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

Abstract

The present invention provides a curable composition, a cured product, a prepreg, a circuit substrate, a build-up film, a semiconductor sealing material, and a semiconductor device. The present invention aims to provide a curable composition and a cured product thereof which exhibit a low dielectric loss tangent and a low moisture absorption rate upon curing. The present invention is a curable composition characterized by containing a polymelamine compound (A) and an amine compound (B), the polymelamine compound (A) containing a monocyclic or condensed polycyclic aromatic group to which two or more straight-chain or branched alkylene groups are bonded.

Description

Technical Field

[0001] This disclosure relates to curable compositions, cured products, prepregs, circuit boards, multilayer films, semiconductor sealants, and semiconductor devices. Background Technology

[0002] Prepregs, obtained by impregnating glass cloth with thermosetting resins such as epoxy resins or BT (bismaleimide-triazine) resins and drying them by heating, laminates obtained by curing the prepregs by heating, and multilayer boards obtained by combining the laminates and the prepregs and curing them by heating, are widely used as circuit board materials for electronic devices. Among them, packaging substrates, which serve as insertion mechanisms for mounting semiconductors in printed circuit boards, are becoming increasingly thinner. Warpage of the packaging substrates during mounting has become a problem. Therefore, materials with high heat resistance are needed to suppress warpage of the packaging substrates during mounting.

[0003] Furthermore, the increasing speed and frequency of signals in recent years has created a demand for thermosetting compositions capable of forming cured materials that maintain sufficiently low dielectric constants and exhibit sufficiently low dielectric loss tangents under these conditions. Particularly recently, there has been a demand for materials and compositions with improved properties, such as heat resistance and dielectric characteristics, in various electrical material applications, especially advanced materials applications. Maleimide resins have attracted attention as materials combining heat resistance and low dielectric constant / low dielectric loss tangent to meet these requirements. However, while conventional maleimide resins exhibit high heat resistance, they also suffer from high hygroscopicity, and their dielectric properties (dielectric constant / dielectric loss tangent) do not meet the levels required for advanced materials applications.

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

[0005] Existing technical documents

[0006] Patent documents

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

[0008] The problem that the invention aims to solve

[0009] However, the thermosetting resin composition in Patent Document 1 does not discuss the dielectric loss tangent, therefore the dielectric constant and dielectric loss tangent do not meet the levels required for advanced material applications, and it does not take into account low hygroscopicity at high temperatures, as well as low dielectric constant and low dielectric loss tangent. Furthermore, transmission loss increases with higher frequencies, therefore, circuit board materials require reduced transmission loss in high-frequency regions. However, the technology in Patent Document 1 only discusses the dielectric properties in currently utilized frequency bands (ranging from several hundred MHz to 3 GHz), without discussing whether it can cope with technologies used in 5G mobile communication systems utilizing so-called Sub-6 and above frequency bands (e.g., above 3.6 GHz).

[0010] Therefore, the technical problem to be solved by this disclosure is to provide a curable composition, cured product, prepreg, circuit board, multilayer film, semiconductor sealant and semiconductor device that has low hygroscopicity during curing and exhibits low dielectric loss tangent and low dielectric constant.

[0011] Methods for solving problems

[0012] In order to solve the above-mentioned problems, the inventors have repeatedly and diligently studied and found that by using a curable composition containing a polymaleimide compound (A) and an amine compound (B), wherein the polymaleimide compound (A) contains a monocyclic or condensed polycyclic aromatic ring with two or more straight-chain or branched alkylene groups attached, it is possible to achieve a high level of hygroscopicity during curing, as well as low dielectric loss tangent and low dielectric constant, thereby completing the present invention.

[0013] The effects of the invention

[0014] According to this disclosure, curable compositions, cured products, prepregs, circuit boards, multilayer films, semiconductor sealants, and semiconductor devices can be provided that can achieve a high level of balance between low hygroscopicity, low dielectric constant, and low dielectric loss tangent during curing.

[0015] According to this disclosure, curable compositions, cured products, prepregs, circuit boards, multilayer films, semiconductor sealants, and semiconductor devices can be provided that maintain a high level of performance in frequency bands above Sub6, while also exhibiting low hygroscopicity, low dielectric constant, and low dielectric loss tangent during curing. Such curable compositions are particularly useful in applications such as sealing materials for electronic components. Attached Figure Description

[0016] [ Figure 1A ] Figure 1A The GPC determination results of the polymaleimide compound (A-1) of Synthetic Example 1 are shown.

[0017] [ Figure 1B ] Figure 1BThe FD-MS results of the polymaleimide compound (A-1) of Synthetic Example 1 are shown.

[0018] [ Figure 1C ] Figure 1C The polymaleimide compound (A-1) of Synthesis Example 1 is shown. 13 C-NMR measurement results. Detailed Implementation

[0019] Hereinafter, embodiments of the present invention (referred to as "this embodiment") will be described in detail, but this disclosure is not limited to the following description and various modifications can be made within its scope.

[0020] [the term]

[0021] In this specification, "reaction material" refers to a compound that partially constitutes the chemical structure of the target compound, used to obtain the target compound through a chemical reaction such as combination or decomposition, excluding substances that act as chemical reaction accelerants such as solvents and catalysts. In particular, when polymaleimide compound (A) is used as the target, "reaction material" refers to a precursor used to obtain the polymaleimide compound (A) or its precursor compound (e.g., an intermediate amine compound (c) obtained by linking the above-mentioned aromatic amine compound (a) with each other through the above-mentioned aromatic divinyl compound (b1)) through a chemical reaction.

[0022] The term "aromatic group" in this specification preferably refers to an aromatic ring having 3 to 30 carbon atoms, and more preferably an aromatic ring having 4 to 26 carbon atoms. Furthermore, regarding the term "aromatic group" in this specification, the hydrogen atoms of the aromatic ring in the aromatic group may be substituted with substituents, such as alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, or halogen atoms. Additionally, "aromatic group" includes heteroaromatic groups, and the -CH2- or -CH= in the "aromatic group" may be substituted with -O-, -S-, or -N= in a non-adjacent manner.

[0023] Examples of aromatic ring types include monocyclic aromatic rings and condensed polycyclic aromatic rings.

[0024] Examples of monocyclic aromatic rings include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, and triazine. Examples of condensed polycyclic aromatic rings include naphthalene, anthracene, phenatene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and acridine. Furthermore, the hydrogen atoms in the aromatic ring of this aromatic group may be substituted, for example, with alkyl, alkenyl, alkoxy, aryl, aralkyl, or halogen atoms having 1 to 10 carbon atoms.

[0025] It should be noted that a monovalent aromatic group refers to a group obtained by removing one hydrogen atom from an aromatic group, a divalent aromatic group refers to a group obtained by removing two arbitrary hydrogen atoms from an aromatic group, and a trivalent to hexavalent aromatic group refers to a group obtained by removing three to six hydrogen atoms from an aromatic group.

[0026] As used in this specification, "aralkyl" may include, for example, benzyl, diphenylmethyl, naphthylmethyl, etc. The hydrogen atom of the aromatic ring in this aralkyl group may be substituted with, for example, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. It should be noted that "arylene" may include divalent groups obtained by removing one arbitrary hydrogen atom from the aforementioned "aralkyl" group.

[0027] In this specification, "alkyl" can be any of the following: linear, branched, or cyclic. Examples include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, tert-pentyl, neopentyl, 1,2-dimethylpropyl, n-hexyl, isohexyl, (n)heptyl, (n)octyl, (n)nonyl, (n)decyl, (n)undecyl, (n)dodecyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, or cyclononyl.

[0028] In this specification, "cycloalkyl" may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, methylcyclobutyl, norbornyl, or adamantyl, etc.

[0029] The term "alkylthio" in this specification may include methylthio, ethylthio, propylthio, butylthio, octylthio, or 2-ethylhexylthio.

[0030] In this specification, "alkenyl" may include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, pentylyl, hexynyl, vinyl, allyl, or isopropenyl, etc.

[0031] In this specification, "alkoxy" may include, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy, hexoxy, 2-ethylhexoxy, octoxy, or nonoxy.

[0032] In this specification, "aryl" may include, for example, phenyl, naphthyl, phenatenyl, phenanthryl, anthraceneyl, azulel, tetrahydronaphthyl, etc. Furthermore, regarding this "aryl," the hydrogen atom of the aromatic ring may be substituted, for example, with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, or a halogen atom. It should be noted that "arylene" may include divalent groups obtained by removing one arbitrary hydrogen atom from the aforementioned "aryl."

[0033] The term "aryloxy" in this specification may include phenoxy, naphthoxy, anthraceneoxy, phenanthroxy, or pyreneoxy, etc.

[0034] The term "aryl thio" in this specification may include phenylthio, naphthio, anthracene thio, phenanthrene thio, or pyrene thio, among other aryl thio groups.

[0035] The term "halogen atom" in this specification may include, for example, fluorine, chlorine, bromine, or iodine atoms.

[0036] In this specification, "structural unit" refers to a (repeating) unit of a chemical structure formed during a reaction or polymerization. In other words, it refers to the portion of the structure in a compound formed through a reaction or polymerization that is not related to the chemical bonds associated with that reaction or polymerization; it refers to a so-called residue.

[0037] [Curing composition]

[0038] The curable composition of this embodiment contains a polymaleimide compound (A) (hereinafter referred to only as polymaleimide compound (A)) and an amine compound (B). The polymaleimide compound (A) contains a monocyclic or condensed polycyclic aromatic ring connected to two or more straight-chain or branched alkylene groups.

[0039] Because of the polymaleimide compound (A) which has a low proportion of polar functional groups in its chemical structure, excellent low dielectric properties and low hygroscopicity can be achieved as a whole composition. In addition, by combining the polymaleimide compound (A) with the amine compound (B), low hygroscopicity, low dielectric constant and low dielectric loss tangent during curing can be maintained at a high level even in the frequency band above Sub6.

[0040] In the curable composition of this embodiment, the mixing ratio (parts by mass) of the polymaleimide compound (A) to the amine compound (B) is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and even more preferably 75:25 to 25:75. By adjusting the mixing ratio within the above range, excellent low hygroscopicity, low dielectric constant, and low dielectric loss tangent can be exhibited, and therefore it is preferred.

[0041] The curable composition of this embodiment may contain a curing agent (C) other than an amine compound (B) within a range that does not impair the curing properties of the present invention. Furthermore, other resins (D) other than polymaleimide compound (A) and amine compound (B), curing accelerators, or additives may be added to the curable composition of this embodiment. Examples of such additives include flame retardants, inorganic fillers, silane coupling agents, mold release agents, antioxidants, light stabilizers, heat stabilizers, pigments, and emulsifiers.

[0042] Hereinafter, the polymaleimide compound (A) and the amine compound (B), which are essential components of the curable composition of this embodiment and have a monocyclic or condensed polycyclic aromatic ring with two or more straight-chain or branched alkylene groups and two or more maleimide groups, will be described in detail. Then, the curing agent (C), other resins (D), curing accelerators and additives other than the amine compound (B) will be described as optional components.

[0043] (Polymaleimide compound (A))

[0044] The polymaleimide compound (A) involved in this embodiment is a compound having a monocyclic or condensed polycyclic aromatic ring connected with two or more straight-chain or branched alkylene groups and two or more maleimide groups.

[0045] The aforementioned monocyclic or polycyclic aromatic ring with two or more straight-chain or branched alkylene groups refers to a monocyclic or polycyclic aromatic ring containing two or more alkylene groups with 1 to 12 carbon atoms in its straight or branched chain, and where one of the alkylene groups is linked to two or more divalent or more groups on the monocyclic or polycyclic aromatic ring. Therefore, the number of alkylene groups in the straight or branched chain attached to the monocyclic or polycyclic aromatic ring is consistent with the valence of the alkylene group containing the aforementioned aromatic ring. In this embodiment, the monocyclic or polycyclic aromatic ring with two or more straight-chain or branched alkylene groups is preferably a divalent to tetravalent group, more preferably a divalent to trivalent group.

[0046] As a monocyclic or condensed polycyclic aromatic ring with two or more straight-chain or branched alkylene groups connected in this embodiment, the group is preferably represented by the following general formula (I).

