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 forming material contains first epoxy resin, a curing agent, a solid filler, an ion capturing agent, a low-stress modifier, a coupling agent, a curing accelerator, a chemical material, a flame retardant and a coloring agent, the first epoxy resin is at least two of bisphenol A type structure epoxy resin, biphenyl phenol type epoxy resin, biphenyl type structure epoxy resin, naphthalene type structure epoxy resin, DCPD type structure epoxy resin, polyfunctional group type structure epoxy resin and bisphenol F type structure epoxy resin; the chemical material is prepared by mixing second epoxy resin, an accelerant, a dispersing agent and a release agent in an inert atmosphere. The epoxy resin molding material has high continuous molding stability, and in semiconductor chip packaging, the surface of a plastic package body has good mechanical properties and fluidity.

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] With the continuous development of science and technology, the application scenarios and application environments of electronic products have become more diversified. Society has put forward higher requirements for semiconductor packaging, and the performance requirements for semiconductor packaging materials have also become higher and higher. In addition to having certain mechanical properties to avoid damage to semiconductor chips, it is also necessary to avoid the risk of moisture absorption during use. In addition, the plastic encapsulation material needs to have stable continuous moldability in packaging production, no defects in appearance, and excellent mold cleaning cycle capabilities. In addition to improving production efficiency and reducing costs, good continuous molding of packaging can also improve product stability and reduce defective rates. The current way to improve continuous moldability is generally to adjust the release agent system in the plastic encapsulation material formula to adapt to the client's mold cleaning glue and mold, thereby improving the continuous moldability of the plastic encapsulation material and meeting the mold cleaning requirements of the packaging client. Summary of the invention

[0003] The purpose of the present invention is to overcome the problems in the prior art that the appearance of the plastic encapsulation material is poor after multiple moldings, resulting in a short mold cleaning cycle, and to provide an epoxy resin molding material and a preparation method and application thereof. The epoxy resin molding material has high continuous molding stability, and in semiconductor chip packaging, the surface of the plastic encapsulation body has good mechanical properties and fluidity.

[0004] In order to achieve the above-mentioned purpose, the first aspect of the present invention provides an epoxy resin molding material, which contains a first epoxy resin, a curing agent, a solid filler, an ion capture agent, a low stress modifier, a coupling agent, a curing accelerator, a chemical material, a flame retardant and a colorant, wherein the first epoxy resin is at least two of bisphenol A type epoxy resin, biphenyl phenol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, DCPD type epoxy resin, multifunctional type epoxy resin and bisphenol F type epoxy resin; the chemical material is prepared by mixing a second epoxy resin, a accelerator, a dispersant and a release agent under an inert atmosphere.

[0005] Preferably, the multifunctional epoxy resin is an o-cresol epoxy resin.

[0006] Preferably, based on the total weight of the chemical materials, the content of the second epoxy resin is 80-90wt%, the content of the accelerator is 0.1-1wt%, the content of the dispersant is 1-10wt%, and the content of the release agent is 1-10wt%.

[0007] Preferably, the second epoxy resin is one of the first epoxy resins.

[0008] Preferably, based on the total weight of the epoxy resin molding material, the content of the first epoxy resin is 2-11wt%, the content of the curing agent is 1-6wt%, the content of the solid filler is 80-90wt%, 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 chemical material is 0.1-2wt%, the content of the flame retardant is 0.2-10wt%, and the content of the colorant is 0.1-1wt%.

[0009] Preferably, the curing agent is XYLOK phenolic resin and / or linear phenolic resin.

[0010] Preferably, the solid filler is at least one of silicon dioxide powder, aluminum oxide powder and magnesium oxide powder.

[0011] Preferably, the ion capture agent is at least one of a first metal hydroxide, a hydrated metal oxide and an acidic metal salt, preferably at least one of aluminum hydroxide, magnesium hydroxide, hydrated aluminum oxide, hydrated magnesium oxide, an aluminum salt and a magnesium salt, more preferably hydrotalcite.

[0012] Preferably, the low stress modifier is rubber and / or organosilane.

[0013] Preferably, the coupling agent is at least one of (3-glycidylpropoxy)trimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, bis-[γ-(triethoxysilyl)propyl]tetrasulfide silane and γ-mercaptopropyltrimethoxysilane.

[0014] Preferably, the curing accelerator is a coupling compound of p-benzoquinone and triphenylphosphine.

[0015] Preferably, the flame retardant is at least one of a second metal hydroxide, a metal oxide, a molybdate, a borate, a phosphorus-containing compound and a nitrogen-containing compound.

[0016] Preferably, the colorant is carbon black.

[0017] Preferably, the preparation method of the chemical material comprises: under an inert atmosphere, melting a portion of the second epoxy resin at 155-170° C., then mixing with another portion of the second epoxy resin and performing a first stirring, then mixing with the release agent and the accelerator and performing a second stirring, then mixing with the dispersant and performing a third stirring, then cooling to 135-145° C., and finally discharging the material through a filter.

