High-adhesion epoxy molding compound as well as preparation method and application thereof

Abstract

The invention relates to the field of epoxy resin materials, and discloses a high-adhesion epoxy molding compound as well as a preparation method and application thereof. Based on the total weight of the high-adhesion epoxy molding compound, the high-adhesion epoxy molding compound is prepared from the following components in percentage by weight: 5 to 18 percent of epoxy resin, 2.5 to 10 percent of phenolic resin, 0.05 to 0.5 percent of curing accelerator, 60 to 90 percent of filler, 0.1 to 2 percent of modifier, 0.1 to 1.5 percent of release agent and 0.1 to 1 percent of coupling agent, wherein the coupling agent is a combination of a first coupling agent and a second coupling agent, and the weight ratio of the first coupling agent to the second coupling agent is 1: (1-6). The high-adhesion epoxy molding compound has excellent adhesion with a chip and a frame in a semiconductor device, and also has good formability and soldering resistance.

Description

Technical Field

[0001] The invention relates to the field of epoxy resin materials, and in particular to a high-adhesion epoxy molding compound and a preparation method and application thereof. Background Art

[0002] Epoxy molding compounds have many excellent properties and have been widely used in the packaging field. They are the mainstream materials for semiconductor components and integrated circuit packaging. In recent years, semiconductors have developed towards high integration, which has led to larger chips and more complex structures. Therefore, higher requirements are required for the adhesion between the molding compound inside the package and the chip and various frame surfaces to ensure the reliability of the device.

[0003] The components of epoxy molding compounds for semiconductor packaging generally include epoxy resin, curing agent, curing accelerator, filler flame retardant, mold release agent, coupling agent, colorant, mechanical modifier, etc. Traditional coupling agents such as KH550 and KH560 have both a methoxy group (or ethoxy group) and another special functional group, such as epoxy group, amino group, etc.; the methoxy group (or ethoxy group) is hydrolyzed to form a hydroxyl group that combines with the hydroxyl group on the surface of the filler or inorganic material, and the ring group and amino group react and combine with the organic resin or metal interface to improve the interfacial compatibility between the resin system and the filler and enhance the bonding strength. However, due to the small molecular chain of a single coupling agent and the complexity of the packaging structure and the material interface, the probability of the chemical reaction on which the interface improvement depends is not high, and it is difficult to meet the demand for high adhesion. Summary of the invention

[0004] The purpose of the present invention is to overcome the problem that the bonding force between the epoxy resin molding compound and the metal interface in the prior art is difficult to meet the application requirements, and provide a high-adhesion epoxy molding compound and its preparation method and application. The high-adhesion epoxy molding compound has excellent bonding force with the chip and frame in the semiconductor device, and also has good solder resistance and formability.

[0005] In order to achieve the above-mentioned object, the first aspect of the present invention provides a high-adhesion epoxy molding compound, which contains 5-18 wt % of epoxy resin, 2.5-10 wt % of phenolic resin, 0.05-0.5 wt % of curing accelerator, 60-90 wt % of filler, 0.1-2 wt % of modifier, 0.1-1.5 wt % of release agent and 0.1-1 wt % of coupling agent based on the total weight of the high-adhesion epoxy molding compound;

[0006] Wherein, the coupling agent is a combination of a first coupling agent and a second coupling agent, and the weight ratio of the first coupling agent to the second coupling agent is 1:1-6, the first coupling agent is γ-mercaptopropyltrimethoxysilane, and the second coupling agent is at least one of γ-glycidylpropyl ether trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane and γ-aminopropyl trimethoxysilane.

[0007] Preferably, the coupling agent is a combination of γ-mercaptopropyltrimethoxysilane, γ-glycidylpropyl ether trimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane, and the weight ratio of γ-mercaptopropyltrimethoxysilane, γ-glycidylpropyl ether trimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane is 1:(0.1-3):(0.1-3).

[0008] Preferably, the epoxy resin is selected from at least one of o-cresol epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, polyphenol glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, alicyclic epoxy resin and heterocyclic epoxy resin.

[0009] Preferably, the phenolic resin is selected from at least one of phenol linear phenolic resin and its derivatives, cresol linear phenolic resin and its derivatives, monohydroxy or dihydroxy naphthol phenolic resin and its derivatives, condensates of p-xylene and phenol or naphthol, and copolymers of dicyclopentadiene and phenol.

[0010] Preferably, the curing accelerator is selected from at least one of imidazole compounds, tertiary amine compounds and organic phosphine compounds.

[0011] Preferably, the imidazole compound is at least one selected from 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-(heptadecanyl)imidazole.

