CN116583943A - Epoxy resin, curable composition, cured product, semiconductor sealing material, semiconductor device, prepreg, circuit board, and laminated film - Google Patents

Abstract

The present invention provides an epoxy resin, which contains: a glycidyl ether compound (E1) of a biphenol compound (P1), and a glycidyl ether compound (E2) of a phenolic hydroxyl-containing resin (P2). The hydroxyl resin (P2) uses a dihydroxy aromatic hydrocarbon compound (α) and an aralkylating agent (β) represented by general formula (1‑1) or (1‑2) as reaction raw materials. [In the following general formulas (1-1) and (1-2), X represents any one of a halogen atom, a hydroxyl group, and an alkoxy group. R ¹ each independently represent any of a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ² each independently represent a hydrogen atom or a methyl group. Ar ¹ represents any of phenyl, naphthyl, and structural sites having one or more aromatic nuclei, halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups. ]

Description

Epoxy resin, curable composition, cured product, semiconductor sealing material, semiconductor device devices, prepregs, circuit substrates, and laminated films

technical field

The present invention relates to an epoxy resin, a curable composition, a cured product, a semiconductor sealing material, a semiconductor device, a prepreg, a circuit board, and a laminated film.

Background technique

Epoxy resin compositions containing epoxy resin and its curing agent as essential components are used in electronic components such as semiconductor sealing materials, printed circuit boards, etc., due to their excellent physical properties such as high heat resistance, moisture resistance, and low viscosity. It is widely used in conductive adhesives such as conductive pastes, other adhesives, substrates for composite materials, paints, photoresist materials, and color-developing materials.

Among the various applications mentioned above, in the field of semiconductor sealing materials, surface mounting of semiconductor packages such as BGA and CSP is progressing. However, in order to perform surface mounting, semiconductor packages are exposed to high temperatures in the reflow process. The resin material used requires high heat resistance.

Furthermore, in order to reduce the warpage of the semiconductor sealing material which occurs in the miniaturization/thinning of the electronic equipment and the mass sealing process in recent years, a resin material imparted with high toughness is required.

In addition to the above-mentioned performances, semiconductor encapsulating materials are required to be filled with inorganic fillers such as silica and used. Therefore, in order to increase the filling rate of fillers, resin materials are also required to have low viscosity and excellent fluidity.

As a sealing material for semiconductors satisfying required properties, for example, the use of an aralkyl-modified poly(oxynaphthylene)-type epoxy resin is disclosed (see Patent Document 1).

However, the obtained cured product of the aforementioned epoxy resin disclosed in Patent Document 1 is excellent in heat resistance, but the melt viscosity of the epoxy resin itself is high, and the fluidity and formability of the epoxy resin composition containing the aforementioned epoxy resin are poor. , It is not clear about the reduction of warpage, etc.

In this way, in the field of sealing materials for semiconductors, for curing epoxy resin compositions that can obtain particularly low viscosity and excellent fluidity and moldability, high heat resistance and high toughness obtained from the aforementioned epoxy resin compositions, As far as the epoxy resin composition for semiconductor sealing of objects is concerned, it is not available at present.

prior art literature

patent documents

Patent Document 1: Japanese Patent No. 5689230

Contents of the invention

The problem to be solved by the invention

Therefore, the problem to be solved by the present invention is to provide: an epoxy resin which has a low melt viscosity and can contribute to fluidity and formability, a curable composition containing the aforementioned epoxy resin, a curable composition obtained by using the aforementioned curable composition, Cured products with high heat resistance and high toughness, semiconductor sealing materials, semiconductor devices, prepregs, circuit boards, and laminated films.

solutions to problems

The inventors of the present invention conducted intensive studies to solve the above-mentioned problems, and as a result, found an epoxy resin capable of contributing to excellent fluidity and formability, a curable composition containing the above-mentioned epoxy resin, a curable composition using the above-mentioned The obtained cured product excellent in high heat resistance and high toughness, semiconductor sealing material, semiconductor device, prepreg, circuit board, and laminated film have completed the present invention.

That is, the present invention relates to an epoxy resin comprising: a glycidyl ether compound (E1) of a biphenol compound (P1) and a glycidyl ether compound (E2) of a phenolic hydroxyl group-containing resin (P2), wherein the The phenolic hydroxy resin (P2) uses a dihydroxy aromatic compound (α) and an aralkylating agent (β) represented by the following general formula (1-1) or (1-2) as reaction raw materials.

[In the above general formulas (1-1) and (1-2), X represents any one of a halogen atom, a hydroxyl group, and an alkoxy group. R ¹ each independently represent any of a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ² each independently represent a hydrogen atom or a methyl group. Ar ¹ represents any of phenyl, naphthyl, and structural sites having one or more aromatic nuclei, halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups. ]

In addition, the present invention relates to an epoxy resin comprising: a glycidyl ether compound (E3) of a mixture of a biphenol compound (P1) and a phenolic hydroxyl-containing resin (P2), the phenolic hydroxyl-containing resin (P2) and A dihydroxy aromatic hydrocarbon compound (α) and an aralkylating agent (β) represented by the following general formula (1-1) or (1-2) are used as reaction raw materials.

[In the above general formulas (1-1) and (1-2), X represents any one of a halogen atom, a hydroxyl group, and an alkoxy group. R ¹ each independently represent any of a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ² each independently represent a hydrogen atom or a methyl group. Ar ¹ represents any of phenyl, naphthyl, and structural sites having one or more aromatic nuclei, halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups. ]

In the epoxy resin of the present invention, the ratio of the biphenol compound (P1) to the total mass of the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2) is preferably 0.5 mass % or more and 40 mass % or less .

In the epoxy resin of this invention, it is preferable that the said phenolic hydroxyl-containing resin (P2) contains the compound (A) which has three naphthalene ring structures in 1 molecule.

In the epoxy resin of the present invention, the content of the compound (A) in the phenolic hydroxyl-containing resin (P2) is preferably 5 to 50% as calculated from the area ratio of the spectrum of gel permeation chromatography (GPC).

In the epoxy resin of the present invention, it is preferable that the melt viscosity at 150° C. measured by an ICI viscometer is 0.01 to 5 dPa·s.

The present invention relates to a curable composition containing the aforementioned epoxy resin and a curing agent for epoxy resin.

The present invention relates to a cured product of the aforementioned curable composition.

The present invention relates to a semiconductor sealing material containing the aforementioned curable composition.

The present invention relates to a semiconductor device including a cured product of the aforementioned semiconductor sealing material.

The present invention relates to a prepreg comprising: a reinforcing base material; and a semi-cured product of the curable composition impregnated into the reinforcing base material.

The present invention relates to a circuit board which is a laminate of the aforementioned prepreg and copper foil.

The present invention relates to a laminated film containing the aforementioned curable composition.

The effect of the invention

The epoxy resin of the present invention is low in viscosity, excellent in fluidity and formability, and the cured product of the curable composition containing the above epoxy resin is excellent in high heat resistance and high toughness, so it is used as an electrical material such as a semiconductor sealing material. Especially useful with resin materials.

Description of drawings

FIG. 1 is a GPC chart of the phenolic hydroxyl-containing resin (P2-1) obtained in Synthesis Example 1. FIG.

