Active ester resin, resin composition, cured product, semiconductor sealing material, semiconductor device, prepreg, circuit board, flexible wiring board, build-up film, multilayer printed wiring board, build-up substrate, fiber-reinforced composite material, molded product, and phenolic hydroxyl group-containing resin

Abstract

To provide an active ester resin having low dielectric constant and dielectric loss tangent in a cured product, an epoxy resin composition containing the active ester resin, and a cured product, a printed wiring board, a build-up film, and a semiconductor sealing material obtained by curing the epoxy resin composition.SOLUTION: There are provided: an active ester resin obtained by reacting a phenolic hydroxyl group-containing resin (A) with an aromatic poly-carboxylic acid or its acid halide (B), wherein the phenolic hydroxyl group-containing resin (A) contains a phenolic hydroxyl group-containing compound (a1) and an indene structure-containing compound (a2) as essential reaction raw materials; an epoxy resin composition containing the active ester resin; and a cured product obtained by curing the epoxy resin composition.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to an active ester resin, an epoxy resin composition containing the active ester resin, a cured product obtained by curing the epoxy resin composition, and the like.

Background Art

[0002] In recent years, with the sophistication of services using networks and the high performance and high functionality of information terminal devices, sensors, etc., the amount of information handled has been increasing in volume and the data processing speed has been increasing. Since the amount of information that can be transmitted increases as the frequency of radio waves increases, the use of high frequency bands of several tens of GHz or more is being considered, and components such as circuit boards and antennas used in corresponding devices require materials with low dielectric loss corresponding to high frequency bands.

[0003] An epoxy resin composition containing an epoxy resin and a curing agent is widely used in electronic component applications such as semiconductors and circuit boards because it exhibits high heat resistance and insulation when the resin composition is cured. As a curing agent, an active ester resin having an ester structure in the molecule has been reported (Patent Document 1). An epoxy resin composition using an active ester resin can obtain a cured product with a low dielectric constant and a low dielectric tangent as compared with the case of using a conventional curing agent such as a phenol novolak resin. However, the cured product using a known active ester resin has insufficient dielectric properties in the high frequency band, and the development of a curing agent for epoxy resin that can provide a cured product showing a lower dielectric tangent in the high frequency band has been demanded.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The problem to be solved by the present invention is to provide an active ester resin having a low dielectric constant and a low dielectric loss tangent in a cured product, an epoxy resin composition containing the active ester resin, a cured product obtained by curing the epoxy resin composition, a printed wiring board, a build-up film, and a semiconductor encapsulating material.

Means for Solving the Problems

[0006] As a result of intensive studies to solve the above problems, the present inventors have developed an active ester resin having a specific structure. That is, the present invention provides an active ester resin obtained by reacting a phenolic hydroxyl group-containing resin (A) with an aromatic (poly) carboxylic acid or its acid halide (B), wherein the phenolic hydroxyl group-containing resin (A) uses a phenolic hydroxyl group-containing compound (a1) and an indene structure-containing compound (a2) as essential reaction raw materials, and provides an epoxy resin composition containing the active ester resin and a cured product obtained by curing the epoxy resin composition.

Effects of the Invention

[0007] Since the active ester resin of the present invention has a low dielectric constant and a low dielectric loss tangent when formed into a cured product, it is useful as a resin composition material such as a printed wiring board, a build-up film, and a semiconductor encapsulating material.

Modes for Carrying Out the Invention

[0008] The present invention provides an active ester resin obtained by reacting a phenolic hydroxyl group-containing resin (A) with an aromatic (poly) carboxylic acid or its acid halide (B), wherein the phenolic hydroxyl group-containing resin (A) uses a phenolic hydroxyl group-containing compound (a1) and an indene structure-containing compound (a2) as essential reaction raw materials.

[0009] In the active ester resin, from the viewpoints of compatibility with other components and solubility in a solvent when added to a resin composition, the phenolic hydroxyl group-containing resin (A) has the following general formula (S).

[0010]

Chemical formula

[0011] (In the formula, A 1 represents an optionally substituted hydrocarbon ring or heterocyclic ring having 3 to 16 carbon atoms, and L has the following formula (L).

[0012]

Chemical formula

[0013] (In the formula, * represents the bonding position with the ring represented by A 1 , R 1 and R 2 each independently represent a group selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, an aryl group having 3 to 20 carbon atoms, and an aralkyl group having 4 to 20 carbon atoms. However, when there are a plurality of R 1 and R 2 , they may be the same or different. R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 each independently represent a group selected from a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, an aryl group having 3 to 20 carbon atoms, and an aralkyl group having 4 to 20 carbon atoms. However, when there are a plurality of R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 , they may be the same or different. r1 represents an integer from 0 to 4, r2 represents an integer from 0 to 5, n1 represents an integer from 1 to 20, n2 represents an integer from 0 to 20, but the order of each repeating unit enclosed by n1 and n2 is not limited, and the bonding pattern may be alternating, block, or random. Each repeating unit enclosed by n1 and n2 may have the same structure or a plurality of different structures. ) represents a group, m is 1 or more, and A 1 represents an integer less than or equal to the number of ring-constituting atoms that can be substituted in the ring represented by ). ) is preferably represented.

[0014] From the viewpoints of ease of synthesis and availability of raw materials, the phenolic hydroxyl group-containing resin (A) has the following general formula (S1)

[0015]

Chemical formula

[0016] (In the formula, A 11 represents an optionally substituted benzene ring or naphthalene ring, and L 1 has the following formula (L1)

[0017]

Chemical formula

[0018] (In the formula, * represents the bonding position with the ring represented by A 11 , R 11 and R 21 each independently represent a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkenyl group having 1 to 5 carbon atoms, a linear or branched alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an aryl group having 4 to 10 carbon atoms, and an aralkyl group having 5 to 11 carbon atoms. However, when there are a plurality of R 11 and R 21 they may be the same or different, R 31 、R 41 、R 51 、R 61 、R 71 、R 81 and R 91 each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkenyl group having 1 to 5 carbon atoms, a linear or branched alkoxy group having 1 to 5 carbon atoms, a fluorine atom, a chlorine atom, a bromine atom, an aryl group having 4 to 10 carbon atoms, and an aralkyl group having 5 to 11 carbon atoms, provided that when there are a plurality of R 31 、R 41 、R 51 、R 61 、R 71 、R 81 and R 91 they may be the same or different when there are a plurality of them, r11 represents 0, 1 or 2, r21 represents 0, 1, 2 or 3, n11 represents an integer from 1 to 20, n21 represents an integer from 0 to 20, provided that the order of each repeating unit enclosed by n11 and n21 is not limited, the bonding mode is random, and each repeating unit enclosed by n11 and n21 may have the same structure or a plurality of different structures. represents a group represented by), and m1 is 1 or more and represents an integer not exceeding the number of ring-constituting atoms that can be substituted in the ring represented by A 11 It is more preferably represented by), and the phenolic hydroxyl group-containing resin (A) has the following general formula (S11)

[0019]

Chemical formula

[0020] (In the formula, A 111 represents a benzene ring or a naphthalene ring which may be substituted by a linear or branched alkyl group having 1 to 5 carbon atoms, and L 11 is the following formula (L11)

[0021] [Chemical formula]

[0022] (In the formula, * represents the bonding position with the ring represented by A 111 and R 111 and R 211 each independently represent a group selected from a linear or branched alkyl group having 1 to 5 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 11 carbon atoms, provided that when there are a plurality of R 111 and R 211 they may be the same or different, R 311 , R 411 , R 511 , R 611 , R 711 , R 811 and R 911 each independently represent a group selected from a hydrogen atom and a linear or branched alkyl group having 1 to 5 carbon atoms, provided that when there are a plurality of R 311 , R 411 , R 511 , R 611 , R 711 , R 811 and R 911 they may be the same or different, r111 and r211 each independently represent 0, 1, or 2, n111 represents an integer from 1 to 12, n211 represents an integer from 0 to 12, provided that the order of each repeating unit enclosed by n111 and n211 is not limited, the bonding mode is random, and each repeating unit enclosed by n111 and n211 may have the same structure or a plurality of different structures. ) represents a group represented by, and m11 is 1 or more and represents an integer not exceeding the number of ring-constituting atoms that can be substituted in the ring represented by A 111 . It is more preferably represented by), and the phenolic hydroxyl group-containing resin (A) is represented by the following formula (S111-1) to formula (S111-3)

[0023] [Chemical formula]

[0024] (In the formula, R A represents a linear or branched alkyl group having 1 to 5 carbon atoms, and L 111 represents the following formula (L111)

[0025] [Chemical formula]

[0026] (In the formula, * represents the bonding position to the ring, and R 7111 represents a hydrogen atom or a methyl group, and when there are a plurality of Rs 7111 they may be the same or different, n1111 represents an integer from 1 to 10, n2111 represents an integer from 0 to 10, but when n2111 represents an integer of 1 or more, the order of each repeating unit enclosed by n1111 and n2111 is not limited, the bonding mode is random, and each repeating unit enclosed by n2111 may have the same structure or a plurality of different structures. ) represents a group represented by, m111 represents an integer from 1 to 7, m112 represents an integer of 1 or more, m113 represents an integer of 1 or more, but m112 + m113 represents an integer of 5 or less. ) is particularly preferably represented by

[0027] When the active ester resin of the present invention is added to an epoxy resin composition to produce a resin plate, particularly when emphasizing the balance between low dielectric loss tangent and high glass transition temperature, the phenolic hydroxyl group-containing resin (A) is represented by the above formula (S111-1), and L 111In the above formula (L111), it is preferable that n2111 represents 0. When the active ester resin of the present invention is added to an epoxy resin composition to produce a resin plate, particularly when emphasizing the low dielectric tangent, the phenolic hydroxyl group-containing resin (A) is preferably represented by the above formula (S111-2) or formula (S111-3). Further, when the active ester resin of the present invention is added to an epoxy resin composition to produce a resin plate, particularly when emphasizing the high glass transition temperature, it is preferable that n2111 represents 0 in the above formulas (S111-1) to (S111-3). When emphasizing the low softening point of the active ester resin of the present invention, it is preferable that n2111 represents an integer of 1 or more in the above formulas (S111-1) to (S111-3).

[0028] In this specification, a group whose bonding position is not fixed to any atom constituting the ring means that it can be bonded to any of the substitutable ring-constituting atoms in the ring. For example, in the structural formula represented by the above formula (S111-1), the group represented by L 111 can be bonded to any of the seven substitutable ring-constituting carbon atoms in the naphthalene ring. Further, in the structural formula represented by the above formula (S111-3), the group represented by L 111 and the group represented by R A can be bonded to different ring-constituting carbon atoms among the five substitutable ring-constituting carbon atoms in the benzene ring.

