Liquid resin composition, semiconductor sealing material, underfill material and semiconductor device

Abstract

This invention provides a liquid resin composition that exhibits high fluidity at high temperatures and can suppress abnormalities and damage to the appearance of hardened materials exposed to high temperatures. The liquid resin composition contains a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), a low-stress agent (D), and a high-fluidity agent (E). The low-stress agent (D) contains an epoxidized fatty acid ester compound (D-1). The high-fluidity agent (E) contains at least one compound selected from the group consisting of compounds having a quaternary phosphonic cationic structure (E-1) and compounds having a silicate anionic structure (E-2).

Description

[Technical Field]

[0001] Field of the Invention This invention generally relates to liquid resin compositions, semiconductor sealing materials, underfill materials and semiconductor devices, and more specifically, to liquid resin compositions containing epoxy compounds, semiconductor sealing materials, underfill materials and semiconductor devices. [Previous Technology]

[0002] Background of the Invention Patent Document 1 discloses a sealing resin composition comprising (A) epoxy resin, (B) hardener, (C) inorganic filler material, and (D) triglyceride having unsaturated fatty acid residues.

[0003] Patent Document 2 discloses an epoxy resin composition comprising (A) an epoxy resin, (B) a curing agent and a premix, the premix comprising at least a portion of either or both of the aforementioned (A) epoxy resin and the aforementioned (B) curing agent and (C) a polysiloxane compound; the aforementioned (C) polysiloxane compound comprises both (c1) and (c2) described below: (c1) is a first polysiloxane compound belonging to a two-terminated epoxy-modified polysiloxane oil, and (c2) is a second polysiloxane compound belonging to a side-chain epoxy-polyether modified polysiloxane oil.

[0004] Prior Art Documents [Patent Documents] [Patent Document 1] Japanese Patent Application Publication No. 2023-113250 [Patent Document 2] Japanese Patent Publication No. 6065358 [Summary of the Invention]

[0005] Summary of the Invention With the increasing density, large area, and heat generation of semiconductor devices, the resin composition for sealing must ensure formability and simultaneously suppress defects such as cracking and discoloration of the hardened material at high temperatures. However, the resin composition described in Patent Document 1 or 2 has the following problems: it is difficult to achieve high fluidity at high temperatures and to suppress abnormal appearance and damage of the hardened material when exposed to high temperatures.

[0006] The subject of this case is to provide a liquid resin composition, a semiconductor sealing material, a bottom filler material, and a semiconductor device that have high fluidity at high temperatures and can suppress abnormal appearance and damage of the hardened material when exposed to high temperatures.

[0007] This invention discloses a liquid resin composition comprising: a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), a low-stress agent (D), and a high-flowability agent (E). The aforementioned low-stress agent (D) comprises an epoxidized fatty acid ester compound (D-1). The aforementioned high-flowability agent (E) comprises at least one compound selected from the group consisting of a compound having a quaternary phosphonic cationic structure (E-1) and a compound having a silicate anionic structure (E-2).

[0008] The semiconductor sealing material of this case contains the aforementioned liquid resin composition.

[0009] The bottom filling material of one type of sample in this case contains the aforementioned liquid resin composition.

[0010] A semiconductor device of this invention includes a substrate, a semiconductor element mounted on the substrate, and a sealing portion located between the substrate and the semiconductor element. The sealing portion includes a hardened version of the bottom filler material.

Implementation Method

[0012] Embodiments for Implementing the Invention 1. Summary Description of Embodiments of the Invention. Furthermore, the following embodiments are only a part of the various embodiments of the invention. Also, if the following embodiments achieve the purpose of the invention, various changes can be made according to design, etc. The dimensions of the constituent elements in the following schematic diagrams may not necessarily reflect the actual dimensions. Although the mechanisms of action in the embodiments are explained below, these explanations include speculative descriptions, and the invention is not limited by these explanations.

[0013] The liquid resin composition of the embodiment (hereinafter also referred to as composition (X)) contains: a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), a low-stress agent (D), and a high-flowability agent (E). The low-stress agent (D) contains an epoxidized fatty acid ester compound (D-1). The high-flowability agent (E) contains at least one compound selected from the group consisting of a compound having a quaternary phosphonic cationic structure (E-1) and a compound having a silicate anionic structure (E-2).

[0014] According to the embodiment, a composition (X) that has high fluidity at high temperatures and can suppress abnormal appearance and damage of the hardened material when exposed to high temperatures can be obtained. The reason why composition (X) achieves the above-mentioned effect is not yet clear, but it is speculated to be due to the following reasons.

[0015] Because the epoxidized fatty acid ester compound (D-1) has an aliphatic backbone, it does not easily hinder the flowability of composition (X). Furthermore, the epoxidized fatty acid ester compound (D-1) improves the flexibility of the cured material, thus inhibiting damage such as cracks. Moreover, when composition (X) is cured, the epoxidized fatty acid ester compound (D-1) reacts with the epoxide compound (A) and the aromatic amine compound (B) and is incorporated into the polymer backbone of the cured material. Therefore, even when the cured material is exposed to high temperatures, the components of the polymer backbone in the cured material are difficult to separate, thus the appearance of the cured material is less likely to become abnormal.

[0016] The composition (X) contains at least one compound selected from the group consisting of a compound having a quadrivalent phosphonium cation (E-1) and a compound having a silicate anion (E-2). The compound having a quadrivalent phosphonium cation (E-1) or the compound having a silicate anion (E-2), by adhering to the surface of the inorganic filler material (C), can suppress the generation of ions from the inorganic filler material (C). This improves the storage stability of the composition (X) and simultaneously enhances its flowability at high temperatures.

[0017] Thus, the composition (X) of the embodiment, by combining an epoxidized fatty acid ester compound (D-1) and at least one of the group consisting of a compound having a quaternary phosphonium cation (E-1) and a compound having a silicate anion (E-2) with an epoxy compound (A), an aromatic amine compound (B) and an inorganic filler material (C), has high fluidity at high temperatures and can suppress abnormal appearance and damage of the hardened material when exposed to high temperatures.

[0018] The composition (X) can be used to fabricate a sealing portion for sealing semiconductors in semiconductor devices, etc. That is, the semiconductor sealing material of the embodiment contains the composition (X). In particular, the composition (X) is suitable for fabricating a sealing portion between a semiconductor element assembled on a substrate in a semiconductor device, etc., and the substrate. That is, the underfill material of the embodiment contains the composition (X). The semiconductor sealing material and underfill material of the embodiment can easily flow between the semiconductor element and the substrate when fabricating the sealing portion, thereby improving the manufacturing efficiency of the semiconductor device and suppressing poor filling of the sealing portion between the semiconductor element and the substrate.

