Resin composition for sealing electronic device

Abstract

The invention relates to the technical field of semiconductor packaging materials, in particular to a resin composition for sealing an electronic device, and the existing epoxy resin composition comprises solid / powder nanoscale filler so as to reduce CTE and inhibit the exudation problem. However, it is very difficult to add a solid / powder nanoscale filler to an epoxy resin composition, which will result in a sharp increase in overall viscosity and even unable to mix evenly. By adding the colloid filler, the viscosity of the prepared resin composition is low, which means that the filler loading capacity in the resin composition (bottom filler) can be further increased, and the overall excellent moisture resistance and better temperature resistance of the composition can be improved. In addition, since the loading amount of the filler is increased, the CTE of the cured resin composition is reduced, and thus the reliability of the cured resin mixture can be improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of semiconductor encapsulating material, and particularly relates to a resin composition for electronic device sealing. BACKGROUND

[0002] With the miniaturization, thinness, lightness and high performance of electronic devices, the packaging form of semiconductors is changing from the lead bonding type to the flip chip type.

[0003] Flip chip is a method of interconnecting a die such as a semiconductor device, an IC chip, an integrated passive device, and a micro electro mechanical system (MEMS) to an external circuit through solder bumps deposited on a chip pad. The flip chip type semiconductor device has a structure in which an electrode on a substrate and a semiconductor element are connected via a solder bump or a copper pillar. When an external temperature change such as temperature cycling is applied to the semiconductor device, stress will be generated in the bump electrode due to the difference in the coefficient of thermal expansion between the substrate (an organic material such as an epoxy resin or a polyimide resin) and the semiconductor element (a Si material). Therefore, a problem of crack occurrence in the bump electrode can occur. In addition, external physical impact or impact also applies stress to the bump electrode, resulting in a bump crack defect. In order to suppress the bump crack defect, a resin composition (so-called underfill) is widely used to fill the gap between the semiconductor element and the substrate.

[0004] In recent years, with finer wiring, multi-layer, high pin count of elements, miniaturization and slimming of packaging, high-density packaging has been developed to achieve cost reduction, more functions and higher performance. Therefore, electronic devices having almost the same size as elements such as integrated circuits, i.e., chip size packaging (CSP), have been widely used. In particular, wafer level chip size packaging has received increasing attention. In such wafer level chip size packaging, a large number of elements are packaged by using compression molding or transfer molding of an epoxy resin composition. However, warpage of the sealed silicon wafer occurs, which affects subsequent transportation, grinding, inspection and singulation. Warpage of the silicon wafer can cause deterioration of the packaging reliability. The cause of warpage of the silicon wafer is stress generated from the curing shrinkage of the epoxy resin composition, CTE (coefficient of thermal expansion) mismatch between the silicon wafer and the epoxy resin composition.

[0005] In the field of element sealing / packaging of electronic devices, the epoxy resin composition as an underfill is still the mainstream in terms of cost, productivity, etc. An effective method for reducing stress in the existing epoxy resin composition is to use a high-filled inorganic filler to reduce the CTE.

[0006] Patent JP2020070347A describes an underfill which contains (A) an epoxy resin; (B) a curing agent; (C) an inorganic filler having an average particle size of 7 nm to 100 nm and (D) a liquid silicone compound having a carboxyl group. The patent discloses a liquid epoxy resin composition which at least includes a liquid epoxy resin, a liquid curing agent and an inorganic filler, as a liquid underfill liquid resin composition, to reduce and redistribute the stress problem between the semiconductor element and the substrate.

[0007] In the case of patent JP2020070347A using nanoscale silica (7 nm~100 nm) and a liquid silicone compound with carboxyl group, the occurrence of bleeding, creep and voids can be inhibited, and the CTE of the epoxy resin cured product can also be reduced. However, there is a problem in the technology of the above patent that it is very difficult to add solid / powder nanoscale fillers to the epoxy resin composition, which will cause the viscosity of the overall composition to increase sharply, and even cannot be mixed uniformly. These unevenly mixed fillers will reduce the performance of the underfill, and even cause poor flowability, creep and reliability problems such as voids, delamination, etc. Generally, in order to achieve a certain balance between viscosity / flowability and the performance of the underfill, the amount of filler is usually reduced to reduce the overall viscosity, but this will increase the CTE of the epoxy resin cured product, thereby risking sacrificing part of the reliability. In addition, while maintaining the same filling load, there is also a method of using larger particle size fillers to reduce the viscosity of the composition. However, for the current trend of smaller and smaller semiconductor elements, the gap between the chip and the substrate will be smaller and smaller. Therefore, larger particle size fillers will be difficult to completely fill the smaller gap between the semiconductor element and the substrate. SUMMARY

[0008] The purpose of the present application is to provide a new resin composition which has good viscosity and flow performance of the composition, and the filler load can be further increased without sacrificing part of the reliability of the resin composition.