Fig. 2 is the GPC graph of the epoxy resin (1) obtained in embodiment 1.

Fig. 3 is the GPC figure of the epoxy resin (2) that obtains in embodiment 2.

Fig. 4 is the GPC figure of the epoxy resin (3) that obtains in embodiment 3.

Detailed ways

The present invention relates to an epoxy resin comprising: a glycidyl ether compound (E1) of a biphenol compound (P1) and a glycidyl ether compound (E2) of a phenolic hydroxyl-containing resin (P2), the phenolic hydroxyl-containing The resin (P2) uses a dihydroxy aromatic compound (α) and an aralkylating agent (β) represented by the following general formula (1-1) or (1-2) as reaction raw materials.

[In the above general formulas (1-1) and (1-2), X represents any one of a halogen atom, a hydroxyl group, and an alkoxy group. R ¹ each independently represent any of a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ² each independently represent a hydrogen atom or a methyl group. Ar ¹ represents any of phenyl, naphthyl, and structural sites having one or more aromatic nuclei, halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups. ]

In addition, the present invention relates to an epoxy resin comprising: a glycidyl ether compound (E3) of a mixture of a biphenol compound (P1) and a phenolic hydroxyl-containing resin (P2), the phenolic hydroxyl-containing resin (P2) A dihydroxy aromatic compound (α) and an aralkylating agent (β) represented by the following general formula (1-1) or (1-2) are used as reaction raw materials.

[In the above general formulas (1-1) and (1-2), X represents any one of a halogen atom, a hydroxyl group, and an alkoxy group. R ¹ each independently represent any of a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ² each independently represent a hydrogen atom or a methyl group. Ar ¹ represents any of phenyl, naphthyl, and structural sites having one or more aromatic nuclei, halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups. ]

<Biphenol compound (P1)>

The biphenol compound (P1) is not particularly limited, and examples thereof include 2,2'-biphenol, 2,4'-biphenol, 3,3'-biphenol, 4,4'-biphenol, And various compounds in which one or more aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, etc. are substituted on their aromatic rings. The aforementioned biphenol compounds (P1) may be used alone or in combination of two or more.

The above-mentioned aliphatic hydrocarbon group may be either straight-chain type or branched-chain type, and may have an unsaturated bond in the structure. Among them, aliphatic hydrocarbon groups having 1 to 4 carbon atoms are preferred because the effect of excellent heat resistance of the cured product is more pronounced. Specifically, methyl, ethyl, propyl, isopropyl, Butyl, tert-butyl, isobutyl, vinyl, allyl, etc. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy and the like. Examples of the aforementioned halogen atom include fluorine atom, chlorine atom, bromine atom and the like. In particular, it is preferable to have substituents on 4,4'-biphenol and its aromatic ring, more preferably 4,4'-biphenol, from the viewpoint of easily adjusting the melt viscosity of the epoxy resin finally obtained to a preferable value. .

<Phenolic hydroxyl-containing resin (P2)>

The above-mentioned phenolic hydroxyl-containing resin (P2) uses a dihydroxy aromatic compound (α) and an aralkylating agent (β) represented by the following general formula (1-1) or (1-2) as reaction raw materials.

[In the above general formulas (1-1) and (1-2), X represents any one of a halogen atom, a hydroxyl group, and an alkoxy group. R ¹ each independently represent any of a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ² each independently represent a hydrogen atom or a methyl group. Ar ¹ represents any of phenyl, naphthyl, and structural sites having one or more aromatic nuclei, halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups. ]

In the above general formulas (1-1) and (1-2), X represents any one of a halogen atom, a hydroxyl group and an alkoxy group. R ¹ each independently represent any of a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ² each independently represent a hydrogen atom or a methyl group. Ar ¹ represents any of phenyl, naphthyl, and structural sites having one or more aromatic nuclei, halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups.

The phenolic hydroxyl group-containing resin (P2) contains a component having a (poly)arylene ether structure produced by the intermolecular dehydration reaction of the dihydroxyarene compound (α). In addition, an aralkyl group is introduced into part or all of the aromatic rings in the phenolic hydroxyl-containing resin (P2) by the aralkylating agent (β). As a result, the distance between the glycidyl ether groups in the molecule of the glycidyl etherified product (E2) of the phenolic hydroxyl-containing resin (P2) is relatively long, and the concentration of the aromatic ring becomes high, so that the obtained Heat resistance and toughness of the cured product.

The above-mentioned dihydroxy aromatic compound (α) is not particularly limited as long as it has two hydroxyl groups on the aromatic ring, and its specific structure is not particularly limited, and various compounds can be used. Specific examples include dihydroxybenzene, dihydroxynaphthalene, and compounds having one or more substituents such as halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups on their aromatic rings. In the present invention, as the aforementioned dihydroxyarene compound (α), one type may be used alone, or two or more types may be used in combination.

In the aforementioned dihydroxybenzene, the substitution position of the two hydroxyl groups is not particularly limited, and may be any of the ortho-position, meta-position, and para-position. In addition, in the aforementioned dihydroxynaphthalene, the substitution positions of the two hydroxyl groups are not particularly limited, for example, 1,2-position, 1,4-position, 1,5-position, 1,6-position, 1,7-position, Any one of 2,3-bit, 2,6-bit, 2,7-bit.

Examples of the aforementioned halogen atom include fluorine atom, chlorine atom, bromine atom and the like. The above-mentioned aliphatic hydrocarbon group may be either straight-chain type or branched-chain type, and may have an unsaturated bond in the structure. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, etc. are mentioned. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy and the like.

Among the aforementioned dihydroxy aromatic hydrocarbon compounds (α), dihydroxy naphthalene and those having one or more halogen atoms on its aromatic ring are preferable in terms of the effect of excellent heat resistance and toughness of the obtained cured product. , aliphatic hydrocarbon group, alkoxy group and other substituent compounds, more preferably dihydroxynaphthalene. The position of the hydroxyl group on the aforementioned dihydroxynaphthalene is preferably 1,6-position or 2,7-position, more preferably 2,7-position. In addition, when two or more types of dihydroxyarene compound (α) are used in combination, dihydroxynaphthalene and one or more substituents such as halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups on its aromatic rings The proportion of the compound of is preferably 50% by mass or more, more preferably 80% by mass or more, particularly preferably 95% by mass or more in the aforementioned dihydroxyarene compound (α).

The aforementioned aralkylating agent (β) has a molecular structure represented by the aforementioned general formula (1-1) or (1-2). In the present invention, as the aforementioned aralkylating agent (β), one type may be used alone, or two or more types may be used in combination.

In the aforementioned general formulas (1-1) and (1-2), the aforementioned X represents any one of a halogen atom, a hydroxyl group, and an alkoxy group. Examples of the aforementioned halogen atom include fluorine atom, chlorine atom, bromine atom and the like. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy and the like. Among them, a halogen atom or a hydroxyl group is preferable, and a hydroxyl group is particularly preferable because of excellent reactivity.

In the aforementioned general formulas (1-1) and (1-2), the aforementioned R ¹ each independently represent any of a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Among them, a hydrogen atom is preferable from the viewpoint of excellent reactivity.

