CN112961626B - Long-acting anti-oxidation high-conductivity conductive adhesive and preparation method thereof - Google Patents
Long-acting anti-oxidation high-conductivity conductive adhesive and preparation method thereof Download PDFInfo
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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
- C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
- C09J9/02—Electrically-conducting adhesives
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/04—Epoxynovolacs
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- 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
- C08K2003/085—Copper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
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Abstract
The invention discloses a long-acting anti-oxidation high-conductivity conductive adhesive, which comprises a component A and a component B, wherein the mass ratio of the component A to the component B is (10-15): 1; the component A comprises the following raw materials in parts by weight: polymer matrix resin, conductive filler, wetting dispersant, thixotropic agent, toughening agent and graphene; the component B comprises the following raw materials in parts by weight: solvent, curing agent and curing accelerator. According to the long-acting anti-oxidation high-conductivity conductive adhesive and the preparation method thereof, the graphene is introduced as the auxiliary conductive filler, so that the anti-oxidation performance of the conductive adhesive is improved, the durability of the conductive adhesive is improved, the graphene with the blocking and conductive functions can prevent the metal filler from being oxidized in a conductive adhesive system, and the stability of the whole conductive adhesive system is ensured.
Description
Technical Field
The invention relates to the technical field of conductive adhesive materials, in particular to a long-acting anti-oxidation high-conductivity conductive adhesive and a preparation method thereof.
Background
The conductive adhesive is a functional adhesive with conductivity after being cured, and is obtained by mainly adding conductive filler and other additives into an organic polymer matrix, and bonding conductive particles together through the bonding effect of matrix resin after being cured to form a conductive path. The conductive adhesive has wide application in the fields of electronic packaging, integrated circuits and the like.
The conductive filler of the current conductive adhesive comprises metal and nonmetal. However, the metal filler conductive adhesive has problems in practical use, such as low conductivity, poor environmental resistance, poor storage stability, and the like. For example, patent application No. 201110289508.4 discloses a one-part epoxy conductive adhesive, wherein the conductive filler is copper powder, the conductivity can only be 10-2Omega cm, the application scene with higher performance requirement cannot be met; the patent application with the application number of 201310571424.9 discloses an epoxy resin conductive adhesive and a preparation method thereof, wherein graphene is used for modifying aluminum powder, and although the high-conductivity conductive adhesive can be obtained, the conductive adhesive obtained by the method has poor stability and can only be stored at low temperature; the patent application with the application number of 201210263296.7 discloses a high-conductivity graphene conductive adhesive and a preparation method thereof, but pure graphene as a filler has insufficient colloidal strength, and the environmental resistance of the graphene conductive adhesive is influenced by brittleness of the graphene conductive adhesive in the environment.
Therefore, how to provide a long-acting anti-oxidation conductive adhesive with high conductivity and a preparation method thereof are technical problems to be solved urgently by technical personnel in the field.
Disclosure of Invention
In view of the above, the invention provides a long-acting anti-oxidation high-conductivity conductive adhesive and a preparation method thereof, and graphene is introduced as an auxiliary conductive filler, so that the anti-oxidation performance of the conductive adhesive is improved, the durability of the conductive adhesive is improved, the graphene with the blocking and conductive functions can prevent a metal filler from being oxidized in a conductive adhesive system, and the stability of the whole conductive adhesive system is ensured, so as to solve the defects of poor conductivity, poor system stability, poor environment resistance and the like of a conductive adhesive in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a long-acting anti-oxidation high-conductivity conductive adhesive comprises a component A and a component B, wherein the mass ratio of the component A to the component B is (10-15): 1;
the component A comprises the following raw materials in parts by weight:
the component B comprises the following raw materials in parts by weight:
10-30 parts of solvent
50-80 parts of curing agent
5-20 parts of a curing accelerator.
