CN115458205A - Conductive paste, preparation method and electronic device comprising conductive paste - Google Patents
Conductive paste, preparation method and electronic device comprising conductive paste Download PDFInfo
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- CN115458205A CN115458205A CN202211175511.8A CN202211175511A CN115458205A CN 115458205 A CN115458205 A CN 115458205A CN 202211175511 A CN202211175511 A CN 202211175511A CN 115458205 A CN115458205 A CN 115458205A
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- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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Abstract
The invention relates to conductive paste, a preparation method and an electronic device comprising the conductive paste, and belongs to the technical field of electronic paste. The conductive paste comprises the following components in parts by mass: 30-90 parts of conductive component, 3-15 parts of resin, 10-65 parts of solvent and 0.1-5 parts of auxiliary agent; the conductive component comprises a conductive main body component and a conductive stretching component, and the mass ratio of the conductive main body component to the conductive stretching component is (30-97): (3-70); the conductive body component includes at least one of a silver-containing material or a copper-containing material; the conductive stretching component comprises at least one of a nano or micron metal material, a carbon material or a polymer-coated conductive material. The invention can improve the flexibility of the conductive paste, has better conductive performance, can overcome the problem of higher resistivity change of the conventional paste in the prior art during stretching, and has better application prospect.
Description
Technical Field
The invention belongs to the technical field of electronic paste, and particularly relates to conductive paste, a preparation method of the conductive paste and an electronic device comprising the conductive paste.
Background
In recent years, with the continuous development of electronic technology, more and more products and devices have made higher demands for miniaturization and flexibility of electronic devices. Meanwhile, the requirements of electronization or chip formation are provided for more product devices including daily articles, and the requirements of conductive paste with various dimensions on different base materials are further promoted. For example, with the advance of internet of things packaging, flexible wearable devices, reality augmentation devices, virtual augmentation devices, flexible sensors, and the like, higher requirements and requirements are provided for high conductivity, high bending, and high stretching which are lower than those of conductive paste.
In the related art, the flexible conductive paste which is mainstream at present can be mainly classified into three types. The first is polymer slurry, and the main product at present is PEDOT (PEDOT is a polymer of EDOT (3, 4-ethylenedioxythiophene monomer)): PSS (polystyrene sulfonic acid) has the advantage of high ductility of a high polymer material, but the conductivity of the PSS is mediocre and can only reach the level of hundreds of omega/\9633andis difficult to meet the requirement of electrical properties for most applications. The second is pure inorganic metal slurry, the main products at present are liquid gallium and liquid alloy thereof, and the liquid metal has certain extensibility on the basis of having better conductive performance of the metal, but the price is high, so that the liquid metal is difficult to be applied to mass-produced products and the application is limited. The third is slurry combining inorganic metal and macromolecule, the inorganic metal can provide better conductivity, and the macromolecule can provide certain flexibility; however, the existing slurry has problems that the resistance is easy to sharply increase under a certain tensile strength, the flexibility of the polymer is not well conducted to the inorganic metal, and the resistance is increased by more than 2 times under a certain degree of stretching, such as 20%, so that it is difficult to meet certain high-stretching requirements.
Disclosure of Invention
In view of the above-mentioned problems, the present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the conductive paste, the preparation method and the electronic device comprising the conductive paste provided by the invention can improve the flexibility of the conductive paste, have better conductive performance and can overcome the problem that the conventional paste in the prior art has higher resistance change during stretching.
The invention relates to conductive paste, which comprises the following components in parts by mass:
30-90 parts of conductive component, 3-15 parts of resin, 10-65 parts of solvent and 0.1-5 parts of auxiliary agent; the conductive component comprises a conductive main body component and a conductive stretching component, and the mass ratio of the conductive main body component to the conductive stretching component is (30-97): (3-70); the conductive body component includes at least one of a silver-containing material or a copper-containing material; the conductive stretching component comprises at least one of a nano or micron metal material, a carbon material or a polymer-coated conductive material.
In some embodiments, the composition comprises the following components in parts by mass: 50-85 parts of conductive component, 4-12 parts of resin, 12-50 parts of solvent and 0.5-2 parts of auxiliary agent. In some embodiments, the composition comprises the following components in parts by mass: 60 to 84 parts of conductive component, 4 to 10 parts of resin, 15 to 45 parts of solvent and 0.8 to 1.5 parts of assistant.
In some embodiments, the mass ratio of the conductive body component to the conductive tensile component is (50-96): (4 to 50). In some embodiments, the mass ratio of the conductive body component to the conductive tensile component is (60-90): (10 to 40).
In some of these embodiments, the conductive body composition includes at least one of silver powder, copper powder, or silver-coated copper powder.
In some embodiments, the silver powder includes at least one of a spherical silver powder, a plate-like silver powder, a rod-like silver powder, or a wire-like silver powder.
In some embodiments, the silver powder is micron-sized silver powder, the copper powder is micron-sized copper powder, and the silver-coated copper powder is micron-sized silver-coated copper powder.
In some embodiments thereof, the nano-sized or micro-sized metallic material comprises at least one of a silver nano-sized or micro-sized material, a copper nano-sized or micro-sized material, a silver-coated copper nano-sized or micro-sized material, a gold-coated copper nano-sized or micro-sized material, and a gold-coated silver nano-sized or micro-sized material.
In some embodiments thereof, the carbon material comprises at least one of graphene, graphene oxide, reduced graphene oxide, chemically functional group-modified graphene, carbon nanotubes, or carbon fibers.
In some embodiments, the polymer-coated conductive material is in a core-shell shape, the core layer is a conductive material, and the shell layer is a polymer material.
In some embodiments thereof, the conductive tensile component further comprises MXene.
In some embodiments thereof, the morphology of the nano-or micro-scale metallic material comprises at least one of a sheet, a wire, a rod, a core-shell, or a cluster.
In some embodiments, the conductive material comprises at least one of silver nanowires, silver powder, copper powder, silver-coated copper powder, graphene, or carbon nanotubes.
In some embodiments thereof, the polymeric material comprises at least one of polyethylene glycol (PEG), polylactic acid (PLA), polyvinylpyrrolidone (PVP), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyoxyethylene (PEO), polylactide (PLLA), polycaprolactone (PCL), polyacrylonitrile (PAN), or Polymethylmethacrylate (PMMA).
In some embodiments, the resin has a number average molecular weight of 1000 or more.
In some embodiments, the solvent has a boiling point ≧ 100 ℃.
In some embodiments thereof, the resin comprises at least one of a TPU resin, a polyester resin, an acrylic resin, an amino resin, a silicone resin, or an epoxy resin.
In some embodiments thereof, the solvent comprises at least one of DBE, MDBE, ethylene glycol, dimethylformamide, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, diethylene glycol butyl ether acetate, diethylene glycol butyl ether, octanol, octyl acetate, xylene, terpineol, or isophorone.
In some embodiments thereof, the adjuvant comprises at least one of a wetting dispersant, a defoamer, an accelerator, a tackifier, a surfactant, a coupling agent, a moldability modifier, or a cure modifier.