In the aforementioned general formulas (1-1) and (1-2), the aforementioned R ² each independently represent a hydrogen atom or a methyl group. Among them, a hydrogen atom is preferable from the viewpoint of excellent reactivity.

In the aforementioned general formulas (1-1) and (1-2), ^the aforementioned Ar is phenyl, naphthyl, one or more halogen atoms, aliphatic hydrocarbon groups, alkoxyl groups having one or more aromatic nuclei Any of the structural parts.

Examples of the aforementioned halogen atom include fluorine atom, chlorine atom, bromine atom and the like. The above-mentioned aliphatic hydrocarbon group may be either straight-chain type or branched-chain type, and may have an unsaturated bond in the structure. Specifically, a methyl group, an ethyl group, a propyl group, a butyl group, etc. are mentioned. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy and the like. Among them, Ar ¹ is preferably a phenyl group or a naphthyl group, more preferably a phenyl group, since the effect of excellent heat resistance and toughness of the cured product is more pronounced.

When two or more aralkylating agents (β) are used in combination, the proportion of the compound in which Ar ¹ is a phenyl group in the aralkylating agent (β) is preferably 50% by mass or more, more preferably It is 80% by mass or more, particularly preferably 95% by mass or more.

The aforementioned phenolic hydroxyl group-containing resin (P2) may use components other than the aforementioned dihydroxy aromatic hydrocarbon compound (α) and the aforementioned aralkylating agent (β) as a part of the reaction raw materials. In this case, the total mass of the aforementioned dihydroxy aromatic compound (α) and the aforementioned aralkylating agent (β) in the total mass of the reaction raw material of the aforementioned phenolic hydroxyl-containing resin (P2) is preferably 80% by mass or more, More preferably, it is 95 mass % or more.

As a method for producing the above-mentioned phenolic hydroxyl-containing resin (P2), for example, a method of reacting the reaction raw materials containing the above-mentioned dihydroxy aromatic compound (α) and the above-mentioned aralkylating agent (β) under an acid catalyst condition . In addition, the reaction can be performed in a solvent as needed.

With regard to the reaction ratio of the aforementioned dihydroxyarene compound (α) and the aforementioned aralkylating agent (β), the molar ratio [(α)/(β)] of the two is considered to be an epoxy resin having excellent fluidity. Preferably it is the range of 1/0.1-1/10, More preferably, it is the range of 1/0.1-1/1.

Examples of the acid catalyst include inorganic acids such as phosphoric acid, sulfuric acid, and hydrochloric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid, aluminum chloride, zinc chloride, tin chloride, Friedel-Crafts catalysts such as ferric chloride, diethylsulfuric acid, etc. These may be used individually or in combination of 2 or more types.

When using an inorganic acid or an organic acid as the said acid catalyst, it is preferable to use it in the range of 0.01-3 mass parts with respect to 100 mass parts of said dihydroxy aromatic hydrocarbon compounds (α). In the case of using a Friedel-Crafts catalyst as the aforementioned acid catalyst, it is preferable to

1 mole is used in the range of 0.5 to 2 moles.

The aforementioned solvents include, for example, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, ethylene glycol dimethyl Diethylene glycol diethyl ether, ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, ethylene glycol mono Methyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol Alcohol monobutyl ether, cellosolve, butyl carbitol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, toluene, xylene, chlorobenzene, etc. These may be used alone, or a mixed solvent of two or more may be used. When using these solvents, it is preferable to use in the range of 20-300 mass % with respect to the gross mass of the reaction raw material of the said phenolic hydroxyl-containing resin (P2).

The reaction of the aforementioned dihydroxy aromatic hydrocarbon compound (α) and the aforementioned aralkylating agent (β) can be carried out at a temperature of about 60-180°C, and the reaction time is about 1-24 hours. The reaction can be performed more efficiently by appropriately distilling off water and the like generated during the reaction. After completion of the reaction, the reaction system can be neutralized with an alkali compound such as an alkali metal hydroxide, or washed with water, and then dried to obtain the aforementioned phenolic hydroxyl-containing resin (P2).

The hydroxyl equivalent of the above-mentioned phenolic hydroxyl-containing resin (P2) is preferably in the range of 100 to 400 g/equivalent, preferably 110 to 300 g/equivalent, from the viewpoint that the effect of excellent heat resistance and toughness of the cured product is more remarkable. scope. In addition, the softening point is preferably in the range of 60 to 140°C.

As an example of the aforementioned phenolic hydroxyl group-containing resin (P2), for example, when using 2,7-dihydroxynaphthalene as the dihydroxyaromatic compound (α) and using benzyl alcohol as the aforementioned aralkylating agent (β), the aforementioned As for the specific structure of each component contained in a phenolic hydroxyl resin (P2), the structure etc. which are shown by any of following structural formula (2-1) - (2-18) are mentioned, for example.

For the aforementioned phenolic hydroxyl group-containing resin (P2), it is preferable to contain the aforementioned structural formulas (2-6) to (2-8), (2-10) from the viewpoint that the effect of excellent heat resistance and toughness of the cured product is more remarkable. A compound (A) having three naphthalene ring structures in one molecule as shown in (2-11).

In addition, the content of the aforementioned compound (A) in the aforementioned phenolic hydroxyl group-containing resin (P2) is preferably 5 to 50%, more preferably 10 to 45%, as calculated from the area ratio of the spectrum of gel permeation chromatography (GPC). %. In addition, gel permeation chromatography (GPC) was measured under the measurement conditions described in the Example mentioned later.

The epoxy resin of the present invention is not particularly limited as long as it contains the glycidyl ether compound (E1) of the aforementioned biphenol compound (P1) and the glycidyl ether compound (E2) of the aforementioned phenolic hydroxyl-containing resin (P2). , can be obtained by any manufacture.

As a method for producing the epoxy resin of the present invention, for example, (1) reacting the aforementioned biphenol compound (P1) with epihalohydrin to synthesize a glycidyl etherified product (E1) that has undergone glycidyl etherification, and The glycidyl-etherified product (E2) obtained by reacting the phenolic hydroxyl-containing resin (P2) with epihalohydrin was synthesized, and what mixed (contained) these was used as the epoxy resin of the present invention.

In addition, (2) epihalohydrin can be added to the mixture of the aforementioned biphenol compound (P1) and the aforementioned phenolic hydroxyl-containing resin (P2), so that the aforementioned biphenol compound (P1) and the aforementioned phenolic hydroxyl-containing resin (P2) ) react with epihalohydrin respectively, thereby synthesizing the glycidyl ether compound (E3) containing the aforementioned glycidyl ether compound (E1) and the aforementioned glycidyl ether compound (E2), and adopting the person containing the glycidyl ether compound (E3) as Epoxy resins of the present invention.

In particular, the production method of (2) above is preferable because of its simplicity and operability.

In the manufacturing method of the epoxy resin of said (1), the reaction of the said biphenol compound (P1) and an epihalohydrin, and the reaction of the said phenolic hydroxyl-containing resin (P2) and an epihalohydrin are mentioned, for example in In the presence of a basic catalyst, a method in which the reaction is usually carried out at 20 to 150° C., preferably 30 to 80° C., for 0.5 to 10 hours, and the like.

