Epoxy resin forming material as well as preparation method and application thereof

Abstract

The invention relates to the technical field of epoxy resin compositions, and discloses an epoxy resin forming material and a preparation method and application thereof. The epoxy resin molding material contains epoxy resin, a curing agent, a filler, an ion capturing agent, a low-stress modifier, a coupling agent, a curing accelerator, a release agent, a flame retardant and a coloring agent, and the coloring agent is black spherical silicon dioxide with a core-shell structure. According to the epoxy resin molding material, on one hand, the insulativity of an epoxy molding compound can be improved, and on the other hand, the layering reliability of a product is improved due to reduction of the elastic modulus.

Description

Technical Field

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

[0002] As semiconductor packaging technology is increasingly moving towards miniaturization, thinness and integration, the products are facing more and more problems. In high-density product packaging, the wiring density increases sharply, resulting in a decrease in wiring spacing. Signal delay, crosstalk, parasitic inductance, etc. will significantly affect the transmission speed and clarity of electrical signals, and higher requirements are placed on the insulation performance of the packaging materials used in conjunction.

[0003] As a packaging material, epoxy resin molding materials are used in large quantities. There are various types of mid- and low-end products packaged on the market. In the field of high-end products, the proportion of epoxy resin molding materials is also increasing. However, epoxy resin molding materials also have many disadvantages, such as the impact of leakage current on signal transmission and the impact of stratification on moisture-sensitive reliability. Epoxy resin molding materials are generally pre-mixed by mixing epoxy resin, curing agent, filler, flame retardant, stress modifier, promoter, colorant and other components, and combined with different molds and packaging processes with chips, welding wires / Bumps, substrates / frames to form functional products. The commonly used colorant in the components is generally carbon black. While meeting the color requirements of the product appearance, due to its conductivity, leakage problems may occur in subsequent applications, such as leakage failure caused by carbon black migration. Summary of the invention

[0004] The purpose of the present invention is to overcome the problems of the prior art that epoxy resin molding materials are prone to leakage and poor delamination performance as packaging materials, and to provide an epoxy resin molding material and a preparation method and application thereof. On the one hand, the epoxy resin molding material can improve the insulation of the epoxy molding compound, and on the other hand, it can improve the product delamination reliability due to the reduced elastic modulus.

[0005] In order to achieve the above-mentioned purpose, the first aspect of the present invention provides an epoxy resin molding material, which contains epoxy resin, curing agent, filler, ion capture agent, low stress modifier, coupling agent, curing accelerator, release agent, flame retardant and colorant, wherein the colorant is black spherical silica with a core-shell structure.

[0006] Preferably, the density of the black spherical silica is 2.05-2.2 g / cm 3 , with a specific surface area of ​​1-2cm 2 / g.

[0007] Preferably, the black spherical silica is prepared according to the following steps: pretreating a spherical organic silicone material, and then sequentially performing a first calcination and a second calcination under an inert atmosphere.

[0008] Preferably, the pretreatment process comprises: immersing the spherical organic silicone material in an unsaturated alcohol under vacuum conditions, and then taking out the solid phase and letting it stand.

[0009] Preferably, the temperature of the second calcination is higher than the temperature of the first calcination.

[0010] Preferably, the difference between the temperature of the second calcination and the temperature of the first calcination is 100-800°C.

[0011] Preferably, the conditions of the first calcination include: a programmed temperature gradient of 1600-2200°C·h and a temperature of 800-1400°C.

[0012] Preferably, the conditions of the second calcination include: a programmed temperature gradient of 3000-6250°C·h and a temperature of 1200-1600°C.

[0013] Preferably, the particle size of the organic silicone material is in the range of 0.5-10 μm.

[0014] Preferably, the organosilicon is polymethylsilicone.

[0015] Preferably, the unsaturated alcohol is isomeric decanol and / or cyclopropanecyclooctyne methanol.

[0016] Preferably, the immersion time is 2-3 hours.

[0017] Preferably, the standing time is 4-6 hours.

[0018] Preferably, based on the total weight of the epoxy resin molding material, the content of the epoxy resin is 2-8wt%, the content of the curing agent is 2-7wt%, the content of the filler is 70-90wt%, the content of the ion capture agent is 0.1-1wt%, the content of the low stress modifier is 0.1-1wt%, the content of the coupling agent is 0.1-1wt%, the content of the curing accelerator is 0.1-1wt%, the content of the release agent is 0.1-2wt%, the content of the flame retardant is 1-10wt%, and the content of the colorant is 0.1-0.9wt%.

[0019] Preferably, the epoxy resin is at least one of o-cresol epoxy resin, biphenyl crystalline epoxy resin, dicyclopentadiene type epoxy resin, phenol biphenyl alkyl type epoxy resin, naphthol aralkyl type epoxy resin, naphthalene ring type epoxy resin, trisphenol methane type multifunctional epoxy resin and tetramethyl bisphenol F type epoxy resin.

[0020] Preferably, the curing agent is at least one of phenol linear phenolic resin, phenol aralkyl resin containing a biphenylene skeleton, trihydroxyphenylmethane type multifunctional phenolic resin and naphthol aralkyl type phenolic resin.

[0021] Preferably, the filler is silicon dioxide powder.

[0022] Preferably, the ion capture agent is at least one of an anion capture agent, a cation capture agent and an anion-cation composite ion capture agent.

