An epoxy resin composition, a method for preparing the same, and an application thereof

Abstract

The present application belongs to the field of underfill adhesive, and particularly relates to an epoxy resin composition, a preparation method and application thereof. The epoxy resin composition contains an epoxy resin, a toughening agent, a curing agent, and optionally toner and a coupling agent, and the curing agent contains at least a cyclic anhydride compound with a structure shown in formula (1). The epoxy resin composition provided by the present application uses a cyclic anhydride compound with a specific structure as a curing agent, and the obtained epoxy resin composition has high high-temperature bonding strength and high Tg, and can meet the requirements of underfill adhesive in the field of semiconductor packaging. Formula (1).

Description

Technical Field

[0001] This invention belongs to the field of bottom-filling adhesives, specifically relating to an epoxy resin composition, its preparation method, and its application. Background Technology

[0002] Underfill adhesives are resin adhesives used in electronic packaging processes. They penetrate micron-level gaps through capillary action and are primarily used in semiconductor packaging. Besides filling the gaps between common PCBs and chips, they are also used between flexible printed circuit boards (FPCBs) and chips. Compared to adhesives used between chips and PCBs, those used between chips and FPCBs present greater challenges in formulation design. In addition to possessing the basic properties of conventional underfill adhesives, these adhesives also need to exhibit stronger bonding strength and toughness.

[0003] Epoxy underfillers typically contain epoxy resin, toughening agents, and curing agents. Common epoxy resins include bisphenol A type epoxy resin, bisphenol F type epoxy resin, and alicyclic epoxy resin. Common curing agents include amine curing agents and acid anhydride curing agents. Increasing the epoxy group content in the epoxy resin generally improves bond strength, but reduces toughness, especially at high temperatures. This is mainly because these epoxy underfillers form a three-dimensional network structure after curing, which restricts molecular chain movement. The increased number of epoxy groups and crosslinking density further exacerbates this restriction, making the material brittle. Furthermore, the internal stress generated by curing shrinkage cannot be released, easily leading to cracking. Moreover, existing epoxy underfillers, after aging at 85℃ and 85% humidity for 120 hours, still only achieve a bond strength of 11 MPa, indicating low high-temperature bond strength. In addition, to ensure the operational stability of electronic products, the glass transition temperature (Tg) of the epoxy underfill must be higher than the operating temperature. If the operating temperature is close to or exceeds Tg, the epoxy underfill will soften rapidly due to the intensified molecular chain movement, resulting in a decrease in strength and affecting the performance of electronic products. Summary of the Invention

[0004] The primary objective of this invention is to provide an epoxy resin composition with high high-temperature adhesive strength and high Tg.

[0005] A second objective of the present invention is to provide a method for preparing the above-mentioned epoxy resin composition.

[0006] A third objective of the present invention is to provide the application of the above-described epoxy resin composition as a bottom filler adhesive for electronic products.

[0007] The epoxy resin composition provided by the present invention contains epoxy resin, toughening agent and curing agent, as well as optional colorant and coupling agent, wherein the curing agent contains at least a cyclic anhydride compound having the structure shown in formula (1').

[0008] Equation (1`),

[0009] In equation (1), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 and R 14 Each is an alkyl group that is independently H or C1 to C6.

[0010] The method for preparing the epoxy resin composition provided by the present invention includes mixing epoxy resin, toughening agent, curing agent, colorant, coupling agent and trifunctional epoxy compound evenly to obtain the epoxy resin composition.

[0011] The epoxy resin composition provided by this invention uses a cyclic anhydride compound with a specific structure as a curing agent. The resulting epoxy resin composition exhibits high high-temperature adhesive strength and high Tg, meeting the requirements of underfill adhesives in the semiconductor packaging field. The reason for this is presumably that the cyclic anhydride compound possesses a multifunctional anhydride structure and an aromatic ring structure, with the anhydride structure linked to the aromatic ring structure via ether bonds. The presence of the multifunctional anhydride structure allows the epoxy resin composition to form a cross-linked network structure, while the rigid aromatic ring structure enhances the stability of the resulting network molecular structure. The covalent bonds forming the aromatic ring structure require higher temperatures to break down. The ether bond linking the anhydride structure to the aromatic ring structure creates strong intermolecular forces between the two. These strong intermolecular forces prevent the molecular chains from undergoing thermal motion and deformation at high temperatures, avoiding excessive relaxation and separation of the molecular chains. Therefore, the epoxy resin composition can withstand higher temperatures, resulting in higher high-temperature adhesive strength and Tg.

[0012] In a preferred embodiment, the method for preparing the cyclic anhydride compounds starts from polyhydroxy aromatic compounds and constructs cyclic anhydride compounds through a three-step reaction of Michael addition, cyano hydrolysis, and intramolecular condensation. It does not require complex protecting group operations, and the reaction temperature is carried out below 70°C, avoiding high temperature and high pressure, which is suitable for industrial scale-up production. At the same time, the yield of the target product is stable at 60%~80%, which has the advantages of simple steps, mild conditions and stable yield, and is suitable for industrial production.

[0013] In a preferred embodiment, the epoxy resin composition further contains a trifunctional epoxy compound having the structure shown in formula (1). The trifunctional epoxy compound has a triethylene glycol structure, a pyridine structure, and three epoxy groups. Two epoxy groups are respectively bonded to the carbon atom adjacent to the nitrogen atom on the pyridine ring, and the remaining epoxy group is bonded to the triethylene glycol structure. This specific trifunctional epoxy compound has unique electronic conjugation characteristics and chemical activity, which can impart good toughness to the epoxy resin composition without affecting its high-temperature bonding strength and high Tg. Detailed Implementation

[0014] The epoxy resin composition provided by this invention contains epoxy resin, toughening agent, curing agent, and optionally colorant and coupling agent. The preferred mass ratio of the epoxy resin, toughening agent, curing agent, colorant, and coupling agent is 100:(20-300):(20-500):(0-20):(0-100). Specifically, the preferred mass ratio of the epoxy resin to the toughening agent is 100:(20-300), such as 100:20, 100:50, 100:80, 100:100, 100:120, 100:150, 100:180, 100:200, 100:220, 100:250, 100:280, 100:300, or any value between them. The preferred mass ratio of epoxy resin to curing agent is 100:(20-500), such as 100:20, 100:50, 100:80, 100:100, 100:120, 100:150, 100:180, 100:200, 100:220, 100:250, 100:280, 100:300, 100:320, 100:350, 100:380, 100:400, 100:420, 100:450, 100:480, 100:500, or any value between them. The preferred mass ratio of epoxy resin to colorant is 100:(0-20), such as 0, 100:1, 100:2, 100:4, 100:6, 100:8, 100:10, 100:12, 100:14, 100:16, 100:18, 100:20, or any value between them. The preferred mass ratio of epoxy resin to coupling agent is 100:(0-100), such as 0, 100:2, 100:5, 100:10, 100:13, 100:15, 100:18, 100:20, 100:50, 100:80, 100:100, or any value between them.

[0015] In a preferred embodiment, the epoxy resin content is 10-50 parts by weight, the toughening agent content is 10-30 parts by weight, the curing agent content is 10-50 parts by weight, the colorant content is 0.5-2 parts by weight, and the coupling agent content is 1-10 parts by weight. This combination allows for better synergistic effects, which is more conducive to improving high-temperature bonding strength and Tg. Specifically, the epoxy resin content can be 10, 15, 20, 25, 30, 35, 40, 45, 50 parts by weight or any value between them. The toughening agent content can be 10, 12, 15, 18, 20, 22, 25, 28, 30 parts by weight or any value between them. The curing agent content can be 10, 15, 20, 25, 30, 35, 40, 45, 50 parts by weight or any value between them. The content of the pigment can be 0.5, 0.8, 1, 1.2, 1.5, 1.8, or 2 parts by weight, or any value between them. The content of the coupling agent can be 1, 2, 4, 6, 8, or 10 parts by weight, or any value between them.

