Epoxy resins, curable compositions, cured products, semiconductor sealing materials, semiconductor devices, prepregs, circuit boards, and multilayer films.

Abstract

This invention provides an epoxy resin comprising: a glycidyl ether of a biphenol compound (P1) (E1) and a glycidyl ether of a phenolic hydroxyl resin (P2) (E2), wherein the phenolic hydroxyl resin (P2) is reacted with a dihydroxy aromatic compound (α) and an aralkylating agent (β) of general formula (1-1) or (1-2). [In the following general formulas (1-1) and (1-2), X represents any one of a halogen atom, a hydroxyl group, or an alkoxy group. R] 1 Each independently represents either a hydrogen atom or any alkyl group having 1 to 4 carbon atoms. R 2 Each can independently represent a hydrogen atom or a methyl group. Ar 1 This refers to any of the following structural sites: phenyl, naphthyl, having one or more halogen atoms on their aromatic nucleus, aliphatic hydrocarbon group, or alkoxy group.

Description

Technical Field

[0001] This invention relates to epoxy resins, curable compositions, cured products, semiconductor sealing materials, semiconductor devices, prepregs, circuit boards, and multilayer films. Background Technology

[0002] Epoxy resin compositions, which use epoxy resin and its curing agent as essential components, are widely used in semiconductor sealing materials, electronic components such as printed circuit boards, conductive adhesives such as conductive pastes, other adhesives, composite material matrices, coatings, photoresist materials, and color development materials, due to their excellent physical properties such as high heat resistance, moisture resistance, and low viscosity.

[0003] Among the various applications, 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 during the reflow soldering process, so the resin materials used for sealing are required to have high heat resistance.

[0004] Furthermore, in order to reduce the warping of semiconductor sealing materials during the miniaturization / thinning of electronic devices and mass sealing processes in recent years, highly tough resin materials are required.

[0005] In addition to the above-mentioned performance requirements, semiconductor sealing materials are required to be used by filling the resin material with inorganic fillers such as silicon dioxide. Therefore, in order to improve the filling rate of the filler, the resin material is also required to have low viscosity and excellent flowability.

[0006] As a semiconductor sealing material that meets the required properties, for example, the use of aralkyl-modified poly(oxonaphthyl) type epoxy resin has been disclosed (see Patent Document 1).

[0007] However, the cured product obtained from the aforementioned epoxy resin disclosed in Patent Document 1 has excellent heat resistance, but the epoxy resin itself has high melt viscosity, and the epoxy resin composition containing the aforementioned epoxy resin has poor flowability and formability, and the reduction of warpage is also unclear.

[0008] Thus, in the field of semiconductor sealing materials, it is currently impossible to obtain epoxy resin compositions for semiconductor sealing that have particularly low viscosity and excellent flowability and formability, as well as epoxy resin compositions with high heat resistance and sufficient toughness of cured products obtained from the aforementioned epoxy resin compositions.

[0009] Existing technical documents

[0010] Patent documents

[0011] Patent Document 1: Japanese Patent No. 5689230 Summary of the Invention

[0012] The problem the invention aims to solve

[0013] Therefore, the problem to be solved by the present invention is to provide: an epoxy resin with low melt viscosity that can help with flowability and formability, a curable composition containing the aforementioned epoxy resin, a cured product obtained using the aforementioned curable composition that has excellent heat resistance and high toughness, a semiconductor sealing material, a semiconductor device, a prepreg, a circuit board, and a multilayer film.

[0014] Solution for solving the problem

[0015] In order to solve the above-mentioned problems, the inventors conducted in-depth research and as a result discovered epoxy resins that contribute to excellent flowability and formability, curable compositions containing the aforementioned epoxy resins, cured products with excellent heat resistance and high toughness obtained using the aforementioned curable compositions, semiconductor sealing materials, semiconductor devices, prepregs, circuit boards, and multilayer films, thereby completing the present invention.

[0016] That is, the present invention relates to an epoxy resin comprising: a glycidyl ether of a biphenol compound (P1) (E1) and a glycidyl ether of a phenolic hydroxyl resin (P2) (E2), wherein the phenolic hydroxyl resin (P2) is reacted with a dihydroxy aromatic compound (α) and an aralkylating agent (β) represented by the following general formula (1-1) or (1-2).

[0017]

[0018] In the above general formulas (1-1) and (1-2), X represents any one of the halogen atom, hydroxyl group, or alkoxy group. R 1 Each independently represents either a hydrogen atom or any alkyl group having 1 to 4 carbon atoms. R 2 Each can independently represent a hydrogen atom or a methyl group. Ar 1 This refers to any of the following structural sites: phenyl, naphthyl, having one or more halogen atoms on their aromatic nucleus, aliphatic hydrocarbon group, or alkoxy group.

[0019] In addition, the present invention relates to an epoxy resin comprising: a glycidyl ether (E3) of a mixture of a biphenol compound (P1) and a phenolic hydroxyl resin (P2), wherein the phenolic hydroxyl resin (P2) is reacted with a dihydroxy aromatic compound (α) and an aralkylating agent (β) represented by the following general formula (1-1) or (1-2).

[0020]

[0021] In the above general formulas (1-1) and (1-2), X represents any one of the halogen atom, hydroxyl group, or alkoxy group. R1 Each independently represents either a hydrogen atom or any alkyl group having 1 to 4 carbon atoms. R 2 Each can independently represent a hydrogen atom or a methyl group. Ar 1 This refers to any of the following structural sites: phenyl, naphthyl, having one or more halogen atoms on their aromatic nucleus, aliphatic hydrocarbon group, or alkoxy group.

[0022] In the epoxy resin of the present invention, the ratio of the aforementioned biphenol compound (P1) to the total mass of the aforementioned biphenol compound (P1) and the aforementioned phenolic hydroxyl-containing resin (P2) is preferably 0.5% by mass or more and 40% by mass or less.

[0023] In the epoxy resin of the present invention, the aforementioned phenolic hydroxyl resin (P2) preferably contains a compound (A) having a structure of 3 naphthalene rings in one molecule.

[0024] In the epoxy resin of the present invention, the content of the aforementioned compound (A) in the aforementioned phenolic hydroxyl resin (P2) is preferably 50% to 50% as calculated based on the area ratio of the gel permeation chromatography (GPC) spectrum.

[0025] In the epoxy resin of the present invention, the melt viscosity at 150°C, as measured by an ICI viscometer, is preferably 0.01 to 5 dPa·s.

[0026] This invention relates to a curable composition comprising the aforementioned epoxy resin and a curing agent for epoxy resin.

[0027] This invention relates to a cured product, which is a cured product of the aforementioned curable composition.

[0028] This invention relates to a semiconductor sealing material containing the aforementioned curable composition.

[0029] The present invention relates to a semiconductor device comprising a cured form of the aforementioned semiconductor sealing material.

[0030] The present invention relates to a prepreg having: a reinforcing substrate and a semi-cured product of the aforementioned curable composition impregnated in the aforementioned reinforcing substrate.

[0031] The present invention relates to a circuit board, which is a laminate of the aforementioned prepreg and copper foil.

[0032] The present invention relates to a laminated film containing the aforementioned curable composition.

[0033] The effects of the invention

[0034] The epoxy resin of the present invention has low viscosity, excellent flowability and formability. In addition, the cured composition containing the aforementioned epoxy resin has excellent heat resistance and high toughness, and is therefore particularly useful as a resin material for electrical materials such as semiconductor sealing materials. Attached Figure Description

[0035] Figure 1 The image shows the GPC diagram of the phenolic hydroxyl-containing resin (P2-1) obtained in Synthesis Example 1.

[0036] Figure 2 The image shows the GPC diagram of the epoxy resin (1) obtained in Example 1.

[0037] Figure 3 The image shows the GPC diagram of the epoxy resin (2) obtained in Example 2.

