CN113163529A - Method for preparing graphene high-temperature electrothermal film based on LIG method - Google Patents
Method for preparing graphene high-temperature electrothermal film based on LIG method Download PDFInfo
- Publication number
- CN113163529A CN113163529A CN202110452303.7A CN202110452303A CN113163529A CN 113163529 A CN113163529 A CN 113163529A CN 202110452303 A CN202110452303 A CN 202110452303A CN 113163529 A CN113163529 A CN 113163529A
- Authority
- CN
- China
- Prior art keywords
- layer
- film
- temperature
- copper electrode
- lig
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 72
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 60
- 229910052802 copper Inorganic materials 0.000 claims abstract description 84
- 239000010949 copper Substances 0.000 claims abstract description 84
- 239000000463 material Substances 0.000 claims abstract description 46
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000011282 treatment Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 238000004806 packaging method and process Methods 0.000 claims abstract description 18
- 239000002131 composite material Substances 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 5
- 230000005540 biological transmission Effects 0.000 claims abstract description 3
- 239000010410 layer Substances 0.000 claims description 66
- 238000001035 drying Methods 0.000 claims description 55
- 229920005575 poly(amic acid) Polymers 0.000 claims description 47
- 238000003825 pressing Methods 0.000 claims description 32
- 239000004952 Polyamide Substances 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 18
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- 229920002647 polyamide Polymers 0.000 claims description 18
- 229920001169 thermoplastic Polymers 0.000 claims description 14
- 239000004416 thermosoftening plastic Substances 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 10
- 238000012545 processing Methods 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 2
- 239000011241 protective layer Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 description 63
- 229920001721 polyimide Polymers 0.000 description 63
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 24
- 229910002092 carbon dioxide Inorganic materials 0.000 description 12
- 239000001569 carbon dioxide Substances 0.000 description 12
- 238000003475 lamination Methods 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 11
- 230000036961 partial effect Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 239000011889 copper foil Substances 0.000 description 5
- 238000005485 electric heating Methods 0.000 description 5
- -1 graphite alkene Chemical class 0.000 description 5
- 230000007547 defect Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 238000001039 wet etching Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000013532 laser treatment Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/145—Carbon only, e.g. carbon black, graphite
-
- 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
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/20—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater
- H05B3/34—Heating elements having extended surface area substantially in a two-dimensional plane, e.g. plate-heater flexible, e.g. heating nets or webs
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/009—Heaters using conductive material in contact with opposing surfaces of the resistive element or resistive layer
- H05B2203/01—Heaters comprising a particular structure with multiple layers
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B2203/00—Aspects relating to Ohmic resistive heating covered by group H05B3/00
- H05B2203/017—Manufacturing methods or apparatus for heaters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a method for preparing a graphene high-temperature electrothermal film based on an L IG method, which comprises the following steps: s1, forming a composite layer of the PI-copper electrode, wherein the copper electrode is wholly embedded or partially embedded in the P I film; s2, forming a PI material layer on the surface of the PI film-copper electrode composite layer to form a P I-copper electrode-PI material layer (waiting for the LIG layer) composite; s3, carrying out L IG treatment on the PI material layer, and carrying out laser transmission to form a graphene heating layer pattern to form a PI film-copper electrode composite layer-patterned graphene layer (L IG layer) structure; and S4, packaging a protective film layer on the surface of the patterned graphene layer.
Description
The invention is a divisional application with a parent application number of 202010646038.1, the parent name is: a method for preparing a graphene high-temperature electrothermal film based on an LIG method.
Technical Field
The invention relates to a method for preparing a graphene high-temperature electrothermal film by adopting a laser induction method.
Background
Graphene is a new strategic material developed in the twenty-first century, and in the development process of the graphene industry, the graphene electrothermal film is developed quickly, so that the production and manufacturing cost is low, and the production process is environment-friendly. Especially, graphite alkene electric heat membrane can launch can realize the far infrared of better resonance absorption effect with the human body, simultaneously still realize the face easily and generate heat, advantage such as fast generates heat, becomes the hot spot of the competitive research in current electric heat membrane field.
The main manufacturing methods of the graphene electrothermal films mainly used at present are divided into the following categories:
the first type is an electrothermal film prepared by adopting graphene slurry, and the heating layer of the electrothermal film generally comprises a high polymer material which has temperature limitation in the using process, and the stability of the electrothermal film is rapidly reduced after a certain temperature is exceeded, specifically, the power fluctuation of the electrothermal film is reached, even irreversible damage is directly generated, so that the electrothermal film is damaged or serious potential safety hazard is generated;
the second type is a graphene electrothermal film prepared by a Chemical Vapor Deposition (CVD) method, which is relatively stable at medium and low temperature, and because an adsorption type chemical doping method is generally adopted in the preparation process of the graphene film, a dopant can generate desorption and graphene defect increase phenomena under the action of high temperature, so that the heating power of the electrothermal film is reduced, and the problem of high-temperature thermal runaway is restrained to a certain extent. However, the use temperature of the CVD graphene electrothermal film is generally below 170 ℃, and after the temperature is exceeded, the power attenuation of the electrothermal film is serious, the defects of the graphene are seriously amplified, and finally the defects are also damaged.