As said epihalohydrin, epichlorohydrin, epibromohydrin, (beta)-methylepichlorohydrin etc. are mentioned. The amount of epihalohydrin to be added is usually 1.5 to 30 moles, preferably 2 moles, relative to the total 1 mole of the hydroxyl groups of the aforementioned biphenol compound (P1) or the aforementioned phenolic hydroxyl-containing resin (P2). ~15 molar range.

As said basic catalyst, an alkaline earth metal hydroxide, an alkali metal carbonate, and an alkali metal hydroxide etc. are mentioned, for example. Among these, alkali metal hydroxides are preferable, and specifically, sodium hydroxide, potassium hydroxide, and the like are more preferable from the viewpoint of excellent catalytic activity. In addition, these basic catalysts may be used in a solid state or in an aqueous solution. It is preferable that the addition amount of the said basic catalyst is the range of 0.9-2 mol with respect to the total 1 mol of the hydroxyl group which the said biphenol compound (P1) or the said phenolic hydroxyl-containing resin (P2) has.

The reaction of the said biphenol compound (P1), and the said phenolic hydroxyl-containing resin (P2) with epihalohydrin can be performed in an organic solvent. Examples of organic solvents to be used include ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, sec-butanol, and tert-butanol, methyl alcohol, and the like. Cellosolves such as ethyl cellosolve and ethyl cellosolve, tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, ethers such as diethoxyethane, acetonitrile, dimethylmethylene Aprotic polar solvents such as sulfone and dimethylformamide, etc. Each of these organic solvents may be used alone, and may be used in combination of two or more as appropriate for polarity adjustment.

After the reaction with the aforementioned epihalohydrin is completed, excess epihalohydrin is distilled off to obtain a crude product. If necessary, the obtained crude product can be dissolved again in an organic solvent, and a basic catalyst can be added to carry out the reaction again, thereby reducing the hydrolyzable halogen. Salts generated during the reaction can be removed by filtration, washing with water, or the like. In addition, when an organic solvent is used, it may be distilled off to extract only the resin solid content, or it may be used as a solution as it is.

In the method for producing an epoxy resin of (1) above, the mass ratio of the glycidyl ether compound (E1) to the glycidyl ether compound (E2) is not particularly limited, and the cured product has excellent fluidity and high toughness characteristics From the viewpoint of an epoxy resin excellent in low hygroscopicity, the ratio of the glycidyl ether compound (E1) to the total mass of both is preferably 0.5% by mass or more, preferably 1% by mass or more, more preferably 5% by mass or more, particularly preferably 15% by mass or more. In addition, the upper limit thereof is preferably 40% by mass or less, more preferably 30% by mass or less.

In the method for producing an epoxy resin of the aforementioned (2), the mass ratio of the two in the mixture of the aforementioned biphenol compound (P1) and the aforementioned phenolic hydroxyl group-containing resin (P2) is excellent in fluidity and a cured product From the viewpoint of an epoxy resin with excellent toughness characteristics and low hygroscopicity, the ratio of the above-mentioned biphenol compound (P1) to the total mass of both is preferably 0.5% by mass or more, preferably 1% by mass or more, and more preferably 1% by mass or more. 5% by mass or more, particularly preferably 15% by mass or more. In addition, the upper limit thereof is preferably 40% by mass or less, more preferably 30% by mass or less.

The reaction of the mixture of the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2) with epihalohydrin can be performed by the same method as the method for producing the epoxy resin of (1) above. The amount of the epihalohydrin added is used in excess of 1 mole of the total of the hydroxyl groups of the biphenol compound (P1) and the phenolic hydroxyl-containing resin (P2), usually 1.5 to 30 moles, preferably 2 moles. ~15 molar range. In addition, a basic catalyst can be used in the same manner as in the method for producing an epoxy resin of (1), and the amount of the basic catalyst added is preferably relative to that of the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2). The total 1 mol of hydroxyl groups is in the range of 0.9 to 2 mol.

The epoxy equivalent of the epoxy resin of this invention becomes like this. Preferably it is 140-400 g/equivalent, More preferably, it is 140-350 g/equivalent. The measurement of the epoxy equivalent here is measured based on JISK7236.

The melt viscosity of the epoxy resin of the present invention at 150° C. measured by an ICI viscometer is preferably 0.01 to 5 dPa·s, more preferably 0.01 to 2 dPa·s, and even more preferably 0.01 to 1 dPa·s. When the melt viscosity of the epoxy resin is within the above range, it is low in viscosity and excellent in fluidity, and therefore it is preferable from the viewpoint of excellent moldability of the obtained cured product. The melt viscosity here is measured with an ICI viscometer in accordance with ASTM D4287.

The epoxy resin of the present invention preferably has a number average molecular weight (Mn) in the range of 200 to 1500, more preferably in the range of 200 to 800, from the viewpoint of low viscosity and excellent fluidity. In addition, the weight average molecular weight (Mw) is preferably in the range of 250-2000, more preferably in the range of 250-800. In addition, the degree of dispersion (Mw/Mn) is preferably in the range of 1-3. In the present invention, the molecular weight and degree of dispersion of the epoxy resin are measured using gel permeation chromatography (GPC) under the measurement conditions described in Examples described later.

Specific examples of the epoxy resin of the present invention include epoxy resins represented by the following structural formulas.

[In the above formula, n is an integer of 0-10. ]

<Curable composition>

The present invention relates to a curable composition containing the aforementioned epoxy resin and a curing agent for epoxy resin. When the curable composition contains the epoxy resin, it is preferable that the cured product obtained is excellent in heat resistance and toughness.

The curable composition of the present invention can use, without particular limitation, a curing agent for epoxy resins capable of a crosslinking reaction with the epoxy groups of the aforementioned epoxy resins. Examples of the curing agent include phenol curing agents, amine curing agents, acid anhydride curing agents, active ester resins, cyanate resins, and the like. The aforementioned curing agents may be used alone or in combination of two or more.

As the aforementioned phenol curing agent, for example, phenol novolak resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Xylock resin, etc.) ), naphthol aralkyl resins, triphenol-based methane resins, tetraphenol-based ethane resins, naphthol novolak resins, naphthol-phenol co-denatured novolak resins, naphthol-cresol co-distilled novolak resins, Benzene-modified phenolic resin (compound containing polyhydric phenolic hydroxyl group formed by linking phenol nucleus with double methylene group), biphenyl modified naphthol resin (polyhydric naphthol compound formed by linking phenol nucleus with double methylene group) compound), aminotriazine-modified phenolic resin (a compound containing polyhydric phenolic hydroxyl group formed by linking phenolic nuclei with melamine, benzoguanamine, etc.), alkoxy-containing aromatic ring-modified novolac resin (formaldehyde A compound containing a polyphenolic hydroxyl group such as a polyphenolic hydroxyl group-containing compound obtained by linking a phenolic nucleus and an alkoxy-containing aromatic ring. Among them, phenol novolac and the like are more preferable from the viewpoint of formability. In addition, the said phenolic hydroxyl group containing compound may be used individually or in combination of 2 or more types.

