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

Abstract

The purpose of this disclosure is to provide curable compositions, cured products, prepregs, circuit boards, multilayer films, semiconductor sealing materials, and semiconductor devices that exhibit low dielectric loss tangent and low moisture absorption upon curing. This disclosure pertains to a curable composition characterized by containing a polymaleimide compound (A) and an unsaturated hydrocarbon compound (B) having a reactive double bond, wherein the polymaleimide compound (A) contains a monocyclic or condensed polycyclic aromatic group attached to two or more straight-chain or branched alkylene groups.

Description

Technical Field

[0001] This disclosure relates to curable compositions, cured products, prepregs, circuit boards, multilayer films, semiconductor sealing materials, 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 heating and curing the prepregs, and multilayer boards obtained by combining the laminates and the prepregs and heating and curing them are widely used as circuit board materials for electronic devices. Among them, as the packaging substrate, which serves as an interposer for mounting semiconductors, continues to become thinner, warpage of the packaging substrate during mounting has become a problem. Therefore, materials with high heat resistance are needed to suppress warpage of the packaging substrate 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 that combine heat resistance with low dielectric constants and low dielectric loss tangents 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 and dielectric loss tangent) do not meet the levels required for advanced materials applications.

[0004] For example, Patent Document 1 discloses a thermosetting 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 composition in Patent Document 1 does not discuss the dielectric loss tangent, so the dielectric constant and dielectric loss tangent do not reach the level required for advanced material applications, and the low hygroscopicity at high temperatures is not taken into account in conjunction with the low dielectric constant and low dielectric loss tangent.

[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 sealing material 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 conducted in-depth research and found that by using a curable composition containing a polymaleimide compound (A) and an unsaturated hydrocarbon compound (B) with reactive double bonds, wherein the polymaleimide compound (A) contains a monocyclic or condensed polycyclic aromatic ring with two or more straight-chain or branched alkylene groups, it is possible to achieve a high level of balance between hygroscopicity during curing and low dielectric loss tangent and low dielectric constant, thus 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 sealing materials, and semiconductor devices can be provided that achieve a high level of balance between 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

[0015] Figure 1A The image shows the GPC chromatogram of polymaleimide compound (A-1), representing the GPC measurement results of polymaleimide compound (A-1) in this example.

[0016] Figure 1B The image shows the FD-MS chromatogram of polymaleimide compound (A-1), representing the FD-MS determination results of polymaleimide compound (A-1) in this embodiment.

[0017] Figure 1C For polymaleimide compound (A-1) 13 The C-NMR spectrum shows the polymaleimide compound (A-1) of this embodiment. 13 C-NMR measurement results. Detailed Implementation

[0018] 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.

[0019] [the term]

[0020] In this specification, "reaction material" refers to a compound that partially constitutes the chemical structure of the target compound and is used to obtain the target compound through a chemical reaction such as combination or decomposition. It does not include substances such as solvents and catalysts that act as auxiliaries in the chemical reaction. Specifically, "reaction material" in this specification refers to, for example, when a polymaleimide compound (A) is used as the target, a precursor used to obtain the polymaleimide compound (A) or its precursor compound (e.g., an intermediate amine compound (c) obtained by linking the aforementioned aromatic amine compounds (a) to each other via the aforementioned aromatic divinyl compound (b1)).

[0021] 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, for the "aromatic group" in this specification, the hydrogen atoms of the aromatic ring in the aromatic group may be replaced by substituents (e.g., alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, or halogen atoms). Additionally, the "aromatic group" includes heteroaromatic groups, and the -CH2- or -CH= in the "aromatic group" may be replaced by -O-, -S-, or -N= in a non-adjacent manner.

[0022] Examples of aromatic rings include monocyclic aromatic rings and condensed polycyclic aromatic rings. 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, teridine, coumarin, indole, benzimidazole, benzofuran, and acridine. Furthermore, the hydrogen atoms in the aromatic ring of the aromatic group can be substituted, for example, with alkyl, alkenyl, alkoxy, aryl, aralkyl, or halogen atoms having 1 to 10 carbon atoms.

[0023] 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 any two 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.

[0024] 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, for example, with 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 any one hydrogen atom from the aforementioned "aralkyl" group.

[0025] In this specification, "alkyl" can be any of the straight-chain, branched, or cyclic forms, such as 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.

[0026] In this specification, "cycloalkyl" may include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, methylcyclobutyl, norbornenyl, or adamantyl, etc.

[0027] In this specification, "alkyl thio" may include methyl thio, ethyl thio, propyl thio, butyl thio, octyl thio, or 2-ethylhexyl thio.

[0028] In this specification, "alkenyl" may include ethynyl, 1-propynyl, 2-propynyl, 2-butynyl, pentylyl, hexynyl, vinyl, allyl, or isopropenyl, etc.

[0029] In this specification, "alkoxy" may include, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, pentoxy, hexoxy, 2-ethylhexyloxy, octyloxy, or nonyloxy.

[0030] In this specification, "aryl" may include, for example, phenyl, naphthyl, phenatenyl, phenanthryl, anthraceneyl, azulenyl, and naphthyl. Furthermore, for this "aryl" group, the hydrogen atom of the aromatic ring may be substituted, for example, by 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 any one hydrogen atom from the aforementioned "aryl" group.

[0031] In this specification, "aryloxy" may include phenoxy, naphthyloxy, anthraceneyloxy, phenanthryloxy, or pyreneyloxy, etc.

[0032] In this specification, "aryl thio" may include aryl thio groups such as phenyl thio, naphthyl thio, anthracene thio, phenanthryl thio, or pyrene thio.

[0033] The term "halogen atom" in this specification may include, for example, fluorine, chlorine, bromine, or iodine atoms.

[0034] In this specification, "structural unit" refers to the (repeating) unit of a chemical structure formed during a reaction or polymerization. In other words, it refers to the part of the structure in the compound formed by a reaction or polymerization that is not involved in the chemical bonds that participate in the reaction or polymerization, and is referred to as a residue.

[0035] [Curing composition]

[0036] The curable composition of this embodiment contains: a polymaleimide compound (A) having a monocyclic or condensed polycyclic aromatic ring with two or more straight-chain or branched alkylene groups attached (hereinafter referred to as polymaleimide compound (A)), and an unsaturated hydrocarbon compound (B) having a reactive double bond (hereinafter referred to as unsaturated hydrocarbon compound (B)).

[0037] Because the polymaleimide compound (A) has a low proportion of polar functional groups in its chemical structure and the unsaturated hydrocarbon compound (B) has reactive double bonds, the composition as a whole can achieve both excellent low dielectric properties and low hygroscopicity.

[0038] In the curable composition of this embodiment, the mixing ratio (parts by mass) of the polymaleimide compound (A) and the unsaturated hydrocarbon compound (B) having reactive double bonds 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 range described above, excellent low hygroscopicity, low dielectric constant, and low dielectric loss tangent can be achieved, and therefore this ratio is preferred.

[0039] The curable composition of this embodiment may contain a curing agent (D) other than an unsaturated hydrocarbon compound (B) having reactive double bonds, within a range that does not impair the curing properties of the present invention. Furthermore, the curable composition of this embodiment may further contain an epoxy resin (C). Moreover, other resins (E) besides epoxy resin (C), 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, release agents, antioxidants, light stabilizers, heat stabilizers, pigments, and emulsifiers.

