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

Abstract

The present invention provides an epoxy resin composition that exhibits suppressed viscosity increase and excellent continuous moldability, or an easily meltable epoxy resin composition, and an electronic component device comprising a cured product of the epoxy resin composition. [Solution] An epoxy resin composition for transfer molding and a method for producing the same, and an epoxy resin composition for compression molding, comprising an epoxy resin, an inorganic filler, and a curing agent containing a compound represented by the following general formula (B). In general formula (B), R 1 ~R 5 Each of the following independently represents a monovalent organic group with 1 to 6 carbon atoms, X1 to X3 independently represent integers from 0 to 4, X4 and X5 independently represent integers from 0 to 3, n1 represents a number from 1 to 10, and n2 represents a number from 1 to 10. JPEG2026102901000032.jpg42162

Description

[Technical Field]

[0001] This disclosure relates to epoxy resin compositions for transfer molding and methods for producing the same, epoxy resin compositions for compression molding, and electronic component devices. [Background technology]

[0002] Epoxy resin compositions have long been widely used in the field of encapsulating electronic components such as transistors and ICs (Integrated Circuits). This is because epoxy resins offer a good balance of electrical properties, moisture resistance, heat resistance, mechanical properties, and adhesion to inserts. Methods for encapsulating electronic components using epoxy resin compositions include transfer molding, injection molding, and compression molding, with transfer molding being the most commonly used method.

[0003] With the recent miniaturization, weight reduction, and performance improvements of electronic devices, mounting density has increased, and electronic component devices are increasingly adopting surface-mount packages instead of conventional pin-insertion type packages. When mounting semiconductor devices to a circuit board, conventional pin-insertion type packages are soldered from the back of the circuit board after the pins are inserted, so the package is not directly exposed to high temperatures. However, with surface-mount type packages, the entire semiconductor device is processed in a solder bath or reflow machine, so it is directly exposed to soldering temperatures. As a result, if the package has absorbed moisture, the absorbed moisture expands rapidly during soldering, causing delamination of the adhesive interface, package cracks, etc., which reduces the reliability of the package during the mounting process. As a countermeasure to solve the above problem, a method is known in which the content of inorganic filler in the element encapsulation molding material is increased in order to reduce the absorbed moisture inside the semiconductor device (see, for example, Patent Document 1).

[0004] Furthermore, in recent years, the field of electronic components has seen advancements in speed and density, leading to a significant increase in the heat generated by these components. Moreover, the demand for electronic components that operate at high temperatures is also increasing. Therefore, improved thermal conductivity is required for plastics used to encapsulate electronic components, particularly for cured epoxy resins. Methods for improving the thermal conductivity of cured epoxy resins include increasing the amount of highly thermally conductive fillers, such as alumina, in the epoxy resin composition (see, for example, Patent Document 2).

[0005] As mentioned above, transfer molding is the most common method for encapsulating electronic components using epoxy resin compositions. However, in transfer molding, the molten epoxy resin composition is forced to flow into the mold under pressure, which can cause wire flow. While methods to increase the fluidity of the epoxy resin composition are being investigated, there are still challenges in suppressing wire flow. Compression molding is known as an alternative molding method to transfer molding. In compression molding, the epoxy resin composition is placed in the cavity of a mold and melted, and the component is encapsulated by closing the mold and applying pressure. With compression molding, the epoxy resin composition is less likely to flow compared to transfer molding, thus suppressing the occurrence of wire flow.

[0006] As an epoxy resin composition for encapsulating semiconductor devices by compression molding, for example, Patent Document 3 proposes a particulate epoxy resin composition containing epoxy resin, a curing agent, a curing accelerator, an inorganic filler, a fatty acid with a melting point of 70°C or less, and a silane coupling agent with a boiling point of 200°C or more, characterized in that 85% or more by mass of the particle size distribution is within the range of 100 μm to 3 mm. It is stated that by using such an epoxy resin composition, sufficient melting can be achieved in compression molding, and the filling performance can be improved. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Application Publication No. 06-224328 [Patent Document 2] Japanese Patent Publication No. 2007-153969 [Patent Document 3] Japanese Patent Publication No. 2011-153173 [Overview of the project] [Problems that the invention aims to solve]

[0008] In epoxy resin compositions for transfer molding, as described above, inorganic fillers are sometimes included in a high proportion to achieve various properties such as low hygroscopicity and high thermal conductivity of the cured product. However, when inorganic fillers are included in a high proportion, the viscosity of the composition may increase, leading to an increased mixing load, or the fluidity may decrease, causing wire flow problems or incomplete filling. Furthermore, in transfer molding, small-particle inorganic fillers (such as ultrafine silica) are sometimes included in the epoxy resin composition to suppress the generation of burrs and improve filling performance in narrow areas. However, in this case, the increase in viscosity and decrease in fluidity are more pronounced. Furthermore, from the viewpoint of mass production, it is desirable for epoxy resin compositions for sealing to have good continuous moldability. However, an epoxy resin composition that suppresses viscosity increase while having good continuous moldability has not been obtained to date. In view of the above circumstances, the first to third embodiments of this disclosure aim to provide an epoxy resin composition for transfer molding that has suppressed viscosity increase and excellent continuous moldability, a method for producing the same, and an electronic component device comprising a cured product of the epoxy resin composition.

[0009] Furthermore, in epoxy resin compositions used for compression molding, the proportion and particle size distribution of inorganic fillers may be adjusted to achieve various properties such as low hygroscopicity and high thermal conductivity of the cured product. Also, from the viewpoint of obtaining desired physical properties, such as maintaining low viscosity while achieving high filler content by adjusting the proportion and particle size distribution of inorganic fillers, it is desirable for epoxy resin compositions to have a high degree of design flexibility. Therefore, it is desirable to obtain epoxy resin compositions that are easily melted and suitable for device encapsulation by compression molding, even by methods other than those described in Patent Document 3. In view of the above circumstances, the object of the fourth embodiment of this disclosure is to provide an easily meltable epoxy resin composition and an electronic component device comprising a cured product of the epoxy resin composition. [Means for solving the problem]

[0010] In the first to third embodiments, the means for solving the above problems include the following aspects. <1> A method for producing an epoxy resin composition for transfer molding, comprising mixing an epoxy resin, an inorganic filler with an average particle size of 50 nm or less, and a curing agent containing a compound represented by the following general formula (B).

[0011] [ka]

[0012] In general formula (B), R 1 ~R 5 Each of these independently represents a monovalent organic group with 1 to 6 carbon atoms. X1 to X3 each independently represent an integer from 0 to 4. X4 and X5 each independently represent integers between 0 and 3. n1 represents a number between 1 and 10. n2 represents a number between 1 and 10. <2> The epoxy resin includes a biphenyl-type epoxy resin. <1> The manufacturing method described above. <3> The content of the biphenyl-type epoxy resin in the epoxy resin composition for transfer molding is 30% to 100% by mass relative to the total mass of the epoxy resin. <2> The manufacturing method described above. <4> The inorganic filler content is 60% by volume or more relative to the total volume of the epoxy resin composition for transfer molding. <1> ~ <3> A manufacturing method described in any one of the following items. <5> The content of the compound represented by the general formula (B) in the epoxy resin composition for transfer molding is 30% to 100% by mass relative to the total mass of the curing agent. <1> ~ <4> A manufacturing method described in any one of the following items. <6> Epoxy resin and Inorganic fillers and A curing agent containing a compound represented by the following general formula (B), It contains, The inorganic filler is a mixture of an inorganic filler with an average particle diameter of 50 nm or less and an inorganic filler with an average particle diameter greater than 50 nm, and the content of the inorganic filler with an average particle diameter of 50 nm or less is 5 parts by mass or more per 100 parts by mass of the epoxy resin. Epoxy resin composition for transfer molding.

[0013] [ka]

[0014] In general formula (B), R 1 ~R 5 Each of these independently represents a monovalent organic group with 1 to 6 carbon atoms. X1 to X3 each independently represent an integer from 0 to 4. X4 and X5 each independently represent integers between 0 and 3. n1 represents a number between 1 and 10. n2 represents a number between 1 and 10. <7> Epoxy resin and Inorganic fillers and A curing agent containing a compound represented by the following general formula (B), It contains, The inorganic filler comprises an inorganic filler with a particle size of 50 nm or less, and the content of the inorganic filler with a particle size of 50 nm or less is 5 parts by mass or more per 100 parts by mass of the epoxy resin. Epoxy resin composition for transfer molding.

[0015] [ka]

[0016] In general formula (B), R 1 ~R 5 Each of these independently represents a monovalent organic group with 1 to 6 carbon atoms. X1 to X3 each independently represent an integer from 0 to 4. X4 and X5 each independently represent integers between 0 and 3. n1 represents a number between 1 and 10. n2 represents a number between 1 and 10. <8> The epoxy resin includes a biphenyl-type epoxy resin. <6> or <7> The epoxy resin composition for transfer molding described above. <9> The content of the biphenyl-type epoxy resin is 30% to 100% by mass relative to the total mass of the epoxy resin. <8> The epoxy resin composition for transfer molding described above. <10> The inorganic filler content is 60% by volume or more relative to the total volume of the epoxy resin composition. <6> ~ <9> An epoxy resin composition for transfer molding as described in any one of the following items. <11> The content of the compound represented by the general formula (B) relative to the total mass of the curing agent is 30% to 100% by mass. <6> ~ <10> An epoxy resin composition for transfer molding as described in any one of the following items. <12> Element and, To seal the aforementioned button, <1> ~ <5> A cured epoxy resin composition obtained by the manufacturing method described in any one of the items, or <6> ~ <11> A cured epoxy resin composition according to any one of the items, An electronic component device equipped with the following features.

[0017] In the fourth embodiment, the means for solving the above problem include the following aspects. <13> Epoxy resin and Inorganic fillers and A curing agent containing a compound represented by the following general formula (B), An epoxy resin composition for compression molding containing [the specified ingredient].

[0018] [ka] In general formula (B), R 1 ~R 5 Each of these independently represents a monovalent organic group with 1 to 6 carbon atoms. X1 to X3 each independently represent an integer from 0 to 4. X4 and X5 each independently represent integers between 0 and 3. n1 represents a number between 1 and 10. n2 represents a number between 1 and 10. <14> The inorganic filler content is 60% by volume or more relative to the total volume of the epoxy resin composition for compression molding. <13> The epoxy resin composition for compression molding described in [reference]. <15> The content of the compound represented by the general formula (B) relative to the total mass of the curing agent is 30% to 100% by mass. <13> or <14> The epoxy resin composition for compression molding described in [reference]. <16> Furthermore, it contains a release agent, wherein the content of the release agent is greater than 0% by mass and 2.0% by mass or less with respect to the total mass of the epoxy resin composition for compression molding. <13> ~ <15> An epoxy resin composition for compression molding according to any one of the following items. <17> Element and, The aforementioned button is sealed. <13> ~ <16> A cured product of an epoxy resin composition for compression molding described in any one of the items, An electronic component device equipped with the following features. [Effects of the Invention]

[0019] According to the first to third embodiments of this disclosure, an epoxy resin composition for transfer molding that has suppressed viscosity increase and excellent continuous moldability, a method for producing the same, and an electronic component device comprising a cured product of the epoxy resin composition are provided.

[0020] According to a fourth embodiment of the present disclosure, an easily meltable epoxy resin composition and an electronic component device comprising a cured product of the epoxy resin composition are provided. [Modes for carrying out the invention]

[0021] The embodiments for carrying out the embodiments of this disclosure will be described in detail below. However, the embodiments of this disclosure are not limited to the embodiments described below. In the embodiments described below, the components (including elemental steps, etc.) are not essential unless otherwise specified. The same applies to numerical values ​​and their ranges, and do not limit the embodiments of this disclosure.

[0022] In this disclosure, the term "process" includes not only processes that are independent of other processes, but also processes that cannot be clearly distinguished from other processes, provided that the purpose of such process is achieved. In this disclosure, the numerical range indicated using "~" includes the numbers before and after "~" as the minimum and maximum values, respectively. In numerical ranges described in stages within this disclosure, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described in stages. Furthermore, in numerical ranges described within this disclosure, the upper or lower limit of that range may be replaced with the values ​​shown in the examples. In this disclosure, each component may contain multiple types of the corresponding substance. If multiple types of the substance corresponding to each component are present in the composition, the content or amount of each component means the total content or amount of the multiple types of substances present in the composition, unless otherwise specified. In the present disclosure, a plurality of types of particles corresponding to each component may be included. When a plurality of types of particles corresponding to each component are present in the composition, the particle diameter of each component means a value for a mixture of the plurality of types of particles present in the composition, unless otherwise specified.

[0023] ≪1. First to Third Embodiments≫ First, the first to third embodiments will be described in detail.

[0024] ≪1.1 Method for Producing Epoxy Resin Composition for Transfer Molding≫ The method for producing an epoxy resin composition for transfer molding according to the first embodiment includes mixing an epoxy resin, an inorganic filler having an average particle diameter of 50 nm or less, and a curing agent containing a compound represented by the following general formula (B).

[0025]

Chemical formula

[0026] In the general formula (B), R 1 ~R 5 each independently represents a monovalent organic group having 1 to 6 carbon atoms, 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 from 1 to 10, n2 represents a number from 1 to 10.

[0027] The epoxy resin composition produced by the method for producing an epoxy resin composition for transfer molding according to the first embodiment is produced by mixing an inorganic filler having an average particle diameter of 50 nm or less. Generally, when a fine inorganic filler is mixed into an epoxy resin composition, the viscosity of the composition tends to increase significantly. However, it has been found that when a compound represented by the general formula (B) is used in combination, the increase in viscosity can be suppressed well, and an epoxy resin composition excellent in continuous moldability can be obtained. Hereinafter, the epoxy resin composition produced by the method for producing the epoxy resin composition for transfer molding according to this embodiment will also be referred to as the "epoxy resin composition according to the first embodiment."

