JP6015912B2 - Liquid epoxy resin composition and semiconductor electronic component - Google Patents

Description

  The present invention relates to a liquid epoxy resin composition and a semiconductor electronic component using the same.

  Conventionally, the liquid epoxy resin composition containing an epoxy resin and a hardening | curing agent is used for adhesion | attachment and sealing of various members.

  A cured product of the epoxy resin can be obtained by curing the composition by applying heat, light, pressure, or the like to the composition containing the epoxy resin and the curing agent. A hardening accelerator, a filler, etc. are added to this composition according to a use.

  The cured epoxy resin has features such as excellent chemical resistance, corrosion resistance, mechanical properties, thermal properties, excellent adhesion to various substrates, electrical properties, and workability regardless of environment. For this reason, epoxy resin compositions are widely used in fields such as adhesives and sealants for electronic materials.

  For example, as a sealing material used for flip chip mounting in the field of electronic materials, a liquid epoxy resin composition containing a liquid epoxy resin as a main ingredient at room temperature and a curing agent, an inorganic filler, etc., is typical. It is used as a thing (refer patent document 1, 2).

  Such a sealing material protects the bumps, relieves the stress at the solder joint caused by the difference in thermal expansion coefficient between the semiconductor device and the substrate, and provides functions such as ensuring moisture resistance and airtightness. be able to.

  In order to provide such a function and suppress the occurrence of cracks at the time of reflow and the peeling of the adhesive interface, it is required to make the sealing material tough and to lower the glass transition temperature and the elastic modulus.

  As a technique for coping with such a demand, it has been proposed to mix an epoxy-modified polybutadiene with an epoxy resin composition (see Patent Document 3).

JP 2009-149820 A JP 2007-091849 A JP 2011-137092 A

  However, since the epoxy-modified polybutadiene has an unsaturated double bond in its molecule, there is a problem that oxidation is accelerated under high temperature conditions, and it becomes brittle and hard.

  By blending an antioxidant, the oxidation of the epoxy-modified polybutadiene can be delayed to some extent, but according to the study by the present inventors, long-term reliability required for semiconductor electronic components and the like is hardly obtained. I know that.

  The present invention has been made in view of the circumstances as described above, and can obtain a cured product having a low glass transition temperature and a low elastic modulus, and can greatly improve the heat deterioration resistance and provide a low elastic modulus for a long period of time. It is an object of the present invention to provide a liquid epoxy resin composition that can be maintained and a semiconductor electronic component using the same.

  In order to solve the above-mentioned problems, the liquid epoxy resin composition of the present invention is characterized by containing an epoxy resin and an epoxy-modified polybutadiene as main components, a curing agent, and a radical initiator.

  In this liquid epoxy resin composition, the epoxy-modified polybutadiene has an epoxy equivalent in the range of 180 to 250 g / eq, and preferably contains 70 mol% of a repeating unit derived from a 1,2-vinyl structure.

  In this liquid epoxy resin composition, the content of the radical initiator is preferably in the range of 0.01 to 3 parts by mass with respect to 100 parts by mass of the epoxy-modified polybutadiene.

  This liquid epoxy resin composition preferably contains an organic peroxide as a radical initiator.

  In this liquid epoxy resin composition, it is preferable that the curing agent contains at least one selected from an acid anhydride curing agent and a phenol curing agent, and further contains a curing accelerator, an inorganic filler, and a coupling agent. .

  The semiconductor electronic component of the present invention is characterized in that a semiconductor device and a substrate are bonded by a cured product of the liquid epoxy resin composition.

  According to the liquid epoxy resin composition of the present invention and a semiconductor electronic component using the liquid epoxy resin composition, a cured product having a low glass transition temperature and a low elastic modulus can be obtained, and the heat deterioration resistance is greatly improved, resulting in low elasticity for a long time. The rate can be maintained.

  The present invention is described in detail below.

  In the liquid epoxy resin composition of the present invention, an epoxy resin that is liquid at room temperature can be used as the epoxy resin blended as the main agent.

  In the present specification, “liquid at normal temperature” means having fluidity in a temperature range of 5 to 28 ° C. under atmospheric pressure, particularly around 18 ° C. at room temperature.

