CN115232589A - High-low temperature resistant conductive adhesive for single-component semiconductor and preparation method thereof - Google Patents
High-low temperature resistant conductive adhesive for single-component semiconductor 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
- C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
- C09J163/04—Epoxynovolacs
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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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Abstract
The invention relates to a high and low temperature resistant single-component conductive adhesive for a semiconductor, which comprises the following raw materials in parts by mass: 10-15 parts of epoxy resin, 2-5 parts of epoxy POSS,40-60 parts of conductive filler, 5-10 parts of anhydride curing agent, 0.5-1 part of curing accelerator and 4-8 parts of diluent; the anhydride curing agent comprises a macromolecule containing a terminal group and/or a side chain containing anhydride; the epoxy resin comprises a tetrafunctional epoxy compound represented by the following formula (I): wherein R is independently selected from H, C1-4 alkyl, C1-4 alkoxy, C1-4 halogenated alkyl and C6-15 aryl. The conductive adhesive provided by the invention has good conductivity, lower storage modulus and excellent high temperature resistance, humidity resistance and heat resistance, andthe conductivity stability of the conductive adhesive is good, the conductivity is not obviously attenuated after multiple high-low temperature cycles, and the stability of the conductive adhesive is obviously improved.
Description
Technical Field
The invention relates to the technical field of semiconductor packaging and bonding, in particular to a high-low temperature resistant conductive adhesive for a single-component semiconductor and a preparation method thereof.
Background
With the development of electronic technology, the development trend of circuit boards for electronic components is to meet the requirements of smaller size (e.g., thinner and smaller volume), lighter weight (high integration level), multiple functions and intelligence. Also, higher requirements are placed on the packaging technology of electronic components. The conductive adhesive is used as a novel adhesive for replacing the traditional soldering tin, has the advantages of environmental protection, simple operation process and low bonding temperature. As the bonding material for chip and substrate, it is necessary to have the functions of high bonding strength, electrical conductivity and thermal conductivity, and whether it reliably and directly affects the service condition, stability and lifetime of electronic components.
At present, the conductive adhesive for electronic components mainly comprises an epoxy resin matrix, conductive filler, a curing agent, a curing accelerator and auxiliary materials. Because the adopted epoxy resin contains polar groups such as ester groups and hydroxyl groups, and the like, the epoxy resin often has certain water absorption, so that the epoxy resin used as the main body resin of the packaging material is not resistant to humidity and heat, and can generate phenomena such as chemical corrosion and the like under high-temperature and high-humidity conditions, so that the contact resistance of the conductive adhesive and the substrate is increased, and the reliability of electronic components is reduced. The conductive adhesive is mainly applied to packaging and bonding of electronic components such as liquid crystal display screens, LEDs, IC chips, printed circuit boards and the like, and often needs a high-temperature use environment. Particularly, the current processes of electronic components basically adopt a reflow soldering process, the temperature is as high as 260 ℃, the high temperature resistance of the current conductive adhesive is poor, the Tg is low, the bonding performance is obviously reduced at the temperature of more than 200 ℃, and the current processing process requirements of the electronic components cannot be met.
Cage Polysilsesquioxanes (POSS) are organosilicon compounds having a cage-like structure, the groups on the Si atoms at the top corners of which can be linked to different functional groups by a rich chemical strategy. The special property and abundant chemical modification of the compound are related to the application in various fields. The epoxy POSS is a POSS derivative which introduces single or multiple epoxy groups on a compound framework of cage-shaped polysilsesquioxane. The application of epoxy-based POSS in the field of adhesives has been disclosed in many prior arts, for example, CN112708325A adopts epoxy-based POSS with different epoxy functionalities, and the curing agent is an anhydride-terminated polyether, which is obtained by combining a rigid group of POSS and a polyether flexible segment in an anhydride curing agent, so as to achieve both hardness and toughness of an epoxy resin coating. However, the curing speed of the patent is relatively slow, and the comprehensive performance cannot meet the requirement by singly adopting epoxy POSS.
