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

Abstract

To provide a curable composition, a prepreg, a resin sheet, a metal foil-clad laminate and a printed wiring board, exhibiting superior compatibility, low thermal expansion, and chemical resistance.SOLUTION: A curable composition contains an alkenyl phenol A, an epoxy-modified silicone B, and an epoxy compound C other than the epoxy-modified silicone B.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a curable composition, a prepreg, a resin sheet, a metal foil-clad laminate, and a printed wiring board. [Background technology]

[0002] In recent years, semiconductor packages widely used in electronic devices, communication devices, personal computers, etc. have become more functional and smaller, and as a result, the integration and high-density packaging of components for semiconductor packages have been accelerating. Accordingly, the properties required of printed wiring boards for semiconductor packages have become increasingly strict. Examples of the properties required of such printed wiring boards include a low coefficient of thermal expansion, 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 foil-clad laminates and multilayer printed wiring boards.

[0004] Patent Document 2 discloses a production method for obtaining a semiconductor encapsulation resin by reacting an addition polymer of polymaleimide, a diglycidyl polysiloxane represented by the following formula (I), and a diallyl bisphenol represented by the following formula (II), with an allylated phenol resin represented by the following formula (III) in a predetermined ratio and under predetermined conditions. This document discloses that the semiconductor encapsulation resin obtained by the above production method has good compatibility between the polymaleimide and the addition polymer, and furthermore, the cured product properties of the composition using the semiconductor encapsulation resin are excellent (e.g., high glass transition temperature, moisture resistance, and strength under heat), making it a highly reliable semiconductor encapsulation resin composition. This document also discloses that component b in formula (III) reacts with the maleimide group in the resin-forming reaction with the polymaleimide, and is an important component that improves the compatibility between the polymaleimide and the polysiloxane. [ka] (In the formula, R 1 represents an alkylene group or a phenylene group, and R 2 each independently represents an alkyl group or a phenyl group, and n represents an integer of 1 to 100. [ka] (In the formula, R 4 represents an ether bond, a methylene group, a propylidene group, or a direct bond (single bond). [ka] (In the above formula, a, b, and c represent the percentage of each component, and 0 <a,b,c<100かつa+b+c=100である。) [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-149154 [Patent Document 2] Japanese Patent Application Publication No. 4-4213 Summary of the Invention [Problem to be solved by the invention]

[0006] As disclosed in Patent Document 1, a resin composition containing a silicone compound having an epoxy group in its molecular structure and a thermosetting resin such as a maleimide compound has excellent low thermal expansion properties. However, the present inventors have found that the above resin composition has problems with moldability due to insufficient compatibility between the silicone compound and the thermosetting resin. Furthermore, the present inventors have found that the above resin composition has insufficient chemical resistance and metal foil peel strength (e.g., copper foil peel strength) when made into a metal foil-clad laminate.

[0007] On the other hand, the resin composition described in Patent Document 2 is used for semiconductor encapsulation, and the low thermal expansion, chemical resistance, and copper foil peel strength required as properties of printed wiring boards are not considered.

[0008] The present invention has been made in view of the above problems, and an object of the present invention is to provide a curable composition, a prepreg, a resin sheet, a metal foil-clad laminate, and a printed wiring board that have excellent compatibility, low thermal expansion, and chemical resistance. [Means for solving the problem]

[0009] The present inventors have conducted extensive research to solve the above-mentioned problems, and as a result have found that the above-mentioned problems can be solved by a curable composition containing an alkenylphenol, an epoxy-modified silicone, and an epoxy compound other than the epoxy-modified silicone, or a curable composition containing a polymer having these as structural units, and have thus completed the present invention.

[0010] That is, the present invention is as follows. [1] An epoxy-modified silicone composition comprising an alkenylphenol A, an epoxy-modified silicone B, and an epoxy compound C other than the epoxy-modified silicone B, Curable composition. [2] the alkenylphenol A has an average number of phenol groups per molecule of 1 or more and less than 3, the epoxy-modified silicone B has an average number of epoxy groups per molecule of 1 or more and less than 3, and the epoxy compound C has an average number of epoxy groups per molecule of 1 or more and less than 3; The curable composition according to [1]. [3] The alkenylphenol A contains diallyl bisphenol and / or dipropenyl bisphenol. The curable composition according to [1] or [2]. [4] The epoxy-modified silicone B contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g / mol. The curable composition according to any one of [1] to [3]. [5] The epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1): The curable composition according to any one of [1] to [4]. [ka] (In the formula, R 1 each independently represents an alkylene group, a phenylene 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 1 or more. [6] The epoxy compound C contains an epoxy compound represented by the following formula (2): The curable composition according to any one of [1] to [5]. [ka] (In the formula, R a each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom. [7] the content of the epoxy compound C is 5 to 50% by mass relative to 100% by mass of the total amount of the epoxy-modified silicone B and the epoxy compound C; The curable composition according to any one of [1] to [6]. [8] The polymer D 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. Curable composition. [9] The weight average molecular weight of the polymer D is 3.0 × 10 3 ~5.0×10 4 That is, The curable composition according to [8].

[10] the content of the structural units derived from the epoxy-modified silicone B in the polymer D is 20 to 60 mass% based on the total mass of the polymer D; The curable composition according to [8] or [9].

[11] The alkenyl group equivalent of the polymer D is 300 to 1500 g / mol. The curable composition according to any one of [8] to

[10] .

[12] The content of the polymer D is 5 to 50% by mass relative to 100% by mass of the resin solid content. The curable composition according to any one of [8] to

[11] .

[13] Further containing a thermosetting resin E, The curable composition according to any one of [1] to

[12] .

[14] the thermosetting resin E contains one or more compounds selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds, alkenyl-substituted nadimide compounds, and epoxy compounds; The curable composition according to

[13] .

[15] The maleimide compound 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, and a maleimide compound represented by the following formula (3): The curable composition according to

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

[16] The cyanate ester compound includes a compound represented by the following formula (4) and / or a compound represented by the following formula (5) excluding the compound represented by the following formula (4): The curable composition according to

[14] or

[15] . [ka] (In the formula, each R6 independently represents a hydrogen atom or a methyl group, and n2 represents an integer of 1 or greater.) [ka] (In the formula, each Rya independently represents an alkenyl group having 2 to 8 carbon atoms, each Ryb independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, each Ryc independently represents an aromatic ring having 4 to 12 carbon atoms, Ryc may form a condensed structure with a benzene ring, Ryc may or may not be present, A 1a 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), and when Ryc is absent, one benzene ring may have two or more Rya and / or Ryb groups, and n represents an integer of 1 to 10.

[17] The epoxy compound contains a compound represented by the following formula (6) or a compound represented by the following formula (7): The curable composition according to any one of

[14] to

[16] . [ka] (In the formula, R 13 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms. [ka] (In the formula, R 14 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms.

[18] Further containing an inorganic filler, The content of the inorganic filler is 50 to 1000 parts by mass per 100 parts by mass of the resin solid content. The curable composition according to any one of [1] to

[17] .

[19] For printed wiring boards, The curable composition according to any one of [1] to

[18] .

