CN102693679A - Anti-counterfeiting identification method by aid of quantum points - Google Patents
Anti-counterfeiting identification method by aid of quantum points Download PDFInfo
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Abstract
The invention relates to an anti-counterfeiting identification method by the aid of quantum points. The anti-counterfeiting identification method includes preparing quantum point ink: dispersing the quantum points in different structures and/or with different sizes into an organic solvent, adding transparent ink into the organic solvent, and uniformly mixing the organic solvent containing the quantum points with the transparent ink to prepare the quantum point ink capable of transmitting light with different wavelengths; loading an anti-counterfeiting identification: loading the prepared quantum point ink into a target product to be marked, forming the anti-counterfeiting identification in such a manner that at least partial areas in various component of the anti-counterfeiting identification contain more than one type of quantum points; detecting and converting the anti-counterfeiting identification: reading the central wavelength of each quantum point in the various components and ratios of luminescence intensities of the various quantum points by a spectrum detecting instrument; and converting the central wavelengths and the luminescence intensities of the various quantum points according to a coding rule to obtain a group of specific identification information, and judging the identification by the information. The anti-counterfeiting identification method has the advantages of difficulty in copying, high information capacity and fine stability.
Description
Technical field
The invention belongs to the anti-counterfeiting mark field, be specifically related to a kind of method of utilizing quantum dot to carry out anti-counterfeiting mark, the difference that relates to a kind of wavelength and emission peak intensity of the emission according to each quantum dot is more specifically carried out the method for anti-counterfeiting mark.
Background technology
In today that quantity of information is increased sharply, the safety of information and accurate identification have become the topic of social extensive concern.Particularly along with the continuous development with science and technology of becoming increasingly prosperous of commodity economy, false proofly become brand-new, a continuous field of development.Present existing security identification technology ubiquity make flow process complicated, cost an arm and a leg, low precision, be prone to crack, unstable and be subject to multiple technologies defective such as extraneous factor interference, can not satisfy the needs of current social information security developments.Therefore, press for the new security identification technology of exploitation to be used for false proof field.Though the market exists some density of encoding high at present; The anti-counterfeiting mark that information content is big, like common black two-dimensional bar, but the content of its printing can be seen intuitively; And use the desk size copying machine or the printing machine that are easy to get just can be easy to duplicate; Though and existing fluorescent ink, anti-false fiber can be accomplished the hidden transmission of information, but their information content is less, can't satisfy the bulky information demand.
" quantum dot " can be described as semiconductor nano again, is a kind of nano particle of being made up of II-VI family or III-V family element.The particle diameter of quantum dot is generally between 1～10nm, because electronics and hole be by quantum confinement, continuous band structure becomes the discrete energy levels structure with molecular characterization, can emitting fluorescence after being excited.Quantum dot is applied to false proof existing instance; Like Chinese patent CN 102296486 A " anti-tamper security band and apply the cheque paper of this anti-tamper security band ", CN 102002365A " transparent nano fluorescent material composition and the application in the concealed anti-false product thereof ", all used quantum dot as main anti-fake material.But patent CN102296486A will comprise embedded photoluminescent material, magnetic material, pressure sensitive and the combination of biological anti-fake material of quanta point material only is applied to cheque paper, and anti-pseudo-range is relatively narrow; And patent CN 102002365A is used for the concealed anti-false field with quantum dot and the metal-organic complex molecular combinations that comprises the inorganic nanometer oxide fluorescent powder of REE, the organic dyestuff that comprises unsaturated link and organic light emission micromolecule and comprise REE; It is mainly differentiated through fluorescence color and spectrum scanner; But because it comprises multiple fluorescent material; Need through optical filter or its fluorescent emission intensity of grating measuring and characteristic spectrum; Flow process is complicated relatively, precision is not high, and the anti-counterfeiting information amount is abundant inadequately.
Summary of the invention
In order to overcome problem and the shortcoming that exists in the above-mentioned prior art, the present invention provides that a kind of difficult quilt is imitated, information capacity is big, the quantum dot anti-counterfeiting mark method of good stability.