[0047] [Chemistry 1]

[0048]

[0049] (In the above general formula (I), Ar) 1 L represents an aromatic group with a (2+h) valence. 1 L 2 and L 3 Each alkylene group independently represents a carbon group with 1 to 12 carbon atoms; h represents an integer between 0 and 2; and * indicates a connection to other atoms.

[0050] It should be noted that in the above general formula (I), when h is 0, the group shown in general formula (I) is divalent, and when h is 2, the group shown in general formula (I) is tetravalent.

[0051] The maleimide group described above is preferably a group represented by the following general formula (II).

[0052] [Chemistry 2]

[0053]

[0054] (In the above general formula (II), Ar) 2 (This indicates an aromatic group; dashed lines indicate its absence or a single bond; asterisks indicate a bond with another atom.)

[0055] It should be noted that in general formula (II), the dashed line indicates absence or represents a single bond. When the dashed line is absent, the maleimide group in general formula (II) can be monovalent. On the other hand, when the dashed line is a single bond, the maleimide group in general formula (II) can be divalent.

[0056] The preferred polymaleimide compound (A) of this embodiment is a compound having the structural unit shown in the following general formula (1) or a compound having one or more alkyl groups (a) (hereinafter also referred to as aromatic amine compound (a)), two vinyl groups (b1) (hereinafter also referred to as aromatic divinyl compound (b1)), and maleic anhydride as reactants (1).

[0057] [Chemistry 3]

[0058]

[0059] (In the above general formula (1), R) 1 Each can be independently represented as an alkyl group.

[0060] R 2Each of these groups independently represents an alkyl, alkoxy, or alkylthio group having 1 to 10 carbon atoms; an aryl, aryloxy, or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl or mercapto group.

[0061] R 3 R 4 R 5 and R 6 Each can independently represent a hydrogen atom or a methyl group, and R 3 and R 4 One side is a hydrogen atom and the other side is a methyl group, R 5 and R 6 One side is a hydrogen atom and the other side is a methyl group.

[0062] X 1 The substituents represented by the following general formula (x) are:

[0063] [Chemistry 4]

[0064]

[0065] (In the general formula (x), R) 7 and R 8 Each can independently represent a hydrogen atom or a methyl group, and R 7 and R 8 One side is a hydrogen atom and the other side is a methyl group, R 9 Each of these groups independently represents an alkyl, alkoxy, or alkylthio group with 1 to 10 carbon atoms; an aryl, aryloxy, or arylthio group with 6 to 10 carbon atoms; a cycloalkyl group with 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group; with t representing an integer from 0 to 4.

[0066] r represents X relative to each connection. 1 X of the benzene ring 1 The average of the substitution numbers, where p represents an integer from 1 to 3, q ​​represents an integer from 0 to 4, and k represents an integer from 1 to 100.

[0067] Therefore, during curing, it is possible to achieve a higher level of balance between low moisture absorption and low dielectric loss tangent.

[0068] <Preferred method for polymaleimide compound (A)>

[0069] The polymaleimide compound (A) of this embodiment preferably has the structural unit shown in the above general formula (1).

[0070] Furthermore, in the above general formula (1), when p is an integer greater than 2, there exist multiple R... 1 They can be the same or different. When q is an integer greater than 2, there exist multiple R... 2They can be the same or different. When t is an integer greater than 2, there exist multiple R... 9 They can be the same or different.

[0071] In the above general formula (1), R 1 Alkyl groups, each individually preferred, represent 1 to 10 carbon atoms; more preferably, they represent 1 to 6 carbon atoms. Furthermore, when p is an integer of 2 or more, multiple R groups are present. 1 They can be the same or different. R is the preferred choice in general formula (1). 1 , which is methyl, ethyl or n-propyl. It should be noted that in general formula (1), the linker is R. 1 The benzene ring can be the benzene ring of an aromatic amine compound (a).

[0072] In the above general formula (1), p preferably represents 1 or 2. It should be noted that R is preferred. 1 The connection to the general formula (1) has R 1 At least one of the 2, 3, 4, 5 or 6 positions of the benzene ring.

[0073] In the above general formula (1), R 2 Each of the following is preferably represented independently: 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, an alkyl group having 1 to 10 carbon atoms; and even more preferably, an alkyl group having 1 to 6 carbon atoms. Furthermore, when q is an integer of 2 or more, a plurality of R groups are present. 2 They can be the same or different. R is the preferred choice in general formula (1). 2 , which is methyl, ethyl or n-propyl. It should be noted that in general formula (1), the linker is R. 2 The benzene ring can be the benzene ring of an aromatic divinyl compound (b1). In addition, in the above general formula (1), q preferably represents 0, 1 or 2.

[0074] In the above general formula (1), R 3 and R 4 One side is a hydrogen atom and the other side is a methyl group, R 5 and R 6 One side is a hydrogen atom and the other side is a methyl group. Therefore, the reactivity of the unsaturated bonds inherent in the polymaleimide compound (A) can be maintained at a high level. R in the above general formula (1) 3 R 4 R 5 and R 6In this compound, if the proportion of alkyl groups increases, the reactivity of the unsaturated bonds in the polymaleimide compound (A) may tend to decrease due to steric hindrance. Therefore, if R... 3 R 4 R 5 and R 6 If all the compounds are alkyl groups, the reactivity of the unsaturated bonds in the polymaleimide compound (A) is reduced, making it impossible to form a cured product efficiently.

[0075] In the above general formula (1), X 1 Represented by the above general formula (x), and in this general formula (x), R 7 Preferably representing a hydrogen atom, R 8 Preferably, it represents a methyl group. Additionally, in the above general formula (x), R... 9 Each of the following is preferably represented independently: 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, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms; and even more preferably, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. Furthermore, in the above general formula (x), t preferably represents an integer from 0 to 4, and more preferably an integer from 0 to 3. It should be noted that when t is an integer of 2 or more, multiple R groups exist. 9 They can be the same or different.

[0076] In the above general formula (1), r means that there is X relative to each connection. 1 X of the benzene ring 1 The average number of substitutions is preferably in the range of 0 to 4, and more preferably in the range of 0 to 3.

[0077] In the above general formula (1), k represents the number of repeating units, preferably an integer from 1 to 100, more preferably an integer from 1 to 90, and even more preferably an integer from 1 to 80.

[0078] <Other preferred methods for polymaleimide compound (A)>

[0079] As another preferred embodiment of the polymaleimide compound (A), it may be a compound using an aromatic amine compound (a) having one or more alkyl groups, an aromatic divinyl compound (b1) having two vinyl groups, and maleic anhydride as reactants (1). In this embodiment, the reactants (1) may further contain an aromatic monovinyl compound (b2) having one vinyl group (hereinafter also referred to as aromatic monovinyl compound (b2)). In addition, the polymaleimide compound (A) of this embodiment is preferably a polymaleimide compound (A) using an intermediate amine compound (c) obtained by crosslinking aromatic amine compounds (a) having one or more alkyl groups with each other through an aromatic divinyl compound (b1) having two vinyl groups, and maleic anhydride as reactants (3). Furthermore, the intermediate amine compound (c) is preferably a compound that uses an aromatic amine compound (a) having one or more alkyl groups but less than three alkyl groups, an aromatic divinyl compound (b1) having two vinyl groups, and an aromatic monovinyl compound (b2) having one vinyl group as an optional addition as a reaction raw material (2).

[0080] In other words, the intermediate amine compound (c) in this embodiment preferably has the following structure: a structural unit of an aromatic amine compound (a) having an aromatic ring with an amino group (including substituted amino groups obtained by further substituting the hydrogen atom of the amino group with an alkyl group having 1 to 6 carbon atoms) and one to three alkyl groups on the aromatic ring, and a structural unit of an aromatic divinyl compound (b1) having two vinyl groups linked by chemical bonds, and, if necessary, a structural unit of an aromatic monovinyl compound (b2) chemically linked to the aromatic ring in the structural unit of the aromatic amine compound (a). Furthermore, the polymaleimide compound (A) in this embodiment has a structure in which the amino groups (including -NH2 and substituted amino groups) linked to the aromatic ring of the intermediate amine compound (c) are replaced with N-substituted maleimide rings.

[0081] Therefore, the "polymaleimide compound (A)" in this embodiment and the "intermediate amine compound (c)" which is the precursor of the "polymaleimide compound (A)" are different polymer compounds in that the amino group (including -NH2 and substituted amino groups) attached to the aromatic ring is replaced with an N-substituted maleimide ring.

[0082] It should be noted that the structural unit of the aromatic amine compound (a) mentioned above refers to the group obtained by removing two hydrogen atoms from the aromatic ring of the aromatic amine compound (a). For example, if the aromatic amine compound (a) is as shown in the general formula (a) described below, the group obtained by removing two hydrogen atoms from the benzene ring of the general formula (a) is called the structural unit of the aromatic amine compound (a). Furthermore, the structural unit of the aromatic divinyl compound (b1) mentioned above refers to the group obtained by breaking the unsaturated bonds of the two vinyl groups in the aromatic divinyl compound (b1).

[0083] In this embodiment, since an aromatic amine compound (a) having a specific aromatic ring structure is used as a reactant, the reaction site with the aromatic divinyl compound (b1) described later is easily controlled, thus easily obtaining a polymaleimide compound (A) with a uniform chemical structure or chain length. As a result, a polymaleimide compound (A) exhibiting low hygroscopicity and low dielectric loss tangent during curing can be provided.

[0084] Hereinafter, after describing the aromatic amine compound (a) having one or more but three or fewer alkyl groups, the aromatic divinyl compound (b1) having two vinyl groups, the aromatic monovinyl compound (b2) having one vinyl group (which may be any component), and maleic anhydride as constituents of the reaction raw material (1) of polymaleimide compound (A), other preferred embodiments of polymaleimide compound (A) and methods for manufacturing polymaleimide compound (A) will be described.

[0085] <<Aromatic Amine Compounds (a)>>

[0086] The aromatic amine compound (a) in this embodiment has an aromatic ring with an amino group (-NH2 or a substituted amino group) attached, and one to three alkyl groups are attached to the aromatic ring. Therefore, the aromatic amine compound (a) can be an amine compound. Furthermore, the aromatic ring forming the central structure of the aromatic amine compound (a) is preferably a monocyclic ring, including an aromatic hydrocarbon ring and an aromatic heterocyclic ring. As an aromatic hydrocarbon ring, a benzene ring is preferred. As an aromatic heterocyclic ring, for example, a hetero-six-membered ring such as a pyran ring or a pyridine ring can be listed. Furthermore, the aromatic amine compound (a) in this embodiment is more preferably an aromatic ring with an unsubstituted amino group (-NH2) attached, and one to three alkyl groups are attached to the aromatic ring.

[0087] In the aromatic amine compound (a) of this embodiment, one to three alkyl groups of the aromatic ring that can be substituted with hydrogen atoms are included. Examples of alkyl groups with 1 to 10 carbon atoms are included, preferably with 1 to 6 carbon atoms, and more preferably with 1 to 3 carbon atoms. The alkyl group can be linear, branched, or cyclic. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, etc. The smaller the molecular weight of the alkyl group, the more significant the effect (low dimensional change rate) achieved by the present invention. Furthermore, the higher the molecular weight of the alkyl group, the more significant the effect (low water absorption) achieved by the present invention.

[0088] Regarding the upper limit on the number of alkyl groups attached to an aromatic ring having an amino group (including -NH2 and substituted amino groups) in an aromatic amine compound (a), considering that the aromatic ring has an amino group (including -NH2 and substituted amino groups) and two connecting bonds are suitable for polymerization, it can be simply the number obtained by subtracting 3 from the number of substituted ring constituent atoms in the unsubstituted aromatic ring. For example, if the aromatic ring is a benzene ring, the number of alkyl groups is 3 or less.

[0089] Furthermore, by setting the number of substituted alkyl groups on the aromatic ring of the aromatic amine compound (a) to two or more, the reaction site with the aromatic divinyl compound (b1) described later can be easily controlled, thus easily obtaining a polymaleimide compound (A) with a uniform chemical structure or chain length. As a result, the cured polymaleimide compound (A) readily exhibits low hygroscopicity and excellent high-frequency electrical properties.

[0090] Taking the case where the aromatic ring of the aromatic amine compound (a) in this embodiment is a benzene ring as an example, the preferred mode of the aromatic amine compound (a) will be described.

