TW202336067A - Epoxy resin - Google Patents

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. 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).

Description

Epoxy resin

This invention relates to epoxy resins.

Thermosetting resins containing epoxy resin and its hardener as essential components are widely used in the fields of electronic components and electronic components such as semiconductor packaging materials and printed circuit boards due to their excellent physical properties such as high heat resistance and moisture resistance. Conductive adhesives such as conductive paste, other adhesives, matrix for composite materials, coatings, photoresist materials, color-developing materials, etc. Among these various uses, in the field of semiconductor packaging materials, there are high requirements for miniaturization and high integration of electronic devices, and the transfer to surface mount packages such as BGA and CSP is developing, and copper with high joint reliability in high temperature environments is being developed. Line adoption.

However, copper wire is more susceptible to corrosion than gold in the past. If the interface between the packaging resin and the lead frame deteriorates, such as peeling, moisture will concentrate in the peeled part due to capillary phenomena, corroding the chip and wire bonding parts. Furthermore, the rapid expansion of water during the reflow step at high temperature becomes the main cause of cracks. Therefore, the characteristics of the packaging resin need to reduce the peeling of the lead frame interface during reflow. Specifically, it is required to reduce the moisture absorption rate, reduce the elastic modulus, and improve the bonding force with the lead frame.

In addition to the above-mentioned properties, it is also desirable for semiconductor encapsulating materials to use resin materials that are highly filled with fillers such as silica for the purpose of suppressing thermal expansion. In order to increase the filling rate, it is important that the resin material has low viscosity and excellent fluidity.

Patent Document 1 discloses an epoxy resin, a derivative of a polyvalent hydroxyl resin obtained by reacting a phenolic compound and an aromatic vinyl compound, as a product that imparts fluidity, moisture resistance, high-temperature low elasticity, flame retardancy, and low A cured resin with excellent dielectric properties. [Prior technical literature] [Patent Document]

[Patent Document 1] Japanese Patent Application Publication No. 2017-066268

[Problem to be solved by the invention]

However, the technology of Patent Document 1 aims to achieve a high degree of balance between excellent formability due to low viscosity when the resin is melted, low moisture absorption of the cured product, low elasticity during heat, and high adhesion to adherends such as copper foil. The resulting excellent reflow resistance has not been reviewed at all, and the revealed characteristics of epoxy resin are not sufficient, leaving room for improvement.

Therefore, the problem to be solved by the present invention is to provide an epoxy resin that can achieve a high degree of low viscosity during melting, low moisture absorption of the cured product, low elasticity during heat, and high adhesion. [Means used to solve problems]

As a result of repeated and careful research in order to solve the above-mentioned problems, the present inventors found that by using 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) An epoxy resin that is the glycidyl etherate of the polyvalent hydroxyl resin as the reaction raw material (1) can obtain a high degree of low viscosity during melting, low moisture absorption of the cured product, low elasticity during heat, and High-adhesion epoxy resin completes the present invention. [Effects of the invention]

According to the present disclosure, it is possible to obtain an epoxy resin that can achieve a high degree of balance between low viscosity during melting, low moisture absorption of the cured product, low elasticity during heat, and high adhesion. Such epoxy resins are particularly useful in applications such as electronic component sealing materials.

[Form used to implement the invention]

Hereinafter, the embodiment of the present invention (referred to as "the present embodiment") will be described in detail. However, the present disclosure is not limited to the following description and can be implemented with various modifications within the scope of the gist.

＜Epoxy resin＞ This disclosure relates to an epoxy resin, which uses 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) as the polyvalent hydroxyl group of the reaction raw material (1). Glycidyl etherate of resin. In addition, the epoxy resin of the present disclosure may also be an epoxy resin using the above-mentioned polyvalent hydroxyl resin and epihalohydrin (C) as the reaction raw material (2). Furthermore, the epoxy resin of the present disclosure may further contain an aromatic monovinyl compound (B2) as the aforementioned reaction raw material (1). In the epoxy resin of the present disclosure, the aromatic compound (A) used as the reaction raw material (1) has a phenolic hydroxyl group and two or more hydrocarbon groups in the aromatic ring, so that it can obtain a highly compatible low viscosity during melting and a hardened product. Epoxy resin has low moisture absorption, low elasticity when heated, and high adhesion, so it is preferred.

The so-called "reaction raw materials" in this specification refer to compounds used in order to obtain the target compound through chemical reactions such as combination or decomposition, and which partially constitute the chemical structure of the target compound, as well as solvents, catalysts and other auxiliaries responsible for chemical reactions. Except for substances that act as agents. Specifically, in this specification, the so-called "reaction raw material" refers to the target polymer compound (epoxy resin) or its precursor compound (for example: polymerization reaction, etherification reaction) used to obtain the target through a chemical reaction (for example: polymerization reaction, etherification reaction) Polyvalent hydroxyl resin) precursor compound.

＜Polyvalent hydroxyl resin＞ The so-called "polyvalent hydroxyl resin" in this embodiment uses 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) as the reaction raw material (1 ) polyvalent hydroxyl resin. Moreover, in this embodiment, an aromatic monovinyl compound (B2) may be further contained as the reaction raw material (1). In other words, the polyvalent hydroxyl resin in this embodiment contains an aromatic compound (A) unit having a phenolic hydroxyl group and an aromatic ring with two or more hydrocarbon groups, chemically bonded to an aromatic divinyl compound (B1) unit, and If necessary, it has a structure in which the unit of the aromatic monovinyl compound (B2) is chemically bonded to the aforementioned aromatic ring in the unit of the aforementioned aromatic compound (A). In addition, the so-called "unit" in this specification refers to the repeating unit of the chemical structure formed during 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 reaction raw material, it becomes easy to control the aromatic divinyl compound (B1) and the reaction site described later. It becomes easy to obtain a polyvalent hydroxyl resin (P2) with a uniform chemical structure or chain length, and as a result, it is possible to provide an epoxy resin composition that exhibits excellent peel strength with respect to metal materials and an elastic modulus at low heat when cured ( = hardening composition). Hereinafter, the aromatic compound (A), the aromatic divinyl compound (B1), and the aromatic monovinyl compound (B2) that are the reaction raw materials of the polyvalent hydroxyl resin (P2) will be described. The preferred form of the polyvalent hydroxyl resin and the epoxy resin disclosed herein will be described as the glycidyl etherate of the multivalent hydroxyl resin.

-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) may be a phenolic compound. Moreover, the aromatic ring forming the central structure of the aromatic compound (A) may be a monocyclic form or a condensed polycyclic form, and may contain an aromatic hydrocarbon ring. Examples of the aromatic hydrocarbon ring include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, and sulfa ring, but are not limited thereto. From the viewpoint of the melt viscosity of the resin, the aromatic ring is preferably monocyclic.

In the aromatic compound (A) of the present embodiment, examples of the two or more hydrocarbon groups (R ^a ) that at least one of the aromatic rings in the aromatic compound (A) have include: C 1 to 6 hydrocarbon groups. hydrocarbyl. Examples of the hydrocarbon group (R ^a ) include aliphatic hydrocarbon groups having 1 to 6 carbon atoms. The aliphatic hydrocarbon group may be either linear or branched. Furthermore, in order to prevent addition reactions with other compounds, the aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group. Examples of the saturated aliphatic hydrocarbon group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, hexyl, and the like. The effect of the present invention (low viscosity during melting) becomes more significant as the molecular weight of the hydrocarbon group becomes lower. In addition, as the molecular weight of the hydrocarbon group (R ^a ) becomes higher, the effect exerted by the present invention (low hygroscopicity when forming a cured product) becomes more significant.

The number of hydrocarbon groups (R ^a ) that the aromatic ring in the aromatic compound (A) of this embodiment has (that is, the number of substitutions) is 2 or more. When the number of the hydrocarbon groups (R ^a ) is 2 or more, it can exhibit low viscosity and low hygroscopicity while exhibiting excellent peel strength and low-heat elastic modulus with respect to metal materials. The upper limit of the number of the hydrocarbon groups (R ^a ) is as long as it is a substitutable ring constituent atom in the unsubstituted aromatic ring from the viewpoint that the aromatic ring has a phenolic hydroxyl group and two bonds are used for polymerization. Just subtract the number of 3 from the number. For example, when the aromatic ring is a benzene ring, the number of the hydrocarbon groups (R ^a ) is 3 or less.

