CN102673203A - Multi-wavelength fluorescent quantum dot anti-counterfeiting method - Google Patents
Multi-wavelength fluorescent quantum dot anti-counterfeiting method Download PDFInfo
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Abstract
The invention discloses a multi-wavelength fluorescent quantum dot anti-counterfeiting method, comprising the following steps of (1) selecting a plurality of fluorescent quantum dots with various grain diameter types, wherein the fluorescence emission spectrums of the fluorescent quantum dots are evenly distributed within a near-infrared area; moreover, no wave bands overlap; and the type of the selected quantum dots is in a number equal to that of the ink boxes of a selected printer, and further is corresponding to the ink boxes of the selected printer one to one; (2) coding a plurality of fluorescent quantum dots of various types in each black bar according to bar codes through the utilization of the presence or absence of the fluorescence peaks of the fluorescent quantum dots of various type within a given wave band; (3) evenly mixing the quantum dots with ink in the corresponding printer ink box; and (4) printing an anti-counterfeiting marker with the ink containing the quantum dots in the step (3) so as to realize the highly anti-counterfeiting of commodities. The anti-counterfeiting marker made by such an anti-counterfeiting method has the advantages of high precision, good hiddenness and large information capacity, and further can be set and assigned by a manufacturer.
Description
Technical field
The invention belongs to field of anti-counterfeit technology, relate to a kind of novel method for anti-counterfeit, the characteristic that can produce fluorescence after utilizing near infrared fluorescence quantum point to be stimulated is stated from customizing messages in the commodity external packing.
Background technology
At present, the anti-counterfeiting technology of comparative maturity has tens of kinds more than, and principle is different, and antifalse effect respectively has superiority.At present common anti-counterfeiting technology has network anti-counterfeit, material false proof (like paper, film anti-counterfeiting technology etc.), printing ink false proof (like temperature-sensitive anti-forgery ink, photosensitive anti-forgery ink etc.), physics false proof (like the refraction that utilizes light, the anti-counterfeiting technology of electromagnetic technique etc.), antiforge (like the laser hologram image anti-counterfeiting technology), package anti-counterfeiting (like anti-fake bottle lid, false proof body etc.), computer false proof etc.To be applied to the false proof fluorescent ink technology of coin be example with comparatively common, and it results from the seventies and eighties in last century, develops into polychrome printing ink afterwards by initial fluorescent fiber silk, in a period of time, obtains good antifalse effect.But along with increasing of anti-forgery ink manufacturer, imitated technology is very ripe, so the effect of this anti-counterfeiting technology has not just had anti-fake and forged effect yet.
Seeing that traditional anti-counterfeiting technology has also all received the restriction of various technical factors and human factor, lost best antifalse effect gradually.The multiple anti-counterfeiting technology that good application prospect is arranged, sealing off anti-counterfeit adhesive tape, nanometer anti-counterfeiting technology etc. like multimedia anti-counterfeiting technology, super nuclear micropore anti-counterfeiting technology, micro secret mark technology, self check all is anti-counterfeiting technology or product preferably.The nanometer anti puppet is just receiving the concern of countries in the world as brand-new high-tech anti-counterfeiting technology.American I BM company had successfully realized minimum in the world nanoscale pictorial trademark in 1989, and 1992, the nano-packaging technology of China, invisible-bar-number were succeeded in developing.The Massachusetts XMX company of the U.S. in 1994 obtains a production and is used for patent printing-ink, evengranular nanoparticle.The rare earth photodeveloper of developing at present, colourless under daylight and visible light, under ultraviolet light, radiate 550nm～580nm light wave, and different complexing methods will present the coloured light that is not quite similar, confidentiality is high.
Quantum dot is claimed the semiconductor nano microcrystal again, be a kind of that form by II-VI family or III-V family element, particle diameter between 1nm-10nm, can accept the semiconductor nanoparticle of excitation light generation fluorescence.Quantum dot has that the polynary emission of an elementary excitation, optical stability are high, fluorescence lifetime is long, the exciting light spectrum width and continuously, fluorescent characteristic such as fluorescence spectrum is narrow and symmetrical, Stokes shift is bigger.
