Epoxy resin composition for transfer molding, method for producing the same, epoxy resin composition for compression molding, and electronic component device

Abstract

A transfer molding epoxy resin composition, a method for producing the same, a compression molding epoxy resin composition, and an electronic component device, wherein the transfer molding epoxy resin composition contains: an epoxy resin; an inorganic filler; and a hardener, and contains a compound represented by General Formula (B) below. In General Formula (B), R 1 ~R 5 each independently represents a monovalent organic group having 1 to 6 carbons, X1 to X3 each independently represents an integer of 0 to 4, X4 and X5 each independently represents an integer of 0 to 3, n1 represents a number of 1 to 10, and n2 represents a number of 1 to 10.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to an epoxy resin composition for transfer molding and a manufacturing method thereof, an epoxy resin composition for compression molding, and an electronic component device. BACKGROUND

[0002] Since before, an epoxy resin composition has been widely used in the field of sealing of electronic components such as transistors, integrated circuits (ICs), and the like. The reason for this is that the epoxy resin achieves a balance of electrical properties, moisture resistance, heat resistance, mechanical properties, adhesion to inserts, and the like. As a method of sealing electronic components using an epoxy resin composition, a transfer molding method, a jet molding method, a compression molding method, and the like are known, of which the transfer molding method is most commonly used.

[0003] With the miniaturization, weight reduction, and high performance of electronic machines in recent years, the mounting density has been increasing, and electronic component devices have been adopting surface mounting type packages from the existing pin insertion type. In the case of mounting a semiconductor device on a wiring board, the existing pin insertion type package is one in which the pins are inserted into the wiring board and then soldered from the back of the wiring board, and thus the package is not directly exposed to high temperatures. However, in the surface mounting type package, the entire semiconductor device is processed using a solder bath or a reflow device, and the like, and thus is directly exposed to soldering temperatures. As a result, in the case where the package absorbs moisture, the absorbed moisture rapidly expands at the time of soldering, and peeling of the adhesion interface, cracking of the package, and the like occur, and there is a problem in that the reliability of the package in the mounting step decreases. As a countermeasure to solve the problem, a method of increasing the content of inorganic fillers in a molding material for element sealing in order to reduce the moisture absorbed in the semiconductor device is known (for example, refer to Patent Literature 1).

[0004] In addition, in recent years, in the field of electronic components, high speed and high density have been increasing, and along with this, the amount of heat generated by electronic components has significantly increased. Furthermore, the demand for electronic components that operate at high temperatures has also increased. Therefore, there is a demand for improvement in the thermal conductivity of the hardened product of plastics, particularly epoxy resins, used in the sealing of electronic components. As a method for improving the thermal conductivity of the hardened product of an epoxy resin, a method of increasing the filling amount of a high thermal conductivity filler such as alumina in an epoxy resin composition, and the like, has been reported (for example, refer to Patent Literature 2).

[0005] In addition, as the method for sealing electronic parts using the epoxy resin composition, as described above, transfer molding is the most common. On the other hand, in transfer molding, the molten epoxy resin composition is made to flow in a mold by pressurization, and thus, sometimes, coil flow is generated by the flow. In relation to this, methods for high flow of the epoxy resin composition have been studied, but the suppression of coil flow remains a problem. As a molding method other than transfer molding, compression molding (compression molding) is known. In compression molding, the epoxy resin composition is put in the cavity of a mold to be molten, the mold is closed and pressurized, and thus, the element is sealed. According to compression molding, compared to transfer molding, it is difficult to cause flow of the epoxy resin composition, and thus, the generation of coil flow can be suppressed.

[0006] As an epoxy resin composition for sealing semiconductor elements by compression molding, for example, Patent Literature 3 proposes a particulate epoxy resin composition characterized by containing an epoxy resin, a hardener, a hardening accelerator, an inorganic filler, a fatty acid having a melting point of 70°C or lower, and a silane coupling agent having a boiling point of 200°C or higher, and having a particle size distribution in which 85% by mass or more is in the range of 100 μm to 3 mm. It is described that by using such an epoxy resin composition, sufficient melting can be achieved in compression molding, and the filling property can be improved.

[0007] [Related Art Documents]

[0008] [Patent Literature]

[0009] Patent Literature 1: Japanese Patent Laid-Open No. 06-224328

[0010] Patent Literature 2: Japanese Patent Laid-Open No. 2007-153969

[0011] Patent Literature 3: Japanese Patent Laid-Open No. 2011-153173 SUMMARY

[0012] [Problems to be Solved by the Invention]

[0013] In the epoxy resin composition for transfer molding, as described above, in order to achieve various properties of the hardened product such as low hygroscopicity, high thermal conductivity, and the like, sometimes, the inorganic filler is contained in a high proportion. However, in the case where the inorganic filler is contained in a high proportion, sometimes, the viscosity of the composition increases and the mixing load increases, or the flowability decreases, and becomes a cause of coil flow, non-filling, and the like.

[0014] In addition, in the transfer molding method, in order to suppress the generation of burrs or improve the filling property to narrow portions, sometimes, an inorganic filler having a small particle size (ultra-fine silica or the like) is contained in the epoxy resin composition, and in the case, the increase in viscosity and the decrease in flowability are more significant.

[0015] In addition, from the viewpoint of mass production, it is desirable for the sealing epoxy resin composition to have good continuous formability. However, an epoxy resin composition that suppresses an increase in viscosity and has good continuous formability has not been obtained to date.

[0016] In view of the circumstances, the first to third embodiments of the present disclosure aim to provide an injection transfer molding epoxy resin composition that can suppress an increase in viscosity and has excellent continuous formability, a method for producing the same, and an electronic component device having a hardened product of the epoxy resin composition.

[0017] Further, in an epoxy resin composition used in compression molding, in order to achieve various characteristics such as low moisture absorption of the hardened product, high thermal conductivity, and the like, the proportion and particle size distribution of the inorganic filler are sometimes adjusted. In addition, from the viewpoint of adjusting the proportion and particle size distribution of the inorganic filler, obtaining the desired respective properties while maintaining a high filling and low viscosity, and the like, a high degree of freedom in design is desired for the epoxy resin composition. Therefore, it is desirable to obtain an epoxy resin composition that is easily meltable and suitable for element sealing using compression molding, by a method other than the method described in Patent Literature 3.

[0018] In view of the circumstances, the fourth embodiment of the present disclosure aims to provide an epoxy resin composition that is easily meltable and an electronic component device having a hardened product of the epoxy resin composition.

[0019] Technical means for solving the problem

[0020] In the first to third embodiments, the means for solving the problem includes the following forms.

[0021] <1> A method for producing an injection transfer molding epoxy resin composition, comprising mixing an epoxy resin, an inorganic filler having an average particle diameter of 50 nm or less, and a hardener including a compound represented by General Formula (B) below.

[0022] [Chemical Formula 1]

[0023]

[0024] In General Formula (B),

[0025] R 1 ~ R 5 each independently represents a monovalent organic group having a carbon number of 1 to 6,

[0026] X1 to X3 each independently represents an integer of 0 to 4,

[0027] X4 and X5 each independently represents an integer of 0 to 3,

[0028] n1 represents a number of 1 to 10,

[0029] n2 represents a number of 1 to 10.

[0030] <2> The production method according to <1>, wherein the epoxy resin comprises a biphenyl-type epoxy resin.

[0031] <3> The production method according to <2>, wherein the content ratio of the biphenyl-type epoxy resin in the transfer molding epoxy resin composition is 30 to 100 mass% with respect to the total mass of the epoxy resin.

[0032] <4> The production method according to any one of <1> to <3>, wherein the content ratio of the inorganic filler is 60% by volume or more with respect to the total volume of the transfer molding epoxy resin composition.

[0033] <5> The production method according to any one of <1> to <4>, wherein the content ratio of the compound represented by General Formula (B) is 30 to 100 mass% with respect to the total mass of the hardening agent in the transfer molding epoxy resin composition.

[0034] <6> A transfer molding epoxy resin composition comprising:

[0035] an epoxy resin;

[0036] an inorganic filler; and

[0037] a hardening agent comprising a compound represented by General Formula (B) below,

[0038] the inorganic filler is a mixture of an inorganic filler having an average particle diameter of 50 nm or less and an inorganic filler having an average particle diameter of more than 50 nm, and the content of the inorganic filler having an average particle diameter of 50 nm or less is 5 mass parts or more with respect to 100 mass parts of the epoxy resin.

[0039] [Chem. 2]

[0040]

[0041] in General Formula (B),

[0042] R 1 ~ R 5 each independently represents a monovalent organic group having a carbon number of 1 to 6,

[0043] X1 to X3 each independently represent an integer of 0 to 4,

[0044] X4 and X5 each independently represent an integer of 0 to 3,

[0045] n1 represents a number of 1 to 10,

[0046] n2 represents a number of 1 to 10.

[0047] <7> An epoxy resin composition for transfer molding, comprising:

[0048] an epoxy resin;

[0049] an inorganic filler; and

[0050] a hardener including a compound represented by General Formula (B) below,

[0051] The inorganic filler includes an inorganic filler having a particle diameter of 50 nm or less, and the content of the inorganic filler having a particle diameter of 50 nm or less is 5 parts by mass or more with respect to 100 parts by mass of the epoxy resin.

[0052] [Chemical 3]

[0053]

[0054] In General Formula (B),

[0055] R 1 ~ R 5 each independently represents a monovalent organic group having a carbon number of 1 to 6,

[0056] X1 to X3 each independently represent an integer of 0 to 4,

[0057] X4 and X5 each independently represent an integer of 0 to 3,

[0058] n1 represents a number of 1 to 10,

[0059] n2 represents a number of 1 to 10.

[0060] <8> The epoxy resin composition for transfer molding according to <6> or <7>, wherein the epoxy resin includes a biphenyl-type epoxy resin.

[0061] <9> The epoxy resin composition for transfer molding according to <8>, wherein the content ratio of the biphenyl-type epoxy resin is 30% to 100% by mass with respect to the total mass of the epoxy resin.

[0062] <10> The epoxy resin composition for transfer molding according to any one of <6> to <9>, wherein the content ratio of the inorganic filler is 60% or more by volume with respect to the total volume of the epoxy resin composition.

[0063] <11> The epoxy resin composition for transfer molding according to any one of <6> to <10>, wherein the content ratio of the compound represented by General Formula (B) is 30% to 100% by mass with respect to the total mass of the hardener.

[0064] An electronic component device including:

[0065] an element; and

[0066] a hardened product of the epoxy resin composition obtained by the production method according to any one of <1> to <5>, or a hardened product of the epoxy resin composition according to any one of <6> to <11> seals the element.

[0067] In a fourth embodiment, a means to solve the problem includes the following form.

[0068] <13> A compression molding epoxy resin composition, comprising:

[0069] an epoxy resin;

[0070] an inorganic filler; and

[0071] a hardener including a compound represented by General Formula (B) below.

[0072] [Chemical Formula 4]

[0073]

[0074] In General Formula (B),

[0075] R 1 ~ R 5 each independently represents a monovalent organic group having a carbon number of 1 to 6,

[0076] X1 to X3 each independently represents an integer of 0 to 4,

[0077] X4 and X5 each independently represents an integer of 0 to 3,

[0078] n1 represents a number of 1 to 10,

[0079] n2 represents a number of 1 to 10.

[0080] <14> The compression molding epoxy resin composition according to <13>, wherein a content ratio of the inorganic filler is 60% by volume or more with respect to a total volume of the compression molding epoxy resin composition.

[0081] <15> The compression molding epoxy resin composition according to <13> or <14>, wherein a content ratio of the compound represented by General Formula (B) is 30% by mass to 100% by mass with respect to a total mass of the hardener.

[0082] The compression-molding epoxy resin composition according to any one of <13> to <15>, further containing a release agent at a content rate exceeding 0 mass% and 2.0 mass% or less with respect to the total mass of the compression-molding epoxy resin composition.

[0083] <17> An electronic component device comprising:

[0084] an element; and

[0085] a hardened product of the compression-molding epoxy resin composition according to any one of <13> to <16> that seals the element.

[0086] [Effects of the Invention]

[0087] According to the first to third embodiments of the present disclosure, an injection transfer molding epoxy resin composition that can suppress an increase in viscosity and has excellent continuous moldability, a method for producing the same, and an electronic component device having a hardened product of the epoxy resin composition can be provided.

[0088] According to the fourth embodiment of the present disclosure, an epoxy resin composition that is easily melted and an electronic component device having a hardened product of the epoxy resin composition can be provided. DETAILED DESCRIPTION

[0089] Hereinafter, the embodiments of the present disclosure will be described in detail. However, the embodiments of the present disclosure are not limited to the following embodiments. In the following embodiments, structural elements (including element steps, etc.) are not necessarily essential unless specifically indicated. The same applies to numerical values and ranges thereof, and the embodiments of the present disclosure are not limited thereto.

[0090] In the present disclosure, in the phrase of "step", even in a case where it is not possible to clearly distinguish from other steps, as long as the purpose of the step is achieved, the step is included.

[0091] In the present disclosure, in a numerical range represented by "~", the numerical values written before and after the "~" are included as the minimum value and the maximum value, respectively.

[0092] In the present disclosure, in a numerical range written in stages, the upper limit value or the lower limit value written in one numerical range can be replaced with the upper limit value or the lower limit value of another numerical range written in stages. In addition, in the numerical range written in the present disclosure, the upper limit value or the lower limit value of the numerical range can be replaced with the value shown in the examples.

[0093] In the present disclosure, a plurality of substances equivalent to each component can also be contained. In the case where a plurality of substances equivalent to each component is present in the composition, unless otherwise specified, the content or amount of each component refers to the total content or amount of the plurality of substances present in the composition.

[0094] In the present disclosure, a plurality of particles equivalent to each component can also be contained. In the case where a plurality of particles equivalent to each component is present in the composition, unless otherwise specified, the particle diameter of each component refers to the value with respect to the mixture of the plurality of particles present in the composition.

[0095] 1. First to third embodiments

[0096] First, the first to third embodiments will be described in detail.

[0097] 1.1 Method for producing an epoxy resin composition for transfer molding

[0098] The method for producing an epoxy resin composition for transfer molding of the first embodiment includes mixing an epoxy resin, an inorganic filler having an average particle diameter of 50 nm or less, and a hardening agent containing a compound represented by General Formula (B) below.

[0099] [Chemical Formula 5]

[0100]

[0101] In General Formula (B),

[0102] R 1 ~ R 5 each independently represents a monovalent organic group having a carbon number of 1 to 6,

[0103] X1to X3each independently represents an integer of 0 to 4,

[0104] X4and X5each independently represents an integer of 0 to 3,

[0105] n1represents a number of 1 to 10,

[0106] n2represents a number of 1 to 10.

