CN117363013A - Polycool imine insulation-nano silver conductive circuit and preparation method and application thereof - Google Patents
Polycool imine insulation-nano silver conductive circuit and preparation method and application thereof Download PDFInfo
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- CN117363013A CN117363013A CN202310927914.1A CN202310927914A CN117363013A CN 117363013 A CN117363013 A CN 117363013A CN 202310927914 A CN202310927914 A CN 202310927914A CN 117363013 A CN117363013 A CN 117363013A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 150000002466 imines Chemical class 0.000 title abstract description 4
- 239000002131 composite material Substances 0.000 claims abstract description 84
- 229910052751 metal Inorganic materials 0.000 claims abstract description 73
- 239000002184 metal Substances 0.000 claims abstract description 73
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229920005575 poly(amic acid) Polymers 0.000 claims abstract description 51
- 239000004952 Polyamide Substances 0.000 claims abstract description 50
- 239000002253 acid Substances 0.000 claims abstract description 50
- 229920002647 polyamide Polymers 0.000 claims abstract description 50
- 238000007639 printing Methods 0.000 claims abstract description 48
- 239000004642 Polyimide Substances 0.000 claims abstract description 32
- 229920001721 polyimide Polymers 0.000 claims abstract description 32
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 238000010146 3D printing Methods 0.000 claims abstract description 28
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003960 organic solvent Substances 0.000 claims abstract description 22
- 230000009467 reduction Effects 0.000 claims abstract description 19
- 238000007740 vapor deposition Methods 0.000 claims abstract description 14
- 238000011065 in-situ storage Methods 0.000 claims abstract description 12
- 238000004321 preservation Methods 0.000 claims description 31
- 239000000047 product Substances 0.000 claims description 21
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 14
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical compound C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- -1 silver tetrafluoroborate Chemical compound 0.000 claims description 8
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 6
- KZJPVUDYAMEDRM-UHFFFAOYSA-M silver;2,2,2-trifluoroacetate Chemical compound [Ag+].[O-]C(=O)C(F)(F)F KZJPVUDYAMEDRM-UHFFFAOYSA-M 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- CHACQUSVOVNARW-LNKPDPKZSA-M silver;(z)-4-oxopent-2-en-2-olate Chemical compound [Ag+].C\C([O-])=C\C(C)=O CHACQUSVOVNARW-LNKPDPKZSA-M 0.000 claims description 5
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 claims description 3
- JKFYKCYQEWQPTM-UHFFFAOYSA-N 2-azaniumyl-2-(4-fluorophenyl)acetate Chemical compound OC(=O)C(N)C1=CC=C(F)C=C1 JKFYKCYQEWQPTM-UHFFFAOYSA-N 0.000 claims description 3
- RYKLZUPYJFFNRR-UHFFFAOYSA-N 3-hydroxypiperidin-2-one Chemical compound OC1CCCNC1=O RYKLZUPYJFFNRR-UHFFFAOYSA-N 0.000 claims description 3
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 3
- 229910021612 Silver iodide Inorganic materials 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 3
- CZKMPDNXOGQMFW-UHFFFAOYSA-N chloro(triethyl)germane Chemical compound CC[Ge](Cl)(CC)CC CZKMPDNXOGQMFW-UHFFFAOYSA-N 0.000 claims description 3
- QEKREONBSFPWTQ-UHFFFAOYSA-N disilver dioxido(dioxo)tungsten Chemical compound [Ag+].[Ag+].[O-][W]([O-])(=O)=O QEKREONBSFPWTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- SNGREZUHAYWORS-UHFFFAOYSA-N perfluorooctanoic acid Chemical compound OC(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F SNGREZUHAYWORS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001958 silver carbonate Inorganic materials 0.000 claims description 3
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 claims description 3
- 229940045105 silver iodide Drugs 0.000 claims description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 3
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 3
- 229910000367 silver sulfate Inorganic materials 0.000 claims description 3
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 claims description 3
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 3
- GPNIJXACCBKBEP-UHFFFAOYSA-M silver;2,2,3,3,4,4,4-heptafluorobutanoate Chemical compound [Ag+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)F GPNIJXACCBKBEP-UHFFFAOYSA-M 0.000 claims description 3
- WXENESFPQCWDHY-UHFFFAOYSA-M silver;2-ethylhexanoate Chemical compound [Ag+].CCCCC(CC)C([O-])=O WXENESFPQCWDHY-UHFFFAOYSA-M 0.000 claims description 3
- 239000013065 commercial product Substances 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- HSYLTRBDKXZSGS-UHFFFAOYSA-N silver;bis(trifluoromethylsulfonyl)azanide Chemical compound [Ag+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HSYLTRBDKXZSGS-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 25
- 229910052709 silver Inorganic materials 0.000 abstract description 15
- 239000004332 silver Substances 0.000 abstract description 14
- 239000000853 adhesive Substances 0.000 abstract description 9
- 230000001070 adhesive effect Effects 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 7
- 238000013461 design Methods 0.000 abstract description 5
- 238000001816 cooling Methods 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 description 11
- 238000009413 insulation Methods 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 239000007787 solid Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000000498 ball milling Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 238000009825 accumulation Methods 0.000 description 4
- 239000000306 component Substances 0.000 description 4
- 239000011231 conductive filler Substances 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000005457 ice water Substances 0.000 description 3
