CN111253933A - Room-temperature phosphorescent anti-counterfeiting material with timeliness, and preparation method and application thereof - Google Patents
Room-temperature phosphorescent anti-counterfeiting material with timeliness, and preparation method and application thereof Download PDFInfo
- Publication number
- CN111253933A CN111253933A CN202010230200.1A CN202010230200A CN111253933A CN 111253933 A CN111253933 A CN 111253933A CN 202010230200 A CN202010230200 A CN 202010230200A CN 111253933 A CN111253933 A CN 111253933A
- Authority
- CN
- China
- Prior art keywords
- water
- room
- room temperature
- temperature phosphorescent
- counterfeiting
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 49
- 229920000642 polymer Polymers 0.000 claims abstract description 47
- 239000000126 substance Substances 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002250 absorbent Substances 0.000 claims abstract description 16
- DZBUGLKDJFMEHC-UHFFFAOYSA-N acridine Chemical compound C1=CC=CC2=CC3=CC=CC=C3N=C21 DZBUGLKDJFMEHC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002861 polymer material Substances 0.000 claims abstract description 7
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 6
- 150000003863 ammonium salts Chemical group 0.000 claims abstract description 5
- 239000001913 cellulose Substances 0.000 claims abstract description 5
- 229920002678 cellulose Polymers 0.000 claims abstract description 5
- 229920000141 poly(maleic anhydride) Polymers 0.000 claims abstract description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 5
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 3
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004584 polyacrylic acid Substances 0.000 claims abstract description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 3
- 229920005989 resin Polymers 0.000 claims abstract description 3
- 239000011347 resin Substances 0.000 claims abstract description 3
- 239000002904 solvent Substances 0.000 claims description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
- 230000008961 swelling Effects 0.000 claims description 12
- GDALETGZDYOOGB-UHFFFAOYSA-N Acridone Natural products C1=C(O)C=C2N(C)C3=CC=CC=C3C(=O)C2=C1O GDALETGZDYOOGB-UHFFFAOYSA-N 0.000 claims description 10
- DPKHZNPWBDQZCN-UHFFFAOYSA-N acridine orange free base Chemical compound C1=CC(N(C)C)=CC2=NC3=CC(N(C)C)=CC=C3C=C21 DPKHZNPWBDQZCN-UHFFFAOYSA-N 0.000 claims description 10
- FZEYVTFCMJSGMP-UHFFFAOYSA-N acridone Chemical group C1=CC=C2C(=O)C3=CC=CC=C3NC2=C1 FZEYVTFCMJSGMP-UHFFFAOYSA-N 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000001704 evaporation Methods 0.000 claims description 9
- BGLGAKMTYHWWKW-UHFFFAOYSA-N acridine yellow Chemical compound [H+].[Cl-].CC1=C(N)C=C2N=C(C=C(C(C)=C3)N)C3=CC2=C1 BGLGAKMTYHWWKW-UHFFFAOYSA-N 0.000 claims description 8
- 238000007334 copolymerization reaction Methods 0.000 claims description 8
- 238000005342 ion exchange Methods 0.000 claims description 8
- 239000000178 monomer Substances 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 229920002401 polyacrylamide Polymers 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000013329 compounding Methods 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 claims description 2
- 238000010128 melt processing Methods 0.000 claims description 2
- 238000004806 packaging method and process Methods 0.000 claims description 2
- 229920000867 polyelectrolyte Polymers 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000007639 printing Methods 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 6
- 230000003679 aging effect Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000010276 construction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 26
- 230000001276 controlling effect Effects 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- QEUYATCJHJUQML-UHFFFAOYSA-N acridine-3,6-diamine;10-methylacridin-10-ium-3,6-diamine;chloride;hydrochloride Chemical compound Cl.[Cl-].C1=CC(N)=CC2=NC3=CC(N)=CC=C3C=C21.C1=C(N)C=C2[N+](C)=C(C=C(N)C=C3)C3=CC2=C1 QEUYATCJHJUQML-UHFFFAOYSA-N 0.000 description 6
- 229940002707 acriflavine hydrochloride Drugs 0.000 description 6
- 230000008859 change Effects 0.000 description 3
- 235000019504 cigarettes Nutrition 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 235000014101 wine Nutrition 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- -1 acridone ethanol Chemical compound 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 229920006125 amorphous polymer Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 239000006223 plastic coating Substances 0.000 description 2
- 230000001550 time effect Effects 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 244000025254 Cannabis sativa Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000001066 destructive effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000024437 response to mechanical stimulus Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Wrappers (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The invention discloses a room temperature phosphorescent anti-counterfeiting material with timeliness, and a preparation method and application thereof. The room temperature phosphorescent material is compounded into the water-absorbent polymer, so that the polymer material with the aging property, long service life and room temperature phosphorescent light-emitting characteristic can be obtained; the room temperature phosphorescent substance is one or more selected from acridine and derivatives thereof, phthalic acid and derivatives thereof, or melamine and derivatives thereof; the water-based polymer is one or more selected from polyacrylic acid resin, cellulose and its derivatives, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt or polyethylene glycol. The anti-counterfeiting label is simple and effective in construction, can quickly realize time-efficient room-temperature phosphorescence anti-counterfeiting, and can effectively discriminate whether the package is unsealed and the real delivery time of the commodity. Moreover, the present invention can be obtained by an aqueous printing process, which has great advantages in terms of cost and environmental friendliness.
