TW202313833A - Curable composition, prepreg, metal foil clad laminate, and printed wiring board - Google Patents

Abstract

An object of the invention is to provide a curable composition, a prepreg, a metal foil clad laminate, and a printed wiring board that are capable of simultaneously achieving low thermal expansion, favorable heat resistance (a high glass transition temperature), and high peel strength (copper foil adhesion). The curable composition of the invention contains: a thermosetting compound (D) containing at least a structural unit derived from an alkenylphenol (A), a structural unit derived from an epoxy modified silicone (B), and a structural unit derived from an epoxy compound (C) other than the epoxy modified silicone (B), an epoxy resin (E), and a cyanate ester compound (F), wherein the epoxy resin (E) differs from the epoxy modified silicone (B) and may be the same as or different from the epoxy resin compound (C), and the functional group equivalence ratio between the cyanate ester compound (F) and the epoxy resin (E) (cyanate group equivalent of the cyanate ester compound (F) / epoxy group equivalent of the epoxy resin (E)) is within a range from 0.25 to 0.85.

Description

Curable composition, prepreg, metal foil-clad laminate, and printed wiring board

The present invention relates to a curable composition, a prepreg, a metal foil-clad laminate, and a printed wiring board.

In recent years, along with the high-performance and miniaturization of semiconductor packages widely used in electronic equipment, communication equipment, and personal computers, the high-integration and high-density mounting of various parts for semiconductor packaging has also been accelerated in recent years. Along with this, many characteristics required for printed wiring boards for semiconductor packaging have become more and more stringent. The characteristics required for such a printed wiring board include, for example, low thermal expansion, heat resistance (high glass transition temperature), high peel strength, and the like.

Patent Document 1 discloses a thermosetting composition containing a specific maleimide compound, a polysiloxane compound having an epoxy group in the molecular structure, and a compound having a phenolic hydroxyl group, which is excellent in heat resistance and low thermal expansion. Ideal for use in metal foil-clad laminates and multilayer printed wiring boards.

Patent Document 2 discloses an addition polymer of polymaleimide, dipoxypropyl polysiloxane represented by the following formula (I), and diallyl bisphenols represented by the following formula (II), and A method for producing a resin for encapsulating semiconductors by reacting an allylated phenolic resin represented by the following formula (III) in a predetermined ratio and conditions. According to this document, the resin for semiconductor sealing obtained by the above-mentioned production method has excellent compatibility between polymaleimide and the above-mentioned addition polymer, and furthermore, the cured product characteristics of the composition using the resin for semiconductor sealing (such as high glass transition temperature, moisture resistance, and strength during heating) are excellent, and they have high reliability as a resin composition for sealing semiconductors. This document reveals that in the following formula (III), component b reacts with maleimide groups during the resin formation reaction with polymaleimide, which improves polymaleimide and polysiloxane important component of compatibility.

[chemical 1]

In the formula, ^R1 represents an alkylene or a phenylene group, ^R2 each independently represents an alkyl group or a phenylene group, and n represents an integer of 1 to 100.

[Chem 2]

In the formula, R ⁴ represents an ether bond, a methylene group, a propylene group, or a direct bond (single bond).

[Chem 3]

In the formula, a, b, and c respectively represent the percentage of each composition, 0<a, b, c<100 and a+b+c=100.

Patent Document 3 describes a thermal compound containing alkenylphenol (A), epoxy-modified polysiloxane (B), and an epoxy compound (C) other than the aforementioned epoxy-modified polysiloxane (B) having excellent compatibility. hardening composition. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2012-149154 [Patent Document 2] Japanese Patent Application Laid-Open No. 4-4213 [Patent Document 3] WO2020/22084

[Problem to be Solved by the Invention]

However, the resin composition described in Patent Document 1 has a problem of insufficient metal foil peel strength (for example, copper foil peel strength) when used as a metal foil-clad laminate, although it has heat resistance.

In addition, in the resin composition described in Patent Document 2, low thermal expansion and metal foil peel strength required as characteristics of a printed wiring board are not considered.

In the resin composition described in Patent Document 3, although the metal foil peel strength is excellent, there is still room for improvement in terms of low thermal expansion.

The present invention is made in view of the above-mentioned problems, and an object thereof is to provide a curable composition, a prepreg, and a coating that simultaneously achieve low thermal expansion, heat resistance (high glass transition temperature), and high peel strength (copper foil adhesion). Metal foil laminated boards, and printed wiring boards. [Means to solve the problem]

That is, the present invention is as follows. [1] A curable composition comprising: A thermosetting compound (D) comprising at least a structural unit derived from alkenylphenol (A), a structural unit derived from epoxy-modified polysiloxane (B), and a compound derived from other than the aforementioned epoxy-modified polysiloxane (B) The structural unit of the epoxy compound (C), epoxy resin (E), and Cyanate compound (F); The aforementioned epoxy resin (E) is different from the aforementioned epoxy-modified polysiloxane (B), and may be the same or different from the aforementioned epoxy compound (C), and the aforementioned cyanate compound (F) is different from the aforementioned epoxy resin The functional group equivalent ratio of (E) (the equivalent of the cyanate group of the cyanate compound (F)/the equivalent of the epoxy group of the epoxy resin (E)) is 0.25-0.85.

[2] The curable composition according to [1], wherein the thermosetting compound (D) is at least the aforementioned alkenylphenol (A), the aforementioned epoxy-modified silicone (B), and the aforementioned A polymer (D1) obtained by polymerizing the aforementioned epoxy compound (C) other than the epoxy-modified silicone (B).

[3] The curable composition according to [1] or [2], wherein the alkenylphenol (A) contains diallyl bisphenol and/or diallyl bisphenol.

[4] The curable composition according to any one of [1] to [3], wherein the epoxy-modified polysiloxane (B) contains epoxy resin having an epoxy equivalent of 140 to 250 g/mol. Modified polysiloxane.

[5] The curable composition according to any one of [1] to [4], wherein the epoxy-modified polysiloxane (B) contains epoxy-modified polysiloxane represented by the following formula (1): oxygen.

[chemical 4]

In formula (1), R ¹ each independently represent a single bond, an alkylene group, an aryl group, or an aralkylene group, R ² each independently represent an alkyl group or a phenyl group with a carbon number of 1 to 10, and n represents 0 to 10 An integer of 100.

[6] The curable composition according to any one of [1] to [5], wherein the epoxy compound (C) includes a compound represented by the following formula (b2).

[chemical 5]

In formula (b2), R ^a each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.

[7] The curable composition according to any one of [1] to [6], wherein the thermosetting compound (D) has a weight average molecular weight of 3.0×10 ³ to 5.0×10 ⁴ .

[8] The curable composition as described in any one of [1] to [7], wherein the epoxy resin (E) is selected from the group consisting of naphthyl cresol novolak type epoxy resins and naphthyl ether type epoxy resins. At least one of the group consisting of epoxy resins.

[9] The curable composition according to any one of [1] to [8], wherein the cyanate compound (F) includes a compound represented by the following formula (4) and/or the following formula (4) Compounds represented by the following formula (5) other than the represented compounds.

[chemical 6]

In formula (4), R ₆ each independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more.

[chemical 7]

In formula (5), R _ya each independently represents an alkenyl group having 2 to 8 carbon atoms, or a hydrogen atom, R _yb each independently represents an alkyl group having 1 to 10 carbon atoms, or a hydrogen atom, and R _yc each independently represents An aromatic ring with 4~12 carbons, R _yc can also form a condensed structure with a benzene ring, R _yc may or may not exist, A ^1a each independently represent an alkylene group with 1~6 carbons, an alkylene group with 7~16 carbons Aralkylene group, arylylene group with 6-10 carbon atoms, terylene group, sulfonyl group, oxygen atom, sulfur atom, or single bond, when R _yc does not exist, there may be two or more in one benzene ring The base of R _ya and/or R _yb , n represents an integer of 1-20.

[10] The curable composition according to any one of [1] to [9], wherein the content of the thermosetting compound (D) is equal to the content of the thermosetting compound (D) and the epoxy The total of 100 mass parts of resin (E) and the said cyanate compound (F) is 25-50 mass parts.

[11] The curable composition according to any one of [1] to [10], wherein the total content of the epoxy resin (E) and the cyanate compound (F) is equal to that of the thermosetting The total of 100 parts by mass of the permanent compound (D), the aforementioned epoxy resin (E), and the aforementioned cyanate compound (F) is 50 to 75 parts by mass.

[12] The curable composition according to any one of [1] to [9], wherein the content of the thermosetting compound (D) is equal to the content of the thermosetting compound (D) and the epoxy The total amount of 100 parts by mass of the resin (E) and the aforementioned cyanate compound (F) is 25 to 50 parts by mass, and The total content of the aforementioned epoxy resin (E) and the aforementioned cyanate compound (F) is 100% of the total of the aforementioned thermosetting compound (D), the aforementioned epoxy resin (E) and the aforementioned cyanate compound (F). Parts by mass are 50 to 75 parts by mass.

[13] The curable composition according to any one of [1] to [12], wherein the thermosetting compound (D), the epoxy resin (E) and the cyanate compound (F) are The total content of is 50 to 99 parts by mass relative to 100 parts by mass of resin solid content in the resin composition.

[14] The curable composition according to any one of [1] to [13], further comprising a maleimide compound.

[15] The curable composition according to [14], wherein the maleimide compound is selected from the group consisting of bis(4-maleimidophenyl)methane, 2,2-bis(4- (4-maleimidophenoxy)phenyl)propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, represented by the following formula (3) At least one of the group consisting of a maleimide compound and a maleimide compound represented by the following formula (3').

[chemical 8]

In formula (3), R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 to 100.

[chemical 9]

In the formula (3′), R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n4 represents an integer of 1 to 10.

[16] The curable composition according to [14] or [15], wherein the content of the maleimide compound is equal to the thermosetting compound (D) and the epoxy resin (E) and The total of 100 parts by mass of the aforementioned cyanate compounds (F) is 5 to 45 parts by mass.

[17] The curable composition according to any one of [1] to [16], further comprising an inorganic filler.

[18] The curable composition according to [17], wherein the content of the inorganic filler is equal to that of the thermosetting compound (D), the epoxy resin (E) and the cyanate compound (F ) is 50 to 350 parts by mass for a total of 100 parts by mass.

[19] The curable composition as described in [17], wherein the inorganic filler is selected from the group consisting of silica, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, At least one selected from the group consisting of titanium oxide, barium titanate, magnesium oxide, and magnesium hydroxide.

[20] A prepreg comprising: base material, and The curable composition described in any one of [1] to [19] impregnated or coated on the aforementioned substrate.

[21] A metal foil-clad laminate comprising: A laminate formed using the prepreg described in [20], and Metal foil arranged on one or both sides of the aforementioned laminate.

[22] A printed wiring board having: insulation, and A conductor layer formed on one or both sides of the aforementioned insulating layer; The insulating layer includes a cured product of the curable composition described in any one of [1] to [19]. [Effect of Invention]

According to the present invention, it is possible to provide curable compositions, prepregs, metal foil-clad laminates, and Printed Wiring Board.

Hereinafter, the mode for carrying out the present invention (hereinafter referred to as "the present embodiment") will be described in detail. The following embodiments are examples for explaining the present invention, and do not limit the present invention to the following concepts. The present invention can be appropriately modified and implemented within the scope of the gist.

In addition, "(meth)acrylate" in this specification means both "acrylate" and the corresponding "methacrylate". In addition, in this embodiment, "resin solid content" or "resin solid content in the resin composition" means that additives such as inorganic fillers, silane coupling agents, and wetting and dispersing agents are excluded from the resin composition unless otherwise specified. , and the components after the solvent, "100 parts by mass of resin solid content" means that the total of the components in the resin composition excluding additives such as inorganic fillers, silane coupling agents, wetting and dispersing agents, and solvents is 100 parts by mass.

[hardening composition] The curable composition of this embodiment contains: at least a structural unit derived from alkenylphenol (A), a structural unit derived from epoxy-modified polysiloxane (B), and a structural unit derived from the aforementioned epoxy-modified polysiloxane (B) ), the thermosetting compound (D), the epoxy resin (E), and the cyanate compound (F), which are constituent units of the epoxy compound (C) other than the epoxy compound (C), the aforementioned epoxy resin (E) and the aforementioned epoxy-modified Polysiloxane (B) is different, and it can be the same or different from the aforementioned epoxy compound (C), the functional group equivalent ratio ((cyanate ester) of the aforementioned cyanate compound (F) to the aforementioned epoxy resin (E) The equivalent of the cyanate group of the compound (F)/the equivalent of the epoxy group of the epoxy resin (E)) is 0.25-0.85.

In this embodiment, low thermal expansion, heat resistance (high glass transition temperature), and high peel strength (copper foil adhesion) can be simultaneously achieved by using the curable composition having the above-mentioned constitution. Regarding this matter, the inventors of the present invention consider as follows. In addition, the following description includes matters to be considered, and this embodiment is not limited by the matters to be considered.

That is, the thermosetting compound (D) of the present embodiment contains a structural unit derived from epoxy-modified polysiloxane (B), and an epoxy compound (C) derived from the aforementioned epoxy-modified polysiloxane (B) As for the constituent units, the thermosetting compound (D), the epoxy resin (E) and the cyanate compound (F) are incompatible when heated and hardened respectively, that is, a so-called reaction-induced phase separation structure is formed. At this time, if the thermosetting compound (D) further contains a structural unit derived from alkenylphenol (A), since it also contains a highly reactive alkenyl group, the aforementioned reaction-induced phase separation structure can be controlled in an appropriate state. Furthermore, it is considered that by setting the functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) in the range of 0.25 to 0.85, the phase separation interface can be enlarged, that is, a finer phase separation can be formed. . As a result, according to the present embodiment, the epoxy resin (E) and the cyanate compound (F) can ideally form the island portion (continuous phase) and the thermosetting compound (D) into the sea portion (continuous phase), that is, a so-called double phase. Continuous (bicontinuous) structure. It is considered that by using such a curable composition, the obtained cured product can have low thermal expansion while maintaining heat resistance (high glass transition temperature) and high peel strength (copper foil adhesion).

First, the functional group equivalent ratio between the cyanate compound (F) and the epoxy resin (E) contained in the curable composition of the present embodiment will be described, and each component will be described later.

＜Functional group equivalent ratio＞ In the curable composition of this embodiment, the functional group equivalent ratio of the cyanate compound (F) described below to the epoxy resin (E) described below (the equivalent of the cyanate group of the cyanate compound (F)/epoxy resin (E) the epoxy group equivalent) is 0.25~0.85. When the functional group equivalent ratio falls within the aforementioned range, excellent low thermal expansion, excellent heat resistance, and high peel strength can be simultaneously achieved. The functional group equivalent ratio is preferably 0.30-0.80, more preferably 0.40-0.70, in view of obtaining better low thermal expansion, heat resistance, and peel strength. In addition, when the functional group equivalent ratio is less than 0.25, it is difficult to obtain excellent heat resistance and peel strength. On the other hand, when the functional group equivalent ratio exceeds 0.85, it becomes difficult to obtain low thermal expansion.

