Aromatic amine resin and application thereof

Abstract

Provided is an aromatic amine resin which is capable of suppressing water absorption of a cured product, and in addition, is capable of suppressing a decrease in dielectric properties (dielectric constant and dielectric loss tangent) and heat resistance. The present invention relates to an aromatic amine resin which is a reaction product of a fluorene compound (wherein the 9-position does not have a substituent), an aromatic amine, and a compound represented by general formula (1), and an application thereof. In addition, the present invention relates to a curable composition containing the aromatic amine resin, a cured product, a prepreg, a circuit board, a build-up film, a semiconductor sealing material, and a semiconductor device. It is preferable that the amine equivalent weight of the aromatic amine resin is 100 g / eq. To 2000 g / eq. The number average molecular weight of the aromatic amine resin is preferably 100 to 10000.

Description

Technical Field

[0001] The present invention relates to an aromatic amine resin, a curable composition, a cured product, a prepreg, a circuit substrate, a build-up film, a semiconductor sealing material and a semiconductor device, and in particular to an aromatic amine resin and application thereof. Background Art

[0002] Aromatic amine resins are intermediates of various polymers represented by polyamide resins, amideimide resins, and polyimide resins, and are also widely used as hardeners for epoxy resins, isocyanate resins, etc., due to their strong nucleophilicity. For example, epoxy resin compositions using aromatic amine resins as hardeners exhibit excellent heat resistance and insulation properties, and are widely used in electronic parts such as semiconductors and multilayer printed circuit boards.

[0003] Patent Document 1 discloses that the heat resistance and hygroscopicity of a cured product can be improved by using an aromatic amine resin having a biphenyl aralkyl structure in an epoxy resin composition.

[0004] [Prior art literature]

[0005] [Patent Document]

[0006] [Patent Document 1] International Publication No. 2016 / 117584 Summary of the invention

[0007] [Problems to be solved by the invention]

[0008] In recent years, the requirements for weather resistance and reliability of electronic parts such as semiconductors and multilayer printed circuit boards have become more stringent. If the hardened material used in electronic parts such as semiconductors and multilayer printed circuit boards absorbs water, the hardened material deteriorates, which may reduce dielectric properties or heat resistance. Therefore, aromatic amine resins that can provide hardened materials with suppressed water absorption are still required.

[0009] [Technical means to solve the problem]

[0010] The present inventors have repeatedly conducted diligent research to solve the above-mentioned problems, and as a result, have found that by using an aromatic amine resin having a structure in which the hydrogen atom at the 9-position of the fluorene structural unit is modified into an aralkyl group, it is possible to suppress the water absorption of a cured product using the resin, and further suppress the reduction in dielectric properties (dielectric constant and dielectric loss tangent) and heat resistance, thereby completing the present invention.

[0011] The gist of the present invention is as follows.

[0012] [1] An aromatic amine resin which is a reaction product of a fluorene compound (wherein the fluorene compound has no substituent at the 9-position), an aromatic amine and a compound represented by the general formula (1).

[0013] [Chemistry 1]

[0014]

[0015] (Here,

[0016] Ar is Ar 1 -Y-Ar 1 or Ar 1 ,

[0017] Ar 1 are each independently an aromatic cyclic group which may have a substituent,

[0018] 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,

[0019] R 1 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms,

[0020] X is a leaving group).

[0021] [2] The aromatic amine resin according to [1], wherein the fluorene compound is contained in an amount of 0.01 mol to 0.99 mol per 1 mol of the compound represented by the general formula (1).

[0022] [3] An aromatic amine resin represented by the general formula (5),

[0023] [Chemistry 2]

[0024]

[0025] (Here,

[0026] Z is independently a structural unit represented by the general formula (2A):

[0027] [Chemistry 3]

[0028]

[0029] or a structural unit represented by the general formula (3A),

[0030] [Chemistry 4]

[0031]

[0032] Z' is independently a structural unit represented by the general formula (2A')

[0033] [Chemistry 5]

[0034]

[0035] or a structural unit represented by the general formula (3A'),

[0036] [Chemistry 6]

[0037]

[0038] Ar are each independently Ar 1 or Ar 1 -Y-Ar 1 ,

[0039] Ar 1 are each independently an aromatic cyclic group which may have a substituent,

[0040] 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,

[0041] R 1 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms,

[0042] R 2 are independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom,

[0043] m is each independently an integer of 0 to 4,

[0044] R 3 are 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, the two R 3 They can also form rings together with the carbon atoms to which they are bonded.

[0045] n is each independently an integer of 0 to 3,

[0046] R b and R c are independently a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group,

[0047] R 2 'are independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom,

[0048] m' is an integer of 0 to 4, respectively independently.

[0049] R 3 ' are 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, the two R 3 ' can also form a ring together with the carbon atoms to which they are bonded,

[0050] n' is an integer of 0 to 4, respectively independently,

[0051] R b ' and R c 'are independently a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group,

[0052] p is the average value, which is a number greater than 0.

[0053] The resin includes structural units represented by the general formula (2A) and / or the general formula (2A′) and structural units represented by the general formula (3A) and / or the general formula (3A′).

[0054] [4] The aromatic amine resin according to [3], comprising at least one of a compound represented by the general formula (5-1) and a compound represented by the general formula (5-2),

[0055] [Chemistry 7]

[0056]

[0057] (Here,

[0058] Ar, Z, R 1 , R 3 ',n',R b ' and R c ' has the same meaning as [3]).

[0059] [5] The aromatic amine resin according to any one of [1] to [4], wherein the amine equivalent is 100 g / eq. to 2000 g / eq.

[0060] [6] The aromatic amine resin according to any one of [1] to [5], wherein the number average molecular weight is 100 to 10,000.

[0061] [7] A curable composition comprising the aromatic amine resin according to any one of [1] to [6] and a curable resin.

[0062] [8] A cured product, which is a cured product of the curable composition according to [7].

[0063] [9] A prepreg comprising a reinforcing substrate and a semi-cured product of the curable composition according to [7] impregnated into the reinforcing substrate.

[0064]

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

[0065]

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

[0066]

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

[0067]

[13] A semiconductor device comprising the hardened product of the semiconductor sealing material according to

[12] .

[0068] [Effects of the Invention]

[0069] The aromatic amine resin of the present invention can suppress water absorption of a cured product using the resin, thereby suppressing the reduction of dielectric properties (dielectric constant and dielectric loss tangent) and heat resistance. By using a curable composition containing the aromatic amine resin and a cured product thereof, a prepreg, a circuit substrate, a build-up film, a semiconductor sealing material and a semiconductor device can be provided, which suppress water absorption, thereby suppressing the reduction of dielectric properties (dielectric constant and dielectric loss tangent) and heat resistance. BRIEF DESCRIPTION OF THE DRAWINGS

[0070] Figure 1 These are the results of GPC measurement of the aromatic amine resin (1) synthesized in Example 1.

[0071] Figure 2 These are the results of 13C-NMR measurement of the aromatic amine resin (1) synthesized in Example 1.

[0072] Figure 3 These are the results of FD-MS measurement of the aromatic amine resin (1) synthesized in Example 1.

[0073] Figure 4 These are the GPC measurement results of the aromatic amine resin (2) synthesized in Example 2.

[0074] Figure 5 These are the results of 13C-NMR measurement of the aromatic amine resin (2) synthesized in Example 2.

[0075] Figure 6 These are the results of FD-MS measurement of the aromatic amine resin (2) synthesized in Example 2.

[0076] Figure 7 These are the GPC measurement results of the aromatic amine resin (3) synthesized in Example 3.

[0077] Figure 8 These are the results of 13C-NMR measurement of the aromatic amine resin (3) synthesized in Example 3.

[0078] Fig. 9 These are the results of FD-MS measurement of the aromatic amine resin (3) synthesized in Example 3.

[0079] Fig.10These are the GPC measurement results of the aromatic amine resin (4) synthesized in Example 4.

[0080] Fig.11 These are the results of 13C-NMR measurement of the aromatic amine resin (4) synthesized in Example 4.

[0081] Fig.12 These are the results of FD-MS measurement of the aromatic amine resin (4) synthesized in Example 4.

[0082] Fig.13 These are the GPC measurement results of the aromatic amine resin (5) synthesized in Example 5.

[0083] Fig.14 These are the results of 13C-NMR measurement of the aromatic amine resin (5) synthesized in Example 5.

[0084] Fig.15 These are the results of FD-MS measurement of the aromatic amine resin (5) synthesized in Example 5. DETAILED DESCRIPTION

[0085] Hereinafter, the mode for carrying out the invention will be described in detail, but the present invention is not limited to the following description and can be carried out with various modifications within the scope of the gist thereof.

