CN113265210A - Adhesive with high electric and heat conductivity and preparation method thereof - Google Patents
Adhesive with high electric and heat conductivity and preparation method thereof Download PDFInfo
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- CN113265210A CN113265210A CN202110535351.2A CN202110535351A CN113265210A CN 113265210 A CN113265210 A CN 113265210A CN 202110535351 A CN202110535351 A CN 202110535351A CN 113265210 A CN113265210 A CN 113265210A
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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
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/08—Macromolecular additives
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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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- 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
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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
- C08K2201/001—Conductive additives
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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
- C08K2201/002—Physical properties
- C08K2201/005—Additives being defined by their particle size in general
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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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
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Abstract
The invention discloses an adhesive with high electric and heat conductivity and a preparation method thereof. The conductive adhesive comprises the following components in parts by weight: 5-10 parts of epoxy resin, 0.5-2 parts of toughening agent, 3-5 parts of curing agent, 0.03-0.06 part of curing accelerator, 0.05-0.2 part of coupling agent, 0.1-0.5 part of thixotropic agent, 3-8 parts of solvent and 82-96 parts of conductive filler, wherein the conductive filler is silver powder, the tap density is 3-6 g/cc, and the average particle size is 2-5 mu m. By applying the technical scheme of the invention, the formula is based on epoxy resin, and silver powder with different particle sizes is used as the conductive filler to prepare the high-heat-conductivity materialThe conductive adhesive has good conductivity and mechanical property; the heat conductivity is more than 10W/m.k, and the heat conductivity coefficient is more than 4 times of that of the conventional conductive adhesive at present; volume resistivity of less than 9 x 10‑5Omega cm; the shear force is greater than 10 Kgf.
Description
Technical Field
The invention relates to the technical field of binders, in particular to an adhesive with high electric and heat conductivity and a preparation method thereof.
Background
The conductive adhesive is an adhesive with both electric conduction and bonding functions, and is generally applied to bonding in the fields of chips, integrated circuits, high-power LEDs, electronic components and the like. Compared with the traditional Sn/Pb solder, the conductive adhesive has the advantages of simple preparation process, low curing temperature, good mechanical property and environmental friendliness, and the conductive adhesive used for replacing the traditional Sn/Pb solder has become a trend and also becomes a key material in the field of electronic packaging and is more and more widely accepted.
At present, the heat conductivity coefficient of the conductive adhesive in the market is generally below 5W/m.k, and the volume resistivity is 5 multiplied by 10-4Around Ω · cm, which still cannot meet the requirements for some high power devices.
Moreover, the high-thermal-conductivity and electric-conductivity adhesives on the market mostly use nano silver wires or reduced silver prepared by chemical preparation and micron silver powder mixed together as electric-conductivity fillers, wherein the process is relatively complex, the cost is high, and the production process is long and the efficiency is low.
Disclosure of Invention
The invention aims to provide an adhesive with high electric and heat conductivity and a preparation method thereof, and provides an electric conductive adhesive with good electric conductivity and mechanical property.
In order to achieve the above object, according to one aspect of the present invention, there is provided an electrically conductive adhesive. The conductive adhesive comprises the following components in parts by weight: 5-10 parts of epoxy resin, 0.5-2 parts of toughening agent, 3-5 parts of curing agent, 0.03-0.06 part of curing accelerator, 0.05-0.2 part of coupling agent, 0.1-0.5 part of thixotropic agent, 3-8 parts of solvent and 82-96 parts of conductive filler, wherein the conductive filler is silver powder, the tap density is 3-6 g/cc, and the average particle size is 2-5 mu m.
Further, the silver powder comprises one or more of 50-100 nm nanometer silver powder, 1-5 mu m sheet silver powder, 1-5 mu m spherical silver powder, 6-10 mu m sheet silver powder, 6-10 mu m spherical silver powder, 10-15 mu m sheet silver powder and 10-15 mu m spherical silver powder.
Further, the silver powder has a tap density of 5.5 to 6g/cc and an average particle diameter of 2 to 3 μm.
Further, the conductive adhesive also comprises an antioxidant and/or a dispersant.
Further, the epoxy resin is one of bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, novolac epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin or glycidyl amine type epoxy resin; preferably, the epoxy resin comprises a multifunctional epoxy resin, and the multifunctional epoxy resin is one or more of trimethylolethane triglycidyl ether, ethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, or epoxidized m-xylylenediamine.
