Liquid resin composition and semiconductor device

Abstract

The present disclosure provides a liquid resin composition with which it is possible to achieve high photo-curability and a reduction in the linear expansion coefficient of a cured product. The liquid resin composition contains a cationically polymerizable component (A), a photocationic polymerization initiator (B), and an inorganic filler (C). The cationically polymerizable component (A) includes a polyfunctional cationically polymerizable compound (A1) and a monofunctional cationically polymerizable compound (A2). The polyfunctional cationically polymerizable compound (A1) comprises at least one selected from the group consisting of a polyfunctional oxetane compound (A11) and a polyfunctional alicyclic epoxy compound (A12).

Description

Liquid resin composition and semiconductor device

[0001] The present disclosure generally relates to a liquid resin composition and a semiconductor device, and more specifically to a liquid resin composition containing a polymerizable compound, and a semiconductor device including a side fill material containing a cured product of the liquid resin composition.

[0002] Patent Document 1 discloses a side fill resin composition used to prepare a side fill material interposed between a substrate and a peripheral portion of a surface of a component mounted on the substrate, the side fill resin composition comprising a cationically polymerizable component (A) and a photocationic polymerization initiator (B), the cationically polymerizable component (A) containing at least one of an oxetane compound (A1) and an alicyclic epoxy compound (A2), the total amount of the oxetane compound (A1) and the alicyclic epoxy compound (A2) being 70% by mass or more relative to the total amount of the cationically polymerizable component (A). It is also disclosed that this side fill resin composition is easily imparted with high UV curability.

[0003] International Publication No. 2022 / 215577

[0004] Patent Document 1 describes improving the UV curability of a resin composition, but if the linear expansion coefficient of the cured product can be reduced in addition to this, the heat resistance reliability of a semiconductor device or device containing a cured product of the resin composition can be improved.

[0005] The present disclosure aims to provide a liquid resin composition that can achieve high photocurability and a reduced linear expansion coefficient of the cured product, and a semiconductor device that includes a side fill material containing the cured product of this liquid resin composition.

[0006] A liquid resin composition according to one embodiment of the present disclosure contains a cationically polymerizable component (A), a photocationic polymerization initiator (B), and an inorganic filler (C). The cationically polymerizable component (A) contains a polyfunctional cationically polymerizable compound (A1) and a monofunctional cationically polymerizable compound (A2). The polyfunctional cationically polymerizable compound (A1) contains at least one compound selected from the group consisting of a polyfunctional oxetane compound (A11) and a polyfunctional alicyclic epoxy compound (A12).

[0007] A semiconductor device according to one aspect of the present disclosure includes a substrate, a mounting component to be surface-mounted on the substrate, and a side fill material interposed between the substrate and a peripheral edge of a surface of the mounting component facing the substrate, the side fill material including a cured product of the liquid resin composition.

[0008] Fig. 1 is a schematic cross-sectional view showing a semiconductor device according to an embodiment of the present disclosure, Fig. 2 is a schematic enlarged view showing an end portion of the semiconductor device shown in Fig. 1 .

[0009] Embodiments of the present disclosure will be described. Note that the following embodiments are merely a portion of various embodiments of the present disclosure. Furthermore, the following embodiments can be modified in various ways depending on the design, etc., as long as the object of the present disclosure can be achieved. The figures referred to below are schematic diagrams, and the dimensional ratios of the components in the figures do not necessarily reflect the actual dimensional ratios. Although the mechanism of action in the embodiments may be described below, the description of the mechanism of action includes an explanation based on speculation, and the present disclosure is not bound by the description of the mechanism of action.

[0010] 1. Overview A liquid resin composition according to an embodiment (hereinafter also referred to as composition (X)) contains a cationically polymerizable component (A), a photocationic polymerization initiator (B), and an inorganic filler (C). The cationically polymerizable component (A) contains a polyfunctional cationically polymerizable compound (A1) and a monofunctional cationically polymerizable compound (A2). The polyfunctional cationically polymerizable compound (A1) contains at least one compound selected from the group consisting of a polyfunctional oxetane compound (A11) and a polyfunctional alicyclic epoxy compound (A12).

[0011] Composition (X) can have high photocurability. Therefore, composition (X) can be used for various applications. For example, composition (X) can be used to produce a semiconductor device. Specifically, composition (X) is suitable for use in producing a side fill material interposed between a substrate and the peripheral portion of a surface of a component mounted on the substrate, the surface of the component facing the substrate, in a semiconductor device. In other words, composition (X) can be used to produce a side fill material. Composition (X) can also be used to produce equipment. Specifically, composition (X) is suitable for use as an adhesive for bonding two components that constitute the equipment. In other words, composition (X) can be used as an adhesive.

[0012] Furthermore, the linear expansion coefficient of the cured product can be reduced. Therefore, semiconductor devices or devices manufactured using such composition (X) can have high heat resistance reliability. Furthermore, the cured product of composition (X) is less likely to lose adhesion even at high temperatures. Therefore, the adhesion between a side fill material or adhesive containing the cured product and a member in contact therewith is less likely to decrease.

[0013] 2. Liquid Resin Composition 2.1 Components As described above, the composition (X) contains the cationically polymerizable component (A), the photocationic polymerization initiator (B), and the inorganic filler (C).

[0014] (Cationically polymerizable component) The cationically polymerizable component (A) contains a compound having a cationically polymerizable reactive functional group. Examples of the cationically polymerizable reactive functional group include an oxetanyl group, an epoxy group, and a vinyl group. The cationically polymerizable reactive functional group is preferably an epoxy group or an oxetanyl group. In other words, the cationically polymerizable component (A) preferably contains at least one selected from the group consisting of a compound having an oxetanyl group and a compound having an epoxy group.

[0015] When the composition (X) contains a compound having an oxetanyl group, when the composition (X) is cured by irradiating light, unreacted oxetanyl groups are less likely to remain in the cured product. Therefore, the proportion of unreacted reactive functional groups in the cured product can be reduced. In other words, the reactivity of the cationically polymerizable component (A) in the composition (X) can be improved.

