TWI711132B - Epoxy resin composition - Google Patents

Abstract

The present invention provides an epoxy resin composition that can be used as an underfill material for three-dimensional installation, which has low uranium content, excellent filling properties and suppressed pore generation. The epoxy resin composition of the present invention is an epoxy resin composition containing (A) liquid epoxy resin, (B) hardener, (C) alumina filler, and is characterized by the aforementioned (C) alumina filler The average particle size is 0.1~4.9μm, and the uranium content is 0.1~9ppb.

Description

Epoxy resin composition

The present invention relates to epoxy resin compositions that can be used as semiconductor sealing materials or adhesives.

With the miniaturization, lighter weight, and higher performance of electronic equipment, the mounting form of semiconductors has changed from wire bonding type to flip chip type.

The flip-chip semiconductor device has a structure in which the electrode on the substrate and the semiconductor element are connected through bump electrodes. When additional heat is applied to the semiconductor device of this structure during thermal cycles, etc., due to the difference in thermal expansion coefficient between the substrate made of organic materials such as epoxy resin and the semiconductor element, stress is applied to the bump electrode, and cracks occur in the bump electrode. The defect becomes a problem. In order to suppress the occurrence of this defect, it has been widely used to seal the gap between the semiconductor element and the substrate by using a liquid semiconductor sealing material called an underfill material to fix the two to each other to improve the heat cycle resistance.

As the supply method of underfill material, generally after connecting the semiconductor element and the electrode part on the substrate, the underfill material (cloth glue) is applied along the outer periphery of the semiconductor element, and the capillary phenomenon is used to inject the gap between the two. Flow into the capillary of the underfill material. After the underfill material is injected, the underfill material is heated and hardened to strengthen the connection between the two.

The underfill material is required to be excellent in injectability, adhesiveness, curability, storage stability, etc. In addition, the parts sealed with the underfill material are required to be excellent in moisture resistance and heat cycle resistance.

In order to meet the above requirements, epoxy resins have been widely used as underfill materials.

In order to improve the moisture resistance and heat cycle resistance of the part sealed by the underfill material, especially the heat cycle resistance, it is known to add a filler made of an inorganic substance to the underfill material (hereinafter referred to as "inorganic filler"). ), it is effective to control the difference in thermal expansion coefficient between a substrate made of an organic material such as epoxy resin and a semiconductor element, or to reinforce bump electrodes (refer to Patent Document 1).

As an inorganic filler added for this purpose, a silica filler is preferably used because of high electrical insulation and low thermal expansion coefficient.

On the other hand, in order to achieve high density. High-performance installation has changed from the two-dimensional installation of the usual plane configuration to the three-dimensional installation of overlapping parts for installation. As a three-dimensional mounting, for example, a three-dimensional package (such as a stacked CSP) using a laminated bare chip, or a package layer where a semiconductor chip is temporarily packaged in a separate board and then stacked in plural to achieve three-dimensionalization Combine the three-dimensional module. Moreover, there are also electronic components (semiconductor chips, passive components, etc.) installed to multi-segment wiring boards to achieve high density. High-performance installation technology.

In the past two-dimensional installation, because the chip is exposed, the self-crystal The heat dissipation of the chip is not a problem, but the three-dimensional installation of the structure of laminated multiple chips is not easy to dissipate heat, so the thermal design becomes a major problem. In order to facilitate thermal design, it is better to use the underfill material with higher thermal conductivity.

The thermal conductivity of silica filler, which is widely used as an inorganic filler, is definitely not high. Therefore, it is better to use inorganic fillers with higher thermal conductivity than silica fillers for underfill materials used for three-dimensional installation. Examples of inorganic fillers with higher thermal conductivity than silica fillers include alumina fillers, or fillers such as magnesium oxide, boron nitride, aluminum nitride, and diamond. Among them, the alumina filler is preferred because of its low cost, easy improvement of sphericity, and excellent moisture resistance.

