Epoxy resin composition and its manufacturing method, curable composition, cured product, semiconductor encapsulating material, semiconductor device, prepreg, circuit board, and build-up film

Abstract

To provide an epoxy resin composition capable of contributing to fluidity and moldability, a curable composition containing the epoxy resin, a cured material obtained by using the curable composition and excellent in toughness, and, low hygroscopicity, a semiconductor sealing material, a semiconductor device, a prepreg, a circuit board, and a build-up film.SOLUTION: The present invention relates to a glycidyl-etherified product (E1) of a biphenol compound (P1), and a glycidyl-etherified product (E2) of a polyhydric hydroxy resin (P2) with a phenolic hydroxyl group-containing compound and an aromatic divinyl compound as reaction raw materials.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an epoxy resin composition and a method for producing the same, a curable composition, a cured product, a semiconductor encapsulating material, a semiconductor device, a prepreg, a circuit board, and a build-up film. [Background technology]

[0002] Epoxy resin compositions, consisting essentially of epoxy resins and their curing agents, are widely used in semiconductor encapsulation materials, electronic components such as printed circuit boards, conductive adhesives such as conductive pastes, other adhesives, composite matrix materials, paints, photoresist materials, and color developers due to their excellent physical properties, including high heat resistance, moisture resistance, and low viscosity. Among these applications, in the field of semiconductor encapsulation materials, there is a growing demand for miniaturization and high integration of electronic devices, making the reliability of plastic-packaged ICs a major issue. For heat dissipation from highly integrated semiconductor devices, copper alloy lead frames, which have higher thermal conductivity and a linear expansion coefficient similar to that of plastics compared to the previously widely used 42 alloy (Fe-42% Ni alloy), are advantageous. Therefore, the adoption of copper alloy lead frames is becoming more common. Furthermore, due to the increasing number of input / output terminals and package size associated with recent trends toward higher density, surface-mount packages such as ball grid arrays (BGAs) and chip-chip packages (CSPs) are becoming increasingly popular. Reflow soldering, which involves simultaneously melting and mounting multiple ICs, has become mainstream.

[0003] However, this method heats the entire semiconductor package to temperatures of over 200°C, which can lead to cracks and interfacial delamination due to stress generated by the evaporation of moisture from the humid semiconductor package during reflow soldering. Therefore, semiconductor encapsulation materials must not only reduce lead frame interfacial delamination, but also reduce moisture absorption and elastic modulus during heating. Furthermore, as wires become thinner due to the increasing number of input / output terminals, suppressing wire deformation during molding is also a major issue, and epoxy resins with low viscosity and excellent flowability are needed to suppress wire deformation.

[0004] Patent Document 1, for example, is an example of a technology that satisfies these required properties. Patent Document 1 discloses a technology that uses a specific granular epoxy resin that is a solid at room temperature and prone to blocking. More specifically, the technology discloses a technology in which the melt viscosity is reduced by reducing the amount of low-molecular-weight components in the granular epoxy resin to a certain level or less, thereby improving fluidity during molding and reducing blocking between granular epoxy resins that are solid at room temperature during storage and transportation, thereby making the resin easier to handle. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2004-307687 Summary of the Invention [Problem to be solved by the invention]

[0006] However, the technology of Patent Document 1 does not consider at all the reduction of peeling at the lead frame interface of a copper substrate or the like, nor the reduction of the moisture absorption rate or the elastic modulus when heated, and the properties of the disclosed epoxy resin are also insufficient. Therefore, an object of the present invention is to provide an epoxy resin composition that exhibits excellent adhesion to metal materials and a low hot elastic modulus when cured, as well as a curable composition containing the epoxy resin composition, and a cured product, semiconductor encapsulation material, semiconductor device, prepreg, circuit board, and build-up film obtained using the curable composition. [Means for solving the problem]

[0007] As a result of extensive research aimed at solving the above-mentioned problems, the present inventors have found that by combining at least two prepolymers having specific chemical structures, it is possible to obtain an epoxy resin composition that exhibits excellent adhesion to metal materials and a low modulus of elasticity when heated, a curable composition containing the epoxy resin composition, and a cured product, a semiconductor encapsulating material, a semiconductor device, a prepreg, a circuit board, and a build-up film obtained using the curable composition, thereby completing the present invention. In the method for producing an epoxy resin composition according to the present disclosure, a prepolymer precursor having ring-assembly hydrocarbons with high crystallinity is mixed as a reaction raw material, thereby making it possible to effectively utilize the prepolymer having ring-assembly hydrocarbons, which is difficult to recover as a simple substance due to its high crystallinity.

[0008] That is, the present disclosure provides an epoxy resin composition containing a glycidyl ether (E1) of a biphenol compound (P1) and a glycidyl ether (E2) of a polyhydric hydroxy resin (P2) obtained by reacting a phenolic hydroxyl group-containing compound with an aromatic divinyl compound as reaction raw materials. [Effects of the Invention]

[0009] According to the present disclosure, there are provided an epoxy resin composition that exhibits excellent adhesion to metal materials and a low hot elastic modulus when cured, a curable composition containing the epoxy resin composition, and a cured product, a semiconductor encapsulation material, a semiconductor device, a prepreg, a circuit board, and a build-up film obtained using the curable composition. In particular, the reflow resistance can be dramatically improved, making the composition particularly useful in applications such as electronic component encapsulation materials. According to the manufacturing method of the present disclosure, by mixing a prepolymer precursor having ring-assembly hydrocarbons that exhibits high crystallinity as a reaction raw material, it is possible to effectively utilize the prepolymer having ring-assembly hydrocarbons, which are difficult to recover as simple substances due to their high crystallinity. DETAILED DESCRIPTION OF THE INVENTION

[0010] Below, we will explain in detail the embodiment of the present disclosure (hereinafter referred to as the "present embodiment"), but the present disclosure is not limited to the description below and can be implemented in various modifications within the scope of its gist. [Epoxy resin composition] The present disclosure provides an epoxy resin composition containing a glycidyl ether (E1) of a biphenol compound (P1) (hereinafter also referred to as component (E1)) and a glycidyl ether (E2) of a polyhydric hydroxy resin (P2) (hereinafter also referred to as component (E2)). The polyhydric hydroxy resin (P2) is a compound produced from an aromatic compound (A) containing an aromatic ring having a phenolic hydroxyl group and two or more hydrocarbon groups (hereinafter also referred to simply as aromatic compound (A)) and an aromatic divinyl compound (B1) as reaction raw materials. The epoxy resin composition of the present embodiment contains glycidyl ethers having at least two types of chemical structures, and also contains a glycidyl ether (E1) having a biphenyl structure that exhibits high crystallinity, and therefore can exhibit excellent adhesion to metal materials and a low modulus of elasticity when heated.

[0011] In the epoxy resin composition of this embodiment, the content of component (E1) is preferably 1 to 50% by mass, more preferably 2 to 40% by mass, and even more preferably 3 to 30% by mass, relative to 100% by mass of the combined total of components (E1) and (E2). By ensuring that the content of component (E1) is 1% by mass or more, the effect of reducing melt viscosity and the effect of improving handleability are exhibited. On the other hand, by ensuring that the content of component (E1) is 50% by mass or less, the effect of low moisture absorption is exhibited. In the epoxy resin composition of this embodiment, the content of component (E2) is preferably 40 to 99% by mass, more preferably 45 to 98% by mass, and even more preferably 50 to 97% by mass, relative to 100% by mass of the combined total of components (E1) and (E2). By ensuring that the content of component (E2) is 40% by mass or more, the effect of a low elastic modulus is exhibited. On the other hand, by ensuring that the content of component (E2) is 99% by mass or less, the effect of reducing melt viscosity and the effect of improving handleability are exhibited.

[0012] The epoxy equivalent of the epoxy resin composition of this embodiment is preferably 150 to 600 g / eq, more preferably 200 to 500 g / eq, and even more preferably 220 to 400 g / eq. When the epoxy equivalent of the epoxy resin composition is within the above range, the generation of active hydroxyl groups that is generated when the epoxy resin composition reacts with a curing agent is suppressed, and the resulting cured product has excellent heat resistance, low moisture absorption, and resulting reflow resistance. The epoxy equivalent in this specification is measured in accordance with JIS K 7236, as described in the Examples section.

[0013] The epoxy resin composition of this embodiment preferably has a melt viscosity at 150°C measured with an ICI viscometer of 0.01 to 5 dPa·s, more preferably 0.01 to 2 dPa·s, and even more preferably 0.01 to 1 dPa·s. It is preferable for the melt viscosity of the epoxy resin composition to be within the above range, since the composition has low viscosity and excellent flowability, resulting in excellent moldability of the resulting cured product. As described in the Examples section, the melt viscosity in this specification is measured with an ICI viscometer in accordance with ASTM D4287.

[0014] Since the epoxy resin composition of this embodiment has low viscosity and excellent fluidity, the number average molecular weight (Mn) of the entire epoxy resin composition is preferably in the range of 300 to 1500. The weight average molecular weight (Mw) of the entire epoxy resin composition is preferably in the range of 350 to 2000. The dispersity (Mw / Mn) is preferably in the range of 1.5 to 3. In the present invention, the molecular weight of the epoxy resin is measured using gel permeation chromatography (hereinafter abbreviated as "GPC") under the measurement conditions described in the examples below.

