Aromatic amine resin, curable composition, cured product, prepreg, circuit board, build-up film, semiconductor sealing material and semiconductor device

Abstract

To provide an aromatic amine resin which suppresses water absorption of a cured product, and can suppress lowering of dielectric characteristics (dielectric constant and dielectric loss tangent) and heat resistance.SOLUTION: An aromatic amine resin is a reaction product of a fluorene compound (provided that it has no substituent on 9-position), aromatic amine and a compound represented by general formula (1). In the formula, Ar is Ar1-Y-Ar1 or Ar1, Ar1 are each independently an aromatic ring group which may have a substituent, Y is a single bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, a -P(=O)Ra- group, an oxygen atom, a sulfur atom or a sulfonyl group, Ra is an aromatic ring group, R1 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, and X is a leaving group.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to an aromatic amine resin, a curable composition, a cured product, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device. [Background technology]

[0002] Aromatic amine resins are intermediates for various polymers including polyamide resins, amide-imide resins, and polyimide resins, and because they have strong nucleophilicity, they are also widely used as curing agents for epoxy resins, isocyanate resins, etc. For example, epoxy resin compositions using aromatic amine resins as curing agents exhibit excellent heat resistance and insulating properties, and are widely used in electronic component applications such as semiconductors and multilayer printed circuit boards. Patent Document 1 discloses that the use of an aromatic amine resin having a biphenylaralkyl structure in an epoxy resin composition improves the heat resistance and moisture absorption of the cured product. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2016 / 117584 Summary of the Invention [Problem to be solved by the invention]

[0004] In recent years, the demand for weather resistance and reliability of electronic components such as semiconductors and multilayer printed circuit boards has become more stringent. If a cured product used in electronic components such as semiconductors and multilayer printed circuit boards absorbs water, the cured product may deteriorate and its dielectric properties and heat resistance may decrease. Therefore, there is still a demand for aromatic amine resins that can provide cured products with reduced water absorption. [Means for solving the problem]

[0005] Means for Solving the Problems The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have discovered that an aromatic amine resin having a structure in which the hydrogen atom at the 9th position of a fluorene structural unit is modified with an aralkyl can suppress water absorption of a cured product using the resin, and can also suppress deterioration of the dielectric properties (dielectric constant and dielectric tangent) and heat resistance, thereby completing the present invention.

[0006] The gist of the present invention is as follows. [1] An aromatic amine resin which is a reaction product of a fluorene compound (not having a substituent at the 9-position), an aromatic amine and a compound represented by general formula (1). [ka] (where: Ar is Ar 1 -Y-Ar 1 Or Ar 1 and Ar 1 each independently represents an aromatic ring group which may have a substituent, Y is a single bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, -P(=O)R a - group, oxygen atom, sulfur atom or sulfonyl group, R a is an aromatic ring group, R 1 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, X is a leaving group. [2] The aromatic amine resin according to [1], wherein the amount of the fluorene compound is 0.01 to 0.99 mol per 1 mol of the compound represented by the general formula (1). [3] An aromatic amine resin represented by general formula (5): [ka] (where: Z is independently a group represented by the general formula (2A): [ka] or a structural unit represented by general formula (3A): [ka] It is a structural unit represented by Z' is independently a group represented by the general formula (2A'): [ka] or a structural unit represented by general formula (3A'): [ka] It is a structural unit represented by Ar is independently Ar 1 Or Ar 1 -Y-Ar 1 and Ar 1 each independently represents an aromatic ring group which may have a substituent, Y is a single bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, -P(=O)R a - group, oxygen atom, sulfur atom or sulfonyl group, R a is an aromatic ring group, R 1 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R 2 each independently represents an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, m is independently an integer of 0 to 4, R 3 are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or when n is 2 or more, two R 3 may form a ring together with the carbon atom to which they are attached, n is independently an integer of 0 to 3, R b and R c each independently represents a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, R 2’ each independently represents an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, m' is independently an integer of 0 to 4, R 3’ are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or when n' is 2 or more, two R 3’ may form a ring together with the carbon atom to which they are attached, Each n' is independently an integer of 0 to 4, R b' and R c' each independently represents a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, p is the average value and is a number greater than 0; * represents a bond, However, the resin contains a structural unit represented by general formula (2A) and / or general formula (2A') and a structural unit represented by general formula (3A) and / or general formula (3A'). [4] The aromatic amine resin according to [3], which contains at least one compound selected from the group consisting of compounds represented by general formula (5-1) and compounds represented by general formula (5-2). [ka] (where: Ar, Z, R 1 , R 3’ , n', R b’ and R c’ is equivalent to [3].) [5] An aromatic amine resin according to any one of [1] to [4], having an amine equivalent of 100 to 2000 g / equivalent. [6] Any of the aromatic amine resins [1] to [5], having a number average molecular weight of 100 to 10,000. [7] A curable composition comprising the aromatic amine resin according to any one of [1] to [6] and a curable resin. [8] A cured product of the curable composition of [7]. [9] A prepreg having a reinforcing substrate and a semi-cured product of the curable composition [7] impregnated into the reinforcing substrate.

[10] [9] A circuit board that is a laminate of prepreg and copper foil.

[11] A build-up film containing the curable composition of [7].

[12] A semiconductor encapsulant comprising the curable composition according to [7].

[13] A semiconductor device comprising the cured semiconductor encapsulant according to

[12] . Effect of the Invention

[0007] According to the aromatic amine resin of the present invention, it is possible to suppress water absorption of a cured product using the resin, and thus suppress deterioration in dielectric properties (dielectric constant and dielectric tangent) and heat resistance. By using a curable composition containing the aromatic amine resin and a cured product thereof, it is possible to provide a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device in which water absorption is suppressed and thus deterioration in dielectric properties (dielectric constant and dielectric tangent) and heat resistance is suppressed. [Brief description of the drawings]

[0008] [Figure 1] 1 shows the results of GPC measurement of the aromatic amine resin (1) synthesized in Example 1. [Diagram 2] 1 is a result of 13C-NMR measurement of the aromatic amine resin (1) synthesized in Example 1. [Diagram 3] 1 shows the results of FD-MS measurement of the aromatic amine resin (1) synthesized in Example 1. [Figure 4] 1 shows the results of GPC measurement of aromatic amine resin (2) synthesized in Example 2. [Diagram 5] 1 shows the results of 13C-NMR measurement of the aromatic amine resin (2) synthesized in Example 2. [Figure 6] 1 shows the results of FD-MS measurement of the aromatic amine resin (2) synthesized in Example 2. [Figure 7] 1 shows the results of GPC measurement of the aromatic amine resin (3) synthesized in Example 3. [Figure 8]1 shows the results of 13C-NMR measurement of the aromatic amine resin (3) synthesized in Example 3. [Figure 9] 1 shows the results of FD-MS measurement of the aromatic amine resin (3) synthesized in Example 3. [Figure 10] 1 shows the results of GPC measurement of the aromatic amine resin (4) synthesized in Example 4. [Figure 11] 1 shows the results of 13C-NMR measurement of the aromatic amine resin (4) synthesized in Example 4. [Figure 12] 1 shows the results of FD-MS measurement of the aromatic amine resin (4) synthesized in Example 4. [Figure 13] 1 shows the results of GPC measurement of the aromatic amine resin (5) synthesized in Example 5. [Figure 14] 1 shows the results of C-NMR measurement of the aromatic amine resin (5) synthesized in Example 5. [Figure 15] 1 shows the results of FD-MS measurement of the aromatic amine resin (5) synthesized in Example 5. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Hereinafter, the mode for carrying out the invention will be described in detail, however, the present invention is not limited to the following description and can be carried out in various modified forms within the scope of the gist thereof.

[0010] [term] In this specification, the term "reaction raw material" refers to a compound that is used to obtain a target compound through a chemical reaction such as synthesis or decomposition and that partially constitutes the chemical structure of the target compound, and excludes substances that play the role of chemical reaction assistants such as solvents and catalysts. In particular, in this specification, the term "reaction raw material" refers to a precursor for obtaining the target aromatic amine resin through a chemical reaction. The term "structural unit" as used herein refers to a (repeating) unit of a chemical structure formed during a reaction or polymerization; in other words, it refers to a partial structure other than the structure of the chemical bonds involved in the reaction or polymerization in a product compound formed by a reaction or polymerization, i.e., a so-called residue.