[0028] The method for producing the epoxy resin composition according to the first embodiment includes the step of mixing an epoxy resin, an inorganic filler having an average particle size of 50 nm or less, and a curing agent containing a compound represented by general formula (B), and other steps are not particularly limited. As an example of a method for preparing the epoxy resin composition according to the first embodiment, one method is to thoroughly mix predetermined amounts of components with a mixer or the like, then melt-knead with a mixing roll, extruder or the like, cool, and pulverize. More specifically, one example is to uniformly stir and mix predetermined amounts of the above-mentioned components, knead with a kneader, roll, extruder or the like that has been preheated to 70°C to 140°C, then cool and pulverize.

[0029] [Epoxy resin composition according to the first embodiment] The epoxy resin composition according to the first embodiment is manufactured by the method for manufacturing the epoxy resin composition for transfer molding according to the first embodiment, and contains an epoxy resin, an inorganic filler, and a curing agent containing a compound represented by general formula (B). The epoxy resin composition according to the first embodiment may further contain a curing accelerator, other additives, etc.

[0030] [Epoxy resin composition according to the second embodiment] The epoxy resin composition according to the second embodiment contains an epoxy resin, an inorganic filler, and a curing agent containing the compound represented by the above-mentioned general formula (B), wherein the inorganic filler is a mixture of an inorganic filler with an average particle diameter of 50 nm or less and an inorganic filler with an average particle diameter greater than 50 nm, and the content of the inorganic filler with an average particle diameter of 50 nm or less is 5 parts by mass or more per 100 parts by mass of the epoxy resin.

[0031] The epoxy resin composition according to the second embodiment contains 5 parts by mass or more of an inorganic filler with an average particle size of 50 nm or less per 100 parts by mass of epoxy resin, but it was found that a significant increase in viscosity was suppressed and that it exhibited excellent continuous moldability.

[0032] [Epoxy resin composition according to the third embodiment] The epoxy resin composition according to the third embodiment contains an epoxy resin, an inorganic filler, and a curing agent containing the compound represented by the general formula (B) described above, wherein the inorganic filler includes an inorganic filler with a particle size of 50 nm or less, and the content of the inorganic filler with a particle size of 50 nm or less is 5 parts by mass or more per 100 parts by mass of the epoxy resin.

[0033] The epoxy resin composition according to the third embodiment contains 5 parts by mass or more of an inorganic filler with a particle size of 50 nm or less per 100 parts by mass of epoxy resin, but it was found that a significant increase in viscosity was suppressed and that it exhibited excellent continuous moldability.

[0034] The epoxy resin, inorganic filler, curing agent, and other optional components included in the epoxy resin compositions according to the first to third embodiments will be described in detail below. In the description of the first to third embodiments, when describing matters common to the epoxy resin compositions according to the first to third embodiments, the epoxy resin compositions according to the first to third embodiments may be collectively referred to simply as "epoxy resin composition."

[0035] <Epoxy resin> The epoxy resin compositions according to the first to third embodiments include an epoxy resin. The type of epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. Specifically, novolac-type epoxy resins (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) are obtained by condensing or co-condensing a novolac resin obtained by condensing or co-condensing a novolac resin obtained by phenol compounds selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, or propionaldehyde, under an acidic catalyst, and then epoxidizing the novolac resin. Copolymer epoxy resins that have been modified; diphenylmethane-type epoxy resins that are diglycidyl ethers of bisphenol A, bisphenol F, etc.; biphenyl-type epoxy resins that are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resins that are diglycidyl ethers of stilbene-based phenol compounds; sulfur atom-containing epoxy resins that are diglycidyl ethers of bisphenol S, etc.; epoxy resins that are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester-type epoxy resins that are glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidylamine-type epoxy resins in which the active hydrogen bonded to the nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, etc. is replaced with a glycidyl group; dicyclopentadiene-type epoxy resins that are epoxidized from a copolymer resin of dicyclopentadiene and a phenol compound;Alicyclic epoxy resins such as vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, which have epoxidized olefin bonds within the molecule; paraxylylene-modified epoxy resins, which are glycidyl ethers of paraxylylene-modified phenol resins; metaxylylene-modified epoxy resins, which are glycidyl ethers of metaxylylene-modified phenol resins; terpene-modified epoxy resins, which are glycidyl ethers of terpene-modified phenol resins; and dicyclopentadiene-modified phenol resins, which are glycidyl ethers of dicyclo Examples of epoxy resins include: pentadiene-modified epoxy resins; cyclopentadiene-modified epoxy resins, which are glycidyl ethers of cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified epoxy resins, which are glycidyl ethers of polycyclic aromatic ring-modified phenolic resins; naphthalene-type epoxy resins, which are glycidyl ethers of naphthalene ring-containing phenolic resins; halogenated phenol novolac-type epoxy resins; hydroquinone-type epoxy resins; trimethylolpropane-type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; and aralkyl-type epoxy resins, which are epoxidized aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins. Furthermore, epoxides of silicone resins and acrylic resins can also be cited as epoxy resins. These epoxy resins may be used individually or in combination of two or more types.

[0036] Among the epoxy resins mentioned above, epoxy resins selected from the group consisting of biphenyl-type epoxy resins, stilbene-type epoxy resins, diphenylmethane-type epoxy resins, sulfur atom-containing epoxy resins, novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, triphenylmethane-type epoxy resins, copolymer-type epoxy resins, and aralkyl-type epoxy resins (these are referred to as "specific epoxy resins") from the viewpoint of balancing reflow resistance and fluidity. Specific epoxy resins may be used individually or in combination of two or more types.

[0037] When the epoxy resin contains a specific epoxy resin, from the viewpoint of exhibiting the performance of the specific epoxy resin, it is preferable that its total content be 30% by mass or more of the total epoxy resin, and more preferably 50% by mass or more.

[0038] Among specific epoxy resins, biphenyl-type epoxy resins, stilbene-type epoxy resins, diphenylmethane-type epoxy resins, and sulfur atom-containing epoxy resins are more preferred from the viewpoint of fluidity, and dicyclopentadiene-type epoxy resins, triphenylmethane-type epoxy resins, and aralkyl-type epoxy resins are preferred from the viewpoint of heat resistance.

[0039] In particular, from the viewpoint of balancing the above-mentioned properties, it is preferable that the epoxy resin contains at least one selected from the group consisting of diphenylmethane type epoxy resin, biphenyl type epoxy resin, and triphenylmethane type epoxy resin, and it is more preferable to use a combination of two or more of these.

[0040] When the epoxy resin contains a diphenylmethane type epoxy resin, the content of the diphenylmethane type epoxy resin may be 40% by mass or more, 50% by mass or more, or 60% by mass or more, based on the total mass of the epoxy resin. Furthermore, the content of the diphenylmethane type epoxy resin may be 90% by mass or less, 80% by mass or less, or 70% by mass or less, based on the total mass of the epoxy resin.

[0041] When the epoxy resin contains a biphenyl-type epoxy resin, the biphenyl-type epoxy resin content may be 10% by mass or more, 20% by mass or more, or 30% by mass or more, based on the total mass of the epoxy resin. Furthermore, the biphenyl-type epoxy resin content may be 70% by mass or less, 60% by mass or less, or 50% by mass or less, based on the total mass of the epoxy resin. Moreover, the biphenyl-type epoxy resin content 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, based on the total mass of the epoxy resin.

[0042] If the epoxy resin contains a triphenylmethane-type epoxy resin, the content of the triphenylmethane-type epoxy resin may be 30% by mass or more, 40% by mass or more, or 50% by mass or more, based on the total mass of the epoxy resin. Furthermore, the content of the triphenylmethane-type epoxy resin may be 70% by mass or less, 60% by mass or less, or 50% by mass or less, based on the total mass of the epoxy resin.

[0043] In one embodiment, the epoxy resin preferably comprises a combination of 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 is preferably 40:60 to 90:10 by mass, more preferably 50:50 to 80:20, and even more preferably 60:40 to 70:30.

[0044] In a further embodiment, the epoxy resin preferably comprises a combination of a biphenyl-type epoxy resin and a triphenylmethane-type epoxy resin. When the epoxy resin comprises a combination of a biphenyl-type epoxy resin and a triphenylmethane-type epoxy resin, the ratio of the biphenyl-type epoxy resin to the triphenylmethane-type epoxy resin is preferably 20:80 to 80:20 by mass, more preferably 30:70 to 70:30, and even more preferably 40:60 to 60:40.

[0045] The following are specific examples of preferred epoxy resins.

[0046] The biphenyl-type epoxy resin is not particularly limited as long as it is an epoxy resin having a biphenyl skeleton. For example, epoxy resins represented by the following general formula (II) are preferred. Among the epoxy resins represented by the following general formula (II), R 8 Of these, when the positions where the oxygen atom is substituted are designated as positions 4 and 4', the positions 3, 3', 5, and 5' are methyl groups, and the other R 8 YX-4000H (Mitsubishi Chemical Corporation, product name), which is a hydrogen atom, all R 8 4,4'-bis(2,3-epoxypropoxy)biphenyl, where the hydrogen atom is, all R 8 When R is a hydrogen atom, and 8 Of these, when the positions where the oxygen atom is substituted are designated as positions 4 and 4', the positions 3, 3', 5, and 5' are methyl groups, and the other R 8 When the atom is a hydrogen atom, a mixed product such as YL-6121H (Mitsubishi Chemical Corporation, product name) is available commercially.

[0047] [ka]

[0048] In formula (II), R 8 '' represents a hydrogen atom, an alkyl group with 1 to 12 carbon atoms, or an aromatic group with 4 to 18 carbon atoms, and these may all be the same or all different. 'n' is an average value, representing a number between 0 and 10.

[0049] The stilbene-type epoxy resin is not particularly limited as long as it is an epoxy resin having a stilbene skeleton. For example, epoxy resins represented by the following general formula (III) are preferred. Among the epoxy resins represented by the following general formula (III), R 9 Of these, when the positions where the oxygen atom is substituted are designated as positions 4 and 4', the positions 3, 3', 5, and 5' are methyl groups, and the other R 9 is a hydrogen atom, and R 10 When all of them are hydrogen atoms, and R 9 Of the 3, 3', 5, and 5' positions, three are methyl groups, one is a t-butyl group, and the other R 9 is a hydrogen atom, and R 10 A mixed product in which all atoms are hydrogen atoms, such as ESLV-210 (Sumitomo Chemical Co., Ltd., product name), is available commercially.

[0050] [ka]

[0051] In formula (III), R 9 and R 10 represents a hydrogen atom or a monovalent organic group with 1 to 18 carbon atoms, and these may all be the same or different. n is the average value and represents a number between 0 and 10.

[0052] The diphenylmethane type epoxy resin is not particularly limited as long as it is an epoxy resin having a diphenylmethane skeleton. For example, epoxy resins represented by the following general formula (IV) are preferred. Among the epoxy resins represented by the following general formula (IV), R 11 All of them are hydrogen atoms, R 12 Of these, when the positions where the oxygen atom is substituted are designated as positions 4 and 4', the positions 3, 3', 5, and 5' are methyl groups, and the other R 12 Products such as YSLV-80XY (Nippon Steel Chemical & Material Co., Ltd., product name), which contains a hydrogen atom, are available commercially.

[0053] [ka]

[0054] In formula (IV), R 11 and R 12 represents a hydrogen atom or a monovalent organic group with 1 to 18 carbon atoms, and these may all be the same or different. n is the average value and represents a number between 0 and 10.

[0055] Sulfur atom-containing epoxy resins are not particularly limited as long as they contain sulfur atoms. For example, epoxy resins represented by the following general formula (V) are included. Among the epoxy resins represented by the following general formula (V), R 13 Of these, when the positions where oxygen atoms are substituted are defined as positions 4 and 4', the 3,3' positions are t-butyl groups, the 6,6' positions are methyl groups, and the other R 13 Products such as YSLV-120TE (Nippon Steel Chemical & Material Co., Ltd., product name), which contains hydrogen atoms, are available commercially.

[0056] [ka]

[0057] In formula (V), R 13 represents a hydrogen atom or a monovalent organic group with 1 to 18 carbon atoms, and these may all be the same or different. n is the average value and represents a number between 0 and 10.

[0058] The novolac-type epoxy resin is not particularly limited as long as it is an epoxy resin obtained by epoxidizing a novolac-type phenolic resin. For example, epoxy resins obtained by epoxidizing novolac-type phenolic resins such as phenol novolac resin, cresol novolac resin, and naphthol novolac resin using methods such as glycidyl etherification are preferred, and epoxy resins represented by the following general formula (VI) are more preferred. Among the epoxy resins represented by the following general formula (VI), R 14 All of them are hydrogen atoms, R 15The methyl group is i=1 in ESCN-190, ESCN-195 (Sumitomo Chemical Co., Ltd., product name), R 14 All of them are hydrogen atoms, i=0, N-770, N-775 (DIC Corporation, product name), R 14 All of them are hydrogen atoms, with parts where i=0 and parts where i=1, R 15 Styrene-modified phenol novolac type epoxy resins having a moiety that is -CH(CH3)-Ph, such as YDAN-1000-10C (Nippon Steel Chemical & Material Co., Ltd., product name), are commercially available.

[0059] [ka]

[0060] In formula (VI), R 14 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and these may all be the same or different. 15 '' represents a monovalent organic group with 1 to 18 carbon atoms, and each group may be identical or different. 'i' independently represents an integer from 0 to 3. 'n' is the average value, representing a number from 0 to 10.

[0061] 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, epoxy resins represented by the following general formula (VII) are preferred. Among the epoxy resins represented by the following general formula (VII), HP-7200 (DIC Corporation, trade name) where i=0 is available commercially.

[0062] [ka]

[0063] In formula (VII), R 16 '' represents a monovalent organic group with 1 to 18 carbon atoms, and each group may be identical or different. 'i' independently represents an integer from 0 to 3. 'n' is the average value, representing a number from 0 to 10.