As another aspect of the present invention, the present invention relates to a method for preparing the conductive paste, comprising:
and stirring and mixing the conductive main body component, the conductive stretching component, the resin, the solvent and the auxiliary agent according to the formula ratio to obtain the conductive slurry.
As a further aspect of the present invention, it relates to an electronic device comprising a substrate and conductive lines formed on the substrate, the conductive lines being prepared from a conductive paste comprising the conductive paste as described above.
In some embodiments, the substrate has a thickness of 20 μm to 500 μm.
In some embodiments, the material of the substrate includes at least one of Polydimethylsiloxane (PDMS), thermoplastic polyurethane elastomer (TPU), polyethylene terephthalate (PET), polyethylene (PE), silicone, polyester, or acrylate.
In some embodiments, the method of making the conductive line comprises: and printing the conductive paste on the base material, and curing to obtain the conductive circuit.
In some embodiments, the curing temperature is 110 to 160 ℃ and the curing time is 10 to 30min.
Compared with the prior art, the technical scheme of the application has at least the following beneficial effects:
the conductive paste comprises a conductive component, resin, a solvent and an auxiliary agent, wherein the conductive component comprises a conductive main body component and a conductive stretching component in a certain proportion, the conductive main body component comprises one or more of a silver-containing material or a copper-containing material, and the conductive stretching component comprises one or more of a nano or micron metal material, a carbon material or a polymer-coated conductive material. Therefore, by using the efficient conductive material as the conductive main body component, the initial resistivity can be reduced, so that the change of the resistivity is relatively small when the conductive material is stretched and bent, and by compounding the conductive material with high tensile property as the conductive stretching component, the resistivity in a stretching state can be ensured, for example, the resistivity can still be kept excellent under the condition that the stretching rate is 50%; meanwhile, the conductivity and the tensile property of the finally obtained conductive paste can meet the requirements of the common conductive electronic industry by optimizing the proportion of the conductive main body component and the conductive tensile component.
The method is simple and easy to implement, easy to operate and easy to realize large-scale production, and the prepared conductive paste has low resistance change rate during stretching and bending, can improve the service life and reliability of electronic devices on the premise of ensuring the conductive performance of the conductive paste, and has good application prospect.
Additional aspects and advantages of embodiments of the present application will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of embodiments of the present application.
Detailed Description
The present application is further illustrated with reference to specific examples. It should be understood that these examples of the present application are for illustrative purposes only and are not intended to limit the scope of the present application.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and these ranges or values should be understood to encompass values close to these ranges or values. For ranges of values, between the endpoints of each range or between the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Herein, percentages, ratios or parts referred to are by mass unless otherwise indicated. The term "part by mass" refers to a basic unit of measure relating to the mass ratio of the components, and 1 part by mass may represent an arbitrary unit mass, and for example, 1 part by mass may be 1g, 1.68g, or 5 g. Herein, the percentages (%) refer to the mass percentage relative to the composition, unless otherwise specified.
In view of the fact that the resistance of the conductive paste in the related art increases sharply when the conductive paste is stretched or bent, the conductive paste cannot meet the requirement of low resistance change of the conductive paste when the conductive paste is stretched or bent, in other words, the conventional conductive paste cannot have good flexibility or ductility while ensuring excellent conductive performance. The embodiment of the application provides an improved conductive paste, which can improve the flexibility of the conductive paste and has excellent conductive performance.
In a first aspect of the present application, there is provided a conductive paste, which comprises the following components in parts by mass: 30-90 parts of conductive component, 3-15 parts of resin, 10-65 parts of solvent and 0.1-5 parts of auxiliary agent;
the conductive component comprises a conductive main body component and a conductive stretching component, and the mass ratio of the conductive main body component to the conductive stretching component is (30-97): (3-70); the conductive body component includes at least one of a silver-containing material or a copper-containing material; the conductive stretching component comprises at least one of a nano or micron metal material, a carbon material or a polymer coated conductive material.
According to the embodiment of the application, the provided conductive paste can effectively provide certain stretching and bending properties for the polymer end by adding a certain amount of flexible polymers, particularly the flexible polymers with larger molecular weight, less rigid structures and more linear chains. Illustratively, the conductive paste contains a resin, and a specific TPU (thermoplastic polyurethane elastomer rubber) resin, a polyester resin, an epoxy resin, and other resin materials can be selected.
According to the embodiment of the application, the conductive paste has better flexibility by adding the conductive material with relative flexibility, namely the conductive stretching component, and can lose the link sites as little as possible in a stretching state, so that the conductive efficiency is basically not influenced. For example, one-dimensional or two-dimensional nano conductive materials such as nano silver sheets and nano silver wires, or carbon materials such as graphene and carbon tubes can be selected. Further, the conductive stretching component in this embodiment includes a polymer-coated conductive material, and by adding a flexible polymer-inorganic conductive composite material, the polymer material is used as a shell layer, the inorganic conductive material is used as a core layer, and the polymer material is completely or partially coated with the inorganic conductive material, the conductive performance can be improved, and only the polymer material is stretched during the stretching process, and the conductive material still maintains its efficient conductive performance.
It is to be understood that the conductive material in the above-described polymer-coated conductive material is preferably an inorganic conductive material. By means of compounding inorganic conductive materials and organic polymer materials, the conductive performance can be improved, and the conductive material can have a small resistance change rate when being stretched or bent.
Therefore, based on the above arrangement, the conductive paste of the embodiment can meet the requirement of low resistance change of the conductive paste during stretching or bending; for example, experiments prove that the resistance change rate of the conductive paste provided by the embodiment can reach 100-150% under the condition of 50% of tensile deformation; meanwhile, under the condition of bending R5, the resistance change rate is less than 20% after bending for ten thousand times, so that the requirement of most flexible stretching conductive circuits can be met, and the flexible stretching conductive circuit has a good application prospect.
In this embodiment, in the conductive stretching component, the nano or micro metal material is preferably a nano metal material. The conductive stretching component at least comprises a polymer coated conductive material, and can also comprise optional nano or micron metal materials and carbon materials. That is, it is preferable to use a polymer-coated conductive material as the conductive stretching component, and in addition, the conductive stretching component may be added with or without a nano-or micro-scale metal material and/or a carbon material.
It is to be noted that the present invention does not limit the sources of the respective components in the conductive paste, such as the conductive component, the resin, the solvent, the auxiliary agent, and the like, and may be prepared by itself or obtained commercially.
In order to realize better matching of the components in the conductive paste, the conductive paste has better flexibility and better conductivity. The conductive paste includes, in parts by mass, 30 to 90 parts of a conductive component, and may typically, but not limited to, be any value in a range of 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, and any two of these point values. The conductive component is used as a conductive core of the conductive slurry and generally accounts for about 30-90% or about 30-85% of the slurry, if the content of the conductive component is too low, the conductive function is difficult to realize, and if the content of the conductive component is too high, the tensile property and the cost are difficult to meet the requirements; therefore, by adding the conductive component in an amount of 30 to 90 parts, a certain tensile property can be satisfied while ensuring a conductive function, and the cost can be reduced.
