Epoxy resin material and preparation method thereof

Abstract

The present invention relates to the field of epoxy resin compositions, and in particular to a kind of epoxy resin material and preparation method thereof. The epoxy resin material is made of a raw material composition containing an epoxy resin component, a phenolic resin, a solid filler, a promoter, an ion trapping agent, a stress modifier, a coupling agent, a release agent and a colorant, wherein the epoxy resin component contains a structural epoxy resin shown in formula (1), wherein, based on the total weight of the epoxy resin component as 100% by weight, the content of the structural epoxy resin shown in formula (1) is 60 to 100% by weight. The epoxy resin material prepared by the present invention can have lower hygroscopicity and elastic modulus at high temperature while having a higher glass transition temperature, and the moisture sensitivity level can reach MSL-1 level.

Description

Technical Field

[0001] The invention relates to the field of epoxy resin compositions, and in particular to an epoxy resin material and a preparation method thereof. Background Art

[0002] The combination of epoxy resin and phenolic resin is the mainstream packaging material for electronic and electrical equipment today. Epoxy resin as the main resin can undergo a curing reaction with the curing agent under the action of a curing accelerator and high temperature. At the same time, with the addition of inorganic fillers such as silicon dioxide and calcium carbonate, as well as flame retardants and various additives with other properties, electronic and electrical packaging materials that meet specific needs can be prepared. Epoxy resin packaging materials have many beneficial properties and have been widely used in the field of electronic and electrical packaging.

[0003] In recent years, with the continuous development of the semiconductor industry, as the core field of the semiconductor industry, automotive electronic products have also been in rapid development. Therefore, the market requirements for epoxy resin packaging materials are getting higher and higher. From the current demand for automotive electronic products, there are mainly requirements for automotive chips and packaging grades of automotive epoxy resin packaging materials. The packaging grade of automotive epoxy resin packaging materials can be designed mainly by increasing the glass transition temperature (Tg) of epoxy resin packaging materials, reducing its stress, and increasing the bonding strength between packaging materials and frames to meet the requirements of vehicle reliability. Among them, the automotive-grade product assessment requires zero failure, and generally requires epoxy resin packaging materials to reach MSL-1. In addition, if the material Tg is low, it cannot meet the product use requirements. At the same time, if the material has high modulus and hygroscopicity at high temperatures, it is easy to have delamination problems after MSL-1.

[0004] Patent CN109467881A discloses a super heat-resistant and high thermal conductivity epoxy molding compound for semiconductor packaging. The composition can increase the crosslinking density of the resin after curing by using a resin with a multifunctional structure, thereby achieving the effect of increasing the glass transition temperature of the material and increasing the heat resistance of the material. However, the epoxy resin composition prepared by this method has a high modulus due to the increase in the crosslinking density in the cured resin, and the molecular chain segments of the resin are not easy to move at high temperatures; at the same time, the increase in crosslinking density also leads to an increase in free volume, and the hygroscopicity will also increase accordingly.

[0005] Patent CN110104993A discloses a high glass transition temperature epoxy molding compound. Although it mentions that the compound has low hygroscopicity while achieving a higher glass transition temperature, no specific description is given, nor is there any technical method for further reducing the high temperature modulus of the material.

[0006] Therefore, it is necessary to prepare an epoxy resin packaging material with a higher glass transition temperature and lower high-temperature elastic modulus and hygroscopicity to meet the current market demand for packaging materials for automotive electronic products. Summary of the invention

[0007] The technical problem to be solved by the present invention is to provide an epoxy resin material and a preparation method thereof in view of the deficiencies in the prior art. The epoxy resin material has the properties of higher Tg, lower high temperature elastic modulus and low moisture absorption rate, and the moisture sensitivity level can reach MSL-1 level, meeting the reliability requirements.

[0008] The inventors have found through research that by using the epoxy resin of the structure shown in formula (1), due to its rigid structure, the molecular chain segments are not easy to move after the resin is cured, which can greatly increase the glass transition temperature of the resin. At the same time, due to its fewer polar groups and free volume, the moisture absorption rate is also greatly reduced. In addition, the epoxy resin of the structure shown in formula (1) also has a long-chain flexible structure, which has both rigidity and flexibility, and can obtain a lower elastic modulus, especially at high temperatures.

