Sealing composition and semiconductor device

Abstract

A sealing composition comprises: a first epoxy resin having at least two benzene rings in the molecule and at least one ether bond connecting the two benzene rings directly or via a linking group, wherein the two benzene rings have no substituents at the ortho and meta positions of the bonding positions of the ether bonds; a hardener; and an inorganic filler.

Description

Technical Field

[0001] The present invention relates to a sealing composition and a semiconductor device. Background Art

[0002] In recent years, with the miniaturization and high integration, there is a concern about the heat inside the semiconductor package. Since there is a risk of performance degradation of electrical or electronic components having the semiconductor package due to heat, high thermal conductivity is required for the components used in the semiconductor package. Therefore, it is required that the sealing material of the semiconductor package has high thermal conductivity.

[0003] On the other hand, members used in semiconductor packages are also required to have durability against temperature cycle tests.

[0004] For example, if the inorganic filler is highly filled, the thermal conductivity of the sealant can be increased, but the elastic coefficient increases, which may reduce the durability in the temperature cycle test. The high thermal conductivity and low elastic coefficient of the sealant are in a trade-off relationship. Therefore, it is difficult to achieve both high thermal conductivity and low elastic coefficient.

[0005] As an example of a sealing material highly filled with an inorganic filler, there is known an epoxy resin composition for semiconductor sealing, which has (A) an epoxy resin, (B) a hardener, and (D) an inorganic filler containing spherical alumina and spherical silica as essential components, wherein the spherical alumina comprises (d1) a first spherical alumina having an average particle size of not less than 40 μm and not more than 70 μm and (d2) a second spherical alumina having an average particle size of not less than 10 μm and not more than 15 μm, wherein the spherical alumina The silica comprises a first spherical silica having an average particle size of (d3) greater than or equal to 4 μm and less than or equal to 8 μm, and a second spherical silica having an average particle size of (d4) greater than or equal to 0.05 μm and less than or equal to 1.0 μm, wherein the total amount of (d3) + (d4) relative to all inorganic fillers is greater than or equal to 17% and less than or equal to 23%, the ratio of (d3) / (d4) is greater than or equal to (d3) / (d4) = 1 / 8 and less than or equal to 5 / 4, and the amount of the inorganic filler in the entire resin composition is 85% to 95% by mass (for example, refer to Patent Document 1).

[0006] [Prior art literature]

[0007] [Patent Document]

[0008] Patent Document 1: Japanese Patent Application Publication No. 2006-273920 Summary of the invention

[0009] [Problems to be solved by the invention]

[0010] However, in the semiconductor sealing epoxy resin composition described in Patent Document 1, the elastic modulus of the sealing material (i.e., the cured product of the semiconductor sealing epoxy resin composition) may be increased due to the high filling of alumina as a high thermal conductive filler. Therefore, the difficulty is to develop a high thermal conductive sealing material with a low elastic modulus.

[0011] The present disclosure has been made in view of the above-mentioned conventional situation, and an object of the present disclosure is to provide a sealing composition and a semiconductor device using the sealing composition, which can suppress the elastic modulus of the cured product at a high temperature (260° C.) to be low and improve the thermal conductivity of the cured product.

[0012] [Technical means to solve the problem]

[0013] The specific means for achieving the above-mentioned objects are as follows.

[0014] <1>

[0015] A sealing composition comprising:

[0016] The first epoxy resin has at least two benzene rings and at least one ether bond connecting the two benzene rings directly or via a linking group in the molecule, and the two benzene rings have no substituents at the ortho and meta positions of the bonding positions of the ether bonds;

[0017] Hardener; and

[0018] Inorganic filler.

[0019] <2>

[0020] The sealing composition according to <1>, wherein the content of the inorganic filler is 78% by volume or more based on the entire sealing composition.

[0021] <3>

[0022] The sealing composition according to <1> or <2>, further comprising a second epoxy resin having a melting point or a softening point of 50° C. or higher.

[0023] <4>

[0024] The sealing composition according to <3>, wherein the content of the second epoxy resin is 80% by mass or less relative to the total amount of the epoxy resin contained in the sealing composition.

[0025] <5>

[0026] The sealing composition according to <3> or <4>, wherein the content of the second epoxy resin is 50% by mass or more relative to the total amount of the epoxy resin contained in the sealing composition.

[0027] <6>

[0028] The sealing composition according to any one of <1> to <5>, wherein the first epoxy resin has two epoxy groups in a molecule.

[0029] <7>

[0030] The sealing composition according to any one of <1> to <6>, wherein the ether bond is directly bonded to at least one of the two benzene rings.

[0031] <8>

[0032] The sealing composition according to any one of <1> to <7>, wherein the group linking the two benzene rings is a group including one ether bond.

[0033] <9>

[0034] The sealing composition according to any one of <1> to <7>, wherein the group linking the two benzene rings is a group containing two or more of the ether bonds.

[0035] <10>

[0036] The sealing composition according to <9>, wherein the group linking the two benzene rings is a divalent linking group represented by the following structural formula (1).

[0037] [Chemistry 1]

[0038]

[0039] In the structural formula (1), * represents a bonding portion to the benzene ring.

[0040] <11>

[0041] The sealing composition according to any one of <1> to <10>, further comprising a third epoxy resin, wherein the third epoxy resin is a resin other than the first epoxy resin and has a benzene ring and at least two epoxy groups bonded to the para position of the benzene ring directly or via a linking group, and the benzene ring has no substituent at the ortho and meta positions of the bonding positions of the two epoxy groups.

[0042] <12>

[0043] A semiconductor device comprising a semiconductor element and a cured product of the sealing composition according to any one of <1> to <11> for sealing the semiconductor element.

[0044] [Effects of the Invention]

[0045] According to the present disclosure, it is possible to provide a sealing composition that suppresses the elastic modulus of a cured product at a high temperature (260° C.) to be low and improves the thermal conductivity of the cured product, and a semiconductor device using the sealing composition. DETAILED DESCRIPTION

[0046] Hereinafter, the sealing composition and the semiconductor device for implementing the present invention will be described in detail. The present invention is not limited to the following embodiments. In the following embodiments, the constituent elements (including element steps, etc.) are not required unless otherwise specifically indicated. The same is true for numerical values ​​and their ranges, and the present invention is not limited thereto.

[0047] In the present disclosure, in a numerical range represented by “to”, numerical values ​​described before and after including “to” are respectively regarded as the minimum value and the maximum value.

[0048] In the numerical ranges recorded in stages in the present disclosure, the upper limit or lower limit recorded in one numerical range may also be replaced by the upper limit or lower limit of the numerical range recorded in other stages. Moreover, in the numerical ranges recorded in the present disclosure, the upper limit or lower limit of the numerical range may also be replaced by the value shown in the embodiments.

[0049] In the present disclosure, each component may include a plurality of corresponding substances. When a plurality of substances corresponding to each component are present in the composition, unless otherwise specified, the content rate or content of each component refers to the total content rate or content of the plurality of substances present in the composition.

[0050] In the present disclosure, multiple types of particles corresponding to each component may be included. When multiple types of particles corresponding to each component are present in the composition, unless otherwise specified, the particle size of each component refers to the value for the mixture of the multiple types of particles present in the composition.

[0051] In the present disclosure, “(meth)acryloyl” refers to at least one of acryloyl and methacryloyl, “(meth)acrylic acid” refers to at least one of acrylic acid and methacrylic acid, and “(meth)acrylate” refers to at least one of acrylate and methacrylate.