The conductive paste includes 3 to 15 parts by mass of a resin, and may typically, but not limited to, be any value in a range of 3 parts, 4 parts, 5 parts, 6 parts, 7 parts, 8 parts, 9 parts, 10 parts, 11 parts, 12 parts, 13 parts, 14 parts, 15 parts, and any two of these values, for example. The flexible resin is used as the key of tensile property, the addition amount is generally about 3-15%, if the addition amount of the resin is too low, the tensile function is difficult to meet, and if the addition amount of the resin is too high, the coated conductor material is too much, so that the resistance is too large, and the application is difficult to realize; therefore, by adding 3 to 15 parts of the resin, both the electrical conductivity and the tensile property can be achieved.
The conductive paste includes 10 to 65 parts by mass of a solvent, and typically, but not limited to, 10 parts, 12 parts, 14 parts, 15 parts, 18 parts, 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts, 50 parts, 55 parts, 60 parts, 65 parts, and any two of these values. In the conductive paste, a solvent is generally used for adjusting viscosity and printing performance, the addition amount is generally 10% to 65%, if the addition amount of the solvent is too small, printing performance is difficult to guarantee, and if the addition amount of the solvent is too large, main active ingredients are too low, and functions such as conductivity are difficult to realize. The conductive paste comprises 0.1-5 parts by mass of an auxiliary agent, and typically, but not limited to, 0.1 part, 0.2 part, 0.5 part, 1 part, 1.2 parts, 1.5 parts, 2 parts, 3 parts, 4 parts, 5 parts and any value in a range formed by any two of the parts. In the conductive paste, the addition amount of the auxiliary agent is relatively small in the conductive paste mainly for improving the printing performance and other comprehensive properties.
The conductive paste of this embodiment is mainly composed of four components, i.e., a conductive component, a resin, a solvent, and an auxiliary agent, and the addition amount and the addition type of each component are different according to different purposes and applications. The conductive paste has the advantages that the conductive paste has good flexibility, good conductivity and stable performance by adjusting the types and the proportions of the raw material components and the synergistic effect of the raw material components and other components, and the components are in the range, so that the requirement on the low resistance change rate of the conductive paste during stretching or bending can be met.
The conductive paste provided by the invention can be applied to flexible electronic devices, such as chips, battery pieces and other devices. In the process of flexible stretching or folding of a flexible electronic device, the quality of the conductive paste directly determines the service life of the device, which puts high technical requirements on the flexibility, durability or conductivity of the material of the conductive paste. The conductive paste provided by the invention fully considers the characteristic requirements of flexible electronic devices, and the components are matched with each other, so that the organic component molecular chains in the paste are high in flexibility, the material toughness is excellent, and the conductive performance is excellent, thereby being beneficial to prolonging the service life and improving the reliability of the electronic devices.
The following is a preferred technical solution of the present invention, but not a limitation to the technical solution provided by the present invention, and the technical objects and advantageous effects of the present invention can be better achieved and achieved by the following preferred technical solution.
In some embodiments, the conductive paste comprises the following components in parts by mass: 50-85 parts of conductive component, 4-12 parts of resin, 12-50 parts of solvent and 0.5-2 parts of auxiliary agent.
In some embodiments, the conductive paste comprises the following components in parts by mass: 60-84 parts of conductive component, 4-10 parts of resin, 15-45 parts of solvent and 0.8-1.5 parts of assistant.
By reasonably adjusting and optimizing the content of each component in the conductive paste, the synergistic cooperation effect among the components is fully exerted, the flexibility or conductivity or comprehensive performance of the conductive paste is further improved, and the production cost of the conductive paste is reduced.
In some embodiments, in the above conductive component, the mass ratio of the conductive body component to the conductive stretching component is (30 to 97): (3 to 70), for example, 30: 70. 40: 60. 50: 50. 60: 40. 70: 30. 80: 20. 85: 15. 90: 10. 92: 8. 95: 5. 97:3, etc., but are not limited to the recited values, and other values not recited within the numerical range are also applicable. Different ratios of the conductive body component to the conductive stretching component may affect the initial resistivity and the stretching resistivity of the paste, for example, when the ratio of the conductive body component to the conductive stretching component is large, the content of the conductive stretching component is low, and the resistivity after stretching is relatively changed, so that it is required to make the ratio of the conductive body component to the conductive stretching component in a proper range. By optimizing the proportion of the conductive main body component and the conductive stretching component, the conductivity and the stretching performance of the finally obtained conductive paste can meet the requirements of the common conductive electronic industry.
In some embodiments, the mass ratio of the conductive body component to the conductive tensile component is (50-96): (4-50). In some embodiments, the mass ratio of the conductive body component to the conductive tensile component is (60-90): (10 to 40). That is, in the above-mentioned conductive component, the conductive main component generally accounts for 30% to 97%, further 30% to 95%, further 50% to 96%, further 60% to 90%, further 65% to 85% of the entire conductive component.
According to the present embodiment, the conductive component is a conductive material of the conductive core, and includes a conductive main material and an auxiliary stretched conductive material, that is, includes a conductive main component and a conductive stretched component. The conductive main body component mainly has the function of providing basic conductive performance and ensuring the conduction of the whole circuit; the main function of the conductive stretching component, i.e. the auxiliary stretching conductive material, is to provide conductive performance during stretching or bending, and the resistance in the non-stretching state is generally larger. In the above-mentioned conductive components, the conductive main component generally accounts for about 30% to 95% of the total conductive component, if the ratio is too low, the resistivity of the total paste cannot be ensured, and if the ratio is too high, a certain flexibility cannot be maintained in a stretched state, resulting in a circuit interruption, and therefore, the ratio of the conductive main component to the conductive stretched component needs to be within the above-mentioned appropriate range.
According to this embodiment, the conductive body component may be a silver-containing material, may be a copper-containing material, or may be a silver-containing material and a copper-containing material. Specifically, in some embodiments, the conductive body composition includes at least one of silver powder, copper powder, or silver-coated copper powder. For example, the conductive main component may be silver powder, copper powder, silver-coated copper powder, silver powder and copper powder, copper powder and silver-coated copper powder, silver powder, copper powder and silver-coated copper powder, and the like.
Optionally, the silver powder includes, but is not limited to, at least one of spherical silver powder, flake silver powder, rod silver powder, or wire silver powder. That is, the morphology of the silver powder includes, but is not limited to, at least one of spherical, plate-like, rod-like, wire-like, and the like. For example, the silver powder may be a spherical silver powder, a flake silver powder, a rod silver powder, or a linear silver powder; the morphology of the silver powder can be a single type, or can be a combination of two or more of the above options, and when the morphology is a combination, the morphology can be combined at will. Preferably, the silver powder is spherical silver powder or flake silver powder. The shapes of the copper powder and the silver-coated copper powder may be spherical, flake, rod, linear, cluster, or the like.
