Epoxy resin composition as well as preparation method and application thereof

Abstract

The invention relates to the technical field of semiconductor packaging materials, and discloses an epoxy resin composition and a preparation method and application thereof. The epoxy resin composition contains epoxy resin, a curing agent, an accelerant, an inorganic filler, a flame retardant, a release agent, a coupling agent, a modifier and a coloring agent, wherein the epoxy resin is a combination of naphthalene type structure epoxy resin and biphenyl type structure epoxy resin or bisphenol F type structure epoxy resin; the curing agent is a combination of XY-lock type phenolic resin and polyfunctional group type phenolic resin. The epoxy resin composition can pass a test that the comparative tracking index CTI is greater than or equal to 600 while ensuring high reliability and excellent operability, has excellent surface anti-creepage tracking endurance capability under wet and dirty working conditions, and has a wide application prospect in the field of semiconductor packaging.

Description

Technical Field

[0001] This invention relates to the field of semiconductor packaging materials technology, specifically to an epoxy resin composition, its preparation method, and its application. Background Technology

[0002] Epoxy resin compositions used in integrated circuit packaging are thermosetting molding compounds made from epoxy resin as a matrix, compounded with curing agents, fillers, coupling agents, flame retardants, colorants, and release agents, etc., through processes such as mixing, cooling, pulverizing, and preforming. Their core function is to encapsulate core components such as the chip and lead frame after the semiconductor chip has been wire-bonded, using a transfer molding process to form a robust and protective encapsulation shell.

[0003] Insulation is a key performance indicator for this epoxy resin composition. When dust, salt, or other contaminants adhere to the material surface and it is in a humid environment, a conductive film easily forms. Under the influence of an electric field, this conductive film can induce partial discharge, causing carbonization of the material surface and forming permanent conductive channels. This can ultimately lead to insulation failure, short circuits, and even serious safety hazards such as fires. Therefore, for applications with stringent insulation requirements, this epoxy resin composition needs to pass the Comparative Tracking Index (CTI) test to verify its relative tolerance to tracking under humid and contaminated conditions. Summary of the Invention

[0004] The purpose of this invention is to overcome the problem that existing epoxy resin compositions used for integrated circuit packaging have insufficient resistance to surface tracking under humid and dirty conditions. This invention provides an epoxy resin composition, its preparation method, and its applications. This epoxy resin composition, while ensuring high reliability and excellent operability, also demonstrates excellent surface resistance to tracking under humid and dirty conditions, as shown by a Comparative Tracking Index (CTI) test of ≥600. Therefore, it has broad application prospects in the semiconductor packaging field.

[0005] To achieve the above objectives, the present invention provides an epoxy resin composition, wherein, based on the total weight of the epoxy resin composition, the epoxy resin composition contains 3-4.5 wt% epoxy resin, 1-5 wt% curing agent, 0.1-0.5 wt% accelerator, 85-94 wt% inorganic filler, 1-7 wt% flame retardant, 0.01-0.1 wt% mold release agent, 0.1-1 wt% coupling agent, 0.1-1 wt% modifier, and 0.01-0.1 wt% colorant;

[0006] The epoxy resin is a combination of naphthalene-type epoxy resin and biphenyl-type epoxy resin or bisphenol F-type epoxy resin.

[0007] The curing agent is a combination of XY-lock type phenolic resin and multifunctional type phenolic resin.

[0008] Preferably, based on the total weight of the epoxy resin composition, the epoxy resin composition contains 3.2-4 wt% of the epoxy resin, 2-4 wt% of the curing agent, 0.15-0.4 wt% of the accelerator, 86-92 wt% of the inorganic filler, 2-6 wt% of the flame retardant, 0.02-0.08 wt% of the release agent, 0.2-0.8 wt% of the coupling agent, 0.2-0.8 wt% of the modifier, and 0.02-0.08 wt% of the colorant.

[0009] Preferably, the epoxy resin is a combination of biphenyl-type epoxy resin and naphthalene-type epoxy resin, and the mass ratio of the biphenyl-type epoxy resin to the naphthalene-type epoxy resin is 0.5-1.5:1.

[0010] Preferably, the epoxy resin is a combination of bisphenol F type epoxy resin and naphthalene type epoxy resin, and the mass ratio of the bisphenol F type epoxy resin to the naphthalene type epoxy resin is 0.5-1.5:1.

[0011] Preferably, the mass ratio of the XY-lock type phenolic resin to the multifunctional type phenolic resin is 2-4:1.

