Epoxy resin composition and application

Abstract

The invention relates to an epoxy resin composition and application thereof, the epoxy resin composition comprises the following raw materials: (A) epoxy resin, (B) a curing agent and (C) an inorganic filler, the component (B) curing agent is a mixture at least comprising the following two components: (B1) diethyltoluenediamine; and (B2) a compound with a structure as shown in a formula 1: in the component (B), the content of the compound with the structure as shown in the formula 1 in the component (B2) is 0.2-40% based on the total weight of the component (B). The epoxy resin composition provided by the invention has relatively high Tg and excellent mechanical properties, is free of void after construction, and is suitable for bottom filling of flip packaging of an integrated circuit.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of chip packaging adhesive, and particularly relates to an epoxy resin composition and application. BACKGROUND

[0002] Flip-chip type chips have a structure in which an electrode portion on a substrate (or an interposer) and a semiconductor element are connected via bump electrodes. In such a chip, when heat is supplied by temperature cycling or the like, stress is applied to the bump electrodes due to a difference in thermal expansion coefficient between the substrate (or the interposer) and the chip element, and the bump electrodes can be cracked or the like. In order to suppress the occurrence of such a defect, it is common practice to use a liquid sealant called an underfill adhesive to seal a gap between the chip element and the substrate (or the interposer) and to fix them to each other, thereby improving heat cycle resistance.

[0003] With the market demand for chip computing power increasing, the number of transistors in a single chip increases, and the chip is required to have a larger size. When the size of the chip increases, the stress on the underfill adhesive increases, and how to continue to protect the interconnection material of the underfill adhesive during temperature cycling becomes a new challenge in the field of underfill adhesive materials. At the same time, the increase in the size of the chip also means that the underfill adhesive must have excellent flow filling properties, and voids (hollows, voids, cavities) and other problems cannot occur during the construction phase to avoid failure of the chip.

[0004] Patent CN106687496A provides a kind of liquid epoxy resin composition, uses liquid epoxy resin, with amine curing agent, the amine curing agent is at least contains diethyl toluene diamine, 4, 4'-diamino-3, 3'-diethyl diphenyl methane and dimethyl sulfide toluene diamine one of them. The patent solves the problem of improving the injection property of liquid epoxy resin composition on semiconductor device, and inhibiting the solder angle crack after curing, and does not mention how to avoid void problem in construction process.

[0005] Patent CN101321799B provides a kind of liquid resin composition, uses liquid epoxy resin, with curing agent containing liquid aromatic amine. The patent aims to improve the injection property of liquid resin composition on semiconductor device by adding non-ionic surfactant, does not particularly study the curing agent, and does not involve how to avoid void problem in construction process.

[0006] Patent CN117757222A provides an epoxy resin composition using an epoxy resin, combined with an amine curing agent, which is a combination of diphenylmethane type amine compound and sulfur-containing benzene ring type amine compound. This patent solves the problem of epoxy resin composition with high Tg and good toughness performance by selecting the curing agent, but does not mention how to avoid void problem during construction. SUMMARY

[0007] Therefore, the present application aims to provide an epoxy resin composition with high glass transition temperature (Tg) and excellent construction performance, no void problem after construction and curing, and can meet the bottom filling of large size flip chip.

[0008] To achieve the above-mentioned purpose, the present application adopts the following technical solutions:

[0009] The present application provides an epoxy resin composition, the raw materials of which include the following components by weight:

[0010] (A) Epoxy resin, 18-30 parts, preferably 20-26 parts;

[0011] (B) Curing agent, 7-20 parts, preferably 10-16 parts;

[0012] (C) Inorganic filler, 50-75 parts, preferably 55-70 parts;

[0013] The curing agent of component (B) is a mixture containing at least the following two components:

[0014] (B1) Diethyl toluene diamine;

[0015] (B2) Compound with structure shown in formula 1:

[0016]

[0017] In formula (1), R1, R2, R3, R4, R5 are each independently selected from any one of hydrogen, hydroxyl, mercapto, amine, C1-C6 alkyl; R6 is selected from any one of methylene, sulfur;

[0018] In component (B), the content of compound with structure shown in formula 1 in component (B2) is 0.2-40%, based on the total weight of component (B).