[20] A substrate; and the curable composition according to any one of [1] to

[19] , which is impregnated into or applied to the substrate. Prepreg. 〔twenty one〕 A support and the curable composition according to any one of [1] to

[19] arranged on the surface of the support. Resin sheet. 〔twenty two〕 A laminate formed of one or more selected from the group consisting of the prepreg according to

[20] and the resin sheet according to

[21] ; A metal foil disposed on one or both sides of the laminate, Metal foil laminate. 〔twenty three〕 An insulating layer formed of one or more selected from the group consisting of the prepreg according to

[20] and the resin sheet according to

[21] ; a conductor layer formed on the surface of the insulating layer, Printed wiring board. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a curable composition, a prepreg, a resin sheet, a metal foil-clad laminate, and a printed wiring board that have excellent compatibility, low thermal expansion, and chemical resistance. DETAILED DESCRIPTION OF THE INVENTION

[0012] Below, we will explain in detail the form for implementing the present invention (hereinafter referred to as the ``present embodiment''), but the present invention is not limited to this and various modifications are possible within the scope of the gist of the present invention.

[0013] Unless otherwise specified, the term "resin solid content" as used in this specification refers to the components excluding the solvent and filler in the curable composition of the present embodiment, and 100 parts by mass of resin solid content means that the total of the components excluding the solvent and filler in the curable composition is 100 parts by mass.

[0014] As used herein, "compatibility" refers to the compatibility of the silicone component, Polymer D, with other thermosetting resins in the curable composition. Due to the excellent compatibility, separation of Polymer D is suppressed during molding, and molded articles with excellent appearance can be obtained, and the resulting molded articles also have excellent isotropy in terms of physical properties.

[0015] [First embodiment: curable composition] The curable composition of the first embodiment contains alkenylphenol A, epoxy-modified silicone B, and epoxy compound C excluding epoxy-modified silicone B (hereinafter, also simply referred to as "epoxy compound C"). Curable compositions containing these components tend to have better compatibility with thermosetting resins that are not sufficiently compatible with epoxy-modified silicone B. This allows the curable composition to exhibit better compatibility. Furthermore, when a portion of each of these components is reacted (polymerized) and used, the curable composition can exhibit better low thermal expansion and chemical resistance.

[0016] [Alkenylphenol A] The alkenylphenol A is not particularly limited as long as it is a compound having a structure in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. By including the alkenylphenol A, the curable composition can exhibit excellent compatibility.

[0017] The alkenyl group is not particularly limited, and examples thereof include alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl. Among these, from the viewpoint of more effectively and reliably achieving the effects of the present invention, the alkenyl group is preferably an allyl group and / or a propenyl group, and more preferably an allyl group. The number of alkenyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 4. From the viewpoint of more effectively and reliably achieving 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.

[0018] 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.

[0019] The phenolic aromatic ring may have a substituent other than an alkenyl group. Examples of such a 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, 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. In addition, the bonding position of the substituent to the phenolic aromatic ring is also not particularly limited.

[0020] The alkenylphenol A may have one or more structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. From the viewpoint of more effectively and reliably achieving the effects of the present invention, the alkenylphenol A preferably has one or two structures in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring, and more preferably has two structures.

[0021] The alkenylphenol A may be, for example, a compound represented by the following formula (1A) or (1B). [ka] (In the formula, each Rxa independently represents an alkenyl group having 2 to 8 carbon atoms; each Rxb independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom; each Rxc independently represents an aromatic ring having 4 to 12 carbon atoms; Rxc may form a condensed structure with a benzene ring; Rxc may or may not be present; 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); and when Rxc is absent, one benzene ring may have two or more Rxa and / or Rxb groups.) [ka] (In the formula, each Rxd independently represents an alkenyl group having 2 to 8 carbon atoms, each Rxe 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, which may form a condensed structure with a benzene ring, and which may or may not be present, and when Rxf is not present, one benzene ring may have two or more Rxd and / or Rxe groups.)

[0022] In formula (1A) and formula (1B), the alkenyl group having 2 to 8 carbon atoms represented by Rxa and Rxd is not particularly limited, but examples thereof include a vinyl group, an allyl group, a propenyl group, a butenyl group, and a hexenyl group.

[0023] In the formulas (1A) and (1B), when the groups represented by Rxc and Rxf form a condensed structure with a benzene ring, for example, a compound containing a naphthol ring as a phenolic aromatic ring can be mentioned. In addition, in the formulas (1A) and (1B), when the groups represented by Rxc and Rxf do not exist, for example, a compound containing a phenol ring as a phenolic aromatic ring can be mentioned.

[0024] In formula (1A) and formula (1B), the alkyl group having 1 to 10 carbon atoms represented by Rxb and Rxe is not particularly limited, and examples thereof include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group, and branched alkyl groups such as an isopropyl group, an isobutyl group, and a tert-butyl group.

[0025] In formula (1A), the alkylene group having 1 to 6 carbon atoms represented by A is not particularly limited, and examples thereof include a methylene group, an ethylene group, a trimethylene group, and a propylene group. 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.

[0026] In the compound represented by formula (1B), Rxf is preferably a benzene ring (a compound containing a dihydroxynaphthalene skeleton), from the viewpoint of more effectively and reliably exhibiting the effects of the present invention.

[0027] From the viewpoint of further improving compatibility, the alkenylphenol A is preferably an alkenylbisphenol in which one alkenyl group is bonded to each of 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 two phenolic aromatic rings of a bisphenol, and / or a dipropenylbisphenol in which one propenyl group is bonded to each of two phenolic aromatic rings of a bisphenol.

[0028] The diallyl bisphenol is not particularly limited, but examples thereof include o,o'-diallyl bisphenol A ("DABPA" manufactured by Daiwa Chemical Industry Co., Ltd.), o,o'-diallyl bisphenol F, o,o'-diallyl bisphenol S, and o,o'-diallyl bisphenol fluorene. The dipropenyl bisphenol is not particularly limited, but examples thereof include o,o'-dipropenyl bisphenol A ("PBA01" manufactured by Gunei Chemical Industry Co., Ltd.), o,o'-diallyl bisphenol F, o,o'-dipropenyl bisphenol S, and o,o'-dipropenyl bisphenol fluorene.

[0029] From the viewpoint of more effectively and reliably achieving the effects of the present invention, the average number of phenol groups per molecule of alkenylphenol A is preferably from 1 to less than 3, and more preferably from 1.5 to 2.5. The average number of phenol groups is calculated by the following formula.

number

[0030] In the formula, Ai represents the number of phenol groups in an alkenylphenol having i phenol groups in the molecule, Xi represents the proportion of alkenylphenols having i phenol groups in the molecule to the total alkenylphenols, and X1 + X2 + ... X n =1.

[0031] [Epoxy-modified silicone B] There are no particular limitations on the epoxy-modified silicone B, as long as it is a silicone compound or resin modified with an epoxy group-containing group. By including the epoxy-modified silicone B, the curable composition can exhibit excellent low thermal expansion properties and chemical resistance.

[0032] The silicone compound or resin is not particularly limited as long as it has a polysiloxane skeleton in which siloxane bonds are repeatedly formed. The polysiloxane skeleton may be a linear skeleton, a cyclic skeleton, or a network skeleton. Among these, a linear skeleton is preferred from the viewpoint of more effectively and reliably achieving the effects of the present invention.

[0033] The epoxy group-containing group is not particularly limited, but examples thereof include groups represented by the following formula (a1): [ka] (In the formula, R 0 represents an alkylene group (for example, an alkylene group having 1 to 5 carbon atoms such as a methylene group, an ethylene group, or a propylene group), and X represents a monovalent group represented by the following formula (a2) or a monovalent group represented by the following formula (a3): [ka] [ka]

[0034] Epoxy-modified silicone B preferably contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g / mol. By containing an epoxy-modified silicone B having an epoxy equivalent within the above range, compatibility with thermosetting resins, low thermal expansion, and chemical resistance tend to be further improved in a well-balanced manner. From the same viewpoint, the epoxy equivalent is more preferably 145 to 245 g / mol, and even more preferably 150 to 240 g / mol.

