CN113554935B - Light response type laser anti-counterfeiting label, preparation method and application thereof - Google Patents
Light response type laser anti-counterfeiting label, preparation method and application thereof Download PDFInfo
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- CN113554935B CN113554935B CN202110674860.3A CN202110674860A CN113554935B CN 113554935 B CN113554935 B CN 113554935B CN 202110674860 A CN202110674860 A CN 202110674860A CN 113554935 B CN113554935 B CN 113554935B
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- G—PHYSICS
- G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
- G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
- G09F3/00—Labels, tag tickets, or similar identification or indication means; Seals; Postage or like stamps
- G09F3/02—Forms or constructions
- G09F3/0291—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time
- G09F3/0294—Labels or tickets undergoing a change under particular conditions, e.g. heat, radiation, passage of time where the change is not permanent, e.g. labels only readable under a special light, temperature indicating labels and the like
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
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- Inks, Pencil-Leads, Or Crayons (AREA)
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Abstract
The application discloses a light response type laser anti-counterfeiting label, a preparation method and application thereof, wherein the light response type laser anti-counterfeiting label comprises a substrate; the organic light-emitting gain layer comprises a laser material layer and an organic ink layer, the laser material layer is coated on the surface of the substrate, and the organic ink layer is coated on the surface of the laser material layer; wherein the laser material layer is prepared from an organic laser material; the organic ink layer is formed by mixing an organic laser material and a photochromic material. The laser label disclosed by the application realizes information encryption by combining a photochromic material with an inkjet printing technology, and has a more visual anti-counterfeiting mode; the printing technology is combined with the traditional organic laser material, so that the laser display label which is easy to prepare and has obvious anti-counterfeiting performance is realized.
Description
Technical Field
The application belongs to the technical field of laser devices, and particularly relates to a light response type laser anti-counterfeit label, a preparation method and application thereof.
Background
Laser displays, unlike displays with incoherent broadband light sources, have higher monochromaticity, wider color gamut, higher contrast, and brighter colors, are very promising next generation display technologies. Organic semiconductor materials have many advantages such as excellent photo-electric properties, wide spectrum coverage, various processing modes, etc., and thus are widely used in the field of multicolor laser devices. The ink jet printing method has great advantages in mass production of patterned structures, and is widely applied to the preparation of organic flexible electronic products.
The ideal anti-counterfeiting technology must be inexpensive, mass-producible, non-destructive, and easy to authenticate to meet the expectations of the anti-counterfeiting technology. Scientific researchers use the advantage of the electrostatic self-assembly strategy to take silver-silicon dioxide core-shell nano particles doped with fluorescein as a building block, and generate a random array of plasmas (metals) as PUF codes, so that multi-optical signal codes and unclonable security labels are generated. Although this fluorescent tag has high security because it is unclonable, there are problems in that verification is inconvenient and it is not easy to observe; researchers can also prepare full color fluorescent security tags by using RGB emissive quantum dots. Although the labels are rich in color and have strong visibility, the labels are microscopic in anti-counterfeiting property, not obvious in property, complex in preparation steps and high in cost.
Disclosure of Invention
This section is intended to outline some aspects of embodiments of the application and to briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section as well as in the description of the application and in the title of the application, which may not be used to limit the scope of the application.
The application has been developed in view of the problems of the above-mentioned and/or prior art that the microscopic anti-counterfeit properties of the label are not significant, the verification is inconvenient and the observation is not easy.
One of the purposes of the application is to provide a light response type laser anti-counterfeit label, wherein the laser label utilizes a photochromic material to combine with an ink-jet printing technology to realize information encryption, and the anti-counterfeit mode is more visual; the printing technology is combined with the traditional organic laser material, so that the laser display label which is easy to prepare and has obvious anti-counterfeiting performance is realized.
In order to solve the technical problems, the application provides the following technical scheme: a light response type laser anti-counterfeit label comprises,
a substrate; the method comprises the steps of,
the organic light-emitting gain layer comprises a laser material layer and an organic ink layer, wherein the laser material layer is coated on the surface of the substrate, and the organic ink layer is coated on the surface of the laser material layer;
wherein the laser material layer is prepared from an organic laser material; the organic ink layer is formed by mixing an organic laser material and a photochromic material.
As a preferable scheme of the light response type laser anti-counterfeiting label, the application comprises the following steps: the photochromic material has reversible color-changing capability.
As a preferable scheme of the light response type laser anti-counterfeiting label, the application comprises the following steps: the emission spectrum of the organic laser material and the absorption spectrum of the photochromic molecule have the same wave band of more than 40 percent.