- 229920000307 polymer substrate Polymers 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000007641 inkjet printing Methods 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229940071575 silver citrate Drugs 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910001339 C alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- 239000004734 Polyphenylene sulfide Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920005570 flexible polymer Polymers 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QMQXDJATSGGYDR-UHFFFAOYSA-N methylidyneiron Chemical compound [C].[Fe] QMQXDJATSGGYDR-UHFFFAOYSA-N 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920000069 polyphenylene sulfide Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001285 shape-memory alloy Inorganic materials 0.000 description 1
- 150000003378 silver Chemical group 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
The invention belongs to the technical field of conductive circuit materials and 3D printing conductive circuit manufacturing, and particularly relates to a cooling imine insulation-nano silver conductive circuit, a preparation method and application thereof. The polyamic acid/metal silver salt composite material provided by the invention comprises polyamic acid, metal silver salt and an organic solvent, has excellent rheological property, formability and stability, and is suitable for direct writing 3D printing on substrates with different structures to perform design printing of conductive circuits. According to the invention, the polyamide acid/metal silver salt composite material is adopted to carry out direct writing 3D printing on the surface of the substrate, and the polyimide insulating-nano silver conductive circuit is obtained through heat-induced in-situ reduction reverse vapor deposition of the polyamide acid/metal silver salt composite circuit. The conductive silver circuit obtained by the invention has good conductivity, internal insulativity, high circuit precision and high adhesive force; and has wide application range.
Description
Technical Field
The invention belongs to the technical field of conductive circuit materials and 3D printing conductive circuit manufacturing thereof, and particularly relates to a cooling imine insulation-nano silver conductive circuit, a preparation method and application thereof.
Background
In recent years, the rapid development of electronic information technology has put increasingly strict requirements on the performance and quality of products in the fields of communication electronics, automobile electronics and the like, and modern electronic products and circuit manufacturing technologies thereof are rapidly developed, and low energy consumption, light weight, high toughness, miniaturization, multiple performances and individuation become the main modern new trend characteristics. The continuous innovation of the manufacturing method of the electronic conducting circuit enables the electronic components, the electronic modules and the core components such as the interconnection wires connected with the electronic components, and the like of the electronic product to be integrated on the surface of a physical object in a three-dimensional, miniaturized and high-precision manner. However, as the modern electronic market demand expands, the product is updated and the manufacturing requirements increase, and meanwhile, the modern electronic industry is limited by the circuit manufacturing technology of the modern electronic product, and the modern electronic industry is continuously faced with new and huge challenges, especially in the field of 3D structure surface circuit manufacturing. For example, the existing electronic circuit manufacturing process cannot manufacture three-dimensional curved surface circuit boards, surface circuits with different structures, surface circuits with inner cavity structures and flexible curved surface electronic circuits, and has the problems of complex manufacturing process, low precision, low efficiency and the like. In order to advance the further development of the fields of 3D structure surface circuit, curved surface circuit manufacturing, complex circuit board and flexible circuit manufacturing, the realization that electronic elements, electronic modules and interconnection wires communicated with the electronic elements and the electronic modules can be simply, quickly and efficiently integrated on the surfaces of various 3D structure objects, and the development of a novel conductive material and a manufacturing process method of a high-precision conductive circuit matched with the conductive material are urgently needed.
The additive manufacturing technology is used as a simple and efficient production and manufacturing technology, is simpler than the traditional electronic circuit manufacturing technology of 'subtractive manufacturing' mainly comprising photoetching and etching, has higher material utilization rate and more environment-friendly, and can meet the personalized requirements of products, such as rapid and integrated printing in three-dimensional non-conformal mode. In recent years, the application research of the 3D printing technology in the electronic equipment manufacturing industry is increasingly vigorous, and the research work of 3D printing circuits, modules, substrates, modules and the like is also deepened into the aspects of precision control technology, multilayer integrated circuit printing quality, circuit conductivity control technology and the like so as to meet the demands of different electronic industries. Current technological development of 3D printing electronic devices and conductive materials thereof is mainly based on conductive patterning of flexible polymer substrates, and the conductive materials include conductive carbon nanotubes, mxene, graphene, liquid metals, common conductive metals, and other inorganic conductive fillers. The metal conductive filler is more common because of higher intrinsic conductivity and no additional chemical modification is needed. In general, 3D printing electronic circuit technology is mainly extrusion printing, inkjet printing, spray printing and Electrohydrodynamic (EHD) inkjet printing, the pattern accuracy of jet printing is high,
however, the adhesion force of the metal conductive filler ink used in the current 3D printing electronic circuit technology on the surface of the polymer is generally low, and the metal conductive filler ink can fall off after sintering and has unstable conductivity.