  In the liquid epoxy resin composition of the present invention, the main agent may be mixed with an epoxy resin that is solid at room temperature as long as the mixture with the epoxy resin that is liquid at room temperature becomes liquid at room temperature.

  If the epoxy resin mix | blended as a main ingredient has 2 or more of epoxy groups in 1 molecule, the molecular weight and molecular structure will not be specifically limited, Various things can be used.

  Specifically, for example, various epoxy resins such as a glycidyl ether type, a glycidyl amine type, a glycidyl ester type, and an olefin oxidation type (alicyclic) can be used.

  More specifically, for example, bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins, hydrogenated bisphenol type epoxy resins such as hydrogenated bisphenol A type epoxy resins and hydrogenated bisphenol F type epoxy resins, Biphenyl type epoxy resin, naphthalene ring-containing epoxy resin, alicyclic epoxy resin, dicyclopentadiene type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, aliphatic epoxy resin, tri Glycidyl isocyanurate or the like can be used. These may be used alone or in combination of two or more.

  Among these, bisphenol type epoxy resin and hydrogenated bisphenol type epoxy resin are preferable as the epoxy resin that is liquid at room temperature, considering the low viscosity of the liquid epoxy resin composition and the improvement of the physical properties of the cured product, and the epoxy equivalent is 150 ~ 200 g / eq is preferred.

  In the liquid epoxy resin composition of the present invention, epoxy-modified polybutadiene is blended as a main agent. By blending the epoxy-modified polybutadiene, a cured product having a low glass transition temperature and a low elastic modulus can be obtained.

  The epoxy-modified polybutadiene used in the present invention has a repeating unit represented by the following formula (A) and a repeating unit represented by the formula (B).

  The epoxy-modified polybutadiene preferably has an epoxy equivalent in the range of 180 to 250 g / eq. Within this range, a cured product having good curability and low glass transition temperature and low elastic modulus can be obtained. The epoxy equivalent is determined by the perchloric acid method.

  The epoxy-modified polybutadiene may have a repeating unit represented by the following formula (C) and a repeating unit represented by the formula (D), but the repeating unit derived from the 1,2-vinyl structure (A), ( B) is preferably contained in an amount of 70 mol% or more, more preferably 75 mol% or more, and even more preferably 85% or more.

  The butadiene homopolymer used for the production of the epoxy-modified polybutadiene preferably has a number average molecular weight (Mn) in the range of 500 to 10,000, and more preferably in the range of 1000 to 4000.

  The viscosity of the epoxy-modified polybutadiene is preferably in the range of 200 to 1500 poise / 45 ° C.

  As the epoxy-modified polybutadiene, for example, one having the following structure can be preferably used.

(In the formula, m represents an integer of 4 to 15, and m + n is in the range of 15 to 45.)
Epoxy-modified polybutadiene is obtained, for example, by epoxidizing a butadiene homopolymer composed of 70 to 100 mol% of repeating units represented by the formula (A) and 30 to 0 mol% of repeating units represented by the formula (C). be able to.

  The production method of the butadiene homopolymer used for the production of the epoxy-modified polybutadiene is not particularly limited, but a homopolymer obtained by a method of living polymerizing a butadiene monomer is preferable.

  Living polymerization techniques include, for example, a method of polymerizing using an organic rare earth metal complex as a polymerization initiator; an organic alkali metal compound as a polymerization initiator, and in the presence of an alkali metal or alkaline earth metal mineral salt. An anion polymerization method using an organic alkali metal compound as a polymerization initiator in the presence of an organoaluminum compound; an atom transfer radical polymerization (ATRP) method and the like.

  Among these living polymerization methods, an anionic polymerization method (sodium polymerization method) using a sodium dispersion as a polymerization initiator can easily obtain a butadiene homopolymer having a large proportion of repeating units represented by the formula (A). It is preferable in that it can be performed. The sodium dispersion is obtained by dispersing fine sodium particles having an average particle diameter of several μm in an inert medium.

  Epoxidation of a butadiene homopolymer can be performed by a reaction in which an oxygen atom is added to a carbon-carbon unsaturated double bond. This reaction is known. For example, in a solvent such as ether, chloroform, acetone, dioxane, acetic acid, butadiene homopolymer with organic peracids such as peracetic acid, perbenzoic acid, permonophthalic acid, hydrogen peroxide, ozone, hydroperoxide, etc. Epoxidation can be performed by acting. This epoxidation reaction is usually performed in a temperature range of 0 to 150 ° C.