[0009] To achieve the purpose of the present application, the technical solution is:

[0010] A resin composition for electronic device sealing, comprising by mass percentage: 10-30% of a thermosetting resin, 15-35% of a curing agent, 0.1-3% of a catalyst, 0.8-5% of an additive, 5-20% of a colloidal filler and 45-68% of a solid filler. The thermosetting resin is selected from epoxy resins, and the thermosetting resin is liquid at 25°C. Further, the thermosetting resin is liquid at 25°C means that when the thermosetting resin is selected from a mixture of two or more, the mixture is liquid at 25°C. It is understood that a solid form of epoxy resin is used in combination with a liquid epoxy resin, the solid form of epoxy resin is dissolved or dispersed in the liquid form of epoxy resin, as long as the mixture is liquid at room temperature of 25°C.

[0011] Further, the colloidal filler is selected from silica sol, alumina sol or a mixture of the two, with a particle size of ≤ 100 nm. Still further, the solid filler is selected from clay, kaolin, talc, mica, silica, calcium carbonate, sodium sulfate, magnesium sulfate, barium sulfate, alumina, boron nitride, aluminum nitride. Preferably, the solid filler is selected from silica, alumina, boron nitride, aluminum nitride or a mixture of any combination of silica, alumina, boron nitride, aluminum nitride. The shape of the solid filler can be spherical or / and flaky or / and random, more preferably spherical solid filler. The particle size of the solid filler is: 0.010 μm ≤ particle size of the solid filler ≤ 10 μm, preferably: 0.015 μm ≤ particle size of the solid filler ≤ 5 μm, more preferably: 0.015 μm ≤ particle size of the solid filler < 5 μm. Particularly preferred solid filler is spherical silica particles. Most of the commercially available spherical silica particles have been surface modified with silane coupling agent, which ensures the compatibility of the filler with the epoxy resin and the flowability of the entire composition, which can be preferably used.

[0012] The colloidal filler is a suspension of silica or aluminum in a liquid phase, and the silica or aluminum particles are fine, amorphous, non-porous and usually spherical. The liquid phase can be selected from organic liquid resin, organic solvent or aqueous solution as a matrix. As a specific example, the organic liquid resin can be selected from liquid epoxy resin, liquid acrylic resin, liquid silicone resin, liquid polyether resin, liquid polyester resin. Preferably, the liquid epoxy resin, liquid acrylic resin, liquid silicone resin. Particularly preferably, the liquid epoxy resin, liquid silicone resin.

[0013] More specifically, the colloidal filler includes Nanocase A410, Nanocase A510, Nanocase A611, Nanocase E430, Nanocase E470, Nanocase E500, Nanocase E601, Nanocase E770, Nanocase F400, Nanocase F440, Nanocase F520, Nanocase F631, Nanocase F700, EVONP-470, LUDOX® HS-30, MAS Colloidal Silica, 406 Colloidal Silica, AEROSIL® Colloidal Silica, AEROPERL® Collidal Silica, AMSol TM 8 SM, AMSol TM 8 SMX, AMSol TM 15, AMSol TM 15 SM, AMSol TM 20 SM, AMSol TM 30, AMSol TM 30 SM, AMSol TM 4012, AMSol TM 4015, AMSol TM 50, AMSol TM HT and the like, but are not limited thereto.

[0014] The filler can be composed of an organic filler, an inorganic filler.

[0015] The resin composition described above can further include an organic filler selected from carbon black, graphite, graphene, carbon nanotube, acrylate beads. The shape of the organic filler can be spherical, flaky or random type. The organic filler can be added as needed, for example, when the resin composition needs to have a color recognition function, the organic filler can be added. When the organic filler is added, the amount of addition is 0.01% to 5% of the total weight of the resin composition, preferably 0.05% to 2%, without affecting the various property requirements of the resin composition.

[0016] Further, the thermosetting resin is selected from one or more of epoxy resin, epoxy novolac resin, phenol resin, unsaturated polyester, polyurethane, diallyl phthalate resin, bismaleimide resin, melamine resin, benzoxazine, polyimide, cyanate ester, furan resin, silicone resin.

[0017] Preferably, from the perspective of the curability and adhesion of the resin composition (underfill), and the heat resistance, mechanical resistance, moisture resistance, durability and electrical insulation of the cured epoxy resin composition, the epoxy resin is selected.

