KR20230174283A - Curable compositions, prepregs, metal foil-clad laminates and printed wiring boards - Google Patents

Abstract

A curable composition containing an alkenylphenol, an epoxy-modified silicone, an epoxy compound other than the epoxy-modified silicone, and a cyclic carbodiimide compound.

Description

Curable compositions, prepregs, metal foil-clad laminates and printed wiring boards

The present invention relates to curable compositions, prepregs, metal foil-clad laminates, and printed wiring boards.

Recently, as semiconductor packages, which are widely used in electronic devices, communication devices, personal computers, etc., have become more functional and miniaturized, the integration and high-density mounting of each component for the semiconductor package have been accelerating in recent years. In line with this, the characteristics required for printed wiring boards for semiconductor packages are becoming increasingly stringent. Characteristics required for such a printed wiring board include, for example, low thermal expansion coefficient, chemical resistance, and peeling strength.

Patent Document 1 states that a thermosetting resin composition containing a specific maleimide compound, a silicone compound having an epoxy group in the molecular structure, and a compound having a phenolic hydroxyl group is excellent in heat resistance and low thermal expansion, and is used in metal foil-clad laminates and multilayer printed wiring boards. It is disclosed that it is preferably used.

Patent Document 2 discloses polymaleimide, an addition polymer of diglycidylpolysiloxane represented by the following formula (I), diallyl bisphenol represented by the following formula (II), and an allylated phenol represented by the following formula (III). A manufacturing method for obtaining a resin for semiconductor encapsulation by reacting a resin at a predetermined ratio and conditions is disclosed. According to this document, the resin for semiconductor encapsulation obtained by the above production method has good compatibility between polymaleimide and the above addition polymer, and further has the properties of a cured product of a composition using the resin for semiconductor encapsulation (e.g. For example, it is disclosed that it is excellent in high glass transition temperature, moisture resistance, and heat strength) and is highly reliable as a resin composition for semiconductor encapsulation. This document discloses that the b component in the following formula (III) is an important component that reacts with maleimide groups in the resin production reaction with polymaleimide and improves the compatibility between polymaleimide and polysiloxane.

[Formula 1]

(In the formula, R ¹ represents an alkylene group or a phenylene group, R ² each independently represents an alkyl group or a phenyl group, and n represents an integer of 1 to 100.)

[Formula 2]

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

[Formula 3]

(In the above formula, a, b, and c each represent the percentage of each composition, and 0 < a, b, c < 100 and a + b + c = 100)

Japanese Patent Publication No. 2012-149154 Japanese Patent Publication No. 4-4213

As in Patent Document 1, a resin composition containing a silicone compound having an epoxy group in its molecular structure and a thermosetting resin such as a maleimide compound is excellent in low thermal expansion property. However, the present inventors found that the resin composition had a problem with moldability due to insufficient compatibility between the silicone compound and the thermosetting resin. Additionally, the present inventors found that the chemical resistance and metal foil peel strength (for example, copper foil peel strength) when used as a metal foil-clad laminate were not sufficient for the resin composition.

On the other hand, the resin composition described in Patent Document 2 is used for semiconductor encapsulation, and the low thermal expansion property, copper foil peel strength, and chemical resistance required as characteristics of a printed wiring board have not been examined.

The present invention was made in view of the above problems, and its purpose is to provide a curable composition, prepreg, metal foil-clad laminate, and printed wiring board having excellent low thermal expansion properties, copper foil peel strength, and chemical resistance.

The present inventors have conducted intensive studies to solve the above problems. As a result, a curable composition containing an alkenylphenol, an epoxy-modified silicone, an epoxy compound other than the epoxy-modified silicone, and a cyclic carbodiimide compound, or a structural unit derived from an alkenylphenol, and an epoxy-modified silicone It was found that the above-mentioned problems can be solved by a curable composition containing a structural unit derived from an epoxy compound other than the epoxy-modified silicone, a polymer containing a structural unit derived from an epoxy compound other than the epoxy-modified silicone, and a cyclic carbodiimide compound, and the present invention has reached completion.

That is, the present invention is as follows.

[One]

A curable composition containing alkenylphenol (A), epoxy modified silicone (B), an epoxy compound (C) other than the epoxy modified silicone (B), and a cyclic carbodiimide compound (D).

[2]

The cyclic carbodiimide compound (D) has a cyclic structure represented by the following formula (D1),

The curable composition according to [1], wherein the number of atoms forming the cyclic structure is 8 to 50.

[Formula 4]

(In the formula, L is a divalent to tetravalent bonding group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and the bonding group may contain a heteroatom and/or a substituent)

[3]

The curable composition according to [1] or [2], wherein the content of the cyclic carbodiimide compound (D) is 2.0 to 15 parts by mass based on 100 parts by mass of the resin solid content.

[4]

The average number of phenol groups per molecule of the alkenylphenol (A) is 1 to 3, the average number of epoxy groups per molecule of the epoxy modified silicone (B) is 1 to 3, and one molecule of the epoxy compound (C) The curable composition according to any one of [1] to [3], wherein the average number of epoxy groups per group is 1 or more and less than 3.

[5]

The curable composition according to any one of [1] to [4], wherein the alkenylphenol (A) contains diallylbisphenol and/or dipropenylbisphenol.

[6]

The curable composition according to any one of [1] to [5], wherein the epoxy modified silicone (B) contains an epoxy modified silicone having an epoxy equivalent of 140 to 250 g/mol.

[7]

The curable composition according to any one of [1] to [6], wherein the epoxy modified silicone (B) contains epoxy modified silicone represented by the following formula (B1).

[Formula 5]

(In the formula, R ¹ each independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, R ² each independently represents an alkyl group or phenyl group having 1 to 10 carbon atoms, and n is 0. represents an integer from ∼ 100)

[8]

The curable composition according to any one of [1] to [7], wherein the epoxy compound (C) contains a compound represented by the following formula (b2).

[Formula 6]

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

[9]

A polymer containing a structural unit derived from alkenylphenol (A), a structural unit derived from epoxy modified silicone (B), and a structural unit derived from an epoxy compound (C) other than the epoxy modified silicone (B) ( E) Wow,

A curable composition containing a cyclic carbodiimide compound (D).

[10]

The curable composition according to [9], wherein the weight average molecular weight of the polymer (E) is 3.0 × 10 ³ to 5.0 × 10 ⁴ .

[11]

The curable composition according to [9] or [10], wherein the content of the polymer (E) is 5 to 50% by mass based on 100% by mass of the resin solid content.

[12]

The cyclic carbodiimide compound (D) has a cyclic structure represented by the following formula (D1),

The curable composition according to any one of [9] to [11], wherein the number of atoms forming the cyclic structure is 8 to 50.

[Formula 7]

(In the formula, L is a divalent to tetravalent bonding group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and the bonding group may contain a heteroatom and/or a substituent)

[13]

The curable composition according to any one of [9] to [12], wherein the content of the cyclic carbodiimide compound (D) is 2.0 to 15 parts by mass based on 100 parts by mass of the resin solid content.

[14]

The average number of phenol groups per molecule of the alkenylphenol (A) is 1 to 3, the average number of epoxy groups per molecule of the epoxy modified silicone (B) is 1 to 3, and one molecule of the epoxy compound (C) The curable composition according to any one of [9] to [13], wherein the average number of epoxy groups per group is 1 or more and less than 3.

[15]

The curable composition according to any one of [9] to [14], wherein the alkenylphenol (A) contains diallylbisphenol and/or dipropenylbisphenol.

[16]

The curable composition according to any one of [9] to [15], wherein the epoxy modified silicone (B) contains an epoxy modified silicone having an epoxy equivalent of 140 to 250 g/mol.

[17]

The curable composition according to any one of [9] to [16], wherein the epoxy modified silicone (B) contains epoxy modified silicone represented by the following formula (B1).

[Formula 8]

(In the formula, R ¹ each independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, R ² each independently represents an alkyl group or phenyl group having 1 to 10 carbon atoms, and n is 0. represents an integer from ∼ 100)

[18]

The curable composition according to any one of [9] to [17], wherein the epoxy compound (C) contains a compound represented by the following formula (b2).

[Formula 9]

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

[19]

[9] to [18], which further contains at least one member selected from the group consisting of alkenylphenol (A), epoxy-modified silicone (B), and epoxy compounds (C) other than the epoxy-modified silicone (B). The curable composition according to any one of the above.

[20]

The curable composition according to [19], wherein the epoxy compound (C) contains a naphthalenecresol novolak-type epoxy resin and/or a naphthylene ether-type epoxy resin.

[21]

[ The curable composition according to any one of 1] to [20].

[22]

additionally containing inorganic fillers,

The curable composition according to any one of [1] to [20], wherein the inorganic filler contains at least one selected from the group consisting of silica, boehmite, and alumina.

[23]

With equipment,

A prepreg comprising the curable composition according to any one of [1] to [22], impregnated or applied to the substrate.

[24]

[23] A laminate containing the prepreg described in,

A metal foil-clad laminate comprising metal foil disposed on one or both sides of the laminate.

[25]

An insulating layer containing the prepreg described in [23],

A printed wiring board including a conductor layer formed on the surface of the insulating layer.

According to the present invention, it is possible to provide a curable composition, prepreg, metal foil-clad laminate, and printed wiring board having excellent low thermal expansion properties, copper foil peel strength, and chemical resistance.

Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “this embodiment”) will be described in detail, but the present invention is not limited to this, and various modifications are possible without departing from the gist. .

As used herein, unless otherwise specified, “resin solid content” refers to components excluding solvents and fillers in the curable composition of the present embodiment, and 100 parts by mass of resin solid content refers to components excluding solvents and fillers in the curable composition. It means that the total of components is 100 parts by mass. In addition, the resin solid content of 100% by mass means that the total of the components in the curable composition excluding the solvent and filler is 100% by mass.

“Compatibility” as used in this specification refers to the following. In the composition of the first embodiment, which will be described in detail later, “excellent compatibility” means alkenylphenol (A), epoxy modified silicone (B), epoxy compound (C), and cyclic carbodiimide compound ( D) In a mixture containing (e.g., varnish), liquid phase separation does not occur. In addition, in the composition of the second embodiment, which will be described in detail later, “excellent compatibility” refers to a mixture (for example, a varnish) containing a polymer (E) and a cyclic carbodiimide compound (D), This means that liquid phase separation does not occur. Because the curable composition of the present embodiment has excellent compatibility, liquid phase separation during the molding process is suppressed, and a molded body with excellent appearance can be obtained. In addition, the obtained molded body tends to have excellent isotropy in physical properties. . In addition, in this specification, when referring to “the curable composition of the present embodiment”, unless otherwise specified, both “the curable composition of the first embodiment” and “the curable composition of the second embodiment” are included. do.

<First embodiment>

[Curable composition of the first embodiment]

The curable composition of the first embodiment includes alkenylphenol (A), epoxy modified silicone (B), and an epoxy compound (C) other than the epoxy modified silicone (B) (hereinafter simply referred to as “epoxy compound (C)”. (also called) and a cyclic carbodiimide compound (D). The curable composition of the first embodiment containing these components has excellent low thermal expansion properties, copper foil peel strength, and chemical resistance. The factors that improve each characteristic are thought to be as follows, but the factors are not limited to these. Since the cyclic carbodiimide compound (D) has a high melting point, for example, at the temperature (about 140°C) during prepreg production, alkenylphenol (A), epoxy modified silicone (B), and epoxy compound Reactivity with each thermosetting resin such as (C) is low, and thus, deterioration of the flow characteristics of the curable composition is suppressed. Then, during press molding at a higher temperature, the cyclic carbodiimide compound (D) is melted, and thermosetting resins such as alkenylphenol (A), epoxy modified silicone (B), and epoxy compound (C) and the cyclic carbodiimide compound (D) are melted. When the type carbodiimide compound (D) reacts, a structure with a higher crosslink density is formed, and thus low thermal expansion property, copper foil peel strength, and chemical resistance are improved.

[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. The curable composition of the present embodiment can exhibit excellent compatibility by containing alkenylphenol (A), thereby improving the balance between heat resistance and low thermal expansion.

The alkenyl group is not particularly limited, but examples include alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl. Among them, from the viewpoint of more effectively and reliably exhibiting the effects of the present invention, the alkenyl group is preferably an allyl group and/or a propenyl group, and more preferably an allyl group. The number of alkenyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 4. From the viewpoint of more effectively and reliably exhibiting the effects of the present invention, the number of alkenyl groups directly bonded to one phenolic aromatic ring is preferably 1 to 2, and more preferably 1. Additionally, the bonding position of the alkenyl group to the phenolic aromatic ring is not particularly limited, but is preferably the ortho position (2, 6 positions).

A phenolic aromatic ring refers to one in which one or more hydroxyl groups are directly bonded to an aromatic ring, and examples include a phenol ring and a naphthol ring. The number of hydroxyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 2, and is preferably 1.

The phenolic aromatic ring may have a substituent other than the alkenyl group. Such substituents include, for example, a linear alkyl group with 1 to 10 carbon atoms, a branched alkyl group with 3 to 10 carbon atoms, a cyclic alkyl group with 3 to 10 carbon atoms, a linear alkoxy group with 1 to 10 carbon atoms, and a C3 group. Examples include a branched alkoxy group having from 10 to 10 carbon atoms, a cyclic alkoxy group having from 3 to 10 carbon atoms, and a halogen atom. When the phenolic aromatic ring has a substituent other than an alkenyl group, the number of the substituents directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 2. Additionally, the bonding position of the substituent 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 a phenolic aromatic ring. From the viewpoint of more effectively and reliably exhibiting the effects of the present invention, the alkenylphenol (A) preferably has one or two structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring, It is desirable to have two.

The alkenylphenol (A) may be, for example, a compound represented by the following formula (A1) or the following formula (A2).