[0009] In order to achieve the above object, the present invention provides an epoxy resin material on one hand, which is made of a raw material composition containing an epoxy resin component, a phenolic resin, a solid filler, an accelerator, an ion capture agent, a stress modifier, a coupling agent, a release agent and a colorant, wherein the epoxy resin component contains a structural epoxy resin represented by formula (1), wherein the content of the structural epoxy resin represented by formula (1) is 60 to 100 weight percent based on the total weight of the epoxy resin component being 100 weight percent,

[0010]

[0011] Preferably, based on the total weight of the raw material composition as 100 weight %, the content of the epoxy resin component is 1 to 20 weight %, the content of the phenolic resin is 1 to 15 weight %, the content of the solid filler is 60 to 90 weight %, the content of the accelerator is 0.01 to 1 weight %, the content of the release agent is 0.1 to 1 weight %, the content of the stress modifier is 0.1 to 1 weight %, the content of the ion capture agent is 0.1 to 1 weight %, the content of the coupling agent is 0.1 to 1 weight %, and the content of the colorant is 0.1 to 1 weight %.

[0012] Preferably, the epoxy resin component further comprises one or more of o-cresol epoxy resin, biphenyl epoxy resin, aralkyl epoxy resin, ester ring epoxy resin, heterocyclic epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, dicyclopentadiene epoxy resin, naphthalene ring epoxy resin and multifunctional epoxy resin. More preferably, the epoxy resin component further comprises one or more of biphenyl epoxy resin, naphthalene ring epoxy resin and o-cresol epoxy resin.

[0013] Preferably, the phenolic resin is selected from one or more of linear phenolic resin, biphenyl phenolic resin, naphthalene phenolic resin, aralkylphenol phenolic resin and multifunctional phenolic resin. More preferably, the phenolic resin is one or more of linear phenolic resin, biphenyl phenolic resin and multifunctional phenolic resin.

[0014] Preferably, the linear phenolic resin is a phenolic resin of the structure shown in formula (2), wherein n=1-20,

[0015]

[0016] Preferably, the multifunctional phenolic resin is a monomer represented by formula (3),

[0017]

[0018] Preferably, the solid filler is silicon dioxide powder. More preferably, the solid filler is crystalline silicon dioxide powder and / or molten silicon dioxide powder. Further preferably, the solid filler is molten silicon dioxide powder. Still further preferably, the median particle size of the solid filler is 15-25 μm.

[0019] Preferably, the accelerator is triphenylphosphine-benzoquinone adduct and / or tetraphenylphosphine salt. More preferably, the accelerator is triphenylphosphine-benzoquinone adduct.

[0020] Preferably, the release agent is carnauba wax and / or oxidized polyethylene wax. More preferably, the release agent is oxidized polyethylene wax.

[0021] Preferably, the stress modifier is selected from one or more of silicone-modified epoxy resin, silicone resin, liquid carboxyl-terminated nitrile rubber and triblock copolymer containing silicone component. More preferably, the stress modifier is silicone-modified epoxy resin and / or liquid carboxyl-terminated nitrile rubber. Further preferably, the stress modifier is silicone-modified epoxy resin.

[0022] Preferably, the coupling agent is selected from one or more of γ-glycidyl ether trimethoxy silane, γ-aminopropyl triethoxy silane, γ-mercaptopropyl trimethoxy silane and γ-glycidyl ether oxypropyl trimethoxy silane; more preferably, γ-glycidyl ether oxypropyl trimethoxy silane.

[0023] Preferably, the ion capture agent is a hydrotalcite compound. More preferably, the ion capture agent is hydrotalcite.

[0024] Preferably, the colorant is carbon black.

[0025] A second aspect of the present invention provides a method for preparing the epoxy resin material described above, the method comprising the following steps:

[0026] (1) heating and melting a phenolic resin, a stress modifier and a release agent, and then cooling and crushing them to obtain an intermediate;

[0027] (2) mixing the intermediate obtained in step (1), an epoxy resin component, a solid filler, an accelerator, a colorant, a coupling agent, an ion capture agent and an optional phenolic resin;

[0028] (3) Extruding and molding the material obtained in step (2) to obtain an epoxy resin material.

