CN118379927B - Novel anti-counterfeiting mark based on multispectral quantum dots and manufacturing method thereof - Google Patents
Novel anti-counterfeiting mark based on multispectral quantum dots and manufacturing method thereof Download PDFInfo
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- CN118379927B CN118379927B CN202410808085.XA CN202410808085A CN118379927B CN 118379927 B CN118379927 B CN 118379927B CN 202410808085 A CN202410808085 A CN 202410808085A CN 118379927 B CN118379927 B CN 118379927B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/14—Security printing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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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
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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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- Wood Science & Technology (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
The application relates to the technical field of nano materials, and provides a novel anti-counterfeiting mark based on multispectral quantum dots and a manufacturing method thereof, wherein the mark comprises a basal layer, an intermediate layer and a protective layer, the intermediate layer comprises a multilayer quantum dot ink coating, the transparent film is arranged between each quantum dot ink coating, the quantum dots in each quantum dot ink coating reflect light rays with different spectrums, and the ink of each quantum dot ink coating is sprayed on the whole or partial plane of the layer. The application utilizes the customizable luminescence characteristic of quantum dots based on the size and the components thereof, realizes the complexity and the diversity of luminescence through the multi-layer quantum dot ink, and improves the imitation difficulty of the anti-counterfeit label.
Description
Technical Field
The application relates to the technical field of nano materials, in particular to a novel anti-counterfeiting mark based on multispectral quantum dots and a manufacturing method thereof.
Background
The statements in this section merely provide background information related to the present disclosure and may not necessarily constitute prior art.
The anti-counterfeit label has the functions of identifying the authenticity of the product and improving the counterfeit difficulty of counterfeit and inferior products, and the traditional anti-counterfeit label such as watermarks, bar codes, two-dimensional codes and the like is easy to tamper and copy, has a short life cycle and is easy to damage by environmental influences.
Along with the development of anti-counterfeiting technology, photoluminescent materials are applied to the anti-counterfeiting field, but the existing fluorescent label has single luminous characteristic and is easy to imitate, and along with the development of technology, the difficulty and cost of imitation can be rapidly reduced, so that the variety of luminous fluorescent labels is realized, the imitation cost is increased, and the technical problem to be solved in the anti-counterfeiting technical field is solved urgently.
Disclosure of Invention
In order to solve the problems in the background technology, the application provides a novel anti-counterfeiting mark based on multispectral quantum dots and a manufacturing method thereof.
The application provides a novel anti-counterfeiting mark based on multispectral quantum dots, which comprises the following components: a substrate layer, an intermediate layer and a protective layer, the intermediate layer comprises a plurality of layers of quantum dot ink coating;
each quantum dot ink coating is spaced by a transparent film, quantum dots in each quantum dot ink coating reflect light rays with different spectrums, and the ink of each quantum dot ink coating is sprayed on the whole or partial plane of the layer;
The light reflected by the quantum dots in each quantum dot ink coating with different spectrums is achieved through different quantum dot components or different sizes of the quantum dots.
Preferably, the substrate layer is made of plastic, paper or a metal film;
The material of the protective layer is transparent adhesive;
the transparent film is made of transparent ultrathin glass or plastic film:
the quantum dot components in the multilayer quantum dot ink coating at least comprise cadmium selenide CdSe, cadmium sulfide CdS, indium phosphide InP and lead sulfide PbS.
The application also provides a manufacturing method of the novel anti-counterfeiting mark based on the multispectral quantum dots, which comprises the following specific steps:
Step 100: quantum dots with different sizes and components are prepared, and surface modification is carried out on the quantum dots;
step 200: preparing quantum dot ink;
step 300: designing patterns of each layer of the anti-counterfeiting mark and selecting quantum dot ink;
Step 400: the preparation of the anti-counterfeiting mark is carried out by using an interlayer injection molding and interlayer isolation method.
Preferably, in the step 100, the preparation method of the quantum dot includes:
CdSe, cdS: dissolving cadmium salt and selenium powder or sulfur powder in trioctyl phosphorus-oxygen solvent, heating to 260-300 ℃, rapidly injecting selenium or sulfur precursor, and controlling time to obtain quantum dots with different sizes;
InP: dissolving indium salt and a phosphorus precursor in trioctylphosphorus-oxygen solvent, heating to about 260-300 ℃, and controlling the reaction time and temperature to form InP quantum dots with different sizes;
PbS: and dissolving lead salt and sodium sulfide in water, and controlling the pH value and the temperature to obtain the PbS quantum dot.