[0064] The triphenylmethane-type epoxy resin is not particularly limited as long as it is an epoxy resin made from a compound having a triphenylmethane skeleton. For example, epoxy resins obtained by glycidyl etherification of triphenylmethane-type phenolic resins such as novolac-type phenolic resins made from a compound having a triphenylmethane skeleton and a compound having a phenolic hydroxyl group are preferred, and epoxy resins represented by the following general formula (VIII) are more preferred. Among the epoxy resins represented by the following general formula (VIII), 1032H60 (Mitsubishi Chemical Corporation, trade name) and EPPN-502H (Nippon Kayaku Co., Ltd., trade name), in which i is 0 and k is 0, are commercially available.

[0065] [ka]

[0066] In formula (VIII), R 17 and R 18 The symbols represent monovalent organic groups with 1 to 18 carbon atoms, and each group may be identical or different. Each i is an independent integer from 0 to 3, and each k is an independent integer from 0 to 4. n is the average value and represents a number from 0 to 10.

[0067] The copolymer epoxy resin obtained by epoxidizing a novolac resin obtained from a naphthol compound, a phenol compound, and an aldehyde compound is not particularly limited as long as it is an epoxy resin that uses compounds having a naphthol skeleton and compounds having a phenol skeleton as raw materials. For example, an epoxy resin obtained by glycidyl etherification of a novolac-type phenol resin using compounds having a naphthol skeleton and compounds having a phenol skeleton is preferred, and an epoxy resin represented by the following general formula (IX) is more preferred. Among the epoxy resins represented by the following general formula (IX), R 21 Products such as NC-7300 (Nippon Kayaku Co., Ltd., trade name), in which the group is a methyl group with i = 1, j = 0, and k = 0, are commercially available.

[0068] [ka]

[0069] In formula (IX), R 19 ~R 21 represents a monovalent organic group having 1 to 18 carbon atoms, and each may be identical or different. i is an independent integer from 0 to 3, j is an independent integer from 0 to 2, and k is an independent integer from 0 to 4. l and m are average values, numbers from 1 to 10, and (l+m) is a number from 2 to 10. The end of the epoxy resin represented by formula (IX) is shown in the following formulas (IX-1) or (IX-2). In formulas (IX-1) and (IX-2), R 19 ~R 21 The definitions of i, j, and k are given by R in equation (IX). 19 ~R 21 The definitions of i, j, and k are the same. n is either 1 (when bonded via a methylene group) or 0 (when not bonded via a methylene group).

[0070] [ka]

[0071] Examples of epoxy resins represented by the above general formula (IX) include random copolymers containing l constituent units and m constituent units randomly, alternating copolymers containing units alternately, copolymers containing units regularly, and block copolymers containing units in a block-like manner. Any one of these may be used alone, or two or more may be used in combination.

[0072] As a copolymer epoxy resin, Epiclon HP-5000 (DIC Corporation, trade name), represented by the following general formula (IX-3), is also preferred, which is a methoxynaphthalene-cresol-formaldehyde cocondensation epoxy resin containing the two structural units in the following general formula (IX-3) in a random, alternating, or block order. In the following general formula (IX-3), n and m are each average values, numbers from 1 to 10, and (n+m) is a number from 2 to 10. Preferably, n and m are each average values, numbers from 1 to 9, and (n+m) is a number from 2 to 10.

[0073] [ka]

[0074] The aralkyl epoxy resin is not particularly limited as long as it is an epoxy resin made from a phenol resin synthesized from at least one selected from the group consisting of phenol compounds such as phenol and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or derivatives thereof. For example, 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 and cresol and naphthol compounds such as naphthol and dimethylnaphthol, and dimethoxyparaxylene, bis(methoxymethyl)biphenyl, or derivatives thereof is preferred, and epoxy resins represented by the following general formulas (X) and (XI) are more preferred.

[0075] Among the epoxy resins represented by the following general formula (X), i is 0 and R 38 NC-3000S (Nippon Kayaku Co., Ltd., product name) has a hydrogen atom, i is 0, and R 38 Epoxy resins in which hydrogen atoms and all R of general formula (II) 8Efficiency-based epoxy resins, such as CER-3000 (Nippon Kayaku Co., Ltd., trade name), which are mixed with an epoxy resin in which i is a hydrogen atom in a mass ratio of 80:20, are commercially available. In addition, among epoxy resins represented by the following general formula (XI), ESN-175 (Nippon Steel Chemical & Material Co., Ltd., trade name), in which i is 0, j is 0, and k is 0, are commercially available.

[0076] [ka]

[0077] In equations (X) and (XI), R 38 R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and these may all be the same or different. 37 , R 39 ~R 41 'i' represents a monovalent organic group with 1 to 18 carbon atoms, and each group may be identical or different. 'i' is an independent integer between 0 and 3, 'j' is an independent integer between 0 and 2, 'k' is an independent integer between 0 and 4, and 'l' is an independent integer between 0 and 6. 'n' is the average value, and each number is an independent number between 0 and 10.

[0078] In the above general formulas (II) to (XI), R 8 ~R 21 and R 37 ~R 41 Regarding this, "they may all be the same or all different" means, for example, the 8 to 88 R in equation (II) 8 This means that all of them may be the same or different. 9 ~R 21 and R 37 ~R 41 Regarding this as well, it means that the number of each element included in the formula may all be the same or different. Also, R 8 ~R 21 and R 37 ~R 41 These can be the same or different. For example, R 9 and R 10All of them may be the same or different. Furthermore, the monovalent organic group having 1 to 18 carbon atoms in general formulas (III) to (XI) is preferably an alkyl group or an aryl group.

[0079] In the above general formulas (II) to (XI), n is an average value, and it is preferable that each value is independently in the range of 0 to 10. When n is 10 or less, the melt viscosity of the resin component does not become too high, the viscosity of the epoxy resin composition during melt molding decreases, and the occurrence of filling defects, deformation of bonding wires (gold wires connecting the element and lead) tends to be suppressed. It is more preferable that n be set in the range of 0 to 4.

[0080] The epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of balancing various properties such as moldability, reflow resistance, and electrical reliability, the epoxy equivalent 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 of the epoxy resin shall be the value measured by the method in accordance with JIS K 7236:2009.

[0081] When the epoxy resin is solid, its softening point or melting point is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably 40°C to 180°C, and from the viewpoint of ease of handling during the preparation of the epoxy resin composition, it is more preferably 50°C to 130°C. The melting point of the epoxy resin shall be the value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin shall be the value measured by the method (ring-ball method) in accordance with JIS K 7234:1986.

[0082] The epoxy resin content in the epoxy resin composition is preferably 0.5% to 50% by mass, and more preferably 2% to 30% by mass, from the viewpoint of strength, fluidity, heat resistance, moldability, etc.

[0083] <Inorganic filler> The epoxy resin compositions according to the first to third embodiments contain an inorganic filler. The material of the inorganic filler is not particularly limited. Specifically, examples of inorganic materials include silica (fused silica, crystalline silica, etc.), glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fossterite, steatite, spinel, mullite, titania, talc, clay, and mica. Inorganic fillers having flame retardant properties may also be used. Examples of inorganic fillers having flame retardant properties include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as magnesium-zinc composite hydroxides, and zinc borate. Among these, silica is preferred from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferred from the viewpoint of high thermal conductivity. One type of inorganic filler may be used alone, or two or more types may be used in combination. Examples of inorganic fillers in the form of powder, beads formed from spherical powder, fibers, etc.

[0084] The shape of the inorganic filler is not particularly limited. From the viewpoint of the fluidity of the epoxy resin composition, the particle shape of the inorganic filler is preferably spherical.

[0085] The epoxy resin composition according to the first embodiment is manufactured by mixing an inorganic filler with an average particle size of 50 nm or less. When an epoxy resin composition is manufactured by mixing an inorganic filler with an average particle size of 50 nm or less, the ability of the epoxy resin composition to fill narrow spaces is improved, and the generation of burrs during molding tends to be suppressed. In the epoxy resin composition according to the first embodiment, it is preferable that an inorganic filler with an average particle diameter of 50 nm or less is mixed with an inorganic filler with an average particle diameter of greater than 50 nm. The inorganic filler with an average particle diameter of 50 nm or less and the inorganic filler with an average particle diameter of greater than 50 nm may each be one type or two or more types.

[0086] In the epoxy resin composition according to the second embodiment, the inorganic filler is a mixture of an inorganic filler with an average particle diameter of 50 nm or less and an inorganic filler with an average particle diameter greater than 50 nm, and the content of the inorganic filler with an average particle diameter of 50 nm or less is 5 parts by mass or more per 100 parts by mass of the epoxy resin. By using a mixture of an inorganic filler with an average particle diameter of 50 nm or less and an inorganic filler with an average particle diameter greater than 50 nm as the inorganic filler, the ability of the epoxy resin composition to fill narrow spaces is improved, and the generation of burrs during molding tends to be suppressed. The inorganic filler with an average particle diameter of 50 nm or less and the inorganic filler with an average particle diameter greater than 50 nm may each be one type or two or more types.

[0087] In the epoxy resin composition according to the third embodiment, the inorganic filler includes an inorganic filler with a particle size of 50 nm or less, and the content of the inorganic filler with a particle size of 50 nm or less is 5 parts by mass or more per 100 parts by mass of epoxy resin. By blending an inorganic filler with a particle size of 50 nm or less in an amount of 5 parts by mass or more per 100 parts by mass of epoxy resin, the ability of the epoxy resin composition to fill narrow spaces is improved, and the generation of burrs during molding tends to be suppressed.

[0088] For inorganic fillers with an average particle diameter of 50 nm or less, the average particle diameter is preferably 5 nm to 50 nm, more preferably 10 nm to 50 nm, and even more preferably 15 nm to 50 nm.

[0089] The maximum particle size of an inorganic filler with an average particle size of 50 nm or less is not particularly limited and may be 2 μm or less, 1 μm or less, 500 nm or less, or 50 nm or less. In this disclosure, the maximum particle diameter of the inorganic filler refers to the particle diameter (D90%) at which the cumulative amount from the smaller diameter side reaches 90% in the volume-based particle size distribution obtained by a laser diffraction scattering particle size distribution analyzer.

[0090] From the viewpoint of improving filling properties in narrow areas and suppressing burrs during molding, the content of inorganic filler with an average particle size of 50 nm or less is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 11 parts by mass or more, particularly preferably 13 parts by mass or more, and extremely preferably 15 parts by mass or more, per 100 parts by mass of epoxy resin. Furthermore, from the viewpoint of suppressing an increase in viscosity, the content of inorganic filler with an average particle size of 50 nm or less may be 30 parts by mass or less, 25% by mass or less, or 20 parts by mass or less, per 100 parts by mass of epoxy resin. From the viewpoint of suitably obtaining effects such as improving filling properties in narrow areas and suppressing burrs during molding, the content of inorganic filler with an average particle size of 50 nm or less is preferably 5 to 30 parts by mass, more preferably 10 to 30 parts by mass, even more preferably 11 to 25 parts by mass, and particularly preferably 13 to 20 parts by mass, per 100 parts by mass of epoxy resin.

[0091] For inorganic fillers with an average particle diameter greater than 50 nm, the average particle diameter is preferably greater than 50 nm and 80 μm or less, more preferably between 0.1 μm and 70 μm, and even more preferably between 0.2 μm and 50 μm.

[0092] In one embodiment, the inorganic filler is a mixture of an inorganic filler with an average particle diameter of 50 nm or less, an inorganic filler with an average particle diameter exceeding 50 nm and 2.0 μm or less, and an inorganic filler with an average particle diameter exceeding 2.0 μm and 80 μm or less. In a more preferred embodiment, the inorganic filler is a mixture of an inorganic filler with an average particle size of 50 nm or less, an inorganic filler with an average particle size of 0.1 μm to 1 μm, and an inorganic filler with an average particle size of 2 μm to 50 μm. In a more preferred embodiment, the inorganic filler is a mixture of an inorganic filler with an average particle size of 50 nm or less, an inorganic filler with an average particle size of 0.2 μm to 1 μm, and an inorganic filler with an average particle size of 5 μm to 30 μm.

[0093] From the viewpoint of improving filling properties in narrow areas and suppressing burrs during molding, the content of inorganic filler with a particle size of 50 nm or less is preferably 5 parts by mass or more, more preferably 10 parts by mass or more, even more preferably 11 parts by mass or more, particularly preferably 13 parts by mass or more, and extremely preferably 15 parts by mass or more, per 100 parts by mass of epoxy resin. Furthermore, from the viewpoint of suppressing an increase in viscosity, the content of inorganic filler with a particle size of 50 nm or less may be 30 parts by mass or less, 25% by mass or less, or 20 parts by mass or less, per 100 parts by mass of epoxy resin. From the viewpoint of suitably obtaining effects such as improving filling properties in narrow areas and suppressing burrs during molding, the content of inorganic filler with a particle size of 50 nm or less may be 5 to 30 parts by mass, 10 to 30 parts by mass, 11 to 25 parts by mass, 13 to 20 parts by mass, or 15 to 20 parts by mass, per 100 parts by mass of epoxy resin.

[0094] The content of inorganic fillers with a particle size of 50 nm or less can be determined by converting the ratio of particles with a particle size of 50 nm or less to the total amount of inorganic fillers in the volume-based particle size distribution measured by a dynamic light scattering particle size analyzer (e.g., NanoTrac manufactured by Microtrac-Bell Corporation) to a mass-based ratio.

[0095] In one embodiment, when obtaining a cured product with high thermal conductivity, the inorganic filler preferably contains alumina, and more preferably contains alumina as the main component (i.e., 50% by volume or more of the inorganic filler). Specifically, for example, it is preferable that silica with an average particle diameter of 50 nm or less and alumina with an average particle diameter greater than 50 nm are mixed.