[0019] Furthermore, the use of composition (X) is not limited to manufacturing semiconductor devices. Composition (X) can be used for various purposes other than manufacturing semiconductor devices.

[0020] 2. Composition 2.1 In the composition embodiment of the composition, composition (X) contains: liquid epoxy compound (A), liquid aromatic amine compound (B), inorganic filler (C), epoxidized fatty acid ester compound (D-1), and at least one selected from the group consisting of a compound having a quaternary phosphonic cationic structure (E-1) and a compound having a silicate anionic structure (E-2).

[0021] (Epoxy Compound) The epoxy compound (A) is liquid as described above. Liquid means having the property of flowing at 25°C. The components of the epoxy compound (A) may all be liquid, but for example, the epoxy compound (A) may contain liquid and solid components, and the epoxy compound (A) may be liquid as a whole by mixing the aforementioned components. In addition, the liquid epoxy compound (A) may impart fluidity to the composition (X).

[0022] The viscosity of the epoxy compound (A) at 25°C is preferably 100 Pa·s or less. This viscosity is more preferably 50 Pa·s or less, and even more preferably 20 Pa·s or less. Furthermore, the viscosity of the epoxy compound (A) at 25°C is, for example, 0.01 Pa·s or more. This viscosity is preferably 0.02 Pa·s or more.

[0023] The epoxy compound (A) preferably contains a compound having two or more epoxy groups in one molecule. This can improve the reactivity of the epoxy compound (A) with the aromatic amine compound (B).

[0024] The epoxy equivalent of the epoxy compound (A) is, for example, 50 g / eq. or more and 500 g / eq. or less. This improves the reactivity of the epoxy compound (A) with the aromatic amine compound (B). The epoxy equivalent of this epoxy compound (A) is preferably 80 g / eq. or more. The epoxy equivalent of this epoxy compound (A) is preferably 300 g / eq. or less.

[0025] The epoxy compound (A) includes, for example, at least one selected from the group consisting of: polysiloxane-modified epoxy compound (a1), glycidylamine type epoxy compound (a2), bisphenol type epoxy compound (a3), p-aminophenol type epoxy compound, naphthalene type epoxy compound, bisphenol type epoxy compound, epoxy compound obtained by epoxidation of phenolic varnish compounds obtained by reacting phenols and aldehydes, represented by o-cresol phenolic varnish type epoxy compound, glycidyl ester type epoxy compound obtained by reacting polybasic acids such as phthalic acid and dimer acids with epichlorohydrin, and aminodiphenylmethane and cyanuric acid type epoxy compound. The epoxy compound (A) preferably includes at least one selected from the group consisting of polysiloxane-modified epoxy compound (a1) and glycidylamine type epoxy compound (a2).

[0026] The polysiloxane-modified epoxy compound (a1) readily maintains the properties of the cured product when exposed to high temperatures and readily improves the fluidity of the composition (X) under heating. We believe this is because the polysiloxane backbone of the polysiloxane-modified epoxy compound (a1) has high heat resistance, and the silicon-oxygen bonds in the polysiloxane backbone make the molecular chains of the polysiloxane-modified epoxy compound (a1) more flexible, thereby reducing the viscosity of the composition (X).

[0027] Furthermore, the glycidylamine type epoxy compound (a2) has nitrogen atoms within its molecule. The nitrogen atoms in the glycidylamine type epoxy compound (a2) can react with the epoxy groups in the epoxy compound (A). This can moderately increase the number of crosslinking points in the cured product. As a result, it becomes easier to suppress abnormalities and damage to the appearance of the cured product when exposed to high temperatures.

[0028] The number of epoxy groups in one molecule of the glycidylamine type epoxy compound (a2) is preferably 3 or more. This makes it easier to maintain the properties of the cured material when exposed to high temperatures. Furthermore, the number of epoxy groups is preferably 10 or less. This prevents excessive bridging points in the cured material, thus inhibiting damage. The number of epoxy groups is preferably 6 or less, and more preferably 4 or less.

[0029] The epoxy compound (A) preferably includes at least one selected from the group consisting of polysiloxane-modified epoxy compound (a1) and glycidylamine type compound (a2), and more preferably includes bisphenol type epoxy compound (a3). In other words, the epoxy compound (A) preferably includes at least one selected from the group consisting of polysiloxane-modified epoxy compound (a1), glycidylamine type epoxy compound (a2) and bisphenol type epoxy compound (a3).

[0030] The bisphenol type epoxy compound (a3) ​​can improve the balance between the heat resistance of the cured material and the flowability of the composition (X). The bisphenol type epoxy compound (a3) ​​includes, for example, at least one selected from the group consisting of bisphenol A type epoxy compounds, bisphenol F type epoxy compounds and bisphenol S type epoxy compounds.

[0031] When the epoxy compound (A) comprises at least one selected from the group consisting of polysiloxane-modified epoxy compound (a1), glycidylamine-type epoxy compound (a2), and bisphenol-type epoxy compound (a3), the total ratio of the polysiloxane-modified epoxy compound (a1), glycidylamine-type epoxy compound (a2), and bisphenol-type epoxy compound (a3) ​​relative to the epoxy compound (A) is preferably 30% by mass or more. In this case, it is easier to obtain a composition (X) that exhibits higher fluidity at high temperatures and can suppress abnormalities and damage to the appearance of the cured product when exposed to high temperatures. This ratio is preferably 50% by mass or more, and more preferably 70% by mass or more.

[0032] (Aromatic Amine Compound) Aromatic amine compound (B) can improve the heat resistance of the hardened material. Aromatic amine compound (B) is liquid as described above. The components contained in aromatic amine compound (B) may all be liquid, for example, aromatic amine compound (B) may contain liquid components and solid components, and the aromatic amine compound (B) may be liquid in its entirety by mixing the aforementioned components. In addition, liquid aromatic amine compound (B) can impart fluidity to composition (X).

[0033] The aromatic amine compound (B) preferably contains an aromatic amine compound having two or more amine groups in one molecule. In this case, the reactivity between the epoxy compound (A) and the aromatic amine compound (B) can be further improved. As a result, the curing properties of the composition (X) and the heat resistance of the cured product can be further improved.