The reason for this has not been elucidated, but the present inventors infer as follows. That is, it is estimated that if the functional group equivalent ratio is less than 0.25, unreacted epoxy residues will increase, so hardening will be poor, and the epoxy resin (E) and cyanate compound (F) will not be ideally formed. As a result, heat resistance and peel strength (copper foil adhesion) decrease. On the other hand, it is inferred that if the functional group equivalent ratio exceeds 0.85, the continuous phase (sea portion) of the thermosetting compound (D) cannot be ideally formed due to insufficient phase separation interface, and as a result, the low elasticity of the cured product is insufficient, Low thermal expansion cannot be achieved.

In this embodiment, the functional group equivalent ratio is based on the equivalent weight of the cyanate group in the cyanate compound (F) contained in the curable composition and the ring ratio in the epoxy resin (E) contained in the curable composition. The ratio of equivalents of oxygen groups is calculated by the following formula (1). In this embodiment, any one of the cyanate compound (F) and the epoxy resin (E) can also be used in two or more kinds, and the calculation method of the functional group equivalent ratio at this time is to calculate the cyanate compound (F) and the number of functional groups of each component in the epoxy resin (E) (that is, the equivalent weight of cyanate groups and the equivalent weight of epoxy groups), and these values are summed up to calculate the total cyanate group equivalent and the equivalent of all epoxy groups. Then, the functional group equivalent ratio is defined as the value obtained by dividing the equivalent weight of all cyanate groups by the equivalent weight of all epoxy groups. In addition, the number of functional groups is a value obtained by dividing the number of parts by mass of a component by the functional group equivalent of the component.

Formula (1): functional group equivalent ratio=(the mass fraction of the cyanate compound (F) in the composition/the functional group equivalent of the cyanate compound (F))/(the epoxy resin (E) in the composition ) in parts by mass/functional group equivalent of epoxy resin (E))

＜Thermosetting compound (D)＞ The curable composition of this embodiment contains at least a structural unit derived from alkenylphenol (A), a structural unit derived from epoxy-modified polysiloxane (B), and a compound derived from epoxy-modified polysiloxane (B) The thermosetting compound (D) of the constituent unit of the epoxy compound (C). Moreover, a thermosetting compound (D) may further contain the structural unit derived from the phenol compound (G) other than alkenylphenol (A) as needed. Hereinafter, each structural unit is also called a structural unit A, B, C, and G, respectively. In addition, in this specification, the "constituent unit derived from alkenyl phenol (A)" means that the thermosetting compound (D) contains a structural unit derived from the polymerization of alkenyl phenol (A), and a reaction that can provide the same structural unit and so on to form the constituent units. In this specification, "constituent unit derived from ..." is also defined and interpreted in the same way. The thermosetting compound (D) can more ideally control the above-mentioned reaction-induced phase separation structure by using the cyanate compound (F) and the epoxy resin (E) in a specific functional group equivalent ratio, so the curable composition Can exhibit low thermal expansion, heat resistance, and high peel strength at the same time. A thermosetting compound (D) can be used individually by 1 type or in appropriate combination of 2 or more types. In addition, alkenyl phenol (A), epoxy-modified silicone (B), epoxy compound (C), and phenol compound (G) are mentioned later.

The content of the constituent unit A is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 10 to 40% by mass, based on the total mass of the thermosetting compound (D). When the content of the constituent unit A falls within the above range, the curable composition will have further excellent compatibility in the varnish, and liquid phase separation will not easily occur (hereinafter also referred to as "varnish compatibility") ). Thereby, the cured product obtained by curing the curable composition of this embodiment tends to be more excellent in low thermal expansion, heat resistance, and peel strength.

The content of the constituent unit B is preferably 20 to 60% by mass, more preferably 25 to 55% by mass, and even more preferably 30 to 50% by mass, based on the total mass of the thermosetting compound (D). When the content of the constituent unit B falls within the above range, the curable composition has further excellent varnish compatibility, so the obtained cured product tends to have better low thermal expansion, heat resistance, and peel strength.

Constituent unit B is preferably derived from epoxy-modified polysiloxane with an epoxy equivalent of 50-350 g/mol (hereinafter also referred to as "low-equivalent epoxy-modified polysiloxane B1"), and an epoxy-modified polysiloxane with an epoxy equivalent of 400-4000 g/mol The constituent unit of epoxy-modified polysiloxane (hereinafter also referred to as "high-equivalent epoxy-modified polysiloxane B2"). Low-equivalent epoxy-modified polysiloxane B1 and high-equivalent epoxy-modified polysiloxane B2 are epoxy-modified polysiloxanes with an epoxy equivalent of 140 to 250 g/mol (hereinafter also referred to as "low-equivalent polysiloxane"). Equivalent epoxy-modified polysiloxane B1'"), and epoxy-modified polysiloxane with an epoxy equivalent of 450~3000g/mol (hereinafter also referred to as "high-equivalent epoxy-modified polysiloxane B2'") ) is better.

The content of the constituent unit derived from low-equivalent epoxy-modified polysiloxane B1 (hereinafter also referred to as "constituent unit B1") is preferably 5 to 25% by mass, 7.5% by mass, relative to the total mass of the thermosetting compound (D). ~20% by mass is more preferable, and even more preferably 10~17% by mass.

The content of the constituent units derived from high-equivalent epoxy-modified polysiloxane B2 (hereinafter also referred to as "constituent unit B2") is preferably 15 to 55% by mass relative to the total mass of the thermosetting compound (D), which is 20 ~52.5% by mass is more preferable, and 25~50% by mass is even more preferable.

The mass ratio of the content of the constituent unit B2 to the content of the constituent unit B1 is preferably 1.5-4, more preferably 1.7-3.5, and even more preferably 1.9-3.1. When the mass ratio falls within the above range, the curable composition has further excellent varnish compatibility, so the obtained cured product tends to have better low thermal expansion, heat resistance, and peel strength.

The content of the constituent unit C is preferably 5 to 40% by mass, more preferably 10 to 30% by mass, and even more preferably 15 to 20% by mass, based on the total mass of the thermosetting compound (D). When the content of the constituent unit C falls within the above range, the curable composition has further excellent varnish compatibility, so the obtained cured product tends to have better low thermal expansion, heat resistance, and peel strength. Furthermore, it tends to exhibit excellent chemical resistance and insulation reliability.

In addition, the content of the constituent unit C is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, more preferably 15 to 60% by mass, and even more preferably 20 to 60% by mass relative to the total mass of the constituent unit B and the constituent unit C. 50% by mass is preferred. The content of the constituent unit B is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, more preferably 40 to 85% by mass, and even more preferably 50 to 80% by mass relative to the total mass of the constituent unit B and the constituent unit C %Excellent. Since the content of the constituent units C and B has the above-mentioned relationship, the curable composition has further excellent varnish compatibility, so the obtained cured product tends to have better low thermal expansion, heat resistance, and peel strength. And there will be a tendency to improve chemical resistance and insulation reliability.

The content of the constituent unit G is preferably 5 to 30% by mass, more preferably 10 to 27.5% by mass, and even more preferably 10 to 25% by mass, based on the total mass of the thermosetting compound (D). When the content of the constituent unit G falls within the above range, the curable composition has further excellent varnish compatibility, so the obtained cured product tends to have better low thermal expansion, heat resistance, and peel strength.

The alkenyl equivalent of the thermosetting compound (D) is preferably 300-1500 g/mol, more preferably 350-1200 g/mol, and even more preferably 400-1000 g/mol. When the alkenyl equivalent is 300 g/mol or more, there will be a continuous phase that can ideally form the thermosetting compound (D), so the elastic modulus of the cured product obtained by curing the curable composition of this embodiment is further reduced As a result, there is a tendency that the low thermal expansion properties of substrates and the like obtained by using cured products can be further reduced. When the alkenyl equivalent is less than 1500 g/mol, the reaction-induced phase separation structure can be controlled more ideally, so the obtained hardened product tends to have better low thermal expansion, heat resistance, and peel strength, and it will be resistant to chemicals The tendency to further improve the performance and insulation reliability.

The weight average molecular weight (Mw) of the thermosetting compound (D) is preferably 3.0×10 ³ to 5.0×10 ⁴ , more preferably 3.0×10 ³ to 2.0×10 ⁴ in terms of polystyrene in the GPC method. When the weight average molecular weight is 3.0×10 ³ or more, the thermal expansion coefficient of the prepreg tends to decrease. When the weight average molecular weight is 5.0×10 ⁴ or less, there will be a tendency to suppress the increase of the viscosity of the curable composition, the increase of the molecular weight, the gelation of the varnish, and the increase of the viscosity of the prepreg, and there will be obtained The cured product tends to be more excellent in low thermal expansion, heat resistance, and peel strength. Specifically, it was measured by the method described in the Example mentioned later.

The content of the thermosetting compound (D) is based on the tendency of the cured product obtained by curing the curable composition of this embodiment to be more excellent in low thermal expansion, heat resistance, and peel strength. (D) and the total of 100 parts by mass of the epoxy resin (E) described later and the cyanate compound (F) described later are preferably 25 to 50 parts by mass, more preferably 30 to 45 parts by mass.

(polymer (D1)) In order to exhibit sufficient varnish compatibility when the thermosetting compound (D) is mixed with a thermosetting resin that lacks varnish compatibility with polysiloxane compounds, at least alkenylphenol (A ), an epoxy-modified silicone (B), and a polymer (D1) obtained by polymerizing an epoxy compound (C) other than the aforementioned epoxy-modified silicone (B) is preferable. In addition, the polymer (D1) is a mixture of at least alkenylphenol (A), epoxy-modified polysiloxane (B), epoxy compounds (C) other than the aforementioned epoxy-modified polysiloxane (B), and phenol A polymer obtained by polymerizing the compound (G) is more preferable. Hereinafter, each component which can be used for synthesis|combination of a polymer (D1) is demonstrated.

･Alkenylphenol (A) The alkenylphenol (A) is not particularly limited as long as it is a compound having a structure in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. Since the thermosetting compound (D) or polymer (D1) contains a constituent unit derived from alkenylphenol (A), since the reaction-induced phase separation structure can be ideally controlled, the obtained cured product can exhibit excellent low thermal expansion , heat resistance, and peel strength.

Examples of the alkenyl group include alkenyl groups having 2 to 30 carbon atoms such as vinyl, allyl, propenyl, butenyl, and hexenyl. Among them, the alkenyl group is preferably an allyl group and/or a propenyl group, more preferably an allyl group, from the viewpoint of more effectively and reliably exerting the effects of the present embodiment. The number of alkenyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1-4. From the viewpoint of more effectively and reliably exerting the effects of this embodiment, the number of alkenyl groups directly bonded to one phenolic aromatic ring is preferably 1-2, more preferably 1. Also, the position where the alkenyl group is bonded to the phenolic aromatic ring is not particularly limited.

The phenolic aromatic ring means that one or more hydroxyl groups are directly bonded to the aromatic ring, and examples thereof include a phenol ring and a naphthol ring. The number of hydroxyl groups directly bonded to one phenolic aromatic ring is, for example, 1 to 2, preferably 1.

The phenolic aromatic ring may have substituents other than alkenyl. Examples of such substituents include straight-chain alkyl groups with 1 to 10 carbons, branched alkyl groups with 3 to 10 carbons, cyclic alkyl groups with 3 to 10 carbons, and straight-chain alkyl groups with 1 to 10 carbons. Shaped alkoxy, branched alkoxy with 3 to 10 carbons, cyclic alkoxy with 3 to 10 carbons, and halogen atoms. When the phenolic aromatic ring has a substituent other than an alkenyl group, the number of the substituent directly bonded to one phenolic aromatic ring is, for example, 1-2. Also, the position where the substituent is bonded to the phenolic aromatic ring is not particularly limited.

The alkenylphenol (A) may have one or more structures in which one or more alkenyl groups are directly bonded to the phenolic aromatic ring. From the viewpoint of more effectively and reliably exerting the effect of this embodiment, alkenylphenol (A) preferably has one or two structures in which one or more alkenyl groups are directly bonded to the phenolic aromatic ring, and has two ideal.

The alkenylphenol (A) may be, for example, a compound represented by the following formula (1A) or the following formula (1B).

[chemical 10]

In the formula (1A), each R _xa independently represents an alkenyl group having 2 to 8 carbon atoms, each R _xb independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and each R _xc independently represents an alkenyl group having 4 to 12 carbon atoms. The aromatic ring, R _xc can also form a condensation structure with the benzene ring, R _xc may or may not exist, A represents an alkylene group with 1~6 carbons, an aralkylene group with 7~16 carbons, and an aralkylene group with 6~16 carbons Arylylene group, fenylene group, sulfonyl group, oxygen atom, sulfur atom, or direct bond (single bond) of 10, when R _xc does not exist, one benzene ring may also have two or more R _xa and/or Or the base of R _xb .

[chemical 11]

In the formula (1B), R _xd independently represents an alkenyl group with 2 to 8 carbons, R _xe independently represents an alkyl group with 1 to 10 carbons or a hydrogen atom, and R _xf represents an aromatic ring with 4 to 12 carbons , R _xf can also form a condensed structure with a benzene ring, R _xf may or may not exist, and when R _xf does not exist, one benzene ring may have two or more R _xd and/or R _xe groups.

In formula (1A) and formula (1B), the alkenyl groups having 2 to 8 carbon atoms represented by R _xa and R _xd include, for example, vinyl, allyl, propenyl, butenyl, hexenyl and the like. R _xa and R _xd are preferably allyl and/or propenyl, more preferably allyl.

In formula (1A) and formula (1B), when the groups represented by R _xc and R _xf form a condensed structure with a benzene ring, for example, a compound containing a naphthol ring as a phenolic aromatic ring is mentioned. Moreover, in formula (1A) and formula (1B), when the group represented by R _xc and R _xf does not exist, for example, the compound which contains a phenol ring as a phenolic aromatic ring is mentioned.

In formula (1A) and formula (1B), the alkyl groups with 1 to 10 carbons represented by _Rxb and _Rxe can include, for example: methyl, ethyl, propyl, butyl, pentyl, hexyl and other linear Alkyl; branched alkyl such as isopropyl, isobutyl, tertiary butyl, etc.

In the formula (1A), the alkylene group having 1 to 6 carbon atoms represented by A includes, for example, a methylene group, an ethylene group, a trimethylene group, and a propylidene group. The aralkylene group with 7~16 carbons represented by A can be exemplified by the formula: -CH ₂ -Ar-CH ₂ -, -CH ₂ -CH ₂ -Ar-CH ₂ -CH ₂ -, or the formula: -CH ₂ A group represented by -Ar-CH ₂ -CH ₂ - (wherein, Ar represents a phenylene group, a naphthylene group, or a biphenylene group). The arylylene group having 6 to 10 carbon atoms represented by A includes, for example, a phenylene ring.

For the compound represented by formula (1B), _Rxf is preferably a benzene ring (a compound containing a dihydroxynaphthalene skeleton) from the viewpoint of more effectively and reliably exerting the effects of the present embodiment.

The alkenyl phenol (A) is preferably one in which one alkenyl group is bonded to two phenolic aromatic rings of bisphenols in consideration of further improving the compatibility of the varnish and more ideally controlling the structure of the reaction-induced phase separation. Alkenyl bisphenols. Considering the same point of view, alkenyl bisphenols should be diallyl bisphenols with one allyl group bonded to the two phenolic aromatic rings of bisphenols, and/or two phenolic aromatic rings in bisphenols. Dipropenylbisphenol in which one propenyl group is bonded to each aromatic ring.