Description
Technical Field
The invention belongs to the technical field of optical anti-counterfeiting materials. More particularly, relates to a room temperature phosphorescent anti-counterfeiting material with timeliness, and a preparation method and application thereof.
Background
Optical anti-counterfeiting is one of the most important anti-counterfeiting means, and a large number of commodities in the market use anti-counterfeiting trademarks, and are particularly commonly used in the industries of cigarettes, wines and cosmetics. However, the conventional anti-counterfeit trademark cannot have the time-efficiency function of marking whether the commodity package is unsealed or not and the real delivery time of the commodity.
Phosphorescence has a larger Stokes shift than fluorescence, and can avoid interference of excitation light. And meanwhile, phosphorescence has longer service life, and can avoid the interference of fluorescence and scattered light with short service life, thereby obtaining lower detection limit. Fluorescence has been widely used in the anti-counterfeit field due to its simple lighting conditions and convenient use, such as the fluorescent technology used in the anti-counterfeit of Renminbi. Phosphorescence requires low temperature conditions for controlling non-radiative transitions of phosphorescent molecules, which greatly limits the application of phosphorescence. The room temperature phosphorescence developed later controls the non-radiative transition of phosphorescent molecules and has mild light emitting condition, so that the room temperature phosphorescence can be widely applied to the fields of life science, environmental science, medical clinic, industrial energy, anti-counterfeiting and the like. The room temperature phosphorescence realizes control methods such as temperature response, mechanical stimulus response and the like to regulate and control the starting and the intensity of the room temperature phosphorescence, but the methods are often destructive and complicated in operation process.
The photoresponse is a nondestructive and non-contact simple control method, and can conveniently realize the starting of room-temperature phosphorescence and the regulation and control of phosphorescence intensity. The professor task group of offer offers and field grass of east China university reports a simple and convenient method for preparing a pure organic high-efficiency room temperature phosphorescent emissive solid amorphous polymer material and application thereof: firstly, monomer compounds containing phosphor dyes are synthesized through simple steps of reaction, then the monomer compounds are copolymerized with acrylamide, and based on the interaction of hydrogen bonds in a polymer system, amorphous polymer materials with efficient room-temperature phosphorescence emission performance are obtained. Because hydrogen bonding in polymer systems is sensitive to water, the room temperature phosphorescent emission of the solid amorphous material responds to air humidity, and the organic solution system also responds to the moisture content in the solid amorphous material. However, the reported monomer compound is complex to synthesize, high in cost, incapable of regulating and controlling the phosphorescence intensity and the timeliness, and inconvenient to use. Especially in the anti-counterfeiting field, the anti-counterfeiting grade is reduced.
Disclosure of Invention
The invention aims to overcome the defects and shortcomings of the prior art and provide a room-temperature phosphorescent anti-counterfeiting material with timeliness, and a preparation method and application thereof.
The above purpose of the invention is realized by the following technical scheme:
a room temperature phosphorescence anti-counterfeiting material with timeliness is prepared by compounding a room temperature phosphorescence substance into a water-absorbent polymer to obtain a polymer material with timeliness, long service life and room temperature phosphorescence luminescence characteristics;
wherein the room temperature phosphorescent substance is one or more selected from acridine and derivatives thereof, phthalic acid and derivatives thereof, or melamine and derivatives thereof;
the water-absorbing polymer is one or more selected from polyacrylic acid resin, cellulose and derivatives thereof, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt or polyethylene glycol.