To sum up, current graphite alkene electric heat membrane because heating material self reason, can't high temperature use, has seriously influenced the use popularization of graphite alkene electric heat membrane in high temperature electric heat field.
The statements in the background section are merely prior art as they are known to the inventors and do not, of course, represent prior art in the field.
Disclosure of Invention
The invention aims to provide a method for preparing a graphene high-temperature electrothermal film based on an LIG method, aiming at one or more problems in the prior art, and the method comprises the following steps:
s1, forming a composite layer of the PI-copper electrode, wherein the copper electrode is wholly embedded or partially embedded in the PI film;
s2, forming a PI material layer on the surface of the PI film-copper electrode composite layer to form a PI-copper electrode-PI material layer (to-be-LIG layer) assembly;
s3, LIG processing is carried out on the PI material layer, laser transmission is carried out to enable the PI material layer to form a graphene heating layer pattern, and a PI film-copper electrode composite layer-patterned graphene layer (LIG layer) structure is formed; and
and S4, packaging a protective film layer on the surface of the patterned graphene layer.
According to an aspect of the present invention, the specific method of S1 is:
and (3) coating a thermoplastic PI prepolymer (polyamide acid) on the surface of the PI film, drying to form a semi-cured polyamide acid film, then pressing the semi-cured polyamide acid film with a copper electrode, performing imidization treatment, and then fusing the polyamide acid film and the PI film into a whole to finally form a PI film-copper electrode composite layer with the copper electrode fully embedded or partially embedded in the PI film.
According to an aspect of the present invention, the specific method of S1 is:
coating thermoplastic PI prepolymer (polyamic acid) on the surface of the copper electrode, drying and semi-curing to form a polyamic acid film, and then carrying out high-temperature pressing and imidization on the polyamic acid film to form a PI-copper electrode complex.
According to an aspect of the present invention, in the two methods of S1, the drying temperature is 120-; preferably, the drying temperature is 150 ℃ and the drying time is 10 min.
According to an aspect of the present invention, in both methods of S1 above, the imidization treatment is performed by applying pressure at a high temperature: the pressing temperature is 250 ℃ and 350 ℃, and the pressure is 2-10 MPa.
According to an aspect of the present invention, the specific method of S2 is:
s2-1, coating a thermoplastic PI prepolymer (polyamide acid) on the surface of a PI film, drying to form a semi-cured polyamide acid film, forming a PI-polyamide acid film material, and opening holes in the PI-polyamide acid film material;
s2-2, covering the PI-polyamic acid film material with the opening on the surface of the PI film-copper electrode complex layer prepared in the step S1, and aligning the opening with the copper electrode to expose the copper electrode through the opening to form a structural member of the PI-copper electrode-polyamic acid film material-PI;
s2-3, pressing the structural member obtained in the S2-2, and performing imidization treatment on the polyamide acid film material to enable the PI-polyamide acid film material to be fused into a whole to form a finished layer of PI material layer, and finally obtaining the PI film-copper electrode-PI material layer (to-be-LIG layer) combination.
According to an aspect of the present invention, the specific method of S2 is:
s2-1, coating a thermoplastic PI prepolymer (polyamic acid) on the surface of the PI film-copper electrode composite body layer prepared in the step S1, drying to form a semi-cured polyamic acid film, carrying out local protection on the terminal area of the copper foil electrode in the process to ensure that the surface terminal area does not cover the PI prepolymer, and drying to enable the PI prepolymer to form the semi-cured polyamic acid film;
s2-2, performing imidization treatment on the formed polyamic acid film, wherein the heat treatment temperature is 350 ℃, and the time is 1h, so as to form a PI-copper electrode-PI material layer (to-be-LIG layer) assembly.
According to an aspect of the present invention, in the two methods of S2, the drying temperature is both 120-; preferably, the drying temperature is 150 ℃ and the drying time is 10 min.
According to an aspect of the present invention, in both methods of S2 above, the imidization treatment is performed by applying pressure at a high temperature: the pressing temperature is 250 ℃ and 350 ℃, and the pressure is 2-10 MPa.
According to an aspect of the present invention, in S3, the LIG processing conditions are: the laser scanning wavelength is 1-20 microns, the power is 2-20W, and the pulse time is 5-30 microseconds. Preferably, the LIG processing conditions are: the wavelength of laser scanning is 10.6 microns, the power is 4.8W, and the pulse time is 20 microseconds;
according to one aspect of the invention, the protective film layer is made of PI material, and the structure of the final product forms a combination of PI-copper electrode-LIG layer-PI, namely the graphene high-temperature electrothermal film.
According to an aspect of the present invention, the specific method of S4 is:
s4-1, taking the PI film as a packaging layer;
s4-2, coating a thermoplastic PI prepolymer (polyamic acid) on the surface of the PI packaging layer, semi-drying to form a polyamic acid film, and performing opening treatment in a local area;
s4-3, then pressing the PI-copper electrode-graphene (LIG) assembly formed in S3, and completing imidization treatment, so that a polyamide acid film on the surface of the PI packaging layer and a PI packaging layer form an integrated PI material as a protective layer, and before pressing, a local copper electrode terminal is exposed through an opening, and thus the PI-copper electrode-LIG layer-PI assembly, namely the graphene high-temperature electrothermal film, is obtained.