[0086] [term]

[0087] The term "reaction raw material" in this specification refers to a compound used to obtain a target compound through a chemical reaction such as combination or decomposition and partially constitutes the chemical structure of the target compound, excluding substances that function as auxiliary agents for chemical reactions such as solvents and catalysts. In this specification, the term "reaction raw material" refers in particular to a precursor used to obtain a target aromatic amine resin through a chemical reaction.

[0088] The "structural unit" in this specification refers to the (repeating) unit of the chemical structure formed during reaction or polymerization. In other words, it refers to the partial structure other than the structure of the chemical bonds participating in the reaction or polymerization in the resulting compound formed by reaction or polymerization, which refers to the so-called residue.

[0089] The aliphatic hydrocarbon group in the present specification may be any of a linear type, a branched type, and a cyclic type, and may have an unsaturated bond in the structure. Examples of the aliphatic hydrocarbon group include groups having 1 to 20 carbon atoms.

[0090] The monovalent aliphatic hydrocarbon group in the present specification includes an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, and a cycloalkynyl group.

[0091] The alkyl group in the present specification may be any of a straight chain type and a branched type, and in terms of the number of carbon atoms, alkyl groups of 1 to 20 may be listed, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, sec-pentyl, tert-pentyl, neopentyl, pentyl, cyclopentyl, hexyl, heptyl, octyl, cumyl, nonyl, decyl, undecyl, dodecyl, and the like.

[0092] The alkenyl group in the present specification may be any of a straight chain type and a branched type, and in terms of the number of carbon atoms, examples include alkenyl groups having 2 to 20 carbon atoms, such as vinyl, allyl, butenyl, butadienyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, and the like.

[0093] The alkynyl group in the present specification may be any of a straight chain type and a branched type, and in terms of the number of carbon atoms, alkynyl groups having 2 to 20 may be listed, such as ethynyl, propargyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl, decynyl, undecynyl, dodecynyl, etc.

[0094] The cycloalkyl group in the present specification may be a monocyclic group or a polycyclic group, and examples of the cycloalkyl group include 3 to 30 carbon atoms, such as cyclopentyl, cyclohexyl, cycloheptyl, adamantyl, methylcyclohexyl, and ethylcyclohexyl.

[0095] The cycloalkenyl group in the present specification may be a monocyclic group or a polycyclic group, and examples of the cycloalkenyl group include cycloalkenyl groups having 3 to 30 carbon atoms, such as cyclohexenyl, methylcyclohexenyl, and ethylcyclohexenyl.

[0096] The cycloalkynyl group in the present specification may be a monocyclic group or a polycyclic group, and examples thereof include cycloalkynyl groups having 4 to 30 carbon atoms, such as cyclohexynyl, methylcyclohexynyl, and ethylcyclohexynyl.

[0097] The divalent aliphatic hydrocarbon group in the present specification includes an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group, a cycloalkenylene group, and a cycloalkynylene group.

[0098] The alkylene group in the present specification may be any of a straight chain type and a branched type, and in terms of the number of carbon atoms, alkylene groups of 1 to 20 may be listed, such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, etc.

[0099] The alkenylene group in the present specification may be either a straight chain type or a branched type, and examples thereof include alkenylene groups having 2 to 20 carbon atoms, such as vinylene, propenylene, butenylene, butadienylene, octenylene, decenylene, and dodecenylene.

[0100] The alkynylene group in the present specification may be any of a straight chain type and a branched type, and in terms of the number of carbon atoms, alkynylene groups having 2 to 20 may be listed, for example, ethynylene, propynylene, butynylene, butadiynylene, pentynylene, hexynylene, heptynylene, octynylene, nonynylene, decynylene, undecynylene, dodecynylene, and the like.

[0101] The alkoxy group in the present specification has the structure of alkyl-O-, and the description of the alkyl group mentioned above can be applied to the alkyl part in the structure, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, allyloxy, etc.

[0102] The cycloalkylene group in the present specification may be a monocyclic group or a polycyclic group, and examples thereof include cycloalkylene groups having 3 to 30 carbon atoms, and are divalent groups corresponding to the groups exemplified in the cycloalkyl group.

[0103] The cycloalkenylene group in the present specification may be a monocyclic group or a polycyclic group, and examples thereof include cycloalkenylene groups having 3 to 30 carbon atoms, and are divalent groups corresponding to the groups exemplified in the cycloalkenyl group.

[0104] The cycloalkynylene group in the present specification may be a monocyclic group or a polycyclic group, and examples thereof include cycloalkynylene groups having 4 to 30 carbon atoms, and are divalent groups corresponding to the groups exemplified in the cycloalkynyl group.

[0105] The aromatic ring in the present specification is a hydrocarbon ring having aromaticity and including a monocyclic ring or a condensed ring, and includes aromatic rings having 6 to 20 carbon atoms, such as benzene ring, naphthalene ring, indene ring, anthracene ring, etc. The aromatic ring group is a residue of an aromatic ring.

[0106] The aromatic hydrocarbon group in the present specification is a residue of an aromatic hydrocarbon compound, including an aryl group. Examples of the aryl group include aryl groups having 6 to 20 carbon atoms, such as phenyl, naphthyl, biphenylyl, and phenanthryl.

[0107] The arylalkyl group in the present specification is an alkyl group substituted with one or more, preferably one or two, and especially one aryl group, and the descriptions of the aryl group and the alkyl group described above can be applied to the aryl group and the alkyl group, for example, benzyl or phenethyl.

[0108] The halogen atom in the present specification is fluorine, chlorine, bromine and iodine.

[0109] The number average molecular weight (Mn) and the weight average molecular weight (Mw) in this specification are values ​​measured using gel permeation chromatography (hereinafter, abbreviated as "GPC") under the measurement conditions described in the examples described later.

[0110] The amine equivalent in this specification is a value measured by a neutralization titration method, and can be measured by the method described in the Examples.

[0111] [Reaction raw materials of aromatic amine resin]

[0112] The aromatic amine resin of the present invention uses a fluorene compound (which has no substituent at the 9-position) (hereinafter also simply referred to as a "fluorene compound"), an aromatic amine, and a compound represented by the general formula (1) as reaction raw materials.

[0113] <Fluorene compounds>

[0114] The fluorene compound is not particularly limited as long as it has no substituent at the 9-position of fluorene, and may be unsubstituted or substituted at a position other than the 9-position.

[0115] Examples of the fluorene compound include compounds represented by the following general formula (2).

[0116] [Chemistry 8]

[0117]

[0118] (Here,

[0119] m is each independently an integer of 0 to 4,

[0120] R 2 are independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom)

[0121] The aliphatic hydrocarbon group is preferably an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, or the like.

[0122] The aryl group is preferably a phenyl group, a tolyl group, a xylyl group, a naphthyl group, an indenyl group, or an indanyl group.

[0123] As the arylalkyl group, benzyl, phenethyl and cumyl are preferred.

[0124] As the alkoxy group, a methoxy group, an ethoxy group, a propoxy group and a butoxy group are preferred.

[0125] The halogen atom is preferably fluorine, chlorine or bromine.

[0126] m is preferably an integer of 0 to 2, more preferably 0 or 1, and particularly preferably 0, each independently.

[0127] The two m's may be the same or different, but are preferably the same.

[0128] When both m are 1 or more, R substituted on the two benzene rings constituting the fluorene skeleton 2 Can be the same or different.

[0129] When any one or both of m are 2 or more, the two or more R substituted on the same benzene ring constituting the fluorene skeleton 2 Can be the same or different.

[0130] Preferred examples of the compound of the general formula (2) include fluorene.

[0131] [Chemistry 9]

[0132]

[0133] The compound of the general formula (2) may be used alone or in combination of two or more at any ratio.

[0134] <Aromatic amines>

[0135] Aromatic amines are aromatic compounds having one unsubstituted or substituted amino group in the molecule. The substituted amino group may be a monosubstituted amino group or a disubstituted amino group. In terms of the breadth of industrial applicability, aromatic amines are preferably unsubstituted or monosubstituted amino groups containing active hydrogen. As substituents in the substituted amino group, aliphatic hydrocarbon groups and aromatic hydrocarbon groups can be cited, preferably alkyl groups (for example, alkyl groups having 1 to 4 carbon atoms) and aryl groups (aryl groups having 6 to 10 carbon atoms).

[0136] Examples of the aromatic amine include compounds represented by the following general formula (3).

[0137] [Chemistry 10]

[0138]

[0139] (Here,

[0140] n" is an integer from 0 to 4,

[0141] R 3 " are 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, the two R 3 " can also form a ring together with the carbon atoms to which they are bonded,

[0142] R b ” and R c " are independently a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group)

[0143] About R 3 ", as the aliphatic hydrocarbon group, an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, and butyl, is preferred.

