JP2021195451A - Epoxy resin composition - Google Patents

Abstract

To provide an epoxy resin composition which does not bleed and enables acquisition of a cured product having low thermal expansion property, low elastic modulus and heat resistance.SOLUTION: An epoxy resin composition is provided which includes the following components (A) to (D): epoxy resin (A), a curing agent (B), polyester polyol (C) having no isocyanate group, and an inorganic filler (D), and in which a number average molecular weight of the component (C) is 1,500-10,000. A semiconductor element sealing material is provided which is made of the epoxy resin composition. A semiconductor device is provided which comprises a semiconductor element sealed with the epoxy resin composition.SELECTED DRAWING: None

Description

The present invention relates to an epoxy resin composition, preferably a thermosetting epoxy resin composition useful for encapsulating semiconductor devices and the like.

In recent years, electronic devices such as mobile phones, smartphones, ultra-thin LCDs, plasma TVs, and lightweight notebook personal computers have been miniaturized. Electronic components used in these electronic devices are being integrated at high densities, and are being mounted at high densities. Further, the resin material used for these electronic parts is required to have a low expansion and a low elastic modulus due to the relationship of thermal stress during manufacturing and use.

Higher filler filling in epoxy resin has been studied for the purpose of reducing thermal stress. By increasing the filling of the filler, it is possible to reduce the coefficient of thermal expansion of the epoxy resin. However, since the elastic modulus of the epoxy resin increases and the strength of the epoxy resin also decreases, there arises a problem that the Si chip or the substrate is destroyed in a heat cycle test or the like.

As another method for reducing thermal stress, addition of a flexible epoxy resin to an epoxy resin has been studied (Patent Documents 1 and 2). Although these methods are effective in reducing thermal stress, they cause problems such as a decrease in the glass transition temperature and an increase in the coefficient of linear expansion.

As a method for solving such a problem, a method of adding a polymer thermoplastic resin to an epoxy resin has been studied (Patent Document 3). By adding the polymer thermoplastic resin to the epoxy resin, it is possible to reduce the thermal stress, but the epoxy resin used causes a problem that the dispersibility is significantly lowered and bleeding occurs.

Japanese Unexamined Patent Publication No. 2011-119605 Japanese Unexamined Patent Publication No. 2018-141143 Japanese Unexamined Patent Publication No. 2017-008312

Therefore, an object of the present invention is to provide an epoxy resin composition capable of obtaining a cured product having low thermal expansion, low elastic modulus, and heat resistance.

As a result of diligent research to solve the above problems, the present inventors have found that the number of polyester polyols in an epoxy resin composition containing an epoxy resin, a curing agent, a polyester polyol having no isocyanate, and an inorganic filler. We have found that the composition obtained by having an average molecular weight in the range of 1,500 to 10,000 gives a cured product having low thermal expansion property, low elasticity and heat resistance without bleeding. Completed the invention.

That is, the present invention provides the following epoxy resin compositions and the like.

[1]
The following components (A) to (D):
(A) Epoxy resin (B) Curing agent (C) Polyester polyol without isocyanate group (D) Inorganic filler, and the number average molecular weight of the component (C) is in the range of 1,500 to 10,000. Is an epoxy resin composition.

[2]
The epoxy resin composition according to [1], wherein the component (B) is any one of an amine-based curing agent, a phenol-based curing agent, and an acid anhydride-based curing agent.

[3]
(C) The epoxy resin composition according to [1] or [2], wherein the hydroxyl value of the component is 10 to 100 mg KOH / g.

[4]
The epoxy resin composition according to any one of [1] to [3], wherein the component (C) is 1 to 40 parts by mass with respect to 100 parts by mass of the epoxy resin (A).

[5]
The epoxy resin composition according to any one of [1] to [4], wherein the component (C) contains an aromatic ring.

[6]
The viscosity of the component (C) at 75 ° C. is 1,000 to 20,000 mPa. The epoxy resin composition according to any one of [1] to [5], which is s.

[7]
The cured product of the epoxy resin composition according to any one of [1] to [6].

[8]
A semiconductor device encapsulant comprising the epoxy resin composition according to any one of [1] to [6].