[0107] The epoxy resin composition produced by the method for producing an epoxy resin composition for transfer molding of the first embodiment is produced by mixing an inorganic filler having an average particle diameter of 50 nm or less. It is generally known that if a fine inorganic filler is mixed in an epoxy resin composition, there is a tendency for the viscosity of the composition to significantly increase, but if the compound represented by General Formula (B) is used in combination, the increase in viscosity can be well suppressed and an epoxy resin composition excellent in continuous moldability can be obtained.

[0108] Hereinafter, the epoxy resin composition manufactured by the manufacturing method of the transfer molding epoxy resin composition of the first embodiment will also be referred to as "the epoxy resin composition of the first embodiment".

[0109] The manufacturing method of the epoxy resin composition of the first embodiment includes a step of mixing an epoxy resin, an inorganic filler having an average particle diameter of 50 nm or less, and a hardening agent containing a compound represented by General Formula (B), and other steps are not particularly limited. As the manufacturing method of the epoxy resin composition of the first embodiment, for example, a method in which a prescribed amount of ingredients is sufficiently mixed by a mixer or the like, and then melt-kneaded by a mixing roll, an extruder, or the like, and then cooled and pulverized can be exemplified. More specifically, for example, a method in which a prescribed amount of the ingredients is uniformly stirred and mixed, and then kneaded and cooled by using a kneader, a roll, an extruder, or the like that is previously heated to 70°C to 140°C, and then pulverized can be exemplified.

[0110] [The epoxy resin composition of the first embodiment]

[0111] The epoxy resin composition of the first embodiment is manufactured by the manufacturing method of the transfer molding epoxy resin composition of the first embodiment, and contains an epoxy resin, an inorganic filler, and a hardening agent containing a compound represented by General Formula (B). The epoxy resin composition of the first embodiment can further contain a hardening accelerator, other additives, or the like.

[0112] [The epoxy resin composition of the second embodiment]

[0113] The epoxy resin composition of the second embodiment contains an epoxy resin, an inorganic filler, and a hardening agent containing a compound represented by General Formula (B), the inorganic filler being a mixture of an inorganic filler having an average particle diameter of 50 nm or less and an inorganic filler having an average particle diameter of more than 50 nm, and the content of the inorganic filler having an average particle diameter of 50 nm or less is 5 parts by mass or more with respect to 100 parts by mass of the epoxy resin.

[0114] As can be understood, the epoxy resin composition of the second embodiment contains the inorganic filler having an average particle diameter of 50 nm or less in an amount of 5 parts by mass or more with respect to 100 parts by mass of the epoxy resin, a significant increase in viscosity is suppressed, and continuous moldability is excellent.

[0115] [The epoxy resin composition of the third embodiment]

[0116] The epoxy resin composition of the third embodiment contains: an epoxy resin; an inorganic filler; and a hardening agent, which contains the compound represented by the general formula (B), the inorganic filler contains an inorganic filler having a particle diameter of 50 nm or less, and the content of the inorganic filler having a particle diameter of 50 nm or less is 5 parts by mass or more with respect to 100 parts by mass of the epoxy resin.

[0117] As is apparent, the epoxy resin composition of the third embodiment contains the inorganic filler having a particle diameter of 50 nm or less in an amount of 5 parts by mass or more with respect to 100 parts by mass of the epoxy resin, a significant increase in viscosity is suppressed, and the continuous moldability is excellent.

[0118] Hereinafter, the epoxy resin, the inorganic filler, the hardening agent, and other arbitrary components contained in the epoxy resin compositions of the first to third embodiments are described in detail. In the description regarding the first to third embodiments, in the description of matters common to the epoxy resin compositions of the first to third embodiments, the epoxy resin compositions of the first to third embodiments are sometimes simply referred to as "epoxy resin compositions".

[0119] < Epoxy Resin >

[0120] The epoxy resin compositions of the first to third embodiments contain an epoxy resin. The epoxy resin is not particularly limited as long as it is an epoxy resin having two or more epoxy groups in one molecule.

[0121] Specifically, the following can be cited: a novolak-type epoxy resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds such as phenol, cresol, dimethylphenol, resorcinol, catechol, bisphenol A, bisphenol F, and naphthol compounds such as a-naphthol, β-naphthol, and dihydronaphthalene, with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde, in the presence of an acid catalyst, and epoxidizing the novolak resin; a triphenylmethane-type epoxy resin obtained by condensing or co-condensing the phenolic compound with an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde, in the presence of an acid catalyst, and epoxidizing the triphenylmethane-type phenol resin; a copolymerization-type epoxy resin obtained by co-condensing the phenol compound and the naphthol compound with an aldehyde compound in the presence of an acid catalyst, and epoxidizing the novolak resin; a diphenylmethane-type epoxy resin that is a diglycidyl ether of bisphenol A, bisphenol F, or the like; a biphenyl-type epoxy resin that is a diglycidyl ether of alkyl-substituted or unsubstituted biphenol; a stilbene-type epoxy resin that is a diglycidyl ether of a stilbene-based phenolic compound; a sulfur atom-containing epoxy resin that is a diglycidyl ether of bisphenol S or the like; an epoxy resin that is a glycidyl ester of a polybasic carboxylic acid compound such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; a glycidyl amine-type epoxy resin obtained by replacing an active hydrogen bonded to a nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, or the like with a glycidyl group; a dicyclopentadiene-type epoxy resin obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound; an alicyclic-type epoxy resin obtained by epoxidizing an olefin bond within 2,3-epoxy-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, 3,4-epoxy cyclohexylmethyl-3,4-epoxy cyclohexane carboxylate, or the like; a p-xylene-modified epoxy resin that is a glycidyl ether of a p-xylene-modified phenol resin; an m-xylene-modified epoxy resin that is a glycidyl ether of an m-xylene-modified phenol resin; a terpene-modified epoxy resin that is a glycidyl ether of a terpene-modified phenol resin; a dicyclopentadiene-modified epoxy resin that is a glycidyl ether of a dicyclopentadiene-modified phenol resin; a cyclopentadiene-modified epoxy resin that is a glycidyl ether of a cyclopentadiene-modified phenol resin; a polycyclic aromatic ring-modified epoxy resin that is a glycidyl ether of a polycyclic aromatic ring-modified phenol resin; a naphthalene-type epoxy resin that is a glycidyl ether of a naphthalene ring-containing phenol resin; a halogenated phenol novolak-type epoxy resin; a hydroquinone-type epoxy resin; a trimethylolpropane-type epoxy resin; a linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid;An epoxy resin of an aralkyl type, such as an epoxydized phenol aralkyl resin, an epoxydized naphthol aralkyl resin, and the like. Further, an epoxydized silicone resin, an epoxydized acrylic resin, and the like can also be cited as the epoxy resin. These epoxy resins can be used singly or in combination of two or more.

[0122] Among the epoxy resins, from the viewpoint of the balance between the reflow resistance and the flowability, an epoxy resin selected from the group consisting of a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, a sulfur atom-containing epoxy resin, a novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin, a copolymerized type epoxy resin, and an aralkyl type epoxy resin (these are referred to as "specific epoxy resins") is preferable. The specific epoxy resins can be used singly or in combination of two or more.

[0123] In the case where the epoxy resin contains the specific epoxy resins, from the viewpoint of exerting the properties of the specific epoxy resins, the total content ratio thereof is preferably 30% by mass or more, more preferably 50% by mass or more, of the entire epoxy resin.

[0124] From the viewpoint of the flowability, the specific epoxy resins are more preferably a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, and a sulfur atom-containing epoxy resin, and from the viewpoint of the heat resistance, a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin, and an aralkyl type epoxy resin are preferable.

[0125] Among them, from the viewpoint of the balance of the properties, the epoxy resin preferably contains at least one selected from the group consisting of a diphenylmethane type epoxy resin, a biphenyl type epoxy resin, and a triphenylmethane type epoxy resin, more preferably two or more of these are used in combination.

[0126] In the case where the epoxy resin contains the diphenylmethane type epoxy resin, the content ratio of the diphenylmethane type epoxy resin can be 40% by mass or more, 50% by mass or more, or 60% by mass or more, relative to the total mass of the epoxy resin. In addition, the content ratio of the diphenylmethane type epoxy resin can be 90% by mass or less, 80% by mass or less, or 70% by mass or less, relative to the total mass of the epoxy resin.

[0127] When the epoxy resin includes a biphenyl-type epoxy resin, the content of the biphenyl-type epoxy resin relative to the total mass of the epoxy resin can be 10% by mass or more, 20% by mass or more, or 30% by mass or more. Furthermore, the content of the biphenyl-type epoxy resin relative to the total mass of the epoxy resin can be 70% by mass or less, 60% by mass or less, or 50% by mass or less. Moreover, the content of the biphenyl-type epoxy resin relative to the total mass of the epoxy resin is preferably 30% by mass to 100% by mass, more preferably 30% by mass to 90% by mass, and even more preferably 30% by mass to 80% by mass.

[0128] When the epoxy resin includes triphenylmethane-type epoxy resin, the content of triphenylmethane-type epoxy resin relative to the total mass of the epoxy resin can be 30% by mass or more, 40% by mass or more, or 50% by mass or more. Alternatively, the content of triphenylmethane-type epoxy resin relative to the total mass of the epoxy resin can be 70% by mass or less, 60% by mass or less, or 50% by mass or less.

[0129] In one embodiment, the epoxy resin is preferably a combination comprising a diphenylmethane-type epoxy resin and a biphenyl-type epoxy resin. When the epoxy resin comprises a combination of a diphenylmethane-type epoxy resin and a biphenyl-type epoxy resin, the ratio of the diphenylmethane-type epoxy resin to the biphenyl-type epoxy resin, based on a mass basis, is preferably 40:60 to 90:10, more preferably 50:50 to 80:20, and even more preferably 60:40 to 70:30.

[0130] In another embodiment, the epoxy resin is preferably a combination comprising biphenyl-type epoxy resin and triphenylmethane-type epoxy resin. When the epoxy resin comprises a combination of biphenyl-type epoxy resin and triphenylmethane-type epoxy resin, the ratio of the biphenyl-type epoxy resin to the triphenylmethane-type epoxy resin, based on a mass basis, is preferably 20:80 to 80:20, more preferably 30:70 to 70:30, and even more preferably 40:60 to 60:40.

[0131] The following are specific examples of preferred epoxy resins.

[0132] There is no particular limitation as long as the biphenyl-type epoxy resin has a biphenyl backbone. For example, epoxy resins represented by the following general formula (II) are preferred. In the epoxy resin 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 all other R groups are methyl groups. 8 YX-4000H (Mitsubishi Chemical Corporation, trade name), which contains hydrogen atoms, has all R... 8 4,4'-bis(2,3-epoxypropoxy)biphenyl with hydrogen atoms, all R8 R is a hydrogen atom, and R 8 R is a hydrogen atom, and R 8 R is a hydrogen atom, and R

[0133] [Chemical Formula 7]

[0134]

[0135] In formula (II), R 8 R represents a hydrogen atom, an alkyl group having 1 to 12 carbons, or an aromatic group having 4 to 18 carbons, and can be the same or different. n is an average value, and represents a number from 0 to 10.

[0136] 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 preferable. In the epoxy resin represented by the following general formula (III), R 9 R is a hydrogen atom, and R 9 R is a hydrogen atom, and R 10 R is a hydrogen atom, and R 9 R is a hydrogen atom, and R 9 R is a hydrogen atom, and R 10 R is a hydrogen atom, and R

[0137] [Chemical Formula 8]

[0138]

[0139] In formula (III), R 9 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbons, and can be the same or different. n is an average value, and represents a number from 0 to 10. 10 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbons, and can be the same or different. n is an average value, and represents a number from 0 to 10.

[0140] 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 preferable. In the epoxy resin represented by the following general formula (IV), R 11 R is a hydrogen atom, and R 12 R is a hydrogen atom, and R 12YSLV-80XY (Nippon Shokubai Co., Ltd., trade name) and the like in which Y is hydrogen atom can be obtained as a commercial product.

[0141] [Chem. 9]

[0142]

[0143] In formula (IV), R 11 and R 12 represent hydrogen atom or monovalent organic group having carbon number 1 to 18, and can be the same or different from each other. n is an average value, and represents a number of 0 to 10.

[0144] The epoxy resin having sulfur atom is not particularly limited as long as it is an epoxy resin having sulfur atom. For example, the epoxy resin represented by the following general formula (V) can be exemplified. In the epoxy resin represented by the following general formula (V), R 13 R1in which the positions of the oxygen atoms are set to 4-position and 4'-position, 3,3'-position is tert-butyl group, 6,6'-position is methyl group, and R 13 YSLV-120TE (Nippon Shokubai Co., Ltd., trade name) and the like in which Y is hydrogen atom can be obtained as a commercial product.

[0145] [Chem. 10]

[0146]

[0147] In formula (V), R 13 represent hydrogen atom or monovalent organic group having carbon number 1 to 18, and can be the same or different from each other. n is an average value, and represents a number of 0 to 10.

[0148] The novolak-type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing novolak-type phenol resin. For example, it is preferable to use an epoxy resin obtained by epoxidizing phenol novolak resin, cresol novolak resin, naphthol novolak resin, or the like by glycidyl etherification or the like, and it is more preferable to use an epoxy resin represented by the following general formula (VI). In the epoxy resin represented by the following general formula (VI), R 14 are all hydrogen atoms, R 15 ESCN-190, ESCN-195 (Sumitomo Chemical Co., Ltd., trade name) in which R 14 are all hydrogen atoms, i = 0, N-770, N-775 (DIC Corporation, trade name) in which R 14 are all hydrogen atoms, i = 0, and R 15A styrene-modified phenol novolac-type epoxy resin in which the moiety of -CH(CH3)-Ph is styrene, i.e., YDAN-1000-10C (Nippon Shokubai Co., Ltd., trade name) and the like are available as commercial products.

[0149] [Chem. 11]

[0150]

[0151] In formula (VI), R 14 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbons, and can be the same or different. 15 represents a monovalent organic group having 1 to 18 carbons, and can be the same or different. Each of i independently represents an integer of 0 to 3. n is an average value, and represents a number of 0 to 10.

[0152] 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, it is preferable to be an epoxy resin represented by the following general formula (VII). Among the epoxy resins represented by the following general formula (VII), HP-7200 (DIC Corporation, trade name) in which i = 0 and the like are available as commercial products.

[0153] [Chem. 12]

[0154]

[0155] In formula (VII), R 16 represents a monovalent organic group having 1 to 18 carbons, and can be the same or different. Each of i independently represents an integer of 0 to 3. n is an average value, and represents a number of 0 to 10.

