Epoxy resin composition as well as preparation method and application thereof

Abstract

The invention provides an epoxy resin composition and a preparation method and application thereof, and belongs to the technical field of integrated circuit packaging, and the epoxy resin composition comprises epoxy resin, a curing agent and a modified inorganic filler; wherein the modified inorganic filler comprises silicon dioxide and a siloxane compound which is grafted on the surface of the silicon dioxide and contains ionic bonds. The epoxy resin composition provided by the embodiment of the invention can reduce the phenomenon that the modified inorganic filler is gathered towards one side, so that the modified inorganic filler is more uniformly distributed in the underfill adhesive, the uniform linear expansion coefficient is ensured, and the cracking risk is reduced.

Description

Technical Field

[0001] The present application relates to the field of materials technology, and particularly relates to an epoxy resin composition, a preparation method thereof, and an application thereof. Background Art

[0002] With the in-depth application of integrated circuits (ICs) in fields such as smart phones, the Internet of Things, automotive electronics, and high-performance computing, the integration degree of ICs is getting higher and higher, and components are continuously developing towards miniaturization and multi-functionality, thus posing more stringent requirements on the packaging technology of ICs.

[0003] During the integrated circuit packaging process, epoxy resin compositions such as epoxy packaging materials, interlayer insulating films, and underfill adhesives are used for packaging. In order to match the difference in the coefficient of thermal expansion, fillers such as silica or alumina with a smaller coefficient of thermal expansion are added to the epoxy resin composition. Since fillers such as silica and alumina carry electric charges, when there is a potential difference on both sides of the epoxy resin composition, it is easy to cause phenomena such as distribution deviation and aggregation of the fillers, and then cause differences in the coefficient of linear thermal expansion in different regions of the epoxy resin composition, and it is easy to occur phenomena such as cracking, affecting the packaging effect of the integrated circuit. Summary of the Invention

[0004] Embodiments of the present application provide an epoxy resin composition, a preparation method thereof, and an integrated circuit packaging structure. The epoxy resin composition can ensure the uniformity of the distribution of modified inorganic fillers in the integrated circuit, reduce the phenomenon of differences in the coefficient of linear thermal expansion in different regions, and ensure the stability of the integrated circuit packaging.

[0005] In a first aspect, embodiments of the present application provide an epoxy resin composition, which includes an epoxy resin, a curing agent, and a modified inorganic filler;

[0006] Among them, the modified inorganic filler includes silica and a siloxane compound containing an ionic bond grafted on the surface of the silica.

[0007] Optionally, the epoxy resin composition includes the following components in parts by weight: 15 parts - 35 parts of epoxy resin, 10 parts - 20 parts of curing agent, and 10 parts - 20 parts of the modified inorganic filler.

[0008] Optionally, the epoxy resin includes the following components in parts by weight: 5 parts - 15 parts of low-viscosity epoxy resin, 10 parts - 20 parts of multi-functional epoxy resin; and / or

[0009] The curing agent includes an aniline curing agent; and / or

[0010] The epoxy resin composition further includes the following components in parts by weight: 0.1 part - 5 parts of colorant, 0.1 part - 5 parts of coupling agent.

[0011] Optionally, the siloxane compound containing an ionic bond includes at least one of an azide siloxane compound and an amino siloxane compound.

[0012] Optionally, the siloxane compound containing an ionic bond includes at least one of (azidomethyl)phenyltrimethoxysilane, p-azidomethylphenyltrimethoxysilane, 3-(azidopropyl)triethoxysilane, 6-azidosulfonylhexyltriethoxysilane, 4-[2-(trimethoxysilyl)ethyl]benzene-1-sulfonyl azide, 11-azidoundecyltrimethoxysilane, 3-{(dimethyl(3-trimethoxysilyl)propyl)ammonio}propane-1-sulfonate, 4-nitro-4'-(n-ethyl-n-trimethoxysilylcarbamate)aminoazobenzene, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, vinylbenzylaminoethylaminopropyltrimethoxysilane hydrochloride, (styrylmethyl)bis(triethoxysilylpropyl)ammonium chloride, N-trimethoxysilylpropyl-N,N,N-tri-n-butylammonium chloride, N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride, and tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride.

[0013] Optionally, the low-viscosity epoxy resin has a viscosity of 0.5 Pa·s - 3 Pa·s and an epoxy value of 0.36 - 0.78 eq / 100 g;

[0014] And / or, the low-viscosity epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol AD epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and hydrogenated bisphenol A epoxy resin.

[0015] Optionally, the polyfunctional epoxy resin includes polyfunctional glycidyl ether epoxy resin and / or polyfunctional glycidyl amine epoxy resin.

[0016] Optionally, the aniline curing agent includes at least one of m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenylmethane (4,4'-methylenedianiline), diethyltoluenediamine, and 3,3'-diethyl-4,4'-diaminodiphenylmethane and its derivatives.

[0017] In a second aspect, an embodiment of the present application further provides a method for preparing an epoxy resin composition for preparing the epoxy resin composition as described above, including:

[0018] Providing a raw material including a modified inorganic filler;

[0019] Mixing the raw materials to obtain an epoxy resin composition.

[0020] Optionally, the method for preparing the modified inorganic filler includes:

[0021] Disperse silica in a solvent to obtain a dispersion solution;

[0022] Add a siloxane compound containing an ionic bond to the dispersion solution and react for 0.5 h - 1.5 h at a temperature of 80°C - 90°C to obtain a modified solution;

[0023] After performing solid-liquid separation and drying on the modified solution, a modified inorganic filler is obtained.

[0024] Optionally, the raw materials include a low-viscosity epoxy resin, a polyfunctional epoxy resin, an aniline curing agent, a modified inorganic filler, a colorant, and a coupling agent;

[0025] Mix the raw materials, including:

[0026] Mix the low-viscosity epoxy resin, the polyfunctional epoxy resin, the colorant, and the coupling agent to obtain a first mixture;

[0027] Add the modified inorganic filler to the first mixture and mix to obtain a second mixture;

[0028] Add the aniline curing agent to the second mixture and mix to obtain an epoxy resin composition.

[0029] In a third aspect, an embodiment of the present application further provides an application of the epoxy resin composition, applying the above epoxy resin composition to the field of electronic materials.

