JP6841285B2 - Manufacturing method of sealing resin composition, cured product, electronic component device and electronic component device - Google Patents

Description

The present invention relates to a sealing resin composition, a cured product, an electronic component device, and a method for manufacturing the electronic component device.

In recent years, high integration of electronic components such as semiconductor chips has been required. For example, a flip chip package in which a semiconductor chip and a substrate are bonded by solder bumps is often used for a semiconductor module.
Such semiconductor modules are installed in small mobile devices such as mobile phones and smartphones, and the demand in the market is increasing year by year. An underfill material is used as a sealing material in the flip chip package in order to ensure its insulating property. Since the underfill material exhibits fluidity at room temperature, the flip-chip package can be sealed by a method such as filling between the chip and the substrate by utilizing the capillary phenomenon and then curing the underfill material.

On the other hand, if the filling speed at the time of filling the underfill material by the capillary phenomenon in the manufacturing process of such a semiconductor module is the capillary speed, there is a problem that the capillary speed is slow and the workability is deteriorated. In general, the capillary velocity depends on the viscosity of the underfill material, and the lower the viscosity, the higher the capillary velocity tends to be. Examples of the method for reducing the viscosity include a method using a low-viscosity dilutable epoxy resin, a method for reducing the amount of filler, and the like. However, the reliability of the semiconductor module (insulation reliability, heat resistance, etc.) due to the decrease in Tg (glass transition temperature) due to the use of low-viscosity dilute epoxy resin and the increase in the coefficient of thermal expansion due to the decrease in the amount of filler. ) Deteriorates, and there is a demand for an underfill material that has both fluidity and reliability.

In response to such a requirement, for example, (A) epoxy resin, (B) curing agent, and (C) inorganic filler are included, and the average particle size and content of the (C) inorganic filler are less than 5 μm, respectively. And a method of using the underfill material, which is 67% by mass or more and less than 85% by mass of the whole underfill material and has a viscosity at 110 ° C. of 0.2 Pa · s or less, is disclosed (for example, Patent Document 1). ). It is described that low viscosity and high reliability can be obtained by manufacturing a semiconductor module using this underfill material.

JP 2015-189847

However, in recent years, semiconductor chips have been increasingly required to be miniaturized, and the bump pitch indicating the distance between the solder bumps connecting the chip and the substrate is as small as about 20 μm. When filling such a miniaturized semiconductor chip with an underfill material, the filler is clogged between bump pitches during flow, and the underfill material is not filled between the chip and the substrate. The problem can occur. The underfill material disclosed in Patent Document 1 does not have sufficient filling property when applied to a semiconductor module that has been miniaturized in recent years, and a composition having better fluidity while maintaining reliability such as heat resistance can be obtained. It has been demanded.

One embodiment of the present invention includes a sealing resin composition having excellent fluidity while maintaining heat resistance, a cured product obtained by curing the sealing resin composition, and an electronic component device including the cured product. Another object of the present invention is to provide a method for manufacturing an electronic component device using this sealing resin composition.

In order to achieve the above object, the inventors of the present application have diligently studied, and as a result, by using a sealing resin composition containing at least one of a metal complex and a metal compound, excellent fluidity is maintained while maintaining heat resistance. It has been found that a sealing resin composition having the above can be obtained.

Specific means for achieving the above-mentioned problems are as follows.

<1> A sealing resin composition containing (A) an epoxy resin, (B) a curing agent having at least one amino group, (C) at least one of a metal complex and a metal compound, and (D) an inorganic filler.
<2> The sealing resin composition according to <1>, wherein at least one of the (C) metal complex and the metal compound contains at least one of the aluminum chelate complex and the aluminum alkoxide compound.
<3> The sealing resin composition according to <2>, wherein at least one of the aluminum chelate complex and the aluminum alkoxide compound has at least one of an ester structure and an unsaturated carbonyl structure.
<4> Any of <1> to <3> in which the total content of at least one of the (C) metal complex and the metal compound is 0.5 parts by mass or less with respect to 100 parts by mass of the (A) epoxy resin. The sealing resin composition according to one.
<5> Any of <1> to <3> in which the total content of at least one of the (C) metal complex and the metal compound is 0.1 part by mass or less with respect to 100 parts by mass of the (A) epoxy resin. The sealing resin composition according to one.
<6> The total content of at least one of the (C) metal complex and the metal compound is 0.005 parts by mass or more and 0.1 parts by mass or less with respect to 100 parts by mass of the (A) epoxy resin. <1> The sealing resin composition according to any one of ~ <3>.
<7> The sealing resin composition according to any one of <1> to <6> used for sealing an electronic component device.

<8> A cured product obtained by curing the sealing resin composition according to any one of <1> to <7>.

<9> The substrate according to <8>, which is arranged in a gap between a substrate having a circuit layer, an electronic component arranged on the substrate and electrically connected to the circuit layer, and the substrate and the electronic component. An electronic component device including a cured product.

<10> The encapsulation of a substrate having a circuit layer and an electronic component arranged on the substrate and electrically connected to the circuit layer according to any one of <1> to <7>. A method for manufacturing an electronic component device, which comprises a step of sealing using a resin composition.

According to one embodiment of the present invention, a sealing resin composition having excellent fluidity while maintaining heat resistance, a cured product obtained by curing the sealing resin composition, and an electron comprising the cured product. It is possible to provide a component device and a method for manufacturing an electronic component device using the sealing resin composition.

6 is a graph showing the relationship between the viscosity at 110 ° C. and the shear rate of the sealing resin compositions in Example 1 and Comparative Example 1.

Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified. The same applies to the numerical values and their ranges, and does not limit the present invention.
In the present disclosure, the term "process" includes not only a process independent of other processes but also the process if the purpose of the process is achieved even if the process cannot be clearly distinguished from the other process. ..
The numerical range indicated by using "~" in the present disclosure includes the numerical values before and after "~" as the minimum value and the maximum value, respectively.
In the numerical range described stepwise in the present disclosure, the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of the numerical range described in another stepwise description. .. Further, in the numerical range described in the present disclosure, the upper limit value or the lower limit value of the numerical range may be replaced with the value shown in the examples.
In the present disclosure, the content rate or content of each component in the composition is the same when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. Means the total content or content of.
In the present disclosure, the particle size of each component in the composition refers to a mixture of the plurality of particles present in the composition when a plurality of particles corresponding to each component are present in the composition, unless otherwise specified. Means the value of.
In the present disclosure, the term "layer" includes not only the case where the layer is formed in the entire region but also the case where the layer is formed only in a part of the region when observing the region where the layer exists. Is done.

