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

Abstract

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

Description

Technical Field

[0001] The present invention relates to a curable composition, a prepreg, a metal foil-clad laminate and a printed circuit board. Background Art

[0002] In recent years, with the advancement of higher functionality and smaller size in semiconductor packages, which are widely used in electronic devices, communications equipment, and personal computers, the integration and high-density packaging of components within semiconductor packages has accelerated. Consequently, the requirements for the various properties of printed circuit boards used in semiconductor packages have become increasingly stringent. Examples of the properties required of such printed circuit boards include low thermal expansion coefficient, chemical resistance, and peel strength.

[0003] Patent Document 1 discloses that a thermosetting resin composition containing a specific maleimide compound, a silicone compound having an epoxy group in its molecular structure, and a compound having a phenolic hydroxyl group has excellent heat resistance and low thermal expansion and is suitable for use in metal-clad laminates and multilayer printed wiring boards.

[0004] Patent Document 2 discloses a manufacturing method, which makes polymaleimide, an addition polymer of diglycidyl polysiloxane represented by the following formula (I) and diallyl bisphenol represented by the following formula (II), and an allylated phenolic resin represented by the following formula (III) react in a specified ratio and under specified conditions to obtain a semiconductor sealing resin. According to the document, it is disclosed that: in the semiconductor sealing resin obtained by the above-mentioned manufacturing method, the polymaleimide has good compatibility with the above-mentioned addition polymer, and the cured product properties (such as high glass transition temperature, moisture resistance and heat strength) of the composition using the semiconductor sealing resin are excellent, and the reliability as a semiconductor sealing resin composition is high. In the document, it is disclosed that: the component b in the following formula (III) reacts with the maleimide group in the resin formation reaction with the polymaleimide, and is an important component for improving the compatibility of the polymaleimide and the polysiloxane.

[0005]

[0006] (Where 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.

[0007]

[0008] (Where R 4 represents an ether bond, a methylene group, a propylidene group, or a direct bond (single bond).

[0009]

[0010] (In the above formula, a, b, and c each represent the percentage of each component, satisfying 0<a, b, c<100 and a+b+c=100.)

[0011] Prior art literature

[0012] Patent Literature

[0013] Patent Document 1: Japanese Patent Application Laid-Open No. 2012-149154

[0014] Patent Document 2: Japanese Patent Application Laid-Open No. 4-4213 Summary of the Invention

[0015] Problems to be solved by the invention

[0016] As described in Patent Document 1, resin compositions containing a silicone compound having an epoxy group in its molecular structure and a thermosetting resin such as a maleimide compound exhibit excellent low thermal expansion properties. However, the present inventors have discovered that these resin compositions suffer from moldability issues due to insufficient compatibility between the silicone compound and the thermosetting resin. Furthermore, the present inventors have discovered that these resin compositions lack sufficient chemical resistance and metal foil peel strength (e.g., copper foil peel strength) when used to form metal-clad laminates.

[0017] On the other hand, the resin composition described in Patent Document 2 is used for semiconductor sealing, but has not been studied for low thermal expansion, copper foil peeling strength, and chemical resistance, which are required properties for printed wiring boards.

[0018] The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a curable composition, a prepreg, a metal foil-clad laminate and a printed wiring board having excellent low thermal expansion, copper foil peel strength and chemical resistance.

[0019] Solutions for solving problems

[0020] The present inventors have conducted intensive research to solve the above-mentioned problems. As a result, they have discovered that a curable composition comprising an alkenylphenol, an epoxy-modified silicone, an epoxy compound other than the epoxy-modified silicone, and a cyclic carbodiimide compound, or a curable composition comprising a polymer comprising a structural unit derived from an alkenylphenol, a structural unit derived from an epoxy-modified silicone, and a structural unit derived from an epoxy compound other than the epoxy-modified silicone, and a cyclic carbodiimide compound, can solve the above-mentioned problems, thereby completing the present invention.

[0021] That is, the present invention is as follows.

[0022] [1]

[0023] A curable composition comprising an alkenylphenol (A), an epoxy-modified silicone (B), an epoxy compound (C) other than the epoxy-modified silicone (B), and a cyclic carbodiimide compound (D).

[0024] [2]

[0025] The curable composition according to [1], wherein the cyclic carbodiimide compound (D) has a cyclic structure represented by the following formula (D1):

[0026] The number of atoms forming the aforementioned ring structure is 8 to 50.

[0027]

[0028] (In the formula, L is a divalent to tetravalent bonding group, and the bonding group is an aliphatic group, an alicyclic group, an aromatic group, or a group composed of these groups. The bonding group may optionally contain heteroatoms and / or substituents.)

[0029] 〔3〕

[0030] 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.

[0031] [4]

[0032] The curable composition according to any one of [1] to [3], wherein the average number of phenol groups per molecule of the alkenylphenol (A) is 1 or more and less than 3, the average number of epoxy groups per molecule of the epoxy-modified silicone (B) is 1 or more and less than 3, and the average number of epoxy groups per molecule of the epoxy compound (C) is 1 or more and less than 3.

[0033] 〔5〕

[0034] The curable composition according to any one of [1] to [4], wherein the alkenylphenol (A) contains diallylbisphenol and / or dipropylenebisphenol.

[0035] [6]

[0036] The curable composition according to any one of [1] to [5], wherein the epoxy-modified silicone (B) comprises an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g / mol.

[0037] [7]

[0038] The curable composition according to any one of [1] to [6], wherein the epoxy-modified silicone (B) contains an epoxy-modified silicone represented by the following formula (B1).

[0039]

[0040] (Where 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 having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 0 to 100.

[0041] 〔8〕

[0042] 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).

[0043]

[0044] (In formula (b2), R a Each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)

[0045] 〔9〕

[0046] A curable composition comprising a polymer (E) and a cyclic carbodiimide compound (D),

[0047] The polymer (E) contains a structural unit derived from an alkenylphenol (A), a structural unit derived from an epoxy-modified silicone (B), and a structural unit derived from an epoxy compound (C) other than the epoxy-modified silicone (B).

[0048]

[10]

[0049] The curable composition according to [9], wherein the weight average molecular weight of the polymer (E) is 3.0×10 3 ~5.0×10 4 .

[0050]

[11]

[0051] The curable composition according to [9] or

[10] , wherein the content of the polymer (E) is 5 to 50% by mass relative to 100% by mass of the resin solid content.

[0052]

[12]

[0053] The curable composition according to any one of [9] to

[11] , wherein the cyclic carbodiimide compound (D) has a cyclic structure represented by the following formula (D1):

[0054] The number of atoms forming the aforementioned ring structure is 8 to 50.

[0055]

[0056] (In the formula, L is a divalent to tetravalent bonding group, and the bonding group is an aliphatic group, an alicyclic group, an aromatic group, or a group composed of these groups. The bonding group may optionally contain heteroatoms and / or substituents.)

[0057]

[13]

[0058] 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.

[0059]

[14]

[0060] The curable composition according to any one of [9] to

[13] , wherein the average number of phenol groups per molecule of the alkenylphenol (A) is 1 or more and less than 3, the average number of epoxy groups per molecule of the epoxy-modified silicone (B) is 1 or more and less than 3, and the average number of epoxy groups per molecule of the epoxy compound (C) is 1 or more and less than 3.

[0061]

[15]

[0062] The curable composition according to any one of [9] to

[14] , wherein the alkenylphenol (A) contains diallylbisphenol and / or dipropylenebisphenol.

[0063]

[16]

[0064] The curable composition according to any one of [9] to

[15] , wherein the epoxy-modified silicone (B) comprises an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g / mol.

[0065]

[17]

[0066] The curable composition according to any one of [9] to

[16] , wherein the epoxy-modified silicone (B) contains an epoxy-modified silicone represented by the following formula (B1).

[0067]

[0068] (Where 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 having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 0 to 100.

[0069]

[18]

[0070] 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).

[0071]

[0072] (In formula (b2), R a Each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)

[0073]

[19]

[0074] The curable composition according to any one of [9] to

[18] , further comprising at least one selected from the group consisting of alkenylphenol (A), epoxy-modified silicone (B), and epoxy compounds (C) other than the epoxy-modified silicone (B).

[0075] 〔20〕

[0076] The curable composition according to

[19] , wherein the epoxy compound (C) comprises a naphthol novolac-type epoxy resin and / or a naphthyl ether-type epoxy resin.

[0077] 〔twenty one〕

[0078] The curable composition according to any one of [1] to

[20] , further comprising one or more compounds (H) selected from the group consisting of maleimide compounds, cyanate compounds, phenol compounds (F) other than the alkenylphenol (A), and alkenyl-substituted nadic imide compounds.

[0079] 〔twenty two〕

[0080] The curable composition according to any one of [1] to

[20] , further comprising an inorganic filler,

[0081] The inorganic filler includes one or more selected from the group consisting of silica, boehmite, and alumina.

[0082] 〔twenty three〕

[0083] A prepreg comprising: a substrate; and the curable composition according to any one of [1] to

[22] impregnated or coated on the substrate.

[0084] 〔twenty four〕

[0085] A metal foil-clad laminate comprising: a laminate containing the prepreg described in

[23] ; and a metal foil disposed on one or both sides of the laminate.

[0086] 〔25〕

[0087] A printed circuit board comprising: an insulating layer containing the prepreg described in

[23] ; and a conductive layer formed on the surface of the insulating layer.

[0088] Effects of the Invention

[0089] According to the present invention, a curable composition, a prepreg, a metal foil-clad laminate, and a printed wiring board having excellent low thermal expansion, copper foil peel strength, and chemical resistance can be provided. DETAILED DESCRIPTION

[0090] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “the present embodiment”) will be described in detail, but the present invention is not limited thereto and various modifications are possible without departing from the spirit and scope of the present invention.

[0091] As used herein, "resin solids" refers to the components of the curable composition of this embodiment excluding the solvent and filler, unless otherwise specified. "100 parts by mass of resin solids" means the total of the components of the curable composition excluding the solvent and filler is 100 parts by mass. Furthermore, "100% by mass of resin solids" means the total of the components of the curable composition excluding the solvent and filler is 100% by mass.

[0092] “Compatibility” in this specification refers to the following. In the composition of the first embodiment described in detail later, “excellent compatibility” means that in a mixture (such as a varnish) containing alkenylphenol (A), epoxy-modified silicone (B), epoxy compound (C), and cyclic carbodiimide compound (D), no liquid phase separation occurs. In addition, in the composition of the second embodiment described in detail later, “excellent compatibility” means that in a mixture (such as a varnish) containing a polymer (E) and a cyclic carbodiimide compound (D), no liquid phase separation occurs. The curable composition of this embodiment has excellent compatibility and suppresses liquid phase separation during the molding process, so that a molded body with excellent appearance can be obtained, and there is a tendency that the physical properties of the obtained molded body are also excellent in isotropy. It should be noted that in this specification, when referring to “the curable composition of this embodiment”, unless otherwise specified, both “the curable composition of the first embodiment” and “the curable composition of the second embodiment” are included.

[0093] <First embodiment>

[0094] [Curable composition of the first embodiment]

[0095] The curable composition of the first embodiment contains alkenylphenol (A), epoxy-modified silicone (B), an epoxy compound (C) other than the epoxy-modified silicone (B) (hereinafter also referred to as "epoxy compound (C)".), and a cyclic carbodiimide compound (D). The curable composition of the first embodiment containing these ingredients has excellent low thermal expansion, copper foil peel strength and chemical resistance. The reasons for improving each property are believed to be as follows, but the reasons are not limited to these. The cyclic carbodiimide compound (D) has a high melting point, so for example, at the temperature when making a prepreg (about 140°C), the reactivity with each thermosetting resin such as alkenylphenol (A), epoxy-modified silicone (B), epoxy compound (C) is low, thereby suppressing the deterioration of the flow characteristics of the curable composition. Furthermore, during press molding at a higher temperature, the cyclic carbodiimide compound (D) melts, and thermosetting resins such as alkenylphenol (A), epoxy-modified silicone (B), and epoxy compound (C) react with the cyclic carbodiimide compound (D), thereby forming a structure with a higher cross-linking density, thereby improving low thermal expansion, copper foil peel strength, and chemical resistance.

[0096] [Alkenylphenol (A)]

[0097] 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 this embodiment can exhibit excellent compatibility by containing alkenylphenol (A), thereby improving the balance between heat resistance and low thermal expansion.

[0098] There are no particular limitations on the alkenyl group, and examples thereof 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 exerting the effects of the present invention, the alkenyl group is preferably an allyl group and / or propenyl, 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 exerting 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. In addition, the bonding position of the alkenyl group on the phenolic aromatic ring is not particularly limited, and is preferably the ortho position (2, 6 positions).

[0099] The phenolic aromatic ring refers to an aromatic ring having one or more hydroxyl groups directly bonded thereto, and examples thereof 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 preferably 1.

[0100] The phenolic aromatic ring may also have a substituent other than an alkenyl group. Examples of such substituents include a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 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 such substituents directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 2. Furthermore, the bonding position of such a substituent on the phenolic aromatic ring is also not particularly limited.

[0101] Alkenylphenol (A) may have one or more structures in which one or more alkenyl groups are directly bonded to the phenolic aromatic ring. From the perspective of more effectively and reliably exerting the effects of the present invention, alkenylphenol (A) preferably has one or two structures in which one or more alkenyl groups are directly bonded to the phenolic aromatic ring, and preferably has two.

[0102] The alkenylphenol (A) may be, for example, a compound represented by the following formula (A1) or the following formula (A2).

[0103]

[0104] (In the formula, Rxa each independently represents an alkenyl group having 2 to 8 carbon atoms, Rxb each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, Rxc each independently represents an aromatic ring having 4 to 12 carbon atoms, Rxc may form a condensed structure with a benzene ring, and Rxc may be present or absent, and A represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, 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). When Rxc is absent, one benzene ring may contain two or more groups of Rxa and / or Rxb.)

[0105]

[0106] (In the formula, Rxd each independently represents an alkenyl group having 2 to 8 carbon atoms, Rxe each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and Rxf represents an aromatic ring having 4 to 12 carbon atoms. Rxf may form a condensed structure with a benzene ring. Rxf may or may not be present. When Rxf is absent, one benzene ring may contain two or more groups of Rxd and / or Rxe.)