Furthermore, the epoxy resin is modified by one or more of polyether polyol, core-shell toughening agent, polyimide and organic silicon epoxy resin.
Further, the toughening agent is one or more of a core-shell toughening agent, carboxyl-terminated butadiene-acrylonitrile rubber or polysulfide rubber; the curing agent is one or more of benzophenonetetracarboxylic dianhydride, methyl nadic anhydride, methyl hexahydrophthalic anhydride or tetrahydrophthalic anhydride; the curing accelerator is one or more of 2-ethyl 4-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, benzyl dimethylamine or triethylamine; the coupling agent is one or more of KH560, KH550, KH792 or DL 602; the thixotropic agent is fumed silica or organic bentonite; the solvent is one or more of terpineol, ethylene glycol butyl ether acetate, benzyl alcohol, propylene glycol methyl ether acetate or dibasic ester.
Further, the conductive adhesive also comprises a silver powder surface treating agent, and preferably, the silver powder surface treating agent is adipic acid.
According to another aspect of the invention, a preparation method of the conductive adhesive is provided. The preparation method comprises the following steps: uniformly dispersing epoxy resin, a toughening agent, a curing accelerator, a coupling agent, a thixotropic agent, a solvent and a conductive filler to prepare a conductive adhesive; preferably, the preparation method further comprises an addition step of the silver powder surface treatment agent.
According to another aspect of the invention, the application of the conductive adhesive in electronic packaging is provided.
By applying the technical scheme of the invention, the high-thermal-conductivity and high-electric-conductivity adhesive is prepared by using the silver powders with different particle sizes as the electric conductive filler based on the epoxy resin, and has good electric conductivity and mechanical properties; the heat conductivity is more than 10W/m.k, and the heat conductivity coefficient is more than 4 times of that of the conventional conductive adhesive at present; volume resistivity of less than 9 x 10-5Omega cm; the shear force is greater than 10 Kgf. The epoxy resin and the curing agent are combined, so that the viscosity of a system can be reduced, the discharge of bubbles is facilitated, the colloid compactness is improved, the lap joint between filler interfaces is promoted, and the electric conduction and heat conduction performance is improved; the toughening agent improves the mechanical property of the adhesive.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
In view of the technical problems described in the background of the invention, the following technical solutions are proposed.
According to an exemplary embodiment of the present invention, an electrically conductive adhesive is provided. The conductive adhesive comprises the following components in parts by weight: 5-10 parts of epoxy resin, 0.5-2 parts of toughening agent, 3-5 parts of curing agent, 0.03-0.06 part of curing accelerator, 0.05-0.2 part of coupling agent, 0.1-0.5 part of thixotropic agent, 3-8 parts of solvent and 82-96 parts of conductive filler, wherein the conductive filler is silver powder, the tap density of the silver powder is 3-6 g/cc, and the average particle size is 2-5 μm (for example, the particle size distribution can be 100-15 μm).
By applying the technical scheme of the invention, the high-thermal-conductivity and electric-conductivity adhesive is prepared by taking silver powders with different particle sizes and specific tap densities as electric-conductivity fillers based on epoxy resin, and has good electric conductivity and mechanical properties; the heat conductivity is more than 10W/m.k, and the heat conductivity coefficient is more than 4 times of that of the conventional conductive adhesive at present; volume resistivity of less than 9 x 10-5Omega cm; the shear force is greater than 10 Kgf. Wherein, the combination of the epoxy resin and the curing agent can reduce the viscosity of the system, is beneficial to discharging air bubbles, improves the compactness of colloid and promotes fillingThe lap joint between material interfaces improves the electric conduction and heat conduction performance; the toughening agent improves the mechanical property of the adhesive.
The inventor of the invention finds that in order to further improve the performance of the conductive adhesive, preferably, the silver powder comprises one or more of 50-100 nm nanometer silver powder, 1-5 μm flake silver powder, 1-5 μm spherical silver powder, 6-10 μm flake silver powder, 6-10 μm spherical silver powder, 10-15 μm flake silver powder and 10-15 μm spherical silver powder. More preferably, the silver powder has a tap density of 5.5 to 6g/cc and an average particle diameter of 2 to 3 μm.
In order to further improve the oxidation resistance and the like of the conductive adhesive, in a typical embodiment of the present invention, the conductive adhesive further includes an antioxidant and/or a dispersant.
