Polymaleimide compound, curable composition, cured product, prepreg, circuit board, build-up film, semiconductor sealing material and semiconductor device

Abstract

To provide a polymaleimide compound which exhibits excellent low thermal expansion coefficient and moisture absorption resistance in a cured product, a curable composition containing the polymaleimide compound and a cured product thereof.SOLUTION: There is provided a polymaleimide compound which comprises an aromatic amine compound (A), a compound (B1) represented by the following general formula and maleic anhydride as essential reaction raw materials (1). [In the formula, X is a divalent hydrocarbon group having a carbon number of 1 to 18 which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom and a halogen atom, an oxygen atom, a sulfur atom, a sulfinyl group and a sulfonyl group and n is a number of 0 or 1.]SELECTED DRAWING: Figure 2A

Description

[Technical field]

[0001] The present disclosure relates to a polymaleimide compound, a curable composition containing the polymaleimide compound and a cured product thereof, a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device. [Background technology]

[0002] As circuit board materials for electronic devices, prepregs obtained by impregnating glass cloth with thermosetting resins such as epoxy resins and BT (bismaleimide-triazine) resins and drying by heating, laminates obtained by heat-curing the prepregs, and multilayer boards obtained by combining the laminates and the prepregs and heat-curing them are widely used. In particular, semiconductor package boards are becoming thinner, and warping of the package boards during mounting is becoming a problem, so materials that exhibit high heat resistance are required to suppress this. Furthermore, in recent years, signals have become faster and higher in frequency, and there is a demand for thermosetting resin compositions that give cured products that exhibit a sufficiently low dielectric tangent while maintaining a sufficiently low dielectric constant under these conditions. In particular, in recent years, in various electrical material applications, particularly in advanced material applications, there has been a demand for materials and compositions thereof that combine various required properties, such as improved performance represented by heat resistance and dielectric properties, as well as moisture absorption resistance to improve the reliability of package substrates. In response to these demands, maleimide resins have been attracting attention as materials that combine heat resistance with low dielectric constant and low dielectric loss tangent. However, while conventional maleimide resins exhibit high heat resistance, they are not satisfactory in terms of low dielectric properties. In response to these problems, for example, Patent Document 1 discloses a polymaleimide resin obtained by reacting an oligomer obtained by reacting an aromatic divinyl compound with an aniline compound with maleic anhydride as a maleimide resin exhibiting excellent dimensional stability and low dielectric properties. However, its thermal expansion coefficient and moisture absorption resistance are not necessarily sufficient, and there is room for further improvement. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent No. 7160151 Summary of the Invention [Problem to be solved by the invention]

[0004] Therefore, an object of the present disclosure is to provide a polymaleimide compound that exhibits an excellent low coefficient of thermal expansion and moisture absorption resistance in a cured product. [Means for solving the problem]

[0005] The present invention relates to a polymaleimide compound which uses an aromatic amine compound (A), a compound (B1) represented by general formula (b1), and maleic anhydride as essential reactive raw materials (1), and which is capable of achieving both an excellent low thermal expansion coefficient and moisture absorption resistance in a cured product at a high level; a curable composition containing the polymaleimide compound; and a cured product thereof.

[0006] Another object of the present invention is to provide a cured product of the curable resin composition, and a prepreg, a circuit board, a build-up film, a semiconductor encapsulant, and a semiconductor device using the curable resin composition. Effect of the Invention

[0007] According to the present disclosure, it is possible to provide a polymaleimide compound capable of achieving both excellent low thermal expansion coefficient and moisture absorption resistance in a cured product, a curable composition containing the polymaleimide compound, and a cured product thereof. Such a polymaleimide compound is particularly useful in applications such as electronic component sealing materials. [Brief description of the drawings]

[0008] [Figure 1A] FIG. 1A shows the results of GPC measurement of the intermediate amine (a-1) of this example. [Figure 1B]FIG. 1B shows the results of FD-MS measurement of the intermediate amine (a-1) of this example. [Figure 1C] FIG. 1C shows the results of 13C-NMR measurement of the intermediate amine (a-1) of this example. [Figure 2A] FIG. 2A shows the results of GPC measurement of the polymaleimide compound (A-1) of this example. [Figure 2B] FIG. 2B shows the results of FD-MS measurement of the polymaleimide compound (A-1) of this example. [Figure 2C] 2C shows the results of 13C-NMR measurement of the polymaleimide compound (A-1) of this example. [Figure 3A] FIG. 3A shows the results of GPC measurement of the intermediate amine (a-2) of this example. [Figure 3B] FIG. 3B shows the results of FD-MS measurement of the intermediate amine (a-2) of this example. [Figure 3C] FIG. 3C shows the results of 13C-NMR measurement of the intermediate amine (a-2) of this example. [Figure 4A] FIG. 4A shows the results of GPC measurement of the polymaleimide compound (A-2) of this example. [Figure 4B] FIG. 4B shows the results of FD-MS measurement of the polymaleimide compound (A-2) of this example. [Figure 4C] FIG. 4C shows the results of 13C-NMR measurement of the polymaleimide compound (A-2) of this example. [Figure 5A] FIG. 5A shows the results of GPC measurement of the intermediate amine (a-3) of this example. [Figure 5B] FIG. 5B shows the results of FD-MS measurement of the intermediate amine (a-3) of this example. [Figure 5C] FIG. 5C shows the results of 13C-NMR measurement of the intermediate amine (a-3) of this example. [Figure 6A] FIG. 6A shows the results of GPC measurement of the polymaleimide compound (A-3) of this example. [Figure 6B] FIG. 6B shows the results of FD-MS measurement of the polymaleimide compound (A-3) of this example. [Figure 6C] FIG. 6C shows the results of 13C-NMR measurement of the polymaleimide compound (A-3) of this example. [Figure 7] FIG. 7 shows the results of GPC measurement of the intermediate amine (a-4) of this example. [Figure 8] FIG. 8 shows the results of GPC measurement of the polymaleimide compound (A-4) of this example. [Figure 9] FIG. 9 shows the results of GPC measurement of the intermediate amine (a-5) of this example. [Figure 10] FIG. 10 shows the results of GPC measurement of the polymaleimide compound (A-5) of this example. [Figure 11] FIG. 11 shows the results of GPC measurement of the intermediate amine (a-6) of this example. [Figure 12] FIG. 12 shows the results of GPC measurement of the polymaleimide compound (A-6) of this example. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] Below, an embodiment of the present invention (hereinafter referred to as the "present embodiment") will be described in detail, but the present disclosure is not limited to the following description and can be implemented in various modifications within the scope of its gist.

[0010] <Terminology> In this specification, the term "reaction raw material" refers to a compound that is used to obtain a target compound by a chemical reaction such as synthesis or decomposition and that partially constitutes the chemical structure of the target compound, and excludes substances that play the role of chemical reaction auxiliaries such as solvents and catalysts. In particular, in this specification, the term "reaction raw material" refers to a precursor for obtaining a target polymaleimide compound or a precursor compound thereof (e.g., an intermediate amine compound (C) in which the aromatic amine compounds (A) are linked to each other via a compound (B1) represented by the general formula (b1)) by a chemical reaction. The "alkyl group" in this specification may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a tert-pentyl group, a neopentyl group, a 1,2-dimethylpropyl group, an n-hexyl group, an isohexyl group, a (n-)heptyl group, a (n-)octyl group, a (n-)nonyl group, a (n-)decyl group, a (n-)undecyl group, and a (n-)dodecyl group. In the present specification, examples of a "cycloalkyl group" include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a norbornyl group, and an adamantyl group. As used herein, the term "alkylthio group" includes a methylthio group, an ethylthio group, a propylthio group, a butylthio group, an octylthio group, and a 2-ethylhexylthio group. In the present specification, examples of the "alkoxy group" include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a 2-ethylhexyloxy group, an octyloxy group, and a nonyloxy group. In the present specification, the "aryl group" includes a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and the like. In the present specification, examples of the "aryloxy group" include a phenoxy group, a naphthyloxy group, an anthryloxy group, a phenanthryloxy group, and a pyrenyloxy group. As used herein, the "arylthio group" includes a phenylthio group, a naphthylthio group, an anthrylthio group, a phenanthrylthio group, a pyrenylthio group, and the like. As used herein, the term "halogen atom" includes, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. The term "structural unit" as used herein refers to a (repeating) unit of a chemical structure formed during a reaction or polymerization, in other words, to a partial structure in a compound produced by a reaction or polymerization other than the structure of the chemical bonds involved in the reaction or polymerization.

