JP2023074975A - Semiconductor sealing resin composition, semiconductor sealing material and semiconductor device - Google Patents

Abstract

To provide a semiconductor sealing resin composition and a semiconductor sealing material which show low hygroscopicity when cured and excellent adhesion to metal material, and a semiconductor device comprising the semiconductor sealing material.SOLUTION: A semiconductor sealing resin composition comprises an epoxy resin (A) that is a glycidyl-etherified, polyhydric hydroxy resin (P) comprising, as a reaction material (1), an aromatic compound (i) comprising a phenolic hydroxy group and two or more hydrocarbon groups in an aromatic ring and an aromatic vinyl compound (ii), a curing agent (B), and an inorganic filler (C).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present disclosure relates to a resin composition for semiconductor encapsulation, a semiconductor encapsulation material, and a semiconductor device.

Epoxy resin compositions, which contain epoxy resins and their curing agents as essential components, are excellent in physical properties such as high heat resistance, moisture resistance, and low viscosity. It is widely used in conductive adhesives, other adhesives, matrices for composite materials, paints, photoresist materials, and developer materials. Among these various applications, in the field of semiconductor encapsulation materials, there is a high demand for miniaturization and high integration of electronic devices, and there is a shift to surface mount packages such as BGA and CSP, or reliability in bonding under high temperature environments. The use of copper wire, which has a high

However, copper wire is more susceptible to corrosion than traditional gold. Therefore, when interface deterioration such as peeling occurs at the interface between the semiconductor encapsulating material and the lead frame, moisture concentrates in the peeled portion due to capillary action, corroding the chip or the wire bonding joint. Furthermore, water rapidly expands in a reflow process at a high temperature, which causes cracks. For this reason, it is essential that semiconductor encapsulating materials should reduce peeling at the lead frame interface during reflow, and furthermore, low hygroscopic properties and improved adhesive properties with lead frames are required. In addition to the above properties, it is desirable to use a semiconductor encapsulating material that is highly filled with a filler such as silica for the purpose of suppressing thermal expansion. Therefore, in order to increase the filling rate, it is important that the resin material in the semiconductor encapsulating material has low viscosity and excellent fluidity.

In order to meet such required properties, for example, Patent Document 1 discloses a technique of epoxidizing the OH groups of a polyhydric hydroxy resin in which a portion of the alkylphenol nucleus is substituted with an ethylphenethyl group with epichlorohydrin.

JP 2017-66268 A

However, in the technique of Patent Document 1, no consideration has been given to reducing peeling at the interface of a lead frame such as a copper substrate, and the properties of the disclosed epoxy resin composition are also insufficient. Therefore, the problem to be solved by the present disclosure is a semiconductor encapsulating resin composition and a semiconductor encapsulating material that exhibit low hygroscopicity when cured and excellent adhesion to metal materials, and a semiconductor having the semiconductor encapsulating material It is to provide a device.

The present inventors have made intensive studies to solve the above-mentioned problems, and found that by using an epoxy resin having a specific chemical structure, semiconductor encapsulation that exhibits low hygroscopicity and excellent adhesion to metal materials. The present inventors have found a resin composition for this purpose, and have completed the present invention.
That is, the present disclosure is a glycidyl polyhydric hydroxy resin (P) using an aromatic compound (i) containing an aromatic ring having a phenolic hydroxyl group and two or more hydrocarbon groups and an aromatic vinyl compound (ii) as reaction raw materials. A resin composition for semiconductor encapsulation containing an epoxy resin (A) which is an etherified product, a curing agent (B), and an inorganic filler (C).

According to the present disclosure, there is provided a resin composition for semiconductor encapsulation that exhibits low hygroscopicity when cured and excellent adhesion to metal materials.

Hereinafter, embodiments of the present disclosure (hereinafter referred to as "present embodiments") will be described in detail. can be implemented.
[Resin composition for semiconductor encapsulation]
The present disclosure comprises an epoxy resin (A) (hereinafter referred to as (A) component), a curing agent (B) (hereinafter referred to as (B) component), and an inorganic filler (C) (hereinafter referred to as (C) component). It is a resin composition for semiconductor encapsulation containing. The epoxy resin (A) comprises an aromatic compound (i) containing an aromatic ring having a phenolic hydroxyl group and two or more hydrocarbon groups (hereinafter also simply referred to as aromatic compound (i)) and an aromatic vinyl It is a glycidyl etherified product of polyhydric hydroxy resin (P) using compound (ii) as a reaction raw material.
As a result, the resin composition for semiconductor encapsulation of the present embodiment as a whole can exhibit the effect of achieving both low hygroscopicity during curing and excellent adhesion to metal materials.
The term "reaction raw material" as used herein refers to a compound that partially constitutes the chemical structure of the target compound and is used to obtain the target compound by a chemical reaction such as compounding or decomposition. , substances that act as auxiliaries for chemical reactions are excluded. In this specification, the term "reaction raw material" particularly refers to a monomer compound that serves as a precursor for obtaining the target prepolymer (polyhydric hydroxy resin (P) or glycidyl etherate) by polymerization reaction.

Each component (the epoxy resin (A), the curing agent (B), the inorganic filler (C) and the optional component (D)) constituting the resin composition for semiconductor encapsulation of the present embodiment will be described below.
"Epoxy resin (A)"
The epoxy resin (A) in the present embodiment is a polyhydric hydroxy resin containing an aromatic compound (i) containing an aromatic ring having a phenolic hydroxyl group and two or more hydrocarbon groups and an aromatic vinyl compound (ii) as reaction raw materials. It is a glycidyl etherate of (P). In addition, the aromatic vinyl compound (ii) in the present embodiment essentially contains the aromatic divinyl compound (ii-1), and may further contain the aromatic monovinyl compound (ii-2) if necessary.
In other words, the epoxy resin (A), which is a glycidyl etherified product in the present embodiment, comprises an aromatic compound (i) unit containing an aromatic ring having a phenolic hydroxyl group and two or more hydrocarbon groups, and an aromatic divinyl compound (ii -1) units are chemically bonded via the aromatic ring, and optionally the aromatic monovinyl compound (ii-2) unit is chemically bonded to the aromatic ring in the aromatic compound (i) unit and has a chemical structure in which the phenolic hydroxyl group is substituted with a glycidyl ether group.
More specifically, the epoxy resin (A) of the present embodiment is formed at a specific position of the aromatic ring in the aromatic compound (i) by an _ArSE reaction with a cationoid agent formed from the aromatic vinyl compound (ii). It is an introduced glycidyl etherate. Therefore, a glycidyl etherate having a uniform chemical structure or chain length can be easily obtained, and as a result, it can exhibit high fluidity, excellent adhesion to metal materials, or low hygroscopicity.
As used herein, the term "compound unit" refers to a repeating unit of a chemical structure formed during reaction or polymerization.

The epoxy equivalent of the epoxy resin (A) of the present embodiment is preferably 150-400 g/eq, more preferably 200-350 g/eq, and even more preferably 240-330 g/eq. When the epoxy equivalent of the epoxy resin (A) is within the above range, the generation of active hydroxyl groups generated when the epoxy resin (A) reacts with the curing agent is suppressed, and the resulting cured product has heat resistance and low moisture absorption. It is preferable because it is excellent in properties and reflow resistance resulting therefrom. The measurement of the epoxy equivalent in this specification is measured based on JIS K 7236 as described in the column of Examples.

The epoxy resin (A) of the present embodiment preferably has a melt viscosity at 150° C. of 0.01 to 5 dPa·s, more preferably 0.01 to 2 dPa·s, as measured by an ICI viscometer. , 0.01 to 0.6 dPa·s. When the melt viscosity of the epoxy resin (A) is within the above range, the viscosity is low and the fluidity is excellent, so that the moldability of the obtained cured product is preferable. The melt viscosity in this specification is measured by an ICI viscometer in accordance with ASTM D4287, as described in the Examples section.

Since the epoxy resin (A) of the present embodiment has low viscosity and excellent fluidity, the number average molecular weight (Mn) is preferably in the range of 200 to 1800, more preferably in the range of 250 to 1500. is more preferable, and a range of 430 to 1,500 is even more preferable. Also, the weight average molecular weight (Mw) is preferably in the range of 250-2000, more preferably in the range of 300-1800. In another form, it is preferably in the range of 800-2000. The molecular weight distribution (Mw/Mn), which is the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn), is preferably in the range of 1 to 1.6. In the present specification, the molecular weight of the epoxy resin (A) is measured using gel permeation chromatography (hereinafter abbreviated as "GPC") under the measurement conditions described in Examples below.
Polyvalent hydroxy resin (P ) is easily obtained, the epoxy resin (A), which is a glycidyl etherified product thereof, also has a narrower molecular weight distribution and a lower viscosity than conventional phenol resins. By using it, high fluidity and excellent moldability can be exhibited.

In the resin composition for semiconductor encapsulation of the present embodiment, the content of component (A) is 5 to 40% by mass with respect to 100% by mass of the total amount of components (A), (B) and (C). is preferably 8 to 30% by mass, and more preferably 10 to 25% by mass. By setting the content of component (A) to 10% by mass or more, good curability is exhibited. On the other hand, when the content of component (A) is 25% by mass or less, low hygroscopicity is exhibited.