  Examples of commercially available products of epoxy-modified polybutadiene include JP-100 and JP-200 (manufactured by Nippon Soda Co., Ltd.).

  The content of the epoxy-modified polybutadiene in the liquid epoxy resin composition of the present invention is preferably within the range of 10 to 90 parts by weight, and preferably 30 to 70 parts by weight with respect to 100 parts by weight of the total amount of the epoxy resin and the epoxy-modified polybutadiene. Within the range is more preferable. Within this range, a cured product having a low glass transition temperature and a low elastic modulus can be obtained, and the curability can be improved.

  A curing agent is blended in the liquid epoxy resin composition of the present invention. The curing agent is not particularly limited, but for example, an acid anhydride curing agent, a phenol curing agent, an amine curing agent, an imidazole curing agent, a hydrazide, a polymercaptan, a Lewis acid-amine complex, or the like is used. Can do. Among these, it is preferable to use an acid anhydride-based curing agent or a phenol-based curing agent in view of lowering the viscosity, storage stability, heat resistance of the cured product, and the like.

  Examples of the acid anhydride-based curing agent include methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hymic anhydride, pyromellitic dianhydride, benzophenone tetracarboxylic acid, and the like. Acid dianhydride, 3,4-dimethyl-6- (2-methyl-1-propenyl) -1,2,3,6-tetrahydrophthalic anhydride, 1-isopropyl-4-methyl-bicyclo [2.2 .2] Oct-5-ene-2,3-dicarboxylic anhydride and the like can be used. These may be used alone or in combination of two or more.

  Examples of phenolic curing agents include bisphenol resin, phenol novolak resin, naphthol novolak resin, allylated phenol novolak resin, biphenol resin, cresol novolak resin, phenol aralkyl resin, cresol naphthol formaldehyde polycondensate, triphenylmethane type polyfunctional Phenol resins, xylylene-modified phenol novolak resins, xylylene-modified naphthol novolak resins, various polyfunctional phenol resins, and the like can be used. These may be used alone or in combination of two or more.

  The content of the curing agent in the liquid epoxy resin composition of the present invention is such that the equivalent ratio of the active hydrogen of the curing agent and the epoxy group equivalent of the main agent ([active hydrogen equivalent] / [epoxy group equivalent]) is 0.5 to 0.5. An amount of 1.5 is preferable, and an amount of equivalent ratio of 0.6 to 1.4 is more preferable. When the equivalent ratio is within this range, insufficient curing and a decrease in heat resistance can be suppressed, and an increase in moisture absorption of the cured product can also be suppressed.

  A radical initiator is blended in the liquid epoxy resin composition of the present invention. By using a radical initiator, it is possible to suppress oxidation under high-temperature conditions caused by the unsaturated double bond of the epoxy-modified polybutadiene and to greatly improve heat resistance degradation.

  As the radical initiator, an organic peroxide is preferable from the viewpoint of suppression of heat-resistant deterioration and availability.

  Examples of the organic peroxide include 1,1-bis (t-hexylperoxy) 3,3,5-trimethylcyclohexane (10-hour half-life temperature 86.7 ° C.), 1,1-bis (t- Hexylperoxy) cyclohexane (10-hour half-life temperature 87.1 ° C.), 1,1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane (10-hour half-life temperature 90.0 ° C.), 1,1-bis (t-butylperoxy) cyclododecane (10-hour half-life temperature 95.0 ° C.), 1,1,3,3-tetramethylbutyl hydroperoxide (10-hour half-life temperature 152.9 ° C.) ), T-hexyl hydroperoxide (10-hour half-life temperature 159.5 ° C.), t-butylcumyl peroxide (10-hour half-life temperature 119.5 ° C.), di-t-butyl peroxide (10-hour half-life temperature 123.7 ° C.), lauroyl peroxide (10-hour half-life temperature 61.6 ° C.), bis (4-tert-butylcyclohexyl) peroxydicarbonate (10-hour half-life temperature 40.8 ° C), 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate (10 hour half-life temperature 65.3 ° C), t-hexylperoxy-2-ethylhexanoate (10 Time half-life temperature 69.9 ° C), t-butylperoxy-2-ethylhexanoate (10-hour half-life temperature 72.1 ° C), t-hexylperoxyisopropyl monocarbonate (10-hour half-life temperature 95) 0.0 ° C), t-butylperoxy-3,5,5-trimethylhexanoate (10 hour half-life temperature 97.1 ° C), t-butylperoxylaurate ( 0-hour half-life temperature 98.3 ° C), t-butyl peroxyisopropyl monocarbonate (10-hour half-life temperature 98.7 ° C), t-butyl peroxy-2-ethylhexyl monocarbonate (10-hour half-life temperature) 99.0 ° C.), t-hexyl peroxybenzoate (10-hour half-life temperature 99.4 ° C.), t-butyl peroxybenzoate (10-hour half-life temperature 104.3 ° C.), and the like. These may be used alone or in combination of two or more.