[0029] Preferably, in step (1), the heating temperature is 100-150°C.

[0030] Preferably, in step (3), the extrusion conditions include: the extrusion equipment used is a twin-screw extruder, and the extrusion temperature is 85-105°C;

[0031] Preferably, in step (3), the equipment used for forming is a pancake maker.

[0032] Compared with the prior art, the main advantages of the epoxy resin material of the present invention are:

[0033] (1) The use of a new type of epoxy resin with a specific structure greatly improves the glass transition temperature (Tg) of the epoxy resin material (>210°C);

[0034] (2) Due to the special structure of the new epoxy resin, the hygroscopicity of the epoxy resin material (≤0.18%) and the elastic modulus at high temperature (≤0.6GPa) are greatly reduced;

[0035] (3) It has extremely high reliability and meets the requirements of moisture sensitivity level MSL-1. DETAILED DESCRIPTION

[0036] 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.

[0037] 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.

[0038] The present invention provides an epoxy resin material on one hand. The epoxy resin material is made of a raw material composition containing an epoxy resin component, a phenolic resin, a solid filler, an accelerator, an ion capture agent, a stress modifier, a coupling agent, a release agent and a colorant. The epoxy resin component contains a structural epoxy resin represented by formula (1). The content of the structural epoxy resin represented by formula (1) is 60 to 100% by weight, based on the total weight of the epoxy resin component being 100% by weight.

[0039]

[0040] In a specific embodiment, based on the total weight of the epoxy resin component as 100 weight%, the content of the structural epoxy resin represented by formula (1) can be 60 weight%, 65 weight%, 70 weight%, 75 weight%, 80 weight%, 85 weight%, 90 weight%, 95 weight%, or 100 weight%.

[0041] In the epoxy resin material of the present invention, in a specific embodiment, based on the total weight of the raw material composition as 100 weight%, the content of the epoxy resin component can be 1 to 20 weight%, the content of the phenolic resin can be 1 to 15 weight%, the content of the solid filler can be 60 to 90 weight%, the content of the accelerator can be 0.01 to 1 weight%, the content of the release agent can be 0.1 to 1 weight%, the content of the stress modifier can be 0.1 to 1 weight%, the content of the ion capture agent can be 0.1 to 1 weight%, the content of the coupling agent can be 0.1 to 1 weight%, and the content of the colorant can be 0.1 to 1 weight%.

[0042] In the epoxy resin material of the present invention, in a preferred embodiment, based on the total weight of the raw material composition as 100 weight%, the content of the epoxy resin component is 5 to 15 weight%, the content of the phenolic resin is 2 to 10 weight%, the content of the solid filler is 75 to 85 weight%, the content of the accelerator is 0.1 to 0.8 weight%, the content of the release agent is 0.2 to 0.5 weight%, the content of the stress modifier is 0.3 to 0.9 weight%, the content of the ion capture agent is 0.1 to 0.6 weight%, the content of the coupling agent is 0.1 to 0.6 weight%, and the content of the colorant is 0.2 to 0.8 weight%.

[0043] In the epoxy resin material of the present invention, in a specific embodiment, the epoxy resin component may also contain one or more of o-cresol epoxy resin, biphenyl epoxy resin, aralkyl epoxy resin, ester ring epoxy resin, heterocyclic epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, dicyclopentadiene epoxy resin, naphthalene ring epoxy resin and multifunctional epoxy resin. In a preferred embodiment, the epoxy resin component also contains one or more of biphenyl epoxy resin, naphthalene ring epoxy resin and o-cresol epoxy resin.