[9]
A semiconductor device including a semiconductor device sealed with the epoxy resin composition according to any one of [1] to [6].

The epoxy resin composition of the present invention provides a cured product that does not bleed and has excellent low thermal expansion, low elastic modulus, and heat resistance. Therefore, the epoxy resin composition of the present invention can be suitably used as a semiconductor device encapsulant or the like.

FIG. 1 is an example of a graph plotting the relationship between the dimensional change and the temperature of the result of measuring the dimensional change of the test piece between 25 ° C. and 300 ° C. in the example, and determining the glass transition temperature. It shows the method.

The epoxy resin composition of the present invention is an epoxy resin composition containing an epoxy resin, a curing agent, a polyester polyol, and an inorganic filler, and the polyester polyol does not have an isocyanate group and has a number average molecular weight of 1,. It is characterized by being 500 to 10,000.
Hereinafter, the present invention will be described in detail.

(A) Epoxy resin The epoxy resin of the component (A) used in the present invention is the main component of the present invention, and a known epoxy resin can be used. Examples of the epoxy resin of the component (A) include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, and bisphenol. F novolak type epoxy resin, stillben type epoxy resin, triazine skeleton-containing epoxy resin, fluorene skeleton-containing epoxy resin, trisphenol alkane type epoxy resin, biphenyl type epoxy resin, xylylene type epoxy resin, biphenyl aralkyl type epoxy resin, naphthalene type epoxy resin , Dicyclopentadiene type epoxy resin, alicyclic epoxy resin, polyfunctional epoxy resin, silicone-modified epoxy resin, polycyclic aromatic diglycidyl ether compound, phosphorus-containing epoxy resin in which a phosphorus compound is introduced, and the like. Be done. These can be used alone or in combination of two or more.

The blending amount of the component (A) is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, still more preferably 7 to 40% by mass, based on the total mass of the epoxy resin composition.

(B) Curing Agent The curing agent of the component (B) used in the present invention is an epoxy resin curing agent, and a known curing agent can be used. This curing agent is three-dimensional by reacting a reactive functional group (amino group, phenolic hydroxyl group, acid anhydride group, etc.) in the molecule of the curing agent with an epoxy group in the epoxy resin of the component (A). It is added to obtain a cured product having a crosslinked structure.

Examples of the curing agent for the component (B) include an amine-based curing agent, a phenol-based curing agent, an acid anhydride-based curing agent, and the like, and among them, an amine-based curing agent is preferable.
Examples of the amine-based curing agent include 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3', 5, Examples thereof include aromatic diaminodiphenylmethane compounds such as 5'-tetraethyl-4,4'-diaminodiphenylmethane, 2,4-diaminotoluene, 1,4-diaminobenzene, 1,3-diaminobenzene and the like. These can be used alone or in combination of two or more.

The molar ratio of the total amino groups in the amine-based curing agent to the total epoxy groups in the component (A) is preferably 0.7 to 1.2, more preferably 0.7 to 1.1, and 0.85-1. 0.05 is more preferred. If the molar ratio is less than 0.7, unreacted epoxy groups may remain, and the glass transition temperature may decrease or the adhesion may decrease. On the other hand, if the molar ratio exceeds 1.2, the cured product becomes hard and brittle, and cracks may occur during reflow or temperature cycle.

Examples of the phenol-based curing agent include phenol novolac resin, naphthalene ring-containing phenol resin, aralkyl-type phenol resin, triphenolalcan-type phenol resin, biphenyl skeleton-containing aralkyl-type phenol resin, biphenyl-type phenol resin, and alicyclic phenol resin. Examples thereof include a heterocyclic phenol resin, a naphthalene ring-containing phenol resin, a resorsinol type phenol resin, an allyl group-containing phenol resin, a bisphenol A type resin, and a bisphenol type phenol resin such as a bisphenol F type resin. These can be used alone or in combination of two or more.

When a phenol resin is used as the curing agent, the molar ratio of the phenolic hydroxyl group contained in the curing agent to 1 mol of the epoxy group contained in the epoxy resin is preferably 0.5 to 1.5, and 0. 8 to 1.2 are more preferable.