[0011] The aliphatic hydrocarbon group in this specification may be any of linear, branched and cyclic types, and may have an unsaturated bond in the structure. Examples of the aliphatic hydrocarbon group include those having 1 to 20 carbon atoms. In this specification, the monovalent aliphatic hydrocarbon group includes an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and a cycloalkynyl group. The alkyl group in this specification may be either a straight-chain or branched type and includes those having 1 to 20 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, an amyl group, a cyclopentyl group, a hexyl group, a heptyl group, an octyl group, a cumyl group, a nonyl group, a decyl group, an undecyl group, and a dodecyl group. The alkenyl group in this specification may be either a straight-chain or branched type and includes those having 2 to 20 carbon atoms, such as a vinyl group, an allyl group, a butenyl group, a butadienyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group, an undecenyl group, and a dodecenyl group. The alkynyl group in this specification may be either a straight-chain or branched type and includes those having 2 to 20 carbon atoms, such as an ethynyl group, a propargyl group, a butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, a decynyl group, an undecynyl group, and a dodecynyl group. The cycloalkyl group in this specification may be a monocyclic group or a polycyclic group and includes those having 3 to 30 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, an adamantyl group, a methylcyclohexyl group, and an ethylcyclohexyl group. The cycloalkenyl group in this specification may be a monocyclic group or a polycyclic group, and examples of the cycloalkenyl group include those having 3 to 30 carbon atoms, such as a cyclohexenyl group, a methylcyclohexenyl group, and an ethylcyclohexenyl group. The cycloalkynyl group in this specification may be a monocyclic group or a polycyclic group, and examples of the cycloalkynyl group include those having 4 to 30 carbon atoms, such as a cyclohexynyl group, a methylcyclohexynyl group, and an ethylcyclohexynyl group. In this specification, the divalent aliphatic hydrocarbon group includes an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkenylene group, and a cycloalkynylene group. The alkylene group in this specification may be either a straight-chain or branched type and includes those having 1 to 20 carbon atoms, such as a methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, and dodecylene group. The alkenylene group in this specification may be either a straight-chain or branched type and includes those having 2 to 20 carbon atoms, such as a vinylene group, a propenylene group, a butenylene group, a butadienylene group, an octenylene group, a decenylene group, and a dodecenylene group. The alkynylene group in this specification may be either a straight-chain or branched type and includes those having 2 to 20 carbon atoms, such as an ethynylene group, a propynylene group, a butynylene group, a butazinylene group, a pentynylene group, a hexynylene group, a heptynylene group, an octynylene group, a nonynylene group, a decynylene group, an undecynylene group, or a dodecynylene group. In the present specification, an alkoxy group has an alkyl-O- structure, and the above description of the alkyl group is applied to the alkyl portion in the structure, such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, a sec-butoxy group, a tert-butoxy group, an allyloxy group, etc. The cycloalkylene group in this specification may be a monocyclic group or a polycyclic group, and can be one having 3 to 30 carbon atoms, such as a divalent group corresponding to the groups exemplified as the cycloalkyl group. The cycloalkenylene group in this specification may be a monocyclic group or a polycyclic group, and can be one having 3 to 30 carbon atoms, such as a divalent group corresponding to the groups exemplified as cycloalkenyl groups. The cycloalkynylene group in this specification may be a monocyclic group or a polycyclic group, and can be one having 4 to 30 carbon atoms, such as a divalent group corresponding to the groups exemplified as cycloalkynyl groups. The aromatic ring in this specification is a hydrocarbon ring consisting of a single ring or condensed rings having aromaticity, and includes those having 6 to 20 carbon atoms, such as a benzene ring, a naphthalene ring, an indene ring, an anthracene ring, etc. The aromatic ring group is a residue of an aromatic ring. The aromatic hydrocarbon group in this specification is a residue of an aromatic hydrocarbon compound, and includes an aryl group. The aryl group includes those having 6 to 20 carbon atoms, such as a phenyl group, a naphthyl group, a biphenyl group, and a phenanthryl group. In the present specification, the arylalkyl group is an alkyl group substituted with one or more, preferably one or two, particularly one, aryl group, and the above description of the aryl group and alkyl group applies to the aryl group and alkyl group, such as a benzyl group or a phenethyl group. Halogen atoms in this specification are fluorine, chlorine, bromine and iodine.

[0012] The number average molecular weight (Mn) and weight average molecular weight (Mw) in this specification are values ​​measured using gel permeation chromatography (hereinafter also referred to as "GPC") under the measurement conditions described in the examples described later. The amine equivalent in this specification is a value measured by neutralization titration, and can be measured by the method described in the Examples.

[0013] [Reaction raw materials for aromatic amine resin] The aromatic amine resin of the present invention is prepared using, as reaction raw materials, a fluorene compound (which does not have a substituent at the 9-position) (hereinafter, also simply referred to as a "fluorene compound"), an aromatic amine, and a compound represented by general formula (1).

[0014] <Fluorene compounds> The fluorene compound is not particularly limited as long as it does not have a substituent at the 9-position of the fluorene, and may be unsubstituted or substituted at a position other than the 9-position.

[0015] The fluorene compound may be a compound represented by the following general formula (2). [ka] (where: m is independently an integer of 0 to 4, R 2 are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom.

[0016] As the aliphatic hydrocarbon group, an alkyl group having 1 to 4 carbon atoms is preferred, such as a methyl group, an ethyl group, a propyl group, or a butyl group. The aryl group is preferably a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an indenyl group, or an indanyl group. The arylalkyl group is preferably a benzyl group, a phenethyl group, or a cumyl group. The alkoxy group is preferably a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. The halogen atom is preferably fluorine, chlorine or bromine.

[0017] Each m is independently preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0. The two m's may be the same or different, but are preferably the same. When both of the two m's are 1 or more, R substituted on the two benzene rings constituting the fluorene skeleton 2 may be the same or different. When either or both of m is 2 or more, two or more R2 may be the same or different.

[0018] A preferred example of the compound of the general formula (2) is fluorene. [ka]

[0019] The compound of formula (2) can be used alone or in combination of two or more kinds in any ratio.

[0020] <Aromatic amine> An aromatic amine is an aromatic compound having one unsubstituted or substituted amino group in the molecule. The substituted amino group may be a mono-substituted or di-substituted amino group. From the viewpoint of industrial applicability, it is preferable that an aromatic amine has an unsubstituted or mono-substituted amino group having active hydrogen. Examples of the substituent in the substituted amino group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group, and preferably an alkyl group (e.g., an alkyl group having 1 to 4 carbon atoms) and an aryl group (e.g., an aryl group having 6 to 10 carbon atoms).

[0021] The aromatic amine may be a compound represented by the following general formula (3). [ka] (where: n'' is an integer from 0 to 4, R 3’’ are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or when n'' is 2 or more, two R 3’’ may form a ring together with the carbon atom to which they are attached, R b’’ and R c’’ are each independently a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group.

[0022] R 3’’Regarding the aliphatic hydrocarbon group, an alkyl group having 1 to 4 carbon atoms is preferred, such as a methyl group, an ethyl group, a propyl group, or a butyl group. The aryl group is preferably a phenyl group, a tolyl group, a xylyl group, or a naphthyl group. The arylalkyl group is preferably a benzyl group, a phenethyl group, or a cumyl group. The alkoxy group is preferably a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. The halogen atom is preferably fluorine, chlorine or bromine. R 3’’ Among these, an alkyl group or an aryl group is preferable. Or, if n'' is 2 or more, two R 3’’ may form a ring together with the carbon atom to which they are bonded. Examples of the ring include a hydrocarbon ring having 6 to 20 ring-constituting atoms, such as a benzene ring, a naphthalene ring, an anthracene ring, an adamantane ring, an indane ring, and an indene ring. These rings may have a substituent, and examples of the substituent include an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, and a halogen atom.

[0023] n'' is preferably 0, 1 or 2. If n'' is 2, then two R 3’’ preferably form a benzene or naphthalene ring together with the carbon atom to which they are attached.