The object of the invention is realized through following technical scheme:
A kind of quantum dot anti-counterfeiting mark method, it may further comprise the steps:
The preparation of quantum dot printing ink: the quantum dot of different structure and/or size is scattered in the organic solvent, adds transparent ink, make the quantum dot printing ink that to launch different wave length after mixing;
Being written into of anti-counterfeiting mark: the above-mentioned quantum dot printing ink that makes is loaded on the target product to be marked, forms anti-counterfeiting mark, make in each ingredient of said anti-counterfeiting mark subregion at least contain more than one quantum dot;
The detection of anti-counterfeiting mark and conversion: the ratio of luminous intensity that reads centre wavelength and each quantum dot of each quantum dot in each ingredient through the spectral detection instrument; The ratio of the luminous intensity of the centre wavelength of each quantum dot and each quantum dot is changed through coding rule, obtained one group of specific identification information, and utilize this information to judge sign.
Preferably, described quantum dot is quantum dot or its corresponding nuclear shell structure quantum point that periodic table of elements II-VI family, III-V family, IV-VI family or IV family semiconducting compound make; Preferably, described periodic table of elements II-VI family semiconducting compound is binary compound CdSe for example, CdTe, ZnS, ZnSe, ZnTe; ZnO, HgS, HgSe, HgTe, or ternary compound CdSeS for example, CdSeTe, CdSTe; ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS; CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe; Or quaternary compound CdZnSeS for example, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe; Said periodic table of elements III-V family semiconducting compound is binary compound GaN for example, GaP, GaAs, GaSb, AlN, AlP, AlAs; AlSb, InN, InP, InAs, InSb, or ternary compound GaNP for example, GaNAs; GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs; AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP; Or quaternary compound GaAlNAs for example, GaAlNSb, GaAlPAs, GaAlP Sb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb; Said periodic table of elements IV-VI family semiconducting compound is for example SnS of binary compound, SnSe, SnTe, PbS, PbSe; PbTe, or ternary compound SnSeS for example, SnSeTe, SnSTe; PbSeS, PbSeTe, PbSTe, SnPbS; SnPbSe, SnPbTe or quaternary compound be SnPbSSe for example, SnPbSeTe, SnPbSTe; Said period of element Table IV family semiconducting compound is Si, and Ge or binary compound be SiC for example, SiGe; Said nucleocapsid structure is for being nuclear with foregoing periodic table of elements II-VI family, III-V family, IV-VI family, IV family semiconducting compound, with CdSe, and CdS, ZnSe, ZnS, CdO, ZnO, one or more among the SiO2 are the nuclear shell structure quantum point of shell.
Preferably; The ink product of described transparent ink for not adding pigment, said ink product of not adding pigment is one or more in epoxy acrylate class printing ink, urethane acrylate class printing ink, polyester acrylate class printing ink, polyether acrylate class printing ink, polyacrylic acid propyl ester or the unsaturated polyester (UP) class printing ink.
Preferably, said quantum dot printing ink is loaded into said target product through the mode of printing, air brushing, coating dipping or transfer.
Preferably, said organic solvent is toluene, chloroform or normal hexane.
Preferably, but said target product can be the film material print product or the textile of cavity, but should print product can be paper, film etc.If target product is a textile, then quantum dot printing ink is loaded into earlier on fiber, silk or the yarn, and said fiber, silk or yarn are being passed through known Weaving method, like woven or braiding, processes target product.
A kind of quantum dot anti-counterfeiting mark method, it may further comprise the steps:
The preparation of the false proof carrier of quantum dot: the quantum dot of different structure and/or size is mixed with macromolecular compound, process the false proof carrier of the quantum dot that to launch different wave length; Or be impregnated in the quantum dot solution that contains different structure and/or size after macromolecule resin processed carrier, make the false proof carrier of the quantum dot that can launch different wave length after the drying;
The making of anti-counterfeiting mark be written into: make anti-counterfeiting mark with the false proof carrier of above-mentioned quantum dot, then anti-counterfeiting mark be written on the false proof target product to be marked;
The detection of anti-counterfeiting mark and conversion: the ratio of luminous intensity that reads centre wavelength and each quantum dot of each quantum dot in each ingredient through the spectral detection instrument; The ratio of the luminous intensity of the centre wavelength of each quantum dot and each quantum dot is changed through coding rule, obtained one group of specific identification information, and utilize this information to judge sign.