[0023] Preferably, the low stress modifier is at least one of polyether-modified polysilicone, silicone block copolymer and carboxyl-terminated nitrile rubber.

[0024] Preferably, the coupling agent is at least one of 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane.

[0025] Preferably, the curing accelerator is at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, triphenylphosphine, triphenylphosphine-benzoquinone adduct and 1,8-diazabicyclo[5.4.0]undec-7-ene.

[0026] Preferably, the release agent is at least one of carnauba wax, montanate wax, polyethylene wax and oxidized polyethylene wax.

[0027] Preferably, the flame retardant is at least one of triphenylphosphine oxide, polyphosphazene, aluminum hydroxide and magnesium hydroxide.

[0028] A second aspect of the present invention provides a method for preparing the above-mentioned epoxy resin molding material, the method comprising the following steps: (1) Mixing and pulverizing epoxy resin, curing agent, filler, ion scavenger, low stress modifier, coupling agent, curing accelerator, release agent, flame retardant and colorant; (2) The mixture obtained in step (1) is melt-kneaded or extruded, and then cooled and pulverized.

[0029] Preferably, the melt-mixing conditions include: temperature of 70-90° C. and time of 7-15 min.

[0030] A third aspect of the present invention provides application of the above-mentioned epoxy resin molding material in semiconductor packaging.

[0031] Through the above technical scheme, the epoxy resin molding material described in the present invention has a higher volume resistivity, exhibits lower leakage, and has better mechanical properties and fluidity, while improving the layered reliability of packaging products in semiconductor packaging. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 This is a transmission electron microscope image of the black spherical silica in Example 1. DETAILED DESCRIPTION

[0033] 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.

[0034] 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.

[0035] The epoxy resin molding material of the present invention contains epoxy resin, curing agent, filler, ion capture agent, low stress modifier, coupling agent, curing accelerator, release agent, flame retardant and colorant, wherein the colorant is black spherical silica with core-shell structure. The epoxy resin molding material of the present invention not only has high volume resistivity and low leakage, but also has low mold opening and 260°C bending modulus.

[0036] In the epoxy resin molding material of the present invention, the density of the black spherical silica can be 2.05-2.2 g / cm 3 , preferably 2.12-2.16 g / cm 3 ; The specific surface area can be 1-2cm 2 / g, preferably 1.1-1.8cm 2 / g. The non-crystalline content of the black spherical silica may be 99.4% or more, preferably 99.4%-99.7%. The hydroxyl content of the black spherical silica may be 120 μg / g or less, preferably 74 μg / g or less, and more preferably 45-74 μg / g.

[0037] In the epoxy resin molding material of the present invention, in order to improve the insulation performance of the epoxy resin molding material and reduce the elastic modulus, the black spherical silica is preferably prepared according to the following steps: pre-treating the spherical organic silicone material, and then sequentially performing a first calcination and a second calcination under an inert atmosphere. The inert atmosphere can be argon and / or nitrogen, preferably nitrogen. In a more preferred case, the purity of the nitrogen is 99.0wt%-99.9wt%.

[0038] In the epoxy resin molding material described in the present invention, the pretreatment process may include: under vacuum conditions, immersing the spherical organic silicone material in an unsaturated alcohol, then removing the solid phase and standing. The immersion conditions include: the temperature can be 20-35°C, preferably 20-30°C; the vacuum degree can be 0.05-0.1MPa, preferably 0.08-0.1MPa; the time can be 2-3h, preferably 2-2.5h. The standing conditions include: the temperature can be 20-35°C, preferably 20-30°C; the time can be 4-6h, preferably 4-5h. The pretreatment can remove excess unsaturated alcohol. In this article, the vacuum degree is atmospheric pressure minus absolute pressure.

[0039] In the epoxy resin molding material of the present invention, the temperature of the second calcination may be higher than the temperature of the first calcination. The difference between the temperature of the second calcination and the temperature of the first calcination may be 100-800°C, preferably 150-800°C, and specifically may be 100°C, 150°C, 200°C, 250°C, 300°C, 350°C, 400°C, 450°C, 500°C, 550°C, 600°C, 650°C, 700°C, 750°C or 800°C.

[0040] In the epoxy resin molding material of the present invention, the first calcination conditions include: the programmed temperature gradient can be 1600-2200°C·h, preferably 1600-1800°C·h; the temperature can be 800-1400°C, preferably 800-900°C. In this article, the programmed temperature gradient is equal to the end temperature of the temperature increase multiplied by the calcination time.

[0041] In the epoxy resin molding material of the present invention, the conditions of the second calcination include: the programmed temperature gradient can be 3000-6250°C·h, preferably 4800-6250°C·h; the temperature can be 1200-1600°C, preferably 1200-1300°C.

[0042] In the epoxy resin molding material of the present invention, the organic silicone is polymethyl silicone. The particle size of the spherical organic silicone material can range from 0.5 to 10 μm, preferably 2 to 8 μm.

[0043] In the epoxy resin molding material of the present invention, the unsaturated alcohol may be isomeric decanol and / or cyclopropanecyclooctyne methanol, preferably cyclopropanecyclooctyne methanol. The mass ratio of the unsaturated alcohol to the spherical organic silicone material may be less than 10%, preferably 5%-10%.

