WO2022118723A1

WO2022118723A1 - Epoxy resin, curable composition, cured product, semiconductor sealing material, semiconductor device, prepreg, circuit board and buildup film

Info

Publication number: WO2022118723A1
Application number: PCT/JP2021/043092
Authority: WO
Inventors: 和賢青山; 和久矢本; 源祐秋元
Original assignee: Dic株式会社
Priority date: 2020-12-03
Filing date: 2021-11-25
Publication date: 2022-06-09
Also published as: TW202231701A; JP7290205B2; CN116583943A; KR20230059829A; JPWO2022118723A1

Abstract

The present invention provides an epoxy resin which contains: a glycidyl etherified product (E1) of a biphenolic compound (P1); and a glycidyl etherified product (E2) of a phenolic hydroxyl group-containing resin (P2) that uses, as reactant materials, a dihydroxyarene compound (α) and an aralkylating agent (β) that is represented by general formula (1-1) or (1-2). (In general formulae (1-1) and (1-2), X represents a halogen atom, a hydroxyl group or an alkoxy group; each R1 independently represents a hydrogen atom or an alkyl group having from 1 to 4 carbon atoms; each R2 independently represents a hydrogen atom or a methyl group; and Ar1 represents a phenyl group, a naphthyl group, or a structural moiety that has one or more halogen atoms, one or more aliphatic hydrocarbon groups, or one or more alkoxy groups on one of these aromatic nuclei.)

Description

Epoxy resin, curable composition, cured product, semiconductor encapsulant material, semiconductor device, prepreg, circuit board, and build-up film

The present invention relates to an epoxy resin, a curable composition, a cured product, a semiconductor encapsulating material, a semiconductor device, a prepreg, a circuit board, and a build-up film.

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

Among these various applications, in the field of semiconductor encapsulation materials, surface mounting of semiconductor packages such as BGA and CSP is progressing, but the semiconductor packages are exposed to high temperatures in the reflow process for surface mounting. , High heat resistance is required for the resin material for sealing.

Further, in order to reduce the warpage of the semiconductor encapsulant generated in the recent miniaturization and thinning of electronic devices and the batch encapsulation process, a resin material with high toughness is required.

Further, in addition to the above-mentioned performances, since the semiconductor encapsulation material is used by filling the resin material with an inorganic filler such as silica, the resin material has a low viscosity and excellent fluidity in order to increase the filling rate of the filler. It is also required.

As a semiconductor encapsulating material that meets the required characteristics, for example, it is disclosed that an aralkyl-modified poly (oxynaphthalethylene) type epoxy resin is used (see Patent Document 1).

However, although the epoxy resin disclosed in Patent Document 1 is excellent in heat resistance of the obtained cured product, the melt viscosity of the epoxy resin itself is high, and the epoxy resin composition containing the epoxy resin has fluidity and moldability. It is inferior to the above, and the reduction of warpage has not been clarified.

As described above, in the field of semiconductor encapsulation materials, an epoxy resin composition having a particularly low viscosity and excellent fluidity and moldability and the epoxy resin composition can be obtained, and have high heat resistance and sufficient toughness. At present, an epoxy resin composition for encapsulating a semiconductor, which can obtain a cured product, has not been obtained.

Japanese Patent No. 5689230

Therefore, the problem to be solved by the present invention is obtained by using an epoxy resin having a low melt viscosity and contributing to fluidity and moldability, a curable composition containing the epoxy resin, and the curable composition. It is an object of the present invention to provide a cured product having high heat resistance and high toughness, a semiconductor encapsulating material, a semiconductor device, a prepreg, a circuit board, and a build-up film.

As a result of diligent research to solve the above-mentioned problems, the present inventors have conducted an epoxy resin that can contribute to excellent fluidity and moldability, a curable composition containing the epoxy resin, and the curable composition. We have found a cured product, a semiconductor encapsulant, a semiconductor device, a prepreg, a circuit board, and a build-up film, which are obtained by using a material and have excellent heat resistance and high toughness, and have completed the present invention. ..

That is, the present invention comprises a glycidyl etherified product (E1) of a biphenol compound (P1), a dihydroxyarene compound (α), and an aralkylating agent represented by the following general formula (1-1) or (1-2). The present invention relates to an epoxy resin containing a glycidyl etherified product (E2) of a phenolic hydroxyl group-containing resin (P2) using β) as a reaction raw material.

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

Further, in the present invention, a biphenol compound (P1) and a dihydroxyarene compound (α) and an aralkylating agent (β) represented by the following general formula (1-1) or (1-2) are used as reaction raw materials. The present invention relates to an epoxy resin containing a glycidyl etherified compound (E3) of a mixture of a phenolic hydroxyl group-containing resin (P2).

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 0.5% by mass or more and 40% by mass or less. It is preferable to have.

The epoxy resin of the present invention preferably contains the compound (A) in which the phenolic hydroxyl group-containing resin (P2) has three naphthalene ring structures in one molecule.

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

The epoxy resin of the present invention preferably has a melt viscosity at 150 ° C. measured by an ICI viscometer of 0.01 to 5 dPa · s.

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

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

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

The present invention relates to a semiconductor device containing a cured product of the semiconductor encapsulating material.

The present invention relates to a prepreg having a reinforcing base material and a semi-cured product of the curable composition impregnated in the reinforcing base material.

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

The present invention relates to a build-up film containing the curable composition.

The epoxy resin of the present invention has a low viscosity and is excellent in fluidity and moldability, and the cured product of the curable composition containing the epoxy resin is excellent in high heat resistance and high toughness. In particular, it is useful as a resin material for electrical materials such as semiconductor encapsulation materials.

6 is a GPC chart of the phenolic hydroxyl group-containing resin (P2-1) obtained in Synthesis Example 1. 6 is a GPC chart of the epoxy resin (1) obtained in Example 1. 6 is a GPC chart of the epoxy resin (2) obtained in Example 2. 6 is a GPC chart of the epoxy resin (3) obtained in Example 3.

