Active ester resin, resin composition, cured product and phenolic hydroxyl group-containing resin

Abstract

The invention provides an active ester resin, a resin composition, a cured product and a phenolic hydroxyl group-containing resin. The present invention provides an active ester resin obtained by reacting a phenolic hydroxyl group-containing resin (A) using a phenolic hydroxyl group-containing compound (a1) and an indene structure-containing compound (a2) as essential reaction raw materials, and an aromatic (polyvalent) carboxylic acid or an acyl halide (B) thereof.

Description

Technical Field

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

[0002] In recent years, the amount of information processed and the speed of data processing have been increasing due to the sophistication of services using the Internet and the performance and functionality of information terminals and sensors. The higher the frequency of radio waves, the greater the amount of information that can be transmitted. Therefore, research is being conducted to utilize high-frequency bands of tens of GHz or more, and components such as circuit boards and antennas used in corresponding devices require materials with low dielectric loss that can support high-frequency bands.

[0003] The epoxy resin composition containing epoxy resin and curing agent shows high heat resistance and insulation when the resin combination is cured, so it is widely used in electronic components such as semiconductors and circuit substrates.As curing agent, active ester resin (patent documentation 1) with ester structure in molecule has been reported.Compared with the situation of curing agent of the existing type using phenol novolac resin and the like, the epoxy resin composition using active ester resin can obtain the low cured product of dielectric constant and dielectric loss tangent.But, the dielectric properties of the cured product using known active ester resin in high frequency band are insufficient, and it is required to develop the epoxy resin curing agent that can provide the cured product showing lower dielectric loss tangent in high frequency band.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2009-235165 Summary of the invention

[0007] Problems to be solved by the invention

[0008] The problem to be solved by the present invention is to provide an active ester resin having a low dielectric constant and dielectric loss tangent when cured, 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 sealing material.

[0009] Means for solving problems

[0010] The present inventors have conducted intensive research to solve the above-mentioned problems, and as a result, have completed the development of an active ester resin having a specific structure. That is, the present invention provides an active ester resin obtained by reacting a phenolic hydroxyl-containing resin (A) with an aromatic (poly) carboxylic acid or an acyl halide thereof (B), wherein the phenolic hydroxyl-containing resin (A) has a phenolic hydroxyl-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.

[0011] Effects of the Invention

[0012] The active ester resin of the present invention has low dielectric constant and dielectric loss tangent when it is cured, and is therefore useful as a resin composition material for printed wiring boards, build-up films, semiconductor sealing materials, and the like. DETAILED DESCRIPTION

[0013] The present invention provides an active ester resin obtained by reacting a phenolic hydroxyl-containing resin (A) with an aromatic (poly)carboxylic acid or an acyl halide thereof (B), wherein the phenolic hydroxyl-containing resin (A) contains a phenolic hydroxyl-containing compound (a1) and an indene structure-containing compound (a2) as essential reaction raw materials.

[0014] Among the above-mentioned active ester resins, the phenolic hydroxyl group-containing resin (A) is preferably represented by the following general formula (S) from the viewpoint of compatibility with other components when added to the resin composition and solubility in the solvent:

[0015] [Chemistry 1]

[0016]

[0017] In the formula, A 1 represents a hydrocarbon ring or heterocyclic ring having 3 to 16 carbon atoms which may be substituted, L represents a group represented by the following formula (L),

[0018] [Chemistry 2]

[0019]

[0020] In the formula, * indicates the 1 The bonding position of the ring indicated, R 1 and R 2 each independently represents 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, and R 1 and R 2 When there are multiple, they can be the same or different.

[0021] R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Each independently 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, a halogen atom, an aryl group having 3 to 20 carbon atoms, and an aralkyl group having 4 to 20 carbon atoms, and R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 When there are multiple, they can be the same or different.

[0022] r1 represents an integer of 0 to 4, r2 represents an integer of 0 to 5, n1 represents an integer of 1 to 20, and n2 represents an integer of 0 to 20. The order of the repeating units enclosed by n1 and n2 is not limited, and the bonding method may be alternating, block, or random. The repeating units enclosed by n1 and n2 may have the same structure or a plurality of different structures.

[0023] m represents 1 or more, and in A 1 An integer equal to or less than the number of substitutable ring atoms in the represented ring.

[0024] From the viewpoint of ease of synthesis and availability of raw materials, the phenolic hydroxyl group-containing resin (A) is more preferably represented by the following general formula (S1):

[0025] [Chemistry 3]

[0026]

[0027] In the formula, A 11 represents a benzene ring or a naphthalene ring which may be substituted, L 1 represents a group represented by the following formula (L1),

[0028] [Chemistry 4]

[0029]

[0030] In the formula, * indicates the 11 The bonding position of the ring indicated, R 11 and R 21each independently represents a group selected from a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkenyl group having 2 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, and R 11 and R 21 When there are multiple, they can be the same or different.

[0031] R 31 , R 41 , R 51 , R 61 , R 71 , R 81 and R 91 each independently represents a group selected from a hydrogen atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a linear or branched alkenyl group having 2 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, and R 31 , R 41 , R 51 , R 61 , R 71 , R 81 and R 91 When there are multiple, they can be the same or different.

[0032] r11 represents 0, 1 or 2, r21 represents 0, 1, 2 or 3, n11 represents an integer of 1 to 20, n21 represents an integer of 0 to 20, the order of the repeating units bracketed by n11 and n21 is not limited, the bonding method is random, the repeating units bracketed by n11 and n21 can be the same structure or a plurality of different structures, m1 represents 1 or more, and in A 11 An integer less than the number of substitutable ring atoms in the ring represented by

[0033] It is further preferred that the phenolic hydroxyl group-containing resin (A) is represented by the following general formula (S11):

[0034] [Chemistry 5]

[0035]

[0036] In the formula, A 111 represents a benzene ring or a naphthalene ring which may be substituted with a linear or branched alkyl group having 1 to 5 carbon atoms, L 11 represents a group represented by the following formula (L11),

[0037] [Chemistry 6]

[0038]

[0039] In the formula, * indicates the 111 The bonding position of the ring indicated, R 111 and R 211 Each independently represents 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, and R 111 and R 211 When there are multiple, they can be the same or different.

[0040] R 311 , R 411 , R 511 , R 611 , R 711 , R 811 and R 911 Each independently represents a group selected from a hydrogen atom and a linear or branched alkyl group having 1 to 5 carbon atoms, and R 311 , R 411 , R 511 , R 611 , R 711 , R 811 and R 911 When there are multiple, they can be the same or different.

[0041] r111 and r211 each independently represent 0, 1 or 2, n111 represents an integer of 1 to 12, n211 represents an integer of 0 to 12, the order of the repeating units bracketed by n111 and n211 is not limited, the bonding method is random, the repeating units bracketed by n111 and n211 may be the same structure or a plurality of different structures, m11 represents 1 or more, and in A 111 An integer equal to or less than the number of substitutable ring atoms in the represented ring.

[0042] It is particularly preferred that the phenolic hydroxyl group-containing resin (A) is represented by the following formula (S111-1) to formula (S111-3):

[0043] [Chemistry 7]

[0044]

[0045] In the formula, R A represents a linear or branched alkyl group having 1 to 5 carbon atoms, L 111 represents a group represented by the following formula (L111),

[0046] [Chemistry 8]

[0047]

[0048] In the formula, * indicates the bonding position to the ring, R 7111 represents a hydrogen atom or a methyl group. 7111 In the case of , they can be the same or different,

[0049] n1111 represents an integer from 1 to 10, n2111 represents an integer from 0 to 10. When n2111 represents an integer greater than 1, the order of the repeating units enclosed by n1111 and n2111 is not limited, the bonding method is random, and the repeating units enclosed by n2111 may have the same structure or multiple different structures. m111 represents an integer from 1 to 7, m112 represents an integer greater than 1, m113 represents an integer greater than 1, and m112+m113 represents an integer less than 5.

[0050] When the active ester resin of the present invention is added to an epoxy resin composition to produce a resin plate, particularly when the balance between low dielectric loss tangent and high glass transition temperature is important, the phenolic hydroxyl group-containing resin (A) is preferably represented by the formula (S111-1), 111 In the aforementioned formula (L111), n2111 represents 0. In the case of adding the active ester resin of the present invention to an epoxy resin composition to produce a resin plate, especially when low dielectric loss tangent is emphasized, the aforementioned phenolic hydroxyl-containing resin (A) is preferably represented by the aforementioned formula (S111-2) or formula (S111-3). In addition, in the case of adding the active ester resin of the present invention to an epoxy resin composition to produce a resin plate, especially when high glass transition temperature is emphasized, it is preferred that n2111 represents 0 in the aforementioned formulas (S111-1) to (S111-3). In the case of emphasizing the low softening point of the active ester resin of the present invention, it is preferred that n2111 represents an integer greater than 1 in the aforementioned formulas (S111-1) to (S111-3).

[0051] In this specification, a group whose bonding position is not fixed to any atom constituting a ring means a group that can be bonded to any substitutable ring-forming atom in the ring. 111 The group represented by can be bonded to any of the 7 substitutable ring-forming carbon atoms in the naphthalene ring. 111 The group represented and R A The represented group may be bonded to different ring-constituting carbon atoms among the five substitutable ring-constituting carbon atoms in the benzene ring.

