CN105778725A - Anti-fake material composition based on fluorescent quantum dots and use method thereof - Google Patents
Anti-fake material composition based on fluorescent quantum dots and use method thereof Download PDFInfo
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- CN105778725A CN105778725A CN201610133107.2A CN201610133107A CN105778725A CN 105778725 A CN105778725 A CN 105778725A CN 201610133107 A CN201610133107 A CN 201610133107A CN 105778725 A CN105778725 A CN 105778725A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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Abstract
The invention relates to an anti-fake material composition based on fluorescent quantum dots and a use method thereof.The use method includes the steps that small organic molecule or carbon materials serve as a carbon source, carbon quantum dots with fluorescence are prepared with a solvothermal method and then mixed with light-cured resin and light activity monomers, a pre-designed colorless transparent pattern can be obtained in a specific area of a base material through the steps of silk-screen printing, nanometer embossing, mask adding exposing and the like, and specific fluorescence can be displayed under excitation of light with certain wavelength and can be used for anti-fake labels.According to the anti-fake material composition and the use method, the preparing process is simple, preparing cost is low, environmentally-friendly and nontoxic effects are achieved, biocompatibility is good, the novel anti-fake material stable in fluorescence property can be obtained, and the broad application prospects are achieved.
Description
Technical field
The present invention relates to a kind of anti-fake material constituent based on fluorescence quantum and using method thereof.
Background technology
Along with the lifting of scientific and technical development and safety consciousness, the requirement of anti-fake material is more come high by people.Current anti-fake material is broadly divided into organic fluorescence materials and the big class of inorganic fluorescent material two.Wherein, organic fluorescence materials is typically the unsaturated molecule of conjugated body on a large scale, due to the unstability of unsaturated molecule, it is easy to oxidation Decomposition, causes material light stability poor, to the toxic effect of organism, and complex manufacturing, relatively costly.And inorganic fluorescent material, such as phosphorus powder etc., mostly it is difficult to dissolve in organic facies, poor water resistance, encapsulating material is had a degree of abrasion and erosion, and there is toxicity mostly, heavy contamination in production process.
Simultaneously, current anti-counterfeiting mark often adopts product surface printing and the mode of papery fluorescence falsification preventing, and the printing-ink used self has certain color, in order to improve the aesthetic property of product appearance, producer has to select the paper identical with fluorescent material ground state color as housing material, greatly limit the attractive in appearance of product and design flexibility.Therefore, we need invention a kind of forwardly or a class is nontoxic, can be used for biological field, and cost of manufacture is low, and fluorescence property is stable, does not affect the false proof fluorescent material of a new generation of appearance design.
Carbonaceous quantum dot is emerging carbonaceous material after CNT, Nano diamond, fullerene and Graphene in recent years.It is the granule or lamellar structure that a kind of particle diameter is very small, and its diameter is typically in below 100nm, less than or close to Exciton Bohr Radius.According to its concrete pattern, granular carbon quantum dot is referred to as carbon quantum dot, and lamellar carbonaceous quantum dot is referred to as graphene quantum dot.Owing to its size is very special, thus there is the specific physical character such as quantum size effect, skin effect, show excellent fluorescence property.Carbonaceous quantum dot, as a kind of novel fluorescent material, has very big advantage compared with traditional organic fluorescence materials and inorganic fluorescent material.Its raw material is extensively easy to get, and can reach to merge completely with living organism, can carry out in vivo marker and detection completely through suitable means, significantly widen the range of application of anti-fake mark；And the monochromatic light of different colours can be produced by its size of regulation and control and surface functional group type, it is possible to well control its fluorescence property；Meanwhile, its fluorescence intensity and life-span are far superior to conventional fluorescent material.And due to the unique dimensional characteristic of quantum dot so that it is it is easy to be processed and post processing, silk screen printing, nano impression can be passed through, add the methods such as mask exposure solidification and obtain the fluorescent anti-fake mark of arbitrary graphic pattern.The phosphor pattern obtained is in water white transparency state under naked eyes, and under the exciting of exciting light, fluorescence is strongly visible, it is possible under ensureing anti-fraud functional premise, efficiently and effectively overcome the fluorescent material constraint to product design.