[0096] In a further embodiment, from the viewpoint of reflow resistance, suppression of viscosity increase, and improvement of fluidity, the inorganic filler preferably contains silica, and more preferably contains silica as the main component (i.e., 50% by volume or more of the inorganic filler). Specifically, for example, it is preferable that silica with an average particle diameter of 50 nm or less and silica with an average particle diameter greater than 50 nm are mixed.

[0097] The average particle size of the inorganic filler as a whole contained in the epoxy resin composition is not particularly limited. For example, the average particle size is preferably 0.2 μm to 80 μm, more preferably 0.5 μm to 70 μm, and even more preferably 1 μm to 50 μm. When the average particle size is 0.2 μm or more, the increase in viscosity of the epoxy resin composition tends to be suppressed. When the average particle size is 80 μm or less, the ability to fill narrow gaps tends to improve. From the viewpoint of the fluidity of the epoxy resin composition, it is preferable that the particle size of the inorganic filler is distributed over a wide range.

[0098] The maximum particle size (also called the cut point) of the inorganic filler is not particularly limited. From the viewpoint of filling narrow gaps, the maximum particle size of the inorganic filler is preferably 150 μm or less, more preferably 75 μm or less, and even more preferably 55 μm or less.

[0099] The content of the inorganic filler is not particularly limited. The inorganic filler content is preferably 50% by volume or more, more preferably 60% by volume or more, even more preferably 70% by volume or more, particularly preferably 75% by volume or more, and most preferably 80% by volume or more, relative to the total volume of the epoxy resin composition. By setting the inorganic filler content to 50% by volume or more of the total epoxy resin composition, it tends to be possible to suitably improve properties such as the coefficient of thermal expansion, thermal conductivity, and elastic modulus of the cured product. Furthermore, the inorganic filler content is preferably 95% by volume or less, more preferably 90% by volume or less, and even more preferably 87% by volume or less, relative to the total volume of the epoxy resin composition. When the inorganic filler content is 95% by volume or less of the total epoxy resin composition, the increase in viscosity of the epoxy resin composition is suppressed, the fluidity is further improved, and the moldability tends to be better. From the above viewpoint, the inorganic filler content is preferably 50% to 95% by volume, more preferably 60% to 95% by volume, even more preferably 70% to 95% by volume, particularly preferably 75% to 90% by volume, and most preferably 80% to 87% by volume, based on the total volume of the epoxy resin composition.

[0100] In this disclosure, the average particle diameter of the inorganic filler is defined as the volume-average particle diameter. The average particle size of the inorganic filler in this disclosure can be measured as the volume-average particle size (D50) using a laser diffraction scattering particle size distribution analyzer. Furthermore, the average particle size of the inorganic filler in an epoxy resin composition or its cured product can be measured specifically by the following method: A crucible containing the epoxy resin composition or its cured product is placed in a muffle furnace and heated to 800°C. The sample is left for approximately 4 hours until it is completely ashed. The sample is allowed to cool naturally to room temperature, and the ash (inorganic filler) is extracted. The inorganic filler is thoroughly dispersed using an ultrasonic disperser or the like to prepare a dispersion. Using this dispersion, the volume-average particle size of the inorganic filler can be measured from the volume-based particle size distribution measured by a laser diffraction scattering particle size distribution analyzer.

[0101] In this disclosure, "using two or more types of inorganic fillers in combination" means, for example, using two or more types of inorganic fillers with the same components but different average particle sizes, using two or more types of inorganic fillers with the same average particle size but different components, and using two or more types of inorganic fillers with different average particle sizes and types.

[0102] <Hardening agent> The epoxy resin compositions according to the first to third embodiments contain a curing agent comprising a compound represented by the following general formula (B) (hereinafter also referred to as a specific curing agent).

[0103] [ka]

[0104] In general formula (B), R 1 ~R 5 Each of these independently represents a monovalent organic group with 1 to 6 carbon atoms. X1 to X3 each independently represent an integer from 0 to 4. X4 and X5 each independently represent integers between 0 and 3. n1 represents a number between 1 and 10. n2 represents a number between 1 and 10.

[0105] R 1 ~R 5 Each of these is independently a monovalent organic group having 1 to 6 carbon atoms, and preferably a monovalent organic group having 1 to 3 carbon atoms. 1 ~R 5 Examples of monovalent organic groups having 1 to 6 carbon atoms, represented by , include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, and t-butyl group.

[0106] Each of X1 to X3 is independently preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0107] X4 and X5 are each preferably 0 to 2, more preferably 0 or 1, and even more preferably 0.

[0108] n1 and n2 are the average number of repetitions of the structural units in parentheses, respectively.

[0109] The hydroxyl equivalent of a specific curing agent is preferably 130 g / eq to 200 g / eq, and more preferably 150 g / eq to 180 g / eq. The hydroxyl equivalent of a specific curing agent is measured by the method described below.

[0110] When a specific curing agent is solid, its softening point or melting point is not particularly limited, but from the viewpoint of moldability and reflow resistance, it is preferably 40°C to 180°C, and from the viewpoint of ease of handling during the manufacture of the epoxy resin composition, it is more preferably 50°C to 130°C. From the viewpoint of improving fluidity and reducing the high-temperature modulus of the cured epoxy resin composition, thereby improving reflow resistance, the softening point or melting point of the specific curing agent is preferably 50°C to 100°C, more preferably 50°C to 75°C, and even more preferably 50°C to 70°C.

[0111] Certain hardening agents may be used individually or in combination of two or more types. In addition to the specified curing agent, other curing agents may be used in combination. The content of the specified curing agent relative to the total mass of the curing agent is preferably 30% to 100% by mass, more preferably 50% to 100% by mass, and even more preferably 70% to 100% by mass.

[0112] Other curing agents include those containing phenolic hydroxyl groups in their molecules, other than compounds represented by general formula (B) (phenol curing agents).

[0113] Examples of phenol curing agents other than compounds represented by general formula (B) include phenol resins and polyhydric phenol compounds having two or more phenolic hydroxyl groups in one molecule. Specifically, these include polyhydric phenol compounds such as resorcinol, catechol, bisphenol A, bisphenol F, and substituted or unsubstituted biphenols; novolac-type phenol resins obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenol compounds such as phenol, m-cresol, p-cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, phenylphenol, aminophenol, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, with an aldehyde compound such as formaldehyde, acetaldehyde, propionaldehyde, benzaldehyde, and salicylaldehyde under an acidic catalyst; and synthesis from the above phenolic compounds with dimethoxyparaxylene, bis(methoxymethyl)biphenyl, etc. Examples of phenol curing agents include aralkyl-type phenol resins such as phenol aralkyl resins and naphthol aralkyl resins (excluding compounds represented by general formula (B)); paraxylylene and / or metaxylylene-modified phenol resins; melamine-modified phenol resins; terpene-modified phenol resins; dicyclopentadiene-type phenol resins and dicyclopentadiene-type naphthol resins synthesized by copolymerization of the above phenolic compounds and dicyclopentadiene; cyclopentadiene-modified phenol resins; polycyclic aromatic ring-modified phenol resins; biphenyl-type phenol resins; triphenylmethane-type phenol resins obtained by condensation or co-condensation of the above phenolic compounds and aromatic aldehyde compounds such as benzaldehyde and salicylaldehyde under an acidic catalyst; and phenol resins obtained by copolymerizing two or more of these. These phenol curing agents may be used individually or in combination of two or more.

[0114] Among phenol curing agents other than the compound represented by general formula (B), at least one selected from the group consisting of aralkyl-type phenol resins (excluding the compound represented by general formula (B)), dicyclopentadiene-type phenol resins, triphenylmethane-type phenol resins, copolymerized phenol resins of benzaldehyde-type phenol resins and aralkyl-type phenol resins, and novolac-type phenol resins (these are referred to as "specific phenol curing agents"). Specific phenol curing agents may be used individually or in combination of two or more.

[0115] Aalkyl-type phenolic resins other than those represented by general formula (B) include phenol aralkyl resins synthesized from phenolic compounds and dimethoxyp-xylene, bis(methoxymethyl)biphenyl, etc., and naphthol aralkyl resins. Aalkyl-type phenolic resins may be further copolymerized with other phenolic resins. Examples of copolymerized aralkyl-type phenolic resins include copolymerized phenolic resins of benzaldehyde-type phenolic resin and aralkyl-type phenolic resin, copolymerized phenolic resins of salicylaldehyde-type phenolic resin and aralkyl-type phenolic resin, and copolymerized phenolic resins of novolac-type phenolic resin and aralkyl-type phenolic resin.

[0116] The aralkyl-type phenolic resin is not particularly limited as long as it is synthesized from at least one compound selected from the group consisting of phenol compounds and naphthol compounds, and dimethoxyp-xylene, bis(methoxymethyl)biphenyl, or derivatives thereof. For example, phenolic resins represented by the following general formulas (XII) to (XIV) are preferred.

[0117] [ka]

[0118] In equations (XII) to (XIV), R 23R represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and these may all be the same or different. 22 , R 24 , R 25 and R 28 R represents a monovalent organic group having 1 to 18 carbon atoms, and each of them may be identical or different. 26 and R 27 '' represents a hydroxyl group or a monovalent organic group having 1 to 18 carbon atoms, and each of these may be the same or different. 'i' is an independent integer between 0 and 3, 'j' is an independent integer between 0 and 2, 'k' is an independent integer between 0 and 4, and 'p' is an independent integer between 0 and 4. 'n' is the average value, and each of these is an independent number between 0 and 10.

[0119] Among the phenolic resins represented by the above general formula (XII), i is 0 and R 23 MEH-7851 (Meiwa Chemicals Co., Ltd., product name), which consists entirely of hydrogen atoms, is available commercially.

[0120] Among the phenolic resins represented by the above general formula (XIII), XL-225, XLC (Mitsui Chemicals, Inc., trade name), MEH-7800 (Meiwa Kasei Co., Ltd., trade name), etc., in which i is 0 and k is 0, are available commercially.

[0121] Among the phenolic resins represented by the above general formula (XIV), SN-170 (Nippon Steel Chemical & Material Co., Ltd., product name) has j = 0, k = 0, and p = 0, while R has j = 0, k = 1. 27 SN-395 (Nippon Steel Chemical & Material Co., Ltd., product name), which has a hydroxyl group and p is 0, is available as a commercially available product.

[0122] The dicyclopentadiene type phenol resin is not particularly limited as long as it is a phenol resin obtained from a compound having a dicyclopentadiene skeleton as a raw material. For example, a phenol resin represented by the following general formula (XV) is preferable. Among the phenol resins represented by the following general formula (XV), DPP (manufactured by Nippon Petrochemical Co., Ltd., trade name) in which i is 0 is available as a commercially available product.

[0123]

Chemical formula

[0124] In formula (XV), R 29 represents a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i independently represents an integer of 0 to 3. n is an average value and represents a number of 0 to 10.

[0125] The triphenylmethane type phenol resin is not particularly limited as long as it is a phenol resin obtained from a compound having a triphenylmethane skeleton as a raw material. For example, a phenol resin represented by the following general formula (XVI) is preferable.

[0126] Among the phenol resins represented by the following general formula (XVI), MEH-7500 (manufactured by Meiwa Kasei Co., Ltd., trade name) in which i is 0 and k is 0 is available as a commercially available product.

[0127]

Chemical formula

[0128] In formula (XVI), R 30 and R 31 represent a monovalent organic group having 1 to 18 carbon atoms, and all of them may be the same or different. i is independently an integer of 0 to 3, and k is independently an integer of 0 to 4. n is an average value and is a number of 0 to 10.

[0129] The copolymerized phenol resin of a benzaldehyde-type phenol resin and an aralkyl-type phenol resin is not particularly limited as long as it is a copolymerized phenol resin of a phenol resin obtained from a compound having a benzaldehyde skeleton as a raw material and an aralkyl-type phenol resin. For example, a phenol resin represented by the following general formula (XVII) is preferred.

[0130] Among the phenolic resins represented by the following general formula (XVII), HE-510 (Air Water Chemical Co., Ltd., product name), in which i is 0, k is 0, and q is 0, is available commercially.

[0131] [ka]

[0132] In formula (XVII), R 32 ~R 34 represents a monovalent organic group with 1 to 18 carbon atoms, and each group may be identical or different. Each i is an independent integer from 0 to 3, each k is an independent integer from 0 to 4, and each q is an independent integer from 0 to 5. l and m are the average values, and each is an independent number from 0 to 11. However, the sum of l and m is a number from 1 to 11.

[0133] The novolac-type phenolic resin is not particularly limited as long as it is a phenolic resin obtained by condensing or co-condensing at least one phenolic compound selected from the group consisting of phenolic compounds and naphthol compounds with an aldehyde compound under an acidic catalyst. For example, a phenolic resin represented by the following general formula (XVIII) is preferred.

[0134] Among the phenolic resins represented by the following general formula (XVIII), i is 0 and R 35 Tamano-L 758, 759 (Arakawa Chemical Industries, Ltd., product name), H-4 (Meiwa Chemicals, Inc., product name), etc., which are all hydrogen atoms, are available commercially.

[0135] [Chemical formula]

[0136] In formula (XVIII), R 35 represents a hydrogen atom or a monovalent organic group having 1 to 18 carbon atoms, and they may all be the same or different from each other. R 36 represents a monovalent organic group having 1 to 18 carbon atoms, and they may all be the same or different from each other. i independently represents an integer from 0 to 3. n is an average value and represents a number from 0 to 10.

[0137] Regarding R 22 ~R 36 described in the above general formulas (XII) to (XVIII), "they may all be the same or different from each other" means that, for example, all of R 22 in formula (XII) may be the same or different from each other. The same applies to other R 23 ~R 36 , meaning that they may all be the same or different from each other for each number included in the formula. Also, R 22 ~R 36 may be the same or different from each other. For example, all of R 22 and R 23 may be the same or different, and all of R 30 and R 31 may be the same or different.

