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

Abstract

To provide a polymaleimide resin that exhibits low dielectric loss tangent and low hygroscopicity after curing, a curable composition containing the polymaleimide resin and a cured product thereof, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device.SOLUTION: A curable composition comprises a polymaleimide resin (A) having a partial structure represented by formula (1) and two specific types of partial structures each having a maleimide group and chemically bonded to the partial structure represented by formula (1), and a compound (D) containing a reactive double bond.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure 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] 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 multilayers obtained by combining the laminates and the prepregs and curing them by heating are widely used as circuit board materials for electronic devices. In particular, package substrates, which are a type of printed wiring board that serves as an interposer for mounting semiconductors, are becoming thinner and warping of the package substrate during mounting is becoming a problem, so that materials that exhibit high heat resistance are required to suppress warping of the package substrate during mounting. In addition, in recent years, signals have become faster and higher in frequency, and it is desirable 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 conditions. In particular, in recent electrical material applications, particularly in advanced material applications, there is a demand for materials and compositions that have improved performance, such as heat resistance and dielectric properties, and that combine these. In addition, when an electrical insulating material has high wettability or hygroscopicity, its dielectric strength decreases compared to when it is in a dry state (normal state), so low hygroscopicity is also required.

[0003] In response to such demands, maleimide resins have attracted attention as materials that combine heat resistance and low dielectric properties. Technologies relating to such maleimide resins include, for example, Patent Documents 1 and 2. Patent Documents 1 and 2 disclose technologies in which a cured product of a curable resin composition using a novel maleimide resin exhibits heat resistance and a low dielectric constant. [Prior art documents] [Patent documents]

[0004] Patent Document 1 Japanese Patent Application Laid-Open No. 2020-176190 Patent Document 2 Japanese Patent Application Laid-Open No. 2020-176191 SUMMARY OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION

[0005] Generally, as the frequency increases, the transmission loss increases, so reduction of transmission loss in the high-frequency region is required. However, in the technologies of Patent Documents 1 and 2, 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 is possible to support the technology for the fifth-generation mobile communication system (5G) using the so-called Sub6 frequency band. Further, Patent Documents 1 and 2 have not studied hygroscopicity either. Therefore, the technical problem to be solved by the present disclosure is to provide a curable composition and a cured product thereof, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device that achieve both low dielectric properties and low moisture absorption rate at a high level after curing. MEANS FOR SOLVING THE PROBLEMS

[0006] As a result of intensive studies to solve the above-described problems, the present inventors have found that by using a curable composition containing a polymaleimide resin (A) having a predetermined chemical structure and a compound (D) containing a reactive double bond, a curable composition and a cured product thereof that achieve both low dielectric properties and low moisture absorption rate at a high level after curing can be obtained, and have completed the following invention.

[0007] [1] A polymaleimide 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 A curable composition characterized by containing a reactive double bond-containing compound (D) having a reactive double bond. [Chemical formula] [In the above general formula (1), each R 13 represents independently 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 where chemical bonding occurs, and the other bond is L in the following general formula (T-2) 11 or L 12 at the position where chemical bonding occurs.] [Chemical formula] [In the above general formula (T-1) or (T-2), R 11 and R 15 each represent independently a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 and R 14 each represent independently a hydrocarbon group having 1 to 18 carbon atoms, L 11 to L 14 each represent independently 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, and L 13 or L 14 is chemically bonded to the partial structure represented by the general formula (1) at the position, and L that is not chemically bonded to the partial structure represented by the general formula (1) 11 to L 14 is a hydrogen atom, m 1 and m 3 each represent 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 (B) having a benzyl ether skeleton, and maleic anhydride as reaction raw materials (1). [Chemical formula] [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, R 2 and R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]

[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] [In the above general formula (1A), R 14 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, R 15 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, m 3 each represents 2, 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 2represents 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 are bonded to a hydrogen atom or a partial structure represented by the general formula (T-3). Further, ran in the general formula (1A) represents a random copolymer.

Chemical formula

[0010] [4] Regarding the average number of repeating units of the polymaleimide resin (A) represented by the general formula (1A), the curable composition according to [3], which contains 10% by mass or more of a component in which the sum of n 1 and n 3 is 1 or more.

[0011] [5] A polymaleimide resin (A) mixture containing a polymaleimide resin (A) 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), and a reactive double bond-containing compound (D) having a reactive double bond, wherein the polymaleimide resin (A) mixture contains 1 to 99% by mass of a polymaleimide 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), based on the total amount of the polymaleimide resin (A) component, and contains 80% by mass or less of the maleimide multimer compound based on the total amount of the polymaleimide resin (A) mixture.

Chemical formula

Chemical formula

Chemical formula

Chemical formula

[0012] [6] The curable composition according to any one of [1] to [5], wherein the polymaleimide resin (A) uses an aromatic amine compound (A-a) represented by the following general formula (a-1), a compound (B) having a benzyl ether skeleton, and maleic anhydride 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, and R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]

[0013] [7] The polymaleimide resin represented by the general formula (1A) according to [3].

[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 described in

[12] . [Advantages of the Invention]

[0020] According to the present disclosure, it is possible to provide a curable composition and a cured product thereof, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device that exhibit a low dielectric tangent and low moisture absorption after curing. [Brief Description of the Drawings]

[0021]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

[0022] Hereinafter, embodiments of the present invention (referred to as "the present embodiments") will be described in detail. However, the present disclosure is not limited to the following description, and various modifications can be made within the scope of the gist thereof and implemented.

[0023] [Terms] Unless otherwise specified in this specification, the following terms can be applied. As used herein, the "reaction raw material" refers to a compound that is used to obtain a target compound through a chemical reaction such as bonding or decomposition and partially constitutes the chemical structure of the target compound, excluding substances that play the role of chemical reaction aids such as solvents and catalysts. In particular, in this specification, the "reaction raw material" refers to a precursor for obtaining the target polymaleimide resin (A) or its precursor compound (for example, an intermediate amine compound (C) in which structural units derived from a compound (B) in which aromatic amine compounds (A-a) have a benzyl ether skeleton are linked via a chemical reaction). As used herein, the "structural unit" refers to a unit of chemical structure formed during a reaction or polymerization. In other words, in the product compound formed by a reaction or polymerization, it refers to a partial structure other than the structure of the chemical bond involved in the reaction or polymerization, that is, a so-called residue. In the case of polymerization, it is also referred to as a repeating unit. The "aromatic hydrocarbon group" in this specification 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 hydrocarbon group" in this specification may have a hydrogen atom of the aromatic ring in the aromatic hydrocarbon group substituted with 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 hydrocarbon group" includes heteroaromatics and may be substituted with -O-, -S-, or -N= so that -CH2- or -CH= in the "aromatic hydrocarbon group" are not adjacent to each other. Examples of the type of the aromatic ring include monocyclic aromatic rings, condensed aromatic rings, and polycyclic aromatic rings. Examples of the monocyclic aromatic rings include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Examples of the condensed aromatic rings include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. Examples of the polycyclic aromatic rings include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, and quaterphenyl. Further, the hydrogen atoms of the aromatic ring in the aromatic hydrocarbon 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 monovalent aromatic hydrocarbon group refers to a group obtained by removing one hydrogen atom from the "aromatic hydrocarbon group", and the divalent aromatic hydrocarbon group refers to a group obtained by removing any two hydrogen atoms from the "aromatic hydrocarbon group". The "alkyl group" in this specification may be linear, branched, or cyclic, and examples thereof include 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. The "cycloalkyl group" in this specification includes cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, norbornyl group, adamantyl group, and the like. The "alkylthio group" in this specification includes a methylthio group, an ethylthio group, a propylthio group, a butylthio group, an octylthio group, or a 2-ethylhexylthio group. The "alkenyl group" in this specification includes an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 2-butynyl group, a pentynyl group, a hexynyl group, a vinyl group, an allyl group, an isopropenyl group, etc. The "alkenylene group" includes a divalent group obtained by removing any one hydrogen atom from the above "alkenyl group". The "alkoxy group" in this specification includes, for example, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, or a nonyloxy group, etc. The "aryl group" in this specification includes, for example, a phenyl group, a naphthyl group, a phenalenyl group, a phenanthrenyl group, an anthryl group, an azulenyl group, an indenyl group, an indanyl group, a tetralinyl group, etc. Also, 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, or a halogen atom. Examples of the "aralkyl group" in this specification include a benzyl group, a diphenylmethyl group, a biphenyl group, a 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. The "aralkylene group" includes a divalent group obtained by removing any one hydrogen atom from the above "aralkyl group". The "aryloxy group" in this specification includes a phenoxy group, a naphthyloxy group, an anthryloxy group, a phenanthryloxy group, or a pyrenyloxy group, etc. The "arylthio group" in this specification includes arylthio groups such as a phenylthio group, a naphthylthio group, an anthrylthio group, a phenanthrylthio group, or a pyrenylthio group. The "halogen atom" in this specification includes, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, etc. 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, etc. 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, etc. The "hydrocarbon group" in this specification is a monovalent group and includes linear, branched or cyclic saturated hydrocarbons, unsaturated hydrocarbons, or aromatic hydrocarbon 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.

[0024] [Curable Composition] The present disclosure relates to a curable composition containing a polymaleimide resin (A) and a reactive double bond-containing compound (D) having a reactive double bond. The polymaleimide resin (A) 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 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). Thereby, it is possible to provide a curable composition that exhibits a low dielectric tangent and low moisture absorption after curing. The curable composition of the present disclosure essentially contains a polymaleimide resin (A) and a reactive double bond-containing compound (D), and optionally contains one or more selected from the group consisting of an epoxy resin (E), other resins (F), a curing agent (G) other than the reactive double bond-containing compound (D) such as an amine compound, and additives as described below. Hereinafter, the polymaleimide resin (A), the reactive double bond-containing compound (D), the epoxy resin (E), other resins (F), the curing agent (G) other than the reactive double bond-containing compound (D), and the additives, which are the constituent components of the curable composition, will be described.

