Curable composition, cured product, prepreg, circuit board, laminate film, semiconductor sealing material, and semiconductor device

Abstract

The invention provides a curable composition, a cured product, a prepreg, a circuit board, a laminated film, a semiconductor sealing material and a semiconductor device, wherein the curable composition has low moisture absorption after being cured and shows low dielectric loss tangent and low dielectric constant; and the cured product, the prepreg, the circuit board, the laminated film, the semiconductor sealing material and the semiconductor device. A curable composition characterized by containing a polymaleimide resin (A) and an amine compound (B), the polymaleimide resin (A) has a partial structure represented by general formula (1), a partial structure represented by general formula (T-1) chemically bonded to the partial structure represented by general formula (1), and a partial structure represented by general formula (T-2) chemically bonded to the partial structure represented by general formula (1). [In general formula (1), each of two * represents a bond end, one bond end is chemically bonded at the position of L13 or L14 in general formula (T-1), and the other bond end is chemically bonded at the position of L11 or L12 in general formula (T-2). ] # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a curable composition, a cured product, a prepreg, a circuit board, a laminated film, a semiconductor sealing material, and a semiconductor device. Background Art

[0002] Conventionally, prepregs obtained by impregnating a thermosetting resin such as an epoxy resin or a BT (bismaleimide-triazine) resin into a glass cloth and heating and drying, laminated boards obtained by heat-curing the prepregs, and multilayer boards obtained by combining the laminated boards and the prepregs and heating and curing have been widely used as circuit board materials for electronic devices. Among them, a package substrate, which is a type of printed wiring board and serves as an intermediate layer for mounting a semiconductor, is being continuously thinned, and warping of the package substrate during installation has become a problem. Therefore, in order to suppress warping of the package substrate during installation, materials that exhibit high heat resistance are required.

[0003] In addition, in recent years, the high speed and high frequency of signals have been continuously advancing, and there is a desire to provide a thermosetting composition that can form a cured product that maintains a sufficiently low dielectric constant and exhibits a sufficiently low dielectric loss tangent in these environments. In particular, recently, in various electrical material applications, especially in advanced material applications, further improvement in properties represented by heat resistance and dielectric properties, as well as materials and compositions that combine them, are required. For these requirements, maleimide resins have attracted attention as materials that combine heat resistance and low dielectric constant / low dielectric loss tangent. However, conventional maleimide resins, although showing high heat resistance, have high hygroscopicity and their dielectric properties (dielectric constant / dielectric loss tangent value) do not reach the level required for advanced material applications.

[0004] For example, in Patent Document 1 below, as a material for a printed circuit board that does not impair heat resistance and has a dielectric constant of 4.0 or less for a laminated board, a thermosetting resin composition containing a polymaleimide resin having an indane ring and triallyl cyanurate or an aromatic diamine is disclosed.

[0005] Prior Art Documents

[0006] Patent Documents

[0007] Patent Document 1: Japanese Patent Laid-Open No. 5-247202 Summary of the Invention

[0008] Problems to be Solved by the Invention

[0009] However, the dielectric constant and the dielectric loss tangent of the thermosetting resin composition disclosed in the above Patent Document 1 do not reach the level required for use in advanced materials, and it is impossible to achieve both low hygroscopicity, low dielectric constant, and low dielectric loss tangent at high temperatures. In addition, since the transmission loss increases as the frequency becomes higher, a circuit board material is required to reduce the transmission loss in the high-frequency region. However, in the technology of the above Patent Document 1, only the dielectric properties in the currently used frequency band (the range of several hundred MHz to 3 GHz) have been studied, and it has not been studied whether it can cope with the technology for the fifth-generation mobile communication system (5G) using a frequency band above Sub6 (for example, 3.6 GHz or higher).

[0010] Therefore, an object of the present invention is to solve the above problems of the prior art and provide a curable composition, a cured product, a prepreg, a circuit board, a laminated film, a semiconductor encapsulant, and a semiconductor device that have low hygroscopicity after curing and exhibit a low dielectric loss tangent and a low dielectric constant.

[0011] Method for solving the problem

[0012] The inventors of the present invention have repeatedly conducted in-depth studies to solve the above problems, and as a result, it has been found that by using a curable composition containing a specific polyimide resin (A) and an amine compound (B), it is possible to highly achieve both low hygroscopicity, low dielectric loss tangent, and low dielectric constant after curing, thereby completing the present invention.

[0013] That is, the main configurations of the curable composition, the cured product, the prepreg, the circuit board, the laminated film, the semiconductor encapsulant, and the semiconductor device of the present invention for solving the above problems are as follows.

[0014] [1] A curable composition, characterized by containing a polyimide resin (A) and an amine compound (B),

[0015] The polyimide resin (A) has a partial structure represented by the following general formula (1), a partial structure represented by the following general formula (T-1) that is chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (T-2) that is chemically bonded to the partial structure represented by the general formula (1),

[0016] [Chemical formula 1]

[0017]

[0018] [In the above general formula (1), R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, and m 2 represents an integer of 0 or more and 4 or less, and n 1represents the average number of repeating units, and the two * respectively represent bonding ends, where one bonding end is at the position of L in the following general formula (T-1) 13 or L 14 for chemical bonding, and the other bonding end is at the position of L in the following general formula (T-2) 11 or L 12 for chemical bonding.]

[0019] [Chemical formula 2]

[0020]

[0021] [In the above general formula (T-1) or (T-2), R 11 and R 15 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms,

[0022] R 12 and R 14 each independently represent a hydrocarbon group having 1 to 18 carbon atoms,

[0023] L 11 to L 14 each independently represent a bonding end or a hydrogen atom, where, at the position of L 11 or L 12 it undergoes chemical bonding with the partial structure represented by the general formula (1), and at the position of L 13 or L 14 it undergoes chemical bonding with the partial structure represented by the general formula (1). Additionally, L 11 to L 14 that does not undergo chemical bonding with the partial structure represented by the general formula (1) is a hydrogen atom,

[0024] m 1 and m 3 each represent 2.]

[0025] [2] The curable composition according to [1], wherein the polyimide 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),

[0026] [Chemical formula 3]

[0027]

[0028] [In the above general formula (a-1), R a1 and R a2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 1 represents a hydrocarbon group having 1 to 18 carbon atoms, R 2and R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.

[0029] [3] The curable composition according to [1] or [2], wherein the polyimide resin (A) is a polyimide resin having a partial structure represented by the following general formula (1A),

[0030] [Chemical formula 4]

[0031]

[0032] [In the above general formula (1A), R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 2 represents an integer of 0 or more and 4 or less, n 1 represents the average number of repeating units, R 11 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 1 each represents 2, n 2 represents the average number of repeating units, ran represents that the arrangement of each structural unit can be random, and the two * respectively represent the bonding ends and are bonded to a hydrogen atom or a partial structure represented by the following general formula (T-3).

[0033] [Chemical formula 5]

[0034]

[0035] [In the above general formula (T-3), R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 2 represents an integer of 0 or more and 4 or less, n 3 represents the average number of repeating units.

[0036] [4] The curable composition according to [3], which contains 10% by mass or more of a component represented by the above general formula (1A) and having a sum of n 1 and n 3 of 1 or more.

[0037] [5] A curable composition, characterized in that it contains a polyimide resin mixture (C) and an amine compound (B),

[0038] The polyimide resin mixture (C) contains a polyimide resin component having a partial structural unit represented by the following general formula (1a) and a maleimide polycompound represented by the following general formula (2),

[0039] The polyimide resin mixture (C) contains 1 to 99% by mass of the polyimide resin (A) relative to the total amount of the polyimide resin component, and contains 80% by mass or less of the maleimide polycompound relative to the total amount of the polyimide resin mixture (C).

[0040] The polyimide resin (A) has a partial structure represented by the following general formula (1), a partial structure represented by the following general formula (T-1) that is chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (T-2) that is chemically bonded to the partial structure represented by the general formula (1).

[0041] [Chemical formula 6]

[0042]

[0043] [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, n 1 represents the average number of repeating units.]

[0044] [Chemical formula 7]

[0045]

[0046] [In the above general formula (2), R 21 and R 25 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 22 and R 24 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 21 represents 2, m 23 represents 3, n 21 represents an integer of 1 or more and 5 or less.]

[0047] [Chemical formula 8]

[0048]

[0049] [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 * respectively represent bonding ends, and one bonding end is L in the following general formula (T-1)13 or L 14 to bond chemically at the position of L in the following general formula (T-2), and the other bonding end is L in the following general formula (T-2) 11 or L 12 to bond chemically at the position of.

[0050] [Chemical Formula 9]

[0051]

[0052] [In the above general formula (T-1) or (T-2), R 11 and R 15 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms,

[0053] R 12 and R 14 each independently represents a hydrocarbon group having 1 to 18 carbon atoms,

[0054] L 11 to L 14 each independently represents a bonding end or a hydrogen atom, wherein, at the position of L 11 or L 12 to bond chemically with the partial structure represented by the general formula (1), and at the position of L 13 or L 14 to bond chemically with the partial structure represented by the general formula (1), and in addition, L 11 to L 14 which does not bond chemically with the partial structure represented by the general formula (1) is a hydrogen atom,

[0055] m 1 and m 3 each represents 2.

[0056] [6] The curable composition according to [5], wherein the polyimide resin (A) is obtained from an aromatic amine compound (A-a) represented by the following general formula (a-1), a compound (A-b) having a benzylic ether skeleton, and maleic anhydride (A-c) as reaction raw materials (1),

[0057] [Chemical Formula 10]

[0058]

[0059] [In the above general formula (a-1), R a1 and R a2 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 1 represents a hydrocarbon group having 1 to 18 carbon atoms, R 2 and R 3 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]

[0060] [7] A polyimide resin, characterized in that it has a partial structure represented by the following general formula (1A),

[0061] [Chemical formula 11]

[0062]

[0063] [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 respectively represent 2, n 2 represents the average number of repeating units, ran represents that the arrangement of each structural unit can be random, and the two * respectively represent the bonding ends, which are bonded to a hydrogen atom or a partial structure represented by the following general formula (T-3).]

[0064] [Chemical formula 12]

[0065]

[0066] [In the above general formula (T-3), R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 2 represents an integer of 0 or more and 4 or less, n 3 represents the average number of repeating units.]

[0067] [8] A cured product of the curable composition according to any one of [1] to [6].

[0068] [9] A prepreg, which has a reinforcing substrate and a semi-cured product of the curable composition according to any one of [1] to [6] impregnated in the reinforcing substrate.

[0069]

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

[0070]

[11] A laminated film, which contains the curable composition according to any one of [1] to [6].

[0071]

[12] A semiconductor sealing material, which contains the curable composition according to any one of [1] to [6].

[0072]

[13] A semiconductor device, which includes a cured product of the semiconductor sealing material according to

[12] .

[0073] Advantages of the Invention

[0074] According to the present invention, there can be provided a curable composition, a cured product, a prepreg, a circuit board, a laminated film, a semiconductor sealing material, and a semiconductor device that can highly balance low hygroscopicity, low dielectric constant, and low dielectric loss tangent after curing.

[0075] In addition, according to the present invention, there can be provided a curable composition, a cured product, a prepreg, a circuit board, a laminated film, a semiconductor sealing material, and a semiconductor device that can highly balance low hygroscopicity, low dielectric constant, and low dielectric loss tangent even in a frequency band of Sub6 or higher. Such a curable composition is particularly useful in applications such as electronic component sealing materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0076] Figure 1 is the FD-MS spectrum of the intermediate amine compound (a-1).

[0077] Figure 2 is of the intermediate amine compound (a-1) 13 C-NMR spectrum.

[0078] Figure 3 is the GPC chart of the polyimide resin (A-1).

[0079] Figure 4 is the FD-MS spectrum of the polyimide resin (A-1).

[0080] Figure 5 is for the polyimide resin (A-1) 13 C-NMR spectrum. DETAILED DESCRIPTION OF THE INVENTION

[0081] Hereinafter, the curable composition, cured product, prepreg, circuit board, laminated film, semiconductor sealing material, and semiconductor device of the present invention will be described in detail by way of examples based on their embodiments.

[0082] It should be noted that the present invention is not limited to the following description and can be implemented with various modifications within the scope of its gist.

[0083] [TERMS]

[0084] In this specification, the following terms can be applied unless otherwise specified.

[0085] The "reaction raw materials" in this specification are used to obtain a target compound through a chemical reaction such as bonding or decomposition, and refer to compounds that partially constitute the chemical structure of the target compound, excluding substances that act as chemical reaction aids such as solvents and catalysts. In this specification, particularly regarding the "reaction raw materials", for example, when the target is a polyimide resin (A), it refers to the precursors used to obtain the polyimide resin (A) or its precursor compounds (for example, an intermediate amine compound (A-ab) formed by linking aromatic amine compounds (A-a) to each other via a structural unit derived from a compound (A-b) having a benzylic ether skeleton) through a chemical reaction.

[0086] The "structural unit" in this specification refers to the (repeating) unit of the chemical structure formed during a reaction or polymerization. In other words, it refers to the partial structure other than the structure of the chemical bond participating in the reaction or polymerization in the resulting compound formed by the reaction or polymerization, and is what is called a residue. Additionally, it is also called a repeating unit during polymerization.

[0087] The "aromatic group" in this specification preferably has an aromatic ring with 3 to 30 carbon atoms, more preferably an aromatic ring with 4 to 26 carbon atoms. Moreover, in the "aromatic group" in this specification, the hydrogen atoms of the aromatic ring in the aromatic group can be 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. Additionally, the "aromatic group" includes heteroaromatics and can be substituted by -O-, -S-, or -N= in such a way that -CH2- or -CH= in the "aromatic group" are not adjacent to each other.

[0088] Examples of the type of the aromatic ring include monocyclic aromatic rings and fused polycyclic aromatic rings. Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, triazine, etc. Examples of the fused polycyclic aromatic ring include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etc.

[0089] Examples of the ring-aggregated aromatic ring include biphenyl, binaphthyl, bipyridine, bithiophene, phenylpyridine, phenylthiophene, terphenyl, diphenylthiophene, quaterphenyl, etc.

[0090] Additionally, the hydrogen atoms of the aromatic ring in the aromatic group can be substituted, for example, by 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.