[0138] In the above general formulas (XII) to (XVIII), n is preferably in the range of 0 to 10. When it is 10 or less, the melt viscosity of the resin component does not become too high, and the viscosity during melt molding of the epoxy resin composition also becomes low, making it difficult for problems such as filling defects and deformation of bonding wires (gold wires connecting the element and the lead) to occur. The average n in one molecule is preferably set in the range of 0 to 4.

[0139] The functional group equivalent (hydroxyl group equivalent in the case of a curing agent having a phenolic hydroxyl group in its molecule) of the curing agent other than the compound represented by general formula (B) is not particularly limited. From the viewpoint of balancing various properties such as moldability, reflow resistance, and electrical reliability, it is preferably 70 g / eq to 1000 g / eq, and more preferably 80 g / eq to 500 g / eq.

[0140] The functional group equivalent of the curing agent (or hydroxyl group equivalent in the case of a curing agent having a phenolic hydroxyl group in its molecule) may be a value measured by, for example, a method in accordance with JIS K 0070:1992.

[0141] When the curing agent other than the compound represented by general formula (B) is a solid, its softening point or melting point is not particularly limited. From the viewpoint of moldability and reflow resistance, it is preferably 40°C to 180°C, and from the viewpoint of ease of handling during the manufacture of the epoxy resin composition, it is more preferably 50°C to 130°C. Furthermore, from the viewpoint of improving fluidity and reducing the high-temperature modulus of the cured epoxy resin composition, thereby improving reflow resistance, the softening point or melting point of the curing agent is preferably 50°C to 100°C, more preferably 50°C to 75°C, and even more preferably 50°C to 65°C.

[0142] The melting point or softening point of the curing agent shall be a value measured in the same manner as the melting point or softening point of the epoxy resin.

[0143] The equivalent ratio of epoxy resin to curing agent, i.e., the ratio of the number of functional groups in the curing agent to the number of epoxy groups in the epoxy resin (number of functional groups in curing agent / number of epoxy groups in epoxy resin), is not particularly limited. From the viewpoint of minimizing unreacted components, it is preferable to set it 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 reflow resistance, it is even more preferable to set it in the range of 0.8 to 1.2.

[0144] <Curing accelerator> The epoxy resin compositions according to the first to third embodiments may contain a curing accelerator. The type of curing accelerator is not particularly limited and can be selected according to the type of epoxy resin, the desired properties of the epoxy resin composition, etc.

[0145] Examples of curing accelerators include diazabicycloalkenes such as 1,5-diazabicyclo[4.3.0]nonene-5 (DBN) and 1,8-diazabicyclo[5.4.0]undecene-7 (DBU), cyclic amidine compounds such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, and 2-heptadecylimidazole; derivatives of the cyclic amidine compounds; phenol novolac salts of the cyclic amidine compounds or their derivatives; and quinone compounds such as maleic anhydride, 1,4-benzoquinone, 2,5-tholquinone, 1,4-naphthoquinone, 2,3-dimethylbenzoquinone, 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, and phenyl-1,4-benzoquinone. Compounds having intramolecular polarization obtained by adding compounds with π bonds, such as zophenylmethane; cyclic amidinium compounds such as tetraphenylborate salt of DBU, tetraphenylborate salt of DBN, tetraphenylborate salt of 2-ethyl-4-methylimidazole, and tetraphenylborate salt of N-methylmorpholine; tertiary amine compounds such as pyridine, triethylamine, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; derivatives of the above tertiary amine compounds; ammonium salt compounds such as tetra-n-butylammonium acetate, tetra-n-butylammonium phosphate, tetraethylammonium acetate, tetra-n-hexylammonium benzoate, and tetrapropylammonium hydroxide;Organic phosphines such as primary phosphines like ethylphosphine and phenylphosphine, secondary phosphines like dimethylphosphine and diphenylphosphine, triphenylphosphine, diphenyl(p-tolyl)phosphine, tris(alkylphenyl)phosphine, tris(alkoxyphenyl)phosphine, tris(alkyl·alkoxyphenyl)phosphine, tris(dialkylphenyl)phosphine, tris(trialkylphenyl)phosphine, tris(tetraalkylphenyl)phosphine, tris(dialkoxyphenyl)phosphine, tris(trialkoxyphenyl)phosphine, tris(tetraalkoxyphenyl)phosphine, trialkylphosphine, dialkylarylphosphine, alkyldiarylphosphine, trinaphthylphosphine, tris(benzyl)phosphine, and other tertiary phosphines; phosphine compounds such as complexes of the above organic phosphines with organoborons; and the above organic phosphines or the above phosphine compounds with maleic anhydride, 1,4-benzoquinone, 2,5-tholquinone, 1,4-naphthoquinone, 2,3-dimethylbenzox Compounds having intramolecular polarization obtained by adding compounds having π bonds, such as quinone compounds like 2,6-dimethylbenzoquinone, 2,3-dimethoxy-5-methyl-1,4-benzoquinone, 2,3-dimethoxy-1,4-benzoquinone, phenyl-1,4-benzoquinone, anthraquinone, and diazophenylmethane; and the aforementioned organophosphine or phosphine compound with 4-bromophenol, 3-bromophenol, 2-bromophenol, 4-chlorophenol, 3-chlorophenol, 2-chlorophenol, and 4-iodidepheno Compounds having intramolecular polarization obtained by reacting halogenated phenol compounds such as 3-iodidephenol, 2-iodidephenol, 4-bromo-2-methylphenol, 4-bromo-3-methylphenol, 4-bromo-2,6-dimethylphenol, 4-bromo-3,5-dimethylphenol, 4-bromo-2,6-di-t-butylphenol, 4-chloro-1-naphthol, 1-bromo-2-naphthol, 6-bromo-2-naphthol, and 4-bromo-4'-hydroxybiphenyl, followed by a dehalogenation step;Examples include tetrasubstituted phosphonium compounds such as tetraphenylphosphonium, tetraphenylborate salts of tetrasubstituted phosphoniums such as tetraphenylphosphonium tetra-p-tolylborate, and salts of tetrasubstituted phosphoniums with phenolic compounds; phosphobetaine compounds; and adducts of phosphonium compounds with silane compounds. Among these, the curing accelerator preferably contains a phosphorus-based curing accelerator, and more preferably contains a phosphonium compound. The curing accelerator may be used alone or in combination of two or more types.

[0146] When an epoxy resin composition contains a curing accelerator, its content is preferably 0.1 to 30 parts by mass, and more preferably 1 to 15 parts by mass, per 100 parts by mass of the resin component (i.e., the total of the resin and the curing agent). When the amount of curing accelerator is 0.1 parts by mass or more per 100 parts by mass of the resin component, it tends to cure well in a short time. When the amount of curing accelerator is 30 parts by mass or less per 100 parts by mass of the resin component, it tends to result in a good molded product with a curing speed that is not too fast.

[0147] <Various additives> The epoxy resin compositions according to the first to third embodiments may contain, in addition to the components described above, various additives such as coupling agents, ion exchangers, mold release agents, flame retardants, colorants, and stress relaxants, as exemplified below. The epoxy resin compositions may also contain, as necessary, various additives well known in the art, in addition to the additives exemplified below.

[0148] (Coupling agent) If the epoxy resin composition contains an inorganic filler, a coupling agent may be included to improve the adhesion between the resin component and the inorganic filler. Examples of known coupling agents include silane compounds such as epoxysilane, mercaptosilane, aminosilane, alkylsilane, ureidosilane, and vinylsilane, as well as titanium compounds, aluminum chelate compounds, and aluminum / zirconium compounds.

[0149] When the epoxy resin composition contains a coupling agent, the amount of the coupling agent is preferably 0.05 to 5 parts by mass, more preferably 0.1 to 2.5 parts by mass, based on 100 parts by mass of the inorganic filler. When the amount of the coupling agent is 0.05 parts by mass or more based on 100 parts by mass of the inorganic filler, the adhesion to the frame tends to be further improved. When the amount of the coupling agent is 5 parts by mass or less based on 100 parts by mass of the inorganic filler, the moldability of the package tends to be further improved.

[0150] (Ion exchanger) The epoxy resin composition may contain an ion exchanger. In particular, when the epoxy resin composition is used as a molding material for encapsulation, it is preferably to contain an ion exchanger from the viewpoint of improving the moisture resistance and high-temperature storage characteristics of an electronic component device including the element to be encapsulated. The ion exchanger is not particularly limited, and a conventionally known one can be used. Specifically, hydrotalcite compounds, and hydrous oxides of at least one element selected from the group consisting of magnesium, aluminum, titanium, zirconium, and bismuth can be mentioned. The ion exchanger may be used alone or in combination of two or more. Among them, hydrotalcite represented by the following general formula (A) is preferable.

[0151] Mg (1-X) Al X (OH)2(CO3) X / 2 ·mH2O ……(A) (0 < X ≦ 0.5, m is a positive number)

[0152] When the epoxy resin composition contains an ion exchanger, its content is not particularly limited as long as it is an amount sufficient to capture ions such as halogen ions. For example, it is preferably 0.1 to 30 parts by mass, more preferably 1 to 15 parts by mass, based on 100 parts by mass of the resin component.

[0153] (Release agent) The epoxy resin composition may contain a release agent to obtain good release properties from the mold during molding. The release agent is not particularly limited, and conventionally known ones can be used. Specifically, examples include carnauba wax, higher fatty acids such as montanic acid and stearic acid, higher fatty acid metal salts, ester waxes such as montanic acid esters, and polyolefin waxes such as oxidized polyethylene and non-oxidized polyethylene. The release agent may be used alone or in combination of two or more types.

[0154] When the epoxy resin composition contains a release agent, the amount is preferably 0.01 to 15 parts by mass, and more preferably 0.1 to 10 parts by mass, per 100 parts by mass of the resin component. When the amount of release agent is 0.01 parts by mass or more per 100 parts by mass of the resin component, sufficient release properties tend to be obtained. When it is 15 parts by mass or less, better adhesion tends to be obtained.

[0155] (Flame retardant) The epoxy resin composition may contain a flame retardant. The flame retardant is not particularly limited, and conventionally known ones can be used. Specifically, examples include organic or inorganic compounds containing halogen atoms, antimony atoms, nitrogen atoms, or phosphorus atoms, and metal hydroxides. The flame retardant may be used alone or in combination of two or more types.

[0156] If the epoxy resin composition contains a flame retardant, the amount is not particularly limited as long as it is sufficient to obtain the desired flame retardant effect. For example, it is preferably 1 to 300 parts by mass, and more preferably 2 to 150 parts by mass, per 100 parts by mass of the resin component.

[0157] (Coloring agent) The epoxy resin composition may further contain a coloring agent. Examples of known coloring agents include carbon black, organic dyes, organic pigments, titanium dioxide, red lead, and red iron oxide. The amount of coloring agent can be appropriately selected depending on the purpose. The coloring agent may be used alone or in combination of two or more types.

[0158] (Stress reliever) The epoxy resin composition may contain stress-relieving agents such as silicone oil and silicone rubber particles. Including stress-relieving agents can further reduce package warping and the occurrence of package cracks. Examples of commonly used stress-relieving agents (flexible agents) include thermoplastic elastomers such as silicone-based, styrene-based, olefin-based, urethane-based, polyester-based, polyether-based, polyamide-based, and polybutadiene-based agents; rubber particles such as NR (natural rubber), NBR (acrylonitrile-butadiene rubber), acrylic rubber, urethane rubber, and silicone powder; and rubber particles having a core-shell structure such as methyl methacrylate-styrene-butadiene copolymer (MBS), methyl methacrylate-silicone copolymer, and methyl methacrylate-butyl acrylate copolymer. One type of stress-relieving agent may be used alone, or two or more types may be used in combination. Among these, silicone-based stress-relieving agents are preferred. Examples of silicone-based stress-relieving agents include those having epoxy groups, those having amino groups, and those modified with polyether.

[0159] [Method for preparing epoxy resin compositions] The method for preparing the epoxy resin composition is not particularly limited. A common method involves thoroughly mixing predetermined amounts of components using a mixer or the like, then melt-kneading them using a mixing roll, extruder, or the like, followed by cooling and pulverization. More specifically, for example, a method can be used in which predetermined amounts of the above-mentioned components are uniformly stirred and mixed, then kneaded using a kneader, roll, extruder, or the like that has been preheated to 70°C to 140°C, followed by cooling and pulverization. The epoxy resin composition according to the first embodiment includes mixing an epoxy resin, an inorganic filler with an average particle size of 50 nm or less, and a curing agent containing a compound represented by the following general formula (B), and other preparations can be made in accordance with the above preparation method.

[0160] [Properties of epoxy resin compositions] The epoxy resin compositions according to the first to third embodiments have been found to have suppressed viscosity increases and excellent continuous moldability. The epoxy resin compositions according to the first to third embodiments are advantageous in that they have excellent fluidity during transfer molding, even when containing a high proportion of inorganic fillers, thereby suppressing wire flow and the occurrence of unfilled areas. Furthermore, while continuous moldability tends to decrease when inorganic fillers such as alumina are included in a high proportion in general, the epoxy resin compositions according to the first to third embodiments are advantageous because they have excellent continuous moldability.

[0161] The epoxy resin composition is preferably solid at room temperature and atmospheric pressure (for example, 25°C and atmospheric pressure). The shape of the epoxy resin composition when it is solid is not particularly limited, and examples include powder, granules, and tablets. When the epoxy resin composition is in tablet form, the dimensions and mass are preferably such that they are suitable for the packaging molding conditions, from the viewpoint of ease of handling.

[0162] The epoxy resin compositions according to the first to third embodiments have been found to exhibit excellent kneadability. Therefore, even when the inorganic filler content is increased, the epoxy resin compositions tend to be well prepared.

[0163] When an epoxy resin composition is molded using a spiral flow measurement mold conforming to EMMI-1-66 under the conditions of a mold temperature of 175°C, a molding pressure of 6.9 MPa, and a curing time of 90 seconds, the flow distance (inches) is preferably 30.0 inches (914 mm) or more, more preferably 37.0 inches (940 mm) or more, and may also be 65.0 inches (1651 mm) or more. Furthermore, the flow distance may be 100 inches (2540 mm) or less. The measurement is specifically performed according to the method described in the examples.

