Low temperature fast curing injection molded epoxy resin composition and method of making same

Abstract

The present application relates to the technical fields of semiconductor packaging injection molding, in particular to a low-temperature fast-curing epoxy resin composition for injection molding and a preparation method thereof, which comprises at least o-cresol formaldehyde epoxy resin, dicyclopentadiene phenol epoxy resin, phenol-aralkyl curing agent, imidazole curing agent, coupling agent, release agent, colorant and silicon dioxide. By optimizing the compound selection of epoxy resin and curing agent, the provided epoxy resin composition has lower packaging injection molding temperature and shorter packaging injection molding time by using o-cresol formaldehyde epoxy resin, dicyclopentadiene phenol epoxy resin, phenol-aralkyl curing agent and imidazole curing agent through low-temperature mixing process, effectively meeting the new demands of the semiconductor packaging industry.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of semiconductor packaging injection molding, in particular to an epoxy resin composition for low-temperature rapid curing injection molding and a preparation method thereof. BACKGROUND

[0002] Semiconductor packaging injection molding is mainly completed in the later stage of semiconductor manufacturing. Semiconductor components and other components are arranged, fixed and connected on a frame or substrate, and terminals are led out and fixed by epoxy encapsulation material to form the overall main structure. The most basic function of packaging is to protect the circuit chip from the influence of the surrounding environment (including physical and chemical effects), and the injection molding temperature is usually 175℃. For some high-temperature-resistant chips or electronic components, it is necessary to reduce the packaging injection molding temperature as much as possible to avoid affecting the high-temperature-resistant chips or electronic components. At the same time, semiconductor packaging factories hope to shorten the time of a single injection molding cycle as much as possible in order to pursue production and work efficiency. Since the traditional injection molding time is generally 120s, a lot of time and energy are wasted. For example, the resin composition for wafer-level packaging sealing disclosed in Chinese Patent Application (Publication No. CN110183818A) has a heat curing temperature of 80-120℃ and a heat curing time of 15 minutes to 45 minutes, which cannot meet the above application requirements. The epoxy resin composition and semiconductor device disclosed in Chinese Patent Application (Publication No. CN107793553A) has an injection molding temperature of 175℃ and a time of 120s, so it cannot simultaneously have a low packaging injection molding temperature and a short packaging injection molding time, and cannot meet the new requirements of the semiconductor packaging industry. SUMMARY

[0003] In order to solve the above problems, the present application provides an epoxy resin composition for low-temperature rapid curing injection molding. By optimizing the compounding selection of epoxy resin and curing agent and using a low-temperature mixing process, the provided epoxy resin composition has a low packaging injection molding temperature and a short packaging injection molding time, effectively meeting the new requirements of the semiconductor packaging industry.

[0004] In one aspect, the present application provides an epoxy resin composition for low-temperature rapid curing injection molding, which at least includes o-cresol formaldehyde epoxy resin, dicyclopentadiene phenol type epoxy resin, phenol-aralkyl type curing agent, imidazole type curing agent, coupling agent, release agent, colorant, and silicon dioxide.

[0005] As a preferred technical solution, the epoxy resin composition comprises, by weight, at least 5-10 parts of o-cresol formaldehyde epoxy resin, 1-3 parts of dicyclopentadiene phenol type epoxy resin, 2-8 parts of phenol-aralkyl type curing agent, 2-8 parts of imidazole type curing agent, 0.1-0.5 parts of coupling agent, 0.3-1 parts of release agent, 0.1-0.5 parts of colorant, and 80-87 parts of silica.

[0006] As a preferred technical solution, the mass ratio of the phenol-aralkyl type curing agent to the imidazole type curing agent is (4-5):(3-4).

[0007] As a preferred technical solution, the epoxy equivalent weight of the o-cresol formaldehyde epoxy resin is 180-220 g / eq, preferably 194-204 g / eq.

[0008] As a preferred technical solution, the epoxy equivalent weight of the dicyclopentadiene phenol type epoxy resin is 250-300 g / eq, preferably 260-280 g / eq.

