CN113506974B - Antenna structure for electronic tag, preparation method and electronic tag - Google Patents
Antenna structure for electronic tag, preparation method and electronic tag Download PDFInfo
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- CN113506974B CN113506974B CN202110571602.2A CN202110571602A CN113506974B CN 113506974 B CN113506974 B CN 113506974B CN 202110571602 A CN202110571602 A CN 202110571602A CN 113506974 B CN113506974 B CN 113506974B
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Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/12—Supports; Mounting means
- H01Q1/22—Supports; Mounting means by structural association with other equipment or articles
- H01Q1/2208—Supports; Mounting means by structural association with other equipment or articles associated with components used in interrogation type services, i.e. in systems for information exchange between an interrogator/reader and a tag/transponder, e.g. in Radio Frequency Identification [RFID] systems
- H01Q1/2225—Supports; Mounting means by structural association with other equipment or articles associated with components used in interrogation type services, i.e. in systems for information exchange between an interrogator/reader and a tag/transponder, e.g. in Radio Frequency Identification [RFID] systems used in active tags, i.e. provided with its own power source or in passive tags, i.e. deriving power from RF signal
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/21—After-treatment
- C01B32/22—Intercalation
- C01B32/225—Expansion; Exfoliation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
- H01Q1/364—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith using a particular conducting material, e.g. superconductor
- H01Q1/368—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith using a particular conducting material, e.g. superconductor using carbon or carbon composite
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
- H01Q1/38—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith formed by a conductive layer on an insulating support
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses an antenna structure for an electronic tag, a preparation method and the electronic tag, wherein the antenna structure is provided with an antenna conducting layer, and the antenna conducting layer at least comprises a layer of graphite paper or graphite paper composite material. The conductive layer of the tag antenna structure is made of the graphite paper material, has the advantages of low cost, easiness in processing and environmental friendliness, can improve the corrosion resistance of the antenna, and solves the problems of complex process, low manufacturing efficiency, high cost, environmental pollution, limited application field and the like in the prior art.
Description
Technical Field
The invention relates to the technical field of radio frequency identification, in particular to an antenna structure for an electronic tag, a preparation method and the electronic tag.
Background
The wireless radio frequency identification technology is a non-contact type automatic data acquisition technology and is also one of core technologies of the Internet of things. The information acquisition device has the advantages that the information acquisition speed is high, mechanical or optical contact is not needed, the information acquisition device is completely completed through a wireless communication technology, hundreds of thousands of object information can be acquired in 1 second at the same time, and the information acquisition accuracy is high. At present, the technology is used in the fields of logistics storage, transportation, safety anti-counterfeiting, mobile payment and the like, but the main bottleneck limiting the popularization and application of the technology is the price, the size and the environmental adaptability of the label.
The antenna materials of the electronic tag commonly used at present are copper, aluminum, silver paste or conductive ink, and the commonly used preparation methods comprise etching, ink-jet printing, chemical plating, electroplating, hot stamping, silk screen, gravure printing and the like. The main flow etching method needs strong acid solution to corrode the unprotected metal layer and strong alkali solution to remove the protective layer, so that the problems of large pollution, serious waste, large carrier limitation, high cost and the like exist; for the screen printing process of the conductive silver paste, the material cost is too high, and the price of the conductive silver paste is different from 360 yuan per kilogram to tens of thousands yuan per kilogram.
In recent years, research shows that the graphene material has a microscopic topological structure, so that the graphene material has high conductivity, and the graphene composite conductive paste or conductive ink is a preferable scheme for replacing the traditional etching method by an electronic tag manufactured by a printing antenna method. However, the conductivity of the existing graphene composite conductive paste or conductive ink is affected by various factors such as the type of conductive material, particle size, shape, filling amount, dispersion state, adhesive type, curing time and the like, so that the conductivity of the graphene composite conductive paste or conductive ink is poor, and the conductivity requirement of an electronic tag antenna cannot be met. In addition, researchers also prepare a mask layer with a preset antenna pattern in advance, transfer the mask layer pattern onto a target substrate in a mode of ion etching a graphene film, and then obtain the graphene antenna through subsequent treatment. The preparation method based on the template is complex in operation, high in cost, long in production period and easy to produce pollution and defects in the pattern transfer process.
Disclosure of Invention
The invention mainly aims to provide an antenna structure for an electronic tag and a preparation method thereof, which are used for solving the problems of complex antenna process, low manufacturing efficiency, high cost, environmental pollution, limited application field and the like in the prior art.
In order to achieve the above object, according to a first aspect of the present invention, there is provided an antenna structure for an electronic tag, in particular, the antenna structure has an antenna conductive layer including at least one layer of graphite paper or graphite paper composite material.
Further, the graphite paper is one or more of flexible graphite paper, ultrathin graphite paper, heat-conducting graphite paper, graphite paper coiled materials or graphite paper boards; the graphite paper composite material is a composite of graphite paper and a carbon material, a metal material or a ceramic material.
Further, the thickness of the graphite paper or the graphite paper composite material is 5 μm-500 μm.
Further, the thickness of the graphite paper or the graphite paper composite material is 5-30 μm.
Further, the antenna structure further comprises a protective layer, and the protective layer is in covering connection with the graphite paper or the graphite paper composite material of the antenna conductive layer.
Further, the antenna conductive layer is formed by performing die cutting or half die cutting after being covered with graphite paper or graphite paper composite material and the protective layer.