[Plastic composition for sealing]
The sealing resin composition of the present disclosure comprises (A) an epoxy resin, (B) a curing agent having at least one amino group, (C) at least one of a metal complex and a metal compound, and (D) an inorganic filler. Including. The sealing resin composition can be used, for example, for sealing electronic components. The sealing resin composition has excellent fluidity while maintaining heat resistance.

In the present disclosure, excellent fluidity refers to the temperature at which the sealing resin composition is applied to a substrate or the like, for example, the temperature at which an electronic component such as a chip is filled between the substrate and the like (underfill). (Temperature), it means low viscosity and low thixotropic property. The underfill temperature is generally 90 ° C to 120 ° C. The viscosity of the sealing resin composition decreases when the shear rate is high at the underfill temperature, but increases when the shear rate is low. When the shear rate is low and the viscosity is high, thixotropic property (thixotropic property) is exhibited, and the thixotropy value becomes large to 1 or more. In other words, when the viscosity at the underfill temperature is large, the shear rate is small due to the influence of drift friction compared to the first half of injection between the electronic component such as a chip and the substrate in the region where the shear rate is high. The viscosity in the latter half of the injection between the electronic component such as a chip and the substrate increases, and as a result, the flow rate decreases and the flow time becomes long. On the other hand, when the thixotropic property at the underfill temperature is small, that is, when the thixotropy value at the underfill temperature is close to 1, the viscosity of the sealing resin composition is less dependent on the shear rate, so that the chip or the like has a small viscosity. There is little change in the flow velocity between the first half of injection and the second half of injection between the electronic component and the substrate.

Here, in the sealing resin composition of the present disclosure, the thixotropy value at the underfill temperature is close to 1, and even if the shear rate is low, the viscosity is small and excellent fluidity is exhibited.

Hereinafter, each component contained in the sealing resin composition will be described.

<(A) Epoxy resin>
The sealing resin composition of the present disclosure contains (A) an epoxy resin. The epoxy resin (A) imparts curability and adhesiveness to the sealing resin composition, and imparts durability and heat resistance to the cured product of the sealing resin composition.

The epoxy resin (A) preferably contains an epoxy resin that is liquid at 25 ° C. from the viewpoint of fluidity. Further, a solid epoxy resin at 25 ° C. may be used in combination, and it is preferable to use a solid epoxy resin at 25 ° C. in combination within a range that does not affect the fluidity of the sealing resin composition.
In the present disclosure, each component contained in the sealing resin composition having a viscosity at 25 ° C. of 50 Pa · s or less is referred to as “liquid at 25 ° C.”.
By containing the epoxy resin liquid at 25 ° C. as the epoxy resin (A), the fluidity of the sealing resin composition tends to be improved.

The viscosity of the epoxy resin (A) at 25 ° C. is preferably 50 Pa · s or less, more preferably 0.01 Pa · s to 40 Pa · s, and 0.5 Pa · s to 30 Pa · s. Is even more preferable.
In the present disclosure, the viscosities of each component contained in the sealing resin composition such as (A) epoxy resin at 25 ° C. are 25 ° C. and 10 rotation speeds using an E-type viscometer (cone angle 3 °). The value measured under the condition of rotation / minute.

The type of epoxy resin (A) is not particularly limited. As the epoxy resin, naphthalene type epoxy resin; diglycidyl ether type epoxy resin such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, hydrogenated bisphenol A; phenols and aldehydes typified by orthocresol novolac type epoxy resin. Epoxy of novolak resin with; glycidyl ester type epoxy resin obtained by reaction of polybasic acids such as phthalic acid and dimer acid with epichlorohydrin; obtained by reaction of amine compounds such as diaminodiphenylmethane and isocyanuric acid with epichlorohydrin. Examples thereof include glycidylamine type epoxy resins.

The epoxy equivalent of the epoxy resin (A) is preferably 80 g / eq to 250 g / eq, more preferably 85 g / eq to 240 g / eq, and 90 g / eq to 230 g / eq from the viewpoint of viscosity adjustment. Is more preferable.
The epoxy equivalent measurement method in the present disclosure is described below.
Dissolve the epoxy resin in methyl ethyl ketone. Glacial acetic acid, cetyltrimethylammonium bromide and screen indicator (prepared by mixing a solution of 0.3 g of patent blue in 100 mL of glacial acetic acid and a solution of 1.5 g of thymol blue in 500 mL of methanol) in the solution. Is added and titrated with a perchlorate solution adjusted to 0.1N, and the point at which the color of the solution changes to pink and lasts for 1 minute in pink is defined as the end point. In addition, a blank test is performed, and the epoxy equivalent is calculated from the following formula.
Epoxy equivalent (g / eq) = (1000 × W) / {(SB) × N}
W: Sample mass B: Amount of 0.1N perchloric acid solution used for blank test S: Amount of 0.1N perchloric acid solution used for sample titration N: Normality of perchloric acid solution (0.1N) )

The weight average molecular weight of the epoxy resin (A) is not particularly limited. The weight average molecular weight of the epoxy resin (A) is preferably 100 to 1,000, more preferably 150 to 800, and even more preferably 200 to 500.
The methods for measuring the weight average molecular weight (Mw) and the number average molecular weight (Mn) in the present disclosure are described below.
The weight average molecular weight and the number average molecular weight are derived by measuring by gel permeation chromatography (GPC) and converting using a standard polystyrene calibration curve. The conditions of GPC are as shown below.
-GPC condition-
Pump: Hitachi L-6000 (manufactured by Hitachi, Ltd.)
Columns: The following 3 in total ・ Gelpack GL-R420
・ Gelpack GL-R430
-Gelpack GL-R440
(The above is a product name manufactured by Hitachi Kasei Co., Ltd.)
Eluent: tetrahydrofuran Measurement temperature: 25 ° C
Flow rate: 2.05 mL / min Detector: Hitachi L-3300 type RI (manufactured by Hitachi, Ltd.)

As the epoxy resin (A), a commercially available product may be used. Commercially available (A) epoxy resins include bisphenol F type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (product name: YDF-8170C), bisphenol A type epoxy resin manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. (product name: YD-128), and Mitsui. Bisphenol A type epoxy resin manufactured by Kagaku Co., Ltd. (product name: R-140P), amine type epoxy resin manufactured by Mitsubishi Chemical Co., Ltd. (product name: jER-630), naphthalene type epoxy resin manufactured by DIC Co., Ltd. (product name: HP-4032), etc. Can be mentioned. The epoxy resin (A) is not limited to these specific examples. As the epoxy resin (A), one type may be used alone or two or more types may be used in combination.