[0029] In the active ester resin of the present invention, the aromatic (poly) carboxylic acid or its acid halide (B) is an aromatic compound that can react with the phenolic hydroxyl group of the phenolic hydroxyl group-containing resin (A) to form an ester bond. The specific structure is not particularly limited, and any compound may be used. Specific examples include benzenedicarboxylic acids such as isophthalic acid and terephthalic acid, benzenetricarboxylic acids such as trimellitic acid, naphthalenedicarboxylic acids such as naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, and naphthalene-2,7-dicarboxylic acid, acid halides thereof, and compounds in which the above-mentioned aliphatic hydrocarbon group, alkoxy group, halogen atom, etc. are substituted on the aromatic nucleus. Examples of the acid halide include acid chlorides, acid bromides, acid fluorides, acid iodides, and the like. These may be used alone or in combination of two or more. Among them, benzenedicarboxylic acids such as isophthalic acid and terephthalic acid or their acid halides are preferred because they result in an active ester resin with high reaction activity and excellent curability.

[0030] Although the active ester resin of the present invention exhibits a low dielectric tangent, from the viewpoint of controlling physical properties such as heat resistance, mechanical strength, and improved adhesion to copper foil and the like of the cured product, a resin obtained by reacting a phenolic hydroxyl group-containing resin (A), an aromatic (poly) carboxylic acid or its acid halide (B), and further a hydroxyl group-containing compound or resin that is a compound or resin (C) different from the phenolic hydroxyl group-containing resin (A) may also be used. In that case, the hydroxyl group-containing compound or resin (C) is not particularly limited in its specific structure as long as it is a compound or resin that can provide desired physical properties, and any compound may be used.

[0031] Specific examples of the hydroxyl group-containing compound or resin (C) include, as examples of compounds having one phenolic hydroxyl group, phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, 2,6-xylenol, o-phenylphenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, 4-(α-cumyl)phenol, α-naphthol, β-naphthol and other aromatic monohydroxy compounds. From the viewpoint of the low dielectric loss tangent of the resulting cured product, α-naphthol, β-naphthol, o-phenylphenol or p-phenylphenol is preferred.

[0032] Specific examples of the hydroxyl group-containing compound or resin (C) also include, as examples of compounds having two or more phenolic hydroxyl groups, resorcinol, hydroquinone, trimethylhydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,6-naphthalenediol, 2,6-naphthalenediol, 2,3-naphthalenediol, 2,7-naphthalenediol, 1,4-naphthalenediol, 3,3',5,5'-tetramethylbisphenol F, 3,3',5,5'-tetramethylbiphenol and other aromatic dihydroxy compounds; 1,3,5-trihydroxybenzene, 1,2,3-trihydroxybenzene, 2,4,4’-trihydroxybenzophenone, triphenolmethane and other aromatic trihydroxy compounds; 2,2',4,4'-tetrahydroxybenzophenone, 1,1,2,2-tetraphenolethane and the like. From the viewpoint of the low dielectric loss tangent of the resulting cured product, bisphenol A, bisphenol F, bisphenol S, 3,3',5,5'-tetramethylbisphenol F or 3,3',5,5'-tetramethylbiphenol is preferred.

[0033] The hydroxyl group-containing compound or resin (C) also has the following general formula (S2)

[0034]

Chemical formula

[0035] (wherein A2 and A 3 and A 4 each independently represents a hydrocarbon ring or heterocyclic ring having 3 to 16 carbon atoms which may be substituted, provided that when there are a plurality of A 3 they may be the same or different, and Z 1 and Z 2 each independently represents a group selected from -O-, -S-, -S(=O)-, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an aralkylene group having 8 to 20 carbon atoms, provided that when there are a plurality of Z 1 they may be the same or different, and m2 represents an integer from 0 to 20.) It may be a compound or resin represented by

[0036] In the compound or resin represented by the general formula (S2), HO-A 2 and A 3 -OH and A 4 -OH, specifically, residues of aromatic monohydroxy compounds such as phenol, o-cresol, m-cresol, p-cresol, 3,5-xylenol, 2,6-xylenol, o-phenylphenol, p-phenylphenol, 2-benzylphenol, 4-benzylphenol, 4-(α-cumyl)phenol, α-naphthol, β-naphthol, etc. can be mentioned.

[0037] In the compound or resin represented by the general formula (S2), Z 1 and Z 2 Specifically, the groups represented by are methylene, ethylene, propylene, 1-methylmethylene, 1,1-dimethylmethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, propylene, butylene, 1-methylpropylene, 2-methylpropylene, pentylene, hexylene, cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cyclopentylene, cycloheptylene, and the following formulas (Z-1) to (Z-10)

[0038]

Chemical formula

[0039] (In the formula, * represents a bond position with the ring represented by A 2 , A 3 and A 4 .) Examples of the group represented by the formula include a group represented by Z 1 and Z 2 . From the viewpoints of adhesion and dielectric properties, the group represented by the formula is preferably a group selected from -O-, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, and an aralkylene group having 8 to 20 carbon atoms, and particularly preferably a group selected from the formulas (Z-3) to (Z-10). Further, from the viewpoint of solubility in a solvent, m2 is preferably an integer of 0 to 5.

[0040] Further, the hydroxyl group-containing compound or resin (C) is represented by the following formula (S2-1)

[0041] [Chemical formula]

[0042] (In the formula, R 21 represents a group selected from a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 3 to 20 carbon atoms, and an aralkyl group having 4 to 20 carbon atoms, and m21 represents an integer of 1 to 20.) Examples of the compound or resin represented by the formula include those represented by the formula.

[0043] In the compound or resin represented by the formula (S2-1), specific examples of R 21 include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a pentyl group, a benzyl group, and the like. m21 preferably represents an integer of 1 to 15, and more preferably represents an integer of 1 to 12.

[0044] Specific examples of the active ester resin of the present invention include, for example, the following formulas (E-1) to (E-16)

[0045]

Chem.

[0046]

Chem.

[0047]

Chem.

[0048]

Chem.

[0049]

Chem.

[0050] (In the formula, L a , L b and L c each represent the following formula (La), formula (Lb) and formula (Lc)

[0051]

Chem.

[0052] (In the formula, * represents the bonding position to the ring, na, nb and nc each independently represent an integer from 1 to 20, but the order of each repeating unit enclosed by na and nb in formula (Lb) and each repeating unit enclosed by na and nc in formula (Lc) is not limited and is random.), n, n’, and n’’ each independently represent an integer from 0 to 40, k represents an integer from 0 to 7, l represents an integer from 0 to 5, p represents an integer from 0 to 4, q represents an integer from 0 to 3, r represents an integer from 0 to 6, s represents 0, 1 or 2, but the sum of k, l, p and q in the molecule is 1 or more.). Examples of the resin represented by

[0053] The active ester resin of the present invention can be produced by the following production methods. (Production Method 1) Production of the active ester resin represented by the following formula (M6)

[0054] [Chemical formula]

[0055] (In the formula, * represents the bonding position to the ring, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , r1, r2, n1 and n2 each represent the same meaning as R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , r1, r2, n1 and n2 in the general formula (S), and k represents an integer from 0 to 7, provided that the total of k contained in the active ester resin represented by the formula (M6) is 1 or more.)

[0056] A phenolic hydroxyl group-containing compound represented by formula (M1) can be reacted with an indene structure-containing compound represented by formula (M2) and a compound represented by formula (M3) in the presence of an acid, for example, to obtain a phenolic hydroxyl group-containing resin represented by formula (M4). Examples of the acid include inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, benzenesulfonic acid, p-toluenesulfonic acid, and methanesulfonic acid; Lewis acids such as aluminum chloride, boron trifluoride, zinc chloride, and iron chloride; and solid acids such as activated clay. The amount of the acid used is preferably 0.001 parts by mass or more and 10 parts by mass or less, more preferably 0.01 parts by mass or more and 5 parts by mass or less, and particularly preferably 0.1 parts by mass or more and 3 parts by mass or less when the theoretical amount of the resulting phenolic hydroxyl group-containing resin is 100 parts by mass. When using a solid acid, it is preferably 0.01 parts by mass or more and 100 parts by mass or less, more preferably 0.1 parts by mass or more and 50 parts by mass or less, and particularly preferably 1 part by mass or more and 20 parts by mass or less when the theoretical amount of the resulting phenolic hydroxyl group-containing resin is 100 parts by mass.

[0057] The reaction of the phenolic hydroxyl group-containing compound represented by formula (M1) with the indene structure-containing compound represented by formula (M2) and the compound represented by formula (M3) may be carried out without a solvent or in a solvent. Examples of the solvent include ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, benzene, toluene, xylene, chlorobenzene, cyclohexane, and dichloromethane. From the viewpoints of reactivity and ease of post-treatment, toluene or xylene is preferred.

[0058] The reaction method may be a method of mixing a phenolic hydroxyl group-containing compound represented by formula (M1), an indene structure-containing compound represented by formula (M2), a compound represented by formula (M3), and a reaction solvent, and then adding an acid, or a method of mixing a phenolic hydroxyl group-containing compound represented by formula (M1), an acid, and a reaction solvent, and then adding an indene structure-containing compound represented by formula (M2) and a compound represented by formula (M3). The reaction temperature is not particularly limited, but from the viewpoints of the viscosity of the resulting phenolic hydroxyl group-containing resin represented by formula (M4), solubility in a solvent, etc., it is preferably -30°C or higher and 200°C or lower, more preferably -20°C or higher and 150°C or lower, and particularly preferably 0°C or higher and 80°C or lower. It is preferable to perform aging to reduce unreacted components after the reaction. The aging temperature is preferably 0°C or higher and 200°C or lower, more preferably 20°C or higher and 150°C or lower, and particularly preferably 40°C or higher and 130°C or lower. After the reaction, the acid is removed by neutralization, washing with water, filtration, or decomposition, and the target phenolic hydroxyl group-containing resin can be separated by general operations such as extraction and distillation. The neutralization treatment and the washing treatment with water may be carried out according to conventional methods. For example, basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, and ammonia can be used as neutralizing agents.

[0059] Next, an active ester resin represented by formula (M6) can be obtained by reacting the phenolic hydroxyl group-containing resin represented by formula (M4) with a compound represented by formula (M5) in the presence of a base, for example. Examples of the base include sodium hydroxide, potassium hydroxide, triethylamine, pyridine, etc. Among these, particularly sodium hydroxide and potassium hydroxide can be used in an aqueous solution state, which is preferable from the viewpoint of good productivity.