[0044] In the epoxy resin molding material of the present invention, based on the total weight of the epoxy resin molding material, the content of the epoxy resin can be 2-8wt%, preferably 2-7wt%, and more preferably 2-6wt%; the content of the curing agent can be 2-7wt%, preferably 2-6wt%, and more preferably 2-5wt%; the content of the filler can be 70-90wt%, preferably 75-88wt%, and more preferably 80-87wt%; the content of the ion capture agent can be 0.1-1wt%, preferably 0.1-0.8wt%, and more preferably 0.1-0.7wt%; the content of the low stress modifier can be 0.1-1wt%, preferably 0.1-0.8wt% , more preferably 0.2-0.8wt%; the content of the coupling agent can be 0.1-1wt%, preferably 0.1-0.8wt%, more preferably 0.2-0.8wt%; the content of the curing accelerator can be 0.1-1wt%, preferably 0.2-1wt%, more preferably 0.2-0.9wt%; the content of the release agent can be 0.1-2wt%, preferably 0.2-2wt%, more preferably 0.5-2wt%; the content of the flame retardant is 1-10wt%, preferably 1-9wt%, more preferably 2-9wt%; the content of the colorant is 0.1-0.9wt%, preferably 0.1-0.8wt%, more preferably 0.1-0.7wt%.

[0045] In the epoxy resin molding material described in the present invention, the epoxy resin can be at least one of o-cresol epoxy resin, biphenyl crystalline epoxy resin, dicyclopentadiene type epoxy resin, phenol biphenyl alkyl type epoxy resin, naphthol aralkyl type epoxy resin, naphthalene ring type epoxy resin, trisphenol methane type multifunctional epoxy resin and tetramethyl bisphenol F type epoxy resin, preferably at least one of o-cresol epoxy resin, biphenyl crystalline epoxy resin, dicyclopentadiene type epoxy resin, phenol biphenyl alkyl type epoxy resin, naphthol aralkyl type epoxy resin and tetramethyl bisphenol F type epoxy resin, more preferably o-cresol epoxy resin and biphenyl crystalline epoxy resin. In some embodiments, the epoxy resin is o-cresol epoxy resin and biphenyl crystalline epoxy resin, and the mass ratio of o-cresol epoxy resin to biphenyl crystalline epoxy resin is 1:(2-7), for example, 1:2, 1:2.4, 1:3, 1:3.8, 1:4, 1:4.5, 1:5, 1:5.5, 1:6, 1:6.6 or 1:7.

[0046] In the epoxy resin molding material of the present invention, the curing agent is at least one of phenol linear phenolic resin, phenol aralkyl resin containing a biphenylene skeleton, trihydroxyphenylmethane type multifunctional phenolic resin and naphthol aralkyl type phenolic resin, preferably phenol linear phenolic resin and phenol aralkyl resin containing a biphenylene skeleton. In some embodiments, the curing agent is phenol linear phenolic resin and phenol aralkyl resin containing a biphenylene skeleton, and the mass ratio of phenol linear phenolic resin to phenol aralkyl resin containing a biphenylene skeleton is 1: (3-6), specifically, for example, 1: 3, 1: 3.2, 1: 3.5, 1: 4, 1: 4.3, 1: 4.8, 1: 5, 1: 5.6 or 1: 6.

[0047] In the epoxy resin molding material of the present invention, the filler is silica powder. The silica powder may be fused silica powder. The particle size of the silica powder may be 45-180 um, preferably 55-130 um.

[0048] In the epoxy resin molding material of the present invention, the ion capture agent can be at least one of an anion capture agent, a cation capture agent and an anion-cation composite ion capture agent, preferably an anion capture agent. The anion capture agent can be hydrotalcite. The cation capture agent can be IXE100. The anion and cation capture agent can be IXE6107.

[0049] In the epoxy resin molding material of the present invention, the low stress modifier may be at least one of polyether-modified polysilicone, silicone block copolymer and carboxyl-terminated nitrile rubber, preferably polyether-modified polysiloxane.

[0050] In the epoxy resin molding material of the present invention, the coupling agent may be at least one of 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane, preferably 3-mercaptopropyltrimethoxysilane.

[0051] In the epoxy resin molding material described in the present invention, the curing accelerator can be at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, triphenylphosphine, triphenylphosphine-benzoquinone adduct and 1,8-diazabicyclo[5.4.0]undec-7-ene, preferably triphenylphosphine and / or triphenylphosphine-benzoquinone adduct, more preferably triphenylphosphine.

[0052] In the epoxy resin molding material of the present invention, the release agent may be at least one of carnauba wax, montanate wax, polyethylene wax and oxidized polyethylene wax, preferably oxidized polyethylene wax (OP wax). In a preferred embodiment, the release agent is oxidized polyethylene wax (OP wax) and carnauba wax, and the mass ratio of oxidized polyethylene wax (OP wax) to carnauba wax is 1:(0-0.75). The mass ratio of oxidized polyethylene wax (OP wax) to carnauba wax may be 1:0.2, 1:0.33, 1:0.5, 1:0.66 or 1:0.75.

[0053] In the epoxy resin molding material of the present invention, the flame retardant may be at least one of triphenylphosphine oxide, polyphosphazene, aluminum hydroxide and magnesium hydroxide, preferably at least one of triphenylphosphine oxide, polyphosphazene and aluminum hydroxide, more preferably triphenylphosphine oxide.

