Epoxy resin composition adhesive as well as preparation method and application thereof

Abstract

The invention relates to an epoxy resin composition adhesive as well as a preparation method and application thereof. The epoxy resin composition adhesive is prepared from the following raw materials: (A) epoxy resin, (B) an amine curing agent, (C) a composite spherical inorganic filler and (D) a coupling agent, wherein the component (C) composite spherical inorganic filler is composed of two parts: a spherical inorganic filler 1, which is spherical silica with an average particle size of 0.1-3 [mu] m, and the surface of the spherical inorganic filler 1 is modified by an epoxy silane coupling agent; the spherical inorganic filler 2 is one or two of spherical silicon dioxide or aluminum oxide with the average particle size of 5-60nm, and the surface of the spherical inorganic filler 2 is modified by a phenyl silane coupling agent. The epoxy resin composition adhesive provided by the invention is suitable for the bottom filling of flip packaging of an integrated circuit, is especially suitable for the bottom filling of a high-density RDL fan-out packaging form, and has excellent flow filling property and reliability under a wafer-level dispensing process and a narrow-spacing heterogeneous chip structure.

Description

Technical Field

[0001] The invention belongs to the technical field of chip packaging adhesives, and specifically relates to an epoxy resin composition adhesive and application thereof. Background Art

[0002] The flip-chip type chip has a structure in which the electrode portion on the substrate (or interposer) and the semiconductor element are connected via a bump electrode. The chip with this structure has the following problem: when heat is supplied by temperature cycling, due to the difference in thermal expansion coefficient between the substrate (or interposer) and the chip element, stress is generated and applied to the bump electrode, and the bump electrode may crack and other undesirable phenomena may occur. In order to suppress the occurrence of such undesirable phenomena, it is common practice to use a liquid sealant called bottom filler to seal the gap between the chip element and the substrate (or interposer) to fix the two to each other, thereby improving the heat cycle resistance.

[0003] With the development of miniaturization, lightweight and high performance of chips, 2.5D / 3D packaging dominated by chiplet packaging has become the leading direction of chip packaging in recent years. High-density RDL fan-out packaging is a form of 2.5D advanced packaging. By replacing the silicon interposer with RDL, the chip cost can be greatly reduced. It is the mainstream technology for balancing the high computing power and cost of chips at this stage. In the high-density RDL fan-out packaging process, heterogeneous chips are integrated by stacking and wafer-level packaging is performed. The liquid sealant used as the bottom filler is required to have excellent injectability, adhesion, curing and storage stability, etc., and no gaps are generated. In addition, due to the increasing integration of heterogeneous chips, the spacing between integrated units on the wafer is getting narrower and narrower, and some designs are even less than 1500μm. This can easily lead to the problem of glue contacting each other between integrated units during continuous dispensing operations, causing product failure, which poses a great challenge to the flow filling performance of the bottom filler.

[0004] Patent CN 106687496 A provides a liquid semiconductor encapsulant that has excellent injectability for a flip-chip semiconductor device with a fine-pitch wiring pattern and inhibits solder fillet cracks after curing. The fluidity of the bottom filler is improved by using a low-viscosity liquid epoxy resin containing aminophenol-type epoxy resin. However, the fluidity test data provided in the patent was obtained by testing on a glass sheet, which is difficult to prove its flow condition in a real chip.

[0005] Patent CN106232763B provides a liquid packaging material, using a silica filler with an average particle size of 7 to 50 nm treated with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and a silica filler with an average particle size of 0.2 to 5 μm, and the ratio (mass ratio) is 1:10.2 to 1:559, so as to achieve good injectability for narrow gap chip packaging. This patent solves the problem that the addition of silica fillers with a particle size of nm leads to increased product viscosity and poor injectability. It is suitable for ordinary flip-chip bottom filling, and does not mention high-density RDL fan-out packaging with narrow unit spacing.

[0006] Patent CN117736676A provides an epoxy resin composition adhesive, which uses an inorganic filler D10 of 0.1μm-0.4μm, D50 of 0.5μm-1.1μm, and D90 of 1.3μm-2.9μm, achieving the effect of low viscosity and high fluidity. However, the patent does not focus on the effect of high-density RDL fan-out packaging under narrow unit spacing, and the adhesive material is still very prone to the problem of adjacent integrated units being glued together under low viscosity. Summary of the invention

[0007] The purpose of the present invention is to address the gaps in the above technology and provide an epoxy resin composition adhesive with excellent flow filling ability under capillary force, which is suitable for bottom filling of high-density RDL fan-out packaging, matching the wafer-level dispensing process, and under the narrow-pitch heterogeneous chip structure, even if a very short dispensing delay parameter is set, it can also show excellent operating performance, thereby improving the overall production efficiency of chip packaging.