[0030] Advantageous effects of the embodiments of the present application:

[0031] In the embodiments of the present application, an epoxy resin composition is provided. The epoxy resin composition includes an epoxy resin, a curing agent, and a modified inorganic filler. Among them, the modified inorganic filler includes silica and a siloxane compound containing an ionic bond grafted on the surface of the silica. The epoxy resin and the curing agent can cooperate to achieve curing, ensure the encapsulation effect, and provide a supporting role. Through the siloxane compound containing an ionic bond, the charge on the surface of the silica can be released to the outside, reducing the charge amount of the silica. When the epoxy resin composition is applied to integrated circuit packaging, due to the small charge amount of the modified inorganic filler, it is less affected by the potential difference, reducing the phenomenon of the modified inorganic filler aggregating to one side, making the modified inorganic filler more evenly distributed in the epoxy resin composition, ensuring a uniform coefficient of linear expansion, and reducing the risk of cracking. Description of the Drawings

[0032] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings required for the description of the embodiments. Obviously, the following drawings are only some embodiments of the present application. For those skilled in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0033] Figure 1 It is a schematic diagram of the filler deviation test system provided by the embodiments of the present application;

[0034] Figure 2 It is a result diagram of the filler distribution deviation of the epoxy resin composition in Example 1 of the present application obtained through the test system;

[0035] Figure 3 It is a result diagram of the filler distribution deviation of the epoxy resin composition in Comparative Example 1 of the present application obtained through the test system;

[0036] Figure 4 It is a result diagram of the filler distribution deviation of the epoxy resin composition in Example 1 of the present application during actual encapsulation;

[0037] Figure 5 It is a result diagram of the filler distribution deviation of the epoxy resin composition in Comparative Example 1 of the present application during actual encapsulation. Specific embodiments

[0038] Next, the technical solutions in the embodiments of the present application will be described clearly and completely. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative efforts belong to the scope of protection of the present application. In addition, it should be understood that the specific embodiments described herein are only used to illustrate and explain the present application, and are not used to limit the present application.

[0039] In the first aspect, the embodiments of the present application provide an epoxy resin composition, which includes an epoxy resin, a curing agent, and a modified inorganic filler. Among them, the modified inorganic filler includes silica and a siloxane compound containing an ionic bond grafted on the surface of silica.

[0040] The cooperation of the epoxy resin and the curing agent can achieve curing, ensure the encapsulation effect, and provide a supporting role. Through the siloxane compound containing an ionic bond, the charge on the surface of silica can be released to the outside, reducing the charge amount of silica. When the epoxy resin composition is applied to integrated circuit encapsulation, due to the small charge amount of the modified inorganic filler, the influence of the potential difference is small, reducing the phenomenon that the modified inorganic filler aggregates to one side, making the modified inorganic filler more evenly distributed in the epoxy resin composition, ensuring a uniform coefficient of linear expansion, and reducing the risk of cracking.

[0041] There are silanol groups (Si-OH) on the surface of silica. When silica is modified with a siloxane compound containing an ionic bond and grafted onto the silica surface, the hydroxyl groups are removed to form Si-O-Si bonds, thereby significantly reducing the charge amount of the modified inorganic filler, further reducing the distribution deviation caused by the potential difference, ensuring a uniform coefficient of linear expansion, reducing the risk of cracking, and improving the stability of integrated circuit packaging.

[0042] Among them, the particle size of silica can be 0.3 μm - 5 μm, which can ensure good filling effect, good dispersibility and fluidity.

[0043] In some embodiments, the epoxy resin composition comprises the following components in parts by weight: 15 - 35 parts of epoxy resin, 10 - 20 parts of curing agent, and 10 - 20 parts of modified inorganic filler.

[0044] By making the epoxy resin, curing agent and modified inorganic filler in the epoxy resin composition meet the above ratios, the epoxy resin composition can have processing performance, and can ensure the bonding performance after curing, thereby ensuring the encapsulation effect. The modified inorganic filler in appropriate proportion can make the coefficient of linear expansion of the epoxy resin composition match that of the integrated circuit, and keep the epoxy resin composition having a higher strength. The modified inorganic filler can inhibit the phenomenon of filler distribution deviation in the curing process of the epoxy resin composition, reduce the phenomenon of excessive difference in the coefficient of linear expansion caused by the filler distribution deviation, and ensure the encapsulation stability.

[0045] In some embodiments, the epoxy resin comprises the following components in parts by weight: 5 - 15 parts of low-viscosity epoxy resin, and 10 - 20 parts of multi-functional epoxy resin.

[0046] By adding low-viscosity epoxy resin, the overall viscosity of the epoxy resin composition can be reduced, the fluidity of the epoxy resin composition can be better, the process efficiency can be improved, the filling effect can be ensured, it can better adapt to the thermal expansion difference between different materials, reduce stress concentration, and improve the reliability of encapsulation. The multi-functional epoxy resin and aniline curing agent cooperate with each other to increase the crosslinking density, thereby increasing the glass transition temperature of the epoxy resin composition, enhancing the high-temperature stability, reducing the internal stress generated due to temperature change, and ensuring the encapsulation reliability.

[0047] In some embodiments, the curing agent includes aniline curing agent. The aniline curing agent has high reaction activity and can generate a curing reaction with epoxy resin in a short time to improve the effect. The aniline curing agent and epoxy resin have a high curing temperature, so that the cured epoxy resin composition has better stability and high-temperature resistance, is not easy to degenerate, and maintains high strength and stiffness. In addition, the cured product formed by the aniline curing agent and epoxy resin has excellent mechanical properties.

[0048] In some embodiments, the epoxy resin composition further comprises 0.1 part to 5 parts of a colorant and 0.1 part to 5 parts of a coupling agent. The colorant can endow the epoxy resin composition with a specific color, facilitating identification and differentiation. Some colorants can also provide functions such as antistatic property and conductivity. Adding a coupling agent can improve the wettability and adhesion of the epoxy resin composition, thereby enhancing the strength of the encapsulation structure. The coupling agent has high heat resistance and weather resistance, improving the high-temperature stability of the epoxy resin composition. Moreover, the coupling agent can also improve the fluidity of the epoxy resin composition, enhance the filling effect, and improve the curing conditions.

[0049] Exemplarily, the colorant can be carbon black. Carbon black has excellent coloring ability, and the color is uniform and stable. When added to the epoxy resin composition, it can also improve the structural strength, wear resistance, and tear resistance of the encapsulated structure. Moreover, it has good dispersibility and high stability, and is not prone to agglomeration or precipitation. The coupling agent can be a silane coupling agent. One end of the silane coupling agent can chemically react with the surface of inorganic materials (such as semiconductor elements, silicon interposers, etc.), and the other end can combine with organic materials (such as epoxy resin in the epoxy resin composition), thereby improving the bonding force between the epoxy resin composition and the encapsulated components, enhancing the interfacial bonding strength, and ensuring the encapsulation stability. The silane coupling agent can also form a protective film on the material surface, thereby improving the long-term stability.

[0050] In some embodiments, the silicon-oxygen compound containing an ionic bond includes at least one of an azide-based silicon-oxygen compound and an amine-based silicon-oxygen compound.

[0051] The azide-based silicon-oxygen compound and the amine-based silicon-oxygen compound have ionic bonds. After modifying silica, they can significantly reduce the charge amount of the modified inorganic filler, thereby reducing the distribution deviation caused by the potential difference, ensuring a uniform coefficient of linear expansion, reducing the cracking risk, and improving the stability of the integrated circuit package. At the same time, the azide-based silicon-oxygen compound and the amine-based silicon-oxygen compound can also improve the physical properties such as the hardness, toughness, and wear resistance of silica, and enhance the comprehensive performance of the modified inorganic filler.