[0018] Preferably, the accelerator is an amine accelerator, preferably at least one of epoxidized acetamide, epoxidized propionamide, diazabicyclo and triethylenediamine.

[0019] Preferably, the dispersant is a copolymer of α-olefin and maleic anhydride.

[0020] Preferably, the release agent is natural wax and / or synthetic wax.

[0021] Preferably, the natural wax is mineral wax and / or vegetable wax.

[0022] Preferably, the synthetic wax is polyethylene and / or polyamide wax.

[0023] The second aspect of the present invention provides a method for preparing the above-mentioned epoxy resin molding material, which comprises: melt-mixing a first epoxy resin, a curing agent, a solid filler, an ion capture agent, a low stress modifier, a coupling agent, a curing accelerator, a chemical material, a flame retardant and a colorant under an inert atmosphere.

[0024] Preferably, the melt mixing conditions include: temperature of 100-110° C. and time of 2-20 min.

[0025] A third aspect of the present invention provides application of the above-mentioned epoxy resin molding material in semiconductor chip packaging.

[0026] Through the above technical scheme, the epoxy resin molding material described in the present invention adopts the chemical material prepared by mixing epoxy resin, accelerator, dispersant and release agent under inert atmosphere, which can significantly improve the continuous molding stability of the epoxy resin molding material. At the same time, when applied to the field of semiconductor chip packaging, it has the characteristics of long mold cleaning cycle, high reliability and good operability, which improves production efficiency and product stability, and reduces cost and defective rate. DETAILED DESCRIPTION

[0027] 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.

[0028] 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.

[0029] The epoxy resin molding material of the present invention contains a first epoxy resin, a curing agent, a solid filler, an ion capture agent, a low stress modifier, a coupling agent, a curing accelerator, a chemical material, a flame retardant and a colorant, wherein the first epoxy resin is at least two of bisphenol A type epoxy resin, biphenyl phenol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, DCPD type epoxy resin, multifunctional type epoxy resin and bisphenol F type epoxy resin; the chemical material is prepared by mixing a second epoxy resin, a accelerator, a dispersant and a release agent under an inert atmosphere. According to the epoxy resin molding material of the present invention, the chemical material prepared by mixing epoxy resin, accelerator, dispersant and release agent is used, which improves the dispersibility of trace components on the one hand, and avoids the oxidation of each component in the process of preparing the chemical material on the other hand, and has very high continuous molding stability.

[0030] In the epoxy resin molding material of the present invention, the multifunctional epoxy resin may be an o-cresol epoxy resin.

[0031] In the epoxy resin molding material described in the present invention, based on the total weight of the chemical material, the content of the second epoxy resin can be 80-90wt%, preferably 82-88wt%; the content of the accelerator can be 0.1-1wt%, preferably 0.2-0.6wt%; the content of the dispersant can be 1-10wt%, preferably 2-8wt%; the content of the release agent can be 1-10wt%, preferably 3-10wt%.

[0032] In the epoxy resin molding material described in the present invention, the second epoxy resin can be one of the first epoxy resins. When the first epoxy resin contains two of bisphenol A type epoxy resin, biphenyl phenol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, DCPD type epoxy resin, multifunctional type epoxy resin and bisphenol F type epoxy resin, the mass ratio of the first epoxy resin to the second epoxy resin can be (0.5-2):1. When the first epoxy resin contains three of bisphenol A type epoxy resin, biphenyl phenol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, DCPD type epoxy resin, multifunctional type epoxy resin and bisphenol F type epoxy resin, the mass ratio of the first epoxy resin, the second epoxy resin and the third epoxy resin can be (0.5-2):(0.5-2):1. In some embodiments, the first epoxy resin is a biphenyl phenol type epoxy resin (MAR resin) and a biphenyl type structural epoxy resin, and the second epoxy resin is a biphenyl phenol type epoxy resin; in the first epoxy resin, the mass ratio of the biphenyl phenol type epoxy resin (MAR resin) to the biphenyl type structural epoxy resin is (0.5-2):1.

[0033] 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 first epoxy resin can be 2-11wt%, preferably 4-10wt%, and more preferably 4-8wt%; the content of the curing agent can be 1-6wt%, preferably 1-5wt%, and more preferably 2-4wt%; the content of the solid filler can be 80-90wt%, preferably 80-89wt%, and more preferably 85-89wt%; the content of the ion capture agent can be 0.1-1wt%, preferably 0.1-0.7wt%, and more preferably 0.2-0.6wt%; the content of the low stress modifier can be 0.1-1wt%, preferably 0.1-0.8wt%, More preferably, it is 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 0.2-0.9wt%, more preferably 0.3-0.9wt%; the content of the chemical material can be 0.1-2wt%, preferably 0.2-1wt%, more preferably 0.5-1wt%; the content of the flame retardant can be 0.2-10wt%, preferably 0.5-9wt%, more preferably 0.5-7wt%; the content of the colorant can be 0.1-1wt%, preferably 0.1-0.8wt%, more preferably 0.1-0.7wt%.

