TW202346427A - Curable composition, cured product, pre-impregnate, circuit board substrate, build-up film, semiconductor packaging material and semiconductor device wherein the curable composition and its cured product exhibit low dielectric loss factor and low moisture absorption rate during curing - Google Patents

Abstract

The purpose of the present invention is to provide a curable composition and its cured product that exhibit low dielectric loss factor and low moisture absorption rate during curing. This invention is a curable composition characterized by containing a polymaleimide compound (A) containing a monocyclic or condensed polycyclic aromatic group to which two or more straight-chain or branched alkylene groups are bonded, and an amine compound (B).

Description

Curable compositions, cured products, prepregs, circuit substrates, build-up films, semiconductor packaging materials and semiconductor devices

The present disclosure relates to curable compositions, cured products, prepregs, circuit substrates, build-up films, semiconductor packaging materials and semiconductor devices.

Epoxy resin or BT (bismaleimide-tris ) is a prepreg obtained by impregnating glass cloth with a thermosetting resin such as resin and drying it by heating, a laminated board obtained by heating and hardening the prepreg, and a combination of the laminated board and the prepreg. Heat-hardened multilayer boards are widely used as circuit board materials for electronic devices. Among them, the package substrate, which is one type of printed wiring board that functions as an interposer for mounting semiconductors, is becoming thinner. Warpage of the package substrate during mounting has become a problem. Therefore, in order to suppress the warpage of the package substrate during mounting, curve, and materials that exhibit high heat resistance are required. In addition, in recent years, as signals have continued to increase in speed and frequency, it is desired to provide a thermal insulation device that can form a hardened material that can maintain a sufficiently low dielectric constant and exhibit a sufficiently low dielectric loss factor in such an environment. Hardening composition. In particular, recently, various electronic material applications, especially cutting-edge material applications, require further improvements in performance represented by heat resistance and dielectric properties, as well as materials and compositions that have these properties. In response to these demands, maleimide resin has attracted attention as a material that has both heat resistance, low dielectric constant and low dielectric dissipation factor. However, although conventional maleimide resins exhibit high heat resistance, they are highly hygroscopic and their dielectric properties (dielectric constant and dielectric dissipation factor values) do not reach the level required for cutting-edge material applications. For example, Patent Document 1 discloses a thermosetting resin composition containing a polymaleimide resin having an indene ring and triallyl cyanurate or an aromatic diamine as non-destructive materials. And heat resistance, and as a printed circuit board material with a dielectric constant of laminated boards of 4.0 or less. [Prior art documents] [Patent documents]

[Patent Document 1] Japanese Patent Application Publication No. 5-247202

[Problem to be solved by the invention]

However, since the dielectric loss factor value of the thermosetting resin composition in Patent Document 1 has not been studied, the dielectric constant and dielectric loss factor value have not reached the level required for cutting-edge material applications, and cannot have both low temperature and low temperature at high temperatures. Hygroscopicity, low dielectric constant and low dielectric loss factor. In addition, since transmission loss increases with high frequency, circuit substrate materials are required to reduce transmission loss in the high frequency region. However, in the technology of Patent Document 1, only the dielectric characteristics of the currently used frequency band (the range of several hundred MHz to 3 GHz) have been studied, but no study has been made on whether it can cope with the so-called use of Sub6 or higher (for example, 3.6 GHz or higher). ) technology of the fifth generation mobile communication system (5G) in the frequency band. Therefore, the technical problem to be solved by this disclosure is to provide a curable composition, cured product, prepreg, circuit substrate, and build-up layer that has low hygroscopicity during curing and exhibits low dielectric loss factor and low dielectric constant. Thin films, semiconductor packaging materials and semiconductor devices. [Means used to solve problems]

The inventors of the present invention conducted repeated studies to solve the above-mentioned problems, and found that by using a curable composition, it is possible to achieve a high degree of low hygroscopicity during curing, low dielectric loss factor and low dielectric constant. The present invention is further completed; wherein the curable composition contains: polymaleimide containing a monocyclic or fused polycyclic aromatic ring bonded with two or more linear or branched alkylene groups. Compound (A), and amine compound (B). [Effects of the invention]

According to the present disclosure, it is possible to provide a curable composition, a cured product, a prepreg, a circuit substrate, and a build-up layer that can achieve a high degree of low hygroscopicity, low dielectric constant, and low dielectric loss factor upon curing. Thin films, semiconductor packaging materials and semiconductor devices. According to the present disclosure, it is possible to provide a curable composition, cured product, and prepreg that can achieve a high degree of low hygroscopicity, low dielectric constant, and low dielectric loss factor during curing even in the frequency band of Sub6 or higher. Objects, circuit substrates, built-up films, semiconductor packaging materials and semiconductor devices. This kind of curable composition is particularly useful in applications such as electronic component packaging materials.

[Form used to implement the invention]

Hereinafter, an embodiment of the present invention (referred to as "the present embodiment") will be described in detail. However, the present disclosure is not limited to the following description and can be implemented with various changes within the scope of the gist.

[Terminology] The so-called "reaction raw materials" in this specification refer to compounds used to obtain the target compound through chemical reactions such as combination or decomposition, and partially constitute the chemical structure of the target compound. Solvents, catalysts, etc. serve as chemical reaction aids. Substances that play the role of agents are excluded. In this specification, in particular, the so-called "reaction raw material" means, for example, when the target substance is a polymaleimide compound (A), it is used to obtain the polymaleimide through a chemical reaction. Compound (A) or a precursor compound thereof (for example, an intermediate amine compound (c) in which the following aromatic amine compounds (a) are connected via the following aromatic divinyl compound (b1)). The "aromatic group" in this specification is preferably an aromatic ring having 3 to 30 carbon atoms, more preferably an aromatic ring having 4 to 26 carbon atoms. Furthermore, the "aromatic group" in this specification means that the hydrogen atom of the aromatic ring in the aromatic group may be substituted by a substituent, such as an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. substituted with halogen atoms. In addition, "aromatic group" includes heteroaromatics, and may be substituted by -O-, -S- or -N=, so that -CH ₂ - or -CH= in the "aromatic group" are not adjacent to each other. catch. Examples of types of the aromatic ring include monocyclic aromatic rings and condensed polycyclic aromatic rings. Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, ethazole, isothiazole, thiazole, isothiazole, pyridine, pyrimidine, and thiazole. , pyridine ,three wait. Examples of the condensed polycyclic aromatic ring include naphthalene, anthracene, pyrene, phenanthrene, quinoline, isoquinoline, quinazoline, and phenanthrene. , pteridine, coumarin, indole, benzimidazole, benzofuran, acridine, etc. Furthermore, the hydrogen atom of the aromatic ring in the aromatic group may be, for example, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a carbon group. Substituted with an aryl group having 1 to 12 atoms, an aralkyl group having 1 to 12 carbon atoms, or a halogen atom. In addition, the so-called monovalent aromatic group refers to a group from which one hydrogen atom has been removed from the "aromatic group", and the so-called divalent aromatic group refers to a group from which any of the "aromatic groups" has been removed. The so-called trivalent to hexavalent aromatic radicals with two hydrogen atoms refer to the radicals with 3 to 6 hydrogen atoms removed from the "aromatic radical". Examples of the "aralkyl group" in this specification include benzyl group, diphenylmethyl group, naphthylmethyl group, and the like. The hydrogen atom of the aromatic ring in the aralkyl group can also be, for example, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, or a halogen atom. replace. In addition, the "aralkylene group" includes a divalent group obtained by removing any one hydrogen atom from the aforementioned "aralkyl group". The "alkyl group" in this specification may be linear, branched or cyclic, and examples include: methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, di- tertiary butyl, tertiary butyl, n-pentyl, isopentyl, tertiary 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, cyclohexyl Octyl or cyclononyl. Examples of "cycloalkyl" in this specification include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, methylcyclobutyl, norbornyl base or adamantyl group, etc. Examples of the "alkylthio group" in this specification include methylthio, ethylthio, propylthio, butylthio, octylthio or 2-ethylhexylthio. Examples of "alkenyl group" in this specification include ethenyl group, 1-propenyl group, 2-propenyl group, 2-butenyl group, pentenyl group, hexenyl group, vinyl group, and allyl group. base or isopropenyl, etc. Examples of "alkoxy" in this specification include methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentyloxy, hexyloxy, and 2-ethylhexyloxy. , octyloxy or nonyloxy, etc. Examples of the "aryl group" in this specification include phenyl, naphthyl, pyrenyl, phenanthrenyl, anthracenyl, azulenyl, tetralinyl, and the like. Moreover, the "aryl" refers to the hydrogen atom of the aromatic ring in the aryl group, and may be, for example, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkyl group having 1 carbon atom. ~10 alkenyl or halogen atoms substituted. In addition, the "arylene group" includes a bivalent group obtained by removing any one hydrogen atom from the aforementioned "aryl group". Examples of the "aryloxy group" in this specification include phenoxy group, naphthyloxy group, anthracenyloxy group, phenanthryloxy group or pyrenyloxy group. Examples of the "arylthio group" in this specification include arylthio groups such as phenylthio group, naphthylthio group, anthracenethio group, phenanthrenethio group or pyrenethio group. Examples of the "halogen atom" in this specification include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom. The so-called "structural unit" in this specification refers to the (repeating) unit of the chemical structure formed during reaction or polymerization. In other words, it refers to the unit that participates in the reaction or polymerization in the resulting compound formed by reaction or polymerization. The part of the structure other than the chemical bond structure is the so-called residue.

[Hardening composition] The curable composition of this embodiment contains a polymaleimide compound (A) containing a monocyclic or fused polycyclic aromatic ring bonded with two or more linear or branched alkylene groups. ) (hereinafter, simply referred to as the polymaleimide compound (A)) and the amine compound (B). Since the polymaleimide compound (A) has a small proportion of polar functional groups in the chemical structure, the composition as a whole can have both excellent low dielectric properties and low hygroscopicity. Furthermore, by combining the polymaleimide compound (A) and the amine compound (B), it is possible to achieve a high degree of low hygroscopicity, low dielectric constant and low curing properties even in the frequency band above Sub6. Dielectric loss factor.

In the curable composition of this embodiment, in terms of the blending ratio (parts by mass) of the components of the polymaleimide compound (A) and the amine compound (B), the polymaleimide compound (A) ): The amine compound (B) is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, further preferably 75:25 to 25:75. By adjusting the blending ratio within the aforementioned range, it is preferable because excellent low hygroscopicity, low dielectric constant, and low dielectric loss factor can be exhibited.

The curable composition of this embodiment may contain a curing agent (C) other than the amine compound (B) as long as it does not impair the curing of the present invention. Moreover, other resins (D), hardening accelerators, or additives other than the polymaleimide compound (A) and the amine compound (B) may be added to the curable composition of this embodiment. Examples of such additives include flame retardants, inorganic fillers, silane coupling agents, release agents, antioxidants, light stabilizers, thermal stabilizers, pigments, and emulsifiers.

The following is the essential components of the curable composition of this embodiment: a monocyclic or fused polycyclic aromatic ring having two or more bonded linear or branched alkylene groups and two or more After describing the maleimide-based polymaleimide compound (A) and the amine compound (B) in detail, the hardener (C) and other resins (D) other than the amine compound (B) as optional components , hardening accelerators and additives are explained.

