CN114686208A - Composite reagent, anti-counterfeiting combined reagent and anti-counterfeiting method - Google Patents
Composite reagent, anti-counterfeiting combined reagent and anti-counterfeiting method Download PDFInfo
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- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
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Abstract
The invention discloses a composite reagent, an anti-counterfeiting combined reagent and an anti-counterfeiting method, wherein the composite reagent comprises a first organic solvent and a composite material dispersed in the first organic solvent, and the composite material comprises a lanthanide metal organic framework and a first quantum dot material combined on the lanthanide metal organic framework. The invention can realize the optical anti-counterfeiting effect under different environmental modes by spraying the composite reagent on the object to be anti-counterfeiting.
Description
Technical Field
The invention relates to the technical field of anti-counterfeiting, in particular to a composite reagent, an anti-counterfeiting combined reagent and an anti-counterfeiting method.
Background
The appearance of counterfeit products has a serious impact on the economy and safety of users with different requirements. Accordingly, anti-counterfeiting technology has evolved and received particular attention. The traditional anti-counterfeiting method has simple technology, and the anti-counterfeiting process is laggard and easy to imitate, thus being incapable of meeting the requirements of the current market. Therefore, it is important to develop a new anti-counterfeit technology with a high security level or a multi-combination mode. Fluorescent materials are widely used in anti-counterfeiting technology due to their high fluorescence quantum efficiency, adjustable emission wavelength, and the like. The mainstream fluorescence anti-counterfeiting technology at present is based on that different fluorescent materials show different fluorescence emissions under different excitation sources, including ultraviolet excitation, infrared excitation and near infrared excitation or thermal activation. However, the existing fluorescent anti-counterfeiting mode is single, the technical content is low, and the fluorescent anti-counterfeiting method is easy to crack and imitate.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a composite reagent, an anti-counterfeiting combined reagent and an anti-counterfeiting method, and aims to solve the problem of single fluorescence anti-counterfeiting mode in the prior art.
The technical scheme of the invention is as follows:
a composite reagent comprising a first organic solvent and a composite material dispersed in the first organic solvent, the composite material comprising a lanthanide metal organic framework and a first quantum dot material bound to the lanthanide metal organic framework.
An anti-counterfeiting combination reagent, which comprises a combination reagent and a second anti-counterfeiting agent matched with the combination reagent, wherein the combination reagent comprises a first organic solvent and a composite material dispersed in the first organic solvent, and the composite material comprises a lanthanide metal organic framework and a first quantum dot material combined on the lanthanide metal organic framework; the second anti-counterfeiting agent comprises a second organic solvent and a second quantum dot material dispersed in the second organic solvent, and the second quantum dot material is used for being combined with the first quantum dot material to form a core-shell quantum dot.
An anti-counterfeiting method, comprising the steps of:
spraying a composite reagent on an object to be anti-counterfeit, the composite reagent being configured to be excited by a first ultraviolet light;
providing a second anti-counterfeiting agent configured to react with the composite reagent to form core-shell quantum dots configured to be excited by a second ultraviolet light.
Has the beneficial effects that: the composite reagent provided by the invention comprises a first organic solvent and a composite material dispersed in the first organic solvent, wherein the composite material comprises a lanthanide metal organic framework and a first quantum dot material bonded on the lanthanide metal organic framework. The invention sprays the compound reagent on the surface of the object to be anti-counterfeiting, and can realize the optical anti-counterfeiting effect in different environmental modes.
Drawings
FIG. 1 is a flow chart of a preferred embodiment of a method for preparing an anti-counterfeiting combination reagent according to the invention.
FIG. 2 is a flow chart of an anti-counterfeiting method according to a preferred embodiment of the invention.
Detailed Description
The invention provides a composite reagent, an anti-counterfeiting combined reagent and an anti-counterfeiting method, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Embodiments of the invention provide a composite reagent comprising a first organic solvent and a composite material dispersed in the first organic solvent, the composite material comprising a lanthanide metal-organic framework and a first quantum dot material bound to the lanthanide metal-organic framework.
In this embodiment, the composite reagent is sprayed on an object to be anti-counterfeit, and after the composite reagent is dried, the object to be anti-counterfeit is colorless under the irradiation of visible light and red light is displayed under the irradiation of first ultraviolet light. Thereby realizing the optical anti-counterfeiting effect. The wavelength range of visible light is 390-780nm, and the lanthanide series metal organic framework and the first quantum dot material do not emit light under the excitation of the visible light; the lanthanide metal organic frame can display red light under the excitation of first ultraviolet light, and the first quantum dot material combined on the lanthanide metal organic frame emits extremely weak fluorescence after being excited by external light, so that light emitted after the lanthanide metal organic frame is excited cannot be interfered.