[0012] Preferably, the tertiary amine compound is at least one selected from triethylaminebenzyldimethylamine, α-methylbenzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol and 1,8-diazabicyclo[5,4,0]undec-7-ene.

[0013] Preferably, the organic phosphine compound is at least one selected from triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine and tri(nonylphenyl)phosphine.

[0014] Preferably, the filler is selected from at least one of alumina micropowder, titanium oxide micropowder, silicon nitride micropowder, aluminum nitride micropowder and silicon dioxide micropowder.

[0015] Preferably, the silica powder is at least one selected from modified silica, crystalline silica, fused silica and a combination of crystalline silica and fused silica.

[0016] Preferably, the release agent is selected from at least one of carnauba wax, synthetic wax and mineral wax.

[0017] Preferably, the modifier is liquid silicone oil and / or silicone rubber.

[0018] Preferably, based on the total weight of the high-adhesion epoxy molding compound, the high-adhesion epoxy molding compound further contains 0.1-10 wt % of a flame retardant and 0.1-3 wt % of a colorant.

[0019] Preferably, the flame retardant is at least one selected from halogen flame retardants, phosphorus flame retardants, nitrogen flame retardants, phosphorus-halogen flame retardants, phosphorus-nitrogen flame retardants and hydroxide flame retardants.

[0020] Preferably, the colorant is selected from at least one of titanium dioxide, zinc oxide, lithopone and carbon black.

[0021] The second aspect of the present invention provides a method for preparing the high-adhesion epoxy molding compound described above, the method comprising: melt-mixing epoxy resin, phenolic resin, curing accelerator, filler, modifier, release agent, coupling agent and optional flame retardant and colorant, and then molding the obtained mixture.

[0022] Preferably, the melt mixing conditions include: temperature of 60-110° C., preferably 70-100° C.; time of 3-8 min, preferably 4-7 min.

[0023] A third aspect of the present invention provides an application of the high-adhesion epoxy molding compound mentioned above in a semiconductor chip packaging process.

[0024] Under high temperature conditions, the high-adhesion epoxy molding compound of the present invention reacts the thiol (-SH) and siloxane (Si-O) groups in the thiol coupling agent molecules with the hydroxyl (-OH) on the surface of the inorganic material to form chemical bonds, thereby forming strong chemical bonds between the material surface and the thiol coupling agent molecules, while improving the surface wettability and antioxidant properties of the material, thereby improving the comprehensive performance of the material, and achieving improved interface bonding strength between the two main components of the epoxy molding compound, the resin and the filler, and the chip and the metal frame in the semiconductor device; at the same time, the high-adhesion epoxy molding compound also has good solder resistance and formability, and can meet the application requirements of the molding compound in the semiconductor device packaging process. DETAILED DESCRIPTION

[0025] The specific embodiments of the present invention are described in detail below. It should be understood that the specific embodiments described herein are only used to illustrate and explain the present invention, and are not used to limit the present invention.

[0026] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0027] Based on the total weight of the high-adhesion epoxy molding compound of the present invention, the high-adhesion epoxy molding compound contains 5-18 weight % of epoxy resin, 2.5-10 weight % of phenolic resin, 0.05-0.5 weight % of curing accelerator, 60-90 weight % of filler, 0.1-2 weight % of modifier, 0.1-1.5 weight % of release agent and 0.1-1 weight % of coupling agent;

[0028] Wherein, the coupling agent is a combination of a first coupling agent and a second coupling agent, and the weight ratio of the first coupling agent to the second coupling agent is 1:1-6, preferably 1:2-5, and more preferably 3-4:1.

[0029] The first coupling agent is γ-mercaptopropyltrimethoxysilane, and its molecular formula is shown in formula (1).

[0030]

[0031] The second coupling agent is at least one of γ-glycidyl propyl ether trimethoxy silane, N-phenyl-3-aminopropyl trimethoxy silane, γ-aminopropyl triethoxy silane and γ-aminopropyl trimethoxy silane.

[0032] In a preferred case, based on the total weight of the high-adhesion epoxy molding compound, the high-adhesion epoxy molding compound contains 8-18 wt% of epoxy resin, 2.5-8 wt% of phenolic resin, 0.1-0.5 wt% of curing accelerator, 70-85 wt% of filler, 0.1-1.5 wt% of modifier, 0.5-1 wt% of release agent and 0.3-1 wt% of coupling agent. When the content of each component of the high-adhesion epoxy molding compound is within the above preferred range, the high-adhesion epoxy molding compound has higher adhesion and excellent comprehensive performance.