[0024] R b’’ and R c’’ In regard to the above, the aliphatic hydrocarbon group is preferably an alkyl group or an aryl group. The alkyl group is more preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, or a butyl group. The aryl group is preferably a phenyl group, a tolyl group, a xylyl group, or a naphthyl group. R b’’ and R c’’It is preferable that both of R are hydrogen atoms, or one of R is a hydrogen atom and the other is an aliphatic hydrocarbon group or an aromatic hydrocarbon group. b’’ and R c’’ more preferably, both are hydrogen atoms, or one of them is a hydrogen atom and the other is an aliphatic hydrocarbon group (preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms) or an aromatic hydrocarbon group (preferably an aryl group, more preferably an aryl group having 6 to 10 carbon atoms).

[0025] Preferred examples of the compound of formula (3) include the following compounds: [ka] Here, R b’’ and R c’’ R is each independently a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group. b’’ and R c’’ It is preferable that both of R are hydrogen atoms, or one of them is a hydrogen atom and the other is an aliphatic hydrocarbon group or an aromatic hydrocarbon group. More preferably, R b’’ and R c’’ Both of the groups are hydrogen atoms, or one of them is a hydrogen atom and the other is an aliphatic hydrocarbon group (preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms) or an aromatic hydrocarbon group (preferably an aryl group, more preferably an aryl group having 6 to 10 carbon atoms).

[0026] The compound of formula (3) can be used alone or in combination of two or more kinds in any ratio.

[0027] <Compound represented by general formula (1)> The compound represented by general formula (1) is a compound in which the hydrogen atom at the 9-position of the fluorene structural unit can be modified to an aralkyl, and at the same time, it can also react with aromatic amines, and thus functions as a binder. [ka] (where: Ar is Ar 1 -Y-Ar 1 Or Ar 1 and Ar 1 each independently represents an aromatic ring group which may have a substituent, Y is a single bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, -P(=O)R a - group, oxygen atom, sulfur atom or sulfonyl group, R a is an aromatic ring group, R 1 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, X is a leaving group.

[0028] Ar 1 is an aromatic ring group which may have a substituent. The aromatic ring group is not particularly limited, and is preferably a phenylene group, a naphthylene group, or an anthracenylene group. In the case of a phenylene group, it is preferable that the bonds are located at the 1- and 4-positions, in the case of a naphthylene group, it is preferable that the bonds are located at the 2- and 6-positions, and in the case of an anthracenylene group, it is preferable that the bonds are located at the 9- and 10-positions. Ar 1 -Y-Ar 1 Two Ar in 1 may be the same or different, but is preferably the same.

[0029] Examples of the substituent include an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, and a halogen atom. The aliphatic hydrocarbon group is preferably an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propylene group, or a butylene group. The aryl group is preferably a phenyl group, a tolyl group, a xylyl group, or a naphthyl group. The arylalkyl group is preferably a benzyl group, a phenethyl group, or a cumyl group. The alkoxy group is preferably a methoxy group, an ethoxy group, a propoxy group, or a butoxy group. The halogen atom is preferably fluorine, chlorine or bromine. Among them, the substituent is preferably an alkyl group, an aryl group, or the like.

[0030] Y is a single bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, -P(=O)R a - group, an oxygen atom, a sulfur atom or a sulfonyl group (-S(=O)2- group). The aliphatic hydrocarbon group having 1 to 6 carbon atoms is not particularly limited, and is preferably a methylene group, an ethylene group, a propylene group, an isopropylidene group, or a butylidene group. -P(=O)R a -R in the group a is an aromatic ring group, preferably a phenyl group. Among these, Y is preferably a single bond, an ethylene group, or a propylene group.

[0031] Ar 1 -Y-Ar 1 As the alkyl group, a biphenylene group and a binaphthylene group are preferable.

[0032] X is a leaving group, and examples thereof include a hydroxyl group, a halogen atom, and an alkoxy group. The halogen atom is preferably chlorine, bromine or iodine. The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propyloxy group, or a butoxy group. Among these, X is preferably a chlorine atom, a bromine atom, an iodine atom, a hydroxyl group, or a methoxy group. The two X's may be the same or different.

[0033] R 1 is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms. The aliphatic hydrocarbon group having 1 to 4 carbon atoms is not particularly limited, and a methyl group, an ethyl group, a propyl group, a butyl group, and the like are preferred. R 1 Among them, hydrogen atom and methyl are preferable. 1may be the same or different, but is preferably the same.

[0034] The compound of general formula (1) is a compound represented by the following general formula (1-1) (wherein Ar is Ar 1 -Y-Ar 1 and a compound of the following general formula (1-2) (Ar is Ar 1 (which is [ka] (where R 1 , Ar 1 The definitions and preferred examples of Y and X are as described above.

[0035] The compound of general formula (1) may be used alone or in combination of two or more kinds. That is, the compound of general formula (1) is a compound of general formula (1-1), a compound of general formula (1-2), or a combination of the compound of general formula (1-1) and the compound of general formula (1-2). The compound of general formula (1-1) and the compound of general formula (1-2) may be used alone or in combination of two kinds. When the compound of general formula (1-1) and the compound of general formula (1-2) are used alone or in combination, it is preferable because it leads to suppression of water absorption caused by the use of aromatic amine resin. When the compound of general formula (1-1) and the compound of general formula (1-2) are used in combination, although there is no particular limitation, their molar ratio (molar number of the compound of general formula (1-1):molar number of the compound of general formula (1-2)) can be 10:90 to 90:10, preferably 20:80 to 80:20.

[0036] Preferred examples of the compound of formula (1-1) include the following. [ka]

[0037] Preferred examples of the compound of formula (1-2) include the following: [ka]

[0038] [Method of producing aromatic amine resin] The aromatic amine resin of the present invention is a reaction product of the above-mentioned reaction raw materials, and specifically, can be produced as follows.

[0039] The amounts of the reaction raw materials, fluorene compound, aromatic amine and compound of general formula (1), used are as follows: From the viewpoint of introducing an aromatic amine, the amount of the compound of general formula (1) may be more than 1 mole relative to 1 mole of the fluorene compound, and is not particularly limited as long as it is more than 1 mole. For example, the amount of the fluorene compound used may be 0.01 moles or more, preferably 0.1 moles or more, more preferably 0.3 moles or more, relative to 1 mole of the compound of general formula (1), and may be 0.99 moles or less, preferably 0.95 moles or less. During the reaction, substantially the entire amount of the fluorene compound and the compound of general formula (1) react, and therefore the molar ratio of the fluorene compound and the compound of general formula (1) used in the reaction is substantially the same as the molar ratio of the structural units derived from the fluorene compound and the structural units derived from the compound of general formula (1) in the obtained aromatic amine resin.

[0040] The amount of the aromatic amine used is not particularly limited, but may be an amount such that the amount of the unsubstituted or substituted amino group of the aromatic amine is 0.1 moles or more, preferably 0.2 moles or more, and may be an amount such that the amount of the unsubstituted or substituted amino group of the aromatic amine is 10 moles or less, preferably 9.5 moles or less, relative to the compound of general formula (1). As for the aromatic amine, some aromatic amine remains unreacted, but the amount of the reacted aromatic amine can be calculated from the amine equivalent of the aromatic amine resin.

[0041] The aromatic amine resin can be produced, for example, by the following steps 1 and 2.

[0042] <Process 1> It is preferable to react the entire amount of the fluorene compound and the entire amount of the compound of general formula (1) in an organic solvent using an alkali catalyst at 10 to 150°C without adding an aromatic amine, or to react the entire amount of the fluorene compound and the entire amount of the compound of general formula (1) with a part or the entire amount of the aromatic amine in an organic solvent using an alkali catalyst at 10 to 150°C.

[0043] The amount of aromatic amine used is not particularly limited, but may be an amount in which the amount of unsubstituted or substituted amino group of aromatic amine is 0.1 moles or more, preferably 0.2 moles or more, and may be an amount in which the amount of unsubstituted or substituted amino group of aromatic amine is 10 moles or less, preferably 9.5 moles or less, relative to the general formula (1). By using such an amount, the generation of by-products can be suppressed.

[0044] Examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, and Solvesso; alcoholic solvents such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, sec-butanol, and tert-butanol; cellosolve solvents such as methyl cellosolve and ethyl cellosolve; ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane; and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide, sulfolane, dimethylformamide, and dimethylacetamide. From the viewpoint of solubility, toluene, xylene, mesitylene, Solvesso, isopropyl alcohol, dimethyl sulfoxide, dimethylformamide, and dimethylacetamide are preferred. These organic solvents can be used alone or in combination of two or more at any ratio. The amount of the organic solvent used is not particularly limited, but is preferably 50 to 500% by mass based on the total amount of the compound of general formula (1) and the fluorene compound charged.

