Thermosetting resin composition and semiconductor device

Abstract

To provide a thermosetting resin composition excellent in reflow resistance.SOLUTION: The thermosetting resin composition contains a thermosetting resin, a curing agent, and an inorganic filler. The inorganic filler contains an inorganic filler surface-treated with a coupling agent containing a primary amino group. The content of the inorganic filler surface-treated with the coupling agent containing the primary amino group is 20-60 mass% based on the whole thermosetting resin composition.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a thermosetting resin composition and a semiconductor device. [Background technology]

[0002] In recent years, electronic devices have become smaller, lighter, and more powerful, leading to higher packaging densities. As a result, the mainstream of electronic component devices is shifting from conventional pin insertion packages to surface mount packages.

[0003] Surface-mount packages differ from conventional pin-insertion packages in their mounting method. Specifically, when attaching pins to a wiring board, conventional pin-insertion packages require soldering from the backside of the wiring board after the pins are inserted into the board. This prevents the package from being directly exposed to high temperatures. However, with surface-mount packages, the entire electronic component device is processed using a solder bath, reflow equipment, or the like, so the package is directly exposed to soldering temperatures (reflow temperatures). As a result, if the package absorbs moisture, the moisture rapidly expands during soldering. The resulting vapor pressure acts as peel stress, causing peeling between the insert (e.g., semiconductor element, lead frame) and the cured product of the encapsulating material (composed of a thermosetting resin composition) that encapsulates the insert. This can lead to package cracking, poor electrical characteristics, and other problems. Therefore, there is a need for an encapsulating material and its cured product that has excellent adhesion to the insert and, ultimately, excellent solder heat resistance (reflow resistance).

[0004] To meet the above demands, the use of silane coupling agents as modifiers for inorganic fillers contained in sealing materials has been investigated. Specifically, the use of epoxy group-containing silane coupling agents or amino group-containing silane coupling agents (see, for example, Patent Document 1), the use of sulfur atom-containing silane coupling agents (see, for example, Patent Document 2), etc. has been investigated.

[0005] Furthermore, as an epoxy resin composition having excellent reflow resistance, an epoxy resin composition containing, as essential components, (A) an epoxy resin, (B) a phenolic resin, (C) a curing accelerator, (D) a phosphazene compound, (E) silica, and (F) at least one silane coupling agent selected from the group consisting of γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidylpropyltriethoxysilane, and γ-glycidylpropyltrimethoxysilane has been disclosed (see, for example, Patent Document 3). Patent Document 3 uses silica that has been surface-treated with a silane coupling agent. The content of the surface-treated silica in the total epoxy resin composition is 85% by mass to 93% by mass. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 11-147939 [Patent Document 2] Japanese Patent Application Laid-Open No. 2000-103940 [Patent Document 3] Japanese Patent Application Laid-Open No. 2004-67774 Summary of the Invention [Problem to be solved by the invention]

[0007] However, even with the sealing materials formed from the epoxy resin compositions described in Patent Documents 1 and 2, the current situation is that they are still unable to provide practically sufficient reflow resistance. On the other hand, the epoxy resin composition described in Patent Document 3 has a high content of surface-treated silica, which may deteriorate the flowability of the epoxy resin composition and cause unfilled areas to easily occur, which tends to deteriorate the reflow resistance. The present disclosure has been made in view of the above-described conventional circumstances, and has an object to provide a thermosetting resin composition having excellent reflow resistance and a semiconductor device using this thermosetting resin composition. [Means for solving the problem]

[0008] Specific means for achieving the above object are as follows. <1> Contains a thermosetting resin, a curing agent, and an inorganic filler, the inorganic filler includes an inorganic filler that has been surface-treated with a coupling agent containing a primary amino group, A thermosetting resin composition, wherein the content of the inorganic filler that has been surface-treated with a coupling agent containing a primary amino group is 20% by mass to 60% by mass relative to the entire thermosetting resin composition. <2> The proportion of the inorganic filler surface-treated with the coupling agent containing a primary amino group in the entire inorganic filler is 75 mass % or less. <1> The thermosetting resin composition according to claim 1. <3> The amount of the coupling agent treated in the inorganic filler surface-treated with the coupling agent containing a primary amino group is 0.1 to 5 parts by mass relative to 100 parts by mass of the inorganic filler before being surface-treated with the coupling agent containing a primary amino group. <1> or <2> The thermosetting resin composition according to claim 1. <4> The coupling agent is an aminoalkyltrialkoxysilane <1> ~ <3> 10. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is a thermosetting resin composition having a viscosity of 1000 MPa or more. <5> The angle of repose of the inorganic filler surface-treated with the coupling agent containing a primary amino group is 50° to 60°. <1> ~ <4> 10. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is a thermosetting resin composition having a viscosity of 1000 MPa or more. <6> The bulk density of the inorganic filler surface-treated with the coupling agent containing a primary amino group is 1.15 g / cm 3 ~1.40g / cm 3 is <1> ~ <5> 10. The thermosetting resin composition according to claim 1, wherein the thermosetting resin composition is a thermosetting resin composition having a viscosity of 1000 MPa or more. <7> A semiconductor element and a device for sealing the semiconductor element <1> ~ <6> and a cured product of the thermosetting resin composition according to any one of the above. <8> It is a surface mount type <7> The semiconductor device according to claim 1. <9> Both surfaces of the semiconductor element are in contact with the cured product directly or via a metal substrate. <7> or <8> The semiconductor device according to claim 1. [Effects of the Invention]

[0009] According to the present disclosure, it is possible to provide a thermosetting resin composition having excellent reflow resistance and a semiconductor device using this thermosetting resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0010] Hereinafter, embodiments of the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments. In the following embodiments, components (including element steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the present disclosure.

[0011] In the present disclosure, the term "process" includes not only a process that is independent of other processes, but also a process that cannot be clearly distinguished from other processes as long as the purpose of the process is achieved. In the present disclosure, numerical ranges indicated using "to" include the numerical values ​​before and after "to" as the minimum and maximum values, respectively. In the numerical ranges described in stages in this disclosure, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in the numerical ranges described in this disclosure, the upper or lower limit value of that numerical range may be replaced with a value shown in the examples. In the present disclosure, each component may contain multiple substances corresponding to the component. When multiple substances corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple substances present in the composition, unless otherwise specified. In the present disclosure, the particles corresponding to each component may contain multiple types of particles. When multiple types of particles corresponding to each component are present in the composition, the particle size of each component means the value for a mixture of the multiple types of particles present in the composition, unless otherwise specified.

[0012] <Thermosetting resin composition> The thermosetting resin composition of the present disclosure contains a thermosetting resin, a curing agent, and an inorganic filler, the inorganic filler being surface-treated with a coupling agent containing a primary amino group, and the content of the inorganic filler surface-treated with the coupling agent containing a primary amino group is 20% by mass to 60% by mass. Hereinafter, the "inorganic filler surface-treated with a coupling agent containing a primary amino group" may be referred to as a specific inorganic filler. The reason why the thermosetting resin composition of the present disclosure has excellent reflow resistance is not clear, but is presumed to be as follows. When the content of the specific inorganic filler is 20% by mass or more, the adhesion of the specific inorganic filler to inserts such as resins, semiconductor elements, and lead frames tends to improve. On the other hand, when the content of the specific inorganic filler is 60% by mass or less, the reaction between the primary amino groups present on the surface of the specific inorganic filler and thermosetting resins such as epoxy resins tends to be suppressed, and the occurrence of unfilled areas due to deterioration of the fluidity of the thermosetting resin composition tends to be suppressed. From the above, it is presumed that a thermosetting resin composition with excellent reflow resistance can be obtained by setting the content of the specific inorganic filler to 20% by mass to 60% by mass.

[0013] The thermosetting resin composition of the present disclosure contains a thermosetting resin, a curing agent, and an inorganic filler, and may contain other components as needed. Each component contained in the thermosetting resin composition of the present disclosure will be described in detail below.

[0014] (thermosetting resin) The thermosetting resin composition contains a thermosetting resin. The type of thermosetting resin is not particularly limited, and examples include epoxy resins, phenolic resins, thiol resins, urea resins, melamine resins, urethane resins, silicone resins, maleimide resins, and unsaturated polyester resins. In the present disclosure, "thermosetting resins" include those that exhibit both thermoplastic and thermosetting properties, such as acrylic resins containing epoxy groups. Thermosetting resins may be solid or liquid at room temperature and normal pressure (e.g., 25°C and atmospheric pressure), and are preferably solid. Thermosetting resins may be used alone or in combination of two or more.