According to an aspect of the present invention, in the above specific method of S4, the drying temperature is 120-200 ℃, and the drying time is 1-20 min; preferably, the drying temperature is 150 ℃ and the drying time is 10 min. Preferably, the imidization treatment is performed by applying pressure at a high temperature: the pressing temperature is 250 ℃ and 350 ℃, and the pressure is 2-10 MPa.
The invention has the beneficial effects that:
based on the market demand of the high-temperature graphene electrothermal film in the high-temperature use field, such as the field of heaters, kitchen appliances and the like, and the technical defect analysis of the existing medium-low temperature graphene electrothermal film, in order to obtain the practical high-temperature graphene electrothermal film, the invention adopts a novel Laser Induced Graphene (LIG) manufacturing method which is started in recent years to manufacture the graphene electrothermal film, and because the graphene heating layer is obtained by high-temperature graphitization caused by laser treatment, the temperature resistance is excellent. The invention provides a method for manufacturing a high-temperature graphene electrothermal film based on laser-induced graphene, which is a manufacturing method for directly generating a graphene heating electrode pattern on the surface of polyimide and then packaging by adopting PI (polyimide), and can meet the requirements of low-cost and large-batch production of the high-temperature graphene electrothermal film. Polyimide (PI) is used as a packaging substrate, and a common binder is not used in the packaging process, so that the stability of high-temperature use is ensured, and the packaging film has good flexibility. Finally obtaining a glue-free high-temperature graphene heating film product. The method has the following two aspects:
1. the process expansibility is good: the heating film can realize roll type automatic production, reduce the production cost and improve the production yield;
2. the performance is better: based on the graphene heating body with high electric-thermal radiation conversion efficiency and no packaging adhesive, compared with the traditional nickel-chromium-aluminum alloy electric heating film (comparative example 1), the graphene electric heating film has obvious advantages in temperature rise speed and uniformity, and the data are shown in table 1.
Detailed Description
In the following, only certain exemplary embodiments are briefly described. As those skilled in the art will recognize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. Accordingly, the description is to be regarded as illustrative in nature and not as restrictive.
The following disclosure provides many different embodiments or examples for implementing different features of the invention. To simplify the disclosure of the present invention, the components and arrangements of specific examples are described below. Of course, they are merely examples and are not intended to limit the present invention. Furthermore, the present invention may repeat reference numerals and/or letters in the various examples, such repetition is for the purpose of simplicity and clarity and does not in itself dictate a relationship between the various embodiments and/or configurations discussed. In addition, the present invention provides examples of various specific processes and materials, but one of ordinary skill in the art may recognize applications of other processes and/or uses of other materials.
Example 1:
1) coating a thermoplastic PI prepolymer (polyamic acid) on the surface of a polyimide insulating film with the thickness of 50 microns, and drying to form a semi-cured polyamic acid film, wherein the drying temperature is 150 ℃ and 10 min;
2) carrying out high-temperature pressing (imidization) on one side of the semi-cured polyamic acid film obtained in the step 1) and a copper foil, wherein the pressing temperature is 350 ℃, the time is 1h, and the pressure is 5MPa, so as to obtain a PI-copper electrode substrate;
3) pre-coating a PI prepolymer on a commercial PI (10-micron-thick) surface, and drying to form a semi-cured polyamic acid film at the drying temperature of 150 ℃ for 10min to form a PI-polyamic acid film material;
4) performing hole opening treatment on a PI-polyamic acid film material, then pressing the PI-copper electrode assembly formed in the step 2), and completing imidization treatment, wherein the pressing temperature is 350 ℃, the time is 1h, and the pressure is 5 MPa. Before pressing, partial copper electrode terminals are ensured to be exposed through the openings, so that a PI-copper electrode-PI (to-be-LIG layer) assembly is obtained.
5) A laser scanning device is adopted to induce and form a graphene heating layer pattern on the surface of a PI, a PI-copper electrode-graphene (LIG) assembly is finally formed, the PI with the front surface covering the surface of the copper electrode is ensured, and all graphene is arranged on a laser scanning part, so that the copper electrode and a heating layer area are electrically connected well, a laser light source is a carbon dioxide laser, the wavelength of the carbon dioxide laser is 10.6 micrometers, the power of the carbon dioxide laser is 4.8W, and the pulse time is 20 microseconds.
6) Pre-coating a thermoplastic PI prepolymer (polyamic acid) on a PI packaging layer with the thickness of 50 microns, and drying to form a polyamic acid film, wherein the drying temperature is 150 ℃ and the drying time is 10 min;
7) performing hole opening treatment on a PI-polyamic acid film material locally, then performing lamination with the PI-copper electrode-graphene (LIG) assembly formed in the step 5), and completing imidization treatment, wherein the lamination temperature is 350 ℃, the time is 1h, and the pressure is 5 MPa. And before lamination, the partial copper electrode terminal is ensured to be exposed through the opening, so that a PI-copper electrode-LIG layer-PI assembly, namely the graphene high-temperature electrothermal film, is obtained.