[0019] In an embodiment, the C1-C6 alkyl in the above formula (1) is selected from any one of methyl, ethyl, propyl, n-butyl, t-butyl, n-hexyl.

[0020] In one embodiment, at least one of R1, R2, R3, R4, R5 of the above formula (1) is hydroxyl, thiol or amine group, and at least one is propyl, n-butyl, t-butyl or n-hexyl.

[0021] In one embodiment, the compound having the structure of formula 1 of component (B2) is selected from at least one of 4,4'-diamino-3,3'-di-t-butyl diphenyl methane, 2,2'-methylene bis(6-t-butyl-4-methyl phenol), 2,2'-thio bis(6-t-butyl-4-methyl phenol), 4,4'-methylene bis(2,6-di-t-butyl phenol).

[0022] In one embodiment, the epoxy resin of component (A) is selected from at least one, preferably at least two, of glycidyl ether epoxy resin, glycidyl ester epoxy resin, aliphatic epoxy resin, cycloaliphatic epoxy resin, polycyclic aromatic epoxy resin, phenol novolac epoxy resin and aminophenol epoxy resin; preferably, the epoxy resin is selected from at least two of aliphatic epoxy resin, polycyclic aromatic epoxy resin and aminophenol epoxy resin.

[0023] In one alternative embodiment, the epoxy resin of component (A) is selected from at least one, preferably at least two, of bisphenol F epoxy resin, bisphenol A epoxy resin, naphthalene diol epoxy resin, N,N-bis(glycidyl) o-toluidine, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trisglycidyl-p-aminophenol epoxy resin.

[0024] In one embodiment, the inorganic filler of component (C) is selected from at least one of silica and alumina, preferably silica.

[0025] In one embodiment, the inorganic filler of component (C) has an average particle size of 0.1-3.0 um, preferably 0.3-2.0 um.

[0026] In one embodiment, the inorganic filler of component (C) has a maximum particle size of ≤10 um, preferably ≤5 um.

[0027] In one embodiment, the inorganic filler of component (C) is selected from spherical inorganic filler.

[0028] In one alternative embodiment, the epoxy resin composition of the present application contains conventional additives, organic solvents and the like, such as one or more of optional coupling agent, accelerator, diluent, wetting agent, dispersant, toughening agent, defoamer, pigment, ion capturing agent and the like.

[0029] In one alternative example, the raw materials of the epoxy resin composition include coupling agent, the content being 0.05-2.0 parts by weight.

[0030] In an alternative example, the epoxy resin composition raw material comprises a pigment, and the content is 0.05-2.0 parts by weight.

[0031] The application also provides the use of the above-mentioned epoxy resin composition, which is suitable for the field of electronic device packaging, especially for the bottom filling of flip chip packaging.

[0032] Compared with the prior art, the application has the following positive effects:

[0033] The epoxy resin composition of the application has high Tg and mechanical strength, and after being used for the bottom filling of flip chip packaging, the epoxy resin body is not prone to cracking in the reliability stage; meanwhile, due to the presence of component (B2), the epoxy resin composition has defoaming effect in the flow filling stage, and is not prone to void; and component (B2) as a curing agent can also become part of the crosslinking system of the epoxy resin in the curing stage, and will not affect the bulk properties of the epoxy resin composition.

[0034] The curing agent of the application uses components (B1) and (B2) in combination, so that the epoxy resin composition has high Tg, high high-temperature modulus and high high-temperature breaking strength, and especially when applied to the form of chip packaging, can effectively avoid the appearance of holes at the edge of the device, thereby improving the reliability of the packaged device. BRIEF DESCRIPTION OF DRAWINGS

[0035] Figures 1-4 SAT test results of Examples 1-4 in sequence;

[0036] Figures 5-6 SAT test results of Comparative Examples 1-2 in sequence;

[0037] Figure 7 Test device used for void condition detection, wherein: ① is a bare chip die1, ② is a bare chip die2, ③ is a copper bump, and ④ is an interposer. DETAILED DESCRIPTION

[0038] Hereinafter, the contents of the application will be described in detail. It should be noted that the endpoints and any values of the ranges disclosed in the present specification are not limited to the precise range or value, and these ranges or values should be understood to include values close thereto. For numerical ranges, the endpoint values of each range, the endpoint values of each range and individual point values, and individual point values can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0039] Preferred embodiments of the present application will be described in more detail below. Although preferred embodiments of the present application are shown in the examples, it should be understood that the present application can be implemented in various forms and should not be limited by the embodiments set forth herein.