[0156] The triphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin using a compound having a triphenylmethane skeleton as a raw material. For example, it is preferable to be an epoxy resin obtained by glycidyl etherification of a triphenylmethane-type phenol resin such as a novolac-type phenol resin using a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group, and it is more preferable to be an epoxy resin represented by the following general formula (VIII). Among the epoxy resins represented by the following general formula (VIII), 1032H60 (Mitsubishi Chemical Corporation, trade name) in which i is 0 and k is 0, EPPN-502H (Nippon Kayaku Co., Ltd., trade name) and the like are available as commercial products.

[0157] [Chem. 13]

[0158]

[0159] In formula (VIII), R 17 and R18 each independently represents a monovalent organic group having 1 to 18 carbons, and can 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.

[0160] The copolymerization type epoxy resin obtained by epoxidizing the novolak resin obtained from the naphthol compound and the phenol compound with the aldehyde compound is not particularly limited as long as it is an epoxy resin using a compound having a naphthol skeleton and a compound having a phenol skeleton as a raw material. For example, it is preferable to use an epoxy resin obtained by glycidyl etherifying a novolak type phenol resin using a compound having a naphthol skeleton and a compound having a phenol skeleton, and it is more preferable to use an epoxy resin represented by the following general formula (IX). In the epoxy resin represented by the following general formula (IX), R 21 NC-7300 (Nippon Kayaku Co., Ltd., trade name) and the like in which R is a methyl group, i is 1, j is 0, and k is 0 are available as commercial products.

[0161] [Chem. 14]

[0162]

[0163] In formula (IX), R 19 ~R 21 each independently represents a monovalent organic group having 1 to 18 carbons, and can 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. l and m are each an average value, and are a number of 1 to 10, and (l+m) represents a number of 2 to 10. The terminal of the epoxy resin represented by formula (IX) is the following formula (IX-1) or formula (IX-2). In formula (IX-1) and formula (IX-2), R 19 ~R 21 , i, j, and k are the same as the definitions of R 19 ~R 21 , i, j, and k. n is 1 (in the case of bonding via a methylene group) or 0 (in the case of not bonding via a methylene group).

[0164] [Chem. 15]

[0165]

[0166] As the epoxy resin represented by the general formula (IX), a random copolymer randomly containing one structural unit and m structural units, an alternating copolymer alternately containing one structural unit and m structural units, a copolymer regularly containing one structural unit and m structural units, a block copolymer containing one structural unit and m structural units in a block shape, and the like can be exemplified. Any one of these can be used alone, or two or more of these can be used in combination.

[0167] As the copolymerization-type epoxy resin, a methoxynaphthalene-cresol formaldehyde co-condensation type epoxy resin containing two structural units in the general formula (IX-3) below in a random, alternating, or block order, i.e., an EPICLON HP-5000 (DIC Corporation, trade name) represented by the general formula (IX-3) below, is also preferable. In the general formula (IX-3) below, n and m are each an average value and are a number of 1 to 10, and (n+m) represents a number of 2 to 10, preferably n and m are each an average value and are a number of 1 to 9, and (n+m) represents a number of 2 to 10.

[0168] [Chemical 16]

[0169]

[0170] The aralkyl-type epoxy resin is not particularly limited as long as it is an epoxy resin synthesized using, as a raw material, a phenol resin synthesized from at least one selected from the group consisting of phenol compounds such as phenol, cresol, and the like, and naphthol compounds such as naphthol, dimethylnaphthol, and the like, and dimethoxy-p-xylene, bis(methoxymethyl) biphenyl, or a derivative of these. For example, it is preferable to use an epoxy resin obtained by glycidyl etherification of a phenol resin synthesized from at least one selected from the group consisting of phenol compounds such as phenol, cresol, and the like, and naphthol compounds such as naphthol, dimethylnaphthol, and the like, and dimethoxy-p-xylene, bis(methoxymethyl) biphenyl, or a derivative of these, and it is more preferable to use an epoxy resin represented by the general formula (X) and the general formula (XI) below.

[0171] In the epoxy resin represented by the general formula (X) below, i is 0 and R 38 NC-3000S (Nippon Kayaku Co., Ltd., trade name) in which i is 0 and R 38 is a hydrogen atom, is mixed with an epoxy resin in which all of R 8 in the general formula (II) is a hydrogen atom, to obtain CER-3000 (Nippon Kayaku Co., Ltd., trade name), and the like, which are available as commercial products. In addition, an epoxy resin represented by the general formula (XI) below in which i is 0, j is 0, and k is 0, such as ESN-175 (Nippon Steel Chemical & Materials Co., Ltd., trade name), is available as a commercial product.

[0172] [Chemical Formula 17]

[0173]

[0174] In formula (X) and formula (XI), R 38 represents a hydrogen atom or a monovalent organic group having a carbon number of 1 to 18, and can be the same or different. 37 , R 39 to R 41 represent a monovalent organic group having a carbon number of 1 to 18, and can be the same or different. i and j each independently represent an integer of 0 to 3, k each independently represents an integer of 0 to 4, and 1 each independently represents an integer of 0 to 6. n is an average value, and each independently represents a number of 0 to 10.

[0175] With respect to R 8 to R 21 and R 37 to R 41 in the general formula (II) to the general formula (XI), the "can be the same or different" means, for example, that 8 to 88 R 8 in formula (II) can be the same or different. With respect to other R 9 to R 21 and R 37 to R 41 , it also means that the number of each contained in the formula can be the same or different. In addition, R 8 to R 21 and R 37 to R 41 can be the same or different. For example, R 9 and R 10 can be the same or different.

[0176] In addition, the monovalent organic group having a carbon number of 1 to 18 in the general formula (III) to the general formula (XI) is preferably an alkyl group or an aryl group.

[0177] n in the general formula (II) to the general formula (XI) is an average value, and is preferably in the range of each independently 0 to 10. If n is 10 or less, the melt viscosity of the resin component does not become excessively high, the viscosity at the time of melt molding of the epoxy resin composition decreases, and there is a tendency to suppress the generation of filling defects, deformation of the bonding wire (metal wire connecting the connection element and the lead wire), and the like. n is more preferably in the range of 0 to 4.

[0178] The epoxy equivalent weight of the epoxy resin is not particularly limited. From the viewpoint of balancing various properties such as moldability, resistance to reflow soldering, and electrical reliability, the epoxy equivalent weight of the epoxy resin is preferably 100 g / eq to 1000 g / eq, more preferably 150 g / eq to 500 g / eq. The epoxy equivalent weight of the epoxy resin is set to a value determined by a method according to Japanese Industrial Standards (JIS) K 7236:2009.

[0179] In the case where the epoxy resin is a solid, the softening point or the melting point thereof is not particularly limited. From the viewpoints of moldability and resistance to reflow soldering, it is preferably 40°C to 180°C, and from the viewpoint of operability at the time of preparation of the epoxy resin composition, it is more preferably 50°C to 130°C. The melting point of the epoxy resin is set to a value determined by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is set to a value determined by a method according to JIS K 7234:1986 (ring and ball method).

[0180] From the viewpoints of strength, flowability, heat resistance, moldability, and the like, the content ratio of the epoxy resin in the epoxy resin composition is preferably 0.5 mass% to 50 mass%, more preferably 2 mass% to 30 mass%.

[0181] <Inorganic Filler>

[0182] The epoxy resin composition of the first to third embodiments contains an inorganic filler. The material of the inorganic filler is not particularly limited. Specifically, inorganic materials such as silica (fused silica, crystalline silica, and the like), glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zirconium oxide, zircon, forsterite, block talc, spinel, mullite, titanium oxide, talc, clay, mica, and the like can be exemplified. An inorganic filler having a flame retardant effect can also be used. As the inorganic filler having a flame retardant effect, a complex metal hydroxide such as aluminum hydroxide, magnesium hydroxide, a composite hydroxide of magnesium and zinc, zinc borate, and the like can be exemplified. Among them, from the viewpoint of reduction in linear expansion coefficient, silica is preferable, and from the viewpoint of high thermal conductivity, alumina is preferable. The inorganic filler can be used alone or in combination of two or more. As the state of the inorganic filler, a powder, a particle in which a powder is spheroidized, a fiber, and the like can be exemplified.

[0183] The shape of the inorganic filler is not particularly limited. From the viewpoint of flowability of the epoxy resin composition, the particle shape of the inorganic filler is preferably spherical.

[0184] The epoxy resin composition of the first embodiment is manufactured by mixing an inorganic filler having an average particle diameter of 50 nm or less. If the epoxy resin composition is manufactured by mixing an inorganic filler having an average particle diameter of 50 nm or less, there is a tendency that the filling property of the epoxy resin composition to a narrow portion is improved and generation of burrs at the time of molding is suppressed.

[0185] In the epoxy resin composition of the first embodiment, it is preferable that, in addition to the inorganic filler having an average particle diameter of 50 nm or less, an inorganic filler having an average particle diameter of more than 50 nm is mixed. The inorganic filler having an average particle diameter of 50 nm or less and the inorganic filler having an average particle diameter of more than 50 nm can each be one kind or two or more kinds.

[0186] In the epoxy resin composition of the second embodiment, the inorganic filler is a mixture of an inorganic filler having an average particle diameter of 50 nm or less and an inorganic filler having an average particle diameter of more than 50 nm, and the content of the inorganic filler having an average particle diameter of 50 nm or less is 5 parts by mass or more with respect to 100 parts by mass of the epoxy resin. By using a mixture of an inorganic filler having an average particle diameter of 50 nm or less and an inorganic filler having an average particle diameter of more than 50 nm as the inorganic filler, there is a tendency that the filling property of the epoxy resin composition to a narrow portion is improved and generation of burrs at the time of molding is suppressed. The inorganic filler having an average particle diameter of 50 nm or less and the inorganic filler having an average particle diameter of more than 50 nm can each be one kind or two or more kinds.

[0187] In the epoxy resin composition of the third embodiment, the inorganic filler includes an inorganic filler having a particle diameter of 50 nm or less, and the content of the inorganic filler having a particle diameter of 50 nm or less is 5 parts by mass or more with respect to 100 parts by mass of the epoxy resin. By adjusting 5 parts by mass or more of the inorganic filler having a particle diameter of 50 nm or less with respect to 100 parts by mass of the epoxy resin, there is a tendency that the filling property of the epoxy resin composition to a narrow portion is improved and generation of burrs at the time of molding is suppressed.

[0188] The average particle diameter of the inorganic filler having an average particle diameter of 50 nm or less is preferably 5 nm to 50 nm, more preferably 10 nm to 50 nm, and further preferably 15 nm to 50 nm.

[0189] The maximum particle diameter of the inorganic filler having an average particle diameter of 50 nm or less is not particularly limited and can be 2 μm or less, 1 μm or less, 500 nm or less, or 50 nm or less.

[0190] In the present disclosure, the maximum particle diameter of the inorganic filler refers to the particle diameter (D90%) at which the cumulative from the small-diameter side is 90% in the particle size distribution on a volume basis obtained by a laser diffraction scattering method particle size distribution measuring device.

[0191] From the viewpoint of improving the filling property for narrow portions, suppressing burrs during molding, and the like, the content of the inorganic filler having an average particle diameter of 50 nm or less is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and further preferably 11 parts by mass or more, and particularly preferably 13 parts by mass or more, and most preferably 15 parts by mass or more, relative to 100 parts by mass of the epoxy resin. In addition, from the viewpoint of suppressing an increase in viscosity, the content of the inorganic filler having an average particle diameter of 50 nm or less can be 30 parts by mass or less, 25 parts by mass or less, or 20 parts by mass or less, relative to 100 parts by mass of the epoxy resin. From the viewpoint of preferably obtaining the effects of improving the filling property for narrow portions, suppressing burrs during molding, and the like, the content of the inorganic filler having an average particle diameter of 50 nm or less is preferably 5 parts by mass to 30 parts by mass, more preferably 10 parts by mass to 30 parts by mass, and further preferably 11 parts by mass to 25 parts by mass, and particularly preferably 13 parts by mass to 20 parts by mass, relative to 100 parts by mass of the epoxy resin.

[0192] The inorganic filler having an average particle diameter of more than 50 nm and 80 μm or less preferably has an average particle diameter of more than 50 nm and 80 μm or less, more preferably 0.1 μm to 70 μm, and further preferably 0.2 μm to 50 μm.

[0193] In one aspect, the inorganic filler has, in addition to the inorganic filler having an average particle diameter of 50 nm or less, an inorganic filler having an average particle diameter of more than 50 nm and 2.0 μm or less and an inorganic filler having an average particle diameter of more than 2.0 μm and 80 μm or less.

[0194] In a more preferable aspect, the inorganic filler has, in addition to the inorganic filler having an average particle diameter of 50 nm or less, an inorganic filler having an average particle diameter of 0.1 μm to 1 μm and an inorganic filler having an average particle diameter of 2 μm to 50 μm.

[0195] In a further preferable aspect, the inorganic filler has, in addition to the inorganic filler having an average particle diameter of 50 nm or less, an inorganic filler having an average particle diameter of 0.2 μm to 1 μm and an inorganic filler having an average particle diameter of 5 μm to 30 μm.

[0196] From the viewpoint of improving the filling property for narrow portions, suppressing burrs during molding, and the like, the content of the inorganic filler having a particle diameter of 50 nm or less is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, further preferably 11 parts by mass or more, particularly preferably 13 parts by mass or more, and most preferably 15 parts by mass or more, relative to 100 parts by mass of the epoxy resin. From the viewpoint of suppressing an increase in viscosity, the content of the inorganic filler having a particle diameter of 50 nm or less can be 30 parts by mass or less, 25 parts by mass or less, or 20 parts by mass or less, relative to 100 parts by mass of the epoxy resin. From the viewpoint of preferably obtaining the effects of improving the filling property for narrow portions, suppressing burrs during molding, and the like, the content of the inorganic filler having a particle diameter of 50 nm or less can be 5 parts by mass to 30 parts by mass, 10 parts by mass to 30 parts by mass, 11 parts by mass to 25 parts by mass, 13 parts by mass to 20 parts by mass, or 15 parts by mass to 20 parts by mass, relative to 100 parts by mass of the epoxy resin.

[0197] The content of the inorganic filler having a particle diameter of 50 nm or less can be found by converting the proportion of particles having a particle diameter of 50 nm or less in the particle size distribution on a volume basis, which is measured by a dynamic light scattering particle size analyzer (for example, nanotrack manufactured by Microtrac BEL, Inc.), to a mass basis, relative to the total amount of the inorganic filler.