[0015] In the epoxy resin composition of the present embodiment, the biphenol compound (P1) units in the glycidyl ether (E1) preferably account for 0.5% by mass or more and 40% by mass or less, and more preferably 1% by mass or more and 35% by mass or less, of the total amount of the biphenol compound (P1) units and the polyhydric hydroxy resin (P2) units in the glycidyl ether (E2). This results in better adhesion to metal materials and a lower hot modulus of elasticity when cured. In this specification, the term "unit" refers to a repeating unit of a chemical structure formed during reaction or polymerization. In this specification, the term "reaction raw material" refers to a compound that is used to obtain a target compound through a chemical reaction such as synthesis or decomposition and that partially constitutes the chemical structure of the target compound, and excludes substances that act as chemical reaction auxiliaries, such as solvents and catalysts. In particular, in this specification, the term "reaction raw material" refers to a monomer compound that serves as a precursor for obtaining a target prepolymer (polyhydric hydroxy resin (P2) or glycidyl ether (E2)) through a polymerization reaction.

[0016] Each component constituting the epoxy resin composition of the present embodiment will be described below. <Biphenol compound (P1)> The biphenol compound (P1) in this embodiment is not particularly limited as long as it has a structure in which two hydroxyphenyl groups are linked, but examples include 2,2'-biphenol, 2,4'-biphenol, 3,3'-biphenol, 4,4'-biphenol, and biphenol derivatives in which one or more hydrogen atoms in the aromatic ring of these compounds are substituted with one or more monovalent substituents. Examples of the substituents include an aliphatic hydrocarbon group, an alkoxy group, and a halogen atom. The biphenol compounds (P1) may be used alone or in combination of two or more. In this specification, the "aliphatic hydrocarbon group" may be either linear or branched, and may have an unsaturated bond in its structure. That is, when the aliphatic hydrocarbon group has two or more carbon atoms, one or more -CH2-CH2- in the aliphatic hydrocarbon group may each independently be replaced by -CH=CH- or -C≡C-. Among these, the "aliphatic hydrocarbon group" is preferably an alkyl or alkenyl group having 1 to 4 carbon atoms, since this makes the effect of the present invention (low moisture absorption) even more pronounced. Specific examples of the alkyl or alkenyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, an isobutyl group, a vinyl group, and an allyl group. The alkoxy group preferably has 1 to 4 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. In particular, the biphenol compound (P1) in this embodiment is preferably 4,4'-biphenol or a compound having a substituent on its aromatic ring, and more preferably 4,4'-biphenol, since this facilitates adjustment of the melt viscosity of the final epoxy resin to a preferred value. The biphenol compound (P1) in this embodiment is preferably represented by the following general formula (P1). [ka] (In the above general formula (P1), R p1 and R p2 each independently represents an aliphatic hydrocarbon group, an alkoxy group, or a halogen atom; n p1 and n p2 each independently represents an integer of 0 to 4. In the above general formula (P1), R p1 and R p2 are each independently preferably an alkyl group, alkenyl group or alkoxy group having 1 to 4 carbon atoms. In the above general formula (P1), n p1 and n p2 preferably each independently represents an integer of 0 to 2.

[0017] <Glycidyl ether (E1)> The glycidyl ether (E1) in this embodiment is a compound obtained by glycidyl-etherifying the biphenol compound (P1), more specifically, a compound in which one or more hydroxyl groups in the biphenol compound are substituted with glycidyl groups. As will be described later in the section on the method for producing the glycidyl ether (E1), the glycidyl ether (E1) can be produced by reacting the biphenol compound (P1) with epihalohydrin. By including the glycidyl ether (E1) in the epoxy resin composition of the present embodiment, the melt viscosity can be reduced, and the handleability can be improved. The glycidyl ether (E1) in this embodiment is preferably represented by the following general formula (E1). [ka] (In the above general formula (E1), G e1 represents a glycidyl group, and R p1 and R p2 represents an aliphatic hydrocarbon group, an alkoxy group, or a halogen atom; n p1 and n p2 represents an integer from 0 to 4.) In the above general formula (E1), R p1 and R p2 are each independently preferably an alkyl group, alkenyl group or alkoxy group having 1 to 4 carbon atoms. In the above general formula (E1), n p1 and n p2 preferably each independently represents an integer of 0 to 2. In addition, specific examples of the aliphatic hydrocarbon group, alkoxy group, or halogen atom in the above general formula (E1) can be those described in the above section on <Biphenol compound (P1)>.

[0018] <Polyhydroxy resin (P2)> The polyhydroxy resin (P2) in this embodiment is prepared using, as reaction raw materials, an aromatic compound (A) containing an aromatic ring having a phenolic hydroxyl group and two or more hydrocarbon groups, and an aromatic divinyl compound (B1). In this embodiment, an aromatic monovinyl compound (B2) may also be included as a reaction raw material. In other words, the polyhydroxy resin (P2) in this embodiment has a structure in which units of the aromatic compound (A) containing an aromatic ring having a phenolic hydroxyl group and two or more hydrocarbon groups are chemically bonded to units of the aromatic divinyl compound (B1), and, if necessary, units of the aromatic monovinyl compound (B2) are chemically bonded to the aromatic ring in the units of the aromatic compound (A). In the present embodiment, the aromatic compound (A), which is a phenolic compound having two or more hydrocarbon groups on an aromatic ring, is used as a reaction raw material. This makes it easier to control the reaction site with the aromatic divinyl compound (B1) described below, and therefore makes it easier to obtain a polyhydroxy resin (P2) with a uniform chemical structure or chain length. As a result, an epoxy resin composition can be provided that, when cured, exhibits excellent adhesion to metal materials and a low hot elastic modulus. Below, we will explain the aromatic compound (A), aromatic divinyl compound (B1) and aromatic monovinyl compound (B2), which are the components of the reaction raw materials for the polyhydroxy resin (P2), and then we will explain preferred forms of the polyhydroxy resin (P2) and the glycidyl ether (E2) of the polyhydroxy resin (P2).

[0019] <Aromatic compounds (A)> The aromatic compound (A) in this embodiment has a phenolic hydroxyl group and two or more hydrocarbon groups (R a ) in the aromatic ring. Therefore, the aromatic compound (A) can be a phenolic compound. The aromatic ring forming the central structure of the aromatic compound (A) may be monocyclic or fused polycyclic, and may further contain an aromatic hydrocarbon ring. Examples of the aromatic hydrocarbon ring include, but are not limited to, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and a phenalene ring. From the viewpoint of the melt viscosity of the resin, the aromatic ring is preferably monocyclic.

[0020] In the aromatic compound (A) of the present embodiment, at least one of the aromatic rings in the aromatic compound (A) has two or more hydrocarbon groups (R a Examples of the hydrocarbon group (R ) include hydrocarbon groups having 1 to 6 carbon atoms. a ) includes a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms. The aliphatic hydrocarbon group may be either a straight-chain or branched type. The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group in order to prevent addition reactions with other compounds. Examples of saturated aliphatic hydrocarbon groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a s-butyl group, a t-butyl group, a pentyl group, and a hexyl group. The lower the molecular weight of the hydrocarbon group, the more remarkable the effect of the present invention (adhesion when cured). In addition, the hydrocarbon group (R a The higher the molecular weight of the copolymer, the more remarkable the effect of the present invention (low moisture absorption).

[0021] The hydrocarbon group (R a The number of the hydrocarbon groups (R a ) is 2 or more, excellent adhesion to metal materials and a low modulus of elasticity when heated can be exhibited. The hydrocarbon group (R a The upper limit of the number of hydrocarbon groups may be a number obtained by subtracting 3 from the number of substitutable ring-constituting atoms in the unsubstituted aromatic ring, from the viewpoint that the aromatic ring has a phenolic hydroxyl group and two bonds are used in polymerization. For example, when the aromatic ring is a benzene ring, the number of hydrocarbon groups is 3 or less. In addition, the hydrocarbon group (R a By making the number of the groups (B1) 2 or more, it becomes easier to control the reaction site with the aromatic divinyl compound (B1) described below, and therefore it becomes easier to obtain a polyhydroxy resin (P2) having a uniform chemical structure or chain length, and as a result, it becomes easier to exhibit excellent melt viscosity, excellent adhesion to metal materials, or a low modulus of elasticity when heated. Furthermore, by using an aromatic compound (A) that is a phenolic compound having two or more substituents, the reactive sites can be controlled, making it easier to obtain a polyhydroxy resin (A) with a uniform chemical structure or chain length. This is thought to optimize the distance between the crosslinking points of the aromatic divinyl compound (B1) that acts as a linking group, thereby reducing the hot elastic modulus.