[0033] In a more preferred embodiment, the coupling agent is a combination of γ-mercaptopropyl trimethoxysilane, γ-glycidyl propyl ether trimethoxysilane and N-phenyl-3-aminopropyl trimethoxysilane, and the weight ratio of γ-mercaptopropyl trimethoxysilane, γ-glycidyl propyl ether trimethoxysilane and N-phenyl-3-aminopropyl trimethoxysilane is 1: (0.1-3): (0.1-3), preferably 1: (0.5-2): (0.5-2). In these embodiments, when the coupling agent contains the above components (especially within the preferred range), the high coupling agent is easier to form a stronger chemical bond with the filler or inorganic material surface, further improving the adhesion of the high adhesion epoxy molding compound.

[0034] In the present invention, the epoxy resin can be at least one of o-cresol epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, polyphenol glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, alicyclic epoxy resin and heterocyclic epoxy resin, preferably a combination of o-cresol epoxy resin and biphenyl epoxy resin, wherein the weight ratio of the o-cresol epoxy resin to the biphenyl epoxy resin is 1-10:1, more preferably 3-8:1. In the present invention, when the epoxy resin is of the above type (especially the preferred type), the high-adhesion epoxy molding compound has a higher adhesion and excellent comprehensive performance.

[0035] In the present invention, the phenolic resin can be at least one of phenol linear phenolic resin and derivatives thereof, cresol linear phenolic resin and derivatives thereof, monohydroxy or dihydroxy naphthol phenolic resin and derivatives thereof, the condensation product of p-xylene and phenol or naphthol and the copolymer of dicyclopentadiene and phenol, preferably phenol linear phenolic resin and / or phenol alkylphenolic resin. In the present invention, when the phenolic resin is the above-mentioned kind (especially the preferred kind), the high-bonding epoxy molding compound has higher bonding force and excellent comprehensive performance.

[0036] In the present invention, the curing accelerator may be at least one of an imidazole compound, a tertiary amine compound and an organic phosphine compound.

[0037] Preferably, the imidazole compound is at least one selected from 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-(heptadecanyl)imidazole, more preferably 2-methylimidazole.

[0038] In a preferred embodiment, the tertiary amine compound is at least one selected from triethylaminebenzyldimethylamine, α-methylbenzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol and 1,8-diazabicyclo[5,4,0]undec-7-ene, and more preferably α-methylbenzyldimethylamine.

[0039] Preferably, the organic phosphine compound is at least one selected from the group consisting of triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine and tri(nonylphenyl)phosphine.

[0040] In a more preferred embodiment, the curing accelerator is a combination of 2-methylimidazole and α-methylbenzyldimethylamine, wherein the weight ratio of the 2-methylimidazole to the α-methylbenzyldimethylamine is 1-5:1, more preferably 1-3:1. According to this preferred embodiment, the high-adhesion epoxy molding compound has further improved adhesion and comprehensive performance.

[0041] In the high-adhesion epoxy molding compound of the present invention, the filler may be at least one of aluminum oxide powder, titanium oxide powder, silicon nitride powder, aluminum nitride powder and silicon dioxide powder, preferably silicon dioxide powder.

[0042] Further preferably, the silicon dioxide powder is selected from at least one of modified silicon dioxide, crystalline silicon dioxide, fused silicon dioxide and a combination of crystalline silicon dioxide and fused silicon dioxide. In the high-adhesion epoxy molding compound of the present invention, the release agent can be at least one of carnauba wax, synthetic wax and mineral wax, preferably carnauba wax.

[0043] In the high-adhesion epoxy molding compound of the present invention, the modifier may be liquid silicone oil and / or silicone rubber, preferably liquid silicone oil.

[0044] In a more preferred embodiment, the release agent is carnauba wax, and the modifier is liquid silicone oil. According to this preferred embodiment, the high-adhesion epoxy molding compound has further improved adhesion and comprehensive performance.

[0045] In the high-adhesion epoxy molding compound of the present invention, the high-adhesion epoxy molding compound may further contain a flame retardant and / or a colorant. In a preferred case, based on the total weight of the high-adhesion epoxy molding compound, the content of the flame retardant is 0.1-10% by weight, preferably 1-10% by weight, and more preferably 2-8% by weight; the content of the colorant is 0.1-3% by weight, preferably 0.1-2% by weight, and more preferably 0.1-1% by weight.

[0046] In the present invention, the flame retardant may be at least one of a halogen flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, a phosphorus-halogen flame retardant, a phosphorus-nitrogen flame retardant and a hydroxide flame retardant.

[0047] In the present invention, the colorant may be at least one of titanium dioxide, zinc oxide, lithopone and carbon black.

