Epoxy resin composition for sealing, and semiconductor device

Abstract

Provided is an epoxy resin composition for sealing which has intact flowability and can be inhibited from shrinking during molding. The epoxy resin composition for sealing comprises an epoxy compound (A), a hardener (B), an inorganic filler (C), and a modified polyamide resin (d1) represented by formula (1). In formula (1), the plurality of X1 moieties are each a divalent dicarboxylic acid residue having a phenolic hydroxyl group skeleton or a divalent dicarboxylic acid residue having no phenolic hydroxyl group skeleton, with the proviso that the plurality of X1 moieties include at least one divalent dicarboxylic acid residue having a phenolic hydroxyl group skeleton and at least one divalent dicarboxylic acid residue having no phenolic hydroxyl group skeleton; and X2 is a divalent diamine residue. The inorganic filler (C) has a volume-based particle size distribution in which the 50% cumulative particle diameter (D50) is 1-25 μm and the proportion of particles of 3 μm or smaller is 8-58%.

Description

Epoxy resin composition for encapsulation and semiconductor device

[0001] The present disclosure generally relates to an encapsulating epoxy resin composition and a semiconductor device, and more particularly to an encapsulating epoxy resin composition that can be used to produce an encapsulated portion in a semiconductor device, and a semiconductor device having an encapsulated portion containing a cured product of the encapsulating epoxy resin composition.

[0002] Patent Document 1 discloses a curable resin composition containing an epoxy resin and a curing agent, the curing agent containing a phenol compound. It is also disclosed that the curable resin composition further contains an inorganic filler.

[0003] Japanese Patent Application Laid-Open No. 2018-104603

[0004] Increasing the proportion of inorganic filler contained in the curable resin composition can suppress shrinkage that occurs during molding, but increasing the proportion of inorganic filler can cause a problem in that the fluidity of the curable resin composition is easily impaired.

[0005] An object of the present disclosure is to provide an encapsulating epoxy resin composition and a semiconductor device that can suppress shrinkage that occurs during molding without impairing fluidity.

[0006] An encapsulated epoxy resin composition according to one embodiment of the present disclosure includes an epoxy compound (A), a curing agent (B), an inorganic filler (C), and a modified polyamide resin (d1) represented by formula (1).

[0007]

[0008] In formula (1), a plurality of X １ Each of X is a divalent dicarboxylic acid residue having a phenolic hydroxyl group skeleton or a divalent dicarboxylic acid residue not having a phenolic hydroxyl group skeleton. １ contains at least one dicarboxylic acid residue having a phenolic hydroxyl group skeleton and at least one dicarboxylic acid residue not having a phenolic hydroxyl group skeleton. ２ is a divalent diamine residue, and n represents the number of repeating units contained in formula (1).

[0009] In the particle size distribution of the inorganic filler (C) on a volume basis, the particle size at 50% cumulative value (D50) is 1 μm or more and 25 μm or less, and the proportion of particles having a size of 3 μm or less is 8% or more and 58% or less.

[0010] A semiconductor device according to one aspect of the present disclosure includes an encapsulating portion including a cured product of the encapsulating epoxy resin composition.

[0011] 1 is a schematic cross-sectional view of a semiconductor device (first semiconductor device: WLP) according to an embodiment of the present disclosure. FIG. 2 is a schematic cross-sectional view of a semiconductor device (second semiconductor device: PoP) according to an embodiment of the present disclosure.

[0012] The embodiments will be described with reference to the drawings. 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 drawings referred to below are schematic diagrams, and the dimensional ratios of the components in the drawings do not necessarily reflect the actual dimensional ratios. While mechanisms related to the effects may be described below, all of the mechanisms are inferred, and the present disclosure is not bound by the descriptions of the mechanisms.

[0013] 1. Overview An encapsulating epoxy resin composition according to an embodiment (hereinafter, referred to as composition (X)) contains an epoxy compound (A), a curing agent (B), an inorganic filler (C), and a modified polyamide resin (d1) represented by formula (1).

[0014]

[0015] In formula (1), a plurality of X １ Each of X is a divalent dicarboxylic acid residue having a phenolic hydroxyl group skeleton or a divalent dicarboxylic acid residue not having a phenolic hydroxyl group skeleton. １ X contains at least one dicarboxylic acid residue having a phenolic hydroxyl group skeleton and at least one dicarboxylic acid residue not having a phenolic hydroxyl group skeleton. ２ is a divalent diamine residue, and n represents the number of repeating units contained in formula (1).

[0016] In the volume-based particle size distribution of the inorganic filler (C), the particle size at 50% cumulative value (D50) is 1 μm or more and 25 μm or less, and the proportion of particles having a size of 3 μm or less is 8% or more and 58% or less.

[0017] The inventors have found that the modified polyamide resin (d1) can improve the fluidity of the composition (X) and the flexibility of the cured product. The reason why the modified polyamide resin (d1) can improve the flexibility of the cured product is presumably because the cured product can form a phase-separated structure having a matrix containing the cured epoxy compound (A) and a dispersed phase containing the modified polyamide resin (d1) dispersed in the matrix.