Summary of the invention
It is desirable to provide a kind of anti-fake material constituent based on fluorescence quantum and using method thereof.The present invention is with organic molecule or material with carbon element for carbon source, prepared by solvent-thermal method and there is epipolic carbonaceous quantum dot, then it is mixed with light-cured resin and photoactive monomer, by silk screen printing, nano impression, add the processes such as mask exposure solidification, the water white transparency pattern that can be designed in advance on base material.This pattern in colourless, can be shown that the fluorescence of different colours under the light of certain wavelength excites, can be applicable to anti-fake mark under natural light.This anti-fake material preparation process is simple, and preparation cost is low, green non-poisonous, and biocompatibility is good, and fluorescence property is stable.
Anti-fake material constituent based on fluorescence quantum provided by the invention, it substantially forms and with mass fraction is:
A carbonaceous quantum dot 0.001～0.1 part；Preferred mass fraction is 0.005～0.01 part；
B activity monomer 10～70 parts；
C resin 20～50 parts；
D light trigger 1～5 part；
E organic solvent 5～10 parts；
Above-mentioned carbonaceous quantum dot is: with organic molecule or material with carbon element for carbon source, adds in solvent, and ultrasonic disperse is uniform, carries out solvent thermal reaction 0.5-10h, obtain carbon quantum dot dispersion liquid under 150-300 DEG C of condition, purifies, and rotation obtains solid carbon quantum dot after steaming.Carbonaceous quantum dot is of a size of 1-100nm, and excitation wavelength is 270-480nm.Solvent is selected from: water, ethanol, ethylene glycol, glycerol, N,N-dimethylformamide or oxolane；Organic molecule is selected from: glucose, fructose, sucrose, ascorbic acid, citric acid, folic acid, glutamic acid, cysteine or glycine；Material with carbon element is selected from CNT, carbon fiber or Graphene, and material with carbon element is preferably through the CNT of oxidation processes, carbon fiber or graphene oxide.Oxidation processes adopts the method adding oxidant (potassium hydrogen persulfate) in solvent thermal reaction to realize, and the oxidant quality of addition is 1-5 times of CNT or carbon fiber quality.
Above-mentioned activated monomer is any in simple function group, difunctional, three kinds of functional group reactive acrylate monomer of polyfunctional group or their mixture.
Monofunctional acrylates's ester monomer is any in following material or their mixture: butyl acrylate, Isooctyl acrylate monomer, 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, glycidyl methacrylate.
Bifunctional acrylate's monomer is any in following material or their mixture: diethylene glycol class diacrylate, triethylene glycol class diacrylate, Polyethylene Glycol (200) diacrylate, dipropylene glycol class diacrylate, tripropylene glycol class diacrylate, 1,4-butanediol diacrylate, 1,6 hexanediol diacrylate, neopentylglycol diacrylate, ethyoxyl neopentylglycol diacrylate, propoxyl group neopentylglycol diacrylate.
Multi-functional acrylate's monomer is any in following material or their mixture: trimethylolpropane trimethacrylate, pentaerythritol triacrylate, ethyoxyl trimethylolpropane trimethacrylate.
Any in the following material of above-mentioned resin: Epocryl, polyurethane acrylic resin, polyester acrylate resin, polyoxyalkylene acrylate resin, acrylate or vinylite.
Any in the following material of above-mentioned light trigger or their mixture: benzil (α; α '-dimethyl benzil ketals); alpha-alcohol ketone (1-hydroxy-cyciohexyl benzophenone, 2-hydroxy-2-methyl-1-phenylacetone, 2-hydroxy-2-methyl-1-are to ethoxy ether phenylacetone); acylphosphine oxide (2; 4,6-trimethyl benzoyl diphenyl base phosphine oxides) etc. light trigger commonly used in the art.
