CN113512223A - Polyimide conductive film - Google Patents
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- CN113512223A CN113512223A CN202110716806.0A CN202110716806A CN113512223A CN 113512223 A CN113512223 A CN 113512223A CN 202110716806 A CN202110716806 A CN 202110716806A CN 113512223 A CN113512223 A CN 113512223A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/044—Forming conductive coatings; Forming coatings having anti-static properties
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1039—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors comprising halogen-containing substituents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1075—Partially aromatic polyimides
- C08G73/1082—Partially aromatic polyimides wholly aromatic in the tetracarboxylic moiety
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/102—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions other than those only involving unsaturated carbon-to-carbon bonds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2475/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
- C08J2475/04—Polyurethanes
Abstract
The invention discloses a polyimide conductive film, which is prepared by coating conductive ink on the surface of a polyimide base film and then drying the polyimide base film, wherein the polyimide is polyimide containing carbamido groups; the raw materials of the conductive ink comprise: the silver nano-wire adhesive comprises silver nano-wires, an adhesive and a solvent, wherein the adhesive is a polyurethane adhesive. The silver nanowires in the polyimide conductive film are not easy to fall off, are uniformly dispersed, and have good conductivity.
Description
Technical Field
The invention relates to the technical field of conductive films, in particular to a polyimide conductive film.
Background
As wearable devices and flexible electronics industries show great commercial prospects, flexible conductive films are also receiving increasing attention. The flexible conductive film mainly comprises a flexible base film and a conductive material. The preparation process generally comprises the steps of coating conductive ink on the surface of a flexible base film and drying to obtain the flexible base film.
Currently, ITO (indium tin oxide) is the most important material for preparing transparent conductive films on the market, but ITO has some insurmountable defects: the ITO film cannot obtain very low sheet resistance and cannot be applied to equipment with larger size; when the film is bent, the surface of the film is easy to crack and break, and the film cannot be used for preparing flexible equipment with good bending resistance; meanwhile, the storage capacity of ITO is limited, the price is gradually increased along with the increase of consumption, and expensive vacuum sputtering equipment is needed for preparing an ITO film.
In recent years, researchers have developed various new technologies to substitute for ITO materials, such as carbon nanotubes, graphene, silver nanowires, metal grids, etc., which have better flexibility than ITO; however, carbon nanotubes and graphene have certain defects in electrical properties and optical properties of metal grids, and are still in the research stage; the nano silver wire has simple coating process and better optical property and sheet resistance than ITO, and can be used for preparing a conductive film.
However, when the base film is made of polyimide, the silver nanowires and the polyimide base film have poor adhesion, and are easy to fall off, so that the conductivity is affected; and when the conductive ink is dried, silver nanowires in the conductive ink are easy to agglomerate, so that the uniformity and the conductivity of the conductive film are influenced, and the subsequent application is not facilitated.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the polyimide conductive film, and the silver nanowires in the polyimide conductive film are not easy to fall off, are uniformly dispersed and have good conductivity.
The invention provides a polyimide conductive film, which is prepared by coating conductive ink on the surface of a polyimide base film and then drying the polyimide base film, wherein the polyimide is polyimide containing carbamido groups; the raw materials of the conductive ink comprise: the silver nano-wire adhesive comprises silver nano-wires, an adhesive and a solvent, wherein the adhesive is a polyurethane adhesive.
Before the conductive ink is coated, the polyimide base film needs to be cleaned and dried, and the cleaning solvent can be acetone, ethanol, water and the like.
Preferably, the content of-CNO in the polyurethane adhesive is 15-18 wt%.
Preferably, the silver nanowires are graft-modified with a silane coupling agent containing isocyanate groups.
The method for graft modification is a silane coupling agent modification method commonly used by those skilled in the art, and the specific steps can be as follows: mixing silver nanowires and a solution of a silane coupling agent containing isocyanate groups uniformly, stirring for 1-2h at the temperature of 70-80 ℃, filtering, washing and drying to obtain the silver nanowire-containing solution.