[0018] Furthermore, as a result of extensive research by the inventors into the composition (X) containing such a modified polyamide resin (d1), it has been found that by controlling the particle size of the inorganic filler (C) within a specific range, specifically by setting the particle size (D50) at 50% cumulative in the volume-based particle size distribution of the inorganic filler (C) to 1 μm or more and 25 μm or less, and by setting the proportion of particles with a size of 3 μm or less in the volume-based particle size distribution of the inorganic filler (C) to 8% or more and 58% or less, it is possible to reduce the linear expansion coefficient while maintaining an appropriate level of enhanced fluidity.

[0019] By combining such a modified polyamide resin (d1) and an inorganic filler (C) having a controlled particle size, the composition (X) can suppress shrinkage that occurs during molding without impairing the flowability.

[0020] 2. Encapsulating Epoxy Resin Composition 2.1 Components The components contained in composition (X) are described below. Composition (X) contains an epoxy compound (A), a curing agent (B), an inorganic filler (C), and a modified polyamide resin (d1). The modified polyamide resin (d1) is contained in a stress relaxation agent (D).

[0021] (Epoxy Compound) The epoxy compound (A) is a compound having an epoxy group. Therefore, the epoxy compound (A) can impart thermosetting properties to the composition (X). The epoxy compound (A) includes, for example, at least one selected from the group consisting of a monomer, an oligomer, a prepolymer, and a polymer. The epoxy compound (A) preferably contains a compound having two or more epoxy groups in one molecule.

[0022] Examples of the epoxy compound (A) include alkylphenol novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins; naphthol novolac type epoxy resins; phenol aralkyl type epoxy resins having a phenylene skeleton, biphenylene skeleton, or the like; biphenyl type epoxy resins; biphenyl aralkyl type epoxy resins; naphthol aralkyl type epoxy resins having a phenylene skeleton, biphenylene skeleton, or the like; naphthylene ether type epoxy resins; polyfunctional aromatic epoxy resins such as triphenolmethane type epoxy resins and alkyl-modified triphenolmethane type epoxy resins; triphenylmethane type epoxy resins; tetrakis The epoxy compound (A) preferably contains at least one selected from the group consisting of bisphenol ethane epoxy resins, dicyclopentadiene epoxy resins, stilbene epoxy resins, bisphenol epoxy resins such as bisphenol A epoxy resins and bisphenol F epoxy resins, naphthalene epoxy resins, alicyclic epoxy resins, bromine-containing epoxy resins such as bisphenol A bromine-containing epoxy resins, glycidylamine epoxy resins obtained by reacting epichlorohydrin with polyamines such as diaminodiphenylmethane and isocyanuric acid, and glycidyl ester epoxy resins obtained by reacting epichlorohydrin with polybasic acids such as phthalic acid and dimer acid. Among these, the epoxy compound (A) preferably contains at least one selected from the group consisting of bisphenol A epoxy resins, naphthylene ether epoxy resins, biphenyl epoxy resins, polyfunctional aromatic epoxy resins, and biphenylaralkyl epoxy resins. In this case, the curability of the composition (X) can be improved.

[0023] (Curing Agent) The curing agent (B) includes, for example, a phenolic compound. In this case, the epoxy compound (A) and the curing agent (B) can efficiently undergo a thermosetting reaction. Note that the curing agent (B) is not limited to a phenolic compound as long as it undergoes a thermosetting reaction with the thermosetting resin. The curing agent (B) can include at least one selected from the group consisting of a phenolic compound, an acid anhydride, an imidazole compound, and an amine compound.

[0024] The phenol compound includes at least one selected from the group consisting of novolac type resins such as phenol novolac resin, cresol novolac resin, and naphthol novolac resin; phenol aralkyl resins having a phenylene skeleton or a biphenylene skeleton; aralkyl type resins such as naphthol aralkyl resins having a phenylene skeleton or a biphenylene skeleton; polyfunctional phenol resins such as triphenolmethane type resins; dicyclopentadiene type phenol resins such as dicyclopentadiene type phenol novolac resin and dicyclopentadiene type naphthol novolac resin; terpene-modified phenol resins; bisphenol type resins such as bisphenol A and bisphenol F; and triazine-modified novolac resins.

[0025] The curing agent (B) is preferably in the range of 0.5 to 1.5 equivalents relative to 1 equivalent of the epoxy compound (A). When the curing agent (B) is 1.5 equivalents or less, good curability of the composition (X) and good heat resistance and strength of the cured product can be achieved. It is more preferable that the curing agent is in the range of 0.6 to 1.4 equivalents.

[0026] (Inorganic Filler) The inorganic filler (C) includes, for example, at least one selected from the group consisting of silica powder, alumina powder, and silicon nitride powder. Among these, it is preferable that the inorganic filler (C) includes silica powder. When the inorganic filler (C) includes silica powder, the cured product is more likely to form a phase-separated structure having the above-mentioned matrix and dispersed phase. This makes it easier to achieve high fluidity of the composition (X) during molding and suppress shrinkage that occurs during molding. The silica powder includes at least one selected from the group consisting of fused silica powder such as fused spherical silica particles and crystalline silica powder. The ratio of silica to the inorganic filler (C) is preferably 20% by mass or more, more preferably 40% by mass or more, even more preferably 60% by mass or more, and particularly preferably 100% by mass.