Examples of the acid anhydride-based curing agent include 3,4-dimethyl-6- (2-methyl-1-propenyl) -1,2,3,6-tetrahydroanhydride phthalic acid and 1-isopropyl-4-methyl-. Bicyclo [2.2.2] Oct-5-en-2, 3-dicarboxylic acid anhydride, methyltetrahydroanhydride, methylhexahydroanhydride, hexahydroanhydride, methylhymic anhydride, pyromellitic acid Dianhydride, maleic aloosimene, benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenyltetrabisbenzophenonetetracarboxylic acid dianhydride, (3,4-dicarboxyphenyl) ether dianhydride , Bis (3,4-dicarboxyphenyl) methane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride and the like. These can be used alone or in combination of two or more.

When an acid anhydride-based curing agent is used, (A) the equivalent ratio of the acid anhydride group (-CO-O-CO-) in the curing agent to the epoxy group in the epoxy resin is 0.5 to 1.5. Is preferable. If the equivalent ratio is less than 0.5, the unreacted epoxy group remains, which may lower the glass transition temperature and further lower the adhesion. If the equivalent ratio exceeds 1.5, the cured product becomes hard and brittle, and cracks may occur during reflow or temperature cycle test.

(C) Polyester polyol having no isocyanate group The polyester polyol as a component of (C) has no isocyanate group, and is obtained by, for example, polycondensation of a polyvalent carboxylic acid or an anhydride thereof with a polyhydric alcohol. Polyester polyols can be used. Among them, those having one or more aromatic rings in one molecule are preferable.
The polyester polyol having an aromatic ring and obtained by polycondensation of the polyvalent carboxylic acid or its anhydride and the polyhydric alcohol is the one using the polyvalent carboxylic acid having an aromatic ring or its anhydride. However, it may be either one using a polyhydric alcohol having an aromatic ring, or one using a polyvalent carboxylic acid having an aromatic ring and a polyhydric alcohol having an aromatic ring. ..

Examples of the polyvalent carboxylic acid include malonic acid, succinic acid, anhydrous succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, anhydrous phthalic acid, hexahydrochloride anhydrous phthalic acid, tetrahydrophthalic anhydride, and isophthalic acid. Examples thereof include acids, terephthalic acid, nadic acid anhydride, maleic acid, maleic anhydride, fumaric acid, itaconic acid, citraconic acid, trimellitic acid, trimellitic anhydride, pyromellitic acid and pyromellitic anhydride. These may be used alone or in combination of two or more.

Examples of the polyvalent alcohol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,2-butylene glycol, and 1,5. -Pentanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, 2,2,4-trimethyl-1,3-pentanediol, cyclohexanediol, bisphenol A ethylene oxide adduct, bisphenol A propylene oxide Additives, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, glycerin, trimethylolpropane, trimethylolethane, pentaerythritol and the like can be mentioned. These may be used alone or in combination of two or more.

The number average molecular weight (Mn) of the polyester polyol as the component (C) is 1,500 to 10,000, preferably 2,000 to 8,000.

The polyester polyol of the component (C) has excellent compatibility with the epoxy resin (A) and the curing agent (B), and is suitable for obtaining a cured product having low expansion and a low elastic modulus, and the hydroxyl value of the polyester polyol is , 10-100 mg KOH / g, more preferably 15-80 mg KOH / g, and most preferably 20-70 mg KOH / g.

The polyester polyol as the component (C) has a viscosity in the range of 1,000 to 20,000 mPa · s at 75 ° C. 2 minutes after the start of measurement measured using an E-type viscometer by the method described in JIS Z 8803: 2011. Is preferable, and those in the range of 1,500 to 15,000 mPa · s are more preferable. Within this range, dispersion in (A) epoxy resin and (B) curing agent becomes easy.

The above number average molecular weight refers to the number average molecular weight using polystyrene as a standard substance measured by gel permeation chromatography (GPC) under the following conditions.