[0011] [Polymaleimide compounds] The polymaleimide compound according to this embodiment is a polymaleimide compound obtained by reacting raw materials (1) with an aromatic amine compound (A), a compound (B1) represented by general formula (b1), and maleic anhydride. This allows the cured product to have both a low coefficient of thermal expansion and excellent moisture absorption resistance at a high level. In this embodiment, a modifying agent ( ) may be contained in the reaction raw material (1). The polymaleimide compound of this embodiment may be a polymaleimide compound in which the reaction raw materials (3) are an intermediate amine compound (C) in which aromatic amine compounds (A) are crosslinked with each other via a compound (B1) represented by general formula (b1), and maleic anhydride. Furthermore, the intermediate amine compound (C) may be a compound in which the reaction raw materials (2) are an aromatic amine compound (A), a compound (B1) represented by general formula (b1), and a modifying agent ( ) added as necessary. In other words, the intermediate amine compound (C) in this embodiment preferably has a structure in which an aromatic ring to which an amino group (including a substituted amino group in which the hydrogen atom of the amino group is further substituted with an alkyl group having 1 to 6 carbon atoms) is bonded, and the structural unit of the aromatic amine compound (A) and the structural unit of the compound (B1) represented by general formula (b1) are linked to the aromatic ring by chemical bonds, and if necessary, a structural unit of the modifier ( ) is chemically bonded to the aromatic ring in the structural unit of the aromatic amino compound (A).The polymaleimide compound in this embodiment has a structure in which the amino group (including -NH2 and a substituted amino group) bonded to the aromatic ring of the intermediate amine compound (C) is substituted with a maleimide group. Therefore, the "polymaleimide compound" in this embodiment and the "intermediate amine compound (C)" which is the precursor of the "polymaleimide compound" are polymer compounds that differ in that the amino group (including -NH2 and substituted amino groups) bonded to the aromatic ring is replaced with a maleimide group. The 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, a group obtained by removing two hydrogen atoms from the benzene ring of the general formula (a) is referred to as a structural unit of the aromatic amine compound (A). In addition, the structural unit of the compound (B1) represented by the general formula (b1) refers to a group obtained by cleaving the unsaturated bonds of the two ethenyl groups of the compound (B1) represented by the general formula (b1). In the present embodiment, since the aromatic amino compound (A) having a specific aromatic ring structure is used as the reaction raw material, it becomes easier to control the reaction site with the compound (B1) represented by general formula (b1) described below, and therefore it becomes easier to obtain a polymaleimide compound having a uniform chemical structure or chain length. As a result, a polymaleimide compound that exhibits low moisture absorption and low dielectric tangent in the cured product can be provided.

[0012] Below, the components of the reaction raw material (1) for the polymaleimide compound, namely the aromatic amine compound (A), the compound (B1) represented by general formula (b1), the optional modifier ( ) and maleic anhydride, will be explained, and then another preferred embodiment of the polymaleimide compound and a method for producing the polymaleimide compound will be explained.

[0013] -Aromatic amine compound (A)- The aromatic amine compound (A) in this embodiment has an aromatic ring to which an amino group (-NH2 or substituted amino group) is bonded. Therefore, the aromatic amine compound (A) can be an amine-based compound. The aromatic ring forming the central structure of the aromatic amine compound (A) is preferably monocyclic and includes an aromatic hydrocarbon ring and an aromatic heterocycle. The aromatic hydrocarbon ring is preferably a benzene ring. Examples of the aromatic heterocycle include a hetero six-membered ring such as a pyran ring or a pyridine ring. The aromatic amine compound (A) in this embodiment more preferably has an aromatic ring to which -NH2 is bonded that does not include a substituted amino group.

[0014] In the aromatic amine compound (A) of the present embodiment, it is preferable that one or more and three or less hydrogen atoms of the aromatic ring of the aromatic amine compound (A) are substituted with a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkyloxy group, or an alkylthio group having 1 to 10 carbon atoms, an aryl group, an aryloxy group, an arylthio group, or an aralkyl group having 6 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. An alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 6 to 10 carbon atoms are preferable, and an alkyl group having 1 to 3 carbon atoms and an aryl group having 6 to 8 carbon atoms are more preferable. The alkyl group having 1 to 10 carbon atoms may be linear or may have a branched structure. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the alkyloxy group include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, and a butylthio group. Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a tolyl group, a xylyl group, a naphthyl group, and an anthryl group. Examples of the aryloxy group include a phenoxy group, a tolyloxy group, a xylyloxy group, and a naphthyloxy group. Examples of the arylthio group include a phenylthio group, a tolylthio group, a xylylthio group, and a naphthylthio group. Examples of the cycloalkyl group having 3 to 10 carbon atoms include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group. Examples of the aralkyl group include a benzyl group, a methylbenzyl group, and a phenethyl group. The smaller the molecular weight of the alkyl group, the more remarkable the effect of the present invention (low thermal expansion coefficient), and the larger the molecular weight of the alkyl group, the more remarkable the effect of the present invention (low moisture absorption).

[0015] The upper limit of the number of alkyl groups bonded to an aromatic ring having an amino group (including -NH2 and a substituted amino group) in the aromatic amine compound (A) may be a number obtained by subtracting 3 from the number of substitutable ring-constituting atoms in the unsubstituted aromatic ring, from the viewpoint that the aromatic ring has an amino group (including -NH2 and a substituted amino group) and two bonds are used in polymerization. For example, when the aromatic ring is a benzene ring, the number of the alkyl groups is 3 or less. In addition, by making the number of alkyl groups substituted on the aromatic ring of the aromatic amine compound (A) 1 or more, it becomes easier to control the reaction site with the compound (B1) represented by general formula (b1) described below, and therefore it becomes easier to obtain a polymaleimide compound with a uniform chemical structure or chain length. As a result, the cured product of the polymaleimide compound tends to exhibit low moisture absorption and excellent high-frequency electrical properties.

[0016] A preferred embodiment of the aromatic amine compound (A) in this embodiment will be described below taking as an example a case where the aromatic ring of the aromatic amine compound (A) is a benzene ring. In the present embodiment, among the carbon atoms in the benzene ring constituting the aromatic amine compound (A), it is preferred that one or more carbon atoms having the largest HOMO electron density (Huckel coefficient) are unsubstituted (or substituted with a hydrogen atom). As a result, the reaction of ArS with a cationoid reagent formed from a compound (B1) represented by the general formula (b1) described later can be carried out. E It becomes easier to control the reaction and molecular design. To explain in more detail, if the carbon atom having the largest HOMO electron density (Huckel coefficient) among the carbon atoms in the benzene ring constituting the aromatic amine compound (A) is unsubstituted, the carbocation of the compound (B1) represented by the general formula (b1), which is a cationoid reagent, is easily reacted with the carbon atom having the largest HOMO electron density. Therefore, by controlling the number and position of the alkyl groups bonded to the carbon atom of the benzene ring, it is possible to adjust the bonding site or number of bonds with the compound (B1) represented by the general formula (b1). It is therefore presumed that it becomes easier to design the chemical structure or molecular chain length of the resulting polymaleimide compound. For example, when the aromatic amine compound (A) has an aniline skeleton having one benzene ring and one amino group, it is preferable that at least one of the carbon atoms at the 2nd, 4th, and 6th positions of the aniline nucleus is substituted with a hydrogen atom. This makes it easier for the cationoid reagent formed from the compound (B1) represented by the general formula (b1) described below to attack at least one of the carbon atoms at the 2nd, 4th, and 6th positions, which are the ortho and para positions with high electron density of the aniline nucleus. In particular, when an aromatic amine compound (A) having an aniline nucleus substituted with an alkyl group at a specific position is used, the bonding site with the compound (B1) represented by the general formula (b1) can be largely controlled, so that a polymaleimide compound with a uniform chemical structure or chain length can be easily obtained. For example, when a 2,6-dialkylamine is used as the aromatic amine compound (A), it is considered that a large amount of polymaleimide compounds bonded to the compound (B1) represented by the general formula (b1) at the 4th position can be obtained.

[0017] Specific examples of the aromatic amine compound (A) of the present embodiment include aniline, dimethylaniline (2,3-xylidine, 2,4-xylidine, 2,6-xylidine, 3,4-xylidine, or 3,5-xylidine), 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, 3,4-diisopropylaniline, or 3,5-diisopropylaniline), ethylmethylaniline (e.g., a methyl group at any one of the 2,3-position, 2,4-position, 2,6-position, 3,4-position, or 3,5-position, and a methyl group at the other position ... is an ethyl group), 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, methylisopropylaniline in which one of the 2,3-position, 2,4-position, 2,6-position, 3,4-position, or 3,5-position is a methyl group and the other is an isopropyl group), or ethylbutylaniline (for example, ethylbutylaniline in which one of the 2,3-position, 2,4-position, 2,6-position, 3,4-position, or 3,5-position is an ethyl group and the other is a butyl group), etc. can be used. The butyl includes n-butyl, tert-butyl, and sec-butyl. The aromatic amine compound (A) in this embodiment may be used alone or in combination of two or more.