Optionally, the silver powder is micron-sized silver powder, the copper powder is micron-sized copper powder, and the silver-coated copper powder is micron-sized silver-coated copper powder. That is, the conductive host component is preferably a micron-sized material; alternatively, in other embodiments, the conductive host component may be a nanoscale material.
Specifically, in some embodiments, the conductive body component is selected from silver ball powder (spherical silver powder), silver flake powder (flake silver powder), silver-coated copper powder, and the like, which have excellent conductive properties. Preferably, the conductive main body component comprises silver ball powder, silver flake powder and/or silver-coated copper powder; the silver ball powder, the silver flake powder or the silver-coated copper powder are all in micron grade.
In some embodiments, the conductive tensile component further comprises MXene. That is, the conductive stretching component includes one or more of a nano-or micro-sized metal material, MXene, a carbon material, or a polymer-coated conductive material. The conductive stretching component of the embodiment needs to have good conductivity and excellent stretching performance. Among them, the nano-sized or micro-sized metal material is preferably a nano-sized metal material. MXene material has excellent conductivity as a novel metal carbide or nitride with a two-dimensional lamellar structure similar to graphene. Preferably, the conductive stretching component comprises a polymer-coated conductive material, and a nanoscale metal material and/or carbon material.
Specifically, in some embodiments, the nano-sized or micro-sized metallic material comprises at least one of a silver nano-sized or micro-sized material, a copper nano-sized or micro-sized material, a silver-coated copper nano-sized or micro-sized material, a gold-coated copper nano-sized or micro-sized material, and a gold-coated silver nano-sized or micro-sized material. For example, the nano or micro metal material may be a silver nano material, a copper nano material, a silver-coated copper nano material, a gold-coated copper nano material, or a gold-coated silver nano material; or the material can be a silver micron material, a copper micron material, a silver-coated copper micron material and the like; the nano-sized or micro-sized metal material may be a single type, or may be a combination of two or more of the above options, and when in combination, may be arbitrarily combined. Preferably, the nano or micron metal material is selected from silver nano material, silver-coated copper nano or micron material. The silver nano material or the silver-coated copper material can obtain better technical effect, has wide source, is beneficial to improving the conductivity and has excellent tensile property.
In some embodiments, the carbon material comprises at least one of graphene, graphene oxide, reduced graphene oxide, chemically functional group-modified graphene, carbon nanotubes, or carbon fibers. For example, the carbon material may be graphene, graphene oxide, reduced graphene oxide, graphene modified with a chemical functional group, carbon nanotubes, carbon fibers, or a combination of any two or more of the foregoing, which is not specifically listed here. Preferably, the carbon material is selected from graphene and carbon nanotubes. The graphene or carbon nanotubes can obtain better technical effects, are wide in source and easy to obtain, contribute to further improving the stretchability and ensure the conductivity.
In addition, in other embodiments, the nano-sized or micro-sized metal material and the carbon material are not limited to the above-mentioned ones, and other types of nano-sized or micro-sized metal material and carbon material may be adopted in the case of satisfying the requirements of better electrical conductivity, excellent tensile property, and the like, and will not be described in detail herein.
In some embodiments, the morphology of the nano-or micro-scale metallic material includes, but is not limited to, at least one of sheet, wire, rod, core-shell, or cluster. For example, the silver nano material, copper nano material or silver-coated copper nano or micro material may have a shape of a sheet, a wire, a rod, a core-shell, a cluster, or the like. Preferably, a sheet or wire-like silver material, a copper material or a silver-clad copper material is used.
It will be appreciated that the morphology or size of the material may affect the tensile properties, and that as a conductive tensile component the morphology of the material is preferably sheet or wire-like, while as a conductive bulk component it may be selected to be spherical or also sheet-like. For example, when the conductive body component and the conductive stretching component both use silver materials, the conductive body component may use spherical silver powder, or use a composition of spherical silver powder and flake silver powder; the conductive drawing component may use a flake silver powder or a wire silver powder.
Alternatively, the carbon material may be a micro-scale or nano-scale material.
In some embodiments, the polymer-coated conductive material is in a core-shell shape, the core layer is a conductive material, and the shell layer is a polymer material, that is, the conductive material is coated with the polymer material. Wherein the conductive material is an inorganic conductive material.
In some embodiments, the conductive material comprises at least one of silver nanowires, silver powder, copper powder, silver-coated copper powder, graphene, or carbon nanotubes. For example, the conductive material may be a silver nanowire, a silver powder, a copper powder, a silver-coated copper powder, graphene, a carbon nanotube, or a combination of any two or more of the foregoing.
In some embodiments, the polymeric material comprises at least one of polyethylene glycol (PEG), polylactic acid (PLA), polyvinylpyrrolidone (PVP), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyoxyethylene (PEO), polylactide (PLLA), polycaprolactone (PCL), polyacrylonitrile (PAN), or Polymethylmethacrylate (PMMA), that is, the polymeric material may be any one of the above, or may be a combination of any two or more of the above. Preferably, the polymer material is selected from PEG, PLA or PVP.
In other embodiments, the conductive material and the polymer material are not limited to the above listed ones, and other types of conductive materials and polymer materials may be adopted in the case of meeting the requirements of better conductivity and excellent tensile property, and the like, and will not be described in detail herein.
Specifically, in some embodiments, the conductive stretching component includes a large silver sheet, a silver wire, a copper wire, a silver-coated copper sheet, a carbon nanotube, graphene oxide, MXene, a polymer-coated conductive material, and the like, which have good conductivity and excellent stretching performance, wherein the conductive material in the polymer-coated conductive material may be selected from a silver nanowire, a silver powder, a copper powder, a silver-coated copper powder, a carbon nanotube, graphene, and the like, and the polymer material may be selected from PEG, PLA, PVP, and the like.
In some embodiments, the resin has a number average molecular weight ≧ 1000. In some embodiments, the resin has a number average molecular weight ≧ 5000. In some embodiments, the resin has a number average molecular weight ≧ 10000.
In some embodiments, the resin comprises at least one of a TPU resin, a polyester resin, an acrylic resin, an amino resin, a silicone resin, or an epoxy resin. For example, the resin may be a TPU resin, a polyester resin, an acrylic resin, an amino resin, a silicone resin, an epoxy resin, or a combination of any two or more of the above. The epoxy resin may be a bisphenol a type epoxy resin, and in other embodiments, the epoxy resin may be a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a glycerin epoxy resin, or the like.
According to this embodiment, the resin serves as a source of flexibility and tensile properties, and also as a source of paste printing properties, and the number average molecular weight of the resin should be not less than 1000, otherwise both the tensile and viscosity are greatly affected. Meanwhile, as for the selection of the resin, TPU resin, polyester resin, acrylic resin, amino resin, silicone resin, epoxy resin, or the like is generally preferable. Thus, the excellent tensile properties of the resin can be guaranteed for the tensile properties of the overall size.
In some embodiments, the solvent has a boiling point ≧ 100 ℃. In some embodiments, the solvent has a boiling point of 120 ℃. In some embodiments, the solvent has a boiling point ≧ 150 ℃.
