Thermosetting resin composition for packaging high-reliability semiconductor device

Abstract

The invention relates to the technical field of electronic packaging materials, in particular to a thermosetting resin composition for packaging a high-reliability semiconductor device. 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 polysiloxane. The modifier has good mechanical compatibility and dispersity in matrix resin; and when being applied to a thermosetting resin system, the epoxy resin can improve the processability and effectively enhance the toughness of a cured product. The composition provided by the invention accords with the processing and forming process of the existing epoxy molding compound; according to the present invention, the spiral flow length of the molding compound is substantially increased, the processing performance is good, the cured product has advantages of good thermal stability, low bending modulus, good impact property and good heat and humidity resistance, and the glass transition temperature is increased. The resin is significantly improved in comprehensive performance, and is suitable for packaging semiconductor devices with high requirements on reliability and environmental stability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electronic packaging materials, and particularly relates to a thermosetting resin composition for high-reliability semiconductor device packaging. BACKGROUND

[0002] Electronic packaging materials play an important supporting and protective role for chips and integrated circuits, effectively resisting the adverse effects of external stress, mechanical impact, thermal shock, moisture erosion, ultraviolet radiation and other environmental factors, while ensuring excellent electrical insulation performance, protecting the reliability and stability of chips during long-term use. Among them, epoxy molding compound (EMC) as an important electronic packaging material has excellent electrical insulation, heat resistance, water resistance, adhesion, chemical and mechanical resistance, as well as good processability and operability, accounting for more than 90% of the entire electronic packaging material. With the continuous progress of electronic packaging technology, the comprehensive performance of packaging materials is increasingly demanding, and the important trends of its development mainly include high purity (low ion content), high heat resistance, high thermal conductivity, low moisture absorption, low stress characteristics and environmental friendliness. Modern high-speed information technology has higher and higher requirements for the reliability of semiconductor devices, and therefore has higher requirements for packaging materials, and sets more stringent standards for the performance indicators of EMC, including high temperature resistance, humidity resistance, low warpage, low stress, etc. An ideal EMC should have the following basic requirements: (1) low thermal expansion coefficient; (2) good thermal conductivity; (3) resistance to the influence of harmful environments such as high temperature, high humidity, corrosion and radiation on electronic devices; (4) high strength and hardness, which supports and protects the chip; (5) good processing and welding performance, etc. Therefore, in order to solve the performance defects of traditional EMC and meet the requirements of high-power devices and advanced packaging, it is of great significance to develop a high-reliability semiconductor device packaging thermosetting resin composition.

[0003] A typical EMC system is composed of base resin, curing accelerator and inorganic filler components. Among them, epoxy resin as an important component of the base resin plays a crucial role in the performance of the entire molding compound; modifying the EMC base resin is one of the effective ways to improve the comprehensive performance of EMC.

[0004] Phthalonitrile resin is a kind of high-performance thermosetting resin capped with phthalonitrile structure, which can form a network structure containing isoindole, triazine ring, phthalocyanine and other aromatic heterocyclic rings after thermal curing, and has excellent heat resistance, chemical corrosion resistance, flame retardance, dielectric properties and low water absorption. However, phthalonitrile resin has high melting point, high curing temperature and long curing period, which is incompatible with the existing EMC processing and molding process; and its cured product has poor toughness, which can cause warpage, cracking and other reliability problems when applied to packaging. And the EMC is a high filler system, and the lack of toughness is also a key performance indicator of the system.

[0005] With the development of semiconductor technology towards high performance, high integration, high frequency and high speed, the requirements for packaging materials are increasingly stringent. Advanced packaging requires that the materials must achieve synergistic optimization and balance in multiple key properties such as high glass transition temperature (T g ), low coefficient of thermal expansion (CTE), low curing stress and low warpage. However, it is often difficult to achieve all these properties; for example, improving heat resistance may increase internal stress, and improving flowability may sacrifice mechanical strength.