[0052] <Sealing composition>

[0053] The sealing composition disclosed herein comprises: a first epoxy resin having at least two benzene rings in a molecule and at least one ether bond connecting the two benzene rings directly or via a linking group, wherein the two benzene rings have no substituents at the ortho and meta positions of the bonding positions of the ether bonds; a hardener; and an inorganic filler.

[0054] Since the sealing composition of the present disclosure contains the first epoxy resin, the elastic coefficient of the cured product at high temperature (260° C.) (hereinafter also referred to as “high temperature elastic coefficient”) is suppressed low and the thermal conductivity of the cured product is improved. The reason is not clear, but it is speculated as follows.

[0055] It is believed that the first epoxy resin without a substituent at the ortho and meta positions is more oriented and has higher crystallinity than the epoxy resin with a substituent, so that molecular vibration is more likely to occur, and heat loss is reduced, so that the thermal conductivity of the cured product can be increased. In addition, it is speculated that the first epoxy resin has flexibility due to the ether bond connecting two benzene rings, so the thermal conductivity of the cured product can be improved while suppressing the increase of the high-temperature elastic coefficient of the cured product.

[0056] Hereinafter, each component constituting the sealing composition will be described. The sealing composition of the present disclosure contains an epoxy resin, a hardener, and an inorganic filler, and may contain other components as necessary.

[0057] -Epoxy resin-

[0058] Examples of epoxy resins include: epoxy resins obtained by epoxidizing a novolac resin obtained by condensing or co-condensing at least one selected from the group consisting of phenolic compounds (phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, etc.) and naphthol compounds (α-naphthol, β-naphthol, dihydroxynaphthalene, etc.) with an aldehyde compound (formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, etc.) under an acidic catalyst (phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, etc.); epoxy resins selected from the group consisting of bisphenols (bisphenol A, bisphenol AD, bisphenol F, bisphenol S, etc.) and biphenols (alkyl-substituted or unsubstituted); At least one diglycidyl ether selected from the group consisting of substituted biphenols, etc.); epoxides of phenol-aralkyl resins; epoxides of adducts or polyadducts of phenol compounds and at least one selected from the group consisting of dicyclopentadiene and terpene compounds; glycidyl ester type epoxy resins obtained by reaction of polyacids (phthalic acid, dimer acid, etc.) with epichlorohydrin; glycidylamine type epoxy resins obtained by reaction of polyamines (diaminodiphenylmethane, isocyanuric acid, etc.) with epichlorohydrin; linear aliphatic epoxy resins obtained by oxidation of olefin bonds with peroxyacids (peracetic acid, etc.); alicyclic epoxy resins, etc. The epoxy resins may be used alone or in combination of two or more.

[0059] Among these epoxy resins, as described above, the sealing composition of the present disclosure contains a first epoxy resin, which has at least two benzene rings and at least one ether bond connecting the two benzene rings directly or via a linking group in the molecule, and the two benzene rings have no substituents at the ortho-position and meta-position of the bonding position of the ether bond.

[0060] Furthermore, the sealing composition of the present disclosure may contain an epoxy resin other than the first epoxy resin and the third epoxy resin described below, if necessary, and preferably further contains a second epoxy resin having a melting point or softening point of 50° C. or higher as a resin other than the first epoxy resin and the third epoxy resin described below.

[0061] Furthermore, the sealing composition of the present disclosure may also contain a third epoxy resin as needed, wherein the third epoxy resin is a resin other than the first epoxy resin and has a benzene ring and at least two epoxy groups bonded to the para position of the benzene ring directly or via a linking group, and the benzene ring has no substituent at the ortho position and meta position of the bonding position of the two epoxy groups.

[0062] The sealing composition of the present disclosure may contain epoxy resins other than the first epoxy resin, the second epoxy resin, and the third epoxy resin as needed (hereinafter also referred to as "other epoxy resins"). The total content of the first epoxy resin and the second epoxy resin and the third epoxy resin as needed relative to the total amount of all epoxy resins contained in the sealing composition is preferably 90% by mass or more, more preferably 95% by mass or more, and even more preferably 98% by mass or more.

[0063] (First Epoxy Resin)

[0064] The first epoxy resin is not particularly limited as long as it has at least two benzene rings in the molecule and at least one ether bond connecting the two benzene rings directly or via a linking group, and the two benzene rings have no substituents at the ortho and meta positions of the bonding positions of the ether bonds.

[0065] Hereinafter, the benzene ring linked via the ether bond is also referred to as a "specific benzene ring".

[0066] The number of specific benzene rings contained in one molecule of the first epoxy resin is not particularly limited as long as it is at least two, and the number may be in the range of 2 to 6, preferably 2 to 4, and more preferably 2.

[0067] The first epoxy resin may also have an aromatic hydrocarbon ring other than a specific benzene ring bonded to the specific benzene ring directly or via a linking group. In the case where the first epoxy resin has an aromatic hydrocarbon ring other than a specific benzene ring, the aromatic hydrocarbon ring possessed by the first epoxy resin may be one type or two or more types. Moreover, in the case where the first epoxy resin has an aromatic hydrocarbon ring other than a specific benzene ring, the number of the aromatic hydrocarbon rings possessed by the first epoxy resin may be 2 or more, may be in the range of 2 to 4, or may be 2. As aromatic hydrocarbon rings other than the specific benzene ring, benzene ring, naphthalene ring, etc. may be listed, among which benzene ring is preferred.

[0068] When the first epoxy resin has a benzene ring as an aromatic hydrocarbon ring other than a specific benzene ring, the benzene ring other than the specific benzene ring preferably has no substituent at the ortho-position and the meta-position of the bonding position of the specific benzene ring.

[0069] The first epoxy resin has at least two epoxy groups in the molecule. The number of epoxy groups in the first epoxy resin in one molecule is not particularly limited as long as it is two or more, and 2 to 8 are examples, 2 to 6 are preferred, 2 to 3 are more preferred, and 2 is particularly preferred.

[0070] The epoxy group may be contained in the molecule of the first epoxy resin as part of at least one selected from glycidyl group, glycidyloxy group, glycidyloxycarbonyl group, glycidylamino group, epoxycycloalkyl group (epoxycyclopentyl group, epoxycyclohexyl group, epoxycyclooctyl group, etc.).

[0071] The first epoxy resin preferably has a glycidyloxy group in the molecule, and more preferably has a glycidyloxy group directly bonded to a specific benzene ring or an aromatic hydrocarbon ring other than the specific benzene ring in the molecule. That is, the glycidyloxy group may be directly bonded to a specific benzene ring or to other aromatic hydrocarbon rings other than the specific benzene ring.

[0072] Moreover, when the first epoxy resin has two or more glycidyloxy groups, it is preferred that all of the two or more glycidyloxy groups are directly bonded to at least one selected from a specific benzene ring and an aromatic hydrocarbon ring other than the specific benzene ring, more preferably all of the two or more glycidyloxy groups are directly bonded to the specific benzene ring or directly bonded to an aromatic hydrocarbon ring other than the specific benzene ring, and even more preferably all of the two or more glycidyloxy groups are directly bonded to the specific benzene ring or directly bonded to a benzene ring other than the specific benzene ring.

[0073] The first epoxy resin only needs to have at least one ether bond between two specific benzene rings in one molecule, and may have two or more ether bonds.