[0027] As mentioned above, by controlling the particle size of the inorganic filler (C) within a specific range, the linear expansion coefficient of the cured product can be reduced without impairing fluidity. Specifically, in other words, the particle size (D50) at 50% cumulative value in the volume-based particle size distribution of the inorganic filler (C) is within a specific range, that is, the inorganic filler (C) contains a moderate amount of particles with a particle size larger than a specific particle size, and the proportion of particles with a particle size of 3 μm or less in the volume-based particle size distribution of the inorganic filler (C) is within a specific range, that is, the inorganic filler (C) contains a moderate amount of particles with a particle size smaller than a specific particle size, so that the linear expansion coefficient of the cured product can be reduced without impairing fluidity. The inorganic filler (C) may be composed of only one type of powder, but for example, by mixing multiple types of powders with different particle size distributions, an inorganic filler (C) with a desired particle size distribution can be obtained.

[0028] In an embodiment, the particle size (D50) at 50% cumulative volumetric particle size distribution of the inorganic filler (C) is 1 μm or more and 25 μm or less. D50 is the particle size corresponding to 50% cumulative volumetric value calculated from particle size distribution measurements by laser diffraction / scattering method, and can be measured using a laser diffraction / scattering particle size distribution analyzer. D50 is preferably 5 μm or more. D50 is preferably 15 μm or less.

[0029] Furthermore, the particle size (D10) at 10% cumulative volumetric particle size distribution of the inorganic filler (C) is preferably 0.1 μm or more and 2.0 μm or less. In this case, the linear expansion coefficient of the cured product can be further reduced without further impairing fluidity. D10 is the particle size corresponding to 10% cumulative volumetric value calculated from the particle size distribution measured by the laser diffraction / scattering method, and can be measured using a laser diffraction / scattering particle size distribution analyzer.

[0030] Furthermore, the particle size (D90) at 90% cumulative volumetric particle size distribution of the inorganic filler (C) is preferably 55 μm or less. In this case, the linear expansion coefficient of the cured product can be easily reduced without further impairing fluidity. D90 is the particle size corresponding to 90% cumulative volumetric value calculated from the particle size distribution measured by the laser diffraction / scattering method, and can be measured using a laser diffraction / scattering particle size distribution analyzer.

[0031] In an embodiment, the proportion of particles having a particle size of 3 μm or less in the volumetric particle size distribution of the inorganic filler (C) is 8% to 58%. This proportion is the proportion of particles having a particle size of 3 μm in the volumetric cumulative distribution obtained from the particle size distribution measured by a laser diffraction / scattering method.

[0032] The proportion of the inorganic filler (C) is preferably 60% by mass or more and 93% by mass or less relative to the composition (X). If the proportion of the inorganic filler (C) is 60% by mass or more, shrinkage that occurs during molding can be particularly suppressed. If the proportion of the inorganic filler (C) is 93% by mass or less, better fluidity of the composition (X) during molding can be ensured. This proportion is more preferably 65% ​​by mass or more, and even more preferably 70% by mass or more. This proportion is more preferably 92% by mass or less, and even more preferably 91% by mass or less.

[0033] The content of the inorganic filler (C) is preferably 400 parts by mass or more and 1,000 parts by mass or less relative to 100 parts by mass of the epoxy compound (A) and the curing agent (B) in total. If this content is 400 parts by mass or more, shrinkage that occurs during molding can be particularly suppressed. If this content is 1,000 parts by mass or less, better fluidity of the composition (X) during molding can be ensured.

[0034] (Stress Relaxant) The composition (X) may contain a stress relaxation agent (D). The stress relaxation agent (D) can relax reaction shrinkage that occurs during curing. Therefore, the rate of shrinkage that occurs during molding (molding shrinkage rate) can be reduced. For example, the stress relaxation agent (D) contains a thermoplastic resin. In an embodiment, the stress relaxation agent (D) contains a modified polyamide resin (d1) represented by formula (1).

[0035]

[0036] In formula (1), a plurality of X １ Each of X is a divalent dicarboxylic acid residue having a phenolic hydroxyl group skeleton or a divalent dicarboxylic acid residue not having a phenolic hydroxyl group skeleton. １ contains at least one dicarboxylic acid residue having a phenolic hydroxyl group skeleton and at least one dicarboxylic acid residue not having a phenolic hydroxyl group skeleton. ２ is a divalent diamine residue, and n represents the number of repeating units contained in formula (1).

[0037] As described above, the modified polyamide resin (d1) allows the cured product to form a phase-separated structure having the matrix and dispersed phase. The reason why the modified polyamide resin (d1) can form the phase-separated structure is not precisely clear, but it is presumed to be due to the following reasons. The interaction between the carboxyl groups located at the molecular terminals of the modified polyamide resin (d1) and the phenolic hydroxyl groups located inside the molecule and the epoxy compound (A) can make the epoxy compound (A) and the modified polyamide resin (d1) compatible in the composition (X). Therefore, the modified polyamide resin (d1) can be dispersed in the composition (X). Furthermore, when some of the phenolic hydroxyl groups of the modified polyamide resin (d1) dispersed in the composition (X) react with the epoxy groups of the epoxy compound (A), the cured product can form a phase-separated structure having the matrix and dispersed phase. Furthermore, since the epoxy compound (A) and the modified polyamide resin (d1) are compatible with each other in the composition (X), there is an advantage that the flowability of the composition (X) is less likely to be impaired.