Disclosure of Invention
The invention aims to provide a polyamide acid/metal silver salt composite material and application thereof, a polyimide insulation-nano silver conductive integrated circuit and a preparation method and application thereof. The polyimide insulating-nano silver conductive circuit prepared from the polyamide acid/metal silver salt composite material provided by the invention is an integrated structure circuit, and has good conductivity, internal insulativity, high circuit precision and high adhesive force.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a polyamide acid/metal silver salt composite material, which comprises polyamide acid, metal silver salt and an organic solvent, wherein the metal silver salt accounts for 10-90% of the mass of the polyamide acid.
Preferably, the organic solvent comprises one or more of N-methyl-2-pyrrolidone, N, N dimethylacetamide, N, N dimethylformamide and dimethylsulfoxide;
the viscosity of the polyamide acid/metallic silver salt composite material is 5000-20000 mPa.s.
Preferably, the polyamic acid is a commercially available product or a self-made product; when the polyamic acid is a commercial product, the polyamic acid comprises one or more of PAA-1001, PAA-4005, SS120L, SG120L, SMW, PAA-3000 and PI-100; when the polyamic acid is a self-made product, the preparation method of the polyamic acid comprises the following steps: 4,4' -diaminodiphenyl ether, 3', 4' -benzophenone tetracarboxylic dianhydride and an organic solvent are mixed for reaction to obtain polyamic acid.
Preferably, the metallic silver salt comprises one or more of silver nitrate, silver chloride, silver iodide, silver trifluoroacetate, silver sulfate, silver bistrifluoromethane sulfonyl imide, silver trifluoromethane sulfonate, silver carbonate, silver methane sulfonate, silver tungstate, silver 2-ethylhexanoate, silver tetrafluoroborate, silver hexafluorophosphate, silver perfluorooctanoate, silver acetylacetonate, silver heptafluorobutyrate, and silver citrate.
The invention provides application of the polyamide acid/metal silver salt composite material in the technical scheme as insulating-metal conductive integrated ink or conductive ink in a 3D printing conductive circuit.
The invention provides a preparation method of a polyimide insulating-nano silver conductive circuit, which comprises the following steps:
the polyamic acid/metal silver salt composite material is adopted to carry out direct writing 3D printing on the surface of the substrate, so as to obtain a polyamic acid/metal silver salt composite circuit;
and carrying out in-situ thermal reduction reverse vapor deposition on the polyamide acid/metal silver salt composite circuit to obtain the polyimide insulation-nano silver conductive integrated circuit.
Preferably, the working parameters of the direct writing 3D printing include: the printing speed is 1-10 mm/s, the printing air pressure is 100-700 kPa, and the printing layer thickness is 50-1000 mu m.
Preferably, the treatment atmosphere of the in-situ thermal reduction reverse vapor deposition is vacuum or a protective gas, and the protective gas comprises nitrogen and/or inert gas; the temperature-raising procedure of the in-situ thermal reduction reverse vapor deposition comprises the following steps: the temperature is raised to a first temperature from room temperature to perform first heat preservation, the temperature is raised to a second temperature from the first temperature to perform second heat preservation, the temperature is raised to a third temperature from the second temperature to perform third heat preservation, the temperature is raised to a fourth temperature from the third temperature to perform fourth heat preservation, and the temperature is raised to a fifth temperature from the fourth temperature to perform fifth heat preservation; the first temperature is 80-100 ℃, the second temperature is 120-150 ℃, the third temperature is 200-240 ℃, the fourth temperature is 280-300 ℃, the fifth temperature is 350-400 ℃, and the first heat preservation time, the second heat preservation time, the third heat preservation time, the fourth heat preservation time and the fifth heat preservation time are independently 0.5-2 h.
The invention provides a polyimide insulation-nano silver conductive integrated circuit prepared by the preparation method, which comprises a polyimide insulation layer and a nano silver conductive layer which are sequentially laminated on the surface of a substrate; the thickness of the nano silver conductive layer is 1-500 mu m.
The invention provides application of the polyimide insulation-nano silver conductive integrated circuit in conformal antennas, flexible sensors, 3D structure surface electronic devices or insulation conductive integrated electronic devices.
The invention provides a polyamide acid/metal silver salt composite material, which comprises polyamide acid, metal silver salt and an organic solvent, wherein the metal silver salt accounts for 10-90% of the mass of the polyamide acid. The polyamide acid/metal silver salt composite material provided by the invention has excellent rheological property, formability and stability, is suitable for direct writing 3D printing on the surfaces of substrates with different complex structures to carry out design printing of conductive circuits, has good conductivity, internal insulativity, high circuit precision and high adhesive force, and can realize integrated design and manufacture of insulation-conductive integrated high-precision conductive circuits and devices thereof on the surfaces of any special-shaped, thin-wall, complex three-dimensional structures, two-dimensional planes, conformal curved surfaces and the like, such as insulation, conduction and the like. Therefore, the polyamide acid/metal silver salt composite material provided by the invention solves the technical problems of poor adhesive force, unstable and poor conductivity and weak printability of the current 3D printing conductive circuit.