Preferably, the drying temperature is 180-.
Preferably, in the preparation process of the polyimide containing the ureido groups, an amino-terminated polyamic acid solution, an isocyanate group-terminated polyurea solution and a dianhydride monomer 1 are reacted in an inert gas atmosphere to obtain an intermediate material, and then imidized to obtain the polyimide containing the ureido groups.
The solvent in the amino-terminated polyamic acid solution and the isocyanate group-terminated polyurea solution may be N-methylpyrrolidone, N-dimethylformamide, dimethylacetamide, or the like.
Preferably, the isocyanate group-terminated polyurea is synthesized from diisocyanate and diamine monomer 1; the synthesis raw materials of the amino-terminated polyamic acid comprise a dianhydride monomer 2 and a diamine monomer 2.
The dianhydride monomer 1 and the dianhydride monomer 2 may be the same or different; the diamine monomer 1 and the diamine monomer 2 may be the same or different.
The dianhydride monomer 1 and the dianhydride monomer 2 may be at least one of: 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (6-FDA), 4- (2, 5-dioxotetrahydrofuran-3-yl) -1,2,3, 4-tetrahydronaphthalene-1, 2-dicarboxylic anhydride (TDA), pyromellitic dianhydride (1,2,4, 5-benzenetetracarboxylic dianhydride, PMDA), Benzophenone Tetracarboxylic Dianhydride (BTDA), biphenyl tetracarboxylic dianhydride (BPDA); and examples of the dianhydride monomer 1 and the dianhydride monomer 2 are not limited thereto.
The diamine monomer 1 and the diamine monomer 2 may be at least one of: diaminodiphenyl ether (ODA), p-phenylenediamine (p-PDA), m-phenylenediamine (m-PDA), p-methylenediamine (p-MDA), m-methylenediamine (m-MDA), bistrifluoromethylbenzidine (TFDB), cyclohexanediamine (13CHD,14 CHD); and examples of the diamine monomer 1 and the diamine monomer 2 are not limited thereto.
The diisocyanate may be at least one of the following: toluene Diisocyanate (TDI), isophorone diisocyanate (IPDI), diphenylmethane diisocyanate (MDI), dicyclohexylmethane diisocyanate (HMDI), Hexamethylene Diisocyanate (HDI), Lysine Diisocyanate (LDI); and examples of the diisocyanate are not limited thereto.
The polyimide conductive film of the present invention is preferably a transparent polyimide conductive film. Can be obtained by selecting suitable dianhydride monomer 1, dianhydride monomer 2, diamine monomer 1 and diamine monomer 2.
Preferably, the molar ratio of diisocyanate to diamine monomer 1 is 1.05-1.1: 1.
Preferably, the molar ratio of dianhydride monomer 2 to diamine monomer 2 is 0.93 to 0.94: 1.
Preferably, the molar ratio of diamine monomer 1 to dianhydride monomer 1 is 1: 0.06-0.08.
Preferably, the molar ratio of diamine monomer 1 to diamine monomer 2 is 0.09 to 0.11: 1.
Preferably, the reaction temperature is 60-80 ℃ and the reaction time is 5-6 h.
Preferably, the imidization procedure is: the temperature is maintained at 80-100 ℃ for 2-2.5h, and then at 120-.
Preferably, the solvent comprises: at least one of N-hexane, cyclohexane, tetrahydrofuran, toluene, xylene, N-dimethylformamide, ethyl acetate or butyl acetate.
Preferably, the raw material of the conductive ink further includes a dispersant.
Preferably, the dispersant comprises: at least one of polyvinylpyrrolidone, cellulose acetate butyrate, cellulose acetate, sodium dodecyl sulfate, hexadecyl dimethyl ammonium bromide, chlorohexadecyl pyridine and fluorocarbon surfactant.