Examples of diallyl bisphenol include o,o'-diallyl bisphenol A (DABPA (trade name), Daiwa Chemical Industry Co., Ltd.), o,o'-diallyl bisphenol F, o,o'-diallyl bisphenol S, o,o'-diallyl bisphenol terpene. Dipropylene bisphenols include, for example: o, o'-dipropylene bisphenol A (PBA01 (trade name), Qunyei Chemical Industry Co., Ltd.), o, o'-dipropylene bisphenol F, o, o'-dipropenyl bisphenol S, and o,o'-dipropenyl bisphenol terpene.

The average number of phenolic groups per molecule of alkenylphenol (A) is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less, in view of more effectively and reliably exerting the effect of the present embodiment. The average number of phenol groups was calculated using the following formula.

[number 1]

In the formula, Ai represents the number of phenolic groups of alkenylphenols with i phenolic groups in the molecule, Xi represents the proportion of alkenylphenols with i phenolic groups in the molecule to the total alkenylphenols, X ₁ +X ₂ +…X _n =1.

･Epoxy modified silicone (B) The epoxy-modified polysiloxane (B) is not particularly limited as long as it is a polysiloxane compound or resin modified with an epoxy group-containing group. When the thermosetting compound (D) or the polymer (D1) contains the structural unit derived from the epoxy-modified polysiloxane (B), the cured product obtained can exhibit excellent low thermal expansion and chemical resistance.

The polysiloxane compound or resin is not particularly limited as long as it has a polysiloxane skeleton formed by repeating siloxane bonds. The polysiloxane skeleton may be a linear skeleton, a cyclic skeleton, or a network skeleton. Among them, the polysiloxane skeleton is preferably a linear skeleton from the viewpoint of more effectively and reliably exerting the effect of the present embodiment.

As a group containing an epoxy group, the group represented by following formula (a1) is mentioned, for example.

[chemical 12]

In the formula (a1), R ⁰ each independently represent a single bond, an alkylene group (for example, an alkylene group with 1 to 5 carbons such as methylene, ethylene, and propylidene), an arylylene group, or an arylene group. In an alkyl group, X represents a monovalent group represented by the following formula (a2) or a monovalent group represented by the following formula (a3).

[chemical 13]

[chemical 14]

Epoxy-modified polysiloxane (B) preferably contains epoxy-modified polysiloxane with an epoxy equivalent of 140~250g/mol, and epoxy-modified polysiloxane with an epoxy equivalent of 145~245g/mol More preferably, it contains epoxy-modified polysiloxane having an epoxy equivalent of 150-240 g/mol, and even more preferably. Epoxy-modified polysiloxane (B) contains epoxy-modified polysiloxane having an epoxy equivalent within the above-mentioned range, and the curable composition has further excellent varnish compatibility, so it is obtained The cured product tends to be more excellent in low thermal expansion, heat resistance, and peel strength, and tends to further improve chemical resistance.

Epoxy-modified polysiloxane (B) considers that the curable composition can have further excellent varnish compatibility, and the low thermal expansion, heat resistance, and peel strength of the obtained cured product are further excellent, and can be further improved. From the viewpoint of improving chemical resistance, it is preferable to contain two or more epoxy-modified polysiloxanes. At this time, two or more epoxy-modified polysiloxanes should have different epoxy equivalents, and epoxy-modified polysiloxanes (low-equivalent epoxy-modified polysiloxanes) with an epoxy equivalent of 50 to 350 g/mol should be used. Siloxane B1) and epoxy-modified polysiloxane (high-equivalent epoxy-modified polysiloxane B2) with an epoxy equivalent of 400-4000 g/mol are more preferred, containing polysiloxane with an epoxy equivalent of 140-250 g/mol Epoxy-modified polysiloxane (low-equivalent epoxy-modified polysiloxane B1') and epoxy-modified polysiloxane with an epoxy equivalent of 450-3000 g/mol (high-equivalent epoxy-modified polysiloxane B2 ') is even better.

When the epoxy-modified polysiloxane (B) contains two or more epoxy-modified polysiloxanes, the average epoxy equivalent of the epoxy-modified polysiloxane (B) should be 140~3000g/mol, 250~ 2000g/mol is more preferable, and 300~1000g/mol is even more preferable. The average epoxy equivalent was calculated using the following formula.

[number 2]

In the formula, Ei represents the epoxy equivalent of one of the two or more epoxy-modified polysiloxanes, and Wi represents the above-mentioned epoxy modified polysiloxane in the epoxy-modified polysiloxane (B). The ratio of permanent polysiloxane, W ₁ +W ₂ +...W _n =1.

Epoxy-modified polysiloxane (B) considers that the curable composition can have further excellent varnish compatibility, and the low thermal expansion, heat resistance, and peel strength of the obtained cured product are further excellent, and can be further improved. From the viewpoint of improving chemical resistance, it is preferable to contain epoxy-modified polysiloxane represented by the following formula (1).

[chemical 15]

In the formula (1), R ¹ each independently represent a single bond, an alkylene group, an arylylene group, or an aralkylene group, R ² each independently represent an alkyl group or a phenyl group with 1 to 10 carbon atoms, and n represents 0 An integer of ~100.

In formula (1), the alkylene group represented by R ¹ may be linear, branched or cyclic. The carbon number of the alkylene group is preferably 1-12, more preferably 1-4. As an alkylene group, a methylene group, an ethylene group, or a propylene group is mentioned, for example. Among them, R ¹ is preferably a propylene group.

In formula (1), the arylylene group represented by R ¹ may have a substituent. The carbon number of the extended aryl group is preferably 6-40, more preferably 6-20. Examples of the arylylene group include: phenylene, cyclohexylphenylene, hydroxyphenylene, cyanophenylene, nitrophenylene, naphthylene, biphenylene, anthracenyl, pyrenyl, and Extended base and so on. These groups may contain an ether bond, a ketone bond, or an ester bond.

In formula (1), the carbon number of the aralkylene group represented by R is preferably ^7-30 , more preferably 7-13. As an aralkylene group, the group represented by following formula (XI) is mentioned, for example.

[chemical 16]

In formula (X-I), * represents an atomic bond.

In the formula (1), the group represented by ^R1 may further have a substituent, and the substituents may include, for example: a linear alkyl group having 1 to 10 carbons, a branched alkyl group having 3 to 10 carbons, a branched alkyl group having 3 carbons, Cyclic alkyl with ~10 carbons, linear alkoxy with 1 to 10 carbons, branched alkoxy with 3 to 10 carbons, and cyclic alkoxy with 3 to 10 carbons.

In the formula (1), R ² each independently represent an alkyl group or a phenyl group having 1 to 10 carbon atoms. The above-mentioned alkyl group and phenyl group may have a substituent. The alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl. Among them, R ² is preferably methyl or phenyl.

In formula (1), n represents an integer of 0 or more, for example, an integer of 0 to 100. Considering that the curable composition has further excellent varnish compatibility, and the obtained cured product has further excellent low thermal expansion, heat resistance, and peel strength, and can further improve chemical resistance, the lower value of n The limit value is preferably 1 or more. Likewise, the upper limit of n is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less.

Epoxy-modified polysiloxane (B) considers that the curable composition can have further excellent varnish compatibility, and the low thermal expansion, heat resistance, and peel strength of the obtained cured product are further excellent, and can be further improved. From the viewpoint of improving chemical resistance, it is preferable to contain two or more epoxy-modified polysiloxanes represented by the formula (1). At this time, the two or more epoxy-modified polysiloxanes contained should have different n respectively, including epoxy-modified polysiloxanes in which n is 1~2 in formula (1) and n in formula (1) is 5~20 epoxy modified polysiloxane is better.

The average number of epoxy groups per molecule of epoxy-modified polysiloxane (B) is preferably 1 or more and less than 3, and 1.5 or more and 2.5 or less in view of more effectively and reliably exerting the effect of this embodiment. better. The average number of epoxy groups was calculated by the following formula.

[number 3]

In the formula, Bi represents the number of epoxy groups of the epoxy-modified polysiloxane with i epoxy groups in the molecule, and Yi represents the epoxy-modified polysiloxane with i epoxy groups in the molecule. The proportion of the whole modified polysiloxane, Y ₁ +Y ₂ +...Y _n =1.

The content of epoxy-modified polysiloxane (B) is considered to have further excellent varnish compatibility, and the obtained hardened product has better low thermal expansion, heat resistance, and peel strength, and can be From the point of view of further exhibiting chemical resistance and insulation reliability, it is preferably 5 to 95% by mass, 10 to 90% by mass based on 100% by mass of the total of epoxy-modified polysiloxane (B) and epoxy compound (C). % is more preferably 40 to 85% by mass, more preferably 50 to 80% by mass.

As the epoxy-modified silicone (B), a commercially available item may be used, or a product manufactured by a known method may be used. Commercially available products include, for example, "X-22-163" and "KF-105" of Shin-Etsu Chemical Co., Ltd.

･Epoxy compound (C) The epoxy compound (C) is an epoxy compound other than epoxy-modified polysiloxane (B), and more specifically, is an epoxy compound which does not have a polysiloxane skeleton. Low thermal expansion, heat resistance, peel strength, chemical resistance, and insulation reliability Good sex.

The epoxy compound (C) is not particularly limited as long as it is an epoxy compound other than epoxy-modified silicone (B). For the epoxy compound (C), it is considered that the curable composition can have further excellent varnish compatibility, and the obtained cured product has better low thermal expansion, heat resistance, and peel strength, and can further exhibit chemical resistance From the viewpoint of insulation reliability, it is preferable to contain a bifunctional epoxy compound having two epoxy groups in one molecule.

The difunctional epoxy compound can enumerate for example: bisphenol type epoxy resin (such as bisphenol A type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, and bisphenol novolak type epoxy resin), phenolic novolak type epoxy resin (such as phenol novolak type epoxy resin, bisphenol A novolac type epoxy resin, cresol novolac type epoxy resin), phenolic methane type epoxy resin, aralkyl type epoxy resin, biphenyl type epoxy resin containing biphenyl skeleton, naphthalene type epoxy resin containing naphthalene skeleton, anthracene type epoxy resin containing dihydroanthracene skeleton, epoxypropylene Base ester type epoxy resin, polyol type epoxy resin, epoxy resin containing isocyanurate ring, dicyclopentadiene type epoxy resin, fennel type epoxy resin containing fennel skeleton, bisphenol A type Epoxy resins composed of structural units and hydrocarbon structural units; their halogen compounds. These epoxy compounds may be used alone or in combination of two or more.

As an aralkyl type epoxy resin, the compound represented by following formula (b1) is mentioned, for example.

[chemical 17]

In formula (b1), Ar ³ each independently represents a benzene ring or a naphthalene ring, Ar ⁴ represents a benzene ring, a naphthalene ring, or a biphenyl ring, R ^3a each independently represent a hydrogen atom or a methyl group, and here, in Ar ³ The benzene ring or naphthalene ring can also have one or more substituents, for example, the substituents can also be substituents other than glycidoxy groups such as alkyl groups with 1 to 5 carbon atoms, phenyl groups, etc., Ar ⁴ The benzene ring, naphthalene ring or biphenyl ring may also have one or more substituents. For example, the substituents may also be substituents other than glycidoxy groups such as alkyl groups with 1 to 5 carbon atoms and phenyl groups. .

As a biphenyl type epoxy resin, the compound (compound b2) represented by following formula (b2) is mentioned, for example.

[chemical 18]

In formula (b2), R ^a each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.

In formula (b2), the alkyl group having 1 to 10 carbon atoms may be linear, branched or cyclic. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl.

When the biphenyl type epoxy resin is the compound b2, the biphenyl type epoxy resin may be in the form of a mixture of compounds b2 in which the number of Ra of the alkyl group is different. Specifically, it is preferably a mixture of biphenyl type epoxy resins having a different number of Ra in the alkyl group, a mixture of compound b2 in which the Ra in the alkyl group is 0 and a compound b2 in which the Ra in the alkyl group is 4. good.

Commercially available products of the compound represented by the above formula (b2) include, for example, "YL-6121H (trade name)" manufactured by Mitsubishi Chemical Corporation.

As a naphthalene type epoxy resin, the compound represented by following formula (b3) is mentioned, for example.

[chemical 19]

In formula (b3), R ^3b each independently represent a hydrogen atom, an alkyl group (such as methyl or ethyl) with 1 to 5 carbons, an aralkyl group, a benzyl group, a naphthyl group, a glycidyl group containing at least one Naphthyl group, or naphthylmethyl group containing at least one glycidoxy group, n represents an integer of 0 or more (for example, 0~2).

Commercial products of the compound represented by the above formula (b3) include, for example, "HP-4032" (n=0 in the above formula (b3)) and "HP-4710" (the above formula (b3) Among them, n=0, and R ^3b is a naphthylmethyl group containing at least one glycidoxyl group) and the like.

As a dicyclopentadiene epoxy resin, the compound represented by following formula (b4) is mentioned, for example.

[chemical 20]

In formula (b4), R ^3c each independently represent a hydrogen atom, or an alkyl group having 1 to 5 carbons (such as methyl or ethyl).

As the dicyclopentadiene type epoxy resin, a commercial item may be used, or a product manufactured by a known method may be used. Commercially available dicyclopentadiene type epoxy resins include "EPICRON HP-7200L", "EPICRON HP-7200", "EPICRON HP-7200H", "EPICRON HP- 7000HH", etc.

As an epoxy resin which consists of a bisphenol A structural unit and a hydrocarbon structural unit, the compound represented by following formula (b5) is mentioned, for example.

[chem 21]

In formula (b5), R ^1x and R ^2x each independently represent a hydrogen atom or a methyl group, R ^3x to R ^6x each independently represent a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom, and X represents an ethyleneoxyethyl group, Di(ethyleneoxy)ethyl, tri(ethyleneoxy)ethyl, propyleneoxypropyl, di(propyleneoxy)propyl, tri(propyleneoxy)propyl, or alkane with 2~15 carbons groups (such as methylene or ethylenyl).

Among them, the epoxy compound (C) is considered to have further excellent varnish compatibility in the curable composition, and the low thermal expansion, heat resistance, and peel strength of the obtained cured product are more excellent, and can further exhibit resistance. From the point of view of drug properties and insulation reliability, it is preferably selected from bisphenol-type epoxy resin, aralkyl-type epoxy resin, biphenyl-type epoxy resin, naphthalene-type epoxy resin, and dicyclopentadiene-type epoxy resin One or more types of the group formed are more preferably biphenyl-type epoxy resins and/or naphthalene-type epoxy resins.

The average number of epoxy groups per molecule of the epoxy compound (C) is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exerting the effects of the present embodiment. The average number of epoxy groups was calculated by the following formula.

[number 4]

In the formula, Ci represents the number of epoxy groups in the epoxy compound with i epoxy groups in the molecule, Zi represents the proportion of the epoxy compound with i epoxy groups in the molecule to the overall epoxy compound, Z ₁ + Z ₂ + . . . Z _n =1.

Considering the content of the epoxy compound (C), the curable composition has further excellent varnish compatibility, and the obtained cured product has better low thermal expansion, heat resistance, and peel strength, and can further exhibit chemical resistance From the viewpoint of insulation reliability, it is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, based on 100% by mass of the total of epoxy-modified polysiloxane (B) and epoxy compound (C). 15 to 60% by mass is still more preferable, and 20 to 50% by mass is still more preferable.

･Phenol compounds (G) other than alkenylphenol (A) The thermosetting compound (D) or polymer (D1) preferably contains a compound derived from alkene in view of further excellent varnish compatibility of the curable composition, and further excellent heat resistance and peel strength of the cured product obtained. Structural unit of phenol compound (G) other than phenol (A).