The content of the epoxy resin (A) is preferably 10% by mass to 50% by mass, and 15% by mass to 40% by mass, based on the sealing resin composition, from the viewpoint of fluidity, insulation reliability, and the like. It is more preferably%, and further preferably 20% by mass to 35% by mass.

<(B) Curing agent having at least one amino group (specific curing agent)>
The sealing resin composition of the present disclosure contains (B) a curing agent having at least one amino group (hereinafter, also referred to as “(B) specified curing agent”). (B) The specific curing agent tends to be able to prepare a sealing resin composition having excellent fluidity and pot life as compared with other curing agents described later.

The specific curing agent (B) is not particularly limited as long as it can cure the epoxy resin (A). (B) The specific curing agent may be one that cures by polymerization together with an epoxy resin, and if the sealing resin composition has fluidity when it is used as a sealing resin composition, it is at 25 ° C. It can be used either in liquid form or in solid form at 25 ° C. (B) By containing a curing agent liquid at 25 ° C. as the specific curing agent, the fluidity of the sealing resin composition tends to be improved.

Examples of the specific curing agent include amine-based curing agents such as chain aliphatic amines, cyclic aliphatic amines, aliphatic aromatic amines, and aromatic amines. As the amine-based curing agent, aromatic amines are preferable from the viewpoint of heat resistance and electrical properties.

Specific examples of the amine-based curing agent include m-phenylenediamine, 1,3-diaminotoluene, 1,4-diaminotoluene, 2,4-diaminotoluene, and 3,5-diethyl-2,4-diaminotoluene. , 3,5-diethyl-2,6-diaminotoluene, 2,4-diaminoanisole and other aromatic amine hardeners with one aromatic ring; 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfone, 4,4'-Diaminodiphenylsulphon, 4,4'-methylenebis (2-ethylaniline), 3,3'-diethyl-4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetramethyl- Aromatic amine curing agent with two aromatic rings such as 4,4'-diaminodiphenylmethane, 3,3', 5,5'-tetraethyl-4,4'-diaminodiphenylmethane; hydrolysis condensation of aromatic amine curing agent Aromatic amine having a polyether structure such as polytetramethylene oxide di-p-aminobenzoic acid ester, polytetramethylene oxide di-p-aminobenzoate; condensate of aromatic diamine and epichlorohydrin; aromatic diamine and Examples include reaction products with styrene.

(B) As the specific curing agent, a commercially available product may be used. Commercially available (B) specific curing agents include amine curing agents manufactured by Nippon Kayaku Co., Ltd. (product name: Kayahard-AA) and amine curing agents manufactured by Mitsubishi Chemical Co., Ltd. (product name: jER Cure (registered trademark) W, jER Cure). (Registered trademark) 113, etc.), amine curing agent manufactured by Albermar Japan Co., Ltd. (product name: EtaCure 300) and the like. (B) The specific curing agent is not limited to these specific examples. (B) As the specific curing agent, one type may be used alone or two or more types may be used in combination.

The content ratio of (A) epoxy resin and (B) specific curing agent in the sealing resin composition is not particularly limited, and the equivalent number of epoxy groups contained in (A) epoxy resin and (B) specific curing agent can be used. The ratio with the equivalent number of amino groups contained is also not particularly limited. In order to reduce the amount of each unreacted component, (A) the ratio of the equivalent number of amino groups contained in the specific curing agent to the equivalent number of epoxy groups contained in the epoxy resin (equivalent number of amino groups / epoxy group). The equivalent number) is preferably in the range of 0.6 to 1.4, more preferably in the range of 0.7 to 1.3, and preferably in the range of 0.8 to 1.2. More preferred.

The content of the specific curing agent (B) in the sealing resin composition is not particularly limited. The content of the specific curing agent (B) is preferably 5 parts by mass to 60 parts by mass with respect to 100 parts by mass of the epoxy resin (A) from the viewpoint of fluidity, insulation reliability and the like. More preferably, it is ~ 50 parts by mass.

The sealing resin composition may contain other curing agents other than (B) the specific curing agent. Examples of other curing agents include phenol-based curing agents, acid anhydride-based curing agents, imidazole-based curing agents, and carboxylic acid dihydrazide-based curing agents.

(B) When other curing agents other than the specified curing agent are used in combination, the content of the other curing agent in the sealing resin composition is (A) epoxy resin 100 from the viewpoint of fluidity, insulation reliability and the like. It is preferably 0.5 parts by mass to 5.0 parts by mass, and more preferably 1.0 part by mass to 3.0 parts by mass with respect to parts by mass.

(B) When other curing agents other than the specified curing agent are used in combination, the content of the other curing agents in the sealing resin composition is based on the total amount of the curing agent components from the viewpoint of fluidity, insulation reliability, etc. It is preferably 1% by mass to 50% by mass, more preferably 5% by mass to 35% by mass, and even more preferably 8% by mass to 20% by mass.

<(C) At least one of a metal complex and a metal compound>
The sealing resin composition of the present disclosure contains (C) at least one of a metal complex and a metal compound. (C) A sealing resin composition containing at least one of a metal complex and a metal compound tends to have high fluidity and high heat resistance.

The reason why the sealing resin composition containing at least one of the metal complex and the metal compound (C) exhibits high fluidity while maintaining heat resistance is not clear, but is presumed as follows. By containing at least one of the metal complex and the metal compound, (D) the surface activity of the inorganic filler is enhanced, (A) the interaction with the epoxy resin is enhanced, and the sealing resin composition is (F). When an alkoxy group-containing compound such as a silane coupling agent is contained, the condensation reaction between (D) the inorganic filler and (F) the alkoxy group-containing compound such as the silane coupling agent can be promoted. As a result, the affinity between the (A) epoxy resin and the (D) inorganic filler becomes good, and the effect of having high fluidity of the sealing resin composition while maintaining heat resistance is exhibited. Conceivable. Further, the metal complex and the metal compound preferably contain at least one of a carbonyl group and an alkoxy group. Since the carbonyl group and the alkoxy group are electron-withdrawing, the metal element in the metal complex and the metal compound becomes electron-deficient, and the Lewis acidity becomes high, so that the above effect tends to be more preferably exhibited.