Furthermore, by setting the number of hydrocarbon groups (R ^a ) in the aromatic ring in the aromatic compound (A) to 2 or more, it becomes easier to control the aromatic divinyl compound (B1) and the reaction site described later, so it becomes possible. It is easy to obtain a polyvalent hydroxyl resin with a uniform chemical structure or chain length, and as a result, it is easy to exhibit low viscosity during melting, low moisture absorption of the cured product, low elasticity during heat, or high adhesion.

Taking as an example the case where the aromatic compound (A) in this embodiment is an aromatic hydrocarbon ring (for example: benzene ring, naphthalene ring) having a phenolic hydroxyl group and two or more hydrocarbon groups (R ^a ), the aromatic compound ( The preferred form of A) will be explained. In this embodiment, it is preferable that among the carbon atoms in the aromatic hydrocarbon ring constituting the aromatic compound (A), there be at least one carbon atom having the largest HOMO electron density (Hückel coefficient). Substituted (or substituted by a hydrogen atom).

This makes it easy to control the _ArSE reaction and molecular design caused by a cationic reagent such as the aromatic divinyl compound (B1) described below. To explain in more detail, among the carbon atoms in the aromatic hydrocarbon ring constituting the aromatic compound (A), if the carbon atom having the largest HOMO electron density (Shock coefficient) is unsubstituted (or bonded to a hydrogen atom junction), the carbocation of the aromatic divinyl compound (B1), which is a cation-like reagent, easily reacts with the carbon atom having the maximum electron density of HOMO. Therefore, by controlling the number and position of the hydrocarbon group (R ^a ) or the number and position of the phenolic hydroxyl group, the bonding sites or the number of bonds with the aromatic divinyl compound can be adjusted. Therefore, it is presumed that it becomes easy to design the chemical structure or molecular chain length of the obtained polyvalent hydroxyl resin (P2).

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 of the carbon atoms at the 2-position, 4-position and 6-position is substituted with a hydrogen atom. Thereby, at least one carbon atom at the 2-position, 4-position, and 6-position of the ortho- and para-positions of the phenol nucleus, which has a high electron density, is converted into a cationic reagent such as the aromatic divinyl compound (B1) described below. Got to be easy to attack. Similarly, for unsubstituted naphthalene rings, the carbon atoms at positions 1, 4, 5 and 8 have the maximum HOMO electron density. The position of the carbon atom with the maximum electron density of HOMO changes according to the bonding position of the phenolic hydroxyl group. For example, in 2-naphthol with one naphthalene ring and one hydroxyl group, for the 1 and 3 positions, it is composed of aromatic divinyl The carbocation generated by the base compound (B1) is easy to react. Therefore, for example, if the hydrogen atom of the CH group at the 1-position is replaced by a hydrocarbon group (R ^a ), the ArS _E reaction becomes easy to proceed with the carbon atom at the 3-position, and therefore the polyvalent hydroxyl resin (P2) obtained can be controlled. Chemical structure, etc. 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 reaction. Therefore, for example, if the hydrocarbon group (R ^a ) is bonded to three carbon atoms at the 1-position, 3-position, and 6-position, the ArS _E reaction becomes easier to proceed with the carbon atom at the 8-position.

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

Specific examples of the aromatic compound (A) in this embodiment include: stubble phenol (2,3-stubble phenol, 2,4-stubble phenol, 2,5-stubble phenol, 2,6-stubble phenol). Phenol, 3,4-trimethylphenol, 3,5-trimethylphenol), 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 composed of their derivatives, etc. Alkylphenol compounds, and the above-mentioned hydrocarbon group (R ^a ) substituted are selected from the group consisting of 1-naphthol, 2-naphthol, 1,2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, and 1,4-dihydroxynaphthalene. Naphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and Among the compounds of the 2,7-dihydroxynaphthalene group, compounds having two or more CH group hydrogen atoms are so-called dialkylhydroxynaphthalene-based compounds, but are not limited thereto. In addition, the aromatic compound (A) in this embodiment can be used individually or in combination of 2 or more types. However, from the viewpoint of low viscosity during melting, dialkylphenol compounds are preferred.

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

(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. The plural R ^a may be the same, or They may be different.) In the above-mentioned general formula (A1), the hydrocarbon group having 1 to 6 carbon atoms is the same as that defined as the above-mentioned hydrocarbon group (R ^a ).

-Aromatic divinyl compound (B1)- The aromatic divinyl compound (B1) in this embodiment has two vinyl groups as substituents on the aromatic ring and can be combined with the above-mentioned aromatic compound (A). reaction, it can be used without particular restrictions. Examples of the aromatic divinyl compound (B1) include divinylbenzene, divinylbiphenyl, divinylnaphthalene, and aromatic rings thereof substituted with one or more alkyl groups or alkoxy groups. Various compounds such as radicals, halogen atoms, etc. The alkyl group may be either linear or branched. Among them, the number of carbon atoms in the alkyl group or alkoxy group is preferably 1 to 4, from the viewpoint of exhibiting excellent peel strength with respect to metal materials and elastic modulus at low heat. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, isobutyl, and the like. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, and the like. Examples of the aforementioned halogen atom include fluorine atom, chlorine atom, bromine atom, etc. As described above, the aromatic divinyl compound (B1) can be introduced into the ring of the aromatic compound (A) through the _ArSE reaction caused by a cationic reagent such as the aromatic divinyl compound (B1). specific location. Therefore, it becomes easy to obtain the polyvalent hydroxyl resin (P2) with a uniform chemical structure or chain length, and as a result, it is possible to provide an epoxy resin composition showing excellent peel strength with respect to metal materials and elastic modulus at low heat.

Specific examples of the aromatic divinyl compound (B1) in this embodiment include 1,2-divinylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene. , 2,5-dimethyl-1,4-divinylbenzene, 2,5-diethyl-1,4-divinylbenzene, cis, cis, β, β'-diethoxy-m-m -Divinylbenzene, 1,4-divinyl-2,5-dibutylbenzene, 1,4-divinyl-2,5-dihexylbenzene, 1,4-divinyl-2,5 -Divinylbenzenes such as dimethoxybenzene and compounds composed of their derivatives, as well as 1,3-divinylnaphthalene, 1,4-divinylnaphthalene, and 1,5-divinylnaphthalene , 1,6-divinylnaphthalene, 1,7-divinylnaphthalene, 2,3-divinylnaphthalene, 2,6-divinylnaphthalene, 2,7-divinylnaphthalene, 3,4- Divinylnaphthalenes such as divinylnaphthalene, 1,8-divinylnaphthalene, 1,5-dimethoxy-4,8-divinylnaphthalene and compounds composed of their derivatives, but not Limited to this.

In addition, the aromatic divinyl compound (B1) in this embodiment can be used alone, or two or more types can be used in combination. In particular, from the viewpoint of fluidity, the aromatic divinyl compound (B1) is preferably divinylbenzene and a compound having a substituent on its aromatic ring, and more preferably divinylbenzene. In addition, in this embodiment, the substitution position of the vinyl group of divinylbenzene is not particularly limited, but it is preferable that the intermediate is the main component. The content of the intermediate in divinylbenzene is preferably 40 mass% or more, more preferably 50 mass% or more, based on the total amount of divinylbenzene.

The aromatic divinyl compound (B1) which is the reaction raw material (1) of the polyvalent hydroxyl resin of the present disclosure can be represented by the following formula (B1).

(In the above general formula (B1), R ^b1 represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group, preferably an alkyl group having 1 to 3 carbon atoms, and p ^b1 represents an integer of 0 to 4 , preferably 0 to 1. In addition, when p ^b1 is an integer of 2 or more, the plural R ^b1 may be the same as each other, or may be different.) In the above general formula (B1), an alkyl group having 1 to 4 carbon atoms Or the alkoxy group is the same as the above-mentioned alkyl group or alkoxy group.