[Formula 10]

(Wherein, Rxa each independently represents an alkenyl group having 2 to 8 carbon atoms, Rxb each independently represents an alkyl group or hydrogen atom having 1 to 10 carbon atoms, and Rxc each independently represents an alkenyl group having 4 to 8 carbon atoms. Represents a 12-membered aromatic ring, Rxc may form a condensed structure with a benzene ring, Rxc may or may not be present, and A is an alkylene group having 1 to 6 carbon atoms, or an alkylene group having 7 to 16 carbon atoms. represents an aralkylene group, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, a sulfur atom, or a direct bond (single bond), and when Rxc does not exist, Rxa and /or you may have 2 or more Rxb groups)

[Formula 11]

(Wherein, Rxd each independently represents an alkenyl group having 2 to 8 carbon atoms, Rxe each independently represents an alkyl group or a hydrogen atom having 1 to 10 carbon atoms, and Rxf is an aromatic ring having 4 to 12 carbon atoms. , Rxf may form a condensed structure with a benzene ring, Rxf may or may not exist, and if Rxf does not exist, the groups Rxd and/or Rxe may be attached to one benzene ring. You can have more than 2)

In formulas (A1) and (A2), the alkenyl group having 2 to 8 carbon atoms represented by Rxa and Rxd is not particularly limited, and examples include vinyl group, allyl group, propenyl group, butenyl group, and hexenyl group. etc. can be mentioned.

In Formula (A1) and Formula (A2), when the groups represented by Rxc and Rxf form a condensed structure with a benzene ring, for example, a compound containing a naphthol ring as a phenolic aromatic ring can be mentioned. . Moreover, in Formula (A1) and Formula (A2), examples of cases in which the groups represented by Rxc and Rxf do not exist include compounds containing a phenol ring as the phenolic aromatic ring.

In Formula (A1) and Formula (A2), the alkyl group having 1 to 10 carbon atoms represented by Rxb and Rxe is not particularly limited, and examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, etc. Examples include branched alkyl groups such as straight-chain alkyl groups, isopropyl groups, isobutyl groups, and tert-butyl groups.

In formula (A1), the alkylene group having 1 to 6 carbon atoms represented by A is not particularly limited, and examples include methylene group, ethylene group, trimethylene group, and propylene group. The aralkylene group having 7 to 16 carbon atoms represented by A is not particularly limited, but examples include formulas: -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 a phenylene group, a naphthylene group, or a biphenylene group). The arylene group having 6 to 10 carbon atoms represented by A is not particularly limited, and examples include a phenylene ring.

The compound represented by formula (A2) is preferably one in which Rxf is a benzene ring (a compound containing a dihydroxynaphthalene skeleton) from the viewpoint of more effectively and reliably exhibiting the effects of the present invention.

From the viewpoint of further improving compatibility, the alkenylphenol (A) is preferably an alkenylbisphenol in which one alkenyl group is bonded to two phenolic aromatic rings of bisphenol. From the same point of view, alkenylbisphenol is diallylbisphenol, in which one allyl group is bonded to each of two phenolic aromatic rings of bisphenols, and/or diphenyl bisphenol, in which one propenyl group is bonded to each of two phenolic aromatic rings of bisphenols. Lophenylbisphenol is preferred.

Diallylbisphenol is not particularly limited and includes, for example, o,o'-diallylbisphenol A ("DABPA" manufactured by Daiwa Chemical Industry Co., Ltd.), o,o'-diallylbisphenol F, o,o' -Diallylbisphenol S, o,o'-diallylbisphenol fluorene can be mentioned. Dipropenylbisphenol is not particularly limited and includes, for example, o,o'-dipropenylbisphenol A ("PBA01" from Gunei Chemical Industry Co., Ltd.), o,o'-dipropenylbisphenol F, o ,o'-dipropenylbisphenol S, o,o'-dipropenylbisphenol fluorene.

The average number of phenol groups per molecule of alkenylphenol (A) is preferably 1 to 3, more preferably 1.5 to 2.5, from the viewpoint of more effectively and reliably exhibiting the effects of the present invention. The average number of phenol groups is calculated by the following formula.

In the formula, Ai represents the number of phenol groups of the alkenylphenol having i phenol groups in the molecule, Xi represents the proportion of alkenylphenol having i phenol groups in the molecule to all alkenylphenols, _{and 2} + … X _n = 1.

[Epoxy modified silicone (B)]

The epoxy-modified silicone (B) is not particularly limited as long as it is a silicone compound or resin modified with an epoxy group-containing group. The curable composition of the present embodiment is excellent in low thermal expansion and chemical resistance by containing epoxy-modified silicone (B).

The silicone compound or resin is not particularly limited as long as it is a compound having a polysiloxane skeleton in which siloxane bonds are formed repeatedly. The polysiloxane skeleton may be a linear skeleton, a cyclic skeleton, or a mesh-like skeleton. Among these, a linear skeleton is preferable from the viewpoint of more effectively and reliably exhibiting the effects of the present invention.

The epoxy group-containing group is not particularly limited, but examples include groups represented by the following formula (a1).

[Formula 12]

(In the formula, R ⁰ represents an alkylene group (for example, an alkylene group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, a propylene group, etc.), and (represents a monovalent group represented by the following formula (a3))

[Formula 13]

[Formula 14]

The epoxy-modified silicone (B) preferably contains epoxy-modified silicone with an epoxy equivalent of 140 to 250 g/mol. The epoxy-modified silicone (B) contains an epoxy-modified silicone having an epoxy equivalent within the above range, so that it has further excellent compatibility and tends to be able to further improve low thermal expansion and chemical resistance with a good balance. there is. From the same viewpoint, the epoxy equivalent is more preferably 145 to 245 g/mol, and even more preferably 150 to 240 g/mol.

The epoxy-modified silicone (B) preferably contains two or more types of epoxy-modified silicone from the viewpoint of having even better compatibility with thermosetting resins and being able to further improve low thermal expansion and chemical resistance with a good balance. do. In this case, it is preferable that the two or more types of epoxy-modified silicone each have a different epoxy equivalent weight, and an epoxy-modified silicone having an epoxy equivalent weight of 50 to 350 g/mol (hereinafter also referred to as “low-equivalent epoxy-modified silicone (B1')”. It is more preferable to contain epoxy-modified silicone (hereinafter also referred to as “high-equivalent epoxy-modified silicone (B2')”) having an epoxy equivalent of 400 to 4000 g/mol, and 140 to 250 g/mol. Containing an epoxy modified silicone having an epoxy equivalent weight (low equivalent weight epoxy modified silicone (B1'')) and an epoxy modified silicone having an epoxy equivalent weight of 450 to 3000 g/mol (high equivalent weight epoxy modified silicone (B2'')). It is more desirable.

When the epoxy modified silicone (B) contains two or more types of epoxy modified silicone, the average epoxy equivalent weight of the epoxy modified silicone (B) is preferably 140 to 3000 g/mol, more preferably 250 to 2000 g/mol. It is preferable, and it is more preferable that it is 300 to 1000 g/mol. The average epoxy equivalent is calculated by the following formula.

(Wherein, Ei represents the epoxy equivalent of one type of epoxy-modified silicone among two or more types of epoxy-modified silicone, Wi represents the ratio of the epoxy-modified silicone in epoxy-modified silicone (B), W ₁ + W ₂ ＋ … W _n = 1)

The epoxy-modified silicone (B) preferably contains epoxy-modified silicone represented by the following formula (B1) from the viewpoint of having further excellent compatibility and being able to further improve low thermal expansion and chemical resistance with a good balance. .

[Formula 15]

(In the formula, R ¹ each independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, R ² each independently represents an alkyl group or phenyl group having 1 to 10 carbon atoms, and n is 0. represents an integer from ∼ 100)

In formula (B1), the alkylene group represented by R ¹ may be linear, branched, or cyclic. The carbon number of the alkylene group is preferably 1 to 12, and more preferably 1 to 4. Examples of the alkylene group include methylene group, ethylene group, or propylene group. Among these, it is preferable that R ¹ is a propylene group.

In formula (B1), the arylene group represented by R ¹ may have a substituent. The number of carbon atoms of the arylene group is preferably 6 to 40, and more preferably 6 to 20. Arylene groups include, for example, phenylene group, cyclohexylphenylene group, hydroxyphenylene group, cyanophenylene group, nitrophenylene group, naphthylylene group, biphenylene group, anthrylene group, pyrenylene group, and fluorenyl. Rengi, etc. can be mentioned. These groups may contain an ether bond, a ketone bond, or an ester bond.

In formula (B1), the carbon number of the aralkylene group represented by R ¹ is preferably 7 to 30, more preferably 7 to 13. The aralkylene group is not particularly limited, but examples include groups represented by the following formula (XI).

[Formula 16]

(In formula (X-I), * represents a bond)

In formula (B1), the group represented by R ¹ may further have a substituent, and examples of the substituent include a straight-chain alkyl group with 1 to 10 carbon atoms, a branched alkyl group with 3 to 10 carbon atoms, and a C3 to 10 carbon alkyl group. Examples include a cyclic alkyl group of 10 carbon atoms, a straight-chain alkoxy group of 1 to 10 carbon atoms, a branched alkoxy group of 3 to 10 carbon atoms, and a cyclic alkoxy group of 3 to 10 carbon atoms. Among these, it is especially preferable that R ¹ is a propylene group.

In formula (B1), R ² each independently represents an alkyl group or phenyl group having 1 to 10 carbon atoms. The alkyl group and phenyl group may have a substituent. The alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic. The alkyl group is not particularly limited, and examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, and cyclohexyl group. Among these, R ² is preferably a methyl group or a phenyl group.

In formula (B1), n represents an integer of 0 or more, for example, 1 to 100. From the viewpoint of having further excellent compatibility and being able to further improve low thermal expansion and chemical resistance with a good balance, n is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less. am.

Epoxy-modified silicone (B) has further excellent compatibility with thermosetting resins, and from the viewpoint of further improving low thermal expansion and chemical resistance with a good balance, two or more types of epoxy-modified silicone represented by formula (B1) are used. It is desirable to contain it. In this case, it is preferable that two or more types of epoxy-modified silicones contained therein each have different n, and that n is 1 to 2 in the formula (B1) and epoxy-modified silicone in which n is 5 to 20 in the formula (B1). It is more preferable to contain phosphorus epoxy modified silicone.

The average number of epoxy groups per molecule of the epoxy-modified silicone (B) is preferably 1 to 3, and more preferably 1.5 to 2.5, from the viewpoint of more effectively and reliably exhibiting the effects of the present invention. The average epoxy group number is calculated by the following formula.

(In the formula, Bi represents the epoxy group number of the epoxy-modified silicone having i epoxy groups in the molecule, Yi represents the ratio of the epoxy-modified silicone having i epoxy groups in the molecule to the entire epoxy-modified silicon, and Y ₁ + Y ₂ + … Y _n = 1)

The content of epoxy-modified silicone (B) is 5 to 95 mass% with respect to a total of 100 mass% of epoxy-modified silicone (B) and epoxy compound (C) from the viewpoint of being able to exhibit even more excellent low thermal expansion and chemical resistance. It is preferably %, more preferably 10 to 90 mass%, more preferably 40 to 85 mass%, and even more preferably 50 to 80 mass%.

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

[Epoxy compound (C)]

The epoxy compound (C) is an epoxy compound other than epoxy modified silicone (B), and more specifically, it is an epoxy compound that does not have a polysiloxane skeleton. The curable composition of the present embodiment can exhibit better compatibility, heat resistance, chemical resistance, copper foil peel strength, and insulation reliability by containing the epoxy compound (C).

The epoxy compound (C) is not particularly limited as long as it is an epoxy compound other than epoxy modified silicone (B). As the epoxy compound (C) in the curable composition of the present embodiment, typically a bifunctional epoxy compound having two epoxy groups in one molecule or a polyfunctional epoxy compound having three or more epoxy groups in one molecule can be used. . The epoxy compound (C) preferably contains a bifunctional epoxy compound and/or a polyfunctional epoxy compound from the viewpoint of being able to exhibit further excellent compatibility, heat resistance, chemical resistance, copper foil peeling strength, and insulation reliability.

The epoxy compound (C) in the curable composition of the present embodiment is not particularly limited, but a compound represented by the following formula (3a) can be used.

[Formula 17]

(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, and R ^3a each independently represents a hydrogen atom or Represents a methyl group, k represents an integer from 1 to 50,

Here, the benzene ring or naphthalene ring in Ar ³ may further have one or more substituents, and the substituent may be a glycidyloxy group not shown, or other substituents, for example, having 1 to 1 carbon atoms. 5 may be an alkyl group, phenyl group, etc.,

The benzene ring, naphthalene ring, or biphenyl ring for Ar ⁴ may further have one or more substituents, and the substituent may be a glycidyloxy group, or other substituents, for example, having 1 to 5 carbon atoms. may be an alkyl group, phenyl group, etc.)

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

[Formula 18]

(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, and R ^3a each independently represents a hydrogen atom or Represents a methyl group,

Here, the benzene ring or naphthalene ring for Ar ³ may further have one or more substituents, and the substituents are, for example, substituted other than a glycidyloxy group such as an alkyl group having 1 to 5 carbon atoms or a phenyl group. You can also contribute,

The benzene ring, naphthalene ring, or biphenyl ring for Ar ⁴ may further have one or more substituents, and the substituents include, for example, an alkyl group having 1 to 5 carbon atoms or a glycidyloxy group such as a phenyl group. may be a substitution contribution)

The compound represented by formula (3a) is preferably a phenolic novolak-type epoxy resin in which Ar ⁴ in formula (3a) is at least substituted with a glycidyloxy group. The phenolic novolak-type epoxy resin is not particularly limited, but examples include compounds having a structure represented by the following formula (3-1) (naphthalene skeleton-containing polyfunctional epoxy resin) and naphthalenecresol novolak. A type epoxy resin is mentioned.

[Formula 19]

(Wherein, Ar ³¹ each independently represents a benzene ring or a naphthalene ring, Ar ⁴¹ each independently represents a benzene ring, a naphthalene ring, or a biphenyl ring, and R ^31a each independently represents a hydrogen atom. Or represents a methyl group, p is an integer from 0 to 2, preferably 0 or 1, kz represents an integer from 1 to 50, and each ring has a substituent other than a glycidyloxy group (for example, may have an alkyl group having 1 to 5 carbon atoms, an alkoxy group or a phenyl group having 1 to 5 carbon atoms, and at least one of Ar ³¹ and Ar ⁴¹ represents a naphthalene ring)

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

[Formula 20]

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

The naphthalene cresol novolak type epoxy resin is not particularly limited, but 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 structural unit of cresol novolac epoxy and a structural unit of naphthol novolac epoxy, and both cresol epoxy and naphthol epoxy can be terminals.