[0044] In the epoxy resin material of the present invention, in a specific embodiment, the phenolic resin can be one or more of linear phenolic resin, biphenyl phenolic resin, naphthalene phenolic resin, aralkylphenol phenolic resin and multifunctional phenolic resin. In a preferred embodiment, the phenolic resin is one or more of linear phenolic resin, biphenyl phenolic resin and multifunctional phenolic resin. In a more preferred embodiment, the linear phenolic resin is a phenolic resin of the structure shown in formula (2), wherein n=1 to 20, In a further preferred embodiment, the multifunctional phenolic resin is a monomer represented by formula (3),

[0045]

[0046] In the epoxy resin material of the present invention, in a specific embodiment, the solid filler can be silicon dioxide powder. In a preferred embodiment, the solid filler is crystalline silicon dioxide powder and / or molten silicon dioxide powder. In a more preferred embodiment, the solid filler is molten silicon dioxide powder. In a further preferred embodiment, the median particle size of the solid filler is 15-25 μm, for example, 15 μm, 17 μm, 19 μm, 21 μm, 23 μm, 25 μm.

[0047] In the epoxy resin material of the present invention, in a specific embodiment, the accelerator can be triphenylphosphine-benzoquinone adduct and / or tetraphenylphosphine salt. In a preferred embodiment, the accelerator is triphenylphosphine-benzoquinone adduct.

[0048] In the epoxy resin material of the present invention, in a specific embodiment, the release agent can be carnauba wax and / or oxidized polyethylene wax. In a preferred embodiment, the release agent is oxidized polyethylene wax.

[0049] In the epoxy resin material of the present invention, in a specific embodiment, the stress modifier can be one or more of silicone-modified epoxy resin, silicone resin, liquid carboxyl-terminated nitrile rubber and triblock copolymer containing silicone components. In a preferred embodiment, the stress modifier is silicone-modified epoxy resin and / or liquid carboxyl-terminated nitrile rubber. In a more preferred embodiment, the stress modifier is silicone-modified epoxy resin.

[0050] In the epoxy resin material of the present invention, in a specific embodiment, the coupling agent can be one or more of γ-glycidyl ether trimethoxy silane, γ-aminopropyl triethoxy silane, γ-mercaptopropyl trimethoxy silane and γ-glycidyl ether oxypropyl trimethoxy silane. In a preferred embodiment, the coupling agent is γ-glycidyl ether oxypropyl trimethoxy silane.

[0051] In the epoxy resin material of the present invention, in a specific embodiment, the ion capture agent can be a hydrotalcite compound. In a preferred embodiment, the ion capture agent is hydrotalcite.

[0052] In the epoxy resin material of the present invention, in a specific embodiment, the colorant may be carbon black.

[0053] A second aspect of the present invention provides a method for preparing the epoxy resin material described above, the method comprising the following steps:

[0054] (1) heating and melting a phenolic resin, a stress modifier and a release agent, and then cooling and crushing them to obtain an intermediate;

[0055] (2) mixing the intermediate obtained in step (1), an epoxy resin component, a solid filler, an accelerator, a colorant, a coupling agent, an ion capture agent and an optional phenolic resin;

[0056] (3) Extruding and molding the material obtained in step (2) to obtain an epoxy resin material.

[0057] In the method of the present invention, in step (1), the heating temperature may be 100-150° C. In a specific embodiment, for example, it may be 100° C., 110° C., 120° C., 130° C., 140° C., 150° C. In a preferred embodiment, the heating temperature is 130° C.

[0058] In the method of the present invention, in step (3), the extrusion equipment can be selected conventionally in the art. In a preferred embodiment, the extrusion equipment is a twin-screw extruder.

[0059] In the method of the present invention, in step (3), the extrusion temperature may be 85-105° C. In a specific embodiment, for example, it may be 85° C., 90° C., 95° C., 100° C., 105° C. In a preferred embodiment, the extrusion molding temperature is 95° C.

[0060] In the method of the present invention, in step (3), the molding equipment can be selected conventionally in the art. In a preferred embodiment, the molding equipment is a pancake maker.

[0061] The present invention will be described in detail below through examples, but the protection scope of the present invention is not limited thereto.