[0052] In some embodiments, the siloxane compound containing an ionic bond includes at least one of (azidomethyl)phenyltrimethoxysilane, p-azidomethylphenyltrimethoxysilane, 3-(azidopropyl)triethoxysilane, 6-azidosulfonylhexyltriethoxysilane, 4-[2-(trimethoxysilyl)ethyl]benzene-1-sulfonyl azide compound, 11-azidoundecyltrimethoxysilane, 3-{(dimethyl(3-trimethoxysilyl)propyl)ammonio}propane-1-sulfonate, 4-nitro-4'-(n-ethyl-n-trimethoxysilylcarbamate)aminoazobenzene, dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, vinylbenzylaminoethylaminopropyltrimethoxysilane hydrochloride, (styrylmethyl)bis(triethoxysilylpropyl)ammonium chloride, N-trimethoxysilylpropyl-N,N,N-tri-n-butylammonium chloride, N-trimethoxysilylpropyl-N,N,N-trimethylammonium chloride, and tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride.

[0053] The above compounds all have siloxane groups, contain ionic bonds, and have stable chemical properties. By grafting these compounds onto the silica surface, the silica can be modified to form Si-O-Si groups, thereby significantly reducing the charge amount of the modified inorganic filler, further reducing the distribution deviation caused by the potential difference, ensuring a uniform coefficient of linear expansion, reducing the risk of cracking, and improving the stability of the integrated circuit package.

[0054] In some embodiments, the low-viscosity epoxy resin has a viscosity of 0.5 Pa·s - 3 Pa·s and an epoxy value of 0.36 - 0.78 eq / 100 g.

[0055] The low-viscosity epoxy resin has a viscosity in the range of 0.5 Pa·s - 3 Pa·s and an epoxy value in the range of 0.36 - 0.78 eq / 100 g, and has excellent fluidity and good permeability. When applied to an epoxy resin composition, it can improve the process efficiency and filling effect.

[0056] In some embodiments, the low-viscosity epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol AD epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, and hydrogenated bisphenol A epoxy resin.

[0057] In some embodiments, the polyfunctional epoxy resin includes polyfunctional glycidyl ether epoxy resin and / or polyfunctional glycidylamine epoxy resin.

[0058] Polyfunctional glycidyl ether epoxy resins have low viscosity, good fluidity, which improves the processing efficiency and filling effect of epoxy resin compositions. And polyfunctional glycidyl ether epoxy resins have high thermal stability, high strength and toughness, good corrosion resistance and insulation properties.

[0059] Polyfunctional glycidylamine epoxy resins have good adhesion, high strength and toughness, and low water absorption rate, which can ensure the reliability of encapsulation and optimize the thermal management after encapsulation.

[0060] Exemplarily, the polyfunctional epoxy resin includes at least one of melamine epoxy resin, hydantoin epoxy resin, 4,5-epoxycyclohexane-1,2-dicarboxylic acid diglycidyl ester (TDE-85 epoxy resin), 4-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline (AFG-90 epoxy resin), N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (AFG-80 epoxy resin), resorcinol formaldehyde tetra diglycidyl ether (F-76), triglycidyl m-aminophenol, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, cyclohexane-1,2-dicarboxylic acid diglycidyl ester and tetrahydrophthalic acid diglycidyl ester epoxy resin.

[0061] In some embodiments, the aniline curing agent includes at least one of m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenylmethane (4,4'-methylenedianiline), diethyltoluenediamine and 3,3'-diethyl-4,4'-diaminodiphenylmethane and its derivatives.

[0062] In a second aspect, an embodiment of the present application provides a preparation method of an epoxy resin composition for preparing the epoxy resin composition as described above, including:

[0063] Providing raw materials including modified inorganic fillers;

[0064] Mixing the raw materials to obtain an epoxy resin composition.

[0065] The preparation method of the epoxy resin composition provided by the embodiments of the present application has all the beneficial effects of the epoxy resin composition as described above, which will not be elaborated here.

[0066] In some embodiments, the preparation method of the modified inorganic filler includes:

[0067] Dispersing silica in a solvent to obtain a dispersion solution;

[0068] Adding a silicon-oxygen compound containing an ionic bond to the dispersion solution and reacting at a temperature of 80°C - 90°C for 0.5 h - 1.5 h to obtain a modified solution;

[0069] After solid-liquid separation and drying of the modified solution, a modified inorganic filler is obtained.

[0070] First, disperse silica in a solvent to facilitate subsequent reaction with the modifier. Then, add a siloxane compound with an ionic bond to the dispersed solution. Since there are hydroxyl groups on the surface of silica, it can react with the siloxane compound with an ionic bond at a temperature of 80°C - 90°C, losing the hydroxyl groups and undergoing modification to reduce the charge of silica. Reacting for 0.5 h - 1.5 h can ensure sufficient modification. After solid-liquid separation and drying, the modified inorganic filler can be obtained.

[0071] In some embodiments, the mass ratio of silica to the siloxane compound with an ionic bond is 100:(0.6 - 2). By controlling the mass ratio of silica to the siloxane compound with an ionic bond within 100:(0.6 - 2), the siloxane compound with an ionic bond can react fully with silica to form a modified inorganic filler, with the modified inorganic filler having a relatively small charge, saving raw materials, ensuring the reaction efficiency, and reducing the production and preparation cost.

[0072] Exemplarily, the mass ratio of silica to the siloxane compound with an ionic bond can be 100:0.6, 100:0.8, 100:1, 100:1.2, 100:1.5, 100:1.8, or 100:2.

[0073] In some embodiments, the raw materials include a low-viscosity epoxy resin, a polyfunctional epoxy resin, an aniline curing agent, a modified inorganic filler, a colorant, and a coupling agent.

[0074] Among them, mixing the raw materials includes:

[0075] Mix the low-viscosity epoxy resin, the polyfunctional epoxy resin, the colorant, and the coupling agent to obtain a first mixture;

[0076] Add the modified inorganic filler to the first mixture and mix to obtain a second mixture;

[0077] Add the aniline curing agent to the second mixture and mix to obtain an epoxy resin composition.

[0078] By first mixing the low-viscosity epoxy resin, the polyfunctional epoxy resin, the colorant, and the coupling agent to obtain a first mixture, and then adding the modified inorganic filler to the first mixture, the aggregation of the modified inorganic filler can be reduced, and the dispersibility and uniformity can be improved. Adding the aniline curing agent last can ensure the uniform distribution of the aniline curing agent.

[0079] Among them, a high-speed method is adopted during the mixing of the first mixture, the second mixture, and the epoxy resin composition to improve the mixing uniformity.

[0080] In some embodiments, during the process of mixing to obtain the first mixture and the second mixture, the mixing is carried out under the condition that the rotation speed is 1000 rpm - 2500 rpm. By carrying out high-speed mixing under the condition that the rotation speed is 1000 rpm - 2500 rpm, the mixing effect can be ensured and the dispersion uniformity can be guaranteed.

[0081] Exemplarily, during the mixing process, the rotation speed can be 1000 rpm, 1200 rpm, 1500 rpm, 1800 rpm, 2000 rpm, 2200 rpm or 2500 rpm.

[0082] In a third aspect, an embodiment of the present application further provides an application of the epoxy resin composition, applying the above epoxy resin composition to the field of electronic materials.