[0052] In the active ester resin of the present invention, as long as the aromatic (poly) carboxylic acid or its acyl halide (B) is an aromatic compound that can react with the phenolic hydroxyl group of the resin (A) containing phenolic hydroxyl groups to form an ester bond, the specific structure is not particularly limited and can be any compound. As a specific example, for example, phthalic acid, terephthalic acid and other benzene dicarboxylic acids, trimellitic acid and other benzene tricarboxylic acids, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid and other naphthalene dicarboxylic acids, their acyl halides, and compounds substituted with the aforementioned aliphatic hydrocarbon groups, alkoxy groups, halogen atoms, etc. on their aromatic nuclei, etc. Acyl halides, for example, acyl chlorides, acyl bromides, acyl fluorides, acyl iodides, etc., can be listed. They can be used alone or in combination of two or more. Among them, from the aspect of becoming an active ester resin with high reaction activity and excellent curability, phthalic acid or its acyl halide such as isophthalic acid and terephthalic acid is preferred.

[0053] The active ester resin of the present invention shows a low dielectric loss tangent. From the viewpoint of improving the heat resistance, mechanical strength, adhesion to copper foil, etc. of the cured product, the resin (A) containing a phenolic hydroxyl group, an aromatic (poly) carboxylic acid or its acyl halide (B), and a hydroxyl-containing compound or resin different from the phenolic hydroxyl-containing resin (A) or a resin (C) may be reacted to obtain a resin. In this case, the hydroxyl-containing compound or resin (C) is not particularly limited in specific structure as long as it is a compound or resin that can bring about the desired physical properties, and may be any compound.

[0054] As the aforementioned hydroxyl-containing compound or resin (C), specifically, as examples of compounds having one phenolic hydroxyl group, there can be cited 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, and β-naphthol. From the viewpoint of low dielectric loss tangent of the obtained cured product, α-naphthol, β-naphthol, o-phenylphenol, or p-phenylphenol is preferred.

[0055] In addition, as the aforementioned hydroxyl-containing compound or resin (C), specifically, as examples of compounds having two or more phenolic hydroxyl groups, there can be listed aromatic dihydroxy compounds such as resorcinol, hydroquinone, trimethylhydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,6-naphthalene diol, 2,6-naphthalene diol, 2,3-naphthalene diol, 2,7-naphthalene diol, 1,4-naphthalene diol, 3,3',5,5'-tetramethylbisphenol F, 3,3',5,5'-tetramethylbiphenol; aromatic trihydroxy compounds such as 1,3,5-trihydroxybenzene, 1,2,3-trihydroxybenzene, 2,4,4'-trihydroxybenzophenone, triphenol methane; 2,2',4,4'-tetrahydroxybenzophenone, 1,1,2,2-tetraphenol ethane, etc. From the viewpoint of low dielectric loss tangent of the obtained cured product, bisphenol A, bisphenol F, bisphenol S, 3,3',5,5'-tetramethylbisphenol F, or 3,3',5,5'-tetramethylbiphenol is preferred.

[0056] In addition, the aforementioned hydroxyl-containing compound or resin (C) may be a compound or resin represented by the following general formula (S2):

[0057] [Chemistry 9]

[0058]

[0059] In the formula, A 2 , A 3 and A 4 Each independently represents a hydrocarbon ring or heterocyclic ring having 3 to 16 carbon atoms which may be substituted, 3 When there are multiple, they can be the same or different, 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, and Z 1 When there are a plurality of them, they may be the same or different, and m2 represents an integer of 0 to 20.

[0060] In the compound or resin represented by the general formula (S2), HO-A 2 , A 3 -OH and A 4 Specific examples of the group represented by -OH include 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, and β-naphthol.

[0061] In the compound or resin represented by the general formula (S2), Z1 and Z 2 Specific examples of the group represented by include 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 groups represented by the following formulas (Z-1) to (Z-10).

[0062] [Chemistry 10]

[0063]

[0064] In the formula, * indicates the 2 , A 3 and A 4 The bonding position of the ring represented by 1 and Z 2 The group represented is preferably 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 from the viewpoint of adhesion and dielectric properties, and is particularly preferably selected from the group in the aforementioned formula (Z-3) to formula (Z-10). In addition, from the viewpoint of solubility in a solvent, m2 is preferably an integer of 0 to 5.

[0065] In addition, the aforementioned hydroxyl-containing compound or resin (C) may be a compound or resin represented by the following formula (S2-1):

[0066] [Chemistry 11]

[0067]

[0068] 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.

[0069] In the compound or resin represented by the aforementioned formula (S2-1), as R 21 Specific examples thereof 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, etc. m21 preferably represents an integer of 1 to 15, and more preferably represents an integer of 1 to 12.

[0070] Specific examples of the active ester resin of the present invention include resins represented by the following formulas (E-1) to (E-16):

[0071] [Chemistry 12]

[0072]

[0073] [Chemistry 13]

[0074]

[0075] [Chemistry 14]

[0076]

[0077] [Chemistry 15]

[0078]

[0079] [Chemistry 16]

[0080]

[0081] Where, L a , L b and L c represent groups represented by the following formula (La), formula (Lb) and formula (Lc), respectively,

[0082] [Chemistry 17]

[0083]

[0084] In the formula, * represents the bonding position to the ring, na, nb and nc each independently represent an integer of 1 to 20, 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 of 0 to 40, k represents an integer of 0 to 7, l represents an integer of 0 to 5, p represents an integer of 0 to 4, q represents an integer of 0 to 3, r represents an integer of 0 to 6, s represents 0, 1 or 2, and the total of k, l, p and q in the molecule is 1 or more.

[0085] The active ester resin of the present invention can be produced by the following production method.

[0086] (Preparation method 1) Preparation of active ester resin represented by the following formula (M6)

[0087] [Chemistry 18]

[0088]

[0089] In the formula, * indicates the bonding position to the ring, R 1 , R 2 , R 3 , R 4 , R 5 , R6 , R 7 , R 8 , R 9 , r1, r2, n1 and n2 respectively represent the R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , r1, r2, n1 and n2 have the same meanings, k represents an integer of 0 to 7, and the total number of k contained in the active ester resin represented by formula (M6) is 1 or more.

[0090] By reacting the phenolic hydroxyl-containing compound represented by formula (M1), for example, with the indene structure-containing compound represented by formula (M2) and the compound represented by formula (M3) in the presence of an acid, a phenolic hydroxyl-containing resin represented by formula (M4) can be obtained. As the acid, for example, 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 ferric chloride; solid acids such as activated clay. When the theoretical amount of the obtained phenolic hydroxyl-containing resin is set to 100 parts by mass, the amount of 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 a solid acid is used, the theoretical amount of the obtained phenolic hydroxyl group-containing resin is preferably 0.01 to 100 parts by mass, more preferably 0.1 to 50 parts by mass, and particularly preferably 1 to 20 parts by mass, based on 100 parts by mass of the theoretical amount of the obtained phenolic hydroxyl group-containing resin.

[0091] The reaction of the compound containing phenolic hydroxyl group represented by formula (M1), the compound containing indene structure represented by formula (M2), and the compound represented by formula (M3) can be carried out without solvent or in solvent. As the solvent, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, benzene, toluene, xylene, chlorobenzene, cyclohexane, and dichloromethane can be listed. From the viewpoint of reactivity and ease of post-treatment, toluene or xylene is preferred.

[0092] The reaction method may be a method of mixing a phenolic hydroxyl-containing compound represented by formula (M1), a compound containing an indene structure 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-containing compound represented by formula (M1), an acid and a reaction solvent and then adding a compound containing an indene structure represented by formula (M2) and a compound represented by formula (M3). The reaction temperature is not particularly limited, and from the viewpoints of the viscosity of the obtained phenolic hydroxyl-containing resin represented by formula (M4), solubility in the solvent, etc., it is preferably -30°C or more and 200°C or less, more preferably -20°C or more and 150°C or less, and particularly preferably 0°C or more and 80°C or less. After the reaction, in order to reduce the unreacted components, aging is preferably performed. As the aging temperature, it is preferably 0°C or more and 200°C or less, more preferably 20°C or more and 150°C or less, and particularly preferably 40°C or more and 130°C or less. After the reaction, the acid is removed by neutralization, water washing, filtration or decomposition, and the target phenolic hydroxyl-containing resin can be separated by general operations such as extraction and distillation. The neutralization treatment and water washing treatment can be carried out according to conventional methods, for example, alkaline substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, and ammonia can be used as neutralizers.

[0093] Next, by reacting the phenolic hydroxyl-containing resin represented by formula (M4) with the compound represented by formula (M5) in the presence of a base, an active ester resin represented by formula (M6) can be obtained. Examples of the base include sodium hydroxide, potassium hydroxide, triethylamine, pyridine, etc. Among them, sodium hydroxide and potassium hydroxide can be used in the form of an aqueous solution, which is particularly preferred from the perspective of good productivity.

[0094] The reaction method may be: in the presence of an organic solvent, a phenolic hydroxyl-containing resin represented by formula (M4) and a compound represented by formula (M5) are mixed, and a base or its aqueous solution is continuously or intermittently added dropwise to react. 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. As organic solvents, toluene, dichloromethane, chloroform, etc. may be cited. After the reaction, the base is neutralized and washed with water, thereby obtaining an active ester resin represented by formula (M6).