[0091] It should be noted that a monovalent aromatic group refers to a group obtained by removing one hydrogen atom from an "aromatic group", and a divalent aromatic group refers to a group obtained by removing any two hydrogen atoms from an "aromatic group".

[0092] The "alkyl group" in this specification can be any of straight-chain, branched-chain or cyclic, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, (n)heptyl, (n)octyl, (n)nonyl, (n)decyl, (n)undecyl, (n)dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl or adamantyl.

[0093] The "cycloalkyl group" in this specification can include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, methylcyclobutyl, norbornyl or adamantyl, etc.

[0094] The "alkylthio group" in this specification can include methylthio, ethylthio, propylthio, butylthio, octylthio or 2-ethylhexylthio.

[0095] The "alkenyl group" in this specification can include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, pentynyl, hexynyl, vinyl, allyl or isopropenyl, etc. It should be noted that the "alkenylene group" can include a divalent group obtained by removing any one hydrogen atom from the above "alkenyl group".

[0096] The "alkoxy group" in this specification can include, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, octyloxy or nonyloxy, etc.

[0097] The "aryl group" in this specification can include, for example, phenyl, naphthyl, phenalenyl, phenanthryl, anthryl, azulenyl, tetrahydronaphthyl, etc. In addition, in this "aryl group", the hydrogen atoms of the aromatic ring in the aryl group can be substituted by, 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. It should be noted that the "arylene group" can include a divalent group obtained by removing any one hydrogen atom from the "aryl group".

[0098] As the "aralkyl group" in this specification, for example, benzyl, diphenylmethyl, biphenyl, naphthylmethyl, etc. can be cited. The hydrogen atoms of the aromatic ring in the aralkyl group can be substituted by, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or a halogen atom. It should be noted that the "aralkylene group" can include a divalent group obtained by removing any one hydrogen atom from the above "aralkyl group".

[0099] The "aryloxy group" in this specification may include phenoxy group, naphthyloxy group, anthryloxy group, phenanthryloxy group, pyrenyloxy group, etc.

[0100] The "arylthio group" in this specification may include arylthio groups such as phenylthio group, naphthylthio group, anthrylthio group, phenanthrylthio group, pyrenylthio group, etc.

[0101] The "halogen atom" in this specification may include, for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.

[0102] The "alkylene group" in this specification may include, for example, methylene group, ethylene group, propylene group, 1-methylmethylene group, 1,1-dimethylmethylene group, 1-methylethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group, propylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, undecylene group, dodecylene group, etc.

[0103] The "alkyloxy group" in this specification may include, for example, oxymethylene group, oxyethylene group, oxypropylene group, oxy(1-methylmethylene) group, oxy(1,1-dimethylmethylene) group, oxy(1-methylethylene) group, oxy(1,1-dimethylethylene) group, oxy(1,2-dimethylethylene) group, oxybutylene group, oxy(1-methylpropylene) group, oxy(2-methylpropylene) group, oxypentylene group, oxyhexylene group, oxyheptylene group, oxyoctylene group, oxynonylene group, oxydecylene group, oxoundecylene group, oxydodecylene group, etc.

[0104] The "hydrocarbon group" in this specification is a monovalent group and includes straight-chain, branched-chain 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 alkyl group (for example, the above-mentioned alkyl group), alkenyl group (for example, the above-mentioned alkenyl group), aryl group (for example, the above-mentioned aryl group), aryloxy group (for example, the above-mentioned aryloxy group), aralkyl group (for example, the above-mentioned aralkyl group) and alkoxy group (for example, the above-mentioned alkoxy group), and may be substituted by -O-, -C(=O)- or -S- in such a way that one or more -CH2- in the group do not adjoin each other, or may be substituted by -CH=CH- in such a way that one or more -CH2-CH2- in the alkyl group do not adjoin each other.

[0105] [Curable Composition]

[0106] The curable composition of the present embodiment is characterized by containing a polyimide resin (A) (hereinafter sometimes simply referred to as "polyimide resin (A)") and an amine compound (B), and the polyimide resin (A) has a partial structure represented by the above general formula (1), a partial structure represented by the above general formula (T-1) which is chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the above general formula (T-2) which is chemically bonded to the partial structure represented by the general formula (1).

[0107] Since the curable composition of the present embodiment contains a polyimide resin (A) having a small proportion of polar functional groups in its chemical structure, excellent low dielectric properties and low moisture absorption can be achieved as a whole for the composition. In addition, by combining the polyimide resin (A) and the amine compound (B), the curable composition of the present embodiment can highly balance low moisture absorption, low dielectric constant and low dielectric loss tangent after curing even in a frequency band of Sub6 or higher.

[0108] In the curable composition of the present embodiment, as the mixing ratio (parts by mass) of the polyimide resin (A) and the amine compound (B), polyimide resin (A):amine compound (B) is preferably 97:3 to 3:97, more preferably 95:5 to 5:95, and further preferably 90:10 to 10:90. By adjusting the mixing ratio to the above range, excellent low moisture absorption, low dielectric constant and low dielectric loss tangent can be exhibited, so it is preferred.

[0109] The curable composition of the present embodiment may contain a curing agent (D) other than the amine compound (B) within a range that does not impair the effects of the present invention. In addition, the curable composition of the present embodiment may also contain other resins (E), a curing accelerator or additives other than the polyimide resin (A) and the amine compound (B). Examples of the additive include a flame retardant, an inorganic filler, a silane coupling agent, a release agent, an antioxidant, a light stabilizer, a heat stabilizer, a pigment and an emulsifier.

[0110] Hereinafter, after a detailed description of the polyimide resin (A) and the amine compound (B) which are essential components of the curable composition of the present embodiment, the curing agent (D) other than the amine compound (B), other resins (E), the curing accelerator and additives will be described.

[0111] <Polyimide resin (A)>

[0112] The polyimide resin (A) has a partial structure represented by the following general formula (1), a partial structure represented by the following general formula (T-1) that is chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (T-2) that is chemically bonded to the partial structure represented by the general formula (1).

[0113] [Chemical formula 13]

[0114]

[0115] [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 * respectively represent bonding ends. One bonding end is chemically bonded at the position of L 13 or L 14 in the following general formula (T-1), and the other bonding end is chemically bonded at the position of L 11 or L 12 in the following general formula (T-2).]

[0116] [Chemical formula 14]

[0117]

[0118] [In the above general formula (T-1) or (T-2), R 11 and R 15 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 and R 14 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, and L 11 to L 14 each independently represents a bonding end or a hydrogen atom. Among them, at the position of L 11 or L 12 it is chemically bonded to the partial structure represented by the general formula (1), and at the position of L 13 or L 14 it is chemically bonded to the partial structure represented by the general formula (1). In addition, L 11 to L 14 that are not chemically bonded to the partial structure represented by the general formula (1) are hydrogen atoms, and m 1 and m 3 each represent 2.]

[0119] Since the polyimide resin (A) has a small proportion of polar functional groups in its chemical structure, its cured product can achieve both excellent low dielectric properties and low moisture absorption. In addition, the polyimide resin (A) has high solubility in solvents, and its cured product exhibits high heat resistance. In the chemical structure of the polyimide resin (A), there is only one bonding site at the ortho and para positions of the benzene ring bonded with the maleimide group, respectively. Therefore, a polyimide resin with a linear chain elongation can be obtained, and thus the molecular weight control is easy, and heat resistance, low dielectric properties and solvent solubility can be achieved at the same time. Therefore, the curable composition containing the polyimide resin (A) has high solubility in solvents. Furthermore, its cured product can highly achieve low moisture absorption, low dielectric constant and low dielectric loss tangent, and in addition, exhibits high heat resistance.

[0120] In the above general formula (1), the two * each represent a bonding end. Moreover, one of the two bonding ends is chemically bonded at the position of L in the above general formula (T-1) 13 or L 14 The other bonding end is chemically bonded at the position of L in the above general formula (T-2) 11 or L 12 Therefore, the polyimide resin (A) has a structural unit in which the partial structure represented by the general formula (T-1) and the partial structure represented by the general formula (T-2) are connected by the partial structure represented by the general formula (1). At the para or one ortho position relative to the maleimide group on the benzene ring in the general formula (T-1) and the general formula (T-2), the partial structure represented by the general formula (1) is chemically bonded.

[0121] It should be noted that in the above general formula (1), when n 1 is 2 or more, there are multiple R 13 which may be the same as or different from each other. When m 2 is 2 or more, there are multiple R 13 which may be the same as or different from each other.

[0122] In the above general formula (1), each R 13 independently represents a hydrocarbon group having 1 to 18 carbon atoms, preferably represents a hydrocarbon group having 1 to 12 carbon atoms, and more preferably represents a hydrocarbon group having 1 to 6 carbon atoms. In addition, when m 2 is an integer of 2 or more, there are multiple R 13 which may be the same as or different from each other. As the preferred R 13 in the general formula (1), it is preferably a linear alkyl group, more preferably methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl or neopentyl.

[0123] It should be noted that R in the general formula (1) 13 The benzene ring to which it is bonded may be the benzene ring of the compound (A-b) having a benzylic ether skeleton.

[0124] 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, and more preferably 2. It should be noted that in the R in the general formula (1) 13 In the benzene ring to which it is bonded, when it is bonded through a methylene group at the 1-position and the 3-position, preferably R 13 are bonded to the 4-position and the 6-position, respectively.

[0125] In the above general formula (1), n 1 represents the average number of repeating units. From the viewpoint of the viscosity of the obtained polyimide resin (A), it is preferably 0 or more and 50 or less, more preferably 0 or more and 30 or less, and further preferably 0 or more and 15 or less. As shown in the Examples section described later, this average number of repeating units can be calculated from the input ratio or NMR, etc.

[0126] Relative to the total amount (100% by mass) of the polyimide resin (A), the polyimide resin (A) preferably contains 1 to 99% by mass of the partial structure represented by the general formula (1), more preferably contains 3 to 97% by mass, and further preferably contains 5 to 95% by mass.

[0127] In the above general formula (T-1), R 15 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, preferably represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and more preferably represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. As a particularly preferred R 15 , it may be a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms. Since m 3 is 2, the two Rs 15 may be the same as or different from each other.

[0128] In the above general formula (T-1), R 14 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. As a particularly preferred R 14 , it may be a linear alkyl group having 1 to 6 carbon atoms.

[0129] By allowing the bonding site of the partial structure represented by the general formula (1) at the ortho-position (6-position) of the benzene ring in the general formula (T-1) or the general formula (T-2), it has higher solubility in solvents, and its cured product shows more excellent low dielectric loss tangent and high heat resistance. It should be noted that R in the general formula (T-1)14 The benzene ring to be bonded may be the benzene ring of the aromatic amine compound (A-a).

[0130] In the above general formula (T-1), L 13 or L 14 each independently represents a bonding end or a hydrogen atom. Among them, at least one position of L 13 or L 14 is chemically bonded to the partial structure represented by the general formula (1) and the partial structure represented by the general formula (T-1). In addition, L 13 or L 14 that is not chemically bonded to the partial structure represented by the general formula (1) is a hydrogen atom. It should be noted that the partial structure represented by the general formula (1) can also be chemically bonded to both L 13 and L 14 at these two positions.

[0131] In the above general formula (T-2), R 11 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, preferably represents a hydrogen atom or a hydrocarbon group having 1 to 12 carbon atoms, and more preferably represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms. As the preferred R 11 , it can be a hydrogen atom or a linear alkyl group having 1 to 6 carbon atoms. Since m 1 is 2, the two Rs 11 can be the same or different from each other.

[0132] In the above general formula (T-2), R 12 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. As the preferred R 12 , it represents a linear alkyl group having 1 to 6 carbon atoms.

[0133] It should be noted that the benzene ring to which R 12 in the general formula (T-2) is bonded may be the benzene ring of the aromatic amine compound (A-a).

[0134] In the above general formula (T-2), L 11 or L 12 each independently represents a bonding end or a hydrogen atom. Among them, at least one position 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 (T-2). In addition, L 11 or L 12 that is not chemically bonded to the partial structure represented by the general formula (1) is a hydrogen atom. It should be noted that the partial structure represented by the general formula (1) can also be chemically bonded to both L 11 and L12 At these two positions.

[0135] Relative to the total amount (100% by mass) of the polyimide resin (A), the polyimide resin (A) preferably contains 1 to 99% by mass of the partial structure represented by the general formula (T-1), more preferably contains 3 to 97% by mass, and still more preferably contains 5 to 95% by mass.

[0136] Relative to the total amount (100% by mass) of the polyimide resin (A), the polyimide resin (A) preferably contains 1 to 99% by mass of the partial structure represented by the general formula (T-2), more preferably contains 3 to 97% by mass, and still more preferably contains 5 to 95% by mass.

[0137] <<Polyimide resin having a partial structure represented by the general formula (1A)>>

[0138] As the polyimide resin (A), a polyimide resin having a partial structure represented by the following general formula (1A) is preferred.

[0139] [Chemical formula 15]

[0140]

[0141] [In the above general formula (1A), R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 2 represents an integer of 0 or more and 4 or less, n 1 represents the average number of repeating units, R 11 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 1 each represents 2, n 2 represents the average number of repeating units, ran represents that the arrangement of each structural unit can be random, and the two * respectively represent the bonding ends, which are bonded to a hydrogen atom or a partial structure represented by the following general formula (T-3).]

[0142] [Chemical formula 16]

[0143]

[0144] [In the above general formula (T-3), R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 2 represents an integer of 0 or more and 4 or less, n 3 represents the average number of repeating units.]

[0145] The polyimide resin having the partial structure represented by the above general formula (1A) can achieve a balance among heat resistance, low dielectric properties, and solvent solubility. Therefore, the curable composition containing the polyimide resin having the partial structure represented by the above general formula (1A) has high solubility in solvents. Furthermore, the cured product thereof can highly balance low hygroscopicity, low dielectric constant, and low dielectric loss tangent, and in addition, exhibits high heat resistance.

[0146] "R 11 , R 12 , R 13 , n 1 , m 1 and m 2 " in the above general formula (1A) has the same meaning as "R 11 , R 12 , R 13 , n 1 , m 1 and m 2 " in the above general formula (1) or general formula (T-2). In addition, regarding "R 11 , R 12 , R 13 , n 1 and m 2 " in the above general formula (1A), the preferred hydrocarbon group, the preferred number of carbon atoms, and the preferred numerical range are also the same as those of "R 11 , R 12 , R 13 , n 1 and m 2 " in the above general formula (1) or general formula (T-2).