[0164] The thermal hardness of the epoxy resin composition when it is cured is not particularly limited. For example, when the epoxy resin composition is molded at 175°C, 90 sec, and a pressure of 7 MPa, the thermal hardness measured using a Shore D hardness tester is preferably 60 or higher, more preferably 65 or higher, even more preferably 70 or higher, and particularly preferably 75 or higher.

[0165] The melt viscosity of the epoxy resin composition at 175°C is not particularly limited, but is preferably 350 Pa·s or less, more preferably 300 Pa·s or less, even more 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-efficiency flow tester) as follows: A predetermined amount of epoxy resin composition is weighed using an electronic balance, and tablets are made using a tablet press. The temperature of the test mold is confirmed to be at the predetermined temperature, and the sample is placed in the pot. The plunger is immediately set, and the measurement is started. The measurement can be carried out specifically by the method described in the examples.

[0166] The thermal conductivity of the epoxy resin composition when cured is not particularly limited. For example, the thermal conductivity of the cured product may be 0.5 W / (m·K) or higher at room temperature (25°C). The thermal conductivity of the cured product can be measured by the xenon flash (Xe-flash) method (for example, a Hyper Flash device manufactured by NETZSCH, trade name: LFA467).

[0167] [Uses of epoxy resin compositions] The epoxy resin compositions according to the first to third embodiments are used for transfer molding. Preferably, the epoxy resin compositions according to the first to third embodiments are used as molding materials for sealing elements by transfer molding.

[0168] ≪1.2 Electronic Components and Equipment≫ The electronic component devices according to the first to third embodiments include an element and a cured product of an epoxy resin composition according to any one of the first to third embodiments for sealing the element. Examples of electronic component devices include those in which elements (active elements such as semiconductor chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils) are mounted on support members such as lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, and organic substrates, and the resulting element section is sealed with an epoxy resin composition. More specifically, common resin-encapsulated ICs such as DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package) have a structure in which elements are fixed on a lead frame, the terminal parts of the elements such as bonding pads are connected to the lead parts by wire bonding, bumps, etc., and then sealed by transfer molding using an epoxy resin composition; TCP (Tape Carrier Package) has a structure in which elements connected to a tape carrier by bumps are sealed with an epoxy resin composition; and COB (Chip On) has a structure in which elements are connected to wiring formed on a support member by wire bonding, flip-chip bonding, solder, etc., and then sealed with an epoxy resin composition. Examples of such modules include boards, hybrid ICs, and multi-chip modules; BGAs (Ball Grid Arrays), CSPs (Chip Size Packages), and MCPs (Multi Chip Packages) which have a structure in which elements are mounted on the surface of a support member having terminals for connecting to a printed circuit board formed on its back surface, the elements are connected to the wiring formed on the support member by bumps or wire bonding, and then the elements are sealed with an epoxy resin composition. Furthermore, epoxy resin compositions can also be suitably used in printed circuit boards.

[0169] One method for encapsulating electronic components using an epoxy resin composition is the low-pressure transfer molding method.

[0170] ≪1.3 Method for Manufacturing Electronic Component Devices≫ The manufacturing method for electronic component devices according to the first to third embodiments includes encapsulating the elements with the epoxy resin composition according to any of the first to third embodiments described above. The encapsulation method is as described above.

[0171] ≪2. Fourth Embodiment≫ Next, we will describe the fourth embodiment in detail.

[0172] ≪2.1 Epoxy Resin Compositions for Compression Molding≫ The epoxy resin composition for compression molding according to the fourth embodiment (hereinafter, in the description of the fourth embodiment, also simply referred to as the "epoxy resin composition") contains an epoxy resin, an inorganic filler, and a curing agent containing a compound represented by the following general formula (B).

[0173] [ka]

[0174] In general formula (B), R 1 ~R 5 Each of these independently represents a monovalent organic group with 1 to 6 carbon atoms. X1 to X3 each independently represent an integer from 0 to 4. X4 and X5 each independently represent integers between 0 and 3. n1 represents a number between 1 and 10. n2 represents a number between 1 and 10.

[0175] The above epoxy resin composition was found to be easily melted. Although the reason for this is not entirely clear, it is presumed that the epoxy resin composition is easily melted because it contains a curing agent containing a compound represented by general formula (B). Therefore, the epoxy resin composition according to the fourth embodiment is considered suitable for compression molding. Hereinafter, the ease with which the epoxy resin composition melts will also be referred to as "solubility".

[0176] The epoxy resin composition according to the fourth embodiment may further contain curing accelerators, other additives, etc. The components that may be included in the epoxy resin composition according to the fourth embodiment will be described in detail below.

[0177] <Epoxy resin> The epoxy resin composition according to the fourth embodiment comprises an epoxy resin. The type of epoxy resin is not particularly limited as long as it has two or more epoxy groups in one molecule. Specifically, novolac-type epoxy resins (phenol novolac-type epoxy resins, orthocresol novolac-type epoxy resins, etc.) are obtained by condensing or co-condensing a novolac resin obtained by condensing or co-condensing a novolac resin obtained by phenol compounds selected from the group consisting of phenol compounds such as phenol, cresol, xylenol, resorcinol, catechol, bisphenol A, bisphenol F, and naphthol compounds such as α-naphthol, β-naphthol, and dihydroxynaphthalene, with an aliphatic aldehyde compound such as formaldehyde, acetaldehyde, or propionaldehyde, under an acidic catalyst, and then epoxidizing the novolac resin. Copolymer epoxy resins that have been modified; diphenylmethane-type epoxy resins that are diglycidyl ethers of bisphenol A, bisphenol F, etc.; biphenyl-type epoxy resins that are diglycidyl ethers of alkyl-substituted or unsubstituted biphenols; stilbene-type epoxy resins that are diglycidyl ethers of stilbene-based phenol compounds; sulfur atom-containing epoxy resins that are diglycidyl ethers of bisphenol S, etc.; epoxy resins that are glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and polypropylene glycol; glycidyl ester-type epoxy resins that are glycidyl esters of polycarboxylic acid compounds such as phthalic acid, isophthalic acid, and tetrahydrophthalic acid; glycidylamine-type epoxy resins in which the active hydrogen bonded to the nitrogen atom of aniline, diaminodiphenylmethane, isocyanuric acid, etc. is replaced with a glycidyl group; dicyclopentadiene-type epoxy resins that are epoxidized from a copolymer resin of dicyclopentadiene and a phenol compound;Alicyclic epoxy resins such as vinylcyclohexene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 2-(3,4-epoxy)cyclohexyl-5,5-spiro(3,4-epoxy)cyclohexane-m-dioxane, which have epoxidized olefin bonds within the molecule; paraxylylene-modified epoxy resins, which are glycidyl ethers of paraxylylene-modified phenol resins; metaxylylene-modified epoxy resins, which are glycidyl ethers of metaxylylene-modified phenol resins; terpene-modified epoxy resins, which are glycidyl ethers of terpene-modified phenol resins; and dicyclopentadiene-modified phenol resins, which are glycidyl ethers of dicyclo Examples of epoxy resins include: pentadiene-modified epoxy resins; cyclopentadiene-modified epoxy resins, which are glycidyl ethers of cyclopentadiene-modified phenolic resins; polycyclic aromatic ring-modified epoxy resins, which are glycidyl ethers of polycyclic aromatic ring-modified phenolic resins; naphthalene-type epoxy resins, which are glycidyl ethers of naphthalene ring-containing phenolic resins; halogenated phenol novolac-type epoxy resins; hydroquinone-type epoxy resins; trimethylolpropane-type epoxy resins; linear aliphatic epoxy resins obtained by oxidizing olefin bonds with peracids such as peracetic acid; and aralkyl-type epoxy resins, which are epoxidized aralkyl-type phenolic resins such as phenol aralkyl resins and naphthol aralkyl resins. Furthermore, epoxides of silicone resins and acrylic resins can also be cited as epoxy resins. These epoxy resins may be used individually or in combination of two or more types.

[0178] Among the epoxy resins mentioned above, epoxy resins selected from the group consisting of biphenyl-type epoxy resins, stilbene-type epoxy resins, diphenylmethane-type epoxy resins, sulfur atom-containing epoxy resins, novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, triphenylmethane-type epoxy resins, copolymer-type epoxy resins, and aralkyl-type epoxy resins (these are referred to as "specific epoxy resins") are preferred from the viewpoint of balancing reflow resistance and viscosity. Details and preferred embodiments of the specific epoxy resin are as described in the section on epoxy resins included in the epoxy resin compositions according to the first to third embodiments. The specific epoxy resin may be used individually or in combination of two or more types.

[0179] When the epoxy resin contains a specific epoxy resin, from the viewpoint of exhibiting the performance of the specific epoxy resin, it is preferable that its total content be 30% by mass or more of the total epoxy resin, and more preferably 50% by mass or more.

[0180] Among specific epoxy resins, biphenyl-type epoxy resins, stilbene-type epoxy resins, diphenylmethane-type epoxy resins, and sulfur atom-containing epoxy resins are more preferred from the viewpoint of viscosity, and dicyclopentadiene-type epoxy resins, triphenylmethane-type epoxy resins, and aralkyl-type epoxy resins are preferred from the viewpoint of heat resistance.

[0181] In a preferred embodiment, the epoxy resin composition may contain at least one selected from the group consisting of diphenylmethane-type epoxy resins and biphenyl-type epoxy resins. When the epoxy resin composition contains a diphenylmethane type epoxy resin, the content of the diphenylmethane type epoxy resin may be 40% to 100% by mass, 50% to 100% by mass, or 60% to 100% by mass, based on the total mass of the epoxy resin. When the epoxy resin composition contains a biphenyl-type epoxy resin, the content of the biphenyl-type epoxy resin may be 20% to 100% by mass or 25% to 100% by mass relative to the total mass of the epoxy resin.

[0182] In a preferred embodiment, a diphenylmethane type epoxy resin and a biphenyl type epoxy resin may be used in combination. In this case, the total content ratio of the diphenylmethane type epoxy resin and the biphenyl type epoxy resin to the total mass of the epoxy resin is preferably 70% by mass or more, more preferably 80% by mass or more, and still more preferably 90% by mass or more. When the diphenylmethane type epoxy resin and the biphenyl type epoxy resin are used in combination, the content ratio (diphenylmethane type epoxy resin: biphenyl type epoxy resin) of the diphenylmethane type epoxy resin and the biphenyl type epoxy resin may be 90:10 to 10:90 on a mass basis, or may be 80:20 to 50:50.

[0183] The epoxy equivalent of the epoxy resin is not particularly limited. From the viewpoint of the balance of various properties such as moldability, reflow resistance, and electrical reliability, the epoxy equivalent 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 of the epoxy resin is a value measured by a method according to JIS K 7236:2009.

[0184] When the epoxy resin is solid, its softening point or melting point is not particularly limited. From the viewpoints of moldability and reflow resistance, it is preferably 40°C to 180°C, and from the viewpoint of handleability during the preparation of the epoxy resin composition, it is more preferably 50°C to 130°C. The melting point of the epoxy resin is a value measured by differential scanning calorimetry (DSC), and the softening point of the epoxy resin is a value measured by a method (ring and ball method) according to JIS K 7234:1986.

[0185] The content ratio 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, from the viewpoints of strength, viscosity, heat resistance, moldability, etc.

[0186] <Inorganic filler> The epoxy resin composition according to the fourth embodiment contains an inorganic filler. The material of the inorganic filler is not particularly limited. Specifically, examples of inorganic materials include silica (fused silica, crystalline silica, etc.), glass, alumina, calcium carbonate, zirconium silicate, calcium silicate, silicon nitride, aluminum nitride, boron nitride, beryllia, zirconia, zircon, fossterite, steatite, spinel, mullite, titania, talc, clay, and mica. An inorganic filler having a flame-retardant effect may also be used. Examples of inorganic fillers having a flame-retardant effect include aluminum hydroxide, magnesium hydroxide, composite metal hydroxides such as magnesium-zinc composite hydroxides, and zinc borate. Among these, fused silica is preferred from the viewpoint of reducing the coefficient of linear expansion, and alumina is preferred from the viewpoint of high thermal conductivity. One type of inorganic filler may be used alone, or two or more types may be used in combination. Examples of inorganic fillers in the form of powder, beads formed from the powder into spheres, fibers, etc.

[0187] The average particle size of the inorganic filler contained in the epoxy resin composition is not particularly limited. For example, the average particle size of the inorganic filler is preferably 0.2 μm to 80 μm, more preferably 0.5 μm to 70 μm, and even more preferably 1 μm to 50 μm. When the average particle size of the inorganic filler is 0.2 μm or more, the increase in viscosity of the epoxy resin composition tends to be suppressed. When the average particle size of the inorganic filler is 80 μm or less, the ability to fill narrow gaps tends to improve. In this disclosure, the average particle diameter of the inorganic filler is defined as the volume-average particle diameter.

[0188] The maximum particle size (also called the cut point) of the inorganic filler is not particularly limited. From the viewpoint of filling narrow gaps, the maximum particle size of the inorganic filler is preferably 150 μm or less, more preferably 75 μm or less, and even more preferably 55 μm or less.

[0189] The shape of the inorganic filler is not particularly limited. From the viewpoint of the kneadability of the epoxy resin composition, the particle shape of the inorganic filler is preferably spherical.

