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

Abstract

To provide a polymaleimide resin exhibiting superior dielectric properties and low hygroscopicity during curing, and to provide a curable composition containing the polymaleimide resin.SOLUTION: A curable composition comprises a polymaleimide resin (A) having a predetermined partial structure, and a cyanate ester (B).SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a curable composition, a polymaleimide resin, 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 bismaleimide-triazine (BT) 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 becomes a problem, so that materials that exhibit high heat resistance are required to suppress warping of the package substrate during mounting.

[0003] In addition, in recent years, signals have become faster and higher in frequency, and it is desired to provide a thermosetting composition capable of forming a cured product that maintains a sufficiently low dielectric constant and exhibits a sufficiently low dielectric loss tangent under such an environment. In particular, in recent years, in various electrical material applications, particularly in advanced material applications, there is a demand for improved performance, such as heat resistance and dielectric properties, and for materials and compositions that combine these.

[0004] In response to such demands, maleimide resins have attracted attention as materials that combine heat resistance and low dielectric properties. In particular, maleimide resins used in materials for printed circuit boards are required to have improved performance in terms of fine pattern processability, dimensional stability, heat resistance, or high-frequency electrical properties. For example, Patent Documents 1 and 2 disclose techniques 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]

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] 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 examined, and it has not been examined whether it can be applied to the technology for the fifth-generation mobile communication system (5G) using the so-called Sub6 frequency band.

[0007] Therefore, the technical problem to be solved by the present disclosure is to provide a polyimide resin showing excellent dielectric properties and low hygroscopicity during curing, a curable composition containing the polyimide resin, a cured product thereof, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device.

Means for Solving the Problems

[0008] The first curable composition according to the present invention has a partial structure represented by the following general formula (1), a partial structure represented by the following general formula (2) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (3) chemically bonded to the partial structure represented by the general formula (1), and a polyimide resin (A); a cyanate ester (B), and is a curable composition characterized by showing excellent dielectric properties and low hygroscopicity during curing.

Chemical Formula

[0009] In one embodiment of the first curable composition according to the present invention, the polyimide resin (A) is a reaction raw material (1) comprising an aromatic amine compound (A-a) represented by the following general formula (a-1), a compound (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c). [Chemical formula] [In the above general formula (a-1), R a1 and R a2Each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 1 represents a hydrocarbon group having 1 to 18 carbon atoms, and R 2 and R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]

[0010] In one embodiment of the first curable composition according to the present invention, 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 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 2 represents an integer of 0 or more and 4 or less, n 1 represents an average repeating unit number, 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 an average repeating unit number, ran represents that the arrangement of each structural 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 (4).] [Chemical formula] [In the above general formula (4), 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 3 represents an average repeating unit number.]

[0011] In one embodiment of the first curable composition according to the present invention, a component represented by the above general formula (1A) and having the sum of n 1 and n 3 of 1 or more is contained in an amount of 10% by mass or more.]

[0012] In addition, the second curable composition according to the present invention contains a polyimide resin component having a partial structural unit represented by the following general formula (1a), and a maleimide multimer compound represented by the following general formula (5), and a maleimide resin mixture (C). It contains a cyanate ester (B). The maleimide resin mixture (C) contains 1 to 99% by mass of a polyimide resin (A) having a partial structure represented by the following general formula (1), a partial structure represented by the following general formula (2) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (3) chemically bonded to the partial structure represented by the general formula (1), based on the total amount of the polyimide resin component, and contains 80% by mass or less of the maleimide multimer compound based on the total amount of the maleimide resin mixture (C). It is a curable composition characterized by this.

Chemical formula

Chemical formula

Chemical formula

[0013] In one embodiment of the second curable composition according to the present invention, the polymaleimide resin (A) uses an aromatic amine compound (A-a) represented by the following general formula (a-1), a compound (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c) as reaction raw materials (1). [Chemical formula] [In the above general formula (a-1), R a1 and R a2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R 1 represents a hydrocarbon group having 1 to 18 carbon atoms, and R 2 and R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]

[0014] The maleimide resin according to the present invention is a polymaleimide resin, characterized by having a partial structure represented by the following general formula (1A). [Chemical formula] [In the above general formula (1A), R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 2 represents an integer of 0 or more and 4 or less, n 1 represents the average number of repeating units, R 11 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 1 each represents 2, n 2 represents the average number of repeating units, ran represents that the arrangement of each constitutional unit can be random, the two * each represent a bond, and are bonded to a hydrogen atom or a partial structure represented by the general formula (4).] [Chemical formula] [In the above general formula (4), 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 3 represents the average number of repeating units.]

[0015] The cured product according to the present invention is a cured product of any of the above curable compositions.

[0016] The prepreg according to the present invention is 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.

[0017] The circuit board according to the present invention is a circuit board which is a laminate having a prepreg and a copper foil.

[0018] The build-up film according to the present invention is a build-up film containing any one of the above curable resin compositions.

[0019] The semiconductor encapsulant according to the present invention is a semiconductor encapsulant containing any one of the above curable compositions.

[0020] The semiconductor device according to the present invention is a semiconductor device containing a cured product of the above semiconductor encapsulant.

Advantages of the Invention

[0021] According to the present invention, it is possible to provide a polyimide resin which exhibits excellent dielectric properties and low moisture absorption during curing, a curable composition containing the polyimide resin and a cured product thereof, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device.

Brief Description of the Drawings

[0022]

Figure 1

Figure 2

Figure 3

Figure 4

Figure 5

Mode for Carrying Out the Invention

[0023] Hereinafter, embodiments of the present invention will be described. These descriptions are for the purpose of exemplifying the present invention and do not limit the present invention in any way.

[0024] In the present invention, two or more embodiments can be arbitrarily combined.

[0025] The materials, components, compounds, resins, structural units, catalysts, and solvents described in this specification may be used alone or in combination of two or more, unless otherwise specified.

[0026] <Terms> Unless otherwise specified in this specification, the following terms can be applied.

[0027] As used herein, the "reaction raw material" refers to a compound used to obtain a target compound through a chemical reaction such as combination or decomposition, and that partially constitutes the chemical structure of the target compound. Substances that play the role of chemical reaction aids, such as solvents and catalysts, are excluded. In this specification, in particular, the "reaction raw material" refers to a precursor for obtaining a target polymaleimide resin or its precursor compound (e.g., an intermediate amine compound (I) in which structural units derived from aromatic amine compounds (A) having a benzyl ether skeleton are linked via a benzyl ether skeleton).

[0028] As used herein, the "structural unit" refers to a unit of chemical structure formed during a reaction or polymerization. In other words, in a 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.

[0029] The "aromatic group" in this specification preferably has an aromatic ring with 3 to 30 carbon atoms, and more preferably has an aromatic ring with 4 to 26 carbon atoms. And the "aromatic group" in this specification may have the hydrogen atoms of the aromatic ring in the aromatic group substituted by substituents such as an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, or a halogen atom. Further, the "aromatic group" includes heteroaromatics, and -CH2- or -CH= in the "aromatic group" may be substituted by -O-, -S- or -N= so that they are not adjacent to each other. Examples of the type of the aromatic ring include a monocyclic aromatic ring, a condensed aromatic ring, or a polycyclic aromatic ring.

[0030] Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, etc.

[0031] Examples of the condensed aromatic ring include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etc.

[0032] Examples of the polycyclic aromatic ring include biphenyl, binaphthalene, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc. Further, the hydrogen atoms of the aromatic ring in the aromatic group may be substituted by, for example, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an aryl group with 1 to 12 carbon atoms, an aralkyl group with 1 to 12 carbon atoms, or a halogen atom. Note that the monovalent aromatic group refers to a group obtained by removing one hydrogen atom from the "aromatic group".

[0033] The "alkyl group" in this specification may be linear, branched or cyclic, and examples thereof include 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, a neopentyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an isohexyl group, an (n-)heptyl group, an (n-)octyl group, an (n-)nonyl group, an (n-)decyl group, an (n-)undecyl group, an (n-)dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group or an adamantyl group.

[0034] The "cycloalkyl group" in this specification includes, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group or an adamantyl group, etc.

[0035] 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.

[0036] The "alkenyl group" in this specification includes, for example, 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 or an isopropenyl group, etc. Note that the "alkenylene group" includes a divalent group obtained by removing one arbitrary hydrogen atom from the above-mentioned "alkenyl group".

[0037] 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.

[0038] As used herein, the "aryl group" 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. Further, in the "aryl group", a hydrogen atom of the aromatic ring in the aryl group may be substituted with, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom.

[0039] Examples of the "aralkyl group" as used herein 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, an alkenyl group having 1 to 10 carbon atoms, or a halogen atom. The "arylene group" includes a divalent group obtained by removing one arbitrary hydrogen atom from the above-mentioned "aryl group".

[0040] Examples of the "aryloxy group" as used herein include a phenoxy group, a naphthyloxy group, an anthryloxy group, a phenanthryloxy group, or a pyrenyloxy group, etc.

[0041] Examples of the "arylthio group" as used herein include arylthio groups such as a phenylthio group, a naphthylthio group, an anthrylthio group, a phenanthrylthio group, or a pyrenylthio group, etc.

[0042] Examples of the "halogen atom" as used herein include a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, etc.

[0043] Examples of the "alkylene group" as used herein include a methylene group, an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1-methylethylene group, a 1,1-dimethylethylene group, a 1,2-dimethylethylene group, a propylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, a dodecylene group, etc.

[0044] In the present specification, the "alkyleneoxy group" includes, for example, an oxymethylene group, an oxyethylene group, an oxypropylene group, an oxy(1-methylmethylene) group, an oxy(1,1-dimethylmethylene) group, an oxy(1-methylethylene) group, an oxy(1,1-dimethylethylene) group, an oxy(1,2-dimethylethylene) group, an oxybutylene group, an oxy(1-methylpropylene) group, an oxy(2-methylpropylene) group, an oxypentylene group, an oxyhexylene group, an oxyheptylene group, an oxyoctylene group, an oxynonylene group, an oxydecylene group, an oxyundecylene group, an oxydodecylene group, and the like.