[0144] The aryl group is preferably a phenyl group, a tolyl group, a xylyl group, or a naphthyl group.

[0145] As the arylalkyl group, benzyl, phenethyl and cumyl are preferred.

[0146] As the alkoxy group, a methoxy group, an ethoxy group, a propoxy group and a butoxy group are preferred.

[0147] The halogen atom is preferably fluorine, chlorine or bromine.

[0148] As R 3 ”, wherein alkyl and aryl are preferred.

[0149] Or, two R 3 " may also form a ring together with the carbon atoms to which they are bonded. Examples of the ring include hydrocarbon rings having 6 to 20 ring-constituting atoms, such as a benzene ring, a naphthalene ring, an anthracene ring, an adamantane ring, an indane ring, an indene ring, and the like. 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, or a halogen atom.

[0150] n" is preferably 0, 1 or 2.

[0151] When n" is 2, preferably two R 3 Together with the carbon atoms to which they are bonded, they form a benzene or naphthalene ring.

[0152] About R b ” and R c ", as the aliphatic hydrocarbon group, an alkyl group and an aryl group are preferred. As the alkyl group, an alkyl group having 1 to 4 carbon atoms, such as a methyl group, an ethyl group, a propyl group, and a butyl group are more preferred. As the aryl group, a phenyl group, a tolyl group, a xylyl group, and a naphthyl group are preferred.

[0153] R b ” and R c "It is preferred that both are hydrogen atoms, or one of them 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).

[0154] Preferred examples of the compound represented by the general formula (3) include the following compounds.

[0155] [Chemistry 11]

[0156]

[0157] Here, R b ” and R c " are independently a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Preferably Rb ” and R c " are both 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 " are both hydrogen atoms, or either 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).

[0158] The compound of the general formula (3) may be used alone or in combination of two or more at any ratio.

[0159] <Compound represented by general formula (1)>

[0160] The compound represented by the general formula (1) is a compound that can modify the hydrogen atom at the 9-position of the fluorene structural unit to an aralkyl group and can also react with an aromatic amine to function as a binder.

[0161] [Chemistry 12]

[0162]

[0163] (Here,

[0164] Ar is Ar 1 -Y-Ar 1 or Ar 1 ,

[0165] Ar 1 are each independently an aromatic cyclic group which may have a substituent,

[0166] 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,

[0167] R 1 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms,

[0168] X is a leaving group)

[0169] Ar 1 It is an aromatic cyclic group which may have a substituent. The aromatic cyclic group is not particularly limited, but is preferably a phenylene group, a naphthylene group, or an anthrylene group. In the case of a phenylene group, it is preferred that there are bonds at the 1 and 4 positions, in the case of a naphthylene group, it is preferred that there are bonds at the 2 and 6 positions, and in the case of an anthrylene group, it is preferred that there are bonds at the 9 and 10 positions.

[0170] Ar 1 -Y-Ar1 The two Ar 1 They may be the same or different, but are preferably the same.

[0171] Examples of the substituent include an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group, and a halogen atom.

[0172] The aliphatic hydrocarbon group is preferably an alkyl group having 1 to 4 carbon atoms, for example, a methyl group, an ethyl group, a propylene group, or a butylene group.

[0173] The aryl group is preferably a phenyl group, a tolyl group, a xylyl group, or a naphthyl group.

[0174] As the arylalkyl group, benzyl, phenethyl and cumyl are preferred.

[0175] As the alkoxy group, a methoxy group, an ethoxy group, a propoxy group and a butoxy group are preferred.

[0176] The halogen atom is preferably fluorine, chlorine or bromine.

[0177] As the substituent, an alkyl group, an aryl group, etc. are preferable among them.

[0178] 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).

[0179] The aliphatic hydrocarbon group having 1 to 6 carbon atoms is not particularly limited, but is preferably a methylene group, an ethylene group, a propylene group, an isopropylene group, or a butylidene group.

[0180] -P(=O)R a -R in the base a It is an aromatic ring group, preferably a phenyl group.

[0181] Among them, Y is preferably a single bond, an ethylene group, or a propylene group.

[0182] As Ar 1 -Y-Ar 1 , preferably biphenylene and binaphthylene.

[0183] X is a leaving group, and examples thereof include a hydroxyl group, a halogen atom, and an alkoxy group.

[0184] The halogen atom is preferably chlorine, bromine or iodine.

[0185] The alkoxy group is preferably an alkoxy group having 1 to 4 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group.

[0186] Among them, X is preferably chlorine, bromine, iodine, a hydroxyl group, or a methoxy group.

[0187] The two Xs may be the same or different.

[0188] R 1 It is a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms.

[0189] The aliphatic hydrocarbon group having 1 to 4 carbon atoms is not particularly limited, but is preferably a methyl group, an ethyl group, a propyl group, a butyl group or the like.

[0190] As R 1 , wherein a hydrogen atom or a methyl group is preferred. 1 They may be the same or different, but are preferably the same.

[0191] The compound of the general formula (1) includes a compound represented by the following general formula (1-1) (Ar is Ar 1 -Y-Ar 1 ) and a compound of the general formula (1-2) (Ar is Ar 1 ).

[0192] [Chemistry 13]

[0193]

[0194] (Here, R 1 ,Ar 1 , Y and X are defined and preferred as above)

[0195] The compound of the general formula (1) can be used alone or in combination of two or more. That is, the compound of the general formula (1) is a compound of the general formula (1-1), a compound of the general formula (1-2), or a compound of the general formula (1-1) and a compound of the general formula (1-2) are used in combination. The compound of the general formula (1-1) and the compound of the general formula (1-2) can be used alone or in combination of two. When the compounds of the general formula (1-1) and the general formula (1-2) are used, the water absorption is suppressed by using an aromatic amine resin, which is preferred. When the compound of the general formula (1-1) and the compound of the general formula (1-2) are used in combination, although there is no particular limitation, their molar ratio (the number of moles of the compound of the general formula (1-1): the number of moles of the compound of the general formula (1-2)) can be set to 10:90 to 90:10, preferably 20:80 to 80:20.

[0196] Preferred examples of the compound represented by the general formula (1-1) include the following compounds.

[0197] [Chemistry 14]

[0198]

[0199] Preferred examples of the compound represented by the general formula (1-2) include the following compounds.

[0200] [Chemistry 15]

[0201]

[0202] [Method for producing aromatic amine resin]

[0203] The aromatic amine resin of the present invention is a reaction product of the above-mentioned reaction raw materials, and can be specifically produced as follows.

[0204] The amounts of the fluorene compound, aromatic amine and compound of the general formula (1) used as the reaction raw materials are as follows.

[0205] From the viewpoint of introducing the aromatic amine, the amount of the compound of the general formula (1) may exceed 1 mol relative to 1 mol of the fluorene compound, and is not particularly limited as long as it exceeds 1 mol.

[0206] For example, the amount of the fluorene compound used may be 0.01 mol or more, preferably 0.1 mol or more, more preferably 0.3 mol or more, and may be 0.99 mol or less, preferably 0.95 mol or less, per 1 mol of the compound of the general formula (1).

[0207] During the reaction, since the fluorene compound and the compound of the general formula (1) react substantially in total amount, the molar ratio of the fluorene compound to the compound of the general formula (1) used in the reaction and the molar ratio of the structural units derived from the fluorene compound to the structural units derived from the compound of the general formula (1) in the obtained aromatic amine resin are substantially the same.

[0208] The amount of the aromatic amine used is not particularly limited. It can be set to an amount in which the unsubstituted or substituted amino group of the aromatic amine is 0.1 mol or more, preferably an amount in which the unsubstituted or substituted amino group of the aromatic amine is 0.2 mol or more, relative to the compound of the general formula (1). In addition, it can be set to an amount in which the unsubstituted or substituted amino group of the aromatic amine is 10 mol or less, preferably an amount in which the unsubstituted or substituted amino group of the aromatic amine is 9.5 mol or less.

[0209] Regarding the aromatic amine, some aromatic amine may remain unreacted, and the amount of the aromatic amine that has reacted can be calculated from the amine equivalent of the aromatic amine resin.

[0210] The aromatic amine resin can be produced by, for example, the following step 1 and step 2.

[0211] <Process 1>

[0212] Preferably, instead of adding an aromatic amine, the total amount of the fluorene compounds and the total amount of the compounds of the general formula (1) are reacted in an organic solvent at 10°C to 150°C using an alkali catalyst; or the total amount of the fluorene compounds and the total amount of the compounds of the general formula (1) are reacted with a portion or the total amount of the aromatic amine in an organic solvent at 10°C to 150°C using an alkali catalyst.