[0018] The epoxy resin is selected from the group consisting of aliphatic epoxy resins, aromatic epoxy resins, saturated epoxy resins or unsaturated epoxy resins. These epoxy resins can be further divided into two types: glycidyl epoxy resins and non-glycidyl resins. Of these, the glycidyl epoxy resins are further divided into glycidyl ether epoxy resins, glycidyl ester epoxy resins and glycidyl amine epoxy resins. The non-glycidyl epoxy resins are divided into aliphatic epoxy resins or cycloaliphatic epoxy resins.

[0019] Preferably, the epoxy resin is selected from the group consisting of novolac type epoxy resins, such as phenol novolac type and cresol novolac type, bisphenol type epoxy resins such as bisphenol A type and bisphenol F type, bisphenol AD type epoxy resins, aromatic glycidyl amine type epoxy resins such as N,N-diglycidyl aniline, N,N-bisglycidyl toluidine, diamino diphenyl methane type glycidyl amine and aminophenol type glycidyl amine epoxy resins, hydroquinone type epoxy resins and stilbene type epoxy resins. Propane type epoxy resins, epoxy resins containing triazine core, dicyclopentadiene modified phenol type epoxy resins, naphthol type epoxy resins, and / or biphenyl skeleton, aliphatic series epoxy resins, such as cycloaliphatic epoxy type resins, such as vinyl cyclohexene dioxide type epoxy resins.

[0020] The bisphenol A epoxy resin can be selected from the group consisting of the following types: NPEL-127, NPEL-127E, NPEL-127H, NPEL-128, NPEL-128E, NPEL-128G, NPEL-128R, NPEL-128S, NPEL-134, NPEL-136, NPEL-231, EPICLON 840, EPICLON 840S, EXA-850CRP, EPICLON 850, EPICLON 850-LC, Araldite® GY 2600, Araldite® GY 6010, Araldite® GY 6020, Araldite® MY 790-1, Araldite® LY 1556, Tactix® 123, Araldite® GY 502, Araldite® GY 506, Araldite® GY 507, Araldite® GY 508, Araldite® GY 509, Araldite® GY 512, Araldite® GY 6004, Araldite® GY 6005, Araldite® GY 9413, Araldite® GY 9513, Araldite® GY 9580, Araldite® GY 9613, Araldite® GY 9615, Araldite® GY 9667, Araldite® LY 1564, BE124A.

[0021] Bisphenol F epoxy resins can be selected from the following types such as NPEF-164X, NPEF-170, NPEF-175, NPEF-176, NPEF-185, NPEF-187, NPEF-198, NPEF-500, EPICLON 830, EPICLON 830-S, EPICLON 835, EXA-830CRP, EXA-830LVP, EXA-835LV, Araldite® GY 281, Araldite® GY 282, Araldite® GY 285, Araldite® PY 306, Araldite® PY 302-2, Araldite® PY 313.

[0022] From the point of view of the flowability and adhesion of the resin composition and the heat resistance, moisture resistance, mechanical resistance, durability and electrical insulation of the cured resin composition, more preferably, the epoxy resin is used.

[0023] The epoxy resin component can be used alone or in combination of two or more. Further, the epoxy resin is selected from the group consisting of solid type, liquid type or a combination of the above two types of epoxy resins. The solid type epoxy resin at room temperature can also be used in combination with the liquid epoxy resin, dissolving or dispersing the solid type epoxy resin in the liquid type epoxy resin, as long as the mixture is preferably liquid at room temperature of 25°C.

[0024] Particularly preferably, the thermosetting resin is liquid at 25°C and has at least two epoxy groups per molecule, more particularly preferably selected from one or more of bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol AD epoxy resins and naphthalene epoxy resins.

[0025] Further, the curing agent can be selected from the group consisting of anhydride, amine type, phenol type, anhydride and phenol blend, amine and phenol blend, polysulfide resin, organic hydrazide. The anhydride and phenol blend is mixed in a weight ratio of 99:1 ~ 60:40, preferably 97:3 ~ 75:25. The amine and phenol blend is mixed in a weight ratio of 10:90 ~ 90:10, preferably 25:75 ~ 75:25.

[0026] The phenolic curing agent is selected from the group consisting of aliphatic polyamines, cycloaliphatic amines, aromatic amines, dicyandiamide. The aliphatic polyamines include linear aliphatic polyamines, cycloaliphatic polyamines, aliphatic aromatic amines. As specific examples, the linear aliphatic polyamines include diethylenetriamine (DETA), triethylenetetramine (TFTA), tetraethylenepentamine (TEPA), dipropylene diamine (DPDA), diethylaminopropylamine (DEAPA), 1,3-bis(aminomethyl)benzene (MXDA), and the like. The cycloaliphatic polyamines include N-aminoethylpiperazine (N-AEP), methanediamine (MDA), isophorone diamine (IPDA), Lamiron C-260, Wandamin HM, and the like. The aliphatic aromatic amines include m-xylylenediamine (m-XDA), tertiary amine X, tertiary amine N, tertiary amine 1001, and the like. The aromatic amines include m-phenylenediamine (MPDA), diaminodiphenylmethane (DDM), diamine diphenyl sulfone (DDS), 4,4'-methylene dianiline, and the like.