[0040] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application.

[0041] In the present application, "at least one" means any one, any two or more than two of the listed items.

[0042] In the present application, in the technical features described in an open form, both the closed technical solution consisting of the listed features and the open technical solution containing the listed features are included.

[0043] In the embodiments of the present application, an epoxy resin composition is provided, which includes the following components in parts by weight:

[0044] (A) an epoxy resin, 18-30 parts, including but not limited to 18 parts, 20 parts, 22 parts, 24 parts, 26 parts, 28 parts, 30 parts or a range consisting of any two of them, preferably 20-26 parts;

[0045] (B) a curing agent, 7-20 parts, including but not limited to 7 parts, 10 parts, 12 parts, 14 parts, 16 parts, 18 parts, 20 parts or a range consisting of any two of them, preferably 10-16 parts;

[0046] (C) an inorganic filler, 50-75 parts, including but not limited to 50 parts, 52 parts, 54 parts, 56 parts, 58 parts, 60 parts, 62 parts, 65 parts or a range consisting of any two of them, preferably 55-70 parts;

[0047] The curing agent of component (B) is a mixture containing at least the following two components:

[0048] (B1) diethyltoluene diamine;

[0049] (B2) a compound having the structure shown in Formula 1:

[0050]

[0051] In formula (1), R1, R2, R3, R4, R5 are each independently selected from any one of hydrogen, hydroxyl (-OH), mercapto (-SH), amine (-NH2), C1-C6 alkyl; R6 is selected from any one of methylene (-CH2-), sulfur (-S-); wherein the C1-C6 alkyl is preferably selected from any one of methyl, ethyl, propyl, n-butyl, t-butyl, n-hexyl;

[0052] In component (B), the content of the compound having the structure shown in formula 1 in component (B2) is 0.2-40%, including but not limited to 0.2%, 0.5%, 1%, 5%, 10%, 15%, 20%, 25%, 30%, 35%, 40% or a range consisting of any two of them, based on the total weight of component (B).

[0053] In some preferred embodiments, at least one of R1, R2, R3, R4, R5 in formula (1) is hydroxyl, mercapto or amine, and at least one is propyl, n-butyl, t-butyl or n-hexyl.

[0054] In the above preferred embodiments, when the substituent of formula (1) structure contains polar groups such as hydroxyl, mercapto or amine, it can provide groups that can react with epoxy resin, and when the substituent contains non-polar groups such as propyl, n-butyl, t-butyl or n-hexyl, the formula (1) structure is easy to spread on the bubble film surface, reducing the surface tension, thereby having better high-temperature defoaming effect. In addition, the presence of groups such as propyl, n-butyl, t-butyl or n-hexyl can produce suitable steric hindrance effect, thereby regulating the moderate reactivity of groups such as hydroxyl, mercapto or amine, ensuring that it reacts with the main chain of the system further after achieving high-temperature defoaming effect.

[0055] In some embodiments, the compound having the structure shown in formula 1 in component (B2) is selected from at least one of 4,4'-diamino-3,3'-di-t-butyl diphenyl methane, 2,2'-methylene bis(6-t-butyl-4-methyl phenol), 2,2'-thio bis(6-t-butyl-4-methyl phenol), 4,4'-methylene bis(2,6-di-t-butyl phenol).

[0056] In practical applications, the source of the compound of component (B2) is not limited, and can be any compound conforming to the structure of Formula 1 disclosed or not disclosed in the prior art, for example, 2,2'-methylenebis(6-tert-butyl-4-methylphenol), CAS: 119-47-1, 2,2'-thiobis(6-tert-butyl-4-methylphenol), CAS: 90-66-4, 4,4'-methylenebis(2,6-di-tert-butylphenol), CAS: 118-82-1, which are common commercially available products and can be directly purchased; for example, 4,4'-diamino-3,3'-di-tert-butyl diphenylmethane is a product disclosed in the prior art, which can be obtained by customization or self-preparation, and one of the preparation methods can refer to the literature “Synthesis of 3,3'-di-tert-butyl-4,4'-diamino diphenylmethane, Thermosetting Resin, 2013, 28(01)”.