[0006] Therefore, it is urgent to develop a new modifier and resin composition to simultaneously optimize its processability, anti-aging property and overall reliability, so as to meet the technical requirements of next-generation semiconductor packaging. SUMMARY

[0007] In order to solve the above problems existing in the prior art, the present application provides a thermosetting resin composition for high-reliability semiconductor device packaging.

[0008] The eugenol-phthalonitrile polysiloxane used in the present application overcomes the shortcomings of traditional phthalonitrile resin, such as high melting point and difficult processing. At the same time, the use of multifunctional epoxy resin, XYLOK phenolic resin and curing accelerator effectively improves the curing reaction activity of the resin system, thereby improving the molding processability and meeting the processing and molding process requirements of existing epoxy molding compounds.

[0009] In addition, the introduced eugenol-phthalonitrile polysiloxane as a modifier has good mechanical compatibility and dispersibility in the matrix resin, which can effectively improve the toughness of the cured product while improving the T g . The cured resin composition has good thermal stability, low bending modulus, good impact performance and wet heat resistance, and the glass transition temperature is significantly improved. By improving its toughness, it helps to avoid problems such as warpage and cracking when applied to electronic packaging materials, and can effectively improve the reliability and environmental stability of semiconductor device packaging.

[0010] In order to achieve the above purpose, the technical scheme adopted by the present application is as follows: The first aspect of the present application provides a thermosetting resin composition for high-reliability semiconductor device packaging, comprising a multifunctional epoxy resin, an XYLOK phenolic resin, a curing accelerator, a modifier and an inorganic filler; The modifier is eugenol-phthalonitrile polysiloxane, which has the structure shown in formula (I): (I) ; In formula (I), m and n are independently integers in the range of 5 to 30; Further, the content of the modifier is 1-30 wt% of the total amount of the multifunctional epoxy resin and the XYLOK phenolic resin; optionally 1-5 wt%, 5-10 wt%, 10-15 wt%, 15-20 wt%, 20-25 wt%, 25-30 wt%; preferably 1-20 wt%, more preferably 5-15 wt%.

[0011] In some embodiments, the mass ratio of the multifunctional epoxy resin and the XYLOK phenolic resin is 5:1-1:5, preferably 2:1-1:3.5; Further, the content of the curing accelerator is 0.5-5 wt% of the total amount of the multifunctional epoxy resin and the XYLOK phenolic resin, preferably 0.5-2 wt%. Further, the content of the inorganic filler is 70-90 wt% of the total amount of the composition, preferably 75-85 wt%.

[0012] Further, the multifunctional epoxy resin comprises a substance with a chemical structure shown in formula (II): (II); In formula (II), R1 is a hydrogen atom or an alkyl group with 1-6 carbon atoms; n is an integer of 0-6; R' is selected from hydrogen, methyl, and ethyl.

[0013] In some preferred embodiments of the present application, the multifunctional epoxy resin is selected from one or more than two of EPPN-501H, EPPN-501HY, or EPPN-502H of Japan Energy Product Co., Ltd.

[0014] Further, the XYLOK phenolic resin comprises a substance with a chemical structure shown in formula (III): (III); In formula (III), R1 and R2 are hydrogen atoms or alkyl groups with 1-6 carbon atoms; each R' represents two substituents, which are independently selected from hydrogen, methyl, and ethyl; n is an integer of 0-6.

[0015] In some preferred embodiments of the present application, the XYLOK phenolic resin can be selected from one or more than two of SH-4064, SH-4070, or SH-4075 of Shandong Shengquan New Material Co., Ltd.