[0213] The amount of the aromatic amine used is not particularly limited, and can be set to an amount of 0.1 mol or more of the unsubstituted or substituted amino group of the aromatic amine relative to the general formula (1), preferably an amount of 0.2 mol or more of the unsubstituted or substituted amino group of the aromatic amine, and can be set to an amount of 10 mol or less of the unsubstituted or substituted amino group of the aromatic amine, preferably an amount of 9.5 mol or less of the unsubstituted or substituted amino group of the aromatic amine. By setting such an amount to be used, the generation of by-products can be suppressed.

[0214] As the organic solvent, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aromatic hydrocarbon solvents such as toluene, xylene, mesitylene, and solvesso, alcohol solvents such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, sec-butyl alcohol, and tert-butyl alcohol, cellosolve solvents such as methyl cellosolve and ethyl cellosolve, ether solvents such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane, and diethoxyethane, acetonitrile, dimethyl sulfoxide, cyclopentane, dimethylformamide, and dimethylacetamide are preferably used. In terms of solubility, toluene, xylene, mesitylene, solvesso, isopropyl alcohol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, etc. are preferably used. These organic solvents can be used alone or in combination of two or more in any ratio.

[0215] The amount of the organic solvent used is not particularly limited, but is preferably 50% by mass to 500% by mass based on the total amount of the compound of the general formula (1) and the fluorene compound added.

[0216] As the base catalyst, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium methoxide, potassium ethoxide, potassium tert-butoxide, triethylamine, pyridine, dimethylaminopyridine, etc. can be cited. In terms of reactivity, sodium hydroxide or potassium hydroxide is preferred. The amount of the base catalyst used can be set to 10 mol% to 1000 mol% relative to the compound of the general formula (1) put in. These catalysts can be used in the form of 1% to 50% by mass aqueous solution.

[0217] Phase transfer catalysts can also be used in the reaction. As phase transfer catalysts, for example, ammonium systems such as tetrabutylammonium chloride, tetrabutylammonium bromide, tetrabutylammonium, tetrabutylammonium iodide, tetrabutylammonium hydroxide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyltriethylammonium iodide, benzyltriethylammonium hydroxide, tetrabutylphosphonium chloride, tetrabutylphosphonium bromide, tetrabutylphosphonium iodide, tetrabutylphosphonium hydroxide, 12-crown-4-ether, 15-crown-5-ether, 18-crown-6-ether, and crown ether systems such as tribenzo-18-crown-6-ether can be listed. In terms of reactivity, tetrabutylammonium bromide, tetrabutylammonium iodide, benzyltriethylammonium chloride, and benzyltriethylammonium iodide are preferably used. Phase transfer catalysts can be used alone or in combination of two or more.

[0218] In order to promote the reaction, additives may also be used. 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 them, sodium iodide and potassium iodide are preferred. The additives may be used alone or in combination of two or more.

[0219] The reaction temperature can be 10° C. to 150° C., and is preferably 20° C. to 140° C. from the viewpoint of reactivity. The reaction time can be 1 hour to 72 hours, and is preferably 2 hours to 70 hours.

[0220] After the reaction is completed, it is suitably separated into an upper layer and a lower layer, and the lower layer as an aqueous layer is removed to obtain a reaction product. At this time, water may be added as needed to dissolve insoluble salts and remove the lower layer. In addition, the aqueous layer may be alkaline, neutralized by neutralization, or acidic. As the neutralizing agent used in the neutralization, for example, inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, sodium dihydrogen phosphate, and ammonium chloride, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid may be cited. These acid catalysts may be used alone or in combination of two or more.

[0221] <Process 2>

[0222] In the case where the aromatic amine is not added or a part of the aromatic amine is added and the reaction is carried out in step 1, the total amount or the remaining part of the aromatic amine is added to the reaction product obtained in step 1, and the reaction is carried out at 60° C. to 250° C. in the presence of an acid catalyst. In the case where the total amount of the aromatic amine is added in step 1, the reaction product obtained in step 1 is reacted at 60° C. to 250° C. in the presence of an acid catalyst.

[0223] The aromatic amine used in step 2 may be the same as or different from the aromatic amine used in step 1.

[0224] As the acid catalyst, any of organic acids, inorganic acids or solid acids can be used. 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 phosphates such as dimethyl phosphate or diethyl phosphate; alkyl sulfates such as dimethyl sulfate, diethyl sulfate, and lauryl sulfate; aromatic sulfuric acids such as phenyl sulfate and phenyl fluorosulfate; and various acids such as oxalic acid.

[0225] 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, heteropoly hydrochloric acid, and strongly acidic ion exchange resins. Examples of the layered silicate include kaolin family such as dickite, nacrite, kaolinite, silicon-rich kaolinite, metahalloysite, and halloysite, serpentine family such as chrysotile, lizardite, and antigorite, montmorillonite, sauconite, beidellite, nontronite, and saponite. The present invention relates to a smectite group such as aponite, taeniolite, hectorite, stevensite, a vermiculite group such as vermiculite, a mica group such as mica, illite, sericite, glauconite, attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, and chlorite group. These layered silicates may form a mixed layer. In addition, the acid catalyst may be used alone or in combination of two or more.

[0226] The amount of the acid catalyst is not particularly limited, but is preferably 0.001% by mass to 50% by mass based on the total amount of the charged reaction raw materials.

[0227] The reaction temperature is preferably 60° C. to 250° C., and in terms of reactivity, is preferably 80° C. to 240° C. The reaction time can be 1 to 72 hours, and is preferably 2 to 70 hours.

[0228] After the reaction is completed, neutralization treatment, water washing treatment, etc. are carried out as necessary, and unreacted reaction raw materials, organic solvents, etc. are distilled off under reduced pressure and heating conditions to obtain an aromatic amine resin.

[0229] The method for producing the aromatic amine resin of the present invention is not limited to the above method. For example, instead of step 1, a fluorene compound and a compound of the general formula (1) may be reacted in an organic solvent in the presence of a catalyst at 10°C to 150°C, and then a portion of an aromatic amine may be added, and after the reaction is carried out at 10°C to 150°C, the water layer is removed, and the reaction product is washed with water, and the obtained reaction product is supplied 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.

[0230] [Aromatic amine resin]

[0231] The aromatic amine resin of the present invention is a reaction product of a fluorene compound, an aromatic amine and a compound of the general formula (1), and has an unsubstituted or substituted amino group, preferably an unsubstituted or monosubstituted amino group.

[0232] The fluorene compound represented by general formula (2), the aromatic amine represented by general formula (3) and the compound of general formula (1) can respectively generate the structural unit represented by general formula (2A) or general formula (2A'), the structural unit represented by general formula (3A) or general formula (3A') and the structural unit represented by general formula (1A).

[0233] [Chemistry 16]

[0234]

[0235] (Here, the definitions, examples and preferred examples of m and m' are the same as those of m in the general formula (2).

[0236] R 2 and R 2 The definition, examples and preferred examples of ' and R in the general formula (2) 2 same,

[0237] *Represents bonding bonds)

[0238] [Chemistry 17]

[0239]

[0240] (Here,

[0241] n is an integer of 0 to 3, preferably 0, 1 or 2,

[0242] n' is an integer of 0 to 4, preferably 0, 1 or 2,

[0243] R 3 and R 3 The definition, examples and preferred examples of ' are the same as those of R" in the general formula (3),

[0244] R b and R c and R b ' and R c The definition, examples and preferred examples of ' and R in the general formula (3) b ” and R c "same,

[0245] *Represents bonding bonds)

[0246] [Chemistry 18]

[0247]

[0248] (Here,

[0249] Ar and R 1 The definitions, examples and preferred embodiments are the same as those of the general formula (1),

[0250] *Represents bonding bonds)

[0251] The aromatic amine resin of the present invention has a structure in which a structural unit of the general formula (1A) is bonded to a structural unit of the general formula (2A) and / or the general formula (2A′).

[0252] Preferably, at least one molecular chain terminal of the aromatic amine resin of the present invention is a structural unit of the general formula (3A'), and more preferably, both molecular chain terminals are structural units of the general formula (3A').

[0253] The aromatic amine resin of the present invention comprises structural units of the general formula (2A) and / or the general formula (2A'), structural units of the general formula (3A) and / or the general formula (3A') and structural units of the general formula (1A), wherein the bonding bonds of the structural units of the general formula (2A) and / or the general formula (2A') may be bonded to the bonding bonds of the structural units of the general formula (1A). In the case where the structural units of the general formula (2A') are present, the structural units constitute the ends of the molecular chains.