Further, the antenna structure further comprises a substrate, the antenna conducting layer is arranged on the substrate, the antenna conducting layer is bonded with the substrate through a back adhesive layer, and the antenna conducting layer is formed by laminating graphite paper or a graphite paper composite material with the protective layer and then sticking the graphite paper or the graphite paper composite material to the substrate for half die cutting.
Further, the antenna structure further comprises a third layer of carrier, the third layer of carrier is arranged on the protective layer, and the third layer of carrier is made of an insulating polymer film material.
In a second aspect, the present application provides a method for manufacturing an antenna structure of an electronic tag, including:
covering and combining graphite paper or a graphite paper composite material with the protective layer to obtain a graphite composite film;
carrying out back glue on the surface of the substrate to obtain a high-conductivity graphite film;
processing the high-conductivity graphite film to obtain an electronic tag antenna structure;
the method further comprises a step of cutting and forming the conductive layer, wherein the cutting mode of cutting and forming specifically comprises laser cutting, flame cutting, manual cutting or die cutting;
The conducting layer cutting and forming step is implemented by directly cutting graphite paper or a graphite paper composite material, or cutting after covering and combining the graphite paper or the graphite paper composite material with a protective layer, or cutting after back gluing the graphite composite film on the surface of a base material.
Further, the processing of the high-conductivity graphite film comprises attaching a third layer of carrier on the surface of the high-conductivity graphite film.
Further, the cutting mode for cutting and forming the conductive layer is specifically die cutting, and the steps specifically include:
After the graphite paper or the graphite paper composite material and the protective layer are covered and combined, the graphite paper or the graphite paper composite material covered and combined on the protective layer is die-cut according to a preset shape to obtain the protective layer and the graphite paper with the same shape, or the graphite paper composite material covered and combined on the protective layer is half-die-cut according to the preset shape, the protective layer is reserved, and part of the graphite paper or the graphite paper composite material is cut off to obtain the graphite composite film;
Or, the die-cutting molding step specifically comprises the following steps:
After the step of obtaining the high-conductivity graphite film or attaching a third layer of carrier on the surface of the high-conductivity graphite film, performing half die cutting on the graphite paper or the graphite paper composite material attached to the surface of the substrate according to a preset shape to obtain a protective layer and the graphite paper with the same shape, and keeping the substrate from being cut.
Further, the covering the graphite paper or the graphite paper composite material with the protective layer includes:
And carrying out hot rolling treatment on the graphite paper or the graphite paper composite material and the protective layer by adopting a pair roller press to enable the graphite paper or the graphite paper composite material and the protective layer to be covered, wherein the upper die temperature of the roller press is 25-400 ℃, and the lower die temperature is 25-400 ℃.
Further, before the step of covering the graphite paper or the graphite paper composite material with the protective layer, the method further comprises: preparing graphite paper or a graphite paper composite material, wherein the prepared graphite paper or graphite paper composite material has a controlled thickness of 5-30 mu m.
Further, the preparing of the graphite paper or the graphite paper composite material comprises:
pretreating a graphite paper raw material to prepare expandable graphite, and then expanding and calendaring the expandable graphite at a preset expansion temperature to prepare graphite paper or a graphite paper composite material;
Wherein the graphite material is one or more of natural crystalline flake graphite, pyrolytic graphite, artificial graphite and graphite oxide; wherein the expansion temperature is 200-1000 ℃.
Further, the preparation of the expandable graphite from the graphite paper raw material through pretreatment comprises the following steps:
Mixing graphite paper raw materials, washing with water and drying after the mixing treatment to obtain expandable graphite;
The rolling specifically comprises rolling treatment for preset times, wherein the preset times are 3-5 times.
Further, the mixing process specifically includes: mixing graphite material and a reaction compound, and stirring at a preset reaction temperature; wherein the preset reaction temperature is 20-50 ℃; the stirring time is 60min-90min.
Further, the mixing process is: immersing graphite material in a reaction solution with a preset proportion, and carrying out electrolysis treatment under constant current, wherein the electrolysis time is 2-3 h.
In a third aspect, an electronic tag is provided, including the antenna structure or the antenna structure manufactured by the manufacturing method.
The tag antenna made of the graphite paper material is adopted, the problem of insufficient conductivity caused by the antenna made of conductive ink and film materials is solved, the manufacturing process is simpler, and in addition, the square resistance of the tag antenna manufactured by the method is far smaller than that of a carbon paste antenna.
In summary, the beneficial technical effects of the invention are as follows:
(1) The application changes the constitution of the original traditional electronic tag antenna, adopts graphite paper material to manufacture the antenna conducting layer of the tag antenna structure, overcomes the problem of insufficient conductivity caused by manufacturing the antenna by conducting ink and film materials, has simpler manufacturing process, and has the square resistance far smaller than that of a carbon paste antenna.
(2) And because the application has simple composition structure, and the antenna tag is prepared on the basis of the graphite paper material only by the processes of covering, cutting, pasting and the like, the preparation structure is simple and environment-friendly.
(3) The graphite paper or the graphite paper composite material which is covered on the protective layer and/or adhered on the base material is subjected to die cutting or half die cutting according to the preset shape, and the die cutting die cuts the shape of the antenna conductive layer according to the preset cutting thickness and shape in a mode of firstly covering or adhering and then die cutting, so that the shape of the required conductive layer can be conveniently and stably obtained without damaging the fragile graphite paper material;
(4) The thickness of the graphite paper or the graphite paper composite material can be better controlled in the process of preparing the graphite paper or the graphite paper composite material by the method for generating the graphite paper, and the generated graphite paper has a clear and stable structure.