(C) At least one of the metal complex and the metal compound can be used in a liquid state or a solid state at 25 ° C. (C) When at least one of the metal complex and the metal compound is liquid, it tends to be easily dissolved in the sealing resin composition. On the other hand, when at least one of the (C) metal complex and the metal compound is in a solid state, at least one of the (C) metal complex and the metal compound is dissolved in at least one of the (A) epoxy resin and (B) the specific curing agent. As a result, the sealing resin composition tends to be uniform, and stable characteristics tend to be obtained.

The metal complex and the metal compound are not particularly limited, and examples thereof include complexes and compounds of metal species such as iron, zinc, indium, magnesium, titanium, zirconium, and aluminum. Among them, the complex and the compound in which the metal type is aluminum are preferable from the viewpoint of the fluidity of the sealing resin composition, the handleability of the metal complex and the metal compound, and the cost. Further, among the complexes and compounds in which the metal type is aluminum, an aluminum chelate complex or an aluminum alkoxide compound is preferable from the viewpoint of fluidity.

Examples of the aluminum chelate complex include a complex in which three β-ketoenolate anions represented by the following general formula (1) are coordinated with aluminum, and the following general formula (2) and the following general formula (3) (3). Examples thereof include a complex in which one or two of the β-ketoenolate anions in 1) are replaced with alkoxide ions.

In the general formulas (1) to (3), R ^{1 to} R ⁶ independently represent an alkyl group having 1 to 25 carbon atoms or an alkoxy group having 1 to 25 carbon atoms. The alkyl group or alkoxy group represented by ^{R 1 to} R ^{6 may be linear or branched.} Further, the ^{alkyl group or alkoxy group represented by R 1 to} R ⁶ may have a substituent or may be unsubstituted, and is preferably unsubstituted. Examples of the substituent of the alkyl group include a fluorine atom, an amino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group and the like. The carbon number of the alkyl group represented by R ^{1 to} R ⁶ does not include the carbon number of the substituent. The ^{alkyl groups represented by R 1 to} R ⁶ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group and n-pentyl group. , N-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group. , N-Hexadecyl group, n-heptadecyl group, n-stearyl group, trifluoromethyl group and the like. Examples of the alkoxy group represented by R ^{1 to R 6} include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, an oleyloxy group and the like. Further, in the general formulas (2) and (3), R ⁷ and R ⁸ each independently represent an alkyl group having 1 to 25 carbon atoms. Examples of the alkyl group represented by R ⁷ and R ⁸ include the same alkyl groups represented by R ^{1 to} R ⁶ described above.

Specific examples of the aluminum chelate complex represented by the general formulas (1) to (3) include aluminum ethyl acetoacetate / disecondary butyrate, aluminum ethyl acetoacetate / diisopropirate, aluminum trisacetylacetonate, and aluminum tris. Examples thereof include ethyl acetoacetate, aluminum monoacetyl acetonate bisoleyl acetoacetate, aluminum ethyl acetoacetate diisopropylate, aluminum alkyl acetate diisopropirate, aluminum bisethyl acetoacetate monoacetyl acetonate and the like.

Examples of the aluminum alkoxide compound include compounds represented by the following general formula (4).

In the general formula (4), R ⁹ represents an alkyl group having 1 to 25 carbon atoms. The ^{alkyl group represented by R 9} may be linear or branched. Further, the ^{alkyl group represented by R 9} may have a substituent or may be unsubstituted, and is preferably unsubstituted. Examples of the substituent of the alkyl group include a fluorine atom, an amino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group and the like. The carbon number of the alkyl group represented by R ⁹ does not include the carbon number of the substituent. Examples of the alkyl group represented by R ⁹ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, s-butyl group, t-butyl group, n-pentyl group and n-. Hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n- Hexadecyl group, n-heptadecyl group, n-stearyl group, trifluoromethyl group and the like can be mentioned.

Examples of the aluminum alkoxide compound represented by the general formula (4) include aluminum triethoxydo, aluminum triisopropoxide, aluminum diisopropoxide monosecondary butoxide, aluminum trisecondary butoxide and the like.

There may be a plurality of elements of aluminum contained in the molecules of the aluminum chelate complex and the aluminum alkoxide compound. Therefore, cyclic aluminum oxide may be used as the aluminum alkoxide compound, and cyclic aluminum oxide represented by the general formula (5) may be preferably used.

In the general formula (5), R ^{10 to} R ¹² represent an acyl group having 1 to 25 carbon atoms. The ^{acyl group represented by R 10 to} R ¹² may be linear or branched. Further, the ^{acyl group represented by R 10 to} R ¹² may have a substituent or may be unsubstituted, and is preferably unsubstituted. Examples of the substituent of the acyl group include a fluorine atom, an amino group, a hydroxy group, a carboxy group, a sulfo group, a nitro group and the like. The carbon number of the acyl group represented by R ^{10 to} R ¹² does not include the carbon number of the substituent. The ^{acyl group represented by R 10 to} R ¹² includes a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a 2-methylpropanoyl group, a pentanoyl group, a hexanoyl group, a heptanoyle group, an octanoyl group, a nonanoyl group and a decanoyle group. , Undecanoyl group, dodecanoyl group, tridecanoyl group, tetradecanoyl group, pentadecanoyl group, hexadecanoyl group, heptadecanoyl group, stearoyl group and the like.

Cyclic aluminum oxide includes cyclic aluminum oxide laurate, cyclic aluminum oxide vegetable fatty acid acylate, cyclic aluminum oxide octylate, cyclic aluminum oxide-2-ethylhexanoate, cyclic aluminum oxide stearate, and cyclic aluminum oxide higher fatty acid condensation. Examples include object acylation.

Further, at least one of the above-mentioned aluminum chelate complex and aluminum alkoxide compound preferably has at least one of an ester structure and an unsaturated carbonyl structure from the viewpoint of further enhancing the fluidity of the sealing resin composition. The aluminum chelate complex preferably has an unsaturated carbonyl structure, and the above-mentioned aluminum alkoxide compound more preferably has an ester structure.

Commercially available products may be used as the metal complex and the metal compound. Commercially available metal complexes and metal compounds include aluminum trisacetylacetonate and aluminum isopropoxide manufactured by Tokyo Kasei Kogyo Co., Ltd., and cyclic aluminum oxide-2-ethylhexanoate manufactured by Kawaken Fine Chemicals Co., Ltd. (Product name: Argomer 800AF) and the like, acetalkoxyaluminum diisopropylate (product name: Plenact AL-M) manufactured by Ajinomoto Fine Techno Co., Ltd., and the like can be mentioned. The metal complex and the metal compound are not limited to these specific examples. (C) As at least one of the metal complex and the metal compound, one type may be used alone, two or more types may be used in combination, or the metal complex and the metal compound may be used in combination.