[0016] In this invention, the curing agent contains at least a cyclic anhydride compound, which may be solely a cyclic anhydride compound or a mixture of a cyclic anhydride compound and a conventional anhydride curing agent. Preferably, the cyclic anhydride compound constitutes 10-100% of the total weight of the curing agent, more preferably 20-100%, further preferably 30-100%, more preferably 40-100%, more preferably 50-100%, more preferably 60-100%, more preferably 70-100%, more preferably 80-100%, more preferably 90-100%, and most preferably 100%. A higher proportion of the cyclic anhydride compound is more beneficial for improving the bonding strength. The conventional anhydride curing agents may include at least one of the following: methylnadic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, hexahydro-4-methylphthalic anhydride (MHHPA), methyltetrahydrophthalic anhydride (MTHPA), methylcyclohexene-1,2-dicarboxylic anhydride, methylbicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, bicyclo[2.2.1]heptane-2,3-dicarboxylic anhydride, (2-dodecen-1-yl)succinic anhydride, glutaric anhydride, citrate anhydride, methylsuccinic anhydride, 2,2,-dimethylsuccinic anhydride, 2,2,-dimethylglutaric anhydride, 3-methylglutaric anhydride, 3,3-tetramethyleneglutaric anhydride, and 3,3-dimethylglutaric anhydride.

[0017] In this invention, the curing agent cyclic anhydride compound has the structure shown in formula (1'):

[0018] Equation (1`),

[0019] In equation (1), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 and R 14 Each of the alkyl groups is independently H or C1-C6. Examples of C1-C6 alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, or neopentyl.

[0020] In this invention, the cyclic anhydride compound preferably has a symmetrical structure, in which case R1, R7, R8, and R... 14 The same applies to R2, R6, R9, and R... 13 Same, R3, R5, R 10 and R 12 Same, R4 and R 11 The same. When cyclic anhydride compounds have a symmetrical structure, the overall structure after curing can be guaranteed to be stable and not easily affected by external conditions (such as temperature changes), resulting in higher high-temperature bonding strength and Tg. In a preferred embodiment, in formula (1), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 and R 14 All are H.

[0021] In a preferred embodiment, the cyclic anhydride compound is prepared by a method comprising the following steps:

[0022] S1'. Michael addition: A polyhydroxy aromatic compound is reacted with acrylonitrile via cyanoethylation to yield a polycyano aromatic compound;

[0023] S2'. Cyano hydrolysis: The polycyano aromatic compound is hydrolyzed to convert the cyano group into a carboxyl group, yielding a polycarboxyl aromatic compound;

[0024] S3`. Intramolecular condensation: Intramolecular anhydride reaction of polycarboxylic aromatic compounds to obtain cyclic anhydride compounds.

[0025] In the preparation of the above-mentioned cyclic anhydride compounds, the polyhydroxy aromatic compounds have the structure shown in formula (2'):

[0026] Equation (2'),

[0027] In equation (2'), R3, R4, R5, R 10 R 11 and R 12 Each of the alkyl groups is independently H or C1-C6. Examples of C1-C6 alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, or neopentyl.

[0028] In the preparation of the above-mentioned cyclic anhydride compounds, the polyhydroxy aromatic compound preferably has a symmetrical structure, in which case R3, R5, and R... 10 and R 12 Same, R4 and R 11 same.

[0029] In a preferred embodiment, in formula (2'), R3, R4, R5, R 10 R 11 and R 12 All are H.

[0030] In the preparation of the above-mentioned cyclic anhydride compounds, in step S1', the cyanoethylation reaction is carried out in the presence of a base and an organic solvent. The molar ratio of the base to the polyhydroxy aromatic compound is preferably 5:1 to 12:1, such as 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12:1, or any value between them. The amount of acrylonitrile used is preferably 5 to 12 times the molar amount of the polyhydroxy aromatic compound, such as 5 times, 6 times, 7 times, 8 times, 9 times, 10 times, 11 times, 12 times, 13 times, 14 times, 15 times, or any value between them. The preferred conditions for the cyanoethylation reaction include a temperature of 20–50°C, such as 20°C, 25°C, 30°C, 35°C, 40°C, 45°C, 50°C, or any value between therewith; and a time of 8–24 h, such as 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h, 24 h, or any value between therewith. The base may include at least one of potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate. The organic solvent is preferably methanol and / or ethanol.

[0031] In the preparation process of the above-mentioned cyclic anhydride compounds, in step S2', the hydrolysis reaction includes reflux reaction of the polycyano aromatic compound in a concentrated hydrochloric acid / methanol system. The volume ratio of the concentrated hydrochloric acid to methanol is preferably 1:3 to 1:5, such as 1:3, 1:3.5, 1:4, 1:4.5, 1:5, or any value between them. The reflux reaction time is preferably 6 h to 24 h, such as 6 h, 8 h, 10 h, 12 h, 14 h, 16 h, 18 h, 20 h, 22 h, 24 h, or any value between them.

[0032] In the preparation of the above-mentioned cyclic anhydride compounds, in step S3', the intramolecular anhydride reaction is preferably carried out in the presence of dicyclohexylcarbodiimide (DCC). The molar ratio of the dicyclohexylcarbodiimide to the polycarboxylic aromatic compound is preferably 2:1 to 3:1, such as 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, or any value between them. The preferred conditions for the intramolecular anhydride reaction include a temperature of 0~30℃, such as 0℃, 2℃, 5℃, 8℃, 10℃, 12℃, 15℃, 18℃, 20℃, 22℃, 25℃, 30℃ or any value between them; and a time of 10~36h, such as 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h, 26h, 28h, 30h, 32h, 34h, 36h or any value between them.

[0033] The reaction mechanism for the preparation of the above-mentioned cyclic anhydride compounds is as follows:

[0034] .

[0035] In the epoxy resin composition, the epoxy resin can be any of the existing aromatic epoxy resins and / or aliphatic epoxy resins, specific examples of which include, but are not limited to: at least one of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, o-hydroxymethyl bisphenol A diglycidyl ether, dihydroxymethyl bisphenol A diglycidyl ether, tetrabromobisphenol A diglycidyl ether, resorcinol diglycidyl ether, and pyromelliticol triglycidyl ether pentaerythritol diglycidyl ether, preferably bisphenol A diglycidyl ether and / or bisphenol F diglycidyl ether.

[0036] In the epoxy resin composition, specific examples of the toughening agent include, but are not limited to, at least one of: polyurethane, cashew nutshell liquid-modified phenolic resin, unsaturated polyester resin, epoxy resin active toughening agent, and SBS thermoplastic elastomer. The unsaturated polyester resin may be at least one of 182 unsaturated polyester resin, 196 unsaturated polyester resin, etc.

[0037] In the epoxy resin composition, the pigment can be selected according to the actual application scenario, without any particular limitation, and can be at least one of titanium dioxide, carbon black, iron oxide red, etc.

[0038] In the epoxy resin composition, the coupling agent is used to improve the compatibility between the organic and inorganic components of the epoxy resin composition and increase the adhesive strength. Examples of coupling agents include at least one selected from: γ-aminopropyltriethylsiloxane, γ-glycidoxypropyltrimethoxysiloxane, γ-methacrylate propyltrimethoxysiloxane, γ-thiol propyltrimethoxysiloxane, vinyltritert-butylperoxide, β-hydroxyethyl-γ-aminopropyltriethoxysiloxane, anilinemethyltriethoxysilane, and diethylenetriaminopropyltriethoxysilane.