[Formula 21]

In the above formula (NE), m and n each represent an integer of 1 or more. There is no particular limitation on the upper limit and ratio of m and n, but from the viewpoint of low thermal expansion, m:n (here, m + n = 100) is preferably 30 to 50:70 to 50, and 45 to 55: 55 to 45 is more preferable.

As the naphthalenecresol novolak-type epoxy resin, a commercial 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" manufactured by Nippon Explosives Co., Ltd., and "HP-9540" and "HP-9500" manufactured by DIC Corporation. possible, and “HP-9540” is particularly preferable.

The compound represented by formula (3a) may be a compound (hereinafter also referred to as “aralkyl type epoxy resin”) that does not correspond to the phenol novolac type epoxy resin described above.

Examples of the aralkyl type epoxy resin include compounds in which Ar ³ is a naphthalene ring and Ar ⁴ is a benzene ring in formula (3a) (also referred to as “naphthol aralkyl type epoxy resin”), and Ar ³ in formula (3a) A compound in which Ar 4 is a benzene ring and Ar ⁴ is a biphenyl ring (also referred to as “biphenyl aralkyl type epoxy resin”) is preferable, and it is more preferable that it is a biphenyl aralkyl type epoxy resin.

As the naphthol aralkyl type epoxy resin, a commercial product 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” manufactured by DIC Corporation, and “ESN-375” and “ESN-475” manufactured by Nittetsu Chemical & Materials Corporation.

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

[Formula 22]

(In the formula, ka represents an integer of 1 or more, preferably 1 to 20, more preferably 1 to 6)

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

As the biphenyl aralkyl type epoxy resin, a commercial product may be used, or a product manufactured by a known method may be used. Commercially available products include, for example, "NC-3000", "NC-3000L", and "NC-3000FH" manufactured by Nippon Explosives Co., Ltd.

Additionally, as the epoxy compound (C) in the curable composition of the present embodiment, it is preferable to use a naphthalene type epoxy resin (excluding those corresponding to the compound represented by formula (3a)). The naphthalene type epoxy resin is preferably a naphthylene ether type epoxy resin from the viewpoint of further improving heat resistance, chemical resistance, copper foil peel strength, and insulation reliability.

From the viewpoint of further improving heat resistance, chemical resistance, copper foil peeling strength, and insulation reliability, the naphthylene ether type epoxy resin is a bifunctional epoxy compound represented by the following formula (3-3) or a bifunctional epoxy compound represented by the following formula (3-4) It is preferable that it is a multifunctional epoxy compound or a mixture thereof.

[Formula 23]

(In the formula, R ₁₃ is each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group or an ethyl group), or an alkenyl group having 2 to 3 carbon atoms (for example, a vinyl group, an allyl group or represents a propenyl group)

[Formula 24]

(In the formula, R ₁₄ is each independently a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (for example, a methyl group or an ethyl group), or an alkenyl group having 2 to 3 carbon atoms (for example, a vinyl group, an allyl group or represents a propenyl group)

As the naphthylene ether type epoxy resin, a commercial product may be used, or a product manufactured by a known method may be used. Commercially available products of naphthylene ether type epoxy resin include, for example, "HP-6000", "EXA-7300", "EXA-7310", "EXA-7311", "EXA-7311L", and "EXA-7311L" manufactured by DIC Corporation. Examples include "EXA7311-G3", "EXA7311-G4", "EXA-7311G4S", and "EXA-7311G5", and HP-6000 is particularly preferable.

Examples of the naphthalene type epoxy resin other than those mentioned above include, but are not limited to, a compound represented by the following formula (b3).

[Formula 25]

(In formula (b3), R ^3b is each independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (for example, a methyl group or an ethyl group), an aralkyl group, a benzyl group, a naphthyl group, or at least one glycidyloxy group. represents a naphthyl group containing a group or a naphthylmethyl group containing at least one glycidyloxy group, and n represents an integer of 0 or more (for example, 0 to 2).

Commercially available products of the compound represented by the above formula (b3) include, for example, “HP-4032” manufactured by DIC Corporation (n = 0 in the above formula (b3)) and “HP-4710” (the above formula (b3) where n = 0 and R ^3b is a naphthylmethyl group containing at least one glycidyloxy group).

In addition, as the epoxy compound (C) in the curable composition of the present embodiment, it is preferable to use a biphenyl type epoxy resin (excluding those corresponding to the epoxy compound (C) described above).

The biphenyl type epoxy resin is not particularly limited, but examples include a compound (compound (b2)) represented by the following formula (b2).

[Formula 26]

(In formula (b2), Ra 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. The alkyl group is not particularly limited, but examples include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, and cyclohexyl group.

When the biphenyl type epoxy resin is compound (b2), the biphenyl type epoxy resin may be in the form of a mixture of compounds (b2) having different numbers of Ra, which is an alkyl group. Specifically, it is preferable that it is a mixture of biphenyl type epoxy resins with different numbers of Ra, which is an alkyl group, and is a mixture of compound (b2) where the number of Ra, which is an alkyl group, is 0, and compound (b2) where the number of Ra, which is an alkyl group, is 4. It is more desirable.

In addition, as the epoxy compound (C) in the curable composition of the present embodiment, a dicyclopentadiene type epoxy resin (excluding those corresponding to the epoxy compound (C) described above) can be used.

The dicyclopentadiene type epoxy resin is not particularly limited, but examples include compounds represented by the following formula (3-5).

[Formula 27]

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

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

[Formula 28]

(In formula (b4), R ^3c each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (for example, a methyl group or an ethyl group).

The dicyclopentadiene type epoxy resin may be a commercially available product or a manufactured product manufactured by a known method. Commercially available products of dicyclopentadiene type epoxy resin include “EPICRON HP-7200L,” “EPICRON HP-7200,” “EPICRON HP-7200H,” and “EPICRON HP-7000HH” manufactured by Dainippon Ink Chemical Industry Co., Ltd. You can.

Among these, the epoxy compound (C) is an epoxy resin represented by formula (3a), a naphthalene-type epoxy resin, and a biphenyl-type epoxy from the viewpoint of being able to exhibit even more excellent heat resistance, chemical resistance, copper foil peeling strength, and insulation reliability. It is preferable that it is at least one selected from the group consisting of resins, and in this case, the epoxy resin represented by formula (3a) includes a naphthalene cresol novolak-type epoxy resin, and the naphthalene-type epoxy resin is a naphthylene ether-type epoxy resin. It is desirable to include.

The epoxy compound (C) may contain other epoxy resins that do not correspond to the above-mentioned epoxy compounds.

Other epoxy resins include, but are not particularly limited to, bisphenol-type epoxy resins, trisphenolmethane-type epoxy resins, anthracene-type epoxy resins, glycidyl ester-type epoxy resins, polyol-type epoxy resins, isocyanurate ring-containing epoxy resins, Examples include fluorene-type epoxy resins and epoxy resins composed of a bisphenol A-type structural unit and a hydrocarbon-based structural unit.

Among the above, other epoxy resins may include bisphenol-type epoxy resins from the viewpoint of further improving chemical resistance, copper foil peel strength, and insulation reliability. Examples of the bisphenol-type epoxy resin include diallyl Bisphenol-type epoxy resins (for example, diallylbisphenol A-type epoxy resin, diallylbisphenol E-type epoxy resin, diallylbisphenol F-type epoxy resin, diallylbisphenol S-type epoxy resin, etc.) can be used.

As an epoxy compound (C), among the epoxy compounds and epoxy resins mentioned above, one type is used individually or in combination of two or more types.

The average number of epoxy groups per molecule of the epoxy compound (C) is preferably 1 to 3, and more preferably 1.5 to 2.5, from the viewpoint of more effectively and reliably exhibiting the effects of the present invention. The average epoxy group number is calculated by the following formula.

(In the formula, Ci represents the epoxy group number of the epoxy compound having i epoxy groups in the molecule, Zi represents the ratio of the epoxy compound having i epoxy groups in the molecule to the entire epoxy compound, Z ₁ + Z ₂ + …Z _n = 1)

The content of the epoxy compound (C) is 100 mass total of the epoxy modified silicone (B) and the epoxy compound (C) from the viewpoint of being able to exhibit further excellent compatibility, heat resistance, chemical resistance, copper foil peeling strength, and insulation reliability. With respect to %, it is preferably 5 to 95 mass%, more preferably 10 to 90 mass%, further preferably 15 to 60 mass%, and especially preferably 20 to 50 mass%.

[Cyclic carbodiimide compound (D)]

The cyclic carbodiimide compound (D) is not particularly limited as long as it has one or more cyclic structures in the molecule and one carbodiimide group in each cyclic structure. By containing the cyclic carbodiimide compound (D), the curable composition of the present embodiment has a high glass transition temperature (Tg), heat resistance, low thermal expansion, and copper foil peel while maintaining sufficient moldability without deteriorating fluidity. Excellent strength and chemical resistance.

The cyclic structure has a carbodiimide group (-N=C=N-), and the first nitrogen atom and the second nitrogen atom are bonded to each other by a linking group. The number of atoms forming the cyclic structure is preferably 8 to 50, more preferably 10 to 30, and still more preferably 10 to 20. Here, the number of atoms forming the cyclic structure means the number of atoms directly forming the cyclic structure. For example, if it is an 8-membered ring, the number of atoms forming a ring-like structure is 8, and if it is a 50-membered ring, the number of atoms forming a ring-like structure is 50. When the number of atoms forming the cyclic structure is 8 or more, the cyclic carbodiimide compound has the advantages of good stability, easy storage, and ease of use. Moreover, it is difficult to synthesize a cyclic carbodiimide compound in which the number of atoms forming a cyclic structure exceeds 50.

The cyclic carbodiimide compound (D) preferably contains a cyclic structure represented by the following formula (D1).

[Formula 29]

(In formula (D1), L is a divalent to tetravalent bonding group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof. The bonding group may contain a hetero atom and/or a substituent.)

Heteroatom refers to O, N, S and P. Among the linking groups, two values are used to form a ring-like structure. When L is a trivalent or tetravalent bonding group, L is bonded to a polymer or other cyclic structure through a single bond, double bond, atom, atom, or atomic group.

(combiner L)

The linking group L is preferably a divalent to tetravalent linking group represented by the following formula (1-1), (1-2) or (1-3).

[Formula 30]

In formula (1-1), Ar ¹⁰¹ and Ar ¹⁰² each independently represent a 2-4 valent aromatic hydrocarbon group having 5-15 carbon atoms which may contain a hetero atom and a substituent.

The aromatic hydrocarbon group represented by Ar ¹⁰¹ and Ar ¹⁰² is not particularly limited, but includes, for example, an arylene group with 5 to 15 carbon atoms and an allentriyl group with 5 to 15 carbon atoms, which may have a heterocyclic ring structure containing a hetero atom. , an aretetrayl group having 5 to 15 carbon atoms. Here, examples of the arylene group (divalent) include phenylene group and naphthalenediyl group. Examples of the allentriyl group (3-valent) include benzene triyl group and naphthalene triyl group. Examples of the arenetetrayl group (tetravalent) include benzenetetrayl group and naphthalenetetrayl group. These aromatic hydrocarbon groups may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, an aldehyde group, etc.

Ar ¹⁰¹ and Ar ¹⁰² are preferably phenylene group, naphthalenediyl group, benzenetriyl group, naphthalenetriyl group, or benzenetetrayl group, and more preferably phenylene group or benzenetriyl group.

In formula (1-2), R ¹⁰¹ and R ¹⁰² each independently represent a 2- to 4-valent aliphatic group (aliphatic hydrocarbon group) having 1 to 20 carbon atoms, which may contain a hetero atom and/or a substituent. Examples include tetravalent alicyclic groups (alicyclic hydrocarbon groups) having 3 to 20 carbon atoms and combinations thereof, or combinations of these aliphatic groups and/or alicyclic groups with 2 to 4 valent aromatic groups (aromatic hydrocarbon groups) having 5 to 15 carbon atoms. You can.

The aliphatic group represented by R ¹⁰¹ and R ¹⁰² is not particularly limited, and examples include an alkylene group with 1 to 20 carbon atoms, an alkanetriyl group with 1 to 20 carbon atoms, and an alkanetetrayl group with 1 to 20 carbon atoms. Examples of the alkylene group include methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, dodecylene group, and hexadecylene group. . The alkane triyl group includes methane triyl group, ethane triyl group, propane triyl group, butane triyl group, pentane triyl group, hexane triyl group, heptane triyl group, octane triyl group, nonantriyl group, decane triyl group, and dodecane triyl group. , hexadecane triyl group, etc. Alkane tetrayl groups include methane tetrayl group, ethane tetrayl group, propane tetrayl group, butane tetrayl group, pentane tetrayl group, hexane tetrayl group, heptane tetrayl group, octane tetrayl group, nonanetetrayl group, decane tetrayl group, and dodecane tetrayl group. , hexadecane tetrayl group, etc. These aliphatic groups may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, an aldehyde group, etc.

Examples of the alicyclic group include a cycloalkylene group with 3 to 20 carbon atoms, a cycloalkanetriyl group with 3 to 20 carbon atoms, and a cycloalkanetetrayl group with 3 to 20 carbon atoms. Cycloalkylene groups include cyclopropylene group, cyclobutylene group, cyclopentylene group, cyclohexylene group, cycloheptylene group, cyclooctylene group, cyclononylene group, cyclodecylene group, cyclododecylene group, and cyclohexadecylene group. etc. can be mentioned. The cycloalkane triyl group includes cyclopropane triyl group, cyclobutane triyl group, cyclopentane triyl group, cyclohexane triyl group, cycloheptane triyl group, cyclooctane triyl group, cyclononane triyl group, cyclodecane triyl group, and cyclododecane. Triyl group, cyclohexadecane triyl group, etc. are mentioned. Cycloalkane tetrayl groups include cyclopropane tetrayl group, cyclobutane tetrayl group, cyclopentane tetrayl group, cyclohexane tetrayl group, cycloheptane tetrayl group, cyclooctane tetrayl group, cyclononanetetrayl group, cyclodecanetetrayl group, and cyclododecane. Tetrayl group, cyclohexadecanetetrayl group, etc. can be mentioned. These alicyclic groups may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, an aldehyde group, etc.

