CN112980356A - Conductive adhesive, flexible circuit, flexible printed circuit board and flexible electronic element - Google Patents

Conductive adhesive, flexible circuit, flexible printed circuit board and flexible electronic element Download PDF

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Publication number
CN112980356A
CN112980356A CN202110214999.XA CN202110214999A CN112980356A CN 112980356 A CN112980356 A CN 112980356A CN 202110214999 A CN202110214999 A CN 202110214999A CN 112980356 A CN112980356 A CN 112980356A
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conductive adhesive
flexible
nanoparticles
water
base material
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郝长祥
田颜清
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Shenzhen Nanke Kangda Technology Co ltd
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Shenzhen Nanke Kangda Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J129/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Adhesives based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Adhesives based on derivatives of such polymers
    • C09J129/02—Homopolymers or copolymers of unsaturated alcohols
    • C09J129/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J167/00—Adhesives based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Adhesives based on derivatives of such polymers
    • C09J167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
    • C09J175/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J177/00—Adhesives based on polyamides obtained by reactions forming a carboxylic amide link in the main chain; Adhesives based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/02—Details
    • H05K1/09—Use of materials for the conductive, e.g. metallic pattern
    • H05K1/092—Dispersed materials, e.g. conductive pastes or inks
    • 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

Abstract

The invention relates to a conductive adhesive, a flexible circuit, a flexible printed circuit board and a flexible electronic element, wherein the conductive adhesive comprises the following components: water-dispersible polymer nanoparticles, silver powder, a resin base material, and a solvent; the content of the water-dispersible polymer nanoparticles is 4% -10%, the content of the silver powder is 60% -80%, and the content of the resin base material is 16% -36%, wherein the total mass of the water-dispersible polymer nanoparticles, the silver powder and the resin base material is 100%. The conductive adhesive provided by the invention can obviously improve the conductivity on the basis of low silver content, is favorable for reducing the cost under the condition of less silver content under the same condition, and can improve the flexibility and the printing performance of the cured conductive adhesive, so that the conductive adhesive has wide application prospect in flexible circuit boards and flexible devices.

Description

Conductive adhesive, flexible circuit, flexible printed circuit board and flexible electronic element
Technical Field
The invention relates to the technical field of conductive materials, in particular to a conductive adhesive, a flexible circuit, a flexible printed circuit board and a flexible electronic element.
Background
The conductive adhesive is an adhesive with certain conductive performance after being cured or dried, and generally takes matrix resin and conductive filler, namely conductive particles as main components, and the conductive particles are combined together through the bonding action of the matrix resin to form a conductive path so as to realize the conductive connection of the bonded materials. The matrix resin of the conductive adhesive is an adhesive, so that the conductive adhesive can be bonded by selecting a proper curing temperature, and meanwhile, the conductive adhesive can be made into slurry to realize high linear resolution due to the rapid development of miniaturization and microminiaturization of electronic elements and high density and high integration of printed circuit boards. And the conductive adhesive has simple process and easy operation, does not contain lead and other toxic metals, so the conductive adhesive is an ideal choice for replacing lead-tin welding and realizing conductive connection. The principle of electric conduction is that the mutual contact among the conductive particles forms a conductive path, so that the conductive adhesive has conductivity, and the stable contact among the particles in the adhesive layer is caused by the solidification or drying of the conductive adhesive. Before the conductive adhesive is cured or dried, the conductive particles are separated in the adhesive and are not in continuous contact with each other, so that the conductive adhesive is in an insulating state. After the conductive paste is cured or dried, the volume of the adhesive shrinks due to the volatilization of the solvent and the curing of the adhesive, so that the conductive particles are in a stable continuous state with each other, thereby exhibiting conductivity.