[0198] In one aspect, in the case of obtaining a hardened product having high thermal conductivity, the inorganic filler preferably contains alumina, and more preferably contains alumina as a main component (i.e., 50% by volume or more of the inorganic filler). Specifically, for example, it is preferable to mix silica having a particle diameter of 50 nm or less and alumina having a particle diameter of more than 50 nm.

[0199] In another aspect, from the viewpoints of resistance to reflow, suppression of an increase in viscosity, and improvement of flowability, the inorganic filler preferably contains silica, and more preferably contains silica as a main component (i.e., 50% by volume or more of the inorganic filler). Specifically, for example, it is preferable to mix silica having a particle diameter of 50 nm or less and silica having a particle diameter of more than 50 nm.

[0200] The average particle diameter of the inorganic filler contained in the epoxy resin composition is not particularly limited. For example, the average particle diameter is preferably 0.2 μm to 80 μm, more preferably 0.5 μm to 70 μm, and further preferably 1 μm to 50 μm. If the average particle diameter is 0.2 μm or more, there is a tendency that an increase in viscosity of the epoxy resin composition is suppressed. If the average particle diameter is 80 μm or less, there is a tendency that the filling property for narrow gaps is improved. From the viewpoint of the flowability of the epoxy resin composition, the particle diameter of the inorganic filler is preferably distributed in a wide range.

[0201] The maximum particle diameter (also referred to as the cut point) of the inorganic filler is not particularly limited. From the viewpoint of the filling property for narrow gaps, the maximum particle diameter of the inorganic filler is preferably 150 μm or less, more preferably 75 μm or less, and further preferably 55 μm or less.

[0202] The content of the inorganic filler is not particularly limited. The content of the inorganic filler is preferably 50% by volume or more, more preferably 60% by volume or more, further preferably 70% by volume or more, particularly preferably 75% by volume or more, and most preferably 80% by volume or more, with respect to the total volume of the epoxy resin composition. By setting the content of the inorganic filler to 50% by volume or more of the entire epoxy resin composition, there is a tendency that the thermal expansion coefficient, the thermal conductivity, the elastic coefficient, and the like of the hardened product can be preferably improved.

[0203] In addition, the content of the inorganic filler is preferably 95% by volume or less, more preferably 90% by volume or less, and further preferably 87% by volume or less, with respect to the total volume of the epoxy resin composition. If the content of the inorganic filler is 95% by volume or less of the entire epoxy resin composition, there is a tendency that the viscosity of the epoxy resin composition is inhibited from increasing, the flowability is further improved, and the moldability becomes even better.

[0204] From the above viewpoints, the content of the inorganic filler is preferably 50% by volume to 95% by volume, more preferably 60% by volume to 95% by volume, further preferably 70% by volume to 95% by volume, particularly preferably 75% by volume to 90% by volume, and most preferably 80% by volume to 87% by volume, with respect to the total volume of the epoxy resin composition.

[0205] Further, the average particle diameter of the inorganic filler in the present disclosure is set to the volume average particle diameter.

[0206] The average particle diameter of the inorganic filler in the present disclosure can be measured using a laser diffraction scattering method particle size distribution measuring device in the form of a volume average particle diameter (D50).

[0207] In addition, the average particle diameter of the inorganic filler in the epoxy resin composition or the hardened product thereof can be specifically measured using the following method. A crucible into which the epoxy resin composition or the hardened product thereof is put is put into a muffle furnace, and heated to 800°C. The sample is left for about 4 hours until the sample is completely ashed. The sample is naturally cooled until it returns to room temperature, and the ash (inorganic filler) is extracted. A dispersion liquid is prepared by sufficiently dispersing the inorganic filler using an ultrasonic disperser or the like. The volume average particle diameter of the inorganic filler can be measured using the dispersion liquid and the particle size distribution on a volume basis measured using a laser diffraction scattering method particle size distribution measuring device.

[0208] In the present disclosure, the so-called "use of two or more kinds of inorganic fillers" can be exemplified by: a case where two or more kinds of inorganic fillers having the same composition but different average particle diameters are used; a case where two or more kinds of inorganic fillers having the same average particle diameter but different compositions are used; and a case where two or more kinds of inorganic fillers having different average particle diameters and different kinds are used.

[0209] <Hardening agent>

[0210] The epoxy resin composition of the first to third embodiments contains a hardening agent including a compound represented by General Formula (B) (hereinafter, also referred to as a specific hardening agent).

[0211] [Chemical Formula 18]

[0212]

[0213] In General Formula (B),

[0214] R 1 ~R 5 each independently represents a monovalent organic group having a carbon number of 1 to 6,

[0215] X1to X3each independently represent an integer of 0 to 4,

[0216] X4and X5each independently represent an integer of 0 to 3,

[0217] n1represents a number of 1 to 10,

[0218] n2represents a number of 1 to 10.

[0219] R 1 ~R 5 each independently is a monovalent organic group having a carbon number of 1 to 6, and preferably a monovalent organic group having a carbon number of 1 to 3. As the monovalent organic group represented by R 1 ~R 5 represented by R1to R6, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a tert-butyl group, and the like can be exemplified.

[0220] X1to X3each independently are preferably 0 to 2, more preferably 0 or 1, and further preferably 0.

[0221] X4and X5each independently are preferably 0 to 2, more preferably 0 or 1, and further preferably 0.

[0222] n1and n2are each an average value of the number of repetitions of the structural units in parentheses.

[0223] The hydroxyl equivalent weight of the specific hardener is preferably 130 g / eq to 200 g / eq, more preferably 150 g / eq to 180 g / eq. The hydroxyl equivalent weight of the specific hardener can be measured using the method described later.

[0224] In the case where the specific hardener is a solid, the softening point or melting point thereof is not particularly limited, and is preferably 40°C to 180°C from the viewpoint of moldability and resistance to reflow, and more preferably 50°C to 130°C from the viewpoint of operability at the time of production of the epoxy resin composition. From the viewpoint of improving flowability and lowering the high-temperature elastic modulus of the hardened product of the epoxy resin composition and improving resistance to reflow, the softening point or melting point of the specific hardener is preferably 50°C to 100°C, more preferably 50°C to 75°C, and further preferably 50°C to 70°C.

[0225] The specific hardener can be used alone or in combination of two or more.

[0226] As the hardener, another hardener can be further used in combination in addition to the specific hardener. The content ratio of the specific hardener with respect to the total mass of the hardener is preferably 30 mass% to 100 mass%, more preferably 50 mass% to 100 mass%, and further preferably 70 mass% to 100 mass%.

[0227] As the other hardener, a hardener having a phenolic hydroxyl group in the molecule other than the compound represented by General Formula (B) (phenolic hardener) can be exemplified.

[0228] As the phenolic hardener other than the compound represented by General Formula (B), for example, a phenol resin having two or more phenolic hydroxyl groups in one molecule and a polyhydric phenol compound can be listed. Specifically, a polyhydric phenol compound such as resorcinol, catechol, bisphenol A, bisphenol F, a substituted or unsubstituted biphenyl phenol, and the like; a novolak-type phenol resin obtained by condensation or co-condensation of at least one phenolic compound selected from the group consisting of phenol compounds such as phenol, m-cresol, p-cresol, dimethylphenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and naphthol compounds such as a-naphthol, β-naphthol, dihydroxynaphthalene, and the like, and an aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, salicylaldehyde, and the like, under an acidic catalyst; a phenol aralkyl resin such as a phenol aralkyl resin synthesized from the phenolic compound and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, and the like, a naphthol aralkyl resin, and the like (except for the compound represented by General Formula (B)); a p-xylene and / or m-xylene-modified phenol resin; a melamine-modified phenol resin; a terpene-modified phenol resin; a dicyclopentadiene-type phenol resin and a dicyclopentadiene-type naphthol resin synthesized by copolymerization of the phenolic compound and dicyclopentadiene; a cyclopentadiene-modified phenol resin; a polycyclic aromatic ring-modified phenol resin; a biphenyl-type phenol resin; a triphenylmethane-type phenol resin obtained by condensation or co-condensation of the phenolic compound and an aromatic aldehyde compound such as benzaldehyde, salicylaldehyde, and the like, under an acidic catalyst; a phenol resin obtained by copolymerization of two or more of these; and the like can be listed. These phenolic hardeners can be used alone or in combination of two or more.

[0229] Among the phenolic hardeners other than the compound represented by General Formula (B), from the viewpoint of resistance to reflow soldering, at least one selected from the group consisting of an aralkyl-type phenol resin (except for the compound represented by General Formula (B)), a dicyclopentadiene-type phenol resin, a triphenylmethane-type phenol resin, a benzaldehyde-type phenol resin, a copolymerization-type phenol resin of an aralkyl-type phenol resin and a benzaldehyde-type phenol resin, and a novolak-type phenol resin (these are referred to as “specific phenolic hardeners”) is preferred. The specific phenolic hardener can be used alone or in combination of two or more.

[0230] As the aralkyl-type phenol resin other than the compound represented by General Formula (B), a phenol aralkyl resin synthesized from a phenolic compound and dimethoxy-p-xylene, bis(methoxymethyl)biphenyl, and the like, a naphthol aralkyl resin, and the like can be listed. The aralkyl-type phenol resin can further be copolymerized with other phenol resins. As the copolymerized aralkyl-type phenol resin, a benzaldehyde-type phenol resin and an aralkyl-type phenol resin, a salicylaldehyde-type phenol resin and an aralkyl-type phenol resin, a novolak-type phenol resin and an aralkyl-type phenol resin, and the like can be listed.

[0231] The aralkyl type phenol resin is not particularly limited as long as it is a phenol resin synthesized from at least one selected from the group consisting of phenol compounds and naphthol compounds and dimethoxy-p-xylene, bis(methoxymethyl) biphenyl, or a derivative thereof. For example, a phenol resin represented by the following general formula (XII) to general formula (XIV) is preferred.

[0232] [Chemical Formula 19]

[0233]

[0234] In the formula (XII) to formula (XIV), R 23 represents a hydrogen atom or a monovalent organic group having a carbon number of 1 to 18, and can be the same or different. 22 , R 24 , R 25 , and R 28 represent a monovalent organic group having a carbon number of 1 to 18, and can be the same or different. 26 , and R 27 represent a hydroxyl group or a monovalent organic group having a carbon number of 1 to 18, and can be the same or different. i and j are each independently an integer of 0 to 3, k is each independently an integer of 0 to 4, and p is each independently an integer of 0 to 4. n is an average value, and is each independently a number of 0 to 10.

[0235] In the phenol resin represented by the general formula (XII), i is 0 and R 23 all of which are hydrogen atoms, are available as commercial products.

[0236] In the phenol resin represented by the general formula (XIII), XL-225, XLC (Mitsui Chemicals, Inc., trade name), MEH-7800 (Meiwa Plastic Industries, Ltd., trade name), and the like in which i is 0 and k is 0 are available as commercial products.

[0237] In the phenol resin represented by the general formula (XIV), SN-170 (Nippon Steel Chemical & Material Co., Ltd., trade name) in which j is 0, k is 0, and p is 0, SN-395 (Nippon Steel Chemical & Material Co., Ltd., trade name) in which j is 0, k is 1, R 27 is a hydroxyl group, and p is 0, and the like are available as commercial products.

[0238] The dicyclopentadiene type phenol resin is not particularly limited as long as it is a phenol resin obtained using a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenol resin represented by the following general formula (XV) is preferred. In the phenol resin represented by the general formula (XV), DPP (New Japan Chemical Co., Ltd., trade name) in which i is 0, and the like are available as commercial products.

[0239] [Chemistry 20]

[0240]

[0241] In formula (XV), R 29 The first group represents a monovalent organic group with 1 to 18 carbon atoms, and they can all be the same or different. Each i represents an integer from 0 to 3 independently. n is the average value, representing a number from 0 to 10.

[0242] Triphenylmethane-type phenolic resins are not particularly limited as long as they are phenolic resins obtained from compounds having a triphenylmethane skeleton as raw materials. For example, phenolic resins represented by the following general formula (XVI) are preferred.

[0243] Among the phenolic resins represented by the following general formula (XVI), MEH-7500 (Maywa Kasei Corporation, trade name), where i is 0 and k is 0, are available as commercially available products.

[0244] [Chemistry 21]

[0245]

[0246] In formula (XVI), R 30 and R 31 Represents monovalent organic groups with carbon numbers from 1 to 18, which may be the same or different. i is an independent integer from 0 to 3, and k is an independent integer from 0 to 4. n is the average value, a number from 0 to 10.

[0247] The copolymer of benzaldehyde-type phenolic resin and aralkyl-type phenolic resin is not particularly limited as long as it is a copolymer of phenolic resin obtained from a compound having a benzaldehyde skeleton and aralkyl-type phenolic resin. For example, the phenolic resin represented by the following general formula (XVII) is preferred.

[0248] Among the phenolic resins represented by the following general formula (XVII), HE-510 (AirWater Chemical Co., Ltd., trade name), in which i is 0, k is 0 and q is 0, is available as a commercially available product.

[0249] [Chemistry 22]

[0250]

[0251] In equation (XVII), R 32 ~R 34R1to R18represent a monovalent organic group having 1 to 18 carbon atoms, and can be the same or different. i and k each independently represent an integer of 0 to 3, and q independently represents an integer of 0 to 5. l and m each independently represent an average value, and are a number of 0 to 11. The sum of l and m is a number of 1 to 11.

[0252] The novolak-type phenol resin is not particularly limited as long as it is a phenol resin obtained by condensation or co-condensation of 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 phenol resin represented by the following general formula (XVIII) is preferred.

[0253] In the phenol resin represented by the following general formula (XVIII), i is 0, R 35 Tamanol 758, 759 (Arakawa Chemical Industries, Ltd., trade name), H-4 (Meiwa Chemical Co., Ltd., trade name), and the like in which each of R

[0254] [Chemical Formula 23]

[0255]

[0256] In formula (XVIII), R 35 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and can be the same or different. R 36 represents a monovalent organic group having 1 to 18 carbon atoms, and can be the same or different. i each independently represents an integer of 0 to 3. n represents an average value, and is a number of 0 to 10.

[0257] As for R 22 to R 36 "may be the same or different" described above means, for example, that R 22 may be the same or different. As for other R 23 to R 36 also means that the number of each of R 22 to R 36 may be the same or different. In addition, R 22 and R 23 may be the same or different, R 30 and R 31 may be the same or different.

[0258] n in the general formula (XII) to the general formula (XVIII) is preferably in the range of 0 to 10. If it is 10 or less, the melt viscosity of the resin component does not become excessively high, the viscosity at the time of melt molding of the epoxy resin composition becomes low, and it is difficult to cause filling failure, deformation of a bonding wire (a metal wire connecting an element and a lead), and the like. The average n in one molecule is preferably in the range of 0 to 4.