[0016] Furthermore, the compound having an epoxy group accelerates the reaction of the cationically polymerizable component (A) and tends to further enhance the photocurability of the composition (X).

[0017] It is preferable that the cationically polymerizable component (A) simultaneously contains both a compound having an oxetanyl group and a compound having an epoxy group. In this case, the reaction of the cationically polymerizable component (A) when the composition (X) is cured can be promoted, thereby improving the reactivity of the cationically polymerizable component (A).

[0018] <Polyfunctional cationically polymerizable compound> The cationically polymerizable component (A) contains a polyfunctional cationically polymerizable compound (A1). The polyfunctional cationically polymerizable compound (A1) is a compound having two or more cationically polymerizable reactive functional groups per molecule. By containing the polyfunctional cationically polymerizable compound (A1), the proportion of reactive functional groups in the cationically polymerizable component (A) is increased. This facilitates the reaction of the cationically polymerizable component (A). This allows the photocurability of the composition (X) to be improved.

[0019] As already mentioned, the polyfunctional cationically polymerizable compound (A1) contains at least one selected from the group consisting of a polyfunctional oxetane compound (A11) and a polyfunctional alicyclic epoxy compound (A12). This can enhance the photocurability of the composition (X) while suppressing an increase in the linear expansion coefficient of the cured product. As a result, high photocurability and a reduced linear expansion coefficient of the cured product can be achieved. The polyfunctional oxetane compound (A11) is included in the above-mentioned compounds having an oxetanyl group. The polyfunctional alicyclic epoxy compound (A12) is included in the above-mentioned compounds having an epoxy group.

[0020] The polyfunctional oxetane compound (A11) is a compound having two or more oxetanyl groups in one molecule. Examples of the polyfunctional oxetane compound (A11) include bis(3-ethyl-3-oxetanylmethyl)ether, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3 The compound contains at least one selected from the group consisting of bis[1-ethyl(3-oxetanyl)]methyl ether, 1,3-bis(3-ethyl-3-oxetanylmethoxy)propane, bis[1-ethyl(3-oxetanyl)]methyl ether, 1,3-bis(3-ethyl-3-oxetanylmethoxy)propane, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,4-bis(3-ethyl-3-oxetanylmethoxymethyl)benzene, 1,3-bis(3-ethyl-3-oxetanylmethoxymethyl)benzene, and 1,2-bis(3-ethyl-3-oxetanylmethoxymethyl)benzene.

[0021] The polyfunctional alicyclic epoxy compound (A12) is a compound having two or more alicyclic epoxy groups per molecule. The alicyclic epoxy group refers to an epoxy group in which two carbon atoms in the cyclic ether constituting the epoxy group are present on a saturated or unsaturated carbon ring that does not have aromaticity. Specifically, the polyfunctional alicyclic epoxy compound (A12) includes at least one selected from the group consisting of 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, ε-caprolactone-modified 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4,3',4'-diepoxybicyclohexyl, and bis(3,4-epoxycyclohexyl)adipate.

[0022] The polyfunctional cationically polymerizable compound (A1) may contain only the polyfunctional oxetane compound (A11) and the polyfunctional alicyclic epoxy compound (A12), or may further contain a compound other than the polyfunctional oxetane compound (A11) and the polyfunctional alicyclic epoxy compound (A12). The compound other than the polyfunctional oxetane compound (A11) and the polyfunctional alicyclic epoxy compound (A12) may include, for example, at least one selected from the group consisting of a polyfunctional epoxy compound (A13) other than the polyfunctional alicyclic epoxy compound (A12) and a polyfunctional vinyl ether compound (A14).

[0023] The polyfunctional epoxy compound (A13) includes at least one selected from the group consisting of biphenyl-type epoxy compounds, bisphenol A-type epoxy compounds, bisphenol F-type epoxy compounds, bisphenol S-type epoxy compounds, naphthalene ring-containing epoxy compounds, anthracene ring-containing epoxy compounds, phenol novolac-type epoxy compounds, cresol novolac-type epoxy compounds, triphenylmethane-type epoxy compounds, bromine-containing epoxy compounds, and triglycidyl isocyanurate. The polyfunctional epoxy compound (A13) is included in the compounds having an epoxy group described above.

[0024] The polyfunctional vinyl ether compound (A14) includes, for example, at least one selected from the group consisting of ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, polypropylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F alkylene oxide divinyl ether.

[0025] <Monofunctional cationically polymerizable compound> The cationically polymerizable component (A) contains a monofunctional cationically polymerizable compound (A2). The monofunctional cationically polymerizable compound (A2) is a compound having only one cationically polymerizable reactive functional group per molecule. The monofunctional cationically polymerizable compound (A2) can reduce the linear expansion coefficient of the cured product. This is presumably because the monofunctional cationically polymerizable compound (A2) reduces the likelihood of unreacted reactive functional groups remaining in the cured product, and therefore, even when the cured product is heated, dimensional changes due to the reaction of the unreacted functional groups are less likely to occur. As a result, a reduction in the linear expansion coefficient of the cured product can be achieved.

[0026] For example, the monofunctional cationically polymerizable compound (A2) includes at least one selected from the group consisting of a monofunctional oxetane compound (A21), a monofunctional epoxy compound (A22), and a monofunctional vinyl ether compound. The monofunctional cationically polymerizable compound (A2) preferably includes at least one selected from the group consisting of a monofunctional oxetane compound (A21) and a monofunctional epoxy compound (A22). In this case, the linear expansion coefficient of the cured product can be further reduced. The monofunctional oxetane compound (A21) is included in the above-mentioned compounds having an oxetanyl group. The monofunctional epoxy compound (A22) is included in the above-mentioned compounds having an epoxy group.