Conductive adhesives have found wide application in the electronics field. The conductivity and the content of the metal filler are one of the important criteria for measuring the quality of the conductive adhesive. In order to improve the conductivity of the conductive adhesive, a great deal of research is carried out by experts at home and abroad, and the research results are introduced respectively: ren et al (Ren, H. -M.; Guo, Y.; Huang, S. -Y.; Zhang, K.; Yuen, M.M.F.; Fu, X. -Z.; Yu, S.; Sun, R.; Wong, C. -P., One-step preparation of silver hexagonal micro;)sheets as electrically conductive adhesive fillers for printed electronics.ACS applied materials&interfaces 2015,7(24),13685-13692.) through a one-step solution phase chemical reduction method, regular hexagonal nano silver flakes are synthesized, compared with commercial silver flakes, the hexagonal nano silver flakes have better conductivity and smoother surface, and the characteristic of being easier to disperse in a polymer substrate, so that the hexagonal nano silver flakes can be combined with the polymer substrate and can be easily printed on various substrates, such as polyethylene terephthalate (PET), glass and other materials. The hexagonal nano silver sheet used as the conductive filler shows lower resistivity (about 8 multiplied by 10) when being applied to the conductive adhesive-5Omega cm) about 66 times lower than that of the commercial conductive adhesive with the same Ag content. Zhang et al (Zhang, y.; Zhu, p.; Li, g.; Cui, z.; Cui, c.; Zhang, k.; Gao, j.; Chen, x.; Zhang, g.; Sun, r., PVP-media rheological Synthesis of Smart Cu-Ag nanofilakes for electric Conductive materials&interfaces 2019, 11, 8382-8390) synthesizes the synthetic oval Cu-Ag alloy nanosheet by an electrochemical replacement method. The alloy nano-flake has high purity and uniformity, and has the size of 700 x 500nm and the thinness of 30 nm. The synthesized nanoflakes are used as fillers for conductive pastes in epoxy matrices. After curing at 150 ℃ for 2 hours, a resistivity of 3.75X 10 was obtained-5A conductive pattern on the flexible substrate of Ω · cm. Cu-Ag alloy nanofilms provide greatly improved conductive interconnects, the advantages of which can be attributed to their nanoscale thickness, compared to conventional silver microfilms. It is also noteworthy that the conductive pattern is able to withstand multiple bends at different angles, with good conductivity even after 200 repeated bends.
Lou et al (Luo, J.; Cheng, Z.; Li, C.; Wang, L.; Yu, C.; Zhao, Y.; Chen, M.; Li, Q.; Yao, Y.; electric conductive additives based on thermoplastic polyurethane fibers with additives and carbon nanotubes, compositions Science and Technology 2016,129,191-197.) use thermoplastic polyurethane as the resin matrix to which carbon nanotubes are added, a mixed system of carbon nanotubes and silver forming a conductive network, and carbon nanotubes may also be added during bendingTo play a connecting role, and simultaneously, the silver powder surfaces are treated by succinic acid to obtain the silver powder with the conductivity of 2.5 multiplied by 104S/m conductive paste (50 wt% silver +4.5 wt% CNTs).
The nano-metal material (such as silver nano-crystal) has a thickness of about 106The extremely high conductivity of S/m is widely applied to the fields of modification of conductive adhesive, energy catalysis and the like, however, the conductive materials are only expensive and are easy to chemically corrode. Polymeric materials are generally relatively inexpensive to manufacture and can withstand various chemical attacks, but they are generally insulating, as compared to nano-metallic materials. The discovery of intrinsically conductive polymers in the 70's of the 20 th century has led to new insights into the chemical structure and electrical properties of polymeric materials. P electrons in the conjugated main chain of these conductive polymers can be delocalized and introduced into the conduction band, thereby improving the conductivity of the conductive polymer. Typical CPs with conjugated bonds include polypyrrole (PPy), Polyaniline (PANI), polythiophene (PTh) and their derivatives. However, neutral conjugated polymers show lower conductivities (from 10)-10To 10-5S/cm), their conductivity can be increased by 10 by doping with various molecules such as protonic acid, inorganic salt, etc4S/cm. Generally, these conductive polymers can provide positive and negative charge carriers and exhibit unique electronic characteristics after the use of a dopant. Such conductive polymer materials, which combine the conductive properties of metallic materials with many of the advantages of polymeric materials, have attracted various researchers to explore their various applications, such as antistatic protection, electromagnetic interference (EMI) shielding, energy storage electrodes, sensors, and flexible electronics, among others. However, the use of these materials in conductive adhesives is still in the beginning, because these conductive adhesive polymers still need further chemical modification or redesign to overcome their inherent disadvantages, such as poor solubility, mostly spherical with low aspect ratio, etc.