[0018] For example, in the case of a chemical structure in which a maleimide group is directly bonded to an unsubstituted benzene ring, such as N-phenylmaleimide, the benzene ring and the five-membered ring of the maleimide are stable in a state in which they are arranged on the same plane, so that they tend to stack, resulting in high crystallinity. This causes poor solvent solubility. In contrast, in the case of the present disclosure, for example, in the case of 2,6-dimethylaniline, where an alkyl group (e.g., a methyl group) is present as a substituent on the benzene ring, the benzene ring and the five-membered ring of the maleimide take a twisted conformation due to the steric hindrance of the methyl group, making it difficult to stack, resulting in reduced crystallinity and improved solvent solubility, which is a preferred embodiment. However, if the steric hindrance is too large, there is a concern that the reactivity during synthesis of the maleimide may be inhibited, so it is preferable to use, for example, an aromatic amine compound (A) having an alkyl group having 1 to 6 carbon atoms.

[0019] The aromatic amine compound (A), which is an essential component of the reaction raw material (1) in this embodiment, can be represented, for example, by the following general formula (a).

[0020] [ka] (a) (In the above general formula (a), R 1a represents a hydrocarbon group, m a represents an integer from 0 to 3. 1a may be the same or different.)

[0021] In the general formula (a), R 1arepresents a hydrocarbon group, and examples of the hydrocarbon group include an alkyl group, alkyloxy group, or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group, arylthio group, or aralkyl group having 6 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms, of which an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 6 to 10 carbon atoms are preferred, and an alkyl group having 1 to 3 carbon atoms and an aryl group having 6 to 8 carbon atoms are more preferred. Examples of the alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, aralkyl group, and cycloalkyl group are the same as those mentioned above. In the general formula (a), m a is preferably 1 or 2. 1a When a plurality of groups are present, they may be the same or different hydrocarbon groups. In the present embodiment, the aromatic amine compound (A) represented by the general formula (a) may be used alone or in combination of two or more kinds.

[0022] -Compound (B1) represented by general formula (b1)- The compound (B1) represented by general formula (b1) in this embodiment contains two aromatic rings, each of which has one aromatic vinyl group (CH2=CH-) (also referred to as a vinyl group) as a substituent on the aromatic ring, and can be used without any particular restriction as long as it can react with the aromatic amine compound (A). In this embodiment, the reaction raw material (1) may contain a mixture of the compound (B1) represented by the general formula (b1) and a modifying agent ( ).

[0023] [ka] (b1)

[0024] In general formula (b1), X represents a divalent hydrocarbon group having 1 to 18 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom, an oxygen atom, a sulfur atom, a sulfinyl group, or a sulfonyl group, and n is the number 0 or 1.

[0025] In general formula (b1), X's each independently represent "a divalent hydrocarbon group having 1 to 18 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom", "a halogen atom", "a hydroxyl group", "a carboxyl group", "an amino group", or "a nitro group". The phrase "which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom" means that a hydrogen atom of the hydrocarbon group may be substituted with a functional group containing a nitrogen atom, an oxygen atom, a sulfur atom, or a halogen atom, such as an amino group (-NH2), a nitro group (-NO2), a hydroxyl group (-OH), a mercapto group (-SH), or a fluoro group (-F), or that a functional group (linking group) containing a nitrogen atom, an oxygen atom, a sulfur atom, or a halogen atom, such as an ether group (-O-) or a thioether group (-S-), may be contained inside or at the end of the carbon skeleton. In addition, the term "divalent hydrocarbon group" refers to a hydrocarbon group having two bonding positions, and is not limited to a linear saturated hydrocarbon group, but may have a carbon-carbon unsaturated bond, a branched structure, or a cyclic structure.

[0026] In general formula (b1), when X is a hydrocarbon group, the number of carbon atoms is preferably 12 or less, more preferably 8 or less, and even more preferably 6 or less. When X is a hydrocarbon group, examples of functional groups contained in the hydrocarbon group include an amino group (-NH2), a nitro group (-NO2), a hydroxyl group (-OH), a carboxyl group (-COOH), a mercapto group (-SH), a fluoro group (fluorine atom, -F), a chloro group (chlorine atom, -Cl), a bromo group (bromine atom, -Br), an iodo group (iodine atom, -I), and the like. Examples of X include a single bond, a methylene group (-CH2-), an ethylene group (-C2H4-), an n-propylene group (-nC3H6-), a phenylene group (-C6H4-), a biphenylene group (-C6H4C6H4-), an oxygen atom, a sulfur atom, a sulfinyl group (-S(=O)-), and a sulfonyl group (-S(=O)2-).

[0027] The compound (B1) represented by general formula (b1) preferably has a structure represented by the following general formula (b1a).

[0028] [ka] (b1a)

[0029] In the general formula (b1a), p represents an integer of 0 to 5, and is preferably an integer of 1 to 2. The smaller p is, the shorter the distance between crosslinking points in the cured product becomes, and the more remarkable the effect of the invention (low thermal expansion coefficient) becomes.

[0030] As the compound (B1) represented by the general formula (b1), for example, bis(vinylphenyl)methane (BVPM), 1,2-bis(vinylphenyl)ethane (BVPE), and 1,6-bis(4-vinylphenyl)hexane (BVPH) are more preferable.

[0031] The compound (B1) represented by general formula (b1) in this embodiment may be used alone or in combination of two or more kinds. In this embodiment, the structural unit of the compound (B1) represented by general formula (b1) is contained in an amount of preferably 10 to 90 mass%, and more preferably 20 to 90 mass%, relative to the total amount (100 mass%) of the polymaleimide compound.

[0032] -Modifier ( )- The polymaleimide compound in this embodiment may use other compounds as reaction raw materials in addition to the aromatic amine compound (A), the compound (B1) represented by the general formula (b1), and maleic anhydride. Examples of such other compounds include a modifier ( ). That is, in the embodiment, the aromatic amine compound (A), the compound (B1) represented by the general formula (b1), the modifier ( ), and maleic anhydride may be used as the reaction raw material (1). It is preferable that the polymaleimide compound in this embodiment uses the modifier ( ) as the reaction raw materials in addition to the aromatic amine compound (A), the compound (B1) represented by the general formula (b1), and maleic anhydride, because the cured product of the finally obtained polymaleimide compound is excellent in terms of low moisture absorption and low dielectric tangent. In addition, the modifying agent ( ) also generates a carbocation like the compound (B1) represented by the general formula (b1), and therefore is likely to react with the carbon atom having the largest HOMO electron density (Huckel coefficient) among the carbon atoms in the aromatic hydrocarbon ring constituting the aromatic amine compound (A).

[0033] The modifier ( ) in this embodiment includes, for example, vinylbenzene (styrene), vinylbiphenyl, vinylnaphthalene, and various compounds in which an aromatic ring of these is substituted with one or more substituents such as an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group. The alkyl group may be either a straight chain type or a branched type, and may have an unsaturated bond in the structure. In particular, when low moisture absorption is important, the alkyl group or the alkoxy group preferably has 1 to 4 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, and an isobutyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propyloxy group, and a butoxy group. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

[0034] The modifying agent ( ) which can be the reaction raw material (1) of the polymaleimide compound of the present disclosure can be represented by the following general formula (d).

[0035] [ka] (d) (In the above general formula (d), Y represents a substituent capable of generating a carbocation, and R 2b each independently represents an alkyl group, an alkoxy group, or an alkylthio group having 1 to 10 carbon atoms; an aryl group, an aryloxy group, or an arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group; b represents an integer from 0 to 5. b If is an integer greater than or equal to 2, there are multiple R 2b may be the same or different.)

[0036] Y in the formula (d) has the ability to generate a carbocation, and specifically represents a vinyl group, a hydroxymethyl group, an alkoxymethyl group, a chloromethyl group, or the like, which is capable of reacting with the aniline compound. 2b each independently preferably 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; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl group, more preferably represents an alkyl group having 1 to 10 carbon atoms, and even more preferably represents an alkyl group having 1 to 6 carbon atoms. In the general formula (b1), t b is preferably 1 to 4. b If is 2 or more, there are multiple R 2b may be the same group or different groups.