[0008] Another object of the present invention is to provide application of the epoxy resin composition adhesive.

[0009] In order to achieve the above object, the present invention adopts the following technical solutions:

[0010] An epoxy resin composition adhesive, the raw materials of which include the following components in parts by weight:

[0011] (A) epoxy resin, 18-30 parts by weight, for example, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30 parts by weight, preferably 20-26 parts by weight;

[0012] (B) an amine curing agent, 7-20 parts by weight, for example, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20 parts by weight, preferably 10-16 parts by weight;

[0013] (C) composite spherical inorganic filler, 50-75 parts by weight, for example, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73,

[0014] 74, 75 parts by weight, preferably 55-70 parts by weight;

[0015] (D) coupling agent, 0.1-5 parts by weight, for example, 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, 1.0, 1.5, 2.0, 2.5, 3.0, 3.5, 4.0, 4.5, 5.0 parts by weight, preferably 0.5-1.0 parts by weight;

[0016] The composite spherical inorganic filler of component (C) is composed of two parts: spherical inorganic filler 1, spherical silica with an average particle size of 0.1 μm-3 μm, such as 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, etc., the surface of which is modified by an epoxy silane coupling agent, and the weight percentage relative to component (C) is 95-99.8wt%, such as 95.5%, 96%, 96.5%, 97%, 97.5%, 98%, 98.5%, 99%, 99.5%, 99.6%, 99.7%, etc.; spherical inorganic filler 2, with an average particle size of 5-6 One or both of spherical silica or alumina with a diameter of 0 nm, for example, 8 nm, 10 nm, 15 nm, 20 nm, 25 nm, 30 nm, 35 nm, 40 nm, 45 nm, 50 nm, 55 nm, 60 nm, etc., the surface of which is modified by a phenyl silane coupling agent, and the weight percentage relative to component (C) is 0.2-5wt%, for example, 0.2wt%, 0.5wt%, 1.0wt%, 1.5wt%, 2.0wt%, 2.5wt%, 3.0wt%, 3.5wt%, 4.0wt%, 4.5wt%, 5.0wt%, etc.

[0017] In the present invention, the epoxysilane coupling agent refers to a coupling agent containing both an epoxy group and a siloxane group, including but not limited to 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, preferably 3-glycidyloxypropyltrimethoxysilane and 3-glycidyloxypropyltriethoxysilane.

[0018] In the present invention, the phenylsilane coupling agent refers to a coupling agent containing both a phenyl group and a siloxane group, including but not limited to one or more of phenyltrimethoxysilane, phenyltriethoxysilane, p-styrenetrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane, preferably phenyltrimethoxysilane and phenyltriethoxysilane.

[0019] In the present invention, the epoxy resin of component (A) is selected from at least two 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 of bisphenol F epoxy resin, bisphenol A epoxy resin, naphthalene diol epoxy resin, N,N-di(glycidyl)-o-toluidine, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and triglycidyl-p-aminophenol epoxy resin.

[0020] In the present invention, the component (B) amine curing agent is at least one of 4,4'-diamino-3,3'-diethyldiphenylmethane, diethyltoluenediamine, diaminodiphenyl sulfone, m-aminomethylamine, benzyl diamine trimer, bis-benzyl amino ether, dimethylthiotoluenediamine, and ethylaniline, preferably at least one of 4,4'-diamino-3,3'-diethyldiphenylmethane, diethyltoluenediamine, and dimethylthiotoluenediamine.

[0021] In the present invention, the roundness of the spherical inorganic filler is 0.8-1, such as 0.85, 0.9, 0.95, etc., preferably 0.9-1.

[0022] In the present invention, the circularity is defined as "the ratio of the minimum particle size to the maximum particle size of particles" in a two-dimensional image observed using a scanning electron microscope (SEM).

[0023] In the present invention, the coupling agent of the component (D) may be a vinyl, epoxy, methacryl, amino, mercapto, or other organic silane coupling agent. Among them, epoxy organic silane coupling agents are preferred because they have excellent effects on improving the sealing properties and mechanical strength of semiconductor resin encapsulation materials when used as an underfill.