Compare with traditional organic fluorescent dye, the superiority of quantum dot is embodied in:
(1) the different emitted fluorescence spectrum of the particle diameter of quantum dot are also different.Size and chemical composition through changing quantum dot can make its emission spectrum cover whole visible region.
(2) quantum dot has wide and continuous excitation spectrum and narrow and symmetrical fluorescence spectrum.Use same excitation source can excite the quantum dot of different-grain diameter, thereby can be used for multi-color marking.And the fluorescence emission peak of quantum dot is narrow and do not have hangover, is not prone to spectrum when multiple quantum dot uses simultaneously and overlaps.
(3) quantum dot has good photostability, and fluorescence lifetime is long.It is high 20 times that the fluorescence intensity ratio of quantum dot is used fluorescent material " rhodamine 6G " always, and stability is more than 100 times of " rhodamine 6G " especially.The fluorescence lifetime of quantum dot is sustainable to reach tens of nanoseconds, makes when optical excitation after, and most autofluorescence background decays and quantum dot fluorescence still exists, and can obtain not having at this moment the fluorescence signal of ambient interferences.
(4) quantum dot has bigger Stokes shift.Can avoid the overlapping of emission spectrum and excitation spectrum, help the detection of fluorescence spectrum signal.
At present, existing company releases the biomarker technology platform based on quantum dot.Quantum Dots Corp company successfully develops quantum dot-labeled biologic product product.Quantum dot is classified as one of scientific and technological ten quantum jumps in 2004.Quantum dot also can replace ink or the dyestuff in the biological screening process, can be used to make the bill bar shaped of marketable securities, is the newest fruits of nanometer anti-counterfeiting technology.
Based on aforementioned analysis, the inventor proposes a kind of quantum dot anti-counterfeiting technology, and this case produces thus.
Summary of the invention
The object of the invention is to provide a kind of multi-wavelength fluorescence quantum method for anti-counterfeit, and its precision height, good concealment, information capacity are big, and can set by producer oneself, assignment.
In order to reach above-mentioned purpose, solution of the present invention is:
A kind of multi-wavelength fluorescence quantum method for anti-counterfeit comprises the steps:
(1) choose the fluorescence quantum of multiple different-grain diameter size, the emitting fluorescence spectrum of this quantum dot evenly distributes in the near infrared light zone, and the wavestrip zero lap, and the species number of selected quantum dot equates with the print cartridge quantity of selected printer, and correspondence one by one;
(2) combine bar code, in each secret note, utilize have unmatchful its of fluorescence peak in given wave band of multiple fluorescence quantum to encode;
(3) quantum dot is evenly mixed with ink in the pairing ink-cases of printers;
(4) utilize the ink printed that contains quantum dot in the step (3) to become anti-fake identification mark, thereby the height of realizing commodity is false proof.
In the above-mentioned steps (3), when quantum dot mixed with ink, its concentration need guarantee that it can normally be detected after printing.
After adopting such scheme; One group of number equates with the print cartridge number, fluorescence peak is positioned near infrared region and the nonoverlapping quantum dot of wavestrip through selecting in the present invention; With its respectively with each print cartridge in ink evenly mix; Bar code raw information is passed through coding rule and is encrypted the anti-fake identification mark that afterwards goes out to contain the quantum dot information by printing of inkjet printer, compares with existing false proof printing technique, mainly contains following advantage:
(1) with near infrared fluorescence quantum point as false proof media.Typical application can produce visible fluorescence in the ultraviolet fluorescent anti-false sign on the coin under ultraviolet irradiation.The near infrared fluorescence quantum point that the present invention adopts is not having can not produce fluorescent emission under the specific exciting light condition, and naked eyes can't be discerned.Excite generation fluorescence even receive, the fluorescence of near infrared band outside visible-range 390～770nm, naked eyes can't be discerned equally, must discern by corresponding anti-counterfeiting detection equipment, so the disguise of near infrared fluorescence quantum point are higher.