[0025] (Polymaleimide resin (A)) The curable composition of the present embodiment contains the polymaleimide resin (A) from the viewpoint of achieving both low moisture absorption and high-order low dielectric constant and low dielectric tangent after curing. The polymaleimide resin (A) of the present embodiment is a resin having a partial structure represented by the following general formula (1), a partial structure represented by the general formula (T-1) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the 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 1represents the average number of repeating units, and the two * each represent a bond, with one bond chemically bonded at the position of L in the following general formula (T-1) 13 or L 14 and the other bond is chemically bonded at the position of L in the following general formula (T-2) 11 or L 12 .] [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 ~L 14 each independently represent a bond or a hydrogen atom, provided that at the position of L 11 or L 12 is chemically bonded to the partial structure represented by the general formula (1), and at the position of L 13 or L 14 is chemically bonded to the partial structure represented by the general formula (1), and further, L 11 ~L 14 that is not chemically bonded to the partial structure represented by the general formula (1) is a hydrogen atom, m 1 represents 2, and m 3 represents 2.] As a result, since the proportion of polar functional groups in the chemical structure of the polymaleimide resin (A) is small, the cured product containing the polymaleimide resin (A) can achieve both low moisture absorption and low dielectric properties. In addition, since there is only one bonding site at each of the ortho and para positions of the benzene ring to which the maleimide group is bonded, a linear-chain extended polymaleimide resin (A) can be obtained, so that molecular weight control is easy and high solubility in solvents can be exhibited.

[0026] As the blending ratio (parts by mass) of the components of the polymaleimide resin (A) and the reactive double bond-containing compound (D) which is an unsaturated hydrocarbon compound having a reactive double bond, it is preferably polymaleimide resin (A): reactive double bond-containing compound (D) having a reactive double bond, 95:5 to 5:95, more preferably 90:10 to 10:90, and still more preferably 88:12 to 12:88. By adjusting the blending ratio within the above range, excellent low hygroscopicity, low dielectric constant and low dielectric tangent can be exhibited, which is preferable.

[0027] In the above general formula (1), the two * each represent a bond. And one of the two bonds is bonded at the position of L 13 or L 14 in the above general formula (T-1). Further, the other bond is bonded at the position of L 11 or L 12 in the above general formula (T-2). Therefore, the polymaleimide resin (A) of the present embodiment 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, the plurality of R 13 may be the same as or different from each other. When m 2 is 2 or more, the plurality of R 13 may be the same as or different from each other.

[0028] In the above general formula (1), each R 13 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. Further, when m 2 is an integer of 2 or more, the plurality of R 13may be the same as or different from each other. Preferred R in the general formula (1) 13 is preferably a linear alkyl group, 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) 13 is attached may be the benzene ring of the compound (B) having a benzyl ether skeleton.

[0029] In the above general formula (1), m 2 represents an integer of 0 or more and 4 or less, preferably an integer of 2 or less, more preferably 2. In the benzene ring to which R in the general formula (1) 13 is attached, when the 1st and 3rd positions are bonded by a methylene group, it is preferable that R 13 is attached to the 4th and 6th positions, respectively. In the above general formula (1), n 1 represents the average number of repeating units. From the viewpoint of the viscosity of the obtained 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 as shown in the examples described later.

[0030] The polymaleimide resin (A) in the present embodiment 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).

[0031] In the above general formula (T-1), each R 15 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. Particularly preferred R 15It may be a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms. m 3 Since m is 2, the two Rs 15 may be the same as or different from each other. In the above general formula (T-1), each R 14 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. Particularly preferred R 14 may 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 a bonding site with the partial structure represented by the general formula (1), it has higher solubility in a solvent, and the cured product of the curable composition exhibits more excellent low dielectric constant and high heat resistance. Note that the benzene ring to which R 14 in the general formula (T-1) is bonded may be the benzene ring of the aromatic amine compound (A-a). In the above general formula (T-1), each L 13 or each L 14 independently represents a bond or a hydrogen atom. However, at at least one position of L 13 or L 14 , the partial structure represented by the general formula (1) and the partial structure represented by the general formula (T-1) are chemically bonded. Also, L 13 or L 14 that is not chemically bonded to the partial structure represented by the general formula (1) is a hydrogen atom. Note that the partial structure represented by the general formula (1) may be chemically bonded to each of the two positions of L 13 and L 14 .

[0032] In the above 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 may be a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms. m 1Since it is 2, the two Rs 11 may be the same as or different from each other. In the general formula (T-2), R 12 each 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). In the general formula (T-2), L 11 or L 12 each independently represents a bond or a hydrogen atom. However, L 11 or L 12 At at least one of the positions, the partial structure represented by the general formula (1) and the partial structure represented by the general formula (T-2) are chemically bonded. Also, L 11 or L 12 that is not chemically bonded to the partial structure represented by the general formula (1) is a hydrogen atom. Note that the partial structure represented by the general formula (1) may be chemically bonded to each of the two positions of L 11 and L 12 respectively.

[0033] The polymaleimide resin (A) in the present embodiment preferably contains 1 to 99% by mass, more preferably 3 to 97% by mass, and even 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 polymaleimide resin (A). The polymaleimide resin (A) in the present embodiment preferably contains 1 to 99% by mass, more preferably 3 to 97% by mass, and even 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 polymaleimide resin (A).

[0034] The polyimide resin (A) of the present embodiment 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 (B) having a benzyl ether skeleton, and maleic anhydride 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, and R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]

[0035] Further, the polyimide resin (A) of the present embodiment preferably uses an intermediate amine compound (C) in which aromatic amine compounds (A-a) are linked via a structural unit derived from a compound (B) having a benzyl ether skeleton and maleic anhydride as reaction raw materials (2). Furthermore, the intermediate amine compound (C) is preferably a compound obtained by using an aromatic amine compound (A-a) and a compound (B) having a benzyl ether skeleton as reaction raw materials (3). In other words, the intermediate amine compound (C) in the present embodiment preferably has a structural unit in which a structural unit of 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 (B) having a benzyl ether skeleton are linked by a chemical bond. And the polyimide resin (A) in the present embodiment has a structure in which the amino group bonded to the aromatic ring of the intermediate amine compound (C) is substituted with an N-substituted maleimide ring. In addition, the "amino group" in the present 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 "polymaleimide resin (A)" in the present embodiment and the "intermediate amine compound (C)", which is a precursor of the "polymaleimide resin (A)", are polymer compounds that differ in that the amino group bonded to the aromatic ring is replaced by 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 later, a group obtained by removing at least one hydrogen atom from the benzene ring of the general formula (a-1) is referred to as the structural unit of the aromatic amine compound (A-a). Further, the structural unit derived from the compound (B) having a benzyl ether skeleton means that -(CH2O)- other than the terminal group in the compound (B) having a benzyl ether skeleton is replaced by -(CH2)- and is directly bonded to the benzene ring b is a group in which all of -(CH2)-R b is replaced by -(CH2)-. Here, R In the present embodiment, since the aromatic amine compound (A-a) having an aromatic ring structure having a substituent at a specific position is used as a reaction raw material, it becomes easy to control the reaction site with the compound (B) having a benzyl ether skeleton described later. As a result, a homogeneous chemical structure and a chain polymaleimide resin (A) can be easily obtained. As a result, it is possible to provide a polymaleimide resin (A) that exhibits excellent solubility in a solvent, low hygroscopicity, and low dielectric tangent in a cured product of a curable composition.

[0036] Hereinafter, after explaining the aromatic amine compound (A-a) represented by the general formula (a-1), the compound (B) having a benzyl ether skeleton, and maleic anhydride, which are the constituent components of the reaction raw material (1) of the polymaleimide resin (A), another preferred form of the polymaleimide resin (A) and a method for producing the polymaleimide resin (A) will be explained.

[0037] - Aromatic amine compound (A-a) represented by general formula (a-1)- In the present embodiment, 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 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.]

[0038] In the aromatic amine compound (A-a) of the present embodiment, the hydrocarbon group (R 2 , R 3 ) which may be substituted for one or two hydrogen atoms of the aromatic ring of the aromatic amine compound (A-a) includes a linear, branched or cyclic hydrocarbon group having 1 to 18 carbon atoms, preferably a linear or branched hydrocarbon group having 1 to 12 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. As described in the above general formula (a-1), it has a binding site with the compound (B) having a benzyl ether skeleton at each of the ortho and para positions of the aromatic ring. In the above general formula (a-1), 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 above general formula (a-1), 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 above general formula (a-1), 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.

[0039] 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 (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 polyimide resin (A), it is easier to exhibit solvent solubility, low moisture absorption, 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 the solubility to improve.

[0040] In the present embodiment, it is preferable that among the carbon atoms in the benzene ring constituting the aromatic amine compound (A-a), 1 or more carbon atoms having the largest HOMO electron density (Hückel coefficient) are unsubstituted (substituted with hydrogen atoms). Therefore, as the aromatic amine compound (A-a) represented by the general formula (a-1) of the present embodiment, it is preferable that any two of the 2, 4, and 6 positions are substituted with hydrogen atoms. A particularly preferable form of the aromatic amine compound (A-a) represented by the general formula (a-1) of the present embodiment 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 (B) having a benzyl ether skeleton described later. As a result, in the cured product of the polyimide resin (A), it is easier to exhibit solvent solubility, heat resistance, and excellent high-frequency electrical properties. In particular, by substituting the 4,6 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.