In addition, in order to prevent malfunctions of devices that are susceptible to the alpha line, it is necessary to reduce the alpha lines emitted from the uranium, nightmare, and degraded substances contained in the inorganic filler contained in the underfill material (Patent Documents 2 to 4). Alumina filler is the above-exemplified inorganic filler whose thermal conductivity is higher than that of silica filler. The amount of alpha ray released is relatively small, but it is still required to further reduce the amount of alpha ray released.

In Patent Documents 2 to 4, the total amount of uranium and nightma in aluminum hydroxide powder used as a raw material or in an alumina filler made from aluminum hydroxide powder is less than 10 ppb.

However, the conventional alumina fillers obtained from Patent Documents 2 to 4 have a large average particle size D50 of 2 μm or more by the laser diffraction scattering method, so when they are added to the underfill material for three-dimensional mounting Because of the low filling properties of the underfill material, pores are prone to occur during filling.

[Prior Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Application Laid-Open No. 10-173103

[Patent Document 2] JP 2005-248087 A

[Patent Document 3] JP 2014-5359 A

[Patent Document 4] JP 2011-236118 A

The present invention is to solve the above-mentioned problems of the prior art, and aims to provide an epoxy resin composition with low uranium content, and when used as an underfill material for three-dimensional installation, the underfill material has excellent filling properties and suppresses the occurrence of pores Things.

In order to achieve the above-mentioned object, the present invention provides an epoxy resin composition containing (A) liquid epoxy resin, (B) hardener, and (C) alumina filler, the characteristics of which are described above (C) The average particle size of the alumina filler is 0.1~4.9μm, and the uranium content is 0.1~9ppb.

In the epoxy resin composition of the present invention, the curing agent (B) is preferably an aromatic amine curing agent.

In the epoxy resin composition of the present invention, the content of the aromatic amine hardener is preferably 0.5 to 1.5 equivalents relative to the epoxy equivalent of the liquid epoxy resin (A).

In the epoxy resin composition of the present invention, the content of the aforementioned (C) alumina filler is preferably 45 to 90 parts by mass relative to 100 parts by mass of the total mass of all components of the epoxy resin composition.

The epoxy resin composition of the present invention preferably has an alpha line amount of 0.0020count/cm ² in the hardened substance. h or less.

The epoxy resin composition of the present invention may further contain (D) a silane coupling agent.

The epoxy resin composition of the present invention preferably has a roundness of 0.9 or more of the aforementioned (C) alumina filler.

Furthermore, the present invention provides a semiconductor sealing agent containing the epoxy resin composition of the present invention.

In addition, the present invention provides an adhesive containing the epoxy resin composition of the present invention.

In addition, the present invention provides a resin cured product obtained by heating the epoxy resin composition of the present invention.

Moreover, the present invention provides a semiconductor device having a flip-chip semiconductor element sealed with the semiconductor sealing material of the present invention.

The epoxy resin composition of the present invention uses alumina filler as an inorganic filler, so when it is used as an underfill material for three-dimensional installation, thermal design is easy.

Since the epoxy resin composition of the present invention uses alumina filler with a uranium content of 0.1-9 ppb as an inorganic filler, the amount of alpha line in the hardened substance is as low as 0.0020count/cm ² . Below h, when used as an underfill material, it can prevent malfunction of devices that are susceptible to alpha rays.

The epoxy resin composition of the present invention uses an alumina filler with an average particle size of 0.1-4.9 μm as an inorganic filler, so when used as an underfill material for three-dimensional mounting, it has good filling properties and suppresses the occurrence of voids.

The following describes the present invention in detail.

The epoxy resin composition of the present invention contains the components (A) to (C) shown below as essential components.

(A) Liquid epoxy resin

(A) The liquid epoxy resin of component is a component which becomes the main agent of the epoxy resin composition of this invention.

The liquid epoxy resin in the present invention means an epoxy resin that is liquid at room temperature.