The present invention comprises a glycidyl etherified product (E1) of a biphenol compound (P1), a dihydroxyarene compound (α), and an aralkylating agent (β) represented by the following general formula (1-1) or (1-2). ) As a reaction raw material, the present invention relates to an epoxy resin containing a glycidyl etherified product (E2) of a phenolic hydroxyl group-containing resin (P2).

<Biphenol compound (P1)>
The biphenol compound (P1) is not particularly limited, and is, for example, 2,2'-biphenol, 2,4'-biphenol, 3,3'-biphenol, 4,4'-biphenol, and on the aromatic ring thereof. Examples thereof include various compounds in which one or a plurality of aliphatic hydrocarbon groups, alkoxy groups, halogen atoms and the like are substituted. The biphenol compound (P1) may be used alone or in combination of two or more.

The aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in the structure. Of these, those having 1 to 4 carbon atoms are preferable, and specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group, because the effect of excellent heat resistance in the cured product becomes more remarkable. , T-butyl group, isobutyl group, vinyl group, allyl group and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a butoxy group and the like. Examples of the halogen atom include a fluorine atom, a chlorine atom and a bromine atom. In particular, since it is easy to adjust the melt viscosity of the finally obtained epoxy resin to a preferable value, it is preferable to have a substituent on 4,4'-biphenol and its aromatic ring, and 4,4'-biphenol is more preferable. ..

<Phenolic hydroxyl group-containing resin (P2)>
The phenolic hydroxyl group-containing resin (P2) uses a dihydroxyarene 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 independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ² independently represents a hydrogen atom or a methyl group. Ar ¹ represents any of a phenyl group, a naphthyl group, and a structural moiety having one or more halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups on these aromatic nuclei.

The phenolic hydroxyl group-containing resin (P2) contains a component having a (poly) arylene ether structure generated by an intramolecular dehydration reaction of the dihydroxyarene compound (α). Further, the olerousyl group is introduced into a part or all of the aromatic ring in the phenolic hydroxyl group-containing resin (P2) by the oleresin agent (β). As a result, the glycidyl etherified product (E2) of the phenolic hydroxyl group-containing resin (P2) has a relatively long distance between the glycidyl ether groups in the molecule and a high aromatic ring concentration, so that the curing can be obtained. It is possible to combine heat resistance and toughness in an object at a high level.

The dihydroxyarene compound (α) may be any compound having two hydroxy groups on the aromatic ring, and its specific structure is not particularly limited, and a wide variety of compounds can be used. Specific examples include dihydroxybenzene, dihydroxynaphthalene, and compounds having one or more substituents such as a halogen atom, an aliphatic hydrocarbon group, and an alkoxy group on their aromatic rings. In the present invention, one type of the dihydroxyarene compound (α) may be used alone, or two or more types may be used in combination.

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

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like. The aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in the structure. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a butyloxy group and the like.

Among the dihydroxyarene compounds (α), a halogen atom, an aliphatic hydrocarbon group, and an alkoxy group are placed on the dihydroxynaphthalene and its aromatic ring because the obtained cured product has more remarkable effects on heat resistance and toughness. Compounds having one or more substituents such as are preferable, and dihydroxynaphthalene is more preferable. The position of the hydroxy group on the dihydroxynaphthalene is preferably 1,6-position or 2,7-position, and more preferably 2,7-position. When a plurality of types of the dihydroxyarene compound (α) are used in combination, dihydroxynaphthalene occupying the dihydroxyarene compound (α) and a halogen atom, an aliphatic hydrocarbon group, an alkoxy group or the like on the aromatic ring thereof. The ratio of the compound having one or a plurality of substituents is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 95% by mass or more.

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

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

In the general formulas (1-1) and (1-2), the R ¹ independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Of these, a hydrogen atom is preferable because of its excellent reactivity.

In the general formulas (1-1) and (1-2), the R ² independently represents a hydrogen atom or a methyl group, respectively. Of these, a hydrogen atom is preferable because of its excellent reactivity.

In the general formulas (1-1) and (1-2), the Ar ¹ has a phenyl group, a naphthyl group, and one or more halogen atoms, an aliphatic hydrocarbon group, and an alkoxy group on these aromatic nuclei. It is one of the structural parts.

Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and the like. The aliphatic hydrocarbon group may be either a linear type or a branched type, and may have an unsaturated bond in the structure. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group and the like. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, a butyloxy group and the like. Among them, the Ar ¹ is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group, because the effect of excellent heat resistance and toughness in the cured product becomes more remarkable.

When a plurality of types are used in combination as the aralkylating agent (β), the ratio of the compound in which Ar ¹ is a phenyl group to the aralkylating agent (β) is preferably 50% by mass or more, and is 80%. It is more preferably mass% or more, and particularly preferably 95% by mass or more.

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

Examples of the method for producing the phenolic hydroxyl group-containing resin (P2) include a method in which a reaction raw material containing the dihydroxyarene compound (α) and the aralkylating agent (β) is reacted under acid catalyst conditions. Further, the reaction may be carried out in a solvent if necessary.

Since the reaction ratio between the dihydroxyarene compound (α) and the aralkylating agent (β) is an epoxy resin having excellent fluidity, the molar ratio [(α) / (β)] of the two is 1/0. It is preferably in the range of 1 to 1/10, and more preferably in the range of 1 / 0.1 to 1/1.

The acid catalyst includes, for example, 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 and chloride. Examples thereof include Friedelcraft catalysts such as ditin, ferric chloride and diethylsulfuric acid. These may be used alone or in combination of two or more.

When an inorganic acid or an organic acid is used as the acid catalyst, it is preferably used in the range of 0.01 to 3 parts by mass with respect to 100 parts by mass of the dihydroxyarene compound (α). When a Friedel-Crafts catalyst is used as the acid catalyst, it is preferably used in the range of 0.5 to 2 mol with respect to 1 mol of the dihydroxyarene compound (α).

The solvent is, for example, acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dipropyl ether, diethylene glycol dimethyl ether, diethylene glycol. Diethyl ether, diethylene glycol dipropyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monopropyl ether, diethylene glycol monobutyl ether, cellosolve, butylcarbitol, dimethyl Examples thereof include formamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, toluene, xylene, chlorobenzene and the like. Each of these may be used alone or as a mixed solvent of two or more kinds. When these solvents are used, it is preferable to use them in the range of 20 to 300% by mass with respect to the total mass of the reaction raw materials of the phenolic hydroxyl group-containing resin (P2).