[0034] The aromatic amine compound (B) includes, for example, at least one selected from the group consisting of: aliphatic aromatic amine compounds such as m-phenylenediamine; aromatic amine compounds having one aromatic ring such as m-phenylenediamine, 1,3-diaminotoluene, 1,4-diaminotoluene, 2,4-diaminotoluene, 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, 2,4-diaminoanisole, and dimethylthiotoluene diamine; 2,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 4,4'-methylenebis(2-ethylaniline), 3,3'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-4,4'-diphenylmethane, etc. Aromatic amine compounds having two aromatic rings, such as diaminodiphenylmethane, 3,3',5,5'-tetramethyl-4,4'-diaminodiphenylmethane, 3,3',5,5'-tetraethyl-4,4'-diaminodiphenylmethane, and polytetramethyleneoxydi-para-aminobenzoic acid ester; condensates of aromatic diamines and epichlorohydrin; and reaction products of aromatic diamines and styrene, etc.

[0035] The amine active hydrogen equivalent of the aromatic amine compound (B) is, for example, 20 g / eq. or more and 500 g / eq. or less. This improves the reactivity between the epoxide compound (A) and the aromatic amine compound (B). Furthermore, the amine active hydrogen equivalent refers to the mass (g) of the aromatic amine compound (B) containing 1 molar of amine active hydrogen. The amine active hydrogen equivalent of the aromatic amine compound (B) is preferably 30 g / eq. or more. The amine active hydrogen equivalent of the aromatic amine compound (B) is preferably 100 g / eq. or less.

[0036] The equivalent ratio of the amine active hydrogen of the aromatic amine compound (B) to the epoxy group of the epoxy compound (A) is preferably 0.5 or more and 1.5 or less. At this ratio, the epoxy compound (A) and the aromatic amine compound (B) can react particularly efficiently. Therefore, the heat resistance of the cured material can be moderately improved. This equivalent ratio is preferably 0.6 or more, more preferably 0.7 or more. This equivalent ratio is preferably 1.3 or less, more preferably 1.2 or less.

[0037] (Inorganic filler material) The inorganic filler material (C) may contain, for example, at least one selected from the group consisting of: fused silica powder, synthetic silica powder, and crystalline silica powder; metal oxide powders such as alumina powder and titanium dioxide powder; sulfate powders or sulfite powders such as barium sulfate powder, calcium sulfate powder, and calcium sulfite powder; borate powders such as lead borate powder, barium metaborate powder, aluminum borate powder, calcium borate powder, and sodium borate powder; and nitride powders such as aluminum nitride powder, boron nitride powder, and silicon nitride powder. The inorganic filler material (C) preferably contains silica powder. Silica powder is particularly beneficial for reducing the coefficient of linear expansion of the hardened material.

[0038] The inorganic filler material (C) may be in the form of fragments, needles, scales or spheres, etc., without particular limitation. In order to improve the dispersibility of the inorganic filler material (C) in the composition (X) and control the viscosity of the composition (X), the inorganic filler material (C) is preferably in the form of spheres.

[0039] The inorganic filler material (C) is preferably surface-treated with a surface treatment agent. This improves the dispersibility of the inorganic filler material (C) in the composition (X). This helps to suppress the decrease in the flowability of the composition (X) caused by the inorganic filler material (C). The surface treatment agent may include, for example, at least one selected from the group consisting of silane compounds, titanium compounds, aluminum chelates, and aluminum / zirconium compounds. The silane compounds may include, for example, at least one selected from the group consisting of silane compounds having an amino group, silane compounds having an acrylonitrile group, silane compounds having a methacrylonitrile group, silane compounds having an epoxy group, mercaptosilanes, alkylsilanes, ureosilanes, and vinylsilanes. Among these, the silane compounds preferably include at least one selected from the group consisting of silane compounds having an amino group, silane compounds having a methacrylic group, and silane compounds having an epoxy group. Furthermore, the silane compounds having an amino group preferably include silane compounds having an aniline group. Therefore, the inorganic filler material (C) preferably comprises silica powder surface-treated with a silane compound having at least one selected from the group consisting of aniline, methacrylic, and epoxy groups. This particularly improves the dispersibility of the inorganic filler material (C) in the composition (X).

[0040] The inorganic filler material (C) preferably comprises a first inorganic filler material (c1) with an average particle size of less than 0.1 μm and a second inorganic filler material (c2) with an average particle size of 0.4 μm or more and 2.0 μm or less. This suppresses the increase in viscosity of the composition (X) caused by the inorganic filler material (C), thereby maintaining the flowability of the composition (X) well. The average particle size of the first inorganic filler material (c1) is preferably 0.08 μm or less, more preferably 0.06 μm or less. The average particle size of the second inorganic filler material (c2) is preferably 0.6 μm or more, more preferably 0.8 μm or more. The average particle size of the second inorganic filler material (c2) is preferably 1.6 μm or less, more preferably 1.3 μm or less.

[0041] When the inorganic filler material (C) contains the first inorganic filler material (c1) and the second inorganic filler material (c2), the total ratio of the first inorganic filler material (c1) and the second inorganic filler material (c2) relative to the inorganic filler material (C) is preferably 20% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more.

[0042] Furthermore, the ratio of inorganic filler material (C) relative to the total amount of composition (X) should preferably be 45% by mass or more and 80% by mass or less. If the ratio of inorganic filler material (C) is 45% by mass or more, damage to the hardened material can be better suppressed. If the ratio of inorganic filler material (C) is 80% by mass or less, the flowability of composition (X) can be well maintained. This ratio is preferably 55% by mass or more, more preferably 60% by mass or more. This ratio is preferably 76% by mass or less, more preferably 72% by mass or less.

[0043] The content of the inorganic filler (C) is preferably 100 parts by mass or more and 500 parts by mass or less, relative to 100 parts by mass of the total of the epoxy compound (A), aromatic amine compound (B), and epoxidized fatty acid ester compound (D-1). This allows for better high fluidity at high temperatures and better suppression of abnormal appearance and damage to the hardened material when exposed to high temperatures. This ratio is preferably 150 parts by mass or more, more preferably 200 parts by mass or more. This ratio is preferably 400 parts by mass or less, more preferably 350 parts by mass or less.

[0044] (Low-stress agent) The low-stress agent (D) is a component that can improve the flexibility of the hardened material and inhibit damage to the hardened material. In the embodiment, the composition (X) contains the low-stress agent (D), and the low-stress agent (D) contains an epoxidized fatty acid ester compound (D-1). Furthermore, the epoxidized fatty acid ester compound (D-1) is a different compound from the epoxy compound (A), therefore, in this case, the epoxidized fatty acid ester compound (D-1) does not contain the epoxy compound (A).