In some embodiments, the solvent comprises at least one of DBE (dibasic ester), MDBE (mixed dibasic dimethyl ester), ethylene glycol, dimethylformamide, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, diethylene glycol butyl ether acetate, diethylene glycol butyl ether, octanol, octyl acetate, xylene, terpineol, or isophorone; that is, the solvent may be any one of the above substances, or may be a combination of any two or more of the above substances, which are not listed here.
According to the embodiment, the solvent is mainly used for the convenience of printing, and the boiling point of the solvent is not lower than 100 ℃, otherwise the printing can be influenced. As the choice of solvent, generally preferred are commonly used high boiling point solvents including, but not limited to DBE, MDBE, ethylene glycol, dimethylformamide, ethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol butyl ether acetate, diethylene glycol butyl ether, octanol, octyl acetate, terpineol, xylene, isophorone and the like. The selection range of the solvent is wide, and in practical application, the solvent can be optimized according to different formulas.
In some embodiments, the adjuvant includes, but is not limited to, at least one of a wetting dispersant, a defoamer, an accelerator, a tackifier, a surfactant, a coupling agent, a moldability modifier, or a cure modifier; that is, the auxiliary may be any one of the above-mentioned substances, or may be a combination of any two or more of the above-mentioned substances. The auxiliary agent can be selected from various conventional auxiliary agents which can be applied to the conductive paste, and different types of auxiliary agents are utilized to exert corresponding functional functions. In addition, in other embodiments, other types of auxiliaries can also be used as the auxiliaries, which is not limited in this example.
According to the embodiment, the selection and range of the assistant are relatively large, and the assistant can be generally selected according to the performance of the conductive paste. For example, the conductive paste with poor wetting dispersion needs to be added with a certain amount of wetting dispersant, and optionally, the wetting dispersant may be BYK-W909 (wetting dispersant for unsaturated polyester resin), BYK-106, and the like. The conductive paste with poor defoaming effect needs to be added with a certain amount of defoaming agent, and optionally, the defoaming agent can be BYK-A500, BYK-066 and the like. If the adhesion of the slurry needs to be improved, some adhesion promoters need to be added, and optionally, the adhesion promoters can be BYK-4511, BYK-C8000 and the like. If the viscosity of the slurry does not meet the requirement, a certain amount of tackifier is required to be added, and optionally, the tackifier can be dextrin, carboxymethyl cellulose, propylene glycol alginate, methyl cellulose, sodium starch phosphate, sodium carboxymethyl cellulose, sodium alginate, casein, sodium polyacrylate, polyoxyethylene, polyvinylpyrrolidone and the like. In addition, if the curing ability of the resin in the conductive paste is insufficient, a corresponding thermosetting auxiliary agent or a photo-curing initiator such as an amino resin, a polyisocyanate resin, a blocked isocyanate resin, a carbodiimide resin, a cleavage-type radical photoinitiator, a hydrogen abstraction-type radical photoinitiator, a cationic photoinitiator, or the like, needs to be added.
It should be noted here that the above-mentioned various additives such as BYK-W909, BYK-106, BYK-A500, BYK-066, etc., are all products known in the art, and can be obtained commercially, and the sources of these additives are not limited in this example.
Based on the same inventive concept, in a second aspect of the present application, embodiments of the present application further provide a method for preparing the conductive paste, where the method for preparing the conductive paste includes:
and stirring and mixing the conductive main body component, the conductive stretching component, the resin, the solvent and the auxiliary agent according to the formula ratio to obtain the conductive slurry.
It should be understood that the specific selection and optimized usage of the conductive main body component, the conductive stretching component, the resin, the solvent and the auxiliary agent used in the preparation method of the conductive paste of the present application are the same as the limitations made in the conductive paste of the first aspect of the present application, and reference may be made to the description of the first aspect, and no further description is provided herein.
The preparation method of the conductive paste is simple in process, all the components are uniformly mixed, the feasibility is high, the conditions are mild, the operation is easy, and the conductive paste is suitable for industrial mass production.
Based on the same inventive concept, the embodiment of the application also provides an electronic device, which comprises a substrate and a conductive line formed on the substrate, wherein the conductive line is prepared from the conductive paste.
It should be understood that the electronic device includes the conductive paste provided in the present embodiment, and thus has at least all the features and advantages of the conductive paste, which are not described herein again.
The electronic device according to the present invention may be various electronic devices well known in the art, and in consideration of the function of the conductive paste according to the present invention, the electronic device may preferably be a flexible electronic device, such as a chip, a battery sheet, and the like.
In some embodiments, the substrate has a thickness of 20 μm to 500 μm. In some embodiments, the substrate has a thickness of 30 μm to 450 μm. In some embodiments, the substrate has a thickness of 50 μm to 300 μm.
In some embodiments, the substrate is a flexible and stretchable substrate, and the material of the substrate includes at least one of Polydimethylsiloxane (PDMS), thermoplastic polyurethane elastomer rubber (TPU), polyethylene terephthalate (PET), polyethylene (PE), silicone, polyester, or acrylate, that is, the substrate may be any one of the above materials, or may be a combination of any two or more of the above materials. Preferably, the base material is selected from silica gel or TPU, and the silica gel or TPU has wide sources, low cost and good use performance.
According to this embodiment, there is a certain limitation on the choice of the flexible and stretchable substrate, for example, after the substrate is stretched and deformed, the surface of the substrate is required to be free from unevenness, white spots, orange peel, etc., which may affect the adhesion and function of the conductive material on the surface. Further, there is a certain demand for the thickness of the base material, and it is generally preferable to select a base material having a thickness in the range of 20 μm to 500 μm, and if the base material is too thin, moldability of the base material is affected to a certain extent, and if the base material is too thick, tensile properties are affected; therefore, the substrate within the above thickness range can satisfy the requirements of tensile properties and moldability. Meanwhile, for the selection of the types of the base materials, PDMS, silica gel, TPU, polyester, PET, acrylate, PE and other materials can be selected, and the base materials have certain tensile property and good use performance.
In some embodiments, the method of making the conductive line comprises: and printing the conductive paste on the base material, and curing to obtain the conductive circuit.
In some embodiments, the curing temperature is 110 to 160 ℃ and the time is 10 to 30min. The curing temperature can be, for example, 110 deg.C, 120 deg.C, 130 deg.C, 140 deg.C, 150 deg.C, 160 deg.C, etc., and the curing time can be 10min, 15min, 20min, 25min, 30min, etc.
Specifically, the preparation method of the electronic device comprises the following steps:
(1) The flexible stretched substrate is slit to divide the substrate into a suitable print size.
(2) Printing the prepared flexible conductive paste on a base material in a proper mode so as to form a conductive circuit; the printing method includes, but is not limited to, screen printing, spraying, screw extrusion, and the like.
(3) And volatilizing the solvent in the conductive paste at a certain temperature to enable the conductive paste to form a solid or form a high-viscosity liquid state.
(4) The slurry in the state of high-viscosity liquid is cured by one or two of heat curing and light curing. For example, the curing is carried out by thermal curing, and the curing temperature can be 110-160 ℃ and the curing time can be 10-30 min.