[0009] As a preferred technical solution, the hydroxyl equivalent weight of the phenol-aralkyl type curing agent is 150-250 g / eq, preferably 168-174 g / eq.

[0010] As a preferred technical solution, the melting point of the imidazole type curing agent is <100℃, preferably <90℃, and further preferably <50℃.

[0011] As a preferred technical solution, the curing time of the epoxy resin composition at 175℃ is ≤20 s.

[0012] As a preferred technical solution, the curing time of the epoxy resin composition at 150℃ is ≤30 s.

[0013] As a preferred technical solution, the curing time of the epoxy resin composition at 100℃ is ≤75 s.

[0014] As a preferred technical solution, the spiral flow length (175℃) of the epoxy resin composition is ≥25 inch.

[0015] As a preferred technical solution, the coupling agent is an amino silane coupling agent, preferably X-12-972F from Shin-Etsu.

[0016] As a preferred technical solution, the release agent is one of natural wax, synthetic wax, fatty acid, and metal salt thereof.

[0017] As a preferred technical solution, the silica is spherical silica, and the particle size of the silica is less than 100 microns; preferably, the maximum particle size of the silica is not more than 80 microns.

[0018] The present application is based on the new requirements of the semiconductor packaging industry for the injection time and temperature of epoxy molding compound, and the epoxy resin composition is designed by optimizing the formula, wherein the o-cresol aldehyde epoxy resin, the dicyclopentadiene phenol type epoxy resin, the phenol-aralkyl type curing agent and the imidazole type curing agent are used to realize low-temperature injection and rapid curing. Especially, the epoxy equivalent weight of the epoxy resin, the hydroxyl equivalent weight of the phenol-aralkyl type curing agent, and the mass ratio of the phenol-aralkyl type curing agent and the imidazole type curing agent are controlled to be (4-5):(3-4), so that the provided epoxy resin composition has a lower curing temperature, a shorter curing time, and a higher bending strength. Further, by introducing 80-87 parts by weight of silica with a maximum particle size of not more than 80 microns, and controlling the mixing temperature of the epoxy resin composition to be 80-100 DEG C, the flowability of the epoxy resin composition is ensured to meet good filling property.

[0019] In another aspect, the present application provides a preparation method of the low-temperature rapid curing injection molding epoxy resin composition. The o-cresol aldehyde epoxy resin, the dicyclopentadiene phenol type epoxy resin, the phenol-aralkyl type curing agent, the imidazole type curing agent, the coupling agent, the release agent, the colorant and the silica are mixed in weight parts, and then sequentially pass through a low-temperature zone, a high-temperature mixing zone and a medium-temperature zone to obtain the epoxy resin composition.

[0020] Preferably, the temperature of the low-temperature zone is 20-30 DEG C, preferably 20-25 DEG C.

[0021] Preferably, the temperature of the high-temperature mixing zone is 80-100 DEG C, preferably 80-85 DEG C.

[0022] Preferably, the temperature of the low-temperature zone is 50-65 DEG C, preferably 60-65 DEG C.

[0023] Advantages

[0024] 1. The present application provides a low-temperature rapid curing injection molding epoxy resin composition, which is prepared by optimizing the compounding and selection of the epoxy resin and the curing agent, and using a low-temperature mixing process, so that the provided epoxy resin composition has a lower packaging injection temperature and a shorter packaging injection time, and effectively meets the new requirements of the semiconductor packaging industry.

[0025] 2. The present application realizes low-temperature injection and rapid curing by using the o-cresol aldehyde epoxy resin, the dicyclopentadiene phenol type epoxy resin, the phenol-aralkyl type curing agent and the imidazole type curing agent.

[0026] 3、The present application provides an epoxy resin composition with low curing temperature, short curing time and high bending strength by controlling the epoxy equivalent weight of the epoxy resin, the hydroxyl equivalent weight of the phenol-aralkyl type curing agent, and the mass ratio of the phenol-aralkyl type curing agent and the imidazole type curing agent being (4-5):(3-4).