Preferably, the conductive filler powder is prepared by the following steps:
(1) preparing modified conductive metal powder: adding dilute hydrochloric acid into metal powder, performing ultrasonic treatment, performing centrifugal separation, cleaning with a solvent a, and performing vacuum drying to obtain modified conductive metal powder;
more specifically, the concentration of the dilute hydrochloric acid is 5-7%, and the dosage ratio of the dilute hydrochloric acid to the metal powder is as follows: 3-5 mL: 1g (dilute hydrochloric acid is required to completely submerge the metal powder); the ultrasonic power is 1200W, the frequency is within the range of 220V 20K Hz +/-10 percent, and the time is 1-2 h; the rotational speed of centrifugation is 4000-; the solvent a is absolute ethyl alcohol, and is washed for 3 to 5 times; the temperature of vacuum drying is 110-120 ℃, the vacuum degree is lower than 100KPa, and the drying time is 2-4 h;
(2) preparing graphene slurry: sequentially adding resin, an anti-settling auxiliary agent and a diluent into the graphene powder, dispersing at a high speed after ultrasonic dispersion, completely and uniformly mixing a system, and drying in vacuum to obtain graphene slurry;
more specifically, the resin is one or a mixture of bisphenol A type and F type liquid epoxy resin, CYD-128 epoxy resin, novolac epoxy resin and hyperbranched epoxy resin; the anti-deposition reducing additive is one or a mixture of more of polyamide wax, a D650 thixotropic agent, a D680 thixotropic agent and a D700 thixotropic agent; the diluent is ethanol; the ultrasonic power is 1200W, the frequency is 220V 50K Hz, and the time is 1-1.5 h; the rotating speed of the high-speed dispersion is 4000-; vacuum drying at 60-deg.C + -10%, vacuum degree below 100KPa, and drying for 1-2 hr;
(3) and adding the graphene slurry into the modified conductive metal powder, adding the solvent b, performing ultrasonic dispersion, and performing vacuum drying to obtain the conductive filling powder.
More specifically, the solvent b is ethanol, and the dosage ratio of the solvent b to the modified conductive metal powder is 3-5 mL: 1g of a compound; the ultrasonic power is 1200W, the frequency is 20K Hz +/-10 percent, and the time is 1-1.5 h; the temperature of vacuum drying is 60 +/-10%, the vacuum degree is lower than 100KPa, and the drying time is 1-2 h.
The technical effect of adopting the technical scheme is as follows: carrying out ultrasonic treatment on metal powder and dilute hydrochloric acid, aiming at removing metal copper oxide generated by oxidation and eliminating the influence of the metal copper oxide on the conductivity; graphene is introduced as an auxiliary conductive filler, the sheet structure of the graphene has a large specific surface area, and the graphene is uniformly distributed around the metal conductive particles to effectively block the permeation of an oxidation medium, so that the oxidation resistance of the conductive adhesive is greatly improved, and the durability of the conductive adhesive is improved; and the graphene has good conductivity, and plays a role in bridging after the graphene is introduced into a system, so that the conductive filler is more fully contacted, the contact area and the contact probability among conductive particles are increased, and a conductive network is more stable.
Preferably, the mass ratio of the graphene to the resin to the anti-settling auxiliary agent to the diluent is 10 (63-77): (13.5-16.5): (4.5-5.5);
the mass ratio of the graphene slurry to the metal powder is (0.1-0.5): 1.
preferably, the metal powder is copper powder.
Preferably, the mass ratio of the polymer matrix resin, the metal conductive filler, the wetting dispersant, the thixotropic agent, the toughening agent and the graphene is 18.5: 70: 3: 3.5: 4: 0.5.
preferably, the polymer matrix resin is one or a mixture of bisphenol A type, F type liquid epoxy resin, CYD-128 epoxy resin, novolac epoxy resin and hyperbranched epoxy resin.
Preferably, the wetting dispersant is a mixture of one or more of triethylhexylphosphoric acid, sodium lauryl sulfate and methylpentanol.
