Low-shrinkage epoxy resin composition and application thereof in IPM packaging

Abstract

The invention relates to the technical field of electronic packaging materials, in particular to a low-shrinkage epoxy resin composition and application thereof in IPM packaging. The epoxy resin composition comprises the following raw materials in parts by weight: 3-18 parts of epoxy resin, 1-10 parts of a curing agent, 50-120 parts of inorganic filler and 0.01-3 parts of a catalyst. The epoxy resin of a specific structure, the curing agent and the like are adopted, the shrinkage rate in the forming process can be greatly reduced, and the characteristic is crucial for ensuring the dimensional stability and precision of a final packaged product. By inhibiting shrinkage, deformation or defects caused by non-uniform shrinkage of the material can be effectively avoided, so that the overall quality and reliability of the product are improved, and the use requirements of electronic packaging (especially an IPM module) workpieces are met.

Description

Technical Field

[0001] The invention relates to the technical field of electronic packaging materials, and in particular to a low-shrinkage epoxy resin composition and application thereof in IPM packaging. Background Art

[0002] In recent years, Intelligent Power Module (IPM), as an important component of electronic equipment, has been widely used in smart home, industrial automation, new energy vehicles and other fields. For semi-encapsulated IPM, because its bottom heat sink generally uses a low thermal expansion coefficient DBC (direct copper) ceramic substrate, the shrinkage rate of the epoxy molding compound must match that of the substrate to meet the low warpage requirements of the module. At the same time, with the continuous development of semiconductor technology, the power density of IPM continues to increase, which also puts higher requirements on the temperature resistance of epoxy molding compounds.

[0003] Chinese patent application CN116751548A discloses an epoxy resin composition for module encapsulation, which is easier to obtain lower modulus and stress by matching a monomer epoxy resin or an epoxy resin with low cross-linking density or small steric hindrance with a suitable curing agent and curing accelerator, so that the resin composition maintains ultra-low stress at both high and low temperatures, and does not produce cracking, delamination and other failures. Chinese patent application CN117487309A discloses an epoxy molding compound and its preparation method and application, which obtains good continuous formability by adjusting the content of each component, thereby achieving good high temperature reliability and continuous formability of the epoxy molding compound while being resistant to high temperature and high pressure. However, these prior arts do not solve the problems of shrinkage rate and temperature resistance of epoxy resin at the same time, and epoxy resin cannot match the substrate well, which affects the encapsulation of IPM modules.

[0004] Under such background, there is an urgent need to provide an epoxy resin material with strong dimensional stability and good temperature resistance to meet the use requirements of electronic packaging (especially IPM module) parts. Summary of the invention

[0005] When the current epoxy resin is used in the field of electronic packaging, the shrinkage rate and high temperature resistance of the plastic packaging material cannot meet the use requirements and cannot be well applied to IPM packaging. In order to solve this problem, the first aspect of the present invention provides a low shrinkage epoxy resin composition, and the raw materials of the epoxy resin composition include, by weight, 3-18 parts of epoxy resin, 1-10 parts of curing agent, 50-120 parts of inorganic filler and 0.01-3 parts of catalyst.

[0006] Preferably, the raw materials of the epoxy resin composition include, by weight: 4-14 parts of epoxy resin, 2-9 parts of curing agent, 75-90 parts of inorganic filler and 0.05-1 part of catalyst.

[0007] In some preferred embodiments, the structural formula of the epoxy resin is a combination of one or more compounds shown in the following formula I, formula II, formula III, formula IV, formula V, and formula VI;

[0008] Formula I:

[0009] Formula II:

[0010] Formula III:

[0011] Formula IV:

[0012] Formula V:

[0013] Formula VI:

[0014] Wherein, n in Formula I, Formula III, Formula IV, Formula V and Formula VI is independently selected from 1, 2 or 3.

[0015] More preferably, the epoxy resin comprises at least the compound represented by formula II.

