CN108929678B - Anti-counterfeiting ink for industrial and commercial management and preparation method thereof - Google Patents
Anti-counterfeiting ink for industrial and commercial management and preparation method thereof Download PDFInfo
- Publication number
- CN108929678B CN108929678B CN201810870786.0A CN201810870786A CN108929678B CN 108929678 B CN108929678 B CN 108929678B CN 201810870786 A CN201810870786 A CN 201810870786A CN 108929678 B CN108929678 B CN 108929678B
- Authority
- CN
- China
- Prior art keywords
- glutathione
- water
- parts
- soluble copper
- copper sulfide
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
- C09K11/562—Chalcogenides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y20/00—Nanooptics, e.g. quantum optics or photonic crystals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
Abstract
The invention belongs to the technical field of anti-counterfeiting ink, and particularly relates to anti-counterfeiting ink for industrial and commercial management and a preparation method thereof. The method takes copper acetate and sodium sulfide as raw materials, takes small molecular ligand glutathione as a surface modifier, and adopts a coprecipitation method to prepare glutathione-modified water-soluble copper sulfide nanocrystalline; the water-soluble copper sulfide nanocrystal has high purity and narrow emission spectrum, has excellent fluorescence luminous intensity under the excitation of ultraviolet light at 510nm, and can be used as a fluorescent agent for preparing anti-counterfeiting ink for industrial and commercial management.
Description
Technical Field
The invention belongs to the technical field of anti-counterfeiting ink, and particularly relates to anti-counterfeiting ink for industrial and commercial management and a preparation method thereof.
Background
Along with the development of market economy, the types of commodities which can be contacted by people are more and more abundant, meanwhile, the number of fake and counterfeit products is increased, various fake and counterfeit products are enriched on the market, particularly the famous brand of tobacco and wine is the most serious, the rights and interests of consumers are damaged by the fake and counterfeit products, and the product supervision difficulty of the national industrial and commercial administration is greatly increased.
At present, various anti-counterfeiting technologies are adopted by merchants to attack counterfeit and shoddy products, and the national industrial and commercial administration also makes requirements on some anti-counterfeiting technologies; the anti-counterfeiting technology used at present mainly comprises an anti-counterfeiting paper technology, an anti-counterfeiting ink technology, an anti-counterfeiting printing technology, a packaging technology and the like, wherein the anti-counterfeiting ink technology is an extremely important anti-counterfeiting technical field and has a wide application range.
The anti-fake ink is ink with anti-fake function, and is especially ink with anti-fake material added into ink as binder and through special technological process. The anti-counterfeiting ink has an anti-counterfeiting effect depending on special functions of pigments and binders in the ink.
In CN 102993219B, a zinc complex of 2-benzimidazole quinoline is used as a fluorescent pigment to prepare the ultraviolet fluorescent anti-counterfeiting ink, but the synthesis steps of a ligand 2-benzimidazole quinoline compound used by the fluorescent pigment are more complicated, and the stability of the complex product is poorer; the luminescent quantum dots have excellent photoelectric properties, and have various advantages compared with the traditional organic metal complex dye molecules as a latest fluorescent material, such as wide excitation spectrum, continuous distribution, good monochromaticity of the emission spectrum and high stability; the Wuhan university Zhouyanhua project group respectively develops water-soluble ultraviolet fluorescent anti-counterfeiting ink containing graphene quantum dots (CN 106752380A) or carbon quantum dots (CN 107057463A), the high-temperature reaction at 200 ℃ is required in the process of preparing the quantum dots, the luminescent performance of the prepared quantum dots is poor, a large amount of graphene quantum dots or carbon quantum dots are required to be added as luminescent materials of the anti-counterfeiting ink, and the anti-counterfeiting ink is not beneficial to consumers and industrial and commercial managers to attack counterfeit and counterfeit products. Therefore, the development of novel anti-counterfeiting ink with high luminous intensity is the key direction in research and development at present.
Disclosure of Invention
In order to reduce the supervision difficulty of counterfeit and shoddy products in the industrial and commercial management process, the invention provides a fluorescent agent for anti-counterfeiting ink with high luminous intensity, wherein copper acetate and sodium sulfide are used as raw materials, a micromolecule ligand glutathione is used as a surface modifier, and a coprecipitation method is adopted to prepare a glutathione-modified water-soluble copper sulfide nanocrystal; the water-soluble copper sulfide nanocrystal has high purity and narrow emission spectrum, has excellent fluorescence luminous intensity under the excitation of ultraviolet light at 510nm, and can be used as a fluorescent agent for preparing anti-counterfeiting ink for industrial and commercial management.