[0040] Hereinafter, the polymaleimide compound (A) containing an aromatic ring and having an alkylene group, and the unsaturated hydrocarbon compound (B), which are essential components of the curable composition of this embodiment, will be described in detail. Then, epoxy resin (C), curing agent (D) other than unsaturated hydrocarbon compound (B), other resin (E) other than epoxy resin (C), curing accelerator and additives, which are optional components, will be described.

[0041] (Polymaleimide compound (A))

[0042] 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.

[0043] The aforementioned monocyclic or polycyclic aromatic ring with two or more straight-chain or branched alkylene groups refers to a divalent or higher group containing two or more straight-chain or branched alkylene groups with 1 to 12 carbon atoms, and having one or more of these alkylene groups linked to a single bond on the monocyclic or polycyclic aromatic ring. Therefore, the number of straight-chain or branched alkylene groups linked to the monocyclic or polycyclic aromatic ring is consistent with the valence of the alkylene groups 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.

[0044] The monocyclic or condensed polycyclic aromatic rings of this embodiment, which are connected to two or more straight-chain or branched alkylene groups, are preferably groups represented by the following general formula (I).

[0045]

[0046] (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 bond with another atom.

[0047] 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.

[0048] The maleimide group is preferably a group represented by the following general formula (II).

[0049]

[0050] (In the above general formula (II), Ar) 2 (Indicates an aromatic group; dashed lines indicate absence or a single bond; * indicates connection to other atoms.)

[0051] 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) may be monovalent. On the other hand, when the dashed line is a single bond, the maleimide group in general formula (II) may be divalent.

[0052] The preferred polymaleimide compound (A) in 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 reactant (1).

[0053]

[0054] (In the above general formula (1), R) 1 Each can be used independently to represent an alkyl group.

[0055] 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.

[0056] 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 of them is a hydrogen atom and the other is a methyl group.

[0057] X 1 The substituents represented by the following general formula (x) are:

[0058]

[0059] (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 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, where t represents an integer from 0 to 4.

[0060] r represents the number of connections with X. 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.

[0061] Therefore, during curing, it is possible to achieve a higher level of balance between low moisture absorption and low dielectric loss tangent.

[0062] <Preferred method for polymaleimide compound (A)>

[0063] The polymaleimide compound (A) of this embodiment preferably has the structural unit shown in the above general formula (1).

[0064] 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... 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.

[0065] 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 R in general formula (1) 1 The benzene ring attached can be the benzene ring of an aromatic amine compound (a).

[0066] In the above general formula (1), p preferably represents 1 or 2. It should be noted that R in general formula (1) is preferably... 1 At least one of the 2, 3, 4, 5, or 6 positions of the connected benzene ring is connected with an R 1 .

[0067] 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 R in general formula (1) 2 The connected 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.

[0068] 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 6 In this compound, if the proportion of alkyl groups increases, the reactivity of the unsaturated bonds inherent in the polymaleimide compound (A) is expected 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 effectively form a cured product.

[0069] 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.

[0070] In the above general formula (1), r means that each connection has X 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.

[0071] 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.

[0072] <Other preferred methods for polymaleimide compound (A)>

[0073] As another preferred embodiment of the polymaleimide compound (A), it may be a compound in which an aromatic amine compound (a) having one or more alkyl groups, an aromatic divinyl compound (b1) having two vinyl groups, and maleic anhydride are used 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) in which 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 are used 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 added as needed as the reaction raw material (2).

[0074] 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 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 an aromatic ring with 1 to 3 alkyl groups on the aromatic ring, and a structural unit of an aromatic divinyl compound (b1) having 2 vinyl groups, connected by chemical bonds, and a structural unit of an aromatic monovinyl compound (b2) chemically bonded to the aromatic ring in the structural unit of the aromatic amine compound (a) as needed. Furthermore, the polymaleimide compound (A) in this embodiment has a structure in which the amino group (including -NH2 and substituted amino groups) connected to the aromatic ring of the intermediate amine compound (c) is replaced by an N-substituted maleimide ring.

[0075] 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 by an N-substituted maleimide ring.

[0076] 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 later, 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).

[0077] In this embodiment, an aromatic amine compound (a) having a specific aromatic ring structure is used as a reactant, thus making it easy to control the reaction site with the aromatic divinyl compound (b1) described later. As a result, a polymaleimide compound (A) with a uniform chemical structure or chain length can be easily obtained. Consequently, a polymaleimide compound (A) exhibiting low hygroscopicity and low dielectric loss tangent during curing can be provided.

[0078] Hereinafter, after describing the aromatic amine compound (a) having one or more but less three alkyl groups, the aromatic divinyl compound (b1) having two vinyl groups, the aromatic monovinyl compound (b2) having one vinyl group (which may be an arbitrary 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.

[0079] <<Aromatic Amine Compounds (a)>>

[0080] The aromatic amine compound (a) in this embodiment has an aromatic ring with an amino group (-NH2 or a substituted amino group) attached to it, 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. A benzene ring is preferred as the aromatic hydrocarbon ring. Examples of heterocyclic rings include, for example, a pyran ring or a pyridine ring, which are hetero-six-membered rings. Furthermore, the aromatic amine compound (a) in this embodiment is more preferably an aromatic ring with an amino group (-NH2) attached to it, and one to three alkyl groups are attached to the aromatic ring.

[0081] In the aromatic amine compound (a) of this embodiment, the alkyl group substituted for one to three hydrogen atoms of the aromatic ring of the aromatic amine compound (a) can be an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 6 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms. The alkyl group can be any of a straight-chain, branched, or cyclic form. 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.

[0082] From the viewpoint that the aromatic ring has an amino group (including -NH2 and substituted amino groups) and that the two connecting bonds are suitable for polymerization, the upper limit for the number of alkyl groups attached to the aromatic ring having an amino group (including -NH2 and substituted amino groups) in the aromatic amine compound (a) can be 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.

[0083] 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.

[0084] 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.

[0085] In this embodiment, preferably, one or more carbon atoms in the benzene ring constituting the aromatic amine compound (a) that have the largest HOMO electron density (Hückel coefficient) are unsubstituted (or substituted by hydrogen atoms).

[0086] Therefore, it is easy to control the ArS generated by the cationic reagent formed from the aromatic divinyl compound (b1) described later. EReaction and Molecular Design. In more detail, 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 having the highest HOMO electron density. Therefore, by controlling the number and position of alkyl groups attached to the carbon atoms of the benzene ring, the connection 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.

[0087] 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 2, 4, and 6 positions, which are the meta and para positions with high electron density, of the aniline core. 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 roughly controlled, thus easily obtaining 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 believed that a large quantity of polymaleimide compounds (A) linked to the aromatic divinyl compound (b1) at the 4 position can be obtained.

[0088] As a specific example of the aromatic amine compound (a) in this embodiment, dimethylaniline (2,3-dimethylaniline, 2,4-dimethylaniline, 2,6-dimethylaniline, 3,4-dimethylaniline or 3,5-dimethylaniline), diethylaniline (2,3-diethylaniline, 2,4-diethylaniline, 2,6-diethylaniline, 3,4-diethylaniline or 3,5-diethylaniline), diisopropylaniline (2,3-diisopropylaniline, 2,4-diisopropylaniline, 2,6-diisopropylaniline, 3,4-diisopropylaniline or 3,5-diethylaniline), ethylmethylaniline (e.g., at the 2,3, 2,4, 2... Ethylmethylaniline (e.g., ethyl methyl aniline with methyl at positions 6, 3, 4, or 3, 5 and ethyl at the other), 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, methyl isopropylaniline (e.g., methyl isopropylaniline with methyl at positions 2, 3, 2, 4, 2, 6, 3, 4, or 3, 5 and methyl at the other) or ethylbutylaniline (e.g., ethyl butylaniline with ethyl at positions 2, 3, 2, 4, 2, 6, 3, 4, or 3, 5 and butyl at the other), 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.