[0038] Figure 4 The image shows the GPC diagram of the epoxy resin (3) obtained in Example 3. Detailed Implementation

[0039] This invention relates to an epoxy resin comprising: a glycidyl ether of a biphenol compound (P1) (E1) and a glycidyl ether of a phenolic hydroxyl resin (P2) (E2), wherein the phenolic hydroxyl resin (P2) is reacted with a dihydroxy aromatic compound (α) and an aralkylating agent (β) represented by the following general formula (1-1) or (1-2).

[0040]

[0041] In the above general formulas (1-1) and (1-2), X represents any one of the halogen atom, hydroxyl group, or alkoxy group. R 1 Each independently represents either a hydrogen atom or any alkyl group having 1 to 4 carbon atoms. R 2 Each can independently represent a hydrogen atom or a methyl group. Ar 1 This refers to any of the following structural sites: phenyl, naphthyl, having one or more halogen atoms on their aromatic nucleus, aliphatic hydrocarbon group, or alkoxy group.

[0042] In addition, the present invention relates to an epoxy resin comprising: a glycidyl ether (E3) of a mixture of a biphenol compound (P1) and a phenolic hydroxyl resin (P2), wherein the phenolic hydroxyl resin (P2) is reacted with a dihydroxy aromatic compound (α) and an aralkylating agent (β) represented by the following general formula (1-1) or (1-2).

[0043]

[0044] In the above general formulas (1-1) and (1-2), X represents any one of the halogen atom, hydroxyl group, or alkoxy group. R1 Each independently represents either a hydrogen atom or any alkyl group having 1 to 4 carbon atoms. R 2 Each can independently represent a hydrogen atom or a methyl group. Ar 1 This refers to any of the following structural sites: phenyl, naphthyl, having one or more halogen atoms on their aromatic nucleus, aliphatic hydrocarbon group, or alkoxy group.

[0045] <Biphenyl compound (P1)>

[0046] There are no particular limitations on the aforementioned biphenol compound (P1). Examples 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 compound (P1) can be used alone or in combination of two or more.

[0047] The aforementioned aliphatic hydrocarbon groups can be either linear or branched, and may contain unsaturated bonds in their structure. From the perspective of achieving superior heat resistance of the cured product, aliphatic hydrocarbon groups with 1 to 4 carbon atoms are preferred; specifically, examples include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, vinyl, and allyl. Examples of alkoxy groups include methoxy, ethoxy, propoxy, and butoxy. Examples of halogen atoms include fluorine, chlorine, and bromine. In particular, from the perspective of easily adjusting the melt viscosity of the final epoxy resin to a preferred value, it is preferable to have substituents on 4,4'-biphenyl and its aromatic ring, more preferably 4,4'-biphenyl.

[0048] <Phenolic hydroxyl resin (P2)>

[0049] The aforementioned phenolic hydroxyl resin (P2) uses a dihydroxy aromatic compound (α) and an aralkylating agent (β) as shown in the following general formula (1-1) or (1-2) as reaction raw materials.

[0050]

[0051] In the above general formulas (1-1) and (1-2), X represents any one of the halogen atom, hydroxyl group, or alkoxy group. R 1 Each independently represents either a hydrogen atom or any alkyl group having 1 to 4 carbon atoms. R 2 Each can independently represent a hydrogen atom or a methyl group. Ar 1 This refers to any of the following structural sites: phenyl, naphthyl, having one or more halogen atoms on their aromatic nucleus, aliphatic hydrocarbon group, or alkoxy group.

[0052] In the above general formulas (1-1) and (1-2), X represents any one of the halogen atom, hydroxyl group, or alkoxy group. R 1 Each independently represents either a hydrogen atom or any alkyl group having 1 to 4 carbon atoms. R 2 Each can independently represent a hydrogen atom or a methyl group. Ar 1 It represents any of the following structural sites: phenyl, naphthyl, having one or more halogen atoms on their aromatic nuclei, aliphatic hydrocarbon group, or alkoxy group.

[0053] The aforementioned phenolic hydroxyl-containing resin (P2) contains a component having a (poly)arylene ether structure generated through the intermolecular dehydration reaction of the aforementioned dihydroxy aromatic compound (α). Furthermore, using the aforementioned aralkylating agent (β), a portion or all of the aromatic rings in the aforementioned phenolic hydroxyl-containing resin (P2) are introduced into the aralkyl group. As a result, the glycidyl ether groups in the molecule of the aforementioned phenolic hydroxyl-containing resin (P2) glycidyl ether (E2) are spaced further apart, and the concentration of aromatic rings is increased, thus achieving a high level of both heat resistance and toughness in the resulting cured product.

[0054] The aforementioned dihydroxy aromatic compound (α) can be any compound having two hydroxyl groups on its aromatic ring, and its specific structure is not particularly limited; a wide variety of compounds can be used. Specific examples include dihydroxybenzene, dihydroxynaphthalene, and compounds having one or more substituents such as halogen atoms, aliphatic hydrocarbon groups, or alkoxy groups on their aromatic rings. In this invention, the aforementioned dihydroxy aromatic compound (α) can be used alone or in combination of two or more.

[0055] In the aforementioned dihydroxybenzene, the substitution positions of the two hydroxyl groups are not particularly limited and can be any of the ortho, meta, or para positions. Similarly, in the aforementioned dihydroxynaphthalene, the substitution positions of the two hydroxyl groups are not particularly limited; for example, they can be any of the 1,2-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6-, or 2,7- positions.

[0056] Examples of halogen atoms mentioned above include fluorine, chlorine, and bromine atoms. The aforementioned aliphatic hydrocarbon groups can be either straight-chain or branched, and may contain unsaturated bonds in their structure. Specifically, examples include methyl, ethyl, propyl, and butyl. Examples of alkoxy groups mentioned above include methoxy, ethoxy, propoxy, and butoxy.

[0057] Among the aforementioned dihydroxy aromatic compounds (α), dihydroxynaphthalene and compounds having one or more substituents such as halogen atoms, aliphatic hydrocarbon groups, or alkoxy groups on their aromatic rings are preferred, with dihydroxynaphthalene being more preferred, considering the superior heat resistance and toughness of the resulting cured product. The hydroxyl group on the aforementioned dihydroxynaphthalene is preferably at the 1,6-position or the 2,7-position, more preferably at the 2,7-position. Furthermore, when multiple dihydroxy aromatic compounds (α) are used in combination, the proportion of dihydroxynaphthalene and compounds having one or more substituents such as halogen atoms, aliphatic hydrocarbon groups, or alkoxy groups on their aromatic rings in the aforementioned dihydroxy aromatic compound (α) is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 95% by mass or more.

[0058] The aforementioned aralkylating agent (β) has the molecular structure shown in the aforementioned general formula (1-1) or (1-2). In this invention, one type of aralkylating agent (β) can be used alone, or two or more types can be used in combination.

[0059] In the aforementioned general formulas (1-1) and (1-2), X represents any one of a halogen atom, a hydroxyl group, or an alkoxy group. Examples of halogen atoms include fluorine, chlorine, and bromine atoms. Examples of alkoxy groups include methoxy, ethoxy, propoxy, and butoxy groups. Among these, from the perspective of superior reactivity, a halogen atom or a hydroxyl group is preferred, and a hydroxyl group is particularly preferred.

[0060] In the aforementioned general formulas (1-1) and (1-2), the aforementioned R 1 Each can be independently represented by a hydrogen atom or any alkyl group having 1 to 4 carbon atoms. Among these, hydrogen atoms are preferred from the perspective of excellent reactivity.

[0061] In the aforementioned general formulas (1-1) and (1-2), the aforementioned R 2 Each can be represented independently as a hydrogen atom or a methyl group. Among them, the hydrogen atom is preferred due to its superior reactivity.