In some embodiments, the composite reagent is for use with a second anti-counterfeiting agent comprising a second organic solvent and a second quantum dot material dispersed in the second organic solvent, the second quantum dot material for forming core-shell quantum dots in combination with the first quantum dot material.
In this embodiment, the complex reagent and the second anti-counterfeiting agent are used in cooperation to form a set of fluorescent anti-counterfeiting system, which can achieve optical anti-counterfeiting effects in different environmental modes. Specifically, in the using process, the composite reagent is sprayed on an object to be anti-counterfeit, after the composite reagent is dried, the object to be anti-counterfeit shows colorless under the irradiation of visible light, and shows red light under the irradiation of first ultraviolet light. The wavelength range of visible light is 390-780nm, and the lanthanide series metal organic framework and the first quantum dot material do not emit light under the excitation of the visible light; the lanthanide metal organic frame displays red light under the excitation of first ultraviolet light, and the first quantum dot material combined on the lanthanide metal organic frame emits extremely weak fluorescence after being excited by external light, so that light emitted after the lanthanide metal organic frame is excited cannot be interfered.
In this embodiment, the second anti-counterfeiting agent is sprayed on the object to be anti-counterfeiting, on which the composite reagent is sprayed, after the second anti-counterfeiting agent is dried, the object to be anti-counterfeiting can display a color different from red under the independent irradiation of second ultraviolet light or the simultaneous irradiation of first ultraviolet light and second ultraviolet light, so as to realize anti-counterfeiting, and the wavelength of the second ultraviolet light is greater than that of the first ultraviolet light. In this embodiment, when the second ultraviolet light is used to independently irradiate the object to be anti-counterfeit, since the second quantum dot in the second anti-counterfeit agent can be combined with the first quantum dot in the composite reagent to generate the core-shell quantum dot, the fluorescence effect of the core-shell quantum dot is obviously enhanced, and the core-shell quantum dot can emit light different from red, such as green light or blue light, under the independent irradiation of the second ultraviolet light; the red light emitted by the lanthanide metal organic framework under the independent irradiation of the second ultraviolet light is very weak and can be ignored. When the object to be anti-counterfeiting is irradiated by the first ultraviolet light and the second ultraviolet light simultaneously, the core-shell quantum dots emit light different from red light, such as green light, under the excitation of the second ultraviolet light, the lanthanide series metal organic frame emits red light under the irradiation of the first ultraviolet light, the red light and the green light can be mixed to display yellow light, and multiple anti-counterfeiting effects can also be realized.
In the embodiment, after the composite reagent is sprayed on the surface of the object to be anti-counterfeiting, the object is colorless under visible light (namely, the object is colorless when seen by naked eyes and cannot see the anti-counterfeiting mark), but the red anti-counterfeiting mark (the object is visible by the naked eyes under ultraviolet light) can be seen by using the first ultraviolet light irradiation to achieve a first anti-counterfeiting effect; after the second anti-counterfeiting agent is sprayed, naked eyes can display light different from red under the independent irradiation of the second ultraviolet light or the simultaneous irradiation of the first ultraviolet light and the second ultraviolet light, so that the second anti-counterfeiting effect is achieved. The embodiment achieves multiple anti-counterfeiting effects through color conversion of the anti-counterfeiting mark.
The embodiment enriches the fluorescent anti-counterfeiting modes, has higher technical content, is not easy to crack and imitate, and can be widely applied to the anti-counterfeiting field.
In some embodiments, there is also provided a security combination comprising a complexing agent and a second security agent for use with the complexing agent, the complexing agent comprising a first organic solvent and a composite material dispersed in the first organic solvent, the composite material comprising a lanthanide metal organic framework and a first quantum dot material bound to the lanthanide metal organic framework; the second anti-counterfeiting agent comprises a second organic solvent and a second quantum dot material dispersed in the second organic solvent, and the second quantum dot material is used for being combined with the first quantum dot material to form a core-shell quantum dot.
In this embodiment, the complex reagent and the second anti-counterfeiting agent are used in cooperation to form a set of fluorescent anti-counterfeiting system, which can achieve optical anti-counterfeiting effects in different environmental modes. Specifically, in the using process, the composite reagent is sprayed on an object to be anti-counterfeit, after the composite reagent is dried, the object to be anti-counterfeit shows colorless under the irradiation of visible light, and shows red light under the irradiation of first ultraviolet light. The wavelength range of visible light is 390-780nm, and the lanthanide series metal organic framework and the first quantum dot material do not emit light under the excitation of the visible light; the lanthanide metal organic frame displays red light under the excitation of first ultraviolet light, and the first quantum dot material combined on the lanthanide metal organic frame emits extremely weak fluorescence after being excited by external light, so that light emitted after the lanthanide metal organic frame is excited cannot be interfered.