Examples of the aromatic group include an arylene group with 5 to 15 carbon atoms, an allentriyl group with 5 to 15 carbon atoms, and an aretetriyl group with 5 to 15 carbon atoms, which may have a heterocyclic structure containing a heteroatom. Examples of the arylene group include phenylene group and naphthalenediyl group. Examples of the allentriyl group (3-valent) include benzene triyl group and naphthalene triyl group. Examples of the arenetetrayl group (tetravalent) include benzenetetrayl group and naphthalenetetrayl group. These aromatic groups may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 15 carbon atoms, a halogen atom, a nitro group, an amide group, a hydroxyl group, an ester group, an ether group, an aldehyde group, etc.

R ¹⁰¹ and R ¹⁰² are each independently preferably a methylene group, an ethylene group, a vinylidene group, a phenylene group, or an ether group, and more preferably a methylene group, a phenylene group, or an ether group.

In formulas (1-1) and (1-2), X ^{1 and} It is a 4-valent alicyclic group having 3 to 20 carbon atoms, a 2-4 valent aromatic group having 5 to 15 carbon atoms, or a combination thereof.

Examples of the aliphatic group, alicyclic group, and aromatic group for X ¹ and X ² include the same as those exemplified for R ¹⁰¹ and R ¹⁰² above. X ^{1 and}

In formulas (1-1) and (1-2), s and k are each independently preferably 0 to 10, more preferably 0 to 3, and still more preferably 0 to 1. Synthesis of cyclic carbodiimide compounds in which s and k each exceed 10 is difficult and costs increase. Additionally, when s or k is 2 or more, X ¹ or X ² as a repeating unit may be different from other X ¹ or X ² .

In formula ( ^1-3 ), It is a tetravalent aromatic group having 5 to 15 carbon atoms or a combination thereof.

Examples of the aliphatic group, alicyclic group ^, and aromatic group for X ³ include the same groups as those exemplified for R ¹⁰¹ , R ^{102 ,} X ³ is preferably a methylene group, an ethylene group, a vinylidene group, or an ether group, and more preferably a methylene group or an ether group.

Additionally, Ar ¹⁰¹ , Ar ¹⁰² , R ^{101 ,} R ¹⁰² , ^{X 1 ,} However, when the hetero atom is an N atom, the N atom exists as a nitro group and/or an amide group.

Additionally, when L is a divalent linking group, all of Ar ¹⁰¹ , Ar ¹⁰² , R ¹⁰¹ , R ¹⁰² , X ¹ , X ² and X ³ are divalent groups. When L is a trivalent linking group, one of Ar ¹⁰¹ , Ar ¹⁰² , R ¹⁰¹ , R ¹⁰² , X ¹ , X ² and X ³ is a trivalent group. When L is a tetravalent linking group, one of Ar ¹⁰¹ , Ar ¹⁰² , R ¹⁰¹ , R ¹⁰² , X ¹ , X ² and X ³ is a tetravalent group, or Ar ¹⁰¹ , Ar ¹⁰² , R ¹⁰¹ and R ¹⁰² , two of X ¹ , X ² and X ³ are trivalent groups.

In the form in which L is a trivalent or tetravalent linking group and is bonded to another cyclic structure having a carbodiimide group, two or more cyclic structures represented by formula (1) include a spiro ring structure, a single bond, bonded through a shared portion of 1 to 15 carbon atoms (preferably 1 to 12) selected from an alkylene group with 1 to 10 carbon atoms, an aromatic ring structure with 6 to 10 carbon atoms, and a cycloalkane ring structure with 4 to 12 carbon atoms. Aspects can be given. Specific examples of such aspects are shown in the following formulas (2), (4), and (5).

[Formula 31]

The cyclic carbodiimide compound (D) may be a cyclic carbodiimide compound represented by the following formula (i). In addition, the cyclic carbodiimide compound represented by the following formula (i) may have two or more carbodiimide groups in the molecule, or may have one carbodiimide group.

[Formula 32]

(In formula (i), Xa is a divalent group represented by the following formulas (i-1) to (i-3) or a tetravalent group represented by the following formula (i-4). When 0 ^{, and} when

[Formula 33]

(In formula (i-1), n is an integer from 1 to 6)

[Formula 34]

(In formula (i-2), m and n are each independently integers from 0 to 3.)

[Formula 35]

(In formula (i-3), R ³⁰¹ and R ³⁰² each independently represent an alkyl group having 1 to 6 carbon atoms or a phenyl group.)

[Formula 36]

In addition, examples of the cyclic carbodiimide compound represented by the formula (i) include several compounds having the following structural formulas.

[Formula 37]

The cyclic carbodiimide compound (D) includes a polyvalent cyclic carbodiimide compound containing two or more carbodiimide groups in one molecule from the viewpoint of superior glass transition temperature (Tg), chemical resistance, and heat resistance. It is desirable to do so. The cyclic carbodiimide compound (D) more preferably contains a polyvalent cyclic carbodiimide compound containing two or three carbodiimide groups in one molecule from the viewpoint of further excellent curing performance. These polyvalent cyclic carbodiimide compounds are used individually or in combination of two or more types.

Examples of the polycyclic carbodiimide compound include those containing two or more carbodiimide groups in one molecule among the carbodiimide compounds described above. Among these, a compound represented by the following formula (D2) is preferable from the viewpoint of further excellent glass transition temperature (Tg), chemical resistance, and heat resistance.

[Formula 38]

( ^In formula (D2) ^, For example, it is a divalent linking group (1,2-naphthalene-diyl group), and the linking group may have a substituent. The substituent includes an alkyl group with 1 to 20 carbon atoms, an aryl group with 6 to 15 carbon atoms, and a halogen atom. , nitro group, amide group, hydroxyl group, ester group, ether group, aldehyde group, etc. Additionally, these linking groups may have a heterocyclic structure containing a hetero atom.)

[Formula 39]

The cyclic carbodiimide compound (D) is preferably a compound represented by the following formula (D3) from the viewpoint of further excellent heat resistance.

[Formula 40]

These cyclic carbodiimide compounds (D) can be produced by known methods (for example, the method described in the pamphlet of International Publication No. 2010/071213).

The content of the cyclic carbodiimide compound (D) is preferably 1.0 to 30 parts by mass, more preferably 2.0 to 15 parts by mass, and even more preferably 2.5 to 12.0 parts by mass, based on 100 parts by mass of the resin solid content. When the content of the cyclic carbodiimide compound (D) is 1.0 parts by mass or more, heat resistance, low thermal expansion, copper foil peel strength, and chemical resistance tend to be further excellent, and the content of the cyclic carbodiimide compound (D) tends to be further excellent. When the amount is 30 parts by mass or less, flame retardancy tends to be further excellent.

[Compound (H)]

The curable composition of the present embodiment contains a maleimide compound, a cyanate ester compound, a phenolic compound (F) other than alkenylphenol (A), and Al from the viewpoint of further improving low thermal expansion properties, chemical resistance, and copper foil peeling strength. It is preferable to further contain at least one compound (H) selected from the group consisting of kenyl substituted nadimide compounds. The compound (H) is not particularly limited, but is preferably bifunctional or more, and may be trifunctional or more polyfunctional.

The content of compound (H) in the curable composition of the present embodiment is preferably 10 to 80% by mass, more preferably 20 to 60% by mass, and 30 to 50% by mass, based on 100% by mass of the resin solid content. It is more preferable that it is mass%.

[Maleimide compound]

The curable composition of the present embodiment preferably contains a maleimide compound from the viewpoint of further improving low thermal expansion properties and chemical resistance. The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule, for example, a monomaleimide compound having one maleimide group in one molecule (for example, N-phenylmaleimide , N-hydroxyphenylmaleimide, etc.), polymaleimide compounds having two or more maleimide groups in one molecule (e.g., bis(4-maleimidephenyl)methane, 2,2-bis{4-(4) -maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3,5) -diethyl-4-maleimidephenyl)methane), m-phenylenebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4 -trimethyl)hexane, maleimide compounds represented by the following formula (H1a), maleimide compounds represented by the following formula (H1b), prepolymers of these maleimide compounds and amine compounds, etc.

[Formula 41]

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

n ₁ is 1 or more, preferably 1 to 100, and more preferably 1 to 10.

These maleimide compounds are used individually by 1 type or in combination of 2 or more types. Among these, from the viewpoint of further improving low thermal expansion and chemical resistance, maleimide compounds include bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy) -phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, at least one selected from the group consisting of a maleimide compound represented by the formula (H1a) and a maleimide compound represented by the following formula (H1b) It is preferable to include one type.

[Formula 42]

(In formula (H1b), R ¹³ each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, and n ⁴ represents an integer from 1 to 10.)

As the maleimide compound, a commercial item may be used, or a product manufactured by a known method may be used. Commercially available maleimide compounds include “BMI-70,” “BMI-80,” and “BMI-1000P” manufactured by K.I Chemical Co., Ltd., and “BMI-3000” and “BMI-4000” manufactured by Daiwa Chemical Industry Co., Ltd. , “BMI-5100”, “BMI-7000”, “BMI-2300”, “MIR-3000” manufactured by Nippon Explosives Co., Ltd., etc.

From the viewpoint of further improving low thermal expansion and chemical resistance, the content of the maleimide compound is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, and 10 to 100 parts by mass, based on 100 parts by mass of the resin solid content. It is more preferable that it is 40 parts by mass.

[Cyanate ester compound]

It is preferable that the curable composition of this embodiment contains a cyanate ester compound from a viewpoint of further improving low thermal expansion property and copper foil peeling strength. The cyanate ester compound is not particularly limited as long as it is a compound having two or more cyanato groups (cyanate ester groups) in one molecule. For example, naphthol aralkyl type cyanide such as the compound represented by the following formula (H2a) Acid ester compounds, novolak-type cyanate compounds such as compounds represented by the following formula (H2b) excluding the compounds represented by formula (H2a), biphenyl aralkyl-type cyanate ester compounds, diallyl bisphenol-type cyanate ester compounds, Bis(3,3-dimethyl-4-cyanatophenyl)methane, bis(4-cyanatophenyl)methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5- Tricyanatobenzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2 ,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)thioether, bis (4-cyanatophenyl)sulfone and 2,2-bis(4-cyanatophenyl)propane. These cyanate ester compounds are used individually or in combination of two or more types. In this embodiment, from the viewpoint of heat resistance, low thermal expansion, and copper foil peel strength, the cyanate ester compound is a polyfunctional cyanate ester compound such as a naphthol aralkyl-type cyanate ester compound and/or a novolak-type cyanate ester compound. It is desirable to include.

[Formula 43]

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

[Formula 44]

(Wherein, Rya each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, Ryb each independently represents an alkyl group or a hydrogen atom having 1 to 10 carbon atoms, and Ryc each independently represents, Represents an aromatic ring having 4 to 12 carbon atoms, Ryc may form a condensed structure with a benzene ring, Ryc may or may not be present, and A ^1a each independently represents a ring having 1 to 6 carbon atoms. Represents an alkylene group, an aralkylene group with 7 to 16 carbon atoms, an arylene group with 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, a sulfur atom, or a direct bond (single bond), and Ryc is not present. may have two or more groups of Rya and/or Ryb in one benzene ring. n represents an integer of 1 to 20.)

Among these, the cyanate ester compound preferably contains a compound represented by formula (H2a) and/or formula (H2b) from the viewpoint of further improving heat resistance, low thermal expansion, and copper foil peeling strength.

In the formula (H2a), n ₂ represents an integer of 1 or more, is preferably an integer of 1 to 20, and is more preferably an integer of 1 to 10.

In formula (H2b), the alkenyl group having 2 to 8 carbon atoms represented by Rya is not particularly limited, and examples include vinyl group, allyl group, propenyl group, butenyl group, and hexenyl group.

In formula (H2b), the alkyl group having 1 to 10 carbon atoms represented by Ryb is not particularly limited, and examples include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups; Branched alkyl groups such as isopropyl group, isobutyl group, and tert-butyl group can be mentioned.

In formula (H2b), the alkylene group having 1 to 6 carbon atoms represented by A ^1a is not particularly limited, and includes methylene group, ethylene group, trimethylene group, and propylene group. In addition, in the formula (H2b), the aralkylene group having 7 to 16 carbon atoms represented by A ^1a is not particularly limited, but examples include the formula: -CH ₂ -Ar-CH ₂ -, -CH ₂ -CH ₂ -Ar-CH ₂ -CH ₂ -, or the formula: -CH ₂ -Ar-CH ₂ -CH ₂ - (wherein Ar represents a phenylene group, naphthylene group, or biphenylene group). You can. In addition, the arylene group having 6 to 10 carbon atoms represented by A ^1a is not particularly limited, and examples include a phenylene ring.

In the formula (H2b), n represents an integer of 1 to 20, is preferably an integer of 1 to 15, and is more preferably an integer of 1 to 10.

The compound represented by formula (H2b) is preferably a compound represented by the following formula (H2c).

[Formula 45]

(Wherein, Rx each independently represents a hydrogen atom or a methyl group, R each independently represents an alkenyl group having 2 to 8 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a hydrogen atom, and n is 1. represents an integer from ∼ 10)

These cyanate ester compounds may be produced according to known methods. Specific manufacturing methods include, for example, the methods described in Japanese Patent Application Publication No. 2017-195334 (particularly paragraphs 0052 to 0057).

The content of the cyanate ester compound is preferably 3 to 70 parts by mass, and more preferably 5 to 60 parts by mass, based on 100 parts by mass of the resin solid content from the viewpoint of further improving low thermal expansion properties and copper foil peeling strength. And, it is more preferable that it is 10 to 40 parts by mass.

(Phenol compounds (F) other than alkenylphenol (A))

The curable composition of the present embodiment preferably contains a phenol compound (F) other than alkenylphenol (A) from the viewpoint of being able to exhibit even more excellent chemical resistance. The phenol compound (F) is not particularly limited, but includes bisphenol-type phenol resins (e.g., bisphenol A-type resin, bisphenol E-type resin, bisphenol F-type resin, bisphenol S-type resin, etc.), phenolic novolac resins (e.g. For example, phenol novolak resin, naphthol novolak resin, cresol novolak resin, aminotriazine novolak resin described later, etc.), glycidyl ester type phenol resin, naphthalene type phenol resin, anthracene type phenol resin, dicyclopentadiene type. Phenol resin, biphenyl type phenol resin, alicyclic phenol resin, polyol type phenol resin, aralkyl type phenol resin, phenol-modified aromatic hydrocarbon formaldehyde resin, fluorene type phenol resin, etc. are mentioned. These phenol compounds are used individually or in combination of two or more types.