[0147] n in the above general formula (1A) 2 represents the average number of repeating units, and from the viewpoint of the viscosity of the obtained polyimide resin, it is preferably 0 or more and 50 or less, more preferably 0 or more and 30 or less, and still more preferably 0 or more and 15 or less. As shown in the Examples section described later, this average number of repeating units can be calculated from the input ratio or NMR, etc.

[0148] ran in the above general formula (1A) means that the arrangement of each structural unit can be random.

[0149] In the above general formula (1A), the two * each represent a bonding end, which is bonded to a hydrogen atom or a partial structure represented by the general formula (T-3).

[0150] In addition, "R 13 and m 2 " in the above general formula (T-3) are each independently the same as "R 13 or m 2 " in the above general formula (1).

[0151] n in the above general formula (T-3) 3 represents the average number of repeating units, and from the viewpoint of the viscosity of the obtained polyimide resin, it is preferably 0 or more and 50 or less, more preferably 0 or more and 30 or less, and still more preferably 0 or more and 15 or less. As shown in the Examples section described later, this average number of repeating units can be calculated from the input ratio or NMR, etc.

[0152] In the above general formula (T-3), * represents a bonding end, which is chemically bonded to the *(bonding end) in the general formula (1A).

[0153] The polyimide resin (A) preferably contains 10% by mass or more of the component represented by the above general formula (1A) and the sum of n 1 and n 3 is 1 or more, more preferably contains 15% by mass or more, and still more preferably contains 20% by mass or more. In addition, from the viewpoint of heat resistance, the polyimide resin (A) preferably contains 5% by mass or more of the component represented by the above general formula (1A) and n 2 is 1 or more, more preferably contains 7% by mass or more, and still more preferably contains 10% by mass or more.

[0154] <<Reaction raw materials>>

[0155] The polyimide resin (A) preferably uses the 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)), the compound (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c) as the reaction raw materials (1).

[0156] [Chemical formula 17]

[0157]

[0158] [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.]

[0159] In addition, the polyimide resin (A) preferably uses an intermediate amine compound (A-ab) formed by linking aromatic amine compounds (A-a) to each other 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 (A-ab) 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).

[0160] In other words, the intermediate amine compound (A-ab) preferably has a structural unit formed by linking a structural unit of an aromatic amine compound (A-a) having an aromatic ring bonded with an amino group to a structural unit derived from a compound (A-b) having a benzyl ether skeleton via a chemical bond. Moreover, the polyimide resin (A) has a structure in which the amino group bonded to the aromatic ring of the intermediate amine compound (A-ab) is substituted with an N-substituted maleimide ring. It should be noted that the "amino group" in this specification also includes a substituted amino group in which a hydrogen atom of -NH2 is further substituted with an alkyl group having 1 to 6 carbon atoms.

[0161] Therefore, the "polyimide resin (A)" and the "intermediate amine compound (A-ab)" which is a precursor of the "polyimide resin (A)" are polymer compounds that are different in that the amino group bonded to the aromatic ring is substituted with an N-substituted maleimide ring.

[0162] It should be noted 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 following general formula (a-1), the group obtained by removing at least one hydrogen atom from the benzene ring of the general formula (a-1) is called the structural unit of the aromatic amine compound (A-a). In addition, the structural unit derived from the compound (A-b) having a benzyl ether skeleton refers to a group in which -(CH2O)- other than the terminal group in the compound (A-b) having a benzyl ether skeleton is substituted with -(CH2)- and -(CH2O)-R directly bonded to the benzene ring b is all substituted with -(CH2)-. It should be noted that the R b represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.

[0163] In this embodiment, since the aromatic amine compound (A-a) having an aromatic ring structure with a substituent at a specific position is used as a reaction raw material, it is easy to control the reaction site with the compound (A-b) having a benzyl ether skeleton described later. Therefore, a homogeneous chemical structure and a chain-like polyimide resin can be easily obtained. As a result, a polyimide resin (A) that exhibits excellent solubility in a solvent, high heat resistance after curing, and a low dielectric loss tangent can be provided.

[0164] 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), the manufacturing method of the polyimide resin (A) and other preferred embodiments of the polyimide resin (A) [polyimide resin mixture (C)] will be explained.

[0165] - Aromatic amine compound (A-a) represented by the general formula (a-1)-

[0166] As represented by the following general formula (a-1), the aromatic amine compound (A-a) must have a structure in which an aromatic ring bonded to an amino group and a hydrocarbon group having 1 to 18 carbon atoms are bonded to one ortho position of the aromatic ring.

[0167] [Chemical formula 18]

[0168]

[0169] [In the above general formula (a-1), R a1 and R a2 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R 1 represents a hydrocarbon group having 1 to 18 carbon atoms, R 2 and R 3 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms.]

[0170] In the aromatic amine compound (A-a), as the hydrocarbon group (R 2 , R 3 ) that can be substituted for one or more and two or less hydrogen atoms of the aromatic ring of the aromatic amine compound (A-a), a linear, branched or cyclic hydrocarbon group having 1 to 18 carbon atoms can be cited, preferably a linear or branched hydrocarbon group having 1 to 12 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. As described in the above general formula (a-1), each of the ortho and para positions of the aromatic ring has a bonding site with the compound (A-b) having a benzyl ether skeleton.

[0171] In the above general formula (a-1), R1 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.

[0172] In the above general formula (a-1), R 2 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms.

[0173] In the above general formula (a-1), R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, preferably a hydrocarbon group having 1 to 12 carbon atoms, more preferably a hydrocarbon group having 1 to 6 carbon atoms.

[0174] In addition, by setting the number of hydrocarbon groups (such as alkyl groups) substituted on the aromatic ring of the aromatic amine compound (A-a) to 1 or more, the reaction site with the compound (A-b) having a benzyl ether skeleton described later can be easily controlled, and thus a polyimide resin (A) having a specific chemical structure can be easily obtained. As a result, in the cured product of the curable composition containing the polyimide resin (A), solvent solubility, heat resistance, and excellent high-frequency electrical properties can be easily exhibited.

[0175] In particular, since a substituent (R 1 ) is introduced into the ortho-position (adjacent position) of the aromatic amine compound (A-a), it is considered that after the amino group derived from the aromatic amine compound (A-a) is maleimidized, 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, and thus the crystallinity derived from the maleimide group is easily destroyed and the solubility is improved.

[0176] In the present embodiment, among the carbon atoms in the benzene ring constituting the aromatic amine compound (A-a), it is preferable that 1 or more carbon atoms having the maximum electron density (Hückel coefficient) of HOMO are unsubstituted (substituted by hydrogen atoms). Therefore, as the aromatic amine compound (A-a) represented by the above general formula (a-1), it is preferable that any 2 of the 2nd, 4th, and 6th positions are substituted by hydrogen atoms. As a particularly preferable mode of the aromatic amine compound (A-a) represented by the above general formula (a-1), the 2nd position is substituted by an alkyl group, and the 4th and 6th positions are hydrogen atoms.

[0177] Thereby, it is easy to control ArS of the cationoid reagent formed by the compound (A-b) having a benzyl ether skeleton described later EReaction and molecular design. As a result, in the cured product of the curable composition containing the polyimide resin (A), solvent solubility, heat resistance, and excellent high-frequency electrical properties are easily exhibited. In particular, by substituting the 4-position and 6-position of the benzene ring of the general formula (a-1) with hydrogen atoms, a polyimide resin (A) (or intermediate amine resin) with a linear molecular elongation can be obtained.

[0178] As specific examples of the aromatic amine compound (A-a), for example, o-toluidine, 2-ethylaniline, 2-propylaniline, 2-butylaniline, 2-cyclobutylaniline, 2-cyclopentylaniline, 2-cyclohexylaniline, dimethylaniline (2,3-dimethylaniline, 2,4-dimethylaniline, or 2,5-dimethylaniline), 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 any one of the 2,3-position, 2,4-position, or 2,5-position is methyl and the other is ethyl), methylisopropylaniline (for example, methylisopropylaniline in which any one of the 2,3-position, 2,4-position, or 2,5-position is methyl and the other is isopropyl), or ethylbutylaniline (for example, ethylbutylaniline in which any one of the 2,3-position, 2,4-position, or 2,5-position is ethyl and the other is butyl) can be used. In addition, the butyl group includes n-butyl, tert-butyl, and sec-butyl. It should be noted that the aromatic amine compound (A-a) can be used alone or in combination of two or more.

[0179] For example, in the case of a chemical structure in which a maleimide group is directly bonded to an unsubstituted benzene ring as in N-phenylmaleimide, the state in which the benzene ring and the 5-membered ring of maleimide are arranged in the same plane is stable, so it is easy to stack and exhibits high crystallinity. Therefore, it becomes a reason for poor solvent solubility. On the other hand, for example, in the case of having an alkyl group (such as ethyl) as a substituent for the benzene ring as in 2-ethylaniline, due to the steric hindrance of ethyl, the benzene ring and the 5-membered ring of maleimide adopt a staggered conformation, making it difficult to stack, so the crystallinity decreases and the solvent solubility increases, which is a preferred mode. However, in the case where the steric hindrance is too large or depending on the substitution position of the alkyl group, there is also a concern that the reactivity during the synthesis of maleimidation and the curability of the maleimide group during the production of the cured product will deteriorate. Therefore, for example, an aromatic amine compound (A-a) having a hydrocarbon group with 1 to 6 carbon atoms is preferably used.

[0180] It should be noted that the aromatic amine compound (A-a) represented by the above general formula (a-1) can be used alone or in combination of two or more.

[0181] - Compound (A-b) having a benzylic ether skeleton -

[0182] The compound (A-b) having a benzylic ether skeleton can be a compound monomer or a mixture. When the compound (A-b) having a benzylic ether skeleton is a compound monomer, it is preferably a compound having a partial structure represented by the following formula (b) described later, more preferably a compound represented by the following formula (b-1), and further preferably a compound represented by the following formula (b-2).

[0183] On the other hand, when the compound (A-b) having a benzylic ether skeleton is a mixture, it is preferably not only a mixture containing a compound having a partial structure represented by the following formula (b) and / or a compound having a benzylic ether skeleton represented by the following formula (b-1), but also a mixture in which the component having a partial structure represented by the following general formula (b-3) accounts for 95% by mass or more and 100% by mass or less of the whole.

[0184] The compound (A-b) having a benzylic ether skeleton is preferably a compound having a benzylic ether skeleton represented by the following formula (b).

[0185] [Chemical formula 19]

[0186]

[0187] [In the above general formula (b), R b3 each independently represents an alkyl group having 1 to 18 carbon atoms, m b2 represents an integer of 0 or more and 4 or less, j 1 and j 2 each independently is an integer of 0 or more and 4 or less, j 1 +j 2 ≥1, k 1 and k 2 each independently is 0 or 1, and * represents a bond with other atoms.]

[0188] The compound (A-b) having a benzylic ether skeleton is preferably a product obtained by reacting an alkylbenzene with formaldehyde under an acid catalyst.

[0189] - Physical properties of the compound (A-b) having a benzylic ether skeleton -

[0190] The compound (A-b) having a benzylic ether skeleton preferably has a benzylic ether skeleton represented by the above formula (b) and satisfies at least one of the following physical property values. Thus, a resin that can exhibit more excellent solvent solubility, heat resistance, and dielectric properties can be synthesized.

[0191] The upper limit of the number average molecular weight (Mn) of the compound (A-b) having a benzylic ether skeleton is preferably 1200 or less, more preferably 800 or less, and still more preferably 500 or less. The lower limit of the number average molecular weight (Mn) of the compound (A-b) having a benzylic ether skeleton is preferably 200 or more, more preferably 240 or more, and still more preferably 250 or more.

[0192] The upper limit of the oxygen content of the compound (A-b) having a benzylic ether skeleton is preferably 15% by mass or less, more preferably 13% by mass or less, and still more preferably 12% by mass or less. The lower limit of the oxygen content of the compound (A-b) having a benzylic ether skeleton is preferably 4% by mass or more, more preferably 5% by mass or more, and still more preferably 7% by mass or more.

[0193] The upper limit of the specific gravity of the compound (A-b) having a benzylic ether skeleton is preferably less than 1.2, more preferably less than 1.15, and still more preferably less than 1.10. The lower limit of the specific gravity of the compound (A-b) having a benzylic ether skeleton is preferably 1.0 or more, more preferably 1.01 or more, and still more preferably 1.02 or more.

[0194] The upper limit of the viscosity (75 °C) of the compound (A-b) having a benzylic ether skeleton is preferably 1500 mPa·s or less, more preferably 1000 mPa·s or less, and still more preferably 900 mPa·s or less. The lower limit of the viscosity (75 °C) of the compound (A-b) having a benzylic ether skeleton is preferably 30 mPa·s or more, more preferably 50 mPa·s or more, and still more preferably 70 mPa·s or more.

[0195] The upper limit of the indirect viscosity (viscosity measured at 20 °C with the resin component diluted to 80% by weight with toluene) of the compound (A-b) having a benzylic ether skeleton is preferably 1000 mPa·s or less, more preferably 800 mPa·s or less, and still more preferably 500 mPa·s or less. The lower limit of the indirect viscosity (20 °C) of the compound (A-b) having a benzylic ether skeleton is preferably 10 mPa·s or more, more preferably 20 mPa·s or more, and still more preferably 30 mPa·s or more.

[0196] The hydroxyl value of the compound (A-b) having a benzylic ether skeleton is preferably 16 to 50 (mgKOH / g), more preferably 18 to 40 (mgKOH / g), and still more preferably 22 to 35 (mgKOH / g).

[0197] —Preferred mode of the compound (A-b) having a benzylic ether skeleton—

[0198] As an example of the compound (A-b) having a benzylic ether skeleton as the reaction raw material (1) of the polyimide resin (A), a compound having a structural unit represented by the following formula (b-1) is preferred.

[0199] [Chemical formula 20]

[0200]

[0201] [In the above general formula (b-1), R b1 each independently represents a hydrogen atom or an alkyl group having 1 to 11 carbon atoms, and one or more -CH2- in the alkyl group may be replaced by -O- or -C(=O)- in a non-adjacent manner 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 replaced by -O- in a non-adjacent manner 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 replaced by -O- or -(C=O)- in a non-adjacent manner 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 and L 2 at least one of them has a -CH2O- group.]

