Epoxy resin molding material for c-mold process and preparation method therefor and use thereof

Abstract

The present invention relates to the technical field of epoxy resin compositions, and specifically relates to an epoxy resin molding material for a C-Mold process and a preparation method therefor and the use thereof. The epoxy resin molding material comprises, in parts by weight, at least the following raw materials: 1-4 parts of a biphenyl epoxy resin, 1-2 parts of a glycidyl amine epoxy resin, 1-2 parts of a naphthalene ring epoxy resin, 3-6 parts of a biphenyl phenolic resin, 85-88 parts of aluminum oxide, 1-3 parts of boron nitride, 0.2-1 parts of silicone, 0.5-3 parts of a compound resin, and 0.5-3 parts of an additive. The compound resin at least comprises one of phenylmethane maleimide, a bisphenol M cyanate ester, and a polyurethane polyol resin. The additive at least comprises a catalyst, a mold release agent, a coupling agent, and a colorant. The epoxy resin molding material has a high fluidity, a low stress, a low expansion coefficient, and a high thermal conductivity, thereby meeting the actual application requirements of the C-Mold process.

Description

Epoxy resin molding compound for C-Mold process and preparation method and application thereof TECHNICAL FIELD

[0001] The present application relates to the technical field of epoxy resin composition, in particular to an epoxy resin molding compound for C-Mold process and preparation method and application thereof. BACKGROUND

[0002] The packaging process of semiconductor chips can be roughly divided into sealing method and molding method. The sealing method is mainly used in a few special fields of equipment, while the molding method using epoxy resin molding compound is mostly used. The molding process includes transfer molding (T-Mold) and compression molding (C-Mold). T-Mold belongs to the early molding packaging process. The epoxy resin molding compound is melted to form a viscous state, and then a certain pressure is applied by a plunger in the mold to make the fluid flow through multiple narrow paths, fill the cavity, and complete the packaging after pressure holding and solidification. C-Mold is a later developed molding packaging process. The epoxy resin molding compound is directly and uniformly placed in the mold, melted, and then the mold is closed to fill the cavity. After pressure holding and solidification, the packaging is completed. With the increase of chip layers and the complexity of wire bonding, it is difficult for the epoxy resin to evenly spread in the T-Mold process, which may cause underfilling or voids or line punching problems, especially to reduce the cost, the size of the printed circuit board (PCB) or lead frame as the carrier is increased, making T-Mold more difficult.

[0003] The C-Mold process can overcome the limitations of the T-Mold process, and higher performance requirements are put forward for epoxy resin molding compounds suitable for the C-Mold process, such as larger package size, thinning of the package, which is easy to cause package warping, and in addition, heat dissipation is also a core problem that needs to be solved for chip packaging, so it is necessary to develop a low-stress, high-thermal-conductivity epoxy resin molding compound for C-Mold. At present, the first consideration for epoxy resin molding compounds suitable for C-Mold is to meet the process requirements and have low stress characteristics, that is, the flowability and low stress of the epoxy resin molding compound are required. In order to improve the heat dissipation of the chip, the better the thermal conductivity of the epoxy resin molding compound, the more conducive to the heat dissipation of the chip. However, if the thermal conductivity of the epoxy resin molding compound is increased, such as increasing the thermal conductivity to more than 3W / (m·K), it is necessary to add inorganic fillers with high thermal conductivity, which may affect the flowability and low stress of the epoxy resin molding compound, etc. For example, a kind of epoxy resin composition for electronic packaging and its preparation method is disclosed in Chinese patent (publication number CN 114685938 A), which introduces spherical aluminum oxide combined with crystalline silicon dioxide to improve the thermal conductivity of the composition. However, with the increase of the content of the thermal conductive filler in the system, the flowability and stress of the product are affected, and the actual application requirements of C-Mold cannot be met. Therefore, it is difficult to make the epoxy resin molding compound simultaneously have high flowability, low stress, low expansion coefficient, and high thermal conductivity to meet the requirements of C-Mold process. SUMMARY

[0004] In order to solve the above problems, the present application provides a kind of epoxy resin molding compound for C-Mold process, through the system of thermal conductive filler, epoxy resin, compound resin and organic silicon, make epoxy resin molding compound simultaneously have high flowability, low stress, low expansion coefficient, high thermal conductivity, meet the actual application requirements of C-Mold process.

