Silicone phthalonitrile modified epoxy molding compound resin composition

Abstract

The invention relates to the technical field of electronic packaging materials, in particular to a phthalonitrile modified thermosetting resin composition containing a siloxane structure and application of the phthalonitrile modified thermosetting resin composition in the electronic packaging materials. The composition comprises multifunctional epoxy resin, XYLOK phenolic resin, a curing accelerator, a modifier and an inorganic filler, and the modifying agent is eugenol phthalonitrile trisiloxane. The modifier disclosed by the invention has good mechanical compatibility and dispersity in matrix resin; when the epoxy resin is applied to a thermosetting resin system, the processability can be improved, and the toughness of a cured product can be effectively improved while the glass-transition temperature is increased, so that the cured product has excellent bending property; the composition has excellent thermal stability, low bending modulus, good impact performance and humidity and heat resistance after being cured, the glass transition temperature of the composition is effectively improved, the comprehensive performance of resin is remarkably improved, and the composition is suitable for improving the packaging reliability and environmental stability of semiconductor devices.

Description

Technical Field

[0001] This invention relates to the field of electronic packaging materials technology, specifically to a phthalonitrile-modified thermosetting resin composition containing a siloxane structure and its application in electronic packaging materials. Background Technology

[0002] Electronic packaging materials play a crucial supporting and protective role in the stable operation of chips and integrated circuits. They can effectively resist the adverse effects of environmental factors such as external stress, mechanical shock, thermal shock, moisture corrosion, and ultraviolet radiation. Simultaneously, they must possess excellent electrical insulation properties to ensure the reliability and stability of chips during long-term service. Among these, epoxy molding compounds (EMCs) are an important type of electronic packaging material. Due to their excellent electrical insulation, heat resistance, water resistance, adhesion, chemical corrosion resistance, and mechanical properties, as well as good processability and operability, they occupy more than 90% of the electronic packaging material market share.

[0003] With the continuous advancement of electronic packaging technology, increasingly stringent requirements have been placed on the comprehensive performance of packaging materials. Their development has shown several important trends, including high purity (low ion content), high heat resistance, high thermal conductivity, low moisture absorption, low stress characteristics, and environmental friendliness. The rapid development of modern information technology has continuously increased the reliability requirements of semiconductor devices, thus setting more stringent standards for the performance indicators of packaging materials, such as high temperature resistance, humid heat resistance, low warpage, and low stress. Ideal EMC must meet the following basic requirements: (1) a low coefficient of thermal expansion; (2) good thermal conductivity; (3) the ability to withstand the effects of harmful environments such as high temperature, high humidity, corrosion, and radiation on electronic devices; (4) high strength and hardness to support and protect the chip; and (5) good processing, forming, and welding performance.

[0004] A typical EMC system consists of components such as matrix resin, curing accelerator, and inorganic fillers. Among them, epoxy resin, as an important component of the matrix resin, plays a crucial role in the overall performance of the molding compound; modifying the EMC matrix resin is one of the effective ways to improve the overall performance of EMC.

[0005] Phthalonil resin is a class of high-performance thermosetting resins end-capped with phthalonitrile structures. After thermosetting, it forms a three-dimensional network structure containing aromatic heterocyclic rings such as isoindole, triazine, and phthalocyanine, exhibiting excellent heat resistance, chemical corrosion resistance, flame retardancy, dielectric properties, and low water absorption. However, phthalonitrile resin suffers from high melting points, high curing temperatures, and long curing cycles, making it incompatible with existing EMC processing and molding technologies. Furthermore, its cured product has poor toughness, which can lead to reliability issues such as warping and cracking when used in encapsulation. In addition, insufficient toughness is a key performance indicator for EMC, a high-filler system.

[0006] As semiconductor technology continues to advance towards higher performance, higher integration, and higher frequency and speed, the requirements for packaging materials are becoming increasingly stringent. Advanced packaging requires materials to operate at high glass transition temperatures (T0). g It achieves synergistic optimization and balance in several key properties, such as low coefficient of thermal expansion (CTE), low curing stress, and low warpage. However, it is often difficult to achieve all these properties simultaneously; for example, improving heat resistance may lead to increased internal stress, while improving flowability may sacrifice mechanical strength.

[0007] Therefore, it is of great significance to develop novel modifiers containing phthalonitrile structures and to further develop thermosetting resin compositions that possess key properties such as thermal stability / toughness and processability. Summary of the Invention

[0008] To address the aforementioned problems in the prior art, this invention provides a thermosetting resin composition for phthalonitrile-modified epoxy electronic packaging materials containing a siloxane structure.