[0259] The functional group equivalent (in the case of a hardening agent having a phenolic hydroxyl group in the molecule, the hydroxyl group equivalent) of the hardening agent other than the compound represented by the general formula (B) is not particularly limited. From the viewpoint of the balance of various characteristics such as moldability, resistance to reflow soldering, and electrical reliability, it is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.

[0260] The functional group equivalent (in the case of a hardening agent having a phenolic hydroxyl group in the molecule, the hydroxyl group equivalent) of the hardening agent may, for example, be a value measured by a method according to JIS K 0070:1992.

[0261] In the case where the hardening agent other than the compound represented by the general formula (B) is a solid, the softening point or the melting point thereof is not particularly limited. From the viewpoint of moldability and resistance to reflow soldering, it is preferably 40°C to 180°C, and from the viewpoint of the operability at the time of production of the epoxy resin composition, it is more preferably 50°C to 130°C. In addition, from the viewpoint of improving fluidity and lowering the high-temperature elastic modulus of the hardened product of the epoxy resin composition and improving resistance to reflow soldering, the softening point or the melting point of the hardening agent is preferably 50°C to 100°C, more preferably 50°C to 75°C, and further preferably 50°C to 65°C.

[0262] The melting point or the softening point of the hardening agent is set to a value measured in the same manner as the melting point or the softening point of the epoxy resin.

[0263] The equivalent ratio of the epoxy resin to the hardening agent, that is, the ratio of the number of functional groups in the hardening agent to the number of epoxy groups in the epoxy resin (the number of functional groups in the hardening agent / the number of epoxy groups in the epoxy resin), is not particularly limited. From the viewpoint of suppressing unreacted components, it is preferably in the range of 0.5 to 2.0, and more preferably in the range of 0.6 to 1.3. From the viewpoint of moldability and resistance to reflow soldering, it is further preferably in the range of 0.8 to 1.2.

[0264] <Hardening Accelerator>

[0265] The epoxy resin composition of the first to third embodiments can also include a hardening accelerator. The kind of the hardening accelerator is not particularly limited, and can be selected in accordance with the kind of the epoxy resin, the desired characteristics of the epoxy resin composition, and the like.

[0266] As the hardening accelerator, mention can be made of: 1,5-diazabicyclo[4.3.0]nonene-5 (1,5-Diazabicyclo[4.3.0]nonene-5, DBN), 1,8-diazabicyclo[5.4.0]undecene-7 (1,8-Diazabicyclo[5.4.0]undecene-7, DBU), and the like diazabicycloalkenes, 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, and the like cyclic amidine compounds; derivatives of the cyclic amidine compounds; phenol novolak salts of the cyclic amidine compounds or the derivatives thereof; compounds having intramolecular polarization formed by addition of 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, phenyl-1,4-benzoquinone, and the like quinone compounds, diazophenylmethane, and the like compounds having a π bond to the cyclic amidine compounds or the derivatives thereof; tetraphenylborate salts of DBU, tetraphenylborate salts of DBN, tetraphenylborate salts of 2-ethyl-4-methylimidazole, tetraphenylborate salts of N-methylmorpholine, and the like cyclic amidinium compounds; pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris(dimethylaminomethyl)phenol, and the like tertiary amine compounds; derivatives of the tertiary amine compounds; tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, tetrapropylammonium hydroxide, and the like ammonium salt compounds; ethylphosphine, phenylphosphine, and the like primary phosphines, dimethylphosphine, diphenylphosphine, and the like secondary phosphines, triphenylphosphine, diphenyl(p-tolyl)phosphine, tri(alkylphenyl)phosphine, tri(alkoxyphenyl)phosphine, tri(alkyl-alkoxyphenyl)phosphine, tri(di-alkylphenyl)phosphine, tri(tri-alkylphenyl)phosphine, tri(tetra-alkylphenyl)phosphine, tri(di-alkoxyphenyl)phosphine, tri(tri-alkoxyphenyl)phosphine, tri(tetra-alkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyl diarylphosphine, trinaphthylphosphine, tri(benzyl)phosphine, and the like tertiary phosphines, and the like organophosphines; complexes of the organophosphines with organoborons, and the like phosphine compounds; compounds having intramolecular polarization formed by addition of 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, phenyl-1,4-benzoquinone, anthraquinone, and the like quinone compounds, diazophenylmethane, and the like compounds having a π bond to the organophosphines or the phosphine compounds;A compound having intramolecular polarization obtained after a dehydrohalogenation step after reacting the organophosphine or the phosphine compound with a halogenated phenol compound such as 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, 6-bromo-2-naphthol, 4-bromo-4'-hydroxybiphenyl, and the like; a tetra-substituted phosphonium such as tetraphenylphosphonium, a tetraphenylborate of a tetra-substituted phosphonium such as tetraphenylphosphonium tetra-p-tolylborate, a salt of a tetra-substituted phosphonium and a phenol compound, and the like; a phosphobetaine compound; an adduct of a phosphine compound and a silane compound; and the like. Among these, the hardening accelerator is preferably a phosphorus-based hardening accelerator, and more preferably a phosphine compound. The hardening accelerator can be used alone or in combination of two or more.

[0267] In the case where the epoxy resin composition contains a hardening accelerator, the content of the hardening accelerator is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass, relative to 100 parts by mass of the resin component (i.e., the total of the resin and the hardening agent). If the amount of the hardening accelerator is 0.1 parts by mass or more relative to 100 parts by mass of the resin component, there is a tendency that the resin is hardened well in a short time. If the amount of the hardening accelerator is 30 parts by mass or less relative to 100 parts by mass of the resin component, there is a tendency that a good molded product having a hardening speed that is not too fast can be obtained.

[0268] <Various additives>

[0269] The epoxy resin composition of the first to third embodiments can contain various additives such as the coupling agent, ion exchanger, release agent, flame retardant, colorant, stress reliever, and the like exemplified below, in addition to the components described above. The epoxy resin composition can contain various additives known in the technical field, as needed, in addition to the additives exemplified below.

[0270] (Coupling agent)

[0271] In the case where the epoxy resin composition contains an inorganic filler, a coupling agent can be contained in order to improve the adhesion between the resin component and the inorganic filler. As the coupling agent, known coupling agents such as an epoxy silane, a mercapto silane, an amino silane, an alkyl silane, a ureido silane, a vinyl silane, a titanium-based compound, an aluminum chelate compound, an aluminum / zirconium-based compound, and the like can be exemplified.

[0272] In the case where the epoxy resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 parts by mass or more and 5 parts by mass or less, more preferably 0.1 parts by mass or more and 2.5 parts by mass or less, relative to 100 parts by mass of the inorganic filler. If the amount of the coupling agent is 0.05 parts by mass or more relative to 100 parts by mass of the inorganic filler, there is a tendency that the adhesion to the frame is further improved. If the amount of the coupling agent is 5 parts by mass or less relative to 100 parts by mass of the inorganic filler, there is a tendency that the moldability of the package is further improved.

[0273] (Ion Exchanger)

[0274] The epoxy resin composition can also contain an ion exchanger. In particular, in the case where the epoxy resin composition is used as a molding material for sealing, it is preferable to contain an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including a sealed element. The ion exchanger is not particularly limited, and a conventionally known ion exchanger can be used. Specifically, a hydrotalcite compound, and a hydroxide containing at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth, and the like can be mentioned. The ion exchanger can be used alone or in combination of two or more. Among them, a hydrotalcite represented by the following general formula (A) is preferable.

[0275] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O ··· (A)

[0276] (0 < X ≤ 0.5, m is a positive number)

[0277] In the case where the epoxy resin composition contains an ion exchanger, the content of the ion exchanger is not particularly limited as long as it is a sufficient amount for capturing ions such as halogen ions. For example, it is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 15 parts by mass or less, relative to 100 parts by mass of the resin component.

[0278] (Release Agent)

[0279] The epoxy resin composition can also contain a release agent from the viewpoint of obtaining good mold releasability at the time of molding. The release agent is not particularly limited, and a conventionally known release agent can be used. Specifically, carnauba wax, octacosanoic acid, stearic acid, and the like, higher fatty acid metal salts, ester-based waxes such as octacosanate, oxidized polyethylene, non-oxidized polyethylene, and the like, and polyolefin-based waxes can be mentioned. The release agent can be used alone or in combination of two or more.

[0280] In the case where the epoxy resin composition contains a release agent, the amount of the release agent is preferably 0.01 to 15 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the resin component. If the amount of the release agent is 0.01 parts by mass or more relative to 100 parts by mass of the resin component, there is a tendency that the releasability can be sufficiently obtained. If it is 15 parts by mass or less, there is a tendency that better adhesion can be obtained.

[0281] (Fire Retardant)

[0282] The epoxy resin composition can also contain a fire retardant. The fire retardant is not particularly limited, and a conventionally known fire retardant can be used. Specifically, an organic compound or an inorganic compound containing a halogen atom, an antimony atom, a nitrogen atom, or a phosphorus atom, a metal hydroxide, or the like can be exemplified. The fire retardant can be used alone or two or more kinds can be used in combination.

[0283] In the case where the epoxy resin composition contains a fire retardant, the amount of the fire retardant is not particularly limited as long as it is a sufficient amount for obtaining a desired fire retardation effect. For example, it is preferably 1 to 300 parts by mass, more preferably 2 to 150 parts by mass, relative to 100 parts by mass of the resin component.

[0284] (Coloring Agent)

[0285] The epoxy resin composition can further contain a coloring agent. As the coloring agent, a conventionally known coloring agent such as carbon black, an organic dye, an organic pigment, titanium oxide, red lead, iron oxide, or the like can be exemplified. The content of the coloring agent can be appropriately selected depending on the purpose or the like. The coloring agent can be used alone or two or more kinds can be used in combination.

[0286] (Stress Relaxing Agent)

[0287] The epoxy resin composition can also contain a silicone oil, silicone rubber particles, or the like as a stress relaxation agent. By including a stress relaxation agent, warping deformation of the package and generation of cracks in the package can be further reduced. As the stress relaxation agent, generally known stress relaxation agents (flexibilizers) used conventionally can be cited. Specifically, thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, polybutadiene-based, natural rubber (NR), acrylonitrile butadiene rubber (NBR), acrylic rubber, urethane rubber, rubber particles such as silicone powder, methylmethacrylate butadiene styrene (MBS), methylmethacrylate-silicone copolymer, methylmethacrylate-butyl acrylate copolymer, and the like having a core-shell structure can be cited. The stress relaxation agent can be used alone or two or more can be used in combination. Among these, a silicone-based stress relaxation agent is preferred. As the silicone-based stress relaxation agent, silicone-based stress relaxation agents having an epoxy group, silicone-based stress relaxation agents having an amino group, silicone-based stress relaxation agents modified with polyether, and the like can be cited.

[0288] 〔Method for producing the epoxy resin composition〕

[0289] The method for producing the epoxy resin composition is not particularly limited. As a general method, a method in which the components in the prescribed amounts are sufficiently mixed by a mixer or the like, then melt-kneaded by a mixing roll, an extruder, or the like, and then cooled and pulverized can be cited. More specifically, for example, a method in which the components in the prescribed amounts are uniformly stirred and mixed, then kneaded and cooled using a kneader, a roll, an extruder, or the like preheated to 70°C to 140°C, and then pulverized can be cited. Further, the epoxy resin composition of the first embodiment includes the epoxy resin, the inorganic filler having an average particle diameter of 50 nm or less, and the hardener containing the compound represented by General Formula (B) below, and can be produced according to the production method described above.

[0290] 〔Properties of the epoxy resin composition〕

[0291] It was found that the epoxy resin composition of the first to third embodiments is excellent in viscosity increase suppression and continuous moldability. The epoxy resin composition of the first to third embodiments is excellent in continuous moldability even if it contains an inorganic filler at a high proportion, and is excellent in flowability at transfer molding, and thus is advantageous in terms of suppression of generation of coil flow, non-filling, and the like. In addition, generally, if an inorganic filler such as alumina is contained at a high proportion, continuous moldability tends to decrease, and as a result, the epoxy resin composition of the first to third embodiments is excellent in continuous moldability, and thus is advantageous.

[0292] The epoxy resin composition is preferably solid at normal temperature and normal pressure (for example, at 25°C, under atmospheric pressure). The shape of the epoxy resin composition when it is solid is not particularly limited, and examples thereof include powder, granules, tablets, and the like. From the viewpoint of workability, the size and mass of the epoxy resin composition when it is in the form of a tablet are preferably such that they are compatible with the molding conditions of the package.

[0293] It was found that the epoxy resin composition of the first to third embodiments has a tendency to be excellent in mixing workability. Thus, there is a tendency that the epoxy resin composition can be favorably produced even if the content of the inorganic filler is increased.

[0294] The flow distance (inch) when the epoxy resin composition is molded under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a hardening time of 90 seconds using a swirl test mold according to EMMI-1-66 is preferably 30.0 inches (914 mm) or more, more preferably 37.0 inches (940 mm) or more, and also can be 65.0 inches (1651 mm) or more. In addition, the flow distance can be 100 inches (2540 mm) or less. The measurement is specifically performed by the method described in the examples.

[0295] The hot hardness of the epoxy resin composition when it is made into a hardened product is not particularly limited. For example, the hot hardness of the epoxy resin composition when it is molded under the conditions of 175°C, 90 seconds, and a pressure of 7 MPa is preferably 60 or more, more preferably 65 or more, further preferably 70 or more, and particularly preferably 75 or more, as measured using a Shore D durometer.

[0296] The melt viscosity of the epoxy resin composition at 175°C is not particularly limited, and is preferably 350 Pa-s or less, more preferably 300 Pa-s or less, further preferably 250 Pa-s or less, and particularly preferably 200 Pa-s or less. The melt viscosity is measured by a flow tester (e.g., a high-precision flow tester) in the following manner. A prescribed amount of the epoxy resin composition is weighed using an electronic balance, and a plate is produced using a tablet machine. After confirming that the temperature of the test mold has reached a prescribed temperature, the test sample is dropped into the mold. Immediately after, the plunger is set, and the measurement is started. The measurement can be performed using the method described in the Examples.

[0297] The thermal conductivity of the epoxy resin composition when it is made into a hardened product is not particularly limited. For example, the thermal conductivity of the hardened product can be 0.5 W / (m-K) or more at room temperature (25°C). The thermal conductivity of the hardened product can be measured using a xenon flash (Xe-flash) method (e.g., a Hyper Flash device manufactured by NETZSCH, trade name: LFA467).

[0298] [Use of the epoxy resin composition]

[0299] The epoxy resin composition according to the first to third embodiments can be used for transfer molding applications. The epoxy resin composition according to the first to third embodiments is preferably used as a sealing molding material for a component based on transfer molding.