Preferably, the weight ratio of the silver nanowires to the adhesive to the solvent is 0.6-0.8:0.6-1.6: 100.
Preferably, the weight ratio of the silver nanowires to the dispersing agent is 6-8: 3-9.
Has the advantages that:
1. the invention selects amino-terminated polyamic acid solution to react with isocyanate group-terminated polyurea solution and imidize, and introduces ureido group into polyimide main chain; under a proper drying temperature, the ureido groups can react with isocyanate groups in the polyurethane adhesive, so that a cross-linked network is formed between the base film and the conductive coating, the adhesion performance is improved, the silver nanowires are fixed, and the silver nanowires are prevented from falling off;
2. proper proportion is selected for diisocyanate, diamine monomer 1, diamine monomer 2, dianhydride monomer 1 and dianhydride monomer 2, and the performance of polyimide can be maintained while a proper amount of ureido groups are introduced into the polyimide main chain; the high temperature resistance of the polyimide base film can be improved;
3. carrying out graft modification treatment on the silver nanowires by adopting a silane coupling agent containing isocyanate groups, so that the surfaces of the silver nanowires are provided with isocyanate groups and can react with urea groups to fix the silver nanowires; and after the grafting modification of the silane coupling agent, the silver nano wires are matched with the dispersing agent, so that the dispersion uniformity of the silver nano wires in the conductive ink can be improved, the agglomeration of the silver nano wires in the conductive coating is avoided, the coating is convenient, and the conductivity can be improved.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A polyimide conductive film is prepared by coating conductive ink on the surface of a polyimide base film, and drying at 190 ℃ for 20min to obtain the polyimide conductive film, wherein the polyimide is polyimide containing carbamido groups; the conductive ink comprises the following raw materials in parts by weight: 0.7g of gamma-isocyanic acid propyl triethoxy silane modified silver nanowire, 1.4g of polyurethane adhesive with 17 wt% of-CNO content, 0.6g of sodium dodecyl sulfate and 100g of N, N-dimethylformamide;
wherein, in the preparation process of the polyimide containing the carbamido group,
0.1mol of cyclohexanediThe amine was dissolved in 250ml of dimethylacetamide and then N was added2Discharging air, slowly adding 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (0.0935 mol) for 3 times, adjusting the temperature to 35 ℃, and carrying out heat preservation reaction for 4 hours to obtain amino-terminated polyamic acid solution;
0.01mol of cyclohexanediamine is dissolved in 50ml of dimethylacetamide and N is then introduced2Discharging air, slowly adding dicyclohexylmethane diisocyanate (0.0107 mol in total) for 3 times, heating to 80 ℃, and stirring for 5 hours under heat preservation to obtain an isocyanate group-terminated polyurea solution;
then in N2In the atmosphere, uniformly mixing the amino-terminated polyamide acid solution and the isocyanate group-terminated polyurea solution, stirring at 70 ℃ for 1h, then adding 0.7mmol of 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, continuously keeping the temperature and stirring for 4.5h, and defoaming to obtain an intermediate material; coating the intermediate material on a clean glass plate, preserving heat for 2.2h at 90 ℃, and preserving heat for 0.7h at 125 ℃, 175 ℃, 220 ℃ and 255 ℃ respectively to obtain the polyimide base film.
