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

Abstract

The purpose of the present invention is to provide: a polymaleimide compound which exhibits excellent low coefficient of thermal expansion and moisture absorption resistance when cured; a curable composition containing the polymaleimide compound; and a cured product thereof. The present invention pertains to: a polymaleimide compound obtained by using a polymaleimide compound in which an aromatic amine compound (A), a compound (B1) represented by general formula (b1), and maleic anhydride are used as essential reaction raw materials (1); a curable composition containing the polymaleimide compound; and a cured product of the curable composition. It is possible to achieve both excellent low coefficient of thermal expansion and moisture absorption resistance when cured. Also provided are: a cured product of the curable composition; and a prepreg, a circuit board, a laminate film, a semiconductor sealing material, and a semiconductor device, each of which uses the curable composition.

Description

Technical Field

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

[0002] Prepregs, made by impregnating glass cloth with a thermosetting resin such as epoxy or BT (bismaleimide-triazine) resin and then heating and drying it, laminates formed by heat-curing these prepregs, and multilayer boards formed by combining these laminates and prepregs and then heat-curing them, are widely used as circuit board materials for electronic devices. However, with the increasing trend toward thinner semiconductor package substrates, warping of the package substrate during assembly has become a problem. To mitigate this problem, materials exhibiting high heat resistance are in high demand.

[0003] Furthermore, in recent years, as signals continue to increase in speed and frequency, there is a demand for a thermosetting resin composition that provides a cured product that maintains a sufficiently low dielectric constant and exhibits a sufficiently low dielectric loss tangent under these conditions.

[0004] In particular, recently, various electrical material applications, especially advanced material applications, have required materials and their compositions that combine various required properties, such as heat resistance, further improvement in performance represented by dielectric properties, and moisture resistance for improving package substrate reliability.

[0005] To meet these demands, maleimide resins are attracting attention as materials that combine heat resistance with a 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.

[0006] Therefore, to address these issues, 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, the thermal expansion coefficient and moisture absorption resistance of the polymaleimide resin cannot be said to be necessarily sufficient, and there is room for further improvement.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent No. 7160151 Summary of the Invention

[0010] Problems to be solved by the invention

[0011] Therefore, an object of the present disclosure is to provide a polymaleimide compound that exhibits excellent low thermal expansion coefficient and moisture absorption resistance when cured.

[0012] Methods for solving problems

[0013] The present invention relates to a polymaleimide compound, a curable composition containing the polymaleimide compound, and a cured product thereof. The polymaleimide compound comprises an aromatic amine compound (A), a compound (B1) represented by the general formula (b1), and maleic anhydride as essential reaction raw materials (1), and is capable of achieving both excellent low thermal expansion coefficient and moisture absorption resistance in the cured product.

[0014] The present invention also provides a cured product of the curable composition, and a prepreg, a circuit board, a build-up film, a semiconductor sealing material, and a semiconductor device using the curable composition.

[0015] Effects of the Invention

[0016] The present disclosure provides a polymaleimide compound that can achieve both excellent low thermal expansion coefficient and hygroscopic 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

[0017] Figure 1A The GPC measurement results of the intermediate amine (a-1) of this example are shown.

[0018] Figure 1B The results of FD-MS measurement of the intermediate amine (a-1) in this example are shown.

[0019] Figure 1C The intermediate amine (a-1) of this example is shown in FIG. 13 C-NMR measurement results.

[0020] Figure 2A The GPC measurement results of the polymaleimide compound (A-1) of this example are shown.

[0021] Figure 2B The results of FD-MS measurement of the polymaleimide compound (A-1) of this example are shown.

[0022] Figure 2C The polymaleimide compound (A-1) of this example is shown. 13 C-NMR measurement results.

[0023] Figure 3AThe GPC measurement results of the intermediate amine (a-2) of this example are shown.

[0024] Figure 3B The results of FD-MS measurement of the intermediate amine (a-2) in this example are shown.

[0025] Figure 3C The intermediate amine (a-2) of this example is shown in FIG. 13 C-NMR measurement results.

[0026] Figure 4A The GPC measurement results of the polymaleimide compound (A-2) of this example are shown.

[0027] Figure 4B The results of FD-MS measurement of the polymaleimide compound (A-2) of this example are shown.

[0028] Figure 4C The polymaleimide compound (A-2) of this example is shown. 13 C-NMR measurement results.

[0029] Figure 5A The GPC measurement results of the intermediate amine (a-3) of this example are shown.

[0030] Figure 5B The results of FD-MS measurement of the intermediate amine (a-3) in this example are shown.

[0031] Figure 5C The intermediate amine (a-3) of this example is shown in FIG. 13 C-NMR measurement results.

[0032] Figure 6A The GPC measurement results of the polymaleimide compound (A-3) of this example are shown.

[0033] Figure 6B The results of FD-MS measurement of the polymaleimide compound (A-3) of this example are shown.

[0034] Figure 6C The polymaleimide compound (A-3) of this example is shown. 13 C-NMR measurement results.

[0035] Figure 7 The GPC measurement results of the intermediate amine (a-4) of this example are shown.

[0036] Figure 8 The GPC measurement results of the polymaleimide compound (A-4) of this example are shown.

[0037] Figure 9The GPC measurement results of the intermediate amine (a-5) of this example are shown.

[0038] Figure 10 The GPC measurement results of the polymaleimide compound (A-5) of this example are shown.

[0039] Figure 11 The GPC measurement results of the intermediate amine (a-6) of this example are shown.

[0040] Figure 12 The GPC measurement results of the polymaleimide compound (A-6) of this example are shown. DETAILED DESCRIPTION

[0041] Hereinafter, an embodiment of the present invention (referred to as “this embodiment”) will be described in detail. However, the present disclosure is not limited to the following description and can be implemented with various modifications within the scope of the gist of the disclosure.

[0042] <Term>

[0043] As used herein, "reaction raw materials" are compounds used to obtain the target compound through a chemical reaction such as combination or decomposition, and refer to compounds that partially constitute the chemical structure of the target compound, excluding substances such as solvents and catalysts that act as chemical reaction aids. As used herein, "reaction raw materials" specifically refer to precursors used to obtain the target polymaleimide compound or its precursor compound (e.g., the intermediate amine compound (C) formed by linking the aromatic amine compounds (A) via the compound (B1) represented by the general formula (b1)) through a chemical reaction.

[0044] The "alkyl group" in this specification may be any of linear, branched or cyclic groups, and examples thereof include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, (n-)heptyl, (n-)octyl, (n-)nonyl, (n-)decyl, (n-)undecyl, and (n-)dodecyl.

[0045] In the present specification, examples of the "cycloalkyl group" include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, norbornyl, and adamantyl.

[0046] Examples of the "alkylthio group" in the present specification include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, an octylthio group, and a 2-ethylhexylthio group.

[0047] 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.

[0048] Examples of the "aryl group" in the present specification include phenyl, 1-naphthyl, and 2-naphthyl.

[0049] Examples of the "aryloxy group" in the present specification include phenoxy, naphthyloxy, anthryloxy, phenanthrenyloxy, and pyreneoxy groups.

[0050] Examples of the "arylthio group" in the present specification include a phenylthio group, a naphthylthio group, an anthrylthio group, a phenanthrenylthio group, and a pyrenylthio group.

[0051] As used herein, the “halogen atom” includes, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

[0052] The term "structural unit" as used herein refers to a (repeating) unit of a chemical structure formed during reaction or polymerization. In other words, it refers to a partial structure other than the structure of chemical bonds involved in the reaction or polymerization in a compound produced by reaction or polymerization.

[0053] [Polymaleimide compound]

[0054] The polymaleimide compound of the present embodiment is a polymaleimide compound comprising an aromatic amine compound (A), a compound (B1) represented by the general formula (b1), and maleic anhydride as reaction raw materials (1).

[0055] As a result, when the cured product is obtained, it is possible to achieve both excellent low thermal expansion coefficient and high moisture absorption resistance.