[0041] Specific examples of the aromatic amine compound (A-a) of the present embodiment 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, 2,4 or 2,5 positions is a methyl group and the other is an ethyl group), methylisopropylaniline (for example, methylisopropylaniline in which one of the 2,3, 2,4 or 2,5 positions is a methyl group and the other is an isopropyl group), or ethylbutylaniline (for example, ethylbutylaniline in which one of the 2,3, 2,4 or 2,5 positions 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. In addition, the aromatic amine compound (A-a) in the present embodiment may be used alone or in combination of two or more kinds.

[0042] 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 and are stable, they are likely to stack, resulting in high crystallinity. Therefore, it causes poor solvent solubility. In contrast, in the case of the present disclosure, for example, when having an alkyl group (e.g., 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 are less likely to stack, resulting in a decrease in crystallinity and an improvement in solvent solubility, which is a preferred 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, it is preferable to use, for example, an aromatic amine compound (A-a) having a hydrocarbon group with 1 to 6 carbon atoms. In addition, in the present embodiment, 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.

[0043] Compound (B) having a -benzyl ether skeleton The compound (B) having a benzyl ether skeleton in the present embodiment may be a single compound or a mixture. When the compound (B) having a benzyl ether skeleton in the present embodiment 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) described later, and even more preferably a compound represented by the following formula (b-2) described later. On the other hand, when the compound (B) having a benzyl ether skeleton in the present embodiment 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 partial structure represented by the following formula (b-1), and 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. The compound (B) having a benzyl ether skeleton in the present embodiment 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 is an integer of 0 or more and 4 or less, and j 1 +j 2 ≧1, k 1 and k 2 each independently is 0 or 1, and * represents a bond with another atom.] The compound (B) having a benzyl ether skeleton in the present embodiment is preferably a product obtained by reacting an alkylbenzene and formaldehyde under an acid catalyst.

[0044] --Physical properties of the compound (B) having a benzyl ether skeleton-- The compound (B) having a benzyl ether skeleton in the present embodiment 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 (B) having a benzyl ether skeleton in the present embodiment is preferably 1200 or less, more preferably 800 or less, and even more preferably 500 or less. The lower limit of the number average molecular weight (Mn) of the compound (B) having a benzyl ether skeleton is preferably 200 or more, more preferably 240 or more, and even more preferably 250 or more. In this embodiment, the upper limit of the oxygen content rate of the compound (B) having a benzyl ether skeleton is preferably 15% by mass or less, more preferably 13% by mass or less, and still more preferably 12% by mass or less. The lower limit of the oxygen content rate of the compound (B) having a benzyl ether skeleton is preferably 4% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass or more. In this embodiment, the upper limit of the specific gravity of the compound (B) having a benzyl ether skeleton is preferably less than 1.2, more preferably less than 1.15, and still more preferably less than 1.10. The lower limit of the specific gravity of the compound (B) having a benzyl ether skeleton is preferably 1.0 or more, more preferably 1.01 or more, and still more preferably 1.02 or more. In this embodiment, the upper limit of the viscosity (at 75 °C) of the compound (B) having a benzyl ether skeleton is preferably 1500 mPa·s or less, more preferably 1000 mPa·s or less, and still more preferably 900 mPa·s or less. The lower limit of the viscosity (at 75 °C) of the compound (B) having a benzyl ether skeleton is preferably 30 mPa·s or more, more preferably 50 mPa·s or more, and still more preferably 70 mPa·s or more. In this embodiment, the upper limit of the indirect viscosity (at 20 °C, the viscosity measured by diluting with toluene to a resin content of 80% by weight) of the compound (B) having a benzyl ether skeleton is preferably 1000 mPa·s or less, more preferably 800 mPa·s or less, and still more preferably 500 mPa·s or less. The lower limit of the indirect viscosity (at 20 °C) of the compound (B) having a benzyl ether skeleton is preferably 10 mPa·s or more, more preferably 20 mPa·s or more, and still more preferably 30 mPa·s or more. In this embodiment, the hydroxyl value of the compound (B) having a benzyl ether skeleton is preferably 16 - 50 (mgKOH / g), more preferably 18 - 40 (mgKOH / g), and still more preferably 22 - 35 (mgKOH / g).

[0045] --Preferred form of the compound (B) having a benzyl ether skeleton-- An example of the compound (B) having a benzyl ether skeleton, which is the reaction raw material (1) of the polyimide resin (A) of the present disclosure, 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.]

[0046] 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. Also, 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.

[0047] In the above general formula (b-1), R b2 and R b3 can each independently correspond to R 13 in the general formula (1). Therefore, R b2 and R b3 in the above general formula (b-1) are preferably each independently 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.

[0048] In the general formula (b-1), each L 1 independently preferably represents 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 is 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.

[0049] In the general formula (b-1), each L 2 independently preferably represents 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, the p1 to p3 and the q1 to q3 each preferably 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 Preferably, at least one of them has a -CH2O- group, and more preferably both R b1 and L 2 have a -CH2O- group.

[0050] 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.

[0051] 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.

[0052] As a preferred form of the compound (B) having a benzyl ether skeleton of the present embodiment, it may be a compound having a structural unit represented by the following general formula (b-2). [Chemical formula] In the above 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 with -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 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 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. In the above 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 are the same as those of the above general formula (b-1).

[0053] The compound (B) having a benzyl ether skeleton in this embodiment may be used alone or in combination of two or more, and may also be a mixture containing two or more compounds (B) having different benzyl ether skeletons. In this specification, for convenience of explanation, among the compounds (B) having a benzyl ether skeleton, a mixture containing two or more compounds (B) having different benzyl ether skeletons is referred to as a mixture (B) having a benzyl ether skeleton. Therefore, the "compound (B) having a benzyl ether skeleton" includes not only the case where only one kind of compound is represented, but also the mixture (B) having a benzyl ether skeleton.

[0054] The mixture (B) having a benzyl ether skeleton of the present embodiment has a partial structure represented by the following general formula (b-3): [Chemical formula] [In the above general formula (b-3), L 3 and L 4 are linking groups, each independently being one kind of group selected from the group consisting of -CH2-, -CH2O-CH2-, -(CH2O)2-CH2-, and -(CH2O)3-CH2-, and * represents a bond with another atom. It is preferable that the component having the structure occupies 95% by mass or more and 100% by mass or less of the entire mixture (B) having a benzyl ether skeleton. The mixture (B) having a benzyl ether skeleton of the present embodiment preferably has a component having the partial structure represented by the above general formula (b-3) occupying 95% by mass or more and 100% by mass or less of the entire mixture (B) having a benzyl ether skeleton and satisfying the following requirement (I) or (II). (I) The total number of linking groups (the total number of L 3 and L 4 ) per molecule constituting the component having the 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 terminal of the molecule constituting the component having the partial structure represented by the above general formula (b-3) is 0.5 or more and 1.5 or less per molecule.

[0055] In the present embodiment, the linking groups (L 3 and L4 ) Examples thereof include one kind of group selected from the group consisting of -CH2-, -CH2O-CH2-, -(CH2O)2-CH2-, and -(CH2O)3-CH2-. In the entire mixture (B) having a benzyl ether skeleton, the following linking group (L per molecule having a benzyl ether skeleton represented by the above general formula (b-3) 3 and L 4 The total number) is preferably in the following composition of (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.

[0056] In the mixture (B) having a benzyl ether skeleton of the present embodiment, 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 terminals of the molecules constituting the component having the partial structure represented by the above general formula (b-3). And in the entire mixture (B) having a benzyl ether skeleton, it is preferable that the number of terminal groups per molecule having a benzyl ether skeleton represented by the above general formula (b-3) is 0.5 or more and 1.5 or less. In the entire mixture (B) having a benzyl ether skeleton, the number of the following terminal groups per molecule having a benzyl ether skeleton is preferably in the following composition of (5) to (10). (5) The number of terminal groups “-CH2-OH” is preferably 0.17 or more and 0.4 or less, more preferably 0.18 or more and 0.25 or less. (6) The number of terminal groups “-CH2O-CH3” is preferably 0.17 or more and 0.7 or less, more preferably 0.18 or more and 0.44 or less. (7) The number of terminal groups “-(CH2O)2-CH3” is preferably 0.08 or more and 0.6 or less, more preferably 0.09 or more and 0.3 or less. (8) The number of terminal groups “-(CH2O)3-CH3” is preferably substantially not contained, more preferably 0.3 or less, still more preferably 0.2 or less. (9) The number of terminal groups “-(CH2O)-COH” is preferably 0 or more and 0.1 or less, more preferably 0.01 or more and 0.1 or less. In the mixture (B) having a benzyl ether skeleton of the present embodiment, the chemical structure and the number of the linking group, and the chemical structure and the number of the terminal group can be calculated from NMR or referred to the catalog of the manufacturer, as shown in the column of the examples described later.

[0057] In the present embodiment, the compound (B) having a benzyl ether skeleton may be a synthetic product or a commercially available product. As the compound (B) having a commercially available benzyl ether skeleton, for example, xylene resin (trade name: Nikanol (Y-50, Y-100, Y-300, Y-1000, LLL, LL, L or H)) manufactured by Fudo Co., Ltd. is preferable. In the present embodiment, with respect to the total amount (100% by mass) of the polymaleimide resin (A), the structural unit of the compound (B) having a benzyl ether skeleton preferably contains 1 to 99% by mass, more preferably 5 to 95% by mass. The structural unit of the compound (B) having a benzyl ether skeleton refers to the group represented by the general formula (1).