[0027] The cycloaliphatic amines can be selected from the group consisting of VERSACURE® RAC 3387, VERSACURE® RAC 3391, VERSACURE® RAC 9961, VERSACURE® RAC 9963, VERSACURE® RAC 9964, VERSACURE® RAC 9965, VERSACURE® RAC 9974, VERSACURE® RAC 9978, VERSACURE® RAC 9982, VERSACURE® RAC 9983, VERSACURE® RAC 9990, VERSACURE® RAC 9991, VERSACURE® RAC 9997, AP 5618, AP 5205, AP 5956, AP 5768, AP 5904, AP 5905…

[0028] The acid anhydrides include phthalic anhydride (PA), hexahydrophthalic anhydride (HHPA), naphthalene anhydride, and the like.

[0029] The polythiol resins include POLYTHIOL™ QE-340M, Three Bond 2104, and the like.

[0030] The organic hydrazines include adipic acid dihydrazide, m-phenylenedihydrazide, sebacic acid dihydrazide, Aradur LDH, Aradur VDH, and the like.

[0031] From the resin composition active regulation and viscosity adaptability (to meet the bottom filling / packaging agent process requirements), preferably organic acid anhydride curing agent. As a specific example, the focus on anhydride varieties are exemplified, but not limited to: methyl hydrogen anhydride: methyl tetrahydrophthalic anhydride (mthpa), hexahydro-4-methyl phthalic anhydride. Bridge ring anhydride: endo-bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride, methyl endomethylene tetrahydrophthalic anhydride. Polycyclic anhydride: bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic dianhydride. Fluorine-containing anhydride: 4,4'-(hexafluoroisopropylidene) diphenyl dicarboxylic anhydride. Aromatic dianhydride: benzophenone-3,3',4,4'-tetracarboxylic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride. Ether chain anhydride: 4,4'-oxydianhydride, 4,4'-(4,4'-isopropylidene diphenyl oxy) bis (phthalic anhydride). Special structure anhydride: dodecenyl succinic anhydride, chloro anhydride, polyazelaic anhydride. Particularly preferred hexahydro-4-methyl phthalic anhydride HHPA, comprehensive balance curing speed, viscosity, heat resistance.

[0032] Further, the catalyst is selected from any one of Lewis acid, imidazole compound, metal complex, amine complex.

[0033] As a specific example, the imidazole compound can be selected from 2-ethyl-4-methylimidazole (2E4MZ), 4-methyl-2-phenyl-1H-imidazole (2P4MZ), 2-phenyl-4,5-dihydroimidazole (2PZ-L), 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole (2E4MZ-CN), 4,5-bis(hydroxymethyl)-2-phenylimidazole (2PHZ), 4-hydroxymethyl-5-methyl-2-phenylimidazole. Lewis acid consists of boron trifluoride (BF3), zinc chloride (ZnCl2), tin (IV) chloride (SnCl4), iron chloride (FeCl3), aluminum chloride (AlCl3) and the like. Amine complex is selected from tri-key 2285B, tri-key 2287, tri-key 2287B and the like. Metal complex is selected from acetylacetone platinum (II), acetylacetone cobalt (II), acetylacetone cobalt (III), acetylacetone nickel (II), acetylacetone copper (II), acetylacetone iron (II), acetylacetone iron (III), acetylacetone chromium (II), acetylacetone chromium (III), acetylacetone manganese (II), acetylacetone manganese (III), acetylacetone magnesium (II)…

[0034] Further, the additive can be added according to the different characteristics required by the resin composition. The additive can be selected from a functional silicone resin, a functional acrylate resin, a coupling agent, or a blend thereof. When the additive is a blend of a functional silicone resin, a functional acrylate resin, and a coupling agent, it means that two or more of these additives are mixed and used, and there is no limitation on the ratio. As long as these additives are added to achieve their intended effects without affecting the characteristics of the existing resin composition, they can be used.

[0035] As specific examples, the coupling agent includes alkoxysilane, silazane, and the like. The alkoxysilane coupling agent includes methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, propyltrimethoxysilane, hexyltrimethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltriethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, 7-octenyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, glycidoxypropyltrimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropylmethyldiethoxysilane, methacryloyloxypropyltriethoxysilane, 8-methacryloyloxyoctyltrimethoxysilane, acryloyloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-8-aminooctyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and the like.