Preferably, described quantum dot is quantum dot or its corresponding nuclear shell structure quantum point that periodic table of elements II-VI family, III-V family, IV-VI family or IV family semiconducting compound make; Preferably, described periodic table of elements II-VI family semiconducting compound is binary compound CdSe for example, CdTe, ZnS, ZnSe, ZnTe; ZnO, HgS, HgSe, HgTe, or ternary compound CdSeS for example, CdSeTe, CdSTe; ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS; CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe; Or quaternary compound CdZnSeS for example, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe; Said periodic table of elements III-V family semiconducting compound is binary compound GaN for example, GaP, GaAs, GaSb, AlN, AlP, AlAs; AlSb, InN, InP, InAs, InSb, or ternary compound GaNP for example, GaNAs; GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs; AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP; Or quaternary compound GaAlNAs for example, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb; Said periodic table of elements IV-VI family semiconducting compound is for example SnS of binary compound, SnSe, SnTe, PbS, PbSe; PbTe, or ternary compound SnSeS for example, SnSeTe, SnSTe; PbSeS, PbSeTe, PbSTe, SnPbS; SnPbSe, SnPbTe or quaternary compound be SnPbSSe for example, SnPbSeTe, SnPbSTe; Said period of element Table IV family semiconducting compound is Si, and Ge or binary compound be SiC for example, SiGe; Said nucleocapsid structure is for being nuclear with foregoing periodic table of elements II-VI family, III-V family, IV-VI family, IV family semiconducting compound, with CdSe, and CdS, ZnSe, ZnS, CdO, ZnO, one or more among the SiO2 are the nuclear shell structure quantum point of shell.
Preferably, described macromolecular compound is resin or fiber.Said resin is polystyrene, tygon, polypropylene, PVC, polyester, phenolics or acryl resin; Said fiber is acetyl cellulose or natural fiber.
Preferably, the said false proof carrier that makes is film or fiber; Said anti-counterfeiting mark is loaded in the target product through the method for pasting or weave.
Among the present invention, term " quantum dot " can be described as semiconductor nano again, is a kind of nano particle of being made up of II-VI family or III-V family element.The particle diameter of quantum dot is generally between 1～10nm, because electronics and hole be by quantum confinement, continuous band structure becomes the discrete energy levels structure with molecular characterization, can emitting fluorescence after being excited.
As long as quantum dot of the present invention has the distinct transmit wavelength, both can be the quantum dot of same composition, different-grain diameter size, also can be same particle size size, the different quantum dot of forming, or different the composition, the quantum dot of different-grain diameter size.
Coding rule of the present invention can be changed through following mode:
Centre wavelength is that the emission peak of 480nm is corresponding to a; Centre wavelength is that the emission peak of 540nm is corresponding to b; Centre wavelength be the emission peak of 600nm corresponding to c, centre wavelength be the emission peak of 640nm corresponding to g, each quantum dot emission peak intensity ratio be 1: 1 o'clock corresponding to 11; Emission peak strength ratio 2: 1 o'clock is corresponding to 21, the emission peak strength ratio be 3: 2: 1 corresponding to 321.A certain ingredient like anti-counterfeiting mark is 540nm and 640nm through the centre wavelength that the detecting instrument detection obtains, and the emission peak strength ratio is 1: 1, then through above-mentioned coding rule, can obtain information bg11; Another ingredient like anti-counterfeiting mark is 480nm and 600nm through the centre wavelength that the detecting instrument detection obtains, and the emission peak strength ratio is 2: 1, then passes through above-mentioned coding rule, can obtain information ac21.Can obtain the information of other ingredient of anti-counterfeiting mark with said method, then with the information combination of each several part at one, just obtained the full detail content of an anti-counterfeiting mark.It is thus clear that along with the increase of quantum dot kind in the increase of the quantity of ingredient and each ingredient, the information content of anti-counterfeiting mark institute load also will increase.Therefore the information content of anti-counterfeiting mark institute load can be controlled the kind of quantum dot according to actual needs.
The wavelength that the present invention is different according to the component of quantum dot, size is not launched simultaneously is different, and in the quantum dot composition each quantum dot concentration proportioning not simultaneously, emission peak intensity is different.Thereby, can realize accurate control through the factors such as size, component, structure of adjustment quantum dot to its luminescence feature peak position.