[0056] In this embodiment, the reaction raw material (1) may contain a modifier (D). In addition, the polymaleimide compound of this embodiment may also be a polymaleimide compound in which an intermediate amine compound (C) formed by cross-linking an aromatic amine compound (A) via a compound (B1) represented by the general formula (b1) and maleic anhydride are used as the reaction raw materials (3). Furthermore, the intermediate amine compound (C) may also be a compound in which an aromatic amine compound (A), a compound (B1) represented by the general formula (b1), and a modifier (D) added as needed are used as the reaction raw materials (2).

[0057] In other words, the intermediate amine compound (C) in this embodiment preferably has a structure in which a structural unit of an aromatic amine compound (A) having 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 chemically bonded and a structural unit of a compound (B1) represented by general formula (b1) is chemically bonded, and optionally, a structural unit of a modifier (D) is chemically bonded to the aromatic ring in the structural unit of the aromatic amine compound (A). Furthermore, the polymaleimide compound in this embodiment has a structure in which the amino group (including -NH2 and substituted amino groups) bonded to the aromatic ring of the intermediate amine compound (C) is substituted with a maleimide group.

[0058] Therefore, the "polymaleimide compound" in this embodiment and the "intermediate amine compound (C)" which is a precursor of the "polymaleimide compound" are polymer compounds that differ in that the amino group (including -NH2 and substituted amino group) bonded to the aromatic ring is replaced by a maleimide group.

[0059] It should be noted that 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, the group obtained by removing two hydrogen atoms from the benzene ring of the general formula (a) is referred to as the 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 vinyl groups of the compound (B1) represented by the general formula (b1).

[0060] In this embodiment, since an aromatic amine compound (A) having a specific aromatic ring structure is used as a reaction raw material, it is easy to control the reaction site with the compound (B1) represented by the general formula (b1) described later, thereby easily obtaining a polymaleimide compound having a uniform chemical structure or chain length. As a result, a polymaleimide compound having low moisture absorption and low dielectric loss tangent when displaying a cured product can be provided.

[0061] Below, after explaining the aromatic amine compound (A), the compound (B1) represented by the general formula (b1), the modifier (D) which can be an optional component, and maleic anhydride as the constituent components of the reaction raw material (1) of the polymaleimide compound, another preferred embodiment of the polymaleimide compound and the method for producing the polymaleimide compound are explained.

[0062] -Aromatic amine compound (A)-

[0063] The aromatic amine compound (A) in the present embodiment has an aromatic ring to which an amino group (-NH2 or a substituted amino group) is bonded. Therefore, the aromatic amine compound (A) may be an amine compound. In addition, the aromatic ring forming the central structure of the aromatic amine compound (A) is preferably a monocyclic type, comprising an aromatic hydrocarbon ring and an aromatic heterocyclic ring. As the aromatic hydrocarbon ring, a benzene ring is preferred. As the aromatic heterocyclic ring, for example, hetero six-membered rings such as a pyran ring or a pyridine ring can be cited. In addition, the aromatic amine compound (A) in the present embodiment more preferably has an aromatic ring to which -NH2 is bonded and which does not contain a substituted amino group.

[0064] In the aromatic amine compound (A) of the present embodiment, it is preferred that a hydrocarbon group is substituted on one or more and three or less hydrogen atoms of the aromatic ring of the aromatic amine compound (A). Examples of the hydrocarbon group include an alkyl group, an alkoxy group or an alkylthio group having 1 to 10 carbon atoms, an aryl group, an aryloxy group, an arylthio group or an arylalkyl group having 6 to 10 carbon atoms, and a cycloalkyl group having 3 to 10 carbon atoms. Preferably, the alkyl group has 1 to 6 carbon atoms, an aryl group has 6 to 10 carbon atoms, and an arylalkyl group has 6 to 10 carbon atoms. More preferably, the alkyl group has 1 to 3 carbon atoms and an aryl group has 6 to 8 carbon atoms. The alkyl group having 1 to 10 carbon atoms may be a straight chain or a branched chain. More specifically, examples include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the alkylthio group include methylthio, ethylthio, propylthio, and butylthio. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, naphthyl, and anthracenyl. Examples of the aryloxy group include phenoxy, tolyloxy, xylyloxy, and naphthyloxy. Examples of the arylthio group include phenylthio, tolylsulfanyl, xylylsulfanyl, and naphthylsulfanyl. Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclopentyl, and cyclohexyl. Examples of the aralkyl group include benzyl, methylbenzyl, and phenethyl. The smaller the molecular weight of the alkyl group, the more significant the effect (low thermal expansion coefficient) of the present invention becomes. In addition, the larger the molecular weight of the alkyl group, the more significant the effect (low hygroscopicity) of the present invention becomes.

[0065] The upper limit of the number of alkyl groups bonded to the aromatic ring having an amino group (including -NH2 and substituted amino groups) in the aromatic amine compound (A) is the number obtained by subtracting 3 from the number of substitutable ring atoms in the unsubstituted aromatic ring, from the viewpoint that the aromatic ring has an amino group (including -NH2 and substituted amino groups) and two bonds are used for polymerization. For example, when the aromatic ring is a benzene ring, the number of alkyl groups is 3 or less.

[0066] Furthermore, by setting the number of alkyl groups substituted on the aromatic ring of the aromatic amine compound (A) to 1 or more, it is easy to control the reaction sites with the compound (B1) represented by the general formula (b1) described below, thereby easily obtaining a polymaleimide compound with a uniform chemical structure and chain length. As a result, the cured product of the polymaleimide compound tends to exhibit low hygroscopicity and excellent high-frequency electrical properties.

[0067] A preferred embodiment of the aromatic amine compound (A) will be described using as an example a case where the aromatic ring of the aromatic amine compound (A) in the present embodiment is a benzene ring.

[0068] In the present embodiment, among the carbon atoms in the benzene ring constituting the aromatic amine compound (A), preferably, at least one carbon atom having the largest HOMO electron density (Huckel coefficient) is unsubstituted (or substituted with a hydrogen atom).

[0069] This makes it easy to control the ArS of the cationic reagent formed by the compound (B1) represented by the general formula (b1) described later. E Reaction and molecular design. To explain in more detail, among the carbon atoms in the benzene ring constituting the aromatic amine compound (A), when the carbon atom with the largest HOMO electron density (Huckel coefficient) is unsubstituted, the carbon cation of the compound (B1) represented by the general formula (b1), which is a quasi-cationic reagent, easily reacts with the carbon atom with the largest HOMO electron density. Therefore, by controlling the number and position of the alkyl groups bonded to the carbon atoms of the benzene ring, the bonding site or number of bonds with the compound (B1) represented by the general formula (b1) can be adjusted. Therefore, it is presumed that the chemical structure or molecular chain length of the resulting polymaleimide compound can be easily designed.

[0070] For example, when the aromatic amine compound (A) has an aniline skeleton comprising one benzene ring and one amino group, it is preferred that at least one carbon atom at the 2-position, 4-position, and 6-position of the aniline core is substituted with a hydrogen atom. As a result, the cationic reagent formed by the compound (B1) represented by the general formula (b1) described later easily attacks at least one carbon atom at the 2-position, 4-position, and 6-position of the aniline core, which has a high electron density at the ortho and para positions. 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 compound (B1) represented by the general formula (b1) can be roughly controlled, thereby easily obtaining a polymaleimide compound with a uniform chemical structure or chain length. For example, it is believed that if 2,6-dialkylamine is used as the aromatic amine compound (A), a polymaleimide compound bonded to the compound (B1) represented by the general formula (b1) at the 4-position can be obtained in large quantities.

[0071] Specific examples of the aromatic amine compound (A) of the present embodiment include aniline, 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, 3,4-diisopropylaniline or 3,5-diisopropylaniline), ethylmethylaniline (for example, at the 2nd and 3rd positions, the 2nd and 4th positions, the 2nd and 6th positions, the 3rd and 5th positions, the 4th and 5th positions, the 6th and 7th positions, the 7th and 8th positions, the 8th and 9th positions, the 9th and 10th positions, the 11th and 12th positions, the 13th and 14th positions, the 15th and 16th positions, the 17th and 18th positions, the 18th and 19th positions, the 19th and 2 ...9th and 20th positions, the 19th and 20th positions, the 19th and 20th positions, the 19th and 20th positions, the 19th and 20th positions, the 19th and Examples of the butyl group include 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 (e.g., methylisopropylaniline wherein any one of positions 2 and 3, 2 and 4, 2 and 6, 3 and 4, or 3 and 5 is a methyl group and the other is isopropyl), or ethylbutylaniline (e.g., ethylbutylaniline wherein any one of positions 2 and 3, 2 and 4, 2 and 6, 3 and 4, or 3 and 5 is an ethyl group and the other is butyl). In addition, the butyl group includes n-butyl, tert-butyl, and sec-butyl. In addition, the aromatic amine compound (A) in this embodiment may be used individually or in combination of 2 or more types.

