Curable composition, cured product, prepreg, circuit board, build-up film, semiconductor encapsulant, and semiconductor device

Abstract

To provide a curable composition which has low hygroscopicity after curing and exhibits low dielectric loss tangent and low dielectric constant.SOLUTION: A curable composition comprises a polymaleimide resin (A) having a partial structure of formula (1), a partial structure of formula (T-1) chemically bonded to the partial structure of formula (1), and a partial structure of formula (T-2) chemically bonded to the partial structure of formula (1), and an amine compound (B).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to 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] Conventionally, prepregs obtained by impregnating a thermosetting resin such as an epoxy resin or a BT (bismaleimide-triazine) resin into a glass cloth and drying it by heating, laminates obtained by heating and curing the prepregs, and multilayer boards obtained by combining the laminates and the prepregs and curing them by heating have been widely used as circuit board materials for electronic devices. In particular, package boards, which are a type of printed wiring board that serves as an interposer for mounting semiconductors, are becoming thinner, and warping of the package board during mounting is becoming a problem. Therefore, materials that exhibit high heat resistance are required to suppress warping of the package board during mounting. In addition, in recent years, signals have become faster and higher in frequency, and it is desired to provide a thermosetting composition capable of forming a cured product that maintains a sufficiently low dielectric constant and exhibits a sufficiently low dielectric loss tangent under these environments. In particular, in recent years, in various electrical material applications, particularly in advanced material applications, there is a demand for further improvement in performance, represented by heat resistance and dielectric properties, and for materials and compositions that combine these. In response to these demands, maleimide resins have attracted attention as materials that combine heat resistance with low dielectric constant and low dielectric loss tangent. However, although conventional maleimide resins exhibit high heat resistance, they are highly hygroscopic, and their dielectric properties (dielectric constant and dielectric loss tangent value) do not reach the level required for advanced material applications. For example, Patent Document 1 below discloses a thermosetting resin composition containing a polymaleimide resin having an indane ring and triallyl cyanurate or an aromatic diamine as a material for printed circuit boards that does not impair heat resistance and has a dielectric constant of 4.0 or less as a laminate. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Japanese Patent Application Laid-Open No. 5-247202 [Summary of the Invention] [Problems to be Solved by the Invention]

[0004] However, the thermosetting resin composition disclosed in Patent Document 1 above does not reach the levels required for advanced material applications in terms of dielectric constant and dielectric tangent, and does not achieve both low moisture absorption at high temperatures and low dielectric constant and low dielectric tangent. In addition, since the transmission loss increases as the frequency increases, reduction of transmission loss in the high-frequency region is required for circuit board materials. However, in the technology of Patent Document 1 above, only the dielectric properties in the currently used frequency band (range of several hundred MHz to 3 GHz) have been studied, and it has not been examined whether it can correspond to the technology for the fifth-generation mobile communication system (5G) using a frequency band of Sub6 or higher (for example, 3.6 GHz or higher).

[0005] Therefore, an object of the present invention is to solve the problems of the above-mentioned prior art and provide a curable composition, a cured product, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device that have low moisture absorption, low dielectric tangent, and low dielectric constant after curing. [Means for Solving the Problems]

[0006] As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that by using a curable composition containing a specific polymaleimide resin (A) and an amine compound (B), it is possible to achieve high-order compatibility of low moisture absorption, low dielectric tangent, and low dielectric constant after curing, and have thus completed the present invention. That is, the gist configurations of the curable composition, cured product, prepreg, circuit board, build-up film, semiconductor encapsulant, and semiconductor device of the present invention for solving the above problems are as follows.

[0007] [1] A polymerimide resin (A) having a partial structure represented by the following general formula (1), a partial structure represented by the following general formula (T-1) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (T-2) chemically bonded to the partial structure represented by the general formula (1), and an amine compound (B), characterized by containing a curable composition. [Chemical formula] [In the above general formula (1), R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 2 represents an integer of 0 or more and 4 or less, n 1 represents an average number of repeating units, and the two * each represent a bond. One bond is chemically bonded at the position of L 13 or L 14 in the following general formula (T-1), and the other bond is chemically bonded at the position of L 11 or L 12 in the following general formula (T-2).] [Chemical formula] [In the above general formula (T-1) or (T-2), R 11 and R 15 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 and R 14 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, L 11 to L 14 each independently represent a bond or a hydrogen atom, provided that L 11 or L 12 is chemically bonded to the partial structure represented by the general formula (1) at the position of, and L 13 or L 14 is chemically bonded to the partial structure represented by the general formula (1) at the position of, and L 11 to L 14 that is not chemically bonded to the partial structure represented by the general formula (1) is a hydrogen atom, m1 and m 3 each represents 2.]

[0008] [2] The curable composition according to [1], wherein the polymaleimide resin (A) uses an aromatic amine compound (A-a) represented by the following general formula (a-1), a compound (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c) as reaction raw materials (1).

Chemical formula

[0009] [3] The curable composition according to [1] or [2], wherein the polymaleimide resin (A) is a polymaleimide resin having a partial structure represented by the following general formula (1A).

Chemical formula

Chemical formula

[0010] [4] The curable composition according to [3], which contains 10% by mass or more of a component represented by the above general formula (1A) and in which the sum of n 1 and n 3 is 1 or more.

[0011] [5] A polymerimide resin mixture (C) containing a polymerimide resin component having a partial structural unit represented by the following general formula (1a) and a maleimide multimer compound represented by the following general formula (2), an amine compound (B), and the polymerimide resin mixture (C) contains 1 to 99% by mass of a polymerimide resin (A) having a partial structure represented by the following general formula (1), a partial structure represented by the following general formula (T-1) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (T-2) chemically bonded to the partial structure represented by the general formula (1), and contains 80% by mass or less of the maleimide multimer compound with respect to the total amount of the polymerimide resin mixture (C). [Chemical formula] [In the above general formula (1a), R 11 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 represents a hydrocarbon group having 1 to 18 carbon atoms, R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 1 represents 2, m 2 represents an integer of 0 or more and 4 or less, and n 1 represents the average number of repeating units.] [Chemical formula] [In the above general formula (2), R 21 and R 25 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R 22 and R 24 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, m 21 represents 2, m 23 represents 3, and n 21 represents an integer of 1 or more and 5 or less.] [Chemical formula] [In the above general formula (1), R 13 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, m 2 represents an integer of 0 or more and 4 or less, n 1 represents the average number of repeating units, and the two * each represent a bond. One bond is chemically bonded at the position of L 13 or L 14 in the following general formula (T-1), and the other bond is chemically bonded at the position of L 11 or L 12 in the following general formula (T-2).] [Chemical formula] [In the above general formula (T-1) or (T-2), R 11 and R 15 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 and R 14 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, L 11 to L 14 each independently represent a bond or a hydrogen atom. However, at the position of L 11 or L 12 it is chemically bonded to the partial structure represented by the general formula (1), and at the position of L 13 or L 14 it is chemically bonded to the partial structure represented by the general formula (1), and further, L that is not chemically bonded to the partial structure represented by the general formula (1)11 ~L 14 is a hydrogen atom, m 1 and m 3 each represent 2.]

[0012] [6] The curable composition according to [5], wherein the polymaleimide resin (A) uses an aromatic amine compound (A-a) represented by the following general formula (a-1), a compound (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c) as reaction raw materials (1). [Chemical formula] [In the above general formula (a-1), R a1 and R a2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 1 represents a hydrocarbon group having 1 to 18 carbon atoms, R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]

[0013] [7] A polymaleimide resin characterized by having a partial structure represented by the following general formula (1A). [Chemical formula] [In the above general formula (1A), R 13 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, m 2 represents an integer of 0 or more and 4 or less, n 1 represents the average number of repeating units, R 11 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, m 1 each represent 2, n 2 represents the average number of repeating units, ran represents that the arrangement of each constitutional unit can be random, two * each represent a bond, and are bonded to a hydrogen atom or a partial structure represented by the following general formula (T-3).] [Chemistry] [In the above general formula (T-3), R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 2 represents an integer of 0 or more and 4 or less, and n 3 represents the average number of repeating units.]

[0014] [8] A cured product of the curable composition according to any one of [1] to [6].

[0015] [9] A prepreg having a reinforcing base material and a semi-cured product of the curable composition according to any one of [1] to [6] impregnated in the reinforcing base material.

[0016]

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

[0017]

[11] A build-up film containing the curable composition according to any one of [1] to [6].

[0018]

[12] A semiconductor encapsulant containing the curable composition according to any one of [1] to [6].

[0019]

[13] A semiconductor device including a cured product of the semiconductor encapsulant according to

[12] . [Advantages of the Invention]

[0020] According to the present invention, it is possible to provide a curable composition, a cured product, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device that can achieve both low moisture absorption after curing and high-order low dielectric constant and low dielectric tangent. Further, according to the present invention, it is possible to provide a curable composition, a cured product, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device that can achieve both low moisture absorption after curing and high-order low dielectric constant and low dielectric tangent even in a frequency band of Sub6 or higher. Such a curable composition is particularly useful in applications such as electronic component encapsulation materials.

Brief Description of the Drawings

[0021]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Modes for Carrying Out the Invention

[0022] Hereinafter, the curable composition, cured product, prepreg, circuit board, build-up film, semiconductor encapsulant, and semiconductor device of the present invention will be exemplified and described in detail based on their embodiments. Note that the present invention is not limited to the following description, and can be variously modified and implemented within the scope of the gist.

[0023] [Terms] Unless otherwise specified in this specification, the following terms can be applied. The "reaction raw material" in this specification refers to a compound used to obtain a target compound by a chemical reaction such as bonding or decomposition, and constitutes a part of the chemical structure of the target compound. Substances that play the role of chemical reaction aids such as solvents and catalysts are excluded. In this specification, in particular, the "reaction raw material" refers to, for example, when the target product is the polymaleimide resin (A), the polymaleimide resin (A) or its precursor compound [e.g., an intermediate amine compound (A-ab) in which structural units derived from a compound (A-b) in which aromatic amine compounds (A-a) have a benzyl ether skeleton are linked via a chemical reaction].

[0024] As used herein, the "structural unit" refers to the (repeating) unit of the chemical structure formed during a reaction or polymerization. In other words, in the resulting compound formed by the reaction or polymerization, it refers to the partial structure other than the structure of the chemical bonds involved in the reaction or polymerization, i.e., the so-called residue. In the case of polymerization, it is also referred to as the repeating unit.

[0025] The "aromatic group" as used herein preferably has an aromatic ring with 3 to 30 carbon atoms, more preferably an aromatic ring with 4 to 26 carbon atoms. And, the "aromatic group" as used herein may have a hydrogen atom of the aromatic ring in the aromatic group substituted by a substituent, for example, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, or a halogen atom. Further, the "aromatic group" includes heteroaromatics and may be substituted by -O-, -S-, or -N= so that -CH2- or -CH= in the "aromatic group" are not adjacent to each other. Examples of the type of the aromatic ring include a monocyclic aromatic ring and a condensed polycyclic aromatic ring. Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, etc. Examples of the condensed polycyclic aromatic ring include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etc. Examples of the fused aromatic ring include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc. Also, the hydrogen atom of the aromatic ring in the aromatic group may be substituted by, for example, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an aryl group with 1 to 12 carbon atoms, an aralkyl group with 1 to 12 carbon atoms, or a halogen atom. The monovalent aromatic group refers to a group obtained by removing one hydrogen atom from the "aromatic group", and the divalent aromatic group refers to a group obtained by removing any two hydrogen atoms from the "aromatic group".

[0026] The "alkyl group" in this specification may be linear, branched or cyclic. For example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, (n-)heptyl group, (n-)octyl group, (n-)nonyl group, (n-)decyl group, (n-)undecyl group, (n-)dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group or adamantyl group can be mentioned.

[0027] The "cycloalkyl group" in this specification includes cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, methylcyclobutyl group, norbornyl group, adamantyl group, etc.

[0028] The "alkylthio group" in this specification includes methylthio group, ethylthio group, propylthio group, butylthio group, octylthio group or 2-ethylhexylthio group.

[0029] The "alkenyl group" in this specification includes ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, pentynyl group, hexynyl group, vinyl group, allyl group or isopropenyl group, etc. Note that the "alkenylene group" refers to a divalent group obtained by removing any one hydrogen atom from the above-mentioned "alkenyl group".

[0030] The "alkoxy group" in this specification includes, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, octyloxy group, nonyloxy group, etc.

[0031] The "aryl group" in this specification includes, for example, phenyl group, naphthyl group, phenalenyl group, phenanthrenyl group, anthryl group, azulenyl group, tetralinyl group, etc. Further, in the "aryl group", a hydrogen atom of the aromatic ring in the aryl group may be substituted with, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or a halogen atom. Note that the "arylene group" includes a divalent group obtained by removing one arbitrary hydrogen atom from the "aryl group".

[0032] Examples of the "aralkyl group" in this specification include benzyl group, diphenylmethyl group, biphenyl group, naphthylmethyl group, etc. A hydrogen atom of the aromatic ring in the aralkyl group may be substituted with, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. Note that the "aralkylene group" includes a divalent group obtained by removing one arbitrary hydrogen atom from the "aralkyl group".

[0033] Examples of the "aryloxy group" in this specification include phenoxy group, naphthyloxy group, anthryloxy group, phenanthryloxy group, pyrenyloxy group, etc.

[0034] Examples of the "arylthio group" in this specification include arylthio groups such as phenylthio group, naphthylthio group, anthrylthio group, phenanthrylthio group, pyrenylthio group, etc.

[0035] Examples of the "halogen atom" in this specification include fluorine atom, chlorine atom, bromine atom, iodine atom, etc.

[0036] The "alkylene group" in this specification includes, for example, methylene group, ethylene group, propylene group, 1-methylmethylene group, 1,1-dimethylmethylene group, 1-methylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, propylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, and the like.