Adopt ultraviolet light as excitation source; Fiber spectrometer reads the geometric scheme and the spectral signature information thereof of quantum dot label as the spectrographic detection terminal; And through computing machine the quantum dot light code is resolved conversion and coincide to analyze, thereby the security identification of realization quantum dot label with data.
Compared with prior art, the present invention has following advantage: the present invention can control its information recorded through the size and the component of regulating quantum dot, and this information not only is difficult for by imitated, and information capacity is big, good stability.
Description of drawings
Cadmium selenide (CdSe) quantum dot wavelength-fluorescence intensity spectrogram of four kinds of different-grain diameters of Fig. 1.
Fig. 2 is the fluorescence spectrum figure of quantum dot A.
Fig. 3 is the fluorescence spectrum figure of quantum dot B.
Fig. 4 is the mixed fluorescence spectrum figure of two kinds of quantum dots of A, B of different proportion.
Fig. 5 is the synoptic diagram that quantum dot is adsorbed on cavity film material.
Fig. 6 is the two-dimensional bar synoptic diagram.
Fig. 7 is that the cellulose fluorescent film that contains different size (CdSe) ZnS quantum dot is processed the synoptic diagram that the LOGO anti-counterfeiting mark is pasted on target product.
Embodiment
Quantum dot anti-counterfeiting mark method of the present invention is mainly used in the anti-counterfeiting mark of product, through embodiment the present invention is further described below, but but following embodiment can not be interpreted as the qualification to the present invention's practical range.
Is example with CdSe quantum dots with (CdSe) ZnS core-shell quanta dots, and the present invention is further described:
Embodiment 1: the preparation of cadmium selenide (CdSe) quantum dot
Step 1: in there-necked flask, add cadmium oxide (CdO) and the 0.4mmol stearic acid (SA) of 0.1mmol, adopt the Schlenk technology, be heated to 150 ℃ after the degassing, the inflation for several times, keep 25min, it is colourless that CdO fully is dissolved to, and is cooled to 50 ℃ subsequently.
Step 2: in there-necked flask, add 1.94g purity greater than 90% three n-octyl phosphine oxides (TOPO) and 1.94g purity greater than 90% cetylamine (HDA).Adopt the Schlenk technology, drain water and oxygen only through vacuum system after, under ar gas environment, be heated to 320 ℃.At this moment, use syringe to inject the storing solution that disposes with 1mmol selenium (Se) and 2ml tri-n-butyl phosphine (TBP) fast, and fast cooling to 260 ℃, insulation reaction 30min withdraws from heating arrangement at last, makes product be cooled to room temperature.
Step 3: in the mixed liquor that step 2 obtains, add and the isopyknic chemical pure chloroform of this mixed liquor, add the chemical pure acetone of 3 times of volumes of this mixed liquor again after, will have solid to separate out, treat that solid separates out deposition and finish, centrifugal 10 minutes with 5000rpm.
Step 4: behind centrifugal the finishing the upper strata mixed liquor is outwelled, the chloroform and the acetone mixed liquor that added volume ratio again and be 1: 3 clean solid, and be centrifugal once more and outwell the upper strata mixed liquor, and remaining pressed powder is cadmium selenide (CdSe) quantum dot.
In the present embodiment, the size of cadmium selenide (CdSe) quantum dot can be controlled preferred 1-30min of this reaction time through the insulation reaction time 260 ℃ time the in the step 2.Fig. 1 is cadmium selenide (CdSe) quantum dot wavelength-fluorescence intensity spectrogram of four kinds of different-grain diameters making according to above-mentioned preparation method, and wherein curve e, f, g, h are respectively the fluorescence spectrum figure of cadmium selenide (CdSe) quantum dot that obtains at 260 ℃ of insulation reaction 2min, 10min, 18min, 30min in the step 2.