  Among these, the 10-hour half-life temperature of the organic peroxide is preferably in the range of 30 to 90 ° C. in consideration of the point of suppressing heat deterioration.

  The content of the radical initiator in the liquid epoxy resin composition is preferably within a range of 0.01 to 3 parts by mass, more preferably within a range of 0.5 to 1.5 parts by mass with respect to 100 parts by mass of the epoxy-modified polybutadiene. preferable. Within this range, heat deterioration can be effectively suppressed.

  The liquid epoxy resin composition of the present invention contains at least one selected from an acid anhydride type curing agent and a phenol type curing agent as a curing agent, and further contains a curing accelerator, an inorganic filler, and a coupling agent. Is preferred. By blending such components, a composition suitable for adhesion and sealing of electronic materials can be obtained.

  Examples of the curing accelerator include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo [5.4.0] undecene- Cycloamidines such as 7,1,5-diazabicyclo [4.3.0] nonene-5,5,6-dibutylamino-1,8-diazabicyclo [5.4.0] undecene-7, 2- (dimethyl Aminomethyl) phenol, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tertiary amines such as tris (dimethylaminomethyl) phenol, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tris (4- Methylphenyl) phosphine, Organic phosphines such as phenylphosphine and phenylphosphine, tetrasubstituted phosphonium / tetrasubstituted borates such as tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / ethyltriphenylborate, tetrabutylphosphonium / tetrabutylborate, 2-ethyl-4 -Tetraphenylboron salts such as methyl imidazole tetraphenylborate and N-methylmorpholine tetraphenylborate can be used. These may be used alone or in combination of two or more.

  0.01-8 mass parts is preferable with respect to 100 mass parts of main agents, and, as for the compounding quantity of a hardening accelerator, 0.1-3 mass parts is more preferable. When the blending amount of the curing accelerator is within this range, a sufficient curing acceleration effect can be obtained.

  The inorganic filler is not particularly limited, and for example, spherical silica, fused silica, crystalline silica, fine silica, alumina, silicon nitride, magnesia and the like can be used. These may be used alone or in combination of two or more. The thermal expansion coefficient of the cured product can be adjusted by blending the inorganic filler.

  The shape of the inorganic filler is not particularly limited, such as a crushed shape, a needle shape, a flake shape, and a spherical shape, but a spherical shape is preferably used from the viewpoint of dispersibility and viscosity control.

  The size of the inorganic filler is preferably an average particle size of 20 μm or less in consideration of the filling property into the gap between the semiconductor device and the substrate when flip-chip connection and viscosity control. The average particle diameter can be measured as a median diameter (d50) by a laser diffraction / scattering method.

  Furthermore, in order to adjust the viscosity and physical properties of the cured product, two or more kinds of inorganic fillers having different particle diameters may be used in combination.

  30-90 mass% is preferable with respect to the whole quantity of a liquid epoxy resin composition, and, as for the compounding quantity of the inorganic filler in the liquid epoxy resin composition of this invention, 40-70 mass% is more preferable. Within this range, the thermal expansion coefficient can be reduced to improve the connection reliability, and it is also possible to suppress the workability from being lowered due to the viscosity becoming too high.

  As the coupling agent, for example, a silane coupling agent or the like can be used. The silane coupling agent is not particularly limited. For example, mercaptosilane such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropylmethyl. Glycidoxy silane such as diethoxysilane, γ-glycidoxypropyltriethoxysilane, secondary amino silane such as γ-anilinopropyltrimethoxysilane, γ-anilinopropyltriethoxysilane, vinyl silane, γ-methacryloxypropyl Methacryloxysilane such as trimethoxysilane can be used. These may be used alone or in combination of two or more.