The liquid epoxy resin of the present invention is exemplified by bisphenol A type epoxy resins with an average molecular weight of about 400 or less; for example, p-glycidoxyphenyl dimethyl ginseng bisphenol A diglycidyl ether has many branches Functional bisphenol A epoxy resin; bisphenol F epoxy resin; phenol novolac epoxy resin with an average molecular weight of about 570 or less; such as vinyl (3,4-cyclohexene) dioxide, 3, 4-Epoxycyclohexylcarboxylic acid (3,4-epoxycyclohexyl) methyl ester, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2-( 3,4-epoxy ring Hexyl) 5,1-spiro (3,4-epoxycyclohexyl)-m-dioxane alicyclic epoxy resin; such as 3,3',5,5'-tetramethyl-4,4 '-Diglycidyloxybiphenyl biphenyl type epoxy resin; such as diglycidyl hexahydrophthalate, diglycidyl 3-methylhexahydrophthalate, and hexahydroterephthalic acid Diglycidyl glycidyl ester type epoxy resin; such as diglycidyl aniline, diglycidyl toluidine, triglycidyl-p-aminophenol, tetraglycidyl-m-xylene diamine, Tetraglycidyl bis (aminomethyl) cyclohexane glycidyl amine epoxy resin; and 1,3-diglycidyl-5-methyl-5-ethylhydantoin Urea type epoxy resin; epoxy resin containing naphthalene ring. In addition, epoxy resins with polysiloxane skeletons such as 1,3-bis(3-glycidoxypropyl)-1,1,3,3-tetramethyldisiloxane can also be used. Furthermore, (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, cyclohexane dimethanol diglycidyl ether are also exemplified. Diepoxy compounds of glycerol ether; such as trimethylolpropane triglycidyl ether, triepoxide compounds of glycerol triglycidyl ether, etc.

Among them, a liquid bisphenol type epoxy resin, a liquid aminophenol type epoxy resin, a silicone modified epoxy resin, and a naphthalene type epoxy resin are preferable. More preferably, liquid bisphenol A type epoxy resin, liquid bisphenol F type epoxy resin, p-aminophenol type liquid epoxy resin, 1,3-bis(3-glycidoxypropyl) ) Tetramethyldisiloxane, naphthalene type epoxy resin.

(A) The liquid epoxy resin as a component may be used individually or may use 2 or more types together.

Moreover, even if the epoxy resin is solid at room temperature, by using a liquid ring Oxygen resin can also be used when the mixture is liquid.

(B) Hardener

(B) If the hardener of component (B) is an epoxy resin hardener, it is not particularly limited, and conventional ones can be used, and any one of amine hardeners, acid anhydride hardeners, and phenol hardeners can be used.

Specific examples of amine hardeners are triethylenetetramine, tetraethylenepentamine, m-xylene diamine, trimethylhexamethylene diamine, 2-methylpentamethylene diamine Aliphatic polyamines such as amines, such as isophorone diamine, 1,3-diaminomethylcyclohexane, bis(4-aminocyclohexyl)methane, norbornene diamine, 1,2-diamine Alicyclic polyamines such as aminocyclohexane, piperidine-type polyamines such as N-aminoethylpiperidine, 1,4-bis(2-amino-2-methylpropyl)piperidine, etc. , Diethyltoluenediamine, dimethylthiotoluenediamine, 4,4'-diamino-3,3'-diethyldiphenylmethane, bis(methylthio)toluenediamine, two Amino diphenylmethane, meta-phenylene diamine, diamino diphenyl sulfide, diethyl toluene diamine, trimethylene bis (4-amino benzoate), polytetramethylene oxide Aromatic polyamines such as bis-p-aminobenzoate. In addition, as a commercially available product, T-12 (trade name, manufactured by Sanyo Chemical Industry Co., Ltd.) (amine equivalent 116) is exemplified.

Specific examples of acid anhydride hardeners include methyl tetrahydrophthalic anhydride, methyl hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, etc. alkylated tetrahydrophthalic acid Acid anhydride, hexahydrophthalic anhydride, methyl humic anhydride, alkenyl substituted succinic anhydride, methyl nadic anhydride, glutaric anhydride, etc.

Specific examples of phenolic hardeners refer to all monomers, oligomers, and polymers having phenolic hydroxyl groups, and examples include phenol novolac resins and their alkyl or allyl compounds, cresol novolac resins, Phenol aralkyl (including phenylene and biphenyl skeleton) resin, naphthol aralkyl resin, trisphenol methane resin, dicyclopentadiene type phenol resin, etc.