[0083] The epoxy resin composition as described above includes an epoxy resin, a curing agent, and a modified inorganic filler. Since the modified inorganic filler has been modified to balance the charge on the surface of the silica, the phenomenon that the modified inorganic filler is separated from the epoxy resin due to charge repulsion is reduced, the distribution uniformity of the modified inorganic filler is ensured, the difference in the coefficient of linear expansion at different positions after the epoxy resin composition is cured is reduced. When the epoxy resin composition is applied to the field of electronic materials, the risk of cracking can be reduced, the encapsulation effect of the integrated circuit packaging structure can be improved, and the encapsulation stability can be guaranteed.

[0084] During the heat curing process of the encapsulation, the inorganic fillers uniformly dispersed in the epoxy resin composition will be separated and agglomerated, resulting in a high proportion of resin on the semiconductor element side and a high coefficient of linear expansion, while the proportion of inorganic fillers on the silicon interposer side is high and the coefficient of linear expansion is small, thereby reducing the encapsulation reliability. After research, it is speculated that the main reason for the separation and agglomeration of the inorganic fillers is that the materials used for the electrode connection surfaces on the semiconductor element side and the silicon interposer side form a potential difference, causing electrophoresis of the inorganic fillers in the epoxy resin composition, and the inorganic fillers aggregate towards the silicon interposer side, resulting in a filler-free region in the epoxy resin composition. The difference in the coefficient of linear expansion between the semiconductor element side and the silicon interposer side is large, thus causing the packaged integrated circuit to be prone to cracking problems.

[0085] Taking the underfill adhesive as an example, by using the epoxy resin composition provided by the embodiment of the present application, the phenomenon that the filler shifts to one side due to the different materials on both sides of the epoxy resin composition can be significantly reduced, and the encapsulation effect can be guaranteed.

[0086] The following further elaborates the embodiments of the present application in conjunction with specific embodiments. It should be understood that these embodiments are only used to illustrate the present application and not to limit the scope of the present application. The experimental methods without specific conditions noted in the following embodiments are usually in accordance with the conditions recommended by the manufacturer.

[0087] It should be noted that in the following examples and comparative examples, unless otherwise specified, the parts are by mass.

[0088] Example 1

[0089] The epoxy resin composition in this example comprises the following components in parts by weight: 8.9 parts of low-viscosity epoxy resin, 15 parts of polyfunctional epoxy resin, 15 parts of aniline curing agent, 60 parts of modified inorganic filler, 0.3 part of colorant, and 0.8 part of coupling agent.

[0090] Among them, the low-viscosity epoxy resin is bisphenol F epoxy resin with an epoxy equivalent of 159.00; the polyfunctional epoxy resin is 4-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline (AFG-90 epoxy resin) with an epoxy equivalent of 95.24; the aniline curing agent is 3,3'-diethyl-4,4'-diaminodiphenylmethane with an active hydrogen equivalent of 63; the colorant is carbon black; the coupling agent is (3-glycidylpropyl)trimethoxysilane;

[0091] The preparation method of the modified inorganic filler includes:

[0092] (1) Disperse 50 g of spherical silica (average particle size of 1 μm and truncated particle size of 5 μm) in 500 ml of absolute ethanol, then add 0.5 g of (azidomethyl)phenyltrimethoxysilane, and stir and reflux at 85 °C for 1 h to obtain a modified solution;

[0093] (2) Cool, centrifuge, and wash the modified solution, then perform solid-liquid separation, and bake the separated solid in an oven at 120 °C for 15 h to obtain the modified inorganic filler; among them, the structural formula of (azidomethyl)phenyltrimethoxysilane is as follows:

[0094]

[0095] The preparation method of the epoxy resin composition includes:

[0096] (1) Add 8.9 parts of low-viscosity epoxy resin, 15 parts of polyfunctional epoxy resin, 0.8 part of silane coupling agent, and 0.3 part of colorant to the mixing tank in sequence, and mix uniformly at high speed to obtain a first mixture;

[0097] (2) Add 60 parts of modified inorganic filler to the first mixture, and mix at high speed to fully disperse and homogenize the inorganic filler to obtain a second mixture;

[0098] (3) Add 15 parts of aniline curing agent to the second mixture, and mix at high speed to obtain the epoxy resin composition.

[0099] Example 2

[0100] In this embodiment, the epoxy resin composition comprises the following components in parts by weight: 8.9 parts of low-viscosity epoxy resin, 15 parts of polyfunctional epoxy resin, 15 parts of aniline curing agent, 60 parts of modified inorganic filler, 0.3 part of colorant, and 0.8 part of coupling agent.

[0101] Among them, the low-viscosity epoxy resin is bisphenol F epoxy resin with an epoxy equivalent of 159.00; the polyfunctional epoxy resin is 4-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline (AFG-90 epoxy resin) with an epoxy equivalent of 95.24; the aniline curing agent is 3,3'-diethyl-4,4'-diaminodiphenylmethane with an active hydrogen equivalent of 63; the colorant is carbon black; the coupling agent is (3-glycidylpropoxy)trimethoxysilane;

[0102] The preparation method of the modified inorganic filler includes:

[0103] (1) Disperse 50 g of spherical silica (average particle size of 1 μm and truncated particle size of 5 μm) in 500 ml of absolute ethanol, then add 0.5 g of p-azidomethylphenyltrimethoxysilane, and stir and reflux at 85 °C for 1 h to obtain a modified solution;

[0104] (2) Cool, centrifuge, and wash the modified solution, then perform solid-liquid separation, and bake the separated solid in an oven at 120 °C for 15 h to obtain the modified inorganic filler; among them, the structural formula of (azidomethyl)phenyltrimethoxysilane is as follows:

[0105]

[0106] The preparation method of the epoxy resin composition includes:

[0107] (1) Add 8.9 parts of low-viscosity epoxy resin, 15 parts of polyfunctional epoxy resin, 0.8 part of silane coupling agent, and 0.3 part of colorant to the mixing tank in sequence, and mix evenly at high speed to obtain a first mixture;

[0108] (2) Add 60 parts of modified inorganic filler to the first mixture, and mix at high speed to fully disperse the inorganic filler evenly to obtain a second mixture;

[0109] (3) Add 15 parts of aniline curing agent to the second mixture, and mix at high speed to obtain the epoxy resin composition.

[0110] Example 3

[0111] In this embodiment, the epoxy resin composition comprises the following components in parts by weight: 8.9 parts of low-viscosity epoxy resin, 15 parts of polyfunctional epoxy resin, 15 parts of aniline curing agent, 60 parts of modified inorganic filler, 0.3 part of colorant, and 0.8 part of coupling agent.