[0009] This invention combines the rigid structure of phthalonitrile resin with the flexible structure of polysiloxane (polysiloxane has excellent heat resistance, UV resistance, flexible Si-O-Si skeleton, low surface energy and chemical stability, etc.) to synergistically modify epoxy resin, and significantly improve its toughness, processability and other key properties while maintaining or even improving EMC thermal stability.

[0010] This invention employs eugenol-phthalonitrile trisiloxane to overcome the shortcomings of traditional phthalonitrile resins, such as high melting point and difficult processing. Simultaneously, the use of multifunctional epoxy resin, XYLOK phenolic resin, and a curing accelerator effectively improves the curing reactivity of the resin system, thereby improving molding processability and meeting the processing and molding requirements of existing epoxy molding compounds. Furthermore, the introduced eugenol-phthalonitrile trisiloxane, as a modifier, exhibits good mechanical compatibility and dispersibility in the matrix resin, and can improve the T... g This effectively improves the toughness of the cured material. The cured resin composition exhibits good thermal stability, low flexural modulus, good impact resistance and humid heat resistance, and its glass transition temperature is increased. This solves problems such as warping and cracking that may occur when applied to electronic packaging materials, and can significantly improve the reliability and environmental stability of semiconductor device packaging.

[0011] To achieve the above objectives, the technical solution adopted by the present invention is as follows: The first aspect of the present invention provides a thermosetting resin composition modified with phthalonitrile containing a siloxane structure, comprising a multifunctional epoxy resin, XYLOK phenolic resin, a curing accelerator, a modifier, and an inorganic filler; Furthermore, the modifier is eugenol-phthalic acid trisiloxane, having the structure shown in formula (I): (I); In formula (I), R1-R6 independently represent at least one of a straight-chain or branched alkyl group having 0-10 carbon atoms, a straight-chain or branched alkoxy group having 0-10 carbon atoms, and an aryl group having 6-20 carbon atoms; at least one of R1-R6 is an aryl group. Furthermore, the mass ratio of the multifunctional epoxy resin to the XYLOK phenolic resin is 5:1 to 1:5; preferably 2:1 to 1:3.5. In some embodiments, the content of the curing accelerator is 0.5 to 5 wt% of the total amount of the multifunctional epoxy resin and XYLOK phenolic resin; preferably 0.5 to 2 wt%. In some embodiments, the content of the modifier is 1 to 30 wt% of the total amount of the multifunctional epoxy resin and XYLOK phenolic resin, optionally 1 to 5 wt%, 5 to 10 wt%, 10 to 15 wt%, 15 to 20 wt%, 20 to 25 wt%, 25 to 30 wt%; preferably 1 to 20 wt%, more preferably 5 to 15 wt%.

[0012] In some embodiments, the content of the inorganic filler is 70-90 wt% of the total composition; preferably 75-85 wt%.

[0013] Furthermore, the multifunctional epoxy resin includes substances with the chemical structure shown in formula (II): (II); In formula (II), R1 is a hydrogen atom or an alkyl group having 1-6 carbon atoms; R' is hydrogen, methyl or ethyl; n is an integer from 0 to 6.

[0014] In some preferred embodiments of the present invention, the multifunctional epoxy resin is selected from one or more of EPPN-501H, EPPN-501HY or EPPN-502H from Nippon Kayaku Co., Ltd.

[0015] Furthermore, the XYLOK phenolic resin comprises substances with the chemical structure shown in formula (III): (III); In formula (III), R1 and R2 are hydrogen atoms or alkyl groups with 1 to 6 carbon atoms; each R' represents two substituents, which are independently selected from hydrogen, methyl, and ethyl; n is an integer from 0 to 6.

[0016] In some preferred embodiments of the present invention, the XYLOK phenolic resin may be one or more of SH-4064, SH-4070 or SH-4075 from Shandong Shengquan New Material Co., Ltd.

