Security element according to claim 39, wherein, the gas-barrier layer is more than to the transmitance of electromagnetic wave
80%.
44. the Security element according to claim 39, wherein, the gas-barrier layer is more than to the transmitance of electromagnetic wave
90%.
45. Security element according to claim 1, first luminescent material and the second luminescent material are positioned at described false proof
In the same false proof region of element.
46. Security element according to claim 1, first luminescent material and the second luminescent material are positioned at described false proof
In the different false proof regions of element.
47. Security element according to claim 46, wherein, first luminescent material and the second luminescent material are deposited respectively
In the first false proof region and the second false proof region in the Security element；Also, in the case where exciting light irradiation, the first false proof area
Intensity ratio of the domain in first gas environment and second gas environment is the first particular value, and the second false proof region is
Intensity ratio in one gaseous environment and second gas environment is the second particular value, wherein, the first particular value is different from the
Two particular values.
48. Security element according to claim 46, wherein, first luminescent material and the second luminescent material are deposited respectively
In the first false proof region and the second false proof region in the Security element；Also, in the case where exciting light irradiation, the first false proof area
The ratio between the luminescent lifetime of domain in first gas environment and second gas environment is the first particular value, and the second false proof region is
The ratio between luminescent lifetime in one gaseous environment and second gas environment is the second particular value, wherein, the first particular value is different from the
Two particular values.
49. the Security element according to claim 47 or 48, wherein, it is described to be different from referring to be below or above.
50. Security element according to claim 46, wherein, first luminescent material and the second luminescent material are deposited respectively
In the first false proof region and the second false proof region in the Security element, also, in the case where exciting light irradiation, in first gas
In environment, the first false proof region and the second false proof region have identical luminous intensity, and in second gas environment, first is false proof
Region and the second false proof region have different luminous intensities.
51. Security element according to claim 46, wherein, first luminescent material and the second luminescent material are deposited respectively
In the first false proof region and the second false proof region in the Security element, also, in the case where exciting light irradiation, in first gas
In environment, the first false proof region and the second false proof region have different luminous intensities, and in second gas environment, first is false proof
Region and the second false proof region have identical luminous intensity.
52. Security element according to claim 46, wherein, first luminescent material and the second luminescent material are deposited respectively
In the first false proof region and the second false proof region in the Security element, also, in the case where exciting light irradiation, in first gas
In environment, the first false proof region and the second false proof region have identical luminous intensity and identical luminescent lifetime, in the second gas
In body environment, the first false proof region and the second false proof region have different luminous intensities and different luminescent lifetimes.
53. Security element according to claim 46, wherein, first luminescent material and the second luminescent material are deposited respectively
In the first false proof region and the second false proof region in the Security element, also, in the case where exciting light irradiation, in first gas
In environment, the first false proof region and the second false proof region have identical glow color, and in second gas environment, first is false proof
Region and the second false proof region have different glow colors.
54. Security element according to claim 46, wherein, first luminescent material and the second luminescent material are deposited respectively
In the first false proof region and the second false proof region in the Security element, also, in the case where exciting light irradiation, in first gas
In environment, the first false proof region and the second false proof region have different glow colors, and in second gas environment, first is false proof
Region and the second false proof region have identical glow color.
55. Security element according to claim 1, it comprises at least the first luminescent material, the second luminescent material and the 3rd
Luminescent material, wherein, first luminescent material includes first gas modulation luminescent material；Second luminescent material be with
The particle of stratum nucleare and gas-barrier layer 1, the stratum nucleare includes the second luminescent material, also, the stratum nucleare is by the institute of gas-barrier layer 1
Cladding；3rd luminescent material is the particle with stratum nucleare and gas-barrier layer 2, and the stratum nucleare includes the 3rd luminescent material,
Also, the stratum nucleare is coated by gas-barrier layer 2.
56. Security element according to claim 55, wherein, the first gas modulation luminescent material, second gas are adjusted
Two or three in luminescent material processed and third gas modulation luminescent material are identicals.
57. Security element according to claim 55, wherein, the first gas modulation luminescent material, second gas are adjusted
Luminescent material processed and third gas modulation luminescent material are identicals.
58. Security element according to claim 55, wherein, first luminescent material, the second luminescent material and the 3rd
Luminescent material is respectively present in the first false proof region, the second false proof region and the 3rd false proof region of the Security element.