[0054] In some embodiments, the epoxy resin molding material of the present invention contains epoxy resin, curing agent, filler, ion capture agent, low stress modifier, coupling agent, curing accelerator, release agent, flame retardant and colorant, wherein, based on the total weight of the epoxy resin molding material, the content of the epoxy resin is 2-8wt%, the content of the curing agent is 2-7wt%, the content of the filler is 70-90wt%, the content of the ion capture agent is 0.1-1wt%, the content of the low stress modifier is 0.1-1wt%, the content of the coupling agent is 0.1-1wt%, and the content of the The content of the curing accelerator is 0.1-1wt%, the content of the release agent is 0.1-2wt%, the content of the flame retardant is 1-10wt%, and the content of the colorant is 0.1-0.9wt%; the epoxy resin is at least one of o-cresol epoxy resin, biphenyl crystalline epoxy resin, dicyclopentadiene epoxy resin, phenol biphenyl alkyl epoxy resin, naphthol aralkyl epoxy resin, naphthalene ring epoxy resin, trisphenol methane multifunctional epoxy resin, and tetramethyl bisphenol F epoxy resin; the curing agent is phenol linear phenolic resin, phenol aralkyl resin containing a biphenyl skeleton, trihydroxy At least one of phenylmethane type multifunctional phenolic resin and naphthol aralkyl type phenolic resin; the filler is silicon dioxide powder; the ion capture agent is at least one of anion capture agent, cation capture agent and anion-cation composite ion capture agent; the low stress modifier is at least one of polyether modified polysilicon, silicone block copolymer and terminal carboxyl nitrile rubber; the coupling agent is at least one of 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane; the curing accelerator is 2- At least one of methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, triphenylphosphine, triphenylphosphine-p-benzoquinone adduct and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU); the release agent is at least one of carnauba wax, montanate wax, polyethylene wax and oxidized polyethylene wax; the flame retardant is at least one of triphenylphosphine oxide, polyphosphazene, aluminum hydroxide and magnesium hydroxide; the colorant is black spherical silica with a core-shell structure, and the density of the black spherical silica is 2.05-2.2 g / cm 3 , with a specific surface area of ​​1-2cm 2 / g, the black spherical silica is prepared according to the following steps: under the conditions of vacuum degree of 0.05-0.1MPa and temperature of 20-35°C, immersing the spherical organic silicone material in unsaturated alcohol for 2-3h, then taking out the solid phase and standing it at a temperature of 20-35°C for 4-6h, then under an inert atmosphere, heating to 800-1400°C with a programmed temperature gradient of 1600-2200°C·h for calcining for 1.5-2.5h, and then heating to 1200-1600°C with a programmed temperature gradient of 3000-6250°C·h for calcining for 2.5-5h; the organic silicone is polymethyl silicone; and the unsaturated alcohol is isomeric decanol and / or cyclopropanecyclooctyne methanol.

[0055] The present invention also provides a method for preparing the above-mentioned epoxy resin molding material, the method comprising the following steps: (1) Mixing and pulverizing epoxy resin, curing agent, filler, ion scavenger, low stress modifier, coupling agent, curing accelerator, release agent, flame retardant and colorant; (2) The mixture obtained in step (1) is melt-kneaded or extruded, and then cooled and pulverized.

[0056] According to the method of the present invention, by using black spherical silica with a core-shell structure as a colorant, the epoxy resin molding material prepared has a higher volume resistivity, exhibits lower leakage, and has better mechanical properties and fluidity.

[0057] In the method of the present invention, the melt mixing conditions include: the temperature can be 70-90°C, preferably 80-90°C; the time can be 7-15 minutes, preferably 10-15 minutes. The melt mixing can be carried out in a twin-roll mixer or an extruder.

[0058] In the method of the present invention, the method may further include: forming a cake from the mixture obtained in step (2).

[0059] In some embodiments, the method for preparing the epoxy resin molding material of the present invention comprises the following steps: (1) Under the conditions of a vacuum degree of 0.05-0.1 MPa and a temperature of 20-35° C., the spherical organic silicone material is immersed in an unsaturated alcohol for 2-3 hours, then the solid phase is taken out and allowed to stand at a temperature of 20-35° C. for 4-6 hours, then the temperature is raised to 800-1400° C. for calcination for 1.5-2.5 hours at a programmed temperature gradient of 1600-2200° C.·h under an inert atmosphere, and then the temperature is raised to 1200-1600° C. for calcination for 2.5-5 hours at a programmed temperature gradient of 3000-6250° C.·h to obtain black spherical silica; (2) Mixing epoxy resin, curing agent, filler, ion scavenger, low stress modifier, coupling agent, curing accelerator, release agent, flame retardant and the black spherical silica obtained in step (1) and crushing them; melt-kneading the obtained mixture at 70-90° C. for 7-15 min or extruding, cooling and crushing, and then forming into cakes.

[0060] The present invention also provides the application of the epoxy resin molding material in semiconductor packaging. According to the application of the present invention, the epoxy resin molding material of the present invention improves the layer reliability of the packaging product in semiconductor packaging.

[0061] The following examples further illustrate the epoxy resin molding material and its preparation method and application of the present invention. The examples are implemented based on the technical solution of the present invention, and provide detailed implementation methods and specific operation processes, but the protection scope of the present invention is not limited to the following examples.

[0062] The experimental methods in the following examples, unless otherwise specified, are all conventional methods in the art. The experimental materials used in the following examples, unless otherwise specified, are all commercially available.

[0063] In the following examples and comparative examples: Polymethylsilicone was purchased from Zhejiang Hangyu Technology Co., Ltd. with a brand name of HY-7000 and a particle size of 0.5-10 μm.