Drawings
FIGS. 1 (a) and (b) are scanning electron microscope images of the graphite paper material of the present invention;
FIG. 2 (a) is a schematic structural diagram of a graphite composite film obtained after half-die cutting in accordance with an embodiment of the present invention;
Fig. 2 (b) is a schematic structural diagram of an antenna conductive layer obtained after cutting and molding graphite paper or a graphite paper composite material according to an embodiment of the present invention;
Fig. 3 is a schematic diagram of an electronic tag antenna without a third layer carrier according to an embodiment of the present invention;
fig. 4 is a schematic diagram of an electronic tag antenna structure including a third layer carrier according to an embodiment of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present application more apparent, the following detailed description of the embodiments of the present application will be given with reference to the accompanying drawings, and it should be noted that the features of the embodiments of the present application may be arbitrarily combined with each other without conflict.
Example 1:
According to the antenna structure for the electronic tag, which is provided by the embodiment of the invention, the antenna structure is provided with the antenna conducting layer, and the antenna conducting layer at least comprises one layer of graphite paper or graphite paper composite material.
In the prior art, graphite paper is often used as a heat dissipation material applied to notebook computers, flat panel displays, digital cameras, mobile phones and personal assistant devices, and a person skilled in the art does not consider the graphite paper as a conductive layer of an antenna structure on an electronic tag, and the graphite paper is mainly limited in that the conventional etching method, the inkjet printing method, the electroless plating method, the electroplating method, the hot stamping method, the silk screen method, the gravure printing method and the like are used for preparing a wire of the electronic tag in the prior art.
At present, the price of the aluminum etching antenna tag on the market is different from 0.1 yuan to several yuan, the price of the conductive ink is different from 180 yuan/kg to thousands yuan, and the price of the conductive silver paste is different from 360 yuan/kg to tens of thousands yuan, so that the price of the graphite paper antenna can be reduced to be within 0.1 yuan, and the price of the electronic tag is greatly reduced. And compared with a carbon paste antenna, the finally prepared electronic tag has lower resistance, and the manufactured RFID tag antenna has good electrical performance and can meet the working requirements of low frequency, high frequency, ultrahigh frequency and microwave frequency bands.
Specifically, in this embodiment, the type of the graphite paper may be selected from the following types: the graphite paper is one or more of flexible graphite paper, ultrathin graphite paper, heat-conducting graphite paper, graphite paper coiled material or graphite paper board; the graphite paper composite material is a composite prepared by jointly processing graphite paper and a carbon material, a metal material or a ceramic material; the carbon material is graphite flake, graphite plate or carbon powder; the metal material is a metal plate or metal powder; the ceramic material is oxide ceramic, nitride ceramic, carbide ceramic or boride ceramic.
Further preferably, in this embodiment, the graphite paper or graphite paper composite material has a thickness of 5 μm to 500 μm, still further preferably 5 μm to 30 μm. The common graphite paper is generally about 1mm thick and is mainly used as a heat dissipation layer of electronic equipment; according to the application, graphite paper with special size and thickness is selected as a component part of the conductive layer of the electronic tag, and the graphite paper has outstanding conductive performance, is easier to process compared with the existing manufacturing process, can be manufactured into antennas with different sizes and shapes, and compared with the traditional linear antenna with the same width, the graphite paper has the advantages of effectively shortening the length of the antenna, reducing the material consumption, further reducing the cost, increasing the width of the antenna, reducing the manufacturing error of the process and improving the yield. Preferably, the thickness of the graphite paper or the graphite paper composite material is 5 μm-30 μm, and compared with the common graphite paper material in the market, the special process is adopted in the application, so that the production place is more suitable for the thickness of the graphite paper material of the electronic tag, and the specific reference is made to the following description.
Further, in this embodiment, the antenna structure further includes a protective layer, and the protective layer is covered and connected with the graphite paper or the graphite paper composite material of the antenna conductive layer. The protective layer not only realizes the protection of the conductive layer, but also considers the graphite paper material which is thinner in size and fragile in the embodiment, the protective layer can prevent the breakage of the graphite paper or the graphite paper composite material, and can process the graphite paper material more stably. Wherein the protective layer is selected from one of polymer film material, paper and fabric.
Specifically, in this embodiment, the shape of the antenna conductive layer is made by die cutting or half die cutting after the graphite paper or the graphite paper composite material and the protective layer are combined. Because of the brittle nature of the material and the thinness of the graphite paper in the electronic tag of the embodiment, the die-cut shape of the antenna conductive layer in the application can be cut out by a mode of covering and then die-cutting, and when the die-cutting is particularly half-die-cutting, namely the die-cutting die is through a preset cutting thickness and shape, but the protective layer is not cut off. Referring specifically to fig. 2, reference numeral 1 denotes an antenna conductive layer 1 formed after die cutting, and reference numeral 2 denotes a protective layer 2. In other embodiments, the protective layer may also be die-cut with the graphite paper or graphite paper composite material, and the protective layer may also protect the graphite paper material having brittle characteristics from damage during die-cutting.