Preferably, the thixotropic agent is a mixture of one or more of a polyamide wax, a D650 thixotropic agent, a D680 thixotropic agent, and a D700 thixotropic agent.
Preferably, the toughening agent is a mixture of one or more of carboxyl liquid nitrile rubber, carboxyl-terminated liquid nitrile rubber and polysulfide rubber.
Preferably, the curing agent is one or a mixture of cardanol modified epoxy curing agent, polyamide curing agent, dicyandiamide and acid anhydride;
the curing accelerator is one or a mixture of DMP-30, 4' -Diamino Diphenyl Sulfone (DDS) and N, N-dimethylaniline;
the solvent is one or the mixture of two of dimethylbenzene and n-butyl alcohol.
The invention also provides a preparation method of the long-acting anti-oxidation high-conductivity conductive adhesive, which comprises the following steps:
s1, carrying out water removal treatment on the polymer matrix resin, adding a wetting dispersant, a thixotropic agent, a toughening agent and graphene, grinding until the components are uniformly dispersed, then adding conductive filler powder step by step, and continuously grinding until the components are uniformly dispersed to obtain a component A;
more specifically, the water removal treatment is drying at the temperature of 110-120 ℃ for 2-3h, the grinding is manual grinding, the grinding time is 5-10min, and the continuous grinding time is 0.5-1 h.
S2, uniformly mixing the solvent, the curing agent and the curing accelerator to obtain a component B;
s3, uniformly mixing the component A obtained in the step S1 with the component B obtained in the step S2 to obtain the long-acting anti-oxidation high-conductivity conductive adhesive.
According to the technical scheme, compared with the prior art, the long-acting anti-oxidation conductive adhesive with high conductivity disclosed by the invention has the following beneficial effects:
(1) graphene is introduced into the long-acting anti-oxidation high-conductivity conductive adhesive as an auxiliary conductive filler, the graphene has a very large specific surface area due to a flaky structure of the graphene, and the graphene is uniformly distributed around metal conductive particles to effectively block the permeation of an oxidation medium, so that the anti-oxidation performance of the conductive adhesive is greatly improved, and the durability of the conductive adhesive is improved; and the graphene has good conductivity, and plays a role in bridging after the graphene is introduced into a system, so that the conductive filler is more fully contacted, the contact area and the contact probability among conductive particles are increased, and a conductive network is more stable.
(2) In the process of preparing the conductive filler, the conductive adhesive A component is in a paste shape, the uniformity of the whole system can be improved by an ultrasonic dispersion process, and the graphene with the functions of blocking and conducting can prevent the metal filler from being oxidized in the conductive adhesive system, so that the stability of the whole conductive adhesive system can be ensured to a great extent, and the conductive adhesive is convenient to store in a natural environment for a long time after being hermetically stored.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise specified, the reagents and materials used in the present invention are commercially available products or products obtained by a known method.
The embodiment of the invention provides a long-acting anti-oxidation high-conductivity conductive adhesive, which comprises a component A and a component B, wherein the mass ratio of the component A to the component B is (10-15): 1;
the component A comprises the following raw materials in parts by weight:
the component B comprises the following raw materials in parts by weight:
10-30 parts of solvent
50-80 parts of curing agent
5-20 parts of a curing accelerator.