[0012] Preferably, the accelerator is selected from at least one of 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-ethylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-substituted imidazole and 2-undecylimidazole.

[0013] Preferably, the inorganic filler is selected from at least one of crystalline silica powder, fused angular silica powder, fused spherical silica powder, alumina powder, and magnesium oxide powder, and more preferably fused spherical silica powder.

[0014] Preferably, the flame retardant is a phosphorus-based flame retardant and / or a hydroxide flame retardant.

[0015] Preferably, the colorant is carbon black.

[0016] Preferably, the release agent is selected from at least one of mineral wax, plant wax, polyethylene and polyamide wax.

[0017] Preferably, the modifier is rubber and / or organosilane.

[0018] A second aspect of the present invention provides a method for preparing the above-mentioned epoxy resin composition, the method comprising: mixing the epoxy resin, the curing agent, the accelerator, the inorganic filler, the flame retardant, the release agent, the coupling agent, the modifier and the colorant, then extruding and kneading the resulting mixture, and then cooling and pulverizing it.

[0019] Preferably, the extrusion compounding conditions include: a temperature of 80-130℃ and a time of 5-15 minutes.

[0020] A third aspect of the present invention provides the application of the above-described epoxy resin composition in the packaging process of integrated circuits.

[0021] The epoxy resin composition of this invention contains 3-4.5 wt% epoxy resin, 1-5 wt% curing agent, 0.1-0.5 wt% accelerator, 85-94 wt% inorganic filler, 1-7 wt% flame retardant, 0.01-0.1 wt% release agent, 0.1-1 wt% modifier, and 0.01-0.1 wt% colorant. When the above components are formulated in a suitable ratio, the material can exhibit higher surface adhesion, lower stress, and good release effect. This allows the epoxy resin composition to ensure high reliability and excellent operability, while also demonstrating excellent surface resistance to tracking under humid and dirty conditions, as indicated by a CTI (Comparative Tracking Index) ≥ 600 test. Therefore, it has broad application prospects in the semiconductor packaging field. Detailed Implementation

[0022] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0023] The endpoints and any values ​​of the ranges disclosed herein 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 the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0024] In the epoxy resin composition of the present invention, based on the total weight of the epoxy resin composition, the epoxy resin composition contains 3-4.5 wt% epoxy resin, 1-5 wt% curing agent, 0.1-0.5 wt% accelerator, 85-94 wt% inorganic filler, 1-7 wt% flame retardant, 0.01-0.1 wt% release agent, 0.1-1 wt% coupling agent, 0.1-1 wt% modifier, and 0.01-0.1 wt% colorant.

[0025] In the epoxy resin composition of the present invention, the epoxy resin is a combination of a naphthalene-type epoxy resin and a biphenyl-type epoxy resin or a bisphenol F-type epoxy resin. The structural formulas of the naphthalene-type epoxy resin, the biphenyl-type epoxy resin, and the bisphenol F-type epoxy resin are shown in formulas (I), (II), and (III), respectively. As a specific example, the naphthalene-type epoxy resin can be HP4700, commercially available from DIC Corporation of Japan; the biphenyl-type epoxy resin can be YX4000H, commercially available from JER Chemical Co., Ltd. of Japan; and the bisphenol F-type epoxy resin can be SQE104, commercially available from Shandong Shengquan New Material Co., Ltd.

[0026]

[0027]

[0028] In equation (I), n1 is an integer between 0 and 5.

[0029] In equation (II), n2 is an integer between 0 and 5.

[0030] In some preferred embodiments, the epoxy resin is a combination of a biphenyl-type epoxy resin and a naphthalene-type epoxy resin, and the mass ratio of the biphenyl-type epoxy resin to the naphthalene-type epoxy resin is 0.5-1.5:1, preferably 0.6-1.3:1, and more preferably 0.8-1.2:1. As a specific example, the mass ratio of the biphenyl-type epoxy resin to the naphthalene-type epoxy resin can be 0.8:1, 0.85:1, 0.9:1, 0.95:1, 1:1, 1.1:1, or 1.2:1.

[0031] In some preferred embodiments, the epoxy resin is a combination of bisphenol F type epoxy resin and naphthalene type epoxy resin, and the mass ratio of the bisphenol F type epoxy resin to the naphthalene type epoxy resin is 0.5-1.5:1, preferably 0.6-1.3:1, and more preferably 0.8-1.2:1. As a specific example, the mass ratio of the bisphenol F type epoxy resin to the naphthalene type epoxy resin can be 0.8:1, 0.85:1, 0.9:1, 0.95:1, 1:1, 1.1:1, or 1.2:1.