[0024] In addition, the resin composition adhesive may further contain additives such as accelerators, diluents, wetting agents, dispersants, toughening agents, defoamers, pigments, ion scavengers, or organic solvents within the range that does not impair the effects of the present invention.

[0025] In the present invention, the accelerator is at least one selected from imidazole derivatives, triphenylphosphine, triphenyl phosphate, quaternary ammonium salts and quaternary phosphonium salts.

[0026] In the present invention, the preparation method of the epoxy resin composition adhesive comprises the following steps:

[0027] Mixing the epoxy resin (A) and the coupling agent (D) uniformly to obtain a first mixture;

[0028] Adding the composite spherical inorganic filler as component (C) to the first mixture and mixing them evenly to obtain a second mixture;

[0029] The component (B) amine curing agent is added into the second mixture, mixed evenly, and vacuum degassed to obtain an epoxy resin composition adhesive.

[0030] The application of the epoxy resin composition adhesive of the present invention in chip packaging is particularly suitable for bottom filling of high-density RDL fan-out packaging.

[0031] Compared with the prior art, the present invention has the following positive effects:

[0032] When the epoxy resin composition adhesive of the present invention is used for bottom filling of a high-density RDL fan-out package, even if a shorter dispensing delay parameter is set, excellent operating performance can be exhibited, and there will be no contact between the epoxy resin composition adhesives of adjacent chip integrated units. As for the cause of the excellent effect, the inventor believes through a large number of experimental investigations that the present invention limits the amount of composite spherical inorganic filler added, the average particle size, and the surface modification treatment method. Under the conditions defined in the present invention, the spherical inorganic filler can effectively form a dense accumulation, and at the same time has a suitable wetting effect on the polyimide substrate, so the flow rate is fast, and it is not easy to have the operational failure problem of contact between the epoxy resin composition adhesives of adjacent chip integrated units. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 It is a schematic diagram of a device for testing the flow rate of the epoxy resin composition adhesive of the present invention.

[0034] Figure 2 It is a schematic diagram of a device for testing the flow and filling effect of the epoxy resin composition adhesive of the present invention. DETAILED DESCRIPTION

[0035] The preferred embodiments of the present invention will be described in more detail below. Although the preferred embodiments of the present invention are shown in the examples, it should be understood that the present invention can be implemented in various forms and should not be limited to the embodiments set forth herein.

[0036] 1. Test method for flow rate of epoxy resin composition adhesive:

[0037] Test device: such as Figure 1As shown, two clean glass sheets parallel to each other are used to perform the flow velocity test, and the upper and lower gaps of the fixed glass sheets are 30 μm and the width is 10 mm.

[0038] Test method: Dispense 0.2g of glue at the gap between the glass sheets, start timing when the glue contacts the gap between the glass sheets, and stop timing when the epoxy resin composition adhesive flows a distance of 30mm, and record the flow time.

[0039] 2. Test method for wetting and spreading of epoxy resin composition adhesive on high-density RDL substrate:

[0040] Test device: A layer of photosensitive polyimide resin was spin-coated on an 8-inch silicon wafer and cured to obtain a polyimide substrate.

[0041] Test method: Use a wafer-level dispenser to dispense the epoxy resin composition adhesive onto the test device, dispense 2.5mg±0.5mg of adhesive each time, and place it on a 100℃ hot stage for 10 minutes. Test the area of ​​the circle formed by the epoxy resin composition adhesive after spreading. The ratio of the circular area to the amount of adhesive is defined as the dot diameter, in mm. 2 / mg.

[0042] 3. Test method for flow filling effect of epoxy resin composition adhesive under wafer-level dispensing process:

[0043] Test device: such as Figure 2 As shown, the device is divided into a top die and an interposer. The main material of the top die is silicon. Two dies form an integrated unit. Each integrated unit is 18mm*18mm in size. The distance between the integrated units is 2500μm. Each integrated unit is implanted with copper bumps through the 1P1M process. The interposer is a 12-inch wafer with a surface material of polyimide. The topdie and the interposer have been welded together through copper bumps, and the SOH is 40±2μm.

[0044] Test method: select any two adjacent integrated units for continuous glue dispensing operation, fix the glue weight of the epoxy resin composition adhesive to 30 mg, fix the glue dispensing procedure for 5 consecutive glue dispensing strokes, and observe whether there is glue contact between the two adjacent integrated units.