[0107] In formula (A1) and formula (A2), the alkenyl group having 2 to 8 carbon atoms represented by Rxa and Rxd is not particularly limited, and examples thereof include vinyl, allyl, propenyl, butenyl, and hexenyl.

[0108] 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 given. In addition, in formula (A1) and formula (A2), when the groups represented by Rxc and Rxf are not present, for example, a compound containing a phenol ring as a phenolic aromatic ring can be given.

[0109] The C1-10 alkyl groups represented by Rxb and Rxe in formula (A1) and formula (A2) are not particularly limited, and examples thereof include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl, and branched alkyl groups such as isopropyl, isobutyl, and tert-butyl.

[0110] In formula (A1), the alkylene group having 1 to 6 carbon atoms represented by A is not particularly limited, and examples thereof include methylene, ethylene, trimethylene, and propylene. The aralkylene group having 7 to 16 carbon atoms represented by A is not particularly limited, and examples thereof include groups represented by the formula: -CH2-Ar-CH2-, -CH2-CH2-Ar-CH2-CH2-, or -CH2-Ar-CH2-CH2- (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 thereof include a phenylene ring.

[0111] From the viewpoint of more effectively and reliably exhibiting the effects of the present invention, the compound represented by formula (A2) preferably has Rxf as a benzene ring (a compound containing a dihydroxynaphthalene skeleton).

[0112] From the viewpoint of further improving compatibility, the alkenylphenol (A) is preferably an alkenylbisphenol in which one alkenyl group is bonded to each of the two phenolic aromatic rings of a bisphenol. From the same viewpoint, the alkenylbisphenol is preferably a diallylbisphenol in which one allyl group is bonded to each of the two phenolic aromatic rings of a bisphenol, and / or a diallylbisphenol in which one propenyl group is bonded to each of the two phenolic aromatic rings of a bisphenol.

[0113] The diallyl bisphenol is not particularly limited, and examples thereof include o,o'-diallyl bisphenol A ("DABPA" manufactured by Daiwa Kasei Industry Co., Ltd.), o,o'-diallyl bisphenol F, o,o'-diallyl bisphenol S, and o,o'-diallyl bisphenol fluorene. The dipropylene bisphenol is not particularly limited, and examples thereof include o,o'-dipropylene bisphenol A ("PBA01" manufactured by Gunei Chemical Industry Co., Ltd.), o,o'-dipropylene bisphenol F, o,o'-dipropylene bisphenol S, and o,o'-dipropylene bisphenol fluorene.

[0114] To more effectively and reliably exhibit the effects of the present invention, the average number of phenol groups per molecule of alkenylphenol (A) is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less. The average number of phenol groups is calculated by the following formula.

[0115]

[0116] Wherein, Ai represents the number of phenolic groups of the alkenylphenol having i phenolic groups in the molecule, Xi represents the ratio of the alkenylphenol having i phenolic groups in the molecule to the total alkenylphenol, X1+X2+…X n =1.

[0117] [Epoxy-modified silicone (B)]

[0118] The epoxy-modified silicone (B) is not particularly limited as long as it is a silicone compound or resin modified with an epoxy-containing group. The curable composition of the present embodiment has excellent low thermal expansion and chemical resistance due to the inclusion of the epoxy-modified silicone (B).

[0119] The silicone compound or resin is not particularly limited as long as it is a compound having a polysiloxane skeleton formed by repeated siloxane bonds. The polysiloxane skeleton may be a linear skeleton, a cyclic skeleton, or a reticular skeleton. Among them, a linear skeleton is preferred for more effectively and reliably exerting the effects of the present invention.

[0120] The epoxy group-containing group is not particularly limited, and examples thereof include groups represented by the following formula (a1).

[0121]

[0122] (Where R 0 represents an alkylene group (for example, an alkylene group having 1 to 5 carbon atoms, such as methylene, ethylene, and propylene), and X represents a monovalent group represented by the following formula (a2) or a monovalent group represented by the following formula (a3).

[0123]

[0124] The epoxy-modified silicone (B) preferably contains an epoxy-modified silicone having an epoxy equivalent weight of 140 to 250 g / mol. By including an epoxy-modified silicone (B) having an epoxy equivalent weight within this range, it exhibits superior compatibility, thereby tending to further improve low thermal expansion and chemical resistance in a well-balanced manner. For the same reason, the epoxy equivalent weight is preferably 145 to 245 g / mol, and more preferably 150 to 240 g / mol.

[0125] The epoxy-modified silicone (B) preferably contains two or more epoxy-modified silicones from the viewpoint of achieving better compatibility with thermosetting resins and further improving low thermal expansion properties and chemical resistance in a well-balanced manner. In this case, the two or more epoxy-modified silicones preferably have different epoxy equivalents, more preferably including an epoxy-modified silicone having an epoxy equivalent of 50 to 350 g / mol (hereinafter also referred to as "low-equivalent epoxy-modified silicone (B1')") and an epoxy-modified silicone having an epoxy equivalent of 400 to 4000 g / mol (hereinafter also referred to as "high-equivalent epoxy-modified silicone (B2')"). Even more preferably, including an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g / mol (low-equivalent epoxy-modified silicone (B1")) and an epoxy-modified silicone having an epoxy equivalent of 450 to 3000 g / mol (high-equivalent epoxy-modified silicone (B2")).

[0126] When the epoxy-modified silicone (B) contains two or more epoxy-modified silicones, the average epoxy equivalent of the epoxy-modified silicone (B) is preferably 140 to 3000 g / mol, more preferably 250 to 2000 g / mol, and even more preferably 300 to 1000 g / mol. The average epoxy equivalent is calculated by the following formula.

[0127]

[0128] (wherein, Ei represents the epoxy equivalent of one of the two or more epoxy-modified silicones, and Wi represents the ratio of the above epoxy-modified silicones in the epoxy-modified silicone (B), which is W1+W2+…W n =1)

[0129] From the viewpoint of having more excellent compatibility and further improving low thermal expansion properties and chemical resistance in a well-balanced manner, the epoxy-modified silicone (B) preferably contains an epoxy-modified silicone represented by the following formula (B1).

[0130]

[0131] (Where 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 having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 0 to 100.

[0132] In formula (B1), R 1 The alkylene group shown in can be any of linear, branched or cyclic. The number of carbon atoms in the alkylene group is preferably 1 to 12, more preferably 1 to 4. Examples of the alkylene group include methylene, ethylene or propylene. Among these, R 1 Preferred is propylene.

[0133] In formula (B1), R 1 The arylene group shown may also have a substituent. The number of carbon atoms in the arylene group is preferably 6 to 40, more preferably 6 to 20. Examples of the arylene group include phenylene, cyclohexylphenylene, hydroxyphenylene, cyanophenylene, nitrophenylene, naphthylene, biphenylene, anthrylene, pyrenylene, and fluorenylene. These groups may also contain an ether bond, a ketone bond, or an ester bond.

[0134] In formula (B1), R 1 The carbon number of the aralkylene group is preferably 7 to 30, more preferably 7 to 13. The aralkylene group is not particularly limited, and examples thereof include groups represented by the following formula (XI).

[0135]

[0136] (In formula (XI), * represents a connecting bond.)

[0137] In formula (B1), R 1 The group shown may further have a substituent, and examples of the substituent include a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, and a cyclic alkoxy group having 3 to 10 carbon atoms. Among these, R 1 A propylene group is particularly preferred.

[0138] In formula (B1), R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group. The above alkyl groups and phenyl groups may also have substituents. The alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic. There are no particular restrictions on the alkyl group, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl. Among these, R 2 Preferred is methyl or phenyl.

[0139] In formula (B1), n represents an integer of 0 or greater, for example, 1 to 100. From the viewpoint of achieving better compatibility and further improving low thermal expansion properties and chemical resistance in a well-balanced manner, n is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less.

[0140] From the perspective of achieving superior compatibility with thermosetting resins and further improving low thermal expansion properties and chemical resistance in a well-balanced manner, the epoxy-modified silicone (B) preferably contains two or more epoxy-modified silicones represented by formula (B1). In this case, the two or more epoxy-modified silicones preferably have different n, and more preferably contain an epoxy-modified silicone in which n in formula (B1) is 1 to 2 and an epoxy-modified silicone in which n in formula (B1) is 5 to 20.

[0141] From the viewpoint of more effectively and reliably exhibiting the effects of the present invention, the average number of epoxy groups per molecule of the epoxy-modified silicone (B) is preferably 1 or more and less than 3, and more preferably 1.5 or more and 2.5 or less.

[0142] The average number of epoxy groups was calculated by the following formula.

[0143]

[0144] (where Bi represents the number of epoxy groups in 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 total epoxy-modified silicone, Y1+Y2+…Y n =1)

[0145] From the viewpoint of exhibiting more excellent low thermal expansion properties and chemical resistance, the content of the epoxy-modified silicone (B) is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, further preferably 40 to 85% by mass, and even more preferably 50 to 80% by mass, relative to 100% by mass of the total of the epoxy-modified silicone (B) and the epoxy compound (C).

[0146] As the epoxy-modified silicone (B), a commercial product or a product produced by a known method may be used. Examples of commercial products include "X-22-163" and "KF-105" manufactured by Shin-Etsu Chemical Co., Ltd.

[0147] [Epoxy compound (C)]

[0148] The epoxy compound (C) is an epoxy compound other than the epoxy-modified silicone (B), more specifically, an epoxy compound without a polysiloxane skeleton. The curable composition of this embodiment exhibits superior compatibility, heat resistance, chemical resistance, copper foil peel strength, and insulation reliability by containing the epoxy compound (C).

[0149] As the epoxy compound (C), there is no particular limitation 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 and a polyfunctional epoxy compound having three or more epoxy groups in one molecule can be used. From the perspective of being able to exhibit better compatibility, heat resistance, chemical resistance, copper foil peel strength and insulation reliability, the epoxy compound (C) preferably contains a bifunctional epoxy compound and / or a polyfunctional epoxy compound.

[0150] The epoxy compound (C) in the curable composition of the present embodiment is not particularly limited, and a compound represented by the following formula (3a) can be used.

[0151]

[0152] (In formula (3a), Ar 3 Each independently represents a benzene ring or a naphthalene ring, Ar 4 represents a benzene ring, a naphthalene ring or a biphenyl ring, R 3a Each independently represents a hydrogen atom or a methyl group, k represents an integer of 1 to 50,

[0153] Here, Ar 3 The benzene ring or naphthalene ring in the ring may further have one or more substituents, and the substituents may be glycidyloxy groups not shown in the figure, or other substituents, such as alkyl groups having 1 to 5 carbon atoms, phenyl groups, etc.

[0154] Ar 4 The benzene ring, naphthalene ring or biphenyl ring in the ring may further have one or more substituents, which may be glycidyloxy groups or other substituents, such as alkyl groups having 1 to 5 carbon atoms, phenyl groups, etc.

[0155] Among the compounds represented by the above formula (3a), examples of bifunctional epoxy compounds include compounds represented by the following formula (b1).

[0156]

[0157] (In formula (b1), Ar 3 Each independently represents a benzene ring or a naphthalene ring, Ar 4 represents a benzene ring, a naphthalene ring or a biphenyl ring, R 3a each independently represents a hydrogen atom or a methyl group,

[0158] Here, Ar 3 The benzene ring or naphthalene ring in the may further have one or more substituents, and the substituents may be, for example, alkyl groups having 1 to 5 carbon atoms, phenyl groups, or other substituents other than glycidyloxy groups.

[0159] Ar 4 The benzene ring, naphthalene ring or biphenyl ring in the ring may also have one or more substituents, and the substituents may be, for example, alkyl groups having 1 to 5 carbon atoms, phenyl groups or other substituents other than glycidyloxy groups.

[0160] The compound represented by formula (3a) is preferably wherein Ar 4 A phenolic novolac-type epoxy resin substituted with at least one glycidyl ether oxy group. The phenolic novolac-type epoxy resin is not particularly limited, and examples thereof include a compound having a structure represented by the following formula (3-1) (a naphthalene skeleton-containing polyfunctional epoxy resin) and a naphthylcresol novolac-type epoxy resin.

[0161]

[0162] (where 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, R 31a Each independently represents a hydrogen atom or a methyl group, p represents an integer of 0 to 2, preferably 0 or 1, kz represents an integer of 1 to 50, and each ring may have a substituent other than a glycidyloxy group (e.g., an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group), Ar 31 and Ar 41 At least one of them represents a naphthalene ring.)

[0163] Examples of the compound having a structure represented by formula (3-1) include compounds having a structure represented by formula (3-2).

[0164]

[0165] (In the formula, R represents a methyl group, and kz has the same meaning as kz in the above formula (3-1).)

[0166] The naphthol cresol novolac-type epoxy resin is not particularly limited, but is preferably, for example, a cresol / naphthol novolac-type epoxy resin represented by the following formula (NE). It should be noted that the compound represented by the following formula (NE) is a random copolymer of a cresol novolac epoxy structural unit and a naphthol novolac epoxy structural unit, and both the cresol epoxy and the naphthol epoxy can be terminal.

[0167]

[0168] In the above formula (NE), m and n each represent an integer greater than 1. The upper limits of m and n and the ratio thereof are not particularly limited, but from the viewpoint of low thermal expansion, m:n (here, m+n=100) is preferably 30-50:70-50, and more preferably 45-55:55-45.

[0169] As the naphthyl cresol novolac type epoxy resin, a commercially available product or a product produced by a known method may be used. Examples of commercially available products include "NC-7000," "NC-7300," and "NC-7300L" manufactured by Nippon Kayaku Co., Ltd., and "HP-9540" and "HP-9500" manufactured by DIC Corporation. "HP-9540" is particularly preferred.

[0170] The compound represented by formula (3a) may be a compound that does not belong to the above-mentioned phenol novolac-type epoxy resin (hereinafter also referred to as "aralkyl-type epoxy resin").