In order to further optimize the technical scheme, the conductive filler powder is prepared by the following steps:
(1) preparing modified conductive metal powder: adding dilute hydrochloric acid into metal powder, performing ultrasonic treatment, performing centrifugal separation, cleaning with a solvent a, and performing vacuum drying to obtain modified conductive metal powder;
more specifically, the concentration of the dilute hydrochloric acid is 5-7%, and the dosage ratio of the dilute hydrochloric acid to the metal powder is as follows: the diluted hydrochloric acid needs to completely submerge 3-5mL of metal powder: 1g of a compound; the ultrasonic power is 1200W, the frequency is within the range of 220V 20K Hz +/-10 percent, and the time is 1-2 h; the rotational speed of centrifugation is 4000-; the solvent a is absolute ethyl alcohol, and is washed for 3 to 5 times; the temperature of vacuum drying is 110-120 ℃, the vacuum degree is lower than 100KPa, and the drying time is 2-4 h;
(2) preparing graphene slurry: sequentially adding resin, an anti-settling auxiliary agent and a diluent into the graphene powder, dispersing at a high speed after ultrasonic dispersion, completely and uniformly mixing a system, and drying in vacuum to obtain graphene slurry;
more specifically, the resin is one or a mixture of bisphenol A type and F type liquid epoxy resin, CYD-128 epoxy resin, novolac epoxy resin and hyperbranched epoxy resin; the anti-deposition reducing additive is one or a mixture of more of polyamide wax, a D650 thixotropic agent, a D680 thixotropic agent and a D700 thixotropic agent; the diluent is ethanol; the ultrasonic power is 1200W, the frequency is 220V 50K Hz, and the time is 1-1.5 h; the rotating speed of the high-speed dispersion is 4000-; vacuum drying at 60-deg.C + -10%, vacuum degree below 100KPa, and drying for 1-2 hr;
(3) and adding the graphene slurry into the modified conductive metal powder, adding the solvent b, performing ultrasonic dispersion, and performing vacuum drying to obtain the conductive filling powder.
More specifically, the solvent b is ethanol, and the dosage ratio of the solvent b to the modified conductive metal powder is 3-5 mL: 1g of a compound; the ultrasonic power is 1200W, the frequency is 20K Hz +/-10 percent, and the time is 1-1.5 h; the temperature of vacuum drying is 60 +/-10%, the vacuum degree is lower than 100KPa, and the drying time is 1-2 h.
In order to further optimize the technical scheme, the mass ratio of the graphene to the resin to the anti-settling auxiliary agent to the diluent is 10 (63-77): (13.5-16.5): (4.5-5.5);
the mass ratio of the graphene slurry to the metal powder is (0.1-0.5): 1.
in order to further optimize the technical scheme, the metal powder is copper powder.
In order to further optimize the above solution, the polymer matrix resin: the mass ratio of the metal conductive filler to the wetting dispersant to the thixotropic agent to the toughening agent to the graphene is 18.5: 70: 3: 3.5: 4: 0.5.
in order to further optimize the technical scheme, the polymer matrix resin is one or a mixture of bisphenol A type and F type liquid epoxy resin, CYD-128 epoxy resin, novolac epoxy resin and hyperbranched epoxy resin.
In order to further optimize the technical scheme, the wetting dispersant is one or more of triethyl hexyl phosphoric acid, sodium dodecyl sulfate and methyl amyl alcohol.
In order to further optimize the technical scheme, the thixotropic agent is a mixture of one or more of polyamide wax, a D650 thixotropic agent, a D680 thixotropic agent and a D700 thixotropic agent;
the toughening agent is one or a mixture of more of carboxyl liquid nitrile rubber, carboxyl-terminated liquid nitrile rubber and polysulfide rubber.
In order to further optimize the technical scheme, the curing agent is one or a mixture of more of cardanol modified epoxy curing agent, polyamide curing agent, dicyandiamide and acid anhydride;
the curing accelerator is one or a mixture of DMP-30, 4' -Diamino Diphenyl Sulfone (DDS) and N, N-dimethylaniline;
the solvent is one or the mixture of two of dimethylbenzene and n-butyl alcohol.
The invention also provides a preparation method of the long-acting anti-oxidation high-conductivity conductive adhesive, which comprises the following steps:
s1, carrying out water removal treatment on the polymer matrix resin, adding a wetting dispersant, a thixotropic agent, a toughening agent and graphene, grinding until the components are uniformly dispersed, then adding conductive filler powder step by step, and continuously grinding until the components are uniformly dispersed to obtain a component A;
more specifically, the water removal treatment is drying at the temperature of 110-120 ℃ for 2-3h, the grinding is manual grinding, the grinding time is 5-10min, and the continuous grinding time is 0.5-1 h.