[0045] 4. Source of raw materials:

[0046] 1. C-1, a composite spherical inorganic filler, wherein component 1, spherical silica with an average particle size of 1.7 μm, the surface of which is modified by 3-glycidyloxypropyltrimethoxysilane coupling agent, accounting for 95.5 wt% of the total composite spherical inorganic filler by weight; component 2, spherical silica with an average particle size of 50 nm, the surface of which is modified by phenyltrimethoxysilane coupling agent, accounting for 4.5 wt% of the total composite spherical inorganic filler by weight.

[0047] 2. C-2, a composite spherical inorganic filler, wherein component 1, spherical silica with an average particle size of 1.0 μm, the surface of which is modified with 3-glycidyloxypropyltriethoxysilane coupling agent, accounting for 98 wt% by weight relative to the overall composite spherical inorganic filler; component 2, spherical silica with an average particle size of 20 nm, the surface of which is modified with phenyltriethoxysilane coupling agent, accounting for 2 wt% by weight relative to the overall composite spherical inorganic filler.

[0048] 3. C-3, a composite spherical inorganic filler, wherein component 1, spherical silica with an average particle size of 0.5 μm, the surface of which is modified with 3-glycidyloxypropyltrimethoxysilane coupling agent, accounting for 99 wt% by weight relative to the overall composite spherical inorganic filler; component 2, spherical alumina with an average particle size of 10 nm, the surface of which is modified with phenyltriethoxysilane coupling agent, accounting for 1 wt% by weight relative to the overall composite spherical inorganic filler.

[0049] 4. C-4, a composite spherical inorganic filler, wherein component 1, spherical silica with an average particle size of 0.3 μm, the surface of which is modified with 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane coupling agent, accounting for 99.7 wt% by weight relative to the overall composite spherical inorganic filler; component 2, spherical silica with an average particle size of 10 nm, the surface of which is modified with phenyltrimethoxysilane coupling agent, accounting for 0.3 wt% by weight relative to the overall composite spherical inorganic filler.

[0050] 5. C-5, a composite spherical inorganic filler, wherein component 1, spherical silica with an average particle size of 0.5 μm, the surface of which is modified by phenyltrimethoxysilane coupling agent, accounting for 99 wt% by weight relative to the overall composite spherical inorganic filler; component 2, spherical silica with an average particle size of 10 nm, the surface of which is modified by phenyltrimethoxysilane coupling agent, accounting for 1 wt% by weight relative to the overall composite spherical inorganic filler.

[0051] 6. C-6, a composite spherical inorganic filler, wherein component 1, spherical silica with an average particle size of 0.5 μm, the surface of which is modified with 3-glycidyloxypropyltrimethoxysilane coupling agent, accounting for 99 wt% by weight relative to the overall composite spherical inorganic filler; component 2, spherical silica with an average particle size of 10 nm, the surface of which is modified with 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane coupling agent, accounting for 1 wt% by weight relative to the overall composite spherical inorganic filler.

[0052] 7. C-7, a composite spherical inorganic filler, wherein component 1, spherical silica with an average particle size of 0.5 μm, the surface of which is modified with a phenyltrimethoxysilane coupling agent, accounting for 99 wt% by weight relative to the overall composite spherical inorganic filler; component 2, spherical silica with an average particle size of 10 nm, the surface of which is modified with a 3-glycidyloxypropyltrimethoxysilane coupling agent, accounting for 1 wt% by weight relative to the overall composite spherical inorganic filler.

[0053] 8.C-8, composite spherical inorganic filler, wherein component 1, spherical silica with an average particle size of 1.0 μm, the surface of which is modified with 3-glycidyloxypropyltrimethoxysilane coupling agent, accounting for 99.9wt% by weight relative to the overall composite spherical inorganic filler; component 2, spherical silica with an average particle size of 10 nm, the surface of which is modified with phenyltrimethoxysilane coupling agent, accounting for 0.1wt% by weight relative to the overall composite spherical inorganic filler.

[0054] 9.C-9, a composite spherical inorganic filler, wherein component 1, spherical silica with an average particle size of 1.7 μm, the surface of which is modified with 3-glycidyloxypropyltrimethoxysilane coupling agent, accounting for 94 wt% of the total composite spherical inorganic filler by weight; component 2, spherical silica with an average particle size of 50 nm, the surface of which is modified with phenyltrimethoxysilane coupling agent, accounting for 6 wt% of the total composite spherical inorganic filler by weight.