[0045] The "hydrocarbon group" in the present specification is a monovalent group and includes linear, branched, or cyclic saturated hydrocarbons, unsaturated hydrocarbons, or aromatic groups. For example, the "hydrocarbon group" is one kind of group selected from the group consisting of an alkyl group (for example, the above alkyl group), an alkenyl group (for example, the above alkenyl group), an aryl group (for example, the above aryl group), an aryloxy group (for example, the above aryloxy group), an aralkyl group (for example, the above aralkyl group), and an alkoxy group (for example, the above alkoxy group), and one or more -CH2- in the group may be substituted with -O-, -C(=O)-, or -S- so as not to be adjacent to each other, or one or more -CH2-CH2- in the alkyl group may be substituted with -CH=CH- so as not to be adjacent to each other.

[0046] In the present specification, signs such as the first, second, (1), (2), etc. are merely signs for distinguishing one element from another element, and are not signs for limiting the quantity or order.

[0047] (First curable composition) The first curable composition according to the present invention includes a polymaleimide resin (A) having a partial structure represented by the following general formula (1), a partial structure represented by the following general formula (2) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (3) chemically bonded to the partial structure represented by the general formula (1), It contains cyanate ester (B) and...

Chemical formula

Chemical formula

[0048] ·Polymaleimide resin (A) The polyimide resin (A) of the first curable composition has a partial structure represented by the general formula (1), a partial structure represented by the general formula (2) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the general formula (3) chemically bonded to the partial structure represented by the general formula (1). Thereby, the cured product exhibits excellent dielectric properties and low moisture absorption. Since the chemical structure of the polyimide resin (A) has only one bonding site at the ortho-position and para-position of the benzene ring to which the maleimide group is bonded, a polyimide resin in which the chain extends linearly can be obtained, so that the molecular weight can be easily controlled, and both heat resistance and low dielectric properties and solvent solubility can be achieved.

[0049] In the general formula (1) above, the two * each represent a bond. And one of the two bonds is at the position of L in the general formula (2) 13 or L 14 and is chemically bonded. Also, the other bond is at the position of L in the general formula (3) 11 or L 12 and is chemically bonded. Therefore, the polyimide resin (A) of the present embodiment has a structural unit in which the partial structure represented by the general formula (2) and the partial structure represented by the general formula (3) are connected 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 (2) and the general formula (3), the partial structure represented by the general formula (1) is chemically bonded.

[0050] In the general formula (1) above, 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.

[0051] In the general formula (1) above, R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, preferably represents a hydrocarbon group having 1 to 12 carbon atoms, and more preferably represents a hydrocarbon group having 1 to 6 carbon atoms. Also, m2 When it is an integer of 2 or more, a plurality of R's exist 13 may be the same as or different from each other. Preferred R's in the general formula (1) 13 are preferably linear alkyl groups, more preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group or a neopentyl group. In addition, the benzene ring to which R in the general formula (1) is bonded 13 may be the benzene ring of the compound (A-b) having a benzyl ether skeleton.

[0052] 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) is bonded, when the 1-position and the 3-position are bonded by a methylene group, R is preferably bonded to the 4-position and the 6-position respectively. 13 13

[0053] 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.

[0054] The polymaleimide resin (A) in the present embodiment preferably contains 1 to 99% by mass, more preferably 3 to 97% by mass, 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).

[0055] In the above general formula (2), R 15 ​​Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Particularly preferred R 15 can be a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms. m 3 Since m is 2, the two R 15 may be the same as or different from each other.

[0056] In the above general formula (2), R 14 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. Particularly preferred R 14 can be a linear alkyl group having 1 to 6 carbon atoms.

[0057] At the ortho position (6-position) of the benzene ring in the above general formula (2) or the above general formula (3), by allowing the bonding site with the partial structure represented by the general formula (1), it has higher solubility in a solvent, and the cured product thereof exhibits more excellent dielectric properties and low moisture absorption. In addition, the benzene ring to which R 14 in the general formula (2) is bonded can be the benzene ring of the aromatic amine compound (A-a).

[0058] In the above general formula (2), L 13 or L 14 each 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 (2) 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. In addition, 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 .

[0059] In the above general formula (3), R11 Each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. Preferred R 11 can be a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms. m 1 Since m is 2, the two R 11 may be the same as or different from each other.

[0060] In the general formula (3) above, 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. In addition, the benzene ring to which R 12 in the general formula (3) is attached may be the benzene ring of the aromatic amine compound (A-a).

[0061] In the general formula (3) above, L 11 or L 12 each independently represents a bond or a hydrogen atom. However, at least one of the positions of L 11 or L 12 is chemically bonded to the partial structure represented by the general formula (1) and the partial structure represented by the general formula (3). 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. In addition, 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 .

[0062] The polymaleimide resin (A) in this 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 (2) with respect to the total amount (100% by mass) of the polymaleimide resin (A).

[0063] In the present embodiment, the polyimide resin (A) 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 (3) with respect to the total amount (100% by mass) of the polyimide resin (A).

[0064] 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 (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c) as reaction raw materials (1). [Chemical formula] [In the above general formula (a-1), R a1 and R a2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 1 represents a hydrocarbon group having 1 to 18 carbon atoms, and R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]

[0065] Further, the polyimide resin (A) of the present embodiment preferably uses an intermediate amine compound (I) in which aromatic amine compounds (A-a) are linked via a structural unit derived from a compound (A-b) having a benzyl ether skeleton and maleic anhydride (A-c) as reaction raw materials (2). Furthermore, the intermediate amine compound (I) is preferably a compound obtained by using an aromatic amine compound (A-a) and a compound (A-b) having a benzyl ether skeleton as reaction raw materials (3).

[0066] In other words, the intermediate amine compound (I) 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 (A-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 an amino group bonded to the aromatic ring of the intermediate amine compound (I) is substituted with an N-substituted maleimide ring. Note that 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.

[0067] Therefore, the "polyimide resin (A)" in the present embodiment and the "intermediate amine compound (I)" which is a precursor of the "polyimide resin (A)" are polymer compounds that differ in that the amino group bonded to the aromatic ring is replaced with an N-substituted maleimide ring.

[0068] Note that 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 (A-b) having a benzyl ether skeleton means that -(CH2O)- other than the terminal group in the compound (A-b) having a benzyl ether skeleton is substituted with -(CH2)- and is directly bonded to the benzene ring -(CH2O)-R b is a group in which all are substituted with -(CH2)-. Note that the R b represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.

[0069] In this embodiment, since the aromatic amino compound (A) having an aromatic ring structure with a substituent at a specific position is used as a reaction raw material, it becomes easier to control the reaction site with the compound (A-b) having a benzyl ether skeleton described later, and a homogeneous chemical structure and a chain polyimide resin (A) can be easily obtained. As a result, a polyimide resin (A) that exhibits excellent solubility in a solvent and whose cured product exhibits high heat resistance and excellent dielectric properties can be provided.

[0070] Hereinafter, after explaining the aromatic amine compound (A-a) represented by the general formula (a-1), the compound (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c), which are the constituent components of the reaction raw material (1) of the polyimide resin (A), another preferred form of the polyimide resin (A) and a method for producing the polyimide resin (A) will be explained.

[0071] -Aromatic amine compound (A-a) represented by the general formula (a-1)- The aromatic amine compound (A-a) in this embodiment 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

[0072] In the aromatic amine compound (A-a) of this embodiment, hydrocarbon groups (R 2 , R 3Examples thereof include linear, branched or cyclic hydrocarbon groups having 1 to 18 carbon atoms, preferably linear or branched hydrocarbon groups having 1 to 12 carbon atoms, and more preferably linear or branched alkyl groups having 1 to 6 carbon atoms. As described in the general formula (a-1) above, it has a binding site with the compound (A-b) having a benzyl ether skeleton at each of the ortho and para positions of the aromatic ring.

[0073] In the general formula (a-1) above, R 1 represents a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 6 carbon atoms.

[0074] In the general formula (a-1) above, R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 6 carbon atoms.

[0075] In the general formula (a-1) above, R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, and more preferably a hydrocarbon group having 1 to 6 carbon atoms.

[0076] In addition, by increasing the number of hydrocarbon groups (for example, alkyl groups) substituted on the aromatic ring of the aromatic amine compound (A-a) to 1 or more, it becomes easier to control the reaction site with the compound (A-b) having a benzyl ether skeleton described later, and thus it becomes easier to obtain a polymaleimide resin (A) having a specific chemical structure. As a result, in the cured product of the polymaleimide resin (A), it is easier to exhibit solvent solubility, heat resistance, and excellent high-frequency electrical properties. In particular, since a substituent (R 1 ) is introduced at the ortho position (adjacent position) of the aromatic amine compound (A-a), after maleimidating the amino group derived from the aromatic amine compound (A-a), the dihedral angle formed by the aromatic ring plane of the aniline skeleton and the nitrogen-containing five-membered ring plane of maleimide becomes large, making it easier to break the crystallinity derived from the maleimide group and improving the solubility.

[0077] In this embodiment, among the carbon atoms in the benzene ring constituting the aromatic amine compound (A-a), it is preferable that one or more carbon atoms having the largest HOMO electron density (Hückel coefficient) are unsubstituted (substituted with a hydrogen atom). Therefore, as the aromatic amine compound (A-a) represented by the general formula (a-1) of this 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 this embodiment is that the 2-position is substituted with an alkyl group, and the 4- and 6-positions are hydrogen atoms. Thereby, the ArS by the cationoid reagent formed from the compound (A-b) having a benzyl ether skeleton described later E The reaction and molecular design become easier to control. As a result, in the cured product of the polymaleimide resin (A), it becomes easier to exhibit solvent solubility, heat resistance, and excellent high-frequency electrical properties. In particular, by substituting the 4- and 6-positions of the benzene ring of the general formula (a-1) with hydrogen atoms, a polymaleimide resin (A) (or an intermediate amine resin) in which the molecules are linearly extended can be obtained.

[0078] 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-position, 2,4-position or 2,5-position is a methyl group and the other is an ethyl group), methylisopropylaniline (for example, methylisopropylaniline in which one of the 2,3-position, 2,4-position or 2,5-position is a methyl group and the other is an isopropyl group), or ethylbutylaniline (for example, ethylbutylaniline in which one of the 2,3-position, 2,4-position or 2,5-position is an ethyl group and the other is a butyl group), etc. can be used. The butyl includes n-butyl, tert-butyl and sec-butyl. The aromatic amine compound (A-a) in the present embodiment may be used alone or in combination of two or more.