[0095] (Preparation method 2) Preparation of active ester resin represented by the following formula (M12)

[0096] [Chemistry 19]

[0097]

[0098] In the formula, * indicates the bonding position to the ring, R 1 , R 3 , R 4 , R 5 , R6 and n1 respectively represent the R 1 , R 3 , R 4 , R 5 , R 6 Same meaning as n1, A 2 , A 4 and Z 2 Respectively represent A in the general formula (S2) 2 , A 4 and Z 2 The same meanings are given, wherein n represents an integer of 0 to 40, k represents an integer of 0 to 7, and the total number of k contained in the active ester resin represented by the formula (M12) is 1 or more.

[0099] The phenolic hydroxyl-containing compound represented by formula (M7) can be reacted with the indene-containing compound represented by formula (M8) in the presence of an acid to obtain a phenolic hydroxyl-containing resin represented by formula (M9). The conditions such as acid, solvent, and temperature are the same as those in Preparation Method 1.

[0100] Next, the phenolic hydroxyl-containing resin represented by formula (M9) is reacted with the compound represented by formula (M10) and the hydroxyl-containing compound represented by formula (M11) in the presence of a base, thereby obtaining an active ester resin represented by formula (M12). Examples of the base include sodium hydroxide, potassium hydroxide, triethylamine, pyridine, etc. Among them, sodium hydroxide and potassium hydroxide can be used in the form of an aqueous solution, which is particularly preferred from the perspective of good productivity.

[0101] The reaction method may be: in the presence of an organic solvent, a phenolic hydroxyl-containing resin represented by formula (M9), a compound represented by formula (M10), and a hydroxyl-containing compound represented by formula (M11) are mixed, and a base or its aqueous solution is continuously or intermittently added dropwise to react. 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. As organic solvents, toluene, dichloromethane, chloroform, etc. may be cited. After the reaction, the base is neutralized and washed with water, thereby obtaining an active ester resin represented by formula (M12).

[0102] When the softening point of the active ester resin of the present invention obtained in this way is 70° C. or higher and 200° C. or lower, the solubility in organic solvents becomes high, and it becomes a material suitable for varnish for circuit boards. In addition, it is preferred from the perspective of excellent balance among heat resistance, flame retardancy, dielectric properties, and resistance to thermal decomposition.

[0103] When the total number of aromatic ester groups in the molecule is taken as the number of functional groups of the active ester, 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 viewpoint of curability and dielectric properties.

[0104] From the viewpoint of curability, dielectric properties, and compatibility with other components, the number average molecular weight (Mn) of the active ester resin of the present invention is preferably 300 to 5000, more preferably 400 to 4000, particularly preferably 500 to 3000.

[0105] <Resin composition>

[0106] The active ester resin of the present invention has a function as a curing agent for epoxy compounds and other compounds. The active ester resin of the present invention can prevent or suppress the generation of hydroxyl groups when reacting with epoxy resins, thereby obtaining a cured product with excellent low dielectric properties, which is useful.

[0107] Specific examples of the epoxy resin used in combination 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 novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac 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 novolac type epoxy resin, naphthol novolac type epoxy resin, naphthalene type epoxy resin, Phenol 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 polyphenol type epoxy resin formed by connecting a phenol skeleton and a biphenyl skeleton through a dimethylene group), biphenyl modified naphthol type epoxy resin (a polynaphthol type epoxy resin formed by connecting a naphthol skeleton and a biphenyl skeleton through a dimethylene group), alkoxy-containing aromatic ring modified novolac type epoxy resin (a resin formed by connecting an aromatic ring containing a glycidyl group and an aromatic ring containing an alkoxy group with formaldehyde), phenylene ether type epoxy resin, naphthylene ether type epoxy resin, aromatic hydrocarbon formaldehyde resin modified novolac type epoxy resin, xanthene type epoxy resin, etc. These can be used alone or in combination of two or more.

[0108] Among the above epoxy resins, phenol novolac type epoxy resins, cresol novolac type epoxy resins, bisphenol A novolac type epoxy resins, polyhydroxy naphthalene type epoxy resins, triphenylmethane type epoxy resins, tetraphenylethane type epoxy resins, biphenyl novolac type epoxy resins, naphthol novolac type epoxy resins, naphthol-phenol co-decanoic acid novolac type epoxy resins, naphthol-cresol co-decanoic acid novolac type epoxy resins, phenylene ether type epoxy resins, naphthylene ether type epoxy resins, xanthene type epoxy resins are preferred, and dicyclopentadiene-phenol addition reaction type epoxy resins, naphthol novolac type epoxy resins, phenol aralkyl type epoxy resins are particularly preferred. Ester, 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 polyphenol type epoxy resin in which a phenol skeleton and a biphenyl skeleton are connected by a dimethylene group), biphenyl modified naphthol type epoxy resin (a polynaphthol type epoxy resin in which a naphthol skeleton and a biphenyl skeleton are connected by a dimethylene group), alkoxy-containing aromatic ring modified novolac type epoxy resin (a resin in which an aromatic ring containing a glycidyl group and an aromatic ring containing an alkoxy group are connected by formaldehyde), aromatic hydrocarbon formaldehyde resin modified novolac type epoxy resin, and naphthylene ether type epoxy resin.

[0109] Specific examples of commercially available epoxy resins to be mixed 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-4850-200, EPICLON HP-4850-300, EPICLON HP-4850-400, EPICLON HP-4850-500, EPICLON HP-4850-600, EPICLON HP-4850-700, EPICLON HP-4850-800, EPICLON HP-4850-900, EPICLON HP-4850-1000, EPICLON HP-4850-1000 HP-4710, EPICLON HP-4770, EPICLON HP-5000, EPICLON HP-9900-75M, EPICLON HP-9500, EPICLON HP-6000, EPICLON HP-6000L (all 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, Epotohto YSLV-120TE (all manufactured by Nippon Steel Chemicals 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, jER8000, jER YX8034, jER YL980, jER YL983U, jER YX7400N, jER YX7105, jER YX7110B80, jERYX7760, jER YX4000, jER YX4000H, jER 4000HS, jER YL6121HA, jER YL6677 (all 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 (all manufactured by Nippon Kayaku Co., Ltd.), etc.

[0110] Regarding the amount of the active ester resin and the epoxy resin in the resin composition of the present invention, the carbonyloxy group constituting the ester group in the active ester resin is preferably in a ratio of 0.8 equivalents to 1.5 equivalents per 1 equivalent of the epoxy group in the resin composition from the viewpoint of improving the curability and various physical properties of the cured product, and is particularly preferably in a ratio of 0.9 equivalents to 1.3 equivalents from the viewpoint of improving the dielectric properties and heat resistance of the cured product while maintaining excellent flame retardancy.

[0111] <Other curing agents>

[0112] In addition to the aforementioned active ester resin and epoxy resin, the resin composition of the present invention can also be used in combination with other epoxy resin curing agents. As other epoxy resin curing agents, for example, amine curing agents, amide curing agents, acid anhydride curing agents, phenol curing agents, etc. can be listed. As amine curing agents, for example, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenyl sulfone, isophoronediamine, imidazole, boron trifluoride-amine complex, guanidine derivatives, etc. can be listed, as amide curing agents, dicyandiamide, polyamide resin synthesized from dimer of linolenic acid and ethylenediamine, etc. can be listed, as acid anhydride curing agents, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc. can be listed, as phenol curing agents, phenol novolac resin can be listed. Resins, cresol novolac resins, phenol-formaldehyde resins modified by aromatic hydrocarbon formaldehyde resins, dicyclopentadiene phenol addition resins, phenol aralkyl resins, naphthol aralkyl resins, trimethylolmethane resins, tetrahydroxyphenylethane resins, naphthol novolac resins, naphthol-phenol co-condensed phenol-formaldehyde resins, naphthol-cresol co-condensed phenol-formaldehyde resins, biphenyl-modified phenol-formaldehyde resins (polyphenol resins in which phenol cores are connected by dimethylene), biphenyl-modified naphthol resins (polyphenol resins in which phenol cores are connected by dimethylene), aminotriazine-modified phenol-formaldehyde resins (polyphenol resins in which phenol cores are connected by melamine, benzoguanamine, etc.), etc.

[0113] Among them, from the viewpoint of flame retardant effect, resins containing a large amount of aromatic skeletons in the molecular structure are particularly preferred, and specifically, phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resins, phenol aralkyl resins, naphthol aralkyl resins, naphthol novolac resins, naphthol-phenol co-condensed phenolic varnish resins, naphthol-cresol co-condensed phenolic varnish resins, biphenyl-modified phenolic resins, biphenyl-modified naphthol resins, and aminotriazine-modified phenolic resins are preferred.