Example 2
A polyimide conductive film is prepared by coating conductive ink on the surface of a polyimide base film, and drying at 180 ℃ for 25min to obtain the polyimide conductive film, wherein the polyimide is polyimide containing carbamido groups; the conductive ink comprises the following raw materials in parts by weight: 0.6g of gamma-isocyanic acid propyl triethoxy silane modified silver nanowire, 0.6g of polyurethane adhesive with 15 wt% of-CNO content, 0.3g of fluorocarbon surfactant and 100g of N, N-dimethylformamide;
wherein, in the preparation process of the polyimide containing the carbamido group,
0.1mol of diaminodiphenyl ether is dissolved in 250ml of dimethylacetamide, and N is then introduced2Discharging air, slowly adding 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (0.094 mol in total) for 3 times, adjusting the temperature to 35 ℃, and carrying out heat preservation reaction for 4 hours to obtain an amino-terminated polyamic acid solution;
0.009mol of diaminodiphenyl ether is dissolved in 50ml of dimethylacetamide, then N is added2The air was vented and diphenylmethane diisocyanate (co 0.00945 mo) was slowly added in 3 portionsl), heating to 80 ℃, and stirring for 5 hours under the condition of heat preservation to obtain an isocyanate group-terminated polyurea solution;
then in N2In the atmosphere, uniformly mixing the amino-terminated polyamide acid solution and the isocyanate group-terminated polyurea solution, stirring at 80 ℃ for 1h, then adding 0.54mmol of 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, continuously keeping the temperature and stirring for 4h, and defoaming to obtain an intermediate material; coating the intermediate material on a clean glass plate, preserving heat for 2h at 100 ℃, and then respectively preserving heat for 0.5h at 130 ℃, 180 ℃, 230 ℃ and 255 ℃ to obtain the polyimide base film.
Example 3
A polyimide conductive film is prepared by coating conductive ink on the surface of a polyimide base film, and drying at 200 ℃ for 15min to obtain the polyimide conductive film, wherein the polyimide is polyimide containing carbamido groups; the conductive ink comprises the following raw materials in parts by weight: 0.8g of gamma-isocyanic acid propyl triethoxy silane modified silver nanowire, 1.6g of polyurethane adhesive with 18 wt% of-CNO content, 0.9g of polyvinylpyrrolidone and 100g of N, N-dimethylformamide;
wherein, in the preparation process of the polyimide containing the carbamido group,
0.1mol of bistrifluoromethylbenzidine is dissolved in 250ml of dimethylacetamide, and N is introduced2Discharging air, slowly adding 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (0.093 mol in total) for 3 times, adjusting the temperature to 35 ℃, and carrying out heat preservation reaction for 4 hours to obtain an amino-terminated polyamic acid solution;
0.011mol of bistrifluoromethylbenzidine was dissolved in 50ml of dimethylacetamide, followed by N2Discharging air, slowly adding isophorone diisocyanate (0.0121 mol in total) for 3 times, heating to 80 ℃, and stirring for 5 hours under heat preservation to obtain an isocyanate group-terminated polyurea solution;
then in N2In the atmosphere, uniformly mixing the amino-terminated polyamide acid solution and the isocyanate group-terminated polyurea solution, stirring at 60 ℃ for 1h, then adding 0.88mmol of 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, continuously keeping the temperature and stirring for 5h, and defoaming to obtain an intermediate material; coating the intermediate material on clean glassAnd (3) insulating the glass plate for 2.5h at 80 ℃, and then insulating the glass plate for 1h at 120 ℃, 170 ℃, 210 ℃ and 250 ℃ respectively to obtain the polyimide basal membrane.
Comparative example 1
A polyimide conducting film is prepared through dissolving 0.1mol of cyclohexanediamine in 250ml of dimethylacetamide, and introducing N2Discharging air, slowly adding 2, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride (0.0935 mol) for 3 times, adjusting the temperature to 35 ℃, and carrying out heat preservation reaction for 4 hours to obtain amino-terminated polyamic acid solution; defoaming, coating on clean glass plate, keeping the temperature at 90 deg.C for 2.2h, and keeping the temperature at 125 deg.C, 175 deg.C, 220 deg.C, 255 deg.C for 0.7h to obtain polyimide-based film, otherwise the same as example 1.
Comparative example 2
The 'gamma-isocyanic acid propyl triethoxy silane modified silver nano-wire' is replaced by the common silver nano-wire, and the rest is the same as the example 1.
The properties of the polyimide conductive films obtained in examples 1 to 3 and comparative examples 1 to 2 were measured, and the results are shown in table 1.