(Polymaleimide compound (A)) The polymaleimide compound (A) according to this embodiment is a compound having two or more linear or branched alkylene groups bonded to each other. Monocyclic or fused polycyclic aromatic ring and more than 2 maleimide groups. The aforementioned monocyclic or fused polycyclic aromatic ring bonded with two or more straight-chain or branched alkylene groups refers to straight-chain or branched alkylene groups with 1 to 12 carbon atoms. There are two or more groups present, and two or more of the above-mentioned alkylene groups on one side are bonded to a bivalent or higher group of a monocyclic or condensed polycyclic aromatic ring. Therefore, the number of linear or branched alkylene groups bonded to a monocyclic or condensed polycyclic aromatic ring is consistent with the valence of the alkylene groups containing the aforementioned aromatic ring. In this embodiment, the monocyclic or fused polycyclic aromatic ring to which two or more linear or branched alkylene groups are bonded is preferably a divalent to tetravalent group, more preferably It is a 2- to 3-valent base. In this embodiment, the monocyclic or fused polycyclic aromatic ring to which two or more linear or branched alkylene groups are bonded is preferably a group represented by the following general formula (I). (In the above general formula (I), Ar ¹ represents an aromatic group with a valence of (2+h), L ¹ , L ² and L ³ each independently represent an alkylene group having 1 to 12 carbon atoms, and h represents 0 or more and 2 or less. is an integer, * represents a bond with other atoms.) In addition, in the above general formula (I), when h is 0, the group represented by the general formula (I) is divalent, and when h is 2, The base represented by general formula (I) is tetravalent. The maleimide group is preferably a group represented by the following general formula (II). (In the above general formula (II), Ar ² represents an aromatic group, the dotted line represents absence or a single bond, and * represents a bond with other atoms.) In addition, in the general formula (II), the dotted line represents absence or a single bond. single key. When the aforementioned dotted line does not exist, the maleimide group of the general formula (II) may become monovalent. On the other hand, when the dotted line is a single bond, the maleimide group of the general formula (II) may become divalent. Suitable polymaleimide compounds (A) of the present embodiment are compounds having a structural unit represented by the following general formula (1), or aromatic amine compounds having one or more and three or less alkyl groups. (a) (hereinafter also referred to as aromatic amine compound (a)), aromatic divinyl compound (b1) having two vinyl groups (hereinafter also referred to as aromatic divinyl compound (b1)), and maleic anhydride as the compound of reaction raw material (1). (In the above general formula (1), R ¹ each independently represents an alkyl group, R ² each independently represents an alkyl group, an alkoxy group or an alkylthio group having 1 to 10 carbon atoms; Aryl group, aryloxy group or arylthio group; cycloalkyl group with 3 to 10 carbon atoms; halogen atom; hydroxyl group; or mercapto group; R ³ , R ⁴ , R ⁵ and R ⁶ are each independent, representing a hydrogen atom or methyl group group, and one of R ³ and R ⁴ is a hydrogen atom, the other is a methyl group, one of R ⁵ and R ⁶ is a hydrogen atom, the other is a methyl group; X ¹ represents the following general formula (x ) the substituent shown; (In the general formula (x), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and one of R ⁷ and R ⁸ is a hydrogen atom, the other is a methyl group, and R ⁹ each independently represents a carbon Alkyl, alkoxy or alkylthio group with 1 to 10 atoms; aryl, aryloxy or arylthio group with 6 to 10 carbon atoms; cycloalkyl group with 3 to 10 carbon atoms; halogen atom ; ^Hydroxyl ; or mercapto; t represents an integer from 0 to 4.) r is the average number of ^{substitutions} of is an integer, q represents an integer from 0 to 4, and k represents an integer from 1 to 100. ) This allows for a higher degree of both low moisture absorption and low dielectric loss factor when hardened.

<Preferred form of the polymaleimide compound (A)> The polymaleimide compound (A) of this embodiment preferably has a structural unit represented by the general formula (1). Moreover, in the above general formula (1), when p is an integer of 2 or more, the plural R ¹ 's may be the same or different from each other. When q is an integer of 2 or more, plural R ² may be the same or different from each other. When t is an integer of 2 or more, plural R ⁹ 's may be the same or different from each other.

In the above general formula (1), R ¹ is each independent, and preferably represents an alkyl group having 1 to 10 carbon atoms, and more preferably represents an alkyl group having 1 to 6 carbon atoms. In addition, when p is an integer of 2 or more, plural R ¹ 's may be the same or different from each other. Preferred R ¹ in general formula (1) is methyl, ethyl or n-propyl. In addition, the benzene ring to which R ¹ in the general formula (1) is bonded may be the benzene ring of the aromatic amine compound (a). In the above general formula (1), p preferably represents 1 or 2. In addition, it is preferable that R ¹ is bonded to at least one of the 2-position, 3-position, 4-position, 5-position or 6-position of the benzene ring to which R ¹ is bonded in the general formula (1).

In the above general formula (1), R ² is each independent, and preferably represents an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms; an aryl group with 6 to 10 carbon atoms; A cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group, more preferably an alkyl group having 1 to 10 carbon atoms, and still more preferably an alkyl group having 1 to 6 carbon atoms. In addition, when q is an integer of 2 or more, plural R ² may be the same or different from each other. Preferred R ² in general formula (1) is methyl, ethyl or n-propyl. In addition, the benzene ring to which R ² in the general formula (1) is bonded may be the benzene ring of the aromatic divinyl compound (b1). In addition, in the above general formula (1), q preferably represents 0, 1 or 2.

In the above general formula (1), one of R ³ and R ⁴ is a hydrogen atom and the other is a methyl group, and one of R ⁵ and R ⁶ is a hydrogen atom and the other is a methyl group. Thereby, the reactivity of the unsaturated bond contained in the polymaleimide compound (A) itself can be maintained at a high level. Among R ³ , R ⁴ , R ⁵ and R ⁶ in the above general formula (1), if the proportion of alkyl groups occupied increases, the polymaleimide compound (A) itself is considered to have steric hindrance. The reactivity of unsaturated bonds may be reduced. Therefore, if R ³ , R ⁴ , R ⁵ and R ⁶ are all alkyl groups, the reactivity of the unsaturated bonds of the polymaleimide compound (A) itself decreases, and the cured product cannot be formed efficiently.

In the above-mentioned general formula (1), it is preferable that X ¹ is represented by the above-mentioned general formula (x), and in the general formula (x), R ⁷ represents a hydrogen atom, and R ⁸ represents a methyl group. Moreover, in the above general formula (x), R ⁹ each independently represents preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; carbon A cycloalkyl group with 3 to 10 atoms; a halogen atom; or a hydroxyl group; more preferably, it represents an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms; further preferably, it represents an alkyl group with 1 to 6 carbon atoms. Alkyl group or aryl group with 6 to 10 carbon atoms. Moreover, in the general formula (x), t preferably represents an integer of 0 to 4, and more preferably represents an integer of 0 to 3. In addition, when t is an integer of 2 or more, plural R ⁹ 's may be the same or different from each other.

In the above general formula (1), ^r means the average number of substitutions of X ¹ per benzene ring to which . In the above general formula (1), k represents the number of repeating units, and is preferably an integer from 1 to 100, more preferably an integer from 1 to 90, and further preferably an integer from 1 to 80.

<Other preferred embodiments of the polymaleimide compound (A)> As another preferred embodiment of the polymaleimide compound (A) of the present embodiment, there may be one or more alkanes having 1 or more and 3 or less alkanes. A compound containing an aromatic amine compound (a) having two vinyl groups, an aromatic divinyl compound (b1) having two vinyl groups, and maleic anhydride as the reaction raw material (1). In this case, in this embodiment, the reaction raw material (1) may further contain an aromatic monovinyl compound (b2) having one vinyl group (hereinafter also referred to as the aromatic monovinyl compound (b2)). ). Moreover, the polymaleimide compound (A) of this embodiment is preferably a polymaleimide compound (A) using the intermediate amine compound (c) and maleic anhydride as the reaction raw materials (3). The intermediate amine compound (c) is formed by cross-linking aromatic amine compounds (a) having one to three alkyl groups through an aromatic divinyl compound (b1) having two vinyl groups. Furthermore, the aforementioned intermediate amine compound (c) is preferably an aromatic amine compound (a) having 1 to 3 alkyl groups, an aromatic divinyl compound (b1) having 2 vinyl groups, A compound with an aromatic monovinyl compound (b2) having one vinyl group added as the reaction raw material (2) if necessary. In other words, the intermediate amine compound (c) in this embodiment is preferably a structural unit of the aromatic amine compound (a) and the structural unit of the aromatic divinyl compound (b1) having two vinyl groups through a chemical bond. connected, and optionally having a structure in which the structural unit of the aromatic monovinyl compound (b2) is chemically bonded to the aforementioned aromatic ring in the structural unit of the aforementioned aromatic amine compound (a), and the aromatic amine compound (a) ) has an aromatic ring to which an amine group (including a substituted amine group in which the hydrogen atom of the amine group is further substituted by an alkyl group having 1 to 6 carbon atoms) is bonded, and the aromatic ring has 1 to 3 of alkyl. Furthermore, the polymaleimine compound (A) in this embodiment has an amine group (including -NH ₂ and a substituted amine group) bonded to the aromatic ring of the intermediate amine compound (c) substituted with N -Replace the structure of maleimine ring. Therefore, the "polymaleimine compound (A)" in this embodiment and the "intermediate amine compound (c)" which is the precursor of the "polymaleimine compound (A)" are bonded Polymer compounds that are different in that the amine group of the aromatic ring (including -NH ₂ and substituted amine groups) is substituted with an N-substituted maleimine ring. In addition, the above-mentioned structural unit of the aromatic amine compound (a) refers to a group obtained by removing two hydrogen atoms from the aromatic ring of the aromatic amine compound (a). For example, when the aromatic amine compound (a) is represented by the general formula (a) described below, the group obtained by removing two hydrogen atoms from the benzene ring of the general formula (a) is called the aromatic amine compound (a). ) structural unit. In addition, the above-mentioned structural unit of the aromatic divinyl compound (b1) refers to a group obtained by cleaving the unsaturated bond of two vinyl groups of the aromatic divinyl compound (b1). In this embodiment, since the aromatic amine compound (a) having a specific aromatic ring structure is used as a reaction raw material, it becomes easy to control the reaction site with the aromatic divinyl compound (b1) described later, so it becomes easy to obtain The polymaleimide compound (A) having a uniform chemical structure or chain length can provide a polymaleimide compound (A) that exhibits low hygroscopicity and low dielectric loss factor when hardened.

Hereinafter, the aromatic amine compound (a) having 1 to 3 alkyl groups, the aromatic amine compound having 2 vinyl groups as the constituent components of the reaction raw material (1) of the polymaleimide compound (A) After describing the divinyl compound (b1), the aromatic monovinyl compound (b2) having one vinyl group and maleic anhydride which can be any components, the other polymaleimide compounds (A) will be explained. A preferred form and a method for producing the polymaleimide compound (A) will be described.

<<Aromatic amine compound (a)>> The aromatic amine compound (a) in this embodiment has an aromatic ring to which an amine group (-NH ₂ or a substituted amino group) is bonded, and is bonded to the aromatic ring. There are more than 1 and less than 3 alkyl groups. Therefore, the aromatic amine compound (a) may be an amine-based compound. Furthermore, the aromatic ring forming the central structure of the aromatic amine compound (a) is preferably a monocyclic ring and includes an aromatic hydrocarbon ring and an aromatic heterocyclic ring. As the aromatic hydrocarbon ring, a benzene ring is preferred. Examples of the aromatic heterocyclic ring include heterocyclic six-membered rings such as a piran ring and a pyridine ring. Furthermore, the aromatic amine compound (a) in this embodiment has an aromatic ring to which -NH ₂ is bonded without a substituted amine group, and one to three alkyl groups are bonded to the aromatic ring. For the better.

In the aromatic amine compound (a) of this embodiment, examples of the alkyl group substituting one to three hydrogen atoms in the aromatic ring of the aromatic amine compound (a) include an alkyl group having 1 to 10 carbon atoms. The alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group may be any one of linear type, branched type, or cyclic type. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, and the like. The smaller the molecular weight of the alkyl group, the more significant the effect (low dimensional change rate) achieved by the present invention is. In addition, the higher the molecular weight of the alkyl group, the more significant the effect (low water absorption) achieved by the present invention is.

The upper limit of the number of alkyl groups bonded to the aromatic ring having an amine group (including -NH ₂ and a substituted amine group) in the aromatic amine compound (a) _is determined by (substituted amino group), and from the viewpoint that two bonds are used for polymerization, the number may be the number minus 3 from the number of substitutable ring constituent atoms in the unsubstituted aromatic ring. For example, when the aromatic ring is a benzene ring, the number of alkyl groups is 3 or less. Furthermore, by setting the number of alkyl groups substituted on the aromatic ring of the aromatic amine compound (a) to 2 or more, it is easy to control the reaction site with the aromatic divinyl compound (b1) described below, so it is easy to A polymaleimide compound (A) with uniform chemical structure or chain length is obtained. As a result, the cured product of the polymaleimide compound (A) can easily exhibit low hygroscopicity and excellent high-frequency electrical characteristics.