[0037] The "alkyleneoxy group" in this specification includes, for example, oxymethylene group, oxyethylene group, oxypropylene group, oxy(1-methylmethylene) group, oxy(1,1-dimethylmethylene) group, oxy(1-methylethylene) group, oxy(1,1-dimethylethylene) group, oxy(1,2-dimethylethylene) group, oxybutylene group, oxy(1-methylpropylene) group, oxy(2-methylpropylene) group, oxypentylene group, oxyhexylene group, oxyheptylene group, oxyoctylene group, oxynonylene group, oxydecylene group, oxyundecylene group, oxydodecylene group, and the like.

[0038] The "hydrocarbon group" in this specification is a monovalent group and includes linear, branched or cyclic saturated hydrocarbons, unsaturated hydrocarbons, or aromatic groups. For example, the "hydrocarbon group" is one kind of group selected from the group consisting of an alkyl group (for example, the above alkyl group), an alkenyl group (for example, the above alkenyl group), an aryl group (for example, the above aryl group), an aryloxy group (for example, the above aryloxy group), an aralkyl group (for example, the above aralkyl group), and an alkoxy group (for example, the above alkoxy group), and one or more -CH2- in the group may be substituted with -O-, -C(=O)- or -S- so as not to be adjacent to each other, or one or more -CH2-CH2- in the alkyl group may be substituted with -CH=CH- so as not to be adjacent to each other.

[0039] [Curable Composition] The curable composition of the present embodiment contains a polymaleimide resin (A) having a partial structure represented by the above general formula (1), a partial structure represented by the above general formula (T-1) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the above general formula (T-2) chemically bonded to the partial structure represented by the general formula (1) (hereinafter, may be simply referred to as "polymaleimide resin (A)"), and an amine compound (B).

[0040] Since the curable composition of the present embodiment contains a polymaleimide resin (A) having a low proportion of polar functional groups in its chemical structure, it can achieve both excellent low dielectric properties and low moisture absorption as a whole composition. Further, by combining the polymaleimide resin (A) and the amine compound (B), the curable composition of the present embodiment can achieve both low moisture absorption and high-order low dielectric constant and low dielectric tangent after curing even in a frequency band of Sub6 or higher.

[0041] In the curable composition of the present embodiment, the blending ratio (parts by mass) of the polymaleimide resin (A) and the amine compound (B) is preferably such that polymaleimide resin (A):amine compound (B) is 97:3 to 3:97, more preferably 95:5 to 5:95, and still more preferably 90:10 to 10:90. Adjusting the blending ratio within the above range is preferable because excellent low moisture absorption, low dielectric constant, and low dielectric tangent can be exhibited.

[0042] The curable composition of the present embodiment may contain a curing agent (D) other than the amine compound (B) within a range that does not impair the effects of the present invention. Further, the curable composition of the present embodiment may contain other resins (E), curing accelerators, or additives other than the polymaleimide resin (A) and the amine compound (B). Examples of the additive include flame retardants, inorganic fillers, silane coupling agents, mold release agents, antioxidants, light stabilizers, heat stabilizers, pigments, and emulsifiers.

[0043] Hereinafter, after the polyimide resin (A) and the amine compound (B), which are essential components of the curable composition of the present embodiment, are described in detail, the curing agent (D) other than the amine compound (B), other resins (E), the curing accelerator, additives, etc., which are optional components, will be described.

[0044] <Polyimide resin (A)> The polyimide resin (A) has a partial structure represented by the following general formula (1), a partial structure represented by the following general formula (T-1) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (T-2) chemically bonded to the partial structure represented by the general formula (1). [Chemical formula] [In the above general formula (1), R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 2 represents an integer of 0 or more and 4 or less, n 1 represents the average number of repeating units, and the two * each represent a bond. One bond is chemically bonded at the position of L 13 or L 14 in the following general formula (T-1), and the other bond is chemically bonded at the position of L 11 or L 12 in the following general formula (T-2).] [Chemical formula] [In the above general formula (T-1) or (T-2), R 11 and R 15 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 and R 14 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, L 11 to L 14 each independently represent a bond or a hydrogen atom, provided that L 11 or L 12 is chemically bonded to the partial structure represented by the general formula (1) at the position of, and L 13 or L14 is chemically bonded to the partial structure represented by the general formula (1) at the position of, and L that is not chemically bonded to the partial structure represented by the general formula (1) 11 ~L 14 is a hydrogen atom, m 1 and m 3 each represent 2.]

[0045] Since the proportion of polar functional groups in the chemical structure of the polyimide resin (A) is small, the cured product thereof can achieve both excellent low dielectric properties and low moisture absorption. Further, the polyimide resin (A) has high solubility in solvents, and the cured product thereof exhibits high heat resistance. Since the chemical structure of the polyimide resin (A) has only one bonding site at the ortho and para positions of the benzene ring to which the maleimide group is bonded, a polyimide resin in which the chain extends linearly can be obtained, so that molecular weight control is easy, and it is possible to achieve both heat resistance and low dielectric properties and solvent solubility. Therefore, the curable composition containing the polyimide resin (A) has high solubility in solvents, and further, the cured product thereof can achieve both low moisture absorption and high-order compatibility of low dielectric constant and low dielectric tangent, and exhibits high heat resistance.

[0046] In the above general formula (1), the two * each represent a bond. And one of the two bonds is bonded to L in the above general formula (T-1) 13 or L 14 at the position. Further, the other bond is bonded to L in the above general formula (T-2) 11 or L 12 at the position. Therefore, the polyimide resin (A) has a structural unit in which the partial structure represented by the general formula (T-1) and the partial structure represented by the general formula (T-2) are linked by the partial structure represented by the general formula (1), and at the para position or one ortho position with respect to the maleimide group on the benzene ring in the general formula (T-1) and the general formula (T-2), the partial structure represented by the general formula (1) is chemically bonded. In the above general formula (1), when n 1 is 2 or more, a plurality of R exist 13They may be the same as or different from each other. m 2 When m is 2 or more, a plurality of Rs exist 13 They may be the same as or different from each other.

[0047] In the general formula (1) above, R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, preferably represents a hydrocarbon group having 1 to 12 carbon atoms, and more preferably represents a hydrocarbon group having 1 to 6 carbon atoms. Also, when m 2 is an integer of 2 or more, a plurality of Rs present 13 may be the same as or different from each other. Preferred R in the general formula (1) 13 is preferably a linear alkyl group, and more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group or a neopentyl group. In addition, the benzene ring to which R in the general formula (1) is attached 13 may be the benzene ring of the compound (A-b) having a benzyl ether skeleton.

[0048] In the general formula (1) above, m 2 represents an integer of 0 or more and 4 or less, preferably an integer of 2 or less, and more preferably 2. In the benzene ring to which R in the general formula (1) is attached, when the 1st and 3rd positions are bonded by a methylene group 13 it is preferable that Rs are respectively bonded to the 4th and 6th positions. 13

[0049] In the general formula (1) above, n 1 represents the average number of repeating units, and from the viewpoint of the viscosity of the resulting polymaleimide resin (A), it is preferably 0 or more and 50 or less, preferably 0 or more and 30 or less, preferably 0 or more and 15 or less. The average number of repeating units can be calculated from the charge ratio or NMR etc. as shown in the column of the examples described later.

[0050] The above-mentioned polymaleimide resin (A) preferably contains 1 to 99% by mass, more preferably 3 to 97% by mass, and still more preferably 5 to 95% by mass of the partial structure represented by the general formula (1) with respect to the total amount (100% by mass) of the polymaleimide resin (A).

[0051] In the above general formula (T-1), R 15 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Particularly preferred R 15 can be a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms. m 3 is 2, so the two R 15 may be the same or different from each other.

[0052] In the above general formula (T-1), R 14 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 6 carbon atoms. Particularly preferred R 14 can be a linear alkyl group having 1 to 6 carbon atoms. At the ortho position (6-position) of the benzene ring of the above general formula (T-1) or the above general formula (T-2), by allowing the bonding site with the partial structure represented by the general formula (1), it has higher solubility in a solvent, and its cured product exhibits more excellent low dielectric tangent and high heat resistance. Note that the benzene ring to which R 14 is bonded in the general formula (T-1) can be the benzene ring of the aromatic amine compound (A-a).

[0053] In the above general formula (T-1), L 13 or L 14 each independently represents a bond or a hydrogen atom. However, L 13 or L 14At least one of the positions, the partial structure represented by the general formula (1) and the partial structure represented by the general formula (T-1) are chemically bonded. Further, L that is not chemically bonded to the partial structure represented by the general formula (1) 13 or L 14 is a hydrogen atom. Note that L 13 and L 14 The partial structure represented by the general formula (1) may be chemically bonded to each of the two positions.

[0054] In the general formula (T-2), each R 11 independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Preferred R 11 can be a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms. Since m 1 is 2, the two R 11 may be the same as or different from each other.

[0055] In the general formula (T-2), each R 12 independently represents a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms. Preferred R 12 represents a linear alkyl group having 1 to 6 carbon atoms. Note that the benzene ring to which R 12 in the general formula (T-2) is bonded may be the benzene ring of the aromatic amine compound (A-a).

[0056] In the general formula (T-2), each L 11 or L 12 independently represents a bond or a hydrogen atom. However, at least one of the positions of L 11 or L 12 The partial structure represented by the general formula (1) and the partial structure represented by the general formula (T-2) are chemically bonded. Further, L 11 or L 12 is a hydrogen atom. Note that L11 and L 12 The partial structure represented by the general formula (1) may be chemically bonded to each of the two locations.

[0057] The polyimide resin (A) preferably contains 1 to 99% by mass, more preferably 3 to 97% by mass, and still more preferably 5 to 95% by mass of the partial structure represented by the general formula (T-1) with respect to the total amount (100% by mass) of the polyimide resin (A). The polyimide resin (A) preferably contains 1 to 99% by mass, more preferably 3 to 97% by mass, and still more preferably 5 to 95% by mass of the partial structure represented by the general formula (T-2) with respect to the total amount (100% by mass) of the polyimide resin (A).

[0058] [[Polyimide resin having a partial structure represented by the general formula (1A)]] As the polyimide resin (A), a polyimide resin having a partial structure represented by the following general formula (1A) is preferable. [Chemical formula] [In the above general formula (1A), R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 2 represents an integer of 0 or more and 4 or less, n 1 represents the average number of repeating units, R 11 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 1 each represents 2, n 2 represents the average number of repeating units, ran represents that the arrangement of each structural unit can be random, the two * each represent a bond, and is bonded to a hydrogen atom or a partial structure represented by the following general formula (T-3).] [Chemical formula] [In the above general formula (T-3), R13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, and m 2 represents an integer of 0 or more and 4 or less, and n 3 represents the average number of repeating units.]

[0059] The polyimide resin having the partial structure represented by the general formula (1A) can achieve both heat resistance, low dielectric properties and solvent solubility. Therefore, the curable composition containing the polyimide resin having the partial structure represented by the general formula (1A) has high solubility in solvents. Furthermore, the cured product thereof can achieve both low hygroscopicity and high-order low dielectric constant and low dielectric tangent, and also exhibits high heat resistance.

[0060] In the general formula (1A), "R 11 , R 12 , R 13 , n 1 , m 1 and m 2 " is synonymous with "R 11 , R 12 , R 13 , n 1 , m 1 and m 2 " in the above-described general formula (1) or general formula (T-2). Also, regarding "R 11 , R 12 , R 13 , n 1 , and m 2 " in the general formula (1A), the preferred hydrocarbon group, the preferred number of carbon atoms, and the preferred numerical range are also the same as those of "R 11 , R 12 , R 13 , n 1 , and m 2 " in the above-described general formula (1) or general formula (T-2). In the general formula (1A), n 2 represents the average number of repeating units. From the viewpoint of the viscosity of the resulting polyimide resin, it is preferably 0 or more and 50 or less, preferably 0 or more and 30 or less, preferably 0 or more and 15 or less. The average number of repeating units can be calculated from the charging ratio or NMR as shown in the examples section described later. In the general formula (1A) above, "ran" indicates that the arrangement of each constitutional unit can be random. In the general formula (1A) above, the two "*" each represent a bond and are bonded to a hydrogen atom or a partial structure represented by the general formula (T-3).

[0061] Also, "R" in the general formula (T-3) 13 and m 2 are each independently synonymous with "R" in the general formula (1) described above 13 or m 2 above. n in the general formula (T-3) 3 represents the average number of repeating units, and from the viewpoint of the viscosity of the resulting polymaleimide resin, it is preferably 0 or more and 50 or less, more preferably 0 or more and 30 or less, and still more preferably 0 or more and 15 or less. The average number of repeating units can be calculated from the charge ratio or NMR as shown in the Examples section described later. In the general formula (T-3) above, "*" represents a bond and is chemically bonded to the "*" (bond) in the general formula (1A).

[0062] The polymaleimide resin (A) is represented by the general formula (1A) above, and preferably contains 10% by mass or more of a component in which the sum of n 1 and n 3 is 1 or more, more preferably 15% by mass or more, and still more preferably 20% by mass or more. Also, from the viewpoint of heat resistance, the polymaleimide resin (A) preferably contains 5% by mass or more of a component in which n 2 is 1 or more, more preferably 7% by mass or more, and still more preferably 10% by mass or more.