[0015] The thermosetting resin preferably includes an epoxy resin. The type of epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. Specifically, novolac epoxy resins (phenol novolac epoxy resins, orthocresol novolac epoxy resins, etc.) are obtained by epoxidizing novolac resins obtained by condensing or co-condensing, under an acid catalyst, at least one phenolic compound selected from the group consisting of phenolic compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, etc., and naphthol compounds such as α-naphthol, β-naphthol, dihydroxynaphthalene, etc., with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, etc.; triphenylmethane epoxy resins are obtained by epoxidizing triphenylmethane phenolic resins obtained by condensing or co-condensing, under an acid catalyst, the above phenolic compounds with aromatic aldehyde compounds such as benzaldehyde, salicylaldehyde, etc.; and novolac resins obtained by co-condensing, under an acid catalyst, the above phenolic compounds and naphthol compounds with an aldehyde compound, etc., are epoxidized. diphenylmethane-type epoxy resins, which are diglycidyl ethers of bisphenol A, bisphenol F, etc.; biphenyl-type epoxy resins, which are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resins, which are diglycidyl ethers of stilbene-based phenolic compounds; sulfur-containing epoxy resins, which are diglycidyl ethers of bisphenol S, etc.; epoxy resins, which are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester-type epoxy resins, which are glycidyl esters of polycarboxylic acids such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidylamine-type epoxy resins, in which the active hydrogen bonded to the nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, etc. is substituted with a glycidyl group; and dicyclopentadiene-type epoxy resins, which are epoxidized co-condensation resins of dicyclopentadiene and phenolic compounds.Alicyclic epoxy resins such as vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, which are produced by epoxidizing the olefin bonds in the molecule; paraxylylene-modified epoxy resins, which are glycidyl ethers of paraxylylene-modified phenolic resins; metaxylylene-modified epoxy resins, which are glycidyl ethers of metaxylylene-modified phenolic resins; terpene-modified epoxy resins, which are glycidyl ethers of terpene-modified phenolic resins; and dicyclopentadiene-modified phenolic resins, which are glycidyl ethers of dicyclopentadiene-modified phenolic resins. Examples of suitable epoxy resins include pentadiene-modified epoxy resins, cyclopentadiene-modified epoxy resins, which are glycidyl ethers of cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified epoxy resins, which are glycidyl ethers of polycyclic aromatic ring-modified phenolic resins; naphthalene-type epoxy resins, which are glycidyl ethers of naphthalene ring-containing phenolic resins; halogenated phenol novolac-type epoxy resins; hydroquinone-type epoxy resins; trimethylolpropane-type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; and aralkyl-type epoxy resins obtained by epoxidizing aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins. Further examples of suitable epoxy resins include epoxidized silicone resins and aminophenol-type epoxy resins, which are glycidyl ethers of aminophenols. These epoxy resins may be used alone or in combination of two or more.

[0016] Among the above epoxy resins, from the viewpoint of a balance between heat resistance and fluidity, epoxy resins selected from the group consisting of biphenyl-type epoxy resins, stilbene-type epoxy resins, diphenylmethane-type epoxy resins, sulfur-atom-containing epoxy resins, novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, triphenylmethane-type epoxy resins, copolymer-type epoxy resins, and aralkyl-type epoxy resins (these are referred to as "specific epoxy resins"). The specific epoxy resins may be used alone or in combination of two or more.

[0017] When the epoxy resin contains a specific epoxy resin, the content of the specific epoxy resin is preferably 30% by mass or more, and more preferably 50% by mass or more, of the total epoxy resin, from the viewpoint of exhibiting the performance of the specific epoxy resin.

[0018] Among the specific epoxy resins, from the viewpoint of fluidity, biphenyl-type epoxy resins, stilbene-type epoxy resins, diphenylmethane-type epoxy resins, and sulfur-atom-containing epoxy resins are more preferred, and from the viewpoint of heat resistance, dicyclopentadiene-type epoxy resins, triphenylmethane-type epoxy resins, and aralkyl-type epoxy resins are preferred. Specific examples of preferred epoxy resins are shown below.

[0019] The biphenyl type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, an epoxy resin represented by the following general formula (II) is preferred. Among the epoxy resins represented by the following general formula (II), R 8 When the oxygen atom is substituted at the 4 and 4' positions, the 3, 3', 5, and 5' positions are methyl groups, and the other R 8 YX-4000H (Mitsubishi Chemical Corporation, product name) where R is a hydrogen atom, 8 4,4'-bis(2,3-epoxypropoxy)biphenyl, where R is a hydrogen atom, 8 When is a hydrogen atom and R 8 When the oxygen atom is substituted at the 4 and 4' positions, the 3, 3', 5, and 5' positions are methyl groups, and the other R8 is a hydrogen atom, YL-6121H (trade name, Mitsubishi Chemical Corporation) and the like are commercially available.

[0020] [ka]

[0021] In formula (II), R 8 represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an aromatic group having 6 to 18 carbon atoms, and may all be the same or different. n is an average value and represents a number of 0 to 10.

[0022] The stilbene type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton. For example, an epoxy resin represented by the following general formula (III) is preferred. Among the epoxy resins represented by the following general formula (III), R 9 When the oxygen atom is substituted at the 4 and 4' positions, the 3, 3', 5, and 5' positions are methyl groups, and the other R 9 is a hydrogen atom, and R 10 are all hydrogen atoms, and R 9 Three of the 3, 3', 5, and 5' positions are methyl groups, one is a t-butyl group, and the remaining R 9 is a hydrogen atom, and R 10 and mixtures of those in which all of the above are hydrogen atoms.

[0023] [ka]

[0024] In formula (III), R 9 and R 10 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different from each other. n is an average value and represents a number of 0 to 10.

[0025] The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, an epoxy resin represented by the following general formula (IV) is preferred. Among the epoxy resins represented by the following general formula (IV), R 11 are all hydrogen atoms, and R 12 When the oxygen atom is substituted at the 4 and 4' positions, the 3, 3', 5, and 5' positions are methyl groups, and the other R 12 YSLV-80XY (Nippon Steel Chemical & Material Co., Ltd., product name) in which is a hydrogen atom is commercially available.

[0026] [ka]

[0027] In formula (IV), R 11 and R 12 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different from each other. n is an average value and represents a number from 0 to 10.

[0028] The sulfur atom-containing epoxy resin is not particularly limited as long as it is an epoxy resin containing a sulfur atom. For example, an epoxy resin represented by the following general formula (V) can be mentioned. Among the epoxy resins represented by the following general formula (V), R 13 When the oxygen atom is substituted at the 4 and 4' positions, the 3 and 3' positions are t-butyl groups, and the 6 and 6' positions are methyl groups. 13 YSLV-120TE (Nippon Steel Chemical & Material Co., Ltd., product name) in which is a hydrogen atom is commercially available.

[0029] [ka]

[0030] In formula (V), R 13represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different from each other. n is an average value and represents a number of 0 to 10.

[0031] The novolac epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolac phenolic resin. For example, epoxy resins obtained by epoxidizing a novolac phenolic resin such as a phenol novolac resin, a cresol novolac resin, or a naphthol novolac resin using a method such as glycidyl etherification are preferred, and epoxy resins represented by the following general formula (VI) are more preferred. Among the epoxy resins represented by the following general formula (VI), R 14 are all hydrogen atoms, and R 15 is a methyl group, and i=1; ESCN-190 and ESCN-195 (product names, Sumitomo Chemical Co., Ltd.); 14 N-770 and N-775 (trade names, DIC Corporation) in which all of R are hydrogen atoms and i=0; 14 are all hydrogen atoms, and the part where i = 0 and the part where i = 1 and R 15 YDAN-1000-10C (Nippon Steel Chemical & Material Co., Ltd., product name), a styrene-modified phenolic novolac epoxy resin having a moiety where R is -CH(CH3)-Ph; 14 are all hydrogen atoms, i=1, and R 15 is a methyl group, and i=2 and R 15 A benzyl group-modified cresol novolac epoxy resin having one methyl group and one benzyl group is commercially available.

[0032] [ka]

[0033] In formula (VI), R 14 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 15represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0034] The dicyclopentadiene-type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a compound having a dicyclopentadiene skeleton as a raw material. For example, an epoxy resin represented by the following general formula (VII) is preferred. Among the epoxy resins represented by the following general formula (VII), HP-7200 (trade name, DIC Corporation), in which i = 0, is commercially available.

[0035] [ka]

[0036] In formula (VII), R 16 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0037] The triphenylmethane epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a triphenylmethane skeleton. For example, an epoxy resin obtained by glycidyl etherifying a triphenylmethane phenolic resin obtained from an aromatic aldehyde compound and a phenolic compound is preferred, and an epoxy resin represented by the following general formula (VIII) is more preferred. Among the epoxy resins represented by the following general formula (VIII), 1032H60 (Mitsubishi Chemical Corporation, trade name) and EPPN-502H (Nippon Kayaku Co., Ltd., trade name), in which i is 0 and k is 0, are commercially available.

[0038] [ka]

[0039] In formula (VIII), R 17 and R 18represents a monovalent organic group having 1 to 18 carbon atoms, and may all be the same or different. Each i independently represents an integer of 0 to 3, and each k independently represents an integer of 0 to 4. n is an average value and represents a number of 0 to 10.

[0040] The copolymerized epoxy resin obtained by epoxidizing a novolac resin obtained from a naphthol compound, a phenol compound, and an aldehyde compound is not particularly limited as long as it is an epoxy resin made from a compound having a naphthol skeleton and a compound having a phenol skeleton as raw materials. For example, an epoxy resin obtained by glycidyl etherifying a novolac phenolic resin using a compound having a naphthol skeleton and a compound having a phenol skeleton is preferred, and an epoxy resin represented by the following general formula (IX) is more preferred. Among the epoxy resins represented by the following general formula (IX), R 21 is a methyl group, i is 1, j is 0, and k is 0, and NC-7300 (trade name, Nippon Kayaku Co., Ltd.) is available as a commercially available product.

[0041] [ka]

[0042] In formula (IX), R 19 ~R 21 represents a monovalent organic group having 1 to 18 carbon atoms, and may all be the same or different. Each i independently represents an integer of 0 to 3, each j independently represents an integer of 0 to 2, and each k independently represents an integer of 0 to 4. Each l and m is an average value and a number of 0 to 10, and (l+m) represents a number of 0 to 10. The terminal of the epoxy resin represented by formula (IX) is either formula (IX-1) or (IX-2) below. In formulas (IX-1) and (IX-2), R 19 ~R 21 , i, j and k are defined as R 19 ~R 21 The definitions of i, j, and k are the same as those of i, j, and k. n is 1 (when the bond is formed via a methylene group) or 0 (when the bond is not formed via a methylene group).