[0036] Functional silicon resins include VQM XP1773, VQM 803, VQM 806, VQM 807, VQM 809, vqm881, VQM-885, EP0408, EP0409, MA0735, MA0736, AL0125, AM0265, AM0281, MS0802, MS0805, SO1455, SO1458, SQ106, SQ107, SQ109, SQ506, SQ511, SQ508, SQ510, KF-868, KF-865, KF-864, KF-859, KF-393, KF-860, KF-880, KF-8002, KF-8004, KF-8005, KF-867, KF-8021, KF-869, KF-861, KF-877, KF-889, X-22-3939A, X-22-343, X-22-2000, KF-101, KF-1001, X-22-2046, KF-102, X-22-4741, KF-1002, KF-1005, X-22-4039, X-22-4015, KF-2001, KF-2004, KF-99, KF-9901, KF-8010, X-22-161A, X-22-161B, KF-8012, KF-8008, KF-105, X-22-163, X-22-163A, X-22-163B, X-22-163C, X-22-169AS, X-22-169B, KF-6000, KF-6001, KF-6002, KF-6003, X-22-164, X-22-164AS, X-22-164A, X-22-164B, X-22-164C, X-22-164E, X-22-4952, X-22-4272, KF-6123, X-22-167B, X-22-167C, KF-2201, KF-9701, X-22-2445, and the like.

[0037] The above combinations have the advantage that they do not show phase separation.

[0038] Further, the resin composition of the present application, wherein all the components are mixed together using a three-roll mill, a bead mill or a planetary mixer, a uniform liquid epoxy resin composition can be obtained.

[0039] Still further, the resin composition of the present application, wherein the colloidal filler is dissolved in a part of the thermosetting resin to form a mixture A, and the solid filler, the curing agent, the catalyst and the additive are dissolved in the remaining thermosetting resin to form a mixture B, and then the mixture A is poured into the mixture B and mixed by stirring, to obtain the resin mixture.

[0040] The resin composition provided by the present application can be used as a sealing agent (underfill agent) when flip-chip mounting or BGA (ball grid array package) / CSP (chip size package) mounting of electronic components such as semiconductor elements is performed. The resin composition can be used as an adhesive when an electronic component is adhered to a substrate or a package. In the case of a sealing agent, the resin composition can also be degassed using a planetary vacuum mixer for the resulting mixture.

[0041] In flip-chip mounting or BGA / CSP mounting, first, a semiconductor element is joined to a substrate (or a package). Next, a sealing agent is injected between the semiconductor element and the substrate, specifically: a resin composition is applied along the outer periphery of the semiconductor element, and the resin composition diffuses into the gap by capillary phenomenon.

[0042] The principle of the present application is:

[0043] Reducing the physical size of the particles while keeping the volume fraction of the solid particles in the composition or mixture constant, results in a dramatic increase in the number of particles. The increased number of particles results in closer proximity of the particles and a much greater interaction (collision, attraction / repulsion, etc.) between the particles. This effect is particularly pronounced for particles with a size of less than 1 micron. Furthermore, these small particles can exhibit a significant increase in the effective hydrodynamic size due to surface attached charge layers, water layers or adsorbed layers, which further exacerbates the interaction between the particles and the complexity of the system as a whole (e.g. making the composition or mixture more viscous and more difficult to flow).

[0044] When the size of the particles suspended in a material is increased, the viscosity of the material as a whole only increases a little bit. This is because for large particles, the increase in the "effective size" due to the charge, water layer or adsorbed layer on the surface of the particle is negligible compared to the already large physical size of the particle. However, under conditions of slow stirring or flow (low shear rates), the particles have the opportunity to experience strong inter-particle forces (colloidal forces). These inter-particle forces are the main factor that actually hinders flow and increases viscosity. Thus, although the direct effect of increasing particle size on viscosity is small, the small change in viscosity due to increasing particle size (and possibly other factors) is amplified and becomes apparent under these conditions of slow flow, due to the increased inter-particle interactions.

[0045] Particles with a wide range of particle sizes (high polydispersity) have a better packing structure than particles with a single particle size (narrow distribution). Individual particles in a wide distribution system have more room to move, resulting in a significant increase in the flowability of the sample, which means a decrease in the viscosity of the system. Therefore, narrowing the particle size distribution can simultaneously increase the viscosity and stability of the suspension.

[0046] When the volume fraction is constant, the viscosity of a sample consisting of larger particles with a small amount of small particles will be lower than that of a system of large or small particles of a single particle size. This is essentially due to a dual mechanism of action: on the one hand, the inter-particle interaction increases with decreasing particle size, leading to an increase in viscosity; on the other hand, other factors caused by the increase in polydispersity will reduce the viscosity. In this particular system, the introduction of small particles significantly reduces the viscosity, making the weakening effect of polydispersity on viscosity more prominent.