[0057] In the present application, the epoxy resin of component (A) is not particularly required in terms of its category, and can be selected from compounds containing an epoxy group, which can be conventionally selected in the art, for example, in the examples, at least one selected from the group consisting of glycidyl ether epoxy resins, glycidyl ester epoxy resins, aliphatic epoxy resins, alicyclic epoxy resins, polycyclic aromatic epoxy resins, phenolic epoxy resins, and aminophenol epoxy resins, preferably at least two selected from the group consisting of aliphatic epoxy resins, polycyclic aromatic epoxy resins, and aminophenol epoxy resins; or other compounds containing an epoxy group, such as N,N-bis(glycidyl) o-toluidine, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, etc., which are also classified as epoxy resins in the industry.

[0058] In some optional embodiments, the epoxy resin of component (A) is at least one, preferably at least two, selected from the group consisting of bisphenol F epoxy resins, bisphenol A epoxy resins, naphthalenediol epoxy resins, N,N-bis(glycidyl) o-toluidine, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and triglycidyl p-aminophenol epoxy resins.

[0059] In the present application, the inorganic filler of component (C) can be selected from materials commonly selected in the art, for example, at least one selected from the group consisting of silicon dioxide and aluminum oxide, preferably silicon dioxide.

[0060] In some optional embodiments, the average particle size (D50) of the inorganic filler of component (C) is 0.1-3.0 um, including but not limited to 0.1 um, 0.5 um, 1.0 um, 1.3 um, 1.5 um, 1.8 um, 2.0 um, 2.3 um, 2.5 um, 2.8 um, 3.0 um, or a range consisting of any two of them, preferably 0.3-2.0 um.

[0061] In some optional embodiments, the inorganic filler has a maximum particle size (D100) of ≤10 um, including but not limited to 10 um, 9 um, 8 um, 7 um, 6 um, 5 um, 4 um, 3 um, 2 um, 1 um, 0.5 um, 0.1 um, or a range between any two of them, preferably ≤5 um.

[0062] In some embodiments, the inorganic filler of component (C) is a spherical inorganic filler.

[0063] In some embodiments, the epoxy resin composition of the present application can further contain conventional additives, organic solvents, and the like, such as coupling agents, accelerators, diluents, wetting agents, dispersants, toughening agents, defoaming agents, pigments, ion capturing agents, and the like, without impairing the technical effects.

[0064] In specific embodiments, the selection and amount thereof can be screened by the skilled person according to experience, and are not specifically limited.

[0065] In some specific embodiments, the epoxy resin composition raw material includes a coupling agent, and the amount of the coupling agent is not particularly limited, and is optionally 0.05-2.0 parts by weight, including but not limited to 0.05 parts, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1.0 parts, 1.3 parts, 1.5 parts, 1.8 parts, 2.0 parts, or a range between any two of them.

[0066] The coupling agent is a conventional selection in the art, and is optionally at least any one of vinyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethane trimethoxysilane, 3-glycidyloxypropyl trimethoxysilane, 3-glycidyloxypropyl triethoxysilane, styryltrimethoxysilane, 3-methacryloyloxypropyl methyldimethoxysilane, 3-acryloxypropyl trimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, (1,3-dimethyl-butylidene)propylaminotrimethoxysilane, N-phenyl-3-aminopropyl trimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl trimethoxysilane, N-(benzyl)-2-aminoethyl-3-aminopropyl trimethoxysilane, 3-ureidopropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, and the like.

[0067] In one specific example, the epoxy resin composition raw material includes a pigment, the amount of which is not particularly limited, and is optionally 0.05-2.0 parts by weight, including but not limited to 0.05 parts, 0.1 parts, 0.3 parts, 0.5 parts, 0.8 parts, 1.0 parts, 1.3 parts, 1.5 parts, 1.8 parts, 2.0 parts, or a range consisting of any two of the foregoing; and preferably 0.1 mass% or more.