[GPC measurement conditions]
Developing solvent: Tetrahydrofuran Flow rate: 0.6 mL / min
column:
TSK Guardcolum SuperH-L
TSKgel SuperH4000 (6.0mm ID x 15cm x 1)
TSKgel SuperH3000 (6.0mm ID x 15cm x 1)
TSKgel SuperH2000 (6.0 mm ID x 15 cm x 2)
(Both manufactured by Tosoh)
Column temperature: 40 ° C
Sample injection amount: 20 μL (sample concentration: 0.5% by mass-tetrahydrofuran solution)
Detector: Differential Refractometer (RI)

The blending amount of the polyester polyol is preferably 1 to 40 parts by mass, more preferably 4 to 35 parts by mass, still more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin (A).

The polyester polyol contained in the epoxy resin composition according to the present invention does not have an isocyanate group. Compared with the case where a polyisocyanate having an isocyanate group is used for the polyester polyol instead of the polyester polyol, the epoxy resin composition containing the polyester polyol having no isocyanate group is excellent in heat resistance and moisture resistance.

(D) Inorganic filler The component (D) is an inorganic filler and is added for the purpose of lowering the coefficient of thermal expansion and improving the moisture resistance reliability of the epoxy resin composition. Examples of the inorganic filler include silicas such as molten silica, crystalline silica and cristobalite, metal oxides such as aluminum oxide, titanium oxide and magnesium oxide, and nitrides such as silicon nitride, aluminum nitride and boron nitride. Kind and so on. Among them, silicas are preferably used in consideration of availability of materials, stability of quality and the like. The average particle size of these inorganic fillers is preferably 0.1 to 50 μm, more preferably 0.5 to 30 μm, and can be selected according to the intended use. The average particle size is a volume average particle size measured by a laser diffraction method. Further, these inorganic fillers may be used alone or in combination of two or more.

The inorganic filler is preferably surface-treated in advance with a coupling agent such as a silane coupling agent or a titanate coupling agent in order to strengthen the bonding strength between the resin component and the inorganic filler. Examples of such a coupling agent include epoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N. -Β- (Aminoethyl) -γ-Aminopropyltrimethoxysilane, reaction product of imidazole and γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane Examples thereof include silane coupling agents such as aminosilane such as γ-mercaptopropyltrimethoxysilane and mercaptosilane such as γ- (thiylanylmethoxy) propyltrimethoxysilane. The amount of the coupling agent used for the surface treatment and the surface treatment method are not particularly limited.

The content of the inorganic filler in the composition of the present invention is preferably 30 to 3,500 parts by mass, more preferably 100 to 3,000 parts by mass, and 150 to 2,000 parts by mass with respect to 100 parts by mass of the component (A). Parts by mass are particularly preferred.

(E) Other Additives The epoxy resin composition of the present invention can be obtained by blending a predetermined amount of the above components (A) to (D), but other additives may be added as necessary for the purpose of the present invention. , Can be added within a range that does not impair the effect. Examples of such additives include curing accelerators, flame retardants, ion trapping agents, antioxidants, adhesion-imparting agents, mold release agents and the like.

The curing accelerator is used to accelerate the curing reaction between the epoxy resin and the curing agent, and is not particularly limited as long as it promotes the curing reaction. For example, phosphorus compounds such as triphenylphosphine, tributylphosphine, tri (p-methylphenyl) phosphine, tri (nonylphenyl) phosphine, triphenylphosphine / triphenylboran, tetraphenylphosphine / tetraphenylborate, triethylamine, benzyldimethylamine. , Α-Methylbenzyldimethylamine, tertiary amine compounds such as 1,8-diazabicyclo [5.4.0] undecene-7, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, Examples thereof include imidazole compounds such as 2-phenyl-4-methylimidazole and 2-phenyl-4,5-dihydroxymethylimidazole.

The flame retardant is added for the purpose of imparting flame retardancy to the resin composition, and any known flame retardant can be used without particular limitation. Examples of the flame retardant include phosphazene compounds, silicone compounds, zinc molybdate-supported talc, zinc molybdate-supported zinc oxide, aluminum hydroxide, magnesium hydroxide, molybdate oxide and the like. Examples of the silicone compound include silicone rubber powder.