Preferable embodiments of the aromatic amine compound (a) will be described below, taking the case where the aromatic ring of the aromatic amine compound (a) in this embodiment is a benzene ring as an example. In this embodiment, among the carbon atoms in the benzene ring constituting the aromatic amine compound (a), the carbon atom having the largest HOMO electron density (Hückel coefficient) is preferably one or more unsubstituted ( or replaced by hydrogen atoms). This makes it easy to control the _ArSE reaction and molecular design caused by a cationoid reagent such as the aromatic divinyl compound (b1) described below. To explain in more detail, among the carbon atoms in the benzene ring constituting the aromatic amine compound (a), if the carbon atom having the electron density (Huckel coefficient) of the maximum HOMO is unsubstituted, then for the carbon atom having the maximum HOMO In terms of the electron density of the carbon atom, the carbocation of the aromatic divinyl compound (b1), which is a cation-like reagent, reacts easily. Therefore, by controlling the number and position of the alkyl groups bonded to the carbon atom of the benzene ring, the bonding site or the number of bonds to the aromatic divinyl compound (b1) can be adjusted. Therefore, it is presumed that the chemical structure or molecular chain length of the obtained polymaleimide compound (A) becomes easy to design. For example, when the aromatic amine compound (a) has an aniline skeleton having one benzene ring and one amino group, at least one of the carbon atoms at the 2-position, 4-position and 6-position of the aniline nucleus is preferably replaced by hydrogen atoms. Thereby, for at least one carbon atom in the 2-position, 4-position, and 6-position of the ortho- and para-positions of the aniline nucleus, which has a high electron density, it is formed from the aromatic divinyl compound (b1) described below. Cationoid reagents become more susceptible to attack. In particular, if an aromatic amine compound (a) having an aniline core substituted with an alkyl group at a specific position is used, the bonding site with the aromatic divinyl compound (b1) can be roughly controlled, making it easier to obtain uniform The chemical structure or chain length of the polymaleimide compound (A). For example, if 2,6-dialkylamine is used as the aromatic amine compound (a), it is considered that a large amount of a polymaleimide compound (b1) bonded to the aromatic divinyl compound (b1) at the 4-position can be obtained A).

As specific examples of the aromatic amine compound (a) in this embodiment, dimethylaniline (2,3-dimethylaniline, 2,4-dimethylaniline, 2,6-dimethylaniline, 3 ,4-dimethylaniline or 3,5-dimethylaniline), diethylaniline (2,3-diethylaniline, 2,4-diethylaniline, 2,6-diethylaniline, 3, 4-diethylaniline or 3,5-diethylaniline), diisopropylaniline (2,3-diisopropylaniline, 2,4-diisopropylaniline, 2,6-diisopropylaniline propylaniline, 3,4-diisopropylaniline or 3,5-diisopropylaniline), ethylmethylaniline (for example, 2,3-position, 2,4-position, 2,6-position, 3 , either 4-position or 3-5 position is methyl and the other is ethyl (ethylmethylaniline), cyclobutylaniline, cyclopentylaniline, cyclohexylaniline, o,m or p-toluidine, o,m or p-ethylaniline, o,m or p-isopropylaniline, o,m or p-propylaniline, o,m or p-butylaniline, Methylisopropylaniline (for example, one of the 2,3-position, 2,4-position, 2,6-position, 3,4-position or 3,5-position is methyl and the other is isopropyl) Methylisopropylaniline), or ethylbutylaniline (for example, any one of the 2,3-position, 2,4-position, 2,6-position, 3,4-position or 3,5-position is ethyl, The other is butyl ethyl butyl aniline) and so on. In addition, the aforementioned butyl group includes n-butyl, tertiary butyl and secondary butyl. In addition, the aromatic amine compound (a) in this embodiment can be used individually or in combination of 2 or more types.

For example, if N-phenylmaleimine has a chemical structure in which a maleimide group is directly bonded to an unsubstituted benzene ring, the benzene ring and the 5-membered ring of maleimine are in They are stable in a state of being arranged on the same plane, so they become easy to stack and exhibit high crystallinity. Therefore, it causes poor solvent solubility. On the other hand, in the case of the present disclosure, when, for example, 2,6-dimethylaniline has an alkyl group (for example, methyl) as a substituent of a phenyl ring, due to the stereoscopic structure of the methyl group The benzene ring and the 5-membered ring of maleimide adopt a staggered conformation, which makes it difficult to stack. Therefore, the crystallinity is reduced and the solvent solubility is improved, making it a better form. However, if the steric hindrance is too large, the reactivity during the synthesis of maleimide may be inhibited. Therefore, it is preferable to use an aromatic amine compound (a) having an alkyl group having 1 to 6 carbon atoms. .

The aromatic amine compound (a) necessary for the reaction raw material (1) in this embodiment can be represented by the following general formula (a), for example. (In the above general formula (a), R ^1a represents an alkyl group, and ^pa represents an integer of 1 to 3. R ^1a existing in plural numbers may be the same or different.)

In the general formula (a), the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms and the alkyl group having 1 to 3 carbon atoms are the same as above. In the above general formula (a), p ^a is preferably 1 or 2. In addition, when R ^1a exists in plural, they may be the same alkyl group or different alkyl groups. Moreover, in this embodiment, the aromatic amine compound (a) represented by the said general formula (a) may be used individually, or may be used in combination of 2 or more types.

<<Aromatic divinyl compound (b1)>> The aromatic divinyl compound (b1) in this embodiment has two vinyl groups (CH ₂ =CH-) (also called vinyl groups) as aromatic compounds. The substituent on the ring can be used without particular limitation if it can react with the aromatic amine compound (a). Moreover, in this embodiment, it is preferable that the reaction raw material (1) contains a mixture of the aromatic divinyl compound (b1) and the aromatic monovinyl compound (b2). Examples of the aromatic divinyl compound (b1) include divinylbenzene, divinylbiphenyl, divinylnaphthalene, and aromatic rings thereof containing 1 to 10 carbon atoms with one or more carbon atoms. Alkyl, alkoxy or alkylthio group; aryl, aryloxy or arylthio group with 6 to 10 carbon atoms; cycloalkyl group with 3 to 10 carbon atoms; halogen atom; hydroxyl; or mercapto group Various compounds substituted by substituents, etc. A preferred form of this substituent is the same as R ² in the above general formula (1). In addition, the aforementioned alkyl group may be either a linear type or a branched type. Among them, from the viewpoint of exhibiting the effect of high heat resistance, the number of carbon atoms in the alkyl group or alkoxy group is preferably 1 to 4. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, isobutyl, and the like. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, and the like. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, etc.

The aromatic divinyl compound (b1) of the reaction raw material (1) of the polymaleimide compound (A) of the present disclosure is preferably represented by the following formula (b1). (In the above general formula (b1), R ^2b each independently represents an alkyl group, alkoxy group or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group or aryl group having 6 to 10 carbon atoms. A thio group; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, q ^1b represents an integer from 0 to 4. In addition, when q ^1b is an integer of 2 or more, the plural R ^2b may Same or different from each other.)

R ^2b in the above formula (b1) may correspond to R ² in the general formula (1). Therefore, R ^2b in the above-mentioned general formula (b1) is the same as the general formula (1), each is independent, and preferably represents an alkyl group with 1 to 10 carbon atoms or an alkoxy group with 1 to 10 carbon atoms; a carbon atom An aryl group with 6 to 10 carbon atoms; a cycloalkyl group with 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group, more preferably an alkyl group with 1 to 10 carbon atoms, further preferably an alkyl group with 1 to 6 carbon atoms base. In the above general formula (b1), q ^1b is preferably 0 to 2. In addition, when q ^1b is 2 or more, plural R ^b1 may be the same group or different groups.

Specific examples of the aromatic divinyl compound (b1) in this embodiment include: 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 2 ,5-dimethyl-1,4-divinylbenzene, 2,5-diethyl-1,4-divinylbenzene, cis,cis,β,β'-diethoxy-m-m-di Vinylbenzene, 1,4-divinyl-2,5-dibutylbenzene, 1,4-divinyl-2,5-dihexylbenzene, 1,4-divinyl-2,5-dibutylbenzene Divinylbenzenes such as methoxybenzene and compounds containing these derivatives, as well as 1,3-divinylnaphthalene, 1,4-divinylnaphthalene, 1,5-divinylnaphthalene, 1 ,6-divinylnaphthalene, 1,7-divinylnaphthalene, 2,3-divinylnaphthalene, 2,6-divinylnaphthalene, 2,7-divinylnaphthalene, 3,4-divinylnaphthalene Divinylnaphthalene, 1,8-divinylnaphthalene, 1,5-dimethoxy-4,8-divinylnaphthalene and compounds containing these derivatives, but are not limited to This and so on. In addition, the aromatic divinyl compound (b1) in this embodiment can be used individually or in combination of 2 or more types. In particular, from the viewpoint of fluidity, the aromatic divinyl compound (b1) is preferably divinylbenzene and a compound having a substituent on its aromatic ring, and more preferably divinylbenzene. In addition, in this embodiment, the substitution position of the vinyl group of divinylbenzene is not particularly limited, but it is preferable that the main component is the meta-form. The meta-body content in divinylbenzene is preferably 40 mass% or more, more preferably 50 mass% or more, relative to the total amount of divinylbenzene. In this embodiment, relative to the total amount (100 mass%) of the polymaleimide compound (A), the structural unit of the aromatic divinyl compound (b1) preferably contains 10 to 90 mass%, more preferably It contains 20 to 90% by mass. The above-mentioned structural unit of the aromatic divinyl compound (b1) refers to a group obtained by removing two hydrogen atoms (a total of four hydrogen atoms) from two vinyl groups of the aromatic divinyl compound (b1).

＜＜Aromatic monovinyl compound (b2)＞＞ In addition to the aromatic amine compound (a), the aromatic divinyl compound (b1), and maleic anhydride, the polymaleimide compound (A) in this embodiment can also use other compounds as reaction raw materials. . Examples of the other compound include an aromatic monovinyl compound (b2) having one vinyl group. That is, in the embodiment, it is preferable to use the aromatic amine compound (a), the aromatic divinyl compound (b1), the aromatic monovinyl compound (b2) and maleic anhydride as the reaction raw materials (1) . The polymaleimide compound (A) of this embodiment uses an aromatic amine compound (a), an aromatic divinyl compound (b1), and maleic anhydride as its reaction raw materials. The group monovinyl compound (b2) is preferred because the cured product of the polymaleimide compound (A) finally obtained is excellent in terms of low dielectric loss factor. In addition, since the aromatic monovinyl compound (b2) also generates a carbocation similarly to the aromatic divinyl compound (b1), among the carbon atoms in the aromatic hydrocarbon ring constituting the aromatic amine compound (a) Carbon atoms with the largest HOMO electron density (Huckel coefficient) react easily.

Examples of the aromatic monovinyl compound (b2) in the present embodiment include vinylbenzene (styrene), vinyl biphenyl, vinyl naphthalene, and the like through one or more carbon atoms in the aromatic ring. Alkyl, alkoxy or alkylthio group with 1 to 10 atoms; aryl, aryloxy or arylthio group with 6 to 10 carbon atoms; cycloalkyl group with 3 to 10 carbon atoms; halogen atom ; Hydroxyl; or various compounds substituted by substituents such as mercapto groups, etc. The alkyl group may be either linear or branched, and may have an unsaturated bond in the structure. Especially, when low hygroscopicity is important, it is preferable that the said alkyl group or the said alkoxy group has 1-4 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, tertiary butyl, isobutyl, and the like. Examples of the alkoxy group include methoxy group, ethoxy group, propoxy group, butoxy group, and the like. Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom, etc.

The aromatic monovinyl compound (b2) that can be used as the reaction raw material (1) of the polymaleimide compound (A) of the present disclosure can be represented by the following general formula (b2). (In the above general formula (b2), R ^9b each independently represents an alkyl group, alkoxy group or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group or aryl group having 6 to 10 carbon atoms. A sulfide group; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, and t ^1b represents an integer of 0 to 5. In addition, when t ^1b is an integer of 2 or more, the plural R ^9b may Same or different from each other.)

R ^9b in the above formula (b2) may correspond to R ⁹ in the general formula (x). Therefore, R ^9b in the above-mentioned general formula (b1) is the same as the general formula (x), each is independent, and preferably represents an alkyl group with 1 to 10 carbon atoms or an alkoxy group with 1 to 10 carbon atoms; carbon atom An aryl group with 6 to 10 carbon atoms; a cycloalkyl group with 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group, more preferably an alkyl group with 1 to 10 carbon atoms, further preferably an alkyl group with 1 to 6 carbon atoms base. In the above general formula (b1), t ^1b is preferably 1 to 4. In addition, when t ^1b is 2 or more, plural R ^9b may be the same group or different groups.