[0254] Preferably, at least one of the molecular chain ends is a structural unit of the general formula (3A'), and more preferably, both molecular chain ends are structural units of the general formula (3A').

[0255] Ar in the structural unit of the general formula (1A) in the aromatic amine resin of the present invention is Ar 1 or Ar 1 -Y-Ar 1 That is, all Ar contained in the aromatic amine resin may be Ar1 , or Ar 1 -Y-Ar 1 , or may contain Ar 1 -Y-Ar 1 with Ar 1 By introducing Ar into the molecular chain of aromatic amine resin 1 with Ar 1 -Y-Ar 1 At least one of the above can suppress water absorption by using an aromatic amine resin, so it is preferred. 1 -Y-Ar 1 with Ar 1 In the case of, although not particularly limited, their molar ratio (Ar 1 -Y-Ar 1 Number of moles: Ar 1 The molar number) can be set to 10:90 to 90:10, preferably 20:80 to 80:20.

[0256] The structural unit of the general formula (1A) is Ar is Ar 1 -Y-Ar 1 The structural unit represented by the following general formula (1-1A) or Ar is Ar 1 The structural unit of the general formula (1-2A) or the structural unit of the following general formula (1-1A) and Ar is Ar 1 The structural unit of the general formula (1-2A) is preferably a structural unit of the general formula (1A) containing the structural unit of the following general formula (1-1A) and the structural unit of the following general formula (1-2A) because the water absorption is suppressed by using an aromatic amine resin.

[0257] [Chemistry 19]

[0258]

[0259] (Here, R 1 ,Ar 1 The definitions and preferred examples of Y are the same as those of the general formula (1),

[0260] *Represents bonding bonds)

[0261] When the structural unit of the general formula (1A) includes the structural unit of the general formula (1-1A) and the structural unit of the general formula (1-2A), although not particularly limited, their molar ratio (the number of moles of the structural unit of the general formula (1-1A): the number of moles of the structural unit of the general formula (1-2)) can be set to 10:90 to 90:10, preferably 20:80 to 80:20.

[0262] Preferred examples of the structural unit of the general formula (1-1A) include the following structural units.

[0263] [Chemistry 20]

[0264]

[0265] Preferred examples of the structural unit of the general formula (1-2A) include the following compounds.

[0266] [Chemistry 21]

[0267]

[0268] Examples of the aromatic amine resin of the present invention include aromatic amine resins represented by the following general formula (5).

[0269] [Chemistry 22]

[0270]

[0271] (Here,

[0272] Z is independently a structural unit represented by the general formula (2A):

[0273] [Chemistry 23]

[0274]

[0275] or a structural unit represented by the general formula (3A),

[0276] [Chemistry 24]

[0277]

[0278] Z' is independently a structural unit represented by the general formula (2A')

[0279] [Chemistry 25]

[0280]

[0281] or a structural unit represented by the general formula (3A'),

[0282] [Chemistry 26]

[0283]

[0284] Ar are each independently Ar 1 or Ar 1 -Y-Ar 1 ,

[0285] Ar 1 are each independently an aromatic cyclic group which may have a substituent,

[0286] 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,

[0287] R 1 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms,

[0288] R 2 are independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom,

[0289] m is each independently an integer of 0 to 4,

[0290] R 3 are 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, the two R 3 They can also form rings together with the carbon atoms to which they are bonded.

[0291] n is each independently an integer of 0 to 3,

[0292] R b and R c are independently a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group,

[0293] R 2 'are independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom,

[0294] m' is an integer of 0 to 4, respectively independently.

[0295] R 3 ' are 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, the two R 3 ' can also form a ring together with the carbon atoms to which they are bonded,

[0296] n' is an integer of 0 to 4, respectively independently,

[0297] R b ' and R c 'are independently a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group,

[0298] p is the average value, which is a number greater than 0.

[0299] The resin comprises structural units represented by the general formula (2A) and / or the general formula (2A') and structural units represented by the general formula (3A) and / or the general formula (3A'), wherein * represents a bonding bond,

[0300] In the above text, Ar, Ar 1 , Y, R 1 , R 2 , R 3 , R b , R c , m, n, R 2 '、R 3 '、R b '、R c The examples and preferred examples of ', m', n' and p are the same as those described above. 1 with Ar 1 -Y-Ar 1 The examples and preferred embodiments are the same as above.

[0301] The aromatic amine resin of general formula (5) is a mixture of compounds of the general formula (5) wherein p is an integer greater than 0 (wherein not all of the compounds are compounds of the general formula (5) wherein p is 0), preferably a compound containing both structural units represented by general formula (2A) and / or general formula (2A') and structural units represented by general formula (3A) and / or general formula (3A') in the molecule.

[0302] In the resin, the total amount of the general formula (2A) and the general formula (2A') is preferably 0.1 mol to 10 mol, more preferably 0.5 mol to 9.5 mol, per 1 mol of the total amount of the structural units of the general formula (3A) and the general formula (3A').

[0303] Preferred examples include aromatic amine resins represented by the following general formula (5-0).

[0304] [Chemistry 27]

[0305]

[0306] (In the formula, Ar, Z, R 1 , R 3 '、R b '、R c ', n' and p are the same as those in general formula (5)

[0307] Here, Ar, Z, R 1 , R 3 , R b '、R c The examples and preferred examples of ', n' and p are the same as those described above. 1 with Ar 1 -Y-Ar 1 The examples and preferred examples are the same as above, and R in Z 2 ,m,R 3 ,n,R b and Rc The examples and preferred embodiments are the same as above.

[0308] As a more preferable example of the aromatic amine resin of the present invention, an aromatic amine resin represented by the following general formula (5-0') can be mentioned.

[0309] [Chemistry 28]

[0310]

[0311] (Here, R 2 ,m,R 3 ,n,R 3 ',n',R b , R c , R b ' and R c 'As mentioned above,

[0312] Ar'

[0313] [Chemistry 29]

[0314]

[0315] s is the average value, which is a number greater than 0.

[0316] t is the average value, which is a number above 0.

[0317] The order of the structural units enclosed by s and the structural units enclosed by t is not limited)

[0318] The aromatic amine resin of the general formula (5) and the aromatic amine resin of the general formula (5-0) may each be a mixture of compounds having a structural unit enclosed by p with an integer greater than 0, but not all of the compounds are compounds of the general formula (5) in which p is 0. The aromatic amine resin of the general formula (5) preferably contains at least one of the compound represented by the general formula (5-1) and the compound represented by the general formula (5-2).

[0319] [Chemistry 30]

[0320]

[0321] (Here,

[0322] Ar, Z, R 1 , R 3 '、R b '、R c ' and n' are as above,

[0323] Z in the general formula (5-1) and at least one Z in the general formula (5-2) are structural units represented by the general formula (2A)

[0324] The aromatic amine resin of the present invention may contain a compound of the general formula (6) in part thereof. The compound of the general formula (6) corresponds to the compound wherein p is 0 in the general formula (5).

[0325] [Chemistry 31]

[0326]

[0327] (Here,

[0328] Ar, R 1 , R 3 '、R b '、R c ' and n' are as above)

[0329] The number average molecular weight (Mn) of the aromatic amine resin may be in the range of 100 to 10,000, preferably 200 to 8000. The weight average molecular weight (Mw) of the aromatic amine resin may be in the range of 100 to 50,000, preferably 300 to 40,000.

[0330] The molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the aromatic amine resin may be in the range of 1-5, and preferably 1-4.

[0331] The amine equivalent of the aromatic amine resin is preferably in the range of 100 to 2,000, more preferably 200 to 1,800.

[0332] [Curing composition]

[0333] The curable composition of the present invention may contain the aromatic amine resin of the present invention and a curable resin. By using the aromatic amine resin of the present invention, water absorption of the cured product obtained from the curable composition can be suppressed, and further, the reduction of dielectric properties (dielectric constant and dielectric loss tangent) and heat resistance can be suppressed.

[0334] The curable composition may also 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, amine resins containing aralkylene groups, and the like. 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 may be appropriately adjusted according to the desired performance of the cured product, and is preferably 50% by mass or more, and more preferably 80% by mass or more.

[0335] The curable resin is not particularly limited as long as it is a compound having a functional group that can react with the aromatic amine resin of the present invention, and examples thereof include epoxy resins. The epoxy resin is not particularly limited, and various epoxy resins can be used. As an example, various bisphenol-type epoxy resins, various novolac-type epoxy resins, and epoxy resins containing aralkylene groups can be mentioned. These can be used alone or in combination.