[0005] In one aspect, the present application provides an epoxy resin molding compound for C-Mold process, which comprises at least the following raw materials in parts by weight: 1-4 parts of biphenyl type epoxy resin, 1-2 parts of glycidyl amine type epoxy resin, 1-2 parts of naphthalene ring type epoxy resin, 3-6 parts of biphenyl type phenolic resin, 85-88 parts of aluminum oxide, 1-3 parts of boron nitride, 0.2-1 parts of organic silicon, 0.5-3 parts of compound resin, and 0.5-3 parts of additives; the compound resin comprises at least one of phenylmethane maleimide, bisphenol M cyanate, and polyurethane polyol resin; and the additives comprise at least a catalyst, a release agent, a coupling agent, and a colorant.

[0006] As a preferred technical solution, the compound resin is a combination of phenylmethane maleimide, bisphenol M cyanate, and polyurethane polyol resin.

[0007] Preferably, the mass ratio of the phenylmethane maleimide, the bisphenol M cyanate ester, and the polyurethane polyol resin is (0.5-1):(0.5-1):(0.1-0.5).

[0008] The phenylmethane maleimide is of model number BMI-2000 and from Japan DOW CORNING; the bisphenol M cyanate ester is of CAS number 127667-44-1 and from Hubei Comdi Chemical Co., Ltd.; and the polyurethane polyol resin is of model number DR-50 and from Yueyang Dongrun Chemical Co., Ltd.

[0009] As a preferred technical solution, the organic silicon is an organic silicon elastomer and / or an epoxy-modified silicone oil.

[0010] Preferably, the organic silicon is a combination of an organic silicon elastomer and an epoxy-modified silicone oil.

[0011] Preferably, the mass ratio of the organic silicon elastomer and the epoxy-modified silicone oil is (0.1-0.5):(0.1-0.5).

[0012] The organic silicon elastomer is of model number EP-2720 and from Dow Corning, USA; and the epoxy-modified silicone oil is of model number DY-E701 and from Shandong Dayi Chemical Co., Ltd.

[0013] As a preferred technical solution, the additives at least include, by weight, 0.1-0.5 parts of a catalyst, 0.1-0.5 parts of a coupling agent, 0.1-0.5 parts of a colorant, and 0.2-1 parts of a release agent.

[0014] As a preferred technical solution, the epoxy resin molding compound for the C-Mold process at least includes, by weight, 2-3 parts of a biphenyl type epoxy resin, 1-1.5 parts of a glycidyl amine type epoxy resin, 1-1.5 parts of a naphthalene ring type epoxy resin, 3.5-4.5 parts of a biphenyl type phenolic resin, 85.5-87 parts of aluminum oxide, 1-3 parts of boron nitride, 0.2-0.5 parts of organic silicon, 1.5-3 parts of a compounded resin, 0.2-0.4 parts of a catalyst, 0.3-0.5 parts of a coupling agent, 0.2-0.3 parts of a colorant, and 0.2-0.5 parts of a release agent.

[0015] As a preferred technical solution, the mass ratio of the compounded resin to the total mass of the biphenyl type epoxy resin, the glycidyl amine type epoxy resin, and the naphthalene ring type epoxy resin is (1.8-2.5):(4-5), preferably (2-2.5):(4.5-5), and most preferably 2.2:4.8.

[0016] As a preferred technical solution, the biphenyl type epoxy resin is a combination of a crystalline biphenyl type epoxy resin with an epoxy equivalent weight of 180-200 g / eq and a biphenyl phenol type self-retardant epoxy resin with an epoxy equivalent weight of 260-300 g / eq.