In the composite material provided in this embodiment, the metal ions in the first quantum dot material form coordination bonds with the coordinating anions in the lanthanide metal-organic framework, so that the first quantum dot material is bonded to the lanthanide metal-organic framework. Because the first quantum dot material is easily quenched by external environmental factors, such as water vapor and oxygen of air, the first quantum dot material which exists independently can be quenched, so that the first quantum dot material cannot be combined with the second quantum dot material in the second anti-counterfeiting reagent and can emit light under the excitation of second ultraviolet light, and the value of subsequent reaction is lost; and the first quantum dot material is easy to agglomerate, and the phenomenon of agglomeration, coagulation and fluorescence quenching is easy to occur. In this embodiment, the lanthanide metal organic frame may fix the first quantum dot material in the frame itself, so as to disperse the first quantum dot material, and the lanthanide metal organic frame may further protect the first quantum dot material, so as to prevent water vapor and oxygen in the air from quenching the first quantum dot material, so as to facilitate subsequent combination with the second quantum dot material in the second anti-counterfeiting agent and fluorescence under excitation of the second ultraviolet light.
In this embodiment, the second anti-counterfeiting agent is sprayed on the object to be anti-counterfeiting, on which the composite reagent is sprayed, after the second anti-counterfeiting agent is dried, the object to be anti-counterfeiting can display a color different from red under the independent irradiation of the second ultraviolet light or the simultaneous irradiation of the first ultraviolet light and the second ultraviolet light, so as to realize anti-counterfeiting, and the wavelength of the second ultraviolet light is greater than that of the first ultraviolet light. In this embodiment, when the second ultraviolet light is used to independently irradiate the object to be anti-counterfeit, since the second quantum dot material in the second anti-counterfeit agent can be combined with the first quantum dot material in the composite reagent to generate the core-shell quantum dot, the fluorescence effect of the core-shell quantum dot is significantly enhanced, and the core-shell quantum dot can emit light different from red, such as green light or blue light, under the independent irradiation of the second ultraviolet light; the red light emitted by the lanthanide metal organic framework under the independent irradiation of the second ultraviolet light is very weak and can be ignored. When the object to be anti-counterfeiting is irradiated by the first ultraviolet light and the second ultraviolet light simultaneously, the core-shell quantum dots emit light different from red light, such as green light, under the excitation of the second ultraviolet light, the lanthanide series metal organic frame emits red light under the irradiation of the first ultraviolet light, and the red light and the green light can be mixed to display yellow light.
In the embodiment, after the composite reagent is used, the composite reagent is colorless under visible light (namely, the composite reagent is colorless when seen by naked eyes, and the anti-counterfeiting mark cannot be seen), but the red anti-counterfeiting mark can be seen by using the first ultraviolet light irradiation (the composite reagent can be seen by the naked eyes under the ultraviolet light), so that a first heavy anti-counterfeiting effect is achieved; after the second anti-counterfeiting agent is sprayed, naked eyes can display light different from red under the independent irradiation of the second ultraviolet light or the simultaneous irradiation of the first ultraviolet light and the second ultraviolet light, so that a second anti-counterfeiting effect is achieved. The embodiment achieves the effect of multiple anti-counterfeiting through the color transformation of the anti-counterfeiting mark.
The anti-counterfeiting combined reagent provided by the embodiment enriches fluorescent anti-counterfeiting modes, has higher technical content, is not easy to crack and imitate, and can be widely applied to the anti-counterfeiting field.
The anti-counterfeiting combined reagent provided by the embodiment also utilizes the characteristic that shell quantum dots are easy to fall off when the core-shell quantum dots meet water, so that fluorescence quenching occurs, and a fluorescence anti-counterfeiting system can be repeatedly used. Specifically, when distilled water is continuously sprayed on an object to be anti-counterfeit, which is sprayed with the composite reagent and the second anti-counterfeit agent in sequence, the object to be anti-counterfeit only shows red color under the simultaneous irradiation of the first ultraviolet light and the second ultraviolet light. The distilled water can decompose the core-shell quantum dots, so that the shell quantum dots fall off, and the capability of generating fluorescence under the excitation of second ultraviolet light is lost; but the distilled water does not produce quenching and decomposition effects on the lanthanide metal organic framework, so the lanthanide metal organic framework has no change in the capability of producing red light under the excitation of the first ultraviolet light. Further, when the second anti-counterfeiting agent is continuously sprayed on the to-be-anti-counterfeiting object sprayed with the distilled water, after the second anti-counterfeiting agent is dried, the to-be-anti-counterfeiting object can still display fluorescence different from red under the independent irradiation of second ultraviolet light or the simultaneous irradiation of the first ultraviolet light and the second ultraviolet light.