[0016] The present invention uses epoxy resins with specific structures and curing agents to significantly reduce the shrinkage rate during the molding process. This feature is crucial to ensuring the dimensional stability and precision of the final packaged product. By suppressing shrinkage, deformation or defects caused by uneven shrinkage of materials can be effectively avoided, thereby improving the overall quality and reliability of the product. Through experimental research, it was found that the epoxy resin at least includes the compound shown in formula II, which can effectively increase the glass transition temperature Tg of the epoxy resin composition and improve the heat resistance of the epoxy resin composition; and the molding shrinkage rate of the final finished product is reduced, and the dimensional stability is strong. When the epoxy resin of formula II or its combination with other multifunctional epoxy resins is used, the shrinkage rate of the molded part can be reduced to less than 0.1%, meeting the requirements of IPM module processing.

[0017] The compounds represented by Formula I, Formula III, Formula IV, Formula V and Formula VI can all be commercially available, including but not limited to the following sources.

[0018] Formula I: Supplier: Changchun Artificial Resin Factory, product model: CNE-195LL.

[0019] Formula II: Supplier: Nippon Kayaku Co., Ltd., product model WHR-991S.

[0020] Formula III: Supplier: Nippon Kayaku Co., Ltd., product model NC-3000.

[0021] Formula IV: Supplier: DIC Epoxy (Malaysia) Sdn. Bhd., product model: HP-7200.

[0022] Formula V: Supplier: Nippon Kayaku Co., Ltd., product model EPPN-501HY.

[0023] Formula VI: Supplier: Mitsubishi Chemical Corporation, product model: jER YX4000.

[0024] In some preferred embodiments, the curing agent includes a phenolic resin, and the structural formula of the phenolic resin is a combination of one or more compounds shown in the following formula VII, formula VIII, and formula IX;

[0025] Formula VII:

[0026] Formula VIII:

[0027] Formula IX:

[0028] Wherein, n in Formula VII, Formula VIII and Formula IX is independently selected from 1, 2 or 3.

[0029] More preferably, the curing agent comprises a combination of one or more of Formula VII and Formula IX.

[0030] The compounds represented by Formula VII, Formula VIII and Formula IX can all be commercially available, including but not limited to the following sources.

[0031] Formula VII: Supplier: Shandong Shengquan New Materials Co., Ltd., product model PF8011.

[0032] Formula VIII: Supplier: Hunan Jiashengde Material Technology Co., Ltd., product model: BPNH9781S.

[0033] Formula IX: Supplier: Airwater Co., Ltd., product model HE910-09.

[0034] In some preferred embodiments, the inorganic filler includes at least one of silicon dioxide and aluminum oxide.

[0035] Preferably, the silica comprises a combination of one or more of angular silica, spherical silica, fibrous silica, and film-like silica; more preferably, it is angular silica or spherical silica; and further preferably, it is spherical silica.

[0036] Preferably, the silicon dioxide may also include crystalline silicon dioxide, and the crystalline silicon dioxide may be exemplified by α-quartz, β-quartz, tridymite, cristobalite, and the like.

[0037] In order to improve the molding performance of the epoxy resin composition, it is more preferred that the particle size D50 value of the spherical silica is 10-50 μm and the specific surface area is 1-10 m 2 / g.

[0038] More preferably, the maximum particle size of the spherical silica is 60-100 μm, preferably 75 μm.

[0039] Most preferably, the maximum particle size of the spherical silica is 75 μm, the particle size D50 value is 20 μm, and the specific surface area is 2.5 m 2 / g; the spherical silica can be commercially available, for example, Jiangsu Lianrui New Materials Co., Ltd.

[0040] More preferably, the particle size D50 of the spherical silica is 15-30 μm, and the specific surface area is 2-5 m 2 / g.

[0041] In some preferred embodiments, the mass ratio of the epoxy resin to the inorganic filler is (4-14): (78-88).

[0042] In some preferred embodiments, the catalyst comprises a combination of one or more of imidazole compounds, triphenylphosphine, and triphenylphosphine-benzoquinone adducts; more preferably, the catalyst comprises a combination of one or more of triphenylphosphine, and triphenylphosphine-benzoquinone adducts; most preferably, the catalyst comprises triphenylphosphine-benzoquinone adducts.

[0043] In some preferred embodiments, the raw materials of the epoxy resin composition further include, by weight: 0-10 parts of additives, excluding endpoint values; more preferably 0-6 parts.

[0044] The present invention can select the type of additives according to actual needs. The additives can be listed as coupling agents, colorants, release agents, toughening agents, stress modifiers, flame retardants, lubricants, antistatic agents, ultraviolet absorbers, etc.