[0202] R in the above general formula (b-1) 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 replaced by -O- in a non-adjacent manner to each other. Preferred R b1 is preferably selected from the group consisting of 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 one of the groups consisting of. Here, the R b4 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. In addition, the p1 to p3 and the 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.

[0203] Furthermore, it is preferred that at least one of R b1 or L 2 has a -CH2O- group, and more preferably both R b1 and L 2 have a -CH2O- group.

[0204] R in the above general formula (b-1) b2 and R b3 can each independently correspond to R in the general formula (1) 13 . Therefore, R in the above general formula (b-1) b2 and R b3 each independently preferably represent an alkyl group having 1 to 18 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, still more preferably an alkyl group having 1 to 6 carbon atoms, in the same manner as in the general formula (1). In addition, when m b1 is an integer of 2 or more, two or more R b2 can be the same as each other or can be different groups. Similarly, when m b2 is an integer of 2 or more, two or more R b3 can be the same as each other or can be different groups.

[0205] In the above general formula (b-1), 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 can be replaced by -O- in a non-adjacent manner. Specifically, L 1 is preferably selected from the group consisting of an alkylene group having 1 to 11 carbon atoms, an alkoxy 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 One selected from the group consisting of. In addition, each of p1 to p3 and q1 to q3 independently preferably represents 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.

[0206] In the above general formula (b-1), L 2 Each independently preferably represents a single bond or an alkylene group having 1 to 11 carbon atoms, more preferably represents a single bond or an alkylene group having 1 to 9 carbon atoms, and one or more -CH2- in the alkylene group may be replaced by -O- in a non-adjacent manner. Specifically, L 2 Is preferably selected from the group consisting of a single bond, an alkylene group having 1 to 11 carbon atoms, an alkoxy 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 - One selected from the group consisting of. In addition, each of p1 to p3 and q1 to q3 independently preferably represents 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.

[0207] Furthermore, it is preferred that at least one of R b1 or L 2 has a -CH2O- group, and more preferably both R b1 and L 2 have a -CH2O- group.

[0208] Z in the above general formula (b-1) 1Preferably represents a hydrogen atom or an alkyl group having 1 to 11 carbon atoms, more preferably represents a hydrogen atom or an alkyl group having 1 to 9 carbon atoms.

[0209] In the above general formula (b-1), k is preferably an integer of 0 to 20, more preferably an integer of 0 to 15, and further preferably an integer of 0 to 10. It should be noted that when k is 2 or more, there are multiple Ls 1 can be the same group as each other, or can also be different groups.

[0210] As a preferred form of the compound (A-b) having a benzyl ether skeleton, it can be a compound having a structural unit represented by the following general formula (b-2).

[0211] [Chemical formula 21]

[0212]

[0213] [In the above general formula (b-2), R b1 each independently represents a hydrogen atom or an alkyl group having 1 to 11 carbon atoms, and one or more -CH2- in the alkyl group can be replaced by -O- or -C(=O)- in a non-adjacent manner 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 can be replaced by -O- in a non-adjacent manner 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 can be replaced by -O- or -(C=O)- in a non-adjacent manner 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 and L 2 at least any one of them has a -CH2O- group.]

[0214] In the above general formula (b-2), R b1 、R b2 and R b3 、L 1 、L 2 、Z 1 、k and m b1 and m b2 The preferred forms of are the same as those of the above general formula (b-1).

[0215] The compound (A-b) having a benzylic ether skeleton may be used alone or in combination of two or more. In addition, it may be a mixture containing two or more different compounds (A-b) having a benzylic ether skeleton.

[0216] It should be noted that in this specification, for the sake of convenience, a mixture containing two or more different compounds (A-b) having a benzylic ether skeleton in the term "compound (A-b) having a benzylic ether skeleton" is referred to as a mixture (A-b) having a benzylic ether skeleton. Therefore, the "compound (A-b) having a benzylic ether skeleton" includes not only the case representing only one compound but also the mixture (A-b) having a benzylic ether skeleton.

[0217] In the mixture (A-b) having a benzylic ether skeleton, the component having the partial structure represented by the following general formula (b-3) preferably accounts for 95% by mass or more and 100% by mass or less of the whole mixture (A-b) having a benzylic ether skeleton.

[0218] [Chemical formula 22]

[0219]

[0220] [In the above general formula (b-3), L 3 and L 4 are linking groups, each independently being one group selected from the group consisting of -CH2-, -CH2O-CH2-, -(CH2O)2-CH2-, and -(CH2O)3-CH2-, and * represents a bond to another atom.]

[0221] The mixture (A-b) having a benzylic ether skeleton preferably has the component having the partial structure represented by the above general formula (b-3) accounting for 95% by mass or more and 100% by mass or less of the whole mixture (A-b) having a benzylic ether skeleton and satisfies the following requirement (I) or (II).

[0222] (I) The total number of linking groups (the sum of L 3 and L 4 ) in each molecule of the component having the partial structure represented by the above general formula (b-3) is 1.1 or more and 2.4 or less.

[0223] (II) The number of terminal groups bonded to the terminal of the molecule of the component having the partial structure represented by the above general formula (b-3) is 0.5 or more and 1.5 or less per 1 molecule.

[0224] In this embodiment, as the linking groups (L 3 and L 4), one group selected from the group consisting of -CH2-, -CH2O-CH2-, -(CH2O)2-CH2- and -(CH2O)3-CH2- can be enumerated.

[0225] In the whole of the mixture (A-b) having a benzyl ether skeleton, the following linking group (L 3 and L 4 The total number of) of each molecule having a benzyl ether skeleton represented by the above general formula (b-3) is preferably the following composition (1) to (4).

[0226] (1) The number of the linking group "-CH2-" is preferably 0.65 or more and 1.4 or less.

[0227] (2) The number of the linking group "-CH2O-CH2-" is preferably 0.07 or more and 0.2 or less, more preferably 0.08 or more and 0.14 or less.

[0228] (3) The number of the linking group "-(CH2O)2-CH2-" is preferably 0.10 or more and 0.8 or less, more preferably 0.2 or more and 0.8 or less. In other embodiments, it is preferably more than 0.41 and 0.8 or less.

[0229] (4) The number of the linking group "-(CH2O)3-CH2-" is preferably 0.05 or more and 0.65 or less, preferably 0.09 or more and 0.6 or less, and further preferably 0.10 or more and 0.55 or less.

[0230] In the mixture (A-b) having a benzyl ether skeleton, it is preferable to have one or more groups selected from the group consisting of -CH2-OH, -CH2O-CH3, -(CH2O)2-CH3, -(CH2O)3-CH3 and -(CH2O)-COH as the terminal groups bonded to the ends of the molecules constituting the partial structure represented by the above general formula (b-3).

[0231] Moreover, in the whole of the mixture (A-b) having a benzyl ether skeleton, it is preferable that each molecule having a benzyl ether skeleton represented by the above general formula (b-3) has 0.5 or more and 1.5 or less terminal groups.

[0232] In the whole of the mixture (A-b) having a benzyl ether skeleton, the number of the following terminal groups of each molecule having a benzyl ether skeleton is preferably the following composition (5) to (10).

[0233] (5) The number of the terminal group "-CH2-OH" is preferably 0.17 or more and 0.4 or less, more preferably 0.18 or more and 0.25 or less.

[0234] (6) The number of the terminal group “-CH2O-CH3” is preferably 0.17 or more and 0.7 or less, more preferably 0.18 or more and 0.44 or less.

[0235] (7) The number of the terminal group “-(CH2O)2-CH3” is preferably 0.08 or more and 0.6 or less, preferably 0.09 or more and 0.3 or less.

[0236] (8) The number of the terminal group “-(CH2O)3-CH3” is preferably substantially not contained, more preferably 0.3 or less, still more preferably 0.2 or less.

[0237] (9) The number of the terminal group “-(CH2O)-COH” is preferably 0 or more and 0.1 or less, more preferably 0.01 or more and 0.1 or less.

[0238] In the mixture (A-b) having a benzyl ether skeleton, the chemical structure and the number of the linking group, and the chemical structure and the number of the terminal group are as shown in the Examples column described later, and can be calculated by NMR or referred to the manufacturer's catalog.

[0239] The compound (A-b) having a benzyl ether skeleton may be a synthetic product or a commercially available product. As the commercially available compound (A-b) having a benzyl ether skeleton, for example, xylene resin [trade name: Nikanol (Y-50, Y-100, Y-300, Y-1000, LLL, LL, L or H)] manufactured by Fudow Co., Ltd. is preferred.

[0240] In the present embodiment, relative to the total amount (100% by mass) of the polyimide resin (A), the structural unit of the compound (A-b) having a benzyl ether skeleton preferably contains 1 to 99% by mass, more preferably 5 to 95% by mass. The structural unit of the compound (A-b) having a benzyl ether skeleton means the group represented by the above general formula (1).

[0241] - Maleic anhydride (A-c)-

[0242] The maleic anhydride (A-c) is an essential component of the reaction raw material (1) of the polyimide resin (A), and is used for the reaction of maleimidizing the amino group derived from the aromatic amine compound (A-a) as described in the manufacturing method column of the polyimide resin (A) described later.

[0243] <<Physical properties of polyimide resin (A)>>

[0244] The number average molecular weight (Mn) of the polyimide resin (A) is preferably in the range of 200 to 1500, more preferably in the range of 300 to 800. In addition, the weight average molecular weight (Mw) of the polyimide resin (A) is preferably in the range of 280 to 2000, more preferably in the range of 330 to 1200.

[0245] From the viewpoints of excellent solvent solubility, heat resistance, and low dielectric loss tangent, the molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the polyimide resin (A) calculated by gel permeation chromatography (GPC) is preferably in the range of 1.01 to 4.0, more preferably in the range of 1.05 to 2.0, and further preferably in the range of 1.10 to 1.8. It should be noted that, according to the GPC chart obtained by GPC measurement, when the molecular weight distribution covers a wide range and there are many high molecular weight components, the proportion of the high molecular weight components contributing to flexibility increases. Therefore, compared with the cured products using maleimide in the past, brittleness is suppressed, and a cured product with excellent flexibility and softness can be obtained, which is a preferred mode.

[0246] It should be noted that 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) are measured under the measurement conditions described in the following examples using gel permeation chromatography (hereinafter simply referred to as "GPC").

[0247] <<Manufacturing method of polyimide resin (A)>>

[0248] Hereinafter, the manufacturing method of the polyimide resin (A) will be described.

[0249] The production method of the polyimide resin (A) is not particularly limited, and it can be produced in any manner as long as it has the partial structure represented by the above general formula (1), the partial structure represented by the above general formula (T-1) that is chemically bonded to the partial structure represented by the general formula (1), and the partial structure represented by the above general formula (T-2) that is chemically bonded to the partial structure represented by the general formula (1). As a preferred mode of the production method of the polyimide resin (A), an aromatic amine compound (A-a) represented by the following general formula (a-1) [hereinafter, also simply referred to as aromatic amine compound (A-a).], a compound (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c) are used as reaction raw materials (1).

[0250] [Chemical formula 23]

[0251]

[0252] [In the above general formula (a-1), Ra1 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.]

[0253] As a specific embodiment of the method for producing the polyimide resin (A), for example, a production method including the following steps (1) and (2) can be cited.

[0254] Step (1): As a reaction raw material (2), a step of reacting the aromatic amine compound (A-a) represented by the above general formula (a-1) with a compound (A-b) having a benzylic ether skeleton to obtain an intermediate amine compound (A-ab);

[0255] Step (2): As a reaction raw material (3), a step of reacting the intermediate amine compound (A-ab) obtained in the above step (1) with maleic anhydride (A-c) to obtain the polyimide resin (A).

[0256] Specifically, the method for producing the polyimide resin (A) preferably includes: a step (1) (also referred to as a crosslinking step) of reacting the aromatic amine compound (A-a) represented by the above general formula (a-1) with a compound (A-b) having a benzylic ether skeleton in the presence of a solid acid catalyst, and a step (2) (also referred to as a condensation step) of condensing the intermediate amine compound (A-ab) generated by the step (1) with maleic anhydride (A-c).

[0257] Hereinafter, each step of the method for producing the polyimide resin (A) will be described in turn.

[0258] - Step (1): Manufacturing step of intermediate amine compound (A-ab)-

[0259] Hereinafter, the manufacturing step of the intermediate amine compound (A-ab) will be described.

[0260] The step (1) is not particularly limited. For example, it is a step of reacting the aromatic amine compound (A-a), the compound (A-b) having a benzylic ether skeleton (such as Nikanol, etc.), and other compounds added as needed in the presence of an acid catalyst. Thereby, the intermediate amine compound (A-ab) can be generated.

[0261] Regarding the mixing ratio of the aromatic amine compound (A-a) and the compound (A-b) having a benzylic ether skeleton, considering the physical property balance of moldability and curability of the obtained cured product during production, the molar ratio of the compound (A-b) having a benzylic ether skeleton is preferably 0.001 to 1 mole, more preferably 0.1 to 0.5 mole, relative to 1 mole of the aromatic amine compound (A-a).

[0262] In addition, when using a mixture such as the mixture (A-b) having a benzylic ether skeleton as the compound (A-b) having a benzylic ether skeleton, the reaction point with the aromatic amine compound (A-a) can be the methoxymethylene group [e.g., benzylic ether part (Ph-CH2O-CH2-), benzylic alcohol part (Ph-CH2O-H), or methoxymethylene group (-CH2-O-)] in the compound (A-b) having a benzylic ether skeleton contained in the mixture. In addition, when the total number of these respective reaction points is set to 1, the compounding 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, relative to 1 mole of the total number of these respective reaction points, the compounding amount of the aromatic amine compound (A-a) is preferably 1 to 10 moles.

[0263] In addition, as a specific method for carrying out the reaction, it is usually the following method: charging all the raw materials at once and directly reacting at a specified temperature, or charging one of the aromatic amine compound (A-a) or the compound (A-b) having a benzylic ether skeleton and an acid catalyst, and while maintaining the specified temperature, adding dropwise the other of the aromatic amine compound (A-a) or the compound (A-b) having a benzylic ether skeleton while reacting. At this time, the dropping time is usually 0.1 to 12 hours, preferably 6 hours or less. After the reaction, in the case of using a solvent, the solvent and unreacted substances can be distilled off as needed to obtain the intermediate amine compound (A-ab), and in the case of not using a solvent, the unreacted substances can be distilled off to obtain the target intermediate amine compound (A-ab).