Preferably, in the step 100, the specific method for surface modification of the quantum dot is:
the original short-chain ligand is replaced by long-chain organic ligand, the quantum dot and the new ligand are mixed in an organic solvent compatible with the ink matrix, and the surface of the quantum dot is completely covered by the ligand through heating and stirring.
Preferably, in the step 200, the method for configuring the quantum dot ink includes:
step 201, mixing an organic solvent and resin, and stirring to ensure complete dissolution of the resin;
step 202: adding a dispersing agent and a stabilizing agent into the mixed solvent, and continuously stirring to form a uniform mixture;
Step 203: adding quantum dots at a constant speed, and ensuring uniform mixing of the quantum dots;
Step 204: adding thickener, optionally light stabilizer or ultraviolet resistance agent.
Preferably, in said step 201, a high-speed homogenizer is used to ensure complete dissolution of the resin;
In step 203, a high-speed homogenizer or ultrasonic waves are used to ensure uniform mixing of the quantum dots.
Preferably, the quantum dot ink comprises the following components in percentage by weight:
1 to 5 percent of quantum dot, 30 to 50 percent of organic solvent, 20 to 40 percent of resin, 2 to 5 percent of dispersing agent,
1-3% Of stabilizer, 1-3% of thickener and 1-2% of light stabilizer;
The organic solvent is any one of acetone, ethanol or isopropanol, the resin is any one of polyurethane resin, polyester resin or acrylic resin, the dispersing agent is Polyoxonol, the stabilizer is an anti-sedimentation agent, and the thickener is hydroxyethyl cellulose or diatomite.
Preferably, in the step 200, the method further comprises preparing a filler based on the steps 201, 202, 204;
in the step 400, the specific method for preparing the anti-counterfeiting mark by using the methods of interlayer injection molding and interlayer isolation is as follows:
Step 401: setting parameters of an injection molding machine based on materials of a base layer and components of quantum dot ink;
Step 402: starting to spray quantum dot ink from a substrate layer, firstly judging whether the current coating is locally sprayed, if so, jumping to a step 403a, and if not, jumping to a step 403b;
Step 403a: firstly, spraying a filler on a non-color-changing area, then spraying corresponding quantum dot ink on the color-changing area, and carrying out ultrasonic treatment on the junction of the filler and the quantum dot ink;
step 403b: carrying out quantum dot ink spraying on the current coating;
Step 404: carrying out initial curing on the current coating, and adding a transparent film at the top of the coating;
Step 405: and (4) circularly performing the operations from step 402 to step 404 until the spraying of all the coatings is completed, and integrally curing the anti-counterfeiting mark.
Compared with the prior art, the application has the beneficial effects that:
(1) The application utilizes the customizable luminescence characteristic of quantum dots based on the size and the components thereof, realizes the complexity and the diversity of luminescence by a plurality of layers of quantum dot ink, improves the imitation difficulty of the anti-counterfeit label, and compared with the traditional anti-counterfeit label, the quantum dot can realize various colors and luminous characteristics, has higher chemical stability and optical stability, can keep the performance unchanged under various environmental conditions, and has longer service life and durable anti-counterfeiting effect.
(2) According to the application, through the design of spraying the local quantum dot ink of each layer, the luminous diversity of the anti-counterfeiting mark is further improved, the quantum dot ink is conveniently saved, and the anti-counterfeiting cost is reduced.
(3) The quantum ink disclosed by the application has the advantages of good stability of components, strong universality and uniform quantum dot distribution, is convenient for the centralized production of quantum dot inks with different sizes and quantum dot components, and further saves the production cost of anti-counterfeiting marks.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application.
Figure 1 is a schematic flow chart of the method of the application,
Figure 2 is a schematic representation of a multi-layered quantum dot combination of the present application,
Fig. 3 is a representation of the present application showing visual and spectrometer identification.
Detailed Description
The application will be further described with reference to the drawings and examples.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments in accordance with the present disclosure. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In the present disclosure, terms such as "upper", "lower", "left", "right", "front", "rear", "vertical", "horizontal", "side", "bottom", and the like indicate an azimuth or a positional relationship based on the azimuth or the positional relationship shown in the drawings, are merely relational terms determined for convenience in describing structural relationships of the various components or elements of the present disclosure, and do not denote any one of the components or elements of the present disclosure, and are not to be construed as limiting the present disclosure.