[0336] The mixing ratio of the aromatic amine resin to the curable resin can be appropriately adjusted according to the desired performance of the cured product, and is preferably in the range of 0.5 to 1.5 mol of reactive groups in the curable resin per 1 mol of unsubstituted or substituted amino groups in the aromatic amine resin. When the other aromatic amine resin is used, it is preferably in the range of 0.5 to 1.5 mol of reactive groups in the curable resin per 1 mol of the total unsubstituted or substituted amino groups in the curable composition.

[0337] When epoxy resin is used as the curable resin, a curing accelerator may be used as needed. As the curing accelerator, various curing accelerators may be used, for example, phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, etc. These can be used alone or in combination. Among them, phosphorus compounds such as triphenylphosphine, or imidazoles are preferred in terms of excellent curability, heat resistance, electrical properties, moisture resistance and reliability. Regarding the amount of curing accelerator added, for example, relative to 100 parts by mass of the total mass of the curable composition (excluding the solvent), it is preferably used in the range of 0.01 parts by mass to 10 parts by mass.

[0338] The curable composition may contain other resin components. Examples of the other resins include active ester resins, maleimide resins, cyanate resins, unsaturated polyester resins, polybutadiene resins, and phenol resins.

[0339] The curable composition may also contain various formulation agents such as a curing accelerator, a silane coupling agent, a release agent, a pigment, an emulsifier, a non-halogen flame retardant, an inorganic filler, a flame retardant (e.g., an inorganic phosphorus flame retardant, an organic phosphorus flame retardant, a halogen flame retardant), and a solvent.

[0340] The curable composition can be obtained by uniformly mixing the aromatic amine resin of the present invention, a curable resin, and any optional components (for example, a curing catalyst, a formulation agent, etc.).

[0341] [Hardened material]

[0342] The hardened product of the present invention can be obtained by hardening the hardening composition of the present invention. The hardening method is not particularly limited, and a known method can be used. The hardened product can be in the form of a laminate, a cast, an adhesive layer, a coating, a film, etc.

[0343] [Semiconductor sealing materials]

[0344] The semiconductor sealing material of the present invention may 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 sealing material containing the curable composition can exhibit excellent dielectric properties (low dielectric constant and low dielectric loss tangent) and high heat resistance.

[0345] The semiconductor sealing material can use a material containing an inorganic filler in 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, aluminum nitride, and the like.

[0346] The amount of the inorganic filler can be 0.5 to 1200 parts by mass based on 100 parts by mass of the curable composition.

[0347] Various compounding agents can be blended into the semiconductor sealing material, and examples of the compounding agent include those described in connection with the curable composition.

[0348] The semiconductor sealing material can be obtained by mixing the curable composition of the present invention and a compounding agent as required. For example, a method of sufficiently performing melt mixing using an extruder, a kneader, a roll, etc. until the mixture becomes uniform can be mentioned.

[0349] [Semiconductor devices]

[0350] The semiconductor device of the present invention may include a cured product of the semiconductor sealing material of the present invention. The semiconductor sealing material used in the semiconductor device of the present invention contains a curable composition containing the aromatic amine resin of the present invention. Since the semiconductor device of the present invention includes the cured product of the semiconductor sealing material, it has excellent heat resistance and dielectric properties.

[0351] The semiconductor device can be obtained by heat-curing the semiconductor sealing material of the present invention, for example, the following methods can be cited: casting, or molding using a transfer molding machine, injection molding machine, etc., and then heat-curing at a temperature range of room temperature (20°C) to 250°C.

[0352] [Prepreg]

[0353] The prepreg of the present invention may include a reinforcing substrate and a semi-cured product of the curable composition of the present invention impregnated in the reinforcing substrate.

[0354] The method for obtaining a prepreg from the curable composition is not particularly limited, and the following method can be mentioned: after impregnating a reinforcing substrate (e.g., paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, etc.) with a curable composition prepared by mixing an organic solvent described later and making a varnish, the curable composition is heated at a heating temperature (preferably 50° C. to 170° C.) corresponding to the type of solvent used to semi-cure (or not cure).

[0355] The mass ratio of the curable composition to the reinforcing base material used is not particularly limited, but the prepreg is preferably prepared so that the resin component in the prepreg is 20% by mass to 60% by mass.

[0356] The semi-cured product of the curable composition can be obtained by adjusting the heating temperature and heating time and stopping the curing reaction halfway when the curing reaction is not completed. The curing degree of the semi-cured product can be set to, for example, 85% or less and 5% or more. Here, the cured product can have a higher curing degree than the semi-cured product.

[0357] The degree of curing of the semi-cured product can be calculated by measuring the curing calorific value when the curable composition is heated and the curing calorific value of the semi-cured product using a differential scanning calorimeter (DSC) and using the following formula.

[0358] Curing degree (%) = [1-(curing calorific value of semi-cured product / curing calorific value of curable composition)] × 100

[0359] As the organic solvent used in the manufacture of the prepreg, for example, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. The selection and usage of the organic solvent can be appropriately selected according to the application. For example, in the case of manufacturing a circuit board from the prepreg, a polar solvent having a boiling point of 160° C. or less, such as methyl ethyl ketone, acetone, and dimethylformamide, is preferably used, and the usage is preferably an amount in which the non-volatile component is 40% by mass to 80% by mass.

[0360] [Circuit board]

[0361] The circuit board of the present invention comprises a laminate of the prepreg of the present invention and copper foil. The method for obtaining the circuit board is not particularly limited, and for example, the following method can be cited: the prepreg of the present invention is laminated as needed, and copper foil is overlapped, and heat-pressed at 170°C to 300°C for 10 minutes to 3 hours under a pressure of 1 MPa to 10 MPa.

[0362] [Build-up film]

[0363] 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 examples thereof include 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.

[0364] The build-up film is required to soften under the lamination temperature conditions (usually 70°C to 140°C) in the vacuum lamination method, and to exhibit fluidity (resin flow) capable of filling the via holes or through-holes present in the circuit substrate while laminating the circuit substrate. Therefore, in order to exhibit such characteristics, the curable composition is preferably formulated with the above-mentioned components.

[0365] Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1mm to 0.5mm, and the depth is usually 0.1mm to 1.2mm, and it is usually preferable to be able to fill the resin within the above range. In the case of laminating both sides of the circuit board, it is ideal to fill about 1 / 2 of the through hole.

[0366] The method for producing the adhesive film described above can be specifically produced in the following manner: after preparing the varnish-like curable composition, the varnish-like composition is applied to the surface of a support film (Y), and then the organic solvent is dried by heating or blowing hot air to form a composition layer (X) containing the curable composition.

[0367] The thickness of the formed composition layer (X) is usually preferably equal to or greater than the thickness of the conductor layer. The thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, so the thickness of the resin composition layer is preferably 10 to 100 μm.

[0368] The composition layer (X) may be protected by a protective film described below. Protection by a protective film can prevent dust and the like from adhering to or damaging the surface of the resin composition layer.

[0369] The support film (Y) and the protective film mentioned above include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes referred to as "PET") and polyethylene naphthalate, polycarbonate, and polyimide, and further include release paper or metal foils such as copper foil and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to a matte treatment and a corona treatment.

[0370] 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.

[0371] The support film (Y) described above is peeled off after being laminated on the circuit substrate or after being heat-cured to form an insulating layer. If the support film (Y) is peeled off after the adhesive film is heat-cured, dust and the like can be prevented from being attached during the curing step. When peeling off after curing, the support film is usually subjected to a demolding treatment in advance.

[0372] [use]

[0373] The hardened material obtained by the curable composition containing the aromatic amine resin of the present invention can be suitably used for heat-resistant components or electronic components because of its excellent heat resistance and dielectric properties. It can be especially suitably used for prepregs, circuit boards, semiconductor sealing materials, semiconductor devices, build-up films, build-up substrates, adhesives or resist materials using conductive pastes, etc. In addition, it can also be suitably used for the matrix resin of fiber-reinforced resins, and is particularly suitable as a prepreg with high heat resistance. In addition, the aromatic amine resin contained in the curable composition can be coated because it shows excellent solubility in various solvents. The heat-resistant components or electronic components thus obtained can be suitably used for various purposes, for example, industrial machinery parts, general machinery parts, parts such as automobiles / railways / vehicles, space / aviation related parts, electronic / electrical parts, building materials, container / packaging components, daily necessities, sports / leisure products, frame components for wind power generation, etc., but are not limited to these.

[0374] [Example]

[0375] The present invention is specifically described by way of Examples and Comparative Examples, but the present invention is not limited to the following description and can be implemented with various modifications within the scope of the gist thereof. Hereinafter, "parts" and "%" are based on mass unless otherwise specified.

[0376] The physical properties of the aromatic amine resin were evaluated in the following manner.

[0377] (1) GPC measurement

[0378] The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the aromatic amine resins obtained in Examples and Comparative Examples were calculated using the following measuring apparatus and measuring conditions.