As a preferable scheme of the light response type laser anti-counterfeiting label, the application comprises the following steps: the organic laser material comprises one of small molecules, star-shaped macromolecules, linear macromolecular materials or binary composites thereof.
As a preferable scheme of the light response type laser anti-counterfeiting label, the application comprises the following steps: the substrate comprises one of fiber paper, quartz plate, polyethylene terephthalate and ITO.
Another object of the present application is to provide a method for preparing a light-responsive laser anti-counterfeit label as described above, comprising,
preparing a solution of an organic laser material and a solution of a photochromic material by using a mixed solvent, so as to ensure that the materials are fully dissolved;
fully mixing the prepared solution of the organic laser material and the prepared solution of the photochromic material according to the volume ratio to obtain an organic mixed solution;
firstly, coating a uniform and flat film prepared from the solution of the organic laser material on a substrate to obtain a laser material layer;
and coating a preset pattern on the preset position of the deposited laser material layer by using the organic mixed solution to obtain the organic ink layer.
As a preferable scheme of the preparation method of the light response type laser anti-counterfeiting label, the preparation method comprises the following steps: the mixed solvent comprises a main solvent and an auxiliary solvent, and the volume ratio of the main solvent to the auxiliary solvent is 1:1-9:1.
Wherein the main solvent is a high boiling point solvent, and the auxiliary solvent is a low boiling point solvent.
As a preferable scheme of the preparation method of the light response type laser anti-counterfeiting label, the preparation method comprises the following steps: the concentration of the organic laser material in the solution of the organic laser material is 5-20 mg/ml; the concentration of the photochromic molecules in the solution of the photochromic material is 5-20 mg/ml; the volume ratio of the solution of the organic laser material to the solution of the photochromic material is 1:1-9:1.
As a preferable scheme of the preparation method of the light response type laser anti-counterfeiting label, the preparation method comprises the following steps: the coating includes one of spin coating, knife coating, or ink jet printing.
Another object of the present application is to provide an application of the light-responsive laser security tag as described above, which is applied as a light emitting device to an organic electroluminescent device, an optically pumped organic laser device or an electrically pumped organic laser device.
Compared with the prior art, the application has the following beneficial effects:
compared with the prior art, the light response type laser anti-counterfeit label, the preparation method and the application thereof provided by the application have the following advantages: based on a doping system of an organic laser material and photochromic molecules, the reversible change of the color of the label under the stimulation of external illumination is realized. And selectively spraying mixed ink doped with photochromic molecules on the film formed by depositing the single organic laser material to form a specific pattern. The anti-counterfeiting laser display label prepared by ultraviolet exposure treatment has the advantages that hidden information is displayed due to color change, and naked eyes can clearly distinguish the information; when the laser label is exposed again by using visible light, the displayed information is re-hidden because the color is restored to the original state, and information encryption is realized.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the description of the embodiments will be briefly described below, it being obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art. Wherein:
FIG. 1 is a schematic diagram of the structure of a light responsive laser security tag of the present application;
FIG. 2 is a graph showing the effect of the light-responsive laser anti-counterfeit label of the embodiment 1 in ultraviolet exposure and visible light exposure;
FIG. 3 is a graph showing the effect contrast of the light-responsive laser anti-counterfeit label in embodiment 3 of the present application;
fig. 4 is a graph showing the comparison of the effects of the light response type laser anti-counterfeit labels with different F8BT concentrations in embodiment 4 of the present application.
Detailed Description
In order that the above-recited objects, features and advantages of the present application will become more apparent, a more particular description of the application will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present application, but the present application may be practiced in other ways other than those described herein, and persons skilled in the art will readily appreciate that the present application is not limited to the specific embodiments disclosed below.
Further, reference herein to "one embodiment" or "an embodiment" means that a particular feature, structure, or characteristic can be included in at least one implementation of the application. The appearances of the phrase "in one embodiment" in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments.
Example 1
(1) The substrate is made of fiber paper, the organic laser material is [ (9, 9-di-n-octyl fluorenyl-2, 7-diyl) -alt- (benzo [2,1,3] thiadiazole-4, 8-diyl) ] (F8 BT), the photochromic material is spiro [1, 3-trimethyl indole chromane ] (SP), the high boiling point solvent is Cyclohexylbenzene (CHB), and the low boiling point solvent is Cyclohexanone (CHN);
(2) CHB and CHN were combined in a volume ratio of 4:1, mixing and configuring in proportion to obtain a mixed solvent;
(3) Preparing F8BT and SP solution by using a mixed solvent, ensuring that the material is fully dissolved, wherein the concentration of the F8BT is 5mg/mL, and the concentration of the SP is 20mg/mL;
(4) Fully mixing the prepared F8BT solution and SP solution according to the volume ratio of 4:1 to obtain an organic mixed solution;
(5) Coating a uniform and flat film prepared from F8BT solution on a substrate in a fume hood by using a spin coater to obtain a laser material layer;
(6) And coating a preset pattern on the preset position of the deposited laser material layer by using the organic mixed solution to obtain the organic ink layer.