[0017] Furthermore, the curing accelerator is selected from one or a combination of tertiary amines, imidazole compounds, organophosphorus compounds, and acetylacetone metal complexes; In some embodiments, the tertiary amine is selected from 1,8-diazabicycloundec-7-ene (DBU), 1,5-diazabicyclonon-5-ene (DBN), N-methylpiperazine, triethylamine, triethanolamine, benzyldimethylamine, dimethylaminomethylphenol (DMP-10), bis-(dimethylaminomethyl)phenol (DMP-20), and tri-(dimethylaminomethyl)phenol (DMP-30). In some embodiments, the imidazole compound is selected from imidazole, 2-methylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-phenyl-2-methylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, and 2-ethyl-4-methylimidazolium-tetraphenylborate. In some embodiments, the organophosphorus compound is selected from triphenylphosphine, triphenylphosphine-p-benzoquinone adduct, tri-p-tolylphosphine-p-benzoquinone adduct, ethyltriphenylacetic acid phosphorus, tetraphenylphosphine-tetraphenylborate, and butyltriphenylphosphine-tetraphenylborate. In some embodiments, the acetylacetone metal complex includes iron acetylacetone, manganese acetylacetone, chromium acetylacetone, platinum acetylacetone, calcium acetylacetone, barium acetylacetone, molybdenum acetylacetone, cadmium acetylacetone, lanthanum acetylacetone, vanadium acetylacetone, titanium acetylacetone, and zirconium acetylacetone. In some preferred embodiments of the present invention, the curing accelerator is preferably 1,8-diazabicycloundec-7-ene (DBU), 1,5-diazabicyclonon-5-ene (DBN), 2-methylimidazole, 2-ethyl-4-methylimidazole, triphenylphosphine, and triphenylphosphine-p-benzoquinone adduct.

[0018] Furthermore, the inorganic filler comprises spherical fused silica, wherein the average particle size of the spherical fused silica is 0.01~30 μm; Furthermore, the content of the spherical fused silica is 50-100 wt% of the total amount of inorganic filler; preferably 90-100 wt%.

[0019] Furthermore, the inorganic filler also includes one or more of the following: crystalline silica, fumed silica, alumina, aluminum hydroxide, calcium carbonate, magnesium oxide, magnesium hydroxide, boron nitride, aluminum nitride, silicon nitride, magnesium carbonate, calcium hydroxide, clay, wollastonite, and talc.

[0020] Furthermore, the composition also includes additives, including one or more of silane coupling agents, colorants, and release agents.

[0021] In some embodiments, the colorant is selected from carbon black and iron oxide red; In some embodiments, the release agent is selected from natural waxes and synthetic waxes.

[0022] The second aspect of the present invention provides a method for preparing the eugenol phthalic acid trisiloxane, specifically comprising steps S1 and S2: S1. Using 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane and eugenol as raw materials, with a molar ratio of reactants of 1:2 to 2.2, eugenol-based trisiloxane is obtained under the action of a catalyst or radiation. S2. The eugenol-based trisiloxane obtained in step S1 is reacted with 4-nitrophthalonitrile in the presence of an acid-binding agent at a molar ratio of 1:2 to 2.2 to obtain eugenol-phthalonitrile-based trisiloxane.

[0023] Further, in step S1, the catalyst is selected from one or a combination of organic base compounds, organic peroxides, azo compounds, and noble metal compounds.

[0024] Further, in step S1, the radiation conditions are selected from ultraviolet rays, alpha rays, beta rays, gamma rays, X-rays, and neutron rays.

[0025] Further, in step S2, the acid-binding agent is selected from one or a combination of triethylamine, pyridine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, tetrabutylammonium bromide, potassium carbonate, ammonium carbonate, sodium carbonate, sodium hydroxide, calcium hydroxide, potassium hydroxide, iron hydroxide, calcium carbonate, cesium carbonate, sodium phosphate, and sodium acetate.

[0026] The production or preparation method of the compositions of the present invention is not particularly limited. For example, multifunctional epoxy resin, XYLOK phenolic resin, curing accelerator, modifier, inorganic filler and other additives are thoroughly mixed together using a mixer or similar device, then melt-kneaded using a heated roller or kneader, and the resulting product is then cooled and pulverized.

[0027] The compositions of the present invention can be cured and molded by transfer molding, compression molding or injection molding, and can be used in electronic packaging materials, including but not limited to the field of semiconductor device packaging.