Among these, the phenol compound (F) contains a bifunctional phenol compound or aminotriazine novolac resin having two phenolic hydroxyl groups in one molecule from the viewpoint of exhibiting even better compatibility and chemical resistance. desirable.

The difunctional phenol compound is not particularly limited, but includes bisphenol, biscresol, bisphenols with a fluorene skeleton (e.g., bisphenol with a fluorene skeleton, biscresol with a fluorene skeleton, etc.), biphenol (e.g. For example, p,p'-biphenol, etc.), dihydroxydiphenyl ether (for example, 4,4'-dihydroxydiphenyl ether, etc.), dihydroxydiphenyl ketone (for example, 4 , 4'-dihydroxydiphenyl ketone, etc.), dihydroxydiphenyl sulfide (e.g., 4,4'-dihydroxydiphenyl sulfide, etc.), dihydroxyarene (e.g., hydro quinone, etc.). These bifunctional phenol compounds are used individually or in combination of two or more types. Among these, the bifunctional phenol compound preferably contains at least one selected from the group consisting of bisphenol, biscresol, and bisphenols having a fluorene skeleton from the viewpoint of exhibiting even more excellent chemical resistance. From the same viewpoint as above, bisphenol having a fluorene skeleton is preferably biscresol fluorene.

Examples of the aralkyl type phenol resin include a compound represented by the following formula (c2).

[Formula 46]

(Wherein, 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, and R ^2a each independently represents a hydrogen atom or a methyl group. represents an integer of 1 to 50, and each ring may have a substituent other than a hydroxyl group (for example, an alkyl group or phenyl group having 1 to 5 carbon atoms, etc.)

The compound represented by formula (c2) is a compound (hereinafter referred to as “naphthol aralkyl type phenol resin”) wherein Ar ¹ is a naphthalene ring and Ar ² is a benzene ring in formula (c2) from the viewpoint of further improving the copper foil peeling strength. "), and in formula (c2), a compound in which Ar ¹ is a benzene ring and Ar ² is a biphenyl ring (hereinafter also referred to as “biphenyl aralkyl type phenol resin”) is preferable.

The naphthol aralkyl type phenol resin is preferably a compound represented by the following formula (8).

[Formula 47]

(In the formula, R ₇ each independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 or more.)

In Formula (8), n ₃ represents an integer of 1 or more, is preferably an integer of 1 to 10, and is more preferably an integer of 1 to 6.

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

[Formula 48]

(In the formula, R ^2b each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group (preferably a hydrogen atom), and m1 is an integer of 1 to 20 (preferably an integer of 1 to 6). ) indicates)

The phenol compound A' preferably contains a compound represented by the above formula (8) from the viewpoint of further improving low thermal expansion and chemical resistance.

The aralkyl type phenol resin may be a commercial product or a product manufactured by a known method. Commercially available aralkyl-type phenol resins include “KAYAHARD GPH-65,” “KAYAHARD GPH-78,” and “KAYAHARD GPH-103” (biphenyl aralkyl-type phenol resin) manufactured by Nippon Kaypowder Co., Ltd. and Nippon Chemical Co., Ltd. "SN-495" (naphthol aralkyl type phenol resin).

As described above, the curable composition of the present embodiment may contain aminotriazine novolak resin as the phenol compound (F). When an aminotriazine novolak resin is included, a terminal hydroxyl group or an epoxy group produced by the reaction of alkenylphenol (A), epoxy modified silicone (B), and an epoxy compound (C) other than epoxy modified silicone (B), The aminotriazine novolac resin tends to react further to increase terminal functional groups such as hydroxyl groups and amino groups. As a result, since many terminal functional groups with high reactivity with the thermosetting resin are present, compatibility and crosslinking density are improved, and the copper foil peeling strength tends to be improved.

The aminotriazine novolak resin is not particularly limited, but from the viewpoint of improving the copper foil peeling strength, it is preferably a novolac resin having 2 to 20 phenol hydroxyl groups per triazine skeleton in the molecule, and one triazine skeleton in the molecule. It is more preferable to be a novolak resin having 2 to 15 phenol hydroxyl groups relative to the triazine skeleton, and even more preferably to be a novolac resin having 2 to 10 phenol hydroxyl groups relative to one triazine skeleton in the molecule.

The content of alkenylphenol (A) in the curable composition of the present embodiment is alkenylphenol (A) and epoxy-modified silicone (B) from the viewpoint of exhibiting even better compatibility, heat resistance, and low thermal expansion properties. , it is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and still more preferably 5 to 20 parts by mass, relative to 100 parts by mass of the total amount of the epoxy compound (C) and the phenol compound (F).

The content of epoxy-modified silicone (B) in the curable composition of the present embodiment is alkenylphenol (A) and epoxy-modified silicone (B) from the viewpoint of being able to express further excellent low thermal expansion and chemical resistance in a good balance. ), the total amount of the epoxy compound (C) and the phenol compound (F) is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 55 parts by mass.

The content of the epoxy compound (C) in the curable composition of the present embodiment is alkenylphenol (A), from the viewpoint of being able to exhibit further excellent compatibility, heat resistance, chemical resistance, copper foil peel strength, and insulation reliability. It is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, and 15 to 25 parts by mass, based on 100 parts by mass of the total amount of epoxy modified silicone (B), epoxy compound (C), and phenol compound (F). It is more desirable.

The content of the phenol compound (F) in the curable composition of the present embodiment is alkenylphenol (A), epoxy modified silicone (B), and epoxy compound (C) from the viewpoint of being able to exhibit even more excellent chemical resistance. and the total amount of the phenol compound (F) is preferably 5 to 30 parts by mass, more preferably 10 to 25 parts by mass, and even more preferably 15 to 20 parts by mass.

In addition, when the curable composition does not contain the phenol compound (F), the respective contents of the alkenylphenol (A), epoxy modified silicone (B), and epoxy compound (C) described above are the alkenylphenol (A) , represents the content with respect to the total amount of 100 parts by mass of epoxy modified silicone (B) and epoxy compound (C).

(Alkenyl substituted nadimide compound)

The curable composition of the present embodiment preferably contains an alkenyl substituted nadimide compound from the viewpoint of further improving heat resistance. The alkenyl substituted nadimide compound is not particularly limited as long as it is a compound having one or more alkenyl substituted nadimide groups in one molecule, but examples include compounds represented by the following formula (H4a).

[Formula 49]

(In the formula, R ₁ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group or an ethyl group), and R ₂ represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, or an alkyl group having 1 to 6 carbon atoms. Represents a phenylene group, a naphthylene group, or a group represented by the following formula (3) or the following formula (4))

[Formula 50]

(In formula (3), R ₃ represents a methylene group, an isopropylidene group, CO, O, S, or SO ₂ )

[Formula 51]

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

The alkenyl substituted nadimide compound represented by formula (H4a) may be a commercial product or a product manufactured according to a known method. Commercially available products include “BANI-M” and “BANI-X” manufactured by Maruzen Petrochemical Co., Ltd.

From the viewpoint of further improving heat resistance, the content of the alkenyl substituted nadimide compound is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass, and more preferably 10 to 30 parts by mass, based on 100 parts by mass of the resin solid content. It is more preferable that it is part by mass.

＜Second Embodiment＞

[Curable composition of the second embodiment]

The curable composition of the second embodiment includes a structural unit derived from alkenylphenol (A), a structural unit derived from epoxy modified silicone (B), and an epoxy compound (C) other than the epoxy modified silicone (B). It includes a polymer (E) containing the structural unit derived from the polymer and a cyclic carbodiimide compound (D). The alkenylphenol (A), epoxy-modified silicone (B), epoxy compound (C), and cyclic carbodiimide compound (D) are the same as described in the first embodiment above. In this specification, the curable composition of the first embodiment is a curable composition that does not contain the polymer (E), and is distinguished from the curable composition of the second embodiment.

The curable composition of the second embodiment contains, in addition to the polymer (E) and the cyclic carbodiimide compound (D), optionally the maleimide compound, cyanate ester compound, and alkenylphenol (A) described above. You may further contain at least one compound (H) selected from the group consisting of other phenol compounds (F) and alkenyl substituted nadiimide compounds. Compound (H) may be an unreacted component remaining after polymerization of polymer (E), or may be a component added again to the synthesized polymer (E).

In addition to the polymer (E), the curable composition of the second embodiment further contains at least one selected from the group consisting of alkenylphenol (A), epoxy modified silicone (B), and epoxy compound (C). You can do it. In this case, alkenylphenol A, epoxy modified silicone (B), or epoxy compound (C) contained in the curable composition of the second embodiment may be unreacted components remaining after polymerization of polymer (E), or may be a synthesized polymer. For (E), the component may be added again.

The curable composition of the second embodiment has excellent low thermal expansion properties, copper foil peel strength, and chemical resistance. The factor for improving each characteristic is the same as the mechanism of action in the curable composition of the first embodiment, depending on the temperature at which the curable composition is placed, the cyclic carbodiimide compound (D), the polymer (E), and optionally added It is assumed that by controlling the reactivity of the thermosetting resin such as compound (H), the compatibility and crosslinking reaction rate are appropriately controlled, and the low thermal expansion property, copper foil peel strength, and chemical resistance are improved. In addition, by containing the polymer (E), the curable composition of the second embodiment has further excellent compatibility, can exhibit better low thermal expansion, copper foil peel strength, and chemical resistance, and is also excellent in insulation reliability. . Polymer (E) can exhibit sufficient compatibility even when mixed with a thermosetting resin that lacks compatibility with a silicone-based compound. As a result, the curable composition containing the polymer (E) and the thermosetting resin can provide a uniform varnish or cured product. In a cured product such as prepreg obtained using the curable composition, each component is uniformly compatible, and the variation in physical properties due to component heterogeneity is further suppressed.

[Polymer (E)]

The polymer (E) contains structural units derived from alkenylphenol (A), structural units derived from epoxy modified silicone (B), and structural units derived from epoxy compound (C), and optionally, It may further contain structural units derived from one or more compounds (H) selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds (F) other than alkenylphenol A, and alkenyl substituted nadimide compounds. do. When the polymer (E) has a structural unit derived from the compound (H), the compound (H) is preferably a bifunctional compound. In addition, in this specification, “structural unit derived from alkenylphenol (A)”, “structural unit derived from epoxy modified silicone (B)”, “structural unit derived from epoxy compound (C)”, and “compound ( The term “structural unit derived from H)” refers to a structural unit obtained by polymerizing each component of alkenylphenol (A), epoxy modified silicone (B), epoxy compound (C), and compound (H) in polymer (E). In addition, it shall include structural units formed through reactions that can give the same structural units. Hereinafter, each structural unit is also referred to as structural unit (A), (B), (C), and (H), respectively.

The weight average molecular weight of the polymer (E) is preferably 3.0 × 10 ³ to 5.0 × 10 ⁴ , and more preferably 3.0 × 10 ³ to 2.0 × 10 ⁴ in terms of polystyrene in gel permeation chromatography. . When the weight average molecular weight is 3.0 × 10 ³ or more, the curable composition of the second embodiment tends to be able to exhibit further excellent low thermal expansion properties, copper foil peel strength, and chemical resistance. When the weight average molecular weight is 5.0 × 10 ⁴ or less, the curable composition of the second embodiment tends to exhibit even more excellent compatibility.

The content of the structural unit (A) in the polymer (E) is preferably 5 to 50% by mass with respect to the total mass of the polymer (E). When the content of the structural unit (A) is within the above range, the curable composition of the second embodiment can exhibit further excellent compatibility, and the balance between heat resistance and low thermal expansion tends to improve. From the same viewpoint, the content of the structural unit (A) is more preferably 10 to 45 mass%, and even more preferably 15 to 40 mass%.

The content of the structural unit (B) in the polymer (E) is preferably 20 to 60% by mass with respect to the total mass of the polymer (E). When the content of the structural unit (B) is within the above range, the curable composition of the second embodiment tends to be able to exhibit further excellent low thermal expansion properties and chemical resistance in a good balance. From the same viewpoint, the content of the structural unit (B) is more preferably 25 to 55% by mass, and even more preferably 30 to 50% by mass.

The structural unit (B) is an epoxy-modified silicone (low-equivalent epoxy-modified silicone (B1')) having an epoxy equivalent of 50 to 350 g/mol, and an epoxy-modified silicone (high-equivalent epoxy-modified silicone (B1')) having an epoxy equivalent of 400 to 4000 g/mol. It is preferred that it contains a structural unit derived from equivalent epoxy-modified silicone (B2')). Low-equivalent epoxy-modified silicone (B1'), high-equivalent epoxy-modified silicone (B2') are epoxy-modified silicones (low-equivalent epoxy-modified silicone (B1'')), each having an epoxy equivalent weight of 140 to 250 g/mol, 450 g/mol. More preferably, it is an epoxy-modified silicone (high-equivalent epoxy-modified silicone (B2'')) having an epoxy equivalent weight of ∼3000 g/mol.

The content of structural unit (B) 1 derived from low-equivalent epoxy-modified silicone (B1') in the polymer (E) is preferably 5 to 25% by mass, and 7.5 to 20%, based on the total mass of the polymer (E). It is more preferable that it is mass %, and it is still more preferable that it is 10-17 mass %.

The content of the structural unit (B) 2 derived from the high-equivalent epoxy-modified silicone (B2') in the polymer (E) is preferably 15 to 55% by mass, and 20 to 52.5%, based on the total mass of the polymer (E). It is more preferable that it is mass %, and it is still more preferable that it is 25-50 mass %.

The mass ratio of the content of structural unit (B) 2 to the content of structural unit (B) 1 is preferably 1.5 to 4, more preferably 1.5 to 3.5, and still more preferably 1.9 to 3.3. When the content of structural unit (B) 1 and structural unit (B) 2 has the above relationship, the copper foil peeling strength and chemical resistance of the curable composition of the second embodiment tend to improve more.

The structural unit (C) in the polymer (E) is a group consisting of a compound represented by the formula (b1), a compound represented by the formula (b2), a compound represented by the formula (b3), and a compound represented by the formula (b4). It is preferable that the unit is derived from at least one type selected from.