TABLE 1 test results
Remarking: the adhesive force is tested by a Baige method, and the coating is 0 grade when 100 percent of the coating is retained; the coating is kept relatively complete, and only a few corners are damaged and are 1 grade; 2 grades when the corners are damaged more and the whole lattice is not fallen off; the corner is seriously damaged, and the number of the whole lattices is 3 when the whole lattices fall off; the corner is seriously damaged, more whole lattices fall off, and the coating is in grade 4 when the reserved area of the coating is more than 65 percent; the coating has a retention area of less than 65% and is grade 5.
As can be seen from table 1, the silver nanowires in the polyimide conductive film of the present invention are not easily exfoliated, and have good conductivity; the common silver nanowires are not uniformly dispersed, so that the sheet resistance is increased.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (10)
1. A polyimide conductive film is characterized in that conductive ink is coated on the surface of a polyimide base film, and then the polyimide conductive film is obtained by drying, wherein the polyimide is polyimide containing carbamido groups; the raw materials of the conductive ink comprise: the silver nano-wire adhesive comprises silver nano-wires, an adhesive and a solvent, wherein the adhesive is a polyurethane adhesive.
2. The polyimide conductive film according to claim 1, wherein the content of-CNO in the polyurethane adhesive is 15 to 18 wt%.
3. The polyimide conductive film according to claim 1 or 2, wherein the silver nanowires are graft-modified with a silane coupling agent containing an isocyanate group.
4. The polyimide conductive film according to any one of claims 1 to 3, wherein the drying temperature is 180 ℃ and 200 ℃, and the drying time is 15 to 25 min.
5. The polyimide conductive film according to any one of claims 1 to 4, wherein in the preparation of the polyimide having a ureido group, an amino-terminated polyamic acid solution, an isocyanate group-terminated polyurea solution and a dianhydride monomer 1 are reacted in an inert gas atmosphere to obtain an intermediate material, and then imidized to obtain the polyimide having a ureido group.
6. The polyimide conductive film according to claim 5, wherein the isocyanate group-terminated polyurea is synthesized from diisocyanate and a diamine monomer 1; the synthesis raw materials of the amino-terminated polyamic acid comprise a dianhydride monomer 2 and a diamine monomer 2; preferably, the molar ratio of diisocyanate to diamine monomer 1 is 1.05-1.1: 1; preferably, the molar ratio of dianhydride monomer 2 to diamine monomer 2 is 0.93-0.94: 1; preferably, the molar ratio of diamine monomer 1 to dianhydride monomer 1 is 1: 0.06-0.08; preferably, the molar ratio of diamine monomer 1 to diamine monomer 2 is 0.09-0.11: 1; preferably, the reaction temperature is 60-80 ℃, and the reaction time is 5-6 h; preferably, the imidization procedure is: the temperature is maintained at 80-100 ℃ for 2-2.5h, and then at 120-.
7. The polyimide conductive film according to any one of claims 1 to 6, wherein the solvent comprises: at least one of N-hexane, cyclohexane, tetrahydrofuran, toluene, xylene, N-dimethylformamide, ethyl acetate or butyl acetate.
8. The polyimide conductive film according to any one of claims 1 to 7, wherein a raw material of the conductive ink further comprises a dispersant; preferably, the dispersant comprises: at least one of polyvinylpyrrolidone, cellulose acetate butyrate, cellulose acetate, sodium dodecyl sulfate, hexadecyl dimethyl ammonium bromide, chlorohexadecyl pyridine and fluorocarbon surfactant.
9. The polyimide conductive film according to any one of claims 1 to 8, wherein the weight ratio of the silver nanowires, the adhesive, and the solvent is 0.6-0.8:0.6-1.6: 100.
10. The polyimide conductive film according to claim 8, wherein the weight ratio of the silver nanowires to the dispersant is 6-8: 3-9.
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