[0045] Examples of the alkali catalyst include lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methoxy, sodium ethoxy, sodium tert-butoxy, potassium methoxy, potassium ethoxy, potassium tert-butoxy, triethylamine, pyridine, and dimethylaminopyridine. From the viewpoint of reactivity, sodium hydroxide or potassium hydroxide is preferred. The amount of the alkali catalyst used can be 10 to 1000 mol% based on the amount of the general formula (1) charged. These catalysts can be used as an aqueous solution of 1 to 50 mass%.

[0046] A phase transfer catalyst may be used in the reaction. Examples of the phase transfer catalyst include ammonium-based catalysts such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium, tetrabutylammonium iodide, tetrabutylammonium hydroxide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltriethylammonium iodide, and benzyltriethylammonium hydroxide; phosphonium-based catalysts such as tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, and tetrabutylphosphonium hydroxide; and crown ether-based catalysts such as 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, and tribenzo-18-crown-6-ether. In terms of reactivity, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, and benzyltriethylammonium iodide are preferred. The phase transfer catalyst may be used alone or in combination of two or more.

[0047] Additives may be used to promote the reaction. Examples of additives include halides such as lithium bromide, sodium bromide, potassium bromide, cesium bromide, lithium iodide, sodium iodide, potassium iodide, and cesium iodide. Among these, sodium iodide and potassium iodide are preferred. The additives may be used alone or in combination of two or more.

[0048] The reaction temperature can be from 10 to 150° C., and from the viewpoint of reactivity, is preferably from 20 to 140° C. The reaction time can be from 1 to 72 hours, and is preferably from 2 to 70 hours.

[0049] After the reaction is completed, the reaction mixture is separated into upper and lower layers as appropriate, and the lower layer, which is the aqueous layer, is removed to obtain the reaction product. At this time, water may be added as necessary to dissolve the insoluble salt and remove the lower layer. The aqueous layer may be basic, neutralized by neutralization, or acidic. Examples of neutralizing agents used for neutralization include inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, sodium monophosphate, and ammonium chloride, and organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid. These acid catalysts may be used alone or in combination of two or more.

[0050] <Process 2> When no aromatic amine is added or only a portion of the aromatic amine is added in step 1, the entire amount or the remainder of the aromatic amine is added to the reaction product obtained in step 1, and the reaction is carried out in the presence of an acid catalyst at 60 to 250° C. When the entire amount of the aromatic amine is added in step 1, the reaction product obtained in step 1 is reacted in the presence of an acid catalyst at 60 to 250° C.

[0051] The aromatic amine used in step 2 may be the same as or different from the aromatic amine used in step 1.

[0052] The acid catalyst can be any of organic acids, inorganic acids, and solid acids. Examples of the organic acid include aliphatic sulfonic acids such as methanesulfonic acid or fluoromethanesulfonic acid; aromatic sulfonic acids such as 3-morpholinopropanesulfonic acid, piperazine-1,4-bis(2-ethanesulfonic acid), 10-camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, or trifluoromethanesulfonic acid; alkyl phosphoric acids such as dimethyl phosphate or diethyl phosphate; alkyl sulfuric acids such as dimethyl sulfate, diethyl sulfate, and lauryl sulfate; aromatic sulfuric acids such as phenyl sulfate and phenyl fluoride sulfate; and oxalic acid. Examples of the inorganic acid include phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, and boric acid. Examples of the solid acid include activated clay, acid clay, alumina, silica alumina, zeolite, layered silicate, heteropolyhydrochloric acid, and strong acid ion exchange resin. Examples of the layered silicate include kaolin group such as dickite, nacrite, kaolinite, anoxite, metahalloysite, and halloysite, serpentine group such as chrysotile, lizardite, and antigorite, smectite group such as montmorillonite, sauconite, beidellite, nontronite, saponite, taeniolite, hectorite, and stevensite, vermiculite group such as vermiculite, mica group such as mica, illite, sericite, and glauconite, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, and chlorite. These layered silicates may form a mixed layer. The above acid catalysts may be used alone or in combination of two or more. The amount of the acid catalyst is not particularly limited, but is preferably 0.001 to 50% by mass based on the total amount of the reaction raw materials charged.

[0053] The reaction temperature is 60 to 250° C., and from the viewpoint of reactivity, is preferably 80 to 240° C. The reaction time can be 1 to 72 hours, and is preferably 2 to 70 hours.

[0054] After the reaction is completed, neutralization and washing with water are carried out as necessary, and unreacted reactants, organic solvents, etc. are distilled off under reduced pressure and heating conditions to obtain an aromatic amine resin.

[0055] The method for producing an aromatic amine resin of the present invention is not limited to the above. For example, instead of step 1, a fluorene compound and a compound of general formula (1) may be reacted in an organic solvent in the presence of a catalyst at 10 to 150°C, and then a part of the aromatic amine may be added and reacted at 10 to 150°C, after which the water layer is removed, a water washing treatment is performed, and the resulting reaction product is subjected to step 2. In this case, the reaction product of step 1 may have a reactive group at the end, and the reactive group may be a reaction product with an aromatic amine, a reaction product with a solvent, a halogen, or a hydroxyl group depending on the type of compound used.

[0056] [Aromatic amine resin] The aromatic amine resin of the present invention is a reaction product of a fluorene compound, an aromatic amine and a compound of general formula (1), and has an unsubstituted or substituted amino group, preferably an unsubstituted or mono-substituted amino group.

[0057] The fluorene compound represented by general formula (2), the aromatic amine represented by general formula (3), and the compound represented by general formula (1) can respectively produce a structural unit represented by general formula (2A) or general formula (2A'), a structural unit represented by general formula (3A) or general formula (3A'), and a structural unit represented by general formula (1A). [ka] (wherein the definition, examples and preferred examples of m and m' are the same as those of m in general formula (2), R 2 and R 2’ The definition, examples and preferred examples of R in the general formula (2) are as follows: 2 is the same as * represents a bond.) [ka] (where: n is an integer from 0 to 3, preferably 0, 1 or 2. n' is an integer of 0 to 4, preferably 0, 1 or 2; R 3 and R3’ The definition, examples and preferred examples of are the same as those of R″ in general formula (3). R b and R c And R b’ and R c’ The definition, examples and preferred examples of R in the general formula (3) are as follows: b’’ and R c’’ is the same as * represents a bond.) [ka] (where: Ar and R 1 The definition, examples and preferred examples are the same as those of general formula (1), * represents a bond.)

[0058] The aromatic amine resin of the present invention contains a structure in which a structural unit of general formula (1A) is bonded to a structural unit of general formula (2A) and / or general formula (2A'). At least one molecular chain terminal of the aromatic amine resin of the present invention is preferably a structural unit of general formula (3A'), and more preferably both molecular chain terminals are structural units of general formula (3A').

[0059] The aromatic amine resin of the present invention is composed of structural units of general formula (2A) and / or general formula (2A'), structural units of general formula (3A) and / or (3A'), and structural units of general formula (1A), with the proviso that a bond of the structural unit of general formula (2A) and / or general formula (2A') may be bonded to a bond of the structural unit of general formula (1A). When a structural unit of general formula (2A') is present, the structural unit constitutes a molecular chain terminal. At least one of the molecular chain terminals is preferably a structural unit of general formula (3A'), and more preferably both of the molecular chain terminals are structural units of general formula (3A').

[0060] In the aromatic amine resin of the present invention, Ar in the structural unit of the general formula (1A) is Ar 1 Or Ar1 -Y-Ar 1 In other words, all of the Ar contained in the aromatic amine resin is Ar 1 or Ar 1 -Y-Ar 1 or Ar 1 -Y-Ar 1 and Ar 1 The aromatic amine resin can be composed of Ar 1 and Ar 1 -Y-Ar 1 By incorporating at least one of the above, it is possible to suppress the water absorption caused by the use of the aromatic amine resin, which is preferable. 1 -Y-Ar 1 and Ar 1 When the compound is composed of the above, the molar ratio of the above (Ar 1 -Y-Ar 1 Number of moles of Ar 1 The molar ratio of the two components (molar ratio) can be 10:90 to 90:10, and is preferably 20:80 to 80:20.