In order to overcome the problems of the conventional optical anti-counterfeiting material, the room-temperature phosphorescent material is compounded with the water-absorbing polymer, so that the anti-counterfeiting label can be simply, quickly and effectively constructed, the room-temperature phosphorescent anti-counterfeiting with timeliness can be quickly realized, and whether a package is unsealed or not and the real delivery time of a commodity can be effectively discriminated. Moreover, the reaction system adopted by the invention can be completely obtained by an aqueous printing process, and has great advantages in terms of cost and environmental friendliness.
The room temperature phosphorescent material is compounded into the water-absorbent polymer, so that the anti-counterfeiting material absorbs moisture in the air to lose phosphorescence after the sealed package is opened through the water absorption of the polymer, the discrimination anti-counterfeiting function of judging whether the commodity package is opened or not and the indication anti-counterfeiting function of indicating the real time of commodity delivery are achieved, and the anti-counterfeiting material has important application value and wide application prospect in the industries with time-efficiency anti-counterfeiting requirements of valuable cigarettes, wines, medicines, foods and the like.
In a preferred embodiment of the present invention, the mass ratio of the room temperature phosphorescent material to the water-absorbent polymer is 1: 1000 to 7000.
Further, in a preferred embodiment of the present invention, the mass ratio of the room temperature phosphorescent material to the water-absorbent polymer is 1: 3000-5000.
Further, in a preferred embodiment of the present invention, the mass ratio of the room temperature phosphorescent material to the water-absorbent polymer is 1: 4000.
the luminous efficiency is reduced due to aggregation caused by the fact that the proportion of the room-temperature phosphorescent substance is too high; too low a proportion of the room-temperature phosphorescent substance also causes insufficient luminous intensity and no phosphorescence to be observed with the naked eye. The applicant found through creative work that the mass ratio of the room temperature phosphorescent material to the water-absorbent polymer is 1: 1000 to 7000, preferably 1: 3000-5000, more preferably 1: 4000 hours, the compound has good luminous efficiency, luminous intensity and luminous life, and the controllable adjustment range of the visible color of naked eyes is wide.
In a preferred embodiment of the present invention, the compounding method is any one of a solution swelling method, an ion exchange method, a copolymerization method, a solution forming method, or a blending method;
wherein the solution swelling method is: swelling the water-absorbing polymer by using a solution of a room-temperature phosphorescent substance, and evaporating to remove the solvent to obtain the water-absorbing polymer;
the ion exchange method comprises the following steps: performing ion exchange on the ionic room-temperature phosphorescent substance and the water-absorbent polymer by using a polyelectrolyte exchange counter ion method, and evaporating to remove the solvent to obtain the compound material;
the copolymerization method comprises the following steps: carrying out copolymerization reaction on the room-temperature phosphorescent material and a water-absorbing polymer monomer or carrying out grafting reaction on the room-temperature phosphorescent material and the water-absorbing polymer monomer to obtain the polymer material;
the solution forming method comprises the following steps: dissolving the room temperature phosphorescent material and the water-absorbing polymer in a solvent together, and evaporating to remove the solvent to obtain the compound;
the blending method comprises the following steps: and (3) carrying out melt processing and blending on the room-temperature phosphorescent substance and the water-absorbing polymer to obtain the polymer.
In a preferred embodiment of the present invention, the phosphorescent substance at room temperature is selected from acridone, acridine orange hydrochloride, acridine yellow hydrochloride or a combination thereof.
In a preferred embodiment of the invention, the water-absorbent polymer is selected from the group consisting of polyacrylamides.
In a preferred embodiment of the present invention, the compounding process is a solution swelling process.
In a preferred embodiment of the invention, the solvent is water.
In a preferred embodiment of the present invention, the mass fraction of the room temperature phosphorescent substance solution is 0.01% to 1%, preferably 0.01% to 0.1%. The mass fraction of the room-temperature phosphorescent substance solution directly determines the mass ratio of the room-temperature phosphorescent substance to the water-absorbent polymer, and the excessively high room-temperature phosphorescent substance ratio causes the reduction of the luminous efficiency caused by aggregation; too low a proportion of the room-temperature phosphorescent substance also causes insufficient luminous intensity and no phosphorescence to be observed with the naked eye. The applicant finds out through creative work that when the mass fraction of the room-temperature phosphorescent substance solution is 0.01-1%, preferably 0.01-0.1%, the luminous efficiency, luminous intensity and luminous life of the compound are good, and the compound also has a wide visible color adjustable range and can be in a full visible spectrum color from blue to red.