The inventor's prior patent CN202210746384.6 discloses a single-component conductive adhesive which uses epoxy group POSS, epoxy resin mixture including polyfunctional condensed polycyclic epoxy resin, and high-molecular anhydride curing agent containing anhydride at side chain and terminal group, and has lower storage modulus, high-temperature adhesion and wet heat resistance. However, through tests, the high and low temperature resistance of the conductive adhesive is not ideal enough, and through a high-low temperature circulation process, cracks and other defects are easy to appear at the bonding part, so that the conductivity is obviously reduced, and the requirements of certain environments which need to experience high and low temperatures on the conductive adhesive cannot be met.
Disclosure of Invention
In order to overcome the defects that the high-temperature adhesive force of the conductive adhesive is insufficient, the damp-heat aging resistance is insufficient, and the adhesive strength and the storage modulus are difficult to balance in the prior art, the invention provides the conductive adhesive which has low resistivity, high adhesive strength under the conditions of high temperature and damp heat, and still keeps good conductive performance after high-low temperature cycle test.
The invention solves the technical problems through the following technical scheme:
a high and low temperature resistant single-component conductive adhesive for semiconductors comprises the following raw materials in parts by mass: 10-15 parts of epoxy resin, 2-5 parts of epoxy POSS,40-60 parts of conductive filler, 5-10 parts of anhydride curing agent, 0.5-1 part of curing accelerator and 4-8 parts of diluent; the anhydride curing agent comprises a macromolecule containing a terminal group and/or a side chain containing anhydride; the epoxy resin comprises a tetrafunctional epoxy compound represented by the following formula (I):
wherein R is independently selected from H, C1-4 alkyl, C1-4 alkoxy, C1-4 halogenated alkyl and C6-15 aryl.
The C1-4 alkyl is selected from methyl, ethyl, propyl and butyl; the alkoxy of C1-4 is selected from methoxy, ethoxy, propoxy and butoxy; the C1-4 haloalkyl is selected from CF 3 、CH 2 CF 3 、CF 2 CHF 2 (ii) a The aryl of C6-15 is selected from phenyl, naphthyl and anthryl.
The inventor finds that the conductive adhesive obtained by adding a certain amount of polyepoxy compound shown in the formula (I) into the epoxy resin keeps higher adhesive force at high temperature (260 ℃) and the conductivity can meet the requirement after a double 85 aging test and a high-temperature-low temperature cycle test, thereby fully verifying the reliability of the conductive adhesive.
Further, the epoxy POSS has a chemical structure shown in the following formula (I):
each R is independently 2, 3-glycidoxypropyl, 3, 4-epoxycyclohexylethyl.
Further, the epoxy resin is a mixture of novolac epoxy resin, bisphenol epoxy resin and tetrafunctional epoxy compound shown in formula (I); the epoxy value of the novolac epoxy resin and the bisphenol epoxy resin is 0.4-0.6, and further, the mass ratio of the novolac epoxy resin, the bisphenol epoxy resin and the tetrafunctional epoxy compound is 13-18:10-15:6-8.
The tetrafunctional epoxy compound shown in the formula (I) is obtained by a preparation method comprising the following steps: dissolving a tetraphenol compound shown in a formula (I') in an organic solvent, adding a catalyst, heating to 80-90 ℃ in a nitrogen atmosphere, slowly adding excessive epoxy chloropropane, reacting for 4-8h, cooling to 60-70 ℃, adding an aqueous solution of NaOH, reacting for 3-5h, distilling under reduced pressure to remove the solvent and excessive epoxy chloropropane, and drying to obtain the compound;
further, the organic solvent is selected from at least one of isopropanol, dichloromethane and ethyl acetate, and the catalyst is tetrabutylammonium bromide. The excessive epichlorohydrin refers to the amount of the epichlorohydrin which is 15-20 times of the amount of the compound shown in the formula (I'); the mass fraction of the NaOH aqueous solution is 30-40wt%, the NaOH is added in multiple batches, for example, 2-5 batches, the difference of the addition amount of each batch does not exceed 20%, and the addition amount of the NaOH is preferably gradually decreased; the amount of NaOH added is not particularly limited, and the epoxidation dechlorination reaction can be carried out, and the amount of NaOH added is generally 15 to 25wt% of the mass of epichlorohydrin.