The content of the structural unit (C) in the polymer (E) is preferably 5 to 40% by mass with respect to the total mass of the polymer (E). When the content of the structural unit (C) is within the above range, the curable composition of the second embodiment has further excellent compatibility and tends to exhibit further excellent heat resistance, chemical resistance, copper foil peel strength, and insulation reliability. There is. From the same viewpoint, the content of the structural unit (C) is preferably 10 to 30 mass%, and more preferably 15 to 25 mass%.

Moreover, the content of structural unit (C) is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, based on the total mass of structural unit (B) and structural unit (C), and is more preferably 15% by mass. It is more preferable that it is -60 mass%, and it is especially preferable that it is 20-50 mass%. When the contents of the structural unit (B) and the structural unit (C) have the above relationship, the curable composition of the second embodiment has further excellent compatibility and has better heat resistance, chemical resistance, copper foil peel strength, and insulation reliability. tends to improve.

When the polymer (E) has a structural unit derived from the compound (H), the content of the structural unit (H) in the polymer (E) is preferably 3 to 40% by mass based on the total mass of the polymer (E). do. When the content of the structural unit (H) is within the above range, the curable composition of the second embodiment tends to be able to exhibit further excellent low thermal expansion properties, chemical resistance, and copper foil peeling strength. From the same viewpoint, the content of the structural unit (H) is preferably 5 to 35 mass%, and more preferably 10 to 30 mass%.

When the polymer (E) has a structural unit (hereinafter also referred to as “structural unit (F)”) derived from a phenol compound (F) other than alkenylphenol (A), the structural unit (F) in the polymer (E) The content is preferably 5 to 30 mass% based on the total mass of the polymer (E). When the content of the structural unit (F) is within the above range, the curable composition of the second embodiment tends to be able to exhibit even more excellent chemical resistance. From the same viewpoint, the content of the structural unit (F) is preferably 10 to 27.5 mass%, and more preferably 10 to 25 mass%.

The alkenyl group equivalent of polymer (E) is preferably 300 to 1500 g/mol. When the alkenyl group equivalent is 300 g/mol or more, the cured product of the curable composition of the second embodiment tends to have a further decrease in elastic modulus, and as a result, the coefficient of thermal expansion of a substrate or the like obtained using the cured product is further reduced. It has a tendency to deteriorate. When the alkenyl group equivalent is 1500 g/mol or less, the compatibility, heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability of the curable composition of the second embodiment tend to be further improved. From the same viewpoint, the alkenyl group equivalent weight is preferably 350 to 1,200 g/mol, and more preferably 400 to 1,000 g/mol.

The content of polymer (E) in the curable composition of the second embodiment is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, based on 100% by mass of the resin solid content. It is more preferable that it is mass%. When the content is within the above range, the curable composition of the second embodiment has further excellent compatibility and tends to be able to further express the low thermal expansion copper foil peel strength and chemical resistance with a good balance.

The polymer (E) is, for example, alkenylphenol (A), epoxy modified silicone (B), epoxy compound (C), and, if necessary, compound (H) in the presence of a polymerization catalyst (G). It is obtained through a reaction process. The reaction may be carried out in the presence of an organic solvent. More specifically, in the above step, an addition reaction between the epoxy group of the epoxy modified silicone (B) and the epoxy compound (C) and the hydroxyl group of the alkenylphenol (A), and the hydroxyl group of the resulting addition reaction product and the epoxy modified silicone As the addition reaction of the epoxy groups of (B) and the epoxy compound (C) proceeds, polymer (E) can be obtained.

The polymerization catalyst (G) is not particularly limited, and examples include imidazole catalysts and phosphorus-based catalysts. These catalysts are used individually or in combination of two or more types. Among these, imidazole catalysts are preferable.

The imidazole catalyst is not particularly limited and includes, for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, and 1-cyanoethyl-2-phenyl. Midazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2 -Phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzoimidazole (“TBZ” manufactured by Shikoku Chemical Industry Co., Ltd.), 2 and imidazoles such as 4,5-triphenylimidazole (“TPIZ” manufactured by Tokyo Chemical Industry Co., Ltd.). Among these, from the viewpoint of preventing homopolymerization of the epoxy component, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and/or 2,4,5-triphenylimidazole are used. desirable.

The amount of the polymerization catalyst (G) (preferably an imidazole catalyst) to be used is not particularly limited and includes, for example, alkenylphenol (A), epoxy modified silicone (B), epoxy compound (C), and compound (H). It is 0.1 to 10 parts by mass with respect to the total amount of 100 parts by mass. From the viewpoint of increasing the weight average molecular weight of the polymer (E), the amount of the polymerization catalyst (G) used is preferably 0.5 parts by mass or more, and more preferably 4.0 parts by mass or less.

The organic solvent is not particularly limited, and for example, a polar solvent or a non-polar solvent can be used. The polar solvent is not particularly limited, and examples include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Cellosolve-based solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; Ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; Amides such as dimethylacetamide and dimethylformamide can be mentioned. The nonpolar solvent is not particularly limited, and examples include aromatic hydrocarbons such as toluene and xylene. These solvents are used individually or in combination of two or more types.

The amount of the organic solvent used is not particularly limited, and is, for example, 50 to 150 parts by mass based on 100 parts by mass of the total amount of alkenylphenol (A), epoxy modified silicone (B), epoxy compound (C), and compound (H). It is the mass part.

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

After completion of the reaction in this step, the polymer (E) may be separated and purified from the reaction mixture by a usual method.

As described above, the curable composition of the second embodiment may further contain a compound (H) as needed in addition to the polymer (E). By further containing the compound (H) in addition to the polymer (E), the curable composition of the second embodiment tends to further improve heat resistance, low thermal expansion, chemical resistance, and copper foil peel strength.

When the curable composition of the second embodiment contains the polymer (E) and the compound (H), the content of the polymer (E) in the curable composition of the second embodiment is that of the polymer (E) and the compound (H). It is preferably 5 to 60 mass%, more preferably 10 to 55 mass%, and even more preferably 20 to 50 mass%, based on a total of 100 mass%. When the content is within the above range, the curable composition has further excellent compatibility and tends to be able to exhibit heat resistance, low thermal expansion, chemical resistance, and copper foil peel strength in a good balance.

When the curable composition of the second embodiment contains the polymer (E) and the compound (H), the content of the compound (H) in the curable composition of the second embodiment is that of the polymer (E) and the compound (H). With respect to a total of 100 mass%, it is preferably 20 to 80 mass%, more preferably 35 to 75 mass%, and even more preferably 45 to 65 mass%.

In addition, the content of the cyclic carbodiimide compound (D) in the curable composition of the second embodiment is the same as the content in the curable composition of the first embodiment. When the content of the cyclic carbodiimide compound (D) is within the range described above, heat resistance, low thermal expansion, copper foil peel strength, and chemical resistance tend to be further excellent.

The curable composition of the present embodiment may further contain other resins, as long as the effects of the curable composition of the present embodiment are not impaired. Other resins include, for example, oxetane resins, benzoxazine compounds, and compounds having a polymerizable unsaturated group. These resins are used individually or in combination of two or more types.

Oxetane resins include, for example, alkyloxetane such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, and 3-methyl- 3-methoxymethyloxetane, 3,3'-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl type oxetane, Toa Examples include “OXT-101” and “OXT-121” manufactured by Synthesis Co., Ltd.

The term “benzoxazine compound” as used herein refers to a compound having two or more dihydrobenzoxazine rings in one molecule. Examples of the benzoxazine compound include "Bisphenol F-type benzoxazine BF-BXZ" and "Bisphenol S-type benzoxazine BS-BXZ" manufactured by Konishi Chemical Co., Ltd.

Examples of the compound having a polymerizable unsaturated group include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; Methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethyl (meth)acrylates of monohydric or polyhydric alcohols, such as allpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; Epoxy (meth)acrylates such as bisphenol A-type epoxy (meth)acrylate and bisphenol F-type epoxy (meth)acrylate; Benzocyclobutene resin, etc. can be mentioned.

[Inorganic filler]

The curable composition of the present embodiment preferably further contains an inorganic filler from the viewpoint of further improving low thermal expansion properties. Inorganic fillers are not particularly limited and include, for example, silica, silicon compounds (e.g., white carbon, etc.), metal oxides (e.g., alumina, titanium white, zinc oxide, magnesium oxide, zirconium oxide, etc.) ), metal nitrides (e.g. boron nitride, agglomerated boron nitride, silicon nitride, aluminum nitride, etc.), metal sulfates (e.g. barium sulfate, etc.), metal hydroxides (e.g. aluminum hydroxide, aluminum hydroxide heat treatment) products (for example, aluminum hydroxide is heated to reduce some of the water of crystallization), boehmite, magnesium hydroxide, etc.), molybdenum compounds (for example, molybdenum oxide, zinc molybdate, etc.), zinc compounds (for example, For example, zinc borate, zinc stannate, etc.), clay, kaolin, 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 fibers (including glass fine powders such as E glass, T glass, D glass, S glass, Q glass, etc.), hollow glass, spherical glass, etc. These inorganic fillers are used individually or in combination of two or more types. Among these, the inorganic filler is preferably at least one selected from the group consisting of silicas, metal hydroxides and metal oxides from the viewpoint of further improving low thermal expansion properties, and is selected from the group consisting of silicas, boehmite and alumina. It is more preferable that it contains at least one type, and it is even more preferable that it is silica.

Examples of silica include natural silica, fused silica, synthetic silica, aerosil, and hollow silica. These silicas are used individually or in combination of two or more types. Among these, fused silica is preferable from the viewpoint of dispersibility, and two or more types of fused silica having different particle sizes are more preferable from the viewpoint of fillability and fluidity.

From the viewpoint of further improving the low thermal expansion property, the content of the inorganic filler is preferably 50 to 1,000 parts by mass, more preferably 70 to 500 parts by mass, and even more preferably 100 to 300 parts by mass, based on 100 parts by mass of the resin solid content. desirable.

[Silane coupling agent]

The curable composition of this embodiment may further contain a silane coupling agent. The curable composition of the present embodiment tends to further improve the dispersibility of the inorganic filler by containing a silane coupling agent, or further improve the adhesive strength between the components of the curable composition of the present embodiment and the substrate described later. There is.

The silane coupling agent is not particularly limited and includes silane coupling agents generally used for surface treatment of inorganic materials, and aminosilane-based compounds (e.g., γ-aminopropyltriethoxysilane, N-β-( aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane-based compounds (e.g., γ-glycidoxypropyltrimethoxysilane, etc.), acrylic silane-based compounds (e.g., γ-acryloxy propyltrimethoxysilane, etc.), cationic silane compounds (e.g., N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), styrylsilane compounds, phenyl Silane-based compounds, etc. can be mentioned. Silane coupling agents are used individually or in combination of two or more types. Among these, it is preferable that the silane coupling agent is an epoxysilane-based compound. Examples of the epoxysilane-based compound include “KBM-403,” “KBM-303,” “KBM-402,” and “KBE-403” manufactured by Shin-Etsu Chemical Co., Ltd.

The content of the silane coupling agent is not particularly limited, but may be 0.1 to 5.0 parts by mass based on 100 parts by mass of the resin solid content.

[Wetting and dispersing agent]

The curable composition of this embodiment may further contain a wetting and dispersing agent. The curable composition tends to further improve the dispersibility of the filler by containing a wetting dispersant.

The wet dispersant may be any known dispersant (dispersion stabilizer) used to disperse the filler, for example, DISPER BYK-110, 111, 118, 180, 161, BYK- manufactured by Big Chemi Japan Co., Ltd. Examples include W996, W9010, and W903.

The content of the wetting and dispersing agent is not particularly limited, but is preferably 0.5 parts by mass or more and 5.0 parts by mass or less with respect to 100 parts by mass of the resin solid content.

[solvent]

The curable composition of this embodiment may further contain a solvent. By containing a solvent, the curable composition of the present embodiment tends to lower the viscosity at the time of preparation of the curable composition, further improve handling properties, and further improve impregnation into the substrate. There is.

The solvent is not particularly limited as long as it can dissolve part or all of the components in the curable composition, but examples include ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (e.g. toluene, xylene, etc.) ), amides (for example, dimethyl formaldehyde, etc.), propylene glycol monomethyl ether and its acetate, etc. These solvents are used individually or in combination of two or more types.

The method for producing the curable composition of the present embodiment is not particularly limited and includes, for example, a method of mixing each component in a solvent all at once or sequentially and stirring them. At this time, known processes such as stirring, mixing, and kneading are used to uniformly dissolve or disperse each component.

[Usage]

As described above, the curable composition of the present embodiment can exhibit excellent low thermal expansion properties, copper foil peel strength, and chemical resistance. For this reason, the curable composition of this embodiment is preferably used for prepreg, metal foil-clad laminate, and printed wiring board. The curable composition of the present embodiment can be applied to the above-described uses by curing it. That is, the cured product of the present embodiment is obtained by curing the curable composition of the present embodiment.

Moreover, especially in the above-mentioned use, the curable composition of the second embodiment contains, in addition to the polymer (E) and the cyclic carbodiimide compound (D), at least an epoxy compound (C) (a structural unit in the polymer (E) ( It is preferred to include an epoxy compound (C) that exists separately from C).

In this case, the polymer (E) preferably has a unit derived from the above-mentioned bifunctional epoxy compound as the unit derived from the epoxy compound (C), and more preferably from the above-described biphenyl type epoxy resin. Compound (b2), which has a unit derived from a compound, more preferably a compound represented by the above formula (b2) (compound (b2)), and even more preferably where the number of R ^a is 0, and which is an alkyl group. It has a unit derived from compound (b2) in which the number of R ^a is 4 (commercially available products include, for example, product name "YL-6121H" manufactured by Mitsubishi Chemical Corporation).

In addition, the epoxy compound (C) that exists separately from the structural unit (C) in the polymer (E) includes the above-mentioned naphthylene ether type epoxy resin (commercially available products include, for example, “HP-6000” manufactured by DIC Corporation). ) and/or a naphthalenecresol novolac type epoxy resin (commercially available products include, for example, “HP-9540” manufactured by DIC Corporation).

[Prepreg]

The prepreg of this embodiment includes a base material and the curable composition of this embodiment impregnated or applied to the base material. As described above, the prepreg may be a prepreg obtained by a known method. Specifically, the curable composition of the present embodiment is impregnated or applied to a substrate, and then heated and dried under conditions of 100 to 200°C. It is obtained by semi-hardening (B staging).