[0037] Specific examples of the modifying agent () of the present embodiment include, but are not limited to, benzenes such as styrene, fluorostyrene, alkylvinylbenzene (o-, m-, p-methylstyrene, o-, m-, p-ethylvinylbenzene), benzyl chloride, α-methylstyrene, and compounds composed of these derivatives; aromatic alcohols such as benzyl alcohol, dimethylphenylcarbinol, and compounds composed of these derivatives; biphenyl compounds such as 4-vinylbiphenyl, 4-vinyl-p-terphenyl, and compounds composed of these derivatives; and vinylnaphthalenes such as 1-vinylnaphthalene, 2-vinylnaphthalene, and compounds composed of these derivatives. In particular, ethylvinylbenzene, styrene and benzyl alcohol are preferred from the viewpoints of raw material availability and reactivity.

[0038] In the case where a modifying agent (D) is used as the reaction raw material (1) of the polymaleimide compound in this embodiment, the molar ratio ((B1) / (D)) of the modifying agent (B1) to the compound (B1) represented by general formula (b1) in the reaction raw material (1) is preferably 99 / 1 to 50 / 50, and more preferably 98 / 2 to 70 / 30.

[0039] -Maleic anhydride- In the present embodiment, maleic anhydride is an essential component of the reaction raw material (1) of the polymaleimide compound, and is used in a reaction for maleimidizing an amino group (including -NH and a substituted amino group) derived from the aromatic amine compound (A), as will be described later in the section on the production method of the polymaleimide compound.

[0040] <Preferable form of polymaleimide compound> Hereinafter, preferred embodiments of the polymaleimide compound of the present disclosure will be described taking as an example a case where each aromatic ring is a benzene ring. The following chemical structural formulas are provided to exemplify the present disclosure, and the scope of the present disclosure is not limited to the following chemical structural formulas.

[0041] -Preferable form of polymaleimide compound- The polymaleimide compound in this embodiment is preferably represented by the following general formula (1).

[0042] [ka] (1)

[0043] In the general formula (1), R 1 each independently represents an alkyl group, alkyloxy group, or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group, arylthio group, or aralkyl group having 6 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 8 carbon atoms. 1 may be the same or different. 1 is a methyl group, an ethyl group, an n-propyl group, a phenyl group, a benzyl group, or a phenylethyl group. 1is derived from the aromatic amine compound (A) and / or the modifying agent (D). 1 The benzene ring to which is bonded can be the benzene ring of the aromatic amine compound (A). In the general formula (1), 1 represents the average number of repeating units and is preferably 0-20, more preferably 0-18, and even more preferably 0-15. In the general formula (1), m represents an integer of 0 to 3. 1 is bonded to at least one of the 2-, 3-, 4-, 5-, or 6-positions of the benzene ring to which R 1 is preferably bonded. In the general formula (1), o represents an integer of 0 to 3. In the general formula (1), X represents a divalent hydrocarbon group having 1 to 18 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom, an oxygen atom, a sulfur atom, a sulfinyl group, or a sulfonyl group, and n is the number 0 or 1.

[0044] The polymaleimide compound in this embodiment is preferably represented by the following general formula (2).

[0045] [ka] (2)

[0046] In the general formula (2), R 1 each independently represents an alkyl group, alkyloxy group, or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group, arylthio group, or aralkyl group having 6 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 6 to 10 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms, or an aryl group having 6 to 8 carbon atoms. 1may be the same or different. 1 is a methyl group, an ethyl group, an n-propyl group, a phenyl group, a benzyl group, or a phenylethyl group. 1 The benzene ring to which is bonded can be the benzene ring of the aromatic amine compound (A). In the general formula (2), 1 represents the average number of repeating units and is preferably 0-20, more preferably 0-18, and even more preferably 0-15. In the general formula (2), m represents an integer of 0 to 3. 1 is bonded to at least one of the 2-, 3-, 4-, 5-, or 6-positions of the benzene ring to which R 1 is preferably bonded. In the general formula (2), o represents an integer of 0 to 3. In the general formula (2), p represents an integer of 0 to 5, and is preferably an integer of 1 or 2.

[0047] The number average molecular weight (Mn) of the polymaleimide compound of the present disclosure is preferably in the range of 350 to 2,000, and more preferably in the range of 400 to 1,500. Moreover, the weight average molecular weight (Mw) of the polymaleimide compound is preferably in the range of 400 to 500,000, and more preferably in the range of 450 to 400,000. In view of the excellent low dielectric constant and low dielectric tangent, the polymaleimide compound of the present disclosure preferably has a molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) calculated from gel permeation chromatography (hereinafter abbreviated as "GPC") measurement in the range of 1.001 to 500, more preferably 1.001 to 400. Note that when the molecular weight distribution is wide and there are many high molecular weight components from the GPC chart obtained from the GPC measurement, the proportion of high molecular weight components that contribute to flexibility increases, and therefore, compared to cured products using conventional maleimides, a cured product with reduced brittleness and excellent flexibility and pliability can be obtained, which is a preferred embodiment. The number average molecular weight (Mn), weight average molecular weight (Mw) and molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymaleimide compound of the present embodiment are measured using GPC under the measurement conditions described in the examples described later.

[0048] <Method of producing polymaleimide compound> A method for producing the polymaleimide compound of the present disclosure will be described below. The polymaleimide compound of the present embodiment may be produced by any method, including using an aromatic amine compound (A), a compound (B1) represented by general formula (b1), and maleic anhydride as reaction raw materials (1), or may be produced in any manner as long as it has a structural unit represented by general formula (1). An example of a method for producing the polymaleimide compound of the present disclosure includes a production method including the following steps (1) and (2). Step (1): A step of reacting an aromatic amine compound (A) as a reaction raw material (2) with a compound (B1) represented by general formula (b1) to obtain an intermediate amine compound (C) of the present embodiment; Step (2): A step of reacting the intermediate amine compound (C) obtained in the step (1) with maleic anhydride as the reaction raw material (3) to obtain the polymaleimide compound of the present disclosure. Specifically, the method for producing a polymaleimide compound of the present embodiment preferably includes a step (1) (also referred to as a crosslinking step) of reacting an aromatic amine compound (A) with a compound (B1) represented by general formula (b1) in the presence of a solid acid catalyst, and a step (2) (also referred to as a condensation step) of condensing an intermediate amine compound (C) produced in the step (1) with maleic anhydride. Hereinafter, each step of the method for producing the polymaleimide compound of the present disclosure will be described in order.

[0049] <Step (1): Production step of intermediate amine compound (C)> The process for producing the intermediate amine compound (C) in this embodiment will be described below. The step (1) in this embodiment is not particularly limited, but is, for example, a step of reacting the above-mentioned aromatic amine compound (A) with the above-mentioned compound (B1) represented by the general formula (b1) (e.g., 1,2-bis(vinylphenyl)ethane (BVPE)) and, if necessary, other compounds such as a modifier () (e.g., styrene) in the presence of an acid catalyst. This can produce an intermediate amine compound (C).

[0050] The blending ratio of the aromatic amine compound (A) and the compound (B1) represented by the general formula (b1) is preferably 0.1 to 10 moles, more preferably 0.2 to 3 moles, as the molar ratio of the compound (B1) represented by the general formula (b1) to 1 mole of the aromatic amine compound (A), in consideration of the balance of the physical properties of moldability and curability during the production of the resulting cured product. In addition, when the modifying agent ( ) is used in combination, the total molar ratio of the compound (B1) represented by the general formula (b1) and the modifying agent ( ) to 1 mole of the aromatic amine compound (A) is preferably 0.1 to 10 moles, more preferably 0.2 to 3 moles. As a specific method for carrying out the reaction, all the raw materials are generally charged at once and reacted at a predetermined temperature, or an aromatic amine compound (A) and an acid catalyst are charged and reacted while maintaining a predetermined temperature and dropping a compound (B1) represented by general formula (b1) or other compounds (e.g., a modifier ( )). In this case, the dropwise addition 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 materials can be distilled off as necessary to obtain the intermediate amine compound (C). When no solvent is used, the intermediate amine compound (C), which is the target product, can be obtained by distilling off the unreacted materials.

