CN110684369A - Water-soluble red organic fluorescent dye and preparation method thereof, and water-based invisible red fluorescent anti-counterfeiting ink and use method thereof - Google Patents
Water-soluble red organic fluorescent dye and preparation method thereof, and water-based invisible red fluorescent anti-counterfeiting ink and use method thereof Download PDFInfo
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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
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B57/00—Other synthetic dyes of known constitution
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/037—Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
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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
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
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Abstract
The invention provides a water-based invisible red fluorescent anti-counterfeiting ink and a preparation method and a use method thereof, fluorescent molecules in a dye aqueous solution used in the ink are not absorbed in a visible light area, so the ink is colorless and transparent under the condition of common sunlight and is completely invisible, and bright fluorescence can be displayed only when the ink is irradiated by ultraviolet light, thereby the contrast and the anti-counterfeiting safety are improved; meanwhile, the water-based invisible fluorescent anti-counterfeiting ink system provided by the invention takes water as a dissolving carrier, is safe and nontoxic, does not generate volatile organic gas, is pollution-free, reduces resource consumption and environmental protection cost, has no burning and explosion risks, and improves the safety of the operating environment compared with the conventional oily dye; in addition, the fluorescent color of the water-based invisible fluorescent anti-counterfeiting ink provided by the invention overcomes the problem that the existing fluorescent anti-counterfeiting dye is single in color.
Description
Technical Field
The invention belongs to the technical field of printing ink, and particularly relates to a water-soluble red organic fluorescent dye and a preparation method thereof, as well as a water-based invisible red fluorescent anti-counterfeiting printing ink and a use method thereof.
Background
Currently, anti-counterfeiting ink can be divided into non-fluorescent anti-counterfeiting ink and fluorescent anti-counterfeiting ink according to the anti-counterfeiting function. The non-fluorescent anti-counterfeiting ink comprises thermochromic ink (such as a thermal response polymer-polyethylene diyne material), photochromic ink (such as azobenzene material and spiropyran material), magnetic color-changing ink (such as ferrocene material), humidity-sensitive color-changing ink (such as siloxane material) and chemical reaction color-changing ink (such as color-changing ink induced by acid-base and indicator reaction, oxidation reduction or enzyme reaction), and the ink is very complex in synthesis, high in cost, poor in stability, short in service life and inconvenient to detect. The second type is fluorescent anti-counterfeiting ink which is prepared from fluorescent dye, namely, corresponding fluorescent compound is added into common ink, and visible fluorescence is displayed under the irradiation of ultraviolet rays. Compared with non-fluorescent ink, the anti-counterfeiting ink has the advantages of convenience and sensitivity in inspection, good safety, good stability and the like, is more concerned in anti-counterfeiting technology, has wider application field, and has been applied to anti-counterfeiting fields of paper money, securities, certificates and the like at home and abroad. The main disadvantages of the fluorescent anti-counterfeiting ink developed at present are as follows: firstly, the materials are absorbed in a visible light area, so that the materials can show a certain color under sunlight, and the anti-counterfeiting effect is reduced; secondly, the fluorescent molecules used in the existing ink are all oil-soluble, only volatile and toxic organic solvents (such as dichloromethane, chloroform, tetrahydrofuran, acetonitrile and the like) can be used in the production and preparation processes, the solvents are not only easy to be absorbed into the body by research and development and workers, causing harm to health, but also easy to diffuse into the atmosphere and polluting the environment, and are all flammable and explosive products, so that great potential safety hazards exist in industrial production (the current frequent chemical plant explosion accidents are mostly caused by the organic solvents and the gases thereof).
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide an aqueous invisible fluorescent anti-counterfeiting ink, a preparation method and a use method thereof, the aqueous invisible red fluorescent anti-counterfeiting ink obtained from the water-soluble red organic fluorescent dye provided by the present invention is colorless and transparent under ordinary sunlight conditions, is completely invisible, shows bright fluorescence only under ultraviolet irradiation, and is safe, non-toxic and pollution-free by using water as a dissolution carrier.
The invention provides a water-soluble red organic fluorescent dye, which has a structure shown in a formula (I):
R1，R2independently selected from hydrophilic aryl, n-3 or 4.
Preferably, said R is1，R2Independently selected from pyridyl, a group obtained by losing hydrogen on one terminal hydroxyl group of polyethylene glycol, a benzene ring modified by hydroxyl, amino or carboxyl, a group obtained by losing hydrogen on one terminal hydroxyl group of polyethylene glycol, and a naphthalene ring modified by hydroxyl, amino or carboxyl.