[0060] The reaction method can be carried out by mixing a phenolic hydroxyl group-containing resin represented by formula (M4) and a compound represented by formula (M5) in the presence of an organic solvent, and reacting while continuously or intermittently dropping a base or an aqueous solution thereof. At this time, the concentration of the aqueous solution of the alkali catalyst is preferably in the range of 3.0 to 30% by mass. Examples of the organic solvent include toluene, dichloromethane, chloroform, and the like. After the reaction, the active ester resin represented by formula (M6) can be obtained by neutralizing the base and washing with water. (Production Method 2) Production of the active ester resin represented by the following formula (M12)

[0061]

Chemical formula

[0062] (In the formula, * represents the bonding position to the ring, R 1 , R 3 , R 4 , R 5 , R 6 and n1 each represent the same meaning as R 1 , R 3 , R 4 , R 5 , R 6 and n1 in the general formula (S), A 2 , A 4 and Z 2 each represent the same meaning as A 2 , A 4 and Z 2 in the general formula (S2), n represents an integer from 0 to 40, k represents an integer from 0 to 7, but the total of k contained in the active ester resin represented by formula (M12) is 1 or more.)

[0063] The phenolic hydroxyl group-containing compound represented by formula (M7) can be reacted with the indene structure-containing compound represented by formula (M8) in the presence of an acid, for example, to obtain the phenolic hydroxyl group-containing resin represented by formula (M9). The conditions such as the acid, solvent, and temperature are the same as those in Production Method 1.

[0064] Next, by reacting the phenolic hydroxyl group-containing resin represented by the formula (M9) with, for example, the compound represented by the formula (M10) and the hydroxyl group-containing compound represented by the formula (M11) in the presence of a base, the active ester resin represented by the formula (M12) can be obtained. Examples of the base include sodium hydroxide, potassium hydroxide, triethylamine, pyridine, and the like. Among these, in particular, sodium hydroxide and potassium hydroxide can be used in an aqueous solution state, which is preferable from the viewpoint of good productivity.

[0065] The reaction method can be carried out by mixing the phenolic hydroxyl group-containing resin represented by the formula (M9), the compound represented by the formula (M10), and the hydroxyl group-containing compound represented by the formula (M11) in the presence of an organic solvent, and reacting while continuously or intermittently dropping a base or its aqueous solution. At this time, the concentration of the aqueous solution of the alkali catalyst is preferably in the range of 3.0 to 30% by mass. Examples of the organic solvent include toluene, dichloromethane, chloroform, and the like. After the reaction, the base is neutralized and washed with water to obtain the active ester resin represented by the formula (M12).

[0066] The active ester resin of the present invention thus obtained preferably has a softening point of 70°C or higher and 200°C or lower, because it has high solubility in an organic solvent and becomes a material suitable for a varnish for a circuit board, and also has an excellent balance among heat resistance, flame retardancy, dielectric properties, and thermal decomposition resistance.

[0067] The functional group equivalent of the active ester resin of the present invention is preferably 50 g / equivalent or more and 1000 g / equivalent or less, more preferably 100 g / equivalent or more and 500 g / equivalent or less, and particularly preferably 120 g / equivalent or more and 400 g / equivalent or less, from the viewpoints of curability and dielectric properties, when the total number of aromatic ester groups in the molecule is used as the number of functional groups of the active ester.

[0068] The number average molecular weight (Mn) of the active ester resin of the present invention is preferably 300 or more and 5000 or less, more preferably 400 or more and 4000 or less, and particularly preferably 500 or more and 3000 or less, from the viewpoints of curability, dielectric properties, and compatibility with other components.

[0069] <Resin composition> The active ester resin of the present invention has a function as a curing agent for epoxy compounds and other compounds. Since the active ester resin of the present invention can prevent or suppress the generation of hydroxyl groups when reacting with an epoxy resin, a cured product excellent in low dielectric properties can be obtained, which is useful.

[0070] Specific examples of the epoxy resin used by mixing with the active ester resin of the present invention include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, bisphenol sulfide type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, polyhydroxynaphthalene type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, biphenyl novolak type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolak type epoxy resin, biphenyl-modified phenol type epoxy resin (a polyhydric phenol type epoxy resin in which a phenol skeleton and a biphenyl skeleton are linked by a bismethylene group), biphenyl-modified naphthol type epoxy resin (a polyhydric naphthol type epoxy resin in which a naphthol skeleton and a biphenyl skeleton are linked by a bismethylene group), alkoxy group-containing aromatic ring-modified novolak type epoxy resin (a resin in which a glycidyl group-containing aromatic ring and an alkoxy group-containing aromatic ring are linked by formaldehyde), phenylene ether type epoxy resin, naphthylene ether type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, xanthene type epoxy resin, and the like. These may be used alone or in combination of two or more kinds.

[0071] Among these epoxy resins, since a cured product with excellent dielectric properties can be obtained, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, polyhydroxynaphthalene type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, phenylene ether type epoxy resin, naphthylene ether type epoxy resin, xanthene type epoxy resin are preferred, and dicyclopentadiene-phenol addition reaction type epoxy resin, naphthol novolac type epoxy resin, phenol aralkyl type epoxy resin, biphenyl aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, biphenyl-modified phenol type epoxy resin (a polyhydric phenol type epoxy resin in which a phenol skeleton and a biphenyl skeleton are linked by a bismethylene group), biphenyl-modified naphthol type epoxy resin (a polyhydric naphthol type epoxy resin in which a naphthol skeleton and a biphenyl skeleton are linked by a bismethylene group), alkoxy group-containing aromatic ring-modified novolac type epoxy resin (a resin in which a glycidyl group-containing aromatic ring and an alkoxy group-containing aromatic ring are linked by formaldehyde), aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, naphthylene ether type epoxy resin are particularly preferred.

[0072] Specific commercially available epoxy resins used in mixture with the active ester resin of the present invention include EPICLON (registered trademark) 840, EPICLON 840-S, EPICLON 850, EPICLON 850-S, EPICLON EXA-850CRP, EPICLON EXA-830LVP, EPICLON HP-7200L, EPICLON HP-7200, EPICLON HP-7200H, EPICLON HP-7200HHH, EPICLON HP-7200H-75M, EPICLON HP-4032SS, EPICLON HP-4032D, EPICLON HP-EXA-4850-150, EPICLON HP-EXA-4850-1000, EPICLON HP-7250, EPICLON HP-4700, EPICLON HP-4710, EPICLON HP-4770, EPICLON HP-5000, EPICLON HP-9900-75M, EPICLON HP-9500, EPICLON HP-6000, EPICLON HP-6000L (all of the above are manufactured by DIC Corporation), Epotohto (registered trademark) YD-128, Epotohto YD-128G, Epotohto YD-128S, Epotohto YD-128CA, Epotohto YD-134, Epotohto YD-011, Epotohto YD-012, Epotohto YD-013, Epotohto YDF-170, Epotohto YDF-170N, Epotohto YDF-2001, Epotohto YD-8125, Epotohto YDF-8170C, Epotohto ZX-1059, Epotohto YD-825GS, Epotohto YDF-870GS, Epotohto YDPN-638, Epotohto YDCN-700-7, Epotohto YDCN-700-10, Epotohto YDCN-704, Epotohto YDCN-704A, Epotohto FX-289BEK75, Epotohto FX-1225EK75, Epotohto ST-3000, Epotohto ST-4000D, Epotohto YDC-1312, Epotohto YSLV-70XY, Epotohto YSLV-80XY, EpotohtoYSLV-120TE (manufactured by Nippon Steel & Chemical & Material Co., Ltd.), jER (registered trademark) 825, jER 827, jER 828, jER 834, jER 801N, jER 811, jER 813, jER 816A, jER 819, jER 806, jER 806H, jER 807, jER 4005P, jER 4007P, jER 4010P, jER 152, jER 154, jER 157S70, jER 1031S, jER 1032H60, jER 604, jER 630, jER 871, jER 872, jER 872X75, jER 890, jER YL6810, jER 1750, jER YX7700, jER 8000, jER YX8034, jER YL980, jER YL983U, jER YX7400N, jER YX7105, jER YX7110B80, jER YX7760, jER YX4000, jER YX4000H, jER 4000HS, jER YL6121HA, jER YL6677 (manufactured by Mitsubishi Chemical Corporation), NC-3100, NC-3000-L, NC-3000, NC-3000-H, NC-3000-FH-75M, NC-2000-L, XD-1000-2L, XD-1000, XD-1000-H, NC-7000-L, NC-7300-L, EPPN-201, RE-305, RE-306, RE-305S, BR-250H, EPPN-501H, EPPN-501HY, EPPN-502H, FAE-2500, GTR-1800, EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (manufactured by Nippon Kayaku Co., Ltd.), etc.

[0073] In the resin composition of the present invention, the blending amounts of the active ester resin and the epoxy resin are such that, from the viewpoint of good curability and various physical properties of the cured product, the carbonyl oxy groups constituting the ester groups in the active ester resin are 0.8 equivalent or more and 1.5 equivalents or less per equivalent of epoxy groups in the resin composition, which is preferably a ratio, and from the viewpoint of being able to improve the dielectric properties and heat resistance while maintaining excellent flame retardancy in the cured product, it is particularly preferably a ratio of 0.9 equivalent or more and 1.3 equivalents or less.

[0074] <Other curing agent> In addition to the active ester resin and epoxy resin described above, the resin composition of the present invention may also be used in combination with other curing agents for epoxy resins. Examples of other curing agents for epoxy resins include amine-based curing agents, amide-based curing agents, acid anhydride-based curing agents, phenol-based curing agents, etc. Examples of amine-based curing agents include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, boron trifluoride-amine complex, guanidine derivatives, etc. Examples of amide-based curing agents include dicyandiamide, polyamide resins synthesized from dimers of linolenic acid and ethylenediamine, etc. Examples of acid anhydride-based curing agents include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. Examples of phenol-based curing agents include phenol novolak resins, cresol novolak resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition-type resins, phenol aralkyl resins, naphthol aralkyl resins, trimethylolmethane resins, tetraphenylol ethane resins, naphthol novolak resins, naphthol-phenol co-condensed novolak resins, naphthol-cresol co-condensed novolak resins, biphenyl-modified phenol resins (polyhydric phenol resins in which phenol nuclei are linked by bismethylene groups), biphenyl-modified naphthol resins (polyhydric naphthol resins in which phenol nuclei are linked by bismethylene groups), aminotriazine-modified phenol resins (polyhydric phenol resins in which phenol nuclei are linked by melamine or benzoguanamine, etc.), etc.

[0075] Among these, those containing a large amount of aromatic skeletons in the molecular structure are particularly preferable from the viewpoint of the flame retardant effect. Specifically, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, phenol aralkyl resin, naphthol aralkyl resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin, biphenyl-modified naphthol resin, aminotriazine-modified phenol resin are preferable.