[0045] Preferably, the additive includes a coupling agent, a colorant, a release agent or a combination of one or more thereof.

[0046] In order to optimize the comprehensive performance of the epoxy resin composition, more preferably, the additives include a coupling agent, a colorant and a release agent in a mass ratio of 1:(1-1.5):(1-1.5).

[0047] Examples of the coupling agent include 3-(glycidyloxypropyl)trimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, and vinyltrimethoxysilane.

[0048] Preferably, the coupling agent includes one or more of 3-(glycidyloxypropyl)trimethoxysilane, 3-mercaptopropyltrimethoxysilane and 3-aminopropyltrimethoxysilane.

[0049] More preferably, the coupling agent includes 3-(glycidyloxypropyl)trimethoxysilane, 3-mercaptopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane in a weight ratio of 1:1:1.

[0050] In some preferred embodiments, the release agent includes at least one of natural wax and synthetic wax; the natural wax can be listed as carnauba wax, candelilla wax, wood wax, beeswax, paraffin wax and its derivatives, etc.; the synthetic wax can be listed as polyethylene wax, polypropylene wax, polyester wax, polyurethane wax, etc.

[0051] More preferably, the release agent is natural wax, and more preferably carnauba wax.

[0052] The colorant may be exemplified by carbon black.

[0053] In some preferred embodiments, the epoxy resin composition satisfies one or more of the following conditions A to D:

[0054] A spiral flow length is 30-45 inches, and the test condition is curing at 175°C for 90 seconds;

[0055] B gelation time is 25-45 seconds, and the test condition is 175°C;

[0056] C molding shrinkage is 0~0.1%;

[0057] D Glass transition temperature Tg (TMA probe method) is 175~200℃.

[0058] More preferably, the epoxy resin composition satisfies conditions A to D simultaneously.

[0059] A second aspect of the present invention provides a method for preparing a low shrinkage epoxy resin composition, the preparation steps of the epoxy resin composition comprising:

[0060] S1. Grind the epoxy resin and curing agent separately, pack and seal them for later use;

[0061] S2. The raw materials except the epoxy resin and the curing agent are mixed, and then the crushed epoxy resin and the curing agent are added to the mixture;

[0062] S3. The material obtained in step S2 is mixed and extruded, and cooled to obtain an epoxy resin composition product.

[0063] In some preferred embodiments, the preparation steps of the epoxy resin composition include:

[0064] S1. Grind the epoxy resin and curing agent separately, seal them separately, and store them at low temperature for later use;

[0065] S2. The inorganic filler, catalyst, and additive are added in batches to a high-speed mixer and mixed, and then the crushed epoxy resin and curing agent are added to the mixture;

[0066] S3. The material obtained in step S2 is transferred to an extruder for mixing and extrusion, and then pulverized after cooling to obtain an epoxy resin composition product.

[0067] Preferably, the product obtained in step S3 is sealed and stored at low temperature; more preferably, the low temperature is below 5°C.

[0068] Preferably, the resin is pulverized in step S1 using a resin pulverizer at an operating temperature of 25°C or below, more preferably 10-20°C, and most preferably 15°C.

[0069] Preferably, the operating temperature of step S2 is below 25°C, more preferably 10-20°C, most preferably 15°C.

[0070] In some embodiments, the extruder comprises a single-screw extruder or a twin-screw extruder; preferably, the extruder is a twin-screw extruder.

[0071] Preferably, the extrusion temperature is 90-120°C, more preferably 95-110°C, most preferably 100°C.

[0072] A third aspect of the present invention provides an application of a low-shrinkage epoxy resin composition, wherein the epoxy resin composition is applied to the field of electronic packaging, and is particularly suitable for IPM packaging.

[0073] Beneficial effects:

[0074] The present invention provides a low shrinkage epoxy resin composition and a preparation method thereof and application in IPM packaging, which has the following advantages:

[0075] (1) The present invention uses epoxy resin with a specific structure and a curing agent to significantly reduce the shrinkage rate during the molding process. This property is crucial to ensuring the dimensional stability and precision of the final packaged product. By suppressing shrinkage, deformation or defects caused by uneven material shrinkage can be effectively avoided, thereby improving the overall quality and reliability of the product.