S2, uniformly mixing the solvent, the curing agent and the curing accelerator to obtain a component B;
s3, uniformly mixing the component A obtained in the step S1 with the component B obtained in the step S2 to obtain the long-acting anti-oxidation high-conductivity conductive adhesive.
Example 1
The embodiment provides a long-acting anti-oxidation high-conductivity conductive adhesive which comprises a component A and a component B, wherein the mass ratio of the component A to the component B is 15:1, and the component A comprises the following raw materials in parts by weight: 13 parts of bisphenol A epoxy resin and 79.5 parts of metal conductive filler; 4 parts of carboxyl-terminated liquid nitrile rubber, 1 part of triethylhexyl phosphoric acid, 2 parts of D680 thixotropic agent and 0.5 part of graphene; the component B comprises the following raw materials in parts by weight: 70 parts of polyamide curing agent, 10 parts of DDS, 20.5 parts of dimethylbenzene and 0.5 part of n-butyl alcohol;
the preparation process of the long-acting anti-oxidation high-conductivity conductive adhesive comprises the following steps:
1): the preparation method of the graphene slurry comprises the following steps: weighing 10g of graphene powder, adding hyperbranched epoxy resin, a D650 thixotropic agent and ethanol, ultrasonically dispersing for 1h under the ultrasonic power of 1200W and the frequency of 220V 50K Hz, then transferring to disperse for 1h at a high speed of 4000 plus 6000r/min, and completely and uniformly mixing the system. And then transferring to vacuum (the vacuum degree is lower than 100KPa) at 60 ℃ for drying for 1h to remove the solvent, so as to obtain the graphene slurry with high solid content, which is convenient for later-stage dispersion.
S2: the preparation method of the metal conductive filler comprises the following steps: adding excessive dilute hydrochloric acid into conductive copper powder, placing the conductive copper powder in an ultrasonic environment for treatment for 1-2h, wherein the ultrasonic power is 1200W, the frequency is 220V 20K Hz +/-10%, then placing the conductive copper powder in a centrifuge device for centrifugation for 1 time, the centrifugation rotation speed is 4000-;
s3: adding 0.1 part of graphene slurry relative to the mass of copper powder into the modified conductive copper powder, adding excessive ethanol to completely cover the solid, and then transferring to ultrasonic dispersion for 1h, wherein the ultrasonic power is 1200W, the frequency is 20K Hz +/-10%, and drying and removing the ethanol in vacuum (the vacuum degree is lower than 100KPa) at the temperature of 60 ℃ to obtain conductive copper powder coated with a small amount of graphene as a conductive filler for later use;
s4: taking 20g of bisphenol A type resin matrix, placing the bisphenol A type resin matrix in an environment with the temperature of 110 ℃, and drying for 2h to remove water;
s5: grinding is used as a conductive adhesive dispersion process, 4g of carboxyl-terminated liquid nitrile rubber, 1 part of triethylhexyl phosphoric acid, 2 parts of D680 thixotropic agent and 0.3 part of graphene are added into 13g of bisphenol A resin, and the mixture is manually ground for 5-10 min;
s6: adding 79.3g of conductive filler into the material of S5 step by step, continuously grinding for 0.5 g until the components are uniformly dispersed to obtain a component A, and sealing at normal temperature for later use;
s7: 70 parts of polyamide curing agent, 10 parts of DDS, 20.5 parts of dimethylbenzene and 0.5 part of n-butyl alcohol to obtain a component B, and sealing the component B at normal temperature for later use.
When in use, the components A and B are mixed according to the mass ratio of 15:1 to obtain the polymer-based conductive adhesive.