[0045] <Epoxidized Fatty Acid Ester Compounds> Epoxidized fatty acid ester compounds (D-1) comprise compounds having the structure described below: compounds in which the unsaturated bonds of unsaturated fatty acids are epoxidized (hereinafter also referred to as epoxidized fatty acids) are linked by ester bonds with polyols such as glycerol. Such compounds can be manufactured by the method described below: in compounds formed by ester bonds between unsaturated fatty acids and polyols (hereinafter also referred to as fatty acid ester compounds), the unsaturated bonds of the unsaturated fatty acids are epoxidized. Epoxidized fatty acids may be achieved by epoxidizing only a portion of the unsaturated bonds present in one molecule of the unsaturated fatty acid; not all unsaturated bonds need to be epoxidized. Furthermore, the epoxy equivalent of epoxidized fatty acid ester compounds (D-1) is not particularly limited, but from the viewpoint of further suppressing abnormal appearance of the hardened product, it is preferable to be 150 g / eq. or more, preferably 180 g / eq. or more, and even more preferably 210 g / eq. or more. There is no particular upper limit to this epoxy equivalent, but it is preferable to be below 1000 g / eq., more preferably below 700 g / eq., and even more preferably below 500 g / eq.

[0046] The polyols that form fatty acid ester compounds are not limited to glycerol. For example, the polyols include at least one selected from the group consisting of glycerol, diglycerol, polyglycerol, sorbitol, maltitol and glycerol glucoside.

[0047] The carbon number of the unsaturated fatty acid should preferably be 4 or more and 40 or less. This improves the fluidity of the composition (X) at high temperatures, enhances the softness of the hardened material, and further inhibits damage to the hardened material. Preferably, the carbon number is 8 or more, and more preferably 12 or more. Preferably, the carbon number is 36 or less, and more preferably 32 or less. Furthermore, specific compounds of unsaturated fatty acids include at least one from the group consisting of the following: crotonic acid, myristic acid, palmitoleic acid, hexadecenoic acid, oleic acid, trans-oleic acid, isoleic acid, codoleic acid, eicosapentaenoic acid, erucic acid, tetradecenoic acid, linoleic acid, eicosadienoic acid, docosahexaenoic acid, linolenic acid, terpineic acid, tung oil acid, meadic acid, dihomo-γ-linolenic acid, eicosatrienoic acid, octadecanoic acid, arachidonic acid, eicosatraenoic acid, docosahexaenoic acid, arachidonic acid, eicosapentaenoic acid, docosapentaenoic acid, tartaric acid, tartaric acid, docosapentaenoic acid, docosahexaenoic acid, and docosahexaenoic acid. Unsaturated fatty acids preferably include at least one selected from the group consisting of oleic acid, linoleic acid, and linolenic acid.

[0048] Furthermore, fatty acid ester compounds may also be oils and fats. Therefore, fatty acid ester compounds include, for example, at least one selected from the group consisting of rapeseed oil, soybean oil, linseed oil, castor oil, coconut oil, palm oil, palm kernel oil, sunflower seed oil, rice bran oil, safflower oil, beef tallow, and lard. Therefore, epoxidized fatty acid ester compounds (D-1) include, for example, at least one epoxidized oil (hereinafter also referred to as epoxidized oil) selected from the group consisting of epoxidized rapeseed oil, epoxidized soybean oil, epoxidized linseed oil, epoxidized castor oil, epoxidized coconut oil, epoxidized palm oil, epoxidized palm kernel oil, epoxidized sunflower seed oil, epoxidized rice bran oil, epoxidized safflower oil, epoxidized beef tallow, and epoxidized lard. In addition, typical rapeseed oil contains: 63.5% oleic acid (an 18-carbon unsaturated fatty acid), 19.3% linoleic acid (an 18-carbon unsaturated fatty acid), 9.0% linolenic acid (an 18-carbon unsaturated fatty acid), 4.1% palmitic acid (a 16-carbon saturated fatty acid), and 1.7% stearic acid (an 18-carbon saturated fatty acid). Similarly, typical flaxseed oil contains: 18.3% oleic acid (an 18-carbon unsaturated fatty acid), 14.3% linoleic acid (an 18-carbon unsaturated fatty acid), 53.4% ​​linolenic acid (an 18-carbon unsaturated fatty acid), 5.1% palmitic acid (a 16-carbon saturated fatty acid), and 3.4% stearic acid (an 18-carbon saturated fatty acid).

[0049] Furthermore, the epoxy fatty acid ester compound (D-1) comprises an epoxy fatty acid alkyl ester compound formed by the bonding of an epoxy fatty acid and an alkyl alcohol. The epoxy fatty acid alkyl ester has a structure in which the epoxy fatty acid and the alkyl alcohol are linked by an ester bond.

[0050] Epoxidized fatty acid alkyl ester compounds can be obtained, for example, by the method described later: removing epoxidized fatty acids from epoxidized oil and subjecting the removed epoxidized fatty acids to an esterification reaction with an alkyl alcohol. Examples of methods for removing epoxidized fatty acids include saponifying the epoxidized oil. Furthermore, if epoxidized fatty acid alkyl ester compounds can be obtained, the manufacturing order is not particularly limited. For example, an unsaturated fatty acid can be removed from a fatty acid ester compound before epoxidation, and then the unsaturated fatty acid can be reacted with an alkyl alcohol and subsequently epoxidized to obtain an epoxidized fatty acid alkyl ester compound. Alternatively, an unsaturated fatty acid can be removed from a fatty acid ester compound before epoxidation, and then the unsaturated fatty acid can be epoxidized and subsequently reacted with an alkyl alcohol to obtain an epoxidized fatty acid alkyl ester compound. The alkyl alcohol is not particularly limited; for example, alkyl alcohols with 1 or more carbon atoms and 20 or fewer carbon atoms can be used. Alkyl alcohols include, for example, at least one selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, hexanol, isobutanol, heptanol, octanol, and 2-ethylhexanol.

[0051] The epoxidized fatty acid ester compound (D-1) particularly preferably includes at least one selected from the group consisting of epoxidized rapeseed fatty acid 2-ethylhexyl ester and epoxidized linseed oil. In this case, it is particularly easy to reduce the viscosity of the composition (X).

[0052] The ratio of the epoxidized fatty acid ester compound (D-1) relative to the composition (X) is preferably 0.2% by mass or more and 4% by mass or less. A ratio of 0.2% by mass or more can further inhibit hardening damage. A ratio of 4.0% by mass or less can maintain the improved flowability of the composition (X). This ratio is more preferably 0.4% by mass or more, and more preferably 0.6% by mass or more. This ratio is more preferably 3.0% by mass or less, and more preferably 2.0% by mass or less.