[0072] For example, as in N-phenylmaleimide, in the case of a chemical structure in which a maleimide group is directly bonded to an unsubstituted benzene ring, the state in which the benzene ring and the 5-membered ring of maleimide are arranged on the same plane is stable, so it is easy to stack and exhibits high crystallinity. Therefore, it becomes a cause of poor solvent solubility. In contrast, in the case of the present disclosure, for example, as in 2,6-dimethylaniline, in the case of having an alkyl group (for example, a methyl group) as a substituent to the benzene ring, due to the steric hindrance of the methyl group, the benzene ring and the 5-membered ring of maleimide adopt a cross-type conformation, which is difficult to stack, so the crystallinity is reduced and the solvent solubility is improved, which becomes a preferred mode. However, if the steric hindrance is too large, there is also concern about hindering the reactivity during the synthesis of maleimide, so for example, it is preferred to use an aromatic amine compound (A) having an alkyl group having 1 to 6 carbon atoms.

[0073] The aromatic amine compound (A) essential for the reaction raw material (1) in the present embodiment can be represented by, for example, the following general formula (a).

[0074] [Chemistry 1]

[0075]

[0076] (In the general formula (a), R 1a represents a hydrocarbon group, m a represents an integer from 0 to 3. 1a Can be the same or different.)

[0077] In the general formula (a), R 1a represents a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkoxy 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. Preferably, the group is 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, the group is an alkyl group having 1 to 3 carbon atoms or an aryl group having 6 to 8 carbon atoms. Examples of the alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, aralkyl group, and cycloalkyl group are the same as those mentioned above.

[0078] In the general formula (a), m a It is preferably 1 or 2. It should be noted that R 1a When there are two or more hydrocarbon groups, they may be the same hydrocarbon groups or different hydrocarbon groups.

[0079] In addition, in this embodiment, the aromatic amine compound (A) represented by the general formula (a) may be used alone or in combination of two or more.

[0080] -Compound (B1) represented by general formula (b1)-

[0081] The compound (B1) represented by the general formula (b1) in this embodiment can be used without particular limitation as long as it contains two aromatic rings, has one aromatic vinyl group (CH2=CH-) (also called vinyl group) as a substituent on each aromatic ring, and can react with the aromatic amine compound (A).

[0082] In the present embodiment, the reaction raw material (1) may contain a mixture of the compound (B1) represented by the general formula (b1) and the modifier (D).

[0083] [Chemistry 2]

[0084]

[0085] In the 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, a sulfinyl group, or a sulfonyl group, and n is 0 or 1.

[0086] In the general formula (b1), X each independently 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", "a halogen atom", "a hydroxyl group", "a carboxyl group", "an amino group", or "a nitro group". "It 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 the hydrogen atom of the hydrocarbon group may be substituted by 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), a fluoro group (-F), etc. In addition, it also means 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, a "divalent hydrocarbon group" refers to a hydrocarbon group having two bonding positions, and is not limited to a straight-chain saturated hydrocarbon group, and may also have a carbon-carbon unsaturated bond, a branched structure, or a cyclic structure.

[0087] In the 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 the functional group 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), and an iodo group (iodine atom, -I). 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-).

[0088] The compound (B1) represented by the general formula (b1) preferably has a structure represented by the following general formula (b1a).

[0089] [Chemistry 3]

[0090]

[0091] In the general formula (b1a), p represents an integer of 0 to 5, preferably an integer of 1 to 2. The smaller p is, the smaller the distance between crosslinking points in the cured product becomes, and the more significant the effect of the invention (low thermal expansion coefficient) becomes.

[0092] As the compound (B1) represented by the general formula (b1), more preferred examples include bis(vinylphenyl)methane (BVPM), 1,2-bis(vinylphenyl)ethane (BVPE), and 1,6-bis(4-vinylphenyl)hexane (BVPH).

[0093] The compound (B1) represented by the general formula (b1) in the present embodiment may be used alone or in combination of two or more.

[0094] In the present embodiment, the structural unit of the compound (B1) represented by the general formula (b1) is contained in an amount of preferably 10 to 90 mass %, more preferably 20 to 90 mass %, based on the total amount (100 mass %) of the polymaleimide compound.

[0095] -Modifier (D)-

[0096] The polymaleimide compound in the present embodiment, in addition to the compound (B1) represented by aromatic amine compound (A), general formula (b1) and maleic anhydride, can also further use other compounds as reaction raw materials.As these other compounds, for example, modifier (D) can be enumerated.That is, in an embodiment, it is possible to use the compound (B1) represented by aromatic amine compound (A), general formula (b1), modifier (D) and maleic anhydride as reaction raw materials (1). The polymaleimide compound in the present embodiment, in addition to the compound (B1) represented by aromatic amine compound (A), general formula (b1) and maleic anhydride, also uses modifier (D) as its reaction raw materials, and the cured product of the polymaleimide compound thus finally obtained is excellent in low moisture absorption, low dielectric loss tangent, therefore preferably.

[0097] In addition, the modifier (D) also generates a carbocation in the same manner as the compound (B1) represented by the general formula (b1), and therefore easily reacts 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).

[0098] The modifier (D) in this embodiment can be exemplified by vinylbenzene (styrene), vinylbiphenyl, vinylnaphthalene, and various compounds substituted with one or more alkyl groups, alkoxy groups or alkylthio groups having 1 to 10 carbon atoms, aryl groups, aryloxy groups or arylthio groups having 6 to 10 carbon atoms, cycloalkyl groups having 3 to 10 carbon atoms, halogen atoms, hydroxyl groups, or mercapto groups on their aromatic rings. The alkyl group can be either linear or branched, and can also have an unsaturated bond in the structure. Among them, when low hygroscopicity is important, the alkyl group or the alkoxy group preferably has 1 to 4 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, and isobutyl groups. Examples of the alkoxy group include methoxy, ethoxy, propoxy, and butoxy groups. Examples of the halogen atom include fluorine atoms, chlorine atoms, and bromine atoms.

[0099] The modifier (D) that can be the reaction raw material (1) of the polymaleimide compound of the present disclosure can be represented by the following general formula (d).

[0100] [Chemistry 4]

[0101]

[0102] (In the general formula (d), Y represents a substituent having a carbocation generating ability, 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 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. It should be noted that, at t b When the number is an integer greater than 2, the presence of multiple R 2b They may be the same as each other or different.)

[0103] Y in the formula (d) has a carbocation-generating ability, and specifically represents a vinyl group, a hydroxymethyl group, an alkoxymethyl group, a chloromethyl group, etc. that can react 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.

[0104] In the general formula (b1), t b It is preferably 1 to 4. It should be noted that, at t b When the value is 2 or more, multiple R 2b They may be the same group or different groups.

[0105] Specific examples of the modifier (D) of the present embodiment include, for example, benzenes such as compounds containing styrene, fluorostyrene, alkylvinylbenzenes (o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylvinylbenzene, m-ethylvinylbenzene, p-ethylvinylbenzene), benzyl chloride, α-methylstyrene, and derivatives thereof; aromatic alcohols such as compounds containing benzyl alcohol, dimethylphenylmethanol, and derivatives thereof; biphenyl compounds such as compounds containing 4-vinylbiphenyl, 4-vinyl-p-terphenyl, and derivatives thereof; and vinylnaphthalenes such as compounds containing 1-vinylnaphthalene, 2-vinylnaphthalene, and derivatives thereof, but are not limited thereto.

[0106] In particular, ethylvinylbenzene, styrene, and benzyl alcohol are preferred from the viewpoints of raw material availability and reactivity.