The invention also relates to the room temperature phosphorescence anti-counterfeiting material with timeliness prepared by the preparation method.
The invention also relates to application of the room temperature phosphorescent anti-counterfeiting material with timeliness prepared by the preparation method in serving as a packaging sealing strip type anti-counterfeiting material or an indicator of delivery time.
Compared with the prior art, the invention has the following beneficial effects:
(1) the room temperature phosphorescent material has timeliness, shows the strongest phosphorescent property when being completely dried, and gradually absorbs moisture to lose phosphorescence after contacting air, thereby realizing the timeliness which is not possessed by a common anti-counterfeiting label.
(2) The room temperature phosphorescent material has water-based printing property, and patterns can be obtained by simple aqueous solution printing, so that the room temperature phosphorescent material has the advantages of low cost and easiness in processing.
Drawings
FIG. 1 is a graph showing the effect of the room temperature phosphorescent material with aging property prepared in example 1.
Fig. 2 is a diagram showing the effect of the printed matter of the room temperature phosphorescent material having the aging property, wherein the left diagram is a state where the printed pattern is under the ultraviolet lamp, and the right diagram is a state where the printed pattern is after the ultraviolet lamp is turned off.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
1. A preparation method of room temperature phosphorescent anti-counterfeiting material with timeliness comprises the following steps:
the preparation method is characterized by adopting a solution forming method, dissolving acridone and polyacrylamide serving as a water-absorbing polymer in solvent water together, and controlling the mass ratio of acridone to polyacrylamide to be 1: 4000, the mass fraction of the acridone solution is 0.1%, and then the solvent water is removed by heating and evaporation at 100 ℃, so as to obtain the room-temperature phosphorescent anti-counterfeiting material with timeliness. As shown in figure 1, the room temperature phosphorescent anti-counterfeiting material presents blue fluorescence under an ultraviolet lamp, long-life green phosphorescence appears after the lamp is turned off, and the room temperature phosphorescent anti-counterfeiting material gradually loses phosphorescence when exposed to air with the relative humidity of 50%, so that the aim of effectively discriminating the real factory leaving time of commodities is fulfilled.
Example 2
1. A preparation method of room temperature phosphorescent anti-counterfeiting material with timeliness comprises the following steps:
the preparation method is characterized by adopting a solution swelling method, dissolving acriflavine hydrochloride in water to form an acriflavine hydrochloride aqueous solution with the mass fraction of 0.03%, using a water-absorbing polymer polyacrylamide film as a base material, and using the acriflavine hydrochloride aqueous solution as ink to perform ink-jet printing; after the pattern is printed, the pattern is dried for 1 hour at the temperature of 90 ℃, and is sealed by plastic coating, so that the green fluorescent-green phosphorescent pattern shown in figure 2 can be formed. When the sealed bag is opened, the phosphorescence characteristic will disappear gradually within 2 hours, and the fluorescence characteristic will not change obviously, thus achieving the discrimination anti-counterfeiting target of whether the commodity package is unsealed.
Example 3
1. A preparation method of room temperature phosphorescent anti-counterfeiting material with timeliness comprises the following steps:
the preparation method is characterized by adopting a solution swelling method, dissolving acriflavine hydrochloride in water to form an acriflavine hydrochloride aqueous solution with the mass fraction of 0.01%, using a water-absorbing polymer polyacrylamide film as a base material, and using the acriflavine hydrochloride aqueous solution as ink to perform ink-jet printing; after the pattern is printed, the pattern is dried for 1 hour at 90 ℃ and sealed by plastic coating, and a green fluorescent-green phosphorescent pattern as shown in figure 2 is also formed. When the sealed pouch is opened, the phosphorescent characteristics gradually disappear within 2 to 3 hours, and the fluorescent characteristics do not significantly change.