[0027] The monofunctional oxetane compound (A21) is a compound having one oxetanyl group per molecule, and includes, for example, at least one selected from the group consisting of 3-methyloxetane, 3-ethyloxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-[(benzyloxy)methyl]-3-ethyloxetane, 3-ethyl-3-(cyclohexyloxymethyl)oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-methyl-3-hydroxymethyloxetane, 3-ethyl-3-hydroxymethyloxetane, and 3-ethyl-3-(chloromethyl)oxetane.

[0028] The monofunctional oxetane compound (A21) more preferably contains at least one selected from the group consisting of 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(phenoxymethyl)oxetane, and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, which can further reduce the linear expansion coefficient of the cured product.

[0029] The monofunctional epoxy compound (A22) is a compound having one epoxy group per molecule. The monofunctional epoxy compound (A22) includes a monofunctional alicyclic epoxy compound (A221) and a monofunctional epoxy compound (A222) different from the monofunctional alicyclic epoxy compound (A221). The monofunctional alicyclic epoxy compound (A221) is a compound having one alicyclic epoxy group per molecule. The monofunctional alicyclic epoxy compound (A221) includes, for example, at least one selected from the group consisting of 3,4-epoxycyclohexylmethyl methacrylate, epoxyethyldivinylcyclohexane, limonene oxide, and cyclohexene oxide. The monofunctional epoxy compound (A222) includes, for example, at least one selected from the group consisting of phenyl glycidyl ether, dibromophenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, vinyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monoxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, and styrene oxide.

[0030] The monofunctional epoxy compound (A22) more preferably contains at least one selected from the group consisting of 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate, and styrene oxide, which can further reduce the linear expansion coefficient of the cured product.

[0031] <Proportions> In the composition (X), it is preferable that the proportions of the compound having an epoxy group and the compound having an oxetanyl group contained in the cationically polymerizable component (A), as well as the proportions of the components contained therein, are adjusted within specific ranges.

[0032] The total amount of the oxetanyl group-containing compounds contained in the cationically polymerizable component (A) is preferably 1% by mass or more and 70% by mass or less relative to the cationically polymerizable component (A). In this case, the linear expansion coefficient of the cured product can be easily reduced. This ratio is more preferably 3% by mass or more, and even more preferably 5% by mass or more. This ratio is more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less.

[0033] The total amount of the epoxy group-containing compounds contained in the cationically polymerizable component (A) is preferably 20% by mass or more and 85% by mass or less relative to the cationically polymerizable component (A). In this case, the photocurability of the composition (X) can be easily improved. This ratio is more preferably 25% by mass or more, and even more preferably 30% by mass or more. This ratio is more preferably 80% by mass or less, and even more preferably 78% by mass or less.

[0034] The total proportion of the polyfunctional oxetane compound (A11) and the polyfunctional alicyclic epoxy compound (A12) is preferably 50% by mass or more and 95% by mass or less relative to the cationically polymerizable component (A). In this case, the photocurability of the composition (X) can be further improved while maintaining a reduced linear expansion coefficient of the cured product. This proportion is more preferably 65% ​​by mass or more, and even more preferably 67% by mass or more. This proportion is more preferably 93% by mass or less.

[0035] The proportion of the monofunctional cationically polymerizable compound (A2) relative to the cationically polymerizable component (A) is preferably 2% by mass or more and 40% by mass or less. If this proportion is 5% by mass or more, the linear expansion coefficient of the cured product can be further reduced. If this proportion is 30% by mass or less, the enhanced photocurability of the composition (X) can be maintained.

[0036] The total proportion of the polyfunctional oxetane compound (A11) and the monofunctional oxetane compound (A21) is preferably 5% by mass or more and 70% by mass or less relative to the cationically polymerizable component (A). This makes it easier to achieve improved photocurability of the composition (X) and a reduced linear expansion coefficient of the cured product. This proportion is more preferably 8% by mass or more, and even more preferably 10% by mass or more. This proportion is more preferably 65% ​​by mass or less, and even more preferably 60% by mass or less.

[0037] When the monofunctional oxetane compound (A21) contains at least one selected from the group consisting of 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(phenoxymethyl)oxetane, and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, the total proportion of 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(phenoxymethyl)oxetane, and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane relative to the cationically polymerizable component (A) is preferably 5% by mass or more and 25% by mass or less. In this case, the linear expansion coefficient of the cured product can be particularly reduced. This proportion is more preferably 10% by mass or more, and even more preferably 12% by mass or more. This proportion is more preferably 20% by mass or less, and even more preferably 18% by mass or less.

[0038] When the monofunctional epoxy compound (A22) contains at least one selected from the group consisting of 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate, and styrene oxide, the total proportion of 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate, and styrene oxide is preferably 5% by mass or more and 25% by mass or less relative to the cationically polymerizable component (A). In this case, it is possible to more easily achieve improved photocurability of the composition (X) and a reduced linear expansion coefficient of the cured product. This proportion is more preferably 10% by mass or more, and even more preferably 12% by mass or more. This proportion is more preferably 20% by mass or less, and even more preferably 18% by mass or less.

[0039] (Photocationic Polymerization Initiator) The photocationic polymerization initiator (B) can promote the reaction of the cationically polymerizable component (A). The photocationic polymerization initiator (B) is preferably a photoacid generator. In this case, the photocationic polymerization initiator (B) can be decomposed by irradiating the composition (X) with light. At this time, an acid is generated, and the reaction of the cationically polymerizable component (A) can proceed efficiently by the acid.

[0040] The cationic photopolymerization initiator (B) preferably generates an acid upon irradiation with light having a wavelength of, for example, 200 nm or more and 400 nm or less. In this case, curing of the composition (X) is facilitated upon irradiation with ultraviolet light.

[0041] The photocationic polymerization initiator (B) contains, for example, an onium cation as a cationic species and an anionic species. The onium cation includes, for example, at least one selected from the group consisting of a sulfonium cation, an ammonium cation, an imidazolium cation, a phosphonium cation, and an iodonium cation. The anionic species includes, for example, PF6. - , B(C6F5)4 - , SbF6 - , CF3SO3 - , CF3(CF2)3SO3 - , p-CH3(CH2) 10 C6H4SO3 - , dinonylnaphthalenesulfonate anion, and p-toluenesulfonate anion.