[0039] In the epoxy resin composition, the epoxy resin composition preferably further contains a trifunctional epoxy compound having the structure shown in formula (1). In this case, the epoxy resin composition can be endowed with good toughness without affecting its high-temperature adhesive strength and high Tg. In addition, the mass ratio of the trifunctional epoxy compound to the epoxy resin is preferably (10-300):100, such as 10:100, 20:100, 50:100, 80:100, 100:100, 120:100, 150:100, 180:100, 200:100, 220:100, 250:100, 280:100, 300:100 or any value between them.

[0040] Equation (1),

[0041] In equation (1), R 1 and R 2 Each alkyl group is independently H or C1-C5, preferably H. Examples of C1-C5 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, or neopentyl.

[0042] In a preferred embodiment, the trifunctional epoxy compound is prepared by a method comprising the following steps:

[0043] S1. Halogenated propylene oxide and tetraethylene glycol are subjected to a first substitution reaction in the presence of base I and catalyst I. The resulting intermediate I is subjected to an active group protection reaction in the presence of base II to obtain intermediate II.

[0044] S2. 2,6-Dicarboxaldehyde-4-hydroxypyridine and phosphorus ylide are subjected to a Wittig reaction. The resulting vinyl hydroxypyridine is then subjected to a second substitution reaction with intermediate II in the presence of base III and catalyst II. Subsequently, the resulting intermediate III is oxidized to obtain a product containing a trifunctional epoxy compound.

[0045] In the preparation process of the above trifunctional epoxy compounds, the halo-epoxypropane has the structure shown in formula (2):

[0046] Equation (2),

[0047] In formula (2), X is a halogen, such as fluorine, chlorine, bromine or iodine.

[0048] In the preparation of the above trifunctional epoxy compound, the triethylene glycol has the structure shown in formula (3):

[0049] Equation (3).

[0050] In the preparation of the above trifunctional epoxy compound, the 2,6-dicarboxaldehyde-4-hydroxypyridine has the structure shown in formula (4):

[0051] Equation (4),

[0052] In equation (4), R 1 and R 2 Each alkyl group is independently H or C1-C5, preferably H. Examples of C1-C5 alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, or neopentyl.

[0053] The reaction equations for the preparation of the above trifunctional epoxy compounds are as follows:

[0054] .

[0055] In the preparation process of the above trifunctional epoxy compound, in step S1, the molar ratio of the halopropylene oxide to triethylene glycol is 1:(1-1.1), such as 1:1, 1:1.01, 1:1.02, 1:1.03, 1:1.04, 1:1.05, 1:1.06, 1:1.07, 1:1.08, 1:1.09, 1:1.1 or any value between them.

[0056] In the preparation process of the above-mentioned trifunctional epoxy compound, in step S1, the molar ratio of the active group protecting agent to triethylene glycol is preferably (0.9-1.1):1, such as 0.9:1, 0.92:1, 0.94:1, 0.96:1, 0.98:1, 1:1, 1.02:1, 1.04:1, 1.06:1, 1.08:1, 1.1:1, or any value between them. The active group protecting agent may include at least one of tert-butyldimethylchlorosilane (TBSCl), trimethylchlorosilane, triethylchlorosilane, triisopropylchlorosilane, dimethylphenylchlorosilane, and tert-butyldiphenylchlorosilane.

[0057] In the preparation process of the above trifunctional epoxy compound, in step S2, the molar ratio of 2,6-dicarboxaldehyde-4-hydroxypyridine to intermediate II is preferably 1:(0.9-1.1), such as 1:0.9, 1:0.92, 1:0.94, 1:0.96, 1:0.98, 1:1, 1:1.02, 1:1.04, 1:1.06, 1:1.08, 1:1.1 or any value between them.

[0058] In the preparation process of the above trifunctional epoxy compound, in step S1, the conditions for the first substitution reaction preferably include a temperature of 50℃-70℃, such as 50℃, 52℃, 55℃, 58℃, 60℃, 62℃, 65℃, 68℃, 70℃ or any value between them; and a time of 10h-24h, such as 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h or any value between them.

[0059] In the preparation process of the above trifunctional epoxy compound, in step S1, the conditions for the active group protection reaction preferably include a temperature of 10℃-30℃, such as 10℃, 12℃, 15℃, 18℃, 20℃, 22℃, 25℃, 28℃, 30℃ or any value between them; and a time of 5h-12h, such as 5h, 8h, 10h, 12h or any value between them.

[0060] In the preparation process of the above trifunctional epoxy compound, in step S2, the Wittig reaction conditions preferably include a temperature of -20℃ to 0℃, such as -20℃, -18℃, -16℃, -14℃, -12℃, -10℃, -8℃, -6℃, -4℃, -2℃, 0℃ or any value between them; and a time of 1h to 24h, such as 1h, 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h, 20h, 22h, 24h or any value between them.

[0061] In the preparation process of the above trifunctional epoxy compound, in step S2, the conditions for the second substitution reaction include a temperature of 25℃-100℃, such as 25℃, 30℃, 35℃, 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃ or any value between them; and a time of 2h-18h, such as 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h, 18h or any value between them.

[0062] In the preparation process of the above trifunctional epoxy compound, in step S2, the oxidation reaction conditions preferably include a temperature of 40℃-100℃, such as 40℃, 45℃, 50℃, 55℃, 60℃, 65℃, 70℃, 75℃, 80℃, 85℃, 90℃, 95℃, 100℃ or any value between them; and a time of 6h-18h, such as 6h, 8h, 10h, 12h, 14h, 16h, 18h or any value between them.

[0063] In a preferred embodiment, in step S1, the method for the first substitution reaction and the active group protection reaction includes dissolving halopropylene oxide, base I, and catalyst I in organic solvent I, heating the resulting mixture to the first substitution reaction temperature under inert gas protection and stirring, then adding tetraethylene glycol trioxide to carry out the first substitution reaction, removing the solvent after the reaction is complete, washing the crude product with water and drying it, then dissolving the obtained intermediate I, base II, and active group protectant in organic solvent II to carry out the active group protection reaction, removing the solvent after the reaction is complete, washing the crude product with water and drying it to obtain intermediate II.

[0064] In a preferred embodiment, step S2, the method for the Wittig reaction, the second substitution reaction, and the oxidation reaction includes dissolving 2,6-dicarboxaldehyde-4-hydroxypyridine and phosphorus ylide in organic solvent III, then reacting at the Wittig reaction temperature under inert gas protection. After the reaction is complete, water is added sequentially for quenching, extraction, solvent removal, and drying to obtain vinylhydroxypyridine. Vinylhydroxypyridine, base III, and catalyst II are dissolved in organic solvent IV, and the temperature is raised to the second substitution reaction temperature under inert gas protection and stirring. Then, intermediate II is added to carry out the second substitution reaction. After the reaction is complete, the solvent is removed to obtain intermediate III. Intermediate III is dissolved in organic solvent V, cooled to -5°C to 5°C, and an oxidant is slowly added. The temperature is then raised to the oxidation reaction temperature to continue the reaction. After the reaction is complete, a product containing a trifunctional epoxy compound is obtained. The phosphorus ylide is generally generated by triphenylmethylphosphorus bromide under the action of a strong base. The strong base may include at least one of n-butyllithium, phenyllithium, potassium tert-butoxide, and sodium tert-butoxide. In the specific reaction process, 2,6-dicarboxaldehyde-4-hydroxypyridine, triphenylmethylphosphorus bromide, and the strong base can be dissolved in organic solvent III, and then the reaction is carried out under inert gas protection at the Wittig reaction temperature.

[0065] In the preparation of the above trifunctional epoxy compounds, the types of organic solvent I, organic solvent II, organic solvent III, organic solvent IV, and organic solvent V are not particularly limited. They can be any existing inert liquid substances that can be used as reaction media, and can be at least one of alcohol solvents, ester solvents, ether solvents, hydrocarbon solvents, ketone solvents, etc. Specifically, they can be selected from at least one of acetonitrile, dichloromethane, tetrahydrofuran, and N,N-dimethylformamide.