[0028] Beneficial effects: Based on the above technical solution, the present invention has the following advantages and beneficial effects: (1) The present invention first provides a eugenol phthalic acid trisiloxane, which can be used as a resin modifier. This modifier has good mechanical compatibility and dispersibility in the matrix resin. Moreover, the preparation method of this material is simple and suitable for large-scale production. (2) This invention further provides a thermosetting epoxy resin based on this modifier. After adding eugenol-phthalonitrile trisiloxane, it can effectively overcome the disadvantages of traditional phthalonitrile resins, such as high melting point and difficult processing. By using multifunctional epoxy resin, XYLOK phenolic resin and curing accelerator in combination, the curing reactivity of the resin system can be significantly improved, thereby improving its molding processability and meeting the processing and molding process requirements of existing epoxy molding compounds. When applied to thermosetting resin systems, it can not only improve processing performance, but also increase the glass transition temperature (T). g At the same time, it effectively improves the toughness of the cured material, giving it excellent bending properties; (3) After the thermosetting resin composition of the present invention is cured, there are flexible siloxane chains and isoindole structures generated by cyano groups in the system, thereby endowing the cured product with excellent thermal stability, low flexural modulus, good impact performance and humid heat resistance, and its glass transition temperature is effectively improved, and the overall performance of the resin is significantly improved. Attached Figure Description

[0029] The accompanying drawings are provided to further illustrate the present application and form part of the specification. They are used together with the embodiments of the present application to explain the application and do not constitute a limitation thereof. In the drawings: Figure 1 The above is the 1H NMR spectrum of eugenol-based trisiloxane (EPS), the modifier intermediate in this embodiment of the invention. Figure 2 The image shows the 1H NMR spectrum of the eugenol-phthalonitrile modified agent eugenol prepared in the embodiments of the present invention. Detailed Implementation

[0030] To make the above-mentioned objects, features, and advantages of the present invention more apparent and understandable, the specific embodiments of the present invention are described in detail below with reference to the examples. The examples are implemented based on the technical solution of the present invention, and detailed implementation methods and processes are given. However, the scope of protection of the present invention is not limited to the following examples. Experimental methods in the following examples that do not specify specific conditions are generally performed under conventional conditions or according to the conditions recommended by the manufacturer.

[0031] The raw materials used in the embodiments of the present invention are shown below, but are not limited thereto: 4-Nitrophthalonitrile, purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No. 31643-49-9; Anhydrous potassium carbonate (K2CO3) was purchased from Shanghai Maclean Biochemical Technology Co., Ltd., CAS No. 584-08-7; N,N-Dimethylformamide (DMF) was purchased from Sinopharm Chemical Reagent Co., Ltd. Multifunctional epoxy resin, purchased from Nippon Kayaku Co., Ltd, model EPPN-501H; XYLOK phenolic resin, purchased from Shandong Shengquan New Material Co., Ltd., model SH-4064, with a hydroxyl equivalent of 168-174 g / eq; 1,1,5,5-Tetramethyl-3,3-diphenyltrisiloxane (TPS) was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No. 17875-55-7; Eugenol (EG) was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No. 97-53-0; 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane platinum (0) (Karstedt catalyst), purchased from Shanghai Titan Technology Co., Ltd., CAS No. 68478-92-2; Triphenylphosphine (TPP) was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., CAS No. 603-35-0; Spherical fused silica with average particle sizes of 20 μm and 8 μm was purchased from Denki Kagaku Co., Ltd., Japan. Silane coupling agent: γ-glycidoxypropyltrimethoxysilane, purchased from Shin-Etsu Chemical Co., Ltd., Japan; Colorant: Carbon black, purchased from Mitsubishi Gas Company; Release agent: Brazilian carnauba wax, purchased from Shanghai Yiba Chemical Trading Co., Ltd.

[0032] The testing methods for various performance indicators in this embodiment of the invention are as follows: (1) Spiral flow length: According to the method shown in SJ / T 11197-2013 Epoxy Molding Compound, take 15 g of the resin composition sample to be tested and inject it into the spiral flow metal mold of EMMI-1-66 on a transfer molding press to determine the spiral flow length of the sample. The temperature of the upper and lower molds is set to 175 ± 3 °C and the transfer pressure is (125 kg ± 5 kg) cm. -2 The transmission speed is (6.0 cm ± 0.1 cm) s. -1 After curing for 120 seconds, the sample is removed from the metal mold, and the spiral flow length is read to an accuracy of 0.5 cm. The same sample is tested three times, and the average value is taken. The transmitted pressure is obtained by dividing the total pressure by the injection head area.

