Epoxy resin

Abstract

To provide an epoxy resin that achieves high compatibility between low viscosity when melted and low moisture absorptivity, low thermal elasticity, and high adhesion of a cured product thereof.SOLUTION: The present invention relates to an epoxy resin that is a glycidyl-etherified, polyhydric hydroxy resin comprising, as a reaction material (1), an aromatic compound (A) comprising a phenolic hydroxy group and two or more hydrocarbon groups in an aromatic ring and an aromatic divinyl compound (B1).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to an epoxy resin. [Background technology]

[0002] Thermosetting resins, which contain epoxy resins and their curing agents as essential ingredients, are widely used in semiconductor encapsulation materials, electronic components such as printed circuit boards, the electronic component field, conductive adhesives such as conductive pastes, other adhesives, matrix materials for composite materials, paints, photoresist materials, color developers, etc. Among these various applications, in the field of semiconductor encapsulation materials, there is a strong demand for miniaturization and high integration of electronic devices, and there is a shift to surface mount packages such as BGA and CSP, and the adoption of copper wire, which has high bonding reliability in high temperature environments, is progressing.

[0003] However, copper wires are more susceptible to corrosion than conventional gold wires. When delamination or other interfacial degradation occurs at the interface between the encapsulating resin and the lead frame, moisture concentrates at the delamination site due to capillary action, corroding the chip and wire bonding joints. Furthermore, the moisture expands rapidly during the high-temperature reflow process, causing cracks. Therefore, it is essential for the encapsulating resin to have properties that reduce delamination at the lead frame interface during reflow. Specifically, reduced moisture absorption and elastic modulus, and improved adhesive strength with the lead frame are required.

[0004] In addition to the above-mentioned properties, it is desirable to use semiconductor encapsulation materials with a high filling rate of filler such as silica in the resin material in order to suppress thermal expansion. To increase the filling rate, it is important that the resin material has low viscosity and excellent fluidity.

[0005] Patent Document 1 discloses an epoxy resin, which is a derivative of a polyhydric hydroxy resin obtained by reacting a phenolic compound with an aromatic vinyl compound, as a resin that gives a cured product with excellent fluidity, moisture resistance, low elasticity at high temperatures, flame retardancy, low dielectric properties, etc. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2017-066268 Summary of the Invention [Problem to be solved by the invention]

[0007] However, the technology of Patent Document 1 does not consider at all achieving a high level of compatibility between excellent moldability due to low viscosity when the resin is molten, and low moisture absorption rate of the cured product, low elasticity when heated, and excellent reflow resistance due to high adhesion to adherends such as copper foil.In addition, the properties of the disclosed epoxy resin are insufficient, leaving room for improvement.

[0008] Therefore, the problem to be solved by the present invention is to provide an epoxy resin that can simultaneously achieve low viscosity when melted, and low moisture absorption rate, low elasticity when hot, and high adhesion of the cured product. [Means for solving the problem]

[0009] As a result of extensive research aimed at solving the above-mentioned problems, the present inventors have found that by using an epoxy resin which is a glycidyl ether of a polyhydric hydroxy resin obtained by reacting, as reaction raw materials (1), an aromatic compound (A) having a phenolic hydroxyl group and two or more hydrocarbon groups on the aromatic ring with an aromatic divinyl compound (B1), it is possible to obtain an epoxy resin which has low viscosity when melted, and which can be cured with a low moisture absorption rate, low elasticity when heated, and high adhesion at a high level, thereby completing the present invention. [Effects of the Invention]

[0010] According to the present disclosure, an epoxy resin can be obtained that exhibits low viscosity when melted, and exhibits low moisture absorption, low elasticity when heated, and high adhesion properties in a cured product at a high level. Such an epoxy resin is particularly useful for applications such as electronic component encapsulation materials. [Brief explanation of the drawings]

[0011] [Figure 1] FIG. 1 shows a GPC chart of the polyhydroxy resin (P-1) obtained in the example. [Figure 2] FIG. 2 shows a GPC chart of the polyhydroxy resin (P-2) obtained in the example. [Figure 3] FIG. 3 shows a GPC chart of the epoxy resin (E-1) obtained in the example. [Figure 4] FIG. 4 shows a GPC chart of the epoxy resin (E-2) obtained in the example. DETAILED DESCRIPTION OF THE INVENTION

[0012] The following describes in detail an embodiment of the present invention (hereinafter referred to as the "present embodiment"); however, the present disclosure is not limited to the following description and can be implemented in various modifications within the scope of its gist.

[0013] <Epoxy resin> The present disclosure relates to an epoxy resin that is a glycidyl ether of a polyhydric hydroxy resin obtained by reacting raw materials (1) with an aromatic compound (A) having a phenolic hydroxyl group and two or more hydrocarbon groups on the aromatic ring and an aromatic divinyl compound (B1). The epoxy resin of the present disclosure may also be an epoxy resin obtained by reacting raw materials (2) with the polyhydric hydroxyl resin and an epihalohydrin (C). Furthermore, the epoxy resin of the present disclosure may further include an aromatic monovinyl compound (B2) as the reactant (1). The epoxy resin of the present disclosure is preferable because the aromatic compound (A) that is the reactant (1) has a phenolic hydroxyl group and two or more hydrocarbon groups on the aromatic ring, thereby achieving low viscosity when melted, and a cured product that exhibits low moisture absorption, low elasticity at high temperatures, and high adhesion.

[0014] 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 precursor compound for obtaining a target polymer compound (epoxy resin) or its precursor compound (e.g., polyhydroxy resin) through a chemical reaction (e.g., polymerization reaction, etherification reaction).

[0015] <Polyhydroxy resin> The "polyhydroxy resin" in this embodiment is a polyhydroxy resin obtained by reacting raw materials (1) with 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 the raw material (1). In other words, the polyhydroxy resin in this embodiment has a structure in which aromatic compound (A) units containing an aromatic ring having a phenolic hydroxyl group and two or more hydrocarbon groups are chemically bonded to aromatic divinyl compound (B1) units, and, if necessary, aromatic monovinyl compound (B2) units are chemically bonded to the aromatic ring in the aromatic compound (A) units. In this specification, the term "unit" refers to a repeating unit of a chemical structure formed during reaction or polymerization. In the present embodiment, the aromatic compound (A), which is a phenolic compound having two or more hydrocarbon groups in the 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 (=curable composition) can be provided that, when cured, exhibits excellent peel strength against 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 and the epoxy resin of the present disclosure, which is a glycidyl ether of the polyhydroxy resin.

[0016] -Aromatic compound (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.

[0017] 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 an aliphatic hydrocarbon group having 1 to 6 carbon atoms. The aliphatic hydrocarbon group may be either linear or branched. Furthermore, 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 pronounced the effect of the present invention (low viscosity when melted). Furthermore, the higher the molecular weight of the hydrocarbon group (Ra), the more pronounced the effect of the present invention (low moisture absorption when cured).

[0018] The hydrocarbon group (R a The number of the hydrocarbon groups (R a ) is 2 or more, the composition can exhibit low viscosity and low moisture absorption, as well as excellent peel strength to metal materials and a low modulus of elasticity when heated. The hydrocarbon group (R a The upper limit of the number of the hydrocarbon groups (R ) 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, a ) is three or less.

[0019] In addition, the hydrocarbon group (R a By making the number of (B1) groups 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 with a uniform chemical structure or chain length, and as a result, it becomes easier to exhibit low viscosity when melted, or a cured product with low moisture absorption, low elasticity when heated, or high adhesion.

[0020] 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).

[0021] This allows the cationoid reagent formed from the aromatic divinyl compound (B1) to be described later to react with ArS 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 aBy 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).

[0022] For example, when the aromatic compound (A) has a phenol skeleton having one benzene ring and one hydroxyl group, it is preferable that at least one carbon atom among the 2-, 4-, and 6-positions is substituted with a hydrogen atom. This allows the cationoid reagent formed from the aromatic divinyl compound (B1) described below to easily attack at least one carbon atom among the 2-, 4-, and 6-positions, which are the ortho- and para-positions of the phenol nucleus, which have high electron density. Similarly, in an unsubstituted naphthalene ring, the carbon atoms at the 1-, 4-, 5-, and 8-positions 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 having one naphthalene ring and one hydroxyl group, the carbocation generated from the aromatic divinyl compound (B1) is likely to react with the 1- and 3-positions. Therefore, for example, the hydrogen atom of the CH group at the 1-position can be easily substituted with 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.

[0023] From the above, two or more hydrocarbon groups (R a ) is thought to make it easier to control the resin structure.

[0024] 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.

[0025] The aromatic compound (A), which is the reaction raw material (1) for the polyhydric hydroxy resin in this embodiment, can be represented by, for example, the following general formula (A1). [ka]

[0026] (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, and p a represents 2 or 3. Multiple R a may be the same or different.) In the general formula (A1), the hydrocarbon group having 1 to 6 carbon atoms is the hydrocarbon group (R a )

[0027] -Aromatic divinyl compound (B1)- The aromatic divinyl compound (B1) in this embodiment may be any compound having two vinyl groups as substituents on the aromatic ring and capable of reacting with the aromatic compound (A). Examples of the aromatic divinyl compound (B1) include divinylbenzene, divinylbiphenyl, divinylnaphthalene, and various compounds in which one or more alkyl or alkoxy groups, halogen atoms, or the like are substituted on the aromatic ring. The alkyl group may be either linear or branched. In particular, from the viewpoint of exhibiting excellent peel strength against metal materials and a low modulus of elasticity under heat, it is preferable that the alkyl or alkoxy group have 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. As mentioned above, the ArS reaction can be carried out by the cationoid reagent formed from the aromatic divinyl compound (B1). E By this reaction, the aromatic divinyl compound (B1) can be introduced into a specific position of the ring in the aromatic compound (A), which makes it easier to obtain a polyhydric hydroxy resin (P2) with a uniform chemical structure or chain length, thereby providing an epoxy resin composition that exhibits excellent peel strength against metal materials and a low modulus of elasticity when heated.

[0028] 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.

[0029] 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.

[0030] The aromatic divinyl compound (B1), which is the reaction raw material (1) for the polyhydric hydroxy resin of the present disclosure, can be represented by the following formula (B1). [ka]

[0031] (In the above general formula (B1), Rb1 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 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.) In the above general formula (B1), the alkyl group or alkoxy group having 1 to 4 carbon atoms is the same as the alkyl group or alkoxy group described above.

[0032] -Aromatic monovinyl compound (B2)- In the present embodiment, the polyhydroxy resin may contain, as a reaction raw material, an aromatic compound (A) and an aromatic divinyl compound (B1), as well as other compounds. Examples of such other compounds include an aromatic monovinyl compound (B2). That is, the polyhydroxy resin of the present embodiment preferably uses, as reaction raw materials (1), an aromatic compound (A), an aromatic divinyl compound (B1), and an aromatic monovinyl compound (B2). The polyhydroxy resin (P2) of the present embodiment preferably uses, as reaction raw materials, an aromatic monovinyl compound (B2) in addition to the aromatic compound (A) and the aromatic divinyl compound (B1). When the resulting polyhydroxy resin (P2) is used as a semiconductor encapsulation material, the resin exhibits excellent fluidity and a cured product with a low modulus of elasticity at elevated temperatures. 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).

[0033] 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.

[0034] 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 being able to reduce the elastic modulus when heated, alkylvinylbenzenes and compounds thereof having a substituent on the aromatic ring are preferred, and ethylvinylbenzene is more preferred. Furthermore, the substitution positions of the vinyl group and the ethyl group in the 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 the ethylvinylbenzene is more preferably 40% by mass or more, and even more preferably 50% by mass or more, based on the total amount of ethylvinylbenzene.

[0035] The aromatic monovinyl compound (B2) that can be used as the reaction raw material (1) for the polyhydric hydroxy resin of the present disclosure can be represented by the following general formula (B2). [ka]

[0036] (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.) 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.

[0037] When the aromatic monovinyl compound (B2) is used as a reaction raw material for the polyhydroxy resin 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. When the mass ratio is within the above range, the handleability of the resulting polyhydroxy resin and the moldability and curability during the production of the epoxy resin obtained from the polyhydroxy resin can be balanced, which is preferable.

[0038] <Preferred Form of Polyhydric Hydroxy Resin> Hereinafter, preferred embodiments of the polyhydric hydroxy resin 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 only, and the scope of the present disclosure is not limited to the following chemical structural formula.

[0039] The polyvalent hydroxy resin 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. 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.)

[0040] In the above general formulas (I) and (II), the hydrocarbon group having 1 to 6 carbon atoms is preferably the same as defined above as the hydrocarbon group (Ra). 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.

[0041] In the above general formula (a), R7 is preferably an alkyl group having 1 to 4 carbon atoms.

[0042] 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-.

[0043] The polyvalent hydroxy resin 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), 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, m represents an integer of 0 to 20; n 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 ~R8 (This is omitted here because it is similar to

[0044] The hydroxyl group equivalent of the polyvalent hydroxy resin of the present 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 is measured by a method based on the neutralization titration method specified in JIS K 0070 (1992).

[0045] The polyhydric hydroxy resin 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, and more preferably in the range of 200 to 1000. The weight average molecular weight (Mw) of the polyhydric hydroxy resin is preferably in the range of 300 to 2000, and more preferably in the range of 400 to 1500. 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 1.1 to 3, and more preferably in the range of 1.1 to 1.8. The polyhydric hydroxy resin of the present embodiment has two or more hydrocarbon groups (R a Since the repeating units of the polyhydroxy resins disclosed herein are aromatic compound (A) units, which are phenolic compounds having one or less hydrocarbon groups on the aromatic ring, it is easy to control the bonding sites with the aromatic divinyl compound (B1) units. On the other hand, in phenolic resins having 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 chain lengths or chemical structures of the resulting phenolic resins tend to be diverse and the molecular weight distribution tends to be broad. Therefore, the polyhydroxy resins disclosed herein can exhibit more uniform molecular weights and more homogeneous properties than conventional phenolic resins.

[0046] <Preferred embodiments of the epoxy resin of the present disclosure> <<Preferred Structure>> The epoxy resin of the present disclosure is a compound obtained by glycidyl-etherifying the polyhydroxy compound of the present embodiment, and more specifically, a compound in which the hydrogen atoms in one or more phenolic hydroxyl groups in the polyhydroxy compound are substituted with glycidyl groups. In other words, the epoxy resin of the present disclosure may have a structure in which aromatic compound (A) units containing an aromatic ring having a phenolic hydroxyl group and two or more hydrocarbon groups are chemically bonded to aromatic divinyl compound (B1) units, and optionally aromatic monovinyl compound (B2) units are chemically bonded to the aromatic ring in the aromatic compound (A) units, and the hydrogen atoms in the phenolic hydroxyl groups are substituted with glycidyl ether groups. As will be explained later in the section on the method for producing the epoxy resin of the present disclosure, the epoxy resin of the present disclosure can be produced by reacting a polyvalent hydroxy compound with an epihalohydrin.

[0047] The epoxy resin of the present disclosure 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 epoxy resin of the present disclosure. 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.

[0048] The epoxy resin of the present disclosure 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, m represents an integer of 0 to 20; n represents an integer of 0 to 20, p is the average R per phenol ring in the entire epoxy resin of the present disclosure. 6 is the number of substitutions, and is more preferably a number of 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

[0049] <<Favorable characteristics>> The epoxy equivalent of the epoxy resin of the present disclosure is preferably 200 to 500 g / eq, more preferably 200 to 4000 g / eq, and even more preferably 240 to 350 g / eq. When the epoxy equivalent of the epoxy resin is within the above range, the generation of active hydroxyl groups generated when the epoxy resin reacts with the 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.

[0050] The epoxy resin of the present disclosure 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 0.6 dPa·s. It is preferable for the melt viscosity of the epoxy resin to be within the above range, since the epoxy resin has low viscosity and excellent fluidity, 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.

[0051] The epoxy resin of the present disclosure has a number average molecular weight (Mn) preferably in the range of 430 to 1500, since it has low viscosity and excellent fluidity. Furthermore, the weight average molecular weight (Mw) is preferably in the range of 800 to 2000. The molecular weight distribution (Mw / Mn), which is the ratio of the number average molecular weight (Mn) to the weight average molecular weight (Mw), is preferably in the range of 1.1 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.

[0052] <Epoxy resin manufacturing method> The method for producing the epoxy resin of the present disclosure will be described below. The epoxy resin of the present embodiment may be produced by any method without particular limitation, as long as it is a glycidyl etherified product of the polyhydric hydroxy resin of the present embodiment. Such a method for producing the epoxy resin of the present disclosure includes, for example, a production method including the following steps. Step (1): A step of reacting an aromatic compound (A), an aromatic divinyl compound (B1), and optionally an aromatic divinyl compound (B1) as reaction raw materials (1) to obtain the polyvalent hydroxy compound of the present embodiment; Step (2): A step of reacting the polyvalent hydroxy compound of the present embodiment obtained in Step (1) as the reaction raw material (2) with epihalohydrin to obtain the epoxy resin of the present disclosure. Each step of the method for producing the epoxy resin of the present disclosure will be described below in order.

[0053] <<Step (1): Polyhydroxy Resin Manufacturing Process>> The process for producing the polyvalent hydroxy compound in this embodiment will be described below. The method for producing the polyvalent hydroxy resin in this embodiment is not particularly limited, but for example, the polyvalent hydroxy resin in this embodiment 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.

[0054] The polyvalent hydroxy resin obtained by the method for producing a polyvalent hydroxy resin 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.

[0055] 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.

[0056] 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 used 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 polyhydroxy resin raw materials. The reaction is typically carried out at 10 to 250°C for 1 to 20 hours.

[0057] 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.

[0058] 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 the aromatic divinyl compound (B1) or other compounds (e.g., aromatic monovinyl compound (B2)). The dropwise addition time is typically 1 to 10 hours, preferably 5 hours or less. If a solvent is used after the reaction, the polyhydroxy resin 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 can be obtained by distilling off the unreacted materials.

[0059] <<Step (2): Glycidyl Etherification Step>> In this step, the polyvalent hydroxy compound obtained in step (1) is subjected to an etherification reaction with epihalohydrin, whereby the hydrogen atoms in the phenolic hydroxyl groups of the polyvalent hydroxy compound are substituted with glycidyl groups, and the epoxy resin of the present disclosure is obtained as a glycidyl ether of the polyvalent hydroxy compound.

[0060] The reaction between the polyhydric hydroxy resin and epihalohydrin can be carried out, for example, in the presence of a basic catalyst, usually at a temperature of 20 to 150° C., preferably 30 to 80° C., for 0.5 to 10 hours.

[0061] 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 hydroxyl groups in the polyhydric hydroxy resin, and is generally 1.5 to 30 moles, and preferably 2 to 15 moles.

[0062] 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 in the polyhydric hydroxy resin.

[0063] In this embodiment, the reaction between the polyhydric hydroxy resin and the 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.

[0064] 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.

[0065] <Curable composition> The epoxy resin of the present disclosure can be used to prepare a curable composition. The curable composition may contain the epoxy resin of the present disclosure, an epoxy resin curing agent, and optionally other components (such as an inorganic filler, a silane coupling agent, or a curing aid). By using the epoxy resin of the present disclosure in a curable composition, the curable composition has low viscosity when melted, resulting in excellent moldability. Furthermore, the cured product obtained from the curable composition has excellent reflow resistance because it exhibits a high degree of both low moisture absorption, low elasticity when heated, and high adhesion. Due to these properties, a curable composition using the epoxy resin of the present disclosure exhibits excellent properties, for example, as a semiconductor encapsulation material.

[0066] <<Epoxy resin curing agent>> The curable composition of this embodiment can use any epoxy resin curing agent capable of crosslinking with the epoxy groups of the epoxy resin, without any particular limitations. 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 can be used alone or in combination of two or more.

[0067] 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.

[0068] 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.

[0069] 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.

[0070] In the curable composition of the present embodiment, the amount of curing agent used relative to the amount of epoxy resin used is not particularly limited, for example, as a functional group equivalent ratio (for example, hydroxyl group equivalent of phenolic curing agent / epoxy equivalent of the epoxy resin). 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 per 1 equivalent of the total of the epoxy groups in the epoxy resin and other epoxy resins used in combination as needed, and more preferably 0.8 to 1.2.

[0071] In addition to the epoxy resin 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 resins described above, 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.

[0072] <<Solvent>> The curable composition of the present embodiment may be prepared without a solvent or may contain a solvent, which has the function of adjusting the viscosity of the curable composition.

[0073] 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.

[0074] The amount of the solvent used 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 use amount of 10% by mass or more is preferred from the viewpoint of ease of handling. On the other hand, a solvent use amount of 90% by mass or less is preferred from the viewpoint of economy.

[0075] <<Additives>> The curable composition of the present embodiment 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.

[0076] <<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.

[0077] 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.

[0078] 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).

[0079] 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.

[0080] 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.

[0081] 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.

[0082] 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.

[0083] The amount of the curing accelerator used 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 used is within the above range, excellent curability and insulation reliability are achieved, which is preferable.

[0084] <<Flame retardants>> 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.

[0085] 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.

[0086] 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.

[0087] 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.

[0088] The amount of the flame retardant used is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the epoxy resin of the present disclosure.

[0089] <<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.

[0090] 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.

[0091] The amount of the inorganic filler used 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 of the present disclosure and the curing agent. When the amount of the inorganic filler used 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.

[0092] The present disclosure relates to a cured product of the curable composition of the present embodiment. By using the epoxy resin of the present disclosure, a cured product obtained from the curable composition of the present embodiment containing the epoxy resin of the present disclosure can exhibit low moisture absorption, a low hot elastic modulus, or high adhesion to metal materials, which is a preferred embodiment. As a method for obtaining a cured product by curing the curable composition of the present embodiment, for example, the heating temperature during heat curing is not particularly limited, but is usually 100 to 300°C, and the heating time is 1 to 24 hours.

[0093] 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.

[0094] <Semiconductor encapsulation materials> The present disclosure relates to a semiconductor encapsulation material containing the curable composition of the present embodiment. The semiconductor encapsulation material obtained using the curable composition of the present embodiment uses the epoxy resin of the present disclosure, and therefore has low viscosity and excellent flowability, and further has improved moisture absorption, hot elastic modulus, and adhesion to metal materials, so that it has excellent processability, moldability, and reflow resistance in the manufacturing process, making it a preferred embodiment.

[0095] The curable composition of the present embodiment used for 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 of the present embodiment.

[0096] Examples of a method for obtaining the semiconductor encapsulating material include a method in which the curable composition of the present embodiment and optional additives are further melt-mixed, as necessary, using an extruder, kneader, rolls, or the like until the mixture becomes homogeneous.

[0097] [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 of the present embodiment uses the epoxy resin of the present disclosure, and therefore has low viscosity and excellent flowability. Furthermore, the semiconductor device 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, making it a preferred embodiment.

[0098] 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.

[0099] [Prepreg] The present disclosure relates to a prepreg having a reinforcing substrate and a semi-cured product of the curable composition of the present embodiment 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.

[0100] 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 solvent and the appropriate amount used can be selected 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 it in a proportion that results in a non-volatile content of 40 to 80% by mass.

[0101] [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 of this embodiment 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.

[0102] [Build-up film] The present disclosure relates to a build-up film containing the curable composition of the present embodiment. 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] 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 10 to 100 μm.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] 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.

[0111] [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]

[0112] The present invention will be described in more detail with reference to examples and comparative examples. In the following, "parts" and "%" are by mass unless otherwise specified. The physical properties of the synthesized epoxy resins were measured as follows, and the results are shown in Tables 1 and 2.

[0113] <Measurement of epoxy equivalent> Measured in accordance with JIS K 7236.

[0114] <Melt Viscosity Measurement Method at 150°C> Measured with an ICI viscometer in accordance with ASTM D4287.

[0115] <Measurement of Softening Point> Measured in accordance with JIS K7234.

[0116] <Measurement of GPC> 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: Based on 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 Tosoh Corporation "F-80" Tosoh Corporation "F-128" Sample: A 1.0% by mass tetrahydrofuran solution (based on resin solids content) of the polyhydroxy resin or epoxy resin obtained in the following examples was filtered through a microfilter (50 μl). The synthesis of the resulting polyhydroxy resin or epoxy resin 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 resulting polyhydroxy resin or epoxy resin were also calculated.

[0117] [Production Example 1: Synthesis of polyhydroxy resin (P-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 (DVB-810, manufactured by Nippon Steel Chemical Co., Ltd., divinylbenzene / ethylvinylbenzene mass ratio = 81 / 19) was added dropwise over 2 hours, and the mixture was allowed to react at 115 °C for 1 hour. After completion of the reaction, the temperature was lowered to 80 °C and the mixture was neutralized using an aqueous NaOH solution. Unreacted 2,6-xylenol and toluene were removed under reduced pressure by heating to obtain polyhydroxy resin (P-1). The physical properties of the resulting polyhydroxy resin (P-1) are shown in Table 1, and its GPC chart is shown in Figure 1.

[0118] [Production Example 2: Synthesis of polyhydroxy resin (P-2)] Polyhydroxy resin (P-2) was obtained by the same reaction as in Production Example 1, except that the ingredients were changed to 544.8 g (4.00 mol) of 2,3,6-trimethylphenol, 270 g of toluene, and 5.45 g of p-toluenesulfonic acid. The physical properties of the obtained polyhydroxy resin (P-2) are shown in Table 1, and its GPC chart is shown in Figure 2.

[0119] Comparative Production Example 1: Synthesis of Polyhydroxy Resin (P-3) A flask equipped with a thermometer, condenser, distillation column, nitrogen gas inlet, and stirrer was charged with 627.4 g (6.66 mol) of phenol and 313 g of toluene, and 6.3 g of p-toluenesulfonic acid was added. The temperature was raised to 115°C. After confirming that the raw materials were completely dissolved, 520.8 g of a mixture of divinylbenzene and ethylvinylbenzene (DVB-810, manufactured by Nippon Steel Chemical Co., Ltd.) was added dropwise over 2 hours, and the mixture was allowed to react at 115°C for 2 hours. After the reaction was completed, the temperature was lowered to 80°C and the mixture was neutralized using an aqueous NaOH solution. Unreacted phenol and toluene were removed under reduced pressure by heating to obtain polyhydroxy resin (P-3). The physical properties of the resulting polyhydroxy resin (P-3) are shown in Table 1.

[0120] [Table 1]

[0121] Example 1: Synthesis of epoxy resin (E-1) A flask equipped with a thermometer, dropping funnel, condenser, and stirrer was charged with 300.0 g of the polyhydric hydroxy resin (P-1) obtained in Production Example 1, 923 g (5.0 equivalents) of epichlorohydrin, 238 g of n-butanol, and 40 g of water, and dissolved under nitrogen gas purging. After heating to 60°C, 134 g (1.1 equivalents) of 49% aqueous sodium hydroxide solution was added dropwise over 5 hours. Stirring was continued under the same conditions for 0.5 hours. Unreacted epichlorohydrin was then removed by vacuum distillation. 700 g of methyl isobutyl ketone was added to the resulting crude epoxy resin and dissolved. 15 g of 5% aqueous sodium hydroxide solution was added to this solution and reacted at 80°C for 2 hours. The solution was then washed three times with 190 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 epoxy resin (E-1). The physical properties of the obtained epoxy resin (E-1) are shown in Table 2, and its GPC chart is shown in Figure 3.

[0122] Example 2: Synthesis of epoxy resin (E-2) Epoxy resin (E-2) was obtained by carrying out a reaction in the same manner as in Example 1, except that 300.0 g of polyhydroxy resin (P-2) obtained in Production Example 2 was used instead of polyhydroxy resin (P-1). The physical properties of the obtained epoxy resin (E-2) are shown in Table 2, and the GPC chart is shown in Figure 4.

[0123] Comparative Example 1: Synthesis of Epoxy Resin (E-3) Epoxy resin (E-3) was obtained by carrying out the reaction in the same manner as in Example 1, except that 300.0 g (1.0 equivalent of hydroxyl group) of polyhydroxy resin (P-3) obtained in Comparative Production Example 1 was used instead of polyhydroxy resin (P-1). The physical properties of the obtained epoxy resin (E-3) are shown in Table 2.

[0124] [Table 2]

[0125] [Examples 3 and 4, and Comparative Example 2] <Preparation of Curable Composition> The components were blended in the proportions shown in Table 3 and melt-kneaded to obtain a curable composition. Details of each component are as follows. Hardener: Phenol novolac phenolic resin (DIC Corporation "TD-2131" hydroxyl equivalent 104g / eq) Curing accelerator: Triphenylphosphine ("TPP" manufactured by Hokko Chemical Industry Co., Ltd.)

[0126] <Preparation and evaluation of moisture absorption test specimens> The curable composition obtained above was cured in a normal pressure press at 150°C for 10 minutes so that the thickness of the cured product was 2.4 mm, and then after-cured at 175°C for 5 hours to obtain a cured product for evaluation.

[0127] <Evaluation of moisture absorption> The cured product was cut into 75 mm x 25 mm pieces using a diamond cutter, and these were used as test pieces for evaluating moisture absorption. The moisture absorption was evaluated by leaving the material in an environment of temperature / humidity: 85°C / 85% for 300 hours. The moisture absorption rate was evaluated as [(weight of test piece after test - weight of test piece before test) ÷ weight of test piece before test × 100 (%)].

[0128] <Evaluation of elastic modulus when heated> The cured product was cut into pieces measuring 5 mm x 54 mm using a diamond cutter, and the storage modulus at 260°C was measured using a viscoelasticity measuring device ("Solid Viscoelasticity Measuring Device RSA II" manufactured by Rheometrics, rectangular tension method: frequency 1 Hz, heating rate 3°C / min).

[0129] [Table 3]

[0130] [Examples 5 and 6, and Comparative Example 3] A die shear test was carried out to test the adhesion to the copper plate. Test specimens were prepared as follows.

[0131] The materials shown in Table 4 were melt-kneaded for 10 minutes at 80° C. using a two-roll mill to obtain curable compositions. Details of each component are as follows. Hardener: Phenol novolac phenolic resin (DIC Corporation "TD-2131" hydroxyl equivalent 104g / eq) Curing accelerator: Triphenylphosphine ("TPP" manufactured by Hokko Chemical Industry Co., Ltd.) Fused silica: "FB-560" manufactured by Denki Kagaku Co., Ltd. Silane coupling agent: γ-glycidoxyethoxysilane ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.)

[0132] <Preparation of test specimens> The curable compositions of the above Examples and Comparative Examples were crushed as evaluation compositions, and then crushed using a transfer molding machine at a pressure of 70 kg / cm. 2The test piece was 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 a test piece with dimensions of 6 mm × 6 mm × 2 mm (thickness: 2 mm). The copper foil used was EFTEC-64T (0.15 mm, manufactured by Furukawa Electric Co., Ltd.).

[0133] <Die shear test evaluation> The die shear test was performed using a bonding tester (RHESCA PTR-1102). The shear speed was 0.1 mm / sec, and the shear strength was N5 for one sample. 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 composition is shown in Table 4, where the strength of the molded product of Comparative Example 6 is set to 1.0.

[0134] [Table 4]

[0135] As can be seen from Table 2, the epoxy resins of the present invention have a low melt viscosity, which is expected to result in improved moldability and filler loading. Furthermore, as shown in Table 3, while epoxy resin E-3 has poor moisture absorption, the epoxy resins of the present invention (E-1 and E-2) have excellent moisture absorption, which is expected to result in improved solder crack resistance and connection reliability. Furthermore, the epoxy resins of the present invention have an extremely small storage modulus near the reflow temperature, which is expected to result in improved peel resistance during reflow. Table 4 shows the results of an adhesion test of the epoxy resins of the present invention to copper foil, which confirmed that the epoxy resins of the present invention exhibit excellent adhesion to copper foil.

[0136] As described above, the epoxy resin of the present invention achieves a high degree of compatibility between low viscosity when melted and moisture absorption and low elasticity when heated, which are mutually exclusive properties, and at the same time exhibits excellent adhesion to copper foil, making it particularly useful in the field of electronic materials, etc.

Claims

1. An epoxy resin which is a glycidyl ether of a polyhydric hydroxy resin, which is produced by reacting an aromatic compound (A) having a phenolic hydroxyl group and two or more hydrocarbon groups on an aromatic ring with an aromatic divinyl compound (B1) as reaction raw materials (1), The reaction raw material (1) does not contain dicyclopentadiene, The aromatic compound (A) is an epoxy resin 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 according to claim 1, wherein the polyhydric hydroxy resin and an epihalohydrin (C) are used as reaction raw materials (2).

3. 3. The epoxy resin according to claim 1, further comprising an aromatic monovinyl compound (B2) as the reaction raw material (1).

4. 4. The epoxy resin according to claim 3, wherein the mass ratio ((B1) / (B2)) of the aromatic divinyl compound (B1) to the aromatic monovinyl compound (B2) is 50 / 50 to 99 / 1.

5. 5. The epoxy resin according to claim 1, wherein the hydrocarbon group is an alkyl group having 1 to 6 carbon atoms.

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

7. A cured product of the curable composition according to claim 6.

8. A prepreg comprising a reinforcing substrate and a semi-cured product of the curable composition according to claim 6 impregnated into the reinforcing substrate.

9. A circuit board which is a laminate comprising the prepreg according to claim 8 and copper foil.

10. A build-up film comprising the curable composition according to claim 6.

11. A semiconductor encapsulant comprising the curable composition according to claim 6.

12. A semiconductor device comprising the cured product of the semiconductor encapsulation material according to claim 11.

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