Embodiment 2
With the CdSe quantum dot independent excitation of two kinds of different-grain diameters sizes of A, B, the fluorescence spectrum figure that obtains as shown in Figures 2 and 3, the centre wavelength of quantum dot A is 567nm, the centre wavelength of quantum dot B is 621nm.A, two kinds of CdSe quantum dots of B were mixed with molar percentage respectively in 2: 1 and 4: 1, and the fluorescence spectrum figure of mixed quantum dot mixed liquor is as shown in Figure 4.Can know by Fig. 4; After quantum dot A and quantum dot B mixed in varing proportions, the wavelength of both emission peak peak values was all constant, and the fluorescent characteristics peak energy of each quantum dot is enough clearly distinguished; And there are corresponding relation in emission peak strength ratio and its blending ratio of quantum dot, and have relative specificity.This show mix the quanta point material of different emission after, the emission wavelength of the emission wavelength of each quantum dot in potpourri during with each quantum dot individualism is identical, and can draw the distinctive optical information of each quantum dot through the respective detection instrument.By that analogy; When a certain ingredient of anti-counterfeiting mark contains the quantum dot of n kind emission wavelength; Just can obtain n centre wavelength and common n+1 the unique information of emission peak strength ratio; This shows that along with the increase of quantum dot kind in the increase of the quantity of ingredient or the ingredient, the information content of anti-counterfeiting mark also can be along with increase.
Embodiment 3
The CdSe quantum dot of different size is dissolved in chloroform; The particle diameter of quantum dot is preferably 2 ~ 8nm, processes mass concentration and be 10% CdSe chloroform mixed liquor, then film material (the film material has a plurality of cavitys) is impregnated in the above-mentioned mixed liquor; The CdSe quantum dot of above-mentioned different size is adsorbed in the cavity of film material; As shown in Figure 5, utilize this film to process anti-counterfeiting mark then, be written into target product through modes such as stickup, packings again.Read the centre wavelength of each quantum dot in the film material cavity through spectral detection instrument such as fiber spectrometer; And the optical information such as luminous intensity of each quantum dot, and emission wavelength that will resulting each quantum dot, the luminous strength ratio that reaches each emission wavelength are changed through coding rule.For example: 480nm is corresponding to a for emission peak centre wavelength, and 540nm is corresponding to b for emission peak centre wavelength, and 600nm is corresponding to c for emission peak centre wavelength; 640nm is corresponding to g for emission peak centre wavelength, and each emission peak strength ratio 1: 1 o'clock is corresponding to 11, and each emission peak strength ratio 2: 1 o'clock is corresponding to 21; Each emission peak strength ratio 3: 2: 1 o'clock is corresponding to 321; A certain ingredient like anti-counterfeiting mark is 540nm and 640nm through the centre wavelength that the detecting instrument detection obtains, and the emission peak strength ratio is 1: 1, then through above-mentioned coding rule; Can obtain information bg11; Can obtain the information of other ingredient of anti-counterfeiting mark with said method, then with the information combination of each several part at one, just obtained the full detail content of anti-counterfeiting mark.
Embodiment 4
(CdSe) ZnS core-shell quanta dots of different size is dissolved in normal hexane, and the particle diameter of quantum dot is preferably 2 ~ 8nm, processes mass concentration and be (CdSe) ZnS normal hexane mixed liquor of 5%.
Cotton linter pulp is put into temperature be-12 ℃, contain in the water mixed liquid of 9wt%KOH and 15wt% urea, stir, can make the transparent mixed liquor of cellulose.With cellulose mixed liquor curtain coating; Coagulating bath solidification forming through containing 6wt% sulfuric acid/glazier's salt obtains cellulose wet-coating; The cellulose wet-coating of gained is immersed in above-mentioned (CdSe) ZnS normal hexane mixed liquor, soak half an hour, promptly obtain the cellulose fluorescent film after the taking-up drying.Can make the various cellulose fluorescent films that comprise (CdSe) ZnS quantum dot of more than one size according to said method, the cellulose fluorescent film of gained is processed anti-counterfeiting mark, be written in the target product through methods such as stickups again.As shown in Figure 6; Can process the two-dimensional bar code that width differs by the cellulose fluorescent film that contains different size (CdSe) ZnS quantum dot that gained is various; Each bar code can be formed by containing identical or different cellulose fluorescent film; Then read the centre wavelength of each quantum dot in each ingredient of anti-counterfeiting mark through spectral detection instrument such as fiber spectrometer, and the optical information such as luminous intensity of each quantum dot.And with the emission wavelength of resulting each quantum dot, and the luminous strength ratio of each emission wavelength change through coding rule.Coding rule is identical with embodiment 3, obtains one group of specific identification information, and utilizes this information to judge sign.As shown in Figure 7, also can process LOGO or pattern by the cellulose fluorescent film that contains different size (CdSe) ZnS quantum dot that gained is various, the different piece on LOGO or the pattern can be formed by containing identical or different cellulose fluorescent film.