Example 2:
1) coating a thermoplastic PI prepolymer (polyamic acid) on the surface of the copper foil, and drying to form a semi-cured polyamic acid film, wherein the drying temperature is 150 ℃ and 10 min;
2) carrying out high-temperature pressing (imidization) on 1) 50-micron-thick PI insulating base material at the pressing temperature of 350 ℃, the pressing time of 1h and the pressure of 5MPa to obtain a PI-copper electrode base material;
3) pre-coating a PI prepolymer on the surface of a PI-copper electrode substrate, drying to form a semi-cured polyamic acid film, wherein the drying temperature is 150 ℃ and 10min to form a PI-polyamic acid film material, and in the process, performing local protection on a copper foil electrode terminal area to ensure that the surface terminal area does not cover the PI prepolymer;
4) imidizing the polyamic acid film formed in the step 3), wherein the heat treatment temperature is 350 ℃, and the time is 1h, so that a PI-copper electrode-PI (to-be-LIG layer) assembly is formed;
5) a laser scanning device is adopted to induce and form a graphene heating layer pattern on the surface of a PI, a PI-copper electrode-graphene (LIG) assembly is finally formed, the PI with the front surface covering the surface of the copper electrode is ensured, and all graphene is arranged on a laser scanning part, so that the copper electrode and a heating layer area are electrically connected well, a laser light source is a carbon dioxide laser, the wavelength of the carbon dioxide laser is 10.6 micrometers, the power of the carbon dioxide laser is 4.8W, and the pulse time is 20 microseconds.
6) Pre-coating a thermoplastic PI prepolymer (polyamic acid) on a PI packaging layer with the thickness of 50 microns, and drying to form a polyamic acid film, wherein the drying temperature is 150 ℃ and the drying time is 10 min;
7) performing hole opening treatment on a PI-polyamic acid film material locally, then performing lamination with the PI-copper electrode-graphene (LIG) assembly formed in the step 5), and completing imidization treatment, wherein the lamination temperature is 350 ℃, the time is 1h, and the pressure is 5 MPa. And before lamination, the partial copper electrode terminal is ensured to be exposed through the opening, so that a PI-copper electrode-LIG layer-PI assembly, namely the graphene high-temperature electrothermal film, is obtained.
Example 3:
1) preparing a patterned copper electrode on the surface of a non-glue PI copper-coated film with the thickness of 50 microns by adopting a wet etching method to obtain a PI-copper electrode substrate;
2) pre-coating a PI prepolymer on a commercial PI (10-micron-thick) surface, and drying to form a semi-cured polyamic acid film at the drying temperature of 150 ℃ for 10min to form a PI-polyamic acid film material;
3) performing hole opening treatment on a PI-polyamic acid film material, then pressing the PI-copper electrode assembly formed in the step 2), and completing imidization treatment, wherein the pressing temperature is 350 ℃, the time is 1h, and the pressure is 5 MPa. Before pressing, partial copper electrode terminals are ensured to be exposed through the openings, so that a PI-copper electrode-PI (to-be-LIG layer) assembly is obtained.
4) A laser scanning device is adopted to induce and form a graphene heating layer pattern on the surface of a PI, a PI-copper electrode-graphene (LIG) assembly is finally formed, the PI with the front surface covering the surface of the copper electrode is ensured, and all graphene is arranged on a laser scanning part, so that the copper electrode and a heating layer area are electrically connected well, a laser light source is a carbon dioxide laser, the wavelength of the carbon dioxide laser is 10.6 micrometers, the power of the carbon dioxide laser is 4.8W, and the pulse time is 20 microseconds.
5) Pre-coating a thermoplastic PI prepolymer (polyamic acid) on a PI packaging layer with the thickness of 50 microns, and drying to form a polyamic acid film, wherein the drying temperature is 150 ℃ and the drying time is 10 min;
6) performing hole opening treatment on a PI-polyamic acid film material locally, then performing lamination with the PI-copper electrode-graphene (LIG) assembly formed in the step 5), and completing imidization treatment, wherein the lamination temperature is 350 ℃, the time is 1h, and the pressure is 5 MPa. And before lamination, the partial copper electrode terminal is ensured to be exposed through the opening, so that a PI-copper electrode-LIG layer-PI assembly, namely the graphene high-temperature electrothermal film, is obtained.
Example 4:
1) preparing a patterned copper electrode on the surface of a non-glue PI copper-coated film with the thickness of 50 microns by adopting a wet etching method to obtain a PI-copper electrode substrate;
2) pre-coating a PI prepolymer on the surface of a PI-copper electrode substrate, drying to form a semi-cured polyamic acid film, wherein the drying temperature is 150 ℃ and 10min to form a PI-polyamic acid film material, and in the process, performing local protection on a copper foil electrode terminal area to ensure that the surface terminal area does not cover the PI prepolymer;
3) performing imidization treatment on the polyamic acid film formed in the step 2), wherein the heat treatment temperature is 350 ℃, and the time is 1h, so as to form a PI-copper electrode-PI (to-be-LIG layer) assembly;
4) a laser scanning device is adopted to induce and form a graphene heating layer pattern on the surface of a PI, a PI-copper electrode-graphene (LIG) assembly is finally formed, the PI with the front surface covering the surface of the copper electrode is ensured, and all graphene is arranged on a laser scanning part, so that the copper electrode and a heating layer area are electrically connected well, a laser light source is a carbon dioxide laser, the wavelength of the carbon dioxide laser is 10.6 micrometers, the power of the carbon dioxide laser is 4.8W, and the pulse time is 20 microseconds.