[0076] (2) It is further preferred that the epoxy resin is an epoxy resin of Formula II or a combination thereof with other multifunctional epoxy resins, which can effectively increase the glass transition temperature Tg of the epoxy resin composition, thereby improving the heat resistance of the epoxy resin composition; and the molding shrinkage of the final product is reduced, and the dimensional stability is strong.

[0077] (4) When the curing agent is preferably a compound represented by formula VII, formula VIII, or formula IX, it can be matched with the new epoxy resin to give the composition suitable cross-linking activity, and can have both strength and stability, giving the epoxy resin composition a strong and stable three-dimensional structure to ensure the dimensional stability and reliability of the molding compound.

[0078] (5) The inorganic filler is preferably spherical silica, the particle size D50 value of the spherical silica is 10-50 μm, and the specific surface area is 1-10 m 2 / g, in order to improve the formability of the epoxy resin composition and ensure that the epoxy resin molding compound has the best performance.

[0079] (6) The present invention adopts an epoxy resin composition with a specific formula, which can effectively improve the comprehensive performance of the epoxy resin composition. The final epoxy resin composition can have a gel time, spiral flow length, molding shrinkage and glass transition temperature that meet the requirements, and meet the processing requirements of downstream parts.

[0080] (7) The shrinkage rate of the epoxy molding compound of the present invention can match that of the substrate to meet the low warpage requirement of the module. The shrinkage rate of the final molded part is reduced to below 0.1%, which is particularly suitable for IPM module processing.

[0081] (8) The preparation method of the present invention is simple, the raw materials are easily available, and the operability is strong. DETAILED DESCRIPTION

[0082] Note: Unless otherwise specified, the raw materials used in the present invention are all commercially available.

[0083] Example

[0084] Examples 1-4

[0085] Examples 1-4 respectively provide a low shrinkage epoxy resin composition, a preparation method thereof, and an application thereof in IPM packaging.

[0086] The formula of the epoxy resin composition is shown in Table 1; the values ​​in Table 1 are the amounts of raw materials added, in parts by weight.

[0087] Table 1 Formula of epoxy resin composition of Examples 1-4

[0088]

[0089]

[0090] Note: / in Table 1 means not added.

[0091] The sources of the raw materials in Table 1 are as follows.

[0092] Formula I: Supplier: Changchun Artificial Resin Factory, product model: CNE-195LL.

[0093] Formula II: Supplier: Nippon Kayaku Co., Ltd., product model WHR-991S.

[0094] Formula VII: Supplier: Shandong Shengquan New Materials Co., Ltd., product model PF8011.

[0095] Formula IX: Supplier: Airwater Co., Ltd., product model HE910-09.

[0096] Spherical silica: maximum particle size is 75μm, particle size D50 value is 20μm, specific surface area is 2.5m 2 / g; Sourced from Jiangsu Lianrui New Materials Co., Ltd.

[0097] Triphenylphosphine-benzoquinone adduct: specifically triphenylphosphine-1,4-benzoquinone adduct, CAS number is 5405-63-0.

[0098] Carnauba wax: Supplier: NIKKO FINE Co., Ltd., product model: Nikko carnauba.

[0099] Carbon black: Supplier: Mitsubishi Chemical Corporation, product model: MA600.

[0100] The preparation steps of the epoxy resin composition include:

[0101] S1. Use a resin crusher to crush the epoxy resin and curing agent separately, and control the operating temperature to 15°C; then pack and seal them, and store them at low temperature for later use;

[0102] S2. The inorganic filler, catalyst, coupling agent, release agent and colorant are added to a high-speed mixer in batches and mixed, and the operating temperature is controlled to 15 ° C; then the crushed epoxy resin and curing agent are added to the mixture;

[0103] S3. The material obtained in step S2 is transferred to a twin-screw extruder, mixed and extruded at 100° C., and crushed after cooling to obtain an epoxy resin composition product, which is stored at low temperature (below 5° C.) for later use.

[0104] Performance Testing Methods

[0105] With reference to the GB / T 40564-2021 method, the gelation time, spiral flow length, molding shrinkage, and glass transition temperature of the epoxy resin compositions prepared in Examples 1-4 were tested. The test results are shown in Table 2.