[0062] In the following examples and comparative examples:

[0063] Epoxy resin with the structure shown in formula (1): purchased from the Institute of Chemistry, Chinese Academy of Sciences, with the brand name FEE-35

[0064]

[0065] o-Cresol epoxy resin: purchased from Jinan Shengquan Group Co., Ltd., brand number SQCN 700-3;

[0066] Naphthalene ring type epoxy resin: purchased from DIC Corporation, brand name HP 4770;

[0067] Biphenyl type epoxy resin: purchased from Mitsubishi Chemical Corporation, brand name YX4000;

[0068] Dicyclopentadiene epoxy resin: purchased from DIC Corporation, brand name HP 7200;

[0069] Linear phenolic resin: purchased from Jinan Shengquan Group Co., Ltd., brand PF 8010;

[0070] Biphenyl phenolic resin: purchased from Meiwa Chemicals Co., Ltd., brand name MEH 7851SS;

[0071] Multifunctional phenolic resin: purchased from Meiwa Chemicals Co., Ltd., brand name MEH 7500;

[0072] Solid filler: fused silica, purchased from Jiangsu Lianrui New Materials Co., Ltd., with a maximum particle size of 75 μm and a median particle size of 15-25 μm;

[0073] Accelerator: triphenylphosphine-1,4-benzoquinone adduct, purchased from Nanjing Lanbian Biochemical Technology Co., Ltd., brand name TPP-BQ;

[0074] Stress modifier: silicone-modified epoxy resin, purchased from Dow Corning, brand SF-8241EG;

[0075] Coupling agent: γ-glycidyloxypropyltrimethoxysilane, purchased from Jiangsu Chenguang Coupling Agent Co., Ltd., brand name KH 560;

[0076] Release agent: oxidized polyethylene wax, purchased from Clariant, brand PED 522;

[0077] Ion scavenger: hydrotalcite, purchased from Kyowa Chemical Industry Co., Ltd., Japan, brand DHT-4C;

[0078] Colorant: Carbon black, purchased from Mitsubishi Chemical Corporation, brand name MA100.

[0079] Example 1

[0080] Example 1 The raw material formula composition for preparing epoxy resin material is shown in Table 1.

[0081] The method for preparing the epoxy resin material in this embodiment is as follows:

[0082] (1) heating and melting a multifunctional phenolic resin, a biphenyl phenolic resin, a release agent, and a stress modifier at 130° C. in proportion, and then cooling and pulverizing to obtain an intermediate;

[0083] (2) stirring and mixing the intermediate obtained in step (1), the epoxy resin having the structure shown in formula (1), the naphthalene ring type epoxy resin, the multifunctional phenolic resin, the solid filler, the colorant, the accelerator, the coupling agent and the ion capture agent in proportion;

[0084] (3) Extruding the material obtained in step (2) through a twin-screw extruder, wherein the temperature of the twin-screw extruder material is controlled at 100° C., crushing the tablets after cooling, and pre-pressing and molding them in a cake press to prepare epoxy resin material.

[0085] Example 2

[0086] Example 2 The raw material formula composition for preparing epoxy resin material is shown in Table 1.

[0087] The method for preparing the epoxy resin material in this embodiment is as follows:

[0088] (1) heating and melting a biphenyl type phenolic resin, a mold release agent, and a stress modifier in proportion at 130° C., and then cooling and crushing to obtain an intermediate;

[0089] (2) stirring and mixing the intermediate obtained in step (1), the epoxy resin having the structure shown in formula (1), o-cresol epoxy resin, linear phenolic resin, solid filler, colorant, accelerator, coupling agent and ion capture agent in proportion;

[0090] (3) Extruding the material obtained in step (2) through a twin-screw extruder, wherein the temperature of the twin-screw extruder material is controlled at 105° C., crushing the tablets after cooling, and pre-pressing them into a cake maker to prepare an epoxy resin material.

[0091] Example 3

[0092] Example 3 The raw material formula composition for preparing epoxy resin material is shown in Table 1.

[0093] The method for preparing the epoxy resin material in this embodiment is as follows:

[0094] (1) heating and melting a linear phenolic resin, a release agent, and a stress modifier in proportion at 130° C., and then cooling and crushing to obtain an intermediate;

[0095] (2) stirring and mixing the intermediate obtained in step (1), the epoxy resin having the structure shown in formula (1), the biphenyl epoxy resin, the multifunctional phenolic resin, the solid filler, the colorant, the accelerator, the coupling agent and the ion capture agent in proportion;

[0096] (3) Extruding the material obtained in step (2) through a twin-screw extruder, wherein the temperature of the twin-screw extruder material is controlled at 100° C., crushing the tablets after cooling, and pre-pressing and molding them in a cake press to prepare epoxy resin material.