In some embodiments, the lanthanide metal organic framework includes a lanthanide metal ion, and an organic ligand that is coordinately bound to the lanthanide metal ion. In this embodiment, the lanthanide metal ions are one or more of lanthanum ions, cerium ions, praseodymium ions, europium ions, and gadolinium ions, but are not limited thereto. The organic ligand is one or more of, but not limited to, trimesic acid, pyromellitic acid, trimesic acid, naphthalene tetracarboxylic acid, naphthalene tetraacetic acid, anthracene tetracarboxylic acid, and anthracene tetraacetic acid.
In some embodiments, the first quantum dot material is one of a group IIB-VIA quantum dot, a group IIIA-VA quantum dot, or a group IVA-VIA quantum dot. In the embodiment, IIB-VIA group quantum dots, IIIA-VA group quantum dots or IVA-VIA group quantum dots are selected as the first quantum dot material, because the fluorescence effect is weak, the interference on the red fluorescence of the lanthanide metal organic framework can not be generated; the first quantum dot material formed by the materials of the IIB-VIA family, the IIIA-VA family and the IVA-VIA family is easy to modify, and a strong fluorescence effect can be obtained by adding a shell layer or modifying an organic ligand; furthermore, the IIB-VIA group quantum dots, IIIA-VA group quantum dots or IVA-VIA group quantum dots all contain metal ions and can form coordination bonds with coordination anions in a lanthanide metal organic framework for connection. By way of example, the group iib-via quantum dots may be one or more of CdSe, CdS, CdTe, CdZnS or CdSeS, but are not limited thereto; the IIIA-VA quantum dots can be one or two of InP and InAs, but are not limited to; the group IVA-VIA quantum dots may be one or two of PbS and PbSe, but are not limited thereto.
In some embodiments, the first organic solvent is one or more of N, N dimethylformamide, N dimethyl sulfoxide, toluene, and chlorobenzene, but is not limited thereto.
In some embodiments, the second quantum dot material is one of, but not limited to, a group IIB-VIA quantum dot, a group IIIA-VA quantum dot, or a group IVA-VIA quantum dot. In this embodiment, the second quantum dot material may be combined with the first quantum dot material in the composite reagent to generate the core-shell quantum dot, the fluorescence effect of the core-shell quantum dot is significantly enhanced, and the core-shell quantum dot may emit strong fluorescence different from red fluorescence when irradiated by the second ultraviolet light. By way of example, the group iib-via quantum dots can be one or more of ZnSe, ZnS, and ZnSeS, but are not limited thereto; the iiia-va quantum dots may be one or more of InAs, InP, and InAsP, but are not limited thereto; one or more of PbSe, PbS, PbSeS, PbSeTe and PbSTe of the groups IVA to VIA, but not limited thereto.
In this embodiment, the core-shell quantum dot formed by combining the first quantum dot material in the composite reagent and the second quantum dot material in the second anti-counterfeiting agent may be a group iib-via quantum dot, for example: CdSe @ ZnSe, CdSe @ ZnS, CdS @ ZnSe, CdS @ ZnS, CdTe @ ZnSe, CdTe @ ZnS, CdS @ ZnS, CdSe @ ZnSeS, CdSeS @ ZnS, etc.; group IIIA-VA quantum dots, for example: InP @ InAs, InAs @ InP, InAs @ InAsP, InP @ InAsP and the like; group IVA-VIA quantum dots, for example: PbS @ PbSe, PbSe @ PbS, PbSe @ PbSeS, PbSe @ PbSeTe, PbSe @ PbSTe and the like.
In some embodiments, the particle size of the core-shell quantum dots is less than 50nm, by way of example, the particle size of the core-shell quantum dots is 5-50 nm. Within the size range, the core-shell quantum dot can emit fluorescence different from red under the irradiation of ultraviolet light, such as green light, blue light and the like.
Taking CdSe as an example of the first quantum dot material, the CdSe does not emit light under the excitation of second ultraviolet light; when the first quantum dot material CdSe and the second quantum dot material ZnS are combined to generate the core-shell quantum dot CdSe @ ZnS, the core-shell quantum dot CdSe @ ZnS can emit green light under the excitation of second ultraviolet light; when the nuclear shell quantum dots CdSe @ ZnS are decomposed after meeting water, a first quantum dot material CdSe (non-luminescence) combined on the lanthanide metal organic framework and a second quantum dot material ZnS washed away by the water are regenerated; when the first quantum dot material CdSe (non-luminescent) meets new second quantum dot material ZnS again, core-shell quantum dots CdSe @ ZnS are regenerated again (green light is regenerated again).