[0038] Furthermore, the physical properties of the modified polyamide resin (d1) are preferably adjusted within specific ranges.

[0039] The weight average molecular weight of the modified polyamide resin (d1) is preferably 25,000 or more and 45,000 or less. If the weight average molecular weight is within the above range, the compatibility between the epoxy compound (A) and the modified polyamide resin (d1) in the composition (X) can be further improved. This makes it easier for the cured product to form the structure having the matrix and dispersed phase described above. The lower limit of the weight average molecular weight may be 28,000 or more, 31,000 or more, or 33,000 or more. The upper limit of the weight average molecular weight may be 39,000 or less. The weight average molecular weight refers to the weight average molecular weight in terms of standard polystyrene measured using gel permeation chromatography (GPC).

[0040] The value of n, which indicates the number of repeating units contained in formula (1), is preferably a value that allows the weight average molecular weight to fall within the above range, for example, 1 or more and 30 or less.

[0041] The acid value of the modified polyamide resin (d1) is preferably 1 mgKOH / g or more and 30 mgKOH / g or less. If the acid value is within the above range, the compatibility between the epoxy compound (A) and the modified polyamide resin (d1) in the composition (X) can be improved. This makes it easier for the cured product to form the phase-separated structure having the matrix and dispersed phase. The lower limit of the acid value may be 3 mgKOH / g or more, or 20 mgKOH / g or more. The upper limit of the acid value may be 15 mgKOH / g or less, or 5 mgKOH / g or less. The acid value can be measured by the measurement method specified in JIS K 2501.

[0042] The phenolic hydroxyl value of the modified polyamide resin (d1) is preferably 4 mgKOH / g or more and 30 mgKOH / g or less. If the phenolic hydroxyl value is within the above range, the compatibility between the epoxy compound (A) and the modified polyamide resin (d1) in the composition (X) can be improved. This makes it easier for the cured product to form a phase-separated structure having the matrix and dispersed phase. The lower limit of the phenolic hydroxyl value is more preferably 8 mgKOH / g or more, and even more preferably 12 mgKOH / g or more. The upper limit of the phenolic hydroxyl value is more preferably 25 mgKOH / g or less, even more preferably 20 mgKOH / g or less, and particularly preferably 14 mgKOH / g or less.

[0043] The phenolic hydroxyl value can be measured by the method described below.

[0044] <Method for measuring phenolic hydroxyl value (phenolic OH value, mgKOH / g)> 25 mL of anhydrous ethylenediamine is weighed into an Erlenmeyer flask using a volumetric pipette, 2 drops of o-nitroaniline indicator is added, and titration is performed with 0.1 N sodium methylate solution until the color turns red. The sample is added and titration is performed again, and the phenolic hydroxyl value in the sample is calculated using formula (2).

[0045] Phenolic hydroxyl value (mgKOH / g)=A×94.11×F / W (2) In equation (2), A is the amount (mL) of 0.1 N sodium methylate solution required for titration of the sample, F is the normality of the sodium methylate solution, and W is the sample weight (g).

[0046] The glass transition temperature of the modified polyamide resin (d1) is preferably 0°C or higher and 180°C or lower. If this glass transition temperature is within the above range, flexibility can be imparted to the cured product. This allows the flexural modulus of the cured product to be reduced. The lower limit of this glass transition temperature may be 20°C or higher, 30°C or higher, or 120°C or higher. The upper limit of this glass transition temperature may be 80°C or lower.

[0047] The content of the modified polyamide resin (d1) is preferably 0.5 parts by mass or more and 50 parts by mass or less relative to 100 parts by mass of the total of the epoxy compound (A) and the curing agent (B). In this case, the cured product is likely to have a structure having the above-mentioned matrix and dispersed phase. This makes it possible to suppress shrinkage that occurs during molding. This content is more preferably 2 parts by mass or more. This content is more preferably 45 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 35 parts by mass or less.

[0048] The stress relaxation agent (D) may contain a stress relaxation agent (hereinafter also referred to as a second stress relaxation agent (d2)) different from the modified polyamide resin (d1) to the extent that the fluidity of the composition (X) is not impaired. The second stress relaxation agent (d2) can further improve the flexibility of the cured product. The second stress relaxation agent (d2) includes, for example, at least one selected from the group consisting of polyamide resins, silicone resins, polyester resins, polybutadiene resins, and (meth)acrylic resins.

[0049] (Additives) The composition (X) may contain components other than the epoxy compound (A), the curing agent (B), the inorganic filler (C), and the stress relaxation agent (D), as long as the effects of the present disclosure are not impaired. The components other than the epoxy compound (A), the curing agent (B), the inorganic filler (C), and the stress relaxation agent (D) include, for example, additives. The additives include, for example, at least one selected from the group consisting of a release agent (E), a curing accelerator (F), a coupling agent (G), a pigment (H), an ion trapping agent, a flame retardant, and the like.