In the embodiment of the application, a mode of compounding the conductive main body component and the conductive stretching component is adopted, and under the condition of adding the preferable conductive stretching component, the better flexible conductive silver paste can be obtained, for example, the resistivity can still be kept good under the condition of 50% of stretching rate, and meanwhile, the bending test of at least R3 level can be tolerated.
In the embodiment of the present application, when the polymer-coated conductive material, i.e., the organic-inorganic composite stretched conductive material is added, although the initial resistivity is not particularly high, the loss of the resistivity can be minimized in the stretched state.
Compared with the prior art, the technical scheme of the embodiment of the application can at least achieve the following technical effects: (1) By using the high-efficiency conductive material as the main body, namely using the high-efficiency conductive material as the conductive main body component, the initial resistivity can be reduced, so that the resistivity is not too large when the final stretching and bending are carried out. (2) By adopting a mode of compounding the conductive main body component and the conductive stretching component, particularly compounding the conductive stretching component with high stretching performance, the resistivity in a stretching state can be ensured, and the high-stretching conductive material has higher requirements on the selection and addition of the high-stretching conductive material. (3) The conductive material coated by the macromolecule, namely the organic-inorganic composite high-tensile conductive material is added, and the conductive effect of the stretching of the organic matter on the inorganic matter is hardly influenced by the stretching.
The conductive paste, the electronic device and the method for manufacturing the same of the present application are further described below with specific examples. It will be appreciated by those skilled in the art that the present invention has been described in relation to only some of the examples and that any other suitable embodiment is within the scope of the invention.
Example 1
1. The conductive paste comprises the following components in parts by mass:
50 parts of conductive main body component, 20 parts of conductive stretching component, 10 parts of resin, 25 parts of solvent and 0.8 part of auxiliary agent.
Wherein the conductive main body component comprises 40 parts of 2-micron spherical silver powder and 10 parts of 10-micron flaky silver powder;
the conductive stretching component comprises 10 parts of nano silver wires, 5 parts of carbon nanotubes and 5 parts of PLA (polylactic acid) coated nano silver wires; the average length of the silver nanowires is 20 mu m, the average wire diameter is 20nm, and the average diameter of the carbon nanotubes is 0.4-20nm;
the resin comprises 7 parts of bisphenol A epoxy resin and 3 parts of amino resin; the solvent is isophorone; the auxiliary agent is ethyl cellulose.
2. An electronic device comprises a substrate and a conductive circuit formed on the substrate, wherein the conductive circuit is prepared from the conductive slurry; wherein the thickness of the base material is 100 μm, and the material of the base material is silica gel.
The preparation of the electronic device comprises: and (3) screen-printing the conductive silver paste on the surface of a 100-micron silica gel substrate, and curing, namely drying and curing at 150 ℃ for 15 min.
Example 2
Embodiment 2 is basically the same as embodiment 1, and the description of the same parts is omitted, except that: in the conductive paste of the present embodiment,
the conductive main body component comprises 45 parts of 2-micron spherical silver powder and 5 parts of 2-micron spherical copper powder; the conductive stretching component comprises 5 parts of silver-coated copper sheets, 5 parts of graphene and 10 parts of PLA-coated silver-coated copper powder.
The rest is the same as in example 1.
Example 3
Embodiment 3 is basically the same as embodiment 1, and the description of the same parts is omitted, except that: the conductive paste of the embodiment comprises the following components in parts by mass:
35 parts of conductive main body component, 35 parts of conductive stretching component, 12 parts of resin, 30 parts of solvent and 1.0 part of auxiliary agent.
Wherein the conductive main body component comprises 30 parts of 2-micron spherical silver powder and 5 parts of 10-micron flaky silver powder;
the conductive stretching component comprises 10 parts of carbon nanotubes and 25 parts of PLA enwrapping the silver nanowires;
the resin comprises 8 parts of bisphenol A epoxy resin and 4 parts of polyester resin; the solvent comprises 20 parts of isophorone and 10 parts of diethylene glycol dimethyl ether; the auxiliary agent comprises 0.5 part of ethyl cellulose and 0.5 part of sodium carboxymethyl cellulose.
The rest is the same as in example 1.
Example 4
1. The conductive paste comprises the following components in parts by mass:
30 parts of conductive main body component, 20 parts of conductive stretching component, 8 parts of resin, 45 parts of solvent and 1.1 parts of auxiliary agent.
Wherein the conductive main body component comprises 20 parts of 1-micron spherical silver powder and 10 parts of 5-micron silver-coated copper powder;
the conductive stretching component comprises 5 parts of 10-micrometer graphene, 5 parts of carbon nano-tubes, 5 parts of PVP (polyvinyl pyrrolidone) coated nano-silver wires and 5 parts of silver-coated copper wires; the average length of the silver-coated copper wire is 30 mu m, and the average wire diameter is 30nm;
the resin is TPU resin; the solvent is terpineol; the auxiliary agent comprises 1 part of BYK-410 and 0.1 part of KH-550.
2. An electronic device comprises a substrate and a conductive circuit formed on the substrate, wherein the conductive circuit is prepared from the conductive slurry; wherein the thickness of the base material is 100 μm, and the material of the base material is silica gel.
The preparation of the electronic device comprises: and (3) screen-printing the conductive silver paste on the surface of a 100-micron silica gel substrate, and curing, namely drying and curing at 130 ℃ for 20 min.
Example 5
Embodiment 5 is basically the same as embodiment 4, and the description of the same parts is omitted, except that: in the conductive paste of the present embodiment,
the conductive main body component comprises 15 parts of 10-micron silver powder and 15 parts of 5-micron silver-coated copper powder;
the conductive stretching component comprises 5 parts of 20-micron graphene oxide, 10 parts of PVA (polyvinyl alcohol) -coated nano silver wires and 5 parts of silver-coated copper wires.
The rest is the same as in example 4.
Example 6
1. The conductive paste comprises the following components in parts by mass:
80 parts of conductive main body component, 4 parts of conductive stretching component, 4 parts of resin, 12 parts of solvent and 0.205 part of auxiliary agent.
Wherein the conductive main body component comprises 60 parts of 5-micron spherical silver powder and 20 parts of 10-micron silver-coated copper powder;
the conductive stretching component comprises 2 parts of PEG-coated nano silver wires and 2 parts of silver-coated copper wires; the average length of the silver-coated copper wire is 30 mu m, and the average wire diameter is 30nm;
the resin is TPU resin; the solvent is ethylene glycol monomethyl ether; the auxiliary agent comprises 0.2 part of BYK-941 and 0.05 part of KH-550.
2. An electronic device comprises a substrate and a conductive circuit formed on the substrate, wherein the conductive circuit is prepared from the conductive slurry; wherein the thickness of the base material is 150 μm, and the base material is TPU.
The preparation of the electronic device comprises: and (3) screen-printing the conductive silver paste on the surface of the TPU substrate with the thickness of 150 microns, and curing, namely drying and curing at the temperature of 120 ℃ for 15 min.