Therefore, the method still has important significance for the development of high-performance conductive adhesive high-molecular materials in the field.
Disclosure of Invention
In view of the defects of the prior art, an object of the present invention is to provide a conductive adhesive, which can significantly improve conductivity on the basis of low silver content, and a small amount of silver content is favorable for reducing cost under the same conditions, and can improve the flexibility and printing performance of the conductive adhesive after curing, so that the conductive adhesive has a wide application prospect in flexible circuit boards and flexible devices.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a conductive adhesive, which comprises the following components: water-dispersible polymer nanoparticles, silver powder, a resin base material, and a solvent;
the water-dispersible polymer nanoparticles are present in an amount of 4% to 10%, e.g., 4.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, etc., the silver powder is present in an amount of 60% to 80%, e.g., 62%, 63%, 64%, 65%, 66%, 67%, 68%, 69%, 70%, 71%, 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, etc., and the resin base material is present in an amount of 16% to 36%, e.g., 17%, 18%, 19%, 20%, 22%, 24%, 26%, 28%, 30%, 32%, 34%, 35%, etc., based on 100% total mass of the water-dispersible polymer nanoparticles, silver powder, and resin base material.
In the present invention, the water-dispersible polymer nanoparticles refer to polymer nanoparticles that can be uniformly dispersed in water.
The invention provides a novel high-molecular conductive adhesive, which can remarkably improve the conductivity on the basis of reducing the silver content by adding a proper amount of water-dispersible polymer nano particles, is favorable for reducing the cost by a small amount of silver content under the same condition, and can improve the flexibility and the printing performance of the cured conductive adhesive, so that the conductive adhesive has wide application prospect in flexible circuit boards and flexible devices.
Preferably, the water dispersible polymer nanoparticles comprise any one or a combination of at least two of polyaniline nanoparticles, polythiophene nanoparticles, or polypyrrole nanoparticles, preferably polyaniline nanoparticles. The combination specifically includes a combination of polyaniline nanoparticles and polythiophene nanoparticles, a combination of polyaniline nanoparticles and polypyrrole nanoparticles, or a combination of polythiophene nanoparticles and polypyrrole nanoparticles.
The polyaniline, polythiophene and polypyrrole polymer nanoparticles are preferably selected in the invention, compared with other water-dispersible polymers, the polyaniline, polythiophene and polypyrrole polymer nanoparticles have the advantages that the conductivity of the conductive adhesive is improved, and the resistance impedance characteristic is reduced, so that the conductivity of the conductive adhesive can be further improved on the premise of the same silver addition amount, and the polyaniline effect is optimal.
In addition, the water-dispersible polymer nanoparticles have good dispersibility in water and alcohol, can be dispersed in nontoxic and low-toxicity solvents, and are environment-friendly.
Preferably, the water dispersible polymer has a particle size of 50 to 500nm, such as 60nm, 70nm, 80nm, 100nm, 120nm, 140nm, 160nm, 180nm, 200nm, 220nm, 240nm, 260nm, 280nm, 300nm, 320nm, 340nm, 360nm, 380nm, 400nm, 420nm, 440nm, 460nm, 480nm, and the like.
Preferably, the preparation method of the polyaniline nanoparticles comprises the following steps:
and mixing a polyvinylpyrrolidone (PVP) aqueous solution, aniline hydrochloride and an oxidant, and reacting to obtain the polyaniline nano-particles.