Among them, amine hardeners are preferred due to their excellent moisture resistance and heat cycle resistance. Among them, diethyltoluenediamine, dimethylthiotoluenediamine, 4,4'-diamino-3,3 Aromatic amine hardeners such as'-diethyldiphenylmethane are preferable from the viewpoints of heat resistance, mechanical properties, adhesion, electrical properties, and moisture resistance. In addition, since it is liquid at room temperature, it is also preferable as a curing agent for the epoxy resin in the epoxy resin composition of the present invention.

(B) The hardener of the component may be used alone or in combination of two or more kinds.

In the resin composition of the present invention, the mixing ratio of the curing agent of the component (B) is not particularly limited, but in the case of an aromatic amine curing agent, it is equivalent to 1 equivalent of the epoxy group of the liquid epoxy resin of the component (A). It is preferably 0.5 to 1.5 equivalents, more preferably 0.7 to 1.3 equivalents.

(C) Alumina filler

When using the epoxy resin composition of the present invention as an underfill material, the alumina filler of component (C) is added for the purpose of improving the moisture resistance and heat cycle resistance of the sealing part, especially the heat cycle resistance. The reason why the heat cycle resistance is improved by adding alumina filler is that by reducing the coefficient of linear expansion, the swelling of the hardened epoxy resin composition caused by thermal cycling can be suppressed. Expansion. Contraction.

The reason for using the alumina filler as the component (C) is that the thermal conductivity is higher than that of the silica filler as described above, so when it is used as an underfill material for three-dimensional mounting, the thermal design becomes easier. In addition, the above-exemplified inorganic fillers with higher thermal conductivity than silica fillers are low-cost, easy to improve sphericity, and are excellent in moisture resistance.

In addition, in order to prevent the malfunction of devices that are susceptible to the alpha line, it is necessary to reduce the alpha line released from the uranium, thorium, and its degrading substances in the inorganic filler contained in the underfill material (Patent Documents 2 to 4).

In the epoxy resin composition of the present invention, the average particle size of the alumina filler of the component (C) is 0.1 to 4.9 μm. The reason is that when used as an underfill material for three-dimensional mounting, it has excellent filling properties and can suppress the occurrence of voids. When the average particle size of the alumina filler of component (C) is less than 0.1μm, the viscosity of the epoxy resin composition becomes very high, so when used as an underfill material for three-dimensional mounting, the filling and workability deteriorate.

On the other hand, when the average particle size of the alumina filler of the component (C) exceeds 4.9 μm, when it is used as an underfill material for three-dimensional mounting, large particles may block the gaps and may cause poor filling. And even if it can be filled, it is not suitable because it is entrained into the pores during filling.

The average particle diameter of the alumina filler of the component (C) is more preferably 0.1 to 3.0 μm, and more preferably 0.1 to 1.7 μm.

(C) The shape of the alumina filler of the component is not particularly limited, and it may be in any form such as granular, powder, and scale. In addition, when the shape of the alumina filler is other than granular, the so-called flat alumina filler The average particle size means the average maximum diameter of the alumina filler.

However, when the roundness of the alumina filler of component (C) is 0.9 or more, it is based on the dispersibility of the alumina filler in the epoxy resin composition and the injection when used as an underfill material for three-dimensional installation It is better to improve the performance and the alumina filler is closer to the densest filling state. The "roundness" in this manual is defined as the "ratio of the smallest diameter to the largest diameter of a particle" in the two-dimensional image observed with a scanning electron microscope (SEM). It means that the ratio of the smallest diameter to the largest diameter in the two-dimensional image observed with a scanning electron microscope (SEM) is 0.9 or more.

As mentioned above, compared with silica fillers, alumina fillers have higher thermal conductivity, so when used as underfill materials for three-dimensional mounting, thermal design becomes easier.

However, because alumina fillers contain uranium as an unavoidable impurity in the filling part of its manufacturing raw materials, the manufactured alumina filler also has uranium as an inevitable impurity, so when used as an underfill material for three-dimensional installation, There is a risk of the device malfunctioning due to the alpha line released from the uranium.