[0112] Among them, the low-viscosity epoxy resin is bisphenol F epoxy resin with an epoxy equivalent of 159.00; the multi-functional epoxy resin is 4-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline (AFG-90 epoxy resin) with an epoxy equivalent of 95.24; the aniline curing agent is 3,3'-diethyl-4,4'-diaminodiphenylmethane with an active hydrogen equivalent of 63; the colorant is carbon black; the coupling agent is (3-glycidylpropyl)trimethoxysilane;

[0113] The preparation method of the modified inorganic filler includes:

[0114] (1) Disperse 50 g of spherical silica (average particle size of 1 μm and truncated particle size of 5 μm) in 500 ml of absolute ethanol, then add 0.5 g of 3-(azidopropyl)triethoxysilane, and stir and reflux at 85 °C for 1 h to obtain a modified solution;

[0115] (2) Cool, centrifuge and wash the modified solution, then perform solid-liquid separation, and bake the separated solid in an oven at 120 °C for 15 h to obtain the modified inorganic filler; among them, the structural formula of 3-(azidopropyl)triethoxysilane is as follows:

[0116]

[0117] The preparation method of the epoxy resin composition includes:

[0118] (1) Add 8.9 parts of low-viscosity epoxy resin, 15 parts of multi-functional epoxy resin, 0.8 part of silane coupling agent, and 0.3 part of colorant to the mixing tank in sequence, and mix evenly at high speed to obtain a first mixture;

[0119] (2) Add 60 parts of modified inorganic filler to the first mixture, and mix at high speed to fully disperse the inorganic filler evenly to obtain a second mixture;

[0120] (3) Add 15 parts of aniline curing agent to the second mixture, and mix at high speed to obtain the epoxy resin composition.

[0121] Example 4

[0122] In this example, the epoxy resin composition includes the following components in parts by weight: 8.9 parts of low-viscosity epoxy resin, 15 parts of multi-functional epoxy resin, 15 parts of aniline curing agent, 60 parts of modified inorganic filler, 0.3 part of colorant, and 0.8 part of coupling agent.

[0123] Among them, the low-viscosity epoxy resin is bisphenol F epoxy resin with an epoxy equivalent of 159.00; the multi-functional epoxy resin is 4-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline (AFG-90 epoxy resin) with an epoxy equivalent of 95.24; the aniline curing agent is 3,3'-diethyl-4,4'-diaminodiphenylmethane with an active hydrogen equivalent of 63; the colorant is carbon black; the coupling agent is (3-glycidylpropyl)trimethoxysilane;

[0124] The preparation method of the modified inorganic filler includes:

[0125] (1) Disperse 50 g of spherical silica (average particle size of 1 μm and truncated particle size of 5 μm) in 500 ml of absolute ethanol, then add 0.5 g of 6-azidosulfonylhexyltriethoxysilane, and stir and reflux at 85 °C for 1 h to obtain a modified solution;

[0126] (2) Cool, centrifuge, and wash the modified solution, then perform solid-liquid separation, and bake the separated solid in an oven at 120 °C for 15 h to obtain the modified inorganic filler; among them, the structural formula of 6-azidosulfonylhexyltriethoxysilane is as follows:

[0127]

[0128] The preparation method of the epoxy resin composition includes:

[0129] (1) Add 8.9 parts of low-viscosity epoxy resin, 15 parts of multi-functional epoxy resin, 0.8 part of silane coupling agent, and 0.3 part of colorant to the mixing tank in sequence, and mix evenly at high speed to obtain the first mixture;

[0130] (2) Add 60 parts of modified inorganic filler to the first mixture, and mix at high speed to fully disperse the inorganic filler evenly to obtain the second mixture;

[0131] (3) Add 15 parts of aniline curing agent to the second mixture, and mix at high speed to obtain the epoxy resin composition.

[0132] Example 5

[0133] In this example, the epoxy resin composition includes the following components in parts by weight: 8.9 parts of low-viscosity epoxy resin, 15 parts of multi-functional epoxy resin, 15 parts of aniline curing agent, 60 parts of modified inorganic filler, 0.3 part of colorant, and 0.8 part of coupling agent.

[0134] Among them, the low-viscosity epoxy resin is bisphenol F epoxy resin with an epoxy equivalent of 159.00; the multi-functional epoxy resin is 4-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline (AFG-90 epoxy resin) with an epoxy equivalent of 95.24; the aniline curing agent is 3,3'-diethyl-4,4'-diaminodiphenylmethane with an active hydrogen equivalent of 63; the colorant is carbon black; the coupling agent is (3-glycidylpropyl)trimethoxysilane;

[0135] The preparation method of the modified inorganic filler includes:

[0136] (1) Disperse 50 g of spherical silica (average particle size of 1 μm and truncated particle size of 5 μm) in 500 ml of absolute ethanol, then add 0.5 g of 4-[2-(trimethoxysilyl)ethyl]benzene-1-sulfonyl azide compound, and stir and reflux at 85 °C for 1 h to obtain a modified solution;

[0137] (2) Cool, centrifuge, and wash the modified solution, then perform solid-liquid separation, and bake the separated solid in an oven at 120 °C for 15 h to obtain the modified inorganic filler; among them, the structural formula of 4-[2-(trimethoxysilyl)ethyl]benzene-1-sulfonyl azide compound is as follows:

[0138]

[0139] The preparation method of the epoxy resin composition includes:

[0140] (1) Add 8.9 parts of low-viscosity epoxy resin, 15 parts of multi-functional epoxy resin, 0.8 part of silane coupling agent, and 0.3 part of colorant to the mixing tank in sequence, and mix uniformly at high speed to obtain a first mixture;

[0141] (2) Add 60 parts of modified inorganic filler to the first mixture, and mix at high speed to fully disperse and homogenize the inorganic filler to obtain a second mixture;

[0142] (3) Add 15 parts of aniline curing agent to the second mixture, and mix at high speed to obtain the epoxy resin composition.

[0143] Example 6

[0144] In this example, the epoxy resin composition includes the following components in parts by weight: 8.9 parts of low-viscosity epoxy resin, 15 parts of multi-functional epoxy resin, 15 parts of aniline curing agent, 60 parts of modified inorganic filler, 0.3 part of colorant, and 0.8 part of coupling agent.

[0145] Among them, the low-viscosity epoxy resin is bisphenol F epoxy resin with an epoxy equivalent of 159.00; the multi-functional epoxy resin is 4-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline (AFG-90 epoxy resin) with an epoxy equivalent of 95.24; the aniline curing agent is 3,3'-diethyl-4,4'-diaminodiphenylmethane with an active hydrogen equivalent of 63; the colorant is carbon black; the coupling agent is (3-glycidylpropyl)trimethoxysilane;

[0146] The preparation method of the modified inorganic filler includes:

[0147] (1) Disperse 50 g of spherical silica (average particle size of 1 μm and truncated particle size of 5 μm) in 500 ml of absolute ethanol, then add 0.5 g of 11-azidoundecyltrimethoxysilane, and stir and reflux at 85 °C for 1 h to obtain a modified solution;

[0148] (2) Cool, centrifuge, and wash the modified solution, then perform solid-liquid separation, and bake the separated solid in an oven at 120 °C for 15 h to obtain the modified inorganic filler; among them, the structural formula of 11-azidoundecyltrimethoxysilane is as follows:

[0149]

[0150] The preparation method of the epoxy resin composition includes:

[0151] (1) Add 8.9 parts of low-viscosity epoxy resin, 15 parts of multi-functional epoxy resin, 0.8 part of silane coupling agent, and 0.3 part of colorant to the mixing tank in sequence, and mix evenly at high speed to obtain a first mixture;

[0152] (2) Add 60 parts of modified inorganic filler to the first mixture, and mix at high speed to fully disperse and homogenize the inorganic filler to obtain a second mixture;

[0153] (3) Add 15 parts of aniline curing agent to the second mixture, and mix at high speed to obtain the epoxy resin composition.