Further, the application also comprises a substrate, the antenna conductive layer is arranged on the substrate, and the antenna conductive layer is adhered to the substrate through the back adhesive layer 3. As shown in fig. 3, includes an antenna conductive layer 1, a protective layer 2, a backing layer 3, and a substrate 4. The antenna conducting layer can also be formed by half die cutting after being attached to the base material, specifically, the shape of the antenna conducting layer is prepared by half die cutting after being attached to the base material after being covered by graphite paper or graphite paper composite material and the protective layer, so that the shape of the protective layer after half die cutting is consistent with that of the antenna conducting layer, and the base material is kept without being cut off. The cutting mode is more stable, and can be cut and molded at one time. Also optionally, in other embodiments, a third layer carrier may be included, where the third layer carrier is provided on the protective layer, and then half die-cut together may be performed to achieve the one-time molding.
In this embodiment, the protective layer and the substrate are each independently selected from one of a polymer film material, paper, and fabric.
Wherein the polymer film material is selected from, but not limited to, polyethylene terephthalate, polybutylene terephthalate, polyimide, polyvinyl chloride, polyethylene, polystyrene, polypropylene, polyvinylidene fluoride, ethylene-vinyl acetate copolymer, polycarbonate, polyurethane, polyamide or polytetrafluoroethylene.
The paper material is selected from, but not limited to, natural fiber paper, synthetic fiber paper, composite paper, glassine paper, silicone paper, coated paper or coated paper.
The fabric is selected from, but not limited to, a woven, knit, woven or nonwoven fabric.
Further preferred are silk, flannelette, oxford, felt, leather.
In addition, in an alternative embodiment, a solution comprising a third layer carrier may also be protected, the protective layer 2 being arranged on the antenna conductive layer 1; the antenna conductive layer 1 is arranged on the base material 4 through the back adhesive layer 3; the third layer carrier 5 is disposed on the protective layer 2, so that the flexibility of the antenna is further improved on the basis of ensuring the working performance of the conductive circuit of the antenna. The third layer carrier is selected according to the actual protection requirement.
Based on the structure of the antenna, the application changes the structure of the original traditional electronic tag antenna, selects graphite paper materials which are not easy to think of the person skilled in the art to manufacture the tag antenna, overcomes the problem of insufficient conductivity caused by manufacturing the antenna by conductive ink and film materials, has simpler manufacturing process, and in addition, the square resistance of the tag antenna manufactured by the application is far smaller than that of a carbon paste antenna.
The RFID tag antenna is made of graphite paper material, and is made of carbon material which is the same as graphite and graphene, and compared with metal antennas such as copper, aluminum, silver and the like, the RFID tag antenna has the advantages of cost saving, environmental protection and corrosion resistance improvement; in the prior art, graphite and graphene conductive ink is generally used for RFID labels by a printing antenna method, the method is influenced by various factors such as conductive material types, particle sizes, shapes, filling quantity, dispersion states, adhesive types, curing time and the like, and phenomena such as ink resistance increase and the like caused by incomplete drying and thin printing thickness can be encountered in the printing process, so that the conductivity of the RFID labels is generally 100 times worse than that of graphite paper materials, and the conductivity requirement of RFID label antennas can not be met. In addition, a mask layer with a preset antenna pattern is prepared in advance, the pattern of the mask layer is transferred to a target substrate in a mode of ion etching of a graphite film or a graphene film, and then the graphene antenna is obtained through subsequent treatment. The preparation method based on the template is complex in operation, high in cost, long in production period and easy to produce pollution and defects in the pattern transfer process.
The tag antenna made of the graphite paper material is adopted, the problem of insufficient conductivity caused by the antenna made of conductive ink and film materials is solved, the manufacturing process is simpler, and in addition, the square resistance of the tag antenna manufactured by the method is far smaller than that of a carbon paste antenna.
At present, the price of the aluminum etching antenna tag on the market is different from 0.1 yuan to several yuan, the price of the conductive ink is different from 180 yuan/kg to thousands yuan, and the price of the conductive silver paste is different from 360 yuan/kg to tens of thousands yuan, so that the price of the graphite paper antenna can be reduced to be within 0.1 yuan, and the price of the electronic tag is greatly reduced. And because the application has simple composition structure, and the antenna tag is prepared on the basis of the graphite paper material only by the processes of laminating, die cutting, pasting and the like, the preparation structure is simple and environment-friendly.
Example 2:
in this embodiment, a method for manufacturing an antenna structure is provided, including:
S1: preparing graphite paper or graphite paper composite material, wherein the thickness of the prepared graphite paper or graphite paper composite material is controlled to be 5-30 mu m.
In this embodiment, the thickness of the graphite paper suitable for manufacturing the antenna structure of the electronic tag needs to be controlled in the process of preparing the graphite paper or the graphite paper composite material, and the existing graphite paper or the graphite paper composite material which is manufactured and conforms to the size can be used for performing the next manufacturing process, so that the step of preparing the graphite paper or the graphite paper composite material is omitted.
S2: covering and combining graphite paper or graphite paper composite material with the protective layer; obtaining a graphite composite film;
specifically, the step of covering the graphite paper or the graphite paper composite material with the protective layer comprises the following steps:
Carrying out hot rolling treatment on the graphite paper or the graphite paper composite material and the protective layer by adopting a double-roller press to enable the graphite paper or the graphite paper composite material and the protective layer to be covered, wherein the upper die temperature of the roller press is 25-400 ℃, the lower die temperature is 25-400 ℃, preferably, the upper die temperature of the roller press is 70-120 ℃, and the lower die temperature is 70-120 ℃;
s3, carrying out back glue on the graphite composite film on the surface of the base material to obtain a high-conductivity graphite film;
The adhesive of the back adhesive is any one or more of aqueous coating adhesive, oily coating adhesive and hot-melt pressure-sensitive adhesive.