[0061] The structural unit of the general formula (1A) is 1 -Y-Ar 1 or Ar is a structural unit represented by the following general formula (1-1A): 1 or a structural unit of the following general formula (1-1A) and Ar is Ar 1 and a structural unit of the following general formula (1-2A): The structural unit of the general formula (1A) is preferably composed of a structural unit of the following general formula (1-1A) and a structural unit of the following general formula (1-2A), since this leads to suppression of water absorption caused by the use of an aromatic amine resin.

[0062] [ka] (where R 1 , Ar 1 The definition and preferred examples of Y are the same as those of general formula (1). * represents a bond.)

[0063] When the structural unit of general formula (1A) is composed of a structural unit of general formula (1-1A) and a structural unit of general formula (1-2A), the molar ratio therebetween (the number of moles of the structural unit of general formula (1-1A):the number of moles of the structural unit of general formula (1-2A)) is not particularly limited, but may be 10:90 to 90:10, and preferably 20:80 to 80:20.

[0064] Preferred examples of the structural unit of the general formula (1-1A) are as follows: [ka]

[0065] Preferred examples of the structural unit of the general formula (1-2A) are as follows: [ka]

[0066] The aromatic amine resin of the present invention includes an aromatic amine resin represented by the following general formula (5). [ka] (where: Z is independently a group represented by the general formula (2A): [ka] or a structural unit represented by general formula (3A): [ka] It is a structural unit represented by Z' is independently a group represented by the general formula (2A'): [ka] or a structural unit represented by general formula (3A'): [ka] It is a structural unit represented by Ar is independently Ar 1 Or Ar 1 -Y-Ar 1 and Ar 1 each independently represents an aromatic ring group which may have a substituent, Y is a single bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, -P(=O)R a - group, oxygen atom, sulfur atom or sulfonyl group, R a is an aromatic ring group, R 1 each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R 2 each independently represents an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, m is independently an integer of 0 to 4, R 3 are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or when n is 2 or more, two R 3 may form a ring together with the carbon atom to which they are attached, n is independently an integer of 0 to 3, R b and R c each independently represents a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, R 2’ each independently represents an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, m' is independently an integer of 0 to 4, R 3’ are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or when n' is 2 or more, two R 3’ may form a ring together with the carbon atom to which they are attached, Each n' is independently an integer of 0 to 4, R b' and R c' each independently represents a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, p is an average value greater than 0; * represents a bond, However, the resin contains a structural unit represented by general formula (2A) and / or general formula (2A') and a structural unit represented by general formula (3A) and / or general formula (3A').

[0067] In the above, Ar, Ar 1 , Y, R 1 、 R 2 , R 3 , R b , R c , m, n, R 2’ , R 3’ , R b' , R c' , m', n' and p are the same as those described above. 1 and Ar 1 -Y-Ar 1 The examples and preferred examples are the same as those mentioned above.

[0068] The aromatic amine resin of general formula (5) is a mixture of compounds in which p in the above general formula (5) is an integer of 0 or more (provided that not all of the compounds are compounds of general formula (5) in which p is 0), and preferably contains a compound containing both a structural unit represented by general formula (2A) and / or general formula (2A') and a structural unit represented by general formula (3A) and / or general formula (3A') in the molecule. In the resin, the total amount of the structural units of general formulae (2A) and (2A') is preferably 0.1 to 10 mol, more preferably 0.5 to 9.5 mol, per 1 mol of the structural units of general formulae (3A) and (3A').

[0069] A preferred example is an aromatic amine resin represented by the following general formula (5-0). [ka] (Wherein, Ar, Z, R 1 , R 3’ , R b' , R c' , n' and p are the same as in general formula (5).

[0070] Where Ar, Z, R 1 , R 3 , R b' , R c' , n' and p are the same as those described above. 1 and Ar 1 -Y-Ar 1 The examples and preferred examples of R in Z are the same as those described above. 2 , m, R 3 , n, R b and R c The examples and preferred examples are the same as those mentioned above.

[0071] More preferred examples of the aromatic amine resin of the present invention include aromatic amine resins represented by the following general formula (5-0'). [ka] (where R 2 , m, R 3 , n, R 3’ , n', R b , R c , R b' and R c' is as above, Each Ar' is independently [ka] and s is the average value, a number greater than 0; t is the average value, and is a number equal to or greater than 0; The order of the structural units bracketed by s and the structural units bracketed by t is not limited.

[0072] The aromatic amine resin of general formula (5) and the aromatic amine resin of general formula (5-0) can be a mixture of compounds each having a structural unit bounded by p with an integer of 0 or more, but not all of the compounds are compounds of general formula (5) in which p is 0. The aromatic amine resin of general formula (5) preferably contains at least one compound selected from the group consisting of compounds represented by general formula (5-1) and compounds represented by general formula (5-2). [ka] (where: Ar, Z, R 1 , R 3' , R b' , R c' and n' are as defined above; Z in general formula (5-1) and at least one Z in general formula (5-2) are structural units represented by general formula (2A).

[0073] The aromatic amine resin of the present invention may contain a compound of general formula (6) as a part thereof. The compound of general formula (6) corresponds to the compound of general formula (5) above in which p is 0. [ka] (where: Ar, R 1 , R 3’ , R b' , R c' and n' are as defined above.

[0074] The number average molecular weight (Mn) of the aromatic amine resin may be in the range of 100 to 10,000, and preferably in the range of 200 to 8,000. The weight average molecular weight (Mw) of the aromatic amine resin may be in the range of 100 to 50,000, and preferably in the range of 300 to 40,000. The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the aromatic amine resin can be in the range of 1-5, and is preferably 1-4.

[0075] The amine equivalent of the aromatic amine resin is preferably in the range of 100 to 2000 g / equivalent, and more preferably 200 to 1800 g / equivalent.

[0076] [Curable composition] The curable composition of the present invention can contain the aromatic amine resin of the present invention and a curable resin. By using the aromatic amine resin of the present invention, it is possible to suppress the water absorption of the cured product obtained from the curable composition, and thus to suppress the deterioration of the dielectric properties (dielectric constant and dielectric loss tangent) and heat resistance.

[0077] The curable composition may contain other aromatic amine resins other than the aromatic amine resin of the present invention. Examples of other aromatic amine resins include various novolac-type amine resins and aralkylene group-containing amine resins. These may be used alone or in combination. The ratio of the aromatic amine resin of the present invention to the total of the aromatic amine resin of the present invention and other aromatic amine resins is appropriately adjusted according to the desired cured product performance, etc., but is preferably 50 mass% or more, more preferably 80 mass% or more.

[0078] The curable resin is not particularly limited as long as it is a compound having a functional group capable of reacting with the aromatic amine resin of the present invention, and examples thereof include epoxy resins. The epoxy resin is not particularly limited, and a wide variety of resins can be used. Examples include various bisphenol-type epoxy resins, various novolac-type epoxy resins, and aralkylene group-containing epoxy resins. These may be used alone or in combination.

[0079] The compounding ratio of the aromatic amine resin and the curable resin is appropriately adjusted depending on the desired performance of the cured product, etc., but it is preferable that the reactive group in the curable resin is in the range of 0.5 to 1.5 moles per mole of unsubstituted or substituted amino group in the aromatic amine resin. When the above-mentioned other aromatic amine resins are used, it is preferable that the reactive group in the curable resin is in the range of 0.5 to 1.5 moles per mole of the total of unsubstituted or substituted amino groups in the curable composition.

[0080] When an epoxy resin is used as the curable resin, a curing accelerator may be used as necessary. Various types of curing accelerators can be used, including phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. These may be used alone or in combination. Among them, phosphorus compounds such as triphenylphosphine or imidazoles are preferred from the viewpoint of excellent curability, heat resistance, electrical properties, and moisture resistance reliability. The amount of the curing accelerator added is preferably in the range of 0.01 to 10 parts by mass with respect to 100 parts by mass of the total mass (excluding the solvent) of the curable composition.

[0081] The curable composition may contain other resin components, such as active ester resins, maleimide resins, cyanate resins, unsaturated polyester resins, polybutadiene resins, and phenol resins.

[0082] The curable composition may contain various compounding agents such as a curing accelerator, a silane coupling agent, a release agent, a pigment, an emulsifier, a non-halogen-based flame retardant, an inorganic filler, a flame retardant (e.g., an inorganic phosphorus-based flame retardant, an organic phosphorus-based flame retardant, or a halogen-based flame retardant), and a solvent.