Example 4
The method comprises the steps of adopting a solution swelling method, dissolving acridone in ethanol to form an acridone solution with the mass fraction of 0.02%, using a cross-linked polyacrylic film as a base material, using an acridone ethanol solution as ink of a stamp, absorbing the ink by using a wooden stamp, covering the ink on the polyacrylic film for 1min, then drying the film at 100 ℃, and performing plastic sealing to obtain the blue fluorescence-green fluorescence anti-counterfeiting pattern. When the sealing bag is opened, the phosphorescence characteristics can gradually disappear within 0.5 hour, and the fluorescence characteristics can not obviously change, so that the time-effect room-temperature phosphorescence anti-counterfeiting after the sealing bag is opened once is realized.
Example 5
1. A preparation method of room temperature phosphorescent anti-counterfeiting material with timeliness comprises the following steps:
dissolving acridine orange hydrochloride in water to form an aqueous solution with the mass fraction of 0.01% by adopting a solution swelling method, printing a label by using polyvinyl alcohol as a base material and acridine orange hydrochloride solution as printing ink, drying the film at 90 ℃, and sealing by using a polyethylene film with the thickness of 0.1mm to obtain the orange fluorescence-yellow fluorescence anti-counterfeiting pattern. The obtained anti-counterfeiting label gradually loses the phosphorescence characteristic in the process of 12 months, and long-acting time-effect room-temperature phosphorescence anti-counterfeiting is realized.
Example 6
1. A preparation method of room temperature phosphorescent anti-counterfeiting material with timeliness comprises the following steps:
the preparation method is characterized by adopting a solution forming method, dissolving acridone and polyvinylpyrrolidone serving as a water-absorbing polymer in ethanol serving as a solvent together, and controlling the mass ratio of acridone to polyvinylpyrrolidone to be 1: 3000, the mass fraction of the acridone solution is 0.05 percent, and then the solvent is removed by heating and evaporation at 100 ℃ to obtain the room-temperature phosphorescent anti-counterfeiting material with timeliness. The room temperature phosphorescence anti-counterfeiting material shows fluorescence under an ultraviolet lamp, long-life phosphorescence appears after the lamp is turned off, and the room temperature phosphorescence anti-counterfeiting material gradually loses phosphorescence when being exposed to air with the relative humidity of 50 percent, so that the aim of effectively discriminating the real factory leaving time of commodities is fulfilled.
Example 7
1. A preparation method of room temperature phosphorescent anti-counterfeiting material with timeliness comprises the following steps:
the preparation method is characterized by adopting an ion exchange method, dissolving acridine orange hydrochloride and water-absorbing polymer polyquaternary ammonium salt into solvent water together for ion exchange, and controlling the mass ratio of the acridine orange hydrochloride to the polyquaternary ammonium salt to be 1: 5000, the mass fraction of the acridine orange hydrochloride solution is 0.5%, and then the solvent water is removed by heating and evaporation at 100 ℃, so as to obtain the room-temperature phosphorescent anti-counterfeiting material with timeliness. The room temperature phosphorescence anti-counterfeiting material shows fluorescence under an ultraviolet lamp, long-life phosphorescence appears after the lamp is turned off, and the room temperature phosphorescence anti-counterfeiting material gradually loses phosphorescence when being exposed to air with relative humidity of 55%, so that the aim of effectively discriminating the real factory leaving time of commodities is fulfilled.
Example 8
1. A preparation method of room temperature phosphorescent anti-counterfeiting material with timeliness comprises the following steps:
the preparation method is characterized by adopting a copolymerization method, dissolving acridine yellow hydrochloride and water-absorbing polymer polymaleic anhydride into solvent water together for grafting, and controlling the mass ratio of the acridine yellow hydrochloride to the polymaleic anhydride to be 1: 1000, the mass fraction of the acridine orange hydrochloride solution is 1%, and removing solvent water to obtain the room-temperature phosphorescent anti-counterfeiting material with timeliness. The room temperature phosphorescence anti-counterfeiting material shows fluorescence under an ultraviolet lamp, long-life phosphorescence appears after the lamp is turned off, and the room temperature phosphorescence anti-counterfeiting material gradually loses phosphorescence when being exposed to air with the relative humidity of 40 percent, so that the aim of effectively discriminating the real factory leaving time of commodities is fulfilled.