The anhydride curing agent comprises a micromolecular anhydride curing agent and a macromolecule with an end group and/or a side chain containing anhydride. Small molecule anhydride curing agents are well known in the art, such as at least one of maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, dodecenyl succinic anhydride, 4-methylhexahydrophthalic anhydride; the anhydride of the macromolecular anhydride curing agent is positioned at the terminal group and/or the side chain of the macromolecule.
Further, the anhydride-terminated polymeric anhydride curing agent is an anhydride-terminated polysiloxane having at least one of the following structures (B1), (B2), and (B3):
wherein R is 1 Independently selected from H and methyl.
The high-molecular anhydride curing agent with the terminal anhydride shown in (B1), (B2) and (B3) is prepared by the following steps: polysiloxane and unsaturated acid anhydride are subjected to Si-H addition reaction to obtain the polysiloxane-modified polysiloxane.
Further, in the above preparation method, the unsaturated anhydride is selected from maleic anhydride, norbornane anhydride or itaconic anhydride, such as platinum group catalyst. The reaction conditions for the Si-H addition are well known in the art, i.e., reaction at 70-90 deg.C for 20-30H in the presence of a platinum-based catalyst under an inert atmosphere.
Further, the polymeric acid anhydride curing agent having an acid anhydride in a side chain is a liquid polybutadiene modified with maleic anhydride.
Preferably, the curing agent is a micromolecular anhydride curing agent, polysiloxane with an end group of anhydride, and liquid polybutadiene modified by maleic anhydride according to a mass ratio of 5-10:10-15: 4-7.
The inventor unexpectedly finds that the complex curing agent, namely the curing agent containing the conventional small-molecular anhydride and the macromolecular curing agent containing the anhydride with the end group/side chain, which is mixed with the polyepoxy compound in the formula (I) in the epoxy resin, can obviously improve the comprehensive properties of the conductive adhesive, including the mechanical property, the heat resistance and the humidity resistance, and particularly improve the conductive performance of the conductive adhesive after the wet heat aging test and the high temperature-cooling cycle test. Presumably, the reason is that the polymer curing agent with the end group of the anhydride and the polymer curing agent with the side chain of the anhydride have certain complementary action, the epoxy compound with the formula (I) is matched with the tetrafunctional epoxy compound with the structure of bicyclo [2, 2] octane, the mechanical strength stability of the cured conductive adhesive is obviously enhanced, no obvious defects such as cracks and the like occur after a high-temperature-low-temperature cycle test, and the mechanical stability and the conductive stability of the conductive adhesive can be obviously enhanced. And the toughness of the conductive adhesive is not obviously lost.
The diluent is a reactive diluent with an epoxy group, which is conventional in the art, and is specifically selected from at least one of tert-butylphenyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, trimethylolethane triglycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and o-tolyl glycidyl ether.
The conductive filler is not particularly limited, and a conductive filler is generally used in the art. Such as silver powder, silver-plated copper powder, silver-plated nickel powder, silver-plated plastic powder, etc.; the conductive filler is spherical powder, flake powder, or dendritic powder, and has a particle diameter of 0.1-10 μm. Silver-plated plastic powder is preferred because it does not settle easily and the conductive paste has good fluidity.
The curing accelerator is imidazole curing accelerator, and is specifically selected from at least one of 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole.
Preferably, the conductive adhesive for a single-component semiconductor further comprises some auxiliary materials, and the types, functions and dosage of the auxiliary materials are well known in the art. For example, the conductive adhesive for the single-component semiconductor also comprises 0.05-0.2 part of anti-settling agent and 0.1-0.5 part of coupling agent.
The anti-settling agent is selected from fumed silica, and the coupling agent is selected from gamma-glycidyloxypropyltrimethoxysilane.