[0076] Specific commercially available curing agents for other epoxy resins used in admixture with the active ester resin of the present invention include, as phenolic curing agents, PHENOLITE® TD-2131, PHENOLITE TD-2093Y, PHENOLITE TD-2093Y-60M, PHENOLITE TD-2090, PHENOLITE TD-2090-60M, PHENOLITE KA-1160, PHENOLITE KA-1163, PHENOLITE KA-1165, PHENOLITE VH-4150, PHENOLITE VH-4170, PHENOLITE KH-6021, PHENOLITE LF-7911, PHENOLITE LF-6161, PHENOLITE LF-4871, EPICLON HPC-9500-60M, EPICLON HPC-9500P-53M, PHENOLITE LA-1356, PHENOLITE LA-3018-50P, PHENOLITE LA-7052, PHENOLITE LA-7054, PHENOLITE LA-7751 (above, manufactured by DIC Corporation), SK Resin HE100C-10, SK Resin HE100C-15, SK Resin HE100C-30, SK Resin HE200C-07, SK Resin HE200C-10, SK Resin HE510-05, SK Resin HE610C-07, SK Resin HE910-10, SK Resin HE910-20 (above, manufactured by Air Water Performance Chemicals, Inc.), KAYAHARD® GPH-65, KAYAHARD GPH-103, KAYAHARD KTG-105 (above, manufactured by Nippon Kayaku Co., Ltd.), jER Cure® 170, jER Cure 171N (above, manufactured by Mitsubishi Chemical Corporation), Milex® XL, Milex RS, Milex RN (above, manufactured by Mitsui Chemicals Fine Inc.), ZX-798P (manufactured by Nippon Steel Chemical & Material Co., Ltd.). As amine curing agents, EPICLON B-065 (manufactured by DIC Corporation), KAYAHARD A-A (manufactured by Nippon Kayaku Co., Ltd.), jER Cure ST14, jER Cure YN100, jER Cure SA1, jER Cure TO184, jER CureWA (manufactured by Mitsubishi Chemical Corporation as above) can be mentioned. As acid anhydride-based curing agents, EPICLON B-4500MC-C, EPICLON B-4500-C, EPICLON B-4500MC (manufactured by DIC Corporation as above), HN-2200, MHAC-P (manufactured by Resonaak Co., Ltd.), KAYAHARD MCD (manufactured by Nippon Kayaku Co., Ltd.), jER Cure YH306, jER Cure YH307 (manufactured by Mitsubishi Chemical Corporation as above) can be mentioned.

[0077] The above other curing agents may be used alone or in combination of two or more.

[0078] In addition, the resin composition of the present invention may also use an active ester resin other than the active ester resin of the present invention as a curing agent for the epoxy resin. Examples of the active ester resin other than the active ester resin of the present invention include EPICLON (registered trademark) HPC-8000-65T, EPICLON HPC-8000L-65MT, EPICLON HPC-8150-62T, EPICLON EXB-8, EPICLON NE-V-1100-70T (manufactured by DIC Corporation as above).

[0079] <Other thermosetting resins> In addition to the active ester resin and epoxy resin described in detail above, the resin composition of the present invention may also be used in combination with other thermosetting resins. Examples of other thermosetting resins include maleimide resins, bismaleimide resins, polymaleimide resins, polyphenylene ether resins, polyimide resins, cyanate ester resins, benzoxazine resins, triazine-containing cresol novolak resins, cyanate ester resins, styrene-maleic anhydride resins, allyl group-containing resins such as diallylbisphenol and triallyl isocyanurate, polyphosphoric acid esters, phosphate ester-carbonate copolymers, etc. These other resins may be used alone or in combination of two or more.

[0080] <Solvent> The resin composition of the present invention may be prepared without a solvent or may contain a solvent. The solvent has functions such as adjusting the viscosity of the resin composition. Examples of the solvent 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, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve 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 N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more.

[0081] The amount of the solvent used is preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, based on the total mass of the resin composition. When the amount of the solvent used is 10% by mass or more, it is preferable because of excellent handleability. 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.

[0082] <Additive> The resin composition of the present invention may contain an additive. Examples of the additive include a curing accelerator, a flame retardant, and a filler.

[0083] <Curing accelerator> Examples of the curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and urea-based curing accelerators.

[0084] Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, tricyclohexylphosphine; organic phosphite compounds such as trimethyl phosphite, triethyl phosphite; phosphonium salts such as ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, butylphosphonium tetraphenylborate, tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenylphosphonium dicyanamide, butylphenylphosphonium dicyanamide, tetrabutylphosphonium decanoate, etc.

[0085] Examples of the amine-based curing accelerator include triethylamine, tributylamine, N,N-dimethylaminopyridine (DMAP), 2,4,6-tris(dimethylaminomethyl)phenol, 1,8-diazabicyclo[5.4.0]undecene (DBU), 1,5-diazabicyclo[4.3.0]nonene-5 (DBN), etc.

[0086] Examples of the imidazole-based curing accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 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-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.

[0087] Examples of the 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]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-butylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and the like.

[0088] Examples of the urea-based curing accelerators include 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, and the like.

[0089] Among the above-mentioned curing accelerators, it is preferable to use 2-ethyl-4-methylimidazole and N,N-dimethylaminopyridine (DMAP). The above-mentioned curing accelerators may be used alone or in combination of two or more.

[0090] The amount of the curing accelerator used can be appropriately adjusted to obtain the desired curability. However, it is preferably 0.01 part by mass or more and 5 parts by mass or less, more preferably 0.1 part by mass or more and 3 parts by mass or less, based on 100 parts by mass of the total amount of the mixture of the epoxy resin and the active ester resin. When the amount of the curing accelerator used is 0.01 part by mass or more, it is preferable because of excellent curability. On the other hand, when the amount of the curing accelerator used is 5 parts by mass or less, it is preferable because of excellent insulation reliability.

[0091] <Flame retardant> The flame retardant is not particularly limited, and examples thereof include inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, and halogen-based flame retardants.

[0092] The inorganic phosphorus-based flame retardant is not particularly limited, and examples thereof include ammonium phosphates such as red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphoric acid amides.

[0093] The organic phosphorus flame retardant is not particularly limited, and examples thereof include phosphate esters such as methyl acid phosphate, ethyl acid phosphate, isopropyl acid phosphate, dibutyl phosphate, monobutyl phosphate, butoxyethyl acid phosphate, 2-ethylhexyl acid phosphate, bis(2-ethylhexyl) phosphate, monoisodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleyl acid phosphate, butyl pyrophosphate, tetracosyl acid phosphate, ethylene glycol acid phosphate, (2-hydroxyethyl) methacrylate acid phosphate; diphenylphosphines such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphine oxide; phosphorus-containing phenols such as 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinyl hydroquinone, diphenylphosphenyl-1,4-dioxynaphthalene, 1,4-cyclooctylene phosphinyl-1,4-phenyldiol, 1,5-cyclooctylene phosphinyl-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, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; compounds obtained by reacting the phosphate ester, the diphenylphosphine, the phosphorus-containing phenol with an epoxy resin, an aldehyde compound, a phenol compound, and the like.

[0094] The halogen-based flame retardant is not particularly limited, and examples thereof include brominated polystyrene, bis(pentabromophenyl)ethane, tetrabromobisphenol A bis(dibromopropyl ether), 1,2-bis(tetrabromophthalimide), 2,4,6-tris(2,4,6-tribromophenoxy)-1,3,5-triazine, tetrabromophthalic acid, and the like.

[0095] The flame retardant may be used alone or in combination of two or more.

[0096] The amount of the flame retardant used is preferably 0.1 part by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 30 parts by mass or less, based on 100 parts by mass of the epoxy resin. When the amount of the flame retardant used is 0.1 part by mass or more, it is preferable because flame retardancy can be imparted. On the other hand, when the amount of the flame retardant used is 50 parts by mass or less, it is preferable because flame retardancy can be imparted while maintaining dielectric properties.

[0097] <Filler> Examples of the filler include organic fillers and inorganic fillers. The organic filler has functions such as improving elongation and mechanical strength. The inorganic filler has functions such as reducing the thermal expansion coefficient and imparting flame retardancy.

[0098] The organic filler is not particularly limited, and examples thereof include polyamide particles.

[0099] The inorganic filler is not particularly limited, and examples thereof include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium 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, carbon black and the like. Among these, it is preferable to use silica. At this time, examples of the silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica.

[0100] Further, the filler may be surface-treated as necessary. The surface treatment agent is not particularly limited, and examples thereof include aminosilane-based coupling agents, epoxysilane-based coupling agents, mercaptosilane-based coupling agents, silane-based coupling agents, organosilazane compounds, titanate-based coupling agents and the like. Specific examples of the surface treatment agent include 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldisilazane and the like.

[0101] The filler may be used alone or in combination of two or more.

[0102] The amount of the filler used is preferably 0.5 parts by mass or more and 95 parts by mass or less, more preferably 5 parts by mass or more and 80 parts by mass or less, based on 100 parts by mass of the epoxy resin. When the amount of the filler used is 0.5 parts by mass or more, it is preferable because the effect of the filler can be sufficiently imparted. On the other hand, in order not to impair the moldability due to the increase in the viscosity of the formulation, it is preferable that the amount of the filler used is 95 parts by mass or less.

[0103] <Cured product> The present invention relates to a cured product obtained by curing the resin composition. Since the active ester resin itself has a low dielectric loss tangent, the cured product obtained from the resin composition containing the active ester resin also has a low dielectric loss tangent, which is a preferred embodiment.

[0104] As a method for producing a cured product obtained by curing the resin composition of the present invention, for example, the heating temperature during heat curing is not particularly limited, but is 100°C or higher and 300°C or lower, and the heating time is preferably 1 hour or longer and 24 hours or shorter.

[0105] <Uses of the resin composition> The uses for which the resin composition of the present invention is used include insulating materials for circuit boards such as printed wiring board materials, resin compositions for flexible printed circuit boards, interlayer insulating materials for build-up boards, adhesive films for build-up, resin casting materials, adhesives, semiconductor encapsulation materials, semiconductor devices, prepregs, conductive pastes, build-up films, build-up boards, fiber-reinforced composite materials, molded products obtained by curing the above composite materials, and the like. Among these various uses, in the cases of printed wiring board materials, insulating materials for circuit boards, and adhesive films for build-up, they can be used as insulating materials for so-called substrates with built-in electronic components in which passive components such as capacitors and active components such as IC chips are embedded in the substrate. Furthermore, among the above, since the cured product has low dielectric characteristics, the resin composition of the present invention is preferably used for semiconductor encapsulation materials, semiconductor devices, prepregs, circuit boards, flexible printed circuit boards, build-up films, multilayer printed wiring boards, build-up boards, fiber-reinforced composite materials, and molded products obtained by curing the above composite materials. Hereinafter, a method for manufacturing the semiconductor encapsulation material and the like from the resin composition will be described.