[0089] For example, in chemical structures like 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 present disclosure, for example, in the case of 2,6-dimethylaniline having an alkyl group (e.g., methyl) as a substituent for the benzene ring, the steric hindrance of the methyl group results in a configuration where the benzene ring and the 5-membered ring of the maleimide are distorted, making stacking difficult. Consequently, 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).

[0090] The aromatic amine compound (a), which is an essential component of the reaction raw material (1) in this embodiment, can be represented by, for example, the following general formula (a).

[0091]

[0092] (In the above general formula (a), R) 1a Indicates alkyl group, p aRepresents integers from 1 to 3. Multiple R exist. 1a They can be the same or different.

[0093] 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.

[0094] 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.

[0095] 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.

[0096] <<Aromatic Divinyl Compounds (b1)>>

[0097] The aromatic divinyl compound (b1) in this embodiment 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).

[0098] 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).

[0099] Examples of aromatic divinyl compounds (b1) include 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, etc., onto their 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.

[0100] 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).

[0101]

[0102] (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 group; or a 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.

[0103] 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.

[0104] 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.

[0105] 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.

[0106] It should be noted that the aromatic divinyl compound (b1) in this embodiment can be used alone or in combination of two or more.

[0107] 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.

[0108] 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).

[0109] <<Aromatic Monovinyl Compounds (b2)>>

[0110] Regarding the polymaleimide compound (A) in this embodiment, in addition to the aromatic amine compound (a), the aromatic divinyl compound (b1), and maleic anhydride, other compounds may be used as reactants. Examples of such other compounds include, for instance, an aromatic monovinyl compound (b2) having one vinyl group. That is, 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). In this embodiment, the polymaleimide compound (A) 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, thereby resulting in a cured polymaleimide compound (A) that exhibits excellent low dielectric loss tangent, and is therefore preferred.

[0111] 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).

[0112] 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, 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, propyloxy, butoxy, etc. Examples of the halogen atom include fluorine, chlorine, bromine, etc.

[0113] 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).

[0114]

[0115] (In the above general formula (b2), R) 9b Each of the following can independently represent 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. 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.

[0116] 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.

[0117] 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.

[0118] Specific examples of aromatic monovinyl compounds (b2) in this embodiment include, for example, vinylbenzene compounds such as styrene, fluorostyrene, vinylbenzyl chloride, alkylvinylbenzene (o-, m-, p-methylstyrene; o-, m-, p-ethylvinylbenzene), o-, m-, p-(chloromethyl)styrene and compounds composed of their derivatives; biphenyl compounds such as 4-vinylbiphenyl, 4-vinyl-p-terphenyl and compounds composed of their derivatives; and vinylnaphthalene compounds such as 1-vinylnaphthalene, 2-vinylnaphthalene and compounds composed of their derivatives, but are not limited to these.

[0119] 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.

[0120] 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.

[0121] 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.

[0122] 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).

[0123] <<Malic anhydride>>

[0124] 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 of the amino group (including -NH2 and substituted amino groups) from aromatic amine compound (a).

[0125] <Preferred method for polymaleimide compound (A)>

[0126] The preferred polymaleimide compound (A) of this disclosure will be described below, taking the case where each aromatic ring is a benzene ring as an example. The following chemical structural formulas are used to illustrate this disclosure, and the scope of this disclosure is not limited to the following chemical structural formulas.

[0127] In this embodiment, the polymaleimide compound (A) is preferably represented by the following general formula (2).

[0128]

[0129] (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 4 One side is a hydrogen atom and the other side is a methyl group, R 5 and R 6 One of them is a hydrogen atom and the other is a methyl group.

[0130] X 1 The substituents represented by the following general formula (x) are:

[0131]

[0132] (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.)

[0133] 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.

[0134]

[0135] In the above general formula (i), R 9R 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 bond 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.

[0136]

[0137] 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.

[0138] r represents the number of connections with X. 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.

[0139] In the above general formula (2), when p is an integer greater than 2, there exist multiple R... 1They 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.

[0140] 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 .

[0141] 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.

[0142] 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 chromatogram 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.

[0143] 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 below.

[0144] 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.

[0145]

[0146] (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 group; or a 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. Also, * indicates a connection to other atoms.

[0147] 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.

[0148] In the curable composition of this embodiment, it is preferable to contain 30% by mass or more and 95% by mass or less of polymaleimide compound (A) relative to the curable composition as a whole; more preferably, it contains 40% by mass or more and 85% by mass or less; and most preferably, it contains 50% by mass or more and 80% by mass or less. When the content of polymaleimide compound (A) is in the range of 50% by mass or more and 80% by mass or less, it is preferable from the viewpoint of heat resistance and low moisture absorption.

[0149] <Method for manufacturing polymaleimide compound (A)>

[0150] The following describes the method for manufacturing the polymaleimide compound (A) disclosed herein.

[0151] The method for preparing the polymaleimide compound (A) in this embodiment is not particularly limited, as long as an aromatic amine compound (a), an aromatic divinyl compound (b1), and maleic anhydride are used as reactants (1), or the compound is prepared in a manner having 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 comprising the following steps (1) and (2) can be listed.

[0152] 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;

[0153] 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.

[0154] 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.

[0155] The following describes each step of the method for manufacturing the polymaleimide compound (A) disclosed herein.

[0156] <<Process (1): Manufacturing process of intermediate amine compound (c)>>

[0157] The manufacturing process of the intermediate amine compound (c) in this embodiment will be described below.

[0158] 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 other compounds such as the aromatic monovinyl compound (b2) (e.g., ethylvinylbenzene) as needed, in the presence of an acid catalyst. This produces an intermediate amine compound (c).

[0159] 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 molar ratio of the total 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.

[0160] Furthermore, as a specific method for carrying out the above reaction, all the raw materials are usually loaded together and reacted directly at a predetermined temperature; or an aromatic amine compound (a) and an acid catalyst are loaded, and while maintaining the predetermined temperature, an aromatic divinyl compound (b1), other compounds (e.g., an aromatic monovinyl compound (b2)), etc., are added dropwise while the reaction is carried out. In this case, the dropwise addition time is usually 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, thereby obtaining the above-mentioned intermediate amine compound (c) as the target substance.

[0161] 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, as well as solid acids such as activated clay, acid clay, silica-alumina, zeolite, strong acid ion exchange resin, and heteropolyhydrochloric acid. From the viewpoint of processability, it is preferable to use a solid acid that 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.

[0162] 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 prepared 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 generally in the range of 100 to 270°C, and is preferably 100 to 220°C to suppress the formation of isomer structures and avoid side reactions such as thermal decomposition.

[0163] In step (1) of this embodiment, the reaction time of the aromatic divinyl compound (b1) or the mixture of aromatic divinyl compound (b1) and aromatic monovinyl compound (b2) and the mixture of aromatic amine compound (a), i.e. the crosslinking reaction time, is such that 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. Therefore, under the above reaction temperature conditions, the reaction time is usually in the range of 1 to 48 hours, and preferably in the range of 1 to 30 hours.

[0164] In the method for producing the intermediate amine compound (c) in this embodiment, aniline or its derivatives also serve as solvents, so other solvents are not necessary, but solvents may also be used. For example, when the reaction is carried out using divinylbenzene as a raw material, the following method can be used: using a solvent that can azeotropically dehydrate, such as toluene, xylene, or chlorobenzene, 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.