In the resin composition of the present invention, since the uranium content of the alumina filler of the component (C) is 0.1-9 ppb, the amount of alpha rays from the hardened substance of the resin composition can be reduced to the extent that the device does not malfunction. Specifically, the amount of alpha rays from the cured product of the resin composition is reduced to 0.0020count/cm ² . h or less.

In the resin composition of the present invention, the uranium content of the alumina filler of the component (C) is preferably 0.1 to 4.9 ppb or less.

According to the methods described in Patent Documents 2 to 4, Aluminum powder can be used to produce alumina fillers whose total amount of uranium and thorium is less than 10ppb. However, the average particle size D50 of this alumina filler obtained by the laser diffraction scattering method is 2μm or more. Alumina filler of 0.1~4.9μm.

Alumina fillers with an average particle size of 0.1 to 4.9 μm and a uranium content of 0.1 to 9 ppb can be obtained by, for example, Japanese Patent Application Publication No. 2002-285003, Japanese Patent Application Publication No. 2003-119019, VMC method (Vapourized Metal Combution Method, Evaporated metal incineration method) manufacturing. The so-called VMC method is to form a chemical flame by a burner in an oxygen-containing atmosphere, in which a part of the metal (here, alumina filler, the same below) will be formed as the target oxide particles It is Al, the same below) A method in which powder is injected in an amount that forms a dust cloud to cause deflagration to synthesize oxide particles.

If it is explained for the VMC method, it is as follows. First, the container is filled with oxygen-containing gas of reaction gas, and a chemical flame is formed in the reaction gas. Secondly, metal powder is thrown into the chemical flame to form a high-concentration (500g/m ³ or more) dust cloud. Then, the chemical flame imparts heat energy to the surface of the metal powder to increase the surface temperature of the metal powder, and the metal vapor from the surface of the metal powder diffuses to the surroundings. The metal vapor powder reacts with oxygen to cause fire and flame. The heat generated by the flame further promotes the vaporization of the metal powder, and the generated metal vapor is mixed with the reaction gas to spread the fire in a chain. At this time, the metal powder itself is destroyed and dispersed, promoting flame propagation. By natural cooling of the gas generated after combustion, it can become a cloud of oxide particles. The resulting oxide particles can be captured by charging with an electric dust collector or the like.

The VMC system uses the principle of dust explosion to obtain a large number of oxide particles in an instant, and the particles become a slightly true spherical shape. The particle size of fine particles can be adjusted by adjusting the particle size, amount, flame temperature, etc. of the injected powder, and alumina filler with an average particle size of 0.1~4.9μm can be synthesized.

In the resin composition of the present invention, the content of the alumina filler of the component (C) is preferably 45 to 90 parts by mass relative to 100 parts by mass of the total mass of all components of the resin composition.

When the content of the alumina filler of component (C) is less than 45 parts by mass, the linear expansion coefficient of the resin composition becomes larger, and when used as an underfill material for three-dimensional installation, the heat cycle resistance of the sealing part is reduced.

On the other hand, when the content of the alumina filler of component (C) exceeds 90 parts by mass, the viscosity of the resin composition increases. When used as an underfill material for three-dimensional mounting, it is used as a liquid sealing material for flip chip packaging. At this time, the implantability into the gap between the semiconductor element and the substrate decreases.

(C) The content of the alumina filler of the component is preferably 50 to 80 parts by mass, and more preferably 55 to 75 parts by mass relative to 100 parts by mass of the total mass of all components of the resin composition.

In addition to the above-mentioned (A) to (C) components, the epoxy resin composition of the present invention may contain the following components as necessary.

(D) Coupling agent

In order to improve the adhesion of the epoxy resin composition of the present invention as an underfill material for three-dimensional installation, it may also contain a coupling agent as (D) Ingredients.

As the coupling agent of the component (D), various silane coupling agents such as epoxy-based, amine-based, vinyl-based, methacrylic-based, acrylic-based, and thiol-based, can be used. Among them, the epoxy-based silane coupling agent is preferable because it has an excellent effect of improving the adhesion and mechanical strength when the epoxy resin composition is used as an underfill material for three-dimensional mounting.