[0079] For example, in the case of a chemical structure in which a maleimide group is directly bonded to an unsubstituted benzene ring, such as N-phenylmaleimide, since the benzene ring and the 5-membered ring of maleimide are arranged in the same plane in a stable state, they are likely to stack, resulting in the manifestation of high crystallinity. Therefore, this causes poor solvent solubility. On the other hand, in the case of the present disclosure, for example, when having an alkyl group (e.g., an ethyl group) as a substituent for the benzene ring, such as 2-ethylaniline, due to the steric hindrance of the ethyl group, the benzene ring and the 5-membered ring of maleimide take a twisted conformation, making it difficult to stack, thus reducing crystallinity and improving solvent solubility, which is a preferable embodiment. However, if the steric hindrance is too large or depending on the substitution position of the alkyl group, there are also concerns about inhibiting the reactivity during the synthesis of maleimidation or deteriorating the curability of the maleimide group when producing a cured product. Therefore, for example, it is preferable to use an aromatic amine compound (A-a) having a hydrocarbon group with 1 to 6 carbon atoms. In addition, in the present embodiment, the aromatic amine compound (A-a) represented by the general formula (a-1) may be used alone or in combination of two or more.

[0080] - Compound (A-b) having a benzyl ether skeleton - The compound (A-b) having a benzyl ether skeleton in the present embodiment may be a single compound or a mixture. When the compound (A-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 (6), more preferably a compound represented by the following formula (7), and even more preferably a compound represented by the following formula (8).

[0081] On the other hand, when the compound (A-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 (6) and / or a compound having a benzyl ether skeleton represented by the following formula (7), and a component having a partial structure represented by the following general formula (9) occupies 95% by mass or more and 100% by mass or less of the whole.

[0082] The compound (A-b) having a benzyl ether skeleton in the present embodiment is preferably a compound having a benzyl ether skeleton represented by the following formula (6). [Chemical formula] [In the above general formula (6), R b3 each independently represents an alkyl group having 1 to 18 carbon atoms, m b2 represents an integer of 0 or more and 4 or less, j 1 and j 2 each independently represents an integer of 0 or more and 4 or less, and j 1 +j 2 ≧1, k 1 and k 2 each independently represents 0 or 1, and * represents a bond with another atom.]

[0083] The compound (A-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.

[0084] --Physical properties of the compound (A-b) having a benzyl ether skeleton-- The compound (A-b) having a benzyl ether skeleton in the present embodiment has a benzyl ether skeleton represented by the above formula (6) 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.

[0085] The upper limit of the number average molecular weight (Mn) of the compound (A-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 (A-b) having a benzyl ether skeleton is preferably 200 or more, more preferably 240 or more, and even more preferably 250 or more.

[0086] In this embodiment, the upper limit of the oxygen content rate of the compound (A-b) having a benzyl ether skeleton is preferably 15% by mass or less, more preferably 13% by mass or less, and even more preferably 12% by mass or less. The lower limit of the oxygen content rate of the compound (A-b) having a benzyl ether skeleton is preferably 4% by mass or more, more preferably 5% by mass or more, and even more preferably 7% by mass or more.

[0087] In this embodiment, the upper limit of the specific gravity of the compound (A-b) having a benzyl ether skeleton is preferably less than 1.2, more preferably less than 1.15, and even more preferably less than 1.10. The lower limit of the specific gravity of the compound (A-b) having a benzyl ether skeleton is preferably 1.0 or more, more preferably 1.01 or more, and even more preferably 1.02 or more.

[0088] In this embodiment, the upper limit of the viscosity (75 ° C) of the compound (A-b) having a benzyl ether skeleton is preferably 1500 mPa·s or less, more preferably 1000 mPa·s or less, and even more preferably 900 mPa·s or less. The lower limit of the viscosity (75 ° C) of the compound (A-b) having a benzyl ether skeleton is preferably 30 mPa·s or more, more preferably 50 mPa·s or more, and even more preferably 70 mPa·s or more.

[0089] In this embodiment, the upper limit of the indirect viscosity (20 ° C, viscosity measured by diluting with toluene to a resin content of 80% by weight) of the compound (A-b) having a benzyl ether skeleton is preferably 1000 mPa·s or less, more preferably 800 mPa·s or less, and even more preferably 500 mPa·s or less. The lower limit of the indirect viscosity (20 ° C) of the compound (A-b) having a benzyl ether skeleton is preferably 10 mPa·s or more, more preferably 20 mPa·s or more, and even more preferably 30 mPa·s or more.

[0090] The hydroxyl value of the compound (A-b) having a benzyl ether skeleton in the present embodiment is preferably 16 to 50 (mgKOH / g), more preferably 18 to 40 (mgKOH / g), still more preferably 22 to 35 (mgKOH / g).

[0091] --Preferred form of the compound (A-b) having a benzyl ether skeleton-- An example of the compound (A-b) having a benzyl ether skeleton, which is the reaction raw material (1) of the polymaleimide resin (A) of the present disclosure, is preferably a compound having a structural unit represented by the following formula (7). [Chemical formula] [In the above general formula (7), 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.]

[0092] R in the general formula (7) above b1 preferably represents a hydrogen atom or a hydrocarbon group having 1 to 11 carbon atoms, more preferably represents 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 b1 is 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 above R b4 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Also, p1 to p3 and 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.

[0093] 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.

[0094] R in the general formula (7) above b2 and R b3Each independently corresponds to R in the general formula (1). 13 Therefore, R in the general formula (7) b2 and R b3 Preferably, each independently represents an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms, similar to the general formula (1). Further, when m b1 is an integer of 2 or more, two or more R b2 may be the same as each other or different groups. Similarly, when m b2 is an integer of 2 or more, two or more R b3 may be the same as each other or different groups.

[0095] In the general formula (7), L 1 Each 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 selected from the group consisting of 1 type. 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, even more preferably an integer of 1 to 3, and particularly preferably an integer of 1 to 2.

[0096] In the general formula (7) above, L 2 each 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 by -O- so as not to be adjacent to each other. Specifically, L 2 represents 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 these. 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.

[0097] 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.

[0098] Z 1 in the general formula (7) above 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.

[0099] In the above general formula (7), k is preferably an integer of 0 to 20, more preferably an integer of 0 to 15, and even more preferably an integer of 0 to 10. When k is 2 or more, a plurality of Ls 1 may be the same group as each other or different groups.

[0100] As a preferred form of the compound (A-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 (8). [Chemical formula] [In the above general formula (8), 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.]

[0101] In the above general formula (8), R b1 , R b2and R b3 、L 1 、L 2 、Z 1 、k, as well as m b1 and m b2 The preferred forms of are the same as the above general formula (7).

[0102] The compound (A-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 (A-b) having different benzyl ether skeletons.

[0103] For convenience of description in this specification, among the terms "compound (A-b) having a benzyl ether skeleton", a mixture containing two or more compounds (A-b) having different benzyl ether skeletons is referred to as a mixture (A-b) having a benzyl ether skeleton. Therefore, the "compound (A-b) having a benzyl ether skeleton" includes not only the case representing only one kind of compound, but also the mixture (A-b) having a benzyl ether skeleton.

[0104] In the mixture (A-b) having a benzyl ether skeleton of this embodiment, it is preferable that the component having the partial structure represented by the following general formula (9) occupies 95% by mass or more and 100% by mass or less of the whole mixture (A-b) having a benzyl ether skeleton. [Chemical formula] [In the above general formula (9), L 3 and L 4 are linking groups, and each independently is 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.]

[0105] The mixture (A-b) having a benzyl ether skeleton in this embodiment preferably has a component having a partial structure represented by the above general formula (9) accounting for 95% by mass or more and 100% by mass or less of the entire mixture (A-b) having a benzyl ether skeleton, and satisfies the following requirement (I) or (II). (I) The total number of linking groups (L 3 and L 4 ) per molecule constituting the component having a partial structure represented by the above general formula (9) 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 a partial structure represented by the above general formula (9) is 0.5 or more and 1.5 or less per molecule.

[0106] In this embodiment, as the linking groups (L 3 and L 4 ) of the molecule constituting the component having a partial structure represented by the above general formula (9), examples include one kind of group selected from the group consisting of -CH2-, -CH2O-CH2-, -(CH2O)2-CH2-, and -(CH2O)3-CH2-.

[0107] In the entire mixture (A-b) having a benzyl ether skeleton, the number of the following linking groups (L 3 and L 4 ) per molecule having a benzyl ether skeleton represented by the above general formula (9) preferably has the following composition (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, more preferably 0.09 or more and 0.6 or less, and even more preferably 0.10 or more and 0.55 or less.

[0108] In the mixture (A-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 general formula (9) above.

[0109] And in the whole mixture (A-b) having a benzyl ether skeleton, it is preferable that the benzyl ether skeleton is represented by the general formula (9) above, and the number of terminal groups per molecule is 0.5 or more and 1.5 or less.

[0110] In the whole mixture (A-b) having a benzyl ether skeleton, it is preferable that the number of the following terminal groups per molecule having a benzyl ether skeleton is in the following composition of (5) to (10). (5) The number of the terminal group “-CH2-OH” is preferably 0.17 or more and 0.4 or less, and more preferably 0.18 or more and 0.25 or less. (6) The number of the terminal group “-CH2O-CH3” is preferably 0.17 or more and 0.7 or less, and more preferably 0.18 or more and 0.44 or less. (7) The number of the terminal group “-(CH2O)2-CH3” is preferably 0.08 or more and 0.6 or less, and more preferably 0.09 or more and 0.3 or less. (8) The number of the terminal group “-(CH2O)3-CH3” is preferably substantially not contained, more preferably 0.3 or less, and even more preferably 0.2 or less. (9) The number of the terminal group “-(CH2O)-COH” is preferably 0 or more and 0.1 or less, and more preferably 0.01 or more and 0.1 or less.

[0111] In the mixture (A-b) having a benzyl ether skeleton according to this embodiment, the chemical structure and number of the linking groups, and the chemical structure and number of the terminal groups can be calculated from NMR as shown in the Examples section described later, or the catalog of the manufacturer can be referred to.

[0112] In this embodiment, the compound (A-b) having a benzyl ether skeleton may be a synthetic product or a commercially available product. As the compound (A-b) having a commercially available benzyl ether skeleton, for example, xylene resin (trade name: Nicanol (Y-50, Y-100, Y-300, Y-1000, LLL, LL, L or H)) manufactured by Fudo Co., Ltd. is preferable.