Examples of the aforementioned amine curing agent include diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), diethylene Aminopropylamine (DEAPA), N-Aminoethylpiperazine, Menthanediamine (MDA), Isophoronediamine (IPDA), 1,3-Diaminomethylcyclohexane (1,3 -BAC), piperidine, N,N-dimethylpiperazine, triethylenediamine and other aliphatic amines; m-xylylenediamine (XDA), methanephenylenediamine (MPDA), diaminodiphenyl dimethylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, 2,4,6-tris(dimethylaminomethyl)phenol and other aromatic amines.

Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis-trimellitate, glycerol trimellitate, and maleic anhydride. , tetrahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, methyl endomethylene tetrahydrophthalic anhydride, methylbutenyl tetrahydro Phthalic anhydride, dodecenyl succinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, methylcyclohexene dicarboxylic anhydride, and the like.

The amount of the aforementioned curing agent used relative to the amount of the aforementioned epoxy resin is not particularly limited, for example, as a functional group equivalent ratio (for example, the hydroxyl equivalent of the phenol curing agent/the epoxy equivalent of the epoxy resin), obtained from From the viewpoint that the mechanical properties of the cured product are good, the active group in the curing agent is preferably 0.5 to 1.5 equivalents to the total of 1 equivalents of the epoxy groups of the aforementioned epoxy resin and other epoxy resins used in combination if necessary. amount, more preferably 0.8 to 1.2 equivalents.

In addition, in the said curable composition, other resins other than the said epoxy resin and the said hardening|curing agent can be used together in the range which does not impair the effect of this invention. For example, epoxy resins other than the aforementioned epoxy resins, maleimide resins, bismaleimide resins, polymaleimide resins, polyphenylene ether resins, polyimide resins, , benzoxazine resin, triazine-containing cresol novolac resin, styrene-maleic anhydride resin, diallyl bisphenol, triallyl isocyanurate and other allyl-containing resins, polyphosphoric acid esters, phosphate-carbonate copolymers, etc. These other resins may be used alone or in combination of two or more.

<solvent>

The curable composition of the present invention may be prepared without a solvent, or may contain a solvent. The aforementioned solvent has a function of adjusting the viscosity of the curable composition, and the like.

Specific examples of the aforementioned solvents are not particularly limited, and include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether-based solvents such as diethyl ether and tetrahydrofuran; ethyl acetate, butyl acetate, and the like; Esters, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate and other ester solvents; cellosolve, butyl carbitol and other carbitols, toluene, xylene, ethyl Benzene, mesitylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene and other aromatic hydrocarbons, dimethylformamide, dimethylacetamide, N-methylpyrrolidone Other amide solvents, etc. These solvents may be used alone or in combination of two or more.

As the usage-amount of the said solvent, it is preferable that it is 10-90 mass % with respect to the gross mass of curable composition, and it is more preferable that it is 20-80 mass %. When the usage-amount of a solvent is 10 mass % or more, it is excellent in terms of handling. On the other hand, when the usage-amount of a solvent is 90 mass % or less, it is preferable from an economical viewpoint.

<additive>

The curable composition of the present invention may contain various additives such as curing accelerators, flame retardants, inorganic fillers, silane coupling agents, mold release agents, pigments, colorants, and emulsifiers as necessary.

<Curing Accelerator>

The curing accelerator is not particularly limited, and examples thereof include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and urea-based curing accelerators. In addition, the said hardening accelerator may be used individually, and may use it in combination of 2 or more types.

Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; trimethylphosphite, Organic phosphite compounds such as triethylphosphite; ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenyl borate, tetraphenylphosphonium tetraphenylboronic acid Esters, tetraphenylphosphonium tetra-p-cresyl borate, triphenylphosphinetriphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyandiamide, butylphenylphosphonium dicyandiamide , Tetrabutylphosphonium decanoate and other phosphonium salts, etc.

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

Examples of the aforementioned imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-pentadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 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-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazolium isocyanurate Adducts, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2 -a] benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline and the like.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, triphenylguanidine, Methylguanidine, Tetramethylguanidine, Pentamethylguanidine, 1,5,7-Triazabicyclo[4.4.0]dec-5-ene, 7-Methyl-1,5,7-Triaza Bicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, etc. .

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

Among the aforementioned curing accelerators, especially when used as a sealing material for semiconductors, triphenylphosphine is preferably used among the phosphorus-based compounds because of its excellent curability, heat resistance, electrical characteristics, and moisture-resistant reliability. Among the tertiary amines, 1,8-diazabicyclo-[5.4.0]-undecene (DBU) is preferably used.

The amount of the above-mentioned curing accelerator can be adjusted appropriately in order to obtain the desired curability, and is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 100 parts by mass of the total amount of the mixture of the epoxy resin and the curing agent. 5 parts by mass. When the usage-amount of the said hardening accelerator is in the said range, it is excellent in curability and insulation reliability, and it 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, and halogen-based flame retardants. In addition, a flame retardant may be used individually or in combination of 2 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 phosphoric acid amides.

The organophosphorus-based flame retardant is not particularly limited, and examples thereof include methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, Butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecane Acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, ethylene glycol Acid phosphate, (2-hydroxyethyl) methacrylate acid phosphate and other phosphates; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenyl Diphenylphosphine such as phosphine oxide; 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(1,4-dioxynaphthalene )-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphenylphosphino-1,4-dioxynaphthalene, 1,4- Phosphorus-containing phenols such as cyclooctylphosphino-1,4-phenyldiol and 1,5-cyclooctylphosphino-1,4-phenyldiol; 9,10-dihydro-9 -Oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2 , 7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and other cyclic phosphorus compounds; the aforementioned phosphoric acid ester, the aforementioned diphenylphosphine, the aforementioned phosphorus-containing phenol and epoxy Compounds obtained by reacting resins, aldehyde compounds, and phenolic compounds, 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-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, tetrabromophthalimide, etc.

It is preferable that the usage-amount of the said flame retardant is 0.1-20 mass parts with respect to 100 mass parts of said epoxy resins.

<Inorganic filler>

The aforementioned inorganic filler is not particularly limited, and examples thereof include silica, alumina, glass, cordierite, organosilicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, Magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, zirconium titanate Barium acid, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, 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, and the like are used. Among these, the above-mentioned fused silica is preferable from the viewpoint that more inorganic fillers can be compounded. The above-mentioned fused silica may be used in any form of crushed or spherical. In order to increase the compounding amount of fused silica and suppress an increase in the melt viscosity of the curable composition, it is preferable to mainly use spherical silica. Furthermore, in order to increase the compounding quantity of spherical silica, it is preferable to adjust the particle size distribution of spherical silica suitably. In addition, the said inorganic filler may be used individually, and may use it in combination of 2 or more types.

In addition, the said inorganic filler may be surface-treated as needed. At this time, the usable surface treatment agent is not particularly limited, and aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, organosilazane compounds, etc. , Titanate coupling agent, etc. Specific examples of surface treatment agents include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl -3-Aminopropyltrimethoxysilane, hexamethyldisilazane and the like.

It is preferable that the usage-amount of the said inorganic filler is 0.5-95 mass parts with respect to 100 mass parts of total amounts of the mixture of the said epoxy resin and the said hardening|curing agent. When the usage-amount of the said inorganic filler is in the said range, it is excellent in flame retardancy and insulation reliability, and it is preferable.