[0165] The intermediate amine compound (c) obtained by the above process (1) preferably has a structural unit represented by the following general formula (4).

[0166]

[0167] (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.

[0168] 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 of them is a hydrogen atom and the other is a methyl group.

[0169] X 1 The substituents represented by the following general formula (x) are:

[0170]

[0171] (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 R8 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.)

[0172] r represents the number of connections with X. 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.

[0173] 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.

[0174] 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), the structure in the general formula (2) above, where the N-substituted maleimide group is replaced with an amino group (including -NH2 and substituted amino groups), which is also a preferred form of the polymaleimide compound (A), can be listed.

[0175] 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.

[0176] It should be noted that the determination of the amine equivalent of the intermediate amine compound (c) in this specification is set as the value determined by the neutralization titration method specified in JISK 0070 (1992).

[0177] <<Process (2): Maleimide>>

[0178] 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 by an N-substituted maleimide ring can be formed, thus obtaining the polymaleimide compound (A) of this disclosure.

[0179] 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.

[0180] 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.

[0181] 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 amount of intermediate amine compound (c) and maleic anhydride.

[0182] As catalysts that can be used in step (2) of this embodiment, examples include inorganic salts such as acetates, chlorides, bromides, sulfates, and nitrates of nickel, cobalt, sodium, calcium, iron, lithium, and manganese; inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid; organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid; solid acids such as activated clay, acid clay, silica-alumina, zeolite, and strongly acidic ion exchange resin; heteropolyhydrochloric acid, etc., with toluenesulfonic acid being particularly preferred.

[0183] As a 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.

[0184] 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.

[0185] 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.

[0186] (Unsaturated hydrocarbon compound (B))

[0187] The curable composition disclosed herein contains, in addition to a polymaleimide compound (A), an unsaturated hydrocarbon compound (B) comprising a group having a reactive double bond. The unsaturated hydrocarbon compound (B) reacts with the maleimide groups of the polymaleimide compound (A) via a reactive double bond (e.g., allyl), thereby obtaining a cured product exhibiting high crosslinking density and reduced polarity. Therefore, by using the curable composition containing the unsaturated hydrocarbon compound (B), it can be used as a molding material for electronic materials, which is useful. Furthermore, by reacting with the polymaleimide compound (A), it acts as a curing agent, generating three-dimensional crosslinks, resulting in a cured product with excellent heat resistance, which is a preferred method. Furthermore, its relationship with the epoxy resin (C), which is an optional component, also acts as a curing agent, improving adhesion to copper, for example, useful in the manufacture of circuit boards using copper foil.

[0188] As the unsaturated hydrocarbon compound (B) in this embodiment, there is no particular limitation as long as it is a compound containing two or more groups with reactive double bonds (carbon-carbon unsaturated bonds) in its molecule. Examples of such reactive double bond groups include allyl, isopropenyl, 1-propenyl, acryloyl, methacryloyl, styryl, and styrylmethyl. Among these, allyl, 1-propenyl, styryl, and styrylmethyl are preferred from the viewpoint of exhibiting good reactivity with the maleimide group of the polymaleimide compound (A) and providing a cured product with high crosslinking density and excellent heat resistance.

[0189] Furthermore, as an unsaturated hydrocarbon compound (B), it may further possess reactive functional groups other than those with reactive double bonds as described above. There are no particular limitations on the aforementioned reactive functional groups; examples include cyanate groups, hydroxyl groups, epoxy groups, reactive ester groups, amino groups, isocyanate groups, glycidyl groups, and phosphate groups. Among these, at least one group consisting of cyanate groups, hydroxyl groups, epoxy groups, and reactive ester groups is preferred, and cyanate groups are more preferred. By possessing hydroxyl groups, cyanate groups, epoxy groups, and reactive ester groups, it tends to have high flexural strength and flexural modulus, low dielectric constant, high glass transition temperature (Tg), and a tendency to reduce the coefficient of thermal expansion and further improve thermal conductivity.

[0190] The aforementioned unsaturated hydrocarbon compound (B) possessing reactive functional groups other than those having reactive double bonds can be used alone or in combination with two or more. When using two or more unsaturated hydrocarbon compounds (B) possessing reactive functional groups other than those having reactive double bonds, the reactive functional groups can be the same or different. Among these, it is preferable to include unsaturated hydrocarbon compounds (B) with a cyanate group as the reactive functional group and unsaturated hydrocarbon compounds (B) with an epoxy group as the reactive functional group. By using such unsaturated hydrocarbon compounds (B) with reactive double bonds in combination, there is a tendency to further improve flexural strength, flexural modulus, glass transition temperature (Tg), and thermal conductivity.

[0191] Examples of unsaturated hydrocarbon compounds (B) in this embodiment include bisphenols (B1) in which the hydrogen atoms of the aromatic ring are substituted with allyl groups, modified phenol compounds (B2) in which the hydrogen atoms of the aromatic ring are substituted with allyl groups and the phenolic hydroxyl group is modified with a reactive functional group other than the hydroxyl group in the reactive functional group other than the aforementioned reactive double bond, or polyphenylene ether compounds (B3) having reactive double bonds. More specifically, examples include diallyl bisphenol A, diallyl bisphenol A cyanate compounds, diallyl bisphenol A type epoxy compounds, and allylphenol terminal reactive ester compounds.

[0192] The bisphenols mentioned above are not particularly limited, and examples include bisphenol A, bisphenol AP, bisphenol AF, bisphenol B, bisphenol BP, bisphenol C, bisphenol E, bisphenol F, bisphenol G, bisphenol M, bisphenol S, bisphenol P, bisphenol PH, bisphenol TMC, and bisphenol Z. Among these, bisphenol A is preferred.

[0193] As for the polyphenylene ether compound (B3) with reactive double bonds in this embodiment, there is no particular limitation as long as it is a polyphenylene ether compound with reactive double bonds in its molecule. For example, it is preferable to have a structural unit selected from the group consisting of partial structures shown in the following general formulas (5) and (6), and a terminal structure containing a group with reactive double bonds connected to the partial structure.

[0194]

[0195]

[0196] (In the above general formulas (5) and (6), R) d1 ~R d8 Each of the following groups independently represents a hydrogen atom, an alkyl group with 1 to 5 carbon atoms, an alkenyl group with 1 to 5 carbon atoms, a cycloalkyl group with 3 to 5 carbon atoms, an alkoxy group with 1 to 5 carbon atoms, a thioether group with 1 to 5 carbon atoms, an alkyl carbonyl group with 2 to 5 carbon atoms, an alkoxy carbonyl group with 2 to 5 carbon atoms, an alkyl carbonyloxy group with 2 to 5 carbon atoms, or an alkyl sulfonyl group with 1 to 5 carbon atoms. In the above general formula (6), Y represents a divalent aromatic group from an aromatic compound having two phenolic hydroxyl groups, v is an integer value from 1 to 30, and w and u are integer values ​​from 1 to 30.

[0197] It should be noted that some structures shown in general formula (5) and / or general formula (6) above have a group containing a reactive double bond in the terminal structure of their structure. Examples of such a group containing a reactive double bond include alkenyl, (meth)acryloyl, styryl, styrylmethyl, etc., having 1 to 5 carbon atoms.

[0198] The polyphenylene ether (PPE) contained in the structure of the reactive double bond polyphenylene ether compound (B3) of this embodiment has excellent dielectric properties such as dielectric constant or dielectric loss tangent. Therefore, it is possible to formulate a curable composition that maintains a sufficiently low dielectric constant and exhibits a sufficiently low dielectric loss tangent even in high-frequency bands (high-frequency regions) such as the MHz band to the GHz band. Therefore, it is useful as a molding material for high-frequency applications. In addition, by reacting with the polymaleimide compound (A), it acts as a curing agent to generate three-dimensional crosslinks, and a cured product with excellent heat resistance can be obtained, which is a preferred method.

[0199] There are no particular limitations on the thioether groups with 1 to 5 carbon atoms mentioned above, and examples include methyl thio, ethyl thio, propyl thio, isopropyl thio, butyl thio, pentyl thio, etc.

[0200] 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.

[0201] There are no particular limitations on the alkoxycarbonyl groups with 2 to 5 carbon atoms mentioned above, and examples include methyloxycarbonyl, ethyloxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, butyloxycarbonyl, etc.

[0202] 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.

[0203] 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.

[0204] 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.

[0205] The Y in the above general formula (6) can be listed as a divalent aromatic group from aromatic compounds having two phenolic hydroxyl groups.

[0206] 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.

[0207] Furthermore, in the aforementioned aromatic compound with two phenolic hydroxyl groups, the two phenolic hydroxyl groups form a phenyl ether bond (the two oxygen atoms connected to Y), thus Y becomes a divalent aromatic group from the aromatic compound with two phenolic hydroxyl groups. In other words, the group obtained by removing any two hydrogen atoms from the aforementioned aromatic compound with two phenolic hydroxyl groups is considered as "a divalent aromatic group from the aromatic compound with two phenolic hydroxyl groups".

[0208] Furthermore, in this embodiment, the weight-average molecular weight (Mw) of the polyphenylene ether compound (B3) having reactive double bonds is preferably 1000 to 5000, more preferably 1200 to 4000, and even more preferably 1400 to 3000. Within this range, a cured product achieving a more substantial balance between excellent dielectric properties and heat resistance can be obtained, which is a preferred approach. It should be noted that the weight-average molecular weight (Mw) here can be obtained by conventional molecular weight determination methods; specifically, the value measured using GPC as described in the Examples section below can be cited.

[0209] In the curable composition of this embodiment, it is preferable to contain 10% by mass or more and 70% by mass or less of an unsaturated hydrocarbon compound (B) relative to the curable composition as a whole; more preferably, it contains 15% by mass or more and 65% by mass or less; and most preferably, it contains 20% by mass or more and 50% by mass or less. From the viewpoint of heat resistance, it is preferable when the content of the unsaturated hydrocarbon compound (B) is in the range of 20% by mass or more and 50% by mass or less.

[0210] (Curing agent (D) other than unsaturated hydrocarbon compound (B))

[0211] In the curable composition of this embodiment, a curing agent (D) other than the unsaturated hydrocarbon compound (B) may also 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 curable composition, the curing agent (D) is preferably 2% by mass or more and 20% by mass or less, and most preferably 5% by mass or more and 10% by mass or less. A curing agent (D) content in the range of 5% by mass or more and 10% by mass or less is preferred from the viewpoint of low hygroscopicity and low dielectric loss tangent.

[0212] Examples of curing agents (D) used in this embodiment include amine compounds, cyanate ester compounds, amide compounds, acid anhydride compounds, phenol compounds, polyphenylene ether compounds with hydroxyl groups at the ends, diene polymers, etc. These curing agents can be used alone or in combination of two or more.

[0213] Examples of the aforementioned amine compounds include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenyl sulfone, isophorone diamine, imidazole, BF3-amine complexes, and guanidine derivatives.

[0214] 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 cyanate resin, naphthol aralkyl type cyanate resin, naphthol-phenol cocondensed phenolic cyanate resin, naphthol-cresol cocondensed phenolic cyanate resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type cyanate resin, biphenyl modified phenolic cyanate resin, anthracene type cyanate resin, etc. They can be used individually or in combination of two or more.

[0215] Examples of the aforementioned amide compounds include dicyandiamide and polyamide resins synthesized from dimers of linolenic acid and ethylenediamine.

[0216] 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.

[0217] Examples of the aforementioned phenolic compounds include phenolic varnish resins, cresol phenolic varnish resins, aromatic hydrocarbon formaldehyde resin-modified phenolic resins, dicyclopentadiene phenol addition-type resins, phenol aralkyl resins (Zyloc resins), polyvalent phenolic varnish resins synthesized from polyvalent hydroxyl compounds represented by resorcinol phenolic varnish resins and formaldehyde, naphthol aralkyl resins, trimethylolpropane resins, tetraphenol ethane resins, naphthol phenolic varnish resins, naphthol-phenol cocondensed phenolic varnish resins, and naphthalene. Phenolic-cresol cocondensed phenolic varnish resin, biphenyl-modified phenolic resin (a polyvalent phenol compound with a phenol core linked by dimethylene groups), biphenyl-modified naphthol resin (a polyvalent naphthol compound with a phenol core linked by dimethylene groups), aminotriazine-modified phenolic resin (a polyvalent phenol compound with a phenol core linked by melamine, benzoguanamine, etc.), and alkoxy-containing aromatic ring-modified phenolic varnish resin (a polyvalent phenol compound with a phenol core and an alkoxy-containing aromatic ring linked by formaldehyde), etc., are all polyvalent phenolic compounds.

[0218] Examples of polyphenylene ether compounds having hydroxyl groups at the ends include partial structures of general formula (5) or general formula (6) and compounds whose terminal structures are hydroxyl groups.

[0219] 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.

[0220] 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 can also be used.

[0221] (Epoxy Resin (C))

[0222] The curable composition of this embodiment preferably further contains epoxy resin (C). The epoxy resin (C) exhibits good flowability during the preparation of the curable composition, making it useful for preparing a curable composition that yields a cured product with excellent adhesion. Furthermore, when the curable composition of this embodiment uses a polymaleimide compound (A), an unsaturated hydrocarbon compound (B), and epoxy resin (C), the adhesion to copper is improved, which is useful, for example, in the manufacture of circuit boards using copper foil.

[0223] The epoxy resin (C) used in this embodiment is not particularly limited, and examples include phenolic epoxy resins such as phenolic varnish epoxy resin, cresol phenolic varnish epoxy resin, α-naphthol phenolic epoxy resin, β-naphthol phenolic epoxy resin, bisphenol A phenolic epoxy resin, and biphenyl phenolic epoxy resin; aralkyl epoxy resins such as phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, and phenol biphenyl aralkyl type epoxy resin; bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol AF type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol C type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and tetrabromobisphenol A type epoxy resin; and biphenyl type epoxy resins. Epoxy resins include: epoxy resins such as tetramethylbiphenyl type epoxy resin and epoxy resins with a biphenyl backbone and a diglycidyloxybenzene backbone; naphthalene type epoxy resins; binatol type epoxy resins; binatyl type epoxy resins; dicyclopentadiene phenol type epoxy resins; tetraglycidyl diaminodiphenylmethane type epoxy resins, triglycidyl-p-aminophenol type epoxy resins, diaminodiphenyl sulfone glycidylamine type epoxy resins; diglycidyl ester type epoxy resins such as 2,6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resins and hexahydrophthalic anhydride glycidyl ester type epoxy resins; and benzopyran type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran. These can be used individually or in combination of two or more types.

[0224] Among these, considering the availability of cured products with excellent heat resistance, phenolic aralkyl type epoxy resins, biphenyl phenolic type epoxy resins, or naphthol phenolic type epoxy resins containing a naphthalene skeleton, naphthol aralkyl type epoxy resins, naphthol-phenol cocondensed phenolic type epoxy resins, naphthol-cresol cocondensed phenolic type epoxy resins, or crystalline biphenyl type epoxy resins, tetramethylbiphenyl type epoxy resins, xanthracene type epoxy resins, or aromatic ring modified phenolic type epoxy resins containing alkoxy groups (compounds containing glycidyl groups and aromatic rings containing alkoxy groups linked by formaldehyde), are particularly preferred.

[0225] In the curable composition of this embodiment, it is preferable to contain 2% by mass or more and 30% by mass or less of epoxy resin (C) relative to the total amount of the curable composition, and most preferably, it contains 5% by mass or more and 25% by mass or less. From the viewpoint of heat resistance, it is preferable when the content of epoxy resin (C) is in the range of 5% by mass or more and 25% by mass or less.

[0226] The preferred curable composition of this embodiment is characterized by containing a polymaleimide compound (A), an unsaturated hydrocarbon compound (B), and an epoxy resin (C). The polymaleimide compound (A) has a chemical structure in which two or more maleimide groups are linked to an alkyl diester having a monocyclic or condensed polycyclic aromatic ring. Therefore, compared to conventional maleimide resins, it exhibits superior solvent solubility, ease of preparation of the curable composition, and excellent processability. Due to the low proportion of polar functional groups in the structure of the polymaleimide compound (A), a cured product with excellent dielectric properties can be obtained. Furthermore, the unsaturated hydrocarbon compound (B), acting as a curing agent, reacts with the maleimide groups through reactive double bonds, contributing to the formation of a cured product with high crosslinking density. Additionally, the epoxy resin (C) exhibits good flowability during the preparation of the curable composition, resulting in a cured product with excellent adhesion. Furthermore, by reacting the unsaturated hydrocarbon compound (B), which acts as a curing agent, with the polymaleimide compound (A) and the epoxy resin (C), three-dimensional cross-linking can be achieved, resulting in a cured product with excellent heat resistance, which is a preferred method. Additionally, the reaction of the unsaturated hydrocarbon compound (B) with the epoxy resin (C) improves the adhesion to copper, which is useful, for example, in the manufacture of circuit boards using copper foil.

[0227] The mixing ratio (parts by mass) of polymaleimide compound (A), unsaturated hydrocarbon compound (B), and epoxy resin (C) is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, even more preferably 65:35 to 35:65, and particularly preferably 55:45 to 45:55. By adjusting the mixing ratio within the above range, heat resistance, low dielectric constant, and low dielectric loss tangent can be achieved, which is preferred.

[0228] In the curable composition of the present invention, the mixing ratio (parts by mass) of the unsaturated hydrocarbon compound (B) to the epoxy resin (C) is not particularly limited. However, considering the good properties of the resulting cured product, the ratio of unsaturated hydrocarbon compound (B):epoxy resin (C) is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and even more preferably 65:35 to 35:65. By adjusting the mixing ratio within the above range, heat resistance, low dielectric constant, and low dielectric loss tangent can be achieved, which is preferred.

[0229] (Other resins (E))

[0230] Furthermore, other resins (E) may be included in addition to the polymaleimide compound (A), unsaturated hydrocarbon compound (B), and epoxy resin (C), provided that this does not impair the purpose of the present disclosure. These other resins (E) may also include bismaleimides other than the aforementioned polymaleimide compound (A), allyl ether compounds, allyl amine compounds, triallyl cyanurate, alkenylphenol compounds, vinyl-containing polyolefin compounds, 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. The content of the other resins (E) is preferably 2% to 20% by mass, and most preferably 5% to 10% by mass, relative to 100% by mass of the total curable composition. When the content of other resins (E) is in the range of 5% by mass to 10% by mass, it is preferred from the viewpoint of heat resistance and compatibility.

[0231] (Curing accelerator)

[0232] 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, the addition of 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.

[0233] (additive)

[0234] 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 additives is preferably 1% to 20% by mass relative to 100% of the total weight of the curable composition, and most preferably 3% to 10% by mass.

[0235] 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.

[0236] 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. When the amount of the inorganic filler is particularly increased, 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 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.

[0237] In the curable composition of this embodiment, the lower limit of the total content of polymaleimide compound (A) and unsaturated hydrocarbon 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 total content is preferably 100%, 99%, 98%, or 97% by mass. The above 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 unsaturated hydrocarbon compound (B) relative to the total curable composition (100% by mass) is preferably 40% by mass or more and 100% by mass or less, more preferably 45% by mass or more and 100% by mass or less, and even more preferably 50% by mass or more and 100% by mass or less.

[0238] In the curable composition of this embodiment, the lower limit of the total content of polymaleimide compound (A), unsaturated hydrocarbon compound (B), inorganic filler, and additives relative to the total curable composition (100% by mass) is preferably 70%, 72%, 75%, 77%, or 80% by mass. Furthermore, the upper limit of the above total content is preferably 100%, 99%, 98%, or 97% by mass. Similar to the range of the total content of polymaleimide compound (A) and unsaturated hydrocarbon compound (B), the above upper and lower limits can be combined arbitrarily.

[0239] In the curable composition of this embodiment, the lower limit of the total content of polymaleimide compound (A), unsaturated hydrocarbon compound (B), epoxy resin (C), 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-mentioned total content is preferably 100%, 99%, 98%, or 97% by mass. Similar to the range of the total content of polymaleimide compound (A) and unsaturated hydrocarbon compound (B), the above-mentioned upper and lower limits can be combined arbitrarily.

[0240] [cured material]

[0241] The cured product disclosed herein is preferably obtained from the above-described curable composition. The cured product is 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.

[0242] The aforementioned curing (thermosetting) 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 composition.

[0243] [Heat-resistant materials and electronic materials]

[0244] The cured product obtained from the curable composition containing the polymaleimide compound (A) and the unsaturated hydrocarbon 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 sealing materials, semiconductor devices, multilayer films, multilayer substrates, adhesives using conductive pastes, and photoresist materials. Furthermore, it is suitable for use 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-described 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 frame components.

[0245] Hereinafter, representative articles (circuit boards, semiconductor sealing materials, semiconductor devices, prepregs, multilayer substrates, multilayer films, conductive pastes) manufactured using the curable compositions of the present invention will be described by way of example.

[0246] [Circuit board]

[0247] This disclosure pertains to a circuit board as a laminate of prepreg and copper foil. As a method for obtaining a printed circuit board from the curable composition of this embodiment, an example is a method in which the following prepreg is laminated using conventional methods, copper foil is appropriately overlapped, and the substrate is heated and pressed at 170-300°C for 10 minutes to 3 hours under a pressure of 1-10 MPa.

[0248] [Semiconductor sealing materials]

[0249] 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 unsaturated hydrocarbon compound (B) of this disclosure. Therefore, it possesses excellent processability, moldability, and reflow resistance during the manufacturing process, making it a preferred method.

[0250] The curable composition of this embodiment used in the aforementioned semiconductor sealing material can 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, can 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.

[0251] As a method for obtaining the aforementioned semiconductor sealing material, methods can be listed such as further using an extruder, kneader, roller, etc., to fully melt and mix curing accelerators and / or additives, which are any components, to achieve uniformity in the curable composition of this embodiment. 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 higher thermal conductivity than fused silica, or fused silica, crystalline silica, alumina, and silicon nitride, can be used. Regarding the 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, and even more preferably 80 parts by mass or more, are used to improve flame retardancy, moisture resistance, solder crack resistance, and reduce the coefficient of linear expansion.

[0252] [Semiconductor Devices]

[0253] 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 unsaturated hydrocarbon compound (B) of this disclosure. Furthermore, they exhibit improved hygroscopicity, thermal modulus of elasticity, and adhesion to metallic materials, resulting in superior processability, moldability, and reflow resistance during manufacturing, making them a preferred method.

[0254] As a method for obtaining the above-mentioned semiconductor device, one example is to form the semiconductor sealing material by means of casting, transfer molding machine, injection molding machine, etc., and then heat and cure it in a temperature range of room temperature (20°C) to 250°C.

[0255] [Prepreg]

[0256] This disclosure pertains to a prepreg having a reinforcing substrate and a curable composition of this embodiment impregnated in the reinforcing substrate. As a method for obtaining the prepreg from the curable composition, one method includes impregnating a reinforcing substrate (paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, glass yarn bundle, etc.) with an organic solvent (described later), and then heating the prepreg at a temperature corresponding to the type of solvent used, preferably 50 to 170°C, thereby partially curing (or not curing) the curable composition to obtain 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 to prepare the prepreg with a resin content of 20 to 60% by mass.

[0257] 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.

[0258] It should be noted that the degree of curing of the semi-cured material can be determined by DSC measurement of the heat release during curing of the curing composition and the heat release during curing of its semi-cured material, and calculated by the following formula.

[0259] Degree of Curing (%) = [1 - (Heat release during curing of the semi-cured product / Heat release during curing of the curable composition)] × 100

[0260] 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.

[0261] 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.

[0262] [Laminated substrate]

[0263] As a method for obtaining a multilayer substrate from the curable composition of this embodiment, the following steps 1 to 3 can be listed. In step 1, firstly, the curable composition, appropriately formulated with 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, if necessary, predetermined through-holes or the like are made on the circuit board coated with the curable composition, then a roughening agent is applied, and the surface is washed with hot water to create an uneven surface on the substrate, followed by plating with metals such as copper. In step 3, steps 1 to 2 are repeated sequentially as desired, alternatingly laminating a resin insulating layer and a conductor layer with a predetermined circuit pattern to form the multilayer substrate. If necessary, in step 2, after predetermined through-holes or the like are made on the circuit board coated with the curable composition, a roughening agent is applied, and the surface is washed with hot water to create an uneven surface on the substrate, followed by plating with metals such as copper. In step 3, the operations of steps 1 and 2 are repeated sequentially as desired, and the resin insulating layer and the conductor layer with the predetermined circuit pattern are alternately deposited to form a multilayer substrate. It should be noted that in the above steps, the opening of the through-hole portion can be performed after the outermost resin insulating layer is formed. In addition, regarding the multilayer substrate in this embodiment, a resin-coated copper foil, which is semi-cured on a copper foil, can also be heated and pressed onto a wiring substrate with a circuit formed by heating at 170 to 300°C, thereby forming a roughened surface and eliminating the need for a plating process to manufacture the multilayer substrate.

[0264] [Laminated membrane]

[0265] 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.

[0266] When manufacturing multilayer films from curable compositions, it is important that the film softens under the lamination temperature conditions (typically 70–140°C) in a vacuum lamination process. During lamination of the circuit board, it should exhibit resin flowability (resin flow) capable of filling vias or through-holes present in the circuit board. Preferably, the aforementioned components are formulated 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, uniform appearance is required in the resulting multilayer film and circuit board (copper clad laminate, etc.).

[0267] 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.

[0268] Specifically, the method for manufacturing the aforementioned adhesive film involves preparing a varnish-like curable composition, coating the varnish-like composition onto the surface of a support film (Y), and further drying the organic solvent by heating or blowing hot air to form a composition layer (X) composed of the curable composition. As the aforementioned organic solvent, ketones such as acetone, methyl ethyl ketone, and cyclohexanone are preferred; acetates such as ethyl acetate, butyl acetate, cellolytic acetate, propylene glycol monomethyl ether acetate, and carbitol acetate are preferred; carbitols such as cellolytic agents and butyl carbitol are preferred; aromatic hydrocarbons such as toluene and xylene are preferred; and dimethylformamide, dimethylacetamide, and N-methylpyrrolidone are preferred. Furthermore, it is preferable to use a non-volatile component at a ratio of 30 to 60% by mass.

[0269] The thickness of the formed composition layer (X) is preferably greater than or equal to the thickness of the conductor layer. The thickness of the conductor layer in the circuit board is typically in the range of 5 to 70 μm, therefore 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., on the surface of the resin composition layer can be prevented.

[0270] The aforementioned support film (Y) and protective film can include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (hereinafter sometimes abbreviated as "PET") and polyethylene naphthalate; polycarbonate, polyimide, and metal foils such as release paper, copper foil, and aluminum foil. It should be noted that, in addition to MAD 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.

[0271] 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.

[0272] 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 them off, lamination is performed on one or both sides of the circuit board by, for example, vacuum lamination, in a manner that the resin composition layer (X) is directly in contact with the circuit board. The lamination method can be intermittent or continuous using rollers. In addition, the laminated film and the circuit board can be preheated as needed before lamination (preheating). Regarding the lamination conditions, it is preferable to set the lamination temperature to 70 to 140°C, and the lamination pressure to 1 to 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).

[0273] <Conductive Paste>

[0274] As a method for obtaining conductive paste from the curable composition of the present invention, a method of dispersing conductive particles in the composition can be cited as an example. The above-mentioned conductive paste can be formulated into a paste resin composition for circuit connection or an anisotropic conductive adhesive, depending on the type of conductive particles used.

[0275] [Example]

[0276] The present invention is specifically illustrated through 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.

[0277] (1) Amine equivalent

[0278] The amine equivalent of intermediate amine compound (c) was determined by the following method.

[0279] 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.

[0280] 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.

[0281] Amine equivalent (g / equivalent) = (S × 2,000) / (blank - A)

[0282] S: Amount of sample (g)

[0283] A: Volume (mL) of 0.5 mol / L potassium hydroxide-ethanol solution consumed.

[0284] Blank: The volume (mL) of 0.5 mol / L potassium hydroxide-ethanol solution consumed in the blank test.

[0285] (2) GPC determination

[0286] 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.

[0287] "Measuring device"

[0288] "HLC-8320GPC" manufactured by TOSOH Co., Ltd.

[0289] "Measurement conditions"

[0290] 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.

[0291] Detector: RI (Differential Refractometer)

[0292] Data processing: "GPC Workstation EcoSEC-WorkStation" manufactured by TOSOH Corporation

[0293] Measurement conditions: column temperature 40℃

[0294] Expand solvent tetrahydrofuran

[0295] Flow rate 1.0 ml / min

[0296] Standard: Based on the above-mentioned "GPC Workstation EcoSEC-WorkStation" test manual, use the following monodisperse polystyrene with known molecular weight.

[0297] (Using polystyrene)

[0298] "A-500" made by TOSOH Co., Ltd.

[0299] "A-1000" made by TOSOH Co., Ltd.

[0300] "A-2500" manufactured by TOSOH Co., Ltd.

[0301] "A-5000" made by TOSOH Co., Ltd.

[0302] "F-1" manufactured by TOSOH Co., Ltd.

[0303] "F-2" manufactured by TOSOH Co., Ltd.

[0304] "F-4" manufactured by TOSOH Co., Ltd.

[0305] "F-10" manufactured by TOSOH Co., Ltd.

[0306] "F-20" manufactured by TOSOH Co., Ltd.

[0307] "F-40" manufactured by TOSOH Co., Ltd.

[0308] "F-80" manufactured by TOSOH Co., Ltd.

[0309] "F-128" manufactured by TOSOH Co., Ltd.

[0310] Sample: A sample (50 μl) was obtained by filtering a tetrahydrofuran solution of the polymaleimide compound (A) obtained in the synthesis example, which was calculated as 1.0% by mass of resin solids, through a microfilter.

[0311] (3) FD-MS determination

[0312] The polymaleimide compound (A) obtained in the examples was determined by FD-MS chromatography using the following measuring apparatus and conditions.

[0313] Measurement device: JMS-T100GC AccuTOF

[0314] Measurement conditions

[0315] Measurement range: m / z = 4.00~2000.00

[0316] Rate of change: 51.2 mA / min

[0317] Final current value: 45mA

[0318] Cathode voltage: -10kV

[0319] Recording interval: 0.07 sec

[0320] (4) 13 C-NMR determination

[0321] The polymaleimide compound (A) obtained in the examples 13 C-NMR chromatography was performed using the following apparatus and conditions.

[0322] 13 C-NMR: "JNM-ECZ400S" manufactured by JEOL RESONANCE

[0323] Resonant frequency: 100MHz

[0324] Points earned: 4000 times

[0325] Solvent: Chloroform-d

[0326] Sample concentration: 12% by mass

[0327] Buffer reagent: Chromium acetylacetonate (III)

[0328] (5) Synthesis of polymaleimide compound (A)

[0329] <Synthetic Example 1> Synthesis of polymaleimide compound (A-1)

[0330] (I) Synthesis of intermediate amine compound (c-1)

[0331] In a flask equipped with a thermometer, cooling tube, Dean-Stark trap, 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 Chemicals & Materials)) was added dropwise over 2 hours, allowing the mixture to react directly for 1 hour. The temperature was then increased 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.

[0332] (II) Maleimide

[0333] In a 2L flask equipped with a thermometer, cooling tube, Dean-Stark trap, 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. After cooling and separating the azeotropic water and toluene under reflux, only the toluene was returned to the system for a 5-hour dehydration reaction. After air cooling to room temperature, the mixture was neutralized with 49% NaOH. Then, toluene and water were removed by vacuum distillation at 60°C. 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 C-NMR confirmation. The measurement results are shown below. Figures 1A to 1C 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.

[0334] <Examples 1-2 and Comparative Examples 1-2>

[0335] <<Preparation of Curable Compositions and Production of Cured Products>>

[0336] The polymaleimide compound (A-1) obtained in the above synthetic example 1, the comparison shown in formula (7) is as follows: maleimide (1) ("BMI-1000", manufactured by Yamato Chemical Industry Co., Ltd.), unsaturated hydrocarbon compound (B-1) as unsaturated hydrocarbon compound (B) ("SA-9000", manufactured by SABIC Corporation, two-terminated methacrylic acid modified polyphenylene ether), unsaturated hydrocarbon compound (B-2) ("NE-V-1100", manufactured by DIC Corporation, two-terminated vinyl resin), and unsaturated hydrocarbon compound (B-3) ("DABPA", manufactured by Yamato Chemical Industry Co., Ltd., 2,2'-diallyl bisphenol A), epoxy resin (C-1) as epoxy resin (C) (BPA type epoxy resin "850-S" equivalent: 188 g / eq, manufactured by DIC Corporation), and DCPO ("PERCUMYL D", manufactured by Nippon Oil Co., Ltd., Dicumyl Peroxide was mixed in the proportions shown in Table 1 below to prepare the curable compositions of Examples 1-3 and Comparative Examples 1-3.

[0337]

[0338] Next, the curable compositions of Examples 1-3 and Comparative Examples 1-3 were cured under the following curing conditions to produce cured products corresponding to the curable compositions of Examples 1-3 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.

[0339] <<Curing Conditions>>

[0340] After being vacuum-pressed at 200°C for 2 hours, it is then heated and cured at 250°C for 2 hours.

[0341] Thickness of the formed plate: 1.3mm

[0342] <<Evaluation of Dielectric Constant and Dielectric Loss Tangent>>

[0343] According to JIS-C-6481, the dielectric constant (Dk) and dielectric loss tangent (Df) of a test piece at 1 GHz after being completely dried and stored indoors at 23°C and 50% humidity for 24 hours were determined using a network analyzer "E8362C" manufactured by Agilent Technologies, using the void resonance method.

[0344] <<Evaluation of Hygroscopicity>>

[0345] In this embodiment and comparative example, the moisture absorption rate (%) was calculated and evaluated as an evaluation method for low hygroscopicity using the following method.

[0346] Cut test pieces with dimensions of 5mm×55mm×1.3mm from the cured material obtained above. For these test pieces, use a pressure cooker to maintain them at 85℃, 85%RH, and 1 atmosphere for 50 hours. Calculate the moisture absorption rate (%) using the following formula and evaluate the results.

[0347] 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

[0348] [Table 1]

[0349]

[0350] Based on the results shown in Table 1 above, when comparing Examples 1-3 with Comparative Examples 1-3, it can be confirmed that by using the curable compositions containing polymaleimide compound (A) and unsaturated hydrocarbon compound (B) of Examples 1-3, low dielectric constant and low dielectric loss tangent, and low moisture absorption under high temperature and high humidity conditions can be achieved.

[0351] [Industry availability]

[0352] 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 in that, contain: A polymaleimide compound (A) having the structural unit shown in the following general formula (1), and Unsaturated hydrocarbon compounds (B) with reactive double bonds, In the above general formula (1), R 1 Each can be used independently to represent 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; a hydroxyl group; or a mercapto 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 4 One side is a hydrogen atom and the other side is a methyl group, R 5 and R 6 One of them is a hydrogen atom and the other is a methyl group. X 1 The substituents represented by the following general formula (x) are: 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 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, where t represents an integer from 0 to 4. r represents the number of connections with X. 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.

2. The curable composition according to claim 1, wherein the mixing ratio of the polymaleimide compound (A) and the unsaturated hydrocarbon compound (B) having reactive double bonds, i.e., the ratio of polymaleimide compound (A): unsaturated hydrocarbon compound (B) having reactive double bonds, is 90:10 to 10:

90.

3. The curable composition according to claim 1 or 2, wherein the mixing ratio of the polymaleimide compound (A) and the unsaturated hydrocarbon compound (B) having reactive double bonds, i.e., the ratio of polymaleimide compound (A): unsaturated hydrocarbon compound (B) having reactive double bonds, is 80:20 to 20:

80.

4. The curable composition according to claim 1 or 2, wherein the mixing ratio of the polymaleimide compound (A) and the unsaturated hydrocarbon compound (B) having reactive double bonds, i.e., the ratio of polymaleimide compound (A): unsaturated hydrocarbon compound (B) having reactive double bonds, is 75:25 to 25:

75.

5. The curable composition according to claim 1 or 2, further comprising epoxy resin (C).

6. The cured product of the curable composition according to any one of claims 1 to 5.

7. A prepreg having a reinforcing substrate and a semi-cured product of a curable composition according to any one of claims 1 to 5 impregnated in the reinforcing substrate.

8. A circuit board having a laminate formed by laminating the prepreg and copper foil as described in claim 7.

9. A laminated film comprising the curable composition according to any one of claims 1 to 5.

10. A semiconductor sealing material comprising the curable composition according to any one of claims 1 to 5.

11. A semiconductor device comprising a cured form of the semiconductor sealing material of claim 10.

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