[0091] In this embodiment, among the carbon atoms in the benzene ring constituting the aromatic amine compound (a), preferably one or more of the carbon atoms having the largest HOMO electron density (Hückel coefficient) are unsubstituted (or substituted with hydrogen atoms).

[0092] Therefore, ArSE reactions and molecular design based on cationic reagents formed from the aromatic divinyl compound (b1) described later can be easily controlled. More specifically, if the carbon atom with the highest HOMO electron density (Hückel coefficient) in the benzene ring constituting the aromatic amine compound (a) is unsubstituted, the carbocation of the aromatic divinyl compound (b1), acting as a cationic reagent, readily reacts with this carbon atom. Therefore, by controlling the number and position of alkyl groups attached to the carbon atoms of the benzene ring, the attachment sites or number of alkyl groups with the aromatic divinyl compound (b1) can be adjusted. Thus, the chemical structure or molecular chain length of the resulting polymaleimide compound (A) can be easily designed.

[0093] 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 carbon atom at the 2, 4, and 6 positions of the aniline core is substituted with a hydrogen atom. Thus, the cationic reagent formed from the aromatic divinyl compound (b1) described later readily attacks at least one carbon atom at the meta and para positions (2, 4, and 6 positions) of the aniline core, where the electron density is high. In particular, if an aromatic amine compound (a) having an aniline core substituted with an alkyl group at a specific position is used, the connection site with the aromatic divinyl compound (b1) can be largely controlled, thus easily yielding a polymaleimide compound (A) with a uniform chemical structure or chain length. For example, if a 2,6-dialkylamine is used as the aromatic amine compound (a), it is considered possible to obtain a large quantity of polymaleimide compounds (A) linked to the aromatic divinyl compound (b1) at the 4 position.

[0094] As a specific example of the aromatic amine compound (a) in this embodiment, for example, the following can be used: 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 (e.g., at the 2,3-position, 2,4-position, ... Ethylmethylaniline, cyclobutylaniline, cyclopentylaniline, cyclohexylaniline, ortho-, meta-, or p-toluidine, ortho-, meta-, or p-ethylaniline, ortho-, meta-, or p-isopropylaniline, ortho-, meta-, or p-propylaniline, ortho-, meta-, or p-butylaniline, methylisopropylaniline (e.g., methylisopropylaniline, methyl isopropylaniline, methyl isopropylaniline, methyl isopropylaniline, methyl isopropylaniline, methyl isopropylaniline, methyl isopropylaniline, methyl isopropylaniline, ethyl ... etc. Additionally, the butyl group mentioned above includes n-butyl, tert-butyl, and sec-butyl. It should be noted that the aromatic amine compound (a) in this embodiment can be used alone or in combination of two or more.

[0095] For example, in the case of N-phenylmaleimide, where the maleimide group is directly attached to an unsubstituted benzene ring, the arrangement of the benzene ring and the 5-membered ring of the maleimide in the same plane is stable, thus facilitating stacking and exhibiting high crystallinity. This results in poor solvent solubility. In contrast, in the case of this disclosure, for example, 2,6-dimethylaniline, where an alkyl group (e.g., methyl) is used as a substituent for the benzene ring, the steric hindrance of the methyl group causes the benzene ring and the 5-membered ring of the maleimide to form a staggered conformation, making stacking difficult. Therefore, crystallinity is reduced, and solvent solubility is improved, making this a preferred approach. However, if the steric hindrance is too large, there are concerns about hindering the reactivity during the synthesis of maleimide. Therefore, it is preferable to use, for example, an aromatic amine compound having an alkyl group having 1 to 6 carbon atoms (a).

[0096] The aromatic amine compound (a) required for the reaction raw material (1) in this embodiment can be represented, for example, by the following general formula (a).

[0097] [Chemistry 5]

[0098]

[0099] (In the above general formula (a), R) 1aIndicates alkyl group, p a Represents integers from 1 to 3. Multiple R exist. 1a They can be the same or different.

[0100] In the above general formula (a), the alkyl group is preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. Examples of alkyl groups having 1 to 6 carbon atoms and alkyl groups having 1 to 3 carbon atoms are the same as those described above.

[0101] In the above general formula (a), p a Preferably, it is 1 or 2. It should be noted that R... 1a When multiple alkyl groups are present, they can be the same alkyl group or they can be different alkyl groups.

[0102] It should be noted that in this embodiment, the aromatic amine compound (a) shown in the above general formula (a) can be used alone or in combination of two or more.

[0103] <<Aromatic Divinyl Compounds (b1)>>

[0104] In this embodiment, the aromatic divinyl compound (b1) can be used without particular limitation as long as it has two vinyl groups (CH2=CH-) (also called vinyl groups) as substituents on the aromatic ring and can react with the above-mentioned aromatic amine compound (a).

[0105] In addition, in this embodiment, it is preferable that the reaction raw material (1) contains a mixture of aromatic divinyl compound (b1) and aromatic monovinyl compound (b2).

[0106] Examples of aromatic divinyl compounds (b1) include, for example, divinylbenzene, divinylbiphenyl, divinylnaphthalene, and various compounds obtained by substituting one or more alkyl, alkoxy, or alkylthio groups having 1 to 10 carbon atoms, aryl, aryloxy, 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 these aromatic rings. A preferred form of this substituent is R in the above general formula (1). 2 The same applies. Furthermore, the aforementioned alkyl group can be either straight-chain or branched. From the viewpoint of exhibiting high heat resistance, the number of carbon atoms in the aforementioned alkyl or alkoxy group is preferably 1 to 4. Specifically, examples of the aforementioned alkyl group include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, and isobutyl. Examples of the aforementioned alkoxy group include methoxy, ethoxy, propoxy, and butoxy. Examples of the aforementioned halogen atom include fluorine, chlorine, and bromine.

[0107] The aromatic divinyl compound (b1) used as the reaction raw material (1) for the polymaleimide compound (A) of this disclosure is preferably represented by the following formula (b1).

[0108] [Chemistry 6]

[0109]

[0110] (In the above general formula (b1), R) 2b Each of the following groups independently represents an alkyl, alkoxy, or alkylthio group having 1 to 10 carbon atoms; an aryl, aryloxy, or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl or mercapto group; q 1b Represents integers from 0 to 4. It should be noted that q... 1b In the case of integers greater than 2, there exist multiple R. 2b They can be the same or they can be different.

[0111] R in the above formula (b1) 2b It can correspond to R in general formula (1) 2 Therefore, R in the above general formula (b1) 2b Similar to general formula (1), each is preferably represented by 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 by an alkyl group having 1 to 10 carbon atoms, and even more preferably by an alkyl group having 1 to 6 carbon atoms.

[0112] In the above general formula (b1), q 1b The preferred value is 0 to 2. It should be noted that q 1b In the case of two or more R, there are multiple R b1 They can be the same group or they can be different groups.

[0113] Specific examples of the aromatic divinyl compound (b1) in this embodiment include, for example, 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, 2,5-dimethyl-1,4-divinylbenzene, 2,5-diethyl-1,4-divinylbenzene, cis,cis,β,β'-diethoxy-m-m-divinylbenzene, 1,4-divinyl-2,5-dibutylbenzene, 1,4-divinyl-2,5-dihexylbenzene, and 1,4-divinyl-2,5-dimethoxy Divinylbenzene compounds, including benzobenzene and compounds derived therefrom, and divinylnaphthalene compounds, including 1,3-divinylnaphthalene, 1,4-divinylnaphthalene, 1,5-divinylnaphthalene, 1,6-divinylnaphthalene, 1,7-divinylnaphthalene, 2,3-divinylnaphthalene, 2,6-divinylnaphthalene, 2,7-divinylnaphthalene, 3,4-divinylnaphthalene, 1,8-divinylnaphthalene, 1,5-dimethoxy-4,8-divinylnaphthalene and compounds derived therefrom, but not limited to these.

[0114] It should be noted that the aromatic divinyl compound (b1) in this embodiment can be used alone or in combination of two or more.

[0115] In particular, from a flowability viewpoint, divinylbenzene and compounds having substituents on their aromatic rings are preferred as aromatic divinyl compounds (b1), with divinylbenzene being more preferred. Furthermore, in this embodiment, the substitution position of the vinyl group in divinylbenzene is not particularly limited, but a meta-form is preferred as the main component. The content of the meta-form in divinylbenzene is preferably 40% by mass or more, more preferably 50% by mass or more, relative to the total amount of divinylbenzene.

[0116] In this embodiment, the structural unit of the aromatic divinyl compound (b1) preferably contains 10 to 90% by mass relative to the total amount (100% by mass) of the polymaleimide compound (A), and more preferably 20 to 90% by mass. The structural unit of the aromatic divinyl compound (b1) refers to a group obtained by removing two hydrogen atoms (a total of four hydrogen atoms) from each of the two vinyl groups of the aromatic divinyl compound (b1).

[0117] <<Aromatic Monovinyl Compounds (b2)>>

[0118] In this embodiment, the polymaleimide compound (A) can be further used with other compounds besides the aromatic amine compound (a), the aromatic divinyl compound (b1), and maleic anhydride as reactants. Examples of such other compounds include, for instance, an aromatic monovinyl compound (b2) having one vinyl group. Specifically, in this embodiment, it is preferable to use the aromatic amine compound (a), the aromatic divinyl compound (b1), the aromatic monovinyl compound (b2), and maleic anhydride as reactants (1). Because the polymaleimide compound (A) of this embodiment uses an aromatic monovinyl compound (b2) as a reactant in addition to the aromatic amine compound (a), the aromatic divinyl compound (b1), and maleic anhydride, the resulting cured polymaleimide compound (A) exhibits excellent low dielectric loss tangent, and is therefore preferred.

[0119] In addition, aromatic monovinyl compounds (b2) also generate carbocations in the same way as aromatic divinyl compounds (b1), and therefore readily react with the carbon atoms in the aromatic hydrocarbon rings that constitute aromatic amine compounds (a) that have the highest HOMO electron density (Hückel coefficient).

[0120] The aromatic monovinyl compound (b2) in this embodiment can be exemplified by vinylbenzene (styrene), vinylbiphenyl, vinylnaphthalene, and various compounds obtained by substituting one or more alkyl, alkoxy, or alkylthio groups having 1 to 10 carbon atoms on these aromatic rings; aryl, aryloxy, or arylthio groups having 6 to 10 carbon atoms; cycloalkyl groups having 3 to 10 carbon atoms; halogen atoms; hydroxyl groups; or mercapto groups, etc. The alkyl group can be either straight-chain or branched, and can have unsaturated bonds in its structure. Where low hygroscopicity is important, the alkyl group or alkoxy group is preferably 1 to 4 carbon atoms. Specifically, examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, isobutyl, etc. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, etc. Examples of the halogen atom include fluorine, chlorine, bromine, etc.

[0121] The aromatic monovinyl compound (b2) that can be used as the reaction raw material (1) of the polymaleimide compound (A) of this disclosure can be represented by the following general formula (b2).

[0122] [Chemistry 7]

[0123]

[0124] (In the above general formula (b2), R) 9bEach of these groups independently represents an alkyl, alkoxy, or alkylthio group with 1 to 10 carbon atoms; an aryl, aryloxy, or arylthio group with 6 to 10 carbon atoms; a cycloalkyl group with 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group. 1b Represents integers from 0 to 5. It should be noted that t... 1b In the case of integers greater than 2, there exist multiple R. 9b They can be the same or they can be different.

[0125] R in equation (b2) above 9b It can correspond to R in the general formula (x) 9 Therefore, R in the above general formula (b1) 9b Similar to general formula (x), each is preferably represented independently as 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 as an alkyl group having 1 to 10 carbon atoms, and even more preferably as an alkyl group having 1 to 6 carbon atoms.

[0126] In the above general formula (b1), t 1b The preferred value is 1 to 4. It should be noted that t 1b In the case of two or more R, there are multiple R 9b They can be the same group or they can be different groups.

[0127] Specific examples of aromatic monovinyl compounds (b2) in this embodiment include, for example, styrene, fluorostyrene, vinylbenzyl chloride, alkylvinylbenzenes (o-, m-, p-methylstyrene, o-, m-, p-ethylvinylbenzene), o-, m-, p-(chloromethyl)styrene and compounds composed of their derivatives, etc.; biphenyl compounds such as 4-vinylbiphenyl, 4-vinyl-p-terphenyl and compounds composed of their derivatives; and vinylnaphthalenes such as 1-vinylnaphthalene, 2-vinylnaphthalene and compounds composed of their derivatives, etc., but are not limited to these.