Example 1
As shown in fig. 1 to 3, the present application provides a novel anti-counterfeiting label based on multispectral quantum dots, comprising: a substrate layer, an intermediate layer and a protective layer, the intermediate layer comprises a plurality of layers of quantum dot ink coating;
each quantum dot ink coating is spaced by a transparent film, quantum dots in each quantum dot ink coating reflect light rays with different spectrums, and the ink of each quantum dot ink coating is sprayed on the whole or partial plane of the layer;
The light reflected by the quantum dots in each quantum dot ink coating with different spectrums is achieved through different quantum dot components or different sizes of the quantum dots.
The quantum dot can realize various colors and luminous characteristics, has higher chemical stability and optical stability, can keep performance unchanged under various environmental conditions, has longer service life and durable anti-counterfeiting effect, further improves the luminous diversity of anti-counterfeiting marks by virtue of the design of spraying the local quantum dot ink of each layer, and is convenient for saving the quantum dot ink and reducing the anti-counterfeiting cost.
In the figure, the shadow parts of a, b and c are respectively single-layer quantum dots, double-layer quantum dots and three-layer quantum dots for composite display, thereby realizing the complexity and diversity of luminescence and improving the imitation difficulty of the anti-counterfeit label.
Specifically, the substrate layer is made of plastic, paper or a metal film;
The protective layer is made of transparent adhesive, and comprises any one of transparent adhesive such as polyurethane, acrylic acid, silicone and the like;
the transparent film is made of transparent ultrathin glass or plastic film, and the plastic film can be any one of PE film, PP film and other films:
the quantum dot components in the multilayer quantum dot ink coating at least comprise cadmium selenide CdSe, cadmium sulfide CdS, indium phosphide InP and lead sulfide PbS, wherein the cadmium selenide CdSe is used for emitting red to green light, the cadmium sulfide CdS is used for emitting blue to green light, the indium phosphide InP is used for emitting green to red light, and the lead sulfide PbS is used for emitting light in an infrared spectrum range.
Based on the quantum dot ink formed by the quantum dots, visual or machine-identified light rays can be realized, and a multi-layer complex pattern can be formed, so that the imitation difficulty is further enhanced.
As shown in fig. 3, the labeling contents are "classical rising wine industry", "classical" and "wine" are labeled by spraying lead sulfide PbS quantum dot ink, the display effect under the naked eye condition is shown in the upper part of fig. 3, and the whole content of "classical rising wine industry" is shown in the lower part of fig. 3 under the spectrometer.
Based on the anti-counterfeiting mark, the application also provides a manufacturing method of the novel anti-counterfeiting mark based on the multispectral quantum dot, which comprises the following steps:
Step 100: quantum dots with different sizes and components are prepared, and surface modification is carried out on the quantum dots;
step 200: preparing quantum dot ink;
step 300: designing patterns of each layer of the anti-counterfeiting mark and selecting quantum dot ink;
Step 400: the preparation of the anti-counterfeiting mark is carried out by using an interlayer injection molding and interlayer isolation method.
Specifically, in the step 100, the preparation method of the quantum dot includes:
CdSe, cdS: dissolving cadmium salt and selenium powder or sulfur powder in trioctyl phosphorus-oxygen solvent, heating to 260-300 ℃, rapidly injecting selenium or sulfur precursor, and controlling time to obtain quantum dots with different sizes;
InP: dissolving indium salt and a phosphorus precursor in trioctylphosphorus-oxygen solvent, heating to about 260-300 ℃, and controlling the reaction time and temperature to form InP quantum dots with different sizes;
PbS: and dissolving lead salt and sodium sulfide in water, and controlling the pH value and the temperature to obtain the PbS quantum dot.
The CdSe, cdS, inP quantum dots are prepared by adopting a hot injection method, and the PbS quantum dots are prepared by adopting a solution method.
Specifically, in the step 100, to prevent the surface of the quantum dot from being incompatible with the ink matrix (organic solvent and resin), the surface modification is performed on the quantum dot, which specifically includes:
the original short-chain ligand is replaced by long-chain organic ligand (such as silane compound, polyvinylpyrrolidone PVP, polystyrene sulfonic acid PSS and the like), the quantum dots and the new ligand are mixed in an organic solvent compatible with the ink matrix, the surface of the quantum dots is completely covered by the ligand through heating and stirring, and the solubility and the dispersibility of the quantum dots in the ink matrix are improved through surface modification.