Preferably, selected from
Wherein m is 1 to 100.
The invention also provides a preparation method of the water-soluble organic fluorescent dye, which comprises the following steps:
A) mixing carboxylic ester compounds and ketone compounds, and carrying out claisen condensation reaction under the catalysis of strong base to obtain beta-diketone compounds;
B) mixing and heating the beta-diketone compound and europium nitrate, and reacting to obtain the water-soluble organic fluorescent dye with the structure shown in the formula (I):
R1，R2independently selected from hydrophilic aryl, n-3 or 4.
Preferably, the carboxylate compound is selected from one or more of methyl nicotinate, ethyl nicotinate, methyl benzoate, ethyl p-methoxybenzoate and ethyl p-hydroxybenzoate;
the ketone compound is selected from one or more of 3-acetylpyridine, acetophenone, p-methoxyacetophenone and p-hydroxyacetophenone;
the strong base is selected from sodium hydroxide, potassium tert-butoxide, sodium tert-butoxide or sodium hydride;
the temperature of the condensation reaction is 35-40 ℃; the condensation reaction time is 2-10 h;
in the step B), the reaction is a heating reflux reaction; the reaction time is 1-1.5 h.
The invention also provides water-based invisible red fluorescent anti-counterfeiting ink which is prepared by mixing the following raw materials in percentage by mass:
10-50 wt% of water-soluble organic fluorescent dye aqueous solution with the structure shown in the formula (I), wherein the mass concentration of the water-soluble organic fluorescent dye in the water-soluble organic fluorescent dye aqueous solution with the structure shown in the formula (I) is 0.5-50 g/L;
50-89 wt% of water-based resin
1 to 3 weight percent of surfactant.
Preferably, the aqueous resin is selected from aqueous acrylic resin, aqueous epoxy resin, aqueous polyurethane resin, aqueous modified polybutadiene resin, aqueous alkyd resin, aqueous amino resin, aqueous polyester resin and aqueous phenolic resin; the surfactant is selected from polyvinylpyrrolidone or sodium dodecyl benzene sulfonate.
The invention also provides a preparation method of the water-based invisible red fluorescent anti-counterfeiting ink, which comprises the following steps:
mixing aqueous resin, a surfactant and an aqueous solution of a water-soluble organic fluorescent dye with a structure shown in a formula (I), and then carrying out ultrasonic treatment to obtain the aqueous invisible red fluorescent anti-counterfeiting ink.
The invention also provides a using method of the water-based invisible red fluorescent anti-counterfeiting ink, which comprises the following steps:
coating or printing the water-based invisible red fluorescent anti-counterfeiting ink on the surface of a product and then drying to obtain an anti-counterfeiting product;
the trace and the color of the water-based invisible fluorescent anti-counterfeiting ink on the surface of the anti-counterfeiting product can not be seen under sunlight, and the area coated or printed with the water-based invisible fluorescent anti-counterfeiting ink on the surface of the product can show fluorescence under the irradiation of an ultraviolet lamp.
Compared with the prior art, the invention provides a water-soluble red organic fluorescent dye, which has a structure shown in a formula (I):
R1，R2independently selected from hydrophilic aryl, n-3 or 4.
The invention provides a water-soluble red organic fluorescent dye, molecules of which do not absorb in a visible light area, so that the obtained ink is colorless and transparent under the condition of common sunlight and is completely invisible, and the obtained ink can only display bright red fluorescence under ultraviolet irradiation, thereby improving the contrast and the anti-counterfeiting safety; meanwhile, the water-based invisible red fluorescent anti-counterfeiting ink system provided by the invention uses water as a dissolving carrier, and compared with the conventional oily dye, the water-based invisible red fluorescent anti-counterfeiting ink system is safe, non-toxic, free of volatile organic gas generation, pollution-free, capable of reducing resource consumption and environmental protection cost, free of burning and explosion risks, and capable of improving the safety of the operation environment; in addition, the fluorescent color of the water-based invisible fluorescent anti-counterfeiting ink provided by the invention is red, and the water-based invisible fluorescent anti-counterfeiting ink can be randomly combined with inks with different colors into different shapes and color patterns, so that the anti-counterfeiting performance is improved, the ink is not easy to copy, and the problem that the existing fluorescent anti-counterfeiting dye is single in color is solved.