[0053] The low-stress agent (D) in composition (X) preferably contains more core-shell type rubber particles (D-2). This further suppresses damage to the hardened material when exposed to high temperatures. The core-shell type rubber particles (D-2) have a core and a shell. The core is a particulate rubber. The shell is a grafted layer that covers the core.

[0054] The core may contain at least one substance selected from the group consisting of polymers of (meth)acrylic acid, polymers of (meth)acrylates, polymers of olefin compounds, and polybutadiene and polysiloxane. The core of the core-shell rubber particles (D-2) preferably contains polysiloxane. In this case, damage to the hardened material can be further suppressed.

[0055] The outer shell, for example, comprises at least one substance selected from the group consisting of styrene-acrylonitrile copolymer, polymer of (meth)acrylic acid, polybutadiene, and polysiloxane. The outer shell of the core-outer shell rubber particles (D-2) preferably comprises polysiloxane. In this case, damage to the hardened material can be further suppressed.

[0056] The core-shell type rubber (D-2) can use commercially available products. Examples of polysiloxane rubber particles include KANEKA's KANE ACE (registered trademark) MX-965. Examples of butadiene rubber particles include KANEKA's KANE ACE (registered trademark) MX-136 and MX-139.

[0057] The average particle size of the core-shell type rubber particles (D-2) is less than 1.0 μm. In this case, if such small core-shell type rubber particles (D-2) with the above-mentioned average particle size are included in the composition (X), it is easier to suppress the damage of the hardened material. Furthermore, there is no particular limitation on the lower limit of the average particle size of the core-shell type rubber particles (D-2), for example, it is 0.1 μm or more. In this case, "average particle size" means the particle size that accounts for 50% of the integral value in the particle size distribution obtained by laser diffraction / scattering method.

[0058] The ratio of the core-shell type rubber particles (D-2) relative to the composition (X) is preferably 0.1% by mass or more and 8.0% by mass or less. A ratio of 0.1% by mass or more further inhibits damage to the hardened material. A ratio of 8.0% by mass or less facilitates the improvement of the flowability of the composition (X). A ratio of 0.5% by mass or more is preferred. A ratio of 4.0% by mass or less is also preferred.

[0059] (High Flowability Agent) The high flowability agent (E) is a component that improves the flowability of the composition (X). Examples of high flowability agents (E) include organic salts. In an embodiment, the composition (X) contains the high flowability agent (E), which contains at least one selected from the group consisting of a compound (E-1) having a quaternary phosphonium cation (hereinafter also referred to as compound (E-1)) and a compound (E-2) having a silicate anion (hereinafter also referred to as compound (E-2)).

[0060] <Compounds having a fourth-order phosphonium cation> Compound (E-1) can reduce the viscosity of the composition (X) when heated, thereby improving its fluidity. The fourth-order phosphonium cation has, for example, the structure shown in formula (1).

[0061] [Chemical Formula 1]

[0062] In formula (1), R1 to R4 represent substituted or unsubstituted hydrocarbon groups, which are the same or different and have 1 or more but less than 12 carbon atoms. From the viewpoint of hardening, storage stability and flowability, R1 to R4 should preferably each have 4 or more but less than 6 carbon atoms. Specific examples of hydrocarbon groups include: methyl, ethyl, propyl, n-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, cyclohexyl, phenyl, methoxymethyl, benzyl, etc., among which n-butyl or phenyl is preferred.

[0063] The anion contained in compound (E-1) is not particularly limited. The anion contained in compound (E-1) may include, for example, at least one selected from the group consisting of: monatomic anions such as Cl-, Br-, I-; inorganic anions with fluorine atoms such as BF4-, PF6-; inorganic anions without fluorine atoms such as NO3-, NO2-; organic anions with fluorine atoms such as CF3SO3-, (CF3SO2)2N-, (CF3SO2)2C-, (C2F5SO2)2N-; and organic anions without fluorine atoms such as (CH3CH2O)2PO-, (CN)2N-, CH3COO-.

[0064] <Compounds having silicate anionic structures> Compound (E-2) can reduce the viscosity of composition (X) when heated, thereby improving its fluidity. The silicate anion has, for example, a skeleton derived from dihydroxynaphthalene or a skeleton derived from catechol. The silicate anion has, for example, the structure shown in formula (2).

[0065] [Chemical Formula 2]

[0066] In formula (2), R5 and R6 are each independently an phenyl or an amylinyl group. R7 is a phenyl or a group shown in formula (3).

[0067] [Chemical Formula 3]

[0068] In formula (3), n is 3 or more and 8 or less. In formula (3), X is -SH, -NH2, -NH-Ph, -Ph-CH=CH2, -NH-C2H4-NH2, -N=C=O, epoxypropyl ether group or the group shown in formula (4).

[0069] [Chemical Formula 4]

[0070] In this case, "-Ph" in "-NH-Ph" means phenyl, and "-Ph-" in "-Ph-CH=CH2" means extended phenyl.

[0071] The cations contained in compound (E-2) are not particularly limited. The cations contained in compound (E-2) may include, for example, at least one selected from the group consisting of: aliphatic onium cations such as ammonium cation, strontium cation, and phosphonium cation; cyclic aliphatic cations such as pyrrolidine cation; and aromatic cations such as imidazolium cation and pyridine cation.

[0072] Furthermore, the high fluidity agent may comprise a compound having a quadrivalent phosphonium cation and a silicate anion. The compound having a quadrivalent phosphonium cation and a silicate anion is a compound that can be equivalent to either compound (E-1) or compound (E-2).

[0073] The total ratio of compounds (E-1) and (E-2) relative to composition (X) is preferably 0.01% by mass or more and 0.5% by mass or less. If this ratio is 0.01% by mass or more, the viscosity of composition (X) at high temperatures can be reduced. If this ratio is 0.5% by mass or less, the storage stability of composition (X) can be further improved, and high hardenability can be adequately maintained. The ratio of these compounds is preferably 0.02% by mass or more, more preferably 0.05% by mass or more. This ratio is preferably 0.3% by mass or less, more preferably 0.2% by mass or less.

[0074] (Silane Coupling Agent) The composition (X) may further include a silane coupling agent (F). By adhering to the surface of the inorganic filler (C), the silane coupling agent (F) can suppress the generation of ions from the inorganic filler (C). This further reduces the viscosity of the composition (X).