[0035] From the viewpoint of achieving a good balance between compatibility with thermosetting resins, low thermal expansion, and chemical resistance, it is preferable that epoxy-modified silicone B contain two or more types of epoxy-modified silicones. In this case, it is preferable that the two or more types of epoxy-modified silicones have different epoxy equivalents, more preferably an epoxy-modified silicone having an epoxy equivalent of 50 to 350 g / mol and an epoxy-modified silicone having an epoxy equivalent of 400 to 4000 g / mol, and even more preferably an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g / mol and an epoxy-modified silicone having an epoxy equivalent of 450 to 3000 g / mol.

[0036] When epoxy-modified silicone B contains two or more types of epoxy-modified silicones, the average epoxy equivalent of 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 using the following formula:

number

[0037] From the viewpoint of achieving a good balance between compatibility with thermosetting resins, low thermal expansion, and chemical resistance, the epoxy-modified silicone B preferably contains an epoxy-modified silicone represented by the following formula (1). [ka] (In the formula, R 1 each independently represents an alkylene group, a phenylene group, or an aralkylene group; R 2each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 1 or more.

[0038] In formula (1), R 1 Each of R independently represents an alkylene group, a phenylene group, or an aralkylene group. 1 The alkylene group represented by the formula (I) may be linear, branched, or cyclic. The number of carbon atoms in the alkylene group is preferably 1 to 12, and more preferably 1 to 4. The alkylene group is not particularly limited, but examples thereof include a methylene group, an ethylene group, and a propylene group.

[0039] In formula (1), R 1 The number of carbon atoms in the aralkylene group represented by the formula (XI) is preferably 7 to 30, and more preferably 7 to 13. The aralkylene group is not particularly limited, but examples thereof include groups represented by the following formula (XI). [ka] Formula (XI) (In formula (XI), * represents a bond.)

[0040] In formula (1), R 1 The group represented by the formula (I) 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 is particularly preferably a propylene group.

[0041] In formula (1), R 2Each of R independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group. The alkyl group and phenyl group may have a substituent. The alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic. The alkyl group is not particularly limited, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, and a cyclohexyl group. Among these, R 2 is preferably a methyl group or a phenyl group.

[0042] In formula (1), n ​​represents an integer of 1 or more, for example, 1 to 100. From the viewpoint of further improving compatibility with thermosetting resins, 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.

[0043] From the viewpoint of further improving compatibility with thermosetting resins, low thermal expansion, and chemical resistance in a well-balanced manner, it is preferable that epoxy-modified silicone B contains two or more types of epoxy-modified silicones represented by formula (1). In this case, it is preferable that the two or more types of epoxy-modified silicones contained each have a different n, and it is more preferable to contain an epoxy-modified silicone in formula (1) where n is 1 to 2, and an epoxy-modified silicone in formula (1) where n is 5 to 20.

[0044] From the viewpoint of more effectively and reliably achieving the effects of the present invention, the average number of epoxy groups per molecule of epoxy-modified silicone B is preferably from 1 to less than 3, and more preferably from 1.5 to 2.5. The average number of epoxy groups is calculated by the following formula:

number

[0045] [Epoxy compound C] Epoxy compound C is an epoxy compound other than epoxy-modified silicone B, and more specifically, an epoxy compound without a polysiloxane skeleton. By containing epoxy compound C, the curable composition can exhibit excellent compatibility, chemical resistance, copper foil adhesion, and insulation reliability.

[0046] The epoxy compound C is not particularly limited as long as it is an epoxy compound other than the epoxy-modified silicone B. From the viewpoint of achieving even better compatibility, chemical resistance, copper foil adhesion, and insulation reliability, the epoxy compound preferably contains a bifunctional epoxy compound having two epoxy groups in one molecule.

[0047] The bifunctional epoxy compound is not particularly limited, but examples thereof include bisphenol-type epoxy resins (e.g., bisphenol A-type epoxy resins, bisphenol E-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, and bisphenol fluorene-type epoxy resins), phenol novolac-type epoxy resins (e.g., phenol novolac-type epoxy resins, bisphenol A novolac-type epoxy resins, and cresol novolac-type epoxy resins), trisphenolmethane-type epoxy resins, aralkyl-type epoxy resins, biphenyl-type epoxy resins containing a biphenyl skeleton, naphthalene-type epoxy resins containing a naphthalene skeleton, anthracene-type epoxy resins containing a dihydroanthracene skeleton, glycidyl ester-type epoxy resins, polyol-type epoxy resins, isocyanurate ring-containing epoxy resins, dicyclopentadiene-type epoxy resins, fluorene-type epoxy resins containing a fluorene skeleton, epoxy resins consisting of bisphenol A-type structural units and hydrocarbon-based structural units, and halogen compounds thereof. These epoxy compounds may be used alone or in combination of two or more.

[0048] The aralkyl epoxy resin is not particularly limited, but examples thereof include compounds represented by the following formula (b1). [ka] (In the formula, 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, and each ring may have a substituent other than a glycidyloxy group (for example, an alkyl group having 1 to 5 carbon atoms or a phenyl group).

[0049] The biphenyl type epoxy resin is not particularly limited, but examples thereof include a compound represented by the following formula (b2) (compound b2). [ka] (In the formula, each Ra independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)

[0050] In formula (b2), the alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic. The alkyl group is not particularly limited, but examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, and a cyclohexyl group.

[0051] 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 Ra. Specifically, a mixture of biphenyl-type epoxy resins having different numbers of alkyl groups Ra is preferred, and a mixture of compound b2 having an alkyl group Ra of 0 and compound b2 having an alkyl group Ra of 4 is more preferred.

[0052] The naphthalene type epoxy resin is not particularly limited, but examples thereof include compounds represented by the following formula (b3). [ka] (In the formula, R 3b each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (e.g., a methyl group or an ethyl group), an aralkyl group, a benzyl group, a naphthyl group, or a naphthyl group containing a glycidyloxy group, and n represents an integer of 0 or more (e.g., 0 to 2).

[0053] The dicyclopentadiene type epoxy resin is not particularly limited, but examples thereof include compounds represented by the following formula (b4). [ka] (In the formula, R 3c are each independently a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (for example, a methyl group or an ethyl group).

[0054] The epoxy resin composed of bisphenol A structural units and hydrocarbon-based structural units is not particularly limited, but examples thereof include compounds represented by the following formula (b5). [ka] (In the formula, R 1x and R 2x each independently represents a hydrogen atom or a methyl group, R 3x ~R 6x each independently represents a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom, and X represents an ethyleneoxyethyl group, a di(ethyleneoxy)ethyl group, a tri(ethyleneoxy)ethyl group, a propyleneoxypropyl group, a di(propyleneoxy)propyl group, a tri(propyleneoxy)propyl group, or an alkylene group having 2 to 15 carbon atoms (for example, a methylene group or an ethylene group).

[0055] Among these, from the viewpoint of achieving even better compatibility, chemical resistance, copper foil adhesion, and insulation reliability, epoxy compound C is preferably at least one selected from the group consisting of bisphenol-type epoxy resins, aralkyl-type epoxy resins, biphenyl-type epoxy resins, naphthalene-type epoxy resins, and dicyclopentadiene-type epoxy resins, and more preferably a biphenyl-type epoxy resin and / or a naphthalene-type epoxy resin.