59. Security element according to claim 58, wherein, in the case where exciting light irradiation, the first false proof region is in the first gas
Intensity ratio in body environment and second gas environment is the first particular value, and the second false proof region is in first gas environment
It is the second particular value with the intensity ratio in second gas environment, the 3rd false proof region is in first gas environment and the second gas
Intensity ratio in body environment is the 3rd particular value；In first particular value, the second particular value and the 3rd particular value
At least two differ.
60. Security element according to claim 58, wherein, in the case where exciting light irradiation, the first false proof region is in the first gas
The ratio between luminescent lifetime in body environment and second gas environment is the first particular value, and the second false proof region is in first gas environment
It is the second particular value with the ratio between the luminescent lifetime in second gas environment, the 3rd false proof region is in first gas environment and the second gas
The ratio between luminescent lifetime in body environment is the 3rd particular value；In first particular value, the second particular value and the 3rd particular value
At least two differ.
61. Security element according to claim 55, wherein, the gas-barrier layer 1 is less than to the barrier property of oxygen
Gas-barrier layer 2.
62. Security element according to claim 61, wherein, the gas-barrier layer 1 is silica barrier layer, described
Gas-barrier layer 2 is polyvinyl alcohol barrier layer.
63. Security element according to claim 58, wherein, in the case where exciting light irradiation, in first gas environment, three are anti-
Pseudo- region has identical luminous intensity, and in second gas environment, the first false proof region has the hair lower than the second false proof region
Luminous intensity, the second light-emitting zone have the luminous intensity lower than the 3rd false proof region.
64. Security element according to claim 63, wherein, the first gas environment is nitrogen atmosphere.
65. Security element according to claim 63, wherein, the second gas environment is oxygen atmosphere.
66. Security element according to claim 1, the false proof region is letter, numeral, word, bar code, Quick Response Code
Or pattern；Or collectively constitute letter, numeral, word, bar code, Quick Response Code or pattern by multiple false proof regions.
67. Security element according to claim 66, wherein, the multiple false proof region includes the first false proof region and the
Two false proof regions.
68. Security element according to claim 66, wherein,, can be with first gas environment in the case where exciting light irradiation
It was observed that occur letter, numeral, word, bar code, Quick Response Code and/or pattern on Security element, and in second gas environment,
The letter, numeral, word, bar code, Quick Response Code and/or pattern can not be observed.
69. Security element according to claim 66, wherein, it is false proof in first gas environment in the case where exciting light irradiation
Occur letter, numeral, word, bar code, Quick Response Code and/or pattern, and the letter, numeral, word, bar shaped on element
Specific color is presented in code, Quick Response Code and/or pattern, and in second gas environment, the letter, numeral, word, bar shaped
Code, Quick Response Code and/or pattern show different colors.
70. according to claim 5,9-11,17,21-23,33,47,48, any one of 50-54,59,60,63,68,69
Security element, in the second gas environment residing for the Security element, the content of oxygen is higher than first gas environment.
71. Security element according to claim 70, wherein, the first gas environment is not oxygenous Ring
Border.
72. Security element according to claim 70, wherein, the second gas environment is air atmosphere or oxygen gas
Atmosphere.
73. Security element according to claim 1, the Security element is ink layer, safety line, pad pasting, labeling, patch
Bar, trade mark, anti-false fiber, label or packaging material.
74. according to any one of claim 1-73 the first luminescent materials defined and the second luminescent material in Security element is prepared
Purposes.
75. the purposes according to claim 74, wherein, the Security element is ink layer, safety line, pad pasting, labeling, patch
Bar, trade mark, anti-false fiber, label or packaging material.
76. the purposes according to claim 74, wherein, first luminescent material and the second luminescent material are with composition
Form is applied.
77. the purposes according to claim 74, wherein, first luminescent material and the second luminescent material are separately applied
With.
A kind of 78. method for making Security element, including the use of the luminous material of first defined according to any one of claim 1-73
Material and the second luminescent material.
79. the method according to claim 78, wherein, first luminescent material and the second luminescent material are present in ink
In, and Security element is formed by way of printing.
80. the method according to claim 79, wherein, the ink be selected from offset ink, letterpress printing ink, base gravure ink,
Flexo ink and silk-screen ink.
81. the method according to claim 78, wherein, first luminescent material and/or the second luminescent material are present in
In fiber.
82. the method according to claim 81, wherein, first luminescent material and/or the second luminescent material are present in
In the different zones of fiber, Security element is formed by way of spinning.
83. the method according to claim 78, wherein, first luminescent material and the second luminescent material are with composition
Form is applied.