[0107] As the reaction raw material (1) of the polymaleimide compound in this embodiment, when a modifier (D) is used, the molar ratio ((B1) / (D)) of the modifier (D) in the reaction raw material (1) to the compound (B1) represented by the general formula (b1) is preferably 99 / 1 to 50 / 50, and more preferably 98 / 2 to 70 / 30.

[0108] -Maleic anhydride-

[0109] In the present embodiment, maleic anhydride is an essential component of the reaction raw material (1) of the polymaleimide compound, and is used to maleimidize the amino group (including -NH2 and substituted amino group) derived from the aromatic amine compound (A), as described in the section on the production method of the polymaleimide compound described later.

[0110] <Preferred Embodiments of Polymaleimide Compound>

[0111] Hereinafter, preferred embodiments of the polymaleimide compound in the present disclosure will be described using the case where each aromatic ring is a benzene ring as an example. The following chemical structural formula is used to illustrate the present disclosure, and the scope of the present disclosure is not limited to the following chemical structural formula.

[0112] -Preferred embodiment of the polymaleimide compound-

[0113] The polymaleimide compound in the present embodiment is preferably represented by the following general formula (1).

[0114] [Chemistry 5]

[0115]

[0116] In the general formula (1), R 1 Each independently represents an alkyl group, alkoxy group or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group, arylthio group or arylalkyl 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 arylalkyl 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. In addition, when m is an integer of 2 or more, the presence of a plurality of R 1 They may be the same as or different from each other. 1 , is methyl, ethyl or n-propyl, phenyl, benzyl, phenylethyl. In addition, R in the general formula (1) 1 It is derived from the aromatic amine compound (A) and / or from the modifier (D). 1 The benzene ring to be bonded may be the benzene ring of the aromatic amine compound (A).

[0117] In the general formula (1), 1 represents the average number of repeating units, which is preferably 0-20, more preferably 0-18, and even more preferably 0-15.

[0118] In the general formula (1), m represents an integer of 0 to 3. It should be noted that it is preferred that R 1 R is bonded to at least one of the 2nd, 3rd, 4th, 5th or 6th positions of the benzene ring. 1 .

[0119] In the general formula (1), o represents an integer of 0 to 3.

[0120] 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, a sulfinyl group, or a sulfonyl group, and n is 0 or 1.

[0121] In the present embodiment, the polymaleimide compound is preferably represented by the following general formula (2).

[0122] [Chemistry 6]

[0123]

[0124] In the general formula (2), R 1 Each independently represents an alkyl group, alkoxy group or alkylthio group having 1 to 10 carbon atoms, an aryl group, aryloxy group, arylthio group or arylalkyl 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 arylalkyl 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. In addition, when m is an integer of 2 or more, the presence of a plurality of R 1 They may be the same as or different from each other. 1 , is methyl, ethyl or n-propyl, phenyl, benzyl, phenylethyl. It should be noted that R in the general formula (1) 1 The benzene ring to be bonded may be the benzene ring of the aromatic amine compound (A).

[0125] In the general formula (2), 1 represents the average number of repeating units, which is preferably 0-20, more preferably 0-18, and even more preferably 0-15.

[0126] In the general formula (2), m represents an integer of 0 to 3. It should be noted that it is preferred that R 1 R is bonded to at least one of the 2nd, 3rd, 4th, 5th or 6th positions of the benzene ring. 1 .

[0127] In the general formula (2), o represents an integer of 0 to 3.

[0128] In the general formula (2), p represents an integer of 0 to 5, and preferably an integer of 1 to 2.

[0129] The number average molecular weight (Mn) of the polymaleimide compound disclosed herein is preferably 350 to 2,000, more preferably 400 to 1,500. The weight average molecular weight (Mw) of the polymaleimide compound is preferably 400 to 500,000, more preferably 450 to 400,000.

[0130] From the perspective of excellent low dielectric constant and low dielectric loss tangent, the molecular weight distribution (weight average molecular weight (Mw) / number average molecular weight (Mn)) of the polymaleimide compound of the present disclosure, as measured and calculated by gel permeation chromatography (hereinafter referred to as "GPC"), is preferably in the range of 1.001 to 500, and more preferably 1.001 to 400. It should be noted that according to the GPC chart obtained by GPC measurement, when the molecular weight distribution is over a wide range and there are many high molecular weight components, the proportion of high molecular weight components that contribute to flexibility increases. Therefore, compared with conventional cured products using maleimide, brittleness is suppressed, and a cured product with excellent flexibility and softness can be obtained, which is a preferred embodiment.

[0131] 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 below.

[0132] <Method for producing polymaleimide compound>

[0133] Hereinafter, the method for producing the polymaleimide compound of the present disclosure will be described.

[0134] The method for producing the polymaleimide compound of this embodiment is not particularly limited. As long as an aromatic amine compound (A), a compound (B1) represented by the general formula (b1), and maleic anhydride are used as the reaction raw materials (1), or as long as the compound has a structural unit represented by the general formula (1), the polymaleimide compound can be produced in any manner. As an example of the method for producing the polymaleimide compound of the present disclosure, a method including the following steps (1) and (2) can be cited.

[0135] Step (1): a step of reacting an aromatic amine compound (A) with a compound (B1) represented by the general formula (b1) as a reaction raw material (2) to obtain an intermediate amine compound (C) in this embodiment;

[0136] Step (2): A step of reacting the intermediate amine compound (C) obtained in the step (1) with maleic anhydride as a reaction raw material (3) to obtain the polymaleimide compound of the present disclosure.

[0137] Specifically, the method for producing a polymaleimide compound of the present embodiment preferably comprises: a step (1) (also referred to as a cross-linking step) of reacting an aromatic amine compound (A) with a compound (B1) represented by the general formula (b1) in the presence of a solid acid catalyst, and a step (2) (also referred to as a condensation step) of condensing the intermediate amine compound (C) generated by the step (1) with maleic anhydride.

[0138] Hereinafter, each step of the method for producing the polymaleimide compound of the present disclosure will be described in order.

[0139] <Step (1): Process for producing an intermediate amine compound (C)>

[0140] Hereinafter, the production process of the intermediate amine compound (C) in this embodiment will be described.

[0141] Step (1) in this embodiment is not particularly limited and is, for example, a step of reacting the aromatic amine compound (A), the 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 (D) (e.g., styrene) in the presence of an acid catalyst. Thus, an intermediate amine compound (C) is produced.

[0142] The mixing ratio of the aromatic amine compound (A) and the compound (B1) represented by the general formula (b1) is preferably 0.1 to 10 mol, more preferably 0.2 to 3 mol, per 1 mol of the aromatic amine compound (A), taking into account the physical property balance of moldability and curability of the resulting cured product during production. Furthermore, when the modifier (D) is used in combination, the molar ratio of the total of the compound (B1) represented by the general formula (b1) and the modifier (D) per 1 mol of the aromatic amine compound (A) is preferably 0.1 to 10 mol, more preferably 0.2 to 3 mol.

[0143] In addition, as a specific method for carrying out the reaction, the following method is generally used: all raw materials are charged at once and reacted directly at a predetermined temperature, or an aromatic amine compound (A) and an acid catalyst are charged and, while maintaining the predetermined temperature, a compound (B1) represented by the general formula (b1), other compounds (e.g., a modifier (D)), etc. are added dropwise while reacting. In this case, the addition time is generally 0.1 to 12 hours, preferably 6 hours or less. After the reaction, when a solvent is used, the solvent and unreacted products are distilled off as needed to obtain the intermediate amine compound (C). When no solvent is used, the unreacted products are distilled off to obtain the target intermediate amine compound (C).

[0144] 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 perspective of operability, solid acids from which the catalyst can be easily removed by filtration after the reaction are also preferred. When other acids are used, neutralization with an alkali and washing with water are preferably performed after the reaction.

[0145] The acid catalyst is added in an amount 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 (D), and aromatic amine compound (A)). From the perspectives of operability and economic efficiency, the acid catalyst is preferably added in an amount of 1 to 60 parts by mass. The reaction temperature is generally in the range of 80 to 270°C, but is preferably 80 to 220°C to suppress the formation of isomers and avoid side reactions such as thermal decomposition.

[0146] In 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 modifier (D) with the aromatic amine compound (A), i.e., the condensation reaction time, is generally in the range of 1 to 48 hours in total, preferably in the range of 1 to 30 hours in total, under the reaction temperature conditions, because the reaction does not proceed completely in a short time and, in addition, side reactions such as thermal decomposition of the product will occur if the reaction is set to a long time.

[0147] In the method for producing the intermediate amine compound (C) of this embodiment, aniline or its derivatives also serve as a solvent, so it is not necessary to use another solvent, or a solvent may be used. For example, when the reaction is conducted using 1,2-bis(vinylphenyl)ethane (BVPE) as a raw material, the following method can be adopted: using a solvent capable of azeotropic dehydration, such as toluene, xylene, or chlorobenzene, azeotropically dehydrating the water contained in the catalyst, etc. as needed, then distilling off the solvent, and then conducting the reaction within the aforementioned reaction temperature range.

[0148] The intermediate amine compound (C) obtained in the above step (1) is preferably represented by the following general formula (3), for example.

[0149] [Chemistry 7]

[0150]

[0151] 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. In addition, when m is an integer greater than 2, there are multiple R 1 They may be the same as or different from each other. 1 , is methyl, ethyl or n-propyl, phenyl, benzyl, phenylethyl. It should be noted that R in the general formula (3) 1 The benzene ring to be bonded may be the benzene ring of the aromatic amine compound (A).

[0152] In the general formula (3), 1 represents the average number of repeating units, which is preferably 0-20, more preferably 0-18, and even more preferably 0-15.

[0153] In the general formula (3), m represents an integer of 0 to 3. It should be noted that it is preferred that R 1 R is bonded to at least one of the 2nd, 3rd, 4th, 5th or 6th positions of the benzene ring. 1 .

[0154] In the general formula (3), o represents an integer of 0 to 3.

[0155] 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, a sulfinyl group, or a sulfonyl group, and n is 0 or 1.

[0156] It should be noted that R in the general formula (3) 1Preferred embodiments of n, m, l, and o are the same as those of the general formula (1). In addition, another preferred embodiment of the intermediate amine compound (C) obtained by the step (1) is a structure in which the maleimide group in the general formula (2) is substituted with an amino group (including -NH2 and substituted amino groups), which is also a preferred embodiment of the polymaleimide compound.

[0157] In this embodiment, the amine equivalent of the intermediate amine compound (C) is preferably 172 to 800 g / equivalent, more preferably 172 to 500 g / equivalent. It should be noted that the amine equivalent of the intermediate amine compound (C) in this specification is determined by a method based on the neutralization titration method specified in JIS K0070 (1992).

[0158] <Step (2): Maleimidation>

[0159] Step (2) in this embodiment 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 be substituted with a maleimide ring through a maleimidation reaction, thereby obtaining the polymaleimide compound of the present disclosure.

[0160] In this embodiment, the intermediate amine compound (C) represented by the general formula (4) obtained in step (1) is placed in 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, and the solvent is removed by decompression, thereby obtaining the target polymaleimide compound. In addition, a dehydrating agent may be used during the reaction as needed.

[0161] Examples of the organic solvent used in step (2) of this embodiment include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone; aprotic polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, and sulfolane; cyclic ethers such as dioxane and tetrahydrofuran; esters such as ethyl acetate and butyl acetate; and aromatic solvents such as benzene, toluene, and xylene. These solvents may be used alone or in combination.

[0162] The following preferred method is adopted: in step (2) of this embodiment, as the mixing ratio of the intermediate amine compound (C) and maleic anhydride, the equivalent ratio of maleic anhydride to the amino equivalent of the intermediate amine compound (C) is preferably in the range of 1 to 5, and more preferably 1 to 3, and the reaction is carried out in an organic solvent.

[0163] Examples of the catalyst that can be used in step (2) of this embodiment include acetates of nickel, cobalt, sodium, calcium, iron, lithium, manganese, etc., inorganic salts such as chlorides, bromides, sulfates, and nitrates, 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 acids. Toluenesulfonic acid is particularly preferably used.

[0164] Examples of the dehydrating agent used in step (2) of the present embodiment include lower aliphatic carboxylic anhydrides such as acetic anhydride, propionic anhydride, and butyric anhydride, oxides such as phosphorus pentoxide, calcium oxide, and barium oxide, inorganic acids such as sulfuric acid, and porous ceramics such as molecular sieves. Preferably, acetic anhydride can be used.

[0165] The amounts of the catalyst and dehydrating agent used in step (2) of the present embodiment are not particularly limited. Generally, 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).

[0166] In step (2) of the present embodiment, as the reaction conditions for maleimide formation, the intermediate amine compound (C) and maleic anhydride can be added, and the reaction can be carried out at a temperature range of 10 to 100°C, preferably 30 to 60°C, for 0.5 to 12 hours, preferably 1 to 4 hours, and then the catalyst can be added and the reaction can be carried out at a temperature range of 90 to 130°C, preferably 105 to 120°C, for 1 to 24 hours, preferably 1 to 10 hours.

[0167] [Curable composition]

[0168] 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 this embodiment has excellent solvent solubility, fluidity during heating and melting, and operability, which can contribute to the dimensional stability, low hygroscopicity, brittleness resistance, heat resistance, and low dielectric constant / low dielectric loss tangent of the cured product. Therefore, the cured product obtained from the curable composition containing the polymaleimide compound shows excellent low thermal expansion coefficient and hygroscopicity resistance.

[0169] The curable composition of the present disclosure may contain a curing agent, and further, as needed, various compounding agents such as a curing accelerator, a silane coupling agent, a 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), and a solvent may be added. Furthermore, in addition to the polymaleimide 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, and the like may be appropriately compounded, as long as the purpose of the present disclosure is not compromised.

[0170] [cured material]

[0171] 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 (such as a curing agent, a compounding agent), and can be easily made into a cured product by the same method as known in the past. As the cured product, a laminate, a casting, an adhesive layer, a coating, a film or other shaped cured product can be listed.

[0172] [Semiconductor sealing materials]

[0173] The present disclosure provides a semiconductor sealing material containing the curable composition of the present embodiment. The semiconductor sealing material obtained using the curable composition of the present embodiment has improved thermal expansion coefficient and moisture absorption resistance by using the polymaleimide compound of the present disclosure, thereby having excellent processability, moldability, and reflow resistance during the manufacturing process, which is a preferred embodiment.

[0174] The curable composition of the present embodiment used in the semiconductor sealing material may contain an inorganic filler. It should be noted that, as the filling rate of the inorganic filler, the inorganic filler can be used in the range of, for example, 0.5 to 1200 parts by mass relative to 100 parts by mass of the curable composition of the present embodiment. In addition, 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, aluminum nitride, etc.

[0175] Examples of a method for obtaining the semiconductor sealing material include a method in which additives as optional components are melt-mixed sufficiently until uniformity is achieved in the curable composition of the present embodiment, if necessary, using an extruder, a kneader, a roll, or the like.

[0176] [Semiconductor devices]

[0177] The present disclosure relates to a semiconductor device comprising a cured product of the semiconductor sealing material. A semiconductor device obtained using the semiconductor sealing material obtained using the curable composition of this embodiment has low viscosity and excellent fluidity due to the use of the polymaleimide compound of the present disclosure, thereby improving hygroscopicity, thermal expansion coefficient, and adhesion to metal materials. This results in excellent processability, moldability, and reflow resistance during the manufacturing process, making it a preferred embodiment.

[0178] Examples of methods for obtaining the semiconductor device include casting the semiconductor sealing material or molding it using a transfer molding machine, injection molding machine, or the like, and then curing it by heating at a temperature ranging from room temperature (20° C.) to 250° C.

[0179] [Prepreg]

[0180] The present disclosure is a kind of prepreg, which has a reinforcing substrate and a semi-cured product of the curable composition of the present embodiment impregnated in the reinforcing substrate. As a method for obtaining a prepreg from the curable composition, the following method can be cited: after impregnating the varnished curable composition into a reinforcing substrate (paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass fiber mat, glass fiber gauze, etc.) with an organic solvent described later, heating at a heating temperature corresponding to the type of solvent used, preferably 50 to 170°C, thereby semi-curing (or uncuring) the curable composition and obtaining a prepreg. As the mass ratio of the curable composition and the reinforcing substrate used at this time, there is no particular limitation, and it is usually preferably prepared in a manner that the amount of resin in the prepreg becomes 20 to 60% by mass.

[0181] In this embodiment, the semi-cured material of the curable composition is obtained by adjusting the heating temperature and heating time so that the curing reaction is not completed but stopped midway. In addition, for example, the semi-cured material can have a degree of cure of, for example, less than 85% and more than 5%. On the other hand, the cured material in this embodiment can have a higher degree of cure than the semi-cured material.

[0182] The degree of curing of the semi-cured product can be calculated from the following formula by measuring the curing heat release when the curable composition is heated and the curing heat release of the semi-cured product by DSC.

[0183] Curing degree (%) = [1-(curing heat release of semi-cured product / curing heat release of curable composition)] × 100

[0184] Examples of the organic solvent used in the production of the prepreg 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 intended use. For example, when a printed circuit board is further produced from the prepreg as described below, it is preferred to use a polar solvent having a boiling point of 160° C. or lower, such as methyl ethyl ketone, acetone, and dimethylformamide. Furthermore, the non-volatile content is preferably 40 to 80% by mass.

[0185] [Circuit board]

[0186] The present disclosure provides a circuit board comprising a laminate of the prepreg and copper foil. A method for obtaining a printed circuit board from the curable composition of this embodiment includes laminating the prepregs using conventional methods, appropriately overlaying copper foil, and heat-compression bonding at 170°C to 300°C under a pressure of 1 to 10 MPa for 10 minutes to 3 hours.

[0187] [Laminated Film]

[0188] The present disclosure provides a laminated film containing the curable composition of this embodiment. A method for producing the laminated film of this embodiment includes coating the curable composition on a support film to form a curable composition layer to form an adhesive film for a multilayer printed circuit board.

[0189] When manufacturing a laminated film from a curable composition, it is important that the film softens under the lamination temperature conditions (usually 70 to 140°C) in the vacuum lamination method and exhibits fluidity (resin flow) that allows the resin to fill the vias or through-holes present in the circuit substrate while laminating the circuit substrate. It is preferred to combine the above-mentioned components to exhibit such characteristics.

[0190] The diameter of the through-holes in a multilayer printed wiring board is generally 0.1 to 0.5 mm, and the depth is generally 0.1 to 1.2 mm. Resin can be preferably filled within this range. When laminating both sides of a circuit board, it is preferable to fill about 1 / 2 of the through-holes.

[0191] The adhesive film can be specifically manufactured as follows: after preparing the varnish-like curable composition, the varnish-like composition is applied to the surface of the support film (Y), and the organic solvent is further dried by heating or blowing hot air, thereby forming a composition layer (X) composed of the curable composition.

[0192] The thickness of the formed composition layer (X) is preferably set to be 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.

[0193] The composition layer (X) in this embodiment may be protected by a protective film described below. Protection with a protective film can prevent dust and the like from adhering to or damaging the surface of the resin composition layer.

[0194] 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 referred to as "PET") and polyethylene naphthalate, polycarbonate, polyimide, release paper, and metal foils such as copper foil and aluminum foil. The support film and protective film may be subjected to a matte treatment or corona treatment and may also be subjected to a release treatment.

[0195] The thickness of the support film is not particularly limited, but is generally 10 to 150 μm, preferably 25 to 50 μm. The thickness of the protective film is preferably 1 to 40 μm.

[0196] The support film (Y) is peeled off after lamination on a circuit board or after forming an insulating layer by heat curing. Peeling off the support film (Y) after heat curing the adhesive film can prevent the adhesion of dust and the like during the curing process. When peeling off after curing, the support film is typically pre-treated with a demolding agent.

[0197] [Heat-resistant materials and electronic materials]

[0198] The cured product obtained by the curable composition containing the polymaleimide compound of the present disclosure shows excellent low thermal expansion coefficient and moisture absorption resistance, and is therefore suitable for use in heat-resistant components or electronic components. It is particularly suitable for use in prepregs, circuit boards, semiconductor sealing materials, semiconductor devices, laminated films, laminated substrates, adhesives using conductive pastes, resist materials, etc. In addition, it can also be suitable for use in the matrix resin of fiber-reinforced resins, and is particularly suitable as a prepreg with high heat resistance or small dimensional change rate. In addition, the polymaleimide compound contained in the curable composition can be coated because it shows excellent solubility in various solvents. The heat-resistant components and electronic components thus obtained can be suitably used in various applications, such as industrial machinery parts, general machinery parts, parts such as automobiles, railways, and vehicles, aerospace-related parts, electronic and electrical components, building materials, container and packaging components, daily necessities, sports and leisure products, and housing components for wind power generation, but are not limited to these.

[0199] Example

[0200] The present invention will be specifically described by way of examples and comparative examples. Hereinafter, unless otherwise specified, "parts" and "%" are based on mass. It should be noted that the physical properties of the synthesized polyimide compound were measured as follows and are shown in Table 1.

[0201] 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 polyimide compounds obtained in the examples and comparative examples were calculated.

[0202] <Measurement of GPC>

[0203] Measuring device: "HLC-8320GPC" manufactured by Tosoh Corporation,

[0204] Column: Guard column "HXL-L" manufactured by Tosoh Corporation

[0205] + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

[0206] + "TSK-GEL G2000HXL" manufactured by Tosoh Corporation

[0207] + "TSK-GEL G3000HXL" manufactured by Tosoh Corporation

[0208] + "TSK-GEL G4000HXL" manufactured by Tosoh Corporation

[0209] Detector: RI (differential refractometer)

[0210] Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Corporation

[0211] Measuring conditions: Column temperature 40 °C

[0212] Elution solvent: Tetrahydrofuran

[0213] Flow rate: 1.0 ml / min

[0214] Standard: According to the measurement manual of the "GPC Workstation EcoSEC-WorkStation", the following monodisperse polystyrene with known molecular weight was used.

[0215] (Using polystyrene)

[0216] "A-500" manufactured by Tosoh Corporation

[0217] "A-1000" manufactured by Tosoh Corporation

[0218] "A-2500" manufactured by Tosoh Corporation

[0219] "A-5000" manufactured by Tosoh Corporation

[0220] "F-1" manufactured by Tosoh Corporation

[0221] "F-2" manufactured by Tosoh Corporation

[0222] "F-4" manufactured by Tosoh Corporation

[0223] "F-10" manufactured by Tosoh Corporation

[0224] "F-20" manufactured by Tosoh Corporation

[0225] "F-40" manufactured by Tosoh Corporation

[0226] "F-80" manufactured by Tosoh Corporation

[0227] "F-128" manufactured by Tosoh Corporation

[0228] Sample: A tetrahydrofuran solution containing 1.0% by mass in terms of resin solid content was filtered through a microfilter (50 μl).

[0229] <Amine Equivalent Weight and Maleimide Equivalent Weight>

[0230] The amine equivalent of the aromatic amine obtained in the examples was measured by the following method.

[0231] About 2.5 g of aromatic amine, 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine were accurately weighed in a 500 mL stoppered Erlenmeyer flask, and then a cooling tube was installed and the mixture was heated under reflux in an oil bath set at 120° C. for 150 minutes.

[0232] After cooling, add 5.0 mL of distilled water, 100 mL of propylene glycol monomethyl ether, and 75 mL of tetrahydrofuran, and titrate with 0.5 mol / L potassium hydroxide-ethanol solution by potentiometric titration. Perform a blank test in the same manner for correction.

[0233] Amine equivalent (g / equivalent) = (S x 2,000) / (Blank-A)

[0234] S: amount of sample (g)

[0235] A: Consumption of 0.5 mol / L potassium hydroxide-ethanol solution (mL)

[0236] Blank: Consumption of 0.5 mol / L potassium hydroxide-ethanol solution in the blank test (mL)

[0237] The maleimide group equivalent of the maleimide resin obtained in the Examples is a value converted from the amine equivalent of the aromatic amine as an intermediate, and is obtained by the following formula.

[0238] Maleimide equivalent (g / equivalent) = amine equivalent + 80

[0239] <FD-MS measurement>

[0240] The FD-MS spectrum of the polyimide compound obtained in the examples was measured using the following measurement apparatus and measurement conditions.

[0241] Measurement apparatus: JMS-T100 GC AccuTOF

[0242] Measurement conditions

[0243] Measurement range: m / z = 4.00 to 2000.00

[0244] Rate of change: 51.2 mA / min

[0245] Final current value: 45 mA<C

[0246] Cathode voltage: -10 kV

[0247] Recording interval: 0.07 sec

[0248] < 13 <C-NMR measurement>

[0249] The polyimide compound obtained in the examples 13 The C-NMR spectrum was measured using the following measurement apparatus and measurement conditions.

[0250] 13 C-NMR: "JNM-ECZ400S" manufactured by JEOL RESONANCE

[0251] Resonance frequency: 100 MHz

[0252] Number of accumulations: 4000 times

[0253] Solvent: chloroform-d

[0254] Sample concentration: 12 mass%

[0255] Relaxing agent: chromium(III) acetylacetonate

[0256] [Example 1] Synthesis of maleimide compound (A-1)

[0257] (1) Synthesis of intermediate amine

[0258] In a flask equipped with a thermometer, a cooling tube, a Dean-Stark separator, and a stirrer, 302.95g (2.5mol) of 2,6-dimethylaniline, 292.93g (1.25mol) of 1,2-bis(vinylphenyl)ethane, 715.05g of xylene and 119.18g of activated clay were added, and the temperature was raised to 130°C while stirring, and maintained for 30 minutes. Then, the temperature was raised to 190°C over 3 hours while distilling off the xylene, and maintained at this temperature for 6 hours. After the maintenance was completed, the mixture was diluted with 500g of xylene and the activated clay was filtered out by filtration. The filtrate was heated and decompressed to distill off the solvent and unreacted 2,6-dimethylaniline to obtain an aromatic amine resin (a-1) (amine equivalent 244g / equivalent). The Mn of the obtained amine resin is 423, and the Mw is 438. The GPC diagram is shown in FIG. Figure 1A , FD-MS shows Figure 1B , 13 C-NMR shows Figure 1C .

[0259] (2) Maleimidation

[0260] In a flask equipped with a thermometer, cooling tube, Dean-Stark separator, and stirrer, 67.84 g (1.3 equivalents) of maleic anhydride and 271 g of toluene were added and stirred at room temperature. Subsequently, a mixed solution of 130 g (1 equivalent) of reactant (a-1) and 73.82 g of DMF was added dropwise over 1 hour, and the mixture was allowed to react for 2 hours. 5.06 g of p-toluenesulfonic acid monohydrate was added to the reaction solution, which was heated to 115°C. After cooling and separating the azeotropic water and toluene under reflux, only the toluene was returned to the system and a dehydration reaction was carried out for 5 hours. After air cooling to room temperature, the mixture was neutralized with 49% NaOH. Then, the toluene and water were removed by vacuum distillation at 60°C, and 600 g of MEK was added to the DMF solution remaining in the flask. After the solution was heated to 60°C, it was subjected to three liquid separation treatments with 200 g of ion-exchanged water to remove the salt in the solution. Sodium sulfate was then added and dried, followed by concentration under reduced pressure. The obtained reaction product was vacuum 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. Figure 2A , FD-MS shows Figure 2B , 13 C-NMR shows Figure 2C .

[0261] [Example 2] Synthesis of maleimide compound (A-2)

[0262] (1) Synthesis of intermediate amines

[0263] In a flask equipped with a thermometer, a cooling tube, a Dean-Stark separator, and a stirrer, 405.54 g (3 mol) of 2-methyl-6-ethyl-aniline, 234.34 g (1 mol) of 1,2-bis(vinylphenyl)ethane, 767.86 g of xylene, and 127.98 g of activated clay were added, and the temperature was raised to 130°C while stirring, and maintained for 30 minutes. Then, the temperature was raised to 190°C over 3 hours while distilling off the xylene, and maintained at this temperature for 6 hours. After the maintenance was completed, it was diluted with 687 g of xylene, and the activated clay was filtered out by filtration. The filtrate was heated and reduced in pressure to distill off the solvent and unreacted 2-methyl-6-ethyl-aniline to obtain an aromatic amine resin (a-2) (amine equivalent 258 g / equivalent). The Mn of the obtained amine resin is 466, and the Mw is 483. The GPC diagram is shown in FIG. Figure 3A , FD-MS shows Figure 3B , 13 C-NMR shows Figure 3C .

[0264] (2) Maleimidation

[0265] In the column "(2) Maleimidation" of Example 1, "Reactant (a-1)" was changed to "Reactant (a-2)", and the amount of input was changed to 64.11 g (1.3 equivalents) of maleic anhydride, 265 g of toluene, and 72.96 g of DMF. The reaction was carried out in the same manner as in Example 1 to obtain a maleimide compound (A-2). The maleimide compound (A-2) had an Mn of 602 and an Mw of 627. The GPC chart is shown in FIG. Figure 4A , FD-MS shows Figure 4B , 13 C-NMR shows Figure 4C .

[0266] [Example 3] Synthesis of maleimide compound (A-3)

[0267] (1) Synthesis of intermediate amines

[0268] In a flask equipped with a thermometer, a cooling tube, a Dean-Stark separator, 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 added, and the temperature was raised to 130°C while stirring, and maintained for 30 minutes. Then, the temperature was raised to 190°C over 3 hours while distilling off the xylene, and maintained at this temperature for 6 hours. After the maintenance was completed, the mixture was diluted with 513.04 g of xylene, and the activated clay was filtered out by filtration. The filtrate was heated and reduced in pressure to distill off the solvent and unreacted 2-ethylaniline to obtain an aromatic amine resin (a-3) (amine equivalent 263 g / equivalent). The Mn of the obtained amine resin was 543, and the Mw was 683. The GPC diagram is shown in FIG. Figure 5A , FD-MS shows Figure 5B , 13 C-NMR shows Figure 5C .

[0269] (2) Maleimidation

[0270] In the column "(2) Maleimidation" of Example 1, "Reactant (a-1)" was changed to "Reactant (a-3)", and the amount of maleic anhydride, toluene, and p-toluenesulfonic acid monohydrate was changed to 63.11 g (1.3 equivalents), 264 g, and 4.71 g, respectively. 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. The GPC chart is shown in FIG. Figure 6A , FD-MS shows Figure 6B , 13 C-NMR shows Figure 6C .

[0271] [Example 4] Synthesis of maleimide compound (A-4)

[0272] (1) Synthesis of intermediate amines

[0273] In a flask equipped with a thermometer, a cooling tube, a Dean-Stark separator, and a stirrer, 228.56 g (1.88 mol) of 2-ethylaniline, 170.00 g (0.73 mol) of 1,2-bis(vinylphenyl)ethane, 85.00 g (0.82 mol) of styrene, 483.56 g of xylene, and 120.89 g of activated clay were added, and the temperature was raised to 130°C while stirring, and maintained for 30 minutes. Then, the temperature was raised to 190°C over 3 hours while distilling off the xylene, and maintained at this temperature for 6 hours. After the maintenance was completed, the mixture was diluted with 483.56 g of xylene, and the activated clay was filtered out by filtration. The filtrate was heated and decompressed to remove the solvent and unreacted 2-ethylaniline, and an aromatic amine resin (a-4) (amine equivalent 305 g / equivalent) was obtained. The Mn of the obtained amine resin was 484, and the Mw was 743. The GPC diagram is shown in FIG. Figure 7 .

[0274] (2) Maleimidation

[0275] In the column "(2) Maleimidation" of Example 1, "Reactant (a-1) 130 g (1.3 equivalents)" was changed to "Reactant (a-4) 100 g (1 equivalent)", and the amount of input was changed to 41.85 g (1.3 equivalents) of maleic anhydride, 193.30 g of toluene, 54.11 g of DMF, and 3.12 g of p-toluenesulfonic acid monohydrate. The reaction was carried out in the same manner as in Example 1 to obtain a maleimide compound (A-4). The maleimide compound (A-4) had an Mn of 635 and an Mw of 937. The GPC chart is shown in FIG. Figure 8 .

[0276] [Example 5] Synthesis of maleimide compound (A-5)

[0277] (1) Synthesis of intermediate amines

[0278] In a flask equipped with a thermometer, a cooling tube, a Dean-Stark separator, 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 placed and heated to 80°C while stirring. The temperature was then slowly raised from 80°C to 150°C. The azeotropic water and xylene were cooled and separated under reflux, and only the xylene was returned to the system for dehydration reaction. The temperature was then maintained at 150°C for 2 hours. The temperature was then raised to 190°C over 3 hours while distilling off the xylene, and maintained at this temperature for 4 hours. After the temperature was maintained, the mixture was diluted with 177.24 g of xylene and the activated clay was filtered off. The filtrate was heated under reduced pressure to distill off the solvent and unreacted benzyl alcohol, yielding an aromatic amine resin (a-5) (amine equivalent: 308 g / equivalent). The Mn of the obtained amine resin is 620 and Mw is 944. The GPC diagram is shown in FIG. Figure 9 .

[0279] (2) Maleimidation

[0280] In the column "(2) Maleimidation" of Example 1, "Reactant (a-1) 130 g (1.3 equivalents)" was changed to "Reactant (a-5) 60 g (1 equivalent)", and the amount of input was changed to 24.83 g (1.3 equivalents) of maleic anhydride, 115.58 g of toluene, 32.39 g of DMF, and 1.85 g of p-toluenesulfonic acid monohydrate. The reaction was carried out in the same manner as in Example 1 to obtain a maleimide compound (A-5). The maleimide compound (A-5) had an Mn of 750 and an Mw of 1141. The GPC chart is shown in FIG. Figure 10 .

[0281] [Example 6] Synthesis of maleimide compound (A-6)

[0282] (1) Synthesis of intermediate amines

[0283] In a flask equipped with a thermometer, a cooling tube, a Dean-Stark separator, and a stirrer, 216.37 g (1.60 mol) of 2-isopropylaniline, 150.00 g (0.64 mol) of 1,2-bis(vinylphenyl)ethane, 439.64 g of xylene, and 73.27 g of activated clay were added, and the temperature was raised to 130°C while stirring, and maintained for 30 minutes. Then, the temperature was raised to 190°C over 3 hours while distilling off the xylene, and maintained at this temperature for 6 hours. After the maintenance was completed, the mixture was diluted with 439.64 g of xylene, and the activated clay was filtered out by filtration. The filtrate was heated and decompressed to distill off the solvent and unreacted 2-isopropylaniline to obtain an aromatic amine resin (a-6) (amine equivalent 281 g / equivalent). The Mn of the obtained amine resin was 1100, and the Mw was 1325. The GPC diagram is shown in FIG. Figure 11 .

[0284] (2) Maleimidation

[0285] In the column "(2) Maleimidation" of Example 1, "Reactant (a-1) 130 g (1.3 equivalents)" was changed to "Reactant (a-6) 110 g (1 equivalent)", and the amount of input was changed to 49.90 g (1.3 equivalents) of maleic anhydride, 218.17 g of toluene, 60.56 g of DMF, and 3.72 g of p-toluenesulfonic acid monohydrate. The reaction was carried out in the same manner as in Example 1 to obtain a maleimide compound (A-6). The maleimide compound (A-6) had an Mn of 1330 and an Mw of 1529. The GPC chart is shown in FIG. Figure 12 .

[0286] [Comparative Example 1] Synthesis of Maleimide Compound (B-1)

[0287] The synthesis was carried out with reference to Example 1 of Japanese Patent No. 71601517 to obtain a comparative maleimide (B-1).

[0288] <Examples 7 to 12 and Comparative Example 1> Preparation of Curable Compositions and Preparation of Cured Products

[0289] To the maleimides (A-1) to (A-6) obtained in Examples 1 to 6 and the comparative maleimide (B-1), DCPO ("PERCUMYL D", manufactured by NOF Corporation, dicumyl peroxide) was added as a catalyst in an amount of 1 part by weight to prepare a curing resin composition.

[0290] Next, the curable compositions of Examples 7 to 12 and Comparative Example 1 were cured using the following curing conditions to produce cured products corresponding to the curable compositions of Examples 7 to 12 and Comparative Example 1, respectively. The water absorption and thermal expansion properties were then evaluated using the following methods. The results are shown in Table 1.

[0291] <Curing Conditions>

[0292] The resulting product was heat-cured at 200°C for 2 hours using a vacuum press, and then heat-cured at 250°C for 2 hours.

[0293] Thickness after forming: 1.3mm

[0294] <Measurement of Moisture Absorption Rate>

[0295] The obtained cured product was cut into a test piece of 5 mm × 55 mm × 1.3 mm using a pressure cooker tester. After being kept under conditions of 85°C, 85% RH, and 1 atmosphere for 50 hours, the moisture absorption rate (%) was calculated using the following formula to evaluate the hygroscopicity.

[0296] Moisture absorption rate (%) = [(weight of test piece after test - weight of test piece before test) ÷ (weight of test piece before test) × 100]

[0297] <Measurement of Thermal Expansion Coefficient>

[0298] A test piece having a size of 5 mm×5 mm×1.3 mm was cut out from the obtained cured product and subjected to thermal analysis in a compression mode using a thermomechanical analyzer (TMA: SS-6100 manufactured by Seiko Instruments) under the following conditions.

[0299] Measuring load: 88.8mN

[0300] Heating rate: 3℃ / min

[0301] Measuring temperature range: -50℃ to 288℃

[0302] The difference in the probe position at 25°C after the measurement was calculated using the original thickness of the test piece and the following formula, and evaluated as the dimensional change rate after the heat history.

[0303] Dimensional change rate (%) = [(probe position of the test piece before measurement - probe position of the test piece after measurement) ÷ thickness of the test piece before measurement × 100]

[0304] [Table 1]

[0305] Example 7 Example 8 Example 9 Example 10 Example 11 Example 12 Comparative Example 1 Maleimide resin (A-1) (A-2) (A-3) (A-4) (A-5) (A-6) (B-1) Moisture absorption rate (%) 1.2 1.2 1.1 0.6 1.0 1.2 1.3 Thermal expansion coefficient (ppm) 92 74 112 96 106 99 118

[0306] From the results shown in Table 1, a comparison between Examples 7 to 12 and Comparative Example 1 confirmed that the use of the polymaleimide compounds of Examples 1 to 6 allowed for a high degree of both low thermal expansion coefficient and moisture absorption resistance to be achieved.

[0307] Industrial Application Possibilities

[0308] Therefore, the polymaleimide compound of the present invention, the curable composition containing the polymaleimide compound, and the cured product thereof can be suitably used in heat-resistant components or electronic components, and in particular, can be suitably used in prepregs, circuit boards, semiconductor sealing materials, semiconductor devices, build-up films, build-up substrates, adhesives using conductive pastes, resist materials, and the like.

Claims

1. A polymaleimide compound comprising an aromatic amine compound (A), a compound (B1) represented by the following general formula (b1) and maleic anhydride as essential reaction raw materials (1), [Chemistry 1] In the 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, a sulfinyl group, or a sulfonyl group, and n is 0 or 1.

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

3. The polymaleimide compound according to claim 1 or 2, which is represented by the following general formula (1): [Chemistry 2] In the general formula (1), R 1 represents an alkyl group, alkoxy group or alkylthio group, aryl group, aryloxy group, arylthio group or arylalkyl group, or cycloalkyl group having 1 to 10 carbon atoms, l represents the average number of repeating units and represents 0 to 20, m represents an integer from 0 to 3, o represents an integer from 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, a sulfinyl group, or a sulfonyl group, and n represents a number of 0 or 1.

4. 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 claim 1 .

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 formed by laminating the prepreg according to claim 7 and copper foil and then heat-compressing and molding them. 9 . A laminated film comprising the curable composition according to claim 5 . 10 . A semiconductor sealing material comprising the curable composition according to claim 5 . 11 . A semiconductor device comprising a cured product of the semiconductor sealing material according to claim 10 .

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