[0058] - maleic anhydride - In this embodiment, maleic anhydride is an essential component of the reaction raw material (1) of the polymaleimide resin (A), and is used in the reaction for maleimidating the amino group derived from the aromatic amine compound (A-a), as described in the section on the method for producing the polymaleimide resin (A) described later.

[0059] <Preferred form of the polymaleimide resin (A)> The polymaleimide resin (A) of this embodiment is preferably a random copolymer represented by the following general formula (1A). [Chemical formula] [In the above general formula (1A), R 14 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, and R 15 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, m 3 each represents 2, 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, the two * each represent a bond, and are bonded to a hydrogen atom or a partial structure represented by the general formula (T-3). Also, "ran" in the above general formula (1A) represents a random copolymer. And -CH2- in the above general formula (1A) is chemically bonded to the carbon atom at the ortho or para position with respect to the carbon atom in the benzene ring bonded to the maleimide group.] [Chemical formula] [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, n 3represents the average number of repeating units. The curable composition containing the polyimide resin (A) which is a random copolymer represented by the general formula (1A) and the compound (D) containing a reactive double bond can exhibit more excellent low dielectric characteristics and hygroscopicity.

[0060] The polyimide resin (A) is represented by the general formula (1A). Among the polyimide resins (A) represented by the general formula (1A), n 1 and n 3 The component whose sum is 1 or more (= the component of the polyimide resin (A) that satisfies the condition that the sum of n 1 and n 3 is 1 or more) is preferably contained in the total polyimide resin (A) in an amount of 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more. Further, with respect to the total polyimide resin (A), the sum of the above n 1 and n 3 The upper limit of the component whose sum is 1 or more can be, for example, 100% by mass or less, 99.5% by mass or less, 99% by mass or less. When emphasizing the viewpoint of heat resistance, among the polyimide resins (A) represented by the general formula (1A), n 2 The component whose value is 1 or more (= the component of the polyimide resin (A) that satisfies the condition that n 2 in the general formula (1A) is 1 or more) is desirably contained in the total polyimide resin (A) in an amount of 5% by mass or more, more preferably 7% by mass or more, and even more preferably 10% by mass or more. Further, with respect to the total polyimide resin (A), the upper limit of the component in which the above n 2 is 1 or more can be, for example, 100% by mass or less, 99.5% by mass or less, 99% by mass or less.

[0061] The present disclosure can be a polyamide resin of a random copolymer represented by the above general formula (1A). A polymerimide resin that is a random copolymer represented by the above general formula (1A) can provide a composition excellent in solvent solubility, low dielectric properties, and hygroscopicity.

[0062] <Physical properties of the polymerimide resin (A)> The number average molecular weight (Mn) of the polymerimide resin (A) of the present disclosure is preferably in the range of 200 to 1500, more preferably in the range of 300 to 800. Also, the weight average molecular weight (Mw) of the polymerimide resin (A) is preferably in the range of 280 to 2000, more preferably in the range of 330 to 1200. The polymerimide resin (A) of the present disclosure is excellent in solvent solubility, heat resistance, and low dielectric tangent. Therefore, 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. Note that from the GPC chart obtained by GPC measurement, when the molecular weight distribution is wide and there are many high molecular weight components, the ratio of high molecular weight components contributing to flexibility increases. Therefore, compared with a cured product using conventional maleimide, brittleness is suppressed, and a cured product excellent in flexibility and softness can be obtained, which is a preferred embodiment. 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 polymerimide resin (A) of the present embodiment are measured under the measurement conditions described in the examples below using gel permeation chromatography (hereinafter abbreviated as "GPC").

[0063] <Production method of the polymerimide resin (A)> Hereinafter, the production method of the polymerimide resin (A) of the present disclosure will be described. The polyimide resin (A) of the present embodiment is not particularly limited in its production method, and may be produced in any manner 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 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). As a preferred embodiment of the method for producing the polyimide resin (A) of the present embodiment, 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 the aromatic amine compound (A-a)), a compound (B) having a benzyl ether skeleton, and maleic anhydride as reaction raw materials (1).

Chemical formula

[0064] As a specific embodiment of the method for producing the polyimide resin (A) of the present disclosure, 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 above general formula (a-1) and a compound (B) having a benzyl ether skeleton as reaction raw materials (2) to obtain an intermediate amine compound (C) in the present embodiment; Step (2): A step of reacting the intermediate amine compound (C) obtained in the above step (1) and maleic anhydride as reaction raw materials (3) to obtain the polyimide resin (A) of the present disclosure. Specifically, the method for producing the polymaleimide resin (A) of the present embodiment includes a step (1) (also referred to as a crosslinking step) of reacting an aromatic amine compound (A-a) represented by the above general formula (a-1) with a compound (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 (C) generated in the step (1) with maleic anhydride. It is preferable to have this.

[0065] Hereinafter, each step of the method for producing the polymaleimide resin (A) of the present disclosure will be described in order. <<Step (1): Production step of intermediate amine compound (C)>> Hereinafter, the production step of the intermediate amine compound (C) in the present embodiment will be described. The step (1) in the present embodiment is not particularly limited. For example, it is a step of reacting the above-described aromatic amine compound (A-a), the above-described compound (B) having a benzyl ether skeleton (for example, Nicanol, etc.), and other compounds added as necessary in the presence of an acid catalyst. Thereby, the intermediate amine compound (C) can be generated.

[0066] Regarding the blending ratio of the aromatic amine compound (A-a) and the compound (B) having a benzyl ether skeleton, considering the moldability and curability physical property balance during the production of the obtained cured product, the molar ratio of the compound (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 above-mentioned mixture (B) having a benzyl ether skeleton as the compound (B) having a benzyl ether skeleton, the reaction point with the aromatic amine compound (A-a) is the methyleneoxy moiety in the compound (B) having a benzyl ether skeleton contained in the mixture (for example, a benzyl ether moiety (Ph-CH2O-CH2-), a benzyl alcohol moiety (Ph-CH2O-H), or a methyleneoxy moiety (-CH2-O-)). Also, 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-mentioned reaction points, the blending amount of the aromatic amine compound (A-a) is preferably 1 to 10 mol.

[0067] As a specific method for carrying out the above reaction, all 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 (B) having a benzyl ether skeleton and an acid catalyst are charged, and while maintaining the temperature at a predetermined level, the other of the aromatic amine compound (A-a) or the compound (B) having a benzyl ether skeleton is added dropwise and reacted. At this time, 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 (C), and when no solvent is used, the unreacted substances are distilled off to obtain the target intermediate amine compound (C).

[0068] As the acid catalyst used in step (1) of this embodiment, any of organic acids, inorganic acids, or solid acids can be used. Examples of the above-mentioned organic acids 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 above-mentioned inorganic acids include phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, or boric acid. Examples of the above-mentioned solid acids 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. Further, the above acid catalyst may be used alone or in combination of two or more. After the reaction in the above 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. Incidentally, 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 tert-butoxide, and potassium tert-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; 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 bicarbonates of alkali metals or alkaline earth metals such as sodium carbonate, potassium carbonate, sodium bicarbonate, and potassium bicarbonate; 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.

[0069] In this embodiment, 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 (compound (B) having a benzyl ether skeleton and aromatic amine compound (A-a)) to be charged. 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 isomeric structures and avoid side reactions such as thermal decomposition, the range of 120 to 250°C is preferable.

[0070] In step (1) of the present embodiment, as for the mixing reaction time of the compound (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 about 1 to 60 hours, preferably in the range of about 1 to 20 hours. In the method for producing the intermediate amine compound (C) in the present embodiment, 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 (B) having a benzyl ether skeleton as a raw material, an azeotropic dehydration solvent 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 is carried out in the above reaction temperature range. A method may be adopted.

[0071] The intermediate amine compound (C) obtained by the above step (1) preferably has a partial structure represented by the following general formula (1), a partial structure represented by the general formula (t-1) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the general formula (t-2) chemically bonded to the partial structure represented by the general formula (1).

Chemical formula

Chemical formula

[0072] In this embodiment, the amine equivalent of the intermediate amine compound (C) 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 (C) in this specification shall be the value measured by a method conforming to the neutralization titration method specified in JIS K 0070 (1992).

[0073] <<Step (2): Maleimidation>> Step (2) in this embodiment is a step of reacting the intermediate amine compound (C) obtained in step (1) with maleic anhydride. Since the amino group of the intermediate amine compound (C) 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) of the present disclosure can be obtained. In this embodiment, the intermediate amine compound (C) 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 step (1) is charged into a reactor, dissolved in an appropriate solvent, and then reacted with maleic anhydride in the presence of a catalyst. After the reaction, unreacted maleic anhydride 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). Further, a dehydrating agent may be used during the reaction if necessary.

[0074] Examples of the organic solvent used in step (2) of this embodiment 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.

[0075] In step (2) of the present embodiment, as the mixing ratio of the intermediate amine compound (C) and maleic anhydride, it is preferable to blend the equivalent ratio of maleic anhydride to the amino equivalent of the intermediate amine compound (C) in the range of 1 to 5, more preferably charge in the range of 1 to 3. It is a preferred embodiment to 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 (C) and maleic anhydride.

[0076] As the catalyst that can be used in step (2) of the present embodiment, there are acetates, chlorides, bromides, sulfates, nitrates and other inorganic salts of nickel, cobalt, sodium, calcium, iron, lithium, manganese, etc., inorganic acids such as phosphoric acid, hydrochloric acid, sulfuric acid, and organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid, etc. Solid acids such as activated clay, acid clay, silica alumina, zeolite, strongly acidic ion exchange resin, heteropolyhydrochloric acid, etc. can be mentioned, and toluenesulfonic acid is particularly preferably used.