Preferably, the concentration of the aqueous solution of the polypyrrolidone is 3 to 8g/L, such as 3.2g/L, 3.5g/L, 4g/L, 4.5g/L, 5g/L, 5.5g/L, 6g/L, 6.5g/L, 7g/L, 7.5g/L, 8g/L, and the like, preferably 5 g/L.
Preferably, the number average molecular weight of the polypyrrolidone is 8000-.
Preferably, the oxidizing agent comprises any one or at least two of ammonium persulfate, potassium permanganate, benzoyl peroxide or hydrogen peroxide in combination.
Preferably, the reaction time is 20-30h, such as 21h, 22h, 23h, 24h, 25h, 26h, 27h, 28h, 29h, etc., preferably 24 h.
Preferably, the preparation method further comprises: after the reaction, filtration is performed, and then the product is washed with a hydrochloric acid solution and dried to obtain the polyaniline nanoparticles.
Preferably, the concentration of the hydrochloric acid solution is 0.8 to 1.2mol/L, such as 0.85mol/L, 0.9mol/L, 0.95mol/L, 1mol/L, 1.1mol/L, etc., preferably 1 mol/L.
Preferably, the number of times of washing is more than or equal to 5 times.
Preferably, the preparation method of the polyaniline nanoparticles comprises the following steps:
and dissolving the polypyrrolidone in deionized water, adding aniline hydrochloride, stirring uniformly, adding ammonium persulfate, reacting for 24 hours, filtering the generated solid, and washing for 5 times by using 1mol/L diluted hydrochloric acid solution to obtain the polyaniline nano-particles.
Preferably, the silver powder has an average particle size of 0.5 to 10 micrometers, such as 1 micrometer, 2 micrometers, 3 micrometers, 4 micrometers, 5 micrometers, 6 micrometers, 7 micrometers, 8 micrometers, 9 micrometers, and the like.
Preferably, the resin base material comprises any one or a combination of at least two of acrylic resin, polyurethane, polyamide, polyvinyl alcohol, polyvinyl butyral, rosin modified alkyd resin, thermoplastic phenolic resin, urea formaldehyde resin or alkyd resin.
The invention preferably adopts water system or alcohol system macromolecule resin base material, and has better close attaching effect to metal, glass and polymer.
Preferably, the resin base material has a number average molecular weight of 8000-.
Preferably, the solvent comprises any one or a combination of at least two of water, ethanol, propanol, butanol, acetic acid, ethyl acetate or butyl acetate, preferably any one or a combination of at least two of water, ethanol, propanol, butanol or acetic acid.
The solvents are low-toxicity or non-toxic substances, are environment-friendly, and particularly can achieve the purposes of environmental protection, no toxicity and quick drying and solidification when ethanol is used as the solvent.
Preferably, the solid content of the conductive adhesive is 40% -60%. The solid content refers to the percentage of the sum of the mass of the water-dispersible polymer nanoparticles, the silver powder and the resin matrix material in the conductive adhesive in the total mass of the conductive adhesive.
Preferably, the resistivity of the conductive adhesive is less than or equal to 1.8 multiplied by 10-3Omega. cm, e.g. 4.2X 10-4Ω.cm、4.8×10-4Ω.cm、0.5×10-3Ω.cm、1×10-3Ω.cm、1.5×10-3Ω. cm, etc.
The conductive adhesive provided by the invention is prepared by simply mixing the formula materials, the preparation method belongs to the common general knowledge in the field, and the conductive adhesive can be adjusted by a person skilled in the art according to the actual needs, and the invention is not particularly limited to this.
Another object of the present invention is to provide a flexible circuit formed by printing the conductive paste according to the first object.
The flexible circuit printed by the conductive adhesive provided by the invention still has good conductivity and excellent flexibility under the bending and folding conditions.