[0379] "Measurement device"

[0380] HLC-8320GPC manufactured by Tosoh Corporation

[0381] "Measurement conditions"

[0382] Column: Protection column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

[0383] Detector: RI (differential refractometer)

[0384] Data processing: "GPC WorkStation EcoSEC-WorkStation" manufactured by Tosoh Corporation

[0385] Measurement conditions: column temperature 40°C

[0386] Solvent: Tetrahydrofuran

[0387] Flow rate 1.0ml / min

[0388] Standard: According to the measurement manual of the "GPC WorkStation EcoSEC WorkStation", the following monodisperse polystyrene with known molecular weight was used.

[0389] (Polystyrene used)

[0390] "A-500" manufactured by Tosoh Co., Ltd.

[0391] "A-1000" manufactured by Tosoh Co., Ltd.

[0392] "A-2500" manufactured by Tosoh Co., Ltd.

[0393] "A-5000" manufactured by Tosoh Co., Ltd.

[0394] "F-1" manufactured by Tosoh Co., Ltd.

[0395] "F-2" manufactured by Tosoh Co., Ltd.

[0396] The "F-4" manufactured by Tosoh Co., Ltd.

[0397] The F-10 manufactured by Tosoh Co., Ltd.

[0398] The F-20 manufactured by Tosoh Corporation

[0399] "F-40" manufactured by Tosoh Co., Ltd.

[0400] "F-80" manufactured by Tosoh Co., Ltd.

[0401] The F-128 manufactured by Tosoh Corporation

[0402] Sample: A sample (50 μl) obtained by filtering a tetrahydrofuran solution containing 1.0% by mass of the aromatic amine resin obtained in Synthesis Example in terms of resin solid content using a microfilter.

[0403] (2) Field Desorption-Mass Spectrometry (FD-MS)

[0404] The FD-MS spectrum of the aromatic amine resin obtained in the examples was measured using the following measuring apparatus and measuring conditions.

[0405] Measurement device: JMS-T100GC AccuTOF

[0406] Measurement conditions

[0407] Measurement range: m / z = 4.00 to 2000.00

[0408] Change rate: 51.2mA / minute

[0409] Final current value: 45mA

[0410] Cathode voltage: -10kV

[0411] Recording interval: 0.07 seconds

[0412] (3) 13 C-NMR ( 13C-Nuclear Magnetic Resonance, 13 C-NMR) determination

[0413] The aromatic amine resin obtained in the embodiment 13 The C-NMR spectrum was measured using the following measuring apparatus and measuring conditions.

[0414] 13 C-NMR: JNM-ECZ400S manufactured by JEOL RESONANCE

[0415] Resonance frequency: 100MHz

[0416] Cumulative times: 4000 times

[0417] Solvent: Chloroform-d

[0418] Sample concentration: 12 mass%

[0419] Moderator: Chromium(III) acetylacetonate

[0420] (4) Amine equivalent

[0421] The amine equivalent of the aromatic amine obtained in the examples was measured by the following method.

[0422] In a 500 mL stoppered Erlenmeyer flask, 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 accurately weighed, and then a cooling tube was installed and heated to reflux in an oil bath set at 120° C. for 150 minutes.

[0423] After cooling, 5.0 mL of distilled water, 100 mL of propylene glycol monomethyl ether, and 75 mL of tetrahydrofuran were added, and titrated using a 0.5 mol / L potassium hydroxide-ethanol solution by potentiometric titration. A blank test was performed in the same manner to make corrections.

[0424] Amine equivalent (g / equivalent) = (S×2,000) / (Blank-A)

[0425] S: Sample quantity (g)

[0426] A: Consumption of 0.5 mol / L potassium hydroxide-ethanol solution (mL)

[0427] Blank: Consumption of 0.5 mol / L potassium hydroxide-ethanol solution in the blank test (mL)

[0428] <Example 1 Synthesis of Aromatic Amine Resin (1)>

[0429] 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, 210.62 parts by mass of α,α'-dichloro-p-xylene (hereinafter referred to as PXDC), 7.76 parts by mass of tetrabutylammonium bromide (hereinafter referred to as TBAB), 3.99 parts by mass of potassium iodide, and 465.9 parts by mass of xylene were added, and the temperature was raised to 60° C. while stirring. Then, 309.4 parts by mass of a 48% by mass potassium hydroxide aqueous solution was slowly added dropwise 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. Then, 117.7 parts by mass of aniline, 155.3 parts by mass of isopropyl alcohol (hereinafter referred to as IPA), and 284.7 parts by mass of water were added, the temperature was raised to 75°C, and the mixture was reacted at the same temperature for 10 hours. The lower layer was separated to remove the water layer, and the mixture was washed four times with 334.9 parts by mass of water.

[0430] Then, 280.1 parts by mass of aniline and 67.0 parts by mass of activated clay were added, the temperature was raised to 200°C, and the mixture was 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 decompressed to distill off the solvent and excess aniline, thereby obtaining the target aromatic amine resin (1) (amine equivalent 305 g / equivalent).

[0431] The obtained aromatic amine resin (1) had a Mn of 635 and a Mw of 1077. 13 C-NMR confirmed the quaternary carbon at the 9-position of fluorene and the remaining amount of N-alkylated products. In addition, FD-MS confirmed the target product at m / z 556.3 and 824.5. Figure 1 The obtained GPC diagram is shown in Figure 2 Shown in 13 C-NMR spectrum, Figure 3 The FD-MS graph is shown in FIG.

[0432] <Example 2 Synthesis of Aromatic Amine Resin (2)>

[0433] 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, 210.62 parts by mass of PXDC, 7.76 parts by mass of TBAB, 3.99 parts by mass of potassium iodide, and 465.9 parts by mass of xylene were added, and the temperature was raised to 60°C while stirring. Then, 309.4 parts by mass of a 48% by mass potassium hydroxide aqueous solution was slowly added dropwise 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. Then, 153.1 parts by mass of 2-ethylaniline, 155.3 parts by mass of IPA, and 284.7 parts by mass of water were added, the temperature was raised to 75°C, and the reaction was carried out at the same temperature for 10 hours, and the lower layer was separated to remove the water layer, and the water layer was washed four times with 368.6 parts by mass of water.

[0434] Then, 364.5 parts by mass of 2-ethylaniline and 73.7 parts by mass of activated clay were added, the temperature was raised to 200°C, and the mixture was 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 decompressed to distill off the solvent and excess 2-ethylaniline, thereby obtaining the target aromatic amine resin (2) (amine equivalent 314 g / equivalent).

[0435] The obtained aromatic amine resin (2) had an Mn of 444 and an Mw of 729. 13 C-NMR confirmed the quaternary carbon at the 9-position of fluorene and the remaining amount of N-alkylated products. In addition, FD-MS confirmed the target product at m / z 612.4 and 880.6. Figure 4 The obtained GPC diagram is shown in Figure 5 Shown in 13 C-NMR spectrum, Figure 6 The FD-MS graph is shown in FIG.

[0436] <Example 3 Synthesis of Aromatic Amine Resin (3)>

[0437] 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, 210.62 parts by mass of PXDC, 7.76 parts by mass of TBAB, 3.99 parts by mass of potassium iodide, and 465.9 parts by mass of xylene were added, and the temperature was raised to 60°C while stirring. Then, 309.4 parts by mass of a 48% potassium hydroxide aqueous solution was slowly added dropwise while paying attention to heat generation, and the reaction was carried out at the same temperature for 6 hours from the end of the addition. Then, 153.1 parts by mass of 2,6-dimethylaniline, 155.3 parts by mass of IPA, and 284.7 parts by mass of water were added, the temperature was raised to 75°C, and after reacting at the same temperature for 17 hours, the lower layer was separated to remove the water layer, and the water layer was washed four times with 368.6 parts by mass of water.

[0438] Then, 211.4 parts by mass of 2,6-dimethylaniline and 73.7 parts by mass of activated clay were added, the temperature was raised to 200°C, and the mixture was 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 decompressed to distill off the solvent and excess 2,6-dimethylaniline, and the target aromatic amine resin (3) (amine equivalent 305 g / equivalent) was obtained.

[0439] The obtained aromatic amine resin (3) had a Mn of 586 and a Mw of 814. 13 C-NMR confirmed the quaternary carbon at the 9-position of fluorene, and almost no residual N-alkylated product was confirmed. In addition, FD-MS confirmed the target product at m / z 612.4 and 880.6. Figure 7 The obtained GPC diagram is shown in Figure 8 Shown in 13 C-NMR spectrum, Fig. 9 The FD-MS graph is shown in FIG.