-Aromatic monovinyl compound (B2)- The polyvalent hydroxyl resin in this embodiment may use other compounds as reaction raw materials in addition to the aromatic compound (A) and the aromatic divinyl compound (B1). Examples of the other compounds include aromatic monovinyl compounds (B2) and the like. That is, the polyvalent hydroxyl resin in the embodiment preferably uses the aromatic compound (A), the aromatic divinyl compound (B1), and the aromatic monovinyl compound (B2) as the reaction raw material (1). The polyvalent hydroxyl resin (P2) of this embodiment uses an aromatic monovinyl compound (B2) in addition to the above-mentioned aromatic compound (A) and the above-mentioned aromatic divinyl compound (B1) as its reaction raw materials. , when the finally obtained polyvalent hydroxyl resin (P2) is used as a semiconductor encapsulation material, it is preferable because the resin has excellent fluidity and the elastic modulus of the cured product becomes low when heated. In addition, use of the above-mentioned aromatic monovinyl compound (B2) is also useful for improving moisture resistance. In addition, the aromatic monovinyl compound (B2) also generates a carbocation in the same manner as the aromatic divinyl compound (B1). Therefore, among the carbon atoms in the aromatic hydrocarbon ring constituting the aromatic compound (A), there is Carbon atoms with the maximum HOMO electron density (shock coefficient) are prone to reactions.

Examples of the aromatic monovinyl compound (B2) in this embodiment include vinylbenzene, vinylbiphenyl, vinylnaphthalene, and one or more alkyl or alkoxy groups substituted on the aromatic ring. , various compounds with substituents such as halogen atoms, etc. The alkyl group or alkoxy group may be either linear or branched, and may have an unsaturated bond in the structure. Among them, when low hygroscopicity is important, the alkyl group or the alkoxy group is preferably a group having 1 to 4 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, isobutyl, and the like. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, and the like. Examples of the aforementioned halogen atom include fluorine atom, chlorine atom, bromine atom, etc.

Specific examples of the aromatic monovinyl compound (B2) in this embodiment include: styrene; fluorostyrene; vinylbenzyl chloride; alkylvinylbenzene (o-, m-, p-methylbenzene). Ethylene; o-, m- and p-ethylvinylbenzene); o-, m- and p-(chloromethyl)styrene and compounds composed of their derivatives and other vinylbenzenes; 4-vinylbiphenyl, 4 - Biphenyl compounds such as vinyl p-terphenyl and compounds composed of derivatives thereof; and vinyl naphthalenes such as 1-vinylnaphthalene; 2-vinylnaphthalene and compounds composed of derivatives thereof, but Not limited to this. In particular, from the viewpoint of being able to reduce the thermal elastic modulus, alkylvinylbenzene and a compound having a substituent on its aromatic ring are preferred, and ethylvinylbenzene is more preferred. In addition, the substitution positions of the vinyl group and the ethyl group of the aforementioned ethylvinylbenzene are not particularly limited, but it is preferable that the intermediate is the main component. The content of the intermediate in ethylvinylbenzene, relative to the ethylvinylbenzene The total amount of benzene is preferably 40 mass% or more, further preferably 50 mass% or more

The aromatic monovinyl compound (B2) that can be used as the reaction raw material (1) of the polyvalent hydroxyl resin of the present disclosure can be represented by the following general formula (B2).

(In the above general formula (B2), R ^b2 represents a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group, preferably an alkyl group having 1 to 3 carbon atoms, and p ^b2 represents an integer of 0 to 5 , preferably 0 to 1. In addition, when p ^b2 is an integer of 2 or more, the plural R ^b2 may be the same as each other, or may be different.) In the above general formula (B2), an alkyl group having 1 to 4 carbon atoms Or the alkoxy group is the same as the above-mentioned alkyl group or alkoxy group.

When using the aromatic monovinyl compound (B2) as a reaction raw material for the polyvalent hydroxyl resin in this embodiment, it is preferable that the aromatic divinyl compound (B1) in the reaction raw material is smaller than the aromatic divinyl compound (B1) in the reaction raw material. The mass ratio ((B1)/(B2)) of the monovinyl compound (B2) is 30/70~99/1, more preferably 50/50~99/1, further preferably 50/50~98/2 . When the mass ratio is within the above range, it is preferable to achieve a balance of physical properties in terms of handleability of the polyvalent hydroxyl resin obtained, moldability during production of the epoxy resin obtained from the polyvalent hydroxyl resin, and curability. .

＜Preferred form of polyvalent hydroxyl resin＞ Hereinafter, aspects of polyvalent hydroxyl resins suitable for the present disclosure will be described, taking the case where each aromatic ring is a benzene ring as an example. The following chemical structural formulas are used to illustrate the present disclosure, and the scope of the present disclosure is not limited to the following chemical structural formulas.

The polyvalent hydroxyl resin in this embodiment preferably has a partial structure represented by the following general formulas (I) and/or (II). (In the above general formulas (I) and (II), R ¹ , R ² , and R ³ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and R ⁴ and R ⁵ each independently represent a hydrogen atom or a carbon An alkyl group having 1 to 3 atoms, R ⁶ represents a substituent represented by the general formula (a), (In the general formula (a), R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) R ⁸ represents a hydrogen atom or an organic group, and p is R ⁶ of each phenolic ring in the entire polyvalent hydroxyl resin. The average number of substitutions represents a number from 0 to 1. In addition, * in the above-mentioned general formulas (I) and (II) represents a bond with other atoms. )

In the above-mentioned general formulas (I) and (II), the hydrocarbon group having 1 to 6 carbon atoms is preferably the same as defined as the above-mentioned hydrocarbon group (R ^a ). Moreover, in the above-mentioned general formulas (I) and (II), R ¹ , R ² and R ³ are preferably each independently an alkyl group having 1 to 4 carbon atoms, and R ⁴ and R ⁵ are preferably each independently an alkyl group having 1 to 4 carbon atoms. Ground is a hydrogen atom or a methyl group.

In the above general formula (a), R ⁷ is preferably an alkyl group having 1 to 4 carbon atoms.

The organic group in the above general formulas (I) and (II) is a monovalent organic group, preferably an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or an alkenyl group having 1 to 6 carbon atoms. of alkoxy. Furthermore, one or two or more non-adjacent -CH ₂ - groups among the alkyl group, alkenyl group and alkoxy group may be substituted by -O-, -COO- or -OCO-.

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), R ¹ , R ² , and R ³ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and R ⁴ and R ⁵ each independently represent a hydrogen atom or a carbon An alkyl group having 1 to 3 atoms, R ⁶ represents a substituent represented by the general formula (a), (In the general formula (a), R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) 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 It is the average substitution number of R ⁶ per phenolic ring, and represents a number from 0 to 1. ) R ¹ to R ⁸ in the general formulas (III) and (IV) are the same as R ¹ to R ⁸ in the above general formulas (I) and (II), so they are omitted here. )

The hydroxyl equivalent weight of the polyvalent hydroxy resin of this embodiment is preferably 200 to 500 g/eq, more preferably 200 to 400 g/eq. In addition, the measurement of the hydroxyl equivalent of the polyvalent hydroxyl resin in this specification is a value measured based on the neutralization titration method specified in JIS K 0070 (1992).

The polyvalent hydroxyl resin of this embodiment has low viscosity and excellent fluidity, so the number average molecular weight (Mn) is preferably in the range of 200 to 1,500, more preferably in the range of 200 to 1,000. Furthermore, the weight average molecular weight (Mw) of the polyvalent hydroxyl resin is preferably in the range of 300 to 2,000, more preferably in the range of 400 to 1,500. The molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably in the range of 1.1 to 3, more preferably in the range of 1.1 to 1.8. The polyvalent hydroxyl resin of this embodiment uses the aromatic compound (A) unit of a phenolic compound having two or more hydrocarbon groups (R ^a ) in the aromatic ring as a repeating unit, so it is easy to control the combination with the aromatic divinyl compound (B1 ) the bonding part of the unit. On the other hand, in a phenol resin having a phenolic compound having one or less hydrocarbon groups in the aromatic ring as a repeating unit, there are many bonding sites with the aromatic divinyl compound units of the phenolic compound, so there are also Depending on the chain length or chemical structure of the phenol resin obtained, the molecular weight distribution will inevitably show a tendency to broaden. Therefore, the polyvalent hydroxyl resin of the present disclosure can exhibit homogeneous characteristics with a consistent molecular weight than conventional phenol resins.