[0064] Epoxy resin: o-cresol epoxy resin was purchased from Shandong Shengquan Group with the brand name SQCN700-1.3; biphenyl crystalline epoxy resin was purchased from Shandong Shengquan Group with the brand name SQE-101; dicyclopentadiene type epoxy resin was purchased from Japan DIC with the brand name HP-7200; phenol biphenyl alkyl type epoxy resin was purchased from Japan Chemical Industry with the brand name NC-3000; naphthol aralkyl type epoxy resin was purchased from Japan Nippon Steel with the brand name ESN-175S; naphthalene ring type epoxy resin was purchased from Japan DIC with the brand name HP-4770; trisphenol methane type multifunctional epoxy resin was purchased from Japan Mitsubishi Chemical with the brand name E1032H60; tetramethyl bisphenol F type epoxy resin was purchased from Japan Nippon Steel with the brand name YSLV-80XY.

[0065] Curing agent: phenol linear phenolic resin was purchased from Shandong Shengquan Group with the brand name PF-8011; phenol aralkyl resin containing a biphenylene skeleton was purchased from Japan Meiwa Chemical with the brand name MEH-7851SS; trihydroxyphenylmethane type multifunctional phenolic resin was purchased from Japan Meiwa Chemical with the brand name MEH-7500; naphthol aralkyl type phenolic resin was purchased from Japan Nippon Steel with the brand name SN-475.

[0066] Filler: Fused silica powder was purchased from Jiangsu Lianrui New Materials Co., Ltd. with a brand name of NQ101 and a particle size of 75 μm.

[0067] Ion scavenger: hydrotalcite was purchased from Kyoto Chemical Industry Co., Ltd., Japan, with the brand name DHT-4A; IXE100 was purchased from Toagosei Co., Ltd.; and IXE6107 was purchased from Toagosei Co., Ltd.

[0068] Low stress modifier: carboxyl-terminated nitrile rubber was purchased from Huntsman, USA, with the brand name CTBN 1300*13; polyether-modified polysilicone was purchased from Dow Corning, with the brand name SF8421EG; and silicone block copolymer was purchased from Wacker, Germany, with the brand name GENIOPERLW35.

[0069] Coupling agent: 3-glycidyloxypropyltrimethoxysilane was purchased from Shin-Etsu of Japan with the brand name KBM-403; 3-aminopropyltriethoxysilane was purchased from Dow Corning with the brand name Z-6011; 3-mercaptopropyltrimethoxysilane was purchased from Shin-Etsu of Japan with the brand name KBM-803; N-phenyl-3-aminopropyltrimethoxysilane was purchased from Shin-Etsu of Japan with the brand name KBM-573.

[0070] Curing accelerator: commercially available.

[0071] Flame retardant: triphenylphosphine oxide, commercially available; polyphosphazene purchased from Otsuka Chemical of Japan, brand name SPB-100; aluminum hydroxide purchased from Albemarle of the United States, brand name OL-104LEO; magnesium hydroxide purchased from Albemarle of the United States, brand name H5IV.

[0072] Release agent: OP wax was purchased from Clariant with the brand name PED522; polyethylene wax was purchased from Klein with the brand name PE520.

[0073] Examples 1-11 and comparative examples all prepared epoxy resin molding materials according to the following method: (1) Under the conditions of vacuum degree of 0.08 MPa and temperature of 25°C, 30 kg of polymethyl silicone was immersed in 3 kg of cyclopropanecyclooctyne methanol for 2 h, then the solid phase was taken out and allowed to stand at 25°C for 4 h, then calcined at a starting temperature of 25°C with a programmed temperature increase gradient of 1600°C·h to 800°C for 2 h in a nitrogen atmosphere, and then calcined at a programmed temperature increase gradient of 4800°C·h to 1200°C for 4 h to obtain black spherical silica (density 2.16 g / cm 3 , with a specific surface area of ​​1.64 cm 2 / g, hydroxyl content is 45μg / g, and non-crystalline content is 99.4%); (2) Biphenyl crystalline epoxy resin, o-cresol epoxy resin, phenol linear phenolic resin, phenol aralkyl resin containing a biphenylene skeleton, fused silica powder, OP wax, carnauba wax, polyether modified polysiloxane, 3-mercaptopropyltrimethoxysilane, triphenylphosphine, triphenylphosphine oxide, hydrotalcite and the black spherical silica obtained in step (1) are mixed and pulverized; the obtained mixture is melt-kneaded at 80° C. for 10 minutes by a double-roll mixer, and then cooled and pulverized.

[0074] The compositions of the epoxy resin molding materials of Examples 1-11 are shown in Table 1.