[0042] As a specific example of the compound, the photocationic polymerization initiator (B) is, for example, triarylsulfonium (Rf) ｎ PF ６－ｎ Salt, Triarylsulfonium PF ６ Salt, triarylsulfonium SbF ６ Salt, Triarylsulfonium B(C ６ F ５ ) ４salt, bis[4-n-alkyl(C10-C13)phenyl]iodonium hexafluorophosphate, bis[4-n-alkyl(C10-C13)phenyl]iodonium hexafluoroantimonate, bis[4-n-alkyl(C10-C13)phenyl]iodonium tetrakis(pentafluorophenyl)borate, and bis(4-tert-butylphenyl)iodonium hexafluorophosphate.

[0043] The proportion of the cationic photopolymerization initiator (B) is preferably 0.1% by mass or more and 3% by mass or less relative to the composition (X), which can further improve the photocurability of the composition (X).

[0044] (Inorganic Filler) The inorganic filler (C) can contribute to reducing the linear expansion coefficient of the cured product. For example, the proportion of the inorganic filler (C) is 50% by mass or more and 90% by mass or less relative to the composition (X).

[0045] As described above, in the composition (X), the cationically polymerizable component (A) contains a polyfunctional cationically polymerizable compound (A1) and a monofunctional cationically polymerizable compound (A2), and the polyfunctional cationically polymerizable compound (A1) contains at least one selected from the group consisting of a polyfunctional oxetane compound (A11) and a polyfunctional alicyclic epoxy compound (A12). This allows for a reduction in the linear expansion coefficient of the cured product. Therefore, the proportion of the inorganic filler (C) contained in the composition (X) can be appropriately reduced. This allows for a reduction in the viscosity of the composition (X). As a result, the advantage of improving the coatability of the composition (X) can be obtained.

[0046] The inorganic filler (C) includes at least one selected from the group consisting of, for example, silica, alumina, clay, mica, talc, aluminum hydroxide, magnesium hydroxide, calcium carbonate, and glass. The silica includes at least one selected from the group consisting of, for example, fused silica, crystalline silica, fumed silica, etc.

[0047] When the inorganic filler (C) contains silica, the silica may be surface-treated. Surface-treated silica can improve compatibility between the cationically polymerizable component (A) and the silica. This can improve the dispersibility of the silica in the composition (X). For example, a silane coupling agent can be used for the surface treatment of the silica. As the silane coupling agent, for example, a compound having at least one functional group selected from the group consisting of an epoxy group, an amino group, a (meth)acryloyl group, and a phenyl group can be used.

[0048] The average particle size of the inorganic filler (C) is preferably, for example, 2.5 μm or more and 200 μm or less. When the average particle size of the inorganic filler (C) is within this range, the fluidity of the composition (X) can be improved. The average particle size is the median diameter D50. The median diameter D50 is calculated from the particle size distribution obtained by measurement using a laser diffraction / scattering method. Therefore, the particle size distribution can be measured using a laser diffraction particle size distribution analyzer.

[0049] (Other Components) The composition (X) may contain components other than those described above, as long as they do not excessively impair the effects of the present disclosure. The composition (X) may further contain components other than the cationically polymerizable component (A), the photocationic polymerization initiator (B), and the inorganic filler (C), as long as the effects of the present disclosure are not impaired. The components other than the cationically polymerizable component (A), the photocationic polymerization initiator (B), and the inorganic filler (C) may contain at least one selected from the group consisting of an additive (D) and a solvent (E).

[0050] The composition (X) may contain an additive (D) within a range that does not excessively impair the effects of the present disclosure. The additive (D) includes, for example, at least one selected from the group consisting of a radical polymerizable compound, a curing agent, a stabilizer, a photosensitizer, a flux, a viscosity modifier, a thixotropy-imparting agent, a surface conditioner, a surfactant, a silane coupling agent, an antifoaming agent, a leveling agent, a stress-reducing agent, and a pigment.

[0051] The radical polymerizable compound can adjust the reactivity of the composition (X). The radical polymerizable compound includes, for example, at least one selected from the group consisting of a (meth)acrylic compound and an allyl compound. The proportion of the radical polymerizable compound is preferably 5 mass% or less relative to the composition (X). In this case, high photocurability and a reduced linear expansion coefficient of the cured product can be maintained.

[0052] The stabilizer can prevent the photocurability of composition (X) from being excessively increased. Examples of the stabilizer include at least one selected from the group consisting of 2,6-tert-butyl-p-cresol, butylated hydroxyanisole, 2,6-tert-butyl-p-ethylphenol, 2,2-methylenebis(4-methyl-6-tert-butylphenol), 2,2-methylenebis(4-ethyl-6-tert-butylphenol), and 4,4′-thiobis(3-methyl-6-tert-butylphenol).

[0053] The thixotropy-imparting agent can adjust the thixotropy of the composition (X), thereby improving the moldability of the composition (X), which makes it easier to prepare a side fill material from the composition (X).

[0054] The photosensitizer can accelerate the curing reaction of the composition (X), thereby shortening the takt time when producing a cured product from the composition (X).

[0055] The surfactant can improve the applicability of the composition (X), which makes it easier to prepare a side fill material from the composition (X).

[0056] The silane coupling agent can improve the dispersibility of the inorganic filler (C) in the composition (X), thereby making it easier to reduce the linear expansion coefficient of the cured product. The silane coupling agent has at least one functional group selected from the group consisting of, for example, an amino group, an epoxy group, an isocyanate group, a vinyl group, a methacryl group, and a styryl group.

[0057] The composition (X) may contain a solvent (E) within a range that does not impair the effects of the present disclosure. However, it is preferable that the composition (X) does not contain the solvent (E), or that the proportion of the solvent (E) is 0.5 mass% or less relative to the solid content of the composition (X). In this case, the viscosity of the composition (X) can be well maintained when molding the composition (X).

[0058] 2.2 Production Method The production method of composition (X) will be described.