Hereinafter, after explaining the constituent components of the reaction raw materials (aromatic compound (i) and aromatic vinyl compound (ii)) of the polyhydroxy resin (P), which is the precursor of the epoxy resin (A), the polyhydroxy resin A preferred form of (P) and a glycidyl etherate of the polyhydric hydroxy resin (P) will be described.
<Polyvalent hydroxy resin (P)>
The polyhydric hydroxy resin (P) in the present embodiment uses an aromatic compound (i) containing an aromatic ring having a phenolic hydroxyl group and two or more hydrocarbon groups and an aromatic vinyl compound (ii) as reaction raw materials. In addition, the aromatic vinyl compound (ii) in the present embodiment essentially contains the aromatic divinyl compound (ii-1), and may further contain the aromatic monovinyl compound (ii-2) if necessary. In other words, the polyhydric hydroxy resin (P) in the present embodiment comprises an aromatic compound (i) unit containing an aromatic ring having a phenolic hydroxyl group and two or more hydrocarbon groups, and an aromatic divinyl compound (ii-1) units are chemically bonded, and if necessary, the aromatic monovinyl compound (ii-2) unit is chemically bonded to the aromatic ring in the aromatic compound (i) unit.
In the present embodiment, since the aromatic compound (i), which is a phenolic compound having two or more hydrocarbon groups in the aromatic ring, is used as a reaction raw material, the aromatic divinyl compound (ii-1) described later and the reaction site are Since it becomes easier to control, it becomes easier to obtain a polyvalent hydroxy resin (P) with a uniform chemical structure or chain length, and as a result, a resin composition for semiconductor encapsulation having low hygroscopicity and excellent adhesion to metal materials. can provide things.

- Aromatic compound (i) -
The aromatic compound (i) in this embodiment has a phenolic hydroxyl group and two or more hydrocarbon groups (R ^a ) in an aromatic ring. Therefore, aromatic compound (i) can be a phenolic compound. Moreover, the aromatic ring forming the central structure of the aromatic compound (i) may be monocyclic or condensed polycyclic, and further includes an aromatic hydrocarbon ring. Examples of aromatic hydrocarbon rings include, but are not limited to, benzene, naphthalene, anthracene, phenanthrene, and phenalene rings. The aromatic ring is preferably monocyclic from the viewpoint of the melt viscosity of the resin.
In addition, the aromatic compound (i) is composed of a plurality of aromatic compounds via the aromatic divinyl compound (ii-1) unit as a linking group bonded to a predetermined site in the aromatic ring of the aromatic compound (i). Compound (i) can form a linkable aromatic compound (i) unit.

In the aromatic compound (i) of the present embodiment, the two or more hydrocarbon groups (R ^a ) possessed by at least one of the aromatic rings in the aromatic compound (i) are hydrocarbons having 1 to 6 carbon atoms groups. Examples of the hydrocarbon group (R ^a ) include monovalent aliphatic hydrocarbon groups having 1 to 6 carbon atoms. The aliphatic hydrocarbon group may be either linear or branched. The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group in order to prevent addition reaction with other compounds. Examples of saturated aliphatic hydrocarbon groups include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group and hexyl group. The lower the molecular weight of the hydrocarbon group, the more remarkable the effect of the present invention (excellent adhesion when cured). Moreover, the higher the molecular weight of the hydrocarbon group (R ^a ), the more remarkable the effect of the present invention (low hygroscopicity when cured).

The number of hydrocarbon groups (R ^a ) possessed by the aromatic ring in the aromatic compound (i) of the present embodiment (that is, the number of substitutions) is 2 or more. When the number of the hydrocarbon groups (R ^a ) is 2 or more, excellent adhesion to metal materials and low hygroscopicity can be exhibited.
The upper limit of the number of hydrocarbon groups (R ^a ) is an unsubstituted state (other than substitution with a hydrogen atom) from the viewpoint that the aromatic ring has a phenolic hydroxyl group and two bonds are used for polymerization. Any number obtained by subtracting 3 from the number of substitutable ring-constituting atoms in the aromatic ring may be used. For example, when the aromatic ring is a benzene ring, the number of hydrocarbon groups is 3 or less.
Further, by setting the number of hydrocarbon groups (R ^a ) of the aromatic ring in the aromatic compound (i) to 2 or more, it becomes easier to control the reaction site with the aromatic divinyl compound (ii-1) described later. Therefore, a polyhydroxy resin (P) having a uniform chemical structure or chain length can be easily obtained, and as a result, excellent melt viscosity, or excellent adhesion to metal materials and low hygroscopicity can be easily exhibited.
In addition, by using the aromatic compound (i), which is a phenolic compound having two or more substituents, it is possible to control the reaction site, so that a polyvalent hydroxy resin (A) having a uniform chemical structure or chain length can be obtained. easier. Therefore, it is considered that the distance between cross-linking points between the so-called linking group and the acting aromatic divinyl compound (ii-1) is optimized, and the thermal elastic modulus can be reduced.

As an example, the aromatic compound (i) in the present embodiment is an aromatic hydrocarbon ring (e.g., benzene ring, naphthalene ring) having a phenolic hydroxyl group and two or more hydrocarbon groups (R ^a ). Preferred forms of compound (i) are described.
In the present embodiment, among the carbon atoms in the aromatic hydrocarbon ring constituting the aromatic compound (i), one or more carbon atoms having the largest HOMO electron density (Hückel coefficient) are unsubstituted (or hydrogen atom) is preferred.
This makes it easier to control the _ArSE reaction and molecular design by the cationoid agent formed from the aromatic divinyl compound (ii-1) described below. More specifically, among the carbon atoms in the aromatic hydrocarbon ring constituting the aromatic compound (i), the carbon atom having the highest HOMO electron density (Hückel coefficient) is unsubstituted (or hydrogen atom ), the carbocation of the aromatic divinyl compound (ii-1), which is a cationoid agent, readily reacts with the carbon atom having the highest HOMO electron density. Therefore, by controlling the number and positions of the hydrocarbon groups (R ^a ) or the number and positions of the phenolic hydroxyl groups, it is possible to adjust the bonding sites or the number of bonds with the aromatic divinyl compound. Therefore, it is assumed that the chemical structure or molecular chain length of the resulting polyhydroxy resin (P) can be easily designed.
For example, when the aromatic compound (i) is a phenol skeleton having one benzene ring and one hydroxyl group, at least one of the 2-, 4- and 6-positions is substituted with a hydrogen atom. is preferred. As a result, the aromatic divinyl compound (ii-1) to be described later is formed with respect to at least one carbon atom among the ortho-position and para-position of the phenol nucleus with high electron density, 2-position, 4-position and 6-position. more susceptible to attack by cationoid agents.
In particular, the cationoid agent formed from the aromatic divinyl compound (ii-1) is preferably added to the 4-position of the phenol nucleus. As a result, since the benzene ring of the phenol nucleus is substituted at the p-position, a crosslinked structure that facilitates stress relaxation is formed due to the symmetrical structure, and adhesion and Charpy impact strength are considered to work favorably. Such a mechanism of action is considered to work similarly whether the polyhydroxy resin (A) is used as an epoxy resin or a phenol resin (curing agent).
Similarly, the unsubstituted naphthalene ring has the highest HOMO electron densities at the 1, 4, 5 and 8 carbon atoms. The position of the carbon atom with the highest HOMO electron density changes depending on the bonding position of the phenolic hydroxyl group. The carbocation generated from the group divinyl compound (ii-1) is likely to react. Therefore, for example, if the hydrogen atom of the CH group at the 1-position is substituted with a hydrocarbon group (R ^a ), the carbon atom at the 3-position is likely to undergo an _ArSE reaction, so the chemical reaction of the resulting polyhydroxy resin (P) You can control the structure, etc. Furthermore, for example, when the aromatic compound (i) has a 2,7-hydroxynaphthalene skeleton, the 1-, 3-, 6- and 8-positions are produced from the aromatic divinyl compound (ii-1) The carbocation that is used is likely to react. Therefore, for example, when a hydrocarbon group (R ^a ) is bonded to three carbon atoms at positions 1, 3, and 6, the carbon atom at position 8 is likely to react with _ArSE .

From the above, it is considered that having two or more hydrocarbon groups (R ^a ) makes it easier to control the resin structure.

Specific examples of the aromatic compound (i) of the present embodiment include xylenol (2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol), trimethylphenol (2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2,4,5-trimethylphenol, 2,4, 6-trimethylphenol, 3,4,5-trimethylphenol) and dialkylphenol compounds such as compounds composed of derivatives thereof, and 1-naphthol, 2-naphthol, 1,2-dihydroxynaphthalene, 1,3-dihydroxy Naphthalene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene, in which the hydrogen atoms of two or more CH groups in the compound are substituted with the above hydrocarbon group (Ra), so-called dialkylhydroxynaphthalene compounds. is not limited to
The aromatic compound (i) in this embodiment may be used alone or in combination of two or more. However, dialkylphenol compounds are preferred from the viewpoint of low viscosity when melted.

（上記一般式（ｉ）中、Ｒ^ｉは炭素原子数１～６の炭化水素基を表し、炭素原子数１～３の炭化水素基であることが好ましく、ｐ^ｉは、２又は３を表す。複数存在するＲ^ｉは同一であっても、あるいは異なっていてもよい。） The aromatic compound (i), which is the reaction raw material of the polyhydric hydroxy resin (P) in the present embodiment, can be represented, for example, by the following general formula (i).