[0055] 10. Triglycidyl p-aminophenol epoxy resin, epoxy equivalent weight 94, JER630, from Mitsubishi Chemical Corporation.

[0056] 11. Bisphenol F epoxy resin, epoxy equivalent 158, KF-8110, from Hunan Saierwei New Materials.

[0057] 12.Naphthalene diol epoxy resin, epoxy equivalent 140, EBA-65, from Shanghai Huayi.

[0058] 13. Bisphenol A epoxy resin, epoxy equivalent 173, ZL-600, from Zhilun Ultrapure Epoxy Resin Co., Ltd.

[0059] 14.Diethyltoluenediamine, DETDA, from Dongying Hairuibao New Materials.

[0060] 15.4,4'-Diamino-3,3'-diethyldiphenylmethane, from Jiangyin Huifeng Synthetic Materials Co., Ltd.

[0061] The present invention will be further described below through more specific examples.

[0062] Embodiment 1:

[0063] An epoxy resin composition adhesive, comprising 13.0 parts by weight of bisphenol F epoxy resin, 5.0 parts by weight of bisphenol A epoxy resin, 72.0 parts by weight of composite spherical inorganic filler C-1, 8.7 parts by weight of curing agent diethyltoluenediamine, 0.8 parts by weight of coupling agent, and 0.5 parts by weight of pigment;

[0064] The preparation method of the epoxy resin composition adhesive is as follows: according to parts by weight, bisphenol F epoxy resin, bisphenol A epoxy resin, coupling agent and pigment are mixed at a rotation speed of 1600 rpm for 20 minutes to obtain a first mixture; composite spherical inorganic filler C-1 is added to the first mixture, and mixed at a rotation speed of 1600 rpm for 30 minutes to obtain a second mixture; diethyltoluenediamine is added to the second mixture, mixed for 10 minutes, and vacuum degassed for 5 minutes to obtain the epoxy resin composition adhesive.

[0065] Embodiment 2:

[0066] An epoxy resin composition adhesive, comprising 6.0 parts by weight of bisphenol F epoxy resin, 20.0 parts by weight of triglycidyl p-aminophenol epoxy resin, 61.0 parts by weight of composite spherical inorganic filler C-2, 3.0 parts by weight of curing agent diethyltoluenediamine, 8.5 parts by weight of curing agent 4,4'-diamino-3,3'-diethyldiphenylmethane, 0.5 parts by weight of coupling agent, and 1.0 parts by weight of pigment;

[0067] The preparation method of the epoxy resin composition adhesive is as follows: according to parts by weight, bisphenol F epoxy resin, aminophenol type epoxy resin, coupling agent and pigment are mixed at a speed of 1600 rpm for 30 minutes to obtain a first mixture; composite spherical inorganic filler C-2 is added to the first mixture, and mixed at a speed of 1600 rpm for 60 minutes to obtain a second mixture; diethyltoluenediamine and 4,4'-diamino-3,3'-diethyldiphenylmethane are added to the second mixture, mixed for 20 minutes, and vacuum degassed for 10 minutes to obtain the epoxy resin composition adhesive.

[0068] Embodiment 3:

[0069] An epoxy resin composition adhesive, comprising 4.0 parts by weight of bisphenol F epoxy resin, 2.0 parts by weight of bisphenol A epoxy resin, 16.0 parts by weight of triglycidyl p-aminophenol epoxy resin, 65.0 parts by weight of composite spherical inorganic filler C-3, 5.0 parts by weight of curing agent diethyltoluenediamine, 6.2 parts by weight of curing agent 4,4'-diamino-3,3'-diethyldiphenylmethane, 1.5 parts by weight of coupling agent, and 0.3 parts by weight of pigment;

[0070] The preparation method of the epoxy resin composition adhesive is as follows: according to parts by weight, bisphenol F epoxy resin, bisphenol A epoxy resin, triglycidyl para-aminophenol epoxy resin, coupling agent and pigment are mixed at a speed of 1600 rpm for 30 minutes to obtain a first mixture; composite spherical inorganic filler C-3 is added to the first mixture, and mixed at a speed of 1600 rpm for 80 minutes to obtain a second mixture; diethyltoluenediamine and 4,4'-diamino-3,3'-diethyldiphenylmethane are added to the second mixture, mixed for 15 minutes, and vacuum degassed for 10 minutes to obtain the epoxy resin composition adhesive.