[0075] Table 1

[0076] Example 12 (1) Under the conditions of vacuum degree of 0.5 MPa and temperature of 20°C, 110 kg of polymethyl silicone was immersed in 11 kg of isodecanol for 3 h. Then, the solid phase was taken out and allowed to stand at 20°C for 6 h. Then, in a nitrogen atmosphere, the starting temperature was 20°C, the temperature was raised from 2100°C·h to 1400°C for 1.5 h, and then the temperature was raised from 6200°C·h to 1550°C for 4 h to obtain black spherical silica (density 2.13 g / cm 3 , with a specific surface area of ​​1.82cm 2 / g, hydroxyl content is 55μg / g, and non-crystalline content is 99.6%); (2) 2.4 parts by weight of dicyclopentadiene epoxy resin, 1.0 parts by weight of o-cresol epoxy resin, 2.5 parts by weight of phenol aralkyl resin containing a biphenylene skeleton, 0.5 parts by weight of phenol linear novolac resin, 80 parts by weight of fused silica powder, 0.35 parts by weight of montanate wax, 0.8 parts by weight of silicone block copolymer, 0.3 parts by weight of 3-aminopropyltriethoxysilane, 0.21 parts by weight of triphenylphosphine p-benzoquinone adduct, 5.0 parts by weight of triphenylphosphine oxide, 0.2 parts by weight of hydrotalcite and 0.3 parts by weight of black spherical silica obtained in step (1) are mixed and pulverized; the obtained mixture is melt-kneaded at 70° C. for 15 minutes by a double-roll mixer, then cooled and pulverized.

[0077] Embodiment 13 (1) Under the conditions of vacuum degree of 0.07 MPa and temperature of 30°C, 110 kg of polymethyl silicone was immersed in 11 kg of cyclopropanecyclooctyne methanol for 2 h, then the solid phase was taken out and allowed to stand at 30°C for 4 h, then calcined at a starting temperature of 30°C with a temperature program of 2200°C·h to 880°C for 2.5 h in a nitrogen atmosphere, and then calcined at a temperature program of 6250°C·h to 1250°C for 5 h to obtain black spherical silica (density 2.15 g / cm 3 , with a specific surface area of ​​1.79 cm 2 / g, hydroxyl content is 72μg / g, and non-crystalline content is 99.6%); (2) 2.4 parts by weight of phenol biphenyl alkyl type epoxy resin, 1.0 part by weight of o-cresol epoxy resin, 2.5 parts by weight of p-trihydroxyphenylmethane type multifunctional phenolic resin, 0.5 parts by weight of phenol linear phenolic resin, 80 parts by weight of fused silica powder, 0.35 parts by weight of carnauba wax, 0.8 parts by weight of terminal carboxyl nitrile rubber, 0.3 parts by weight of N-phenyl-3-aminopropyltrimethoxysilane, 0.21 parts by weight of 2-methylimidazole, 5.0 parts by weight of aluminum hydroxide flame retardant, 0.2 parts by weight of hydrotalcite and 0.3 parts by weight of black spherical silica obtained in step (1) are mixed and pulverized; the obtained mixture is melt-kneaded at 90° C. for 7 minutes by a double-roll mixer, then cooled and pulverized.

[0078] Embodiment 14 (1) Under the conditions of vacuum degree of 0.08 MPa and temperature of 35°C, 60 kg of polymethyl silicone was immersed in 6 kg of isodecanol for 2 h. Then, the solid phase was taken out and allowed to stand at 35°C for 4 h. Then, in a nitrogen atmosphere, the starting temperature was 35°C and the temperature was raised from 1600°C / h to 800°C for 2 h. Then, the temperature was raised from 3000°C / h to 1200°C for 2.5 h to obtain black spherical silica (density 2.14 g / cm 3 , with a specific surface area of ​​1.72cm 2 / g, hydroxyl content is 74μg / g, and non-crystalline content is 99.7%); (2) 2.4 parts by weight of naphthol aralkyl epoxy resin, 1.0 part by weight of o-cresol epoxy resin, 2.5 parts by weight of naphthol aralkyl phenolic resin, 0.5 parts by weight of phenol linear phenolic resin, 80 parts by weight of fused silica powder, 0.35 parts by weight of polyethylene wax, 0.8 parts by weight of polyether modified polysilicone, 0.3 parts by weight of 3-glycidyloxypropyltrimethoxysilane, 0.21 parts by weight of 2-ethyl-4-methylimidazole, 5.0 parts by weight of polyphosphazene, 0.2 parts by weight of IXE100 and 0.3 parts by weight of black spherical silica obtained in step (1) are mixed and pulverized; the obtained mixture is melt-kneaded at 70° C. for 15 minutes by a double-roll mixer, then cooled and pulverized.

[0079] Embodiment 15 (1) Under the conditions of vacuum degree of 0.10 MPa and temperature of 25°C, 100 kg of polymethyl silicone was immersed in 10 kg of cyclopropanecyclooctyne methanol for 2 h, then the solid phase was taken out and allowed to stand at 25°C for 4 h, then calcined at a starting temperature of 25°C with a programmed temperature increase gradient of 2000°C·h to 800°C for 2.5 h in a nitrogen atmosphere, then calcined at a programmed temperature increase gradient of 5600°C·h to 1600°C for 3.5 h to obtain black spherical silica (density 2.12 g / cm 3 , with a specific surface area of ​​1.76 cm 2 / g, hydroxyl content is 58μg / g, and non-crystalline content is 99.6%); (2) 2.4 parts by weight of tetramethylbisphenol F epoxy resin, 1.0 parts by weight of o-cresol epoxy resin, 2.5 parts by weight of phenol aralkyl resin containing a biphenylene skeleton, 0.5 parts by weight of phenol linear novolac resin, 80 parts by weight of fused silica powder, 0.35 parts by weight of OP wax, 0.8 parts by weight of silicone block copolymer, 0.3 parts by weight of 3-mercaptopropyltrimethoxysilane, 0.21 parts by weight of 1,8-diazabicyclo[5.4.0]undec-7-ene, 5.0 parts by weight of magnesium hydroxide, 0.2 parts by weight of IXE6107 and 0.3 parts by weight of black spherical silica obtained in step (1) are mixed and pulverized; the obtained mixture is melt-kneaded at 70° C. for 15 minutes by a double-roll mixer, then cooled and pulverized.