(In general formula (i) above, R ⁱ represents a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrocarbon group having 1 to 3 carbon atoms, and p ⁱ represents 2 or 3. (R ⁱ present in plurality may be the same or different.)

In general formula (i) above, the hydrocarbon group having 1 to 6 carbon atoms is the same as defined above for the hydrocarbon group (R ^a ).

- Aromatic vinyl compound (ii) -
The aromatic vinyl compound (ii) in this embodiment essentially contains the aromatic divinyl compound (ii-1). The aromatic vinyl compound (ii) preferably contains an aromatic divinyl compound (ii-1) and an aromatic monovinyl compound (ii-2).
The proportion of the aromatic divinyl compound (ii-1) in the aromatic vinyl compound is preferably 45% by mass or more and 100% by mass or less with respect to the total amount of the aromatic vinyl compound, and 50 to 92% by mass. A range is more preferred.
Also, the aromatic divinyl compound (ii-1) forms an aromatic divinyl compound (ii-1) unit as a linking group that links the aromatic compounds (i) to each other via a predetermined site. Furthermore, the aromatic monovinyl compound (ii-2) is a group optionally substituting a hydrogen atom of the ring structure in the aromatic compound (i).

-- Aromatic divinyl compound (ii-1) --
The aromatic divinyl compound (ii-1) in the present embodiment can be used without particular limitation as long as it has two vinyl groups as substituents on the aromatic ring and can react with the aromatic compound (i). Examples of the aromatic divinyl compound (ii-1) include divinylbenzene, divinylbiphenyl, divinylnaphthalene, and various compounds in which the aromatic ring thereof is substituted with one or more alkyl groups, alkoxy groups, halogen atoms, etc. is mentioned. The alkyl group or alkoxy group may be either linear or branched. Among them, the number of carbon atoms in the alkyl group or alkoxy group is preferably 1 to 4 from the viewpoint of exhibiting excellent melt viscosity, excellent adhesion to metal materials, and low hygroscopicity. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group and isobutyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and the like.
As described above, the aromatic divinyl compound (ii-1) is introduced into a specific position of the ring in the aromatic compound (i) by an _ArSE reaction with a cationoid agent formed from the aromatic divinyl compound (ii-1). I can. Therefore, it becomes easy to obtain a polyvalent hydroxy resin (P) with a uniform chemical structure or chain length, and as a result, for semiconductor encapsulation that exhibits excellent melt viscosity, or excellent adhesion to metal materials and low hygroscopicity. A resin composition may be provided.

Specific examples of the aromatic divinyl compound (ii-1) of the present embodiment include 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 2,5-dimethyl-1, 4-divinylbenzene, 2,5-diethyl-1,4-divinylbenzene, cis,cis,β,β'-diethoxy-mm-divinylbenzene, 1,4-divinyl-2,5-dibutylbenzene, 1 ,4-divinyl-2,5-dihexylbenzene, 1,4-divinyl-2,5-dimethoxybenzene, divinylbenzenes such as compounds composed of derivatives thereof, 1,3-divinylnaphthalene, 1,4- Divinylnaphthalene, 1,5-divinylnaphthalene, 1,6-divinylnaphthalene, 1,7-divinylnaphthalene, 2,3-divinylnaphthalene, 2,6-divinylnaphthalene, 2,7-divinylnaphthalene, 3,4-divinyl Divinylnaphthalenes such as naphthalene, 1,8-divinylnaphthalene, 1,5-dimethoxy-4,8-divinylnaphthalene, and compounds composed of derivatives thereof, but are not limited thereto.
The aromatic divinyl compound (ii-1) in this embodiment may be used alone or in combination of two or more.
In particular, from the viewpoint of fluidity, the aromatic divinyl compound (ii-1) is preferably divinylbenzene or a compound having a substituent on its aromatic ring, more preferably divinylbenzene. Further, in the present embodiment, the substitution position of the vinyl group of divinylbenzene is not particularly limited, but it is preferable that the main component is the meta-isomer. The content of the meta-body in divinylbenzene is preferably 40% by mass or more, more preferably 50% by mass or more, relative to the total amount of divinylbenzene.

（上記一般式（ｉｉ－１）中、Ｒ^ｉｉは、ハロゲン原子又は炭素原子数１～４のアルキル基若しくはアルコキシ基を表し、炭素原子数１～３のアルキル基であることが好ましく、ｐ^ｉｉは０～４の整数を表し、０～１であることが好ましい。なお、ｐ^ｉｉが２以上の整数の場合、複数存在するＲ^ｉｉは互いに同一であっても、あるいは異なっていてもよい。） The aromatic divinyl compound (ii-1), which is a reaction raw material of the polyhydric hydroxy resin (P) of the present disclosure, can be represented by the following formula (ii-1).

(In general formula (ii-1) above, R ⁱⁱ represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group, preferably an alkyl group having 1 to 3 carbon atoms, and p ⁱⁱ represents an integer of 0 to 4, preferably 0 to 1. When p ⁱⁱ is an integer of 2 or more, a plurality of R ⁱⁱ may be the same or different. )

Examples of the alkyl group or alkoxy group having 1 to 4 carbon atoms in the general formula (ii-1) are the same as the above alkyl group or alkoxy group.

-- aromatic monovinyl compound (ii-2) --
Polyhydric hydroxy resin (P) in the present embodiment may use aromatic compound (i), aromatic divinyl compound (ii-1), and other compounds as reaction raw materials. Examples of the other compounds include aromatic monovinyl compounds (ii-2). That is, the polyhydric hydroxy resin (P) in the embodiment can use the aromatic compound (i), the aromatic divinyl compound (ii-1), and the aromatic monovinyl compound (ii-2) as reaction raw materials. preferable. The polyhydric hydroxy resin (P) of the present embodiment uses an aromatic monovinyl compound (ii-2) in addition to the aromatic compound (i) and the aromatic divinyl compound (ii-1) as reaction raw materials. Therefore, when the glycidyl etherified product of the polyhydric hydroxy resin (P) finally obtained is used as a semiconductor encapsulating material, the resin has excellent fluidity and the cured product thereof has a low thermal elastic modulus. preferable. In addition, the use of the aromatic monovinyl compound (ii-2) improves aromaticity and is useful for improving moisture resistance.
In addition, since the aromatic monovinyl compound (ii-2) also produces a carbocation similarly to the aromatic divinyl compound (ii-1), the number of carbon atoms in the aromatic hydrocarbon ring constituting the aromatic compound (i) Among them, the carbon atom having the highest HOMO electron density (Hückel coefficient) is likely to react.

The aromatic monovinyl compound (ii-2) in the present embodiment is, for example, vinylbenzene, vinylbiphenyl, vinylnaphthalene, and one or more substituents such as an alkyl group, an alkoxy group, or a halogen atom on the aromatic ring thereof. Examples include various substituted compounds. The alkyl group or alkoxy group may be linear or branched, and may have an unsaturated bond in its structure. Above all, when low hygroscopicity is emphasized, the alkyl group or the alkoxy group is preferably a group having 1 to 4 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group and isobutyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. The halogen atom includes a fluorine atom, a chlorine atom, a bromine atom, and the like.

Specific examples of the aromatic monovinyl compound (ii-2) of the present embodiment include styrene, fluorostyrene, vinyl benzyl chloride, alkylvinylbenzene (o-, m-, p-methylstyrene, o-, m- , p-ethylvinylbenzene), o-, m-, p-(chloromethyl)styrene and vinylbenzenes such as compounds composed of derivatives thereof; 4-vinylbiphenyl, 4-vinyl-p-terphenyl and their Biphenyl compounds such as compounds comprising derivatives; and vinylnaphthalenes such as 1-vinylnaphthalene, 2-vinylnaphthalene and compounds comprising derivatives thereof, but are not limited thereto.
In particular, alkylvinylbenzene and a compound having a substituent on its aromatic ring are preferred, and ethylvinylbenzene is more preferred, from the viewpoint of lowering the thermal elastic modulus.
Further, the substitution positions of the vinyl group and the ethyl group of the ethylvinylbenzene are not particularly limited, but it is preferable that the meta-body is the main component, and the content of the meta-body in the ethylvinylbenzene is the total amount of the ethylvinylbenzene. It is more preferably 40% by mass or more, and even more preferably 50% by mass or more.

（上記一般式（ｉｉ－２）中、Ｒ^ｉｉは、ハロゲン原子又は炭素原子数１～４のアルキル基若しくはアルコキシ基を表し、炭素原子数１～３のアルキル基であることが好ましく、ｐ^ｉｉは０～５の整数を表し、０～１であることが好ましい。なお、ｐ^ｉｉが２以上の整数の場合、複数存在するＲ^ｉｉは互いに同一であっても、あるいは異なっていてもよい。） The aromatic monovinyl compound (ii-2) that can be used as a reaction raw material for the polyhydric hydroxy resin (P) of the present disclosure can be represented by the following general formula (ii-2).

(In general formula (ii-2) above, R ⁱⁱ represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group, preferably an alkyl group having 1 to 3 carbon atoms, and p ⁱⁱ represents an integer of 0 to 5, preferably 0 to 1. When p ⁱⁱ is an integer of 2 or more, a plurality of R ⁱⁱ may be the same or different. )

In general formula (ii) above, the alkyl group or alkoxy group having 1 to 4 carbon atoms is the same as the above alkyl group or alkoxy group.