Fluorescence quantum is synthetic technical very strong with preparation itself simultaneously; The slight change of environmental factor can both produce tangible influence to the fluorescence spectrum of synthetic back quantum dot in the building-up process; Therefore same batch synthetic fluorescence quantum such as need duplicate; Ambient parameter is strict, and imitation difficulty is high, has operational non-reproduction.
(2) adopt the encode false-proof mode.The synthetic fluorescence quantum of different batches is applied to anti-counterfeiting technology; Have only the different coding of setting rule to realize antiforge function; The present invention adopts cryptographic technique, and information is carried in the fluorescence signal, in anti-counterfeit detecting system, utilizes the decoding of inverse operation method again; Restore information has advantages such as capacity is big, encryption is strong.
Description of drawings
Fig. 1 is an integrated stand composition of the present invention.
The specific embodiment
The present invention provides a kind of multi-wavelength fluorescence quantum method for anti-counterfeit, comprises the steps:
(1) choose the fluorescence quantum of multiple different-grain diameter size, the emitting fluorescence spectrum of this quantum dot evenly distributes in the near infrared light zone, and the wavestrip zero lap, and the species number of selected quantum dot equates with the print cartridge quantity of selected printer, and correspondence one by one;
(2) combine bar code, in each secret note, utilize have unmatchful its of fluorescence peak in given wave band of multiple fluorescence quantum to encode;
(3) quantum dot is evenly mixed with ink in the pairing ink-cases of printers, its concentration is advisable to guarantee that it can normally be detected after printing, and described ink can be colored, black or colourless;
(4) utilize the ink printed that contains quantum dot in the step (3) to become anti-fake identification mark, can be printed in the optional position of commodity, thereby the height of realizing commodity is false proof.
Below will combine specific embodiment, technical scheme of the present invention will be further elaborated.
1. the selection of quantum dot: but quantum dot is excited emitting fluorescence; For making detected fluorescence spectrum not overlapping as far as possible; The present invention selects one group of quantum dot, and its fluorescence peak place wavelength evenly distributes in visible light and near infrared band, and selected kind number should equate with the ink-cases of printers number.Because the fluorescence peak of quantum dot place wavelength is relevant with its size, can confirm the grain size of corresponding quantum dot according to the two relation.As shown in Figure 1, be example with four print cartridge printers, select fluorescence peak place wavelength to be respectively four kinds of quantum dots of 410nm, 480nm, 560nm, 620nm.With the CdTe quantum dot is example, and the fluorescence peak place wavelength (λ) of CdTe quantum dot is λ=155.01*ln (d)+415.5 with particle diameter (d) relation, can try to achieve corresponding quantum point grain diameter and be respectively 0.965nm, 1.51nm, 2.54nm, 3.74nm.
2. the realization of coding rule: the present invention provides the coding rule of four print cartridge printers, six print cartridge printers.