[0083] The curable composition can be obtained by uniformly mixing the aromatic amine resin of the present invention, a curable resin, and any optional components (eg, a curing catalyst, compounding agents, etc.).

[0084] [Cured product] The cured product of the present invention can be obtained by curing the curable composition of the present invention. The curing method is not particularly limited, and a known method can be adopted. The cured product can be in the form of a laminate, a cast product, an adhesive layer, a coating film, a film, etc.

[0085] [Semiconductor encapsulation materials] The semiconductor encapsulant of the present invention can contain the curable composition of the present invention. Since the curable composition of the present invention contains the aromatic amine resin of the present invention, the semiconductor encapsulant containing the curable composition can exhibit excellent dielectric properties (low dielectric constant and low dielectric loss tangent) and high heat resistance.

[0086] The semiconductor encapsulant may be prepared by adding an inorganic filler to the curable composition of the present invention. The inorganic filler is not particularly limited, and examples thereof include barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, and aluminum nitride. The amount of the inorganic filler may be 0.5 to 1200 parts by mass based on 100 parts by mass of the curable composition.

[0087] The semiconductor encapsulant may contain various compounding agents, including those described for the curable composition.

[0088] The semiconductor encapsulant can be obtained by mixing the curable composition of the present invention and, if necessary, compounding ingredients. For example, a method of thoroughly melt-mixing the composition using an extruder, kneader, roll, or the like until the composition becomes homogeneous can be mentioned.

[0089] [Semiconductor Devices] The semiconductor device of the present invention can include a cured product of the semiconductor encapsulant of the present invention. The semiconductor encapsulant used in the semiconductor device of the present invention contains a curable composition containing the aromatic amine resin of the present invention. The semiconductor device of the present invention has excellent heat resistance and dielectric properties because it includes a cured product of the semiconductor encapsulant.

[0090] A semiconductor device can be obtained by heating and curing the semiconductor encapsulant of the present invention, for example, by casting or molding using a transfer molding machine, injection molding machine, or the like, and then heating and curing the material at a temperature range of room temperature (20°C) to 250°C.

[0091] [Prepreg] The prepreg of the present invention may have a reinforcing substrate and a semi-cured product of the curable composition of the present invention impregnated into the reinforcing substrate. The method for obtaining a prepreg from the curable composition is not particularly limited, and examples of the method include a method in which the curable composition is made into a varnish by blending an organic solvent described later into a reinforcing base material (e.g., paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, etc.), and then heated at a heating temperature (preferably 50 to 170°C) according to the type of solvent used to semi-cure (or uncure) the curable composition. The mass ratio between the curable composition and the reinforcing base material used is not particularly limited, but it is preferable to adjust the resin content in the prepreg to 20 to 60 mass %.

[0092] The semi-cured product of the curable composition can be obtained by adjusting the heating temperature and heating time to stop the curing reaction midway without completing it. The degree of curing of the semi-cured product can be, for example, 5% or more and 85% or less. Here, the cured product can have a higher degree of curing than the semi-cured product. The degree of curing of the semi-cured product can be calculated from the following formula by measuring the amount of heat generated during curing when the curable composition is heated and the amount of heat generated during curing of the semi-cured product by DSC. Degree of cure (%)=[1-(cure heat generation amount of semi-cured product / cure heat generation amount of curable composition)]×100

[0093] Examples of organic solvents used in the production of prepregs include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. The selection of the organic solvent and the amount used can be appropriately selected depending on the application, and for example, when producing a circuit board from a prepreg, polar solvents with a boiling point of 160° C. or less such as methyl ethyl ketone, acetone, dimethylformamide, etc. are preferred, and the amount used is preferably an amount such that the nonvolatile content is 40 to 80 mass%.

[0094] [Circuit board] The circuit board of the present invention is made of a laminate of the prepreg of the present invention and copper foil. The method for obtaining the circuit board is not particularly limited, and an example thereof is a method in which the prepreg of the present invention is laminated as necessary, copper foil is superimposed, and the laminate is heated and compressed at 170 to 300° C. under a pressure of 1 to 10 MPa for 10 minutes to 3 hours.

[0095] [Build-up film] The build-up film of the present invention may contain the curable composition of the present invention. The method for producing the build-up film is not particularly limited, and may be, for example, a method in which the curable composition of the present invention is applied onto a support film to form a curable composition layer to form an adhesive film for a multilayer printed wiring board.

[0096] The build-up film is required to soften under the temperature conditions for lamination in the vacuum lamination method (usually 70 to 140°C) and to exhibit fluidity (resin flow) that allows resin to fill via holes or through holes present in the circuit board at the same time as lamination of the circuit board. Therefore, it is preferable that the curable composition contains the above-mentioned components so as to exhibit such properties.

[0097] Here, the diameter of the through-holes in the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to make it possible to fill the resin within this range. When both sides of the circuit board are laminated, it is preferable to fill about 1 / 2 of the through-holes.

[0098] Specifically, the adhesive film can be produced by preparing the curable composition in a varnish form, applying the varnish-like composition to the surface of the support film (Y), and then drying the organic solvent by heating or blowing hot air or the like to form a composition layer (X) made of the curable composition.

[0099] The thickness of the composition layer (X) formed is usually preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

[0100] The composition layer (X) may be protected with a protective film described below. By protecting the resin composition layer with a protective film, the surface of the resin composition layer can be prevented from being scratched or from being contaminated by dirt or the like.

[0101] Examples of the above-mentioned support film (Y) and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and further release paper and metal foils such as copper foil and aluminum foil. The support film and protective film may be subjected to a release treatment in addition to a mud treatment and a corona treatment.

[0102] The thickness of the support film is not particularly limited, but is usually in the range of 10 to 150 μm, preferably 25 to 50 μm, and the thickness of the protective film is preferably 1 to 40 μm.

[0103] The above-mentioned support film (Y) is peeled off after laminating it onto 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, the adhesion of dust and the like during the curing process can be prevented. When peeling off after curing, the support film is usually subjected to a release treatment in advance.

[0104] [Application] The cured product obtained by the curable composition containing the aromatic amine resin of the present invention has excellent heat resistance and dielectric properties, and therefore can be suitably used for heat-resistant or electronic components. In particular, it can be suitably used for prepregs, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up boards, adhesives using conductive pastes, resist materials, and the like. It can also be suitably used for matrix resins of fiber-reinforced resins, and is particularly suitable as highly heat-resistant prepregs. In addition, the aromatic amine resin contained in the curable composition exhibits excellent solubility in various solvents, and can be made into paint. The heat-resistant or electronic components thus obtained can be suitably used for various applications, including, but not limited to, industrial machine parts, general machine parts, automobile, railway, and vehicle parts, space and aviation-related parts, electronic and electrical parts, building materials, containers and packaging materials, daily necessities, sports and leisure goods, and housing members for wind power generation. EXAMPLES

[0105] The present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to the following description and can be practiced with various modifications within the scope of the gist. In the following, "parts" and "%" are based on mass unless otherwise specified.

[0106] The physical properties of the aromatic amine resin were evaluated as follows.

[0107] (1) GPC measurement The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the aromatic amine resins obtained in the examples and comparative examples were calculated using the following measuring equipment and conditions. "Measuring device" Tosoh Corporation "HLC-8320 GPC" "Measurement conditions" Column: Tosoh Corporation guard column "HXL-L" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G2000HXL" + Tosoh Corporation "TSK-GEL G3000HXL" + Tosoh Corporation "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40℃ Developing solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: In accordance with the measurement manual for the "GPC Workstation EcoSEC-WorkStation," the following monodisperse polystyrene with known molecular weight was used. (Polystyrene used) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation Sample: A tetrahydrofuran solution (1.0% by mass, calculated as resin solid content) of the aromatic amine resin obtained in Synthesis Example was filtered through a microfilter (50 μl).