[0017] Preferably, the glycidyl amine type epoxy resin is a tetrafunctional glycidyl amine type epoxy resin, and the epoxy equivalent weight of the tetrafunctional glycidyl amine type epoxy resin is 100-120 g / eq.

[0018] Preferably, the naphthalene ring type epoxy resin has an epoxy equivalent weight of 140-204 g / eq.

[0019] As a preferred technical solution, the mass ratio of the crystalline biphenyl type epoxy resin, the biphenyl phenol type self-retardant epoxy resin, the glycidyl amine type epoxy resin, and the naphthalene ring type epoxy resin is (1.1-1.3):(1.1-1.3):(1.1-1.3):(1.1-1.3).

[0020] The model of the crystalline biphenyl type epoxy resin is JX9000H, and the model of the biphenyl phenol type self-retardant epoxy resin is BPNE3501LL, both of which are from Hunan Jia Shengde Material Science and Technology Co., Ltd.; the model of the tetrafunctional glycidyl amine type epoxy resin is XB9721, which is from Guangzhou Yihuisheng Chemical Co., Ltd.; and the model of the naphthalene ring type epoxy resin is HP4700, which is from Dainippon Ink and Chemicals, Inc.

[0021] As a preferred technical solution, the model of the biphenyl type phenolic resin is SH-5075, which is from Shandong Shengquan New Material Co., Ltd.

[0022] As a preferred technical solution, the mass ratio of the aluminum oxide and the boron nitride is (85.5-87):(1-3).

[0023] As a preferred technical solution, the aluminum oxide is spherical aluminum oxide with a model of AX3-32, which is from New Japan Steel.

[0024] As a preferred technical solution, the boron nitride is spherical boron nitride with a model of CFA 50M * , which is from 3M, USA.

[0025] As a preferred technical solution, the catalyst is triphenylphosphine and / or imidazole.

[0026] Preferably, the catalyst is a combination of triphenylphosphine and imidazole, and the mass ratio of the triphenylphosphine and the imidazole is (1.5-3):1.

[0027] As a preferred technical solution, the coupling agent is a silane coupling agent, model KH560, from Xuanhao New Materials.

[0028] As a preferred technical solution, the colorant is carbon black, model MA100, from Mitsubishi, Japan.

[0029] As a preferred technical solution, the release agent is oxidized polyethylene, model PE105, from Qihong Holdings Limited.

[0030] As a preferred technical solution, the C-Mold process uses epoxy resin molding compound with one or more of the following properties:

[0031] a. Spiral flow length, 175℃ > 50 inch;

[0032] b. Viscosity < 15 Pa.s;

[0033] c. 40-80℃ thermal expansion coefficient < 7ppm;

[0034] d. 200-240℃ thermal expansion coefficient < 26ppm;

[0035] e. Molding shrinkage < 0.010%;

[0036] f. Thermal conductivity > 3.5 W / (m·K).

[0037] The application improves the thermal conductivity of the product to more than 3.5 W / (m·K) by optimizing the combination of inorganic fillers, spherical alumina and spherical boron nitride, and further controlling the addition amount of the two inorganic fillers in the epoxy resin molding compound system, and guarantees the heat dissipation of the chip after C-Mold process packaging. Due to the addition of a large amount of spherical alumina in the system, the flowability of the product is reduced, the stress is increased, and the thermal expansion coefficient is higher, which cannot meet the subsequent C-Mold process requirements. The inventor found in the exploration process that by optimizing the epoxy resin system including crystalline biphenyl type epoxy resin, biphenyl phenol type self-retardant epoxy resin, glycidyl amine type epoxy resin, naphthalene ring type epoxy resin, the stress and thermal expansion coefficient of the product can be reduced, but the low stress requirement of the C-Mold process cannot be met. Further, the application introduces a complex resin composed of phenylmethane maleimide, bisphenol M cyanate, and polyurethane polyol resin into the epoxy resin molding compound system, and further controls the mass ratio of the complex resin to the total mass of the biphenyl type epoxy resin, glycidyl amine type epoxy resin, and naphthalene ring type epoxy resin to be (1.8-2.5):(4-5), which effectively reduces the molding shrinkage and thermal expansion coefficient of the product, but the flowability of the product needs to be further improved. Further, the application introduces organic silicone elastomer and epoxy modified silicone oil into the system by optimizing the system and controlling the addition amount, and cooperates with the epoxy resin and the complex resin, so that the provided product has the following properties: spiral flow length, 175℃>50 inch; viscosity <15 Pa.s; 40-80℃ thermal expansion coefficient <7ppm; 200-240℃ thermal expansion coefficient <26ppm; molding shrinkage <0.010%; thermal conductivity >3.5 W / (m·K).