[0051] Examples of the acid catalyst used in step (1) of the present embodiment include inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid; solid acids such as activated clay, acid clay, silica alumina, zeolite, and strongly acidic ion exchange resins; and heteropolyhydrochloric acid. From the viewpoint of handling, however, solid acids that allow the catalyst to be easily removed by filtration after the reaction are preferred. When other acids are used, it is preferable to neutralize with a base and wash with water after the reaction. The amount of the acid catalyst is in the range of 1 to 100 parts by mass per 100 parts by mass of the total amount of the raw materials (compound (B1) represented by general formula (b1) or a mixture of compound (B1) represented by general formula (b1) and modifier (), and aromatic amine compound (A)) to be charged, and from the viewpoint of handling and economic efficiency, the amount is preferably 1 to 60 parts by mass. The reaction temperature is usually in the range of 80 to 270°C, but in order to suppress the formation of isomeric structures and to avoid side reactions such as thermal decomposition, 80 to 220°C is preferred.

[0052] In the step (1) of the present embodiment, the reaction time of the mixture of the compound (B1) represented by the general formula (b1) or the compound (B1) represented by the general formula (b1) and the modifying agent ( ) with the aromatic amine compound (A), i.e., the time of the condensation reaction, is usually in the range of 1 to 48 hours in total under the above reaction temperature conditions, and preferably in the range of 1 to 30 hours in total, since the reaction does not proceed completely in a short time and side reactions such as thermal decomposition of the product occur in a long time. In the method for producing the intermediate amine compound (C) in this embodiment, since aniline or a derivative thereof also serves as a solvent, other solvents are not necessarily used, but it is also possible to use a solvent. For example, when 1,2-bis(vinylphenyl)ethane (BVPE) is used as a raw material for reaction, a method may be adopted in which a solvent capable of azeotropic dehydration, such as toluene, xylene, or chlorobenzene, is used, and if necessary, water contained in the catalyst, etc. is azeotropically dehydrated, and then the solvent is distilled off, followed by reaction within the above-mentioned reaction temperature range.

[0053] The intermediate amine compound (C) obtained in the step (1) is preferably represented by the following general formula (3), for example.

[0054] [ka] (3)

[0055] In the general formula (3), R 1 each independently represents a hydrocarbon group having 1 to 10 carbon atoms, preferably an alkyl group or an aromatic group, more preferably an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or a cycloalkyl group having 3 to 10 carbon atoms. 1 may be the same or different. 1 is a methyl group, an ethyl group, an n-propyl group, a phenyl group, a benzyl group, or a phenylethyl group. 1 The benzene ring to which is bonded can be the benzene ring of the aromatic amine compound (A). In the general formula (3), l represents the average number of repeating units and is preferably 0-20, more preferably 0-18, and even more preferably 0-15. In the general formula (3), m represents an integer of 0 to 3. 1 is bonded to at least one of the 2-, 3-, 4-, 5-, or 6-positions of the benzene ring to which R 1 is preferably bonded. In the general formula (3), o represents an integer of 0 to 3. In the general formula (3), X represents a divalent hydrocarbon group having 1 to 18 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom, an oxygen atom, a sulfur atom, a sulfinyl group, or a sulfonyl group, and n is the number 0 or 1.

[0056] In addition, R in the general formula (3) 1The preferred forms of n, m, l, and o are the same as those in the general formula (1). Another preferred form of the intermediate amine compound (C) obtained by the step (1) includes a structure in which the maleimide group in the general formula (2), which is also a preferred form of the polymaleimide compound, is replaced with an amino group (including -NH2 and a substituted amino group).

[0057] In the present embodiment, the amine equivalent of the intermediate amine compound (C) is preferably from 172 to 800 g / equivalent, and more preferably from 172 to 500 g / equivalent. In this specification, the amine equivalent of the intermediate amine compound (C) is a value measured by a method based on the neutralization titration method specified in JIS K 0070 (1992).

[0058] <Step (2): Maleimidation> In the present embodiment, step (2) is a step of reacting the intermediate amine compound (C) obtained in step (1) with maleic anhydride. The amino group (including -NH2 and substituted amino groups) of the intermediate amine compound (C) can undergo a maleimidization reaction to form a chemical structure in which the amino group is substituted with a maleimide ring, thereby obtaining the polymaleimide compound of the present disclosure. In this embodiment, the intermediate amine compound (C) represented by the general formula (4) obtained in step (1) is charged into a reactor, dissolved in a suitable solvent, and then reacted with maleic anhydride in the presence of a catalyst. After the reaction, unreacted maleic anhydride or other impurities are removed by washing with water or the like, and the solvent is removed under reduced pressure to obtain the target polymaleimide compound. If necessary, a dehydrating agent may be used during the reaction.

[0059] Examples of the organic solvent used in step (2) of the present embodiment include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, acetophenone, etc.; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, sulfolane, etc.; cyclic ethers such as dioxane, tetrahydrofuran, etc.; esters such as ethyl acetate, butyl acetate, etc.; aromatic solvents such as benzene, toluene, xylene, etc.; and the like, and these may be used alone or in combination.

[0060] In step (2) of the present embodiment, the mixing ratio of the intermediate amine compound (C) and maleic anhydride is preferably such that the equivalent ratio of maleic anhydride to the amino equivalent of the intermediate amine compound (C) is in the range of 1 to 5, more preferably 1 to 3, and the reaction is carried out in an organic solvent.

[0061] Examples of the catalyst that can be used in step (2) of the present embodiment include inorganic salts such as acetates, chlorides, bromides, sulfates, and nitrates of nickel, cobalt, sodium, calcium, iron, lithium, manganese, or the like; inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid; solid acids such as activated clay, acid clay, silica alumina, zeolites, and strongly acidic ion exchange resins; and heteropolyhydrochloric acids. Toluenesulfonic acid is particularly preferred.

[0062] Examples of the dehydrating agent used in step (2) of the present embodiment include lower aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride; oxides such as phosphorus pentoxide, calcium oxide, and barium oxide; inorganic acids such as sulfuric acid; and porous ceramics such as molecular sieves. Of these, acetic anhydride is preferably used. The amounts of the catalyst and the dehydrating agent used in step (2) of the present embodiment are not particularly limited, but typically, the catalyst can be used in an amount of 0.0001 to 1.0 mol, preferably 0.01 to 0.5 mol, and the dehydrating agent can be used in an amount of 1 to 3 mol, preferably 1 to 1.5 mol, relative to 1 equivalent of the amino group (-NH2) of the intermediate amine compound (C). In step (2) of the present embodiment, the reaction conditions for maleimidization are as follows: the intermediate amine compound (C) and maleic anhydride are charged and reacted at a temperature range of 10 to 100°C, preferably 30 to 60°C, for 0.5 to 12 hours, preferably 1 to 4 hours, and then the catalyst is added and the reaction is continued at a temperature range of 90 to 130°C, preferably 105 to 120°C, for 1 to 24 hours, preferably 1 to 10 hours.

[0063] [Curable composition] The polymaleimide compound of the present disclosure can be used to prepare a curable composition. The curable composition of the present disclosure preferably contains the above-mentioned polymaleimide compound. The polymaleimide compound of the present embodiment is excellent in solvent solubility, fluidity when heated and melted, and handleability, and further contributes to the development of dimensional stability, low moisture absorption, brittleness resistance, heat resistance, and low dielectric constant and low dielectric loss tangent of the cured product, so that the cured product obtained from the curable composition containing the polymaleimide compound exhibits excellent low thermal expansion coefficient and moisture absorption resistance.

[0064] The curable composition of the present disclosure may contain a curing agent, and further, if necessary, various compounding agents such as a curing accelerator, a silane coupling agent, a mold release agent, a pigment, an emulsifier, a non-halogen flame retardant, an inorganic filler, a flame retardant (e.g., an inorganic phosphorus flame retardant, an organic phosphorus flame retardant, a halogen flame retardant), a solvent, etc. may be added. In addition, in addition to the polymaleimide compound, it is also possible to appropriately compound epoxy resins, phenolic resins, active ester resins, cyanate resins, polyphenylene ether resins, benzoxazine resins, styrene-maleic anhydride copolymers, polybutadiene and modified products thereof, polyacetal resins, polyvinyl alcohol resins, liquid crystal polymers, fluororesins, polystyrene, polyethylene, polyimide resins, silicone gels, silicone oils, etc., within the scope of the present disclosure.

[0065] [Cured product] The cured product of the present disclosure is preferably obtained from the curable composition. The cured product can be obtained by subjecting the curable composition to a curing reaction. The curable composition can be obtained by uniformly mixing the above-mentioned components (e.g., curing agent, compounding agent), and can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

[0066] [Semiconductor encapsulation materials] The present disclosure relates to a semiconductor encapsulation material containing the curable composition of the present embodiment. The semiconductor encapsulation material obtained using the curable composition of the present embodiment has an improved thermal expansion coefficient and moisture absorption resistance due to the use of the polymaleimide compound of the present disclosure, and therefore has excellent processability, moldability, and reflow resistance in the manufacturing process, making it a preferred embodiment. The curable composition of the present embodiment used for the semiconductor encapsulation material may contain an inorganic filler. The filling rate of the inorganic filler may be, for example, in the range of 0.5 to 1200 parts by mass per 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 silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, aluminum oxide, aluminum hydroxide, silicon nitride, and aluminum nitride.