[0440] <Example 4 Synthesis of Aromatic Amine Resin (4)>

[0441] 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, 210.62 parts by mass of PXDC, 7.76 parts by mass of TBAB, 3.99 parts by mass of potassium iodide, and 465.9 parts by mass of xylene were added, and the temperature was raised to 60°C while stirring. Then, 309.4 parts by mass of a 48% potassium hydroxide aqueous solution was slowly added dropwise while paying attention to heat generation, and the reaction was carried out at the same temperature for 6 hours from the end of the addition. Then, 153.1 parts by mass of 2,3-dimethylaniline, 155.3 parts by mass of IPA, and 284.7 parts by mass of water were added, the temperature was raised to 75°C, and after reacting at the same temperature for 15 hours, the lower layer was separated to remove the water layer, and the water layer was washed four times with 368.6 parts by mass of water.

[0442] Then, 211.4 parts by mass of 2,3-dimethylaniline and 73.7 parts by mass of activated clay were added, the temperature was raised to 200°C, and the mixture was 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 decompressed to distill off the solvent and excess 2,3-dimethylaniline, and the target aromatic amine resin (4) (amine equivalent 319 g / equivalent) was obtained.

[0443] The obtained aromatic amine resin (4) had a Mn of 598 and a Mw of 1021. 13C-NMR confirmed the quaternary carbon at the 9-position of fluorene and the remaining amount of N-alkylated products. In addition, FD-MS confirmed the target product at m / z 612.4 and 880.6. Fig.10 The obtained GPC diagram is shown in Fig.11 Shown in 13 C-NMR spectrum, Fig.12 The FD-MS graph is shown in FIG.

[0444] <Example 5 Synthesis of Aromatic Amine Resin (5)>

[0445] 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 added, and the temperature was raised to 60°C while stirring. Then, 253.2 parts by mass of a 48% potassium hydroxide aqueous solution was slowly added dropwise while paying attention to heat generation, and the reaction was carried out at the same temperature for 10 hours from the end of the addition. Then, 153.1 parts by mass of 2,6-dimethylaniline, 163.3 parts by mass of IPA, and 232.9 parts by mass of water were added, the temperature was raised to 75°C, and after reacting at the same temperature for 15 hours, the lower layer was separated to remove the water layer, and the water layer was washed four times with 406.6 parts by mass of water.

[0446] Then, 211.4 parts by mass of 2,6-dimethylaniline and 81.3 parts by mass of activated clay were added, the temperature was raised to 200°C, and the mixture was 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 decompressed to distill off the solvent and excess 2,6-dimethylaniline, and the target aromatic amine resin (5) (amine equivalent 433 g / equivalent) was obtained.

[0447] The obtained aromatic amine resin (5) had a Mn of 761 and a Mw of 1167. 13 C-NMR confirmed the quaternary carbon at the 9th position of fluorene, and almost no residual N-alkylated product was confirmed. In addition, FD-MS confirmed the target product at m / z 764.5 and 1108.7. Fig.13 The obtained GPC diagram is shown in Fig.14 Shown in 13 C-NMR spectrum, Fig.15 The FD-MS graph is shown in FIG.

[0448] <Examples 6 to 10 and Comparative Example 1>

[0449] Liquid epoxy resin (Epiclon 850-S manufactured by DIC Corporation, epoxy equivalent 188 g / equivalent) and aromatic amine resin or diaminodiphenylmethane were heated and mixed at a temperature of 150°C or less in the mass ratio shown in Table 1, and then poured into a template 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 performed on the obtained cured product. The results are shown in Table 1.

[0450] (1) Water absorption

[0451] A test piece (about 0.6 g) including a cured product was treated at 121° C. and a humidity of 100% for 6 hours, and the water absorption (%) was determined from the difference in mass before and after the treatment.

[0452] Water absorption (%) =

[0453] ((mass of the test piece before treatment - mass of the test piece after treatment) ÷ mass of the test piece before treatment) × 100

[0454] (2) Dielectric constant and dielectric loss tangent

[0455] According to Japanese Industrial Standards (JIS)-C-6481, the dielectric constant and dielectric loss tangent at 10 GHz of the test piece after absolute drying and storage in a room at 23°C and 50% humidity for 24 hours were measured using the cavity resonance method using the network analyzer "E8362C" manufactured by Agilent Technologies Co., Ltd. The difference between the dielectric constant and dielectric loss tangent after treatment under the conditions of 121°C and 100% humidity and the dielectric constant and dielectric loss tangent before treatment was calculated.

[0456] Difference in dielectric constant = dielectric constant after treatment - dielectric constant before treatment

[0457] Difference in dielectric loss tangent = dielectric loss tangent after treatment - dielectric loss tangent before treatment

[0458] (3) Heat resistance (Dynamic Mechanical Analysis (DMA) Tg)

[0459] Using a viscoelasticity measuring device ("Solid Viscoelasticity Measuring Device RSAII" manufactured by Rheometrics, rectangular tension method: frequency 1 Hz, heating rate 3°C / min), the temperature on the low temperature side where the Tanδ change rate is the largest is evaluated as the glass transition temperature (Tg). The difference between the Tg after treatment and the Tg before treatment under the conditions of 121°C and 100% humidity is calculated.

[0460] Tg difference (℃) =

[0461] Glass transition temperature after treatment - Glass transition temperature before treatment

[0462] [Table 1]

[0463]

[0464] *The values ​​for epoxy resin, aromatic amine resin and diaminodiphenylmethane are parts by mass

[0465] The results shown in Table 1 indicate that the use of the aromatic amine resins of Examples 1 to 5 can suppress water absorption of the cured products using the resins, thereby suppressing reduction in dielectric properties (dielectric constant and dielectric loss tangent) and heat resistance.

[0466] [Industrial Applicability]

[0467] According to the present invention, a resin can be provided, which is an aromatic amine resin, and can suppress water absorption of a cured product using the resin, thereby suppressing the reduction of dielectric properties (dielectric constant and dielectric loss tangent) and heat resistance. By using a curable composition containing the aromatic amine resin and a cured product thereof, a prepreg, a circuit substrate, a build-up film, a semiconductor sealing material and a semiconductor device can be provided, which suppress water absorption, thereby suppressing the reduction of dielectric properties (dielectric constant and dielectric loss tangent) and heat resistance.

Claims

1. An aromatic amine resin, which is a reaction product of a fluorene compound, an aromatic amine and a compound represented by the general formula (1), wherein the fluorene compound has no substituent at the 9-position, Here, Ar is Ar 1 -Y-Ar 1 Or 1 , Ar 1 are each independently an aromatic cyclic 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 are each independently 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 claim 1 , wherein the fluorene compound is contained in an amount of 0.01 mol to 0.99 mol per 1 mol of the compound represented by the general formula (1).

3. An aromatic amine resin represented by the general formula (5), Here, Z is independently a structural unit represented by the general formula (2A): or a structural unit represented by the general formula (3A), Z' is independently a structural unit represented by the general formula (2A') or a structural unit represented by the general formula (3A'), Ar are each independently Ar 1 or Ar 1 -Y-Ar 1 , Ar 1 are each independently an aromatic cyclic 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 are each independently a hydrogen atom or an aliphatic hydrocarbon group having 1 to 4 carbon atoms, R 2 are independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom, m is each independently an integer of 0 to 4, R 3 are 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, the two R 3 They can also form rings together with the carbon atoms to which they are bonded. n is each independently an integer of 0 to 3, R b and R c are independently a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, R 2 'are independently an aliphatic hydrocarbon group, an aryl group, an arylalkyl group, an alkoxy group or a halogen atom, m' is an integer of 0 to 4, respectively independently. R 3 ' are 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, the two R 3 ' can also form a ring together with the carbon atoms to which they are bonded, n' is an integer of 0 to 4, respectively independently, R b ' and R c 'are independently a hydrogen atom, an aliphatic hydrocarbon group or an aromatic hydrocarbon group, p is the average value, which is a number greater than 0. in, The resin includes structural units represented by the general formula (2A) and / or the general formula (2A′) and structural units represented by the general formula (3A) and / or the general formula (3A′), and * represents a bonding bond.

4. The aromatic amine resin according to claim 3, comprising at least one of a compound represented by the general formula (5-1) and a compound represented by the general formula (5-2), Here, Ar, Z, R 1 , R 3 ',n',R b ' and R c ' has the same meaning as claim 3.

5. The aromatic amine resin according to claim 1 or 3, wherein the amine equivalent is 100 g / eq. to 2000 g / eq.

6. The aromatic amine resin according to claim 1 or 3, wherein the number average molecular weight is 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, which is 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 a copper foil.

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

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

13. A semiconductor device comprising the hardened product of the semiconductor sealing material according to claim 12.

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