[0043] [ka]

[0044] Examples of the epoxy resin represented by the general formula (IX) include random copolymers containing l structural units and m structural units randomly, alternating copolymers containing them alternately, copolymers containing them regularly, block copolymers containing them in blocks, etc. Any of these may be used alone or in combination of two or more.

[0045] Another preferred copolymer epoxy resin is Epiclon HP-5000 (trade name, DIC Corporation), a methoxynaphthalene-cresol-formaldehyde co-condensation epoxy resin containing the following two structural units in a random, alternating, or block order: In the following general formula, n and m each represent an average value and are numbers from 0 to 10, and (n+m) represents a number from 0 to 10, preferably n and m each represent an average value and are numbers from 1 to 9, and (n+m) represents a number from 2 to 10.

[0046] [ka]

[0047] The aralkyl epoxy resin is not particularly limited as long as it is an epoxy resin made from a phenolic resin synthesized from at least one selected from the group consisting of phenolic compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or a derivative thereof. For example, epoxy resins obtained by glycidyl etherifying a phenolic resin synthesized from at least one selected from the group consisting of phenolic compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or a derivative thereof are preferred, and epoxy resins represented by the following general formulas (X) and (XI) are more preferred.

[0048] Among the epoxy resins represented by the following general formula (X), those in which i is 0 and R 38 is a hydrogen atom, i is 0, and R 38 is a hydrogen atom and all R 8 CER-3000 (trade name, Nippon Kayaku Co., Ltd.), which is a mixture of an epoxy resin in which l is a hydrogen atom and an epoxy resin in which k is a hydrogen atom at a mass ratio of 80:20, is commercially available. Furthermore, among the epoxy resins represented by the following general formula (XI), ESN-175 (trade name, Nippon Steel Chemical & Material Co., Ltd.), in which l is 0, j is 0, and k is 0, is commercially available.

[0049] [ka]

[0050] In formulas (X) and (XI), R 38 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 37 , R 39 ~R 41 represents a monovalent organic group having 1 to 18 carbon atoms, and may all be the same or different. Each i is independently an integer of 0 to 3, each j is independently an integer of 0 to 2, each k is independently an integer of 0 to 4, and each l is independently an integer of 0 to 4. Each n is an average value and is independently a number of 0 to 10.

[0051] R in the above general formulas (II) to (XI) 8 ~R 21 and R 37 ~R 41 In the formula (II), "all of them may be the same or different" means, for example, that 8 to 88 R 8 This means that all of the R may be the same or different. 9 ~R 21 and R 37 ~R 41In addition, the numbers of R may all be the same or different. 8 ~R 21 and R 37 ~R 41 may be the same or different. For example, R 9 and R 10 may all be the same or different. Furthermore, the monovalent organic group having 1 to 18 carbon atoms in the general formulae (III) to (XI) is preferably an alkyl group or an aryl group.

[0052] In the general formulas (II) to (XI), n is an average value, and each independently is preferably in the range of 0 to 10. When n is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity of the thermosetting resin composition during melt molding tends to decrease, and the occurrence of filling defects, deformation of bonding wires (gold wires connecting semiconductor elements to leads), etc. is more preferably set in the range of 0 to 4.

[0053] Specific examples of preferred epoxy resins that can be used in the thermosetting resin composition have been described above in accordance with the general formulas (II) to (XI). More specific preferred epoxy resins include 4,4'-bis(2,3-epoxypropoxy)-3,3',5,5'-tetramethylbiphenyl from the viewpoint of heat resistance, and 4,4'-bis(2,3-epoxypropoxy)-biphenyl from the viewpoint of moldability and heat resistance.

[0054] The epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of a balance of various properties such as moldability, heat resistance, and electrical reliability, the epoxy equivalent of the epoxy resin is preferably 60 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.

[0055] The epoxy resin may be liquid or solid. When the epoxy resin is solid, the softening point or melting point of the epoxy resin is not particularly limited. From the viewpoints of moldability and heat resistance, it is preferably 40°C to 180°C, and from the viewpoint of handleability during preparation of the thermosetting resin composition, it is more preferably 50°C to 130°C. In the present disclosure, the softening point refers to a value measured by the ring and ball method of JIS K 7234:1986. In the present disclosure, the melting point refers to a value measured in accordance with the visual method of JIS K 0064:1992.

[0056] From the viewpoints of strength, fluidity, heat resistance, moldability, etc., the content of the epoxy resin in the thermosetting resin composition is preferably 0.5 to 60% by mass, and more preferably 2 to 50% by mass.

[0057] (hardening agent) The thermosetting resin composition contains a curing agent. The type of curing agent is not particularly limited, as long as it is a compound that undergoes a curing reaction with the thermosetting resin used in combination. For example, curing agents that can be used in combination with an epoxy resin include phenol-based curing agents, amine-based curing agents, acid anhydride-based curing agents, polymercaptan-based curing agents, polyaminoamide-based curing agents, isocyanate-based curing agents, and blocked isocyanate-based curing agents. One type of curing agent may be used alone, or two or more types may be used in combination. The curing agent may be solid or liquid at room temperature and normal pressure (e.g., 25°C, atmospheric pressure), and is preferably solid. When the thermosetting resin is an epoxy resin, the curing agent is preferably a phenol-based curing agent or an amine-based curing agent from the viewpoint of heat resistance. Examples of phenolic curing agents include phenolic resins and polyhydric phenolic compounds having two or more phenolic hydroxyl groups per molecule. Specific examples include polyhydric phenolic compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols; novolac phenolic resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic 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, or propionaldehyde, under an acidic catalyst; and phenolic resins synthesized from the above phenolic compounds and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or the like. Examples of suitable curing agents include aralkyl-type phenolic resins such as aryl aralkyl resins and naphthol aralkyl resins; paraxylylene- and / or metaxylylene-modified phenolic resins; melamine-modified phenolic resins; terpene-modified phenolic resins; dicyclopentadiene-type phenolic resins and dicyclopentadiene-type naphthol resins synthesized by copolymerization of the above-mentioned phenolic compounds with dicyclopentadiene; cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified phenolic resins; biphenyl-type phenolic resins; triphenylmethane-type phenolic resins obtained by condensing or co-condensing the above-mentioned phenolic compounds with aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; and phenolic resins obtained by copolymerizing two or more of these. Furthermore, examples of phenolic curing agents include monohydric phenolic compounds having one phenolic hydroxyl group per molecule. These phenolic curing agents may be used alone or in combination.

[0058] Among phenolic curing agents, from the viewpoint of heat resistance, at least one selected from the group consisting of aralkyl phenolic resins, dicyclopentadiene phenolic resins, triphenylmethane phenolic resins, copolymerized phenolic resins of triphenylmethane phenolic resins and aralkyl phenolic resins, and novolac phenolic resins (these are referred to as "specific phenolic curing agents"). The specific phenolic curing agents may be used alone or in combination of two or more.

[0059] The total proportion of the aralkyl phenolic resin and the melamine-modified phenolic resin in the entire phenolic curing agent is preferably 40% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and even more preferably 80% by mass to 100% by mass. The proportion of the aralkyl phenol resin in the entire phenol-based curing agent is preferably 40% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and even more preferably 80% by mass to 100% by mass. The total proportion of the melamine-modified phenolic resins in the entire phenolic curing agent is preferably 0% by mass to 15% by mass, more preferably 0% by mass to 10% by mass, and even more preferably 0% by mass to 5% by mass.

[0060] The melamine-modified phenolic resin may be obtained by mixing a phenolic compound such as phenol, melamine, and formalin, and then subjecting the mixture to a heating reaction.

[0061] Examples of aralkyl phenolic resins include phenol aralkyl resins and naphthol aralkyl resins synthesized from a phenolic compound and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc. The aralkyl phenolic resin may be further copolymerized with other phenolic resins. Examples of copolymerized aralkyl phenolic resins include copolymerized phenolic resins of triphenylmethane phenolic resin and aralkyl phenolic resin, copolymerized phenolic resins of salicylaldehyde phenolic resin and aralkyl phenolic resin, and copolymerized phenolic resins of novolac phenolic resin and aralkyl phenolic resin.

[0062] The aralkyl phenolic resin is not particularly limited as long as it is a phenolic resin synthesized from at least one compound selected from the group consisting of phenol compounds and naphthol compounds, and dimethoxy-para-xylene, bis(methoxymethyl)biphenyl, or a derivative thereof. For example, phenolic resins represented by the following general formulas (XII) to (XIV) are preferred.

[0063] [ka]

[0064] In formulas (XII) to (XIV), R 23 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 22 , R 24 , R 25 and R 28 R represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 26 and R 27 represents a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and may all be the same or different. Each i is independently an integer of 0 to 3, each j is independently an integer of 0 to 2, each k is independently an integer of 0 to 4, and each p is independently an integer of 0 to 4. Each n is an average value and is independently a number of 0 to 10.

[0065] Among the phenolic resins represented by the general formula (XII), i is 0 and R 23 MEH-7851 (product name, Meiwa Kasei Co., Ltd.), in which all are hydrogen atoms, is commercially available.