[0113] In this embodiment, it is preferable that the structural unit of the compound (A-b) having a benzyl ether skeleton is contained in an amount of 1 to 99% by mass, more preferably 5 to 95% by mass, based on the total amount (100% by mass) of the polyimide resin (A). The structural unit of the compound (A-b) having a benzyl ether skeleton refers to the group represented by the above general formula (1).

[0114] - maleic anhydride (A-c)- In this embodiment, maleic anhydride (A-c) is an essential component of the reaction raw material (1) of the polyimide 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 production method of the polyimide resin (A) described later.

[0115] In one embodiment of the first curable composition according to the present invention, the polyimide resin (A) is a polyimide resin having a partial structure represented by the following general formula (1A).

Chemical formula

Chemical formula

[0116] In one embodiment of the first curable composition according to the present invention, it is represented by the above general formula (1A), and n 1 and n 3 contains 10% by mass or more of a component whose sum is 1 or more.

[0117] In the general formula (1A), the preferred forms of R 11 , R 12 , R 13 , m 1 , m 2 and n 1 are the same as those in the above general formula (1). Further, in the general formula (4), the preferred forms of R 13 and m 2 are the same as those in the above general formula (1).

[0118] In the general formula (1A), the average number of repeating units n 2 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, from the viewpoint of the viscosity of the resulting polymaleimide resin.

[0119] In the general formula (4), the average number of repeating units n 3 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, from the viewpoint of the viscosity of the resulting polymaleimide resin.

[0120] ran indicates that the arrangement of each structural unit can be random. Therefore, the polymaleimide resin having the partial structure represented by the general formula (1A) may be any of a random copolymer, a block copolymer, and an alternating copolymer.

[0121] In one embodiment of the first curable composition according to the present invention, it is represented by the above general formula (1A), and n1 and n 3 Preferably contains 10% by mass or more, more preferably 15% by mass or more, and even more preferably 20% by mass or more of a component whose sum with n 2 is 1 or more. Also, from the viewpoint of heat resistance, it is desirable to contain 5% by mass or more, more preferably 7% by mass or more, and even more preferably 10% by mass or more of a component where n

[0122] <Physical properties of the polyimide resin (A)> The number average molecular weight (Mn) of the polyimide resin (A) of the present disclosure is preferably in the range of 200 to 1500, and more preferably in the range of 300 to 800. Also, the weight average molecular weight (Mw) of the polyimide resin (A) is preferably in the range of 280 to 2000, and more preferably in the range of 330 to 1200.

[0123] The polyimide resin (A) of the present disclosure is excellent in solvent solubility, heat resistance, and low dielectric constant. From this point, 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 even 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 proportion of high molecular weight components contributing to flexibility increases. Therefore, compared with cured products using conventional maleimide, brittleness is suppressed, and a cured product excellent in flexibility and softness can be obtained, which is a preferred embodiment.

[0124] 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 polyimide resin (A) of the present embodiment were measured under the measurement conditions described in the examples below using gel permeation chromatography (hereinafter abbreviated as "GPC").

[0125] The amount of the polymaleimide resin (A) in the curable composition may be adjusted as appropriate. For example, as the blending ratio (parts by mass) of the polymaleimide resin (A) and the cyanate ester (B), it is preferably 90:10 to 10:90 for the polymaleimide resin (A): cyanate ester (B), more preferably 85:15 to 15:85, and even more preferably 80:20 to 20:80. By adjusting the blending ratio within the above range, excellent low moisture absorption, low dielectric constant, and low dielectric tangent can be exhibited, which is preferable.

[0126] <Production Method of Polymaleimide Resin (A)> The production method of the polymaleimide resin (A) of the present embodiment is not particularly limited. As long as it has a partial structure represented by the above general formula (1), a partial structure represented by the above general formula (2) chemically bonded to the partial structure represented by the above general formula (1), and a partial structure represented by the above general formula (3) chemically bonded to the partial structure represented by the above general formula (1), it may be produced in any manner. As a preferred embodiment of the production method of the polymaleimide 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 (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c) as the reaction raw material (1). [Chemical formula] [In the above general formula (a-1), R a1 and R a2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 1 represents a hydrocarbon group having 1 to 18 carbon atoms, and R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]

[0127] As a specific embodiment of the production method of the polymaleimide resin (A) of the present disclosure, for example, a production method including the following steps (1) and (2) may be mentioned. Step (1): As reaction raw materials, an aromatic amine compound (A-a) represented by the above general formula (a-1) and a compound (A-b) having a benzyl ether skeleton are reacted to obtain an intermediate amine compound (I) in this embodiment; Step (2): As reaction raw material (3), the intermediate amine compound (I) obtained in the above step (1) and maleic anhydride (A-c) are reacted to obtain the polyimide resin (A) of the present disclosure.

[0128] Specifically, the method for producing the polyimide resin (A) of this embodiment includes a step (1) (also referred to as a cross-linking step) of reacting an aromatic amine compound (A-a) represented by the above general formula (a-1) and a compound (A-b) having a benzyl ether skeleton under a solid acid catalyst, and a step (2) (also referred to as a condensation step) of condensing the intermediate amine compound (I) generated in the step (1) and maleic anhydride (A-c). It is preferred to have these steps.

[0129] Hereinafter, each step of the method for producing the polyimide resin (A) of the present disclosure will be described in order.

[0130] <<Step (1): Production step of intermediate amine compound (I)>> Step (1) in this embodiment is not particularly limited. For example, the above-mentioned aromatic amine compound (A-a), the above-mentioned compound (A-b) having a benzyl ether skeleton (such as nicanol, etc.), and other compounds added as necessary are reacted in the presence of an acid catalyst. Thereby, the intermediate amine compound (I) can be generated.

[0131] Regarding the mixing ratio of the aromatic amine compound (A-a) and the compound (A-b) having a benzyl ether skeleton, considering the moldability and curability physical property balance during the production of the resulting cured product, the molar ratio of the compound (A-b) having a benzyl ether skeleton to 1 mol of the aromatic amine compound (A-a) is preferably 0.001 to 1 mol, and more preferably 0.1 to 0.5 mol.

[0132] When using a mixture such as the above-mentioned mixture (A-b) having a benzyl ether skeleton as the compound (A-b) having a benzyl ether skeleton, the reaction point with the aromatic amine compound (A-a) is the methyleneoxy moiety in the compound (A-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 mole of the total number of the above reaction points, the blending amount of the aromatic amine compound (A-a) is preferably 1 to 10 moles.

[0133] As a specific method for carrying out the above reaction, all the raw materials are charged at once and reacted at a predetermined temperature as it is, or one of the aromatic amine compound (A-a) or the compound (A-b) having a benzyl ether skeleton and an acid catalyst are charged, and while maintaining the temperature at a predetermined value, the other of the aromatic amine compound (A-a) or the compound (A-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 (I), and when no solvent is used, the unreacted substances are distilled off to obtain the target intermediate amine compound (I).

[0134] As the acid catalyst used in step (1) of this embodiment, any of organic acids, inorganic acids, or solid acids can be used.

[0135] 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.

[0136] Examples of the above-mentioned inorganic acids include phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid or boric acid.

[0137] 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.

[0138] 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.

[0139] Further, the above acid catalyst may be used alone or in combination of two or more.

[0140] 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.

[0141] Note that 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 hydrogen carbonates of alkali metals or alkaline earth metals such as sodium carbonate, potassium carbonate, sodium hydrogen carbonate, and potassium hydrogen carbonate; 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.

[0142] 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 (A-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.

[0143] The reaction temperature is usually in the range of 100 to 300 °C. However, in order to suppress the formation of isomer structures and avoid side reactions such as thermal decomposition, the range of 120 to 250 °C is preferable.

[0144] In step (1) of this embodiment, as the reaction time of the mixture of the compound (A-b) having a benzyl ether skeleton and the aromatic amine compound (A-a), that is, the crosslinking reaction time, if it is too short, the reaction will not proceed completely, and if it is too long, side reactions such as thermal decomposition reaction of the product will 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.

[0145] In the method for producing the intermediate amine compound (I) in this embodiment, since the aromatic amine compound (A-a) or its derivative also serves as a solvent, it is not necessarily necessary to use another solvent, but it is also possible to use a solvent. For example, when reacting nicanol L as the compound (A-b) having a benzyl ether skeleton as a raw material, an azeotropic dehydration solvent such as toluene, xylene, or chlorobenzene can be used to azeotropically dehydrate the water contained in the catalyst or the like as necessary, and then the solvent is distilled off, and then the reaction is carried out in the above reaction temperature range.

[0146] The intermediate amine compound (I) 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 (10) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the general formula (11) chemically bonded to the partial structure represented by the general formula (1). [In the above general formula (1), each R independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 13 represents an integer of 0 or more and 4 or less, n 2 represents the average number of repeating units, two * each represent a bond, one bond is chemically bonded at the position of L 1 or L 13 in the following general formula (10), and the other bond is chemically bonded at the position of L 14 or L 11 in the following general formula (11).] 12

Chemical formula

[0147] "R 13 , m 2 and n 1 " in the general formula (1) above has the same meaning as "R 13 , m 2 and n 1 " in the general formula (1) described above. Also, "L 11 , L 12 , L 13 , L 13 , R 11 , R 12 , R 14 , R 15 , m 1 and m 3 " in the general formulas (10) and (11) has the same meaning as "L 11 , L 12 , L 13 , L 13 , R 11 , R 12 , R 14 , R 15 , m 1 and m 3 " in the general formulas (2) and (3).

[0148] In this embodiment, the amine equivalent of the intermediate amine compound (I) is preferably 160 to 1200 g / equivalent, more preferably 180 to 600 g / equivalent. The measurement of the amine equivalent of the intermediate amine compound (I) in this specification is the value measured by a method based on the neutralization titration method specified in JIS K 0070 (1992).

[0149] <<Step (2): Maleimidation>> Step (2) in this embodiment is a step of reacting the intermediate amine compound (I) obtained in step (1) with maleic anhydride (A-c). Since the amino group of the intermediate amine compound (I) 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.