The ion trapping agent is added for the purpose of capturing ionic impurities contained in the resin composition and preventing thermal deterioration and hygroscopic deterioration, and any known ion trapping agent can be used without particular limitation. Examples of the ion trapping agent include hydrotalcites, bismuth hydroxide compounds, rare earth oxides and the like.

The antioxidant is added for the purpose of preventing thermal deterioration of the resin composition, and any known antioxidant can be used without particular limitation. Examples of the antioxidant include phenol-based, phosphorus-based, and sulfur-based antioxidants.

The adhesive-imparting agent is added for the purpose of strengthening the adhesive strength with a metal base material such as copper or silver or an inorganic ceramic base material such as silicon or alumina, and all known adhesives are used without particular limitation. can do. Examples of the adhesion-imparting agent include coupling agents such as a silane coupling agent and a titanate coupling agent.

The mold release agent is added for the purpose of enhancing the mold release property at the time of molding, and all known mold release agents can be used without particular limitation. Examples of the mold release agent include natural waxes such as carnauba wax and rice wax, acid waxes, polyethylene waxes, synthetic waxes such as fatty acid esters, and the like.

The blending amount of the above other components varies depending on the use of the epoxy resin composition of the present invention, but the total amount may be 5% by mass or less of the total composition.

Method for Producing Epoxy Resin Composition The method for producing the epoxy resin composition of the present invention is not particularly limited. For example, (A) epoxy resin, (B) curing agent, (C) polyester polyol, and (D) inorganic filler are mixed, stirred, dissolved, and / or mixed at the same time or separately while heat-treating as necessary. The composition can be obtained by dispersing. Depending on the application, other additives such as a curing accelerator, a flame retardant, an ion trapping agent, an antioxidant, an adhesion-imparting agent, and a mold release agent are added to the mixture of the components (A) to (D) and mixed. However, the epoxy resin composition of the present invention (for example, a semiconductor element encapsulant or the like) may be obtained.

The apparatus for mixing, stirring and dispersing in the above production method is not particularly limited. For example, a Raikai machine equipped with a stirring and heating device, a two-roll mill, a three-roll mill, a ball mill, a planetary mixer, a mass colloider, or the like can be used, and these devices may be used in combination as appropriate.

The curing conditions of the epoxy resin composition of the present invention are not particularly limited, but for example, heating may be performed at a temperature of 60 to 200 ° C., preferably 80 to 180 ° C. for 30 minutes to 10 hours, preferably 1 to 5 hours.

The cured product of the epoxy resin composition of the present invention thus obtained preferably has a glass transition temperature (Tg) determined by the following measurement conditions in the range of 100 to 200 ° C., preferably 120 to 200 ° C. It is more preferable that it is in the range of. Within this range, the obtained cured product has excellent heat resistance.

Measurement of glass transition temperature (Tg) After processing the cured epoxy resin into a 5 × 5 × 15 mm test piece, the test piece was set in a thermal expansion meter TMA8140C (manufactured by Rigaku Co., Ltd.). Then, the temperature rise program was set to a temperature rise rate of 5 ° C./min, and a constant load of 19.6 mN was set, and then the dimensional change of the test piece was measured between 25 ° C. and 300 ° C. The relationship between this dimensional change and temperature was plotted on a graph (an example of the graph is shown in FIG. 1). From the graph of the dimensional change and the temperature obtained in this way, the glass transition temperature was obtained by the method for determining the glass transition temperature described below.

_{Method for determining the glass transition temperature As shown in Fig. 1, T 1} and T ₂ are two arbitrary temperatures at which the tangent of the dimensional change-temperature curve can be obtained below the temperature of the inflection point, and above the temperature of the inflection point. any temperature two points similar tangent obtained was T ₁ 'and T _2'. T ₁ and the dimensional change in T ₂ as D ₁ and D _2, respectively, the dimensional change in the linear and, T ₁ 'and T _2' connecting the point and (T _1, D ₁₎ and the point (T _2, D ₂₎ as D ₁ 'and D _2', respectively, the point _{(T 1 ', D 1'} ) to a point _{(T 2 ', D 2'} ) and the intersection point of the glass transition temperature of the straight line connecting the (T _g).