[0171] As the aralkyl type epoxy resin, Ar in formula (3a) is preferably 3 is a naphthalene ring and Ar 4 A compound having a benzene ring (also called a "naphthol aralkyl type epoxy resin"), and Ar in formula (3a) 3 is a benzene ring and Ar 4 The compound is a biphenyl ring compound (also referred to as a "biphenyl aralkyl type epoxy resin"), and more preferably a biphenyl aralkyl type epoxy resin.

[0172] As the naphthol aralkyl type epoxy resin, a commercial product or a product produced by a known method may be used. Examples of commercial products include "HP-5000" and "HP-9900" manufactured by DIC Corporation, and "ESN-375" and "ESN-475" manufactured by Nippon Steel Chemical & Material Co., Ltd.

[0173] The biphenyl aralkyl type epoxy resin is preferably a compound represented by the following formula (3b).

[0174]

[0175] (wherein, ka represents an integer greater than 1, preferably 1 to 20, more preferably 1 to 6)

[0176] Among the compounds represented by the above formula (3b), examples of the bifunctional epoxy compound include compounds wherein ka in the formula (3b) is 1.

[0177] As the biphenyl aralkyl type epoxy resin, a commercial product or a product produced by a known method may be used. Examples of commercial products include "NC-3000," "NC-3000L," and "NC-3000FH" manufactured by Nippon Kayaku Co., Ltd.

[0178] Furthermore, as the epoxy compound (C) in the curable composition of this embodiment, a naphthalene-type epoxy resin (excluding compounds represented by formula (3a)) is preferably used. As the naphthalene-type epoxy resin, a naphthyl ether-type epoxy resin is preferred from the viewpoint of further improving heat resistance, chemical resistance, copper foil peel strength, and insulation reliability.

[0179] From the viewpoint of further improving heat resistance, chemical resistance, copper foil peel strength, and insulation reliability, the naphthyl ether epoxy resin is preferably a bifunctional epoxy compound represented by the following formula (3-3) or a polyfunctional epoxy compound represented by the following formula (3-4), or a mixture thereof.

[0180]

[0181] (Where R 13 Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., methyl or ethyl), or an alkenyl group having 2 to 3 carbon atoms (e.g., vinyl, allyl, or propenyl).

[0182]

[0183] (Where R 14 Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., methyl or ethyl), or an alkenyl group having 2 to 3 carbon atoms (e.g., vinyl, allyl, or propenyl).

[0184] A commercially available naphthyl ether epoxy resin may be used, or a product produced by a known method may be used. Examples of commercially available naphthyl ether epoxy resins include "HP-6000," "EXA-7300," "EXA-7310," "EXA-7311," "EXA-7311L," "EXA7311-G3," "EXA7311-G4," "EXA-7311G4S," and "EXA-7311G5" manufactured by DIC Corporation. HP-6000 is particularly preferred.

[0185] Examples of naphthalene-type epoxy resins other than those described above include, but are not limited to, compounds represented by the following formula (b3).

[0186]

[0187] (In formula (b3), R 3bEach independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (e.g., methyl or ethyl), an aralkyl group, a benzyl group, a naphthyl group, a naphthyl group containing at least one glycidyloxy group, or a naphthylmethyl group containing at least one glycidyloxy group, and n represents an integer greater than 0 (e.g., 0 to 2).

[0188] Examples of commercially available compounds represented by the formula (b3) include "HP-4032" (n=0 in the formula (b3)) and "HP-4710" (n=0, R in the formula (b3)) manufactured by DIC Corporation. 3b is a naphthylmethyl group containing at least one glycidyl ether oxy group) and the like.

[0189] Furthermore, 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 belonging to the above-mentioned epoxy compound (C)).

[0190] The biphenyl-type epoxy resin is not particularly limited, and examples thereof include compounds represented by the following formula (b2) (compound (b2)).

[0191]

[0192] (In formula (b2), each Ra independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)

[0193] In formula (b2), the alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic. Examples of the alkyl group include, but are not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl.

[0194] 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 alkyl groups, i.e., Ra. Specifically, a mixture of biphenyl-type epoxy resins having different numbers of alkyl groups, i.e., Ra, is preferred, and a mixture of a compound (b2) having 0 alkyl groups, i.e., Ra, and a compound (b2) having 4 alkyl groups, i.e., Ra, is more preferred.

[0195] Furthermore, as the epoxy compound (C) in the curable composition of the present embodiment, a dicyclopentadiene-type epoxy resin (excluding those belonging to the above-mentioned epoxy compound (C)) can be used.

[0196] The dicyclopentadiene-type epoxy resin is not particularly limited, and examples thereof include compounds represented by the following formula (3-5).

[0197]

[0198] (Where R 3cEach independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and k2 represents an integer from 0 to 10.

[0199] The compound represented by the above formula (3-5) is not particularly limited, and may be, for example, a compound represented by the following formula (b4).

[0200]

[0201] (In formula (b4), R 3c Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (e.g., a methyl group or an ethyl group).

[0202] Commercially available dicyclopentadiene epoxy resins or products produced by known methods may be used. Examples of commercially available dicyclopentadiene epoxy resins include "EPICRON HP-7200L," "EPICRON HP-7200," "EPICRON HP-7200H," and "EPICRON HP-7000HH," all manufactured by Dainippon Ink and Chemicals, Incorporated.

[0203] Among these, the epoxy compound (C) is preferably one or more selected from the group consisting of an epoxy resin represented by formula (3a), a naphthalene-type epoxy resin and a biphenyl-type epoxy resin, from the viewpoint of exhibiting better heat resistance, chemical resistance, copper foil peel strength and insulation reliability. In this case, it is preferred that the epoxy resin represented by formula (3a) includes a naphthol novolac-type epoxy resin, and the naphthalene-type epoxy resin includes a naphthyl ether-type epoxy resin.

[0204] As the epoxy compound (C), other epoxy resins that do not belong to the above-mentioned epoxy compounds may be contained.

[0205] Other epoxy resins are not particularly limited, and examples thereof include bisphenol-type epoxy resins, trisphenol methane-type epoxy resins, anthracene-type epoxy resins, glycidyl ester-type epoxy resins, polyol-type epoxy resins, isocyanurate ring-containing epoxy resins, fluorene-type epoxy resins, and epoxy resins composed of bisphenol A-type structural units and hydrocarbon-based structural units.

[0206] Among the above, as other epoxy resins, bisphenol-type epoxy resins may be contained from the viewpoint of further improving chemical resistance, copper foil peeling strength and insulation reliability. As the bisphenol-type epoxy resin, for example, diallyl bisphenol-type epoxy resins (such as diallyl bisphenol A epoxy resin, diallyl bisphenol E epoxy resin, diallyl bisphenol F epoxy resin, diallyl bisphenol S epoxy resin, etc.) may be used.

[0207] As the epoxy compound (C), among the above-mentioned epoxy compounds and epoxy resins, one kind may be used alone or two or more kinds may be used in combination.

[0208] In order to more effectively and reliably exhibit the effects of the present invention, the average number of epoxy groups per molecule of the epoxy compound (C) is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less. The average number of epoxy groups is calculated by the following formula.

[0209]

[0210] (where Ci represents the number of epoxy groups in 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 total epoxy compound, Z1+Z2+…Z n =1.)

[0211] From the viewpoint of exhibiting more excellent compatibility, heat resistance, chemical resistance, copper foil peel strength and insulation reliability, the content of the epoxy compound (C) is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, further preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass, relative to 100% by mass of the total amount of the epoxy-modified silicone (B) and the epoxy compound (C).

[0212] [Cyclic carbodiimide compound (D)]

[0213] 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. The curable composition of this embodiment, by containing the cyclic carbodiimide compound (D), maintains sufficient formability without deteriorating fluidity, has a high glass transition temperature (Tg), and exhibits excellent heat resistance, low thermal expansion, copper foil peel strength, and chemical resistance.

[0214] The cyclic structure has a carbodiimide group (-N=C=N-), and its first nitrogen atom is bonded to the second nitrogen atom through a bonding group. The number of atoms forming the cyclic structure is preferably 8 to 50, more preferably 10 to 30, and further preferably 10 to 20. Here, the number of atoms forming the cyclic structure refers to the number of atoms that directly constitute the cyclic structure. For example, if it is an 8-membered ring, the number of atoms forming the cyclic structure is 8, and if it is a 50-membered ring, the number of atoms forming the cyclic structure is 50. By making the number of atoms forming the cyclic structure 8 or more, the stability of the cyclic carbodiimide compound is good, and it has the advantages of being easy to store and easy to use. In addition, the synthesis of cyclic carbodiimide compounds with more than 50 atoms forming the cyclic structure is difficult.

[0215] The cyclic carbodiimide compound (D) preferably includes a cyclic structure represented by the following formula (D1).

[0216]

[0217] (In formula (D1), L is a divalent to tetravalent bonding group, and the bonding group is an aliphatic group, an alicyclic group, an aromatic group, or a group composed of a combination thereof. The bonding group may also contain a heteroatom and / or a substituent.)

[0218] Heteroatoms include O, N, S, and P. Two valences of the bonding group are used to form a cyclic structure. When L is a trivalent or tetravalent bonding group, L is bonded to the polymer or other cyclic structure via a single bond, a double bond, an atom, or an atomic group.

[0219] (Bonding Group L)

[0220] The bonding group L is preferably a divalent to tetravalent bonding group represented by the following formula (1-1), (1-2) or (1-3).

[0221]

[0222] In formula (1-1), Ar 101 and Ar 102 Each independently represents a di- to tetravalent aromatic hydrocarbon group having 5 to 15 carbon atoms, which may contain a heteroatom and a substituent.

[0223] As Ar 101 and Ar 102 The aromatic hydrocarbon group shown is not particularly limited, and examples thereof include an arylene group having 5 to 15 carbon atoms, an aromatic triyl group having 5 to 15 carbon atoms, and an aromatic tetrayl group having 5 to 15 carbon atoms, which may optionally have a heterocyclic structure containing a heteroatom. Here, examples of the arylene group (divalent) include phenylene and naphthalenediyl. Examples of the aromatic triyl group (trivalent) include benzenetriyl and naphthalenetriyl. Examples of the aromatic tetrayl group (quadrivalent) include benzenetetrayl and naphthalenetetrayl. 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, and the like.

[0224] As Ar 101 and Ar 102 , preferably phenylene, naphthalenediyl, benzenetriyl, naphthalenetriyl or benzenetetrayl, more preferably phenylene or benzenetriyl.

[0225] In formula (1-2), R 101 and R 102Examples thereof include, independently of one another, a di- to tetravalent aliphatic group having 1 to 20 carbon atoms (aliphatic hydrocarbon group), a di- to tetravalent alicyclic group having 3 to 20 carbon atoms (alicyclic hydrocarbon group), and combinations thereof, or combinations of these aliphatic groups and / or alicyclic groups with a di- to tetravalent aromatic group having 5 to 15 carbon atoms (aromatic hydrocarbon group).

[0226] As R 101 and R 102 The aliphatic group shown is not particularly limited, and examples thereof include alkylene groups having 1 to 20 carbon atoms, alkanetriyl groups having 1 to 20 carbon atoms, and alkanetetrayl groups having 1 to 20 carbon atoms. Examples of the alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, dodecylene, and hexadecylene. Examples of the alkanetriyl group include methanetriyl, ethanetriyl, propanetriyl, butanetriyl, pentanetriyl, hexanetriyl, heptanetriyl, octanetriyl, nonanetriyl, decanetriyl, dodecylene, and hexadecylene. Examples of the alkanetetrayl group include methanetetrayl, ethanetetrayl, propanetetrayl, butanetetrayl, pentanetetrayl, hexanetetrayl, heptanetetrayl, octanetetrayl, nonanetetrayl, decanetetrayl, dodecylene, and hexadecylene. These aliphatic groups may have a substituent, and 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, and an aldehyde group.

[0227] Examples of the alicyclic group include cycloalkylene groups having 3 to 20 carbon atoms, cycloalkanetriyl groups having 3 to 20 carbon atoms, and cycloalkanetetrayl groups having 3 to 20 carbon atoms. Examples of the cycloalkylene group include cyclopropylene, cyclobutylene, cyclopentylene, cyclohexylene, cycloheptylene, cyclooctylene, cyclononylene, cyclodecylene, cyclododecylene, and cyclohexadecylene. Examples of the cycloalkanetriyl group include cyclopropanetriyl, cyclobutanetriyl, cyclopentanetriyl, cyclohexanetriyl, cycloheptanetriyl, cyclooctanetriyl, cyclononanetriyl, cyclodecanetriyl, cyclododecanetriyl, and cyclohexadecanetriyl. Examples of the cycloalkane tetrayl group include cyclopropane tetrayl group, cyclobutane tetrayl group, cyclopentane tetrayl group, cyclohexane tetrayl group, cycloheptane tetrayl group, cyclooctane tetrayl group, cyclononane tetrayl group, cyclodecane tetrayl group, cyclododecane tetrayl group, and cyclohexadecane tetrayl group. These alicyclic groups may have substituents. Examples of the substituents include alkyl groups having 1 to 20 carbon atoms, aryl groups having 6 to 15 carbon atoms, halogen atoms, nitro groups, amide groups, hydroxyl groups, ester groups, ether groups, and aldehyde groups.

[0228] Examples of the aromatic group include an arylene group having 5 to 15 carbon atoms, an arene triyl group having 5 to 15 carbon atoms, and an arene tetrayl group having 5 to 15 carbon atoms, which may optionally have a heterocyclic structure containing a heteroatom. Examples of the arylene group include a phenylene group and a naphthalenediyl group. Examples of the arene triyl group (trivalent) include a benzene triyl group and a naphthalene triyl group. Examples of the arene tetrayl group (quadrivalent) include a benzene tetrayl group and a naphthalene tetrayl 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, and the like.

[0229] As R 101 and R 102 , preferably each independently represents a methylene group, an ethylene group, a vinylidene group, a phenylene group or an ether group, more preferably a methylene group, a phenylene group or an ether group.