[0059] First, the components that can be contained in composition (X) described above are mixed simultaneously or sequentially to obtain a mixture. This mixture is stirred and mixed while optionally being heated or cooled. In this manner, composition (X) can be produced. For example, a disperser, planetary mixer, ball mill, three-roll mill, bead mill, and the like can be used in appropriate combination as needed to stir the mixture.

[0060] 2.3 Physical Properties The physical properties of composition (X) and its cured product are described below. By adjusting the components listed above within the ranges specified in "2.1 Components," the following physical properties can be achieved.

[0061] (Viscosity, Thixotropy Ratio) Composition (X) is liquid, i.e., has fluidity at 25° C. Composition (X) can be considered to be liquid when the viscosity at 1 rpm of composition (X) at 25° C. is 1500 Pa s or less, when the viscosity at 10 rpm of composition (X) at 25° C. is 150 Pa s or less, or when the viscosity at 1 rpm of composition (X) at 25° C. is 1500 Pa s or less and the viscosity at 10 rpm of composition (X) at 25° C. is 150 Pa s or less.

[0062] The viscosity of composition (X) at 10 rpm at 25°C is preferably 50 Pa s or less. In this case, the fluidity of composition (X) can be maintained. This makes it easier to fill composition (X). This viscosity is more preferably 40 Pa s or less, and even more preferably 30 Pa s or less.

[0063] The 10 rpm viscosity of composition (X) at 25°C can be measured using an E-type viscometer at a temperature of 25°C under the conditions of a 3°R9.7 cone, a rotation speed of 10 rpm, and a measurement time of 60 seconds. The 1 rpm viscosity of composition (X) at 25°C is the viscosity of composition (X) measured under the same conditions as the 10 rpm viscosity, except that the rotation speed is 1 rpm.

[0064] Furthermore, the thixotropic ratio of composition (X) at 25°C is preferably 2 or more and 10 or less. In this case, the fluidity of composition (X) can be maintained. This makes it easier to fill composition (X). This viscosity is more preferably 3 or more and 7 or less, and even more preferably 4 or more and 6 or less. The thixotropic ratio is calculated from the 1 rpm viscosity / 10 rpm viscosity. The 10 rpm viscosity is the 10 rpm viscosity of the above composition (X) at 25°C. The 1 rpm viscosity is the 1 rpm viscosity of the above composition (X) at 25°C.

[0065] (Photocurability) As already described, the composition (X) of the embodiment has photocurability. Therefore, the composition (X) can be cured by irradiating it with light. For example, the conditions for irradiating light, such as the light irradiation wavelength, light irradiation intensity (light amount), and light irradiation time, can be appropriately adjusted depending on the components contained in the composition (X), specifically the type of cationically polymerizable component (A) and the type of photocationic polymerization initiator (B). Any appropriate light source can be used as the light source for irradiating the composition (X). Examples of light sources include chemical lamps, low-pressure mercury lamps, medium-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, metal halide lamps, LEDs, YAG, g-rays (436 nm), h-rays (405 nm), and i-rays (365 nm). These may also be used in combination. The light source is not particularly limited as long as it can irradiate light capable of curing the composition (X).

[0066] (Linear expansion coefficient) The linear expansion coefficient of the cured product of composition (X) at 20° C. or higher and 40° C. or lower is preferably less than 25 ppm / ° C. In this case, the cured product is less likely to warp at 20° C. or higher and 40° C. or lower. This linear expansion coefficient is more preferably 20 ppm / ° C. or lower, and even more preferably 15 ppm / ° C. or lower.

[0067] The linear expansion coefficient of the cured product of composition (X) at 50° C. or higher and 70° C. or lower is preferably less than 50 ppm / ° C. In this case, the cured product is less likely to warp at 50° C. or higher and 70° C. or lower. This linear expansion coefficient is more preferably 40 ppm / ° C. or lower, and even more preferably 30 ppm / ° C. or lower.

[0068] If the linear expansion coefficient of the cured product is adjusted to be within the above range, the heat resistance reliability of a semiconductor device or device produced from composition (X) can be further improved. The linear expansion coefficient of the cured product of composition (X) can be measured by the TMA method.

[0069] 3. Application Examples Application examples of composition (X) will be described.

[0070] 3.1 Side Fill Material As described above, the composition (X) can be used to prepare a side fill material. In particular, the composition (X) can be suitably used to prepare a side fill material 4 that reinforces the substrate 2 and the mounted components 3 in the semiconductor device 1.

[0071] A semiconductor device 1 according to the embodiment includes a substrate 2, a mounting component 3, and a side fill material 4 (see FIG. 1 ). The mounting component 3 is surface-mounted on the substrate 2. More specifically, the mounting component 3 is surface-mounted face-down on the substrate 2. The substrate 2 is, for example, a motherboard, a package substrate, or an interposer substrate. For example, the substrate 2 includes conductor wiring 21. The conductor wiring 21 may be made of copper. The mounting component 3 is, for example, a semiconductor chip. The mounting component 3 may include a plurality of bump electrodes 33. For example, the bump electrode 33 includes a pillar 31 and a solder bump 32 provided at the tip of the pillar 31. The pillar 31 may be made of copper.

[0072] The side fill material 4 can be made from composition (X). That is, the side fill material 4 contains a cured product of composition (X). The side fill material 4 is interposed between the substrate 2 and the peripheral edge of the surface of the mounting component 3 that faces the substrate 2. The side fill material 4 supports the substrate 2 and the mounting component 3.

[0073] In the semiconductor device 1 of the embodiment, the side fill material 4 is interposed in the gap between the substrate 2 and the mounted component 3, only between the substrate 2 and a portion of the peripheral edge of the surface of the mounted component 3 facing the substrate 2.