Comparative example 1
The conductive adhesive and the preparation method of the comparative example are basically the same as those of the example 1, and the difference is only that: graphene is not added in the component A.
Comparative example 2
The conductive adhesive and the preparation method of the comparative example are basically the same as those of the example 1, and the difference is only that: the conductive filler in the component A is not coated with graphene.
Comparative example 3
The conductive adhesive and the preparation method of the comparative example are basically the same as those of the example 1, and the difference is only that: the conductive filler in the component A is not coated with graphene, and graphene is not added.
To further illustrate the technical effects of the present invention, the conductive paste obtained in example 1 and comparative examples 1 to 3 was subjected to a performance test, which included the following:
test method of conductivity: testing the volume resistivity of the conductive adhesive sample: QJ 1523-88 conductive adhesive resistivity test method;
the method for testing the oxidation resistance of the conductive adhesive comprises the following steps: and (3) processing the conductive adhesive in a 10% hydrochloric acid environment, a 10% sodium hydroxide environment, a neutral salt spray environment and an ultraviolet aging environment for 1000h, and observing the conductivity change condition of the conductive adhesive.
The conductive adhesive bars prepared in example 1 and comparative examples 1 to 3 were completely cured and then tested for resistivity, recorded as the volume resistivity of the bars at 0h of cure, and then the bars were subjected to different environments for 1000h and then tested for volume resistivity, the results of which are shown in table 1.
Table 1 comparison of resistivity of conductive pastes of example 1 and comparative examples 1 to 3
As is clear from the data in the table, it can be seen that the conductive paste of example 1 is excellent in conductivity at 0h, and can reach 10-4The resistivity value of Ω · cm, while that of comparative example 1, the resistivity of the conductive paste made of the metal filler without any treatment is an order of magnitude higher than that of example 1; after the conductive adhesive is placed in a natural environment for 1000 hours, the conductivity of the conductive adhesive of the embodiment 1 is basically not changed; after treatment in each environment, the resistivity is only changed in a numerical value, and the change of magnitude order is not generated, because in the embodiment 1, the graphene is uniformly distributed around the conductive copper powder, so that the oxidation medium is effectively blocked, the oxidation resistance of the conductive adhesive is greatly improved, the influence on the conductivity of the conductive adhesive due to the corrosion of the conductive filler is avoided, and the self long-acting oxidation resistance is realized; and the graphene has good conductivity, and after the graphene is introduced, except the direct contact between copper and copper, the possibility that metal powder particles which are not in direct contact are communicated with each other is increased, namely, a bridge is erected among the metal particles, so that the contact mode of the conductive filler is diversified, the contact area is enlarged, and the conductive network is more stable. The conductive adhesive of comparative example 1 has a greatly reduced resistivity of 10 after standing for 1000h in a natural environment-1Omega cm, other environmental treatments are more severe. The method for coating the graphene on the surface of the copper powder and filling the graphene in a system has the advantages that the conductivity is superior to that of a pure metal filler, and the environment resistance is greatly superior to that of the pure metal filler.
Compared with the conductive performance of the conductive adhesive in the embodiment 1 and the comparative example 2, the conductive performance and the stability of the embodiment are good; comparative example 3 after graphene is introduced into the system, the contact mode of the conductive filler can be diversified, and the contact area is enlarged. Therefore, the conductivity is improved, but the metal particles are easy to oxidize, the conductivity is still reduced after the metal particles are placed in a natural environment for 1000 hours, and the conductivity is reduced more seriously through various environmental treatments to 10-2In the order of Ω · cm.