[0097] Example 4

[0098] Example 4 The raw material formula composition for preparing epoxy resin material is shown in Table 1.

[0099] The method for preparing the epoxy resin material in this embodiment is as follows:

[0100] (1) heating and melting a biphenyl type phenolic resin, a mold release agent, and a stress modifier in proportion at 130° C., and then cooling and crushing to obtain an intermediate;

[0101] (2) stirring and mixing the intermediate obtained in step (1), the epoxy resin having the structure shown in formula (1), a solid filler, a colorant, an accelerator, a coupling agent and an ion capture agent in proportion;

[0102] (3) Extruding the material obtained in step (2) through a twin-screw extruder, wherein the temperature of the twin-screw extruder material is controlled at 85° C., crushing the tablets after cooling, and pre-pressing them into a cake maker to prepare an epoxy resin material.

[0103] Example 5

[0104] Example 5 The raw material formula composition for preparing epoxy resin material is shown in Table 1.

[0105] The method for preparing the epoxy resin material in this embodiment is as follows:

[0106] (1) heating and melting a linear phenolic resin, a release agent, and a stress modifier in proportion at 130° C., and then cooling and crushing to obtain an intermediate;

[0107] (2) stirring and mixing the intermediate obtained in step (1), the epoxy resin having the structure shown in formula (1), the biphenyl epoxy resin, the solid filler, the colorant, the accelerator, the coupling agent and the ion capture agent in proportion;

[0108] (3) Extruding the material obtained in step (2) through a twin-screw extruder, wherein the temperature of the twin-screw extruder material is controlled at 100° C., crushing the tablets after cooling, and pre-pressing and molding them in a cake press to prepare epoxy resin material.

[0109] Example 6

[0110] Example 6 The raw material formula composition for preparing epoxy resin material is shown in Table 1.

[0111] The method for preparing the epoxy resin material in this embodiment is as follows:

[0112] (1) heating and melting a multifunctional phenolic resin, a mold release agent, and a stress modifier in proportion at 130° C., and then cooling and crushing to obtain an intermediate;

[0113] (2) stirring and mixing the intermediate obtained in step (1), the epoxy resin having the structure shown in formula (1), the naphthalene ring type epoxy resin, the solid filler, the colorant, the accelerator, the coupling agent and the ion capture agent in proportion;

[0114] (3) Extruding the material obtained in step (2) through a twin-screw extruder, wherein the temperature of the twin-screw extruder material is controlled at 100° C., crushing the tablets after cooling, and pre-pressing and molding them in a cake press to prepare epoxy resin material.

[0115] Comparative Example 1

[0116] The epoxy resin material was prepared according to the method of Example 1, except that all the epoxy resins with the structure shown in formula (1) in the formula were replaced by multifunctional epoxy resins to prepare the epoxy resin material.

[0117] Comparative Example 2

[0118] The epoxy resin material was prepared according to the method of Example 2, except that the amount of the epoxy resin with the structure represented by formula (1) in step (1) was reduced from 6.5 g to 4 g to prepare the epoxy resin material.

[0119] Comparative Example 3

[0120] The epoxy resin material was prepared according to the method of Example 4, except that all the epoxy resins with the structure represented by formula (1) were replaced by a combination of dicyclopentadiene epoxy resin and biphenyl epoxy resin to prepare the epoxy resin material.

[0121] Comparative Example 4

[0122] The epoxy resin material was prepared according to the method of Example 4, except that all the epoxy resins with the structure shown in formula (1) were replaced by biphenyl epoxy resins to prepare the epoxy resin material.

[0123] Comparative Example 5

[0124] The epoxy resin material was prepared according to the method of Example 6, except that the epoxy resin with the structure shown in formula (1) was 2.2 g and the naphthalene ring type epoxy resin was 8.8 g.