[0068] The pigment type is not particularly limited and is routinely selected in the art, and for example, can be at least any one of carbon black, titanium black such as titanium nitride, black organic pigments, mixed color organic pigments, and inorganic pigments. The pigment can be used alone or in combination of two or more.

[0069] The epoxy resin composition provided by the present application does not have a particular requirement for its preparation method, and can be prepared by routine operation in the art, for example, in some specific examples, a physical blending method is used, and the raw materials are mixed.

[0070] In some optional embodiments, the preparation method of the epoxy resin composition is as follows: the epoxy resin, coupling agent, and pigment are mixed (for example, mixed at a speed of 800-2000 rpm for 20-60 min) to obtain a first mixture; the inorganic filler is added to the first mixture and mixed (for example, mixed at a speed of 800-2000 rpm for 30-60 min) to obtain a second mixture; the curing agent is added to the second mixture and mixed (mixed for 10-30 min), and vacuum degassing (5-30 min) is performed to obtain the epoxy resin composition.

[0071] The epoxy resin composition provided by the present application has a relatively high glass transition temperature Tg, which can reach 150℃ or more, and excellent construction performance, and has no void problem after construction, and can meet the bottom filling of 2.5D and other complex packaging forms.

[0072] The epoxy resin composition of the present application is used in the field of electronic device packaging, such as the bottom filling of flip chip packaging, and does not have a particular requirement for the operating conditions, and can be used by using a routine method in the art.

[0073] Hereinafter, the epoxy resin composition provided by the present application is described in detail through specific examples.

[0074] Unless otherwise specified, the reagents, materials, and instruments used in the following examples are all conventional reagents, conventional materials, and conventional instruments in the art, and can be obtained by commercial purchase, and the reagents involved can also be obtained by a conventional method in the art.

[0075] The sources of the main raw materials used in the embodiments and comparative examples of the present application are as follows, and other raw materials and reagents are purchased from commercial suppliers unless otherwise specified:

[0076] Diethyltoluene diamine: Henan Leibai Rui New Material Science and Technology Co., Ltd.;

[0077] 4,4'-Methylene bis(2,6-di-tert-butylphenol): Araldite Reagent (Shanghai) Co., Ltd.;

[0078] 2,2'-Thiobis(6-tert-butyl-4-methylphenol): Araldite Reagent (Shanghai) Co., Ltd.;

[0079] 4,4'-Methylene bis(2,6-di-tert-butylphenol): Araldite Reagent (Shanghai) Co., Ltd.;

[0080] 4,4'-Diamino-3,3'-di-tert-butyl diphenylmethane: that is, 3,3'-di-tert-butyl-4,4'-diamino diphenylmethane, which is prepared according to the method disclosed in “Synthesis of 3,3'-Di-tert-butyl-4,4'-diamino diphenylmethane, Thermosetting Resin, 2013, 28(01)”;

[0081] Triglycidyl p-aminophenol epoxy resin: epoxy equivalent weight 94, JER630, Mitsubishi Chemical Corporation;

[0082] Bisphenol F epoxy resin: epoxy equivalent weight 158, KF-8110, Hunan Sailve New Material;

[0083] Naphthalene diol epoxy resin: epoxy equivalent weight 140, EBA-65, Shanghai Huayi Resin Co., Ltd.;

[0084] Bisphenol A epoxy resin: epoxy equivalent weight 173, ZL-600, Zhi Lun Super Pure Epoxy Resin Co., Ltd.;

[0085] Spherical silica filler: BQ025, D50 is 0.95 um, D100≤5 um, Suzhou Jin Yi New Material Science and Technology Co., Ltd.;

[0086] Spherical silica filler: BQ0011, D50 is 0.6 um, D100≤5 um, Suzhou Jin Yi New Material Science and Technology Co., Ltd.;

[0087] Spherical alumina filler: QY2, D50 is 2.3 um, D100≤10 um, Suzhou Jin Yi New Material Science and Technology Co., Ltd.;

[0088] Coupling agent KBM403, Shin-Etsu Chemical Co., Ltd.;

[0089] Pigment MA600, Mitsubishi Chemical Corporation.