[0114] Examples of commercially available curing agents for other epoxy resins used in combination with the active ester resin of the present invention include PHENOLITE (registered trademark) 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 (all 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 (all manufactured by Air Water Performance Chemicals Co., Ltd.), KAYAHARD (registered trademark) GPH-65, KAYAHARD GPH-103, KAYAHARD KTG-105 (manufactured by Nippon Kayaku Co., Ltd.), jERCURE (registered trademark) 170, jERCURE 171N (manufactured by Mitsubishi Chemical Corporation), Milex (registered trademark) XL, Milex RS, Milex RN (manufactured by Mitsui Chemicals Fine Chemicals, Ltd.), ZX-798P (manufactured by Nippon Steel Chemicals Co., Ltd.), as amine-based curing agents, EPICLON B-065 (manufactured by DIC Corporation), KAYAHARD AA (manufactured by Nippon Kayaku Co., Ltd.), jERCURE ST14, jERCURE YN100, jERCURE SA1, jERCURE TO184, jERCURE WA (manufactured by Mitsubishi Chemical Corporation), as acid anhydride-based curing agents,Examples include EPICLON B-4500MC-C, EPICLON B-4500-C, EPICLON B-4500MC (all manufactured by DIC Corporation), HN-2200, MHAC-P (all manufactured by Resonac Corporation), KAYAHARD MCD (manufactured by Nippon Kayaku Co., Ltd.), jERCURE YH306, and jERCURE YH307 (all manufactured by Mitsubishi Chemical Corporation).

[0115] The above-mentioned other curing agents may be used alone or in combination of two or more.

[0116] In addition, the resin composition of the present invention can also use active ester resins other than the active ester resin of the present invention as epoxy resin curing agent. As active ester resins other than the active ester resin of the present invention, for example, EPICLON (registered trademark) HPC-8000-65T, EPICLON HPC-8000L-65MT, EPICLON HPC-8150-62T, EPICLONEXB-8, EPICLON NE-V-1100-70T (the above are made by DIC Corporation).

[0117] <Other thermosetting resins>

[0118] The resin composition of the present invention can also be used in combination with other thermosetting resins in addition to the above-described active ester resins and epoxy resins. As other thermosetting resins, for example, maleimide resins, bismaleimide resins, polymaleimide resins, polyphenylene oxide resins, polyimide resins, cyanate resins, benzoxazine resins, cresol novolac resins containing triazine, cyanate resins, styrene-maleic anhydride resins, diallyl bisphenol, triallyl isocyanurate and other allyl-containing resins, polyphosphates, phosphate-carbonate copolymers, etc. can be cited. These other resins can be used alone or in combination of two or more.

[0119] <Solvent>

[0120] The resin composition of the present invention can be prepared without solvent, or it can contain a solvent. The solvent has functions such as adjusting the viscosity of the resin composition. As a solvent, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ether solvents such as diethyl ether, tetrahydrofuran, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate and other ester solvents, cellosolve, butyl carbitol and other carbitols, toluene, xylene, ethylbenzene, mesitylene, 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene and other aromatic hydrocarbons, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone and other amide solvents can be listed. These solvents can be used alone or in combination of two or more.

[0121] As the usage amount of the aforementioned solvent, relative to the gross mass of the resin combination, it is preferably more than 10 mass % and less than 90 mass %, more preferably more than 20 mass % and less than 80 mass %. When the usage amount of the solvent is more than 10 mass %, it is excellent in operability, so it is preferred. On the other hand, from the viewpoint of economy, the usage amount of the preferred solvent is less than 90 mass %.

[0122] <Additives>

[0123] The resin composition of the present invention may contain additives, such as curing accelerators, flame retardants, and fillers.

[0124] <Curing Accelerator>

[0125] Examples of the curing accelerator include a phosphorus-based curing accelerator, an amine-based curing accelerator, an imidazole-based curing accelerator, a guanidine-based curing accelerator, and a urea-based curing accelerator.

[0126] Examples of the phosphorus-based curing accelerator include organic phosphine compounds such as triphenylphosphine, tributylphosphine, tri-p-tolylphosphine, diphenylcyclohexylphosphine, and tricyclohexylphosphine, organic phosphite compounds such as trimethyl phosphite and triethyl phosphite, ethyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, butyltetraphenylphosphonium borate, tetraphenylphosphonium borate, tetraphenyltetra-p-tolylphosphonium borate, triphenylphosphine triphenylborane, tetraphenylphosphonium thiocyanate, tetraphenyldicyanamide phosphonium, butylphenyldicyanamide phosphonium, and phosphonium salts such as tetrabutyldecanoate.

[0127] 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), and 1,5-diazabicyclo[4.3.0]-nonene-5-(DBN).

[0128] Examples of the imidazole curing accelerator 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, and 1-cyanoethyl-2-methylimidazole. 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-benzylimidazole chloride, 2-methylimidazoline, etc.

[0129] Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-butylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, and 1-phenylbiguanidine.

[0130] Examples of the urea-based curing accelerator include 3-phenyl-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, chlorophenylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, and 3-(3,4-dichlorophenyl)-1,1-dimethylurea.

[0131] Among the above-mentioned curing accelerators, 2-ethyl-4-methylimidazole and N,N-dimethylaminopyridine (DMAP) are preferably used. It should be noted that the above-mentioned curing accelerators may be used alone or in combination of two or more.

[0132] The amount of the curing accelerator used can be appropriately adjusted to obtain the desired curability, and is preferably 0.01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, relative to 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 parts by mass or more, the curability is excellent, so it is preferred. On the other hand, when the amount of the curing accelerator used is 5 parts by mass or less, the insulation reliability is excellent, so it is preferred.

[0133] <Flame retardant>

[0134] 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.

[0135] The inorganic phosphorus-based flame retardant is not particularly limited, and examples thereof include red phosphorus, ammonium phosphates such as monoammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate, and phosphoric acid amides.

[0136] 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, lignoceryl acid phosphate, ethylene glycol acid phosphate, and methacrylate (2-hydroxyethyl) acid phosphate; diphenylphosphines such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and diphenylphosphine oxide; and 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10 -oxide, 10-(1,4-dioxynaphthalene)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, diphenylphosphinylhydroquinone, diphenylphosphinyl-1,4-dioxynaphthalene, 1,4-cyclooctylphosphinyl-1,4-phenyldiphenol, 1,5-cyclooctylphosphinyl-1,4-phenyldiphenol and the like phosphorus-containing phenols; 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,5-dihydrooxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and the like cyclic phosphorus compounds; compounds obtained by reacting the aforementioned phosphate esters, the aforementioned diphenylphosphine, the aforementioned phosphorus-containing phenols with epoxy resins, aldehyde compounds, phenol compounds, and the like.

[0137] The halogen 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, and tetrabromophthalic acid.

[0138] The flame retardants mentioned above may be used alone or in combination of two or more.

[0139] The amount of the flame retardant is preferably 0.1 to 50 parts by mass, more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the epoxy resin. When the amount of the flame retardant is 0.1 parts by mass or more, it is preferred because it can impart flame retardancy. On the other hand, when the amount of the flame retardant is 50 parts by mass or less, it is preferred because it can impart flame retardancy while maintaining dielectric properties.

[0140] <Filling Agent>

[0141] Examples of fillers include organic fillers and inorganic fillers. Organic fillers have functions of increasing elongation and mechanical strength, while inorganic fillers have functions of reducing thermal expansion coefficient and imparting flame retardancy.

[0142] The organic filler is not particularly limited, and examples thereof include polyamide particles.

[0143] As the aforementioned inorganic filler, there is no particular restriction, and silicon dioxide, aluminum oxide, 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, barium zirconate, calcium zirconate, zirconium phosphate, zirconium tungstate phosphate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, carbon black, etc. can be listed. Among them, silicon dioxide is preferably used. At this time, as silicon dioxide, amorphous silicon dioxide, fused silica, crystalline silica, synthetic silica, and hollow silica can be listed.

[0144] In addition, the aforementioned filler can be surface treated as needed. As a surface treatment agent, there is no particular limitation, and aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organic silicon azane compounds, titanate coupling agents, etc. can be listed. As a specific example of a surface treatment agent, 3-glycidoxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, hexamethyldisilazane, etc. can be listed.

[0145] The aforementioned fillers may be used alone or in combination of two or more.

[0146] Relative to 100 parts by mass of epoxy resin, the usage amount of the aforementioned filler 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. When the usage amount of the filler is 0.5 parts by mass or more, the effect of the filler can be fully imparted, so it is preferred. On the other hand, in order not to damage the moldability due to the viscosity of the compound becoming high, the usage amount of the filler is preferably 95 parts by mass or less.

[0147] <Cured product>

[0148] The present invention relates to a cured product obtained by curing the resin composition. The active ester resin itself has a low dielectric loss tangent, so 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.

[0149] 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 preferably 100° C. to 300° C., and the heating time is preferably 1 hour to 24 hours.

[0150] <Application of resin composition>

[0151] As the purposes of using the resin composition of the present invention, the insulating materials for circuit substrates such as printed wiring board materials, flexible wiring substrate resin compositions, laminated substrate interlayer insulating materials, laminated adhesive films, resin casting materials, adhesives, semiconductor sealing materials, semiconductor devices, prepregs, conductive pastes, laminated films, laminated substrates, fiber-reinforced composite materials, and molded products formed by curing the above-mentioned composite materials can be listed. In these various purposes, in printed wiring board materials, circuit substrate insulating materials, and laminated adhesive films, it is possible to use the insulating materials used for the so-called electronic component built-in substrates that passive components such as capacitors and active components such as IC chips are buried in the substrate. And then, among the above, because the cured product has low dielectric properties, the resin composition of the present invention is preferably used for semiconductor sealing materials, semiconductor devices, prepregs, circuit substrates, flexible wiring substrates, laminated films, multilayer printed wiring boards, laminated substrates, fiber-reinforced composite materials, and molded products formed by curing the above-mentioned composite materials. Below, the method for manufacturing the above-mentioned semiconductor sealing materials, etc. by resin composition is described.