[0071] Embodiment 4:

[0072] An epoxy resin composition adhesive, comprising 4.0 parts by weight of bisphenol F epoxy resin, 18.0 parts by weight of triglycidyl p-aminophenol epoxy resin, 66.0 parts by weight of composite spherical inorganic filler C-4, 10.5 parts by weight of curing agent diethyltoluenediamine, 1.0 parts by weight of coupling agent, and 0.5 parts by weight of pigment;

[0073] The preparation method of the epoxy resin composition adhesive is as follows: according to parts by weight, bisphenol F epoxy resin, triglycidyl para-aminophenol epoxy resin, coupling agent and pigment are mixed at a rotation speed of 1600 rpm for 30 minutes to obtain a first mixture; composite spherical inorganic filler C-4 is added to the first mixture, and mixed at a rotation speed of 1600 rpm for 80 minutes to obtain a second mixture; diethyltoluenediamine is added to the second mixture, mixed for 15 minutes, and vacuum degassed for 10 minutes to obtain the epoxy resin composition adhesive.

[0074] Embodiment 5:

[0075] An epoxy resin composition adhesive, comprising 4.0 parts by weight of bisphenol F epoxy resin, 2.0 parts by weight of bisphenol A epoxy resin, 22.0 parts by weight of triglycidyl p-aminophenol epoxy resin, 55.0 parts by weight of composite spherical inorganic filler C-2, 15.5 parts by weight of curing agent 4,4'-diamino-3,3'-diethyldiphenylmethane, 1.0 parts by weight of coupling agent, and 0.5 parts by weight of pigment;

[0076] The preparation method of the epoxy resin composition adhesive is as follows: according to parts by weight, bisphenol F epoxy resin, bisphenol A epoxy resin, triglycidyl para-aminophenol epoxy resin, coupling agent and pigment are mixed at a speed of 1600 rpm for 30 minutes to obtain a first mixture; the composite spherical inorganic filler C-2 is added to the first mixture, and mixed at a speed of 1600 rpm for 60 minutes to obtain a second mixture; 4,4'-diamino-3,3'-diethyldiphenylmethane is added to the second mixture, mixed for 15 minutes, and vacuum degassed for 10 minutes to obtain the epoxy resin composition adhesive.

[0077] Comparative Example 1:

[0078] An epoxy resin composition adhesive, comprising 4.0 parts by weight of bisphenol F epoxy resin, 2.0 parts by weight of bisphenol A epoxy resin, 16.0 parts by weight of triglycidyl p-aminophenol epoxy resin, 65.0 parts by weight of composite spherical inorganic filler C-5, 5.0 parts by weight of curing agent diethyltoluenediamine, 6.2 parts by weight of curing agent 4,4'-diamino-3,3'-diethyldiphenylmethane, 1.5 parts by weight of coupling agent, and 0.3 parts by weight of pigment;

[0079] The preparation method of the epoxy resin composition adhesive is as follows: according to parts by weight, bisphenol F epoxy resin, bisphenol A epoxy resin, aminophenol type epoxy resin, coupling agent and pigment are mixed at a speed of 1600 rpm for 20 minutes to obtain a first mixture; the composite spherical inorganic filler C-5 is added to the first mixture, and mixed at a speed of 1600 rpm for 30 minutes to obtain a second mixture; diethyltoluenediamine and 4,4'-diamino-3,3'-diethyldiphenylmethane are added to the second mixture, mixed for 10 minutes, and vacuum degassed for 5 minutes to obtain the epoxy resin composition adhesive.

[0080] Comparative Example 2:

[0081] An epoxy resin composition adhesive, comprising 4.0 parts by weight of bisphenol F epoxy resin, 2.0 parts by weight of bisphenol A epoxy resin, 16.0 parts by weight of triglycidyl p-aminophenol epoxy resin, 65.0 parts by weight of composite spherical inorganic filler C-6, 5.0 parts by weight of curing agent diethyltoluenediamine, 6.2 parts by weight of curing agent 4,4'-diamino-3,3'-diethyldiphenylmethane, 1.5 parts by weight of coupling agent, and 0.3 parts by weight of pigment;

[0082] The preparation method of the epoxy resin composition adhesive is as follows: according to parts by weight, bisphenol F epoxy resin, bisphenol A epoxy resin, triglycidyl para-aminophenol epoxy resin, coupling agent and pigment are mixed at a speed of 1600 rpm for 20 minutes to obtain a first mixture; composite spherical inorganic filler C-6 is added to the first mixture, and mixed at a speed of 1600 rpm for 30 minutes to obtain a second mixture; diethyltoluenediamine and 4,4'-diamino-3,3'-diethyldiphenylmethane are added to the second mixture, mixed for 10 minutes, and vacuum degassed for 5 minutes to obtain the epoxy resin composition adhesive.