  By blending a coupling agent with the liquid epoxy resin composition of the present invention, the wettability between the inorganic filler and the resin and the adhesion with the adherend can be improved.

  Although content of the coupling agent in the liquid epoxy resin composition of this invention is not specifically limited, 0.01-2 mass% is preferable with respect to the whole quantity of a liquid epoxy resin composition. Within this range, the adhesion of the cured product can be improved, and the generation of voids in the cured product can also be suppressed.

  The liquid epoxy resin composition of the present invention may further contain other additives within a range not impairing the effects of the present invention. Examples of such other additives include a colorant and an antifoaming agent.

  The liquid epoxy resin composition of this invention can be manufactured in the following procedure, for example. The main agent, curing agent, radical initiator, and other additives are blended simultaneously or separately, and stirring, dissolution, mixing, and dispersion are performed while performing heat treatment and cooling treatment as necessary. Next, the liquid epoxy resin composition of the present invention can be obtained by adding an inorganic filler to the mixture and performing stirring, mixing, and dispersion again while performing heat treatment or cooling treatment as necessary. . For this stirring, dissolution, mixing, and dispersion, a disper, a planetary mixer, a ball mill, three rolls, or the like can be used in combination.

  The liquid epoxy resin composition of the present invention is preferably liquid at 25 ° C. from the viewpoint of workability and workability. Further, the viscosity of the liquid epoxy resin composition of the present invention is preferably 50 Pa · s or less, more preferably 30 Pa · s or less at 25 ° C. as measured by a B-type viscometer. When the viscosity is within this range, workability can be improved.

  The liquid epoxy resin composition of the present invention can obtain a cured product having a low glass transition temperature and a low elastic modulus, and can greatly improve the heat deterioration resistance and maintain a low elastic modulus for a long time. It can use suitably for adhesion | attachment and sealing of this member. In particular, it is suitable for bonding and sealing between a semiconductor device and a substrate.

  In the semiconductor electronic component of the present invention, the semiconductor device and the substrate are bonded by the cured product of the liquid epoxy resin composition of the present invention described above.

  For example, the liquid epoxy resin composition of the present invention can be used for bonding a semiconductor device (chip) having a plurality of bumps and a substrate having a plurality of electrodes electrically connected to the bumps.

  The semiconductor electronic component includes a semiconductor device on which a plurality of bumps are formed, a substrate having a plurality of electrodes electrically connected to the bumps, and a sealing resin disposed between the substrate and the semiconductor device. ing.

  The sealing resin is formed from a cured product of the liquid epoxy resin composition of the present invention, and seals the gap between the substrate and the semiconductor device.

  The substrate includes an insulating substrate such as an interposer and wiring provided on one surface of the substrate. The wiring of the substrate and the semiconductor device are electrically connected by a plurality of bumps. The substrate has an electrode pad on the surface opposite to the surface on which the wiring is provided and a solder ball provided on the electrode pad, and can be connected to other circuit members. .

  For the substrate, for example, a metal layer made of a metal material such as copper is formed on an insulating substrate such as glass epoxy, polyimide, polyester, or ceramic, and a wiring pattern is formed by removing unnecessary portions of the metal layer by etching. In other words, a wiring pattern formed by printing a conductive material on the surface of the insulating substrate can be used. A metal layer made of low melting point solder, high melting point solder, tin, indium, gold, nickel, silver, copper, palladium, or the like may be formed on the surface of the wiring. This metal layer may be composed of only a single component or may be composed of a plurality of components. Moreover, you may have the structure where the some metal layer was laminated | stacked.

  There are no particular limitations on the semiconductor device, and various semiconductors such as elemental semiconductors such as silicon and germanium, and compound semiconductors such as gallium arsenide and indium phosphide can be used.

  Examples of the material of the bump include low melting point solder, high melting point solder, tin, indium, gold, silver, and copper. The bump may be composed of only a single component or may be composed of a plurality of components. The bump may have a laminated structure including a metal layer made of these components. Note that the bump may be formed on the semiconductor device, may be formed on the substrate, or may be formed on both the semiconductor device and the substrate.