The structure of the obtained light response type laser anti-counterfeit label is shown in fig. 1, and the structure comprises a substrate 100 and an organic light emitting gain layer 200, wherein the organic light emitting gain layer 200 comprises a laser material layer 201 and an organic ink layer 202, the laser material layer 201 is coated on the surface of the substrate 100, and the organic ink layer 202 is coated on the surface of the laser material layer 201.
Irradiating the obtained light response type laser anti-counterfeiting label for 60s, 120s and 240s by using an ultraviolet lamp, wherein as shown in fig. 2, the hidden pattern in the label is reddish from yellow, and finally an obvious red preset pattern is displayed; after the label is irradiated under visible light again, the red pattern rapidly changes to yellow, finally disappears, and the information can be clearly seen by naked eyes.
Example 2
This example 2 was prepared in the same manner as example 1, except that the substrate material was selected as a quartz plate. The obtained light response type laser anti-counterfeiting label is stimulated by ultraviolet light, patterns hidden in the label start to reddish from yellow, and finally obvious red preset patterns are displayed; after the label is irradiated again under visible light, the red pattern rapidly changes to yellow and finally disappears. Both the visualization and the hiding of the information can be clearly seen by the naked eye.
Example 3
This example 3 was prepared in the same manner as in example 1, except that the concentration of F8BT was adjusted to 10mg/mL.
As shown in FIG. 3, compared with the photo-responsive laser anti-counterfeit label of the embodiment 1, the prepared pattern details cannot be perfectly displayed, the pattern accuracy is difficult to realize, and the finished product effect is affected. This may be due to the increased concentration of F8BT in the ink, affecting the ejection head of the inkjet printer.
Example 4
This example 4 was the same as the preparation method of example 1, except that the concentration of SP was adjusted to 5 or 10mg/mL. The obtained photo-responsive laser anti-counterfeit label was irradiated with ultraviolet lamp for 0s, 60s, 120s, 240s, and the effect graph of the obtained photo-responsive laser anti-counterfeit label was as shown in fig. 4, and when the SP concentration in the prepared ink was smaller than that of the photo-responsive laser anti-counterfeit label of example 1, the discoloration performance of the label remained, but the degree of discoloration was weaker, and particularly when the degree of discoloration was 5mg/mL, the color change was difficult to verify.
Example 5
(1) The substrate is made of fiber paper, the organic laser material is poly [ 2-methoxy-5- (2-ethylhexyl oxy) -1, 4-phenylacetylene ] (MEH-PPV), the photochromic material is SP, the high boiling point solvent is CHB, and the low boiling point solvent is CHN;
(2) CHB and CHN were combined in a volume ratio of 4:1, mixing and configuring in proportion to obtain a mixed solvent;
(3) Preparing MEH-PPV and SP solution by using a mixed solvent, ensuring that the material is fully dissolved, wherein the concentration of the MEH-PPV is 10mg/mL, and the concentration of the SP is 20mg/mL;
(4) Fully mixing the prepared MEH-PPV solution and the SP solution according to the volume ratio of 4:1 to obtain an organic mixed solution;
(5) Coating a uniform and flat film prepared from MEH-PPV solution on a substrate in a fume hood by using a spin coater to obtain a laser material layer;
(6) And coating a preset pattern on the preset position of the deposited laser material layer by using the organic mixed solution to obtain the organic ink layer.
The obtained light response type laser anti-counterfeiting label is stimulated by ultraviolet light, the hidden pattern in the label is deepened by red, and finally an obvious red preset pattern is displayed; after the label is irradiated under visible light again, the dark red pattern rapidly lightens, and finally the pattern disappears. Both the appearance and the concealment of the information are visible to the naked eye but are not obvious.
Example 6
(1) The substrate is made of fiber paper, the organic laser material is [ (9, 9-di-n-octyl fluorenyl-2, 7-diyl) -alt- (benzo [2,1,3] thiadiazole-4, 8-diyl) ] (F8 BT), the photochromic material is spiro [1, 3-trimethyl indole chromane ] (SP), the high boiling point solvent is Cyclohexylbenzene (CHB), and the low boiling point solvent is Cyclohexanone (CHN);
(2) Mixing CHB and CHN according to the volume ratio of 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1 and 9:1 to obtain a mixed solvent;
the steps (3), (4), (5) and (6) were completed according to the procedure of example 1.