The second purpose of the invention is to provide a preparation method of the conductive adhesive for the single-component semiconductor with high reliability, which comprises the following steps:
(S1) uniformly mixing epoxy resin, epoxy POSS, a curing agent, a curing accelerator and auxiliary materials, grinding and defoaming to obtain a resin matrix;
and (S2) adding a diluent and a conductive filler into the resin matrix obtained in the step (S1), and continuously grinding until the fineness of the mixture meets the requirement to obtain the conductive adhesive.
Further, the grinding is carried out in an agate mortar for 10-30min; the defoaming treatment is carried out for 0.5-1h under the vacuum degree of 0.01-0.1 MPa.
Further, the grinding in the step (S2) is carried out to make the fineness of the mixture to 3 to 10 μm.
Detailed Description
The hydrogen terminated poly (dimethyl poly silicon) in the embodiment of the inventionSiloxane) was purchased from hebei constant solvent chemical priority corporation with number average molecular weights of 1560, 2200, 3000, 3800, respectively. The liquid polybutadiene modified by maleic anhydride is
MA-75; the anti-settling agent fumed silica is purchased from the winning and creating company of Germany
R-974, silver-coated plastic granules of conductive filler, purchased from CONPART, norway under the designation Ag-401 (G1), with a particle size D50 of about 5 μm; the coupling agent gamma-glycidyloxypropyltrimethoxysilane was KBM-403E manufactured by shin-Etsu chemical Co., ltd.
Preparation example 1
0.1mol of a compound of the formula (I') wherein R is methyl, i.e., 9,10 dimethyl-9, 10-dihydro-9, 10-diphenylbicyclo [2, 2] octyl-2, 3,6, 7-tetraphenol (CAS registry No.: 95156-77-7), dissolved in 80mL of isopropanol, heated to 80 ℃ under reflux conditions under nitrogen atmosphere, slowly added 1.8mol of epichlorohydrin within 1h, reacted for 10h while maintaining 80 ℃, cooled to 60 ℃, added 10g of 40wt aqueous NaOH solution, reacted for 1h while maintaining 60 ℃, added again with 8g of 40wt aqueous NaOH solution, reacted for 1h while maintaining 60 ℃, added again with 4g of 40wt aqueous NaOH solution, reacted for 2h while maintaining 60 ℃, distilled off the solvent and excess epichlorohydrin under reduced pressure, and dried to give a product shown below, hereinafter referred to as epoxy resin A, yield 87.3%.
Preparation example 2
Hydrogen terminated poly (dimethylsiloxane) having a number average molecular weight of 1560 (n about 20) and maleic anhydride in a molar ratio of 1:2.2 feeding materials, adding chloroplatinic acid with the mass of 0.5wt% of that of hydrogen poly (dimethyl siloxane) as a catalyst, reacting for 24 hours at 80 ℃ in a nitrogen atmosphere, and decompressing to remove the solvent and excessive maleic anhydride to obtain viscous liquid which is a product:
Further, hydrogen-terminated poly (dimethylsiloxane) having a number average molecular weight of 2300, 3000, 3800 was used as a starting material, and maleic anhydride was added thereto in the same manner as described above to obtain products of the formula (B1) having n of about 30, n of about 40, and n of about 50, which were designated as B1-30, B1-40, and B1-50, respectively.
Preparation example 3
Other conditions are the same as the preparation example 2, hydrogen-terminated poly (dimethyl siloxane) with the number-average molecular weight of 2300 is adopted as a raw material to react with norbornane dilute anhydride, and the molar ratio of the hydrogen-terminated poly (dimethyl siloxane) to the norbornane dilute anhydride is 1:2.2 feeding to obtain a product of formula (B2-30) having n of about 30:
Hydrogen-terminated poly (dimethylsiloxane) with a number average molecular weight of 3000 was also used as a starting material, and norbornadic anhydride was used according to the above method to obtain a product represented by formula (B2-40) with n of about 40, respectively.