Specific examples of the aromatic monovinyl compound (b2) in this embodiment include styrene, fluorostyrene, vinyl chlorotoluene, alkylvinylbenzene (o-,m-,p-methyl Vinylbenzenes such as styrene, o-,m-,p-ethylvinylbenzene), o-,m-,p-(chloromethyl)styrene and compounds containing these derivatives; 4 - Biphenyl compounds such as vinylbiphenyl, 4-vinyl-p-terphenyl and compounds containing their derivatives; and 1-vinylnaphthalene, 2-vinylnaphthalene and their derivatives Compounds such as vinyl naphthalenes, but are not limited to these. In particular, from the viewpoint of raw material acquisition, alkylvinylbenzene and a compound having a substituent on its aromatic ring are preferred, and ethylvinylbenzene is more preferred. In addition, the substitution positions of the vinyl group and the ethyl group of ethylvinylbenzene are not particularly limited, but it is preferable that the meta form is used as the main component, and relative to the total amount of ethylvinylbenzene, ethylvinylbenzene The content of the metabody in is more preferably 40% by mass or more, further preferably 50% by mass or more.

When using the aromatic monovinyl compound (b2) as the reaction raw material (1) of the polymaleimide compound (A) in this embodiment, the aromatic divinyl compound in the reaction raw material (1) The molar ratio ((b1)/(b2)) of (b1) relative to the aromatic monovinyl compound (b2) is preferably 99/1 to 50/50, more preferably 98/2 to 70/30. In this embodiment, the structural unit of the aromatic monovinyl compound (b2) preferably contains 0 to 40 mass%, more preferably, relative to the total amount (100 mass%) of the polymaleimide compound (A). It contains 0 to 30% by mass. The above-mentioned structural unit of the aromatic monovinyl compound (b2) refers to a group obtained by removing two hydrogen atoms from one vinyl group of the aromatic monovinyl compound (b2).

-Maleic anhydride- In this embodiment, maleic anhydride is an essential component of the reaction raw material (1) of the polymaleimide compound (A), such as the method for producing the polymaleimide compound (A) described below. It is described in the column that it is used for the reaction of maleyl imidization of the amine group (including -NH ₂ and substituted amine group) derived from the aromatic amine compound (a).

＜Preferred form of polymaleimide compound (A)＞ Hereinafter, the aspect of the polymaleimide compound (A) suitable for the present disclosure will be described, taking the case where each aromatic ring is a benzene ring as an example. The following chemical structural formulas are used to illustrate the present disclosure, and the scope of the present disclosure is not limited by the following chemical structural formulas.

In this embodiment, the polymaleimide compound (A) is preferably represented by the following general formula (2). (In the above general formula (2), R ¹ each independently represents an alkyl group, R ² each independently represents an alkyl group with 1 to 10 carbon atoms or an alkoxy group with 1 to 10 carbon atoms; each of R 1 independently represents an alkyl group with 6 to 10 carbon atoms. 10 aryl group; cycloalkyl group with 3 to 10 carbon atoms; halogen atom; or hydroxyl group, R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom or a methyl group, and the one between R ³ and R ⁴ One is a hydrogen atom and the other is a methyl group; one of R ⁵ and R ⁶ is a hydrogen atom and the other is a methyl group; X ¹ represents a substituent represented by the following general formula (x); (In the general formula (x), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and one of R ⁷ and R ⁸ is a hydrogen atom, the other is a methyl group, and R ⁹ represents a carbon atom of 1 ~10 alkyl group, alkoxy group with 1 to 10 carbon atoms; aryl group with 6 to 10 carbon atoms; cycloalkyl group with 3 to 10 carbon atoms; halogen atom; or hydroxyl group, t represents 0 to 4 Integer.) M ²¹ represents a hydrogen atom or a group represented by the following general formula (i), M ²² represents a hydrogen atom, a group represented by the following general formula (ii) or a group represented by the following general formula (iii) ; [In the above general formula (i), R ⁹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; Cycloalkyl group; halogen atom; or hydroxyl group, R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and one of R ⁷ and R ⁸ is a hydrogen atom, the other is a methyl group, t represents 0 to 4 is an integer, * represents the bond with other atoms. In addition, when t is an integer of 2 or more, plural R ⁹ 's may be the same or different from each other. ] [In the above general formula (ii), R ¹ⁱⁱ represents an alkyl group, and p ⁱⁱ represents an integer of 0 to 4. In addition, when p ⁱⁱ is an integer of 2 or more, plural R ¹ⁱⁱ may be the same or different from each other. In the above general formula (iii), R ¹ⁱⁱⁱ represents an alkyl group, R ⁹ represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; carbon atom A cycloalkyl group with a number of 3 to 10; a halogen atom; or a hydroxyl group, R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and one of R ⁷ and R ⁸ is a hydrogen atom, and the other is a methyl group, p ⁱⁱⁱ represents an integer from 0 to 3, t represents an integer from 0 to 4, r ¹ⁱⁱⁱ is the average number of substitutions per ^benzene ring bonded with The bond. In addition, when p ⁱⁱⁱ is an integer of 2 or more, the plural R ¹ⁱⁱⁱ may be the same or different from each other. When t is an integer of 2 or more, the plural R ⁹ may be the same or different from each other. ] ^r is the average number of substitutions of X ¹ per benzene ring bound to ~100 integer. ) In the above general formula (2), when p is an integer of 2 or more, the plural R ^1's may be the same or different from each other. When q is an integer of 2 or more, the plural R ² may be the same or different from each other. Different, when t is an integer of 2 or more, the plural R ⁹ 's may be the same or different from each other. In addition, preferred aspects of R ¹ to R ⁹ , X ¹ , p, q, r, t and k in the above general formula (2) are the same as those in the above general formula (1). Furthermore, the above-mentioned general formula (i) corresponds to the above-mentioned general formula (x), R ¹ⁱⁱ in the above-mentioned general formula (ii) corresponds to R ¹ in the above-mentioned general formula (1), and R in the above-mentioned general formula (iii) ¹ⁱⁱⁱ corresponds to R ¹ in the above general formula (1).

The number average molecular weight (Mn) of the polymaleimide compound (A) of the present disclosure is preferably in the range of 350 to 2,000, more preferably in the range of 400 to 1,500. Moreover, the weight average molecular weight (Mw) of the polymaleimide compound (A) is preferably in the range of 400 to 500,000, more preferably in the range of 450 to 400,000. From the viewpoint of being excellent in low dielectric constant and low dielectric loss factor, the polymaleimide compound (A) of the present disclosure has a molecular weight distribution (weight average) calculated by gel permeation chromatography (GPC) measurement. Molecular weight (Mw)/number average molecular weight (Mn)) is preferably in the range of 1.001 to 500, more preferably 1.001 to 400. In addition, according to the GPC chart obtained by GPC measurement, the molecular weight distribution spans a wide range and there are many high molecular weight components. The proportion of high molecular weight components that contribute to flexibility increases. Therefore, it is different from using conventional maleic acid. Compared with the cured product of imine, a cured product with suppressed brittleness and excellent flexibility and softness can be obtained, which is a preferable aspect. In addition, the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the polymaleimide compound (A) of this embodiment are: Gel permeation chromatography (hereinafter referred to as "GPC") was used to measure under the measurement conditions described in the examples below.

When the polymaleimide compound (A) in this embodiment contains an indene skeleton (or a structural unit having an indene skeleton) represented by the following general formula (3), relative to the polymaleimide compound (A), The total amount (100 mass %) of the acyl imine compound (A) and the ratio of the indene skeleton are preferably 10 mass % or less, more preferably 5 mass % or less, further preferably 3 mass % or less, still more preferably It is 2 mass % or less, especially preferably 0.9 mass % or less. (In the above general formula (3), R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ³⁴ each independently represents an alkyl group having 1 to 10 carbon atoms. Alkoxy group or alkylthio group; aryl group, aryloxy group or arylthio group with 6 to 10 carbon atoms; cycloalkyl group with 3 to 10 carbon atoms; halogen atom; hydroxyl group; or mercapto group, q ³ represents is an integer from 0 to 3, and when q ³ is an integer of 2 or more, the plural R ^34s may be the same or different from each other. Also, * represents a bond with other atoms.) In the above general formula (3), R ³⁴ is each independent, preferably represents an alkyl group having 1 to 6 carbon atoms, more preferably represents an alkyl group having 1 to 3 carbon atoms. Moreover, in the above general formula (3), R ³¹ , R ³² and R ³³ are preferably a hydrogen atom or a methyl group. In the curable composition of this embodiment, it is preferable that the polymaleimide compound (A) contains 60 mass % or more and 95 mass % or less, and more preferably 70 mass % or more and 93 mass % or less, based on the entire curable composition. mass % or less, preferably 80 mass % or more and 90 mass % or less. It is preferable from the viewpoint of heat resistance that the content of the polymaleimide compound (A) is in the range of 60 mass % or more and 95 mass % or less.

＜Production method of polymaleimide compound (A)＞ Hereinafter, a method for producing the polymaleimide compound (A) of the present disclosure will be described. The production method of the polymaleimide compound (A) of this embodiment is not particularly limited, as long as the aromatic amine compound (a), the aromatic divinyl compound (b1) and maleic anhydride are used as the reaction raw materials (1 ), or it can be produced in any way as long as it has the structural unit represented by the above general formula (1). As an example of the manufacturing method of the polymaleimide compound (A) of this disclosure, there can be mentioned, for example, a manufacturing method including the following steps (1) and (2). Step (1): reacting the aromatic amine compound (a) as the reaction raw material (2) with the aromatic divinyl compound (b1) to obtain the intermediate amine compound (c) in this embodiment; Step (2): The step of reacting the intermediate amine compound (c) obtained in the above step (1) as the reaction raw material (3) with maleic anhydride to obtain the polymaleimide compound (A) of the present disclosure. . Specifically, the manufacturing method of the polymaleimide compound (A) of this embodiment preferably includes: making the aromatic amine compound (a) and the aromatic divinyl compound (b1) under a solid acid catalyst The step (1) of the reaction (also called the cross-linking step), and the step (2) of condensing the intermediate amine compound (c) generated by the aforementioned step (1) with maleic anhydride (also called the condensation step) ). Hereinafter, each step of the method for producing the polymaleimide compound (A) of the present disclosure will be described in order.

＜＜Step (1): Production step of intermediate amine compound (c)>> Hereinafter, the steps for producing the intermediate amine compound (c) in this embodiment will be described. Step (1) in this embodiment is not particularly limited, but for example, the above aromatic amine compound (a), the above aromatic divinyl compound (b1) (for example, divinylbenzene), and further A step in which other compounds such as the desired aromatic monovinyl compound (b2) (for example, ethylvinylbenzene) are reacted in the presence of an acid catalyst. Thereby, the intermediate amine compound (c) can be produced.

As a blending ratio of the aromatic amine compound (a) and the aromatic divinyl compound (b1), considering the physical property balance of formability and curability during the production of the obtained cured product, relative to the aromatic amine The molar ratio of the aromatic divinyl compound (b1) per 1 mole of compound (a) is preferably 0.1 to 10 moles, more preferably 0.2 to 3 moles. Moreover, when the aforementioned aromatic monovinyl compound (b2) is used together, as the aforementioned aromatic divinyl compound (b1) and the aforementioned aromatic monovinyl compound are The total molar ratio of the base compound (b2) is preferably 0.1 to 10 moles, more preferably 0.2 to 3 moles. In addition, as a specific method for carrying out the above reaction, generally, all the raw materials are charged at once and reacted directly at a specified temperature, or the aromatic amine compound (a) and an acid catalyst are charged while maintaining the specified temperature. A method in which the aromatic divinyl compound (b1), other compounds (for example, the aromatic monovinyl compound (b2)), etc. are dropped and reacted simultaneously. At this time, the dropping time is usually 0.1 to 12 hours, preferably 6 hours or less. After the reaction, when a solvent is used, the solvent and unreacted substances are distilled off as necessary to obtain the aforementioned intermediate amine compound (c). When a solvent is not used, the target compound is obtained by distilling off unreacted substances. The aforementioned intermediate amine compound (c).