[0074] The ether bond is preferably directly bonded to the specific benzene ring, and may be bonded to the specific benzene ring via other linking groups other than the ether bond (a hydrocarbon group such as a substituted or unsubstituted alkylene group, a carbonyl group, etc.). The group linking the two specific benzene rings may be a group including one ether bond, a group including an ether bond and other linking groups other than the ether bond, a group including two or more ether bonds, or a group including two or more ether bonds and other linking groups other than the ether bond.

[0075] Examples of the group containing two or more ether bonds and other linking groups other than ether bonds include a divalent linking group represented by the following structural formula (1).

[0076] In the following structural formula (1), * represents a bonding portion to a specific benzene ring.

[0077] [Chemistry 2]

[0078]

[0079] The first epoxy resin may further have other substituents (alkyl group, alkoxy group, aryl group, aralkyl group, amino group, etc.).

[0080] As the first epoxy resin, for example, an epoxy resin represented by the following general formula (2) can be mentioned.

[0081] [Chemistry 3]

[0082]

[0083] In the general formula (2), E 1 and E 2 Each independently represents a monovalent group containing an epoxy group, L 1 represents a divalent linking group containing an ether bond, L 2 and L 3 Each independently represents a divalent linking group including an aromatic hydrocarbon ring, a1 and a2 each independently represent an integer of 0 to 3, and n represents an integer of 1 to 4.

[0084] As E in the general formula (2) 1 and E 2 Examples of the monovalent group represented by include glycidyl group, glycidyloxy group, glycidyloxycarbonyl group, glycidylamino group, epoxycycloalkyl group (epoxycyclopentyl group, epoxycyclohexyl group, epoxycyclooctyl group, etc.), and among them, glycidyloxy group is preferred.

[0085] As L in the general formula (2) 1 Examples of the divalent linking group represented by include an ether bond, the divalent linking group represented by the structural formula (1), a peroxy group, and an acetal group.

[0086] As L in the general formula (2) 2 and L 3 Examples of the divalent linking group represented by include phenylene and naphthylene, preferably phenylene, and more preferably p-phenylene.

[0087] In the general formula (2), a1 and a2 are preferably integers of 0-2, and more preferably integers of 0-1.

[0088] In the general formula (2), n is preferably 1 to 3, more preferably 1 to 2, and even more preferably 1.

[0089] When the sealing composition does not contain the third epoxy resin described later, the epoxy group equivalent in the first epoxy resin can be, for example, 180 g / eq or less. From the viewpoint of achieving both improvement in thermal conductivity and suppression of increase in high-temperature elastic coefficient, it is preferably 130 g / eq to 180 g / eq, more preferably 135 g / eq to 175 g / eq, and even more preferably 140 g / eq to 170 g / eq.

[0090] Moreover, when the sealing composition contains the third epoxy resin described later, the epoxy group equivalent in the mixture of the first epoxy resin and the third epoxy resin can be, for example, 180 g / eq or less. From the viewpoint of achieving both improvement in thermal conductivity and suppression of increase in high-temperature elastic coefficient, it is preferably 125 g / eq to 180 g / eq, more preferably 130 g / eq to 175 g / eq, and even more preferably 135 g / eq to 170 g / eq.

[0091] Here, the "epoxy equivalent" is measured as follows. Specifically, the epoxy resin to be measured is weighed and dissolved in a solvent such as methyl ethyl ketone, and acetic acid and tetraethylammonium bromide acetic acid solution are added, and then potentiometric titration is performed using a perchloric acid acetic acid standard solution to measure. An indicator may also be used in the titration.

[0092] In the case where the sealing composition does not contain the third epoxy resin described later, from the perspective of both suppressing the rise of the high-temperature elastic coefficient and improving the thermal conductivity, the content of the first epoxy resin is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 25% by mass or more relative to the total amount of all epoxy resins contained in the sealing composition. In addition, in the case where the sealing composition does not contain the third epoxy resin described later, from the perspective of the formability of the sealing composition, the content of the first epoxy resin is preferably 70% by mass or less, more preferably 50% by mass or less, and more preferably 40% by mass or less relative to the total amount of all epoxy resins contained in the sealing composition. In the case where the sealing composition does not contain the third epoxy resin described later, from the perspective of suppressing the rise of the high-temperature elastic coefficient, improving the thermal conductivity and the formability of the sealing composition, the content of the first epoxy resin is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 50% by mass, and more preferably 25% by mass to 40% by mass relative to the total amount of all epoxy resins contained in the sealing composition.

[0093] In the case where the sealing composition includes the third epoxy resin described later, from the perspective of both suppressing the rise of the high-temperature elastic coefficient and improving the thermal conductivity, the total content of the first epoxy resin and the third epoxy resin relative to the total amount of all epoxy resins contained in the sealing composition is preferably 10% by mass or more, more preferably 20% by mass or more, and more preferably 25% by mass or more. Moreover, in the case where the sealing composition includes the third epoxy resin described later, from the perspective of the formability of the sealing composition, the total content of the first epoxy resin and the third epoxy resin is preferably 70% by mass or less, more preferably 50% by mass or less, and more preferably 40% by mass or less. In the case where the sealing composition includes the third epoxy resin described later, from the perspective of suppressing the rise of the high-temperature elastic coefficient, improving the thermal conductivity and the formability of the sealing composition, the total content of the first epoxy resin and the third epoxy resin is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 50% by mass, and more preferably 25% by mass to 40% by mass.

[0094] Moreover, when the sealing composition includes the third epoxy resin described later, the content of the first epoxy resin relative to the total of the first epoxy resin and the third epoxy resin can be, for example, 5 mass % to 35 mass %, and from the viewpoint of suppressing the increase in the high-temperature elastic coefficient, it is preferably 10 mass % to 35 mass %, and more preferably 20 mass % to 35 mass %.

[0095] When the sealing composition does not contain the third epoxy resin described below, the content of the first epoxy resin relative to the entire sealing composition is preferably 0.2 to 3.0 mass %, more preferably 0.4 to 1.5 mass %, and further preferably 0.6 to 1.1 mass %.

[0096] When the sealing composition contains the third epoxy resin described below, the total content of the first epoxy resin and the third epoxy resin is preferably 0.2 to 3.0% by mass, more preferably 0.4 to 1.5% by mass, and even more preferably 0.6 to 1.1% by mass relative to the entire sealing composition.

[0097] (Second epoxy resin)

[0098] The second epoxy resin is not particularly limited as long as it is an epoxy resin other than the first epoxy resin and the third epoxy resin described later and has a melting point or a softening point of 50° C. or higher.

[0099] Here, the melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method (ring and ball method) in accordance with Japanese Industrial Standards (JIS) K 7234:1986.

[0100] In addition, from the viewpoint of the moldability of the sealing composition, the melting point or softening point in the second epoxy resin is preferably 50°C or higher, more preferably 60°C or higher, and further preferably 70°C or higher. Furthermore, from the viewpoint of kneading properties during production, the melting point or softening point in the second epoxy resin is preferably 150°C or lower, more preferably 130°C or lower, and further preferably 120°C or lower. From the viewpoint of the moldability of the sealing composition and kneading properties during production, the melting point or softening point in the second epoxy resin is preferably 50°C to 150°C, more preferably 60°C to 130°C, and further preferably 70°C to 120°C.