Specifically, in the step 200, the method for configuring the quantum dot ink includes:
step 201, mixing an organic solvent and resin, and stirring to ensure complete dissolution of the resin;
step 202: adding a dispersing agent and a stabilizing agent into the mixed solvent, and continuously stirring to form a uniform mixture;
Step 203: adding quantum dots at a constant speed, and ensuring uniform mixing of the quantum dots;
Step 204: adding thickener, optionally light stabilizer or ultraviolet resistance agent.
Preferably, in the step 201, a high-speed homogenizer is used to ensure complete dissolution of the resin, and in the step 203, a high-speed homogenizer or ultrasonic waves are used to ensure uniform mixing of the quantum dots.
Specifically, the quantum dot ink comprises the following components in percentage by weight:
1% -5% of quantum dots, and adjusting according to the required optical effect and color intensity;
30% -50% of organic solvent, which is used for dissolving other components and adjusting the viscosity of the ink;
20% -40% of a resin to provide adhesion and drying characteristics of the ink;
2% -5% of dispersing agent, which helps quantum dots disperse uniformly in solvent;
1% -3% of stabilizer to prevent quantum dot from precipitating;
1-3% of thickener, and adjusting rheological property of the printing ink;
1% -2% of light stabilizer, improve the stability of the ink under sunlight;
The organic solvent is any one of acetone, ethanol or isopropanol, the resin is any one of polyurethane resin, polyester resin or acrylic resin, the dispersing agent is Polyoxonol, the stabilizer is an anti-sedimentation agent, and the thickener is hydroxyethyl cellulose or diatomite.
In the step 200, the method further comprises the steps of preparing a filler based on the steps 201, 202 and 204;
in the step 400, the specific method for preparing the anti-counterfeiting mark by using the methods of interlayer injection molding and interlayer isolation is as follows:
Step 401: setting parameters of an injection molding machine based on materials of a base layer and components of quantum dot ink;
Step 402: starting to spray quantum dot ink from a substrate layer, firstly judging whether the current coating is locally sprayed, if so, jumping to a step 403a, and if not, jumping to a step 403b;
Step 403a: firstly, spraying a filler on a non-color-changing area, then spraying corresponding quantum dot ink on the color-changing area, and carrying out ultrasonic treatment on the junction of the filler and the quantum dot ink;
step 403b: carrying out quantum dot ink spraying on the current coating;
Step 404: carrying out initial curing on the current coating, and adding a transparent film at the top of the coating;
Step 405: and (4) circularly performing the operations from step 402 to step 404 until the spraying of all the coatings is completed, and integrally curing the anti-counterfeiting mark.
In the steps 404 and 405, the curing operation may be performed by UV light irradiation or heat treatment.
Example 2
Based on the manufacturing method of the novel anti-counterfeiting mark based on the multispectral quantum dots in the embodiment 1, the configuration of the cadmium selenide CdSe quantum dots and the corresponding quantum dot ink is described in the embodiment.
Preparation of cadmium selenide CdSe quantum dots: and (3) dissolving cadmium salt and selenium powder in trioctyl phosphorus-oxygen solvent, heating to 285 ℃, rapidly injecting selenium precursor, and controlling the time to obtain quantum dots with different sizes.
The quantum dot ink based on the 5nm cadmium selenide CdSe quantum dot configuration comprises the following components in percentage by weight:
CdSe quantum dot, weight ratio is 4%;
isopropyl alcohol is used as the organic solvent, and the weight ratio is 48%;
The resin uses polyurethane resin with the weight ratio of 39%;
The dispersant is Polyoxonol with the weight ratio of 2.5%;
the stabilizer uses an anti-sedimentation agent, and the weight ratio is 2.8%;
The thickener is hydroxyethyl cellulose, and the weight ratio is 2.5%;
The weight ratio of the light stabilizer is 1.2%.
The above is only a preferred embodiment of the present application, and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
While the foregoing description of the embodiments of the present application has been presented in conjunction with the drawings, it should be understood that it is not intended to limit the scope of the application, but rather, it is intended to cover all modifications or variations within the scope of the application as defined by the claims of the present application.