Illustratively, the flexible circuit is as shown in fig. 2.
Preferably, the printing method includes any one of a brush coating method, a knife coating method, a roll coating method, or a spray coating method.
Preferably, the method for manufacturing the flexible circuit comprises the following steps: and coating the conductive adhesive of one purpose on a substrate, drying, and printing by using a mask plate to obtain the flexible circuit.
Preferably, the coating thickness of the conductive paste is 20-40 μm, such as 22 μm, 24 μm, 26 μm, 28 μm, 30 μm, 32 μm, 34 μm, 36 μm, 38 μm, etc., preferably 30 μm.
Preferably, the drying time is 20-40min, such as 22min, 24min, 26min, 28min, 30min, 32min, 34min, 36min, 38min, etc., preferably 30 min.
The present invention also provides a flexible printed circuit board including a substrate and the flexible circuit disposed on the substrate.
It is a fourth object of the present invention to provide a flexible electronic component including the second flexible circuit or the third flexible printed circuit board.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel high-molecular conductive adhesive, which can remarkably improve the conductivity on the basis of reducing the silver content by adding a proper amount of water-dispersible polymer nano particles, is favorable for reducing the cost by a small amount of silver content under the same condition, and can improve the flexibility and the printing performance of the cured conductive adhesive, so that the conductive adhesive has wide application prospect in flexible circuit boards and flexible devices.
Drawings
Fig. 1 is an SEM image of polyaniline nanoparticles used in example 1 of the present invention.
Fig. 2 is a schematic diagram of a flexible circuit in accordance with an embodiment of the present invention.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The details of the raw materials used in the following examples and comparative examples are as follows:
(mono) Water dispersible Polymer nanoparticles
The preparation method of the polyaniline nanoparticles comprises the following steps:
dissolving 5g of PVP (Mn ═ 10000) in 1000mL of deionized water, adding 13 g of aniline hydrochloride, stirring uniformly, adding 40g of ammonium persulfate, reacting for 24 hours, filtering the generated solid, washing the solid for 5 times by using a 1mol/L dilute hydrochloric acid solution, and drying the obtained solid to obtain a product with yield: 80% and the average grain diameter is between 80 nm.
The appearance of the polyaniline nanoparticles is measured by a scanning electron microscope, and is shown in figure 1.
Polythiophene nanoparticles, available from Kyoho industries, Inc. of Shanghai under the designation KS1001, having an average particle size of 70 nm.
Polypyrrole nanoparticles, available from Sigma-Aldrich Sigma Aldrich trade ltd under the trade designation MFCD00284347, with an average particle size of 100 nm.
(II) silver powder
Purchased from south china Longjin alloy materials, Inc. under the designation Ag1127 and having an average particle size of 5 microns.
(III) resin base Material
The acrylic resin is purchased from Jitian chemical industry Co., Ltd, Shenzhen, and has the brand number of E0502 and the number average molecular weight of 8500.
Polyurethane, purchased from Jitian chemical Co., Ltd, Shenzhen, brand number F0401, number average molecular weight 10000.
Polyamide available from Shanghai Yu-Tiao plastics materials Ltd under the designation ST801 having a number average molecular weight of 12000.
Polyvinyl alcohol, available from Kyowa chemical Co., Ltd, Guangzhou under the designation 05-88(088-05), has a number average molecular weight of 8000.
The rosin modified alkyd resin is purchased from Jitian chemical Co., Ltd, Shenzhen, and has the brand number of BZ05 and the number average molecular weight of 15000.
Examples 1 to 9
The above embodiments respectively provide a conductive adhesive, which is composed of the following components: water-dispersible polymer nanoparticles, silver powder, a resin base material, and a solvent;
the content of the water-dispersible polymer nanoparticles, the silver powder and the resin substrate material is detailed in table 1 by taking the total mass of the water-dispersible polymer nanoparticles, the silver powder and the resin substrate material as 100%;
specific types of the water-dispersible polymer nanoparticles, the silver powder, the resin base material and the solvent and the solid content of the conductive adhesive are also detailed in table 1;
the preparation method of the conductive adhesive is to simply and uniformly mix the substances in the formula.