[0056] From the viewpoint of more effectively and reliably achieving 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, and more preferably 1.5 or more and 2.5 or less. The average number of epoxy groups is calculated by the following formula.

number

[0057] From the viewpoint of achieving even better compatibility, chemical resistance, copper foil adhesion, and insulation reliability, the content of epoxy compound C is preferably 5 to 95 mass%, more preferably 5 to 90 mass%, even more preferably 5 to 50 mass%, and particularly preferably 20 to 50 mass%, relative to 100 mass% of the total amount of epoxy-modified silicone B and epoxy compound C.

[0058] [Phenol compounds F other than alkenylphenol A] From the viewpoint of achieving even better copper foil adhesion, the curable composition of the first embodiment preferably contains a phenolic compound F other than alkenylphenol A. Examples of the phenolic compound F include, but are not limited to, bisphenol-type phenolic resins (e.g., bisphenol A-type resin, bisphenol E-type resin, bisphenol F-type resin, bisphenol S-type resin, etc.), phenol novolac resins (e.g., phenol novolac resin, naphthol novolac resin, cresol novolac resin, etc.), glycidyl ester-type phenolic resins, naphthalene-type phenolic resins, anthracene-type phenolic resins, dicyclopentadiene-type phenolic resins, biphenyl-type phenolic resins, alicyclic phenolic resins, polyol-type phenolic resins, aralkyl-type phenolic resins, phenol-modified aromatic hydrocarbon formaldehyde resins, and fluorene-type phenolic resins. These phenolic compounds may be used alone or in combination of two or more.

[0059] Among these, the phenol compound F is preferably a bifunctional phenol compound having two phenolic hydroxyl groups in one molecule, from the viewpoint of achieving even better compatibility and copper foil adhesion.

[0060] The bifunctional phenol compound is not particularly limited, but examples thereof include bisphenol, biscresol, bisphenols having a fluorene skeleton (e.g., bisphenols having a fluorene skeleton, biscresols having a fluorene skeleton, etc.), biphenols (e.g., p,p'-biphenol, etc.), dihydroxydiphenyl ethers (e.g., 4,4'-dihydroxydiphenyl ether, etc.), dihydroxydiphenyl ketones (e.g., 4,4'-dihydroxydiphenyl ketone, etc.), dihydroxydiphenyl sulfides (e.g., 4,4'-dihydroxydiphenyl sulfide, etc.), and dihydroxyarenes (e.g., hydroquinone, etc.). These bifunctional phenol compounds may be used alone or in combination of two or more. Among these, the bifunctional phenol compounds are preferably bisphenol, biscresol, or bisphenols having a fluorene skeleton, from the viewpoint of achieving even better copper foil adhesion.

[0061] From the viewpoint of achieving even better compatibility, the content of alkenylphenol A is preferably 1 to 50 parts by mass, more preferably 10 to 45 parts by mass, and even more preferably 15 to 40 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.

[0062] From the viewpoint of achieving a better balance between low thermal expansion and chemical resistance, the content of the epoxy-modified silicone B is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 40 to 50 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.

[0063] From the viewpoint of achieving even better compatibility, chemical resistance, copper foil adhesion, and insulation reliability, the content of epoxy compound C is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 10 to 30 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.

[0064] From the viewpoint of achieving even better copper foil adhesion, the content of the phenol compound F is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 10 to 30 parts by mass, relative to 100 parts by mass of the total amount of the alkenyl phenol A, the epoxy-modified silicone B, the epoxy compound C, and the phenol compound F.

[0065] When the curable composition does not contain the phenol compound F, the contents of the alkenyl phenol A, the epoxy-modified silicone B, and the epoxy compound C described above represent the contents relative to 100 parts by mass of the total amount of the alkenyl phenol A, the epoxy-modified silicone B, and the epoxy compound C.

[0066] [Second embodiment: curable composition] The curable composition of the second embodiment contains a polymer D containing 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. As the alkenylphenol A, the epoxy-modified silicone B, and the epoxy compound C, those described in the first embodiment above can be used.

[0067] Polymer D can exhibit sufficient compatibility even when mixed with a thermosetting resin that has poor compatibility with silicone-based compounds. As a result, a curable composition containing Polymer D and a thermosetting resin can provide a uniform varnish or cured product. A cured product such as a prepreg obtained using the curable composition has the components uniformly mixed with each other, and variations in physical properties due to non-uniformity of the components are suppressed.

[0068] The curable composition of the second embodiment may contain, in addition to the polymer D, one or more selected from the group consisting of an alkenylphenol A, an epoxy-modified silicone B, and an epoxy compound C. In this case, the alkenylphenol A, the epoxy-modified silicone B, or the epoxy compound C contained in the curable composition of the second embodiment may be an unreacted component remaining after polymerization of the polymer D, or may be a component newly added to the purified polymer D.

[0069] [Polymer D] Polymer D contains a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, and a structural unit derived from epoxy compound C, and may further contain a structural unit derived from phenol compound F, as necessary. Hereinafter, these structural units will also be referred to as structural units A, B, C, and F, respectively. By using polymer D, the curable composition of the second embodiment can exhibit even better compatibility, thermal expansion properties, chemical resistance, peel strength, and insulation reliability.

[0070] The weight average molecular weight of polymer D is 3.0 x 10 in terms of polystyrene measured by gel permeation chromatography. 3 ~5.0×10 4 Preferably, it is 3.0 × 10 3 ~2.0×10 4 It is more preferable that the weight average molecular weight is 3.0×10 3 When the weight average molecular weight is 5.0×10 or more, the curable composition tends to exhibit even better copper foil adhesion and chemical resistance. 4 When the ratio is equal to or less than 1, it is likely that even better compatibility can be exhibited.

[0071] The content of structural unit A in polymer D is preferably 5 to 50 mass % relative to the total mass of polymer D. When the content of structural unit A is within the above range, the curable composition tends to exhibit even better compatibility. From the same viewpoint, the content of structural unit A is more preferably 10 to 45 mass %, and even more preferably 15 to 40 mass %.

[0072] The content of structural unit B in polymer D is preferably 20 to 60 mass % relative to the total mass of polymer D. When the content of structural unit B is within the above range, the curable composition tends to exhibit even better balance between low thermal expansion and chemical resistance. From the same viewpoint, the content of structural unit B is more preferably 25 to 55 mass %, and even more preferably 30 to 50 mass %.

[0073] Structural unit B is preferably a structural unit derived from an epoxy-modified silicone having an epoxy equivalent of 50 to 350 g / mol (hereinafter also referred to as "low equivalent weight 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 weight epoxy-modified silicone B2").

[0074] The content of structural units B1 derived from low equivalent weight epoxy-modified silicone B1 in polymer D is preferably 5 to 22.5 mass %, more preferably 10 to 20 mass %, and even more preferably 10 to 17 mass %, relative to the total mass of polymer D.

[0075] The content of structural unit B2 derived from high equivalent weight epoxy-modified silicone B2 in polymer D is preferably 15 to 55 mass %, more preferably 20 to 52.5 mass %, and even more preferably 25 to 50 mass %, relative to the total mass of polymer D.

[0076] The mass ratio of the content of structural unit B2 to the content of structural unit B1 is preferably 1.5 to 4, more preferably 1.7 to 3.5, and even more preferably 1.9 to 3.1. When the contents of structural unit B1 and structural unit B2 satisfy the above relationship, copper foil adhesion and chemical resistance tend to be further improved.