Examples of the acid catalyst used in step (1) of this embodiment include inorganic acids such as phosphoric acid, hydrochloric acid, sulfuric acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid, etc. Organic acids, such as activated clay, acidic clay, silica alumina, zeolite, solid acid of strongly acidic ion exchange resin, heteropoly acid salt, etc. However, from the perspective of handleability, it is better to use The solid acid of the catalyst can be easily removed by filtration. When using other acids, it is preferable to neutralize with an alkali and wash with water after the reaction. Relative to the total amount of the input raw materials (aromatic divinyl compound (b1) or a mixture of aromatic divinyl compound (b1) and aromatic monovinyl compound (b2), and aromatic amine compound (a)) 100 parts by mass, the blending amount of the aforementioned acid catalyst is in the range of 1 to 100 parts by mass, but from the viewpoint of handleability and economy, it is preferably 1 to 60 parts by mass. The reaction temperature usually suffices within the range of 100 to 270°C. However, in order to suppress the formation of isomer structures and avoid side reactions such as thermal decomposition, the reaction temperature is preferably 100 to 220°C.

In the step (1) of this embodiment, as the aromatic divinyl compound (b1) or the mixture of the aromatic divinyl compound (b1) and the aromatic monovinyl compound (b2) and the aromatic amine compound (a ) mixture reaction time, that is, the cross-linking reaction time, because if the time is short, the reaction will not proceed completely, and if the time is long, side reactions such as thermal decomposition of the product will occur, so under the aforementioned reaction temperature conditions, usually It is in the range of 1 to 48 hours in total, and preferably in the range of 1 to 30 hours in total. In the method for producing the intermediate amine compound (c) in this embodiment, since aniline or a derivative thereof also serves as a solvent, it is not necessary to use another solvent, but a solvent may be used. For example, when reacting using divinylbenzene as a raw material, a solvent capable of azeotropic dehydration, such as toluene, xylene, or chlorobenzene, may be used, and the moisture contained in the catalyst, etc. may be azeotropically dehydrated if necessary. The solvent is first distilled off, and then the reaction is carried out within the above reaction temperature range.

The intermediate amine compound (c) obtained through the above step (1) is preferably represented by the following general formula (4), for example. (In the above general formula (4), R ¹ each independently represents an alkyl group, R ² each independently represents an alkyl group, an alkoxy group or an alkylthio group having 1 to 10 carbon atoms; Aryl, aryloxy or arylthio; cycloalkyl with 3 to 10 carbon atoms; halogen atom; hydroxyl or mercapto group, R ³ , R ⁴ , R ⁵ and R ⁶ are each independent, representing a hydrogen atom or a methyl group , and one of R ³ and R ⁴ is a hydrogen atom and the other is a methyl group, one of R ⁵ and R ⁶ is a hydrogen atom and the other is a methyl group; X ¹ represents the following general formula (x) The substituents shown; (In the general formula (x), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and one of R ⁷ and R ⁸ is a hydrogen atom, the other is a methyl group, R ⁹ represents an alkyl group, t Indicates an integer from 0 to 4.) ^r is the average number of substitutions of X ¹ per benzene ring to which An integer of 4, k represents an integer of 1 to 100. )

Moreover, in the above general formula (4), when p is an integer of 2 or more, the plural R ¹ 's may be the same or different from each other. When q is an integer of 2 or more, plural R ² may be the same or different from each other. When t is an integer of 2 or more, plural R ⁹ 's may be the same or different from each other.

In addition, preferred aspects of R ¹ to R ⁹ , X ¹ , p, q, r, t and k in the above general formula (4) are the same as those in the above general formula (1). Moreover, as another preferred form of the intermediate amine compound (c) obtained through the above-mentioned step (1), the above-mentioned general formula (2) which is also a preferred form of the polymaleimide compound (A) can be cited The N-substituted maleimide group is substituted into an amine group (including -NH ₂ and substituted amine groups).

In this embodiment, the amine equivalent of the intermediate amine compound (c) is preferably 172 to 400 g/equivalent, more preferably 172 to 350 g/equivalent. In addition, the measurement of the amine equivalent of the intermediate amine compound (c) in this specification is a value measured based on the neutralization titration method specified in JIS K 0070 (1992).

<<Step (2): Maleic imidization>> Step (2) in this embodiment is a step of reacting the intermediate amine compound (c) obtained in step (1) with maleic anhydride. Since the amine group (including -NH ₂ and substituted amine group) of the intermediate amine compound (c) undergoes a maleyl imidization reaction, the aforementioned amine group can be substituted into an N-substituted maleimine ring. Chemical structure, therefore the polymaleimide compound (A) of the present disclosure can be obtained. In this embodiment, the intermediate amine compound (c) represented by the above general formula (4) obtained through step (1) is put into the reactor, dissolved in an appropriate solvent, and then mixed with Malay in the presence of a catalyst. Anhydride reaction. After the reaction, unreacted maleic anhydride or other impurities are removed by washing with water, and the solvent is removed under reduced pressure to obtain the target polymaleimide compound (A). In addition, a dehydrating agent may be used during the reaction if necessary.

Examples of the organic solvent used in step (2) of this embodiment include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone, N, Aprotic solvents such as N-dimethylformamide, N,N-dimethylacetamide, dimethyl styrene, N-methyl-2-pyrrolidinone, acetonitrile, cyclotenine, etc. Cyclic ethers such as hexane and tetrahydrofuran, esters such as ethyl acetate and butyl acetate, aromatic solvents such as benzene, toluene, xylene, etc. These can be used alone or in mixture.

In the step (2) of this embodiment, the mixing ratio of the intermediate amine compound (c) and maleic anhydride is preferably, in terms of the amine equivalent of the intermediate amine compound (c), maleic anhydride The equivalent ratio is blended in the range of 1 to 5, more preferably 1 to 3, and the mass ratio is 0.1 to 10, preferably 0.2, relative to the total amount of the intermediate amine compound (c) and maleic anhydride. Among the organic solvents with a mass ratio of ~5, the one that reacts is the best.

Catalysts that can be used in step (2) of this embodiment include acetates, chlorides, bromides, sulfates, nitrates, etc. of nickel, cobalt, sodium, calcium, iron, lithium, manganese, etc. Inorganic salts, inorganic acids such as phosphoric acid, hydrochloric acid, sulfuric acid, oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, fluoromethanesulfonic acid and other organic acids, such as activated clay, acidic clay, silica alumina, zeolite , solid acids, heteropolyacid salts, etc. of strongly acidic ion exchange resins. Toluenesulfonic acid is particularly preferred.

Examples of the dehydrating agent used in step (2) of this embodiment include lower aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride, oxides of phosphorus pentoxide, calcium oxide, barium oxide, and the like, and sulfuric acid. For inorganic acids, molecular sieves and other porous ceramics, acetic anhydride can be preferably used. The usage amounts of the catalyst and dehydrating agent used in step (2) of this embodiment are not particularly limited, but _generally the catalyst can be The dehydrating agent can be used at 0.0001 to 1.0 mol, preferably 0.01 to 0.3 mol, and the dehydrating agent can be used at 1 to 3 mol, preferably 1 to 1.5 mol. In step (2) of this embodiment, as the reaction conditions for maleyl imidization, the above-mentioned intermediate amine compound (c) and maleic anhydride can be added, and the reaction temperature is 10 to 100°C, preferably 30 to 60°C. The temperature range is: react for 0.5 to 12 hours, preferably 1 to 4 hours, then add the aforementioned catalyst, and react at a temperature range of 90 to 130°C, preferably 105 to 120°C, for 1 to 24 hours, preferably 1 to 10 hours.

(Amine compound (B)) The curable composition of this embodiment contains an amine compound (B). By combining the amine compound (B) and the polymaleimide compound (A), the entire composition can contribute to low-temperature hardening and exhibit excellent molding processability, so it can be used for molding as structural materials. material, and useful. In addition, by reacting with the polymaleimide compound (A), it functions as a hardening agent and generates three-dimensional cross-linking, so that a hardened product with excellent heat resistance can be obtained, which is a preferred aspect. Examples of the amine compound (B) in this embodiment include compounds having primary to tertiary amine groups, with 1 or more carbon atoms, preferably hydrocarbons with 3 to 25 carbon atoms, and one molecule having 2 The above primary amine-based hydrocarbon compounds are more preferred. 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. In addition, the aromatic amine compound includes an aromatic heterocyclic compound, and the aliphatic amine compound includes an alicyclic aliphatic compound. Specific examples of the aliphatic amine compound in this embodiment include ethylenediamine, diethylenetriamine, hexamethylenediamine, triethylenetetramine, isophoronediamine, and guanidine derivatives. , guanamine derivatives, 1,3-bisaminomethylcyclohexane, pholine, 4,4-methylenebiscyclohexylamine and 4,4-ethylidenebiscyclohexylamine. This aliphatic amine compound can be used individually or in mixture of 2 or more types. Specific examples of the aromatic amine compound in this embodiment include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, and 3-methyl-1,4-diamine. Benzene, 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 ester (For example, 4,4'-diaminodiphenyl sulfide, 3,3'-diaminodiphenyl sulfide), 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'-bis(4-aminophenoxy)biphenyl, bis(4-( 4-Aminophenoxy)phenyl)sine, bis(4-(3-aminophenoxy)phenyl)sine, 9,9-bis(4-aminophenyl)benzine and imidazole, etc. This aromatic amine compound can be used individually or in mixture of 2 or more types. Among the above aromatic amine compounds, when mechanical properties during hardening are important, m-phenylenediamine, p-phenylenediamine, 3-methyl-1,4-diaminobenzene or 2, 5-Dimethyl-1,4-diaminobenzene. On the other hand, when heat resistance is important, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, and 4,4' are more preferred. -Diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-bis(4 -Aminophenoxy)biphenyl or 2,2-bis(4-(4-aminophenoxy)phenyl)propane. Moreover, when solubility in a solvent or workability are important, 4,4'-diaminodiphenylmethane and 3,3'-dimethyl-4,4'-diaminobiphenyl are more preferred. , 4,4'-diamino-3,3'-diethyl-diphenylmethane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane. Furthermore, when low dielectric properties are important, 4,4'-diamino-3,3'-diethyl-diphenylmethane or 2,2-bis(4-(4-amine phenoxy)phenyl)propane. Examples of the amine compound (B) other than the aliphatic amine compound and the aromatic amine compound include hydroxylammonium sulfate, BF ₃ -amine complex, and the like. As the preferred amine compound (B) in this embodiment, when control of the curing reaction and formability are important, an aromatic amine compound is preferred. Aliphatic amine compounds act as catalysts and tend to advance the hardening reaction. Therefore, when moldability is important, aromatic amine compounds are preferably used.

The curable composition of this embodiment preferably contains the amine compound (B) in an amount of not less than 5% by mass and not more than 50% by mass, more preferably not less than 7% by mass and not more than 30% by mass, based on the entire curable composition. Preferably, the content is not less than 10% by mass and not more than 20% by mass. It is preferable from the viewpoint of heat resistance that the content of the amine compound (B) is in the range of 10% by mass or more and 20% by mass or less.

(Hardening agent (C) other than amine compound (B)) A curing agent (C) other than the amine compound (B) may be added to the curable composition of this embodiment within the scope that does not impair the curing of the present invention. In addition, the curing agent (C) is preferably 2 mass % or more and 20 mass % or less, and most preferably 5 mass % or more and 10 mass % or less based on 100 mass % of the total amount of the curable composition. If the content of the hardener (C) is in the range of 5% by mass or more and 10% by mass or less, it is preferable from the viewpoint of hardening properties and low dielectric loss factor.

Examples of the curing agent (C) in this embodiment include cyanate ester compounds, amide compounds, acid anhydride compounds, phenol compounds, polyphenylene ether compounds, and compounds having a substituent containing an unsaturated double bond. , diene polymers, etc. These hardeners may be used alone or in combination of two or more types.

Examples of the cyanate ester compound include bisphenol A-type cyanate ester resin, bisphenol F-type cyanate ester resin, bisphenol E-type cyanate ester resin, bisphenol S-type cyanate ester resin, and bisphenol sulfide. Type cyanate ester resin, phenyl ether type cyanate ester resin, naphthyl ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethyldiphenyl type cyanate ester resin, polyhydroxy naphthalene type cyanate ester resin Acid ester resin, phenol novolak type cyanate ester resin, cresol novolak type cyanate ester resin, triphenylmethane type cyanate ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol Addition reaction type cyanate ester resin, phenol aralkyl type cyanate ester resin, naphthol novolac type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol co-novolac type cyanate ester resin Acid ester resin, naphthol-cresol novolak type cyanate ester resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type cyanate ester resin, biphenyl modified novolac type cyanate ester resin, anthracene type cyanate ester resin Ester resin, etc. These may be used individually, or 2 or more types may be used together.