In addition, as long as the characteristics of the present invention are not impaired, an organic filler may be blended in addition to the aforementioned inorganic filler. As said organic filler, polyamide particle etc. are mentioned, for example.

<cured product>

The present invention relates to a cured product of the aforementioned curable composition. By using the epoxy resin, a cured product obtained from the curable composition containing the epoxy resin can exhibit high heat resistance and high toughness, which is a preferred aspect.

As a method of obtaining a cured product by subjecting the curable composition to a curing reaction, for example, the heating temperature during heating and curing is not particularly limited, but is usually 100 to 300° C., and the heating time is 1 to 24 hours.

The glass transition temperature (Tg) of the cured product of the present invention is preferably 160° C. or higher. The measurement method of the aforementioned glass transition temperature (Tg) is the same as the evaluation method in the examples of the present application.

In addition, the Charpy impact strength of the cured product of the present invention is preferably 6.5 J/cm ² or higher, more preferably 7.3 J/cm ² or higher, particularly preferably 7.8 J/cm ² or higher. The measurement method of the Charpy impact strength is the same as the evaluation method of the examples of the present application.

<Semiconductor sealing material>

The present invention relates to a semiconductor sealing material containing the aforementioned curable composition. The semiconductor encapsulating material obtained by using the above-mentioned curable composition has low viscosity and excellent fluidity due to the use of the above-mentioned epoxy resin, and furthermore, the heat resistance and toughness of the cured product are improved, so the processability and moldability in the manufacturing process are excellent. , is the preferred way.

An inorganic filler may be contained in the said curable composition used for the said semiconductor sealing material. In addition, as a filling rate of the said inorganic filler, an inorganic filler can be used in the range of 0.5-95 mass parts with respect to 100 mass parts of said curable compositions, for example.

As a method of obtaining the semiconductor sealing material, a method of sufficiently mixing the curable composition and additives as optional components, if necessary, to uniformity using an extruder, kneader, roll, etc. is mentioned.

<Semiconductor device>

The present invention relates to a semiconductor device including a cured product of the aforementioned semiconductor sealing material. The semiconductor device obtained by using the semiconductor sealing material obtained by using the above-mentioned curable composition has low viscosity and excellent fluidity due to the use of the above-mentioned epoxy resin, and the heat resistance and toughness of the cured product are improved. It is a preferred embodiment because it is excellent in processability and formability.

As a method of obtaining the aforementioned semiconductor device, the method of molding the aforementioned semiconductor sealing material using a casting molding machine, a transfer molding machine, an injection molding machine, or the like, and further performing the molding at a temperature range of room temperature (20° C.) to 250° C. Heat to cure.

<prepreg>

The present invention relates to a prepreg comprising a reinforcing base material and a semi-cured product of the curable composition impregnated into the reinforcing base material. As a method of obtaining a prepreg from the above-mentioned curable composition, a method obtained by mixing an organic solvent described later and impregnating the varnished curable composition into a reinforcing base material (paper , glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass mat, glass grit cloth, etc.), heat at a heating temperature in accordance with the type of solvent used, preferably 50-170°C. The mass ratio of the curable composition used at this time to the reinforcing base material is not particularly limited, but usually it is preferably prepared so that the resin component in the prepreg is 20 to 60 mass%.

Examples of organic solvents used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol Acetate, propylene glycol monomethyl ether acetate, and the like can be appropriately selected according to the application for its selection and appropriate amount. For example, when a printed circuit board is further produced from a prepreg as described below, it is preferable Polar solvents having a boiling point of 160° C. or lower such as methyl ethyl ketone, acetone, and dimethylformamide are used, and are preferably used at a ratio of 40 to 80% by mass of non-volatile components.

<circuit board>

The present invention relates to a circuit board which is a laminate of the aforementioned prepreg and copper foil. As a method of obtaining a printed circuit board from the above-mentioned curable composition, the following method is mentioned: the above-mentioned prepreg is laminated by a conventional method, and the copper foil is stacked as appropriate, and the pressure is 1-10MPa at 170-300°C. The thermocompression bonding is performed for 10 minutes to 3 hours.

<Laminated film>

The present invention relates to a laminated film containing the aforementioned curable composition. As a method of producing the laminated film of the present invention, 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 is exemplified.

In the case of producing a laminated film from a curable composition, it is important that the film is softened under the lamination temperature conditions (usually 70 to 140°C) of the vacuum lamination method, and that the film exhibits resin while being laminated with the circuit board. In order to express the fluidity (resin flow) that can be filled into the via hole existing in the circuit board or in the via hole, it is preferable to compound 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, and it is generally preferable that the resin can be filled within this range. In addition, when laminating both surfaces of a circuit board, it is desirable to fill about 1/2 of a via hole.

The method for producing the above-mentioned adhesive film can be produced specifically by: after preparing the above-mentioned curable composition in the form of a varnish, coating the composition in the form of a varnish on the surface of the support film (Y), and performing heating Alternatively, the organic solvent is dried by blowing hot air or the like to form a composition layer (X) made of a curable composition.

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

In addition, the composition layer (X) in this invention can be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent adhesion and damage of dust and the like on the surface of the resin composition layer.

Examples of the aforementioned support film and protective film include polyethylene, polypropylene, polyolefins such as polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate Such as polyester, polycarbonate, polyimide, and release paper, copper foil, aluminum foil and other metal foils. It should be noted that the support film and the protective film may be subjected to matting treatment, corona treatment, and mold release treatment.

The thickness of the support film is not particularly limited, but it is usually 10 to 150 μm, preferably used in a range of 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 peeled off after being laminated on a circuit board or after forming an insulating layer by heating and curing. When the support film (Y) is peeled off after heating and curing the adhesive film, it is possible to prevent adhesion of dust and the like in the curing step. In the case of peeling after curing, the support film is usually subjected to release treatment in advance.

<Other uses>

The cured product obtained from the curable composition of the present invention is excellent in heat resistance, toughness, etc., so it is suitable not only for applications such as semiconductor sealing materials, semiconductor devices, prepregs, circuit boards, and laminated films. , It is also suitable for use in various applications such as laminated substrates, adhesives, anti-corrosion materials, and matrix resins for fiber-reinforced resins, and the applications are not limited to these.

Example

Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to these ranges. In addition, the measurement/evaluation of a physical property/characteristic was implemented as follows, and the evaluation result is shown in Table 1 and Table 2 below.

<softening point>

The softening point (° C.) was measured in accordance with JIS K 7234 (ring and ball method).

<Measurement of epoxy equivalent>

Measurement was performed based on JIS K 7236.

<Measurement method of melt viscosity at 150°C>

Based on ASTM D4287, it measures with an ICI viscometer.

<Measurement by Gel Permeation Chromatography (GPC)>

GPC measurement was performed under the conditions shown below, and the obtained GPC chart was continuously evaluated to calculate the number average molecular weight (Mn), weight average molecular weight (Mw), and degree of dispersion (Mw/Mn) of the epoxy resin obtained.

Measuring device: "HLC-8320GPC" manufactured by Tosoh Corporation,

Column: Guard column "HXL-L" manufactured by Tosoh Corporation

+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation

+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

Detector: RI (differential refractometer)

Data processing: "GPC workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation

Determination conditions: column temperature 40°C

developing solvent tetrahydrofuran

Flow rate 1.0ml/min

Standard: According to the measurement manual of the aforementioned "GPC Workstation EcoSEC-WorkStation", the following monodisperse polystyrene with a known molecular weight was used.