In a typical embodiment of the present invention, the epoxy resin is one of a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a novolac epoxy resin, an alicyclic epoxy resin, an aliphatic epoxy resin, or a glycidylamine type epoxy resin. In order to further improve the performance of the conductive adhesive, preferably, the epoxy resin comprises a multifunctional epoxy resin, and the multifunctional epoxy resin is one or more of trimethylolethane triglycidyl ether, ethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester or epoxidized m-xylylenediamine. Preferably, when the epoxy resin is modified by one or more of polyether polyol, a core-shell toughening agent, polyimide and organic silicon epoxy resin, the performance index of the conductive adhesive is further improved.
According to a typical embodiment of the invention, the toughening agent is one or more of a core-shell toughening agent, carboxyl-terminated butadiene-acrylonitrile rubber or polysulfide rubber; the curing agent is one or more of benzophenonetetracarboxylic dianhydride, methyl nadic anhydride, methyl hexahydrophthalic anhydride or tetrahydrophthalic anhydride; the curing accelerator is one or more of 2-ethyl 4-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, benzyl dimethylamine or triethylamine; the coupling agent is one or more of KH560, KH550, KH792 or DL 602; the thixotropic agent is fumed silica or organic bentonite; the solvent is one or more of terpineol, ethylene glycol butyl ether acetate, benzyl alcohol, propylene glycol methyl ether acetate or dibasic ester.
In order to further improve the performance of the conductive adhesive, the toughening agent of the invention can also comprise a silver powder surface treatment agent, and preferably, the silver powder surface treatment agent is adipic acid.
According to another aspect of the invention, a preparation method of the conductive adhesive is provided. The preparation method comprises the following steps: uniformly dispersing epoxy resin, a toughening agent, a curing accelerator, a coupling agent, a thixotropic agent, a solvent and a conductive filler to prepare a conductive adhesive; preferably, the preparation method further comprises an addition step of the silver powder surface treatment agent.
According to another aspect of the invention, the application of the conductive adhesive in electronic packaging is provided.
The following examples are provided to further illustrate the advantageous effects of the present invention.
Example 1
Firstly, premixing a resin matrix, taking 2.7g of bisphenol A type epoxy resin, adding 0.3g of polyether polyol, and carrying out polyether toughening modification. Adding 0.75g of polyfunctional epoxy resin (trimethylolethane triglycidyl ether), 0.75g of core-shell toughening agent to toughen and modify the epoxy resin, grinding for 10 minutes to obtain a uniformly dispersed resin matrix, adding 3g of anhydride curing agent (benzophenone tetracarboxylic dianhydride), 0.04g of imidazole accelerator (2-ethyl 4-methylimidazole), 0.02g of coupling agent (KH560) and 0.04g of thixotropic agent (fumed silica), grinding for 10 minutes, performing ultrasonic dispersion to uniformly mix an auxiliary agent and the resin, mechanically vacuumizing and defoaming for 30 minutes, taking out a reaction cup to obtain an organic mixture, adding 30g of flaky silver powder with the average particle size of 3 mu m and the tap density of 6g/cc, 6g of flaky silver powder with the average particle size of 10 mu m and the tap density of 3g/cc, 1g of spherical silver powder conductive filler with the particle size of 50-100 nm and 1.5g of solvent terpineol, and fully mixing the organic mixture, and stirring for 10 minutes by a planet to disperse and defoam to obtain the high-heat-conductivity and electric-conductivity adhesive.
Example 2
Firstly, premixing a resin matrix, taking 0.9g of phenolic epoxy resin, 1.8g of bisphenol A type epoxy resin and adding 0.3g of polyether polyol, and toughening and modifying polyether. Adding 0.75g of polyfunctional epoxy resin (cyclohexyl dimethanol diglycidyl ether), 0.75g of core-shell toughening agent to toughen and modify the epoxy resin, grinding for 10 minutes to obtain a uniformly dispersed resin matrix, adding 3g of anhydride curing agent (tetrahydrophthalic anhydride), 0.4g of imidazole accelerator (2-methylimidazole), 0.2g of coupling agent (KH550) and 0.04g of thixotropic agent (organic bentonite), grinding for 10 minutes, ultrasonically dispersing to uniformly mix the auxiliary agent and the resin, mechanically vacuumizing and defoaming for 30 minutes, taking out a reaction cup to obtain an organic mixture, adding 42g of spherical silver powder with the average particle size of 2 mu m and the tap density of 6g/cc, flaky silver powder with the average particle size of 6 mu m and the tap density of 6g of 4.5g/cc, flaky silver powder with the average particle size of 10 mu m and the tap density of 3g/cc and 1.5g of solvent propylene glycol monomethyl ether acetate, 0.05g of silver powder surface treating agent (adipic acid) is fully mixed with the organic mixture, ground for 15-30 minutes, and dispersed and defoamed for 10 minutes by using a planetary gravity mixer to obtain the high-thermal-conductivity and electric-conductivity adhesive.