[0154] Example 7

[0155] In this example, the epoxy resin composition includes the following components in parts by weight: 8.9 parts of low-viscosity epoxy resin, 15 parts of multi-functional epoxy resin, 15 parts of aniline curing agent, 60 parts of modified inorganic filler, 0.3 part of colorant, and 0.8 part of coupling agent.

[0156] Among them, the low-viscosity epoxy resin is bisphenol F epoxy resin with an epoxy equivalent of 159.00; the multi-functional epoxy resin is 4-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline (AFG-90 epoxy resin) with an epoxy equivalent of 95.24; the aniline curing agent is 3,3'-diethyl-4,4'-diaminodiphenylmethane with an active hydrogen equivalent of 63; the colorant is carbon black; the coupling agent is (3-glycidylpropyl)trimethoxysilane;

[0157] The preparation method of the modified inorganic filler includes:

[0158] (1) Disperse 50 g of spherical silica (average particle size of 1 μm and truncated particle size of 5 μm) in 500 ml of absolute ethanol, then add 0.5 g of 3-{(dimethyl(3-trimethoxysilyl)propyl)ammonio}propane-1-sulfonate, and stir and reflux at 85 °C for 1 h to obtain a modified solution;

[0159] (2) Cool, centrifuge, and wash the modified solution, then perform solid-liquid separation, and bake the separated solid in an oven at 120 °C for 15 h to obtain the modified inorganic filler; among them, the structural formula of 3-{(dimethyl(3-trimethoxysilyl)propyl)ammonio}propane-1-sulfonate is as follows:

[0160]

[0161] The preparation method of the epoxy resin composition includes:

[0162] (1) Add 8.9 parts of low-viscosity epoxy resin, 15 parts of multi-functional epoxy resin, 0.8 part of silane coupling agent, and 0.3 part of colorant to the mixing tank in sequence, and mix evenly at high speed to obtain a first mixture;

[0163] (2) Add 60 parts of modified inorganic filler to the first mixture, and mix at high speed to fully disperse and homogenize the inorganic filler to obtain a second mixture;

[0164] (3) Add 15 parts of aniline curing agent to the second mixture, and mix at high speed to obtain the epoxy resin composition.

[0165] Example 8

[0166] In this example, the epoxy resin composition includes the following components in parts by weight: 8.9 parts of low-viscosity epoxy resin, 15 parts of multi-functional epoxy resin, 15 parts of aniline curing agent, 60 parts of modified inorganic filler, 0.3 part of colorant, and 0.8 part of coupling agent.

[0167] Among them, the low-viscosity epoxy resin is bisphenol F epoxy resin with an epoxy equivalent of 159.00; the multi-functional epoxy resin is 4-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline (AFG-90 epoxy resin) with an epoxy equivalent of 95.24; the aniline curing agent is 3,3'-diethyl-4,4'-diaminodiphenylmethane with an active hydrogen equivalent of 63; the colorant is carbon black; the coupling agent is (3-glycidylpropoxy)trimethoxysilane;

[0168] The preparation method of the modified inorganic filler includes:

[0169] (1) Disperse 50 g of spherical silica (average particle size of 1 μm and truncated particle size of 5 μm) in 500 ml of absolute ethanol, then add 0.5 g of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride, and stir and reflux at 85 °C for 1 h to obtain a modified solution;

[0170] (2) Cool, centrifuge, and wash the modified solution, then perform solid-liquid separation, and bake the separated solid in an oven at 120 °C for 15 h to obtain the modified inorganic filler; among them, the structural formula of dimethyloctadecyl[3-(trimethoxysilyl)propyl]ammonium chloride is as follows:

[0171]

[0172] The preparation method of the epoxy resin composition includes:

[0173] (1) Add 8.9 parts of low-viscosity epoxy resin, 15 parts of multi-functional epoxy resin, 0.8 part of silane coupling agent, and 0.3 part of colorant to the mixing tank in sequence, and mix evenly at high speed to obtain a first mixture;

[0174] (2) Add 60 parts of modified inorganic filler to the first mixture, and mix at high speed to fully disperse the inorganic filler evenly to obtain a second mixture;

[0175] (3) Add 15 parts of aniline curing agent to the second mixture, and mix at high speed to obtain the epoxy resin composition.

[0176] Example 9

[0177] In this example, the epoxy resin composition includes the following components in parts by weight: 8.9 parts of low-viscosity epoxy resin, 15 parts of multi-functional epoxy resin, 15 parts of aniline curing agent, 60 parts of modified inorganic filler, 0.3 part of colorant, and 0.8 part of coupling agent.

[0178] Among them, the low-viscosity epoxy resin is bisphenol F epoxy resin with an epoxy equivalent of 159.00; the multi-functional epoxy resin is 4-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline (AFG-90 epoxy resin) with an epoxy equivalent of 95.24; the aniline curing agent is 3,3'-diethyl-4,4'-diaminodiphenylmethane with an active hydrogen equivalent of 63; the colorant is carbon black; the coupling agent is (3-glycidoxypropyl)trimethoxysilane;

[0179] The preparation method of the modified inorganic filler includes:

[0180] (1) Disperse 50 g of spherical silica (average particle size of 1 μm and truncated particle size of 5 μm) in 500 ml of absolute ethanol, then add 0.5 g of (styrylmethyl)bis(triethoxysilylpropyl)ammonium chloride, and stir and reflux at 85 °C for 1 h to obtain a modified solution;

[0181] (2) Cool, centrifuge, and wash the modified solution, then perform solid-liquid separation, and bake the separated solid in an oven at 120 °C for 15 h to obtain the modified inorganic filler; among them, the structural formula of (styrylmethyl)bis(triethoxysilylpropyl)ammonium chloride is as follows:

[0182]

[0183] The preparation method of the epoxy resin composition includes:

[0184] (1) Add 8.9 parts of low-viscosity epoxy resin, 15 parts of multi-functional epoxy resin, 0.8 part of silane coupling agent, and 0.3 part of colorant to the mixing tank in sequence, and mix evenly at high speed to obtain the first mixture;

[0185] (2) Add 60 parts of modified inorganic filler to the first mixture, and mix at high speed to fully disperse and homogenize the inorganic filler to obtain the second mixture;

[0186] (3) Add 15 parts of aniline curing agent to the second mixture, and mix at high speed to obtain the epoxy resin composition.

[0187] Example 10

[0188] In this example, the epoxy resin composition includes the following components in parts by weight: 11 parts of low-viscosity epoxy resin, 18.9 parts of multi-functional epoxy resin, 19 parts of aniline curing agent, 50 parts of modified inorganic filler, 0.3 part of colorant, and 0.8 part of coupling agent.