Examples of the above-mentioned amide-based compound include dicyandiamide, a polyamide resin synthesized from a dimer of perilla oleic acid and ethylenediamine, and the like.

Examples of the acid anhydride-based compound include phthalic anhydride, trimellitic anhydride, pyromelite anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, and hexanhydride. Hydrophthalic anhydride, methyl hexahydrophthalic anhydride, etc.

Examples of the phenolic compound include: phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (XYLOK resin) )), polyvalent phenol novolak resins, represented by resorcin novolac resins, which are synthesized from polyvalent hydroxy compounds and formaldehyde, naphthol aralkyl resins, trimethylolmethane resins, tetraphenol ethane resins Alkane resin, naphthol novolak resin, naphthol-phenol novolac resin, naphthol-cresol novolac resin, biphenyl-modified phenol resin (polyphenol formed by linking phenol core with bismethylene) compound), biphenyl-modified naphthol resin (polymeric naphthol compound formed by linking phenol core with bismethylene), amine tris Modified phenol resin (polymeric phenol compound formed by linking phenol core with melamine, benzoguanamine, etc.), alkoxy-containing aromatic ring modified novolak resin (formaldehyde linked with phenol core and containing alkoxy group) Polyvalent phenol compounds composed of aromatic rings) and other polyvalent phenol compounds.

Preferable examples of the polyphenylene ether-based compound include those having a structure represented by the following general formula (5) or (6).

In the above general formulas (5) and (6), R ^d1 to R ^d8 are each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 1 to 5 carbon atoms, and an alkenyl group having 3 to 5 carbon atoms. 5 cycloalkyl group, alkoxy group with 1 to 5 carbon atoms, thioether group with 1 to 5 carbon atoms, alkylcarbonyl group with 2 to 5 carbon atoms, alkyloxy group with 2 to 5 carbon atoms Carbonyl group, alkylcarbonyloxy group having 2 to 5 carbon atoms, alkylsulfonyl group having 1 to 5 carbon atoms, etc. Examples of terminal structures of the structures of the general formulas (5) and (6) include those having a hydroxyl group or a group containing a reactive double bond. In addition, v is an integer value of 1 to 30, and w and u are also integer values of 1 to 30.

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

The alkylcarbonyl group having 2 to 5 carbon atoms is not particularly limited, and examples thereof include methylcarbonyl, ethylcarbonyl, propylcarbonyl, isopropylcarbonyl, butylcarbonyl, and the like.

The alkyloxycarbonyl group having 2 to 5 carbon atoms is not particularly limited, but examples thereof include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, and butyl. Oxycarbonyl, etc.

The alkylcarbonyloxy group having 2 to 5 carbon atoms is not particularly limited, but examples thereof include methylcarbonyloxy, ethylcarbonyloxy, propylcarbonyloxy, isopropylcarbonyloxy, and butyl. Carbonyloxy etc.

The alkylsulfonyl group having 1 to 5 carbon atoms is not particularly limited, but examples thereof include methylsulfonyl, ethylsulfonyl, propylsulfonyl, isopropylsulfonyl, and butyl. Sulfonyl group, amyl sulfonyl group, etc.

In this embodiment, R ^d1 to R ^d8 in the above general formulas (5) and (6) may be the same or different from each other, and are preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or an alkyl group having 3 to 5 carbon atoms. The cycloalkyl group of 5 is more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, further preferably a hydrogen atom, a methyl group, or an ethyl group, and particularly preferably a hydrogen atom or a methyl group.

Examples of Y in the general formula (6) include a divalent aromatic group derived from an aromatic compound having two phenolic hydroxyl groups. Furthermore, the aromatic compound having two phenolic hydroxyl groups is not particularly limited, but examples thereof include catechol, resorcinol, hydroquinone, 1,4-dihydroxynaphthalene, and 1,5-dihydroxynaphthalene. 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 these, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol E, and bisphenol F are preferred, and more preferred are 4,4'-bisphenol, bisphenol A, tetramethylbisphenol A. In addition, since the two phenolic hydroxyl groups of the aromatic compound having two phenolic hydroxyl groups form a phenylene ether bond (two oxygen atoms bonded to Y), Y is derived from the aromatic compound having two phenolic hydroxyl groups. A divalent aromatic group of aromatic compounds with a hydroxyl group. In other words, the group obtained by removing any two hydrogen atoms from the above-mentioned aromatic compound having two phenolic hydroxyl groups is regarded as "a divalent aromatic group derived from the aromatic compound having two phenolic hydroxyl groups".

The above-mentioned compound having a substituent containing an unsaturated double bond is not particularly limited as long as it has a substituent containing two or more unsaturated bonds in the molecule, for example, but examples thereof include allyl and isopropylene. group, 1-propenyl group, acrylyl group, methacrylyl group, styryl group, styrylmethyl group, etc. as the aforementioned substituent compound containing an unsaturated bond.

Examples of the diene polymer include non-modified diene polymers that have not been modified with polar groups. Here, the polar group is a functional group that affects the dielectric properties, and examples thereof include phenol group, amine group, epoxy group, and the like. The diene polymer is not particularly limited, and examples thereof include 1,2-polybutadiene, 1,4-polybutadiene, and the like.

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

(Other resins (D)) In addition to the polymaleimide compound (A) and the amine compound (B), other resins (D) may be contained as long as the purpose of the present disclosure is not impaired. As the other resin (D), bismaleimines, allyl ether compounds, allylamine compounds, trisulfide compounds other than the polymaleimide compound (A) may be suitably blended. Triallyl polycyanate, alkenyl phenol compounds, vinyl-containing polyolefin compounds, etc., epoxy resin, phenol resin, active ester resin, polyphenylene ether resin, benzo Resin, styrene maleic anhydride copolymer, polybutadiene and its modifications, polyacetal resin, polyvinyl alcohol resin, liquid crystal polymer, fluororesin, polystyrene, polyethylene, polyimide resin, Thermosetting polyimide resin, silicone rubber, silicone oil, etc. In addition, since the curable composition of this embodiment contains the amine compound (B), an epoxy resin may be selected as the other resin (D). Thereby, in the curable composition containing the polymaleimide compound (A), the amine compound (B) and the epoxy resin, the amine compound (B) acts as a hardener, so the copper density is reduced. Improved adhesion can be useful, for example, in the production of circuit boards using copper foil.

The epoxy resin is not particularly limited, but examples thereof include: phenol novolak type epoxy resin, cresol novolak type epoxy resin, α-naphthol novolak type epoxy resin, and β-naphthol novolak type epoxy resin. Novolak-type epoxy resin, bisphenol A novolac-type epoxy resin, biphenyl novolac-type epoxy resin, etc.; phenol aralkyl-type epoxy resin, naphthol aralkyl-type epoxy resin , phenol biphenyl aralkyl epoxy resin and other aralkyl epoxy resins; bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin Oxygen 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 ring Bisphenol-type epoxy resins such as oxy resins; biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, epoxy resins with biphenyl skeleton and diepoxypropyloxybenzene skeleton, etc. type epoxy resin; naphthalene type epoxy resin; binaphthol type epoxy resin; binaphthyl type epoxy resin; dicyclopentadiene type epoxy resin such as dicyclopentadiene phenol type epoxy resin; tetraepoxypropylene Epoxy resins such as diaminodiphenylmethane type epoxy resin, tripoxypropyl-p-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, etc. Propylamine type epoxy resin; 2,6-naphthalenedicarboxylic acid dialpoxypropyl ester type epoxy resin, hexahydrophthalic anhydride glycidyl ester type epoxy resin, etc. Oxygen resin; benzopyran-type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, 7-phenylhexamethyldibenzopyran, etc. These may be used individually, or 2 or more types may be used together. The content of other resin (D) is preferably 2 mass% or more and 20 mass% or less, and most preferably 5 mass% or more and 10 mass% or less based on 100 mass% of the total amount of the curable composition. It is preferable from the viewpoint of heat resistance that the content of the other resin (D) is in the range of 5% by mass or more and 10% by mass or less.

(hardening accelerator) In the curable composition of this embodiment, a curing accelerator may be appropriately used in combination as needed. As the aforementioned hardening accelerator, various hardening accelerators can be used. For example, the addition of polymerization initiators such as organic peroxides and azo compounds, or alkaline catalysts such as phosphine compounds and tertiary amines is effective. Specific examples of the hardening accelerator include benzyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, TPP-MK, TPP-K, triethylamine, Imidazoles etc. The hardening accelerator can be used alone, or two or more types can be used in combination. The blending amount of the curing accelerator in this embodiment is preferably 0.05 to 5% by mass of the entire curable resin composition.

(additive) The curable composition of this embodiment may be appropriately combined with additives as necessary. Examples of the additives include silane coupling agents, release agents, pigments, emulsifiers, non-halogen flame retardants, inorganic fillers, flame retardants, solvents, and the like. The content of the additive is preferably not less than 1% by mass and not more than 20% by mass, and most preferably not less than 3% by mass and not more than 10% by mass, based on 100% by mass of the total amount of the curable composition.

Examples of the flame retardant include inorganic phosphorus flame retardants, organic phosphorus flame retardants, halogen flame retardants, and non-halogen flame retardants. The curable composition of this embodiment is preferably blended with a non-halogen flame retardant that does not substantially contain halogen atoms in order to exhibit flame retardancy within a range that does not impair the purpose. Examples of the aforementioned non-halogen flame retardants include: phosphorus flame retardants, nitrogen flame retardants, polysiloxane flame retardants, inorganic flame retardants, organic metal salt flame retardants, etc., which can be used individually Use these, or use them in combination.

The curable composition of this embodiment may also be blended with an inorganic filler material if necessary. Examples of the inorganic filler include fused silica, crystalline silica, aluminum oxide, silicon nitride, aluminum hydroxide, and the like. When the blending amount of the inorganic filler is particularly large, it is preferable to use fused silica. The fused silica may be in a crushed or spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of spherical silica, it is preferable to appropriately adjust the particle size distribution of spherical silica. In consideration of flame retardancy, a high filling rate is preferable, and a particularly preferable filling rate is 30 mass % or more and 50 mass % or less based on the total amount of the curable composition. In addition, when the aforementioned curable composition is used for a conductive paste, etc. described in detail below, conductive fillers such as silver powder and copper powder can be used.

In the curable composition of this embodiment, the lower limit of the total content of the polymaleimide compound (A) and the amine compound (B) is preferably 40 mass%, based on the entire curable composition (100 mass%). 42% by mass, 45% by mass, 47% by mass, 48% by mass or 50% by mass. Moreover, the upper limit of the total content is preferably 100% by mass, 99% by mass, 98% by mass, or 97% by mass. The above-mentioned upper limit value and the above-mentioned lower limit value can be combined arbitrarily. Therefore, for example, in the curable composition of this embodiment, the total content of the polymaleimide compound (A) and the amine compound (B) is preferably 40% by mass relative to the entire curable composition (100% by mass). % or more and 100 mass % or less, the total content of the polymaleimide compound (A) and the amine compound (B) is more preferably 45 mass % or more and 100 mass % or less, the polymaleimine compound (A) and the amine compound The total content of compound (B) is more preferably 50 mass% or more and 100 mass% or less. In the curable composition of this embodiment, the lower limit of the total content of the polymaleimide compound (A), the amine compound (B) and the inorganic filler relative to the entire curable composition (100% by mass) is preferably: 70% by mass, 73% by mass, 75% by mass, 77% by mass or 80% by mass. Moreover, the upper limit of the total content is preferably 100% by mass, 99% by mass, 98% by mass, or 97% by mass. The aforementioned upper limit and the aforementioned lower limit can be combined arbitrarily as well as the range of the total content of the polymaleimide compound (A) and the amine compound (B). In the curable composition of this embodiment, the lower limit of the total content of the polymaleimide compound (A), the amine compound (B) and the additive is preferably 43% by mass relative to the entire curable composition (100% by mass). %, 45 mass%, 48 mass%, 50 mass% or 53 mass%. Moreover, the upper limit of the total content is preferably 100% by mass, 99% by mass, 98% by mass, or 97% by mass. The aforementioned upper limit and the aforementioned lower limit can be combined arbitrarily as well as the range of the total content of the polymaleimide compound (A) and the amine compound (B).