[0062] In the aforementioned general formulas (1-1) and (1-2), the aforementioned Ar 1 It is any of the following structural sites: phenyl, naphthyl, having one or more halogen atoms on their aromatic nuclei, aliphatic hydrocarbon group, or alkoxy group.

[0063] Examples of halogen atoms mentioned above include fluorine, chlorine, and bromine atoms. The aforementioned aliphatic hydrocarbon groups can be either straight-chain or branched, and can contain unsaturated bonds in their structure. Specifically, examples include methyl, ethyl, propyl, and butyl. Examples of alkoxy groups mentioned above include methoxy, ethoxy, propoxy, and butoxy. Among these, considering the more pronounced effect of superior heat resistance and toughness of the cured product, the aforementioned Ar... 1Preferably phenyl or naphthyl, more preferably phenyl.

[0064] When multiple aralkylating agents (β) are used in combination as mentioned above, the aforementioned Ar 1 The proportion of the phenyl compound in the aforementioned aralkylating agent (β) is preferably 50% by mass or more, more preferably 80% by mass or more, and particularly preferably 95% by mass or more.

[0065] The aforementioned phenolic hydroxyl resin (P2) may use components other than the aforementioned dihydroxy aromatic compound (α) and the aforementioned aralkylating agent (β) as 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) that constitute the total mass of the reaction raw materials of the aforementioned phenolic hydroxyl resin (P2) is preferably 80% by mass or more, more preferably 95% by mass or more.

[0066] As a method for manufacturing the aforementioned phenolic hydroxyl-containing resin (P2), for example, a method can be described by reacting the reaction raw materials containing the aforementioned dihydroxy aromatic compound (α) and the aforementioned aralkylating agent (β) under acid catalytic conditions. Alternatively, the reaction can be carried out in a solvent as needed.

[0067] Regarding the reaction ratio of the aforementioned dihydroxy aromatic compound (α) to the aforementioned aralkylating agent (β), from the perspective of obtaining an epoxy resin with excellent flowability, the molar ratio of the two [(α) / (β)] is preferably in the range of 1 / 0.1 to 1 / 10, more preferably in the range of 1 / 0.1 to 1 / 1.

[0068] Examples of the aforementioned acid catalysts 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; and Friedel-Crafts catalysts such as aluminum chloride, zinc chloride, tin chloride, ferric chloride, and diethylsulfuric acid. These can be used individually or in combination of two or more.

[0069] When using an inorganic or organic acid as the aforementioned acid catalyst, it is preferable to use an amount in the range of 0.01 to 3 parts by mass relative to 100 parts by mass of the aforementioned dihydroxy aromatic compound (α). When using a Friedel-Crafts catalyst as the aforementioned acid catalyst, it is preferable to use an amount in the range of 0.01 to 3 parts by mass relative to 100 parts by mass of the aforementioned dihydroxy aromatic compound (α).

[0070] One mole is used in the range of 0.5 to 2 moles.

[0071] Examples of the aforementioned solvents include acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellolytic esters, 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, cellolytic agent, butyl carbitol, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, toluene, xylene, chlorobenzene, etc. These can be used individually or in mixtures of two or more solvents. When using these solvents, it is preferable to use them in the range of 20% to 300% by mass relative to the total mass of the aforementioned phenolic hydroxyl resin (P2) reaction raw materials.

[0072] The reaction between the aforementioned dihydroxy aromatic compound (α) and the aforementioned aralkylating agent (β) can be carried out at a temperature of approximately 60–180°C for a reaction time of approximately 1–24 hours. The reaction can be carried out more efficiently by removing water and other substances generated during the reaction through appropriate distillation. After the reaction is complete, the reaction system can be neutralized with an alkaline compound such as an alkali metal hydroxide, or washed with water and then dried to obtain the aforementioned phenolic hydroxyl-containing resin (P2).

[0073] For the aforementioned phenolic hydroxyl resin (P2), from the perspective of more significant effects on the heat resistance and toughness of the cured product, the hydroxyl equivalent is preferably in the range of 100 to 400 g / equivalent, and more preferably in the range of 110 to 300 g / equivalent. Furthermore, its softening point is preferably in the range of 60 to 140°C.

[0074] As an example of the aforementioned phenolic hydroxyl resin (P2), for example, if 2,7-dihydroxynaphthalene is used as the dihydroxy aromatic compound (α) and benzyl alcohol is used as the aforementioned aralkylating agent (β), the specific structures of each component contained in the aforementioned phenolic hydroxyl resin (P2) can be given as, for example, the structures shown in any of the following structural formulas (2-1) to (2-18).

[0075]

[0076]

[0077]

[0078] For the aforementioned phenolic hydroxyl resin (P2), from the perspective of more obvious effects of excellent heat resistance and toughness of the cured product, it is preferable to have a compound (A) containing three naphthalene ring structures in one molecule, as shown in the aforementioned structural formulas (2-6) to (2-8), (2-10), and (2-11).

[0079] Furthermore, the content of the aforementioned compound (A) in the aforementioned phenolic hydroxyl resin (P2), calculated based on the area ratio of the gel permeation chromatography (GPC) chromatogram, is preferably 5-50%, more preferably 10-45%. It should be noted that the gel permeation chromatography (GPC) was performed under the measurement conditions described in the examples described later.

[0080] The epoxy resin of the present invention is not particularly limited in its preparation method as long as it contains the glycidyl ether (E1) of the aforementioned biphenol compound (P1) and the glycidyl ether (E2) of the aforementioned phenolic hydroxyl resin (P2). It can be obtained by any manufacturing process.

[0081] As a method for manufacturing the epoxy resin of the present invention, for example, (1) the aforementioned biphenol compound (P1) can be reacted with epoxy halopropane to synthesize glycidyl etherified product (E1) and the aforementioned phenolic hydroxyl resin (P2) can be reacted with epoxy halopropane to synthesize glycidyl etherified product (E2) and the mixture thereof can be used as the epoxy resin of the present invention.

[0082] Alternatively, (2) epoxy halopropane can be added to the mixture of the aforementioned biphenol compound (P1) and the aforementioned phenolic hydroxyl resin (P2), so that the aforementioned biphenol compound (P1) and the aforementioned phenolic hydroxyl resin (P2) react with epoxy halopropane respectively, thereby synthesizing a glycidyl ether (E3) containing the aforementioned glycidyl ether (E1) and the aforementioned glycidyl ether (E2), and the one containing glycidyl ether (E3) is used as the epoxy resin of the present invention.

[0083] In particular, the manufacturing method described in (2) above is preferred due to its ease of use and operability.

[0084] In the aforementioned method for manufacturing epoxy resin (1), the reaction of the aforementioned biphenol compound (P1) with epoxy halopropane and the reaction of the aforementioned phenolic hydroxyl resin (P2) with epoxy halopropane can be exemplified by a method in which the reaction is carried out in the presence of an alkaline catalyst, typically at a temperature of 20 to 150°C, preferably 30 to 80°C, for 0.5 to 10 hours.

[0085] Examples of the aforementioned epichlorohydrin halide include epichlorohydrin, epibromohydrin, and β-methylepoxychlorohydrin. The amount of epichlorohydrin added is typically 1.5 to 30 moles, preferably 2 to 15 moles, in excess of the total hydroxyl groups of the aforementioned biphenol compound (P1) or the aforementioned phenolic hydroxyl-containing resin (P2).

[0086] Examples of alkaline catalysts include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. Among these, alkali metal hydroxides are preferred for their superior catalytic activity; more specifically, sodium hydroxide and potassium hydroxide are preferred. Furthermore, these alkaline catalysts can be used in solid or aqueous solution form. The amount of the aforementioned alkaline catalyst added is preferably in the range of 0.9 to 2 moles per mole of the total number of hydroxyl groups present in the aforementioned biphenol compound (P1) or the aforementioned phenolic hydroxyl-containing resin (P2).