[0038] The application further provides a preparation method of the epoxy resin molding compound for C-Mold process, which at least includes the following steps:

[0039] (1) adding biphenyl type phenolic resin, phenylmethane maleimide and release agent into a heated stirring tank, stirring at 130-160℃ for 20-60min to obtain mixture 1;

[0040] (2) adding biphenyl type epoxy resin, glycidyl amine type epoxy resin, naphthalene ring type epoxy resin, bisphenol M cyanate, polyurethane polyol, alumina, boron nitride, organic silicon, catalyst, coupling agent and colorant into a vertical stainless steel stirring tank, stirring for 20-60min to obtain mixture 2;

[0041] (3) mixing mixture 2 through a double screw extruder, cooling, crushing and then obtaining the epoxy resin molding compound for C-Mold process.

[0042] The application further provides an application of the epoxy resin molding compound for C-Mold process, which is applied to C-Mold process. Beneficial effects

[0043] 1. The present application provides an epoxy resin molding compound for C-Mold process, which has high flowability, low stress, low expansion coefficient, high thermal conductivity by using heat-conducting fillers, epoxy resin, compounded resin and silicone system, and meets the practical application requirements of C-Mold process.

[0044] 2. The present application further controls the addition amount of two kinds of inorganic fillers in the epoxy resin molding compound system by optimizing the combination of spherical aluminum oxide and spherical boron nitride, and increases the thermal conductivity of the product to more than 3.5 W / (m·K), thereby ensuring the heat dissipation of the chip after C-Mold process packaging.

[0045] 3. The present application reduces the stress and thermal expansion coefficient of the product by optimizing the epoxy resin system including crystalline biphenyl type epoxy resin, biphenyl phenol type self-retardant epoxy resin, glycidyl amine type epoxy resin and naphthalene ring type epoxy resin.

[0046] 4. The present application further controls the mass ratio of the compounded resin to the total mass of biphenyl type epoxy resin, glycidyl amine type epoxy resin and naphthalene ring type epoxy resin to be (1.8-2.5):(4-5) by introducing the compounded resin composed of phenyl methane maleimide, bisphenol M cyanate and polyurethane polyol resin into the epoxy resin molding compound system, thereby effectively reducing the molding shrinkage and thermal expansion coefficient of the product, but the flowability of the product needs to be further improved.

[0047] 5. The present application introduces organic silicone elastomer and epoxy modified silicone oil into the system and controls the addition amount, cooperates with epoxy resin and compounded resin, so that the provided product has the following properties: spiral flow length, 175℃> 50 inch; viscosity < 15 Pa.s; 40-80℃ thermal expansion coefficient < 7 ppm; 200-240℃ thermal expansion coefficient < 26 ppm; molding shrinkage < 0.010%; thermal conductivity > 3.5 W / (m·K). DETAILED DESCRIPTION