[0101] The epoxy group equivalent in the second epoxy resin is not particularly limited, but is preferably less than 300 g / eq, more preferably 120 g / eq to 270 g / eq, and further preferably 150 g / eq to 240 g / eq from the viewpoint of achieving both moldability and suppression of increase in high temperature elastic coefficient.

[0102] The second epoxy resin has at least two epoxy groups in the molecule. The number of epoxy groups in the second epoxy resin in one molecule is not particularly limited, but may be 2 to 8, preferably 2 to 6, more preferably 2 to 3, and particularly preferably 2.

[0103] The epoxy group may be contained in the molecule of the second epoxy resin as part of at least one selected from glycidyl group, glycidyloxy group, glycidyloxycarbonyl group, glycidylamino group, epoxycycloalkyl group (epoxycyclopentyl group, epoxycyclohexyl group, epoxycyclooctyl group, etc.).

[0104] The second epoxy resin preferably has a divalent linking group represented by the following general formula (3) in addition to two or more epoxy groups in the molecule.

[0105] In the following general formula (3), * represents a bonding portion, and R 1 ~R 8 Each independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aromatic group having 4 to 18 carbon atoms.

[0106] [Chemistry 4]

[0107]

[0108] In the general formula (3), R 1 ~R 4 Each of them independently is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and still more preferably a methyl group.

[0109] Furthermore, in the general formula (3), R 5 ~R 8 Each of them independently is preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.

[0110] From the viewpoint of achieving both suppression of increase in high-temperature elastic coefficient and formability, the content of the second epoxy resin relative to the total amount of all epoxy resins contained in the sealing composition is preferably 30% to 90% by mass, more preferably 50% to 80% by mass, and even more preferably 60% to 75% by mass.

[0111] The content of the second epoxy resin relative to the entire sealing composition is preferably 1.0% by mass to 5.0% by mass, more preferably 1.5% by mass to 4.0% by mass, and still more preferably 1.7% by mass to 3.0% by mass.

[0112] (Third epoxy resin)

[0113] The third epoxy resin is not particularly limited as long as it is a resin other than the first epoxy resin and is an epoxy resin having a benzene ring and at least two epoxy groups bonded to the para position of the benzene ring directly or via a linking group, and the benzene ring has no substituents at the ortho and meta positions of the bonding positions of the two epoxy groups.

[0114] The number of benzene rings in one molecule of the third epoxy resin is not particularly limited, and may be in the range of 1 to 3, preferably 1 to 2, and more preferably 1.

[0115] When the third epoxy resin has two or more benzene rings, it is preferred that the two or more benzene rings are substituted only at the para position (ie, have no substituent at the ortho position and the meta position).

[0116] The third epoxy resin may further have an aromatic hydrocarbon ring other than the benzene ring.

[0117] The number of epoxy groups in one molecule of the third epoxy resin is not particularly limited as long as it is two or more, but is preferably two.

[0118] The epoxy group may be contained in the molecule of the third epoxy resin as part of at least one selected from glycidyl group, glycidyloxy group, glycidyloxycarbonyl group, glycidylamino group, epoxycycloalkyl group (epoxycyclopentyl group, epoxycyclohexyl group, epoxycyclooctyl group, etc.).

[0119] The third epoxy resin preferably has a glycidyloxy group in the molecule, and more preferably has a glycidyloxy group directly bonded to a benzene ring in the molecule. Furthermore, when the third epoxy resin has two or more glycidyloxy groups, it is preferred that all of the two or more glycidyloxy groups are directly bonded to the benzene ring.

[0120] Examples of the third epoxy resin include epoxy resins represented by the following general formula (4).

[0121] [Chemistry 5]

[0122]

[0123] In the general formula (4), E 1 、E 2 and L 2 Respectively represent E in the general formula (2) 1 、E 2 and L 2 In the general formula (4), a1 represents the same number as a1 in the general formula (2).

[0124] The content of the total epoxy resin in the sealing composition is preferably 2.0% by mass to 6% by mass, more preferably 3.0% by mass to 5.5% by mass, and still more preferably 3.0% by mass to 5.0% by mass.

[0125] The content of the total epoxy resin in the sealing composition excluding the inorganic filler is preferably 40% by mass to 70% by mass, more preferably 45% by mass to 64% by mass, and still more preferably 48% by mass to 55% by mass.

[0126] - Hardener -

[0127] The sealing composition contains a curing agent. The type of the curing agent is not particularly limited, and a known curing agent can be used.

[0128] Examples of the curing agent include phenol curing agents, amine curing agents, anhydride curing agents, polythiol curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents. From the perspective of obtaining a sealing composition that maintains fluidity and has excellent reflow resistance, the curing agent is preferably a phenol curing agent, an amine curing agent, and an anhydride curing agent, and more preferably a phenol curing agent. One type of the curing agent may be used alone, or two or more types may be used in combination.

[0129] Examples of the phenol curing agent include phenol resins and polyphenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, polyphenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted bisphenols; novolac-type phenol resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, and aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene with an aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde under an acidic catalyst; aralkyl-type phenol resins (phenylene) synthesized from the phenolic compounds and dimethoxy-p-xylene (p-xylene), bis(methoxymethyl)biphenyl, and the like; The present invention also includes phenol resins modified by polyols (such as phenol aralkyl resins, naphthol aralkyl resins, etc.); p-xylylene (p-xylylene) modified phenol resins; m-xylylene (m-xylylene) modified phenol resins; melamine modified phenol resins; terpene modified phenol resins; dicyclopentadiene type phenol resins and dicyclopentadiene type naphthol resins synthesized by copolymerization of the phenolic compounds and dicyclopentadiene; cyclopentadiene modified phenol resins; polycyclic aromatic ring modified phenol resins; biphenyl type phenol resins; triphenylmethane type phenol resins obtained by condensing or co-condensing the phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; phenol resins obtained by copolymerizing two or more of these, etc. These phenol resins and polyphenol compounds may be used alone or in combination of two or more.

[0130] Among these, the phenol curing agent is preferably a polyfunctional phenol resin, among which a novolac-type phenol resin, an aralkyl-type phenol resin, and a triphenylmethane-type phenol resin are preferred, and a triphenylmethane-type phenol resin is more preferred.

[0131] Examples of the triphenylmethane type phenol resin include phenol resins represented by the following general formula (5).

[0132] [Chemistry 6]

[0133]

[0134] In the general formula (5), R 11 ~R 15 Each independently represents a monovalent organic group having 1 to 18 carbon atoms, b1 and b2 each independently represent an integer of 0 to 4, b3 represents an integer of 0 to 3, b4 and b5 each independently represent an integer of 0 to 4, and n represents 0 to 10.

[0135] As R in the general formula (5) 11 ~R 15Examples of the monovalent organic group having 1 to 18 carbon atoms include a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted aralkyl group.

[0136] b1 to b5 in the general formula (5) are preferably integers of 0 to 1, and more preferably 0.

[0137] In the general formula (5), n is preferably 1-7, more preferably 2-5.

[0138] The functional group equivalent of the curing agent is not particularly limited, but is preferably 70 g / eq to 500 g / eq, more preferably 70 g / eq to 300 g / eq, and still more preferably 80 g / eq to 250 g / eq from the viewpoint of moldability. The functional group equivalent refers to a value measured in accordance with JIS K0070:1992.