<Preferred form of epoxy resin disclosed herein> ＜＜Better structure＞＞ The epoxy resin of the present disclosure is a compound obtained by etherifying the polyvalent hydroxy compound in the present embodiment with glycidyl. More specifically, it is a hydrogen atom in one or more phenolic hydroxyl groups in the polyvalent hydroxy compound. Compounds substituted with glycidyl. In other words, the epoxy resin of the present disclosure contains an aromatic compound (A) unit having a phenolic hydroxyl group and an aromatic ring with two or more hydrocarbon groups chemically bonded with an aromatic divinyl compound (B1) unit, and if necessary, has The unit of the aromatic monovinyl compound (B2) is chemically bonded to the structure of the aforementioned aromatic ring in the unit of the aforementioned aromatic compound (A), and may be one in which the hydrogen atom in the aforementioned phenolic hydroxyl group is substituted with a glycidyl ether group. chemical structure. The epoxy resin of the present disclosure can be produced by reacting a polyvalent hydroxy compound and an epihalohydrin, as will be described later in the column for the method for producing the epoxy resin of the present disclosure.

The epoxy resin of the present disclosure preferably has a partial structure represented by the following general formulas (V) and/or (VI). (In the above general formulas (V) and (VI), R ¹ , R ² , and R ³ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and R ⁴ and R ⁵ each independently represent a hydrogen atom or a carbon An alkyl group having 1 to 3 atoms, R ⁶ represents a substituent represented by the general formula (a), (In the general formula (a), R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) R ⁸ represents a hydrogen atom or an organic group, and p is R of each phenolic ring in the entire epoxy resin of the present disclosure. The average substitution number of ⁶ represents a number from 0 to 1. In addition, * in the above-mentioned general formulas (V) and (VI) represents a bond with other atoms. ) In the above general formulas (V) and (VI), R ¹ to R ⁸ are the same as R ¹ to R ⁸ in the above general formulas (I) and (II), so they are omitted here.

The epoxy resin of the present disclosure is preferably represented by the following general formulas (VII) and/or (VIII). (In the above-mentioned general formulas (VII) and (VIII), G represents a glycidyl group, R ¹ , R ² , and R ³ each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and R ⁴ and R ⁵ each independently represent a hydrocarbon group having 1 to 6 carbon atoms. independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ⁶ represents a substituent represented by the general formula (a), (In the general formula (a), R ⁷ represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.) 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 It is the average substitution number of R ⁶ per phenolic ring in the entire epoxy resin of the present disclosure, and is more preferably a number of 0 to 1. ) R ¹ to R ⁸ in the general formulas (VII) and (VIII) are the same as R ¹ to R ⁸ in the above general formulas (I) and (II), so they are omitted here. )

＜＜Better 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/eg, and further preferably 240 to 350 g/eq. If the epoxy equivalent of the epoxy resin is within the above range, the generation of active hydroxyl groups that occurs when the epoxy resin reacts with the hardener can be suppressed, and the resulting cured product will have improved heat resistance and low moisture absorption, and the resulting It is also preferred because it has excellent reflow resistance. The measurement of epoxy equivalent in this specification is also based on JIS K 7236 as described in the column of Examples.

The epoxy resin of the present disclosure preferably has a melt viscosity of 0.01 to 5 dPa at 150°C measured with an ICI viscometer. s, preferably 0.01~2dPa. s, more preferably 0.01~0.6dPa. s. When the melt viscosity of the epoxy resin is within the above range, it is preferable because the viscosity is low and the fluidity is excellent, and the resulting cured product has excellent formability. The melt viscosity in this specification is measured using an ICI viscometer in accordance with ASTM D4287, as described in the column of Examples.

The epoxy resin of the present disclosure has low viscosity and excellent fluidity, so the number average molecular weight (Mn) is preferably in the range of 430 to 1500. Moreover, the weight average molecular weight (Mw) is preferably in the range of 800 to 2,000. The molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably in the range of 1.1 to 3. The molecular weight of the epoxy resin in the present invention is measured using gel permeation chromatography (hereinafter referred to as "GPC") under the measurement conditions described in the examples described below.

＜How to manufacture epoxy resin＞ Hereinafter, the manufacturing method of the epoxy resin of this disclosure is demonstrated. If the epoxy resin in this embodiment is a glycidyl etherate of the polyvalent hydroxyl resin in this embodiment, its production method is not particularly limited, and it can be produced by any method. Examples of the method for producing the epoxy resin disclosed in the present disclosure include a method including the following steps. Step (1): As the reaction raw material (1), the aromatic compound (A), the aromatic divinyl compound (B1), and any aromatic divinyl compound (B1) are reacted to obtain as many as in this embodiment. Steps to prepare hydroxyl compounds; Step (2): As the reaction raw material (2), the polyvalent hydroxy compound in this embodiment obtained in step (1) is reacted with epihalohydrin to obtain the epoxy resin of the present disclosure. Each step of the method for manufacturing the epoxy resin of the present disclosure is described in sequence below.

＜＜Step (1): Manufacturing steps of polyvalent hydroxyl resin＞＞ The steps for producing the polyvalent hydroxy compound in this embodiment will be described below. The method for producing the polyvalent hydroxyl resin in this embodiment is not particularly limited. For example, an aromatic compound (A) containing a phenolic hydroxyl group and two or more hydrocarbon groups can be mixed with an aromatic compound in the presence of an acid catalyst. The divinyl compound (B1) (for example: divinylbenzene), and further the aromatic monovinyl compound (B2) (for example: ethylvinylbenzene) and other other compounds are reacted as needed to produce many of the compounds in this embodiment. Valent hydroxyl resin.

The polyvalent hydroxyl resin obtained by the method for producing the polyvalent hydroxyl resin of this embodiment can be adjusted to the blending ratio of the aromatic divinyl compound (B1) and the usable aromatic monovinyl compound (B2). Control hydroxyl equivalent, etc.

Regarding the blending ratio of the aromatic compound (A), the aromatic divinyl compound (B1), and the aromatic monovinyl compound (B2), when considering the formability during production of the obtained cured product , the physical property balance of curability is preferably ethylene contained in the above-mentioned aromatic divinyl compound (B1) and the above-mentioned aromatic monovinyl compound (B2) relative to 1 mol of the above-mentioned aromatic compound (A). The base molar number is 0.1 to 1 mol, preferably 0.1 to 0.95 mol.

In this embodiment, the reaction between the aromatic compound (A) and the aromatic divinyl compound (B1) and/or the 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 acids 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, dimethyl sulfate, and diethyl sulfate; zinc chloride, Lewis acids such as aluminum chloride, ferric chloride, boron trifluoride or solid acids such as ion exchange resin, activated clay, silica-alumina, zeolite, etc. The usage amount of the aforementioned acid catalyst is preferably 0.01 to 50 parts by mass, more preferably 0.01 to 10 parts by mass, and still more preferably 0.1 to 5 parts per mass of 100 parts by mass in total of the raw materials of the polyvalent hydroxyl resin. parts by mass. In addition, the above reaction is usually carried out at 10 to 250°C for 1 to 20 hours.

Examples of solvents that can be used in the above reaction include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol, methylceluso, and ethylceluso; acetone, methyl ethyl ketone, Ketones such as methyl isobutyl ketone; ethers such as dimethyl ether, diethyl ether, diisopropyl ether, tetrahydrofuran, and dihexane; aromatic compounds such as benzene, toluene, chlorobenzene, dichlorobenzene, etc. .

As for the specific method of carrying out the above reaction, generally all the reaction raw materials are charged at once and reacted at a prescribed temperature; or the aromatic compound (A) and an acid catalyst are charged and maintained at a prescribed temperature. , a method in which the aromatic divinyl compound (B1), other compounds (for example, the aromatic monovinyl compound (B2)), etc. are dropped and allowed to react. At this time, the dropping time is usually 1 to 10 hours, preferably 5 hours or less. After the reaction, when using a solvent, the solvent and unreacted matter can be distilled off as needed to obtain the aforementioned polyvalent hydroxyl resin. On the other hand, when a solvent is not used, the target polyvalent hydroxyl resin can be obtained by distilling off unreacted substances.