[0067] The method for obtaining the semiconductor encapsulation material may include a method in which the curable composition of the present embodiment and, if necessary, additives as optional components are thoroughly melt-mixed until homogeneous using an extruder, kneader, roll, or the like.

[0068] [Semiconductor Devices] The present disclosure relates to a semiconductor device including a cured product of the semiconductor encapsulation material. The semiconductor device obtained using the semiconductor encapsulation material obtained using the curable composition of the present embodiment uses the polymaleimide compound of the present disclosure, and therefore has low viscosity and excellent flowability, and further has improved moisture absorption, thermal expansion coefficient, and adhesion to metal materials, and therefore has excellent processability, moldability, and reflow resistance in the manufacturing process, which is a preferred embodiment.

[0069] The semiconductor device can be obtained by molding the semiconductor encapsulation material using a casting machine, a transfer molding machine, an injection molding machine or the like, and then curing the material by heating in a temperature range of room temperature (20°C) to 250°C.

[0070] [Prepreg] The present disclosure relates to a prepreg having a reinforcing substrate and a semi-cured product of the curable composition of the present embodiment impregnated into the reinforcing substrate. As a method for obtaining a prepreg from the curable composition, a method is given in which the curable composition is impregnated into a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, etc.) by blending an organic solvent described later and turning it into a varnish, and then heating it at a heating temperature according to the type of solvent used, preferably at 50 to 170°C, to semi-cure (or uncur) the curable composition to obtain a prepreg. The mass ratio of the curable composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable to prepare the resin content in the prepreg to be 20 to 60% by mass. In this embodiment, the semi-cured product of the curable composition is obtained by adjusting the heating temperature and heating time to stop the curing reaction midway without completing it. Also, for example, the semi-cured product may have a degree of curing of, for example, 5% or more and 85% or less. On the other hand, the cured product in this embodiment may have a higher degree of curing than the semi-cured product. The degree of curing of the semi-cured product can be calculated from the following formula by measuring the amount of heat generated during curing when the curable composition is heated and the amount of heat generated during curing of the semi-cured product by DSC. Degree of cure (%)=[1-(cure heat generation amount of semi-cured product / cure heat generation amount of curable composition)]×100

[0071] Examples of organic solvents used in the production of prepregs include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, and propylene glycol monomethyl ether acetate. The selection and appropriate amount of the organic solvent used can be appropriately selected depending on the application. For example, when a printed circuit board is further produced from the prepreg as described below, it is preferable to use a polar solvent having a boiling point of 160° C. or less, such as methyl ethyl ketone, acetone, or dimethylformamide, and it is also preferable to use such a solvent in such a proportion that the nonvolatile content is 40 to 80 mass%.

[0072] [Circuit board] The present disclosure relates to a circuit board which is a laminate of the prepreg and copper foil. A method for obtaining a printed circuit board from the curable composition of the present embodiment includes a method in which the prepreg is laminated by a conventional method, copper foil is appropriately laminated, and the laminate is heated and compressed at 170 to 300° C. under a pressure of 1 to 10 MPa for 10 minutes to 3 hours.

[0073] [Build-up film] The present disclosure relates to a build-up film containing the curable composition of the present embodiment. A method for producing the build-up film of the present embodiment includes a method for producing the build-up film by applying the curable composition onto a support film to form a curable composition layer to form an adhesive film for a multilayer printed wiring board.

[0074] When producing a build-up film from the curable composition, it is essential that the film softens under the lamination temperature conditions (usually 70 to 140°C) in the vacuum lamination method and exhibits fluidity (resin flow) that allows the resin to fill via holes or through holes present in the circuit board at the same time as lamination of the circuit board, and it is preferable to mix the above-mentioned components so as to exhibit such properties.

[0075] Here, the diameter of the through-holes in the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to make it possible to fill the resin within this range. When both sides of the circuit board are laminated, it is preferable to fill about 1 / 2 of the through-holes.

[0076] Specifically, the adhesive film can be produced by preparing the curable composition in a varnish form, applying the varnish-like composition to the surface of the support film (Y), and then drying the organic solvent by heating or blowing hot air or the like to form a composition layer (X) made of the curable composition.

[0077] The thickness of the composition layer (X) formed is usually preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

[0078] The composition layer (X) in this embodiment may be protected with a protective film described later. By protecting the resin composition layer with a protective film, it is possible to prevent the adhesion of dirt and the like to the surface of the resin composition layer and prevent scratches.

[0079] Examples of the support film (Y) and protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate, polycarbonate, polyimide, and further release paper and metal foils such as copper foil and aluminum foil. The support film and protective film may be subjected to a release treatment in addition to a mud treatment and a corona treatment.

[0080] The thickness of the support film is not particularly limited, but is usually in the range of 10 to 150 μm, preferably 25 to 50 μm, and the thickness of the protective film is preferably 1 to 40 μm.

[0081] The support film (Y) is peeled off after laminating it onto the circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled off after the adhesive film is heat cured, the adhesion of dust and the like during the curing process can be prevented. When peeling off after curing, the support film is usually subjected to a release treatment in advance.

[0082] [Heat-resistant materials and electronic materials] Since the cured product obtained from the curable composition containing the polymaleimide compound of the present disclosure exhibits excellent low thermal expansion rate and moisture absorption resistance, it can be suitably used for heat-resistant members or electronic members. In particular, it can be suitably used for prepregs, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up boards, adhesives using conductive pastes, resist materials, etc. It can also be suitably used as a matrix resin for fiber-reinforced resins, and is particularly suitable as a prepreg having high heat resistance or a small dimensional change rate. Further, since the polymaleimide compound contained in the curable composition exhibits excellent solubility in various solvents, it can be made into a paint. The heat-resistant members and electronic members thus obtained can be suitably used for various applications, for example, industrial machine parts, general machine parts, parts of automobiles, railways, vehicles, etc., space and aviation-related parts, electronic and electrical parts, building materials, container and packaging members, daily necessities, sports and leisure goods, housing members for wind power generation, etc., but are not limited thereto.

Examples

[0083] The present invention will be specifically described with reference to Examples and Comparative Examples. In the following, "parts" and "%" are based on mass unless otherwise specified. The physical properties of the synthesized polymaleimide compound were measured as follows and are shown in Table 1.

[0084] 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 compounds obtained in Examples and Comparative Examples were calculated. <Measurement of GPC> Measuring device: "HLC-8320 GPC" manufactured by Tosoh Corporation Column: Guard column "HXL-L" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation Detector: RI (differential refractometer) Data processing: Tosoh Corporation's "GPC Workstation EcoSEC-WorkStation" Measurement conditions: Column temperature 40℃ Developing solvent: Tetrahydrofuran Flow rate 1.0ml / min Standard: In accordance with the measurement manual for the aforementioned "GPC Workstation EcoSEC-WorkStation," the following monodisperse polystyrene with known molecular weight was used. (Polystyrene used) "A-500" manufactured by Tosoh Corporation "A-1000" manufactured by Tosoh Corporation "A-2500" manufactured by Tosoh Corporation "A-5000" manufactured by Tosoh Corporation "F-1" manufactured by Tosoh Corporation "F-2" manufactured by Tosoh Corporation "F-4" manufactured by Tosoh Corporation "F-10" manufactured by Tosoh Corporation "F-20" manufactured by Tosoh Corporation "F-40" manufactured by Tosoh Corporation "F-80" manufactured by Tosoh Corporation "F-128" manufactured by Tosoh Corporation Sample: A tetrahydrofuran solution (1.0 mass % in terms of resin solid content) filtered through a microfilter (50 μl).

[0085] <Amine equivalent and maleimide group equivalent> The amine equivalent of the aromatic amine obtained in the examples was measured by the following method. Approximately 2.5 g of aromatic amine, 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine were precisely weighed into a 500 mL Erlenmeyer flask equipped with a stopper, and then the mixture was heated to reflux for 150 minutes in an oil bath equipped with a cooling tube and set to 120°C. After cooling, 5.0 mL of distilled water, 100 mL of propylene glycol monomethyl ether, and 75 mL of tetrahydrofuran were added, and titration was performed by potentiometric titration with a 0.5 mol / L potassium hydroxide-ethanol solution. A blank test was conducted in the same manner for correction. Amine equivalent (g / equivalent) = (S × 2,000) / (Blank - A) S: Amount of sample (g) A: Consumption of 0.5 mol / L potassium hydroxide-ethanol solution (mL) Blank: Consumption of 0.5 mol / L potassium hydroxide-ethanol solution in the blank test (mL) The maleimide group equivalent of the maleimide resin obtained in the example is a value converted from the amine equivalent of the aromatic amine in the intermediate and is calculated by the following formula. Maleimide equivalent (g / equivalent) = Amine equivalent + 80

[0086] <FD-MS measurement> The FD-MS spectrum of the polymaleimide compound obtained in the example was measured using the following measuring apparatus and measuring conditions. Measuring apparatus: JMS-T100GC AccuTOF Measuring conditions Measuring range: m / z = 4.00 - 2000.00 Rate of change: 51.2 mA / min Final current value: 45 mA Cathode voltage: -10 kV Recording interval: 0.07 sec

[0087] < 13 <13C-NMR measurement> The 13 13C-NMR spectrum of the polymaleimide compound obtained in the example was measured under the following measuring apparatus and measuring conditions. 13 13C-NMR: "JNM-ECZ400S" manufactured by JEOL RESONANCE Resonance frequency: 100 MHz Number of integrations: 4000 times Solvent: chloroform-d Sample concentration: 12 mass% Mitigation agent: Chromium(III) acetylacetonate

[0088] [Example 1] Synthesis of maleimide compound (A-1) (1) Synthesis of intermediate amine In a flask equipped with a thermometer, a condenser, a Dean-Stark trap, and a stirrer, 302.95 g (2.5 mol) of 2,6-xylidine, 292.93 g (1.25 mol) of 1,2-bis(vinylphenyl)ethane, 715.05 g of xylene, and 119.18 g of activated clay were charged, and the mixture was heated to 130°C while stirring, and held for 30 minutes. The mixture was then heated to 190°C over 3 hours while distilling off the xylene, and held at the same temperature for 6 hours. After the hold was completed, the mixture was diluted with 500 g of xylene, and the activated clay was filtered off. The filtrate was heated and reduced pressure to distill off the solvent and unreacted 2,6-xylidine, and aromatic amine resin (a-1) was obtained (amine equivalent: 244 g / equivalent). The Mn of the obtained amine resin was 423 and Mw was 438. The GPC chart is shown in FIG. 1A, the FD-MS chart is shown in FIG. 1B, 13 C-NMR is shown in Figure 1C. (2) Maleimidation A flask equipped with a thermometer, a condenser, a Dean-Stark trap, and a stirrer was charged with 67.84g (1.3 equivalents) of maleic anhydride and 271g of toluene, and stirred at room temperature. Next, a mixed solution of 130g (1 equivalent) of reactant (a-1) and 73.82g of DMF was dropped over 1 hour, and then reacted for 2 hours. 5.06g of p-toluenesulfonic acid monohydrate was added to the reaction solution, heated to 115°C, and the water and toluene that were azeotroped under reflux were cooled and separated, and only the toluene was returned to the system and the dehydration reaction was carried out for 5 hours. After air-cooling to room temperature, the mixture was neutralized with 49% NaOH. Then, toluene and water were distilled off under reduced pressure at 60°C, and 600g of MEK was added to the DMF solution remaining in the flask. The solution was heated to 60°C, and the solution was separated three times with 200g of ion-exchanged water to remove salts in the solution. Sodium sulfate was further added to dry the mixture, and the mixture was concentrated under reduced pressure and dried at 80° C. to obtain a maleimide compound (A-1). The maleimide compound (A-1) had an Mn of 569 and an Mw of 593. The GPC chart is shown in FIG. 2A, the FD-MS chart is shown in FIG. 2B, and the FT-MS chart is shown in FIG. 13C-NMR is shown in Figure 2C.

[0089] [Example 2] Synthesis of maleimide compound (A-2) (1) Synthesis of intermediate amine In a flask equipped with a thermometer, a condenser, a Dean-Stark trap, and a stirrer, 405.54g (3mol) of 2-methyl-6-ethyl-aniline, 234.34g (1mol) of 1,2-bis(vinylphenyl)ethane, 767.86g of xylene, and 127.98g of activated clay were charged, and the mixture was heated to 130°C while stirring, and held for 30 minutes. The mixture was then heated to 190°C over 3 hours while distilling off the xylene, and held at the same temperature for 6 hours. After the hold was completed, the mixture was diluted with 687g of xylene, and the activated clay was filtered off. The filtrate was heated and reduced pressure to distill off the solvent and unreacted 2-methyl-6-ethyl-aniline, and aromatic amine resin (a-2) was obtained (amine equivalent: 258g / equivalent). The Mn of the obtained amine resin was 466 and Mw was 483. The GPC chart is shown in FIG. 3A, the FD-MS chart is shown in FIG. 3B, 13 C-NMR is shown in Figure 3C. (2) Maleimidation In the section "(2) Maleimidation" of Example 1, "Reactant (a-1)" was changed to "Reactant (a-2)" and the amounts of maleic anhydride were changed to 64.11 g (1.3 equivalents), toluene to 265 g, and DMF to 72.96 g, respectively, but the reaction was carried out in the same manner as in Example 1 to obtain maleimide compound (A-2). This maleimide compound (A-2) had an Mn of 602 and an Mw of 627. The GPC chart is shown in FIG. 4A, the FD-MS chart is shown in FIG. 4B, 13 C-NMR is shown in Figure 4C.

[0090] [Example 3] Synthesis of maleimide compound (A-3) (1) Synthesis of intermediate amine In a flask equipped with a thermometer, a condenser, a Dean-Stark trap, and a stirrer, 227.53 g (1.88 mol) of 2-ethylaniline, 200.00 g (0.85 mol) of 1,2-bis(vinylphenyl)ethane, 513.04 g of xylene, and 85.51 g of activated clay were charged, and the mixture was heated to 130°C while stirring, and held for 30 minutes. The mixture was then heated to 190°C over 3 hours while distilling off the xylene, and held at the same temperature for 6 hours. After the hold was completed, the mixture was diluted with 513.04 g of xylene, and the activated clay was filtered off. The filtrate was heated and reduced pressure to distill off the solvent and unreacted 2-ethylaniline, and an aromatic amine resin (a-3) was obtained (amine equivalent: 263 g / equivalent). The Mn of the obtained amine resin was 543 and Mw was 683. The GPC chart is shown in FIG. 5A, the FD-MS chart is shown in FIG. 5B, 13 C-NMR is shown in Figure 5C. (2) Maleimidation In the section "(2) Maleimidation" of Example 1, "reactant (a-1)" was changed to "reactant (a-3)" and the amounts of maleic anhydride were changed to 63.11 g (1.3 equivalents), toluene to 264 g, and p-toluenesulfonic acid monohydrate to 4.71 g, respectively, but the reaction was carried out in the same manner as in Example 1 to obtain a maleimide compound (A-3). The maleimide compound (A-3) had an Mn of 690 and an Mw of 833, and its GPC chart is shown in FIG. 6A, its FD-MS chart is shown in FIG. 6B, and its FT-MS chart is shown in FIG. 6C. 13 C-NMR is shown in Figure 6C.

[0091] [Example 4] Synthesis of maleimide compound (A-4) (1) Synthesis of intermediate amine In a flask equipped with a thermometer, a condenser, a Dean-Stark trap, and a stirrer, 228.56g (1.88mol) of 2-ethylaniline, 170.00g (0.73mol) of 1,2-bis(vinylphenyl)ethane, 85.00g (0.82mol) of styrene, 483.56 xylene, and 120.89g of activated clay were charged, and the mixture was heated to 130°C while stirring, and held for 30 minutes. The mixture was then heated to 190°C over 3 hours while distilling off the xylene, and held at the same temperature for 6 hours. After the hold was completed, the mixture was diluted with 483.56g of xylene, and the activated clay was filtered off. The filtrate was heated and reduced pressure to distill off the solvent and unreacted 2-ethylaniline, and an aromatic amine resin (a-4) was obtained (amine equivalent 305g / equivalent). The Mn of the obtained amine resin was 484, and the Mw was 743, and the GPC chart is shown in Figure 7. (2) Maleimidation In the section "(2) Maleimidization" of Example 1, "130 g (1.3 equivalents) of reactant (a-1)" was changed to "100 g (1 equivalent) of reactant (a-4)." The amounts of maleic anhydride, toluene, DMF, and p-toluenesulfonic acid monohydrate were changed to 41.85 g (1.3 equivalents), 193.30 g, 54.11 g, and 3.12 g, respectively. The reaction was carried out in the same manner as in Example 1. Thus, a maleimide compound (A-4) was obtained. This maleimide compound (A-4) had an Mn of 635 and an Mw of 937, and its GPC chart is shown in FIG.

[0092] [Example 5] Synthesis of maleimide compound (A-5) (1) Synthesis of intermediate amine In a flask equipped with a thermometer, a condenser, a Dean-Stark trap, and a stirrer, 142.19 g of the reactant (a-3), 35.05 g of benzyl alcohol, 177.24 g of xylene, and 38.99 g of activated clay were charged, and the temperature was raised to 80°C while stirring. The temperature was then gradually raised from 80°C to 150°C, and the water and xylene that were azeotroped under reflux were cooled and separated, after which only the xylene was returned to the system to proceed with the dehydration reaction, and the system was held at 150°C for 2 hours. The temperature was then raised to 190°C over 3 hours while distilling off the xylene, and the system was held at the same temperature for 4 hours. After the hold was completed, the system was diluted with 177.24 g of xylene, and the activated clay was filtered off. The filtrate was heated and reduced pressure to remove the solvent and unreacted benzyl alcohol, and aromatic amine resin (a-5) was obtained (amine equivalent: 308 g / equivalent). The resulting amine resin had an Mn of 620 and an Mw of 944, and its GPC is shown in FIG. (2) Maleimidation In the section "(2) Maleimidation" of Example 1, "130 g (1.3 equivalents) of reactant (a-1)" was changed to "60 g (1 equivalent) of reactant (a-5)" and the amounts of maleic anhydride were changed to 24.83 g (1.3 equivalents), toluene to 115.58 g, DMF to 32.39 g, and p-toluenesulfonic acid monohydrate to 1.85 g, respectively, but the reaction was carried out in the same manner as in Example 1 to obtain maleimide compound (A-5). This maleimide compound (A-5) had an Mn of 750 and an Mw of 1141, and its GPC chart is shown in FIG.

[0093] [Example 6] Synthesis of maleimide compound (A-6) (1) Synthesis of intermediate amine In a flask equipped with a thermometer, a condenser, a Dean-Stark trap, and a stirrer, 216.37g (1.60mol) of 2-isopropylaniline, 150.00g (0.64mol) of 1,2-bis(vinylphenyl)ethane, 439.64g of xylene, and 73.27g of activated clay were charged, and the mixture was heated to 130°C while stirring, and held for 30 minutes. The mixture was then heated to 190°C over 3 hours while distilling off the xylene, and held at the same temperature for 6 hours. After the hold was completed, the mixture was diluted with 439.64g of xylene, and the activated clay was separated by filtration. The filtrate was heated and reduced pressure to distill off the solvent and unreacted 2-isopropylaniline, and an aromatic amine resin (a-6) was obtained (amine equivalent 281g / equivalent). The Mn of the obtained amine resin was 1100, and the Mw was 1325, and the GPC chart is shown in Figure 11. (2) Maleimidation In the section "(2) Maleimidation" of Example 1, "130 g (1.3 equivalents) of reactant (a-1)" was changed to "110 g (1 equivalent) of reactant (a-6)" and the amounts of maleic anhydride were changed to 49.90 g (1.3 equivalents), toluene to 218.17 g, DMF to 60.56 g, and p-toluenesulfonic acid monohydrate to 3.72 g, respectively, but the reaction was carried out in the same manner as in Example 1 to obtain maleimide compound (A-6). The maleimide compound (A-6) had an Mn of 1330 and an Mw of 1529, and its GPC chart is shown in FIG.

[0094] [Comparative Example 1] Synthesis of maleimide compound (B-1) Comparative maleimide (B-1) was obtained by synthesis with reference to Example 1 of Japanese Patent No. 71601517.

[0095] <Examples 6 to 10 and Comparative Example 1> Preparation of curable composition and production of cured product The maleimides (A-1) to (A-6) obtained in Examples 1 to 6 and the comparative maleimide (B-1) were mixed with DCPO ("Percumyl D", dicumyl peroxide, manufactured by NOF Corporation) as a catalyst in an amount of 1 part by weight to prepare a curable resin composition.

[0096] Next, the curable compositions of Examples 7 to 12 and Comparative Example 1 were cured under the following curing conditions to produce cured products corresponding to the curable compositions of Examples 7 to 12 and Comparative Example 1. The physical properties of the curable compositions, such as water absorption and thermal expansion coefficient, were evaluated by the following method. The results are shown in Table 1. <Curing conditions> Heat cure at 200℃ for 2 hours using a vacuum press, then at 250℃ for 2 hours Thickness after molding: 1.3mm <Moisture absorption rate measurement> Test pieces with dimensions of 5 mm × 55 mm × 1.3 mm were cut out from the obtained cured product and kept at 85°C, 85% RH, and 1 atmosphere for 50 hours using a pressure cooker tester, and then the moisture absorption rate (%) was calculated using the following formula to evaluate the moisture absorption. Moisture absorption rate (%) = [(weight of test piece after test - weight of test piece before test) ÷ (weight of test piece before test) × 100] <Measurement of thermal expansion coefficient> A test piece having dimensions of 5 mm×5 mm×1.3 mm was cut out from the obtained cured product and subjected to thermal analysis in compression mode using a thermomechanical analyzer (TMA: SS-6100 manufactured by Seiko Instruments Inc.) under the following conditions. Measurement load: 88.8mN Heating rate: 3℃ / min Measurement temperature range: -50℃ to 288℃ The difference between the initial position of the probe and the position at 25°C after the measurement was completed was calculated using the original thickness of the test piece and the formula below, and evaluated as the dimensional change rate after thermal history. Dimensional change rate (%) = [(probe position of test piece before measurement - probe position of test piece after measurement) ÷ thickness of test piece before measurement × 100]

[0097] [Table 1]

[0098] From the results shown in Table 1, when comparing Examples 7 to 12 with Comparative Example 2, it was confirmed that by using the polymaleimide compounds of Examples 1 to 5, it is possible to achieve both a low thermal expansion coefficient and moisture absorption resistance to a high degree. [Industrial Applicability]

[0099] Therefore, the polymaleimide compound of the present invention, the curable composition containing the polymaleimide compound, and the cured product thereof can be suitably used for heat-resistant components or electronic components, and can be particularly suitably used for prepregs, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up boards, adhesives using conductive pastes, resist materials, and the like.

Claims

1. A polymaleimide compound having an aromatic amine compound (A), a compound (B1) represented by the following general formula (b1), and maleic anhydride as essential reactant materials (1). 【Chemistry 1】 ... (b1) [In general formula (b1), X represents a divalent hydrocarbon group having 1 to 18 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom, an oxygen atom, a sulfur atom, a sulfinyl group, or a sulfonyl group, and n is the number 0 or 1.]

2. 2. The polymaleimide compound according to claim 1, wherein the essential reaction raw materials (3) are the maleic anhydride and an intermediate amine compound (C) in which the aromatic amine compounds (A) are linked to each other via a compound (B1) represented by the general formula (b1).

3. The polymaleimide compound according to any one of claims 1 to 2, represented by the following general formula (1): 【Chemistry 2】 ・・・（１） (In the general formula (1), R １ represents an alkyl group, alkyloxy group or alkylthio group having 1 to 10 carbon atoms, an aryl group, an aryloxy group, an arylthio group or an aralkyl group, or a cycloalkyl group; l is the average number of repeating units and is 0 to 20; m is an integer of 0 to 3; o is an integer of 0 to 3; X represents a divalent hydrocarbon group having 1 to 18 carbon atoms which may contain at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, a sulfur atom, and a halogen atom, an oxygen atom, a sulfur atom, a sulfinyl group, or a sulfonyl group; and n is the number 0 or 1.

4. 3. The polymaleimide compound according to claim 2, wherein the amine equivalent of the intermediate amine compound (C) is in the range of 172 to 400 g / equivalent.

5. A curable composition comprising the polymaleimide compound according to any one of claims 1 to 4.

6. A cured product of the curable composition according to claim 5.

7. A prepreg comprising a reinforcing substrate and a semi-cured product of the curable composition according to claim 5 impregnated into the reinforcing substrate.

8. A circuit board obtained by laminating the prepreg according to claim 7 and copper foil and subjecting the laminate to thermocompression molding.

9. A build-up film comprising the curable composition according to claim 5 .

10. A semiconductor encapsulant comprising the curable composition according to claim 5 .

11. A semiconductor device comprising the cured product of the semiconductor encapsulation material according to claim 10.

Images