[0139] When the curing agent is solid, the softening point or melting point is not particularly limited. From the viewpoint of formability and reflow resistance, it is preferably 40°C to 180°C, and from the viewpoint of handleability during the manufacture of the sealing composition, the softening point or melting point is more preferably 50°C to 130°C, and further preferably 55°C to 100°C.

[0140] The melting point or softening point of the curing agent is set to a value measured in the same manner as the melting point or softening point of the epoxy resin.

[0141] Regarding the mixing ratio of the epoxy resin and the hardener, from the viewpoint of suppressing the respective unreacted components to a minimum, it is preferred to mix the hardener so that the equivalent of the functional group of the hardener (for example, the phenolic hydroxyl group in the case of the phenol resin) becomes 0.5 to 1.5 equivalents per 1 equivalent of the epoxy group of the epoxy resin, and it is particularly preferred to mix the hardener so that it becomes 0.7 to 1.2 equivalents.

[0142] -Inorganic fillers-

[0143] The inorganic filler may be used alone or in combination of two or more.

[0144] As a case where two or more inorganic fillers are used in combination, there is mentioned a case where two or more inorganic fillers different in composition, average particle diameter, shape, etc. are used.

[0145] The shape of the inorganic filler is not particularly limited, and examples thereof include powder, spherical, and fibrous shapes. A spherical shape is preferred from the viewpoint of fluidity during molding of the sealing composition and mold wear resistance.

[0146] As the inorganic filler, it is preferred that alumina is contained from the viewpoint of high thermal conductivity. The inorganic filler may be entirely alumina, or alumina and other inorganic fillers may be used in combination.

[0147] Other inorganic fillers that can be used together with alumina include spherical silica, crystalline silica and other silicon dioxide, zircon, magnesium oxide, calcium silicate, calcium carbonate, potassium titanate, silicon carbide, silicon nitride, boron nitride, beryllium oxide, zirconium oxide, etc. Furthermore, inorganic fillers having a flame retardant effect include aluminum hydroxide, zinc borate, etc.

[0148] When alumina and another inorganic filler are used together as the inorganic filler, it is preferred to use silica as the other inorganic filler from the viewpoint of fluidity.

[0149] When alumina and silica are used together as inorganic fillers, the content of alumina in the inorganic filler is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 85% by mass or more, and particularly preferably 95% by mass or more. Furthermore, the content of alumina in the inorganic filler may be 99.6% by mass or less.

[0150] The content of the inorganic filler is preferably 60% by volume or more, more preferably 70% by volume or more, and even more preferably 75% by volume or more, based on the total volume of the sealing composition, from the viewpoints of hygroscopicity, reduction in linear expansion coefficient, improvement in strength, and solder heat resistance.

[0151] Moreover, from the viewpoint of high thermal conductivity, the content of the inorganic filler is particularly preferably 78% by volume or more, and extremely preferably 80% by volume or more, relative to the entirety of the sealing composition. From the viewpoint of the formability and fluidity of the sealing composition, the content of the inorganic filler is preferably 95% by volume or less, more preferably 90% by volume or less, and further preferably 85% by volume or less, relative to the entirety of the sealing composition. From the viewpoint of taking into account both high thermal conductivity and the formability and fluidity of the sealing composition, the content of the inorganic filler is preferably 78% by volume to 90% by volume, more preferably 78% by volume to 85% by volume, and further preferably 80% by volume to 85% by volume.

[0152] The average particle size of the inorganic filler is preferably 4 μm to 100 μm, more preferably 7 μm to 70 μm, and still more preferably 7 μm to 40 μm. In the present disclosure, the average particle size of the inorganic filler refers to the average particle size of alumina when alumina is used alone as the inorganic filler, and refers to the average particle size of the inorganic filler as a whole when alumina and other inorganic fillers are used as the inorganic filler.

[0153] The thermal conductivity of the cured product of the sealing composition tends to increase as the average particle size of the inorganic filler increases.

[0154] The average particle size of the inorganic filler can be measured by the following method.

[0155] Add 1% to 5% by mass of the inorganic filler as the object of measurement and 1% to 8% by mass of the surfactant to the solvent (pure water), and vibrate for 30 seconds to 5 minutes using a 110W ultrasonic cleaner to disperse the inorganic filler. Inject about 3 mL of the dispersion into the measuring unit and measure at 25°C. The measuring device uses a laser diffraction particle size distribution meter (Horiba, Ltd., LA920) to measure the volume-based particle size distribution. The average particle size is calculated as the particle size (D50%) when the accumulation from the small diameter side becomes 50% in the volume-based particle size distribution. In addition, the refractive index is the refractive index of aluminum oxide. When the inorganic filler is a mixture of aluminum oxide and other inorganic fillers, the refractive index is set to the refractive index of aluminum oxide.

[0156] The specific surface area of ​​the inorganic filler is preferably 0.7 m2 from the viewpoint of fluidity and formability. 2 / g~4.0m 2 / g, more preferably 0.9m 2 / g~3.0m 2 / g, and more preferably 1.0 m 2 / g~2.5m 2 / g.

[0157] The fluidity of the sealing composition tends to increase as the specific surface area of ​​the inorganic filler decreases.

[0158] In the present disclosure, the specific surface area of ​​an inorganic filler refers to the specific surface area of ​​alumina when alumina is used alone as an inorganic filler, and refers to the specific surface area of ​​a mixture of inorganic fillers when alumina and other inorganic fillers are used together as inorganic fillers.

[0159] The specific surface area (Brunauer-Emmett-Teller, BET) specific surface area) of the inorganic filler can be measured according to JIS Z 8830:2013 and based on nitrogen absorption energy. As an evaluation device, QUANTACHROME: AUTOSORB-1 (trade name) can be used. When measuring the BET specific surface area, it is believed that the moisture adsorbed on the sample surface and structure will affect the gas adsorption energy, so it is preferred to first remove the moisture by heating.

[0160] In the pretreatment, the measuring cell into which 0.05 g of the measuring sample was put was depressurized to 10 Pa or less by a vacuum pump, and then heated at 110° C. for more than 3 hours, and then naturally cooled to room temperature (25° C.) while maintaining the depressurized state. After the pretreatment, the evaluation temperature was set to 77 K, and the evaluation pressure range was set to be less than 1 in relative pressure (equilibrium pressure relative to saturated vapor pressure) for measurement.

[0161] -Other ingredients-

[0162] (hardening accelerator)

[0163] The sealing composition may further contain a hardening accelerator. The type of the hardening accelerator is not particularly limited, and a known hardening accelerator can be used.

[0164] Specific examples of the curing accelerator include cyclic amidine compounds such as 1,8-diaza-bicyclo[5.4.0]undecene-7, 1,5-diaza-bicyclo[4.3.0]nonene, and 5,6-dibutylamino-1,8-diaza-bicyclo[5.4.0]undecene-7; compounds having intramolecular polarization obtained by adding maleic anhydride, 1,4-benzoquinone, 2,5-toluoquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone to the cyclic amidine compounds; compounds having a π bond such as diazonophenylmethane and phenol resins; and compounds having intramolecular polarization such as benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol. Tertiary amine compounds; derivatives of tertiary amine compounds; imidazole compounds such as 2-methylimidazole, 2-phenylimidazole, and 2-phenyl-4-methylimidazole; derivatives of imidazole compounds; organic phosphine compounds such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, tri(4-methylphenyl)phosphine, diphenylphosphine, and phenylphosphine; phosphorus compounds with intramolecular polarization formed by adding maleic anhydride, the quinone compounds, diazonophenylmethane, phenol resin, and other compounds having π bonds to organic phosphine compounds; tetraphenylboron salts such as tetraphenylphosphonium tetraphenylborate, triphenylphosphine tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, and N-methylmorpholine tetraphenylborate; derivatives of tetraphenylboron salts; adducts of phosphine compounds such as triphenylphosphonium-triphenylborane and N-methylmorpholine tetraphenylphosphonium-tetraphenylborate and tetraphenylboron salts, etc. The hardening accelerator may be used alone or in combination of two or more.