[0066] Among the phenolic resins represented by the general formula (XIII) above, XL-225, XLC (Mitsui Chemicals, Inc., trade name), MEH-7800 (Meiwa Chemical Industry Co., Ltd., trade name), etc., in which i is 0 and k is 0, are commercially available.

[0067] Among the phenolic resins represented by the general formula (XIV), SN-170 (trade name, Nippon Steel Chemical & Material Co., Ltd.), in which j is 0, k is 0, and p is 0, and R 27 is a hydroxyl group and p is 0, and SN-395 (trade name, Nippon Steel Chemical & Material Co., Ltd.) is available as a commercially available product.

[0068] The dicyclopentadiene-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained from a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenolic resin represented by the following general formula (XV) is preferred. Among the phenolic resins represented by the following general formula (XV), phenolic resins in which i is 0 are commercially available.

[0069] [ka]

[0070] In formula (XV), R 29 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0071] The triphenylmethane type phenolic resin is not particularly limited as long as it is a phenolic resin obtained from an aromatic aldehyde compound as a raw material. For example, a phenolic resin represented by the following general formula (XVI) is preferred.

[0072] Among the phenolic resins represented by the following general formula (XVI), MEH-7500 (trade name, Meiwa Kasei Co., Ltd.), in which i and k are 0, is commercially available.

[0073] [ka]

[0074] In formula (XVI), R 30 and R 31 represents a monovalent organic group having 1 to 18 carbon atoms, and may all be the same or different. Each i is independently an integer of 0 to 3, and each k is independently an integer of 0 to 4. n is an average value and is a number of 0 to 10.

[0075] The copolymerized phenolic resin of a triphenylmethane type phenolic resin and an aralkyl type phenolic resin is not particularly limited as long as it is a copolymerized phenolic resin of a phenolic resin obtained from a compound having a benzaldehyde skeleton as a raw material and an aralkyl type phenolic resin. For example, a phenolic resin represented by the following general formula (XVII) is preferred.

[0076] Among the phenolic resins represented by the following general formula (XVII), HE-510 (trade name, Air Water Chemical Co., Ltd.), in which i is 0, k is 0, and q is 0, is commercially available.

[0077] [ka]

[0078] In formula (XVII), R 32 ~R 34represents a monovalent organic group having 1 to 18 carbon atoms, and may all be the same or different. Each i is independently an integer of 0 to 3, each k is independently an integer of 0 to 4, and each q is independently an integer of 0 to 5. Each l and m is an average value and independently a number of 0 to 11, provided that the sum of l and m is a number of 1 to 11.

[0079] The novolac phenolic resin is not particularly limited as long as it is a phenolic resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds and naphthol compounds with an aldehyde compound in the presence of an acid catalyst. For example, a phenolic resin represented by the following general formula (XVIII) is preferred.

[0080] Among the phenolic resins represented by the following general formula (XVIII), those in which i is 0 and R 35 are all hydrogen atoms, such as Tamanol 758 and 759 (trade names, Arakawa Chemical Industries, Ltd.) and H-4 (trade name, Meiwa Chemical Industry Co., Ltd.).

[0081] [ka]

[0082] In formula (XVIII), R 35 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. 36 represents a monovalent organic group having 1 to 18 carbon atoms, and may be the same or different. Each i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0083] R in the above general formulas (XII) to (XVIII) 22 ~R 36 The expression "may be the same or different" means, for example, that i R 22 This means that all of the R may be the same or different from each other. 23 ~R 36In addition, the numbers of R may be the same or different from each other. 22 ~R 36 may be the same or different. For example, R 22 and R 23 may be the same or different, and R 30 and R 31 may all be the same or different.

[0084] In the general formulas (XII) to (XVIII), n is preferably in the range of 0 to 10. If n is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity of the thermosetting resin composition during melt molding also becomes low, making it less likely that filling defects, deformation of bonding wires (gold wires connecting semiconductor elements to leads), etc. will occur. The average n in one molecule is preferably set in the range of 0 to 4.

[0085] Examples of monohydric phenol compounds include "Tinuvin 405," "Tinuvin 900," "Tinuvin 99-2," "Tinuvin 326," "Tinuvin 384-2," and "Tinuvin 928" (all manufactured by BASF). In one embodiment, the proportion of the monohydric phenol compound in the entire phenol-based curing agent is preferably 5% by mass to 20% by mass, more preferably 10% by mass to 19% by mass, and even more preferably 12% by mass to 18% by mass. In another embodiment, the proportion may be 5% by mass or less, 2% by mass or less, 1% by mass or less, or even 0% by mass.

[0086] Specific examples of amine curing agents include aliphatic amine compounds such as diethylenetriamine, triethylenetetramine, n-propylamine, 2-hydroxyethylaminopropylamine, cyclohexylamine, and 4,4'-diamino-dicyclohexylmethane, aromatic amine compounds such as diethyltoluenediamine, 3,3'-diethyl-4,4'-diaminodiphenylmethane, dimethylthiotoluenediamine, and 2-methylaniline, imidazole compounds such as imidazole, 2-methylimidazole, 2-ethylimidazole, and 2-isopropylimidazole, and imidazoline compounds such as imidazoline, 2-methylimidazoline, and 2-ethylimidazoline. Among these, aromatic amine compounds are preferred from the viewpoint of storage stability, and diethyltoluenediamine, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and dimethylthiotoluenediamine are more preferred.

[0087] The functional group equivalent of the curing agent (hydroxyl group equivalent for phenolic curing agents, active hydrogen equivalent for amine curing agents) is not particularly limited. From the viewpoint of the balance of various properties such as moldability, heat resistance, and electrical reliability, it is preferably 10 g / eq to 1000 g / eq, and more preferably 30 g / eq to 500 g / eq. The hydroxyl equivalent weight for phenolic curing agents is a value calculated based on the hydroxyl value measured in accordance with JIS K0070:1992, and the active hydrogen equivalent weight for amine curing agents is a value calculated based on the amine value measured in accordance with JIS K7237:1995.

[0088] When the curing agent is solid, the softening point or melting point is not particularly limited, but from the viewpoints of moldability and heat resistance, it is preferably 40°C to 180°C, and from the viewpoint of handleability during production of the thermosetting resin composition, it is more preferably 50°C to 130°C.

[0089] When the thermosetting resin is an epoxy resin, the equivalent ratio of the epoxy resin to the curing agent (molar number of epoxy groups in the resin / molar number of active hydrogens in the curing agent) is not particularly limited, but is preferably, for example, 0.7 to 1.3 from the viewpoint of minimizing unreacted amounts of each.

[0090] (curing accelerator) The thermosetting resin composition may contain a curing accelerator. The type of curing accelerator is not particularly limited and can be selected depending on the type of curable resin, the desired properties of the thermosetting resin composition, and the like.

[0091] From the viewpoint of curability and fluidity, the curing accelerator preferably contains a phosphonium compound. Specific examples of the phosphonium compound include triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkylalkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, and tris(tetraalkoxyphenyl)phosphine. Tertiary phosphines such as sphines, trialkylphosphines, dialkylarylphosphines, and alkyldiarylphosphines are combined with quinone compounds such as maleic anhydride, 1,4-benzoquinone, 2,5-toluquinone, 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, and compounds with π bonds such as diazophenylmethane, which have intramolecular polarization. Compounds which react with tertiary phosphines include 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, 4-iodophenol, 3-iodophenol, 2-iodophenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-tert-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, Examples of such compounds include compounds having intramolecular polarization obtained by reacting a halogenated phenol compound such as 2-naphthol, 6-bromo-2-naphthol, or 4-bromo-4'-hydroxybiphenyl, followed by a dehydrohalogenation step; salts of tetra-substituted phosphonium such as tetraphenylphosphonium and tetra-substituted borates such as tetra-p-tolylborate; salts of tetra-substituted phosphonium and anions obtained by removing a proton from a phenol compound, and salts of tetra-substituted phosphonium and anions obtained by removing a proton from a carboxylic acid compound.

[0092] The phosphonium compound preferably contains a compound represented by the following general formula (I-1) (hereinafter also referred to as a specific curing accelerator).

[0093] [ka]

[0094] In formula (I-1), R 1 ~R 3 are each independently a hydrocarbon group having 1 to 18 carbon atoms, and R 1 ~R 3 Two or more of R may be bonded to each other to form a cyclic structure; 4 ~R 7 are each independently a hydrogen atom, a hydroxyl group, or an organic group having 1 to 18 carbon atoms, and R 4 ~R 7 Two or more of these may be bonded to each other to form a cyclic structure.

[0095] R in general formula (I-1) 1 ~R 3 The "hydrocarbon group having 1 to 18 carbon atoms" described above includes an aliphatic hydrocarbon group having 1 to 18 carbon atoms and an aromatic hydrocarbon group having 6 to 18 carbon atoms.

[0096] From the viewpoint of flowability, the aliphatic hydrocarbon group having 1 to 18 carbon atoms preferably has 1 to 8 carbon atoms, more preferably 2 to 6 carbon atoms, and even more preferably 4 to 6 carbon atoms.

[0097] The aliphatic hydrocarbon group having 1 to 18 carbon atoms may be a linear or branched aliphatic hydrocarbon group having 1 to 18 carbon atoms, or an alicyclic hydrocarbon group having 3 to 18 carbon atoms. From the viewpoint of ease of production, a linear or branched aliphatic hydrocarbon group is preferred.