(using polystyrene)

Tosoh Corporation "A-500"

"A-1000" manufactured by Tosoh Corporation

"A-2500" manufactured by Tosoh Corporation

"A-5000" manufactured by Tosoh Corporation

"F-1" manufactured by Tosoh Corporation

"F-2" manufactured by Tosoh Corporation

"F-4" manufactured by Tosoh Corporation

"F-10" manufactured by Tosoh Corporation

"F-20" manufactured by Tosoh Corporation

"F-40" manufactured by Tosoh Corporation

"F-80" manufactured by Tosoh Corporation

"F-128" manufactured by Tosoh Corporation

Sample: what filtered the tetrahydrofuran solution of 1.0 mass % in conversion of resin solid content with the microfilter (50 microliters).

(Synthesis Example 1: Synthesis of Phenolic Hydroxyl-Containing Resin (P2-1))

In a flask equipped with a thermometer, a condenser tube, a fractionation tube, a nitrogen inlet tube, and a stirrer, 160 g (1.0 mole) of 2,7-dihydroxynaphthalene and 27.0 g (0.25 mole) of benzyl alcohol were dropped into the flask, and at room temperature, the side It stirred while blowing in nitrogen gas. Next, 2.7 g of p-toluenesulfonic acid monohydrate was added. Then, it heated to 150 degreeC, paying attention to heat|fever in an oil bath, and after taking out the produced|generated water using the fractionating tube, reaction was further performed for 5 hours. After completion of the reaction, 1000 g of methyl isobutyl ketone was added to dissolve the reaction product, and then transferred to a separatory funnel. After washing with water until the washing water showed neutrality, the solvent was removed from the organic layer under heating and reduced pressure to obtain 240 g of the target phenolic hydroxyl group-containing resin (P2-1). The obtained phenolic hydroxyl-containing resin (P2-1) had a softening point of 97° C. and a hydroxyl group equivalent of 146 g/equivalent. Moreover, content of the compound (A) which has three naphthalene ring structures in 1 molecule of phenolic hydroxyl-containing resin (P2-1) was 33%. The GPC chart of the phenolic hydroxyl-containing resin (P2-1) is shown in FIG. 1 . In addition, content of the said compound (A) was calculated from the area ratio of a GPC chart.

In addition, the compound (A) contained in the phenolic hydroxyl-containing resin (P2-1) obtained above is a compound represented by the following structural formula.

(Example 1: Synthesis of epoxy resin (1))

Into a flask equipped with a thermometer, dropping funnel, condenser, and stirrer, 180.0 g of the phenolic hydroxyl-containing resin (P2-1) obtained in Synthesis Example 1, 4,4'-linked 60.0 g of phenol, 1157 g of epichlorohydrin, 347 g of n-butanol, and 58 g of water were dissolved. After heating up to 60° C., 480 g of a 20 mass % sodium hydroxide aqueous solution was added dropwise over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. Thereafter, unreacted epichlorohydrin was distilled off by distillation under reduced pressure to obtain a crude product. 600 g of methyl isobutyl ketone was added and dissolved in the obtained crude product. 33 g of 5 mass % sodium hydroxide aqueous solution was added to this solution, and it reacted at 80 degreeC for 2 hours. 180 g of water was added to the reaction mixture to wash with water. Washing with water was repeated 3 times until the pH of the cleaning solution was neutral. Next, dehydration was performed by azeotroping the inside of the system, and after microfiltration, the solvent was distilled off under reduced pressure to obtain an epoxy resin (1). The epoxy equivalent of the obtained epoxy resin (1) is 197g/equivalent, and the melt viscosity at 150°C is 0.2dPa·s, the number average molecular weight (Mn) is 314, the weight average molecular weight (Mw) is 372, and the degree of dispersion ( Mw/Mn) was 1.2. The GPC chart of epoxy resin (1) is shown in FIG. 2 .

The epoxy resin (1) obtained above contains the epoxy resin represented by the following structural formula.

[In the above formula, n is an integer of 0-10. ]

(Example 2: Synthesis of epoxy resin (2))

In Example 1, except changing to 192.0 g of phenolic hydroxyl-containing resin (P2-1) and 48.0 g of 4,4'-biphenol, it reacted similarly to Example 1, and obtained epoxy resin (2) . The epoxy equivalent of obtained epoxy resin (2) is 203g/equivalent, the melt viscosity at 150 ℃ is 0.3dPa·s, number average molecular weight (Mn) is 319, weight average molecular weight (Mw) is 381, dispersity ( Mw/Mn) was 1.2. The GPC profile is shown in FIG. 3 .

The epoxy resin (2) obtained above contains the epoxy resin represented by the following structural formula.

[In the above formula, n is an integer of 0-10. ]

(Example 3: Synthesis of epoxy resin (3))

In Example 1, except changing to 232.8 g of phenolic hydroxyl-containing resin (P2-1) and 7.2 g of 4,4'-biphenol, it reacted similarly to Example 1, and obtained epoxy resin (3) . The epoxy equivalent of obtained epoxy resin (3) is 213g/equivalent, the melt viscosity at 150 ℃ is 0.4dPa·s, the number average molecular weight (Mn) is 336, the weight average molecular weight (Mw) is 412, the degree of dispersion ( Mw/Mn) was 1.2. The GPC profile is shown in FIG. 4 .

The epoxy resin (3) obtained above contains the epoxy resin represented by the following structural formula.

[In the above formula, n is an integer of 0-10. ]

(comparative synthesis example 1: synthesis of phenolic hydroxyl-containing resin (1'))

432.4 g (4.0 moles) of o-cresol, 158.2 g (1.0 moles) of 2-methoxynaphthalene, and 41 mass % formaldehyde aqueous solution 179.3 g (2.45 mol), 9.0 g of oxalic acid was added, it heated up to 100 degreeC, and it reacted at 100 degreeC for 3 hours. Next, water was collected in a fractionating tube, and 73.2 g (1.0 mol) of a 41% by mass formaldehyde aqueous solution was added dropwise over 1 hour. After completion of the dropwise addition, the temperature was raised to 150° C. over 1 hour, and the reaction was performed at the same temperature for 2 hours. After the reaction was completed, 1500 g of methyl isobutyl ketone was added and transferred to a separatory funnel. After washing with water until the washing water becomes neutral, remove unreacted o-cresol, 2-methoxynaphthalene, and methyl isobutyl ketone from the organic layer under heating and reduced pressure to obtain a phenolic hydroxyl-containing resin (1'). The obtained phenolic hydroxyl-containing resin (1') had a softening point of 76°C and a hydroxyl equivalent of 164 g/equivalent.