[0090] The present application will be further described by more specific examples.

[0091] Example 1:

[0092] The raw material weight parts of the epoxy resin composition are composed of:

[0093] Epoxy resin: 12.0 parts of triglycidyl-p-aminophenol epoxy resin, 6.0 parts of bisphenol A epoxy resin;

[0094] Curing agent: 8.7 parts, in which diethyl toluene diamine accounts for 65wt%, 4,4'-diamino-3,3'-di-tert-butyl diphenyl methane accounts for 35wt%;

[0095] Spherical silica filler BQ025: 72.0 parts;

[0096] Coupling agent KBM403: 0.8 parts;

[0097] Pigment MA600: 0.5 parts.

[0098] The preparation method of the above epoxy resin composition is: according to weight parts, mix the triglycidyl-p-aminophenol epoxy resin, bisphenol A epoxy resin, coupling agent, pigment at 1600 rpm for 20 min to obtain a first mixture; add the spherical silica filler to the first mixture, mix at 1600 rpm for 30 min to obtain a second mixture; add the curing agent to the second mixture, mix for 10 min, and vacuum degassing for 5 min to obtain the epoxy resin composition.

[0099] Example 2:

[0100] The raw material weight parts of the epoxy resin composition are composed of:

[0101] Epoxy resin: 5.0 parts of bisphenol F epoxy resin, 21.0 parts of triglycidyl-p-aminophenol epoxy resin;

[0102] Curing agent: 11.5 parts, in which diethyl toluene diamine accounts for 99.2wt%, 4,4'-methylene bis(2,6-di-tert-butyl phenol) accounts for 0.8wt%;

[0103] Spherical silica filler BQ025: 61.0 parts;

[0104] Coupling agent KBM403: 0.5 parts;

[0105] Pigment MA600: 1.0 parts.

[0106] The preparation method of the epoxy resin composition is as follows: by weight parts, the bisphenol F epoxy resin, the trisglycidyl-p-aminophenol epoxy resin, the coupling agent, and the pigment are mixed at a speed of 1600 rpm for 30 min to obtain a first mixture; the spherical inorganic filler is added into the first mixture, and mixed at a speed of 1600 rpm for 60 min to obtain a second mixture; the curing agent is added into the second mixture, mixed for 20 min, and vacuum degassed for 10 min to obtain the epoxy resin composition.

[0107] Example 3:

[0108] The raw material weight parts of the epoxy resin composition are as follows:

[0109] Epoxy resin: bisphenol F epoxy resin 3.0 parts, bisphenol A epoxy resin 3.0 parts, trisglycidyl-p-aminophenol epoxy resin 16.0 parts;

[0110] Curing agent: 11.2 parts, wherein the diethyl toluene diamine accounts for 90wt%, and the 2,2'-methylene bis(6-tert-butyl-4-methylphenol) accounts for 10wt%;

[0111] Spherical alumina filler QY2: 65.0 parts;

[0112] Coupling agent KBM403: 1.5 parts;

[0113] Pigment MA600: 0.3 parts.

[0114] The preparation method of the epoxy resin composition is as follows: by weight parts, the bisphenol F epoxy resin, the bisphenol A epoxy resin, the trisglycidyl-p-aminophenol epoxy resin, the coupling agent, and the pigment are mixed at a speed of 1600 rpm for 30 min to obtain a first mixture; the spherical inorganic filler is added into the first mixture, and mixed at a speed of 1600 rpm for 80 min to obtain a second mixture; the curing agent is added into the second mixture, mixed for 15 min, and vacuum degassed for 10 min to obtain the epoxy resin composition.

[0115] Example 4:

[0116] The raw material weight parts of the epoxy resin composition are as follows:

[0117] Epoxy resin: bisphenol F epoxy resin 3.5 parts, trisglycidyl-p-aminophenol epoxy resin 17.6 parts;

[0118] Curing agent: 11.6 parts, wherein the diethyl toluene diamine accounts for 75wt%, and the 4,4'-diamino-3,3'-di-tert-butyl diphenyl methane accounts for 25wt%;

[0119] Spherical silica filler BQ0011: 66.0 parts;

[0120] Coupling agent KBM403: 1.0 part;

[0121] Pigment MA600: 0.5 parts.