[0066] In the preparation of the above-mentioned trifunctional epoxy compounds, the types of catalysts I and II are not particularly limited, and can be any existing substances that can improve the rate of substitution reactions. Catalyst I can include at least one of benzyltriethylammonium chloride, 18-crown ether-6, tetrabutylammonium chloride, and tetrabutylammonium bromide, with tetrabutylammonium bromide being particularly preferred. Catalyst II can include at least one of 4-dimethylaminopyridine, tetrabutylammonium hydroxide, trioctylmethylammonium chloride, 15-crown ether-5, tetradecyltrimethylammonium chloride, triphenylmethylphosphine bromide, and trioctylmethylphosphine chloride, with 15-crown ether-5 being preferred. When catalysts I and II are selected as the above-mentioned preferred catalysts, it is more beneficial to improve the yield of the trifunctional epoxy compounds.

[0067] In the preparation of the above trifunctional epoxy compounds, the terms "Ⅰ", "Ⅱ", "Ⅲ", "Ⅳ" and "Ⅴ" are merely used to distinguish the same type of substance used in different steps for ease of description, and have no other special meaning.

[0068] In the preparation of the above-mentioned trifunctional epoxy compounds, the type of oxidant is not particularly limited and can be any existing substance that can improve the reaction rate, such as at least one of potassium permanganate, manganese dioxide, potassium peroxymonosulfonate, and m-chloroperoxybenzoic acid (m-CPBA), with m-CPBA being particularly preferred. When m-CPBA is selected as the oxidant, it is more beneficial to improve the yield of the trifunctional epoxy compounds.

[0069] The method for preparing the epoxy resin composition provided by this invention includes uniformly mixing epoxy resin, toughening agent, curing agent, and optionally colorant, coupling agent, and trifunctional epoxy compound to obtain the epoxy resin composition. The mixing method is not particularly limited; the materials can be added and mixed uniformly in any order. For example, the epoxy resin, toughening agent, curing agent, and optionally colorant, coupling agent, and trifunctional epoxy compound can be stirred and mixed in a container. Every 10-20 minutes of stirring, the container walls are opened and scraped, then stirring continues. After the micelles are mixed, vacuum degassing is initiated while stirring is performed. After vacuum degassing for 10-20 minutes, the material is discharged to obtain the epoxy resin composition.

[0070] The present invention also provides the application of the epoxy resin composition as a bottom filler adhesive for electronic products.

[0071] The present invention will be described in detail below through embodiments. These embodiments are intended to explain the invention and should not be construed as limiting it. Where specific techniques or conditions are not specified in the embodiments, they shall be performed in accordance with the techniques or conditions described in the literature in the art or according to the product instructions. Reagents or instruments whose manufacturers are not specified are all conventional products that can be obtained commercially.

[0072] In the following examples and comparative examples, bisphenol F diglycidyl ether was purchased from Mitsubishi Chemical Corporation, grade 806, with an epoxy equivalent of 160 g / eq; bisphenol A diglycidyl ether was purchased from Mitsubishi Chemical Corporation, grade 828, with an epoxy equivalent of 184 g / eq; and SBS thermoelastic resin was purchased from Kraton, grade D1155.

[0073] Preparation Example 1-1: Preparation of Trifunctional Epoxides

[0074] S1. 9.2 g (0.1 mol, 1 eq) of epichlorohydrin was dissolved in 200 mL of acetonitrile, followed by the addition of 41.5 g (0.3 mol, 3.05 eq) of potassium carbonate and 3.2 g (0.01 mol, 0.1 eq) of tetrabutylammonium bromide. The mixture was heated to 60 °C and stirred for 20 min under inert gas protection. Then, 19.4 g (0.1 mol, 1 eq) of tetraethylene glycol was slowly added and the mixture was reacted for 12 h. The solvent was then recovered by vacuum distillation, followed by washing with water and drying to obtain 23 g of intermediate I. 23 g (91 mmol, 1 eq) of intermediate I was dissolved in 200 mL of dichloromethane. After nitrogen purging, 13.8 g (136.5 mmol, 1.5 eq) of triethylamine and 15 g (0.1 mol, 1 eq) of TBSCl were added. The mixture was stirred at 10 °C for 6 h. After the reaction was completed, the solvent was removed by vacuum distillation. The crude product was washed with water and dried to obtain 27 g of intermediate II.

[0075] S2. 15.1 g (0.1 mol, 1 eq) of 2,6-dicarboxaldehyde-4-hydroxypyridine was dissolved in 200 mL of tetrahydrofuran, cooled to 0 °C, and 6.4 g (0.1 mol, 1 eq) of n-butyllithium and 37.3 g (0.11 mol, 1.1 eq) of triphenylmethylphosphorus bromide were added under argon protection. The mixture was stirred for 1 h, and after the reaction was completed, it was quenched with water. The mixture was then extracted with 200 mL of dichloromethane, and the organic phase was distilled under reduced pressure to remove the solvent, yielding 12 g of 2,6-diethylene-4-hydroxypyridine. 12 g (80 mmol, 1 eq) of 2,6-diethylene-4-hydroxypyridine was dissolved in 160 mL of N,N-dimethylformamide, followed by the addition of 33.7 g (244 mmol, 3.05 eq) of potassium carbonate and 1 g (DMAP, 8 mmol, 0.1 eq) of 4-dimethylaminopyridine. After heating to 70 °C, 40 g (0.11 mol, 1.1 eq) of intermediate II was slowly added. After the addition was complete, the reaction was stirred for 8 h. After the reaction was completed, water was added to quench the reaction, and the solvent was removed by extraction and vacuum distillation to obtain 40.2 g of intermediate III. 40.2 g (84 mmol, 1 eq) of intermediate III was dissolved in 160 mL of dichloromethane, cooled to 0 °C, and 43.5 g (252 mmol, 3 eq) of m-CPBA was slowly added. The temperature was then raised to 40 °C, and the reaction was continued at this temperature for 12 h. The solution was then diluted with dichloromethane and washed three times with saturated sodium bicarbonate aqueous solution and two times with saturated sodium thiosulfate aqueous solution. The organic phase was collected and evaporated to dryness to obtain 36.9 g of trifunctional epoxy compound, denoted as EP-1.

[0076] The overall yield of the reaction was 72.1%. The NMR results are as follows: 1H NMR (400 MHz, DMSO-d6) δ 7.05(s, 2H), 4.16 (dt, J = 12.3, 6.1 Hz, 1H), 4.02 (dt, J = 12.4, 6.2 Hz, 1H), 3.94(t, J =5.1 Hz, 2H), 3.82 (dt, J = 12.4, 6.2 Hz, 1H), 3.77 -3.71 (m, 3H), 3.74-3.55 (m, 15H), 3.42 (dd, J = 7.2, 5.5 Hz, 1H), 2.97 (dd, J = 7.2, 5.5 Hz, 1H), 2.89 (p, J =5.6 Hz, 1H). The NMR results show that the trifunctional epoxy compound has the structure shown in formula (1).

[0077] Preparation Examples 1-2: Preparation of Trifunctional Epoxides

[0078] S1. 46 g (0.5 mol, 1 eq) of epichlorohydrin was dissolved in 1 L of acetonitrile, followed by the addition of 207.3 g (1.5 mol, 3.05 eq) of potassium carbonate and 16 g (0.05 mol, 0.1 eq) of tetrabutylammonium bromide. The mixture was heated to 50 °C and stirred for 20 min under inert gas protection. Then, 97 g (0.5 mol, 1 eq) of tetraethylene glycol was slowly added and the mixture was reacted for 24 h. The solvent was then recovered by vacuum distillation, followed by washing with water and drying to obtain 107 g of intermediate I. 107 g (0.42 mol, 1 eq) of intermediate I was dissolved in 1 L of dichloromethane. After nitrogen purging, 63.7 g (0.63 mol, 1.5 eq) of triethylamine and 63.3 g (0.42 mol, 1 eq) of TBSCl were added. The mixture was stirred at 30 °C for 5 h. After the reaction was completed, the solvent was removed by vacuum distillation. The crude product was washed with water and dried to obtain 119 g of intermediate II.