[0034] In the epoxy resin molding material of the present invention, the curing agent can be used to react with the epoxy resin. The curing agent can be a conventional choice in the art. The curing agent can be XYLOK phenolic resin and / or linear phenolic resin, preferably XYLOK phenolic resin.

[0035] In the epoxy resin molding material described in the present invention, the solid filler may be at least one of silica powder, alumina powder and magnesium oxide powder, preferably silica powder. The silica powder may be molten spherical silica powder. The molten spherical silica powder contains a first molten spherical silica powder and a second molten spherical silica powder. The particle size of the first molten spherical silica powder may be 132 μm or less. The particle size of the second molten spherical silica powder may be 132 μm or less. The mass ratio of the first molten spherical silica powder to the second molten spherical silica powder may be (5-7): 1. The molten spherical silica powder is purchased from Jiangsu Lianrui New Materials Co., Ltd. In some embodiments, the cut point of the particle size of the molten spherical silica powder is 75 μm. The particle size of the solid filler may be 150 μm or less, preferably 25-75 μm.

[0036] In the epoxy resin molding material of the present invention, the ion capture agent may be at least one of a first metal hydroxide, a hydrated metal oxide and an acidic metal salt, preferably at least one of aluminum hydroxide, magnesium hydroxide, hydrated aluminum oxide, hydrated magnesium oxide, an aluminum salt and a magnesium salt, and more preferably hydrotalcite. The main component of the hydrotalcite is a layered double metal hydroxide.

[0037] In the epoxy resin molding material of the present invention, the low stress modifier may be rubber and / or organosilane, preferably organosilane. The organosilane may be silicone oil.

[0038] In the epoxy resin molding material of the present invention, the coupling agent can be at least one of (3-glycidyl propoxy) trimethoxy silane, N-phenyl-3-aminopropyl trimethoxy silane, bis-[γ-(triethoxysilyl)propyl] tetrasulfide silane and γ-mercaptopropyl trimethoxy silane, preferably (3-glycidyl propoxy) trimethoxy silane. The (3-glycidyl propoxy) trimethoxy silane is KH560.

[0039] In the epoxy resin molding material of the present invention, the curing accelerator may be a coupling compound of p-benzoquinone and triphenylphosphine.

[0040] In the epoxy resin molding material of the present invention, the flame retardant may be at least one of a second metal hydroxide, a metal oxide, a molybdate, a borate, a phosphorus-containing compound and a nitrogen-containing compound, preferably a phosphorus-containing compound, and more preferably triphenylphosphine oxide.

[0041] In the epoxy resin molding material of the present invention, the colorant can be a conventional choice in the art. In some embodiments, the colorant is carbon black.

[0042] In the epoxy resin molding material of the present invention, the preparation method of the chemical material includes: in an inert atmosphere, a part of the second epoxy resin is melted at 155-170°C, then mixed with another part of the second epoxy resin and stirred for the first time, then mixed with the release agent and the accelerator and stirred for the second time, then mixed with the dispersant and stirred for the third time, then cooled to 135-145°C, and finally discharged with a filter. 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%. The mass of the amount of the second epoxy resin and the other part of the second epoxy resin can be (0.8-1.2): 1. The conditions of the first stirring include: the temperature can be 155-170°C, preferably 160-170°C; the stirring rate can be 100-150rpm, preferably 120-150rpm; the time can be 8-15min, preferably 8-12min. The conditions for the second stirring include: the temperature can be 155-170°C, preferably 160-170°C; the stirring rate can be 100-150rpm, preferably 120-150rpm; the time can be 2.5-3.5h, preferably 2.8-3.2h. The conditions for the third stirring include: the temperature can be 155-170°C, preferably 160-170°C; the stirring rate can be 100-150rpm, preferably 120-150rpm; the time can be 0.5-1.5h, preferably 0.8-1.2h. The mesh number of the filter can be 100-200 mesh. The filter is used to slow down the discharge speed and remove impurities. The preparation of the chemical material is carried out in a reactor.

[0043] In the epoxy resin molding material of the present invention, the accelerator may be an amine accelerator. The amine accelerator may be purchased from Xinhua Wanbo Company with a brand name of DBU. The accelerator helps to promote the internal reaction of the raw materials.

[0044] In the epoxy resin molding material of the present invention, the dispersant may be a copolymer of α-olefin and maleic anhydride. The dispersant helps to improve the stability of continuous molding.

[0045] In the epoxy resin molding material of the present invention, the release agent may be natural wax and / or synthetic wax, preferably natural wax. The natural wax may be mineral wax and / or vegetable wax, preferably vegetable wax. The vegetable wax may be carnauba wax (E53). The synthetic wax may be polyethylene and / or polyamide wax.