Example 3
Firstly, premixing a resin matrix, taking 2.7g of bisphenol S type epoxy resin, adding 0.3g of polyether polyol, and carrying out polyether toughening modification. Adding 0.75g of polyfunctional epoxy resin (ethylene glycol diglycidyl ether), 0.75g of core-shell toughening agent to toughen and modify the epoxy resin, grinding for 10 minutes to obtain a uniformly dispersed resin matrix, adding 3g of anhydride curing agent (methylhexahydrophthalic anhydride), 0.03g of imidazole accelerator (1-benzyl-2-methylimidazole), 0.02g of coupling agent (KH792) and 0.1g of thixotropic agent (fumed silica), grinding for 10 minutes, performing ultrasonic dispersion to uniformly mix an auxiliary agent and the resin, mechanically vacuumizing and defoaming for 30 minutes, taking out a reaction cup to obtain an organic mixture, adding 70g of flake silver powder conductive filler (namely micron silver powder) with the average particle size of 3 mu m and the tap density of 6g/cc, 6.5g of solvent ethylene glycol butyl ether acetate and 0.05g of silver powder surface treatment agent, fully mixing with the organic mixture, grinding for 15-30 minutes, and dispersing and defoaming for 10 minutes by using a planetary gravity mixer to obtain the high-thermal-conductivity and high-electric-conductivity adhesive.
Example 4
The same as in example 3, except that the silver powder was 40g of the plate-like silver powder conductive filler having an average particle diameter of 4 μm and a tap density of 4 g/cc.
Example 5
The same as in example 3, except that the silver powder was 50.5g of the plate-like silver powder conductive filler having an average particle diameter of 4 μm and a tap density of 5 g/cc.
Example 6
The same as in example 3, except that the silver powder was 60g of the plate-like silver powder conductive filler having an average particle diameter of 4 μm and a tap density of 5.5 g/cc.
Example 7
The same as in example 3 except that the silver powder was 70g of a plate-like silver powder conductive filler having an average particle diameter of 4 μm and a tap density of 5.5 g/cc;
example 8
The same as example 3, except that: firstly, premixing a resin matrix, taking 2.7g of bisphenol A type epoxy resin, adding 0.3g of polyether polyol, and carrying out polyether toughening modification. 0.75g of polyfunctional epoxy resin (trimethylolethane triglycidyl ether) and 1.5g of core-shell toughening agent are added to toughen and modify the epoxy resin, the epoxy resin is ground for 10 minutes to obtain a uniformly dispersed resin matrix, and 5g of anhydride curing agent (benzophenonetetracarboxylic dianhydride), 0.06g of imidazole accelerator (2-ethyl 4-methylimidazole), 0.1g of coupling agent (KH560) and 0.2g of thixotropic agent (fumed silica) are added and ground for 10 minutes.
Example 9
The same as example 3, except that: firstly, premixing a resin matrix, taking 2.7g of bisphenol A type epoxy resin, adding 0.3g of polyether polyol, and carrying out polyether toughening modification. 0.75g of polyfunctional epoxy resin (trimethylolethane triglycidyl ether) and 2g of core-shell toughening agent are added to toughen and modify the epoxy resin, the epoxy resin is ground for 10 minutes to obtain a uniformly dispersed resin matrix, and then 3g of anhydride curing agent (benzophenone tetracarboxylic dianhydride), 0.03g of imidazole accelerator (2-ethyl 4-methylimidazole), 0.05g of coupling agent (KH560) and 0.5g of thixotropic agent (fumed silica) are added to grind for 10 minutes.