[0063] <<Reaction raw materials>> The polymaleimide resin (A) preferably uses an aromatic amine compound (A-a) represented by the following general formula (a-1) (hereinafter, also simply referred to as the aromatic amine compound (A-a)), a compound (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c) as reaction raw material (1). [Chemical formula] [In the general formula (a-1), R a1 and R a2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 1 represents a hydrocarbon group having 1 to 18 carbon atoms, and R 2 and R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]

[0064] Further, it is preferable that the polymer maleimide resin (A) uses an intermediate amine compound (A-ab) in which aromatic amine compounds (A-a) are linked via a structural unit derived from a compound (A-b) having a benzyl ether skeleton and maleic anhydride (A-c) as reaction raw materials (2). Furthermore, it is preferable that the intermediate amine compound (A-ab) is a compound obtained by using an aromatic amine compound (A-a) and a compound (A-b) having a benzyl ether skeleton as reaction raw materials (3). In other words, it is preferable that the intermediate amine compound (A-ab) has a structural unit in which a structural unit derived from an aromatic amine compound (A-a) having an aromatic ring to which an amino group is bonded and a structural unit derived from a compound (A-b) having a benzyl ether skeleton are linked by a chemical bond. And the polymer maleimide resin (A) has a structure in which the amino group bonded to the aromatic ring of the intermediate amine compound (A-ab) is substituted with an N-substituted maleimide ring. Note that the "amino group" in this specification also includes a substituted amino group in which a hydrogen atom of -NH2 is further substituted with an alkyl group having 1 to 6 carbon atoms. Therefore, the "polymer maleimide resin (A)" and the "intermediate amine compound (A-ab)" which is a precursor of the "polymer maleimide resin (A)" are polymer compounds that differ in that the amino group bonded to the aromatic ring is replaced with an N-substituted maleimide ring. The structural unit of the aromatic amine compound (A-a) refers to a group obtained by removing at least one hydrogen atom from the aromatic ring of the aromatic amine compound (A-a). For example, when the aromatic amine compound (A-a) is represented by the general formula (a-1) described below, a group obtained by removing at least one hydrogen atom from the benzene ring of the general formula (a-1) is defined as the structural unit of the aromatic amine compound (A-a). Further, the structural unit derived from the compound (A-b) having a benzyl ether skeleton means that -(CH2O)- other than the terminal group in the compound (A-b) having a benzyl ether skeleton is replaced by -(CH2)- and is directly bonded to the benzene ring, and - (CH2O)-R b is all replaced by -(CH2)-. Note that the above R b represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.

[0065] In the present embodiment, since an aromatic amine compound (A-a) having an aromatic ring structure with a substituent at a specific position is used as a reaction raw material, it becomes easier to control the reaction site with the compound (A-b) having a benzyl ether skeleton described below. As a result, a homogeneous chemical structure and a chain-like polymaleimide resin can be easily obtained. As a result, a polymaleimide resin (A) having excellent solubility in a solvent and high heat resistance and low dielectric tangent after curing can be provided.

[0066] Hereinafter, after explaining the aromatic amine compound (A-a) represented by the general formula (a-1), the compound (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c), which are the constituent components of the reaction raw material (1) of the polymaleimide resin (A), the production method of the polymaleimide resin (A) and another preferred form of the polymaleimide resin (A) [polymaleimide resin mixture (C)] will be described.

[0067] - Aromatic amine compound (A-a) represented by the general formula (a-1) - The aromatic amine compound (A-a) has an aromatic ring to which an amino group is bonded and has a structure in which a hydrocarbon group having 1 to 18 carbon atoms is bonded to one of the ortho positions of the aromatic ring, as represented by the following general formula (a-1). [Chemical formula] [In the general formula (a-1), R a1 and R a2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 1 represents a hydrocarbon group having 1 to 18 carbon atoms, and R 2 and R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]

[0068] In the aromatic amine compound (A-a), as the hydrocarbon group (R 2 , R 3 ) which may be substituted for one or two or less hydrogen atoms of the aromatic ring of the aromatic amine compound (A-a), there may be mentioned linear, branched or cyclic hydrocarbon groups having 1 to 18 carbon atoms, preferably linear or branched hydrocarbon groups having 1 to 12 carbon atoms, and more preferably linear or branched alkyl groups having 1 to 6 carbon atoms. As described in the general formula (a-1) above, it has a bonding site with the compound (A-b) having a benzyl ether skeleton at each of the ortho and para positions of the aromatic ring. In the general formula (a-1) above, R 1 represents a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 6 carbon atoms. In the general formula (a-1) above, R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 6 carbon atoms. In the general formula (a-1) above, R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 6 carbon atoms.

[0069] In addition, by making the number of hydrocarbon groups (e.g., alkyl groups) substituted on the aromatic ring of the aromatic amine compound (A-a) 1 or more, it becomes easier to control the reaction site with the compound (A-b) having a benzyl ether skeleton described later, and thus it becomes easier to obtain a polyimide resin (A) having a specific chemical structure. As a result, in the cured product of the curable composition containing the polyimide resin (A), it becomes easier to exhibit solvent solubility, heat resistance, and excellent high-frequency electrical properties. In particular, since a substituent (R 1 ) is introduced at the ortho position (adjacent position) of the aromatic amine compound (A-a), after maleimidating the amino group derived from the aromatic amine compound (A-a), the dihedral angle formed by the aromatic ring plane of the aniline skeleton and the nitrogen-containing five-membered ring plane of maleimide becomes large, making it easier for the crystallinity derived from the maleimide group to collapse and improving solubility.

[0070] In the present embodiment, it is preferable that among the carbon atoms in the benzene ring constituting the aromatic amine compound (A-a), at least one carbon atom having the largest HOMO electron density (Hückel coefficient) is unsubstituted (substituted with a hydrogen atom). Therefore, as the aromatic amine compound (A-a) represented by the above general formula (a-1), it is preferable that any two of the 2-position, 4-position, and 6-position are substituted with hydrogen atoms. A particularly preferable form of the aromatic amine compound (A-a) represented by the above general formula (a-1) is that the 2-position is substituted with an alkyl group, and the 4-position and 6-position are hydrogen atoms. Thereby, it becomes easier to control the ArS E reaction and molecular design by the cationoid reagent formed from the compound (A-b) having a benzyl ether skeleton described later. As a result, in the cured product of the curable composition containing the polyimide resin (A), it becomes easier to exhibit solvent solubility, heat resistance, and excellent high-frequency electrical properties. In particular, by substituting the 4- and 6-positions of the benzene ring of the general formula (a-1) with hydrogen atoms, a polyimide resin (A) (or intermediate amine resin) with a linearly extended molecule can be obtained.

[0071] Specific examples of the aromatic amine compound (A-a) include, for example, o-toluidine, 2-ethylaniline, 2-propylaniline, 2-butylaniline, 2-cyclobutylaniline, 2-cyclopentylaniline, 2-cyclohexylaniline, dimethylaniline (2,3-xylidine, 2,4-xylidine or 2,5-xylidine), diethylaniline (2,3-diethylaniline, 2,4-diethylaniline or 2,5-diethylaniline), diisopropylaniline (2,3-diisopropylaniline, 2,4-diisopropylaniline or 2,5-diisopropylaniline), ethylmethylaniline (for example, ethylmethylaniline in which one of the 2,3-position, 2,4-position or 2,5-position is a methyl group and the other is an ethyl group), methylisopropylaniline (for example, methylisopropylaniline in which one of the 2,3-position, 2,4-position or 2,5-position is a methyl group and the other is an isopropyl group), or ethylbutylaniline (for example, ethylbutylaniline in which one of the 2,3-position, 2,4-position or 2,5-position is an ethyl group and the other is a butyl group), etc. can be used. The butyl includes n-butyl, tert-butyl and sec-butyl. The aromatic amine compound (A-a) may be used alone or in combination of two or more.

[0072] For example, in the case of a chemical structure in which a maleimide group is directly bonded to an unsubstituted benzene ring, such as N-phenylmaleimide, since the benzene ring and the 5-membered ring of maleimide are arranged in the same plane in a stable state, they are likely to stack, resulting in the manifestation of high crystallinity. Therefore, this causes poor solvent solubility. On the other hand, for example, in the case of having an alkyl group (e.g., an ethyl group) as a substituent for the benzene ring, such as 2-ethylaniline, due to the steric hindrance of the ethyl group, the benzene ring and the 5-membered ring of maleimide take a twisted conformation and it becomes difficult to stack, so the crystallinity decreases, the solvent solubility improves, and it becomes a preferable embodiment. However, if the steric hindrance is too large or depending on the substitution position of the alkyl group, there are also concerns about inhibiting the reactivity during the synthesis of maleimidation and deteriorating the curability of the maleimide group when producing a cured product. Therefore, for example, it is preferable to use an aromatic amine compound (A-a) having a hydrocarbon group with 1 to 6 carbon atoms. In addition, the aromatic amine compound (A-a) represented by the above general formula (a-1) may be used alone or in combination of two or more.

[0073] - Compound (A-b) having a benzyl ether skeleton - The compound (A-b) having the benzyl ether skeleton may be a single compound or a mixture. When the compound (A-b) having the benzyl ether skeleton is a single compound, it is preferably a compound having a partial structure represented by the following formula (b) described later, more preferably a compound represented by the following formula (b-1), and even more preferably a compound represented by the following formula (b-2). On the other hand, when the compound (A-b) having the benzyl ether skeleton is a mixture, it is preferably a mixture containing a compound having a partial structure represented by the following formula (b) and / or a compound having a benzyl ether skeleton represented by the following formula (b-1), and a mixture in which a component having a partial structure represented by the following general formula (b-3) occupies 95% by mass or more and 100% by mass or less of the whole.

[0074] The compound (A-b) having the benzyl ether skeleton is preferably a compound having a benzyl ether skeleton represented by the following formula (b). [Chemical formula] [In the above general formula (b), R b3 each independently represents an alkyl group having 1 to 18 carbon atoms, m b2 represents an integer of 0 or more and 4 or less, j 1 and j 2 each independently represents an integer of 0 or more and 4 or less, and j 1 +j 2 ≧1, k 1 and k 2 each independently represents 0 or 1, and * represents a bond with another atom.] The compound (A-b) having the benzyl ether skeleton is preferably a product obtained by reacting an alkylbenzene and formaldehyde under an acid catalyst.

[0075] -- Physical properties of the compound (A-b) having a benzyl ether skeleton -- The compound (A-b) having the benzyl ether skeleton has a benzyl ether skeleton represented by the above formula (b) and preferably satisfies at least one of the following physical property values. Thereby, a resin that can exhibit more excellent solvent solubility, heat resistance, and dielectric properties can be synthesized. The upper limit of the number average molecular weight (Mn) of the compound (A-b) having the benzyl ether skeleton is preferably 1200 or less, more preferably 800 or less, and still more preferably 500 or less. The lower limit of the number average molecular weight (Mn) of the compound (A-b) having the benzyl ether skeleton is preferably 200 or more, more preferably 240 or more, and still more preferably 250 or more. The upper limit of the oxygen content rate of the compound (A-b) having the benzyl ether skeleton is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 12% by mass or less. The lower limit of the oxygen content rate of the compound (A-b) having the benzyl ether skeleton is preferably 4% by mass or more, more preferably 5% by mass or more, and even more preferably 7% by mass or more. The upper limit of the specific gravity of the compound (A-b) having the benzyl ether skeleton is preferably less than 1.2, more preferably less than 1.15, and even more preferably less than 1.10. The lower limit of the specific gravity of the compound (A-b) having the benzyl ether skeleton is preferably 1.0 or more, more preferably 1.01 or more, and even more preferably 1.02 or more. The upper limit of the viscosity (75 °C) of the compound (A-b) having the benzyl ether skeleton is preferably 1500 mPa·s or less, more preferably 1000 mPa·s or less, and even more preferably 900 mPa·s or less. The lower limit of the viscosity (75 °C) of the compound (A-b) having the benzyl ether skeleton is preferably 30 mPa·s or more, more preferably 50 mPa·s or more, and even more preferably 70 mPa·s or more. The upper limit of the indirect viscosity (20 °C, viscosity measured by diluting to 80% by weight of resin content with toluene) of the compound (A-b) having the benzyl ether skeleton is preferably 1000 mPa·s or less, more preferably 800 mPa·s or less, and even more preferably 500 mPa·s or less. The lower limit of the indirect viscosity (20 °C) of the compound (A-b) having the benzyl ether skeleton is preferably 10 mPa·s or more, more preferably 20 mPa·s or more, and even more preferably 30 mPa·s or more. The hydroxyl value of the compound (A-b) having the benzyl ether skeleton is preferably 16 to 50 (mgKOH / g), more preferably 18 to 40 (mgKOH / g), and even more preferably 22 to 35 (mgKOH / g).

[0076] -- Preferred form of the compound (A-b) having a benzyl ether skeleton -- As an example of the compound (A-b) having a benzyl ether skeleton which is the reaction raw material (1) of the above-mentioned polymaleimide resin (A), it is preferably a compound having a structural unit represented by the following formula (b-1). [Chemical formula] [In the above general formula (b-1), R b1 each independently represents a hydrogen atom or an alkyl group having 1 to 11 carbon atoms, and one or more -CH2- in the alkyl group may be substituted with -O- or -C(=O)- so as not to be adjacent to each other, R b2 and R b3 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, L 1 each independently represents an alkylene group having 1 to 11 carbon atoms, and one or more -CH2- in the alkylene group may be substituted with -O- so as not to be adjacent to each other, L 2 represents a single bond or an alkylene group having 1 to 11 carbon atoms, and one or more -CH2- in the alkylene group may be substituted with -O- or -(C=O)- so as not to be adjacent to each other, Z 1 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, k represents an integer of 0 or more and 20 or less, m b1 and m b2 each independently represents an integer of 0 or more and 4 or less, R b1 or L 2 has a -CH2O- group in at least one of them.]

[0077] In the above general formula (b-1), R b1 preferably represents a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 9 carbon atoms, and one or more -CH2- in the hydrocarbon group may be substituted with -O- so as not to be adjacent to each other. Preferred R b1is a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, an alkoxy group having 1 to 9 carbon atoms, a hydroxyalkyl group having 1 to 9 carbon atoms, -(CH2O) p1 -C(=O)-R b4 、-(CH2O) p1 -R b4 、-(CH2O) p1 -(CH2) p2 -R b4 、-(CH2) p3 -(CH2O) p1 -(CH2) p2 -R b4 、-(OCH2) q1 -R b4 、-(OCH2) q1 -(CH2) q2 -R b4 and -(CH2) q3 -(OCH2) q1 -(CH2) q2 -R b4 is preferably one selected from the group consisting of. Here, the said R b4 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Further, it is preferable that the said p1 to p3 and the said q1 to q3 each independently represent an integer of 1 to 11, more preferably an integer of 1 to 6, still more preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2. Furthermore, it is preferable that at least one of R b1 or L 2 has a -CH2O- group, and it is more preferable that both R b1 and L 2 have a -CH2O- group.