Semiconductor device A semiconductor device can be manufactured by encapsulating a semiconductor element with the epoxy resin composition of the present invention obtained by the above manufacturing method. The method for sealing the semiconductor element and the method for manufacturing the semiconductor device are not particularly limited.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

The components used in Examples 1 to 13 and Comparative Examples 1 to 5 are as follows.

(A) Epoxy resin (A1) Epoxy resin: A mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin (ZX1059: manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.)
(A2) Epoxy resin: Polyfunctional epoxy resin (jER630: manufactured by Mitsubishi Chemical Corporation)
(A3) Epoxy resin: Cresol novolac type epoxy resin (N-655-EXP-S: manufactured by DIC Corporation)
(A4) Epoxy resin: Silicone modified epoxy resin (Manufacturing method is shown below)

で表されるアリルグリシジルエーテルで変性されたフェノールノボラック樹脂（フェノール当量１２５、アリル当量１，１００）２００ｇ、クロロメチルオキシラン８００ｇ、セチルトリメチルアンモニウムブロマイド０．６ｇをそれぞれ入れて加熱し、温度１１０℃で３時間撹拌混合した。これを冷却して温度７０℃とし、１６０ｍｍＨｇに減圧してから、この中に水酸化ナトリウムの５０％水溶液１２８ｇを共沸脱水しながら３時間かけて滴下した。得られた内容物を減圧して溶剤を留去し、次いでメチルイソブチルケトン３００ｇとアセトン３００ｇの混合溶剤にて溶解させた後、水洗し、これを減圧下で溶剤留去して下記式（２）

で表されるアリル基含有のエポキシ樹脂（アリル当量１５９０、エポキシ当量１９０）を得た。このエポキシ樹脂とメチルイソブチルケトン１７０ｇ、トルエン３３０ｇ、２質量％の白金濃度の２−エチルヘキサノール変性塩化白金酸溶液０．０７ｇを入れ、１時間の共沸脱水を行ない、還流温度にて下記式（３）

で表されるオルガノポリシロキサン１３３ｇを滴下時間３０分にて滴下した。更に、同一温度で４時間撹拌して反応させた後、得られた内容物を水洗し、溶剤を減圧下で留去したところ黄白色不透明固体の共重合体が得られた。エポキシ当量は２８０であり、ＡＳＴＭ Ｄ４２８７に従い、コーン／プレート粘度計を用いて測定した１５０℃でのＩＣＩ溶融粘度は８００ｍＰａ．ｓであり、ケイ素含有量３１質量％であった。 Manufacturing method of silicone-modified epoxy resin (A4) To a four-necked flask with an internal volume of 1 liter equipped with a reflux condenser, a thermometer, a stirrer and a dropping funnel, the following formula (1)

200 g of a phenol novolac resin (phenol equivalent 125, allyl equivalent 1,100) modified with allyl glycidyl ether represented by, 800 g of chloromethyloxylan, and 0.6 g of cetyltrimethylammonium bromide are added and heated at a temperature of 110 ° C. The mixture was stirred and mixed for 3 hours. This was cooled to a temperature of 70 ° C., the pressure was reduced to 160 mmHg, and then 128 g of a 50% aqueous solution of sodium hydroxide was added dropwise over 3 hours while azeotropically dehydrating. The obtained content was reduced under reduced pressure to distill off the solvent, then dissolved in a mixed solvent of 300 g of methyl isobutyl ketone and 300 g of acetone, washed with water, and the solvent was distilled off under reduced pressure to obtain the following formula (2). )

An epoxy resin containing an allyl group represented by (allyl equivalent 1590, epoxy equivalent 190) was obtained. 170 g of this epoxy resin, 170 g of methyl isobutyl ketone, 330 g of toluene, 0.07 g of a 2-ethylhexanol-modified platinum chloride acid solution having a platinum concentration of 2% by mass were added, and azeotropic dehydration was performed for 1 hour. 3)

133 g of the organopolysiloxane represented by (1) was added dropwise over a dropping time of 30 minutes. Further, after stirring and reacting at the same temperature for 4 hours, the obtained contents were washed with water and the solvent was distilled off under reduced pressure to obtain a yellow-white opaque solid copolymer. The epoxy equivalent is 280 and the ICI melt viscosity at 150 ° C. measured with a cone / plate viscometer according to ASTM D4287 is 800 mPa. The silicon content was 31% by mass.