Above-mentioned organic solvent is any in following material or their mixture: ethanol, isopropanol, n-butyl alcohol, ethyl acetate, butyl acetate, acetone, hexamethylene, dichloromethane, chloroform, N, N dimethylformamide, the compatibility of itself and activated monomer and resin is depended in the selection of organic solvent.
Using method based on the anti-fake material constituent of fluorescence quantum provided by the invention is: being added in organic solvent by solid carbonaceous quantum dot, after ultrasound wave is uniformly dispersed, then be proportionally added into activated monomer, resin, light trigger, ultrasonic disperse is uniform；Mixed dispersion liquid is coated on base material, cover the mask with pierced pattern, under high voltage mercury lamp (dominant wavelength is 365nm), expose 1-20min, after removing mask, with organic solvent, mixed dispersion liquid uncured on substrate is rinsed out, obtain water white transparency security pattern.This pattern excites the lower fluorescence that can send different colours at the light of specific wavelength.
Instant invention overcomes the problems such as the organic facies difficulty dispersion of the toxicity of organic fluorescence anti-fake material in conventional fluorescent material and easy aging characteristics and inorganic fluorescent anti-fake material, using carbonaceous quantum dot as anti-fake material, by silk screen printing, nano impression, adding the technology such as mask exposure solidification, to prepare non-toxic, colorless transparent, biocompatibility is good, the security pattern that fluorescence property is stable.
Accompanying drawing explanation
Fig. 1 is the security pattern (glass substrate) (left side) prepared by embodiment 1 and the blue-green fluorescent security pattern (glass substrate) (right side) under ultraviolet excitation.
Detailed description of the invention:
Embodiment 1:
0.8g graphene oxide is dissolved in 30mLN, and in dinethylformamide, ultrasonic disperse is uniform.This dispersion liquid is transferred in the reactor of politef, reacts 7h in 200 DEG C.After being cooled to room temperature, obtain dark thick thing, be centrifuged separating, take upper strata light brown clear liquid, with the quantum dot DMF dispersion liquid obtaining light brown clear after the nylon-66 membrane filtration of 0.22 μm.Solid state quantum point is obtained through revolving steamed journey.The average diameter of gained quantum dot is 20nm, and maximum excitation wavelength is 420nm, and maximum emission wavelength is 510nm.
0.1mg solid state quantum point is joined in 0.20mL acetone, ultrasonic disperse is uniform, being added to by dispersant liquid drop in the mixed liquor of 0.50g esters of acrylic acid low viscosity resin CN294E, 0.50g butyl acrylate, 0.30g neopentylglycol diacrylate and 0.06g2-hydroxy-2-methyl-1-phenylacetone, ultrasonic disperse is uniform again.Mixed dispersion liquid is coated on quartz glass substrate.After this quartz glass is covered the chromium plate mask with specific pierced pattern, 15min is solidified under high voltage mercury lamp (dominant wavelength is 365nm), clean with acetone soln subsequently and remove uncured mixed dispersion liquid, obtain the security pattern that water white transparency is corresponding with openwork part, it is of a size of 10 × 10mm, thickness is about 0.30mm, sends blue-green fluorescent under the ultraviolet excitation of 420nm.
Embodiment 2:
1g multi-walled carbon nano-tubes being dissolved in 100mLN, in dinethylformamide, adds 2g oxidant potassium hydrogen persulfate, ultrasonic disperse is uniform.This dispersion liquid is transferred in the reactor of politef, reacts 10h in 200 DEG C.After being cooled to room temperature, obtain black suspension.After the nylon-66 membrane filtration of 0.22 μm, the product obtained is dialysed with 2000 daltonian bag filters, remove small molecular weight impurity, obtain flaxen quantum dot DMF dispersion liquid.Solid state quantum point is obtained through revolving steamed journey.The average diameter of gained quantum dot is 5nm, and maximum excitation wavelength is 360nm, and maximum emission wavelength is 430nm.