[0078] R in the above general formula (b-1) b2 and R b3 can each independently correspond to R in the general formula (1) 13 . Therefore, R in the above general formula (b-1) b2 and R b3 are each independently preferably an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and still more preferably an alkyl group having 1 to 6 carbon atoms, in the same manner as in the general formula (1). Also, mb1 When n is an integer of 2 or more, two or more Rs b2 may be the same as each other or may be different groups. Similarly, when m b2 is an integer of 2 or more, two or more Rs b3 may be the same as each other or may be different groups.

[0079] In the general formula (b-1), each L 1 independently represents preferably an alkylene group having 1 to 11 carbon atoms, more preferably an alkylene group having 1 to 9 carbon atoms, and one or more -CH2- in the alkylene group may be substituted with -O- so as not to be adjacent to each other. Specifically, L 1 represents an alkylene group having 1 to 11 carbon atoms, an alkyleneoxy group having 1 to 11 carbon atoms, -(CH2O) p1 -C(=O)-, -(CH2O) p1 -, -(CH2O) p1 -(CH2) p2 -, -(CH2) p3 -(CH2O) p1 -(CH2) p2 -, -(OCH2) q1 -, -(OCH2) q1 -(CH2) q2 -, and -(CH2) q3 -(OCH2) q1 -(CH2) q2 - and is preferably one selected from the group consisting of. Further, p1 to p3 and q1 to q3 each independently preferably represent an integer of 1 to 11, more preferably an integer of 1 to 6, still more preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2.

[0080] In the general formula (b-1), each L 2 independently represents preferably a single bond or an alkylene group having 1 to 11 carbon atoms, more preferably a single bond or an alkylene group having 1 to 9 carbon atoms, and one or more -CH2- in the alkylene group may be substituted with -O- so as not to be adjacent to each other. Specifically, L 2is a single bond, an alkylene group having 1 to 11 carbon atoms, an alkyleneoxy group having 1 to 11 carbon atoms, -(CH2O) p1 -C(=O)-, -(CH2O) p1 -, -(CH2O) p1 -(CH2) p2 -, -(CH2) p3 -(CH2O) p1 -(CH2) p2 -, -(OCH2) q1 -, -(OCH2) q1 -(CH2) q2 - and -(CH2) q3 -(OCH2) q1 -(CH2) q2 - and is preferably one selected from the group consisting of. Further, it is preferable that p1 to p3 and q1 to q3 each independently represent an integer of 1 to 11, more preferably an integer of 1 to 6, still more preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2. Furthermore, R b1 or L 2 is preferably to have a -CH2O- group in at least one of, R b1 and L 2 is more preferably to have a -CH2O- group in both of.

[0081] Z in the general formula (b-1) above 1 preferably represents a hydrogen atom or an alkyl group having 1 to 11 carbon atoms, and more preferably represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.

[0082] In the general formula (b-1) above, k is preferably an integer of 0 to 20, more preferably an integer of 0 to 15, and still more preferably an integer of 0 to 10. When k is 2 or more, a plurality of Ls present 1 may be the same group as each other or different groups.

[0083] A preferred form of the compound (A-b) having the benzyl ether skeleton may be a compound having a structural unit represented by the following general formula (b-2). [Chemical formula] [In the general formula (b-2), R b1 each independently represents a hydrogen atom or an alkyl group having 1 to 11 carbon atoms, and one or more -CH2- in the alkyl group may be substituted by -O- or -C(=O)- so as not to be adjacent to each other. R b2 and R b3 each independently represents an alkyl group having 1 to 18 carbon atoms. L 1 each independently represents an alkylene group having 1 to 11 carbon atoms, and one or more -CH2- in the alkylene group may be substituted by -O- so as not to be adjacent to each other. L 2 represents a single bond or an alkylene group having 1 to 11 carbon atoms, and one or more -CH2- in the alkylene group may be substituted by -O- or -(C=O)- so as not to be adjacent to each other. Z 1 each independently represents a hydrogen atom or an alkyl group having 1 to 11 carbon atoms. k represents an integer of 0 or more and 20 or less. m b1 and m b2 each independently represents an integer of 0 or more and 4 or less. R b1 or L 2 has a -CH2O- group in at least one of them.]

[0084] In the general formula (b-2), R b1 , R b2 and R b3 , L 1 , L 2 , Z 1 , k, and m b1 and m b2 The preferred forms of are the same as those of the general formula (b-1).

[0085] The compound (A-b) having the benzyl ether skeleton may be used alone or in combination of two or more, and may also be a mixture containing two or more compounds (A-b) having different benzyl ether skeletons. In the present specification, for convenience of explanation, among the terms "compound (A-b) having a benzyl ether skeleton", a mixture containing two or more compounds (A-b) having different benzyl ether skeletons is referred to as a mixture (A-b) having a benzyl ether skeleton. Therefore, the "compound (A-b) having a benzyl ether skeleton" includes not only the case where only one kind of compound is represented, but also the mixture (A-b) having a benzyl ether skeleton.

[0086] The mixture (A-b) having the benzyl ether skeleton has a partial structure represented by the following general formula (b-3):

Chemical formula

[0087] The mixture (A-b) having the benzyl ether skeleton preferably has a component having a partial structure represented by the above general formula (b-3) occupying 95% by mass or more and 100% by mass or less of the whole mixture (A-b) having a benzyl ether skeleton and satisfying the following requirement (I) or (II). (I) The total number of linking groups per molecule (the total number of L 3 and L 4 ) constituting the component having a partial structure represented by the above general formula (b-3) is 1.1 or more and 2.4 or less. (II) The number of terminal groups bonded to the ends of the molecules constituting the component having the partial structure represented by the general formula (b-3) is 0.5 or more and 1.5 or less per molecule of the said molecule.

[0088] In the present embodiment, the linking group (L 3 and L 4 ) of the molecule constituting the component having the partial structure represented by the general formula (b-3) includes one kind of group selected from the group consisting of -CH2-, -CH2O-CH2-, -(CH2O)2-CH2- and -(CH2O)3-CH2-. In the entire mixture (A-b) having the benzyl ether skeleton, the following linking group (L 3 and L 4 The total number of) per molecule having a benzyl ether skeleton represented by the general formula (b-3) is preferably the composition of the following (1) to (4). (1) The number of the linking group "-CH2-" is preferably 0.65 or more and 1.4 or less. (2) The number of the linking group "-CH2O-CH2-" is preferably 0.07 or more and 0.2 or less, and more preferably 0.08 or more and 0.14 or less. (3) The number of the linking group "-(CH2O)2-CH2-" is preferably 0.10 or more and 0.8 or less, and more preferably 0.2 or more and 0.8 or less. In another form, it is preferably more than 0.41 and 0.8 or less. (4) The number of the linking group "-(CH2O)3-CH2-" is preferably 0.05 or more and 0.65 or less, preferably 0.09 or more and 0.6 or less, and more preferably 0.10 or more and 0.55 or less.

[0089] In the mixture (A-b) having the benzyl ether skeleton, it is preferable to have one or more groups selected from the group consisting of -CH2-OH, -CH2O-CH3, -(CH2O)2-CH3, -(CH2O)3-CH3 and -(CH2O)-COH as terminal groups bonded to the ends of the molecules constituting the component having the partial structure represented by the general formula (b-3). Then, in the entire mixture (A-b) having a benzyl ether skeleton, it preferably has a benzyl ether skeleton represented by the above general formula (b-3) and the number of terminal groups per molecule is 0.5 or more and 1.5 or less. In the entire mixture (A-b) having the benzyl ether skeleton, the number of the following terminal groups per molecule having a benzyl ether skeleton is preferably in the following composition (5) to (10). (5) The number of the terminal group "-CH2-OH" is preferably 0.17 or more and 0.4 or less, and more preferably 0.18 or more and 0.25 or less. (6) The number of the terminal group "-CH2O-CH3" is preferably 0.17 or more and 0.7 or less, and more preferably 0.18 or more and 0.44 or less. (7) The number of the terminal group "-(CH2O)2-CH3" is preferably 0.08 or more and 0.6 or less, and preferably 0.09 or more and 0.3 or less. (8) The number of the terminal group "-(CH2O)3-CH3" is preferably substantially not contained, more preferably 0.3 or less, and still more preferably 0.2 or less. (9) The number of the terminal group "-(CH2O)-COH" is preferably 0 or more and 0.1 or less, and more preferably 0.01 or more and 0.1 or less. In the mixture (A-b) having the benzyl ether skeleton, the chemical structure and number of the linking group, and the chemical structure and number of the terminal group can be calculated from NMR as shown in the column of the following examples, or the catalog of the manufacturer can be referred to.

[0090] The compound (A-b) having the benzyl ether skeleton may be a synthetic product or a commercially available product. Examples of the commercially available compound (A-b) having a benzyl ether skeleton include xylene resins [trade names: Nikanol (Y-50, Y-100, Y-300, Y-1000, LLL, LL, L or H)] manufactured by Fudo Co., Ltd.

[0091] In this embodiment, it is preferable that the structural unit of the compound (A-b) having a benzyl ether skeleton is contained in an amount of 1 to 99% by mass, more preferably 5 to 95% by mass, based on the total amount (100% by mass) of the polymaleimide resin (A). The structural unit of the compound (A-b) having a benzyl ether skeleton refers to the group represented by the above general formula (1).

[0092] - Maleic anhydride (A-c) - The maleic anhydride (A-c) is an essential component of the reaction raw material (1) of the polymaleimide resin (A), and is used in the reaction for maleimidizing the amino group derived from the aromatic amine compound (A-a) as described in the section of the production method of the polymaleimide resin (A) described later.

[0093] <<Physical properties of the polymaleimide resin (A)>> The number average molecular weight (Mn) of the polymaleimide resin (A) is preferably in the range of 200 to 1500, more preferably in the range of 300 to 800. Further, the weight average molecular weight (Mw) of the polymaleimide resin (A) is preferably in the range of 280 to 2000, more preferably in the range of 330 to 1200. The polymaleimide resin (A) is excellent in solvent solubility, heat resistance and low dielectric constant. From the viewpoint of excellent properties, the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] calculated from gel permeation chromatography (GPC) measurement is preferably in the range of 1.01 to 4.0, more preferably 1.05 to 2.0, and still more preferably 1.10 to 1.8. When the molecular weight distribution is wide and the high molecular weight component is large from the GPC chart obtained by GPC measurement, the ratio of the high molecular weight component contributing to flexibility increases. Therefore, compared with the cured product using conventional maleimide, brittleness is suppressed and a cured product excellent in flexibility and softness can be obtained, which is a preferable aspect. The number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the polymaleimide resin (A) were measured under the measurement conditions described in the examples below using gel permeation chromatography (hereinafter abbreviated as "GPC").

[0094] <<Production Method of Polymaleimide Resin (A)>> Hereinafter, the production method of the polymaleimide resin (A) will be described. The production method of the polymaleimide resin (A) is not particularly limited. As long as it has a partial structure represented by the above general formula (1), a partial structure represented by the above general formula (T-1) chemically bonded to the partial structure represented by the above general formula (1), and a partial structure represented by the above general formula (T-2) chemically bonded to the partial structure represented by the above general formula (1), it may be produced by any method. As a preferred embodiment of the production method of the polymaleimide resin (A), it is preferable to use an aromatic amine compound (A-a) represented by the following general formula (a-1) [hereinafter also simply referred to as aromatic amine compound (A-a)], a compound (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c) as reaction raw material (1). [Chemical formula] [In the above general formula (a-1), R a1 and R a2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 1 represents a hydrocarbon group having 1 to 18 carbon atoms, and R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]

[0095] As a specific embodiment of the production method of the polymaleimide resin (A), for example, a production method including the following steps (1) and (2) can be mentioned. Step (1): A step of reacting an aromatic amine compound (A-a) represented by the general formula (a-1) and a compound (A-b) having a benzyl ether skeleton as reaction raw materials (2) to obtain an intermediate amine compound (A-ab); Step (2): A step of reacting the intermediate amine compound (A-ab) obtained in the above step (1) and maleic anhydride (A-c) as reaction raw materials (3) to obtain a polymaleimide resin (A). Specifically, the method for producing the polymaleimide resin (A) includes a step (1) (also referred to as a crosslinking step) of reacting an aromatic amine compound (A-a) represented by the general formula (a-1) and a compound (A-b) having a benzyl ether skeleton under a solid acid catalyst, and a step (2) (also referred to as a condensation step) of condensing the intermediate amine compound (A-ab) generated in the step (1) and maleic anhydride (A-c). It is preferable to have these steps. Hereinafter, each step of the method for producing the polymaleimide resin (A) will be described in order.

[0096] - Step (1): A step for producing an intermediate amine compound (A-ab) - The step for producing the intermediate amine compound (A-ab) will be described below. The step (1) is not particularly limited. For example, it is a step of reacting the above-described aromatic amine compound (A-a), the above-described compound (A-b) having a benzyl ether skeleton (such as nicanol, etc.), and other compounds added as necessary in the presence of an acid catalyst. Thereby, the intermediate amine compound (A-ab) can be generated.

[0097] Regarding the blending ratio of the aromatic amine compound (A-a) and the compound (A-b) having a benzyl ether skeleton, considering the formability and curability physical property balance during the production of the resulting cured product, the molar ratio of the compound (A-b) having a benzyl ether skeleton is preferably 0.001 to 1 mol, more preferably 0.1 to 0.5 mol, per 1 mol of the aromatic amine compound (A-a). Also, when using a mixture such as the mixture (A-b) having a benzyl ether skeleton as the compound (A-b) having a benzyl ether skeleton, the reaction point with the aromatic amine compound (A-a) is the methyleneoxy part [for example, benzyl ether part (Ph-CH2O-CH2-), benzyl alcohol part (Ph-CH2O-H) or methyleneoxy part (-CH2-O-)] in the compound (A-b) having a benzyl ether skeleton contained in the mixture. Further, when the total number of these reaction points is taken as 1, the blending amount of the aromatic amine compound (A-a) is preferably equal to or more than the equivalent amount and 10 times or less. For example, with respect to 1 mol of the total number of the above reaction points, the blending amount of the aromatic amine compound (A-a) is preferably 1 to 10 mol.