In some embodiments, the second organic solvent is one or more of ethanol, methanol, butanol, propanol, and isopropanol, but is not limited thereto.
In some embodiments, there is also provided a method for preparing an anti-counterfeit combination reagent, as shown in fig. 1, comprising the steps of:
s10, dispersing the lanthanide metal compound and the organic ligand into a first organic solvent, and mixing to prepare lanthanide metal organic framework solution;
s20, adding a first quantum dot material into the lanthanide metal organic framework solution, and heating to combine the first quantum dot material on the lanthanide metal organic framework to obtain a composite reagent;
and S30, dispersing the second quantum dot material in a second organic solvent to obtain a second anti-counterfeiting agent.
In this embodiment, the organic ligand firstly performs a coordination reaction with a lanthanide metal ion in the lanthanide metal compound to generate a stable lanthanide metal organic framework, and then a coordination anion in the lanthanide metal organic framework forms a coordination bond with a metal ion in the first quantum dot material, so that the quantum dot is bonded to the lanthanide metal organic framework, thereby preparing the composite reagent.
In a specific embodiment, 0.2-0.8g of lanthanide metal compound and 1-3g of organic ligand are weighed and added into 5-10g of first organic solvent, and ultrasonic treatment is carried out in a polytetrafluoroethylene reaction kettle until a transparent clear solution is obtained; then 0.5-1.5g of first quantum dot material solution is added, and the composite reagent is prepared after reaction for a period of time at high temperature. In this embodiment, the lanthanide metal compound includes, but is not limited to, lanthanum nitrate, cerium nitrate, praseodymium nitrate, europium nitrate, gadolinium nitrate, etc.; the organic ligands include, but are not limited to, trimesic acid, pyromellitic acid, trimesic acid, naphthalene tetracarboxylic acid, and naphthalene tetraacetic acid. Anthracenetetracarboxylic acid, anthracenetetraacetic acid, and the like; the first organic solvent includes, but is not limited to, N dimethylformamide, N dimethylsulfoxide, toluene, chlorobenzene, and the like; the first quantum dot material includes, but is not limited to: group IIB-VIA CdSe, CdS, CdTe, CdSnZnS, CdSeS, etc., group IIIA-VA InP, InAs, etc., group IVA-VIA PbS, PbSe, etc.
In a specific embodiment, 1-2g of the second quantum dot material is dissolved in 2-5g of the second organic solvent to prepare the second anti-counterfeiting agent. In this embodiment, the second quantum dot material includes, but is not limited to, IIB-VIA group quantum dots ZnSe, ZnS, ZnSeS, etc., IIIA-VA group InAs, InP, InAsP, etc., IVA-VIA group PbSe, PbS, PbSeS, PbSeTe, PbSTe, etc.; the second organic solvent includes, but is not limited to, ethanol, methanol, butanol, propanol, isopropanol, and the like.
In some embodiments, there is also provided an anti-counterfeiting method, as shown in fig. 2, comprising the steps of:
s100, spraying a composite reagent on an object to be anti-counterfeit, wherein the composite reagent is configured to be excited by first ultraviolet light;
s200, providing a second anti-counterfeiting agent, wherein the second anti-counterfeiting agent is configured to react with the composite reagent to form a core-shell quantum dot, and the core-shell quantum dot is configured to be excited by second ultraviolet light.
In this embodiment, the first ultraviolet light is used to excite the lanthanide metal organic framework in the composite reagent to emit light of a first color, the second ultraviolet light is used to excite the core-shell quantum dot to emit light of a second color, and the first color is different from the second color. The compound reagent and the second anti-counterfeiting agent are matched with each other to form a set of fluorescent anti-counterfeiting system, and the optical anti-counterfeiting effect under different environmental modes can be realized. Specifically, the composite reagent is sprayed on an object to be anti-counterfeit, and after the composite reagent is dried, the object to be anti-counterfeit is colorless under visible light irradiation and red light under first ultraviolet light irradiation. The wavelength range of visible light is 390-780nm, and the lanthanide series metal organic framework and the first quantum dot material do not emit light under the excitation of the visible light; the lanthanide metal organic frame displays red light under the excitation of first ultraviolet light, and the first quantum dot material combined on the lanthanide metal organic frame emits extremely weak fluorescence after being excited by external light, so that light emitted after the lanthanide metal organic frame is excited cannot be interfered.