[0300] 1.2 Electronic component device

[0301] The electronic component device according to the first to third embodiments includes: a component; and a hardened product of the epoxy resin composition according to any one of the first to third embodiments that seals the component.

[0302] As the electronic component device, an electronic component device obtained by sealing an element portion with the epoxy resin composition can be exemplified, the element portion being obtained by mounting a component (an active component such as a semiconductor chip, a transistor, a diode, a thyristor, a passive component such as a capacitor, a resistor, a coil, and the like) on a support member such as a lead frame, a wired carrier tape, a wiring board, glass, a silicon wafer, an organic substrate, and the like.

[0303] More specifically, there are, for example, Dual Inline Package (DIP), Plastic Leaded Chip Carrier (PLCC), Quad Flat Package (QFP), Small Outline Package (SOP), Small Outline J-lead package (SOJ), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), and the like, which are general resin-sealed ICs having a structure in which, after terminals of an element are connected to lead portions by wire bonding, bumping, or the like, an epoxy resin composition is used and sealing is performed by transfer molding; Tape Carrier Package (TCP) having a structure in which an element connected to a tape carrier by a bump is sealed with an epoxy resin composition; Chip On Board (COB) module, hybrid IC, multi-chip module, and the like, having a structure in which an element connected to a wiring formed on a support member by wire bonding, flip chip bonding, solder, or the like is sealed with an epoxy resin composition; Ball Grid Array (BGA), Chip Size Package (CSP), Multi Chip Package (MCP), and the like, having a structure in which an element is mounted on a surface of a support member in which a terminal for wiring board connection is formed on the back surface, and the element is connected to a wiring formed on the support member by a bump or wire bonding, and then the element is sealed with an epoxy resin composition. In addition, the epoxy resin composition can be preferably used in a printed wiring board.

[0304] As a method of sealing an electronic component device using an epoxy resin composition, a low-pressure transfer molding method can be exemplified.

[0305] "1.3. Method for manufacturing electronic component device"

[0306] The method for manufacturing an electronic component device of the first to third embodiments includes sealing an element with the epoxy resin composition of any one of the first to third embodiments. As a sealing method, the above-described method can be exemplified.

[0307] "2. Fourth embodiment"

[0308] Next, the fourth embodiment will be described in detail.

[0309] 2.1 Epoxy resin composition for compression molding

[0310] The epoxy resin composition for compression molding of the fourth embodiment (hereinafter, also referred to simply as "epoxy resin composition" in the description of the fourth embodiment) contains: an epoxy resin; an inorganic filler; and a hardening agent, and contains a compound represented by General Formula (B) below.

[0311] [Chemical Formula 24]

[0312]

[0313] In General Formula (B),

[0314] R 1 ~ R 5 each independently represents a monovalent organic group having a carbon number of 1 to 6,

[0315] X1to X3each independently represents an integer of 0 to 4,

[0316] X4and X5each independently represents an integer of 0 to 3,

[0317] n1represents a number of 1 to 10,

[0318] n2represents a number of 1 to 10.

[0319] It is found that the epoxy resin composition is easily melt. The reason is not necessarily clear, but it is presumed that the epoxy resin composition is easily melt because it contains a hardening agent containing a compound represented by General Formula (B). Therefore, it is considered that the epoxy resin composition of the fourth embodiment is suitable for compression molding. Hereinafter, the meltability of the epoxy resin composition is also referred to as "dissolvability".

[0320] The epoxy resin composition of the fourth embodiment can further contain a hardening accelerator, other additives, and the like. Hereinafter, the components that can be contained in the epoxy resin composition of the fourth embodiment are described in detail.

[0321] < Epoxy resin >

[0322] The epoxy resin composition of the fourth embodiment contains an epoxy resin. The epoxy resin is not particularly limited as long as it is an epoxy resin having two or more epoxy groups in one molecule.

[0323] Specifically, the following can be cited: a novolak-type epoxy resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds such as phenol, cresol, dimethylphenol, resorcinol, catechol, bisphenol A, bisphenol F, and naphthol compounds such as a-naphthol, β-naphthol, and dihydronaphthalene, with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, and propionaldehyde, in the presence of an acid catalyst, and epoxidizing the novolak resin; a triphenylmethane-type epoxy resin obtained by condensing or co-condensing the phenolic compound with an aromatic aldehyde compound such as benzaldehyde and salicylaldehyde, in the presence of an acid catalyst, and epoxidizing the triphenylmethane-type phenol resin; a copolymerization-type epoxy resin obtained by co-condensing the phenol compound and the naphthol compound with an aldehyde compound in the presence of an acid catalyst, and epoxidizing the novolak resin; a diphenylmethane-type epoxy resin that is a diglycidyl ether of bisphenol A, bisphenol F, or the like; a biphenyl-type epoxy resin that is a diglycidyl ether of alkyl-substituted or unsubstituted biphenol; a stilbene-type epoxy resin that is a diglycidyl ether of a stilbene-based phenolic compound; a sulfur atom-containing epoxy resin that is a diglycidyl ether of bisphenol S or the like; an epoxy resin that is a glycidyl ester of a polybasic carboxylic acid compound such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; a glycidyl amine-type epoxy resin obtained by replacing an active hydrogen bonded to a nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, or the like with a glycidyl group; a dicyclopentadiene-type epoxy resin obtained by epoxidizing a co-condensation resin of dicyclopentadiene and a phenol compound; an alicyclic-type epoxy resin obtained by epoxidizing an olefin bond within 2,3-epoxy-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, 3,4-epoxy cyclohexylmethyl-3,4-epoxy cyclohexane carboxylate, or the like; a p-xylene-modified epoxy resin that is a glycidyl ether of a p-xylene-modified phenol resin; an m-xylene-modified epoxy resin that is a glycidyl ether of an m-xylene-modified phenol resin; a terpene-modified epoxy resin that is a glycidyl ether of a terpene-modified phenol resin; a dicyclopentadiene-modified epoxy resin that is a glycidyl ether of a dicyclopentadiene-modified phenol resin; a cyclopentadiene-modified epoxy resin that is a glycidyl ether of a cyclopentadiene-modified phenol resin; a polycyclic aromatic ring-modified epoxy resin that is a glycidyl ether of a polycyclic aromatic ring-modified phenol resin; a naphthalene-type epoxy resin that is a glycidyl ether of a naphthalene ring-containing phenol resin; a halogenated phenol novolak-type epoxy resin; a hydroquinone-type epoxy resin; a trimethylolpropane-type epoxy resin; a linear aliphatic epoxy resin obtained by oxidizing an olefin bond with a peracid such as peracetic acid;An epoxy resin of an aralkyl type such as an aralkyl phenol resin, a naphthol aralkyl resin, or the like, which is obtained by epoxidizing an aralkyl type phenol resin. Further, an epoxide of a silicone resin, an epoxide of an acrylic resin, or the like can also be cited as the epoxy resin. These epoxy resins can be used singly or in combination of two or more.

[0324] Among the epoxy resins, from the viewpoint of the balance between the reflow soldering resistance and the viscosity, an epoxy resin selected from the group consisting of a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, a sulfur atom-containing epoxy resin, a novolak type epoxy resin, a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin, a copolymerization type epoxy resin, and an aralkyl type epoxy resin (these are referred to as "specific epoxy resins") is preferable.

[0325] Details and preferable modes of the specific epoxy resins are as described in the items of the epoxy resins contained in the epoxy resin compositions of the first to third embodiment modes.

[0326] The specific epoxy resins can be used singly or in combination of two or more.

[0327] In the case where the epoxy resin contains the specific epoxy resins, from the viewpoint of exerting the properties of the specific epoxy resins, the total content ratio thereof is preferably 30% by mass or more, more preferably 50% by mass or more, of the entire epoxy resin.

[0328] From the viewpoint of the viscosity, the specific epoxy resins are more preferably a biphenyl type epoxy resin, a stilbene type epoxy resin, a diphenylmethane type epoxy resin, and a sulfur atom-containing epoxy resin, and from the viewpoint of the heat resistance, a dicyclopentadiene type epoxy resin, a triphenylmethane type epoxy resin, and an aralkyl type epoxy resin are preferable.

[0329] In a preferable mode, the epoxy resin composition can contain at least one selected from the group consisting of a diphenylmethane type epoxy resin and a biphenyl type epoxy resin.

[0330] In the case where the epoxy resin composition contains the diphenylmethane type epoxy resin, the content ratio of the diphenylmethane type epoxy resin can be 40% by mass to 100% by mass, 50% by mass to 100% by mass, or 60% by mass to 100% by mass, with respect to the total mass of the epoxy resin.

[0331] In the case where the epoxy resin composition contains the biphenyl type epoxy resin, the content ratio of the biphenyl type epoxy resin can be 20% by mass to 100% by mass, or 25% by mass to 100% by mass, with respect to the total mass of the epoxy resin.

[0332] In a preferred embodiment, the diphenylmethane type epoxy resin is used in combination with a biphenyl type epoxy resin. In this case, the total content of the diphenylmethane type epoxy resin and the biphenyl type epoxy resin is preferably 70% by mass or more, more preferably 80% by mass or more, and further preferably 90% by mass or more, relative to the total mass of the epoxy resin.

[0333] In the case where the diphenylmethane type epoxy resin is used in combination with the biphenyl type epoxy resin, the content ratio of the diphenylmethane type epoxy resin and the biphenyl type epoxy resin (diphenylmethane type epoxy resin : biphenyl type epoxy resin) can be 90 : 10 to 10 : 90, or 80 : 20 to 50 : 50, on a mass basis.

[0334] The epoxy equivalent weight of the epoxy resin is not particularly limited. From the viewpoint of the balance of various properties such as moldability, reflow soldering resistance, and electrical reliability, the epoxy equivalent weight of the epoxy resin is preferably 100 g / eq to 1000 g / eq, and more preferably 150 g / eq to 500 g / eq. The epoxy equivalent weight of the epoxy resin is set to a value determined by the method according to JIS K 7236:2009.

[0335] In the case where the epoxy resin is a solid, the softening point or the melting point thereof is not particularly limited. From the viewpoint of moldability and reflow soldering resistance, it is preferably 40°C to 180°C, and from the viewpoint of the operability at the time of preparation of the epoxy resin composition, it is more preferably 50°C to 130°C. The melting point of the epoxy resin is set to a value determined by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is set to a value determined by the method according to JIS K 7234:1986 (Globe method).

[0336] From the viewpoint of strength, viscosity, heat resistance, moldability, and the like, the content of the epoxy resin in the epoxy resin composition is preferably 0.5% by mass to 50% by mass, and more preferably 2% by mass to 30% by mass.

[0337] <Inorganic Filler>

[0338] The epoxy resin composition of the fourth embodiment contains an inorganic filler. The material of the inorganic filler is not particularly limited. Specifically, inorganic materials such as silica (fused silica, crystalline silica, etc.), glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllium oxide, zirconium oxide, zircon, forsterite, block talc, spinel, mullite, titanium oxide, talc, clay, mica, etc. can be listed. An inorganic filler having a flame retardant effect can also be used. As the inorganic filler having a flame retardant effect, a composite metal hydroxide such as aluminum hydroxide, magnesium hydroxide, a composite hydroxide of magnesium and zinc, zinc borate, etc. can be listed. Among them, from the viewpoint of reducing the linear expansion coefficient, fused silica is preferable, and from the viewpoint of high thermal conductivity, alumina is preferable. The inorganic filler can be used alone or in combination of two or more. As the state of the inorganic filler, powder, particles in which the powder is spheroidized, fibers, etc. can be listed.

[0339] The average particle diameter of the inorganic filler contained in the epoxy resin composition is not particularly limited. For example, the average particle diameter of the inorganic filler is preferably 0.2 μm to 80 μm, more preferably 0.5 μm to 70 μm, and further preferably 1 μm to 50 μm. If the average particle diameter of the inorganic filler is 0.2 μm or more, there is a tendency that the increase in the viscosity of the epoxy resin composition is suppressed. If the average particle diameter of the inorganic filler is 80 μm or less, there is a tendency that the filling property to a narrow gap is improved.

[0340] The average particle diameter of the inorganic filler in the present disclosure is set to the volume average particle diameter.

[0341] The maximum particle diameter (also referred to as the cut point) of the inorganic filler is not particularly limited. From the viewpoint of the filling property to a narrow gap, the maximum particle diameter of the inorganic filler is preferably 150 μm or less, more preferably 75 μm or less, and further preferably 55 μm or less.

[0342] The shape of the inorganic filler is not particularly limited. From the viewpoint of the mixing property of the epoxy resin composition, the particle shape of the inorganic filler is preferably spherical.

[0343] The content rate of the inorganic filler is not particularly limited. The content rate of the inorganic filler is preferably 50% by volume or more, more preferably 60% by volume or more, further preferably 70% by volume or more, particularly preferably 75% by volume or more, and most preferably 80% by volume or more, with respect to the total volume of the epoxy resin composition. By setting the content rate of the inorganic filler to 50% by volume or more of the entire epoxy resin composition, there is a tendency that the characteristics of the hardened product such as the thermal expansion coefficient, the thermal conductivity, the elastic coefficient, etc. can be preferably improved.

[0344] In addition, the content of the inorganic filler with respect to the total volume of the epoxy resin composition is preferably 95% by volume or less, more preferably 90% by volume or less, and further preferably 87% by volume or less. If the content of the inorganic filler is 95% by volume or less of the entire epoxy resin composition, there is a tendency that the increase in the viscosity of the epoxy resin composition is suppressed.

[0345] From the above viewpoint, the content of the inorganic filler with respect to the total volume of the epoxy resin composition is preferably 50% by volume to 95% by volume, more preferably 60% by volume to 95% by volume, further preferably 70% by volume to 95% by volume, particularly preferably 75% by volume to 90% by volume, and most preferably 80% by volume to 87% by volume.

[0346] In addition, there is a tendency in the epoxy resin composition that even if the content of the inorganic filler is, for example, 82% by volume or more, more preferably 84% by volume or more, further preferably 85% by volume or more, particularly preferably 86% by volume or more, and most preferably 87% by volume or more of the epoxy resin composition, it can be mixed well. For example, by using an inorganic filler having high thermal conductivity such as alumina and setting the content of the inorganic filler to the above proportions, a hardened product having high thermal conductivity can be obtained.

[0347] In addition, there is a tendency in the epoxy resin composition that even if the content of the inorganic filler is, for example, 90% by mass or more, and more preferably 92% by mass or more, it can be mixed well.