[0050] The release agent (E) contains at least one selected from the group consisting of, for example, natural waxes such as carnauba wax; synthetic waxes such as Montan acid ester wax and oxidized polyethylene wax; higher fatty acids and metal salts thereof such as zinc stearate; paraffin; and carboxylic acid amides such as erucic acid amide.

[0051] Examples of the curing accelerator (F) include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-phenylimidazole, and 2-ethyl-4-methylimidazole; cycloamidines such as 1,8-diazabicyclo[5.4.0]undecene-7, 1,5-diazabicyclo[4.3.0]nonene-5,5,6-dibutylamino-1,8-diazabicyclo[5.4.0]undecene-7; tertiary amines such as 2-(dimethylaminomethyl)phenol, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; tributylphosphine, methyldiphenylphosphine, and triphenylphosphine. the compound includes at least one selected from the group consisting of organic phosphines such as phenylphosphine, tris(4-methylphenyl)phosphine, diphenylphosphine, an addition reaction product of triphenylphosphine and parabenzoquinone, and phenylphosphine; tetra-substituted phosphonium and tetra-substituted borates such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium ethyltriphenylborate, and tetrabutylphosphonium tetrabutylborate; quaternary phosphonium salts having a counter anion other than borate; and tetraphenylboron salts such as 2-ethyl-4-methylimidazole tetraphenylborate and N-methylmorpholine tetraphenylborate.

[0052] The proportion of the curing accelerator (F) is preferably 0.001 mass % or more and 0.5 mass % or less relative to the composition (X).

[0053] The coupling agent (G) can improve the affinity between the epoxy compound (A) and the inorganic filler (C), thereby making it easier to reduce warpage that occurs in the cured product.

[0054] The coupling agent (G) includes at least one selected from the group consisting of silane coupling agents, titanate coupling agents, aluminum coupling agents, and aluminum / zirconium coupling agents. Examples of the silane coupling agent include at least one selected from the group consisting of glycidoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; aminosilanes such as N-β(aminoethyl)-γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and N-phenyl-γ-aminopropyltrimethoxysilane; alkylsilanes; ureidosilanes; and vinylsilanes.

[0055] The proportion of the coupling agent (G) is preferably 0.1% by mass or more and 2.0% by mass or less based on the total amount of the inorganic filler (C) and the coupling agent (G), which can particularly improve the affinity between the epoxy compound (A) and the inorganic filler (C).

[0056] 2.2 Production Method The production method of composition (X) will be explained in detail below.

[0057] Composition (X) can be prepared by mixing the components of composition (X). In this case, for example, the components are mixed in a mixer, blender, or the like until sufficiently uniform, then kneaded under heating in a kneading machine such as a heat roll or kneader, and then cooled to room temperature.

[0058] Composition (X) in powder form may be produced by pulverizing composition (X) prepared by the above method. Furthermore, composition (X) in tablet form may be produced by tableting powder composition (X). In addition to these, composition (X) may have any other appropriate shape. It is preferable that composition (X) according to the embodiment is solid at 25°C.

[0059] 2.3 Properties The properties of composition (X) and its cured product are described below.

[0060] (Fluidity) Composition (X) preferably has moderately high fluidity at high temperatures. The fluidity of composition (X) can be confirmed by a spiral flow test. Molding temperature: 170°C, injection pressure: 70 kgf / cm ２ It is preferable that the composition (X) is molded under the conditions of 180 seconds, 180 seconds, and the flow distance (flow distance) from the start of molding is 100 cm or more. If this flow distance is 100 cm or more, the ease of molding can be improved.

[0061] Since the composition (X) contains the particle size-controlled inorganic filler (C) and the modified polyamide resin (d1), it has suitably high fluidity at high temperatures and can achieve the above-mentioned spiral flow value.

[0062] (Curing Speed) It is preferable that the time from heating to curing of the composition (X), i.e., the curing speed, is adjusted within a specific range. The curing speed of the composition (X) can be confirmed by measuring the gel time. That is, the time (gel time) required for 1.67 mL of the composition (X) to reach a torque value of 0.1 kgf cm measured under conditions of a temperature of 170°C is preferably 20 seconds or more and 150 seconds or less. If this time is 20 seconds or more, sufficient molding time can be ensured. If this time is 150 seconds or less, the curing speed of the composition (X) can be maintained satisfactorily.

[0063] (Elastic Modulus) The flexural modulus of the cured product of composition (X) is preferably appropriately low. The flexural modulus of the cured product is preferably 35 GPa or less. If the flexural modulus is adjusted within the above range, warpage occurring during molding can be particularly suppressed. The method for measuring the flexural modulus will be explained in detail in the Examples section.

[0064] The composition (X) can achieve the above-mentioned flexural modulus value by containing the modified polyamide resin (d1).

[0065] (Molding shrinkage rate) It is preferable that the rate of shrinkage occurring during molding (mold shrinkage rate) is suppressed. The mold shrinkage rate is preferably 0.6% or less. In this case, warpage occurring in the cured product or a semiconductor device containing the cured product can be reduced. The mold shrinkage rate is more preferably 0.3% or less. The method for measuring the mold shrinkage rate will be explained in detail in the Examples section.

[0066] 3. Semiconductor Device The composition (X) is used to manufacture a semiconductor device.