(Comparative Example 1: Synthesis of Epoxy Resin (1'))

In the flask that thermometer, dropping funnel, condensation tube, stirrer are installed, carry out nitrogen purging on the one hand, drop into the phenolic hydroxyl-containing resin (1 ') 137.1g (hydroxyl 0.84 equivalents) that obtains in comparative synthesis example 1, 4 15.3 g of 4'-biphenol (hydroxyl equivalent: 0.16 equivalent), 463 g (5.0 mol) of epichlorohydrin, 139 g of n-butanol, and 2 g of tetraethylbenzyl ammonium chloride were dissolved. After heating up to 70 degreeC, 220 g (1.1 mol) of 20 mass % sodium hydroxide aqueous solutions were dripped over 5 hours. Thereafter, stirring was continued for 0.5 hours under the same conditions. Unreacted epichlorohydrin was distilled off by vacuum distillation to obtain a crude product. 1000 g of methyl isobutyl ketone and 350 g of n-butanol were added to the obtained crude product and dissolved. To this solution, 10 g of a 10% by mass sodium hydroxide aqueous solution was added, and after reacting at 80° C. for 2 hours, water washing with 150 g of water was repeated three times until the pH of the washing solution became neutral. Dehydration was carried out by azeotroping in the system, and after precision filtration, the solvent was distilled off under reduced pressure to obtain 176 g of epoxy resin (1'). The obtained epoxy resin (1') had an epoxy equivalent of 230 g/equivalent, a melt viscosity at 150° C. of 0.3 dPa·s, a number average molecular weight (Mn) of 426, a weight average molecular weight (Mw) of 666, and a degree of dispersion of (Mw/Mn) was 1.6.

[Table 1]

(Examples 4-6 and Comparative Example 2: Preparation of Epoxy Resin Composition)

Each component was mixed with the composition shown in Table 2, melt-kneaded, and each epoxy resin composition was obtained. The details of each component in Table 2 are as follows.

Curing agent: phenol novolac type phenolic resin ("TD-2131" manufactured by DIC Corporation, hydroxyl equivalent: 104 g/equivalent)

Curing accelerator: triphenylphosphine ("TPP" manufactured by Hokko Chemical Industry Co., Ltd.)

<Heat Resistance Evaluation>

Each of the above-mentioned epoxy resin compositions was cured at 150° C. for 10 minutes in normal pressure pressing so that the thickness of the cured product was 2.4 mm, and then post-cured at 175° C. for 5 hours to obtain Cured product for evaluation.

This cured product was cut into a size of 5 mm×54 mm with a diamond cutter, and this was used as a test piece for heat resistance evaluation. For heat resistance evaluation, using a viscoelasticity measuring device (Rheometrics, Inc. "solid viscoelasticity measuring device RSAII", rectangular tension (rectangular tension) method: frequency 1Hz, heating rate 3°C/min), the elastic modulus change The maximum temperature (at which the rate of change of tan δ is also the maximum) was defined as the glass transition temperature (Tg) (° C.), and the heat resistance was evaluated.

<Toughness Evaluation>

Using each epoxy resin composition, according to JIS K 6911, transfer molding was performed at 175°C for 120 seconds and a molding pressure of 6.9MPa, and then post-cured at 175°C for 5 hours to produce Test piece for Charpy impact strength test. The Charpy impact strength (J/cm ² ) of the obtained test piece was measured using Pendulum Impact Tester Zwick5102, and the toughness was evaluated.

[Table 2]

Example 4 Example 5 Example 6 Comparative example 2 Epoxy Resin(1) 70.3 Epoxy Resin(2) 66.1 Epoxy Resin(3) 67.2 Epoxy Resin(1') 68.9 TD-2131 29.7 28.5 27.4 31.1 TPP 1 1 1 1 DMA-Tg(°C) 164 166 169 149 Charpy impact strength (J/cm ² ) 8.0 7.5 6.7 4.0

From the evaluation results in Table 1 and Table 2 above, it can be confirmed that the epoxy resins obtained in all the examples are low in viscosity and excellent in high fluidity, and can contribute to good formability. The cured product obtained from the composition (curable composition) has a high glass transition temperature and high heat resistance. It also shows a high value in the Charpy impact test and has high toughness. It can be confirmed that high heat resistance and The combination of high toughness.

On the other hand, based on the evaluation results in Table 1 and Table 2 above, in Comparative Example 1, the epoxy resin (1') was synthesized without using the desired phenolic hydroxyl-containing resin, and the epoxy resin (1') was synthesized by using the epoxy resin (1'). ') The comparative example 2 of the epoxy resin composition (curable composition) was inferior to an Example in heat resistance and toughness as a result.

Claims (13)

1. An epoxy resin comprising: a glycidyl ether compound (E1) of a biphenol compound (P1) and a glycidyl ether compound (E2) of a phenolic hydroxyl-containing resin (P2), the phenolic hydroxyl-containing Resin (P2) uses dihydroxy aromatic compound (α) and aralkylating agent (β) represented by the following general formula (1-1) or (1-2) as reaction raw materials, In the general formulas (1-1) and (1-2), X represents any one of a halogen atom, a hydroxyl group, and an alkoxy group, and R ¹ each independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. Any one, R ² each independently represents a hydrogen atom or a methyl group, Ar ¹ represents a phenyl group, a naphthyl group, one or more on their aromatic nuclei, a halogen atom, an aliphatic hydrocarbon group, an alkoxyl group Any of the structural parts. 2. An epoxy resin, which contains: a glycidyl etherified product (E3) of a mixture of a biphenol compound (P1) and a phenolic hydroxyl-containing resin (P2), and the phenolic hydroxyl-containing resin (P2) is dihydroxyl The aromatic hydrocarbon compound (α) and the aralkylating agent (β) represented by the following general formula (1-1) or (1-2) are reaction raw materials, In the general formulas (1-1) and (1-2), X represents any one of a halogen atom, a hydroxyl group, and an alkoxy group, and R ¹ each independently represents a hydrogen atom or an alkyl group with 1 to 4 carbon atoms. Any one, R ² each independently represents a hydrogen atom or a methyl group, Ar ¹ represents a phenyl group, a naphthyl group, those having one or more aromatic nuclei, a halogen atom, an aliphatic hydrocarbon group, an alkoxy group Any of the structural parts. 3. epoxy resin according to claim 2, wherein, the ratio of described biphenol compound (P1) with respect to the gross mass of described biphenol compound (P1) and described phenolic hydroxyl resin (P2) is 0.5% by mass to 40% by mass. 4 . The epoxy resin according to claim 1 , wherein the phenolic hydroxyl-containing resin (P2) contains a compound (A) having three naphthalene ring structures in one molecule. 5. The epoxy resin according to claim 4, wherein the content of the compound (A) in the phenolic hydroxyl resin (P2) is calculated according to the area ratio of the spectrogram of gel permeation chromatography (GPC). The value is 5-50%. 6 . The epoxy resin according to claim 1 , which has a melt viscosity at 150° C. measured with an ICI viscometer of 0.01 to 5 dPa·s. The curable composition containing the epoxy resin and the hardening|curing agent for epoxy resins in any one of Claims 1-6. 8. A cured product of the curable composition according to claim 7. 9. A semiconductor sealing material comprising the curable composition according to claim 7. 10. A semiconductor device comprising a cured product of the semiconductor sealing material according to claim 9. 11. A prepreg comprising: a reinforcing base material; and a semi-cured product of the curable composition according to claim 7 impregnated into the reinforcing base material. 12. A circuit board which is a laminate of the prepreg and copper foil according to claim 11. 13. A laminated film comprising the curable composition according to claim 7.