[0032] In the phenolic resin composition of the present invention, the curing agent is a combination of an XY-lock type phenolic resin and a multifunctional phenolic resin. The structural formulas of the XY-lock type phenolic resin and the multifunctional phenolic resin are shown in Formula (IV) and Formula (V), respectively. As a specific example, the XY-lock type phenolic resin can be MEH7800-4S, commercially available from Meiwa Chemical Co., Ltd.; the multifunctional phenolic resin can be MEH7500, commercially available from Meiwa Chemical Co., Ltd.

[0033]

[0034] In equation (IV), n3 is an integer between 0 and 5.

[0035] In equation (V), n4 is an integer from 1 to 10.

[0036] In some preferred embodiments, the mass ratio of the XY-lock type phenolic resin to the multifunctional phenolic resin is 2-4:1, preferably 2.5-3.5:1, and more preferably 2.8-3.2:1. As specific examples, the mass ratio of the XY-lock type phenolic resin to the multifunctional phenolic resin can be 2.8:1, 2.85:1, 2.9:1, 2.95:1, 3:1, 3.05:1, 3.1:1, 3.15:1, or 3.2:1.

[0037] In this invention, the accelerator generally determines the resin crosslinking structure, reaction process, and conditions. Preferably, the accelerator is selected from at least one of 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-ethylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-substituted imidazole, and 2-undecylimidazole. In a further preferred embodiment, the accelerator is 2-undecylimidazole.

[0038] In this invention, the inorganic filler generally determines the mechanical properties of the material, such as strength, density, thermal conductivity, and water absorption. Preferably, the inorganic filler is selected from at least one of crystalline silica powder, fused angular silica powder, fused spherical silica powder, alumina powder, and magnesium oxide powder. In a further preferred embodiment, the inorganic filler is fused spherical silica powder.

[0039] In this invention, the flame retardant determines the flame retardant rating of the material. Preferably, the flame retardant is a phosphorus-based flame retardant and / or a hydroxide flame retardant. More preferably, the flame retardant is a hydroxide flame retardant.

[0040] In this invention, the release agent ensures smooth demolding and avoids material defects. Preferably, the release agent is selected from at least one of mineral wax, plant wax, polyethylene, and polyamide wax. More preferably, the release agent is a plant wax, such as carnauba wax.

[0041] In this invention, the coupling agent enables better bonding between inorganic fillers and organic materials. Preferably, the coupling agent is γ-glycidoxypropyltrimethoxysilane (KH560) and / or γ-aminopropyltriethoxysilane (KH550).

[0042] In this invention, the modifier can reduce the internal stress of the material. Preferably, the modifier is a rubber and / or an organosilane. More preferably, the modifier is a rubber, for example, a carboxyl-terminated liquid nitrile butadiene rubber (CTBN).

[0043] In this invention, the colorant can impart color properties to the material. Preferably, the colorant is carbon black.

[0044] In some preferred embodiments, based on the total weight of the epoxy resin composition, the epoxy resin composition contains 3.2-4 wt% epoxy resin, 2-4 wt% curing agent, 0.15-0.4 wt% accelerator, 86-92 wt% inorganic filler, 2-6 wt% flame retardant, 0.02-0.08 wt% release agent, 0.2-0.8 wt% coupling agent, 0.2-0.8 wt% modifier, and 0.02-0.08 wt% colorant.

[0045] In a further preferred embodiment, based on the total weight of the epoxy resin composition, the epoxy resin composition contains 3.5-3.9 wt% epoxy resin, 2.5-3 wt% curing agent, 0.2-0.3 wt% accelerator, 87-89 wt% inorganic filler, 3-5 wt% flame retardant, 0.03-0.07 wt% release agent, 0.5-0.7 wt% coupling agent, 0.4-0.6 wt% modifier, and 0.03-0.07 wt% colorant.

[0046] In some embodiments, the coupling agent, colorant, and modifier can be used to treat the material as a whole or individually to treat the filler.

[0047] The oxygen resin composition of this invention, while ensuring high reliability and excellent operability, also demonstrates excellent surface resistance to tracking under humid and dirty conditions, as indicated by a Comparative Tracking Index (CTI) ≥ 600 test. In this invention, the CTI value is the highest voltage (volts) at which the material does not exhibit tracking even after 100 drops of electrolyte.

[0048] The present invention also provides a method for preparing the above-mentioned epoxy resin composition, the method comprising: mixing the epoxy resin, the curing agent, the accelerator, the inorganic filler, the flame retardant, the release agent, the modifier and the colorant, then extruding and kneading the resulting mixture, and then cooling and pulverizing it.