[0077] As the dehydrating agent used in step (2) of the present embodiment, there are lower aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, butyric anhydride, oxides such as phosphorus pentoxide, calcium oxide, barium oxide, inorganic acids such as sulfuric acid, and porous ceramics such as molecular sieves. etc., and acetic anhydride can preferably be used. There is no particular limitation on the amount of the catalyst and dehydrating agent used in step (2) of the present embodiment. Usually, per 1 equivalent of the amino group (-NH2) of the intermediate amine compound (C), the catalyst is 0.0001 to 1 mol, preferably 0.01 to 0.3 mol, and the dehydrating agent is 1 to 3 mol, preferably 1 to 1.5 mol. In step (2) of the present embodiment, as the reaction conditions for maleimidation, the above intermediate amine compound (C) and maleic anhydride are charged and reacted 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 can be added and reacted at a temperature range of 90 to 130 ° C, preferably 105 to 120 ° C for 1 to 24 hours, preferably 1 to 10 hours.

[0078] <Polyimide resin (A) mixture> The polyimide resin (A) of this embodiment may be a mixture. For example, when a resin using an aromatic amine compound (A-a) represented by the above general formula (a-1), a compound (B) having the above benzyl ether skeleton, and maleic anhydride as reaction raw materials (1) is used, since there are a plurality of reaction points of the compound (B) having the benzyl ether skeleton with respect to the aromatic amine compound (A-a) represented by the above general formula (a-1), the resulting intermediate amine compound (C) itself can be a mixture in which a plurality of them are mixed. Therefore, the polyimide resin (A) can also be a mixture of compounds having various chemical structures. In this specification, the term "polyimide resin (A)" includes a single substance and a mixture. On the other hand, it is referred to as a polyimide resin (A) mixture only when the polyimide resin (A) means only a mixture. The present disclosure is a polyimide resin (A) mixture containing a polyimide resin (A) 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), and with respect to the total amount of the polyimide resin (A) component, a polyimide 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 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) is contained in an amount of 1 to 99% by mass, A polyimide resin (A) mixture containing 80% by mass or less of the maleimide multimer compound with respect to the total amount of the polyimide resin (A) mixture. [Chemical formula] [In the above 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 13Each independently represents an alkyl group having 1 to 18 carbon atoms, and m 1 represents an integer of 0 or more and 2 or less, and 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, and R 22 and R 24 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, and m 21 represents 2, and m 23 represents 3, and n 21 represents an integer of 1 or more and 5 or less.] As a result, it shows high solubility in a solvent or low dielectric constant and low moisture absorption in the cured product after curing. Further, in the maleimide multimer compound represented by the general formula (2), when n 21 is 1, the dimer has high crystallinity, and as it becomes a trimer or tetramer where n 21 is 2 or more, the solubility tends to improve. In addition, by setting the number and position of the substituents (R 11 or R 15 , R 12 or R 14 ) in the partial structure represented by the general formula (T-1) or the general formula (T-2) as in the present invention, the ratio of trimers and tetramers with excellent solubility can be increased. "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 above-described general formula (1) or general formula (T-1). Further, "R 21 and R25 " is independently, "R" in the general formula (T-1) and the general formula (T-2) 11 or R 15 " is synonymous. "R" in the general formula (2) 22 and R 24 " is independently, "R" in the general formula (T-1) and the general formula (T-2) 12 or R 14 " is synonymous.

[0079] It is preferable that the amount of the maleimide multimer compound is 1% by mass or more and 80% by mass or less, more preferably 2% by mass or more and 79% by mass or less, and most preferably 3% by mass or more and 78% by mass or less with respect to the polymer maleimide resin (A) mixture (100% by mass) of the present embodiment. An increase in the polymer maleimide resin (A) is preferable from the viewpoints of low dielectric characteristics, low hygroscopicity, and solvent solubility, and an increase in the maleimide multimer compound is preferable from the viewpoint of heat resistance.

[0080] In the polymer maleimide resin (A) mixture of the present embodiment, with respect to the total amount of the polymer maleimide resin (A) component, the partial structure represented by the general formula (1), the partial structure represented by the following general formula (T-1) chemically bonded to the partial structure represented by the general formula (1), and the partial structure represented by the following general formula (T-2) chemically bonded to the partial structure represented by the general formula (1), the polymer maleimide resin (A) having them 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, and still more preferably 20% by mass to 97% by mass, and with respect to the total amount of the polymer maleimide 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, and still more preferably 10% by mass or more to 80% by mass or less.

[0081] As a preferable polymer maleimide resin (A) mixture of the present embodiment, it contains a polymer maleimide resin represented by the general formula (1A) (however, in the general formula (1A), a polymer maleimide resin in which n1 is 1 or more) and a maleimide multimer compound represented by the general formula (2). With respect to the polymaleimide resin (A) mixture, the content of the polymaleimide resin represented by the general formula (1A) (wherein, in the general formula (1A), the polymaleimide 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, and still more preferably 20% by mass to 97% by mass. With respect to the polymaleimide 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, and still more preferably 10% by mass or more to 80% by mass.

[0082] Another preferred polymaleimide resin (A) mixture of the present embodiment is composed of the polymaleimide 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 (B) having the benzyl ether skeleton, and maleic anhydride 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 at 5 to 98% by mass, more preferably at 10 to 95% by mass, still more preferably at 15 to 90% by mass, the compound (B) having the benzyl ether skeleton preferably at 1 to 90% by mass, more preferably at 2 to 85% by mass, still more preferably at 3 to 80% by mass, and maleic anhydride preferably at 2 to 90% by mass, more preferably at 3 to 85% by mass, still more preferably at 4 to 80% by mass.

[0083] (Compound (D) containing reactive double bonds) The curable composition of the present embodiment contains a reactive double bond-containing compound (D) (also simply referred to as the reactive double bond-containing compound (D)) having a reactive double bond. The reactive double bond-containing compound (D) can exhibit a high crosslink density when the reactive double bond (for example, an allyl group) reacts with the maleimide group of the polymaleimide resin (A), and a cured product with low polarity can be obtained. Therefore, by using a curable composition containing the reactive double bond-containing compound (D), it can be used as a molding material for electronic materials and is useful. Further, by reacting with the polymaleimide resin (A), it acts as a curing agent, can cause three-dimensional crosslinking, and a cured product excellent in heat resistance can be obtained, which is a preferable embodiment. Furthermore, also in relation to the epoxy resin (E) which is an optional component, it acts as a curing agent, improves the adhesion to copper, and is useful, for example, in the production of a circuit board using a copper foil.

[0084] In the curable composition of the present embodiment, it is preferable to contain 10% by mass or more and 70% by mass or less of the reactive double bond-containing compound (D) with respect to the entire curable composition (100% by mass), more preferably 15% by mass or more and 65% by mass or less, and most preferably 20% by mass or more and 50% by mass or less. When the content of the reactive double bond-containing compound (D) is in the range of 20% by mass or more and 50% by mass or less, it is preferable from the viewpoints of low dielectric characteristics and low moisture absorption.

[0085] The reactive double bond-containing compound (D) of the present embodiment is not particularly limited as long as it is a compound containing a group having two or more reactive double bonds (carbon-carbon unsaturated bonds) in the molecule. Examples of the reactive double bond include an allyl group, an isopropenyl group, a vinyl group, a 1-propenyl group, an acryloyl group, a methacryloyl group, a styryl group, and a styrylmethyl group. Among these, an allyl group, a vinyl group, a 1-propenyl group, a styryl group, a styrylmethyl group, etc. are preferable in that they show good reactivity with the maleimide group of the polymaleimide resin (A) and give a cured product with high crosslink density and excellent heat resistance. In addition, the reactive double bond-containing compound (D) may further have a reactive functional group other than the group having the reactive double bond. The reactive functional group is not particularly limited, and examples thereof include a cyanate group (cyanic acid ester group), a hydroxyl group, an epoxy group, an active ester group, an amine group, an isocyanate group, a glycidyl group, and a phosphate group. Among these, at least one selected from the group consisting of a cyanate group (cyanic acid ester group), a hydroxyl group, an epoxy group, and an active ester group is preferable, and a cyanate group (cyanic acid ester group) is more preferable. By having a hydroxyl group, a cyanate group (cyanic acid ester group), an epoxy group, or an active ester group, it has high flexural strength and flexural modulus, low dielectric constant, high glass transition temperature (Tg), low coefficient of thermal expansion, and tends to have improved thermal conductivity.

[0086] The reactive double bond-containing compound (D) having a reactive functional group other than the group having the reactive double bond may be used alone or in combination of two or more. When two or more reactive double bond-containing compounds (D) having a reactive functional group other than the group having the reactive double bond are used in combination, the reactive functional groups other than the reactive double bonds may be the same or different. Among these, it is preferable to include a reactive double bond-containing compound (D) in which the reactive functional group is a cyanate group (cyanic acid ester group) and a reactive double bond-containing compound (D) in which the reactive functional group is an epoxy group. By using such reactive double bond-containing compounds (D) having reactive double bonds in combination, the flexural strength, flexural modulus, glass transition temperature (Tg), and thermal conductivity tend to be further improved. As the reactive double bond-containing compound (D) of the present embodiment, for example, a bisphenol compound (B1) in which a hydrogen atom of an aromatic ring is substituted with an allyl group, a modified phenol compound (B2) in which a hydrogen atom of an aromatic ring is substituted with an allyl group and a phenolic hydroxyl group is modified with a reactive functional group other than a hydroxyl group among reactive functional groups other than the reactive double bond, or a polyphenylene ether compound (B3) having a reactive double bond can be mentioned. More specifically, diallylbisphenol A, a cyanate ester compound of diallylbisphenol A, a diallylbisphenol A-type epoxy compound, an allylphenol-terminated active ester compound, etc. can be mentioned. The bisphenol structure in the bisphenol compound is not particularly limited, and examples thereof include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z. Among these, bisphenol A is preferable.