[0106] "Semiconductor encapsulation material" The present invention relates to a semiconductor encapsulating material characterized by containing the resin composition. As a method for obtaining a semiconductor encapsulating material from the resin composition of the present invention, there is a method of sufficiently melt-mixing a compounding agent such as the resin composition of the present invention, a curing accelerator, and an inorganic filler using an extruder, kneader, roll, etc. until it becomes uniform as needed. At this time, as the inorganic filler, fused silica is usually used, but when used as a high thermal conductivity semiconductor encapsulating material for power transistors and power ICs, it is preferable to use crystalline silica, alumina, silicon nitride, etc. having a higher thermal conductivity than fused silica. The filling rate is preferably in the range of 30 parts by mass or more and 95 parts by mass or less of the inorganic filler per 100 parts by mass of the resin composition. In order to improve flame retardancy, moisture resistance, solder crack resistance, and reduce the linear expansion coefficient, 70 parts by mass or more is more preferable, and 80 parts by mass or more is even more preferable.

[0107] "Semiconductor device" The present invention relates to a semiconductor device including a cured product obtained by heat-curing the semiconductor encapsulating material. As a method for obtaining a semiconductor device from the resin composition of the present invention, there is a method of molding the semiconductor encapsulating material by casting, or using a transfer molding machine, injection molding machine, etc., and further heating at 50°C or more and 200°C or less for 2 hours or more and 10 hours or less.

[0108] "Prepreg" The present invention relates to a prepreg having a reinforcing base material and a semi-cured product of the resin composition impregnated in the reinforcing base material. As a method for obtaining a prepreg from the resin composition of the present invention, there is a method of impregnating a resin composition made into a varnish by blending an organic solvent into a reinforcing base material (paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass mat, glass rovings cloth, etc.), and then heating at a heating temperature corresponding to the type of solvent used, preferably 50°C or more and 170°C or less. The mass ratio of the resin composition and the reinforcing base material used at this time is not particularly limited, but usually, it is preferable to prepare so that the resin content in the prepreg is 20% by mass or more and 60% by mass or less.

[0109] Examples of the organic solvent used herein include methyl ethyl ketone, acetone, N,N-dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. The selection and appropriate amount of use can be appropriately selected depending on the application. For example, when further manufacturing a printed circuit board from a prepreg 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, N,N-dimethylformamide, etc., and it is also preferable to use it at a ratio such that the non-volatile content is 40% by mass or more and 80% by mass or less.

[0110] "Circuit board" The present invention relates to a circuit board obtained by laminating the prepreg and a copper foil and performing thermocompression bonding molding. As a method for obtaining a printed circuit board from the resin composition of the present invention, there is a method of laminating the prepreg, appropriately stacking a copper foil, and performing thermocompression bonding at 170°C or higher and 300°C or lower for 10 minutes or more and 3 hours or less under a pressure of 1 MPa or higher and 10 MPa or lower.

[0111] "Flexible wiring board" As a method for manufacturing a flexible wiring board from the resin composition of the present invention, there is a method comprising the following three steps. The first step is a step of applying a resin composition containing an active ester resin, an epoxy resin, and an organic solvent to an electrically insulating film using a coater such as a reverse roll coater or a comma coater. The second step is a step of heating the electrically insulating film coated with the resin composition at 60°C or higher and 170°C or lower for 1 minute or more and 15 minutes or less using a heater to volatilize the solvent from the electrically insulating film and B-stage the resin composition. The third step is a step of thermocompression bonding a metal foil to the adhesive (the bonding pressure is 2 N / cm 2 or more and 200 N / cm 2Hereinafter, the crimping temperature is preferably 40°C or higher and 200°C or lower. ) This is the process. Note that if sufficient adhesion performance is obtained through the above three processes, it may end here. However, if complete adhesion performance is required, it is preferable to further post-cure under the conditions of 100°C or higher and 200°C or lower for 1 hour or more and 24 hours or less. The thickness of the cured resin composition film after final curing is preferably in the range of 5 μm or more and 100 μm or less.

[0112] "Build-up film" The present invention relates to a build-up film containing the resin composition of the present invention. As a method for manufacturing the build-up film of the present invention, there is a method of applying the resin composition of the present invention onto a support film to form a resin composition layer to obtain an adhesive film for a multilayer printed wiring board.

[0113] When manufacturing a build-up film from a resin composition, the film softens under the temperature conditions of lamination in the vacuum lamination method (usually 70°C or higher and 140°C or lower), and it is essential that it exhibits fluidity (resin flow) that enables resin filling in the via holes or through holes present in the circuit board simultaneously with the lamination of the circuit board. It is preferable to blend the above components so as to exhibit such characteristics.

[0114] Here, the diameter of the through holes of the multilayer printed wiring board is usually 0.1 mm or more and 0.5 mm or less, and the depth is usually 0.1 mm or more and 1.2 mm or less. Usually, it is preferable to enable resin filling within this range. When laminating both sides of the circuit board, it is desirable that the through holes are filled to about half.

[0115] The method for manufacturing the adhesive film is specifically as follows: After preparing the varnish-like resin composition, the varnish-like composition is applied to the surface of the support film (Y), and then the organic solvent is dried by heating, hot air blowing, or the like to form a composition layer (X) made of the resin composition. The thickness of the formed composition layer (X) is preferably usually 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 μm or more and 70 μm or less, the resin composition layer preferably has a thickness of 10 μm or more and 100 μm or less. In addition, 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 adhesion of dust or the like and scratches on the surface of the resin composition layer.

[0116] Examples of the support film and the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate, polycarbonate, polyimide, and further release paper, copper foil, metal foils such as aluminum foil, and the like. In addition, the support film and the protective film may be subjected to a matting treatment, a corona treatment, or a release treatment.

[0117] The thickness of the support film is not particularly limited, but is usually 10 μm or more and 150 μm or less, and is preferably used in the range of 25 μm or more and 50 μm or less. The thickness of the protective film is preferably 1 μm or more and 40 μm or less.

[0118] The support film (Y) is peeled off after being laminated on the 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 adhesion of dust or the like in the curing process. When peeling off after curing, usually, the support film is previously subjected to a release treatment.

[0119] "Multilayer printed wiring board" A multilayer printed wiring board can be manufactured using the build-up film produced by the above method. For example, in the case where the composition layer (X) is protected by a protective film, after peeling them off, the composition layer (X) is laminated directly onto one or both sides of the circuit board by, for example, a vacuum lamination method. The lamination method may be a batch type or a continuous roll type. Also, the adhesive film and the circuit board may be heated (preheated) if necessary before lamination. The lamination conditions are preferably such that the crimping temperature (lamination temperature) is 70°C or higher and 140°C or lower, and the crimping pressure is preferably 1 kgf / cm 2 or higher and 11 kgf / cm 2 or lower (9.8×10 4 N / m 2 or higher and 107.9×10 4 N / m 2 or lower), and it is preferable to laminate under a reduced pressure of 20 mmHg (26.7 hPa) or lower.

[0120] "Build-up substrate" As a method for manufacturing a build-up substrate from the resin composition of the present invention, those manufactured by a method consisting of the following three steps can be mentioned. The first step is a step of applying a resin composition appropriately blended with rubber, filler, etc. to a circuit board on which a circuit is formed by a spray coating method, a curtain coating method, etc., and then curing it. The second step is a step of, after that, drilling holes such as a predetermined through-hole portion as necessary, treating it with a roughening agent, and forming unevenness by hot washing the surface thereof, and plating a metal such as copper. The third step is a step of sequentially repeating such operations as desired to alternately build up a resin insulating layer and a conductor layer of a predetermined circuit pattern. Note that it is preferable to drill the holes in the through-hole portion after forming the outermost resin insulating layer. The first step can also be performed by a method of laminating a build-up film that has been pre-coated to a desired thickness and dried, in addition to the above-described solution application. Further, for the build-up substrate of the present invention, a copper foil with resin in which the resin composition is semi-cured on a copper foil is heat-pressed onto a wiring board on which a circuit is formed at 170°C or higher and 250°C or lower to form a roughened surface, omitting the step of plating treatment, and it is also possible to manufacture a build-up substrate.

[0121] "Fiber Reinforced Composite Material" As a method for manufacturing a fiber-reinforced composite material from the resin composition of the present invention, each component constituting the resin composition is uniformly mixed to prepare a varnish, which is then impregnated into a reinforcing base material made of reinforcing fibers and then cured. Specifically, the curing temperature is preferably in the range of 50°C or higher and 250°C or lower. In particular, it is cured at 50°C or higher and 100°C or lower to obtain a tack-free cured product, and then it is preferably treated under the temperature condition of 120°C or higher and 200°C or lower. As the reinforcing fibers, any of twisted yarns, untwisted yarns, or non-twisted yarns may be used, but untwisted yarns and non-twisted yarns are preferred because they can achieve both the moldability and mechanical strength of the fiber-reinforced plastic member. Furthermore, as the form of the reinforcing fibers, those with the fiber directions aligned in one direction or woven fabrics can be used. In the case of woven fabrics, plain weave, twill weave, etc. can be freely selected according to the part and application to be used. Specifically, carbon fibers, glass fibers, aramid fibers, boron fibers, alumina fibers, silicon carbide fibers, etc. are mentioned because they are excellent in mechanical strength and durability, and two or more of these can also be used in combination. Among these, carbon fibers are preferred because they provide good strength of the molded product. Such carbon fibers can be of various types such as polyacrylonitrile-based, pitch-based, and rayon-based. Among them, polyacrylonitrile-based carbon fibers, from which high-strength carbon fibers can be easily obtained, are preferred. Here, when impregnating the varnish into a reinforcing base material made of reinforcing fibers to obtain a fiber-reinforced composite material, the amount of the reinforcing fibers used is preferably such that the volume content of the reinforcing fibers in the fiber-reinforced composite material is in the range of 40% or more and 85% or less.