[0098] Specific examples of linear or branched aliphatic hydrocarbon groups having 1 to 18 carbon atoms include alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, pentyl, hexyl, octyl, decyl, and dodecyl, as well as allyl and vinyl groups. The linear or branched aliphatic hydrocarbon groups may or may not have a substituent. Examples of the substituent include alkoxy groups such as methoxy, ethoxy, n-butoxy, and t-butoxy, aryl groups such as phenyl and naphthyl, hydroxyl groups, amino groups, and halogen atoms. The linear or branched aliphatic hydrocarbon groups may have two or more substituents, and in such cases, the substituents may be the same or different. When the linear or branched aliphatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aliphatic hydrocarbon group and the substituent is preferably 1 to 18. From the viewpoint of curability, unsubstituted alkyl groups are preferred, unsubstituted alkyl groups having 1 to 8 carbon atoms are more preferred, and n-butyl, isobutyl, n-pentyl, n-hexyl and n-octyl groups are even more preferred.

[0099] Specific examples of alicyclic hydrocarbon groups having 3 to 18 carbon atoms include cycloalkyl groups such as cyclopentyl, cyclohexyl, and cycloheptyl, and cycloalkenyl groups such as cyclopentenyl and cyclohexenyl. The alicyclic hydrocarbon group may or may not have a substituent. Examples of the substituent include alkyl groups such as methyl, ethyl, n-butyl, and t-butyl; alkoxy groups such as methoxy, ethoxy, n-butoxy, and t-butoxy; aryl groups such as phenyl and naphthyl; hydroxyl groups; amino groups; and halogen atoms. The alicyclic hydrocarbon group may have two or more substituents, and in such cases, the substituents may be the same or different. When the alicyclic hydrocarbon group has a substituent, the total number of carbon atoms contained in the alicyclic hydrocarbon group and the substituent is preferably 3 to 18. When the alicyclic hydrocarbon group has a substituent, the position of the substituent is not particularly limited. From the viewpoint of curability, unsubstituted cycloalkyl groups are preferred, unsubstituted cycloalkyl groups having 4 to 10 carbon atoms are more preferred, and cyclohexyl, cyclopentyl and cycloheptyl groups are even more preferred.

[0100] The aromatic hydrocarbon group having 6 to 18 carbon atoms preferably has 6 to 14 carbon atoms, and more preferably 6 to 10 carbon atoms. The aromatic hydrocarbon group may or may not have a substituent. Examples of the substituent include alkyl groups such as methyl, ethyl, n-butyl, and t-butyl; alkoxy groups such as methoxy, ethoxy, n-butoxy, and t-butoxy; aryl groups such as phenyl and naphthyl; hydroxyl groups; amino groups; and halogen atoms. The aromatic hydrocarbon group may have two or more substituents, and in such cases, the substituents may be the same or different. When the aromatic hydrocarbon group has a substituent, the total number of carbon atoms contained in the aromatic hydrocarbon group and the substituent is preferably 6 to 18. When the aromatic hydrocarbon group has a substituent, the position of the substituent is not particularly limited.

[0101] Specific examples of aromatic hydrocarbon groups having 6 to 18 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, tolyl, dimethylphenyl, ethylphenyl, butylphenyl, t-butylphenyl, methoxyphenyl, ethoxyphenyl, n-butoxyphenyl, and t-butoxyphenyl. The position of the substituent in these aromatic hydrocarbon groups may be any of ortho, meta, and para positions. From the viewpoint of fluidity, unsubstituted aryl groups having 6 to 12 carbon atoms or 6 to 12 carbon atoms including substituents are preferred, unsubstituted aryl groups having 6 to 10 carbon atoms or 6 to 10 carbon atoms including substituents are more preferred, and phenyl, p-tolyl, and p-methoxyphenyl are even more preferred.

[0102] R in general formula (I-1) 1 ~R 3 The term "R" is written as 1 ~R 3 Two or more of R may be bonded to each other to form a cyclic structure. 1 ~R 3 In this case, two or three of the R 1 ~R 3 Examples of the substituent include alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene, alkenylene groups such as ethyleneylene, propylene, butylene, and butylene, aralkylene groups such as methylenephenylene, and arylene groups such as phenylene, naphthylene, and anthracenylene. These substituents may be further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, or the like.

[0103] R in the above general formula (I-1) 4 ~R 7The "organic group having 1 to 18 carbon atoms" described above is intended to include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aliphatic hydrocarbonoxy group, an aromatic hydrocarbonoxy group, an acyl group, a hydrocarbonoxycarbonyl group, and an acyloxy group, which have 1 to 18 carbon atoms and may be substituted or unsubstituted.

[0104] Examples of the aliphatic hydrocarbon group and aromatic hydrocarbon group include R 1 ~R 3 Examples of the aliphatic hydrocarbon group and aromatic hydrocarbon group represented by the formula (I) include those mentioned above.

[0105] Examples of the aliphatic hydrocarbon oxy group include oxy groups having a structure in which an oxygen atom is bonded to the above-mentioned aliphatic hydrocarbon group, such as a methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, 2-butoxy group, t-butoxy group, cyclopropyloxy group, cyclohexyloxy group, cyclopentyloxy group, allyloxy group, and vinyloxy group, as well as those aliphatic hydrocarbon oxy groups which are further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, or the like.

[0106] Examples of the aromatic hydrocarbon oxy group include oxy groups having a structure in which an oxygen atom is bonded to the above-mentioned aromatic hydrocarbon group, such as a phenoxy group, a methylphenoxy group, an ethylphenoxy group, a methoxyphenoxy group, a butoxyphenoxy group, or a phenoxyphenoxy group, and these aromatic hydrocarbon oxy groups are further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like.

[0107] Examples of the acyl group include aliphatic hydrocarbon carbonyl groups such as formyl, acetyl, ethylcarbonyl, butyryl, cyclohexylcarbonyl, and allylcarbonyl; aromatic hydrocarbon carbonyl groups such as phenylcarbonyl and methylphenylcarbonyl; and these aliphatic hydrocarbon carbonyl groups or aromatic hydrocarbon carbonyl groups which are further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like.

[0108] Examples of the hydrocarbon oxycarbonyl group include aliphatic hydrocarbon oxycarbonyl groups such as a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, an allyloxycarbonyl group, and a cyclohexyloxycarbonyl group; aromatic hydrocarbon oxycarbonyl groups such as a phenoxycarbonyl group and a methylphenoxycarbonyl group; and these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups which are further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like.

[0109] Examples of the acyloxy group include aliphatic hydrocarbon carbonyloxy groups such as a methylcarbonyloxy group, an ethylcarbonyloxy group, a butylcarbonyloxy group, an allylcarbonyloxy group, and a cyclohexylcarbonyloxy group; aromatic hydrocarbon carbonyloxy groups such as a phenylcarbonyloxy group and a methylphenylcarbonyloxy group; and these aliphatic hydrocarbon carbonyloxy groups or aromatic hydrocarbon carbonyloxy groups which are further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a halogen atom, or the like.

[0110] R in the above general formula (I-1) 4 ~R 7 The term "R" is written as 4 ~R 7 The phrase "two or more of R may be bonded to each other to form a cyclic structure" means that two to four R 4 ~R 7may be bonded to form a single divalent to tetravalent organic group as a whole. 4 ~R 7 Examples of the cyclic group include substituents capable of forming a cyclic structure, such as alkylene groups such as ethylene, propylene, butylene, pentylene, and hexylene, alkenylene groups such as ethyleneylene, propylene, and butylene, aralkylene groups such as methylenephenylene, and arylene groups such as phenylene, naphthylene, and anthracenylene, as well as oxy or dioxy groups thereof. These substituents may be further substituted with an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an amino group, a hydroxyl group, a halogen atom, or the like.

[0111] R in the above general formula (I-1) 4 ~R 7 is not particularly limited. For example, it is preferable that each independently be selected from a hydrogen atom, a hydroxyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryloxy group. Among these, from the viewpoint of availability of raw materials, a hydrogen atom, a hydroxyl group, an aryl group unsubstituted or substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group, or a linear or cyclic alkyl group is preferred. Examples of an unsubstituted aryl group or substituted with at least one selected from the group consisting of an alkyl group and an alkoxy group include a phenyl group, a p-tolyl group, a m-tolyl group, an o-tolyl group, and a p-methoxyphenyl group. Examples of linear or cyclic alkyl groups include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a 2-butyl group, a t-butyl group, an octyl group, and a cyclohexyl group. From the viewpoint of curability, R 4 ~R 7 are all hydrogen atoms, or R 4 ~R 7 It is preferred that at least one of the groups is a hydroxyl group and the rest are all hydrogen atoms.

[0112] In the general formula (I-1), R 1 ~R 3two or more of R are alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms; 4 ~R 7 are all hydrogen atoms, or at least one is a hydroxyl group and the rest are all hydrogen atoms. 1 ~R 3 are all alkyl groups having 1 to 18 carbon atoms or cycloalkyl groups having 3 to 18 carbon atoms, and R 4 ~R 7 are all hydrogen atoms, or at least one is a hydroxyl group and the rest are all hydrogen atoms.

[0113] From the viewpoint of rapid curing properties, the specific curing accelerator preferably contains a compound represented by the following general formula (I-2).

[0114] [ka]

[0115] In formula (I-2), R 1 ~R 3 are each independently a hydrocarbon group having 1 to 18 carbon atoms, and R 1 ~R 3 Two or more of R may be bonded to each other to form a cyclic structure; 4 ~R 6 are each independently a hydrogen atom or an organic group having 1 to 18 carbon atoms, and R 4 ~R 6 Two or more of these may be bonded to each other to form a cyclic structure.