Example 1
(S1) 15 parts of an epoxy resin (a mixed epoxy resin of novolac epoxy resin F51, bisphenol a epoxy resin E43 and tetrafunctional epoxy resin a obtained in preparation example 1 in a mass ratio of 15
MA-75 according to the mass ratio of 5:10: 4), 0.7 part of 2-ethyl-4-methylimidazole and 0.1 part of anti-settling agent
R-974,0.2 portion of coupling agent KBM-403E, uniformly mixed, ground for 10min in an agate mortar, and removed by vacuum degree of 0.05MPaPerforming soaking treatment for 10min to obtain a resin matrix;
(S2) adding 10 parts of diluent (compounding trimethylolethane triglycidyl ether and ethylene glycol diglycidyl ether according to the mass ratio of 1.
Example 2
Other conditions were the same as in example 1 except that 6 parts of an acid anhydride curing agent was tetrahydrophthalic anhydride, B1-30, maleic anhydride-modified liquid polybutadiene obtained in preparation example 2
MA-75 according to the mass ratio of 5:10:4, namely replacing B1-20 with n =20 by B1-30 with equal mass n = 30.
Example 3
Other conditions were the same as in example 1 except that 6 parts of an acid anhydride curing agent was tetrahydrophthalic anhydride, B1-40 obtained in preparation example 2, maleic anhydride-modified liquid polybutadiene
MA-75 according to the mass ratio of 5:10:4, namely replacing B1-20 with n =20 with B1-40 with n =40 with equal mass.
Example 4
Other conditions were the same as in example 1 except that 6 parts of an acid anhydride curing agent was tetrahydrophthalic anhydride, B1-50, maleic anhydride-modified liquid polybutadiene obtained in preparation example 2
MA-75 according to the mass ratio of 5:10:4, namely replacing B1-20 with n =20 with B1-50 with n =50 with equal mass.
Example 5
Other conditions were the same as in example 1 except that 6 parts of an acid anhydride curing agent was tetrahydrophthalic anhydride, B2-30, maleic anhydride-modified liquid polybutadiene obtained in preparation example 3
MA-75 according to the mass ratio of 5:10:4, namely replacing B1-20 with n =20 with B2-30 with n =30 with equal mass.
Example 6
Other conditions were the same as in example 1 except that 6 parts of an acid anhydride curing agent was tetrahydrophthalic anhydride, B2-40, maleic anhydride-modified liquid polybutadiene obtained in preparation example 3
MA-75 according to the mass ratio of 5:10:4, namely replacing B1-20 with n =20 with B2-40 with n =40 with equal mass.
Example 7
The other conditions were the same as in example 5 except that 15 parts of the epoxy-epoxy resin was novolac epoxy resin F51, bisphenol a epoxy resin E43 and tetrafunctional epoxy resin a obtained in preparation example 1 in a mass ratio of 15:15:8, a mixed epoxy resin.
Example 8
The other conditions were the same as in example 5 except that 15 parts of the epoxy-epoxy resin was novolac epoxy resin F51, bisphenol a epoxy resin E43 and tetrafunctional epoxy resin A2 obtained in preparation example 1 in a mass ratio of 15:10:5, a hybrid epoxy resin.
Example 9
The other conditions were the same as in example 5 except that 15 parts of the epoxy-epoxy resin was novolac epoxy resin F51, bisphenol a epoxy resin E43 and tetrafunctional epoxy resin A2 obtained in preparation example 1 in a mass ratio of 15:10:10 of a hybrid epoxy resin.
Example 10
Other conditions were the same as in example 5 except that the acid anhydride curing agent 6 parts was tetrahydrophthalic anhydride, B2-30 obtained in preparation example 3, maleic anhydride-modified liquid polybutadiene
MA-75 is mixed according to the mass ratio of 10:15:7, compounding.
Comparative example 1
The other conditions were the same as in example 5 except that 15 parts of the epoxy-epoxy resin was novolac epoxy resin F51, and bisphenol a epoxy resin E43 was used in a mass ratio of 15:10, i.e. no tetrafunctional epoxy resin a is added.