Phenolic compounds (G) include bisphenol-type phenolic resins (such as bisphenol A-type resins, bisphenol-E-type resins, bisphenol-F-type resins, bisphenol-S-type resins, etc.), phenolic novolac resins (such as phenol novolac varnish resin, naphthol novolac resin, cresol novolac resin, etc.), glycidyl ester type phenolic resin, naphthalene type phenolic resin, anthracene type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, Alicyclic phenolic resins, polyol-type phenolic resins, aralkyl-type phenolic resins, phenol-modified aromatic hydrocarbon formaldehyde resins, fennel-type phenolic resins, etc. These phenolic compounds (G) may be used alone or in combination of two or more.

Among them, the phenolic compound (G) is preferably phenolic compound (G) in 1 molecule from the viewpoint that the curable composition has further excellent varnish compatibility, and the obtained cured product is more excellent in low thermal expansion, heat resistance, and peel strength. Bifunctional phenolic compound with 2 phenolic hydroxyl groups.

Examples of bifunctional phenolic compounds include bisphenol, biscresol, bisphenols with a fennel skeleton (such as bisphenol with a fennel skeleton, biscresol with a fennel skeleton, etc.), biphenols (such as p,p'-linked phenol, etc.), dihydroxydiphenyl ether (such as 4,4'-dihydroxydiphenyl ether, etc.), dihydroxybenzophenone (such as 4,4'-dihydroxybenzophenone, etc.), dihydroxy Diphenylsulfide (such as 4,4'-dihydroxydiphenylsulfide, etc.), dihydroxyaromatic hydrocarbon (such as hydroquinone, etc.). These bifunctional phenol compounds may be used alone or in combination of two or more. Among them, the bifunctional phenol compound is preferably at least one selected from the group consisting of bisphenols, biscresols, and bisphenols having a fenugreek skeleton from the viewpoint of low thermal expansion, heat resistance, and better peel strength. 1 type, preferably bisphenols having a fenugreek skeleton. Considering the same point of view as above, the bisphenols having a fennel skeleton are preferably biscresol fennel.

･Method for producing thermosetting compound (D) or polymer (D1) Thermosetting compound (D) or polymer (D1) is not particularly limited, for example, alkenylphenol (A), epoxy-modified polysiloxane (B), epoxy compound (C), and The phenolic compound (G) is obtained by performing a reaction step in the presence of a polymerization catalyst described later. This reaction can also be carried out in the presence of an organic solvent. More specifically, in the above steps, by carrying out the addition reaction of the epoxy group possessed by the epoxy-modified polysiloxane (B) and the epoxy compound (C) and the hydroxyl group possessed by the alkenylphenol (A) , and the addition reaction of the hydroxyl group of the obtained addition reaction product with the epoxy group of the epoxy-modified polysiloxane (B) and the epoxy compound (C), etc., can obtain the thermosetting compound (D ) or polymer (D1).

In the production of thermosetting compound (D) or polymer (D1), the compounding amount of alkenylphenol (A) is considered to have further excellent varnish compatibility of the curable composition, and the obtained cured product is low. From the point of view of better thermal expansion, heat resistance, and peel strength, compared to the total of alkenylphenol (A), epoxy-modified polysiloxane (B), epoxy compound (C), and phenol compound (G) 100 Parts by mass are preferably 1 to 50 parts by mass, more preferably 3 to 40 parts by mass, and even more preferably 5 to 30 parts by mass.

The blending amount of epoxy-modified polysiloxane (B) considers that the curable composition has further excellent varnish compatibility, and the obtained cured product has better low thermal expansion, heat resistance, and peel strength, and From the viewpoint of exhibiting a balance between low thermal expansion and chemical resistance, 100% of the total of alkenylphenol (A), epoxy-modified polysiloxane (B), epoxy compound (C), and phenol compound (G) The parts by mass are preferably 5-70 parts by mass, more preferably 10-60 parts by mass, and more preferably 20-55 parts by mass.

The blending amount of the epoxy compound (C) considers that the curable composition has further excellent varnish compatibility, and the obtained cured product has better low thermal expansion, heat resistance, and peel strength, and can further exhibit From the viewpoint of chemical resistance and insulation reliability, it is preferable to 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 15 to 25 parts by mass.

The blending amount of the phenolic compound (G) is based on the viewpoint that the curable composition has further excellent varnish compatibility, and the obtained cured product has better low thermal expansion, heat resistance, and peel strength. The total amount of phenol (A), epoxy-modified polysiloxane (B), epoxy compound (C), and phenol compound (G) is 100 parts by mass, preferably 5-30 parts by mass, more preferably 10-30 parts by mass Best, more preferably 15 to 25 parts by mass.

In addition, when the thermosetting compound (D) or the polymer (D1) does not contain the phenol compound (G), the above-mentioned alkenylphenol (A), epoxy-modified silicone (B), and epoxy compound (C) Each compounding quantity of each shows the compounding quantity with respect to the total of 100 mass parts of alkenylphenol (A), epoxy-modified polysiloxane (B), and an epoxy compound (C).

As a polymerization catalyst, an imidazole catalyst and a phosphorus catalyst are mentioned, for example. These catalysts may be used alone or in combination of two or more. Among them, an imidazole catalyst is preferable.

Examples of imidazole catalysts include: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2- Phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dimethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Imidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole (TBZ (trade name), Shikoku Chemical Industry Co., Ltd.), 2,4,5-triphenylimidazole (TPIZ (trade name), Tokyo Chemical Industry Co., Ltd.) and other imidazoles. Among them, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and/or 2,4,5-triphenylimidazole are preferable from the viewpoint of preventing homopolymerization of the epoxy component.

The amount of polymerization catalyst (preferably imidazole catalyst) used, for example, relative to the total of alkenylphenol (A), epoxy-modified polysiloxane (B), epoxy compound (C), and phenolic compound (G) 100 parts by mass is 0.1 to 10 parts by mass. From the viewpoint of increasing the weight average molecular weight of the thermosetting compound (D) or polymer (D1), the amount of the polymerization catalyst used is preferably 0.5 parts by mass or more, more preferably 4.0 parts by mass or less.

As the organic solvent, for example, a polar solvent or a nonpolar solvent can be used. Polar solvents include, for example: ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; celluloid-based solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethyl lactate, methyl acetate, and ethyl acetate. , butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate and other ester solvents; dimethylacetamide, dimethylformamide and other amides wait. As a nonpolar solvent, aromatic hydrocarbons, such as toluene and xylene, etc. are mentioned, for example. These solvents may be used alone or in combination of two or more.

The amount of the organic solvent used is not particularly limited, for example, with respect to a total of 100 parts by mass of alkenylphenol (A), epoxy-modified polysiloxane (B), epoxy compound (C), and phenol compound (G), 50 to 150 parts by mass.

The reaction temperature is not particularly limited, and may be, for example, 100 to 170°C. The reaction time is not particularly limited, for example, it can be 3-8 hours.

After the reaction in this step is completed, the thermosetting compound (D) or polymer (D1) can also be isolated and purified from the reaction mixture by a conventional method.

＜Epoxy resin (E)＞ The curable composition of this embodiment contains an epoxy resin (E). The epoxy resin (E) is different from the epoxy-modified polysiloxane (B), but may be the same as or different from the epoxy compound (C). By using the epoxy resin (E) and the cyanate compound (F) together with the thermosetting compound (D) at a specific functional group equivalent ratio, further excellent varnish compatibility can be obtained, and the hardened product can simultaneously exhibit Low thermal expansion, heat resistance, and high peel strength, and further improve chemical resistance and insulation reliability. An epoxy resin (E) can be used individually by 1 type or in appropriate combination of 2 or more types.

As an epoxy resin (E), typically, the bifunctional epoxy compound which has 2 epoxy groups in 1 molecule, and the polyfunctional epoxy compound which has 3 or more epoxy groups in 1 molecule can be used. Epoxy compound (E) considers that the curable composition can have further excellent varnish compatibility, and the obtained cured product has better low thermal expansion, heat resistance, and peel strength, and can further exhibit chemical resistance and From the viewpoint of insulation reliability, it is preferable to contain a bifunctional epoxy compound and/or a polyfunctional epoxy compound.

The epoxy compound (E) is not particularly limited, and a compound represented by the following formula (3a) can be used.

[chem 22]

In formula (3a), Ar ³ each independently represents a benzene ring or a naphthalene ring, Ar ⁴ represents a benzene ring, a naphthalene ring, or a biphenyl ring, R ^3a each independently represent a hydrogen atom or a methyl group, and k represents 1 to 50 Integer, here, the benzene ring or naphthalene ring in Ar ³ can also have one or more substituents, and the substituents can also be glycidyloxy groups not shown in the figure, and other substituents can also be, for example, carbon number 1 to 5 alkyl, phenyl, etc., the benzene ring in Ar ⁴ , naphthalene ring, or biphenyl ring can also have one or more substituents, the substituents can also be glycidyloxy, other substitutions The group may be, for example, an alkyl group having 1 to 5 carbon atoms, a phenyl group, or the like.

Among the compounds represented by the above-mentioned formula (3a), examples of the bifunctional epoxy compound include compounds represented by the following formula (b1).

[chem 23]

In formula (b1), Ar ³ each independently represents a benzene ring or a naphthalene ring, Ar ⁴ represents a benzene ring, a naphthalene ring, or a biphenyl ring, R ^3a each independently represent a hydrogen atom or a methyl group, and here, in Ar ³ The benzene ring or naphthalene ring can also have one or more substituents, for example, the substituents can also be substituents other than glycidoxy groups such as alkyl groups with 1 to 5 carbon atoms, phenyl groups, etc., Ar ⁴ The benzene ring, naphthalene ring or biphenyl ring may also have one or more substituents. For example, the substituents may also be substituents other than glycidoxy groups such as alkyl groups with 1 to 5 carbon atoms and phenyl groups. .

The compound represented by formula (3a) is preferably a phenolic novolac epoxy resin in which Ar ⁴ is at least substituted by glycidoxy in formula (3a). Phenolic novolak-type epoxy resins are not particularly limited, and examples thereof include compounds represented by the following formula (3-1) (polyfunctional epoxy resins having a naphthalene skeleton and containing a naphthalene skeleton), naphthalene-cresol novolac-type ring oxygen resin.

[chem 24]

In formula (3-1), Ar ³¹ each independently represents a benzene ring or a naphthalene ring, Ar ⁴¹ each independently represent a benzene ring, a naphthalene ring or a biphenyl ring, R ^31a each independently represent a hydrogen atom or a methyl group, and kz represents An integer of 1 to 50, each ring may also have a substituent other than glycidoxy (such as an alkyl group with 1 to 5 carbons, an alkoxy group with 1 to 5 carbons, or a phenyl group), Ar ³¹ and Ar ⁴¹ At least one of them represents a naphthalene ring.

Examples of the compound represented by formula (3-1) include compounds represented by formula (3-2).

[chem 25]

In the formula (3-2), R represents a methyl group, and kz has the same meaning as kz in the above formula (3-1).

The naphthyl cresol novolak type epoxy resin is not particularly limited, for example, a cresol/naphthol novolak type epoxy resin represented by the following formula (NE) is preferable. In addition, the compound represented by the following formula (NE) is a random copolymer of a constituent unit of a cresol novolak resin epoxy and a constituent unit of a naphthol novolac resin epoxy, and the cresol epoxy and the naphthol ring Any of the oxides may serve as the terminal.

[chem 26]

m and n in the formula (NE) each represent an integer of 1 or more. The upper limit and ratio of m and n are not particularly limited. Considering low thermal expansion, m:n (here, m+n=100) should be 30~50:70~50, 45~55:55~ 45 is better.

As the naphthylcresol novolak-type epoxy resin, a commercially available product may be used, or a product manufactured by a known method may be used. Commercially available products include, for example: "NC-7000", "NC-7300", and "NC-7300L" produced by Nippon Kayaku Co., Ltd., or "HP-9540" and "HP-9500L" produced by DIC Co., Ltd. ", etc., especially "HP-9540".

The compound represented by formula (3a) may be a compound other than the aforementioned phenolic novolac epoxy resin (hereinafter also referred to as "aralkyl epoxy resin"). The aralkyl type epoxy resin is preferably Ar in the formula (3a) ³ is a naphthalene ring, and Ar ⁴ is a compound of a benzene ring (also known as "naphthol aralkyl type epoxy resin"), and the formula (3a) Among them, Ar ³ is a benzene ring, and Ar ⁴ is a compound of a biphenyl ring (also called "biphenyl aralkyl type epoxy resin"), preferably a biphenyl aralkyl type epoxy resin.

As the naphthol aralkyl type epoxy resin, a commercial item may be used, or a product manufactured by a known method may be used. Commercially available products include, for example, "HP-5000" and "HP-9900" produced by DIC Co., Ltd., "ESN-375" and "ESN-475" produced by Nippon Steel Chemical Materials Co., Ltd., and the like.

The biphenyl aralkyl type epoxy resin is preferably a compound represented by formula (3b).

[chem 27]

In the formula (3b), ka represents an integer of 1 or more, preferably 1-20, more preferably 1-6.

Among the compounds represented by the above-mentioned formula (3b), examples of the bifunctional epoxy compound include compounds in which ka is 1 in the formula (3b).

As the biphenyl aralkyl type epoxy resin, a commercial item may be used, or a product manufactured by a known method may be used. Examples of commercially available products include "NC-3000", "NC-3000L", and "NC-3000FH" produced by Nippon Kayaku Co., Ltd.

Also, as the epoxy compound (E), naphthalene-type epoxy resins (excluding those represented by the formula (3a)) are preferably used. Naphthalene-type epoxy resins are considered to have further excellent varnish compatibility, and the obtained cured product has better low thermal expansion, heat resistance, and peel strength, and can further demonstrate chemical resistance and insulation reliability. It is preferably a naphthyl ether type epoxy resin.

The naphthyl ether-type epoxy resin is preferably the following formula (3-3) in view of the low thermal expansion, heat resistance, and peel strength of the hardened product that can be further improved, and the chemical resistance and insulation reliability can be further improved. The difunctional epoxy compound represented by or the polyfunctional epoxy compound represented by following formula (3-4), or their mixture.

[chem 28]

In formula (3-3), R ₁₃ each independently represents a hydrogen atom, an alkyl group with 1 to 3 carbons (such as methyl or ethyl), or an alkenyl with 2 to 3 carbons (such as vinyl, allyl, etc.) base or propenyl).

[chem 29]

In formula (3-4), R ₁₄ each independently represents a hydrogen atom, an alkyl group with 1 to 3 carbons (such as methyl or ethyl), or an alkenyl with 2 to 3 carbons (such as vinyl, allyl, etc.) base or propenyl).

As the naphthyl ether type epoxy resin, a commercial item may be used, or a product manufactured by a known method may be used. Commercially available naphthyl ether type epoxy resins include, for example, "HP-6000", "EXA-7300", "EXA-7310", "EXA-7311", "EXA-7311L" of DIC Co., Ltd. ", "EXA7311-G3", "EXA7311-G4", "EXA-7311G4S", "EXA-7311G5", etc., especially "HP-6000".

Examples of naphthalene-type epoxy resins other than the above are not limited to the following, but compounds represented by the following formula (b3) are exemplified.