Drawings
FIG. 1 is a photograph of the aqueous invisible red fluorescent anti-counterfeiting ink prepared in example 2 under sunlight (left) and ultraviolet light (right);
FIG. 2 is a fluorescence spectrum of the aqueous invisible red fluorescent anti-counterfeiting ink prepared in example 2;
FIG. 3 is a photograph of the aqueous invisible red fluorescent anti-counterfeiting ink prepared in example 4 under sunlight (left) and ultraviolet light (right);
FIG. 4 is a fluorescence spectrum of the aqueous invisible red fluorescent anti-counterfeiting ink prepared in example 4.
Detailed Description
The invention provides a water-soluble red organic fluorescent dye, which has a structure shown in a formula (I):
R1，R2independently selected from hydrophilic aryl, n-3 or 4.
In some embodiments of the invention, R is1，R2Independently selected from pyridyl, a group obtained by losing hydrogen on one terminal hydroxyl group of polyethylene glycol, a benzene ring modified by hydroxyl, amino or carboxyl, a group obtained by losing hydrogen on one terminal hydroxyl group of polyethylene glycol, and a naphthalene ring modified by hydroxyl, amino or carboxyl.
In some embodiments of the invention, R is1，R2Independently selected from pyridyl, a group obtained by losing hydrogen on one terminal hydroxyl of polyethylene glycol, hydroxyl, amino or carboxyl modified benzene ring.
In some embodiments of the invention, the water-soluble red organic fluorescent dye is selected from
The invention also provides a preparation method of the water-soluble organic fluorescent dye, which comprises the following steps:
A) mixing carboxylic ester compounds and ketone compounds, and carrying out claisen condensation reaction under the catalysis of strong base to obtain beta-diketone compounds;
B) mixing and heating the beta-diketone compound and europium nitrate, and reacting to obtain the water-soluble organic fluorescent dye with the structure shown in the formula (I):
R1，R2independently selected from hydrophilic aryl, n-3 or 4.
Specifically, according to the invention, firstly, carboxylic ester compounds and ketone compounds are mixed according to the weight ratio of 1: 1 equivalent was mixed to obtain a mixture. Wherein the carboxylic ester compound is selected from one or more of methyl nicotinate, ethyl nicotinate, methyl benzoate, ethyl p-methoxybenzoate and ethyl p-hydroxybenzoate; the ketone compound is one or more selected from 3-acetylpyridine, acetophenone, p-methoxyacetophenone and p-hydroxyacetophenone.
And then, carrying out a claisen condensation reaction on the mixture under the catalysis of strong alkali to obtain the beta-diketone compound.
Wherein the strong base is selected from sodium hydroxide, potassium tert-butoxide, sodium tert-butoxide or sodium hydride; the temperature of the condensation reaction is 35-40 ℃; the condensation reaction time is 2-10 hours, preferably 4-8 hours;
and then, mixing and heating the beta-diketone compound and europium nitrate for reaction to obtain the water-soluble organic fluorescent dye with the structure shown in the formula (I).
Wherein the reaction is a heating reflux reaction; the reaction time is 1-1.5 h.
The invention also provides water-based invisible red fluorescent anti-counterfeiting ink which is prepared by mixing the following raw materials in percentage by mass:
10-50 wt% of water-soluble organic fluorescent dye aqueous solution with the structure shown in the formula (I), wherein the mass concentration of the water-soluble organic fluorescent dye in the water-soluble organic fluorescent dye aqueous solution with the structure shown in the formula (I) is 0.5-50 g/L;
50-89 wt% of water-based resin
1 to 3 weight percent of surfactant.
The water-based invisible red fluorescent anti-counterfeiting ink provided by the invention comprises 10-50 wt% of water solution of water-soluble organic fluorescent dye with the structure shown in the formula (I), preferably 20-40 wt%, and more preferably 25-35 wt%.
Wherein the mass concentration of the water-soluble organic fluorescent dye in the water solution of the water-soluble organic fluorescent dye with the structure shown in the formula (I) is 0.5-50 g/L, preferably 1.0-30 g/L, and more preferably 5-20 g/L.
The water-based invisible red fluorescent anti-counterfeiting ink provided by the invention also comprises 50 wt% -89 wt% of water-based resin, preferably 55 wt% -80 wt%, and more preferably 60 wt% -70 wt%. The water-based resin is selected from water-based acrylic resin, water-based epoxy resin, water-based polyurethane resin, water-based modified polybutadiene resin, water-based alkyd resin, water-based amino resin, water-based polyester resin and water-based phenolic resin; more preferably an aqueous acrylic resin or an aqueous urethane resin.