[0116] R in general formula (I-2) 1 ~R 6 Specific examples of R in general formula (I-1) 1 ~R 7 The specific examples and preferred ranges are the same as those of the above.

[0117] Specific examples of the specific curing accelerator include an addition reaction product of triphenylphosphine and 1,4-benzoquinone, an addition reaction product of tri-n-butylphosphine and 1,4-benzoquinone, an addition reaction product of tricyclohexylphosphine and 1,4-benzoquinone, an addition reaction product of dicyclohexylphenylphosphine and 1,4-benzoquinone, an addition reaction product of cyclohexyldiphenylphosphine and 1,4-benzoquinone, an addition reaction product of triisobutylphosphine and 1,4-benzoquinone, and an addition reaction product of tricyclopentylphosphine and 1,4-benzoquinone.

[0118] The specific curing accelerator can be obtained, for example, as an adduct of a tertiary phosphine compound and a quinone compound. Specific examples of the tertiary phosphine compound include triphenylphosphine, tributylphosphine, dibutylphenylphosphine, butyldiphenylphosphine, ethyldiphenylphosphine, triphenylphosphine, tris(4-methylphenyl)phosphine, tris(4-ethylphenyl)phosphine, tris(4-n-propylphenyl)phosphine, tris(4-n-butylphenyl)phosphine, tris(isopropylphenyl)phosphine, tris(t-butylphenyl)phosphine, tris(2,4-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, etc. From the viewpoint of moldability, triphenylphosphine and tributylphosphine are preferred.

[0119] Specific examples of the quinone compound include o-benzoquinone, p-benzoquinone, diphenoquinone, 1,4-naphthoquinone, anthraquinone, etc. From the viewpoints of moisture resistance and storage stability, p-benzoquinone is preferred.

[0120] The thermosetting resin composition may contain a curing accelerator other than the phosphonium compound. Specific examples of curing accelerators other than phosphonium compounds include diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the above cyclic amidine compounds; phenol novolac salts of the above cyclic amidine compounds or their derivatives; and combinations of these compounds with maleic anhydride, quinone compounds such as 1,4-benzoquinone, 2,5-toluquinone, 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. compounds having intramolecular polarization obtained by adding a compound having a π bond, such as a tetraphenylborate salt of DBU, a tetraphenylborate salt of DBN, a tetraphenylborate salt of 2-ethyl-4-methylimidazole, or a tetraphenylborate salt of N-methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the above-mentioned tertiary amine compounds; and ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and tetrapropylammonium hydroxide.

[0121] When the thermosetting resin composition contains a specific curing accelerator as a curing accelerator, the content of the specific curing accelerator is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more of the total curing accelerator.

[0122] When the thermosetting resin composition contains a curing accelerator, the amount thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass, per 100 parts by mass of the total of the thermosetting resin and the curing agent. When the amount of the curing accelerator is 0.1 parts by mass or more per 100 parts by mass of the total of the thermosetting resin and the curing agent, the composition tends to cure well in a short time. When the amount of the curing accelerator is 30 parts by mass or less per 100 parts by mass of the total of the thermosetting resin and the curing agent, the curing speed is not too fast, and a good molded product tends to be obtained.

[0123] (Inorganic filler) The thermosetting resin composition contains an inorganic filler, which includes the specific inorganic filler as well as other inorganic fillers such as inorganic fillers that have not been surface-treated with a coupling agent and inorganic fillers that have been surface-treated with a coupling agent other than a coupling agent containing a primary amino group. The type of inorganic filler is not particularly limited. Specific examples include inorganic materials such as silica (e.g., spherical silica, crystalline silica), glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fosterite, steatite, spinel, mullite, titania, talc, clay, and mica. Inorganic fillers with flame retardant properties may also be used. Examples of inorganic fillers with flame retardant properties include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides (e.g., magnesium-zinc composite hydroxide), and zinc borate. Among these, spherical silica is preferred from the viewpoint of reducing the linear expansion coefficient, and alumina is preferred from the viewpoint of high thermal conductivity. One type of inorganic filler may be used alone, or two or more types may be used in combination. The inorganic filler may be in the form of powder, beads formed by spheroidizing powder, or fibers.

[0124] The content of the inorganic filler in the thermosetting resin composition is not particularly limited. From the viewpoint of fluidity and strength, it is preferably 80% by mass to 95% by mass, more preferably 82% by mass to 93% by mass, and even more preferably 84% by mass to 91% by mass of the entire thermosetting resin composition. When the content of the inorganic filler is 80% by mass or more of the entire thermosetting resin composition, the properties of the cured product, such as the thermal expansion coefficient, thermal conductivity, and elastic modulus, tend to be further improved. When the content of the inorganic filler is 95% by mass or less of the entire thermosetting resin composition, an increase in the viscosity of the thermosetting resin composition is suppressed, and the fluidity is further improved, tending to result in better moldability. The content of the inorganic filler in the thermosetting resin composition is not particularly limited. From the viewpoint of fluidity and strength, it is preferably 70 to 90% by volume, more preferably 72 to 88% by volume, and even more preferably 75 to 85% by volume of the entire thermosetting resin composition. When the content of the inorganic filler is 70% by volume or more of the entire thermosetting resin composition, the properties of the cured product, such as the thermal expansion coefficient, thermal conductivity, and elastic modulus, tend to be further improved. When the content of the inorganic filler is 90% by volume or less of the entire thermosetting resin composition, an increase in the viscosity of the thermosetting resin composition is suppressed, and the fluidity is further improved, tending to result in better moldability.

[0125] The average particle size of the inorganic filler is not particularly limited, but for example, the volume average particle size is preferably 0.2 μm to 50 μm, and more preferably 0.5 μm to 30 μm. When the volume average particle diameter is 0.2 μm or more, the increase in viscosity of the thermosetting resin composition tends to be further suppressed. When the volume average particle diameter is 50 μm or less, the filling ability into narrow gaps tends to be further improved. The volume average particle diameter of the inorganic filler refers to the value measured as the volume average particle diameter (D50) using a laser diffraction scattering particle size distribution analyzer.

[0126] From the viewpoint of the flowability of the thermosetting resin composition, the particle shape of the inorganic filler is preferably spherical rather than angular, and the particle size distribution of the inorganic filler is preferably wide.

[0127] In the present disclosure, the inorganic filler includes a specific inorganic filler, and the content of the specific inorganic filler is 20% by mass to 60% by mass of the entire thermosetting resin composition. The content of the specific inorganic filler is preferably 21% by mass to 55% by mass, more preferably 22% by mass to 50% by mass of the entire thermosetting resin composition.

[0128] In the present disclosure, the proportion of the specific inorganic filler in the total inorganic filler is preferably 75% by mass or less, more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less. If the proportion of the specific inorganic filler in the inorganic filler is 75% by mass or less, thickening of the thermosetting resin composition tends to be suppressed and storage stability tends to be improved. The proportion of the specific inorganic filler in the inorganic filler may be 20% by mass or more.

[0129] The surface treatment method of the inorganic filler is appropriately selected depending on the type of inorganic filler. For example, when the inorganic filler is silica, the surface treatment method of the silica can be exemplified by a method in which a solution containing a coupling agent is added to a slurry containing silica, the mixture is stirred, and then the surface-treated silica is separated by filtration or the like and dried, or a method in which a coupling agent is sprayed onto the silica and the mixture is dried.

[0130] The amount of the specific inorganic filler treated with a coupling agent is preferably 0.1 to 5 parts by mass, more preferably 0.3 to 4 parts by mass, and even more preferably 0.5 to 3 parts by mass, per 100 parts by mass of the inorganic filler before surface treatment with a coupling agent containing a primary amino group. If the amount of the specific inorganic filler treated with a coupling agent is 0.1 part by mass or more, the dispersibility of the specific inorganic filler is improved, and the adhesiveness and moldability of the thermosetting resin composition tend to be improved. If the amount of the specific inorganic filler treated with a coupling agent is 5 parts by mass or less, the specific inorganic filler tends to be less likely to aggregate.

[0131] The coupling agent containing a primary amino group used for the surface treatment of inorganic fillers may be any coupling agent having at least one primary amino group (-NH2 group) in the molecule. Specific examples of coupling agents having a primary amino group in the molecule include 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-aminopropyltrimethoxysilane, and isopropyltri(N-aminoethyl-aminoethyl)titanate. As the coupling agent having a primary amino group in the molecule, a silane coupling agent having a primary amino group in the molecule is preferred, and an aminoalkyltrialkoxysilane is more preferred. Examples of the aminoalkyltrialkoxysilane include 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane. Among these, at least one of 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane is more preferred, and 3-aminopropyltriethoxysilane is particularly preferred.

[0132] The bulk density of the specified inorganic filler is 1.15 g / cm 3 ~1.40g / cm 3 is preferred, and 1.20 g / cm 3 ~1.38g / cm 3 more preferably 1.25 g / cm 3 ~1.35g / cm 3 The bulk density of the specific inorganic filler is more preferably 1.15 g / cm. 3 If the bulk density of the specific inorganic filler is 1.40 g / cm or more, the dispersibility of the specific inorganic filler in the thermosetting resin composition tends to be further improved. 3 If it is less than this, the flowability of the thermosetting resin composition tends to be further improved. In the present disclosure, bulk density refers to a value measured by the following method. Bulk density is measured by tilting a 200 ml measuring cylinder, gradually pouring the sample powder into it using a spoon up to the 200 ml mark, then plugging the measuring cylinder and dropping it from a height of 5 cm 400 times, after which the bulk density is calculated from the mass and volume of the sample powder.