The total content of at least one of the (C) metal complex and the metal compound in the sealing resin composition is not particularly limited. From the viewpoint of fluidity, the total content of at least one of the (C) metal complex and the metal compound is preferably 0.5 parts by mass or less with respect to 100 parts by mass of the (A) epoxy resin. It is more preferably 1 part by mass or less, further preferably 0.005 part by mass to 0.1 part by mass, and particularly preferably 0.03 part by mass to 0.05 part by mass. In particular, when the total content of at least one of the (C) metal complex and the metal compound is 0.1 part by mass or less with respect to 100 parts by mass of the (A) epoxy resin, it is preferable to increase the viscosity by cationic polymerization of the epoxy resin. It can be suppressed and tends to be superior in fluidity. Further, when the total content of at least one of the (C) metal complex and the metal compound is 0.005 parts by mass or more with respect to 100 parts by mass of the (A) epoxy resin, the surface of the (D) inorganic filler described later. , Preferably, the dehydration condensation of the surface of the silica particles and the silane coupling agent (F) described later proceeds favorably, and there is a tendency that better fluidity can be obtained.

<(D) Inorganic filler>
The sealing resin composition of the present disclosure contains (D) an inorganic filler.
(D) The cured product of the sealing resin composition containing the inorganic filler tends to be excellent in heat cycle resistance, moisture resistance, and stress reduction.

(D) The inorganic filler is not particularly limited. Specific examples of the inorganic filler (D) include colloidal silica, hydrophobic silica, silica such as spherical silica, talc, and the like, and spherical silica is preferable from the viewpoint of fluidity at the time of coating.

In the present disclosure, silica is "spherical" as follows.
First, when natural silica or synthetic silica is heat-treated to be spheroidized, the particles that are not completely melted may not be spherical in shape. In addition, a plurality of molten particles fused together may coexist. Further, the evaporated silica vapor may adhere to the surface of other particles and solidify, resulting in spherical silica particles to which fine particles are attached. The fact that silica is substantially spherical allows a mixture of particles having such a shape. For example, the sphericity of a particle is changed to the sphericity of Wardel [(diameter of a circle equal to the projected area of the particle) / (particle). (Diameter of the smallest circle circumscribing the projected image of)], when particles with this value of 0.9 or more are 90% by mass or more of the total silica, it is said that the silica is "spherical". To do.

As the inorganic filler (D), spherical silica having an average particle diameter of 0.01 μm to 20 μm is preferable, and spherical silica having an average particle diameter of 0.02 μm to 10 μm is more preferable from the viewpoint of fluidity.
The method for measuring the average particle size in the present disclosure is described below.
The average particle size refers to a value measured by a particle size distribution based on the number of particles and the frequency thereof using a laser diffraction / scattering type particle size distribution measuring device LA-920 (manufactured by HORIBA, Ltd.). As the dispersion solvent, it is preferable to use either water, acetone or ethanol for dispersing the particles. As the measurement conditions, the particle concentration is tens to hundreds of ppm on the basis of mass, the ultrasonic treatment time is 30 minutes, and the measurement temperature is room temperature (25 ° C.).

As the (D) inorganic filler, a commercially available product may be used. Examples of the commercially available (D) inorganic filler include spherical silica manufactured by Admatex Co., Ltd. (product names: SO-E2, SE2300, SE2200-SEJ, etc.). (D) The inorganic filler is not limited to these specific examples. (D) As the inorganic filler, one type may be used alone or two or more types may be used in combination.

As the (D) inorganic filler, one which has been surface-treated with at least one of the following (F) coupling agents may be used, and (F) the surface-treated with the coupling agent (D). The inorganic filler and the (D) inorganic filler which has not been surface-treated may be used in combination. By using the (D) inorganic filler whose surface has been treated with the (F) coupling agent, the affinity between the (D) inorganic filler and the resin component is improved, and the workability of the sealing resin composition is improved. And the fluidity, as well as the toughness, elastic modulus and adhesive strength of the cured product tend to be improved.

When the (D) inorganic filler is surface-treated with the (F) coupling agent, the ratio of the (D) inorganic filler to the (F) coupling agent is (D) cup with respect to the (D) inorganic filler. The ring agent is preferably 0.2% by mass to 5.0% by mass, more preferably 0.3% by mass to 3.0% by mass, and 0.4% by mass to 2.0% by mass. It is more preferable to have.

The content of the inorganic filler (D) is preferably 5 parts by mass to 80 parts by mass, preferably 20 parts by mass with respect to 100 parts by mass of the (A) epoxy resin, from the viewpoint of fluidity, insulation reliability and the like. More preferably, it is ~ 70 parts by mass.

The content of the inorganic filler (D) is preferably 40% by mass to 85% by mass, and 50% by mass to 75% by mass, based on the sealing resin composition, from the viewpoint of fluidity, insulation reliability, and the like. It is more preferably mass%, and even more preferably 55% by mass to 70% by mass.

When the sealing resin composition contains (F) an inorganic filler that has been surface-treated with a coupling agent (F), (F) has been surface-treated with a coupling agent (D). From the viewpoint of fluidity, adhesiveness, etc., the content of the inorganic filler is preferably 5 parts by mass to 80 parts by mass, and 20 parts by mass to 70 parts by mass with respect to 100 parts by mass of the epoxy resin (A). Is more preferable.

When the sealing resin composition contains (D) an inorganic filler that has been surface-treated with (F) a coupling agent in advance, its content is sealed from the viewpoint of fluidity, adhesiveness, and the like. It is preferably 40% by mass to 85% by mass, more preferably 50% by mass to 75% by mass, and further preferably 55% by mass to 70% by mass with respect to the resin composition for use.

<(E) Rubber additive>
The sealing resin composition of the present disclosure may contain (E) a rubber additive, if necessary.
(E) The cured product of the sealing resin composition containing the rubber additive tends to be excellent in stress relaxation.

The type of the rubber additive (E) is not particularly limited, and can be appropriately selected from conventionally known ones. Specific examples of the rubber additive (E) include acrylic rubber, urethane rubber, silicone rubber, butadiene rubber and the like. The rubber additive (E) can be used either in a liquid state at 25 ° C. or in a solid state at 25 ° C.