When the aromatic monovinyl compound (ii-2) is used as a reaction raw material for the polyhydric hydroxy resin (P) in the present embodiment, the aromatic monovinyl compound of the aromatic divinyl compound (ii-1) in the reaction raw material The mass ratio ((ii-1)/(ii-2)) to compound (ii-2) is preferably 30/70 to 99/1, more preferably 50/50 to 99/1. , more preferably 50/50 to 98/2. When the mass ratio of the aromatic divinyl compound (ii-1) and the aromatic monovinyl compound (ii-2) is within the above range, the resulting polyvalent hydroxy resin (P) can be easily handled and the polyvalent It is preferable because the physical properties of moldability and curability can be balanced during the production of the epoxy resin obtained from the hydroxy resin (P).

Hereinafter, preferred aspects of the polyhydric hydroxy resin (P) of the present disclosure will be described by taking as an example the case where each aromatic ring is a benzene ring. The following chemical structural formulas are provided to exemplify the present disclosure, and the scope of the present disclosure is not limited to the following chemical structural formulas.

（上記一般式（Ｉ）及び（ＩＩ）中、Ｒ^１、Ｒ^２、及びＲ^３は、各々独立して、炭素原子数１～６の炭化水素基を表し、
Ｒ^４及びＲ^５は、各々独立して、水素原子又は炭素原子数１～３のアルキル基を表し、
Ｒ^６は、一般式（ａ）

（一般式（ａ）中、Ｒ^７は水素原子又は炭素原子数１～６の炭化水素基を表す。）
で表される置換基を表し、
Ｒ^８は、水素原子又は有機基を表し、
ｐは、多価ヒドロキシ樹脂（Ｐ）全体における、フェノール環１つ当たりのＲ^６の置換数の平均値であり、０～１の数を表す。尚、上記一般式（Ｉ）及び（ＩＩ）中の＊は、他の原子との結合を表す。）
上記一般式（Ｉ）及び（ＩＩ）中、炭素原子数１～６の炭化水素基は、上述した炭化水素基（Ｒ^ａ）として定義したものと同様であることが好ましい。また、上記一般式（Ｉ）及び（ＩＩ）中、Ｒ^１、Ｒ^２、及びＲ^３は、各々独立して、炭素原子数１～４のアルキル基であることが好ましく、Ｒ^４及びＲ^５は、各々独立して、水素原子又はメチル基であることが好ましい。
上記一般式（ａ）中、Ｒ^７は、炭素原子数１～４のアルキル基であることが好ましい。
上記一般式（Ｉ）及び（ＩＩ）中の有機基は、一価の有機基であり、炭素原子数１～６のアルキル基、炭素原子数１～６のアルケニル基又は炭素原子数１～６のアルコキシ基であることが好ましい。また、当該アルキル基、アルケニル基、アルコキシ基中の１個又は隣接しない２個以上の－ＣＨ_２－は、－Ｏ－、－ＣＯＯ－又は－ＯＣＯ－で置換されてもよい。 The polyhydric hydroxy resin (P) in this embodiment preferably has a partial structure represented by the following general formulas (I) and/or (II).

(In general formulas (I) and (II) above, R ¹ , R ² and R ³ each independently represent a hydrocarbon group having 1 to 6 carbon atoms,
R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ⁶ has the general formula (a)

(In general formula (a), R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)
represents a substituent represented by
R ⁸ represents a hydrogen atom or an organic group,
p is the average number of substitutions of R ⁶ per phenol ring in the entire polyhydric hydroxy resin (P), and represents a number from 0 to 1; Note that * in the above general formulas (I) and (II) represents a bond with another atom. )
In general formulas (I) and (II) above, the hydrocarbon group having 1 to 6 carbon atoms is preferably the same as defined above for the hydrocarbon group (R ^a ). In general formulas (I) and (II), R ¹ , R ² and R ³ are each independently preferably an alkyl group having 1 to 4 carbon atoms, and R ⁴ and R ⁵ are each independently preferably a hydrogen atom or a methyl group.
In general formula (a) above, R ⁷ is preferably an alkyl group having 1 to 4 carbon atoms.
The organic group in the general formulas (I) and (II) is a monovalent organic group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms or an alkenyl group having 1 to 6 carbon atoms. is preferably an alkoxy group of In addition, one or two or more non-adjacent -CH ₂ - in the alkyl group, alkenyl group or alkoxy group may be substituted with -O-, -COO- or -OCO-.

（上記一般式（ＩＩＩ）及び（ＩＶ）中、Ｒ^１、Ｒ^２、及びＲ^３は、各々独立して、炭素原子数１～６の炭化水素基を表し、
Ｒ^４及びＲ^５は、各々独立して、水素原子又は炭素原子数１～３のアルキル基を表し、
Ｒ^６は、一般式（ａ）

（一般式（ａ）中、Ｒ^７は水素原子又は炭素原子数１～６の炭化水素基を表す。）
で表される置換基を表し、
Ｒ^８は、水素原子又は有機基を表し、
ｎは、０～２０の整数を表し、
ｍは、０～２０の整数を表し、
ｐは、フェノール環１つ当たりの平均のＲ^６の置換数であり、０～１の数であることが好ましい。）
一般式（ＩＩＩ）及び（ＩＶ）中のＲ^１～Ｒ^８は、上記一般式（Ｉ）及び（ＩＩ）中のＲ^１～Ｒ^８と同様であるためここでは省略する。） The polyhydric hydroxy resin (P) in this embodiment is preferably represented by the following general formulas (III) and/or (IV).

(In general formulas (III) and (IV) above, R ¹ , R ² and R ³ each independently represent a hydrocarbon group having 1 to 6 carbon atoms,
R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ⁶ has the general formula (a)

(In general formula (a), R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)
represents a substituent represented by
R ⁸ represents a hydrogen atom or an organic group,
n represents an integer from 0 to 20,
m represents an integer from 0 to 20,
p is the average number of R ⁶ substitutions per phenol ring and is preferably a number between 0 and 1; )
R ¹ to R ⁸ in general formulas (III) and (IV) are the same as R ¹ to R ⁸ in general formulas (I) and (II) above, and are omitted here. )

The hydroxyl equivalent weight of the polyhydric hydroxy resin (P) of the present embodiment is preferably 200-500 g/eq, more preferably 200-400 g/eq.
In addition, the measurement of the hydroxyl group equivalent of the polyhydric hydroxy resin (P) in this specification is a value measured by a method based on the neutralization titration method defined in JIS K 0070 (1992).
The softening point of the polyhydric hydroxy resin (P) of the present embodiment is preferably 40 to 150°C, preferably 50 to 120°C. The softening point here is measured based on JIS K 7234 (ring and ball method) under the measurement conditions described in the Examples section below.
Since the polyhydric hydroxy resin (P) of the present embodiment has low viscosity and excellent fluidity, the number average molecular weight (Mn) is preferably in the range of 200 to 1,500, and in the range of 220 to 1,000. It is more preferable to have Further, the weight average molecular weight (Mw) of the polyhydric hydroxy resin (P) is preferably in the range of 250 to 2000, more preferably in the range of 300 to 1500, and more preferably in the range of 400 to 1200. More preferred. The molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably in the range of 1.1 to 3, preferably 1.1 to 1.8. A range is more preferred.
Since the polyhydric hydroxy resin (P) of the present embodiment has repeating units of the aromatic compound (i), which is a phenolic compound having two or more hydrocarbon groups (R ^a ) in the aromatic ring, the aromatic divinyl It is easy to control the binding site with the compound (ii-1) unit. On the other hand, in a phenolic resin having a repeating unit of a phenolic compound having one or less hydrocarbon groups in the aromatic ring, since there are many bonding sites with the aromatic divinyl compound unit for the phenolic compound, the resulting phenolic resin There is also a large number of chain lengths or chemical structures, and the molecular weight distribution tends to be broad. Therefore, the polyhydric hydroxy resin (P) of the present disclosure can exhibit homogeneous properties with more uniform molecular weights than conventional phenolic resins.

<Glycidyl etherate>
The epoxy resin (A) in this embodiment is a compound obtained by substituting one or more hydroxyl groups in the polyhydroxy resin (P) with a glycidyl group. In other words, the epoxy resin (A), which is a glycidyl ether compound in the present embodiment, comprises an aromatic compound (A) unit containing an aromatic ring having a phenolic hydroxyl group and two or more hydrocarbon groups, and an aromatic divinyl compound (B1 ) unit is chemically bonded, and optionally the aromatic monovinyl compound (B2) unit is chemically bonded to the aromatic ring in the aromatic compound (A) unit, and the phenolic hydroxyl group is glycidyl It has a chemical structure substituted with an ether group. As will be explained later in the column of the method for producing a glycidyl ether compound, a glycidyl ether compound can be produced by reacting the polyhydric hydroxy resin (P) with epihalohydrin. As described above, the aromatic divinyl compound (ii-1) is introduced into a specific position of the ring in the aromatic compound (i) by an _ArSE reaction with a cationoid agent formed from the aromatic divinyl compound (ii-1). I can. Therefore, the polyhydroxy resin (P) having a uniform chemical structure or chain length is likely to be obtained, and the glycidyl etherate thereof is also likely to have a uniform chemical structure or chain length. As a result, the elastic modulus of the entire glycidyl etherified product during heating can be easily controlled, and the internal stress during the curing reaction is alleviated, so that a resin composition for semiconductor encapsulation having low hygroscopicity can be provided. .