[0047] Therefore, mixing fillers of different particle sizes, especially nanoscale fillers, can maintain the flowability and permeability of the underfill adhesive without excessively increasing the viscosity of the underfill adhesive. However, as Figure 2 As shown in A, due to the small particle size (nanoscale) of filler 2, agglomeration easily occurs, making it difficult to uniformly disperse in the thermosetting resin 1 along with filler 1 during preparation. In addition to the agglomeration problem, the overall viscosity of the system is significantly increased and the flowability is deteriorated. Due to the sharp increase in viscosity and deterioration of flowability, the filling amount of the underfill adhesive must be reduced, thereby leading to a decrease in moisture resistance and temperature resistance.

[0048] In the technical solution protected in the present application, as shown in Figure 2 B, the nanoscale filler 2 has been uniformly dispersed in the liquid phase system (colloidal inorganic filler) in advance, and when the larger particle size filler 1 (micron scale) is further mixed in, the nanoparticles can quickly fill the gaps between large particles and are not prone to agglomeration. Therefore, compared with method Figure 2 A, the underfill adhesive prepared using the colloidal inorganic filler has lower viscosity and better flowability under the same filling amount.

[0049] Based on the low viscosity characteristics of the colloidal filler system, the filling amount of the underfill adhesive can be further increased, thereby imparting excellent moisture resistance and temperature resistance to the product.

[0050] Compared with the prior art, the present application has the following significant advantages:

[0051] The resin composition prepared using this colloidal filler has lower viscosity, which means that the filler load in the resin composition (underfill) can be further increased, further resulting in excellent moisture resistance and better temperature resistance. In addition, since the filler load is increased, the CTE of the cured resin composition should be reduced, thereby improving the reliability of the cured resin mixture. BRIEF DESCRIPTION OF DRAWINGS

[0052] Figure 1 is a schematic diagram of the liquid flowability evaluation method of the embodiment of the present application.

[0053] Figure 2 is a principle introduction diagram of the present application.

[0054] Wherein, 1 substrate, 2 glass plate, 3 gap filling, 4 resin composition. DETAILED DESCRIPTION

[0055] The embodiments of the present application will be described in detail below with reference to the accompanying drawings.

[0056] Example 1

[0057] A resin composition for electronic device sealing is prepared by mixing the following components in the following proportions by mass: an epoxy resin selected from bisphenol A type BE124A 16.5%, a curing agent selected from hexahydrophthalic anhydride HHPA 19.9%, a catalyst selected from 2-ethyl-4-methylimidazole 2E4MZ 0.4%, an additive 3-glycidyloxypropyltrimethoxysilane GLYMO 1.6%, a colloidal filler selected from colloidal silica (particle size 10-20 nm) EVONP-470 8.5%, and a solid filler selected from spherical silica powder (average particle size 0.5 μm) ANAD-E22 53.1%. The mixture is kneaded using a three-roll mill, and after mixing is complete, the resulting mixture is degassed using a planetary vacuum mixer to obtain the resin composition.

[0058] Example 2

[0059] A resin composition is prepared and mixed as in Example 1, except that the solid filler is selected from spherical silica powder (average particle size 0.5 μm) EM-DCS-005 53.1%.

[0060] Example 3

[0061] A resin composition is prepared and mixed as in Example 1, except that the solid filler is selected from spherical silica powder (average particle size 2.0 μm) EM-SQB-2020 53.1%.

[0062] Example 4

[0063] A resin composition is prepared and mixed as in Example 1, except that the solid filler is selected from spherical silica powder (average particle size 4.0 μm) EM-SQL-1028 53.1%.

[0064] Comparative Example 1

[0065] A resin composition is prepared by mixing the following components in the following proportions by mass: an epoxy resin selected from the group consisting of bisphenol A type BE124A 20.1%, a curing agent selected from the group consisting of hexahydrophthalic anhydride HHPA 21.1%, a catalyst selected from the group consisting of 2-ethyl-4-methylimidazole 2E4MZ 0.4%, an additive 3-glycidyloxypropyltrimethoxysilane GLYMO 1.7%, and a solid filler selected from the group consisting of spherical silica powder (average particle size 0.5 μm) ANAD-E22 53.2% and spherical silica powder (average particle size 8.0 nm) EM-BCF-007 3.5%. The mixture is kneaded with a three-roll mill, and after mixing is complete, the resulting mixture is degassed with a planetary vacuum mixer to obtain the resin composition.