[0022] In this embodiment, the aromatic compound (A) contains a phenolic hydroxyl group and two or more hydrocarbon groups (R a A preferred embodiment of the aromatic compound (A) will be described below, taking as an example a case where the aromatic compound (A) has an aromatic hydrocarbon ring (for example, a benzene ring or a naphthalene ring) having the formula (I). In this embodiment, among the carbon atoms in the aromatic hydrocarbon ring constituting the aromatic compound (A), it is preferred that one or more carbon atoms having the largest HOMO electron density (Huckel coefficient) are unsubstituted (or substituted with a hydrogen atom). This allows the formation of ArS by the cationoid reagent formed from the aromatic divinyl compound (B1) described below. E This makes it easier to control the reaction and molecular design. More specifically, if the carbon atom in the aromatic hydrocarbon ring constituting the aromatic compound (A) that has the largest HOMO electron density (Huckel coefficient) is unsubstituted (or bonded to a hydrogen atom), the carbocation of the aromatic divinyl compound (B1), which is a cationoid reagent, is likely to react with the carbon atom with the largest HOMO electron density. Therefore, the hydrocarbon group (R a By controlling the number and position of the hydroxyl groups or the number and position of the phenolic hydroxyl groups, it is possible to adjust the bonding sites or number of bonds with the aromatic divinyl compound. Therefore, it is presumed that it will be easier to design the chemical structure or molecular chain length of the resulting polyhydroxy resin (P2). For example, when the aromatic compound (A) has a phenol skeleton containing one benzene ring and one hydroxyl group, it is preferable that at least one carbon atom among the 2-, 4-, and 6-positions be substituted with a hydrogen atom. This facilitates attack by the cationoid reagent formed from the aromatic divinyl compound (B1) described below on at least one carbon atom among the 2-, 4-, and 6-positions, which are the electron-dense ortho and para positions of the phenol nucleus. In particular, it is preferable that the cationoid reagent formed from the aromatic divinyl compound (B1) be added to the 4-position of the phenol nucleus. This results in p-substitution of the benzene ring of the phenol nucleus, which, due to its symmetrical structure, forms a crosslinked structure that is easy to relax stress, which is believed to be advantageous for improving adhesion and Charpy impact strength. This mechanism of action is believed to work similarly whether the polyhydric hydroxy resin (P2) is used as an epoxy resin or a phenolic resin (curing agent). Similarly, in an unsubstituted naphthalene ring, the carbon atoms at positions 1, 4, 5, and 8 have the highest HOMO electron density. The position of the carbon atom with the highest HOMO electron density varies depending on the bonding position of the phenolic hydroxyl group. For example, in 2-naphthol, which has one naphthalene ring and one hydroxyl group, the carbocation generated from the aromatic divinyl compound (B1) is more likely to react with the 1st and 3rd positions. Therefore, for example, the hydrogen atom of the CH group at position 1 can be easily bonded to a hydrocarbon group (R a ) to the carbon atom at the 3rd position, E Since the aromatic compound (A) is easily reactive, the chemical structure of the resulting polyhydroxy resin (P2) can be controlled. Furthermore, for example, when the aromatic compound (A) has a 2,7-hydroxynaphthalene skeleton, the carbocation generated from the aromatic divinyl compound (B1) is easily reactive with the 1st, 3rd, 6th, and 8th carbon atoms. Therefore, for example, when hydrocarbon groups (R a ) is bonded, ArS is bonded to the 8th carbon atom. E It becomes easier to react. From the above, two or more hydrocarbon groups (R a ) is thought to make it easier to control the resin structure.

[0023] Specific examples of the aromatic compound (A) of this 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 compounds consisting of derivatives thereof. The hydrogen atoms of two or more CH groups in a compound selected from the group consisting of a dialkylphenol compound, 1-naphthol, 2-naphthol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 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, may be substituted with the hydrocarbon group (R a ) substituted compounds, so-called dialkylhydroxynaphthalene compounds, but are not limited to these. The aromatic compound (A) in this embodiment may be used alone or in combination of two or more kinds, however, from the viewpoint of low viscosity when melted, a dialkylphenol compound is preferred.

[0024] The aromatic compound (A), which is a reaction raw material for the polyhydric hydroxy resin (P2) in this embodiment, can be represented by, for example, the following general formula (A1). [ka] (In the above general formula (A1), R a represents a hydrocarbon group having 1 to 6 carbon atoms, preferably a hydrocarbon group having 1 to 3 carbon atoms; p a represents 2 or 3. Multiple R a may be the same or different.)

[0025] In the general formula (A1), the hydrocarbon group having 1 to 6 carbon atoms is the hydrocarbon group (R a )

[0026] -Aromatic divinyl compound (B1)- The aromatic divinyl compound (B1) in this embodiment can be any compound as long as it has two vinyl groups as substituents on the aromatic ring and can react with the aromatic compound (A). That is, the aromatic divinyl compound (B1) can form a linking group that connects the aromatic compounds (A) together via a predetermined site. Examples of the aromatic divinyl compound (B1) include divinylbenzene, divinylbiphenyl, divinylnaphthalene, and various compounds in which one or more alkyl groups, alkoxy groups, halogen atoms, etc. are substituted on the aromatic ring. The alkyl group or alkoxy group may be either linear or branched. In particular, from the viewpoint of exhibiting excellent adhesion to metal materials and a low modulus of elasticity at elevated temperatures, the alkyl group or alkoxy group preferably has 1 to 4 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, and isobutyl groups. Examples of the alkoxy group include methoxy, ethoxy, propyloxy, and butoxy groups. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. As mentioned above, the ArS reaction can be carried out by the cationoid reagent formed from the aromatic divinyl compound (B1). E By the reaction, the aromatic divinyl compound (B1) can be introduced into a specific position of the aromatic ring in the aromatic compound (A), which makes it easier to obtain a polyhydroxy resin (P2) with a uniform chemical structure or chain length, thereby providing an epoxy resin composition that exhibits excellent adhesion to metal materials and a low modulus of elasticity when heated.

[0027] Specific examples of the aromatic divinyl compound (B1) of this 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, and compounds composed of derivatives thereof. and divinylnaphthalenes such as 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-divinylnaphthalene, 1,8-divinylnaphthalene, 1,5-dimethoxy-4,8-divinylnaphthalene, and compounds consisting of derivatives thereof, but are not limited to these. The aromatic divinyl compounds (B1) in the present embodiment may be used alone or in combination of two or more. In particular, from the viewpoint of flowability, the aromatic divinyl compound (B1) is preferably divinylbenzene or a compound having a substituent on its aromatic ring, and more preferably divinylbenzene. In the present embodiment, the substitution position of the vinyl group in divinylbenzene is not particularly limited, but it is preferable that the meta isomer is the main component. The content of the meta isomer in divinylbenzene is preferably 40% by mass or more, more preferably 50% by mass or more, based on the total amount of divinylbenzene.

[0028] The aromatic divinyl compound (B1), which is a reaction raw material for the polyhydric hydroxy resin (P2) of the present disclosure, can be represented by the following formula (B1). [ka] (In the above general formula (B1), R b1represents a halogen atom or an alkyl or alkoxy group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms; p b1 represents an integer of 0 to 4, preferably 0 to 1. b1 If is an integer greater than or equal to 2, there are multiple R b1 may be the same or different.)

[0029] In the above general formula (B1), examples of the alkyl group or alkoxy group having 1 to 4 carbon atoms are the same as the above alkyl group or alkoxy group.

[0030] <Aromatic monovinyl compounds (B2)> In the present embodiment, the polyhydroxy resin (P2) may use, as a reaction raw material, other compounds in addition to the aromatic compound (A) and the aromatic divinyl compound (B1). Examples of such other compounds include an aromatic monovinyl compound (B2). That is, in the present embodiment, the polyhydroxy resin (P2) is preferably produced using, as reaction raw materials, the aromatic compound (A), the aromatic divinyl compound (B1), and the aromatic monovinyl compound (B2). Therefore, the aromatic monovinyl compound (B2) is a group that optionally substitutes a hydrogen atom in the ring structure of the aromatic compound (A). The polyhydroxy resin (P2) of this embodiment is prepared by using, as its reaction raw materials, the aromatic compound (A), the aromatic divinyl compound (B1), and an aromatic monovinyl compound (B2), and the resulting glycidyl ether (E2) of the polyhydroxy resin (P2) exhibits excellent low moisture absorption and therefore good reliability when used as a semiconductor encapsulation material, which is preferable. Furthermore, the use of the aromatic monovinyl compound (B2) is also useful for improving moisture resistance. In addition, the aromatic monovinyl compound (B2) also generates a carbocation like the aromatic divinyl compound (B1), and therefore it is more likely to react with the carbon atom in the aromatic hydrocarbon ring that constitutes the aromatic compound (A) that has the largest HOMO electron density (Hückel coefficient).

[0031] Examples of the aromatic monovinyl compound (B2) in this embodiment include vinylbenzene, vinylbiphenyl, vinylnaphthalene, and various compounds in which one or more substituents such as alkyl groups, alkoxy groups, and halogen atoms are substituted on the aromatic ring of these compounds. The alkyl group or alkoxy group may be either linear or branched, and may have an unsaturated bond in its structure. In particular, when low moisture absorption is important, the alkyl group or alkoxy group is preferably a group having 1 to 4 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, and an isobutyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0032] Specific examples of the aromatic monovinyl compound (B2) of this embodiment include, but are not limited to, vinylbenzenes such as styrene, fluorostyrene, vinylbenzyl chloride, alkylvinylbenzenes (o-, m-, p-methylstyrene, o-, m-, p-ethylvinylbenzene), o-, m-, p-(chloromethyl)styrene, and compounds composed of derivatives thereof; biphenyl compounds such as 4-vinylbiphenyl, 4-vinyl-p-terphenyl, and compounds composed of derivatives thereof; and vinylnaphthalenes such as 1-vinylnaphthalene, 2-vinylnaphthalene, and compounds composed of derivatives thereof. In particular, from the viewpoint of low moisture absorption, alkylvinylbenzenes and compounds having a substituent on the aromatic ring thereof are preferred, and ethylvinylbenzene is more preferred. Furthermore, the substitution positions of the vinyl group and the ethyl group in ethylvinylbenzene are not particularly limited, but it is preferable that the meta isomer is the main component, and the content of the meta isomer in ethylvinylbenzene is more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total amount of the ethylvinylbenzene.

[0033] The aromatic monovinyl compound (B2) that can be a reaction raw material for the polyhydric hydroxy resin (P2) of the present disclosure can be represented by the following general formula (B2). [ka] (In the above general formula (B2), R b2 represents a halogen atom or an alkyl or alkoxy group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms; p b2 represents an integer of 0 to 5, preferably 0 to 1. b2 If is an integer greater than or equal to 2, there are multiple R b2 may be the same or different.)