（上記一般式（Ｖ）及び（ＶＩ）中、Ｒ^１、Ｒ^２、及びＲ^３は、各々独立して、炭素原子数１～６の炭化水素基を表し、
Ｒ^４及びＲ^５は、各々独立して、水素原子又は炭素原子数１～３のアルキル基を表し、
Ｒ^６は、一般式（ａ）

（一般式（ａ）中、Ｒ^７は水素原子又は炭素原子数１～６の炭化水素基を表す。）
で表される置換基を表し、
Ｒ^８は、水素原子又は有機基を表し、
ｐは、エポキシ樹脂（Ａ）全体における、フェノール環１つ当たりのＲ^６の置換数の平均値であり、０～１の数であることがより好ましい。尚、上記一般式（Ｖ）及び（ＶＩ）中の＊は、他の原子との結合を表す。）
上記一般式（Ｖ）及び（ＶＩ）中、Ｒ^１～Ｒ^８は、上記一般式（Ｉ）及び（ＩＩ）中のＲ^１～Ｒ^８と同様であるためここでは省略する。 The epoxy resin (A) in this embodiment preferably has a partial structure represented by the following general formulas (V) and/or (VI).

(In general formulas (V) and (VI) above, R ¹ , R ² and R ³ each independently represent a hydrocarbon group having 1 to 6 carbon atoms,
R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ⁶ has the general formula (a)

(In general formula (a), R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)
represents a substituent represented by
R ⁸ represents a hydrogen atom or an organic group,
p is the average number of substitutions of R ⁶ per phenol ring in the entire epoxy resin (A), and is more preferably 0-1. Note that * in the general formulas (V) and (VI) represents a bond with another atom. )
R ¹ to R ⁸ in general formulas (V) and (VI) above are the same as R ¹ to R ⁸ in general formulas (I) and (II) above, and are omitted here.

（上記一般式（ＶＩＩ）及び（ＶＩＩＩ）中、Ｇはグリシジル基を表し、Ｒ^１、Ｒ^２、及びＲ^３は、各々独立して、炭素原子数１～６の炭化水素基を表し、
Ｒ^４及びＲ^５は、各々独立して、水素原子又は炭素原子数１～３のアルキル基を表し、
Ｒ^６は、一般式（ａ）

（一般式（ａ）中、Ｒ^７は水素原子又は炭素原子数１～６の炭化水素基を表す。）
で表される置換基を表し、
Ｒ^８は、水素原子又は有機基を表し、
ｎは、０～２０の整数を表し、
ｍは、０～２０の整数を表し、
ｐは、エポキシ樹脂（Ａ）全体における、フェノール環１つ当たりの平均のＲ^６の置換数であり、０～１の数であることがより好ましい。）を表す。
一般式（ＶＩＩ）及び（ＶＩＩＩ）中のＲ^１～Ｒ^８は、上記一般式（Ｉ）及び（ＩＩ）中のＲ^１～Ｒ^８と同様であるためここでは省略する。） The epoxy resin (A) in this embodiment is preferably represented by the following general formulas (VII) and/or (VIII).

(In general formulas (VII) and (VIII) above, G represents a glycidyl group, R ¹ , R ² and R ³ each independently represent a hydrocarbon group having 1 to 6 carbon atoms,
R ⁴ and R ⁵ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms,
R ⁶ has the general formula (a)

(In general formula (a), R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)
represents a substituent represented by
R ⁸ represents a hydrogen atom or an organic group,
n represents an integer from 0 to 20,
m represents an integer from 0 to 20,
p is the average number of R ⁶ substitutions per phenol ring in the entire epoxy resin (A), and is more preferably 0-1. ).
R ¹ to R ⁸ in general formulas (VII) and (VIII) are the same as R ¹ to R ⁸ in general formulas (I) and (II) above, and are omitted here. )

The steps from the production of the polyhydric hydroxy resin (P) to the production of the glycidyl etherate will be described in order below.
<Method for producing polyhydric hydroxy resin (P)>
A method for producing the polyhydric hydroxy resin (P) will be described below.
The method for producing the polyhydric hydroxy resin (P) in the present embodiment is not particularly limited. -1) (e.g., divinylbenzene) and, if necessary, other compounds such as the aromatic monovinyl compound (ii-2) (e.g., ethylvinylbenzene) are reacted in the presence of an acid catalyst to obtain a multi- hydroxy resin (P) can be produced.

The polyhydroxy resin (P) obtained by the method for producing the polyhydroxy resin (P) of the present embodiment is an aromatic divinyl compound (ii-1) or an aromatic monovinyl compound (ii-2) that can be further used. The hydroxyl equivalent and the like can be controlled according to the blending ratio.
The blending ratio of the aromatic compound (i) and the aromatic divinyl compound (ii-1) is determined by considering the physical property balance of moldability and curability during production of the resulting cured product. i) The molar ratio of the aromatic divinyl compound (ii-1) to 1 mol is preferably 0.1 to 1 mol, more preferably 0.1 to 0.8 mol. Further, when the aromatic monovinyl compound (ii-2) is used in combination, the aromatic divinyl compound (ii-1) and the aromatic monovinyl compound (ii) are -2) is preferably 0.1 to 1 mol, more preferably 0.1 to 0.8 mol.
The blending ratio of the aromatic compound (i), the aromatic divinyl compound (ii-1) and the aromatic monovinyl compound (ii-2) should be Considering the balance of physical properties, the number of moles of vinyl groups contained in the aromatic divinyl compound (ii-1) and the aromatic monovinyl compound (ii-2) is 0 with respect to 1 mole of the aromatic compound (i). 0.1 to 1 mol, preferably 0.1 to 0.95 mol.

In the present embodiment, the reaction of aromatic compound (i) with aromatic divinyl compound (ii-1) and/or aromatic monovinyl compound (ii-2) can be carried out in the presence of an acid catalyst. . The acid catalyst can be appropriately selected from well-known inorganic acids and organic acids. For example, mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as formic acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, p-toluenesulfonic acid hydrate, dimethylsulfuric acid and diethylsulfuric acid; and zinc chloride. , aluminum chloride, iron chloride, and boron trifluoride, or solid acids such as ion-exchange resins, activated clay, silica-alumina, and zeolite. The blending amount of the acid catalyst is preferably 0.01 to 50 parts by mass, more preferably 0.01 to 10 parts by mass, with respect to 100 parts by mass of the raw materials of the polyhydric hydroxy resin (P). and more preferably 0.1 to 5 parts by mass. Moreover, the above reaction is usually carried out at 10 to 250° C. for 1 to 20 hours.

Solvents that can be used in the above reaction include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, and ethyl cellosolve, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, dimethyl ether, diethyl ether, and diisopropyl. Ether, ethers such as tetrahydrofuran and dioxane, aromatic compounds such as benzene, toluene, chlorobenzene and dichlorobenzene, and the like.

As a specific method for carrying out the above reaction, all the raw materials are charged at once and reacted at a predetermined temperature as they are, or the aromatic compound (i) and the acid catalyst are charged and kept at a predetermined temperature. It is common to carry out the reaction while dropping the aromatic divinyl compound (ii-1) or other compound (eg, the aromatic monovinyl compound (ii-2)). At this time, the dropping time is usually 1 to 10 hours, preferably 5 hours or less. After the reaction, when a solvent is used, if necessary, the solvent and unreacted substances are distilled off to obtain the polyhydric hydroxy resin (P). It is possible to obtain the polyhydric hydroxy resin (P), which is the target product, by removing it.

<Glycidyl etherification>
The reaction between the polyhydric hydroxy resin (P) and epihalohydrin is carried out, for example, in the presence of a basic catalyst at a temperature of generally 20 to 150°C, preferably 30 to 80°C for 0.5 to 10 hours. is mentioned.

In this embodiment, the epihalohydrin includes epichlorohydrin, epibromohydrin, β-methylepichlorohydrin and the like. The amount of epihalohydrin to be added is used in excess with respect to the total 1 mol of hydroxyl groups possessed by the polyhydric hydroxy resin (P), and is usually 1.5 to 30 mol, preferably in the range of 2 to 15 mol. is.

Examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. Among them, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity, and specifically, sodium hydroxide, potassium hydroxide, and the like are more preferable. Moreover, these basic catalysts may be used in a solid state or in an aqueous solution state. The amount of the basic catalyst to be added is preferably in the range of 0.9 to 2 mol with respect to 1 mol of hydroxyl groups in the polyhydric hydroxy resin (P).

In this embodiment, the reaction of the polyhydric hydroxy resin (P) and epihalohydrin may be carried out in an organic solvent. Organic solvents to be used include, for example, ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol and tertiary butanol; Ethers such as cellosolves, tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethylsulfoxide and dimethylformamide. These organic solvents may be used alone, or two or more of them may be used in combination to adjust the polarity.

After completion of the reaction with the epihalohydrin, excess epihalohydrin is distilled off to obtain a crude product. If necessary, hydrolyzable halogen may be reduced by dissolving the obtained crude product again in an organic solvent, adding a basic catalyst, and reacting again. A salt produced by the reaction can be removed by filtration, washing with water, or the like. Moreover, when an organic solvent is used, only the resin solid content may be taken out by distillation, or it may be used as a solution as it is.