[0190] The content of the inorganic filler is not particularly limited. The inorganic filler content is preferably 50% by volume or more, more preferably 60% by volume or more, even more preferably 70% by volume or more, particularly preferably 75% by volume or more, and most preferably 80% by volume or more, relative to the total volume of the epoxy resin composition. By setting the inorganic filler content to 50% by volume or more of the total epoxy resin composition, it tends to be possible to suitably improve properties such as the coefficient of thermal expansion, thermal conductivity, and elastic modulus of the cured product. Furthermore, the inorganic filler content is preferably 95% by volume or less, more preferably 90% by volume or less, and even more preferably 87% by volume or less, relative to the total volume of the epoxy resin composition. When the inorganic filler content is 95% by volume or less of the total epoxy resin composition, the increase in viscosity of the epoxy resin composition tends to be suppressed. From the above viewpoint, the inorganic filler content is preferably 50% to 95% by volume, more preferably 60% to 95% by volume, even more preferably 70% to 95% by volume, particularly preferably 75% to 90% by volume, and most preferably 80% to 87% by volume, based on the total volume of the epoxy resin composition.

[0191] Furthermore, in epoxy resin compositions, even if the inorganic filler content is, for example, 82% by volume or more, more preferably 84% by volume or more, even more preferably 85% by volume or more, particularly preferably 86% by volume or more, and most preferably 87% by volume or more, the epoxy resin composition tends to be able to be kneaded well. For example, by using a highly thermally conductive inorganic filler such as alumina and setting the inorganic filler content to the above proportions, a highly thermally conductive cured product can be obtained.

[0192] Furthermore, in epoxy resin compositions, even if the inorganic filler content is, for example, 90% by mass or more, more preferably 92% by mass or more, of the epoxy resin composition, it tends to be able to be kneaded well.

[0193] -alumina- When obtaining a cured product with high thermal conductivity, the inorganic filler preferably contains alumina, and more preferably contains alumina as the main component (i.e., 50% or more by volume relative to the total volume of the inorganic filler). The average particle size of alumina when the inorganic filler contains alumina is not particularly limited. For example, the average particle size of alumina is preferably 0.2 μm to 80 μm, more preferably 0.5 μm to 70 μm, and even more preferably 1 μm to 50 μm. When the average particle size is 0.2 μm or more, the increase in viscosity of the epoxy resin composition tends to be suppressed. When the average particle size is 80 μm or less, the ability to fill narrow gaps tends to improve.

[0194] The maximum particle size of alumina is not particularly limited. From the viewpoint of filling narrow gaps, the maximum particle size of alumina is preferably 150 μm or less, more preferably 75 μm or less, and even more preferably 55 μm or less.

[0195] In one preferred embodiment, alumina with an average particle size of 0.1 μm to 2.0 μm, preferably 0.2 μm to 1.5 μm, more preferably 0.3 μm to 1.0 μm, may be used in combination with alumina with an average particle size exceeding 2.0 μm and 75 μm or less, preferably 5.0 μm to 55 μm, more preferably 8.0 μm to 20 μm. Using two or more types of alumina with different average particle sizes tends to improve packing properties and fluidity.

[0196] The shape of the alumina is not particularly limited. From the viewpoint of the kneadability of the epoxy resin composition, the alumina particles are preferably spherical.

[0197] When the inorganic filler contains alumina, from the viewpoint of high thermal conductivity, the alumina content relative to the total mass of the inorganic filler is preferably 75% by mass or more, more preferably 80% by mass or more, even more preferably 85% by mass or more, particularly preferably 90% by mass or more, and extremely preferably 95% by mass or more. Furthermore, from the viewpoint of lower viscosity and ease of mixing, the alumina content relative 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 even more preferably 99.7% by mass or less.

[0198] When the inorganic filler contains alumina, it is preferable that the inorganic filler also contains silica in addition to alumina. When the inorganic filler contains silica in addition to alumina, the kneadability tends to be improved compared to when it contains only alumina. For example, the inorganic filler may contain fine silica (for example, silica with an average particle size of 0.1 μm to 2.0 μm, preferably 0.2 μm to 1.5 μm, more preferably 0.3 μm to 1.0 μm) in addition to alumina. Alternatively, the inorganic filler may contain particularly fine silica (for example, silica with an average particle size of 1 nm to 500 nm, more preferably 5 nm to 300 nm, and even more preferably 10 nm to 200 nm) in addition to alumina. When the inorganic filler contains fine silica, the generation of burrs when the product is cured tends to be suppressed. When alumina and silica are used together as inorganic fillers, from the viewpoint of kneadability, the silica content is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, and even more preferably 0.3% by mass or more, relative to the total mass of the inorganic filler. Furthermore, from the viewpoint of high thermal conductivity, the silica content is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 2% by mass or less, relative to the total amount of the inorganic filler.

[0199] -silica- From the viewpoints of reflow resistance and suppression of viscosity increase, etc., it is preferable that the inorganic filler contains silica, and it may contain silica as the main component (that is, 50% by volume or more based on 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 0.2 μm to 80 μm, more preferably 0.5 μm to 70 μm, and even more preferably 1 μm to 50 μm. When the average particle diameter is 0.2 μm or more, the tendency of the viscosity of the epoxy resin composition to increase is suppressed. When the average particle diameter is 80 μm or less, the filling property into narrow gaps tends to improve.

[0200] Also, the inorganic filler may contain fine silica (for example, silica having an average particle diameter of 0.1 μm to 2.0 μm, preferably 0.2 μm to 1.5 μm, and more preferably 0.3 μm to 1.0 μm).

[0201] Also, the inorganic filler may contain particularly fine silica (for example, silica having an average particle diameter of 1 nm to 500 nm, more preferably 5 nm to 300 nm, and even more preferably 10 nm to 200 nm). When the inorganic filler contains fine silica, the generation of burrs when formed into a cured product tends to be suppressed.

[0202] From the viewpoints of reduction of elastic modulus and reduction of linear expansion coefficient, the inorganic filler may contain large particle diameter silica. Examples of the large particle diameter silica include large particle diameter silica having an average particle diameter exceeding 2.0 μm and 75 μm or less, preferably 5.0 μm to 55 μm, and more preferably 8.0 μm to 20 μm.

[0203] The maximum particle diameter of silica is not particularly limited. From the viewpoint of filling property into narrow gaps, the maximum particle diameter of silica is preferably 150 μm or less, more preferably 75 μm or less, and even more preferably 55 μm or less.

[0204] The shape of silica is not particularly limited. From the viewpoint of the kneadability of the epoxy resin composition, the particle shape of silica is preferably spherical.

[0205] When the inorganic filler contains silica, the silica content is not particularly limited and may be 70% to 100% by mass, 80% to 100% by mass, or 90% to 100% by mass relative to the total mass of the inorganic filler. Furthermore, when silica is used in combination with alumina, the silica content is as described above.

[0206] <Hardening agent> The epoxy resin composition according to the fourth embodiment contains a curing agent comprising a compound represented by general formula (B) (a specific curing agent), and may also contain other curing agents. Details of the curing agent are as described in the section on curing agents contained in the epoxy resin compositions according to the first to third embodiments.

[0207] <Curing accelerator> The epoxy resin composition according to the fourth embodiment may contain a curing accelerator. Details of the curing accelerator are as described in the section on curing accelerators that may be included in the epoxy resin compositions according to the first to third embodiments.

[0208] <Various additives> The epoxy resin composition according to the fourth embodiment may contain various additives such as coupling agents, ion exchangers, mold release agents, flame retardants, colorants, and stress relaxants. Details of the additives are as described in the section on additives that may be included in the epoxy resin compositions according to the first to third embodiments.

[0209] In particular, the epoxy resin composition contains a release agent, and it is preferable that the content of the release agent is greater than 0% by mass and 2.0% by mass or less, more preferably greater than 0% by mass and 1.5% by mass or less, and even more preferably greater than 0% by mass and 1.2% by mass or less, relative to the total mass of the epoxy resin composition. By including the release agent at the above content, it is possible to suppress a significant decrease in appearance, adhesive strength, and laser marking properties compared to cases where a higher content is included. Furthermore, according to an epoxy resin composition according to one embodiment of the fourth embodiment, it is possible to maintain good release properties even when the content of the release agent is within the above range.

[0210] [Method for preparing epoxy resin compositions] The method for preparing the epoxy resin composition according to the fourth embodiment is not particularly limited, and specific examples are as described in the sections on the epoxy resin compositions according to the first to third embodiments.

[0211] The epoxy resin composition according to the fourth embodiment is preferably solid at room temperature and atmospheric pressure (for example, 25°C and atmospheric pressure). The shape of the epoxy resin composition when it is solid is not particularly limited and can be in the form of powder, granules, tablets, etc. When the epoxy resin composition is in tablet form, the dimensions and mass should preferably be such that they are suitable for the molding conditions of the package, from the viewpoint of ease of handling.

[0212] It has been found that epoxy resin compositions according to one embodiment of the fourth embodiment tend to have excellent kneadability. Therefore, even when the inorganic filler content is increased or inorganic fillers with small particle sizes are used, epoxy resin compositions tend to be prepared well.

[0213] [Uses of epoxy resin compositions] The epoxy resin composition according to the fourth embodiment is used for compression molding. Preferably, the epoxy resin composition is used as a molding material for sealing elements by compression molding.

[0214] [Properties of epoxy resin compositions] The epoxy resin composition according to the fourth embodiment has been found to have excellent solubility. Therefore, the epoxy resin composition according to the fourth embodiment is suitable for sealing elements by compression molding. Furthermore, while generally improving the solubility of an epoxy resin composition tends to reduce its curability, the epoxy resin composition according to the fourth embodiment tends to maintain excellent curability.

[0215] The thermal hardness of the epoxy resin composition when it is cured is not particularly limited. For example, when the epoxy resin composition is molded at 175°C, 90 sec, and a pressure of 7 MPa, the thermal hardness measured using a Shore D hardness tester is preferably 60 or higher, more preferably 65 or higher, even more preferably 70 or higher, and particularly preferably 75 or higher.

[0216] When 5 g of epoxy resin composition is compression molded using a flat plate mold for disc flow measurement at 180°C, with a load of 78 N and a curing time of 90 seconds, the disc flow is preferably 75.0 mm or more, more preferably 78.0 mm or more, and even more preferably 80.0 mm or more. The disc flow may also be 110 mm or less.

[0217] The melt viscosity of the epoxy resin composition at 175°C is not particularly limited, but is preferably 250 Pa·s or less, more preferably 240 Pa·s or less, and even more preferably 230 Pa·s or less. The melt viscosity is measured by a flow tester (e.g., a high-efficiency flow tester) as follows: A predetermined amount of epoxy resin composition is weighed using an electronic balance, and tablets are made using a tablet press. After confirming that the temperature of the test mold is at the predetermined temperature, the sample is placed in the pot. The plunger is immediately set, and the measurement is started.

[0218] The thermal conductivity of the epoxy resin composition when cured is not particularly limited. For example, the thermal conductivity of the cured product may be 0.5 W / (m·K) or higher at room temperature (25°C). The thermal conductivity of the cured product can be measured by the xenon flash (Xe-flash) method (for example, a Hyper Flash device manufactured by NETZSCH, trade name: LFA467).

[0219] The epoxy resin composition according to one embodiment of the fourth embodiment tends to have excellent mold release properties when cured. Therefore, even if the amount of mold release agent is reduced to improve, for example, the appearance, adhesive strength, and laser marking properties of the cured product, good mold release properties tend to be maintained.

[0220] ≪2.2 Electronic Components and Equipment≫ The electronic component device according to the fourth embodiment comprises an element and a cured product of the epoxy resin composition according to the fourth embodiment described above, which encapsulates the element. Examples of electronic component devices include those in which elements (active elements such as semiconductor chips, transistors, diodes, and thyristors, and passive elements such as capacitors, resistors, and coils) are mounted on support members such as lead frames, pre-wired tape carriers, wiring boards, glass, silicon wafers, and organic substrates, and the resulting element section is sealed with an epoxy resin composition. More specifically, common resin-encapsulated ICs such as DIP (Dual Inline Package), PLCC (Plastic Leaded Chip Carrier), QFP (Quad Flat Package), SOP (Small Outline Package), SOJ (Small Outline J-lead package), TSOP (Thin Small Outline Package), and TQFP (Thin Quad Flat Package) have a structure in which elements are fixed on a lead frame, the terminal parts of the elements such as bonding pads are connected to the lead parts by wire bonding, bumps, etc., and then sealed with an epoxy resin composition; TCP (Tape Carrier Package) has a structure in which elements connected to a tape carrier by bumps are sealed with an epoxy resin composition; and COB (Chip On) has a structure in which elements are connected to wiring formed on a support member by wire bonding, flip-chip bonding, solder, etc., and then sealed with an epoxy resin composition. Examples of such modules include boards, hybrid ICs, and multi-chip modules; BGAs (Ball Grid Arrays), CSPs (Chip Size Packages), and MCPs (Multi Chip Packages) which have a structure in which elements are mounted on the surface of a support member having terminals for connecting to a printed circuit board formed on its back surface, the elements are connected to the wiring formed on the support member by bumps or wire bonding, and then the elements are sealed with an epoxy resin composition. Furthermore, epoxy resin compositions can also be suitably used in printed circuit boards.

[0221] ≪2.3 Method for Manufacturing Electronic Component Devices≫ A method for manufacturing an electronic component device according to the fourth embodiment includes sealing the element by compression molding of the epoxy resin composition according to the fourth embodiment described above. [Examples]

[0222] The embodiments of this disclosure will be described in detail below with reference to examples, but the embodiments of this disclosure are not limited to these examples.

[0223] ≪Examples of the First to Third Embodiments≫ [Preparation of epoxy resin composition] The epoxy resin compositions of the examples and comparative examples were prepared by mixing the following materials in the compositions shown in Table 1 and performing roll kneading at a kneading temperature of 80°C for a kneading time of 15 minutes. In Table 1, "-" indicates that the component was not included.