[0098] Also, as a specific method for carrying out the reaction, all the raw materials are charged at once and reacted at a predetermined temperature as it is, or one of the aromatic amine compound (A-a) or the compound (A-b) having a benzyl ether skeleton and an acid catalyst are charged, and while maintaining at a predetermined temperature, the other of the aromatic amine compound (A-a) or the compound (A-b) having a benzyl ether skeleton is added dropwise and reacted. In this case, the dropping time is usually 0.1 to 12 hours, and preferably 6 hours or less. After the reaction, when a solvent is used, if necessary, the solvent and unreacted substances are distilled off to obtain the intermediate amine compound (A-ab), and when no solvent is used, the unreacted substances are distilled off to obtain the target intermediate amine compound (A-ab).

[0099] As the acid catalyst used in the step (1), 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 or lauryl sulfate; aromatic sulfates such as phenyl sulfate or phenyl fluorosulfate; and various acids such as oxalic acid. Examples of the inorganic acid include phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid or boric acid. Examples of the solid acid include activated clay, acid clay, alumina, silica alumina, zeolite, layered silicate, heteropolyacid or strongly acidic ion exchange resin. Examples of the layered silicate include kaolin group such as dickite, nacrite, kaolinite, anauxite, metahalloysite, halloysite; serpentine group such as chrysotile, lizardite, antigorite; smectite group such as montmorillonite, sauconite, beidellite, nontronite, saponite, teniolite, hectorite, stevensite; vermiculite group such as vermiculite; mica group such as mica, illite, sericite, glauconite; and attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite group. These layered silicates may form a mixed layer. The acid catalyst may be used alone or in combination of two or more.

[0100] After the reaction in the step (1), a solid acid that can be easily removed by filtration is preferable from the viewpoint of handleability. When using other acids, it is preferable to perform neutralization with a base and washing with water after the reaction. The base is not particularly limited and may be an organic base or an inorganic salt. Examples of the organic base include alkali metal alkoxides such as sodium methoxide, lithium methoxide, sodium ethoxide, lithium ethoxide, sodium tertiary butoxide, and potassium tertiary butoxide; trialkylamines such as triethylamine and ethyldiisopropylamine; aniline derivatives having an alkyl group with 1 to 4 carbon atoms such as N,N-dimethylaniline and N,N-diethylaniline; pyridine derivatives which may have an alkyl substituent with 1 to 4 carbon atoms such as pyridine and 2,6-lutidine; and nitrogen-containing heterocyclic compounds such as 1,8-diazabicyclo[5.4.0]-7-undecene. On the other hand, examples of the inorganic base include alkali metal hydrides such as sodium hydride and lithium hydride; alkaline earth metal hydrides such as calcium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; carbonates or hydrogen carbonates of alkali metals or alkaline earth metals such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate; and halogenated compounds of alkali metals or alkaline earth metals such as potassium fluoride, cesium fluoride, and potassium iodide. These bases may be used alone or in combination of two or more.

[0101] The compounding amount of the acid catalyst is in the range of 0.1 to 50 parts by mass with respect to 100 parts by mass of the total amount of the raw materials to be charged (compound (A-b) having a benzyl ether skeleton and aromatic amine compound (A-a)). From the viewpoints of handleability and economy, the range of 1 to 20 parts by mass is preferable. The reaction temperature is usually in the range of 100 to 300 °C, but in order to suppress the formation of isomer structures and avoid side reactions such as thermal decomposition, the range of 120 to 250 °C is preferable.

[0102] In the above step (1), regarding the reaction time of the mixture of the compound (A-b) having a benzyl ether skeleton and the aromatic amine compound (A-a), that is, the time of the crosslinking reaction, if the time is short, the reaction does not proceed completely, and if the time is long, side reactions such as thermal decomposition reaction of the product occur. Therefore, under the above reaction temperature conditions, usually, it is in the range of 1 to 60 hours in total, preferably in the range of 1 to 20 hours in total. In the method for producing the intermediate amine compound (A-ab), since the aromatic amine compound (A-a) or its derivative also serves as a solvent, it is not always necessary to use another solvent, but it is also possible to use a solvent. For example, when reacting nicanol L as the compound (A-b) having a benzyl ether skeleton as a raw material, a solvent capable of azeotropic dehydration such as toluene, xylene, or chlorobenzene is used, and if necessary, the water contained in the catalyst or the like is subjected to azeotropic dehydration, and then the solvent is distilled off, and then the reaction may be carried out within the above reaction temperature range.

[0103] The intermediate amine compound (A-ab) obtained by the above step (1) preferably has a partial structure represented by the following general formula (1), a partial structure represented by the following general formula (t-1) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (t-2) chemically bonded to the partial structure represented by the general formula (1).

Chemical formula

Chemical formula

[0104] "R 13 , m 2 and n 1 " in the above general formula (1) is synonymous with "R 13 , m 2 and n 1 " in the general formula (1) described above. Also, "L 11 , L 12 , L 13 , L 14 , R 11 , R 12 , R 14 , R 15 , m 1 and m 3 " in the above general formula (t-1) and general formula (t-2) is synonymous with "L 11 , L 12 , L 13 , L 14 , R 11 , R 12 , R 14 , R 15 , m 1 and m 3 " in the general formula (T-1) and (T-2).

[0105] In this embodiment, the amine equivalent of the intermediate amine compound (A-ab) is preferably 160 to 1200 g / equivalent, more preferably 180 to 600 g / equivalent. In addition, the measurement of the amine equivalent of the intermediate amine compound (A-ab) in this specification is taken as the value measured by a method conforming to the neutralization titration method specified in JIS K 0070 (1992).

[0106] - Step (2): Maleimidation - The said step (2) is a step of reacting the intermediate amine compound (A-ab) obtained in the said step (1) with maleic anhydride (A-c). Since the amino group of the intermediate amine compound (A-ab) can form a chemical structure in which the amino group is substituted with an N-substituted maleimide ring by the maleimidation reaction, the polymaleimide resin (A) can be obtained. The intermediate amine compound (A-ab) having the partial structure represented by the general formula (1), the partial structure represented by the general formula (t-1), and the partial structure represented by the general formula (t-2) obtained in the said step (1) is charged into a reactor, dissolved in an appropriate solvent, and then reacted with maleic anhydride (A-c) in the presence of a catalyst. After the reaction, unreacted maleic anhydride (A-c) or other impurities are removed by washing with water or the like, and the solvent is removed under reduced pressure to obtain the target polymaleimide resin (A). Also, a dehydrating agent may be used during the reaction if necessary.

[0107] Examples of the organic solvent used in the said step (2) include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane; cyclic ethers such as dioxane and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; and aromatic solvents such as benzene, toluene, and xylene. These may be used alone or in combination.

[0108] In the step (2), as the mixing ratio of the intermediate amine compound (A-ab) and maleic anhydride (A-c), it is preferable to blend the equivalent ratio of maleic anhydride (A-c) to the amino equivalent of the intermediate amine compound (A-ab) in the range of 1 to 5, more preferably charged at 1 to 3, and react in an organic solvent having a mass ratio of 0.1 to 10, preferably 0.2 to 5, based on the total amount of the intermediate amine compound (A-ab) and maleic anhydride (A-c).

[0109] Examples of the catalyst that can be used in the step (2) include inorganic salts such as acetates, chlorides, bromides, sulfates, and nitrates of nickel, cobalt, sodium, calcium, iron, lithium, manganese, etc., inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid, solid acids such as activated clay, acid clay, silica alumina, zeolite, and strongly acidic ion exchange resin, and heteropoly hydrochloric acid, etc. Among them, toluenesulfonic acid is particularly preferably used.

[0110] Examples of the dehydrating agent used in the step (2) include lower aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride, oxides such as phosphorus pentoxide, calcium oxide, and barium oxide, inorganic acids such as sulfuric acid, and porous ceramics such as molecular sieves. Preferably, acetic anhydride can be used.

[0111] There is no particular limitation on the amount of the catalyst and dehydrating agent used in the step (2). Usually, based on 1 equivalent of the amino group (-NH2) of the intermediate amine compound (A-ab), the catalyst can be used in an amount of 0.0001 to 1 mol, preferably 0.01 to 0.3 mol, and the dehydrating agent can be used in an amount of 1 to 3 mol, preferably 1 to 1.5 mol.

[0112] In the above step (2), as the reaction conditions for maleimidation, the above intermediate amine compound (A-ab) and maleic anhydride (A-c) are charged, and the reaction is carried out at a temperature range of 10 to 100 °C, preferably 30 to 60 °C, for 0.5 to 12 hours, preferably 1 to 4 hours. After that, the catalyst is added, and the reaction can be carried out at a temperature range of 90 to 130 °C, preferably 105 to 120 °C, for 1 to 24 hours, preferably 1 to 10 hours.

[0113] <<Polymaleimide resin mixture (C)>> The polymaleimide resin (A) of this embodiment may be a mixture. For example, when using, as the polymaleimide resin (A), a resin using the aromatic amine compound (A-a) represented by the above general formula (a-1), the compound (A-b) having the above benzyl ether skeleton, and maleic anhydride (A-c) as the reaction raw material (1), since there are a plurality of reaction points of the compound (A-b) having the above benzyl ether skeleton with respect to the aromatic amine compound (A-a) represented by the above general formula (a-1), the obtained intermediate amine compound (A-ab) itself can be a mixture in which a plurality of them are mixed. Therefore, the polymaleimide resin (A) can also be a mixture of compounds having various chemical structures. In this specification, the term "polymaleimide resin (A)" includes both a single substance and a mixture. On the other hand, only when the polymaleimide resin (A) means only a mixture, it is referred to as a polymaleimide resin mixture (C). The curable composition of this embodiment may be a composition containing a specific polymaleimide resin mixture (C) containing the above-described polymaleimide resin (A) and the above amine compound (B). According to the method for producing the above-described polymaleimide resin (A), a mixture containing the polymaleimide resin (A) and a maleimide multimer compound described later may be obtained. However, even if this mixture is blended into the curable composition, a curable composition having both low moisture absorption and high-order compatibility of low dielectric constant and low dielectric tangent after curing can be obtained. Hereinafter, the polymaleimide resin mixture (C) will be described in detail.

[0114] The polyimide resin mixture (C) contains a polyimide resin component having a partial structural unit represented by the following general formula (1a) and a maleimide multimer compound represented by the following general formula (2). The polyimide resin mixture (C) contains 1 to 99% by mass of the above polyimide resin (A) based on the total amount of the polyimide resin component, and contains 80% by mass or less of the maleimide multimer compound based on the total amount of the polyimide resin mixture (C). [Chemical formula] [In the above general formula (1a), R 11 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 represents a hydrocarbon group having 1 to 18 carbon atoms, R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 1 represents 2, m 2 represents an integer of 0 or more and 4 or less, and n 1 represents the average number of repeating units.] [Chemical formula] [In the above general formula (2), R 21 and R 25 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 22 and R 24 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 21 represents 2, m 23 represents 3, and n 21 represents an integer of 1 or more and 5 or less.]

[0115] The polyimide resin mixture (C) has high solubility in a solvent and exhibits a low dielectric tangent and high heat resistance after curing. Further, in the maleimide multimer compound represented by the general formula (2), the dimer in which n 21 is 1 has high crystallinity, and the solubility tends to improve as the trimer or tetramer in which n 21 is 2 or more. In addition, the substituents (R11 or R 15 , R 12 or R 14 By setting the number and position of ()) as in the present invention, the ratios of trimers and tetramers with excellent solubility can be increased. In addition, the curable composition containing the polymaleimide resin mixture (C) exhibits a low dielectric tangent and a low dielectric constant after curing.

[0116] "R 11 , R 12 , R 13 , n 1 , m 1 and m 2 " in the above general formula (1a) is synonymous with "R 11 , R 12 , R 13 , n 1 , m 1 and m 2 " in the general formula (1) or general formula (T-2) described above. In addition, "R 21 and R 25 " in the general formula (2) are each independently synonymous with "R 11 or R 15 " in the general formula (T-1) and general formula (T-2). In addition, "R 22 and R 24 " in the general formula (2) are each independently synonymous with "R 12 or R 14 " in the general formula (T-1) and general formula (T-2).

[0117] In the polyimide resin mixture (C) of the present embodiment, with respect to the total amount of the polyimide resin component, a polyimide resin (A) having a partial structure represented by the general formula (1), a partial structure represented by the following general formula (T-1) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (T-2) chemically bonded to the partial structure represented by the general formula (1) is preferably contained in an amount of 10% by mass to 99% by mass, more preferably 15% by mass or more to 98% by mass, still more preferably 20% by mass to 97% by mass. And, with respect to the total amount of the polyimide resin mixture (C), the maleimide multimer compound represented by the general formula (2) is preferably contained in an amount of 5% by mass to 80% by mass or less, more preferably 7% by mass to 80% by mass or less, still more preferably 10% by mass or more to 80% by mass or less.

[0118] As a preferable polyimide resin mixture (C) of the present embodiment, it contains a polyimide resin represented by the general formula (1A) (however, in the general formula (1A), a polyimide resin in which n1 is 1 or more) and a maleimide multimer compound represented by the general formula (2). With respect to the polyimide resin mixture (C), the content of the polyimide resin represented by the general formula (1A) (however, in the general formula (1A), a polyimide resin in which n1 is 1 or more) is preferably 10% by mass to 99% by mass, more preferably 15% by mass or more to 98% by mass, still more preferably 20% by mass to 97% by mass. With respect to the polyimide resin mixture (C), the content of the maleimide multimer compound represented by the general formula (2) is preferably 5% by mass to 80% by mass, more preferably 7% by mass to 80% by mass, still more preferably 10% by mass or more to 80% by mass.

[0119] Another preferable polyimide resin mixture (C) of the present embodiment is composed of the polyimide resin represented by the general formula (1A). The polymaleimide resin represented by the general formula (1A) is a resin using the aromatic amine compound (A-a) represented by the general formula (a-1), the compound (A-b) having the benzyl ether skeleton, and maleic anhydride (A-c) as reaction raw materials (1). The reaction raw materials (1) may be blended with the aromatic amine compound (A-a) represented by the general formula (a-1), preferably 5 to 98% by mass, more preferably 10 to 95% by mass, still more preferably 15 to 90% by mass, the compound (A-b) having the benzyl ether skeleton, preferably 1 to 90% by mass, more preferably 2 to 85% by mass, still more preferably 3 to 80% by mass, and maleic anhydride (A-c), preferably 2 to 90% by mass, more preferably 3 to 85% by mass, still more preferably 4 to 80% by mass.