The invention provides a preparation method of a polyimide insulating-nano silver conductive circuit, which comprises the following steps: the polyamic acid/metal silver salt composite material is adopted to carry out direct writing 3D printing on the surface of the substrate, so as to obtain a polyamic acid/metal silver salt composite circuit; and carrying out in-situ thermal reduction reverse vapor deposition on the polyamide acid/metal silver salt composite circuit to obtain the polyimide insulating-nano silver conductive circuit. According to the preparation method provided by the invention, the polyamide acid/metal silver salt composite material is used as the ink for direct writing 3D printing, and the ink has excellent rheological property, so that a composite circuit with uniform components can be obtained on the surface of a substrate through 3D printing; then under the action of high temperature heat induction and no need of adding reducing agent, adopting the high temperature reduction characteristic of polyamide acid high temperature imidization to metal silver salt, reducing metal silver ions in the composite circuit into metal silver atom particles by the imidization and reverse vapor deposition principles of polyamide acid, and forming a compact metal silver conductive layer by surface migration and aggregation, and simultaneously, closing a loop by polyamide acid at high temperature to form polyimide, thereby obtaining a polyimide insulating inner layer with strong adhesive force with a substrate and a nano silver surface conductive layer with high conductivity and high stability, namely a composite circuit integrating polyimide-conductive silver insulation and conductivity, so as to realize successful preparation of the conductive circuit; the conductive silver circuit prepared by the preparation method provided by the invention by adopting a two-step method has good conductivity, internal insulativity, high circuit precision and high adhesive force; the preparation method can realize the integrated design and manufacture of the insulating-conducting integrated high-precision conducting circuit and devices thereof on the surfaces of any special-shaped, thin-wall, complex three-dimensional structure, two-dimensional plane, conformal curved surface and the like, such as insulation, conduction and the like, has wide application range and is suitable for industrial application.
Further, in the present invention, the working parameters of the direct writing 3D printing include: the printing speed is 1-10 mm/s, the printing air pressure is 100-700 KPa, and the printing layer thickness is 50-1000 mu m. According to the invention, by controlling the working parameters and combining polyamide acid/metal silver salt composite materials with excellent rheological properties as printing ink, the direct writing 3D printing on the surfaces of any special-shaped, thin-wall, complex three-dimensional structure, two-dimensional plane, conformal curved surface and the like such as insulation, conduction and the like can be realized.
Drawings
FIG. 1 is a schematic diagram showing the effect and resistance test of the printed circuit according to example 1;
FIG. 2 is the effect of printing conductive circuits on a metal sphere according to example 2;
FIG. 3 is a print-on fabrication of conductive circuits and their conductivity test on PI films of example 3;
FIG. 4 is a cross-sectional SEM image of a nano-silver conductive circuit obtained in example 4;
fig. 5 is an SEM image of the surface nano silver particle packing of the conductive circuits obtained in examples 1 to 4.
Detailed Description
The invention provides a polyamide acid/metal silver salt composite material, which comprises polyamide acid, metal silver salt and an organic solvent, wherein the metal silver salt accounts for 10-90% of the mass of the polyamide acid.
In the present invention, all preparation materials/components are commercially available products well known to those skilled in the art unless specified otherwise.
The polyamic acid/metal silver salt composite material provided by the invention comprises polyamic acid.
In the present invention, the polyamic acid is preferably a commercially available product or a homemade product, more preferably a homemade product. In the present invention, when the polyamic acid is preferably a commercially available product, the polyamic acid preferably includes one or more of PAA-1001, PAA-4005, SS120L, SG120L, SMW, PAA-3000, and PI-100. In the present invention, when the polyamic acid is preferably a homemade product, the preparation method of the polyamic acid preferably comprises the following steps: 4,4' -diaminodiphenyl ether, 3', 4' -benzophenone tetracarboxylic dianhydride and an organic solvent (hereinafter referred to as a first organic solvent) are mixed and reacted to obtain an organic solution of polyamic acid. In the present invention, the first organic solvent preferably includes one or more of N-methyl-2-pyrrolidone (NMP), N dimethylacetamide, N dimethylformamide, and dimethylsulfoxide, more preferably NMP. In the present invention, when the polyamic acid is preferably a self-made product, the type of the first organic solvent used for preparing the polyamic acid is preferably the same as the type of the organic solvent in the polyamic acid/metallic silver salt composite material. The molar ratio of the 4,4' -diaminodiphenyl ether to the 3,3', 4' -benzophenone tetracarboxylic dianhydride is preferably 1:1.01. The ratio of the amount of the substance of the 4,4' -diaminodiphenyl ether to the volume of the first organic solvent is preferably 1mol:2.5L. The mixing is preferably: under ice-water bath, dissolving the 4,4 '-diaminodiphenyl ether in a first organic solvent to obtain a 4,4' -diaminodiphenyl ether solution; and adding the 3,3', 4' -benzophenone tetracarboxylic dianhydride into the 4,4' -diaminodiphenyl ether solution in batches under an ice-water bath. The 3,3', 4' -benzophenone tetracarboxylic dianhydride is added in three batches, and the addition amount of each batch is the same. The reaction temperature is preferably 0-5 ℃, and the heat preservation time is preferably 12h. The reaction is carried out with stirring. The organic solution of the polyamic acid obtained in the present invention preferably has a solid content of 15 to 25wt%, more preferably 20wt%.