[0074] For example, the length (penetration distance) of the side fill material 4 that penetrates from a position corresponding to the outer peripheral edge of the mounted component 3 in a plan view on the surface of the mounted component 3 facing the base material 2 to a position inside the surface where the mounted component 3 and the base material 2 face can be adjusted as appropriate. For example, it is preferable that the penetration distance b be the same as or shorter than the distance a (i.e., b≦a) from the position of the side fill material 4 that corresponds to the outer peripheral edge of the mounted component 3 to a position outside the surface where the mounted component 3 and the base material 2 face (see FIG. 2 ).

[0075] The state in which the substrate 2 and the peripheral portion of the mounting component 3 are reinforced with the side fill material 4 is not particularly limited and can be modified as appropriate depending on the intended use. For example, a side fill material 4 containing a cured product of composition (X) may be formed on the entire peripheral edge of the surface of the mounting component 3 facing the substrate 2. Alternatively, a side fill material 4 containing a cured product of composition (X) may be formed on the substrate 2 and on multiple corners of the peripheral edge of the surface of the mounting component 3 facing the substrate 2 (more specifically, locations including the four corners of the mounting component 3 that is approximately rectangular in plan view). Furthermore, a side fill material 4 containing a cured product of composition (X) may be formed on the corners of the peripheral edge of the surface of the mounting component 3 facing the substrate 2 and on two opposing sides.

[0076] Thus, in the semiconductor device 1 according to the embodiment, the composition (X) is not supplied deep into the gap between the substrate 2 and the mounting component 3, for example, the entire gap including the central lower portion of the mounting component 3. However, by using the composition (X), the substrate 2 and the mounting component 3 in the semiconductor device 1 can be sufficiently reinforced even by simply supplying the composition (X) to the peripheral portion of the mounting component 3. Furthermore, in the embodiment, the side fill material 4 is not present in the entire gap between the substrate 2 and the mounting component 3, and only supports the peripheral portion with the side fill material 4, which makes it less likely for the substrate 2 and the mounting component 3 to warp.

[0077] The method for manufacturing the semiconductor device 1 also includes supplying the composition (X) to the peripheral portion of the surface of the mounting component 3 surface-mounted on the substrate 2, the surface facing the substrate 2, and irradiating the supplied composition (X) with light. First, the composition (X) is supplied to the peripheral portion of the surface of the mounting component 3 surface-mounted on the substrate 2, the surface facing the substrate 2. Next, the supplied composition (X) is irradiated with light to harden the composition (X), thereby producing the side fill material 4. In this manner, the semiconductor device 1 can be manufactured.

[0078] As described above, composition (X) can be used as an adhesive. That is, a cured product can be obtained by curing composition (X), and this cured product can be used to bond, for example, two components (hereinafter also referred to as a first component and a second component) that constitute a device.

[0079] The device according to the embodiment includes a first component, a second component, and a cured product interposed between the first component and the second component to bond the first component and the second component. The cured product is obtained by curing composition (X). The device is, for example, an optical device such as a camera module, but is not limited thereto.

[0080] When the device is a camera module, bonding the first component and the second component means bonding the components of the camera module together. The components include optical components and peripheral components other than the optical components. In other words, the camera module includes optical components and peripheral components other than the optical components. In this case, the optical components may be the first component, and the peripheral components may be the second component. An example of bonding the first component and the second component is joining a lens unit to a camera housing.

[0081] The method for manufacturing a device also includes bonding a first component and a second component using an adhesive. First, a composition (X) serving as an adhesive is interposed between the first component and the second component. Then, in this state, the composition (X) is cured by irradiating it with light, thereby bonding the first component and the second component. In this manner, the device can be manufactured.

[0082] 3.3 Summary In this way, a semiconductor device 1 or device can be produced from composition (X). The heat resistance reliability of the semiconductor device 1 or device produced from composition (X) is improved. Specifically, the performance of the semiconductor device 1 or device can be maintained even if the semiconductor device 1 or device is repeatedly heated and cooled. If the performance of the semiconductor device 1 or device can be maintained, the semiconductor device 1 or device is less likely to malfunction. The heat resistance reliability of the semiconductor device 1 or device can be confirmed by conducting a heat cycle test. Details of the test method will be explained in the Examples section below.

[0083] Furthermore, the cured product does not easily lose its adhesion even at high temperatures. For example, in a semiconductor device 1, a side fill material 4 containing the cured product is interposed between a substrate 2 and a mounted component 3, and even when the semiconductor device 1 is placed at a high temperature (e.g., 125°C), the adhesion between the side fill material 4 and the substrate 2 and the mounted component 3 is not easily lost. Also, in a device, an adhesive containing the cured product is interposed between a first component and a second component, and even when the device is placed at a high temperature (e.g., 125°C), the adhesion between the first component and the second component is not easily lost.

[0084] 4. Aspects As is apparent from the above-described embodiments, the present disclosure includes the following aspects. In the following, reference numerals are given in parentheses only to clarify the correspondence with the embodiments.

[0085] The composition (X) according to the first aspect contains a cationically polymerizable component (A), a photocationic polymerization initiator (B), and an inorganic filler (C). The cationically polymerizable component (A) contains a polyfunctional cationically polymerizable compound (A1) and a monofunctional cationically polymerizable compound (A2). The polyfunctional cationically polymerizable compound (A1) contains at least one compound selected from the group consisting of a polyfunctional oxetane compound (A11) and a polyfunctional alicyclic epoxy compound (A12).

[0086] According to this embodiment, high photocurability and a reduced linear expansion coefficient of the cured product can be achieved.

[0087] The composition (X) according to the second aspect is the first aspect, wherein the proportion of the monofunctional cationically polymerizable compound (A2) is 5% by mass or more and 30% by mass or less relative to the cationically polymerizable component (A).

[0088] The composition (X) according to the third aspect is the first or second aspect, wherein the total ratio of the polyfunctional oxetane compound (A11) and the polyfunctional alicyclic epoxy compound (A12) is 50% by mass or more and 95% by mass or less relative to the cationically polymerizable component (A).

[0089] The composition (X) according to the fourth aspect is any one of the first to third aspects, in which the monofunctional cationically polymerizable compound (A2) includes at least one selected from the group consisting of a monofunctional oxetane compound (A21) and a monofunctional epoxy compound (A22).