[0016] Further, the curing accelerator is selected from one or a combination of tertiary amines, imidazole compounds, organic phosphorus compounds, and acetylacetone metal complexes. In some embodiments, the tertiary amine is selected from the group consisting of 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), tris-(dimethylaminomethyl)phenol (DMP-30); In some embodiments, the imidazole compound is selected from the group consisting of imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4- methylimidazole, 1-phenyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1- cyanoethyl-2-phenylimidazole, 2-ethyl-4-methylimidazole-tetraphenylborate; In some embodiments, the organophosphorus compound is selected from the group consisting of triphenylphosphine, triphenylphosphine-p-benzoquinone adduct, tri-p-tolylphosphine- p-benzoquinone adduct, ethyltriphenylphosphonium acetate, tetraphenylphosphonium- tetraphenylborate, butyltriphenylphosphonium-tetraphenylborate; In some embodiments, the acetylacetone metal complex comprises acetylacetone iron, acetylacetone manganese, acetylacetone chromium, acetylacetone platinum, acetylacetone calcium, acetylacetone barium, acetylacetone molybdenum, acetylacetone cadmium, acetylacetone lanthanum, acetylacetone vanadyl, acetylacetone titanium, acetylacetone zirconium; In some preferred embodiments of the present application, the curing accelerator is preferably 1,8- diazabicycloundec-7-ene (DBU), 1,5-diazabicyclonon-5-ene (DBN), 2-methylimidazole, 2- ethylimidazole, triphenylphosphine, and triphenylphosphine-p-benzoquinone adduct.

[0017] Further, the inorganic filler comprises spherical fused silica, wherein the average particle size of the spherical fused silica is 0.01-30 μm; further, the content of the spherical fused silica is 50-100 wt% of the total amount of the inorganic filler; preferably 90-100 wt%.

[0018] Further, the inorganic filler further comprises one or more of 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, talcum powder.

[0019] Further, the composition further comprises an additive, wherein the additive comprises one or more of a silane coupling agent, a colorant, and a release agent. In some embodiments, the colorant is selected from the group consisting of carbon black and red iron oxide; in some embodiments, the release agent is selected from the group consisting of natural wax and synthetic wax.

[0020] The second aspect of the present application provides that the modifier eugenol phthalonitrile polysiloxane is prepared by a three-step method, specifically comprising steps S1, S2, S3; S1. With octamethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,1,3,3-tetramethyl disiloxane as raw materials, under the action of cationic initiator, polymerization reaction is carried out to obtain hydrogen-containing polysiloxane; S2. The hydrogen-containing polysiloxane prepared in step S1 is reacted with eugenol under the action of a catalyst or radiation to obtain eugenol-based polysiloxane; S3. The eugenol-based polysiloxane prepared in step S2 is reacted with 4-nitrophthalonitrile in the presence of an acid-binding agent to obtain eugenol phthalonitrile polysiloxane.

[0021] In a preferred embodiment, in step S1, the molar ratio of octamethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, 1,1,3,3-tetramethyl disiloxane is 0.364:0.199:0.123, respectively; In a preferred embodiment, in step S2, the molar ratio of hydrogen polysiloxane to eugenol is 0.041:0.615; In a preferred embodiment, in step S3, the molar ratio of eugenol-based polysiloxane to 4-nitrophthalonitrile is 2:5.

[0022] Further, in step S1, the cationic initiator is selected from protonic acids, Lewis acids or other cationic initiators; the other cationic initiator is selected from iodine, oxonium ion, perchlorate, cycloheptatriene salt and triphenylmethyl salt; Further, in step S2, the catalyst includes organic base compounds, organic peroxides, azo compounds, noble metal compounds; Further, in step S2, the catalyst is selected from one or a combination of organic base compounds, organic peroxides, azo compounds, noble metal compounds; Further, in step S2, the radiation conditions include ultraviolet rays, alpha rays, beta rays, gamma rays, X-rays, neutron rays; Further, in step S3, the acid-binding agent is selected from one or a combination of triethylamine, pyridine, N,N-diisopropyl ethylamine, 4-dimethylamino pyridine, triethanolamine, tetrabutyl ammonium bromide, potassium carbonate, ammonium carbonate, sodium carbonate, sodium hydroxide, calcium hydroxide, potassium hydroxide, iron hydroxide, calcium carbonate, cesium carbonate, sodium phosphate, sodium acetate.

[0023] The third aspect of the present application provides an epoxy molding compound prepared from the thermosetting resin composition.

[0024] In some embodiments, the epoxy molding compound has a spiral flow length of 36 inches or greater; T g ≥158°C.