The high thermal conductivity and electric conductivity adhesive prepared in the embodiment is subjected to performance test, and the specific test method is as follows:
(1) volume resistivity test
To determine the volume resistivity of the conductive adhesive, samples were prepared using a 2.54cm by 7.62cm glass slide. The holder holding the slide has two score lines parallel to the long side and spaced 2.54mm apart to serve as a control base line for application of two strips of tape. The thickness of the adhesive tape is 0.1mm, and no wrinkles or bubbles are formed on the surface of the adhesive tape after the adhesive tape is pasted. The slides should be cleaned with ethanol and blown dry with air. And placing a proper amount of conductive adhesive in the area between the two adhesive tapes. A single-sided blade was used to maintain a 30 degree nip between the slide surface and the blade to squeeze the material between the two strips of scotch tape. The transparent tape used is at least 6.35cm long. The tape was then peeled off and the conductive adhesive cured according to the curing process recommended in the product specification. After curing the sample should be allowed to cool to room temperature.
The resistance was measured using a dedicated four-probe test fixture and milliohmmeter. The four contact probes fix and stabilize the contact conductive adhesive, so that the distance between the two current contact probes is 5.08cm, the two voltage contact probes are positioned between the current contact probes, and the distance between the voltage contact probe and the adjacent current contact probe is 1.27 cm. A four probe fixture was placed on the conductive gel sample piece at 25 ℃ to ensure electrical contact between each probe and the material. The measured resistance values (in ohms) were recorded and the resistivity was calculated using equation (1):
in the formula:
ρ -resistivity, Ω · μm;
r-resistance measurement, Ω;
w is sample width, mm;
t-sample thickness (equal to the total thickness of material plus glass slide, the value of the sensory metric minus the thickness of the glass slide), μm;
l-distance between the two middle probes (i.e. the two probes measuring the voltage), mm.
The detection results are shown in Table 1
TABLE 1
| Test items | Example 1 | Example 2 | Example 3 |
| Volume resistivity omega cm | 9.0×10-5 | 5.6×10-5 | 1.5×10-5 |
| Test items | Example 4 | Example 5 | Example 6 |
| Volume resistivity omega cm | 8.2×10-5 | 5.5×10-5 | 3.2×10-5 |
| Test items | Example 7 | Example 8 | Example 9 |
| Volume resistivity omega cm | 4.7×10-5 | 2.6×10-5 | 2.0×10-5 |
(2) Test of Heat conductivity
And measuring the thermal diffusivity or the thermal conductivity by using the GB/T22588-2008 flash method. Grinding the cured heat conduction sample into a cylinder with flat upper and lower surfaces, a diameter of about 12mm and a thickness of more than 1mm, performing carbon spraying treatment on the surface of the sample, measuring a thermal diffusion system of the sample by using a flash method heat conduction instrument, measuring a specific heat capacity of the sample by using a differential scanning calorimeter, measuring a density of the sample by using a densimeter, and calculating to obtain the heat conductivity (heat conductivity is thermal diffusion coefficient, specific heat capacity, density) of the sample. The results are shown in Table 2.
TABLE 2
| Test items | Example 1 | Example 2 | Example 3 |
| Coefficient of thermal conductivity W/m.k | 12.6 | 16.3 | 25.5 |
| Test items | Example 4 | Example 5 | Example 6 |
| Coefficient of thermal conductivity W/m.k | 13.2 | 16.7 | 23.6 |
| Test items | Example 7 | Example 8 | Example 9 |
| Coefficient of thermal conductivity W/m.k | 24.5 | 20.4 | 22.7 |
(3) Chip shear force testing
And (3) testing at 25 ℃, and adopting equipment meeting the requirements in the shear strength of the GJB 548B-2005 method 2019.2 chip. Using 0.2cm2The gold-plated Kovar sheet is a sample with a thickness of about 20 μm, wherein 5 silicon-based chips with the size of 2mm multiplied by 2mm are adhered on a substrate. And testing the shear strength of the chip by using a push-pull force tester, and taking the average value of 5 test data as the chip shear strength of the conductive adhesive.