[chem 30]

In formula (b3), R ^3b each independently represent a hydrogen atom, an alkyl group (such as methyl or ethyl) with 1 to 5 carbons, an aralkyl group, a benzyl group, a naphthyl group, a glycidyl group containing at least one Naphthyl group, or naphthylmethyl group containing at least one glycidoxy group, n represents an integer of 0 or more (for example, 0~2).

Commercial products of the compound represented by the above formula (b3) include, for example, "HP-4032" (n=0 in the above formula (b3)) and "HP-4710" (the above formula (b3) Among them, n=0, and R ^3b is a naphthylmethyl group containing at least one glycidoxyl group) and the like.

Moreover, the epoxy compound (E) can use a dicyclopentadiene type epoxy resin (those belonging to the said epoxy compound (C) are excluded). The dicyclopentadiene epoxy resin is not particularly limited, and examples thereof include compounds represented by formula (3-5).

[chem 31]

In the formula (3-5), R ^3c each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbons, and k2 represents an integer of 0 to 10.

The compound represented by the above formula (3-5) is not particularly limited, and may be, for example, a compound represented by the following formula (b4).

[chem 32]

In formula (b4), R ^3c each independently represent a hydrogen atom, or an alkyl group having 1 to 5 carbons (such as methyl or ethyl).

As the dicyclopentadiene type epoxy resin, a commercial item may be used, or a product manufactured by a known method may be used. Commercially available dicyclopentadiene type epoxy resins include "EPICRON HP-7200L", "EPICRON HP-7200", "EPICRON HP-7200H", "EPICRON HP- 7000HH", etc.

Among them, the epoxy compound (E) is considered to have further excellent varnish compatibility, and the obtained cured product is more excellent in low thermal expansion, heat resistance, and peel strength, and can exhibit further chemical resistance. , and from the viewpoint of insulation reliability, it is preferable to contain at least one selected from the group consisting of epoxy compounds represented by formula (3a), naphthalene-type epoxy resins, and dicyclopentadiene-type epoxy resins. At least one kind selected from the group consisting of an epoxy compound represented by formula (3a) and a naphthalene-type epoxy resin is more preferable. In this case, the epoxy compound represented by the formula (3a) preferably contains a naphthyl cresol novolak type epoxy resin, and the naphthalene type epoxy resin preferably contains a naphthyl ether type epoxy resin.

The epoxy compound (E) may contain other epoxy resins other than the aforementioned epoxy compounds. Other epoxy resins are not particularly limited, and examples include: bisphenol-type epoxy resins, paraphenolmethane-type epoxy resins, anthracene-type epoxy resins, glycidyl ester-type epoxy resins, polyol-type epoxy resins, Epoxy resins containing isocyanurate rings, fennel-type epoxy resins, and epoxy resins composed of bisphenol A-type structural units and hydrocarbon-based structural units, etc. Among the above, other epoxy resins are considered to have further excellent varnish compatibility, and the obtained cured product has better low thermal expansion, heat resistance, and peel strength, and can further exhibit chemical resistance and insulation reliability. From the point of view of property, bisphenol type epoxy resin can be contained, bisphenol type epoxy resin can use for example: diallyl bisphenol type epoxy resin (for example diallyl bisphenol A type epoxy resin, diallyl base bisphenol E epoxy resin, diallyl bisphenol F epoxy resin, diallyl bisphenol S epoxy resin, etc.), etc.

The epoxy compound (E) can be used individually by 1 type or in combination of 2 or more types among the said epoxy compounds.

The average number of epoxy groups per molecule of the epoxy compound (E) is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exerting the effects of the present embodiment. The average number of epoxy groups was calculated by the following formula.

[number 5]

In the above formula, Ci represents the number of epoxy groups in the epoxy compound with i epoxy groups in the molecule, Zi represents the ratio of the epoxy compound with i epoxy groups in the molecule to the overall epoxy compound, Z ₁ + Z ₂ + . . . Z _n =1.

The content of the total of the epoxy resin (E) and the cyanate compound (F) described later is higher than that of the thermosetting compound (D) in view of the low thermal expansion, heat resistance, and peel strength of the obtained cured product. It is preferably 50 to 75 parts by mass, more preferably 55 to 70 parts by mass, based on 100 parts by mass of the total of the epoxy resin (E) and the cyanate compound (F) described later.

The total content of the thermosetting compound (D), the epoxy resin (E) described later, and the cyanate compound (F) described later in the curable composition of this embodiment is determined by considering the low thermal expansion and heat resistance of the obtained cured product. From the point of view of the tendency to have better properties and peel strength, it is preferably 50 to 99 parts by mass, more preferably 60 to 95 parts by mass, and more preferably 70 to 90 parts by mass relative to 100 parts by mass of resin solid content in the resin composition. better.

＜Cyanate compound (F)＞ The curable composition of this embodiment contains a cyanate compound (F). By using the cyanate compound (F) and the epoxy resin (E) together with the thermosetting compound (D) at a specific functional group equivalent ratio, the cured product can simultaneously exhibit low thermal expansion, heat resistance, and high peeling Strength, and can further improve chemical resistance. A cyanate compound (F) can be used individually by 1 type or in appropriate combination of 2 or more types.

The cyanate compound (F) is not particularly limited if it is a compound having two or more cyanate groups (cyanate groups) in one molecule, and examples thereof include naphthol aromatic compounds such as compounds represented by formula (4). Alkyl type cyanate compounds, novolak type cyanate compounds such as compounds represented by formula (5) other than compounds represented by formula (4), biphenyl aralkyl type cyanate compounds, diallyl bis Phenolic cyanate compounds, bis(3,3-dimethyl-4-cyanooxyphenyl)methane, bis(4-cyanooxyphenyl)methane, 1,3-dicyanooxybenzene, 1 ,4-dicyanoxybenzene, 1,3,5-tricyanoxybenzene, 1,3-dicyanoxynaphthalene, 1,4-dicyanoxynaphthalene, 1,6-dicyanoxynaphthalene , 1,8-dicyanoxynaphthalene, 2,6-dicyanoxynaphthalene, 2,7-dicyanoxynaphthalene, 1,3,6-tricyanoxynaphthalene, 4,4'-dicyanooxynaphthalene Oxybiphenyl, Bis(4-Cyanooxyphenyl) Ether, Bis(4-Cyanoxyphenyl) Sulfide, Bis(4-Cyanoxyphenyl) Phenyl, 2,2-Bis(4- Cyanooxyphenyl) propane.

Among them, the cyanate compound (F) preferably includes a naphthol aralkyl type cyanide compound from the viewpoint that the obtained hardened product is more excellent in low thermal expansion, heat resistance, and peel strength, and can further improve chemical resistance. The ester compound and/or the novolak type cyanate compound, preferably including the naphthol aralkyl type cyanate compound.

Considering the low thermal expansion, heat resistance, and peel strength of the cured product obtained, and the viewpoint of further improving chemical resistance, it is more preferable that the naphthol aralkyl type cyanate compound includes the compound represented by formula (4) . It is still more preferable that the novolac-type cyanate compound contains a compound represented by formula (5) other than the compound represented by formula (4).

[chem 33]

In formula (4), R ₆ each independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more. n ₂ is preferably an integer of 1 to 20, more preferably an integer of 1 to 10, and even more preferably an integer of 1 to 6.

[chem 34]

In formula (5), R _ya each independently represents an alkenyl group having 2 to 8 carbon atoms, or a hydrogen atom, R _yb each independently represents an alkyl group having 1 to 10 carbon atoms, or a hydrogen atom, and R _yc each independently represents An aromatic ring with 4~12 carbons, R _yc can also form a condensed structure with a benzene ring, R _yc may or may not exist, A ^1a each independently represent an alkylene group with 1~6 carbons, an alkylene group with 7~16 carbons Aralkylene group, arylylene group with 6~10 carbons, fenylene group, sulfonyl group, oxygen atom, sulfur atom, or single bond (direct bond), when R _yc does not exist, there is also a benzene ring It may have two or more R _ya and/or R _yb groups. n represents an integer from 1 to 20.

In formula (5), the alkenyl group having 2 to 8 carbon atoms represented by R _ya includes, for example, vinyl group, allyl group, propenyl group, butenyl group, hexenyl group and the like.

In formula (5), the alkyl group of the carbon number 1～10 represented by _Ryb can enumerate for example: methyl, ethyl, propyl, butyl, pentyl, hexyl and other linear alkyl groups; isopropyl, iso Butyl, tertiary butyl and other branched alkyl groups.

In formula (5), the alkylene group having 1 to 6 carbon atoms represented by A ^1a includes methylene, ethylene, trimethylene, and propylidene. In addition, in formula (5), the aralkylene group having 7 to 16 carbon atoms represented by A ^1a can be exemplified by the formula: -CH ₂ -Ar-CH ₂ -, -CH ₂ -CH ₂ -Ar-CH ₂ -CH ₂ -, or a group represented by the formula: -CH ₂ -Ar-CH ₂ -CH ₂ - (wherein, Ar represents phenylene, naphthylene, or biphenylene). In addition, the arylylene group having 6 to 10 carbon atoms represented by A ^1a includes, for example, a phenylene ring.

In formula (5), n represents an integer of 1 to 20, preferably an integer of 1 to 15, more preferably an integer of 1 to 10.

The compound represented by formula (5) is preferably a phenol novolac type cyanate compound, and the phenol novolac type cyanate compound is preferably a compound represented by formula (c1).

[chem 35]

In the formula (c1), Rx each independently represent a hydrogen atom or a methyl group, each R independently represents an alkenyl group having 2 to 8 carbons, an alkyl group having 1 to 10 carbons, or a hydrogen atom, and n represents a group of 1 to 10 integer.

These cyanate compounds (F) can also be produced according to known methods. The specific production method can be, for example, the method described in JP-A-2017-195334 (particularly paragraphs 0052-0057).

＜Maleimide compound＞ In the curable composition of this embodiment, it is preferable to further contain a maleimide compound in consideration of the low thermal expansion, heat resistance, and peel strength of the obtained cured product, and to further improve the chemical resistance. . The maleimide compound can be used alone or in appropriate combination of two or more.

The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule, and examples thereof include monomaleimide compounds having one maleimide group in one molecule. Amide compounds (such as N-phenylmaleimide, N-hydroxyphenylmaleimide, etc.), polymaleimides having two or more maleimide groups in one molecule Compounds (such as bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis(3-ethyl -5-methyl-4-maleiminophenyl)methane, bis(3,5-dimethyl-4-maleiminophenyl)methane, bis(3,5-diethyl Base-4-maleimidophenyl) methane), m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6' -Bismaleimide-(2,2,4-trimethyl)hexane, a maleimide compound represented by the following formula (3), a maleimide compound represented by the following formula (3') , Prepolymers of these maleimide compounds and amine compounds, etc.

[chem 36]

In formula (3), R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 to 100.

n ₁ is 1 or more, preferably 1-100, more preferably 1-10.

[chem 37]

In the formula (3′), R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n4 represents an integer of 1 to 10.

Among them, the maleimide compound preferably contains a compound selected from bis(4-maleimidophenyl)methane, 2 ,2-bis(4-(4-maleiminophenoxy)phenyl)propane, bis(3-ethyl-5-methyl-4-maleiminophenyl)methane, At least one of the group consisting of a maleimide compound represented by formula (3) and a maleimide compound represented by formula (3′).

As the maleimide compound, a commercially available product may be used, or a product produced by a known method may be used. Commercially available maleimide compounds include "BMI-70", "BMI-80", and "BMI-1000P" produced by K･I Chemicals Co., Ltd., and "BMI-1000P" produced by Daiwa Chemical Industry Co., Ltd. -3000", "BMI-4000", "BMI-5100", "BMI-7000", "BMI-2300", "MIR-3000-70MT" of Nippon Kayaku Co., Ltd. (Formula (3') R ¹³ are all hydrogen atoms, and n4 is a mixture of 1 to 10), etc.

The content of the maleimide compound is lower than that of the thermosetting compound (D), epoxy resin (E) and cyanate The total of 100 parts by mass of the compound (F) is preferably 5 to 45 parts by mass, more preferably 20 to 45 parts by mass.

＜Phenolic compounds＞ The curable composition of this embodiment may further contain a phenolic compound as long as it does not hinder the effect of the curable composition of this embodiment. Among the phenol compounds, the alkenyl phenol (A) and the phenol compounds (G) other than the alkenyl phenol (A) may be the same or different from each other. The phenolic compound can be used individually by 1 type or in appropriate combination of 2 or more types.

The phenolic compound is not particularly limited as long as it is a compound having two or more phenolic hydroxyl groups in one molecule, and examples thereof include phenols having two or more phenolic hydroxyl groups in one molecule, bisphenols (such as bisphenol A , bisphenol E, bisphenol F, bisphenol S, etc.), diallyl bisphenols (such as diallyl bisphenol A, diallyl bisphenol E, diallyl bisphenol F, diene Propyl bisphenol S, etc.), phenolic novolac resins (such as phenol novolac resins, naphthol novolac resins, cresol novolak resins, etc.), naphthalene-type phenolic resins, dihydroanthracene-type phenolic resins, dicyclopentadiene Type phenolic resin, biphenyl type phenolic resin, and aralkyl type phenolic resin. These phenolic compounds may be used alone or in combination of two or more. Among them, the phenolic compound preferably contains an aralkyl type phenolic resin from the viewpoint that the obtained cured product is more excellent in low thermal expansion, heat resistance, and peel strength.

(Aralkyl type phenolic resin) As an aralkyl type phenolic resin, the compound represented by formula (c2) is mentioned, for example.

[chem 38]

In formula (c2), Ar ¹ each independently represents a benzene ring or a naphthalene ring, Ar ² represents a benzene ring, a naphthalene ring, or a biphenyl ring, R ^2a each independently represent a hydrogen atom or a methyl group, and m represents 1 to 50 Integers, each ring may have a substituent other than hydroxyl (for example, an alkyl group having 1 to 5 carbon atoms or a phenyl group, etc.).

The compound represented by the formula (c2) is preferably a compound in which Ar ¹ is a naphthalene ring and Ar ² is a benzene ring in the formula (c2) in view of the low thermal expansion, heat resistance, and peel strength of the obtained cured product (hereinafter Also known as "naphthol aralkyl type phenolic resin"), and compounds in which Ar ¹ is a benzene ring and Ar ² is a biphenyl ring in formula (c2) (hereinafter also referred to as "biphenyl aralkyl type phenolic resin" ).

The naphthol aralkyl type phenolic resin is preferably a compound represented by formula (2b).

[chem 39]

In the formula (2b), R ^2a each independently represent a hydrogen atom or a methyl group (preferably a hydrogen atom), and m represents an integer of 1 to 10 (preferably an integer of 1 to 6).

The biphenyl aralkyl type phenolic resin is preferably a compound represented by formula (2c).

[chemical 40]

In formula (2c), R ^{and 2b} each independently represent a hydrogen atom, an alkyl group with 1 to 5 carbons, or a phenyl group (preferably a hydrogen atom), m1 represents an integer of 1 to 20 (preferably an integer of 1 to 6) .

As the aralkyl type phenolic resin, a commercial item may be used, or a product synthesized by a known method may be used. Commercially available aralkyl type phenolic resins include: "KAYAHARD GPH-65", "KAYAHARD GPH-78", "KAYAHARD GPH-103" (biphenyl aralkyl type phenolic resins) manufactured by Nippon Kayaku Co., Ltd. ), "SN-495" (naphthol aralkyl type phenolic resin) produced by Nippon Steel Chemical Materials Co., Ltd.