[0264] As the acid catalyst used in the step (1), an organic acid, an inorganic acid, or a solid acid can be used.

[0265] Examples of the organic acid include aliphatic sulfonic acids such as methanesulfonic acid or fluoromethanesulfonic acid; aromatic sulfonic acids such as 3-morpholinopropanesulfonic acid, piperazine-1,4-bis(2-ethanesulfonic acid), 10-camphorsulfonic acid, 4-chlorobenzenesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, or trifluoromethanesulfonic acid; alkyl phosphates such as dimethyl phosphate or diethyl phosphate; alkyl sulfates such as dimethyl sulfate, diethyl sulfate, or lauryl sulfate; aromatic sulfates such as phenyl sulfate or fluorophenyl sulfate; and various acids such as oxalic acid.

[0266] Examples of the inorganic acid include phosphoric acid, hydrochloric acid, sulfuric acid, nitric acid, boric acid, etc. Examples of the solid acid include activated clay, acid clay, alumina, silica-alumina, zeolite, layered silicate, heteropolyacid, strongly acidic ion exchange resin, etc. Examples of the layered silicate include dickite, nacrite, kaolinite, anauxite, metahalloysite, halloysite, etc. of the kaolin group; chrysotile, lizardite, antigorite, etc. of the serpentine group; montmorillonite, sauconite, beidellite, nontronite, saponite, taeniolite, hectorite, stevensite, etc. of the montmorillonite group; vermiculite of the vermiculite group; mica, illite, sericite, glauconite, etc. of the mica group; attapulgite, sepiolite, palygorskite, bentonite, pyrophyllite, talc, chlorite group. These layered silicates may also form a mixed layer. In addition, the acid catalyst may be used alone or in combination of two or more kinds.

[0267] After the reaction in the step (1), from the viewpoint of operability, it is also preferable to use a solid acid that can be easily removed by filtration as the catalyst. When using other acids, it is preferable to perform neutralization with an alkali and washing with water after the reaction.

[0268] It should be noted that the alkali is not particularly limited and may be an organic base or an inorganic base. Examples of the organic base include alkali metal alkoxides such as sodium methoxide, lithium methoxide, sodium ethoxide, lithium ethoxide, sodium tert-butoxide, potassium tert-butoxide; trialkylamines such as triethylamine, ethyldiisopropylamine; aniline derivatives having an alkyl group with 1 to 4 carbon atoms such as N,N-dimethylaniline, N,N-diethylaniline; pyridine derivatives that may have an alkyl group substituent with 1 to 4 carbon atoms such as pyridine, 2,6-dimethylpyridine; 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, lithium hydride; alkaline earth metal hydrides such as calcium hydride; alkali metal hydroxides such as sodium hydroxide, potassium hydroxide; carbonates or bicarbonates of alkali metals or alkaline earth metals such as sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate; halides of alkali metals or alkaline earth metals such as potassium fluoride, cesium fluoride, potassium iodide. These alkalis may be used alone or in combination of two or more kinds.

[0269] Regarding the blending amount of the acid catalyst, relative to 100 parts by mass of the total amount of the raw materials (compound (A-b) having a benzylic ether skeleton and aromatic amine compound (A-a)) charged, the acid catalyst is blended in the range of 0.1 to 50 parts by mass, and in terms of operability and economy, it is preferably in the range of 1 to 20 parts by mass. The reaction temperature is usually in the range of 100 to 300 °C, but in order to suppress the formation of isomeric structures and avoid side reactions such as thermal decomposition, it is preferably in the range of 120 to 250 °C.

[0270] In the said step (1), as the reaction time of the mixture of the compound (A-b) having a benzylic ether skeleton and the aromatic amine compound (A-a), that is, the crosslinking reaction time, since the reaction does not proceed completely in a short time, and on the other hand, side reactions such as thermal decomposition reaction of the product occur when it is set to a long time, it is usually in the range of 1 to 60 hours in total, preferably in the range of 1 to 20 hours in total under the said reaction temperature conditions.

[0271] In the method for producing the intermediate amine compound (A-ab), the aromatic amine compound (A-a) or its derivative also serves as a solvent, so it is not necessary to use other solvents, and solvents can also be used. For example, in the case of reacting Nikanol L as the compound (A-b) having a benzylic ether skeleton as a raw material, the following method can be adopted: using a solvent capable of azeotropic dehydration such as toluene, xylene or chlorobenzene, azeotropically dehydrating the water contained in the catalyst etc. as needed, then distilling off the solvent, and then carrying out the reaction within the above-mentioned reaction temperature range.

[0272] The intermediate amine compound (A-ab) obtained through the said step (1) preferably has a partial structure represented by the following general formula (1), a partial structure represented by the following general formula (t-1) which is chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (t-2) which is chemically bonded to the partial structure represented by the general formula (1).

[0273] [Chemical formula 24]

[0274]

[0275] [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 * respectively represent bonding ends, and it means that one bonding end is chemically bonded at the position of L 13 or L 14 in the following general formula (t-1), and the other bonding end is at the position of L 11 or L12 Bonding is carried out at the position.

[0276] [Chemical formula 25]

[0277]

[0278] [In the above general formula (t-1) or (t-2), R 11 and R 15 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 and R 14 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, L 11 to L 14 each independently represents a bonding end, and at the position of L 11 or L 12 bonding is carried out with the partial structure represented by the general formula (1), and at the position of L 13 or L 14 bonding is carried out with the partial structure represented by the general formula (1), m 1 represents an integer of 0 or more and 2 or less, and m 3 represents an integer of 0 or more and 2 or less.]

[0279] "R 13 , m 2 and n 1 " in the above general formula (1) has the same meaning as "R 13 , m 2 and n 1 " in the above general formula (1).

[0280] In addition, "L 11 , L 12 , L 13 , L 14 , R 11 , R 12 , R 14 , R 15 , m 1 and m 3 " in the above general formula (t-1) and general formula (t-2) has the same meaning as "L 11 , L 12 , L 13 , L 14 , R 11 , R 12 , R 14 , R 15 , m 1 and m 3 " in the general formula (T-1) and (T-2).

[0281] In the present embodiment, the amine equivalent of the intermediate amine compound (A-ab) is preferably 160 to 1200 g / equivalent, more preferably 180 to 600 g / equivalent.

[0282] It should be noted that the measurement of the amine equivalent of the intermediate amine compound (A-ab) in this specification is a value measured by the method of neutralization titration specified in JIS K 0070 (1992).

[0283] - Step (2): Maleimidation -

[0284] The step (2) is a step of reacting the intermediate amine compound (A-ab) obtained in the step (1) with maleic anhydride (A-c). Since the amino group of the intermediate amine compound (A-ab) can form a chemical structure in which the amino group is substituted by an N-substituted maleimide ring through a maleimidation reaction, the polyimide resin (A) can be obtained.

[0285] The intermediate amine compound (A-ab) having the partial structure represented by the above general formula (1), the partial structure represented by the general formula (t-1), and the partial structure represented by the general formula (t-2) obtained through the step (1) is put into a reactor, dissolved in an appropriate solvent, and then reacted with maleic anhydride (A-c) in the presence of a catalyst. Then, 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 by reduced pressure, whereby the polyimide resin (A) as the target product can be obtained. In addition, a dehydrating agent can be used during the reaction as needed.

[0286] Examples of the organic solvent used in the step (2) include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone; aprotic solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane; cyclic ethers such as dioxane and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; and aromatic solvents such as benzene, toluene, and xylene. In addition, they can be used alone or in combination.

[0287] In the step (2), as the mixing ratio of the intermediate amine compound (A-ab) and maleic anhydride (A-c), it is preferable to adjust the equivalent ratio of maleic anhydride (A-c) to the amino equivalent of the intermediate amine compound (A-ab) to be in the range of 1 to 5, more preferably to add it in the range of 1 to 3. It is a preferable mode to carry out the reaction in an organic solvent having a mass ratio of 0.1 to 10, preferably 0.2 to 5, based on the total amount of the intermediate amine compound (A-ab) and maleic anhydride (A-c).

[0288] Examples of the catalyst that can be used in the step (2) include inorganic salts such as acetates, chlorides, bromides, sulfates, and nitrates of nickel, cobalt, sodium, calcium, iron, lithium, and manganese; inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid; solid acids such as activated clay, acid clay, silica-alumina, zeolite, and strongly acidic ion exchange resin; heteropolyhydrochloric acid, etc. Toluene sulfonic acid is particularly preferably used.

[0289] Examples of the dehydrating agent used in the step (2) include lower aliphatic carboxylic anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride; oxides such as phosphorus pentoxide, calcium oxide, and barium oxide; inorganic acids such as sulfuric acid; porous ceramics such as molecular sieves, etc. Acetic anhydride is preferably used.

[0290] There is no particular limitation on the amount of the catalyst and dehydrating agent that can be used in the step (2). Generally, per 1 equivalent of the amino group (-NH2) of the intermediate amine compound (A-ab), 0.0001 to 1 mol, preferably 0.01 to 0.3 mol of the catalyst can be used, and 1 to 3 mol, preferably 1 to 1.5 mol of the dehydrating agent can be used.

[0291] In the step (2), as the reaction conditions for maleimidation, the above intermediate amine compound (A-ab) and maleic anhydride (A-c) can be introduced, and after reacting in the temperature range of 10 to 100 °C, preferably 30 to 60 °C for 0.5 to 12 hours, preferably 1 to 4 hours, the catalyst is added, and then reacted in the temperature range of 90 to 130 °C, preferably 105 to 120 °C for 1 to 24 hours, preferably 1 to 10 hours.

[0292] <<Polyimide resin mixture (C)>>

[0293] The polyimide resin (A) of the present embodiment may be a mixture. For example, when using the aromatic amine compound (A-a) represented by the above general formula (a-1), the compound (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c) as the reaction raw material (1) as the polyimide resin (A), since there are multiple reaction points of the compound (A-b) having a benzyl ether skeleton relative to the aromatic amine compound (A-a) represented by the above general formula (a-1), the resulting intermediate amine compound (A-ab) itself can be a mixture of various types. Therefore, the polyimide resin (A) can also be a mixture of compounds having various chemical structures.

[0294] It should be noted that in this specification, the term "polymaleimide resin (A)" includes monomers and mixtures. On the other hand, when the polymaleimide resin (A) only represents a mixture, it is called a polymaleimide resin mixture (C).

[0295] The curable composition of the present embodiment may be a composition containing a specific polymaleimide resin mixture (C) and the above amine compound (B), and the specific polymaleimide resin mixture (C) contains the above polymaleimide resin (A). According to the manufacturing method of the above polymaleimide resin (A), sometimes a mixture containing the polymaleimide resin (A) and a maleimide polybody compound described later can be obtained. Even if this mixture is incorporated into the curable composition, a curable composition that highly balances low hygroscopicity, low dielectric constant, and low dielectric loss tangent after curing can be obtained.

[0296] Hereinafter, the polymaleimide resin mixture (C) will be described in detail.

[0297] The polymaleimide resin mixture (C) contains a polymaleimide resin component having a partial structural unit represented by the following general formula (1a) and a maleimide polybody compound represented by the following general formula (2). Relative to the total amount of the polymaleimide resin component, it contains 1 to 99% by mass of the above polymaleimide resin (A), and relative to the total amount of the polymaleimide resin mixture (C), it contains 80% by mass or less of the maleimide polybody compound.

[0298] [Chemical formula 26]

[0299]

[0300] [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.]

[0301] [Chemical formula 27]

[0302]

[0303] [In the above general formula (2), R 21 and R 25 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 22 and R24 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.]

[0304] The polyimide resin mixture (C) has high solubility in solvents and exhibits low dielectric loss tangent and high heat resistance after curing. In addition, among the maleimide oligomer compounds represented by the general formula (2), n 21 for the dimer with n being 1 has high crystallinity, and as it becomes a trimer or tetramer with n 21 being 2 or more, a tendency for improved solubility is shown. It should be noted that by setting the substituents (R 11 or R 15 , R 12 or R 14 ) in the partial structure represented by the general formula (T-1) or the general formula (T-2) as in the present invention, the proportion of trimers and tetramers with excellent solubility can be increased.

[0305] In addition, the curable composition containing the polyimide resin mixture (C) exhibits low dielectric loss tangent and low dielectric constant after curing.

[0306] "R 11 , R 12 , R 13 , n 1 , m 1 and m 2 " in the above general formula (1a) has the same meaning as "R 11 , R 12 , R 13 , n 1 , m 1 and m 2 " in the above general formula (1) or the general formula (T-2).

[0307] In addition, "R 21 and R 25 " in the general formula (2) each independently has the same meaning as "R 11 or R 15 " in the general formula (T-1) and the general formula (T-2).

[0308] In addition, "R 22 and R 24 " in the general formula (2) each independently has the same meaning as "R 12 or R 14 " in the general formula (T-1) and the general formula (T-2).

[0309] In the polyimide resin mixture (C) of the present embodiment, relative to the total amount of the polyimide resin component, it preferably contains 10% to 99% by mass, more preferably 15% or more to 98% by mass, and still more preferably 20% to 97% by mass of a polyimide resin (A) having a partial structure represented by the above general formula (1), a partial structure represented by the following general formula (T-1) that is chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (T-2) that is chemically bonded to the partial structure represented by the general formula (1). And, relative to the total amount of the polyimide resin mixture (C), it preferably contains 5% to 80% by mass, more preferably 7% to 80% by mass, and still more preferably 10% or more to 80% by mass of the maleimide oligomer compound represented by the general formula (2).

[0310] As a preferred polyimide resin mixture (C) of the present embodiment, it contains a polyimide resin represented by the general formula (1A) (wherein, in the general formula (1A), n1 is a polyimide resin of 1 or more) and the maleimide oligomer compound represented by the general formula (2). Relative to the polyimide resin mixture (C), the content of the polyimide resin represented by the general formula (1A) (wherein, in the general formula (1A), n1 is a polyimide resin of 1 or more) is preferably 10% to 99% by mass, more preferably 15% or more to 98% by mass, and still more preferably 20% to 97% by mass. Relative to the polyimide resin mixture (C), the content of the maleimide oligomer compound represented by the general formula (2) is preferably 5% to 80% by mass, more preferably 7% to 80% by mass, and still more preferably 10% to 80% by mass.