And spraying the second anti-counterfeiting agent on an object to be anti-counterfeiting sprayed with the composite reagent, wherein after the second anti-counterfeiting agent is dried, the object to be anti-counterfeiting can display a color different from red under the independent irradiation of second ultraviolet light or the simultaneous irradiation of the first ultraviolet light and the second ultraviolet light, so that the anti-counterfeiting is realized, and the wavelength of the second ultraviolet light is greater than that of the first ultraviolet light. In this embodiment, when the second ultraviolet light is used to irradiate the object to be anti-counterfeit separately, since the second quantum dot material in the second anti-counterfeit agent can be combined with the first quantum dot material in the composite reagent to generate the core-shell quantum dot, the fluorescence effect of the core-shell quantum dot is significantly enhanced, and the core-shell quantum dot can emit light different from red, such as green light or blue light, under the separate irradiation of the second ultraviolet light; the red light emitted by the lanthanide metal organic framework under the independent irradiation of the second ultraviolet light is very weak and can be ignored. When the object to be anti-counterfeiting is irradiated by the first ultraviolet light and the second ultraviolet light simultaneously, the core-shell quantum dots emit light different from red light, such as green light, under the excitation of the second ultraviolet light, the lanthanide series metal organic frame emits red light under the irradiation of the first ultraviolet light, and the red light and the green light can be mixed to display yellow light.
In some embodiments, the first ultraviolet light has a wavelength of 200-280nm and the second ultraviolet light has a wavelength of 300-380 nm. The lanthanide metal organic frame can emit stronger red light under the irradiation of 200-280nm ultraviolet light, for example, the lanthanide metal organic frame emits the strongest red light under the irradiation of 254nm ultraviolet light; the nuclear shell quantum dots can emit stronger fluorescence under the irradiation of ultraviolet light with the wavelength of 300-380nm, and quantum dots made of different materials and with different particle sizes can emit fluorescence with different colors under the irradiation of ultraviolet light with the wavelength of 300-380 nm. By way of example, quantum dots with particle sizes less than 50nm can emit fluorescence different from red light, such as blue light, green light, etc., under the irradiation of ultraviolet light at 300-380 nm.
For example, in the using process, the composite reagent is sprayed on an object to be anti-counterfeit, and after the composite reagent is dried, the object to be anti-counterfeit shows colorless under the irradiation of visible light and shows red light under the irradiation of 254nm ultraviolet light. And spraying the second anti-counterfeiting agent on an object to be anti-counterfeiting sprayed with the composite reagent, and after the second anti-counterfeiting agent is dried, irradiating the object to be anti-counterfeiting under 254nm and 365nm ultraviolet light to generate yellow light formed by mixing red light and green light. The second quantum dot material in the second anti-counterfeiting agent can be combined with the first quantum dot material in the composite reagent to generate the core-shell quantum dot, the fluorescence effect of the core-shell quantum dot is obviously enhanced, and the 365nm ultraviolet light irradiates to enable the core-shell quantum dot to emit strong green fluorescence, so that the object to be anti-counterfeiting shows yellow light under the 254nm and 365nm ultraviolet light.
The embodiment provides a fluorescent anti-counterfeiting method with abundant fluorescent changes, has high technical content, is not easy to crack and imitate, and can be widely applied to the anti-counterfeiting field.
In some embodiments, the core-shell quantum dots are configured to be water-quenched. And after the second anti-counterfeiting agent is sprayed on the object to be anti-counterfeiting, the surface of which is sprayed with the composite reagent, the object to be anti-counterfeiting is sprayed with distilled water, and then only red is displayed under the simultaneous irradiation of the first ultraviolet light and the second ultraviolet light. Specifically, when distilled water is continuously sprayed on an object to be anti-counterfeit, which is sprayed with a composite reagent and a second anti-counterfeit agent in sequence, the object to be anti-counterfeit only shows red color under the simultaneous irradiation of a first ultraviolet light and a second ultraviolet light. The core-shell quantum dots can be decomposed by the distilled water, so that the second quantum dot material falls off, and the capability of generating fluorescence under the excitation of second ultraviolet light is lost; but the distilled water does not produce quenching and decomposition effects on the lanthanide metal organic framework, so the lanthanide metal organic framework has no change in the capability of producing red light under the excitation of the first ultraviolet light. Further, when the second anti-counterfeiting agent is continuously sprayed on the to-be-anti-counterfeiting object sprayed with the distilled water, after the second anti-counterfeiting agent is dried, the to-be-anti-counterfeiting object can still display fluorescence different from red under the independent irradiation of second ultraviolet light or the simultaneous irradiation of the first ultraviolet light and the second ultraviolet light. The embodiment utilizes the characteristic that the second quantum dot material is easy to fall off when the quantum dots meet water, so that fluorescence quenching occurs, and the fluorescence anti-counterfeiting system can be repeatedly used. .
The preparation method and the anti-counterfeiting method of the anti-counterfeiting combination reagent of the invention are further explained by the following specific embodiments:
example 1
1) 0.2g of lanthanum nitrate and 1g of trimesic acid are weighed, added into 5g N, N-dimethylformamide and transferred into a polytetrafluoroethylene reaction kettle, and reacted for 10 minutes under 200 watts of ultrasonic power.