(B) Curing agent (B1) Curing agent: 3,3'-diethyl-4,4'-diaminodiphenylmethane (Kayahard AA, manufactured by Nippon Kayaku Co., Ltd.)
(B2) Curing agent: 4-Methylhexahydrophthalic anhydride (Ricacid MH: manufactured by Shin Nihon Rika Co., Ltd.)
(B3) Curing agent: Phenol novolac resin (DL-92, manufactured by Meiwa Kasei Co., Ltd.)

(C) Polyester polyol (C1) Polyester polyol: Aromatic ring-containing polyester polyol (OD-X-2360T, manufactured by DIC, number average molecular weight 2000, hydroxyl value 58 mg KOH / g, viscosity: 2,100 mPa.s at 75 ° C. )
(C2) Polyester polyol: Aromatic ring-containing polyester polyol (OD-X-3100, manufactured by DIC Corporation, number average molecular weight 3,000, hydroxyl value 39 mg KOH / g, viscosity: 9,200 mPa.s at 75 ° C.)
(C3) Polyester polyol: Aromatic ring-containing polyester polyol (OD-X-3110, manufactured by DIC Corporation, number average molecular weight 7,500, hydroxyl value 16 mg KOH / g, viscosity: 8,600 mPa.s at 75 ° C.)
(C4) Polyester polyol: Isocyanate group-containing polyester polyol (Pandex 390E, manufactured by DIC, number average molecular weight 2,400, viscosity: 2,500 mPa.s at 75 ° C.) (for comparative example)
(C5) Polyester polyol: Aromatic ring-containing polyester polyol (OD-X-2586, manufactured by DIC Corporation, number average molecular weight 850, hydroxyl value 200 mg KOH / g, viscosity: 200 mPa.s at 75 ° C.) (for comparative example)
(C6) Polyester polyol: Aliphatic polyester polyol (OD-X-2027, manufactured by DIC, number average molecular weight 2000, hydroxyl value 55 mg KOH / g, viscosity: 500 mPa.s at 75 ° C.) (for comparative example)

(D) Inorganic filler (D1) Fused silica: Fused spherical silica with an average particle size of 14 μm (manufactured by Ryumori Co., Ltd.)

(E) Other components (E1) Curing accelerator: 2-phenyl-4,5-dihydroxymethylimidazole (2PHZ-PW, manufactured by Shikoku Chemicals Corporation)
(E2) Silicone rubber powder: Silicone rubber powder with an average particle size of 5 μm (KMP-600, manufactured by Shin-Etsu Chemical Co., Ltd.)

Each of the above components was mixed in the blending amount (part by mass) shown in Table 1 to obtain an epoxy resin composition. For each composition and the cured product obtained by curing each composition, the presence or absence of bleeding, the glass transition temperature, the coefficient of linear expansion (CTE1), the flexural modulus, the bending strength, and the amount of warpage were obtained by the methods shown below. The heat resistance and moisture resistance reliability were evaluated. The results are shown in Table 1.

Preparation of Cured Product Samples Each of the epoxy resin compositions of Examples and Comparative Examples was heat-cured at 120 ° C. × 1 hour and further at 180 ° C. × 2 hours to be molded to obtain a cured product.

Confirmation of the presence or absence of bleeding 1 g of each epoxy resin composition was weighed on a glass plate and cured under the above curing conditions. The surface of the obtained cured product was observed, and those in which the oil-like component did not exude to the surface of the cured product were marked with ◯, and those in which the oil-like component exuded to the surface of the cured product were marked with x.