[0048] The high-adhesion epoxy molding compound of the present invention can be prepared by conventional methods in the art. In a preferred embodiment, the preparation method of the high-adhesion epoxy molding compound comprises: melt-mixing epoxy resin, phenolic resin, curing accelerator, filler, modifier, release agent, coupling agent, and optional flame retardant and colorant, and then molding the obtained mixture.

[0049] In the method of the present invention, the melt-kneading conditions may include: a temperature of 60-110° C., preferably 70-100° C.; and a time of 3-8 min, preferably 4-7 min.

[0050] In some embodiments, the method for preparing the high-adhesion epoxy molding compound is specifically as follows: based on the total weight of the high-adhesion epoxy molding compound, 5-18 weight % of epoxy resin, 2.5-10 weight % of phenolic resin, 0.05-0.5 weight % of curing accelerator, 60-90 weight % of filler, 0.1-2 weight % of modifier, 0.1-1 weight % of coupling agent, 0.1-10 weight % of flame retardant, 0.1-1.5 weight % of release agent and 0.1-3 weight % of colorant are uniformly mixed, wherein the coupling agent is a combination of a first coupling agent and a second coupling agent, and the The weight ratio of the first coupling agent to the second coupling agent is 1:1-6, the first coupling agent is γ-mercaptopropyl trimethoxysilane, and the second coupling agent is at least one of γ-glycidyl propyl ether trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane and γ-aminopropyl trimethoxysilane; then the obtained mixture is melt-mixed on an open rubber mixer preheated at a temperature of 60-110°C for 4-7 minutes, the obtained product is removed from the open rubber mixer, naturally cooled, crushed to obtain a powdery material, preformed into a cake material, and an epoxy molding compound molding material is obtained. When the preparation method is implemented according to this embodiment, the prepared high-adhesion epoxy molding compound has a high adhesion and excellent comprehensive performance.

[0051] The high-adhesion epoxy molding compound described in the present invention can be applied to the semiconductor chip packaging process. In the high-adhesion epoxy molding compound described in the present invention, a strong chemical bond can be formed between the surface of the inorganic material and the mercapto coupling agent molecules, while improving the surface wettability and antioxidant properties of the material, thereby improving the comprehensive performance of the material, and achieving the improvement of the interface bonding strength between the two main components of the epoxy molding compound, the resin and the filler, and the chip and the metal frame in the semiconductor device, respectively. The copper surface bonding force is ≥905N, and the silver surface bonding force is ≥587N; at the same time, the high-adhesion epoxy molding compound also has good solder resistance and formability, which can meet the application requirements of the molding compound in the semiconductor device packaging process.

[0052] The following examples further illustrate the high adhesion epoxy molding compound and its preparation method and application of the present invention. The examples are implemented based on the technical solution of the present invention, and provide detailed implementation methods and specific operation processes, but the protection scope of the present invention is not limited to the following examples.

[0053] The experimental methods in the following examples, unless otherwise specified, are conventional methods in the art.

[0054] The o-cresol epoxy resins used in the following examples and comparative examples are all "CYDCN-200H" produced by Baling Petrochemical;

[0055] The biphenyl type epoxy resins were all "YX-4000" manufactured by Japan Epoxy Resins Co.

[0056] The phenol linear phenolic resins were all “TD-2131” manufactured by DIC Corporation of Japan;

[0057] The phenol alkylphenol-formaldehyde resins were all "XLC-4L" manufactured by Mitsui Chemicals, Inc.

[0058] Unless otherwise specified, the experimental materials used in the following examples and comparative examples are all commercially available.

[0059] Example 1

[0060] Based on the total weight of the high-adhesion epoxy molding compound, 9.82 g of o-cresol type epoxy resin, 1.9 g of biphenyl type epoxy resin, 4.95 g of phenol linear phenolic resin, 0.18 g of 2-methylimidazole, 0.1 g of α-methylbenzyldimethylamine, 72.91 g of silica powder with a particle size D50 of 22 μm, 7.7 g of aluminum hydroxide, 0.2 g of γ-mercaptopropyltrimethoxysilane, 0.2 g of N-phenyl-3-aminopropyltrimethoxysilane, 0.15 g of γ-glycidyloxypropyltrimethoxysilane, Methoxysilane, 1g of liquid silicone oil, 0.95g of carnauba wax and 0.3g of carbon black are mixed evenly, wherein the weight ratio of γ-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and γ-glycidyloxypropyltrimethoxysilane is 1:1:0.75; then the obtained mixture is melt-kneaded on an open rubber mixer preheated at 80°C for 7 minutes, the obtained product is removed from the open rubber mixer, naturally cooled, and crushed to obtain a powdery material, which is preformed into a cake material to obtain an epoxy molding compound molding material.