Comparative examples 1 to 3
The above comparative examples respectively provide a conductive paste consisting of the following components: silver powder, a resin base material and a solvent;
the content of the silver powder and the resin base material is detailed in table 1 by taking the total mass of the silver powder and the resin base material as 100%;
the specific types of the silver powder, the resin base material and the solvent and the solid content of the conductive adhesive are also detailed in table 1;
the preparation method of the conductive adhesive is to simply and uniformly mix the substances in the formula.
Performance test 1:
(1) and (3) resistivity testing:
the conductive pastes of the above examples and comparative examples were respectively coated with a film thickness controlled at 30 μm. After drying at room temperature for more than 30 minutes, the resistivity was measured by means of a four-probe.
(2) Flexibility test:
the resistance change before and after bending was tested on a circuit made of conductive paste under a condition of bending a radius of 6 mm by 180 degrees. Flexibility is defined as a change of less than 10%, flexibility is defined as a change of less than 50% and greater than 10%, flexibility is defined as a change of less than 200% and greater than 50%, and brittleness is defined as a change of resistance of greater than 200% or a break of the circuit.
The test results are shown in table 1.
TABLE 1
Figure BDA0002952857370000101
Figure BDA0002952857370000111
In Table 1, -.
As can be seen from Table 1, the conductive paste of the present invention, which has significantly improved conductivity by adding water-dispersible polymer nanoparticles to the conductive paste, has high conductivity even when the amount of silver powder added is only 60%, and has a resistivity of less than 9.6X 10-3Omega, cm, even less than 2.1X 10-3Omega cm, and less silver powder is beneficial to improving the conductivityThe flexibility of the glue makes it applicable to flexible circuits, flexible electronic components, etc.
As can be seen from comparative examples 1, 4 and 5, polyaniline nanoparticles are more advantageous in improving conductivity than polythiophene and polypyrrole.
Performance test 2
The circuit diagram prepared from the material of example 2 by screen printing is communicated with the light emitting diode, the circuit is bent to different degrees, the brightness of the light emitting diode is observed, the result shows that the light emitting diode is still lightened under the bending and folding conditions, and the circuit is proved to still have good conductivity.
The applicant states that the present invention is illustrated in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e. it is not meant that the present invention must rely on the above detailed methods for its implementation. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. The conductive adhesive is characterized by comprising the following components: water-dispersible polymer nanoparticles, silver powder, a resin base material, and a solvent;
the content of the water-dispersible polymer nanoparticles is 4% -10%, the content of the silver powder is 60% -80%, and the content of the resin base material is 16% -36%, wherein the total mass of the water-dispersible polymer nanoparticles, the silver powder and the resin base material is 100%.
2. The conductive adhesive of claim 1, wherein the water dispersible polymer nanoparticles comprise any one or a combination of at least two of polyaniline nanoparticles, polythiophene nanoparticles, or polypyrrole nanoparticles, preferably polyaniline nanoparticles;
preferably, the particle size of the water dispersible polymer is 50 to 500 nm;
preferably, the preparation method of the polyaniline nanoparticles comprises the following steps:
mixing a polypyrrolidone aqueous solution, aniline hydrochloride and an oxidant, and reacting to obtain polyaniline nanoparticles;
preferably, the concentration of the aqueous solution of the polypyrrolidone is 3-8g/L, preferably 5 g/L;
preferably, the number average molecular weight of the polypyrrolidone is 8000-;
preferably, the oxidant comprises any one or at least two of ammonium persulfate, potassium permanganate, benzoyl peroxide or hydrogen peroxide;
preferably, the reaction time is 20-30h, preferably 24 h;
preferably, the preparation method further comprises: after the reaction, filtering is carried out, and then a product is washed by using a hydrochloric acid solution and dried to obtain the polyaniline nanoparticles;
preferably, the concentration of the hydrochloric acid solution is 0.8-1.2mol/L, preferably 1 mol/L;
preferably, the number of times of washing is more than or equal to 5 times.