The reaction between the dihydroxyarene compound (α) and the aralkylating agent (β) can be carried out under temperature conditions of about 60 to 180 ° C., and the reaction time is about 1 to 24 hours. The reaction can be promoted more efficiently by appropriately distilling off water or the like generated during the reaction. After completion of the reaction, the inside of the reaction system is neutralized with an alkaline compound such as an alkali metal hydroxide, or water is recommended and then dried to obtain the phenolic hydroxyl group-containing resin (P2). Can be done.

The hydroxyl group equivalent of the phenolic hydroxyl group-containing resin (P2) is preferably in the range of 100 to 400 g / equivalent, and 110 to 300 g / equivalent, because the effect of excellent heat resistance and toughness in the cured product becomes more remarkable. It is preferably in the range of. The softening point is preferably in the range of 60 to 140 ° C.

As an example of the phenolic hydroxyl group-containing resin (P2), for example, when 2,7-dihydroxynaphthalene is used as the dihydroxyarene compound (α) and benzyl alcohol is used as the aralkylating agent (β), the phenolic property is used. Specific examples of the specific structure of each component contained in the hydroxyl group-containing resin (P2) include those represented by any of the following structural formulas (2-1) to (2-18).

Since the phenolic hydroxyl group-containing resin (P2) has a more remarkable effect on the cured product in terms of heat resistance and toughness, the structural formulas (2-6) to (2-8) and (2-10), It is preferable to contain the compound (A) having three naphthalene ring structures in one molecule as represented by (2-11).

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

If the epoxy resin of the present invention contains the glycidyl etherified product (E1) of the biphenol compound (P1) and the glycidyl etherified product (E2) of the phenolic hydroxyl group-containing resin (P2), the production method thereof may be as follows. It is not particularly limited, and may be manufactured in any way.

As a method for producing an epoxy resin of the present invention, for example, (1) a glycidyl etherified product (E1) obtained by reacting the biphenol compound (P1) with epihalohydrin to form a glycidyl etherified product is synthesized, and the phenolic hydroxyl group-containing resin is separately prepared. The epoxy resin of the present invention can be obtained by reacting (P2) with epihalohydrin to synthesize a glycidyl etherified product (E2) that has been glycidyl etherified, and mixing (containing) these.

Further, (2) epihalohydrin is added to a mixture of the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2), and the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2) are combined with each other. By reacting with epihalohydrin, a glycidyl ether compound (E3) containing the glycidyl ether compound (E1) and the glycidyl ether compound (E2) is synthesized, and the one containing the glycidyl ether compound (E3) is used as the epoxy resin of the present invention. Can be done.

In particular, the manufacturing method of (2) above is preferable because it is excellent in convenience and workability.

In the method for producing an epoxy resin according to (1), the reaction between the biphenol compound (P1) and epihalohydrin and the reaction between the phenolic hydroxyl group-containing resin (P2) and epihalohydrin are carried out, for example, in the presence of a basic catalyst. Examples thereof include a method of reacting at 20 to 150 ° C., preferably 30 to 80 ° C. for 0.5 to 10 hours.

Examples of the epichlorohydrin include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin and the like. The amount of epihalohydrin added is excessively used with respect to a total of 1 mol of the hydroxyl groups of the biphenol compound (P1) or the phenolic hydroxyl group-containing resin (P2), but is usually 1.5 to 30 mol. Yes, preferably in the range of 2 to 15 mol.

Examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. Of these, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity, and specifically, sodium hydroxide, potassium hydroxide and the like are more preferable. Further, these basic catalysts may be used in a solid state or in an aqueous solution state. The amount of the basic catalyst added may be in the range of 0.9 to 2 mol with respect to a total of 1 mol of the hydroxyl groups of the biphenol compound (P1) or the phenolic hydroxyl group-containing resin (P2). preferable.

The reaction between the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2) and epihalohydrin may be carried out in an organic solvent. Examples of the organic solvent used include ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol and tertiary butanol, methyl cellosolve and ethyl cellosolve. Examples thereof include cellosolves, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotonic polar solvents such as acetonitrile, dimethylsulfoxide and dimethylformamide. Each of these organic solvents may be used alone, or two or more thereof may be used in combination as appropriate for adjusting the polarity.

After the reaction with the epihalohydrin is completed, a crude product can be obtained by distilling off the excess epihalohydrin. If necessary, the hydrolyzable halogen may be reduced by dissolving the obtained crude product in an organic solvent again, adding a basic catalyst and reacting again. The salt generated in the reaction can be removed by filtration, washing with water, or the like. When an organic solvent is used, it may be distilled off to take out only the resin solid content, or it may be used as it is as a solution.

In the method for producing an epoxy resin according to (1), the mass ratio of the glycidyl etherified product (E1) to the glycidyl etherified product (E2) is not particularly limited, but the fluidity is excellent and the toughness property of the cured product is high. The ratio of the glycidyl etherified product (E1) to the total mass of both is preferably 0.5% by mass or more, and preferably 1% by mass or more, because the epoxy resin has excellent low moisture absorption. It is more preferably 5% by mass or more, and particularly preferably 15% by mass or more. 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 according to (2), the mass ratio of both in the mixture of the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2) is excellent in fluidity and in the cured product. Since the epoxy resin has high toughness and low moisture absorption, the ratio of the biphenol compound (P1) to the total mass of both is preferably 0.5% by mass or more, preferably 1% by mass or more. Is preferable, 5% by mass or more is more preferable, and 15% by mass or more is particularly preferable. 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 carried out by the same method as the method for producing the epoxy resin of (1). The amount of the epihalohydrin added is excessively used with respect to a total of 1 mol of the hydroxyl groups of the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2), but is usually 1.5 to 30 mol, preferably 1.5 to 30 mol. It ranges from 2 to 15 mol. Further, as in the method for producing the epoxy resin of (1), a basic catalyst can be used, and the amount of the basic catalyst added is the biphenol compound (P1) and the phenolic hydroxyl group-containing resin (P2). It is preferably in the range of 0.9 to 2 mol with respect to 1 mol of the total hydroxyl group contained in.