[0046] In some embodiments, the epoxy resin molding material of the present invention contains a first epoxy resin, a curing agent, a solid filler, an ion capture agent, a low stress modifier, a coupling agent, a curing accelerator, a chemical material, a flame retardant and a colorant, wherein, based on the total weight of the epoxy resin molding material, the content of the first epoxy resin is 2-11wt%, the content of the curing agent is 1-6wt%, the content of the solid filler is 80-90wt%, 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 chemical material is 0.1-2wt%, and the content of the The content of the flame retardant is 0.2-10wt%, and the content of the colorant is 0.1-1wt%; the first epoxy resin is at least two of bisphenol A type epoxy resin, biphenyl phenol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, DCPD type epoxy resin, multifunctional type epoxy resin and bisphenol F type epoxy resin; the curing agent is XYLOK phenolic resin and / or linear phenolic resin; the solid filler is at least one of silicon dioxide powder, aluminum oxide powder and magnesium oxide powder; the ion capture agent is at least one of a first metal hydroxide, a hydrated metal oxide and an acidic metal salt; the low stress modifier is rubber and / or an organic silane; the coupling agent is (3- The curing accelerator is a coupling compound of p-benzoquinone and triphenylphosphine; the flame retardant is at least one of a second metal hydroxide, a metal oxide, a molybdate, a borate, a phosphorus-containing compound and a nitrogen-containing compound; the colorant is carbon black; the preparation method of the chemical material comprises: in an inert atmosphere, melting a part of the second epoxy resin at 155-170° C., then mixing with another part of the second epoxy resin and stirring at 155-170° C. at a stirring rate of 100-150 rpm for 8-15 minutes, and then The mixture is mixed with the release agent and the accelerator and stirred at 155-170°C at a stirring rate of 100-150 rpm for 2.5-3.5 hours, then mixed with the dispersant and stirred at 155-170°C at a stirring rate of 100-150 rpm for 0.5-1.5 hours, then cooled to 135-145°C, and finally discharged through a 100-200 mesh filter; the second epoxy resin is one of the first epoxy resins; the accelerator is an amine accelerator; the dispersant is an α-olefin and maleic anhydride copolymer; the release agent is a natural wax and / or a synthetic wax; based on the total weight of the chemical material, the content of the second epoxy resin is 80-90wt%, and the content of the accelerator is 0.1-1wt%, the content of the dispersant is 1-10wt%, and the content of the release agent is 1-10wt%. .

[0047] The second aspect of the present invention provides a method for preparing the above-mentioned epoxy resin molding material, the method comprising: melt-mixing a first epoxy resin, a curing agent, a solid filler, an ion capture agent, a low stress modifier, a coupling agent, a curing accelerator, a chemical material, a flame retardant and a colorant under an inert atmosphere. According to the method of the present invention, the epoxy resin molding material prepared by using the chemical material can significantly improve the continuous molding stability of the resin composition, has good mechanical properties and fluidity, and at the same time improves production efficiency and product stability, and reduces costs and defective rates.

[0048] In the method of the present invention, the inert atmosphere can be argon and / or nitrogen, preferably nitrogen. In a more preferred embodiment, the purity of the nitrogen is 99.0wt%-99.9wt%.

[0049] In the method of the present invention, the melt-mixing conditions include: the temperature can be 100-110° C., preferably 105-110° C.; the time can be 2-20 min, preferably 5-15 min. The melt-mixing is carried out in a twin-screw extruder.

[0050] In the method of the present invention, the method may further include: extruding the material obtained by melt-kneading into sheets, followed by cooling and then pulverizing.

[0051] The third aspect of the present invention provides the application of the above-mentioned epoxy resin molding material in semiconductor chip packaging. According to the application described in the present invention, the appearance of the plastic package can be improved and the mold cleaning cycle can be extended; after continuous packaging, the surface appearance of the plastic package is good, and it has good mechanical properties and good fluidity. The epoxy resin molding material is formed into a cake material through a subsequent molding step and used for semiconductor chip packaging.

[0052] 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.

[0053] 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.

[0054] In the following examples and comparative examples:

[0055] Epoxy resin: Biphenyl phenol type epoxy resin was purchased from Shengquan Company with the brand name SQXN323; biphenyl type structural epoxy resin was purchased from Shengquan Company with the brand name SQE101; naphthalene type structural epoxy resin was purchased from Dainippon Ink & Printing Co., Ltd. with the brand name HP5600; DCPD type structural epoxy resin was purchased from Dainippon Ink & Printing Co., Ltd. with the brand name HP7200; o-cresol type structural epoxy resin was purchased from Shengquan Company with the brand name SQCN700-1; bisphenol F type structural epoxy resin was purchased from Shengquan Company with the brand name SQE104; bisphenol A type structural epoxy resin was purchased from Mitsubishi Corporation with the brand name YL6810.

[0056] Curing agent: XYLOK phenolic resin was purchased from Shengquan Company with the brand name SH-4064; linear phenolic resin was purchased from Hengfeng Company with the brand name Resicare3010.