"Curing agent (B)"
The resin composition for semiconductor encapsulation of the present disclosure contains a curing agent (B). The curing agent (B) in the present embodiment can be used without particular limitation as long as it is a curing agent capable of undergoing a cross-linking reaction with the epoxy groups of the epoxy resin (A).
In the resin composition for semiconductor encapsulation of the present embodiment, the content of component (B) is 3 to 30% by mass with respect to 100% by mass of the total amount of components (A), (B) and (C). is preferred, more preferably 4 to 25% by mass, and still more preferably 5 to 20% by mass. By setting the content of the component (B) to 5% by mass or more, a good curability effect is exhibited. On the other hand, by setting the content of component (B) to 20% by mass or less, the effect of low hygroscopicity is exhibited.

The curing agent (B) of the present embodiment includes a phenol-based curing agent, an amine-based curing agent, an amide-based curing agent, an acid anhydride-based curing agent, an active ester-based resin, a cyanate ester-based resin, and a polyhydric hydroxy resin (P ) and the like. The curing agents may be used alone or in combination of two or more.

Examples of the phenol-based curing agent include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyloc resin), naphthol aralkyl resin, triphenyl roll methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (containing polyhydric phenolic hydroxyl group with phenol nucleus linked by bismethylene group) compounds), biphenyl-modified naphthol resins (polyhydric naphthol compounds with phenolic nuclei linked by bismethylene groups), aminotriazine-modified phenolic resins (polyphenolic hydroxyl-containing compounds with phenolic nuclei linked with melamine, benzoguanamine, etc.), alkoxy Polyphenolic hydroxyl group-containing compounds such as group-containing aromatic ring-modified novolak resins (polyphenolic hydroxyl group-containing compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde) can be mentioned. Among them, a phenol novolac tree or the like is more preferable from the viewpoint of moldability. These may be used alone or in combination of two or more.

Examples of the amine curing agent include diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine, and mensene. Aliphatic amines such as diamine (MDA), isophoronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N,-dimethylpiperazine, triethylenediamine; m-xylenediamine (XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol and aromatic amines such as Each of these may be used alone, or two or more of them may be used in combination.

Examples of the amide-based curing agent include dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, and the like. Each of these may be used alone, or two or more of them may be used in combination.

Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis trimellitate, glycerol tri trimellitate, maleic anhydride, tetrahydro phthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, and methylcyclohexenedicarboxylic anhydride. Each of these may be used alone, or two or more of them may be used in combination.

Examples of the active ester resin include an active ester resin containing a dicyclopentadiene-phenol addition structure, an active ester resin containing a naphthalene structure, an active ester resin that is an acetylated product of phenol novolak, and a benzoylated product of phenol novolak. Active ester resins and the like are preferable, and active ester resins containing a dicyclopentadiene-phenol addition structure and active ester resins containing a naphthalene structure are more preferable in that they are excellent in improving peel strength. Each of these may be used alone, or two or more of them may be used in combination.

Examples of the cyanate ester resin include bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol sulfide type cyanate ester resin, and phenylene ether type cyanate ester. Resin, naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxy naphthalene type cyanate ester resin, phenol novolac type cyanate ester resin, cresol novolac type cyanate ester resin, triphenylmethane type Cyanate ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolac type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol cocondensation Novolak-type cyanate ester resins, naphthol-cresol cocondensation novolac-type cyanate ester resins, aromatic hydrocarbon-formaldehyde resin-modified phenol resin-type cyanate ester resins, biphenyl-modified novolak-type cyanate ester resins, anthracene-type cyanate ester resins, and the like. Each of these may be used alone, or two or more of them may be used in combination.

In the resin composition for semiconductor encapsulation of the present embodiment, the blending amount of the curing agent (B) with respect to the blending amount of the epoxy resin (A) is, for example, the functional group equivalent ratio (active hydrogen atoms (e.g., phenol-based curing agent The ratio of hydroxyl group equivalent of (B))/(epoxy equivalent of epoxy resin (A)) is not particularly limited, but the epoxy resin ( 0.5 to 1.5 equivalents of active groups in the curing agent (B) with respect to a total of 1 equivalent of the epoxy groups of A) and other epoxy resins (F) that are used in combination as necessary. is preferred, and 0.8 to 1.2 is more preferred.

"Inorganic filler (C)"
The resin composition for semiconductor encapsulation of the present disclosure contains an inorganic filler (C). The inorganic filler (C)) in this embodiment can be used without any particular limitation.
In the resin composition for semiconductor encapsulation of the present embodiment, the content of component (C) is 40 to 95% by mass with respect to 100% by mass of the total amount of components (A), (B) and (C). , more preferably 50 to 92% by mass, and still more preferably 60 to 90% by mass. By setting the content of component (C) to 60% by mass or more, high dimensional stability and high flame retardancy are exhibited. On the other hand, by setting the content of the component (C) to 90% by mass or less, a high moldability effect is exhibited.
In the resin composition for semiconductor encapsulation of the present embodiment, the filling rate of the inorganic filler (C) in the resin composition for semiconductor encapsulation is preferably 50 to 92%, more preferably 60 to 90%. is more preferable.
Since the resin composition for semiconductor encapsulation of the present embodiment uses the epoxy resin (A), which has excellent fluidity, the component (C) can be filled in a relatively high amount.

Examples of the inorganic filler (C) of the present embodiment include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, oxide magnesium, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black and the like. Among these, it is preferable to use silica. At this time, as silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, and the like can be used. Among them, fused silica is preferable because it allows a larger amount of the inorganic filler (C) to be blended. Either crushed or spherical fused silica can be used, but spherical fused silica is mainly used in order to increase the blending amount of fused silica and to suppress the increase in melt viscosity of the curable composition. is preferred. Furthermore, in order to increase the compounding amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica. In addition, each of these may be used alone, or two or more of them may be used in combination.

In addition, the inorganic filler (C) may be surface-treated as necessary. At this time, the surface treatment agent that can be used is not particularly limited, but aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, organosilazane compounds, titanate-based cups. A ring agent or the like may be used. Specific examples of surface treatment agents include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldimethoxysilane, silazane and the like.

The amount of the inorganic filler (C) in the present embodiment is preferably 0.5 to 95 parts by mass with respect to 100 parts by mass of the total amount of the mixture of the epoxy resin (A) and the curing agent (B). . When the blending amount of the inorganic filler (C) is within the above range, excellent flame retardancy and insulation reliability are obtained, which is preferable.
Moreover, in addition to the inorganic filler (C), an organic filler can be blended as long as it does not impair the characteristics of the present disclosure. Examples of the organic filler include polyamide particles.

"Optional component (D)"
The resin composition for semiconductor encapsulation of the present embodiment includes, in addition to the essential components, the epoxy resin (A), the curing agent (B) and the inorganic filler (C), optional components within a range that does not impair the effects of the present disclosure. Component (D) may be blended.
The optional component (D) includes other resins (E) and additives. Examples of such additives include curing accelerators, flame retardants, silane coupling agents, release agents, pigments, colorants, emulsifiers, and the like.

<Other resin (E)>
The resin composition for semiconductor encapsulation in the present embodiment may contain other resin (E). Examples of the other resin (E) include epoxy resins (F) other than the epoxy resin (A), maleimide resins, bismaleimide resins, polymaleimide resins, polyphenylene ether resins, polyimide resins, benzoxazine resins, and triazine-containing resins. Cresol novolak resins, styrene-maleic anhydride resins, allyl group-containing resins such as diallyl bisphenol and triallyl isocyanurate, polyphosphate esters, phosphate ester-carbonate copolymers, and the like. Each of these may be used alone, or two or more of them may be used in combination.

Other epoxy resins (F) of the present embodiment are specifically 2,7-diglycidyloxynaphthalene, α-naphthol novolak type epoxy resin, β-naphthol novolak type epoxy resin, α-naphthol/β-naphthol. Polyglycidyl ether of cocondensed novolac, naphthol aralkyl type epoxy resin, naphthalene skeleton-containing epoxy resin such as 1,1-bis(2,7-diglycidyloxy-1-naphthyl)alkane; bisphenol A type epoxy resin, bisphenol F bisphenol type epoxy resins such as type epoxy resins; biphenyl type epoxy resins such as biphenyl type epoxy resins and tetramethylbiphenyl type epoxy resins; phenol novolak type epoxy resins, cresol novolak type epoxy resins, bisphenol A novolac type epoxy resins, phenolic compounds Epoxidized products of condensates of aromatic aldehydes with phenolic hydroxyl groups, novolak type epoxy resins such as biphenyl novolak type epoxy resins; triphenylmethane type epoxy resins; tetraphenylethane type epoxy resins; dicyclopentadiene-phenol addition reaction type epoxy resin; phenol aralkyl type epoxy resin; phosphorus atom-containing epoxy resin and the like.

When the other epoxy resin (F) is used, it is excellent in fluidity, and the effect of excellent adhesiveness and hygroscopicity to metal materials in the cured product is sufficiently exhibited. It is preferable to use the epoxy resin (A) in an amount of 50% by mass or more in the total epoxy components in the composition.

In addition, when other epoxy resins (F) are used, the compounding ratio of the resin composition for semiconductor encapsulation is such that the resin composition has excellent curability, and the cured product has excellent melt viscosity, adhesion to metal materials, and hygroscopicity. is obtained, the equivalent ratio (epoxy group/active hydrogen atom) of the epoxy groups in all the epoxy components in the resin composition for semiconductor encapsulation and the active hydrogen atoms in the curing agent (B) is 1/0 A ratio of 0.5 to 1/1.5 is preferable.

<Solvent>
The resin composition for semiconductor encapsulation of the present disclosure may be prepared without a solvent, or may contain a solvent. The solvent has a function of adjusting the viscosity of the resin composition for semiconductor encapsulation. Specific examples of the solvent include, but are not limited to, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ethyl acetate, butyl acetate, cellosolve acetate, and propylene glycol monomethyl. ester solvents such as ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol; toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene and 1,2,4-trimethylbenzene Examples include aromatic hydrocarbons, amide solvents such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

The blending amount of the solvent is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, based on the total mass of the resin composition for semiconductor encapsulation. It is preferable that the solvent content is 10% by mass or more because the handling property is excellent. On the other hand, it is preferable from the economical point of view that the solvent content is 90% by mass or less.

<Additive>
The resin composition for semiconductor encapsulation of the present disclosure may optionally contain various additives such as curing accelerators, flame retardants, silane coupling agents, release agents, pigments, colorants, and emulsifiers. can.

- Curing accelerator -
Examples of the curing accelerator include, but are not limited to, phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and urea-based curing accelerators. In addition, the said hardening accelerator may be used individually, or may be used in combination of 2 or more type.

Examples of the phosphorus curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, tripparatolylphosphine, diphenylcyclohexylphosphine and tricyclohexylphosphine; organic phosphine compounds such as trimethylphosphite and triethylphosphite; ethyltriphenyl phosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, Examples include phosphonium salts such as butylphenylphosphonium dicyanamide and tetrabutylphosphonium decanoate.

Examples of the amine curing accelerator include triethylamine, tributylamine, N,N-dimethyl-4-aminopyridine (4-dimethylaminopyridine, DMAP), 2,4,6-tris(dimethylaminomethyl)phenol, 1, 8-diazabicyclo[5.4.0]-undecene-7 (DBU), 1,5-diazabicyclo[4.3.0]-nonene-5 (DBN) and the like.

Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl -4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl -4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazole isocyanuric acid adduct , 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2 -methyl-3-benzylimidazolium chloride, 2-methylimidazoline and the like.

Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1, 5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide , 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide and the like.

As the urea-based curing accelerator, 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1 -dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea and the like.

Among the above-mentioned curing accelerators, triphenylphosphine and tertiary amines are phosphorus-based compounds because they are excellent in curability, heat resistance, electrical properties, moisture resistance reliability, etc., especially when used as a semiconductor encapsulating material. 1,8-diazabicyclo-[5.4.0]-undecene (DBU) is preferably used.

The amount of the curing accelerator can be appropriately adjusted in order to obtain the desired curability. It is preferably 10 parts by mass, more preferably 0.1 to 5 parts by mass. When the amount of the curing accelerator is within the above range, the curability and insulation reliability are excellent, which is preferable.

<Flame retardant>
Examples of the flame retardant include, but are not particularly limited to, inorganic phosphorus flame retardants, organic phosphorus flame retardants, and halogen flame retardants. In addition, a flame retardant may be used individually or may be used in combination of 2 or more type.

Examples of the inorganic phosphorus-based flame retardant include, but are not limited to, red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and phosphate amides.
The organic phosphorus flame retardant is not particularly limited, but methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, (2-hydroxyethyl ) Phosphate esters such as methacrylate acid phosphate; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine oxide and the like diphenylphosphine; 9-oxa-10-phosphaphenanthrene-10-oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphosphine Phosphorus-containing phenols such as phenyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol and 1,5-cyclooctylenephosphinyl-1,4-phenyldiol 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10 Cyclic phosphorus compounds such as -(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; Aldehyde compounds, compounds obtained by reacting with phenol compounds, and the like.

The halogen-based flame retardant is not particularly limited, but brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2, -bis(tetrabromophthalimide), 2, 4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, tetrabromophthalic acid and the like.

The amount of the flame retardant compounded is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin (A).

[Cured product]
The present disclosure is a cured product of a resin composition for semiconductor encapsulation. A cured product obtained from the resin composition for encapsulating a semiconductor can exhibit low hygroscopicity and high adhesiveness to metal materials, which is a preferred embodiment. As a method for obtaining a cured product obtained by subjecting the resin composition for semiconductor encapsulation to a curing reaction, for example, the heating temperature during heat curing is not particularly limited, but is usually 100 to 300° C., and the heating time is , from 1 to 24 hours.

The cured product of the present embodiment preferably has a moisture absorption rate of 1.3% or less. The method for measuring the moisture absorption rate is the same as the evaluation method described in the Examples section.
The cured product of the present embodiment preferably has a Charpy impact strength of 3 J/cm ² or more, more preferably 3.5 J/cm ² or more, and particularly preferably 4 J/cm ² or more. . The method for measuring Charpy impact strength is based on JIS K 6911, under the conditions of 175 ° C. for 120 seconds and a molding pressure of 6.9 MPa, transfer molding, and post curing at 175 ° C. for 5 hours. After preparing the specimen for impact strength testing, the specimen was measured using a Pendulum Impact Tester Zwick 5102.

[Semiconductor encapsulation materials]
The present disclosure is a semiconductor encapsulating material containing a semiconductor encapsulating resin composition. The semiconductor encapsulating material obtained by using the semiconductor encapsulating resin composition has improved hygroscopicity and adhesion to metal materials, so that it is excellent in workability, moldability, and reflow resistance in the manufacturing process. This is a preferred embodiment.

As a method for obtaining the semiconductor encapsulating material of the present embodiment, an extruder, a kneader, a roll, or the like is used to add additives, which are optional components, to the resin composition for encapsulating a semiconductor, if necessary. and a method of sufficiently melting and mixing until the mixture becomes uniform.

[Semiconductor device]
The present disclosure is a semiconductor device including a cured product of the semiconductor encapsulating material. Since the semiconductor device obtained using the semiconductor encapsulating material uses the epoxy resin (A), it has improved hygroscopicity and adhesion to metal materials. This is a preferred embodiment because of its excellent properties.

As a method for obtaining the semiconductor device, the semiconductor encapsulating material is cast, or molded using a transfer molding machine, an injection molding machine, etc., and further cured by heating at a temperature range of room temperature (20 ° C.) to 250 ° C. method.

The cured product obtained from the resin composition for semiconductor encapsulation of the present embodiment has low hygroscopicity and high adhesion to metal materials, and therefore can be suitably used for semiconductor encapsulation materials and semiconductor devices. In addition, it can be suitably used for various applications such as prepreg, circuit board, build-up film, build-up board, adhesive, resist material, matrix resin of fiber reinforced resin, etc. It is not limited to these.

EXAMPLES The present invention will be described in more detail below using examples, but the present invention is not limited to these scopes.
[Evaluation method]
<Epoxy equivalent>
Measured based on JIS K7236.

<Melt viscosity at 150°C>
Based on ASTM D4287, it was measured with an ICI viscometer.

<Softening point>
The softening point (°C) was measured according to JIS K7234 (ring and ball method). In Table 2, a softening point of less than 50°C was rated as x, and a softening point of 50°C or higher was rated as ◯.

<GPC measurement>
Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation,
Column: Guard column "HXL-L" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40°C
Developing solvent Tetrahydrofuran
Flow rate 1.0 ml/min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of the "GPC Workstation EcoSEC-WorkStation".
(Polystyrene used)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
Sample: A tetrahydrofuran solution of 1.0% by mass in terms of solid content of resins obtained in the following production examples, synthesis examples, examples, etc. was filtered through a microfilter (50 μl), and the GPC was performed. Synthesis of the obtained resin and the like was confirmed from the measurement results. Also, the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw/Mn) of the obtained resin were calculated.

(Production Example 1: Synthesis of polyhydric hydroxy resin (P1))
488.6 g (4.00 mol) of 2,6-xylenol and 244 g of toluene were charged into a flask equipped with a thermometer, a condenser tube, a fractionating tube, a nitrogen gas inlet tube and a stirrer. .9 g was added and the temperature was raised to 115°C. After confirming that the raw materials were completely dissolved, 260.4 g of a mixture of divinylbenzene and ethylvinylbenzene (“DVB-810” manufactured by Nippon Steel Chemical Co., Ltd.) was added dropwise over 2 hours and allowed to react at 115°C for 1 hour. rice field. After completion of the reaction, the temperature was lowered to 80° C. and neutralized using an aqueous sodium hydroxide solution. Unreacted 2,6-xylenol and toluene were removed under heating and reduced pressure to obtain a polyhydric hydroxy resin (P1). Table 1 shows the hydroxyl equivalent weight of the obtained polyhydric hydroxy resin (P1).

(Production Example 2: Synthesis of polyhydric hydroxy resin (P2))
Same as Production Example 1 above, except that "2,6-xylenol 488.6 g (4.00 mol)" used in Production Example 1 above was changed to "2,4-xylenol 488.6 g (4.00 mol)". A reaction was carried out under the same conditions to obtain a polyhydric hydroxy resin (P2). Table 1 shows the hydroxyl group equivalent weight of the obtained polyhydric hydroxy resin (P2).