The epoxy equivalent of the epoxy resin of the present invention is preferably 140 to 400 g / equivalent, more preferably 140 to 350 g / equivalent. The measurement of the epoxy equivalent here is based on JIS K7236.

The epoxy resin of the present invention preferably has a melt viscosity at 150 ° C. measured by an ICI viscometer of 0.01 to 5 dPa · s, more preferably 0.01 to 2 dPa · s, and 0.01. It is more preferably ~ 1 dPa · s. When the melt viscosity of the epoxy resin is within the above range, the viscosity is low and the fluidity is excellent, and the moldability of the obtained cured product is excellent, which is preferable. The melt viscosity here is based on ASTM D4287 and is measured by an ICI viscometer.

Since the epoxy resin of the present invention has a low viscosity and excellent fluidity, the number average molecular weight (Mn) is preferably in the range of 200 to 1500, more preferably in the range of 200 to 800. The weight average molecular weight (Mw) is preferably in the range of 250 to 2000, more preferably in the range of 250 to 800. The dispersity (Mw / Mn) is preferably in the range of 1 to 3. In the present invention, the molecular weight and the degree of dispersion of the epoxy resin are measured by 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 to 10. ]

<Curable composition>
The present invention relates to a curable composition containing the epoxy resin and a curing agent for an epoxy resin. When the curable composition contains the epoxy resin, the obtained cured product has excellent heat resistance and toughness, which is preferable.

In the curable composition of the present invention, an epoxy resin curing agent capable of cross-linking reaction with the epoxy group of the epoxy resin can be used without particular limitation. Examples of the curing agent include a phenol curing agent, an amine curing agent, an acid anhydride curing agent, an active ester resin, and a cyanate ester resin. The curing agent may be used alone or in combination of two or more.

Examples of the phenol curing agent include phenol novolac resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin (Zyroc resin), naphthol aralkyl resin, and triphenylol. Methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (polyvalent phenolic hydroxyl group-containing compound in which phenol nuclei are linked by bismethylene groups). ), Biphenyl-modified naphthol resin (polyvalent naphthol compound in which phenol nuclei are linked by bismethylene groups), aminotriazine-modified phenol resin (polyvalent phenolic hydroxyl group-containing compound in which phenol nuclei are linked by melamine, benzoguanamine, etc.) and alkoxy groups. Examples thereof include polyvalent phenolic hydroxyl group-containing compounds such as a contained aromatic ring-modified novolak resin (a polyvalent phenolic hydroxyl group-containing compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde). Among them, phenol novolac trees and the like are more preferable from the viewpoint of moldability. The compound containing the phenolic hydroxyl group may be used alone or in combination of two or more.

Examples of the amine curing agent include diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), diproprendamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine and mensendiamine. (MDA), Isophorondiamine (IPDA), 1,3-bisaminomethylcyclohexane (1,3-BAC), piperidine, N, N, -dimethylpiperazine, triethylenediamine and other aliphatic amines; m-xylenediamine ( XDA), methanephenylenediamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenylsulfone (DDS), benzylmethylamine, 2- (dimethylaminomethyl) phenol, 2,4,6-tris (dimethylaminomethyl) phenol, etc. Aromatic amines and the like can be mentioned.

Examples of the acid anhydride curing agent include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bistrimeritate, glycerol tristrimeritate, maleic anhydride, and tetrahydrophthalic anhydride. Methyltetrahydrochloride phthalic acid, endomethylenetetrahydrochloride phthalic acid, methylendomethylenetetrahydrochloride phthalic acid, methylbutenyltetrahydrochloride phthalic acid, dodecenyl succinic anhydride, hexahydrochloride phthalic acid, methylhexahydrohydride phthalic acid, succinic anhydride, Methylcyclohexene dicarboxylic acid anhydride and the like can be mentioned.

The amount of the curing agent used with respect to the amount of the epoxy resin used is not particularly limited as, for example, the functional group equivalent ratio (for example, the hydroxyl group equivalent of the phenol curing agent / the epoxy equivalent of the epoxy resin). Since the mechanical properties of the cured product to be obtained are good, the number of active groups in the curing agent is 0 with respect to a total of 1 equivalent of the epoxy group with the epoxy resin and other epoxy resins used in combination as needed. The amount is preferably 5.5 to 1.5 equivalents, more preferably 0.8 to 1.2 equivalents.

In addition to the epoxy resin and the curing agent, other resins can be used in combination with the curable composition as long as the effects of the present invention are not impaired. For example, epoxy resins other than the epoxy resin, maleimide resin, bismaleimide resin, polymaleimide resin, polyphenylene ether resin, polyimide resin, benzoxazine resin, triazine-containing cresol novolak resin, styrene-maleic anhydride resin, diallyl bisphenol and triallyl. Examples thereof include an allyl group-containing resin such as isocyanurate, a polyphosphate ester, and a phosphate ester-carbonate copolymer. 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 solvent has a function of adjusting the viscosity of the curable composition and the like.

Specific examples of the solvent are not particularly limited, but are ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ethyl acetate, butyl acetate, cellosolve acetate and propylene glycol monomethyl. Ester solvents such as ether acetate and carbitol acetate; carbitols such as cellosolve and butyl carbitol, toluene, xylene, ethylbenzene, mecitylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene and the like. Examples thereof include amide-based solvents such as aromatic hydrocarbons, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents may 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, based on the total mass of the curable composition. When the amount of the solvent used is 10% by mass or more, it is preferable because the handling property is excellent. On the other hand, when the amount of the solvent used is 90% by mass or less, it is preferable from the viewpoint of economy.

<Additives>
The curable composition of the present invention contains various additives such as a curing accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a mold release agent, a pigment, a colorant, and an emulsifier, if necessary. Can be done.

<Curing accelerator>
The curing accelerator is not particularly limited, and examples thereof include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, and a urea-based curing accelerator. The curing accelerator may be used alone or in combination of two or more.

Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, triparatrilphosphine, diphenylcyclohexylphosphine and tricyclohexylphosphine; organic phosphite compounds such as trimethylphosphine and triethylphosphine; ethyltriphenyl. Phosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-trilborate, triphenylphosphine triphenylboran, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium disianamide, Examples thereof include phosphonium salts such as butylphenylphosphonium dicyanamide and tetrabutylphosphonium decanoate.

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

Examples of the imidazole-based curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 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-phenylimidazole isocyanuric acid adduct , 2-Phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5 hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole, 1-dodecyl-2 -Methyl-3-benzylimidazolium chloride, 2-methylimidazoline and the like can be mentioned.

Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1, 5,7-Triazabicyclo [4.4.0] deca-5-ene, 7-methyl-1,5,7-triazabicyclo [4.4.0] deca-5-ene, 1-methylbiguanide , 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide and the like.

Examples of the urea-based curing accelerator include 3-phenyl-1,1-dimethylurea, 3- (4-methylphenyl) -1,1-dimethylurea, chlorophenylurea, and 3- (4-chlorophenyl) -1,1. -Dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea and the like can be mentioned.

Among the curing accelerators, triphenylphosphine and tertiary amines are used as phosphorus compounds because they are excellent in curability, heat resistance, electrical properties, moisture resistance reliability, etc., especially when used as a semiconductor encapsulating material. It is preferable to use 1,8-diazabicyclo- [5.4.0] -undecene (DBU).

The amount of the curing accelerator used can be appropriately adjusted in order to obtain the desired curability, but it is 0.01 to 10 parts by mass with respect to 100 parts by mass of the total amount of the mixture of the epoxy resin and the curing agent. Is preferable, and 0.1 to 5 parts by mass is more preferable. When the amount of the curing accelerator used is within the above range, the curing property and the insulation reliability are excellent, which is preferable.

<Flame retardant>
The flame retardant is not particularly limited, and examples thereof include an inorganic phosphorus flame retardant, an organic phosphorus flame retardant, and a halogen flame retardant. The flame retardant may be used alone or in combination of two or more.

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

The organic phosphorus-based flame retardant is not particularly limited, but is limited to methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, and bis (2-ethylhexyl). Phosphate, Monoisodecyl Acid Phosphate, Lauryl Acid Phosphate, Tridecyl Acid Phosphate, Stearyl Acid Phosphate, Isostearyl Acid Phosphate, Oleyl Acid Phosphate, Butyl Pyrophosphate, Tetracosyl Acid Phosphate, Ethylene Glycol Acid Phosphate, (2-Hydroxyethyl) ) Phosphate esters such as methacrylate acid phosphate; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine oxide and the like diphenylphosphine; 10- (2,5-dihydroxyphenyl) -10H- 9-Oxa-10-phosphaphenanthrene-10-oxide, 10- (1,4-dioxynaphthalene) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphos Phosphorus-containing phenols such as phenyl-1,4-dioxynaphthalin, 1,4-cyclooctylenephosphinyl-1,4-phenyldiol, 1,5-cyclooctylenephosphinyl-1,4-phenyldiol 9,10-Dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10 -Cyclic phosphorus compounds such as (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; the phosphoric acid ester, the diphenylphosphine, the phosphorus-containing phenol, and epoxy resins. Examples thereof include an aldehyde compound and a compound obtained by reacting with a phenol compound.

The halogen-based flame retardant is not particularly limited, but is limited to brominated polystyrene, bis (pentabromophenyl) ethane, tetrabromobisphenol A bis (dibromopropyl ether), 1,2, -bis (tetrabromophthalimide), 2, Examples thereof include 4,6-tris (2,4,6-tribromophenoxy) -1,3,5-triazine and tetrabromophthalic acid.

The amount of the flame retardant used is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the epoxy resin.

<Inorganic filler>
The inorganic filler is not particularly limited, but is silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, and nitrided. Boron, aluminum hydroxide, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, barium zirconate , Calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black and the like. Of these, it is preferable to use silica. At this time, as the silica, amorphous silica, fused silica, crystalline silica, synthetic silica, hollow silica and the like can be used. Above all, the molten silica is preferable because it is possible to add a larger amount of the inorganic filler. The fused silica can be used in either a crushed form or a spherical shape, but in order to increase the blending amount of the fused silica and suppress the increase in the melt viscosity of the curable composition, a spherical one is mainly used. Is preferable. Further, in order to increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica. The inorganic filler may be used alone or in combination of two or more.

Further, the inorganic filler may be surface-treated if necessary. At this time, the surface treatment agent that can be used is not particularly limited, but is an aminosilane-based coupling agent, an epoxysilane-based coupling agent, a mercaptosilane-based coupling agent, a silane-based coupling agent, an organosilazane compound, and a titanate-based cup. Ring agents and the like can be used. Specific examples of the surface treatment agent include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and hexamethyldi. Silazan and the like can be mentioned.

The amount of the inorganic filler used is preferably 0.5 to 95 parts by mass with respect to 100 parts by mass of the total amount of the mixture of the epoxy resin and the curing agent. When the amount of the inorganic filler used is within the above range, flame retardancy and insulation reliability are excellent, which is preferable.

Further, an organic filler can be blended in addition to the inorganic filler as long as the characteristics of the present invention are not impaired. Examples of the organic filler include polyamide particles and the like.

<Curing product>
The present invention relates to a cured product of the curable composition. By using the epoxy resin, the cured product obtained from the curable composition containing the epoxy resin can exhibit high heat resistance and high toughness, which is a preferable embodiment.

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

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

Further, the cured product of the present invention preferably has a Charpy impact strength of 6.5 J / cm ² or more, more preferably 7.3 J / cm ² or more, and 7.8 J / cm ² or more. Is particularly preferable. The method for measuring the Charpy impact strength is the same as the evaluation method in the examples of the present application.

<Semiconductor encapsulation material>
The present invention relates to a semiconductor encapsulating material containing the curable composition. Since the semiconductor encapsulation material obtained by using the curable composition uses the epoxy resin, it has a low viscosity and excellent fluidity, and further, the heat resistance and toughness of the cured product are improved, so that in the manufacturing process. It is excellent in processability and moldability, and is a preferable embodiment.