[0049] In some embodiments, the extrusion compounding conditions include: a temperature of 80-130°C, preferably 90-120°C; and a time of 5-15 min, preferably 8-12 min.

[0050] The preparation method of the epoxy resin composition described in this invention includes, but is not limited to, heating and mixing with processing equipment such as a two-roll mill, a single-screw extruder, a twin-screw extruder, a kneader, and a mixer.

[0051] This invention further provides the application of the above-mentioned epoxy resin composition in the packaging process of integrated circuits. Because the epoxy resin composition ensures high reliability and excellent operability, it also demonstrates excellent surface resistance to tracking under humid and contaminated conditions, as indicated by a CTI (Contrast Indicator Index) ≥ 600 test. Based on these performance advantages, this epoxy resin composition can be used as a high-performance packaging material in the encapsulation process of integrated circuits. It can effectively block external moisture and contaminants from corroding the chip and lead frame, significantly reducing the risk of insulation failure and short circuits caused by surface tracking, and improving the long-term reliability of integrated circuit packages.

[0052] The following examples further illustrate the epoxy resin composition, its preparation method, and its application according to the present invention. These examples are implemented based on the technical solution of the present invention, providing detailed implementation methods and specific operating procedures; however, the scope of protection of the present invention is not limited to the following examples.

[0053] Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods in the art. Unless otherwise specified, the experimental materials used in the following embodiments are commercially available.

[0054] In the following embodiments and comparative examples,

[0055] Epoxy resins: biphenyl type A1 (purchased from JER Chemical Co., Ltd., Japan, grade YX4000H), naphthalene type A2 (purchased from DIC Corporation, Japan, grade HP4700), bisphenol F type A3 (purchased from Shandong Shengquan New Material Co., Ltd., grade SQE104).

[0056] Curing agents: linear phenolic resin B1 (purchased from Shandong Shengquan New Material Co., Ltd., brand name PF 8011), XY-lock phenolic resin B2 (purchased from Meiwa Kasei Corporation, brand name MEH7800-4S), and multifunctional phenolic resin B3 (purchased from Meiwa Kasei Corporation, brand name MEH 7500).

[0057] Accelerator: 2-Undecylimidazole C (purchased from Shikoku Chemical Industry Co., Ltd., Japan);

[0058] Inorganic filler: fused spherical silica D (purchased from Jiangsu Lianrui New Materials Co., Ltd.);

[0059] Flame retardant: Aluminum hydroxide E (purchased from Bengbu Zhongheng New Material Technology Co., Ltd.);

[0060] Release agent: Carnauba wax F (Yikeshu (Guangzhou) Technology Co., Ltd.);

[0061] Coupling agents: KH560 G1 (purchased from Jiangsu Chenguang Coupling Agent Co., Ltd.), KH550 G2 (purchased from Jiangsu Chenguang Coupling Agent Co., Ltd.);

[0062] Modifier: CTBN (Dow Chemical, USA);

[0063] Colorant: Carbon black MA600 (Mitsubishi Chemical Corporation).

[0064] Example 1

[0065] Biphenyl-type, naphthalene-type, XY-lock phenolic resin, multifunctional phenolic resin, 2-undecylimidazole, molten spherical silica, aluminum hydroxide, carnauba wax, KH560, KH550, CTBN, and carbon black MA600 were mixed. The mixture was then placed in a twin-screw extruder and extruded and compounded at 100°C for 10 minutes. The resulting material was then cooled and pulverized to obtain the epoxy resin composition. The formulation composition of each raw material is shown in Table 1.

[0066] The formulations (unit: g) of the epoxy resin compositions of Examples 1-5 and Comparative Examples 1-4 are shown in Table 1, wherein the total weight of the epoxy resin compositions is 1000 g.

[0067] Table 1

[0068]

[0069] Test case

[0070] (1) The epoxy resin compositions prepared in the examples and comparative examples of this invention were subjected to CTI testing using the following method, and the results are shown in Table 2. The specific testing process was as follows: two electrodes were placed on the surface of the material, a specific electrolyte (usually ammonium chloride solution) was dripped on, and the voltage was gradually increased until a stable trace was formed on the surface of the material.

[0071] (2) The flexural strength of the epoxy resin compositions prepared in the examples and comparative examples was tested using the method of GB / T 9341-2008. The results are shown in Table 2.