5) Pre-coating a thermoplastic PI prepolymer (polyamic acid) on a PI packaging layer with the thickness of 50 microns, and drying to form a polyamic acid film, wherein the drying temperature is 150 ℃ and the drying time is 10 min;
6) performing hole opening treatment on a PI-polyamic acid film material locally, then performing lamination with the PI-copper electrode-graphene (LIG) assembly formed in the step 5), and completing imidization treatment, wherein the lamination temperature is 350 ℃, the time is 1h, and the pressure is 5 MPa. And before lamination, the partial copper electrode terminal is ensured to be exposed through the opening, so that a PI-copper electrode-LIG layer-PI assembly, namely the graphene high-temperature electrothermal film, is obtained.
Comparative example 1:
the traditional nickel-chromium-aluminum alloy electric heating film purchased in the market is purchased from Shenzhen Shenzhong Shenbailin electric heating product factories.
Table 1: testing temperature rise rate and temperature uniformity of electric heating film
Finally, it should be noted that: although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing a graphene high-temperature electrothermal film based on an LIG method is characterized by comprising the following steps:
s1, forming a composite layer of the PI-copper electrode, wherein the copper electrode is wholly embedded or partially embedded in the PI film;
s2, forming a PI material layer on the surface of the PI film-copper electrode composite layer to form a PI-copper electrode-PI material layer (to-be-LIG layer) assembly;
s3, LIG processing is carried out on the PI material layer, laser transmission is carried out to enable the PI material layer to form a graphene heating layer pattern, and a PI film-copper electrode composite layer-patterned graphene layer (LIG layer) structure is formed; and
s4, packaging a protective film layer on the surface of the patterned graphene layer;
the specific method of S1 is as follows:
coating a thermoplastic PI prepolymer (polyamic acid) on the surface of the copper electrode, drying and semi-curing to form a polyamic acid film, and then carrying out high-temperature pressing and imidization on the polyamic acid film to form a PI-copper electrode complex;
the specific method of S2 is as follows:
s2-1, coating a thermoplastic PI prepolymer (polyamide acid) on the surface of a PI film, drying to form a semi-cured polyamide acid film, forming a PI-polyamide acid film material, and opening holes in the PI-polyamide acid film material;
s2-2, covering the PI-polyamic acid film material with the opening on the surface of the PI film-copper electrode complex layer prepared in the step S1, and aligning the opening with the copper electrode to expose the copper electrode through the opening to form a structural member of the PI-copper electrode-polyamic acid film material-PI;
s2-3, pressing the structural member obtained in the S2-2, and performing imidization treatment on the polyamide acid film material to enable the PI-polyamide acid film material to be fused into a whole to form a finished layer of PI material layer, and finally obtaining the PI film-copper electrode-PI material layer (to-be-LIG layer) combination.
2. The method for preparing the graphene high-temperature electrothermal film based on the LIG method as claimed in claim 1, wherein in the step S1, the drying temperature is 120-200 ℃, and the drying time is 1-20 min;
preferably, in the step S1, the drying temperature is 150 ℃ and the drying time is 10 min;
preferably, in S1, the imidization treatment is performed by applying pressure at a high temperature: the pressing temperature is 250 ℃ and 350 ℃, and the pressure is 2-10 MPa.
3. The method for preparing the graphene high-temperature electrothermal film based on the LIG method as claimed in claim 1, wherein in the step S2-1, the drying temperature is 120-200 ℃, and the drying time is 1-20 min;
preferably, in the S2-1, the drying temperature is 150 ℃ and the drying time is 10 min.
4. The method of claim 1, wherein in step S2-3, the imidization process is performed by applying pressure at high temperature: the pressing temperature is 250 ℃ and 350 ℃, and the pressure is 2-10 MPa.
5. The method for preparing the graphene high-temperature electrothermal film based on the LIG method as claimed in claim 1, wherein in S3, LIG processing conditions are as follows: the wavelength of laser scanning is 1-20 microns, the power is 2-20W, and the pulse time is 5-30 microseconds;
preferably, in S3, the LIG processing conditions are: the wavelength of the laser scan was 10.6 microns, the power was 4.8W, and the pulse time was 20 microseconds.
6. The method for preparing the graphene high-temperature electrothermal film based on the LIG method as claimed in claim 1, wherein the protective film layer is made of PI material, and the structure of the final product forms a combination of PI-copper electrode-LIG layer-PI, namely the graphene high-temperature electrothermal film.
7. The method for preparing the graphene high-temperature electrothermal film based on the LIG method as claimed in claim 1, wherein the specific method of S4 is as follows:
s4-1, taking the PI film as a packaging layer;
s4-2, coating a thermoplastic PI prepolymer (polyamic acid) on the surface of the PI packaging layer, semi-drying to form a polyamic acid film, and performing opening treatment in a local area;
s4-3, then pressing the PI-copper electrode-graphene (LIG) assembly formed in S3, and completing imidization treatment, so that a polyamide acid film on the surface of the PI packaging layer and a PI packaging layer form an integrated PI material as a protective layer, and before pressing, a local copper electrode terminal is exposed through an opening, and thus the PI-copper electrode-LIG layer-PI assembly, namely the graphene high-temperature electrothermal film, is obtained.