Example 7
Embodiment 7 is basically the same as embodiment 6, and the description of the same parts is omitted, except that: the conductive paste comprises the following components in parts by mass:
80 parts of conductive main body component, 20 parts of conductive stretching component, 6 parts of resin, 15 parts of solvent and 0.205 part of auxiliary agent.
The conductive stretching component comprises 10 parts of PEG-coated nano silver wires and 10 parts of silver-coated copper wires; the average length of the silver-coated copper wire is 30 mu m, and the average wire diameter is 30nm;
the rest is the same as example 6.
Example 8
Embodiment 8 is basically the same as embodiment 6, and the description of the same parts is omitted, except that: the conductive paste comprises the following components in parts by mass:
20 parts of conductive main body component, 18 parts of conductive stretching component, 15 parts of resin, 50 parts of solvent and 2 parts of auxiliary agent.
Wherein the conductive main body component comprises 10 parts of 3-micron spherical silver powder and 10 parts of 5-micron silver-coated copper powder;
the conductive stretching component comprises 10 parts of PEG-coated nano silver wires, 5 parts of silver-coated copper wires and 3 parts of graphene; the average length of the silver-coated copper wire is 20 mu m, and the average wire diameter is 20nm;
the resin comprises 8 parts of bisphenol A epoxy resin and 7 parts of TPU resin; the solvent comprises 30 parts of ethylene glycol monomethyl ether and 20 parts of dimethylformamide; the auxiliary agent comprises 1.0 part of BYK-941,0.5 part of BYK-C8000 and 0.5 part of carboxymethyl cellulose.
The rest is the same as example 6.
Comparative example 1
The conductive paste comprises the following components in parts by mass:
70 parts of conductive main body component, 10 parts of resin, 25 parts of solvent and 0.8 part of auxiliary agent.
Wherein the conductive main body component comprises 50 parts of 2 μm spherical silver powder and 20 parts of 10 μm flake silver powder.
Comparative example 1 is different from example 1 in that the conductive stretching component in example 1 is omitted and the amount of the conductive body component is increased accordingly, and the rest is the same as example 1.
Comparative example 2
The conductive paste comprises the following components in parts by mass:
70 parts of conductive stretching component, 10 parts of resin, 25 parts of solvent and 0.8 part of auxiliary agent.
The conductive stretching component comprises 40 parts of nano-silver wires, 15 parts of carbon nano-tubes and 15 parts of PLA (polylactic acid) wrapped nano-silver wires; the average length of the silver nanowires is 20 μm, the average wire diameter is 20nm, and the average length of the carbon nanotubes is 20 μm, and the average diameter is 0.4-20nm.
Comparative example 2 is different from example 1 in that the conductive body component of example 1 is omitted and the amount of the conductive stretching component is increased accordingly, and the rest is the same as example 1.
Comparative example 3
The conductive paste comprises the following components in parts by mass:
5 parts of conductive main component, 15 parts of conductive stretching component, 1.5 parts of resin, 55 parts of solvent and 0.5 part of auxiliary agent.
The conductive main body component comprises 5 parts of 2-micron spherical silver powder, the conductive stretching component comprises 10 parts of nano silver wires and 5 parts of carbon nano tubes.
Comparative example 3 is different from example 1 in that the amounts of the conductive main component, the conductive stretching component and the resin are not within the range of the present application, and the rest is the same as example 1.
Performance testing
The electronic devices comprising the conductive paste of the present application of examples 1 to 8 and the electronic devices comprising the conductive paste of comparative examples 1 to 3 were subjected to performance tests in the present invention, and the results of the performance tests are shown in table 1 below.
The test method comprises the following steps:
the conductive pastes provided in the respective examples and comparative examples were tested for initial resistivity using a resistivity tester.
The electronic device is subjected to a stretching treatment, and after stretching by 50% or 100%, the resistivity after stretching by 50% or 100% is measured using a resistivity tester.
Bending the electronic device, bending R5 or R4 or R3 for 10 times, testing the resistivity after bending for 10 times by using a resistivity tester, and recording the resistance change rate after bending.
TABLE 1
Note: in the table, "-" indicates that the test for the item was not performed.
As can be seen from the data in table 1, the conductive paste provided in the embodiment of the present application has excellent conductivity and flexibility, and can meet the requirements of general conductive electronic industry. Specifically, the electrical resistivity and the tensile property of the conductive paste of example 1 are both excellent, the initial electrical resistivity is 25 μ Ω · cm, after being stretched by 50%, the electrical resistivity of 50 μ Ω · cm can be measured, and meanwhile, R5 is bent 10 times, the resistance change is less than 5%, and the stretching and bending properties of the conductive paste can completely meet the requirements of the general conductive electronic industry. Compared with the embodiment 1, the conductive paste of the embodiment 4 has the advantages that the silver content is reduced, the cost can be greatly reduced, and the resistivity can be influenced to a certain extent, but the tensile property of the carbon material is better, the conductive performance in a tensile state is excellent, the initial resistivity is 50 mu omega cm, after the carbon material is stretched by 50%, the resistivity of 85 mu omega cm can be measured, and under the condition of stretching by 100%, the resistivity can reach 125 mu omega cm, and meanwhile, R3 is bent for 10 times, the resistance change is less than 5%, and the resistivity and the tensile property can meet the requirements of the general conductive electronic industry. Compared with example 1, the conductive paste of example 6 has excellent initial resistivity, the initial resistivity is 15 μ Ω · cm, and after 50% stretching, the resistivity of 50 μ Ω · cm can be measured, and although the resistance change rate after stretching is large, the final resistivity and the stretching performance can meet the requirements of the general conductive electronic industry due to the excellent initial resistivity. In addition, the embodiments 2, 3, 5, 7-8 can achieve similar effects with the above embodiments 1, 4 or 6, and both the resistivity and the tensile property can meet the requirements of the general conductive electronic industry.
Meanwhile, through the above embodiments, it is obvious that the kinds and proportions of different conductive main body components, conductive tensile components and resins have certain influence on the initial resistivity and the tensile resistivity. Three typical examples are taken as examples for analytical illustration, namely example 1, example 4 and example 6; as can be seen from comparative analysis of example 1 and example 4, when 50 parts of the conductive body component and 20 parts of the conductive stretching component were added, the initial resistivity may be as small as 25 μ Ω · cm but the rate of change after stretching reached 100%, whereas in example 4, when 30 parts of the conductive body component and 20 parts of the conductive stretching component were added and the content of the flexible resin was higher, the initial resistivity was remarkably improved but the rate of change after final stretching reached 70% and the material cost was relatively lower. From the comparative analysis of example 4 and example 6, it can be seen that the change of the tensile resistivity of example 6 is more significant, and when 80 parts of the conductive body component and 4 parts of the conductive stretching component are added, the change rate after stretching reaches 233%, but the initial resistivity is smaller, so that the resistance after stretching can still substantially meet the requirement.