[0066] Comparative Example 2

[0067] A resin composition is prepared by mixing the following components in the following proportions by mass: an epoxy resin selected from the group consisting of bisphenol A type BE124A 20.1%, a curing agent selected from the group consisting of hexahydrophthalic anhydride HHPA 21.1%, a catalyst selected from the group consisting of 2-ethyl-4-methylimidazole 2E4MZ 0.4%, an additive 3-glycidyloxypropyltrimethoxysilane GLYMO 1.7%, and a solid filler selected from the group consisting of spherical silica powder (average particle size 0.5 μm) EM-DCS-005 53.2% and spherical silica powder (average particle size 8.0 nm) EM-BCF-007 3.5%. The mixture is kneaded with a three-roll mill, and after mixing is complete, the resulting mixture is degassed with a planetary vacuum mixer to obtain the resin composition.

[0068] Comparative Example 3

[0069] A resin composition is prepared by mixing the following components in the following proportions by mass: an epoxy resin selected from the group consisting of bisphenol A type BE124A 20.1%, a curing agent selected from the group consisting of hexahydrophthalic anhydride HHPA 21.1%, a catalyst selected from the group consisting of 2-ethyl-4-methylimidazole 2E4MZ 0.4%, an additive 3-glycidyloxypropyltrimethoxysilane GLYMO 1.7%, and a solid filler selected from the group consisting of spherical silica powder (average particle size 2.0 μm) EM-SQB-2020 53.2% and spherical silica powder (average particle size 8.0 nm) EM-BCF-007 3.5%. The mixture is kneaded with a three-roll mill, and after mixing is complete, the resulting mixture is degassed with a planetary vacuum mixer to obtain the resin composition.

[0070] Comparative Example 4

[0071] A resin composition is prepared by mixing the following components in the following proportions by mass: an epoxy resin selected from the group consisting of bisphenol A type BE124A 20.1%, a curing agent selected from the group consisting of hexahydrophthalic anhydride HHPA 21.1%, a catalyst selected from the group consisting of 2-ethyl-4-methylimidazole 2E4MZ 0.4%, an additive 3-glycidyloxypropyltrimethoxysilane GLYMO 1.7%, and a solid filler selected from the group consisting of spherical silica powder (average particle size 4.0 μm) EM-SQL-1028 53.2% and spherical silica powder (average particle size 8.0 nm) EM-BCF-007 3.5%. The mixture is kneaded with a three-roll mill, and after mixing is complete, the resulting mixture is degassed with a planetary vacuum mixer to obtain the resin composition.

[0072] The above components used are purchased from the following suppliers:

[0073] 1: Bisphenol A type epoxy resin BE124A (manufacturer: Changchun Synthetic Resin Factory Co., Ltd.)

[0074] 2: Hexahydrophthalic anhydride HHPA (manufacturer: Merck)

[0075] 3: 2-Ethyl-4-methylimidazole 2E4MZ (manufacturer: Merck, Germany)

[0076] 4: 3-Glycidyloxypropyltrimethoxysilane GLYMO (manufacturer: Merck, Germany)

[0077] 5: Colloidal filler (particle size 10-20 nm) EVONP-470 (Supplier: Wellion Trade Company)

[0078] 6: Spherical silica powder ANAD-E22 (average particle size: 0.5 μm) (Supplier: Genhok Technology Co., Ltd.)

[0079] 7: Spherical silica powder EM-SQB-2020 (average particle size 2.0 μm) (Supplier: Wellion Trade Company)

[0080] 8: Spherical silica powder EM-SQL-1028 (average particle size 4.0 μm) (Supplier: Wellion Trade Company

[0081] 9: Spherical silica powder EM-DCS-005 (average particle size 0.5 μm) (Supplier: Wellion Trade Company

[0082] 10: Spherical silica powder EM-BCF-007 (average particle size 8.0 nm) (Supplier: Wellion Trade Company

[0083] The component ratio is shown in Table 1:

[0084] Table 1

[0085]

[0086] The above prepared resin composition was subjected to viscosity and flow property test, specifically as follows:

[0087] 1. Viscosity measurement: Viscosity was measured by a BROOKFIELD DV-1 viscometer equipped with ASTM spindle at 25°C.

[0088] 2. Flowability test: As shown in Figure 1 , the liquid flowability evaluation method includes the following steps: first, as shown in Figure 1 A, a test carrier was manufactured: a gap of 30 μm or 60 μm was provided on the substrate 1, and was fixed on the glass plate 2 instead of the semiconductor element. However, as the substrate 1, a glass substrate was used instead of a flexible substrate; as shown in Figure 1 B, the test carrier was placed on a hot plate with a temperature of 70°C and the prepared resin composition 4 of Examples 1-4, Comparative Examples 1-4 was placed at one end of the glass plate 2. As shown in Figure 1 C, the distance and time of the resin composition 4 filling the gap 3 flow were measured, and the results are shown in Table 2.