The content of the phenolic compound is lower than that of the thermosetting compound (D), epoxy resin (E) and cyanate compound (F) in consideration of the low thermal expansion, heat resistance, and peel strength of the obtained cured product. 100 parts by mass in total, preferably 1 to 40 parts by mass.

<Alkenyl-substituted nadiimide compounds> In the curable composition of this embodiment, as long as the effect of the curable composition of this embodiment is not hindered, an alkenyl-substituted nadicimide compound may be further contained. The alkenyl-substituted nadicimide compound can be used alone or in appropriate combination of two or more.

The alkenyl-substituted nadicimide compound is not particularly limited if it is a compound having one or more alkenyl-substituted nadicimide groups in one molecule, and examples thereof include the following formula (2d): compound.

[chem 41]

In formula (2d), R ₁ each independently represents a hydrogen atom, or an alkyl group (such as methyl or ethyl) with 1 to 6 carbons, and R ₂ represents an alkylene group, phenylene group, or phenylene group with 1 to 6 carbons. A biphenylene group, a naphthylene group, or a group represented by the following formula (6) or the following formula (7).

[chem 42]

In formula (6), R ₃ represents methylene, isopropylidene, CO, O, S or SO ₂ .

[chem 43]

In the formula (7), R ₄ each independently represent an alkylene group having 1 to 4 carbon atoms, or a cycloalkylene group having 5 to 8 carbon atoms.

The alkenyl-substituted nadicimide compound represented by the formula (2d) may be a commercially available product, or a product produced by a known method may be used. Commercially available products include "BANI-M" and "BANI-X" produced by Maruzen Petrochemical Co., Ltd.

The content of the alkenyl-substituted nadicimide compound is considered to be more excellent in low thermal expansion, heat resistance, and peel strength of the cured product. Compared with the thermosetting compound (D) and the epoxy resin (E ) and the total of 100 parts by mass of the cyanate compound (F), preferably 1 to 40 parts by mass.

＜Other resins＞ In the curable composition of the present embodiment, other resins may be further contained as long as the effects of the curable composition of the present embodiment are not hindered. Other resins include, for example, oxetane resins, benzodiazepine compounds, and compounds having polymerizable unsaturated groups. These resins or compounds can be used individually by 1 type or in appropriate combination of 2 or more types.

Oxetane resins include, for example: oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3 ,3-Dimethyloxetane and other alkyloxetanes, 3-methyl-3-methoxymethyloxetane, 3,3'-bis(trifluoromethyl) Perfluorooxetane, 2-chloromethyl oxetane, 3,3-bis(chloromethyl) oxetane, biphenyl type oxetane, product of Toa Gosei Co., Ltd. "OXT-101", "OXT-121" and so on.

The term "benzohexacompound" in this specification refers to a compound having two or more dihydrobenzoxaha rings in one molecule. Examples of the benzo㗁𠯤 compound include "Bisphenol F-type benzo㗁𠯤 BF-BXZ" and "Bisphenol S-type benzo㗁𠯤BS-BXZ" produced by Konishi Chemical Co., Ltd.

Examples of compounds having polymerizable unsaturated groups include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth)acrylate, (meth)acrylic acid-2 -Hydroxyethyl ester, -2-Hydroxypropyl (meth)acrylate, Polypropylene glycol di(meth)acrylate, Trimethylolpropane di(meth)acrylate, Trimethylolpropane tri(methyl) Acrylic ester, neopentylthritol tetra(meth)acrylate, dipentynerythritol hexa(meth)acrylate and other units or (meth)acrylates of polyols; bisphenol A epoxy (methyl) ) acrylate, bisphenol F epoxy (meth)acrylate and other epoxy (meth)acrylates; benzocyclobutene resin, etc.

＜Inorganic filler＞ In the curable composition of this embodiment, it is preferable to further contain an inorganic filler from the viewpoint of further improving the low thermal expansion property of the obtained cured product.

Examples of inorganic fillers include silicon dioxide, silicon compounds (such as white carbon, etc.), metal oxides (such as alumina, titanium dioxide, titanium oxide, barium titanate, zinc oxide, magnesium oxide, zirconia, etc.), metal Nitride (such as boron nitride, condensed boron nitride, silicon nitride, aluminum nitride, etc.), metal oxysulfide (such as barium sulfate, etc.), metal hydroxide (such as aluminum hydroxide, aluminum hydroxide heat treatment products (such as heat-treating aluminum hydroxide and subtracting part of the water of crystallization), boehmite, magnesium hydroxide, etc.), zinc compounds (such as zinc borate, zinc stannate, etc.), clay, kaolin, talc (talc), calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass Fiber (including E glass, T glass, D glass, S glass, Q glass and other glass powders), hollow glass, spherical glass, etc. These inorganic fillers may be used alone or in combination of two or more. Among them, the inorganic filler is preferably selected from silicon dioxide, aluminum hydroxide, alumina, boehmite, boron nitride, aluminum nitride, At least one member selected from the group consisting of titanium oxide, barium titanate, magnesium oxide, and magnesium hydroxide is more preferably silicon dioxide.

Examples of silica include natural silica, fused silica, synthetic silica, aerosil, and hollow silica. These silicas may be used alone or in combination of two or more. Among them, fused silica is preferable from the viewpoint of being ideally dispersible in the curable composition.

The content of the inorganic filler is considered to further improve the formability of the curable composition and the low thermal expansion of the cured product. Compared with the thermosetting compound (D), epoxy resin (E), and cyanate compound ( The total of 100 parts by mass of F) is preferably 50 to 350 parts by mass, more preferably 100 to 300 parts by mass.

＜Silane coupling agent＞ The curable composition of this embodiment may further contain a silane coupling agent. When the curable composition contains a silane coupling agent, the dispersibility of the inorganic filler is further improved, and the bonding strength between each component contained in the curable composition and the substrate described later tends to be further improved.

The silane coupling agent is not particularly limited, and silane coupling agents commonly used in surface treatment of inorganic substances are exemplified. Examples include: aminosilane compounds (such as γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane Compounds (such as γ-glycidoxypropyltrimethoxysilane, etc.), acrylic silane-based compounds (such as γ-acryloxypropyltrimethoxysilane, etc.), cationic silane-based compounds (such as N- β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), styrene silane compounds, phenyl silane compounds, etc. A silane coupling agent can be used individually by 1 type, or in combination of 2 or more types. Among them, the silane coupling agent is preferably an epoxy silane compound. Examples of the epoxysilane compound include "KBM-403", "KBM-303", "KBM-402", and "KBE-403" produced by Shin-Etsu Chemical Co., Ltd.

The content of the silane coupling agent is not particularly limited, and may be 0.1 to 10 parts by mass relative to 100 parts by mass of the total of the thermosetting compound (D), epoxy resin (E), and cyanate compound (F). .

＜Wetting and Dispersing Agent＞ The curable composition of this embodiment may further contain a wetting and dispersing agent. When the curable composition contains a wetting and dispersing agent, the dispersibility of the inorganic filler tends to be further improved.

As long as the wetting and dispersing agent is a known dispersing agent (dispersion stabilizer) used to disperse the filler, examples include DISPER BYK-110, 111, 118, 180, 161, BYK- W996, W9010, W903, etc.

The content of the wetting and dispersing agent is not particularly limited, but it is preferably at least 0.5 parts by mass and 5.0 parts by mass relative to 100 parts by mass of the total of the thermosetting compound (D), epoxy resin (E), and cyanate compound (F). servings or less.

<Solvent> The curable composition of this embodiment may further contain a solvent. When the curable composition contains a solvent, the viscosity at the time of preparation of the curable composition is lowered, the handleability (workability) is further improved, and the impregnation property to the base material tends to be further improved.

The solvent is not particularly limited as long as it can dissolve some or all of the components in the curable composition. Examples include: ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (such as toluene, xylene, etc.), amides (such as dimethylformamide, etc.), propylene glycol monomethyl ether and its acetate, etc. . These solvents may be used alone or in combination of two or more.

[Manufacturing method of curable composition] The method for producing the curable composition of the present embodiment is not particularly limited, and examples thereof include a method of mixing the above-mentioned components in a solvent one at a time or one by one and stirring them. At this time, well-known treatments such as stirring, mixing, and kneading can be used in order to dissolve or disperse each component uniformly.

[use] The curable composition of this embodiment can be ideally used as cured products, resin sheets, prepregs, laminates, metal foil-clad laminates, and printed wiring boards. Hereinafter, these are demonstrated.

[hardened object] The cured product is obtained by curing the curable composition of this embodiment. The production method of the cured product is not particularly limited, for example, it can be obtained by melting or dissolving the curable composition of this embodiment in a solvent, pouring it into a mold, and curing it under normal conditions using heat, light, etc. get. In thermosetting, the curing temperature is preferably in the range of 120 to 300° C. in consideration of efficient curing and prevention of deterioration of the obtained cured product.

[resin sheet] The resin sheet of this embodiment has a support body, and the resin layer arrange|positioned on one side or both sides of a support body, and a resin layer contains the curable composition of this embodiment. The resin sheet may be formed, for example, by applying the curable composition of the present embodiment to one or both sides of a support. The resin sheet can be produced, for example, by directly applying and drying the curable composition of the present embodiment on a support such as a metal foil or a film.

As the support, for example, known ones used for various printed wiring board materials can be used, and resin films or metal foils are preferable. Examples of resin films and metal foils include polyimide films, polyamide films, polyester films, polyethylene terephthalate (PET) films, polybutylene terephthalate (PBT) films, Resin films such as polypropylene (PP) film and polyethylene (PE) film, and metal foils such as aluminum foil, copper foil, and gold foil. Among them, the support is preferably electrolytic copper foil or PET film.

The resin sheet can be obtained, for example, by applying the curable composition of this embodiment to a support, and then semi-hardening (B-staging). The method for producing the resin sheet is preferably a method for usually producing a composite of a B-stage resin and a support. Specifically, for example, a method of applying a curable composition to a support such as copper foil and then heating it in a dryer at 100 to 200°C for 1 to 60 minutes to semi-harden and manufacture The method of the resin sheet, etc. The adhesion amount of the curable composition to the support is preferably in the range of 1.0 to 300 μm in terms of the resin thickness of the resin sheet. The resin sheet can be used as a stacking material for printed wiring boards.

[Prepreg] The prepreg of this embodiment includes: a base material, and the curable composition of this embodiment impregnated or coated on the base material. The method for forming the prepreg may be a known method, specifically, by impregnating or coating the base material with the curable composition of this embodiment, and then heating and drying it at 100 to 200°C, And it can be obtained by making it semi-hardened (B-stage).

The prepreg of the present embodiment also includes the form of a cured product obtained by thermally curing a semi-cured prepreg at a heating temperature of 180 to 230° C. and a heating time of 60 to 180 minutes.

The content of the curable composition in the prepreg relative to the total amount of the prepreg is preferably 30~90% by volume, more preferably 35~85% by volume, and 40~ 80% by volume is even better. When the content of the curable composition falls within the above range, formability tends to be further improved. In addition, the solid content of the prepreg here refers to a component obtained by removing the solvent from the prepreg, for example, a filler is included in the solid content of the prepreg.

As a base material, the well-known base material used for the material of various printed wiring boards is mentioned, for example. Examples include: glass substrates, inorganic substrates other than glass (for example, inorganic substrates made of inorganic fibers other than glass such as quartz), organic substrates (for example, made of wholly aromatic polyamide, polyester, Organic substrates composed of organic fibers such as phenylbenzobisoxazole and polyimide), etc. These base materials may be used alone or in combination of two or more. Among them, a glass substrate is preferable from the viewpoint of further improving heating dimensional stability.

Examples of fibers constituting the glass substrate include fibers such as E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. Among them, the fibers constituting the glass base material are preferably selected from E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass from the viewpoint of further excellent strength and low water absorption. More than one fiber in the group.

Examples of the form of the base material include forms such as woven fabric, non-woven fabric, roving, cut strand mat, and surface-treated felt. The weaving method of the woven fabric is not particularly limited, and known examples include plain weave, diagonal weave, and twill weave, and can be appropriately selected from among these known ones depending on the intended use and performance. In addition, glass woven fabrics subjected to fiber opening treatment or surface-treated with a silane coupling agent or the like can be preferably used. The thickness and mass of the base material are usually about 0.01 to 0.1 mm ideally.

[Metal Foil Clad Laminates] The metal foil-clad laminate includes a laminate formed using the prepreg of this embodiment, and metal foils arranged on one or both sides of the laminate. Moreover, a laminated body can also be formed using the resin sheet of this embodiment. That is, the laminate can be formed with one resin sheet or prepreg, or can be formed with a plurality of resin sheets and/or prepregs.

Metal foil (conductor layer) should just be the metal foil used for various printed wiring board materials, For example, metal foils, such as copper and aluminum, are mentioned. Examples of the metal foil of copper include copper foils such as rolled copper foil and electrolytic copper foil. The thickness of the conductor layer is, for example, 1 to 70 μm, preferably 1.5 to 35 μm.

The forming method and forming conditions of the metal foil-clad laminate are not particularly limited, and methods and conditions generally used for laminates and multilayer boards of printed wiring boards can be used. For example, a multilayer press, multilayer vacuum press, continuous molding machine, high temperature and high pressure (autoclave) molding machine, etc. can be used for forming a laminate (the above-mentioned laminate) or a metal foil-clad laminate. In addition, in the forming of the laminate (the above-mentioned laminate) or the metal foil-clad laminate (lamination forming), the temperature is 100~300°C, the pressure is 2~100kgf/cm ² , and the heating time is 0.05~ The range of 5 hours is normal. In addition, post-hardening can also be performed at a temperature of 150~300°C as required. Especially when using a multi-layer press machine, considering the viewpoint of fully accelerating the hardening of the prepreg, the temperature is 200~250°C, the pressure is 10~40kgf/cm ² , and the heating time is 80~130 minutes. The temperature is 215~235°C, the pressure 25~35kgf/cm ² , preferably heating time 90~120 minutes. In addition, a multilayer board can also be produced by combining a prepreg and a wiring board for an inner layer produced separately and performing lamination molding.

[Printed Wiring Board] The printed wiring board of this embodiment has an insulating layer and conductor layers formed on one or both sides of the insulating layer, and the insulating layer contains a cured product of the curable composition of this embodiment. The insulating layer is preferably formed using the resin sheet and/or prepreg of this embodiment. The printed wiring board can be formed, for example, by etching the metal foil of the metal foil-clad laminate into a predetermined wiring pattern as a conductor layer.

A printed wiring board can be manufactured by the following method, for example. First, prepare the metal foil-clad laminate. The metal foil of the metal foil-clad laminate is etched into a predetermined wiring pattern to produce an inner substrate having a conductor layer (inner circuit). Then, by stacking a predetermined number of prepregs and metal foil for outer layer circuits in order on the surface of the conductor layer (inner layer circuit) of the inner layer substrate, and heat and press to form an integral body (lamination molding) to obtain stacks. In addition, the lamination forming method and its forming conditions are the same as the lamination forming method and its forming conditions of the above-mentioned laminate and metal foil-clad laminate. Then, the laminated body is provided with through-holes and hole-drilling for guide holes, and metal plating for conducting conduction between the conductor layer (inner layer circuit) and the metal foil for the outer layer circuit is formed on the wall surface of the hole thus formed. film. Then, the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to produce an outer layer substrate having a conductor layer (outer layer circuit). A printed wiring board is manufactured in this way.