[0077] The content of structural unit C in polymer D is preferably 5 to 30 mass% relative to the total mass of polymer D. When the content of structural unit C is within the above range, the curable composition tends to exhibit even better compatibility, chemical resistance, copper foil adhesion, and insulation reliability. From the same viewpoint, the content of structural unit C is preferably 10 to 25 mass%, and more preferably 15 to 20 mass%.

[0078] Furthermore, the content of structural unit C is preferably 5 to 95 mass%, more preferably 5 to 90 mass%, even more preferably 5 to 50 mass%, and particularly preferably 20 to 50 mass%, relative to the total mass of structural unit B and structural unit C. When the contents of structural unit B and structural unit C satisfy the above relationship, there is a tendency for even better compatibility, chemical resistance, copper foil adhesion, and insulation reliability to be further improved.

[0079] The content of structural unit F in polymer D is preferably 5 to 30 mass % relative to the total mass of polymer D. When the content of structural unit F is within the above range, the curable composition tends to exhibit even better copper foil adhesion. From the same viewpoint, the content of structural unit F is preferably 10 to 25 mass %, and more preferably 15 to 20 mass %.

[0080] The alkenyl group equivalent of polymer D is preferably 300 to 1500 g / mol. When the alkenyl group equivalent is 300 g / mol or more, the elastic modulus of the cured product of the curable composition tends to be further reduced, and as a result, the thermal expansion of substrates and the like obtained using the cured product tends to be further reduced. When the alkenyl group equivalent is 1500 g / mol or less, the compatibility, chemical resistance, and reliability of the curable composition tend to be further improved. From the same viewpoint, the alkenyl group equivalent is preferably 350 to 1200 g / mol, and more preferably 400 to 1000 g / mol.

[0081] Polymer D can be obtained, for example, by a step of reacting alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and, if necessary, phenol compound F, in the presence of polymerization catalyst G. This reaction may be carried out in the presence of an organic solvent. More specifically, in the above step, polymer D can be obtained by the addition reaction between the epoxy groups of epoxy-modified silicone B and epoxy compound C and the hydroxyl groups of alkenylphenol A, and the addition reaction between the hydroxyl groups of the resulting addition reaction product and the epoxy groups of epoxy-modified silicone B and epoxy compound C.

[0082] 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.

[0083] 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-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 ("TPIZ" available from Tokyo Chemical Industry Co., Ltd.) are preferred from the viewpoint of preventing homopolymerization of the epoxy component.

[0084] The amount of polymerization catalyst G (preferably an imidazole catalyst) used is not particularly limited and is, for example, 0.1 to 10 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. From the viewpoint of increasing the weight-average molecular weight of polymer D, the amount of polymerization catalyst G used is preferably 1.0 part by mass or more, and more preferably 4.0 parts by mass or less.

[0085] The organic solvent is not particularly limited, and for example, a polar solvent or a non-polar solvent can be used. Examples of polar solvents include, but are not limited to, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cellosolve-based solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ester-based 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. Examples of non-polar solvents include, but are not limited to, aromatic hydrocarbons such as toluene and xylene. These solvents can be used alone or in combination of two or more.

[0086] The amount of the organic solvent used is not particularly limited, and is, for example, 50 to 150 parts by mass per 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and phenol compound F.

[0087] The heating temperature is not particularly limited and may be, for example, 100 to 170° C. The heating time is also not particularly limited and may be, for example, 3 to 8 hours.

[0088] After the reaction in this step is completed, polymer D may be separated and purified from the reaction mixture by a conventional method.

[0089] [Thermosetting resin E] The curable compositions of the first and second embodiments preferably contain a thermosetting resin E. The polymer D having a silicone skeleton exhibits excellent compatibility even with thermosetting resins that have poor compatibility with silicone compounds. Therefore, even when the polymer D and the thermosetting resin E are combined, the components do not separate within the curable composition, and compatibility is excellent. Furthermore, the curable composition of the second embodiment contains the polymer D and the thermosetting resin E, thereby exhibiting even more excellent low thermal expansion properties and chemical resistance.

[0090] From the viewpoint of further improving low thermal expansion properties, chemical resistance, and copper foil adhesion, the thermosetting resin E preferably contains one or more compounds selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds, alkenyl-substituted nadimide compounds, and epoxy compounds, and more preferably contains one or more compounds selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds, and epoxy compounds.

[0091] The content of the thermosetting resin E is preferably 10 to 90 mass %, more preferably 20 to 80 mass %, and even more preferably 30 to 75 mass %, relative to 100 mass % of the resin solid content.

[0092] [Maleimide compounds] From the viewpoint of further improving low thermal expansion and chemical resistance, the thermosetting resin E preferably contains a maleimide compound. The maleimide compound is not particularly limited as long as it has one or more maleimide groups per molecule. Examples of the maleimide compound include monomaleimide compounds having one maleimide group per molecule (e.g., N-phenylmaleimide, N-hydroxyphenylmaleimide, etc.), polymaleimide compounds having two or more maleimide groups per molecule (e.g., bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, bis(3,5-dimethyl-4-maleimidophenyl)methane, bis(3,5-diethyl-4-maleimidophenyl)methane), m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide-(2 ,2,4-trimethyl)hexane, maleimide compounds represented by the following formula (3), prepolymers of these maleimide compounds and amine compounds, and the like. [ka] (In the formula, each R5 independently represents a hydrogen atom or a methyl group, and n1 represents an integer of 1 or greater.)

[0093] n1 is 1 or more, preferably 1-100, and more preferably 1-10.

[0094] These maleimide compounds may be used singly or in combination of two or more. Among these, 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, and the maleimide compound represented by formula (3).

[0095] The maleimide compound may be a commercially available product or a preparation prepared by a known method. Examples of commercially available maleimide compounds include "BMI-70," "BMI-80," and "BMI-1000P" manufactured by K.I. Kasei Co., Ltd., "BMI-3000," "BMI-4000," "BMI-5100," "BMI-7000," and "BMI-2300" manufactured by Daiwa Kasei Kogyo Co., Ltd., and "MIR-3000" manufactured by Nippon Kayaku Co., Ltd.

[0096] From the viewpoint of further improving low thermal expansion properties 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, relative to 100 parts by mass of the resin solid content.

[0097] [Cyanate ester compounds] From the viewpoint of further improving low thermal expansion and chemical resistance, the thermosetting resin E preferably contains a cyanate ester compound. The cyanate ester compound is not particularly limited as long as it is a compound having two or more cyanato groups (cyanate ester groups) in one molecule, but examples thereof include a compound represented by the following formula (4), a compound represented by the following formula (5) excluding the compound represented by formula (4), a biphenylaralkyl cyanate ester, bis(3,3-dimethyl-4-cyanatophenyl)methane, bis(4-cyanatophenyl)methane, 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, Examples of cyanate ester compounds include benzene, 1,3-dicyanatonaphthalene, 1,4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4,4'-dicyanatobiphenyl, bis(4-cyanatophenyl)ether, bis(4-cyanatophenyl)thioether, bis(4-cyanatophenyl)sulfone, and 2,2-bis(4-cyanatophenyl)propane. These cyanate ester compounds may be used alone or in combination of two or more. [ka] (In the formula, each R6 independently represents a hydrogen atom or a methyl group, and n2 represents an integer of 1 or greater.) [ka] (In the formula, each Rya independently represents an alkenyl group having 2 to 8 carbon atoms, each Ryb independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, each Ryc independently represents an aromatic ring having 4 to 12 carbon atoms, Ryc may form a condensed structure with a benzene ring, Ryc may or may not be present, A 1a 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), and when Ryc is absent, one benzene ring may have two or more Rya and / or Ryb groups. n represents an integer of 1 to 10.