[0057] Solid filler: The molten spherical silica powder was purchased from Lianrui Company with a particle size of 75 μm. The molten spherical silica powder contains a first molten spherical silica powder and a second molten spherical silica powder. The first molten spherical silica powder is NQ101 and the second molten spherical silica powder is NQ1350D.

[0058] Ion scavenger: Hydrotalcite was purchased from Kyowa Chemical Industry Co., Ltd., Japan, with the brand name DHT-4A.

[0059] Low stress modifier: rubber was purchased from Banglu Trading Co., Ltd. with the brand name H-100; silicone oil was purchased from Dow with the brand name SF 8421EG.

[0060] Coupling agent: (3-glycidylpropoxy)trimethoxysilane was purchased from Danyang Dolly Company with the brand name KH560; N-phenyl-3-aminopropyltrimethoxysilane was purchased from Andy Light Technology (Shenzhen) Company with the brand name KBM-573; bis-[γ-(triethoxysilyl)propyl]tetrasulfide silane was purchased from Danyang Dolly Company with the brand name DL-69; γ-mercaptopropyltrimethoxysilane was purchased from Danyang Dolly Company with the brand name KH590.

[0061] Curing accelerator: p-Benzoquinone and triphenylphosphine coupling agent purchased from Lanbi Company, brand TB;

[0062] Flame retardant: Triphenylphosphine oxide was purchased from Hubei Nona Company.

[0063] Colorant: Carbon black.

[0064] Accelerator: Amine accelerator was purchased from Xinhua Wanbo Company with the brand name DBU.

[0065] Dispersant: α-olefin and maleic anhydride copolymer purchased from Mitsubishi Chemical Corporation, brand 30M.

[0066] Release agent: Carnauba wax was purchased from Shanghai Yuexiang Industrial Co., Ltd. with a brand number of E53.

[0067] Examples 1-6 and the comparative example all prepared epoxy resin molding materials according to the following method:

[0068] (1) a portion of biphenyl phenol type epoxy resin is put into a reaction kettle, nitrogen is introduced, and the mixture is melted at 160° C., then mixed with another portion of biphenyl phenol type epoxy resin and stirred at 160° C. at a stirring rate of 150 rpm for 10 min, then mixed with carnauba wax (E53) and an amine accelerator (DBU) and stirred at 160° C. at a stirring rate of 150 rpm for 3 h, then mixed with an α-olefin and maleic anhydride copolymer (30M) and stirred at 160° C. at a stirring rate of 150 rpm for 1 h, then cooled to 140° C., and finally discharged through a 100-mesh filter to obtain a chemical material;

[0069] (2) Biphenyl phenol type epoxy resin, biphenyl type structural epoxy resin, XYLOK phenolic resin, molten spherical silica powder, chemical material, para-benzoquinone and triphenylphosphine coupling (TB), rubber (H-100), (3-glycidyl propoxy) trimethoxysilane (KH560), triphenylphosphine oxide, hydrotalcite and carbon black are introduced into a twin-screw extruder, nitrogen is introduced, and melt-mixed at 110° C. for 10 minutes. The obtained material is extruded into sheets, then cooled and then crushed.

[0070] The compositions of the epoxy resin molding materials of Examples 1-6 are shown in Table 1.

[0071] Table 1

[0072]

[0073] Example 7

[0074] The method of Example 1 was followed, except that the amount of carnauba wax (E53) was replaced from 0.105 parts by weight to 0.115 parts by weight.

[0075] Example 8

[0076] The method of Example 1 was followed, except that the amount of carnauba wax (E53) was replaced from 0.105 parts by weight to 0.125 parts by weight.

[0077] Example 9

[0078] The method of Example 1 was followed, except that the amount of the copolymer of α-olefin and maleic anhydride (30M) was changed from 0.053 parts by weight to 0.058 parts by weight.

[0079] Example 10

[0080] The method of Example 1 was followed, except that the amount of the copolymer of α-olefin and maleic anhydride (30M) was changed from 0.053 parts by weight to 0.063 parts by weight.

[0081] Embodiment 11

[0082] The method of Example 1 was followed, except that the amount of the copolymer of α-olefin and maleic anhydride (30M) was changed from 0.053 parts by weight to 0.068 parts by weight.