84. the method according to claim 78, wherein, first luminescent material and the second luminescent material are separately applied
With.
85. a kind of ink, first luminescent material of its definition containing any one of with good grounds claim 1-73 and/or the second luminous material
Material.
86. the ink according to claim 85, wherein, the ink be selected from offset ink, letterpress printing ink, base gravure ink,
Flexo ink and silk-screen ink.
87. the ink according to claim 85, wherein, the ink be used to manufacture Security element.
88. a kind of anti-fake product, the Security element according to claim any one of 1-73 is included in the anti-fake product.
89. the anti-fake product according to claim 88, wherein, described Security element with pad pasting, labeling, joint strip, label,
The form of trade mark, safety line or packaging material is arranged on the anti-fake product.
90. the anti-fake product according to claim 88, wherein, described anti-fake product is banknote, security, bill, commodity
Mark, commodity packaging, documentary evidence or antifake certificate card.
91. the anti-fake product according to claim 90, wherein, the security are stock.
92. the anti-fake product according to claim 90, wherein, the bill is check, admission ticket or ticket.
93. the anti-fake product according to claim 90, wherein, the documentary evidence is certificate, identity card or passport.
94. the anti-fake product according to claim 90, wherein, the antifake certificate card is credit card or bank book.
95. a kind of differentiate Security element according to claim any one of 1-73 or according to any one of claim 88-94
The method of described anti-fake product, it comprises the following steps：
Step 1：Exciting light is acted on into Security element, observes the color in false proof region in Security element, or the false proof member of detection
The luminescent spectrum and/or luminescent lifetime in false proof region in part；
Step 2：Change the gaseous environment residing for Security element, above-mentioned exciting light is acted on into the Security element, described in observation
The color in false proof region, or the luminescent spectrum and/or luminescent lifetime in the detection false proof region；
Step 3：Whether color, luminescent spectrum and/or the luminescent lifetime in the false proof region are sent out before and after contrast gaseous environment changes
Raw expected change, to determine the true and false of Security element or anti-fake product.
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| CN201610712780.1A CN106142890B (en) | 2016-08-24 | 2016-08-24 | Gas modulation lights Security element |
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| CN201610712780.1A CN106142890B (en) | 2016-08-24 | 2016-08-24 | Gas modulation lights Security element |
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| CN108443718B (en) * | 2017-02-16 | 2020-04-07 | 清华大学 | Friction luminescence method |
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| EP1295929B1 (en) * | 2001-09-25 | 2009-01-07 | MERCK PATENT GmbH | Anisotropic polymer film |
| CN102282218A (en) * | 2008-12-15 | 2011-12-14 | 科学与工业研究委员会 | Surface modified optically variable product for security feature |
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| GB2242161A (en) * | 1990-03-02 | 1991-09-25 | Robert Peter Sunman | Security document |
| EP1295929B1 (en) * | 2001-09-25 | 2009-01-07 | MERCK PATENT GmbH | Anisotropic polymer film |
| CN102282218A (en) * | 2008-12-15 | 2011-12-14 | 科学与工业研究委员会 | Surface modified optically variable product for security feature |
| CN102906558A (en) * | 2010-02-04 | 2013-01-30 | 光谱系统公司 | Gas activated changes to ligth absorption and emission characteristics for security articles |
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Effective date of registration: 20210428 Address after: 100070 8th floor, building 2, No.5 Zhonghe Road, Fengtai Science City, Fengtai District, Beijing Patentee after: China Banknote Printing Technology Research Institute Co.,Ltd. Patentee after: CHINA BANKNOTE PRINTING AND MINTING Corp. Address before: 100070 science Road 5, Beijing, Fengtai District Patentee before: SECURITY PRINTING INSTITUTE OF PEOPLE'S BANK OF CHINA Patentee before: CHINA BANKNOTE PRINTING AND MINTING Corp. |
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Address after: 100070 8th floor, building 2, No.5 Zhonghe Road, Fengtai Science City, Fengtai District, Beijing Patentee after: China Banknote Printing Technology Research Institute Co.,Ltd. Patentee after: China Banknote Printing and Minting Group Co.,Ltd. Address before: 100070 8th floor, building 2, No.5 Zhonghe Road, Fengtai Science City, Fengtai District, Beijing Patentee before: China Banknote Printing Technology Research Institute Co.,Ltd. Patentee before: CHINA BANKNOTE PRINTING AND MINTING Corp. |