[0087] The polyphenylene ether compound (B3) having a reactive double bond of the present embodiment is not particularly limited as long as it is a polyphenylene ether compound having a reactive double bond in its molecule. For example, it preferably has a structural unit selected from the group consisting of partial structures represented by the following general formula (3) and general formula (4), and a terminal structure containing a group having a reactive double bond bonded to the partial structure. [Chemical formula] [Chemical formula] [In the above general formulas (3) and (4), R d1 ~R d8Each independently represents 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 or an alkylsulfonyl group having 1 to 5 carbon atoms; Y in the general formula (4) represents a divalent aromatic hydrocarbon group derived from an aromatic compound having two phenolic hydroxyl groups; v is an integer value of 1 to 30; and w and u are integer values of 1 to 30. In addition, the partial structure represented by the general formula (3) and / or the general formula (4) has a group containing a reactive double bond at the terminal structure of the structure. Examples of the group containing a reactive double bond include an alkenyl group having 1 to 5 carbon atoms, a (meth)acryloyl group, a styryl group, a styrylmethyl group, etc.

[0088] The polyphenylene ether (PPE) contained in the structure of the polyphenylene ether compound (B3) having a reactive double bond of the present embodiment is excellent in dielectric properties such as dielectric constant or dielectric tangent. Therefore, even in a high-frequency band (high-frequency region) from the MHz band to the GHz band, a curable composition capable of obtaining a cured product exhibiting a sufficiently low dielectric tangent while maintaining a sufficiently low dielectric constant can be prepared. Thus, it can be used as a molding material for high frequencies and is useful. Further, by reacting with the polymaleimide resin (A), it acts as a curing agent and can cause three-dimensional crosslinking, and a cured product excellent in heat resistance can be obtained, which is a preferable embodiment.

[0089] 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, a pentylthio group, etc.

[0090] 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, a butylcarbonyl group, etc.

[0091] 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, a butyloxycarbonyl group, and the like.

[0092] 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, a butylcarbonyloxy group, and the like.

[0093] 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, a pentylsulfonyl group, and the like.

[0094] R in the above general formulas (3) and (4) d1 ~R d8 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.

[0095] Y in the above general formula (4) is a divalent aromatic hydrocarbon 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, tetramethyl bisphenol A, and the like. 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. Further, 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 hydrocarbon group derived from the aromatic compound having two phenolic hydroxyl groups. In other words, a group obtained by removing two arbitrary hydrogen atoms from the aromatic compound having two phenolic hydroxyl groups is defined as a "divalent aromatic hydrocarbon group derived from the aromatic compound having two phenolic hydroxyl groups".

[0096] In addition, in the present embodiment, the weight average molecular weight (Mw) of the polyphenylene ether compound (B3) having a reactive double bond is preferably from 1000 to 5000, more preferably from 1200 to 4000, and even more preferably from 1400 to 3000. Within the above range, a cured product with more reliable excellent dielectric properties and a well-balanced heat resistance can be obtained, which is a preferable aspect. Here, the weight average molecular weight (Mw) may be measured by a general molecular weight measurement method, and specifically, values measured using GPC described in the examples section below can be mentioned.

[0097] (Hardener (G) other than the reactive double bond-containing compound (D)) In the curable composition of this embodiment, a curing agent (G) other than the reactive double bond-containing compound (D) can also be added within a range that does not impair the curing of the present invention. With respect to the entire curable composition (100% by mass), the curing agent (G) 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 curing agent (G) is in the range of 5% by mass or more and 10% by mass or less, it is preferable from the viewpoints of low moisture absorption and low dielectric tangent.

[0098] Examples of the curing agent (G) of this embodiment include amine compounds, cyanate ester compounds, amide compounds, acid anhydride compounds, phenol compounds, polyphenylene ether compounds having a hydroxyl group at the terminal, diene polymers, and the like. These curing agents may be used alone or in combination of two or more.

[0099] Examples of the above amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivatives, and the like.

[0100] Examples of the cyanate ester 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 novolac type cyanate ester resin, cresol novolac 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 novolac type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-condensed novolac type cyanate ester resin, naphthol-cresol co-condensed novolac type cyanate ester resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type cyanate ester resin, biphenyl-modified novolac type cyanate ester resin, anthracene type cyanate ester resin, and the like. These may be used alone or in combination of two or more.

[0101] Examples of the amide compound include dicyandiamide, polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, and the like.

[0102] 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.

[0103] 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 (Zylok 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.

[0104] Examples of the polyphenylene ether-based compound having a hydroxyl group at the terminal include compounds having a partial structure represented by the general formula (3) or (4) and a terminal structure in which a hydroxyl group is bonded to the partial structure.

[0105] Examples of the diene-based polymer include non-modified diene-based polymers not modified by polar groups. Here, the polar group is a functional group that affects dielectric properties, and examples thereof include a phenol group, an amino group, and an epoxy group. The diene-based polymer is not particularly limited, and for example, 1,2-polybutadiene, 1,4-polybutadiene, or the like can be used.

[0106] As the diene-based polymer, a homopolymer 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.

[0107] (Epoxy resin (E)) The curable composition of this embodiment preferably further contains an epoxy resin (E). The epoxy resin (E) can be used to prepare a curable composition that has good fluidity during the preparation of the curable composition and can obtain a cured product with excellent adhesion, and is useful. In addition, when a polymaleimide resin (A), a reactive double bond-containing compound (D), and an epoxy resin (E) are used as the curable composition of this embodiment, the adhesion to copper is improved, and it is useful, for example, in the production of circuit boards using copper foil.

[0108] The epoxy resin (E) of the present embodiment is not particularly limited. For example, novolak type epoxy resins such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, α-naphthol novolak type epoxy resin, β-naphthol novolak type epoxy resin, bisphenol A novolak type epoxy resin, biphenyl novolak 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-naphthalene dicarboxylic acid diglycidyl ester type epoxy resin, glycidyl ester type epoxy resin of hexahydrophthalic anhydride; benzopyran type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, 7-phenylhexamethyldibenzopyran and the like. These may be used alone or in combination of two or more kinds.

[0109] Among these, phenolic aralkyl type epoxy resins, biphenyl novolak type epoxy resins, naphthol novolak type epoxy resins containing a naphthalene skeleton, naphthol aralkyl type epoxy resins, naphthol-phenol co-condensed novolak type epoxy resins, naphthol-cresol co-condensed novolak type epoxy resins, crystalline biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, xanthene type epoxy resins, alkoxy group-containing aromatic ring-modified novolak type epoxy resins (compounds in which a glycidyl group-containing aromatic ring and an alkoxy group-containing aromatic ring are linked by formaldehyde), etc. are particularly preferable in that cured products having excellent heat resistance can be obtained.

[0110] When the curable composition of this embodiment contains an epoxy resin (E), the epoxy resin (E) is preferably contained in an amount of 2% by mass or more and 30% by mass or less, and most preferably 5% by mass or more and 25% by mass or less, based on the total amount (100% by mass) of the curable composition. When the content of the epoxy resin (E) is in the range of 5% by mass or more and 25% by mass or less, it is preferable from the viewpoint of heat resistance.

[0111] The preferred curable composition of this embodiment is characterized by containing a polymaleimide resin (A), a reactive double bond-containing compound (D), and an epoxy resin (E). The polymaleimide resin (A) has a chemical structure in which two or more maleimide groups are linked to an alkanediyl group having an aromatic ring. Compared with conventional maleimide resins, it has excellent solvent solubility, is easy to prepare a curable composition, has excellent handling properties, and has a small proportion of polar functional groups in the structure of the polymaleimide resin (A), so a cured product with excellent dielectric properties can be obtained. Further, the reactive double bond-containing compound (D) acting as a curing agent can contribute to the formation of a cured product with a high crosslink density by the reaction of the reactive double bond in the reactive double bond-containing compound (D) with the maleimide group. Furthermore, the epoxy resin (E) has good fluidity during the preparation of the curable composition and can obtain a cured product with excellent adhesion. Also, when the reactive double bond-containing compound (D) acting as a curing agent reacts with the polymaleimide resin (A) and the epoxy resin (E), three-dimensional crosslinking can occur, and a cured product with excellent heat resistance can be obtained, which is a preferred embodiment. In addition, the reaction between the reactive double bond-containing compound (D) and the epoxy resin (E) improves the adhesion to copper and is useful, for example, in the manufacture of circuit boards using copper foil.

[0112] As the blending ratio (parts by mass) of the polymaleimide resin (A), the reactive double bond-containing compound (D), and the epoxy resin (E), the blending amount of the polymaleimide resin (A): the total blending amount of the reactive double bond-containing compound (D) and the epoxy resin (E) is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, still more preferably 65:35 to 35:65, and particularly preferably 55:45 to 45:55. By adjusting the blending ratio within the above range, heat resistance, low dielectric constant, and low dielectric tangent can be achieved, which is preferable.

[0113] In the curable composition of the present invention, the blending ratio (parts by mass) of the reactive double bond-containing compound (D) and the epoxy resin (E) is not particularly limited. However, from the viewpoint of obtaining good cured product properties, the ratio of the reactive double bond-containing compound (D):epoxy resin (E) is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and even more preferably 65:35 to 35:65. By adjusting the blending ratio within the above range, heat resistance, low dielectric constant, and low dielectric tangent can be achieved, which is preferable.