As shown in Figure 1, be example with four print cartridge printers, four print cartridges hold the ink of C (cyan), M (magenta), Y (Huang), four kinds of colors of K (deceiving) respectively, and four kinds of fluorescence quantums are added to respectively in the middle of four print cartridges.Suppose that corresponding relation is following:
Print cartridge: C M Y K
Fluorescence quantum: a b c d
During printing,, reach the output of each print cartridge ink inside of control, and reach the output of control fluorescence quantum through the color of control output.When printing a color lump, every kind of fluorescence quantum has only output and does not export two kinds of situation.The quantity of the fluorescence quantum of output can be different, but remain on more than certain threshold value.Under the condition of four print cartridges, to remove and do not export entirely and two kinds of full outputs, the output situation one of fluorescence quantum has 14 kinds.Each output situation corresponding a fluorescence quantum-dot coding.Represent the situation that quantum dot is not exported with 0, the situation of 1 expression quantum dot output then has quantum dot output combination as shown in table 1:
Table 1
| Quantum dot output combination | Quantum dot output combination |
| 1:0:0:0 | 0:1:1:0 |
| 0:1:0:0 | 0:1:0:1 |
| 0:0:1:0 | 0:0:1:1 |
| 0:0:0:1 | 1:1:1:0 |
| 1:1:0:0 | 1:1:0:1 |
| 1:0:1:0 | 1:0:1:1 |
| 1:0:0:1 | 0:1:1:1 |
We call the proportioning combination to quantum dot output combination.We make up with a kind of proportioning and represent a raw information, and like " 1: 0: 0: 0 " this proportioning combination expression " 1 ", " 0: 1: 0: 0 " expression " 2 " by that analogy, then has the coding schedule shown in the table 2:
Table 2
| Raw information | The proportioning combination | Raw information | The |
| 0 | 1 ：0 ：0 ：0 | 7 | 0 ：1 ：1 ：0 |
| 1 | 0 ：1 ：0 ：0 | 8 | 0 ：1 ：0 ：1 |
| 2 | 0 ：0 ：1 ：0 | 9 | 0 ：0 ：1 ：1 |
| 3 | 0 ：0 ：0 ：1 | Self-defined | 1 ：1 ：1 ：0 |
| 4 | 1 ：1 ：0 ：0 | Self-defined | 1 ：1 ：0 ：1 |
| 5 | 1 ：0 ：1 ：0 | Self-defined | 1 ：0 ：1 ：1 |
| 6 | 1 ：0 ：0 ：1 | Self-defined | 0 ：1 ：1 ：1 |
Different raw information is represented in each proportioning combination immediately, that is to say that shown in the table 2 is the wherein a kind of of this coding.
Above encoding relation can be generalized in six print cartridges, the eight print cartridge printers and goes.Be example with six print cartridge printers below.The print cartridge that magenta (M), cyan (C), yellow (Y), light magenta (LM), nattierblue (LC), black (K) are arranged in the six print cartridge printers.We select six kinds of different quantum dots of particle diameter, are respectively quantum dot a, b, and c, d, e, f adds them in the middle of the above-mentioned print cartridge successively, then has:
Print cartridge: M C Y LM LC K
Quantum dot: a b c d e f
Be similar to the situation of four print cartridge printers, under the condition that six print cartridges are printed, remove and do not export entirely and two kinds of full outputs, fluorescence quantum has 40 kinds of output situation.Wherein a kind of encoding relation is seen table 3:
Table 3
| Raw information | The proportioning combination | Raw information | The proportioning combination | Raw information | The |
| 1 | 1:0:0:0:0:0 | F | 1:1:0:0:0:1 | T | 0:1:1:1:0:1 |
| 2 | 0:1:0:0:0:0 | G | 1:1:1:1:0:0 | U | 0:1:1:1:1:1 |
| 3 | 0:0:1:0:0:0 | H | 1:1:1:0:1:0 | V | 0:0:1:1:0:0 |
| 4 | 0:0:0:1:0:0 | I | 1:1:1:0:0:1 | W | 0:0:1:0:1:0 |
| 5 | 0:0:0:0:1:0 | J | 1:1:1:1:1:0 | X | 0:0:1:0:0:1 |
| 6 | 0:0:0:0:0:1 | K | 1:1:1:1:0:1 | Y | 0:0:1:1:1:0 |
| 7 | 1:1:0:0:0:0 | L | 0:1:1:0:0:0 | Z | 0:0:1:1:0:1 |
| 8 | 1:0:1:0:0:0 | M | 0:1:0:1:0:0 | ！ | 0:0:1:1:1:1 |
| 9 | 1:0:0:1:0:0 | N | 0:1:0:0:1:0 | 0:0:0:1:1:0 | |
| A | 1:0:0:0:1:0 | O | 0:1:0:0:0:1 | # | 0:0:0:1:0:1 |
| B | 1:0:0:0:0:1 | P | 0:1:1:1:0:0 | % | 0:0:0:0:1:1 |
| C | 1:1:1:0:0:0 | Q | 0:1:1:0:1:0 | $ | 0:0:0:1:1:1 |
| D | 1:1:0:1:0:0 | R | 0:1:1:0:0:1 | ? | ? |
| E | 1:1:0:0:1:0 | S | 0:1:1:1:1:0 | ? | ? |
Among the present invention, the China ink that goes out that raw information is encrypted back control print cartridge through coding rule is measured, and then prints the anti-fake identification mark that contains fluorescence quantum.