[0090] The composition (X) according to the fifth aspect is the composition according to the fourth aspect, wherein the monofunctional cationically polymerizable compound (A2) contains a monofunctional oxetane compound (A21), and the monofunctional oxetane compound (A21) contains at least one selected from the group consisting of 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(phenoxymethyl)oxetane, and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane.

[0091] The composition (X) according to the sixth aspect is the composition of the fourth aspect, wherein the monofunctional cationically polymerizable compound (A2) contains a monofunctional epoxy compound (A22), and the monofunctional epoxy compound (A22) contains at least one selected from the group consisting of 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate, and styrene oxide.

[0092] The composition (X) according to the seventh aspect is any one of the first to sixth aspects, wherein the total amount of compounds having an oxetanyl group contained in the cationically polymerizable component (A) is 5% by mass or more and 65% by mass or less, relative to the cationically polymerizable component (A), and the total amount of compounds having an epoxy group contained in the cationically polymerizable component (A) is 40% by mass or more and 80% by mass or less, relative to the cationically polymerizable component (A).

[0093] The composition (X) according to an eighth aspect is for producing a side fill material in any one of the first to seventh aspects.

[0094] The composition (X) according to a ninth aspect is an adhesive in any one of the first to seventh aspects.

[0095] A semiconductor device (1) according to a tenth aspect includes a substrate (2), a mounting component (3) surface-mounted on the substrate (2), and a side fill material (4) interposed between the substrate (2) and the peripheral edge of the surface of the mounting component (3) facing the substrate (2). The side fill material (4) includes a cured product of the composition (X) according to any one of the first to eighth aspects.

[0096] Specific examples of the present disclosure will be presented below, but the present disclosure is not limited to the examples.

[0097] 1. Preparation of Composition The components shown in the table below were charged into a planetary mixer in the blending ratios (parts by mass) shown in the table, stirred and mixed, and uniformly dispersed using a three-roll mill to obtain a composition. Details of the components shown in the table are as follows.

[0098] (Cationically Polymerizable Component) Polyfunctional oxetane compound #1: 3-ethyl-3-{[(3-ethyloxetan-3-yl)methoxy]methyl}oxetane (product name OXT-221, manufactured by Toagosei Co., Ltd.).

[0099] Monofunctional oxetane compound #1: 3-ethyl-3-hydroxymethyloxetane (manufactured by Toagosei Co., Ltd., product name OXT-101).

[0100] Monofunctional oxetane compound #2: 3-ethyl-3-(phenoxymethyl)oxetane (manufactured by Toagosei Co., Ltd., product name OXT-211).

[0101] Monofunctional oxetane compound #3: 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane (manufactured by Toagosei Co., Ltd., product name OXT-212).

[0102] - Polyfunctional alicyclic epoxy compound #1: 3',4'-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate (manufactured by Daicel Corporation, product name: Celloxide 2021P).

[0103] - Polyfunctional alicyclic epoxy compound #2: (3,3'-bi(7-oxabicyclo[4.1.0]heptane)) (manufactured by Daicel Corporation, product name: Celloxide 8010).

[0104] - Multifunctional epoxy compound #1: hydrogenated bisphenol A glycidyl ether (manufactured by Mitsubishi Chemical Corporation, product name YX8000).

[0105] - Multifunctional epoxy compound #2: alicyclic epoxy compound (manufactured by Daicel Corporation, product name EHPE3150).

[0106] Monofunctional alicyclic epoxy compound #1: 1,2-epoxy-4-vinylcyclohexane (manufactured by Daicel Corporation, product name: Celloxide 2000).

[0107] Monofunctional alicyclic epoxy compound #2: (manufactured by Daicel Corporation, product name: Cyclomer M100).

[0108] - Monofunctional epoxy compound #1: styrene oxide.

[0109] (Photocationic Polymerization Initiator) Cationic polymerization initiator #1: triarylsulfonium tetrakis-(pentafluorophenyl)borate (manufactured by BASF, product name IRGACURE 290 (photocationic polymerization initiator, non-antimony photoacid generator)).

[0110] (Inorganic Filler) Inorganic Filler #1: Silica particles (manufactured by Denka Co., Ltd., product name QS-6 (30 μm cut)).

[0111] (Additives) Additive #1: Thixotropic agent (manufactured by Nippon Aerosil Co., Ltd., product name RY200).

[0112] Additive #2: Polyfunctional allyl ether compound (manufactured by Osaka Soda Co., Ltd., product name Neoallyl P-30M).

[0113] Additive #3: Silane coupling agent (γ-glycidoxypropyltrimethoxysilane) (manufactured by Momentive Performance Materials Japan LLC, product name SILQUEST A187J).

[0114] 2. Evaluation 2.1 Viscosity The viscosity of the composition was measured at 25°C using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., model number TP200-EH) with a 3°R9.7 cone, rotation speeds of 1 rpm and 10 rpm, and a measurement time of 60 seconds. The Ti value was calculated from the value at a rotation speed of 1 rpm (1 rpm viscosity) and the value at a rotation speed of 10 rpm (10 rpm viscosity). As described above, a composition is considered to be liquid if its 1 rpm viscosity at 25°C is 1500 Pa s or less, its 10 rpm viscosity at 25°C is 150 Pa s or less, or its 1 rpm viscosity at 25°C is 1500 Pa s or less and its 10 rpm viscosity at 25°C is 150 Pa s or less.

[0115] 2.2 Photocurability 10 mg of the composition was placed in an aluminum pan (φ5 mm) for DSC (Differential Scanning Calorimetry). The composition was irradiated with light of 365 nm wavelength at an irradiation intensity of 500 mW / cm using a UV light source (model LA-410UV manufactured by Hayashi Repic Co., Ltd.). ２ The heat of reaction due to the photocuring reaction during this irradiation was measured using a DSC measuring device manufactured by Hitachi High-Tech Science Co., Ltd. The results are shown in the table below.