[0348] - Alumina -

[0349] In the case where a hardened product having high thermal conductivity is obtained, the inorganic filler preferably contains alumina, and more preferably contains alumina as a main component (i.e., 50% by volume or more with respect to the total volume of the inorganic filler). The average particle diameter of the alumina when the inorganic filler contains alumina is not particularly limited. For example, the average particle diameter of the alumina is preferably 0.2 μm to 80 μm, more preferably 0.5 μm to 70 μm, and further preferably 1 μm to 50 μm. If the average particle diameter is 0.2 μm or more, there is a tendency that the increase in the viscosity of the epoxy resin composition is suppressed. If the average particle diameter is 80 μm or less, there is a tendency that the filling property to a narrow gap is improved.

[0350] The maximum particle diameter of the alumina is not particularly limited. From the viewpoint of the filling property to a narrow gap, the maximum particle diameter of the alumina is preferably 150 μm or less, more preferably 75 μm or less, and further preferably 55 μm or less.

[0351] In a preferred embodiment, alumina having an average particle diameter of 0.1 to 2.0 μm, preferably 0.2 to 1.5 μm, more preferably 0.3 to 1.0 μm, and alumina having an average particle diameter of more than 2.0 μm and 75 μm or less, preferably 5.0 to 55 μm, more preferably 8.0 to 20 μm, can be used in combination. By using two or more kinds of alumina having different average particle diameters in combination, it is possible to improve the filling property and the flowability.

[0352] The shape of the alumina is not particularly limited. From the viewpoint of the kneadability of the epoxy resin composition, the particle shape of the alumina is preferably spherical.

[0353] In the case where the inorganic filler contains alumina, the content ratio of the alumina with respect to the total mass of the inorganic filler is preferably 75% by mass or more, more preferably 80% by mass or more, further preferably 85% by mass or more, particularly preferably 90% by mass or more, and most preferably 95% by mass or more, from the viewpoint of high thermal conductivity. In addition, the content ratio of the alumina with respect to the total mass of the inorganic filler is preferably 99.9% by mass or less, more preferably 99.8% by mass or less, and further preferably 99.7% by mass or less, from the viewpoint of low viscosity, workability in kneading, and the like.

[0354] In the case where the inorganic filler contains alumina, the inorganic filler preferably contains silica in addition to the alumina. If the inorganic filler contains silica in addition to the alumina, it is possible to improve the kneadability compared to the case where the inorganic filler contains only the alumina. For example, the inorganic filler can contain particulate silica (for example, silica having an average particle diameter of 0.1 to 2.0 μm, preferably 0.2 to 1.5 μm, and more preferably 0.3 to 1.0 μm) in addition to the alumina. In addition, the inorganic filler can particularly contain fine silica (for example, silica having an average particle diameter of 1 to 500 nm, more preferably 5 to 300 nm, and further preferably 10 to 200 nm) in addition to the alumina. By containing fine silica in the inorganic filler, it is possible to suppress the generation of burrs when a hardened product is produced.

[0355] In the case where alumina and silica are used in combination as the inorganic filler, the content ratio of the silica with respect to the total mass of the inorganic filler is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and further preferably 0.3% by mass or more, from the viewpoint of the kneadability and the like. In addition, the content ratio of the silica with respect to the total mass of the inorganic filler is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 2% by mass or less, from the viewpoint of high thermal conductivity.

[0356] Silica

[0357] From the viewpoint of resistance to reflow soldering, suppression of an increase in viscosity, and the like, the inorganic filler preferably contains silica, and silica can also be contained as a main component (i.e., 50% by volume or more relative to the total volume of the inorganic filler). The average particle diameter of silica when the inorganic filler contains silica is not particularly limited. For example, the average particle diameter of silica is preferably from 0.2 μm to 80 μm, more preferably from 0.5 μm to 70 μm, and further preferably from 1 μm to 50 μm. If the average particle diameter is 0.2 μm or more, there is a tendency for the increase in viscosity of the epoxy resin composition to be suppressed. If the average particle diameter is 80 μm or less, there is a tendency for the filling property for narrow gaps to be improved.

[0358] In addition, the inorganic filler can also contain fine particulate silica (for example, silica having an average particle diameter of from 0.1 μm to 2.0 μm, preferably from 0.2 μm to 1.5 μm, and more preferably from 0.3 μm to 1.0 μm).

[0359] In addition, the inorganic filler can particularly also contain fine silica (for example, silica having an average particle diameter of from 1 nm to 500 nm, more preferably from 5 nm to 300 nm, and further preferably from 10 nm to 200 nm). By the inorganic filler containing fine silica, there is a tendency for the generation of burrs when a hardened product is produced to be suppressed.

[0360] From the viewpoint of reduction in the modulus of elasticity and reduction in the linear expansion coefficient, the inorganic filler can also contain large-particle-diameter silica. As the large-particle-diameter silica, there can be mentioned large-particle-diameter silica having an average particle diameter of more than 2.0 μm and 75 μm or less, preferably from 5.0 μm to 55 μm, and more preferably from 8.0 μm to 20 μm.

[0361] The maximum particle diameter of the silica is not particularly limited. From the viewpoint of the filling property for narrow gaps, the maximum particle diameter of the silica is preferably 150 μm or less, more preferably 75 μm or less, and further preferably 55 μm or less.

[0362] The shape of the silica is not particularly limited. From the viewpoint of the kneadability of the epoxy resin composition, the particle shape of the silica is preferably spherical.

[0363] In the case where the inorganic filler contains silica, the content rate of the silica is not particularly limited, and can be from 70% by mass to 100% by mass, from 80% by mass to 100% by mass, or from 90% by mass to 100% by mass, relative to the total mass of the inorganic filler. In addition, the content rate of the silica when silica is used in combination with alumina is as described above.

[0364] <Hardening Agent>

[0365] The epoxy resin composition of the fourth embodiment contains a hardening agent containing a compound represented by General Formula (B) (specific hardening agent), and can also contain other hardening agents. Details of the hardening agent are as described in the item of the hardening agent contained in the epoxy resin compositions of the first to third embodiments.

[0366] <Hardening accelerator>

[0367] The epoxy resin composition of the fourth embodiment can also contain a hardening accelerator. Details of the hardening accelerator are as described in the item of the hardening accelerator that can be contained in the epoxy resin compositions of the first to third embodiments.

[0368] <Various additives>

[0369] The epoxy resin composition of the fourth embodiment can also contain various additives such as a coupling agent, ion exchanger, release agent, flame retardant, colorant, stress relaxation agent, and the like. Details of the additives are as described in the item of the additives that can be contained in the epoxy resin compositions of the first to third embodiments.

[0370] Among them, the epoxy resin composition contains a release agent, and the content ratio of the release agent with respect to the total mass of the epoxy resin composition is preferably more than 0 mass% and 2.0 mass% or less, more preferably more than 0 mass% and 1.5 mass% or less, and further preferably more than 0 mass% and 1.2 mass% or less. By containing the release agent at the content ratio, there is a tendency to suppress a significant decrease in appearance, adhesion, and laser marking property, as compared with a case where the release agent is contained at more than the content ratio. In addition, according to the epoxy resin composition of one aspect of the fourth embodiment, there is a tendency to maintain good releasability even if the content ratio of the release agent is in the range.

[0371] [Method for producing epoxy resin composition]

[0372] The method for producing the epoxy resin composition of the fourth embodiment is not particularly limited, and specific examples are as described in the items of the epoxy resin compositions of the first to third embodiments.

[0373] The epoxy resin composition of the fourth embodiment is preferably a solid at normal temperature and normal pressure (for example, 25°C, atmospheric pressure). The shape of the epoxy resin composition when it is a solid is not particularly limited, and examples that can be given are powder, granules, tablets, and the like. From the viewpoint of workability, the size and mass of the epoxy resin composition when it is a tablet are preferably such that they become a size and mass that are compatible with the molding conditions of the package.

[0374] The epoxy resin composition of the fourth embodiment has a tendency to have excellent kneading properties. Therefore, the epoxy resin composition can be favorably produced even if the content of the inorganic filler is increased or a small-particle inorganic filler is used.

[0375]

[0376] The epoxy resin composition of the fourth embodiment can be used for compression molding applications. The epoxy resin composition is preferably used as a sealing molding material for a compression-molding-based component.

[0377]

[0378] The epoxy resin composition of the fourth embodiment has excellent solubility. Therefore, the epoxy resin composition of the fourth embodiment is suitable for sealing of a compression-molding-based component. In addition, generally, if solubility is improved in an epoxy resin composition, there is a tendency for the hardening properties to decrease, but according to the epoxy resin composition of the fourth embodiment, there is a tendency for excellent hardening properties to be maintained.

[0379] The hot hardness of the epoxy resin composition when it is formed into a hardened product is not particularly limited. For example, the hot hardness of the epoxy resin composition when it is formed at 175°C, 90 seconds, and a pressure of 7 MPa, as measured using a Shore D durometer, is preferably 60 or greater, more preferably 65 or greater, further preferably 70 or greater, and particularly preferably 75 or greater.

[0380] The disc flow of the epoxy resin composition 5 g when it is compression molded at 180°C, a load of 78 N, and a hardening time of 90 seconds, using a flat plate mold for circular plate flow measurement, is preferably 75.0 mm or greater, more preferably 78.0 mm or greater, and further preferably 80.0 mm or greater. In addition, the disc flow can be 110 mm or less.

[0381] The melt viscosity of the epoxy resin composition at 175°C is not particularly limited, and is preferably 250 Pa-s or less, more preferably 240 Pa-s or less, and further preferably 230 Pa-s or less. The melt viscosity is measured by a flow tester (e.g., a high-temperature flow tester) in the following manner. A prescribed amount of the epoxy resin composition is weighed using an electronic balance, and a plate is produced using a tablet machine. After confirming that the temperature of the test mold has reached a prescribed temperature, the sample is placed in the mold. Immediately after, the plunger is set, and the measurement is started.

[0382] ​​The thermal conductivity of the hardened product of the epoxy resin composition is not particularly limited. For example, the thermal conductivity of the hardened product can be 0.5 W / (m·K) or more at room temperature (25°C). The thermal conductivity of the hardened product can be measured by a xenon flash (Xe-flash) method (for example, a Hyper Flash device manufactured by NETZSCH, trade name: LFA467).

[0383] The epoxy resin composition of one aspect of the fourth embodiment has a tendency to have excellent mold releasability when a hardened product is produced. Therefore, there is a tendency to maintain good mold releasability even if the amount of mold release agent is reduced in order to improve, for example, the appearance, adhesion, and laser marking properties of the hardened product.

[0384] 2.2 Electronic component device

[0385] The electronic component device of the fourth embodiment includes: an element; and a hardened product of the epoxy resin composition of the fourth embodiment that seals the element.

[0386] As the electronic component device, an electronic component device obtained by sealing an element portion of an element portion obtained by mounting an element (an active element such as a semiconductor chip, a transistor, a diode, a thyristor, a passive element such as a capacitor, a resistor, a coil, or the like) on a support member such as a lead frame, a wired carrier tape, a wiring board, glass, a silicon wafer, an organic substrate, or the like with the epoxy resin composition can be cited.

[0387] More specifically, the following can be cited: a dual inline package (DIP), a plastic leaded chip carrier (PLCC), a quad flat package (QFP), a small outline package (SOP), a small outline J-lead package (SOJ), a thin small outline package (TSOP), a thin quad flat package (TQFP), and the like, which are general resin-sealed ICs having a structure in which, after terminals of an element are connected to lead portions by wire bonding, bumping, or the like, the element is sealed using an epoxy resin composition; a tape carrier package (TCP) having a structure in which an element connected to a tape carrier by a bump is sealed using an epoxy resin composition; a chip on board (COB) module, a hybrid IC, a multi-chip module, and the like, having a structure in which an element connected to a wiring formed on a support member by wire bonding, flip chip bonding, solder, or the like is sealed using an epoxy resin composition; a ball grid array (BGA), a chip size package (CSP), a multi-chip package (MCP), and the like, having a structure in which an element is mounted on a surface of a support member in which a terminal for connection to a wiring board is formed on the back surface, and the element is connected to a wiring formed on the support member by a bump or wire bonding, and then the element is sealed using an epoxy resin composition. In addition, the epoxy resin composition can be preferably used in a printed wiring board.

[0388] "2.3 Manufacturing method of electronic component device"

[0389] The manufacturing method of the electronic component device of the fourth embodiment includes sealing an element by compression molding of the epoxy resin composition of the fourth embodiment.

[0390] [Examples]

[0391] Hereinafter, the embodiments of the present disclosure will be specifically described by examples, but the embodiments of the present disclosure are not limited to these examples.

[0392] "Examples of the first to third embodiments"

[0393] [Preparation of epoxy resin composition]

[0394] The following materials were mixed at the compositions described in Table 1, and roll-mixed at a mixing temperature of 80°C for 15 minutes, to thereby produce the epoxy resin compositions of the Examples and Comparative Examples, respectively. Further, "-" in Table 1 means that the ingredient was not formulated.

[0395] (Epoxy Resin)

[0396] • Epoxy Resin 1: Diphenylmethane-type epoxy resin (bisphenol-type epoxy resin) (trade name: YSLV-80XY, Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 190 g / eq)

[0397] • Epoxy Resin 2: Biphenyl-type epoxy resin (trade name: YX-4000, Mitsubishi Chemical Corporation, epoxy equivalent 190 g / eq)

[0398] • Epoxy Resin 3: Triphenylmethane-type epoxy resin (trade name: 1032H60, Mitsubishi Chemical Corporation, epoxy equivalent 170 g / eq)

[0399] (Hardening Agent)

[0400] • Hardening Agent 1: Compound in which all of x1 to x5 in General Formula (B) are 0, n1 is 1 to 10, and n2 is 1 to 10 (trade name: MEHC7841-4S, Meiwa Chemical Co., Ltd., hydroxyl equivalent 164 g / eq to 168 g / eq, softening point 58°C to 65°C)

[0401] • Hardening Agent 2: Arylalkyl-type phenol resin other than General Formula (B); compound in which i is 0, R 23 all of which are hydrogen atoms (trade name: MEHC7851-SS, Meiwa Chemical Co., Ltd., hydroxyl equivalent 201 g / eq to 205 g / eq, softening point 64°C to 69°C)

[0402] • Hardening Agent 3: Triphenylmethane-type phenol resin (trade name: MEH7500, Meiwa Chemical Co., Ltd., hydroxyl equivalent 95 g / eq to 105 g / eq, softening point 105°C to 115°C)

[0403] (Inorganic Filler)

[0404] • Inorganic Filler 1: Microparticle alumina (average particle diameter 0.4 μm, maximum particle diameter about 2.0 μm)

[0405] • Inorganic Filler 2: Macroparticle alumina (average particle diameter 10 μm, maximum particle diameter 75 μm)

[0406] • Inorganic Filler 3: Ultrafine silica (average particle diameter 25 nm, maximum particle diameter 50 nm)

[0407] • Inorganic filler 4: particulate silica (average particle diameter 0.6 μm, maximum particle diameter 5.0 μm)

[0408] • Inorganic filler 5: large particle silica (average particle diameter 10 μm, maximum particle diameter 75 μm)

[0409] (Hardening accelerator)

[0410] • Hardening accelerator: phosphorus-based hardening accelerator

[0411] (Other additives)

[0412] • Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane (trade name: KBM-573, Shin-Etsu Chemical Co., Ltd.)