The prepreg of this embodiment also includes the form of a cured product obtained by heat curing a prepreg in a semi-cured state under the conditions of 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 is preferably 30 to 90 volume%, more preferably 35 to 85 volume%, in terms of solid content of the prepreg, relative to the total amount of prepreg, and even more preferably It is 40 to 80 volume%. When the content of the curable composition is within the above range, moldability tends to be further improved. In addition, the content calculation of the curable composition referred to herein also includes the cured product of the curable composition of the present embodiment. In addition, the solid content of the prepreg referred to here refers to the component from which the solvent has been removed from the prepreg, and for example, the filler is included in the solid content of the prepreg.

The base material is not particularly limited, and examples include known base materials used for materials of various printed wiring boards. Specific examples of the substrate include glass substrates, inorganic substrates other than glass (e.g., inorganic substrates made of inorganic fibers other than glass, such as quartz), and organic substrates (e.g., wholly aromatic polyamide, polyester, poly and organic substrates composed of organic fibers such as paraphenylenebenzoxazole and polyimide. These base materials are used individually or in combination of two or more types. Among these, a glass substrate is preferable from the viewpoint of further excellent heating dimensional stability.

Examples of the 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 these, the fibers constituting the glass substrate are selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass from the viewpoint of superior strength and low water absorption. It is preferable that at least one type of fiber is selected.

The form of the base material is not particularly limited, but examples include woven fabric, non-woven fabric, roving, chopped strand mat, and surfacing mat. The weaving method of the woven fabric is not particularly limited, but for example, plain weave, twill weave, and twill weave are known, and these known weaves can be appropriately selected and used depending on the intended use or performance. In addition, glass woven fabrics that have been opened or surface-treated with a silane coupling agent or the like are preferably used. The thickness or mass of the base material is not particularly limited, but is usually preferably around 0.01 to 0.1 mm.

[Metal foil clad laminate]

The metal foil-clad laminate of the present embodiment includes a laminate containing the prepreg of the present embodiment, and metal foil disposed on one side or both surfaces of the laminate. The above-mentioned laminate may be formed of one prepreg or may be formed of a plurality of prepregs. Moreover, the said laminated body may contain a resin sheet other than the prepreg of this embodiment.

The metal foil (conductor layer) may be any metal foil used in various printed wiring board materials, and examples include metal foils such as copper and aluminum. Examples of the copper foil include copper foils such as rolled copper foil and electrolytic copper foil. You can. The thickness of the conductor layer is, for example, 1 to 70 μm, and is preferably 1.5 to 35 μm.

The forming method and conditions for forming the metal foil-clad laminate are not particularly limited, and general methods and conditions for laminates and multilayer boards for printed wiring boards can be applied. For example, when forming a laminated board (the above-described laminated body) or a metal foil-clad laminated board, a multi-stage press machine, a multi-stage vacuum press machine, a continuous molding machine, an autoclave molding machine, etc. can be used. In addition, in the molding (lamination molding) of a laminate (the above-mentioned laminate) or a metal foil-clad laminate, the temperature is 100 to 300° C., the pressure is 2 to 100 kgf/cm ² , and the heating time is 0.05 to 5 hours. The range is general. Additionally, if necessary, post-curing may be performed at a temperature of 150 to 300°C. Especially when a multi-stage press machine is used, from the viewpoint of sufficiently promoting curing of the prepreg, a temperature of 200°C to 250°C, a pressure of 10 to 40 kgf/cm ² , and a heating time of 80 to 130 minutes are preferable, and a temperature of 215°C to 235°C is preferable. C, a pressure of 25 to 35 kgf/cm ² , and a heating time of 90 to 120 minutes are more preferable. In addition, it is also possible to form a multilayer board by combining the above-mentioned prepreg and a separately manufactured wiring board for the inner layer and lamination molding.

[Printed wiring board]

The printed wiring board of this embodiment includes an insulating layer containing the prepreg of this embodiment, and a conductor layer formed on the surface of the insulating layer. Here, the insulating layer may be a cured product obtained by curing the prepreg of the present embodiment. The printed wiring board of this embodiment can be formed, for example, by etching the metal foil of the metal foil-clad laminate of this embodiment into a predetermined wiring pattern to form a conductor layer.

The printed wiring board of this embodiment can be specifically manufactured, for example, by the following method. First, the metal foil-clad laminate of this embodiment is prepared. The metal foil of the metal foil-clad laminate is etched into a predetermined wiring pattern to produce an inner layer substrate having a conductor layer (inner layer circuit). Next, a predetermined number of insulating layers and a metal foil for the outer layer circuit are laminated on the surface of the conductor layer (built-in circuit) of the inner layer substrate in this order, heated and pressed, and integrally molded (lamination molding) to obtain a laminate. In addition, the method of lamination molding and its molding conditions are the same as the method and molding conditions of lamination molding for the above-described laminated board and metal foil-clad laminated board. Next, the laminate is subjected to perforation processing for through holes and via holes, and a plating metal film is formed on the walls of the holes thus formed to connect the conductor layer (built-in circuit) and the metal foil for the outer layer circuit. Next, the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to manufacture an outer layer substrate having a conductor layer (outer layer circuit). In this way, a printed wiring board is manufactured.

In addition, when a metal foil-clad laminate is not used, a printed wiring board may be manufactured by forming a conductor layer that becomes a circuit on the insulating layer. At this time, electroless plating may be used to form the conductor layer.

Example

Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

(Preparation Example 1) Synthesis of cyclic carbodiimide compound

200 ml of o-nitrophenol (0.11 mol), pentaerythrityltetrabromide (0.025 mol), potassium carbonate (0.33 mol), and N,N-dimethylformamide (DMF) were mixed with a stirring device and a heating device. It was injected into the reaction apparatus under N ₂ atmosphere and reacted at 130°C for 12 hours. After that, DMF was removed under reduced pressure, the obtained solid was dissolved in 200 ml of dichloromethane, and the liquid separation operation was performed three times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and dichloromethane was removed under reduced pressure to obtain an intermediate product (nitroform).

Next, the obtained intermediate product (nitrobody, 0.1 mol), 5% palladium carbon (Pd/C) (2 g), and 400 ml of ethanol/dichloromethane (70/30) were injected into a reaction device equipped with a stirring device. Then, hydrogen substitution was performed five times, and the reaction was carried out at 25°C with hydrogen always supplied, and the reaction was terminated when the reduction in hydrogen ceased. Pd/C was recovered, the mixed solvent was removed, and an intermediate product (amine body) was obtained.

Next, triphenylphosphine dibromide (0.11 mol) and 150 ml of 1,2-dichloroethane were injected into a reaction device equipped with a stirring device, a heating device, and a dropping funnel under an N ₂ atmosphere, and stirred. Thereto, a solution of the intermediate product (amine form, 0.025 mol) and triethylamine (0.25 mol) dissolved in 50 ml of 1,2-dichloroethane was slowly added dropwise at 25°C. After completion of dropwise addition, reaction was performed at 70°C for 5 hours. After that, the reaction solution was filtered, and the filtrate was subjected to liquid separation with 100 ml of water 5 times. The organic layer was dehydrated with 5 g of sodium sulfate, and 1,2-dichloroethane was removed under reduced pressure to obtain an intermediate product (triphenylphosphine body).

Next, in a reaction apparatus equipped with a stirring device and a dropping funnel, di-tert-butyldicarbonate (0.11 mol), N,N-dimethyl-4-aminopyridine (0.055 mol), and dichloromethane 150% were added in a N ₂ atmosphere. ml was injected and stirred. There, 100 ml of dichloromethane in which the intermediate product (0.025 mol) was dissolved was slowly added dropwise at 25°C. After dropwise addition, it was allowed to react for 12 hours. Afterwards, dichloromethane was removed and the obtained solid was purified to obtain a cyclic carbodiimide compound.

(Example 1)

In a three-necked flask equipped with a thermometer and Dimroth, 5.0 parts by mass of diallylbisphenol A (DABPA, Daiwa Chemical Industry Co., Ltd.), 5.4 parts by mass of biscresol fluorene (BCF, Osaka Gas Chemical Co., Ltd.), and epoxy-modified Silicone (B) 1 (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g/mol) 3.7 parts by mass, epoxy modified silicone (B) 2 (KF-105, Shin-Etsu Chemical Co., Ltd., functional group Equivalent weight 490 g/mol) 11.0 parts by mass, biphenyl type epoxy resin (C) 1 (YL-6121H, Mitsubishi Chemical Co., Ltd.) 4.9 parts by mass, propylene glycol monomethyl ether acetate as solvent (DOWANOLPMA, Dow Chemical Nippon) Note)) 30 parts by mass were added, heated and stirred in an oil bath to 120°C. After confirming that the raw material was dissolved in the solvent, 0.3 parts by mass of imidazole catalyst g1 (TBZ, Shikoku Chemical Industry Co., Ltd.) was added, the temperature was raised to 140 ° C., stirred for 5 hours, and after cooling, the phenoxy polymer solution (solid content 50 mass%) was obtained (polymer production process).

In addition, diallylbisphenol A corresponds to “alkenylphenol (A)”, epoxy-modified silicone (B) 1 and epoxy-modified silicone (B) 2 correspond to “epoxy-modified silicone (B)”, and Phenyl type epoxy resin (C) 1 corresponds to “epoxy compound (C)”. In addition, the phenoxy polymer solution contains a polymer (E) containing structural units derived from alkenylphenol (A), structural units derived from epoxy modified silicone (B), and structural units derived from epoxy compound (C). ) was included. Hereinafter, polymer (E) is also called phenoxy polymer.

The content of the structural unit derived from epoxy-modified silicone (B) in the polymer (E) was 48.8 mass%.

The content of the structural units derived from the epoxy compound (C) relative to the total amount of the structural units derived from the epoxy modified silicone (B) and the structural units derived from the epoxy compound (C) was 25% by mass.

Measurement of weight average molecular weight Mw:

The weight average molecular weight Mw of the phenoxy polymer obtained as described above was measured as follows. 20 μL of 0.5 g of the phenoxy polymer solution dissolved in 2 g of THF was injected into high-performance liquid chromatography (manufactured by Shimadzu Corporation, pump: LC-20AD) and analyzed. The columns are Shodex GPC KF-804 (length 30 cm ), a total of 4 Shodex GPC KF-801 (length 30 cm . The weight average molecular weight Mw was determined using standard polystyrene as a standard material by GPC method. The weight average molecular weight Mw of the phenoxy polymer measured as described above was 12,000.

30 parts by mass of this phenoxy polymer solution (solid content conversion), 14 parts by mass of a novolak-type cyanate ester compound (PT-30, Ronder Co., Ltd.), and a novolak-type maleimide compound (BMI-2300, Daiwa Chemical Industry Co., Ltd.) Note)) 17 parts by mass, bismaleimide compound (BMI-80, K.I Chemical Co., Ltd.) 6 parts by mass, naphthalenecresol novolac type epoxy compound (HP-9540, DIC Co., Ltd.) 28 parts by mass, preparation example 5 parts by mass of the cyclic carbodiimide compound obtained in 1, 140 parts by mass of spherical silica (SC-2050MB, Admatex Co., Ltd.), 1 part by mass of wetting and dispersing agent (DISPERBYK-161, Big Chemi Japan Co., Ltd.), A varnish was obtained by mixing 5 parts by mass of a silane coupling agent (KMB-403, Shin-Etsu Chemical Co., Ltd.). This varnish was impregnated and coated on S glass woven fabric (thickness 100 μm), heated and dried at 165°C for 5 minutes, and a prepreg with a resin composition solid content (including filler) of 47.4% by mass was obtained (prepreg manufacturing process) .

(Example 2)

In the prepreg manufacturing process, 14 parts by mass of a novolak-type cyanate ester compound (PT-30, Ronder Co., Ltd.) is replaced by 13 parts by mass, and 17 parts by mass of a novolac-type maleimide compound (BMI-2300, Daiwa Chemical Industry Co., Ltd.) 16 parts by mass, bismaleimide compound (BMI-80, K.I Chemical Co., Ltd.) 6 parts by mass, 5 parts by mass, naphthalenecresol novolac type epoxy compound (HP-9540, DIC Co., Ltd.) 28 parts by mass, 26 parts by mass. A prep with a resin composition solid content (including filler) of 47.4% by mass was prepared in the same manner as in Example 1, except that 5 parts by mass of the cyclic carbodiimide compound obtained in Production Example 1 was changed to 10 parts by mass. Got the leg.

(Example 3)

In the polymer production process, 5.0 parts by mass of diallylbisphenol A (DABPA, Daiwa Chemical Industry Co., Ltd.) was modified to 5.1 parts by mass, and 5.4 parts by mass of bisresol fluorene (BCF, Osaka Gas Chemical Co., Ltd.) was modified to 5.6 parts by mass. Silicone (B) 1 (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g/mol) 3.7 parts by mass to 4.2 parts by mass, epoxy-modified silicone (B) 2 (KF-105, Shin-Etsu Chemical Co., Ltd.) ), functional group equivalent weight 490 g/mol), Example 1, except that 11.0 parts by mass were changed to 8.5 parts by mass, and 4.9 parts by mass of biphenyl type epoxy resin (C) 1 (YL-6121H, Mitsubishi Chemical Co., Ltd.) was changed to 5.6 parts by mass. A phenoxy polymer solution (solid content: 50% by mass) was obtained through the same operation as above (polymer production step).

After heating this phenoxy polymer solution to 100°C in an oil bath, 1.0 parts by mass of aminotriazine novolak (LA-3018) was added, stirred for 2 hours, and after cooling, a modified phenoxy polymer solution (solid content: 50 mass%). was obtained (polymer modification process). In addition, the modified phenoxy polymer solution contains a structural unit derived from alkenylphenol (A), a structural unit derived from epoxy modified silicone (B), a structural unit derived from an epoxy compound (C), and aminotriazinno. A polymer (E) containing structural units derived from rockfish was contained. The weight average molecular weight Mw of the modified phenoxy polymer measured in the same manner as above was 12,000. The polymer modification process may be performed continuously with the polymer production process.