[0025] The method of producing or preparing the composition of the present application is not particularly limited. For example, the multifunctional epoxy resin, XYLOK phenolic resin, curing accelerator, modifier, inorganic filler and other additives are mixed together using a mixer or similar device, followed by melt kneading using a heating roller or kneader, and then the resulting product is cooled and pulverized.

[0026] The composition of the present application can be cured and formed by transfer molding, compression molding or injection molding, and is applied in electronic packaging materials, including but not limited to the field of semiconductor device packaging.

[0027] Advantages and beneficial effects: Based on the above technical solutions, the present application has the following advantages and beneficial effects: (1) The present application first provides a eugenol-phthalonitrile polysiloxane and a preparation method thereof. The rigid structure of phthalonitrile is combined with the flexible structure of siloxane, which can be added as a modifier to the resin system, and has good mechanical compatibility and dispersibility; (2) The present application further provides a resin composition containing eugenol-phthalonitrile polysiloxane as a modifier, which can effectively improve the processing performance and overcome the shortcomings of traditional phthalonitrile resin, such as high melting point and difficult processing. In combination with the use of multifunctional epoxy resin, XYLOK phenolic resin and curing accelerator, the curing reaction activity of the resin system is effectively improved, thereby improving the molding process and meeting the processing and molding process requirements of existing epoxy molding compounds.

[0028] (3) After curing of the resin composition of the present application, there are flexible siloxane chains and isoinde structures generated by cyano groups in the system, which endow the cured product with good thermal stability, low flexural modulus, good impact performance and moisture resistance, and the glass transition temperature is also improved.

[0029] (4) The resin cured product of the present application has both flexible siloxane chains and rigid phthalonitrile, which enhances the movement ability of molecular chain segments, making the cured product easy to produce plastic deformation to absorb energy under external force, and has better toughness; and can effectively improve the toughness of the cured product while improving the T g , so that the cured product has good bending performance. BRIEF DESCRIPTION OF DRAWINGS

[0030] The accompanying drawings are included to provide a further understanding of the present application, and constitute a part of the specification, which together with the embodiments of the present application, serve to explain the present application, and do not constitute a limitation on the present application. In the drawings: Figure 1 The nuclear magnetic resonance hydrogen spectrum of the intermediate of the modifier in the embodiment of the present application, hydrogen-containing polysiloxane PMHS; Figure 2 The nuclear magnetic resonance hydrogen spectrum of the intermediate of the modifier in the embodiment of the present application, eugenol-based polysiloxane PMES; Figure 3 The nuclear magnetic resonance hydrogen spectrum of the prepared modifier, eugenol-phthalonitrile polysiloxane PMNS in the embodiment of the present application. DETAILED DESCRIPTION

[0031] In order to make the above-mentioned purposes, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application will be described in detail below. The embodiments are implemented on the premise of the technical scheme of the present application, and detailed implementation methods and processes are given, but the protection scope of the present application is not limited to the following embodiments. The experimental methods not marked with specific conditions in the following embodiments are usually carried out according to conventional conditions or according to the conditions recommended by the manufacturers.