Example 9
1. A preparation method of room temperature phosphorescent anti-counterfeiting material with timeliness comprises the following steps:
the preparation method is characterized by adopting a copolymerization method, dissolving acridine yellow hydrochloride and water-absorbing polymer polyvinyl alcohol into solvent water together for grafting, and controlling the mass ratio of the acridine yellow hydrochloride to the polyvinyl alcohol to be 1: 7000, the mass fraction of the acridine orange hydrochloride solution is 0.8%, and the solvent water is removed to obtain the room-temperature phosphorescent anti-counterfeiting material with timeliness. The room temperature phosphorescence anti-counterfeiting material shows fluorescence under an ultraviolet lamp, long-life phosphorescence appears after the lamp is turned off, and the room temperature phosphorescence anti-counterfeiting material gradually loses phosphorescence when being exposed to air with the relative humidity of 45 percent, so that the aim of effectively discriminating the real factory leaving time of commodities is fulfilled.
Example 10
1. A preparation method of room temperature phosphorescent anti-counterfeiting material with timeliness comprises the following steps:
the preparation method is characterized by adopting a solution swelling method, dissolving acridine yellow hydrochloride and water-absorbing polymer cellulose in ethanol as a solvent for composite reaction, and controlling the mass ratio of the acridine yellow hydrochloride to the cellulose to be 1: 6000, the mass fraction of the acridine orange hydrochloride solution is 0.7 percent, and the solvent is removed to obtain the room-temperature phosphorescent anti-counterfeiting material with timeliness. The room temperature phosphorescence anti-counterfeiting material shows fluorescence under an ultraviolet lamp, long-life phosphorescence appears after the lamp is turned off, and the room temperature phosphorescence anti-counterfeiting material gradually loses phosphorescence when being exposed to air with the relative humidity of 60%, so that the aim of effectively discriminating the real factory leaving time of commodities is fulfilled.
The room temperature phosphorescent material has timeliness, shows the strongest phosphorescent property when being completely dried, and gradually absorbs moisture to lose phosphorescence after contacting air, thereby realizing the timeliness which is not possessed by a common anti-counterfeiting label; and has water-based printability, and can obtain patterns by simple aqueous solution printing, so that the printing ink has the advantages of low cost and easy processing.
The room temperature phosphorescent material is compounded into the water-absorbent polymer, so that the anti-counterfeiting material absorbs moisture in the air to lose phosphorescence after the sealed package is opened through the water absorption of the polymer, the discrimination anti-counterfeiting function of judging whether the commodity package is opened or not and the indication anti-counterfeiting function of indicating the real time of commodity delivery are achieved, and the anti-counterfeiting material has important application value and wide application prospect in the industries with time-efficiency anti-counterfeiting requirements of valuable cigarettes, wines, medicines, foods and the like.
The applicant declares that the above detailed description is a preferred embodiment described for the convenience of understanding the present invention, but the present invention is not limited to the above embodiment, i.e. it does not mean that the present invention must be implemented by means of the above embodiment. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (10)
1. A preparation method of room temperature phosphorescence anti-counterfeiting material with timeliness is characterized in that room temperature phosphorescence material is compounded into water-absorbing polymer, so that polymer material with timeliness, long service life and room temperature phosphorescence luminescence characteristics can be obtained;
wherein the room temperature phosphorescent substance is one or more selected from acridine and derivatives thereof, phthalic acid and derivatives thereof, or melamine and derivatives thereof;
the water-absorbing polymer is one or more selected from polyacrylic acid resin, cellulose and derivatives thereof, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt or polyethylene glycol.
2. The production method according to claim 1, wherein the mass ratio of the room-temperature phosphorescent substance to the water-absorbent polymer is 1: 1000 to 7000.
3. The production method according to claim 2, wherein the mass ratio of the room-temperature phosphorescent substance to the water-absorbent polymer is 1: 3000-5000.
4. The production method according to claim 3, wherein the mass ratio of the room-temperature phosphorescent substance to the water-absorbent polymer is 1: 4000.
5. the method according to claim 1, wherein the compounding method is any one of a solution swelling method, an ion exchange method, a copolymerization method, a solution forming method, or a blending method;
the solution swelling method comprises the following steps: swelling the water-absorbing polymer by using a solution of a room-temperature phosphorescent substance, and evaporating to remove the solvent to obtain the water-absorbing polymer;
the ion exchange method comprises the following steps: performing ion exchange on the ionic room-temperature phosphorescent substance and the water-absorbent polymer by using a polyelectrolyte exchange counter ion method, and evaporating to remove the solvent to obtain the compound material;
the copolymerization method comprises the following steps: carrying out copolymerization reaction on the room-temperature phosphorescent material and a water-absorbing polymer monomer or carrying out grafting reaction on the room-temperature phosphorescent material and the water-absorbing polymer monomer to obtain the polymer material;
the solution forming method comprises the following steps: dissolving the room temperature phosphorescent material and the water-absorbing polymer in a solvent together, and evaporating to remove the solvent to obtain the compound;
the blending method comprises the following steps: and (3) carrying out melt processing and blending on the room-temperature phosphorescent substance and the water-absorbing polymer to obtain the polymer.