When the rubber additive (E) is solid at 25 ° C., the form of the rubber additive (E) is not particularly limited, and examples thereof include particles, powders, and pellets. From the viewpoint of heat resistance, the rubber additive (E) is preferably in the form of particles. When the rubber additive (E) is in the form of particles, the average particle size of the rubber additive (E) is preferably 0.01 μm to 20 μm, more preferably 0.02 μm to 10 μm, and 0.03 μm to 0.03 μm. It is more preferably 5 μm.

When the (E) rubber additive is liquid at 25 ° C., examples of the (E) rubber additive include low molecular weight components such as polybutadiene, butadiene / acrylonitrile copolymer, polyisoprene, polypropylene oxide, and polydiorganosiloxane. The weight average molecular weight of the low molecular weight component is preferably 5,000 to 80,000, more preferably 8,000 to 50,000.

When the rubber additive (E) is solid at 25 ° C., it is preferable to heat it and dissolve it in (A) an epoxy resin or (B) a specific curing agent before use. Further, as the rubber additive (E), one having a group that reacts with an epoxy group at the end may be used. The rubber additive (E) having a group that reacts with an epoxy group at the end can be used either in a liquid state at 25 ° C. or in a solid state at 25 ° C. Examples of the group that reacts with the epoxy group include a carboxy group, a hydroxyl group, an amino group and the like.

As the rubber additive (E), a commercially available product may be used. Commercially available (E) rubber additives include CTBN1300, ATBN1300-16, CTBN10008-SP manufactured by Ube Kosan Co., Ltd., silicone rubber powder manufactured by Toray Dow Corning Co., Ltd. (product name: AY42-119), manufactured by JSR Corporation. Examples include rubber powder (product name: XER81). (E) The rubber additive is not limited to these specific examples. (E) As the rubber additive, one type may be used alone or two or more types may be used in combination.

When the sealing resin composition contains (E) a rubber additive, the content of the (E) rubber additive is based on 100 parts by mass of the (A) epoxy resin from the viewpoint of fluidity, adhesion, and the like. , 0.2 parts by mass to 5.0 parts by mass, and more preferably 0.5 parts by mass to 3.0 parts by mass.

When the sealing resin composition contains (E) a rubber additive, the content of the (E) rubber additive is 0. It is preferably 05% by mass to 5.0% by mass, more preferably 0.1% by mass to 4.0% by mass, and further preferably 0.4% by mass to 3.0% by mass. ..

<(F) Coupling agent>
The sealing resin composition may contain (F) a coupling agent, if necessary.
(F) The sealing resin composition containing the coupling agent tends to have excellent adhesion. Further, when the sealing resin composition contains (F) a coupling agent and (D) the inorganic filler is silica, between the silanol group on the silica surface and the epoxy group contained in the silane coupling agent. Condensation is promoted, the compatibility between (A) epoxy resin and (D) inorganic filler becomes better, and more excellent fluidity tends to be obtained.

The type of the coupling agent (F) is not particularly limited, and can be appropriately selected from conventionally known ones. Specific examples of the (F) coupling agent include a silane compound having at least one selected from the group consisting of a primary amino group, a secondary amino group and a tertiary amino group, a silane compound having an epoxy group, and a mercapto group. Silane compounds such as silane compounds having, silane compounds having alkyl groups, silane compounds having phenyl groups, silane compounds having ureido groups, silane compounds having methacrylic groups, silane compounds having acrylic groups, and silane compounds having vinyl groups. ; Titanate compounds and the like can be mentioned. Among these, a silane compound having an epoxy group is preferable from the viewpoint of adhesion of the sealing resin composition.

(F) As the coupling agent, a commercially available product may be used. Commercially available (F) coupling agents include KBM-303, KBM-402, KBM-403, KBE-403, KBE-903, KBE-9103, KBM-573, KBM-502, manufactured by Shin-Etsu Chemical Co., Ltd. KBM-503, KBE-502, KBE-503, KBM-5103, KBM-1003, KBE-585, KBM-9569, KBM-803, KBE-846, KBE-9007, X-12-967C, KBM-103, KBM-202SS and the like can be mentioned. (F) The coupling agent is not limited to these specific examples. (F) As the coupling agent, one type may be used alone or two or more types may be used in combination.

The (F) coupling agent may be contained in the sealing resin composition as a surface treatment agent for the (D) inorganic filler in a state of being attached to the surface of the (D) inorganic filler.

When the sealing resin composition contains (F) a coupling agent, the content of the (F) coupling agent is based on 100 parts by mass of the (A) epoxy resin from the viewpoint of fluidity, heat resistance and the like. It is preferably 0.2 parts by mass to 5.0 parts by mass, and more preferably 0.5 parts by mass to 3.0 parts by mass.

When the sealing resin composition contains (F) a coupling agent, the content of the (F) coupling agent is 0. It is preferably 05% by mass to 5.0% by mass, more preferably 0.1% by mass to 4.0% by mass, and further preferably 0.4% by mass to 3.0% by mass. ..

<Other ingredients>
The sealing resin composition can be used as long as the effect of suppressing the occurrence of the bleeding phenomenon can be obtained, and if necessary, a rocking agent for improving workability, a pigment such as carbon black, a dye, an ion trapper, and a diluent. It may contain a foaming agent, a leveling agent, an antioxidant, a curing accelerator, a reactive diluent, an organic solvent and the like.

<Preparation method of resin composition for sealing>
The sealing resin composition of the present disclosure includes (A) an epoxy resin, (B) a specific curing agent, (C) at least one of a metal complex and a metal compound, (D) an inorganic filler, and (E) a rubber additive. , (F) Other additives such as a coupling agent can be obtained by stirring, melting, mixing, dispersing, etc., collectively or separately, while subjecting heat treatment as necessary. In particular, when at least one of (A) epoxy resin, (B) specific curing agent, (C) metal complex and metal compound is solid, the viscosity increases and workability decreases when the solid is blended. Therefore, it is preferable to liquefy it by heating in advance and mix it. The apparatus for mixing, stirring, dispersing, etc., is not particularly limited, and examples thereof include a Raikai machine equipped with a stirring device, a heating device, a three-roll mill, a ball mill, a planetary mixer, and a bead mill. The sealing resin composition can be obtained by mixing the above components using these devices, kneading the components, and defoaming if necessary.

<Physical characteristics of resin composition for sealing>
The viscosity of the sealing resin composition is not particularly limited. Above all, from the viewpoint of fluidity, the viscosity of the sealing resin composition is preferably 0.1 Pa · s to 100.0 Pa · s at 25 ° C., and 0.1 Pa · s to 80.0 Pa · s at 25 ° C. More preferably, it is s. The viscosity of the sealing resin composition at 25 ° C. can be measured using an E-type viscometer (cone angle 3 °, rotation speed 10 rotations / minute).