[0033] (2) Gel time: According to the method shown in SJ / T 11197-2013 Epoxy Molding Compound, heat the hot plate to 175 °C ± 2 °C, take 0.3~0.5 g of resin composition sample and place it on the hot plate. The sample spread area is about 5 cm². 2 Start stirring with a needle-shaped stirring tip or a flat spatula until the powder gradually becomes a gel (the sample cannot be drawn into threads). Read the time required. Repeat the same operation twice and take the average value.

[0034] (3) Thermal stability: The resin composition was molded at 175 °C using an injection molding machine, followed by post-curing under the following conditions: 200 °C for 2 h, 230 °C for 2 h, and 260 °C for 2 h. Then, thermogravimetric analysis (TGA) was performed using a TGA / 1100SF instrument under N2 atmosphere, in a temperature range of 50–800 °C. The heating rate was 10 °C / min, the flow rate was 50 mL / min, and 5–10 mg of each sample was used. The degradation temperature (T0) at 5% mass loss was determined. 5% ).

[0035] (4) Flexural strength and flexural modulus: The resin composition was molded at 175 °C using an injection molding machine, followed by post-curing under the following conditions: 200 °C for 2 h, 230 °C for 2 h, and 260 °C for 2 h. Then, the tests were conducted according to the People's Republic of China National Standard GB / T 9341-2008 "Determination of Flexural Properties of Plastics". A double 85 test was performed by placing the cured material in a constant temperature and humidity chamber (model LHS-50CH) at 85 °C and 85% relative humidity for a test period of 96 h.

[0036] (5) Impact strength: The resin composition was molded at 175 °C using an injection molding machine and then post-cured under the following conditions: 200 °C for 2 h, 230 °C for 2 h, and 260 °C for 2 h; then the test was carried out in accordance with the People's Republic of China National Standard GB / T-1843-2008 "Determination of impact properties of plastics".

[0037] (6) Glass transition temperature (T) g The resin composition was molded using an injection molding machine at 175 °C and then post-cured under the following conditions: 200 °C for 2 hours, 230 °C for 2 hours, and 260 °C for 2 hours. Dynamic thermomechanical analysis was performed according to standard ASTM E1640-2013, "Standard Test Method for Glass Transition Temperature Distribution Using Dynamic Mechanical Analysis". g The test.

[0038] Examples 1-4: The raw materials and dosages used in Examples 1-4 of this invention are shown in Table 1: Table 1 shows the modifier addition amounts in Examples 1-4: 5.00%, 10.00%, 15.00%, and 20.00%, respectively. The preparation method of the modifier used in the examples—eugenol-containing phthalic acid nitrile trisiloxane (EPSN)—includes the following two steps: (1) Preparation of eugenol-based trisiloxane (EPS): Eugenol (19.7 g, 0.1 mol), Karstedt catalyst (5 ppm, 9.7 μL) and toluene (100 mL) were added sequentially to a flask, and the mixture was heated to 80 °C and stirred for 20 min under a N2 atmosphere. 1,1,5,5-Tetramethyl-3,3-diphenyltrisiloxane TPS (0.05 mol, 16.68 g) was dissolved in 100 mL of toluene and then added dropwise to the flask using a dropping funnel, with the addition completed within 3 h. The temperature was then raised to 120 ℃ and reacted for 2 h. After the reaction was completed, the mixture was purified by rotary evaporation and dried to obtain a pale yellow liquid, 4,4'-(((1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane-1,5-diyl)bis(propane-3,1-diyl))bis(2-methoxyphenol), which is eugenoltrisiloxane (EPS), with a yield of 92%. The reaction equation is as follows: (2) Preparation of eugenol-phthalonitrile-modified polysiloxane (EPSN): 4-nitrophthalonitrile (3.46 g, 0.02 mol), EPS (6.61 g, 0.01 mol), potassium carbonate (2.764 g, 0.02 mol), and N,N-dimethylformamide (150 ml) were mixed in a flask and stirred vigorously at 85 °C for 8 h; then the reaction solution was added dropwise to a 0.1 mol / L sodium hydroxide aqueous solution to precipitate the precipitate. The precipitate was washed with water until neutral and then dried under vacuum at 60 °C for 12 h. h, yielding 4,4'-((((1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane-1,5-diyl)bis(propane-3,1-diyl))bis(2-methoxy-4,1-phenylene))bis(oxy))diphthalonitrile, which is eugenol phthalonitrile trisiloxane (EPSN), with a yield of 83%.

[0039] The reaction equation is as follows: The preparation method of the thermosetting resin composition of phthalonitrile-modified epoxy electronic packaging material containing a siloxane structure according to Examples 1-4 of the present invention is as follows: According to the proportions shown in Table 1, the multifunctional epoxy resin (EPPN-501H), XYLOK phenolic resin (SH-4064), triphenylphosphine (TPP), eugenol phthalic acid trisiloxane (EPSN), spherical fused silica (average particle size of 20 μm and 8 μm), silane coupling agent (γ-epoxypropoxypropyltrimethoxysilane), colorant (carbon black), and release agent (carnauba wax) were thoroughly mixed in a high-speed mixer at a speed of 1000 rpm at room temperature. Then, the mixture was melt-kneaded in a twin-screw kneader at 80~110 °C. The kneaded material was then cooled and pulverized to obtain the thermosetting resin composition.

[0040] Comparative Examples 1-2: The raw materials and amounts used in Comparative Examples 1 and 2 of this invention are shown in Table 2 below: Table 2 Comparative Example 1 illustrates a traditional method for preparing epoxy molding compound, while Comparative Example 2 involves adding 10% of commonly used core-shell rubber particles (purchased from Wuxi Chuangda New Materials Co., Ltd., model EXL2655). The specific steps are as follows: According to the proportions shown in Table 2, multifunctional epoxy resin (EPPN-501H), XYLOK phenolic resin (SH-4064), triphenylphosphine (TPP), spherical fused silica (average particle size of 8 μm and 20 μm), silane coupling agent (KBM-403), colorant (carbon black), and release agent (carnauba wax) are thoroughly mixed in a high-speed mixer at 1000 rpm at room temperature; the prepared mixture is then melt-kneaded in a twin-screw kneader at 80~110 ℃; the kneaded mixture is then cooled and pulverized to obtain the epoxy molding compound.

[0041] The performance test results of the embodiments and Comparative Example 1 are shown in Table 3 below: Table 3 As shown in Table 3, the thermosetting resin composition of the present invention exhibits superior flowability and curing efficiency: the spiral flow length is generally higher than that of the comparative examples, especially Example 4, which reaches 49 inches, far superior to the 34 and 35 inches of Comparative Examples 1 and 2, indicating better filling and molding flowability; at the same time, the gel time is shorter, with Examples 3 / 4 requiring only about 20 seconds, and the curing speed is significantly faster than that of the comparative examples, which helps to improve production efficiency. This indicates that the resin composition of the present invention has good curing activity, can fully fill the mold, and meets the current curing and molding process of commercial electronic packaging epoxy molding compounds.

[0042] The thermosetting resin composition of the present invention also exhibits excellent mechanical properties and heat resistance. The initial flexural strength and modulus of the embodiments are generally high, and after "double 85" aging, their performance retention rate is significantly better than that of the comparative example. The change rate of flexural strength after aging in each embodiment is less than 5%; while the change in flexural strength after aging in the comparative example exceeds 10%. This indicates that the material of the present invention has better stability in humid and hot environments. Furthermore, the thermal decomposition temperature (T... 5% ) and glass transition temperature (T g The thermal stability and long-term reliability of the resin composition of this invention are generally higher than those of the comparative example. The impact strength of the cured resin composition of this invention is also superior to (or equivalent to) that of the comparative example. The resin composition of this invention achieves synergistic improvements in flowability, curing speed, mechanical strength, and environmental aging resistance, balancing processing performance with end-application requirements, and has high practical value.

[0043] Phthalonil resins typically exhibit high crosslinking density after curing and form rigid structures containing aromatic heterocycles such as isoindole, triazine rings, and phthalocyanine, resulting in brittleness and insufficient toughness in the cured product, often exhibiting a high flexural modulus. This invention combines the rigid structure of phthalonitrile with the flexible structure of siloxanes to achieve toughening and reinforcement of epoxy molding compounds, simultaneously improving toughness and other key properties while maintaining the thermal stability of the molding compound. The eugenol-phthalonitrile trisiloxane contained in the resin composition of this invention acts as a modifier, exhibiting good mechanical compatibility and dispersibility in the matrix resin. The cured resin composition of this invention possesses flexible siloxane chains and rigid phthalonitrile, enhancing the mobility of molecular chain segments and allowing the cured product to easily undergo plastic deformation under external forces to absorb energy, resulting in better toughness. Simultaneously, due to the low polarity of siloxanes, the overall molding compound exhibits hydrophobicity after addition, and its mechanical properties remain essentially unchanged after double 85 treatment. The cured resin composition of this invention exhibits excellent thermal stability and a higher TT. g It features lower flexural modulus, higher impact strength, and better resistance to damp heat. This is especially true in increasing the glass transition temperature (Tg). g At the same time, it effectively improves the toughness of the cured material. It has higher reliability and environmental stability.