Comparative example 2
The other conditions were the same as in example 5 except that no cage octa (2, 3-glycidoxypropyl) POSS was added, and the amount of epoxy resin was increased from 15 parts to 20 parts.
Comparative example 3
Other conditions were the same as in example 5 except that 6 parts of an acid anhydride curing agent was tetrahydrophthalic anhydride and maleic anhydride-modified liquid polybutadiene
MA-75 is mixed according to the mass ratio of 5:4, compounding. That is, B2-30 prepared in preparation example 3 was not added.
Application example
The conductive adhesives obtained in the above examples and comparative examples were cured at 150 ℃ for 2 hours, and the following performance tests were performed, with the results shown in table 1.
And (3) conductivity test: the test was performed with reference to ASTM D257 standard.
Storage modulus test: the test was performed with reference to astm d4065 standard.
Testing the bonding force of the copper substrate: 2 x 2mm silicon chips were mounted on a copper frame under curing conditions of 30 minutes from 25 ℃ to 175 ℃ and then held at 175 ℃ for a further 60 minutes and cured in an oven. After curing, the shear strength of the wafer was measured at 25 ℃ and 260 ℃ using an automatic adhesion measuring apparatus.
High and low temperature stability: and (3) placing the component made of the conductive adhesive at the temperature of minus 40 ℃ for 10min, recovering to the room temperature, then placing the component at the temperature of 85 ℃ for 10min, recovering to the room temperature, carrying out cold and hot circulation at the temperature of minus 40 ℃ to 85 ℃ for 200 times in total according to the operation, and testing the conductivity again.
TABLE 1 conductive adhesive Performance test results
As can be seen from the data in Table 1, the conductive adhesive for single-component semiconductor prepared by the invention has excellent comprehensive performance, good conductivity, lower storage modulus and excellent high temperature resistance and humidity resistance. Through comparison between the examples and the comparative examples, the invention can find that through specific selection of the components, namely compounding of the epoxy resin A with four functionality degrees in the epoxy resin, the epoxy POSS and the curing agent with the end group of anhydride and the side chain of anhydride, the conductive adhesive of the invention achieves satisfactory performance indexes at the same time, particularly the conductive adhesive has good high and low temperature conductivity stability, and after 200 times of low-temperature and high-temperature circulation, the conductivity is not obviously attenuated, so that the conductive adhesive can meet the requirement of being subjected to high and low temperature recycling use environments.
Claims (10)
1. The conductive adhesive for the high and low temperature resistant single-component semiconductor is characterized by comprising the following raw materials in parts by mass: 10-15 parts of epoxy resin, 2-5 parts of epoxy POSS,40-60 parts of conductive filler, 5-10 parts of anhydride curing agent, 0.5-1 part of curing accelerator and 4-8 parts of diluent; the anhydride curing agent comprises a macromolecule containing a terminal group and/or a side chain containing anhydride; the epoxy resin comprises a tetrafunctional epoxy compound represented by the following formula (I):
wherein R is independently selected from H, C1-4 alkyl, C1-4 alkoxy, C1-4 halogenated alkyl and C6-15 aryl.
2. The conductive paste according to claim 1, wherein the C1-4 alkyl group is selected from the group consisting of methyl, ethyl, propyl, butyl; the C1-4 alkoxy is selected from methoxy, ethoxy, propoxy and butoxy; the C1-4 haloalkyl is selected from CF 3 、CH 2 CF 3 、CF 2 CHF 2 (ii) a The aryl of C6-15 is selected from phenyl, naphthyl and anthryl.
3. The conductive paste of claim 1, wherein the epoxy-based POSS has a chemical structure represented by formula (I):
each R is independently 2, 3-glycidoxypropyl, 3, 4-epoxycyclohexylethyl.
4. The conductive paste of claim 1, wherein the epoxy resin is a mixture of a novolac epoxy resin, a bisphenol type epoxy resin, and a tetrafunctional epoxy compound represented by formula (I); the epoxy value of the phenolic epoxy resin and the bisphenol type epoxy resin is 0.4-0.6; further, the mass ratio of the novolac epoxy resin, the bisphenol epoxy resin and the tetrafunctional epoxy compound is 13-18:10-15:6-8.