Further preferred are epoxy resin adhesives, polyurethane adhesives, acrylic resin adhesives, polyvinylidene fluoride resin adhesives, chlorinated rubber, polyacrylate adhesives, and hot melt adhesives.
S4: and processing the high-conductivity graphite film to obtain the antenna structure of the electronic tag. Specifically, the treatment of the high-conductivity graphite film may include attaching a third layer of carrier to the surface of the high-conductivity graphite film, or attaching other relevant layered structures according to the need, or may be a finishing treatment.
The preparation method of the embodiment further comprises a step of cutting and forming the conductive layer, wherein the cutting mode of cutting and forming specifically comprises laser cutting, flame cutting, manual cutting, electric arc cutting or die cutting;
the implementation process of the conducting layer cutting and forming step can be selected according to the requirement on the actual operation step sequence:
The method comprises the steps of directly cutting graphite paper or a graphite paper composite material, or cutting after covering and combining the graphite paper or the graphite paper composite material with a protective layer, or cutting after carrying out back glue on the surface of a substrate on a graphite composite film, or cutting after processing a high-conductivity graphite film.
The method comprises the steps of directly cutting graphite paper or a graphite paper composite material, and selecting a cutting mode which is not easy to damage a structure and has small vibration, wherein the brittle characteristic of the graphite paper is required to be considered;
preferably, the cutting mode for cutting and forming the conductive layer is specifically die cutting, and the steps specifically include:
After the graphite paper or the graphite paper composite material and the protective layer are covered and combined, the graphite paper or the graphite paper composite material covered and combined on the protective layer is die-cut according to a preset shape to obtain the protective layer and the graphite paper with the same shape, or the graphite paper composite material covered and combined on the protective layer is half-die-cut according to the preset shape, the protective layer is reserved, and part of the graphite paper or the graphite paper composite material is cut off to obtain the graphite composite film; the protective layer not only realizes the protection of the conductive layer, but also considers the graphite paper material which is thinner in size and fragile in the embodiment, the protective layer can prevent the breakage of the graphite paper or the graphite paper composite material, and can process the graphite paper material more stably.
The cutting mode of cutting and forming the conductive layer is specifically die cutting, or the step of die cutting and forming can be performed after the step of obtaining the high-conductivity graphite film or attaching a third layer of carrier on the surface of the high-conductivity graphite film, specifically: and performing half die cutting on the graphite paper or the graphite paper composite material attached to the surface of the base material according to a preset shape to obtain a protective layer and the graphite paper with the same shape, and keeping the base material from being cut off. The cutting mode is more stable, and can be cut and molded at one time. When the third layer carrier is arranged, the third layer carrier can be arranged on the protective layer and then half die cut together, so that one-time molding is realized.
Based on the composition of the electronic antenna structure, in the preparation process, the antenna label is prepared on the basis of the graphite paper material only by the processes of covering, die cutting, sticking and the like, and the preparation composition is simple and environment-friendly. The process of obtaining the graphite paper material requires careful control of the thickness to conform to the dimensions of the conductive layer of the electronic antenna structure. Because of the brittle nature of the material and the thinness of the graphite paper in the electronic tag in this embodiment, the graphite paper or the graphite paper composite material covered on the protective layer and/or adhered on the substrate can be die-cut or half-die-cut according to a preset shape by a mode of firstly covering or attaching and then cutting and forming, particularly preferably a die-cutting mode, that is, the die-cutting shape of the antenna conductive layer in the application is cut by a die-cutting die through a preset cutting thickness and shape, but the material needing to be reserved is not cut. The shape of the required conductive layer can be conveniently and stably obtained, and the problems of complex antenna process, low manufacturing efficiency, high cost, environmental pollution, limited application field and the like in the prior art are solved.
Based on the above embodiment, the present application further provides an electronic tag, where the electronic tag includes the antenna structure described above or the antenna structure manufactured by the manufacturing method described above.
Example 3:
In this embodiment, the step of preparing the graphite paper or the graphite paper composite material in step S1 is further defined, specifically,
The preparation of graphite paper or graphite paper composite material comprises the following steps:
pretreating a graphite paper raw material to prepare expandable graphite, and then expanding and calendaring the expandable graphite at a preset expansion temperature to prepare graphite paper or a graphite paper composite material;
wherein the graphite material is one or more of natural crystalline flake graphite, pyrolytic graphite, artificial graphite and graphite oxide; wherein the expansion temperature is 200-1000 ℃.
The preparation of expandable graphite from graphite paper raw materials by pretreatment comprises the following steps:
Mixing graphite paper raw materials, washing with water and drying after the mixing treatment to obtain expandable graphite;
Wherein, the mixing treatment is as follows: mixing graphite material and a reaction compound, and stirring at a preset reaction temperature; wherein the preset reaction temperature is 20-50 ℃; stirring for 60-90 min;
Or, the mixing process is as follows: immersing a graphite material in a reaction solution with a preset proportion, and carrying out electrolytic treatment under constant current, wherein the electrolytic time is 2-3 h;
The rolling specifically comprises rolling treatment for preset times, wherein the preset times are 3-5 times.
In the method steps, the graphite paper composite material has a plurality of working procedures compared with the graphite paper, and the graphite paper composite material is prepared by jointly processing the graphite paper and a carbon material, a metal material or a ceramic material after the graphite paper is prepared.