[0079] S2. 75.5 g (0.5 mol, 1 eq) of 2,6-dicarboxaldehyde-4-hydroxypyridine was dissolved in 1 L of tetrahydrofuran, cooled to -20 °C, and 32 g (0.5 mol, 1 eq) of n-butyllithium and 188.76 g (0.55 mol, 1.1 eq) of triphenylphosphine bromide were added under argon protection. The mixture was stirred for 24 h. After the reaction was completed, the mixture was quenched with water, extracted with 500 mL of dichloromethane, and the organic phase was then distilled under reduced pressure to remove the solvent, yielding 62 g of 2,6-diethylene-4-hydroxypyridine. 62 g (0.41 mol, 1 eq) of 2,6-diethylene-4-hydroxypyridine was dissolved in 800 mL of N,N-dimethylformamide, followed by the addition of 33.7 g (1.25 mol, 3.05 eq) of potassium carbonate and 4.9 g (40.1 mmol, 0.1 eq) of DMAP. The temperature was maintained at 25 °C, and then 112.8 g (0.45 mol, 1.1 eq) of intermediate II was slowly added. After the addition was complete, the reaction was stirred for 18 h. After the reaction was completed, water was added to quench the reaction, and the solvent was removed by extraction and vacuum distillation to obtain 204 g of intermediate III. 204 g (0.43 mol, 1 eq) of intermediate III was dissolved in 800 mL of dichloromethane, cooled to 0 °C, and 220.8 g (1.28 mol, 3 eq) of m-CPBA was slowly added. The temperature was raised to 60 °C, and the reaction was continued at this temperature for 18 h. Then, dichloromethane was added to dilute the solution, and the solution was washed three times with saturated sodium bicarbonate aqueous solution and then twice with saturated sodium thiosulfate aqueous solution. The organic phase was collected and evaporated to dryness to obtain 172 g of trifunctional epoxy compound, denoted as EP-2.

[0080] The overall yield of the reaction was 67.4%. The NMR results are as follows: 1 H NMR (400 MHz, DMSO-d6) δ 7.05(s, 2H), 4.16 (dt, J = 12.3, 6.1 Hz, 1H), 4.02 (dt, J = 12.4, 6.2 Hz, 1H), 3.94(t, J =5.1 Hz, 2H), 3.82 (dt, J = 12.4, 6.2 Hz, 1H), 3.77 -3.71 (m, 3H), 3.74-3.55 (m, 15H), 3.42 (dd, J = 7.2, 5.5 Hz, 1H), 2.97 (dd, J = 7.2, 5.5 Hz, 1H), 2.89 (p, J=5.6 Hz, 1H). The NMR results show that the trifunctional epoxy compound has the structure shown in formula (1).

[0081] Preparation Examples 1-3: Preparation of Trifunctional Epoxides

[0082] S1. 92 g (1 mol, 1 eq) of epichlorohydrin was dissolved in 2 L of acetonitrile, followed by the addition of 414.6 g (3 mol, 3.05 eq) of potassium carbonate and 32 g (0.1 mol, 0.1 eq) of tetrabutylammonium bromide. The mixture was heated to 70 °C and stirred for 20 min under inert gas protection. Then, 213 g (1.1 mol, 1.1 eq) of tetraethylene glycol was slowly added and the mixture was reacted for 10 h. The solvent was then recovered by vacuum distillation, washed with water, and dried to obtain 240 g of intermediate I. 240 g (0.6 mol, 1 eq) of intermediate I was dissolved in 1200 mL of dichloromethane. After nitrogen purging, 91 g (0.9 mol, 1.5 eq) of triethylamine and 90.4 g (0.6 mol, 1 eq) of TBSCl were added. The mixture was stirred at 20 °C for 12 h. After the reaction was complete, the solvent was removed by vacuum distillation. The crude product was washed with water and dried to obtain 290 g of intermediate II.

[0083] S2. 151.1 g (1 mol, 1 eq) of 2,6-dicarboxaldehyde-4-hydroxypyridine was dissolved in 2 L of tetrahydrofuran, cooled to -10 °C, and 64 g (1 mol, 1 eq) of n-butyllithium and 377.5 g (1.1 mol, 1.1 eq) of triphenylphosphine bromide were added under argon protection. The mixture was stirred for 10 h. After the reaction was completed, water was added to quench the reaction, followed by extraction with 800 mL of dichloromethane. The organic phase was then distilled under reduced pressure to remove the solvent, yielding 140 g of 2,6-diethylene-4-hydroxypyridine. 140 g (0.94 mol, 1 eq) of 2,6-diethylene-4-hydroxypyridine was dissolved in 1.6 L of N,N-dimethylformamide, followed by the addition of 1.3 kg (9.38 mol, 3.05 eq) of potassium carbonate and 10 g (80 mmol, 0.1 eq) of DMAP. After heating to 100 °C, 400 g (1.1 mol, 1.1 eq) of intermediate II was slowly added. After the addition was complete, the mixture was stirred for 2 h. After the reaction was completed, water was added to quench the reaction, and the solvent was removed by extraction and vacuum distillation to obtain 410 g of intermediate III. 410 g (0.86 mol, 1 eq) of intermediate III was dissolved in 1600 mL of dichloromethane, cooled to 0 °C, and 445 g (2.58 mol, 3 eq) of m-CPBA was slowly added. The temperature was raised to 100 °C, and the reaction was continued at this temperature for 6 h. Then, dichloromethane was added to dilute the solution, and the solution was washed three times with saturated sodium bicarbonate aqueous solution and then twice with saturated sodium thiosulfate. The organic phase was collected and evaporated to dryness to obtain 382 g of trifunctional epoxy compound, denoted as EP-1.

[0084] The overall yield of the reaction was 74.8%. The NMR results are as follows: 1 H NMR (400 MHz, DMSO-d6) δ 7.05(s, 2H), 4.16 (dt, J = 12.3, 6.1 Hz, 1H), 4.02 (dt, J = 12.4, 6.2 Hz, 1H), 3.94(t, J =5.1 Hz, 2H), 3.82 (dt, J = 12.4, 6.2 Hz, 1H), 3.77 -3.71 (m, 3H), 3.74-3.55 (m, 15H), 3.42 (dd, J = 7.2, 5.5 Hz, 1H), 2.97 (dd, J = 7.2, 5.5 Hz, 1H), 2.89 (p, J=5.6 Hz, 1H). The NMR results show that the trifunctional epoxy compound has the structure shown in formula (1).

[0085] Preparation Example 2-1: Preparation of Cyclic Anhydride Compounds

[0086] S1`. A polyhydroxy aromatic compound (having the structure shown in formula (II), R3, R4, R5, R 10 R 11 and R 12 All of the above (0.6 g, 3.0 mmol) were dissolved in methanol (30 mL), and KOH (1.0 g, 18 mmol) was added. The mixture was stirred until clear, and acrylonitrile (2.4 mL, 36 mmol) was added dropwise under ice bath conditions. The mixture was stirred at 20 °C for 24 h. After the reaction was completed, the reaction was quenched with water. The resulting product was then extracted three times with dichloromethane. The organic phase was washed successively with saturated NaCl solution, dried over anhydrous Na2SO4, the organic solvent was removed under reduced pressure, and purified by column chromatography to obtain a polycyano aromatic compound (white solid).

[0087] S2. Dissolve the polycyano aromatic compound (0.73 g, 1.5 mmol) in methanol (20 mL), add concentrated hydrochloric acid (5 mL), and reflux for 12 h. After the reaction is complete, remove the methanol by rotary evaporation, dissolve the residue in water, extract three times with dichloromethane, acidify the aqueous phase to pH 2 with concentrated hydrochloric acid, precipitate a white solid, filter, and dry to obtain the polycarboxylic aromatic compound.

[0088] S3. A polycarboxylated aromatic compound (0.34 g, 0.7 mmol) was dissolved in dichloromethane (20 mL), and DCC (0.3 g, 1.5 mmol) was added. The mixture was stirred at 25 °C for 24 h. After the reaction was complete, dicyclohexylurea was removed by filtration, and the filtrate was concentrated by rotary evaporation and purified by column chromatography to give 0.25 g of a cyclic anhydride compound (white solid, denoted as AH-1), with a yield of 80%.

[0089] The NMR data and characteristic data of this cyclic anhydride compound are as follows: 1 H NMR (400 MHz, DMSO-d6) δ7.20 (p, J = 1.0 Hz, 2H), 4.57 (d, J = 1.0 Hz, 8H), 3.75 (t, J = 7.1 Hz, 8H), 2.62(t, J = 7.1 Hz, 8H). From the above results, it can be seen that this cyclic anhydride compound has the structure shown in formula (1'), and R1, R2, R3, R4, R5, R6, R7, R8, R9, R... 10 R11 R 12 R 13 and R 14 All are H.

[0090] Preparation Example 2-2: Preparation of Cyclic Anhydride Compounds

[0091] S1`. A polyhydroxy aromatic compound (having the structure shown in formula (II), R3, R4, R5, R 10 R 11 and R 12 All of the above (0.6 g, 3.0 mmol) were dissolved in ethanol (30 mL), and NaOH (0.6 g, 15 mmol) was added. The mixture was stirred until clear, and acrylonitrile (1 mL, 15 mmol) was added dropwise under ice bath conditions. The mixture was stirred at 50 °C for 8 h. After the reaction was completed, the reaction was quenched with water. The resulting product was then extracted three times with dichloromethane. The organic phase was washed successively with saturated NaCl solution, dried over anhydrous Na2SO4, the organic solvent was removed under reduced pressure, and purified by column chromatography to obtain a polycyano aromatic compound (white solid).

[0092] S2. Dissolve the polycyano aromatic compound (0.73 g, 1.5 mmol) in methanol (15 mL), add concentrated hydrochloric acid (5 mL), and reflux for 24 h. After the reaction is complete, remove the methanol by rotary evaporation, dissolve the residue in water, extract three times with dichloromethane, acidify the aqueous phase to pH 2 with concentrated hydrochloric acid, precipitate a white solid, filter, and dry to obtain the polycarboxylic aromatic compound.

[0093] S3. A polycarboxylated aromatic compound (0.34 g, 0.7 mmol) was dissolved in dichloromethane (20 mL), and DCC (0.35 g, 1.75 mmol) was added. The mixture was stirred at 0 °C for 36 h. After the reaction was complete, dicyclohexylurea was removed by filtration, and the filtrate was concentrated by rotary evaporation and purified by column chromatography to give 0.24 g of a cyclic anhydride compound (white solid, denoted as AH-2), with a yield of 78%.

[0094] The NMR data and characteristic data of this cyclic anhydride compound are basically the same as those of Preparation Example 2-1. It can be seen that this cyclic anhydride compound has the structure shown in formula (1'), and R1, R2, R3, R4, R5, R6, R7, R8, R9, R... 10 R 11 R 12 R 13 and R 14 All are H.

[0095] Preparation Examples 2-3: Preparation of Cyclic Anhydride Compounds

[0096] S1`. A polyhydroxy aromatic compound (having the structure shown in formula (II), R3, R4, R5, R 10 R 11 and R 12 All of the above (0.6 g, 3.0 mmol) were dissolved in ethanol (30 mL), and K2CO3 (3.3 g, 24 mmol) was added. The mixture was stirred until clear, and acrylonitrile (2 mL, 30 mmol) was added dropwise under ice bath conditions. The mixture was stirred at 35 °C for 15 h. After the reaction was completed, the reaction was quenched with water. The resulting product was then extracted three times with dichloromethane. The organic phase was washed successively with saturated NaCl solution, dried over anhydrous Na2SO4, the organic solvent was removed under reduced pressure, and purified by column chromatography to obtain a polycyano aromatic compound (white solid).

[0097] S2. Dissolve 0.73 g (1.5 mmol) of a polycyano aromatic compound in methanol (25 mL), add concentrated hydrochloric acid (5 mL), and reflux for 6 h. After the reaction is complete, remove methanol by rotary evaporation, dissolve the residue in water, extract three times with dichloromethane, acidify the aqueous phase to pH 2 with concentrated hydrochloric acid, precipitate a white solid, filter, and dry to obtain the polycarboxylic aromatic compound.

[0098] S3. A polycarboxylated aromatic compound (0.34 g, 0.7 mmol) was dissolved in dichloromethane (20 mL), and DCC (0.42 g, 2.1 mmol) was added. The mixture was stirred at 30 °C for 10 h. After the reaction was complete, dicyclohexylurea was removed by filtration, and the filtrate was concentrated by rotary evaporation and purified by column chromatography to give 0.23 g of a cyclic anhydride compound (white solid, denoted as AH-3), with a yield of 75%.

[0099] The NMR data and characteristic data of this cyclic anhydride compound are basically the same as those of Preparation Example 2-1. It can be seen that this cyclic anhydride compound has the structure shown in formula (1'), and R1, R2, R3, R4, R5, R6, R7, R8, R9, R... 10 R 11 R 12 R 13 and R 14 All are H.

[0100] Example 1: Epoxy Resin Composition and its Preparation Method

[0101] (1) The raw material composition is as follows:

[0102] 19 parts by weight of bisphenol A diglycidyl ether;

[0103] 25 parts by weight of bisphenol F diglycidyl ether;

[0104] 20 parts by weight of SBS thermoelastic resin;

[0105] 30 parts by weight of cyclic acid anhydride compound (AH-1);

[0106] 1 part by weight of carbon black;

[0107] 5 parts by weight of γ-epoxypropoxypropyltrimethoxysiloxane.

[0108] (2) Preparation method of epoxy resin composition:

[0109] Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, SBS thermoelastic resin, cyclic anhydride compounds, carbon black, and γ-epoxypropoxypropyltrimethoxysiloxane were stirred and mixed in a dual planetary hybrid stirring tank for 30 minutes. The tank walls were scraped every 15 minutes of stirring, and then stirring was continued. After the micelles were mixed, vacuum degassing was started while stirring was started. After vacuum degassing for 10 minutes, the material was discharged to obtain the epoxy resin composition.

[0110] Example 2: Epoxy Resin Composition and its Preparation Method

[0111] (1) The raw material composition is as follows:

[0112] 19 parts by weight of bisphenol A diglycidyl ether;

[0113] 25 parts by weight of bisphenol F diglycidyl ether;

[0114] 20 parts by weight of SBS thermoelastic resin;

[0115] 15 parts by weight of cyclic acid anhydride compound (AH-2);

[0116] 15 parts by weight of methylnadic anhydride;

[0117] 1 part by weight of carbon black;

[0118] 5 parts by weight of γ-epoxypropoxypropyltrimethoxysiloxane.

[0119] (2) Preparation method of epoxy resin composition:

[0120] Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, SBS thermoelastic resin, cyclic anhydride compounds, methyl nadic anhydride, carbon black, and γ-epoxypropoxypropyltrimethoxysiloxane were stirred and mixed in a dual planetary hybrid stirred tank for 30 minutes. The tank walls were scraped every 15 minutes of stirring, and then stirring was continued. After the micelles were mixed, vacuum degassing was started while stirring was started. After vacuum degassing for 10 minutes, the material was discharged to obtain the epoxy resin composition.

[0121] Example 3: Epoxy Resin Composition and its Preparation Method

[0122] (1) The raw material composition is as follows:

[0123] 19 parts by weight of bisphenol A diglycidyl ether;

[0124] 25 parts by weight of bisphenol F diglycidyl ether;

[0125] 20 parts by weight of SBS thermoelastic resin;

[0126] 5 parts by weight of cyclic acid anhydride compound (AH-3);

[0127] 25 parts by weight of methylnadic anhydride;

[0128] 1 part by weight of carbon black;

[0129] 5 parts by weight of γ-epoxypropoxypropyltrimethoxysiloxane.

[0130] (2) Preparation method of epoxy resin composition:

[0131] Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, SBS thermoelastic resin, cyclic anhydride compounds, methyl nadic anhydride, carbon black, and γ-epoxypropoxypropyltrimethoxysiloxane were stirred and mixed in a dual planetary hybrid stirred tank for 30 minutes. The tank walls were scraped every 15 minutes of stirring, and then stirring was continued. After the micelles were mixed, vacuum degassing was started while stirring was started. After vacuum degassing for 10 minutes, the material was discharged to obtain the epoxy resin composition.

[0132] Example 4: Epoxy Resin Composition and its Preparation Method

[0133] An epoxy resin composition was prepared according to the method of Example 1, except that 30 parts by weight of the cyclic anhydride compound (AH-1) was replaced by a mixture of 25 parts by weight of the cyclic anhydride compound (AH-1) and 5 parts by weight of methylnadic anhydride, and the other conditions were the same as in Example 1, to obtain the epoxy resin composition.

[0134] Example 5: Epoxy Resin Composition and its Preparation Method

[0135] (1) The raw material composition is as follows:

[0136] 10 parts by weight of bisphenol A diglycidyl ether;

[0137] 30 parts by weight of SBS thermoelastic resin;

[0138] 20 parts by weight of cyclic acid anhydride compound (AH-1);

[0139] 30 parts by weight of trifunctional epoxy compound (EP-1);

[0140] 1 part by weight of carbon black;

[0141] 9 parts by weight of γ-epoxypropoxypropyltrimethoxysiloxane.

[0142] (2) Preparation method of epoxy resin composition:

[0143] Bisphenol A diglycidyl ether, SBS thermoelastic resin, cyclic anhydride compounds, trifunctional epoxy compounds, carbon black, and γ-epoxypropoxypropyltrimethoxysiloxane were stirred and mixed in a dual planetary hybrid stirring vessel for 30 minutes. The vessel walls were scraped every 15 minutes of stirring, and then stirring was continued. After the micelles were mixed, vacuum degassing was started while stirring was started. After vacuum degassing for 10 minutes, the material was discharged to obtain the epoxy resin composition.

[0144] Example 6: Epoxy Resin Composition and its Preparation Method

[0145] (1) The raw material composition is as follows:

[0146] 25 parts by weight of bisphenol F diglycidyl ether;

[0147] 28 parts by weight of SBS thermoelastic resin;

[0148] 20 parts by weight of cyclic acid anhydride compound (AH-1);

[0149] 15 parts by weight of trifunctional epoxy compound (EP-1);

[0150] 2 parts by weight of carbon black;

[0151] 10 parts by weight of γ-epoxypropoxypropyltrimethoxysiloxane.

[0152] (2) Preparation method of epoxy resin composition:

[0153] Bisphenol F diglycidyl ether, SBS thermoelastic resin, cyclic anhydride compounds, trifunctional epoxy compounds, carbon black, and γ-epoxypropoxypropyltrimethoxysiloxane were stirred and mixed in a dual planetary hybrid stirring tank for 30 minutes. The tank walls were scraped every 15 minutes of stirring, and then stirring was continued. After the micelles were mixed, vacuum degassing was started while stirring was started. After vacuum degassing for 10 minutes, the material was discharged to obtain the epoxy resin composition.

[0154] Example 7: Epoxy Resin Composition and its Preparation Method

[0155] (1) The raw material composition is as follows:

[0156] 20 parts by weight of bisphenol F diglycidyl ether;

[0157] 20 parts by weight of bisphenol A diglycidyl ether;

[0158] 10 parts by weight of SBS thermoelastic resin;

[0159] 40 parts by weight of cyclic acid anhydride compound (AH-1);

[0160] 5 parts by weight of trifunctional epoxy compound (EP-1);

[0161] 1 part by weight of carbon black;

[0162] 4 parts by mass of γ-epoxypropoxypropyltrimethoxysiloxane.

[0163] (2) Preparation method of epoxy resin composition:

[0164] Bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, SBS thermoelastic resin, cyclic anhydride compounds, trifunctional epoxy compounds, carbon black, and γ-epoxypropoxypropyltrimethoxysiloxane were stirred and mixed in a dual planetary hybrid stirring tank for 30 minutes. The tank walls were scraped every 15 minutes of stirring, and then stirring was continued. After the micelles were mixed, vacuum degassing was started while stirring was started. After vacuum degassing for 10 minutes, the material was discharged to obtain the epoxy resin composition.

[0165] Example 8: Epoxy Resin Composition and its Preparation Method

[0166] An epoxy resin composition was prepared according to the method of Example 1, except that 19 parts by weight of bisphenol A bisglycidyl ether was replaced by a mixture of 10 parts by weight of bisphenol A bisglycidyl ether and 9 parts by weight of trifunctional epoxy compound (EP-1), and the other conditions were the same as in Example 1, to obtain the epoxy resin composition.

[0167] Comparative Example 1: Reference epoxy resin composition and its preparation method

[0168] An epoxy resin composition was prepared according to the method of Example 2, except that the cyclic anhydride compound (AH-2) was replaced with the same amount of methyl nadic anhydride, and the other conditions were the same as in Example 2, to obtain a reference epoxy resin composition.

[0169] Comparative Example 2

[0170] An epoxy resin composition was prepared according to the method of Comparative Example 1, except that bisphenol A bisglycidyl ether was replaced with the same amount of bisphenol F bisglycidyl ether by weight, and the other conditions were the same as those of Comparative Example 1, to obtain a reference epoxy resin composition.

[0171] Comparative Example 3

[0172] An epoxy resin composition was prepared according to the method of Comparative Example 1, except that bisphenol F bisglycidyl ether was replaced with the same amount of bisphenol A bisglycidyl ether by weight, and the other conditions were the same as those of Comparative Example 1, to obtain a reference epoxy resin composition.

[0173] Test case

[0174] (1) Tg (glass transition temperature): The epoxy resin compositions obtained in the above examples and the reference epoxy resin composition obtained in the comparative example were cured at 150°C for 120 min, and then the Tg was measured using a differential calorimeter with a heating rate of 10°C / min. The results are shown in Table 1.

[0175] (2) Adhesive strength: The epoxy resin compositions obtained in the above embodiments and the reference epoxy resin composition obtained in the comparative example were coated on a silicon wafer, and then covered and pressed onto an FR5 substrate to make test samples. The bonding area was 2mm × 2.5mm and the adhesive layer thickness was 45μm. The samples were cured at 150℃ for 120min. The cured samples were then pushed sideways using a Dage 4000 and tested under high temperature (260℃) conditions. The measured force values ​​were recorded as high temperature adhesive strength (MPa). After curing, the samples were treated under heating and humidification conditions of 85℃ / 85%RH for 120h, and then the adhesive strength was tested under high temperature (255℃) conditions. The measured force values ​​were recorded as aging high temperature adhesive strength (MPa). The results are shown in Table 1.