[0133] The angle of repose of the specific inorganic filler is preferably 50° to 60°, more preferably 51° to 58°, and even more preferably 52° to 57°. If the angle of repose of the specific inorganic filler is 50° or more, uneven distribution of the specific inorganic filler in the thermosetting resin composition tends to be further suppressed. If the angle of repose of the specific inorganic filler is 60° or less, aggregation of the specific inorganic filler in the thermosetting resin composition tends to be further suppressed. In the present disclosure, the angle of repose refers to a value measured by the injection method.

[0134] [Various additives] In addition to the above-mentioned components, the thermosetting resin composition may contain various additives such as a coupling agent, an ion exchanger, a release agent, a flame retardant, a colorant, a stress relaxation agent, etc. In addition to the additives exemplified below, the thermosetting resin composition may also contain various additives known in the art, such as an ultraviolet absorber, as needed.

[0135] (coupling agent) The thermosetting resin composition may contain a coupling agent. In the present disclosure, the term "the thermosetting resin composition contains a coupling agent" means that the coupling agent is integrally blended into the thermosetting resin composition. The type of coupling agent is not particularly limited, and known coupling agents can be used. Examples of coupling agents include silane coupling agents and titanium coupling agents. One type of coupling agent may be used alone, or two or more types may be used in combination.

[0136] Specific examples of the silane coupling agent include epoxy-based silane coupling agents such as 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, and glycidoxyoctyltrimethoxysilane; amine-based silane coupling agents such as 3-aminopropyltriethoxysilane, 3-(2-aminoethylamino)propyltrimethoxysilane, 3-(2-aminoethylamino)propyltriethoxysilane, 3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltrimethoxysilane; mercapto-based silane coupling agents such as 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane; 3-ureidopropyltriethoxysilane, octenyltrimethoxysilane, and methacryloxyoctyltrimethoxysilane.

[0137] Examples of titanium coupling agents include isopropyl triisostearoyl titanate, isopropyl tris(dioctyl pyrophosphate) titanate, isopropyl tri(N-aminoethyl-aminoethyl) titanate, tetraoctyl bis(ditridecyl phosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(ditridecyl phosphite) titanate, bis(dioctyl pyrophosphate)oxyacetate titanate, bis(dioctyl pyrophosphate)ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryl isostearoyl titanate, isopropyl tridodecyl benzenesulfonyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctyl phosphate) titanate, isopropyl tricumyl phenyl titanate, and tetraisopropyl bis(dioctyl phosphite) titanate.

[0138] When the thermosetting resin composition contains a coupling agent, from the viewpoint of improving the adhesiveness and moldability of the thermosetting resin composition, at least one of an amine-based silane coupling agent and an epoxy-based silane coupling agent is preferable as the coupling agent. When the thermosetting resin composition contains a coupling agent, from the viewpoint of the adhesion of the interface between the thermosetting resin and the inorganic filler, the content of the coupling agent is preferably 0.001 parts by mass to 10 parts by mass, more preferably 0.01 parts by mass to 8 parts by mass, and even more preferably 0.05 parts by mass to 5 parts by mass with respect to 100 parts by mass of the inorganic filler.

[0139] (Ion exchanger) The thermosetting resin composition may contain an ion exchanger. In particular, when the thermosetting resin composition is used as a molding material for sealing, from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of the electronic component device, it is preferable to contain an ion exchanger. The ion exchanger is not particularly limited, and conventionally known ones can be used. Specifically, hydrotalcite compounds, and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth, etc. can be mentioned. The ion exchanger may be used alone or in combination of two or more. Among them, hydrotalcite represented by the following general formula (B) is preferable.

[0140] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O ……(B) (0 < X ≦ 0.5, m is a positive number)

[0141] When the thermosetting resin composition contains an ion exchanger, its content is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions. For example, it is preferably 0.1 parts by mass to 30 parts by mass, more preferably 1 part by mass to 15 parts by mass with respect to 100 parts by mass in total of the thermosetting resin and the curing agent.

[0142] (Release agent) The thermosetting resin composition may contain a mold release agent from the viewpoint of obtaining good releasability from the mold during molding. There are no particular limitations on the mold release agent, and conventionally known ones can be used. Specific examples include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as polyethylene oxide and non-oxidized polyethylene. One type of mold release agent may be used alone, or two or more types may be used in combination.

[0143] When the thermosetting resin composition contains a release agent, the amount thereof is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the thermosetting resin and curing agent combined. When the amount of the release agent is 0.01 parts by mass or more per 100 parts by mass of the thermosetting resin and curing agent combined, sufficient release properties tend to be obtained. When the amount of the release agent is 15 parts by mass or less per 100 parts by mass of the thermosetting resin and curing agent combined, better adhesion tends to be obtained.

[0144] (Flame retardant) The thermosetting resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known flame retardants can be used. Specific examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, and metal hydroxides. The flame retardants may be used alone or in combination of two or more.

[0145] When the thermosetting resin composition contains a flame retardant, the amount thereof is not particularly limited as long as it is an amount sufficient to obtain the desired flame retardant effect. For example, the amount is preferably 1 to 300 parts by mass, more preferably 2 to 150 parts by mass, per 100 parts by mass of the total of the thermosetting resin and the curing agent.

[0146] (coloring agent) The thermosetting resin composition may further contain a colorant. Examples of the colorant include known colorants such as carbon black, organic dyes, organic pigments, titanium oxide, red lead, and red iron oxide. The content of the colorant can be appropriately selected depending on the purpose, etc. One type of colorant may be used alone, or two or more types may be used in combination.

[0147] (Stress reliever) The thermosetting resin composition may contain a stress relief agent such as silicone oil or silicone rubber particles. The inclusion of a stress relief agent can further reduce package warpage and package cracking. Examples of stress relief agents include commonly used known stress relief agents (flexibilizers). Specific examples include thermoplastic elastomers such as silicone, styrene, olefin, urethane, polyester, polyether, polyamide, and polybutadiene elastomers; rubber particles such as NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, urethane rubber, and silicone powder; methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, methyl methacrylate-butyl acrylate copolymer; copolymers of indenes (e.g., indene and alkylindene) with styrenes (e.g., alkylstyrene) and phenols, containing aromatic olefins such as coumarone as other constituent monomers; and epoxy-modified silicone resins. The stress relief agents may be used alone or in combination of two or more. When the thermosetting resin composition contains a stress relaxation agent, the content of the stress relaxation agent is preferably 1 to 50 parts by mass per 100 parts by mass of the total of the thermosetting resin and the curing agent.

[0148] (Method for preparing thermosetting resin composition) The method for preparing the thermosetting resin composition is not particularly limited. A common method includes thoroughly mixing predetermined amounts of components using a mixer or the like, then melt-kneading the mixture using a mixing roll, extruder, or the like, cooling, and pulverizing the mixture. More specifically, for example, a method includes uniformly stirring and mixing predetermined amounts of the components described above, kneading the mixture using a kneader, roll, extruder, or the like that has been preheated to 70°C to 140°C, cooling, and pulverizing the mixture.

[0149] The thermosetting resin composition is preferably solid at room temperature and normal pressure (for example, 25°C, atmospheric pressure). When the thermosetting resin composition is solid, its shape is not particularly limited, and examples thereof include powder, granules, tablets, pellets, and granules. When the thermosetting resin composition is in tablet or pellet form, it is preferable that the dimensions and mass of the composition be set to suit the molding conditions of the package, from the viewpoint of ease of handling.

[0150] The method for curing the thermosetting resin composition is not particularly limited. The thermosetting resin composition may be cured by low-pressure transfer molding, injection molding, compression molding, or the like, and then post-cured. The post-curing conditions can be appropriately set in consideration of the composition of the thermosetting resin composition, etc. The post-curing temperature is, for example, preferably 160° C. to 240° C., more preferably 160° C. to 220° C., and even more preferably 175° C. to 200° C. The post-curing time is, for example, preferably 1 hour to 48 hours, more preferably 3 hours to 24 hours, and even more preferably 5 hours to 24 hours.

[0151] <Semiconductor device> The semiconductor device of the present disclosure includes a semiconductor element and a cured product of the thermosetting resin composition of the present disclosure that encapsulates the semiconductor element. The semiconductor element is not particularly limited, and examples thereof include a diode, a transistor, a thyristor, an IC (Integrated Circuit), and an LSI (Large Scale Integration). Specific examples of semiconductor devices include general resin-sealed ICs such as DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead Package), TSOP (Thin Small Outline Package), TQFP (Thin Quad Flat Package), and QFN (Quad Flat Non-leaded), which have a structure in which a semiconductor element is fixed on a lead frame, and terminal portions of the semiconductor element such as bonding pads are connected to lead portions by wire bonding, bumps, or the like, and then sealed using a thermosetting resin composition by transfer molding or the like; TCP (Tape Carrier Package), which has a structure in which a semiconductor element connected to a tape carrier by bumps is sealed with a thermosetting resin composition; and COB (Chip On Board) which has a structure in which a semiconductor element is connected to wiring formed on a support member by wire bonding, flip chip bonding, solder, or the like, and then sealed with a thermosetting resin composition. Examples of semiconductor devices include a ball grid array (BGA), a chip size package (CSP), and a multi-chip package (MCP), each of which has a structure in which a semiconductor element is mounted on the surface of a support member having terminals for connecting a wiring board formed on the back surface thereof, the semiconductor element is connected to wiring formed on the support member by bump or wire bonding, and the semiconductor element is then sealed with a thermosetting resin composition. These semiconductor devices may be stacked packages in which two or more semiconductor elements are mounted on a substrate in a stacked configuration, or may be lumped molded packages in which two or more semiconductor elements are sealed at the same time with a thermosetting resin composition.