The ink of different colours can be used for different demands among the present invention: color inks can be printed trade mark, name of product, special pattern etc., and its color is mixed printing by multiple ink by different proportionings and formed, and can contain certain raw information, to identify the ture or false; Black ink can be printed the bar code of customizing messages, and the information that bar code itself contains can be discerned as selling, and the fluorescence quantum-dot coding information that it contains can be used for multi-enciphering and false proof; Colorless ink can be printed on the optional position of commodity; And externally do not announce; Can whether contain information with the detection ad-hoc location by relevant quality supervision department or enterprises personal identification, and whether this information is identical with original start information, to play the effect of anti-counterfeiting mark.
Above embodiment is merely explanation technological thought of the present invention, can not limit protection scope of the present invention with this, every technological thought that proposes according to the present invention, and any change of on the technical scheme basis, being done all falls within the protection domain of the present invention.
Claims (2)
1. a multi-wavelength fluorescence quantum method for anti-counterfeit is characterized in that comprising the steps:
(1) choose the fluorescence quantum of multiple different-grain diameter size, the emitting fluorescence spectrum of this quantum dot evenly distributes in the near infrared light zone, and the wavestrip zero lap, and the species number of selected quantum dot equates with the print cartridge quantity of selected printer, and correspondence one by one;
(2) combine bar code, in each secret note, utilize have unmatchful its of fluorescence peak in given wave band of multiple fluorescence quantum to encode;
(3) quantum dot is evenly mixed with ink in the pairing ink-cases of printers;
(4) utilize the ink printed that contains quantum dot in the step (3) to become anti-fake identification mark, thereby the height of realizing commodity is false proof.
2. a kind of multi-wavelength fluorescence quantum method for anti-counterfeit as claimed in claim 1 is characterized in that: in the said step (3), when quantum dot mixed with ink, its concentration need guarantee that it can normally be detected after printing.
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Cited By (5)
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| CN103559475A (en) * | 2013-11-22 | 2014-02-05 | 广州优库电子有限公司 | Multi-wavelength laser modulation one-dimensional bar code reader and implementing mode thereof |
| US9940566B2 (en) | 2016-01-15 | 2018-04-10 | International Business Machines Corporation | Extracting information from surface coatings |
| CN108182868A (en) * | 2018-01-25 | 2018-06-19 | 福州大学 | A kind of anti-counterfeiting mark based on quantum dot light Photoluminescence Properties and Film patterning technology |
| CN108694427A (en) * | 2017-04-07 | 2018-10-23 | 中国科学院化学研究所 | A kind of coding of bar code, hidden method and its application as identification label |
| CN109073553A (en) * | 2015-09-21 | 2018-12-21 | 悠蓓秋蒂公司 | Quantum dot safety ink |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103559475A (en) * | 2013-11-22 | 2014-02-05 | 广州优库电子有限公司 | Multi-wavelength laser modulation one-dimensional bar code reader and implementing mode thereof |
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| US10223627B2 (en) | 2016-01-15 | 2019-03-05 | International Business Machines Corporation | Extracting information from surface coatings |
| US10546221B2 (en) | 2016-01-15 | 2020-01-28 | International Business Machines Corporation | Extracting information from surface coatings |
| CN108694427A (en) * | 2017-04-07 | 2018-10-23 | 中国科学院化学研究所 | A kind of coding of bar code, hidden method and its application as identification label |
| CN108694427B (en) * | 2017-04-07 | 2021-06-22 | 中国科学院化学研究所 | Method for coding and hiding bar code and application of bar code as identification label |
| CN108182868A (en) * | 2018-01-25 | 2018-06-19 | 福州大学 | A kind of anti-counterfeiting mark based on quantum dot light Photoluminescence Properties and Film patterning technology |
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Application publication date: 20120919 |