The polyamide acid/metal silver salt composite material provided by the invention comprises poly metal silver salt.
In the present invention, the metallic silver salt preferably includes one or more of silver nitrate, silver chloride, silver iodide, silver trifluoroacetate, silver sulfate, silver bistrifluoromethane sulfonyl imide, silver trifluoromethane sulfonate, silver carbonate, silver methane sulfonate, silver tungstate, silver 2-ethylhexanoate, silver tetrafluoroborate, silver hexafluorophosphate, silver perfluorooctanoate, silver acetylacetonate, silver heptafluorobutyrate, and silver citrate.
In the present invention, the metal silver salt accounts for 10 to 90% by mass of the polyamic acid, preferably 20 to 60% by mass, and more preferably 30 to 50% by mass.
The polyamide acid/metal silver salt composite material provided by the invention comprises an organic solvent.
In the present invention, the organic solvent preferably includes one or more of N-methyl-2-pyrrolidone, N dimethylacetamide, N dimethylformamide and dimethylsulfoxide, more preferably N-methyl-2-pyrrolidone.
In the present invention, the viscosity of the polyamic acid/metallic silver salt composite material is preferably 5000 to 20000mpa·s, more preferably 5000 to 15000mpa·s, and even more preferably 5000 to 10000mpa·s.
In the present invention, the amount of the organic solvent in the polyamic acid/metal silver salt composite material is preferably determined by the viscosity of the polyamic acid/metal silver salt composite material.
The preparation method of the polyamide acid/metal silver salt composite material provided by the technical scheme comprises the following steps: and ball-milling and mixing the polyamic acid, the metal silver salt and the organic solvent to obtain the polyamic acid/metal silver salt composite material. In the present invention, the ball milling is preferably performed in a ball mill for a time of preferably 10 to 30 minutes.
In the present invention, the polyamic acid is used in the form of an organic solution of the polyamic acid, whether it is a commercially available product or a self-made product. In the invention, when the viscosity of the composite material obtained by mixing the organic solution of the polyamic acid and the metallic silver salt meets the viscosity requirement, the invention does not need to additionally add an organic solvent; when the viscosity of the composite material obtained after the organic solution of the polyamic acid and the metallic silver salt are mixed does not meet the viscosity requirement, the viscosity of the composite material is regulated by additionally adding the organic solvent so as to meet the requirement.
The invention provides application of the polyamide acid/metal silver salt composite material in the technical scheme as insulating-metal conductive integrated ink or conductive ink in a 3D printing conductive circuit.
The printable composite material of the polyamide acid/metal silver salt provided by the invention can be used for designing and printing conductive circuits on the surfaces of substrates with different complex structures through the formability and the stability of the printing material.
The invention provides a preparation method of a polyimide insulating-nano silver conductive circuit, which comprises the following steps:
the polyamic acid/metal silver salt composite material is adopted to carry out direct writing 3D printing on the surface of the substrate, so as to obtain a polyamic acid/metal silver salt composite circuit;
and carrying out in-situ thermal reduction reverse vapor deposition on the polyamide acid/metal silver salt composite circuit to obtain the polyimide insulation-nano silver conductive integrated circuit.
According to the technical scheme, the polyamide acid/metal silver salt composite material is adopted to carry out direct writing 3D printing on the surface of the substrate, so that a polyamide acid/metal silver salt composite circuit is obtained. In the present invention, the polyamic acid/metallic silver salt composite material is preferably subjected to a bubble removal treatment before the direct writing 3D printing is performed. The de-bubbling treatment is preferably centrifugation of the polyamic acid/metallic silver salt composite material. In the invention, the substrate surface is specifically a 3D complex structure surface, a two-dimensional plane surface and a conformal curved surface. The substrate is preferably a metal substrate, a ceramic substrate or a polymer substrate, more preferably a metal substrate or a ceramic substrate. The metal substrate is preferably an iron substrate, an alloy substrate, a copper substrate or an aluminum substrate; the alloy substrate preferably comprises a copper alloy, an iron carbon alloy, an aluminum alloy, a gold alloy or a shape memory alloy. The polymer substrate is preferably a polymer substrate resistant to the temperature of 300 ℃, and particularly preferably a polyimide substrate, a polyether-ether-ketone substrate or a polyphenylene sulfide substrate. In the invention, the working parameters of the direct writing 3D printing comprise: the printing rate is preferably 1 to 10mm/s, more preferably 2 to 5mm/s, still more preferably 3 to 4mm/s; the air pressure for printing is preferably 100 to 700kPa, more preferably 300 to 500kPa, still more preferably 300 to 400kPa; the thickness of the printed layer is preferably 50 to 1000. Mu.m, more preferably 50 to 500. Mu.m, still more preferably 50 to 300. Mu.m.