In addition, when the metal foil-clad laminate is not used, a conductor layer as a circuit may be formed on the above-mentioned insulating layer to produce a printed wiring board. In this case, electroless plating can also be used for the formation of the conductor layer. [Example]

Hereinafter, this embodiment is demonstrated more concretely using an Example and a comparative example. This embodiment is not limited by the following examples.

[Measuring method of weight average molecular weight Mw] The weight average molecular weight Mw of the obtained polymer (D1) was measured as follows. 20 μL of a solution obtained by dissolving 0.5 g of a polymer (D1) solution (solid content: 50% by mass) containing a thermosetting compound (D) in 2 g of tetrahydrofuran (THF) was injected into a high performance liquid chromatograph (Shimadzu Corporation ( stock), pump: LC-20AD) and analyzed. Shodex (registered trademark) GPC KF-804 (trade name, length 30 cm×inner diameter 8 mm) and Shodex (registered trademark) GPC KF-803 (trade name, length 30 cm×inner diameter 8 mm) manufactured by Showa Denko Co., Ltd. were used. , Shodex (registered trademark) GPC KF-802 (trade name, length 30cm×inner diameter 8mm), Shodex (registered trademark) GPC KF-801 (trade name, length 30cm×inner diameter 8mm), a total of 4 pieces, using THF for mobile phase (solvent), the flow rate was set at 1 mL/min, and RID-10A (differential refractive index detector, Shimadzu Corporation Co., Ltd.) was used as a detector. The weight average molecular weight Mw was calculated|required by the GPC method using standard polystyrene as a standard substance.

[Synthesis Example 1] Synthesis of 1-naphthol aralkyl-type cyanate compound (SN495V-CN) α-naphthol in which R ^{and 2a} in the above formula (2b) are all hydrogen atoms and m is an integer of 1 to 10 Aralkyl type phenolic resin (SN495V, OH group equivalent: 236g/eq., manufactured by Nippon Steel Chemical Co., Ltd.) 300g (1.28mol in terms of OH group) and 194.6g (1.92mol) of triethylamine (relative to 1mol of hydroxyl group) 1.5mol) was dissolved in 1800g of dichloromethane to make it solution 1. 125.9 g (2.05 mol) of cyanogen chloride (1.6 mol relative to 1 mol of hydroxyl), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol relative to 1 mol of hydroxyl), and 1205.9 g of water The mixture was poured into solution 1 for 30 minutes while maintaining the liquid temperature at -2~-0.5°C under stirring. After the injection of solution 1 was completed, after stirring at the same temperature for 30 minutes, a solution obtained by dissolving 65 g (0.64 mol) of triethylamine (0.5 mol relative to 1 mol of hydroxyl groups) in 65 g of dichloromethane was injected over 10 minutes (solution 2). After solution 2 was injected, it was stirred at the same temperature for 30 minutes to terminate the reaction. Thereafter, the reaction solution was left to stand, and the organic phase and the aqueous phase were separated. The obtained organic phase was washed 5 times with 1300 g of water. The electrical conductivity of the wastewater washed for the fifth time was 5 μS/cm, and it was confirmed that the ionic compounds that could be removed by washing with water were sufficiently removed. The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated and dried at 90° C. for 1 hour to obtain the target 1-naphthol aralkyl cyanate compound (SN495V-CN, cyanate group (functional base) equivalent weight: 261g/eq.) (orange sticky substance) 331g. The obtained infrared absorption spectrum of SN495V-CN showed the absorption at 2250 cm ^-1 (cyanate group) and did not show the absorption of hydroxyl group.

[Example 1] (Manufacture of Polymer (D1)) In a three-necked flask equipped with a thermometer and a Dimroth condenser, 5.0 parts by mass of diallyl bisphenol A (DABPA (trade name), Daiwa Chemical Industry Co., Ltd.) and biscresol (BCF ( Trade name), Osaka Gas Chemical Co., Ltd.) 5.4 parts by mass, epoxy-modified polysiloxane b1 (X-22-163 (trade name), Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g/mol) 3.7 parts by mass Parts, epoxy-modified polysiloxane b2 (KF-105 (trade name), Shin-Etsu Chemical Co., Ltd., functional group equivalent 490g/mol) 11.0 parts by mass, biphenyl type epoxy resin c1 (YL-6121H (commodity Name), Mitsubishi Chemical Co., Ltd.) 4.9 parts by mass, 30 parts by mass of propylene glycol monomethyl ether acetate (DOWANOL PMA (trade name), Dow Chemical Japan Co., Ltd.) as a solvent, and heated and stirred in an oil bath to 120°C. After confirming that the raw materials are dissolved in the solvent, add 0.3 parts by mass of imidazole catalyst (TBZ (trade name), Shikoku Chemical Industry Co., Ltd.) and raise the temperature to 140°C, stir for 5 hours, and cool to obtain a thermosetting compound containing (D) The solution (50 mass % of solid content) of the polymer (D1).

In addition, diallyl bisphenol A is equivalent to "alkenylphenol A", epoxy-modified silicone b1 and epoxy-modified silicone b2 are equivalent to "epoxy-modified silicone B", biphenyl Type epoxy resin c1 corresponds to "epoxy compound C".

The polymer (D1) contains a constituent unit derived from alkenylphenol A (constituent unit A), a constituent unit derived from epoxy-modified polysiloxane B (constituent unit B), and a constituent unit derived from epoxy compound C (constituent unit C). Content of structural unit B with respect to polymer (D1) was 48.8 mass %. The content of the structural unit C relative to the total amount of the structural unit B and the structural unit C was 25% by mass. The weight average molecular weight (Mw) of the polymer (D1) was 12,000 in terms of polystyrene in the GPC method as a result of measurement by the aforementioned method.

(manufacturing of prepreg) A phenol novolac type cyanate compound (cyanate group (functional group) equivalent: 127 g/eq, Primaset PT-30 (commercial product name), Lonza Japan Co., Ltd.) 14 parts by mass, naphthyl cresol novolac type epoxy resin (epoxy group (functional group) equivalent: 244 g/eq, HP-9540 (trade name), DIC (stock)) 36 parts by mass, novolak-type maleimide compound (maleimide group (functional group) equivalent: 275 g/eq, BMI-2300 (trade name), Daiwa Chemical Industry Co., Ltd.) 15 parts by mass, Laimide compound (maleimide group (functional group) equivalent: 285g/eq, BMI-80 (trade name), K･I Chemical Industry Co., Ltd.) 5 parts by mass, silica silica (SC- 2050MB (trade name), Admatechs (stock)) 140 parts by mass, epoxy silane coupling agent (KBM-403 (trade name), Toray Dow Corning (stock)) 5 parts by mass, and wetting dispersant (DISPERBYK-161 (trade name), BYK Co., Ltd.) 1 part by mass to obtain a varnish (curable composition). The functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) was 0.75. The obtained varnish was dip-coated on S glass fiber (T2116 (trade name), Nittobo Co., Ltd., thickness 100 μm), and heated and dried at 165°C for 5 minutes to obtain the solid content of the curable composition (including the filler) A prepreg with a content of 58.2% by volume.

(Manufacturing of metal foil-clad laminates) The obtained prepregs were laminated in two sheets to form a laminate, and 12 μm thick electrolytic copper foil (3EC-VLP (trade name), manufactured by Mitsui Metal Mining Co., Ltd.), vacuum pressing at 30kgf/cm ² , 230°C, and 100 minutes for lamination forming to obtain the thickness of the insulating layer derived from the laminate It is a 0.2mm metal foil clad laminate (double-sided copper clad laminate).

[Example 2] In the manufacture of the prepreg, 14 parts by mass of the phenol novolak type cyanate compound (PT-30 (trade name)) was replaced by 12 parts by mass, and the naphthylcresol novolak type epoxy resin (HP- 9540 (trade name)) 36 parts by mass were replaced by 38 parts by mass. In the same manner as in Example 1, a prepreg with a solid content (including filler) of the curable composition of 58.2% by volume was obtained. body. In addition, in the varnish (curable composition), the functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) was 0.61. Using the obtained prepreg, it carried out similarly to Example 1, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness derived from the insulating layer of a laminated body was 0.2 mm.

[Example 3] In the manufacture of the prepreg, 10 parts by mass of the phenol novolak type cyanate compound (PT-30 (trade name)) was replaced by 10 parts by mass, and the naphthyl cresol novolak type epoxy resin (HP- 9540 (trade name)) 36 parts by mass were replaced by 40 parts by mass, and in the same manner as in Example 1, a prepreg containing 58.2% by volume of the solid content (including the filler) of the curable composition was obtained. body. In addition, in the varnish (curable composition), the functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) was 0.48. Using the obtained prepreg, it carried out similarly to Example 1, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness derived from the insulating layer of a laminated body was 0.2 mm.

[Example 4] In the manufacture of the prepreg, 14 parts by mass of the phenol novolak type cyanate compound (PT-30 (trade name)) was replaced by the 1-naphthol aralkyl type cyanate compound obtained in Synthesis Example 1 ( Cyanate group (functional group) equivalent: 261g/eq., SN495V-CN) 20 parts by mass, and replace 36 parts by mass of naphthylcresol novolac type epoxy resin (HP-9540 (trade name)) with 30 parts by mass Except that, it carried out similarly to Example 1, and obtained the varnish (curable composition). The functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) was 0.62. The obtained varnish was dip-coated on S glass fiber (T2116 (trade name), Nittobo Co., Ltd., thickness 100 μm), and heated and dried at 155° C. for 5 minutes to obtain the solid content of the curable composition (including the filler) ) content of 58.2% by volume of the prepreg. Using the obtained prepreg, it carried out similarly to Example 1, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness derived from the insulating layer of a laminated body was 0.2 mm.

[Example 5] In the manufacture of the prepreg, 14 parts by mass of the phenol novolak type cyanate compound (PT-30 (trade name)) was replaced by the 1-naphthol aralkyl type cyanate compound obtained in Synthesis Example 1 ( SN495V-CN) 18 mass parts, and 36 mass parts of naphthyl cresol novolak type epoxy resins (HP-9540 (trade name)) are replaced into using 32 mass parts, except that, carry out in the same way as Example 1 , and in the same manner as in Example 1, a varnish (curable composition) was obtained. The functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) was 0.53. The obtained varnish was dip-coated on S glass fiber (T2116 (trade name), Nittobo Co., Ltd., thickness 100 μm), and heated and dried at 155° C. for 5 minutes to obtain the solid content of the curable composition (including the filler) ) content of 58.2% by volume of the prepreg. Using the obtained prepreg, it carried out similarly to Example 1, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness derived from the insulating layer of a laminated body was 0.2 mm.

[Example 6] In the manufacture of the prepreg, 14 parts by mass of the phenol novolak type cyanate compound (PT-30 (trade name)) was replaced by the 1-naphthol aralkyl type cyanate compound obtained in Synthesis Example 1 ( SN495V-CN) 15 mass parts, and 36 mass parts of naphthyl cresol novolac type epoxy resins (HP-9540 (trade name)) are replaced into using 35 mass parts, except that, carry out in the same way as Example 1 , and in the same manner as in Example 1, a varnish (curable composition) was obtained. The functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) was 0.40. The obtained varnish was dip-coated on S glass fiber (T2116 (trade name), Nittobo Co., Ltd., thickness 100 μm), and heated and dried at 155° C. for 5 minutes to obtain the solid content of the curable composition (including the filler) ) content of 58.2% by volume of the prepreg. Using the obtained prepreg, it carried out similarly to Example 1, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness derived from the insulating layer of a laminated body was 0.2 mm.

[Example 7] In the manufacture of the prepreg, 14 parts by mass of the phenol novolak type cyanate compound (PT-30 (trade name)) was replaced by the 1-naphthol aralkyl type cyanate compound obtained in Synthesis Example 1 ( SN495V-CN) 12 mass parts, and 36 mass parts of naphthyl cresol novolac type epoxy resins (HP-9540 (trade name)) are replaced into using 38 mass parts, except that, carry out in the same way as Example 1 , and in the same manner as in Example 1, a varnish (curable composition) was obtained. The functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) was 0.30. The obtained varnish was dip-coated on S glass fiber (T2116 (trade name), Nittobo Co., Ltd., thickness 100 μm), and heated and dried at 155° C. for 5 minutes to obtain the solid content of the curable composition (including the filler) ) content of 58.2% by volume of the prepreg. Using the obtained prepreg, it carried out similarly to Example 1, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness derived from the insulating layer of a laminated body was 0.2 mm.

[Example 8] (Manufacturing of prepregs and metal foil-clad laminates) 16 parts by mass of the 1-naphthol aralkyl type cyanate compound (SN495V-CN) obtained in Synthesis Example 1 was mixed in 30 parts by mass (in terms of solid content) of the solution containing the polymer (D1) obtained in Example 1 , Naphthalene cresol novolak type epoxy resin (HP-9540 (trade name)) 32.5 mass parts, novolac type maleimide compound (BMI-2300 (trade name)) 16 mass parts, maleimide Compound (BMI-80 (trade name)) 5.5 mass parts, slurry silica (SC-2050MB (trade name)) 200 mass parts, epoxy silane coupling agent (KBM-403 (trade name)) 5 mass parts , and 1 part by mass of a wetting and dispersing agent (DISPERBYK-161 (trade name)) to obtain a varnish (curable composition). The functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) was 0.46. The obtained varnish was dip-coated on S glass fiber (T2116 (trade name), Nittobo Co., Ltd., thickness 100 μm), and heated and dried at 155° C. for 5 minutes to obtain the solid content of the curable composition (including the filler) ) content of 58.2% by volume of the prepreg. Using the obtained prepreg, it carried out similarly to Example 1, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness derived from the insulating layer of a laminated body was 0.2 mm.

[Example 9] (Manufacturing of prepregs and metal foil-clad laminates) 15 parts by mass of the 1-naphthol aralkyl type cyanate compound (SN495V-CN) obtained in Synthesis Example 1 was mixed in 30 parts by mass (in terms of solid content) of the solution containing the polymer (D1) obtained in Example 1 , 25 parts by mass of naphthyl cresol novolak type epoxy resin (HP-9540 (trade name)), 22.5 parts by mass of novolak type maleimide compound (BMI-2300 (trade name)), maleimide Compound (BMI-80 (trade name)) 7.5 mass parts, slurry silica (SC-2050MB (trade name)) 140 mass parts, epoxy silane coupling agent (KBM-403 (trade name)) 5 mass parts , and 1 part by mass of a wetting and dispersing agent (DISPERBYK-161 (trade name)) to obtain a varnish (curable composition). The functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) was 0.56. The obtained varnish was dip-coated on S glass fiber (T2116 (trade name), Nittobo Co., Ltd., thickness 100 μm), and heated and dried at 165° C. for 5 minutes to obtain the solid content of the curable composition (including the filler) ) content of 58.2% by volume of the prepreg. Using the obtained prepreg, it carried out similarly to Example 1, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness derived from the insulating layer of a laminated body was 0.2 mm.