[0032] The raw materials used in the embodiments of the present application are as follows, but are not limited thereto: 4-nitrophthalonitrile, purchased from Shanghai Aldrin Biochemical Technology Co., Ltd., CAS No. 31643-49-9; Anhydrous potassium carbonate (K2CO3), purchased from Shanghai Maikelin Biochemical Technology Co., Ltd., CAS No. 584-08-7; N,N-dimethylformamide (DMF), purchased from China National Pharmaceutical Group Chemical Reagent Co., Ltd.; Polyfunctional 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, hydroxyl equivalent weight 168-174 g / eq; Octamethylcyclotetrasiloxane (D4), purchased from Shanghai Titan Technology Co., Ltd., CAS No. 556-67-2; 1,3,5,7-tetramethylcyclotetrasiloxane (D4H), purchased from Shanghai Titan Technology Co., Ltd., CAS No. 2370-88-9; 1,1,3,3-tetramethyldisiloxane (TMDS), purchased from Shanghai Titan Technology Co., Ltd., CAS No. 3277-26-7; Trifluoromethanesulfonic acid (TfOH), purchased from Shanghai Aldrin Biochemical Technology Co., Ltd., CAS No. 1493-13-6; Eugenol (EG), purchased from Shanghai Aldrin 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 Science and Technology Co., Ltd., CAS No. 68478-92-2; Triphenylphosphine (TPP), purchased from Shanghai Aladdin Bio-Chem Technology Co., Ltd., CAS No. 603-35-0; Spherical fused silica, average particle size of 20 μm and 8 μm, purchased from Nippon Sheet Glass Co., Ltd.; Silane coupling agent: γ-glycidoxypropyltrimethoxysilane (KBM-403), purchased from Japan Shin-Etsu Chemical Co., Ltd.; Colorant: carbon black, purchased from Mitsubishi Gas Chemical Company, Inc.; Release agent: Brazil palm wax, purchased from Shanghai Yiba Chemical Trade Co., Ltd.

[0033] Test method of each performance index in the embodiment of the present application: (1) Spiral flow length: according to the method shown in SJ / T 11197-2013 Epoxy Plastic Encapsulating Material, take 15 g of the resin composition sample to be tested, inject it into the spiral flow metal mold of EMMI-1-66 on the transfer molding press, and measure the spiral flow length of the sample. Set the upper and lower mold temperature to 175 ± 3 °C, the transfer pressure to (125 kg ± 5 kg) cm -2 , the transfer speed to (6.0 cm ± 0.1 cm) s -1 , and cure for 120 s. Then take out the sample from the metal mold and read the spiral flow length, accurate to 0.5 cm. Test the same sample three times and take the average value. The transfer pressure is obtained by dividing the total pressure by the injection head area.

[0034] (2) Gel time: according to the method shown in SJ / T 11197-2013 Epoxy Plastic Encapsulating Material, heat the hot plate to 175 °C ± 2 °C, take 0.3~0.5 g of the resin composition sample and place it on the hot plate. The sample spreading area is about 5 cm 2 . Start counting the melting time, stir with a needle-shaped stirring tip or a flat shovel, and gradually change the powder into a gelatinous state (the sample cannot be pulled into a silk) as the end point. Read the required time, repeat the same operation twice, and take the average value.

[0035] (3) Thermal stability: the resin composition was molded at 175 °C using an injection molding machine, and then post-cured under the conditions of 200 °C for 2 h, 230 °C for 2 h, and 260 °C for 2 h; then, a thermogravimetric analysis (TGA) test was performed using a TGA / 1100SF instrument under an N2 atmosphere at a temperature range of 50-800 °C, a temperature increase rate of 10 °C / min, a flow rate of 50 mL / min, and 5-10 mg of each sample, to determine the degradation temperature (T 5% ).

[0036] (4) Bending strength and bending modulus: the resin composition was molded at 175 °C using an injection molding machine, and then post-cured under the conditions of 200 °C for 2 h, 230 °C for 2 h, and 260 °C for 2 h; then, a test was performed according to the national standard GB / T 9341-2008 "Determination of Bending Properties of Plastics" of the People's Republic of China. Double 85 testing was performed, the cured product was placed in a constant temperature and humidity chamber with a model of LHS-50CH, and the test was performed under the conditions of 85 °C and 85 % relative humidity, and the test cycle was 96 h.

[0037] (5) Impact strength: the resin composition was molded at 175 °C using an injection molding machine, and then post-cured under the conditions of 200 °C for 2 h, 230 °C for 2 h, and 260 °C for 2 h; then, a test was performed according to the national standard GB / T-1843-2008 "Determination of Impact Properties of Plastics" of the People's Republic of China.