6. The method according to claim 5, wherein the phosphorescent substance at room temperature is selected from acridone, acridine orange hydrochloride, acridine yellow hydrochloride, or a combination thereof.
7. A production method according to claim 6, characterized in that the water-absorbent polymer is selected from polyacrylamides.
8. The method according to claim 5, wherein the solvent is water; the mass fraction of the room temperature phosphorescent substance solution is 0.01-1%.
9. The room temperature phosphorescent anti-counterfeiting material with timeliness prepared by the preparation method of any one of claims 1 to 8.
10. The application of the room-temperature phosphorescent anti-counterfeiting material with timeliness prepared by the preparation method of any one of claims 1 to 8 in serving as a packaging sealing strip type anti-counterfeiting material or an indicator of delivery time.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010230200.1A CN111253933B (en) | 2020-03-27 | 2020-03-27 | Room-temperature phosphorescent anti-counterfeiting material with timeliness, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010230200.1A CN111253933B (en) | 2020-03-27 | 2020-03-27 | Room-temperature phosphorescent anti-counterfeiting material with timeliness, and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111253933A true CN111253933A (en) | 2020-06-09 |
| CN111253933B CN111253933B (en) | 2021-08-13 |
Family
ID=70949981
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010230200.1A Active CN111253933B (en) | 2020-03-27 | 2020-03-27 | Room-temperature phosphorescent anti-counterfeiting material with timeliness, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111253933B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111607394A (en) * | 2020-06-17 | 2020-09-01 | 太原理工大学 | Room temperature phosphorescent carbon dot compound and preparation method thereof |
| CN111763512A (en) * | 2020-06-24 | 2020-10-13 | 中山大学 | Application of polyvinyl benzene sulfonic acid or salt thereof as room temperature phosphorescent material |
| CN112707922A (en) * | 2020-12-24 | 2021-04-27 | 河北工业大学 | Color-adjustable hectorite and 4,4' -biphenyldicarboxylic acid hybridized room temperature phosphorescent material |
| CN113025325A (en) * | 2021-03-25 | 2021-06-25 | 盐城工学院 | Preparation method and application of room-temperature phosphorescent carbon-based composite material capable of changing color under single excitation source |
| CN113789168A (en) * | 2021-10-08 | 2021-12-14 | 中山大学 | Thermal activation delayed fluorescence material and preparation method and application thereof |
| CN114621752A (en) * | 2021-12-03 | 2022-06-14 | 昆明理工大学 | Room-temperature phosphorescent waterborne polymer anti-counterfeiting material and preparation method and application thereof |
| CN115161014A (en) * | 2022-06-09 | 2022-10-11 | 昆明理工大学 | Preparation method and application of doped room temperature phosphorescent waterborne polymer anti-counterfeiting material |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188391A (en) * | 2016-07-18 | 2016-12-07 | 华东理工大学 | A kind of pure organic room temperature phosphorimetry fluorescence double polymeric material launched of humidity response |
-
2020
- 2020-03-27 CN CN202010230200.1A patent/CN111253933B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106188391A (en) * | 2016-07-18 | 2016-12-07 | 华东理工大学 | A kind of pure organic room temperature phosphorimetry fluorescence double polymeric material launched of humidity response |
Non-Patent Citations (2)
| Title |
|---|
| [美]T.VO-DINH著: "《室温磷光化学分析法》", 30 November 1988 * |
| 朱若华等著: "《室温磷光分析法原理与应用》", 31 March 2006 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111607394A (en) * | 2020-06-17 | 2020-09-01 | 太原理工大学 | Room temperature phosphorescent carbon dot compound and preparation method thereof |
| CN111763512A (en) * | 2020-06-24 | 2020-10-13 | 中山大学 | Application of polyvinyl benzene sulfonic acid or salt thereof as room temperature phosphorescent material |
| CN112707922A (en) * | 2020-12-24 | 2021-04-27 | 河北工业大学 | Color-adjustable hectorite and 4,4' -biphenyldicarboxylic acid hybridized room temperature phosphorescent material |
| CN113025325A (en) * | 2021-03-25 | 2021-06-25 | 盐城工学院 | Preparation method and application of room-temperature phosphorescent carbon-based composite material capable of changing color under single excitation source |