According to a first aspect of the present invention, the present invention provides a method for preparing a glutathione-modified water-soluble copper sulfide nanocrystal:
1) adding copper acetate and glutathione into water, ultrasonically dissolving, then dropwise adding ammonia water to adjust the pH value of the aqueous solution to 9.0-9.5, and stirring at 50-60 ℃ for 30-60min to obtain a light green solution;
2) dropwise adding a sodium sulfide aqueous solution into the light green solution, transferring the reaction solution into a hydrothermal reaction kettle for hydrothermal reaction at the temperature of 160-180 ℃ for 6-8h after dropwise adding is finished, and cooling to 20-30 ℃ to obtain homogeneous phase hydrosol;
3) adding the homogeneous phase hydrosol into acetone for sedimentation, then centrifuging, pulping and purifying a centrifugal substance by adopting a mixed solution of ethanol and acetone, filtering and drying to obtain the glutathione-modified water-soluble copper sulfide nanocrystal; the volume ratio of ethanol to acetone in the mixed solution is =1: 2.
Preferably, the molar ratio of copper acetate: glutathione =1: 2-5; more preferably copper acetate: glutathione =1: 3;
preferably, the molar ratio of copper acetate: sodium sulfide = 2-4: 1, more preferably copper acetate sodium sulfide =3: 1.
According to another aspect of the invention, the invention provides a use of glutathione-modified water-soluble copper sulfide nanocrystals as fluorescent agents for preparing anti-counterfeiting ink;
preferably, the anti-counterfeiting ink comprises the following components in parts by weight: 38-40 parts of maleic acid modified rosin pentaerythritol ester, 16-18 parts of water-based acrylic resin emulsion, 15-20 parts of pigment, 4-6 parts of glutathione-modified water-soluble copper sulfide nanocrystalline, 2.0-3.0 parts of wollastonite powder with the particle size of 800 meshes, 5-8 parts of isopropanol, 3-5 parts of ethanol, 10-15 parts of deionized water and a proper amount of ethanolamine, wherein the ethanolamine is used for adjusting the pH value of the anti-counterfeiting ink to be alkalescent, and the proper amount refers to that the pH value of an anti-counterfeiting ink system is alkalescent when the ethanolamine is added;
preferably, said weakly basic means pH = 7.5-8.5; the ethanolamine plays a role of an acid-base regulator and an emulsifier, is beneficial to promoting the dissolution of maleic acid modified rosin pentaerythritol ester, balances the stability of a latex polymer in the anti-counterfeiting ink and enables the relative luminous intensity of the anti-counterfeiting ink to be in a stronger state.
Preferably, the pigment is titanium dioxide, gold bright red, benzidine yellow G or phthalocyanine blue BGS;
according to another aspect of the invention, the invention provides a preparation method of the anti-counterfeiting ink, which comprises the following steps: adding isopropanol, ethanol and deionized water into a reaction kettle, heating to 70-75 ℃, adding maleic acid modified rosin pentaerythritol ester in batches, and stirring; adding wollastonite powder with the granularity of 800 meshes after maleic acid modified pentaerythritol rosin ester is completely dissolved, stirring for 1-2h, cooling to 40-45 ℃, adding aqueous acrylic resin emulsion, pigment and glutathione modified water-soluble copper sulfide nanocrystalline, stirring for dissolution, and finally adding ethanolamine to adjust the pH of the system to be alkalescent so as to obtain the anti-counterfeiting ink.
Compared with the prior art, the invention has the following advantages:
1) the method adopts a coprecipitation method to screen out the glutathione-modified water-soluble copper sulfide nanocrystalline with high fluorescence intensity by screening the organic ligand modifier, and the copper sulfide is taken as a non-radioactive fluorescent material, which meets the requirements of green environmental protection compared with a rare earth-doped fluorescent material;
2) in the process of preparing the anti-counterfeiting ink, the prepared anti-counterfeiting ink has excellent fluorescence luminescence property and stability by controlling the addition amount of the ethanolamine.