[0038] (6) Glass transition temperature (T g ): the resin composition was molded at 175 °C using an injection molding machine, and then post-cured under the conditions of 200 °C for 2 h, 230 °C for 2 h, and 260 °C for 2 h; a dynamic mechanical analyzer was used to perform a T g test according to the standard ASTM E1640-2013 "Standard Test Method for Assignment of the Glass Transition Temperature by Dynamic Mechanical Analysis".

[0039] Examples 1-4: The raw materials used in Examples 1-4 of the present application and their amounts are shown in Table 1: In the examples, the preparation method of the modifier, i.e., the eugenol-containing phthalonitrile polysiloxane (PMNS), includes the following three steps: S1, Preparation of hydrogen-containing polysiloxane (PMHS): octamethylcyclotetrasiloxane D4 (108 g, 0.364 mol), 1,3,5,7-tetramethylcyclotetrasiloxane D4H (48 g, 0.199 mol), 1,1,3,3-tetramethyldisiloxane TMDS (16.5 g, 0.123 mol) and initiator trifluoromethanesulfonic acid TfOH (0.3 wt% of total reactants) were sequentially added into a flask and stirred at 25 °C for 24 h; concentrated by rotary evaporation and vacuum dried at 70 °C for 12 h to obtain a colorless transparent liquid, which was hydrogen-containing polysiloxane PMHS with a yield of 74%, the ratio of m and n was 12:10, and the molecular weight of PMHS was 1642; the proton nuclear magnetic resonance spectrum of PMHS is shown in Figure 1 .

[0040] The reaction equation is as follows: S2, Preparation of eugenol-based polysiloxane (PMES): eugenol EG (67.3 g, 0.615 mol), Karstedt catalyst (5 ppm, 37 μL) and toluene (200 mL) were sequentially added into a flask, stirred under N2 atmosphere for 15 min, and heated to 80 °C at the same time. PMHS (60 g, 0.041 mol) was dissolved in 100 ml of toluene and then added dropwise into the flask using a dropping funnel, and the dropwise addition was completed within 90 min. Then the temperature was increased to 100 °C and the reaction was continued for 24 h; after the reaction was completed, toluene was removed by rotary evaporation, followed by repeated extraction with n-hexane to remove excess eugenol, and then rotary evaporation and vacuum drying were performed again to obtain eugenol-based polysiloxane (PMES) with a yield of 75%, and the molecular weight of PMES was 3406; the proton nuclear magnetic resonance spectrum of PMES is shown in Figure 2 .

[0041] The reaction equation is as follows: S3, Preparation of eugenol-phthalonitrile polysiloxane (PMNS): 4-nitrophthalonitrile 4-PN (72.7 g, 0.14 mol), PMES (95.1 g, 0.028 mol), potassium carbonate (22.1 g, 0.16 mol), N,N-dimethylformamide (300 ml) were mixed in a flask and stirred vigorously at 80 °C for 8 h; then the reaction solution was added dropwise into 0.1 mol / L aqueous sodium hydroxide solution for precipitation, and the precipitate was washed with water until it was neutral, and then vacuum dried at 60 °C for 12 h to obtain eugenol-phthalonitrile polysiloxane (PMNS) with a yield of 80%, and the molecular weight of PMNS was 3742; the proton nuclear magnetic resonance spectrum of PMNS is shown inFigure 3 as shown.

[0042] The reaction equation is as follows: Table 1 The modifier addition amounts of Examples 1-4 are 5.00%, 10.00%, 15.00% and 20.00%, respectively The preparation method of the thermosetting resin composition for high-reliability semiconductor device packaging according to Examples 1-4 is as follows: the above-mentioned multifunctional epoxy resin (EPPN-501H), XYLOK phenolic resin (SH-4064), triphenylphosphine (TPP), syzygium aromaticum o-phenylenedinitrile polysiloxane (PMNS), spherical fused silica (average particle size of 20 μm, 8 μm), silane coupling agent (γ-glycidoxypropyltrimethoxysilane), colorant (carbon black) and release agent (carnauba wax) are mixed at room temperature by a high-speed mixer at a rotation speed of 1000 rpm according to the proportions shown in Table 1, and then melt-kneaded by a twin-screw kneader at 80-110 °C. The kneaded material is then cooled and pulverized to obtain the thermosetting resin composition.