[0116] 2.3 Linear expansion coefficient The composition was applied to a substrate, and the upper surface of the substrate (the side on which the composition was applied) was irradiated with an LED UV irradiator (Model Aicure UD40, manufactured by Panasonic Industrial Devices SUNX Co., Ltd.) at an illuminance of 1000 mW / cm 2 The composition was cured by irradiating light for 4 seconds under the conditions of

[0043] . Subsequently, the obtained cured product was cut into a size of 3 mm wide, 3 mm long, and 15 mm thick to prepare test specimens. Each of the prepared test specimens was heated at a temperature rise rate of 5°C / min at a measurement temperature of 0 to 260°C using a thermal analyzer (Model TMA7100, manufactured by Hitachi High-Tech Science Corporation) by the TMA method, and the linear expansion coefficient (ppm / °C) in the temperature range of 20°C to 40°C, the linear expansion coefficient (ppm / °C) in the temperature range of 50°C to 70°C, and the linear expansion coefficient (ppm / °C) in the temperature range of 20°C to 70°C were measured.

[0117] 2.4 Adhesion at 125°C A button-shaped test piece was prepared by supplying resin through a 3mm diameter opening in a 0.5mm thick silicone rubber on a solder resist-treated glass epoxy substrate (substrate: CS-3355 FR4 manufactured by Risho Kogyo Co., Ltd., plate thickness 0.6mmt / resist: PSR800 manufactured by Taiyo Ink Mfg. Co., Ltd.) and curing it under the same conditions as in "2.3 Linear expansion coefficient". Next, the test piece was placed on the heating stage of a bond tester (Dage Bond Tester 4000plus) and heated so that the surface temperature of the substrate reached 125°C. Shear strength was measured using a load cell DS100 and evaluated according to the following criteria: A: 15 MPa or more B: 10 MPa or more to less than 15 MPa C: Less than 10 MPa

[0118] 2.5 Heat Resistance Reliability (Temperature Cycle Resistance) A TEG (Test Element Group) was prepared by mounting an IC chip (WLP TEG <0.3 mm pitch BGA>, 6 mm, manufactured by Waltz Corporation) on an FR-4 circuit board (WALTS KITWLP300P, manufactured by Waltz Corporation) having daisy-chain electrodes. A composition was applied to the entire periphery of the chip (see FIG. 2 ) between the substrate and the peripheral edge of the surface of the IC chip facing the substrate, to a width of 0.8 mm and a height of 0.4 mm. The length of the contact portion between the composition and the IC chip was 2.5 mm. The applied composition was cured under the same conditions as in "2.3 Linear Expansion Coefficient" to prepare a test specimen having a cured product. Next, a heat cycle test was performed on the prepared test specimens using a thermal shock tester (Model TSE-12-A, manufactured by Espec Corporation). The heat cycle test involved applying temperature changes in a gas phase, with one cycle consisting of 30 minutes at -40°C and 30 minutes at 125°C, for a total of 2000 cycles. Operation was confirmed by measuring the resistance of the test specimen every 100 cycles. A test specimen whose resistance change from the start of the test increased by 5% or more was determined to be malfunctioning, and was evaluated according to the following criteria: A: No malfunction occurred even after more than 2000 cycles. B: Malfunction occurred between 500 and 2000 cycles. C: Malfunction occurred less than 500 cycles.

[0119]

[0120]

[0121] 1 Semiconductor device 2 Substrate 3 Mounted component

Claims

1. A liquid resin composition comprising a cationically polymerizable component (A), a photocationic polymerization initiator (B), and an inorganic filler (C), wherein the cationically polymerizable component (A) comprises a polyfunctional cationically polymerizable compound (A1) and a monofunctional cationically polymerizable compound (A2), and the polyfunctional cationically polymerizable compound (A1) comprises at least one compound selected from the group consisting of a polyfunctional oxetane compound (A11) and a polyfunctional alicyclic epoxy compound (A12).

2. The liquid resin composition according to claim 1, wherein the proportion of the monofunctional cationically polymerizable compound (A2) is 5% by mass or more and 30% by mass or less relative to the cationically polymerizable component (A).

3. The liquid resin composition according to claim 1, wherein the total proportion of the polyfunctional oxetane compound (A11) and the polyfunctional alicyclic epoxy compound (A12) is 50% by mass or more and 95% by mass or less relative to the cationically polymerizable component (A).

4. The liquid resin composition according to claim 1, wherein the monofunctional cationically polymerizable compound (A2) comprises at least one selected from the group consisting of a monofunctional oxetane compound (A21) and a monofunctional epoxy compound (A22).

5. The liquid resin composition according to claim 4, wherein the monofunctional cationically polymerizable compound (A2) contains the monofunctional oxetane compound (A21), and the monofunctional oxetane compound (A21) includes at least one compound selected from the group consisting of 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(phenoxymethyl)oxetane, and 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane.

6. The liquid resin composition according to claim 4, wherein the monofunctional cationically polymerizable compound (A2) contains the monofunctional epoxy compound (A22), and the monofunctional epoxy compound (A22) contains at least one selected from the group consisting of 1,2-epoxy-4-vinylcyclohexane, 3,4-epoxycyclohexylmethyl methacrylate, and styrene oxide.

7. A liquid resin composition according to claim 1, wherein the total amount of compounds having an oxetanyl group contained in the cationically polymerizable component (A) is 5% by mass or more and 65% by mass or less relative to the cationically polymerizable component (A), and the total amount of compounds having an epoxy group contained in the cationically polymerizable component (A) is 40% by mass or more and 80% by mass or less relative to the cationically polymerizable component (A).

8. The liquid resin composition according to claim 1, which is used to prepare a side fill material.

9. The liquid resin composition according to claim 1, which is an adhesive.

10. A semiconductor device comprising: a substrate; a mounting component to be surface-mounted on the substrate; and a side fill material interposed between the substrate and the peripheral edge of the surface of the mounting component facing the substrate, wherein the side fill material comprises a cured product of the liquid resin composition described in claim 1.

Images