Drawings
FIG. 1 is a photoluminescence chart of water-soluble copper sulfide nanocrystals prepared by modification of different organic small molecule ligands;
FIG. 2 is a photoluminescence chart of water-soluble copper sulfide nanocrystals prepared by different molar addition amounts of glutathione;
FIG. 3 is a photoluminescence chart of water-soluble copper sulfide nanocrystals prepared by modification with different molar addition amounts of sodium sulfide;
FIG. 4 is a scanning image of a glutathione-modified water-soluble copper sulfide nanocrystalline transmission electron microscope;
FIG. 5 is a photoluminescence graph of security inks obtained at different pH values measured at an excitation wavelength of 410 nm.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention.
Reagent: the maleic acid modified rosin pentaerythritol ester is from PiNOVA of Pinova chemical of America, the type of the Pentalyn G and the acid value of the maleic acid modified rosin pentaerythritol ester are 145mg KOH/G; the water-based acrylic resin emulsion is water-based acrylic resin emulsion 2038 from Shanghao blue treasure Kogyo, the solid content is 38% +/-1, and the pH value is 7.0-7.5.
Example 1
The organic micromolecule ligand is used for carrying out surface modification on the copper sulfide nanocrystal, so that the water solubility of the nanocrystal can be adjusted, and the fluorescence intensity of the nanocrystal can be changed, and in the prior art (Journal of biological Optics 2002, 7(4), 532-537), the fluorescence intensity of the nanocrystal prepared by the organic micromolecule ligand can be enhanced or weakened while the water solubility is improved by modifying the nanocrystal quantum dots; in order to obtain the nanocrystalline with high fluorescence intensity as the anti-counterfeiting ink fluorescent agent, the invention screens the types of the organic micromolecule ligands, and the method comprises the following steps:
1) adding 1.99g of copper acetate monohydrate (10 mmol) and 20mmol of micromolecular ligand into 200ml of water, ultrasonically dissolving, then dropwise adding ammonia water to adjust the pH value of the aqueous solution to 9.0-9.5, and stirring for 30-60min at 50-60 ℃ to obtain a light green solution;
2) dropwise adding a sodium sulfide aqueous solution (containing 20mmol of sodium sulfide) with the concentration of 50mmol/L into the light green solution, transferring the reaction solution into a hydrothermal reaction kettle for hydrothermal reaction at 160-180 ℃ for 6-8h after dropwise adding is finished, and cooling to 20-30 ℃ to obtain homogeneous phase hydrosol;
3) adding the homogeneous hydrosol into 600ml of acetone for sedimentation, centrifuging, pulping 50ml of mixed solution of ethanol and acetone (the volume ratio is calculated, ethanol/acetone =1:2) at 40-45 ℃ for 12-16h, filtering, and drying at 60 ℃ to obtain the organic micromolecule modified water-soluble copper sulfide nanocrystal.
The photoluminescence performance of the water-soluble copper sulfide nanocrystals prepared by modifying different organic small molecules is measured by a fluorescence spectrophotometer (F-4500, manufactured by Hitachi Limited company, Japan), and the excitation wavelength is 410 nm.
The invention tries six organic micromolecule ligands of 3-mercaptopropionic acid (MPA), L-cysteine (Cys), N-acetyl-L-cysteine (NAC), Glutathione (GSH), dihydrolipoic acid (DHLA) and mercaptoethylamine (CA), wherein the 3-mercaptopropionic acid (MPA), the dihydrolipoic acid (DHLA) and the mercaptoethylamine (CA) do not play a role in enhancing the fluorescence intensity; the L-cysteine (Cys), the N-acetyl-L-cysteine (NAC) and the Glutathione (GSH) play a role in enhancing the fluorescence intensity to different degrees, and particularly, the fluorescence intensity of the water-soluble copper sulfide nanocrystal prepared by adopting the Glutathione (GSH) as an organic micromolecule ligand is obviously enhanced.