After the polyamide acid/metal silver salt composite circuit is obtained, the polyamide acid/metal silver salt composite circuit is subjected to in-situ thermal reduction reverse vapor deposition, and the polyimide insulation-nano silver conductive integrated circuit is obtained.
In the present invention, the processing atmosphere of the in-situ thermal reduction reverse vapor deposition is preferably vacuum or a shielding gas, and the shielding gas preferably comprises nitrogen and/or inert gas; the inert gas is preferably argon. In the present invention, the temperature-increasing procedure of the in-situ thermal reduction reverse vapor deposition preferably includes: the temperature is raised to the first temperature from the room temperature to carry out first heat preservation, the temperature is raised to the second temperature from the first temperature to carry out second heat preservation, the temperature is raised to the third temperature from the second temperature to carry out third heat preservation, the temperature is raised to the fourth temperature from the third temperature to carry out fourth heat preservation, and the temperature is raised to the fifth temperature from the fourth temperature to carry out fifth heat preservation. The first temperature is preferably 80 to 100 ℃, more preferably 85 to 95 ℃; the time of the first heat preservation is preferably 0.5-2 h, more preferably 1h; the second temperature is preferably 120-150 ℃, more preferably 125-145 ℃; the second heat preservation time is preferably 0.5-2 h, more preferably 1h; the third temperature is preferably 200-240 ℃, more preferably 210-230 ℃; the time of the third heat preservation is preferably 0.5-2 h, more preferably 2h; the fourth temperature is preferably 280-300 ℃, more preferably 285-295 ℃; the fourth heat preservation time is preferably 0.5-2 h, more preferably 1h; the fifth temperature is preferably 350 to 400 ℃, more preferably 360 to 390 ℃; the time of the fifth heat preservation is preferably 0.5 to 2 hours, more preferably 0.5 hours. In the present invention, the temperature increase rate during the temperature increase program is preferably 0.5 to 2℃per minute, more preferably 1 to 1.5℃per minute.
The invention provides a polyimide insulation-nano silver conductive integrated circuit prepared by the preparation method, which comprises a polyimide insulation layer and a nano silver conductive layer which are sequentially laminated on the surface of a substrate; the thickness of the nano silver conductive layer is 1 to 500 μm, preferably 10 to 450 μm, more preferably 50 to 400 μm, and even more preferably 100 to 350 μm.
The polyimide insulating-nano silver conductive circuit provided by the invention has excellent insulativity, conductivity and high adhesive force.
The invention provides application of the polyimide insulation-nano silver conductive integrated circuit in conformal antennas, flexible sensors, 3D structure surface electronic devices or insulation conductive integrated electronic devices.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing and uniformly stirring purchased commercial polyamide acid PAA-100 and silver trifluoroacetate powder, adding 50mLNMP, and putting the uniformly stirred composite material into a ball mill for ball milling for 10min to prepare a directly writable 3D-printable polyamide acid/metal silver salt composite material containing silver trifluoroacetate accounting for 20% of the solid mass of the polyamide acid PAA-100, wherein the viscosity of the composite material is 5570 mPa.s; further centrifuging the prepared composite material to remove bubbles to obtain a pale yellow direct-writing printing composite material with good rheological property; further, the prepared composite material was printed with a circuit pattern on a 40mm×100mm commercial PI film by a direct writing printing apparatus at a printing air pressure of 400kPa, a printing speed of 3mm/s and a thickness of 200. Mu.m. Finally, transferring the printed circuit pattern into a vacuum oven after printing, sequentially heating from room temperature to 80 ℃ at a heating rate of 1 ℃/min, 1h, 150 ℃,1h, 200 ℃,2h, 280 ℃,1h, 350 ℃ and 0.5h, and performing high-temperature induced thermal reduction to obtain the polyimide/silver composite circuit with high conductivity, wherein the thickness of the circuit layer is 135 mu m. The conductivity of the conductive composite material is shown in table 1, the effect of printing a conductive circuit is shown in fig. 1, and a in fig. 5 is an SEM image of the surface nano silver particle accumulation of the conductive circuit obtained in example 1.