[0043] Comparative Examples 1-2: The raw materials and amounts used in Comparative Examples 1 and 2 are shown in Table 2: Table 2 Comparative Example 1 is a preparation method of a conventional epoxy molding compound, and Comparative Example 2 is a preparation method of an epoxy molding compound added with 10% of a commonly used core-shell rubber particle (purchased from Wuxi Chuanda New Material Co., Ltd., model EXL2655). The specific steps are as follows: the multifunctional epoxy resin (EPPN-501H), XYLOK phenolic resin (SH-4064), triphenylphosphine (TPP), core-shell rubber particle (EXL2655), spherical fused silica (average particle size of 8 μm, 20 μm), silane coupling agent (KBM-403), colorant (carbon black) and release agent (carnauba wax) are mixed at room temperature by a high-speed mixer at a rotation speed of 1000 rpm according to the proportions shown in Table 2; and then the prepared mixture is melt-kneaded by a twin-screw kneader at 80-110 °C. The kneaded mixture is then cooled and pulverized to obtain the epoxy molding compound.

[0044] The performance test results of Examples and Comparative Example 1 are shown in Table 3: Table 3 According to the test results in Table 3, the resin composition of the present application shows significant advantages compared with the comparative examples. The spiral flow length (36-48) of the examples is higher than that of the comparative examples, indicating that the modifier of the present application effectively improves the flowability of the resin system, and can better fill and form. The gel time of each example is significantly shorter than that of Comparative Example 1, and the gel time of Examples 3 / 4 is shorter than that of Comparative Example 2, indicating that the present application effectively improves the curing efficiency on the basis of maintaining good flowability, which helps to improve the production efficiency. It is consistent with the current curing and molding process of commercial electronic packaging epoxy molding compound. It is mainly due to the fact that the viscosity of the eugenol o-phthalodinitrile polysiloxane is lower than that of the multifunctional epoxy resin (EPPN-501H) and the XYLOK phenolic resin (SH-4064).

[0045] The mechanical properties and heat resistance of the thermosetting resin composition of the present application are also excellent. The bending strength and modulus of the examples are at a relatively high level as a whole, and after "double 85" aging, the performance retention rate is also significantly better than that of the comparative examples. After the "double 85" aging test, the performance retention rate is significantly better than that of the control group: especially the bending strength, indicating that the composition of the present application has good structural stability in a high temperature and high humidity environment; compared with Example 1, the addition of the modifier of the present application significantly reduces the bending modulus of the system. The impact strength of Examples 1-4 is higher than that of Comparative Examples 1-2, and the toughness is better. The heat resistance of the composition of the present application is good, and the glass transition temperature (T g ) of the examples reaches 158-163°C, which is significantly improved compared with Comparative Examples 1-2, and the application in high temperature fields is widened. The resin composition of the present application realizes the synergistic improvement in flowability, curing efficiency, mechanical strength, environmental durability and heat resistance, balances the processing performance and terminal application requirements, and has high practical value.

[0046] The o-phthalodinitrile resin after curing usually has a high crosslinking density, and a rigid structure containing isoindole, triazine ring, phthalocyanine and other aromatic heterocycles is formed, resulting in a large brittleness and insufficient toughness of the cured product, which often shows a high bending modulus. In order to solve this problem, the rigid structure of o-phthalodinitrile and the flexible structure of siloxane are combined in the present application, and the eugenol o-phthalodinitrile polysiloxane prepared as a modifier is added to the resin system, which has good mechanical compatibility and dispersibility in the base resin; the resin composition of the present application has flexible siloxane chains and rigid o-phthalodinitrile, which enhances the movement ability of the molecular chain segments, so that the cured product is easy to produce plastic deformation to absorb energy under external force, and has better toughness. At the same time, due to the low polarity of siloxane, the overall hydrophobicity is shown after adding the molding compound, and the mechanical properties are basically unchanged after double 85 treatment. The resin composition of the present application has excellent thermal stability, higher T g , lower bending modulus, higher impact strength, and better wet heat resistance after curing; especially, the glass transition temperature (Tg ) while effectively improving the toughness of the cured product. Application to electronic device packaging has higher reliability and environmental stability.