[0114] (Other resin (F)) Also, within a range that does not impair the object of the present disclosure, in addition to the polymaleimide resin (A), the reactive double bond-containing compound (D), and the epoxy resin (E), other resins (F) may be contained. Examples of the other resin (F) include bismaleimides other than the polymaleimide resin (A), allyl ether compounds, allylamine compounds, triallyl cyanurate, alkenylphenol compounds, vinyl group-containing polyolefin compounds, etc., phenolic resins, active ester resins, polyphenylene ether resins, cyanate 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. The content of the other resin (F) 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, based on 100% by mass of the total amount of the curable composition. When the content of the other resin (F) is in the range of 5% by mass or more and 10% by mass or less, it is preferable from the viewpoints of heat resistance and compatibility.

[0115] (Additive) The curable composition of the present embodiment can also appropriately use additives in combination as needed. Examples of the additives include one or more selected from the group consisting of a curing accelerator, an inorganic filler, a flame retardant, a silane coupling agent, a mold release agent, a pigment, an emulsifier, and a solvent. The content of the additive 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.

[0116] <Curing accelerator> The curable composition of the present embodiment can also appropriately use a curing accelerator in combination as needed. Various types of 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 in the present embodiment is preferably 0.05 to 5% by mass of the whole curable composition.

[0117] <Additives other than the curing accelerator> Examples of the flame retardant include an inorganic phosphorus-based flame retardant, an organic phosphorus-based flame retardant, a halogen-based flame retardant, or a non-halogen-based flame retardant. In the curable composition of the present embodiment, in order to exhibit flame retardancy within a range not impairing the purpose, it is more preferable to blend a non-halogen-based flame retardant that substantially does not contain a halogen atom. Examples of the non-halogen-based flame retardant include a phosphorus-based flame retardant, a nitrogen-based flame retardant, a silicone-based flame retardant, an inorganic-based flame retardant, an organic metal salt-based flame retardant, and the like, and these can be used alone or in combination.

[0118] In the curable composition of the present embodiment, an inorganic filler can be blended as needed. 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 crushed or 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. Furthermore, in order to increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. Considering the flame retardancy, the filling rate is preferably high, 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 the conductive paste described in detail below, a conductive filler such as silver powder or copper powder can be used. Also, the above silane coupling agent, the above mold release agent, the above pigment, the above emulsifier, and the above solvent are not particularly limited, and known ones can be used. As the above solvent, the organic solvents described in this specification may also be used.

[0119] In the curable composition of the present embodiment, with respect to the entire curable composition (100% by mass), the lower limit of the total content of the polymaleimide resin (A) and the reactive double bond-containing compound (D) is preferably 40% by mass, 42% by mass, 45% by mass, 47% by mass, 48% by mass, or 50% 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 the present embodiment, with respect to the entire curable composition (100% by mass), the total content of the polymaleimide resin (A) and the reactive double bond-containing compound (D) is preferably 40% by mass or more and 100% by mass or less, more preferably 45% by mass or more and 100% by mass or less, and even more preferably 50% by mass or more and 100% by mass or less. The curable composition of the present embodiment preferably has a lower limit of the total content of the polymaleimide resin (A), the reactive double bond-containing compound (D), the inorganic filler, and the additive of 70% by mass, 72% 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 polymaleimide resin (A) and the reactive double bond-containing compound (D). The curable composition of the present embodiment preferably has a lower limit of the total content of the polymaleimide resin (A), the reactive double bond-containing compound (D), the epoxy resin (E), and the additive of 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 polymaleimide resin (A) and the reactive double bond-containing compound (D).

[0120] When the curable composition of the present disclosure contains a compound having two or more cyanate groups (N≡C - O-), the content of the compound having two or more cyanate groups (N≡C - O-) is preferably less than 43% by mass, more preferably less than 10% by mass, more preferably less than 4% by mass, and even more preferably less than 0.5% by mass with respect to the total amount of the compound having two or more cyanate groups (N≡C - O-) and the polymaleimide resin (A). In a more preferred form of the curable composition of the present disclosure, when the curable composition contains a compound having one or more cyanate groups (N≡C - O-), the content of the compound having one or more cyanate groups (N≡C - O-) is preferably less than 15% by mass, more preferably less than 10% by mass, more preferably less than 4% by mass, and even more preferably less than 0.5% by mass with respect to the entire curable composition (100% by mass).

[0121] [Cured product] The cured product of the present disclosure is preferably obtained from the 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, a compounding agent), 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. As the curing (thermosetting) reaction, it can be easily carried out even without a catalyst. However, when it is desired to react more quickly, 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. The blending amount is preferably 0.05 to 5% by mass of the entire curable composition.

[0122] (Heat-resistant material and electronic material) Since the cured product obtained from the curable composition of the present disclosure exhibits low hygroscopicity and is excellent in heat resistance and dielectric properties, it can be suitably used for a heat-resistant member or an electronic member. In particular, it can be suitably used for a prepreg, a circuit board, a semiconductor encapsulation material, a semiconductor device, a build-up film, a build-up board, an adhesive using a conductive paste, a resist material, etc. Further, it can also be suitably used as a matrix resin of a fiber-reinforced resin, and is particularly suitable as a prepreg having high heat resistance. Further, the polymaleimide resin (A) contained in the curable composition can be made into a paint because it exhibits excellent solubility in various solvents. The heat-resistant member and the electronic member thus obtained can be suitably used for various applications. For example, industrial machine parts, general machine parts, parts of automobiles, railways, vehicles, etc., parts related to space and aviation, electronic and electrical parts, building materials, container and packaging members, daily necessities, sports and leisure goods, housing members for wind power generation, etc. can be mentioned, but it is not limited to these.

[0123] <Semiconductor encapsulation material> The present disclosure relates to a semiconductor encapsulating material containing the curable composition of the present embodiment. The semiconductor encapsulating material obtained by using the curable composition of the present embodiment has improved hygroscopicity, low dielectric tangent rate or dimensional stability by using the curable composition of the present disclosure, and thus is excellent in processability, moldability and reflow resistance in the manufacturing process, which is a preferable embodiment. The curable composition of the present embodiment used in the semiconductor encapsulating material may contain an inorganic filler. The filling rate of the inorganic filler can be, for example, in the range of 0.5 to 1200 parts by mass of the inorganic filler with respect to 100 parts by mass of the curable composition of the present embodiment. Examples of the inorganic filler include 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, and the like. Examples of the method for obtaining the semiconductor encapsulating material include a method of sufficiently melt-mixing the curable composition of the present embodiment with an additive, which is an optional component, as needed using an extruder, kneader, roll, etc. until it becomes uniform. When used as a high thermal conductivity semiconductor encapsulating material 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 fused silica, crystalline silica, alum ina, silicon nitride, etc. may be used. 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.

[0124] <Semiconductor device> The present disclosure relates to a semiconductor device including a cured product of the semiconductor encapsulating material. Since the semiconductor device obtained using the semiconductor encapsulating material obtained using the curable composition of the present embodiment contains the polymerimide resin (A) and the reactive double bond-containing compound (D) of the present disclosure, it has a low viscosity and excellent fluidity. Furthermore, because its hygroscopicity, storage modulus at high temperatures, or adhesiveness to metal materials is improved, it is excellent in workability, moldability, and reflow resistance in the manufacturing process, which is a preferred embodiment. 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.

[0125] <Prepreg> The present disclosure relates to a prepreg having a reinforcing base material and a semi-cured product of the curable composition of the present embodiment impregnated in the reinforcing base material. As a method for obtaining a prepreg from the above curable composition, an organic solvent described later is blended to form a varnish, and the varnish-like curable composition is impregnated into a reinforcing base material (paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass mat, glass rovings 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 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 halfway 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

[0126] Examples of the organic solvent used for manufacturing the prepreg 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 amount of use can be appropriately selected depending on the application. For example, when further manufacturing a printed circuit board from the prepreg as described below, it is preferable to use a polar solvent having a boiling point of 160°C or lower such as methyl ethyl ketone, acetone, 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.

[0127] <Circuit board> The present disclosure is a circuit board which is a laminate of the prepreg and a copper foil. Examples of the method for obtaining a printed circuit board from the curable composition of the present embodiment include a method of laminating the above prepreg by a conventional method, appropriately stacking a copper foil, and thermocompression bonding at 170 to 300°C for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.

[0128] <Build-up board> As a method for obtaining a build-up substrate from the curable composition of the present embodiment, a method via the following steps 1 to 3 can be mentioned. In step 1, first, the curable composition appropriately blended with rubber, filler, etc. is applied to a circuit board on which a circuit is formed using a spray coating method, a curtain coating method, etc., and then cured. In step 2, if necessary, after drilling holes such as predetermined through-hole parts in the circuit board coated with the curable composition, it is treated with a roughening agent, and its surface is rinsed with hot water to form irregularities on the substrate, and a metal such as copper is plated. In step 3, the operations of steps 1 to 2 are sequentially repeated as desired to alternately build up a resin insulation 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 insulation layer. Further, in the build-up substrate of the present embodiment, a copper foil with resin in which the composition is semi-cured on a copper foil is heat-pressed at 170 to 300 °C onto a wiring board on which a circuit is formed to form a roughened surface, and it is also possible to produce a build-up substrate by omitting the plating process step.

[0129] <Build-up film> The present disclosure is a build-up film containing the curable composition of the present embodiment. As a method for manufacturing the build-up film of the present embodiment, a method can be mentioned in which the above curable composition is applied onto a support film (Y), dried, and a curable composition layer is formed on the support film (Y) to obtain an adhesive film for a multilayer printed wiring board.