In the test process, the materials are found to be poor in dissolution when mixed and configured in the volume ratio of 5:1, 6:1, 7:1, 8:1 and 9:1; when the components are mixed and disposed in a volume ratio of 1:1, 2:1, and 3:1, ink ejection is impossible.
Example 7
Completing (1), (2) and (3) according to the procedure of example 1;
(4) Fully mixing the prepared F8BT solution and SP solution according to the volume ratio of 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1 and 9:1 respectively to obtain an organic mixed solution;
the steps (5) and (6) were completed according to example 1.
In the test process, the larger the F8BT solution proportion is, the more the spray nozzle is blocked, and the ink cannot be sprayed when the F8BT solution and the SP solution are mixed according to the volume ratio of 5:1, 6:1, 7:1, 8:1 and 9:1.
Compared with the prior art, the light response type laser anti-counterfeit label, the preparation method and the application thereof provided by the application have the following advantages: based on a doping system of an organic laser material and photochromic molecules, the reversible change of the color of the label under the stimulation of external illumination is realized. And selectively spraying mixed ink doped with photochromic molecules on the film formed by depositing the single organic laser material to form a specific pattern. The anti-counterfeiting laser display label prepared by ultraviolet exposure treatment has the advantages that hidden information is displayed due to color change, and naked eyes can clearly distinguish the information; when the laser label is exposed again by using visible light, the displayed information is re-hidden because the color is restored to the original state, and information encryption is realized.
It should be noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that the technical solution of the present application may be modified or substituted without departing from the spirit and scope of the technical solution of the present application, which is intended to be covered in the scope of the claims of the present application.
Claims (8)
1. A light response type laser anti-counterfeiting label is characterized in that: comprising the steps of (a) a step of,
a substrate comprising one of fiber paper, quartz plate, polyethylene terephthalate, and ITO; the method comprises the steps of,
the organic light-emitting gain layer comprises a laser material layer and an organic ink layer, wherein the laser material layer is coated on the surface of the substrate, and the organic ink layer is coated on the surface of the laser material layer;
wherein the laser material layer is prepared from an organic laser material; the organic ink layer is formed by mixing an organic laser material and a photochromic material; the emission spectrum of the organic laser material and the absorption spectrum of the photochromic material have the same wave band of more than 40 percent.
2. The light-responsive laser security tag of claim 1, wherein: the photochromic material has reversible color-changing capability.
3. The light-responsive laser security tag of claim 1, wherein: the organic laser material comprises one of small molecules, star-shaped macromolecules, linear macromolecular materials or binary composites thereof.
4. A method for preparing the light-responsive laser anti-counterfeit label as claimed in any one of claims 1 to 3, characterized in that: comprising the steps of (a) a step of,
preparing a solution of an organic laser material and a solution of a photochromic material by using a mixed solvent, so as to ensure that the materials are fully dissolved;
fully mixing the prepared solution of the organic laser material and the prepared solution of the photochromic material according to the volume ratio to obtain an organic mixed solution;
firstly, coating a uniform and flat film prepared from the solution of the organic laser material on a substrate to obtain a laser material layer;
and coating a preset pattern on the preset position of the deposited laser material layer by using the organic mixed solution to obtain the organic ink layer.
5. The method for preparing the light response type laser anti-counterfeiting label according to claim 4, wherein the method comprises the following steps of: the mixed solvent comprises a main solvent and an auxiliary solvent, and the volume ratio of the main solvent to the auxiliary solvent is 1:1-9:1;
wherein the main solvent is a high boiling point solvent, and the auxiliary solvent is a low boiling point solvent.
6. The method for preparing the light response type laser anti-counterfeiting label according to claim 4, wherein the method comprises the following steps of: the concentration of the organic laser material in the solution of the organic laser material is 5-20 mg/ml; the concentration of the solution of the photochromic material is 5-20 mg/ml; the volume ratio of the solution of the organic laser material to the solution of the photochromic material is 1:1-9:1.
7. The method for preparing the light response type laser anti-counterfeiting label according to claim 4, wherein the method comprises the following steps of: the coating includes one of spin coating, knife coating, or ink jet printing.
8. Use of a photo-responsive laser security tag as claimed in any one of claims 1 to 3 as a light emitting device for an organic electroluminescent device, an optically pumped organic laser device or an electrically pumped organic laser device.
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