＜＜Step (2): Glycidyl etherification step＞＞ In this step, the polyvalent hydroxy compound obtained in step (1) is subjected to an etherification reaction with epihalohydrin, and the hydrogen atom in the phenolic hydroxyl group of the polyvalent hydroxy compound is replaced with an epoxypropyl group, thereby obtaining the disclosed method. Epoxy resin is a glycidyl etherate of a polyvalent hydroxyl compound.

Examples of the reaction of the polyvalent hydroxyl resin and epihalohydrin include a method of reacting in the presence of an alkaline catalyst, usually in the range of 20 to 150°C, preferably 30 to 80°C, for 0.5 to 10 hours. wait.

In this embodiment, examples of the epihalohydrin include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. The amount of epihalohydrin added may be used in excess based on 1 mole of the total hydroxyl groups of the polyvalent hydroxyl resin, but is usually 1.5 to 30 moles, preferably 2 to 15 moles.

Examples of the alkaline catalyst include alkaline earth metal hydroxides, alkali metal carbonates, alkali metal hydroxides, and the like. Among these, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity, and specifically, sodium hydroxide, potassium hydroxide, etc. are more preferable. In addition, these alkaline catalysts can be used in a solid state or in an aqueous solution state. The amount of the alkaline catalyst added is preferably in the range of 0.9 to 2 moles per mole of the total hydroxyl groups of the polyvalent hydroxyl resin.

In this embodiment, the reaction between the polyvalent hydroxyl resin and epihalohydrin can be carried out in an organic solvent. Examples of organic solvents used include ketones such as acetone and methyl ethyl ketone; methanol, ethanol, 1-propanol, isopropanol, 1-butanol, secondary butanol, and tertiary butanol. Alcohols such as alcohol; methyl silusa, ethyl silusa and other ethers; ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, diethoxyethane; Aprotic polar solvents such as acetonitrile, dimethylsulfoxide, dimethylformamide, etc. Each of these organic solvents may be used alone, or two or more of them may be used in combination appropriately to adjust the polarity.

After the reaction with the epihalohydrin is completed, the excess epihalohydrin is distilled off to obtain a crude product. If necessary, the obtained crude product can be dissolved in an organic solvent again, and an alkaline catalyst can be added to react again, thereby reducing hydrolyzable halogen. The salt generated by the reaction can be removed by filtration, water washing, etc. Moreover, when an organic solvent is used, it can be distilled off and only the resin solid content can be taken out, or it can be used as a solution as it is.

＜Cureable composition＞ The epoxy resin of this disclosure can be used for preparing a curable composition. The curable composition may contain the epoxy resin of the present disclosure, the curing agent for epoxy resin, and any other components (inorganic filler, silane coupling agent, curing aid, etc.). By using the epoxy resin of the present disclosure in a curable composition, the curable composition has low viscosity when melted and has excellent formability. In addition, the cured product obtained from the curable composition has a high degree of balance between low moisture absorption, low elasticity during heat, and high adhesion, and therefore has excellent reflow resistance. Due to these characteristics, the curable composition using the epoxy resin of the present disclosure exhibits excellent characteristics as a semiconductor packaging material, for example.

＜＜Hardening agent for epoxy resin＞＞ The curable composition of this embodiment can use a curing agent for epoxy resin that can carry out a cross-linking reaction with the epoxy group of the epoxy resin without particular limitation. Examples of the curing agent include phenol curing agents, amine curing agents, acid anhydride curing agents, active ester resins, cyanate ester resins, and the like. The aforementioned hardener may be used alone or in combination of two or more types.

Examples of the phenol hardener include: phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadienyl phenol addition type resin, phenol aralkyl resin (ZYLOCK Resin), naphthol aralkyl resin, trisphenol methane resin, tetraphenol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl Modified phenol resin (a compound containing polyvalent phenolic hydroxyl groups whose phenol core is linked by bismethylene), biphenyl-modified naphthol resin (a polyvalent naphthol compound whose phenol core is linked by bismethylene), amine group Tri-modified phenolic resin (a compound containing polyvalent phenolic hydroxyl groups in which the phenol core is connected with melamine, phenylguanidine, etc.), aromatic ring-modified novolac resin containing alkoxy groups (phenol core and aromatic compounds containing alkoxy groups) Compounds containing polyvalent phenolic hydroxyl groups (compounds containing polyvalent phenolic hydroxyl groups whose rings are linked by formaldehyde). Among them, from the viewpoint of formability, phenol novolac resin and the like are more preferred. Moreover, the compound containing the said phenolic hydroxyl group may be used individually or in combination of 2 or more types.

Examples of the aforementioned amine hardener include diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), and diethylamine. DEAPA, N-aminoethylpiperidine, menthendiamine (MDA), isophoronediamine (IPDA), 1,3-bisaminomethylcyclohexane (1, 3-BAC), piperidine, N,N-dimethylpiperdine , aliphatic amines such as triethylenediamine; m-diamine (XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzyl Aromatic amines such as methylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-shen(dimethylaminomethyl)phenol, etc.

Examples of the acid anhydride hardener include: phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, diphenyl ketone tetracarboxylic anhydride, ethylene glycol bis-trimellitic acid ester, glycerol ginseng trimellitic acid ester, Maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, methyl Butenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexenedicarboxylic anhydride, etc.

In the curable composition of this embodiment, the amount of the hardener used relative to the amount of the epoxy resin used is, for example, a functional group equivalent ratio (for example: hydroxyl equivalent of the phenol hardener/the epoxy resin). The epoxy equivalent) is not particularly limited, but from the viewpoint of good mechanical properties of the obtained cured product, it is 1 equivalent of the total epoxy groups of the above-mentioned epoxy resin and other epoxy resins used together as necessary. , the active group in the hardener is preferably in an amount of 0.5 to 1.5 equivalents, more preferably 0.8 to 1.2.

In addition, in the curable composition of this embodiment, in addition to the above-mentioned epoxy resin and the above-mentioned curing agent, other resins can be used together in a range that does not impair the effects of the present disclosure. Examples include epoxy resins other than the aforementioned epoxy resins, maleimide resins, bismaleimide resins, polymaleimide resins, polyphenylene ether resins, and polyimide resins. Benzophenol resin, cresol novolak resin containing trimethylbenzene, styrene-maleic anhydride resin, allyl-containing resins such as diallyl bisphenol or triallyl tripolyisocyanate, polyphosphate ester, Phosphate-carbonate copolymer, etc. These other resins can be used alone or in combination of two or more types.

＜＜Solution＞＞ The curable composition of this embodiment may be prepared without a solvent, or may contain a solvent. The aforementioned solvent has the function of adjusting the viscosity of the curable composition, etc.

Specific examples of the aforementioned solvent are not particularly limited, and may 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, seluso acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as seluso and butyl carbitol; Toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene and other aromatic hydrocarbons; dimethylformamide, dimethyl Acetamide, N-methylpyrrolidone and other amide solvents. These solvents can be used alone or in combination of two or more.

The amount of the solvent used is preferably 10 to 90% by mass, more preferably 20 to 80% by mass relative to the total mass of the curable composition. When the usage amount of the solvent is 10% by mass or more, it is preferable because the workability is excellent. On the other hand, it is preferable from the viewpoint of economic efficiency if the usage amount of the solvent is 90 mass % or less.

＜＜Additive＞＞ The curable composition of this embodiment can be blended with various additives such as a hardening accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a release agent, a pigment, a colorant, and an emulsifier as needed.

＜＜Harding accelerator＞＞ The hardening accelerator is not particularly limited, and examples thereof include phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, guanidine-based hardening accelerators, and urea-based hardening accelerators. In addition, the aforementioned hardening accelerator may be used alone or in combination of two or more types.

Examples of the phosphorus-based hardening accelerator include: triphenylphosphine, tributylphosphine, triphenylphosphine, diphenylcyclohexylphosphine, tricyclohexylphosphine and other organic phosphine compounds; trimethyl phosphite , triethyl phosphite and other organic phosphite compounds; ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetrabutylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, Tetraphenylphosphonium p-tolylborate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, dicyanimine tetraphenylphosphonium, dicyanimine butylphenylphosphonium, tetrabutylphosphonium Decanoate and other phosphonium salts, etc.