[0150] In this embodiment, the intermediate amine compound (I) having the partial structure represented by the general formula (1), the partial structure represented by the general formula (10), and the partial structure represented by the general formula (11), obtained in step (1), is charged into a reactor, dissolved in an appropriate solvent, and then reacted with maleic anhydride (A-c) in the presence of a catalyst. After the reaction, unreacted maleic anhydride (A-c) or other impurities are removed by washing with water or the like, and the solvent is removed under reduced pressure to obtain the target polymaleimide resin (A). Further, a dehydrating agent may be used during the reaction if necessary.

[0151] 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.

[0152] In step (2) of this embodiment, as the mixing ratio of the intermediate amine compound (I) and maleic anhydride (A-c), it is preferable to blend the equivalent ratio of maleic anhydride (A-c) to the amino equivalent of the intermediate amine compound (I) in the range of 1 to 5, more preferably charge at 1 to 3, and react in an organic solvent having a mass ratio of 0.1 to 10, preferably 0.2 to 5, based on the total amount of the intermediate amine compound (I) and maleic anhydride (A-c).

[0153] As the catalyst that can be used in step (2) of this embodiment, there can be mentioned inorganic salts such as acetates, chlorides, bromides, sulfates, nitrates of nickel, cobalt, sodium, calcium, iron, lithium, manganese, etc., inorganic acids such as phosphoric acid, hydrochloric acid, sulfuric acid, 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, heteropoly hydrochloric acid, etc., and particularly toluenesulfonic acid is preferably used.

[0154] As the dehydrating agent used in step (2) of this embodiment, there can be mentioned 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, porous ceramics such as molecular sieves, etc., and preferably acetic anhydride can be used.

[0155] There is no particular limitation on the amount of the catalyst and dehydrating agent used in step (2) of this embodiment, but usually, per 1 equivalent of the amino group (-NH2) of the intermediate amine compound (I), the catalyst can be used in an amount of 0.0001 to 1 mol, preferably 0.01 to 0.3 mol, and the dehydrating agent can be used in an amount of 1 to 3 mol, preferably 1 to 1.5 mol.

[0156] In step (2) of the present embodiment, as the reaction conditions for maleimidation, the above intermediate amine compound (I) and maleic anhydride (A-c) are charged, and the reaction is carried out at a temperature range of 10 to 100°C, preferably 30 to 60°C, for 0.5 to 12 hours, preferably 1 to 4 hours. Then, the catalyst is added and the reaction is carried out at a temperature range of 90 to 130°C, preferably 105 to 120°C, for 1 to 24 hours, preferably 1 to 10 hours.

[0157] · Cyanate ester (B) The curable composition of the present disclosure contains a cyanate ester (B) in addition to the polymaleimide resin (A). Since the cyanate ester (B) is excellent in dielectric properties such as dielectric constant or dielectric tangent, a cured product that exhibits a sufficiently low dielectric tangent while maintaining a sufficiently low dielectric constant can be obtained even in a high-frequency band (high-frequency region) from the MHz band to the GHz band. Therefore, 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, so that a cured product excellent in heat resistance, low thermal expansion, adhesion, and further mechanical properties or chemical resistance can be obtained, which is a preferable embodiment.

[0158] The cyanate ester (B) of this embodiment can be a compound having one or more cyanate groups (cyanic acid ester: -O-C≡N). Examples of the cyanate ester (B) 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. Among the cyanate esters (B), bisphenol A type cyanate ester resin, bisphenol F type cyanate ester resin, bisphenol E type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, naphthylene ether type cyanate ester resin, and novolac type cyanate ester resin are preferably used in terms of obtaining a cured product having particularly excellent heat resistance, and dicyclopentadiene-phenol addition reaction type cyanate ester resin is preferable in terms of obtaining a cured product having excellent dielectric properties.

[0159] In the curable composition of the present embodiment, it is preferable to contain 5% by mass or more and 60% by mass or less of the cyanate ester (B) with respect to the whole curable composition, more preferably 10% by mass or more and 50% by mass or less, still more preferably 12% by mass or more and 45% by mass or less, particularly preferably 15% by mass or more and 40% by mass or less, and most preferably 20% by mass or more and 30% by mass or less. When the content of the cyanate ester (B) is in the range of 20% by mass or more and 30% by mass or less, it is preferable from the viewpoint of heat resistance.

[0160] (Hardening agent (D) other than cyanate ester (B)) In the curable composition of the present embodiment, a hardening agent (D) other than the cyanate ester (B) can also be added within a range not impairing the hardening of the present invention. Incidentally, with respect to 100% by mass of the total amount of the curable composition, the hardening agent (D) is preferably 2% by mass or more and 20% by mass or less, and most preferably 5% by mass or more and 10% by mass or less. When the content of the hardening agent (D) is in the range of 5% by mass or more and 10% by mass or less, it is preferable from the viewpoints of curability and low dielectric tangent.

[0161] Examples of the hardening agent (D) of the present embodiment include amine compounds, amide compounds, acid anhydride compounds, phenol compounds, polyphenylene ether compounds, compounds having an unsaturated double bond-containing substituent, diene polymers, and the like. These hardening agents may be used alone or in combination of two or more.

[0162] Examples of the above amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivatives, and the like.

[0163] Examples of the above amide compounds include dicyandiamide, polyamide resins synthesized from dimers of linolenic acid and ethylenediamine, and the like.

[0164] 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.

[0165] Examples of the phenolic compound include phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zylock resin), polyhydric phenol novolak resin synthesized from polyhydric hydroxy compounds typified by resorcinol novolak resin and formaldehyde, 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 (polyhydric phenol compound in which phenol nuclei are linked by bismethylene groups), biphenyl-modified naphthol resin (polyhydric naphthol compound in which phenol nuclei are linked by bismethylene groups), aminotriazine-modified phenol resin (polyhydric phenol compound in which phenol nuclei are linked by melamine, benzoguanamine, etc.), alkoxy group-containing aromatic ring-modified novolak resin (polyhydric phenol compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked by formaldehyde), and other polyhydric phenol compounds.

[0166] The polyphenylene ether compound preferably has a structure represented by the following general formula (12) or (13).

Chemical formula

Chemical formula

[0167] In the general formulas (12) and (13), R d1 ~R d8Each is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a thioether group having 1 to 5 carbon atoms, an alkylcarbonyl group having 2 to 5 carbon atoms, an alkyloxycarbonyl group having 2 to 5 carbon atoms, an alkylcarbonyloxy group having 2 to 5 carbon atoms, an alkylsulfonyl group having 1 to 5 carbon atoms, etc. Examples of the terminal structure of the structures represented by the general formulas (12) and (13) include those having a hydroxyl group or a reactive double bond-containing group. Further, v is an integer value of 1 to 30, and w and u are also integer values of 1 to 30.

[0168] 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.

[0169] 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.

[0170] 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, etc.

[0171] 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, etc.

[0172] 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, etc.

[0173] In this embodiment, R in the general formulas (12) and (13) 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.

[0174] Y in the general formula (13) includes a divalent aromatic group derived from an aromatic compound having two phenolic hydroxyl groups. The aromatic compound having two phenolic hydroxyl groups is not particularly limited, and examples thereof include catechol, resorcinol, hydroquinone, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol B, bisphenol BP, bisphenol C, bisphenol F, and tetramethyl bisphenol A. Among these, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol E, and bisphenol F are preferable, and 4,4'-biphenol, bisphenol A, and tetramethyl bisphenol A are more preferable. 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 group derived from an aromatic compound having two phenolic hydroxyl groups. In other words, a group obtained by removing any two hydrogen atoms from the aromatic compound having two phenolic hydroxyl groups is defined as a "divalent aromatic group derived from an aromatic compound having two phenolic hydroxyl groups".

[0175] Examples of the compound having the unsaturated double bond-containing substituent include, but are not particularly limited to, compounds having two or more unsaturated bond-containing substituents in the molecule. Examples of the unsaturated bond-containing substituent include compounds having an allyl group, an isopropenyl group, a 1-propenyl group, an acryloyl group, a methacryloyl group, a styryl group, a styrylmethyl group, and the like.

[0176] Examples of the diene polymer include non-modified diene polymers that are 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, an epoxy group, and the like. The diene polymer is not particularly limited, and for example, 1,2-polybutadiene, 1,4-polybutadiene, or the like can be used.

[0177] As the diene 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.

[0178] (Other resin (E)) In addition, as long as the object of the present disclosure is not impaired, other resins (E) may be contained in addition to the polyimide resin (A) and the cyanate ester (B). Examples of the other resin (E) include bismaleimides other than the polyimide resin (A), allyl ether compounds, allylamine compounds, triallyl cyanurate, alkenylphenol compounds, vinyl group-containing polyolefin compounds, etc., epoxy resins, phenol resins, active ester resins, polyphenylene ether resins, benzoxazine resins, styrene maleic anhydride copolymers, polybutadiene and its modified products, polyacetal resins, polyvinyl alcohol resins, liquid crystal polymers, fluororesins, polystyrene, polyethylene, polyimide resins, thermosetting polyimide resins, silicone gels, silicone oils, etc. can be appropriately blended. The content of the other resin (E) is preferably 2% by mass or more and 20% by mass or less, and most preferably 5% by mass or more and 10% by mass or less, based on 100% by mass of the total amount of the curable composition. When the content of the other resin (E) is in the range of 5% by mass or more and 10% by mass or less, it is preferable from the viewpoints of heat resistance and compatibility.

[0179] (Curing accelerator) The curable composition of the present embodiment can also be appropriately used in combination with a curing accelerator as needed. Although various materials can be used as the curing accelerator, since the cyanate ester (B) is used, for example, phenols, amines, Lewis acids, tertiary sulfonium salts, quaternary ammonium salts, quaternary phosphonium salts, epoxy group-containing compounds, etc. can be mentioned. Among these, nonylphenol, 2,4,6-tris(dimethylaminomethyl)phenol, carboxylic acid salts of copper, lead, tin, manganese, nickel, iron, zinc, cobalt, etc., titanium tetra-n-butoxide and its polymer, pentadionate salts of copper, nickel, cobalt, etc., tetrabutylammonium bromide, tetrabutylphosphonium chloride, tetraphenylphosphonium tetra(methylphenyl)borate, zinc octylate, etc. can be used. Further, the curing accelerator is preferably highly compatible with the cyanate ester (B) and allows the curing reaction to proceed smoothly. Furthermore, among these, tetraphenylphosphonium tetra(methylphenyl)borate is particularly preferred. By using tetraphenylphosphonium tetra(methylphenyl)borate as the curing accelerator, the curing reaction proceeds faster than other materials, which is preferable. Also, the addition amount of the curing accelerator is preferably, for example, 0.001 to 1.00 parts by mass with respect to 100 parts by mass of the cyanate ester (B).