[0152] "Semiconductor sealing materials"

[0153] The present invention relates to a semiconductor sealing material, characterized in that it contains the aforementioned resin composition. As a method for obtaining a semiconductor sealing material from the resin composition of the present invention, it can be cited that the resin composition of the present invention, a curing accelerator and an inorganic filler and other compounding agents are fully melt-mixed to a uniform method using an extruder, a kneader, a roller, etc. as needed. At this time, as an inorganic filler, fused silica is generally used, but in the case of being used as a power transistor, a power IC with a high thermal conductivity semiconductor sealing material, crystalline silica, alumina, silicon nitride, etc. having a thermal conductivity higher than fused silica can be used. Its filling rate is relative to every 100 parts by mass of the resin composition, preferably using an inorganic filler in a range of more than 30 parts by mass and less than 95 parts by mass, in order to achieve flame retardancy, moisture resistance, improvement of solder crack resistance, reduction of linear expansion coefficient, more preferably more than 70 parts by mass, more preferably more than 80 parts by mass.

[0154] "Semiconductor device"

[0155] The present invention relates to a semiconductor device comprising a cured product obtained by heating and curing the semiconductor sealing material. As a method for obtaining a semiconductor device from the resin composition of the present invention, there can be cited a method in which the semiconductor sealing material is cast, or molded using a transfer molding machine, an injection molding machine, etc., and then heated at 50° C. to 200° C. for 2 hours to 10 hours.

[0156] "Prepreg"

[0157] The present invention relates to a prepreg having a reinforcing substrate and a semi-cured product of the resin composition impregnated in the reinforcing substrate. As a method for obtaining a prepreg from the resin composition of the present invention, the following method can be cited: after impregnating a reinforcing substrate (paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass fiber mat, glass fiber untwisted yarn (glass roving cloth) etc.) with a resin composition varnished with an organic solvent, the prepreg is obtained by heating at a heating temperature corresponding to the type of solvent used, preferably above 50°C and below 170°C. The mass ratio of the resin composition to the reinforcing substrate used at this time is not particularly limited, and it is generally preferred to prepare the prepreg in a manner such that the resin component in the prepreg is 20% by mass or more and 60% by mass or less.

[0158] 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, and the like. The selection and appropriate amount of the organic solvent used can be appropriately selected depending on the intended use. For example, in the case of further manufacturing a printed circuit board from the prepreg as described below, it is preferred to use a polar solvent having a boiling point of 160° C. or less, such as methyl ethyl ketone, acetone, and N,N-dimethylformamide. In addition, it is preferred to use the organic solvent in a ratio where the non-volatile component is 40% by mass or more and 80% by mass or less.

[0159] "Circuit board"

[0160] The present invention relates to a circuit board obtained by laminating the above-mentioned prepreg and copper foil and heat-compression-bonding. As a method for obtaining a printed circuit board from the resin composition of the present invention, there can be cited a method of laminating the above-mentioned prepreg, appropriately overlapping copper foil, and heat-compression-bonding at a pressure of 1 MPa to 10 MPa, at a temperature of 170° C. to 300° C. for 10 minutes to 3 hours.

[0161] "Flexible wiring board"

[0162] As a method for manufacturing a flexible wiring substrate from the resin composition of the present invention, a method of manufacturing by a method consisting of the following three steps can be cited. 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 coating machine such as a reverse roll coater or a comma coater. The second step is a step of using a heater to heat the electrically insulating film coated with the resin composition at a temperature of 60°C to 170°C for a period of 1 minute to 15 minutes to volatilize the solvent from the electrically insulating film and convert the resin composition into a B-stage. The third step is to use a heating roller or the like to hot-press a metal foil on an adhesive on the electrically insulating film after the resin composition has been converted into a B-stage (the pressing pressure is preferably 2N / cm 2 Above and 200N / cm 2 The process of pressing the resin composition film after the final curing is preferably in the range of 5 μm to 100 μm. The process of pressing the resin composition film after the final curing is preferably in the range of 5 μm to 100 μm.

[0163] "Laminated Film"

[0164] The present invention relates to a laminated film containing the resin composition of the present invention. As a method for producing the laminated film of the present invention, there can be mentioned a method of producing an adhesive film for a multilayer printed wiring board by coating the resin composition of the present invention on a support film to form a resin composition layer.

[0165] In the case of manufacturing a laminated film from a resin composition, it is important that the film softens under the lamination temperature conditions in the vacuum lamination method (usually above 70°C and below 140°C) and exhibits fluidity (resin flow) capable of filling the vias or through holes of the circuit substrate while laminating the circuit substrate. It is preferred to combine the above-mentioned components to exhibit such characteristics.

[0166] Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 mm to 0.5 mm, and the depth is usually 0.1 mm to 1.2 mm, and it is usually preferable to fill the resin within this range. It should be noted that in the case of laminating both sides of the circuit board, it is preferable to fill about 1 / 2 of the through hole.

[0167] The method for manufacturing the above-mentioned adhesive film can be specifically manufactured as follows: after preparing the above-mentioned varnish-like resin composition, the varnish-like composition is applied to the surface of the support film (Y), and the organic solvent is further dried by heating or blowing hot air, etc. to form a composition layer (X) composed of the resin composition. The thickness of the formed composition layer (X) is usually preferably greater than the thickness of the conductor layer. The thickness of the conductor layer possessed by the circuit substrate is usually in the range of more than 5 μm and less than 70 μm, so the thickness of the resin composition layer preferably has a thickness of more than 10 μm and less than 100 μm. It should be noted that the composition layer (X) in the present invention can be protected by a protective film described later. By protecting with a protective film, dust and the like can be prevented from adhering to the surface of the resin composition layer or being damaged.

[0168] The supporting film and the protective film may include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and release paper, copper foil, aluminum foil, and other metal foils. It should be noted that the supporting film and the protective film may be subjected to a release treatment in addition to a matte treatment and a corona treatment.

[0169] The thickness of the support film is not particularly limited, but is usually 10 μm to 150 μm, preferably 25 μm to 50 μm. The thickness of the protective film is preferably 1 μm to 40 μm.

[0170] 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 the adhesion of dust and the like during the curing process. In the case of peeling off after curing, the support film is usually subjected to a demolding treatment in advance.

[0171] "Multilayer printed wiring board"

[0172] A multilayer printed wiring board can be manufactured using the laminated film produced by the above method. Regarding the method for manufacturing such a multilayer printed wiring board, for example, when the composition layer (X) is protected by a protective film, after peeling them off, the composition layer (X) is directly laminated on one or both sides of the circuit substrate by, for example, a vacuum lamination method. The lamination method can be intermittent or continuous using a roller. In addition, the adhesive film and the circuit substrate can be heated (preheated) as needed before lamination. The lamination conditions are: preferably, the crimping temperature (lamination temperature) is set to above 70°C and below 140°C, and the crimping pressure is preferably set to 1kgf / cm 2 Above and 11kgf / cm 2 Below (9.8×10 4 N / m 2 Above and 107.9×10 4 N / m 2 The lamination is preferably carried out under a reduced pressure of 20 mmHg (26.7 hPa) or less.

[0173] "Laminated substrate"

[0174] As a method for manufacturing a laminated substrate from the resin composition of the present invention, there can be cited a method of manufacturing by a method consisting of the following three steps. The first step is to apply a resin composition appropriately mixed with rubber, filler, etc. to a circuit substrate formed with a circuit by spraying, curtain coating, etc., and then solidify it. The second step is to open a predetermined through-hole portion, etc. as needed, treat it with a roughening agent, wash its surface with hot water to form unevenness, and plate it with metals such as copper and treat it. The third step is to repeat such operations in sequence as desired, and alternately laminate to form a resin insulating layer and a conductor layer of a predetermined circuit pattern. It should be noted that the opening of the through-hole portion is preferably performed after the outermost resin insulating layer is formed. In addition to the method of coating the above-mentioned solution, the first step can also be performed by laminating a laminated film that has been pre-coated to a desired thickness and dried. In addition, the laminated substrate of the present invention can also be manufactured by heat-compression bonding a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil to a wiring substrate formed with a circuit at a temperature of 170° C. to 250° C., thereby omitting the steps of forming a roughened surface and plating treatment.