By the method, the thickness of the graphite paper or the graphite paper composite material can be better controlled in the process of preparing the graphite paper or the graphite paper composite material, and the generated graphite paper has clear and stable structure, and can be seen from the attached figures 1 (a) and (b), so that the generated graphite paper can better meet the requirements of an electronic tag antenna.
Example 4:
In this embodiment, step S2 of laminating the graphite paper or the graphite paper composite material with the protective layer specifically includes: the method for covering the graphite paper or the graphite paper composite material with the protective layer comprises the following steps:
And carrying out hot rolling treatment on the graphite paper or the graphite paper composite material and the protective layer by adopting a pair roller press to enable the graphite paper or the graphite paper composite material and the protective layer to be covered, wherein the upper die temperature of the roller press is 25-400 ℃, and the lower die temperature is 25-400 ℃. The temperature of the upper and lower dies of the roll squeezer is selected according to the materials and thickness of the graphite paper and the protective layer.
The following examples will list a few specific material selections and specific environmental parameters of preparation, etc., to demonstrate the outstanding conductive properties of the tag antenna of the present application in combination with the tag antenna block resistance values that are ultimately obtained:
Example 5:
S1, natural crystalline flake graphite, nitric acid, acetic anhydride and potassium permanganate are mixed according to the mass ratio of 1:0.7:1.5:0.4, stirring for 90min at 35 ℃, washing with water, drying to obtain sulfur-free expandable graphite, puffing at 900 ℃, and finally rolling at room temperature for 5 times to obtain a graphite paper material; wherein, the thickness of the graphite paper material prepared in the embodiment is 20 μm;
S2, carrying out hot rolling treatment on the graphite paper material and the PET film by adopting a double-roller press, wherein the upper die temperature of the roller press is 120 ℃, and the lower die temperature is 120 ℃, and laminating to obtain a graphite composite film;
s3: compounding the graphite composite film and the silk cloth by using a compounding machine through polyester glue to obtain a high-conductivity graphite film;
and S4, attaching a PE film on the surface of the high-conductivity graphite film by using a roll squeezer, and half die cutting to obtain the RFID tag antenna.
The block resistance of the finally obtained tag antenna conductive layer is 10mΩ·sq -1.
Example 6
S1, natural crystalline flake graphite, perchloric acid and potassium permanganate are mixed according to the mass ratio of 1:3:0.4, uniformly mixing, stirring for 1h at room temperature, washing and drying to obtain expandable graphite, expanding at a low temperature of 300 ℃, and finally rolling for 3 times at room temperature to obtain a graphite paper material; the thickness of the graphite paper material prepared in this example was 15. Mu.m;
S2, carrying out hot rolling treatment on the graphite paper material and the polyvinyl chloride film by adopting a double-roller press, wherein the upper die temperature of the roller press is 80 ℃, and the lower die temperature is 80 ℃, and laminating to obtain a graphite composite film;
S3, compounding the graphite composite film and the glassine paper through hot melt adhesive by using a compounding machine to obtain a high-conductivity graphite film;
And S4, attaching a polyurethane film on the surface of the high-conductivity graphite film by using a roll squeezer, and obtaining the RFID tag antenna after laser cutting.
The block resistance of the finally obtained tag antenna conductive layer is 8mΩ·sq -1.
Example 7
S1, immersing 10g of natural crystalline flake graphite in a solution with a volume ratio of sulfuric acid to phosphoric acid of 1:1, fixing current of 0.3A, using a stainless steel net as an anode current collector, using a stainless steel plate as both a cathode and an anode, wherein the effective area of an electrode plate is about 20cm < 2 >, carrying out water washing, suction filtration and drying after electrolysis for 3 hours, expanding at 900 ℃, and finally carrying out 3 times of rolling at room temperature to obtain a graphite paper material; the thickness of the graphite paper material prepared in this example was 30. Mu.m;
S2, carrying out hot rolling treatment on the graphite paper material and polyethylene by adopting a double-roller press, wherein the upper die temperature of the roller press is 110 ℃, and the lower die temperature is 110 ℃, and laminating to obtain a graphite composite film;
S3, compounding the graphite composite film and the felt cloth through epoxy resin glue by using a compounding machine to obtain a high-conductivity graphite film;
and S4, attaching a polyvinyl chloride film on the surface of the high-conductivity graphite film by using a roll squeezer, and half die cutting to obtain the RFID tag antenna.
The block resistance of the finally obtained tag antenna conductive layer is 12mΩ·sq -1.
Example 8:
S1, mixing artificial graphite, potassium dichromate, nitric acid and ammonium phosphate according to a mass ratio of 5: uniformly mixing the materials in a ratio of 0.6:10:15, reacting for 60min at 50 ℃, washing with water, drying to obtain sulfur-free expandable graphite, puffing at 900 ℃, and finally rolling for 5 times at room temperature to obtain a graphite paper material; the thickness of the graphite paper material prepared in this example was 10. Mu.m;
S2, carrying out hot rolling treatment on the graphite paper material and polyimide by adopting a double-roller press, wherein the upper die temperature of the roller press is 260 ℃, and the lower die temperature is 260 ℃, and laminating to obtain a graphite composite film;
S3, compounding the graphite composite film and the fiber paper through chlorinated rubber by using a compounding machine to obtain a high-conductivity graphite film;
and S4, attaching a PET film on the surface of the high-conductivity graphite film by using a roll squeezer, and obtaining the RFID tag antenna after laser cutting.