Cellulosic dissolving in this instance, with the blend of quanta point material and regeneration all be physical process, chemical reaction does not take place, mild condition, pollution-free, be easy to industrialization.
Embodiment 5
Adding particle diameter in the transparent ink is the CdSe quantum dot of 2 ~ 8nm, and to make mass percent be 0.1% through mixing, contain the CdSe quantum dot printing ink of more than one size.Through methods such as printing, air brushing, coatings CdSe quantum dot printing ink is printed anti-counterfeiting mark on target product then; The shape as shown in Figure 6 such as the anti-counterfeiting mark of two-dimensional bar; Then read the centre wavelength of each quantum dot in each ingredient of anti-counterfeiting mark through spectral detection instrument such as fiber spectrometer, and the optical information such as luminous intensity of each quantum dot.And with the emission wavelength of resulting each quantum dot, and the luminous strength ratio of each emission wavelength change through coding rule.Coding rule is identical with embodiment 3.Obtain one group of specific identification information, and utilize this information to judge sign.
The anti-counterfeiting mark that the transparent ink of above-mentioned interpolation quantum dot prints is transparent; Naked eyes can't be told anti-counterfeiting mark in the daily use; But just can very clearly obtain identification information through the spectral detection instrument and verify the true and false, make this anti-counterfeiting mark disguised better, be difficult for by imitated.Quantum dot also can be produced fluorescence by ultraviolet excitation, can just slightly differentiate the true and false of product.
Embodiment 6
The CdSe quantum dot of different size is dissolved in the toluene, and quantum point grain diameter is preferably 2 ~ 8nm, processes mass concentration and be 4% CdSe toluene mixture liquid; Join polystyrene in the above-mentioned toluene mixture liquid then; After the dissolving, the mass concentration of polystyrene is 30%, is uniformly dispersed through ultrasonic fully; Obtain the polystyrene spinning liquid, then this spinning liquid is spun into fiber through spinning technique.Can make the various fibers that contain more than one quantum dots according to said method.With above-mentioned one or more fibrages or the woven anti-counterfeiting mark that goes out to design, like LOGO, pattern etc.This anti-counterfeiting mark can directly weave or be woven on products such as clothing, shoes and hats, also can weave earlier or woven one-tenth anti-counterfeiting mark, is written in the target product through modes such as pendant, decorations again.Then read the centre wavelength of each quantum dot in each ingredient of anti-counterfeiting mark through spectral detection instrument such as fiber spectrometer, and the optical information such as luminous intensity of each quantum dot.And with the emission wavelength of resulting each quantum dot, and the luminous strength ratio of each emission wavelength change through coding rule, coding rule is identical with embodiment 3, obtains one group of specific identification information, and utilizes this information to judge sign.
Therefore above-mentioned quantum dot solution itself is water white, and adding quantum dot is consistent with not adding the fiber color that the spinning of quantum dot polystyrene spinning liquid comes out.This fiber applications is when clothing, shoes and hats etc. false proof, and naked eyes can't be told anti-counterfeiting mark in the daily use, but just can very clearly obtain identification information through the spectral detection instrument verifies the true and false, makes this anti-counterfeiting mark disguised better, is difficult for being copied.
The present invention is not limited to above-mentioned embodiment; If various changes of the present invention or distortion are not broken away from the spirit and scope of the present invention; If these changes and distortion belong within claim of the present invention and the equivalent technologies scope, then the present invention also is intended to comprise these changes and distortion.
Claims (9)
1. quantum dot anti-counterfeiting mark method, it may further comprise the steps:
The preparation of quantum dot printing ink: the quantum dot of different structure and/or size is scattered in the organic solvent, adds transparent ink, make the quantum dot printing ink that to launch different wave length after mixing;
Being written into of anti-counterfeiting mark: the above-mentioned quantum dot printing ink that makes is loaded on the target product to be marked, forms anti-counterfeiting mark, make in each ingredient of said anti-counterfeiting mark subregion at least contain more than one quantum dot;
The detection of anti-counterfeiting mark and conversion: the ratio of luminous intensity that reads centre wavelength and each quantum dot of each quantum dot in each ingredient through the spectral detection instrument; The ratio of the luminous intensity of the centre wavelength of each quantum dot and each quantum dot is changed through coding rule, obtained one group of specific identification information, and utilize this information to judge sign.