[0224] (Epoxy resin) • Epoxy resin 1: Diphenylmethane type epoxy resin (bisphenol type epoxy resin) (Product name: YSLV-80XY, Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 190g / eq) • Epoxy resin 2: Biphenyl-type epoxy resin (Product name: YX-4000, Mitsubishi Chemical Corporation, epoxy equivalent weight 190g / eq) • Epoxy resin 3: Triphenylmethane type epoxy resin (product name: 1032H60, Mitsubishi Chemical Corporation, epoxy equivalent 170g / eq)

[0225] (Hardening agent) • Hardener 1: A compound in general formula (B) where x1 to x5 are all 0, n1 is 1 to 10, and n2 is 1 to 10 (product name: MEHC7841-4S, Meiwa Kasei Co., Ltd., hydroxyl group equivalent 164 g / eq to 168 g / eq, softening point 58°C to 65°C) • Curing agent 2: Aralkyl type phenolic resin other than general formula (B); in general formula (XII), i is 0 and R 23 A compound in which all atoms are hydrogen atoms (Product name: MEHC7851-SS, Meiwa Chemicals Co., Ltd., Hydroxyl group equivalent 201g / eq~205g / eq, Softening point 64℃~69℃) • Hardener 3: Triphenylmethane-type phenolic resin (product name: MEH7500, Meiwa Chemicals Co., Ltd., hydroxyl group equivalent 95-105 g / eq, softening point 105°C-115°C)

[0226] (Inorganic filler) • Inorganic filler 1: Fine particle alumina (average particle size 0.4 μm, maximum particle size approximately 2.0 μm) • Inorganic filler 2: Large particle alumina (average particle size 10 μm, maximum particle size 75 μm) • Inorganic filler 3: Ultrafine silica (average particle size 25 nm, maximum particle size 50 nm) • Inorganic filler 4: Fine particle silica (average particle size 0.6 μm, maximum particle size 5.0 μm) • Inorganic filler 5: Large particle silica (average particle size 10 μm, maximum particle size 75 μm)

[0227] (Curing accelerator) • Curing accelerator: Phosphorus-based curing accelerator

[0228] (Other additives) • Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane (product name: KBM-573, Shin-Etsu Chemical Co., Ltd.) • Release agent: Carnauba wax • Coloring agent: Carbon black • Ion exchanger: Hydrotalcite compounds (Product name: DHT-4A, Kyowa Chemical Industry Co., Ltd.)

[0229] [Evaluation of epoxy resin compositions] The properties of the epoxy resin compositions prepared in the examples and comparative examples were evaluated by the following property tests. Unless otherwise specified, the epoxy resin compositions were molded using a transfer molding machine under the following conditions: mold temperature of 175°C, molding pressure of 6.9 MPa, and curing time of 90 seconds. Post-curing was also performed at 175°C for 5 hours as needed.

[0230] (1) Spiral Flow An epoxy resin composition was molded under the above conditions using a spiral flow measurement mold conforming to EMMI-1-66, and the flow distance (inch) was determined.

[0231] (2) Evaluation of Bali 15 g of epoxy resin composition was placed on a mold heated to 180°C on a press hot plate and molded for a curing time of 90 seconds. After molding, the length of the longest portion through which the epoxy resin composition flowed in the 50 μm, 30 μm, 20 μm, 10 μm, 5 μm, and 2 μm slits created in the mold was measured using calipers, and this measurement was defined as the burr length.

[0232] (3) Hardness when heated The epoxy resin composition was molded into a disc with a diameter of 50 mm and a thickness of 3 mm under the above conditions, and immediately after molding, the hardness was measured using a Shore D hardness tester (HD-1120 (Type D) manufactured by Ueshima Seisakusho Co., Ltd.).

[0233] (4) Continuous moldability (evaluation of shear release force) A chrome-plated stainless steel plate measuring 50 mm in length, 35 mm in width, and 0.4 mm in thickness was inserted into a mold that forms a 20 mm diameter disc on top of it. An epoxy resin composition was then molded under the above conditions, and immediately after molding, the stainless steel plate was pulled out and the maximum pull-out force was recorded. This was repeated 10 times consecutively on the same stainless steel plate, and the average pull-out force from the 2nd to the 10th time was calculated and evaluated.

[0234] (5) Melt viscosity (ηFT) The melt viscosity of the epoxy resin composition heated to 175°C was measured using a flow tester. The epoxy resin composition was weighed using an electronic balance, and tablets were made using a tablet press. After confirming that the temperature of the test mold was 175°C, the sample was placed in the pot. The plunger was immediately set, and the measurement was started.

[0235] [Table 1]

[0236] [Table 2]

[0237] [Table 3]

[0238] As can be seen from Tables 1-3, the epoxy resin compositions of the examples have low viscosity and excellent continuous molding properties. Furthermore, as can be seen from the evaluation of burrs, burrs can be suitably suppressed in the examples using ultrafine silica. Moreover, even when using ultrafine silica, the epoxy resin compositions of the examples maintain excellent fluidity.

[0239] ≪Example of the Fourth Embodiment≫ [Preparation of epoxy resin composition] The epoxy resin compositions of the examples and comparative examples were prepared by mixing the following materials in the compositions shown in Table 4 and performing roll kneading at a kneading temperature of 80°C for a kneading time of 15 minutes. In Table 4, "-" indicates that the component was not included.

[0240] (Epoxy resin) Epoxy resin 1: Diphenylmethane type epoxy resin (bisphenol type epoxy resin) (Product name: YSLV-80XY, Nippon Steel Chemical & Material Co., Ltd., epoxy equivalent 190g / eq) Epoxy resin 2: Biphenyl-type epoxy resin (Product name: YX-4000, Mitsubishi Chemical Corporation, epoxy equivalent weight 190g / eq)

[0241] (Hardening agent) • Hardener 1: Novolac-type phenolic resin (product name: H-4, Meiwa Chemicals Co., Ltd., hydroxyl group equivalent 103g / eq~107g / eq, softening point 67℃~75℃) • Hardener 2: Aalkyl-type phenolic resin (product name: MEHC7800-4S, hydroxyl group equivalent 167g / eq~179g / eq, softening point 61℃~65℃) • Hardener 3: A compound in general formula (B) where x1 to x5 are all 0, n1 is 1 to 10, and n2 is 1 to 10 (product name: MEHC7841-4S, Meiwa Kasei Co., Ltd., hydroxyl group equivalent 164 g / eq to 168 g / eq, softening point 58°C to 65°C) • Hardener 4: Aalkyl-type phenolic resin (Product name: MEHC7851-SS, Meiwa Kasei Co., Ltd., Hydroxyl group equivalent 201g / eq~205g / eq, Softening point 64℃~69℃)

[0242] (Inorganic filler) • Inorganic filler 1: Fine particle alumina (average particle size 0.4 μm, maximum particle size approximately 2.0 μm) • Inorganic filler 2: Large particle alumina (average particle size 10 μm, maximum particle size 75 μm) • Inorganic filler 3: Ultrafine silica (average particle size 0.1 μm, maximum particle size approximately 2.0 μm)

[0243] (Curing accelerator) • Curing accelerator: Phosphorus-based curing accelerator

[0244] (Other additives) • Coupling agent: N-phenyl-3-aminopropyltrimethoxysilane (product name: KBM-573, Shin-Etsu Chemical Co., Ltd.) • Release agent: Carnauba wax • Coloring agent: Carbon black • Ion exchanger: Hydrotalcite compounds (Product name: DHT-4A, Kyowa Chemical Industry Co., Ltd.)

[0245] [Evaluation of epoxy resin compositions] The properties of the epoxy resin compositions prepared in the examples and comparative examples were evaluated by the following property tests.

[0246] (1) Solubility Approximately 1.5 g of epoxy resin composition powder (3.5 mm mesh pass, 1.0 mm mesh on) was prepared. The epoxy resin composition powder was placed in a circular shape within the surface on a hot plate (lower mold) heated to 175°C, to a height of approximately 3 mm. A 200 g upper mold, also heated to 175°C, was dropped horizontally onto the placed epoxy resin composition. The upper mold was supported by the lower mold and vertical supports, so that a constant load was applied within the surface. The moment the upper mold fell (i.e., when the upper mold reached the top surface of the powder) was defined as 0 seconds, and the distance the upper mold fell after the epoxy resin composition powder began to melt was measured using a laser displacement meter. The height of the top surface of the epoxy resin composition at 0 seconds was defined as A, and the height at 1 second was defined as B. The solubility of the powder was investigated by calculating B / A × 100 (%).

[0247] (2) Thermal conductivity Using an epoxy resin composition, semiconductor elements were sealed 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 curing time of 150 seconds to prepare test specimens for evaluating thermal conductivity. Subsequently, the thermal conductivity of the test specimens was measured using the xenon flash (Xe-flash) method.

[0248] (3) Continuous moldability (evaluation of shear release force) A chrome-plated stainless steel plate measuring 50 mm in length, 35 mm in width, and 0.4 mm in thickness was inserted into a mold that forms a 20 mm diameter disc on top of it. Using this mold, epoxy resin molding material for sealing was molded under the above conditions, and immediately after molding, the stainless steel plate was pulled out and the maximum pull-out force was recorded. This was repeated 10 times consecutively on the same stainless steel plate, and the average pull-out force from the 2nd to the 10th time was calculated to evaluate the continuous moldability.

[0249] (4) Mixability (temperature of the mixed material) The heating zone of the mixer was set to 90°C, and the temperature of the mixed material was measured at four locations within the mixer. The degree of temperature rise was used as an indicator of mixability. The temperature of the mixed material tends to rise above the set temperature due to factors such as the solubility of the epoxy resin composition, shear heating, and friction of the inorganic filler. The closer the average temperature of the mixed material at the four locations was to the set temperature, the better the mixability was judged to be.

[0250] [Table 4]

[0251] As can be seen from Table 4, the epoxy resin compositions of the examples exhibit excellent solubility. Furthermore, the epoxy resin compositions of the examples also yielded good results in evaluations of kneadability, continuous moldability, and thermal conductivity of the cured product.

[0252] The disclosures of Japanese Patent Applications No. 2020-19082 and No. 2020-19083 are incorporated herein by reference in their entirety. All documents, patent applications, and technical standards described herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually noted as being incorporated by reference.

Claims

1. A method for producing an epoxy resin composition for transfer molding, comprising mixing an epoxy resin, an inorganic filler with an average particle size of 50 nm or less, and a curing agent containing a compound represented by the following general formula (B). 【Chemistry 1】 In general formula (B), R １ ~R ５ Each of these independently represents a monovalent organic group with 1 to 6 carbon atoms. X1 to X3 each independently represent an integer from 0 to 4. X4 and X5 each independently represent integers from 0 to 3. n1 represents a number between 1 and 10. n2 represents a number between 1 and 10.

2. The manufacturing method according to claim 1, wherein the epoxy resin includes a biphenyl-type epoxy resin.

3. The manufacturing method according to claim 2, wherein the content of the biphenyl-type epoxy resin in the epoxy resin composition for transfer molding is 30% to 100% by mass relative to the total mass of the epoxy resin.

4. The manufacturing method according to any one of claims 1 to 3, wherein the inorganic filler content is 60% by volume or more with respect to the total volume of the epoxy resin composition for transfer molding.

5. The manufacturing method according to any one of claims 1 to 4, wherein the content of the compound represented by the general formula (B) in the epoxy resin composition for transfer molding is 30% to 100% by mass relative to the total mass of the curing agent.

6. Epoxy resin and Inorganic fillers and A curing agent containing a compound represented by the following general formula (B), It contains, The inorganic filler is a mixture of an inorganic filler with an average particle diameter of 50 nm or less and an inorganic filler with an average particle diameter greater than 50 nm, and the content of the inorganic filler with an average particle diameter of 50 nm or less is 5 parts by mass or more per 100 parts by mass of the epoxy resin. Epoxy resin composition for transfer molding. 【Chemistry 2】 In general formula (B), R １ ~R ５ Each of these independently represents a monovalent organic group with 1 to 6 carbon atoms. X1 to X3 each independently represent an integer from 0 to 4. X4 and X5 each independently represent integers from 0 to 3. n1 represents a number between 1 and 10. n2 represents a number between 1 and 10.

7. Epoxy resin and Inorganic fillers and A curing agent containing a compound represented by the following general formula (B), It contains, The inorganic filler comprises an inorganic filler with a particle size of 50 nm or less, and the content of the inorganic filler with a particle size of 50 nm or less is 5 parts by mass or more per 100 parts by mass of the epoxy resin. Epoxy resin composition for transfer molding. 【Transformation 3】 In general formula (B), R １ ~R ５ Each of these independently represents a monovalent organic group with 1 to 6 carbon atoms. X1 to X3 each independently represent an integer from 0 to 4. X4 and X5 each independently represent integers from 0 to 3. n1 represents a number between 1 and 10. n2 represents a number between 1 and 10.

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

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

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

11. The epoxy resin composition for transfer molding according to any one of claims 6 to 10, wherein the content of the compound represented by the general formula (B) relative to the total mass of the curing agent is 30% to 100% by mass.

12. Element and, A cured epoxy resin composition obtained by the manufacturing method described in any one of claims 1 to 5, or a cured epoxy resin composition described in any one of claims 6 to 11, which seals the element. An electronic component device equipped with the following features.

13. Epoxy resin and Inorganic fillers and A curing agent containing a compound represented by the following general formula (B), An epoxy resin composition for compression molding containing [the specified ingredient]. 【Chemistry 4】 In general formula (B), R １ ~R ５ Each of these independently represents a monovalent organic group with 1 to 6 carbon atoms. X1 to X3 each independently represent an integer from 0 to 4. X4 and X5 each independently represent integers from 0 to 3. n1 represents a number between 1 and 10. n2 represents a number between 1 and 10.

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

15. The epoxy resin composition for compression molding according to claim 13 or claim 14, wherein the content of the compound represented by the general formula (B) relative to the total mass of the curing agent is 30% to 100% by mass.

16. The epoxy resin composition for compression molding according to any one of claims 13 to 15, further containing a release agent, wherein the content of the release agent is greater than 0% by mass and less than or equal to 2.0% by mass with respect to the total mass of the epoxy resin composition for compression molding.

17. Element and, A cured product of the epoxy resin composition for compression molding according to any one of claims 13 to 16 for sealing the element, An electronic component device equipped with the following features.

Images