The water-based invisible red fluorescent anti-counterfeiting ink provided by the invention also comprises 1 wt% -3 wt% of a surfactant, preferably polyvinylpyrrolidone or sodium dodecyl benzene sulfonate.
The invention also provides a preparation method of the water-based invisible red fluorescent anti-counterfeiting ink, which comprises the following steps:
mixing aqueous resin, a surfactant and an aqueous solution of a water-soluble organic fluorescent dye with a structure shown in a formula (I), and then carrying out ultrasonic treatment to obtain the aqueous invisible red fluorescent anti-counterfeiting ink.
Wherein the time of ultrasonic treatment is 2-5 min, preferably 3 min.
The invention also provides a using method of the water-based red invisible fluorescent anti-counterfeiting ink, which comprises the following steps:
coating or printing the water-based invisible red fluorescent anti-counterfeiting ink on the surface of a product and then drying to obtain an anti-counterfeiting product;
the trace and the color of the water-based invisible red fluorescent anti-counterfeiting ink on the surface of the anti-counterfeiting product can not be seen under sunlight, and the area coated or printed with the water-based invisible fluorescent anti-counterfeiting ink on the surface of the product can show fluorescence under the irradiation of an ultraviolet lamp.
The invention provides water-based invisible red fluorescent anti-counterfeiting ink, wherein fluorescent molecules in a dye aqueous solution used in the ink are not absorbed in a visible light area, so that the ink is colorless and transparent under the condition of common sunlight and is completely invisible, and the ink can display bright fluorescence only under ultraviolet irradiation, thereby improving the contrast and anti-counterfeiting safety; meanwhile, the water-based invisible red fluorescent anti-counterfeiting ink system provided by the invention uses water as a dissolving carrier, and compared with the conventional oily dye, the water-based invisible red fluorescent anti-counterfeiting ink system is safe, non-toxic, free of volatile organic gas generation, pollution-free, capable of reducing resource consumption and environmental protection cost, free of burning and explosion risks, and capable of improving the safety of the operation environment; in addition, the fluorescent color of the water-based invisible fluorescent anti-counterfeiting ink provided by the invention is red, and the water-based invisible fluorescent anti-counterfeiting ink can be randomly combined with inks with different colors into different shapes and color patterns, so that the anti-counterfeiting performance is improved, the ink is not easy to copy, and the problem that the existing fluorescent anti-counterfeiting dye is single in color is solved.
For further understanding of the present invention, the following examples are provided to illustrate the water-soluble red organic fluorescent dye and the preparation method thereof, and the aqueous invisible red fluorescent anti-counterfeiting ink and the using method thereof, and the scope of the present invention is not limited by the following examples.
Example 1
(H1)
The synthesis of (2):
mixing methyl nicotinate and 3-acetylpyridine according to the weight ratio of 1: 1, adding one equivalent of potassium tert-butoxide, and reacting at 40 ℃. Adding a proper amount of water into the mixture obtained after the reaction to completely dissolve the mixture, adjusting the pH value to be neutral by using acetic acid to obtain a large amount of precipitate, and performing suction filtration to obtain the 1, 3-di (pyridine-3-yl) propane-1, 3-diketone.
1, 3-bis (pyridin-3-yl) propane-1, 3-dione (1.47g, 6.5mmol) was dissolved in anhydrous ethanol (25ml) under reflux. After complete dissolution, triethylamine (0.97ml, 7mmol) and europium nitrate (0.89g, 2mmol, dissolved in 10ml ethanol) were added and the reaction was carried out under heating reflux for 1 hour. After the reaction is finished, the product (H1) is obtained by a method of temperature reduction and recrystallization.
MS(ESL,m/z):[M+H]+Calculating C39H28EuN6O6Comprises the following steps: 828.640, results in: 828.639.