FIG. 1 is a photoluminescence graph of L-cysteine (Cys), N-acetyl-L-cysteine (NAC) and Glutathione (GSH) modified water-soluble copper sulfide nanocrystals at an excitation wavelength of 410nm, wherein a curve a is a photoluminescence graph of copper sulfide nanocrystals prepared without adding small organic molecules, namely a blank control of copper sulfide nanocrystals without adding small molecular ligands, a curve b is a photoluminescence graph of L-cysteine (Cys) modified water-soluble copper sulfide nanocrystals, a curve c is a photoluminescence graph of N-acetyl-L-cysteine (NAC) modified water-soluble copper sulfide nanocrystals, and a curve d is a photoluminescence graph of Glutathione (GSH) modified water-soluble copper sulfide nanocrystals;
as can be seen from FIG. 1, Glutathione (GSH) is used as a surface modifier of copper sulfide, and the prepared nanocrystal has remarkably enhanced fluorescence intensity and plays a surprising role in enhancing fluorescence; and the fluorescent wavelength of the nanocrystalline prepared by different modifiers generates small-amplitude fluctuation around 510 nm.
Example 2
When Glutathione (GSH) is determined as a modifier, the molar ratio of copper acetate monohydrate to Glutathione (GSH) is optimized by the following method:
1) adding 1.99g of copper acetate monohydrate (10 mmol) and 10-50mmol of glutathione (glutathione) into 200ml of water, ultrasonically dissolving, then dropwise adding ammonia water to adjust the pH value of the aqueous solution to 9.0-9.5, and stirring for 30-60min at 50-60 ℃ to obtain a light green solution;
2) dropwise adding a sodium sulfide aqueous solution (containing 20mmol of sodium sulfide) with the concentration of 50mmol/L into the light green solution, transferring the reaction solution into a hydrothermal reaction kettle for hydrothermal reaction at 160-180 ℃ for 6-8h after dropwise adding is finished, and cooling to 20-30 ℃ to obtain homogeneous phase hydrosol;
3) adding the homogeneous hydrosol into 600ml of acetone for sedimentation, centrifuging, pulping the centrifuged substance by using 50ml of mixed solution of ethanol and acetone (the volume ratio is calculated, ethanol/acetone =1:2) at 40-45 ℃ for 12-16h, filtering, and drying at 60 ℃ to obtain the glutathione-modified water-soluble copper sulfide nano-crystal.
The photoluminescence graphs of the water-soluble copper sulfide nanocrystals prepared by modifying the molar addition amount of different glutathione at the excitation wavelength of 410nm are shown in figure 2: the curve 1 represents the addition amount of 10mmol, the curve 2 represents the addition amount of 20mmol, the curve 3 represents the addition amount of 50mmol, and the curve 4 represents the addition amount of 30 mmol; as can be seen from FIG. 2, the fluorescence intensity of the prepared water-soluble copper sulfide nanocrystal is enhanced with the increase of the molar amount of glutathione, and when the amount of glutathione exceeds 30mmol, the fluorescence intensity is reduced on the contrary, probably because the effective luminescence center of the copper sulfide surface defect is reduced due to excessive glutathione, so that the fluorescence intensity is reduced; therefore, the molar amount of glutathione added was finally determined to be 30 mmol.
Example 3
After the optimal molar addition amount of glutathione is determined, the invention researches the influence of the sodium sulfide dosage on the fluorescence intensity of the product, and the method comprises the following steps:
1) adding 1.99g of copper acetate monohydrate (10 mmol) and 30mmol of glutathione (glutathione) into 200ml of water, ultrasonically dissolving, then dropwise adding ammonia water to adjust the pH value of the aqueous solution to 9.0-9.5, and stirring for 30-60min at 50-60 ℃ to obtain a light green solution;
2) dropwise adding a sodium sulfide aqueous solution (10-50 mmol of sodium sulfide) with the concentration of 50mmol/L into the light green solution, transferring the reaction solution into a hydrothermal reaction kettle for hydrothermal reaction at 160-180 ℃ for 6-8h after dropwise adding, and cooling to 20-30 ℃ to obtain homogeneous hydrosol;
3) adding the homogeneous hydrosol into 600ml of acetone for sedimentation, centrifuging, pulping the centrifuged substance by using 50ml of mixed solution of ethanol and acetone (the volume ratio is calculated, ethanol/acetone =1:2) at 40-45 ℃ for 12-16h, filtering, and drying at 60 ℃ to obtain the glutathione-modified water-soluble copper sulfide nano-crystal.
The photoluminescence patterns of the water-soluble copper sulfide nanocrystals prepared by modifying with different molar addition amounts of sodium sulfide at the excitation wavelength of 410nm are shown in fig. 3: the curve L represents the addition amount of 10mmol, the curve N represents the addition amount of 30mmol, and the curve M represents the addition amount of 50mmol, and it can be seen from the photoluminescence chart that the fluorescence intensity is strongest when the addition amount of sodium sulfide is 30 mmol.