[0311] As another preferred polyimide resin mixture (C) of the present embodiment, it is composed of the polyimide resin represented by the general formula (1A). The polyimide resin represented by the general formula (1A) is a resin using the aromatic amine compound (A-a) represented by the above general formula (a-1), the compound (A-b) having a benzyl ether skeleton, and maleic anhydride (A-c) as reaction raw materials (1). The reaction raw materials (1) can be formulated as follows: the aromatic amine compound (A-a) represented by the above general formula (a-1) is preferably 5 to 98% by mass, more preferably 10 to 95% by mass, and still more preferably 15 to 90% by mass; the compound (A-b) having a benzyl ether skeleton is preferably 1 to 90% by mass, more preferably 2 to 85% by mass, and still more preferably 3 to 80% by mass; maleic anhydride (A-c) is preferably 2 to 90% by mass, more preferably 3 to 85% by mass, and still more preferably 4 to 80% by mass.

[0312] <Amine compound (B)>

[0313] The curable composition of the present embodiment contains an amine compound (B). By combining the amine compound (B) with the polymaleimide resin (A), the whole composition can contribute to low-temperature curing and exhibit excellent moldability, so it can be used as a molding material for structural materials and is useful. In addition, the amine compound (B) acts as a curing agent through the reaction with the polymaleimide resin (A), can generate three-dimensional crosslinking, and can obtain a cured product with excellent heat resistance, which is a preferred mode.

[0314] Examples of the amine compound (B) include compounds having primary to tertiary amino groups, preferably hydrocarbons having 1 or more carbon atoms, preferably 3 to 25 carbon atoms, and more preferably hydrocarbon compounds having 2 or more primary amino groups in one molecule. As the amine compound (B), an aliphatic amine compound or an aromatic amine compound is preferred, and an aliphatic primary diamine compound or an aromatic primary diamine compound is more preferred.

[0315] It should be noted that aromatic amine compounds include aromatic heterocyclic compounds, and aliphatic amine compounds include alicyclic aliphatics.

[0316] Specific examples of the aliphatic amine compound include, for example, ethylenediamine, diethylenetriamine, hexamethylenediamine, triethylenetetramine, isophoronediamine, guanidine derivatives, guanamine derivatives, 1,3-bis(aminomethyl)cyclohexane, morpholine, 4,4'-methylenebis(cyclohexylamine), and 4,4'-ethylenebis(cyclohexylamine). The aliphatic amine compound can be used alone or in combination of two or more.

[0317] Specific examples of the aromatic amine compound include, for example, o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3-methyl-1,4-diaminobenzene, m-xylenediamine, p-xylenediamine, diethyltoluenediamine, 2,5-dimethyl-1,4-diaminobenzene, diaminodiphenylmethane (e.g., 4,4'-diaminodiphenylmethane), diaminodiphenylethane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, diaminodiphenyl ether (e.g., 4,4'-diaminodiphenyl ether), diaminodiphenyl sulfone (e.g., 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone), 4,4'-diaminodiphenyl ketone, benzidine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-methylenebis(2-ethyl-6-methylaniline), 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl) sulfone, bis(4-(3-aminophenoxy)phenyl) sulfone, 9,9-bis(4-aminophenyl)fluorene, and imidazole. The aromatic amine compound may be used alone or in combination of two or more.

[0318] Among the aromatic amine compounds, m-phenylenediamine, p-phenylenediamine, 3-methyl-1,4-diaminobenzene, or 2,5-dimethyl-1,4-diaminobenzene is more preferable when paying attention to the mechanical properties after curing. On the other hand, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-bis(4-aminophenoxy)biphenyl, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, or 4,4'-methylenebis(2-ethyl-6-methylaniline) is more preferable when paying attention to heat resistance.

[0319] In addition, when solubility or operability in a solvent is emphasized, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-diethyldiphenylmethane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 4,4'-methylenebis(2-ethyl-6-methylaniline) are more preferable. Further, when low dielectric properties are emphasized, 4,4'-diamino-3,3'-diethyl-diphenylmethane and 2,2-bis(4-(4-aminophenoxy)phenyl)propane are more preferable.

[0320] In addition, as other amine compounds (B) other than the aliphatic amine compound and the aromatic amine compound, hydroxylamine sulfate, BF3-amine complex, etc. can be cited.

[0321] As the amine compound (B), when control of the curing reaction and moldability are emphasized, an aromatic amine compound is preferable. The aliphatic amine compound acts as a catalyst and shows a tendency for the curing reaction to proceed rapidly. Therefore, when moldability is emphasized, it is preferable to use an aromatic amine compound.

[0322] In the curable composition of the present embodiment, relative to the entire curable composition, it is preferable to contain 5% by mass or more and 50% by mass or less of the amine compound (B), more preferably 7% by mass or more and 30% by mass or less, and most preferably 10% by mass or more and 20% by mass or less. From the viewpoint of heat resistance, it is preferable that the content of the amine compound (B) is in the range of 10% by mass or more and 20% by mass or less.

[0323] <Curing agent (D) other than amine compound>

[0324] In the curable composition of the present embodiment, a curing agent (D) other than the above amine compound (B) may be added within a range that does not impair the effects of the present invention. It should be noted that relative to 100% by mass of the total amount of the curable composition, the curing 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. From the viewpoints of curability and low dielectric loss tangent, it is preferable that the content of the curing agent (D) is in the range of 5% by mass or more and 10% by mass or less.

[0325] As the curing agent (D), for example, cyanate ester compounds, amide-based compounds, acid anhydride-based compounds, phenol-based compounds, polyphenylene ether-based compounds, compounds having a substituent containing an unsaturated double bond, diene-based polymers, etc. can be cited. These curing agents can be used alone or in combination of two or more.

[0326] Examples of the cyanate ester compound include bisphenol A cyanate ester resin, bisphenol F cyanate ester resin, bisphenol E cyanate ester resin, bisphenol S cyanate ester resin, bisphenol thioether cyanate ester resin, phenylene ether cyanate ester resin, naphthalene ether cyanate ester resin, biphenyl cyanate ester resin, tetramethylbiphenyl cyanate ester resin, polyhydroxynaphthalene cyanate ester resin, phenol novolak cyanate ester resin, cresol novolak cyanate ester resin, triphenylmethane cyanate ester resin, tetraphenylethane cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl cyanate ester resin, naphthol novolak cyanate ester resin, naphthol aralkyl cyanate ester resin, naphthol-phenol co-condensed novolak cyanate ester resin, naphthol-cresol co-condensed novolak cyanate ester resin, aromatic hydrocarbon formaldehyde resin-modified phenolic resin type cyanate ester resin, biphenyl-modified novolak cyanate ester resin, anthracene type cyanate ester resin, etc. They may be used individually as one kind, or two or more kinds may be used in combination.

[0327] Examples of the amide compound include dicyandiamide, polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, etc.

[0328] Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.

[0329] Examples of the phenolic compound include phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (ZYLOCK resin), polyhydric phenol novolak resin synthesized from a polyhydric hydroxy compound represented by resorcinol novolak resin and formaldehyde, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolak resin, biphenyl-modified phenolic resin (a polyhydric phenol compound in which phenolic nuclei are linked by a bis-methylene group), biphenyl-modified naphthol resin (a polyhydric naphthol compound in which phenolic nuclei are linked by a bis-methylene group), amino triazine-modified phenolic resin (a polyhydric phenol compound in which phenolic nuclei are linked by melamine, benzoguanamine, etc.), polyhydric phenol compounds such as aromatic ring-modified novolak resin containing an alkoxy group (a polyhydric phenol compound in which a phenolic nucleus and an aromatic ring containing an alkoxy group are linked by formaldehyde), etc.

[0330] Examples of the polyphenylene ether compound preferably have a structure represented by the following general formula (3-1) or (3-2).

[0331] [Chemical formula 28]

[0332]

[0333] [Chemical Formula 29]

[0334]

[0335] In the above general formulas (3-1) and (3-2), R 31 ~R 38 can each independently be, for example, 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 alkoxycarbonyl 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. As the terminal structure of the structure of the above general formulas (3-1) and (3-2), a terminal structure having a hydroxyl group or a group containing a reactive double bond, etc. can be mentioned. Further, v is an integer from 1 to 30, and w and u are also integers from 1 to 30.

[0336] 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.

[0337] 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.

[0338] The alkoxycarbonyl group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, etc.

[0339] 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.

[0340] 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.

[0341] R 31 ~R 38 in the above general formulas (3-1) and (3-2) can be the same as or different from each other, and are preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a cycloalkyl group having 3 to 5 carbon atoms, more preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, further preferably a hydrogen atom, a methyl group, an ethyl group, and particularly preferably a hydrogen atom, a methyl group.

[0342] Y in the above general formula (3-2) can be a divalent aromatic group derived from an aromatic compound having two phenolic hydroxyl groups.

[0343] Moreover, the aromatic compound having two phenolic hydroxyl groups is not particularly limited, and examples thereof include catechol, resorcinol, hydroquinone, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol B, bisphenol BP, bisphenol C, bisphenol F, tetramethyl bisphenol A, etc. Among them, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol E, and bisphenol F are preferred, and 4,4'-biphenol, bisphenol A, and tetramethyl bisphenol A are more preferred.

[0344] In addition, 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), so Y becomes a divalent aromatic group derived from the aromatic compound having two phenolic hydroxyl groups. In other words, the group obtained by removing two arbitrary hydrogen atoms from the above-mentioned aromatic compound having two phenolic hydroxyl groups is defined as the "divalent aromatic group derived from the aromatic compound having two phenolic hydroxyl groups".

[0345] As the compound having a substituent containing an unsaturated double bond, for example, as long as it is a compound having two or more substituents containing an unsaturated bond in the molecule, there is no particular limitation, and examples thereof include compounds having allyl, isopropenyl, 1-propenyl, acryloyl, methacryloyl, styryl, styrylmethyl, etc. as the substituent containing an unsaturated bond.

[0346] As the diene polymer, for example, an unmodified diene polymer not modified with a polar group can be mentioned. Here, the polar group refers to a functional group that affects the dielectric properties, and examples thereof include a phenolic group, an amino group, an epoxy group, etc. The diene polymer is not particularly limited, and for example, 1,2-polybutadiene, 1,4-polybutadiene, etc. can be used.

[0347] As the diene polymer, a homopolymer of butadiene and its derivatives in which 50% or more of the butadiene units in the polymer chain are 1,2-bonds can also be used.

[0348] <Other resin (E)>

[0349] Within the scope that does not impair the object of the present invention, the curable composition of the present embodiment may contain other resins (E) in addition to the polyimide resin (A) and the amine compound (B). As the other resin (E), it is also possible to appropriately blend bismaleimide compounds other than the polyimide resin (A), allyl ether compounds, allyl amine compounds, triallyl cyanurate, vinyl phenol compounds, vinyl-containing polyolefin compounds, etc., epoxy resins, phenolic 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.

[0350] In addition, since the curable composition of the present embodiment contains the amine compound (B), an epoxy resin can also be selected as the other resin (E). Thus, in the curable composition containing the polyimide resin (A), the amine compound (B), and the epoxy resin, the amine compound (B) functions as a curing agent, so the adhesion to copper is improved. For example, it can be useful in the manufacture of circuit boards using copper foils.

[0351] The epoxy resin is not particularly limited. For example, there can be mentioned novolak type epoxy resins such as phenol novolak type epoxy resin, cresol novolak type epoxy resin, α-naphthol novolak type epoxy resin, β-naphthol novolak type epoxy resin, bisphenol A novolak type epoxy resin, biphenol novolak type epoxy resin; aralkyl type epoxy resins such as phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin; bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol A type epoxy resin; biphenyl type epoxy resins such as biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, epoxy resin having a biphenyl skeleton and a diglycidoxybenzene skeleton; naphthalene type epoxy resin; binaphthol type epoxy resin; binaphthalene type epoxy resin; dicyclopentadiene phenol type epoxy resin; glycidylamine type epoxy resins such as tetraglycidyl diaminodiphenylmethane type epoxy resin, triglycidyl p-aminophenol type epoxy resin, glycidylamine type epoxy resin of diaminodiphenyl sulfone; diglycidyl ester type epoxy resins such as 2,6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resin, glycidyl ester type epoxy resin of hexahydrophthalic anhydride; benzopyran type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, 7-phenylhexamethyldibenzopyran, etc. They can be used alone, one kind each, or two or more kinds can be used in combination.

[0352] Relative to 100% by mass of the total amount of the curable composition, 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. If the content of the other resin (E) is in the range of 5% by mass or more and 10% by mass or less, it is preferable from the viewpoint of heat resistance.

[0353] <Curing accelerator>

[0354] The curable composition of the present embodiment may also be appropriately used in combination with a curing accelerator as needed. As the curing accelerator, various curing accelerators can be used. For example, it is effective to add a polymerization initiator such as an organic peroxide or an azo compound, or a basic catalyst such as a phosphine compound or a tertiary amine. Specific examples of the curing accelerator include, for example, benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, TPP-MK, TPP-K, triethylamine, imidazoles, etc. The curing accelerator can be used alone or in combination of two or more. As the blending amount of the curing accelerator, it is preferably 0.05 to 5% by mass of the entire curable resin composition.

[0355] <Additive>

[0356] The curable composition of the present embodiment may also be appropriately used in combination with additives as needed. As the additives, silane coupling agents, mold release agents, pigments, emulsifiers, non-halogen flame retardants, inorganic fillers, flame retardants, solvents, etc. can be cited. Relative to 100% by mass of the total amount of the 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.

[0357] As the flame retardant, inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, halogen-based flame retardants or non-halogen flame retardants can be cited. In the curable composition of the present embodiment, within the range not impairing the purpose, in order to exhibit flame retardancy, it is more preferable to blend a non-halogen flame retardant substantially free of halogen atoms. As the non-halogen flame retardant, for example, phosphorus-based flame retardants, nitrogen-based flame retardants, organosilicon-based flame retardants, inorganic-based flame retardants, organic metal salt-based flame retardants, etc. can be cited, and they can be used alone or in combination.