[0047] It should be noted that the above examples are only used to illustrate the technical solutions of the present application and are not limiting. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or equivalently replaced without departing from the spirit and scope of the present application, and they should be covered in the scope of the present application.

Claims

1. A thermosetting resin composition for electronic device encapsulation, characterized in that, The composition comprises a multifunctional epoxy resin, an XYLOK phenolic resin, a curing accelerator, a modifier, and an inorganic filler; The modifier is a eugenol-phthalonitrile polysiloxane, having a structure shown in formula (I): （I）； In formula (I), m and n are independently integers in the range of 5-30; The content of the modifier is 1-30 wt% of the total amount of the multifunctional epoxy resin and the XYLOK phenolic resin, preferably 1-20 wt%.

2. The thermosetting resin composition for electronic device packaging according to claim 1, wherein: The mass ratio of the multifunctional epoxy resin and the XYLOK phenolic resin is 5:1-1:5; The content of the curing accelerator is 0.5-5 wt% of the total amount of the multifunctional epoxy resin and the XYLOK phenolic resin; The content of the inorganic filler is 70-90 wt% of the total amount of the composition.

3. The thermosetting resin composition for electronic device packaging according to any one of claims 1 to 2, characterized by, The multifunctional epoxy resin comprises a substance having a chemical structure shown in formula (II): (I); (II); (III); (IV); (V); ( In formula (II), R1 is a hydrogen atom or an alkyl group having 1-6 carbon atoms; n is an integer of 0-6; R' is selected from hydrogen, methyl, and ethyl.

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

5. The thermosetting resin composition for electronic device packaging according to any one of claims 1 to 2, characterized by, The eugenol-phthalonitrile polysiloxane is prepared by a three-step method, specifically comprising steps S1, S2, and S3. S1. A hydrogen-containing polysiloxane is obtained by polymerization of octamethylcyclotetrasiloxane, 1,3,5,7-tetramethylcyclotetrasiloxane, and 1,1,3,3-tetramethyl disiloxane in the presence of a cationic initiator; S2. The eugenol-based polysiloxane is obtained by reacting the hydrogen-containing polysiloxane prepared in step S1 with eugenol in the presence of a catalyst or under radiation conditions; S3. The eugenol-phthalonitrile polysiloxane is obtained by reacting the eugenol-based polysiloxane prepared in step S2 with 4-nitrophthalonitrile in the presence of an acid-binding agent.

6. The thermosetting resin composition for electronic device packaging according to claim 5, wherein: In step S1, the cationic initiator is selected from protonic acids, Lewis acids, or other cationic initiators; the other cationic initiators are selected from iodine, oxonium ions, perchlorate salts, cycloheptatriene salts, and triphenylmethyl salts; and / or, In step S2, the catalyst comprises organic base compounds, organic peroxides, azo compounds, and noble metal compounds; and / or, In step S2, 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 S2, the radiation conditions include ultraviolet rays, alpha rays, beta rays, gamma rays, X-rays, and neutron rays; and / or, In step S3, 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, sodium acetate.

7. The thermosetting resin composition for electronic device packaging according to any one of claims 1 to 2, characterized by, The curing accelerator is selected from one or a combination of tertiary amines, imidazole compounds, organophosphorus compounds, acetylacetone metal complexes.

8. The thermosetting resin composition for electronic device packaging according to any one of claims 1 to 2, characterized by, The inorganic filler includes spherical fused silica, the average particle size of the spherical fused silica is 0.01-30 μm; and / or, The content of the spherical fused silica is 50-100 wt% of the total amount of the inorganic filler.

9. The thermosetting resin composition for electronic device packaging according to any one of claims 1 to 2, characterized by, The additives include one or more of silane coupling agents, colorants, mold release agents.

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

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