[0120] <amine compound (B)> The curable composition of this embodiment contains an amine compound (B). By combining the amine compound (B) and the polymaleimide resin (A), it can contribute to low-temperature curing as a whole composition and exhibit excellent moldability, so it can be used as a molding material for structural materials and is useful. Further, the amine compound (B) acts as a curing agent by reacting with the polymaleimide resin (A), can cause three-dimensional crosslinking, and can obtain a cured product excellent in heat resistance, which is a preferable embodiment.

[0121] Examples of the amine compound (B) include compounds having primary to tertiary amino groups, preferably hydrocarbons having 1 or more carbon atoms, more preferably 3 to 25 carbon atoms, and more preferably hydrocarbon compounds having 2 or more primary amino groups in one molecule. The amine compound (B) is preferably an aliphatic amine compound or an aromatic amine compound, and more preferably an aliphatic primary diamine compound or an aromatic primary diamine compound. Note that the aromatic amine compound includes aromatic heterocyclic compounds, and the aliphatic amine compound includes alicyclic aliphatics.

[0122] Specific examples of the aliphatic amine compound include, for example, ethylenediamine, diethylenetriamine, hexamethylenediamine, triethylenetetramine, isophoronediamine, guanidine derivatives, guanamine derivatives, 1,3-bis(aminomethyl)cyclohexane, morpholine, 4,4-methylenebiscyclohexaneamine, and 4,4-ethylenebiscyclohexaneamine. The aliphatic amine compound may be used alone or in combination of two or more.

[0123] Specific examples of the aromatic amine compound include, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3-methyl-1,4-diaminobenzene, m-xylenediamine, p-xylenediamine, diethyltoluenediamine, 2,5-dimethyl-1,4-diaminobenzene, diaminodiphenylmethane (e.g., 4,4'-diaminodiphenylmethane), diaminodiphenylethane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, diaminodiphenyl ether (e.g., 4,4'-diaminodiphenyl ether), diaminodiphenyl sulfone (e.g., 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone), 4,4'-diaminodiphenyl ketone, benzidine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-methylenebis(2-ethyl-6-methylaniline), 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, 9,9-bis(4-aminophenyl)fluorene, and imidazole, etc. The aromatic amine compound may be used alone or in combination of two or more. Among the aromatic amine compounds, when emphasizing the mechanical properties after curing, m-phenylenediamine, p-phenylenediamine, 3-methyl-1,4-diaminobenzene, or 2,5-dimethyl-1,4-diaminobenzene is more preferable. On the other hand, when emphasizing heat resistance, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-bis(4-aminophenoxy)biphenyl, or 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4'-methylenebis(2-ethyl-6-methylaniline) is more preferable. Also, when emphasizing solubility in a solvent or handleability, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4'-methylenebis(2-ethyl-6-methylaniline) is more preferable. Furthermore, when emphasizing low dielectric properties, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane is more preferable.

[0124] Examples of the other amine compound (B) other than the aliphatic amine compound and the aromatic amine compound include hydroxylammonium sulfate, BF3-amine complex, and the like.

[0125] As the amine compound (B), when emphasizing the control of the curing reaction and moldability, an aromatic amine compound is preferable. Since the aliphatic amine compound acts as a catalyst and the curing reaction tends to proceed rapidly, when emphasizing moldability, it is more preferable to use an aromatic amine compound.

[0126] In the curable composition of the present embodiment, it is preferable to contain the amine compound (B) in an amount of 5% by mass or more and 50% by mass or less, more preferably 7% by mass or more and 30% by mass or less, and most preferably 10% by mass or more and 20% by mass or less, based on the total amount of the curable composition. When the content of the amine compound (B) is in the range of 10% by mass or more and 20% by mass or less, it is preferable from the viewpoint of heat resistance.

[0127] <Hardener (D) other than amine compounds> In the curable composition of the present embodiment, a hardener (D) other than the above-mentioned amine compound (B) can also be added within a range that does not impair the effects of the present invention. In addition, with respect to 100% by mass of the total amount of the curable composition, the hardener (D) is preferably 2% by mass or more and 20% by mass or less, and most preferably 5% by mass or more and 10% by mass or less. When the content of the hardener (D) is in the range of 5% by mass or more and 10% by mass or less, it is preferable from the viewpoints of curability and low dielectric tangent.

[0128] Examples of the hardener (D) include cyanate compounds, amide compounds, acid anhydride compounds, phenol compounds, polyphenylene ether compounds, compounds having an unsaturated double bond-containing substituent, diene polymers, and the like. These hardeners may be used alone or in combination of two or more.

[0129] Examples of the cyanate compound include bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, bisphenol S type cyanate ester resin, bisphenol sulfide type cyanate ester resin, phenylene ether type cyanate ester resin, naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethylbiphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolak type cyanate ester resin, cresol novolak type cyanate ester resin, triphenylmethane type cyanate ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-condensed novolak type cyanate ester resin, naphthol-cresol co-condensed novolak type cyanate ester resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type cyanate ester resin, biphenyl-modified novolak type cyanate ester resin, anthracene type cyanate ester resin, and the like. These may be used alone or in combination of two or more.

[0130] Examples of the amide compound include dicyandiamide, polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, and the like.

[0131] Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like.

[0132] Examples of the phenolic compound include polyphenol novolak resins synthesized from polyhydric hydroxy compounds and formaldehyde, such as phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zylock resin), resorcinol novolak resin, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked by bismethylene groups), biphenyl-modified naphthol resin (a polyhydric naphthol compound in which phenol nuclei are linked by bismethylene groups), aminotriazine-modified phenol resin (a polyhydric phenol compound in which phenol nuclei are linked by melamine, benzoguanamine, etc.), alkoxy group-containing aromatic ring-modified novolak resin (a polyhydric phenol compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked by formaldehyde), and the like.

[0133] The polyphenylene ether-based compound preferably has a structure represented by the following general formula (3-1) or (3-2).

Chemical formula

Chemical formula

[0134] In the above general formulas (3-1) and (3-2), R 31 ~R 38Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioether group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 5 carbon atoms, an alkyloxycarbonyl group having 2 to 5 carbon atoms, an alkylcarbonyloxy group having 2 to 5 carbon atoms, an alkylsulfonyl group having 1 to 5 carbon atoms, and the like. Examples of the terminal structure of the structures represented by the general formulas (3-1) and (3-2) include those having a hydroxyl group or a reactive double bond-containing group. Further, v is an integer of 1 to 30, and w and u are also integers of 1 to 30.

[0135] The thioether group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a methylthio group, an ethylthio group, a propylthio group, an isopropylthio group, a butylthio group, and a pentylthio group.

[0136] The alkylcarbonyl group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include a methylcarbonyl group, an ethylcarbonyl group, a propylcarbonyl group, an isopropylcarbonyl group, and a butylcarbonyl group.

[0137] The alkyloxycarbonyl group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group, an isopropyloxycarbonyl group, and a butyloxycarbonyl group.

[0138] The alkylcarbonyloxy group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include a methylcarbonyloxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, and a butylcarbonyloxy group.

[0139] The alkylsulfonyl group having 1 to 5 carbon atoms is not particularly limited, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, and a pentylsulfonyl group.

[0140] In the above general formulas (3-1) and (3-2), R 31 ~R 38 may be the same as or different from each other, and is preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a cycloalkyl group having 3 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, still more preferably a hydrogen atom, a methyl group, or an ethyl group, and particularly preferably a hydrogen atom or a methyl group.

[0141] In the above general formula (3-2), Y may be a divalent aromatic group derived from an aromatic compound having two phenolic hydroxyl groups. The aromatic compound having two phenolic hydroxyl groups is not particularly limited, and examples thereof include catechol, resorcinol, hydroquinone, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol B, bisphenol BP, bisphenol C, bisphenol F, and tetramethyl bisphenol A. Among these, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol E, and bisphenol F are preferable, and 4,4'-biphenol, bisphenol A, and tetramethyl bisphenol A are more preferable. In addition, since the two phenolic hydroxyl groups of the aromatic compound having two phenolic hydroxyl groups form a phenylene ether bond (two oxygen atoms bonded to Y), Y is a divalent aromatic group derived from an aromatic compound having two phenolic hydroxyl groups. In other words, a group obtained by removing two arbitrary hydrogen atoms from the above aromatic compound having two phenolic hydroxyl groups is defined as a "divalent aromatic group derived from an aromatic compound having two phenolic hydroxyl groups".

[0142] Examples of the compound having an unsaturated double bond-containing substituent include, but are not particularly limited to, compounds having two or more unsaturated bond-containing substituents in the molecule. Examples of the unsaturated bond-containing substituent include compounds having an allyl group, isopropenyl group, 1-propenyl group, acryloyl group, methacryloyl group, styryl group, styrylmethyl group, etc.

[0143] Examples of the diene polymer include non-modified diene polymers not modified by polar groups. Here, the polar group is a functional group that affects dielectric properties, and examples include a phenol group, amino group, epoxy group, etc. The diene polymer is not particularly limited, and for example, 1,2-polybutadiene, 1,4-polybutadiene, etc. can be used.

[0144] As the diene polymer, homopolymers of butadiene in which 50% or more of the butadiene units in the polymer chain are 1,2-bonds and derivatives thereof can also be used.

[0145] <Other resin (E)> The curable composition of the present embodiment may contain other resins (E) in addition to the polymaleimide resin (A) and the amine compound (B) as long as the object of the present invention is not impaired. Examples of the other resin (E) include bismaleimides other than the polymaleimide resin (A), allyl ether compounds, allylamine compounds, triallyl cyanurate, alkenylphenol compounds, vinyl group-containing polyolefin compounds, etc., epoxy resins, phenol resins, active ester resins, polyphenylene ether resins, benzoxazine resins, styrene maleic anhydride copolymers, polybutadiene and its modified products, polyacetal resins, polyvinyl alcohol resins, liquid crystal polymers, fluorine resins, polystyrene, polyethylene, polyimide resins, thermosetting polyimide resins, silicone gels, silicone oils, etc., which can be appropriately blended. In addition, since the curable composition of the present embodiment contains the amine compound (B), an epoxy resin may be selected as the other resin (E). As a result, in the curable composition containing the polymaleimide resin (A), the amine compound (B), and the epoxy resin, since the amine compound (B) acts as a curing agent, the adhesion to copper is improved, and thus it can be useful, for example, in the production of a circuit board using a copper foil.

[0146] The epoxy resin is not particularly limited. For example, novolac type epoxy resins such as phenol novolac type epoxy resin, cresol novolac type epoxy resin, α-naphthol novolac type epoxy resin, β-naphthol novolac type epoxy resin, bisphenol A novolac type epoxy resin, biphenyl novolac type epoxy resin; aralkyl type epoxy resins such as phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin; bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol A type epoxy resin; biphenyl type epoxy resins such as biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, epoxy resin having a biphenyl skeleton and a diglycidyl oxybenzene skeleton; naphthalene type epoxy resin; binaphthol type epoxy resin; binaphthyl type epoxy resin; dicyclopentadiene type epoxy resins such as dicyclopentadiene phenol type epoxy resin; glycidylamine type epoxy resins such as tetraglycidyl diaminodiphenylmethane type epoxy resin, triglycidyl-p-aminophenol type epoxy resin, glycidylamine type epoxy resin of diaminodiphenyl sulfone; diglycidyl ester type epoxy resins such as 2,6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resin, glycidyl ester type epoxy resin of hexahydrophthalic anhydride; benzopyran type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, 7-phenylhexamethyldibenzopyran, etc. These may be used individually by one type or in combination of two or more types.

[0147] The content of the other resin (E) is preferably 2% by mass or more and 20% by mass or less, and most preferably 5% by mass or more and 10% by mass or less with respect to 100% by mass of the total amount of the curable composition. When the content of the other resin (E) is in the range of 5% by mass or more and 10% by mass or less, it is preferable from the viewpoint of heat resistance.

[0148] <Curing accelerator> The curable composition of the present embodiment can also be appropriately used in combination with a curing accelerator as needed. Various curing accelerators can be used. For example, the addition of a polymerization initiator such as an organic peroxide or an azo compound, or a basic catalyst such as a phosphine-based compound or a tertiary amine is effective. Specific examples of the curing accelerator include, for example, benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, TPP-MK, TPP-K, triethylamine, imidazoles, and the like. The curing accelerator can be used alone or in combination of two or more. The blending amount of the curing accelerator is preferably 0.05 to 5% by mass of the entire curable resin composition.

[0149] <Additive> The curable composition of the present embodiment can also be appropriately used in combination with additives as needed. Examples of the additives include silane coupling agents, mold release agents, pigments, emulsifiers, non-halogen flame retardants, inorganic fillers, flame retardants, solvents, and the like. The content of the additives is preferably 1% by mass or more and 20% by mass or less, and most preferably 3% by mass or more and 10% by mass or less with respect to 100% by mass of the total amount of the curable composition.

[0150] Examples of the flame retardant include inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, halogen-based flame retardants, or non-halogen-based flame retardants. In the curable composition of the present embodiment, in order to exhibit flame retardancy within a range that does not impair the purpose, it is more preferable to blend a non-halogen-based flame retardant that substantially does not contain halogen atoms. Examples of the non-halogen-based flame retardant include, for example, phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic-based flame retardants, organic metal salt-based flame retardants, and the like, and these can be used alone or in combination.

[0151] In the curable composition of this embodiment, an inorganic filler can be blended as necessary. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, and the like. When the blending amount of the inorganic filler is particularly increased, it is preferable to use fused silica. The fused silica can be used in either a crushed form or a spherical form, but in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use spherical ones. Further, in order to increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 30% by mass or more and 50% by mass or less based on the total amount of the curable composition. Also, when the curable composition is used for applications such as conductive paste described in detail below, a conductive filler such as silver powder or copper powder can be used.