Specific examples of epoxy-based silane coupling agents include 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (trade name: KBM- 303, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropylmethyldimethoxysilane (trade name: KBM-402, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyl trimethyl Oxyoxysilane (trade name: KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropylmethyl diethoxysilane (trade name: KBE-402, manufactured by Shin-Etsu Chemical Co., Ltd.), 3-glycidoxypropyltriethoxysilane (trade name: KBE-403, manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

When a silane coupling agent is contained as component (D), it is preferably 0.1 to 3.0% by mass in terms of mass percentage relative to the total mass of the liquid epoxy resin of component (A) and hardener of component (B), and more It is preferably 0.3 to 2.0% by mass, and more preferably 0.5 to 1.5% by mass.

(E) Hardening accelerator

The liquid sealing material of the present invention may contain a hardening accelerator as the (E) component. As the hardener of component (B), use acid anhydride hardener or phenol hardener In the case of an agent, it is preferable to contain a hardening accelerator as the component (E).

If the hardening accelerator as the component (E) is an epoxy resin hardening accelerator, it is not particularly limited, and a conventional one can be used. Examples include imidazole hardening accelerators (including microcapsule type and epoxy addition molding), tertiary amine hardening accelerators, phosphorus compound hardening accelerators, and the like.

These imidazole-based hardening accelerators are preferable because they are excellent in compatibility with other components of the semiconductor resin sealing material and the hardening speed of the semiconductor resin sealing material.

Specific examples of imidazole-based hardening accelerators include 2-methylimidazole, 2-undecylimidazole, 2-pentadecylimidazole, 2-ethyl-4-methylimidazole, and 2-phenylimidazole. , 2-Phenyl-4-methylimidazole and other imidazole compounds.

In addition, encapsulated imidazoles called microencapsulated imidazoles or epoxy addition-formed imidazoles can also be used. That is, it is also possible to use an imidazole-based latent hardener whose surface is blocked and encapsulated with urea or isocyanate compound, or an imidazole compound is added with epoxy compound, and its surface Imidazole is a latent hardener that is blocked and encapsulated by isocyanate compounds. Specifically, for example, NOVACURE HX3941HP, NOVACURE HXA3042HP, NOVACURE HXA3922HP, NOVACURE HXA3792, NOVACURE HX3748, NOVACURE HX3721, NOVACURE HX3722, NOVACURE HX3088, NOVACURE HX3741, NOVACURE HX3741, NOVACURE HX3742, manufactured by Asahi Chemical Etc., AMICURE PN-40J (Ajinomoto Precision Technology FUJICURE FXR-1121 (manufactured by Fuji Chemical Co., Ltd., trade name), FUJICURE FXR-1121 (manufactured by Fuji Chemical Industry Co., Ltd., trade name).

(Other formulations)

The liquid sealing material of the present invention may further contain components other than the aforementioned (A) to (E) components. As specific examples of such components, elastomers, hardening accelerators, metal complexes, leveling agents, colorants, ion scavengers, defoamers, flame retardants, etc. can be formulated. The type and amount of each compounding agent are as usual.

(Preparation of epoxy resin composition)

The liquid sealing material of the present invention is prepared by mixing and stirring the above-mentioned (A) to (C) components and, when contained, the (D) component, (E) component, and other compounding agents that are further compounded as necessary.

Mixing and stirring can be performed using a roll mill, but of course it is not limited to this. (A) When the epoxy resin of the component is in a solid form, it is preferably liquefied and fluidized by heating or the like to be mixed.

The ingredients can be mixed at the same time, or a part can be mixed first, and then the rest can be mixed, etc., and it can be changed appropriately.

Next, the characteristics of the epoxy resin composition of the present invention will be described.

The epoxy resin composition of the present invention preferably has a viscosity of 200Pa at normal temperature (25°C). Below s, it can be used as an underfill material for three-dimensional installation with good injectability.

The viscosity of the epoxy resin composition of the present invention at room temperature (25°C) is better 150Pa. s or less.

Furthermore, the glass transition temperature (Tg) of the heat-hardened product of the epoxy resin composition of the present invention is preferably 50°C or higher. When used as an underfill material for three-dimensional installation, heat resistance cycle of the part sealed with the underfill material Excellent performance.