The block resistance of the finally prepared tag antenna conductive layer is 15mΩ·sq -1.
Example 9
S1, uniformly mixing pyrolytic graphite, perchloric acid, phosphoric acid, acetic anhydride and chromium trioxide according to the mass ratio of 1:3:2.3:1.4:0.18, reacting for 70min at the temperature of 40 ℃, washing with water, drying to obtain sulfur-free expandable graphite, puffing at 300 ℃, and finally rolling for 5 times at room temperature to obtain a graphite paper material; the thickness of the graphite paper material prepared in this example was 30 μm,
S2, carrying out hot rolling treatment on the graphite paper material and the polyurethane film by adopting a double-roller press, wherein the upper die temperature of the roller press is 120 ℃, and the lower die temperature of the roller press is 120 ℃, and laminating to obtain a graphite composite film;
s3, compounding the graphite composite film and the coated paper through polyacrylate adhesive by using a compounding machine to obtain a high-conductivity graphite film;
and S4, attaching a polyurethane film on the surface of the high-conductivity graphite film by using a roller press, and half die cutting to obtain the RFID tag antenna.
The block resistance of the finally prepared tag antenna conductive layer is 20mΩ·sq -1.
Example 10:
S1, using a 200-mesh stainless steel net to contain 10g of graphite oxide, adopting a stainless steel plate for the anode and the cathode, wherein the effective area of an electrode plate is 20cm < 2 >, immersing the electrode plate in a mixed solution of sulfuric acid and phosphoric acid with the volume ratio of 1:1, electrolyzing for 3 hours under a constant current of 20mA/cm < 2 >, washing with water, filtering, drying, expanding at 800 ℃, and finally rolling for 3 times at room temperature to obtain a graphite paper material; the thickness of the graphite paper material prepared in this example was 5. Mu.m;
S2, carrying out hot rolling treatment on the graphite paper material and the polyamide film by adopting a double-roller press, wherein the upper die temperature of the roller press is 150 ℃, and the lower die temperature of the roller press is 150 ℃, so as to obtain a graphite composite film by covering;
s3, compounding the graphite composite film and oxford cloth through polyvinylidene fluoride resin glue by using a compounding machine to obtain a high-conductivity graphite film;
and S4, attaching a polyimide film on the surface of the high-conductivity graphite film by using a roll squeezer, and obtaining the RFID tag antenna after laser cutting.
The block resistance of the finally obtained tag antenna conductive layer is 1mΩ·sq -1.
Comparative example 1
The comparative example provides an RFID tag antenna, the antenna conductive layer material of which mainly consists of graphene conductive ink, the preparation method of the RFID tag antenna mainly comprises the steps of printing the graphene conductive ink on a base material, thermally curing the graphene conductive ink, and drying the printed graphene conductive ink at 80 ℃ for 3 hours, wherein the square resistance value of the cured RFID antenna conductive layer is 2000mΩ -sq -1.
Comparative example 2
The comparative example provides an RFID tag antenna, the antenna conductive layer material of which mainly consists of conductive silver paste, the preparation method of the antenna conductive layer material mainly comprises the steps of printing the conductive silver paste on a base material, thermally curing the conductive silver paste, and drying the conductive silver paste at 80 ℃ for 5min, wherein the sheet resistance of the conductive layer of the RFID tag antenna after curing is 15mΩ & sq-1.
As can be seen from the specific content of the above embodiments and the analysis of the comparative examples, the technical solution of the present application has the following beneficial effects:
(1) The application changes the constitution of the original traditional electronic tag antenna, selects graphite paper materials which are not easy to think of the person skilled in the art to manufacture the antenna conducting layer of the tag antenna structure, overcomes the problem of insufficient conductivity caused by manufacturing the antenna by conducting ink and film materials, has simpler manufacturing process, and in addition, the square resistance of the tag antenna manufactured by the application is far smaller than that of a carbon paste antenna.
(2) And because the application has simple composition structure, and the antenna tag is prepared on the basis of the graphite paper material only by the processes of covering, cutting, pasting and the like, the preparation structure is simple and environment-friendly.
(3) The graphite paper or graphite paper composite material covered on the protective layer and/or adhered on the base material is subjected to die cutting or half die cutting according to the preset shape, and the die cutting is specifically half die cutting in a mode of firstly covering or adhering and then die cutting, namely the die cutting die cuts the die cutting shape of the antenna conductive layer according to the preset cutting thickness and shape, but the protective layer is not cut. The shape of the required conductive layer can be conveniently and stably obtained without damaging fragile graphite paper materials;
(4) The thickness of the graphite paper or the graphite paper composite material can be better controlled in the process of preparing the graphite paper or the graphite paper composite material by the method for generating the graphite paper, and the generated graphite paper has a clear and stable structure.
The examples selected above are exemplary embodiments and the above description is only intended to aid in understanding the method of the present invention and its core ideas. It should be noted that it will be apparent to those skilled in the art that various modifications and adaptations of the invention can be made without departing from the principles of the invention and these modifications and adaptations are intended to be within the scope of the invention as defined in the following claims.
Claims (17)
1. An antenna structure for an electronic tag, wherein the antenna structure has an antenna conductive layer comprising at least one layer of graphite paper composite material; the graphite paper composite material is prepared by preparing expandable graphite from a graphite paper raw material through pretreatment, and then expanding and calendaring at a preset expansion temperature; the graphite paper composite material is a composite of graphite paper and a metal material or a ceramic material.