[0413] • Release agent: palm wax

[0414] • Colorant: carbon black

[0415] • Ion exchanger: hydrotalcite compound (trade name: DHT-4A, Kyowa Chemical Industry Co., Ltd.)

[0416] [Evaluation of epoxy resin composition]

[0417] The properties of the epoxy resin compositions produced in the examples and comparative examples were evaluated by the following property tests. Furthermore, unless otherwise specified, the molding of the epoxy resin composition was performed by a transfer molding machine under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a hardening time of 90 seconds. In addition, post-hardening was performed as necessary under the conditions of 175°C for 5 hours.

[0418] (1) Spiral flow

[0419] The epoxy resin composition was molded under the conditions using a spiral flow measuring mold according to EMMI-1-66, and the flow distance (inches) was determined.

[0420] (2) Evaluation of flash

[0421] The epoxy resin composition 15 g was placed on a mold at 180°C on a press hot plate, and molding was performed with a hardening time of 90 seconds. After molding, the length of the longest portion of the epoxy resin composition flowing through slits of 50 μm, 30 μm, 20 μm, 10 μm, 5 μm, and 2 μm made on the mold was measured using a vernier caliper, and the measured value was taken as the length of the flash.

[0422] (3) Hot hardness

[0423] The epoxy resin composition was molded into a round plate of 50 mm in diameter x 3 mm in thickness under the conditions, and immediately after the molding, the Shore D hardness was measured using a Shore D hardness tester (manufactured by Ohsaka Phsical Instruments Co., Ltd., HD-1120 (D type)).

[0424] (4) Continuous moldability (shear debonding force evaluation)

[0425] A mold in which a chromium-plated stainless steel plate of 50 mm in length x 35 mm in width x 0.4 mm in thickness was inserted and a round plate of 20 mm in diameter was molded on the chromium-plated stainless steel plate was used, the epoxy resin composition was molded under the conditions, and immediately after the molding, the stainless steel plate was pulled, and the maximum pulling force was recorded. The operation was repeated 10 times continuously using the same stainless steel plate, and the average value of the pulling force from the second to the tenth time was calculated to evaluate.

[0426] (5) Melt viscosity (ηFT)

[0427] Using a flow tester, the melt viscosity of the epoxy resin composition heated to 175°C was measured. The epoxy resin composition was weighed using an electronic balance, and a plate was produced using a tablet press. After confirming that the temperature of the test mold reached 175°C, the sample was dropped into the pan. Immediately, the plunger was set, and the measurement was started.

[0428] [Table 1]

[0429]

[0430] [Table 2]

[0431]

[0432]

[0433] [Table 3]

[0434]

[0435]

[0436] As is apparent from Tables 1 to 3, the epoxy resin composition of the examples has low viscosity and excellent continuous moldability. In addition, as is apparent from the evaluation of burrs, burrs can be preferably suppressed in the examples using ultrafine silica. In addition, even in the case of using ultrafine silica, the epoxy resin composition of the examples maintains excellent flowability.

[0437] Examples of the fourth embodiment

[0438] Preparation of the epoxy resin composition

[0439] The following materials were mixed at the compositions described in Table 4, and roll-mixed at a mixing temperature of 80°C for 15 minutes, to thereby produce the epoxy resin compositions of the Examples and Comparative Examples, respectively. Further, "-" in Table 4 means that the ingredient was not formulated.

[0440] (Epoxy Resin)

[0441] Epoxy Resin 1: Diphenylmethane-type epoxy resin (bisphenol-type epoxy resin) (trade name: YSLV-80XY, Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 190 g / eq)

[0442] Epoxy Resin 2: Biphenyl-type epoxy resin (trade name: YX-4000, Mitsubishi Chemical Corporation, epoxy equivalent 190 g / eq)

[0443] (Hardening Agent)

[0444] • Hardening Agent 1: Novolac-type phenol resin (trade name: H-4, Meicen Chemical Co., Ltd., hydroxyl equivalent 103 g / eq to 107 g / eq, softening point 67°C to 75°C)

[0445] • Hardening Agent 2: Arylalkyl-type phenol resin (trade name: MEHC7800-4S, hydroxyl equivalent 167 g / eq to 179 g / eq, softening point 61°C to 65°C)

[0446] • Hardening Agent 3: Compound in which x1 to x5 in General Formula (B) are all 0, n1 is 1 to 10, and n2 is 1 to 10 (trade name: MEHC7841-4S, Meicen Chemical Co., Ltd., hydroxyl equivalent 164 g / eq to 168 g / eq, softening point 58°C to 65°C)

[0447] • Hardening Agent 4: Arylalkyl-type phenol resin (trade name: MEHC7851-SS, Meicen Chemical Co., Ltd., hydroxyl equivalent 201 g / eq to 205 g / eq, softening point 64°C to 69°C)

[0448] (Inorganic Filler)

[0449] • Inorganic Filler 1: Microparticle alumina (average particle diameter 0.4 μm, maximum particle diameter about 2.0 μm)

[0450] • Inorganic Filler 2: Macroparticle alumina (average particle diameter 10 μm, maximum particle diameter 75 μm)

[0451] • Inorganic Filler 3: Ultrafine silica (average particle diameter 0.1 μm, maximum particle diameter about 2.0 μm)

[0452] (Hardening Accelerator)

[0453] • Hardening accelerator: phosphorus-based hardening accelerator

[0454] (Other additives)

[0455] • Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane (trade name: KBM-573, Shin-Etsu Chemical Co., Ltd.)

[0456] • Release agent: palm wax

[0457] • Colorant: carbon black

[0458] • Ion exchanger: hydrotalcite compound (trade name: DHT-4A, Kyowa Chemical Industry Co., Ltd.)

[0459] [Evaluation of epoxy resin composition]

[0460] The properties of the epoxy resin compositions prepared in the examples and comparative examples were evaluated by the following property tests.

[0461] (1) Meltability

[0462] About 1.5 g of the epoxy resin composition powder (passing through a 3.5 mm mesh, not passing through a 1.0 mm mesh) was prepared. The epoxy resin composition powder was set on a circular pattern on a hot plate (lower mold) heated to 175°C with a height of about 3 mm. A 200 g upper mold, also heated to 175°C, was allowed to freely fall in the horizontal direction on the set epoxy resin composition. The upper mold was supported by the lower mold and a vertical support, and was thus set on the surface with a certain load applied. The time point at which the upper mold fell (i.e., the time point at which the upper mold reached the upper surface of the powder) was set as 0 seconds, and the falling distance of the upper mold after the epoxy resin composition powder started to melt was measured by a laser displacement meter. The height of the upper surface of the epoxy resin composition at the time point of 0 seconds was set as A, and the height after one second was set as B, and the meltability of the powder was investigated by calculating B / A x 100 (%).

[0463] (2) Thermal conductivity

[0464] Using the epoxy resin composition, a test piece for thermal conductivity evaluation was produced by sealing a semiconductor element in a compression molding machine under the conditions of a mold temperature of 175°C to 180°C, a molding pressure of 7 MPa, and a hardening time of 150 seconds. Subsequently, the thermal conductivity of the test piece was measured by the Xe-flash method.

[0465] (3) Continuous moldability (shear release force evaluation)

[0466] A mold in which a 50 mm long by 35 mm wide by 0.4 mm thick chromium-plated stainless steel plate was inserted and a 20 mm diameter round plate was formed on the chromium-plated stainless steel plate was used to form an epoxy resin sealing material under the conditions, the stainless steel plate was immediately drawn after formation, and the maximum drawing force was recorded. The operation was repeated 10 times continuously for the same stainless steel plate, and the average of the drawing forces from the second to the tenth time was calculated to evaluate the continuous formability.

[0467] (4) Mixability (mixate temperature)

[0468] The set temperature of the warming area of the mixing machine was set to 90°C, the temperature of the 4 mixates in the mixing machine was measured, and the degree of temperature rise was used as an index of mixability. The temperature of the mixate tends to rise compared to the set temperature due to the melting property of the epoxy resin composition, shear heat, friction of the inorganic filler, and the like. The closer the average of the temperatures of the 4 mixates is to the set temperature, the more excellent the mixability.

[0469] [Table 4]

[0470]

[0471] As can be seen from Table 4, the melting property of the epoxy resin composition of the examples is excellent. In addition, good results were also obtained in the evaluation of the mixability, continuous formability, and thermal conductivity of the hardened material in the epoxy resin composition of the examples.

[0472] The entire contents of the disclosures of Japanese Patent Application No. 2020-19082 and Japanese Patent Application No. 2020-19083 are incorporated by reference into the present specification.

[0473] As to all documents, patent applications and technical standards described in the present specification, to the same extent as the case where it is specifically and separately described that each document, patent application and technical standard is incorporated by reference, the documents, patent applications and technical standards are cited and incorporated into the present specification.

Claims

1. A production method of a transfer molding epoxy resin composition, comprising mixing an epoxy resin, an inorganic filler having an average particle diameter of 50 nm or less, and a hardening agent containing a compound represented by General Formula (B) below; the content of the inorganic filler having an average particle diameter of 50 nm or less is 5 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin, the melt viscosity at 175°C of the transfer molding epoxy resin composition is 350 Pa-s or less, General Formula (B) is ###0001### (B) wherein X1 to X3 each independently represent an integer of 0 to 4, X4 and X5 each independently represent an integer of 0 to 3, nl represents a number of 1 to 10, and n2 represents a number of 1 to 10.

2. The production method of a transfer molding epoxy resin composition according to claim 1, wherein the epoxy resin contains a biphenyl type epoxy resin.

3. The production method of a transfer molding epoxy resin composition according to claim 2, wherein the content of the biphenyl type epoxy resin in the transfer molding epoxy resin composition is 30 to 100 mass% with respect to the total mass of the epoxy resin. （B） 4. The production method of a transfer molding epoxy resin composition according to any one of claims 1 to 3, wherein the content of the inorganic filler is 60% by volume or more with respect to the total volume of the transfer molding epoxy resin composition. R 1 ~R 5 each independently represents a monovalent organic group having 1 to 6 carbons, 5. The production method of a transfer molding epoxy resin composition according to any one of claims 1 to 3, wherein the content of the compound represented by General Formula (B) with respect to the total mass of the hardening agent in the transfer molding epoxy resin composition is 30 to 100 mass%.

6. A transfer molding epoxy resin composition containing: an epoxy resin; an inorganic filler; and a hardening agent containing a compound represented by General Formula (B) below, the inorganic filler being a mixture of an inorganic filler having an average particle diameter of 50 nm or less and an inorganic filler having an average particle diameter of more than 50 nm, the content of the inorganic filler having an average particle diameter of 50 nm or less being 5 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin, the melt viscosity at 175°C of the transfer molding epoxy resin composition being 350 Pa-s or less, General Formula (B) is ###0002### (B) wherein X1 to X3 each independently represent an integer of 0 to 4, X4 and X5 each independently represent an integer of 0 to 3, nl represents a number of 1 to 10, and n2 represents a number of 1 to 10.

7. A transfer molding epoxy resin composition containing: an epoxy resin; an inorganic filler; and a hardening agent containing a compound represented by General Formula (B) below, the inorganic filler containing an inorganic filler having a particle diameter of 50 nm or less, the content of the inorganic filler having a particle diameter of 50 nm or less being 5 to 30 parts by mass with respect to 100 parts by mass of the epoxy resin, the melt viscosity at 175°C of the transfer molding epoxy resin composition being 350 Pa-s or less, General Formula (B) is ###0003### (B) wherein X1 to X3 each independently represent an integer of 0 to 4. ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ （B） ​ R 1 ~R 5 each independently represents a monovalent organic group having 1 to 6 carbons, ​ ​ ​ ​ ​ ​ ​ ​ ​ ​ （B） ​ R 1 ~R 5 each independently represents a monovalent organic group having 1 to 6 carbons, ​ X4and X5each independently represent an integer of 0 to 3, n1represents a number of 1 to 10, n2represents a number of 1 to 10.

8. The transfer molding epoxy resin composition according to claim 6 or 7, wherein the epoxy resin comprises a biphenyl type epoxy resin.

9. The transfer molding epoxy resin composition according to claim 8, wherein the content of the biphenyl type epoxy resin is 30 mass% to 100 mass% with respect to the total mass of the epoxy resin.

10. The transfer molding epoxy resin composition according to claim 6 or 7, wherein the content of the inorganic filler is 60 vol% or more with respect to the total volume of the transfer molding epoxy resin composition.

11. The transfer molding epoxy resin composition according to claim 6 or 7, wherein the content of the compound represented by General Formula (B) is 30 mass% to 100 mass% with respect to the total mass of the hardening agent.

12. An electronic component device comprising: a component; and a hardened product of an epoxy resin composition obtained by the production method of the transfer molding epoxy resin composition according to any one of claims 1 to 5, or a hardened product of the transfer molding epoxy resin composition according to any one of claims 6 to 11, which seals the component.

13. A compression molding epoxy resin composition comprising: an epoxy resin; an inorganic filler; and a hardening agent comprising a compound represented by General Formula (B) below, the content of the inorganic filler is 50 vol% to 95 vol% with respect to the total volume of the compression molding epoxy resin composition, the melt viscosity at 175°C of the compression molding epoxy resin composition is 250 Pa-s or less, （B） in General Formula (B), R 1 ~R 5 each independently represents a monovalent organic group having 1 to 6 carbons, X1to X3each independently represent an integer of 0 to 4, X4and X5each independently represent an integer of 0 to 3, n1represents a number of 1 to 10, n2represents a number of 1 to 10.

14. The compression molding epoxy resin composition according to claim 13, wherein the content of the inorganic filler is 60 vol% or more with respect to the total volume of the compression molding epoxy resin composition.

15. The compression molding epoxy resin composition according to claim 13 or 14, wherein the content of the compound represented by General Formula (B) is 30 mass% to 100 mass% with respect to the total mass of the hardening agent.

16. The compression molding epoxy resin composition according to claim 13 or 14, further comprising a release agent, the content of the release agent being more than 0 mass% and 2.0 mass% or less with respect to the total mass of the compression molding epoxy resin composition.

17. An electronic component device comprising: a component; and a hardened product of the compression molding epoxy resin composition according to any one of claims 13 to 16, which seals the component.

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