[0122] The preparation method of the above epoxy resin composition is as follows: the bisphenol F epoxy resin, the trisglycidyl-p-aminophenol epoxy resin, the coupling agent, and the pigment are mixed at 1600 rpm for 30 min to obtain a first mixture; the spherical silica filler is added to the first mixture, and mixed at 1600 rpm for 80 min to obtain a second mixture; the curing agent is added to the second mixture, mixed for 15 min, and vacuum degassed for 10 min to obtain the epoxy resin composition.

[0123] Comparative Example 1:

[0124] With reference to Example 4, the only difference is that the curing agent is as follows: the diethyl toluene diamine accounts for 99.85wt%, and the 4,4'-methylene bis(2,6-di-tert-butyl phenol) accounts for 0.15wt%, and other operations and conditions remain unchanged, to obtain the epoxy resin composition.

[0125] Comparative Example 2:

[0126] With reference to Example 4, the only difference is that the curing agent is as follows:

[0127] The curing agent is as follows: the diethyl toluene diamine accounts for 58wt%, and the 4,4'-methylene bis(2,6-di-tert-butyl phenol) accounts for 42wt%, and other operations and conditions remain unchanged, to obtain the epoxy resin composition.

[0128] The epoxy resin compositions of Examples 1-4 and Comparative Examples 1-2 are tested for performance as follows:

[0129] I. Test method for glass transition temperature Tg and 240℃ storage modulus of the epoxy resin composition:

[0130] The epoxy resin composition is cured at 150℃ for 2h, and then the cured block is cut into

[0131] a sample bar with a shape of 60mm*12.5mm*3.3mm;

[0132] Using the DMA450 equipment of TA company, the sample bar is tested for temperature rise from 25℃ to 300℃ in a double cantilever measurement mode, the temperature rise rate is 5℃ / min, the temperature corresponding to the peak value of tanδ is taken as the glass transition temperature Tg of the epoxy resin composition, and the value of the storage modulus at 240℃ is read.

[0133] II. Test method for high temperature tensile strength of the epoxy resin composition:

[0134] The epoxy resin composition was cured at 150°C for 2h, and then the cured block was cut into

[0135] 8mm*3.2mm*0.2mm shaped sample;

[0136] The sample was tested at 270°C with a force loading of 5N / min using a DMA450 device of TA Corporation in a tensile measurement mode, and the corresponding strength value at the time of sample fracture was read.

[0137] III. Test method of bending strength of the epoxy resin composition:

[0138] The epoxy resin composition was cured at 150°C for 2h, and then the cured block was cut into

[0139] 80mm*12.5mm*3.3mm shaped sample;

[0140] The sample was tested at room temperature in a three-point bending mode using a universal testing machine device, and the stress at the time of sample fracture was read, and the bending strength σb of the epoxy resin composition was calculated according to Formula 1.

[0141]

[0142] IV. Void detection method: After the epoxy resin composition is cured, the SAT (ultrasonic scanning microscope) method is used for testing, and the testing device is as shown in Figure 7 The main structure of the testing device is composed of two bare chips (Die1 and Die2), copper bumps and an interposer, and the overall size is about 18mm*18mm*1.5mm. The main material of the bare chip is silicon; the copper bump is composed of a copper column and a tin cap (not shown in the figure), the distance between the copper bump and the copper bump is 35-100um; the surface material of the interposer is polyimide (PI); the bare chip and the interposer are welded together through the copper bump, and the distance between the bare chip and the interposer is 40±2um. Figure 7

[0143] Specific test method: continuous dispensing operation was performed on the testing device, the dispensing weight of the epoxy resin composition was fixed at 30mg, and the dispensing program of continuous 5 dispensing was fixed. After dispensing, the device was placed in a pressure oven for curing, and the curing conditions were: stage I: 100°C for 1h, pressure 7kg; stage II: 150°C

[0144] 2h, pressure 7kg.

[0145] The performance indicators of the epoxy resin composition tested according to the above method are shown in Table 1.