[0358] In the curable composition of the present embodiment, an inorganic filler may be blended as needed. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide, and the like. When the blending amount of the inorganic filler is particularly increased, fused silica is preferably used. The fused silica may be in the form of crushed or spherical particles, but in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, spherical fused silica is preferably mainly used. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. Considering flame retardancy, its filling rate is preferably high, and particularly preferably 30% by mass or more and 50% by mass or less based on the total amount of the curable composition. In addition, when the curable composition is used for applications such as conductive paste described in detail below, conductive fillers such as silver powder and copper powder can be used.

[0359] <Content of each component>

[0360] In the curable composition of the present embodiment, based on the entire curable composition (100% by mass), the lower limit of the total content of the polyimide resin (A) and the amine compound (B) is preferably 40% by mass, 42% by mass, 45% by mass, 47% by mass, 48% by mass, or 50% by mass. In addition, 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, based on the entire curable composition (100% by mass), the total content of the polyimide resin (A) and the amine compound (B) is preferably 40% by mass or more and 100% by mass or less, more preferably 45% by mass or more and 100% by mass or less, and still more preferably 50% by mass or more and 100% by mass or less.

[0361] In the curable composition of the present embodiment, based on the entire curable composition (100% by mass), the lower limit of the total content of the polyimide resin (A), the amine compound (B), and the inorganic filler is preferably 70% by mass, 73% by mass, 75% by mass, 77% by mass, or 80% by mass. In addition, the upper limit of the total content is preferably 100% by mass, 99% by mass, 98% by mass, or 97% by mass. The upper limit value and the lower limit value can be arbitrarily combined in the same manner as the range of the total content of the polyimide resin (A) and the amine compound (B).

[0362] In the curable composition of the present embodiment, with respect to the entire curable composition (100% by mass), the lower limit of the total content of the polymaleimide resin (A), the amine compound (B), and the additive is preferably 43% by mass, 45% by mass, 48% by mass, 50% by mass, or 53% by mass. Further, the upper limit of the total content is preferably 100% by mass, 99% by mass, 98% by mass, or 97% by mass. The upper limit value and the lower limit value can be arbitrarily combined in the same manner as the range of the total content of the polymaleimide resin (A) and the amine compound (B).

[0363] The curable composition of the present embodiment preferably contains 10% by mass or more of a component represented by the above general formula (1A) and having a sum of n 1 and n 3 of 1 or more as the polymaleimide resin (A). In the curable composition, by making the content of the specific polymaleimide resin represented by the above general formula (1A) 10% by mass or more, the cured product thereof can further highly achieve both low hygroscopicity and low dielectric loss tangent and low dielectric constant. Further, from the viewpoint of heat resistance, the curable composition of the present embodiment preferably contains 5% by mass or more of a component represented by the above general formula (1A) and having n 2 of 1 or more.

[0364] [Cured product]

[0365] The cured product of the present embodiment is preferably obtained from the above curable composition. The cured product can be obtained by subjecting the curable composition to a curing reaction. The curable composition can be obtained by uniformly mixing the above components (for example, a curing agent, a 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 a laminate, a casting, an adhesive layer, a coating film, and a film.

[0366] As the curing (thermal curing) reaction, it is easy to proceed even without a catalyst, but in the case where a further rapid reaction is desired, it is effective to add a polymerization initiator such as an organic peroxide or an azo compound, a basic catalyst such as a phosphine compound or a tertiary amine. For example, there are benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazoles, etc., and as the compounding amount, it is preferably 0.05 to 5% by mass of the entire curable resin composition.

[0367] The cured product obtained from the curable composition containing the polyimide resin (A) and the amine compound (B) has both excellent low moisture absorption and low dielectric properties, and thus 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, laminated films, laminated substrates, adhesives using conductive paste, resist materials, etc. In addition, it can also be suitably used as the matrix resin of fiber-reinforced resins, and is particularly suitable as a prepreg with high heat resistance or a small dimensional change rate. In addition, the polyimide resin (A) contained in the curable composition can be made into a coating because it exhibits excellent solubility in various solvents. The heat-resistant members and electronic members thus obtained can be suitably used for various purposes, such as 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, wind power generation housing members, etc., but are not limited to these.

[0368] Hereinafter, representative products (prepregs, circuit boards, laminated substrates, laminated films, semiconductor encapsulants, semiconductor devices, conductive paste) manufactured using the curable composition of the present embodiment will be described by way of example.

[0369] <Prepreg>

[0370] The prepreg of the present embodiment has a reinforcing substrate and a semi-cured product of the curable composition of the present embodiment impregnated in the reinforcing substrate. As a method for obtaining a prepreg from the curable composition, the following method can be cited: After impregnating a varnished curable composition into a reinforcing substrate (paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass fiber mat, glass fiber gauze, etc.) in combination with an organic solvent described later, heating is performed at a heating temperature corresponding to the type of solvent used, preferably 50 to 170 °C, whereby the curable composition is semi-cured (or uncured) to obtain a prepreg. As the mass ratio of the curable composition to the reinforcing substrate used at this time, there is no particular limitation, and it is generally preferably prepared such that the resin amount contained in the composition in the prepreg becomes 20 to 60% by mass.

[0371] In the present embodiment, the semi-cured product of the curable composition is obtained by adjusting the heating temperature and heating time so that the curing reaction does not complete but stops midway. In addition, for example, the semi-cured product can have a curing degree of, for example, 85% or less and 5% or more. On the other hand, the cured product in the present embodiment can have a higher curing degree than the semi-cured product.

[0372] It should be noted that the degree of cure of the semi-cured product can be calculated by the following formula by measuring the heat of cure released during heating of the curable composition and the heat of cure released by the semi-cured product using DSC.

[0373] Degree of cure (%) = [1 - (heat of cure released by semi-cured product / heat of cure released by curable composition)] × 100

[0374] 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 or appropriate amount of use can be appropriately selected according to the application. For example, in the case of further manufacturing a printed circuit board from the prepreg as described below, it is preferable to use a polar solvent having a boiling point of 160 °C or lower such as methyl ethyl ketone, acetone, or dimethylformamide. In addition, it is preferably used in a proportion such that the non-volatile component is 40 to 80% by mass.

[0375] In addition, as the reinforcing substrate used in the production of the prepreg of the present embodiment, there are woven fabrics, non-woven fabrics, or mats, papers, etc. formed of inorganic fibers and organic fibers such as glass fibers, polyester fibers, and polyamide fibers, and they can be used alone or in combination.

[0376] As the heat treatment conditions of the prepreg of the present embodiment, they are appropriately selected according to the type and amount of use of the organic solvent, catalyst, various additives, etc., and are usually preferably carried out under the conditions of a temperature of 80 to 220 °C and a time of 3 minutes to 30 minutes.

[0377] <Circuit board>

[0378] The circuit board of the present embodiment is a laminate having the above prepreg and copper foil. As a method for obtaining a printed circuit board from the curable composition of the present embodiment, there can be mentioned a method of laminating the above prepreg by a conventional method, appropriately overlapping copper foil, and heating and pressing at 170 to 300 °C under a pressure of 1 to 10 MPa for 10 minutes to 3 hours.

[0379] <Multilayer substrate>

[0380] As a method for obtaining a multilayer substrate from the curable composition of the present embodiment, there can be mentioned a method via the following steps 1 to 3.

[0381] In step 1, first, the curable composition appropriately blended with rubber, filler, etc. is applied to the circuit board having a circuit formed thereon using a spraying method, a curtain coating method, etc., and then cured.

[0382] In Step 2, as needed, after opening a prescribed via hole portion or the like in the circuit board coated with the curable composition, it is treated with a roughening agent, and its surface is washed with hot water, thereby forming unevenness on the substrate, and a plating treatment of a metal such as copper is performed.

[0383] In Step 3, as needed, the operations of Steps 1 to 2 are sequentially repeated to form a laminated substrate by alternately laminating a resin insulating layer and a conductor layer of a prescribed circuit pattern.

[0384] It should be noted that, in the above steps, the opening of the via hole portion can be performed after forming the outermost resin insulating layer. In addition, the laminated substrate in the present embodiment can also be manufactured by heat-pressing a resin-coated copper foil obtained by semi-curing the composition on a copper foil at 170 to 300 °C on a wiring substrate formed with a circuit, thereby omitting the steps of forming a roughened surface and a plating treatment.

[0385] <Laminated film>

[0386] The laminated film of the present embodiment contains the curable composition of the present embodiment. As a method for manufacturing the laminated film of the present embodiment, the following method can be cited: after coating the above curable composition on a support film (Y), it is dried to form a curable composition layer on the support film (Y), and a bonding film for a multilayer printed wiring board is manufactured, thereby performing the manufacturing.

[0387] When manufacturing a laminated film from a curable composition, it is important that the film softens under the lamination temperature conditions (usually 70 to 140 °C) in the vacuum lamination method, and while laminating the circuit board, it exhibits fluidity (resin flow) such that the resin can fill into the vias or through holes present in the circuit board. It is preferably formulated with the above components to exhibit such characteristics. It should be noted that in the obtained laminated film and circuit board (copper-clad laminate, etc.), in order not to cause a phenomenon such as locally showing different characteristic values due to phase separation, etc., and to exhibit constant performance at any part, appearance uniformity is required.

[0388] Here, the diameter of the via hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually preferred that the resin can be filled within this range. It should be noted that when laminating both sides of the circuit board, it is preferred to fill about 1 / 2 of the via hole.

[0389] The method for manufacturing the above-mentioned adhesive film can be specifically carried out as follows: After preparing the above-mentioned curable composition in a varnish form, coat the varnish-like composition on the surface of the support film (Y), and further dry the organic solvent by heating or blowing hot air, etc., to form a composition layer (X) formed from the curable composition. As the organic solvent, for example, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, cellosolves, carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used. In addition, it is preferably used in a proportion of 30 to 60% by mass of the non-volatile component.

[0390] The thickness of the formed composition layer (X) is usually preferably equal to or greater than the thickness of the conductor layer. The thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, so the resin composition layer preferably has a thickness of 10 to 100 μm. It should be noted that the composition layer (X) in the present embodiment can be protected by a protective film described later. By protecting with a protective film, it is possible to prevent the adhesion and damage of dust, etc. on the surface of the resin composition layer.

[0391] Examples of the above-mentioned support film (Y) and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes simply referred to as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and metal foils such as release paper, copper foil, and aluminum foil. It should be noted that in addition to matte treatment and corona treatment, the support film and the protective film can also be subjected to release treatment.

[0392] The thickness of the support film is not particularly limited, usually 10 to 150 μm, and it is preferably used in the range of 25 to 50 μm. In addition, the thickness of the protective film is preferably 1 to 40 μm.

[0393] 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 heating and curing the adhesive film, it is possible to prevent the adhesion of dust, etc. during the curing process. In the case of peeling off after curing, usually, a release treatment is pre-implemented on the support film.

[0394] It should be noted that a multilayer printed circuit board can be manufactured from the laminated film obtained as described above. For example, when the resin composition layer (X) is protected by a protective film, after peeling them off, the layer (X) of the resin composition is laminated on one or both sides of the circuit board by, for example, vacuum lamination in a manner of direct contact with the circuit board. The lamination method can be intermittent or continuous using rollers. Additionally, if necessary, the laminated film and the circuit board can be heated (preheated) as needed before lamination. Regarding the lamination conditions, it is preferable to set the crimping temperature (lamination temperature) to 70 to 140 °C, and it is preferable to set the crimping pressure to 1 to 11 kgf / cm 2 (9.8×10 4 ~107.9×10 4 N / m 2 ), and it is preferably laminated under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

[0395] <Semiconductor encapsulant>

[0396] The semiconductor encapsulant of the present embodiment contains the curable composition of the present embodiment. The semiconductor encapsulant obtained by using the curable composition of the present embodiment reduces the moisture absorption, dielectric constant, and dielectric loss tangent by using the polyimide resin (A) and the amine compound (B), and thus has excellent processability, moldability, and reflow resistance during the manufacturing process, which is a preferred mode.

[0397] The curable composition of the present embodiment used in the semiconductor encapsulant may contain an inorganic filler. It should be noted that as the filling rate of the inorganic filler, relative to 100 parts by mass of the curable composition of the present embodiment, the inorganic filler can be used, for example, in the range of 0.5 to 1200 parts by mass. Additionally, as the inorganic filler, as described above, for example, barium sulfate, barium titanate, amorphous silica, crystalline silica, Noritake silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, silicon nitride, aluminum nitride, etc. can be cited.

[0398] As a method for obtaining the semiconductor sealing material, methods such as further melting and mixing a curing accelerator and / or an additive, which are optional components, until they become uniform using an extruder, a kneader, a roll, etc. as needed in the curable composition of the present embodiment can be cited. In the case of using it as a highly thermally conductive semiconductor sealing material for power transistors and power ICs, high filling of crystalline silica, alumina, silicon nitride, etc. having a higher thermal conductivity than fused silica can be carried out, or fused silica, crystalline silica, alumina, silicon nitride, etc. can be used. Regarding the filling rate, relative to 100 parts by mass of the curable composition, it is preferable to use an inorganic filler in the range of 30 to 95 parts by mass. Among them, in order to achieve improvements in flame retardancy, moisture resistance, solder crack resistance, and reduction of the linear expansion coefficient, it is more preferably 70 parts by mass or more, and further preferably 80 parts by mass or more.

[0399] <Semiconductor device>

[0400] The semiconductor device of the present embodiment includes a cured product of the above semiconductor sealing material. Since the polyimide resin (A) and the amine compound (B) are used in the semiconductor device obtained using the semiconductor sealing material obtained from the curable composition of the present embodiment, the viscosity is low and the fluidity is excellent. Furthermore, the hygroscopicity, the thermal elastic modulus, or the adhesiveness to the metal material is improved. Therefore, the processability, moldability, and reflow resistance during the manufacturing process are excellent, which is a preferred mode.

[0401] As a method for obtaining the semiconductor device, methods such as casting the semiconductor sealing material or molding it using a transfer molding machine, an injection molding machine, etc., and then heating and curing it in the temperature range of room temperature (20 °C) to 250 °C can be cited.