Examples of the amine-based hardening accelerator include: triethylamine, tributylamine, N,N-dimethyl-4-aminopyridine (4-dimethylaminopyridine, DMAP), 2,4 ,6-Shen(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]-undecene-7(DBU), 1,5-diazabicyclo[4.3.0 ]-Nonene-5 (DBN), etc.

Examples of the imidazole-based hardening accelerator include: 2-methylimidazole, 2-undecylimidazole, 2-heptadecanylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4methyl Imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2- Methylimidazole, 1-cyanoethyl 2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-benzene Isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5hydroxymethylimidazole, 2,3-dihydro-1H -Pyrrole[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, etc.

Examples of the guanidine-based hardening accelerator include: dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, and diphenylguanidine. Guanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dode-5-ene, 7-methyl-1,5,7- Triazabicyclo[4.4.0]dode-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenyl Biguanide etc.

Examples of the urea-based hardening accelerator include: 3-phenyl 1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and chlorophenyl urea. , 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, etc.

Among the above-mentioned curing accelerators, especially when used as a semiconductor packaging material, triphenylphosphine is preferably used as a phosphorus-based compound from the viewpoint of excellent curing properties, heat resistance, electrical properties, moisture resistance reliability, etc. As the tertiary amine, 1,8-diazabicyclo-[5.4.0]-undecene (DBU) is preferably used.

The amount of the hardening accelerator used can be appropriately adjusted in order to obtain the desired hardening property, but it is preferably 0.01 to 10 parts by mass, more preferably 0.1, based on 100 parts by mass of the total amount of the mixture of the epoxy resin and the hardener. ~5 parts by mass. When the usage amount of the hardening accelerator is within the above range, the hardening property and insulation reliability are excellent, which is preferable.

＜＜Flame retardant＞＞ The flame retardant is not particularly limited, and examples thereof include inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, halogen-based flame retardants, and the like. In addition, the flame retardant can be used alone or in combination of two or more types.

The inorganic phosphorus-based flame retardant is not particularly limited, and examples thereof include red phosphorus; ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; and amide phosphates.

The aforementioned organophosphorus flame retardants are not particularly limited, and examples include: methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, and monobutyl phosphate. Ester, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis (2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, ten acid phosphate Tryster, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, methacrylic acid (2 -Hydroxyethyl) ester acid phosphate and other phosphates; 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide, diphenylphosphine oxide and other diphenylphosphine; 10-( 2,5-Dihydroxyphenyl)-10H-9-oxa-10-phosphenanthrene-10-oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphorus Phenanthrene-10-oxide, diphenylphosphinohydroquinone, diphenylphosphino-1,4-dioxonaphthalene, 1,4-cyclooctylphosphino-1,4-phenyldiol, Phosphorus-containing phenols such as 1,5-cyclooctylphosphino-1,4-phenyldiol; 9,10-dihydro-9-oxa-10-phosphophenanthrene-10 oxide, 10-(2 ,5-dihydroxyphenyl)-10H-9-oxa-10-phosphenanthrene-10-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphophenanthrene Cyclic phosphorus compounds such as -10-oxide; compounds obtained by reacting the above-mentioned phosphate ester, the above-mentioned diphenylphosphine, the above-mentioned phosphorus-containing phenol with an epoxy resin, an aldehyde compound, and a phenol compound, etc.

The aforementioned halogen-based flame retardant is not particularly limited, and examples thereof include: brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2 -Bis(tetrabromophthalimide), 2,4,6-bis(2,4,6-tribromophenoxy)-1,3,5-tribromophthalic acid, tetrabromophthalic acid wait.

The usage amount of the aforementioned flame retardant is preferably 0.1 to 20 parts by mass relative to 100 parts by mass of the epoxy resin of the present disclosure.

＜＜Inorganic filler＞＞ The aforementioned inorganic filler is not particularly limited, and examples thereof include silicon dioxide, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, and 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, zirconium titanium Barium acid, barium zirconate, calcium zirconate, zirconium phosphate, zirconium phosphotungstate, talc, clay, mica powder, zinc oxide, hydrotalcite, diaspore, carbon black, etc. Among these, silica is preferably used. At this time, as the silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica, etc. can be used. Among them, since more inorganic fillers can be blended, the aforementioned fused silica is preferred. The fused silica may be in a crushed or spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the curable composition, it is preferable to mainly use a spherical shape. Furthermore, in order to increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica. In addition, the above-mentioned inorganic filler may be used alone or in combination of two or more kinds.

In addition, the aforementioned inorganic filler can be surface treated as needed. At this time, the surface treatment agent that can be used is not particularly limited, and aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, and organosilazane compounds can be used. , titanate coupling agent, etc. Specific examples of the surface treatment agent include: 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N -Phenyl-3-aminopropyltrimethoxysilane, hexamethyldisilazane, etc.

The usage amount of the above-mentioned inorganic filler is preferably 0.5 to 95 parts by mass relative to 100 parts by mass of the total amount of the mixture of the epoxy resin and the above-mentioned hardener disclosed in the present disclosure. When the usage amount of the above-mentioned inorganic filler is within the above-mentioned range, the flame retardancy and insulation reliability are excellent, which is preferable. Moreover, in addition to the above-mentioned inorganic filler, an organic filler can also be blended within the range which does not impair the characteristics of this disclosure. Examples of the organic filler include polyamide particles.

This disclosure is a cured product of the curable composition of this embodiment. By using the epoxy resin of the present disclosure, the cured product obtained from the curable composition of the present embodiment containing the epoxy resin of the present disclosure can exhibit low hygroscopicity, elastic modulus at low heat, or high elasticity with metal materials. The adhesion becomes better. As for the method of obtaining a cured product in which the curable composition of the present embodiment undergoes a curing reaction, for example, the heating temperature during heat curing is not particularly limited, but is usually 100 to 300°C, and the heating time is 1~24 hours.

The cured product of this embodiment preferably has a moisture absorption rate of 1.3% or less. The method for measuring the moisture absorption rate is the same as the evaluation method described in the column of Examples.

＜Semiconductor packaging materials＞ This disclosure is a semiconductor packaging material containing the curable composition of this embodiment. The semiconductor packaging material obtained by using the curable composition of this embodiment uses the epoxy resin of the present disclosure, which has low viscosity and excellent fluidity, and further improves hygroscopicity, thermal elastic modulus, and adhesion with metal materials. Therefore, the processability, formability, and reflow resistance of the manufacturing step are excellent, making it a preferred aspect.

The curable composition of this embodiment used for the semiconductor encapsulating material may contain an inorganic filler. In addition, the filling ratio of the inorganic filler can be used in the range of, for example, 0.5 to 95 parts by mass relative to 100 parts by mass of the curable composition of the present embodiment.

An example of a method for obtaining the semiconductor encapsulating material is to use an extruder, a kneader, a roller, etc. to fully melt and mix the curable composition of the present embodiment with optional additives until they are uniform. methods, etc.

[Semiconductor device] The present disclosure is a semiconductor device containing a cured product of the aforementioned semiconductor packaging material. The semiconductor device obtained by using the semiconductor packaging material obtained by using the curable composition of the present embodiment has low viscosity and excellent fluidity due to the use of the epoxy resin of the present disclosure, and further improves hygroscopicity, thermal elastic modulus, or combination with Due to the adhesion of metal materials, the processability, formability, and reflow resistance of the manufacturing steps are excellent, making it a preferred aspect.

Examples of methods for obtaining the semiconductor device include molding the semiconductor packaging material using a casting or transfer molding machine, an injection molding machine, etc., and further heating and hardening it at a temperature ranging from room temperature (20°C) to 250°C. .

[Prepreg] The present disclosure is a prepreg having a reinforcing base material and a semi-cured material impregnated with the curable composition of this embodiment in the reinforcing base material. A method for obtaining a prepreg from the above-mentioned curable composition includes blending an organic solvent described below and impregnating the varnished curable composition into a reinforcing base material (paper, glass cloth, glass non-woven fabric, polyaromatic amide paper, polyarylamide cloth, glass mat, glass gauze cloth, etc.), and then heat it at a heating temperature corresponding to the type of solvent used, preferably 50 to 170°C. The mass ratio of the curable composition and the reinforcing base material used at this time is not particularly limited, but it is usually preferably prepared so that the resin component in the prepreg becomes 20 to 60 mass %.