[0087] The reactions of the aforementioned biphenol compound (P1) and the aforementioned phenolic hydroxyl-containing resin (P2) with epoxy halides can be carried out in organic solvents. Examples of organic solvents 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; cellosolves such as methyl and ethyl cellosolves; ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane; and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, and dimethylformamide. These organic solvents can be used individually, or, to adjust polarity, two or more can be used in combination.

[0088] After the reaction with the aforementioned epoxy halide is complete, excess epoxy halide is removed by distillation, yielding a crude product. If necessary, the crude product can be redissolved in an organic solvent, and a basic catalyst can be added for further reaction, thereby reducing hydrolyzable halogens. Salts generated during the reaction can be removed by filtration, washing with water, etc. Alternatively, when using an organic solvent, distillation can be performed to remove only the solid resin component, or the product can be used directly as a solution.

[0089] In the aforementioned method for manufacturing epoxy resin (1), the mass ratio of the aforementioned glycidyl ether (E1) to the aforementioned glycidyl ether (E2) is not particularly limited. However, from the perspective of producing an epoxy resin with excellent flowability and high toughness and low hygroscopicity of the cured product, the proportion of the aforementioned glycidyl ether (E1) to the total mass of the two is preferably 0.5% by mass or more, preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 15% by mass or more. Furthermore, the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.

[0090] In the aforementioned method for manufacturing epoxy resin (2), the mass ratio of the aforementioned biphenol compound (P1) to the aforementioned phenolic hydroxyl-containing resin (P2) is preferably 0.5% by mass or more, preferably 1% by mass or more, more preferably 5% by mass or more, and particularly preferably 15% by mass or more, from the perspective of producing an epoxy resin with excellent flowability and high toughness and low moisture absorption of the cured product. Furthermore, the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less.

[0091] The reaction of the mixture of the aforementioned biphenol compound (P1) and the aforementioned phenolic hydroxyl-containing resin (P2) with epoxy halopropane can be carried out by the same method as the epoxy resin manufacturing method described in (1) above. The amount of epoxy halopropane added is typically 1.5 to 30 moles, preferably 2 to 15 moles, in excess of the total number of hydroxyl groups present in the aforementioned biphenol compound (P1) and the aforementioned phenolic hydroxyl-containing resin (P2). Furthermore, an alkaline catalyst can be used in the same manner as in the epoxy resin manufacturing method described in (1) above, and the amount of the alkaline catalyst added is preferably 0.9 to 2 moles, relative to the total number of hydroxyl groups present in the aforementioned biphenol compound (P1) and the aforementioned phenolic hydroxyl-containing resin (P2).

[0092] The epoxy equivalent of the epoxy resin of the present invention is preferably 140-400 g / equivalent, more preferably 140-350 g / equivalent. The epoxy equivalent here is determined based on JIS K 7236.

[0093] The melt viscosity of the epoxy resin of the present invention, as measured by an ICI viscometer at 150°C, is preferably 0.01–5 dPa·s, more preferably 0.01–2 dPa·s, and even more preferably 0.01–1 dPa·s. When the melt viscosity of the aforementioned epoxy resin is within the aforementioned range, it exhibits low viscosity and excellent flowability, and is therefore preferred from the perspective of excellent formability of the resulting cured product. The melt viscosity here is measured using an ICI viscometer according to ASTM D4287.

[0094] For the epoxy resin of the present invention, from the perspective of low viscosity and excellent flowability, the number average molecular weight (Mn) is preferably in the range of 200 to 1500, more preferably in the range of 200 to 800. Furthermore, the weight average molecular weight (Mw) is preferably in the range of 250 to 2000, more preferably in the range of 250 to 800. Additionally, the dispersity (Mw / Mn) is preferably in the range of 1 to 3. In the present invention, the molecular weight and dispersity of the epoxy resin are measured using gel permeation chromatography (GPC) under the measurement conditions described in the examples described later.

[0095] As a specific example of the epoxy resin of the present invention, the epoxy resin shown in the following structural formula can be cited.

[0096]

[0097] [In the above formula, n is an integer from 0 to 10.]

[0098] <Curing Compositions>

[0099] This invention relates to a curable composition comprising the aforementioned epoxy resin and a curing agent for epoxy resin. The curable composition, by containing the aforementioned epoxy resin, yields a cured product with excellent heat resistance and toughness, and is therefore preferred.

[0100] The curable composition of the present invention can use epoxy resin curing agents capable of crosslinking with the epoxy groups of the aforementioned epoxy resin without particular limitation. Examples of such curing agents include phenolic curing agents, amine curing agents, acid anhydride curing agents, reactive ester resins, and cyanate ester resins. The aforementioned curing agents can be used alone or in combination of two or more.

[0101] Examples of phenol curing agents include phenol-formaldehyde varnish resin, cresol-formaldehyde varnish resin, aromatic hydrocarbon formaldehyde resin modified phenol-formaldehyde resin, dicyclopentadiene-phenol addition-type resin, phenol aralkyl resin (Xylock resin), naphthol aralkyl resin, triphenolmethane resin, tetraphenol ethane resin, naphthol-formaldehyde varnish resin, naphthol-phenol cocondensed phenol-formaldehyde varnish resin, naphthol-cresol cocondensed phenol-formaldehyde varnish resin, biphenyl-modified phenol-formaldehyde resin (a compound containing polyphenolic hydroxyl groups formed by linking the phenol nucleus with dimethylene groups), biphenyl-modified naphthol resin (a polynatrol compound formed by linking the phenol nucleus with dimethylene groups), aminotriazine-modified phenol-formaldehyde resin (a compound containing polyphenolic hydroxyl groups formed by linking the phenol nucleus with melamine, benzoguanamine, etc.), and alkoxy-containing aromatic ring-modified phenol-formaldehyde varnish resin (a compound containing polyphenolic hydroxyl groups formed by linking the phenol nucleus and alkoxy-containing aromatic ring with formaldehyde). From a formability perspective, phenolic varnishes and similar compounds are preferred. It should be noted that the aforementioned compounds containing phenolic hydroxyl groups can be used alone or in combination of two or more.

[0102] Examples of aliphatic amines that can be used as amine curing agents include diethylenetriamine (DTA), triethylenetetramine (TTA), tetraethylenepentamine (TEPA), dipropylenediamine (DPDA), diethylaminopropylamine (DEAPA), N-aminoethylpiperazine, montananediamine (MDA), isophoronediamine (IPDA), 1,3-diaminomethylcyclohexane (1,3-BAC), piperidine, N,N-dimethylpiperazine, and triethylenediamine; and aromatic amines such as m-phenylenediamine (XDA), methanephenylene diamine (MPDA), diaminodiphenylmethane (DDM), diaminodiphenyl sulfone (DDS), benzylmethylamine, 2-(dimethylaminomethyl)phenol, and 2,4,6-tris(dimethylaminomethyl)phenol.

[0103] Examples of the aforementioned anhydride curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol dipreptyltrimethacrylate, glycerol trimellitic trimethacrylate, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylne-methylenetetrahydrophthalic anhydride, methylne-methylenetetrahydrophthalic anhydride, methylbutenyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, succinic anhydride, and methylcyclohexene dicarboxylic anhydride.

[0104] The amount of curing agent relative to the amount of epoxy resin is not particularly limited, for example, as a functional group equivalent ratio (e.g., hydroxyl equivalent of phenolic curing agent / epoxy equivalent of epoxy resin). From the perspective of good mechanical properties of the obtained cured product, the active groups in the curing agent are preferably 0.5 to 1.5 equivalents, more preferably 0.8 to 1.2 equivalents, relative to the total equivalent of epoxy groups of the aforementioned epoxy resin and other epoxy resins used in combination as needed.