[0165] Among these, the curing accelerator is preferably a phosphorus-based curing accelerator, more preferably an organic phosphine compound, an adduct of an organic phosphine compound, and an adduct of a phosphine compound and a tetraphenylborate salt, still more preferably an organic phosphine compound and an adduct of an organic phosphine compound, and particularly preferably a compound formed by adding a quinone compound to an organic phosphine compound.

[0166] The content rate of the curing accelerator is preferably 0.1% by mass to 8% by mass with respect to the total amount of the epoxy resin and the curing agent.

[0167] (Ion scavenger)

[0168] The sealing composition may further contain an ion scavenger.

[0169] The ion scavenger that can be used in the present disclosure is not particularly limited as long as it is an ion scavenger generally used in a sealing material for semiconductor device manufacturing applications. Examples of the ion scavenger include compounds represented by the following general formula (6) or the following general formula (7).

[0170] Mg 1-a Al a (OH)2(CO3) a / 2 ·uH2O (6)

[0171] (In the general formula (6), a is 0 < a ≤ 0.5, and u is a positive number)

[0172] BiO b (OH) c (NO3) d (7)

[0173] (In the general formula (7), b is 0.9 ≤ b ≤ 1.1, c is 0.6 ≤ c ≤ 0.8, and d is 0.2 ≤ d ≤ 0.4)

[0174] The ion scavenger can be obtained as a commercially available product. As the compound represented by the general formula (6), for example, "DHT-4A" (trade name, Kyowa Chemical Industry Co., Ltd.) can be obtained as a commercially available product. Moreover, as the compound represented by the general formula (7), for example, "IXE500" (trade name, Toagosei Co., Ltd.) can be obtained as a commercially available product.

[0175] Moreover, as ion scavengers other than those described above, hydrous oxides of elements selected from magnesium, aluminum, titanium, zirconium, antimony, etc. can be cited.

[0176] The ion scavenger can be used alone or in combination of two or more.

[0177] When the sealing composition contains an ion scavenger, the content of the ion scavenger is preferably 1 part by mass or more relative to 100 parts by mass of the epoxy resin from the viewpoint of achieving sufficient moisture-resistant reliability. From the viewpoint of fully exerting the effects of other components, the content of the ion scavenger is preferably 15 parts by mass or less relative to 100 parts by mass of the epoxy resin.

[0178] The average particle size of the ion scavenger is preferably 0.1 μm to 3.0 μm, and the maximum particle size is preferably 10 μm or less. The average particle size of the ion scavenger can be measured in the same manner as in the case of the inorganic filler.

[0179] (Coupling agent)

[0180] The sealing composition may further contain a coupling agent. The type of the coupling agent is not particularly limited, and a known coupling agent may be used. As the coupling agent, silane coupling agents, titanium coupling agents, etc. may be listed. The coupling agent may be used alone or in combination of two or more.

[0181] Examples of the silane coupling agent include vinyl trichlorosilane, vinyl triethoxysilane, vinyl tri(β-methoxyethoxy)silane, γ-methacryloxypropyl trimethoxysilane, 8-methacryloxyoctyl trimethoxysilane, β-(3,4-epoxycyclohexyl)ethyl trimethoxysilane, γ-glycidoxypropyl trimethoxysilane, vinyl triacetoxysilane, γ-mercaptopropyl trimethoxysilane, γ-aminopropyl triethoxysilane, γ-[bis(β-hydroxyethyl)]aminopropyl triethoxysilane, N-β- (Aminoethyl)-γ-aminopropyltrimethoxysilane, γ-(β-aminoethyl)aminopropyldimethoxymethylsilane, N-(trimethoxysilylpropyl)ethylenediamine, N-(dimethoxymethylsilylisopropyl)ethylenediamine, methyltrimethoxysilane, methyltriethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, etc.

[0182] Examples of the titanium coupling agent include isopropyl triisostearoyl titanate, isopropyl tri(dioctyl pyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(di-tridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl phosphite) titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, bis(dioctyl pyrophosphate)ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryloyl isostearyl titanate, isopropyl tri-dodecylbenzenesulfonyl titanate, isopropyl isostearyl diacryloyl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumylphenyl titanate, and tetraisopropyl bis(dioctyl phosphite) titanate.

[0183] -Specific silane compounds-

[0184] The sealing composition may contain a silane compound having a structure in which a chain hydrocarbon group having 6 or more carbon atoms is bonded to a silicon atom (hereinafter also referred to as a "specific silane compound") as the coupling agent.

[0185] The chain hydrocarbon group may be branched or may have a substituent. In addition, in the present disclosure, the carbon number of the chain hydrocarbon group refers to the carbon number of the carbon excluding the branch or the substituent. The chain hydrocarbon group may contain an unsaturated bond or may not contain it, preferably not containing an unsaturated bond.

[0186] The number of chain hydrocarbon groups bonded to the silicon atom in the specific silane compound may be 1 to 4, preferably 1 to 3, more preferably 1 or 2, and still more preferably 1.

[0187] When the number of chain hydrocarbon groups bonded to silicon atoms in the specific silane compound is 1 to 3, the atoms or atomic groups other than the chain hydrocarbon groups bonded to the silicon atoms are not particularly limited, and may be independently hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, alkoxy groups, aryl groups, aryloxy groups, etc. Among them, it is preferred that one or more alkoxy groups are bonded to the silicon atom in addition to the chain hydrocarbon group, and it is more preferred that one chain hydrocarbon group and three alkoxy groups are bonded to the silicon atom.

[0188] The carbon number of the chain hydrocarbon group of the specific silane compound is 6 or more, preferably 7 or more, and more preferably 8 or more from the viewpoint of suppressing viscosity. The upper limit of the carbon number of the chain hydrocarbon group of the specific silane compound is not particularly limited, but is preferably 12 or less, more preferably 11 or less, and further preferably 10 or less from the viewpoints of dispersibility in the resin, balance of physical properties of the cured product, and the like.

[0189] When the chain hydrocarbon group has a substituent, the substituent is not particularly limited. The substituent may be present at the terminal of the chain hydrocarbon group or may be present in the side chain of the chain hydrocarbon group.

[0190] The chain hydrocarbon group preferably has at least one functional group selected from (meth)acryloyl, epoxy and alkoxy (hereinafter also referred to as a specific functional group), more preferably has at least one functional group selected from (meth)acryloyl and epoxy, and further preferably has a (meth)acryloyl. The specific functional group may be present at the end of the chain hydrocarbon group or at the side chain of the chain hydrocarbon group. From the viewpoint of suppressing viscosity, the specific functional group is preferably present at the end of the chain hydrocarbon group.