Compared with the conductive paste of the embodiment 1, the conductive pastes of the comparative examples 1 to 3 have lower conductive performance and tensile performance test results than the product of the embodiment 1, and cannot meet the requirements. The conductive paste as in comparative example 1, since the conductive stretching component is not added, the rate of change in resistance after stretching is drastically increased, and the stretching property cannot be required; the conductive paste of comparative example 2 has a high initial resistivity and is not required for conductive performance because no conductive host component is added.
The invention has not been described in detail and is in part known to those of skill in the art.
It should be noted that the term "and/or"/"used herein is only one kind of association relationship describing associated objects, and means that there may be three relationships, for example, a and/or B, and may mean: a exists alone, A and B exist simultaneously, and B exists alone. As used in the examples of the present invention and the appended claims, the singular forms "a," "an," and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
In the detailed description and claims, a list of items linked by the term "at least one of," "at least one of," or other similar terms may mean any combination of the listed items. For example, if items a, B are listed, the phrase "at least one of a, B" means a only; only B; or A and B. In another example, if items a, B, C are listed, the phrase "at least one of a, B, C" means a only; or only B; only C; a and B (excluding C); a and C (excluding B); b and C (excluding A); or all of A, B and C. Item a may comprise a single element or multiple elements. Item B may comprise a single element or multiple elements. Item C may comprise a single element or multiple elements.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. The conductive paste is characterized by comprising the following components in parts by mass:
30 to 90 parts of conductive component, 3 to 15 parts of resin, 10 to 65 parts of solvent and 0.1 to 5 parts of auxiliary agent;
the conductive component comprises a conductive main body component and a conductive stretching component, and the mass ratio of the conductive main body component to the conductive stretching component is (30-97): (3-70);
the conductive body component includes at least one of a silver-containing material or a copper-containing material;
the conductive stretching component comprises at least one of a nano or micron metal material, a carbon material or a polymer coated conductive material.
2. The conductive paste according to claim 1, comprising the following components in parts by mass: 50-85 parts of conductive component, 4-12 parts of resin, 12-50 parts of solvent and 0.5-2 parts of assistant;
and/or the mass ratio of the conductive main body component to the conductive stretching component is (50-96): (4-50).
3. The conductive paste of claim 1, wherein the conductive body composition comprises at least one of silver powder, copper powder, or silver-coated copper powder;
preferably, the silver powder includes at least one of a spherical silver powder, a flake silver powder, a rod-like silver powder, or a linear silver powder;
preferably, the silver powder is micron-sized silver powder, the copper powder is micron-sized copper powder, and the silver-coated copper powder is micron-sized silver-coated copper powder.
4. The conductive paste of claim 1, wherein the nano-or micro-scale metallic material comprises at least one of a silver nano-or micro-material, a copper nano-or micro-material, a silver-coated copper nano-or micro-material, a gold-coated copper nano-or micro-material, a gold-coated silver nano-or micro-material;
and/or the carbon material comprises at least one of graphene, graphene oxide, reduced graphene oxide, graphene modified by chemical functional groups, carbon nanotubes or carbon fibers;
and/or the conducting material coated by the polymer is in a core-shell shape, the core layer is a conducting material, and the shell layer is a polymer material;
and/or the conductive tensile component further comprises MXene.
5. The conductive paste as claimed in claim 4, wherein the morphology of the nano-or micro-scale metallic material comprises at least one of a sheet, a wire, a rod, a core-shell, or a cluster;
and/or the conductive material comprises at least one of a nano silver wire, a silver powder, a copper powder, a silver-coated copper powder, graphene or a carbon nanotube;
and/or the high polymer material comprises at least one of polyethylene glycol (PEG), polylactic acid (PLA), polyvinylpyrrolidone (PVP), polyacrylic acid (PAA), polyvinyl alcohol (PVA), polyoxyethylene (PEO), polylactide (PLLA), polycaprolactone (PCL), polyacrylonitrile (PAN) or polymethyl methacrylate (PMMA).
6. The conductive paste as claimed in any one of claims 1 to 5, wherein the resin has a number average molecular weight of 1000 or more;
and/or the boiling point of the solvent is more than or equal to 100 ℃.
7. The conductive paste according to claim 6, wherein the resin comprises at least one of TPU resin, polyester resin, acrylic resin, amino resin, silicone resin, or epoxy resin;
and/or the solvent comprises at least one of DBE, MDBE, ethylene glycol, dimethylformamide, diethylene glycol dimethyl ether, ethylene glycol monomethyl ether, diethylene glycol butyl ether acetate, diethylene glycol butyl ether, octanol, octyl acetate, xylene, terpineol or isophorone;
and/or the auxiliary agent comprises at least one of a wetting dispersant, a defoaming agent, an accelerator, a tackifier, a surfactant, a coupling agent, a moldability modifier or a curing modifier.
8. A method for preparing the electroconductive paste according to any one of claims 1 to 7, comprising:
and stirring and mixing the conductive main body component, the conductive stretching component, the resin, the solvent and the auxiliary agent according to the formula ratio to obtain the conductive slurry.
9. An electronic device comprising a substrate and a conductive wiring formed on the substrate, the conductive wiring being prepared from the conductive paste according to any one of claims 1 to 7.
10. The electronic device according to claim 9, wherein the substrate has a thickness of 20 μm to 500 μm;
preferably, the material of the substrate includes at least one of Polydimethylsiloxane (PDMS), thermoplastic polyurethane elastomer rubber (TPU), polyethylene terephthalate (PET), polyethylene (PE), silicone, polyester, or acrylate;
preferably, the method of preparing the conductive line includes: printing the conductive paste on the base material, and curing to obtain the conductive circuit;
preferably, the curing temperature is 110-160 ℃ and the curing time is 10-30 min.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116130142A (en) * | 2022-12-28 | 2023-05-16 | 北京交通大学 | High-conductivity, anti-corrosion and anti-aging electric power composite grease and preparation method thereof |
| CN117079860A (en) * | 2023-10-12 | 2023-11-17 | 上海银浆科技有限公司 | Low-temperature silver paste for low-consumption silver heterojunction solar cell, and preparation method and application thereof |
| CN117091727A (en) * | 2023-08-24 | 2023-11-21 | 哈尔滨理工大学 | PEO-based implantable battery temperature sensor and preparation method and application thereof |
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2022
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116130142A (en) * | 2022-12-28 | 2023-05-16 | 北京交通大学 | High-conductivity, anti-corrosion and anti-aging electric power composite grease and preparation method thereof |
| CN116130142B (en) * | 2022-12-28 | 2023-09-22 | 北京交通大学 | Preparation method of high-conductivity, anti-corrosion and anti-aging electric power composite grease |
| CN117091727A (en) * | 2023-08-24 | 2023-11-21 | 哈尔滨理工大学 | PEO-based implantable battery temperature sensor and preparation method and application thereof |
| CN117091727B (en) * | 2023-08-24 | 2024-04-23 | 哈尔滨理工大学 | PEO-based implantable battery temperature sensor and preparation method and application thereof |
| CN117079860A (en) * | 2023-10-12 | 2023-11-17 | 上海银浆科技有限公司 | Low-temperature silver paste for low-consumption silver heterojunction solar cell, and preparation method and application thereof |
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