[0105] It should be noted that, in addition to the aforementioned epoxy resin and curing agent, other resins may be used in combination in the aforementioned curing composition without impairing the effects of the present invention. Examples include epoxy resins other than the aforementioned epoxy resin, maleimide resins, bismaleimide resins, polymaleimide resins, polyphenylene ether resins, polyimide resins, benzoxazine resins, triazine-containing cresol phenolic varnish resins, styrene-maleic anhydride resins, diallyl bisphenol, triallyl isocyanurate and other allyl-containing resins, polyphosphate esters, phosphate ester-carbonate copolymers, etc. These other resins may be used alone or in combination of two or more.

[0106] Solvent

[0107] The curable composition of the present invention can be prepared in a solvent-free manner or may contain a solvent. The aforementioned solvent has functions such as adjusting the viscosity of the curable composition.

[0108] Specific examples of the aforementioned solvents are not particularly limited and can include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ether solvents such as diethyl ether and tetrahydrofuran; ester solvents such as ethyl acetate, butyl acetate, cellosol acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosol and butyl carbitol; aromatic hydrocarbons such as toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene, and 1,2,4-trimethylbenzene; and amide solvents such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. These solvents can be used alone or in combination of two or more.

[0109] The amount of solvent used, relative to the total mass of the curable composition, is preferably 10 to 90% by mass, more preferably 20 to 80% by mass. A solvent amount of 10% by mass or more is excellent from a processing perspective. On the other hand, a solvent amount of 90% by mass or less is preferred from an economic point of view.

[0110] <Additives>

[0111] The curing composition of the present invention can be mixed with various additives such as curing accelerators, flame retardants, inorganic fillers, silane coupling agents, release agents, pigments, colorants, and emulsifiers as needed.

[0112] <Curing Accelerator>

[0113] There are no particular limitations on the aforementioned curing accelerators, and examples include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and urea-based curing accelerators. It should be noted that the aforementioned curing accelerators can be used alone or in combination of two or more.

[0114] Examples of phosphorus-based curing accelerators include organophosphorus compounds such as triphenylphosphine, tributylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine; organophosphite compounds such as trimethylphosphite and triethylphosphite; and phosphite salts such as ethyltriphenylphosphine bromide, benzyltriphenylphosphine chloride, butylphosphine tetraphenylboronic acid ester, tetraphenylphosphine tetraphenylboronic acid ester, tetraphenylphosphine tetra-p-tolylboronic acid ester, triphenylphosphine triphenylborane, tetraphenylphosphine thiocyanate, tetraphenylphosphine dicyandiamide, butylphenylphosphine dicyandiamide, and tetrabutylphosphine decanoate.

[0115] Examples of amine-based curing accelerators include triethylamine, tributylamine, N,N-dimethyl-4-aminopyridine (4-dimethylaminopyridine, DMAP), 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]-undecene-7 (DBU), and 1,5-diazabicyclo[4.3.0]-nonene-5 (DBN).

[0116] Examples of imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-pentadedecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, etc. 2-phenylimidazolium, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2-phenylimidazolium isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazolium, 2-phenyl-4-methyl-5-hydroxymethylimidazolium, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, etc.

[0117] Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]decane-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]decane-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-butylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, and 1-phenylbiguanidine.

[0118] Examples of urea-based curing accelerators include 3-phenyl-1,1-dimethyl urea, 3-(4-methylphenyl)-1,1-dimethyl urea, chlorophenyl urea, 3-(4-chlorophenyl)-1,1-dimethyl urea, and 3-(3,4-dichlorophenyl)-1,1-dimethyl urea.

[0119] Among the aforementioned curing accelerators, especially when used as semiconductor sealing materials, triphenylphosphine is preferred among phosphorus compounds due to its superior curing properties, heat resistance, electrical properties, and moisture resistance reliability, and 1,8-diazabicyclo-[5.4.0]-undecene (DBU) is preferred among tertiary amines.

[0120] The amount of the aforementioned curing accelerator can be appropriately adjusted to obtain the desired curing properties. It is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the mixture of epoxy resin and curing agent. When the amount of the aforementioned curing accelerator is within the aforementioned range, excellent curing properties and insulation reliability are achieved, which is preferred.

[0121] Flame retardants

[0122] There are no particular limitations on the aforementioned flame retardants; examples include inorganic phosphorus-based flame retardants, organophosphorus-based flame retardants, and halogen-based flame retardants. It should be noted that flame retardants can be used alone or in combination of two or more.

[0123] As for the aforementioned inorganic phosphorus-based flame retardants, there are no particular limitations, and examples include red phosphorus; monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium polyphosphate, etc.; and phosphoramide, etc.

[0124] As for the aforementioned organophosphorus flame retardants, there are no particular limitations, and examples include methyl phosphate, ethyl phosphate, isopropyl phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl phosphate, 2-ethylhexyl phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl phosphate, lauryl phosphate, tridecyl phosphate, stearyl phosphate, isostearyl phosphate, oleyl phosphate, butyl pyrophosphate, tetracosyl phosphate, glycolic acid phosphate, (2-hydroxyethyl) methacrylate phosphate, etc.; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine oxide, etc.; 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine oxide, etc. Phosphorus-containing phenols such as phenanthrene-10-oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine hydroquinone, diphenylphosphino-1,4-dioxynaphthalene, 1,4-cyclo(octylphosphine)-1,4-phenyldiol, and 1,5-cyclo(octylphosphine)-1,4-phenyldiol; cyclic phosphorus compounds such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; and compounds obtained by reacting the aforementioned phosphate esters, the aforementioned diphenylphosphine, and the aforementioned phosphorus-containing phenols with epoxy resins, aldehyde compounds, and phenolic compounds.

[0125] There are no particular limitations on the aforementioned halogen-based flame retardants, and examples include brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2-bis(tetrabromophthalimide), 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, and tetrabromophthalic acid.

[0126] The amount of the aforementioned flame retardant is preferably 0.1 to 20 parts by weight relative to 100 parts by weight of the aforementioned epoxy resin.

[0127] <Inorganic fillers>

[0128] There are no particular limitations on the aforementioned inorganic fillers, and examples include silica, alumina, glass, cordierite, organosilicon oxides, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, and carbon black. Among these, silica is preferred. Amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica are used as silica. From the perspective of allowing for the mixing of more inorganic fillers, fused silica is preferred. The aforementioned molten silica can be used in any form, including broken or spherical shapes. To increase the amount of molten silica incorporated and to suppress the increase in the melt viscosity of the curable composition, it is preferable to primarily use spherical silica. Furthermore, to increase the amount of spherical silica incorporated, it is preferable to appropriately adjust the particle size distribution of the spherical silica. It should be noted that the aforementioned inorganic filler can be used alone or in combination of two or more types.

[0129] Furthermore, the aforementioned inorganic filler can be surface-treated as needed. In this case, there are no particular limitations on the surface treatment agents that can be used, such as aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, etc. Specific examples of surface treatment agents include 3-epoxypropoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldisilazane, etc.

[0130] The amount of the aforementioned inorganic filler relative to 100 parts by weight of the mixture of the aforementioned epoxy resin and the aforementioned curing agent is preferably 0.5 to 95 parts by weight. When the amount of the aforementioned inorganic filler is within the aforementioned range, the flame retardancy and insulation reliability are excellent, which is preferred.

[0131] Furthermore, organic fillers may be formulated in addition to the aforementioned inorganic fillers, provided that the characteristics of the present invention are not impaired. Examples of such organic fillers include polyamide particles.

[0132] <Cured product>

[0133] This invention relates to cured products of the aforementioned curable compositions. The use of the aforementioned epoxy resin results in cured products from the aforementioned curable compositions containing the aforementioned epoxy resin exhibiting high heat resistance and high toughness, which is a preferred approach.