[0230] In formulas (1-1) and (1-2), X 1 and X 2 Each is independently a di- to tetravalent aliphatic group having 1 to 20 carbon atoms, a di- to tetravalent alicyclic group having 3 to 20 carbon atoms, a di- to tetravalent aromatic group having 5 to 15 carbon atoms, or a combination thereof, which may contain a heteroatom and / or a substituent.

[0231] As X 1 and X 2 Examples of the aliphatic group, alicyclic group and aromatic group in the above R 101 and R 102 The same as those exemplified in . 1 and X 2 It is preferably a methylene group, an ethylene group, a vinylene group or an ether group, and more preferably a methylene group or an ether group.

[0232] In formulas (1-1) and (1-2), s and k are each independently preferably 0 to 10, more preferably 0 to 3, and even more preferably 0 to 1. Synthesis of cyclic carbodiimide compounds in which s and k each exceed 10 is difficult and the cost increases. In addition, when s or k is 2 or more, X as a repeating unit is 1 or X 2 Can be used with other X 1 or X 2 different.

[0233] In formula (1-3), X 3 It is a di- to tetravalent aliphatic group having 1 to 20 carbon atoms, a di- to tetravalent alicyclic group having 3 to 20 carbon atoms, a di- to tetravalent aromatic group having 5 to 15 carbon atoms, or a combination thereof, which may contain a heteroatom and / or a substituent.

[0234] As X 3Examples of the aliphatic group, alicyclic group and aromatic group in the above R 101 、R 102 、X 1 and X 2 The same as those exemplified in . 3 , preferably a methylene group, an ethylene group, a vinylene group or an ether group, more preferably a methylene group or an ether group.

[0235] In addition, Ar 101 、Ar 102 、R 101 、R 102 、X 1 、X 2 and X 3 It may have a heteroatom selected from an O atom, a N atom, an S atom, and a P atom. When the heteroatom is a N atom, the N atom is present in the form of a nitro group and / or an amide group.

[0236] When L is a divalent bonding group, Ar 101 、Ar 102 、R 101 、R 102 、X 1 、X 2 and X 3 All are divalent groups. When L is a trivalent bonding group, Ar 101 、Ar 102 、R 101 、R 102 、X 1 、X 2 and X 3 When L is a tetravalent bonding group, Ar 101 、Ar 102 、R 101 、R 102 、X 1 、X 2 and X 3 One of them is a tetravalent group, or Ar 101 、Ar 102 、R 101 、R 102 、X 1 、X 2 and X 3 Two of them are trivalent groups.

[0237] As an embodiment in which L is a trivalent or tetravalent bonding group and L is bonded to another cyclic structure having a carbodiimide group, an embodiment in which two or more cyclic structures represented by formula (1) are bonded via a common portion having 1 to 15 carbon atoms (preferably 1 to 12 carbon atoms) selected from a spiro structure, a single bond, an alkylene ring structure having 1 to 10 carbon atoms, an aromatic ring structure having 6 to 10 carbon atoms, a cycloalkane ring structure having 4 to 12 carbon atoms, and the like can be mentioned. Specific examples of such an embodiment are shown in the following formulas (2), (4), and (5).

[0238]

[0239] The cyclic carbodiimide compound (D) may be a cyclic carbodiimide compound represented by the following formula (i). 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.

[0240]

[0241] (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 Xa is divalent, q is 0, and when Xa is tetravalent, q is 1. Ar 201 ~Ar 204 Each is independently an aromatic hydrocarbon group. These aromatic hydrocarbon groups may have an alkyl group having 1 to 6 carbon atoms or a phenyl group as a substituent.

[0242]

[0243] (In formula (i-1), n is an integer from 1 to 6.)

[0244]

[0245] (In formula (i-2), m and n are each independently an integer of 0 to 3.)

[0246]

[0247] (In formula (i-3), R 301 and R 302 Each independently represents an alkyl group having 1 to 6 carbon atoms or a phenyl group.)

[0248]

[0249] In addition, as the cyclic carbodiimide compound represented by the above formula (i), compounds having the following structural formulas are exemplified.

[0250]

[0251] From the perspective of achieving higher glass transition temperature (Tg), chemical resistance, and heat resistance, the cyclic carbodiimide compound (D) preferably comprises a polycyclic carbodiimide compound containing two or more carbodiimide groups per molecule. From the perspective of achieving higher curing performance, the cyclic carbodiimide compound (D) more preferably comprises a polycyclic carbodiimide compound containing two or three carbodiimide groups per molecule. These polycyclic carbodiimide compounds may be used alone or in combination of two or more.

[0252] Examples of polycyclic carbodiimide compounds include those containing two or more carbodiimide groups in one molecule among the above-mentioned carbodiimide compounds. Among these, compounds represented by the following formula (D2) are preferred from the viewpoint of having higher glass transition temperature (Tg), chemical resistance, and heat resistance.

[0253]

[0254] (In formula (D2), X is a tetravalent group represented by the following formula (3), Ar 1 ~Ar 4 Each independently represents a divalent bonding group that is a phenylene group (e.g., o-phenylene) or a naphthalenediyl group (e.g., 1,2-naphthalenediyl), and the bonding group 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, and an aldehyde group. Furthermore, these bonding groups may have a heterocyclic structure containing a heteroatom.

[0255]

[0256] From the viewpoint of achieving better heat resistance, the cyclic carbodiimide compound (D) is preferably a compound represented by the following formula (D3).

[0257]

[0258] These cyclic carbodiimide compounds (D) can be produced by a known method (for example, the method described in International Publication No. 2010 / 071213 pamphlet).

[0259] 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, relative to 100 parts by mass of the resin solids. When the content of the cyclic carbodiimide compound (D) is 1.0 parts by mass or greater, heat resistance, low thermal expansion, copper foil peel strength, and chemical resistance tend to be more excellent. When the content of the cyclic carbodiimide compound (D) is 30 parts by mass or less, flame retardancy tends to be more excellent.

[0260] [Compound (H)]

[0261] In order to further improve low thermal expansion properties, chemical resistance, and copper foil peel strength, the curable composition of this embodiment preferably further contains 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 nadic imide compounds. The compound (H) is not particularly limited, but is preferably difunctional or higher, and may be polyfunctional or higher.

[0262] The content of the compound (H) in the curable composition of the present embodiment is preferably 10 to 80 mass %, more preferably 20 to 60 mass %, and even more preferably 30 to 50 mass %, relative to 100 mass % of the resin solid content.

[0263] [Maleimide compound]

[0264] From the viewpoint of further improving low thermal expansion and chemical resistance, the curable composition of the present embodiment preferably contains a maleimide compound. As the maleimide compound, there is no particular limitation as long as it is a compound having one or more maleimide groups in one molecule, and examples thereof include a monomaleimide compound having one maleimide group in one molecule (e.g., N-phenylmaleimide, N-hydroxyphenylmaleimide, etc.), a polymaleimide compound having two or more maleimide groups in one molecule (e.g., bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-1-oxadiazole)-1-propane) and bis(3-ethyl-5-methyl-1-oxadiazole)-1-propane). bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane), m-phenylenebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimido-(2,2,4-trimethyl)hexane, a maleimide compound represented by the following formula (H1a), a maleimide compound represented by the following formula (H1b), prepolymers of these maleimide compounds and amine compounds, and the like.

[0265]

[0266] (In the formula, R5 each independently represents a hydrogen atom or a methyl group, and n1 represents an integer greater than 1.)

[0267] n1 is 1 or more, preferably 1-100, and more preferably 1-10.

[0268] These maleimide compounds may be used alone or in combination of two or more. Among them, from the viewpoint of further improving low thermal expansion and chemical resistance, the maleimide compound preferably includes at least one selected from the group consisting of bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, the maleimide compound represented by formula (H1a), and the maleimide compound represented by the following formula (H1b).

[0269]

[0270] (In formula (H1b), R 13 Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, n 4 represents an integer greater than or equal to 1 and less than or equal to 10.)

[0271] The maleimide compound may be a commercially available product or a product produced by a known method. Examples of commercially available maleimide compounds include "BMI-70," "BMI-80," and "BMI-1000P" manufactured by K.I. Chemical Industry Co., Ltd., "BMI-3000," "BMI-4000," "BMI-5100," "BMI-7000," and "BMI-2300" manufactured by Daiwa Kasei Industry Co., Ltd., and "MIR-3000" manufactured by Nippon Kayaku Co., Ltd.

[0272] 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 even more preferably 10 to 40 parts by mass per 100 parts by mass of the resin solids.

[0273] [Cyanate ester compound]

[0274] In order to further improve the low thermal expansion property and the copper foil peel strength, the curable composition of the present embodiment preferably contains a cyanate compound. The cyanate compound is not particularly limited as long as it is a compound having two or more cyano groups (cyanate groups) in one molecule. Examples thereof include naphthol aralkyl cyanate compounds represented by the following formula (H2a), novolac cyanate compounds such as compounds represented by the following formula (H2b) other than the compound represented by the following formula (H2a), biphenyl aralkyl cyanate, diallyl bisphenol cyanate, bis(3,3-dimethyl-4-cyanophenyl)methane, bis(4-cyanophenyl) Methane, 1,3-dicyanobenzene, 1,4-dicyanobenzene, 1,3,5-tricyanobenzene, 1,3-dicyanonaphthalene, 1,4-dicyanonaphthalene, 1,6-dicyanonaphthalene, 1,8-dicyanonaphthalene, 2,6-dicyanonaphthalene, 2,7-dicyanonaphthalene, 1,3,6-tricyanonaphthalene, 4,4'-dicyanobiphenyl, bis(4-cyanophenyl)ether, bis(4-cyanophenyl)sulfide, bis(4-cyanophenyl)sulfone, 2,2-bis(4-cyanophenyl)propane. These cyanate compounds can be used alone or in combination of two or more. In the present embodiment, from the viewpoint of heat resistance, low thermal expansion and copper foil peel strength, the cyanate compound preferably includes a polyfunctional cyanate compound such as a naphthol aralkyl type cyanate compound and / or a novolac type cyanate compound.

[0275]

[0276] (In the formula, R6 each independently represents a hydrogen atom or a methyl group, and n2 represents an integer greater than 1.)

[0277]

[0278] In the formula, Rya each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, Ryb each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, Ryc each independently represents an aromatic ring having 4 to 12 carbon atoms, Ryc may form a condensed structure with a benzene ring, and Ryc may or may not exist, A 1a Each independently represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, 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). When Ryc is absent, two or more Rya and / or Ryb groups may be present on one benzene ring. n represents an integer of 1 to 20.

[0279] Among them, the cyanate compound preferably contains a compound represented by Formula (H2a) and / or Formula (H2b) from the viewpoint of further improving heat resistance, low thermal expansion properties, and copper foil peeling strength.

[0280] In formula (H2a), n2 represents an integer of 1 or greater, preferably an integer of 1 to 20, and more preferably an integer of 1 to 10.

[0281] In formula (H2b), the alkenyl group having 2 to 8 carbon atoms represented by Rya is not particularly limited, and examples thereof include vinyl, allyl, propenyl, butenyl, and hexenyl.

[0282] In formula (H2b), the C1-10 alkyl group represented by Ryb is not particularly limited, and examples thereof include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; and branched alkyl groups such as isopropyl, isobutyl, and tert-butyl.

[0283] In formula (H2b), A 1a The alkylene group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include methylene, ethylene, trimethylene, and propylene. 1a The aralkylene group having 7 to 16 carbon atoms is not particularly limited, and examples thereof include groups represented by the formula: -CH2-Ar-CH2-, -CH2-CH2-Ar-CH2-CH2-, or -CH2-Ar-CH2-CH2- (wherein Ar represents a phenylene group, a naphthylene group, or a biphenylene group). 1a The arylene group having 6 to 10 carbon atoms is not particularly limited, and examples thereof include a phenylene ring.

[0284] In formula (H2b), n represents an integer of 1 to 20, preferably an integer of 1 to 15, and more preferably an integer of 1 to 10.

[0285] The compound represented by formula (H2b) is preferably a compound represented by the following formula (H2c).

[0286]

[0287] (In the formula, 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 represents an integer of 1 to 10.)

[0288] These cyanate compounds can also be produced according to known methods. As a specific production method, for example, the method described in Japanese Patent Application Laid-Open No. 2017-195334 (particularly paragraphs 0052 to 0057) can be mentioned.

[0289] From the viewpoint of further improving low thermal expansion and copper foil peel strength, the content of the cyanate compound is preferably 3 to 70 parts by mass, more preferably 5 to 60 parts by mass, and even more preferably 10 to 40 parts by mass per 100 parts by mass of the resin solids.

[0290] (Phenolic compound (F) other than alkenylphenol (A))

[0291] For the viewpoint of showing more excellent chemical resistance, the curable composition of the present embodiment preferably contains phenolic compounds (F) other than alkenylphenol (A). As phenolic compound (F), it is not particularly limited, and bisphenol type phenolic resin (such as bisphenol A type resin, bisphenol E type resin, bisphenol F type resin, bisphenol S type resin, etc.), phenolic novolac resin (such as phenol novolac resin, naphthol novolac resin, cresol novolac resin, aminotriazine novolac resin described later, etc.), glycidyl ester phenolic resin, naphthalene type phenolic resin, anthracene type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, alicyclic phenolic resin, polyol type phenolic resin, aralkyl type phenolic resin, phenol modified aromatic hydrocarbon formaldehyde resin, fluorene type phenolic resin, etc. can be enumerated. These phenolic compounds can be used alone or in combination of two or more.

[0292] Among them, the phenol compound (F) preferably contains a bifunctional phenol compound having two phenolic hydroxyl groups in one molecule or an aminotriazine novolac resin from the viewpoint of exhibiting more excellent compatibility and chemical resistance.