[0108] (2) FD-MS measurement The FD-MS spectra of the aromatic amine resins obtained in the examples were measured using the following measuring device and under the following measuring conditions. Measurement equipment: JMS-T100GC AccuTOF Measurement conditions Measurement range: m / z=4.00~2000.00 Rate of change: 51.2mA / min Final current value: 45mA Cathode voltage: -10kV Recording interval: 0.07 seconds

[0109] (3) 13 C-NMR measurement The aromatic amine resin obtained in the examples 13 C-NMR spectra were measured using the following measuring device and conditions. 13 C-NMR: “JNM-ECZ400S” manufactured by JEOL RESONANCE Resonance frequency: 100MHz Number of times: 4000 Solvent: Chloroform-d Sample concentration: 12% by mass Relaxation agent: Chromium(III) acetylacetonate

[0110] (4) Amine equivalent The amine equivalent of the aromatic amine obtained in the examples was measured by the following method. Approximately 2.5 g of aromatic amine, 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine were precisely weighed into a 500 mL Erlenmeyer flask equipped with a stopper, and then the mixture was heated to reflux for 150 minutes in an oil bath equipped with a cooling tube and set to 120°C. After cooling, 5.0 mL of distilled water, 100 mL of propylene glycol monomethyl ether, and 75 mL of tetrahydrofuran were added, and the mixture was titrated potentiometrically with 0.5 mol / L potassium hydroxide-ethanol solution. A blank test was performed in the same manner to correct the value. Amine equivalent (g / equivalent) = (S x 2,000) / (Blank-A) S: Amount of sample (g) A: Consumption of 0.5 mol / L potassium hydroxide-ethanol solution (mL) Blank: Amount of 0.5 mol / L potassium hydroxide-ethanol solution consumed in the blank test (mL)

[0111] Example 1: Synthesis of aromatic amine resin (1) In a flask equipped with a thermometer, dropping funnel, condenser, distillation column, and stirrer, 100.0 parts by mass of fluorene and 210.62 parts by mass of α,α'-dichloro-p-xylene (hereinafter abbreviated as PXDC) were added. Parts by mass of aniline, 7.76 parts by mass of tetrabutylammonium bromide (hereinafter abbreviated as TBAB), 3.99 parts by mass of potassium iodide, and 465.9 parts by mass of xylene were charged, and the temperature was raised to 60°C while stirring. Next, 309.4 parts by mass of 48% by mass of potassium hydroxide aqueous solution was slowly dropped while paying attention to heat generation, and the reaction was carried out at the same temperature for 6 hours from the end of the dropwise addition. Next, 117.7 parts by mass of aniline, 155.3 parts by mass of isopropyl alcohol (hereinafter abbreviated as IPA), and 284.7 parts by mass of water were charged, and the temperature was raised to 75°C, and the reaction was carried out at the same temperature for 10 hours, after which the water layer was removed by separating the lower layer, and the mixture was washed four times with 334.9 parts by mass of water.

[0112] Then, 280.1 parts by mass of aniline and 67.0 parts by mass of activated clay were added, and the mixture was heated to 200°C and reacted at the same temperature for 20 hours. After the reaction was completed, the mixture was cooled, diluted with xylene, and the activated clay was separated by filtration. The filtrate was heated and reduced pressure to remove the solvent and excess aniline, and the desired aromatic amine resin (1) was obtained (amine equivalent: 305 g / equivalent).

[0113] The resulting aromatic amine resin (1) had an Mn of 635 and an Mw of 1077. 13 C-NMR confirmed the presence of the quaternary carbon at the 9-position of fluorene as well as the remaining N-alkylated product. FD-MS confirmed the presence of the target product at m / z 556.3 and 824.5. The resulting GPC chart is shown in Figure 1. 13 The C-NMR chart is shown in Figure 2, and the FD-MS chart is shown in Figure 3.

[0114] Example 2: Synthesis of aromatic amine resin (2) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 100.0 parts by mass of fluorene, 10.62 parts by mass of PXDC2, 7.76 parts by mass of TBAB, 3.99 parts by mass of potassium iodide, and 465.9 parts by mass of xylene, and the temperature was raised to 60°C while stirring. Next, 309.4 parts by mass of a 48% by mass aqueous potassium hydroxide solution was slowly dropped while paying attention to heat generation, and the reaction was carried out at the same temperature for 6 hours from the end of the drop. Next, 153.1 parts by mass of 2-ethylaniline, 155.3 parts by mass of IPA, and 284.7 parts by mass of water were charged, the temperature was raised to 75°C, and the reaction was carried out at the same temperature for 10 hours, after which the lower layer was separated to remove the water layer, and the mixture was washed four times with 368.6 parts by mass of water.

[0115] Next, 364.5 parts by mass of 2-ethylaniline and 73.7 parts by mass of activated clay were added, and the mixture was heated to 200°C and reacted at the same temperature for 15 hours. After the reaction was completed, the mixture was cooled, diluted with xylene, and the activated clay was separated by filtration. The filtrate was heated and reduced pressure to remove the solvent and excess 2-ethylaniline, and the desired aromatic amine resin (2) was obtained (amine equivalent: 314 g / equivalent).

[0116] The resulting aromatic amine resin (2) had an Mn of 444 and an Mw of 729. 13 C-NMR confirmed the presence of the remaining N-alkylated product along with the quaternary carbon at the 9-position of fluorene. FD-MS confirmed the presence of the target product at m / z 612.4 and 880.6. The GPC chart is shown in Figure 4. 13 The C-NMR chart is shown in Figure 5, and the FD-MS chart is shown in Figure 6.

[0117] Example 3: Synthesis of aromatic amine resin (3) A flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer was charged with 100.0 parts by mass of fluorene, 10.62 parts by mass of PXDC2, 7.76 parts by mass of TBAB, 3.99 parts by mass of potassium iodide, and 465.9 parts by mass of xylene, and the temperature was raised to 60°C while stirring. Next, 309.4 parts by mass of a 48% by mass aqueous potassium hydroxide solution was slowly dropped while paying attention to heat generation, and the reaction was carried out at the same temperature for 6 hours from the end of the dropwise addition. Next, 153.1 parts by mass of 2,6-xylidine, 155.3 parts by mass of IPA, and 284.7 parts by mass of water were charged, the temperature was raised to 75°C, and the reaction was carried out at the same temperature for 17 hours, after which the lower layer was separated to remove the water layer, and the mixture was washed four times with 368.6 parts by mass of water.

[0118] Next, 211.4 parts by mass of 2,6-xylidine and 73.7 parts by mass of activated clay were added, and the mixture was heated to 200°C and reacted at the same temperature for 12 hours. After the reaction was completed, the mixture was cooled, diluted with xylene, and the activated clay was separated by filtration. The filtrate was heated and reduced pressure to distill off the solvent and excess 2,6-xylidine, and the desired aromatic amine resin (3) was obtained (amine equivalent: 305 g / equivalent).

[0119] The resulting aromatic amine resin (3) had an Mn of 586 and an Mw of 814. 13 C-NMR confirmed the quaternary carbon at the 9th position of fluorene, and the remaining N-alkylated product was hardly detected. In addition, FD-MS confirmed the presence of the target compound at m / z 612.4 and 880.6. The GPC chart obtained is shown in Figure 7. 13 The C-NMR chart is shown in Figure 8, and the FD-MS chart is shown in Figure 9.

[0120] Example 4: Synthesis of aromatic amine resin (4) In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 100.0 parts by mass of fluorene, 10.62 parts by mass of PXDC2, 7.76 parts by mass of TBAB, 3.99 parts by mass of potassium iodide, and 465.9 parts by mass of xylene were charged, and the temperature was raised to 60°C while stirring. Next, 309.4 parts by mass of a 48% by mass aqueous potassium hydroxide solution was slowly dropped while paying attention to heat generation, and the reaction was carried out at the same temperature for 6 hours from the end of the dropwise addition. Next, 153.1 parts by mass of 2,3-xylidine, 155.3 parts by mass of IPA, and 284.7 parts by mass of water were charged, the temperature was raised to 75°C, and the reaction was carried out at the same temperature for 15 hours, after which the lower layer was separated to remove the water layer, and the mixture was washed four times with 368.6 parts by mass of water.

[0121] Next, 211.4 parts by mass of 2,3-xylidine and 73.7 parts by mass of activated clay were added, and the mixture was heated to 200°C and reacted at the same temperature for 17 hours. After the reaction was completed, the mixture was cooled, diluted with xylene, and the activated clay was separated by filtration. The filtrate was heated and reduced pressure to distill off the solvent and excess 2,3-xylidine, and the desired aromatic amine resin (4) was obtained (amine equivalent: 319 g / equivalent).