Claims (5)
1. The manufacturing method of the novel anti-counterfeiting mark based on the multispectral quantum dots is characterized by comprising a substrate layer, an intermediate layer and a protective layer, wherein the intermediate layer comprises a plurality of layers of quantum dot ink coatings, each quantum dot ink coating is provided with a transparent film at intervals, the quantum dots in each quantum dot ink coating reflect light rays with different spectrums, the ink of each quantum dot ink coating is sprayed on the whole or partial plane of the substrate layer, and the light rays with different spectrums reflected by the quantum dots in each quantum dot ink coating are achieved through different quantum dot components or different sizes of the quantum dots;
The method specifically comprises the following steps:
Step 100: quantum dots with different sizes and components are prepared, and surface modification is carried out on the quantum dots;
step 200: preparing quantum dot ink;
step 300: designing patterns of each layer of the anti-counterfeiting mark and selecting quantum dot ink;
Step 400: preparing an anti-counterfeiting mark by using an interlayer injection molding and interlayer isolation method;
In the step 200, the method for configuring the quantum dot ink includes:
step 201, mixing an organic solvent and resin, and stirring to ensure complete dissolution of the resin;
step 202: adding a dispersing agent and a stabilizing agent into the mixed solvent, and continuously stirring to form a uniform mixture;
Step 203: adding quantum dots at a constant speed, and ensuring uniform mixing of the quantum dots;
Step 204: adding a thickening agent, optionally a light stabilizer or an ultraviolet resistance agent;
In the step 200, the method further comprises the steps of preparing a filler based on the steps 201, 202 and 204;
in the step 400, the specific method for preparing the anti-counterfeiting mark by using the methods of interlayer injection molding and interlayer isolation is as follows:
Step 401: setting parameters of an injection molding machine based on materials of a base layer and components of quantum dot ink;
Step 402: starting to spray quantum dot ink from a substrate layer, firstly judging whether the current coating is locally sprayed, if so, jumping to a step 403a, and if not, jumping to a step 403b;
Step 403a: firstly, spraying a filler on a non-color-changing area, then spraying corresponding quantum dot ink on the color-changing area, and carrying out ultrasonic treatment on the junction of the filler and the quantum dot ink;
step 403b: carrying out quantum dot ink spraying on the current coating;
Step 404: carrying out initial curing on the current coating, and adding a transparent film at the top of the coating;
Step 405: and (4) circularly performing the operations from step 402 to step 404 until the spraying of all the coatings is completed, and integrally curing the anti-counterfeiting mark.
2. The method for manufacturing the novel anti-counterfeiting mark based on the multispectral quantum dots according to claim 1, which is characterized by comprising the following steps:
In the step 100, the preparation method of the quantum dot includes:
CdSe, cdS: dissolving cadmium salt and selenium powder or sulfur powder in trioctyl phosphorus-oxygen solvent, heating to 260-300 ℃, rapidly injecting selenium or sulfur precursor, and controlling time to obtain quantum dots with different sizes;
InP: dissolving indium salt and a phosphorus precursor in trioctylphosphorus-oxygen solvent, heating to 260-300 ℃, and controlling the reaction time and temperature to form InP quantum dots with different sizes;
PbS: and dissolving lead salt and sodium sulfide in water, and controlling the pH value and the temperature to obtain the PbS quantum dot.
3. The method for manufacturing the novel anti-counterfeiting mark based on the multispectral quantum dots, which is characterized by comprising the following steps of:
in the step 100, the specific method for performing surface modification on the quantum dots is as follows:
the original short-chain ligand is replaced by long-chain organic ligand, the quantum dot and the new ligand are mixed in an organic solvent compatible with the ink matrix, and the surface of the quantum dot is completely covered by the ligand through heating and stirring.
4. The method for manufacturing the novel anti-counterfeiting mark based on the multispectral quantum dots, which is characterized by comprising the following steps of:
in step 201, a high speed homogenizer is used to ensure complete dissolution of the resin;
In step 203, a high-speed homogenizer or ultrasonic waves are used to ensure uniform mixing of the quantum dots.
5. The method for manufacturing the novel anti-counterfeiting mark based on the multispectral quantum dots, which is characterized by comprising the following steps of:
The quantum dot ink comprises the following components in percentage by weight:
1-5% of quantum dots, 30-50% of organic solvents, 20-40% of resins, 2-5% of dispersing agents, 1-3% of stabilizers, 1-3% of thickeners and 1-2% of light stabilizers;
The organic solvent is any one of acetone, ethanol or isopropanol, the resin is any one of polyurethane resin, polyester resin or acrylic resin, the dispersing agent is Polyoxonol, the stabilizer is an anti-sedimentation agent, and the thickener is hydroxyethyl cellulose or diatomite.
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CN108538187A (en) * | 2018-04-16 | 2018-09-14 | 上海印钞有限公司 | A kind of combination phosphor pattern and its application |
CN109649031A (en) * | 2018-11-19 | 2019-04-19 | 江苏学泰印务有限公司 | A kind of laminated multi-layer formula is without chromatography side transfer film |
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