[0061] Example 2

[0062] Based on the total weight of the high-adhesion epoxy molding compound, 9.82g of o-cresol epoxy resin, 1.9g of biphenyl epoxy resin, 2.9g of phenol linear phenolic resin, 2.05g of phenol alkyl phenolic resin, 0.18g of 2-methylimidazole, 0.1g of α-methylbenzyldimethylamine, 72.64g of silica powder with a particle size D50 of 22μm, 7.7g of aluminum hydroxide, 0.2g of γ-mercaptopropyltrimethoxysilane, 0.2g of N-phenyl-3-aminopropyltrimethoxysilane, 0.15g of γ-glycidyl Oleyl etheroxypropyl trimethoxysilane, 1.27g of liquid silicone oil, 0.95g of carnauba wax and 0.3g of carbon black are mixed evenly, wherein the weight ratio of γ-mercaptopropyl trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane and γ-glycidyl etheroxypropyl trimethoxysilane is 1:1:0.75; then the obtained mixture is melt-kneaded evenly on an open rubber mixer preheated at 80°C, the obtained product is removed from the open rubber mixer, naturally cooled, and crushed to obtain a powdery material, which is preformed into a cake material to obtain an epoxy molding compound molding material.

[0063] Example 3

[0064] Based on the total weight of the high-adhesion epoxy molding compound, 9.82 g of o-cresol epoxy resin, 1.9 g of biphenyl epoxy resin, 3 g of phenol linear phenolic resin, 2.05 g of phenol alkyl phenolic resin, 0.18 g of 2-methylimidazole, 0.1 g of α-methylbenzyldimethylamine, 73.25 g of silica powder with a particle size D50 of 22 μm, 7.7 g of aluminum hydroxide, 0.2 g of γ-mercaptopropyltrimethoxysilane, 0.2 g of N-phenyl-3-aminopropyltrimethoxysilane, 0.15 g of γ-glycidol Etheroxypropyl trimethoxysilane, 0.65g of liquid silicone oil, 0.95g of carnauba wax and 0.3g of carbon black are mixed evenly, wherein the weight ratio of γ-mercaptopropyl trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane and γ-glycidyl etheroxypropyl trimethoxysilane is 1:1:0.75; then the obtained mixture is melt-kneaded evenly on an open rubber mixer preheated at 80°C, the obtained product is removed from the open rubber mixer, naturally cooled, and crushed to obtain a powdery material, which is preformed into a cake material to obtain an epoxy molding compound molding material.

[0065] Example 4

[0066] Based on the total weight of the high-adhesion epoxy molding compound, 9.82 g of o-cresol type epoxy resin, 1.9 g of biphenyl type epoxy resin, 2.95 g of phenol linear phenolic resin, 0.18 g of 2-methylimidazole, 0.1 g of α-methylbenzyldimethylamine, 74.8 g of silica powder with a particle size D50 of 22 μm, 7.7 g of aluminum hydroxide, 0.2 g of γ-mercaptopropyltrimethoxysilane, 0.1 g of N-phenyl-3-aminopropyltrimethoxysilane, 0.15 g of γ-glycidyloxypropyltrimethoxysilane, 0.85 g of liquid silicone oil, 0.95 g of carnauba wax and 0.3 g of carbon black are uniformly mixed, wherein the weight ratio of γ-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and γ-glycidyloxypropyltrimethoxysilane is 2:1:1.5; then the obtained mixture is melt-kneaded uniformly on an open rubber mixer preheated at 80°C, the obtained product is removed from the open rubber mixer, naturally cooled, and crushed to obtain a powdery material, which is preformed into a cake material to obtain an epoxy molding compound molding material.

[0067] Example 5

[0068] Based on the total weight of the high-adhesion epoxy molding compound, 9.82 g of o-cresol type epoxy resin, 1.9 g of biphenyl type epoxy resin, 2.95 g of phenol linear phenolic resin, 0.18 g of 2-methylimidazole and 0.1 g of α-methylbenzyldimethylamine, 75.55 g of silica powder with a particle size D50 of 22 μm, 7.7 g of aluminum hydroxide, 0.2 g of γ-mercaptopropyltrimethoxysilane, 0.1 g of N-phenyl-3-aminopropyltrimethoxysilane, 0.15 g of γ-glycidyloxypropyltrimethoxysilane and 0.2 g of γ-glycidyloxypropyltrimethoxysilane were added. Methoxysilane, 0.1 g of liquid silicone oil, 0.95 g of carnauba wax and 0.3 g of carbon black are mixed evenly, wherein the weight ratio of γ-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and γ-glycidyloxypropyltrimethoxysilane is 2:1:1.5; then the obtained mixture is melt-kneaded evenly on an open rubber mixer preheated at 80°C, the obtained product is removed from the open rubber mixer, naturally cooled, and crushed to obtain a powdery material, which is preformed into a cake material to obtain an epoxy molding compound molding material.