[0048] In Tables 1 and 2: the phenylmethane maleimide is model BMI-2000, sourced from Daiwa Chemical Co., Ltd., Japan; the CAS number of the bisphenol M cyanate is 127667-44-1, sourced from Hubei Kemaidi Chemical Co., Ltd.; the polyurethane polyol resin is model DR-50, sourced from Yueyang Dongrun Chemical Co., Ltd.; the organosilicon elastomer is model EP-2720, sourced from Dow Corning, USA; the epoxy modified silicone oil is model DY-E701, sourced from Shandong Dayi Chemical Co., Ltd.; and the crystalline biphenyl epoxy resin is model JX9000H, a biphenyl-phenol type. The self-flame-retardant epoxy resin, model BPNE3501LL, is sourced from Hunan Jiashengde Materials Technology Co., Ltd.; the tetrafunctional glycidylamine epoxy resin, model XB9721, is sourced from Guangzhou Yihuisheng Chemical Co., Ltd.; the naphthalene ring epoxy resin, model HP4700, is sourced from Dai Nippon Ink Chemical Co., Ltd.; the biphenyl phenolic resin, model SH-5075, is sourced from Shandong Shengquan New Materials Co., Ltd.; the alumina is spherical alumina, model AX3-32, sourced from Nippon Steel Corporation; and the boron nitride is spherical boron nitride, model CFA 50M. * The silane coupling agent is KH560, sourced from Xuanhao New Materials; the carbon black is MA100, sourced from Mitsubishi, Japan; and the oxidized polyethylene is PE105, sourced from Qihong Holdings Co., Ltd.

[0049] Examples 1-4

[0050] Examples 1-4 of the present invention provide an epoxy resin molding compound for C-Mold process, the formulation of which is shown in Table 1 by weight.

[0051] Table 1

[0052] Embodiments 1-4 of the present invention provide a method for preparing epoxy resin molding compound for C-Mold process, comprising the following steps:

[0053] (1) Add biphenyl phenolic resin, phenylmethane maleimide and oxidized polyethylene to a heated mixing tank and stir at 140°C for 30 min to obtain mixture 1;

[0054] (2) Add biphenyl epoxy resin, glycidyl amine epoxy resin, naphthalene ring epoxy resin, bisphenol M cyanate, polyurethane polyol resin, alumina, boron nitride, organosilicon elastomer, epoxy modified silicone oil, triphenylphosphine, imidazole, silane coupling agent and carbon black into a vertical stainless steel mixing tank and stir for 30 minutes to obtain mixture 2.

[0055] (3) The mixed material 2 is mixed by a double screw extruder, the temperature zones of the first to fourth zones are set to 20℃, 70℃, 110℃ and 70℃ respectively, and the C-Mold process epoxy resin molding compound is obtained after cooling and crushing.

[0056] Comparative Examples 1-7

[0057] The epoxy resin molding compound provided by Comparative Examples 1-7 of the present application has a formula as shown in Table 2.

[0058] Table 2

[0059] Comparative Examples 1-7 of the present application also provide a method for preparing an epoxy resin molding compound, comprising the following steps:

[0060] (1) The biphenyl type phenolic resin, phenyl methane maleimide and oxidized polyethylene are added to a heated stirring tank, and stirred at 140℃ for 30 min to obtain a mixed material 1;

[0061] (2) The biphenyl type epoxy resin, glycidyl amine type epoxy resin, naphthalene ring type epoxy resin, bisphenol M type cyanate, polyurethane polyol tree, aluminum oxide, boron nitride, silicone elastomer, epoxy modified silicone oil, triphenyl phosphine, imidazole, silane coupling agent and carbon black are added to a vertical stainless steel stirring tank and stirred for 30 min to obtain a mixed material 2;

[0062] (3) The mixed material 2 is mixed by a double screw extruder, the temperature zones of the first to fourth zones are set to 20℃, 70℃, 110℃ and 70℃ respectively, and the C-Mold process epoxy resin molding compound is obtained after cooling and crushing.

[0063] Performance test

[0064] The curing time, spiral flow length, viscosity, thermal expansion coefficient, molding shrinkage and thermal conductivity of the epoxy resin molding compounds prepared in Examples 1-4 and Comparative Examples 1-7 are tested according to the national standard GBT 40564-2021, and the results are shown in Table 3.