[0122] The resulting aromatic amine resin (4) had an Mn of 598 and an Mw of 1021. 13 C-NMR confirmed the presence of the remaining N-alkylated product along with the quaternary carbon at the 9-position of fluorene. FD-MS confirmed the presence of the target product at m / z 612.4 and 880.6. The resulting GPC chart is shown in Figure 10. 13 The C-NMR chart is shown in Figure 11, and the FD-MS chart is shown in Figure 12.

[0123] <Example 5: Synthesis of aromatic amine resin (5)> In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 100.0 parts by mass of fluorene, 224.6 parts by mass of 4,4'-bis(chloromethyl)biphenyl, 14.6 parts by mass of TBAB, 6.76 parts by mass of sodium iodide, and 490.0 parts by mass of xylene were charged, and the temperature was raised to 60°C while stirring. Next, 253.2 parts by mass of a 48% by mass aqueous potassium hydroxide solution was slowly dropped while paying attention to heat generation, and the reaction was carried out at the same temperature for 10 hours from the end of the dropwise addition. Next, 153.1 parts by mass of 2,6-xylidine, 163.3 parts by mass of IPA, and 232.9 parts by mass of water were charged, the temperature was raised to 75°C, and the reaction was carried out at the same temperature for 15 hours, after which the lower layer was separated to remove the water layer, and the mixture was washed four times with 406.6 parts by mass of water.

[0124] Then, 211.4 parts by mass of 2,6-xylidine and 81.3 parts by mass of activated clay were added, and the mixture was heated to 200°C and reacted at the same temperature for 11 hours. After the reaction was completed, the mixture was cooled, diluted with xylene, and the activated clay was separated by filtration. The filtrate was heated and reduced pressure to remove the solvent and excess 2,6-xylidine, and the desired aromatic amine resin (5) was obtained (amine equivalent: 433 g / equivalent).

[0125] The resulting aromatic amine resin (5) had an Mn of 761 and an Mw of 1,167. 13 C-NMR confirmed the quaternary carbon at the 9th position of fluorene, and the remaining N-alkylated product was hardly detected. In addition, FD-MS confirmed the target compounds at m / z 764.5 and 1108.7. The GPC chart obtained is shown in Figure 13. 13 The C-NMR chart is shown in Figure 14, and the FD-MS chart is shown in Figure 15.

[0126] <Examples 6 to 10 and Comparative Example 1> Liquid epoxy resin (EPICLON 850-S, manufactured by DIC Corporation, epoxy equivalent 188 g / equivalent) and aromatic amine resin or diaminodiphenylmethane were mixed at a temperature of 150°C or less in the mass ratio shown in Table 1, and then poured into a mold processed to a thickness of 2 mm and heated and cured at 180°C for 5 hours to obtain a cured product. The following measurements were carried out on the obtained cured product. The results are shown in Table 1.

[0127] (1) Water absorption rate A test piece (approximately 0.6 g) made of the cured material was treated at 121°C and 100% humidity for 6 hours. The water absorption rate (%) was calculated from the difference in mass before and after the treatment. Water absorption rate (%)= ((mass of test piece before treatment - mass of test piece after treatment) ÷ mass of test piece before treatment) x 100

[0128] (2) Dielectric constant and dielectric tangent In accordance with JIS-C-6481, the dielectric constant and dielectric loss tangent at 10 GHz of the test piece were measured by the cavity resonance method using the network analyzer "E8362C" manufactured by Agilent Technologies, Inc., after drying and storing it indoors at 23°C and 50% humidity for 24 hours. The difference between the dielectric constant and dielectric loss tangent after treatment under conditions of 121°C and 100% humidity and the dielectric constant and dielectric loss tangent before treatment was calculated. Dielectric constant difference = dielectric constant after treatment - dielectric constant before treatment Difference in dielectric tangent = dielectric tangent after treatment - dielectric tangent before treatment

[0129] (3) Heat resistance (DMA Tg) Using a viscoelasticity measuring device (Rheometrics' "Solid Viscoelasticity Measuring Device RSAII", rectangular tension method: frequency 1 Hz, heating rate 3°C / min), the low temperature at which the rate of change in Tan δ was greatest was evaluated as the glass transition temperature (Tg). The difference between Tg after treatment and Tg before treatment under conditions of 121°C and 100% humidity was calculated. Tg difference (℃) = Glass transition temperature after treatment - Glass transition temperature before treatment

[0130] [Table 1]

[0131] The results shown in Table 1 above show that by using the aromatic amine resins of Examples 1 to 5, it is possible to suppress the water absorption of the cured product using the resin, and thus to suppress the deterioration of the dielectric properties (dielectric constant and dielectric tangent) and heat resistance. [Industrial Applicability]

[0132] According to the present invention, it is possible to provide an aromatic amine resin that can suppress water absorption in a cured product using the resin, and thus can suppress deterioration in dielectric properties (dielectric constant and dielectric tangent) and heat resistance. By using a curable composition containing the aromatic amine resin and a cured product thereof, it is possible to provide a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device in which water absorption is suppressed and thus deterioration in dielectric properties (dielectric constant and dielectric tangent) and heat resistance is suppressed.

Claims

1. An aromatic amine resin which is a reaction product of a fluorene compound (not having a substituent at the 9-position), an aromatic amine and a compound represented by general formula (1). 【Chemistry 1】 (where: Ar is Ar １ -Y-Ar １ Or Ar １ and Ar １ each independently represents an aromatic ring group which may have a substituent, Y is a single bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, -P(=O)R ａ - group, an oxygen atom, a sulfur atom or a sulfonyl group, and R ａ is an aromatic ring group, R １ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, X is a leaving group.

2. 2. The aromatic amine resin according to claim 1, wherein the fluorene compound is 0.01 to 0.99 moles per mole of the compound represented by the general formula (1).

3. An aromatic amine resin represented by general formula (5): 【Chemistry 2】 (where: Z is independently a group represented by general formula (2A): 【Chemistry 3】 or a structural unit represented by general formula (3A): 【Chemistry 4】 It is a structural unit represented by Z' is independently a group represented by general formula (2A'): 【Chemistry 5】 or a structural unit represented by general formula (3A'): 【Chemistry 6】 It is a structural unit represented by Ar is independently Ar １ Or Ar １ -Y-Ar １ and Ar １ each independently represents an aromatic ring group which may have a substituent, Y is a single bond, an aliphatic hydrocarbon group having 1 to 6 carbon atoms, -P(=O)R ａ - group, an oxygen atom, a sulfur atom or a sulfonyl group, and R ａ is an aromatic ring group, R １ each independently represents a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R ２ each independently represents an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, m is independently an integer from 0 to 4; R ３ are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or when n is 2 or more, two R ３ may form a ring together with the carbon atom to which they are attached, n is independently an integer from 0 to 3; R ｂ and R ｃ each independently represents a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, R ２’ each independently represents an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, m' is independently an integer from 0 to 4; R ３’ are each independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, or a halogen atom, or when n′ is 2 or more, two R ３’ may form a ring together with the carbon atom to which they are attached, Each n' is independently an integer from 0 to 4; R ｂ' and R ｃ' each independently represents a hydrogen atom, an aliphatic hydrocarbon group, or an aromatic hydrocarbon group, p is an average value and is a number greater than 0; * represents a bond, However, the resin contains a structural unit represented by general formula (2A) and / or general formula (2A') and a structural unit represented by general formula (3A) and / or general formula (3A').

4. The aromatic amine resin according to claim 3, comprising at least one compound selected from the group consisting of compounds represented by general formula (5-1) and compounds represented by general formula (5-2): 【Chemistry 7】 (where: Ar, Z, R １ , R ３’ , n′, R ｂ’ and R ｃ’ has the same meaning as in claim 3.

5. 4. The aromatic amine resin according to claim 1, wherein the amine equivalent is from 100 to 2000 g / equivalent.

6. The aromatic amine resin according to claim 1 or 3, having a number average molecular weight of 100 to 10,000.

7. A curable composition comprising the aromatic amine resin according to claim 1 or 3 and a curable resin.

8. A cured product of the curable composition according to claim 7.

9. A prepreg comprising a reinforcing substrate and a semi-cured product of the curable composition according to claim 7 impregnated into the reinforcing substrate.

10. A circuit board which is a laminate of the prepreg according to claim 9 and copper foil.

11. A build-up film comprising the curable composition according to claim 7.

12. A semiconductor encapsulant comprising the curable composition according to claim 7.

13. A semiconductor device comprising the cured product of the semiconductor encapsulation material according to claim 12.

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