30 parts by mass of this modified phenoxy polymer solution (solid content conversion), 8 parts by mass of a novolak-type maleimide compound (BMI-2300, Daiwa Chemical Industry Co., Ltd.), and a bismaleimide compound (BMI-80, K.I Chemical Co., Ltd.) Note)) 8 parts by mass, naphthylene ether type epoxy compound (HP-6000, DIC Co., Ltd.) 25 parts by mass, naphthol aralkyl type phenol compound (SN495V, Nittetsu Chemical Co., Ltd.) 24 parts by mass, Preparation Example 1 5 parts by mass of the cyclic carbodiimide compound obtained from , 200 parts by mass of spherical silica (SC-2050MB, Admatex Co., Ltd.), 1 part by mass of silane, wetting and dispersing agent (DISPERBYK-161, Big Chemi Japan Co., Ltd.) A varnish was obtained by mixing 5 parts by mass of a coupling agent (KMB-403, Shin-Etsu Chemical Co., Ltd.). This varnish was impregnated and coated on S glass woven fabric (thickness 100 μm), heated and dried at 150°C for 3 minutes, and a prepreg with a resin composition solid content (including filler) of 48.8% by mass was obtained (prepreg manufacturing process) .

(Example 4)

To 30 parts by mass (solid content conversion) of the modified phenoxy polymer solution obtained in the same manner as in Example 3, 7.5 parts by mass of a novolak-type maleimide compound (BMI-2300, Daiwa Chemical Industry Co., Ltd.), and a bismaleimide compound (BMI) -80, K.I Chemical Co., Ltd.) 7.5 parts by mass, naphthylene ether type epoxy compound (HP-6000, DIC Co., Ltd.) 23 parts by mass, naphthol aralkyl type phenolic compound (SN495V, Nittetsu Chemical Co., Ltd.) 22 parts by mass, 10 parts by mass of the cyclic carbodiimide compound obtained in Production Example 1, spherical silica (SC-2050MB, Admatex Co., Ltd.) 200 parts by mass, wetting and dispersing agent (DISPERBYK-161, Big Chemi Japan Co., Ltd. )) 1 part by mass and 5 parts by mass of a silane coupling agent (KMB-403, Shin-Etsu Chemical Co., Ltd.) were mixed to obtain a varnish. This varnish was impregnated and coated on S glass woven fabric (thickness 100 μm), heated and dried at 140°C for 3 minutes, and a prepreg with a resin composition solid content (including filler) of 48.8% by mass was obtained (prepreg manufacturing process) .

(Comparative Example 1)

30 parts by mass (in terms of solid content) of the phenoxy polymer solution obtained in the same manner as in Example 1, 15 parts by mass of a novolak-type cyanate ester compound (PT-30, Ronder Co., Ltd.), and a novolak-type maleimide compound (BMI) -2300, Daiwa Chemical Industry Co., Ltd.) 18 parts by mass, bismaleimide compound (BMI-80, K.I Chemical Co., Ltd.) 6 parts by mass, naphthalenecresol novolac type epoxy compound (HP-9540, DIC Co., Ltd.) ) 30 parts by mass, spherical silica (SC-2050MB, Admatex Co., Ltd.) 140 parts by mass, wetting and dispersing agent (DISPERBYK-161, Big Chemi Japan Co., Ltd.) 1 part by mass, silane coupling agent (KMB-403, Shin-Etsu Chemical Co., Ltd.) was mixed with 5 parts by mass to obtain a varnish. This varnish was impregnated and coated on S glass woven fabric (thickness 100 μm), heated and dried at 165°C for 5 minutes, and a prepreg with a resin composition solid content (including filler) of 47.4% by mass was obtained (prepreg manufacturing process) .

(Comparative Example 2)

30 parts by mass (in terms of solid content) of the modified phenoxy polymer solution obtained in the same manner as in Example 3, 9 parts by mass of a novolak-type maleimide compound (BMI-2300, Daiwa Chemical Industry Co., Ltd.), and a bismaleimide compound (BMI) -80, K.I Chemical Co., Ltd.) 9 parts by mass, naphthylene ether type epoxy compound (HP-6000, DIC Co., Ltd.) 27 parts by mass, naphthol aralkyl type phenol compound (SN495V, Nittetsu Chemical Co., Ltd.) 25 parts by mass, spherical silica (SC-2050MB, Admatex Co., Ltd.) 200 parts by mass, wetting and dispersing agent (DISPERBYK-161, Big Chemi Japan Co., Ltd.) 1 part by mass, silane coupling agent (KMB-403, Shinetsu Chemical Industry Co., Ltd.) was mixed with 5 parts by mass to obtain a varnish. This varnish was impregnated and coated on S glass woven fabric (thickness 100 μm), heated and dried at 140°C for 3 minutes, and a prepreg with a resin composition solid content (including filler) of 48.8% by mass was obtained (prepreg manufacturing process) .

(Comparative Example 3)

Novolak-type maleimide compound (BMI-2300, Daiwa Chemical Industry Co., Ltd.) 22.5 parts by mass, naphthylene ether-type epoxy compound (HP-6000, DIC Co., Ltd.) 35.1 parts by mass, naphthol aralkyl-type phenolic compound (SN495V) , Nittetsu Chemical Co., Ltd.) 33.5 parts by mass, 9.1 parts by mass of the cyclic carbodiimide compound obtained in Production Example 1, 200 parts by mass of spherical silica (SC-2050MB, Admatex Co., Ltd.), wetting and dispersing agent (DISPERBYK- A varnish was obtained by mixing 1 part by mass of No. 161 (Big Chemi Japan Co., Ltd.) and 5 parts by mass of a silane coupling agent (KMB-403, Shin-Etsu Chemical Co., Ltd.). This varnish was impregnated and coated on S glass woven fabric (thickness 100 μm), heated and dried at 140°C for 3 minutes, and a prepreg with a resin composition solid content (including filler) of 48.8% by mass was obtained (prepreg manufacturing process) .

(Comparative Example 4)

Novolak-type maleimide compound (BMI-2300, Daiwa Chemical Industry Co., Ltd.) 24.6 parts by mass, naphthylene ether-type epoxy compound (HP-6000, DIC Co., Ltd.) 38.6 parts by mass, naphthol aralkyl-type phenolic compound (SN495V) , Nittetsu Chemical Co., Ltd.) 36.8 parts by mass, spherical silica (SC-2050MB, Admatex Co., Ltd.) 200 parts by mass, wetting and dispersing agent (DISPERBYK-161, Big Chemi Japan Co., Ltd.) 1 part by mass, silane A varnish was obtained by mixing 5 parts by mass of a coupling agent (KMB-403, Shin-Etsu Chemical Co., Ltd.). This varnish was impregnated and coated on S glass woven fabric (thickness 100 μm), heated and dried at 140°C for 3 minutes, and a prepreg with a resin composition solid content (including filler) of 48.8% by mass was obtained (prepreg manufacturing process) .

[Production of metal foil-clad laminate]

Two prepregs obtained in each of Examples 1 to 4 and Comparative Examples 1 to 4 were overlapped, and an electrolytic copper foil (3EC-VLP, manufactured by Mitsui Metal Mining Co., Ltd.) having a thickness of 12 μm was placed above and below, and pressure was applied. Lamination molding was performed at 30 kgf/cm2 and a temperature of 230°C for 100 minutes to obtain a copper foil-clad laminate containing an insulating layer with a thickness of 0.2 mm as a metal foil-clad laminate. The properties of the obtained copper foil-clad laminate were evaluated by the method shown below. The results are shown in Table 1.

[Tg (glass transition temperature)]

After removing the copper foil on both sides of the metal foil-clad laminate (20 mm × 5 mm × 0.2 mm) obtained by the above method by etching, the glass transition temperature (Tg) was measured with a dynamic viscoelasticity measuring device (manufactured by TA Instruments) in accordance with JISC6481. , (unit: ℃) was measured.

[CTE (Coefficient of Linear Thermal Expansion)]

The coefficient of linear thermal expansion in the longitudinal direction of the glass cloth was measured for the insulating layer of the metal foil-clad laminate. Specifically, the copper foil on both sides of the copper foil-clad laminate (10 mm x 6 mm x 0.2 mm) obtained by the above method was removed by etching, and then heated in a constant temperature bath at 220°C for 2 hours to remove stress caused by molding. Thereafter, using a thermal expansion coefficient measuring device (horizontal dilatometer manufactured by Linseis), the temperature was raised from 40°C to 320°C at 10°C per minute, and the coefficient of linear thermal expansion (CTE) at 60°C to 260°C (unit: ppm/℃) was measured.

[Copper foil peel strength (copper foil adhesion)]

Using the copper foil-clad laminate (10 mm × 150 mm × 0.2 mm) obtained by the above method, the copper foil peel strength (copper foil adhesion) (unit: kN/m) was measured according to JIS C6481.

[endometriosis]

After removing the copper foil on both sides of the copper foil-clad laminate (50 mm Next, it is immersed in Concentrate Compact CP of Atotech Japan Co., Ltd., which is a conditioning liquid, at 80°C for 5 minutes, and finally, it is immersed in a reduction conditioner Securigant P500 of Atotech Japan Co., Ltd., which is a neutralizing liquid. It was immersed at 45°C for 10 minutes. This treatment was repeated three times. The mass of the copper foil-clad laminate before and after treatment was measured, and the mass reduction (unit: mass%) based on the sample mass before treatment was determined. The smaller the absolute value of the mass reduction amount, the better the desmear resistance.

This application is based on a Japanese patent application (Japanese patent application 2021-128756) filed with the Japan Patent Office on August 5, 2021, the contents of which are incorporated herein by reference.

Claims (25)

A curable composition containing alkenylphenol (A), epoxy modified silicone (B), an epoxy compound (C) other than the epoxy modified silicone (B), and a cyclic carbodiimide compound (D). According to claim 1,
The cyclic carbodiimide compound (D) has a cyclic structure represented by the following formula (D1),
A curable composition wherein the number of atoms forming the cyclic structure is 8 to 50.

(In the formula, L is a divalent to tetravalent bonding group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and the bonding group may contain a heteroatom and/or a substituent) The method of claim 1 or 2,
A curable composition wherein the content of the cyclic carbodiimide compound (D) is 2.0 to 15 parts by mass based on 100 parts by mass of the resin solid content. The method of claim 1 or 2,
The average number of phenol groups per molecule of the alkenylphenol (A) is 1 to 3, the average number of epoxy groups per molecule of the epoxy modified silicone (B) is 1 to 3, and one molecule of the epoxy compound (C) A curable composition having an average epoxy group number of 1 or more and less than 3. The method of claim 1 or 2,
A curable composition wherein the alkenylphenol (A) contains diallylbisphenol and/or dipropenylbisphenol. The method of claim 1 or 2,
A curable composition in which the epoxy-modified silicone (B) contains epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol. The method of claim 1 or 2,
A curable composition in which the epoxy-modified silicone (B) contains epoxy-modified silicone represented by the following formula (B1).

(In the formula, R ¹ each independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, R ² each independently represents an alkyl group or phenyl group having 1 to 10 carbon atoms, and n is 0. represents an integer from ∼ 100) The method of claim 1 or 2,
A curable composition in which the epoxy compound (C) contains 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.) A polymer containing a structural unit derived from alkenylphenol (A), a structural unit derived from epoxy modified silicone (B), and a structural unit derived from an epoxy compound (C) other than the epoxy modified silicone (B) ( E) Wow,
A curable composition containing a cyclic carbodiimide compound (D). According to clause 9,
A curable composition in which the weight average molecular weight of the polymer (E) is 3.0 × 10 ³ to 5.0 × 10 ⁴ . According to claim 9 or 10,
A curable composition wherein the content of the polymer (E) is 5 to 50% by mass based on 100% by mass of the resin solid content. According to claim 9 or 10,
The cyclic carbodiimide compound (D) has a cyclic structure represented by the following formula (D1),
A curable composition wherein the number of atoms forming the cyclic structure is 8 to 50.

(In the formula, L is a divalent to tetravalent bonding group that is an aliphatic group, an alicyclic group, an aromatic group, or a combination thereof, and the bonding group may contain a hetero atom and/or a substituent) According to claim 9 or 10,
A curable composition wherein the content of the cyclic carbodiimide compound (D) is 2.0 to 15 parts by mass based on 100 parts by mass of the resin solid content. According to claim 9 or 10,
The average number of phenol groups per molecule of the alkenylphenol (A) is 1 to 3, the average number of epoxy groups per molecule of the epoxy modified silicone (B) is 1 to 3, and one molecule of the epoxy compound (C) A curable composition having an average epoxy group number of 1 or more and less than 3. According to claim 9 or 10,
A curable composition wherein the alkenylphenol (A) contains diallylbisphenol and/or dipropenylbisphenol. According to claim 9 or 10,
A curable composition in which the epoxy-modified silicone (B) contains epoxy-modified silicone having an epoxy equivalent of 140 to 250 g/mol. According to claim 9 or 10,
A curable composition in which the epoxy-modified silicone (B) contains epoxy-modified silicone represented by the following formula (B1).

(In the formula, R ¹ each independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, R ² each independently represents an alkyl group or phenyl group having 1 to 10 carbon atoms, and n is 0. represents an integer from ∼ 100) According to claim 9 or 10,
A curable composition in which the epoxy compound (C) contains 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.) According to claim 9 or 10,
A curable composition further containing at least one member selected from the group consisting of alkenylphenol (A), epoxy-modified silicone (B), and epoxy compounds (C) other than the epoxy-modified silicone (B). According to claim 19,
A curable composition in which the epoxy compound (C) contains a naphthalenecresol novolak-type epoxy resin and/or a naphthylene ether-type epoxy resin. The method of claim 1 or 9,
A curable compound further containing at least one compound (H) selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound (F) other than the alkenylphenol (A), and an alkenyl substituted nadimide compound. Composition. The method of claim 1 or 9,
additionally containing inorganic fillers,
A curable composition wherein the inorganic filler includes one or more types selected from the group consisting of silica, boehmite, and alumina. With equipment,
A prepreg comprising the curable composition according to claim 1 or 9 impregnated or applied to the substrate. A laminate comprising the prepreg according to claim 23,
A metal foil-clad laminate comprising metal foil disposed on one or both sides of the laminate. An insulating layer comprising the prepreg according to claim 23,
A printed wiring board including a conductor layer formed on the surface of the insulating layer.