[0106] The spiral flow length was tested under the conditions of curing at 175°C for 90 seconds, the gel time was tested at 175°C, the molding shrinkage was tested after PMC (Post Mold Cure), and the glass transition temperature Tg was tested using the TMA probe method.

[0107] Performance Test Results

[0108] The test results of the epoxy resin compositions prepared in Examples 1-4 are shown in Table 2.

[0109] Table 2 Performance test results of epoxy resin compositions of Examples 1-4

[0110]

[0111]

[0112] It can be seen from the data in Table 2 that by adding the preferred epoxy resin and curing agent of the present invention, the glass transition temperature Tg of the epoxy resin composition is significantly improved, and the heat resistance is improved; and the molding shrinkage of the final product is reduced, and the dimensional stability is strong. In particular, the combination of the epoxy resin of formula II and other multifunctional epoxy resins can further increase the Tg of the epoxy resin composition, thereby improving the temperature resistance. When the epoxy resin of formula II is not added to the composition, the performance of the product is deteriorated, which is manifested as a slight decrease in the Tg of the epoxy resin composition and a relatively high molding shrinkage of the product. It can be seen from the experimental results that Examples 2, 3, and 4 of the present invention can meet the requirements of IPM module formability and warping, and have high application value.

Claims

1. A low shrinkage epoxy resin composition, characterized in that: In parts by weight, the raw materials of the epoxy resin composition include: 3-18 parts of epoxy resin, 1-10 parts of curing agent, 50-120 parts of inorganic filler and 0.01-3 parts of catalyst.

2. The low shrinkage epoxy resin composition according to claim 1, characterized in that: In parts by weight, the raw materials of the epoxy resin composition further include: 0-10 parts of additives, excluding endpoint values; The additives include one or more combinations of coupling agents, colorants, and release agents.

3. The low shrinkage epoxy resin composition according to claim 1, characterized in that: The structural formula of the epoxy resin is a combination of one or more compounds shown in the following formula I, formula II, formula III, formula IV, formula V, and formula VI; Formula I: Formula II: Formula III: Formula IV: Formula V: Formula VI: Wherein, n in Formula I, Formula III, Formula IV, Formula V and Formula VI is independently selected from 1, 2 or 3.

4. The low shrinkage epoxy resin composition according to claim 3, characterized in that: The curing agent includes a phenolic resin, and the structural formula of the phenolic resin is a combination of one or more compounds shown in the following formula VII, formula VIII, and formula IX; Formula VII: Formula VIII: Formula IX: Wherein, n in Formula VII, Formula VIII and Formula IX is independently selected from 1, 2 or 3.

5. The low shrinkage epoxy resin composition according to claim 1, characterized in that: The inorganic filler includes at least one of silicon dioxide and aluminum oxide; The silica includes one or more of angular silica, spherical silica, fibrous silica, and film-like silica.

6. The low shrinkage epoxy resin composition according to claim 5, characterized in that: The inorganic filler comprises spherical silica, the particle size D50 value of the spherical silica is 10-50 μm, and the specific surface area is 1-10 m 2 / g.

7. The low shrinkage epoxy resin composition according to any one of claims 1 to 6, characterized in that: The epoxy resin composition satisfies one or more of the following conditions A to D: A spiral flow length is 30-45 inches, and the test condition is curing at 175°C for 90 seconds; B gelation time is 25-45 seconds, and the test condition is 175°C; C molding shrinkage is 0~0.1%; D The glass transition temperature is 175~200℃.

8. A method for preparing a low shrinkage epoxy resin composition according to claim 1 or 2, characterized in that: The preparation steps of the epoxy resin composition include: S1. Grind the epoxy resin and curing agent separately, pack and seal them for later use; S2. The raw materials except the epoxy resin and the curing agent are mixed, and then the crushed epoxy resin and the curing agent are added to the mixture; S3. The material obtained in step S2 is mixed and extruded, and cooled to obtain an epoxy resin composition product.

9. The method for preparing the low shrinkage epoxy resin composition according to claim 8, characterized in that: The extrusion temperature is 90-120°C.

10. Use of the low shrinkage epoxy resin composition according to claim 1 or 2, wherein the epoxy resin composition is used in IPM packaging.

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