[0175] "Fiber-reinforced composites"

[0176] As a method for manufacturing a fiber-reinforced composite material from the resin composition of the present invention, a varnish can be prepared by uniformly mixing the components constituting the resin composition, and then impregnating it into a reinforcing substrate composed of reinforcing fibers and curing it. Specifically, the curing temperature is preferably a temperature range of 50°C or more and 250°C or less, and it is particularly preferred to cure it at 50°C or more and 100°C or less to form a non-sticky cured product, and then further treat it at a temperature condition of 120°C or more and 200°C or less. As reinforcing fibers, twisted yarns, untwisted yarns or untwisted yarns can be used. From the perspective of both the moldability and mechanical strength of fiber-reinforced plastic components, untwisted yarns and untwisted yarns are preferred. Furthermore, the form of the reinforcing fibers can use a form or fabric in which the fiber direction is aligned in one direction. For fabrics, it can be freely selected from plain weaves, satin weaves, etc. according to the location and purpose of use. Specifically, from the perspective of excellent mechanical strength and durability, carbon fibers, glass fibers, aramid fibers, boron fibers, alumina fibers, silicon carbide fibers, etc. can be listed, and two or more of them can also be used in combination. Among them, carbon fibers are preferred from the viewpoint of good strength of the molded product, and various carbon fibers such as polyacrylonitrile, pitch, and rayon can be used as the carbon fibers. Among them, polyacrylonitrile carbon fibers are preferred because they can easily produce high-strength carbon fibers. Here, the amount of reinforcing fibers used when the varnish is impregnated into a reinforcing substrate composed of reinforcing fibers to prepare a fiber-reinforced composite material is preferably an amount that makes the volume content of the reinforcing fibers in the fiber-reinforced composite material range from 40% to 85%.

[0177] "Fiber-reinforced resin molded products"

[0178] As a method for manufacturing a fiber-reinforced resin molded article from the resin composition of the present invention, examples include: the hand lay-up method of laying fiber aggregates on a mold and laminating the aforementioned varnish in multiple layers, the spraying method; manufacturing a prepreg in which the aforementioned varnish is impregnated into reinforcing fibers by methods such as the vacuum bag method, the SMC pressing method, and the RTM method, and then baking and solidifying it in a large autoclave. Among them, in the vacuum bag method, either a male mold or a female mold is used, and while impregnating the varnish into a base material composed of reinforcing fibers, lamination and molding are performed, and then a flexible mold capable of applying pressure to the molded article is covered, and the airtight sealed product is subjected to vacuum (reduced pressure) molding. In the SMC pressing method, a product in which a varnish containing reinforcing fibers has been previously formed into a sheet is compression molded using a mold. In the RTM method, the aforementioned varnish is injected into a combined mold covered with fibers. The obtained fiber-reinforced resin molded article is a molded article having a cured product of reinforcing fibers and a resin composition. Specifically, the amount of reinforcing fibers 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.

[0179] The method for manufacturing a semiconductor sealing material, etc. has been described above, but 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 following the general curing method of resin compositions. For example, the heating temperature conditions can be appropriately selected according to the type and use of the curing agent combined, etc.

[0180] Examples

[0181] Hereinafter, examples are listed to further describe the present invention, but the present invention is not limited to these examples. In addition, "%" in the compositions of the following examples and comparative examples refers to "% by mass". It should be noted that the measurement conditions of GPC, 13 13C NMR, and MALDI-TOF-MS in this example are as described below.

[0182] <Measurement conditions of GPC>

[0183] Measuring device: "HLC-8320GPC (registered trademark)" manufactured by Tosoh Corporation

[0184] Column: Guard column "TSKgel (registered trademark) HXL-L" manufactured by Tosoh Corporation

[0185] + "TSKgel G4000 HXL" manufactured by Tosoh Corporation

[0186] + "TSKgel G3000 HXL" manufactured by Tosoh Corporation

[0187] + "TSKgel G2000 HXL" manufactured by Tosoh Corporation

[0188] + "TSKgel G2000 HXL" manufactured by Tosoh Corporation

[0189] Detector: RI (differential refractometer)

[0190] Data processing: Tosoh Corporation's "GPC Workstation EcoSEC (registered trademark) Workstation"

[0191] Determination conditions: column temperature 40°C

[0192] Developing solvent: tetrahydrofuran

[0193] Flow rate 1.0mL / min

[0194] Standard sample: According to the measurement manual of the aforementioned GPC apparatus, the following monodisperse polystyrene having a known molecular weight was used.

[0195] "A-500" manufactured by Tosoh Corporation

[0196] "A-1000" manufactured by Tosoh Corporation

[0197] "A-2500" manufactured by Tosoh Corporation

[0198] "A-5000" manufactured by Tosoh Corporation

[0199] "F-1" manufactured by Tosoh Corporation

[0200] "F-2" manufactured by Tosoh Corporation

[0201] "F-4" manufactured by Tosoh Corporation

[0202] "F-10" manufactured by Tosoh Corporation

[0203] "F-20" manufactured by Tosoh Corporation

[0204] "F-40" manufactured by Tosoh Corporation

[0205] "F-80" manufactured by Tosoh Corporation

[0206] "F-128" manufactured by Tosoh Corporation

[0207] Sample to be measured: A sample (50 μL) obtained by filtering a tetrahydrofuran solution having a content of 1.0% by mass in terms of resin solid content through a microfilter.

[0208] < 13 C NMR measurement conditions>

[0209] Apparatus: "JNM-ECA500" manufactured by JEOL Ltd.

[0210] Measurement mode: SINGLE-PULSE-DEC (NOE-suppressed 1 1H complete decoupling method)

[0211] Solvent: chloroform-d

[0212] Pulse angle: 30° pulse

[0213] Sample concentration: 30 wt%

[0214] Number of accumulations: 4000 times

[0215] <Measurement conditions of MALDI-TOF-MS>

[0216] Apparatus: AXIMA-TOF manufactured by Shimadzu / Kratos Co., Ltd. 2 (Registered trademark)

[0217] Ionization method: matrix-assisted laser desorption ionization method

[0218] (Example 1) Production of active ester resin (I-1)

[0219] 30.0 g of Galleon Earth (registered trademark) V2R (manufactured by Mizusawa Chemical Industry Co., Ltd.) and 300.0 g of toluene were added to a reaction vessel equipped with a thermometer, a dropping funnel, a condenser, a fractionating column, and a stirring device, and the inside of the system was purged with nitrogen under reduced pressure. While purging with nitrogen, 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 and 210.0 g of indene were added, and the mixture was stirred at room temperature. After the exothermic reaction ended, the mixture was heated and stirred at 90 °C for 2 hours. After cooling to room temperature, Galleon Earth V2R was removed by filtration. A part of toluene was distilled off under heating and reduced pressure to produce 410.0 g of a toluene solution of resin (s-1) containing phenolic hydroxyl groups (non-volatile content: 58%). The hydroxyl equivalent of resin (s-1) containing phenolic hydroxyl groups was 451 g / equivalent.

[0220] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirring device, 0.4 g of tetrabutylammonium fluoride, 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 replaced with nitrogen under reduced pressure. While purging with nitrogen, 96.8 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 the addition was completed, 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 portion of the toluene was distilled off under heating and reduced pressure 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 in accordance with JIS K7234 was 151°C.

[0221] (Example 2) Production of Active Ester Resin (I-2)

[0222] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube 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 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 nitrogen. After the exotherm was completed, the mixture was heated and stirred at 90°C for 2 hours. After cooling to room temperature, 100 g of 8% sodium bicarbonate aqueous solution was added and stirred for 30 minutes. After the organic layer was neutralized with 30% sodium dihydrogen phosphate aqueous solution, the organic layer was washed with water until the pH of the aqueous layer reached 7. A portion of the toluene was distilled off under heating and reduced pressure conditions to produce 486.0 g (52% non-volatile matter) of a toluene solution of a phenolic hydroxyl-containing resin (s-2). The hydroxyl equivalent of the phenolic hydroxyl-containing resin (s-2) is 450 g / equivalent.

[0223] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirring device, 0.4 g of tetrabutylammonium fluoride, 50.9 g of isophthaloyl chloride, 434.4 g of a toluene solution of a phenolic hydroxyl group-containing resin (s-2) (non-volatile content 52%), and 777.6 g of toluene were added, and the system was replaced with nitrogen under reduced pressure. While purging with nitrogen, 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 the addition was completed, 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 portion of the toluene was distilled off under heating and reduced pressure to produce 441.0 g of a toluene solution of an active ester resin (I-2) (non-volatile content 65%). The functional group equivalent of the active ester resin (I-2) was 514 g / equivalent, and the softening point measured in accordance with JIS K7234 was 102°C.

[0224] (Example 3) Production of Active Ester Resin (I-3)

[0225] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirring device, 105.0 g of phenol, 195.0 g of indene and 300.0 g of toluene were added, and 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 nitrogen. After the exotherm was completed, the mixture was heated and stirred at 90°C for 2 hours. After cooling to room temperature, 100 g of 8% sodium bicarbonate aqueous solution was added and stirred for 30 minutes. After the organic layer was neutralized with 30% sodium dihydrogen phosphate aqueous 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-containing resin (s-3). The hydroxyl equivalent of the phenolic hydroxyl-containing resin (s-3) is 446 g / equivalent.

[0226] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirring device, 0.3 g of tetrabutylammonium fluoride, 40.4 g of isophthaloyl chloride, 178.4 g of a phenolic hydroxyl group-containing resin (s-3), and 612.7 g of toluene were added, and the system was replaced with nitrogen under reduced pressure. While purging nitrogen, 82.4 g of a 20% aqueous sodium hydroxide solution was added dropwise over 1 hour while stirring so that the temperature of the reaction liquid did not exceed 40°C. After the addition was completed, 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 portion of the toluene was distilled off under heating and reduced pressure to produce 340.0 g of a toluene solution of an active ester resin (I-3) (58% non-volatile matter). 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.