[0152] The semiconductor device of the present disclosure is preferably a surface-mount type semiconductor device from the viewpoint of high-density packaging. In the semiconductor device of the present disclosure, both surfaces of the semiconductor element may be in contact with the cured product of the thermosetting resin composition of the present disclosure, either directly or via a metal substrate, such as a lead frame, an Ag-plated substrate, an Au-plated substrate, or a Ni / Pd / Au-plated substrate. When both surfaces of the semiconductor element contact the cured product of the thermosetting resin composition directly or via a metal substrate, the contact area between the semiconductor element and the cured product increases. When the contact area between the semiconductor element and the cured product increases, peeling tends to occur at the interface between the semiconductor element and the cured product, which can result in deterioration of reflow resistance. Because the thermosetting resin composition of the present disclosure has excellent reflow resistance, applying the thermosetting resin composition of the present disclosure to a semiconductor device configured such that both surfaces of the semiconductor element contact the cured product of the thermosetting resin composition directly or via a metal substrate tends to be effective in preventing deterioration of reflow resistance. [Example]

[0153] The present disclosure will be specifically described below using examples, but the scope of the present disclosure is not limited to these examples.

[0154] [Preparation of Thermosetting Resin Composition] The thermosetting resin compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were prepared by mixing the following materials in the composition (parts by mass) shown in Table 1 and performing roll kneading under conditions of a kneading temperature of 80°C and a kneading time of 15 minutes. When a thermosetting resin composition was prepared with the same composition as in Example 1 except that all of the inorganic fillers were replaced with Inorganic Filler 2, kneading became difficult. Therefore, the thermosetting resin composition in which all of the inorganic fillers were replaced with Inorganic Filler 2 was not evaluated. In Table 1, "equivalent ratio (epoxy / phenol)" means the equivalent ratio between the epoxy resin and the curing agent.

[0155] Epoxy resin 1: Copolymerized epoxy resin of methoxynaphthalene, cresol and formaldehyde with an epoxy equivalent of 250g / eq and a softening point of 58℃ Epoxy resin 2: Biphenyl type epoxy resin with an epoxy equivalent of 196 g / eq and a softening point of 106°C Hardener 1: Aralkyl phenolic resin with a hydroxyl equivalent of 175g / eq and a softening point of 70°C Hardener 2: Melamine-modified phenolic resin with a hydroxyl equivalent of 120 g / eq and a softening point of 90°C Hardener 3: 2-[4-[(2-hydroxy-3-(2'-ethyl)hexyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine Curing accelerator: Addition product of triphenylphosphine and 1,4-benzoquinone Coupling agent 1: 3-glycidoxypropyltrimethoxysilane Coupling agent 2: N-phenyl-3-aminopropyltrimethoxysilane Release agent 1: Montan acid ester Release agent 2: Polyethylene oxide Colorant: Carbon black Ion exchanger: Hydrotalcite Stress relaxation agent 1: Indene-containing copolymer Stress relaxation agent 2: Epoxy-modified silicone resin Inorganic filler 1: Silica filler not surface-treated with a coupling agent (spherical silica with an average particle size of 20 μm, angle of repose: 49°, bulk density: 1.42 g / cm 3 ) Inorganic filler 2: 3-aminopropyltriethoxysilane-treated silica filler (spherical silica with a volume average particle size of 20 μm, angle of repose: 53°, bulk density: 1.28 g / cm 3 (Amount of 3-aminopropyltriethoxysilane treated per 100 parts by mass of silica before treatment with a coupling agent: 1 part by mass)

[0156] [evaluation] Each thermosetting resin composition was evaluated under the following conditions. The cured products of the thermosetting resin compositions were evaluated using cured products prepared under the following conditions. The evaluation results are shown in Table 1. The cured product was obtained by molding the thermosetting resin composition using a transfer molding machine at a mold temperature of 175°C, a molding pressure of 8.3 MPa, and a curing time of 120 seconds, followed by post-curing at 175°C for 6 hours.

[0157] <Liquidity> (Spiral Flow (SF) Evaluation) Using a spiral flow measurement mold conforming to EMMI-1-66, the thermosetting resin composition was molded with a transfer molding machine under conditions of a mold temperature of 180°C, a molding pressure of 6.9 MPa, and a curing time of 120 seconds, and the flow distance (inches) was determined.

[0158] (Gel time measurement) The gel time (GT) of the thermosetting resin composition was measured using a Curastometer manufactured by JSR Trading Co., Ltd. Measurement was carried out at 180°C using 3 g of the thermosetting resin composition using a Curastometer manufactured by JSR Trading Co., Ltd., and the time until the torque curve rose was taken as the gel time (seconds).

[0159] -Adhesive strength after moisture absorption- The thermosetting resin composition was applied to a Cu lead frame that was silver-plated (adhesion strength after moisture absorption 1) or Ni-Pd-Au-plated (adhesion strength after moisture absorption 2) as the adherend, and the thermosetting resin composition was cured under the above conditions. 2 ) was prepared. The test specimen was then humidified for 96 hours under conditions of 85°C and 85% RH. Using a DAGE bond tester, the shear speed (jig movement speed) was set to 50 μm / sec, and a force was applied in the shear direction to the obtained test specimen at a position approximately 100 μm above the adherend surface of the cured product, thereby measuring the force at which the adherend and the cured product of the thermosetting resin composition broke or peeled. The force at which the adherend broke or peeled was measured while the test specimen was heated to 260°C.

[0160] -Reflow resistance 1- A 28-pin SO (Small Outline) package (lead frame material: copper alloy, die pad top surface and lead tips silver-plated) with a 3.2 mm × 2.2 mm × 0.37 mm silicon chip mounted on a 5.2 mm × 4.1 mm die pad was encapsulated using the curable resin compositions of Examples 1 and 2 and Comparative Examples 1 and 2, followed by post-curing under the conditions described above. The resulting molded products were visually inspected for the absence of external cracks and confirmed for the absence of internal delamination using an ultrasonic flaw detector (Hitachi, Ltd., FS-200). The molded products were dried at 125°C for 12 hours and then humidified at 60°C and 60% RH for 120 hours. The reflow temperature was set to 260°C in accordance with JEDEC regulations, and the reflow process was performed three times at the same temperature. The external cracks on the package were visually inspected, and the internal delamination on the package was confirmed using an ultrasonic flaw detector. The percentage of packages in which either cracks or peeling occurred was calculated out of 16 test packages.

[0161] -Reflow resistance 2- A QFN (Quad Flat Non-leaded) package (lead frame material: copper alloy, Ni-Pd-Au plated) with a 3.0 mm × 3.0 mm × 0.37 mm silicon chip mounted on a 6.0 mm × 6.0 mm die pad was encapsulated using the curable resin compositions of Example 3 and Comparative Example 3 and then post-cured under the conditions described above. The resulting molded product was visually inspected for the absence of external cracks and confirmed for the absence of internal delamination using an ultrasonic flaw detector (Hitachi, Ltd., FS-200). The molded product was dried at 125°C for 12 hours and then humidified at 85°C and 60% RH for 168 hours. The reflow temperature was then set to 260°C in accordance with JEDEC regulations, and the reflow process was performed three times at the same temperature. The presence or absence of external cracks on the package was visually inspected, and the presence or absence of internal delamination on the package was confirmed using an ultrasonic flaw detector. The percentage of packages in which either cracks or peeling occurred was calculated out of 16 test packages.

[0162] [Table 1]

[0163] It can be seen from Table 1 that the thermosetting resin compositions of the examples are superior in reflow resistance to the thermosetting resin compositions of the comparative examples.

Claims

1. Contains a thermosetting resin, a curing agent, and an inorganic filler, the inorganic filler includes an inorganic filler that has been surface-treated with a coupling agent containing a primary amino group and an inorganic filler that has not been surface-treated with a coupling agent, the proportion of the inorganic filler surface-treated with the coupling agent containing a primary amino group in the entire inorganic filler is 30% by mass to 50% by mass; A thermosetting resin composition, in which the content of the inorganic filler surface-treated with the coupling agent containing a primary amino group relative to the entire thermosetting resin composition is 20% by mass to 60% by mass (excluding those in which the amount of the coupling agent treatment of the inorganic filler surface-treated with the coupling agent containing a primary amino group is 3 parts by mass or more relative to 100 parts by mass of the inorganic filler before being surface-treated with the coupling agent containing a primary amino group).

2. 2. The thermosetting resin composition according to claim 1, wherein the coupling agent is an aminoalkyltrialkoxysilane.

3. 3. The thermosetting resin composition according to claim 1, wherein the inorganic filler surface-treated with the coupling agent containing a primary amino group has an angle of repose of 50° to 60°.

4. The bulk density of the inorganic filler surface-treated with the coupling agent containing a primary amino group is 1.15 g / cm ３ ~1.40 g / cm ３ The thermosetting resin composition according to any one of claims 1 to 3, wherein

5. A semiconductor device comprising: a semiconductor element; and a cured product of the thermosetting resin composition according to any one of claims 1 to 4, which seals the semiconductor element.

6. 6. The semiconductor device according to claim 5, which is a surface mount type.

7. 7. The semiconductor device according to claim 5, wherein both surfaces of the semiconductor element are in contact with the cured product directly or via a metal substrate.

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