5. The conductive paste as claimed in claim 1, wherein the tetrafunctional epoxy compound of formula (I) is obtained by a preparation method comprising the steps of: dissolving a tetraphenol compound shown as a formula (I') in an organic solvent, adding a catalyst, heating to 80-90 ℃ in a nitrogen atmosphere, slowly adding excessive epichlorohydrin, reacting for 4-8h, cooling to 60-70 ℃, adding a NaOH aqueous solution, reacting for 3-5h, distilling under reduced pressure to remove the solvent and the excessive epichlorohydrin, and drying to obtain the tetraphenol compound;
6. the conductive adhesive according to claim 1, wherein the acid anhydride curing agent comprises a small-molecule acid anhydride curing agent, and a polymer having an acid anhydride in a terminal group and/or a side chain; the small molecular anhydride curing agent is at least one selected from maleic anhydride, tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl nadic anhydride, hydrogenated methyl nadic anhydride, dodecenyl succinic anhydride and 4-methyl hexahydrophthalic anhydride; the anhydride of the macromolecular anhydride curing agent is positioned at the terminal group and/or the side chain of the macromolecule.
7. The conductive paste of claim 6, wherein the anhydride-terminated polymeric anhydride curing agent is an anhydride-terminated polysiloxane having at least one of the following structures (B1), (B2) and (B3):
wherein R is 1 Independently selected from H, methyl;
further, the polymeric acid anhydride curing agent with acid anhydride in the side chain is maleic anhydride modified liquid polybutadiene.
8. The conductive adhesive according to claim 6, wherein the curing agent is a small-molecule anhydride curing agent, polysiloxane with an anhydride terminal group, and maleic anhydride-modified liquid polybutadiene in a mass ratio of 5-10:10-15: 4-7.
9. The conductive paste as claimed in claim 1, wherein the diluent is at least one selected from the group consisting of t-butylphenyl glycidyl ether, phenyl glycidyl ether, benzyl glycidyl ether, trimethylolethane triglycidyl ether, ethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and o-tolyl glycidyl ether; and/or
The electric conduction is selected from at least one of silver powder, silver-plated copper powder, silver-plated nickel powder and silver-plated plastic powder; the shape of the conductive filler is spherical powder, flaky powder or dendritic powder, and the particle diameter of the conductive filler is 0.1-10 mu m; and/or
The curing accelerator is imidazole curing accelerator, and is specifically selected from at least one of 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole.
10. A method for preparing the conductive paste of any one of claims 1-9, comprising the steps of:
(S1) uniformly mixing epoxy resin, epoxy POSS, a curing agent, a curing accelerator and auxiliary materials, grinding and defoaming to obtain a resin matrix;
and (S2) adding a diluent and a conductive filler into the resin matrix obtained in the step (S1), and continuously grinding until the fineness of the mixture meets the requirement to obtain the conductive adhesive.
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| CN115651586A (en) * | 2022-10-28 | 2023-01-31 | 东莞市德聚胶接技术有限公司 | Anti-migration epoxy conductive silver adhesive and preparation method thereof |
| CN116375727A (en) * | 2023-03-31 | 2023-07-04 | 苏州大学 | Bio-based epoxy monomer, medium-temperature curing epoxy resin system and preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115651586A (en) * | 2022-10-28 | 2023-01-31 | 东莞市德聚胶接技术有限公司 | Anti-migration epoxy conductive silver adhesive and preparation method thereof |
| CN115651586B (en) * | 2022-10-28 | 2023-08-15 | 广东德聚技术股份有限公司 | Anti-migration epoxy conductive silver adhesive and preparation method thereof |
| CN116375727A (en) * | 2023-03-31 | 2023-07-04 | 苏州大学 | Bio-based epoxy monomer, medium-temperature curing epoxy resin system and preparation method |
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| CN115232589B (en) | 2023-05-02 |
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