8. The method for preparing the graphene high-temperature electrothermal film based on the LIG method as claimed in claim 7, wherein in the step S4-2, the drying temperature is 120-200 ℃ and the drying time is 1-20 min.
9. The method for preparing the graphene high-temperature electrothermal film based on the LIG method as claimed in claim 8, wherein in the step S4-2, the drying temperature is 150 ℃ and the drying time is 10 min.
10. The method of claim 7, wherein in step S4-3, the imidization process is performed by applying pressure at high temperature: the pressing temperature is 250 ℃ and 350 ℃, and the pressure is 2-10 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110452303.7A CN113163529B (en) | 2020-07-07 | 2020-07-07 | Method for preparing graphene high-temperature electrothermal film based on LIG method |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110452303.7A CN113163529B (en) | 2020-07-07 | 2020-07-07 | Method for preparing graphene high-temperature electrothermal film based on LIG method |
| CN202010646038.1A CN111818674B (en) | 2020-07-07 | 2020-07-07 | Method for preparing graphene high-temperature electrothermal film based on LIG method |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010646038.1A Division CN111818674B (en) | 2020-07-07 | 2020-07-07 | Method for preparing graphene high-temperature electrothermal film based on LIG method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113163529A true CN113163529A (en) | 2021-07-23 |
| CN113163529B CN113163529B (en) | 2022-08-05 |
Family
ID=72843425
Family Applications (4)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110463858.1A Active CN113242616B (en) | 2020-07-07 | 2020-07-07 | Method for preparing graphene high-temperature electrothermal film based on LIG method |
| CN202110452303.7A Active CN113163529B (en) | 2020-07-07 | 2020-07-07 | Method for preparing graphene high-temperature electrothermal film based on LIG method |
| CN202110463860.9A Active CN113225856B (en) | 2020-07-07 | 2020-07-07 | Method for preparing graphene high-temperature electrothermal film based on LIG method |
| CN202010646038.1A Active CN111818674B (en) | 2020-07-07 | 2020-07-07 | Method for preparing graphene high-temperature electrothermal film based on LIG method |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110463858.1A Active CN113242616B (en) | 2020-07-07 | 2020-07-07 | Method for preparing graphene high-temperature electrothermal film based on LIG method |
Family Applications After (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110463860.9A Active CN113225856B (en) | 2020-07-07 | 2020-07-07 | Method for preparing graphene high-temperature electrothermal film based on LIG method |
| CN202010646038.1A Active CN111818674B (en) | 2020-07-07 | 2020-07-07 | Method for preparing graphene high-temperature electrothermal film based on LIG method |
Country Status (1)
| Country | Link |
|---|---|
| CN (4) | CN113242616B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112911741A (en) * | 2021-01-18 | 2021-06-04 | 安徽宇航派蒙健康科技股份有限公司 | Preparation method of flexible graphene electrothermal film |
| CN112788801A (en) * | 2021-01-18 | 2021-05-11 | 安徽宇航派蒙健康科技股份有限公司 | Preparation method of graphene polymer electrothermal film |
Citations (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1209719A (en) * | 1998-06-23 | 1999-03-03 | 北京化工大学 | Heat-resistant fire-retardant plane-shaped exothermic body and producing method therefor |
| US20060083939A1 (en) * | 2004-10-20 | 2006-04-20 | Dunbar Meredith L | Light activatable polyimide compositions for receiving selective metalization, and methods and compositions related thereto |
| US20090129421A1 (en) * | 2007-11-21 | 2009-05-21 | Takeshi Kitatani | Semiconductor laser diode |
| CN101699920A (en) * | 2009-11-20 | 2010-04-28 | 宁波今山电子材料有限公司 | Method for preparing polyimide heating film |
| WO2013124454A1 (en) * | 2012-02-22 | 2013-08-29 | Sgl Carbon Se | Method for producing a graphite film, a graphite film produced using this method, and the use thereof |
| WO2014073402A1 (en) * | 2012-11-08 | 2014-05-15 | 保土谷化学工業株式会社 | Planar heater |
| CN104151582A (en) * | 2014-07-17 | 2014-11-19 | 哈尔滨工业大学 | Method for preparing graphene-polyimide conductive black film |
| US20160128187A1 (en) * | 2014-10-30 | 2016-05-05 | National Taiwan University | Flexible and transparent electrode and manufacturing method thereof |
| CN106744865A (en) * | 2016-12-01 | 2017-05-31 | 无锡格菲电子薄膜科技有限公司 | A kind of laser donor membrane and preparation method thereof, the method using laser donor film transfer graphene film |
| CN107039257A (en) * | 2017-04-06 | 2017-08-11 | 清华大学深圳研究生院 | A kind of graphical preparation method of induced with laser graphene and extent product |
| CN107206741A (en) * | 2014-11-26 | 2017-09-26 | 威廉马歇莱思大学 | Graphene mixing material for the induced with laser of electronic installation |