[0134] As a method for curing the aforementioned curable composition to obtain a cured product, for example, the heating temperature during heat curing is not particularly limited, and is usually 100 to 300°C, and the heating time is 1 to 24 hours.

[0135] The glass transition temperature (Tg) of the cured product of the present invention is preferably 160°C or higher. The method for determining the glass transition temperature (Tg) is the same as the evaluation method in the embodiments of this application.

[0136] Furthermore, the Charpy impact strength of the cured product of the present invention is preferably 6.5 J / cm. 2 The above, and more preferably 7.3 J / cm 2 The above, and especially preferred, value is 7.8 J / cm. 2 The method for determining Charpy impact strength is the same as the evaluation method used in the embodiments of this application.

[0137] Semiconductor sealing materials

[0138] This invention relates to semiconductor sealing materials containing the aforementioned curable composition. Semiconductor sealing materials obtained using the aforementioned curable composition, due to the use of the aforementioned epoxy resin, have low viscosity and excellent flowability, thereby improving the heat resistance and toughness of the cured product. Therefore, they exhibit excellent processability and formability during the manufacturing process, making them a preferred option.

[0139] The aforementioned curable composition used in the aforementioned semiconductor sealing material may contain an inorganic filler. It should be noted that, as the filling rate of the aforementioned inorganic filler, relative to 100 parts by weight of the aforementioned curable composition, the inorganic filler may be used in the range of 0.5 to 95 parts by weight, for example.

[0140] As a method for obtaining the aforementioned semiconductor sealing material, the following methods can be cited: the aforementioned curable composition and, further, an additive as an arbitrary component, are thoroughly mixed to uniformity using an extruder, kneader, roller, etc., as needed.

[0141] Semiconductor Devices

[0142] This invention relates to a semiconductor device comprising a cured product of the aforementioned semiconductor sealing material. The semiconductor device obtained using the semiconductor sealing material obtained through the aforementioned curable composition has low viscosity and excellent flowability due to the use of the aforementioned epoxy resin, thereby improving the heat resistance and toughness of the cured product. Therefore, it exhibits excellent processability and formability during the manufacturing process, making it a preferred method.

[0143] As a method for obtaining the aforementioned semiconductor device, the following method can be cited: the aforementioned semiconductor sealing material is formed using a casting molding machine, a transfer molding machine, an injection molding machine, etc., and then heated and cured in a temperature range of room temperature (20°C) to 250°C.

[0144] <Prepreg>

[0145] This invention relates to a prepreg having a reinforcing substrate and a semi-cured product of the aforementioned curable composition impregnated in the reinforcing substrate. As a method for obtaining the prepreg from the aforementioned curable composition, an example is obtained by: mixing an organic solvent (described later), impregnating the varnished curable composition into a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass pad, glass coarse sandpaper, etc.), and then heating at a temperature appropriate to the type of solvent used, preferably 50–170°C. The mass ratio of the curable composition to the reinforcing substrate used in this process is not particularly limited, but it is generally preferred that the resin content in the prepreg is 20–60% by mass.

[0146] Examples of organic solvents used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diethylene glycol acetate, and propylene glycol monomethyl ether acetate. The selection and appropriate amount of these solvents can be chosen according to the application. For example, in the case of further manufacturing printed circuit boards from prepreg as described below, polar solvents with a boiling point of 160°C or below, such as methyl ethyl ketone, acetone, and dimethylformamide, are preferred. In addition, it is preferable to use them at a ratio of 40 to 80% by mass of non-volatile components.

[0147] <Circuit substrate>

[0148] This invention relates to a circuit board, which is a laminate of the aforementioned prepreg and copper foil. As a method for obtaining a printed circuit board from the aforementioned curable composition, the following method can be cited: the aforementioned prepreg is laminated using conventional methods, copper foil is appropriately overlapped, and heat-pressed at 170-300°C for 10 minutes to 3 hours under a pressure of 1-10 MPa.

[0149] <Laminated Thin Films>

[0150] This invention relates to a multilayer film containing the aforementioned curable composition. As a method for manufacturing the multilayer film of this invention, one example is a method of coating the aforementioned curable composition onto a support film to form a curable composition layer, thereby producing an adhesive film for a multilayer printed circuit board.

[0151] When manufacturing a laminated film from a curable composition, it is important that the film softens under the lamination temperature conditions (typically 70–140°C) of the vacuum lamination method, and exhibits the fluidity (resin flow) of the resin to fill the vias or holes present in the circuit board while being laminated with the circuit board. To exhibit such characteristics, it is preferable to blend the above-mentioned components.

[0152] Here, the diameter of the through-holes in the multilayer printed circuit board is typically 0.1–0.5 mm, and the depth is typically 0.1–1.2 mm. It is generally preferred that resin be filled within this range. It should be noted that when laminating both sides of the circuit board, ideally, approximately half of the through-hole should be filled.

[0153] Specifically, the method for manufacturing the above-mentioned adhesive film can be as follows: after preparing the above-mentioned curable composition in the form of a varnish, the varnish-like composition is coated on the surface of a support film (Y), and the organic solvent is dried by heating or blowing hot air to form a composition layer (X) formed by the curable composition.

[0154] The thickness of the formed composition layer (X) is preferably set to be greater than or equal to the thickness of the conductor layer. The thickness of the conductor layer in the circuit board is typically in the range of 5 to 70 μm, therefore, the thickness of the resin composition layer is preferably 10 to 100 μm.

[0155] It should be noted that the composition layer (X) in this invention can be protected by the protective film described later. By using the protective film, the adhesion and damage of debris or the like to the surface of the resin composition layer can be prevented.

[0156] Examples of the aforementioned support and protective films include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate; polycarbonate; polyimide; and further, release paper, copper foil, aluminum foil, and other metal foils. It should be noted that the support and protective films can undergo matte finishing, corona treatment, and release treatment.

[0157] The thickness of the support film is not particularly limited, and is typically 10–150 μm, preferably in the range of 25–50 μm. Furthermore, the thickness of the protective film is preferably set to 1–40 μm.

[0158] The aforementioned support film (Y) is laminated onto the circuit board or, after being cured by heat to form an insulating layer, is then peeled off. Peeling off the support film (Y) after the adhesive film has been cured by heat prevents the adhesion of debris or other contaminants from the curing process. When peeling after curing, the support film is typically pre-molded.

[0159] <Other uses>

[0160] The cured products obtained by the curable composition of the present invention have excellent heat resistance, toughness and other properties, so they are suitable for use not only in semiconductor sealing materials, semiconductor devices, prepregs, circuit boards and multilayer films, but also in various applications such as multilayer boards, adhesives, corrosion-resistant materials, and matrix resins for fiber-reinforced resins. The applications are not limited to these.

[0161] Example

[0162] The present invention will now be described in more detail using examples, but the invention is not limited to these scopes. It should be noted that the determination / evaluation of physical properties / characteristics were carried out as follows, and the evaluation results are shown in Tables 1 and 2 below.

[0163] <Softening Point>

[0164] The softening point (°C) was determined according to JIS K 7234 (ring and ball method).

[0165] <Determination of Epoxy Equivalent>

[0166] The determination was based on JIS K 7236.

[0167] <Method for determining melt viscosity at 150℃>

[0168] The measurements were performed using an ICI viscometer in accordance with ASTM D4287.

[0169] <Determination by Gel Permeation Chromatography (GPC)>

[0170] GPC was performed under the conditions shown below, and the resulting GPC graph was further evaluated to calculate the number-average molecular weight (Mn), weight-average molecular weight (Mw), and dispersity (Mw / Mn) of the epoxy resin.