[0191] When the chain hydrocarbon group has a (meth)acryloyl group, the (meth)acryloyl group may be directly bonded to the chain hydrocarbon group or may be bonded via other atoms or atomic groups. For example, the chain hydrocarbon group may also have a (meth)acryloyloxy group. Among them, the chain hydrocarbon group preferably has a methacryloyloxy group.

[0192] When the chain hydrocarbon group has an epoxy group, the epoxy group may be directly bonded to the chain hydrocarbon group or may be bonded via other atoms or atomic groups. For example, the chain hydrocarbon group may also have a glycidyloxy group, an alicyclic epoxy group, etc. Among them, the chain hydrocarbon group preferably has a glycidyloxy group.

[0193] In the case where the chain hydrocarbon group has an alkoxy group, the alkoxy group may be directly bonded to the chain hydrocarbon group, or may be bonded via other atoms or atomic groups, preferably directly bonded to the chain hydrocarbon group. The alkoxy group is not particularly limited, and may be a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, etc. Among them, the chain hydrocarbon group preferably has a methoxy group from the viewpoint of easy availability.

[0194] The equivalent weight (molecular weight / number of functional groups) of at least one functional group selected from (meth)acryloyl, epoxy and alkoxy in the specific silane compound is not particularly limited. From the viewpoint of reducing the viscosity of the sealing composition, it is preferably 200 g / eq to 420 g / eq, more preferably 210 g / eq to 405 g / eq, and further preferably 230 g / eq to 390 g / eq.

[0195] As specific silane compounds, hexyl trimethoxysilane, heptyl trimethoxysilane, octyl trimethoxysilane, hexyl triethoxysilane, heptyl triethoxysilane, octyl triethoxysilane, 6-glycidyloxy hexyl trimethoxysilane, 7-glycidyloxy heptyl trimethoxysilane, 8-glycidyloxy octyl trimethoxysilane, 6-(methyl) acryloxy hexyl trimethoxysilane, 7-(methyl) acryloxy heptyl trimethoxysilane, 8-(methyl) acryloxy octyl trimethoxysilane, decyl trimethoxysilane, etc. can be listed. Among them, from the perspective of low viscosity of the sealing composition, 8-glycidyloxy octyl trimethoxysilane and 8-methacryloxy octyl trimethoxysilane are preferred. The specific silane compound can be used alone or in combination of two or more.

[0196] The specific silane compound can be synthesized, or a commercially available specific silane compound can be used. Examples of commercially available specific silane compounds include KBM-3063 (hexyltrimethoxysilane), KBE-3063 (hexyltriethoxysilane), KBE-3083 (octyltriethoxysilane), KBM-4803 (8-glycidyloxyoctyltrimethoxysilane), KBM-5803 (8-methacryloyloxyoctyltrimethoxysilane), and KBM-3103C (decyltrimethoxysilane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0197] When the sealing composition contains a coupling agent, the content of the coupling agent is preferably 3 mass % or less, more preferably 2 mass % or less, and further preferably 1 mass % or less, based on the entire sealing composition. From the viewpoint of exerting its effect, it is preferably 0.1 mass % or more, more preferably 0.15 mass % or more, and further preferably 0.2 mass % or more.

[0198] Moreover, the content of the coupling agent may be 0.01 parts by mass or more, and may be 0.02 parts by mass or more, relative to 100 parts by mass of the inorganic filler. The content of the coupling agent is preferably 5 parts by mass or less, and more preferably 2.5 parts by mass or less, relative to 100 parts by mass of the inorganic filler. From the perspective of both fluidity and formability of the package, the content of the coupling agent is preferably 0.05 parts by mass to 2.0 parts by mass, more preferably 0.1 parts by mass to 1.5 parts by mass, and further preferably 0.2 parts by mass to 1.0 parts by mass, relative to 100 parts by mass of the inorganic filler.

[0199] (Release Agent)

[0200] The sealing composition may further contain a release agent. The type of the release agent is not particularly limited, and known release agents can be used. Specifically, higher fatty acids, palm wax, montan wax, polyethylene wax, etc. can be mentioned. The release agent can be used alone or in combination of two or more.

[0201] When the sealing composition contains a release agent, the content of the release agent is preferably 10% by mass or less, and is preferably 0.5% by mass or more, based on the total amount of the epoxy resin and the curing agent, in order to exhibit its effect.

[0202] (Colorants and Modifiers)

[0203] The sealing composition may contain a colorant (carbon black, etc.). Furthermore, the sealing composition may contain a modifier (silicone, silicone rubber, etc.). The colorant and the modifier may be used alone or in combination of two or more.

[0204] When conductive particles such as carbon black are used as a colorant, the content of conductive particles having a particle size of 10 μm or more is preferably 1% by mass or less.

[0205] When the sealing composition contains conductive particles, the content of the conductive particles is preferably 3% by mass or less relative to the total amount of the epoxy resin and the curing agent.

[0206] (Other additives)

[0207] The sealing composition may further contain other additives as required.

[0208] Examples of other additives include flame retardants, anion exchangers, plasticizers, etc. Furthermore, various additives well known in the above technical field may be added to the composition as necessary.

[0209] <Method for producing sealing composition>

[0210] The method for preparing the sealing composition is not particularly limited and can be carried out by a known method. For example, the sealing composition can be prepared by fully mixing a mixture of raw materials in a predetermined amount using a mixer, kneading it using a hot roll, an extruder, etc., and then cooling, pulverizing, etc. The state of the sealing composition is not particularly limited and can be powder, solid, liquid, etc.

[0211] <Semiconductor devices>

[0212] The semiconductor device of the present disclosure includes a semiconductor element and a cured product of the sealing composition of the present disclosure that seals the semiconductor element.

[0213] The method for sealing the semiconductor element using the sealing composition is not particularly limited, and a known method can be applied, such as transfer molding or the like, but compression molding, injection molding, compression molding, or the like can also be used.

[0214] The semiconductor device disclosed in the present invention is preferably used as an integrated circuit (IC), a large-scale integration (LSI), or the like.

[0215] [Example]

[0216] Hereinafter, examples of the present invention will be described, but the present invention is not limited thereto. In addition, the numerical values ​​in the tables are "parts by mass" unless otherwise specified.

[0217] <Examples 1 to 6 and Comparative Examples 1 and 2>

[0218] The components shown below were preliminarily mixed (dry blended) at the blending ratios (parts by mass) shown in Table 1, kneaded using a biaxial kneader, and cooled and pulverized to produce a powdered sealing composition.

[0219] In addition, the details of the components shown in Table 1 are as follows.