| CN107808818A (en) * | 2017-09-21 | 2018-03-16 | 天津大学 | A kind of preparation method of flexible capacitor |
| CN108289345A (en) * | 2018-01-29 | 2018-07-17 | 杭州白熊科技有限公司 | Preparation method, graphene Electric radiant Heating Film, electrothermal device and the application of graphene Electric radiant Heating Film |
| CN207854207U (en) * | 2018-01-11 | 2018-09-11 | 安徽宇航派蒙防辐射科技股份有限公司 | A kind of intelligence wearable dress ornament graphene heating film |
| CN108684084A (en) * | 2018-03-30 | 2018-10-19 | 重庆墨希科技有限公司 | The preparation process of graphene heating film |
| US20180352611A1 (en) * | 2017-05-30 | 2018-12-06 | Korea Institute Of Science And Technology | Metal nanowire heater and method of fabricating the same |
| CN109275210A (en) * | 2018-10-12 | 2019-01-25 | 重庆墨希科技有限公司 | A kind of heating film of high reliability and preparation method thereof based on graphene |
| CN109421402A (en) * | 2017-08-29 | 2019-03-05 | 武汉大学 | A kind of laser engraving preparation method of highly conductive graphene film array |
| CN109729605A (en) * | 2018-12-27 | 2019-05-07 | 桂林清扬科技有限公司 | A kind of electric heating film and preparation method thereof |
| CN110098302A (en) * | 2019-05-06 | 2019-08-06 | 华南理工大学 | A kind of flexible polyimide substrate and preparation method thereof for miniature LED component |
| CN110769527A (en) * | 2019-09-12 | 2020-02-07 | 宁波科诺佳新材料有限公司 | Organic high-temperature electric heating composite film and preparation method thereof |
| CN111349255A (en) * | 2020-04-14 | 2020-06-30 | 安徽宇航派蒙健康科技股份有限公司 | Graphene-polyimide conductive film and preparation method thereof |
| CN111372336A (en) * | 2020-03-25 | 2020-07-03 | 广州智慧医疗科技有限公司 | Infrared electrothermal film and preparation method thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5356656A (en) * | 1993-03-26 | 1994-10-18 | Industrial Technology Research Institute | Method for manufacturing flexible amorphous silicon solar cell |
| JP4051900B2 (en) * | 2000-12-20 | 2008-02-27 | 富士ゼロックス株式会社 | Heat resistant resin film having metal thin film and method for producing the same, endless belt, method for producing the same and image forming apparatus |
| JP5356088B2 (en) * | 2009-03-27 | 2013-12-04 | 古河電気工業株式会社 | Semiconductor laser, method for generating laser beam, and method for narrowing spectral line width of laser beam |
| WO2015151923A1 (en) * | 2014-03-31 | 2015-10-08 | 東レ株式会社 | Substrate film, catalyst transfer sheet, method for producing membrane electrode assembly, and method for producing catalyst layer-coated electrolyte membrane |
| CN104637789A (en) * | 2015-02-13 | 2015-05-20 | 中国科学院重庆绿色智能技术研究院 | Method for preparing patterned graphene and graphene flexible transparent electrothermal film |
| CN105174250A (en) * | 2015-09-17 | 2015-12-23 | 清华大学 | Method for preparing graphene by virtue of photoreduction of organic thin film |
| CN108770096A (en) * | 2018-08-20 | 2018-11-06 | 深圳市同益高新电子科技有限公司 | A kind of preparation process of heating film |
| CN110267375B (en) * | 2019-06-25 | 2022-03-08 | 宁波柔碳电子科技有限公司 | Preparation process of graphene electric heating film and graphene electric heating film |
| CN111114062A (en) * | 2019-12-03 | 2020-05-08 | 浙江工业大学 | Composite electrothermal film suitable for high-temperature heating and preparation method thereof |
| CN110952741A (en) * | 2019-12-31 | 2020-04-03 | 浙江攀猿侠户外运动发展有限公司 | Electric heating wallpaper with three built-in electrodes |
-
2020
- 2020-07-07 CN CN202110463858.1A patent/CN113242616B/en active Active
- 2020-07-07 CN CN202110452303.7A patent/CN113163529B/en active Active
- 2020-07-07 CN CN202110463860.9A patent/CN113225856B/en active Active
- 2020-07-07 CN CN202010646038.1A patent/CN111818674B/en active Active
Patent Citations (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1209719A (en) * | 1998-06-23 | 1999-03-03 | 北京化工大学 | Heat-resistant fire-retardant plane-shaped exothermic body and producing method therefor |
| US20060083939A1 (en) * | 2004-10-20 | 2006-04-20 | Dunbar Meredith L | Light activatable polyimide compositions for receiving selective metalization, and methods and compositions related thereto |
| US20090129421A1 (en) * | 2007-11-21 | 2009-05-21 | Takeshi Kitatani | Semiconductor laser diode |
| CN101699920A (en) * | 2009-11-20 | 2010-04-28 | 宁波今山电子材料有限公司 | Method for preparing polyimide heating film |
| WO2013124454A1 (en) * | 2012-02-22 | 2013-08-29 | Sgl Carbon Se | Method for producing a graphite film, a graphite film produced using this method, and the use thereof |
| WO2014073402A1 (en) * | 2012-11-08 | 2014-05-15 | 保土谷化学工業株式会社 | Planar heater |
| CN104151582A (en) * | 2014-07-17 | 2014-11-19 | 哈尔滨工业大学 | Method for preparing graphene-polyimide conductive black film |
| US20160128187A1 (en) * | 2014-10-30 | 2016-05-05 | National Taiwan University | Flexible and transparent electrode and manufacturing method thereof |