[0098] Among these, the cyanate ester compound preferably contains a compound represented by formula (4) and / or formula (5) from the viewpoint of further improving low thermal expansion and chemical resistance.

[0099] In formula (4), n2 represents an integer of 1 or more, preferably an integer of 1-20, and more preferably an integer of 1-10.

[0100] In formula (5), the alkenyl group having 2 to 8 carbon atoms represented by Rya is not particularly limited, but examples thereof include a vinyl group, an allyl group, a propenyl group, a butenyl group, and a hexenyl group.

[0101] In formula (5), the alkyl group having 1 to 10 carbon atoms represented by Ryb is not particularly limited, but examples thereof include linear alkyl groups such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, and a hexyl group; and branched alkyl groups such as an isopropyl group, an isobutyl group, and a tert-butyl group.

[0102] In formula (5), A1a The alkylene group having 1 to 6 carbon atoms represented by the formula (5) is not particularly limited, but examples thereof include a methylene group, an ethylene group, a trimethylene group, and a propylene group. 1a The aralkylene group having 7 to 16 carbon atoms represented by the formula (I) is not particularly limited, but 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 represented by the following formula is not particularly limited, but examples thereof include a phenylene ring.

[0103] In formula (5), n represents an integer of 1 to 10, preferably an integer of 1 to 20, and more preferably an integer of 1 to 10.

[0104] The compound represented by formula (5) is preferably a compound represented by the following formula (c1). [ka] (In the formula, each Rx independently represents a hydrogen atom or a methyl group, each R 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.)

[0105] These cyanate ester compounds may be produced according to known methods, such as those described in JP-A-2017-195334 (particularly paragraphs 0052 to 0057).

[0106] From the viewpoint of further improving low thermal expansion properties and chemical resistance, the content of the cyanate ester compound as the thermosetting resin E is preferably 10 to 70 parts by mass, more preferably 15 to 60 parts by mass, and even more preferably 20 to 50 parts by mass, per 100 parts by mass of the resin solid content.

[0107] [Phenol compounds] The thermosetting resin E preferably contains a phenolic compound from the viewpoint of further improving copper foil adhesion. The phenolic compound is not particularly limited as long as it has two or more phenolic hydroxyl groups per molecule. Examples of the phenolic compound include phenols having two or more phenolic hydroxyl groups per molecule, bisphenols (e.g., bisphenol A, bisphenol E, bisphenol F, bisphenol S, etc.), diallyl bisphenols (e.g., diallyl bisphenol A, diallyl bisphenol E, diallyl bisphenol F, diallyl bisphenol S, etc.), phenolic novolac resins (e.g., phenol novolac resin, naphthol novolac resin, cresol novolac resin, etc.), naphthalene-type phenolic resins, dihydroanthracene-type phenolic resins, dicyclopentadiene-type phenolic resins, biphenyl-type phenolic resins, and aralkyl-type phenolic resins. These phenolic compounds may be used alone or in combination of two or more. Among these, the phenolic compound preferably contains an aralkyl-type phenolic resin from the viewpoint of further improving copper foil adhesion.

[0108] (Aralkyl phenolic resin) An example of the aralkyl phenol resin is a compound represented by the following formula (c2). [ka] (In the formula, Ar 1 each independently represents a benzene ring or a naphthalene ring; Ar 2 represents a benzene ring, a naphthalene ring, or a biphenyl ring; R 2a each independently 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).

[0109] The compound represented by formula (c2) is, from the viewpoint of further improving copper foil adhesion, 1 is a naphthalene ring, and Ar2 is a benzene ring (hereinafter also referred to as "naphthol aralkyl phenolic resin"), and 1 is a benzene ring, and Ar 2 is a biphenyl ring (hereinafter also referred to as "biphenylaralkyl type phenol resin").

[0110] The naphthol aralkyl phenol resin is preferably a compound represented by the following formula (2b). [ka] (In the formula, R 2a each independently represents a hydrogen atom or a methyl group (preferably a hydrogen atom), and m represents an integer of 1 to 10 (preferably an integer of 1 to 6).

[0111] The biphenylaralkyl phenol resin is preferably a compound represented by the following formula (2c). [ka] (In the formula, R 2b each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group (preferably a hydrogen atom), and m1 represents an integer of 1 to 20 (preferably an integer of 1 to 6).

[0112] The aralkyl phenol resin may be a commercially available product, or a product synthesized by a known method. Commercially available aralkyl phenol resins include "KAYAHARD GPH-65," "KAYAHARD GPH-78," and "KAYAHARD GPH-103" (biphenyl aralkyl phenol resins) manufactured by Nippon Kayaku Co., Ltd., and "SN-495" (naphthol aralkyl phenol resin) manufactured by Nippon Steel Chemical Co., Ltd.

[0113] From the viewpoint of further improving copper foil adhesion, the content of the phenol compound as thermosetting resin E is preferably 10 to 40 parts by mass, more preferably 15 to 35 parts by mass, and even more preferably 20 to 30 parts by mass, per 100 parts by mass of the resin solid content.

[0114] [Alkenyl-substituted nadimide compounds] From the viewpoint of further improving heat resistance, it is preferable that the thermosetting resin E contains an alkenyl-substituted nadiimide compound. The alkenyl-substituted nadiimide compound is not particularly limited as long as it is a compound having one or more alkenyl-substituted nadiimide groups in one molecule, and examples thereof include compounds represented by the following formula (2d): [ka] (In the formula, each R1 independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (for example, a methyl group or an ethyl group), and 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 (6) or (7): [ka] (In formula (6), R3 represents a methylene group, an isopropylidene group, CO, O, S, or SO2.) [ka] (In formula (7), each R4 independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)

[0115] The alkenyl-substituted nadimide compound represented by formula (6) or (7) may be a commercially available product, or a product produced according to a known method. Examples of commercially available products include "BANI-M" and "BANI-X" manufactured by Maruzen Petrochemical Co., Ltd.

[0116] The content of the alkenyl-substituted nadimide compound as the thermosetting resin E 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 solid content.

[0117] [Epoxy compounds] From the viewpoint of further improving chemical resistance, copper foil adhesion, and insulation reliability, it is preferable that the thermosetting resin E contains an epoxy compound. Note that this epoxy compound refers to an epoxy compound different from the epoxy-modified silicone B and epoxy compound C that constitute the polymer D.

[0118] The epoxy compound is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule, and examples thereof include bisphenol-type epoxy resins (e.g., bisphenol A-type epoxy resins, bisphenol E-type epoxy resins, bisphenol F-type epoxy resins, and bisphenol S-type epoxy resins), diallyl bisphenol-type epoxy resins (e.g., diallyl bisphenol A-type epoxy resins, diallyl bisphenol E-type epoxy resins, diallyl bisphenol F-type epoxy resins, and diallyl bisphenol S-type epoxy resins), phenol novolac-type epoxy resins (e.g., phenol novolac-type epoxy resins, bisphenol A novolac-type epoxy resins, and cresol novolac-type epoxy resins), aralkyl-type epoxy resins, biphenyl-type epoxy resins containing a biphenyl skeleton, naphthalene-type epoxy resins containing a naphthalene skeleton, anthracene-type epoxy resins containing a dihydroanthracene skeleton, glycidyl esters, polyol-type epoxy resins, isocyanurate ring-containing epoxy resins, dicyclopentadiene-type epoxy resins, epoxy resins composed of bisphenol A-type structural units and hydrocarbon-based structural units, and halogen compounds thereof. These epoxy compounds may be used singly or in combination of two or more.