[0180] (Additive) The curable composition of the present embodiment can also be appropriately used in combination with additives as needed. Examples of the additives include silane coupling agents, mold release agents, pigments, emulsifiers, non-halogen flame retardants, inorganic fillers, flame retardants, solvents, etc. The content of the additives is preferably 1% by mass or more and 20% by mass or less, and most preferably 3% by mass or more and 10% by mass or less with respect to 100% by mass of the total amount of the curable composition.

[0181] Examples of the flame retardant include inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, halogen-based flame retardants, or non-halogen-based flame retardants. In the curable composition of the present embodiment, in a range not impairing the object, it is more preferable to blend a non-halogen-based flame retardant that substantially does not contain a halogen atom in order to exhibit flame retardancy. Examples of the non-halogen-based flame retardant include phosphorus-based flame retardants, nitrogen-based flame retardants, silicone-based flame retardants, inorganic-based flame retardants, organic metal salt-based flame retardants, etc., and these can be used alone or in combination.

[0182] An inorganic filler can be blended in the curable composition of the present embodiment as needed. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, etc. When the blending amount of the inorganic filler is particularly increased, it is preferable to use fused silica. The fused silica can be used in either a crushed form or a spherical form, but in order to increase the blending amount of the fused silica and suppress the increase in the melt viscosity of the molding material, it is preferable to mainly use spherical ones. Further, in order to increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica. The filling rate is preferably high in consideration of flame retardancy, and particularly preferably 30% by mass or more and 50% by mass or less with respect to the total amount of the curable composition. Further, when the curable composition is used for applications such as conductive paste described in detail below, a conductive filler such as silver powder or copper powder can be used.

[0183] In the curable composition of the present embodiment, the lower limit of the total content of the polyimide resin (A) and the cyanate ester (B) is preferably 40% by mass, 42% by mass, 45% by mass, 47% by mass, 48% by mass, or 50% by mass with respect to the entire curable composition (100% by mass). Further, 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, the total content of the polyimide resin (A) and the cyanate ester (B) is preferably 40% by mass or more and 100% by mass or less with respect to the entire curable composition (100% by mass), more preferably 45% by mass or more and 100% by mass or less, and even more preferably 50% by mass or more and 100% by mass or less. In the curable composition of the present embodiment, the lower limit of the total content of the polyimide resin (A), the cyanate ester (B), the inorganic filler, and the additive is preferably 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 above upper limit value and the above lower limit value can be arbitrarily combined in the same manner as the range of the total content of the polyimide resin (A) and the cyanate ester (B). In the curable composition of the present embodiment, the lower limit of the total content of the polyimide resin (A), the cyanate ester (B), and the additive is preferably 43% by mass, 45% by mass, 48% by mass, 50% by mass, or 53% by mass with respect to the entire curable composition (100% by mass). Further, the upper limit of the total content is preferably 100% by mass, 99% by mass, 98% by mass, or 97% by mass. The above upper limit value and the above lower limit value can be arbitrarily combined in the same manner as the range of the total content of the polyimide resin (A) and the cyanate ester (B).

[0184] (Second curable composition) The second curable composition according to the present invention contains a polyimide resin component having a partial structural unit represented by the following general formula (1a), and a maleimide multimer compound represented by the following general formula (5), and a maleimide resin mixture (C). a cyanate ester (B), and the maleimide resin mixture (C) contains 1 to 99% by mass of a polyimide resin (A) having a partial structure represented by the following general formula (1), a partial structure represented by the following general formula (2) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (3) chemically bonded to the partial structure represented by the general formula (1), based on the total amount of the polyimide resin component, and contains 80% by mass or less of the maleimide multimer compound based on the total amount of the maleimide resin mixture (C). [Chemical formula] [In the above general formula (1a), R 11 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 represents a hydrocarbon group having 1 to 18 carbon atoms, R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 1 represents 2, m 2 represents an integer of 0 or more and 4 or less, and n 1 represents the average number of repeating units.] [Chemical formula] [In the above general formula (5), R 21 and R 25 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 22 and R 24 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 21 represents 2, m 23 represents 3, and n 21 represents an integer of 1 or more and 5 or less.] [Chemical formula] [In the above general formula (1), R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 2 represents an integer of 0 or more and 4 or less, n 1 represents the average number of repeating units, and the two * each represent a bond. One bond is L in the following general formula (2) 13 or L 14 and is chemically bonded at the position, and the other bond is L in the following general formula (3) 11 or L 12 and is chemically bonded at the position.] [Chemical formula] [In the above general formula (2) or (3), R 11 and R 15 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 and R 14 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, L 11 to L 14 each independently represent a bond or a hydrogen atom, provided that L 11 or L 12 is chemically bonded to the partial structure represented by the general formula (1) at the position, 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.]

[0185] ·Maleimide resin mixture (C) The polyimide resin (A) of this embodiment may be a mixture. For example, when using, as the polyimide resin (A), a resin having as reaction raw materials (1) an aromatic amine compound (A-a) represented by the above general formula (a-1), a compound (A-b) having the above benzyl ether skeleton, and maleic anhydride (A-c), since there are a plurality of reaction points of the compound (A-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 (I) itself can be a mixture in which a plurality 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 both a single substance and a mixture. On the other hand, it is referred to as a maleimide resin mixture (C) only when the polyimide resin (A) means only a mixture. The maleimide resin mixture (C) contains a polyimide resin component having a partial structural unit represented by the general formula (1a) and a maleimide multimer compound represented by the following general formula (5).

[0186] (Maleimide resin component) "R 11 , R 12 , R 13 , n 1 , m 1 and m 2 " in the above general formula (1a) is synonymous with "R 11 , R 12 , R 13 , n 1 , m 1 and m 2 " in the general formula (1) or general formula (2) described above.

[0187] (Maleimide multimer compound) Also, "R 21 and R 25 " in the general formula (5) are each independently synonymous with "R 11 or R 15 " in the general formula (2) and general formula (3). "R 22 and R 24" is independently synonymous with "R" in General Formula (2) and General Formula (3). 12 or R 14 ".

[0188] The amount of the maleimide multimer compound in the maleimide resin mixture (C) is 80% by mass or less.

[0189] The polymaleimide resin (A) contained in the polymaleimide resin component having the partial structural unit represented by General Formula (1a) is the same as the polymaleimide resin (A) described in the first curable composition.

[0190] In one embodiment of the second curable composition according to the present invention, the polymaleimide resin (A) uses an aromatic amine compound (A-a) represented by General Formula (a-1), a compound (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c) as reaction raw materials (1). The aromatic amine compound (A-a), the compound (A-b) having a benzyl ether skeleton, maleic anhydride (A-c), and the reaction raw materials (1) are the same as the polymaleimide resin (A) described in the first curable composition.

[0191] The amount of the polymaleimide resin (A) in the maleimide resin mixture (C) is 1 to 99% by mass based on the total amount of the maleimide resin component.

[0192] In the maleimide resin mixture (C) of the present embodiment, with respect to the total amount of the maleimide resin components, a polymaleimide resin (A) having a partial structure represented by the general formula (1), a partial structure represented by the following general formula (2) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (3) chemically bonded to the partial structure represented by the general formula (1) is preferably contained in an amount of 10% by mass to 99% by mass, more preferably 15% by mass or more to 98% by mass, still more preferably 20% by mass to 97% by mass. And, with respect to the total amount of the maleimide resin mixture (C), the maleimide multimer compound represented by the general formula (5) is preferably contained in an amount of 5% by mass to 80% by mass or less, more preferably 7% by mass to 80% by mass or less, still more preferably 10% by mass or more to 80% by mass or less.

[0193] As a preferred maleimide resin mixture (C) of the present embodiment, it contains a polymaleimide resin represented by the general formula (1A) (however, in the general formula (1A), a polymaleimide resin in which n1 is 1 or more) and a maleimide multimer compound represented by the general formula (2). With respect to the maleimide resin mixture (C), the content of the polymaleimide resin represented by the general formula (1A) (however, in the general formula (1A), a 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, still more preferably 20% by mass to 97% by mass. With respect to the maleimide resin mixture (C), the content of the maleimide multimer compound represented by the general formula (5) is preferably 5% by mass to 80% by mass, more preferably 7% by mass to 80% by mass, still more preferably 10% by mass or more to 80% by mass.

[0194] Another preferred maleimide resin mixture (C) 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 an aromatic amine compound (A-a) represented by the general formula (a-1), a compound (A-b) having the benzyl ether skeleton, and maleic anhydride (A-c) as reaction raw materials (1). The reaction raw material (1) may be formulated with the aromatic amine compound (A-a) represented by the general formula (a-1), preferably 5 to 98% by mass, more preferably 10 to 95% by mass, still more preferably 15 to 90% by mass, the compound (A-b) having a benzyl ether skeleton, preferably 1 to 90% by mass, more preferably 2 to 85% by mass, still more preferably 3 to 80% by mass, and maleic anhydride (A-c), preferably 2 to 90% by mass, more preferably 3 to 85% by mass, still more preferably 4 to 80% by mass.

[0195] [Preparation of curable composition] Since the polyimide resin (A) of this embodiment is excellent in solvent solubility, dielectric loss tangent and heat resistance, and can further contribute to fluidity, handleability, dimensional stability, low hygroscopicity, brittleness resistance, and low dielectric constant during heat melting, the cured product obtained from the curable composition containing the polyimide resin (A) is excellent in solvent solubility, dielectric properties and heat resistance.

[0196] The second curable composition may contain a curing agent (D) other than the cyanate ester (B), another resin (E), and a curing accelerator, which are the same as those described for the first curable composition. The second curable composition can further appropriately use additives in combination as needed. The additives are the same as those described for the first curable composition. The content of the additives is preferably 1% by mass or more and 20% by mass or less, and most preferably 3% by mass or more and 10% by mass or less based on 100% by mass of the total amount of the curable composition.