When the sealing resin composition is used as an underfill material for flip chips, etc., the sealing resin composition is used as an index when filling in a narrow gap of several tens of μm to several hundreds of μm at around 100 ° C to 120 ° C. The viscosity of is preferably 0.40 Pa · s or less at 110 ° C., more preferably 0.30 Pa · s or less at 110 ° C., and even more preferably 0.25 Pa · s or less at 110 ° C. , 0.20 Pa · s or less at 110 ° C. is particularly preferable. The viscosity of the sealing resin composition at 110 ° C. shall be measured using a rheometer AR2000 (manufactured by TA Instruments Japan Co., Ltd., aluminum cone 40 mm, shear rate 32.5 / s). Can be done.

In the sealing resin composition, the thixotropy value at 25 ° C. is preferably 0.48 or more and 1.5 or less, preferably 0.5 or more and 1 or more, from the viewpoint of filling property and fillet forming property in underfill material applications. It is more preferably 5.5 or less, and further preferably 0.8 or more and 1.2 or less. Here, the thixotropy value at 25 ° C. can be calculated by the method described in Examples described later.

The thixotropy value at 110 ° C. is preferably 2.2 or less, more preferably 2.0 or less, and even more preferably 1.5 or less. The thixotropy value at 110 ° C. assumes an effect on the speeds of the first half and the second half of the injection of the sealing resin composition between the electronic component such as a chip and the substrate. The thixotropy value of the sealing resin composition at 110 ° C. can be calculated by the method described in Examples described later.

The viscosity and thixotropy (thixotropic index) of the sealing resin composition can be set in a desired range by appropriately selecting the composition ratio of each component.

The pot life, which is an index for the storage stability of the sealing resin composition, is the rate of change in viscosity before and after storage in an atmosphere of 25 ° C. for 24 hours, and is calculated by the following formula.
Pot life (%) = 100 x [(Viscosity after storage-Viscosity before storage) / Viscosity before storage]

The smaller the value of the pot life, the higher the storage stability, and the pot life is preferably 150% or less, more preferably 130% or less, and further preferably 100% or less.

[Cured product]
The cured product of the present disclosure is obtained by curing a sealing resin composition having excellent fluidity while maintaining heat resistance. The cured product can be produced by curing the sealing resin composition by, for example, heat-treating it at 80 ° C. to 165 ° C. for 1 minute to 150 minutes, and sealing the electronic component as described later. It is used as a sealing material to stop.

[Electronic component equipment]
The electronic component device of the present disclosure includes a substrate having a circuit layer, an electronic component arranged on the substrate and electrically connected to the circuit layer, and a book arranged in a gap between the substrate and the electronic component. With the disclosed cured product. The electronic component device of the present disclosure can be obtained by sealing an electronic component with the sealing resin composition of the present disclosure. Since the electronic component is sealed by the sealing resin composition of the present disclosure, the electronic component device of the present disclosure is excellent in temperature cycle resistance.

Electronic component devices include lead frames, pre-wired tape carriers, rigid wiring boards, flexible wiring boards, glass, silicon wafers and other circuit layers, semiconductor chips, transistors, diodes, thyristors and other active elements, and capacitors. Examples thereof include an electronic component device obtained by mounting electronic components such as a resistor, a resistance array, a coil, and a switch, and sealing the necessary portion with the sealing resin composition of the present disclosure.
In particular, a semiconductor device in which a semiconductor element is flip-chip bonded by bump connection to a rigid wiring board, a flexible wiring board, or a wiring formed on glass is mentioned as one of the objects to which the present disclosure can be applied. Specific examples include electronic component devices such as flip-chip BGA (Ball Grid Array), LGA (Land Grid Array), and COF (Chip On Film).

The sealing resin composition of the present disclosure is suitable as an underfill material for flip chips having excellent reliability. In the field of flip chips to which the sealing resin composition of the present disclosure is particularly preferably applied, the bump material for connecting the wiring board and the semiconductor element is not the conventional lead-containing solder, but a Sn-Ag-Cu system or the like. It is a flip-chip semiconductor component using lead-free solder. The sealing resin composition of the present disclosure can maintain good reliability even for flip chips in which bump connections are made using lead-free solder, which is physically fragile as compared with conventional lead solder. Further, when a chip scale package such as a wafer level CSP is mounted on a substrate, the reliability can be improved by applying the sealing resin composition of the present disclosure.

[Manufacturing method of electronic component equipment]
In the method for manufacturing an electronic component device of the present disclosure, a substrate having a circuit layer and an electronic component arranged on the substrate and electrically connected to the circuit layer are combined with the sealing resin composition of the present disclosure. It has a step of sealing using.
The step of sealing the substrate having the circuit layer and the electronic component by using the sealing resin composition of the present disclosure is not particularly limited. For example, after connecting an electronic component and a substrate having a circuit layer, a sealing resin composition is applied to a gap between the electronic component and the substrate by utilizing the capillary phenomenon, and then a curing reaction of the sealing resin composition is applied. When the sealing resin composition of the present disclosure is applied to at least one surface of a substrate having a circuit layer and an electronic component in advance and heat-pressed to connect the electronic component to the substrate. , A pre-coating method in which the connection of electronic components and substrates and the curing reaction of the sealing resin composition are collectively performed can be mentioned.
Examples of the method for applying the sealing resin composition include a casting method, a dispensing method, and a printing method.

The curing conditions for curing the sealing resin composition applied to the gap between the electronic component and the substrate are not particularly limited, and for example, heat treatment is performed at 80 ° C. to 165 ° C. for 1 minute to 150 minutes. Is preferable.

By using the sealing resin composition of the present disclosure, it is possible to manufacture an electronic component device provided with a cured product having excellent narrow gap filling property in a short working time.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited to the following examples. In the following examples, parts and% indicate parts by mass and% by mass unless otherwise specified.

(Examples 1 to 14, Comparative Example 1)
Each component was blended so as to have the compositions shown in Tables 1 and 2, and kneaded and dispersed with a three-roll machine and a vacuum raikai machine to prepare a sealing resin composition of Examples 1 to 14 and Comparative Example 1. did. The compounding unit in the table is a part by mass, and "-" indicates "no compounding". Further, the content rate (mass%) of the inorganic filler in the sealing resin composition was calculated from the blending amount of each component.