Measurement of glass transition temperature (Tg) After processing each of the cured products obtained above into 5 × 5 × 15 mm test pieces, those test pieces were set in a thermal expansion meter TMA8140C (manufactured by Rigaku Co., Ltd.). .. Then, the temperature rise program was set to a temperature rise rate of 5 ° C./min, and a constant load of 19.6 mN was set, and then the dimensional change of the test piece was measured between 25 ° C. and 300 ° C. The relationship between this dimensional change and temperature was plotted on a graph (an example of the graph is shown in FIG. 1). From the graph of the dimensional change and the temperature obtained in this way, the glass transition temperature in Examples and Comparative Examples was obtained by the method for determining the glass transition temperature described below.

_{Method for determining the glass transition temperature As shown in Fig. 1, T 1} and T ₂ are two arbitrary temperatures at which the tangent of the dimensional change-temperature curve can be obtained below the temperature of the inflection point, and above the temperature of the inflection point. any temperature two points similar tangent obtained was T ₁ 'and T _2'. T ₁ and the dimensional change in T ₂ as D ₁ and D _2, respectively, the dimensional change in the linear and, T ₁ 'and T _2' connecting the point and (T _1, D ₁₎ and the point (T _2, D ₂₎ as D ₁ 'and D _2', respectively, the point _{(T 1 ', D 1'} ) to a point _{(T 2 ', D 2'} ) and the intersection point of the glass transition temperature of the straight line connecting the (T _g).

Method for determining the coefficient of linear expansion (CTE1) Thermomechanical analysis of the cured product was performed under the same conditions as the above glass transition temperature measurement, and the coefficient of linear expansion was calculated from the measurement results in the temperature range of 40 ° C to 80 ° C. did.

Flexural modulus was measured using the above-mentioned cured product according to JIS K 6911: 2006.

Flexural strength Measured using the above-mentioned cured product according to JIS K 6911: 2006.

Warpage measurement Using a Cu lead frame with a PPS frame having a size of 50 × 70 mm, the compositions prepared in Examples and Comparative Examples were injected at 80 ° C. to a thickness of 5 mm, and 120 ° C. Molding was performed at × 1 hour and further at 180 ° C. × 2 hours to obtain a molded product. After molding, the amount of warpage of the molded product was measured using a laser coordinate measuring machine.

Heat cycle test (heat resistance)
Using the molded product obtained by measuring the amount of warpage, it was subjected to a heat cycle test (holding at -65 ° C for 30 minutes, holding at 200 ° C for 30 minutes was repeated for 1,000 cycles), and the resin and Cu lead after the heat cycle test were performed. The state of separation from the frame was confirmed using an ultrasonic exploration device. The number of molded products in which peeling was observed out of a total of 5 molded products was counted.

Moisture-resistant reliability test Using the molded product obtained by measuring the amount of warpage, it was subjected to a moisture-resistant reliability ^{test (exposure at 121 ° C with a pressure cooker under saturated steam of 2.03 × 10 5 Pa for 48 hours).} The peeled state between the resin and the Cu lead frame after the sex test was confirmed using an ultrasonic probe. The number of molded products in which peeling was observed out of a total of 5 molded products was counted.

Claims (9)

The following components (A) to (D):
(A) Epoxy resin (B) Curing agent (C) Polyester polyol without isocyanate group (D) Inorganic filler, and the number average molecular weight of the component (C) is in the range of 1,500 to 10,000. Is an epoxy resin composition. The epoxy resin composition according to claim 1, wherein the component (B) is any one of an amine-based curing agent, a phenol-based curing agent, and an acid anhydride-based curing agent. The epoxy resin composition according to claim 1 or 2, wherein the hydroxyl value of the component (C) is 10 to 100 mg KOH / g. The epoxy resin composition according to any one of claims 1 to 3, wherein the component (C) is 1 to 40 parts by mass with respect to 100 parts by mass of the epoxy resin (A). The epoxy resin composition according to any one of claims 1 to 4, wherein the component (C) contains an aromatic ring. The viscosity of the component (C) at 75 ° C. is 1,000 to 20,000 mPa. The epoxy resin composition according to any one of claims 1 to 5, which is s. The cured product of the epoxy resin composition according to any one of claims 1 to 6. A semiconductor device encapsulant comprising the epoxy resin composition according to any one of claims 1 to 6. A semiconductor device comprising a semiconductor device sealed with the epoxy resin composition according to any one of claims 1 to 6.

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