[0122] "Fiber-reinforced resin molded product" As a method for manufacturing a fiber-reinforced resin molded article from the resin composition of the present invention, there are a hand lay-up method, a spray-up method, and a spray-up method in which a fiber aggregate is laid in a mold and the varnish is multilaminated, a male mold or a female mold is used, and a flexible mold capable of applying pressure to the molded article is covered while impregnating a base material made of reinforcing fibers with the varnish and stacking and molding, a vacuum bag method in which airtight sealing is performed and vacuum (reduced pressure) molding is performed, an SMC press method in which a varnish containing reinforcing fibers in advance is formed into a sheet and compression molded with a mold, an RTM method in which the varnish is injected into a combined mold in which fibers are spread, etc. A prepreg impregnated with the varnish in the reinforcing fibers is manufactured, and a method of baking this in a large autoclave can be mentioned. The obtained fiber-reinforced resin molded article is a molded article having a reinforcing fiber and a cured product of the resin composition. Specifically, the amount of the reinforcing fiber in the fiber-reinforced resin molded article is preferably in the range of 40% by mass or more and 70% by mass or less, and particularly preferably in the range of 50% by mass or more and 70% by mass or less from the viewpoint of strength.

[0123] Although the method for manufacturing a semiconductor encapsulating material or the like has been described above, other cured products can also be manufactured from the resin composition of the present invention. As a method for manufacturing other cured products, it can be manufactured by conforming to a general method for curing a resin composition. For example, the heating temperature conditions may be appropriately selected depending on the type and use of the curing agent to be combined.

Examples

[0124] Hereinafter, the present invention will be further described with reference to examples, but the present invention is not limited to these examples. In addition, "%" in the compositions of the following examples and comparative examples means "% by mass". In addition, GPC in this example, 13 The measurement conditions for 13C NMR and MALDI-TOF-MS are as follows.

[0125] <Measurement conditions for GPC> Measuring device: "HLC-8320GPC (registered trademark)" manufactured by Tosoh Corporation, Column: Guard column "TSKgel (registered trademark) HXL-L" manufactured by Tosoh Corporation + “TSKgel G4000HXL” manufactured by Tosoh Corporation + “TSKgel G3000HXL” manufactured by Tosoh Corporation + “TSKgel G2000HXL” manufactured by Tosoh Corporation + “TSKgel G2000HXL” manufactured by Tosoh Corporation Detector: RI (Differential Refractometer) Data processing: “GPC Workstation EcoSEC (registered trademark) Workstation” manufactured by Tosoh Corporation Measurement conditions: Column temperature 40 °C Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Standard sample: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual of the GPC apparatus. “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 to be measured: A 1.0 mass% tetrahydrofuran solution converted to resin solids, filtered through a microfilter (50 μL)

[0126] < 13 Measurement conditions of 13C NMR Apparatus: “JNM-ECA500” manufactured by JEOL Ltd. Measurement mode: SINGLE-PULSE-DEC (H complete decoupling method with NOE suppression) 1 Solvent: Deuterated chloroform ​Pulse angle: 30° pulse Sample concentration: 30 wt% Number of integrations: 4000 times

[0127] <Measurement conditions of MALDI-TOF-MS> Apparatus: AXIMA-TOF manufactured by Shimadzu / Kratos Co., Ltd. 2 (Registered trademark) Ionization method: Matrix-assisted laser desorption ionization method

[0128] (Example 1) Production of active ester resin (I-1) Into a reaction vessel equipped with a thermometer, a dropping funnel, a condenser, a fractionating column and a stirrer, 30.0 g of Galeon Earth (registered trademark) V2R (manufactured by Mizusawa Chemical Industry Co., Ltd.) and 300.0 g of toluene were added, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen gas, the mixture was heated to reflux at 120 °C for 1 hour to remove moisture. After cooling to 40 °C, 90.0 g of 1-naphthol and 210.0 g of indene were added, and the mixture was stirred at room temperature. After the exotherm subsided, the mixture was heated and stirred at 90 °C for 2 hours. After cooling to room temperature, Galeon Earth V2R was removed by filtration. A part of toluene was distilled off under heating and reduced pressure conditions to produce 410.0 g (non-volatile content 58%) of a toluene solution of a phenolic hydroxyl group-containing resin (s-1). The hydroxyl group equivalent of the phenolic hydroxyl group-containing resin (s-1) was 451 g / equivalent. In a reaction vessel equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirring device, 0.4 g of tetrabutylammonium bromide, 47.5 g of isophthaloyl chloride, 368.3 g of a toluene solution of a phenolic hydroxyl group-containing resin (s-1) (non-volatile content 58%), and 726.8 g of toluene were added, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen gas, 96.8 g of a 20% aqueous sodium hydroxide solution was added dropwise over 1 hour with stirring so that the temperature of the reaction solution did not exceed 40°C. After completion of the dropwise addition, the mixture was heated and stirred at 40°C for 1 hour and at 60°C for 4 hours. After neutralization with a 30% aqueous sodium dihydrogen phosphate solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A part of toluene was distilled off under heating and reduced pressure conditions to produce 394.0 g of a toluene solution of an active ester resin (I-1) (non-volatile content 67%). The functional group equivalent of the active ester resin (I-1) was 515 g / equivalent, and the softening point measured based on JIS K7234 was 151°C.

[0129] (Example 2) Production of active ester resin (I-2) In a reaction vessel equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirring device, 90.0 g of 2-naphthol, 105.0 g of indene, 105.0 g of styrene, and 300.0 g of toluene were added, and the system was purged with nitrogen under reduced pressure. 3.0 g of boron trifluoride diethyl ether complex was added, and the mixture was stirred at room temperature while purging with nitrogen gas. After the exotherm subsided, the mixture was heated and stirred at 90°C for 2 hours. After cooling to room temperature, 100 g of an 8% aqueous sodium hydrogen carbonate solution was added, and the mixture was stirred for 30 minutes. After neutralizing the organic layer with a 30% aqueous sodium dihydrogen phosphate solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A part of toluene was distilled off under heating and reduced pressure conditions to produce 486.0 g of a toluene solution of a phenolic hydroxyl group-containing resin (s-2) (non-volatile content 52%). The hydroxyl group equivalent of the phenolic hydroxyl group-containing resin (s-2) was 450 g / equivalent. Into a reaction vessel equipped with a thermometer, dropping funnel, condenser, fractionating column and stirrer, 0.4 g of tetrabutylammonium bromide, 50.9 g of isophthaloyl chloride, 434.4 g of a toluene solution of a phenolic hydroxyl group-containing resin (s-2) (nonvolatile content 52%), and 777.6 g of toluene were added, and the inside of the system was replaced with nitrogen under reduced pressure. While purging with nitrogen gas, 103.8 g of a 20% aqueous sodium hydroxide solution was added dropwise over 1 hour while stirring so that the temperature of the reaction solution did not exceed 40 °C. After completion of the dropwise addition, the mixture was heated and stirred at 40 °C for 1 hour and at 60 °C for 4 hours. After neutralization with a 30% aqueous sodium dihydrogen phosphate solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A part of toluene was distilled off under heating and reduced pressure conditions to produce 441.0 g of a toluene solution of an active ester resin (I-2) (nonvolatile content 65%). The functional group equivalent of the active ester resin (I-2) was 514 g / equivalent, and the softening point measured based on JIS K7234 was 102 °C.

[0130] (Example 3) Production of active ester resin (I-3) Into a reaction vessel equipped with a thermometer, dropping funnel, condenser, fractionating column and stirrer, 105.0 g of phenol, 195.0 g of indene, and 300.0 g of toluene were added, and the inside of the system was replaced with nitrogen under reduced pressure. 3.0 g of boron trifluoride diethyl ether complex was added, and the mixture was stirred at room temperature while purging with nitrogen gas. After the heat generation had subsided, the mixture was heated and stirred at 90 °C for 2 hours. After cooling to room temperature, 100 g of an 8% aqueous sodium hydrogen carbonate solution was added, and the mixture was stirred for 30 minutes. After neutralizing the organic layer with a 30% aqueous sodium dihydrogen phosphate solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. Toluene and unreacted phenol were distilled off under heating and reduced pressure conditions to produce 195.0 g of a phenolic hydroxyl group-containing resin (s-3). The hydroxyl group equivalent of the phenolic hydroxyl group-containing resin (s-3) was 446 g / equivalent. Into a reaction vessel equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer were added 0.3 g of tetrabutylammonium bromide, 40.4 g of isophthaloyl chloride, 178.4 g of a phenolic hydroxyl group-containing resin (s-3), and 612.7 g of toluene, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen gas, 82.4 g of a 20% aqueous sodium hydroxide solution was added dropwise over 1 hour with stirring so that the temperature of the reaction solution did not exceed 40°C. After completion of the dropwise addition, the mixture was heated and stirred at 40°C for 1 hour and at 60°C for 4 hours. After neutralization with a 30% aqueous sodium dihydrogen phosphate solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A part of toluene was distilled off under heating and reduced pressure conditions to produce 340.0 g of a toluene solution of an active ester resin (I-3) (nonvolatile content 58%). The functional group equivalent of the active ester resin (I-3) was 511 g / equivalent, and the softening point measured based on JIS K7234 was 127°C.

[0131] (Example 4) Production of active ester resin (I-4) Into a reaction vessel equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer were added 105.0 g of o-cresol, 195.0 g of indene, and 300.0 g of toluene, and the system was purged with nitrogen under reduced pressure. 3.0 g of boron trifluoride diethyl ether complex was added, and the mixture was stirred at room temperature while purging with nitrogen gas. After the exotherm subsided, the mixture was heated and stirred at 90°C for 2 hours. After cooling to room temperature, 100 g of an 8% aqueous sodium hydrogen carbonate solution was added and stirred for 30 minutes. After neutralizing the organic layer with a 30% aqueous sodium dihydrogen phosphate solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. Toluene and unreacted o-cresol were distilled off under heating and reduced pressure conditions to produce 238.6 g of a phenolic hydroxyl group-containing resin (s-4). The hydroxyl group equivalent of the phenolic hydroxyl group-containing resin (s-4) was 350 g / equivalent. In a reaction vessel equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirring device, 0.4 g of tetrabutylammonium bromide, 65.7 g of isophthaloyl chloride, 227.8 g of a phenolic hydroxyl group-containing resin (s-4), and 809.1 g of toluene were added, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen gas, 133.9 g of a 20% aqueous sodium hydroxide solution was added dropwise over 1 hour with stirring so that the temperature of the reaction solution did not exceed 40 °C. After completion of the dropwise addition, the mixture was heated and stirred at 40 °C for 1 hour and at 60 °C for 4 hours. After neutralization with a 30% aqueous sodium dihydrogen phosphate solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A part of toluene was distilled off under heating and reduced pressure conditions to produce 432.2 g of a toluene solution of the active ester resin (I-4) (nonvolatile content 61%). The functional group equivalent of the active ester resin (I-4) was 415 g / equivalent, and the softening point measured based on JIS K7234 was 121 °C.