As for the organic solvent used here, examples include: methyl ethyl ketone, acetone, dimethyl formamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methylceluso, Ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. can be selected and used in an appropriate amount according to the application. For example, when further manufacturing a printed circuit board from a prepreg as follows, it is preferred. In order to use polar solvents such as methyl ethyl ketone, acetone, and dimethylformamide with a boiling point of 160° C. or lower, it is preferred to use a ratio of 40 to 80% by mass of non-volatile components.

[Circuit board] The present disclosure is a circuit substrate of a laminate of the prepreg and copper foil. An example of a method for obtaining a printed circuit board from the curable composition of this embodiment is to laminate the above-mentioned prepregs by a conventional method, appropriately overlap copper foils, and heat at 170 to 300°C under a pressure of 1 to 10 MPa. The method is to press for 10 minutes to 3 hours.

[build up film] This disclosure is a deposited film containing the curable composition of this embodiment. An example of a method for producing the deposited film of the present embodiment is a method of applying the above-mentioned curable composition on a support film to form a curable composition layer to form an adhesive film for a multilayer printed wiring board. .

When producing a deposited film from a curable composition, it is important that the film is softened under the lamination temperature conditions of the vacuum lamination method (usually 70 to 140°C), and that the film can be filled with resin until it exists in the circuit while being laminated with the circuit board. In order to exhibit the fluidity (resin flow) in the through-hole or through-hole of the substrate, it is preferable to blend the above-mentioned components.

Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is generally preferable that the resin can be filled within this range. In addition, when laminating both sides of the circuit board, it is desirable to fill approximately 1/2 of the through hole.

The method of manufacturing the above-mentioned adhesive film can be, specifically, by preparing the above-mentioned curable composition in the form of varnish, applying the varnish-like composition to the surface of the support film (Y), and further using heating or blowing. It is produced by drying the organic solvent with hot air or the like to form a composition layer (X) composed of a curable composition.

The thickness of the formed composition layer (X) is generally preferably greater than the thickness of the conductor layer. The thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, so the thickness of the composition layer (X) is preferably in the range of 10 to 100 μm.

In addition, the composition layer (X) in this embodiment can be protected by a protective film described below. By protecting it with a protective film, adhesion and damage of dust and the like on the surface of the composition layer (X) can be prevented.

Examples of the above-mentioned support film and protective film include: polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyethylene terephthalate (hereinafter sometimes referred to as "PET"), polyethylene naphthalate Diester and other polyesters; polycarbonate; polyimide; and release paper, copper foil, aluminum foil and other metal foils. In addition, in addition to MAD treatment and corona treatment, the support film and protective film can also be subjected to release treatment.

The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, preferably 25 to 50 μm. In addition, the thickness of the protective film is preferably 1 to 40 μm.

The above-mentioned support film (Y) is laminated on the circuit substrate or is cured by heating to form an insulating layer and then peeled off. If the supporting film (Y) is peeled off after heat-hardening the adhesive film, adhesion of dust and the like during the hardening step can be prevented. When peeling off after hardening, the support film is usually subjected to release treatment in advance.

[Other uses] Since the cured product obtained from the curable composition of this embodiment is excellent in low moisture absorption and high toughness, it can be used not only for semiconductor packaging materials, semiconductor devices, prepregs, circuit substrates, and deposited films, but also It is suitable for use in various applications such as stacking substrates, adhesives, photoresist materials, and matrix resins for fiber-reinforced resins, but the applications are not limited to these. [Example]

The present invention will be explained concretely through Examples and Comparative Examples. The following "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 Table 1 and Table 2.

＜Measurement of epoxy equivalent＞ Measurement was performed in accordance with JIS K 7236.

<Method for measuring melt viscosity at 150°C> Measured using ICI viscometer according to ASTM D4287.

＜Measurement of Softening Point＞ Measurement was performed in accordance with JIS K7234.

＜Measurement of GPC＞ Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation, Column: Protection column "HXL-L" manufactured by Tosoh Co., Ltd. +Made by Tosoh Co., Ltd. "TSK-GEL G2000HXL" +Made by Tosoh Co., Ltd. "TSK-GEL G2000HXL" +Made by Tosoh Co., Ltd. "TSK-GEL G3000HXL" +Made by Tosoh Co., Ltd. "TSK-GEL G4000HXL" Detector: RI (differential refractor) Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation Measurement conditions: Column temperature 40℃ Expansion solvent Tetrahydrofuran Flow rate 1.0ml/minute Standard: According to the measurement manual of the aforementioned "GPC Workstation EcoSEC-WorkStation", use the following monodisperse polystyrene with a known molecular weight. (use polystyrene) Tosoh Co., Ltd. "A-500" Tosoh Co., Ltd. "A-1000" Tosoh Co., Ltd. "A-2500" Tosoh Co., Ltd. "A-5000" Tosoh Co., Ltd. "F-1" Tosoh Co., Ltd. "F-2" Tosoh Co., Ltd. "F-4" Tosoh Co., Ltd. "F-10" Tosoh Co., Ltd. "F-20" Manufactured by Tosoh Co., Ltd. "F-40" Manufactured by Tosoh Co., Ltd. "F-80" Made by Tosoh Co., Ltd. "F-128" Sample: A tetrahydrofuran solution (50 μl) obtained by converting the resin solid content of the polyvalent hydroxy resin or epoxy resin obtained in the Examples shown below into 1.0% by mass was filtered with a microfilter, and measured by the aforementioned GPC. As a result, the synthesis of the obtained polyvalent hydroxyl resin or epoxy resin was confirmed. 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.

[Manufacturing Example 1: Synthesis of polyvalent hydroxyl resin (P-1)] In a flask equipped with a thermometer, cooling tube, fractionating tube, nitrogen introduction tube, and stirrer, feed 488.6g (4.00 mol) of 2,6-stubble phenol and 244g of toluene, and add 4.9g of p-toluenesulfonic acid. Raise temperature to 115°C. After confirming that the raw materials were completely dissolved, 260.4 g of a mixture of divinylbenzene and ethylvinylbenzene (DVB-810, manufactured by Nippon Steel Chemical Co., Ltd., mass ratio of divinylbenzene/ethylvinylbenzene) was dropped over 2 hours. =81/19), and reacted at 115°C for 1 hour. After the reaction was completed, the temperature was lowered to 80°C, and a NaOH aqueous solution was used for neutralization. Unreacted 2,6-stylphenol and toluene were removed under heating and reduced pressure to obtain polyvalent hydroxyl resin (P-1). The physical property values of the obtained polyvalent hydroxyl resin (P-1) are shown in Table 1, and the GPC chart is shown in Figure 1.

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

[Comparative Production Example 1: Synthesis of polyvalent hydroxyl resin (P-3)] In a flask equipped with a thermometer, cooling tube, fractionating tube, nitrogen introduction tube, and stirrer, feed 627.4g (6.66 mol) of phenol and 313g of toluene, add 6.3g of p-toluenesulfonic acid, and raise the temperature 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 dropped 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 a NaOH aqueous solution was used for neutralization. Unreacted phenol and toluene were removed under heating and reduced pressure to obtain polyvalent hydroxyl resin (P-3). Table 1 shows the physical property values of the obtained polyvalent hydroxyl resin (P-3).

[Table 1] Table 1 Manufacturing example 1 Manufacturing example 2 Comparative manufacturing example 1 Polyvalent hydroxyl resin 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

[Example 1: Synthesis of epoxy resin (E-1)] Into a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, 300.0 g of the polyvalent hydroxyl resin (P-1) obtained in Production Example 1 and 923 g (5.0 equivalent) of Dissolve epichlorohydrin, 238g of n-butanol, and 40g of water. After the temperature was raised to 60° C., 134 g (1.1 equivalent) of 49% sodium hydroxide aqueous solution was dropped over 5 hours. After that, stirring was continued for 0.5 hours under the same conditions. Then, unreacted epichlorohydrin was distilled off by distillation under reduced pressure. 700 g of methyl isobutyl ketone was added to the obtained crude epoxy resin and dissolved. Further, 15 g of 5% sodium hydroxide aqueous solution was added to this solution, and the mixture was reacted at 80° C. for 2 hours, and then washed three times with 190 g of water until the pH of the cleaning solution became neutral. Then, the system is dehydrated by azeotropy, and after precision filtration, the solvent is distilled off under reduced pressure to obtain epoxy resin (E-1). The physical property values of the obtained epoxy resin (E-1) are shown in Table 2, and the GPC chart is shown in Figure 3.