The curable composition used for the semiconductor encapsulant material can contain an inorganic filler. As the filling rate of the inorganic filler, for example, the inorganic filler can be used in the range of 0.5 to 95 parts by mass with respect to 100 parts by mass of the curable composition.

As a method for obtaining the semiconductor encapsulating material, the curable composition is further added with an additive as an optional component, if necessary, using an extruder, a feeder, a roll, or the like until the composition becomes uniform. Examples thereof include a method of sufficiently melting and mixing.

<Semiconductor device>
The present invention relates to a semiconductor device containing a cured product of the semiconductor encapsulating material. Since the semiconductor device obtained by using the semiconductor encapsulating material obtained by using the curable composition uses the epoxy resin, it has low viscosity and excellent fluidity, and further, heat resistance and toughness in the cured product are obtained. Since it has been improved, it is excellent in processability and molding in the manufacturing process, which is a preferable embodiment.

As a method for obtaining the semiconductor device, the semiconductor encapsulant material is cast or molded using a transfer molding machine, an injection molding machine, or the like, and further heat-cured in a temperature range of room temperature (20 ° C.) to 250 ° C. There is a way to do it.

<Prepreg>
The present invention relates to a prepreg having a reinforcing base material and a semi-cured product of the curable composition impregnated in the reinforcing base material. As a method for obtaining a prepreg from the curable composition, a curable composition varnished by blending an organic solvent described later is used as a reinforcing base material (paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass). A method of obtaining the material by impregnating it with a mat, a glass roving cloth, etc.) and then heating it at a heating temperature according to the solvent type used, preferably 50 to 170 ° C. can be mentioned. The mass ratio of the curable composition and the reinforcing base material used at this time is not particularly limited, but it is usually preferable to prepare the resin content in the prepreg to be 20 to 60% by mass.

Examples of the organic solvent 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. It can be appropriately selected depending on the application, but for example, when further producing a printed circuit board from prepylene as described below, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, or dimethylformamide. , It is preferable to use the non-volatile content at a ratio of 40 to 80% by mass.

<Circuit board>
The present invention relates to the circuit board which is a laminated body of the prepreg and a copper foil. As a method for obtaining a printed circuit board from the curable composition, the prepregs are laminated by a conventional method, copper foils are appropriately laminated, and the pressure is 170 to 300 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa. An example is a method of heat-bonding.

<Build-up film>
The present invention relates to a build-up film containing the curable composition. As a method for producing the build-up film of the present invention, the curable composition is applied onto a support film to form a curable composition layer to form an adhesive film for a multilayer printed wiring board. The method can be mentioned.

When a build-up film is produced from a curable composition, the film is softened under the temperature conditions of laminating (usually 70 to 140 ° C.) in the vacuum laminating method, and at the same time as laminating the circuit board, via holes existing in the circuit board. Alternatively, it is important to show fluidity (resin flow) capable of filling the through hole with the resin, and it is preferable to blend each of the above components so as to exhibit such characteristics.

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 usually preferable to enable resin filling in this range. .. When laminating both sides of the circuit board, it is desirable to fill about 1/2 of the through hole.

Specifically, in the method for producing the adhesive film described above, after preparing the varnish-like curable composition, the varnish-like composition is applied to the surface of the support film (Y), and further heated. Alternatively, it can be produced by drying an organic solvent 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 conductor layer of 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.

The composition layer (X) in the present invention may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent dust and the like from adhering to the surface of the resin composition layer and scratches.

The above-mentioned support film and protective film include polyolefins such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter, may be abbreviated as "PET"), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples include metal foils such as patterns, copper foils, and aluminum foils. The support film and the protective film may be subjected to a mold release treatment in addition to the mud treatment and the corona treatment.

The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and is preferably used in the range of 25 to 50 μm. 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 heat curing. If the support film (Y) is peeled off after the adhesive film is heat-cured, it is possible to prevent dust and the like from adhering in the curing step. When peeling after curing, the support film is usually subjected to a mold release treatment in advance.

<Other uses>
Since the cured product obtained by the curable composition of the present invention is excellent in heat resistance and toughness in the cured product, it can be used only for applications such as semiconductor encapsulation materials, semiconductor devices, prepregs, circuit boards, and build-up films. However, it can be suitably used for various applications such as build-up substrates, adhesives, resist materials, and matrix resins of fiber-reinforced resins, and the applications are not limited to these.

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these scopes. The measurement and evaluation of physical properties and characteristics were carried out as follows, and the evaluation results are shown in Tables 1 and 2 below.

<Softening point>
The softening point (° C.) was measured according to JIS K7234 (ring ball method).

<Measurement of epoxy equivalent>
Measured based on JIS K 7236.

<Measurement method of melt viscosity at 150 ° C>
It was measured with an ICI viscometer according to ASTM D4287.

<Measurement of gel permeation chromatography (GPC)>
GPC measurement was performed under the conditions shown below, and the obtained GPC chart was evaluated to obtain the number average molecular weight (Mn), weight average molecular weight (Mw), and dispersity (Mw / Mn) of the obtained epoxy resin. Was calculated.
Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation,
Column: Guard column "HXL-L" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G3000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G4000HXL" manufactured by Tosoh Corporation
Detector: RI (Differential Refractometer)
Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran Flow rate 1.0 ml / min Standard: The following monodisperse polystyrene with a known molecular weight was used in accordance with the measurement manual of the above-mentioned "GPC workstation EcoSEC-WorkStation".
(Polystyrene used)
"A-500" manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
"F-1" manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
"F-4" manufactured by Tosoh Corporation
"F-10" manufactured by Tosoh Corporation
"F-20" manufactured by Tosoh Corporation
"F-40" manufactured by Tosoh Corporation
"F-80" manufactured by Tosoh Corporation
"F-128" manufactured by Tosoh Corporation
Sample: A solution of 1.0% by mass in tetrahydrofuran in terms of resin solid content filtered through a microfilter (50 μl).