[0189] Among them, the low-viscosity epoxy resin is bisphenol F epoxy resin with an epoxy equivalent of 159.00; the multi-functional epoxy resin is 4-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline (AFG-90 epoxy resin) with an epoxy equivalent of 95.24; the aniline curing agent is 3,3'-diethyl-4,4'-diaminodiphenylmethane with an active hydrogen equivalent of 63; the colorant is carbon black; the coupling agent is (3-glycidylpropyl)trimethoxysilane;

[0190] The preparation method of the modified inorganic filler includes:

[0191] (1) Disperse 50 g of spherical silica (average particle size of 1 μm and truncated particle size of 5 μm) in 500 ml of absolute ethanol, then add 0.5 g of (azidomethyl)phenyltrimethoxysilane, and stir and reflux at 85 °C for 1 h to obtain a modified solution;

[0192] (2) Cool, centrifuge, and wash the modified solution, then perform solid-liquid separation, and bake the separated solid in an oven at 120 °C for 15 h to obtain the modified inorganic filler; among them, the structural formula of (azidomethyl)phenyltrimethoxysilane is as follows:

[0193]

[0194] The preparation method of the epoxy resin composition includes:

[0195] (1) Add 11 parts of low-viscosity epoxy resin, 18.9 parts of multi-functional epoxy resin, 0.8 part of silane coupling agent, and 0.3 part of colorant to the mixing tank in sequence, and mix evenly at high speed to obtain the first mixture;

[0196] (2) Add 50 parts of modified inorganic filler to the first mixture, and mix at high speed to fully disperse the inorganic filler evenly to obtain the second mixture;

[0197] (3) Add 19 parts of aniline curing agent to the second mixture, and mix at high speed to obtain the epoxy resin composition.

[0198] Example 11

[0199] In this example, the epoxy resin composition includes the following components in parts by weight: 6.6 parts of low-viscosity epoxy resin, 11 parts of multi-functional epoxy resin, 11.3 parts of aniline curing agent, 70 parts of modified inorganic filler, 0.3 part of colorant, and 0.8 part of coupling agent.

[0200] Among them, the low-viscosity epoxy resin is bisphenol F epoxy resin with an epoxy equivalent of 159.00; the multi-functional epoxy resin is 4-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline (AFG-90 epoxy resin) with an epoxy equivalent of 95.24; the aniline curing agent is 3,3'-diethyl-4,4'-diaminodiphenylmethane with an active hydrogen equivalent of 63; the colorant is carbon black; the coupling agent is (3-glycidylpropyl)trimethoxysilane;

[0201] The preparation method of the modified inorganic filler includes:

[0202] (1) Disperse 50 g of spherical silica (average particle size of 1 μm and truncated particle size of 5 μm) in 500 ml of absolute ethanol, then add 0.5 g of (azidomethyl)phenyltrimethoxysilane, and stir and reflux at 85 °C for 1 h to obtain a modified solution;

[0203] (2) Cool, centrifuge, and wash the modified solution, then perform solid-liquid separation, and bake the separated solid in an oven at 120 °C for 15 h to obtain the modified inorganic filler; among them, the structural formula of (azidomethyl)phenyltrimethoxysilane is as follows:

[0204]

[0205] The preparation method of the epoxy resin composition includes:

[0206] (1) Add 6.6 parts of low-viscosity epoxy resin, 11 parts of multi-functional epoxy resin, 0.8 part of silane coupling agent, and 0.3 part of colorant to the mixing tank in sequence, and mix uniformly at high speed to obtain the first mixture;

[0207] (2) Add 70 parts of modified inorganic filler to the first mixture, and mix at high speed to fully disperse and homogenize the inorganic filler to obtain the second mixture;

[0208] (3) Add 11.3 parts of aniline curing agent to the second mixture, and mix at high speed to obtain the epoxy resin composition.

[0209] Example 12

[0210] In this example, the epoxy resin composition includes the following components in parts by weight: 8.9 parts of low-viscosity epoxy resin, 15 parts of multi-functional epoxy resin, 15 parts of aniline curing agent, 60 parts of modified inorganic filler, 0.3 part of colorant, and 0.8 part of coupling agent.

[0211] Among them, the low-viscosity epoxy resin is bisphenol F epoxy resin with an epoxy equivalent of 159.00; the multi-functional epoxy resin is 4-(2,3-epoxypropoxy)-N,N-bis(2,3-epoxypropyl)aniline (AFG-90 epoxy resin) with an epoxy equivalent of 95.24; the aniline curing agent is 3,3'-diethyl-4,4'-diaminodiphenylmethane with an active hydrogen equivalent of 63; the colorant is carbon black; the coupling agent is (3-glycidylpropyl)trimethoxysilane;

[0212] The preparation method of the modified inorganic filler includes:

[0213] (1) Disperse 50 g of spherical silica (average particle size of 1 μm and truncated particle size of 5 μm) in 500 ml of absolute ethanol, then add 1 g of (azidomethyl)phenyltrimethoxysilane, and stir and reflux at 85 °C for 1 h to obtain a modified solution;

[0214] (2) Cool, centrifuge and wash the modified solution, then perform solid-liquid separation, and bake the separated solid in an oven at 120 °C for 15 h to obtain the modified inorganic filler; among them, the structural formula of (azidomethyl)phenyltrimethoxysilane is as follows:

[0215]

[0216] The preparation method of the epoxy resin composition includes:

[0217] (1) Add 8.9 parts of low-viscosity epoxy resin, 15 parts of multi-functional epoxy resin, 0.8 part of silane coupling agent, and 0.3 part of colorant to the mixing tank in sequence, and mix evenly at high speed to obtain a first mixture;

[0218] (2) Add 60 parts of modified inorganic filler to the first mixture, and mix at high speed to make the inorganic filler fully dispersed and uniform to obtain a second mixture;

[0219] (3) Add 15 parts of aniline curing agent to the second mixture, and mix at high speed to obtain the epoxy resin composition.

[0220] Example 13

[0221] The difference between this example and Example 1 is that the epoxy resin composition includes the following components in parts by weight: 26.9 parts of low-viscosity epoxy resin, 12 parts of aniline curing agent, 60 parts of modified inorganic filler, 0.3 part of colorant, and 0.8 part of coupling agent. The remaining conditions are the same as those in Example 1.

[0222] Example 14

[0223] The difference between this embodiment and Embodiment 1 lies in that the epoxy resin composition comprises the following components in parts by weight: 22.4 parts of multi-functional epoxy resin, 16.5 parts of aniline curing agent, 60 parts of modified inorganic filler, 0.3 part of colorant, and 0.8 part of coupling agent. Other conditions are the same as those in Embodiment 1.

[0224] Comparative Example 1

[0225] In this embodiment, the epoxy resin composition comprises the following components in parts by weight: 8.9 parts of low-viscosity epoxy resin, 15 parts of multi-functional epoxy resin, 15 parts of aniline curing agent, 60 parts of silicon dioxide, 0.3 part of colorant, and 0.8 part of coupling agent.

[0226] The preparation method of the epoxy resin composition includes:

[0227] (1) Add 8.9 parts of low-viscosity epoxy resin, 5 parts of multi-functional epoxy resin, 0.8 part of silane coupling agent, and 0.3 part of colorant into a mixing tank in sequence, and mix them uniformly at high speed to obtain a first mixture;

[0228] (2) Add 60 parts of modified inorganic filler into the first mixture, and mix at high speed to fully disperse the inorganic filler uniformly to obtain a second mixture;

[0229] (3) Add 15 parts of aniline curing agent into the second mixture, and mix at high speed to obtain the epoxy resin composition.

[0230] Thermodynamic property tests, viscosity tests, and filler distribution deviation tests are carried out on the epoxy resin compositions in Examples 1-14 and Comparative Example 1.