[0197] [Cured product] The cured product of this embodiment is preferably obtained by the above-described curable composition. The cured product can be obtained by subjecting the curable composition to a curing reaction. The curable composition is obtained by uniformly mixing the above-described respective components (for example, curing agent, compounding agent), and can be easily made into a cured product by the same method as a conventionally known method. Examples of the cured product include molded cured products such as laminates, castings, adhesive layers, coating films, and films. As the above-mentioned curing (thermosetting) reaction can be easily carried out even without a catalyst, when it is desired to make the reaction proceed even faster, the addition of polymerization initiators such as organic peroxides and azo compounds, and basic catalysts such as phosphine-based compounds and tertiary amines is effective. For example, there are benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazoles, etc. As the compounding amount, 0.05 to 5% by mass of the entire curable resin composition is preferable.

[0198] Since the cured product obtained from the curable composition containing the polymaleimide resin (A) and the cyanate ester (B) has both excellent low moisture absorption and low dielectric properties, it can be suitably used for heat-resistant members or electronic members. In particular, it can be suitably used for prepregs, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up boards, adhesives using conductive pastes, resist materials, etc. Further, it can also be suitably used as a matrix resin for fiber-reinforced resins, and is particularly suitable as a prepreg having high heat resistance or a small dimensional change rate. Further, since the polymaleimide resin (A) contained in the curable composition exhibits excellent solubility in various solvents, it can be made into a paint. The heat-resistant members and electronic members thus obtained can be suitably used for various applications, and examples include industrial machine parts, general machine parts, parts of automobiles, railways, vehicles, etc., space and aviation-related parts, electronic and electrical parts, building materials, container and packaging members, daily necessities, sports and leisure goods, housing members for wind power generation, etc., but are not limited thereto.

[0199] Hereinafter, examples will be given and explained for typical products (prepregs, circuit boards, build-up boards, build-up films, semiconductor encapsulants, semiconductor devices, conductive pastes) manufactured using the curable composition of the present embodiment.

[0200] <Prepreg> The prepreg of the present embodiment has 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 curable composition, an organic solvent described later is blended to form a varnished curable composition, which is impregnated into a reinforcing base material (such as paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, etc.), and then heated at a heating temperature corresponding to the type of solvent used, preferably 50 to 170 °C, to semi-cure (or uncure) the curable composition to obtain a prepreg. The mass ratio of the curable composition to the reinforcing base material used at this time is not particularly limited, but usually, it is preferably prepared so that the resin content contained in the composition in the prepreg is 20 to 60% by mass. In the present embodiment, the semi-cured product of the curable composition is obtained by adjusting the heating temperature and heating time to stop the curing reaction halfway without completing it. Also, for example, the semi-cured product can have a degree of cure 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 degree of cure than the semi-cured product. Note that the degree of cure 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 by DSC. Degree of cure (%) = [1 - (Heat of curing of semi-cured product / Heat of curing of curable composition)] × 100

[0201] Examples of the organic solvent used in the production of the prepreg of the present embodiment include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. The selection and appropriate usage amount thereof can be appropriately selected according to 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 less, such as methyl ethyl ketone, acetone, dimethylformamide, etc., and it is also preferable to use it in a ratio such that the non-volatile content is 40 to 80% by mass. In addition, as the reinforcing base material used in the production of the prepreg of the present embodiment, there are woven fabrics and non-woven fabrics made of inorganic fibers such as glass fibers, polyester fibers, and polyamide fibers, organic fibers, or mats, paper, etc., and these can be used alone or in combination.

[0202] The heat treatment conditions of the prepreg of the present embodiment are appropriately selected according to the type and amount of the organic solvent, catalyst, various additives used, etc., but usually, it is preferably carried out under the conditions of a temperature of 80 to 220°C for 3 minutes to 30 minutes.

[0203] <Circuit board> The circuit board of the present embodiment is a laminate having the above-mentioned prepreg and copper foil. As a method for obtaining a printed circuit board from the curable composition of the above-mentioned present embodiment, there is a method of laminating the above prepreg by a conventional method, appropriately laminating copper foil, and heating and pressure-bonding at 170 to 300°C for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.

[0204] <Build-up board> As a method for obtaining a build-up board from the curable composition of the present embodiment, there is a method that passes through the following steps 1 to 3. In step 1, first, the curable composition appropriately blended with rubber, filler, etc. is applied to the circuit board on which a circuit is formed using a spray coating method, a curtain coating method, etc., and then cured. In step 2, if necessary, after making holes such as a predetermined through-hole part in the circuit board coated with the curable composition, treating it with a roughening agent, and rinsing its surface with hot water, unevenness is formed 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 insulating layer and a conductor layer of a predetermined circuit pattern to form a build-up board. In addition, in the above process, the drilling of the through-hole 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 obtained by semi-curing the composition on a copper foil is heat-pressed onto a wiring substrate on which a circuit is formed at 170 to 300 °C, thereby forming a roughened surface and omitting the plating process, and it is also possible to produce a build-up substrate.

[0205] <Build-up film> The build-up film of the present embodiment contains the curable composition of the above-described present embodiment. As a method for manufacturing the build-up film of the present embodiment, the curable composition is applied onto a support film (Y) and then dried to form a curable composition layer on the support film (Y) to obtain an adhesive film for a multilayer printed wiring board.

[0206] When manufacturing a build-up film from a curable composition, the film softens under the temperature conditions of lamination in the vacuum lamination method (usually 70 to 140 °C), and it is important that the film exhibits fluidity (resin flow) that enables resin filling in the via holes or through-holes present in the circuit board simultaneously with the lamination of the circuit board. It is preferable to blend the above components so as to exhibit such characteristics. In addition, in the obtained build-up film and circuit board (copper-clad laminate, etc.), in order to avoid a phenomenon in which locally different characteristic values are exhibited due to phase separation or the like and to exhibit a certain performance at any site, appearance uniformity is required.

[0207] Here, the diameter of the through-hole of 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-hole be filled to about half its depth.

[0208] The method for manufacturing the above-described adhesive film specifically comprises: after preparing the varnish-like curable composition, applying this varnish-like composition onto the surface of the support film (Y), and further drying the organic solvent by heating, hot air blowing, or the like to form a composition layer (X) composed of the curable composition. As the organic solvent, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate; carbitols such as cellosolve, butyl carbitol; aromatic hydrocarbons such as toluene, xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and it is also preferably used at a ratio such that the non-volatile content is 30 to 60% by mass.

[0209] The thickness of the formed composition layer (X) is usually preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the resin composition layer preferably has a thickness of 10 to 100 μm. 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.

[0210] Examples of the above-described support film (Y) and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate; polycarbonate, polyimide; and further metal foils such as release paper, copper foil, and aluminum foil. Note that the support film and the protective film may be subjected to matting treatment, corona treatment, or release treatment in addition to these. The thickness of the support film is not particularly limited, but it is usually 10 to 150 μm, and preferably used in the range of 25 to 50 μm. Also, the thickness of the protective film is preferably 1 to 40 μm.

[0211] The above-mentioned support film (Y) is peeled off after being laminated on the circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the adhesive film is heat cured, it is possible to prevent the adhesion of dust and the like during the curing process. When peeling off after curing, usually, the support film is subjected to a release treatment in advance. In addition, a multilayer printed circuit board can be manufactured from the build-up film obtained as described above. For example, when the resin composition layer (X) is protected by a protective film, after peeling these, the layer (X) of the resin composition is laminated on one or both sides of the circuit board so as to be directly in contact with the circuit board, for example, by a vacuum lamination method. The lamination method may be a batch type or a continuous type using a roll. 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, and a crimping pressure of 1 to 11 kgf / cm 2 (9.8×10 4 ~107.9×10 4 N / m 2 ), and it is preferable to laminate under a reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

[0212] <Semiconductor encapsulant> The semiconductor encapsulant of the present embodiment contains the curable composition of the present embodiment described above. The semiconductor encapsulant obtained by using the curable composition of the present embodiment has reduced hygroscopicity, dielectric constant, and dielectric tangent by using the polymaleimide resin (A) and the cyanate ester (B), and thus is excellent in processability, moldability, and reflow resistance in the manufacturing process, which is a preferable aspect.

[0213] The curable composition of the present embodiment used for the semiconductor encapsulant can contain an inorganic filler. As the filling rate of the inorganic filler, for example, the inorganic filler can be used in the range of 0.5 to 1200 parts by mass with respect to 100 parts by mass of the curable composition of the present embodiment. Further, as the inorganic filler, as described above, for example, barium sulfate, barium titanate, amorphous silica, crystalline silica, noble silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, etc. can be mentioned.

[0214] As a method for obtaining the semiconductor encapsulant, to the curable composition of the present embodiment, a curing accelerator and / or an additive, which are optional components, are added as necessary, and melt-mixed uniformly using an extruder, kneader, roll, etc. until it becomes uniform. When used as a high thermal conductivity semiconductor encapsulant for power transistors and power ICs, it is preferable to use highly filled crystalline silica, alumina, silicon nitride, etc., which have a higher thermal conductivity than fused silica, or fused silica, crystalline silica, alumina, silicon nitride, etc. 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.

[0215] <Semiconductor device> The semiconductor device of the present embodiment includes a cured product of the above-described semiconductor encapsulant. The semiconductor device obtained by using the semiconductor encapsulant obtained by using the curable composition of the present embodiment uses the polymaleimide resin (A) and the cyanate ester (B), so it has a low viscosity and excellent fluidity. Furthermore, since its hygroscopicity, elastic modulus at high temperature, or adhesiveness to a metal material is improved, it is excellent in processability, moldability, and reflow resistance in the manufacturing process, which is a preferable aspect.

[0216] 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 thermosetting it in a temperature range of room temperature (20°C) to 250°C.

[0217] <Conductive paste> As a method for obtaining a conductive paste from the curable composition of the present embodiment, 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

[0218] 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 were measured as follows and are shown in Table 1 and Table 2.

[0219] (1) Measurement of GPC Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation, Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation Measurement conditions: Column temperature 40°C Developing solvent: Tetrahydrofuran Flow rate: 1.0 ml / min Standard: In accordance with the measurement manual of the "GPC Workstation EcoSEC-WorkStation", the following monodisperse polystyrene with a known molecular weight was used. (Using polystyrene) "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 in terms of resin solid content, filtered through a microfilter (50 μL).