[0083] Example 12

[0084] (1) 0.5 parts by weight of bisphenol A epoxy resin is put into a reaction kettle, nitrogen is introduced, and the mixture is melted at 155° C., then mixed with 0.55 parts by weight of bisphenol A epoxy resin and stirred at 155° C. at a stirring rate of 100 rpm for 8 min, then mixed with 0.105 parts by weight of carnauba wax (E53) and 0.005 parts by weight of amine accelerator (DBU) and stirred at 155° C. at a stirring rate of 100 rpm for 2.5 h, then mixed with 0.053 parts by weight of α-olefin and maleic anhydride copolymer (30M) and stirred at 155° C. at a stirring rate of 100 rpm for 0.5 h, then cooled to 135° C., and finally discharged through a 100-mesh filter to obtain a chemical material;

[0085] (2) 1.6 parts by weight of bisphenol A type epoxy resin, 2.24 parts by weight of naphthalene type epoxy resin, 2.9 parts by weight of linear phenolic resin, 73 parts by weight of first molten spherical silica powder, 13 parts by weight of second molten spherical silica powder, 1.213 parts by weight of chemical material, 1.6 parts by weight of a coupling compound of p-benzoquinone and triphenylphosphine (TB), 0.6 parts by weight of rubber (H-100), 0.6 parts by weight of N-phenyl-3-aminopropyltrimethoxysilane (KBM-573), 0.8 parts by weight of triphenylphosphine oxide, 0.3 parts by weight of carbon black and 0.25 parts by weight of hydrotalcite are introduced into a twin-screw extruder, nitrogen is introduced, and the mixture is melt-kneaded at 100° C. for 20 minutes. The obtained material is extruded into sheets, cooled, and then crushed.

[0086] Example 13

[0087] (1) 0.5 parts by weight of a DCPD-type epoxy resin is put into a reaction kettle, nitrogen is introduced, and the mixture is melted at 170° C., then mixed with 0.55 parts by weight of a DCPD-type epoxy resin and stirred at 170° C. at a stirring rate of 150 rpm for 15 min, then mixed with 0.105 parts by weight of carnauba wax (E53) and 0.005 parts by weight of an amine accelerator (DBU) and stirred at 170° C. at a stirring rate of 150 rpm for 3.5 h, then mixed with 0.053 parts by weight of an α-olefin and maleic anhydride copolymer (30M) and stirred at 170° C. at a stirring rate of 150 rpm for 1.5 h, then cooled to 145° C., and finally discharged through a 100-mesh filter to obtain a chemical material;

[0088] (2) 1.6 parts by weight of a DCPD-type epoxy resin, 2.24 parts by weight of an o-cresol-type epoxy resin, 2.9 parts by weight of a linear phenolic resin, 73 parts by weight of a first molten spherical silica powder, 13 parts by weight of a second molten spherical silica powder, 1.213 parts by weight of a chemical material, 1.6 parts by weight of a coupling product of p-benzoquinone and triphenylphosphine (TB), 0.6 parts by weight of a rubber (H-100), 0.6 parts by weight of bis-[γ-(triethoxysilyl)propyl]tetrasulfide silane, 0.8 parts by weight of triphenylphosphine oxide, 0.3 parts by weight of carbon black and 0.25 parts by weight of hydrotalcite are introduced into a twin-screw extruder, nitrogen is introduced, and the mixture is melt-kneaded at 110° C. for 2 min. The resulting material is extruded into sheets, cooled, and then crushed.

[0089] Embodiment 14

[0090] (1) 0.5 parts by weight of phenolic epoxy resin is put into a reaction kettle, nitrogen is introduced, and the mixture is melted at 160° C., then mixed with 0.55 parts by weight of phenolic epoxy resin and stirred at 160° C. at a stirring rate of 150 rpm for 10 min, then mixed with 0.105 parts by weight of carnauba wax (E53) and 0.005 parts by weight of amine accelerator (DBU) and stirred at 160° C. at a stirring rate of 150 rpm for 3 h, then mixed with 0.053 parts by weight of α-olefin and maleic anhydride copolymer (30M) and stirred at 160° C. at a stirring rate of 150 rpm for 1 h, then cooled to 140° C., and finally discharged through a 100-mesh filter to obtain a chemical material;

[0091] (2) 1.6 parts by weight of phenolic epoxy resin, 1.12 parts by weight of o-cresol epoxy resin, 1.12 parts by weight of bisphenol F epoxy resin, 2.9 parts by weight of linear phenolic resin, 73 parts by weight of first molten spherical silica powder, 13 parts by weight of second molten spherical silica powder, 1.213 parts by weight of chemical material, 1.6 parts by weight of a coupling product of p-benzoquinone and triphenylphosphine (TB), 0.6 parts by weight of silicone oil, 0.6 parts by weight of γ-mercaptopropyltrimethoxysilane, 0.8 parts by weight of triphenylphosphine oxide, 0.3 parts by weight of carbon black and 0.25 parts by weight of hydrotalcite are introduced into a twin-screw extruder, nitrogen is introduced, and the mixture is melt-kneaded at 110° C. for 10 min. The obtained material is extruded into sheets, cooled, and then crushed.

[0092] Comparative Example 1

[0093] The method of Example 1 was followed, except that 0.053 parts by weight of the α-olefin and maleic anhydride copolymer (30M) was replaced by 0.053 parts by weight of a biphenylphenol-based epoxy resin.