1H NMR(400MHz,DMSO):δ9.21(d,J＝16Hz,6H),8.80(dd,J＝48,17Hz, 6H),8.28(ddd,J＝80,20,18Hz,6H),7.47(ddd,J＝80,40,0.8Hz,6H),6.87(s, 3H).13C NMR:δ184.1,162.1,149.6,136.7,133.8,124.5,123.8,83.7.
example 2:
uniformly mixing an aqueous solution (accounting for 10% of the total mass of the ink and having a mass concentration of 5g/L) of the dye with the structural formula in the embodiment 1, an aqueous acrylic resin aqueous solution (accounting for 87% of the total mass of the ink) and polyvinylpyrrolidone (accounting for 3% of the total mass of the ink), and then carrying out ultrasonic treatment for 3 minutes to obtain the aqueous invisible red fluorescent anti-counterfeiting ink; after the coating is coated on cigarette packaging card paper, ink marks and colors on the card paper can not be seen under ordinary sunlight after moisture is dried, and the card paper shows strong red fluorescence under the irradiation of an ultraviolet lamp (figure 1). The emission wavelength was 613nm (FIG. 2) and the quantum yield was 55%.
Example 3
Synthesis of H2:
polyethylene glycol MeO-PEG-Br modified with methoxy and bromo at both ends can be obtained commercially. MeO-PEG-Br and 4-hydroxyacetophenone were mixed as 1: 5, adding 5 equivalents of potassium carbonate, reacting in acetone for 3 days, and performing rotary evaporation and extraction to obtain the PEG functionalized acetophenone. PEG functionalized methyl benzoate can be prepared by the same method. The PEG-functionalized acetophenone and PEG-functionalized methyl benzoate obtained in the previous step were mixed according to the following ratio of 1: 1, adding 2 equivalents of sodium hydride, reacting in tetrahydrofuran solvent for 3 days, neutralizing, extracting, and purifying with silica gel column chromatography to obtain H2 ligand
1H NMR(300MHz,CDCl3):δ17.08(s,0.2H),7.93(m,4H),6.96(m,4H), 6.73(s,1H),4.18(m,4H),3.86(m,4H),3.96～3.53(m,4H),3.37(s,6H).13C NMR (100MHz,CDCl3):δ58.9,67.6,69.5,70.4,71.9,91.6,114.5,129.0,132.1,162.3, 184.6.
The ligand was dissolved in refluxing absolute ethanol, triethylamine and europium nitrate (in which the equivalent ratio of europium nitrate to ligand is 1:3) were added (dissolved in ethanol) to react under heating reflux for 1 hour. After the reaction is finished, the product (H2) is obtained by a method of temperature reduction and recrystallization.
Example 4
Uniformly mixing an aqueous solution (accounting for 10% of the total mass of the ink and having a mass concentration of 5g/L) of the dye with the structural formula (H2) prepared in example 3, an aqueous polyurethane aqueous solution (accounting for 87% of the total mass of the ink) and polyvinylpyrrolidone (accounting for 3% of the total mass of the ink), and performing ultrasonic treatment for 3 minutes to obtain the water-based invisible yellow fluorescent anti-counterfeiting ink; after the coating is coated on cigarette packaging card paper, ink marks and colors on the card paper can not be seen under ordinary sunlight after moisture is dried, and the card paper shows strong red fluorescence under the irradiation of an ultraviolet lamp (figure 3). The emission wavelength was 613nm (FIG. 4) and the quantum yield was 55%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (9)
1. A water-soluble red organic fluorescent dye, which is characterized by having a structure shown in formula (I):
R1，R2independently selected from hydrophilic aryl, n-3 or 4.
2. The water-soluble organic fluorescent dye according to claim 1, wherein R is1，R2Independently selected from pyridyl, a group obtained by losing hydrogen on one terminal hydroxyl group of polyethylene glycol, a benzene ring modified by hydroxyl, amino or carboxyl, a group obtained by losing hydrogen on one terminal hydroxyl group of polyethylene glycol, and a naphthalene ring modified by hydroxyl, amino or carboxyl.
3. The water-soluble organic fluorescent dye according to claim 1, selected from
4. A method for preparing the water-soluble organic fluorescent dye according to claim 1, comprising the steps of:
A) mixing carboxylic ester compounds and ketone compounds, and carrying out claisen condensation reaction under the catalysis of strong base to obtain beta-diketone compounds;
B) mixing and heating the beta-diketone compound and europium nitrate, and reacting to obtain the water-soluble organic fluorescent dye with the structure shown in the formula (I):
R1，R2independently selected from hydrophilic aryl, n-3 or 4.