0.20mg solid state quantum point is joined in 0.40mL acetone, ultrasonic disperse is uniform, dispersant liquid drop is added to 0.80g esters of acrylic acid low viscosity resin CN294E, 1.00g 2-(Acryloyloxy)ethanol, 0.80g tripropylene glycol class diacrylate and 0.10g α again, in the mixed liquor of α '-dimethyl benzil ketals, ultrasonic disperse is uniform.Mixed dispersion liquid is coated on quartz glass substrate.After this quartz glass is covered the chromium plate mask with specific pierced pattern, 15min is solidified under high voltage mercury lamp (dominant wavelength is 365nm), clean with acetone soln subsequently and remove uncured mixed dispersion liquid, obtain the security pattern that water white transparency is corresponding with openwork part, it is of a size of 10 × 10mm, thickness is about 0.30mm, sends blue-fluorescence under the ultraviolet excitation of 360nm.
Embodiment 3:
Being dissolved in 25mL deionized water by 1.1g ascorbic acid, be simultaneously introduced 25mL ethanol what stir, ultrasonic disperse is uniform, is transferred in the reactor of politef by this dispersion liquid, reacts 4h in 180 DEG C.After being cooled to room temperature, obtain dark brown solution product.By this solution product of dichloromethane extraction, take the daltonian bag filter dialysis of the aqueous phase 8000-14000 after extraction, remove small molecular weight impurity, obtain flaxen quantum dot aqueous dispersion liquid.Solid carbon quantum dot is obtained through revolving steamed journey.The average ball diameter of gained carbon quantum dot is 30nm, and maximum excitation wavelength is 370nm, and maximum emission wavelength is 550nm.
0.20mg solid carbon quantum dot is joined in 0.5mL acetone, ultrasonic disperse is uniform, dispersant liquid drop is added to 1.00g esters of acrylic acid low viscosity resin CNEB81,1.20g hydroxyethyl methylacrylate, 1.20g Polyethylene Glycol (200) diacrylate and 0.15g α again, in the mixed liquor of α '-dimethyl benzil ketals, ultrasonic disperse is uniform.Mixed dispersion liquid is coated on quartz glass substrate.After this quartz glass is covered the chromium plate mask with specific pierced pattern, 15min is solidified under high voltage mercury lamp (dominant wavelength is 365nm), clean with acetone soln subsequently and remove uncured mixed dispersion liquid, obtain the security pattern that water white transparency is corresponding with openwork part, it is of a size of 10 × 10mm, thickness is about 0.20mm, sends green fluorescence under the ultraviolet excitation of 370nm.
Embodiment 4:
Being dissolved in 20mL deionized water by 1.15g citric acid, ultrasonic disperse is uniform.This dispersion liquid is transferred in the reactor of politef, reacts 4h in 200 DEG C.After being cooled to room temperature, obtain dark-brown transparency liquid.It is centrifuged separating, takes upper strata light brown clear liquid, successively with the water system membrane filtration of 0.45 μm, 0.22 μm, obtain flaxen quantum dot aqueous dispersion liquid.Solid state quantum point is obtained through revolving steamed journey.The average ball diameter of gained quantum dot is 3nm, and maximum excitation wavelength is 310nm, and maximum emission wavelength is 415nm.
0.15mg solid state quantum point is joined in 0.30mL acetone, ultrasonic disperse is uniform, being added to by dispersant liquid drop in 0.75g esters of acrylic acid low viscosity resin CNEB81,0.75g Isooctyl acrylate monomer, 0.75g ethyoxyl neopentylglycol diacrylate and the 0.10g2-hydroxy-2-methyl-1-mixed liquor to ethoxy ether phenylacetone, ultrasonic disperse is uniform again.Mixed dispersion liquid is coated on quartz glass.After this quartz glass is covered the chromium plate mask with specific pierced pattern, 15min is solidified under high voltage mercury lamp (dominant wavelength is 365nm), clean with acetone soln subsequently and remove uncured mixed dispersion liquid, obtain the security pattern that water white transparency is corresponding with openwork part, it is of a size of 10 × 10mm, thickness is about 0.20mm, sends blue-fluorescence under the ultraviolet excitation of 310nm.