The following materials were prepared as the epoxy resin (A).
-Epoxy resin 1: Bisphenol F type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., trade name "YDF8170C")
-Epoxy resin 2: Naphthalene type epoxy resin (manufactured by DIC Corporation, trade name "HP-4032")
-Epoxy resin 3: Bisphenol A type epoxy resin (manufactured by Mitsui Chemicals, Inc., trade name "R-140P")

(B) The following materials were prepared as specific curing agents.
-Curing agent 1: Diaminophenylmethane type amine curing agent (manufactured by Nippon Kayaku Co., Ltd., trade name "Kayahard-AA")
-Curing agent 2: Dimethylthiotoluenediamine curing agent (manufactured by Albermar Japan Co., Ltd., trade name "Etacure 300")

The following materials were prepared as the metal complex and the metal compound.
-Metal complex 1: Aluminum trisacetylacetone (manufactured by Tokyo Chemical Industry Co., Ltd.)
-Metallic compound 1: Cyclic aluminum oxide-2-ethylhexanoate (manufactured by Kawaken Fine Chemical Co., Ltd., trade name "Argomer 800AF")
-Metallic compound 2: Aluminum isopropoxide (manufactured by Tokyo Chemical Industry Co., Ltd.)
-Metal complex 2: Acetalkoxyaluminum diisopropilate (manufactured by Ajinomoto Fine-Techno Co., Ltd., trade name "Plenact AL-M")

(D) The following materials were prepared as the inorganic filler.
-Inorganic filler 1: Spherical silica treated with a silane compound having an epoxy group with an average particle size of 0.6 μm (manufactured by Admatex Co., Ltd., trade name "SE2200-SEJ").

(F) The following materials were prepared as the silane coupling agent.
-Silane coupling agent 1: Epoxy group-containing silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-403")
-Silane coupling agent 2: Alicyclic epoxy group-containing silane coupling agent (manufactured by Shin-Etsu Chemical Co., Ltd., trade name "KBM-303")

Carbon black (manufactured by Mitsubishi Chemical Corporation, trade name "MA-100") was prepared as the colorant 1.

Various properties of the sealing resin composition obtained by using the above materials were evaluated as follows. The numerical values are shown in Tables 1 and 2 below.

(1) Fluidity: Viscosity and thixotropy The viscosity of the sealing resin composition at 25 ° C (viscosity at room temperature, Pa · s) is measured with an E-type viscometer (cone angle 3 °, rotation speed 10 rotations / minute). ) Was used for measurement. Further, the chixo value at 25 ° C. is the number of rotations with respect to the viscosity (η2) when measured at a rotation speed of 10 rotations / minute using an E-type viscometer (VISCONIC manufactured by Tokimec Co., Ltd., cone angle 3 °). The ratio (η1 / η2) of the viscosity (η1) when measured at 5 rpm.
The viscosity (Pa · s) at 110 ° C. was measured at a shear rate of 32.5 / s using a rheometer (AR2000 manufactured by TA Instrument Co., Ltd., aluminum cone 40 mm). For Example 1 and Comparative Example 1, the viscosity (Pa · s) at 110 ° C. when the shear rate was changed was measured. The results are shown in FIG.
The thixotropy value at 110 ° C. is 2.5 / s with respect to the viscosity (η4) when measured using a rheometer (AR2000 manufactured by TA Instrument Co., Ltd., aluminum cone 40 mm, shear rate 32.5 / s). The ratio of the viscosity (η3) measured in (η3 / η4) was used.

(2) Filling time A 20 mm square glass substrate is laminated with a gap of 25 μm, and the sealing resin composition is injected into the gap by capillary action, and the arrival time at 10 mm in the first half of injection and 20 mm in the second half of injection is achieved. Were measured respectively.

(3) Heat resistance: glass transition temperature (Tg) and coefficient of thermal expansion (CTE)
The sealing resin composition was cured under the conditions of 150 ° C. and 120 minutes to prepare a test piece (φ4 mm × 20 mm). The prepared test piece was subjected to a load of 15 g, a measurement temperature of -50 ° C to 220 ° C, and a temperature rise rate of 5 ° C / min using a thermomechanical analyzer (manufactured by TA Instruments Japan Co., Ltd., trade name TMAQ400). The glass transition temperature (Tg) and the coefficient of thermal expansion (CTE) were measured under the conditions of.
The coefficient of thermal expansion in the temperature range below Tg was defined as CTE1, and the coefficient of thermal expansion in the temperature range above Tg was defined as CTE2. Tg and CTE show thermal stability, Tg is preferably around 100 ° C., and CTE1 and CTE2 are preferably lower.

As can be seen from Table 1, Table 2 and FIG. 1, it can be seen that the sealing resin composition of this example exhibits high fluidity during underfilling while maintaining heat resistance.

All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.

Claims (10)

(A) an epoxy resin, saw including the at least one, and (D) an inorganic filler (B) a curing agent having at least one amino group, (C) a metal complex and a metal compound other than the metal complex,
A sealing resin composition in which the total content of at least one of the (C) metal complex and a metal compound other than the metal complex is 0.1 part by mass or less with respect to 100 parts by mass of the (A) epoxy resin. The sealing resin composition according to claim 1, wherein at least one of the metal complex (C) and a metal compound other than the metal complex contains at least one of an aluminum chelate complex and an aluminum alkoxide compound. The sealing resin composition according to claim 2, wherein at least one of the aluminum chelate complex and the aluminum alkoxide compound has at least one of an ester structure and an unsaturated carbonyl structure. A claim that the total content of at least one of the (C) metal complex and a metal compound other than the metal complex is 0.005 parts by mass or more and 0.1 parts by mass or less with respect to 100 parts by mass of the (A) epoxy resin. The sealing resin composition according to any one of Items 1 to 3. The sealing resin composition according to any one of claims 1 to 4, wherein the (A) epoxy resin contains a bisphenol F type epoxy resin, a bisphenol A type epoxy resin, and a naphthalene type epoxy resin. The sealing resin composition according to any one of claims 1 to 5, which is used for sealing an electronic component device. The sealing resin composition according to any one of claims 1 to 6, which is used for underfilling. A cured product obtained by curing the sealing resin composition according to any one of claims 1 to 7. A board with a circuit layer and
Electronic components placed on the substrate and electrically connected to the circuit layer
The cured product according to claim 8, which is arranged in a gap between the substrate and the electronic component.
Electronic component device equipped with. The sealing resin composition according to any one of claims 1 to 7, wherein a substrate having a circuit layer and an electronic component arranged on the substrate and electrically connected to the circuit layer are provided. A method of manufacturing an electronic component device having a step of sealing using.