(Synthesis Example 1: Synthesis of phenolic hydroxyl group-containing resin (P2-1))
A flask equipped with a thermometer, a cooling tube, a fractional distillation tube, a nitrogen gas introduction tube, and a stirrer is charged with 160 g (1.0 mol) of 2,7-dihydroxynaphthalene and 27.0 g (0.25 mol) of benzyl alcohol. , Stirred while blowing nitrogen under room temperature conditions. Then, 2.7 g of p-toluenesulfonic acid / monohydrate was added. Then, the mixture was heated to 150 ° C. in an oil bath while paying attention to heat generation, and the water produced was extracted using a fractional distillation tube, and then the reaction was carried out for another 5 hours. After completion of the reaction, 1000 g of methyl isobutyl ketone was added to dissolve the reaction product, and then the reaction product was transferred to a separating funnel. After washing with water until the washing water became neutral, the solvent was removed from the organic layer under heating and reduced pressure conditions to obtain 240 g of the desired phenolic hydroxyl group-containing resin (P2-1). The obtained phenolic hydroxyl group-containing resin (P2-1) had a softening point of 97 ° C. and a hydroxyl group equivalent of 146 g / equivalent. Further, the content of the compound (A) having three naphthalene ring structures in one molecule of the phenolic hydroxyl group-containing resin (P2-1) was 33%. The GPC chart of the phenolic hydroxyl group-containing resin (P2-1) is shown in FIG. The content of the compound (A) was calculated from the area ratio of the GPC chart.

The compound (A) contained in the phenolic hydroxyl group-containing resin (P2-1) obtained above was represented by the following structural formula.

(Example 1: Synthesis of epoxy resin (1))
180.0 g of the phenolic hydroxyl group-containing resin (P2-1) obtained in Synthesis Example 1 while performing nitrogen gas purging on a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer, 4,4'-biphenol. 60.0 g, epichlorhydrin 1157 g, n-butanol 347 g, and water 58 g were charged and dissolved. After raising the temperature to 60 ° C., 480 g of a 20 mass% sodium hydroxide aqueous solution was added dropwise over 5 hours. Then, stirring was continued for 0.5 hours under the same conditions. Then, unreacted epichlorohydrin was distilled off by vacuum distillation to obtain a crude product. 600 g of methyl isobutyl ketone was added to the obtained crude product and dissolved. 33 g of a 5 mass% sodium hydroxide aqueous solution was added to this solution, and the mixture was reacted at 80 ° C. for 2 hours. 180 g of water was added to the reaction mixture, and the mixture was washed with water. Washing with water was repeated 3 times until the pH of the washing liquid became neutral. Then, the inside of the system was azeotropically boiled to dehydrate, and after undergoing microfiltration, the solvent was distilled off under reduced pressure to obtain an epoxy resin (1). The obtained epoxy resin (1) has an epoxy equivalent of 197 g / equivalent, a melt viscosity at 150 ° C. of 0.2 dPa · s, a number average molecular weight (Mn) of 314, a weight average molecular weight (Mw) of 372, and a degree of dispersion (Mw). / Mn) was 1.2. The GPC chart of the epoxy resin (1) is shown in FIG.

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

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

(Example 2: Synthesis of epoxy resin (2))
In Example 1, the reaction was carried out in the same manner as in Example 1 except that the phenolic hydroxyl group-containing resin (P2-1) was changed to 192.0 g and 4,4'-biphenol 48.0 g, and the epoxy resin (2) was used. Obtained. The obtained epoxy resin (2) has an epoxy equivalent of 203 g / equivalent, a melt viscosity at 150 ° C. of 0.3 dPa · s, a number average molecular weight (Mn) of 319, a weight average molecular weight (Mw) of 381, and a degree of dispersion (Mw). / Mn) was 1.2. The GPC chart is shown in FIG.

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

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

(Example 3: Synthesis of epoxy resin (3))
In Example 1, the reaction was carried out in the same manner as in Example 1 except that the phenolic hydroxyl group-containing resin (P2-1) was changed to 232.8 g and 4,4'-biphenol 7.2 g, and the epoxy resin (3) was used. Obtained. The obtained epoxy resin (3) has an epoxy equivalent of 213 g / equivalent, a melt viscosity at 150 ° C. of 0.4 dPa · s, a number average molecular weight (Mn) of 336, a weight average molecular weight (Mw) of 412, and a degree of dispersion (Mw). / Mn) was 1.2. The GPC chart is shown in FIG.

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

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

(Comparative Synthesis Example 1: Synthesis of Phenolic Hydroxyl Group-Containing Resin (1'))
432.4 g (4.0 mol) of o-cresol, 158.2 g (1.0 mol) of 2-methoxynaphthalene, in a flask equipped with a thermometer, a cooling tube, a fractional distillation tube, a nitrogen gas introduction tube, and a stirrer. 179.3 g (2.45 mol) of a 41 mass% formaldehyde aqueous solution was charged, 9.0 g of oxalic acid was added, the temperature was raised to 100 ° C., and the reaction was carried out at 100 ° C. for 3 hours. Then, while collecting water with a fractional distillation tube, 73.2 g (1.0 mol) of a 41 mass% formaldehyde aqueous solution was added dropwise over 1 hour. After completion of the dropping, the temperature was raised to 150 ° C. over 1 hour, and the reaction was carried out at the same temperature for 2 hours. After completion of the reaction, 1500 g of methyl isobutyl ketone was added and transferred to a separating funnel. After washing with water until the washing water becomes neutral, unreacted o-cresol, 2-methoxynaphthalene, and methyl isobutyl ketone are removed from the organic layer under heating and reduced pressure conditions, and the phenolic hydroxyl group-containing resin (1') is removed. Got The obtained phenolic hydroxyl group-containing resin (1') had a softening point of 76 ° C. and a hydroxyl group equivalent of 164 g / equivalent.