[0094] Comparative Example 2

[0095] The method of Example 1 was followed, except that 0.005 parts by weight of the amine accelerator (DBU) was replaced with 0.005 parts by weight of a biphenylphenol epoxy resin.

[0096] Comparative Example 3

[0097] The method of Example 1 was followed, except that 0.105 parts by weight of carnauba wax (E53) was replaced by 0.105 parts by weight of biphenylphenol type epoxy resin.

[0098] Comparative Example 4

[0099] The method of Example 1 was followed, except that the preparation of the chemical material in step (1) was not performed, and 1.213 parts by weight of the chemical material was replaced by 1.213 parts by weight of biphenyl phenol type epoxy resin.

[0100] Comparative Example 5

[0101] The method of Example 1 is followed, except that the composition of the chemical material is changed to linear phenolic resin (curing agent), sodium hexametaphosphate (dispersant), oxidized polyethylene wax (release agent) and monoglyceride wax (release agent). Specifically, the preparation process of the chemical material in step (1) includes:

[0102] 0.105 parts by weight of linear phenolic resin was put into a reaction kettle, nitrogen was introduced, melted at 160°C and stirred at 150 rpm for 10 min at 160°C, then mixed with 0.105 parts by weight of oxidized polyethylene wax and 0.005 parts by weight of monoglyceride wax and stirred at 160°C at 150 rpm for 3 h, then mixed with 0.053 parts by weight of sodium hexametaphosphate and stirred at 160°C at 150 rpm for 1 h, then cooled to 140°C, and finally discharged through a 100-mesh filter to obtain a chemical material.

[0103] Test Case

[0104] The epoxy resin molding materials prepared in Examples 1-14 and Comparative Examples 1-5 were tested as follows:

[0105] (1) Gelation time: Heat the electric hot plate to 175°C, take 3 g of the sample and place it on the iron plate, test the time it takes for the epoxy resin molding material to change from a fluid to a gel state and record the gelation time in Table 2;

[0106] (2) Flowability: 30 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 kgf / cm 2 , the mold temperature was 175°C, and the fluidity was recorded in Table 2;

[0107] (3) Water absorption: The water absorption test was conducted according to the "PCT24" method. The epoxy resin molding material was molded into a cake by a press, wherein the size of the cake was 50 mm*3 mm (diameter*thickness). The test conditions were 121°C, 100 RH%, 2 atm, and 24 h. The water absorption was calculated as follows: the weight increase of the sample after PCT24 / the initial weight of the sample*100%. The water absorption was recorded in Table 2.

[0108] (4) Mold opening bending strength and mold opening bending modulus: 110g of powdered epoxy resin molding material was put into an injection molding machine. Under the conditions of injection pressure of 60 bar and injection time of 15 s, the epoxy resin molding material was injected into a special bending strength test mold at 175°C to form a 15.41*10.78*120mm sample. After 120s of curing, the resin product was hardened and formed. Within 15s, the heat-cured molded sample was quickly taken out and placed in the test area of ​​the universal testing machine. The pressure test was started. The method was based on the national standard GB / T 9341-2008. The mold opening bending strength and mold opening bending modulus were recorded in Table 3.

[0109] (5) Glass transition temperature (Tg): The Tg of the epoxy resin molding material in the present invention can be determined by dynamic mechanical analysis (DMA) or thermomechanical analysis (TMA). The TMA method refers to the national standard GB / T 36800.2-2018. The epoxy resin molding material is first cured at a mold temperature of 180°C for 150s in a molding machine to form a sample strip and a sample sheet, and then placed in an oven at 180°C for post-curing for 6h. The sample size for TMA test is 5 mm*5 mm (diameter*thickness). Tg is recorded in Table 3.

[0110] (6) Thermal expansion coefficient (CTE1 / CTE2): measured by the above-mentioned TMA, the method refers to the national standard GB / T36800.2-2018, and the linear expansion coefficient α1 and the linear expansion coefficient α2 are recorded in Table 3;

[0111] (7) Continuous molding stability: The epoxy resin molding material is molded into cakes by a cake making machine, where the size of the cake is 16mm*11mm (diameter*thickness), and the injection pressure is 75kg / cm 2 , mold clamping pressure 160kg / cm 2 , the mold closing time is 120s, and continuous packaging is performed. The surface of the semiconductor device is observed until irregular color difference or dirt appears on the surface, and the mold number of continuous packaging is recorded as shown in Table 3 to characterize the stability of continuous molding.