[0227] (Example 4) Production of Active Ester Resin (I-4)

[0228] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirring device, 105.0 g of o-cresol, 195.0 g of indene and 300.0 g of toluene were added, and 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 nitrogen. After the exotherm was completed, the mixture was heated and stirred at 90°C for 2 hours. After cooling to room temperature, 100 g of 8% sodium bicarbonate aqueous solution was added and stirred for 30 minutes. After the organic layer was neutralized with 30% sodium dihydrogen phosphate aqueous 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-containing resin (s-4). The hydroxyl equivalent of the phenolic hydroxyl-containing resin (s-4) is 350 g / equivalent.

[0229] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirring device, 0.4 g of tetrabutylammonium fluoride, 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 replaced with nitrogen under reduced pressure. While purging nitrogen, 133.9 g of a 20% aqueous sodium hydroxide solution was added dropwise over 1 hour while stirring in such a way that the temperature of the reaction liquid did not exceed 40°C. After the addition was completed, 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 portion of the toluene was distilled off under heating and reduced pressure conditions to produce 432.2 g (61% non-volatile content) of a toluene solution of an active ester resin (I-4). The functional group equivalent of the active ester resin (I-4) was 415 g / equivalent, and the softening point measured in accordance with JIS K7234 was 121°C.

[0230] (Example 5) Production of Active Ester Resin (I-5)

[0231] 249.0 g of a phenolic hydroxyl group-containing resin (s-5) was produced by the same method except that 60.0 g of phenol and 240.0 g of indene were used instead of those in Example 3. The hydroxyl group equivalent of the phenolic hydroxyl group-containing resin (s-5) was 646 g / equivalent.

[0232] In Example 3, 358.0 g of a toluene solution of an active ester resin (I-5) (63% nonvolatile content) was prepared in the same manner except that 0.4 g of tetrabutylammonium fluoride, 32.9 g of isophthalic acid chloride, 210.7 g of a phenolic hydroxyl group-containing resin (s-5), 695.2 g of toluene, and 67.2 g of a 20% sodium hydroxide aqueous solution were used instead. The functional group equivalent of the active ester resin (I-5) was 711 g / equivalent, and the softening point measured in accordance with JIS K7234 was 147°C.

[0233] (Example 6) Production of Active Ester Resin (I-6)

[0234] 164.0 g of a phenolic hydroxyl group-containing resin (s-6) was produced by the same method except that 150.0 g of phenol and 150.0 g of indene were used instead of those in Example 3. The hydroxyl group equivalent of the phenolic hydroxyl group-containing resin (s-6) was 341 g / equivalent.

[0235] In Example 3, 289.0 g of a toluene solution of an active ester resin (I-6) (58% nonvolatile content) was prepared 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% sodium hydroxide aqueous solution were used instead. The functional group equivalent of the active ester resin (I-6) was 406 g / equivalent, and the softening point measured in accordance with JIS K7234 was 111°C.

[0236] (Example 7) Production of Active Ester Resin (I-7)

[0237] 235.0 g of a phenolic hydroxyl group-containing resin (s-7) was produced by the same method except that 75.0 g of o-cresol and 225.0 g of indene were used instead of those in Example 4. The hydroxyl group equivalent of the phenolic hydroxyl group-containing resin (s-7) was 500 g / equivalent.

[0238] In Example 4, 419.5 g of a toluene solution of an active ester resin (I-7) (61% nonvolatile content) was prepared in the same manner except that 0.4 g of tetrabutylammonium fluoride, 45.7 g of isophthalic acid 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% sodium hydroxide aqueous solution were used instead. The functional group equivalent of the active ester resin (I-7) was 565 g / equivalent, and the softening point measured in accordance with JIS K7234 was 137°C.

[0239] (Example 8) Production of Active Ester Resin (I-8)

[0240] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirring device, 30.0 g of Galleon Earth (registered trademark) V2R (manufactured by Mizusawa Chemical Industry Co., Ltd.) and 300.0 g of toluene are added, and the system is replaced with nitrogen under reduced pressure. Heat and reflux at 120°C for 1 hour while purging nitrogen to remove moisture. After cooling to 40°C, 90.0 g of 1-naphthol is added. While stirring at room temperature, 210.0 g of indene is added dropwise. After the addition is completed, heat and reflux at 120°C for 2 hours. After cooling to room temperature, Galleon Earth V2R is removed by filtration. A portion of the toluene is distilled off under heating and reduced pressure conditions to produce 459.0 g (55% non-volatile matter) of a toluene solution of a phenolic hydroxyl-containing resin (s-8). The hydroxyl equivalent of the phenolic hydroxyl-containing resin (s-8) is 460 g / equivalent.

[0241] 453.9 g of a toluene solution of an active ester resin (I-8) (63% nonvolatile content) was prepared in the same manner as in Example 1 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 in accordance with JIS K7234 was 145°C.

[0242] (Example 9) Production of Active Ester Resin (I-9)

[0243] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirring device, 60.0 g of Galleon Earth (registered trademark) V2R (manufactured by Mizusawa Chemical Industry Co., Ltd.) and 600.0 g of toluene are added, and the system is replaced with nitrogen under reduced pressure. Heat and reflux at 120°C for 1 hour while purging nitrogen to remove moisture. After cooling to 40°C, 180.0 g of 1-naphthol is added. While stirring at room temperature, 420.0 g of indene is added dropwise. After the addition is completed, heat and reflux at 120°C for 2 hours. After cooling to room temperature, Galleon Earth V2R is removed by filtration. A portion of the toluene is distilled off under heating and reduced pressure conditions to produce 898.0 g (49% non-volatile matter) of a toluene solution of a phenolic hydroxyl-containing resin (s-9). The hydroxyl equivalent of the phenolic hydroxyl-containing resin (s-9) is 437 g / equivalent.

[0244] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirring device, 0.5 g of tetrabutylammonium fluoride, 66.7 g of isophthalic acid chloride, 292.7 g of a toluene solution of a phenolic hydroxyl group-containing resin (s-9) (49% non-volatile content), 54.5 g of a polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g / equivalent, softening point 85°C), and 1086.3 g of toluene were added, and the system was replaced with nitrogen under reduced pressure. While purging with nitrogen, 136.0 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 the addition was completed, 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 portion of toluene was distilled off under heating and reduced pressure to prepare 557.1 g (nonvolatile content 65%) of a toluene solution of active ester resin (I-9). The functional group equivalent of active ester resin (I-9) was 549 g / equivalent, and the softening point measured in accordance with JIS K7234 was 164°C.

[0245] (Example 10) Production of Active Ester Resin (I-10)

[0246] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a 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 replaced with nitrogen under reduced pressure. While purging nitrogen, the mixture was heated and refluxed at 150°C for 4 hours to remove moisture. After cooling to below 100°C, 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 tank, 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 to produce 260.0 g of a benzyl-modified naphthalene compound (s'-10). The hydroxyl equivalent of the benzyl-modified naphthalene compound (s'-10) was 173 g / equivalent.

[0247] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirring device, 0.5 g of tetrabutylammonium fluoride, 84.8 g of isophthaloyl chloride, 248.3 g of a toluene solution of a phenolic hydroxyl group-containing resin (s-9) (49% non-volatile content), 96.9 g of a benzyl-modified naphthalene compound (s'-10), and 1050.8 g of toluene were added, and the system was replaced with nitrogen under reduced pressure. While purging with nitrogen, 173.0 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 the addition was completed, 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 portion of the toluene was distilled off under heating and reduced pressure to produce 539.0 g of a toluene solution of an active ester resin (I-10) (65% non-volatile content). The functional group equivalent of the active ester resin (I-10) was 417 g / equivalent, and the softening point measured in accordance with JIS K7234 was 169°C.

[0248] (Example 11) Production of Active Ester Resin (I-11)

[0249] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirrer, 375.0 g of 3,3',5,5'-tetramethylbiphenyl-4,4'-diphenol, 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 replaced with nitrogen under reduced pressure. The mixture was heated and refluxed at 150°C for 4 hours while purging nitrogen to remove moisture. After cooling to below 100°C, 187.5 g of xylene and 7.5 g of a 20% aqueous sodium hydroxide solution were added and stirred. After removing the water tank, the organic layer was washed three times with 170.0 g of water. Xylene and unreacted benzyl alcohol were distilled off under heating and reduced pressure to produce 580.0 g of a benzyl-modified biphenyl compound (s'-11). The hydroxyl equivalent of the benzyl-modified biphenyl compound (s'-11) was 211 g / equivalent.

[0250] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirring device, 0.5 g of tetrabutylammonium fluoride, 64.6 g of isophthaloyl chloride, 283.8 g of a toluene solution of a phenolic hydroxyl group-containing resin (s-9) (49% non-volatile content), 67.6 g of a benzyl-modified biphenyl compound (s'-11), and 1075.3 g of toluene were added, and the system was replaced with nitrogen under reduced pressure. While purging with nitrogen, 131.8 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 the addition was completed, 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 portion of the toluene was distilled off under heating and reduced pressure to produce 551.0 g of a toluene solution of an active ester resin (I-11) (65% non-volatile content). The functional group equivalent of the active ester resin (I-11) was 560 g / equivalent, and the softening point measured in accordance with JIS K7234 was 165°C.