Embodiment 5:
Taking 0.09g glucose to be dissolved in 20mL deionized water, ultrasonic disperse is uniform.This dispersion liquid is transferred in the reactor of politef, reacts 8h in 180 DEG C.After being cooled to room temperature, the brown liquid obtained, it is thick product carbon quantum dot.Thick product is performing centrifugal separation on, takes supernatant, obtain carbon quantum dot aqueous dispersion liquid with the water system membrane filtration that aperture is 0.22 μm.After being purified with glucosan G-25 gel column further by dispersion liquid, obtain quantum dot aqueous dispersion liquid.Solid state quantum point is obtained through revolving steamed journey.The average ball diameter of the quantum dot obtained is 5nm, and maximum excitation wavelength is 310nm, and maximum emission wavelength is 440nm.
0.15mg solid state quantum point is distributed in 0.25mL acetone, ultrasonic disperse is uniform, being added to by dispersant liquid drop in 0.60g esters of acrylic acid low viscosity resin CN5850F, 0.80g butyl acrylate, 0.50g diethylene glycol class diacrylate and the 0.10g2-hydroxy-2-methyl-1-mixed liquor to ethoxy ether phenylacetone, ultrasonic disperse is uniform again.Mixed dispersion liquid is coated with on a pet film.After PET film is covered the chromium plate mask with specific pierced pattern, 15min is solidified under high voltage mercury lamp (dominant wavelength is 365nm), clean with acetone soln subsequently and remove uncured mixed dispersion liquid, obtain the security pattern that water white transparency is corresponding with openwork part, it is of a size of 10 × 10mm, thickness is about 0.20mm, sends blue-fluorescence under the ultraviolet excitation of 310nm.
Claims (10)
1., based on an anti-fake material constituent for fluorescence quantum, it substantially forms and with mass fraction is:
A carbonaceous quantum dot 0.001～0.1 part；
B activity monomer 10～70 parts；
C resin 20～50 parts；
D light trigger 1～5 part；
E organic solvent 5～10 parts.
2. anti-fake material constituent according to claim 1, is characterized in that: the mass fraction of carbonaceous quantum dot is 0.005～0.01 part.
3. the anti-fake material constituent according to claim 1 or 2, it is characterized in that: carbonaceous quantum dot is adopted and prepared with the following method: with organic molecule or material with carbon element for carbon source, add in solvent, ultrasonic disperse is uniform, under 150-300 DEG C of condition, carry out solvent thermal reaction 0.5-10h, obtain carbon quantum dot dispersion liquid, purify, rotation obtains solid carbonaceous quantum dot after steaming；Organic molecule is selected from: glucose, fructose, sucrose, ascorbic acid, citric acid, folic acid, glutamic acid, cysteine or glycine；Material with carbon element is selected from: CNT, carbon fiber or Graphene.
4. anti-fake material constituent according to claim 3, is characterized in that: material with carbon element is through the CNT of oxidation processes, carbon fiber or graphene oxide.
5. anti-fake material constituent according to claim 1, is characterized in that: activated monomer is any in simple function group, difunctional, three kinds of functional group reactive acrylate monomer of polyfunctional group or their mixture；
Wherein monofunctional acrylates's ester monomer is any or any two in following material or two or more mixture: butyl acrylate, Isooctyl acrylate monomer, 2-(Acryloyloxy)ethanol, Hydroxypropyl acrylate, hydroxyethyl methylacrylate, Hydroxypropyl methacrylate, glycidyl methacrylate；
Bifunctional acrylate's monomer is any or any two in following material or two or more mixture: diethylene glycol class diacrylate, triethylene glycol class diacrylate, Polyethylene Glycol (200) diacrylate, dipropylene glycol class diacrylate, tripropylene glycol class diacrylate, 1,4-butanediol diacrylate, 1,6 hexanediol diacrylate, neopentylglycol diacrylate, ethyoxyl neopentylglycol diacrylate, propoxyl group neopentylglycol diacrylate；
Multi-functional acrylate's monomer is any or any two in following material or two or more mixture: trimethylolpropane trimethacrylate, pentaerythritol triacrylate, ethyoxyl trimethylolpropane trimethacrylate.