(Production Example 3: Synthesis of polyhydric hydroxy resin (P3))
The above production except that "2,6-xylenol 488.6 g (4.00 mol)" used in Production Example 1 above was changed to "2,3,6-trimethylphenol 544.8 g (4.00 mol)" A reaction was carried out under the same conditions as in Example 1 to obtain a polyhydric hydroxy resin (P3). Table 1 shows the hydroxyl group equivalent weight of the obtained polyhydric hydroxy resin (P3).

(Production Example 4: Synthesis of phenolic resin (1))
A reaction was carried out under the same conditions as in Production Example 1 above, except that "488.6 g (4.00 mol) of 2,6-xylenol" was changed to "376.4 g of phenol" to obtain a phenol resin (1). Table 1 shows the hydroxyl equivalent weight of the obtained phenol resin (1).

(Synthesis Example 1: Synthesis of epoxy resin (1))
300.0 g of the polyhydroxy resin (P1) obtained in Production Example 1 and 923 g (5.0 equivalents) of epichlorohydrin were added to a flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer while purging with nitrogen gas. , 238 g of n-butanol, and 90 g of water were charged and dissolved to prepare a mixed solution. After raising the temperature of the mixed solution to 60° C., 134 g (1.1 equivalents) of a 49% sodium hydroxide aqueous solution was added dropwise over 5 hours. After that, stirring was continued for 0.5 hours under the same conditions. Then, unreacted epichlorohydrin was removed by distillation under reduced pressure. Subsequently, 700 g of methyl isobutyl ketone was added to the resulting crude epoxy resin and dissolved to obtain a crude epoxy resin solution. Further, 15 g of a 5% aqueous sodium hydroxide solution was added to this crude epoxy resin solution and reacted at 80° C. for 2 hours, followed by washing with 190 g of water three times until the pH of the washing solution became neutral. Then, the inside of the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain epoxy resin (1) (=glycidyl etherate of polyhydric hydroxy resin (P1) (1)). . Table 2 shows the property values of the obtained epoxy resin (1).

(Synthesis Example 2: Synthesis of epoxy resin (2))
In Synthesis Example 1, the same conditions as in Synthesis Example 1 except that "300.0 g of polyhydroxy resin (P1)" was changed to "300.0 g of polyhydroxy resin (P2) (1.0 equivalent of hydroxyl group)". A reaction was carried out to obtain an epoxy resin (2) (=glycidyl etherified product (2) of polyhydric hydroxy resin (P2)). Table 2 shows the property values of the obtained epoxy resin (2).

(Synthesis Example 3: Synthesis of epoxy resin (3))
In Synthesis Example 1, the conditions were the same as in Synthesis Example 1, except that "300.0 g of polyhydroxy resin (P1)" was changed to "300.0 g of polyhydroxy resin (P3) (1.0 equivalent of hydroxyl group)". A reaction was carried out to obtain an epoxy resin (3) (=glycidyl etherified product (3) of polyhydric hydroxy resin (P3)). Table 2 shows the property values of the obtained epoxy resin (3).

(Comparative Synthesis Example 1: Synthesis of epoxy resin (4))
In Synthesis Example 1, the reaction was carried out under the same conditions as in Synthesis Example 1 except that "300.0 g of polyhydric hydroxy resin (P1)" was changed to "300.0 g of phenol resin (1) (1.0 equivalent of hydroxyl group)". Epoxy resin (4) (=glycidyl etherified product (4) of phenol resin (1)) was obtained. Table 2 shows the property values of the obtained epoxy resin (3).

(Comparative Synthesis Example 2: Epoxy Resin (5))
A biphenol type epoxy resin ("YX-4000K" manufactured by Mitsubishi Chemical Corporation) was used. Table 2 shows the property values of the epoxy resin (5).

(Examples 1-3 and Comparative Examples 1-2)
<Preparation of Resin Composition for Semiconductor Encapsulation>
Using the epoxy resins produced in Synthesis Examples 1 to 3 and Comparative Synthesis Examples 1 and 2, each component was blended according to the composition shown in Table 3 below, and melt-kneaded for 5 minutes at a temperature of 90°C using a twin roll. By doing so, the curable compositions of Examples 1 to 3 and Comparative Examples 1 and 2 (collective term for the resin compositions for semiconductor encapsulation of Examples 1 to 3 and the compositions of Comparative Examples 1 and 2) were prepared.
Then, from the curable compositions of Examples 1 to 3 and Comparative Examples 1 and 2, by the method described below, after preparing a cured product for evaluation used in various evaluations, hygroscopic evaluation and adhesion evaluation were performed. . Table 3 shows the results.

<Preparation of cured product for evaluation>
The curable resin composition obtained above was pulverized and molded using a transfer molding machine at a pressure of 70 kg/cm ² , a ram speed of 5 cm/sec, a temperature of 180°C and a time of 600 seconds. A cured product for evaluation was obtained by heating for 5 hours.
<Hygroscopic evaluation>
Each cured product for evaluation was cut with a diamond cutter into a size of 75 mm×25 mm×2.4 mm (thickness: 2.4 mm), and these were used as test pieces (a) for hygroscopic evaluation. The hygroscopicity was evaluated by leaving it for 300 hours in an environment of temperature/humidity of 85°C/85%, and then calculating the hygroscopicity (%) according to the following formula.
Moisture absorption = [(mass of test piece (a) after test - mass of test piece (a) before test) / mass of test piece (a) before test x 100 (%)]
<Adhesion evaluation>
Adhesion was evaluated by a die shear test. The cured product for evaluation was pulverized, and a transfer molding machine was used at a pressure of 70 kg/cm ² , a ram speed of 5 cm/sec, a temperature of 175°C, and a time of 600 seconds to obtain a molded product with dimensions of 6 mm × 6 mm × 2 mm (thickness 2 mm) to obtain a test piece. The test was conducted using a bonding tester (“PTR-1102” manufactured by RHESCA). The shear rate was 0.1 mm/sec, one test was performed at N5, and the average peel strength (gf) from the copper foil was calculated. The peel strength was a relative evaluation, and the strength of each composition was calculated when the molded article of Comparative Example 2 was set to 1.0. EFTEC-64T (0.15 mmt, manufactured by Furukawa Electric Co., Ltd.) was used as the copper foil.

注）上記表３中の硬化剤は、フェノールノボラック型フェノール樹脂（ＤＩＣ株式会社製「ＴＤ－２１３１」水酸基当量１０４ｇ／ｅｑ）である。また、硬化促進剤は、トリフェニルホスフィン（北興化学工業株式会社製「ＴＰＰ」）である。さらに、溶融シリカは、電気化学株式会社製「ＦＢ－５６０」であり、シランカップリング剤は、γ－グリシドキシエトキシシラン（信越化学工業株式会社製「ＫＢＭ－４０３」）を使用した。離型剤は、カルナバワックス（大日本化学株式会社製「Ｆ１－１００」）、着色剤は、カーボンブラック（三菱化学株式会社製「ＭＡ１００」）を使用した。

Note) The curing agent in Table 3 above is a phenol novolac type phenolic resin (manufactured by DIC Corporation "TD-2131" hydroxyl equivalent 104 g/eq). The curing accelerator is triphenylphosphine (“TPP” manufactured by Hokko Chemical Industry Co., Ltd.). Further, fused silica was “FB-560” manufactured by Denki Kagaku Co., Ltd., and γ-glycidoxyethoxysilane (“KBM-403” manufactured by Shin-Etsu Chemical Co., Ltd.) was used as the silane coupling agent. Carnauba wax (“F1-100” manufactured by Dainippon Chemical Co., Ltd.) was used as the release agent, and carbon black (“MA100” manufactured by Mitsubishi Chemical Corporation) was used as the coloring agent.

From the evaluation results in Tables 2 and 3 above, the resin compositions for semiconductor encapsulation obtained in all the examples had lower hygroscopicity during curing than the curable resin compositions obtained in the comparative examples. and excellent adhesion to metal materials.

Claims (7)

A glycidyl etherified product of a polyhydric hydroxy resin (P) using an aromatic compound (i) containing an aromatic ring having a phenolic hydroxyl group and two or more hydrocarbon groups and an aromatic vinyl compound (ii) as reaction raw materials (1) an epoxy resin (A);
a curing agent (B);
A resin composition for semiconductor encapsulation, containing an inorganic filler (C). The content of the epoxy resin (A) is 5 to 40% by mass with respect to the total amount of the epoxy resin (A), the curing agent (B), and the inorganic filler (C). The resin composition for semiconductor encapsulation according to claim 1 . The content of the curing agent (B) is 5 to 40% by mass with respect to the total amount of the epoxy resin (A), the curing agent (B), and the inorganic filler (C). The resin composition for semiconductor encapsulation according to claim 1 or 2. The content of the inorganic filler (C) is 60 to 95% by mass with respect to the total amount of the epoxy resin (A), the curing agent (B), and the inorganic filler (C). The resin composition for semiconductor encapsulation according to any one of claims 1 to 3. The molecular weight distribution indicating the ratio (Mw/Mn) of the weight average molecular weight (Mw) of the epoxy resin (A) to the number average molecular weight (Mn) of the epoxy resin (A) is 1.1 to 1.8. The resin composition for semiconductor encapsulation according to any one of claims 1 to 4, which is within the range. A semiconductor encapsulating material containing the semiconductor encapsulating resin composition according to any one of claims 1 to 5. A semiconductor device comprising a cured product of the resin composition for semiconductor encapsulation according to any one of claims 1 to 5.