2. quantum dot anti-counterfeiting mark method according to claim 1 is characterized in that: described quantum dot is quantum dot or its corresponding nuclear shell structure quantum point that periodic table of elements II-VI family, III-V family, IV-VI family or IV family semiconducting compound make; Said II-VI family semiconducting compound is CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe; HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS; HgZnSe CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe or HgZnSTe; Said III-V family semiconducting compound is GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP; InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb; AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP GaAlNAs, GaAlNSb, GaAlPAs; GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs or InAlPSb; Said IV-VI family semiconducting compound is SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe SnPbSSe, SnPbSeTe or SnPbSTe; Said IV family semiconducting compound is Si, Ge, SiC or SiGe; Said nuclear shell structure quantum point is for being nuclear with described II-VI family, III-V family, IV-VI family, IV family semiconducting compound, with CdSe, and CdS, ZnSe, ZnS, CdO, ZnO, SiO
2In one or more be the nuclear shell structure quantum point of shell.
3. quantum dot anti-counterfeiting mark method according to claim 1 is characterized in that described organic solvent is toluene, chloroform and normal hexane.
4. quantum dot anti-counterfeiting mark method according to claim 1; It is characterized in that: the ink product of described transparent ink for not adding pigment, said ink product of not adding pigment is one or more in epoxy acrylate class printing ink, urethane acrylate class printing ink, polyester acrylate class printing ink, polyether acrylate class printing ink, polyacrylic acid propyl ester and the unsaturated polyester (UP) class printing ink.
5. according to each described quantum dot anti-counterfeiting mark method of claim 1-4, it is characterized in that: said quantum dot printing ink is loaded into said target product through the mode of printing, air brushing, coating dipping or transfer.
6. quantum dot anti-counterfeiting mark method, it may further comprise the steps:
The preparation of the false proof carrier of quantum dot: the quantum dot of different structure and/or size is mixed with macromolecular compound, process the false proof carrier of the quantum dot that to launch different wave length; Or be impregnated in the quantum dot solution that contains different structure and/or size after macromolecule resin processed carrier, make the false proof carrier of the quantum dot that can launch different wave length after the drying;
The making of anti-counterfeiting mark be written into: make anti-counterfeiting mark with the false proof carrier of above-mentioned quantum dot, then anti-counterfeiting mark be written on the false proof target product to be marked;
The detection of anti-counterfeiting mark and conversion: the ratio of luminous intensity that reads centre wavelength and each quantum dot of each quantum dot in each ingredient through the spectral detection instrument; The ratio of the luminous intensity of the centre wavelength of each quantum dot and each quantum dot is changed through coding rule, obtained one group of specific identification information, and utilize this information to judge sign.
7. quantum dot anti-counterfeiting mark method according to claim 6 is characterized in that: described quantum dot is quantum dot or its corresponding nuclear shell structure quantum point that periodic table of elements II-VI family, III-V family, IV-VI family or IV family semiconducting compound make; Said II-VI family semiconducting compound is CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe; HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS; HgZnSe CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe or HgZnSTe; Said III-V family semiconducting compound is GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP; InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb; AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP GaAlNAs, GaAlNSb, GaAlPAs; GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs or InAlPSb; Said IV-VI family semiconducting compound is SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe SnPbSSe, SnPbSeTe or SnPbSTe; Said IV family semiconducting compound is Si, Ge, SiC or SiGe; Said nuclear shell structure quantum point is for being nuclear with described II-VI family, III-V family, IV-VI family, IV family semiconducting compound, with CdSe, and CdS, ZnSe, ZnS, CdO, ZnO, SiO
2In one or more be the nuclear shell structure quantum point of shell.
8. quantum dot anti-counterfeiting mark method according to claim 6 is characterized in that described macromolecular compound is polystyrene, tygon, polypropylene, PVC, polyester, acetyl cellulose or natural fiber.
9. according to each described quantum dot anti-counterfeiting mark method of claim 6-8, it is characterized in that the said false proof carrier that makes is film or fiber; Said anti-counterfeiting mark is loaded in the target product through the method for pasting or weave.
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