Example 4
1) Adding 1.99g of copper acetate monohydrate (10 mmol) and 30mmol of glutathione (glutathione) into 200ml of water, ultrasonically dissolving, then dropwise adding ammonia water to adjust the pH value of the aqueous solution to 9.0-9.5, and stirring for 30-60min at 50-60 ℃ to obtain a light green solution;
2) dropwise adding a sodium sulfide aqueous solution (containing 30mmol of sodium sulfide) with the concentration of 50mmol/L into the light green solution, transferring the reaction solution into a hydrothermal reaction kettle for hydrothermal reaction at 160-180 ℃ for 6-8h after dropwise adding is finished, and cooling to 20-30 ℃ to obtain homogeneous phase hydrosol;
3) adding the homogeneous hydrosol into 600ml of acetone for sedimentation, centrifuging, pulping 50ml of a mixed solution of ethanol and acetone (ethanol/acetone =1:2) at 40-45 ℃ for 12-16h by using a centrifuge, filtering, and drying at 60 ℃ to obtain the glutathione-modified water-soluble copper sulfide nanocrystal, wherein a scanning image of a transmission electron microscope of the glutathione-modified water-soluble copper sulfide nanocrystal is shown in figure 4, and the glutathione-modified water-soluble copper sulfide nanocrystal is spherical in shape and relatively uniform in particle size distribution and is below 10 nm.
Example 5
The method for preparing the anti-counterfeiting ink by using the glutathione-modified water-soluble copper sulfide nanocrystalline prepared in the embodiment 4 of the invention as a fluorescent agent comprises the following steps:
adding 7 parts by weight of isopropanol, 4 parts by weight of ethanol and 12 parts by weight of deionized water into a reaction kettle, heating to 70-75 ℃, adding 38 parts by weight of maleic acid modified rosin pentaerythritol ester in batches, and stirring; adding 2.5 parts by weight of wollastonite powder with the granularity of 800 meshes after maleic acid modified pentaerythritol rosin ester is completely dissolved, stirring for 1-2h, cooling to 40-45 ℃, adding 17 parts by weight of aqueous acrylic resin emulsion, 5 parts by weight of pigment titanium dioxide and glutathione modified water-soluble copper sulfide nanocrystalline, stirring for dissolution, finally adding acetic acid or ethanolamine to adjust the pH of the system to different values to obtain anti-counterfeiting ink, and measuring different pH values under the condition that the excitation wavelength is 410nm to obtain photoluminescence graphs (only scanning main peak wave bands) of the anti-counterfeiting ink, wherein the photoluminescence graphs are shown in figure 5.
Although the embodiments of the present invention have been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and scope of the invention.
Claims (4)
1. The application of the glutathione-modified water-soluble copper sulfide nanocrystalline is characterized in that: the fluorescent agent is used for preparing anti-counterfeiting ink;
the glutathione-modified water-soluble copper sulfide nanocrystalline is prepared by the following method:
1) adding 1.99g, 10mmol of copper acetate monohydrate and 30mmol of glutathione into 200ml of water, ultrasonically dissolving, then dropwise adding ammonia water to adjust the pH value of the aqueous solution to 9.0-9.5, and stirring for 30-60min at 50-60 ℃ to obtain a light green solution;
2) dropwise adding a sodium sulfide aqueous solution with the concentration of 50mmol/L into the light green solution, wherein the sodium sulfide aqueous solution contains 30mmol of sodium sulfide, transferring the reaction solution into a hydrothermal reaction kettle after dropwise adding, carrying out hydrothermal reaction at the temperature of 160-180 ℃ for 6-8h, and cooling to the temperature of 20-30 ℃ to obtain homogeneous phase hydrosol;
3) adding the homogeneous hydrosol into 600ml of acetone for sedimentation, centrifuging, adopting 50ml of mixed solution of ethanol and acetone as a centrifugal substance, calculating the volume ratio, pulping at 40-45 ℃ for 12-16h with ethanol/acetone =1:2, filtering, and drying at 60 ℃ to obtain the glutathione-modified water-soluble copper sulfide nanocrystal.