[0075] The silane coupling agent (F) may, for example, comprise at least one selected from the group consisting of: vinyltrimethoxysilane, vinyltriethoxysilane, and other vinyl silanes; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-epoxypropoxypropylmethyldimethoxysilane, 3-epoxypropoxypropyltrimethoxysilane, 3-epoxypropoxypropylmethyldiethoxysilane, 3-epoxypropoxypropyltriethoxysilane, and other epoxy silanes; p-styrenetrimethoxysilane and other styrene silanes; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane Isomethacrylsilane; 3-propenyloxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene) Aminosilanes such as propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and anilinepropyltrimethoxysilane; isocyanate silanes; alkylsilanes; ureosilanes such as 3-ureopropyltrialkoxysilane; mercaptosilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; and isocyanate silanes such as 3-isocyanatepropyltriethoxysilane.

[0076] The ratio of silane coupling agent (F) is 0.1% by mass or more and 2.0% by mass or less relative to composition (X).

[0077] (Additives) The composition (X) may contain ingredients other than those listed above (hereinafter also referred to as additives (G)) as required. Additives (G) may contain, for example, at least one selected from the group consisting of antioxidants, hardening agents, colorants, colorants, ion trapping agents, defoamers, leveling agents, and antioxidants. The proportion of additives (G) relative to composition (X) should preferably be 1.0% by mass or less.

[0078] (Solvent) The composition (X) may contain solvent (H). However, the composition (X) should preferably not contain solvent (H), or contain only trace amounts of solvent (H) that are unavoidably mixed in. The ratio of solvent (H) relative to the solid content of the composition (X) should preferably be 1.0% by mass or less. The solid content of the composition (X) refers to the components contained in the composition (X) excluding volatile components such as solvent (H).

[0079] (Viscosity) In this embodiment, the component (X) is liquid. The liquid state of component (X) means that component (X) is fluid at 25°C. If the viscosity of component (X) at 25°C, measured using a type B rotational viscometer (Toki Sangyo Co., Ltd., TVB-10) at a rotational speed of 20 rpm, is 200 Pa·s or less, then component (X) can be considered liquid. The viscosity of component (X) is preferably 100 Pa·s or less, more preferably 50 Pa·s or less, and even more preferably 30 Pa·s or less. Furthermore, the viscosity of component (X) at 110°C is preferably 1 Pa·s or less, more preferably 0.5 Pa·s or less, and even more preferably 0.3 Pa·s or less. The method for measuring this viscosity at 110°C will be described in the embodiments section below.

[0080] 3. Semiconductor Device (Semiconductor Sealing Material and Underfill Material) The component (X) can be applied to the semiconductor sealing material, and is particularly suitable for the underfill material. That is, the semiconductor sealing material of the embodiment contains the component (X), and the underfill material of the embodiment contains the component (X). Furthermore, the semiconductor sealing material is the material used to make the sealing portion 5, which protects the semiconductor element 3 by covering part or all of the semiconductor element 3. Also, the underfill material in the semiconductor sealing material is the material used to make the sealing portion 5, which is the gap between the substrate 2 and the semiconductor element 3 mounted on the surface of the substrate 2. If the sealing portion 5 is made by the semiconductor sealing material or the underfill material of the embodiment, the component (X) will have high fluidity at high temperature when making the sealing portion 5, thus suppressing poor filling and other molding defects. Furthermore, it can suppress cracks and other damage to the sealing portion 5 at high temperature, and can suppress abnormal appearance of the sealing portion 5 at high temperature.

[0081] (Semiconductor device) The semiconductor device 1 of the embodiment includes a sealing part 5 made of semiconductor sealing material or bottom filling material of the embodiment.

[0082] When the semiconductor device 1 has a sealing portion 5 made of bottom filling material, the semiconductor device 1 has a substrate 2, a semiconductor element 3 mounted on the substrate 2, and a sealing portion 5 between the substrate 2 and the semiconductor element 3, the sealing portion 5 including a hardened form of the bottom filling material.

[0083] The substrate 2 includes, for example, an insulating substrate such as a glass epoxy substrate, a polyimide substrate, a polyester substrate, or a ceramic substrate, and conductor wiring 21 superimposed on the insulating substrate. The conductor wiring 21 includes, for example, electrode pads. The substrate 2 is, for example, a motherboard, a package board, or an interposer.

[0084] The semiconductor element 3 may be a suitable surface-mount element. The semiconductor element 3 has bump electrodes 31 on the surface opposite to the substrate 2. The semiconductor element 3 may be a bare die, a packaged component, or a wafer-level package. The semiconductor element 3 may be, for example, a flip-chip such as a BGA (Ball Grid Array), LGA (Land Grid Array), or CSP (Chip Size Package). The semiconductor element 3 may also be a PoP (Package on Package) type die.

[0085] The semiconductor element 3 is mounted on the surface of the substrate 2. Specifically, the surface of the semiconductor element 3 having the bump electrode 31 faces the substrate 2. The bump electrode 31 of the semiconductor element 3 is joined to the electrode pad of the conductor wiring 21 in the substrate 2 via solder bumps 4, and the bump electrode 31 and the electrode pad are electrically connected via the solder bumps 4. Furthermore, if the semiconductor element 3 is mounted on the substrate 2 with a gap between it and the substrate 2, the connection state between the semiconductor element 3 and the substrate 2 is not limited to the aforementioned.

[0086] The sealing part 5 is located in the gap between the semiconductor element 3 and the substrate 2. Therefore, the bump electrode 31, the solder bump 4 and the electrode pad of the conductor wiring 21 are embedded in the sealing part 5.

[0087] (Method for manufacturing a semiconductor device) An example of a method for manufacturing a semiconductor device 1 will be explained.

[0088] First, prepare the above-mentioned substrate 2, semiconductor element 3 and bottom filling material.

[0089] Next, a semiconductor element 3 is mounted on the surface of the substrate 2. Specifically, the surface of the semiconductor element 3 having bump electrodes 31 is positioned opposite to the substrate 2, and a solder bump 4 is positioned between the bump electrodes 31 of the semiconductor element 3 and the electrode pads of the conductor wiring 21 in the substrate 2. The solder contained in the solder bump 4 is, for example, a lead-free solder with a melting point of 210°C or higher, such as Sn-3.5Ag (melting point 221°C), Sn-2.5Ag-0.5Cu-1Bi (melting point 214°C), Sn-0.7Cu (melting point 227°C), or Sn-3Ag-0.5Cu (melting point 217°C). In this state, the solder bump 4 is heated by a suitable heating method, such as reflow heating, until it melts and solidifies. The heating temperature can be set according to the solder bump 4 to a temperature that melts the solder bump 4, for example, a maximum heating temperature of 180°C or higher and 300°C or lower. In this way, the conductor wire 21 and the electrode pad are joined through the solder bump 4, and the conductor wire 21 and the electrode pad are electrically connected through the solder bump 4.