[0065] Table 3

[0066] As can be seen from the above table, the epoxy resin molding compound provided by Examples 1-4 relative to Comparative Examples 1-7 can simultaneously meet the spiral flow length of 175℃>50 inch, viscosity of <15 Pa.s, 40-80℃ thermal expansion coefficient of <7 ppm, 200-240℃ thermal expansion coefficient of <26 ppm, molding shrinkage of <0.010%, and thermal conductivity of >3.5 W / (m·K).

Claims

1. An epoxy resin molding compound for a C-Mold process, characterized by, At least comprising the following raw materials by weight: biphenyl type epoxy resin 1-4 parts, glycidyl amine type epoxy resin 1-2 parts, naphthalene ring type epoxy resin 1-2 parts, biphenyl type phenolic resin 3-6 parts, aluminum oxide 85-88 parts, boron nitride 1-3 parts, silicone 0.2-1 part, compounded resin 0.5-3 parts, and additive 0.5-3 parts; the compounded resin at least comprises one of phenylmethane maleimide, bisphenol M cyanate, and polyurethane polyol resin; and the additive at least comprises catalyst, release agent, coupling agent, and colorant.

2. An epoxy molding compound for C-Mold process according to claim 1, characterized in that, The compounded resin is a combination of phenylmethane maleimide, bisphenol M cyanate, and polyurethane polyol resin.

3. An epoxy molding compound for C-Mold process according to claim 2, characterized in that, The mass ratio of the phenylmethane maleimide, bisphenol M cyanate, and polyurethane polyol resin is (0.5-1):(0.5-1):(0.1-0.5).

4. An epoxy molding compound for C-Mold process according to claim 1, characterized in that, The silicone is silicone elastomer and / or epoxy-modified silicone oil.

5. An epoxy molding compound for C-Mold process according to claim 4, characterized in that, The mass ratio of the aluminum oxide and boron nitride is (85.5-87):(1-3).

6. An epoxy molding compound for C-Mold process according to claim 2, characterized in that, The ratio of the total mass of the compounded resin, biphenyl type epoxy resin, glycidyl amine type epoxy resin, and naphthalene ring type epoxy resin is (1.8-2.5):(4-5).

7. An epoxy molding compound for C-Mold process according to claim 6, characterized in that, The biphenyl type epoxy resin is a combination of crystalline biphenyl type epoxy resin with an epoxy equivalent weight of 180-200 g / eq and biphenyl phenol type self-retardant epoxy resin with an epoxy equivalent weight of 260-300 g / eq.

8. An epoxy molding compound for C-Mold process according to claim 7, characterized in that, The mass ratio of the crystalline biphenyl type epoxy resin, biphenyl phenol type self-retardant epoxy resin, glycidyl amine type epoxy resin, and naphthalene ring type epoxy resin is (1.1-1.3):(1.1-1.3):(1.1-1.3):(1.1-1.3).

9. A process for the preparation of an epoxy resin molding compound for use in a C-Mold process according to any one of claims 2 to 8, characterized in that, At least comprising the following steps: (1) adding biphenyl type phenolic resin, phenylmethane maleimide, and release agent into a heated stirring tank, stirring at 130-160℃ for 20-60 min to obtain mixture 1; (2) adding biphenyl type epoxy resin, glycidyl amine type epoxy resin, naphthalene ring type epoxy resin, bisphenol M cyanate, polyurethane polyol resin, aluminum oxide, boron nitride, silicone, catalyst, coupling agent, and colorant into a vertical stainless steel stirring tank, stirring for 20-60 min to obtain mixture 2; (3) mixing mixture 2 through a double-screw extruder, cooling, and crushing to obtain C-Mold process epoxy resin molding compound.

10. Use of an epoxy resin molding compound for a C-Mold process according to any one of claims 1 to 8, characterized in that, Applied to C-Mold process.

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