(Comparative Example 1: Synthesis of Epoxy Resin (1'))
137.1 g (0.84 equivalent of hydroxyl group) of the phenolic hydroxyl group-containing resin (1') obtained in Comparative Synthesis Example 1 while performing nitrogen gas purging on a flask equipped with a thermometer, a dropping funnel, a cooling tube, and a stirrer. 14.3'-biphenol 15.3 g (hydroxyl equivalent 0.16 equivalent), epichlorohydrin 463 g (5.0 mol), n-butanol 139 g, and tetraethylbenzylammonium chloride 2 g were charged and dissolved. After raising the temperature to 70 ° C., 220 g (1.1 mol) of a 20 mass% sodium hydroxide aqueous solution was added dropwise over 5 hours. Then, stirring was continued for 0.5 hours under the same conditions. Unreacted epichlorohydrin was distilled off by vacuum distillation to obtain a crude product. To the obtained crude product, 1000 g of methyl isobutyl ketone and 350 g of n-butanol were added and dissolved. After adding 10 g of a 10 mass% sodium hydroxide aqueous solution to this solution and reacting at 80 ° C. for 2 hours, washing with 150 g of water was repeated 3 times until the pH of the washing liquid became neutral. The inside of the system was azeotropically boiled to dehydrate, and after undergoing microfiltration, the solvent was distilled off under reduced pressure conditions to obtain 176 g of epoxy resin (1'). The obtained epoxy resin (1') has 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 (Mw). Mw / Mn) was 1.6.

(Examples 4 to 6 and Comparative Example 2: Preparation of epoxy resin composition)
Each component was blended in the composition shown in Table 2 and melt-kneaded to obtain each epoxy resin composition. The details of each component in Table 2 are as follows.
Curing agent: Phenolic novolak type phenol resin ("TD-2131" manufactured by DIC Corporation, hydroxyl group equivalent 104 g / equivalent)
Curing accelerator: Triphenylphosphine ("TPP" manufactured by Hokuko Chemical Industry Co., Ltd.)

<Heat resistance evaluation>
Each of the above epoxy resin compositions was cured in a normal pressure press at 150 ° C. for 10 minutes so that the thickness of the cured product was 2.4 mm, and then aftercure was performed at 175 ° C. for 5 hours. A cured product for evaluation was obtained.
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. The heat resistance is evaluated using a viscoelasticity measuring device (Reometric's "solid viscoelasticity measuring device RSAII", rectangular tension method: frequency 1 Hz, temperature rise rate 3 ° C./min), and the change in elasticity is maximized (tanδ). The temperature (with the largest rate of change) was defined as the glass transition temperature (Tg) (° C.), and the heat resistance was evaluated.

<Toughness evaluation>
Using each epoxy resin composition, transfer molding was performed at 175 ° C. for 120 seconds at a molding pressure of 6.9 MPa in accordance with JIS K 6911, and further, as post-cure, treatment at 175 ° C. for 5 hours was performed. A test piece for Charpy impact strength test was prepared. The obtained test piece was measured for Charpy impact strength (J / cm ² ) using a Pendulum Impact Tester Zwick 5102, and the toughness was evaluated.

From the evaluation results in Tables 1 and 2 above, the epoxy resins obtained in all the examples have low viscosity, excellent high fluidity, can contribute to good moldability, and are epoxy resins containing the epoxy resin. The cured product obtained by using the composition (curable composition) has a high glass transition temperature, high heat resistance, shows a high value even in a Charpy impact test, and can be confirmed to have high toughness. It was confirmed that both heat resistance and high toughness were achieved.

On the other hand, from the evaluation results of Tables 1 and 2 above, in Comparative Example 1, an epoxy resin (1') was synthesized without using a desired phenolic hydroxyl group-containing resin, and an epoxy resin composition using this was synthesized. In Comparative Example 2 using (curable composition), the results were inferior in heat resistance and toughness as compared with Examples.

Claims

The reaction raw material is a glycidyl etherified product (E1) of a biphenol compound (P1) and a dihydroxyarene compound (α) and an aralkylating agent (β) represented by the following general formula (1-1) or (1-2). An epoxy resin containing a glycidyl etherified compound (E2) of a phenolic hydroxyl group-containing resin (P2).

[In the above general formulas (1-1) and (1-2), X represents any of a halogen atom, a hydroxyl group, and an alkoxy group. R 1 independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 2 independently represents a hydrogen atom or a methyl group. Ar 1 represents any of a phenyl group, a naphthyl group, and a structural moiety having one or more halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups on these aromatic nuclei. ]
A phenolic hydroxyl group-containing resin using a biphenol compound (P1) and a dihydroxyarene compound (α) as a reaction raw material with an aralkylating agent (β) represented by the following general formula (1-1) or (1-2). An epoxy resin containing the glycidyl etherified compound (E3) of the mixture of (P2).

[In the above general formulas (1-1) and (1-2), X represents any of a halogen atom, a hydroxyl group, and an alkoxy group. R 1 independently represents either a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R 2 independently represents a hydrogen atom or a methyl group. Ar 1 represents any of a phenyl group, a naphthyl group, and a structural moiety having one or more halogen atoms, aliphatic hydrocarbon groups, and alkoxy groups on these aromatic nuclei. ]
The second aspect of claim 2, wherein 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 0.5% by mass or more and 40% by mass or less. Epoxy resin.
The epoxy resin according to any one of claims 1 to 3, wherein the phenolic hydroxyl group-containing resin (P2) contains a compound (A) having three naphthalene ring structures in one molecule.
According to claim 4, the content of the compound (A) in the phenolic hydroxyl group-containing resin (P2) is 5 to 50% as a value calculated from the area ratio of the chart diagram of gel permeation chromatography (GPC). The epoxy resin described.
The epoxy resin according to any one of claims 1 to 5, wherein the melt viscosity at 150 ° C. measured by an ICI viscometer is 0.01 to 5 dPa · s.
A curable composition containing the epoxy resin according to any one of claims 1 to 6 and a curing agent for an epoxy resin.
A cured product of the curable composition according to claim 7.
A semiconductor encapsulating material containing the curable composition according to claim 7.
A semiconductor device containing a cured product of the semiconductor encapsulating material according to claim 9.
A prepreg having a reinforcing base material and a semi-cured product of the curable composition according to claim 7, which is impregnated with the reinforcing base material.
The circuit board which is a laminated body of the prepreg and the copper foil according to claim 11.
A build-up film containing the curable composition according to claim 7.