3. The conductive paste according to claim 1 or 2, wherein the silver powder has an average particle diameter of 0.5 to 10 μm.
4. The conductive adhesive as claimed in any one of claims 1 to 3, wherein the resin base material comprises any one or a combination of at least two of acrylic resin, polyurethane, polyamide, polyvinyl alcohol, polyvinyl butyral, rosin modified alkyd resin, phenol-formaldehyde thermoplastic resin, urea-formaldehyde resin or alkyd resin;
preferably, the resin base material has a number average molecular weight of 8000-.
5. The conductive paste according to any one of claims 1 to 4, wherein the solvent comprises any one or a combination of at least two of water, ethanol, propanol, butanol, acetic acid, ethyl acetate, or butyl acetate, preferably any one or a combination of at least two of water, ethanol, propanol, butanol, or acetic acid;
preferably, the solid content of the conductive adhesive is 40% -60%.
6. The conductive adhesive according to any one of claims 1 to 5, wherein the conductive adhesive has a resistivity of 1.8 x 10 or less-3Ω.cm。
7. A flexible circuit produced by printing the conductive paste according to any one of claims 1 to 6.
8. The flexible circuit of claim 7, wherein the printing method comprises any one of brushing, doctor blading, roller coating, or spraying;
preferably, the method for manufacturing the flexible circuit comprises the following steps: coating the conductive adhesive of any one of claims 1-6 on a substrate, drying, and obtaining the flexible circuit by mask printing;
preferably, the coating thickness of the conductive adhesive is 20-40 μm, preferably 30 μm;
preferably, the drying time is 20-40min, preferably 30 min.
9. A flexible printed circuit board comprising a substrate and the flexible circuit of claim 7 or 8 disposed on the substrate.
10. A flexible electronic component, characterized in that the flexible circuit of claim 7 or 8 or the flexible printed circuit board of claim 9 is contained in the electronic component.
CN202110214999.XA 2021-02-25 2021-02-25 Conductive adhesive, flexible circuit, flexible printed circuit board and flexible electronic element Pending CN112980356A (en)

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CN113658875A (en) * 2021-08-18 2021-11-16 深圳市振华微电子有限公司 Method for assembling medium and small power hybrid integrated circuit
CN113831876A (en) * 2021-09-24 2021-12-24 深圳市南科康达科技有限公司 Conductive adhesive, solid conductive adhesive film, and preparation method and application thereof
CN114634791A (en) * 2022-03-09 2022-06-17 南京工业大学 Poly-o-epoxy-N-methylaniline conductive bonding resin, preparation method thereof, conductive organic thermosetting material and application

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113388354A (en) * 2021-07-06 2021-09-14 南方科技大学 Conductive silver adhesive and conductive adhesive film
CN113658875A (en) * 2021-08-18 2021-11-16 深圳市振华微电子有限公司 Method for assembling medium and small power hybrid integrated circuit
CN113658875B (en) * 2021-08-18 2022-06-21 深圳市振华微电子有限公司 Method for assembling medium and small power hybrid integrated circuit
CN113831876A (en) * 2021-09-24 2021-12-24 深圳市南科康达科技有限公司 Conductive adhesive, solid conductive adhesive film, and preparation method and application thereof
CN114634791A (en) * 2022-03-09 2022-06-17 南京工业大学 Poly-o-epoxy-N-methylaniline conductive bonding resin, preparation method thereof, conductive organic thermosetting material and application
CN114634791B (en) * 2022-03-09 2023-10-13 南京工业大学 Poly-o-epoxy-N-methylaniline conductive adhesive resin, preparation method thereof, conductive organic thermosetting material and application

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