[0130] When manufacturing a build-up film from a curable composition, the film should soften under the temperature conditions of lamination in the vacuum lamination method (usually 70 to 140 °C), and it is essential that, simultaneously with the lamination of the circuit board, it exhibits fluidity (resin flow) that enables resin filling in the via holes or through holes present in the circuit board. It is preferable to blend the above components so as to exhibit such characteristics. In addition, in the resulting build-up film and circuit board (copper-clad laminate, etc.), in order to avoid phenomena such as locally different characteristic values caused by phase separation and to exhibit constant performance at any site, appearance uniformity is required.

[0131] Here, the diameter of the through holes in a 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 holes be filled to about half.

[0132] Specifically, the method for manufacturing the above 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 or hot air blowing, etc. 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, and it is also preferable to use them in a proportion such that the non-volatile content is 30 to 60% by mass.

[0133] The thickness of the formed composition layer (X) is preferably usually equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm.

[0134] In addition, 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 adhesion of dust or the like and scratches on the surface of the resin composition layer.

[0135] Examples of the above-mentioned support film (Y) and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET"), polyethylene naphthalate, polycarbonate, polyimide, and further release paper, copper foil, metal foils such as aluminum foil, etc. In addition, the support film and the protective film may be subjected to a matting treatment, a corona treatment, or a release treatment.

[0136] The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and is preferably used in the range of 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0137] 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 heat curing the adhesive film, it is possible to prevent adhesion of dust or the like in the curing process. When peeling off after curing, usually, the support film is previously subjected to a release treatment. 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 in direct contact with the circuit board, for example, by a vacuum lamination method. The lamination method may be a batch type or a continuous roll type. Further, 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, a crimping pressure of 1 to 11 kgf / cm 2 (9.8×10 4 ~107.9×10 4 N / m 2 ), and it is preferable to laminate under a reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

[0138] <Conductive paste> As a method for obtaining a conductive paste from the curable composition of the present invention, for example, a method of dispersing conductive particles in the composition can be mentioned. The above conductive paste can be a circuit connection paste resin composition or an anisotropic conductive adhesive depending on the type of conductive particles used.

Examples

[0139] The present invention will be specifically described with reference to Examples and Comparative Examples. In the following, "parts" and "%" are based on mass unless otherwise specified. The physical properties of the synthesized polymaleimide resin (A) were measured as follows.

[0140] (1) Amine equivalent and maleimide group equivalent The amine equivalent of the intermediate amine compound (C) was measured by the following measurement method. In a 500 mL Erlenmeyer flask with a stopper, about 2.5 g of each of the above intermediate amine compounds (C) as samples, 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine were precisely weighed, then a condenser was attached and heated under reflux in an oil bath set at 120°C 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 carried out 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

[0141] (2) GPC measurement Using the following measuring device and measuring conditions, the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the polymaleimide resin (A) used in the examples and comparative examples were calculated. "Measuring device" "HLC-8320 GPC" manufactured by Tosoh Corporation "Measuring conditions" 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 Measuring 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 polymaleimide resin (A) obtained in the synthesis example, filtered through a microfilter (50 μl), in terms of resin solid content.

[0142] (3) 13 C-NMR measurement Of the polymaleimide resin obtained in the synthesis example 13 The C-NMR spectrum was measured under the following measuring apparatus and measuring conditions. · 13 C-NMR: "JNM-ECZ400S" manufactured by JEOL RESONANCE Resonance frequency: 100 MHz Number of integrations: 4000 times Solvent: chloroform-d Sample concentration: 12 mass% Relaxation reagent: chromium(III) acetylacetonate

[0143] (4) FD-MS measurement The FD-MS spectrum of the polymaleimide resin obtained in the synthesis example was measured using the following measuring apparatus and measuring 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

[0144] [Synthesis Example 1] Synthesis of polymaleimide resin (A-1) (1) Synthesis of intermediate amine compound (c-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 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 under heating and reduced pressure to obtain an intermediate aromatic amine compound (c-1) (= hereinafter intermediate amine compound (c-1)) (amine equivalent 218 g / eq.). The FD-MS spectrum of the obtained intermediate amine compound (c-1) is shown in Figure 1, 13 and the C-NMR spectrum is shown in Figure 2.

[0145] (II) 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 intermediate amine compound (c-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, cooled and separated, then heated to 115 °C and the water and toluene that came out under reflux were cooled and separated, and 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, the obtained brown solution was dissolved in 600 g of ethyl acetate, washed 3 times with 200 g of ion-exchanged water and 3 times with 150 g of 2% aqueous sodium hydrogen carbonate solution, sodium sulfate was added, dried, and then concentrated under reduced pressure. The obtained reaction product was vacuum dried at 80 °C for 4 hours to obtain a product containing polymaleimide resin (A-1). The GPC chart of this polymaleimide 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 etc., the obtained polymaleimide 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 is 1 or more and contains 10% by mass or more of the component was confirmed.

[0146] For each peak of the FD-MS spectrum shown in Figure 4, the repeating number in the polymaleimide resin (A-1) was confirmed. The correspondence between each peak, the repeating numbers [n 1 and n 2 in the general formula (1A) and the bonding destination of * is shown in Table 1 below.

[0147] [Table 1]

[0148] [Examples 1 to 3 and Comparative Examples 1 to 3] [Preparation of curable composition] The polyimide resin (A-1) obtained in Synthesis Example 1, the comparative maleimide compound (A-2) ("BMI-1000" manufactured by Daiwa Kasei Kogyo Co., Ltd., phenylmethane maleimide, formula (i)), as the reactive double bond-containing compound (D), resin (D-1) ("SA-9000", manufactured by SABIC, methacryl-modified polyphenylene ether with both ends), resin (D-2) ("NE-V-1100", manufactured by DIC, vinyl resin with both ends) and resin (D-3) ("DABAP", manufactured by Daiwa Kasei Kogyo Co., Ltd., 2,2'-diallylbisphenol A), and as the epoxy resin (E), resin (E-1) (BPA-type epoxy resin "850-S" equivalent: 188 g / eq, manufactured by DIC Corporation), and DCPO ("Parkmill D", manufactured by NOF Corporation, Dicumyl Peroxide) as a curing catalyst were blended at the ratios shown in Table 1 below to prepare the curable compositions of Examples 1 to 3 and Comparative Examples 1 to 3. [Chemical formula]

[0149] [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 further 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 loss tangent, and moisture absorption rate were performed by the following methods. The results are shown in Table 1.

[0150] [Measurement of dielectric loss tangent] In accordance with JIS-C-6481, using the network analyzer "E8362C" manufactured by Agilent Technologies, Inc., the dielectric constant (Dk) and dielectric loss tangent (Df) at 1 GHz of a test piece, which was a cured product stored in a room at 23 °C and 50% humidity for 24 hours after being completely dried, were measured by the cavity resonance method. [Measurement of moisture absorption rate] In this Example and Comparative Examples, as an evaluation method for low moisture absorption, the moisture absorption rate (%) was calculated and evaluated by the following method. A test piece cut from the above-mentioned cured product 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

[0151]

Table 2

[0152] From the results shown in Table 2 above, when comparing the examples and the comparative examples, it can be confirmed that by using the curable composition containing the polymerimide resin (A) and the reactive double bond-containing compound (D) of the examples, low dielectric constant, low dielectric tangent, and low moisture absorption rate were achieved. Also, for the cured products obtained in Examples 1 to 3 and Comparative Examples 1 to 3 above, the dielectric constant (Dk) and dielectric tangent (Df) at 10 GHz were also measured in the same manner as the measurement at 1 GHz. However, all of the cured products obtained in Examples 1 to 3 showed a lower dielectric constant (Dk) and dielectric tangent (Df) than the cured products of Comparative Examples 1 to 3.

Industrial Applicability

[0153] According to the present disclosure, a curable composition and a cured product thereof that achieve both high-order low dielectric characteristics and low moisture absorption rate after curing can be provided.

Claims

1. A polymer maleimide 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 A curable composition comprising a reactive double bond-containing compound (D) having a reactive double bond. 【Chemical Formula 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, 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 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 polymer maleimide resin (A) uses an aromatic amine compound (A-a) represented by the following general formula (a-1), a compound (B) having a benzyl ether skeleton, and maleic anhydride as reaction raw materials (1). [Chemical Formula 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 polymer maleimide resin (A) is a polymer maleimide resin having a partial structure represented by the following general formula (1A). 【Chemical Formula 4】 In the general formula (1A) above, R １４ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, and R １５ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and m ３ each represents 2, 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, and the two * each represent a bond and are bonded to a hydrogen atom or a partial structure represented by the 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. Regarding the average number of repeating units of the polymaleimide resin (A) represented by the general formula (1A), n １ and n ３ The curable composition according to claim 3, containing 10% by mass or more of a component in which the sum of and is 1 or more.

5. A polymer maleimide resin (A) mixture containing a polymer maleimide resin (A) 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), and A reactive double bond-containing compound (D) having a reactive double bond, and The polymer maleimide resin (A) mixture contains 1 to 99% by mass of a polymer maleimide 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 polymer maleimide resin (A) component, and contains 80% by mass or less of the maleimide multimer compound with respect to the total amount of the polymer maleimide resin (A) mixture. A curable composition characterized by the above. [Chemical Formula 6] [In the general formula (1a) above, 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, n １ represents the average number of repeating units. ] [Chemical Formula 7] [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 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 at the position of, indicating that they are chemically bonded.] 【Chemical Formula 9】 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 to 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 to L １４ is a hydrogen atom, m １ and m ３ each represent 2.]

6. The curable composition according to claim 5, wherein the polymer maleimide resin (A) uses an aromatic amine compound (A-a) represented by the following general formula (a-1), a compound (B) having a benzyl ether skeleton, and maleic anhydride as reaction raw materials (1). 【Chemical 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. The polymer maleimide resin according to claim 3, represented by the general formula (1A).

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 laminate having the prepreg according to Claim 9 and 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.

Images