[0069] Example 6

[0070] Based on the total weight of the high-adhesion epoxy molding compound, 9.82g of o-cresol epoxy resin, 1.9g of biphenyl epoxy resin, 2.95g of phenol linear phenolic resin, 0.18g of 2-methylimidazole, 0.1g of α-methylbenzyldimethylamine, 75.38g of silica powder with a particle size D50 of 22μm, 7.7g of aluminum hydroxide, 0.2g of γ-mercaptopropyltrimethoxysilane, 0.1g of N-phenyl-3-aminopropyltrimethoxysilane, 0.15g of γ-glycidyloxypropyltrimethoxysilane, Methoxysilane, 0.27 g of liquid silicone oil, 0.95 g of carnauba wax and 0.3 g of carbon black are mixed evenly, wherein the weight ratio of γ-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and γ-glycidyloxypropyltrimethoxysilane is 2:1:1.5; then the obtained mixture is melt-kneaded evenly on an open rubber mixer preheated at 80°C, the obtained product is removed from the open rubber mixer, naturally cooled, and crushed to obtain a powdery material, which is preformed into a cake material to obtain an epoxy molding compound molding material.

[0071] Example 7

[0072] Based on the total weight of the high-adhesion epoxy molding compound, 9.82 g of o-cresol epoxy resin, 1.9 g of biphenyl epoxy resin, 4.95 g of phenol linear phenolic resin, 0.18 g of 2-methylimidazole, 0.1 g of α-methylbenzyldimethylamine, 73 g of silica powder with a particle size D50 of 22 μm, 7.7 g of aluminum hydroxide, 0.15 g of γ-mercaptopropyltrimethoxysilane, 0.15 g of N-phenyl-3-aminopropyltrimethoxysilane, 0.15 g of γ-glycidyloxypropyl Trimethoxysilane, 0.65 g of liquid silicone oil, 0.95 g of carnauba wax and 0.3 g of carbon black are uniformly mixed, wherein the weight ratio of γ-mercaptopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane and γ-glycidyloxypropyltrimethoxysilane is 1:1:1; then the obtained mixture is melt-kneaded uniformly on an open rubber mixer preheated at a temperature of 80°C, the obtained product is removed from the open rubber mixer, naturally cooled, and crushed to obtain a powdery material, which is preformed into a cake material to obtain an epoxy molding compound molding material.

[0073] Example 8

[0074] Based on the total weight of the high-adhesion epoxy molding compound, 9.82g of o-cresol type epoxy resin, 1.9g of biphenyl type epoxy resin, 3.5g of phenol linear phenolic resin, 1.35g of phenol alkyl phenolic resin, 0.18g of 2-methylimidazole, 0.1g of α-methylbenzyldimethylamine, 72.9g of silicon dioxide powder with a particle size D50 of 22μm, 7.7g of aluminum hydroxide, 0.15g of γ-mercaptopropyltrimethoxysilane, 0.15g of N-phenyl-3-aminopropyltrimethoxysilane, 0.15g of γ-condensed Glycidyloxypropyl trimethoxysilane, 0.85g of liquid silicone oil, 0.95g of carnauba wax and 0.3g of carbon black are uniformly mixed, wherein the weight ratio of γ-mercaptopropyl trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane and γ-glycidyloxypropyl trimethoxysilane is 1:1:1; then the obtained mixture is melt-kneaded uniformly on an open rubber mixer preheated at 80°C, the obtained product is removed from the open rubber mixer, naturally cooled, and crushed to obtain a powdery material, which is preformed into a cake material to obtain an epoxy molding compound molding material.

[0075] Example 9

[0076] This example was carried out according to the method described in Example 1, except that the second coupling agent was 0.2 g of γ-glycidyl propyl ether trimethoxy silane and 0.15 g of γ-aminopropyl trimethoxy silane.

[0077] Example 10

[0078] This example was carried out according to the method described in Example 1, except that the second coupling agent was 0.2 g of γ-glycidyl propyl ether trimethoxy silane and 0.15 g of γ-aminopropyl triethoxy silane.

[0079] Comparative Example 1

[0080] This comparative example was implemented according to the method shown in Example 1, except that only 0.55 g of γ-mercaptopropyltrimethoxysilane was added.