[0293] The bifunctional phenol compound is not particularly limited, and examples thereof include bisphenol, biscresol, bisphenols having a fluorene skeleton (e.g., bisphenol having a fluorene skeleton, biscresol having a fluorene skeleton), biphenols (e.g., p,p'-biphenol), dihydroxydiphenyl ethers (e.g., 4,4'-dihydroxydiphenyl ether), dihydroxydiphenyl ketones (e.g., 4,4'-dihydroxydiphenyl ketone), dihydroxydiphenyl sulfides (e.g., 4,4'-dihydroxydiphenyl sulfide), and dihydroxyaromatic hydrocarbons (e.g., hydroquinone). These bifunctional phenol compounds can be used alone or in combination of two or more. Among these, from the perspective of exhibiting superior chemical resistance, the bifunctional phenol compound preferably includes at least one selected from the group consisting of bisphenol, biscresol, and bisphenols having a fluorene skeleton. From the same perspective as above, biscresol fluorene is preferred as the bisphenol having a fluorene skeleton.

[0294] Examples of the aralkyl-type phenol resin include compounds represented by the following formula (c2).

[0295]

[0296] (where Ar 1 Each independently represents a benzene ring or a naphthalene ring, Ar 2 represents a benzene ring, a naphthalene ring, or a biphenyl ring, R 2aEach independently represents a hydrogen atom or a methyl group, m represents an integer of 1 to 50, and each ring may have a substituent other than a hydroxyl group (for example, an alkyl group having 1 to 5 carbon atoms or a phenyl group).

[0297] From the viewpoint of further improving the peel strength of the copper foil, the compound represented by formula (c2) is preferably 1 is a naphthalene ring and Ar 2 A compound having a benzene ring (hereinafter also referred to as "naphthol aralkyl type phenolic resin"), and Ar in formula (c2) 1 is a benzene ring and Ar 2 A compound containing a biphenyl ring (hereinafter also referred to as a "biphenyl aralkyl type phenol resin").

[0298] The naphthol aralkyl type phenol resin is preferably a compound represented by the following formula (8).

[0299]

[0300] (In the formula, R7 each independently represents a hydrogen atom or a methyl group, and n3 represents an integer greater than 1.)

[0301] In formula (8), n3 represents an integer of 1 or greater, preferably an integer of 1 to 10, and more preferably an integer of 1 to 6.

[0302] The biphenyl aralkyl phenol resin is preferably a compound represented by the following formula (2c).

[0303]

[0304] (Where 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 represents an integer of 1 to 20 (preferably an integer of 1 to 6).

[0305] From the viewpoint of further improving low thermal expansion properties and chemical resistance, the phenol compound A' preferably contains a compound represented by the above formula (8).

[0306] The aralkyl phenolic resin may be a commercially available product or a product produced by a known method. Examples of commercially available aralkyl phenolic resins include "KAYAHARD GPH-65," "KAYAHARD GPH-78," and "KAYAHARD GPH-103" (biphenyl aralkyl phenolic resins) manufactured by Nippon Kayaku Co., Ltd., and "SN-495" (naphthol aralkyl phenolic resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.

[0307] As described above, the curable composition of this embodiment may also contain an aminotriazine novolac resin as the phenol compound (F). When the aminotriazine novolac resin is contained, there is a tendency for the terminal hydroxyl group and epoxy group generated by the reaction of the alkenylphenol (A), the epoxy-modified silicone (B), and the epoxy compound (C) other than the epoxy-modified silicone (B) to further react with the aminotriazine novolac resin, thereby increasing the number of terminal functional groups such as hydroxyl groups and amino groups. As a result, due to the presence of a large number of terminal functional groups highly reactive with thermosetting resins, there is a tendency to improve compatibility and crosslinking density, and thus improve copper foil peel strength.

[0308] The aminotriazine novolac resin is not particularly limited. However, from the viewpoint of improving the copper foil peel strength, a novolac resin having 2 to 20 phenolic hydroxyl groups relative to one triazine skeleton in the molecule is preferred, a novolac resin having 2 to 15 phenolic hydroxyl groups relative to one triazine skeleton in the molecule is more preferred, and a novolac resin having 2 to 10 phenolic hydroxyl groups relative to one triazine skeleton in the molecule is further preferred.

[0309] From the viewpoint of exhibiting more excellent compatibility, heat resistance and low thermal expansion, the content of the alkenylphenol (A) in the curable composition of the present embodiment is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, relative to 100 parts by mass of the total amount of the alkenylphenol (A), the epoxy-modified silicone (B), the epoxy compound (C) and the phenol compound (F).

[0310] From the viewpoint of achieving a well-balanced and more excellent low thermal expansion and chemical resistance, the content of the epoxy-modified silicone (B) in the curable composition of the present embodiment 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, relative to 100 parts by mass of the total amount of alkenylphenol (A), epoxy-modified silicone (B), epoxy compound (C), and phenol compound (F).

[0311] From the viewpoint of exhibiting superior compatibility, heat resistance, chemical resistance, copper foil peel strength, and insulation reliability, the content of the epoxy compound (C) in the curable composition of the present embodiment is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 15 to 25 parts by mass, relative to 100 parts by mass of the total amount of alkenylphenol (A), epoxy-modified silicone (B), epoxy compound (C), and phenol compound (F).

[0312] From the viewpoint of exhibiting superior chemical resistance, the content of the phenol compound (F) in the curable composition of the present embodiment 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, relative to 100 parts by mass of the total amount of alkenylphenol (A), epoxy-modified silicone (B), epoxy compound (C), and phenol compound (F).

[0313] In addition, when the curable composition does not contain the phenol compound (F), the content of each of the alkenylphenol (A), epoxy-modified silicone (B) and epoxy compound (C) mentioned above represents the content relative to 100 parts by mass of the total amount of alkenylphenol (A), epoxy-modified silicone (B) and epoxy compound (C).

[0314] (Alkenyl-substituted nadic imide compound)

[0315] To further improve heat resistance, the curable composition of this embodiment preferably contains an alkenyl-substituted nadic imide compound. The alkenyl-substituted nadic imide compound is not particularly limited as long as it has one or more alkenyl-substituted nadic imide groups per molecule, and examples thereof include the compound represented by the following formula (H4a).

[0316]

[0317] (In the formula, R1 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group or an ethyl group), and R2 represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, or a group represented by the following formula (3) or the following formula (4).)

[0318]

[0319] (In formula (3), R3 represents methylene, isopropylidene, CO, O, S or SO2.)

[0320]

[0321] (In formula (4), R4 each independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)

[0322] The alkenyl-substituted nadic acid imide compound represented by formula (H4a) may be a commercially available product or a product produced by a known method. Examples of commercially available products include "BANI-M" and "BANI-X" manufactured by Maruzen Petrochemical Co., Ltd.

[0323] From the viewpoint of further improving heat resistance, the content of the alkenyl-substituted nadic imide compound is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass, and even more preferably 10 to 30 parts by mass per 100 parts by mass of the resin solids.

[0324] <Second embodiment>

[0325] [Curable composition of the second embodiment]

[0326] The curable composition of the second embodiment contains a polymer (E) and a cyclic carbodiimide compound (D). The polymer (E) contains structural units derived from an alkenylphenol (A), structural units derived from an epoxy-modified silicone (B), and structural units derived from an epoxy compound (C) other than the epoxy-modified silicone (B). The alkenylphenol (A), epoxy-modified silicone (B), epoxy compound (C), and cyclic carbodiimide compound (D) are as described above in the first embodiment. In this specification, the curable composition of the first embodiment is a curable composition that does not contain a polymer (E), and is distinguished from the curable composition of the second embodiment.

[0327] The curable composition of the second embodiment may further contain, in addition to the polymer (E) and the cyclic carbodiimide compound (D), one or more compounds (H) selected from the group consisting of the maleimide compounds, cyanate compounds, phenol compounds (F) other than the alkenylphenol (A), and alkenyl-substituted nadic imide compounds, as needed. The compound (H) may be an unreacted component remaining after polymerization of the polymer (E) or a component added separately to the synthesized polymer (E).

[0328] The curable composition of the second embodiment may further contain one or more selected from the group consisting of alkenylphenol (A), epoxy-modified silicone (B), and epoxy compound (C) in addition to the polymer (E). In this case, the alkenylphenol (A), epoxy-modified silicone (B), or epoxy compound (C) contained in the curable composition of the second embodiment may be an unreacted component remaining after polymerization of the polymer (E), or may be a component separately added to the synthesized polymer (E).

[0329] The curable composition of the second embodiment has excellent low thermal expansion, copper foil peeling strength and chemical resistance. As for the reason for improving each characteristic, it is speculated that the mechanism of action is the same as that in the curable composition of the first embodiment. By controlling the reactivity of the cyclic carbodiimide compound (D) with the polymer (E) and the arbitrarily added compound (H) and other thermosetting resins generated by controlling the placement temperature of the curable composition, the compatibility and cross-linking reaction rate can be appropriately controlled, thereby improving low thermal expansion, copper foil peeling strength and chemical resistance. In addition, the curable composition of the second embodiment has better compatibility by containing polymer (E), can show better low thermal expansion, copper foil peeling strength and chemical resistance, and excellent insulation reliability. Polymer (E) can also exert sufficient compatibility even when mixed with a thermosetting resin with poor compatibility of silicone compounds. Thus, the curable composition comprising polymer (E) and a thermosetting resin can provide a uniform varnish and a cured product. In a cured product such as a prepreg obtained using the curable composition, the components are uniformly compatible, and variations in physical properties due to non-uniformity of the components are further suppressed.

[0330] [Polymer (E)]

[0331] The polymer (E) contains structural units derived from alkenylphenol (A), structural units derived from epoxy-modified silicone (B), and structural units derived from epoxy compounds (C). It may further contain structural units derived from one or more compounds (H) selected from the group consisting of maleimide compounds, cyanate compounds, phenol compounds other than alkenylphenol A, and alkenyl-substituted nadic imide compounds as needed. When the polymer (E) has structural units derived from compound (H), the compound (H) is preferably a bifunctional compound. It should be noted that, in this specification, "structural units derived from alkenylphenol (A)", "structural units derived from epoxy-modified silicone (B)", "structural units derived from epoxy compounds (C)" and "structural units derived from compound (H)" refer to structural units in the polymer (E) obtained by polymerizing the components of alkenylphenol (A), epoxy-modified silicone (B), epoxy compounds (C) and compound (H), and structural units formed by reactions that can impart the same structural units. Hereinafter, each structural unit is referred to as a structural unit (A), (B), (C), and (H).

[0332] The weight average molecular weight of the polymer (E) is preferably 3.0×10 3 ~5.0×10 4 , more preferably 3.0×10 3 ~2.0×10 4 By making the weight average molecular weight 3.0×10 3As described above, the curable composition of the second embodiment tends to exhibit more excellent low thermal expansion, copper foil peeling strength, and chemical resistance. 4 Hereinafter, the curable composition of the second embodiment tends to exhibit more excellent compatibility.

[0333] Relative to the gross mass of polymer (E), the content of structural unit (A) in polymer (E) is preferably 5 to 50% by mass. By making the content of structural unit (A) within the above range, the curable composition of the second embodiment has a tendency to exhibit more excellent compatibility, improve the balance between heat resistance and low thermal expansion. From the same viewpoint, the content of structural unit (A) is preferably 10 to 45% by mass, more preferably 15 to 40% by mass.

[0334] Relative to the gross mass of polymer (E), the content of structural unit (B) in polymer (E) is preferably 20 to 60% by mass. By making the content of structural unit (B) within the above range, the curable composition of the second embodiment has a tendency to exhibit better low thermal expansion and chemical resistance in a well-balanced manner. From the same viewpoint, the content of structural unit (B) is more preferably 25 to 55% by mass, and further preferably 30 to 50% by mass.

[0335] Structural unit (B) preferably comprises structural units derived from an epoxy-modified silicone having an epoxy equivalent weight of 50 to 350 g / mol (low-equivalent epoxy-modified silicone (B1')) and an epoxy-modified silicone having an epoxy equivalent weight of 400 to 4000 g / mol (high-equivalent epoxy-modified silicone (B2')). The low-equivalent epoxy-modified silicone (B1') and the high-equivalent epoxy-modified silicone (B2') are more preferably an epoxy-modified silicone having an epoxy equivalent weight of 140 to 250 g / mol (low-equivalent epoxy-modified silicone (B1")) and an epoxy-modified silicone having an epoxy equivalent weight of 450 to 3000 g / mol (high-equivalent epoxy-modified silicone (B2"), respectively.

[0336] The content of the structural unit (B) 1 derived from the low equivalent weight epoxy-modified silicone (B1′) in the polymer (E) is preferably 5 to 25% by mass, more preferably 7.5 to 20% by mass, and even more preferably 10 to 17% by mass, relative to the total mass of the polymer (E).

[0337] The content of the structural unit (B) 2 derived from the high equivalent weight epoxy-modified silicone (B2′) in the polymer (E) is preferably 15 to 55% by mass, more preferably 20 to 52.5% by mass, and even more preferably 25 to 50% by mass, relative to the total mass of the polymer (E).

[0338] 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 even more preferably 1.9 to 3.3. By having the above relationship between the contents of structural unit (B) 1 and structural unit (B) 2, the curable composition of the second embodiment tends to have further improved copper foil peel strength and chemical resistance.

[0339] The structural unit (C) in the polymer (E) is preferably a unit derived from at least one selected from the group consisting of the compound represented by the above formula (b1), the compound represented by the above formula (b2), the compound represented by the above formula (b3), and the compound represented by the above formula (b4).

[0340] The content of the structural unit (C) in the polymer (E) is preferably 5 to 40% by mass relative to the total mass of the polymer (E). If the content of the structural unit (C) is within the above range, the curable composition of the second embodiment has a tendency to have better compatibility, and to exhibit better heat resistance, chemical resistance, copper foil peel strength, and insulation reliability. From the same viewpoint, the content of the structural unit (C) is preferably 10 to 30% by mass, and more preferably 15 to 25% by mass.

[0341] Furthermore, the content of the structural unit (C) relative to the total mass of the structural unit (B) and the structural unit (C) is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, further preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass. By maintaining the above relationship between the contents of the structural unit (B) and the structural unit (C), the curable composition of the second embodiment tends to have better compatibility, and further improved heat resistance, chemical resistance, copper foil peel strength, and insulation reliability.