[0231] Among them, the method for the thermodynamic property test is: use the double-cantilever mode of a dynamic thermomechanical analyzer to test the glass transition temperature and storage modulus of the cured epoxy resin composition. The method for the viscosity test is: use a rotational rheometer to measure the viscosity of the freshly prepared epoxy resin composition at a liquid temperature of 25°C and a rotation speed of 50 rpm. Filler distribution deviation test: It is carried out using the self-made test system as shown in Figure 1 to evaluate the distribution deviation of the epoxy resin composition during the curing process by simulating the potential difference between the metals used for metal bumps and the metals used for solders in the actual encapsulation process. The results are shown in Table 1:

[0232] Table 1 Performance test results of epoxy resin compositions in different examples and comparative examples

[0233]

[0234] Through Table 1 and Figures 2 - 5It can be seen that the epoxy resin compositions prepared in Examples 1-14 of the present application can effectively inhibit the deviation of filler distribution during the curing process, thereby ensuring the encapsulation effect and long-term stability. Among them, for the epoxy resin compositions prepared in Examples 1-9, the glass transition temperatures all reach above 180°C, the storage moduli are all greater than 8 GPa, and the viscosities at 25°C are all less than 30 Pa·s. The workability can meet the narrow pitch filling of 2.5D packaging. For example, as Figure 2 and Figure 4 shown, in Example 1, the separation length of the modified inorganic filler is less than 20 μm, with better effects. In the epoxy resin composition prepared in Example 11, the addition ratio of the modified inorganic filler is relatively large, resulting in a relatively high viscosity of the epoxy resin composition. In the epoxy resin composition prepared in Example 13, no multi-functional epoxy resin is added, resulting in a relatively low glass transition temperature of the epoxy resin composition and a decrease in viscosity. In the epoxy resin composition prepared in Example 14, no low-viscosity epoxy resin is added, resulting in a significant increase in the glass transition temperature of the epoxy resin composition and an increase in viscosity. As Figure 3 and Figure 5 shown, in Comparative Example 1, the viscosity of the epoxy resin composition at 25°C is greater than 30 Pa·s, and obvious filler distribution deviation occurs, making it difficult to meet the requirements of 2.5D packaging.

[0235] The above has introduced the embodiments of the present application in detail. Specific examples are used in this article to elaborate on the principle and implementation manner of the present application. The description of the above embodiments is only used to help understand the method and its core idea of the present application; at the same time, for those skilled in the art, according to the idea of the present application, there will be changes in the specific implementation manner and application scope. In summary, the content of this specification should not be construed as a limitation to the present application.

Claims

1. An epoxy resin composition, characterized in that Including epoxy resin, curing agent and modified inorganic filler; The modified inorganic filler includes silicon dioxide and a siloxane compound containing an ionic bond grafted on the surface of the silicon dioxide.

2. The epoxy resin composition according to claim 1, characterized in that The invention comprises the following components in parts by weight: 15 to 35 parts of epoxy resin, 10 to 20 parts of curing agent and 10 to 20 parts of the modified inorganic filler.

3. The epoxy resin composition according to claim 2, characterized in that The epoxy resin comprises the following components by weight: 5-15 parts of low-viscosity epoxy resin and 10-20 parts of multifunctional epoxy resin; and / or The curing agent comprises an aniline curing agent; and / or The epoxy resin composition further comprises the following components in parts by weight: 0.1 to 5 parts of a colorant and 0.1 to 5 parts of a coupling agent.

4. The epoxy resin composition according to any one of claims 1 to 3, characterized in that The ionic bond-containing siloxane compound includes at least one of an azide-based siloxane compound and an amine-based siloxane compound.

5. The epoxy resin composition according to any one of claims 1 to 3, characterized in that The siloxane compounds containing ionic bonds include (azidomethyl)phenyltrimethoxysilane, p-azidomethylphenyltrimethoxysilane, 3-(azidopropyl)triethoxysilane, 6-azidosulfonylhexyltriethoxysilane, 4-[2-(trimethoxysilyl)ethyl]benzene-1-sulfonyl azide, 11-azidoundecyltrimethoxysilane, 3-{(dimethyl(3-trimethoxysilyl)propyl)ammonium}propane-1-sulfonate, 4-nitro-4'(n-ethyl-n-butyl)propane-1-sulfonate, At least one of trimethoxysilylcarbamate) aminoazobenzene, dimethyloctadecyl [3-(trimethoxysilyl) propyl] ammonium chloride, vinylbenzylaminoethylaminopropyl trimethoxysilane hydrochloride, (styrylmethyl)bis (triethoxysilylpropyl) ammonium chloride, N-trimethoxysilylpropyl-N,N,N-tri-n-butylammonium chloride, nitrogen-trimethoxysilylpropyl-nitrogen, nitrogen, nitrogen-trimethylammonium chloride and tetradecyldimethyl (3-trimethoxysilylpropyl) ammonium chloride.

6. The epoxy resin composition according to claim 3, characterized in that The viscosity of the low-viscosity epoxy resin is 0.5Pa·s-3Pa·s, and the epoxy value is 0.36-0.78eq / 100g; And / or, the low viscosity epoxy resin includes at least one of bisphenol A epoxy resin, bisphenol AD ​​epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin and hydrogenated bisphenol A epoxy resin.

7. The epoxy resin composition according to claim 3, characterized in that The multifunctional epoxy resin includes a multifunctional glycidyl ether epoxy resin and / or a multifunctional glycidyl amine epoxy resin.

8. The epoxy resin composition according to claim 3, characterized in that The aniline curing agent includes at least one of m-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, diaminodiphenylmethane (4,4'-methylenedianiline), diethyltoluenediamine, 3,3'-diethyl-4,4'-diaminodiphenylmethane and derivatives thereof.

9. A method for preparing an epoxy resin composition, for preparing the epoxy resin composition according to any one of claims 1 to 8, characterized in that: include: Providing raw materials including modified inorganic fillers; The raw materials are mixed to obtain an epoxy resin composition.

10. The method for preparing the epoxy resin composition according to claim 9, characterized in that: The preparation method of the modified inorganic filler comprises: dispersing silicon dioxide in a solvent to obtain a dispersed solution; Adding a siloxane compound containing an ionic bond to the dispersed solution, reacting at a temperature of 80° C. to 90° C. for 0.5 h to 1.5 h to obtain a modified solution; The modified inorganic filler is obtained by performing solid-liquid separation and drying on the modified solution.

11. The method for preparing the epoxy resin composition according to claim 9, characterized in that: The raw materials include low-viscosity epoxy resin, multifunctional epoxy resin, aniline curing agent, modified inorganic filler, colorant and coupling agent; The mixing of the raw materials comprises: The low-viscosity epoxy resin, the multifunctional epoxy resin, the colorant and the coupling agent are mixed to obtain a first mixture; Adding the modified inorganic filler into the first mixed material, and mixing to obtain a second mixed material; The aniline curing agent is added to the second mixed material, and the mixture is mixed to obtain an epoxy resin composition.

12. An application of an epoxy resin composition, characterized in that: The epoxy resin composition as claimed in any one of claims 1 to 8 is applied to the field of electronic materials.

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