[0089] Table 2

[0090]

[0091] Note: In Table 2, 30 μm Gap / 2 cm / 9 min: represents that in 30 μm Gap, it takes 9 min to flow, and can run 2 cm of flow distance. 30 μm Gap / 0.4 cm / >30 min: represents that in 30 μm Gap, even if it is allowed to flow for more than 30 min, its flow distance is only 0.4 cm. 60 μm Gap: 0.5 cm / Time: >30 min, represents that in 60 μm Gap, although it flows for 30 min, it can only flow 0.5 cm of distance. 30 μm Gap: 0 cm / Time: >30 min represents that in 30 μm Gap, although it flows for 30 min, it cannot flow at all (0 cm). 60 μm Gap: 0 cm / Time: >30 min represents that in 60 μm Gap, although it flows for 30 min, it cannot flow at all (0 cm).

[0092] From the experimental results in Table 2 (Comparative Examples 1-4), if the nanoparticles (EM-BCF-007, particle size: 8.0 nm) are directly added to the powder / solid form of the formulation, the viscosity of the formulation will significantly increase due to the serious caking problem, and it is impossible to produce a uniformly dispersed resin composition. In comparison with the present application (Examples 1-4), by adding colloidal particles (EVONP-470, particle size: 10-20 nm), a uniformly dispersed resin composition can be formed. The viscosity of the epoxy resin composition formed by this scheme does not significantly increase, and the flowability in a narrow gap (30 μm) is excellent.

[0093] Note: The particle size of the silica filler in Example 1 and Example 2 is 0.5 μm (generally, the particle size of the filler is determined by D50), but different filler products may cause a huge difference in the viscosity of the bottom filler due to different particle size distribution and surface treatment. In Comparative Examples 1-4, solid SiO2 is used as the filler, and in the absence of additional colloidal fillers, the mixture formulation forms a thick mass due to the inability to uniformly disperse in the epoxy resin BE124A, thereby making it impossible to measure the viscosity.

Claims

1. A resin composition for electronic device sealing, characterized in that: The resin composition comprises, by mass percentage, 10-30% of a thermosetting resin, 15-35% of a curing agent, 0.1-3% of a catalyst, 0.8-5% of an additive, 5-20% of a colloidal filler, and 45-68% of a solid filler; the thermosetting resin is selected from an epoxy resin, and the thermosetting resin is liquid at 25°C.

2. The resin composition according to claim 1, wherein: The colloidal filler is selected from silica sol, aluminum sol or a mixture of the two, and the particle size is ≤100nm.

3. The resin composition according to claim 1, wherein: The solid filler is selected from silicon dioxide, aluminum oxide, boron nitride, aluminum nitride or a mixture of any combination of silicon dioxide, aluminum oxide, boron nitride and aluminum nitride; the particle size of the solid filler is 0.010 μm ≤ 10 μm.

4. The resin composition according to claim 2, wherein: The colloidal filler is selected from Nanobox A410, Nanobox A510, Nanobox A611, Nanobox E430, Nanobox E470, Nanobox E500, Nanobox E601, Nanobox E770, Nanobox F400, Nanobox F440, Nanobox F520, Nanobox F631, Nanobox F700, EVONP-470, LUDOX® HS-30, MAS colloidal silica, 406 colloidal silica, AEROSIL® Colloidal Silica, AEROPERL® CollidalSilica, AMSol TM 8 SM, AMSol TM 8 SMX, AMSol TM 15. AMSol TM 15 SM, AMSol TM 20 SM、AMSol TM 30. AMSol TM 30 SM、AMSol TM 4012、AMSol TM 4015、AMSol TM 50. AMSol TM HT.

5. The resin composition according to claim 1, wherein: The thermosetting resin is selected from one or more of epoxy resin, epoxy novolac resin, phenolic resin, unsaturated polyester, polyurethane, diallyl phthalate resin, bismaleimide resin, melamine resin, benzoxazine, polyimide, cyanate ester, furan resin, and silicone resin.

6. The resin composition according to claim 1, wherein: Thermosetting resins are liquid at 25°C and have at least two epoxy groups per molecule.

7. The resin composition according to claim 1, wherein: The curing agent can be selected from acid anhydride, amine type, phenol type, acid anhydride and phenol blend, amine and phenol blend, polysulfide resin, organic hydrazide.

8. The resin composition according to claim 1, wherein: The catalyst is selected from any one of Lewis acid, imidazole compound, metal complex and amine complex; the additive is selected from functional silicone resin, functional acrylate resin, coupling agent or a blend thereof.

9. A semiconductor sealant, characterized in that: The semiconductor sealant uses the resin composition according to any one of claims 1 to 8.

10. A semiconductor device, characterized in that: The semiconductor device uses the semiconductor sealing agent according to claim 9.

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