Compared with the conductive performance of the conductive adhesive in the embodiment 1 and the comparative example 3, the conductive performance and the stability of the embodiment are good; comparative example 3 in MetalAfter the surface of the conductive filler is coated with graphene, the metal particles can be prevented from being easily oxidized, but because gaps exist and the conductive network is unstable after the conductive filler is contacted between systems, the conductivity is reduced to 10 after 1000 hours-2In the order of Ω · cm.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. The long-acting anti-oxidation high-conductivity conductive adhesive is characterized by comprising a component A and a component B, wherein the mass ratio of the component A to the component B is (10-15): 1;
the component A comprises the following raw materials in parts by weight:
the component B comprises the following raw materials in parts by weight:
10-30 parts of solvent
50-80 parts of curing agent
5-20 parts of a curing accelerator;
the conductive filling powder is prepared by the following steps:
(1) preparing modified conductive metal powder: adding dilute hydrochloric acid into metal powder, performing ultrasonic treatment, performing centrifugal separation, cleaning with a solvent a, and performing vacuum drying to obtain modified conductive metal powder;
(2) preparing graphene slurry: sequentially adding resin, an anti-settling auxiliary agent and a diluent into the graphene powder, dispersing at a high speed after ultrasonic dispersion, completely and uniformly mixing a system, and drying in vacuum to obtain graphene slurry;
(3) adding graphene slurry into the modified conductive metal powder, adding a solvent b, performing ultrasonic dispersion, and performing vacuum drying to obtain conductive filler powder;
the mass ratio of the graphene to the resin to the anti-settling auxiliary agent to the diluent is 10 (63-77): (13.5-16.5): (4.5-5.5);
the mass ratio of the graphene slurry to the metal powder is (0.1-0.5): 1.
2. the long-acting anti-oxidation high-conductivity conductive adhesive as claimed in claim 1, wherein the metal powder is copper powder.
3. The long-acting anti-oxidation high-conductivity conductive adhesive as claimed in claim 1, wherein the mass ratio of the polymer matrix resin, the metal conductive filler, the wetting dispersant, the thixotropic agent, the toughening agent and the graphene is 18.5: 70: 3: 3.5: 4: 0.5.
4. the long-acting anti-oxidation high-conductivity conductive adhesive according to claim 1, wherein the polymer matrix resin is a mixture of one or more of bisphenol a type, F type liquid epoxy resin, CYD-128 epoxy resin, novolac epoxy resin and hyperbranched epoxy resin.
5. The long-acting anti-oxidation high-conductivity conductive adhesive as claimed in claim 1, wherein the wetting dispersant is a mixture of one or more of triethylhexylphosphoric acid, sodium dodecyl sulfate and methylpentanol.
6. The long-acting anti-oxidation high-conductivity conductive adhesive according to claim 1, wherein the thixotropic agent is a mixture of one or more of polyamide wax, a D650 thixotropic agent, a D680 thixotropic agent and a D700 thixotropic agent;
the toughening agent is one or a mixture of more of carboxyl liquid nitrile rubber, carboxyl-terminated liquid nitrile rubber and polysulfide rubber.
7. The long-acting anti-oxidation high-conductivity conductive adhesive as claimed in claim 1, wherein the curing agent is one or a mixture of cardanol modified epoxy curing agent, polyamide curing agent, dicyandiamide and acid anhydride;
the curing accelerator is one or a mixture of DMP-30, 4' -Diamino Diphenyl Sulfone (DDS) and N, N-dimethylaniline;
the solvent is one or the mixture of two of dimethylbenzene and n-butyl alcohol.
8. A method for preparing the long-acting anti-oxidation high-conductivity conductive adhesive as claimed in any one of claims 1 to 7, which is characterized by comprising the following steps:
s1, carrying out water removal treatment on the polymer matrix resin, adding a wetting dispersant, a thixotropic agent, a toughening agent and graphene, grinding until the components are uniformly dispersed, then adding conductive filler powder step by step, and continuously grinding until the components are uniformly dispersed to obtain a component A;
s2, uniformly mixing the solvent, the curing agent and the curing accelerator to obtain a component B;
s3, uniformly mixing the component A obtained in the step S1 with the component B obtained in the step S2 to obtain the long-acting anti-oxidation high-conductivity conductive adhesive.
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