2) Adding 0.5g of CdS into 1g of ethanol, then transferring the solution into the polytetrafluoroethylene reaction kettle in the step 1, reacting for 20 minutes at 200 ℃, and naturally cooling to obtain a CdS @ lanthanum porous metal organic framework material precursor.
3) 1g of ZnSe was added to 2g of ethanol and dispersed to obtain a uniform solution.
4) Spraying the precursor solution of the CdS @ lanthanum porous metal organic framework material prepared in the step 2) on a material to be anti-counterfeiting, and displaying colorless under visible light after the precursor solution is dried completely; it showed red color under uv-visible light source at 254 nm. And (3) when anti-counterfeiting verification is required, uniformly spraying the ZnSe solution prepared in the step (3) on the surface of the object to be anti-counterfeiting, and drying for a period of time by using a hot air gun. The yellow light formed by mixing red light and green light can be displayed by simultaneously irradiating the red light and the green light by ultraviolet and visible light sources under 254nm and 365 nm.
5) After the verification is finished, a layer of distilled water is sprayed on the surface of the object to be anti-counterfeiting, and the green light anti-counterfeiting mark can be eliminated.
6) And then repeating the step 4, namely the yellow-displayed anti-counterfeiting mark can be obtained again.
Example 2
1) 0.8g of gadolinium nitrate and 3g of naphthalene tetracarboxylic acid are weighed and added into 10g N N dimethyl sulfoxide, and the mixture is transferred into a polytetrafluoroethylene reaction kettle and reacts for 8 minutes under the ultrasonic power of 300 watts.
2) Adding 1.5g of InP into 3g of isopropanol, then transferring the mixture into a polytetrafluoroethylene reaction kettle in the step 1 to react for 15 minutes at 250 ℃, and naturally cooling to obtain an InP @ gadolinium porous metal organic framework material precursor.
3) And 2g of InAs is added into 3g of butanol, and the mixture is dispersed to obtain a uniform solution.
4) Spraying the precursor solution of the InP @ gadolinium porous metal organic framework material prepared in the step 2) on a material to be anti-counterfeit, and displaying the material to be anti-counterfeit colorless under visible light after the material is dried and dried completely; it showed red color under uv-visible light source at 254 nm. And (3) when anti-counterfeiting verification is required, uniformly spraying the InAs solution prepared in the step (3) on the surface of the object to be anti-counterfeiting, and drying for a period of time by using a hot air gun. The yellow light formed by mixing red light and green light can be displayed by simultaneously irradiating the red light and the green light by ultraviolet and visible light sources under 254nm and 365 nm.
5) After the verification is finished, a layer of distilled water is sprayed on the surface of the object to be anti-counterfeiting, and the green light anti-counterfeiting mark can be eliminated.
6) And then repeating the step 4, so that the yellow-light-displayed anti-counterfeiting mark can be obtained again.
Example 3
1) 0.5g of europium nitrate and 2g of anthracene tetraacetic acid are weighed, added into 7.5g of chlorobenzene and transferred into a polytetrafluoroethylene reaction kettle, and reacted for 15 minutes under the ultrasonic power of 250 watts.
2) Adding 1g of PbSe into 2g of butanol, transferring the mixture into a polytetrafluoroethylene reaction kettle in the step 1, reacting for 20 minutes at 300 ℃, and naturally cooling to obtain a precursor of the PbSe @ europium porous metal organic framework material.
3) 1.5g of PbS was added to 2g of butanol, and dispersed to obtain a uniform solution.
4) Spraying the precursor solution of the PbSe @ europium porous metal organic framework material prepared in the step 2) on a material to be anti-counterfeit, and displaying colorless under visible light after the precursor solution is dried and dried completely; it showed red color under uv-visible light source at 254 nm. And (3) when anti-counterfeiting verification is required, uniformly spraying the PbS solution prepared in the step (3) on the surface of the object to be anti-counterfeiting, and drying for a period of time by using a hot air gun. The yellow light formed by mixing red light and green light can be displayed by simultaneously irradiating the red light and the green light by ultraviolet and visible light sources under 254nm and 365 nm.
5) After the verification is finished, a layer of distilled water is sprayed on the surface of the object to be anti-counterfeiting, and the green light anti-counterfeiting mark can be eliminated.
6) And then repeating the step 4), namely the yellow-displayed anti-counterfeiting mark can be obtained again.