[0402] <Conductive paste>

[0403] 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 cited. The above conductive paste can be made into a paste resin composition for circuit connection or an anisotropic conductive adhesive according to the type of conductive particles used.

[0404] Examples

[0405] The present invention will be specifically described through examples and comparative examples. Hereinafter, unless otherwise specified, "parts" and "%" are based on mass. It should be noted that the physical properties of the synthesized polyimide resin were measured as follows. In addition, the physical properties of the prepared curable composition were measured as follows, and the results are shown in Table 1.

[0406] (1) GPC measurement

[0407] Using the following measuring device and measuring conditions, calculate the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the polyimide resin obtained in the synthesis example.

[0408] · Measuring device: "HLC-8320GPC" manufactured by Tosoh Corporation

[0409] Column: Guard column "HXL-L" manufactured by Tosoh Corporation

[0410] + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

[0411] + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

[0412] + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation

[0413] + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

[0414] Detector: RI (differential refractometer)

[0415] Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation

[0416] · Measuring conditions: Column temperature 40 °C

[0417] Eluent solvent: Tetrahydrofuran

[0418] Flow rate: 1.0 mL / minute

[0419] · Standard: According to the measurement manual of the "GPC Workstation EcoSEC-WorkStation", use the following monodisperse polystyrene with known molecular weight.

[0420] (Using polystyrene)

[0421] "A-500" manufactured by Tosoh Corporation

[0422] "A-1000" manufactured by Tosoh Corporation

[0423] "A-2500" manufactured by Tosoh Corporation

[0424] "A-5000" manufactured by Tosoh Corporation

[0425] "F-1" manufactured by Tosoh Corporation

[0426] "F-2" manufactured by Tosoh Corporation

[0427] "F-4" manufactured by Tosoh Corporation

[0428] “F-10” manufactured by Tosoh Corporation

[0429] “F-20” manufactured by Tosoh Corporation

[0430] “F-40” manufactured by Tosoh Corporation

[0431] “F-80” manufactured by Tosoh Corporation

[0432] “F-128” manufactured by Tosoh Corporation

[0433] · Specimen: The substance obtained by filtering a 1.0 mass% solution of the polyimide resin (A) obtained in the synthesis example in tetrahydrofuran through a microfilter (50 μL), in terms of resin solid content.

[0434] (2) Amine equivalent and maleimide group equivalent

[0435] The amine equivalent of the aromatic amine obtained in the synthesis example was measured by the following method.

[0436] Precisely weigh approximately 2.5 g of the intermediate amine compound, 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine into a 500 mL stoppered Erlenmeyer flask, then install a condenser and heat under reflux in an oil bath set at 120 °C for 150 minutes.

[0437] After cooling, add 5.0 mL of distilled water, 100 mL of propylene glycol monomethyl ether, and 75 mL of tetrahydrofuran, and titrate with a 0.5 mol / L potassium hydroxide-ethanol solution by potentiometric titration. A blank test was carried out in the same way for correction.

[0438] Amine equivalent (g / equivalent) = (S × 2,000) / (Blank - A)

[0439] S: Amount of specimen (g)

[0440] A: Consumption of 0.5 mol / L potassium hydroxide-ethanol solution (mL)

[0441] Blank: Consumption of 0.5 mol / L potassium hydroxide-ethanol solution in the blank test (mL)

[0442] The maleimide group equivalent of the polyimide resin obtained in the synthesis example is a value converted from the amine equivalent of the intermediate amine compound and is obtained by the following formula.

[0443] Maleimide equivalent (g / equivalent) = Amine equivalent + 80

[0444] (3) FD-MS measurement

[0445] The FD-MS spectrum of the polyimide resin obtained in the synthesis example was measured using the following measuring apparatus and measuring conditions.

[0446] · Measuring apparatus: JMS-T100GC AccuTOF

[0447] · Measuring conditions

[0448] Measuring range: m / z = 4.00 to 2000.00

[0449] Rate of change: 51.2 mA / min

[0450] Final current value: 45 mA

[0451] Cathode voltage: -10 kV

[0452] Recording interval: 0.07 sec

[0453] (4) 13 13C-NMR measurement

[0454] The 13C-NMR spectrum of the polyimide resin obtained in the synthesis example 13 was measured using the following measuring apparatus and measuring conditions.

[0455] · 13 13C-NMR: "JNM-ECZ400S" manufactured by JEOL RESONANCE

[0456] Resonance frequency: 100 MHz

[0457] Number of accumulations: 4000 times

[0458] Solvent: deuterated chloroform

[0459] Sample concentration: 12 mass%

[0460] Relaxing agent: chromium(III) acetylacetonate

[0461] [Synthesis Example 1] Synthesis of polyimide resin (A-1)

[0462] (1) Synthesis of intermediate amine compound (a-1)

[0463] In a flask equipped with a thermometer, a cooling tube, a Dean-Stark separator, and a stirrer, 350 g of 2,3-dimethylaniline, 127.3 g of xylene formaldehyde resin (Nikanol L, manufactured by Fudow Co., Ltd.), 240 g of toluene, and 133.7 g of activated clay were charged, and the temperature was raised to 120 °C with stirring and maintained for 30 minutes. Then, the temperature was raised to 160 °C and maintained for 4 hours. After the maintenance, the temperature was raised to 200 °C in 60 minutes and maintained for 15 hours. After the maintenance, it was diluted with 240 g of toluene, and the activated clay was filtered out by filtration. The filtrate was distilled to remove the solvent and excess 2,3-dimethylaniline under heating and reduced pressure to obtain an intermediate aromatic amine compound (a-1) (amine equivalent: 218 g / eq.). The FD-MS spectrum of the obtained intermediate amine compound (a-1) is shown in Figure 1 , 13 The C-NMR spectrum is shown in Figure 2 .

[0464] (2) Maleimidation

[0465] 70.08 g (1.3 equivalents) of maleic anhydride and 260.4 g of toluene were charged into a 2 L flask equipped with a thermometer, a cooling tube, a Dean-Stark separator, and a stirrer, and stirred at room temperature. Then, a mixed solution of 120.0 g (1 equivalent) of the intermediate amine compound (a-1) and 32.6 g of DMF was added dropwise over 1 hour, and then the reaction was carried out for 2 hours. 5.23 g of p-toluenesulfonic acid monohydrate was added to the reaction solution, the reaction solution was heated, and the azeotropic water and toluene were cooled and separated under reflux, then heated to 115 °C, and the azeotropic water and toluene were cooled and separated under reflux, and only toluene was returned to the system for a 5-hour dehydration reaction. After air-cooling to room temperature, it was concentrated under reduced pressure, the obtained brown solution was dissolved in 600 g of ethyl acetate, washed 3 times with 200 g of ion-exchanged water, and washed 3 times with 150 g of 2% aqueous sodium bicarbonate solution. Then, sodium sulfate was added to the oil layer for drying, and concentrated under reduced pressure. The obtained reaction product was vacuum-dried at 80 °C for 4 hours to obtain a product containing the polymaleimide resin (A-1). The GPC chart of the polymaleimide resin (A-1) is shown in Figure 3 , the FD-MS spectrum is shown in Figure 4 , 13 The C-NMR spectrum is shown in Figure 5 .

[0466] Based on the results of GPC and the like, it was confirmed that the obtained polymaleimide resin (A-1) contained 20% by mass or more of the component represented by the above general formula (1A) and the sum of n 1 and n 3 was 1 or more, and in addition, contained 10% by mass or more of the component with n 2 being 1 or more.

[0467] For each peak of the FD-MS spectrum shown Figure 4 confirm the repeat number in the polymaleimide resin (A-1). Compare each peak with the repeat numbers [n in general formula (1A) 1 and n 2 and the corresponding bonding objects of * are shown in Table 1.

[0468] [Table 1]

[0469] MS NO <![CDATA[n 1 > <![CDATA[n 2 > *Bonding object 319.2 1 0 H 414.2 0 1 H 437.3 2 0 H 532.3 1 1 H 555.4 3 0 H 627.3 0 2 H 650.4 2 1 H 745.4 1 2 H 768.5 3 1 H 863.5 2 2 H 958.5 1 3 H 981.6 3 2 H 1076.6 2 3 H

[0470] [Examples 1-2 and Comparative Examples 1-3]

[0471] [Preparation of Curable Composition]

[0472] The polymaleimide resin (A-1) obtained in Synthesis Example 1, the comparative maleimide compound (A-2) ("BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd., phenylmethane maleimide), the comparative maleimide compound (A-3) ("BMI-5100" manufactured by Daiwa Kasei Kogyo Co., Ltd., 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide), the amine compound (B-1) [4,4'-diaminodiphenylmethane, manufactured by Tokyo Chemical Industry Co., Ltd.], the amine compound (B-2) [4,4'-methylenebis(2-ethyl-6-methylaniline))], and DCPO (manufactured by NOF Corporation, "PERCUMYL D", dicumyl peroxide) as a curing catalyst were mixed in the proportions shown in Table 2 to prepare a curable composition.

[0473] [Production of Cured Product]

[0474] The curable composition was cured under the following conditions to obtain a cured product.

[0475] Curing conditions: After heating and curing at 200 °C for 2 hours using a vacuum press, then heating and curing at 250 °C for 2 hours. The plate thickness after molding was 1.3 mm. For this cured product, the physical properties of the dielectric constant, dielectric loss tangent, and moisture absorption rate were evaluated by the following methods. The results are shown in Table 2.

[0476] [Measurement of Dielectric Constant and Dielectric Loss Tangent]

[0477] According to JIS-C-6481, using the network analyzer "E8362C" manufactured by Agilent Technologies, Inc., the dielectric constant (Dk) and dielectric loss tangent (Df) of the test piece after being stored in a room at 23 °C and 50% humidity for 24 hours after absolute drying were measured by the cavity resonance method at 10 GHz.

[0478] <Determination of moisture absorption>

[0479] In the present examples and comparative examples, as a method for evaluating low hygroscopicity, the moisture absorption rate (%) was calculated and evaluated by the following method.

[0480] A test piece of 5 mm×55 mm×1.3 mm in size was cut out from the obtained cured product using a pressure cooker tester and kept under conditions of 85° C., 85% RH, and 1 atmosphere for 50 hours. The moisture absorption rate (%) was calculated and evaluated using the following formula.

[0481] Moisture absorption rate (%) = (mass of test piece after test - mass of test piece before test) / (mass of test piece before test) × 100

[0482] [Table 2]

[0483]

[0484] According to Table 2, it was confirmed that Examples 1 and 2 highly possessed low dielectric constant, low dielectric loss tangent, and low hygroscopicity.

[0485] Possibility of Industrial Application

[0486] The curable composition of the present invention and its cured product can be used for prepregs, circuit boards, build-up films, semiconductor sealing materials, semiconductor devices, and the like.

Claims

1. A curable composition, characterized in that, Containing a polyimide resin (A) and an amine compound (B), The polyimide resin (A) has a partial structure represented by the following general formula (1), a partial structure represented by the following general formula (T-1) that is chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (T-2) that is chemically bonded to the partial structure represented by the general formula (1), [Chemical formula 1] In the above general formula (1), R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 2 represents an integer of 0 or more and 4 or less, n 1 represents the average number of repeating units, and the two * respectively represent bonding ends, and one bonding end is bonded by a chemical bond at the position of L 13 or L 14 in the following general formula (T-1), and the other bonding end is bonded by a chemical bond at the position of L 11 or L 12 in the following general formula (T-2). [Chemical formula 2] In the above general formula (T-1) or (T-2), R 11 and R 15 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 and R 14 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, L 11 to L 14 each independently represents a bonding end or a hydrogen atom, wherein, at the position of L 11 or L 12 a chemical bond is formed with the partial structure represented by the general formula (1), and at the position of L 13 or L 14 a chemical bond is formed with the partial structure represented by the general formula (1), and further, L 11 to L 14 which do not form a chemical bond with the partial structure represented by the general formula (1) are hydrogen atoms, m 1 and m 3 respectively represent 2.

2. The curable composition according to claim 1, wherein, The polyimide 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 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, 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.

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

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

5. A curable composition, characterized in that, Containing a polyimide resin mixture (C) and an amine compound (B), The polyimide resin mixture (C) contains a polyimide resin component having a partial structural unit represented by the following general formula (1a) and a maleimide polybody compound represented by the following general formula (2), The polyimide resin mixture (C) contains 1 to 99% by mass of the polyimide resin (A) relative to the total amount of the polyimide resin component, and contains 80% by mass or less of the maleimide polybody compound relative to the total amount of the polyimide resin mixture (C), The polyimide resin (A) has a partial structure represented by the following general formula (1), a partial structure represented by the following general formula (T-1) that is chemically bonded to the partial structure represented by the general formula (1), and a partial structure represented by the following general formula (T-2) that is chemically bonded to the partial structure represented by the general formula (1), [Chemical formula 6] In the above general formula (1a), R 11 represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, and R 12 represents a hydrocarbon group having 1 to 18 carbon atoms, and R 13 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, m 1 represents 2, and m 2 represents an integer of 0 or more and 4 or less, and n 1 represents the average number of repeating units. [Chemical formula 7] In the above general formula (2), R 21 and R 25 each independently represent a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 22 and R 24 each independently represent a hydrocarbon group having 1 to 18 carbon atoms, m 21 represents 2, m 23 represents 3, n 21 represents an integer of 1 or more and 5 or less. [Chemical formula 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, and the two * respectively represent bonding ends, and one bonding end is chemically bonded at the position of L in the following general formula (T-1) 13 or L 14 and the other bonding end is chemically bonded at the position of L in the following general formula (T-2) 11 or L 12 . [Chemical formula 9] In the above general formula (T-1) or (T-2), R 11 and R 15 each independently represents a hydrogen atom or a hydrocarbon group having 1 to 18 carbon atoms, R 12 and R 14 each independently represents a hydrocarbon group having 1 to 18 carbon atoms, L 11 to L 14 each independently represents a bonding end or a hydrogen atom, wherein, at the position of L 11 or L 12 a chemical bond is formed with the partial structure represented by the general formula (1), and at the position of L 13 or L 14 a chemical bond is formed with the partial structure represented by the general formula (1), and in addition, L 11 to L 14 which do not form a chemical bond with the partial structure represented by the general formula (1) are hydrogen atoms m 1 and m 3 represent 2 respectively.

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

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

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

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

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

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

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

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

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