[0128] In particular, from the viewpoint of obtaining raw materials, alkyl vinylbenzenes and compounds having substituents on their aromatic rings are preferred, and ethyl vinylbenzenes are more preferred.

[0129] Furthermore, the substitution positions of vinyl and ethyl groups in ethyl vinylbenzene are not particularly limited, but the meta group is preferred as the main component. The content of the meta group in ethyl vinylbenzene is more preferably 40% by mass or more relative to the total amount of ethyl vinylbenzene, and even more preferably 50% by mass or more.

[0130] When using an aromatic monovinyl compound (b2) as the reaction raw material (1) for the polymaleimide compound (A) in this embodiment, the molar ratio ((b1) / (b2)) of the aromatic monovinyl compound (b2) to the aromatic divinyl compound (b1) in the above-mentioned reaction raw material (1) is preferably 99 / 1 to 50 / 50, more preferably 98 / 2 to 70 / 30.

[0131] In this embodiment, relative to the total amount (100% by mass) of the polymaleimide compound (A), the structural unit of the aromatic monovinyl compound (b2) preferably contains 0 to 40% by mass, more preferably 0 to 30% by mass. The structural unit of the aromatic monovinyl compound (b2) refers to a group obtained by removing two hydrogen atoms from one vinyl group of the aromatic monovinyl compound (b2).

[0132] -Maleic anhydride-

[0133] In this embodiment, maleic anhydride is an essential component of the reaction raw material (1) of polymaleimide compound (A), as described later in the section on the method of manufacturing polymaleimide compound (A), and is used for the maleimization reaction of the amino group (including -NH2 and substituted amino groups) from aromatic amine compound (a).

[0134] <Preferred method for polymaleimide compound (A)>

[0135] The preferred polymaleimide compound (A) of this disclosure will be described below using the case where each aromatic ring is a benzene ring as an example. The following chemical structural formulas are for illustrative purposes only, and the scope of this disclosure is not limited to the following chemical structural formulas.

[0136] In this embodiment, the polymaleimide compound (A) is preferably represented by the following general formula (2).

[0137] [Chemistry 8]

[0138]

[0139] (In the above general formula (2), R) 1 Each independently represents an alkyl group, R 2 Each of the following independently 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; R 3 R 4 R 5 and R 6 Each can independently represent a hydrogen atom or a methyl group, and R 3 and R 4One side is a hydrogen atom and the other side is a methyl group, R 5 and R 6 One side is a hydrogen atom and the other side is a methyl group.

[0140] X 1 The substituents represented by the following general formula (x) are:

[0141] [Chemistry 9]

[0142]

[0143] (In the general formula (x), R) 7 and R 8 Each can independently represent a hydrogen atom or a methyl group, and R 7 and R 8 One side is a hydrogen atom and the other side is a methyl group, R 9 (This indicates an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an aryl group with 6 to 10 carbon atoms, a cycloalkyl group with 3 to 10 carbon atoms, a halogen atom, or a hydroxyl group; t represents an integer from 0 to 4.)

[0144] M 21 M represents a hydrogen atom or a group represented by the following general formula (i). 22 Represents a hydrogen atom, a group represented by general formula (ii) below, or a group represented by general formula (iii) below.

[0145] [Chemistry 10]

[0146]

[0147] In the above general formula (i), R 9 R 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. 7 and R 8 Each can independently represent a hydrogen atom or a methyl group, and R 7 and R 8 One side is a hydrogen atom and the other side is a methyl group, t represents an integer from 0 to 4, and * indicates a connection with other atoms. It should be noted that when t is an integer greater than 2, multiple R groups exist. 9 They can be the same or different.

[0148] [Chemistry 11]

[0149]

[0150] In the above general formula (ii), R 1ii Indicates alkyl group, p ii Represents integers from 0 to 4. It should be noted that p...ii In the case of integers greater than 2, there exist multiple R. 1ii They can be the same or different. In the above general formula (iii), R 1iii R represents an alkyl group. 9 R 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. 7 and R 8 Each can independently represent a hydrogen atom or a methyl group, and R 7 and R 8 One side is a hydrogen atom and the other side is a methyl group, p iii t represents integers from 0 to 3, r represents integers from 0 to 4, and r represents integers from 0 to 4. 1iii For each connection, there is X 1 The average number of substitutions on the benzene ring, representing numbers from 1 to 4, with * indicating bonds to other atoms. It should be noted that p... iii In the case of integers greater than 2, there exist multiple R. 1iii They can be the same or different. When t is an integer greater than 2, there exist multiple R. 9 They can be the same or different.

[0151] r represents X relative to each connection. 1 X of the benzene ring 1 The average of the substitution numbers, where p represents an integer from 1 to 3, q ​​represents an integer from 0 to 4, and k represents an integer from 1 to 100.

[0152] In the above general formula (2), when p is an integer greater than 2, there exist multiple R... 1 They can be the same or different. When q is an integer greater than 2, there exist multiple R. 2 They can be the same or different. When t is an integer greater than 2, there exist multiple R. 9 They can be the same or different.

[0153] It should be noted that R in the above general formula (2) 1 ~R 9 X 1 The preferred methods for p, q, r, t, and k are the same as those in the general formula (1) above. Furthermore, the general formula (i) above corresponds to the general formula (x) above, and R in the general formula (ii) above... 1ii R corresponds to the above general formula (1) 1 R in the above general formula (iii) 1iii R corresponds to the above general formula (1) 1 .

[0154] The number-average molecular weight (Mn) of the polymaleimide compound (A) disclosed herein is preferably in the range of 350 to 2,000, more preferably in the range of 400 to 1,500. Furthermore, the weight-average molecular weight (Mw) of the polymaleimide compound (A) is preferably in the range of 400 to 500,000, more preferably in the range of 450 to 400,000.

[0155] Regarding the polymaleimide compound (A) of this disclosure, considering its excellent low dielectric constant and low dielectric loss tangent, the molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) calculated by gel permeation chromatography (GPC) is preferably in the range of 1.001 to 500, more preferably 1.001 to 400. It should be noted that, according to the GPC curve obtained by GPC, when the molecular weight distribution spans a wide range and contains a high proportion of 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 suppleness can be obtained, which is a preferred approach.

[0156] It should be noted that the number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (weight-average molecular weight (Mw) / number-average molecular weight (Mn)) of the polymaleimide compound (A) in this embodiment were determined by gel permeation chromatography (hereinafter referred to as "GPC") under the measurement conditions described in the examples described later.

[0157] In this embodiment, when the polymaleimide compound (A) contains an indmium skeleton (or a structural unit having an indmium skeleton) as shown in the following general formula (3), the ratio of the indmium skeleton to the total amount (100% by mass) of the polymaleimide compound (A) is preferably 10% by mass or less, preferably 5% by mass or less, more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 0.9% by mass or less.

[0158] [Chemistry 12]

[0159]

[0160] (In the above general formula (3), R) 31 R 32 and R 33 R represents either a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, respectively. 34 Each of the following groups independently represents an alkyl, alkoxy, or alkylthio group having 1 to 10 carbon atoms; an aryl, aryloxy, or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl or mercapto group; q 3 q represents an integer from 0 to 3.3 In the case of integers greater than 2, there exist multiple R. 34 They can be the same or different. Additionally, * indicates a connection to other atoms.

[0161] In the above general formula (3), R 34 Preferably, each alkyl group independently represents 1 to 6 carbon atoms, and more preferably, it represents 1 to 3 carbon atoms. Furthermore, in the above general formula (3), R... 31 R 32 and R 33 Preferably, it contains hydrogen atoms or methyl groups.

[0162] In the curable composition of this embodiment, the polymaleimide compound (A) preferably contains 60% by mass or more and 95% by mass or less, more preferably 70% by mass or more and 93% by mass or less, and most preferably 80% by mass or more and 90% by mass or less, relative to the total curable composition. From the viewpoint of heat resistance, a content of 60% by mass or more and 95% by mass or less of polymaleimide compound (A) is preferred.

[0163] <Method for manufacturing polymaleimide compound (A)>

[0164] The following describes the method for manufacturing the polymaleimide compound (A) disclosed herein.

[0165] The method for preparing the polymaleimide compound (A) of this embodiment is not particularly limited. It can be prepared by any means, as long as an aromatic amine compound (a), an aromatic divinyl compound (b1), and maleic anhydride are used as reactants (1) or the compound has the structural unit shown in the above general formula (1). As an example of the method for preparing the polymaleimide compound (A) of this disclosure, a method including the following steps (1) and (2) can be listed.

[0166] Step (1): The step of reacting an aromatic amine compound (a) with an aromatic divinyl compound (b1) as a reaction raw material (2) to obtain the intermediate amine compound (c) in this embodiment;

[0167] Step (2): The process of reacting the intermediate amine compound (c) obtained in step (1) with maleic anhydride as a reaction raw material (3) to obtain the polymaleimide compound (A) disclosed herein.

[0168] Specifically, the method for manufacturing the polymaleimide compound (A) of this embodiment preferably includes: a step (1) (also called a crosslinking step) in which an aromatic amine compound (a) and an aromatic divinyl compound (b1) are reacted under a solid acid catalyst; and a step (2) (also called a condensation step) in which the intermediate amine compound (c) generated by the above step (1) is condensed with maleic anhydride.

[0169] The following describes each step of the method for manufacturing the polymaleimide compound (A) disclosed herein.

[0170] <<Process (1): Manufacturing process of intermediate amine compound (c)>>

[0171] The manufacturing process of the intermediate amine compound (c) in this embodiment will be described below.

[0172] Step (1) in this embodiment is not particularly limited, and may be a step of reacting the above-mentioned aromatic amine compound (a), the above-mentioned aromatic divinyl compound (b1) (e.g., divinylbenzene), and further, as needed, other compounds such as aromatic monovinyl compound (b2) (e.g., ethylvinylbenzene) in the presence of an acid catalyst. This produces an intermediate amine compound (c).

[0173] As for the mixing ratio of the aromatic amine compound (a) and the aromatic divinyl compound (b1), considering the balance of formability and curability during the manufacture of the resulting cured product, the molar ratio of the aromatic divinyl compound (b1) to 1 mole of the aromatic amine compound (a) is preferably 0.1 to 10 moles, more preferably 0.2 to 3 moles. Furthermore, when using the aromatic monovinyl compound (b2), the total molar ratio of the aromatic divinyl compound (b1) and the aromatic monovinyl compound (b2) to 1 mole of the aromatic amine compound (a) is preferably 0.1 to 10 moles, more preferably 0.2 to 3 moles.

[0174] Furthermore, as a specific method for carrying out the above reaction, a common approach is to charge all the raw materials together and react them directly at a specified temperature; or to charge the aromatic amine compound (a) and the acid catalyst, maintain the reaction at a specified temperature, and simultaneously add the aromatic divinyl compound (b1), other compounds (e.g., the aromatic monovinyl compound (b2)), etc., dropwise while allowing them to react. In this case, the dropwise addition time is typically 0.1 to 12 hours, preferably 6 hours or less. After the reaction, if a solvent is used, the solvent and unreacted substances are removed by distillation as needed to obtain the above-mentioned intermediate amine compound (c); if no solvent is used, the unreacted substances are removed by distillation to obtain the above-mentioned intermediate amine compound (c) as the target compound.

[0175] For the acid catalyst used in step (1) of this embodiment, examples 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, strong acid ion exchange resin, and heteropoly hydrochloric acid. From the viewpoint of processability, it is preferable that the solid acid of the catalyst can be easily removed by filtration after the reaction. When using other acids, it is preferable to perform base-based neutralization and water-based washing after the reaction.

[0176] Regarding the amount of the acid catalyst, relative to 100 parts by mass of the total amount of added raw materials (aromatic divinyl compound (b1) or a mixture of aromatic divinyl compound (b1) and aromatic monovinyl compound (b2) and aromatic amine compound (a)), the acid catalyst is added in the range of 1 to 100 parts by mass. Considering processability and economy, 1 to 60 parts by mass is preferred. The reaction temperature is usually in the range of 100 to 270°C, and in order to suppress the formation of isomer structures and avoid side reactions such as thermal decomposition, 100 to 220°C is preferred.

[0177] In step (1) of this embodiment, the reaction time of the mixture of aromatic divinyl compound (b1) or a mixture of aromatic divinyl compound (b1) and aromatic monovinyl compound (b2) with aromatic amine compound (a), i.e. the crosslinking reaction time, is generally in the range of 1 to 48 hours under the above reaction temperature conditions, and preferably in the range of 1 to 30 hours. Since the reaction will not proceed completely if the time is short, and side reactions such as thermal decomposition of the product will occur if the time is long, the reaction will generally not proceed completely.

[0178] In the method for producing the intermediate amine compound (c) in this embodiment, aniline or its derivatives also serve as a solvent, so it is not necessary to use other solvents, but a solvent may also be used. For example, when the reaction is carried out using divinylbenzene as a raw material, a solvent that can be azeotropically dehydrated, such as toluene, xylene, or chlorobenzene, can be used. The water contained in the catalyst, etc., is azeotropically dehydrated as needed, the solvent is removed by distillation, and then the reaction is carried out within the above-mentioned reaction temperature range.

[0179] The intermediate amine compound (c) obtained by the above process (1) is preferably represented by the following general formula (4).

[0180] [Chemistry 13]

[0181]

[0182] (In the above general formula (4), R) 1 Each independently represents an alkyl group, R 2 Each of these groups independently represents an alkyl, alkoxy, or alkylthio group having 1 to 10 carbon atoms; an aryl, aryloxy, or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; or a hydroxyl or mercapto group.

[0183] R 3 R 4 R 5 and R 6 Each can independently represent a hydrogen atom or a methyl group, and R 3 and R 4 One side is a hydrogen atom and the other side is a methyl group, R 5 and R 6 One side is a hydrogen atom and the other side is a methyl group.

[0184] X 1 The substituents represented by the following general formula (x) are:

[0185] [Chemistry 14]

[0186]

[0187] (In the general formula (x), R) 7 and R 8 Each can independently represent a hydrogen atom or a methyl group, and R 7 and R 8 One side is a hydrogen atom and the other side is a methyl group, R 9 (This indicates an alkyl group, and t represents an integer from 0 to 4.)

[0188] r represents X relative to each connection. 1 X of the benzene ring 1The average of the substitution numbers, where p represents an integer from 1 to 3, q ​​represents an integer from 0 to 4, and k represents an integer from 1 to 100.

[0189] Furthermore, in the above general formula (4), when p is an integer greater than 2, there exist multiple R... 1 They can be the same or different. When q is an integer greater than 2, there exist multiple R... 2 They can be the same or different. When t is an integer greater than 2, there exist multiple R... 9 They can be the same or different.

[0190] It should be noted that R in the above general formula (4) 1 ~R 9 X 1 The preferred forms of , p, q, r, t, and k are the same as those in the general formula (1) above. Additionally, as another preferred form of the intermediate amine compound (c) obtained through the above process (1), a structure in which the N-substituted maleimide group in the above general formula (2), which is also a preferred form of the polymaleimide compound (A), is replaced with an amino group (including -NH2 and substituted amino groups).

[0191] In this embodiment, the amine equivalent of the intermediate amine compound (c) is preferably 172 to 400 g / equivalent, and more preferably 172 to 350 g / equivalent.

[0192] It should be noted that the determination of the amine equivalent of the intermediate amine compound (c) in this specification is set as a value determined by a method based on the neutralization titration method specified in JIS K0070 (1992).

[0193] <<Process (2): Maleimide>>

[0194] In this embodiment, step (2) is a step of reacting the intermediate amine compound (c) obtained in step (1) with maleic anhydride. By performing a maleimide reaction on the amino group (including -NH2 and substituted amino groups) of the intermediate amine compound (c), a chemical structure in which the above-mentioned amino group is substituted with an N-substituted maleimide ring can be formed, thus obtaining the polymaleimide compound (A) of this disclosure.

[0195] In this embodiment, the intermediate amine compound (c) of the above general formula (4) obtained by step (1) is loaded 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, and the solvent is removed by depressurization, thereby obtaining the polymaleimide compound (A) as the target. In addition, a dehydrating agent may be used during the reaction as needed.

[0196] Organic solvents that can be used in step (2) of this embodiment include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone; nonprotic 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. They can be used alone or in combination.

[0197] In step (2) of this embodiment, the preferred method is to mix the intermediate amine compound (c) and maleic anhydride in a ratio of maleic anhydride to the amino equivalent of intermediate amine compound (c) in the range of 1 to 5, more preferably in a ratio of 1 to 3, and react them in an organic solvent in a mass ratio of 0.1 to 10, preferably 0.2 to 5, relative to the total mass of intermediate amine compound (c) and maleic anhydride.

[0198] As catalysts that can be used in step (2) of this embodiment, examples include inorganic salts such as acetates of nickel, cobalt, sodium, calcium, iron, lithium, and manganese, 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, activated clay, acid clay, silica-alumina, zeolite, strong acid ion exchange resins, and heteropolyhydrochloric acid, etc. Toluenesulfonic acid is particularly preferred.

[0199] As the dehydrating agent used in step (2) of this embodiment, examples 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. Acetic anhydride is preferred.

[0200] In step (2) of this embodiment, there are no particular restrictions on the amount of catalyst and dehydrating agent that can be used. Generally, relative to the amino (-NH2)1 equivalent of the intermediate amine compound (c), the catalyst can be used in amounts of 0.0001 to 1.0 moles, preferably 0.01 to 0.3 moles, and the dehydrating agent can be used in amounts of 1 to 3 moles, preferably 1 to 1.5 moles.

[0201] In step (2) of this embodiment, as the reaction conditions for maleimide formation, the above-mentioned intermediate amine compound (c) and maleic anhydride are loaded 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. Then, the above-mentioned catalyst is added and reacted at a temperature range of 90 to 130°C, preferably 105 to 120°C, for 1 to 24 hours, preferably 1 to 10 hours.

[0202] (Amine compound (B))

[0203] The curable composition of this embodiment contains an amine compound (B). By combining this amine compound (B) and the polymaleimide compound (A), the composition as a whole can facilitate low-temperature curing and exhibit excellent molding processability, thus making it useful as a molding material for structural materials. Furthermore, by reacting with the polymaleimide compound (A), it acts as a curing agent, generating three-dimensional cross-links, resulting in a cured product with excellent heat resistance, which is a preferred method.

[0204] As the amine compound (B) in this embodiment, compounds having primary to tertiary amino groups can be listed, preferably hydrocarbons having 1 or more carbon atoms, more preferably hydrocarbons having 3 to 25 carbon atoms, and more preferably hydrocarbon compounds having 2 or more primary amino groups per molecule. As this amine compound (B), aliphatic amine compounds or aromatic amine compounds are preferred, and aliphatic primary diamine compounds or aromatic primary diamine compounds are more preferred.

[0205] It should be noted that aromatic amine compounds include aromatic heterocyclic compounds, and aliphatic amine compounds include alicyclic aliphatic compounds.

[0206] Specific examples of aliphatic amine compounds used in this embodiment include ethylenediamine, diethylenetriamine, hexamethylenediamine, triethylenetetramine, isophoronediamine, guanidine derivatives, guanidineamine derivatives, 1,3-diaminomethylcyclohexane, morpholine, 4,4-methylenebicyclohexaneamine, and 4,4-ethylenebicyclohexaneamine. These aliphatic amine compounds can be used alone or in combination of two or more.

[0207] Specific examples of aromatic amine compounds used in this embodiment include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3-methyl-1,4-diaminobenzene, m-xylenediamine, p-xylenediamine, diethyltoluenediamine, 2,5-dimethyl-1,4-diaminobenzene, diaminodiphenylmethane (e.g., 4,4'-diaminodiphenylmethane), diaminodiphenylethane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, diaminodiphenyl ether (e.g., 4,4'-diaminodiphenyl ether), diaminodiphenyl sulfone (e.g., 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone), 4,4'-diaminodiphenyl ketone, benzidine, 3, 3'-Dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, bis(4-(3-aminophenoxy)phenyl)sulfone, 9,9-bis(4-aminophenyl)fluorene, and imidazole, etc. These aromatic amine compounds can be used alone or in mixtures of two or more.

[0208] Among the aforementioned aromatic amine compounds, when mechanical properties during curing are of primary concern, m-phenylenediamine, p-phenylenediamine, 3-methyl-1,4-diaminobenzene, or 2,5-dimethyl-1,4-diaminobenzene are preferred. On the other hand, when heat resistance is of primary concern, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-bis(4-aminophenoxy)biphenyl, or 2,2-bis(4-(4-aminophenoxy)phenyl)propane are preferred.

[0209] Furthermore, when solubility or processability in solvents is a primary concern, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-diethyl-diphenylmethane, and 2,2-bis(4-(4-aminophenoxy)phenyl)propane are preferred. Moreover, when low dielectric properties are a primary concern, 4,4'-diamino-3,3'-diethyl-diphenylmethane and 2,2-bis(4-(4-aminophenoxy)phenyl)propane are preferred.

[0210] In addition, other amine compounds (B) besides the aforementioned aliphatic amine compounds and aromatic amine compounds can be listed as hydroxyl ammonium sulfate, BF3-amine complex, etc.

[0211] As the preferred amine compound (B) in this embodiment, aromatic amine compounds are preferred when it is important to control the curing reaction and ensure moldability. Aliphatic amine compounds act as catalysts and tend to have a rapid curing reaction; therefore, aromatic amine compounds are preferred when moldability is important.

[0212] In the curable composition of this embodiment, the amine compound (B) preferably contains 5% by mass or more and 50% by mass or less, more preferably 7% by mass or more and 30% by mass or less, and most preferably 10% by mass or more and 20% by mass or less, relative to the total curable composition. From the viewpoint of heat resistance, it is preferable when the content of amine compound (B) is in the range of 10% by mass or more and 20% by mass or less.

[0213] (Curning agent other than amine compound (B))

[0214] In the curing composition of this embodiment, a curing agent (C) other than the amine compound (B) may be added within a range that does not impair the curing properties of the present invention. It should be noted that, relative to 100% by mass of the total curing composition, the curing agent (C) is preferably 2% by mass or more and 20% by mass or less, and most preferably 5% by mass or more and 10% by mass or less. A curing agent (C) content in the range of 5% by mass or more and 10% by mass or less is preferred from the viewpoint of curability and low dielectric loss tangent.

[0215] Examples of curing agents (C) used in this embodiment include cyanate ester compounds, amide compounds, acid anhydride compounds, phenol compounds, polyphenylene ether compounds, compounds with substituents containing unsaturated double bonds, diene polymers, etc. These curing agents can be used alone or in combination of two or more.

[0216] Examples of the aforementioned cyanate compounds include, for example, bisphenol A type cyanate resin, bisphenol F type cyanate resin, bisphenol E type cyanate resin, bisphenol S type cyanate resin, bisphenol sulfide type cyanate resin, phenyl ether type cyanate resin, naphthyl ether type cyanate resin, biphenyl type cyanate resin, tetramethylbiphenyl type cyanate resin, polyhydroxynaphthalene type cyanate resin, phenol phenolic varnish type cyanate resin, cresol phenolic varnish type cyanate resin, triphenylmethane type cyanate resin, tetraphenylethane type cyanate resin, dicyclopentadiene-phenol addition reaction type cyanate resin, phenol aralkyl type cyanate resin, naphthol phenolic varnish type cyanate resin, naphthol aralkyl type cyanate resin, naphthol-phenol cocondensed phenolic varnish type cyanate resin, naphthol-cresol cocondensed phenolic varnish type cyanate resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type cyanate resin, biphenyl modified phenolic varnish type cyanate resin, anthracene type cyanate resin, etc. They can be used individually or in combination of two or more.

[0217] Examples of the aforementioned amide compounds include dicyandiamide and polyamide resins synthesized from dimers of linolenic acid and ethylenediamine.

[0218] Examples of the aforementioned anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.

[0219] Examples of the aforementioned phenolic compounds include phenolic varnish resins, cresol varnish resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resins, dicyclopentadiene phenol addition-type resins, phenol aralkyl resins (Zyloc resins), polyphenolic varnish resins synthesized from polyhydroxy compounds and formaldehyde, represented by resorcinol varnish resins, naphthol aralkyl resins, trimethylolpropane resins, tetraphenol ethane resins, naphthol varnish resins, naphthol-phenol cocondensed phenolic varnish resins, and naphthol. - Cresol cocondensed phenolic varnish resin, biphenyl modified phenolic resin (a multi-functional phenolic compound with a phenol nucleus linked by dimethylene groups), biphenyl modified naphthol resin (a multi-functional naphthol compound with a phenol nucleus linked by dimethylene groups), aminotriazine modified phenolic resin (a multi-functional phenolic compound with a phenol nucleus linked by melamine, benzoguanamine, etc.), and alkoxy-containing aromatic ring modified phenolic varnish resin (a multi-functional phenolic compound with a phenol nucleus linked by formaldehyde and an aromatic ring containing alkoxy groups), etc., are all multi-functional phenolic compounds.

[0220] As the above-mentioned polyphenylene ether compounds, it is preferred, for example, to have the structure shown in the following general formula (5) or (6).

[0221] [Chemistry 15]

[0222]

[0223] [Chemistry 16]

[0224]

[0225] In the above general formulas (5) and (6), R d1 ~R d8 Examples of structures that can be independently listed include hydrogen atoms, alkyl groups with 1 to 5 carbon atoms, alkenyl groups with 1 to 5 carbon atoms, cycloalkyl groups with 3 to 5 carbon atoms, alkoxy groups with 1 to 5 carbon atoms, thioether groups with 1 to 5 carbon atoms, alkyl carbonyl groups with 2 to 5 carbon atoms, alkoxy carbonyl groups with 2 to 5 carbon atoms, alkyl carbonyloxy groups with 2 to 5 carbon atoms, and alkyl sulfonyl groups with 1 to 5 carbon atoms. As terminal structures of the structures in the above general formulas (5) and (6), structures having hydroxyl groups or groups containing reactive double bonds can be listed. Furthermore, v is an integer value from 1 to 30, and w and u are also integer values ​​from 1 to 30.

[0226] There are no particular limitations on the thioether groups with 1 to 5 carbon atoms mentioned above, and examples include methylthio, ethylthio, propylthio, isopropylthio, butylthio, pentylthio, etc.

[0227] There are no particular limitations on the alkyl carbonyl groups with 2 to 5 carbon atoms mentioned above, and examples include methyl carbonyl, ethyl carbonyl, propyl carbonyl, isopropyl carbonyl, butyl carbonyl, etc.

[0228] There are no particular limitations on the alkoxycarbonyl groups with 2 to 5 carbon atoms mentioned above, and examples include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, etc.

[0229] There are no particular limitations on the alkyl carbonyloxy groups with 2 to 5 carbon atoms mentioned above, and examples include methyl carbonyloxy, ethyl carbonyloxy, propyl carbonyloxy, isopropyl carbonyloxy, butyl carbonyloxy, etc.

[0230] There are no particular limitations on the alkyl sulfonyl groups with 1 to 5 carbon atoms mentioned above, and examples include methyl sulfonyl, ethyl sulfonyl, propyl sulfonyl, isopropyl sulfonyl, butyl sulfonyl, pentyl sulfonyl, etc.

[0231] In this embodiment, R in the above general formulas (5) and (6) d1 ~R d8 They may be the same or different from each other, preferably hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, or cycloalkyl groups having 3 to 5 carbon atoms, more preferably hydrogen atoms or alkyl groups having 1 to 5 carbon atoms, even more preferably hydrogen atoms, methyl, or ethyl, and particularly preferably hydrogen atoms or methyl.

[0232] The Y in the above general formula (6) can be listed as a divalent aromatic group from aromatic compounds having two phenolic hydroxyl groups.

[0233] Furthermore, there are no particular limitations on the aromatic compounds having two phenolic hydroxyl groups mentioned above, and examples include catechol, resorcinol, hydroquinone, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol B, bisphenol BP, bisphenol C, bisphenol F, and tetramethylbisphenol A. Among these, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol E, and bisphenol F are preferred, and 4,4'-biphenol, bisphenol A, and tetramethylbisphenol A are more preferred.

[0234] Furthermore, since the two phenolic hydroxyl groups of the aforementioned aromatic compound with two phenolic hydroxyl groups form a phenyl ether bond (the two oxygen atoms connected to Y), Y becomes a divalent aromatic group from the aromatic compound with two phenolic hydroxyl groups. In other words, the group obtained by removing two arbitrary hydrogen atoms from the aforementioned aromatic compound with two phenolic hydroxyl groups is defined as "a divalent aromatic group from the aromatic compound with two phenolic hydroxyl groups".

[0235] As for the above-mentioned compounds having substituents containing unsaturated double bonds, there is no particular limitation as long as the molecule has two or more substituents containing unsaturated bonds. Examples include compounds having allyl, isopropenyl, 1-propenyl, acryloyl, methacryloyl, styryl, styrylmethyl, etc., as the above-mentioned substituents containing unsaturated bonds.

[0236] Examples of diene polymers mentioned above include unmodified diene polymers that have not been modified by polar groups. Here, polar groups are functional groups that affect dielectric properties; examples include phenolic groups, amino groups, and epoxy groups. There are no particular limitations on the diene polymers mentioned above; for example, 1,2-polybutadiene and 1,4-polybutadiene can be used.

[0237] As the diene-based polymers mentioned above, homopolymers of butadiene in which more than 50% of the butadiene units in the polymer chain are 1,2-bonded, and their derivatives may also be used.

[0238] (Other resins (D))

[0239] Furthermore, other resins (D) may be included in addition to the polymaleimide compound (A) and the amine compound (B), provided that this does not impair the purpose of this disclosure. As such other resins (D), suitable formulations may include bismaleimides other than the aforementioned polymaleimide compound (A), allyl ether compounds, allyl amine compounds, triallyl cyanurate, alkenylphenol compounds, vinyl-containing polyolefin compounds, epoxy resins, phenolic resins, reactive ester resins, polyphenylene ether resins, benzoxazine resins, styrene-maleic anhydride copolymers, polybutadiene and its modified forms, polyacetal resins, polyvinyl alcohol resins, liquid crystal polymers, fluoropolymers, polystyrene, polyethylene, polyimide resins, thermosetting polyimide resins, silicone, silicone oil, etc.

[0240] Furthermore, since the curable composition of this embodiment contains an amine compound (B), epoxy resin can be selected as the other resin (D). Thus, in the curable composition containing polymaleimide compound (A), amine compound (B), and epoxy resin, the amine compound (B) acts as a curing agent, thereby improving adhesion to copper, which is useful, for example, in the manufacture of circuit boards using copper foil.

[0241] The term "epoxy resin" is not specifically limited to any particular type. Examples include phenolic varnish-type epoxy resins such as phenolic resin, cresol varnish-type epoxy resin, α-naphthol varnish-type epoxy resin, β-naphthol varnish-type epoxy resin, bisphenol A varnish-type epoxy resin, and biphenyl varnish-type epoxy resin; aralkyl-type epoxy resins such as phenolic aryl alkyl-type epoxy resin, naphtholic aryl alkyl-type epoxy resin, and phenolic biphenyl aryl alkyl-type epoxy resin; and bisphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and tetrabromobisphenol A type epoxy resin. Biphenyl-type epoxy resins include benzene-type epoxy resins, tetramethylbiphenyl-type epoxy resins, biphenyl backbones, and epoxy resins with a diglycidyloxybenzene backbone; naphthalene-type epoxy resins; binatol-type epoxy resins; binatol-type epoxy resins; dicyclopentadiene-phenol-type epoxy resins; tetraglycidyldiaminodiphenylmethane-type epoxy resins, triglycidyl-p-aminophenol-type epoxy resins, and diaminodiphenyl sulfone glycidylamine-type epoxy resins; diglycidyl ester-type epoxy resins include 2,6-naphthalenedicarboxylic acid diglycidyl ester-type epoxy resins and hexahydrophthalic anhydride glycidyl ester-type epoxy resins; and benzopyran-type epoxy resins include dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran. These can be used individually or in combination of two or more types.

[0242] The content of other resins (D) relative to 100% by mass of the total curable composition is preferably 2% by mass or more and 20% by mass or less, and most preferably 5% by mass or more and 10% by mass or less. A content of other resins (D) in the range of 5% by mass or more and 10% by mass or less is preferred from the viewpoint of heat resistance.

[0243] (Curing accelerator)

[0244] The curing composition of this embodiment can also be appropriately combined with a curing accelerator as needed. Various substances can be used as the curing accelerator; for example, adding polymerization initiators such as organic peroxides and azo compounds, or basic catalysts such as phosphine compounds and tertiary amines is effective. Specific examples of the curing accelerator include benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, TPP-MK, TPP-K, triethylamine, imidazoles, etc. The curing accelerator can be used alone or in combination with two or more. The preferred amount of the curing accelerator in this embodiment is 0.05% to 5% by mass of the total curing resin composition.

[0245] (additive)

[0246] The curable composition of this embodiment may also be appropriately combined with additives as needed. Examples of such additives include silane coupling agents, release agents, pigments, emulsifiers, non-halogenated flame retardants, inorganic fillers, flame retardants, and solvents. The content of the additives relative to 100% by mass of the total curable composition is preferably 1% by mass or more and 20% by mass or less, and most preferably 3% by mass or more and 10% by mass or less.

[0247] Examples of flame retardants include inorganic phosphorus-based flame retardants, organophosphorus-based flame retardants, halogen-based flame retardants, and non-halogen-based flame retardants. In the curable composition of this embodiment, to achieve flame retardancy without compromising the intended purpose, it is more preferable to incorporate a non-halogen-based flame retardant that substantially does not contain halogen atoms. Examples of such non-halogen-based flame retardants include phosphorus-based flame retardants, nitrogen-based flame retardants, organosilicon-based flame retardants, inorganic flame retardants, and organometallic salt-based flame retardants, which can be used alone or in combination.

[0248] In the curable composition of this embodiment, inorganic fillers can be added as needed. Examples of such inorganic fillers include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Especially when the amount of the aforementioned inorganic filler is set to be particularly large, fused silica is preferred. The fused silica can be either crushed or spherical; to increase the amount of fused silica and suppress the increase in the melt viscosity of the molding material, spherical fused silica is preferred. Furthermore, to increase the amount of spherical silica, the particle size distribution of the spherical silica is preferably appropriately adjusted. Regarding its filling rate, considering flame retardancy, a high rate is preferred, particularly 30% by mass or more and 50% by mass or less relative to the total amount of the curable composition. Additionally, when the above-mentioned curable composition is used for applications such as conductive pastes detailed below, conductive fillers such as silver powder and copper powder can be used.

[0249] In the curable composition of this embodiment, the lower limit of the total content of polymaleimide compound (A) and amine compound (B) relative to the total curable composition (100% by mass) is preferably 40%, 42%, 45%, 47%, 48%, or 50% by mass. Furthermore, the upper limit of the above-mentioned total content is preferably 100%, 99%, 98%, or 97% by mass. The above-mentioned upper and lower limits can be combined arbitrarily. Therefore, for example, in the curable composition of this embodiment, the total content of polymaleimide compound (A) and amine compound (B) relative to the total curable composition (100% by mass) is preferably 40% by mass or more and 100% by mass or less, the total content of polymaleimide compound (A) and amine compound (B) is more preferably 45% by mass or more and 100% by mass or less, and the total content of polymaleimide compound (A) and amine compound (B) is even more preferably 50% by mass or more and 100% by mass or less.

[0250] In the curable composition of this embodiment, the lower limit of the total content of polymaleimide compound (A), amine compound (B), and inorganic filler relative to the total curable composition (100% by mass) is preferably 70%, 73%, 75%, 77%, or 80% by mass. Furthermore, the upper limit of the above total content is preferably 100%, 99%, 98%, or 97% by mass. The above upper and lower limits can be arbitrarily combined in the same way as the range of the total content of polymaleimide compound (A) and amine compound (B).

[0251] In the curable composition of this embodiment, the lower limit of the total content of polymaleimide compound (A), amine compound (B), and additives relative to the total curable composition (100% by mass) is preferably 43%, 45%, 48%, 50%, or 53% by mass. Furthermore, the upper limit of the above total content is preferably 100%, 99%, 98%, or 97% by mass. The above upper and lower limits can be arbitrarily combined in the same way as the range of the total content of polymaleimide compound (A) and amine compound (B).

[0252] [cured material]

[0253] The cured product disclosed herein is preferably obtained from the above-described curable composition. The cured product can be obtained by subjecting the above-described curable composition to a curing reaction. The above-described curable composition can be obtained by uniformly mixing the above-described components (e.g., curing agent, compounding agent), and the cured product can be easily prepared using methods similar to those known in the past. Examples of the above-described cured products include laminates, castings, adhesive layers, coatings, films, and other molded cured products.

[0254] The aforementioned curing (thermal curing) reaction can be easily carried out without a catalyst, but for a faster reaction, the addition of polymerization initiators such as organic peroxides and azo compounds, or basic catalysts such as phosphine compounds and tertiary amines, is effective. Examples include benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, and imidazoles, preferably in amounts of 0.05 to 5% by mass of the total curable resin composition.

[0255] [Heat-resistant materials and electronic materials]

[0256] The cured product obtained from the curable composition containing polymaleimide compound (A) and amine compound (B) disclosed herein possesses excellent low moisture absorption and low dielectric properties, making it suitable for use in heat-resistant components or electronic components. It is particularly suitable for use in prepregs, circuit boards, semiconductor sealants, semiconductor devices, multilayer films, multilayer substrates, adhesives using conductive pastes, and photoresist materials. Furthermore, it is suitable as a matrix resin for fiber-reinforced resins, and is particularly suitable as a prepreg with high heat resistance or low dimensional change rate. In addition, the polymaleimide compound (A) contained in the above-mentioned curable composition exhibits excellent solubility in various solvents, thus enabling coating. The heat-resistant components and electronic components thus obtained are suitable for a wide range of applications, including, but not limited to, industrial machinery parts, general machinery parts, automotive / railway / vehicle parts, aerospace-related parts, electronic / electrical parts, building materials, container / packaging components, consumer goods, sports / leisure products, and wind power generation housing components.

[0257] Hereinafter, representative articles (circuit boards, semiconductor sealing materials, semiconductor devices, prepregs, multilayer substrates, multilayer films, conductive pastes) manufactured using the curable resin compositions of the present invention will be described by way of example.

[0258] [Circuit board]

[0259] This disclosure pertains to a circuit board as a laminate of the prepreg and copper foil described below. As a method for obtaining a printed circuit board from the curable composition of this embodiment, an example is to laminate the prepreg using conventional methods, appropriately overlap the copper foil, and heat and press it at 170-300°C for 10 minutes to 3 hours under a pressure of 1-10 MPa.

[0260] [Semiconductor sealing materials]

[0261] This disclosure pertains to a semiconductor sealing material containing the curable composition of this embodiment. The semiconductor sealing material obtained using the curable composition of this embodiment exhibits improved hygroscopicity and low dielectric loss tangent through the use of the polymaleimide compound (A) and amine compound (B) of this disclosure. Therefore, it possesses excellent processability, moldability, and reflow resistance during the manufacturing process, making it a preferred method.

[0262] The curable composition of this embodiment used in the aforementioned semiconductor sealing material may contain an inorganic filler. It should be noted that the filling rate of the inorganic filler, relative to 100 parts by weight of the curable composition of this embodiment, may be, for example, in the range of 0.5 to 1200 parts by weight. Furthermore, as described above, examples of such inorganic fillers include barium sulfate, barium titanate, amorphous silica, crystalline silica, Noiburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, alumina, aluminum hydroxide, silicon nitride, and aluminum nitride.

[0263] As a method for obtaining the aforementioned semiconductor sealing material, methods can be listed such as using an extruder, kneader, roller, etc., to further melt and uniformly mix the curing accelerator and / or additive, which are arbitrary components, in the curable composition of this embodiment as needed. When used as a high thermal conductivity semiconductor sealing material for power transistors and power ICs, highly filled materials such as crystalline silica, alumina, and silicon nitride, which have a thermal conductivity higher than fused silica, or fused silica, crystalline silica, alumina, and silicon nitride, can be used. Regarding its filling rate, inorganic fillers are preferably used in the range of 30 to 95 parts by mass relative to 100 parts by mass of the curable composition. More preferably, 70 parts by mass or more is used to improve flame retardancy, moisture resistance, solder crack resistance, and reduce the coefficient of linear expansion. More preferably, 80 parts by mass or more is used.

[0264] [Semiconductor Devices]

[0265] This disclosure pertains to a semiconductor device comprising a cured semiconductor sealing material as described above. Semiconductor devices obtained using the semiconductor sealing material derived from the curable composition of this embodiment exhibit low viscosity and excellent flowability due to the use of the polymaleimide compound (A) and amine compound (B) of this disclosure. Furthermore, they exhibit improved hygroscopicity, thermoelastic modulus, and adhesion to metallic materials, resulting in excellent processability, moldability, and reflow resistance during manufacturing, making them a preferred method.

[0266] As a method for obtaining the above-mentioned semiconductor device, one example is to use a casting or transfer molding machine, an injection molding machine, or the like to mold the semiconductor sealing material, and then heat and cure it in a temperature range of room temperature (20°C) to 250°C.

[0267] [Prepreg]

[0268] This disclosure pertains to a prepreg having a reinforcing substrate and a curable composition of this embodiment impregnated in the reinforcing substrate. A method for obtaining the prepreg from the curable composition described above can be listed as follows: The curable composition, which has been varnished, is impregnated in a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass fiber untwisted yarn, etc.) using an organic solvent described later. The substrate is then heated at a temperature corresponding to the type of solvent used, preferably 50 to 170°C, to partially cure (or not cure) the curable composition, thereby obtaining the prepreg. The mass ratio of the curable composition to the reinforcing substrate used in this process is not particularly limited, but it is generally preferred that the resin content in the composition of the prepreg is 20 to 60% by mass.

[0269] 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, preventing it from completing. Furthermore, the semi-cured product may have a degree of curing of 5% or less (below 85%). On the other hand, the cured product in this embodiment may have a higher degree of curing than the semi-cured product.

[0270] It should be noted that the degree of curing of the semi-cured product can be determined by DSC measurement of the heat release during the curing of the curable composition and the heat release during the curing of its semi-cured product, and calculated by the following formula.

[0271] Degree of Curing (%) = [1 - (Heat release during curing of the semi-cured product / Heat release during curing of the curable composition)] × 100

[0272] Examples of organic solvents used in the manufacture of the prepreg in this embodiment include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diethylene glycol acetate, and propylene glycol monomethyl ether acetate. The selection and appropriate amount of these solvents can be chosen according to the intended use. For example, in the case of further manufacturing a printed circuit board from the prepreg as described below, polar solvents with a boiling point of 160°C or lower, such as methyl ethyl ketone, acetone, and dimethylformamide, are preferred. Furthermore, the non-volatile components are preferably used at a ratio of 40-80% by mass. Additionally, the reinforcing substrate used in the manufacture of the prepreg in this embodiment can be woven fabric, nonwoven fabric, felt, or paper made of inorganic or organic fibers such as glass fiber, polyester fiber, or polyamide fiber; these can be used individually or in combination.

[0273] The heat treatment conditions for the prepreg in this embodiment can be appropriately selected according to the type and amount of organic solvent, catalyst, and various additives used, and are usually carried out at a temperature of 80 to 220°C for 3 to 30 minutes.

[0274] [Laminated substrate]

[0275] As a method for obtaining a multilayer substrate from the curable composition of this embodiment, the following steps 1 to 3 can be described. In step 1, firstly, the curable composition, appropriately incorporating rubber, fillers, etc., is applied to a circuit board on which a circuit is formed using a spraying method, curtain coating method, etc., and then cured. In step 2, as needed, predetermined through-holes, etc., are made on the circuit board coated with the curable composition, then treated with a roughening agent, and its surface is washed with hot water to create an uneven surface on the substrate, and then a metal such as copper is plated. In step 3, the operations of steps 1 to 2 are repeated sequentially as desired, alternately layering resin insulating layers and conductor layers with predetermined circuit patterns to form a multilayer substrate. It should be noted that in the above steps, the through-holes can be made after the outermost resin insulating layer is formed. Furthermore, regarding the multilayer substrate in this embodiment, by heating and pressing a resin-containing copper foil, which is formed by semi-curing the composition on a copper foil, onto a wiring substrate on which a circuit is formed, a roughened surface can also be formed, eliminating the need for a plating process, and thus producing a multilayer substrate.

[0276] [Laminated membrane]

[0277] This disclosure pertains to a multilayer film containing the curable composition of this embodiment. A method for manufacturing the multilayer film of this embodiment can be exemplified by the following steps: applying the curable composition onto a support film (Y), drying it, forming a layer of the curable composition on the support film (Y), and thus producing an adhesive film for a multilayer printed circuit board.

[0278] When manufacturing a multilayer film from a curable composition, it is important that the film softens under the lamination temperature conditions (typically 70–140°C) in a vacuum lamination process. During lamination onto the circuit board, it should exhibit good flowability (resin flow) to fill the vias or through holes present in the circuit board. It is preferable to combine the aforementioned components in a manner that exhibits such characteristics. It should be noted that, in order to prevent localized differences in characteristic values ​​caused by phase separation or other factors, the resulting multilayer film and circuit board (such as a copper-clad laminate) should exhibit consistent performance at any given location, requiring uniform appearance.

[0279] Here, the diameter of the through-hole in the multilayer printed circuit board is typically 0.1–0.5 mm, and the depth is typically 0.1–1.2 mm. It is generally preferred that resin filling be performed within this range. It should be noted that when laminating both sides of the circuit board, it is preferable to fill approximately 1 / 2 of the through-hole.

[0280] Regarding the method for manufacturing the aforementioned adhesive film, specifically, after preparing the aforementioned curable composition in the form of a varnish, the varnish-like composition is coated onto the surface of a support film (Y), and then dried by heating or hot air blowing to form a composition layer (X) composed of the curable composition, thereby enabling the manufacture. As the aforementioned organic solvent, ketones such as acetone, methyl ethyl ketone, and cyclohexanone are preferably used, as well as ethyl acetate, butyl acetate, cellolytic acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and other acetates, cellolytic agents, carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone, etc. Furthermore, it is preferable to use a proportion of 30 to 60% by mass for the non-volatile components.

[0281] The thickness of the formed composition layer (X) is preferably greater than or equal to the thickness of the conductor layer. Since the thickness of the conductor layer in a circuit board is typically in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm. It should be noted that the composition layer (X) in this embodiment can be protected by the protective film described later. By using the protective film, the adhesion of dust, scratches, etc., to the surface of the resin composition layer can be prevented.

[0282] The aforementioned support film (Y) and protective film can be categorized as polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate; polycarbonate; polyimide; and metal foils such as release paper, copper foil, and aluminum foil. It should be noted that, in addition to matte treatment and corona treatment, the support film and protective film can also undergo release treatment. The thickness of the support film is not particularly limited, typically ranging from 10 to 150 μm, preferably in the range of 25 to 50 μm. Furthermore, the thickness of the protective film is preferably set to 1 to 40 μm.

[0283] The aforementioned support film (Y) is peeled off after being laminated onto the circuit board or after forming an insulating layer through heat curing. Peeling off the support film (Y) after the adhesive film has been heat-cured prevents the adhesion of dust and other contaminants during the curing process. When peeling is performed after curing, the support film is typically pre-treated with a demolding process.

[0284] It should be noted that multilayer printed circuit boards can be manufactured from the laminated film obtained as described above. For example, when the resin composition layer (X) is protected by a protective film, after peeling it off, the resin composition layer (X) is laminated onto one or both sides of the circuit board in a manner that allows direct contact with the circuit board, for example, by vacuum lamination. The lamination method can be intermittent or continuous using rollers. Additionally, the laminated film and the circuit board can be heated (preheated) as needed before lamination. Regarding lamination conditions, the lamination temperature is preferably set to 70–140°C, and the lamination pressure is preferably set to 1–11 kgf / cm². 2 (9.8×10 4 ~107.9×10 4 N / m 2 It is preferable to perform lamination under reduced pressure, with the air pressure set to below 20 mmHg (26.7 hPa).

[0285] <Conductive Paste>

[0286] As a method for obtaining conductive paste from the curable composition of the present invention, for example, a method of dispersing conductive particles in the composition can be listed. The above-mentioned conductive paste can be formulated into a circuit connection paste resin composition or an anisotropic conductive adhesive, depending on the type of conductive particles used.

[0287] [Example]

[0288] The present invention will be specifically illustrated by examples and comparative examples. Unless otherwise specified, "parts" and "%" refer to mass. It should be noted that the physical properties of the synthesized polymaleimide compound (A) were determined as follows, as shown in Table 1.

[0289] (1) Amine equivalent

[0290] The amine equivalent of intermediate amine compound (c) was determined by the following method.

[0291] In a 500 mL Erlenmeyer flask with a stopper, accurately weigh approximately 2.5 g of the intermediate amine compound (c), 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine as the sample. Then, install a cooling tube and heat under reflux in an oil bath set at 120 °C for 150 minutes.

[0292] After cooling, add 5.0 mL of distilled water, 100 mL of propylene glycol monomethyl ether, and 75 mL of tetrahydrofuran. Titrate with 0.5 mol / L potassium hydroxide-ethanol solution using potentiometric titration. Perform a blank test using the same method to correct the titration.

[0293] Amine equivalent (g / equivalent) = (S × 2,000) / (Blank-A)

[0294] S: Amount of sample (g)

[0295] A: Volume (mL) of 0.5 mol / L potassium hydroxide-ethanol solution consumed.

[0296] Blank: Volume (mL) of 0.5 mol / L potassium hydroxide-ethanol solution consumed in the blank test.

[0297] (2) GPC determination

[0298] Using the following measuring apparatus and conditions, the number-average molecular weight (Mn), weight-average molecular weight (Mw), and molecular weight distribution (Mw / Mn) of the polymaleimide compound (A) obtained in the examples and comparative examples were calculated.

[0299] "Measuring device"

[0300] "HLC-8320GPC" manufactured by TOSOH Co., Ltd.

[0301] "Measurement conditions"

[0302] Column: Guard column "HXL-L" made by TOSOH Co., Ltd. + "TSK-GEL G2000HXL" made by TOSOH Co., Ltd. + "TSK-GEL G2000HXL" made by TOSOH Co., Ltd. + "TSK-GEL G3000HXL" made by TOSOH Co., Ltd. + "TSK-GEL G4000HXL" made by TOSOH Co., Ltd.

[0303] Detector: RI (Differential Refractometer)

[0304] Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by TOSOH Corporation

[0305] Measurement conditions: column temperature 40℃

[0306] Expand solvent tetrahydrofuran

[0307] Flow rate 1.0 ml / min

[0308] Standard: According to the above-mentioned "GPC Workstation EcoSEC-WorkStation" test manual, use the following monodisperse polystyrene with a known molecular weight.

[0309] (Using polystyrene)

[0310] "A-500" manufactured by TOSOH Co., Ltd.

[0311] "A-1000" made by TOSOH Co., Ltd.

[0312] "A-2500" manufactured by TOSOH Co., Ltd.

[0313] "A-5000" manufactured by TOSOH Co., Ltd.

[0314] "F-1" manufactured by TOSOH Co., Ltd.

[0315] "F-2" manufactured by TOSOH Co., Ltd.

[0316] "F-4" manufactured by TOSOH Co., Ltd.

[0317] "F-10" manufactured by TOSOH Co., Ltd.

[0318] "F-20" manufactured by TOSOH Co., Ltd.

[0319] "F-40" manufactured by TOSOH Co., Ltd.

[0320] "F-80" manufactured by TOSOH Co., Ltd.

[0321] "F-128" manufactured by TOSOH Co., Ltd.

[0322] Sample: 50 μl of a tetrahydrofuran solution containing 1.0% by weight of polymaleimide compound (A) obtained in the synthesis example was filtered through a microfilter.

[0323] (3) FD-MS determination

[0324] The polymaleimide compound (A) obtained in the examples was determined by FD-MS chromatography using the following assay apparatus and assay conditions.

[0325] Measurement device: JMS-T100GC AccuTOF

[0326] Measurement conditions

[0327] Measurement range: m / z = 4.00~2000.00

[0328] Rate of change: 51.2 mA / min

[0329] Final current value: 45mA

[0330] Cathode voltage: -10kV

[0331] Recording interval: 0.07 sec

[0332] (4) 13 C-NMR determination

[0333] The polymaleimide compound (A) obtained in the examples has a 1 3 C-NMR chromatography was performed using the following apparatus and under the following conditions.

[0334] 13 C-NMR: "JNM-ECZ400S" manufactured by JEOL RESONANCE

[0335] Resonant frequency: 100MHz

[0336] Total number of times: 4000

[0337] Solvent: Chloroform-d

[0338] Sample concentration: 12% by mass

[0339] Buffer reagent: Chromium acetylacetonate (III)

[0340] (5) Synthesis of polymaleimide compound (A)

[0341] <Synthetic Example 1> Synthesis of polymaleimide compound (A-1)

[0342] (I) Synthesis of intermediate amine compound (c-1)

[0343] In a flask equipped with a thermometer, cooling tube, Dean-Stokes water separator, and stirrer, 242.4 g (2.0 mol) of 2-ethylaniline, 242 g of xylene, and 80 g of activated clay were added. The mixture was heated to 130°C with stirring and maintained for 30 minutes. Then, 272.0 g of DVB-810 (a mixture of divinylbenzene / ethylstyrene (divinylbenzene / ethylstyrene = 81 / 19 (mol)%), manufactured by JITCO Chemical & Materials) was added dropwise over 2 hours, allowing the reaction to proceed directly for 1 hour. The temperature was then raised to 190°C over 6 hours and maintained for 10 hours. After the reaction, the mixture was cooled to 100°C with air, diluted with 300 g of toluene, and the activated clay was removed by filtration. Solvent and unreacted low-molecular-weight substances were removed by distillation under reduced pressure to obtain the intermediate amine compound (c-1). The amine equivalent of the intermediate amine compound (c-1) was 214 g / equivalent.

[0344] (II) Maleimide

[0345] In a 2L flask equipped with a thermometer, cooling tube, Dean-Stokes separator, and stirrer, 117.7 g (1.2 mol) of maleic anhydride and 700 g of toluene were added and stirred at room temperature. Next, a mixed solution of 214 g (1 equivalent) of intermediate amine compound (c-1) and 175 g of DMF was added dropwise over 1 hour, and the reaction was allowed to proceed for 2 hours. Then, 37.1 g of p-toluenesulfonic acid monohydrate was added to the reaction solution, and the mixture was heated to 115°C and azeotropically refluxed. After cooling and separating the water and toluene, only the toluene was returned to the system for dehydration reaction for 5 hours. After cooling to room temperature, the mixture was neutralized with 49% NaOH. Then, toluene and water were removed by vacuum distillation at 60°C, and 600 g of MEK (methyl ethyl ketone) was added to the remaining DMF solution in the flask. The solution was then heated to 60°C and subjected to three separate treatments with 200 g of deionized water to remove salts from the solution. After further addition of sodium sulfate and drying, the mixture was concentrated under reduced pressure and then dried under vacuum at 80°C to obtain the polymaleimide compound (A-1). The chemical structure and properties of this polymaleimide compound (A-1) were determined using GPC, FD-MS, and... 13 Confirmed by C-NMR. The measurement results are shown below. Figures 1A to 1C In addition, according to GPC measurements, the Mn of the polymaleimide compound (A-1) is 998, the Mw is 367,834, and the Mw / Mn ratio is 368.697.

[0346] <Examples 1-2 and Comparative Examples 1-2>

[0347] <<Preparation of Curable Compositions and Production of Cured Products>>

[0348] The polymaleimide compound (A-1) obtained in Synthesis Example 1 above, comparative maleimide (1) ("BMI-2300", manufactured by Yamato Chemical Industry Co., Ltd.), comparative maleimide (2) ("BMI-5100", manufactured by Yamato Chemical Industry Co., Ltd.), amine compound (B-1) (4,4'-diaminodiphenylmethane (manufactured by Tokyo Chemical Industry Co., Ltd.)) as amine compound (B), amine compound (B-2) (4,4'-methylenebis(2-ethyl-6-methylaniline)), and DCPO ("PERCUMYL D", manufactured by Nippon Oil Co., Ltd., Dicumyl Peroxide) as curing catalyst were prepared in the proportions shown in Table 1 below to prepare the curable compositions of Examples 1-2 and Comparative Examples 1-3.

[0349] Next, the curable compositions of Examples 1-2 and Comparative Examples 1-3 were cured under the following curing conditions to produce cured products corresponding to the curable compositions of Examples 1-2 and Comparative Examples 1-3, respectively. Furthermore, the physical properties of dielectric constant, dielectric loss tangent, and hygroscopicity were evaluated using the methods described below. The results are shown in Table 1.

[0350] <<Curing Conditions>>

[0351] After curing at 200°C for 2 hours using a vacuum press, it is then cured at 250°C for another 2 hours.

[0352] Thickness of the formed plate: 1.3mm

[0353] <<Evaluation of Dielectric Constant and Dielectric Loss Tangent>>

[0354] According to JIS-C-6481, using an Agilent Technologies E8362C network analyzer, the dielectric constant (Dk) and dielectric loss tangent (Df) of a test piece after being dried and stored indoors at 23°C and 50% humidity for 24 hours were determined at 10 GHz by the void resonance method.

[0355] <<Evaluation of Hygroscopicity>>

[0356] In this embodiment / comparative example, as an evaluation method for low hygroscopicity, the hygroscopicity rate (%) was calculated and evaluated using the following method.

[0357] For test pieces with dimensions of 5mm×55mm×1.3mm cut from the cured material obtained above, the moisture absorption rate (%) was calculated using the following formula after being kept in a high-pressure steam tester at 85°C, 85%RH, and 1 atmosphere for 50 hours, and then evaluated.

[0358] Moisture absorption rate (%) = (mass of the test piece after the test - mass of the test piece before the test) / (mass of the test piece before the test) × 100 [Table 1]

[0359]

[0360] The results shown in Table 1 above confirm that, when comparing Examples 1-2 and Comparative Examples 1-3, the curable compositions containing polymaleimide compound (A) and amine compound (B) of Examples 1-2 achieved low dielectric constant, low dielectric loss tangent, and low moisture absorption under high temperature and humidity conditions. Furthermore, it was confirmed that, even in frequency bands above Sub6, the curable compositions containing polymaleimide compound (A) and amine compound (B) of Examples 1-2 maintained a high level of balance between low moisture absorption, low dielectric constant, and low dielectric loss tangent during curing.

[0361] [Industry availability]

[0362] According to this disclosure, it is possible to provide curable compositions and cured products that exhibit low dielectric properties and low moisture absorption upon curing.

Claims

1. A curable composition characterized by comprising: A poly-maleimide compound (A) containing a monocyclic or condensed polycyclic aromatic group to which two or more straight-chain or branched alkylene groups are attached, and an amine compound (B), The poly-maleimide compound (A) has a structural unit represented by the following general formula (1), In the above general formula (1), R 1 respectively and independently represent an alkyl group, R 2 each independently represents an alkyl, alkoxy or alkylthio group having 1 to 10 carbon atoms; an aryl, aryloxy 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, R 3 , R 4 , R 5 , and R 6 each independently represent a hydrogen atom or a methyl group, and one of R 3 and R 4 is a hydrogen atom and the other is a methyl group, one of R 5 and R 6 is a hydrogen atom and the other is a methyl group, X 1 represents a substituent represented by General Formula (x) below, In General Formula (x), R 7 and R 8 each independently represent a hydrogen atom or a methyl group, and one of R 7 and R 8 is a hydrogen atom and the other is a methyl group, R 9 each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group or an alkylthio group; 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, and t represents an integer of 0 to 4, r is the average value of the number of X 1 substituted per 1 phenyl ring having X 1 , and represents a number of 1 to 4, p represents an integer of 1 to 3, q represents an integer of 0 to 4, and k represents an integer of 1 to 100.

2. A cured product of the curable composition according to claim 1.

3. A prepreg having a reinforcing base material and a semi-cured product of the curable composition according to claim 1 impregnated in the reinforcing base material.

4. A circuit board which is a laminate of the prepreg according to claim 3 and a copper foil.

5. A build-up film containing the curable composition according to claim 1.

6. A semiconductor sealing material containing the curable composition according to claim 1.

7. A semiconductor device comprising a cured product of the semiconductor sealing material according to claim 6.

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