[0083] Comparative Example 3:

[0084] An epoxy resin composition adhesive, comprising 4.0 parts by weight of bisphenol F epoxy resin, 2.0 parts by weight of bisphenol A epoxy resin, 16.0 parts by weight of triglycidyl p-aminophenol epoxy resin, 65.0 parts by weight of composite spherical inorganic filler C-7, 5.0 parts by weight of curing agent diethyltoluenediamine, 6.2 parts by weight of curing agent 4,4'-diamino-3,3'-diethyldiphenylmethane, 1.5 parts by weight of coupling agent, and 0.3 parts by weight of pigment;

[0085] The preparation method of the epoxy resin composition adhesive is as follows: according to parts by weight, bisphenol F epoxy resin, bisphenol A epoxy resin, triglycidyl para-aminophenol epoxy resin, coupling agent and pigment are mixed at a speed of 1600 rpm for 20 minutes to obtain a first mixture; composite spherical inorganic filler C-7 is added to the first mixture, and mixed at a speed of 1600 rpm for 30 minutes to obtain a second mixture; diethyltoluenediamine and 4,4'-diamino-3,3'-diethyldiphenylmethane are added to the second mixture, mixed for 10 minutes, and vacuum degassed for 5 minutes to obtain the epoxy resin composition adhesive.

[0086] Comparative Example 4:

[0087] An epoxy resin composition adhesive, comprising 4.0 parts by weight of bisphenol F epoxy resin, 2.0 parts by weight of bisphenol A epoxy resin, 16.0 parts by weight of triglycidyl p-aminophenol epoxy resin, 65.0 parts by weight of composite spherical inorganic filler C-8, 5.0 parts by weight of curing agent diethyltoluenediamine, 6.2 parts by weight of curing agent 4,4'-diamino-3,3'-diethyldiphenylmethane, 1.5 parts by weight of coupling agent, and 0.3 parts by weight of pigment;

[0088] The preparation method of the epoxy resin composition adhesive is as follows: according to parts by weight, bisphenol F epoxy resin, triglycidyl para-aminophenol epoxy resin, coupling agent and pigment are mixed at a rotation speed of 1600 rpm for 20 minutes to obtain a first mixture; composite spherical inorganic filler C-8 is added to the first mixture, and mixed at a rotation speed of 1600 rpm for 30 minutes to obtain a second mixture; diethyltoluenediamine and 4,4'-diamino-3,3'-diethyldiphenylmethane are added to the second mixture, mixed for 10 minutes, and vacuum degassed for 5 minutes to obtain the epoxy resin composition adhesive.

[0089] Comparative Example 5:

[0090] An epoxy resin composition adhesive, comprising 4.0 parts by weight of bisphenol F epoxy resin, 2.0 parts by weight of bisphenol A epoxy resin, 16.0 parts by weight of triglycidyl p-aminophenol epoxy resin, 65.0 parts by weight of composite spherical inorganic filler C-9, 5.0 parts by weight of curing agent diethyltoluenediamine, 6.2 parts by weight of curing agent 4,4'-diamino-3,3'-diethyldiphenylmethane, 1.5 parts by weight of coupling agent, and 0.3 parts by weight of pigment;

[0091] The preparation method of the epoxy resin composition adhesive is as follows: according to parts by weight, bisphenol F epoxy resin, bisphenol A epoxy resin, triglycidyl para-aminophenol epoxy resin, coupling agent and pigment are mixed at a speed of 1600 rpm for 20 minutes to obtain a first mixture; composite spherical inorganic filler C-9 is added to the first mixture, and mixed at a speed of 1600 rpm for 30 minutes to obtain a second mixture; diethyltoluenediamine and 4,4'-diamino-3,3'-diethyldiphenylmethane are added to the second mixture, mixed for 10 minutes, and vacuum degassed for 5 minutes to obtain the epoxy resin composition adhesive.

[0092] The performance indicators of the obtained epoxy resin composition adhesive are shown in Table 1.