2. An antenna structure for an electronic tag according to claim 1, wherein the graphite paper composite material has a thickness of 5 μm to 500 μm.
3. An antenna structure for an electronic tag according to claim 2, wherein the graphite paper composite material has a thickness of 5 μm to 30 μm.
4. An antenna structure for an electronic tag according to any one of claims 1-3, further comprising a protective layer in overlying connection with the graphite paper composite of the antenna conductive layer.
5. The antenna structure for an electronic tag of claim 4, wherein the antenna conductive layer is formed by die cutting or half die cutting after the graphite paper composite material and the protective layer are combined.
6. The antenna structure for an electronic tag of claim 4, further comprising a substrate, wherein the antenna conductive layer is disposed on the substrate, the antenna conductive layer is bonded to the substrate through a backing layer, and the antenna conductive layer is formed by laminating a graphite paper composite material and the protective layer and then attaching the graphite paper composite material and the protective layer to the substrate for half die cutting.
7. The antenna structure for an electronic tag of claim 4, further comprising a third layer of carrier disposed on the protective layer, the third layer of carrier being an insulating polymer film material.
8. The preparation method of the electronic tag antenna structure is characterized by comprising the following steps of:
Covering and combining the graphite paper composite material with the protective layer to obtain a graphite composite film;
carrying out back glue on the surface of the substrate to obtain a high-conductivity graphite film;
processing the high-conductivity graphite film to obtain an electronic tag antenna structure;
The method further comprises a step of cutting and forming the conductive layer, wherein the cutting mode of cutting and forming specifically comprises laser cutting, flame cutting, manual cutting, electric arc cutting or die cutting;
The conducting layer cutting and forming step is implemented by directly cutting the graphite paper composite material, or cutting after covering and combining the graphite paper composite material and the protective layer, or cutting after back gluing the graphite composite film on the surface of the base material, or cutting after processing the high-conductivity graphite film;
The graphite paper composite material is prepared by preparing expandable graphite from a graphite paper raw material through pretreatment, and then expanding and calendaring at a preset expansion temperature; the graphite paper composite material is a composite of graphite paper and a metal material or a ceramic material.
9. The method of claim 8, wherein the treating the high conductivity graphite film comprises attaching a third layer of carrier to the surface of the high conductivity graphite film.
10. The method according to claim 8 or 9, wherein,
The cutting mode for cutting and forming the conductive layer is specifically die cutting, and the steps specifically comprise:
After the graphite paper composite material and the protective layer are covered, die cutting is carried out on the graphite paper composite material covered on the protective layer according to a preset shape to obtain the protective layer and the graphite paper with the same shape, or half die cutting is carried out on the graphite paper composite material covered on the protective layer according to the preset shape, the protective layer is reserved, and part of the graphite paper composite material is cut off to obtain the graphite composite film;
Or, the die-cutting molding step specifically comprises the following steps:
after the step of obtaining the high-conductivity graphite film or attaching a third layer of carrier on the surface of the high-conductivity graphite film, performing half die cutting on the graphite paper composite material attached to the surface of the base material according to a preset shape to obtain a protective layer and graphite paper with the same shape, and keeping the base material from being cut off.
11. The method according to claim 8, wherein,
The method for covering the graphite paper composite material and the protective layer comprises the following steps:
And carrying out hot rolling treatment on the graphite paper composite material and the protective layer by adopting a double-roller press to cover the graphite paper composite material and the protective layer, wherein the upper die temperature of the roller press is 25-400 ℃, and the lower die temperature is 25-400 ℃.
12. The method according to claim 8, wherein,
The step of covering the graphite paper composite material and the protective layer further comprises the following steps: preparing a graphite paper composite material, wherein the prepared graphite paper composite material has a controlled thickness of 5-30 mu m.
13. The method according to claim 11, wherein,
The preparation of the graphite paper composite material comprises the following steps:
Pretreating a graphite paper raw material to prepare expandable graphite, and then expanding and calendaring the expandable graphite at a preset expansion temperature to prepare a graphite paper composite material;
Wherein the graphite material is one or more of natural crystalline flake graphite, pyrolytic graphite, artificial graphite and graphite oxide; wherein the expansion temperature is 200-1000 ℃.
14. The method of claim 13, wherein the process comprises,
The preparation of the expandable graphite from the graphite paper raw material through pretreatment comprises the following steps:
Mixing graphite paper raw materials, washing with water and drying after the mixing treatment to obtain expandable graphite;
The rolling specifically comprises rolling treatment for preset times, wherein the preset times are 3-5 times.
15. The method of claim 14, wherein the process comprises,
The mixing treatment specifically comprises the following steps: mixing graphite material and a reaction compound, and stirring at a preset reaction temperature; wherein the preset reaction temperature is 20-50 ℃; the stirring time is 60min-90min.
16. The method of claim 14, wherein the process comprises,
The mixing treatment is as follows: immersing graphite material in a reaction solution with a preset proportion, and carrying out electrolysis treatment under constant current, wherein the electrolysis time is 2-3 h.
17. An electronic tag comprising an antenna structure according to any one of claims 1-7 or an antenna structure manufactured by a manufacturing method according to any one of claims 8-16.
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| PCT/CN2021/139458 WO2022247248A1 (en) | 2021-05-25 | 2021-12-20 | Antenna structure for electronic tag, preparation method therefor, and electronic tag |
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