[0176] (3) Modulus: The epoxy resin compositions obtained in the above examples and the reference epoxy resin composition obtained in the comparative example were cured at 160℃ / 100min and then made into specimens with dimensions of 55mm×5mm×2mm. The specimens were tested on a DMA. The measurement mode was dual cantilever mode, the vibration frequency was 1Hz, the amplitude was 10μm, the heating rate was 10°C / min, and the temperature range was -65℃~300℃. The modulus data at 200℃ were selected for comparison. The results are shown in Table 1.

[0177] (4) Elongation at break: The epoxy resin compositions obtained in the above examples and the reference epoxy resin composition obtained in the comparative example were cured and made into dog bone samples. The samples were heated to 250°C at room temperature and held at the high temperature for 1.2 min on a DMA instrument in tensile mode, and then loaded with 6 N / min to 18 N. The results are shown in Table 1.

[0178] Table 1

[0179]

[0180] As can be seen from the results in Table 1, the epoxy resin compositions provided in Examples 1-6, which contain cyclic anhydride compounds with the structure shown in formula (1), exhibit high-temperature adhesive strength exceeding 20.88 MPa, high-temperature adhesive strength after aging exceeding 12.95 MPa, and a Tg exceeding 118°C. This demonstrates high high-temperature adhesive strength and high Tg, meeting the requirements of underfill adhesives in the semiconductor packaging field. Comparative Example 1 differs from Example 2 only in that the cyclic anhydride compound is replaced with the same weight of methyl nadic anhydride. The results show that the high-temperature adhesive strength of Comparative Example 1 decreases to 15.23 MPa, the high-temperature adhesive strength after aging decreases to 10.44 MPa, and the Tg decreases to 109°C. A comparison between Examples 1 and 8 shows that when the epoxy resin composition also contains a trifunctional epoxy compound with the structure shown in formula (1), it can impart better toughness to the epoxy resin composition.

[0181] Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Those skilled in the art can make changes, modifications, substitutions and variations to the above embodiments within the scope of the present invention without departing from the principles and spirit of the present invention.

Claims

1. An epoxy resin composition, characterized in that, The epoxy resin composition contains epoxy resin, toughening agent and curing agent, as well as optional colorant and coupling agent, wherein the curing agent contains at least a cyclic anhydride compound having the structure shown in formula (1'). Equation (1`), In equation (1), R1, R2, R3, R4, R5, R6, R7, R8, R9, R 10 R 11 R 12 R 13 and R 14 Each is an alkyl group that is independently H or C1 to C6.

2. The epoxy resin composition according to claim 1, characterized in that, The epoxy resin content is 10-50 parts by weight, the toughening agent content is 10-30 parts by weight, the curing agent content is 10-50 parts by weight, the colorant content is 0.5-2 parts by weight, and the coupling agent content is 1-10 parts by weight.

3. The epoxy resin composition according to claim 1, characterized in that, The cyclic anhydride compounds account for 10-100% of the total weight of the curing agent.

4. The epoxy resin composition according to claim 1, characterized in that, The cyclic anhydride compounds have a symmetrical structure.

5. The epoxy resin composition according to any one of claims 1-4, characterized in that, The cyclic anhydride compound is prepared by a method comprising the following steps: S1`. Michael addition: The polyhydroxy aromatic compound shown in formula (2`) is reacted with acrylonitrile by cyanoethylation to obtain a polycyano aromatic compound; S2'. Cyano hydrolysis: The polycyano aromatic compound is hydrolyzed to convert the cyano group into a carboxyl group, yielding a polycarboxyl aromatic compound; S3'. Intramolecular condensation: Intramolecular anhydride reaction of polycarboxylic aromatic compounds to obtain cyclic anhydride compounds; Equation (2'), In equation (2'), R3, R4, R5, R 10 R 11 and R 12 Each is an alkyl group that is independently H or C1 to C6.

6. The epoxy resin composition according to claim 5, characterized in that, In step S1', the cyanoethylation reaction is carried out in the presence of an alkali and an organic solvent.

7. The epoxy resin composition according to claim 6, characterized in that, In step S1', the molar ratio of the alkali to the polyhydroxy aromatic compound is 5:1 to 12:

1.

8. The epoxy resin composition according to claim 6, characterized in that, In step S1', the amount of acrylonitrile used is 5 to 12 times the molar amount of the polyhydroxy aromatic compound.

9. The epoxy resin composition according to claim 6, characterized in that, In step S1', the conditions for the cyanoethylation reaction include a temperature of 20~50℃ and a time of 8~24h.

10. The epoxy resin composition according to claim 6, characterized in that, In step S1', the alkali is selected from at least one of potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate.

11. The epoxy resin composition according to claim 6, characterized in that, In step S1', the organic solvent is methanol and / or ethanol.

12. The epoxy resin composition according to claim 5, characterized in that, In step S2', the hydrolysis reaction is carried out by reflux reaction of the polycyano aromatic compound in a concentrated hydrochloric acid / methanol system.

13. The epoxy resin composition according to claim 12, characterized in that, In step S2', the volume ratio of concentrated hydrochloric acid to methanol is 1:3 to 1:

5.

14. The epoxy resin composition according to claim 12, characterized in that, In step S2, the reflux reaction time is 6h to 24h.

15. The epoxy resin composition according to claim 5, characterized in that, In step S3', the intramolecular anhydride reaction is carried out in the presence of dicyclohexylcarbodiimide.

16. The epoxy resin composition according to claim 15, characterized in that, In step S3', the molar ratio of the dicyclohexylcarbodiimide to the polycarboxylic aromatic compound is 2:1 to 3:

1.

17. The epoxy resin composition according to claim 15, characterized in that, In step S3', the conditions for the intramolecular anhydride reaction include a temperature of 0~30℃ and a time of 10~36h.

18. The epoxy resin composition according to claim 1, characterized in that, The epoxy resin is selected from at least one of bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, o-hydroxymethyl bisphenol A diglycidyl ether, dihydroxymethyl bisphenol A diglycidyl ether, tetrabromobisphenol A diglycidyl ether, resorcinol diglycidyl ether, pyrogallol triglycidyl ether, and pentaerythritol diglycidyl ether.

19. The epoxy resin composition according to claim 18, characterized in that, The epoxy resin is bisphenol A bisglycidyl ether and / or bisphenol F bisglycidyl ether.

20. The epoxy resin composition according to claim 1, characterized in that, The toughening agent is selected from at least one of polyurethane, cashew nut shell liquid modified phenolic resin, unsaturated polyester resin, epoxy resin active toughening agent and SBS thermoplastic elastomer.

21. The epoxy resin composition according to claim 1, characterized in that, The coupling agent is selected from at least one of γ-aminopropyltriethylsiloxane, γ-epoxypropoxypropyltrimethoxysiloxane, γ-methacrylate propyltrimethoxysiloxane, γ-thiol propyltrimethoxysiloxane, vinyltritert-butylperoxide, β-hydroxyethyl-γ-aminopropyltriethoxysiloxane, anilinemethyltriethoxysilane, and diethylenetriaminopropyltriethoxysilane.

22. The epoxy resin composition according to claim 1, characterized in that, The epoxy resin composition also contains a trifunctional epoxy compound having the structure shown in formula (1); Equation (1), In equation (1), R 1 and R 2 Each is independently an H or C1-C5 alkyl group.

23. The epoxy resin composition according to claim 22, characterized in that, The mass ratio of the trifunctional epoxy compound to the epoxy resin is (10-300):

100.

24. A method for preparing the epoxy resin composition according to any one of claims 1-23, characterized in that, The method involves uniformly mixing epoxy resin, toughening agent, curing agent, and optionally colorant, coupling agent, and trifunctional epoxy compound to obtain an epoxy resin composition.

25. The use of the epoxy resin composition according to any one of claims 1-23 as a bottom filler adhesive for electronic products.

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