[0125] Table 1 Raw material formula composition of epoxy resin material of Examples 1-6

[0126]

[0127]

[0128] Test Case

[0129] (1) Glass transition temperature: tested using a thermomechanical analyzer (TMA);

[0130] (2) Gelation time: Heat the hot plate to 175 ± 1 °C, take 2-3 g of sample and place it on the iron plate, stir it continuously with a small needle, and test the time it takes for the sample to change from a fluid to a gel state;

[0131] (3) Fluidity: 20 g of sample was measured using a resin transfer injection molding machine with a spiral flow metal mold, and the injection pressure was 70 kgf / cm 2 , mold temperature is 175±1℃;

[0132] (4) High temperature modulus: The prepared 15 mm × 10 mm × 125 mm bending specimen was tested at 260 °C using a universal material testing machine;

[0133] (5) Hygroscopicity: Tested according to 6.10 of GB / T 40564 using the PCT 24h high pressure cooking method;

[0134] (6) Determination of humidity sensitivity level: The qualified products were baked at 125°C for 24 hours, and then placed in a humidity chamber at 85°C / 85% RH for 168 hours to absorb moisture. They were directly subjected to infrared reflow soldering for 3 times (maximum temperature 260°C), and the product stratification was tested with an ultrasonic scanner.

[0135] The results of testing the gel time, fluidity, glass transition temperature, flexural modulus, hygroscopicity and reliability of the epoxy resin compositions prepared in Examples 1-6 and Comparative Examples 1-5 are shown in Table 2.

[0136] Table 2

[0137]

[0138] It can be seen from the test results of Examples 1-6 and Comparative Examples 1-5 that by comparing the epoxy resin composition prepared by using the epoxy resin containing the structure of formula (1) with the epoxy resin composition not using the epoxy resin containing the structure of formula (1), since the epoxy resin containing the structure of formula (1) has a rigid structure, a long-chain flexible structure, fewer polar groups and free volume, the epoxy resin composition containing the epoxy resin containing the structure of formula (1) can improve the glass transition temperature while having lower hygroscopicity and elastic modulus at high temperature, and the moisture sensitivity level can reach MSL-1 level; by using the epoxy resin containing the structure of formula (1) as 100% by weight, the content of the epoxy resin containing the structure of formula (1) accounts for 60 to 100% by weight of the total epoxy resin content and the epoxy resin containing the structure of formula (1) as 100% by weight. The content of the structural epoxy resin shown in the formula accounts for less than 60% by weight of the total epoxy resin content. The epoxy resin compositions prepared by the two are compared. The epoxy resin composition prepared by the composition containing the structural epoxy resin shown in the formula (1) accounting for 60 to 100% by weight of the total epoxy resin content can increase the glass transition temperature while having lower hygroscopicity and elastic modulus at high temperature, and the moisture sensitivity level can reach MSL-1 level.

[0139] The above are only embodiments of the present invention, and are not intended to limit the patent scope of the present invention. Any equivalent transformations made using the contents of the present invention specification, or directly or indirectly applied in other related technical fields, are also included in the patent protection scope of the present invention.

Claims

1. An epoxy resin material, characterized in that: The epoxy resin material is prepared from a raw material composition containing an epoxy resin component, a phenolic resin, a solid filler, an accelerator, an ion capture agent, a stress modifier, a coupling agent, a release agent and a colorant, wherein the epoxy resin component contains a structural epoxy resin represented by formula (1), wherein the content of the structural epoxy resin represented by formula (1) is greater than or equal to 60% by weight and less than 100% by weight, based on the total weight of the epoxy resin component being 100% by weight, The epoxy resin component further contains a biphenyl type epoxy resin, and / or the phenolic resin contains a biphenyl type phenolic resin; Based on the total weight of the raw material composition as 100 weight percent, the content of the epoxy resin component is 1 to 20 weight percent, the content of the phenolic resin is 1 to 15 weight percent, the content of the solid filler is 60 to 90 weight percent, the content of the accelerator is 0.01 to 1 weight percent, the content of the release agent is 0.1 to 1 weight percent, the content of the stress modifier is 0.1 to 1 weight percent, the content of the ion capture agent is 0.1 to 1 weight percent, the content of the coupling agent is 0.1 to 1 weight percent, and the content of the colorant is 0.1 to 1 weight percent.