[0132] (Example 5) Production of active ester resin (I-5) In Example 3, 249.0 g of a phenolic hydroxyl group-containing resin (s-5) was produced in the same manner except that 60.0 g of phenol and 240.0 g of indene were used instead. The hydroxyl group equivalent of the phenolic hydroxyl group-containing resin (s-5) was 646 g / equivalent. In Example 3, a toluene solution of 358.0 g (nonvolatile content 63%) of the active ester resin (I-5) was produced in the same manner except that 0.4 g of tetrabutylammonium bromide, 32.9 g of isophthaloyl chloride, 210.7 g of the phenolic hydroxyl group-containing resin (s-5), 695.2 g of toluene, and 67.2 g of a 20% aqueous sodium hydroxide solution were used instead. The functional group equivalent of the active ester resin (I-5) was 711 g / equivalent, and the softening point measured based on JIS K7234 was 147 °C.

[0133] (Example 6) Production of active ester resin (I-6) In Example 3, 164.0 g of a phenolic hydroxyl group-containing resin (s-6) was produced in the same manner except that 150.0 g of phenol and 150.0 g of indene were used instead. The hydroxyl equivalent of the phenolic hydroxyl group-containing resin (s-6) was 341 g / equivalent. In Example 3, 289.0 g of a toluene solution (nonvolatile content 58%) of an active ester resin (I-6) was produced in the same manner except that 44.0 g of isophthaloyl chloride, 148.8 g of a phenolic hydroxyl group-containing resin (s-6), 530.7 g of toluene, and 89.8 g of a 20% aqueous sodium hydroxide solution were used instead. The functional group equivalent of the active ester resin (I-6) was 406 g / equivalent, and the softening point measured based on JIS K7234 was 111°C.

[0134] (Example 7) Production of active ester resin (I-7) In Example 4, 235.0 g of a phenolic hydroxyl group-containing resin (s-7) was produced in the same manner except that 75.0 g of o-cresol and 225.0 g of indene were used instead. The hydroxyl equivalent of the phenolic hydroxyl group-containing resin (s-7) was 500 g / equivalent. In Example 4, 419.5 g of a toluene solution (nonvolatile content 61%) of an active ester resin (I-7) was produced in the same manner except that 0.4 g of tetrabutylammonium bromide, 45.7 g of isophthaloyl chloride, 226.0 g of a phenolic hydroxyl group-containing resin (s-7), 765.6 g of toluene, and 93.1 g of a 20% aqueous sodium hydroxide solution were used instead. The functional group equivalent of the active ester resin (I-7) was 565 g / equivalent, and the softening point measured based on JIS K7234 was 137°C.

[0135] (Example 8) Production of active ester resin (I-8) Into a reaction vessel equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer were added 30.0 g of Galeon Earth (registered trademark) V2R (manufactured by Mizusawa Chemical Industry Co., Ltd.) and 300.0 g of toluene, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen gas, the mixture was heated under reflux at 120 °C for 1 hour to remove moisture. After cooling to 40 °C, 90.0 g of 1-naphthol was added. While stirring at room temperature, 210.0 g of indene was added dropwise. After completion of the dropwise addition, the mixture was heated under reflux at 120 °C for 2 hours. After cooling to room temperature, Galeon Earth V2R was removed by filtration. A part of toluene was distilled off under heating and reduced pressure conditions to produce 459.0 g of a toluene solution of a phenolic hydroxyl group-containing resin (s-8) (nonvolatile content 55%). The hydroxyl equivalent of the phenolic hydroxyl group-containing resin (s-8) was 460 g / equivalent. In Example 1, a toluene solution of an active ester resin (I-8) (nonvolatile content 63%) was produced in the same manner except that 51.1 g of isophthaloyl chloride, 425.7 g of a 55% toluene solution of a phenolic hydroxyl group-containing resin (s-8), 796.0 g of toluene, and 104.2 g of a 20% aqueous sodium hydroxide solution were used instead. The functional group equivalent of the active ester resin (I-8) was 524 g / equivalent, and the softening point measured based on JIS K7234 was 145 °C.

[0136] (Example 9) Production of active ester resin (I-9) Into a reaction vessel equipped with a thermometer, dropping funnel, condenser, fractionating column, and stirrer were added 60.0 g of Galeon Earth (registered trademark) V2R (manufactured by Mizusawa Chemical Industry Co., Ltd.) and 600.0 g of toluene, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen gas, the mixture was heated under reflux at 120 °C for 1 hour to remove moisture. After cooling to 40 °C, 180.0 g of 1-naphthol was added. While stirring at room temperature, 420.0 g of indene was added dropwise. After completion of the dropwise addition, the mixture was heated under reflux at 120 °C for 2 hours. After cooling to room temperature, Galeon Earth V2R was removed by filtration. A part of toluene was distilled off under heating and reduced pressure conditions to produce 898.0 g of a toluene solution of a phenolic hydroxyl group-containing resin (s-9) (nonvolatile content 49%). The hydroxyl equivalent of the phenolic hydroxyl group-containing resin (s-9) was 437 g / equivalent. Into a reaction vessel equipped with a thermometer, dropping funnel, condenser, fractionating column and stirrer, 0.5 g of tetrabutylammonium bromide, 66.7 g of isophthaloyl chloride, 292.7 g of a toluene solution of a phenolic hydroxyl group-containing resin (s-9) (non-volatile content 49%), 54.5 g of a polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl group equivalent: 165 g / equivalent, softening point 85 °C), and 1086.3 g of toluene were added, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen gas, 136.0 g of a 20% aqueous sodium hydroxide solution was added dropwise over 1 hour with stirring so that the temperature of the reaction solution did not exceed 40 °C. After completion of the dropwise addition, the mixture was heated and stirred at 40 °C for 1 hour and at 60 °C for 4 hours. After neutralizing with a 30% aqueous solution of sodium dihydrogen phosphate, the organic layer was washed with water until the pH of the aqueous layer reached 7. A part of toluene was distilled off under heating and reduced pressure conditions to produce 557.1 g of a toluene solution of an active ester resin (I-9) (non-volatile content 65%). The functional group equivalent of the active ester resin (I-9) was 549 g / equivalent, and the softening point measured based on JIS K7234 was 164 °C.

[0137] (Example 10) Production of active ester resin (I-10) Into a reaction vessel equipped with a thermometer, dropping funnel, condenser, fractionating column and stirrer, 160.2 g of 2,7-dihydroxynaphthalene, 162.2 g of benzyl alcohol, 160.2 g of xylene, and 3.8 g of p-toluenesulfonic acid monohydrate were added, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen gas, the mixture was heated under reflux at 150 °C for 4 hours to remove water. After cooling to 100 °C or lower, 680.0 g of methyl isobutyl ketone and 4.0 g of a 20% aqueous sodium hydroxide solution were added and stirred. After removing the water layer, the organic layer was washed 3 times with 170.0 g of water. Methyl isobutyl ketone and unreacted benzyl alcohol were distilled off under heating and reduced pressure conditions to produce 260.0 g of a benzyl-modified naphthalene compound (s'-10). The hydroxyl group equivalent of the benzyl-modified naphthalene compound (s'-10) was 173 g / equivalent. In a reaction vessel equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer, 0.5 g of tetrabutylammonium bromide, 84.8 g of isophthaloyl chloride, 248.3 g of a toluene solution of a phenolic hydroxyl group-containing resin (s-9) (nonvolatile content 49%), 96.9 g of a benzyl-modified naphthalene compound (s'-10), and 1050.8 g of toluene were added, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen gas, 173.0 g of a 20% aqueous sodium hydroxide solution was added dropwise over 1 hour with stirring so that the temperature of the reaction solution did not exceed 40°C. After completion of the dropwise addition, the mixture was heated and stirred at 40°C for 1 hour and at 60°C for 4 hours. After neutralization with a 30% aqueous sodium dihydrogen phosphate solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A part of toluene was distilled off under heating and reduced pressure conditions to produce 539.0 g of a toluene solution of an active ester resin (I-10) (nonvolatile content 65%). The functional group equivalent of the active ester resin (I-10) was 417 g / equivalent, and the softening point measured based on JIS K7234 was 169°C.

[0138] (Example 11) Production of active ester resin (I-11) In a reaction vessel equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirrer, 375.0 g of 3,3',5,5'-tetramethylbiphenyl-4,4'-diol, 334.7 g of benzyl alcohol, 375.0 g of xylene, and 7.1 g of p-toluenesulfonic acid monohydrate were added, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen gas, the mixture was heated under reflux at 150°C for 4 hours to remove water. After cooling to 100°C or lower, 187.5 g of xylene and 7.5 g of a 20% aqueous sodium hydroxide solution were added and stirred. After removing the water layer, the organic layer was washed 3 times with 170.0 g of water. Xylene and unreacted benzyl alcohol were distilled off under heating and reduced pressure conditions to produce 580.0 g of a benzyl-modified biphenyl compound (s'-11). The hydroxyl group equivalent of the benzyl-modified biphenyl compound (s'-11) was 211 g / equivalent. Into a reaction vessel equipped with a thermometer, dropping funnel, condenser, fractionating column and stirrer, 0.5 g of tetrabutylammonium bromide, 64.6 g of isophthaloyl chloride, 283.8 g of a toluene solution of a phenolic hydroxyl group-containing resin (s-9) (nonvolatile content 49%), 67.6 g of a benzyl-modified biphenyl compound (s'-11), and 1075.3 g of toluene were added, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen gas, 131.8 g of a 20% aqueous sodium hydroxide solution was added dropwise over 1 hour with stirring so that the temperature of the reaction solution did not exceed 40°C. After completion of the dropwise addition, the mixture was heated and stirred at 40°C for 1 hour and at 60°C for 4 hours. After neutralization with a 30% aqueous sodium dihydrogen phosphate solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A part of toluene was distilled off under heating and reduced pressure conditions to produce 551.0 g of a toluene solution of an active ester resin (I-11) (nonvolatile content 65%). The functional group equivalent of the active ester resin (I-11) was 560 g / equivalent, and the softening point measured based on JIS K7234 was 165°C.