[0027] 4、The present application provides an epoxy resin composition with good flowability by introducing 80-87 parts by weight of silica with a maximum particle size of not more than 80 μm and controlling the mixing temperature of the epoxy resin composition to be 80-100°C. DETAILED DESCRIPTION

[0028] Examples 1-6

[0029] Examples 1-6 of the present application provide a low-temperature rapid curing injection molding epoxy resin composition, and the preparation raw materials are shown in Table 1.

[0030] Table 1

[0031]

[0032]

[0033] Examples 1-6 of the present application provide a low-temperature rapid curing injection molding epoxy resin composition, and the preparation raw materials are shown in Table 1.

[0034] Performance test

[0035] 1、According to GB / T 33316-2016, the curing time of the epoxy resin provided by Examples 1-6 is tested, and the test results are shown in Table 2.

[0036] 2、The spiral flow length of the epoxy resin provided by Examples 1-6 at 175°C is tested, and the test results are shown in Table 2.

[0037] 3、According to GB / T 22567-2008, the glass transition temperature of the epoxy resin provided by Examples 1-6 is tested, and the test results are shown in Table 2.

[0038] 4、According to ASTM 790D-17, the bending modulus and bending strength of the epoxy resin provided by Examples 1-6 are tested, and the test results are shown in Table 2.

[0039] 5、According to GB / T40564-2021, the thermal expansion coefficient of the epoxy resin provided in Examples 1-6 was tested, and the test results are shown in Table 2.

[0040] 6、According to GB / T40564-2021, the molding shrinkage of the epoxy resin provided in Examples 1-6 was tested, and the test results are shown in Table 2.

[0041] 7、According to GB / T3139-2005, the thermal conductivity of the epoxy resin provided in Examples 1-6 was tested, and the test results are shown in Table 2.

[0042] Table 2

[0043]

[0044] Note: Example 2 failed to mix, and subsequent tests were not performed.

Claims

1. A low temperature fast curing injection molded epoxy resin composition characterized in that, The low-temperature rapid curing injection molding epoxy resin composition comprises, by weight, at least 5-10 parts of o-cresol aldehyde epoxy resin, 1-3 parts of dicyclopentadiene phenol type epoxy resin, 2-8 parts of phenol-aralkyl type curing agent, 2-8 parts of imidazole type curing agent, 0.1-0.5 parts of coupling agent, 0.3-1 parts of release agent, 0.1-0.5 parts of colorant, and 80-87 parts of silicon dioxide; the mass ratio of the phenol-aralkyl type curing agent to the imidazole type curing agent is (4-5):(3-4); the epoxy equivalent weight of the o-cresol aldehyde epoxy resin is 180-220 g / eq; the epoxy equivalent weight of the dicyclopentadiene phenol type epoxy resin is 250-300 g / eq; and the hydroxyl equivalent weight of the phenol-aralkyl type curing agent is 150-250 g / eq. The preparation method of the low-temperature rapid curing injection molding epoxy resin composition comprises the following steps: mixing, by weight, o-cresol aldehyde epoxy resin, dicyclopentadiene phenol type epoxy resin, phenol-aralkyl type curing agent, imidazole type curing agent, coupling agent, release agent, colorant, and silicon dioxide, and then sequentially passing through a low-temperature zone, a high-temperature mixing zone, and a medium-temperature zone to obtain the epoxy resin composition, wherein the temperature of the high-temperature mixing zone is 80-100 DEG C.

2. The low temperature rapid solidification injection molded epoxy resin composition of claim 1, wherein, The melting point of the imidazole type curing agent is less than 100 DEG C.

3. The low temperature rapid solidification injection molded epoxy resin composition of claim 1, wherein, The epoxy resin composition has at least one of the following properties: A. The curing time of the epoxy resin composition at 175 DEG C. is less than or equal to 20 s; B. The curing time of the epoxy resin composition at 150 DEG C. is less than or equal to 30 s; C. The curing time of the epoxy resin composition at 100 DEG C. is less than or equal to 75 s.

4. The low temperature rapid solidification injection molded epoxy resin composition of claim 1, wherein, The spiral flow length of the epoxy resin composition is greater than or equal to 25 inches.

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