[0342] When polymer (E) has a structural unit derived from compound (H), the content of the structural unit (H) in polymer (E) is preferably 3 to 40% by mass relative to the total mass of polymer (E). By making the content of the structural unit (H) within the above range, the curable composition of the second embodiment has a tendency to exhibit more excellent low thermal expansion, chemical resistance and copper foil peel strength. From the same viewpoint, the content of the structural unit (H) is preferably 5 to 35% by mass, more preferably 10 to 30% by mass.

[0343] When the polymer (E) has a structural unit derived from a phenol compound (F) other than alkenylphenol (A) (hereinafter also referred to as "structural unit (F)"), the content of the structural unit (F) in the polymer (E) is preferably 5 to 30% by mass relative to the total mass of the polymer (E). By making the content of the structural unit (F) within the above range, the curable composition of the second embodiment tends to exhibit better chemical resistance. From the same viewpoint, the content of the structural unit (F) is more preferably 10 to 27.5% by mass, and even more preferably 10 to 25% by mass.

[0344] The alkenyl equivalent of polymer (E) is preferably 300 to 1500 g / mol. By making the alkenyl equivalent 300 g / mol or more, the cured product of the curable composition of the second embodiment tends to have a further decreased elastic modulus, and as a result, there is a tendency to be able to further reduce the thermal expansion coefficient of the substrate etc. obtained using the cured product. By making the alkenyl equivalent 1500 g / mol or less, there is a tendency to further improve the compatibility, heat resistance, chemical resistance, low thermal expansion, copper foil peel strength and insulation reliability of the curable composition of the second embodiment. From the same viewpoint, the alkenyl equivalent is preferably 350 to 1200 g / mol, more preferably 400 to 1000 g / mol.

[0345] The content of the polymer (E) in the curable composition of the second embodiment is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 10 to 40% by mass relative to 100% by mass of the resin solids. When the content is within this range, the curable composition of the second embodiment tends to have better compatibility and exhibit a better balance of low thermal expansion, copper foil peel strength, and chemical resistance.

[0346] The polymer (E) can be obtained, for example, by reacting an alkenylphenol (A), an epoxy-modified silicone (B), an epoxy compound (C), and a compound (H) as required in the presence of a polymerization catalyst (G). The reaction can be carried out in the presence of an organic solvent. More specifically, in the above-mentioned step, the polymer (E) can be obtained by performing an addition reaction between the epoxy groups possessed by the epoxy-modified silicone (B) and the epoxy compound (C) and the hydroxyl groups possessed by the alkenylphenol (A), and performing an addition reaction between the hydroxyl groups possessed by the obtained addition reactants and the epoxy groups possessed by the epoxy-modified silicone (B) and the epoxy compound (C).

[0347] The polymerization catalyst (G) is not particularly limited, and examples thereof include imidazole catalysts and phosphorus-based catalysts. These catalysts may be used alone or in combination of two or more. Among these, imidazole catalysts are preferred.

[0348] The imidazole catalyst is not particularly limited, and examples thereof include imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 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]benzimidazole ("TBZ" manufactured by Shikoku Chemical Industry Co., Ltd.), and 2,4,5-triphenylimidazole ("TPIZ" manufactured by Tokyo Chemical Industry Co., Ltd.). Among these, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and / or 2,4,5-triphenylimidazole are preferred from the viewpoint of preventing the epoxy component from polymerizing independently.

[0349] The amount of the polymerization catalyst (G) (preferably an imidazole catalyst) used is not particularly limited, but is, for example, 0.1 to 10 parts by mass relative to 100 parts by mass of the total amount of the alkenylphenol (A), epoxy-modified silicone (B), epoxy compound (C), and compound (H). From the perspective 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.

[0350] There are no particular limitations on the organic solvent, and for example, polar solvents or non-polar solvents can be used. There are no particular limitations on the polar solvent, and examples include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Cellosolve 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; and amides such as dimethylacetamide and dimethylformamide. There are no particular limitations on the non-polar solvent, and examples include aromatic hydrocarbons such as toluene and xylene. These solvents can be used alone or in combination of two or more.

[0351] 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).

[0352] 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.

[0353] After completion of the reaction in this step, the polymer (E) can be isolated and purified from the reaction mixture by a conventional method.

[0354] As described above, the curable composition of the second embodiment may further contain a compound (H) in addition to the polymer (E) as needed. By containing the compound (H) in addition to the polymer (E), the curable composition of the second embodiment tends to have further improved heat resistance, low thermal expansion, chemical resistance, and copper foil peel strength.

[0355] When the curable composition of the second embodiment contains a polymer (E) and a compound (H), the content of the polymer (E) in the curable composition of the second embodiment is preferably 5 to 60% by mass, more preferably 10 to 55% by mass, and even more preferably 20 to 50% by mass, relative to 100% by mass of the total of the polymer (E) and the compound (H). When the content is within this range, the curable composition tends to have better compatibility and exhibit well-balanced heat resistance, low thermal expansion, chemical resistance, and copper foil peel strength.

[0356] When the curable composition of the second embodiment contains a polymer (E) and a compound (H), the content of the compound (H) in the curable composition of the second embodiment is preferably 20 to 80 mass %, more preferably 35 to 75 mass %, and even more preferably 45 to 65 mass %, relative to 100 mass % of the total of the polymer (E) and the compound (H).

[0357] The content of the cyclic carbodiimide compound (D) in the curable composition of the second embodiment is the same as that in the curable composition of the first embodiment. By setting the content of the cyclic carbodiimide compound (D) within the above range, there is a tendency for heat resistance, low thermal expansion, copper foil peel strength, and chemical resistance to be further improved.

[0358] The curable composition of this embodiment may further contain other resins without impairing the effects of the curable composition of this embodiment. Examples of other resins include oxetane resins, benzoxazine compounds, and compounds having polymerizable unsaturated groups. These resins may be used alone or in combination of two or more.

[0359] Examples of the oxetane resin include oxetane, alkyloxetanes such as 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3′-bis(trifluoromethyl)perfluorooxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetanes, and “OXT-101” and “OXT-121” manufactured by Toagose Co., Ltd.

[0360] As used herein, a "benzoxazine compound" refers to a compound having two or more dihydrobenzoxazine rings in one molecule. Examples of benzoxazine compounds include "Bisphenol F-type benzoxazine BF-BXZ" and "Bisphenol S-type benzoxazine BS-BXZ" manufactured by KONISHI CHEMICAL INDCO., LTD.

[0361] Examples of the compound having a polymerizable unsaturated group include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; (meth)acrylates of monohydric or polyhydric alcohols such as methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; epoxy (meth)acrylates such as bisphenol A epoxy (meth)acrylate and bisphenol F epoxy (meth)acrylate; and benzocyclobutene resins.

[0362] [Inorganic fillers]

[0363] From the viewpoint of further improving the low thermal expansion property, the curable composition of the present embodiment preferably further contains an inorganic filler. The inorganic filler is not particularly limited, and examples thereof include silica, silicon compounds (e.g., white carbon), metal oxides (e.g., aluminum oxide, titanium dioxide, zinc oxide, magnesium oxide, zirconium oxide, etc.), metal nitrides (e.g., boron nitride, condensed boron nitride, silicon nitride, aluminum nitride, etc.), metal sulfates (e.g., barium sulfate, etc.), metal hydroxides (e.g., aluminum hydroxide, heat-treated aluminum hydroxide (e.g., aluminum hydroxide subjected to heat treatment to remove some of the crystalline water), boehmite, magnesium hydroxide, etc.), molybdenum compounds (e.g., molybdenum oxide, zinc molybdate, etc.), zinc compounds (e.g., 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 fine glass powders such as E-glass, T-glass, D-glass, S-glass, and Q-glass), hollow glass, spherical glass, etc. These inorganic fillers can be used alone or in combination of two or more. Among these, from the viewpoint of further improving low thermal expansion, the inorganic filler is preferably at least one selected from the group consisting of silica, metal hydroxides, and metal oxides, more preferably at least one selected from the group consisting of silica, boehmite, and alumina, and further preferably silica.

[0364] Examples of silicas include natural silica, fused silica, synthetic silica, AEROSIL, and hollow silica. These silicas may be used alone or in combination of two or more. Of these, fused silica is preferred for dispersibility, and two or more fused silicas having different particle sizes are more preferred for filling properties and fluidity.

[0365] From the viewpoint of further improving low thermal expansion properties, the content of the inorganic filler is preferably 50 to 1000 parts by mass, more preferably 70 to 500 parts by mass, and even more preferably 100 to 300 parts by mass per 100 parts by mass of the resin solid content.

[0366] [Silane coupling agent]

[0367] The curable composition of this embodiment may further contain a silane coupling agent. The inclusion of a silane coupling agent in the curable composition of this embodiment tends to further improve the dispersibility of the inorganic filler and the bonding strength between the components of the curable composition of this embodiment and the substrate described below.

[0368] The silane coupling agent is not particularly limited, and examples thereof include those generally used for surface treatment of inorganic materials, such as aminosilane compounds (e.g., γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (e.g., γ-glycidoxypropyltrimethoxysilane, etc.), acrylic silane compounds (e.g., γ-acryloxypropyltrimethoxysilane, etc.), cationic silane compounds (e.g., N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), styrylsilane compounds, and phenylsilane compounds. Silane coupling agents may be used alone or in combination of two or more. Among these, epoxysilane compounds are preferred. Examples of the epoxysilane-based compound include "KBM-403," "KBM-303," "KBM-402," and "KBE-403" manufactured by Shin-Etsu Chemical Co., Ltd.

[0369] The content of the silane coupling agent is not particularly limited, but may be 0.1 to 5.0 parts by mass relative to 100 parts by mass of the resin solid content.

[0370] [Wetting and dispersing agent]

[0371] The curable composition of this embodiment may further contain a wetting and dispersing agent. When the curable composition contains a wetting and dispersing agent, the dispersibility of the filler tends to be further improved.

[0372] The wetting dispersant may be any known dispersant (dispersion stabilizer) for dispersing fillers, and examples thereof include DISPER BYK-110, 111, 118, 180, 161, BYK-W996, W9010, and W903 manufactured by BYK JAPAN KK.

[0373] 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 relative to 100 parts by mass of the resin solid content.

[0374] [Solvent]

[0375] The curable composition of this embodiment may further contain a solvent. The curable composition of this embodiment contains a solvent, which tends to reduce viscosity during preparation of the curable composition, further improve workability (handling properties), or further improve impregnation properties into a substrate.

[0376] The solvent is not particularly limited as long as it can dissolve part or all of the components in the curable composition, and examples thereof include ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (such as toluene, xylene, etc.), amides (such as dimethyl formaldehyde, etc.), propylene glycol monomethyl ether and its acetate, etc. These solvents can be used alone or in combination of two or more.

[0377] The method for producing the curable composition of the present embodiment is not particularly limited, and examples thereof include a method of mixing each component into a solvent at once or in portions and stirring. In this case, known processes such as stirring, mixing, and kneading can be used to uniformly dissolve or disperse each component.

[0378] [use]

[0379] As described above, the curable composition of the present embodiment can exhibit excellent low thermal expansion, copper foil peel strength and chemical resistance. Therefore, the curable composition of the present embodiment can be suitable for use in prepregs, metal foil laminates and printed circuit boards. The curable composition of the present embodiment can be applied to the above-mentioned purposes by being cured. In other words, the cured product of the present embodiment is formed by curing the curable composition of the present embodiment.

[0380] It should be noted that, particularly in the above-mentioned applications, the curable composition of the second embodiment preferably contains at least an epoxy compound (C) (an epoxy compound (C) existing separately from the structural unit (C) in the polymer (E)) in addition to the polymer (E) and the cyclic carbodiimide compound (D).

[0381] In this case, the polymer (E) preferably has, as the unit derived from the epoxy compound (C), a unit derived from the above-mentioned bifunctional epoxy compound, more preferably a unit derived from the above-mentioned biphenyl-type epoxy resin, more preferably a unit derived from the compound represented by the above-mentioned formula (b2) (compound (b2)), and even more preferably a unit derived from R a The number of compounds (b2) is 0, and the alkyl group R a The number of units of the compound (b2) is 4 (commercially available products include, for example, "YL-6121H" manufactured by Mitsubishi Chemical Corporation).

[0382] In addition, as an epoxy compound (C) existing separately from the structural unit (C) in the polymer (E), it is preferred to contain the aforementioned naphthyl ether type epoxy resin (as a commercial product, for example, "HP-6000" manufactured by DIC Corporation, etc.) and / or naphthyl phenol formaldehyde varnish type epoxy resin (as a commercial product, for example, "HP-9540" manufactured by DIC Corporation, etc.).

[0383] [Prepreg]

[0384] The prepreg of this embodiment comprises a substrate and the curable composition of this embodiment impregnated or coated on the substrate. As described above, the prepreg can be obtained by a known method. Specifically, it can be obtained by impregnating or coating the substrate with the curable composition of this embodiment and then heating and drying it at 100-200°C to semi-cure (B-stage).

[0385] The prepreg of the present embodiment also includes a cured product obtained by thermally curing a semi-cured prepreg at a heating temperature of 180 to 230° C. and a heating time of 60 to 180 minutes.

[0386] Relative to the total amount of prepreg, the content of the curable composition in the prepreg is preferably 30 to 90 volume %, more preferably 35 to 85 volume %, and further preferably 40 to 80 volume % based on the solid content of the prepreg. By making the content of the curable composition within the above range, there is a tendency to further improve formability. It should be noted that the content of the curable composition described herein is calculated to also include the cured product of the curable composition of the present embodiment. In addition, the solid content of the prepreg described herein refers to the component after excluding the solvent from the prepreg, such as the filling material contained in the solid content of the prepreg.

[0387] As base material, it is not particularly limited, and the known base material used in the material of various printed circuit boards can be enumerated. As the specific example of base material, inorganic base materials other than glass base material, glass (for example, inorganic base materials consisting of inorganic fibers other than glass such as quartz), organic base materials (for example, organic base materials consisting of organic fibers such as wholly aromatic polyamide, polyester, poly-p-phenylene benzoxazole, polyimide) etc. can be enumerated. These base materials can be used alone as one or in combination as two or more. Among them, for the viewpoint that heating dimensional stability is more excellent, preferably glass base material.