[0139] (Example 12) Production of active ester resin (I-12) Into a reaction vessel equipped with a thermometer, dropping funnel, condenser, fractionating column and stirrer, 75.0 g of 2,6-xylenol, 238.5 g of α,α'-dihydroxy-1,3-diisopropylbenzene, 269.3 g of toluene, and 9.41 g of p-toluenesulfonic acid monohydrate were added, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen gas, the mixture was heated to reflux at 120°C for 12 hours to remove water. After cooling to 100°C or lower, 134.7 g of water and 6.7 g of a 20% aqueous sodium hydroxide solution were added and stirred. After removing the aqueous layer, the organic layer was washed 3 times with 134.7 g of water. Toluene and unreacted 2,6-xylenol were distilled off under heating and reduced pressure conditions to produce 210.0 g of a bisphenol resin (s'-12). The hydroxyl group equivalent of the bisphenol resin (s'-12) was 598 g / equivalent. In a reaction vessel equipped with a thermometer, dropping funnel, condenser, fractionating column and stirrer, 0.5 g of tetrabutylammonium bromide, 59.4 g of isophthaloyl chloride, 262.5 g of a toluene solution of a phenolic hydroxyl group-containing resin (s-9) (non-volatile content 49%), 168.8 g of bisphenol resin (s'-12), and 1151.0 g of toluene were added, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen gas, 121.1 g of a 20% aqueous sodium hydroxide solution was added dropwise over 1 hour with stirring so that the temperature of the reaction solution did not exceed 40°C. After completion of the dropwise addition, the mixture was heated and stirred at 40°C for 1 hour and at 60°C for 4 hours. After neutralizing with a 30% aqueous sodium dihydrogen phosphate solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A part of toluene was distilled off under heating and reduced pressure conditions to produce 580.0 g of a toluene solution of an active ester resin (I-12) (non-volatile content 65%). The functional group equivalent of the active ester resin (I-12) was 652 g / equivalent, and the softening point measured based on JIS K7234 was 174°C.

[0140] (Synthesis Reference Example 1) Production of Active Ester Resin (R-1) In a reaction vessel equipped with a thermometer, dropping funnel, condenser, fractionating column and stirrer, 0.6 g of tetrabutylammonium bromide, 152 g of isophthaloyl chloride, 72 g of 1-naphthol, 165 g of a polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl group equivalent: 165 g / equivalent, softening point 85°C), and 630 g of toluene were added, and the system was purged with nitrogen under reduced pressure. While purging with nitrogen gas, 315 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours with stirring so that the temperature of the reaction solution did not exceed 60°C. After completion of the dropwise addition, the mixture was heated and stirred at 60°C for 3 hours. After neutralizing with a 30% aqueous sodium dihydrogen phosphate solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A part of toluene was distilled off under heating and reduced pressure conditions to produce a 65% toluene solution of an active ester resin (R-1). The functional group equivalent of the active ester resin (R-1) was 223 g / equivalent, and the softening point measured based on JIS K7234 was 150°C.

[0141] (Examples 13 to 23, Comparative Example 1) Preparation of Resin Composition For the active ester resins (I-1) to (I-7) and (I-9) to (I-12) produced in Examples 1 to 7 and Examples 9 to 12, after distilling off the solvent, the solid of the resin was obtained by heating and vacuum drying at 180 °C for 2 hours. Using the obtained active ester resin solid, each component was blended at the ratios shown in Tables 1 and 2 below to prepare a resin composition. For Examples 13 to 19, cresol novolak type polyfunctional epoxy resin EPICLON® N-655-EXP-S (manufactured by DIC Corporation, epoxy equivalent 197 - 207 g / equivalent) was used as the epoxy resin. For Examples 20 to 23 and Comparative Example 1, bisphenol-A type epoxy resin EPICLON 850S (manufactured by DIC Corporation, epoxy equivalent 184 - 194 g / equivalent) was used. 4-Dimethylaminopyridine was used as the curing catalyst. Also, as the active ester resin in Comparative Example 1, the active ester resin (R-1) produced in Synthetic Reference Example 1 was used.

[0142]

Table 1

[0143]

Table 2

[0144] (Examples 24 to 34, Comparative Example 2) Preparation of Resin Cured Product The resin compositions prepared in Examples 13 to 23 and Comparative Example 1 were poured into a mold (11 cm × 9 cm × 2.4 mm) and heated at 180 °C and 0.5 MPa for 30 minutes using a press machine. The obtained molded product was taken out of the mold and cured at 175 °C for 5 hours to prepare the resin cured products shown in Table 3 below. For the prepared resin cured products, after heating and vacuum drying at 105 °C for 2 hours and storing in a room at a temperature of 23 °C and a humidity of 50% for 24 hours, the dielectric constant and dielectric tangent were measured. A network analyzer E8362C (manufactured by Agilent Technologies, Inc.) was used for the measurement, and the measurement was performed by the cavity resonance method. The measurement results are shown in Table 2 below.

[0145]

Table 3

[0146] As shown in Table 3, it can be seen that the active ester resins (I-1) to (I-7) and (I-9) to (I-12) of the present invention exhibit a lower dielectric tangent at 10 GHz compared to the active ester resin (R-1) of the comparative example.

[0147] (Examples 35 to 40, Comparative Example 3) Preparation of Resin Composition Regarding the active ester resins (I-1) to (I-4) and (I-8) produced in Examples 1 to 4 and Example 8, after distilling off the solvent, the resin solids were obtained by heating under vacuum at 180 °C for 2 hours. Each of the obtained resin solids was dissolved in methyl ethyl ketone to prepare a 65% methyl ethyl ketone solution of each active ester resin. Using the obtained resin solution, each component was blended at the ratios shown in Table 4 below, and then diluted with methyl ethyl ketone so that the non-volatile content (NV) after blending was 60% to prepare a resin composition. As the epoxy resin, dicyclopentadiene phenol type epoxy resin EPICLON HP-7200H-75M (manufactured by DIC Corporation, epoxy equivalent 279 g / equivalent) was used, and 4-dimethylaminopyridine was used as the curing catalyst. The blending ratio of the curing catalyst represents the ratio to the solid content of the active ester resin and the epoxy resin. Further, as the active ester resin of Comparative Example 3, the active ester resin (R-1) produced in Synthesis Reference Example 1 was used.

[0148]

Table 4

[0149] (Examples 41 to 46, Comparative Example 4) Fabrication of Laminated Board Using the resin compositions prepared in Examples 35 to 40 and Comparative Example 3, a laminated board was fabricated under the following conditions. Base material: Glass cloth "#2116" (210 × 280 mm) manufactured by Nitto Boseki Co., Ltd. Copper foil: "JTCSLC foil" (18 μm) manufactured by JX Metals Co., Ltd. Number of plies: 6 Curing conditions: 200 °C, 29 kg / cm 2 for 1.5 hours Thickness after molding: 0.8 mm For the obtained laminate, the dielectric constant and dielectric tangent were measured by the same method as described above. The measurement results are shown in Table 5 below.

[0150]

Table 5

[0151] As shown in Table 5, it can be seen that the active ester resins (I-1) to (I-4) and (I-8) of the present invention exhibit a lower dielectric tangent at 10 GHz compared to the active ester resin (R-1) of the comparative example. Further, it can be seen that the active ester resin of the present invention exhibits a lower dielectric tangent at 10 GHz even when used in combination with an active ester resin other than the present invention. From the above results, it can be seen that the active ester resin of the present invention is a curing agent for epoxy resins capable of providing a cured product having a lower dielectric tangent in the high frequency band.

Claims

1. An active ester resin obtained by reacting a phenolic hydroxyl group-containing resin (A) with an aromatic (poly) carboxylic acid or its acid halide (B), wherein the phenolic hydroxyl group-containing resin (A) uses a phenolic hydroxyl group-containing compound (a1) and an indene structure-containing compound (a2) as essential reaction raw materials, said active ester resin.

2. The phenolic hydroxyl group-containing resin (A) has the following general formula (S) 【Chemical Formula 1】 (In the formula, A １ represents an optionally substituted hydrocarbon ring or heterocyclic ring having 3 to 16 carbon atoms, and L has the following formula (L) 【Chemical Formula 2】 (In the formula, * represents the bonding position with the ring represented by A １ and R １ and R ２ each independently represent a group selected from an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, an aryl group having 3 to 20 carbon atoms, and an aralkyl group having 4 to 20 carbon atoms, provided that when there are a plurality of R １ and R ２ they may be the same or different, R ３ 、R ４ 、R ５ 、R ６ 、R ７ 、R ８ and R ９ each independently represent a group selected from a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a halogen atom, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, provided that when there are a plurality of R ３ 、R ４ 、R ５ 、R ６ 、R ７ 、R ８ and R ９ they may be the same or different, r1 represents an integer from 0 to 4, r2 represents an integer from 0 to 5, n1 represents an integer from 1 to 20, n2 represents an integer from 0 to 20, but the order of each repeating unit enclosed by n1 and n2 is not limited, and the bonding pattern may be alternating, block, or random, and each repeating unit enclosed by n1 and n2 may have the same structure or a plurality of different structures. ) represents a group represented by m, where m is 1 or more and A １ represents an integer less than or equal to the number of ring-constituting atoms that can be substituted in the ring represented by. ) The active ester resin according to claim 1.

3. A phenolic hydroxyl group-containing resin (A), an aromatic (poly) carboxylic acid or its acid halide (B), a hydroxyl group-containing compound or resin, which is a compound or resin (C) different from the phenolic hydroxyl group-containing resin (A), and is obtained by reacting the active ester resin according to claim 1 or claim 2.

4. A resin composition containing the active ester resin according to any one of claims 1 to 3.

5. The resin composition according to claim 4, containing an epoxy resin.

6. The resin composition according to claim 4 or claim 5, containing a phenol resin and / or an active ester resin other than those described in any one of claims 1 to 3.

7. A cured product obtained by curing the resin composition according to any one of claims 4 to 6.

8. A semiconductor encapsulating material, a semiconductor device, a prepreg, a circuit board, a flexible wiring board, a build-up film, a multilayer printed wiring board, a build-up substrate, a fiber-reinforced composite material, or a molded product obtained by curing the fiber-reinforced composite material, using the resin composition according to any one of claims 4 to 6.

9. From the following formula (S111-1) to formula (S111-3) 【Chemical formula 3】 (In the formula, R Ａ represents a linear or branched alkyl group having 1 to 5 carbon atoms, and L １１１ represents the following formula (L111) 【Chemical formula 4】 (In the formula, * represents the bonding position to the ring, and R ７１１１ represents a hydrogen atom or a methyl group, but when there are a plurality of Rs ７１１１ they may be the same or different, n1111 represents an integer from 1 to 10, n2111 represents an integer from 0 to 10, but when n2111 represents an integer of 1 or more, the order of each repeating unit enclosed by n1111 and n2111 is not limited, the bonding mode is random, and each repeating unit enclosed by n2111 may have the same structure or a plurality of different structures.) represents a group represented by, m111 represents an integer from 1 to 7, m112 represents an integer of 1 or more, m113 represents an integer of 1 or more, but m112 + m113 represents an integer of 5 or less.) A phenolic hydroxyl group-containing resin represented by.

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