[0220] (2) Amine equivalent and maleimide group equivalent The amine equivalent of the aromatic amine obtained in the synthesis example was measured by the following method. Approximately 2.5 g of aromatic amine, 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine were accurately weighed into a 500 mL Erlenmeyer flask with a stopper. After attaching a condenser, the mixture was heated under reflux for 150 minutes in an oil bath set at 120 °C. After cooling, 5.0 mL of distilled water, 100 mL of propylene glycol monomethyl ether, and 75 mL of tetrahydrofuran were added, and titration was performed by potentiometric titration with a 0.5 mol / L potassium hydroxide-ethanol solution. A blank test was conducted in the same manner for correction. Amine equivalent (g / equivalent) = (S × 2,000) / (Blank - A) S: Amount of sample (g) A: Consumption of 0.5 mol / L potassium hydroxide-ethanol solution (mL) Blank: Consumption of 0.5 mol / L potassium hydroxide-ethanol solution in the blank test (mL) The maleimide group equivalent of the polymaleimide resin obtained in the synthesis example is a value converted from the amine equivalent of the intermediate amine compound and is calculated by the following formula. Maleimide equivalent (g / equivalent) = amine equivalent + 80

[0221] (3) FD-MS measurement The FD-MS spectrum of the polymaleimide resin obtained in the synthesis example was measured using the following measuring apparatus and measuring conditions. · Measuring apparatus: JMS-T100GC AccuTOF · Measuring conditions Measurement range: m / z = 4.00 to 2000.00 Rate of change: 51.2 mA / min Final current value: 45 mA Cathode voltage: -10 kV Recording interval: 0.07 sec

[0222] (4) 13 13C-NMR measurement The 13 13C-NMR spectrum of the polymaleimide resin obtained in the synthesis example was measured under the following measuring apparatus and measuring conditions. · 13 13C-NMR: "JNM-ECZ400S" manufactured by JEOL RESONANCE Resonance frequency: 100 MHz Number of integrations: 4000 times Solvent: chloroform-d Sample concentration: 12 mass% Relaxation reagent: chromium(III) acetylacetonate

[0223] The materials and apparatuses used in the synthesis examples and examples are as follows. Xylene formalin resin: manufactured by Fudo Co., Ltd., product name "Nikanol L" Comparative maleimide resin (A-2): 4,4'-diphenylmethane bismaleimide, BMI-1000, manufactured by Daiwa Kasei Kogyo Co., Ltd. Cyanate ester (B): 2,2-bis(4-cyanatophenyl)propane, manufactured by Tokyo Chemical Industry Co., Ltd. Curing catalyst: tetraphenylphosphonium tetra-p-tolyl borate, manufactured by Hokko Chemical Industry Co., Ltd., product name "TPP-MK (registered trademark)" Network Analyzer: Manufactured by Agilent Technologies, product name "E8362C"

[0224] [Synthesis Example 1] Synthesis of maleimide resin (A-1) (1) Synthesis of intermediate amine To 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, 240 g of toluene and 133.7 g of activated clay were added. The mixture was heated to 120 °C with stirring and held for 30 minutes. Then, it was heated to 160 °C and held for 4 hours. Next, it was heated to 200 °C over 60 minutes and held for 15 hours. Then, the mixture was diluted with 240 g of toluene, and the activated clay was filtered off by filtration. The filtrate was heated under reduced pressure to distill off the solvent and excess 2,3-dimethylaniline to obtain an intermediate aromatic amine resin (a-1) (amine equivalent: 218 g / equivalent). The obtained amine resin's 13 13C-NMR spectrum and FD-MS spectrum are shown in FIGS. 1 and 2, respectively.

[0225] (2) Maleimidation 70.08 g (1.3 equivalents) of maleic anhydride and 260.4 g of toluene were added to a 2 L flask equipped with a thermometer, a cooling tube, a Dean-Stark trap, and a stirrer. The mixture was stirred at room temperature. Then, a mixed solution of 120.0 g (1 equivalent) of the aromatic amine resin (a-1) and 32.6 g of DMF was added dropwise to the mixture over 1 hour. The mixture was reacted for 2 hours. 5.23 g of p-toluenesulfonic acid monohydrate was added to the reaction solution. Then, the reaction solution was heated to azeotropically distill the water and toluene that came out under reflux, and the water and toluene were cooled and separated. Then, the mixture was heated to 115 °C to azeotropically distill the water and toluene that came out under reflux, and the water and toluene were cooled and separated. Then, only toluene was returned to the system and the dehydration reaction was carried out for 5 hours. After air-cooling to room temperature, it was concentrated under reduced pressure, and the obtained brown solution was dissolved in 600 g of ethyl acetate and washed 3 times with 200 g of ion-exchanged water and 3 times with 150 g of a 2% aqueous sodium hydrogen carbonate solution. Then, sodium sulfate was added to the oil layer for drying, and it was concentrated under reduced pressure. The obtained reaction product was vacuum dried at 80 °C for 4 hours to obtain a product containing the maleimide resin (A-1). The GPC chart of this maleimide resin (A-1) is shown in Figure 3, the FD-MS spectrum is shown in Figure 4, 13 The results of the 13C NMR spectrum are shown in Figure 5. From the results such as GPC, the obtained polymaleimide resin (A-1) is represented by the above general formula (1A), and n 1 and n 3 It was confirmed that the component in which the sum of is 1 or more contains 20% by mass or more, and the component in which n 2 is 1 or more contains 10% by mass or more.

[0226] Regarding each peak of the FD-MS spectrum shown in Figure 4, the number of repetitions in the polymaleimide resin (A-1) was confirmed. The results are shown in Table 1.

Table 1

[0227] 〔Example 1〕Preparation of Composition and Molded Article The maleimide resin (A-1) obtained in Synthesis Example 1, the cyanate ester (B), and a curing catalyst were blended in the amounts shown in Table 2 to prepare a curable composition.

[0228] 〔Examples 2 and Comparative Examples 1 - 2〕 A curable composition was prepared in the same manner as in Example 1, except that the maleimide resin and the curing catalyst were changed as shown in Table 2.

[0229] <Cured Product> The curable composition was cured under the following conditions to obtain a cured product. Curing conditions: After heating at 200 °C for 2 hours using a vacuum press, it was heat - cured at 250 °C for 2 hours. The thickness after molding was 1.3 mm. For this cured product, physical property evaluations of dielectric properties and moisture absorption rate were performed by the following methods. The results are shown in Table 2.

[0230] <Measurement of Dielectric Properties> In accordance with JIS C 6481, using a network analyzer manufactured by Agilent Technologies, Inc., the dielectric constant (Dk) and dielectric tangent (Df) at 1 GHz of the test piece (cured product) after storing in a room at 23 °C and 50% humidity for 24 hours after being completely dried were measured by the cavity resonance method.

[0231] <Moisture Absorption Rate> In this example and comparative examples, as a method for evaluating low moisture absorption, the moisture absorption rate (%) was calculated and evaluated by the following method. A test piece cut from the above - obtained 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

[0232]

Table 2

[0233] According to the present invention, a polymaleimide resin showing excellent dielectric properties and low moisture absorption during curing, and a curable composition containing the polymaleimide resin could be provided.

Industrial Applicability

[0234] According to the present invention, it is possible to provide a polyimide resin that exhibits excellent dielectric properties and low moisture absorption during curing, a curable composition containing the polyimide resin, a cured product thereof, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device.

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 (2) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (3) chemically bonded to the partial structure represented by the general formula (1), and a cyanate ester (B), characterized in that it contains a curable composition. 【Chemical 1】 [In the above general formula (1), R １３ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m ２ represents an integer of 0 or more and 4 or less, n １ represents the average number of repeating units, two * each represent a bond, and one bond is L in the following general formula (2) １３ or L １４ at the position of chemical bonding, and the other bond is L in the following general formula (3) １１ or L １２ at the position of chemical bonding.] [Chemical 2] In the above general formula (2) or (3), 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. ]

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 (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c) as reaction raw materials (1). 【Chemical 3】 In the above general formula (a-1), R ａ１ and R ａ２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R １ represents a hydrocarbon group having 1 to 18 carbon atoms, and R ２ and R ３ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]

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

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

5. A maleimide resin mixture (C) containing a polymer maleimide resin component having a partial structural unit represented by the following general formula (1a) and a maleimide multimer compound represented by the following general formula (5), and a cyanate ester (B), and the maleimide resin mixture (C) 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 (2) chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (3) chemically bonded to the partial structure represented by the general formula (1) with respect to the total amount of the polymer maleimide resin component, and contains 80% by mass or less of the maleimide multimer compound with respect to the total amount of the maleimide resin mixture (C), characterized in that it is a curable composition. 【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 general formula (5) above, R ２１ and R ２５ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R ２２ and R ２４ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m ２１ represents 2, m ２３ represents 3, 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, the two * each represent a bond, one bond is at the position of L １３ or L １４ in the following general formula (2) is chemically bonded, and the other bond is at the position of L １１ or L １２ in the following general formula (3) is chemically bonded.] 【Chemical Formula 9】 In the general formula (2) or (3) above, R １１ and R １５ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R １２ and R １４ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, L １１ ~L １４ each independently represents a bond or a hydrogen atom, provided that L １１ or L １２ is chemically bonded to the partial structure represented by the general formula (1) at the position of, and L １３ or L １４ is chemically bonded to the partial structure represented by the general formula (1) at the position of, and L that is not chemically bonded to the partial structure represented by the general formula (1) １１ ~L １４ is a hydrogen atom, m １ and m ３ each represent 2.]

6. The curable composition according to claim 5, wherein the polymer maleimide resin (A) uses an aromatic amine compound (A-a) represented by the following general formula (a-1), a compound (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c) as reaction raw materials (1). 【Chemical 10】 [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.]

7. A polymer maleimide resin, characterized in that it has a partial structure represented by the following general formula (1A). 【Chemical 11】 In the above general formula (1A), R １３ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m ２ represents an integer of 0 or more and 4 or less, n １ represents the average number of repeating units, R １１ each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R １２ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m １ each represents 2, n ２ represents the average number of repeating units, ran represents that the arrangement of each constitutional unit 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 (4).] 【Chemical 12】 [In the general formula (4) above, R １３ each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m ２ represents an integer of 0 or more and 4 or less, and n ３ represents the average number of repeating units.]

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

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

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

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

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

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

Images