[0067] The semiconductor device according to the embodiment includes a substrate, a semiconductor chip mounted on the substrate, and a sealing portion covering the semiconductor chip. The sealing portion may cover the entire semiconductor chip or may cover only a portion of the semiconductor chip. The sealing portion includes a cured product of composition (X).

[0068] A semiconductor device is manufactured by forming an encapsulation portion on one side of a substrate. For example, if the shrinkage during molding of the encapsulation portion is large, the difference in dimensional change between the substrate and the encapsulation portion also becomes large. As a result, warpage of the semiconductor device is likely to occur. However, according to an embodiment, shrinkage that occurs during molding of the encapsulation portion from composition (X) is suppressed, thereby reducing warpage of the semiconductor device.

[0069] 1 shows a semiconductor device 1 (first semiconductor device 11) according to this embodiment. The first semiconductor device 11 includes a substrate 5, a semiconductor chip 2 mounted on the substrate 5, and a sealing portion 3 that covers the semiconductor chip 2. The sealing portion 3 contains a cured product of composition (X). The first semiconductor device 11 is a so-called wafer-level package (WLP).

[0070] The semiconductor chip 2 is a substantially rectangular parallelepiped chip. That is, the semiconductor chip 2 is a bare semiconductor that is a functional unit cut from a wafer. In this embodiment, the semiconductor chip 2 has solder bumps 4 arranged in a grid pattern as connection terminals.

[0071] The substrate 5 is, for example, a package substrate or an interposer. The substrate 5 is not particularly limited, but may be, for example, an embedded trace substrate (ETS). The ETS is a substrate with built-in conductor wiring. The ETS may be a coreless substrate. The coreless substrate is a substrate composed only of a build-up layer. The thickness of the substrate 5 is not particularly limited, but may be, for example, in the range of 0.1 mm to 0.3 mm.

[0072] The dimensions of the semiconductor chip 2 are not particularly limited. The length of the semiconductor chip 2 is, for example, within a range of 5 mm to 30 mm. The width of the semiconductor chip 2 is, for example, within a range of 5 mm to 30 mm. The thickness of the semiconductor chip 2 (excluding the solder bumps 4) is, for example, within a range of 50 μm to 500 μm. The semiconductor chip 2 is flip-chip mounted (face-down mounted) on the substrate 5. That is, the solder bumps 4 of the semiconductor chip 2 are bonded to the lands or pads of the substrate 5.

[0073] The sealing portion 3 seals the semiconductor chip 2. The sealing portion 3 is adhered to the substrate 5. The sealing portion 3 has an outer shape of a substantially rectangular parallelepiped. The outer dimensions of the sealing portion 3 are not particularly limited. The length of the sealing portion 3 is, for example, within a range of 6 mm to 35 mm. The width of the sealing portion 3 is, for example, within a range of 6 mm to 35 mm. The thickness of the sealing portion 3 is, for example, within a range of 0.15 mm to 0.5 mm.

[0074] The sealing portion 3 is formed from the composition (X). Therefore, it is possible to suppress shrinkage that occurs when the sealing portion 3 is molded, and thereby it is possible to reduce warpage that occurs in the first semiconductor device 11.

[0075] 3.2 Second Embodiment A semiconductor device 1 according to a second embodiment will be described. Note that the description of the configuration common to the first embodiment may be omitted.

[0076] 2 shows a semiconductor device 1 (second semiconductor device 12) according to an embodiment. The second semiconductor device 12 includes a substrate 5, a semiconductor chip 2 mounted on the substrate 5, and a sealing portion 3 that covers the semiconductor chip 2. The sealing portion 3 is a package that constitutes the outer shape of the second semiconductor device 12 and includes a cured product of composition (X). The second semiconductor device 12 is a so-called package-on-package (PoP).

[0077] In this embodiment, the second semiconductor device 12 includes a semiconductor chip 2 (also referred to as a second semiconductor chip 22) on a substrate 5, and another semiconductor chip 2 (also referred to as a first semiconductor chip 21) on the second semiconductor chip 22. The second semiconductor device 12 includes wires 8 (first wires 81) that electrically connect the first semiconductor chip 21 and the second semiconductor chip 22, and wires 8 (second wires 82) that electrically connect the substrate 5 and the second semiconductor chip 22. Note that the connection of the wires 8 can be changed as appropriate. For example, the first wires 81 may electrically connect the substrate 5 and the first semiconductor chip 21. The second semiconductor device 12 may include solder bumps 7 provided on the underside of the substrate 5.

[0078] As in the first embodiment, the sealing portion 3 is formed from the composition (X). Therefore, it is possible to suppress shrinkage that occurs when the sealing portion 3 is formed. This makes it possible to reduce warpage that occurs in the first semiconductor device 11.

[0079] Furthermore, the second semiconductor device 12 can be placed on an interposer. However, such a second semiconductor device 12 is less likely to warp, and therefore does not require the use of a thick substrate such as an organic substrate including a core layer in the interposer. In other words, the height of the interposer can be easily reduced. This can also contribute to the miniaturization of electronic devices incorporating the second semiconductor device 12.