[0090] Next, an underfill material is injected into the gap between the semiconductor element 3 and the substrate 2 using a dispensing device or the like. The underfill material flows into the gap between the semiconductor element 3 and the substrate 2 due to capillary action. As the composition (X) flows, the composition (X) can be heated as needed to reduce its viscosity. The heating temperature of the composition (X) at this time is, for example, 80°C or higher and 130°C or lower. This allows the underfill material to fill the gap between the semiconductor element 3 and the substrate 2. In this embodiment, heating the underfill material as described above can improve its flowability. Therefore, the underfill material can fill the gap between the semiconductor element 3 and the substrate 2 well. The underfill material is then heated in this state to harden it. The heating conditions at this time can be appropriately set according to the composition of the composition (X), with the heating temperature being, for example, 80°C or higher and 180°C or lower, and the heating time being 60 minutes or higher and 300 minutes or lower. This allows the creation of a sealing portion 5 that exists in the gap between the semiconductor element 3 and the substrate 2 and includes a hardened material with a bottom filling material.

[0091] In this embodiment, the bottom filler material has high fluidity. Therefore, poor filling of the component (X) between the semiconductor element 3 and the substrate 2 and the sealing portion 5 can be suppressed.

[0092] Furthermore, the manufacturing method of semiconductor device 1 is not limited to the above.

[0093] 4. As can be seen from the above implementation forms, this case includes the following implementation forms.

[0094] The liquid resin composition of the first state of this case contains: a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), a low-stress agent (D), and a high-flowability agent (E). The low-stress agent (D) contains an epoxidized fatty acid ester compound (D-1). The high-flowability agent (E) contains at least one compound selected from the group consisting of a compound having a quaternary phosphonic cationic structure (E-1) and a compound having a silicate anionic structure (E-2).

[0095] According to this sample, a liquid resin composition that has high fluidity at high temperatures and can suppress abnormal appearance and damage to the hardened material when exposed to high temperatures can be provided.

[0096] The liquid resin composition of the second state sample in this case is the epoxy compound (A) of the first state sample, with a viscosity of less than 100 Pa·s at 25°C.

[0097] The liquid resin composition of the third state sample in this case is the epoxidized fatty acid ester compound (D-1) of the first or second state sample, which includes at least one selected from the group consisting of epoxidized rapeseed fatty acid 2-ethylhexyl ester and epoxidized linseed oil.

[0098] The liquid resin composition of the fourth state sample in this case is that, in any of the first to third state samples, the low-stress agent (D) further contains core-shell type rubber particles (D-2).

[0099] The liquid resin composition of the fifth state sample in this case is, in any of the first to fourth state samples, the epoxy compound (A) includes at least one selected from the group consisting of polysiloxane-modified epoxy compound (a1) and epoxypropylamine type epoxy compound (a2).

[0100] The liquid resin composition of the sixth state sample in this case is that, in any of the first to fifth state samples, the epoxy compound (A) further includes a bisphenol type epoxy compound (a3).

[0101] The liquid resin composition of the seventh state sample in this case is such that, in any of the first to sixth state samples, the content of inorganic filler (C) is more than 100 parts by mass and less than 500 parts by mass relative to a total of 100 parts by mass of epoxy compound (A), aromatic amine compound (B), and epoxidized fatty acid ester compound (D-1).

[0102] The liquid resin composition of the eighth state sample in this case is, in any of the first to seventh state samples, the inorganic filler material (C) includes a first inorganic filler material (c1) with an average particle size of less than 0.1 μm and a second inorganic filler material (c2) with an average particle size of more than 0.4 μm and less than 2.0 μm.

[0103] The liquid resin composition of the ninth state sample in this case is any of the first to eighth state samples, and the liquid resin composition further contains a silane coupling agent (F).

[0104] The semiconductor sealing material of the 10th state of this case contains a liquid resin composition of any one of the 1st to 9th states.

[0105] The bottom filling material of the 11th state sample in this case contains a liquid resin composition of any one of the 1st to 9th states.

[0106] The semiconductor device (1) of the 12th state of this case includes a substrate (2), a semiconductor element (3) mounted on the substrate (2), and a sealing portion (5) between the substrate (2) and the semiconductor element (3). The sealing portion (5) includes a hardened version of the bottom filling material of the 11th state.

[0107] [Example] Hereinafter, specific embodiments of the relevant implementation will be described. However, this case is not limited to these embodiments.

[0108] 1. The composition is prepared by mixing the ingredients shown in the table. Details of the ingredients in the table are as follows: (Epoxy Compounds) - Epoxy Compound #1: Manufactured by Momentive Performance Materials Japan LLC. Product name: TSL9906. Liquid polysiloxane-modified epoxy resin (siloxane oligomer with epoxypropoxypropyl groups at both ends). Epoxy equivalent: 181 g / eq. - Epoxy Compound #2: Manufactured by ADEKA Corporation. Product name: EP-3950S. Liquid epoxypropylamine type epoxy resin. Epoxy equivalent: 94 g / eq. - Epoxy Compound #3: Manufactured by NIPPON STEEL Chemical & Material Corporation. Product name: YDF8170. Liquid bisphenol F type epoxy resin. Epoxy equivalent: 160 g / eq.

[0109] (Aromatic Amine Compounds) - Aromatic Amine Compound #1: Manufactured by Nippon Kayaku Co., Ltd. Product Name: KAYAHARD AA. Liquid aromatic amine resin. Amine active hydrogen equivalent: 63.5 g / eq. - Aromatic Amine Compound #2: Manufactured by Mitsubishi Chemical Co., Ltd. Product Name: JER Cure WA. Liquid aromatic amine compound. Amine equivalent: 45 g / eq. - Aromatic Amine Compound #3: Manufactured by ADEKA Co., Ltd. Product Name: EH-105L. Liquid aromatic amine compound. Amine equivalent: 61 g / eq.

[0110] (Inorganic Filler Material) -Inorganic Filler Material #1: Silica with an average particle size of 0.7 μm, surface-treated with N-phenyl-3-aminopropyltrimethoxysilane. -Inorganic Filler Material #2: Silica with an average particle size of 0.1 μm, surface-treated with phenyltrimethoxysilane. -Inorganic Filler Material #3: Manufactured by Admatechs Corporation. Product name YA-050A-JER. A mixture of bisphenol F type epoxy resin with an epoxy equivalent of 160 g / eq. and silica with an average particle size of 50 nm. Silica concentration 50% by mass.