[Example 2: Synthesis of epoxy resin (E-2)] The reaction was carried out in the same manner as in Example 1 except that 300.0 g of the polyvalent hydroxyl resin (P-2) obtained in Production Example 2 was used instead of the polyvalent hydroxyl resin (P-1) to obtain an epoxy resin (E-2). The physical property values of the obtained epoxy resin (E-2) are shown in Table 2, and the GPC chart is shown in Figure 4.

[Comparative Example 1: Synthesis of epoxy resin (E-3)] The reaction was carried out in the same manner as in Example 1, except that 300.0 g (1.0 equivalent of hydroxyl group) of the polyvalent hydroxyl resin (P-3) obtained in Comparative Production Example 1 was used instead of the polyvalent hydroxyl resin (P-1). (E-3). Table 2 shows the physical property values of the obtained epoxy resin (E-3).

[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

[Examples 3, 4, and Comparative Example 2] ＜Preparation of curable composition＞ Each component was blended in the composition shown in Table 3 to obtain a curable composition that was melt-kneaded. The details of each ingredient are as follows. Hardener: Phenol novolac type phenol resin (DIC Co., Ltd. "TD-2131" hydroxyl equivalent 104g/eq) Hardening accelerator: Triphenylphosphine ("TPP" manufactured by Hokuho Chemical Industry)

<Preparation and evaluation of test pieces for moisture absorption tests> The curable composition obtained above was cured under normal pressure pressure at 150°C for 10 minutes so that the thickness of the cured product became 2.4 mm, and then post-cured at 175°C for 5 hours, and then evaluated. Use hardener.

＜Evaluation of hygroscopicity＞ The hardened material was cut into a size of 75 mm×25 mm with a diamond cutter, and this was used as a test piece for hygroscopicity evaluation. Hygroscopicity evaluation is based on placing it in an environment of temperature/humidity: 85°C/85% for 300 hours. [(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 (%)] was evaluated as the moisture absorption rate.

＜Evaluation of hot elastic modulus＞ The aforementioned hardened material was cut into a size of 5 mm × 54 mm with a diamond cutter, and a viscoelasticity measuring device ("Solid Viscoelasticity Measuring Device RSA II" manufactured by Rheometric Company, rectangular tension method: frequency 1 Hz, temperature rise rate 3°C/min) was used. The storage modulus value at 260°C was measured.

[table 3] table 3 unit Example 3 Example 4 Comparative example 2 The composition of the hardening composition Epoxy resin E-1 parts by mass 73.2 E-2 parts by mass 74.3 E-3 parts by mass 73.1 Hardener TD-2131 parts by mass 26.8 25.7 26.9 hardening accelerator TPP parts by mass 1 1 1 Physical properties of hardened material Hygroscopicity % 0.9 0.7 1 Thermal elastic modulus MPa 6 5 15

[Examples 5, 6, and Comparative Example 3] A grain shear test was performed as an adhesion test to the copper plate. The test piece was prepared as follows.

Various materials shown in Table 4 were melt-kneaded using two rollers at a temperature of 80° C. for 10 minutes to obtain a curable composition. The details of each ingredient are as follows. Hardener: Phenol novolac type phenol resin (DIC Co., Ltd. "TD-2131" hydroxyl equivalent 104g/eq) Hardening accelerator: Triphenylphosphine ("TPP" manufactured by Hokuho Chemical Industry) Molten silica: "FB-560" manufactured by Denki Chemical Co., Ltd. Silane coupling agent: γ-glycidoxyethoxysilane ("KBM-403" manufactured by Shin-Etsu Chemical Industry Co., Ltd.)

<Preparation of test pieces> The curable compositions of the above-mentioned examples and comparative examples were pulverized to prepare evaluation compositions, and a transfer molding machine was used at a pressure of 70 kg/cm ² , a pressing speed of 5 cm/second, a temperature of 175°C, and a time of 600 seconds. Under the conditions, the molded product was molded on copper foil so that the size of the molded product became 6 mm × 6 mm × 2 mmt (thickness 2 mm), and a test piece was obtained. In addition, the copper foil system uses EFTEC-64T (0.15mmt, manufactured by Furukawa Electric Industries, Ltd.).

＜Grain Shear Test Evaluation＞ The test system uses an adhesion test ("PTR-1102" manufactured by RHESCA Corporation) to conduct a grain shear test. The shearing speed was 0.1 mm/second, and it was implemented as N5 for one sample, and the average value (gf) of the peeling strength from the copper foil was calculated. The peel strength is shown by relative evaluation, and the strength of each composition when the molded article of Comparative Example 6 is taken as 1.0 is shown in Table 4.

[Table 4] Table 4 unit Example 5 Example 6 Comparative example 3 The composition of the hardening composition Epoxy resin E-1 parts by mass 58.6 E-2 parts by mass 59.5 E-3 parts by mass 58.5 Hardener TD-2131 parts by mass 21.4 20.5 21.5 hardening accelerator TPP parts by mass 1 1 1 fused silica FB-560 parts by mass 81 81 81 Coupling agent KBM-403 parts by mass 0.8 0.8 0.8 Physical properties of hardened material Peel strength gf 1.3 1.5 1

According to Table 2, the epoxy resin-based resin of the present invention has a low melt viscosity, so improvements in moldability and filler filling rate can be expected. In addition, as shown in Table 3, the epoxy resin E-3 series has poor hygroscopicity, and the epoxy resin (E-1, E-2) series of the present invention has excellent hygroscopicity, so welding crack resistance and reliable connection can be expected. sexual enhancement. Furthermore, the epoxy resin system of the present invention has an extremely small storage modulus near the reflow temperature, and can be expected to improve peeling resistance during reflow. Table 4 shows the results of the adhesion test of the epoxy resin of the present invention to copper foil, and it was confirmed that the epoxy resin of the present invention shows excellent adhesion to copper foil.

Based on the above, the epoxy resin of the present invention is highly compatible with low viscosity during melting, moisture absorption, and low elasticity during heat, which are inversely related to each other, and exhibits excellent adhesion to copper foil. Therefore, it is widely used in the field of electronic materials. etc. are particularly useful.

without.

Figure 1 shows the GPC chart of the polyvalent hydroxyl resin (P-1) obtained in Example. Figure 2 shows the GPC chart of the polyvalent hydroxyl resin (P-2) obtained in Example. Figure 3 shows the GPC chart of the epoxy resin (E-1) obtained in Example. Figure 4 shows the GPC chart of the epoxy resin (E-2) obtained in Example.

without.

Claims (12)

An epoxy resin, which is a polyvalent hydroxyl resin ring using 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) as the reaction raw material (1) Oxypropyl etherate. For example, the epoxy resin of claim 1 uses the polyvalent hydroxyl resin and epihalohydrin (C) as reaction raw materials (2). The epoxy resin of claim 1 or 2 further contains an aromatic monovinyl compound (B2) as the reaction raw material (1). The epoxy resin of claim 3, wherein the mass ratio ((B1)/(B2)) of the aromatic divinyl compound (B1) to the aromatic monovinyl compound (B2) is 50/50~99 /1. The epoxy resin according to any one of claims 1 to 4, wherein the hydrocarbon group is an alkyl group having 1 to 6 carbon atoms. A curable composition containing the epoxy resin according to any one of claims 1 to 5, and a hardener. A hardened product, which is a hardened product of the curable composition of claim 6. A prepreg having a reinforcing base material and a semi-hardened product impregnated with the curing composition according to claim 6 in the reinforcing base material. A circuit board having the prepreg according to claim 8 and a laminate of copper foil. A build up film containing the curable composition of claim 6. A semiconductor packaging material containing the curable composition according to claim 6. A semiconductor device including a cured product of the semiconductor packaging material according to claim 11.