[0251] (Example 12) Production of Active Ester Resin (I-12)

[0252] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a 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 replaced with nitrogen under reduced pressure. While purging nitrogen, the mixture was heated and refluxed at 120°C for 12 hours to remove moisture. After cooling to below 100°C, 134.7 g of water and 6.7 g of a 20% aqueous sodium hydroxide solution were added and stirred. After removing the water tank, the organic layer was washed three 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 bisphenol resin (s'-12). The hydroxyl equivalent of bisphenol resin (s'-12) is 598 g / equivalent.

[0253] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirring device, 0.5 g of tetrabutylammonium fluoride, 59.4 g of isophthalic acid chloride, 262.5 g of a toluene solution of a phenolic hydroxyl group-containing resin (s-9) (49% non-volatile content), 168.8 g of a bisphenol resin (s'-12) and 1151.0 g of toluene were added, and the system was replaced with nitrogen under reduced pressure. While purging with nitrogen, 121.1 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 the addition was completed, 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 portion of the toluene was distilled off under heating and reduced pressure to produce 580.0 g of a toluene solution of an active ester resin (I-12) (65% non-volatile content). The functional group equivalent of the active ester resin (I-12) was 652 g / equivalent, and the softening point measured in accordance with JIS K7234 was 174°C.

[0254] (Synthesis Reference Example 1) Preparation of Active Ester Resin (R-1)

[0255] In a reaction vessel equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube and a stirring device, 0.6 g of tetrabutylammonium fluoride, 152 g of isophthaloyl chloride, 72 g of 1-naphthol, 165 g of a polyaddition reaction resin of dicyclopentadiene and phenol (hydroxyl equivalent: 165 g / equivalent, softening point 85°C) and 630 g of toluene were added, and the system was replaced with nitrogen under reduced pressure. While purging nitrogen, 315 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while stirring in such a way that the temperature of the reaction liquid did not exceed 60°C. After the addition was completed, the mixture was heated and stirred at 60°C for 3 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 portion of the toluene was distilled off under heating and reduced pressure conditions to prepare a 65% toluene solution of the 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 in accordance with JIS K7234 was 150°C.

[0256] (Examples 13 to 23, Comparative Example 1) Preparation of resin composition

[0257] 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 resin solid was obtained by heating and vacuum drying at 180°C for 2 hours. The obtained active ester resin solid was used to prepare a resin composition by mixing the components in the proportions shown in Tables 1 and 2 below. As the epoxy resin, for Examples 13 to 19, a cresol novolac type multifunctional epoxy resin EPICLON (registered trademark) N-655-EXP-S (manufactured by DIC Corporation, epoxy equivalent 197 to 207 g / equivalent) was used, and for Examples 20 to 23 and Comparative Example 1, a bisphenol-A type epoxy resin EPICLON 850S (manufactured by DIC Corporation, epoxy equivalent 184 to 194 g / equivalent) was used. 4-Dimethylaminopyridine was used as a curing catalyst. In addition, as the active ester resin of Comparative Example 1, the active ester resin (R-1) produced in Synthesis Reference Example 1 was used.

[0258] [Table 1]

[0259]

[0260] [Table 2]

[0261]

[0262] (Examples 24 to 34, Comparative Example 2) Preparation of Cured Resin

[0263] 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. The resulting molded product was removed from the mold and cured at 175°C for 5 hours to produce the resin cured products shown in Table 3 below.

[0264] The prepared resin cured product was heated and vacuum dried at 105°C for 2 hours, and then stored in a room at a temperature of 23°C and a humidity of 50% for 24 hours, and then the dielectric constant and dielectric loss tangent were measured. The measurement was performed using a network analyzer E8362C (manufactured by Agilent Technologies, Inc.) by the cavity resonance method. The measurement results are shown in Table 3 below.

[0265] [Table 3]

[0266]

[0267] 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 show lower dielectric loss tangent at 10 GHz than the active ester resin (R-1) of the comparative example.

[0268] (Examples 35 to 40, Comparative Example 3) Preparation of resin composition

[0269] For the active ester resins (I-1) to (I-4) and (I-8) prepared in Examples 1 to 4 and 8, after the solvent was distilled off, the resin was heated and vacuum dried at 180°C for 2 hours to obtain a solid resin. The obtained resin solids were dissolved in methyl ethyl ketone to prepare a 65% methyl ethyl ketone solution of each active ester resin. Using the obtained resin solution, after mixing the components in the ratio shown in Table 4 below, the resin composition was prepared by diluting with methyl ethyl ketone in such a way that the non-volatile component (NV) after mixing was 60%. Dicyclopentadiene phenol type epoxy resin EPICLON HP-7200H-75M (manufactured by DIC Corporation, epoxy equivalent 279g / equivalent) was used as the epoxy resin, and 4-dimethylaminopyridine was used as the curing catalyst. The mixing ratio of the curing catalyst represents the ratio relative to the solid content of the active ester resin and the epoxy resin. In addition, as the active ester resin of Comparative Example 3, the active ester resin (R-1) prepared in Synthesis Reference Example 1 was used.

[0270] [Table 4]

[0271]

[0272] (Examples 41 to 46, Comparative Example 4) Preparation of Laminated Plate

[0273] Using the resin compositions prepared in Examples 35 to 40 and Comparative Example 3, laminated plates were produced under the following conditions.

[0274] Base material: Glass cloth "#2116" (210×280mm) manufactured by Nitto Bosho Co., Ltd.

[0275] Copper foil: JTC SLC foil manufactured by JX Metal Co., Ltd. (18 μm)

[0276] Number of layers: 6

[0277] Curing conditions: 200°C, 29kg / cm 2 Next 1.5 hours

[0278] Thickness after forming: 0.8mm

[0279] The dielectric constant and dielectric loss tangent of the obtained laminate were measured by the same method as above. The measurement results are shown in Table 5 below.

[0280] [Table 5]

[0281]

[0282] 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 show lower dielectric loss tangent at 10 GHz than the active ester resin (R-1) of the comparative example. It can also be seen that the active ester resin of the present invention shows lower dielectric loss tangent at 10 GHz even when used in combination with an active ester resin other than the present invention.

[0283] From the above results, it is understood that the active ester resin of the present invention is a curing agent for epoxy resins that can provide a cured product that exhibits a lower dielectric loss tangent in a high frequency band.

Claims

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

2. The active ester resin according to claim 1, wherein The phenolic hydroxyl group-containing resin (A) is represented by the following general formula (S): [Chemistry 1] In the formula, A 1 represents a hydrocarbon ring or heterocyclic ring having 3 to 16 carbon atoms which may be substituted, L represents a group represented by the following formula (L), [Chemistry 2] In the formula, * indicates the 1 The bonding position of the ring indicated, R 1 and R 2 each independently represents 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, and R 1 and R 2 When there are multiple, they can be the same or different. R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 Each independently 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, a halogen atom, an aryl group having 6 to 20 carbon atoms, and an aralkyl group having 7 to 20 carbon atoms, and R 3 , R 4 , R 5 , R 6 , R 7 , R 8 and R 9 When there are multiple, they can be the same or different. r1 represents an integer of 0 to 4, r2 represents an integer of 0 to 5, n1 represents an integer of 1 to 20, and n2 represents an integer of 0 to 20. The order of the repeating units enclosed by n1 and n2 is not limited, and the bonding method may be alternating, block, or random. The repeating units enclosed by n1 and n2 may have the same structure or a plurality of different structures. m represents 1 or more, and in A 1 An integer equal to or less than the number of substitutable ring atoms in the represented ring.

3. The active ester resin according to claim 1 or 2, which is a resin obtained by reacting a phenolic hydroxyl group-containing resin (A), an aromatic (poly)carboxylic acid or an acid halide thereof (B), and a compound or resin (C) different from the phenolic hydroxyl group-containing resin (A) as a hydroxyl group-containing compound or resin. 4 . A resin composition comprising the active ester resin according to claim 1 . The resin composition according to claim 4 , comprising an epoxy resin. 6 . The resin composition according to claim 4 , comprising a phenolic resin and / or an active ester resin other than the active ester resin according to claim 1 . 7 . A cured product obtained by curing the resin composition according to claim 4 .

8. A semiconductor sealing 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. A phenolic hydroxyl-containing resin represented by the following formula (S111-1) to formula (S111-3), [Chemistry 3] In the formula, R A represents a linear or branched alkyl group having 1 to 5 carbon atoms, L 111 represents a group represented by the following formula (L111), [Chemistry 4] In the formula, * indicates the bonding position to the ring, R 7111 represents a hydrogen atom or a methyl group. 7111 In the case of , they can be the same or different, n1111 represents an integer of 1 to 10, and n2111 represents an integer of 0 to 10. When n2111 represents an integer greater than 1, the order of the repeating units enclosed by n1111 and n2111 is not limited, the bonding method is random, and the repeating units enclosed by n2111 may have the same structure or a plurality of different structures. m111 represents an integer of 1 to 7, m112 represents an integer greater than or equal to 1, m113 represents an integer greater than or equal to 1, and m112+m113 represents an integer less than or equal to 5.

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