TABLE 3
| Test items | Example 1 | Practice ofExample 2 | Example 3 |
| Shear strength of chip kgf | 22.1 | 15.6 | 12.2 |
| Test items | Example 4 | Example 5 | Example 6 |
| Shear strength of chip kgf | 16.7 | 15.3 | 13.8 |
| Test items | Example 7 | Example 8 | Example 9 |
| Shear strength of chip kgf | 12.3 | 14.4 | 13.5 |
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: by applying the technical scheme of the invention, the high-thermal-conductivity and high-electric-conductivity adhesive is prepared by using the silver powders with different particle sizes as the electric conductive filler based on the epoxy resin, and has good electric conductivity and mechanical properties; the heat conductivity is more than 10W/m.k, and the heat conductivity coefficient is more than 4 times of that of the conventional conductive adhesive at present; volume resistanceThe rate is lower than 9 x 10-5Omega cm; the shear force is greater than 10 Kgf.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The conductive adhesive is characterized by comprising the following components in parts by weight: 5-10 parts of epoxy resin, 0.5-2 parts of toughening agent, 3-5 parts of curing agent, 0.03-0.06 part of curing accelerator, 0.05-0.2 part of coupling agent, 0.1-0.5 part of thixotropic agent, 3-8 parts of solvent and 82-96 parts of conductive filler, wherein the conductive filler is silver powder, the tap density of the silver powder is 3-6 g/cc, and the average particle size is 2-5 mu m.
2. The conductive adhesive according to claim 1, wherein the silver powder comprises one or more of 50 to 100nm nano silver powder, 1 to 5 μm plate-like silver powder, 1 to 5 μm spherical silver powder, 6 to 10 μm plate-like silver powder, 6 to 10 μm spherical silver powder, 10 to 15 μm plate-like silver powder, and 10 to 15 μm spherical silver powder.
3. The electrically conductive adhesive according to claim 1, wherein the silver powder has a tap density of 5.5 to 6g/cc and an average particle diameter of 2 to 3 μm.
4. The electrically conductive adhesive of claim 1, further comprising an antioxidant and/or a dispersant.
5. The conductive adhesive according to claim 1, wherein the epoxy resin is one of bisphenol a epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, novolac epoxy resin, alicyclic epoxy resin, aliphatic epoxy resin, or glycidyl amine epoxy resin;
preferably, the epoxy resin comprises a multifunctional epoxy resin, and the multifunctional epoxy resin is one or more of trimethylolethane triglycidyl ether, ethylene glycol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, 4, 5-epoxycyclohexane-1, 2-dicarboxylic acid diglycidyl ester, or epoxidized m-xylylenediamine.
6. The electrically conductive adhesive of claim 5, wherein the epoxy resin is modified with one or more of polyether polyol, core-shell toughener, polyimide, and silicone epoxy resin.
7. The conductive adhesive of claim 1, wherein the toughening agent is one or more of a core-shell toughening agent, carboxyl-terminated butadiene-acrylonitrile rubber or polysulfide rubber; the curing agent is one or more of benzophenonetetracarboxylic dianhydride, methyl nadic anhydride, methyl hexahydrophthalic anhydride or tetrahydrophthalic anhydride; the curing accelerator is one or more of 2-ethyl 4-methylimidazole, 2-methylimidazole, 1-benzyl-2-methylimidazole, benzyl dimethylamine or triethylamine; the coupling agent is one or more of KH560, KH550, KH792 or DL 602; the thixotropic agent is fumed silica or organic bentonite; the solvent is one or more of terpineol, ethylene glycol butyl ether acetate, benzyl alcohol, propylene glycol methyl ether acetate or dibasic ester.
8. The conductive adhesive according to claim 1, further comprising a silver powder surface treatment agent, preferably, the silver powder surface treatment agent is adipic acid.
9. The preparation method of the conductive adhesive according to any one of claims 1 to 8, comprising the following steps: uniformly dispersing epoxy resin, a toughening agent, a curing accelerator, a coupling agent, a thixotropic agent, a solvent and a conductive filler to prepare the conductive adhesive;
preferably, the preparation method further comprises an addition step of a silver powder surface treatment agent.
10. Use of the electrically conductive adhesive of any one of claims 1 to 8 in electronic packaging.
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| CN113930202A (en) * | 2021-11-25 | 2022-01-14 | 苏州锐朗新材料有限公司 | Low-temperature semi-sintered conductive and heat-conductive adhesive and preparation method thereof |
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| CN114210597A (en) * | 2022-02-22 | 2022-03-22 | 深圳市正和兴电子有限公司 | Conductive adhesive recommendation method and system for semiconductor device and readable storage medium |
| CN114989762A (en) * | 2022-06-29 | 2022-09-02 | 东莞市德聚胶接技术有限公司 | Conductive adhesive for single-component semiconductor and preparation method thereof |
| CN115910427A (en) * | 2023-01-16 | 2023-04-04 | 北京中科纳通电子技术有限公司 | Preparation method of PDS antenna silver paste |
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