[0171] Measuring apparatus: HLC-8320GPC manufactured by Tosoh Corporation;

[0172] Column: Protective column "HXL-L" manufactured by Tosoh Corporation

[0173] + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

[0174] + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

[0175] + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation

[0176] + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

[0177] Detector: RI (Differential Refractometer)

[0178] Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation"

[0179] Measurement conditions: column temperature 40℃

[0180] Expand solvent tetrahydrofuran

[0181] Flow rate 1.0 ml / min

[0182] Standard: Based on the aforementioned "GPC Workstation EcoSEC-WorkStation" test manual, use the following monodisperse polystyrene with known molecular weight.

[0183] (Using polystyrene)

[0184] "A-500" manufactured by Tosoh Corporation

[0185] "A-1000" manufactured by Tosoh Corporation

[0186] "A-2500" manufactured by Tosoh Corporation

[0187] "A-5000" manufactured by Tosoh Corporation

[0188] "F-1" manufactured by Tosoh Corporation

[0189] "F-2" manufactured by Tosoh Corporation

[0190] "F-4" manufactured by Tosoh Corporation

[0191] "F-10" manufactured by Tosoh Corporation

[0192] "F-20" manufactured by Tosoh Corporation

[0193] "F-40" manufactured by Tosoh Corporation

[0194] "F-80" manufactured by Tosoh Corporation

[0195] "F-128" manufactured by Tosoh Corporation

[0196] Sample: 50 μl of substance obtained by filtering a tetrahydrofuran solution, which is calculated as 1.0% by mass of resin solids, through a microfilter.

[0197] (Synthesis Example 1: Synthesis of phenolic hydroxyl resin (P2-1))

[0198] In a flask equipped with a thermometer, condenser, distillation tube, nitrogen inlet tube, and stirrer, 160 g (1.0 mol) of 2,7-dihydroxynaphthalene and 27.0 g (0.25 mol) of benzyl alcohol were added. The mixture was stirred while being purged with nitrogen at room temperature. Next, 2.7 g of p-toluenesulfonic acid monohydrate was added. The mixture was then heated to 150°C in an oil bath while maintaining heat. The generated water was removed using a distillation tube, and the reaction proceeded for 5 hours. After the reaction was complete, 1000 g of methyl isobutyl ketone was added to dissolve the reaction product, which was then transferred to a separatory funnel. The product was washed with water until the washing water was neutral. The solvent was then removed from the organic layer under reduced pressure to obtain 240 g of the target phenolic hydroxyl resin (P2-1). The obtained phenolic hydroxyl resin (P2-1) had a softening point of 97°C and a hydroxyl equivalent of 146 g / equivalent. In addition, the content of compound (A) containing phenolic hydroxyl resin (P2-1) and having three naphthalene ring structures in one molecule is 33%. The GPC diagram of phenolic hydroxyl resin (P2-1) is shown below. Figure 1 It should be noted that the content of the aforementioned compound (A) was calculated based on the area ratio of the GPC plot.

[0199] It should be noted that the compound (A) contained in the phenolic hydroxyl resin (P2-1) obtained above is the compound shown in the following structural formula.

[0200]

[0201] (Example 1: Synthesis of epoxy resin (1))

[0202] In a flask equipped with a thermometer, dropping funnel, condenser, and stirrer, 180.0 g of the phenolic hydroxyl resin (P2-1) obtained in Synthesis Example 1, 60.0 g of 4,4'-biphenol, 1157 g of epichlorohydrin, 347 g of n-butanol, and 58 g of water were added and dissolved while purging with nitrogen. The mixture was heated to 60°C, and 480 g of a 20% (w / w) sodium hydroxide aqueous solution was added dropwise over 5 hours. Stirring continued for 0.5 hours under the same conditions. Unreacted epichlorohydrin was then removed by vacuum distillation to obtain a crude product. 600 g of methyl isobutyl ketone was added to the crude product and dissolved. 33 g of a 5% (w / w) sodium hydroxide aqueous solution was added to this solution, and the reaction was carried out at 80°C for 2 hours. 180 g of water was added to the reaction mixture for washing. This washing was repeated three times until the pH of the washing solution was neutral. Next, the system was dehydrated by azeotropic distillation. After precision filtration, the solvent was removed by distillation under reduced pressure to obtain epoxy resin (1). The obtained epoxy resin (1) had an epoxy equivalent of 197 g / equivalent, a melt viscosity of 0.2 dPa·s at 150°C, a number-average molecular weight (Mn) of 314, a weight-average molecular weight (Mw) of 372, and a dispersion (Mw / Mn) of 1.2. The GPC diagram of epoxy resin (1) is shown in the figure. Figure 2 .

[0203] The epoxy resin (1) obtained above contains epoxy resin with the following structural formula.

[0204]

[0205] [In the above formula, n is an integer from 0 to 10.]

[0206] (Example 2: Synthesis of epoxy resin (2))

[0207] In Example 1, the phenolic hydroxyl resin (P2-1) was changed to 192.0 g and 4,4'-biphenyl to 48.0 g. Otherwise, the reaction was carried out in the same manner as in Example 1 to obtain epoxy resin (2). The obtained epoxy resin (2) had an epoxy equivalent of 203 g / equivalent, a melt viscosity of 0.3 dPa·s at 150°C, a number-average molecular weight (Mn) of 319, a weight-average molecular weight (Mw) of 381, and a dispersity (Mw / Mn) of 1.2. The GPC diagram is shown below. Figure 3 .

[0208] The epoxy resin (2) obtained above contains epoxy resin with the following structural formula.

[0209]

[0210] [In the above formula, n is an integer from 0 to 10.]

[0211] (Example 3: Synthesis of epoxy resin (3))

[0212] In Example 1, the phenolic hydroxyl resin (P2-1) 232.8g and 4,4'-biphenyl 7.2g were used instead. Otherwise, the reaction was carried out in the same manner as in Example 1 to obtain epoxy resin (3). The obtained epoxy resin (3) had an epoxy equivalent of 213g / equivalent, a melt viscosity of 0.4dPa·s at 150°C, a number-average molecular weight (Mn) of 336, a weight-average molecular weight (Mw) of 412, and a dispersion (Mw / Mn) of 1.2. The GPC diagram is shown below. Figure 4 .

[0213] The epoxy resin (3) obtained above contains epoxy resin with the following structural formula.

[0214]

[0215] [In the above formula, n is an integer from 0 to 10.]

[0216] (Comparative Synthesis Example 1: Synthesis of Phenolic Hydroxyl Resin (1'))

[0217] In a flask equipped with a thermometer, condenser, distillation tube, nitrogen inlet tube, and stirrer, 432.4 g (4.0 mol) of o-cresol, 158.2 g (1.0 mol) of 2-methoxynaphthalene, and 179.3 g (2.45 mol) of 41% formaldehyde aqueous solution were added, along with 9.0 g of oxalic acid. The mixture was heated to 100°C and reacted at 100°C for 3 hours. Next, water was collected using a distillation tube, and 73.2 g (1.0 mol) of 41% formaldehyde aqueous solution was added dropwise over 1 hour. After the addition was complete, the temperature was raised to 150°C over 1 hour, and the reaction was carried out at the same temperature for 2 hours. After the reaction was complete, 1500 g of methyl isobutyl ketone was added and transferred to a separatory funnel. The mixture was washed with water until the washing water was neutral. Unreacted o-cresol, 2-methoxynaphthalene, and methyl isobutyl ketone were removed from the organic layer under heating and reduced pressure to obtain a phenolic hydroxyl resin (1'). The obtained phenolic hydroxyl resin (1') has a softening point of 76℃ and a hydroxyl equivalent of 164 g / equivalent.