The glass transition temperature (Tg) of the heat-hardened product of the epoxy resin composition of the present invention is more preferably 80°C or higher.

Furthermore, the thermal conductivity of the heat-cured product of the epoxy resin composition of the present invention is preferably 0.3 W/(m.K) or higher, and when used as an underfill material for three-dimensional installation, thermal design is easy.

The thermal conductivity of the heat-hardened product of the epoxy resin composition of the present invention is more preferably 0.5 W/(m.K) or more, and more preferably 0.7 W/(m.K) or more.

In addition, the amount of α line in the cured product of the epoxy resin composition of the present invention is preferably 0.0020 count/cm ² . Below h, when used as an underfill material for three-dimensional installation, it can prevent malfunctions of devices that are susceptible to α-line.

Furthermore, the amount of alpha line in the cured product of the epoxy resin composition of the present invention is more preferably 0.0015 count/cm ² . Below h, it is more preferably 0.0010count/cm ² . h or less.

In addition, when the epoxy resin composition of the present invention is used as an underfill material for three-dimensional mounting, the injectability by the capillary tube is good. Specifically, when evaluating the injectability into the gap in the order described in the examples described later, the injection time into the 20 μm gap is preferably 800 seconds or less, more preferably 750 seconds or less, and still more preferably 650 seconds or less.

Moreover, no porosity occurs when the gap is injected.

Next, the use method of the epoxy resin composition of the present invention will be described as an example of using it as an underfill material.

When the epoxy resin composition of the present invention is used as an underfill material, the epoxy resin composition of the present invention is filled in the gap between the substrate and the semiconductor element by the following procedure.

While heating the substrate to 70~130°C, for example, the epoxy resin composition of the present invention is applied to one end of the semiconductor element, and the epoxy resin composition of the present invention is filled between the substrate and the semiconductor element by capillary phenomenon之 gap. At this time, in order to shorten the time required for filling the epoxy resin composition of the present invention, the substrate may be tilted to cause a pressure difference between the inside and outside of the gap.

After filling the gap with the epoxy resin composition of the present invention, the substrate is heated at a specific temperature for a specific time, specifically, heated at 80-200°C for 0.2-6 hours, and the epoxy resin composition is cured by heating And seal the gap.

The semiconductor device of the present invention uses the epoxy resin composition of the present invention as an underfill material to seal the sealing portion, that is, the gap between the substrate and the semiconductor element, in the above-mentioned order. Here, the semiconductor element to be sealed is an integrated circuit, a large integrated circuit, a transistor, a thyristor, a diode, a capacitor, etc., and is not particularly limited.

However, due to the high thermal conductivity of the above-mentioned heat-cured material, it is better to use a three-dimensional package (such as a stacked CSP) in which bare chips are laminated, or to use a semiconductor chip that is temporarily packaged with independent monomers and then overlapped The three-dimensional package and laminated three-dimensional module have three-dimensional safety Semiconductor device with structure.

In addition, the epoxy resin composition of the present invention can also be used for applications such as adhesives and solder resists.

[Example]

Hereinafter, the present invention will be described in detail with examples, but the present invention is not limited thereto.

(Examples 1 to 4, Comparative Examples 1 to 2)

The raw materials were kneaded using a roll mill to prepare the epoxy resin compositions of Examples 1 to 4 and Comparative Examples 1 to 2 so as to have the mixing ratio shown in the following table. In addition, the numerical values related to each composition in the table indicate parts by mass.

(A) Epoxy resin

Epoxy resin A1: Bisphenol F type epoxy resin, product name YDF8170, manufactured by Nippon Steel Chemical Co., Ltd., epoxy equivalent 158g/eq

(B) Hardener

Hardener B1: Amine hardener, 4,4’-diamino-3,3’-diethyldiphenylmethane, product name Kayahard A-A, manufactured by Nippon Kayaku Co., Ltd.