Example 2
Mixing and uniformly stirring commercialized polyamide acid PAA-4005 and silver acetylacetonate, wherein the mass of the silver acetylacetonate is 30% of the solid mass of polyamide acid PAA-4005; putting the uniformly stirred composite material into a ball mill for ball milling for 10min, and preparing the polyamide acid/metal silver salt composite material capable of being directly written and printed in 3D, wherein the viscosity of the composite material is 6972 mPa.s; and centrifuging the prepared composite material to take out bubbles to obtain the dark brown direct writing 3D printing composite material. And printing circuit patterns on the spherical surface of the round semicircular sphere block by using the prepared composite material through a direct writing printing device, wherein the printing air pressure is 500kPa, the printing speed is 3.5mm/s and the thickness is 250 mu m. Finally, transferring the printed circuit pattern into a vacuum oven after printing, sequentially heating from room temperature to 90 ℃ at a heating rate of 1 ℃/min, 1h, 180 ℃,1h, 220 ℃,1h, 300 ℃,1h, 380 ℃ and 0.5h, and performing high-temperature induced thermal reduction to obtain the polyimide/silver composite circuit with high conductivity, wherein the thickness of the conductive silver layer is 245 mu m. The conductivity of the finally obtained conductive circuit is shown in table 1, the conductive effect after printing and forming and high-temperature reduction is shown in fig. 2, and b in fig. 5 is an SEM image of the surface nano silver particle accumulation of the conductive circuit obtained in example 2.
Example 3
Under ice-water bath, 1mol of 4,4' -diaminodiphenyl ether is added into 2.5 LN-methyl-2-pyrrolidone, the solution is stirred uniformly and the temperature is reduced to 0 ℃, then 1.01mol of 3,3', 4' -benzophenone tetracarboxylic dianhydride is added in three batches, and then the mixture is stirred and reacted for 12 hours, finally the polyamide acid solution with the solid content of 20 weight percent is prepared.
Mixing and uniformly stirring a self-made polyamide acid solution with the solid content of 20% and trisilver citrate, wherein the mass of the trisilver citrate is 40% of the mass of the self-made PAA solid; putting the uniformly stirred composite material into a ball mill for ball milling for 20min, and preparing the polyamide acid/metal silver salt composite material capable of being directly written and printed in 3D, wherein the viscosity of the composite material is 8567 mPa.s; and then transferring into a printing cylinder, putting into a high-speed centrifuge for centrifugation to remove bubbles, and printing a circuit pattern on the PI film by the prepared composite material through a direct writing printing device, wherein the printing air pressure is 350kPa, the printing speed is 3mm/s and the printing thickness is 100 mu m. Transferring the printed pattern into a high-temperature sintering furnace in nitrogen atmosphere, sequentially heating from room temperature to 100 ℃ at a heating rate of 1 ℃/min, 1h, 150 ℃,1h, 200 ℃,1h, 300 ℃,2h, 380 ℃ and 0.5h, and performing high-temperature induced reduction to obtain the polyimide/silver composite circuit with high conductivity, wherein the thickness of a silver conductive layer is 325 mu m. The conductivity of the conductive circuit is shown in table 1, and fig. 5 c is an SEM image of the surface nano silver particle accumulation of the conductive circuit obtained in example 3.
Example 4
The preparation method of the polyamic acid was the same as in example 3.
Mixing self-made polyamide acid containing 20% of solid content with trifluoroacetic acid, and uniformly stirring, wherein silver trifluoroacetate accounts for 50% of the self-made PAA solid mass; putting the uniformly stirred composite material into a ball mill for ball milling for 30min, and preparing the polyamide acid/metal silver salt composite material capable of being directly written and printed in 3D, wherein the viscosity of the composite material is 9653 mPa.s; and then transferring the printing cylinder into a high-speed centrifugal bubble removing machine to obtain the transparent pale yellow printing composite material. Further, the designed line pattern was printed on a commercially available PI film by a direct writing printing apparatus at a printing air pressure of 450kPa, a printing speed of 4mm/s and a printing thickness of 50. Mu.m. Transferring the printed circuit pattern into a vacuum oven, sequentially heating from room temperature to 80 ℃ at a heating rate of 1 ℃/min, 1h, 150 ℃,1h, 220 ℃,1h, 280 ℃,1h, 350 ℃ and 1h, and performing high-temperature induced reduction to obtain the PI/silver composite circuit with high conductivity, wherein the thickness of the conductive silver layer is 350 mu m. The SEM image and layer thickness of the obtained silver circuit are shown in fig. 4, the conductivity of the conductive circuit is shown in table 1, and the SEM image of the surface nano silver particle accumulation of the conductive circuit obtained in example 4 in fig. 5 d.