2. A security ink for use according to claim 1, wherein: the composition comprises the following components in parts by weight: 38-40 parts of maleic acid modified rosin pentaerythritol ester, 16-18 parts of water-based acrylic resin emulsion, 15-20 parts of pigment, 4-6 parts of glutathione-modified water-soluble copper sulfide nanocrystalline, 2.0-3.0 parts of wollastonite powder with the particle size of 800 meshes, 5-8 parts of isopropanol, 3-5 parts of ethanol, 10-15 parts of deionized water and a proper amount of ethanolamine, wherein the ethanolamine is used for adjusting the pH value of the anti-counterfeiting ink to be alkalescent, and the proper amount refers to that the pH value of an anti-counterfeiting ink system is alkalescent when the ethanolamine is added.
3. A security ink as claimed in claim 2, wherein: the weak alkalinity refers to pH = 7.5-8.5.
4. A method of preparing a security ink as claimed in claim 2 comprising the steps of: adding isopropanol, ethanol and deionized water into a reaction kettle, heating to 70-75 ℃, adding maleic acid modified rosin pentaerythritol ester in batches, and stirring; adding wollastonite powder with the granularity of 800 meshes after maleic acid modified pentaerythritol rosin ester is completely dissolved, stirring for 1-2h, cooling to 40-45 ℃, adding aqueous acrylic resin emulsion, pigment and glutathione modified water-soluble copper sulfide nanocrystalline, stirring for dissolution, and finally adding ethanolamine to adjust the pH of the system to be alkalescent so as to obtain the anti-counterfeiting ink.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810870786.0A CN108929678B (en) | 2018-08-02 | 2018-08-02 | Anti-counterfeiting ink for industrial and commercial management and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810870786.0A CN108929678B (en) | 2018-08-02 | 2018-08-02 | Anti-counterfeiting ink for industrial and commercial management and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108929678A CN108929678A (en) | 2018-12-04 |
| CN108929678B true CN108929678B (en) | 2021-06-25 |
Family
ID=64445248
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810870786.0A Active CN108929678B (en) | 2018-08-02 | 2018-08-02 | Anti-counterfeiting ink for industrial and commercial management and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108929678B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111777093B (en) * | 2020-07-07 | 2022-02-08 | 上海大学 | Preparation method of short rod-shaped nano copper sulfide material |
| CN115094679B (en) * | 2022-07-12 | 2024-01-19 | 山东泰宝包装制品有限公司 | Nitrogen and fluorine co-doped carbon point holographic anti-counterfeiting paper and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100744351B1 (en) * | 2006-03-24 | 2007-07-30 | 삼성전자주식회사 | Ultraviolet luminescence ink and security apparatus using the same |
| CN102838899A (en) * | 2012-09-11 | 2012-12-26 | 东莞市锐达涂料有限公司 | Water-soluble environmental-protection composite printing ink and preparation method thereof |
| CN103073946A (en) * | 2013-01-14 | 2013-05-01 | 山西大学 | Waterborne fluorescent falsification-resistant ink and preparation method thereof |
| CN103121705A (en) * | 2012-12-14 | 2013-05-29 | 深圳先进技术研究院 | Preparation method of CuS nanoparticles, product and application thereof |
| CN104693653A (en) * | 2013-12-05 | 2015-06-10 | 大连奥林匹克电子城利辉通讯器材商行 | Material for preparation of fluorescent anti-counterfeiting mark |
| WO2016090507A1 (en) * | 2014-12-11 | 2016-06-16 | Universidad Andrés Bello | Chemical synthesis of nanoparticles of copper sulphide |
| CN107880651A (en) * | 2017-11-22 | 2018-04-06 | 天津环球磁卡股份有限公司 | A kind of oiliness Antiforge fluorescent ink based on luminescent quantum dot |
-
2018
- 2018-08-02 CN CN201810870786.0A patent/CN108929678B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100744351B1 (en) * | 2006-03-24 | 2007-07-30 | 삼성전자주식회사 | Ultraviolet luminescence ink and security apparatus using the same |
| CN102838899A (en) * | 2012-09-11 | 2012-12-26 | 东莞市锐达涂料有限公司 | Water-soluble environmental-protection composite printing ink and preparation method thereof |
| CN103121705A (en) * | 2012-12-14 | 2013-05-29 | 深圳先进技术研究院 | Preparation method of CuS nanoparticles, product and application thereof |