[0388] 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 preferably fibers of one or more types 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.

[0389] The form of the substrate is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, short glass fiber mats, and surfacing mats. The weaving method of the woven fabric is not particularly limited, and examples thereof include plain weaves, basket weaves, and twill weaves. These can be appropriately selected from among these known fabrics according to the intended use and performance. Furthermore, glass fabrics obtained by fiberizing these fabrics or surface-treating them with a silane coupling agent or the like are suitable. The thickness and mass of the substrate are not particularly limited, and those of approximately 0.01 to 0.1 mm are generally suitable.

[0390] [Metal foil-clad laminate]

[0391] The metal foil-clad laminate of this embodiment comprises a laminate containing the prepreg of this embodiment and metal foil disposed on one or both sides of the laminate. The laminate can be formed from a single prepreg or multiple prepregs. Furthermore, the laminate may contain a resin sheet other than the prepreg of this embodiment.

[0392] The metal foil (conductor layer) may be any metal foil used in various printed circuit board materials, and examples thereof include copper and aluminum foils. Examples of copper foil include rolled copper foil and electrolytic copper foil. The thickness of the conductor layer is, for example, 1 to 70 μm, preferably 1.5 to 35 μm.

[0393] The forming method and forming conditions of the metal foil-clad laminate are not particularly limited, and the methods and conditions for forming laminates and multilayer boards for general printed circuit boards can be used. For example, a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, etc. can be used when forming the laminate (the above-mentioned laminate) or the metal foil-clad laminate. In addition, in the forming (laminate forming) of the laminate (the above-mentioned laminate) or the metal foil-clad laminate, the temperature is generally 100 to 300°C and the pressure is 2 to 100 kgf / cm2. 2 , the heating time is in the range of 0.05 to 5 hours. Furthermore, post-curing can be performed at a temperature of 150 to 300°C as needed. In particular, when a multi-stage press is used, the temperature is preferably 200 to 250°C and the pressure is preferably 10 to 40 kgf / cm 2 , heating time 80 minutes to 130 minutes, more preferably temperature 215 ℃ to 235 ℃, pressure 25 to 35 kgf / cm 2 , heating time 90 minutes to 120 minutes. In addition, a multilayer board can also be produced by combining the above-mentioned prepreg and a separately produced inner layer wiring board and laminating them.

[0394] [Printed Circuit Board]

[0395] The printed wiring board of this embodiment comprises an insulating layer comprising the prepreg of this embodiment, and a conductive layer formed on the surface of the insulating layer. The insulating layer may also be a cured product of the prepreg of this embodiment. For example, the printed wiring board of this embodiment can be formed by etching the metal foil of the metal-clad laminate of this embodiment into a predetermined wiring pattern to form the conductive layer.

[0396] Specifically, the printed circuit board of the present embodiment can be manufactured by the following method, for example. First, prepare the metal foil clad laminate of the present embodiment. Etch the metal foil of the metal foil clad laminate into a specified wiring pattern to produce an inner substrate with a conductor layer (inner circuit). Then, on the surface of the conductor layer (built-in circuit) of the inner substrate, a specified number of insulating layers and metal foil for the outer layer circuit are sequentially stacked, heated and pressed to form an integral body (laminate forming), thereby obtaining a laminate. It should be noted that the method of laminate forming and its forming conditions are the same as the method of laminate forming and its forming conditions in the above-mentioned laminate and metal foil clad laminate. Then, a through hole (through hole) and a via hole (via hole) are formed on the laminate, and a plated metal film for conducting the metal foil for the conductor layer (built-in circuit) and the outer layer circuit is formed on the wall surface of the hole thus formed. Then, the metal foil for the outer layer circuit is etched into a specified wiring pattern to produce an outer substrate with a conductor layer (outer layer circuit). In this way, a printed circuit board is manufactured.

[0397] Furthermore, when a metal foil-clad laminate is not used, a conductor layer forming a circuit can be formed on the insulating layer to produce a printed wiring board. In this case, the conductor layer can also be formed by chemical plating.

[0398] Example

[0399] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0400] (Production Example 1) Synthesis of Cyclic Carbodiimide Compound

[0401] o-Nitrophenol (0.11 mol), pentaerythritol tetrabromide (0.025 mol), potassium carbonate (0.33 mol), and 200 ml of N,N-dimethylformamide (DMF) were added to a reaction apparatus equipped with a stirrer and a heater under a N2 atmosphere and reacted at 130°C for 12 hours. DMF was then removed under reduced pressure, and the resulting solid was dissolved in 200 ml of dichloromethane and separated three times with 100 ml of water. The organic layer was dehydrated with 5 g of sodium sulfate, and the dichloromethane was removed under reduced pressure to obtain an intermediate product (nitro compound).

[0402] Then, the obtained intermediate product (nitro form, 0.1 mol), 5% palladium on carbon (Pd / C) (2 g), and 400 ml of ethanol / dichloromethane (70 / 30) were added to a reactor equipped with a stirrer, and hydrogen was replaced five times. The reaction was allowed to proceed at 25° C. with a continuous supply of hydrogen, and the reaction was terminated when the hydrogen gas no longer decreased. The Pd / C was recovered, and the mixed solvent was removed to obtain the intermediate product (amine form).

[0403] Then, in a reaction apparatus equipped with a stirring device, a heating device, and a dropping funnel, triphenylphosphine dibromide (0.11 mol) and 150 ml of 1,2-dichloroethane were added and stirred under an N2 atmosphere. A solution prepared by dissolving the intermediate product (amine body, 0.025 mol) and triethylamine (0.25 mol) in 50 ml of 1,2-dichloroethane was slowly added dropwise at 25°C. After the addition was completed, the reaction was allowed to react at 70°C for 5 hours. Afterwards, the reaction solution was filtered, and the filtrate was subjected to a liquid separation operation 5 times with 100 ml of water. 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).

[0404] Next, in a reaction apparatus equipped with a stirrer and a dropping funnel, di-tert-butyl dicarbonate (0.11 mol), N,N-dimethyl-4-aminopyridine (0.055 mol), and 150 ml of dichloromethane were added and stirred under a N2 atmosphere. To this mixture, 100 ml of dichloromethane, in which the intermediate product (0.025 mol) had been dissolved, was slowly added dropwise at 25°C. After the addition, the reaction was allowed to proceed for 12 hours. The dichloromethane was then removed, and the resulting solid component was purified to obtain a cyclic carbodiimide compound.

[0405] (Example 1)

[0406] In a three-necked flask equipped with a thermometer and a Dimrod condenser, 5.0 parts by mass of diallylbisphenol A (DABPA, Daiwa Kasei Industry Co., Ltd.), 5.4 parts by mass of biscresol fluorene (BCF, Osaka Gas Chemicals Co., Ltd.), 3.7 parts by mass of epoxy-modified silicone (B) 1 (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent weight 200 g / mol), 11.0 parts by mass of epoxy-modified silicone (B) 2 (KF-105, Shin-Etsu Chemical Co., Ltd., functional group equivalent weight 490 g / mol), 4.9 parts by mass of biphenyl epoxy resin (C) 1 (YL-6121H, Mitsubishi Chemical Corporation), and propylene glycol monomethyl ether acetate (DOWANOLPMA, Dow Chemical) as a solvent were added. Japan), heated to 120°C in an oil bath with stirring. After confirming that the raw materials had dissolved in the solvent, 0.3 parts by mass of imidazole catalyst g1 (TBZ, Shikoku Chemicals Co., Ltd.) was added. The mixture was heated to 140°C and stirred for 5 hours. After cooling, a phenoxy polymer solution (solids content 50% by mass) was obtained (polymer formation step).

[0407] Note that diallyl bisphenol A corresponds to "alkenylphenol (A)", epoxy-modified silicone (B) 1 and epoxy-modified silicone (B) 2 correspond to "epoxy-modified silicone (B)", and biphenyl-type epoxy resin (C) 1 corresponds to "epoxy compound (C)". Furthermore, the phenoxy polymer solution contains polymer (E), which contains structural units derived from alkenylphenol (A), structural units derived from epoxy-modified silicone (B), and structural units derived from epoxy compound (C). Hereinafter, polymer (E) will also be referred to as phenoxy polymer.

[0408] The content of the structural unit derived from the epoxy-modified silicone (B) was 48.8% by mass relative to the polymer (E).

[0409] The content of the structural unit derived from the epoxy compound (C) was 25% by mass relative to the total amount of the structural unit derived from the epoxy-modified silicone (B) and the structural unit derived from the epoxy compound (C).

[0410] Determination of weight average molecular weight Mw:

[0411] The weight average molecular weight (Mw) of the phenoxy polymer obtained in the above manner was measured as follows. 20 μL of the solution obtained by dissolving 0.5 g of the phenoxy polymer solution in 2 g of THF was injected into a high-speed liquid chromatograph (manufactured by Shimadzu Corporation, pump: LC-20AD) for analysis. Four columns were used: Shodex GPC KF-804 (length 30 cm × inner diameter 8 mm), Shodex GPC KF-803 (length 30 cm × inner diameter 8 mm), Shodex GPC KF-802 (length 30 cm × inner diameter 8 mm), and Shodex GPC KF-801 (length 30 cm × inner diameter 8 mm) manufactured by Showa Denko. THF (solvent) was used as the mobile phase, the flow rate was set to 1 mL / min, and the detector used was RID-10A. The weight average molecular weight (Mw) was determined by GPC using standard polystyrene as a standard substance. The weight average molecular weight Mw of the phenoxy polymer measured in the above manner was 12,000.

[0412] To 30 parts by mass of the phenoxy polymer solution (in terms of solid content), 14 parts by mass of a novolac-type cyanate compound (PT-30, Lonza KK), 17 parts by mass of a novolac-type maleimide compound (BMI-2300, Daiwa Kasei Industry Co., Ltd.), 6 parts by mass of a bismaleimide compound (BMI-80, K.I. Chemical Industry Co., Ltd.), 28 parts by mass of a naphthylcresol novolac-type epoxy compound (HP-9540, DIC Corporation), 5 parts by mass of the cyclic carbodiimide compound obtained in Preparation Example 1, 140 parts by mass of spherical silica (SC-2050MB, ADMATECHS COMPANY LIMITED), 1 part by mass of a wetting and dispersing agent (DISPERBYK-161, BYK Japan), and silane coupling agent (KMB-403, Shin-Etsu Chemical) were mixed. Co., Ltd.) to obtain a varnish. This varnish was dip-coated onto S-glass woven fabric (thickness 100 μm) and dried by heating at 165°C for 5 minutes to obtain a prepreg having a resin composition solid content (including filler) of 47.4% by mass (prepreg production process).

[0413] (Example 2)

[0414] In the prepreg production process, the same procedures as in Example 1 were followed, except that the amount of the novolac-type cyanate ester compound (PT-30, Lonza KK) was changed from 14 parts by mass to 13 parts by mass, the amount of the novolac-type maleimide compound (BMI-2300, Daiwa Kasei Industry Co., Ltd.) was changed from 17 parts by mass to 16 parts by mass, the amount of the bismaleimide compound (BMI-80, K.I. Chemical Industry Co., Ltd.) was changed from 6 parts by mass to 5 parts by mass, the amount of the naphthylcresol novolac-type epoxy compound (HP-9540, DIC Corporation) was changed from 28 parts by mass to 26 parts by mass, and the amount of the cyclic carbodiimide compound obtained in Production Example 1 was changed from 5 parts by mass to 10 parts by mass. A prepreg having a resin composition solid content (including filler) of 47.4% by mass was obtained.

[0415] (Example 3)

[0416] In the polymer production step, diallylbisphenol A (DABPA, Daiwa Kasei Industry Co., Ltd.) was changed from 5.0 parts by mass to 5.1 parts by mass, biscresol fluorene (BCF, Osaka Gas Chemicals Co., Ltd.) was changed from 5.4 parts by mass to 5.6 parts by mass, epoxy-modified silicone (B) 1 (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g / mol) was changed from 3.7 parts by mass to 4.2 parts by mass, and epoxy-modified silicone (B) 2 (KF-105, Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g / mol) was changed from 1. Co., Ltd., functional group equivalent 490 g / mol) was changed from 11.0 parts by mass to 8.5 parts by mass, and biphenyl type epoxy resin (C) 1 (YL-6121H, Mitsubishi Chemical Corporation) was changed from 4.9 parts by mass to 5.6 parts by mass. Except for this, a phenoxy polymer solution (solid content 50% by mass) was obtained by the same operation as in Example 1 (polymer formation step).

[0417] After the phenoxy polymer solution is heated to 100°C in an oil bath, 1.0 parts by mass of aminotriazine novolac (LA-3018) is added, stirred for 2 hours, and cooled to obtain a modified phenoxy polymer solution (solid content 50% by mass) (polymer modification step). In addition, the modified phenoxy polymer solution contains a polymer (E), which 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 a structural unit derived from aminotriazine novolac. The weight average molecular weight Mw of the modified phenoxy polymer measured in the same manner as above is 12,000. The polymer modification step can also be carried out continuously with the polymer generation step.

[0418] To 30 parts by mass of the modified phenoxy polymer solution (based on solid content), 8 parts by mass of a novolac-type maleimide compound (BMI-2300, Daiwa Kasei Industry Co., Ltd.), 8 parts by mass of a bismaleimide compound (BMI-80, K.I. Chemical Industry Co., Ltd.), 25 parts by mass of a naphthol-type epoxy compound (HP-6000, DIC Corporation), 24 parts by mass of a naphthol aralkyl-type phenol compound (SN495V, NIPPON STEEL Chemical & Material Co., Ltd.), 5 parts by mass of the cyclic carbodiimide compound obtained in Preparation Example 1, 200 parts by mass of spherical silica (SC-2050MB, ADMATECHS COMPANY LIMITED), 1 part by mass of a wetting and dispersing agent (DISPERBYK-161, BYK Japan), and a silane coupling agent (KMB-403, Shin-Etsu) were mixed. Chemical Co., Ltd.) to obtain a varnish. This varnish was dip-coated onto S-glass woven fabric (thickness 100 μm) and dried by heating at 150°C for 3 minutes to obtain a prepreg having a resin composition solid content (including filler) of 48.8% by mass (prepreg production process).