[0152] <Content of each component> In the curable composition of this embodiment, the lower limit of the total content of the polymaleimide resin (A) and the amine compound (B) is preferably 40% by mass, 42% by mass, 45% by mass, 47% by mass, 48% by mass, or 50% by mass with respect to the entire curable composition (100% by mass). Also, the upper limit of the total content is preferably 100% by mass, 99% by mass, 98% by mass, or 97% by mass. The above upper limit value and the above lower limit value can be arbitrarily combined. Therefore, for example, in the curable composition of this embodiment, the total content of the polymaleimide resin (A) and the amine compound (B) is preferably 40% by mass or more and 100% by mass or less with respect to the entire curable composition (100% by mass), more preferably 45% by mass or more and 100% by mass or less, and still more preferably 50% by mass or more and 100% by mass or less.

[0153] In the curable composition of the present embodiment, the lower limit of the total content of the polyimide resin (A), the amine compound (B), and the inorganic filler is preferably 70% by mass, 73% by mass, 75% by mass, 77% by mass, or 80% by mass with respect to the entire curable composition (100% by mass). Further, the upper limit of the total content is preferably 100% by mass, 99% by mass, 98% by mass, or 97% by mass. The upper limit value and the lower limit value can be arbitrarily combined in the same manner as the range of the total content of the polyimide resin (A) and the amine compound (B).

[0154] In the curable composition of the present embodiment, the lower limit of the total content of the polyimide resin (A), the amine compound (B), and the additive is preferably 43% by mass, 45% by mass, 48% by mass, 50% by mass, or 53% by mass with respect to the entire curable composition (100% by mass). Further, the upper limit of the total content is preferably 100% by mass, 99% by mass, 98% by mass, or 97% by mass. The upper limit value and the lower limit value can be arbitrarily combined in the same manner as the range of the total content of the polyimide resin (A) and the amine compound (B).

[0155] In the curable composition of the present embodiment, as the polyimide resin (A), a component represented by the above general formula (1A) and having the sum of n 1 and n 3 of 1 or more is preferably contained in an amount of 10% by mass or more. In the curable composition, when the content of the specific polyimide resin represented by the above general formula (1A) is 10% by mass or more, the cured product can achieve both low moisture absorption and high levels of low dielectric tangent and low dielectric constant. Further, from the viewpoint of heat resistance, the curable composition of the present embodiment desirably contains a component represented by the above general formula (1A) and having n 2 of 1 or more in an amount of 5% by mass or more.

[0156] [Cured product] The cured product of this embodiment is preferably obtained from the above-described curable composition. The cured product can be obtained by subjecting the curable composition to a curing reaction. The curable composition can be obtained by uniformly mixing the above-described respective components (for example, a curing agent, compounding agents), and can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as a laminate, a cast product, an adhesive layer, a coating film, and a film. The curing (thermosetting) reaction can be easily carried out even without a catalyst. However, when it is desired to make the reaction proceed more rapidly, the addition of a polymerization initiator such as an organic peroxide or an azo compound, or a basic catalyst such as a phosphine-based compound or a tertiary amine is effective. For example, there are benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazoles, etc., and the blending amount is preferably 0.05 to 5% by mass of the entire curable resin composition.

[0157] Since the cured product obtained from the curable composition containing the polymaleimide resin (A) and the amine compound (B) achieves both excellent low moisture absorption and low dielectric properties, it can be suitably used for heat-resistant members or electronic members. 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, etc. Further, it can also be suitably used as a matrix resin for fiber-reinforced resins, and is particularly suitable as a prepreg having high heat resistance or a small dimensional change rate. Further, the polymaleimide resin (A) contained in the curable composition can be made into a paint since it exhibits excellent solubility in various solvents. The heat-resistant members and electronic members thus obtained can be suitably used for various applications, and examples include industrial machine parts, general machine parts, parts of automobiles, railways, vehicles, etc., space and aviation-related parts, electronic and electrical parts, building materials, container and packaging members, daily necessities, sports and leisure goods, housing members for wind power generation, etc., but are not limited thereto.

[0158] Hereinafter, examples of typical products (prepregs, circuit boards, build-up boards, build-up films, semiconductor encapsulants, semiconductor devices, conductive pastes) manufactured using the curable composition of the present embodiment will be described with examples.

[0159] <Prepreg> The prepreg of the present embodiment has a reinforcing base material and a semi-cured product of the above-described curable composition of the present embodiment impregnated in the reinforcing base material. As a method for obtaining a prepreg from the curable composition, an organic solvent described later is blended to form a varnish-like curable composition, which is impregnated into a reinforcing base material (paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, etc.), and then heated at a heating temperature corresponding to the type of solvent used, preferably 50 to 170 °C, to semi-cure (or uncure) the curable composition to obtain a prepreg. The mass ratio of the curable composition to the reinforcing base material used at this time is not particularly limited, but usually, it is preferably prepared so that the resin content contained in the composition in the prepreg is 20 to 60% by mass. In the present embodiment, the semi-cured product of the curable composition is obtained by adjusting the heating temperature and heating time to stop the curing reaction midway without completing it. Also, for example, the semi-cured product can have a curing degree of, for example, 85% or less and 5% or more. On the other hand, the cured product in the present embodiment can have a higher curing degree than the semi-cured product. Note that the curing degree of the semi-cured product can be calculated from the following formula by measuring the heat of curing during heating of the curable composition and the heat of curing of the semi-cured product using DSC. Curing degree (%) = [1 - (Heat of curing of semi-cured product / Heat of curing of curable composition)] × 100

[0160] Examples of the organic solvent used for manufacturing the prepreg of the present embodiment include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. The selection and appropriate usage amount can be appropriately selected according to the application. For example, when further manufacturing a printed circuit board from the prepreg as follows, it is preferable to use a polar solvent having a boiling point of 160°C or lower, such as methyl ethyl ketone, acetone, dimethylformamide, etc., and it is also preferable to use it at a ratio such that the non-volatile content is 40 to 80% by mass. In addition, examples of the reinforcing base material used for manufacturing the prepreg of the present embodiment include woven fabrics, non-woven fabrics, or mats, paper, etc. made of inorganic fibers and organic fibers such as glass fibers, polyester fibers, and polyamide fibers, and these can be used alone or in combination.

[0161] The heat treatment conditions of the prepreg of the present embodiment are appropriately selected according to the type and usage amount of the organic solvent, catalyst, various additives, etc. used, but usually, it is preferably carried out under conditions of a temperature of 80 to 220°C for 3 minutes to 30 minutes.

[0162] <Circuit board> The circuit board of the present embodiment is a laminate having the above-mentioned prepreg and copper foil. Examples of the method for obtaining a printed circuit board from the curable composition of the above-mentioned present embodiment include a method of laminating the above prepreg by a conventional method, appropriately stacking copper foil, and thermocompression bonding at 170 to 300°C for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.

[0163] <Build-up board> Examples of the method for obtaining a build-up board from the curable composition of the present embodiment include a method that passes through the following steps 1 to 3. In step 1, first, the curable composition appropriately blended with rubber, filler, etc. is applied to the circuit board on which a circuit is formed using a spray coating method, a curtain coating method, etc., and then cured. In Step 2, after drilling holes such as predetermined through-hole parts in the circuit board coated with the curable composition as needed, the surface is treated with a roughening agent and then rinsed with hot water to form unevenness on the substrate, and a metal such as copper is plated. In Step 3, the operations of Steps 1 and 2 are sequentially repeated as desired to alternately build up a resin insulating layer and a conductor layer of a predetermined circuit pattern to form a build-up substrate. In addition, in the above steps, the drilling of the through-hole parts may be performed after the formation of the outermost resin insulating layer. Further, the build-up substrate in the present embodiment can be manufactured by heat-pressing a copper foil with resin obtained by semi-curing the composition on a copper foil at 170 to 300 °C onto a wiring board on which a circuit is formed, thereby forming a roughened surface and omitting the plating process.

[0164] <Build-up film> The build-up film of the present embodiment contains the curable composition of the present embodiment described above. As a method for manufacturing the build-up film of the present embodiment, a method is exemplified in which the curable composition is applied onto a support film (Y) and then dried to form a curable composition layer on the support film (Y) to obtain an adhesive film for a multilayer printed wiring board.

[0165] When manufacturing a build-up film from a curable composition, the film softens under the temperature conditions of lamination in the vacuum lamination method (usually 70 to 140 °C), and it is important that the film exhibits fluidity (resin flow) that enables resin filling in via holes or through-holes existing in the circuit board simultaneously with the lamination of the circuit board. It is preferable to blend the above components so as to exhibit such characteristics. In addition, in the obtained build-up film and circuit board (copper-clad laminate, etc.), in order to prevent phenomena such as locally different characteristic values caused by phase separation, etc., and to exhibit constant performance at any site, appearance uniformity is required.

[0166] Here, the diameter of the through-hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. Usually, it is preferable to enable resin filling within this range. When laminating both sides of the circuit board, it is desirable that the through-hole be filled to about half its depth.

[0167] Specifically, the method for manufacturing the above-described adhesive film is as follows: After preparing the varnish-like curable composition, the varnish-like composition is applied to the surface of the support film (Y), and then the organic solvent is dried by heating, hot air blowing, or the like to form a composition layer (X) composed of the curable composition. As the organic solvent, for example, ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used. Also, it is preferably used at a ratio such that the non-volatile content is 30 to 60% by mass.

[0168] The thickness of the formed composition layer (X) 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 resin composition layer preferably has a thickness of 10 to 100 μm. Note that the composition layer (X) in the present embodiment may be protected by a protective film described later. By protecting with a protective film, it is possible to prevent the adhesion of dust and the like and scratches on the surface of the resin composition layer.

[0169] The above-mentioned support film (Y) and protective film can include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate, polycarbonate, polyimide, and further metal foils such as release paper, 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 mat treatment or a corona treatment. The thickness of the support film is not particularly limited, but it is usually 10 to 150 μm, and preferably used in the range of 25 to 50 μm. Also, the thickness of the protective film is preferably 1 to 40 μm.

[0170] The above-mentioned support film (Y) is peeled off after being laminated on the circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the adhesive film is heat cured, it is possible to prevent the adhesion of dust and the like during the curing process. When peeling off after curing, usually, the support film is previously subjected to a release treatment. In addition, a multilayer printed circuit board can be manufactured from the build-up film obtained as described above. For example, when the resin composition layer (X) is protected by a protective film, after peeling these, the layer (X) of the resin composition is laminated on one or both sides of the circuit board so as to be directly in contact with the circuit board, for example, by a vacuum lamination method. The lamination method may be a batch type or a continuous type on a roll. Also, if necessary, the build-up film and the circuit board may be heated (preheated) as necessary before lamination. The lamination conditions preferably have a crimping temperature (lamination temperature) of 70 to 140 °C, and a crimping pressure of 1 to 11 kgf / cm 2 (9.8×10 4 ~107.9×10 4 N / m 2 ) and it is preferably laminated under a reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

[0171] <Semiconductor encapsulant> The semiconductor encapsulant of this embodiment contains the curable composition of this embodiment described above. The semiconductor encapsulant obtained by using the curable composition of this embodiment has reduced hygroscopicity, dielectric constant, and dielectric tangent by using the polymerimide resin (A) and the amine compound (B), so it is excellent in processability, moldability, and reflow resistance in the manufacturing process, which is a preferable aspect.

[0172] The curable composition of this embodiment used for the semiconductor encapsulant may contain an inorganic filler. As the filling rate of the inorganic filler, for example, the inorganic filler can be used in the range of 0.5 to 1200 parts by mass with respect to 100 parts by mass of the curable composition of this embodiment. As the inorganic filler, as described above, for example, barium sulfate, barium titanate, amorphous silica, crystalline silica, noble silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, etc. can be mentioned.

[0173] As a method for obtaining the semiconductor encapsulant, to the curable composition of this embodiment, a curing accelerator and / or an additive, which are optional components, are added as necessary, and a method of sufficiently melt-mixing uniformly using an extruder, a kneader, a roll, etc. can be mentioned. When used as a high thermal conductivity semiconductor encapsulant for power transistors and power ICs, high filling of crystalline silica, alumina, silicon nitride, etc., which have a higher thermal conductivity than fused silica, or the use of fused silica, crystalline silica, alumina, silicon nitride, etc. is preferable. The filling rate is preferably in the range of 30 to 95 parts by mass of the inorganic filler per 100 parts by mass of the curable composition. Among them, in order to improve flame retardancy, moisture resistance, solder crack resistance, and reduce the linear expansion coefficient, 70 parts by mass or more is more preferable, and 80 parts by mass or more is even more preferable.

[0174] <Semiconductor device> The semiconductor device of this embodiment includes a cured product of the above-described semiconductor encapsulant. Since the semiconductor device obtained using the semiconductor encapsulant obtained using the curable composition of this embodiment uses the polyimide resin (A) and the amine compound (B), it has a low viscosity and excellent fluidity. Furthermore, since its hygroscopicity, elastic modulus at high temperatures, or adhesiveness to a metal material is improved, it is excellent in workability, moldability, and reflow resistance in the manufacturing process, which is a preferable aspect.

[0175] As a method for obtaining the semiconductor device, there is a method of casting the semiconductor encapsulating material or molding it using a transfer molding machine, an injection molding machine, etc., and further heat-curing it in a temperature range of room temperature (20 °C) to 250 °C.

[0176] <Conductive paste> As a method for obtaining a conductive paste from the curable composition of this embodiment, for example, a method of dispersing conductive particles in the composition can be mentioned. The above conductive paste can be made into a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the type of conductive particles used.

Examples

[0177] The present invention will be specifically described by way of examples and comparative examples. Hereinafter, "parts" and "%" are based on mass unless otherwise specified. The physical properties of the synthesized polyimide resin were measured as follows. Also, the physical properties of the prepared curable composition were measured as follows, and the results are shown in Table 1.