| CN113025325B (en) * | 2021-03-25 | 2022-11-01 | 盐城工学院 | Preparation method and application of room temperature phosphorescent carbon-based composite material capable of changing color under single excitation source |
| CN113789168A (en) * | 2021-10-08 | 2021-12-14 | 中山大学 | Thermal activation delayed fluorescence material and preparation method and application thereof |
| CN114621752A (en) * | 2021-12-03 | 2022-06-14 | 昆明理工大学 | Room-temperature phosphorescent waterborne polymer anti-counterfeiting material and preparation method and application thereof |
| CN115161014A (en) * | 2022-06-09 | 2022-10-11 | 昆明理工大学 | Preparation method and application of doped room temperature phosphorescent waterborne polymer anti-counterfeiting material |
| CN115161014B (en) * | 2022-06-09 | 2023-04-07 | 昆明理工大学 | Preparation method and application of doped room temperature phosphorescent waterborne polymer anti-counterfeiting material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111253933B (en) | 2021-08-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111253933B (en) | Room-temperature phosphorescent anti-counterfeiting material with timeliness, and preparation method and application thereof | |
| CN111363537B (en) | Halogen-free and heavy atom-free room temperature phosphorescent material and preparation method and application thereof | |
| CN102120931B (en) | Red fluorophor and preparation method thereof | |
| CN110079301B (en) | Organic long-afterglow material and preparation method and application thereof | |
| CN101092563A (en) | Phosphor powder in use for light emitting diode (LED), and preparation method | |
| WO2003016428A2 (en) | Triboluminescent materials and devices containing them | |
| CN101691718B (en) | Method for preparing long afterglow luminous paper | |
| CN106497560B (en) | The controllable carbon dots based compound nano material and the preparation method and application thereof of luminescent properties | |
| CN104086683B (en) | A kind of preparation method of steady persistence high-molecular luminous material | |
| CN114621752B (en) | Room-temperature phosphorescent waterborne polymer anti-counterfeiting material and preparation method and application thereof | |
| CN114478852A (en) | Color-adjustable organic room temperature phosphorescent film material with hydrothermal stimulus response, and preparation and application thereof | |
| CN104152145A (en) | Three-activator single-matrix white light phosphor and preparation method thereof | |
| Snari et al. | Preparation of photoluminescent nanocomposite ink for detection and mapping of fingermarks | |
| CN114752256A (en) | MOG fluorescent ink and preparation method thereof, and information encryption and anti-counterfeiting application | |
| CN108659843B (en) | Anti-counterfeit label material | |
| CN102277167B (en) | Europium ion-doped aluminum magnesium phosphate fluorescent powder and preparation method thereof | |
| CN114276797A (en) | Photochromic gel material, preparation method thereof, multicolor regulation and control method and application | |
| CN115161014B (en) | Preparation method and application of doped room temperature phosphorescent waterborne polymer anti-counterfeiting material | |
| CN106010528B (en) | Bismuth and manganese doped blue fluorescent powder and preparation method and application thereof | |
| CN113462382B (en) | Rare earth color light conversion material, color converter containing same and light-emitting device | |
| CN110093064B (en) | Preparation method and application of long-afterglow luminescent ink | |
| JP7187019B2 (en) | Color polymer compound, humidity indicator ink, humidity indicator card, and humidity indicator silica gel | |
| CN111763512A (en) | Application of polyvinyl benzene sulfonic acid or salt thereof as room temperature phosphorescent material | |
| CN109097031B (en) | Mn (manganese)4+Strontium lithium fluoroaluminate doped red light material and preparation method thereof | |
| CN102899042A (en) | Pr, Eu/Tb co-doped tungstate/molybdate fluorescent powder and preparation method thereof |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20200609 Assignee: Guangzhou Shuangyingli Biotechnology Co.,Ltd. Assignor: SUN YAT-SEN University Contract record no.: X2023440000011 Denomination of invention: An aging room temperature phosphorescent anti-counterfeiting material and its preparation method and application Granted publication date: 20210813 License type: Common License Record date: 20230302 |
|
| EE01 | Entry into force of recordation of patent licensing contract |