(C) Alumina filler

Alumina filler C1: average particle size 0.7μm, uranium content 0.1ppb

Alumina filler C2: average particle size 0.7μm, uranium content 3ppb

Alumina filler C3: average particle size 0.7μm, uranium content 9ppb

Alumina filler C4: average particle size 0.7μm, uranium content 16ppb

Alumina filler C5: average particle size 4.9μm, uranium content 9ppb

Alumina filler C6: average particle size 5μm, uranium content 9ppb

(D) Coupling agent

Coupling agent D1: Epoxy silane coupling agent (3-glycidoxypropyltrimethoxysilane), product name KBM403 (manufactured by Shin-Etsu Chemical Co., Ltd.)

The prepared epoxy resin composition was used as an evaluation sample and subjected to the following evaluations.

(Viscosity)

Using a BrookField viscometer, the viscosity of the evaluation sample immediately after preparation was measured at a liquid temperature of 25°C and 50 rpm.

(Glass transition temperature (Tg))

×200mm之圓柱狀之硬化物，使用BRUKER ASX製TMA4000S，藉由TMA法測定玻璃轉移溫度。 For the evaluation sample, heat and harden at 165°C for 120 minutes to form 8mm

The cylindrical hardened product of ×200mm uses TMA4000S manufactured by BRUKER ASX, and the glass transition temperature is measured by the TMA method.

(Thermal conductivity)

The thermal conductivity of the cured product of the evaluation sample was measured by the following procedure.

The resin cured product of the evaluation sample heated and cured at 165°C for 120 minutes was cut into 10 mm × 10 mm, and the thermal conductivity was measured using a thermal conductivity measuring device (LFA447 NANOFLASH, manufactured by NETZSCH).

(Injection)

Use aluminum tape to set a gap of 20 μm between the two glass substrates, instead of semiconductor elements, fix the glass plate to make a test piece. The test piece was placed on a hot plate set at 110°C, a sample for evaluation was applied to one end of the glass plate, and the injection distance was measured until it reached 20 mm. This sequence is performed twice, and the average value of the measured value is set as the measured value of the injection time.

In addition, the presence or absence of voids in the injected sample for evaluation was confirmed visually.

The viscosity of Examples 1 to 4 at room temperature (25°C) are all 200Pa. Below s, the Tg of the heat-cured material is below 200℃, the thermal conductivity is above 0.3W/(m.K), and the amount of α line is 0.020count/cm ² . The injection time for a gap of less than h and 20μm is less than 800 seconds, and no voids are confirmed during injection. (C) In Comparative Example 1, where the uranium content of the alumina filler of component (C) exceeds 9ppb, the alpha line amount of the hardened product exceeds 0.020count/cm ² . h. In Comparative Example 2 where the average particle size of the alumina filler of component (C) exceeded 4.9 μm, the injection time in the 20 μm gap exceeded 800 seconds, and voids were confirmed during injection.

Claims (10)

An epoxy resin composition containing (A) liquid epoxy resin, (B) hardener, and (C) alumina filler, characterized by the aforementioned (C) alumina filler The average particle size is 0.1~4.9μm, and the uranium content is 0.1~9ppb. The content of the above-mentioned (C) alumina filler is 45~90 relative to the total mass of all components of the epoxy resin composition Mass parts. The epoxy resin composition of claim 1, wherein the aforementioned (B) hardener is an aromatic amine hardener. The epoxy resin composition of claim 2, wherein the content of the aromatic amine hardener is 0.5 to 1.5 equivalents relative to the epoxy equivalent of the (A) liquid epoxy resin. . Such as the epoxy resin composition of any one of claims 1 to 3, in which the amount of alpha line in the hardened substance is 0.0020count/cm ² . h or less. Such as the epoxy resin composition of any one of claims 1 to 3, which further contains (D) a silane coupling agent. The epoxy resin composition according to any one of claims 1 to 3, wherein the roundness of the aforementioned (C) alumina filler is 0.8 or more. A semiconductor encapsulant containing the epoxy resin composition according to any one of claims 1 to 6. An adhesive containing the epoxy resin composition according to any one of claims 1 to 6. A hardened resin obtained by heating the epoxy resin composition of any one of claims 1 to 6. A semiconductor device having a flip-chip semiconductor element sealed with a semiconductor sealing material as in claim 7.