[0080] Example 16 (1) Under the conditions of vacuum degree of 0.10 MPa and temperature of 25°C, 100 kg of polymethyl silicone was immersed in 10 kg of cyclopropanecyclooctyne methanol for 2 h, then the solid phase was taken out and allowed to stand at 25°C for 4 h, then calcined at a starting temperature of 25°C with a programmed temperature increase gradient of 2000°C·h to 800°C for 2.5 h in a nitrogen atmosphere, then calcined at a programmed temperature increase gradient of 5600°C·h to 1600°C for 3.5 h to obtain black spherical silica (density 2.12 g / cm 3 , with a specific surface area of ​​1.76 cm 2 / g, hydroxyl content is 58μg / g, and non-crystalline content is 99.6%); (2) 2.4 parts by weight of naphthalene ring type epoxy resin, 1.0 parts by weight of trisphenol methane type multifunctional epoxy resin, 2.5 parts by weight of phenol aralkyl resin containing a biphenylene skeleton, 0.5 parts by weight of phenol linear novolac resin, 80 parts by weight of fused silica powder, 0.35 parts by weight of OP wax, 0.8 parts by weight of organic silicon block copolymer, 0.3 parts by weight of 3-mercaptopropyltrimethoxysilane, 0.21 parts by weight of 2-phenyl-4-methylimidazole, 5.0 parts by weight of triphenylphosphine oxide, 0.2 parts by weight of hydrotalcite and 0.3 parts by weight of black spherical silica obtained in step (1) are mixed and pulverized; the obtained mixture is melt-kneaded at 70° C. for 15 minutes by a double-roll mixer, then cooled and pulverized.

[0081] Embodiment 17 The method of Example 16 was followed, except that the 2-phenyl-4-methylimidazole was replaced by 1-benzyl-2-methylimidazole.

[0082] Comparative Example 1 The method of Example 1 is followed, except that the black spherical silica is replaced by carbon black.

[0083] Comparative Example 2 The method of Example 1 was followed, except that the black spherical silica was replaced with commercially available silica particles (purchased from Jiangsu Lianrui New Materials Co., Ltd., brand NQ101, particle size 75 μm).

[0084] Comparative Example 3 The method of Example 1 was followed, except that the preparation method of the black spherical silica was changed to the following method: 0.12 g of dodecyl phosphate and 28 g of deionized water were mixed and stirred, and then 6 g of concentrated hydrochloric acid with a mass fraction of 38%, 1.2 g of n-butanol and 2.2 g of tetraethyl orthosilicate were added, and the mixture was stirred in a water bath at 40°C for 26 hours to obtain a mixed solution; the mixed solution was transferred to a polytetrafluoroethylene autoclave, placed in an oven at 110°C for reaction for 26 hours, and after the reaction was completed, the mixture was centrifuged, washed with deionized water for 5 times, and dried at 65°C. The obtained solid was placed in a sintering furnace, and sintered at 550°C for 7 hours under an argon atmosphere to obtain black spherical silica.

[0085] Test Case The epoxy resin molding materials prepared in Examples 1-17 and Comparative Examples 1-3 were tested as follows: (1) The black spherical silica prepared in Example 1 was characterized by transmission electron microscopy. Figure 1 As shown, it can be seen that the black spherical silica of the present invention presents a core-shell structure. The transmission electron microscopy images of the black spherical silica prepared in Examples 2-15 are similar to those in Example 1, and will not be described in detail here; (2) Gelation time: Heat the electric heating plate to 175°C, take 0.3 g of epoxy resin molding material and place it on the iron plate, stir it continuously with a flat spatula, and test the time it takes for the epoxy resin molding material to change from a fluid to a gel state. Record the gelation time in Table 2. (3) Spiral flow length: 20 g of epoxy resin molding material was measured using a resin transfer injection molding machine with a spiral flow metal mold. The injection pressure was 70 bar and the mold temperature was 175 °C. The flowability was recorded in Table 2. (4) Open mold bending modulus and high temperature bending modulus: 110g of powdered epoxy resin molding material was put into the injection molding machine. Under the conditions of injection pressure of 70bar and injection time of 15s, the material was injected into a special bending strength test mold at 175℃ to make a 15.41*10.78*125mm specification sample. After 120s of curing, the resin product was hardened and formed. The heat-cured molded sample was quickly taken out within 10s and tested for open mold bending modulus on a universal testing machine. The bending specimen after mold opening was post-cured in a 175℃ oven for 4h, and a bending test was performed in a high temperature test box using a universal testing machine. The test box temperature was 260℃. The open mold bending modulus and high temperature bending modulus were recorded in Table 2. (5) Volume resistivity: 55 g of epoxy resin molding material was used to prepare a sample using a resin transfer injection molding machine with the aid of a resistivity test sample mold. The injection pressure was 70 bar and the mold temperature was 175 ± 1 °C. After 120 seconds of curing, the resin product was hardened and formed. The product was post-cured in a 175 °C oven for 4 hours. After the sample was cooled to 25 °C, it was tested on a Keithley 6517B resistivity tester under the conditions of 1000 V DC voltage for 2 minutes. The volume resistivity was recorded in Table 2. (6) TCT1000cyc stratification: The epoxy resin molding material is formed into cakes, and the product SOP8 is packaged using the client equipment. After curing at 175℃ for 4 hours, 22 products are taken for TCT1000cyc assessment. The stratification is fully scanned before and after the assessment to confirm the stratification situation. The TCT conditions are: -65℃-150℃. The TCT1000 stratification is recorded in Table 2.