[0218] (Comparative Example 1: Synthesis of epoxy resin (1'))

[0219] In a flask equipped with a thermometer, dropping funnel, condenser, and stirrer, 137.1 g (0.84 hydroxyl equivalents) of the phenolic hydroxyl resin (1') obtained in Comparative Synthesis Example 1, 15.3 g (0.16 hydroxyl equivalents) of 4,4'-biphenol, 463 g (5.0 mol) of epichlorohydrin, 139 g of n-butanol, and 2 g of tetraethylbenzylammonium chloride were added and dissolved while purging with nitrogen. The temperature was raised to 70°C, and 220 g (1.1 mol) of a 20% (w / w) sodium hydroxide aqueous solution was added dropwise over 5 hours. Stirring continued for 0.5 hours under the same conditions. Unreacted epichlorohydrin was removed by vacuum distillation to obtain a crude product. 1000 g of methyl isobutyl ketone and 350 g of n-butanol were added to the crude product and dissolved. 10 g of 10% sodium hydroxide aqueous solution was added to the solution, and the reaction was carried out at 80 °C for 2 hours. The solution was then washed three times with 150 g of water until the pH of the washing solution was neutral. The system was dehydrated by azeotropic distillation. After precision filtration, the solvent was removed by distillation 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 of 0.3 dPa·s at 150 °C, a number-average molecular weight (Mn) of 426, a weight-average molecular weight (Mw) of 666, and a dispersion (Mw / Mn) of 1.6.

[0220] [Table 1]

[0221]

[0222] (Examples 4-6 and Comparative Example 2: Preparation of epoxy resin compositions)

[0223] The components were blended according to the compositions shown in Table 2 and then melt-blended to obtain the various epoxy resin compositions. Details of each component in Table 2 are as follows.

[0224] Curing agent: Phenolic resin for varnish type (DIC Corporation "TD-2131", hydroxyl equivalent 104g / equivalent)

[0225] Curing accelerator: Triphenylphosphine (manufactured by Hokko Chemical Industry Co., Ltd., "TPP")

[0226] <Heat Resistance Evaluation>

[0227] The above epoxy resin compositions were cured at 150°C for 10 minutes under normal pressure with a cured thickness of 2.4 mm, and then post-cured at 175°C for 5 hours to obtain the cured product for evaluation.

[0228] The cured material was cut into 5mm × 54mm pieces using a diamond cutter and used as test pieces for heat resistance evaluation. For the heat resistance evaluation, a viscoelasticity measuring apparatus (Rheometrics, Inc. "Solid Viscoelasticity Measuring Apparatus RSAII", rectangular tension method: frequency 1Hz, heating rate 3℃ / min) was used. The temperature at which the elastic modulus changed the most (and the rate of change of tanδ was also the greatest) was taken as the glass transition temperature (Tg) (℃) to evaluate the heat resistance.

[0229] <Resilience Assessment>

[0230] Using various epoxy resin compositions, transfer molding was performed according to JIS K 6911 at 175°C for 120 seconds and a molding pressure of 6.9 MPa. This was followed by post-curing at 175°C for 5 hours to prepare Charpy impact strength test specimens. The Charpy impact strength (J / cm²) of the obtained test specimens was measured using a Pendulum Impact Tester Zwick 5102. 2 And evaluate resilience.

[0231] [Table 2]

[0232] 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 <![CDATA[Charpy impact strength (J / cm 2 )]]> 8.0 7.5 6.7 4.0

[0233] Based on the evaluation results in Tables 1 and 2 above, it can be confirmed that the epoxy resins obtained in all examples have low viscosity and excellent flowability, which contributes to good formability. The cured products obtained by using epoxy resin compositions (curing compositions) containing the aforementioned epoxy resins have high glass transition temperatures and high heat resistance. They also show high values ​​in Charpy impact tests, indicating high toughness. It can be confirmed that a balance between high heat resistance and high toughness can be achieved.

[0234] On the other hand, based on the evaluation results in Tables 1 and 2 above, in Comparative Example 1, epoxy resin (1') was synthesized without using the desired phenolic hydroxyl resin. Compared with the Examples, Comparative Example 2, which used epoxy resin (1') to synthesize epoxy resin (curable composition), showed poor heat resistance and toughness.

Claims

1. An epoxy resin comprising: a glycidyl ether of a biphenol compound (P1) (E1) and a glycidyl ether of a phenolic hydroxyl resin (P2) (E2), wherein the phenolic hydroxyl resin (P2) is reacted with a dihydroxy aromatic compound (α) and an aralkylating agent (β) represented by the following general formula (1-1) or (1-2), wherein the total mass of the dihydroxy aromatic compound (α) and the aralkylating agent (β) in the total mass of the reactant material of the phenolic hydroxyl resin (P2) accounts for more than 80% by mass, and the molar ratio of the dihydroxy aromatic compound (α) to the aralkylating agent (β) [(α) / (β)] is in the range of 1 / 0.1 to 1 / 10. In the general formulas (1-1) and (1-2), X represents any one of the halogen atom, hydroxyl group, and alkoxy group, and R... 1 Each independently represents either a hydrogen atom or any alkyl group having 1 to 4 carbon atoms, R 2 Each independently represents a hydrogen atom or a methyl group, Ar 1 It represents any of the following structural sites: phenyl, naphthyl, having one or more halogen atoms on their aromatic nuclei, aliphatic hydrocarbon groups, and alkoxy groups; The glycidyl ether (E1) is present in a proportion of 0.5% by mass or more and 40% by mass or less relative to the total mass of the glycidyl ether (E1) and the glycidyl ether (E2).

2. An epoxy resin comprising: a glycidyl ether (E3) of a mixture of a biphenol compound (P1) and a phenolic hydroxyl resin (P2), wherein the phenolic hydroxyl resin (P2) is reacted with a dihydroxy aromatic compound (α) and an aralkylating agent (β) represented by the following general formula (1-1) or (1-2), wherein the total mass of the dihydroxy aromatic compound (α) and the aralkylating agent (β) in the total mass of the reactant material containing the phenolic hydroxyl resin (P2) accounts for more than 80% by mass, and the molar ratio of the dihydroxy aromatic compound (α) to the aralkylating agent (β) [(α) / (β)] is in the range of 1 / 0.1 to 1 / 10. In the general formulas (1-1) and (1-2), X represents any one of the halogen atom, hydroxyl group, and alkoxy group, and R... 1 Each independently represents either a hydrogen atom or any alkyl group having 1 to 4 carbon atoms, R 2 Each independently represents a hydrogen atom or a methyl group, Ar 1 It represents any of the following structural sites: phenyl, naphthyl, having one or more halogen atoms on their aromatic nuclei, aliphatic hydrocarbon groups, and alkoxy groups; The proportion of the biphenol compound (P1) to the total mass of the biphenol compound (P1) and the phenolic hydroxyl resin (P2) is 0.5% by mass or more and 40% by mass or less.

3. The epoxy resin according to claim 1 or 2, wherein, The phenolic hydroxyl resin (P2) contains a compound (A) having a structure of 3 naphthalene rings in one molecule.

4. The epoxy resin according to claim 3, wherein, The content of compound (A) in the phenolic hydroxyl resin (P2) is 5-50% as calculated based on the area ratio of the gel permeation chromatography (GPC) chromatogram.

5. The epoxy resin according to any one of claims 1, 2, and 4, wherein the melt viscosity at 150°C, as measured by an ICI viscometer, is 0.01~5 dPa·s.

6. A curable composition comprising the epoxy resin and the curing agent for epoxy resin as described in any one of claims 1 to 5.

7. A cured product, which is a cured product of the curable composition of claim 6.

8. A semiconductor sealing material comprising the curable composition of claim 6.

9. A semiconductor device comprising a cured form of the semiconductor sealing material of claim 8.

10. A prepreg comprising: a reinforcing substrate and a semi-cured product of the curable composition of claim 6 impregnated in the reinforcing substrate.

11. A circuit board, which is a laminate of the prepreg and copper foil as described in claim 10.

12. A laminated film comprising the curable composition of claim 6.

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