2. The epoxy resin material according to claim 1, characterized in that: The epoxy resin component further contains one or more of heterocyclic epoxy resin, dicyclopentadiene epoxy resin, naphthalene ring epoxy resin and multifunctional epoxy resin.

3. The epoxy resin material according to claim 1, characterized in that: The epoxy resin component further contains one or more of aralkyl epoxy resin, o-cresol epoxy resin and ester ring epoxy resin.

4. The epoxy resin material according to claim 1, characterized in that: The epoxy resin component further contains bisphenol A epoxy resin and / or bisphenol F epoxy resin.

5. The epoxy resin material according to claim 1, characterized in that: The phenolic resin also contains a multifunctional phenolic resin.

6. The epoxy resin material according to claim 1, characterized in that: The phenolic resin further comprises at least one of a linear phenolic resin, a naphthyl phenolic resin and an aralkylphenol type phenolic resin.

7. The epoxy resin material according to claim 1, characterized in that: The solid filler is silicon dioxide powder.

8. The epoxy resin material according to claim 7, characterized in that: The solid filler is crystalline silicon dioxide powder and / or fused silicon dioxide powder.

9. The epoxy resin material according to claim 8, characterized in that: The solid filler is fused silica powder.

10. The epoxy resin material according to claim 7, characterized in that: The median particle size of the solid filler is 15-25 μm.

11. The epoxy resin material according to claim 1, characterized in that: The accelerator is triphenylphosphine-benzoquinone adduct and / or tetraphenylphosphine salt.

12. The epoxy resin material according to claim 11, characterized in that: The accelerator is triphenylphosphine-benzoquinone adduct.

13. The epoxy resin material according to claim 1, characterized in that: The release agent is carnauba wax and / or oxidized polyethylene wax.

14. The epoxy resin material according to claim 13, characterized in that: The release agent is oxidized polyethylene wax.

15. The epoxy resin material according to claim 1, characterized in that: The stress modifier is selected from one or more of silicone-modified epoxy resin, silicone resin, liquid carboxyl-terminated nitrile rubber and triblock copolymer containing silicone components.

16. The epoxy resin material according to claim 15, characterized in that: The stress modifier is organic silicon modified epoxy resin and / or liquid carboxyl-terminated nitrile rubber.

17. The epoxy resin material according to claim 16, characterized in that: The stress modifier is an organosilicon-modified epoxy resin.

18. The epoxy resin material according to claim 1, characterized in that: The coupling agent is selected from one or more of γ-glycidyl ether trimethoxy silane, γ-aminopropyl triethoxy silane, γ-mercaptopropyl trimethoxy silane and γ-glycidyl ether oxypropyl trimethoxy silane.

19. The epoxy resin material according to claim 18, characterized in that: The coupling agent is γ-glycidyloxypropyltrimethoxysilane.

20. The epoxy resin material according to claim 1, characterized in that: The ion capture agent is a hydrotalcite compound.

21. The epoxy resin material according to claim 20, characterized in that: The ion capture agent is hydrotalcite.

22. The epoxy resin material according to claim 1, characterized in that: The colorant is carbon black.

23. A method for preparing the epoxy resin material according to any one of claims 1 to 22, characterized in that: The method comprises the following steps: (1) heating and melting a phenolic resin, a stress modifier and a release agent, and then cooling and crushing them to obtain an intermediate; (2) mixing the intermediate obtained in step (1), an epoxy resin component, a solid filler, an accelerator, a colorant, a coupling agent, an ion capture agent and an optional phenolic resin; (3) Extruding and molding the material obtained in step (2) to obtain an epoxy resin material.

24. The method according to claim 23, characterized in that In step (1), the heating temperature is 100-150°C.

25. The method according to claim 23, characterized in that In step (3), the extrusion conditions include: the extrusion equipment used is a twin-screw extruder, and the extrusion temperature is 85-105°C.

26. The method according to claim 23, characterized in that In step (3), the equipment used for forming is a pancake making machine.

Images