[0178] (1) GPC measurement Using the following measuring device and measurement conditions, the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the polyimide resin obtained in the synthesis example were calculated. · Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation Column: Guard 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 Detector: RI (Differential Refractometer) Data processing: “GPC Workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation · Measurement conditions: Column temperature 40°C Developing solvent: Tetrahydrofuran Flow rate: 1.0 mL / min · Standard: The following monodisperse polystyrenes with known molecular weights were used in accordance with the measurement manual of the “GPC Workstation EcoSEC-WorkStation”. (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 1.0 mass% tetrahydrofuran solution of the polymer maleimide resin (A) obtained in the synthesis example, filtered through a microfilter (50 μL), in terms of resin solids content.

[0179] (2) Amine equivalent and maleimide group equivalent The amine equivalent of the aromatic amine obtained in the synthesis example was measured by the following method. Approximately 2.5 g of the intermediate amine compound, 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine were accurately weighed into a 500 mL conical flask with a stopper, a condenser was attached, and the mixture was heated under reflux at 120°C in an oil bath for 150 minutes. After cooling, 5.0 mL of distilled water, 100 mL of propylene glycol monomethyl ether, and 75 mL of tetrahydrofuran were added, and titration was performed by potentiometric titration with a 0.5 mol / L potassium hydroxide-ethanol solution. A blank test was conducted in the same manner for correction. Amine equivalent (g / equivalent) = (S × 2,000) / (Blank - A) S: Amount of sample (g) A: Consumption of 0.5 mol / L potassium hydroxide-ethanol solution (mL) Blank: Consumption of 0.5 mol / L potassium hydroxide-ethanol solution in the blank test (mL) The maleimide group equivalent of the polymaleimide resin obtained in the synthesis example is a value converted from the amine equivalent of the intermediate amine compound and is calculated by the following formula. Maleimide equivalent (g / equivalent) = Amine equivalent + 80

[0180] (3) FD-MS measurement The FD-MS spectrum of the polymaleimide resin obtained in the synthesis example was measured using the following measuring apparatus and measurement conditions. · Measuring apparatus: JMS-T100GC AccuTOF · Measurement conditions Measurement range: m / z = 4.00 - 2000.00 Rate of change: 51.2 mA / min Final current value: 45 mA Cathode voltage: -10 kV Recording interval: 0.07 sec

[0181] (4) 13 13C-NMR measurement The 13C-NMR spectrum of the polymaleimide resin obtained in the synthesis example 13 was measured under the following measuring apparatus and measurement conditions. · 13 13C-NMR: "JNM-ECZ400S" manufactured by JEOL RESONANCE Resonance frequency: 100 MHz Number of integrations: 4000 times Solvent: chloroform-d Sample concentration: 12 mass% Relaxing reagent: Chromium(III) acetylacetonate

[0182] [Synthesis Example 1] Synthesis of Polymaleimide Resin (A-1) (1) Synthesis of Intermediate Amine Compound (a-1) Into a flask equipped with a thermometer, a condenser, a Dean-Stark trap, and a stirrer, 350 g of 2,3-dimethylaniline, 127.3 g of xylene formaldehyde resin (Nicanol L, manufactured by Fudo Co., Ltd.), 240 g of toluene, and 133.7 g of activated clay were charged. While stirring, the temperature was raised to 120 °C and held for 30 minutes. Then, the temperature was raised to 160 °C and held for 4 hours. After the holding was completed, the temperature was raised to 200 °C over 60 minutes and held for 15 hours. After the holding was completed, it was diluted with 240 g of toluene, and the activated clay was filtered off by filtration. The filtrate was distilled off the solvent and excess 2,3-dimethylaniline by heating under reduced pressure to obtain an intermediate aromatic amine compound (a-1) (amine equivalent 218 g / eq.). The FD-MS spectrum of the obtained intermediate amine compound (a-1) is shown in Figure 1, 13 and the C-NMR spectrum is shown in Figure 2.

[0183] (2) Maleimidation 70.08 g (1.3 equivalents) of maleic anhydride and 260.4 g of toluene were charged into a 2 L flask equipped with a thermometer, a cooling tube, a Dean-Stark trap, and a stirrer, and stirred at room temperature. Next, a mixed solution of 120.0 g (1 equivalent) of the intermediate amine compound (a-1) and 32.6 g of DMF was added dropwise over 1 hour, and then reacted for 2 hours. 5.23 g of p-toluenesulfonic acid monohydrate was added to the reaction solution, and the reaction solution was heated to azeotropically distill the water and toluene that came out under reflux. After cooling and separating them, the reaction solution was heated to 115 °C and the water and toluene that came out under reflux were cooled and separated. Then, only toluene was returned to the system and the dehydration reaction was carried out for 5 hours. After air-cooling to room temperature, it was concentrated under reduced pressure, and the obtained brown solution was dissolved in 600 g of ethyl acetate and washed 3 times with 200 g of ion-exchanged water and 3 times with 150 g of 2% aqueous sodium hydrogen carbonate solution. Then, sodium sulfate was added to the oil layer for drying and concentrated under reduced pressure. The obtained reaction product was vacuum-dried at 80 °C for 4 hours to obtain a product containing the polyimide resin (A-1). The GPC chart of this polyimide resin (A-1) is shown in Figure 3, the FD-MS spectrum is shown in Figure 4, 13 The C-NMR spectrum is shown in Figure 5. From the results of GPC and the like, the obtained polyimide resin (A-1) is represented by the above general formula (1A), and n 1 and n 3 The sum of is 1 or more and contains 20% by mass or more of the component, and n 2 It was confirmed that the component in which is 1 or more contains 10% by mass or more.

[0184] Regarding each peak of the FD-MS spectrum shown in Figure 4, the number of repetitions in the polyimide resin (A-1) was confirmed. Table 1 shows the correspondence between each peak, the number of repetitions [n 1 and n 2 in the general formula (1A) and the bonding position of *.

Table 1

[0185] [Examples 1 to 2 and Comparative Examples 1 to 3] <Preparation of curable composition> The polyimide resin (A-1) obtained in Synthesis Example 1, a comparative maleimide compound (A-2) ("BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd., phenylmethane maleimide), a comparative maleimide compound (A-3) ("BMI-5100" manufactured by Daiwa Kasei Kogyo Co., Ltd., 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide), an amine compound (B-1) [4,4'-diaminodiphenylmethane, manufactured by Tokyo Chemical Industry Co., Ltd.], an amine compound (B-2) [4,4'-methylenebis(2-ethyl-6-methylaniline)], and DCPO ("Parkmill D" manufactured by NOF Corporation, dicumyl peroxide) as a curing catalyst were blended at the ratios shown in Table 2 to prepare a curable composition.

[0186] <Preparation of cured product> The curable composition was cured under the following conditions to obtain a cured product. Curing conditions: After heating at 200°C for 2 hours using a vacuum press, it was heat-cured at 250°C for 2 hours. The plate thickness after molding was 1.3 mm. For this cured product, physical property evaluations of dielectric constant, dielectric tangent, and moisture absorption rate were performed by the following methods. The results are shown in Table 2.

[0187] <Measurement of dielectric constant and dielectric tangent> In accordance with JIS-C-6481, using the network analyzer "E8362C" manufactured by Agilent Technologies, Inc., the dielectric constant (Dk) and dielectric tangent (Df) at 10 GHz of the test piece after storing in a room at 23°C and 50% humidity for 24 hours after being completely dried were measured by the cavity resonance method.

[0188] <Measurement of moisture absorption rate> In this example and comparative examples, as a method for evaluating low moisture absorption, the moisture absorption rate (%) was calculated and evaluated by the following method. A test piece cut out from the cured product obtained above to dimensions of 5 mm × 55 mm × 1.3 mm was held under the conditions of 85°C, 85% RH, and 1 atm for 50 hours using a pressure cooker tester, and the moisture absorption rate (%) was calculated and evaluated by the following formula. Moisture absorption rate (%) = (mass of the test piece after the test - mass of the test piece before the test) / (mass of the test piece before the test) × 100

[0189]

Table 2

[0190] From Table 2, it was confirmed that Examples 1 and 2 have high-order compatibility of low dielectric constant, low dielectric tangent, and low moisture absorption.

Industrial Applicability

[0191] The curable composition and the cured product thereof of the present invention can be used in prepregs, circuit boards, build-up films, semiconductor encapsulants, semiconductor devices, and the like.

Claims

1. A polymerimide resin (A) having a partial structure represented by the following general formula (1), a partial structure represented by the following general formula (T-1) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (T-2) chemically bonded to the partial structure represented by the general formula (1), and an amine compound (B), wherein the curable composition is characterized by containing the same. 【Chemical 1】 [In the above general formula (1), R １３ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m ２ represents an integer of 0 or more and 4 or less, n １ represents the average number of repeating units, two * each represent a bond, and one bond is L in the following general formula (T-1) １３ or L １４ at the position of, and the other bond is L in the following general formula (T-2) １１ or L １２ at the position of, indicating that they are chemically bonded.] 【Chemical 2】 In the above general formula (T-1) or (T-2), R １１ and R １５ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R １２ and R １４ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, L １１ ~L １４ each independently represents a bond or a hydrogen atom, provided that L １１ or L １２ is chemically bonded to the partial structure represented by the general formula (1) at the position of, and L １３ or L １４ is chemically bonded to the partial structure represented by the general formula (1) at the position of, and L that is not chemically bonded to the partial structure represented by the general formula (1) １１ ~L １４ is a hydrogen atom, m １ and m ３ each represent 2.]

2. The curable composition according to Claim 1, wherein the polymerimide resin (A) uses an aromatic amine compound (A-a) represented by the following general formula (a-1), a compound (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c) as reaction raw materials (1). [Chemical 3] [In the above general formula (a-1), R ａ１ and R ａ２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R １ represents a hydrocarbon group having 1 to 18 carbon atoms, and R ２ and R ３ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]

3. The curable composition according to Claim 1, wherein the polymerimide resin (A) is a polymerimide resin having a partial structure represented by the following general formula (1A). 【Chemical 4】 [In the general formula (1A), R １３ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m ２ represents an integer of 0 or more and 4 or less, n １ represents the average number of repeating units, R １１ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R １２ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m １ each represents 2, n ２ represents the average number of repeating units, ran represents that the arrangement of each constitutional unit can be random, the two * each represent a bond, and are bonded to a hydrogen atom or a partial structure represented by the following general formula (T-3). ] [Chemical Formula 5] [In the above general formula (T-3), R １３ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m ２ represents an integer of 0 or more and 4 or less, and n ３ represents the average number of repeating units. ]

4. The component represented by the general formula (1A) and having the sum of n １ and n ３ of 1 or more is contained in an amount of 10% by mass or more. The curable composition according to claim 3.

5. A polymerimide resin mixture (C) containing a polymerimide resin component having a partial structure unit represented by the following general formula (1a) and a maleimide multimer compound represented by the following general formula (2), and an amine compound (B), wherein the polymerimide resin mixture (C) contains 1 to 99% by mass of a polymerimide resin (A) having a partial structure represented by the following general formula (1), a partial structure represented by the following general formula (T-1) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (T-2) chemically bonded to the partial structure represented by the general formula (1) with respect to the total amount of the polymerimide resin component, and contains 80% by mass or less of the maleimide multimer compound with respect to the total amount of the polymerimide resin mixture (C), and the curable composition is characterized by the same. 【Chemical Formula 6】 [In the general formula (1a), R １１ represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R １２ represents a hydrocarbon group having 1 to 18 carbon atoms, and R １３ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m １ represents 2, m ２ represents an integer of 0 or more and 4 or less, and n １ represents the average number of repeating units. ] 【Chemical Formula 7】 [In the general formula (2) above, R ２１ and R ２５ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R ２２ and R ２４ each independently represent a hydrocarbon group having 1 to 18 carbon atoms, m ２１ represents 2, m ２３ represents 3, n ２１ represents an integer of 1 or more and 5 or less. ] [Chemical 8] [In the above general formula (1), R １３ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m ２ represents an integer of 0 or more and 4 or less, n １ represents the average number of repeating units, two * each represent a bond, and one bond is L in the following general formula (T-1) １３ or L １４ at the position of, and the other bond is L in the following general formula (T-2) １１ or L １２ is chemically bonded at the position of. ] 【Chemical Formula 9】 In the general formula (T-1) or (T-2), R １１ and R １５ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R １２ and R １４ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, L １１ ~L １４ each independently represents a bond or a hydrogen atom, provided that L １１ or L １２ is chemically bonded to the partial structure represented by the general formula (1) at the position of, and L １３ or L １４ is chemically bonded to the partial structure represented by the general formula (1) at the position of, and L that is not chemically bonded to the partial structure represented by the general formula (1) １１ ~L １４ is a hydrogen atom, m １ and m ３ each represent 2.]

6. The curable composition according to Claim 5, wherein the polymerimide resin (A) uses an aromatic amine compound (A-a) represented by the following general formula (a-1), a compound (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c) as reaction raw materials (1). 【Chemical Formula 10】 In the general formula (a-1) above, R ａ１ and R ａ２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R １ represents a hydrocarbon group having 1 to 18 carbon atoms, and R ２ and R ３ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]

7. A polymerimide resin characterized by having a partial structure represented by the following general formula (1A). 【Chemical Formula 11】 [In the above general formula (1A), R １３ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m ２ represents an integer of 0 or more and 4 or less, n １ represents the average number of repeating units, R １１ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R １２ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m １ each represents 2, n ２ represents the average number of repeating units, ran represents that the arrangement of each constitutional unit may be random, the two * each represent a bond, and are bonded to a hydrogen atom or a partial structure represented by the following general formula (T-3). ] 【Chemical 12】 [In the general formula (T-3) above, R １３ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m ２ represents an integer of 0 or more and 4 or less, and n ３ represents the average number of repeating units.]

8. A cured product of the curable composition according to any one of Claims 1 to 6.

9. A prepreg having a reinforcing base material and a semi-cured product of the curable composition according to any one of Claims 1 to 6 impregnated in the reinforcing base material.

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

11. A build-up film containing the curable composition according to any one of claims 1 to 6.

12. A semiconductor encapsulant containing the curable composition according to any one of claims 1 to 6.

13. A semiconductor device including a cured product of the semiconductor encapsulant according to claim 12.

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