[0080] 3.3 Summary Two examples of semiconductor devices 1 having an encapsulating portion 3 containing a cured product of composition (X) have been given, but the types of semiconductor devices to which composition (X) can be applied are not limited to those described above, and composition (X) can be used for various semiconductor devices. Furthermore, composition (X) can be used for various purposes, not limited to the manufacture of semiconductor devices.

[0081] 4. Aspects The present disclosure includes the following aspects.

[0082] The composition (X) according to the first aspect of the present disclosure contains an epoxy compound (A), a curing agent (B), an inorganic filler (C), and a modified polyamide resin (d1) represented by formula (1).

[0083]

[0084] In formula (1), a plurality of X １ each of X is a divalent dicarboxylic acid residue having a phenolic hydroxyl group skeleton or a divalent dicarboxylic acid residue not having a phenolic hydroxyl group skeleton, and １ contains at least one dicarboxylic acid residue having a phenolic hydroxyl group skeleton, and at least one dicarboxylic acid residue not having a phenolic hydroxyl group skeleton. ２ is a divalent diamine residue, and n represents the number of repeating units contained in formula (1).

[0085] The particle size (D50) at 50% cumulative volumetric particle size distribution of the inorganic filler (C) is 1 μm or more and 25 μm or less, and the proportion of particles with a size of 3 μm or less is 8% or more and 58% or less.

[0086] According to this embodiment, shrinkage that occurs during molding can be suppressed without impairing the fluidity of the composition (X).

[0087] In the composition (X) according to the second aspect of the present disclosure, in the first aspect, the inorganic filler (C) includes silica particles.

[0088] In the composition (X) according to the third aspect of the present disclosure, in the first or second aspect, the content of the inorganic filler (C) is 400 parts by mass or more and 1000 parts by mass or less relative to 100 parts by mass in total of the epoxy compound (A) and the curing agent (B).

[0089] In the composition (X) according to the fourth aspect of the present disclosure, in any one of the first to third aspects, the weight average molecular weight of the modified polyamide resin (d1) is 25,000 or more and 45,000 or less.

[0090] The composition (X) according to the fifth aspect of the present disclosure is any one of the first to fourth aspects, in which the content of the modified polyamide resin (d1) is 0.5 parts by mass or more and 50 parts by mass or less, relative to 100 parts by mass in total of the epoxy compound (A) and the curing agent (B).

[0091] The composition (X) according to the sixth aspect of the present disclosure is any one of the first to fifth aspects, in which the epoxy compound (A) comprises at least one selected from the group consisting of bisphenol A-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, polyfunctional aromatic epoxy resins, and biphenylaralkyl-type epoxy resins.

[0092] A semiconductor device according to a seventh aspect of the present disclosure includes a sealing portion including a cured product of the composition (X) according to any one of the first to sixth aspects.

[0093] The effects of this embodiment will be described in more detail below with reference to examples, but the present disclosure is not limited to these examples.

[0094] 1. Preparation of Composition The following raw materials were prepared as components of the composition.

[0095] (Epoxy Compounds) - Epoxy compound #1: Bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, product name YL6810. - Epoxy compound #2: Naphthylene ether type epoxy resin, manufactured by DIC Corporation, product name HP6000L. - Epoxy compound #3: Biphenyl type epoxy resin, manufactured by Mitsubishi Chemical Corporation, product name YX4000. - Epoxy compound #4: Multifunctional aromatic epoxy resin, manufactured by Printec Co., Ltd., product name VG3101L. - Epoxy compound #5: Biphenyl aralkyl type epoxy resin, manufactured by Nippon Kayaku Co., Ltd., product name NC3000.

[0096] (Hardening Agents) - Hardener #1: Phenolic hardener, manufactured by Meiwa Kasei Co., Ltd., product name MEH-7500-3S. - Hardener #2: Phenolic hardener, manufactured by Meiwa Kasei Co., Ltd., product name MEH-7851-3S. - Hardener #3: Phenolic hardener, manufactured by Meiwa Kasei Co., Ltd., product name H-3M.

[0097] (Inorganic Fillers) - Inorganic Filler #1: Spherical fused silica powder, D10 0.2 μm, D50 7 μm, D90 14 μm, containing 30% particles of 3 μm or less. - Inorganic Filler #2: Spherical fused silica powder, D10 0.6 μm, D50 12 μm, D90 39 μm, containing 27% particles of 3 μm or less. - Inorganic Filler #3: Spherical fused silica powder, D10 3.0 μm, D50 16 μm, D90 39 μm, containing 11% particles of 3 μm or less. - Inorganic Filler #4: Spherical fused silica powder, D10 0.4 μm, D50 2 μm, D90 33 μm, containing 55% silica particles of 3 μm or less. Inorganic filler #5: spherical fused silica powder, D10 3 μm, D50 7 μm, D90 14 μm, containing 7% particles of 3 μm or less. Inorganic filler #6: spherical fused silica powder, D10 0.4 μm, D50 1 μm, D90 30 μm, containing 60% particles of 3 μm or less.