Table 1 viscosity and electrical properties of the conductive composite printing materials of examples
In summary, the invention realizes the forming and manufacturing of the Ag conductive circuit with high conductivity and high adhesive force by a two-step method, the first step is to prepare the composite printing material of the polyimide and the silver salt for direct writing 3D printing with rheological composite and good printability, the second step is to adopt the high-temperature reduction characteristic of polyimide high-temperature imidization to metal silver salt, and the deposition and polymerization of the nano silver conductive layer are carried out by the principle of polyimide imidization reverse vapor deposition, thereby realizing the successful preparation of the conductive circuit; the conductive silver circuit manufactured by the method has good conductivity, internal insulativity, high circuit precision and high adhesive force, and the polyimide/Ag composite conductive circuit manufacturing method can realize the integrated design and manufacture of the insulating-conductive integrated high-precision conductive circuit and devices thereof on the surfaces of any special-shaped, thin-wall, complex three-dimensional structure, two-dimensional plane, conformal curved surface and the like such as insulation, conduction and the like.
Although the foregoing embodiments have been described in some, but not all embodiments of the invention, other embodiments may be obtained according to the present embodiments without departing from the scope of the invention.
Claims (10)
1. The polyamide acid/metal silver salt composite material is characterized by comprising polyamide acid, metal silver salt and an organic solvent, wherein the metal silver salt accounts for 10-90% of the polyamide acid in percentage by mass.
2. The polyamic acid/metal silver salt composite material according to claim 1, wherein the organic solvent comprises one or more of N-methyl-2-pyrrolidone, N, N dimethylacetamide, N, N dimethylformamide and dimethylsulfoxide;
the viscosity of the polyamide acid/metallic silver salt composite material is 5000-20000 mPa.s.
3. The polyamic acid/metallic silver salt composite material according to claim 1 or 2, characterized in that the polyamic acid is a commercially available product or a self-made product; when the polyamic acid is a commercial product, the polyamic acid comprises one or more of PAA-1001, PAA-4005, SS120L, SG120L, SMW, PAA-3000 and PI-100; when the polyamic acid is a self-made product, the preparation method of the polyamic acid comprises the following steps: 4,4' -diaminodiphenyl ether, 3', 4' -benzophenone tetracarboxylic dianhydride and an organic solvent are mixed for reaction to obtain polyamic acid.
4. The polyamic acid/metal silver salt composite material according to claim 1 or 2, wherein the metal silver salt comprises one or more of silver nitrate, silver chloride, silver iodide, silver trifluoroacetate, silver sulfate, silver bistrifluoromethane sulfonimide, silver trifluoromethane sulfonate, silver carbonate, silver methane sulfonate, silver tungstate, silver 2-ethylhexanoate, silver tetrafluoroborate, silver hexafluorophosphate, silver perfluorooctanoate, silver acetylacetonate, silver heptafluorobutyrate, and trisilver citrate.
5. Use of the polyamic acid/metallic silver salt composite material according to any one of claims 1 to 4 as an integrated insulating-metallic conductive ink or conductive ink in a 3D printed conductive circuit.
6. The preparation method of the polyimide insulating-nano silver conductive circuit is characterized by comprising the following steps of:
performing direct writing 3D printing on the surface of a substrate by adopting the polyamic acid/metal silver salt composite material according to any one of claims 1 to 4 to obtain a polyamic acid/metal silver salt composite circuit;
and carrying out in-situ thermal reduction reverse vapor deposition on the polyamide acid/metal silver salt composite circuit to obtain the polyimide insulation-nano silver conductive integrated circuit.
7. The method of claim 6, wherein the operating parameters of the direct-write 3D printing include: the printing speed is 1-10 mm/s, the printing air pressure is 100-700 kPa, and the printing layer thickness is 50-1000 mu m.
8. The method according to claim 6, wherein the processing atmosphere of the in-situ thermal reduction reverse vapor deposition is vacuum or a shielding gas comprising nitrogen and/or an inert gas; the temperature-raising procedure of the in-situ thermal reduction reverse vapor deposition comprises the following steps: the temperature is raised to a first temperature from room temperature to perform first heat preservation, the temperature is raised to a second temperature from the first temperature to perform second heat preservation, the temperature is raised to a third temperature from the second temperature to perform third heat preservation, the temperature is raised to a fourth temperature from the third temperature to perform fourth heat preservation, and the temperature is raised to a fifth temperature from the fourth temperature to perform fifth heat preservation; the first temperature is 80-100 ℃, the second temperature is 120-150 ℃, the third temperature is 200-240 ℃, the fourth temperature is 280-300 ℃, the fifth temperature is 350-400 ℃, and the first heat preservation time, the second heat preservation time, the third heat preservation time, the fourth heat preservation time and the fifth heat preservation time are independently 0.5-2 h.
9. The polyimide insulating-nano silver conductive integrated circuit prepared by the preparation method of any one of claims 6 to 8, which is characterized by comprising a polyimide insulating layer and a nano silver conductive layer which are sequentially laminated on the surface of a substrate; the thickness of the nano silver conductive layer is 1-500 mu m.
10. Use of the polyimide insulation-nanosilver conductive integrated circuit of claim 9 in a conformal antenna, a flexible sensor, a 3D structured surface electronics, or an insulated conductive integrated electronics.
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