[0112] Table 2

[0113] serial number Gel time (s) Fluidity(cm) Water absorption (%) Example 1 22 143 0.20 Example 2 23 145 0.19 Example 3 22 143 0.18 Example 4 24 147 0.2 Example 5 22 140 0.18 Example 6 23 140 0.19 Example 7 24 143 0.20 Example 8 23 145 0.20 Example 9 24 150 0.19 Example 10 23 140 0.19 Embodiment 11 25 145 0.18 Example 12 24 143 0.20 Example 13 23 145 0.20 Embodiment 14 24 147 0.19 Comparative Example 1 23 140 0.19 Comparative Example 2 22 145 0.18 Comparative Example 3 22 143 0.19 Comparative Example 4 24 141 0.20 Comparative Example 5 23 142 0.20

[0114] Table 3

[0115]

[0116]

[0117] It can be seen from the results of Table 2 and Table 3 that the epoxy resin composition of the present invention has very high continuous molding stability. After 160-250 molds of continuous packaging, the surface appearance of the plastic package is good, without undesirable phenomena such as mold sticking, mold stains, and rough surfaces. At the same time, it has good mechanical properties, and has good fluidity, water resistance and flame retardancy, which can meet the stability requirements of semiconductor devices in the continuous packaging process, reduce costs, and improve the efficiency and reliability of the packaging process.

[0118] 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 a first epoxy resin, a curing agent, a solid filler, an ion capture agent, a low stress modifier, a coupling agent, a curing accelerator, a chemical, a flame retardant and a colorant. Wherein, the first epoxy resin is at least two of bisphenol A type epoxy resin, biphenyl phenol type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, DCPD type epoxy resin, multifunctional type epoxy resin and bisphenol F type epoxy resin; The chemical material is prepared by mixing a second epoxy resin, a promoter, a dispersant and a release agent under an inert atmosphere.

2. The epoxy resin molding material according to claim 1, characterized in that: The multifunctional epoxy resin is an o-cresol epoxy resin.

3. The epoxy resin molding material according to claim 1 or 2, characterized in that: Based on the total weight of the chemical material, the content of the second epoxy resin is 80-90wt%, the content of the accelerator is 0.1-1wt%, the content of the dispersant is 1-10wt%, and the content of the release agent is 1-10wt%; Preferably, the second epoxy resin is one of the first epoxy resins.

4. The epoxy resin molding material according to any one of claims 1 to 3, characterized in that: Based on the total weight of the epoxy resin molding material, the content of the first epoxy resin is 2-11wt%, the content of the curing agent is 1-6wt%, the content of the solid filler is 80-90wt%, 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 chemical material is 0.1-2wt%, the content of the flame retardant is 0.2-10wt%, and the content of the colorant is 0.1-1wt%; Preferably, the curing agent is XYLOK phenolic resin and / or linear phenolic resin; Preferably, the solid filler is at least one of silicon dioxide powder, aluminum oxide powder and magnesium oxide powder; Preferably, the ion capture agent is at least one of a first metal hydroxide, a hydrated metal oxide and an acidic metal salt, preferably at least one of aluminum hydroxide, magnesium hydroxide, hydrated aluminum oxide, hydrated magnesium oxide, an aluminum salt and a magnesium salt, more preferably hydrotalcite; Preferably, the low stress modifier is rubber and / or organosilane; Preferably, the coupling agent is at least one of (3-glycidylpropoxy)trimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, bis-[γ-(triethoxysilyl)propyl]tetrasulfide silane and γ-mercaptopropyltrimethoxysilane; Preferably, the curing accelerator is a coupling compound of p-benzoquinone and triphenylphosphine; Preferably, the flame retardant is at least one of a second metal hydroxide, a metal oxide, a molybdate, a borate, a phosphorus-containing compound, and a nitrogen-containing compound; Preferably, the colorant is carbon black.

5. The epoxy resin molding material according to any one of claims 1 to 4, characterized in that: The preparation method of the chemical material comprises: in an inert atmosphere, melting a portion of the second epoxy resin at 155-170° C., then mixing with another portion of the second epoxy resin and performing a first stirring, then mixing with the release agent and the accelerator and performing a second stirring, then mixing with the dispersant and performing a third stirring, then cooling to 135-145° C., and finally discharging the material through a filter screen.

6. The epoxy resin molding material according to any one of claims 1 to 5, characterized in that: The accelerator is an amine accelerator, preferably at least one of epoxidized acetamide, epoxidized propionamide, diazabicyclo and triethylenediamine.

7. The epoxy resin molding material according to any one of claims 1 to 6, characterized in that: The dispersant is a copolymer of α-olefin and maleic anhydride.

8. The epoxy resin molding material according to any one of claims 1 to 7, characterized in that: The release agent is natural wax and / or synthetic wax; Preferably, the natural wax is mineral wax and / or vegetable wax; Preferably, the synthetic wax is polyethylene and / or polyamide wax.

9. A method for preparing the epoxy resin molding material according to any one of claims 1 to 8, characterized in that: The method comprises: in an inert atmosphere, melting and mixing a first epoxy resin, a curing agent, a solid filler, an ion capture agent, a low stress modifier, a coupling agent, a curing accelerator, a chemical material, a flame retardant and a colorant.

10. The method according to claim 9, characterized in that The conditions for the melt mixing include: a temperature of 100-110° C. and a time of 2-20 min.

11. Use of the epoxy resin molding material according to any one of claims 1 to 8 in semiconductor chip packaging.

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