[0119] Among these, from the viewpoint of further improving chemical resistance, copper foil adhesion, and insulation reliability, the epoxy compound is preferably at least one selected from the group consisting of aralkyl epoxy resins, naphthalene epoxy resins, dicyclopentadiene epoxy resins, and epoxy resins comprising bisphenol A structural units and hydrocarbon-based structural units, and more preferably contains a naphthalene epoxy resin.

[0120] (Aralkyl epoxy resin) The aralkyl epoxy resin is not particularly limited, but examples thereof include compounds represented by the following formula (3a). [ka] (In the formula, 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, and each ring may have a substituent other than a glycidyloxy group (for example, an alkyl group having 1 to 5 carbon atoms or a phenyl group).

[0121] The compound represented by formula (3a) is Ar 3 is a naphthalene ring, and Ar 4 is a benzene ring (also called "naphthalene aralkyl type epoxy resin"), and Ar 3 is a benzene ring, and Ar 4 is a biphenyl ring (also referred to as a "biphenyl aralkyl type epoxy resin"), and a biphenyl aralkyl type epoxy resin is more preferred.

[0122] The biphenylaralkyl epoxy resin is preferably a compound represented by the following formula (3b). [ka] (In the formula, ka represents an integer of 1 or more, preferably 1 to 20, and more preferably 1 to 6.)

[0123] The aralkyl epoxy resin may also be a compound represented by the following formula (3c): [ka] (In the formula, ky represents an integer of 1 to 10.)

[0124] The aralkyl epoxy resin may be a commercially available product, or a preparation prepared by a known method may be used. Commercially available naphthalene aralkyl epoxy resins include Nippon Steel & Sumikin Chemical Co., Ltd.'s "Epotohto (registered trademark) ESN-155," "Epotohto (registered trademark) ESN-355," "Epotohto (registered trademark) ESN-375," "Epotohto (registered trademark) ESN-475V," "Epotohto (registered trademark) ESN-485," and "Epotohto (registered trademark) ESN-175," Nippon Kayaku Co., Ltd.'s "NC-7000," "NC-7300," and "NC-7300L," and DIC Corporation's "HP-5000" and "HP-9900." Commercially available biphenyl aralkyl epoxy resins include Nippon Kayaku Co., Ltd.'s "NC-3000," "NC-3000L," and "NC-3000FH."

[0125] (Naphthalene-type epoxy resin) The naphthalene-type epoxy resin is not particularly limited, but examples thereof include naphthalene-skeleton-containing polyfunctional epoxy resins having a naphthalene skeleton represented by the following formula (3-1), and epoxy resins having a naphthalene skeleton, excluding the above-mentioned naphthalene aralkyl-type epoxy resins. Specific examples of naphthalene-type epoxy resins include naphthylene ether-type epoxy resins, and naphthylene ether-type epoxy resins are preferred from the viewpoint of further improving chemical resistance, copper foil adhesion, and insulation reliability. [ka] (In the formula, Ar 31 each independently represents a benzene ring or a naphthalene ring; Ar 41 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; each ring may have a substituent other than a glycidyloxy group (for example, 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 the groups represents a naphthalene ring.

[0126] The compound represented by formula (3-1) includes a compound represented by formula (3-2). [ka] (In the formula, R represents a methyl group, and kz has the same meaning as kz in the above formula (3-1).)

[0127] The naphthalene skeleton-containing polyfunctional epoxy resin may be a commercially available product or a product prepared by a known method. Examples of commercially available naphthalene skeleton-containing polyfunctional epoxy resins include "HP-9540" and "HP-9500" manufactured by DIC Corporation.

[0128] From the viewpoint of further improving chemical resistance, copper foil adhesion, and insulation reliability, the naphthylene ether type epoxy resin is preferably a compound represented by the following formula (3-3) or a compound represented by the following formula (3-4). [ka] (In the formula, R 13 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., a methyl group or an ethyl group), or an alkenyl group having 2 to 3 carbon atoms (e.g., a vinyl group, an allyl group, or a propenyl group). [ka] (In the formula, R 14 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., a methyl group or an ethyl group), or an alkenyl group having 2 to 3 carbon atoms (e.g., a vinyl group, an allyl group, or a propenyl group).

[0129] The naphthylene ether type epoxy resin may be a commercially available product or a product prepared by a known method. Examples of commercially available naphthylene ether type 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.

[0130] (Dicyclopentadiene type epoxy resin) The dicyclopentadiene type epoxy resin is not particularly limited, but examples thereof include compounds represented by the following formula (3-5). [ka] (In the formula, R 3c each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and k2 represents an integer of 0 to 10.

[0131] The dicyclopentadiene-type epoxy resin may be a commercially available product or a preparation prepared by a known method. Commercially available dicyclopentadiene-type epoxy resins include "EPICRON HP-7200L," "EPICRON HP-7200," "EPICRON HP-7200H," and "EPICRON HP-7000HH" manufactured by Dainippon Ink and Chemicals, Inc.

[0132] (Epoxy resin consisting of bisphenol A structural units and hydrocarbon structural units) An epoxy resin composed of bisphenol A structural units and hydrocarbon-based structural units (also referred to as a "specific epoxy resin") has one or more bisphenol A structural units and one or more hydrocarbon-based structural units in the molecule. An example of the specific epoxy resin is a compound represented by the following formula (3e): [ka] (In the formula, R 1x and R 2x each independently represents a hydrogen atom or a methyl group, R 3x ~R 6x each independently represents a hydrogen atom, a methyl group, a chlorine atom, or a bromine atom; X represents an ethyleneoxyethyl group, a di(ethyleneoxy)ethyl group, a tri(ethyleneoxy)ethyl group, a propyleneoxypropyl group, a di(propyleneoxy)propyl group, a tri(propyleneoxy)propyl group, or an alkylene group having 2 to 15 carbon atoms; and k3 represents a natural number.

[0133] k3 represents a natural number, preferably 1 to 100, and more preferably 1 to 10.

[0134] The specific epoxy resin may be a commercially available product or a product prepared by a known method. Examples of commercially available specific epoxy resins include "EPICLON EXA-4850-150" and "EPICLON EXA-4816" manufactured by DIC Corporation.

[0135] From the viewpoint of further improving chemical resistance, copper foil adhesion, and insulation reliability, the content of the epoxy compound as the thermosetting resin E is preferably 10 to 70 parts by mass, more preferably 15 to 60 parts by mass, and even more preferably 20 to 50 parts by mass, per 100 parts by mass of the resin solid content.

[0136] The thermosetting resin E may further contain other resins as long as they do not impair the effects of the curable compositions of the first and second embodiments. Examples of other resins include oxetane resins, benzoxazine compounds, and compounds having a polymerizable unsaturated group. These resins may be used alone or in combination of two or more.

[0137] Examples of oxetane resins include alkyl oxetanes such as oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3'-di(trifluoromethyl)perfluoxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetane, and products of Toagosei Co., Ltd. such as "OXT-101" and "OXT-121."

[0138] As used herein, the term "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," both of which are products of Konishi Chemical Co., Ltd.

[0139] Examples of compounds 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-type epoxy(meth)acrylate and bisphenol F-type epoxy(meth)acrylate; and benzocyclobutene resins.