[0034] In the above general formula (B2), the alkyl group or alkoxy group having 1 to 4 carbon atoms is the same as the alkyl group or alkoxy group described above. In addition, p b2 If is 2 or more, there are multiple R b2 may be the same group or different groups.

[0035] When the aromatic monovinyl compound (B2) is used as a reaction raw material for the polyhydroxy resin (P2) in this embodiment, the mass ratio ((B1) / (B2)) of the aromatic divinyl compound (B1) to the aromatic monovinyl compound (B2) in the reaction raw materials is preferably 30 / 70 to 99 / 1, more preferably 50 / 50 to 99 / 1, and even more preferably 50 / 50 to 98 / 2. Having the mass ratio of the aromatic divinyl compound (B1) to the aromatic monovinyl compound (B2) within the above range is preferable because it allows for a balance of the handleability of the resulting polyhydroxy resin (P2) and the moldability and curability during the production of epoxy resins obtained from the polyhydroxy resin (P2), making it possible to achieve a good balance of physical properties.

[0036] In the polyhydric hydroxy resin (P2) of the present embodiment, the proportion of the aromatic compound (A) units, the aromatic divinyl compound (B1) units, and the aromatic monovinyl compound (B2) units contained as needed in the reaction raw materials is preferably 80 mass% or more, and more preferably 90 mass% or more, based on the total amount (100 mass%) of the polyhydric hydroxy resin (P2).

[0037] Hereinafter, preferred embodiments of the polyhydric hydroxy resin (P2) of the present disclosure will be described taking as an example a case where each aromatic ring is a benzene ring. The following chemical structural formula is provided for illustrative purposes, and the scope of the present disclosure is not limited to the following chemical structural formula.

[0038] The polyhydric hydroxy resin (P2) in this embodiment preferably has a partial structure represented by the following general formula (I) and / or (II). [ka] [ka] (In the above general formulas (I) and (II), R 1 , R 2 , and R 3 each independently represents a hydrocarbon group having 1 to 6 carbon atoms, R 4 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 6 is represented by the general formula (a) [ka] (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 R per phenol ring in the entire polyhydric hydroxy resin (P2).6 is the average number of substitutions, and represents a number of 0 to 1. In addition, * in the above general formulas (I) and (II) represents a bond to another atom.) In the above general formulas (I) and (II), the hydrocarbon group having 1 to 6 carbon atoms is the hydrocarbon group (R a In the above general formulas (I) and (II), R 1 , R 2 , and R 3 are each preferably independently an alkyl group having 1 to 4 carbon atoms, and R 4 and R 5 are preferably each independently a hydrogen atom or a methyl group. In the above general formula (a), 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, and is preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. In addition, one or two or more non-adjacent -CH2- groups in the alkyl group, alkenyl group, or alkoxy group may be substituted with -O-, -COO-, or -OCO-.

[0039] The polyhydric hydroxy resin (P2) in this embodiment is preferably represented by the following general formula (III) and / or (IV). [ka] (In the above general formulas (III) and (IV), R 1 , R 2 , and R 3 each independently represents a hydrocarbon group having 1 to 6 carbon atoms, R 4 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 6 is represented by the general formula (a) [ka] (In general formula (a), R7 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 of 0 to 20, m represents an integer of 0 to 20; p is the average R per phenol ring 6 is the number of substitutions and represents the numbers 0 to 1.) R in general formulas (III) and (IV) 1 ~R 8 represents R in the above general formulas (I) and (II). 1 ~R 8 (This is omitted here because it is similar to

[0040] The hydroxyl group equivalent of the polyhydric hydroxy resin (P2) of this embodiment is preferably 200 to 500 g / eq, and more preferably 200 to 400 g / eq. In this specification, the hydroxyl group equivalent of the polyhydric hydroxy resin (P2) is measured by a method based on the neutralization titration method specified in JIS K 0070 (1992). The softening point of the polyhydric hydroxy resin (P2) of this embodiment may be 40 to 150° C., and preferably 50 to 120° C. The softening point here is measured in accordance with JIS K 7234 (ring and ball method) under the measurement conditions described in the Examples section below. The polyhydroxy resin (P2) of this embodiment preferably has a melt viscosity at 150°C measured with an ICI viscometer of 0.01 to 5 dPa·s, more preferably 0.01 to 2 dPa·s, and even more preferably 0.01 to 1 dPa·s. When the melt viscosity of the polyhydroxy resin (P2) is within the above range, the polyhydroxy resin (P2) has low viscosity and excellent fluidity, and therefore the cured product obtained from the polyhydroxy resin (P2) has excellent moldability, which is preferable. The polyhydric hydroxy resin (P2) of this embodiment has low viscosity and excellent fluidity, so that the number average molecular weight (Mn) is preferably in the range of 200 to 1500, more preferably in the range of 220 to 1000. 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 even more preferably in the range of 400 to 1200. 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 1.5 to 3, more preferably in the range of 1.1 to 1.8. The polyhydroxy resin (P2) of this embodiment contains repeating units of aromatic compound (A) units, which are phenolic compounds having two or more hydrocarbon groups (Ra) on the aromatic ring, making it easy to control the bonding sites with the aromatic divinyl compound (B1) units. On the other hand, in phenolic resins containing repeating units of phenolic compounds having one or less hydrocarbon groups on the aromatic ring, there are many bonding sites between the phenolic compound and the aromatic divinyl compound units, so the resulting phenolic resins tend to have a wide variety of chain lengths or chemical structures, resulting in a broad molecular weight distribution. Therefore, the polyhydroxy resin (P2) of the present disclosure can exhibit more uniform molecular weights and more homogeneous properties than conventional phenolic resins.

[0041] <Glycidyl ether (E2)> The glycidyl ether (E2) in this embodiment is a compound obtained by glycidyl-etherifying the polyhydroxy compound (P2), and more specifically, a compound in which one or more hydroxyl groups in the polyhydroxy compound (P2) have been substituted with a glycidyl group. In other words, the glycidyl ether (E2) in this embodiment may have a structure in which an aromatic compound (A) unit containing an aromatic ring having a phenolic hydroxyl group and two or more hydrocarbon groups is chemically bonded to an aromatic divinyl compound (B1) unit, and optionally an aromatic monovinyl compound (B2) unit is chemically bonded to the aromatic ring in the aromatic compound (A) unit, and the phenolic hydroxyl group has been substituted with a glycidyl ether group. As will be explained later in the section on the production method of the glycidyl ether (E2), the glycidyl ether (E2) can be produced by reacting the polyhydric hydroxy compound (P2) with epihalohydrin.

[0042] The glycidyl ether (E2) in this embodiment preferably has a partial structure represented by the following general formula (V) and / or (VI). [ka] [ka] (In the above general formulas (V) and (VI), R 1 , R 2 , and R 3 each independently represents a hydrocarbon group having 1 to 6 carbon atoms, R 4 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 6 is represented by the general formula (a) [ka] (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 R per phenol ring in the entire glycidyl ether (E2). 6 is the average number of substitutions, and represents a number of 0 to 1. In addition, * in the above general formulas (V) and (VI) represents a bond to another atom.) In the above general formulas (V) and (VI), R 1 ~R 8 represents R in the above general formulas (I) and (II). 1 ~R 8 Since it is similar to the above, it will be omitted here.

[0043] The glycidyl ether (E2) in this embodiment is preferably represented by the following general formula (VII) and / or (VIII). [ka] [ka] (In the above general formulas (VII) and (VIII), G represents a glycidyl group, and R 1 , R 2 , and R 3 each independently represents a hydrocarbon group having 1 to 6 carbon atoms, R 4 and R 5 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, R 6 is represented by the general formula (a) [ka] (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 of 0 to 20, m represents an integer of 0 to 20; p is the average R per phenol ring in the entire glycidyl ether (E2). 6 is the number of substitutions and represents the numbers 0 to 1.) R in general formulas (VII) and (VIII) 1 ~R 8 represents R in the above general formulas (I) and (II). 1 ~R 8 (This is omitted here because it is similar to

[0044] The epoxy equivalent of the glycidyl ether (E2) of this embodiment is preferably 200 to 1500 g / eq, more preferably 220 to 1000 g / eq, and even more preferably 240 to 800 g / eq. The glycidyl ether (E2) of this embodiment preferably has a melt viscosity at 150°C measured with an ICI viscometer of 0.01 to 10 dPa·s, more preferably 0.01 to 5 dPa·s, and even more preferably 0.01 to 1 dPa·s. The glycidyl ether (E2) of this embodiment has low viscosity and excellent fluidity, and therefore preferably has a number-average molecular weight (Mn) in the range of 200 to 1,800, more preferably 250 to 1,500, and even more preferably 430 to 1,500. The weight-average molecular weight (Mw) is preferably in the range of 250 to 2,000, more preferably 300 to 1,800. In another embodiment, it is preferably in the range of 800 to 2,000. The molecular weight distribution (Mw / Mn), expressed as 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, and more preferably 1.1 to 1.8. As described above, the (P2) component has a more uniform molecular weight than conventional phenolic resins, and therefore the glycidyl ether (E2) obtained from the (P2) component can also exhibit uniform molecular weight and homogeneous properties.

[0045] <Method of producing epoxy resin composition> Hereinafter, a method for producing the epoxy resin composition of the present disclosure will be described. The epoxy resin composition of the present embodiment may be produced by any method, and may be any product produced by any method, as long as it contains a glycidyl ether (E1) of a biphenol compound (P1) and a glycidyl ether (E2) of a polyhydric hydroxy resin (P2). Examples of methods for producing such an epoxy resin composition include the following production methods (1) and (2). In the production method (1), a glycidyl etherified product (E1) is synthesized by glycidyl-etherifying a biphenol compound (P1) using epihalohydrin, and separately, a glycidyl etherified product (E2) is synthesized by glycidyl-etherifying a polyhydric hydroxy resin (P2) obtained by reacting an aromatic compound (A) with an aromatic divinyl compound (B1) or the like using epihalohydrin, and a mixture of (containing) these products can be used as the epoxy resin composition of the present disclosure. In addition, in the production method (2), epihalohydrin is added to a mixture of a biphenol compound (P1) and a polyhydric hydroxy resin (P2) obtained by reacting an aromatic compound (A) with an aromatic divinyl compound (B1) or the like, and the biphenol compound (P1) and the polyhydric hydroxy resin (P2) are reacted with the epihalohydrin, respectively, to synthesize a glycidyl etherified product (E3) containing the glycidyl etherified product (E1) and the glycidyl etherified product (E2). A product containing this glycidyl etherified product can be used as the epoxy resin composition of the present disclosure. In particular, the above-mentioned production method (2) is preferred because of its simplicity and excellent workability. Furthermore, in method (2), a prepolymer precursor (biphenol compound (P1)) having ring-assembly hydrocarbons and exhibiting high crystallinity is mixed as a reaction raw material, thereby making it possible to effectively utilize the prepolymer having ring-assembly hydrocarbons, which is difficult to recover as a simple substance due to its high crystallinity. The steps from the production of the polyhydric hydroxy resin (P2) to the production of the epoxy resin composition will be explained below in order.

[0046] <Method for producing polyhydroxy resin (P2)> The method for producing the polyhydric hydroxy resin (P2) will be described below. The method for producing the polyhydric hydroxy resin (P2) in this embodiment is not particularly limited, but for example, the polyhydric hydroxy resin (P2) can be produced by reacting an aromatic compound (A) containing a phenolic hydroxyl group and two or more hydrocarbon groups with an aromatic divinyl compound (B1) (e.g., divinylbenzene), and, if necessary, other compounds such as an aromatic monovinyl compound (B2) (e.g., ethylvinylbenzene), in the presence of an acid catalyst.

[0047] The polyhydric hydroxy resin (P2) obtained by the method for producing the polyhydric hydroxy resin (P2) of the present embodiment can have a hydroxyl group equivalent and the like controlled according to the blending ratio of the aromatic divinyl compound (B1) and the aromatic monovinyl compound (B2) that can be further used. The blending ratio of the aromatic compound (A) and the aromatic divinyl compound (B1) is preferably 0.1 to 1 mol, more preferably 0.1 to 0.8 mol, as the molar ratio of the aromatic divinyl compound (B1) per 1 mol of the aromatic compound (A), taking into consideration the balance of physical properties between moldability during production of the resulting cured product and curability. When the aromatic monovinyl compound (B2) is used in combination, the total molar ratio of the aromatic divinyl compound (B1) and the aromatic monovinyl compound (B2) per 1 mol of the aromatic compound (A) is preferably 0.1 to 1 mol, more preferably 0.1 to 0.8 mol. Regarding the blending ratio of the aromatic compound (A), the aromatic divinyl compound (B1), and the aromatic monovinyl compound (B2), taking into consideration the balance of physical properties such as moldability during production of the resulting cured product and curability, the number of moles of vinyl groups contained in the aromatic divinyl compound (B1) and the aromatic monovinyl compound (B2) per mole of the aromatic compound (A) is preferably 0.1 to 1 mole, and more preferably 0.1 to 0.95 moles.

[0048] In this embodiment, the reaction of the aromatic compound (A) with the aromatic divinyl compound (B1) and / or aromatic monovinyl compound (B2) can be carried out in the presence of an acid catalyst. The acid catalyst can be appropriately selected from well-known inorganic and organic acids. Examples of the acid catalyst include 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, dimethyl sulfate, and diethyl sulfate; Lewis acids such as zinc chloride, aluminum chloride, iron chloride, and boron trifluoride; and solid acids such as ion exchange resins, activated clay, silica-alumina, and zeolites. The amount of the acid catalyst is preferably 0.01 to 50 parts by mass, more preferably 0.01 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the raw materials for the polyhydric hydroxy resin (P2). The reaction is typically carried out at 10 to 250°C for 1 to 20 hours.

[0049] Examples of 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; ethers such as dimethyl ether, diethyl ether, diisopropyl ether, tetrahydrofuran, and dioxane; and aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene.

[0050] Specific methods for carrying out the above reaction include charging all the reaction raw materials at once and reacting them at a predetermined temperature, or charging the aromatic compound (A) and an acid catalyst and maintaining the temperature at a predetermined level while adding dropwise an aromatic divinyl compound (B1) or other compounds (e.g., aromatic monovinyl compound (B2)). The dropwise addition time is usually 1 to 10 hours, preferably 5 hours or less. If a solvent is used after the reaction, the polyhydroxy resin (P2) can be obtained by distilling off the solvent and unreacted materials, if necessary. On the other hand, if no solvent is used, the desired polyhydroxy resin (P2) can be obtained by distilling off the unreacted materials.

[0051] <Glycidyl etherification> In the above production method (1), the reaction of the biphenol compound (P1) with epihalohydrin and the reaction of the polyhydric hydroxy resin (P2) with epihalohydrin can be carried out, for example, in the presence of a basic catalyst, usually at a temperature in the range of 20 to 150°C, preferably 30 to 80°C, for 0.5 to 10 hours.

[0052] In the present embodiment, examples of the epihalohydrin include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, etc. The amount of epihalohydrin added is an excess amount per mole of the total of hydroxyl groups possessed by the biphenol compound (P1) or the polyhydric hydroxy resin (P2), and is generally 1.5 to 30 moles, and preferably 2 to 15 moles.

[0053] Examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. Among these, alkali metal hydroxides are preferred because of their excellent catalytic activity, and specifically, sodium hydroxide and potassium hydroxide are more preferred. These basic catalysts may be used in a solid state or in the form of an aqueous solution. The amount of the basic catalyst added is preferably in the range of 0.9 to 2 moles per mole of the total hydroxyl groups of the biphenol compound (P1) or the polyhydric hydroxy resin (P2).

[0054] In this embodiment, the reaction of the biphenol compound (P1) and / or the polyhydric hydroxy resin (P2) with epihalohydrin may be carried out in an organic solvent. Examples of the organic solvent include 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; cellosolves such as methyl cellosolve and ethyl cellosolve; ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane; and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, and dimethylformamide. These organic solvents may be used alone or in combination to adjust the polarity.

[0055] After the reaction with epihalohydrin is completed, excess epihalohydrin can be distilled off to obtain a crude product. If necessary, the obtained crude product may be dissolved again in an organic solvent, and a basic catalyst may be added to carry out the reaction again to reduce the hydrolyzable halogen. Salts produced in the reaction can be removed by filtration, washing with water, or the like. Furthermore, when an organic solvent is used, the organic solvent may be distilled off to extract only the resin solid content, or the solution may be used as is.

[0056] In the production method (1), the mass ratio of the glycidyl ether (E1) to the glycidyl ether (E2) is not particularly limited, but in order to obtain an epoxy resin having excellent fluidity and excellent toughness and low moisture absorption in the cured product, the proportion of the glycidyl ether (E1) to the total mass of both ((E1)+(E2)) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 5% by mass or more. The upper limit is preferably 40% by mass or less, more preferably 25% by mass or less.

[0057] In the production method (2), the mass ratio of the biphenol compound (P1) to the total mass of the biphenol compound (P1) and the polyhydric hydroxy resin (P2) in the mixture is preferably 0.5 mass% or more, more preferably 1 mass% or more, and even more preferably 5 mass% or more, in order to obtain an epoxy resin having excellent fluidity and a low hot elastic modulus and low moisture absorption in the cured product. The upper limit is preferably 40 mass% or less, and more preferably 25 mass% or less. The reaction of the mixture of the biphenol compound (P1) and the polyhydric hydroxy resin (P2) with epihalohydrin can be carried out in the same manner as in the production method (1). The amount of epihalohydrin added is an excess, typically 1.5 to 30 moles, and preferably 2 to 15 moles, per mole of the total hydroxyl groups possessed by the biphenol compound (P1) and the polyhydric hydroxy resin (P2). As in the production method for epoxy resins (1), a basic catalyst can be used, and the amount of the basic catalyst added is preferably 0.9 to 2 moles per mole of the total hydroxyl groups possessed by the biphenol compound (P1) and the polyhydric hydroxy resin (P2).

[0058] <Curable composition> The present disclosure relates to a curable composition containing an epoxy resin composition and a curing agent. The epoxy resin composition also contains a glycidyl ether (E1) and a glycidyl ether (E2). By including the epoxy resin composition in the curable composition, the resulting cured product has improved moisture absorption resistance, adhesion to metal materials, and elastic modulus at elevated temperatures, which is advantageous because it can reduce warpage in semiconductor encapsulation materials, for example.

[0059] In the curable composition of the present disclosure, any curing agent capable of undergoing a crosslinking reaction with the epoxy groups of the epoxy resin composition (or the epoxy groups of the glycidyl ethers (E1) and (E2)) can be used without particular limitation. Examples of the curing agent include phenol curing agents, amine curing agents, acid anhydride curing agents, active ester resins, and cyanate ester resins. The curing agents may be used alone or in combination of two or more.

[0060] Examples of the phenol curing agent include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zylok resin), naphthol aralkyl resin, triphenylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl modified phenol resin (bismethylene group phenol Examples of suitable polyphenolic hydroxyl group-containing compounds include polyphenolic hydroxyl group-containing compounds in which phenol nuclei are linked together, biphenyl-modified naphthol resins (polyphenolic naphthol compounds in which phenol nuclei are linked together via bismethylene groups), aminotriazine-modified phenolic resins (polyphenolic hydroxyl group-containing compounds in which phenol nuclei are linked together via melamine, benzoguanamine, or the like), and alkoxy-group-containing aromatic ring-modified novolac resins (polyphenolic hydroxyl group-containing compounds in which phenol nuclei and alkoxy-group-containing aromatic rings are linked together via formaldehyde). Among these, phenolic novolac resins are more preferred from the viewpoint of moldability. The phenolic hydroxyl group-containing compounds may be used alone or in combination of two or more.

[0061] Examples of the amine curing agent include aliphatic amines such as diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine, menthenediamine (MDA), isophoronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N,N-dimethylpiperazine, and triethylenediamine; and aromatic amines such as m-xylenediamine (XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol.

[0062] Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bistrimellitate, glycerol tristrimellitate, maleic anhydride, tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, methylbutenyl tetrahydrophthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, and methylcyclohexene dicarboxylic anhydride.

[0063] In the curable composition of the present embodiment, the amount of curing agent to be blended relative to the amount of the epoxy resin composition is not particularly limited, for example, as a functional group equivalent ratio (e.g., hydroxyl group equivalent of the phenolic curing agent / epoxy equivalent of the epoxy resin composition). However, in terms of good mechanical properties of the resulting cured product, the amount is preferably such that the active groups in the curing agent are 0.5 to 1.5 equivalents, and more preferably 0.8 to 1.2, per 1 equivalent of the total of the epoxy groups in the epoxy resin composition and other epoxy resins used in combination as needed.

[0064] In addition to the epoxy resin composition and the curing agent, the curable composition of this embodiment can contain other resins in combination, as long as the effects of the present disclosure are not impaired. Examples of such resins include epoxy resins other than the epoxy resin compositions (glycidyl ethers (E1) and (E2)), maleimide resins, bismaleimide resins, polymaleimide resins, polyphenylene ether resins, polyimide resins, benzoxazine resins, triazine-containing cresol novolac resins, styrene-maleic anhydride resins, allyl group-containing resins such as diallyl bisphenol and triallyl isocyanurate, polyphosphate esters, and phosphate ester-carbonate copolymers. These other resins may be used alone or in combination of two or more.

[0065] <Solvent> The curable composition of the present disclosure may be prepared without solvent or may contain a solvent, which has the function of adjusting the viscosity of the curable composition, for example.

[0066] 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; ester solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene, and 1,2,4-trimethylbenzene; and amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

[0067] The amount of the solvent is preferably 10 to 90% by mass, and more preferably 20 to 80% by mass, based on the total mass of the curable composition. A solvent amount of 10% by mass or more is preferred because of excellent handleability. On the other hand, a solvent amount of 90% by mass or less is preferred from the standpoint of economy.

[0068] <Additives> The curable composition of the present disclosure may contain various additives, such as a curing accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a release agent, a pigment, a colorant, and an emulsifier, as needed.

[0069] <Curing accelerator> The curing accelerator is not particularly limited, but examples thereof include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, urea-based curing accelerators, etc. The curing accelerators may be used alone or in combination of two or more.

[0070] Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, tripartylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organic phosphite compounds such as trimethyl phosphite and triethyl phosphite; and phosphonium salts such as ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphinetriphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, butylphenylphosphonium dicyanamide, and tetrabutylphosphonium decanoate.

[0071] 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), and 1,5-diazabicyclo[4.3.0]-nonene-5 (DBN).

[0072] Examples of the imidazole-based 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 ... Examples of such an alkyl acrylate include ethyl-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-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, and 2-methylimidazoline.

[0073] 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, and 1-phenylbiguanide.

[0074] Examples of the urea-based curing accelerator include 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, and 3-(3,4-dichlorophenyl)-1,1-dimethylurea.

[0075] Of the above curing accelerators, it is preferable to use triphenylphosphine as a phosphorus-based compound or 1,8-diazabicyclo-[5.4.0]-undecene (DBU) as a tertiary amine, particularly when used for semiconductor encapsulation materials, because they have excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc.

[0076] The amount of the curing accelerator can be adjusted as appropriate to obtain the desired curability, but is preferably 0.01 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the total amount of the mixture of the epoxy resin and the curing agent. When the amount of the curing accelerator is within the above range, the curability and insulation reliability are excellent, which is preferable.

[0077] <Flame retardant> The flame retardant is not particularly limited, but examples thereof include inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, halogen-based flame retardants, etc. The flame retardants may be used alone or in combination of two or more.

[0078] The inorganic phosphorus-based flame retardant is not particularly limited, but examples thereof include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and phosphoric acid amides.

[0079] The organic phosphorus flame retardant is not particularly limited, but examples thereof include 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, and stearyl acid phosphate. phosphate esters such as isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, and (2-hydroxyethyl) methacrylate acid phosphate; diphenylphosphines such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and diphenylphosphine oxide; 10-(2,5-dihydroxyphenyl)-10H-9-oxa phosphorus-containing phenols such as 10-phosphaphenanthrene-10-oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphosphinyl-1,4-dioxynaphthalene, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol, and 1,5-cyclooctylenephosphinyl-1,4-phenyldiol; 9,10-dihydro-9-oxa-10-phos cyclic phosphorus compounds such as 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; and compounds obtained by reacting the above-mentioned phosphate esters, diphenylphosphine, or phosphorus-containing phenols with epoxy resins, aldehyde compounds, or phenol compounds.

[0080] The halogen-based flame retardant is not particularly limited, but examples thereof include 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, and tetrabromophthalic acid.

[0081] The amount of the flame retardant to be added is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin.

[0082] <Inorganic fillers> The inorganic filler is not particularly limited, but may include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, 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 titanate zirconate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black, etc. Among these, silica is preferred. In this case, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. can be used as the silica. Among these, fused silica is preferred because it allows for a larger amount of inorganic filler to be incorporated. The fused silica can be used in either crushed or spherical form, but it is preferable to mainly use spherical fused silica in order to increase the amount of fused silica blended and suppress an increase in the melt viscosity of the curable composition. Furthermore, in order to increase the amount of spherical silica blended, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The inorganic fillers can be used alone or in combination of two or more types.

[0083] The inorganic filler may be surface-treated as needed. The surface treatment agent that can be used is not particularly limited, but may include aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, and titanate coupling agents. Specific examples of the surface treatment agent include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and hexamethyldisilazane.

[0084] The blending amount of the inorganic filler is preferably 0.5 to 95 parts by mass per 100 parts by mass of the total amount of the mixture of the epoxy resin and the curing agent. When the blending amount of the inorganic filler is within this range, excellent flame retardancy and insulation reliability are achieved, which is preferable. In addition to the inorganic filler, an organic filler such as polyamide particles can be added within a range that does not impair the properties of the present disclosure.

[0085] The present disclosure relates to a cured product of the curable composition. By using the epoxy resin composition, a cured product obtained from the curable composition containing the epoxy resin composition can exhibit low moisture absorption, a low hot elastic modulus, or high adhesion to metal materials, which is a preferred embodiment. Regarding a method for obtaining a cured product by a curing reaction of the curable composition, for example, the heating temperature during heat curing is not particularly limited, but is typically 100 to 300°C, and the heating time is typically 1 to 24 hours.

[0086] The cured product of this embodiment preferably has a moisture absorption rate of 1.3% or less. The moisture absorption rate can be measured by the same method as the evaluation method described in the Examples section.

[0087] Furthermore, the cured product of this embodiment has a Charpy impact strength of 3 J / cm 2 It is preferable that the concentration is 3.5 J / cm or more. 2More preferably, it is 4 J / cm or more. 2 The Charpy impact strength was measured in accordance with JIS K 6911 by transfer molding at 175°C for 120 seconds under a molding pressure of 6.9 MPa, followed by post-curing at 175°C for 5 hours to prepare a test piece for the Charpy impact strength test, which was then measured using a Pendulum Impact Tester Zwick 5102.

[0088] <Semiconductor encapsulation materials> The present disclosure relates to a semiconductor encapsulation material containing the curable composition. The semiconductor encapsulation material obtained using the curable composition has low viscosity and excellent flowability due to the use of the epoxy resin composition, and further has improved moisture absorption, hot elastic modulus, and adhesion to metal materials, and therefore has excellent processability, moldability, and reflow resistance in the manufacturing process, which is a preferred embodiment.

[0089] The curable composition used in the semiconductor encapsulation material may contain an inorganic filler, and the filling rate of the inorganic filler may be, for example, in the range of 0.5 to 95 parts by mass per 100 parts by mass of the curable composition.

[0090] Examples of a method for obtaining the semiconductor encapsulating material include a method in which the curable composition and optional additives are thoroughly melt-mixed, as needed, using an extruder, kneader, roll, or the like until the mixture becomes homogeneous.

[0091] [Semiconductor Devices] The present disclosure relates to a semiconductor device including a cured product of the semiconductor encapsulation material. The semiconductor device obtained using the semiconductor encapsulation material obtained using the curable composition has low viscosity and excellent flowability due to the use of the epoxy resin composition, and further has improved moisture absorption, hot elastic modulus, and adhesion to metal materials, resulting in excellent processability, moldability, and reflow resistance in the manufacturing process, making it a preferred embodiment.

[0092] The semiconductor device can be obtained by molding the semiconductor encapsulating material using a casting machine, a transfer molding machine, an injection molding machine, or the like, and then heat-curing the material at a temperature ranging from room temperature (20°C) to 250°C.

[0093] [Prepreg] The present disclosure relates to a prepreg having a reinforcing substrate and a semi-cured product of the curable composition impregnated into the reinforcing substrate. A method for obtaining a prepreg from the curable composition includes blending an organic solvent (described below) to form a varnish of the curable composition, impregnating a reinforcing substrate (such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, or glass roving cloth) with the curable composition, and then heating the resulting prepreg at a temperature appropriate for the type of solvent used, preferably 50 to 170°C. The mass ratio of the curable composition to the reinforcing substrate used in this process is not particularly limited, but it is generally preferable to prepare the prepreg so that the resin content in the prepreg is 20 to 60% by mass.

[0094] Examples of organic solvents that can be used include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. The selection and appropriate blending amount of the organic solvent can be determined appropriately depending on the application. For example, when a printed circuit board is further produced from the prepreg as described below, it is preferable to use a polar solvent with a boiling point of 160°C or less, such as methyl ethyl ketone, acetone, or dimethylformamide, and it is also preferable to use the solvent in a proportion that results in a non-volatile content of 40 to 80% by mass.

[0095] [Circuit board] The present disclosure relates to a circuit board that is a laminate of the prepreg and copper foil. A method for obtaining a printed circuit board from the curable composition includes laminating the prepreg by a conventional method, overlaying copper foil as appropriate, and subjecting the laminate to heat-pressure bonding at 170 to 300°C under a pressure of 1 to 10 MPa for 10 minutes to 3 hours.

[0096] [Build-up film] The present disclosure relates to a build-up film containing the curable composition. A method for producing the build-up film of the present embodiment includes applying the curable composition to a support film to form a curable composition layer, thereby forming an adhesive film for a multilayer printed wiring board.

[0097] When a build-up film is produced from the curable composition, it is essential that the film softens under the lamination temperature conditions (usually 70 to 140°C) in the vacuum lamination method, and exhibits fluidity (resin flow) that allows resin to fill via holes or through holes present in the circuit board simultaneously with lamination of the circuit board. It is preferable to blend the above-mentioned components so as to exhibit such properties.

[0098] Here, the diameter of the through-holes in the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to make it possible to fill the resin within this range. When laminating both sides of the circuit board, it is desirable to fill about half of the through-holes.

[0099] Specifically, the adhesive film can be produced by preparing the curable composition in a varnish form, applying the varnish to the surface of the support film (Y), and then drying the organic solvent by heating or blowing hot air or the like to form a composition layer (X) made of the curable composition.

[0100] The thickness of the composition layer (X) to be formed is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of a circuit board is usually in the range of 5 to 70 μm, the thickness of the composition layer (X) is preferably in the range of 10 to 100 μm.

[0101] The composition layer (X) in this embodiment may be protected with a protective film described below. By protecting the composition layer (X) with a protective film, it is possible to prevent the adhesion of dust and the like to the surface of the composition layer (X) and to prevent scratches.

[0102] Examples of the support film and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and even release paper and metal foils such as copper foil and aluminum foil. The support film and protective film may be subjected to a mud treatment, a corona treatment, or a release treatment.

[0103] The thickness of the support film is not particularly limited, but is usually in the range of 10 to 150 μm, preferably 25 to 50 μm, and the thickness of the protective film is preferably 1 to 40 μm.

[0104] The support film (Y) is peeled off after laminating it onto the circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the adhesive film is heat cured, adhesion of dust and the like during the curing process can be prevented. When peeling off after curing, the support film is usually subjected to a release treatment in advance.

[0105] [Other uses] The cured product obtained from the curable composition of the present embodiment has excellent properties such as low moisture absorption and high toughness, and therefore can be suitably used not only for applications such as semiconductor encapsulation materials, semiconductor devices, prepregs, circuit boards, and build-up films, but also for various other applications such as build-up boards, adhesives, resist materials, and matrix resins for fiber-reinforced resins, but is not limited to these. [Example]

[0106] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. [Evaluation method] <Epoxy equivalent> Measurement was carried out based on JIS K 7236.

[0107] <Melting Viscosity at 150°C> Measured with an ICI viscometer in accordance with ASTM D4287.

[0108] <Softening Point> The softening point (°C) was measured in accordance with JIS K7234 (ring method). For the handling properties in Table 2, a softening point temperature of less than 50°C was marked as ×, and 50°C or higher was marked as 〇.

[0109] <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 Eluent: Tetrahydrofuran Flow rate 1.0 ml / min Standard: In accordance with the measurement manual of the "GPC Workstation EcoSEC-WorkStation", the following monodisperse polystyrenes with known molecular weights were used. (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 Tosoh Corporation "F-128" Sample: A 1.0% by mass tetrahydrofuran solution (solid content equivalent) of the epoxy resins obtained in the following Synthesis Examples and Examples was filtered through a microfilter (50 μl). The synthesis of the epoxy resins was confirmed from the GPC measurement results. The number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the obtained epoxy resins were also calculated.

[0110] (Synthesis Example 1: Synthesis of polyhydroxy resin (P2-1)) A flask equipped with a thermometer, condenser, distillation column, nitrogen gas inlet, and stirrer was charged with 488.6 g (4.00 mol) of 2,6-xylenol and 244 g of toluene. 4.9 g of p-toluenesulfonic acid was added and the temperature was raised to 115 °C. After confirming complete dissolution of the raw materials, 260.4 g of a mixture of divinylbenzene and ethylvinylbenzene (Nippon Steel Chemical Co., Ltd., "DVB-810") was added dropwise over 2 hours, and the mixture was allowed to react at 115 °C for 1 hour. After the reaction was completed, the temperature was lowered to 80 °C and the mixture was neutralized with aqueous sodium hydroxide. Unreacted 2,6-xylenol and toluene were removed under reduced pressure by heating to obtain polyhydroxy resin (P2-1). The hydroxyl equivalent of the resulting polyhydroxy resin (P2-1) is shown in Table 1.

[0111] (Synthesis Example 2: Synthesis of polyhydroxy resin (P2-2)) A polyhydric hydroxy resin (P2-2) was obtained by carrying out the reaction under the same conditions as in Synthesis Example 1, except that 544.8 g (4.00 mol) of 2,3,6-trimethylphenol was used instead of 488.6 g (4.00 mol) of 2,6-xylenol. The hydroxyl equivalent of the resulting polyhydric hydroxy resin (P2-2) is shown in Table 1.

[0112] (Synthesis Example 3: Synthesis of phenolic resin (1)) Phenolic resin (1) was obtained by synthesis according to the method described in Synthesis Example 1 of Japanese Patent No. 5689230. The hydroxyl group equivalent of the obtained phenolic resin (1) is shown in Table 1.

[0113] [Table 1]

[0114] (Example 1: Synthesis of epoxy resin composition (1)) A flask equipped with a thermometer, dropping funnel, condenser, and stirrer was purged with nitrogen gas. 224.0 g of the polyhydric hydroxy resin (P2-1) obtained in Synthesis Example 1, 56.0 g of 4,4'-biphenol, 1261 g of epichlorohydrin, 390 g of n-butanol, and 90 g of water were charged and dissolved to prepare a mixed solution. The mixed solution was heated to 60°C, and 392 g of a 20% by weight aqueous sodium hydroxide solution was added dropwise over 5 hours. Stirring was then continued under the same conditions for 0.5 hours. Unreacted epichlorohydrin was then removed by vacuum distillation. Subsequently, 638 g of methyl isobutyl ketone was added to the crude epoxy resin and dissolved to obtain a crude epoxy resin solution. 24 g of a 5% by weight aqueous sodium hydroxide solution was added to the crude epoxy resin solution, and the mixture was reacted at 80°C for 2 hours. The mixture was then washed three times with 180 g of water until the pH of the washings became neutral. The system was then dehydrated by azeotropy, and after microfiltration, the solvent was distilled off under reduced pressure to obtain an epoxy resin composition (1) (containing a glycidyl ether of the polyhydric hydroxy resin (P2-1) and a glycidyl ether of 4,4'-biphenol). The properties of the obtained epoxy resin composition (1) are shown in Table 2.

[0115] (Example 2: Synthesis of epoxy resin composition (2)) The reaction was carried out under the same conditions as in Example 1, except that 224.0 g of polyhydroxy resin (P2-1) was replaced with 238.0 g of polyhydroxy resin (P2-1) and 56.0 g of 4,4'-biphenol was replaced with 42.0 g of 4,4'-biphenol, to obtain epoxy resin composition (2) (= containing a glycidyl ether of polyhydroxy resin (P2-1) and a glycidyl ether of 4,4'-biphenol, but with a different mixing ratio of the two glycidyl ethers from that in epoxy resin composition (1)). The properties of the obtained epoxy resin composition (2) are shown in Table 2.

[0116] (Example 3: Synthesis of epoxy resin composition (3)) The reaction was carried out under the same conditions as in Example 1, except that 224.0 g of "polyhydroxy resin (P2-1)" was replaced with 271.6 g of "polyhydroxy resin (P2-1)" and 56.0 g of "4,4'-biphenol" was replaced with 8.4 g of 4,4'-biphenol, to obtain epoxy resin composition (3) (= containing a glycidyl ether of polyhydroxy resin (P2-1) and a glycidyl ether of 4,4'-biphenol, but with a different mixing ratio between the two glycidyl ethers than in epoxy resin compositions (1) and (2)). The properties of the obtained epoxy resin composition (3) are shown in Table 2.

[0117] (Example 4: Synthesis of epoxy resin composition (4)) The reaction was carried out under the same conditions as in Example 1, except that 224.0 g of "polyhydroxy resin (P2-1)" was replaced with 238.0 g of "polyhydroxy resin (P2-2)" and 56.0 g of "4,4'-biphenol" was replaced with "42.0 g of 4,4'-biphenol," to obtain an epoxy resin composition (4) (containing a glycidyl ether of polyhydroxy resin (P2-2) and a glycidyl ether of 4,4'-biphenol). The properties of the obtained epoxy resin composition (4) are shown in Table 2.

[0118] (Comparative Example 1: Synthesis of epoxy resin composition (5)) The reaction was carried out under the same conditions as in Example 1, except that 238.0 g of polyhydric hydroxy resin (P2-1) was replaced with 280.0 g of phenolic resin (1) and 56.0 g of 4,4'-biphenol was replaced with 0.0 g of 4,4'-biphenol, to obtain an epoxy resin composition (5) (= not containing a glycidyl ether of 4,4'-biphenol). The property values ​​of the obtained epoxy resin composition (5) are shown in Table 2.

[0119] (Comparative Example 2: Synthesis of epoxy resin composition (6)) The phenolic resin (1) synthesized in Synthesis Example 3 above was used as a raw material, and an epoxy resin composition (6) was obtained by synthesis according to Example 2 described in Japanese Patent No. 5689230. The property values ​​of the obtained epoxy resin composition (6) are shown in Table 2.

[0120] (Comparative Example 3: Preparation of epoxy resin composition (7)) As the epoxy resin composition (7), a biphenol-type epoxy resin (YX-4000K manufactured by Mitsubishi Chemical Corporation) was used. The property values ​​of the epoxy resin composition (7) are shown in Table 2.

[0121] [Table 2]

[0122] (Examples 5 to 8 and Comparative Examples 4 to 6) <Preparation of Curable Composition> The epoxy resins, curing agents, and curing accelerators produced in Examples 1 to 4 and Comparative Examples 1 to 3 were blended according to the compositions shown in Table 3 below, and the curable compositions of Examples 5 to 8 and Comparative Examples 4 to 6 (a collective term for the epoxy resin compositions for semiconductor encapsulation of Examples 5 to 8 and the curable compositions of Comparative Examples 4 to 6) were prepared by melt-kneading the components (see Table 3). Cured products for evaluation used in the evaluation of Examples 5 to 8 and Comparative Examples 4 to 6 were prepared from the curable compositions of Examples 5 to 8 and Comparative Examples 4 to 6 by the methods described below, and then moisture absorption and hot elastic modulus were evaluated. The results are shown in Table 3.

[0123] <Preparation of cured product for evaluation> Each of the curable compositions described in Examples 5 to 8 and Comparative Examples 4 to 6 was cured in a normal pressure press at 150°C for 10 minutes so that the thickness of the cured product became 2.4 mm, and then after-cured at 175°C for 5 hours to obtain each cured product for evaluation. <Evaluation of moisture absorption> Each of the cured products for evaluation was cut using a diamond cutter to a size of 75 mm x 25 mm x 2.4 mm (2.4 mm thick), and these were used as test pieces (a) for evaluating moisture absorption. The moisture absorption was evaluated by leaving the test pieces for 300 hours in an environment of temperature / humidity: 85°C / 85%, and then calculating the moisture absorption rate (%) using the following formula. Moisture absorption rate = [(mass of test piece (a) after test - mass of test piece (a) before test) / mass of test piece (a) before test × 100 (%)]

[0124] <Evaluation of elastic modulus when heated> Each of the cured products for evaluation was cut into pieces measuring 5 mm × 54 mm using a diamond cutter, and these were used as test pieces (b) for evaluating the hot elastic modulus. The storage modulus of each test piece (b) was then measured at 260°C using a viscoelasticity measuring device (Rheometrics "Solid Viscoelasticity Measuring Device RSAII"; rectangular tension method: frequency 1 Hz, heating rate 3°C / min).

[0125] [Table 3] Note: The curing agent in Table 3 above is a phenol novolac phenolic resin ("TD-2131" manufactured by DIC Corporation, hydroxyl equivalent: 104 g / eq). The curing accelerator is triphenylphosphine ("TPP" manufactured by Hokko Chemical Industry Co., Ltd.).

[0126] (Examples 9 to 12 and Comparative Examples 7 to 9) The epoxy resins produced in Examples 1 to 4 and Comparative Examples 1 to 3, curing agents, curing accelerators, fused silica, and silane coupling agents were blended according to the compositions shown in Table 4 below, and the components were melt-kneaded using a twin roll mill at a temperature of 80°C for 10 minutes to produce epoxy resin compositions for evaluation (a collective term for the epoxy resin compositions for evaluation in Examples 9 to 12 and the curable compositions in Comparative Examples 7 to 9). Then, the respective test pieces (c) used in Examples 9 to 12 and Comparative Examples 7 to 9 were prepared from the epoxy resin compositions for evaluation of Examples 9 to 12 and Comparative Examples 7 to 9 by the method described below, and then a die shear test was carried out as a test of adhesion to a copper plate. <Preparation of test piece (c)> Each of the above epoxy resin compositions for evaluation was crushed and subjected to a pressure of 70 kg / cm using a transfer molding machine. 2 The specimens were molded onto copper foil at a ram speed of 5 cm / sec, a temperature of 175°C, and a time of 600 sec to obtain test pieces (c) measuring 6 mm x 6 mm x 2 mm (2 mm thick). The copper foil used was EFTEC-64T (0.15 mm thick, manufactured by Furukawa Electric Co., Ltd.).

[0127] <Die shear test (adhesion evaluation)> A die shear test was performed on each test piece (c) using a bonding tester (RHESCA PTR-1102). The shear speed was 0.1 mm / sec, and one test was performed at N5, and the average peel strength (gf) from the copper foil was calculated. The peel strength was expressed as a relative evaluation, and the strength of each test piece (c) was calculated when the test piece (c) of Comparative Example 9 was set to 1.0.

[0128] [Table 4] Note: The curing agent in Table 4 above is a phenol novolac phenolic resin ("TD-2131" manufactured by DIC Corporation, hydroxyl equivalent: 104 g / eq). The curing accelerator is triphenylphosphine ("TPP" manufactured by Hokko Chemical Industry Co., Ltd.). The fused silica is "FB-560" manufactured by Denki Kagaku Co., Ltd., and the silane coupling agent is γ-glycidoxyethoxysilane ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.).

[0129] From the evaluation results in Tables 3 and 4 above, it was confirmed that the epoxy resin compositions obtained in all Examples exhibited excellent adhesion to metal materials and a low hot elastic modulus when cured, compared to the resin compositions obtained in Comparative Examples.

Claims

1. a glycidyl ether (E1) of a biphenol compound (P1); and a glycidyl ether (E2) of a polyhydric hydroxy resin (P2) obtained by reacting, as reaction raw materials, an aromatic compound (A) containing an aromatic ring having a phenolic hydroxyl group and two or more hydrocarbon groups and an aromatic divinyl compound (B1), an epoxy resin composition, wherein the aromatic compound (A) is represented by the following general formula (A1): 【Chemical 1】 (In the above general formula (A1), R a represents a hydrocarbon group having 1 to 6 carbon atoms, and p a represents 2 or 3. Multiple R a s may be the same or different.

2. 2. The epoxy resin composition according to claim 1, wherein the biphenol compound (P1) units in the glycidyl etherified product (E1) are contained in an amount of 0.5% by mass or more and 40% by mass or less based on the total amount of the biphenol compound (P1) units and the polyhydric hydroxy resin (P2) units in the glycidyl etherified product (E2).

3. the polyhydric hydroxy resin (P2) is a polymer obtained by reacting the aromatic compound (A), the aromatic divinyl compound (B1), and the aromatic monovinyl compound (B2) as reaction raw materials, 3. The epoxy resin composition according to claim 1, wherein a mass ratio (B1 / B2) of the aromatic divinyl compound (B1) to the aromatic monovinyl compound (B2) is in the range of 99 / 1 to 50 / 50.

4. The epoxy resin composition according to any one of claims 1 to 3, wherein the aromatic divinyl compound (B1) contains divinylbenzene.

5. 5. The epoxy resin composition according to claim 1, wherein the melt viscosity at 150°C measured with an ICI viscometer is in the range of 0.01 to 5 dPa·s.

6. The method for producing an epoxy resin composition according to any one of claims 1 to 5, wherein a mixture of the biphenol compound (P1) and the polyhydric hydroxy resin (P2) is prepared, and then the mixture is subjected to a glycidyl etherification reaction.

7. A curable composition comprising the epoxy resin according to any one of claims 1 to 5 and a curing agent.

8. A cured product of the curable composition according to claim 7.

9. A prepreg comprising a reinforcing substrate and a semi-cured product of the curable composition according to claim 7 impregnated into the reinforcing substrate.

10. A circuit board which is a laminate comprising the prepreg according to claim 9 and copper foil.

11. A build-up film comprising the curable composition according to claim 7.

12. A semiconductor encapsulant comprising the curable composition according to claim 7.

13. A semiconductor device comprising the cured product of the semiconductor encapsulation material according to claim 12.

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