[0093] Table 1 Performance comparison between the embodiments and comparative examples

[0094]

[0095]

[0096] It can be seen from the above table that when the epoxy resin composition adhesive of the embodiment of the present invention is used for bottom filling of a high-density RDL fan-out packaging form, even if a very short dispensing delay parameter is set, it can still show excellent operating performance, and there will be no phenomenon of the epoxy resin composition adhesive between adjacent chip integrated units contacting each other.

Claims

1. An epoxy resin composition adhesive, characterized in that: The raw materials include the following components by weight: (A) epoxy resin, 18-30 parts by weight, preferably 20-26 parts by weight; (B) an amine curing agent, 7-20 parts by weight, preferably 10-16 parts by weight; (C) composite spherical inorganic filler, 50-75 parts by weight, preferably 55-70 parts by weight; (D) coupling agent, 0.1-5 parts by weight, preferably 0.5-1.0 parts by weight; The component (C) composite spherical inorganic filler consists of two parts: spherical inorganic filler 1, spherical silica with an average particle size of 0.1 μm-3 μm, the surface of which is modified by an epoxy silane coupling agent, accounting for 95-99.8 wt% of component (C) by weight percentage; spherical inorganic filler 2, one or both of spherical silica or alumina with an average particle size of 5-60 nm, the surface of which is modified by a phenyl silane coupling agent, accounting for 0.2-5 wt% of component (C) by weight percentage.

2. The epoxy resin composition adhesive according to claim 1, characterized in that: The epoxysilane coupling agent is a coupling agent containing both epoxy groups and siloxane groups.

3. The epoxy resin composition adhesive according to claim 2, characterized in that: The epoxysilane coupling agent is selected from one or more of 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, and 2-(3,4-epoxycyclohexyl)ethylmethyldiethoxysilane, preferably 3-glycidyloxypropyltrimethoxysilane and 3-glycidyloxypropyltriethoxysilane.

4. The epoxy resin composition adhesive according to any one of claims 1 to 3, characterized in that: The phenylsilane coupling agent is a coupling agent containing both a phenyl group and a siloxane group; Preferably, the phenylsilane coupling agent is selected from one or more of phenyltrimethoxysilane, phenyltriethoxysilane, p-styrenetrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane, preferably phenyltrimethoxysilane and phenyltriethoxysilane.

5. The epoxy resin composition adhesive according to any one of claims 1 to 4, characterized in that: The epoxy resin of component (A) is selected from at least two 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 of bisphenol F epoxy resin, bisphenol A epoxy resin, naphthalene diol epoxy resin, N,N-di(glycidyl)-o-toluidine, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether and triglycidyl p-aminophenol epoxy resin.

6. The epoxy resin composition adhesive according to any one of claims 1 to 5, characterized in that: The component (B) amine curing agent is selected from at least one of 4,4'-diamino-3,3'-diethyldiphenylmethane, diethyltoluenediamine, diaminodiphenyl sulfone, m-aminomethylamine, benzyl diamine trimer, bis-benzyl amino ether, dimethylthiotoluenediamine, and ethylaniline, preferably at least one of 4,4'-diamino-3,3'-diethyldiphenylmethane, diethyltoluenediamine, and dimethylthiotoluenediamine.

7. The epoxy resin composition adhesive according to any one of claims 1 to 6, characterized in that: The true roundness of the spherical inorganic filler is 0.8-1, preferably 0.9-1; The circularity is defined as "the ratio of the minimum particle size to the maximum particle size of particles" in a two-dimensional image observed using a scanning electron microscope (SEM).

8. The epoxy resin composition adhesive according to any one of claims 1 to 7, characterized in that: The coupling agent of component (D) is selected from any one of vinyl, epoxy, methacryl, amino and mercapto organic silane coupling agents, preferably an epoxy organic silane coupling agent.

9. The method for preparing the epoxy resin composition adhesive according to any one of claims 1 to 8, characterized in that: The following steps are involved: Mixing the epoxy resin (A) and the coupling agent (D) uniformly to obtain a first mixture; Adding the composite spherical inorganic filler as component (C) to the first mixture and mixing them evenly to obtain a second mixture; The component (B) amine curing agent is added into the second mixture, mixed evenly, and vacuum degassed to obtain an epoxy resin composition adhesive.

10. Use of the epoxy resin composition adhesive according to any one of claims 1 to 8 or the epoxy resin composition adhesive prepared by the preparation method according to claim 9 in chip packaging, particularly suitable for bottom filling of high-density RDL fan-out packaging.

Images