[0111] (Low-stress agent) - Low-stress agent #1: Manufactured by KANEKA Corporation, product name KANE ACE (registered trademark) MX-965, a mixture of bisphenol F type epoxy resin with an epoxy equivalent of 160g / eq. and core-shell type rubber particles with polysiloxane rubber as the core, the concentration of rubber particles is 25% by mass. - Low-stress agent #2: Manufactured by ADEKA Corporation, product name ADK CIZER D-32, epoxidized rapeseed fatty acid 2-ethylhexyl ester. Ethylene oxide content is 4.3% by mass. - Low-stress agent #3: Manufactured by ADEKA Corporation, product name ADK CIZER O-180A, epoxidized linseed oil. Ethylene oxide content is 8.5% by mass. - Low-stress agent #4: Manufactured by Riken Agricultural Chemicals Co., Ltd. Product name: Domestic soybean oil. Soybean oil (fatty acid ester compound). - Low-stress agent #5: Manufactured by NIPPN Corporation, product name: NIPPN linseed oil. Flaxseed oil (fatty acid ester compound). - Low-stress agent #6: Manufactured by Dow Toray Corporation, product name FZ-3736, epoxidized polysiloxane compound.

[0112] (High Flowability Agent) - High Flowability Agent #1: The compound shown in the following formula.

[0113] [Chemical Formula 5]

[0114] -High flowability agent #2: The compound shown in the following formula.

[0115] [Chemical Formula 6]

[0116] -High flowability agent #3: The compound shown in the following formula.

[0117] [Chemical Formula 7]

[0118] (Silane Coupling Agent) -Silane Coupling Agent #1: Manufactured by Momentive Performance Materials Japan LLC, product name SILQUEST A-187 SILANE, 3-epoxypropoxypropyltrimethoxysilane.

[0119] 2. Evaluation: The following evaluation was conducted on the components. The results are presented in the table.

[0120] (1) The viscosity at 25°C was measured using a Type B rotational viscometer (TVB-10, manufactured by Toki Sangyo Co., Ltd.) at a rotational speed of 20 rpm.

[0121] (2) Viscosity at 110℃: The temperature dependence of the composition was determined using a rheometer (Anton Paar, MCR-102) at a rotation speed of 1 rpm, a spacing of 300 μm, and a heating rate of 5℃ / min. The viscosity of the composition at 110℃ was read from the results. The results showed that the fluidity was good when it was below 0.4 Pa·s, and particularly good when it was below 0.2 Pa·s.

[0122] (3) High-temperature resistance retention characteristics 1) Preparation method of evaluation sample 10 mg of composition was coated in an X shape on a silicon substrate with dimensions of 25 mm × 25 mm × 775 μm. A 7 mm square (7 mm × 7 mm × 775 μm) silicon substrate was placed on the coated composition. In this state, the two silicon substrates and the composition were heated at 80°C for 60 seconds and then cooled to 25°C. In this way, the composition expanded between the two silicon substrates, and the rounded corners of the composition protruded from the outer periphery of the 7 mm square silicon substrate. Next, the silicon substrate and the composition were heated at 100°C for 2 hours and then heated at 165°C for 2 hours to prepare the evaluation sample.

[0123] 2) Crack evaluation will follow the method for preparing the sample for evaluation in "1)". The sample will be heated at 175°C for 250 hours. The corner portion of the side of the 7mm square silicon substrate and other areas will be checked for cracks using an optical microscope (200x magnification). In addition, corner cracks refer to cracks that occur at the rounded corners of the hardened material of the component in the area near the 7mm square silicon substrate.

[0124] 3) Whether separation exists will be determined by following the method for preparing the sample for evaluation in "1)". The sample will be heated at 175°C for 250 hours and then observed with an optical microscope (magnification 200x). In this observation, separation will be defined as the presence of a fraction of 0.1 mm or more along the long axis.

[0125] 4) Whether the separated part has changed color: Compare the color of the separated material observed in the evaluation of "3) whether there is separation" with the color of the hardened material of the surrounding part. If a change in color is confirmed, the situation is considered as having changed color. For example, a change in color to black.

[0126] [Table 1]

[0127] [Table 2] [Simplified Explanation of the Diagram]

[0011] [Figure 1] is a cross-sectional view of the semiconductor device in the embodiment of this case.

Claims

1. A liquid resin composition comprising: a liquid epoxy compound (A), a liquid aromatic amine compound (B), an inorganic filler (C), a low-stress agent (D), and a high-flowability agent (E), wherein the aforementioned inorganic filler (C) comprises a first inorganic filler (c1) with an average particle size of less than 0.1 μm and a second inorganic filler (c2) with an average particle size of 0.4 μm or more and 2.0 μm or less, the aforementioned low-stress agent (D) comprises an epoxidized fatty acid ester compound (D-1), and the aforementioned high-flowability agent (E) comprises at least one compound selected from the group consisting of a compound having a quaternary phosphonic cationic structure (E-1) and a compound having a silicate anionic structure (E-2).

2. The liquid resin composition of claim 1, wherein the aforementioned epoxy compound (A) has a viscosity of 100 Pa·s or less at 25°C.

3. The liquid resin composition of claim 1, wherein the aforementioned epoxidized fatty acid ester compound (D-1) comprises at least one selected from the group consisting of epoxidized rapeseed fatty acid 2-ethylhexyl ester and epoxidized linseed oil.

4. The liquid resin composition of claim 1, wherein the aforementioned low-stress agent (D) further contains core-shell type rubber particles (D-2).

5. The liquid resin composition of claim 1, wherein the aforementioned epoxy compound (A) comprises at least one selected from the group consisting of polysiloxane-modified epoxy compound (a1) and glycidylamine type epoxy compound (a2).

6. The liquid resin composition of claim 5, wherein the aforementioned epoxy compound (A) further comprises a bisphenol type epoxy compound (a3).

7. The liquid resin composition of claim 1, wherein the content of the inorganic filler (C) is 100 parts by mass or more and 500 parts by mass or less relative to a total of 100 parts by mass of the aforementioned epoxy compound (A), the aforementioned aromatic amine compound (B), and the aforementioned epoxidized fatty acid ester compound (D-1).

8. The liquid resin composition of claim 1 further contains a silane coupling agent (F).

9. A semiconductor sealing material comprising a liquid resin composition as claimed in any one of claims 1 to 8.

10. A bottom filler material comprising a liquid resin composition as claimed in any one of claims 1 to 8.

11. A semiconductor device comprising a substrate, a semiconductor element mounted on the substrate, and a sealing portion therebetween the substrate and the semiconductor element, the sealing portion comprising a hardened form of the underfill material as claimed in claim 10.

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