5. The preparation method according to claim 4, wherein the carboxylic ester compound is selected from one or more of methyl nicotinate, ethyl nicotinate, methyl benzoate, ethyl p-methoxybenzoate and ethyl p-hydroxybenzoate;
the ketone compound is selected from one or more of 3-acetylpyridine, acetophenone, p-methoxyacetophenone and p-hydroxyacetophenone;
the strong base is selected from sodium hydroxide, potassium tert-butoxide, sodium tert-butoxide or sodium hydride;
the temperature of the condensation reaction is 35-40 ℃; the condensation reaction time is 2-10 h;
in the step B), the reaction is a heating reflux reaction; the reaction time is 1-1.5 h.
6. The water-based invisible red fluorescent anti-counterfeiting ink is characterized by comprising the following components in parts by weight: the material is prepared by mixing the following raw materials in percentage by mass:
10-50 wt% of water-soluble organic fluorescent dye aqueous solution with the structure shown in the formula (I), wherein the mass concentration of the water-soluble organic fluorescent dye in the water-soluble organic fluorescent dye aqueous solution with the structure shown in the formula (I) is 0.5-50 g/L;
50-89 wt% of water-based resin
1 to 3 weight percent of surfactant.
7. The aqueous invisible red fluorescent anti-counterfeiting ink according to claim 1, wherein the aqueous resin is selected from aqueous acrylic resin, aqueous epoxy resin, aqueous polyurethane resin, aqueous modified polybutadiene resin, aqueous alkyd resin, aqueous amino resin, aqueous polyester resin and aqueous phenolic resin; the surfactant is selected from polyvinylpyrrolidone or sodium dodecyl benzene sulfonate.
8. The preparation method of the water-based invisible red fluorescent anti-counterfeiting ink according to any one of claims 6 to 7, characterized by comprising the following steps:
mixing aqueous resin, a surfactant and an aqueous solution of a water-soluble organic fluorescent dye with a structure shown in a formula (I), and then carrying out ultrasonic treatment to obtain the aqueous invisible red fluorescent anti-counterfeiting ink.
9. The use method of the water-based invisible red fluorescent anti-counterfeiting ink according to any one of claims 6 to 7, characterized by comprising the following steps:
coating or printing the water-based invisible red fluorescent anti-counterfeiting ink as claimed in any one of claims 6 to 7 on the surface of a product, and drying to obtain an anti-counterfeiting product;
the trace and the color of the water-based invisible fluorescent anti-counterfeiting ink on the surface of the anti-counterfeiting product can not be seen under sunlight, and the area coated or printed with the water-based invisible fluorescent anti-counterfeiting ink on the surface of the product can show fluorescence under the irradiation of an ultraviolet lamp.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112430462A (en) * | 2020-10-27 | 2021-03-02 | 西安理工大学 | Fluorescent pigment, water-based fluorescent anti-counterfeiting ink, and preparation and application thereof |
| CN113754521A (en) * | 2020-06-03 | 2021-12-07 | 马鞍山科思化学有限公司 | Synthetic process method of avobenzone |
| CN117510785A (en) * | 2023-11-02 | 2024-02-06 | 廊坊市安鼎新材料科技有限公司 | Water-based polyurethane with visible light color change and ultraviolet light excited fluorescence, preparation method thereof and application thereof in anti-counterfeiting ink |
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| JP2005044930A (en) * | 2003-07-25 | 2005-02-17 | Toshiba Corp | Led device and ink for forming light emitting layer thereof |
| CN1639281A (en) * | 2002-02-26 | 2005-07-13 | 西巴特殊化学品控股有限公司 | Ink compositions containing lanthanide complexes |
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2018
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113754521A (en) * | 2020-06-03 | 2021-12-07 | 马鞍山科思化学有限公司 | Synthetic process method of avobenzone |
| CN113754521B (en) * | 2020-06-03 | 2023-12-19 | 马鞍山科思化学有限公司 | Synthesis process method of avobenzone |
| CN112430462A (en) * | 2020-10-27 | 2021-03-02 | 西安理工大学 | Fluorescent pigment, water-based fluorescent anti-counterfeiting ink, and preparation and application thereof |
| CN112430462B (en) * | 2020-10-27 | 2024-01-19 | 西安理工大学 | Fluorescent pigment, water-based fluorescent anti-counterfeiting ink and preparation and application thereof |
| CN117510785A (en) * | 2023-11-02 | 2024-02-06 | 廊坊市安鼎新材料科技有限公司 | Water-based polyurethane with visible light color change and ultraviolet light excited fluorescence, preparation method thereof and application thereof in anti-counterfeiting ink |
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