[0098] (Stress Relaxants) Stress Relaxant #1: Modified polyamide resin having the structure shown in formula (1), manufactured by Toyochem Co., Ltd., product name DYNALEOVA-9501S (weight average molecular weight 35,000, acid value 9 mgKOH / g, phenolic hydroxyl value 15 mgKOH / g, glass transition temperature 55°C). Stress Relaxant #2: Silicone resin, manufactured by Dow Toray Industries, Inc., product name DOWSIL EP-2601. Stress Relaxant #3: Silicone resin (polymethylsilsesquioxane particles), manufactured by Nikko Rica Corporation, Silcrush-A3500. Stress Relaxant #4: Butadiene resin, manufactured by Kaneka Corporation, KANEACE MZ-150.

[0099] (Release Agents) -Release Agent #1: Carnauba wax, manufactured by Dainichi Chemical Industry Co., Ltd., product name Carnauba F-100.

[0100] (Curing accelerators) - Curing accelerator #1: Phosphorus-based curing accelerator, manufactured by San-Apro Co., Ltd., product name U-CAT RP701. - Curing accelerator #2: Imidazole-based compound, manufactured by Shikoku Chemicals Co., Ltd., product name Curesol 2PHZ.

[0101] (Coupling Agent) Coupling Agent #1: 3-glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Chemical Co., Ltd., product name KBM403.

[0102] (Pigments) - Pigment #1: Carbon black, manufactured by Mitsubishi Chemical Corporation, product name MA600.

[0103] The raw materials were blended in the compositions shown in Tables 1 and 2, mixed for 10 minutes using a mixer, and then kneaded using a two-screw roll while heating at 110°C. The mixture was cooled and then pulverized. The powder thus obtained was compressed into tablets to obtain tablet-shaped compositions.

[0104] 2. Evaluation Tests The following evaluation tests were carried out on the compositions, and the results are shown in Tables 1 and 2.

[0105] (1) Spiral flow: According to ASTM D3123, a spiral flow measurement mold was used, and the molding temperature was 170°C and the injection pressure was 70 kgf / cm. ２ The composition was molded under the conditions of 180 seconds molding time, and the distance it flowed (flow distance) for 180 seconds from the start of molding was measured.

[0106] (2) Gel Time Using a Curastometer testing device (manufactured by JSR Corporation, product name: Curastometer III PS type), the surface temperatures of both the upper and lower sides of a mold were set to 170°C, 1.67 mL of a composition sample was charged, and the torque value was measured. The time required for the torque value to reach 0.1 kgf cm was read as the gel time.

[0107] (3) Flexural Modulus Using a transfer molding machine (manufactured by Shinto Metal Industries Co., Ltd., product name ETA-30D), the composition was molded under conditions of an injection pressure of 6.86 MPa, a mold temperature of 175°C, and a holding time of 150 seconds, and then the composition was cured by heating at 175°C for 4 hours. This yielded test pieces measuring 10 mm x 80 mm x 4 mm.

[0108] Subsequently, a three-point bending test was carried out on the test piece using a universal material testing machine (Instron, product name 5965), and the flexural modulus of the test piece was determined from the resulting stress-strain curve.

[0109] (4) Mold shrinkage The dimensions of the test piece obtained by the method described in "(3) Flexural modulus" were measured, and the mold shrinkage was calculated according to the following formula (3).

[0110] Mold shrinkage rate = {1 - (test piece size / mold size)} × 100 (3)

[0111]

[0112]

[0113] 1 semiconductor device 3 sealing portion

Claims

1. A composition comprising an epoxy compound (A), a curing agent (B), an inorganic filler (C), and a modified polyamide resin (d1) represented by formula (1), In formula (1), a plurality of X １ each of X is a divalent dicarboxylic acid residue having a phenolic hydroxyl group skeleton or a divalent dicarboxylic acid residue not having a phenolic hydroxyl group skeleton, １ contains at least one dicarboxylic acid residue having a phenolic hydroxyl group skeleton and at least one dicarboxylic acid residue not having a phenolic hydroxyl group skeleton, and X ２ is a divalent diamine residue, and n represents the number of repeating units contained in formula (1), and the particle size (D50) at 50% cumulative in a volume-based particle size distribution of the inorganic filler (C) is 1 μm or more and 25 μm or less, and the proportion of particles with a size of 3 μm or less is 8% or more and 58% or less.

2. The encapsulating epoxy resin composition according to claim 1, wherein the inorganic filler (C) contains silica powder.

3. The encapsulating epoxy resin composition according to claim 1, wherein the content of the inorganic filler (C) is 400 parts by mass or more and 1,000 parts by mass or less per 100 parts by mass of the epoxy compound (A) and the curing agent (B) in total.

4. The encapsulating epoxy resin composition according to claim 1, wherein the weight average molecular weight of the modified polyamide resin (d1) is 25,000 or more and 45,000 or less.

5. The encapsulating epoxy resin composition according to claim 1, wherein the content of the modified polyamide resin (d1) is 0.5 parts by mass or more and 50 parts by mass or less per 100 parts by mass of the epoxy compound (A) and the curing agent (B) in total.

6. The encapsulating epoxy resin composition according to claim 1, wherein the epoxy compound (A) comprises at least one selected from the group consisting of bisphenol A-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, polyfunctional aromatic epoxy resins, and biphenylaralkyl-type epoxy resins.

7. A semiconductor device having an encapsulating part comprising a cured product of the encapsulating epoxy resin composition according to any one of claims 1 to 6.

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