[0419] (Example 4)

[0420] To 30 parts by mass (in terms of solid content) of the modified phenoxy polymer solution obtained in the same manner as in Example 3 were mixed 7.5 parts by mass of a novolac-type maleimide compound (BMI-2300, Daiwa Kasei Industry Co., Ltd.), 7.5 parts by mass of a bismaleimide compound (BMI-80, K.I. Chemical Industry Co., Ltd.), 23 parts by mass of a naphthol-type epoxy compound (HP-6000, DIC Corporation), 22 parts by mass of a naphthol aralkyl-type phenol compound (SN495V, NIPPON STEEL Chemical & Material Co., Ltd.), 10 parts by mass of the cyclic carbodiimide compound obtained in Preparation Example 1, 200 parts by mass of spherical silica (SC-2050MB, ADMATECHS COMPANY LIMITED), and a wetting and dispersing agent (DISPERBYK-161, BYK A varnish was obtained by adding 1 part by mass of a silane coupling agent (KMB-403, Shin-Etsu Chemical Co., Ltd., Japan) and 5 parts by mass of a silane coupling agent (KMB-403, Shin-Etsu Chemical Co., Ltd.). This varnish was dip-coated onto an S-glass woven fabric (100 μm thick) and then heat-dried at 140°C for 3 minutes to obtain a prepreg having a resin composition solid content (including filler) of 48.8% by mass (prepreg production process).

[0421] (Comparative Example 1)

[0422] To 30 parts by mass (solid content conversion) of the phenoxy polymer solution obtained in the same manner as in Example 1 were mixed 15 parts by mass of a novolac-type cyanate compound (PT-30, Lonza KK), 18 parts by mass of a novolac-type maleimide compound (BMI-2300, Daiwa Kasei Industry Co., Ltd.), 6 parts by mass of a bismaleimide compound (BMI-80, K.I. Chemical Industry Co., Ltd.), 30 parts by mass of a naphthylcresol novolac-type epoxy compound (HP-9540, DIC Corporation), 140 parts by mass of spherical silica (SC-2050MB, ADMATECHS COMPANY LIMITED), 1 part by mass of a wetting and dispersing agent (DISPERBYK-161, BYK Japan), and 5 parts by mass of a silane coupling agent (KMB-403, Shin-Etsu Chemical Co., Ltd.) to obtain a varnish. The varnish was dip-coated on S glass woven fabric (thickness 100 μm) and dried by heating at 165° C. for 5 minutes to obtain a prepreg having a resin composition solid content (including filler) of 47.4% by mass (prepreg production process).

[0423] (Comparative Example 2)

[0424] To 30 parts by mass (solid content conversion) of the modified phenoxy polymer solution obtained in the same manner as in Example 3 were mixed 9 parts by mass of a novolac-type maleimide compound (BMI-2300, Daiwa Kasei Industry Co., Ltd.), 9 parts by mass of a bismaleimide compound (BMI-80, K.I. Chemical Industry Co., Ltd.), 27 parts by mass of a naphthol-type epoxy compound (HP-6000, DIC Corporation), 25 parts by mass of a naphthol aralkyl-type phenol compound (SN495V, NIPPONSTEEL Chemical & Material Co., Ltd.), 200 parts by mass of spherical silica (SC-2050MB, ADMATECHS COMPANY LIMITED), 1 part by mass of a wetting and dispersing agent (DISPERBYK-161, BYK Japan), and 1 part by mass of a silane coupling agent (KMB-403, Shin-Etsu Chemical Co., Ltd.). Co., Ltd.) to obtain a varnish. This varnish was dip-coated onto S-glass woven fabric (thickness 100 μm) and dried by heating at 140°C for 3 minutes to obtain a prepreg having a resin composition solid content (including filler) of 48.8% by mass (prepreg production process).

[0425] (Comparative Example 3)

[0426] A varnish was obtained by mixing 22.5 parts by mass of a novolac-type maleimide compound (BMI-2300, Daiwa Kasei Industry Co., Ltd.), 35.1 parts by mass of a naphthol ether-type epoxy compound (HP-6000, DIC Corporation), 33.5 parts by mass of a naphthol aralkyl-type phenol compound (SN495V, NIPPON STEEL Chemical & Material Co., Ltd.), 9.1 parts by mass of the cyclic carbodiimide compound obtained in Production Example 1, 200 parts by mass of spherical silica (SC-2050MB, ADMATECHS COMPANY LIMITED), 1 part by mass of a wetting and dispersing agent (DISPERBYK-161, BYK Japan), and 5 parts by mass of a silane coupling agent (KMB-403, Shin-Etsu Chemical Co., Ltd.). The varnish was dip-coated on S glass woven fabric (thickness 100 μm) and dried by heating at 140° C. for 3 minutes to obtain a prepreg having a resin composition solid content (including filler) of 48.8% by mass (prepreg production process).

[0427] (Comparative Example 4)

[0428] A varnish was obtained by mixing 24.6 parts by mass of a novolac-type maleimide compound (BMI-2300, Daiwa Kasei Industry Co., Ltd.), 38.6 parts by mass of a naphthol ether-type epoxy compound (HP-6000, DIC Corporation), 36.8 parts by mass of a naphthol aralkyl-type phenol compound (SN495V, Nippon Steel Chemical Co., Ltd.), 200 parts by mass of spherical silica (SC-2050MB, ADMATECHS COMPANY LIMITED), 1 part by mass of a wetting and dispersing agent (DISPERBYK-161, BYK Japan), and 5 parts by mass of a silane coupling agent (KMB-403, Shin-Etsu Chemical Co., Ltd.). The varnish was dip-coated on S glass woven fabric (thickness 100 μm) and dried by heating at 140° C. for 3 minutes to obtain a prepreg having a resin composition solid content (including filler) of 48.8% by mass (prepreg production process).

[0429] [Production of Metal Foil-Clad Laminated Sheets]

[0430] Two prepregs obtained in Examples 1 to 4 and Comparative Examples 1 to 4 were stacked, and electrolytic copper foils (3EC-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) having a thickness of 12 μm were placed above and below. 2 The laminate was laminated at 230°C for 100 minutes to obtain a 0.2 mm thick copper-clad laminate including an insulating layer. The properties of the resulting copper-clad laminate were evaluated using the following methods. The results are shown in Table 1.

[0431] [Tg (glass transition temperature)]

[0432] The copper foil on both sides of the metal-clad laminate (20 mm×5 mm×0.2 mm) obtained by the above method was removed by etching, and then the glass transition temperature (Tg) (unit: ° C.) was measured using a dynamic viscoelasticity measuring apparatus (manufactured by TA Instruments) in accordance with JIS C6481.

[0433] [CTE (Coefficient of Thermal Expansion)]

[0434] The linear thermal expansion coefficient of the insulating layer of the metal-clad laminate was measured in the longitudinal direction of the glass cloth. Specifically, the copper foil on both sides of the copper-clad laminate (10 mm × 6 mm × 0.2 mm) obtained by the above method was removed by etching. The laminate was then heated in a 220°C thermostat for 2 hours to remove stress caused by forming. Subsequently, the temperature was increased from 40°C to 320°C at a rate of 10°C per minute using a thermal expansion coefficient measuring device (horizontal dilatometer manufactured by LINSEIS). The linear thermal expansion coefficient (CTE) was measured from 60°C to 260°C (unit: ppm / °C).

[0435] [Copper foil peel strength (copper foil adhesion)]

[0436] Using the copper-clad laminate (10 mm×150 mm×0.2 mm) obtained by the above method, the copper foil peel strength (copper foil adhesion) was measured in accordance with JIS C6481 (unit: kN / m).

[0437] [Desmear resistance]

[0438] After removing the copper foil on both sides of the copper-clad laminate (50 mm × 50 mm × 0.2 mm) obtained by the above method by etching, immerse it in a swelling liquid, namely Swelling Dip Securiganth P of Atotech Japan KK, at 80 ° C for 10 minutes, then immerse it in a roughening liquid, namely concentrates Compact CP of Atotech Japan KK, at 80 ° C for 5 minutes, and finally immerse it in a neutralizing liquid, namely Reduction Conditioner Securiganth P500 of Atotech Japan KK, at 45 ° C for 10 minutes. Repeat this treatment 3 times. The mass of the copper-clad laminate before and after treatment is measured, and the mass reduction (unit: mass %) is calculated based on the mass of the sample before treatment. The smaller the absolute value of the mass reduction, the better the decontamination resistance.

[0439] [Table 1]

[0440]

[0441] This application is based on Japanese patent application (Japanese Patent Application No. 2021-128756) filed with the Japan Patent Office on August 5, 2021, the contents of which are incorporated herein by reference.

Claims

1. A curable composition comprising an alkenylphenol (A), an epoxy-modified silicone (B), an epoxy compound (C) other than the epoxy-modified silicone (B), and a cyclic carbodiimide compound (D). The content of the epoxy-modified silicone (B) is 5 to 95% by mass relative to 100% by mass of the total of the epoxy-modified silicone (B) and the epoxy compound (C). The content of the epoxy compound (C) is 5 to 95% by mass relative to 100% by mass of the total amount of the epoxy-modified silicone (B) and the epoxy compound (C). The content of the cyclic carbodiimide compound (D) is 1.0 to 30 parts by mass relative to 100 parts by mass of the resin solid content.

2. The curable composition according to claim 1, wherein The cyclic carbodiimide compound (D) has a cyclic structure represented by the following formula (D1): In the formula, L is a divalent to tetravalent bonding group, the bonding group is an aliphatic group, an alicyclic group, an aromatic group or a group composed of these, and the bonding group optionally contains heteroatoms and / or substituents. The number of atoms forming the ring structure is 8 to 50.

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

4. The curable composition according to claim 1 or 2, wherein The average number of phenol groups per molecule of the alkenylphenol (A) is 1 or more and less than 3, the average number of epoxy groups per molecule of the epoxy-modified silicone (B) is 1 or more and less than 3, and the average number of epoxy groups per molecule of the epoxy compound (C) is 1 or more and less than 3.

5. The curable composition according to claim 1 or 2, wherein The alkenylphenol (A) contains diallyl bisphenol and / or dipropylene bisphenol.

6. The curable composition according to claim 1 or 2, wherein The epoxy-modified silicone (B) includes an epoxy-modified silicone having an epoxy equivalent weight of 140 to 250 g / mol.

7. The curable composition according to claim 1 or 2, wherein The epoxy-modified silicone (B) contains epoxy-modified silicone represented by the following formula (B1), Where 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 having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 0 to 100.

8. The curable composition according to claim 1 or 2, wherein The epoxy compound (C) includes 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.

9. A curable composition comprising a polymer (E) and a cyclic carbodiimide compound (D), The polymer (E) contains 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). The content of the polymer (E) is 5 to 50 parts by mass relative to 100 parts by mass of the resin solid content, and the content of the cyclic carbodiimide compound (D) is 1.0 to 30 parts by mass relative to 100 parts by mass of the resin solid content. The content of the structural unit derived from the alkenylphenol (A) in the polymer (E) is 5 to 50% by mass, the content of the structural unit derived from the epoxy-modified silicone (B) in the polymer (E) is 20 to 60% by mass, and the content of the structural unit derived from the epoxy compound (C) other than the epoxy-modified silicone (B) in the polymer (E) is 5 to 40% by mass, relative to the total mass of the polymer (E).

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

11. The curable composition according to claim 9 or 10, wherein The cyclic carbodiimide compound (D) has a cyclic structure represented by the following formula (D1): In the formula, L is a divalent to tetravalent bonding group, the bonding group is an aliphatic group, an alicyclic group, an aromatic group or a group composed of these, and the bonding group optionally contains heteroatoms and / or substituents. The number of atoms forming the ring structure is 8 to 50.

12. The curable composition according to claim 9 or 10, wherein The content of the cyclic carbodiimide compound (D) is 2.0 to 15 parts by mass relative to 100 parts by mass of the resin solid content.

13. The curable composition according to claim 9 or 10, wherein The average number of phenol groups per molecule of the alkenylphenol (A) is 1 or more and less than 3, the average number of epoxy groups per molecule of the epoxy-modified silicone (B) is 1 or more and less than 3, and the average number of epoxy groups per molecule of the epoxy compound (C) is 1 or more and less than 3.

14. The curable composition according to claim 9 or 10, wherein The alkenylphenol (A) contains diallyl bisphenol and / or dipropylene bisphenol.

15. The curable composition according to claim 9 or 10, wherein The epoxy-modified silicone (B) includes an epoxy-modified silicone having an epoxy equivalent weight of 140 to 250 g / mol.

16. The curable composition according to claim 9 or 10, wherein The epoxy-modified silicone (B) contains epoxy-modified silicone represented by the following formula (B1), Where 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 having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 0 to 100.

17. The curable composition according to claim 9 or 10, wherein The epoxy compound (C) includes 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.

18. The curable composition according to claim 9 or 10, further comprising at least one selected from the group consisting of alkenylphenol (A), epoxy-modified silicone (B), and epoxy compounds (C) other than the epoxy-modified silicone (B).

19. The curable composition according to claim 18, wherein The epoxy compound (C) includes a naphthyl cresol novolac type epoxy resin and / or a naphthyl ether type epoxy resin.

20. The curable composition according to claim 1 or 9, further comprising one or more compounds (H) selected from the group consisting of maleimide compounds, cyanate compounds, phenol compounds (F) other than the alkenylphenol (A), and alkenyl-substituted nadic imide compounds.

21. The curable composition according to claim 1 or 9, further comprising an inorganic filler, The inorganic filler includes one or more selected from the group consisting of silica, boehmite, and alumina.

22. A prepreg comprising: a substrate; and the curable composition according to claim 1 or 9 impregnated or coated on the substrate. 23 . A metal foil-clad laminate comprising: a laminate comprising the prepreg according to claim 22 ; and a metal foil disposed on one or both surfaces of the laminate. 24 . A printed wiring board comprising: an insulating layer comprising the prepreg according to claim 22 ; and a conductive layer formed on a surface of the insulating layer.

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