[0072] (3) The adhesive strength of the epoxy resin compositions prepared in the examples and comparative examples was tested using the following method, and the results are shown in Table 2. The specific testing process of this method includes: encapsulating the sample on the substrate of the flip chip at 175°C using a transfer molding process, and after demolding, curing the encapsulated sample at 175°C for 4 hours, and then testing the adhesive strength on a universal testing machine.

[0073] (4) The reliability of the epoxy resin compositions prepared in the examples and comparative examples of this invention is tested using the following method, specifically the MSL3 assessment (humidity sensitivity level 3 assessment), and the results are shown in Table 2. The specific testing process of this method includes: encapsulating the sample on the substrate of a flip chip at 175°C using a transfer molding process; after demolding, curing the encapsulated sample at 175°C for 4 hours, and then assessing it at the MSL-3 level according to the requirements of IPC J-STD-020C-2004 (humidity reflow sensitivity classification of non-hermetic solid surface mount components); and then using an ultrasonic scanning device to scan for delamination.

[0074] Table 2

[0075]

[0076] As can be seen from the results in Table 2, the epoxy resin composition of the present invention, while ensuring high reliability and excellent operability, also has excellent surface resistance to tracking under humid and dirty conditions, as demonstrated by the comparison tracking index (CTI) test of ≥600.

[0077] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. An epoxy resin composition, characterized in that, Based on the total weight of the epoxy resin composition, the epoxy resin composition contains 3-4.5 wt% epoxy resin, 1-5 wt% curing agent, 0.1-0.5 wt% accelerator, 85-94 wt% inorganic filler, 1-7 wt% flame retardant, 0.01-0.1 wt% release agent, 0.1-1 wt% coupling agent, 0.1-1 wt% modifier, and 0.01-0.1 wt% colorant; The epoxy resin is a combination of naphthalene-type epoxy resin and biphenyl-type epoxy resin or bisphenol F-type epoxy resin. The curing agent is a combination of XY-lock type phenolic resin and multifunctional type phenolic resin.

2. The epoxy resin composition according to claim 1, characterized in that, Based on the total weight of the epoxy resin composition, the epoxy resin composition contains 3.2-4 wt% of the epoxy resin, 2-4 wt% of the curing agent, 0.15-0.4 wt% of the accelerator, 86-92 wt% of the inorganic filler, 2-6 wt% of the flame retardant, 0.02-0.08 wt% of the release agent, 0.2-0.8 wt% of the coupling agent, 0.2-0.8 wt% of the modifier, and 0.02-0.08 wt% of the colorant.

3. The epoxy resin composition according to claim 1 or 2, characterized in that, The epoxy resin is a combination of biphenyl-type epoxy resin and naphthalene-type epoxy resin, and the mass ratio of the biphenyl-type epoxy resin to the naphthalene-type epoxy resin is 0.5-1.5:1; and / or The epoxy resin is a combination of bisphenol F type epoxy resin and naphthalene type epoxy resin, and the mass ratio of the bisphenol F type epoxy resin to the naphthalene type epoxy resin is 0.5-1.5:1; and / or The mass ratio of the XY-lock type phenolic resin to the multifunctional type phenolic resin is 2-4:

1.

4. The epoxy resin composition according to claim 1 or 2, characterized in that, The accelerator is selected from at least one of 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-ethylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-substituted imidazole, and 2-undecylimidazole.

5. The epoxy resin composition according to claim 1 or 2, characterized in that, The inorganic filler is selected from at least one of crystalline silica powder, fused angular silica powder, fused spherical silica powder, alumina powder and magnesium oxide powder, preferably fused spherical silica powder.

6. The epoxy resin composition according to claim 1 or 2, characterized in that, The flame retardant is a phosphorus-based flame retardant and / or a hydroxide flame retardant.

7. The epoxy resin composition according to claim 1 or 2, characterized in that, The colorant is carbon black; and / or The release agent is selected from at least one of mineral wax, vegetable wax, polyethylene and polyamide wax; and / or The modifier is rubber and / or organosilane.

8. A method for preparing the epoxy resin composition according to any one of claims 1-7, characterized in that, The method includes: mixing the epoxy resin, the curing agent, the accelerator, the inorganic filler, the flame retardant, the release agent, the coupling agent, the modifier, and the colorant; then extruding and mixing the resulting mixture; and finally cooling and pulverizing it.

9. The method according to claim 8, characterized in that, The extrusion compounding conditions include: a temperature of 80-130℃ and a time of 5-15 minutes.

10. The use of the epoxy resin composition according to any one of claims 1-7 in the packaging process of integrated circuits.

Images