In summary, the anti-counterfeiting combination reagent provided by the present invention comprises a composite reagent and a second anti-counterfeiting agent, wherein the composite reagent comprises a first anti-counterfeiting material dispersed in a first organic solvent, and the first anti-counterfeiting material comprises a lanthanide metal organic framework and a first quantum dot material bonded on the lanthanide metal organic framework; the second anti-counterfeiting agent comprises a second anti-counterfeiting material dispersed in a second organic solvent, and the second anti-counterfeiting material is a second quantum dot material. The composite reagent and the second anti-counterfeiting agent are matched with each other to form a set of fluorescent anti-counterfeiting system, so that the optical anti-counterfeiting effect under different environmental modes can be realized; meanwhile, the characteristic that the quantum dot quenches a water solvent is utilized, so that the fluorescent anti-counterfeiting system can be repeatedly used.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (10)
1. A composite reagent comprising a first organic solvent and a composite material dispersed in the first organic solvent, the composite material comprising a lanthanide metal-organic framework and a first quantum dot material bound to the lanthanide metal-organic framework.
2. The composite reagent of claim 1, wherein the composite reagent is used in combination with a second anti-counterfeiting agent, the second anti-counterfeiting agent comprises a second organic solvent and a second quantum dot material dispersed in the second organic solvent, and the second quantum dot material is used to form a core-shell quantum dot in combination with the first quantum dot material.
3. The complexing reagent of claim 1, wherein said lanthanide metal organic framework comprises a lanthanide metal ion and an organic ligand that is coordinately bound to said lanthanide metal ion.
4. The composite reagent of claim 3, wherein the lanthanide metal ions are one or more of lanthanum ions, cerium ions, praseodymium ions, europium ions, and gadolinium ions; and/or the presence of a gas in the gas,
the organic ligand is one or more of trimesic acid, pyromellitic acid, trimesic acid, naphthalene tetracarboxylic acid, naphthalene tetraacetic acid, anthracene tetracarboxylic acid and anthracene tetraacetic acid; and/or the presence of a gas in the gas,
the first quantum dot material is one of IIB-VIA group quantum dots, IIIA-VA group quantum dots or IVA-VIA group quantum dots; and/or the presence of a gas in the gas,
the first organic solvent is one or more of N, N dimethylformamide, N, N dimethyl sulfoxide, toluene and chlorobenzene; and/or the presence of a gas in the gas,
the second quantum dot material is one of IIB-VIA group quantum dots, IIIA-VA group quantum dots or IVA-VIA group quantum dots; and/or the presence of a gas in the gas,
the second organic solvent is one or more of ethanol, methanol, butanol, propanol and isopropanol.
5. An anti-counterfeiting combination reagent, which is characterized by comprising a combination reagent and a second anti-counterfeiting agent matched with the combination reagent, wherein the combination reagent comprises a first organic solvent and a composite material dispersed in the first organic solvent, and the composite material comprises a lanthanide metal organic framework and a first quantum dot material combined on the lanthanide metal organic framework; the second anti-counterfeiting agent comprises a second organic solvent and a second quantum dot material dispersed in the second organic solvent, and the second quantum dot material is used for being combined with the first quantum dot material to form a core-shell quantum dot.
6. The anti-counterfeiting combination reagent according to claim 5, wherein the first quantum dot material is one of IIB-VIA group quantum dots, IIIA-VA group quantum dots or IVA-VIA group quantum dots; and/or the presence of a gas in the gas,
the first organic solvent is one or more of N, N dimethylformamide, N, N dimethyl sulfoxide, toluene and chlorobenzene; and/or the presence of a gas in the gas,
the second quantum dot material is one of IIB-VIA group quantum dots, IIIA-VA group quantum dots or IVA-VIA group quantum dots; and/or the presence of a gas in the gas,
the second organic solvent is one or more of ethanol, methanol, butanol, propanol and isopropanol.
7. An anti-counterfeiting method based on the composite reagent according to any one of claims 1 to 4 or the anti-counterfeiting combination reagent according to any one of claims 5 to 6, which is characterized by comprising the following steps:
spraying a composite reagent on an object to be anti-counterfeit, the composite reagent being configured to be excited by a first ultraviolet light;
providing a second anti-counterfeiting agent, wherein the second anti-counterfeiting agent is configured to react with the composite reagent to form core-shell quantum dots, and the core-shell quantum dots are configured to be excited by second ultraviolet light.
8. The anti-counterfeiting method according to claim 7, wherein the first ultraviolet light excites the composite reagent to show a first color, the second ultraviolet light excites the core-shell quantum dot to show a second color, and the first color and the second color are different.
9. The anti-counterfeiting method according to claim 8, wherein the core-shell quantum dots are configured to be water-quenched.
10. The anti-counterfeit method according to any one of claims 7-9, wherein the wavelength of the first ultraviolet light is 200 nm and 280 nm; the wavelength of the second ultraviolet light is 300-380 nm.
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