[0220] (A) Epoxy resin

[0221] Epoxy resin A1-1: a first epoxy resin, the epoxy resin represented by the general formula (2) (E 1 and E 2 All are glycidyloxy, L 1 is an ether bond, a1 and a2 are both 0, n is 1), epoxy equivalent "165g / eq", melting point "83°C"

[0222] Epoxy resin A1-2: a mixture of a first epoxy resin and a third epoxy resin, wherein the epoxy resin (E 1 and E 2 All are glycidyloxy, L 1 is the linking group represented by the structural formula (1), L 2 and L 3 are all p-phenylene, a1 and a2 are both 0 or 1, n is 1) and the epoxy resin (E 1 and E 2 All are glycidyloxy, L 2 is p-phenylene, a1 is 0 or 1), epoxy equivalent "140g / eq"

[0223] Epoxy resin A2-1: Second epoxy resin, Mitsubishi Chemical Co., Ltd., trade name "YX4000H", epoxy equivalent "192 g / eq", softening point "107°C", biphenyl type epoxy resin

[0224] Epoxy resin A2-2: Second epoxy resin, Nippon Steel Chemical & Material Co., Ltd., trade name "YSLV-70XY", epoxy equivalent "192 g / eq", melting point "67°C", bisphenol type epoxy resin

[0225] (B) Hardener

[0226] Phenolic resin B1: triphenylmethane type phenolic resin, AirWater Co., Ltd., trade name "HE910-09", hydroxyl equivalent "92g / eq to 104g / eq", softening point "75°C to 85°C"

[0227] (C) Hardening accelerator

[0228] Hardening accelerator C1: Phosphorus-based hardening accelerator (addition product of tributylphosphine and benzoquinone)

[0229] (D) Coupling agent

[0230] Coupling agent D1: 8-methacryloyloxyoctyltrimethoxysilane, Shin-Etsu Chemical Co., Ltd., trade name "KBM-5803"

[0231] (E) Release agent

[0232] Release agent E1: Montan wax, Clariant, trade name "HW-E"

[0233] (F) Colorant

[0234] Pigment F1: Carbon black, Mitsubishi Chemical Corporation, trade name "MA600"

[0235] (G) Additives

[0236] Additive G1: triphenylphosphine oxide, Beixing Chemical Industry Co., Ltd., trade name "TP-50"

[0237] (H) Modifier

[0238] Modifier H1: Silicone, Toray Dow Corning Co., Ltd., trade name "BY16-876"

[0239] (I) Inorganic fillers

[0240] Filler I1: Silica particles, Tokuyama Co., Ltd., trade name "CP-102", spherical, specific surface area "190m 2 / g~230m 2 / g”

[0241] Filler I2: Alumina particles, Admatechs, trade name "AE2000", spherical, average particle size "0.7 μm"

[0242] Filler I3: Alumina particles, Denka Co., Ltd., trade name "DAB10SITS1", spherical, average particle size "10 μm"

[0243] -evaluate-

[0244] The properties of the sealing compositions prepared in Examples and Comparative Examples were evaluated by the following property tests. The evaluation results are shown in Table 1 below.

[0245] (High temperature elastic coefficient)

[0246] Using the sealing composition obtained above, a test piece with a shape of 127mm×12.7mm×4mm was made by a transfer molding machine under the conditions of a metal mold temperature of 175°C, a molding pressure of 6.9MPa, and a curing time of 90 seconds. After that, post-curing was carried out at 175°C for 6 hours. Tensilon (A&D Company) was used as an evaluation device, and a three-point support bending test according to JIS-K-7171 (2016) was carried out at 260°C to obtain the bending elastic coefficient of the test piece.

[0247] The flexural elastic coefficient E is defined by the following formula, and the flexural elastic coefficient obtained by measurement at 260° C. is referred to as “high-temperature elastic coefficient”.

[0248] In the following formula, E is the bending elastic coefficient (MPa), P is the value of the load cell (N), y is the displacement (mm), l is the interval (span) = 64mm, w is the test piece width = 12.7mm, and h is the test piece thickness = 4mm.

[0249] [Number 1]

[0250]

[0251] (Thermal conductivity)

[0252] Using the sealing composition obtained above, a test piece for thermal conductivity evaluation was prepared by a transfer molding machine under the conditions of a metal mold temperature of 175°C to 180°C, a molding pressure of 7MPa, and a curing time of 300 seconds. Then, the thermal diffusivity in the thickness direction of the molded test piece was measured. The thermal diffusivity was measured by the Laser Flash method (device: LFA467 nanoflash, NETZSCH). Pulse light irradiation was carried out under the conditions of a pulse width of 0.31 (ms) and an applied voltage of 247V. The measurement was carried out at an ambient temperature of 25°C±1°C. In addition, the density of the test piece was measured using an electronic densimeter (AUX220, Shimadzu Corporation). The specific heat is the theoretical specific heat of the sealing composition calculated using the literature value of the specific heat of each material and the blending ratio.

[0253] Then, the specific heat and density are multiplied by the thermal diffusivity using equation (8) to obtain the value of thermal conductivity.

[0254] λ=α×Cp×ρ ···Formula (8)

[0255] (In formula (8), λ represents thermal conductivity (W / (m·K)), α represents thermal diffusivity (m 2 / s), Cp represents specific heat (J / (kg·K)), ρ represents density (kg / m 3 ))

[0256] [Table 1]

[0257]

[0258] According to the evaluation results in Table 1, it is clear that the sealing compositions of Examples 1 to 6 containing the first epoxy resin obtain a cured product with a high thermal conductivity compared to the sealing compositions of Comparative Examples 1 and 2 not containing the first epoxy resin. Moreover, the high-temperature elastic coefficient of the cured product of the sealing compositions of Examples 1 to 6 is equal to the high-temperature elastic coefficient of the cured product of the sealing compositions of Comparative Examples 1 and 2. In other words, it can be seen that the sealing compositions of Examples 1 to 6 suppress the high-temperature elastic coefficient of the cured product to a low level compared to the sealing compositions of Comparative Examples 1 and 2, and the thermal conductivity of the cured product is improved.

[0259] The entire disclosure of Japanese Patent Application No. 2019-035227 is incorporated into the present disclosure by reference.

[0260] All documents, patent applications, and technical specifications in the present disclosure are hereby incorporated by reference into the present disclosure to the same extent as if each individual document, patent application, or technical specification was specifically and individually indicated to be incorporated by reference.

Claims

1. A sealing composition comprising: The first epoxy resin has at least two benzene rings and at least one ether bond connecting the two benzene rings directly or via a linking group in the molecule, and the two benzene rings have no substituents at the ortho and meta positions of the bonding positions of the ether bonds; The second epoxy resin has a melting point or softening point of 50°C or more; Hardener; and Inorganic filler, wherein the inorganic filler is alumina and silica, wherein the content of alumina in the inorganic filler is 50 mass % or more, The first epoxy resin comprises an epoxy resin represented by the following general formula (2): In the general formula (2), E 1 and E 2 Each independently represents a monovalent group containing an epoxy group, L 1 represents a divalent linking group represented by the following structural formula (1), L 2 and L 3 Each independently represents an aromatic hydrocarbon ring, a1 and a2 are 0 or 1, and n represents an integer of 1 to 2, In the structural formula (1), * represents a bonding portion to a benzene ring. 2 . The sealing composition according to claim 1 , wherein the content of the inorganic filler is 78% by volume or more based on the entire sealing composition. 3 . The sealing composition according to claim 1 , wherein a content of the second epoxy resin is 80% by mass or less based on a total amount of the epoxy resin contained in the sealing composition. 4 . The sealing composition according to claim 1 , wherein a content of the second epoxy resin is 50% by mass or more based on a total amount of the epoxy resin contained in the sealing composition. 5 . The sealing composition according to claim 1 , wherein the first epoxy resin has two epoxy groups in a molecule.

6. The sealing composition according to claim 1 or 2, further comprising a third epoxy resin, wherein the third epoxy resin is a resin other than the first epoxy resin, and comprises a benzene ring and at least two epoxy groups bonded to the para position of the benzene ring directly or via a linking group, and the benzene ring has no substituent at the ortho position and the meta position of the bonding position of the two epoxy groups. 7 . A semiconductor device comprising a semiconductor element and a cured product of the sealing composition according to claim 1 for sealing the semiconductor element.

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