  Specific examples of the semiconductor device include CSP (chip size package) and BGA (ball grid array).

  The semiconductor electronic component of the present invention can be manufactured, for example, by the following method. After applying the rosin-based flux to the solder bump surface formed on the semiconductor device using the flux coating device, the semiconductor device and the circuit board are aligned using a chip mounter, and then the semiconductor device is bonded onto the substrate by pressure bonding. Arranged at a predetermined position. Next, using a reflow apparatus, heat treatment is performed with a predetermined heating profile to melt the solder bumps, and the semiconductor device and the substrate are flip-chip connected. Next, after the residue of the flux is washed with a solvent, the liquid epoxy resin composition of the present invention is dropped in a state where the residue is heated to 100 to 120 ° C., and the capillary phenomenon is used in the gap between the semiconductor device and the substrate. inject. After completion of the injection, in order to cure the liquid epoxy resin composition, heat treatment is performed in a heating oven heated to 120 to 170 ° C. for 0.5 to 5 hours.

  The semiconductor electronic component of the present invention can be manufactured, for example, by the following pre-sealing method. In this method, after applying the liquid epoxy resin composition of the present invention to the surface of the substrate in advance, the semiconductor device is disposed and mounted on the coating layer. Next, heating and pressing are performed from the back surface of the semiconductor device to perform electrode connection and resin curing in one step.

  The liquid epoxy resin composition of the present invention can also be applied to, for example, resin sealing in a technique called WL-CSP (wafer level chip size package). For example, first, a metal as a post that penetrates the resin layer is formed on a pad portion on a wafer at a position where a bump is formed when the CSP is formed. Next, the liquid epoxy resin composition of the present invention is printed on a wafer on which a metal as a post is formed, and is cured by heating. Next, the wafer after curing of the liquid epoxy resin composition is polished from the resin layer side, and the heights of the post and the resin layer are made uniform. Next, CSP bumps are formed using solder or the like. When the wafer thus obtained is separated into pieces by dicing, a CSP having metal electrodes composed of posts and bumps can be obtained.

  The liquid epoxy resin composition of the present invention can also be applied to package sealing by wire bonding connection. For example, a semiconductor electronic component can be manufactured by sealing a semiconductor device connected by wire bonding by potting, printing, liquid mold molding, or the like.

  The liquid epoxy resin composition of the present invention can also be used for adhesion (sealing) between a semiconductor package such as CSP or BGA as a semiconductor device and a substrate on which these are mounted.

  EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In addition, the compounding quantity shown in Table 1 represents a mass part.

As the blending components shown in Table 1, the following were used.
(Main agent)
Epoxy-modified polybutadiene, “JP-200” manufactured by Nippon Soda Co., Ltd., number average molecular weight 2,200, repeating unit 70 mol% or more derived from 1,2-vinyl structure, epoxy equivalent 210-240 eq / g, viscosity 1000 poise / 45 ° C.
-Bisphenol A type epoxy resin, “Epicoat 828” manufactured by Japan Epoxy Resin Co., Ltd., viscosity 120-150 P / 25 ° C., epoxy equivalent 184-194 eq / g
(Curing agent)
・ Acid anhydride curing agent, methyltetrahydrophthalic anhydride, “MH-700” manufactured by Shin Nippon Rika Co., Ltd., acid anhydride equivalent 166
・ Phenol-based curing agent, “MEH-8000H-4L” manufactured by Meiwa Kasei Co., Ltd.
(Curing accelerator)
・ Imidazole-based curing catalyst, "1M2PZ" manufactured by Shikoku Chemicals Co., Ltd.
(Inorganic filler)
・ Spherical silica, “SE15” manufactured by Tokuyama Corporation, average particle size of 15 μm
(Coupling agent)
・ Mercaptosilane coupling agent, 3-mercaptopropylmethyldimethoxysilane, “KBM803” manufactured by Shin-Etsu Chemical Co., Ltd.
(Radical initiator)
・ 1,1-bis (t-hexylperoxy) cyclohexane, “Perhexa HC” manufactured by NOF Corporation
(Antioxidant)
"Nocrack NS-6" manufactured by Ouchi Shinsei Chemical Co., Ltd.
Each component was mix | blended with the compounding quantity shown in Table 1, and liquid epoxy resin composition was prepared by stirring, melt | dissolving, mixing, and disperse | distributing each component, such as a main ingredient and a hardening | curing agent, according to a conventional method.