[0081] Comparative Example 2

[0082] This comparative example was implemented according to the method shown in Example 1, except that only 0.31 g of N-phenyl-3-aminopropyltrimethoxysilane and 0.24 g of γ-glycidyloxypropyltrimethoxysilane were added.

[0083] Comparative Example 3

[0084] This comparative example was implemented according to the method shown in Example 1, except that, based on the total weight of the high-adhesion epoxy molding compound, the second coupling agent added was 0.31 g of epoxy silicone glycidyl resin and 0.24 g of C8-Eopoxy.

[0085] Comparative Example 4

[0086] This comparative example was implemented according to the method shown in Example 1, except that 0.05 g of γ-mercaptopropyltrimethoxysilane, 0.29 g of N-phenyl-3-aminopropyltrimethoxysilane and 0.21 g of γ-glycidyloxypropyltrimethoxysilane were added, and the weight ratio of the first coupling agent to the second coupling agent was 1:10.

[0087] Test Example 1

[0088] This test example is used to illustrate the adhesion of the epoxy molding compound prepared in Examples 1-10 and Comparative Examples 1-4. The specific experimental steps include:

[0089] Sample preparation: Using a low-pressure transfer molding machine, the epoxy molding materials prepared in Examples 1-10 and Comparative Examples 1-4 were molded on the surface of the sample at a mold temperature of 175°C, an injection pressure of 60 bar, and a curing time of 110 seconds. The sample sheets were bare copper sheets and copper sheets with a silver-plated surface.

[0090] Adhesion test: A shear force is applied along the surface of the sample at a speed of 20 mm / min to test the maximum force value before the plastic sealant and the sample are separated. For the adhesion test, 5 samples are tested for each embodiment (or comparative example), and the average of the 5 test results is taken as the adhesion test result of the embodiment (or comparative example).

[0091] The results are shown in Tables 1 to 3.

[0092] Test Example 2

[0093] This test example is used to illustrate the solder resistance of the epoxy molding compound prepared in Examples 1-10 and Comparative Examples 1-4. The specific experimental steps include:

[0094] The obtained epoxy resin composition molding material was molded into SOP8L using a low-pressure transfer molding machine (produced by Shanghai Rishen Machinery Equipment Co., Ltd., SY-250T) at a mold temperature of 175°C, an injection pressure of 9.8MPa, and a curing time of 120s, and then post-cured at 175°C for 8 hours. 10 samples were selected and stored for 96 hours at a temperature of 85°C and a relative humidity of 60%, followed by 260°C infrared reflow soldering treatment 3 times. Thereafter, an ultrasonic scanning device was used to test whether there was peeling or cracks inside the packaged sample, and the number of defective samples was counted. When the number of defective samples is n, it is expressed as "n / 10".

[0095] The results are shown in Tables 1 to 3.

[0096] Test Example 3

[0097] This test example is used to illustrate the moldability of the epoxy molding compound prepared in Examples 1-10 and Comparative Examples 1-4. The specific experimental steps include:

[0098] The obtained epoxy resin composition material was formed into a cake shape using a hydraulic cake making machine (produced by Tengzhou Hexing CNC Machine Tool Co., Ltd., YD32-80T) under the conditions of an injection pressure of 5T and a holding time of 1s.

[0099] Observe the appearance of the formed cakes with the naked eye to see if there are pores, cracks or lid lifts, and count the number of defective samples. When the number of defective samples is n, it is expressed as "n / 10".

[0100] The results are shown in Tables 1 to 3.

[0101] Table 1

[0102]

[0103]

[0104] Table 2

[0105]

[0106]

[0107] Table 3

[0108]

[0109] It can be seen from the data in Tables 1 to 3 that by adopting the technical scheme described in the present invention, the epoxy molding compound prepared in Examples 1 to 10 has good adhesion, solder resistance and formability, the copper surface adhesion is ≥905N, the silver surface adhesion is ≥643N, and there are no defective samples in the solder resistance and formability tests. It has good comprehensive performance and adhesion, and can meet the application requirements of molding compounds in the semiconductor device packaging process. The epoxy molding compound prepared in Comparative Example 1 contains only γ-mercaptopropyltrimethoxysilane, and its adhesion and solder resistance are far worse than those of Examples 1-10; the epoxy molding compound prepared in Comparative Example 2 contains only N-phenyl-3-aminopropyltrimethoxysilane and γ-glycidyloxypropyltrimethoxysilane, and its adhesion, solder resistance and formability are far worse than those of Examples 1-10; the coupling agent added in Comparative Example 3 is epoxy silicone glycidyl resin and 0.24g of C8-Eopoxy, and its solder resistance and formability are greatly affected; Comparative Example 4 adds too much amino coupling agent and epoxy coupling agent, and less mercapto coupling agent, and its adhesion, solder resistance and formability are far worse than those of Examples 1-10.