[hardened material] The cured product of the present disclosure is preferably obtained from the aforementioned curable composition. The cured material can be obtained by subjecting the curable composition to a curing reaction. The curable composition is obtained by uniformly mixing the above-mentioned components (for example, a curing agent, a blending agent), and can be easily produced as a cured product in the same manner as a conventional method. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coatings, and films. As for the aforementioned hardening (thermal hardening) reaction, it is easy to proceed even without a catalyst. However, if you want to further accelerate the reaction, add a polymerization initiator such as an organic peroxide or an azo compound, such as Alkaline catalysts such as phosphine compounds and tertiary amines are effective. For example, there are benzyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazoles, etc. In terms of the blending amount, curable resin compositions are preferred. 0.05 to 5% by mass of the entire substance.

[Heat-resistant materials and electronic materials] The cured product obtained by the curable composition containing the polymaleimide compound (A) and the amine compound (B) of the present disclosure has both excellent low hygroscopicity and low dielectric properties, so it is applicable For heat-resistant components or electronic components. It is particularly suitable for use in prepregs, circuit substrates, semiconductor packaging materials, semiconductor devices, build-up films, build-up substrates, adhesives or resist materials using conductive pastes, etc. . Furthermore, it can also be used as a matrix resin of fiber-reinforced resin, and is particularly suitable as a prepreg with high heat resistance or a small dimensional change rate. Furthermore, since the polymaleimide compound (A) contained in the curable composition exhibits excellent solubility in various solvents, it can be formed into a paint. The heat-resistant members and electronic members thus obtained can be used in various applications, including: industrial machine parts, general machine parts, automobile, railway, vehicle and other parts, aerospace and aviation-related parts, electronic and electrical parts, building materials, and containers.・Packaging components, daily necessities, sports and leisure products, casing components for wind power generation, etc., but are not limited to these.

Hereinafter, typical products (circuit substrates, semiconductor packaging materials, semiconductor devices, prepregs, build-up substrates, build-up films, and conductive pastes) manufactured using the curable resin composition of the present invention will be described.

[Circuit board] This disclosure is a circuit board of a laminate of the following prepreg and copper foil. As a method of obtaining a printed circuit board from the curable composition of the present embodiment, the above-mentioned prepreg is laminated by a common method, copper foil is overlapped appropriately, and the press is heated and pressed at 170 to 300°C under a pressure of 1 to 10 MPa. Take 10 minutes to 3 hours.

[Semiconductor packaging materials] The present disclosure is a semiconductor packaging material containing the curable composition of this embodiment. The semiconductor packaging material obtained by using the curable composition of this embodiment has improved hygroscopicity and low dielectric loss factor by using the polymaleimide compound (A) and the amine compound (B) of the present disclosure. properties, so it is a preferred aspect due to its excellent processability, formability, and reflow resistance in the manufacturing process. The curable composition of this embodiment used in the aforementioned semiconductor packaging material may contain an inorganic filler. In addition, the filling rate of the inorganic filler may be, for example, in the range of 0.5 to 1,200 parts by mass relative to 100 parts by mass of the curable composition of the present embodiment. Examples of the inorganic filler include barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg Siliceous Earth, fused silica, and spherical silica. Silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, etc.

An example of a method for obtaining the aforementioned semiconductor encapsulating material is to use an extruder, a kneader, a roller machine, etc., and further add any component of the curing accelerator and/or additive to the curable composition according to the present embodiment as necessary. Melt and mix until uniform. When used as a high thermal conductivity semiconductor packaging material for power transistors and power ICs, highly filled crystalline silica, aluminum oxide, silicon nitride, etc. with higher thermal conductivity than fused silica, or fused silica can be used , crystalline silica, alumina, silicon nitride, etc. The filling rate is preferably in the range of 30 to 95 parts by mass per 100 parts by mass of the curable composition. Among them, in order to improve flame retardancy, moisture resistance, and solder crack resistance, the linear expansion coefficient The reduction is preferably 70 parts by mass or more, further preferably 80 parts by mass or more.

[Semiconductor device] The present disclosure relates to a semiconductor device including a cured product of the aforementioned semiconductor packaging material. The semiconductor device obtained by using the curable composition of the present embodiment to obtain a semiconductor encapsulating material and then using the semiconductor encapsulating material is low in temperature because it uses the polymaleimide compound (A) and the amine compound (B) of the present disclosure. It has excellent viscosity and fluidity. In addition, since it improves hygroscopicity, thermoelastic modulus, and adhesion to metal materials, it has excellent processability, formability, and reflow resistance in the manufacturing process, making it a preferred aspect.

As a method of obtaining the semiconductor device, there is a method of molding the semiconductor packaging material using casting molding, transfer molding machine, injection molding machine, etc., and further heating and hardening at a temperature range of room temperature (20°C) to 250°C.

[prepreg] The present invention discloses a prepreg having a reinforcing base material and a semi-cured material impregnated with the curable composition of the present embodiment in the reinforcing base material. An example of a method for obtaining a prepreg from the above-mentioned curable composition is to blend an organic solvent described below and impregnate the varnished curable composition into a reinforcing base material (paper, glass cloth, glass nonwoven fabric, polyarylene). (aramid paper, polyarylamide cloth, glass mat, fiberglass gauze cloth, etc.), and then heat it at a heating temperature corresponding to the type of solvent used, preferably 50 to 170°C, to make the aforementioned curable composition A method of semi-hardening (or unhardening) to obtain prepreg. The mass ratio of the curable composition and the reinforcing base material used in this case is not particularly limited, but it is generally preferable to adjust the resin component contained in the prepreg to 20 to 60 mass %. In this embodiment, the semi-cured product of the curable composition is obtained by adjusting the heating temperature and heating time so that the curing reaction is not completed but is stopped midway. Furthermore, for example, the semi-hardened material may have a degree of hardening of 85% or less and 5% or more. On the other hand, the cured product in this embodiment may have a higher degree of hardening than the semi-cured product. In addition, the degree of hardening of the semi-cured material can be calculated by measuring the curing calorific value when the curable composition is heated and the curing calorific value of the semi-cured material using DSC. Degree of hardening (%) = [1-(hardening heat of semi-hardened material/hardening heat of curable composition)]×100

Examples of the organic solvent used in the production of the prepreg of this embodiment include methyl ethyl ketone, acetone, dimethyl formamide, methyl isobutyl ketone, methoxypropanol, and cyclohexanone. Hexanone, methylcerosu, ethyl diglycol acetate, prolylene glycol monomethyl ether acetate, etc., the selection and appropriate usage amount can be based on However, for example, when manufacturing a printed circuit board from a prepreg, it is preferable to use methyl ethyl ketone, acetone, dimethylformamide, etc., with a boiling point of 160°C or lower, as described below. As for the polar solvent, the non-volatile component is preferably used in a ratio of 40 to 80% by mass. In addition, as the reinforcing base material used in the production of the prepreg of this embodiment, inorganic fibers containing glass fiber, polyester fiber, polyamide fiber, etc., woven or non-woven fabrics containing organic fibers, or mats, paper etc., and may be used alone or in combination.

The heat treatment conditions for the prepreg in this embodiment are appropriately selected depending on the types and amounts of organic solvents, catalysts, and various additives used, but generally a temperature of 80 to 220°C is preferred. 3 minutes to 30 minutes.

[Build-up substrate] An example of a method for obtaining a build-up substrate from the curable composition of this embodiment is through the following steps 1 to 3. In step 1, first, the above-mentioned curable composition suitably mixed with rubber, filler, etc. is applied on the circuit substrate on which the circuit is formed using a spray coating method, a curtain coating method, etc., and then hardens it. In step 2, if necessary, after opening designated through-holes, etc., on the circuit substrate coated with the curable composition, the substrate is treated with a roughening agent, and the surface is washed with hot water. Concave and convex are formed on the surface, and metals such as copper are plated. In step 3, the operations of steps 1 to 2 are repeated in sequence as required, and the resin insulating layer and the conductor layer of the designated circuit pattern are alternately stacked (build up) to form a build-up substrate. In addition, in the aforementioned steps, the opening of the through-hole portion may be performed after the outermost resin insulating layer is formed. In addition, the build-up substrate in this embodiment can also be made by heating and pressing the copper foil with resin, which is obtained by semi-hardening the composition on the copper foil, at 170 to 300° C. to the wiring substrate on which the circuit is formed. In this way, the steps of forming a roughened surface and plating treatment are omitted, and a build-up substrate is produced.

[Build-up film] The present disclosure is a build-up film containing the curable composition of this embodiment. An example of a method for producing the build-up film of this embodiment is to apply the above-mentioned curable composition on the support film (Y) and then dry it to form a curable composition layer on the support film (Y). , a method of manufacturing an adhesive film for multilayer printed wiring boards. When a build-up film is produced from a curable composition, it is important that the film softens under the temperature conditions of lamination by the vacuum lamination method (usually 70 to 140°C), and that the circuit substrate is laminated while the circuit substrate is being laminated. The resin filling in the existing through holes or through holes allows fluidity (resin flow), and it is preferable to blend the above-mentioned components in a manner to exhibit such characteristics. In addition, in the resulting build-up film and circuit board (copper-clad laminate, etc.), it is required to exhibit certain performance at any location in order to prevent the phenomenon of locally different characteristic values due to phase separation, etc. Uniformity of appearance.

Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. Usually, it is better to fill the resin within this range. Furthermore, when laminating both sides of the circuit board, it is appropriate to fill approximately 1/2 of the through hole.

The method of producing the above-mentioned adhesive film can be specifically prepared by preparing the above-mentioned curable resin composition in the form of varnish, coating the varnish-like composition on the surface of the support film (Y), and further heating or spraying. The organic solvent is dried by blowing hot air or the like to form a composition layer (X) composed of a curable composition, whereby the composition layer (X) is produced. As the aforementioned organic solvent, for example, it is preferable to use ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, celus acetate, propylene glycol monomethyl ether acetate, carbitol, etc. Acetate esters such as alcohol acetate, carbitols such as carbitol and butylcarbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide , N-methylpyrrolidone, etc., and it is preferably used in a ratio of 30 to 60 mass % of non-volatile components.

The thickness of the formed composition layer (X) is generally preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit substrate is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably in the range of 10 to 100 μm. Furthermore, the composition layer (X) in this embodiment may be protected by a protective film described below. By protecting it with a protective film, dust and the like can be prevented from adhering to and damaging the surface of the resin composition layer.

Examples of the above support film (Y) and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter also referred to as "PET"), and polyethylene naphthalate. Such as polyester, polycarbonate, polyimide, and even metal foil such as release paper, copper foil, aluminum foil, etc. In addition, in addition to matting treatment and corona treatment, the support film and protective film can also be subjected to mold release treatment. Although the thickness of the support film is not particularly limited, it is usually in the range of 10 to 150 μm, preferably in the range of 25 to 50 μm. In addition, the thickness of the protective film is preferably 1 to 40 μm.

The support film (Y) is peeled off after being laminated on the circuit board or forming an insulating layer by heating and curing. If the support film (Y) is peeled off after heating and hardening the adhesive film, dust and the like in the hardening step can be prevented from adhering. In the case of peeling after hardening, the support film is usually subjected to a release treatment in advance. In addition, a multilayer printed circuit board can be produced from the build-up film obtained as described above. For example, when the resin composition layer (X) is protected by a protective film, after peeling off the resin composition layer (X), the resin composition layer (X) is laminated on one side of the circuit board by, for example, a vacuum lamination method or Both sides are in direct contact with the circuit board. The lamination method can be batch type or continuous in roll type. Moreover, if necessary, the build-up film and the circuit board may be heated (preheated) before lamination. The conditions for lamination are preferably to set the crimping temperature (lamination temperature) to 70 to 140°C, and to set the crimping pressure to 1 to 11kgf/cm ² (9.8×10 ⁴ to 107.9×10 ⁴ N/m ² ), preferably lamination under reduced pressure of 20mmHg (26.7hPa) or less.

＜Conductive Paste＞ An example of a method for obtaining a conductive paste from the curable composition of the present invention is a method of dispersing conductive particles into the composition. The above-mentioned conductive paste can be used as a paste resin composition for circuit connection or an anisotropic conductive adhesive according to the type of conductive particles used. [Example]

The present invention will be explained more specifically through Examples and Comparative Examples. However, the following "parts" and "%" are based on mass unless otherwise specified in advance. In addition, the physical properties of the synthesized polymaleimide compound (A) were measured as follows, and are shown in Table 1.