| CN107206741A (en) * | 2014-11-26 | 2017-09-26 | 威廉马歇莱思大学 | Graphene mixing material for the induced with laser of electronic installation |
| CN106744865A (en) * | 2016-12-01 | 2017-05-31 | 无锡格菲电子薄膜科技有限公司 | A kind of laser donor membrane and preparation method thereof, the method using laser donor film transfer graphene film |
| CN107039257A (en) * | 2017-04-06 | 2017-08-11 | 清华大学深圳研究生院 | A kind of graphical preparation method of induced with laser graphene and extent product |
| US20180352611A1 (en) * | 2017-05-30 | 2018-12-06 | Korea Institute Of Science And Technology | Metal nanowire heater and method of fabricating the same |
| CN109421402A (en) * | 2017-08-29 | 2019-03-05 | 武汉大学 | A kind of laser engraving preparation method of highly conductive graphene film array |
| CN107808818A (en) * | 2017-09-21 | 2018-03-16 | 天津大学 | A kind of preparation method of flexible capacitor |
| CN207854207U (en) * | 2018-01-11 | 2018-09-11 | 安徽宇航派蒙防辐射科技股份有限公司 | A kind of intelligence wearable dress ornament graphene heating film |
| CN108289345A (en) * | 2018-01-29 | 2018-07-17 | 杭州白熊科技有限公司 | Preparation method, graphene Electric radiant Heating Film, electrothermal device and the application of graphene Electric radiant Heating Film |
| CN108684084A (en) * | 2018-03-30 | 2018-10-19 | 重庆墨希科技有限公司 | The preparation process of graphene heating film |
| CN109275210A (en) * | 2018-10-12 | 2019-01-25 | 重庆墨希科技有限公司 | A kind of heating film of high reliability and preparation method thereof based on graphene |
| CN109729605A (en) * | 2018-12-27 | 2019-05-07 | 桂林清扬科技有限公司 | A kind of electric heating film and preparation method thereof |
| CN110098302A (en) * | 2019-05-06 | 2019-08-06 | 华南理工大学 | A kind of flexible polyimide substrate and preparation method thereof for miniature LED component |
| CN110769527A (en) * | 2019-09-12 | 2020-02-07 | 宁波科诺佳新材料有限公司 | Organic high-temperature electric heating composite film and preparation method thereof |
| CN111372336A (en) * | 2020-03-25 | 2020-07-03 | 广州智慧医疗科技有限公司 | Infrared electrothermal film and preparation method thereof |
| CN111349255A (en) * | 2020-04-14 | 2020-06-30 | 安徽宇航派蒙健康科技股份有限公司 | Graphene-polyimide conductive film and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111818674A (en) | 2020-10-23 |
| CN113163529B (en) | 2022-08-05 |
| CN113225856B (en) | 2022-08-05 |
| CN113242616B (en) | 2022-08-05 |
| CN113242616A (en) | 2021-08-10 |
| CN113225856A (en) | 2021-08-06 |
| CN111818674B (en) | 2021-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113225856B (en) | Method for preparing graphene high-temperature electrothermal film based on LIG method | |
| US11542411B2 (en) | Method for preparing composites on basis of graphene bonding | |
| CN105818504A (en) | Single-sided corona-resistant polyimide composite thin film and preparation method thereof | |
| CN110885964A (en) | One-time evaporation preparation method of metal-plated film for battery | |
| WO2018219000A1 (en) | Polyimide-based composite carbon film with high thermal conductivity and preparation method therefor | |
| CN108755144A (en) | A kind of preparation method of crosslinked polyimide tunica fibrosa | |
| CN206193284U (en) | And simultaneously, | |
| CN1093730C (en) | Heat-resistant fire-retardant plane-shaped exothermic body and producing method therefor | |
| WO2024119745A1 (en) | Glass heating sheet and preparation method therefor | |
| CN109750245A (en) | A kind of preparation method of copper covered steel wire | |
| CN103367490B (en) | Solar battery back film of a kind of low temperature plasma process and preparation method thereof | |
| CN108207044A (en) | A kind of flexible electric heating module and preparation method thereof | |
| CN114014679A (en) | Reinforced graphite film and preparation method thereof | |
| CN108517050A (en) | A kind of preparation method of high strength fibre element conductive film | |
| CN114290769B (en) | Metal plate, insulated metal plate and preparation method and application of insulated metal plate | |
| CN110524978A (en) | A kind of Copper Clad Laminates Based On Polytetrafluoroethylene and preparation method thereof of long-acting bonding | |
| CN113105657A (en) | High-orientation and high-power graphene heating film and preparation method and application thereof | |
| CN220012520U (en) | Color-changing identification film | |
| CN112010296A (en) | Impurity removal method for hydrogen halide reduced graphene oxide film, graphene heat conduction film and preparation method thereof | |
| CN210765111U (en) | High-insulation hot melt adhesive film structure | |
| CN116761286A (en) | Heating film and preparation method thereof | |
| CN208284606U (en) | New-energy automobile dynamic lithium battery heating plate | |
| CN220189696U (en) | Safety current collector | |
| CN208558572U (en) | A kind of laminated substrate and laminating machine | |
| JP2005276789A (en) | Method for manufacturing fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |