Epoxy resin

Abstract

The objective of this invention is to provide an epoxy resin that can highly balance low viscosity during melting, low moisture absorption of the cured product, low elasticity at heat, and high adhesion. The solution of this invention relates to an epoxy resin, which is an epoxypropyl etherified form of a polyvalent hydroxyl resin using an aromatic compound (A) having phenolic hydroxyl groups and two or more hydrocarbon groups on the aromatic ring and an aromatic diene compound (B1) as reactants (1).

Description

Technical Field

[0001] This invention relates to epoxy resins. Prior Technology

[0002] Thermosetting resins, with epoxy resin and its hardener as essential components, are widely used in semiconductor packaging materials, printed circuit boards and other electronic components, conductive adhesives such as conductive pastes, other adhesives, composite material matrices, coatings, photoresist materials, and color developing materials due to their excellent physical properties such as high heat resistance and moisture resistance. Among these various applications, the semiconductor packaging materials field has high requirements for the miniaturization and high integration of electronic devices, and is developing towards surface mount packaging such as BGA and CSP, as well as the use of copper wires with high bonding reliability in high-temperature environments.

[0003] However, copper wires are more susceptible to corrosion than traditional gold. If interface degradation occurs at the leadframe interface, such as delamination, moisture will concentrate at the delamination point due to capillary action, corroding the chip and wire bonding joints. Furthermore, the rapid expansion of moisture during the high-temperature reflow process becomes a contributing factor to crack formation. Therefore, the properties of the encapsulation resin need to reduce delamination at the leadframe interface during reflow; specifically, this requires reducing moisture absorption, reducing the elastic modulus, and improving adhesion to the leadframe.

[0004] Furthermore, in addition to the aforementioned properties, semiconductor packaging materials also require high filler content, such as silicon dioxide, in the resin material to suppress thermal expansion. To improve the filler content, it is important that the resin material has low viscosity and excellent flowability.

[0005] Patent document 1 discloses an epoxy resin derived from a polyvalent hydroxyl resin obtained by reacting phenolic compounds with aromatic vinyl compounds, which is used as a resin that imparts excellent properties such as flowability, moisture resistance, high temperature low elasticity, flame retardancy, and low dielectric properties to the cured material. [Previous Technical Documents] [Patent Literature]

[0006] [Patent Document 1] Japanese Patent Application Publication No. 2017-066268 Summary of the Invention

[0007] [The problem the invention aims to solve]

[0008] However, the technology in Patent Document 1 does not address the excellent formability resulting from the low viscosity of the resin during melting, the low moisture absorption of the hardened material, the low elasticity during heating, or the excellent reflow resistance resulting from the high adhesion to the adhered materials such as copper foil. Furthermore, the properties of the epoxy resin disclosed are insufficient, leaving room for improvement.

[0009] Therefore, the problem to be solved by the present invention is to provide an epoxy resin that can highly balance low viscosity during melting, low moisture absorption of the hardened product, low elasticity when heated, and high adhesion. [Methods used to solve problems]

[0010] The inventors, through repeated and careful research in order to solve the above-mentioned problems, discovered that by using an epoxy resin of a polyvalent hydroxyl resin containing an aromatic compound (A) having phenolic hydroxyl groups and two or more hydrocarbon groups on the aromatic ring and an aromatic divinyl compound (B1) as reactants (1), an epoxy resin that can highly balance low viscosity during melting, low moisture absorption of the cured product, low elasticity at heat, and high adhesion can be obtained, thus completing the present invention. [Effects of the Invention]

[0011] According to this disclosure, an epoxy resin can be obtained that highly balances low viscosity during melting, low moisture absorption of the cured product, low elasticity at heat, and high adhesion. Such an epoxy resin is particularly useful in applications such as electronic component encapsulation materials. Simple Explanation of the Diagram

[0012] Figure 1 shows the GPC graph of the polyvalent hydroxyl resin (P-1) obtained in the example. Figure 2 shows the GPC graph of the polyvalent hydroxyl resin (P-2) obtained in the example. Figure 3 shows the GPC graph of the epoxy resin (E-1) obtained in the example. Figure 4 shows the GPC graph of the epoxy resin (E-2) obtained in the example. Implementation

[0013] [The form in which the invention is carried out]

[0014] Hereinafter, a detailed description will be given of an embodiment of the present invention (referred to as "this embodiment"), but this disclosure is not limited to the following description and various modifications can be made within the scope of its spirit.

[0015] <Epoxy Resin> This disclosure relates to epoxy resin, specifically an epoxypropyl ether of a polyvalent hydroxyl resin reacted with an aromatic compound (A) having phenolic hydroxyl groups and two or more hydrocarbon groups on its aromatic ring, and an aromatic divinyl compound (B1) as reactants (1). Furthermore, the epoxy resin disclosed herein can also be an epoxy resin reacted with the aforementioned polyvalent hydroxyl resin and epihalohydrin (C) as reactants (2). Moreover, the epoxy resin disclosed herein may further contain an aromatic monovinyl compound (B2) as the aforementioned reactant (1). The epoxy resin disclosed herein, by having phenolic hydroxyl groups and two or more hydrocarbon groups on its aromatic ring, as the aromatic compound (A) of reactant (1), can achieve a high degree of balance between low viscosity during melting, low moisture absorption of the cured product, low elasticity at heat, and high adhesion, thus providing a superior epoxy resin.

[0016] In this specification, "reaction raw materials" refers to compounds used to partially constitute the chemical structure of the target compound in order to obtain the target compound through chemical reactions such as combination or decomposition, excluding substances such as solvents and catalysts that act as auxiliaries in the chemical reaction. Specifically, in this specification, "reaction raw materials" refers to polymer compounds (epoxy resins) or precursor compounds (e.g., polyvalent hydroxyl resins) used to obtain the target polymer compound (epoxy resin) or its precursor compounds (e.g., polyvalent hydroxyl resins) through chemical reactions (e.g., polymerization reactions, etherification reactions).

[0017] <Multivalent Hydroxyl Resins> The "polyvalent hydroxyl resin" in this embodiment refers to a polyvalent hydroxyl resin that uses an aromatic compound (A) containing an aromatic ring with phenolic hydroxyl groups and two or more hydrocarbon groups, and an aromatic divinyl compound (B1) as reactants (1). Furthermore, in this embodiment, an aromatic monovinyl compound (B2) may be further included as the aforementioned reactant (1). In other words, the polyvalent hydroxyl resin in this embodiment contains an aromatic compound (A) unit with an aromatic ring containing phenolic hydroxyl groups and two or more hydrocarbon groups, chemically bonded to an aromatic divinyl compound (B1) unit, and, as needed, has an aromatic monovinyl compound (B2) unit chemically bonded to the aforementioned aromatic ring in the aforementioned aromatic compound (A) unit. Furthermore, the term "unit" as used in this specification refers to a repeating unit of a chemical structure formed during a reaction or polymerization. In this embodiment, since the aromatic compound (A), which is a phenolic compound having two or more hydrocarbon groups in the aromatic ring, is used as the reactant, it becomes easier to control the aromatic divinyl compound (B1) and the reaction site. Therefore, it becomes easier to obtain a polyvalent hydroxyl resin (P2) with a uniform chemical structure or chain length. As a result, an epoxy resin composition (=curable composition) that exhibits excellent peel strength to metal materials and elastic modulus at low heat can be provided. The following describes the aromatic compound (A), aromatic divinyl compound (B1), and aromatic monovinyl compound (B2) that are the constituent components of the reaction raw materials for the polyvalent hydroxyl resin (P2), and then describes the preferred form of the polyvalent hydroxyl resin and the epoxy propylene oxide of the polyvalent hydroxyl resin disclosed herein.

[0018] -Aromatic compound (A)- The aromatic compound (A) in this embodiment has a phenolic hydroxyl group and two or more hydrocarbon groups (Ra) in its aromatic ring. Therefore, the aromatic compound (A) can be a phenolic compound. Furthermore, the aromatic ring forming the central structure of the aromatic compound (A) can be monocyclic or condensed polycyclic, and contains an aromatic hydrocarbon ring. Examples of aromatic hydrocarbon rings include, but are not limited to, benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, and terephthalic rings. From the viewpoint of resin melt viscosity, a monocyclic aromatic ring is preferred.

[0019] In the aromatic compound (A) of this embodiment, regarding the presence of at least two or more hydrocarbon groups (Ra) in the aromatic ring of the aromatic compound (A), examples include hydrocarbon groups having 1 to 6 carbon atoms. Examples of the aforementioned hydrocarbon groups (Ra) include aliphatic hydrocarbon groups having 1 to 6 carbon atoms. The aforementioned aliphatic hydrocarbon groups can be either linear or branched. Furthermore, to prevent addition reactions with other compounds, the aforementioned aliphatic hydrocarbon groups are preferably saturated aliphatic hydrocarbon groups. Examples of saturated aliphatic hydrocarbon groups include, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, hexyl, etc. The lower the molecular weight of the aforementioned hydrocarbon groups, the more significant the effect of the present invention (low viscosity at melt). Furthermore, the higher the molecular weight of the aforementioned hydrocarbon groups (Ra), the more significant the effect of the present invention (low hygroscopicity when formed into a hardened product).

[0020] The aromatic compound (A) of this embodiment has 2 or more hydrocarbon groups (Ra) in its aromatic ring (i.e., the number of substitutions). By having 2 or more hydrocarbon groups (Ra), it can exhibit both low viscosity and low hygroscopicity, as well as excellent peel strength to metallic materials and low thermal modulus of elasticity. The upper limit for the number of the aforementioned hydrocarbon groups (Ra) can be determined from the viewpoint that the aforementioned aromatic ring has phenolic hydroxyl groups and two bonds used for polymerization by simply subtracting 3 from the number of substituted ring-forming atoms in the unsubstituted aromatic ring. For example, when the aforementioned aromatic ring is a benzene ring, the number of the aforementioned hydrocarbon groups (Ra) is 3 or less.

[0021] Furthermore, by making the number of hydrocarbon groups (Ra) in the aromatic ring of the aromatic compound (A) more than 2, it becomes easier to control the aromatic divinyl compound (B1) and the reaction site, thus making it easier to obtain polyvalent hydroxyl resins with uniform chemical structure or chain length. As a result, it becomes easier to achieve low viscosity when melted, or low moisture absorption of the hardened material, low elasticity when heated, or high adhesion.

[0022] Taking the case where the aromatic compound (A) in this embodiment is an aromatic hydrocarbon ring (e.g., benzene ring, naphthalene ring) having a phenolic hydroxyl group and two or more hydrocarbon groups (Ra) as an example, a preferred form of aromatic compound (A) will be described. In this embodiment, it is preferable that among the carbon atoms in the aromatic hydrocarbon ring constituting the aromatic compound (A), the carbon atom with the highest HOMO electron density (Hückel coefficient) is one or more unsubstituted (or substituted with hydrogen atoms).

[0023] This makes it easier to control the ArS E reaction and molecular design induced by the cationic reagent formed by the aromatic divinyl compound (B1) described later. To explain in more detail, if the carbon atom with the highest HOMO electron density (Huckel's law) among the carbon atoms constituting the aromatic hydrocarbon ring of the aromatic compound (A) is unsubstituted (or bonded to a hydrogen atom), then the carbocation of the aromatic divinyl compound (B1), which is a cationic reagent, readily reacts with that carbon atom. Therefore, by controlling the number and position of the hydrocarbon group (Ra), or the number and position of the phenolic hydroxyl groups, the bonding sites or number of bonds with the aromatic divinyl compound can be adjusted. Therefore, it becomes easier to predict and design the chemical structure or molecular chain length of the resulting polyvalent hydroxyl resin (P2).

[0024] For example, when the aromatic compound (A) is a phenolic skeleton having a benzene ring and a hydroxyl group, it is preferable that at least one carbon atom at positions 2, 4, and 6 is substituted with a hydrogen atom. This makes it easier for the cationic reagent formed by the aromatic divinyl compound (B1) to attack at least one carbon atom at positions 2, 4, and 6 (ortho and para positions) where the electron density of the phenolic nucleus is high. 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 having a naphthalene ring and a hydroxyl group, the carbocation formed by the aromatic divinyl compound (B1) readily reacts at positions 1 and 3. Therefore, for example, if a hydrocarbon group (Ra) replaces the hydrogen atom of the CH group at position 1, the carbon atom at position 3 readily undergoes an ArS E reaction, thus allowing control over the chemical structure of the resulting polyvalent hydroxyl resin (P2). Furthermore, for example, when an aromatic compound (A) has a 2,7-hydroxynaphthalene skeleton, the carbocations generated from the aromatic divinyl compound (B1) readily react at positions 1, 3, 6, and 8. Therefore, for example, if the hydrocarbon group (Ra) is bonded to the three carbon atoms at positions 1, 3, and 6, the carbon atom at position 8 readily undergoes an ArS E reaction.

[0025] From the above, it can be concluded that the resin structure becomes easier to control by having two or more hydrocarbon groups (Ra).

[0026] Specific examples of the aromatic compound (A) in this embodiment include, for example, dialkylphenol compounds such as phenols (2,3-phenol, 2,4-phenol, 2,5-phenol, 2,6-phenol, 3,4-phenol, 3,5-phenol), trimethylphenols (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 their derivatives, and compounds with the above-mentioned hydrocarbon group (R a) Compounds that replace two or more hydrogen atoms of the CH group selected from the group consisting of 1-naphthol, 2-naphthol, 1,2-dihydroxynaphthol, 1,3-dihydroxynaphthol, 1,4-dihydroxynaphthol, 1,5-dihydroxynaphthol, 1,6-dihydroxynaphthol, 1,7-dihydroxynaphthol, 1,8-dihydroxynaphthol, 2,3-dihydroxynaphthol, 2,6-dihydroxynaphthol and 2,7-dihydroxynaphthol, namely, dialkylhydroxynaphthol compounds, but not limited to these. Furthermore, the aromatic compound (A) in this embodiment can be used alone or in combination of two or more. However, from the viewpoint of low viscosity upon melting, a dialkylphenol compound is preferred.

[0027] The aromatic compound (A) of the reaction raw material (1) of the polyvalent hydroxy resin in this embodiment can be represented by, for example, the following general formula (A1).

[0028] (In the above general formula (A1), Ra represents a hydrocarbon group with 1 to 6 carbon atoms, preferably a hydrocarbon group with 1 to 3 carbon atoms, and pa represents 2 or 3. The complex Ra can be the same or different.) In the above general formula (A1), the hydrocarbon groups with 1 to 6 carbon atoms are the same as those defined as hydrocarbon groups (Ra) above.

[0029] -Aromatic divinyl compounds (B1)- The aromatic divinyl compound (B1) in this embodiment can be used without particular limitation as long as it has two vinyl groups as substituents on the aromatic ring and can react with the aforementioned aromatic compound (A). Examples of aromatic divinyl compounds (B1) include: divinylbenzene, divinylbiphenyl, divinylnaphthalene, and various compounds in which one or more alkyl or alkoxy groups, halogen atoms, etc., are substituted on the aromatic ring. The aforementioned alkyl group can be either linear or branched. From the viewpoint of exhibiting excellent peel strength and elastic modulus at low temperatures for metallic materials, the aforementioned alkyl or alkoxy group preferably has 1 to 4 carbon atoms. Specifically, examples of the aforementioned alkyl group include: methyl, ethyl, propyl, isopropyl, butyl, tributyl, isobutyl, etc. Examples of the aforementioned alkoxy group include: methoxy, ethoxy, propoxy, butoxy, etc. Examples of the aforementioned halogen atom include: fluorine, chlorine, bromine, etc. As described above, the aromatic divinyl compound (B1) can be introduced into a specific position on the ring of the aromatic compound (A) via an ArSE reaction induced by a cationic reagent formed from the aromatic divinyl compound (B1). This makes it easier to obtain a polyvalent hydroxyl resin (P2) with a uniform chemical structure or chain length, resulting in epoxy resin compositions exhibiting excellent peel strength against metallic materials and a low-heat modulus of elasticity.

[0030] Specific examples of the aromatic divinyl compounds (B1) of this embodiment include, for example: 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-dimethoxy Divinylbenzene compounds, including compounds composed of benzene and its derivatives, and divinylnaphthalene compounds, including compounds composed of 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 its derivatives, but not limited to these.

[0031] Furthermore, the aromatic divinyl compound (B1) in this embodiment can be used alone or in combination of two or more. In particular, from a flowability perspective, as an aromatic divinyl compound (B1), divinylbenzene and compounds having substituents on their aromatic rings are preferred, with divinylbenzene being even more preferred. Furthermore, in this embodiment, the substitution position of the vinyl group in divinylbenzene is not particularly limited, but it is preferred that the intermediate component is the main component. The content of the intermediate component in divinylbenzene is preferably 40% by mass or more, and more preferably 50% by mass or more, relative to the total amount of divinylbenzene.

[0032] The aromatic divinyl compound (B1) of the reaction raw material (1) of the polyvalent hydroxy resin disclosed herein can be represented by the following formula (B1).

[0033] (In the above general formula (B1), Rb1 represents a halogen atom or an alkyl or alkoxy group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and pb1 represents an integer from 0 to 4, preferably 0 to 1. Furthermore, when pb1 is an integer of 2 or more, the complex Rb1s may be the same or different.) In the above general formula (B1), the alkyl or alkoxy group having 1 to 4 carbon atoms is the same as the alkyl or alkoxy group mentioned above.

[0034] -Aromatic monovinyl compounds (B2)- In this embodiment, the polyvalent hydroxyl resin, in addition to aromatic compound (A) and aromatic divinyl compound (B1), can further use other compounds as reactants. Examples of such other compounds include aromatic monovinyl compound (B2). That is, the polyvalent hydroxyl resin in this embodiment preferably uses aromatic compound (A), aromatic divinyl compound (B1), and aromatic monovinyl compound (B2) as reactants (1). In this embodiment, the polyvalent hydroxyl resin (P2), in addition to the aforementioned aromatic compound (A) and aromatic divinyl compound (B1) as reactants, uses aromatic monovinyl compound (B2). When the resulting polyvalent hydroxyl resin (P2) is used as a semiconductor packaging material, the resin exhibits excellent flowability, and its cured product has a lower thermal modulus of elasticity, which is therefore preferable. Furthermore, the use of the aforementioned aromatic monovinyl compound (B2) is also beneficial for improving moisture resistance. Furthermore, aromatic monovinyl compounds (B2) also generate carbocations in the same way as aromatic divinyl compounds (B1). Therefore, among the carbon atoms in the aromatic hydrocarbon ring that constitutes aromatic compound (A), the carbon atoms with the largest HOMO electron density (Huckel coefficient) are more likely to react.

[0035] The aromatic monovinyl compound (B2) in this embodiment can be exemplified by, for example, vinylbenzene, vinylbiphenyl, vinylnaphthalene, and various compounds in which one or more alkyl or alkoxy groups, halogen atoms, or other substituents are substituted on the aromatic ring. The aforementioned alkyl or alkoxy groups can be either straight-chain or branched, and may contain unsaturated bonds in their structure. Where low hygroscopicity is important, the aforementioned alkyl or alkoxy groups are preferably groups having 1 to 4 carbon atoms. Specifically, examples of the aforementioned alkyl groups include: methyl, ethyl, propyl, isopropyl, butyl, tributyl, isobutyl, etc. Examples of the aforementioned alkoxy groups include: methoxy, ethoxy, propoxy, butoxy, etc. Examples of the aforementioned halogen atoms include: fluorine atoms, chlorine atoms, bromine atoms, etc.

[0036] Specific examples of the aromatic monovinyl compounds (B2) of this embodiment include, for example: styrene; fluorostyrene; vinylbenzyl chloride; alkylvinylbenzenes (o-, m-, p-methylstyrene; o-, m-, p-ethylvinylbenzene); o-, m-, p-(chloromethyl)styrene and compounds thereof; biphenyl compounds such as compounds such as compounds such as 4-vinylbiphenyl, 4-vinyl-p-terphenyl and compounds thereof; and vinylnaphthalenes such as compounds such as 1-vinylnaphthalene; 2-vinylnaphthalene and compounds thereof, but are not limited to these. In particular, from the viewpoint of being able to reduce the elastic modulus at heat, alkyl vinylbenzene and compounds having substituents on their aromatic rings are preferred, and ethyl vinylbenzene is even more preferred. Furthermore, the substitution positions of the vinyl and ethyl groups in the aforementioned ethyl vinylbenzene are not particularly limited, but it is preferable that the intermediate is the main component, and the content of the intermediate in the ethyl vinylbenzene is preferably 40% by mass or more, and more preferably 50% by mass or more, relative to the total amount of ethyl vinylbenzene.

[0037] The aromatic monovinyl compound (B2), which can be the reaction raw material (1) of the polyvalent hydroxy resin disclosed herein, can be represented by the following general formula (B2).

[0038] (In the above general formula (B2), Rb2 represents a halogen atom or an alkyl or alkoxy group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, and pb2 represents an integer from 0 to 5, preferably 0 to 1. Furthermore, when pb2 is an integer of 2 or more, the complex Rb2s may be the same or different.) In the above general formula (B2), the alkyl or alkoxy group having 1 to 4 carbon atoms is the same as the alkyl or alkoxy group mentioned above.

[0039] When using the aforementioned aromatic monovinyl compound (B2) as a reactant for the polyvalent hydroxyl resin in this embodiment, the mass ratio ((B1) / (B2)) of the aforementioned aromatic divinyl compound (B1) to the aforementioned aromatic monovinyl compound (B2) is preferably 30 / 70 to 99 / 1, more preferably 50 / 50 to 99 / 1, and even more preferably 50 / 50 to 98 / 2. By using the aforementioned mass ratio within the aforementioned range, a balance can be achieved in the processability of the resulting polyvalent hydroxyl resin, the molding properties during the manufacture of the epoxy resin obtained from the aforementioned polyvalent hydroxyl resin, and the curing properties.

[0040] <Preferred Forms of Polyvalent Hydroxyl Resins> The following description focuses on the morphology of polyvalent hydroxyl resins suitable for this disclosure, using the case where each aromatic ring is a benzene ring as an example. The following chemical structural formulas are illustrative of this disclosure, and the scope of this disclosure is not limited to the following chemical structural formulas.

[0041] The polyvalent hydroxyl resin in this embodiment preferably has a partial structure as shown in the following general formula (I) and / or (II). In the above general formulas (I) and (II), R1, R2, and R3 each independently represent hydrocarbon groups with 1 to 6 carbon atoms. R4 and R5 each independently represent alkyl groups having 1 to 3 hydrogen atoms or carbon atoms. R6 represents the substituent shown in general formula (a). (In general formula (a), R 7 represents a hydrogen atom or a hydrocarbon group with 1 to 6 carbon atoms.) R 8 represents a hydrogen atom or an organic group. p represents the average number of R6 substitutions for each phenolic ring in the polyvalent hydroxyl resin as a whole, indicating a number between 0 and 1. Furthermore, * in the above general formulas (I) and (II) indicates bonds with other atoms.

[0042] In the above general formulas (I) and (II), the hydrocarbon group having 1 to 6 carbon atoms is preferably the same as that defined as the hydrocarbon group (Ra) above. Furthermore, in the above general formulas (I) and (II), R1, R2, and R3 are preferably each independently an alkyl group having 1 to 4 carbon atoms, and R4 and R5 are preferably each independently a hydrogen atom or a methyl group.

[0043] In the above general formula (a), R7 is preferably an alkyl group having 1 to 4 carbon atoms.

[0044] The organogroups in the above general formulas (I) and (II) are monovalent organogroups, preferably alkyl groups with 1 to 6 carbon atoms, alkenyl groups with 1 to 6 carbon atoms, or alkoxy groups with 1 to 6 carbon atoms. Furthermore, one or more of the non-adjacent -CH 2- groups of the alkyl, alkenyl, or alkoxy group may be substituted with -O-, -COO-, or -OCO-.

[0045] The polyvalent hydroxyl resin in this embodiment is preferably represented by the following general formulas (III) and / or (IV). (In the above general formulas (III) and (IV), R1, R2, and R3 each independently represent hydrocarbon groups with 1 to 6 carbon atoms.) R4 and R5 each independently represent alkyl groups having 1 to 3 hydrogen atoms or carbon atoms. R6 represents the substituent shown in general formula (a). (In general formula (a), R 7 represents a hydrogen atom or a hydrocarbon group with 1 to 6 carbon atoms.) R 8 represents a hydrogen atom or an organic group. m represents an integer from 0 to 20. n represents an integer from 0 to 20. p represents the average number of R6 substitutions per phenolic ring, ranging from 0 to 1. R1 to R8 in general formulas (III) and (IV) are the same as R1 to R8 in general formulas (I) and (II) above, therefore they are omitted here.

[0046] Regarding the hydroxyl equivalent of the polyvalent hydroxyl resin in this embodiment, it is preferably 200~500 g / eq, more preferably 200~400 g / eq. Furthermore, the determination of the hydroxyl equivalent of the polyvalent hydroxyl resin in this specification is assumed to be the value determined by the neutralization titration method specified in JIS K 0070 (1992).

[0047] The polyvalent hydroxyl resin of this embodiment has low viscosity and excellent flowability; therefore, its number average molecular weight (Mn) is preferably in the range of 200 to 1500, more preferably in the range of 200 to 1000. Furthermore, the weight average molecular weight (Mw) of this polyvalent hydroxyl resin is preferably in the range of 300 to 2000, more preferably in the range of 400 to 1500. The molecular weight distribution (Mw / Mn) shown by the ratio of the aforementioned weight average molecular weight (Mw) to the aforementioned number average molecular weight (Mn) is preferably in the range of 1.1 to 3, more preferably in the range of 1.1 to 1.8. In this embodiment of the polyvalent hydroxyl resin, the aromatic compound (A) unit of a phenolic compound having two or more hydrocarbon groups (Ra) on the aromatic ring is used as the repeating unit, thus making it easy to control the bonding sites with the aromatic divinyl compound (B1) unit. On the other hand, in phenolic resins using phenolic compounds having one or fewer hydrocarbon groups on the aromatic ring as the repeating unit, there are numerous bonding sites with the aromatic divinyl compound unit of the phenolic compound, thus resulting in numerous chain lengths or chemical structures of the obtained phenolic resin, inevitably showing a tendency to broaden the molecular weight distribution. Therefore, the polyvalent hydroxyl resin disclosed herein is more able to exhibit homogeneous characteristics with consistent molecular weight than conventional phenolic resins.

[0048] <Preferred form of epoxy resin disclosed herein> <<Optimal Structure>> The epoxy resin disclosed herein is a compound in which the polyvalent hydroxyl compound of the present embodiment is etherified with glycidyl ether. More specifically, it is a compound in which the hydrogen atom of one or more phenolic hydroxyl groups in the polyvalent hydroxyl compound is replaced with glycidyl groups. In other words, the epoxy resin disclosed herein contains an aromatic compound (A) unit having an aromatic ring with phenolic hydroxyl groups and two or more hydrocarbon groups, chemically bonded to an aromatic divinyl compound (B1) unit, and, as needed, has an aromatic monovinyl compound (B2) unit chemically bonded to the aforementioned aromatic ring in the aforementioned aromatic compound (A) unit, and may have a chemical structure in which the hydrogen atom of the aforementioned phenolic hydroxyl group is replaced with a glycidyl ether group. The method for manufacturing the epoxy resin disclosed herein is also described later in the section on the method of manufacturing the epoxy resin disclosed herein, which can be manufactured by reacting a polyvalent hydroxyl compound with a surface haloalcohol.

[0049] The epoxy resin disclosed herein preferably has a partial structure as shown in the following general formula (V) and / or (VI). (In the above general formulas (V) and (VI), R1, R2, and R3 each independently represent hydrocarbon groups with 1 to 6 carbon atoms.) R4 and R5 each independently represent alkyl groups having 1 to 3 hydrogen atoms or carbon atoms. R6 represents the substituent shown in general formula (a). (In general formula (a), R 7 represents a hydrogen atom or a hydrocarbon group with 1 to 6 carbon atoms.) R 8 represents a hydrogen atom or an organic group. p represents the average number of R6 substitutions for each phenolic ring in the epoxy resin monolith disclosed herein, indicating a number from 0 to 1. Furthermore, * in the above general formulas (V) and (VI) indicates bonds with other atoms. In the above general formulas (V) and (VI), R1 to R8 are the same as R1 to R8 in the above general formulas (I) and (II), so they are omitted here.

[0050] The epoxy resin disclosed herein is preferably represented by the following general formulas (VII) and / or (VIII). In the above general formulas (VII) and (VIII), G represents glycidyl oxide, and R1, R2, and R3 each independently represent a hydrocarbon group with 1 to 6 carbon atoms. R4 and R5 each independently represent alkyl groups having 1 to 3 hydrogen atoms or carbon atoms. R6 represents the substituent shown in general formula (a). (In general formula (a), R 7 represents a hydrogen atom or a hydrocarbon group with 1 to 6 carbon atoms.) R 8 represents a hydrogen atom or an organic group. m represents an integer from 0 to 20. n represents an integer from 0 to 20. p represents the average R6 substitution number of each phenolic ring in the epoxy resin monolith disclosed herein, preferably a number between 0 and 1. R1 to R8 in general formulas (VII) and (VIII) are the same as R1 to R8 in general formulas (I) and (II) above, therefore they are omitted here.

[0051] <<Superior Characteristics>> The epoxy equivalent of the epoxy resin disclosed herein is preferably 200-500 g / eq, more preferably 200-4000 g / eq, and even more preferably 240-350 g / eq. If the epoxy equivalent of the aforementioned epoxy resin is within the aforementioned range, the generation of active hydroxyl groups during the reaction between the epoxy resin and the curing agent can be suppressed, resulting in excellent heat resistance, low moisture absorption, and consequently, excellent reflow resistance of the cured product. The determination of the epoxy equivalent in this specification, as described in the examples section, is performed in accordance with JIS K 7236.

[0052] The epoxy resin disclosed herein preferably has a melt viscosity of 0.01~5 dPa·s at 150°C, as measured by an ICI viscometer, more preferably 0.01~2 dPa·s, and even more preferably 0.01~0.6 dPa·s. If the melt viscosity of the aforementioned epoxy resin is within the aforementioned range, the resulting cured product exhibits excellent formability due to its low viscosity and excellent flowability, thus being preferable. The melt viscosity described in this specification, as described in the Examples section, is measured using an ICI viscometer according to ASTM D4287.

[0053] The epoxy resin disclosed herein exhibits low viscosity and excellent flowability; therefore, its number average molecular weight (Mn) is preferably in the range of 430 to 1500. Furthermore, its weight average molecular weight (Mw) is preferably in the range of 800 to 2000. The molecular weight distribution (Mw / Mn) represented by the ratio of the aforementioned weight average molecular weight (Mw) to the aforementioned number average molecular weight (Mn) is preferably in the range of 1.1 to 3. The molecular weight of the epoxy resin in this invention was determined using gel permeation chromatography (hereinafter referred to as "GPC") under the measurement conditions described in the examples below.

[0054] <Methods for manufacturing epoxy resin> The following describes the manufacturing method of the epoxy resin disclosed herein. If the epoxy resin in this embodiment is an epoxypropyl ether of the polyvalent hydroxyl resin in this embodiment, its preparation method is not particularly limited and can be manufactured by any method. Regarding the manufacturing method of the epoxy resin disclosed herein, examples include manufacturing methods comprising the following steps. Step (1): Using reactant (1), aromatic compound (A), aromatic divinyl compound (B1), and any aromatic divinyl compound (B1) are reacted to obtain the polyvalent hydroxyl compound of this embodiment; Step (2): As a reaction raw material (2), the polyvalent hydroxy compound obtained in step (1) of this embodiment is reacted with epihaloalcohol to obtain the epoxy resin disclosed herein. The following steps describe the method for manufacturing the epoxy resin disclosed herein in sequence.

[0055] <<Step (1): Manufacturing steps of polyvalent hydroxyl resin>> The following describes the manufacturing steps of the polyvalent hydroxyl compound in this embodiment. The method for manufacturing the polyvalent hydroxyl resin in this embodiment is not particularly limited. For example, an aromatic compound (A) containing phenolic hydroxyl groups and two or more hydrocarbon groups can be reacted with an aromatic divinyl compound (B1) (e.g., divinylbenzene) and other compounds such as an aromatic monovinyl compound (B2) (e.g., ethylvinylbenzene) as needed, in the presence of an acid catalyst to manufacture the polyvalent hydroxyl resin in this embodiment.

[0056] The polyvalent hydroxyl resin obtained by the manufacturing method of the polyvalent hydroxyl resin of this embodiment can control the hydroxyl equivalent and other properties according to the blending ratio of the aromatic divinyl compound (B1) and the aromatic monovinyl compound (B2).

[0057] Regarding the blending ratio of the aforementioned aromatic compound (A), the aforementioned aromatic divinyl compound (B1), and the aforementioned aromatic monovinyl compound (B2), considering the balance of formability and curability during the manufacture of the resulting cured product, it is preferable that the number of moles of vinyl groups contained in the aforementioned aromatic divinyl compound (B1) and the aforementioned aromatic monovinyl compound (B2) is 0.1 to 1 mole, more preferably 0.1 to 0.95 moles, relative to 1 mole of the aforementioned aromatic compound (A).

[0058] In this embodiment, the reaction between the aforementioned aromatic compound (A) and the aforementioned 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 known inorganic and organic acids. Examples 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, dimethylsulfuric acid, and diethylsulfuric acid; Lewis acids such as zinc chloride, aluminum chloride, ferric chloride, and boron trifluoride; or solid acids such as ion exchange resins, activated clay, silica-alumina, and zeolites. The amount of the aforementioned acid catalyst used is preferably 0.01 to 50 parts by mass relative to 100 parts by mass of the raw materials of the aforementioned polyvalent hydroxyl resin, more preferably 0.01 to 10 parts by mass, and even more preferably 0.1 to 5 parts by mass. Furthermore, the above reaction is typically carried out at 10 to 250°C for 1 to 20 hours.

[0059] Examples of solvents that can be used in the above reactions include: alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl celecoxib, and ethyl celecoxib; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethers such as dimethyl ether, diethyl ether, diisopropyl ether, tetrahydrofuran, and dialkyl; and aromatic compounds such as benzene, toluene, chlorobenzene, and dichlorobenzene.

[0060] Regarding the specific methods for carrying out the above reaction, generally, all reactants are loaded at once and the reaction is carried out at a specified temperature; or, an aromatic compound (A) and an acid catalyst are loaded, and while maintaining a specified temperature, an aromatic divinyl compound (B1) and other compounds (e.g., an aromatic monovinyl compound (B2)) are added dropwise while the reaction is carried out. In this case, the dropwise addition time is usually 1 to 10 hours, preferably less than 5 hours. After the reaction, if a solvent is used, the aforementioned polyvalent hydroxyl resin can be obtained by distilling off the solvent and unreacted products as needed. On the other hand, if no solvent is used, the aforementioned polyvalent hydroxyl resin can be obtained by distilling off the unreacted products.

[0061] <<Step (2): Epioxypropyl Etherification Step>> In this step, by etherifying the polyvalent hydroxy compound obtained in step (1) with epihaloalcohol, the hydrogen atom in the phenolic hydroxyl group of the polyvalent hydroxy compound is replaced by epoxypropyl, and the epoxy resin disclosed herein as an epoxypropyl etherified polyvalent hydroxy compound can be obtained.

[0062] Examples of the aforementioned reactions between polyvalent hydroxyl resins and epihalools include, for instance, reacting the resins at a temperature typically between 20 and 150°C, preferably between 30 and 80°C, for 0.5 to 10 hours in the presence of an alkaline catalyst.

[0063] In this embodiment, epihalohydrins include epichlorohydrin, epibromohydrin, β-methylepiochlorohydrin, etc. The amount of epihalohydrin added can be excessive relative to 1 mole of the total number of hydroxyl groups in the polyvalent hydroxyl resin, but it is usually in the range of 1.5 to 30 moles, preferably in the range of 2 to 15 moles.

[0064] Examples of alkaline catalysts include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. Among these, alkali metal hydroxides are preferred for their superior catalytic activity; specifically, sodium hydroxide and potassium hydroxide are more preferred. Furthermore, these alkaline catalysts can be used in solid or aqueous solution form. The amount of the aforementioned alkaline catalyst added is preferably in the range of 0.9 to 2 mol relative to 1 mol of the total number of hydroxyl groups in the polyvalent hydroxyl resin.

[0065] In this embodiment, the reaction between the polyvalent hydroxyl resin and the epihaloalcohol can be carried out in an organic solvent. Examples of organic solvents used include: ketones such as acetone and methyl ethyl ketone; alcohols such as methanol, ethanol, 1-propanol, isopropanol, 1-butanol, secondary butanol, and tertiary butanol; celusol derivatives such as methyl celusol and ethyl celusol; ethers such as tetrahydrofuran, 1,4-dimethylethane, 1,3-dimethylethane, and diethoxyethane; and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, and dimethylformamide. These organic solvents can be used individually, or two or more can be used in combination to adjust the polarity.

[0066] After the reaction with the aforementioned epihaloalcohol is complete, the excess epihaloalcohol can be distilled off to obtain the crude product. Alternatively, if necessary, the obtained crude product can be redissolved in an organic solvent, and an alkaline catalyst can be added to allow for a second reaction, thereby reducing the amount of hydrolyzable halogens. The salts generated in the reaction can be removed by filtration, washing with water, etc. Furthermore, when using an organic solvent, only the resin solids can be distilled off, and the solution can be used as is.

[0067] <Hardened composition> The epoxy resin disclosed herein can be used to formulate curable compositions. These curable compositions may contain the epoxy resin disclosed herein, an epoxy resin curing agent, and any other components (inorganic fillers, silane coupling agents, curing aids, etc.). By using the epoxy resin disclosed herein in the curable composition, the curable composition exhibits excellent formability due to its low viscosity at melt temperature. Furthermore, the cured product obtained from the curable composition highly balances low moisture absorption, low elasticity at heat, and high adhesion, thus exhibiting excellent reflow resistance. With these characteristics, curable compositions using the epoxy resin disclosed herein demonstrate excellent properties, for example, as semiconductor packaging materials.

[0068] <<Curing Agents for Epoxy Resins>> The curing composition of this embodiment allows for the use of epoxy resin curing agents capable of crosslinking with the epoxy groups of epoxy resins without particular limitation. Examples of such curing agents include phenolic curing agents, amine curing agents, acid anhydride curing agents, reactive ester resins, and cyanate ester resins. These curing agents can be used alone or in combination of two or more.

[0069] Regarding the aforementioned phenolic curing agents, examples include: phenolic varnish resin, cresol varnish resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadienol addition-type resin, phenolic aralkyl resin (ZYLOCK resin), naphthol aralkyl resin, triphenol methane resin, tetraphenol ethane resin, naphthol varnish resin, naphthol-phenol cocondensed phenolic varnish resin, naphthol-cresol cocondensed phenolic varnish resin, biphenyl modified phenolic resin (a compound containing polyvalent phenolic hydroxyl groups with a phenolic core linked by dimethylene), biphenyl modified naphthol resin (a polyvalent naphthol compound with a phenolic core linked by dimethylene), aminotrimethylamine modified phenolic resin (a compound containing polyvalent phenolic hydroxyl groups with a phenolic core linked by melamine, benzoguanidine, etc.), and alkoxy-containing aromatic ring modified phenolic varnish resin (a compound containing polyvalent phenolic hydroxyl groups with a phenolic core and an alkoxy-containing aromatic ring linked by formaldehyde), etc., which contain polyvalent phenolic hydroxyl groups. From a formability perspective, phenolic resins are preferred. Furthermore, compounds containing the aforementioned phenolic hydroxyl groups can be used alone or in combination of two or more.

[0070] Regarding the aforementioned amine curing agents, examples include: diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethylpiperidine, menthenediamine (MDA), isophoronediamine (IPDA), 1,3-diaminomethylcyclohexane (1,3-BAC), piperidine, and N,N-dimethylpiperidine. Aliphatic amines such as triethylenediamine; aromatic amines such as meta-diamine (XDA), methanephenyl diamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylmethane (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-trimethyl(dimethylaminomethyl)phenol.

[0071] Examples of the aforementioned anhydride curing agents include: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, diphenyl ketone tetracarboxylic anhydride, ethylene glycol ditriptyltrimethyl ester, glycerol trimellitic ester, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylmethylenetetrahydrophthalic anhydride, methylmethylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexenedicarboxylic anhydride, etc.

[0072] In the curable composition of this embodiment, the amount of curing agent used relative to the amount of epoxy resin used is not particularly limited, for example, as the functional group equivalent ratio (e.g., hydroxyl equivalent of phenolic curing agent / epoxy equivalent of epoxy resin). However, from the perspective of good mechanical properties of the obtained cured product, the active group in the curing agent is preferably 0.5 to 1.5 equivalents relative to the total epoxy groups of the aforementioned epoxy resin and other epoxy resins used as needed. More preferably, it is 0.8 to 1.2 equivalents.

[0073] Furthermore, in addition to the aforementioned epoxy resin and hardener, other resins can be used in combination with the curing components of this embodiment without impairing the effects disclosed herein. Examples include: epoxy resins other than the aforementioned epoxy resins, maleimide resins, bismaleimide resins, polymaleimide resins, polyphenylene ether resins, polyimide resins, benzo[a]pyrene resins, cresol phenolic varnish resins containing trimethylolpropionate, styrene-maleic anhydride resins, allyl esters such as diallyl bisphenol or triallyl triisocyanate, polyphosphate esters, phosphate ester-carbonate copolymers, etc. These other resins can be used alone or in combination of two or more.

[0074] <<Solvent>> The curing composition of this embodiment can be prepared without solvents or may contain a solvent. The aforementioned solvent has the function of adjusting the viscosity of the curing composition, etc.

[0075] Regarding specific examples of the aforementioned solvents, without particular limitation, examples include: 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, celux ester, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as celux ester and butyl carbitol; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene, and 1,2,4-trimethylbenzene; and acetamide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents can be used alone or in combination of two or more.

[0076] Regarding the aforementioned amount of solvent used, it is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, relative to the total mass of the curing component. If the amount of solvent used is 10% by mass or more, the workability is excellent and therefore preferred. On the other hand, if the amount of solvent used is 90% by mass or less, it is preferred from an economic point of view.

[0077] <<Additives>> The curing composition of this embodiment can be mixed with various additives such as curing accelerators, flame retardants, inorganic fillers, silane coupling agents, release agents, pigments, colorants, and emulsifiers as needed.

[0078] Hardening Accelerator Regarding the aforementioned curing accelerators, there are no particular limitations; examples include: phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, urea-based curing accelerators, etc. Furthermore, the aforementioned curing accelerators can be used alone or in combination of two or more.

[0079] Regarding the aforementioned phosphorus-based hardening accelerators, examples include: organophosphorus compounds such as triphenylphosphine, tributylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organophosphite compounds such as trimethyl phosphite and triethyl phosphite; and phosphite salts such as ethyltriphenylphosphine bromide, benzyltriphenylphosphine chloride, tetrabutylphosphine tetraphenylborate, tetraphenylphosphine tetraphenylborate, tetra-p-tolylborate tetraphenylphosphine, triphenylphosphine triphenylborane, tetraphenylphosphine thiocyanate, dicyanimide tetraphenylphosphine, dicyanimide butylphenylphosphine, and tetrabutylphosphine decanoate.

[0080] Regarding the aforementioned amine-based hardening accelerators, examples 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), etc.

[0081] Regarding the aforementioned imidazole-based hardening accelerators, examples include: 2-methylimidazolium, 2-undecylimidazolium, 2-heptadecylimidazolium, 1,2-dimethylimidazolium, 2-ethyl-4-methylimidazolium, 2-phenylimidazolium, 2-phenyl-4-methylimidazolium, 1-benzyl-2-methylimidazolium, 1-benzyl-2-phenylimidazolium, 1-cyanoethyl-2-methylimidazolium, 1-cyanoethyl-2-undecylimidazolium, 1-cyanoethyl-2-ethyl-4-methylimidazolium, 1-cyanoethyl-2-phenylimidazolium, and 1-cyanoethyl-2-undecylimidazolium onmephthalic acid trioxide. Trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazolium isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrole[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, etc.

[0082] Regarding the aforementioned guanidine-based hardening accelerators, examples include: dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dodecyl-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dodecyl-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-butylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, etc.

[0083] Regarding the aforementioned urea-based hardening accelerators, examples include: 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, etc.

[0084] Among the aforementioned curing accelerators, especially when used as semiconductor packaging materials, in terms of superior curing properties, heat resistance, electrical properties, and moisture resistance, triphenylphosphine is preferred among phosphorus compounds, and 1,8-diazabicyclo-[5.4.0]-undecene (DBU) is preferred among tertiary amines.

[0085] The amount of the aforementioned curing accelerator can be adjusted appropriately to obtain the desired curing properties, but it is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the mixture of epoxy resin and curing agent. If the amount of the aforementioned curing accelerator is within the aforementioned range, the curing properties and insulation reliability are excellent and superior.

[0086] Flame retardants Regarding the aforementioned flame retardants, there are no particular limitations; examples include inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, and halogen-based flame retardants. Furthermore, flame retardants can be used alone or in combination of two or more.

[0087] Regarding the aforementioned inorganic phosphorus-based flame retardants, there are no particular limitations, but examples include: red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and polyammonium phosphate; and amide phosphate.

[0088] Regarding the aforementioned organophosphorus flame retardants, without particular limitation, the following can be listed: 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 phosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleic acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, 2-hydroxyethyl methacrylate acid phosphate, etc.; diphenylphosphine such as 9,10-dihydro-9-oxa-10-phenanthroline-10-oxide and diphenylphosphine oxide; 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phenanthroline-10-oxide, 10-(1,4-dihydroxyphenyl)-10H-9-oxa-10-phenanthroline-10-oxide, 10-(1,4-dihydroxyphenyl)-10H-9-oxa-10-phenanthroline-10-oxide, etc. Phosphorus-containing phenols such as 9,10-dihydro-9-oxa-10-phenanthroline-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phenanthroline-10-oxide, and 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phenanthroline-10-oxide; and compounds obtained by reacting the aforementioned phosphate esters, the aforementioned diphenylphosphine, the aforementioned phosphorus-containing phenols with epoxy resins, aldehyde compounds, and phenolic compounds.

[0089] Regarding the aforementioned halogen-based flame retardants, there are no particular limitations, but examples 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-tris(tribromophthalic acid), tetrabromophthalic acid, etc.

[0090] The amount of the aforementioned flame retardant used is preferably 0.1 to 20 parts by weight relative to 100 parts by weight of the epoxy resin disclosed herein.

[0091] <<Inorganic Fillers>> Regarding the aforementioned inorganic fillers, there are no particular limitations, but examples include: silicon dioxide, 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 dioxide, zirconium oxide, barium titanate, barium zirconium titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphotungstenate, talc, clay, mica powder, zinc oxide, hydrotalcite, gibbsite, carbon black, etc. Among these, silicon dioxide is preferred. Specifically, amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, hollow silicon dioxide, etc., can be used. Since more inorganic fillers can be incorporated, fused silicon dioxide is preferred. The aforementioned molten silica can be either crushed or spherical, but to increase the incorporation amount of molten silica and suppress the increase in the melt viscosity of the hardening component, it is preferable to primarily use spherical silica. Furthermore, to increase the incorporation amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. In addition, the aforementioned inorganic filler can be used alone or in combination of two or more.

[0092] Furthermore, the aforementioned inorganic filler may be surface-treated as needed. In this case, there are no particular limitations on the surface treatment agent that can be used; aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, etc., can be used. Specific examples of surface treatment agents include: 3-epoxypropoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldisilazane, etc.

[0093] The amount of the aforementioned inorganic filler used is preferably 0.5 to 95 parts by weight relative to 100 parts by weight of the mixture of the epoxy resin and the aforementioned hardener disclosed herein. If the amount of the aforementioned inorganic filler used is within the aforementioned range, the flame retardancy and insulation reliability are superior. Furthermore, in order not to impair the scope of the characteristics disclosed herein, organic fillers may be incorporated in addition to the aforementioned inorganic fillers. Examples of such organic fillers include polyamide particles.

[0094] This disclosure describes a cured product of the curable composition of this embodiment. By using the epoxy resin disclosed herein, the cured product obtained from the curable composition of this embodiment containing the epoxy resin disclosed herein exhibits low hygroscopicity, low modulus of elasticity at low temperatures, or high adhesion to metallic materials, making it a preferred product. Regarding the method for obtaining a cured product by subjecting the curable composition of this embodiment to a curing reaction, for example, the heating temperature during heat curing is not particularly limited, but is typically 100~300°C, and the heating time is 1~24 hours.

[0095] The cured material of this embodiment preferably has a moisture absorption rate of 1.3% or less. The method for measuring the aforementioned moisture absorption rate is the same as the evaluation method described in the examples section.

[0096] Semiconductor Packaging Materials This disclosure relates to semiconductor packaging materials containing the curable composition of this embodiment. Semiconductor packaging materials obtained using the curable composition of this embodiment, due to the use of the epoxy resin disclosed herein, have low viscosity and excellent flowability, further improving hygroscopicity, thermal modulus of elasticity, and adhesion to metal materials. Therefore, they exhibit excellent processability, formability, and reflow resistance in the manufacturing process, making them a superior product.

[0097] The curable composition of the present embodiment used in the aforementioned semiconductor packaging material may contain an inorganic filler. Furthermore, regarding the filling rate of the aforementioned inorganic filler, for example, 0.5 to 95 parts by mass may be used relative to 100 parts by mass of the curable composition of the present embodiment.

[0098] Regarding methods for obtaining the aforementioned semiconductor packaging material, examples include: methods that, as needed, use an extruder, kneader, roller, or the like to further melt and mix the hardened component of this embodiment with any additive until it becomes homogeneous.

[0099] [Semiconductor Devices] This disclosure pertains to a semiconductor device containing a cured semiconductor packaging material as described above. Semiconductor devices using semiconductor packaging materials derived from the cured composition of this embodiment exhibit superior properties due to the use of the epoxy resin disclosed herein, which has low viscosity and excellent flowability, further improving hygroscopicity, thermal modulus of elasticity, and adhesion to metal materials. Consequently, the manufacturing process exhibits excellent processability, formability, and reflow resistance, making it a preferred embodiment.

[0100] Regarding the method of obtaining the aforementioned semiconductor device, examples include: forming the aforementioned semiconductor packaging material using a casting or transfer molding machine, an injection molding machine, etc., and then heat-curing it in a temperature range of room temperature (20°C) to 250°C.

[0101] [Prepreg] This disclosure describes a prepreg having a reinforcing substrate and a curable composition impregnated in the reinforcing substrate according to this embodiment. A method for obtaining the prepreg from the aforementioned curable composition includes: mixing the organic solvent described later, impregnating the varnished curable composition into a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, polyaramid paper, polyaramid cloth, glass pad, glass yarn bundle, etc.), and then heating at a temperature appropriate to the type of solvent used, preferably 50-170°C. The mass ratio of the curable composition to the reinforcing substrate used in this process is not particularly limited, but it is generally preferred that the resin content in the prepreg is 20-60% by mass.

[0102] Examples of organic solvents used here include: methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl celecoxib, ethyl diethylene glycol acetate, propylene glycol monomethyl ether acetate, etc. The selection and appropriate amount of these solvents can be chosen according to the application. For example, when further manufacturing printed circuit boards from prepreg as described below, it is preferable to use polar solvents with a boiling point of less than 160°C, such as methyl ethyl ketone, acetone, and dimethylformamide. Furthermore, it is preferable to use them at a ratio of 40 to 80% by mass of non-volatile components.

[0103] [Circuit board] This disclosure pertains to a circuit board comprising the aforementioned prepreg and copper foil laminate. Regarding a method for obtaining a printed circuit board from the curable composition of this embodiment, an example is a method of conventionally laminating the aforementioned prepreg, appropriately overlapping copper foil, and heating and pressing at 170-300°C for 10 minutes to 3 hours under a pressure of 1-10 MPa.

[0104] [Build up a thin film] This disclosure pertains to a deposited thin film containing a curable composition of this embodiment. Regarding methods for manufacturing the deposited thin film of this embodiment, an example is a method of manufacturing an adhesive film for a multilayer printed circuit board by coating the aforementioned curable composition onto a support film to form a curable composition layer.

[0105] When manufacturing a stacked thin film from a curable component, it is important that the film is softened under the temperature conditions of vacuum deposition (typically 70~140°C) and exhibits fluidity (resin flow) to fill the vias or through holes in the circuit board while being deposited with the circuit board. To exhibit such characteristics, it is preferable to incorporate the aforementioned components.

[0106] Here, the diameter of the through-holes in the multilayer printed circuit board is typically 0.1~0.5mm, and the depth is typically 0.1~1.2mm, preferably filled with resin within this range. Furthermore, when multiplying the circuit board on both sides, it is desirable to fill approximately half of the through-hole.

[0107] Specifically, the method for manufacturing the aforementioned adhesive film can be achieved by applying the varnish-like curable composition to the surface of a support film (Y) after preparing the varnish-like curable composition, and then drying the organic solvent by heating or blowing hot air to form a composition layer (X) composed of the curable composition.

[0108] The thickness of the constituent layer (X) is preferably greater than or equal to the thickness of the conductor layer. The thickness of the conductor layer in the circuit board is typically in the range of 5 to 70 μm, therefore the thickness of the constituent layer (X) is preferably 10 to 100 μm.

[0109] Furthermore, the constituent layer (X) in this embodiment can be protected by a protective film, which will be described later. By protecting it with a protective film, the adhesion and damage of dust and other contaminants on the surface of the constituent layer (X) can be prevented.

[0110] The aforementioned support films and protective films can include: polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter referred to as "PET") and polyethylene naphthalate; polycarbonate; polyimide; and metal foils such as release paper, copper foil, and aluminum foil. Furthermore, in addition to MAD treatment and corona treatment, release treatment can also be applied to the support films and protective films.

[0111] The thickness of the support film is not particularly limited, but it is usually 10 to 150 μm, preferably in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0112] The above-mentioned support film (Y) is peeled off after being laminated on the circuit substrate or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after heat curing the film, it is possible to prevent the adhesion of dust and the like during the curing step. When peeling off after curing, a release treatment is usually applied to the support film in advance.

[0113] [Other uses] Since the cured product obtained from the curable composition of this embodiment is excellent in low hygroscopicity, high toughness, etc., it is not only suitable for uses such as semiconductor packaging materials, semiconductor devices, prepregs, circuit substrates, and deposited films, but also can be suitably used for various uses such as deposited substrates, adhesives, photoresist materials, and matrix resins of fiber reinforced resins. In terms of uses, it is not limited to these. [Examples]

[0114] The present invention will be specifically described by way of examples and comparative examples. Hereinafter, "parts" and "%" are based on mass unless otherwise specified. In addition, the physical properties of the synthesized epoxy resin were measured as follows and are shown in Tables 1 and 2.

[0115] <Measurement of epoxy equivalent> The measurement was carried out in accordance with JIS K 7236.

[0116] <Measurement method of melt viscosity at 150°C> The measurement was carried out using an ICI viscometer in accordance with ASTM D4287.

[0117] <Measurement of softening point> The measurement was carried out in accordance with JIS K7234.

[0118] <Measurement of GPC> Measurement device: "HLC-8320 GPC" manufactured by Tosoh Corporation, Column: Protective 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: Produced by Tosoh Corporation, "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40℃ Expand the solvent tetrahydrofuran Flow rate 1.0 ml / min Standard: Based on the aforementioned "GPC Workstation EcoSEC-WorkStation" test manual, use the following monodisperse polystyrene with a known molecular weight. (Using polystyrene) Tosoh Corporation manufactured "A-500". Tosoh Corporation manufactured "A-1000" Tosoh Corporation manufactured "A-2500". Tosoh Corporation manufactured "A-5000" Tosoh Corporation's "F-1" Tosoh Corporation manufactured the "F-2" Tosoh Corporation manufactured the "F-4". Tosoh Corporation manufactured the "F-10". Tosoh Corporation manufactured the "F-20". Tosoh Corporation manufactured the "F-40". Tosoh Corporation manufactured the "F-80". Tosoh Corporation manufactured the "F-128". Sample: 50 μl of a tetrahydrofuran solution was filtered through a microfilter to convert the solids content of the polyvalent hydroxyl resin or epoxy resin obtained in the examples described below to 1.0% by mass. The synthesis of the obtained polyvalent hydroxyl resin or epoxy resin was confirmed by the aforementioned GPC test results. Furthermore, the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the obtained polyvalent hydroxyl resin or epoxy resin were calculated.

[0119] [Manufacturing Example 1: Synthesis of a polyvalent hydroxyl resin (P-1)] In a flask equipped with a thermometer, cooling tube, fractionating tube, nitrogen inlet tube, and stirrer, 488.6 g (4.00 moles) of 2,6-divinylphenol and 244 g of toluene were fed, along with 4.9 g of p-toluenesulfonic acid. 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 reaction was allowed to proceed at 115°C for 1 hour. After the reaction was completed, the temperature was lowered to 80°C, and neutralization was performed using an aqueous NaOH solution. Unreacted 2,6-divinylphenol and toluene were removed under reduced pressure to obtain a polyvalent hydroxyl resin (P-1). The physical properties of the obtained polyvalent hydroxyl resin (P-1) are shown in Table 1, and the GPC graph is shown in Figure 1.

[0120] [Manufacturing Example 2: Synthesis of Polyvalent Hydroxyl Resin (P-2)] In Manufacturing Example 1, the reaction was carried out in the same manner, except that 544.8 g (4.00 moles) of 2,3,6-trimethylphenol, 270 g of toluene, and 5.45 g of p-toluenesulfonic acid were changed to obtain a polyvalent hydroxyl resin (P-2). The physical properties of the obtained polyvalent hydroxyl resin (P-2) are shown in Table 1, and the GPC chart is shown in Figure 2.

[0121] [Comparative Manufacturing Example 1: Synthesis of Polyvalent Hydroxyl Resin (P-3)] In a flask equipped with a thermometer, cooling tube, fractionating tube, nitrogen inlet tube, and stirrer, 627.4 g (6.66 moles) of phenol and 313 g of toluene were fed, along with 6.3 g of p-toluenesulfonic acid. The temperature was raised to 115°C. After confirming complete dissolution of the raw materials, a mixture of 520.8 g of divinylbenzene and ethylvinylbenzene (DVB-810, manufactured by Nippon Steel Chemical Co., Ltd.) was added dropwise over 2 hours, and the reaction was allowed to proceed at 115°C for 2 hours. After the reaction was completed, the temperature was lowered to 80°C, and neutralization was performed using an aqueous NaOH solution. Unreacted phenol and toluene were removed under reduced pressure to obtain a polyvalent hydroxyl resin (P-3). The physical properties of the obtained polyvalent hydroxyl resin (P-3) are shown in Table 1.

[0122] [Table 1] Table 1 Manufacturing Example 1 Manufacturing Example 2 Comparative Manufacturing Example 1 Polyhydroxy resins P-1 P-2 P-3 Hydroxyl equivalent (g / eq) 209 301 208 Number average molecular weight (Mn) 523 262 477 Weight-average molecular weight (Mw) 587 345 914 Molecular weight distribution (Mw / Mn) 1.1 1.3 1.9

[0123] [Example 1: Synthesis of epoxy resin (E-1)] In a flask equipped with a thermometer, dropping funnel, cooling tube, and stirrer, 300.0 g of the polyvalent hydroxyl resin (P-1) obtained in Manufacturing Example 1, 923 g (5.0 equivalents) of epichlorohydrin, 238 g of n-butanol, and 40 g of water were fed and dissolved while being purged with nitrogen. The temperature was raised to 60°C, and 134 g (1.1 equivalents) of a 49% sodium hydroxide aqueous solution was added dropwise over 5 hours. The mixture was then stirred continuously for 0.5 hours under the same conditions. Unreacted epichlorohydrin was then distilled off under reduced pressure. 700 g of methyl isobutyl ketone was added to the resulting crude epoxy resin and dissolved. 15 g of a 5% sodium hydroxide aqueous solution was further added to this solution, and the mixture was reacted at 80°C for 2 hours. The solution was then washed three times with 190 g of water until the pH of the washing solution became neutral. The system was then dehydrated by azeotropic distillation, and after fine filtration, 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 the GPC chart is shown in Figure 3.

[0124] [Example 2: Synthesis of epoxy resin (E-2)] Except that the polyvalent hydroxyl resin (P-1) obtained from Manufacturing Example 2 was replaced with 300.0 g of the polyvalent hydroxyl resin (P-2), the reaction was carried out in the same manner as in Example 1 to obtain epoxy resin (E-2). The physical properties of the obtained epoxy resin (E-2) are shown in Table 2, and the GPC chart is shown in Figure 4.

[0125] [Comparative Example 1: Synthesis of epoxy resin (E-3)] Except that 300.0 g (1.0 equivalent of hydroxyl groups) of the polyvalent hydroxyl resin (P-3) obtained in Comparative Manufacturing Example 1 was used instead of the polyvalent hydroxyl resin (P-1), the reaction was carried out in the same manner as in Example 1 to obtain epoxy resin (E-3). The physical properties of the obtained epoxy resin (E-3) are shown in Table 2.

[0126] [Table 2] Table 2 Example 1 Example 2 Comparative Example 1 Epoxy resin E-1 E-2 E-3 Epoxy equivalent (g / eq) 285 301 283 Melt viscosity (dPa.s) 0.1 0.3 0.5 Number average molecular weight (Mn) 407 314 747 Weight-average molecular weight (Mw) 547 438 1439 Molecular weight distribution (Mw / Mn) 1.3 1.4 1.9

[0127] [Examples 3, 4, and Comparative Example 2] <Modulation of hardening components> The components shown in Table 3 were combined to obtain a hardening composition for melt mixing. Details of each component are as follows. Hardener: Phenolic resin for varnish (DIC Corporation "TD-2131", hydroxyl equivalent 104g / eq) Hardening accelerator: Triphenylphosphine (manufactured by Beixing Chemical Industry, "TPP")

[0128] <Preparation and Evaluation of Test Strips for Moisture Absorption Test> The curable composition obtained above was cured at 150°C for 10 minutes under normal pressure with a thickness of 2.4 mm, and then post-cured at 175°C for 5 hours to obtain a curable for evaluation.

[0129] <Evaluation of Hygroscopicity> The hardened material was cut into 75mm × 25mm pieces using a diamond cutter, which were then used as test pieces for moisture absorption evaluation. Moisture absorption was evaluated by placing the sample in an environment with a temperature / humidity of 85℃ / 85% for 300 hours. The moisture absorption rate was calculated as [(weight of the test piece after the test - weight of the test piece before the test) ÷ weight of the test piece before the test × 100 (%)].

[0130] <Evaluation of Thermal Elastic Modulus> The hardened material was cut into pieces of 5mm × 54mm size using a diamond cutter. The storage modulus at 260°C was measured using a viscoelasticity measuring device (Rheometric "Solid Viscoelasticity Measuring Device RSA II", rectangular tension method: frequency 1Hz, heating rate 3°C / min).

[0131] [Table 3] Table 3 unit Example 3 Example 4 Comparative Example 2 Composition of hardening components Epoxy resin E-1 Quality 73.2 E-2 Quality 74.3 E-3 Quality 73.1 hardener TD-2131 Quality 26.8 25.7 26.9 hardening accelerator TPP Quality 1 1 1 Physical properties of hardened materials hygroscopic % 0.9 0.7 1 Thermal modulus of elasticity MPa 6 5 15

[0132] [Examples 5, 6, and Comparative Example 3] Grain shear force testing was conducted as an adhesion test for copper plates. The test pieces were prepared as follows.

[0133] Using the materials shown in Table 4, a hardened composition was obtained by melt-kneading at 80°C for 10 minutes using a two-roll mill. Details of each component are as follows. Hardener: Phenolic resin for varnish (DIC Corporation "TD-2131", hydroxyl equivalent 104g / eq) Hardening accelerator: Triphenylphosphine (manufactured by Beixing Chemical Industry, "TPP") Fused silicon dioxide: "FB-560" manufactured by Denki Kagaku Co., Ltd. Silane coupling agent: γ-epoxypropoxyethoxysilane (Shin-Etsu Chemical Co., Ltd. "KBM-403")

[0134] <Production of Experimental Films> The hardening components of the above-described examples and comparative examples were pulverized and used as evaluation components. Using a transfer molding machine, under conditions of 70 kg / cm² pressure, 5 cm / s stamping speed, 175°C temperature, and 600 seconds, the components were formed on copper foil to obtain test pieces with dimensions of 6 mm × 6 mm × 2 mm (2 mm thickness). Furthermore, the copper foil used was EFTEC-64T (0.15 mm, manufactured by Furukawa Electric Industries, Ltd.).

[0135] <Grain Shear Force Test Evaluation> The grain shear strength test was performed using an adhesion test (RHESCA PTR-1102). The shear rate was 0.1 mm / s, and the test was conducted at N5 for one sample. The average peel strength (gf) from the copper foil was calculated. The peel strength is shown as a relative evaluation, and the strength of each component is shown in Table 4 with the molded product of Comparative Example 6 as 1.0.

[0136] [Table 4] Table 4 unit Example 5 Example 6 Comparative Example 3 Composition of hardening components Epoxy resin E-1 Quality 58.6 E-2 Quality 59.5 E-3 Quality 58.5 hardener TD-2131 Quality 21.4 20.5 21.5 hardening accelerator TPP Quality 1 1 1 Molten silicon dioxide FB-560 Quality 81 81 81 Coupling agent KBM-403 Quality 0.8 0.8 0.8 Physical properties of hardened materials Peel strength gf 1.3 1.5 1

[0137] According to Table 2, the epoxy resin of the present invention has a low melt viscosity, thus improving formability and filler filling rate. Furthermore, as shown in Table 3, epoxy resin E-3 has poor hygroscopicity, while the epoxy resins (E-1, E-2) of the present invention have excellent hygroscopicity, thus improving weld crack resistance and connection reliability. Moreover, the epoxy resin of the present invention has a very low storage modulus near the reflow temperature, thus improving peel resistance during reflow. Table 4 shows the results of the adhesion test of the epoxy resin of the present invention to copper foil, confirming that the epoxy resin of the present invention exhibits excellent adhesion to copper foil.

[0138] Based on the above, the epoxy resin of the present invention highly balances the opposite properties of low viscosity and moisture absorption during melting and low elasticity during heating, while exhibiting excellent adhesion to copper foil, and is therefore particularly useful in the field of electronic materials.

[0139] none.

Claims

1. An epoxy resin, which is an epoxypropyl etherified of a polyvalent hydroxyl resin in which an aromatic compound (A) having a phenolic hydroxyl group and two or more hydrocarbon groups in the aromatic ring and an aromatic divinyl compound (B1) are reactants (1), wherein the aromatic compound (A) is represented by the following general formula (A1); (in the above general formula (A1), Ra represents a hydrocarbon group having 1 to 6 carbon atoms, pa represents 2 or 3, and the multiple Ra may be the same or different).

2. The epoxy resin of claim 1 is reacted with the polyvalent hydroxyl resin and epihalohydrin (C) as raw materials (2).

3. The epoxy resin of claim 1 or 2 further contains an aromatic monovinyl compound (B2) as the reactant (1).

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

5. The epoxy resin of claim 1 or 2, wherein the hydrocarbon group is an alkyl group having 1 to 6 carbon atoms.

6. A curable composition comprising an epoxy resin as claimed in any one of claims 1 to 5, and a curing agent.

7. A hardening compound, which is a hardening compound of the hardening composition as claimed in claim 6.

8. A prepreg having a reinforcing substrate and a semi-cured material impregnated in the reinforcing substrate with a curable composition as claimed in claim 6.

9. A circuit board having a prepreg as described in claim 8 and a laminate of copper foil.

10. A build-up film containing a curable composition as claimed in claim 6.

11. A semiconductor packaging material comprising a curable composition as claimed in claim 6.

12. A semiconductor device comprising a hardened semiconductor package material as claimed in claim 11.

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