The following evaluation was performed about the liquid epoxy resin composition of the Example and comparative example which were prepared in this way.
[viscosity]
The liquid epoxy resin composition was weighed into a 200 cc plastic bottle and measured with a B-type viscometer. The viscosity was evaluated based on the following criteria from the measured value of viscosity.
○: 10 Pa · s or more and less than 30 Pa · s Δ: 30 Pa · s or more and less than 50 Pa · s ×: 50 Pa · s or more
[Glass transition temperature (Tg)]
After the liquid epoxy resin composition was sandwiched between glass plates and cured, a test piece having a length of 15 mm, a thickness of 3 mm, and a width of 3 mm was produced. The curing conditions were 150 ° C / 2h. Tg was measured by TMA and evaluated based on the following criteria.
○: 0 ° C or higher and lower than 30 ° C Δ: 30 ° C or higher and lower than 50 ° C ×: 50 ° C or higher
[Bending strain after 125 ℃ / 500h]
After the liquid epoxy resin composition was sandwiched between glass plates and cured, a test piece having a length of 58 mm, a thickness of 7 mm, and a width of 14 mm was produced. The curing conditions were 150 ° C / 2h. As heat treatment, it was left in a dryer at 125 ° C. for 500 hours.

A three-point bending test by an autograph was performed, the amount of strain (%) until rupture was measured, and toughness was evaluated based on the following criteria.
○: 3% or more Δ: 2% or more and less than 3% ×: less than 2%
[Elastic modulus at 125 ° C / 500h]
The elastic modulus (GPa) by the above bending test was measured and evaluated based on the following criteria.
○: Less than 6 GPa Δ: 6 GPa or more and less than 8 GPa x: 8 GPa or more Table 1 shows the evaluation results.

  From Table 1, in Examples 1 and 2 in which an epoxy resin and an epoxy-modified polybutadiene as a main agent, a curing agent, and a radical initiator were blended, a composition having an appropriate viscosity was obtained, and a glass transition temperature and an elastic modulus were obtained. A low cured product could be obtained. And the increase in the amount of bending strain and elastic modulus after 125 ° C./500 h was also suppressed, and the heat deterioration resistance could be greatly improved.

  In contrast, in Comparative Examples 1 and 2 in which an antioxidant was blended instead of the radical initiator and the other compositions were the same as those in Examples 1 and 2, the bending strain amount and the elastic modulus after 125 ° C./500 h. And the deterioration due to heat resistance was remarkable. In Comparative Example 2, the blending amount of the antioxidant was increased to 1.0 part by mass as compared with Comparative Example 1, but no improvement in heat resistance was observed, and an increase in viscosity was further observed.

Claims (3)

A liquid epoxy resin composition for bonding a semiconductor device and a substrate in a semiconductor electronic component,
Contains an epoxy resin and epoxy-modified polybutadiene as a main agent, a curing agent, and a radical initiator ,
The epoxy-modified polybutadiene has an epoxy equivalent in the range of 180 to 250 g / eq, contains 70 mol% or more of repeating units derived from 1,2-vinyl structure,
The compound having a double bond capable of radical polymerization in the resin component is only the epoxy-modified polybutadiene,
Containing an acid anhydride curing agent and a phenol curing agent as the curing agent,
The content of the curing agent is such that the equivalent ratio of the active hydrogen of the curing agent and the epoxy group equivalent of the main agent ([active hydrogen equivalent] / [epoxy group equivalent]) is 0.5 to 1.5. And
Containing an organic peroxide as the radical initiator,
The organic peroxide has a 10-hour half-life temperature in the range of 30 to 90 ° C.,
The liquid epoxy resin composition , wherein a content of the radical initiator is in a range of 0.01 to 3 parts by mass with respect to 100 parts by mass of the epoxy-modified polybutadiene . The liquid epoxy resin composition according to claim 1 , further comprising a curing accelerator, an inorganic filler, and a coupling agent. A semiconductor electronic component, wherein the semiconductor device and the substrate are bonded by a cured product of the liquid epoxy resin composition according to claim 1 .