[0110] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A high-adhesion epoxy molding compound, characterized in that: Based on the total weight of the high-adhesion epoxy molding compound, the high-adhesion epoxy molding compound contains 5-18 weight % of epoxy resin, 2.5-10 weight % of phenolic resin, 0.05-0.5 weight % of curing accelerator, 60-90 weight % of filler, 0.1-2 weight % of modifier, 0.1-1.5 weight % of release agent and 0.1-1 weight % of coupling agent; Wherein, the coupling agent is a combination of a first coupling agent and a second coupling agent, and the weight ratio of the first coupling agent to the second coupling agent is 1:1-6, the first coupling agent is γ-mercaptopropyltrimethoxysilane, and the second coupling agent is at least one of γ-glycidylpropyl ether trimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, γ-aminopropyl triethoxysilane and γ-aminopropyl trimethoxysilane.

2. The high adhesion epoxy molding compound according to claim 1, characterized in that: The coupling agent is a combination of γ-mercaptopropyltrimethoxysilane, γ-glycidylpropyl ether trimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane, and the weight ratio of γ-mercaptopropyltrimethoxysilane, γ-glycidylpropyl ether trimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane is 1:(0.1-3):(0.1-3).

3. The high adhesion epoxy molding compound according to claim 1 or 2, characterized in that: The epoxy resin is selected from at least one of o-cresol epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, polyphenol glycidyl ether epoxy resin, aliphatic glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, biphenyl epoxy resin, dicyclopentadiene epoxy resin, alicyclic epoxy resin and heterocyclic epoxy resin.

4. The high adhesion epoxy molding compound according to claim 1 or 2, characterized in that: The phenolic resin is selected from at least one of phenol linear phenolic resin and its derivatives, cresol linear phenolic resin and its derivatives, monohydroxy or dihydroxy naphthol phenolic resin and its derivatives, condensates of p-xylene and phenol or naphthol, and copolymers of dicyclopentadiene and phenol.

5. The high adhesion epoxy molding compound according to claim 1 or 2, characterized in that: The curing accelerator is selected from at least one of an imidazole compound, a tertiary amine compound and an organic phosphine compound; Preferably, the imidazole compound is selected from at least one of 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-(heptadecanyl)imidazole; Preferably, the tertiary amine compound is selected from at least one of triethylamine benzyldimethylamine, α-methylbenzyldimethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol and 1,8-diazabicyclo[5,4,0]undec-7-ene; Preferably, the organic phosphine compound is at least one selected from triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri(p-methylphenyl)phosphine and tri(nonylphenyl)phosphine.

6. The high adhesion epoxy molding compound according to any one of claims 1 to 5, characterized in that: The filler is selected from at least one of aluminum oxide micropowder, titanium oxide micropowder, silicon nitride micropowder, aluminum nitride micropowder and silicon dioxide micropowder; Preferably, the silica powder is selected from at least one of modified silica, crystalline silica, fused silica and a combination of crystalline silica and fused silica; and / or The release agent is selected from at least one of carnauba wax, synthetic wax and mineral wax; and / or The modifier is liquid silicone oil and / or silicone rubber.

7. The high adhesion epoxy molding compound according to any one of claims 1 to 6, characterized in that: Based on the total weight of the high-adhesion epoxy molding compound, the high-adhesion epoxy molding compound further contains 0.1-10 wt % of a flame retardant and 0.1-3 wt % of a colorant; Preferably, the flame retardant is selected from at least one of a halogen flame retardant, a phosphorus flame retardant, a nitrogen flame retardant, a phosphorus-halogen flame retardant, a phosphorus-nitrogen flame retardant and a hydroxide flame retardant; Preferably, the colorant is selected from at least one of titanium dioxide, zinc oxide, lithopone and carbon black.

8. A method for preparing the high-adhesion epoxy molding compound according to any one of claims 1 to 7, characterized in that: The method comprises: melting and kneading epoxy resin, phenolic resin, curing accelerator, filler, modifier, release agent, coupling agent and optional flame retardant and colorant, and then molding the obtained mixture.

9. The preparation method according to claim 8, characterized in that: The melt mixing conditions include: temperature of 60-110° C., preferably 70-100° C.; time of 3-8 min, preferably 4-7 min.

10. Use of the high-adhesion epoxy molding compound according to any one of claims 1 to 7 in a semiconductor chip packaging process.

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