| CN103073946A (en) * | 2013-01-14 | 2013-05-01 | 山西大学 | Waterborne fluorescent falsification-resistant ink and preparation method thereof |
| CN104693653A (en) * | 2013-12-05 | 2015-06-10 | 大连奥林匹克电子城利辉通讯器材商行 | Material for preparation of fluorescent anti-counterfeiting mark |
| WO2016090507A1 (en) * | 2014-12-11 | 2016-06-16 | Universidad Andrés Bello | Chemical synthesis of nanoparticles of copper sulphide |
| CN107880651A (en) * | 2017-11-22 | 2018-04-06 | 天津环球磁卡股份有限公司 | A kind of oiliness Antiforge fluorescent ink based on luminescent quantum dot |
Non-Patent Citations (3)
| Title |
|---|
| Glutathione-capped, renal-clearable CuS nanodots for photoacoustic imaging and photothermal therapy;Guohai Liang et al.,;《Journal of Materials Chemistry B》;20170628;第5卷;第6366-6375页 * |
| Guohai Liang et al.,.Glutathione-capped, renal-clearable CuS nanodots for photoacoustic imaging and photothermal therapy.《Journal of Materials Chemistry B》.2017,第5卷 * |
| 阳离子掺杂型水溶性ZnS量子点的制备及其应用研究;薛继武;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20140415(第04期);第B018-18页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108929678A (en) | 2018-12-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Liu et al. | Carbon dots: synthesis, formation mechanism, fluorescence origin and sensing applications | |
| CN108192602B (en) | Metal-free polymer carbon dot with room-temperature phosphorescence property, and preparation method and application thereof | |
| Ma et al. | Synthesis and enhancement of carbon quantum dots from Mopan persimmons for Fe3+ sensing and anti-counterfeiting applications | |
| Al-Qahtani et al. | Development of fluorescent carbon dots ink from rice straw waste toward security authentication | |
| CN109021970A (en) | A kind of AgInS2Or CuInS2Extra small quantum dot and its preparation method and application | |
| CN107043576B (en) | Preparation of dual-mode luminous ink, silk-screen printing method and anti-counterfeiting application thereof | |
| CN102517003B (en) | Hydro-thermal preparation method for novel near infrared water-soluble copper-indium-sulfur three-element quantum dots | |
| CN108929678B (en) | Anti-counterfeiting ink for industrial and commercial management and preparation method thereof | |
| CN101503624B (en) | Aqueous phase synthesizing method for transient metal Mn doped ZnSe quantum dot | |
| Huang et al. | Synthesis, size control and fluorescence studies of gold nanoparticles in carboxymethylated chitosan aqueous solutions | |
| Ding et al. | Water-soluble gold nanoclusters with pH-dependent fluorescence and high colloidal stability over a wide pH range via co-reduction of glutathione and citrate | |
| CN106563814A (en) | Method for controllable preparation of triangular silver nanometer plate through photo-induction method and application of triangular silver nanometer plate | |
| Ramanery et al. | Green and facile synthesis of water-soluble ZnS quantum dots nanohybrids using chitosan derivative ligands | |
| CN113817466B (en) | Preparation method of luminescent MOF and perovskite composite nano material | |
| CN105154084A (en) | Preparation method for color-adjustable ternary AgInSe2 fluorescent quantum dots through aqueous-phase synthesis | |
| CN103774502B (en) | A kind of magnetic fluorescence paper false proof coating and preparation method thereof | |
| CN106497560A (en) | Controllable carbon point based compound nano material of luminescent properties and preparation method and application | |
| CN111057537B (en) | Mannose functionalized protein gold nanocluster and preparation method and application thereof | |
| CN109679370A (en) | Preparation method, color lake and its application in color lake | |
| Zhang et al. | NaYF4: Yb, Er with N-GQDs mixture: One-pot hydrothermal synthesis and its luminescent film | |
| CN113736465B (en) | Dual-mode fluorescent nanoparticle composite material, preparation method and application | |
| CN115432673B (en) | Preparation method and application of fluorescent carbon quantum dot-nano selenium | |
| CN103525412B (en) | Method for one-step synthesis of fluorescent carbon nano-particle solution | |
| CN109794618A (en) | The preparation of the copper nano-cluster of sericin package and fluorescence probe | |
| CN111704828B (en) | Encryption ink, anti-counterfeiting encryption method, multiple encryption system and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |