KR20230141564A - Curable composition, cured product, prepreg, circuit board, build-up film, semiconductor sealing material and semiconductor device - Google Patents

Abstract

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

Description

Curable composition, cured material, prepreg, circuit board, build-up film, semiconductor sealing material and semiconductor device {CURABLE COMPOSITION, CURED PRODUCT, PREPREG, CIRCUIT BOARD, BUILD-UP FILM, SEMICONDUCTOR SEALING MATERIAL AND SEMICONDUCTOR DEVICE}

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

A prepreg obtained by impregnating a glass cloth with a thermosetting resin such as an epoxy resin or a BT (bismaleimide-triazine) resin and heating and drying it, a laminate obtained by heat-curing the prepreg, and a combination of the laminate and the prepreg. Heat-cured multilayer boards are widely used as circuit board materials for electronic devices. Among them, package boards, which are a type of printed wiring board that acts as an interposer for mounting semiconductors, are becoming thinner, and warping of the package board during mounting has become a problem, so it is important to suppress the warping of the package board during mounting. For this purpose, materials that exhibit high heat resistance are required.

In addition, in recent years, signals have become faster and have higher frequencies, and there is a demand for a thermosetting composition that can form a cured product that maintains a sufficiently low dielectric constant under these environments and exhibits a sufficiently low dielectric loss tangent. In particular, in recent years, in various electrical material applications, especially tip material applications, there has been a demand for materials and compositions that further improve performance, including heat resistance and dielectric properties, and that combine these properties. In response to these requirements, maleimide resin is attracting attention as a material that combines heat resistance, low dielectric constant, and low dielectric loss tangent. However, although conventional maleimide resins exhibit high heat resistance, they have high hygroscopicity, and their dielectric properties (dielectric constant and dielectric loss tangent value) do not reach the level required for use as a tip material.

For example, Patent Document 1 discloses a thermosetting resin composition containing a polymaleimide resin having an indane ring and triallyl cyanurate or aromatic diamine as a material for a printed board having a dielectric constant of 4.0 or less as a laminated board without impairing heat resistance. This is disclosed.

Japanese Patent Publication No. 5-247202

However, since the thermosetting resin composition of Patent Document 1 does not examine the dielectric loss tangent value, the dielectric constant and dielectric loss tangent value do not reach the level required for use as a tip material, and have low hygroscopicity at high temperatures, low dielectric constant, and low dielectric constant. The positive and negative properties are not compatible. Additionally, since transmission loss increases as the frequency increases, circuit board materials are required to reduce transmission loss in the high frequency region. However, in the technology of Patent Document 1, only the dielectric properties in the currently used frequency band (range of hundreds of MHz to 3 GHz) have been examined, and the dielectric properties using the so-called Sub6 or higher frequency band (for example, 3.6 GHz or higher) have been examined. We are not examining whether it can support technology for the 5th generation mobile communication system (5G).

Therefore, the technical problem to be solved by the present disclosure is to provide a curable composition, cured product, prepreg, circuit board, build-up film, semiconductor sealant, and semiconductor that has low hygroscopicity and exhibits low dielectric loss tangent and low dielectric constant during curing. To provide a device.

As a result of extensive research to solve the above-mentioned problems, the present inventors have developed a polymaleimide compound (A) containing a monocyclic or fused polycyclic aromatic ring to which two or more straight-chain or branched alkylene groups are bonded, By using a curable composition containing an amine compound (B), it was found that hygroscopicity during curing, low dielectric loss tangent, and low dielectric constant could be achieved at a high level, and the present invention was completed.

According to the present disclosure, a curable composition, a cured product, a prepreg, a circuit board, a build-up film, a semiconductor sealant, and a semiconductor device are provided that can achieve high levels of low hygroscopicity, low dielectric constant, and low dielectric dissipation property during curing. can do.

According to the present disclosure, a curable composition, cured product, prepreg, circuit board, build-up film, and semiconductor that can achieve high levels of low hygroscopicity, low dielectric constant, and low dielectric loss tangent during curing even in the frequency range of Sub6 or higher. Sealing materials and semiconductor devices can be provided. This curable composition is particularly useful in applications such as electronic component encapsulation materials.

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

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

[Terms]

In this specification, “reaction raw material” refers to a compound that is used to obtain a target compound through a chemical reaction such as compounding or decomposition and partially constitutes the chemical structure of the target compound, and includes chemical substances such as solvents and catalysts. Substances that act as reaction auxiliaries are excluded. In this specification, “reaction raw material” specifically refers to, for example, when the target product is polymaleimide compound (A), the polymaleimide compound (A) or its precursor compound (e.g., the aromatic amine compound (a) refers to a precursor for obtaining the intermediate amine compound (c)) linked through the aromatic divinyl compound (b1) through a chemical reaction.

The "aromatic group" in this specification preferably has an aromatic ring with 3 to 30 carbon atoms, and more preferably has an aromatic ring with 4 to 26 carbon atoms. In addition, the "aromatic group" in this specification means that the hydrogen atom of the aromatic ring in the aromatic group is substituted with a substituent, for example, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, or a halogen atom. It's okay. In addition, the “aromatic group” includes heteroaromatics, and may be substituted with -O-, -S-, or -N= so that -CH ₂ - or -CH= in the “aromatic group” are not adjacent to each other.

Types of the aromatic ring include, for example, a monocyclic aromatic ring and a condensed polycyclic aromatic ring.

Examples of the monocyclic aromatic ring include benzene, furan, pyrrole, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, pyridine, pyrimidine, pyridazine, pyrazine, Triazine, etc. can be mentioned. Examples of the condensed polycyclic aromatic ring include naphthalene, anthracene, phenalene, phenanthrene, quinoline, isoquinoline, quinazoline, phthalazine, pteridine, coumarin, indole, benzimidazole, benzofuran, and Cridin, etc. can be mentioned. In addition, the hydrogen atom of the aromatic ring in the aromatic group is, for example, an alkyl group with 1 to 10 carbon atoms, an alkenyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, and 1 to 12 carbon atoms. may be substituted with an aryl group, an aralkyl group having 1 to 12 carbon atoms, or a halogen atom.

In addition, a monovalent aromatic group refers to a group in which one hydrogen atom in an “aromatic group” has been removed, a divalent aromatic group refers to a group in which two arbitrary hydrogen atoms in an “aromatic group” have been removed, and a trivalent to hexavalent aromatic group means, “Aromatic group” refers to a group in which 3 to 6 hydrogen atoms have been removed.

Examples of the “aralkyl group” in this specification include benzyl group, diphenylmethyl group, and naphthylmethyl group. The hydrogen atom of the aromatic ring in the aralkyl group may be substituted with, for example, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen atom. Additionally, the “aralkyl group” may be a divalent group obtained by removing one arbitrary hydrogen atom from the “aralkyl group” above.

The “alkyl group” in this specification may be straight-chain, branched, or cyclic, and may be, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, and sec-butyl group. group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, (n-)heptyl group, ( n-) octyl group, (n-) nonyl group, (n-) decyl group, (n-) undecyl group, (n-) dodecyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, Cycloheptyl group, cyclooctyl group, or cyclononyl group may be mentioned.

“Cycloalkyl group” in this specification includes cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, methylcyclobutyl group, and norbor group. Nyl group or adamantyl group, etc. can be mentioned.

The “alkylthio group” in this specification includes methylthio group, ethylthio group, propylthio group, butylthio group, octylthio group, or 2-ethylhexylthio group.

The “alkenyl group” in this specification includes ethynyl group, 1-propynyl group, 2-propynyl group, 2-butynyl group, pentynyl group, hexynyl group, vinyl group, allyl group, or isopropenyl group.

The “alkoxy group” in this specification includes, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, and octyloxy group. A group or a nonyloxy group can be mentioned.

The “aryl group” in this specification includes, for example, a phenyl group, naphthyl group, phenalenyl group, phenanthrenyl group, anthryl group, azulenyl group, tetralinyl group, etc. In addition, the "aryl group" refers to a hydrogen atom of an aromatic ring in the aryl group, for example, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, or an alkenyl group with 1 to 10 carbon atoms. Alternatively, it may be substituted with a halogen atom. Additionally, the “arylene group” may be a divalent group obtained by removing one arbitrary hydrogen atom from the “aryl group” above.

The “aryloxy group” in this specification includes a phenoxy group, naphthyloxy group, anthryloxy group, phenanthryloxy group, or pyrenyloxy group.

The “arylthio group” in this specification includes arylthio groups such as phenylthio group, naphthylthio group, anthrylthio group, phenanthrylthio group, or pyrenylthio group.

The “halogen atom” in this specification includes, for example, a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

“Structural unit” in this specification refers to a (repeating) unit of a chemical structure formed during a reaction or polymerization. In other words, in a product compound formed by a reaction or polymerization, a unit involved in the reaction or polymerization Refers to partial structures other than those of chemical bonds, and refers to so-called residues.

[Curable composition]

The curable composition of the present embodiment is a polymaleimide compound (A) (hereinafter simply referred to as polymaleimide compound (A)) containing a monocyclic or fused polycyclic aromatic ring to which two or more straight-chain or branched alkylene groups are bonded. ) and an amine compound (B).

Since the polymaleimide compound (A) has a small proportion of polar functional groups in its chemical structure, the composition as a whole can achieve both excellent low dielectric properties and low hygroscopicity. Furthermore, by combining the polymaleimide compound (A) and the amine compound (B), low hygroscopicity, low dielectric constant, and low dielectric loss tangent properties during curing can be achieved at a high degree of coexistence even in the frequency band of Sub6 or higher.

In the curable composition of the present embodiment, the mixing ratio (parts by mass) of the components of the polymaleimide compound (A) and the amine compound (B) is polymaleimide compound (A):amine compound (B), 90:10 to 90:10. It is preferably 10:90, more preferably 80:20 to 20:80, and even more preferably 75:25 to 25:75. By adjusting the mixing ratio within the above range, excellent low hygroscopicity, low dielectric constant, and low dielectric loss tangent can be achieved, so it is preferable.

The curable composition of the present embodiment may contain a curing agent (C) other than the amine compound (B) to the extent that the curing of the present invention is not impaired. In addition, the curable composition of the present embodiment may contain other resins (D), curing accelerators, or additives other than the polymaleimide compound (A) and the amine compound (B). Examples of the additive include flame retardants, inorganic fillers, silane coupling agents, mold release agents, antioxidants, light stabilizers, heat stabilizers, pigments, and emulsifiers.

Hereinafter, polymaleimide compound (A) and amine compound (A) and amine compound ( After explaining B) in detail, the optional components other than the amine compound (B), the curing agent (C), the other resin (D), the curing accelerator, and the additives are explained.

(polymaleimide compound (A))

The polymaleimide compound (A) according to the present embodiment is a compound having a monocyclic or condensed polycyclic aromatic ring to which two or more straight-chain or branched alkylene groups are bonded and two or more maleimide groups.

The monocyclic or condensed polycyclic aromatic ring to which two or more straight-chain or branched alkylene groups are bonded means that two or more straight-chain or branched alkylene groups having 1 to 12 carbon atoms are present, and one of the alkylene groups is It refers to a divalent or higher group in which two or more bonding hands are bonded to a monocyclic or condensed polycyclic aromatic ring. Therefore, the number of linear or branched alkylene groups bonded to the monocyclic or fused polycyclic aromatic ring matches the valence of the alkylene group containing the aromatic ring. The monocyclic or condensed polycyclic aromatic ring in which two or more straight-chain or branched alkylene groups are bonded in the present embodiment is preferably a divalent to tetravalent group, and more preferably a divalent to trivalent group.

The monocyclic or condensed polycyclic aromatic ring in which two or more straight-chain or branched alkylene groups are bonded in the present embodiment is preferably a group represented by the following general formula (I).

(In the general formula (I), Ar ¹ represents an aromatic group of (2+h) valence, L ¹ , L ² and L ³ each independently represent an alkylene group having 1 to 12 carbon atoms, and h is Represents an integer between 0 and 2, and * indicates a bond with another atom.)

In addition, in the general formula (I), when h is 0, the group represented by general formula (I) is divalent, and when h is 2, the group represented by general formula (I) is tetravalent.

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

(In the general formula (II), Ar ² represents an aromatic group, the broken line is absent or represents a single bond, and * represents a bond with another atom.)

In addition, in General Formula (II), the broken line is absent or represents a single bond. When the broken line is absent, the maleimide group of the general formula (II) may be monovalent. Meanwhile, when the dashed line is a single bond, the maleimide group of the general formula (II) may be divalent.

A suitable polymaleimide compound (A) of the present embodiment is a compound having a structural unit represented by the following general formula (1), or an aromatic amine compound (a) (hereinafter referred to as an aromatic amine compound) having 1 to 3 alkyl groups. (a)), an aromatic divinyl compound (b1) having two ethenyl groups (hereinafter also referred to as aromatic divinyl compound (b1)), and a compound using maleic anhydride as the reaction raw material (1). am.

(In the general formula (1), R ¹ each independently represents an alkyl group,

R ² is each independently an alkyl group, an alkoxy group, or an alkylthio group having 1 to 10 carbon atoms; Aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; Cycloalkyl group having 3 to 10 carbon atoms; halogen atom; hydroxyl group; Or represents a mercapto group,

R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, one of R ³ and R ⁴ is a hydrogen atom, the other is a methyl group, and one of R ⁵ and R ⁶ is a hydrogen atom. atom, the other side is a methyl group,

X ¹ has the following general formula (x):

(In general formula (x), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, one of R ⁷ and R ⁸ is a hydrogen atom and the other is a methyl group, and R ⁹ is each independently, An alkyl group, alkoxy group or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or represents a mercapto group, and t represents an integer of 0 to 4.)

represents a substituent ^represented by, r is the average value of the number of substitutions for X ¹ per benzene ring to which represents an integer from 1 to 4, and k represents an integer from 1 to 100.)

Thereby, at the time of hardening, low hygroscopicity and low dielectric loss tangent can be achieved to a higher degree.

<Preferred form of polymaleimide compound (A)>

The polymaleimide compound (A) of the present embodiment preferably has a structural unit represented by the general formula (1).

In addition, in the above general formula (1), when p is an integer of 2 or more, the plurality of R ¹ may be the same or different from each other. When q is an integer of 2 or more, the plurality of R ² may be the same or different from each other. When t is an integer of 2 or more, multiple R ^9s may be the same or different from each other.

In the general formula (1), R ¹ each independently preferably represents an alkyl group having 1 to 10 carbon atoms, and more preferably represents an alkyl group having 1 to 6 carbon atoms. In addition, when p is an integer of 2 or more, plural R ¹ 's may be the same or different from each other. Preferred examples of R ¹ in General Formula (1) include methyl group, ethyl group, or n-propyl group. In addition, the benzene ring to which R ¹ in General Formula (1) is bonded may be the benzene ring of the aromatic amine compound (a).

In the general formula (1), p preferably represents 1 or 2. In addition, it is preferable that R ¹ is bonded to at least one of the 2nd, 3rd, 4th, 5th, or 6th positions of the benzene ring to which R ¹ is bonded in General Formula (1).

In the general formula (1), R ² is each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; Aryl group having 6 to 10 carbon atoms; Cycloalkyl group having 3 to 10 carbon atoms; halogen atom; Alternatively, it is preferable to represent a hydroxyl group, more preferably to represent an alkyl group with 1 to 10 carbon atoms, and even more preferably to represent an alkyl group with 1 to 6 carbon atoms. In addition, when q is an integer of 2 or more, the plurality of R ² may be the same or different from each other. Preferred examples of R ² in General Formula (1) include methyl group, ethyl group, or n-propyl group. In addition, the benzene ring to which R ² in General Formula (1) is bonded may be the benzene ring of the aromatic divinyl compound (b1). Additionally, in the general formula (1), q preferably represents 0, 1, or 2.

In the general formula (1), one of R ³ and R ⁴ is a hydrogen atom and the other is a methyl group, and one of R ⁵ and R ⁶ is a hydrogen atom and the other is a methyl group. Thereby, the reactivity of the unsaturated bond of the polymaleimide compound (A) itself can be maintained at a high level. In R ³ , R ⁴ , R ⁵ and R ⁶ in the general formula (1), as the proportion of alkyl groups increases, the reactivity of the unsaturated bond of the polymaleimide compound (A) itself decreases due to steric hindrance. You can see the trend. Therefore, if R ³ , R ⁴ , R ⁵ and R ⁶ are all alkyl groups, the reactivity of the unsaturated bond of the polymaleimide compound (A) itself decreases, and a cured product cannot be formed efficiently.

In the general formula (1), it is preferable that X ¹ is represented by the general formula (x), and in the general formula (x), R ⁷ is a hydrogen atom and R ⁸ is a methyl group. In addition, in the general formula (x), R ⁹ is each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; Aryl group having 6 to 10 carbon atoms; Cycloalkyl group having 3 to 10 carbon atoms; halogen atom; Or it preferably represents a hydroxyl group, and more preferably represents an alkyl group with 1 to 10 carbon atoms or an aryl group with 6 to 10 carbon atoms, and more preferably represents an alkyl group with 1 to 6 carbon atoms or an aryl group with 6 to 10 carbon atoms. It is more desirable to indicate Moreover, in the general formula (x), t preferably represents an integer of 0 to 4, and more preferably represents an integer of 0 to 3. In addition, when t is an integer of 2 or more, plural R ^9s may be the same or different from each other.

In the general formula (1), r refers to the average value of ^the number of substitutions of X ¹ per benzene ring to which desirable.

In the general formula (1), k represents the number of repeating units, and is preferably an integer of 1 to 100, more preferably an integer of 1 to 90, and still more preferably an integer of 1 to 80.

<Other preferred forms of polymaleimide compound (A)>

Other preferred forms of the polymaleimide compound (A) of the present embodiment include an aromatic amine compound (a) having 1 to 3 alkyl groups, an aromatic divinyl compound (b1) having 2 ethenyl groups, and maleic anhydride. It may be a compound using as the reaction raw material (1). At this time, in this embodiment, an aromatic monovinyl compound (b2) having one ethenyl group (hereinafter also referred to as aromatic monovinyl compound (b2)) may be further contained in the reaction raw material (1). In addition, the polymaleimide compound (A) of the present embodiment is an intermediate amine compound ( c) and a polymaleimide compound (A) using maleic anhydride as the reaction raw material (3) are preferable. Furthermore, the intermediate amine compound (c) includes an aromatic amine compound (a) having 1 to 3 alkyl groups, an aromatic divinyl compound (b1) having two ethenyl groups, and one ethenyl group added as necessary. It is preferable that it is a compound that uses an aromatic monovinyl compound (b2) as the reaction raw material (2).

In other words, the intermediate amine compound (c) in the present embodiment is an aromatic ring to which an amino group (including a substituted amino group in which the hydrogen atom of the amino group is further substituted with an alkyl group having 1 to 6 carbon atoms) is bonded, and the aromatic ring The structural unit of the aromatic amine compound (a) having 1 to 3 alkyl groups and the structural unit of the aromatic divinyl compound (b1) having 2 ethenyl groups are linked by a chemical bond, and if necessary, aromatic monovinyl It is preferable that the structural unit of compound (b2) has a structure chemically bonded to the aromatic ring in the structural unit of the aromatic amine compound (a). In addition, the polymaleimide compound (A) in the present embodiment has an amino group (including -NH ₂ and a substituted amino group) bonded to the aromatic ring of the intermediate amine compound (c) substituted with an N-substituted maleimide ring. It has a structured structure.

Therefore, the "polymaleimide compound (A)" in this embodiment and the "intermediate amine compound (c)" which is a precursor of the "polymaleimide compound (A)" are amino groups (-NH) bonded to an aromatic ring. ₂ and a substituted amino group.) is a polymer compound that differs in that it is substituted with an N-substituted maleimide ring.

In addition, the structural unit of the aromatic amine compound (a) refers to a group obtained by removing two hydrogen atoms from the aromatic ring of the aromatic amine compound (a). For example, when the aromatic amine compound (a) is represented by the general formula (a) described 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). . In addition, the structural unit of the aromatic divinyl compound (b1) refers to a group in which the unsaturated bonds of two ethenyl groups of the aromatic divinyl compound (b1) are cleaved.

In this embodiment, since the aromatic amine compound (a) having a specific aromatic ring structure is used as the reaction raw material, it becomes easy to control the reaction site with the aromatic divinyl compound (b1) described later, thereby achieving uniform chemical chemistry. It becomes easy to obtain a polymaleimide compound (A) having a certain structure or chain length, and as a result, a polymaleimide compound (A) that exhibits low hygroscopicity and low dielectric loss factor during curing can be provided.

Hereinafter, the aromatic amine compound (a) having 1 to 3 alkyl groups, the aromatic divinyl compound (b1) having 2 ethenyl groups, and optional components of the reaction raw material (1) of the polymaleimide compound (A). After explaining the aromatic monovinyl compound (b2) having one ethenyl group and maleic anhydride, other preferred forms of the polymaleimide compound (A) and the method for producing the polymaleimide compound (A) are explained. do.

<<Aromatic amine compound (a)>>

The aromatic amine compound (a) in the present embodiment has an aromatic ring to which an amino group (-NH ₂ or substituted amino group) is bonded, and 1 to 3 alkyl groups are bonded to the aromatic ring. Therefore, the aromatic amine compound (a) may be an amine-based compound. Additionally, the aromatic ring forming the central structure of the aromatic amine compound (a) is preferably monocyclic and includes an aromatic hydrocarbon ring and an aromatic heterocycle. The aromatic hydrocarbon ring is preferably a benzene ring. Examples of aromatic heterocycles include hetero 6-membered rings such as pyran rings and pyridine rings. Moreover, it is more preferable that the aromatic amine compound (a) in the present embodiment has an aromatic ring bonded to -NH ₂ that does not contain a substituted amino group, and that at least 1 and not more than 3 alkyl groups are bonded to the aromatic ring. .

In the aromatic amine compound (a) of the present embodiment, the alkyl group substituted with 1 to 3 hydrogen atoms in the aromatic ring of the aromatic amine compound (a) includes an alkyl group having 1 to 10 carbon atoms, and a carbon atom An alkyl group with 1 to 6 carbon atoms is preferred, and an alkyl group with 1 to 3 carbon atoms is more preferred. The alkyl group may be straight-chain, branched, or cyclic. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, etc. The smaller the molecular weight of the alkyl group, the more remarkable the effect (low dimensional change rate) achieved by the present invention. Additionally, as the molecular weight of the alkyl group increases, the effect (low absorption) achieved by the present invention becomes more significant.

The upper limit of the number of alkyl groups bonded to an aromatic ring containing an amino group (-NH ₂ and a substituted amino group) in the aromatic amine compound (a) is that the aromatic ring contains an amino group (-NH ₂ and a substituted amino group). .), and from the viewpoint of two bonding hands being used for polymerization, the number may be obtained by subtracting 3 from the number of replaceable ring atoms in the unsubstituted aromatic ring.

For example, when the aromatic ring is a benzene ring, the number of alkyl groups is 3 or less.

In addition, by setting the number of alkyl groups substituted by the aromatic ring of the aromatic amine compound (a) to 2 or more, it becomes easier to control the reaction site with the aromatic divinyl compound (b1) described later, so that it has a uniform chemical structure or chain length. The polymaleimide compound (A) becomes easy to obtain. As a result, the cured product of the polymaleimide compound (A) easily exhibits low hygroscopicity and excellent high-frequency electrical properties.

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

In this embodiment, among the carbon atoms in the benzene ring constituting the aromatic amine compound (a), it is preferable that at least one carbon atom with the largest HOMO electron density (Hückel coefficient) is unsubstituted (or substituted with a hydrogen atom). do.

This makes it easy to control the ArSE reaction and molecular design using the cationoid reagent formed from the aromatic divinyl compound (b1) described later. In more detail, if the carbon atom with the largest HOMO electron density (Hückel coefficient) among the carbon atoms in the benzene ring constituting the aromatic amine compound (a) is unsubstituted, then the carbon atom with the largest HOMO electron density In contrast, the carbocation of the aromatic divinyl compound (b1), which is a cationoid reagent, is prone to reaction. Therefore, by controlling the number and position of the alkyl group bonded to the carbon atom of the benzene ring, the bonding site or number of bonds with the aromatic divinyl compound (b1) can be adjusted. Therefore, it is assumed that it will become easier to design the chemical structure or molecular chain length of the resulting polymaleimide compound (A).

For example, when the aromatic amine compound (a) has an aniline skeleton having one benzene ring and one amino group, at least one carbon atom among the 2nd, 4th, and 6th positions of the aniline nucleus is substituted with a hydrogen atom. desirable. As a result, the cationoid agent formed from the aromatic divinyl compound (b1) described later attacks at least one carbon atom among the 2nd, 4th, and 6th positions, which are the ortho and para positions with high electron density of the aniline nucleus. It becomes easier to do. In particular, when an aromatic amine compound (a) having an aniline nucleus substituted with an alkyl group is used at a specific position, the binding site with the aromatic divinyl compound (b1) can be roughly controlled, so that it has a uniform chemical structure or chain length. The polymaleimide compound (A) becomes easy to obtain. For example, if 2,6-dialkylamine is used as the aromatic amine compound (a), it is thought that many polymaleimide compounds (A) bonded to the aromatic divinyl compound (b1) at the 4-position will be obtained.

Specific examples of the aromatic amine compound (a) of the present embodiment include, for example, dimethylaniline (2,3-xylidine, 2,4-xylidine, 2,6-xylidine, 3,4-xylidine silidine or 3,5-xylidine), diethylaniline (2,3-diethylaniline, 2,4-diethylaniline, 2,6-diethylaniline, 3,4-diethylaniline or 3, 5-diethylaniline), diisopropylaniline (2,3-diisopropylaniline, 2,4-diisopropylaniline, 2,6-diisopropylaniline, 3,4-diisopropylaniline or 3, 5-diisopropylaniline), ethylmethylaniline (e.g., one of the 2,3, 2,4, 2,6, 3,4, or 3,5 positions is a methyl group, and the other ethyl group (ethylmethylaniline), cyclobutylaniline, cyclopentylaniline, cyclohexylaniline, o,m, or p-toluidine, o,m, or p-ethylaniline, o,m, or p-isopropylaniline, o ,m, or p-propylaniline, o,m, or p-butylaniline, methylisopropylaniline (e.g., positions 2,3, 2,4, 2,6, 3,4, or 3, One of the 5 positions is a methyl group, and the other is an isopropyl group (methylisopropylaniline), or ethylbutylaniline (e.g., 2,3 positions, 2,4 positions, 2,6 positions, 3,4 positions, or Ethylbutylaniline, where one of the 3 and 5 positions is an ethyl group and the other is a butyl group, etc. can be used. The butyl also includes n-butyl, tert-butyl, and sec-butyl. In addition, the aromatic amine compound (a) in this embodiment may be used individually, or may be used in combination of 2 or more types.

For example, in the case of a chemical structure such as N-phenylmaleimide, in which a maleimide group is directly bonded to an unsubstituted benzene ring, the five-membered ring of the benzene ring and maleimide is stable when arranged on the same plane, Stacking becomes easy and high crystallinity is achieved. Therefore, it causes poor solvent solubility. On the other hand, in the case of the present disclosure, when it has an alkyl group (for example, a methyl group) as a substituent for the benzene ring, such as 2,6-dimethylaniline, the benzene ring and the maleimide can be formed from the steric hindrance of the methyl group. The five-membered ring adopts a twisted configuration, which makes stacking difficult, which reduces crystallinity and improves solvent solubility, making it a preferred embodiment. However, if the steric hindrance is too large, there is concern that the reactivity during the synthesis of maleimide may be impaired, so for example, it is preferable to use an aromatic amine compound (a) having an alkyl group having 1 to 6 carbon atoms. do.

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

(In the general formula (a), R ^1a represents an alkyl group, and p ^a represents an integer of 1 to 3. Multiple R ^1a may be the same or different.)

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

In the general formula (a), p ^a is preferably 1 or 2. Moreover, when there are two or more R ^<1a> , they may be the same alkyl groups, or may be different alkyl groups.

In addition, in this embodiment, the aromatic amine compound (a) represented by the general formula (a) may be used individually, or may be used in combination of two or more types.

<<aromatic divinyl compound (b1)>>

The aromatic divinyl compound (b1) in the present embodiment has two ethenyl groups (CH ₂ =CH-) (also referred to as vinyl groups) as substituents on the aromatic ring, and reacts with the aromatic amine compound (a). If possible, it can be used without any particular restrictions.

Additionally, in this embodiment, it is preferable that the reaction raw material (1) contains a mixture of an aromatic divinyl compound (b1) and an aromatic monovinyl compound (b2).

Examples of the aromatic divinyl compound (b1) include divinylbenzene, divinylbiphenyl, divinylnaphthalene, and an alkyl group, alkoxy group, or alkylthio group having 1 to 10 carbon atoms on these aromatic rings; Aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; Cycloalkyl group having 3 to 10 carbon atoms; halogen atom; hydroxyl group; Or, various compounds substituted with one or more substituents such as a mercapto group can be mentioned. The preferred form of the substituent is the same as R ² in the general formula (1). Additionally, the alkyl group may be either straight-chain or branched. Among them, from the viewpoint of exhibiting the effect of high heat resistance, the number of carbon atoms of the alkyl group or alkoxy group is preferably 1 to 4. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, and isobutyl group. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, butoxy group, etc. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

The aromatic divinyl compound (b1), which is the reaction raw material (1) of the polymaleimide compound (A) of the present disclosure, is preferably represented by the following formula (b1).

(In the general formula (b1), R ^2b is each independently an alkyl group, an alkoxy group, or an alkylthio group having 1 to 10 carbon atoms; an aryl group, an aryloxy group, or an arylthio group having 6 to 10 carbon atoms; represents a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group, and q ^1b represents an integer from 0 to 4. In addition, when q ^1b is an integer of 2 or more, the plurality of R ^2b is the same as each other. You can do it, or it can be different.)

R ^2b in the formula (b1) may correspond to R ² in the general formula (1). Therefore, R ^2b in the general formula (b1) is each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, as in general formula (1); Aryl group having 6 to 10 carbon atoms; Cycloalkyl group having 3 to 10 carbon atoms; halogen atom; Alternatively, it is preferable to represent a hydroxyl group, more preferably to represent an alkyl group with 1 to 10 carbon atoms, and even more preferably to represent an alkyl group with 1 to 6 carbon atoms.

In the general formula (b1), q ^1b is preferably 0 to 2. Additionally, when q ^1b is 2 or more, a plurality of R ^b1 may have the same contribution or different contributions.

Specific examples of the aromatic divinyl compound (b1) of the present embodiment include, for example, 1,2-divinylbenzene, 1,3-divinylbenzene, 1,4-divinylbenzene, and 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 -Divinylbenzenes such as dibutylbenzene, 1,4-divinyl-2,5-dihexylbenzene, 1,4-divinyl-2,5-dimethoxybenzene, and compounds containing their derivatives, and , 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 their derivatives. Compounds such as divinylnaphthalene may be mentioned, but are not limited to these.

In addition, the aromatic divinyl compound (b1) in this embodiment may be used individually, or may be used in combination of 2 or more types.

In particular, from the viewpoint of fluidity, divinylbenzene and a compound having a substituent on its aromatic ring are preferable as the aromatic divinyl compound (b1), and divinylbenzene is more preferable. In addition, in this embodiment, the substitution position of the vinyl group of divinylbenzene is not particularly limited, but it is preferable that the meta body is used as the main component. The content of the meta body in divinylbenzene is preferably 40% by mass or more, and more preferably 50% by mass or more, relative to the total amount of divinylbenzene.

In the present embodiment, the structural unit of the aromatic divinyl compound (b1) is preferably contained in an amount of 10 to 90% by mass, and preferably 20 to 90% by mass, relative to the total amount (100% by mass) of the polymaleimide compound (A). It is more desirable to do so. The structural unit of the aromatic divinyl compound (b1) refers to a group obtained by removing two hydrogen atoms (total of four hydrogen atoms) from two ethenyl groups of the aromatic divinyl compound (b1).

<<aromatic monovinyl compound (b2)>>

In addition to the aromatic amine compound (a), aromatic divinyl compound (b1), and maleic anhydride, the polymaleimide compound (A) in this embodiment may also use other compounds as reaction raw materials. Examples of the other compounds include aromatic monovinyl compound (b2) having one ethenyl group. That is, in the embodiment, it is preferable to use aromatic amine compound (a), aromatic divinyl compound (b1), aromatic monovinyl compound (b2), and maleic anhydride as reaction raw materials (1). The polymaleimide compound (A) of the present embodiment uses an aromatic monovinyl compound (b2) as its reaction raw material in addition to the aromatic amine compound (a), aromatic divinyl compound (b1), and maleic anhydride, The cured product of the polymaleimide compound (A) finally obtained is preferable because it has an excellent low dielectric loss tangent.

In addition, since the aromatic monovinyl compound (b2) also generates a carbocation like the aromatic divinyl compound (b1), the electron density of HOMO is the largest among the carbon atoms in the aromatic hydrocarbon ring constituting the aromatic amine compound (a). (Hückel coefficient) is easy to react with carbon atoms.

The aromatic monovinyl compound (b2) in the present embodiment includes, for example, vinylbenzene (styrene), vinylbiphenyl, vinylnaphthalene, and an alkyl group, alkoxy group, or alkyl group having 1 to 10 carbon atoms on these aromatic rings. Thiogy; Aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; Cycloalkyl group having 3 to 10 carbon atoms; halogen atom; hydroxyl group; Or, various compounds substituted with one or more substituents such as a mercapto group can be mentioned. The alkyl group may be either straight-chain or branched, and may have an unsaturated bond in the structure. Among these, when low hygroscopicity is emphasized, it is preferable that the alkyl group or the alkoxy group has 1 to 4 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group, and isobutyl group. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, butoxy group, etc. Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom.

The aromatic monovinyl compound (b2), which can be the reaction raw material (1) of the polymaleimide compound (A) of the present disclosure, can be represented by the following general formula (b2).

(In the general formula (b2), R ^9b is each independently an alkyl group, an alkoxy group, or an alkylthio group having 1 to 10 carbon atoms; an aryl group, an aryloxy group, or an arylthio group having 6 to 10 carbon atoms; A cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or a mercapto group; and t ^1b represents an integer from 0 to 5. In addition, when t ^1b is an integer of 2 or more, the plurality of R ^9b is the same as each other. You can do it, or it can be different.)

R ^9b in the formula (b2) may correspond to R ⁹ in the general formula (x). Therefore, R ^9b in the general formula (b1), like general formula (x), each independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; Aryl group having 6 to 10 carbon atoms; Cycloalkyl group having 3 to 10 carbon atoms; halogen atom; Alternatively, it is preferable to represent a hydroxyl group, more preferably to represent an alkyl group with 1 to 10 carbon atoms, and even more preferably to represent an alkyl group with 1 to 6 carbon atoms.

In the general formula (b1), t ^1b is preferably 1 to 4. In addition, when t ^1b is 2 or more, the plurality of R ^9b may have the same contribution or different contributions.

Specific examples of the aromatic monovinyl compound (b2) of the present embodiment include, for example, styrene, fluorostyrene, vinyl benzyl chloride, alkyl vinyl benzene (o-, m-, p-methylstyrene, o-, m-, vinylbenzenes such as compounds containing p-ethylvinylbenzene), o-,m-,p-(chloromethyl)styrene, and their derivatives; Biphenyl compounds such as 4-vinylbiphenyl, 4-vinyl-p-terphenyl, and compounds containing their derivatives; In addition, vinylnaphthalenes such as 1-vinylnaphthalene, 2-vinylnaphthalene, and compounds containing derivatives thereof may be mentioned, but are not limited to these.

In particular, from the viewpoint of raw material availability, alkylvinylbenzene and compounds having a substituent on its aromatic ring are preferable, and ethylvinylbenzene is more preferable.

In addition, the substitution positions of the vinyl group and the ethyl group of ethylvinylbenzene are not particularly limited, but it is preferable that the meta form is used as the main component, and the content of the meta form in ethyl vinylbenzene is 40% by mass with respect to the total amount of ethylvinylbenzene. It is more preferable that it is 50 mass% or more, and it is still more preferable that it is 50 mass % or more.

When an aromatic monovinyl compound (b2) is used as the reaction raw material (1) for the polymaleimide compound (A) in the present embodiment, the aromatic divinyl compound (b1) in the reaction raw material (1) is The molar ratio ((b1)/(b2)) of the monovinyl compound (b2) is preferably 99/1 to 50/50, more preferably 98/2 to 70/30.

In the present embodiment, the structural unit of the aromatic monovinyl compound (b2) is preferably contained in an amount of 0 to 40% by mass, and 0 to 30% by mass, relative to the total amount (100% by mass) of the polymaleimide compound (A). It is more desirable to do so. 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).

-Maleic Anhydride-

In the present embodiment, maleic anhydride is an essential component of the reaction raw material (1) of the polymaleimide compound (A), and as explained in the section on the production method of the polymaleimide compound (A) described later, aromatic amine It is used in the maleimide reaction of amino groups (including -NH ₂ and substituted amino groups) derived from compound (a).

<Preferred form of polymaleimide compound (A)>

Hereinafter, preferred embodiments of the polymaleimide compound (A) of the present disclosure will be described taking the case where each aromatic ring is a benzene ring as an example. The following chemical structural formula is for exemplary explanation of the present disclosure, and the scope of the present disclosure is not limited to the following chemical structural formula.

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

(In the general formula (2), R ¹ each independently represents an alkyl group, and R ² each independently represents an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms; 6 carbon atoms an aryl group having 3 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 independently represent a hydrogen atom or a methyl group, and R ³ and one side of R ⁴ is a hydrogen atom and the other side is a methyl group, and one side of R ⁵ and R ⁶ is a hydrogen atom and the other side is a methyl group,

X ¹ has the following general formula (x):

(In general formula (x), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, one of R ⁷ and R ⁸ is a hydrogen atom, the other is a methyl group, and R ⁹ has 1 carbon atom. 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, and t is an integer of 0 to 4. represents.)

Represents a substituent represented by,

M ²¹ represents a hydrogen atom or a group represented by the general formula (i) below, and M ²² represents a hydrogen atom, a group represented by the general formula (ii) below, or a group represented by the general formula (iii) below,

[In the general formula (i), R ⁹ is an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms; Aryl group having 6 to 10 carbon atoms; Cycloalkyl group having 3 to 10 carbon atoms; halogen atom; or represents a hydroxyl group, R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, one of R ⁷ and R ⁸ is a hydrogen atom, the other is a methyl group, t represents an integer of 0 to 4, * indicates a bond with another atom. Additionally, when t is an integer of 2 or more, multiple R ^9s may be the same or different from each other.]

[In the general formula (ii), R ¹ⁱⁱ represents an alkyl group, and p ⁱⁱ represents an integer of 0 to 4. In addition, when p ⁱⁱ is an integer of 2 or more, plural R ¹ⁱⁱ may be the same or different from each other. In the general formula (iii), R ¹ⁱⁱⁱ represents an alkyl group, R ⁹ represents an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms; Aryl group having 6 to 10 carbon atoms; Cycloalkyl group having 3 to 10 carbon atoms; halogen atom; or represents a hydroxyl group, R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, one of R ⁷ and R ⁸ is a hydrogen atom and the other is a methyl group, and p ⁱⁱⁱ represents an integer of 0 to 3. , t represents an integer from 0 to 4, r ¹ⁱⁱⁱ is the average value of the number of substitutions per benzene ring to which X ¹ is bonded, represents a number from 1 to 4, and * represents a bond with another atom. In addition, when p ⁱⁱⁱ is an integer of 2 or more, a plurality of R ¹ⁱⁱⁱ may be the same or different from each other, and when t is an integer of 2 or more, a plurality of R ⁹ may be the same or different from each other.]

r ^is the average value of the number of substitutions of X ¹ per benzene ring to which k represents an integer from 1 to 100.)

In the general formula (2), when p is an integer of 2 or more, the plurality of R ¹ may be the same or different from each other, and when q is an integer of 2 or more, the plurality of R ² may be the same or different from each other. When t is an integer of 2 or more, multiple R ^9s may be the same or different from each other.).

In addition, the preferred forms of R ¹ to R ⁹ , X ¹ , p, q, r, t and k in the general formula (2) are the same as those in the general formula (1). Furthermore, the general formula (i) corresponds to the general formula (x), R ¹ⁱⁱ in the general formula (ii) corresponds to R ¹ in the general formula (1), and R in the general formula (iii) ¹ⁱⁱⁱ corresponds to R ¹ in the general formula (1) above.

The number average molecular weight (Mn) of the polymaleimide compound (A) of the present disclosure is preferably in the range of 350 to 2,000, and more preferably in the range of 400 to 1,500. Additionally, the weight average molecular weight (Mw) of the polymaleimide compound (A) is preferably in the range of 400 to 500,000, and more preferably in the range of 450 to 400,000.

Since the polymaleimide compound (A) of the present disclosure is excellent in low dielectric constant and low dielectric loss tangent, it has a molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) calculated from gel permeation chromatography (GPC) measurement. It is preferable that it is in the range of 1.001 to 500, and more preferably, it is 1.001 to 400. In addition, from the GPC chart obtained from GPC measurement, when the molecular weight distribution is wide and there are many high molecular weight components, the proportion of high molecular weight components contributing to flexibility increases, so compared to the cured product using conventional maleimide, , brittleness is suppressed, and a cured product with excellent flexibility and softness can be obtained, making it a desirable embodiment.

In addition, the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (weight average molecular weight (Mw)/number average molecular weight (Mn)) of the polymaleimide compound (A) of the present embodiment were determined using gel permeation chromatography. (hereinafter abbreviated as “GPC”) was measured under the measurement conditions described in the examples described later.

When the polymaleimide compound (A) in the present embodiment contains an indane skeleton (or a structural unit having an indane skeleton) represented by the following general formula (3), the total amount of the polymaleimide compound (A) ( The ratio of the indane skeleton to 100 mass%) is preferably 10 mass% or less, preferably 5 mass% or less, more preferably 3 mass% or less, even more preferably 2 mass% or less, and 0.9 mass%. The following is particularly preferable.

(In the general formula (3), R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ³⁴ each independently represents an alkyl group having 1 to 10 carbon atoms. Alkyl group, alkoxy group or alkylthio group; Aryl group, aryloxy group or arylthio group having 6 to 10 carbon atoms; Cycloalkyl group having 3 to 10 carbon atoms; Halogen atom; Hydroxyl group; or mercapto group, q ³ represents an integer of 0 to 3, and when q ³ is an integer of 2 or more, the plurality of R ³⁴ may be the same or different from each other. Additionally, * represents a bond with another atom.)

In the general formula (3), R ³⁴ each independently preferably represents an alkyl group having 1 to 6 carbon atoms, and more preferably represents an alkyl group having 1 to 3 carbon atoms. Additionally, in the general formula (3), R ³¹ , R ³² and R ³³ are preferably hydrogen atoms or methyl groups.

In the curable composition of the present embodiment, it is preferable to contain 60% by mass or more and 95% by mass or less of the polymaleimide compound (A) relative to the entire curable composition, and it is more preferable to contain 70% by mass or more and 93% by mass or less. , it is most preferable to contain 80% by mass or more and 90% by mass or less. It is preferable from the viewpoint of heat resistance that the content of the polymaleimide compound (A) is in the range of 60% by mass or more and 95% by mass or less.

<Method for producing polymaleimide compound (A)>

Hereinafter, a method for producing the polymaleimide compound (A) of the present disclosure will be described.

The production method of the polymaleimide compound (A) of the present embodiment is not particularly limited, and an aromatic amine compound (a), an aromatic divinyl compound (b1), and maleic anhydride are used as reaction raw materials (1), Alternatively, it may be manufactured in any way as long as it has a structural unit represented by the above general formula (1). An example of a method for producing the polymaleimide compound (A) of the present disclosure includes, for example, a production method including the following steps (1) and (2).

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

Step (2): A step of obtaining the polymaleimide compound (A) of the present disclosure by reacting the intermediate amine compound (c) obtained in the above step (1) with maleic anhydride as the reaction raw material (3).

Specifically, the method for producing the polymaleimide compound (A) of the present embodiment includes step (1) (also referred to as the crosslinking step) of reacting the aromatic amine compound (a) and the aromatic divinyl compound (b1) in the presence of a solid acid catalyst. It is preferable to have a step (2) (also called a condensation step) of condensing the intermediate amine compound (c) produced in step (1) and maleic anhydride.

Hereinafter, each step of the method for producing the polymaleimide compound (A) of the present disclosure will be described in turn.

<<Step (1): Manufacturing process of intermediate amine compound (c)>>

Below, the manufacturing process of the intermediate amine compound (c) in this embodiment is explained.

The step (1) in the present embodiment is not particularly limited, but includes, for example, the aromatic amine compound (a) described above, the aromatic divinyl compound (b1) (e.g., divinylbenzene) described above, Additionally, if necessary, this is a step of reacting other compounds such as aromatic monovinyl compound (b2) (for example, ethylvinylbenzene) in the presence of an acid catalyst. Thereby, the intermediate amine compound (c) can be produced.

The mixing ratio of the aromatic amine compound (a) and the aromatic divinyl compound (b1) is 1 mole of the aromatic amine compound (a), considering the physical property balance of moldability and curability during production of the resulting cured product. The molar ratio of the aromatic divinyl compound (b1) is preferably 0.1 to 10 mol, and more preferably 0.2 to 3 mol. In addition, when the aromatic monovinyl compound (b2) is used in combination, the molar ratio of the sum of the aromatic divinyl compound (b1) and the aromatic monovinyl compound (b2) relative to 1 mole of the aromatic amine compound (a) is , 0.1 to 10 mol is preferable, and 0.2 to 3 mol is more preferable.

In addition, as a specific method of carrying out the above reaction, all raw materials are charged in batches and allowed to react as is at a predetermined temperature, or an aromatic amine compound (a) and an acid catalyst are charged and the aromatic amine compound (a) is maintained at a predetermined temperature while maintaining the aromatic amine compound (a) at a predetermined temperature. A common method is to carry out the reaction while dropping divinyl compound (b1) or other compounds (for example, aromatic monovinyl compound (b2)). At this time, the dropping time is usually 0.1 to 12 hours, and is preferably 6 hours or less. After the reaction, when a solvent is used, the solvent and unreacted substances are distilled off as necessary to obtain the intermediate amine compound (c), and when a solvent is not used, the unreacted substances are distilled off to obtain the target product. The intermediate amine compound (c) can be obtained.

The acid catalyst used in step (1) of this embodiment includes, for example, inorganic acids such as phosphoric acid, hydrochloric acid, and sulfuric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid, activated clay, Examples include solid acids such as acid clay, silica alumina, zeolite, strongly acidic ion exchange resin, heteropoly hydrochloric acid, etc. Solid acids that can easily remove the catalyst by filtration after reaction are preferable from the viewpoint of hand linking, and other acids can be used. In this case, it is preferable to perform neutralization with a base and washing with water after the reaction.

The mixing amount of the acid catalyst is 100 parts by mass of the total amount of the input raw materials (aromatic divinyl compound (b1) or a mixture of aromatic divinyl compound (b1) and aromatic monovinyl compound (b2) and aromatic amine compound (a)). In contrast, the acid catalyst is blended in the range of 1 to 100 parts by mass, but 1 to 60 parts by mass is preferable from the viewpoint of handling and economic efficiency. The reaction temperature can generally be in the range of 100 to 270°C, but is preferably 100 to 220°C to suppress the formation of isomeric structures and avoid side reactions such as thermal decomposition.

In step (1) of the present embodiment, the reaction time of the aromatic divinyl compound (b1) or the mixture of the aromatic divinyl compound (b1) and the aromatic monovinyl compound (b2) and the aromatic amine compound (a), that is, The time for the crosslinking reaction is that the reaction does not proceed completely in a short time, and if it is prolonged, side reactions such as thermal decomposition reaction of the product occur, so under the above reaction temperature conditions, it is usually in the range of 1 to 48 hours in total. Preferably, it ranges from 1 to 30 hours in total.

In the method for producing the intermediate amine compound (c) in the present embodiment, aniline or a derivative thereof also serves as a solvent, so it is not necessarily necessary to use another solvent, but it is also possible to use a solvent. For example, when reacting with divinylbenzene as a raw material, a solvent that can be azeotropically dehydrated, such as toluene, xylene, or chlorobenzene, is used to azeotropically dehydrate moisture contained in the catalyst, etc., if necessary, and then the solvent is distilled off. After that, a method of performing the reaction within the above reaction temperature range may be adopted.

The intermediate amine compound (c) obtained by the above step (1) is preferably represented by the following general formula (4), for example.

(In the general formula (4), R ¹ each independently represents an alkyl group, and R ² each independently represents an alkyl group, an alkoxy group, or an alkylthio group having 1 to 10 carbon atoms; Represents an aryl group, an aryloxy group or an arylthio group; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group or a mercapto group,

R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, one of R ³ and R ⁴ is a hydrogen atom, the other is a methyl group, and one of R ⁵ and R ⁶ is a hydrogen atom. atom, the other side is a methyl group,

X ¹ has the following general formula (x):

(In general formula (x), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, one of R ⁷ and R ⁸ is a hydrogen atom, the other is a methyl group, and R ⁹ represents an alkyl group, t represents an integer from 0 to 4.)

represents a substituent ^represented by, r is the average value of the number of substitutions for X ¹ per benzene ring to which represents an integer from 1 to 4, and k represents an integer from 1 to 100.) It is preferable to have a structural unit represented by.

In addition, in the above general formula (4), when p is an integer of 2 or more, the plurality of R ¹ may be the same or different from each other. When q is an integer of 2 or more, the plurality of R ² may be the same or different from each other. When t is an integer of 2 or more, multiple R ^9s may be the same or different from each other.

In addition, the preferred forms of R ¹ to R ⁹ , X ¹ , p, q, r, t and k in the general formula (4) are the same as those in the general formula (1). In addition, as another preferred form of the intermediate amine compound (c) obtained by the above step (1), the N-substituted maleimide group in the general formula (2), which is also a preferred form of the polymaleimide compound (A), is replaced with an amino group (- Includes NH ₂ and substituted amino groups.) Substituted structures may be mentioned.

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

In addition, the measurement of the amine equivalent weight of the intermediate amine compound (c) in this specification is the value measured by a method based on the neutralization titration method specified in JIS K 0070 (1992).

<<Process (2): Maleimide>>

Step (2) in this embodiment is a step of reacting the intermediate amine compound (c) obtained in step (1) with maleic anhydride. Because the amino group (including -NH ₂ and a substituted amino group) of the intermediate amine compound (c) can form a chemical structure in which the amino group is substituted with an N-substituted maleimide ring through a maleimide reaction, this The polymaleimide compound (A) of the disclosure is obtained.

In this embodiment, the intermediate amine compound (c) represented by the general formula (4) obtained in step (1) is charged to a reactor, dissolved in an appropriate 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, etc., and the solvent is removed by reduced pressure to obtain the target polymaleimide compound (A). Additionally, if necessary, a dehydrating agent may be used during the reaction.

Organic solvents used in step (2) of this embodiment include ketones such as acetone, methyl ethyl ketone (MEK), methyl isobutyl ketone, cyclohexanone, and acetophenone, N,N-dimethylformamide, N, Aprotic solvents such as N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, acetonitrile, sulfolane, cyclic ethers such as dioxane and tetrahydrofuran, ethyl acetate, butyl acetate, etc. esters, and aromatic solvents such as benzene, toluene, and xylene, and these may be used individually or in combination.

In step (2) of the present embodiment, the mixing ratio of the intermediate amine compound (c) and maleic anhydride is the equivalent ratio of maleic anhydride to the amino equivalent of the intermediate amine compound (c) in the range of 1 to 5. It is preferable to mix, more preferably 1 to 3, and react in an organic solvent at a mass ratio of 0.1 to 10, preferably 0.2 to 5, relative to the total amount of the intermediate amine compound (c) and maleic anhydride. It is desirable to do so.

Catalysts that can be used in step (2) of this embodiment include acetates such as nickel, cobalt, sodium, calcium, iron, lithium, and manganese, inorganic salts such as chloride, bromide, sulfate, and nitrate, phosphoric acid, hydrochloric acid, Inorganic acids such as sulfuric acid, organic acids such as oxalic acid, benzenesulfonic acid, toluenesulfonic acid, methanesulfonic acid, and fluoromethanesulfonic acid, activated clay, acid clay, silica alumina, zeolite, solid acids such as strongly acidic ion exchange resin, heteropoly hydrochloric acid, etc. In particular, toluenesulfonic acid is preferably used.

Dehydrating agents used in step (2) of this embodiment include lower aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic anhydride, and butyric acid, oxides such as phosphorus pentoxide, calcium oxide, and barium oxide, inorganic acids such as sulfuric acid, and molecular sieves. Porous ceramics such as the like, and preferably acetic anhydride can be used.

There is no particular limitation on the amount of catalyst and dehydrating agent used in step (2) of the present embodiment, but usually, the amount of catalyst is 0.0001 to 1.0 mol per equivalent of the amino group (-NH ₂ ) of the intermediate amine compound (c). Preferably 0.01 to 0.3 mol, dehydrating agent can be used in 1 to 3 mol, preferably 1 to 1.5 mol.

In step (2) of the present embodiment, the reaction conditions for maleimidization include adding the intermediate amine compound (c) and maleic anhydride, and reacting at a temperature in the range of 10 to 100°C, preferably 30 to 60°C. , after reacting for 0.5 to 12 hours, preferably 1 to 4 hours, the catalyst is added, and reacted for 1 to 24 hours, preferably 1 to 120°C, in a temperature range of 90 to 130°C, preferably 105 to 120°C. The reaction can take 10 hours.

(Amine compound (B))

The curable composition of this embodiment contains an amine compound (B). By combining the amine compound (B) and the polymaleimide compound (A), the composition as a whole can contribute to low-temperature curing and exhibit excellent molding processability, making it useful as it can be used as a molding material for structural materials. In addition, through reaction with the polymaleimide compound (A), it acts as a curing agent, can generate three-dimensional crosslinking, and a cured product with excellent heat resistance can be obtained, making it a preferred embodiment.

The amine compound (B) in the present embodiment includes compounds having primary to tertiary amino groups, and is preferably a hydrocarbon having 1 or more carbon atoms, preferably 3 to 25 carbon atoms, and 1 Hydrocarbon compounds having two or more primary amino groups in the molecule are more preferable. As the amine compound (B), an aliphatic amine compound or an aromatic amine compound is preferable, and an aliphatic primary diamine compound or an aromatic primary diamine compound is more preferable.

Additionally, aromatic amine compounds include aromatic heterocyclic compounds, and aliphatic amine compounds include alicyclic aliphatics.

Specific examples of the aliphatic amine compound of the present embodiment include ethylenediamine, diethylenetriamine, hexamethylenediamine, triethylenetetramine, isophoronediamine, guanidine derivatives, guanamine derivatives, and 1,3-bisaminomethyl. Cyclohexane, morpholine, 4,4-methylenebiscyclohexanamine, and 4,4-ethylenebiscyclohexanamine can be mentioned. The aliphatic amine compounds may be used individually or in combination of two or more types.

Specific examples of the aromatic amine compound of the present embodiment include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 3-methyl-1,4-diaminobenzene, m-xylenediamine, p-xylenediamine, diethyltoluenediamine, 2,5-dimethyl-1,4-diaminobenzene, diaminodiphenylmethane (e.g. 4,4'-diaminodiphenylmethane), diaminodiphenyl Ethane, 4,4'-diamino-3,3'-dimethyl-diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, diaminodiphenyl ether (e.g. , 4,4'-diaminodiphenyl ether), diaminodiphenylsulfone (e.g., 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone), 4,4' -Diaminodiphenyl ketone, benzidine, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihyde Roxybenzidine, 2,2-bis (3-amino-4-hydroxyphenyl) propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis (4 -aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy) ) Benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, bis (4- (4-aminophenoxy) phenyl) sulfone, bis ( Examples include 4-(3-aminophenoxy)phenyl)sulfone, 9,9-bis(4-aminophenyl)fluorene, and imidazole. The aromatic amine compounds may be used individually or in mixture of two or more types.

Among the above aromatic amine compounds, when importance is placed on mechanical properties during curing, m-phenylenediamine, p-phenylenediamine, 3-methyl-1,4-diaminobenzene or 2,5-dimethyl-1,4- Diaminobenzene is more preferred. On the other hand, when heat resistance is important, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-dimethyl -Diphenylmethane, 4,4'-diamino-3,3'-diethyl-diphenylmethane, 4,4'-bis(4-aminophenoxy)biphenyl or 2,2-bis(4-( 4-aminophenoxy)phenyl)propane is more preferred.

In addition, when solubility in solvents or handleability is important, 4,4'-diaminodiphenylmethane, 3,3'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino- 3,3'-diethyl-diphenylmethane and 2,2-bis(4-(4-aminophenoxy)phenyl)propane are more preferred. Furthermore, if low dielectric properties are important, 4,4'-diamino-3,3'-diethyl-diphenylmethane and 2,2-bis(4-(4-aminophenoxy)phenyl)propane are preferred. desirable.

In addition, other amine compounds (B) other than the aliphatic amine compound and the aromatic amine compound include hydroxylammonium sulfate, BF ₃ -amine complex, and the like.

As a preferred amine compound (B) of the present embodiment, an aromatic amine compound is preferred when control of the curing reaction and moldability are emphasized. Since the aliphatic amine compound acts as a catalyst and tends to cause the curing reaction to proceed quickly, when moldability is emphasized, it is preferable to use an aromatic amine compound.

In the curable composition of the present embodiment, it is preferable to contain 5 mass% or more and 50 mass% or less of the amine compound (B) relative to the entire curable composition, more preferably 7 mass% or more and 30 mass% or less, and 10 It is most preferable to contain at least 20 mass% by mass. It is preferable from the viewpoint of heat resistance that the content of the amine compound (B) is in the range of 10 mass% or more and 20 mass% or less.

(Hardener (C) other than amine compound (B))

A curing agent (C) other than the amine compound (B) may be added to the curable composition of the present embodiment as long as it does not impair the curing of the present invention. Furthermore, the curing agent (C) is preferably 2% by mass or more and 20% by mass or less, and most preferably 5% by mass or more and 10% by mass or less, relative to 100% by mass of the total amount of the curable composition. It is preferable from the viewpoint of curability and low dielectric loss tangent that the content of the curing agent (C) is in the range of 5 mass% or more and 10 mass% or less.

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

Examples of the cyanate compound include bisphenol A cyanate ester resin, bisphenol F cyanate ester resin, bisphenol E cyanate ester resin, bisphenol S cyanate ester resin, and bisphenol sulfide cyanate ester resin. , phenylene ether type cyanate ester resin, naphthylene ether type cyanate ester resin, biphenyl type cyanate ester resin, tetramethyl biphenyl type cyanate ester resin, polyhydroxynaphthalene type cyanate ester resin, phenol novolak. type cyanate ester resin, cresol novolac type cyanate ester resin, triphenylmethane type cyanate ester resin, tetraphenylethane type cyanate ester resin, dicyclopentadiene-phenol addition reaction type cyanate ester resin, phenol aralkyl Type cyanate ester resin, naphthol novolak type cyanate ester resin, naphthol aralkyl type cyanate ester resin, naphthol-phenol coaxial novolac type cyanate ester resin, naphthol-cresol coaxial novolac type cyanate ester resin, aromatic hydrocarbon Formaldehyde resin-modified phenol resin-type cyanate ester resin, biphenyl-modified novolak-type cyanate ester resin, and anthracene-type cyanate ester resin can be mentioned. These may be used individually, or two or more types may be used together.

Examples of the amide-based compounds include dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid, and ethylenediamine.

Examples of the acid anhydride-based compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methyl. Hexahydrophthalic anhydride, etc. can be mentioned.

Examples of the phenolic compounds include phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol addition type resin, phenol aralkyl resin (xylock resin), and resorcinol. Polyhydric phenol novolak resin, naphthol aralkyl resin, trimethylolmethane resin, tetraphenylolethane resin, naphthol novolak resin, naphthol-phenol coaxial novolak resin, synthesized from polyvalent hydroxy compounds represented by rockfish resin and formaldehyde, Naphthol-cresol coaxial novolac resin, biphenyl-modified phenol resin (polyhydric phenol compound whose phenol core is linked to a bismethylene group), biphenyl-modified naphthol resin (polyhydric naphthol compound whose phenol core is linked to a bismethylene group), aminotriazine-modified phenol resin Examples include polyhydric phenol compounds such as (polyhydric phenol compounds whose phenol nuclei are linked with melamine, benzoguanamine, etc.) and aromatic ring-modified novolak resins containing alkoxy groups (polyhydric phenol compounds where phenol nuclei and alkoxy group-containing aromatic rings are linked with formaldehyde). You can.

As the polyphenylene ether-based compound, for example, it is preferable to have a structure represented by the following general formula (5) or (16).

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

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

The alkylcarbonyl group having 2 to 5 carbon atoms is not particularly limited, and includes methylcarbonyl group, ethylcarbonyl group, propylcarbonyl group, isopropylcarbonyl group, butylcarbonyl group, etc.

The alkyloxycarbonyl group having 2 to 5 carbon atoms is not particularly limited, and includes methyloxycarbonyl group, ethyloxycarbonyl group, propyloxycarbonyl group, isopropyloxycarbonyl group, butyloxycarbonyl group, etc.

The alkylcarbonyloxy group having 2 to 5 carbon atoms is not particularly limited, but includes methylcarbonyloxy group, ethylcarbonyloxy group, propylcarbonyloxy group, isopropylcarbonyloxy group, and butylcarbonyloxy group. etc. can be mentioned.

The alkylsulfonyl group having 1 to 5 carbon atoms is not particularly limited, and includes methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, and pentylsulfonyl group.

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

Y in the general formula (6) includes a divalent aromatic group derived from an aromatic compound having two phenolic hydroxyl groups.

The aromatic compound having two phenolic hydroxyl groups is not particularly limited, but includes catechol, resorcinol, hydroquinone, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene. Dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol B, bisphenol BP, bisphenol C, bisphenol F, tetramethylbisphenol A, etc. Among these, hydroquinone, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, 4,4'-biphenol, bisphenol A, bisphenol E, and bisphenol F are preferred, and 4,4'-bisphenol Phenol, bisphenol A, and tetramethylbisphenol A are more preferable.

In addition, since the two phenolic hydroxyl groups of the aromatic compound having two phenolic hydroxyl groups form a phenylene ether bond (two oxygen atoms bonded to Y), Y is an aromatic compound having two phenolic hydroxyl groups. It becomes a divalent aromatic group derived from a compound. In other words, a group obtained by removing two arbitrary hydrogen atoms from the aromatic compound having two phenolic hydroxyl groups is referred to as a “divalent aromatic group derived from an aromatic compound having two phenolic hydroxyl groups.”

The compound having the unsaturated double bond-containing substituent is not particularly limited, for example, as long as it is a compound having two or more unsaturated bond-containing substituents in the molecule. Examples of the unsaturated bond-containing substituent include allyl group, isopropenyl group, and 1-propenyl group. Compounds having a phenyl group, acryloyl group, methacryloyl group, styryl group, styrylmethyl group, etc. can be mentioned.

Examples of the diene polymer include unmodified diene polymers that are not modified by a polar group. Here, a polar group is a functional group that affects dielectric properties, and examples include phenol group, amino group, and epoxy group. The diene-based polymer is not particularly limited, and for example, 1,2-polybutadiene, 1,4-polybutadiene, etc. can be used.

As the diene-based polymer, a homopolymer of butadiene and its derivatives in which 50% or more of the butadiene units in the polymer chain are 1,2-links can also be used.

(Other Resins (D))

In addition, other resins (D) may be contained in addition to the polymaleimide compound (A) and the amine compound (B), as long as they do not impair the purpose of the present disclosure. Examples of the other resin (D) include bismaleimides other than the polymaleimide compound (A), allyl ether compounds, allylamine compounds, triallyl cyanurate, alkenylphenol compounds, and vinyl group-containing polyolefins. Compounds, etc., epoxy resin, phenol resin, activated ester resin, polyphenylene ether resin, benzoxazine resin, styrene maleic anhydride copolymer, polybutadiene and its modified products, polyacetal resin, polyvinyl alcohol resin, liquid crystal polymer, It is also possible to appropriately mix fluororesin, polystyrene, polyethylene, polyimide resin, thermosetting polyimide resin, silicone gel, silicone oil, etc.

Additionally, since the curable composition of the present embodiment contains an amine compound (B), an epoxy resin may be selected as the other resin (D). Thereby, in the curable composition containing the polymaleimide compound (A), the amine compound (B), and the epoxy resin, the amine compound (B) acts as a curing agent, and thus the adhesion to copper is improved, for example , it can be useful in the manufacture of circuit boards using copper foil.

The epoxy resin is not particularly limited, but includes, for example, phenol novolak-type epoxy resin, cresol novolak-type epoxy resin, α-naphthol novolak-type epoxy resin, β-naphthol novolak-type epoxy resin, and bisphenol A novolak. Novolak-type epoxy resins such as epoxy resins and biphenyl novolak-type epoxy resins; Aralkyl type epoxy resins such as phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin, and phenol biphenyl aralkyl type epoxy resin; 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 Bisphenol type epoxy resins such as type epoxy resin and tetrabromobisphenol A type epoxy resin; Biphenyl-type epoxy resins such as biphenyl-type epoxy resins, tetramethylbiphenyl-type epoxy resins, and epoxy resins having a biphenyl skeleton and a diglycidyloxybenzene skeleton; Naphthalene type epoxy resin; Binaphthol type epoxy resin; Binaphthyl type epoxy resin; Dicyclopentadiene type epoxy resins such as dicyclopentadiene phenol type epoxy resin; Glycidylamine type epoxy resins such as tetraglycidyldiaminodiphenylmethane type epoxy resin, triglycidyl-p-aminophenol type epoxy resin, and glycidylamine type epoxy resin of diaminodiphenylsulfone; diglycidyl ester type epoxy resins such as 2,6-naphthalenedicarboxylic acid diglycidyl ester type epoxy resin and hexahydrophthalic anhydride glycidyl ester type epoxy resin; and benzopyran-type epoxy resins such as dibenzopyran, hexamethyldibenzopyran, and 7-phenylhexamethyldibenzopyran. These may be used individually, or two or more types may be used together.

The content of the other resin (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, based on 100% by mass of the total amount of the curable composition. It is preferable from the viewpoint of heat resistance that the content of the other resin (D) is in the range of 5 mass% or more and 10 mass% or less.

(curing accelerator)

The curable composition of this embodiment can also be used in combination with a curing accelerator as needed. Various curing accelerators can be used. For example, the addition of a polymerization initiator such as an organic peroxide or an azo compound or a basic catalyst such as a phosphine compound or a tertiary amine is effective. Specific examples of the curing accelerator include benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, TPP-MK, TPP-K, triethylamine, imidazole, etc. You can. A hardening accelerator may be used individually, or two or more types may be used together. The compounding amount of the curing accelerator in this embodiment is preferably 0.05 to 5 mass% of the entire curable resin composition.

(additive)

The curable composition of the present embodiment may be used in combination with additives as needed. Examples of the additive include silane coupling agents, mold release agents, pigments, emulsifiers, non-halogen-based flame retardants, inorganic fillers, flame retardants, solvents, etc. The content of the additive is preferably 1% by mass or more and 20% by mass or less, and most preferably 3% by mass or more and 10% by mass or less, based on the total amount of 100% by mass of the curable composition.

Examples of the flame retardant include inorganic phosphorus-based flame retardants, organic phosphorus-based flame retardants, halogen-based flame retardants, or non-halogen-based flame retardants. In order to exhibit flame retardancy within a range that does not impair the purpose, it is more preferable to mix a non-halogen-based flame retardant that does not substantially contain a halogen atom in the curable composition of the present embodiment. Examples of the non-halogen-based flame retardants include phosphorus-based flame retardants, nitrogen-based flame retardants, silicon-based flame retardants, inorganic flame retardants, and organic metal salt-based flame retardants, and these can be used alone or in combination.

If necessary, an inorganic filler can be added to the curable composition of this embodiment. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When the compounding amount of the above inorganic filler is particularly large, it is preferable to use fused silica. The fused silica can be used in either crushed or spherical form, but in order to increase the amount of fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use the spherical form. Furthermore, in order to increase the compounding amount of spherical silica, it is desirable to appropriately adjust the particle size distribution of spherical silica. Taking flame retardancy into consideration, the higher the filling rate, the higher it is preferable, and it is especially preferably 30% by mass or more and 50% by mass or less with respect to the total amount of the curable composition. Additionally, when using the curable composition for purposes such as a conductive paste described in detail below, a conductive filler such as silver powder or copper powder can be used.

In the curable composition of the present embodiment, the lower limit of the total content of the polymaleimide compound (A) and the amine compound (B) relative to the entire curable composition (100 mass%) is 40 mass%, 42 mass%, 45 mass%, It is preferable that it is 47 mass %, 48 mass %, or 50 mass %. In addition, the upper limit of the total content is preferably 100% by mass, 99% by mass, 98% by mass, or 97% by mass. The upper limit value and the lower limit value can be arbitrarily combined. Therefore, for example, the curable composition of the present embodiment has a total content of the polymaleimide compound (A) and the amine compound (B) of 40% by mass or more and 100% by mass or less with respect to the entire curable composition (100% by mass). Preferably, the total content of the polymaleimide compound (A) and the amine compound (B) is more preferably 45% by mass or more and 100% by mass or less, and the total content of the polymaleimide compound (A) and the amine compound (B) is It is more preferable that it is 50 mass % or more and 100 mass % or less.

The curable composition of the present embodiment has a lower limit of the total content of the polymaleimide compound (A), the amine compound (B), and the inorganic filler relative to the entire curable composition (100 mass%) of 70 mass%, 73 mass%, and 75 mass%. It is preferable that it is mass %, 77 mass %, or 80 mass %. In addition, the upper limit of the total content is preferably 100% by mass, 99% by mass, 98% by mass, or 97% by mass. The upper limit and the lower limit can be arbitrarily combined in the same manner as the range of the total content of the polymaleimide compound (A) and the amine compound (B).

In the curable composition of the present embodiment, the lower limit of the total content of the polymaleimide compound (A), amine compound (B), and additives relative to the entire curable composition (100 mass%) is 43 mass%, 45 mass%, and 48 mass%. %, 50 mass % or 53 mass % is preferable. In addition, the upper limit of the total content is preferably 100% by mass, 99% by mass, 98% by mass, or 97% by mass. The upper limit and the lower limit can be arbitrarily combined in the same manner as the range of the total content of the polymaleimide compound (A) and the amine compound (B).

[Hardened product]

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

The curing (thermal curing) reaction can be easily carried out without a catalyst, but when a faster reaction is desired, a polymerization initiator such as an organic peroxide or azo compound or a basic catalyst such as a phosphine compound or tertiary amine must be added. is effective. For example, there are benzoyl peroxide, dicumyl peroxide, azobisisobutyronitrile, triphenylphosphine, triethylamine, imidazole, etc., and the blending amount is 0.05 to 5% by mass of the entire curable resin composition. desirable.

[Heat-resistant materials and electronic materials]

Since the cured product obtained from the curable composition containing the polymaleimide compound (A) and the amine compound (B) of the present disclosure has both excellent low hygroscopicity and low dielectric properties, it is suitable for use in heat-resistant members or electronic components. possible. In particular, it can be suitably used for prepreg, circuit boards, semiconductor encapsulants, semiconductor devices, build-up films, build-up substrates, adhesives and resist materials using conductive paste, etc. In addition, it can be suitably used as a matrix resin of fiber-reinforced resin, and is particularly suitable as a prepreg with high heat resistance or a small dimensional change rate. In addition, the polymaleimide compound (A) contained in the curable composition exhibits excellent solubility in various solvents and can be converted into paint. The heat-resistant members and electronic members obtained in this way can be suitably used for various purposes, for example, industrial machine parts, general machine parts, parts for automobiles, railways, vehicles, etc., aerospace and aviation-related parts, and electronic and electrical parts. , building materials, containers/packaging members, household goods, sports/leisure products, housing members for wind power generation, etc., but are not limited to these.

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

[Circuit board]

This disclosure is a circuit board that is a laminate of the following prepreg and copper foil. As a method of obtaining a printed circuit board from the curable composition of the present embodiment, the prepreg is laminated by a conventional method, copper foil is appropriately overlapped, and the prepreg is heated at 170 to 300° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa. , and methods of heat compression.

[Semiconductor sealing material]

This disclosure is a semiconductor encapsulating material containing the curable composition of the present embodiment. The semiconductor encapsulating material obtained using the curable composition of the present embodiment has improved hygroscopicity and low dielectric dissipation rate by using the polymaleimide compound (A) and amine compound (B) of the present disclosure, and is therefore suitable for the manufacturing process. It is excellent in processability, moldability, and reflow properties, making it a desirable aspect.

The curable composition of this embodiment used for the semiconductor encapsulating material may contain an inorganic filler. In addition, as the filling rate of the inorganic filler, for example, the inorganic filler can be used in the range of 0.5 to 1200 parts by mass with respect to 100 parts by mass of the curable composition of the present embodiment. In addition, as the inorganic filler, as mentioned above, for example, barium sulfate, barium titanate, amorphous silica, crystalline silica, Neuburg silica, fused silica, spherical silica, talc, clay, magnesium carbonate, calcium carbonate, Aluminum oxide, aluminum hydroxide, silicon nitride, aluminum nitride, etc. can be mentioned.

As a method of obtaining the semiconductor encapsulating material, the curable composition of the present embodiment is sufficiently melted and mixed with optional components, such as a curing accelerator and/or additives, as needed, using an extruder, kneader, roll, etc., until uniform. Methods, etc. may be mentioned. When used as a high thermal conductivity semiconductor sealing material for power transistors and power ICs, highly charged 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, may be used. The filling rate is preferably in the range of 30 to 95 parts by mass of the inorganic filler per 100 parts by mass of the curable composition, and in particular, in order to improve flame retardancy, moisture resistance, and solder crack resistance, and reduce the coefficient of linear expansion, it is 70 parts by mass. It is more preferable that it is more than 80 parts by mass, and it is more preferable that it is 80 parts by mass or more.

[Semiconductor device]

The present disclosure is a semiconductor device including a cured product of the above semiconductor encapsulating material. The semiconductor device obtained using the semiconductor encapsulating material obtained using the curable composition of the present embodiment has low viscosity and excellent fluidity because the polymaleimide compound (A) and amine compound (B) of the present disclosure are used, In addition, since hygroscopicity, thermal modulus of elasticity, or adhesion to metal materials are improved, processability, moldability, and reflow properties in the manufacturing process are excellent, making it a desirable aspect.

A method of obtaining the semiconductor device includes molding the semiconductor encapsulating material using a mold, transfer molding machine, injection molding machine, etc., and heating and curing it at a temperature range from room temperature (20°C) to 250°C. .

[Prepreg]

The present disclosure is a prepreg having a reinforcing base material and a semi-cured product of the curable composition of the present embodiment impregnated into the reinforcing base material. As a method of obtaining a prepreg from the curable composition, the organic solvent described later is mixed and the varnished curable composition is mixed with a reinforcing substrate (paper, glass cloth, glass non-woven fabric, aramid paper, aramid cloth, glass mat, glass roving cloth, etc. ) and then heating at a heating temperature depending on the type of solvent used, preferably 50 to 170°C, to semi-cure (or uncure) the curable composition to obtain a prepreg. The mass ratio of the curable composition and the reinforcing base material used at this time is not particularly limited, but is usually preferably adjusted so that the resin content contained in the composition in the prepreg is 20 to 60% by mass.

In this embodiment, the semi-cured product of the curable composition is obtained by adjusting the heating temperature and heating time and stopping the curing reaction midway without completing it. Also, for example, the semi-cured product may have a degree of curing of, for example, 85% or less and 5% or more. On the other hand, the cured product in this embodiment can have a higher degree of curing than the semi-cured product.

In addition, the degree of cure of the semi-cured product can be calculated by measuring the curing calorific value of the curing composition when heating the curable composition and the curing calorific value of the semi-cured product by DSC and calculating it from the following formula.

Curing degree (%) = [1-(curing heating value of semi-cured material/curing heating value of curable composition)] × 100

Organic solvents used in the production of the prepreg of this embodiment include, for example, methyl ethyl ketone, acetone, dimethyl formamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, and ethyl diglycol. Acetate, propylene glycol monomethyl ether acetate, etc. can be mentioned, and its selection and appropriate usage amount can be appropriately selected depending on the application. For example, in the case of manufacturing printed circuit boards from prepreg as shown below, methyl ethyl It is preferable to use a polar solvent with a boiling point of 160°C or lower, such as ketone, acetone, and dimethylformamide, and it is also preferable to use it in a ratio that makes the non-volatile content 40 to 80% by mass. In addition, the reinforcing base material used in the production of the prepreg of this embodiment is woven or non-woven fabric containing inorganic fibers such as glass fiber, polyester fiber, polyamide fiber, or organic fiber, or mat, paper, etc., and these may be used alone. , or can be used in combination.

The conditions for the heat treatment of the prepreg of this embodiment are appropriately selected depending on the type and amount of the organic solvent, catalyst, and various additives used, but are usually at a temperature of 80 to 220 ° C. and under the conditions of 3 to 30 minutes. It is desirable to do this.

[Build-up board]

A method of obtaining a build-up substrate from the curable composition of this embodiment includes a method via the following steps 1 to 3. In step 1, the curable composition in which rubber, filler, etc. are appropriately mixed is first applied to a circuit board on which a circuit is formed using a spray coating method, curtain coating method, etc., and then cured. In step 2, if necessary, the circuit board coated with the curable composition is punched into a predetermined through-hole portion, etc., then treated with a roughening agent and the surface is washed with hot water to form irregularities on the board, and copper Metals such as plating are treated. In Step 3, the operations of Steps 1 to 2 are sequentially repeated depending on the purpose to alternately build up resin insulating layers and conductor layers with a predetermined circuit pattern to form a build-up substrate. In addition, in the above process, the punching of the through-hole portion may be performed after the formation of the outermost resin insulating layer. In addition, the build-up substrate in this embodiment forms a roughened surface by heat-pressing a resin-equipped copper foil in which the composition is semi-cured on the copper foil at 170 to 300° C. on a wiring board on which a circuit is formed, It is also possible to produce a build-up substrate by omitting the plating process.

[Build-up film]

This disclosure is a build-up film containing the curable composition of this embodiment. As a method for manufacturing the build-up film of this embodiment, the curable composition is applied on a support film (Y), then dried, and a curable composition layer is formed on the support film (Y) to form a layer for a multilayer printed wiring board. A method of manufacturing it by making it into an adhesive film can be mentioned.

When manufacturing a build-up film from a curable composition, the film is softened under the temperature conditions of the laminate in the vacuum lamination method (usually 70 to 140°C), and simultaneously with the laminate of the circuit board, the vias present in the circuit board are softened. It is important to exhibit fluidity (resin flow) that allows resin filling in holes or through holes, and it is desirable to mix the above components to express these characteristics. In addition, in the resulting build-up film or circuit board (copper-clad laminate, etc.), a uniform appearance is achieved in order to achieve consistent performance in any area without causing locally different characteristic values due to phase separation, etc. Last name is required.

Here, the diameter of the through hole of the multilayer printed wiring board is typically 0.1 to 0.5 mm, and the depth is typically 0.1 to 1.2 mm, and it is generally desirable to enable resin filling within this range. Additionally, when laminating both sides of a circuit board, it is desirable to fill about 1/2 of the through hole.

The method of producing the above-mentioned adhesive film is specifically, after preparing the curable composition in the form of varnish, applying this composition in form of varnish to the surface of the support film (Y), and further applying an organic solvent by heating or spraying hot air, etc. It can be manufactured by drying to form a composition layer (X) containing the curable composition. Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetic acid esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; and cellosolve. , carbitols such as butylcarbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and the non-volatile content is 30 to 60% by mass. It is desirable to use it in a ratio of .

The thickness of the formed composition layer (X) is usually preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer of a circuit board is usually in the range of 5 to 70 ㎛, the thickness of the resin composition layer is preferably 10 to 100 ㎛. In addition, the composition layer (X) in this embodiment may be protected with a protective film described later. By protecting with a protective film, adhesion of dust or the like to the surface of the resin composition layer and scratches can be prevented.

The above-mentioned support film (Y) and protective film are polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, and polyester. Carbonate, polyimide, and further metal foil such as release paper, copper foil, and aluminum foil can be mentioned. In addition, the support film and the protective film may be subjected to mold release treatment in addition to mud treatment and corona treatment. The thickness of the support film is not particularly limited, but is usually 10 to 150 μm, and is preferably used in the range of 25 to 50 μm. Additionally, the thickness of the protective film is preferably 1 to 40 μm.

The above-described support film (Y) is peeled off after being laminated to a circuit board or after forming an insulating layer by heat-curing. If the support film (Y) is peeled off after heat-curing the adhesive film, adhesion of dust, etc. during the curing process can be prevented. When peeling after curing, a release treatment is usually performed in advance on the support film.

Additionally, a multilayer printed circuit board can be manufactured from the build-up film obtained as described above. For example, when the resin composition layer (X) is protected with a protective film, after peeling off the resin composition layer ( For example, it is laminated by the vacuum lamination method. The lamination method may be a batch method or a continuous method using a roll. Additionally, if necessary, the build-up film and circuit board may be heated (preheated) as needed before laminating. As for the laminate conditions, the pressing temperature (lamination temperature) is preferably 70 to 140°C, and the pressing pressure is preferably 1 to 11 kgf/cm2 (9.8×10 ⁴ to 107.9×10 ⁴ N/m2), It is preferable to laminate under reduced air pressure of 20 mmHg (26.7 hPa) or less.

<Challenge paste>

As a method of obtaining an electrically conductive paste from the curable composition of the present invention, for example, a method of dispersing electrically conductive particles in the composition is included. The electrically conductive paste can be a paste resin composition for circuit connection or an anisotropic conductive adhesive depending on the type of electrically conductive particles used.

[Example]

The present invention will be specifically explained by examples and comparative examples. However, in the following, “part” and “%” are based on mass unless otherwise specified. In addition, the physical properties of the synthesized polymaleimide compound (A) were measured as follows and are shown in Table 1.

(1) Amine equivalent

The amine equivalent weight of the intermediate amine compound (c) was measured using the following measurement method.

In a 500 mL stopper-equipped Erlenmeyer flask, weigh approximately 2.5 g of the sample intermediate amine compound (c), 7.5 g of pyridine, 2.5 g of acetic anhydride, and 7.5 g of triphenylphosphine, then attach a cooling tube and store at 120°C. Heat and reflux for 150 minutes in an oil bath set to .

After cooling, 5.0 mL of distilled water, 100 mL of propylene glycol monomethyl ether, and 75 mL of tetrahydrofuran were added, and the mixture was titrated with a 0.5 mol/L potassium hydroxide-ethanol solution by potentiometric titration. A blank test was performed and corrected in the same manner.

Amine equivalent weight (g/equivalent weight) = (S × 2,000) / (Blank-A)

S: Amount of sample (g)

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

Blank: Consumption amount of 0.5mol/L potassium hydroxide-ethanol solution in blank test (mL)

(2) GPC measurement

Using the following measuring device and measuring conditions, the number average molecular weight (Mn), weight average molecular weight (Mw), and molecular weight distribution (Mw/Mn) of the polymaleimide compound (A) obtained in Examples and Comparative Examples were measured. Calculated.

“Measurement device”

“HLC-8320 GPC” manufactured by Tosoh Corporation

"Measuring conditions"

Column: Guard column “HXL-L” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G2000HXL” manufactured by Tosoh Corporation + “TSK-GEL G3000HXL” manufactured by Tosoh Corporation +Tosoh Corporation “TSK-GEL G4000HXL”

Detector: RI (differential refractometer)

Data processing: “GPC workstation EcoSEC-WorkStation” manufactured by Tosoh Corporation.

Measurement conditions: column temperature 40℃

Development solvent tetrahydrofuran

Flow rate 1.0ml/min

Standard: In accordance with the measurement manual of the above-mentioned “GPC Workstation EcoSEC-WorkStation,” the following monodisperse polystyrene with a known molecular weight was used.

(Used polystyrene)

“A-500” made by Tosoh Corporation

“A-1000” manufactured by Tosoh Corporation.

“A-2500” manufactured by Tosoh Corporation.

“A-5000” manufactured by Tosoh Corporation.

“F-1” made by Tosoh Corporation

“F-2” made by Tosoh Corporation

“F-4” made by Tosoh Corporation

“F-10” made by Tosoh Corporation

“F-20” made by Tosoh Corporation

“F-40” made by Tosoh Corporation

“F-80” made by Tosoh Corporation

“F-128” made by Tosoh Corporation

Sample: A 1.0% by mass tetrahydrofuran solution of the polymaleimide compound (A) obtained in the synthesis example in terms of resin solid content was filtered through a microfilter (50 μl).

(3) FD-MS measurement

The FD-MS spectrum of the polymaleimide compound (A) obtained in the examples was measured using the following measurement equipment and measurement conditions.

Measurement device: JMS-T100GC AccuTOF

Measuring conditions

Measurement range: m/z=4.00 to 2000.00

Rate of change: 51.2mA/min

Final current value: 45mA

Cathode voltage: -10kV

Recording interval: 0.07sec

(4) ¹³ C-NMR measurement

The ¹³ C-NMR spectrum of the polymaleimide compound (A) obtained in the examples was measured under the following measurement equipment and measurement conditions.

¹³ C-NMR: “JNM-ECZ400S” manufactured by JEOL RESONANCE

Resonant frequency: 100MHz

Integration count: 4000 times

Solvent: Chloroform-d

Sample concentration: 12 mass%

Relieving reagent: Chromium(III) acetylacetonate

(5) Synthesis of polymaleimide compound (A)

<Synthesis Example 1> Synthesis of polymaleimide compound (A-1)

(I) Synthesis of intermediate amine compound (c-1)

Into a flask equipped with a thermometer, cooling pipe, 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 temperature was raised to 130°C while stirring, and held for 30 minutes. After that, 272.0 g of (DVB-810 (mixture of divinylbenzene/ethylstyrene (divinylbenzene/ethylstyrene=81/19(mol)%), manufactured by Nittetsu Chemical & Materials) was added dropwise over 2 hours, It was allowed to react as is for 1 hour. After that, the temperature was raised to 190°C over 6 hours and held for 10 hours. After reaction, it was air-cooled to 100°C, diluted with 300 g of toluene, activated clay was removed by filtration, and the solvent was dissolved under reduced pressure. and low molecular weight substances such as unreacted products were distilled off to obtain intermediate amine compound (c-1).The amine equivalent weight of intermediate amine compound (c-1) was 214 g/equivalent.

(II) Maleimide

117.7 g (1.2 mol) of maleic anhydride and 700 g of toluene were added to a 2L flask equipped with a thermometer, cooling pipe, Dean-Stark trap, and stirrer, 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 then reacted for 2 hours. 37.1 g of p-toluenesulfonic acid monohydrate was added to the reaction solution, heated to 115°C, and the azeotropic water and toluene were cooled and separated under reflux, and then only toluene was returned to the system and a dehydration reaction was performed for 5 hours. After air cooling to room temperature, it was neutralized with 49% NaOH. Afterwards, toluene and water were distilled off under reduced pressure at 60°C, and 600 g of MEK (methyl ethyl ketone) was added to the DMF solution remaining in the flask. After raising the temperature of the solution to 60°C, the solution was separated into 200 g of ion-exchanged water three times to remove salts in the solution. Furthermore, sodium sulfate was added, dried, and then concentrated under reduced pressure. The obtained reaction product was vacuum dried at 80°C to obtain polymaleimide compound (A-1). The chemical structure and characteristic analysis of the polymaleimide compound (A-1) were confirmed using GPC, FD-MS, and ¹³ C-NMR. The measurement results are shown in FIGS. 1A to 1C. Additionally, from the GPC measurement results, the Mn of the polymaleimide compound (A-1) was 998, the Mw was 367,834, and the Mw/Mn was 368.697.

<Examples 1 to 2 and Comparative Examples 1 to 2>

<<Preparation of curable composition and production of cured product>>

Polymaleimide compound (A-1) obtained in Synthesis Example 1, comparative maleimide (1) (“BMI-2300” manufactured by Daiwa Kasei Kogyo Co., Ltd.), and comparative maleimide (2) (“BMI -5100" manufactured by Daiwa Kasei Kogyo Co., Ltd.), amine compound (B-1) (4,4'-diaminodiphenylmethane (manufactured by Tokyo Kasei Kogyo Co., Ltd.)) as amine compound (B), and amine compound (B-2) (4,4'-methylenebis(2-ethyl-6-methylaniline)) and DCPO (“Percumyl D”, Nichiyu Co., Ltd., Dicumyl Peroxide) as a curing catalyst as follows. By mixing in the ratio shown in Table 1, the curable compositions of Examples 1 to 2 and Comparative Examples 1 to 3 were prepared.

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

<<Curing conditions>>

Using a vacuum press, it was cured by heating at 200°C for 2 hours and then at 250°C for 2 hours.

Plate thickness after molding: 1.3mm

<<Evaluation of permittivity and dielectric loss tangent>>

In accordance with JIS-C-6481, the cavity resonance method was used using a network analyzer "E8362C" manufactured by Agilent Technology Co., Ltd., and the test specimen was stored at 10 GHz for 24 hours in a room at 23°C and 50% humidity after absolute drying. The dielectric constant (Dk) and dielectric loss tangent (Df) were measured.

<<Evaluation of hygroscopicity>>

In this Example and Comparative Example, as an evaluation method for low hygroscopicity, the moisture absorption rate (%) was calculated and evaluated using the following method.

A test piece cut to a size of 5 mm %) was calculated and evaluated.

Moisture absorption rate (%) = (mass of test piece after test - mass of test piece before test)/(mass of test piece before test) x 100

From the results shown in Table 1, comparing Examples 1 to 2 and Comparative Examples 1 to 3, by using a curable composition containing the polymaleimide compound (A) and amine compound (B) of Examples 1 to 2, , it can be confirmed that low dielectric constant, low dielectric loss tangent, and low moisture absorption under high temperature and high humidity were achieved. In addition, by using the curable composition containing the polymaleimide compound (A) and the amine compound (B) of Examples 1 and 2, low hygroscopicity, low dielectric constant and low dielectric loss tangent during curing even in the frequency band of Sub6 or higher. It was confirmed that gender was compatible to a high degree.

According to the present disclosure, a curable composition and a cured product thereof that exhibit low dielectric properties and low moisture absorption during curing can be provided.

Claims (8)

A polymaleimide compound (A) containing a monocyclic or condensed polycyclic aromatic group to which two or more straight-chain or branched alkylene groups are bonded,
A curable composition comprising an amine compound (B). The curable composition according to claim 1, wherein the polymaleimide compound (A) has a structural unit represented by the following general formula (1).

(In the general formula (1), R ¹ each independently represents an alkyl group,
R ² is each independently an alkyl group, an alkoxy group, or an alkylthio group having 1 to 10 carbon atoms; Aryl group, aryloxy group, or arylthio group having 6 to 10 carbon atoms; Cycloalkyl group having 3 to 10 carbon atoms; halogen atom; hydroxyl group; Or represents a mercapto group,
R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a methyl group, one of R ³ and R ⁴ is a hydrogen atom, the other is a methyl group, and one of R ⁵ and R ⁶ is a hydrogen atom. atom, the other side is a methyl group,
X ¹ has the following general formula (x):

(In general formula (x), R ⁷ and R ⁸ each independently represent a hydrogen atom or a methyl group, one of R ⁷ and R ⁸ is a hydrogen atom and the other is a methyl group, and R ⁹ is each independently, An alkyl group, alkoxy group or alkylthio group having 1 to 10 carbon atoms; an aryl group, aryloxy group or arylthio group having 6 to 10 carbon atoms; a cycloalkyl group having 3 to 10 carbon atoms; a halogen atom; a hydroxyl group; or represents a mercapto group, and t represents an integer of 0 to 4.)
represents a substituent ^represented by, r is the average value of the number of substitutions for X ¹ per benzene ring to which represents an integer from 1 to 4, and k represents an integer from 1 to 100.) A cured product of the curable composition according to claim 1 or 2. A prepreg comprising a reinforcing base material and a semi-cured product of the curable composition according to claim 1 or 2 impregnated into the reinforcing base material. A circuit board that is a laminate having the prepreg according to claim 4 and copper foil. A build-up film containing the curable composition according to claim 1 or 2. A semiconductor encapsulating material containing the curable composition according to claim 1 or 2. A semiconductor device comprising a cured product of the semiconductor encapsulant according to claim 7.

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