[0146] Table 1 Performance comparison in examples and comparative examples ​

[0147]

[0148] From the above table, it can be seen that the epoxy resin composition of the embodiment of the present application has high Tg and bending strength when bottom filling in the form of flip-chip packaging, and does not have the problem of void after curing.

Claims

1. An epoxy resin composition, characterized by comprising: The raw materials include the following components by weight: (A) an epoxy resin, 18-30 parts, preferably 20-26 parts; (B) a curing agent, 7-20 parts, preferably 10-16 parts; (C) an inorganic filler, 50-75 parts, preferably 55-70 parts; The curing agent of component (B) is a mixture comprising at least the following two components: (B1) diethyl toluene diamine; (B2) a compound having the structure shown in formula 1: In formula (1), R1, R2, R3, R4, R5 are each independently selected from any one of hydrogen, hydroxyl, mercapto, amine, C1-C6 alkyl; R6 is selected from any one of methylene, sulfur; In component (B), the content of the compound having the structure shown in formula 1 of component (B2) is 0.2-40% based on the total weight of component (B).

2. The epoxy resin composition according to claim 1, characterized in that, The C1-C6 alkyl of formula (1) is selected from any one of methyl, ethyl, propyl, n-butyl, t-butyl, n-hexyl.

3. The epoxy resin composition according to claim 1 or 2, characterized in that, At least one of R1, R2, R3, R4, R5 of the above formula (1) is hydroxyl, mercapto or amine, and at least one is propyl, n-butyl, t-butyl or n-hexyl.

4. The epoxy resin composition according to any one of claims 1 to 3, characterized in that, The compound having the structure shown in formula (1) of component (B2) is selected from at least one of 4,4'-diamino-3,3'-di-t-butyl diphenyl methane, 2,2'-methylene bis(6-t-butyl-4-methyl phenol), 2,2'-thio bis(6-t-butyl-4-methyl phenol), 4,4'-methylene bis(2,6-di-t-butyl phenol).

5. The epoxy resin composition according to any one of claims 1 to 4, characterized in that, The epoxy resin of component (A) is selected from at least one of glycidyl ether epoxy resin, glycidyl ester epoxy resin, aliphatic epoxy resin, alicyclic epoxy resin, polycyclic aromatic epoxy resin, phenolic type epoxy resin and aminophenol type epoxy resin, preferably at least two; Preferably, the epoxy resin is selected from at least two of aliphatic epoxy resin, polycyclic aromatic epoxy resin, aminophenol type epoxy resin.

6. The epoxy resin composition according to any one of claims 1 to 5, characterized in that, The epoxy resin of component (A) is selected from at least one of bisphenol F epoxy resin, bisphenol A epoxy resin, naphthalenediol epoxy resin, N,N-bis(glycidyl) o-toluidine, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, trisglycidyl p-aminophenol epoxy resin, preferably at least two.

7. The epoxy resin composition according to any one of claims 1 to 6, characterized in that, The inorganic filler of component (C) is selected from at least one of silica, alumina, preferably silica; and / or The inorganic filler of component (C) has an average particle size of 0.1-3.0 um, preferably 0.3-2.0 um; and / or The inorganic filler of component (C) has a maximum particle size of ≤10 um, preferably ≤5 um; and / or The inorganic filler of component (C) is selected from spherical inorganic fillers.

8. The epoxy resin composition according to any one of claims 1 to 7, characterized in that, The epoxy resin composition contains one or more of conventional additives, organic solvents, such as optional coupling agents, accelerators, diluents, wetting agents, dispersants, toughening agents, defoamers, pigments, ion capture agents.

9. The epoxy resin composition according to any one of claims 1 to 8, characterized in that, The raw materials of the epoxy resin composition include a coupling agent, the content of which is 0.05-2.0 parts by weight; and / or The raw material of the epoxy resin composition comprises pigments, the content being 0.05-2.0 parts by weight.

10. Use of the epoxy resin composition according to any one of claims 1 to 9, characterized in that The present application relates to a method for encapsulating electronic devices, and more particularly to a method for encapsulating electronic devices using a bottom filler, especially for flip chip packaging.

Images