[0086] Table 2

[0087] It can be seen from the results in Table 1 that, by comparing the test results of Examples 1-17 with Comparative Examples 1-3, the epoxy resin molding material of the present invention has a higher volume resistivity, exhibits a lower leakage current, and exhibits a lower mold opening and 260°C bending modulus, and has better delamination performance after TCT1000cyc; while the epoxy resin molding material in Comparative Example 1 has a lower volume resistivity and exhibits a higher leakage current; the epoxy resin molding materials in Comparative Examples 2 and 3 exhibit poor delamination performance after TCT1000cyc.

[0088] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. An epoxy resin molding material, characterized in that: The epoxy resin molding material contains epoxy resin, curing agent, filler, ion capture agent, low stress modifier, coupling agent, curing accelerator, release agent, flame retardant and colorant. Wherein, the colorant is black spherical silica with a core-shell structure.

2. The epoxy resin molding material according to claim 1, characterized in that: The density of the black spherical silica is 2.05-2.2 g / cm 3 , with a specific surface area of ​​1-2cm 2 / g.

3. The epoxy resin molding material according to claim 1 or 2, characterized in that: The black spherical silica is prepared according to the following steps: pre-treating the spherical organic silicone material, and then sequentially performing a first calcination and a second calcination under an inert atmosphere; Preferably, the pretreatment process comprises: immersing the spherical organic silicone material in an unsaturated alcohol under vacuum conditions, then taking out the solid phase and letting it stand; Preferably, the temperature of the second calcination is higher than the temperature of the first calcination; Preferably, the difference between the temperature of the second calcination and the temperature of the first calcination is 100-800°C; Preferably, the conditions of the first calcination include: a programmed temperature gradient of 1600-2200°C·h, a temperature of 800-1400°C; Preferably, the conditions of the second calcination include: a programmed temperature gradient of 3000-6250°C·h and a temperature of 1200-1600°C.

4. The epoxy resin molding material according to claim 3, characterized in that: The particle size range of organic silicone materials is 0.5-10μm; Preferably, the organosilicon is polymethylsilicone.

5. The epoxy resin molding material according to claim 3 or 4, characterized in that: The unsaturated alcohol is isomeric decanol and / or cyclopropanecyclooctyne methanol.

6. The epoxy resin molding material according to claim 3, characterized in that: The immersion time is 2-3 hours; and / or The standing time is 4-6h.

7. The epoxy resin molding material according to any one of claims 1 to 4, characterized in that: Based on the total weight of the epoxy resin molding material, the content of the epoxy resin is 2-8wt%, the content of the curing agent is 2-7wt%, the content of the filler is 70-90wt%, the content of the ion capture agent is 0.1-1wt%, the content of the low stress modifier is 0.1-1wt%, the content of the coupling agent is 0.1-1wt%, the content of the curing accelerator is 0.1-1wt%, the content of the release agent is 0.1-2wt%, the content of the flame retardant is 1-10wt%, and the content of the colorant is 0.1-0.9wt%; Preferably, the epoxy resin is at least one of o-cresol epoxy resin, biphenyl crystalline epoxy resin, dicyclopentadiene type epoxy resin, phenol biphenyl alkyl type epoxy resin, naphthol aralkyl type epoxy resin, naphthalene ring type epoxy resin, trisphenol methane type multifunctional epoxy resin and tetramethyl bisphenol F type epoxy resin; Preferably, the curing agent is at least one of phenol linear phenolic resin, phenol aralkyl resin containing a biphenylene skeleton, trihydroxyphenylmethane type multifunctional phenolic resin and naphthol aralkyl type phenolic resin; Preferably, the filler is silicon dioxide powder; Preferably, the ion capture agent is at least one of an anion capture agent, a cation capture agent and an anion-cation composite ion capture agent; Preferably, the low stress modifier is at least one of polyether-modified polysilicone, silicone block copolymer and carboxyl-terminated nitrile rubber; Preferably, the coupling agent is at least one of 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane and N-phenyl-3-aminopropyltrimethoxysilane; Preferably, the curing accelerator is at least one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, triphenylphosphine, triphenylphosphine-benzoquinone adduct and 1,8-diazabicyclo[5.4.0]undec-7-ene; Preferably, the release agent is at least one of carnauba wax, montanate wax, polyethylene wax and oxidized polyethylene wax; Preferably, the flame retardant is at least one of triphenylphosphine oxide, polyphosphazene, aluminum hydroxide and magnesium hydroxide.

8. A method for preparing the epoxy resin molding material according to any one of claims 1 to 7, characterized in that: The method comprises the following steps: (1) Mixing and pulverizing epoxy resin, curing agent, filler, ion scavenger, low stress modifier, coupling agent, curing accelerator, release agent, flame retardant and colorant; (2) The mixture obtained in step (1) is melt-kneaded or extruded, and then cooled and pulverized.

9. The method according to claim 8, characterized in that The melt mixing conditions include: temperature of 70-90° C. and time of 7-15 min.

10. Use of the epoxy resin molding material according to any one of claims 1 to 7 in semiconductor packaging.

Images