[0044] It should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and are not intended to limit it. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, and all such modifications or substitutions should be covered within the scope of the present invention.

Claims

1. A thermosetting resin composition for epoxy electronic packaging containing phthalonitrile with a siloxane structure, characterized in that, Including multifunctional epoxy resins, XYLOK phenolic resins, curing accelerators, modifiers, and inorganic fillers; The modifier is eugenol-phthalic acid trisiloxane, having the structure shown in formula (I): （I）； In formula (I), R1-R6 independently represent at least one of a straight-chain or branched alkyl group with 0-10 carbon atoms, a straight-chain or branched alkoxy group with 0-10 carbon atoms, and an aryl group with 6-20 carbon atoms; at least one of R1-R6 is an aryl group.

2. The thermosetting resin composition according to claim 1, characterized in that, The mass ratio of the multifunctional epoxy resin to XYLOK phenolic resin is 5:1 to 1:

5. The curing accelerator is present in an amount of 0.5-5 wt% of the total amount of the multifunctional epoxy resin and XYLOK phenolic resin. The content of the modifier is 1-30 wt% of the total amount of the multifunctional epoxy resin and XYLOK phenolic resin, preferably 5-20 wt%. The content of the inorganic filler is 70-90 wt% of the total composition.

3. The thermosetting resin composition according to any one of claims 1-2, characterized in that, The multifunctional epoxy resin includes substances with the chemical structure shown in formula (II): (II); In formula (II), R1 is a hydrogen atom or an alkyl group having 1-6 carbon atoms; R' is a hydrogen atom, methyl or ethyl; n is an integer from 0 to 6.

4. The thermosetting resin composition according to any one of claims 1-2, characterized in that, The XYLOK phenolic resin comprises substances with the chemical structure shown in formula (III): (III); In formula (III), R1 and R2 are hydrogen atoms or alkyl groups with 1 to 6 carbon atoms; n is an integer from 0 to 6; Each R' represents two substituents, independently selected from hydrogen, methyl, and ethyl groups.

5. The thermosetting resin composition according to any one of claims 1-2, characterized in that, The modifier is prepared by a two-step method, specifically including the following steps: S1. Using 1,1,5,5-tetramethyl-3,3-diphenyltrisiloxane and eugenol as raw materials, eugenol-based trisiloxane is obtained by reaction under the action of a catalyst or radiation. S2. The eugenol-based trisiloxane obtained in step S1 is reacted with 4-nitrophthalonitrile in the presence of an acid-binding agent to obtain eugenol-phthalonitrile-based trisiloxane.

6. The thermosetting resin composition according to claim 5, characterized in that, In step S1, the catalyst is selected from one or a combination of organic base compounds, organic peroxides, azo compounds, and noble metal compounds; and / or, In step S1, the radiation conditions are selected from ultraviolet rays, alpha rays, beta rays, gamma rays, X-rays, neutron rays; and / or, In step S2, the acid-binding agent is selected from one or a combination of triethylamine, pyridine, N,N-diisopropylethylamine, 4-dimethylaminopyridine, triethanolamine, tetrabutylammonium bromide, potassium carbonate, ammonium carbonate, sodium carbonate, sodium hydroxide, calcium hydroxide, potassium hydroxide, iron hydroxide, calcium carbonate, cesium carbonate, sodium phosphate, and sodium acetate.

7. The thermosetting resin composition according to any one of claims 1-2, characterized in that, The curing accelerator is selected from one or a combination of tertiary amines, imidazole compounds, organophosphorus compounds, and acetylacetone metal complexes.

8. The thermosetting resin composition according to any one of claims 1-2, characterized in that, The inorganic filler includes spherical fused silica, wherein the average particle size of the spherical fused silica is 0.01~30μm; The content of the spherical fused silica is 50-100 wt% of the total amount of inorganic filler.

9. The thermosetting resin composition according to any one of claims 1-2, characterized in that, It also includes additives, which include one or more of silane coupling agents, colorants, and release agents.

10. An epoxy molding compound made from the thermosetting resin composition of any one of claims 1-9.

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