(1)Amine equivalent The amine equivalent of the intermediate amine compound (c) is measured by the following measurement method. In a 500 mL Erlenmeyer flask with a stopper, approximately 2.5 g of the intermediate amine compound (c) as the sample, 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine were accurately weighed, and then a cooling tube was installed and set at 120 Heat to reflux in an oil bath at °C for 150 minutes. 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. Carry out a blank test in the same way and make corrections. Amine equivalent (g/equivalent)=(S×2,000)/(Blank-A) S: Amount of sample (g) A: Consumption of 0.5mol/L potassium hydroxide-ethanol solution (mL) Blank: Consumption of 0.5mol/L potassium hydroxide-ethanol solution in the blank test (mL)

(2)GPC measurement Using the following measuring devices and measuring conditions, the number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (Mw/Mn) of the polymaleimide compound (A) obtained in the Examples and Comparative Examples were calculated. ). "Measuring device" "HLC-8320 GPC" manufactured by Tosoh Co., Ltd. "Measurement conditions" Column: Protection column "HXL-L" made by Tosoh Co., Ltd. + "TSK-GEL G2000HXL" made by Tosoh Co., Ltd. + "TSK-GEL G2000HXL" made by Tosoh Co., Ltd. + "TSK-GEL G3000HXL" made by Tosoh Co., Ltd. + Tosoh Co., Ltd. "TSK-GEL G4000HXL" Detector: RI (differential refractometer) Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Co., Ltd. Measuring conditions: Tube string temperature 40℃ Expansion solvent Tetrahydrofuran Flow rate: 1.0ml/minute Standard: According to the measurement manual of the aforementioned "GPC Workstation EcoSEC-WorkStation", use the following monodisperse polystyrene with a known molecular weight. (use polystyrene) Made by Tosoh Co., Ltd. "A-500" Made by Tosoh Co., Ltd. "A-1000" Made by Tosoh Co., Ltd. "A-2500" Made by Tosoh Co., Ltd. "A-5000" Tosoh Co., Ltd. "F-1" Tosoh Co., Ltd. "F-2" Tosoh Co., Ltd. "F-4" Tosoh Co., Ltd. "F-10" Made by Tosoh Co., Ltd. "F-20" Made by Tosoh Co., Ltd. "F-40" Made by Tosoh Co., Ltd. "F-80" Made by Tosoh Co., Ltd. "F-128" Sample: A tetrahydrofuran solution whose resin solid content of the polymaleimide compound (A) obtained in the synthesis example was converted into 1.0% by mass was filtered with a microfilter (50 μl).

(3)FD-MS measurement The FD-MS spectrum of the polymaleimide compound (A) obtained in the Example was measured using the following measuring device and measuring conditions. Measuring device: JMS-T100GC AccuTOF Measurement conditions Measuring range: m/z＝4.00～2000.00 Change rate: 51.2mA/min Final current value: 45mA Cathode voltage: -10kV Recording interval: 0.07sec

(4) ¹³ C-NMR Measurement The ¹³ C-NMR spectrum of the polymaleimide compound (A) obtained in Examples was measured using the following measurement device and measurement conditions. ¹³ C-NMR: "JNM-ECZ400S" manufactured by JEOL RESONANCE Resonance frequency: 100MHz Accumulated times: 4000 times Solvent: Chloroform-d Sample concentration: 12 mass% Relaxation reagent: Chromium acetyl acetonate (III)

(5) Synthesis of polymaleimide compound (A) <Synthesis Example 1> Synthesis of polymaleimide compound (A-1) (I) Synthesis of intermediate amine compound (c-1) Installation In a flask equipped with a thermometer, cooling tube, Dean-Stark trap and stirrer, add 242.4g (2.0mol) of 2-ethylaniline, 242g of xylene and 80g of activated clay. While stirring, raise the temperature to 130°C and keep it for 30 minutes. Then, DVB-810 (mixture of divinylbenzene/ethylstyrene (divinylbenzene/ethylstyrene=81/19(mol)%), manufactured by NIPPON STEEL Chemical & Material) 272.0 was dropped dropwise over 2 hours. g, let it react directly for 1 hour. Then, it took 6 hours to raise the temperature to 190°C and maintain it for 10 hours. After the reaction, the reaction mixture was air-cooled to 100°C, diluted with 300 g of toluene, filtered to remove activated clay, and low molecular weight substances such as the solvent and unreacted matter were distilled off under reduced pressure to obtain the intermediate amine compound (c-1). . The amine equivalent of the intermediate amine compound (c-1) was 214 g/equivalent. (II) Maleic imidization In a 2L flask equipped with a thermometer, cooling tube, Dean-Stark trap and stirrer, add 117.7g (1.2mol) maleic anhydride and 700g toluene, and stir at room temperature. Next, a mixed solution of 214 g (1 equivalent) of the intermediate amine compound (c-1) and 175 g of DMF was dropped over 1 hour and allowed to react for 2 hours. 37.1 g of p-toluenesulfonic acid monohydrate was added to the reaction solution and heated to 115°C. After cooling and separating the azeotropic water and toluene under reflux, only toluene was returned to the system and dehydration reaction was performed for 5 hours. After the air was cooled to room temperature, it was neutralized with 49% NaOH. Then, toluene and water were distilled off under reduced pressure at 60° C., and 600 g of MEK (methyl ethyl ketone) was added to the DMF solution remaining in the flask. After the solution was heated to 60° C., 200 g of ion-exchange water was used to perform liquid separation three times to remove salt in the solution. Furthermore, sodium sulfate was added for drying, and then concentrated under reduced pressure. The resulting reaction product was vacuum-dried at 80° C. to obtain a polymaleimide compound (A-1). The chemical structure and characteristic analysis of the polymaleimide compound (A-1) were confirmed using GPC, FD-MS and ¹³ C-NMR. The measurement results are shown in Figures 1A to 1C. Moreover, according to the GPC measurement results, the Mn of the polymaleimide compound (A-1) was 998, Mw was 367,834, and Mw/Mn was 368.697.

<Examples 1 to 2 and Comparative Examples 1 to 3> ＜＜Preparation of hardening composition and production of hardened material>> The polymaleimide compound (A-1) obtained in the above synthesis example 1 and the comparative maleimide (1) ("BMI-2300" Daiwa Chemical Industry Co., Ltd. were used in the ratio shown in Table 1 below. Co., Ltd.), maleimide (2) for comparison ("BMI-5100" manufactured by Yamato Chemical Industry Co., Ltd.), amine compound (B-1) (4,4'-) as amine compound (B) Diaminodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.), amine compound (B-2) (4,4'-methylenebis(2-ethyl-6-methylaniline)), and DCPO ("PERCUMYL D", manufactured by NOF Co., Ltd., Dicumyl Peroxide) was blended as a curing catalyst to prepare curable compositions of Examples 1 to 2 and Comparative Examples 1 to 3.

Next, the curable compositions of Examples 1 to 2 and Comparative Examples 1 to 3 were cured by using the following curing conditions to produce curable compositions corresponding to Examples 1 to 2 and Comparative Examples 1 to 3 respectively. of hardened matter. Furthermore, the physical properties of dielectric constant, dielectric loss factor, and hygroscopicity were evaluated by the following methods. The results are shown in Table 1. ＜＜Hardening conditions＞＞ Using a vacuum press, heat and harden at 250°C for 2 hours after 2 hours at 200°C. Plate thickness after forming: 1.3mm ＜＜Evaluation of dielectric constant and dielectric loss factor>> According to JIS-C-6481, using the network analyzer "E8362C" manufactured by Agilent Technologies Co., Ltd., using the cavity resonance method, after absolute drying, the test piece was measured after being stored in a room at 23°C and a humidity of 50% for 24 hours. Dielectric constant (Dk) and dielectric loss factor (Df) at 10GHz. ＜＜Evaluation of hygroscopicity＞＞ In the present Examples and Comparative Examples, as an evaluation method for low hygroscopicity, the moisture absorption rate (%) was calculated and evaluated by the following method. A test piece with a size of 5 mm × 55 mm × 1.3 mm was cut out from the hardened material obtained above, and maintained at 85°C, 85% RH, and 1 atmosphere for 50 hours using a pressure cooker testing machine. The moisture absorption rate was calculated according to the following formula ( %) for evaluation. Moisture absorption rate (%) = (mass of the test piece after the test - mass of the test piece before the test)/(mass of the test piece before the test) × 100

[Table 1] Table 1 Example 1 Example 2 Comparative example 1 Comparative example 2 Comparative example 3 Polymaleimide compound (A-1) (mass part) 20 20 Polymaleimide (1) for comparison (parts by mass) 20 Polymaleimide (2) for comparison (parts by mass) 20 20 Amine compound (B-1) (mass part) 3 3 3 Amine compound (B-2) (mass part) 3 3 Catalyst (DCPO) (parts by mass) 0.23 0.23 0.23 0.23 0.23 characteristic Dielectric constant Dk(10GHz) 2.52 2.53 Unable to evaluate due to cracked resin board 2.67 2.69 Dielectric loss factor Df(10GHz) 0.0033 0.0026 0.0039 0.0035 Moisture absorption rate (%) 1.22 0.91 2.22 1.99

From the results shown in Table 1 above, when Examples 1 to 2 are compared with Comparative Examples 1 to 3, it can be confirmed that by using the polymaleimide compound (A) and the amine compound (B) of Examples 1 to 2, )'s curable composition achieves low dielectric constant, low dielectric dissipation factor, and low moisture absorption under high temperature and humidity. Furthermore, it was confirmed that by using the curable composition containing the polymaleimide compound (A) and the amine compound (B) of Examples 1 to 2, it was possible to achieve high curing performance even in the frequency band of Sub6 or higher. It has low hygroscopicity, low dielectric constant and low dielectric loss factor. [Possibility of industrial application]

According to the present disclosure, it is possible to provide a curable composition and a cured product thereof that exhibit low dielectric characteristics and low moisture absorption when cured.

without

Figure 1A shows the GPC measurement results of the polymaleimide compound (A-1) of Synthesis Example 1. FIG. 1B shows the FD-MS measurement results of the polymaleimide compound (A-1) of Synthesis Example 1. FIG. 1C shows the ¹³ C-NMR measurement results of the polymaleimide compound (A-1) of Synthesis Example 1.

without.

Claims (8)

A curable composition characterized by containing: a polymaleimide compound containing a monocyclic or condensed polycyclic aromatic group with two or more linear or branched alkylene groups bonded A), and amine compound (B). In the curable composition of claim 1, the polymaleimide compound (A) has a structural unit represented by the following general formula (1), (In the above general formula (1), R ¹ each independently represents an alkyl group, R ² each independently represents an alkyl group, an alkoxy group or an alkylthio group having 1 to 10 carbon atoms; Aryl group, aryloxy group or arylthio group; cycloalkyl group with 3 to 10 carbon atoms; halogen atom; hydroxyl group; or mercapto group; R ³ , R ⁴ , R ⁵ and R ⁶ are each independent, representing a hydrogen atom or methyl group group, and one of R ³ and R ⁴ is a hydrogen atom, the other is a methyl group, one of R ⁵ and R ⁶ is a hydrogen atom, the other is a methyl group; X ¹ represents the following general formula (x ) the substituent shown; (In the general formula (x), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, and one of R ⁷ and R ⁸ is a hydrogen atom, the other is a methyl group, and R ⁹ each independently represents a carbon Alkyl, alkoxy or alkylthio group with 1 to 10 atoms; aryl, aryloxy or arylthio group with 6 to 10 carbon atoms; cycloalkyl group with 3 to 10 carbon atoms; halogen atom ; Hydroxyl; or ^mercapto ; t represents an integer from 0 to 4;) r is the average number of ^{substitutions} of an integer, q represents an integer from 0 to 4, k represents an integer from 1 to 100). A hardened product of the hardenable composition of claim 1 or 2. A prepreg having a reinforcing base material and a semi-cured product impregnated with the curing composition of claim 1 or 2 in the reinforcing base material. A circuit board comprising a laminate of the prepreg according to claim 4 and copper foil. A build-up film containing the curable composition of claim 1 or 2. A semiconductor packaging material containing the curable composition of claim 1 or 2. A semiconductor device including a cured product of the semiconductor packaging material of claim 7.