[Example 10] (Manufacturing of prepregs and metal foil-clad laminates) 22 parts by mass of the 1-naphthol aralkyl type cyanate compound (SN495V-CN) obtained in Synthesis Example 1 was mixed in 30 parts by mass (in terms of solid content) of the solution containing the polymer (D1) obtained in Example 1 , Naphthalene cresol novolak type epoxy resin (HP-9540 (trade name)) 38 mass parts, novolak type maleimide compound (BMI-2300 (trade name)) 7.5 mass parts, maleimide Compound (BMI-80 (trade name)) 2.5 mass parts, slurry silica (SC-2050MB (trade name)) 140 mass parts, epoxy silane coupling agent (KBM-403 (trade name)) 5 mass parts , and 1 part by mass of a wetting and dispersing agent (DISPERBYK-161 (trade name)) to obtain a varnish (curable composition). The functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) was 0.54. The obtained varnish was dip-coated on S glass fiber (T2116 (trade name), Nittobo Co., Ltd., thickness 100 μm), and heated and dried at 165° C. for 5 minutes to obtain the solid content of the curable composition (including the filler) ) content of 58.2% by volume of the prepreg. Using the obtained prepreg, it carried out similarly to Example 1, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness derived from the insulating layer of a laminated body was 0.2 mm.

[Example 11] (Manufacturing of prepregs and metal foil-clad laminates) 18 parts by mass of the 1-naphthol aralkyl type cyanate compound (SN495V-CN) obtained in Synthesis Example 1 was mixed in 30 parts by mass (in terms of solid content) of the solution containing the polymer (D1) obtained in Example 1 , naphthyl ether type epoxy resin (epoxy group (functional group) equivalent: 250g/eq, HP-6000 (trade name), DIC (stock)) 32 mass parts, novolac type maleimide compound ( BMI-2300 (trade name)) 15 mass parts, maleimide compound (BMI-80 (trade name)) 5 mass parts, slurry silica (SC-2050MB (trade name)) 140 mass parts, ring A varnish (curable composition) was obtained with 5 parts by mass of an oxysilane coupling agent (KBM-403 (trade name)) and 1 part by mass of a wetting and dispersing agent (DISPERBYK-161 (trade name)). The functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) was 0.54. The obtained varnish was dip-coated on S glass fiber (T2116 (trade name), Nittobo Co., Ltd., thickness 100 μm), and heated and dried at 155° C. for 5 minutes to obtain the solid content of the curable composition (including the filler) ) content of 58.2% by volume of the prepreg. Using the obtained prepreg, it carried out similarly to Example 1, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness derived from the insulating layer of a laminated body was 0.2 mm.

[Comparative example 1] In the manufacture of the prepreg, 14 parts by mass of the phenol novolak type cyanate compound (PT-30 (trade name)) was replaced by 18 parts by mass, and the naphthylcresol novolak type epoxy resin (HP- 9540 (trade name)) 36 parts by mass were replaced by 32 parts by mass, and in the same manner as in Example 1, a prepreg with a solid content (including filler) of the curable composition of 58.2% by volume was obtained. body. In addition, in the varnish (curable composition), the functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) was 1.08. Using the obtained prepreg, it carried out similarly to Example 1, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness derived from the insulating layer of a laminated body was 0.2 mm.

[Comparative example 2] In the manufacture of the prepreg, 14 parts by mass of the phenol novolac type cyanate compound (PT-30 (trade name)) was replaced by 5 parts by mass, and the naphthylcresol novolak type epoxy resin (HP- 9540 (trade name)) 36 parts by mass were replaced by 45 parts by mass. In the same manner as in Example 1, a prepreg with a solid content (including filler) of the curable composition of 58.2% by volume was obtained. body. In addition, in the varnish (curable composition), the functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) was 0.21. Using the obtained prepreg, it carried out similarly to Example 1, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness derived from the insulating layer of a laminated body was 0.2 mm.

[Comparative example 3] In the manufacture of the prepreg, 20 parts by mass of the 1-naphthol aralkyl-type cyanate compound (SN495V-CN) obtained in Synthesis Example 1 was replaced by 28 parts by mass, and the naphthol novolak-type ring 30 parts by mass of oxygen resin (HP-9540 (trade name)) was replaced by 22 parts by mass. In addition, it was carried out in the same manner as in Example 4, and the content of the solid content (including the filler) of the curable composition was 58.2 Volume % prepreg. In addition, in the varnish (curable composition), the functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) was 1.19. Using the obtained prepreg, it carried out similarly to Example 4, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness derived from the insulating layer of a laminated body was 0.2 mm.

[Comparative example 4] In the manufacture of the prepreg, 20 parts by mass of the 1-naphthol aralkyl-type cyanate compound (SN495V-CN) obtained in Synthesis Example 1 was replaced by 10 parts by mass, and the naphthol novolak-type ring 30 parts by mass of oxygen resin (HP-9540 (trade name)) was replaced by 40 parts by mass, except that, it was carried out in the same manner as in Example 4, and the content of the solid content (including the filler) of the curable composition was 58.2 Volume % prepreg. In addition, in the varnish (curable composition), the functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) was 0.23. Using the obtained prepreg, it carried out similarly to Example 4, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness derived from the insulating layer of a laminated body was 0.2 mm.

[Comparative Example 5] (Manufacturing of prepregs and metal foil-clad laminates) 26 parts by mass of the 1-naphthol aralkyl type cyanate compound (SN495V-CN) obtained in Synthesis Example 1 was mixed in 30 parts by mass (in terms of solid content) of the solution containing the polymer (D1) obtained in Example 1 , naphthyl ether type epoxy resin (HP-6000 (trade name)) 27 mass parts, novolak type maleimide compound (BMI-2300 (trade name)) 17 mass parts, slurry silica ( SC-2050MB (trade name)) 140 mass parts, epoxy silane coupling agent (KBM-403 (trade name)) 5 mass parts, and wetting dispersant (DISPERBYK-161 (trade name)) 1 mass part, obtain varnish (hardening composition). The functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) was 0.92. The obtained varnish was dip-coated on S glass fiber (T2116 (trade name), Nittobo Co., Ltd., thickness 100 μm), and heated and dried at 165° C. for 5 minutes to obtain the solid content of the curable composition (including the filler) ) content of 58.2% by volume of the prepreg. Using the obtained prepreg, it carried out similarly to Example 1, and obtained the metal foil clad laminated board (double-sided copper clad laminated board) whose thickness derived from the insulating layer of a laminated body was 0.2 mm.

[evaluate] Using the metal foil-clad laminates obtained in Examples and Comparative Examples, the coefficient of thermal expansion, heat resistance, and copper foil peel strength were evaluated by the following methods. The results are shown in Tables 1 and 2.

(coefficient of thermal expansion (CTE)) The coefficient of linear thermal expansion was determined for the insulating layer from the laminate in the metal foil-clad laminate. Specifically, after cutting the obtained metal foil-clad laminate into a size of 6mm×10mm×0.22mm with a dicing saw, the copper foil on both sides was removed by etching, and then heated in a constant temperature bath at 220°C for 2 hours to remove Stresses caused by forming. Thereafter, using a thermal dilatometer (L75H horizontal dilatometer manufactured by LINSEIS Co., Ltd.), the temperature was raised from 40°C to 320°C at 10°C per minute, and the linear coefficient of thermal expansion (CTE) (ppm/ ℃).

(Heat Resistance: Glass Transition Temperature (Tg)) The obtained metal foil-clad laminate was cut into a size of 5mm×100mm×0.22mm with a dicing saw, and the copper foil on the surface was removed by etching to obtain 3 samples for measurement. Using these measurement samples, according to JIS C6481, using a dynamic viscoelasticity analyzer (manufactured by TA Instruments), using the DMA method, under the conditions of a measurement start temperature of 20°C, an end temperature of 500°C, and a temperature increase rate of 10°C/min, in nitrogen gas Measure the mass in the environment, and measure the temperature at which the mass loss rate reaches 5%. The average value was calculated|required from the measured value in 3 samples, and this average value was defined as a glass transition temperature (Tg, degreeC).

(Copper foil peel strength (copper foil adhesion)) Using the obtained metal foil-clad laminate (10 mm×150 mm×0.22 mm), the metal foil peel strength (copper foil adhesion, kgf/cm) was measured in accordance with JIS C6481.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 hardening composition Functional group equivalent ratio 0.75 0.61 0.48 0.62 0.53 0.40 0.30 0.46 0.56 0.54 0.54 Evaluation results Coefficient of thermal expansion (ppm/℃) 6.2 6.2 5.8 6.3 6.2 6.0 5.6 5.7 6.0 6.2 6.1 Heat resistance (℃) 272 271 268 276 269 255 237 270 254 265 295 Copper foil peel strength (kgf/cm) 0.73 0.69 0.64 0.89 0.84 0.76 0.65 0.88 0.64 0.66 0.82

[Table 2] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 hardening composition Functional group equivalent ratio 1.08 0.21 1.19 0.23 0.92 Evaluation results Coefficient of thermal expansion (ppm/℃) 6.6 5.3 6.4 5.3 6.5 Heat resistance (℃) 273 231 285 217 295 Copper foil peel strength (kgf/cm) 0.85 0.32 0.94 0.47 0.75

This application is based on the Japanese patent application (Japanese Patent Application No. 2021-128816) filed on August 5, 2021, and the contents thereof are incorporated herein by reference. [industrial availability]

The curable composition of the present invention simultaneously achieves low thermal expansion, heat resistance (high glass transition temperature), and high peel strength (copper foil adhesion). Therefore, the curable composition of the present invention can be ideally used as, for example, cured products, prepregs, film-like underfill materials, resin sheets, laminates, build-up materials, metal foil-clad laminates, printed wiring boards, and The raw material of fiber-reinforced composite materials may be ideally used in the manufacture of semiconductor devices.

Claims (22)

A sclerosing composition comprising: A thermosetting compound (D) comprising at least a constituent unit derived from alkenylphenol (A), a constituent unit derived from epoxy-modified polysiloxane (B), and a constituent unit derived from epoxy-modified polysiloxane (B) The structural unit of the epoxy compound (C), epoxy resin (E), and Cyanate compound (F); The epoxy resin (E) is different from the epoxy-modified polysiloxane (B), and can be the same or different from the epoxy compound (C), The functional group equivalent ratio of the cyanate compound (F) to the epoxy resin (E) (the equivalent of the cyanate group of the cyanate compound (F)/the equivalent of the epoxy group of the epoxy resin (E)) It is 0.25~0.85. The curable composition according to claim 1, wherein the thermosetting compound (D) is at least the alkenylphenol (A), the epoxy-modified polysiloxane (B), and the epoxy-modified polysiloxane A polymer (D1) obtained by polymerizing the epoxy compound (C) other than the silicone (B). The curable composition according to claim 1 or 2, wherein the alkenyl phenol (A) includes diallyl bisphenol and/or diallyl bisphenol. The curable composition according to claim 1 or 2, wherein the epoxy-modified polysiloxane (B) includes epoxy-modified polysiloxane having an epoxy equivalent of 140-250 g/mol. The curable composition according to claim 1 or 2, wherein the epoxy-modified polysiloxane (B) comprises epoxy-modified polysiloxane represented by the following formula (1);

(1) In formula (1), R ¹ each independently represent a single bond, alkylene, aryl, or aralkylene, R ² each independently represent an alkyl or phenyl group with 1 to 10 carbon atoms, n Represents an integer from 0 to 100. The curable composition according to claim 1 or 2, wherein the epoxy compound (C) comprises a compound represented by the following formula (b2);

In formula (b2), R ^a each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom. The curable composition according to claim 1 or 2, wherein the weight average molecular weight of the thermosetting compound (D) is 3.0×10 ³ to 5.0×10 ⁴ . The curable composition according to claim 1 or 2, wherein the epoxy resin (E) contains at least 1 selected from the group consisting of naphthylcresol novolac epoxy resins and naphthyl ether epoxy resins. kind. The curable composition according to claim 1 or 2, wherein the cyanate compound (F) includes the compound represented by the following formula (4) and/or the following formula (5) other than the compound represented by the following formula (4) the indicated compound;

In formula (4), R ₆ each independently represent a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more;

In formula (5), R _ya each independently represents an alkenyl group having 2 to 8 carbon atoms, or a hydrogen atom, R _yb each independently represents an alkyl group having 1 to 10 carbon atoms, or a hydrogen atom, and R _yc each independently represents An aromatic ring with 4~12 carbons, R _yc can also form a condensed structure with a benzene ring, R _yc may or may not exist, A ^1a each independently represent an alkylene group with 1~6 carbons, an alkylene group with 7~16 carbons Aralkylene group, arylylene group with 6-10 carbon atoms, terylene group, sulfonyl group, oxygen atom, sulfur atom, or single bond, when R _yc does not exist, there may be two or more in one benzene ring The base of R _ya and/or R _yb , n represents an integer of 1-20. The curable composition according to claim 1 or 2, wherein the content of the thermosetting compound (D) is relative to the thermosetting compound (D), the epoxy resin (E) and the cyanate compound ( The total of 100 parts by mass of F) is 25 to 50 parts by mass. The curable composition according to claim 1 or 2, wherein the total content of the epoxy resin (E) and the cyanate compound (F) is higher than that of the thermosetting compound (D) and the epoxy resin ( The total of 100 parts by mass of E) and the cyanate compound (F) is 50 to 75 parts by mass. The curable composition according to claim 1 or 2, wherein the content of the thermosetting compound (D) is relative to the thermosetting compound (D), the epoxy resin (E) and the cyanate compound ( The total of 100 parts by mass of F) is 25 to 50 parts by mass, and The total content of the epoxy resin (E) and the cyanate compound (F) is 100% of the total of the thermosetting compound (D), the epoxy resin (E) and the cyanate compound (F) Parts by mass are 50 to 75 parts by mass. The curable composition according to claim 1 or 2, wherein the total content of the thermosetting compound (D), the epoxy resin (E) and the cyanate compound (F) is higher than the total content of the cyanate compound (F) in the resin composition 100 mass parts of resin solid content is 50-99 mass parts. The curable composition of claim 1 or 2 further contains a maleimide compound. The curable composition of claim 14, wherein the maleimide compound comprises bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimide) Iminophenoxy)phenyl)propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, maleimide represented by the following formula (3) Compound, and at least one of the group consisting of a maleimide compound represented by the following formula (3');

In formula (3), R ₅ each independently represent a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 to 100;

In the formula (3′), R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n4 represents an integer of 1 to 10. The curable composition according to claim 14, wherein, the content of the maleimide compound, relative to the thermosetting compound (D), the epoxy resin (E) and the cyanate compound (F) A total of 100 parts by mass is 5 to 45 parts by mass. The curable composition of claim 1 or 2 further contains an inorganic filler. The curable composition according to claim 17, wherein the content of the inorganic filler is 100% by mass of the total of the thermosetting compound (D), the epoxy resin (E) and the cyanate compound (F) Parts are 50 to 350 parts by mass. The curable composition according to claim 17, wherein the inorganic filler is selected from silicon dioxide, aluminum hydroxide, aluminum oxide, boehmite, boron nitride, aluminum nitride, titanium oxide, titanic acid At least one selected from the group consisting of barium, magnesium oxide, and magnesium hydroxide. A prepreg comprising: base material, and The curable composition according to any one of claims 1 to 19 impregnated or coated on the substrate. A metal foil-clad laminate comprising: A laminate formed using the prepreg according to claim 20, and Metal foil disposed on one or both sides of the laminate. A printed wiring board having: insulation, and A conductor layer formed on one or both sides of the insulating layer; The insulating layer contains a cured product of the curable composition according to any one of claims 1 to 19.