6. anti-fake material constituent according to claim 1, is characterized in that: any in the following material of resin: Epocryl, polyurethane acrylic resin, polyester acrylate resin, polyoxyalkylene acrylate resin, acrylate or vinylite.
7. anti-fake material constituent according to claim 1, is characterized in that: any in the following material of light trigger or their mixture: benzil, alpha-alcohol ketone, acylphosphine oxide.
8. anti-fake material constituent according to claim 7; it is characterized in that: any in the following material of light trigger or their mixture: α; α '-dimethyl benzil ketals, 1-hydroxy-cyciohexyl benzophenone, 2-hydroxy-2-methyl-1-phenylacetone, 2-hydroxy-2-methyl-1-are to ethoxy ether phenylacetone or 2; 4,6-trimethylbenzoy-dipheny phosphine oxides.
9. anti-fake material constituent according to claim 1, it is characterized in that: organic solvent is any in following material or their mixture: ethanol, isopropanol, n-butyl alcohol, ethyl acetate, butyl acetate, acetone, hexamethylene, dichloromethane, chloroform, DMF.
10. based on the using method of the anti-fake material constituent of fluorescence quantum described in a claim 1: be added in organic solvent by carbonaceous quantum dot, after ultrasonic disperse is uniform, then being proportionally added into activated monomer, resin, light trigger, ultrasonic disperse is equal；Mixed dispersion liquid is coated on base material, covers the mask with pierced pattern, under high voltage mercury lamp, expose 1-20min, after removing mask, with organic solvent, mixed dispersion liquid uncured on substrate is rinsed out, obtain water white security pattern.
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| CN106947476A (en) * | 2017-04-03 | 2017-07-14 | 桂林理工大学 | A kind of N doping fluorescence graphene quantum dot and preparation method thereof |
| CN107033884A (en) * | 2016-11-07 | 2017-08-11 | 兰州大学 | A kind of preparation method of carbon quantum dot for Visual retrieval heavy metal ion |
| CN107525790A (en) * | 2017-06-28 | 2017-12-29 | 昆明理工大学 | Method based on magnetic SPME carbon quantum dot fluorescent quenching detection folic acid |
| CN108241262A (en) * | 2016-12-27 | 2018-07-03 | 三星电子株式会社 | Hard mask compositions, the hard mask for forming the method for pattern using hard mask compositions and being formed by hard mask compositions |
| CN110189621A (en) * | 2019-06-27 | 2019-08-30 | 上海碳源汇谷新材料科技有限公司 | A kind of antifalsification label based on graphene |
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| CN108241262A (en) * | 2016-12-27 | 2018-07-03 | 三星电子株式会社 | Hard mask compositions, the hard mask for forming the method for pattern using hard mask compositions and being formed by hard mask compositions |
| CN106947476B (en) * | 2017-04-03 | 2020-06-05 | 桂林理工大学 | Nitrogen-doped fluorescent graphene quantum dot and preparation method thereof |
| CN106947476A (en) * | 2017-04-03 | 2017-07-14 | 桂林理工大学 | A kind of N doping fluorescence graphene quantum dot and preparation method thereof |
| CN107525790A (en) * | 2017-06-28 | 2017-12-29 | 昆明理工大学 | Method based on magnetic SPME carbon quantum dot fluorescent quenching detection folic acid |
| CN110189621A (en) * | 2019-06-27 | 2019-08-30 | 上海碳源汇谷新材料科技有限公司 | A kind of antifalsification label based on graphene |
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