[0140] The content of polymer D is preferably 5 to 50 mass%, more preferably 10 to 45 mass%, and even more preferably 10 to 30 mass%, relative to 100 mass% of the resin solid content. When the content is within the above range, the curable composition tends to exhibit even better compatibility, low thermal expansion, and chemical resistance in a well-balanced manner.

[0141] The content of polymer D is preferably 5 to 50 mass%, more preferably 10 to 45 mass%, and even more preferably 10 to 30 mass%, relative to 100 mass% of the total of polymer D and thermosetting resin E. When the content is within the above range, the curable composition tends to exhibit even better compatibility, low thermal expansion, and chemical resistance in a well-balanced manner.

[0142] [Inorganic filler] The curable compositions of the first and second embodiments preferably further contain an inorganic filler from the viewpoint of further improving low thermal expansion. The inorganic filler is not particularly limited, and examples thereof include silicas, silicon compounds (e.g., white carbon, etc.), metal oxides (e.g., alumina, titanium white, zinc oxide, magnesium oxide, zirconium oxide, etc.), metal nitrides (e.g., boron nitride, aggregated 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 heat-treated to remove some of the water of crystallization)). , 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, glass short fibers (including glass fine powders such as E-glass, T-glass, D-glass, S-glass, and Q-glass), hollow glass, spherical glass, etc. These inorganic fillers may 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 metal hydroxides and metal oxides, more preferably at least one selected from the group consisting of silica, boehmite, and alumina, and even more preferably silica.

[0143] Examples of silicas include natural silica, fused silica, synthetic silica, aerosil, hollow silica, etc. These silicas may be used alone or in combination of two or more. Among these, fused silica is preferred from the viewpoint of dispersibility, and two or more types of fused silica having different particle sizes are more preferred from the viewpoints of packing ability and flowability.

[0144] From the viewpoint of further improving low thermal expansion, 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.

[0145] [Silane coupling agents] The curable compositions of the first and second embodiments may further contain a silane coupling agent. By containing a silane coupling agent, the curable compositions of the first and second embodiments tend to further improve the dispersibility of the inorganic filler and further improve the adhesive strength between the components of the curable compositions of the first and second embodiments and the substrate described below.

[0146] The silane coupling agent is not particularly limited, and examples thereof include silane coupling agents generally used for the 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.), acrylicsilane 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 epoxysilane compounds include "KBM-403," "KBM-303," "KBM-402," and "KBE-403," both of which are products of Shin-Etsu Chemical Co., Ltd.

[0147] 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.

[0148] [Wetting and dispersing agent] The curable compositions of the first and second embodiments may further contain a wetting dispersant. By containing a wetting dispersant, the curable compositions of the first and second embodiments tend to further improve the dispersibility of the filler.

[0149] The wetting dispersant may be any known dispersant (dispersion stabilizer) used to disperse fillers, such as DISPER BYK-110, 111, 118, 180, 161, BYK-W996, W9010, and W903 manufactured by BYK-Chemie Japan Co., Ltd.

[0150] 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 per 100 parts by mass of the resin solid content.

[0151] [solvent] The curable compositions of the first and second embodiments may further contain a solvent. By including a solvent in the curable compositions of the first and second embodiments, the viscosity of the curable composition during preparation tends to decrease, and the handleability (ease of handling) and the impregnation into a substrate tend to be further improved.

[0152] The solvent is not particularly limited as long as it can dissolve a part or all of the components in the curable composition, and examples thereof include ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (toluene, xylene, etc.), amides (dimethylformaldehyde, etc.), propylene glycol monomethyl ether and its acetate, etc. These solvents may be used alone or in combination of two or more.

[0153] The curable compositions of the first and second embodiments can be produced, for example, by blending the components in a solvent all at once or sequentially and stirring the blended components. In this case, known processes such as stirring, mixing, and kneading are used to uniformly dissolve or disperse the components.

[0154] [Application] As described above, the curable composition of the present embodiment can exhibit excellent compatibility, low thermal expansion, and chemical resistance, and is therefore suitable for use in metal foil-clad laminates and printed wiring boards.

[0155] [Prepreg] The prepreg of this embodiment includes a substrate and the curable composition of this embodiment impregnated into or coated on the substrate. As described above, the prepreg may be a prepreg obtained by a known method, and specifically, the prepreg is obtained by impregnating or coating the substrate with the curable composition of this embodiment, and then semi-curing (B-staging) the composition by heating and drying at 100 to 200°C.

[0156] The prepreg of this embodiment also encompasses the form of a cured product obtained by thermally curing a semi-cured prepreg at a heating temperature of 180 to 230° C. for a heating time of 60 to 180 minutes.

[0157] The content of the curable composition in the prepreg is preferably 30 to 90% by volume, more preferably 35 to 85% by volume, and even more preferably 40 to 80% by volume, calculated as the solid content of the prepreg relative to the total amount of the prepreg. When the content of the curable composition is within the above range, moldability tends to be further improved. The solid content of the prepreg referred to here refers to the components remaining after removing the solvent from the prepreg, and for example, a filler is included in the solid content of the prepreg.

[0158] The substrate is not particularly limited, and examples thereof include known substrates used as materials for various printed wiring boards. Specific examples of the substrate include glass substrates, inorganic substrates other than glass (for example, inorganic substrates composed of inorganic fibers other than glass, such as quartz), and organic substrates (for example, organic substrates composed of organic fibers, such as wholly aromatic polyamide, polyester, polyparaphenylenebenzoxazole, and polyimide). These substrates may be used alone or in combination of two or more. Among these, glass substrates are preferred from the viewpoint of being more excellent in dimensional stability under heating.

[0159] Examples of fibers constituting the glass substrate include fibers such as E-glass, D-glass, S-glass, T-glass, Q-glass, L-glass, NE-glass, and HME-glass. Among these, the fibers constituting the glass substrate are preferably one or more types of fibers 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 achieving even greater strength and low water absorption.

[0160] The form of the substrate is not particularly limited, but examples thereof include woven fabric, nonwoven fabric, roving, chopped strand mat, surfacing mat, etc. The weaving method of the woven fabric is not particularly limited, but known weaves include plain weave, sieve weave, twill weave, etc., and an appropriate weave can be selected from these known weaves depending on the intended use and performance. Furthermore, glass woven fabrics that have been subjected to fiber opening treatment or surface treatment with a silane coupling agent or the like are preferably used. The thickness and mass of the substrate are not particularly limited, but typically those of about 0.01 to 0.1 mm are preferably used.

[0161] The resin sheet of this embodiment includes a support and the curable composition of this embodiment disposed on the surface of the support. The resin sheet of this embodiment may be formed, for example, by applying the curable composition of this embodiment to one or both sides of the support. The resin sheet of this embodiment can be produced, for example, by applying a curable composition used in prepregs directly to a support such as a metal foil or film, followed by drying.

[0162] The support is not particularly limited, but may be, for example, a known material used in various printed wiring board materials, and is preferably a resin sheet or metal foil. Examples of the resin sheet and metal foil include resin sheets such as polyimide film, polyamide film, polyester film, polyethylene terephthalate (PET) film, polybutylene terephthalate (PBT) film, polypropylene (PP) film, and polyethylene (PE) film, and metal foils such as aluminum foil, copper foil, and gold foil. Among these, electrolytic copper foil and PET film are preferred as the support.

[0163] The resin sheet of this embodiment can be obtained, for example, by applying the curable composition of this embodiment to a support and then semi-curing (B-staging). A method for producing a resin sheet of this embodiment is generally preferred, which involves producing a composite of a B-stage resin and a support. Specifically, for example, a resin sheet can be produced by applying the curable composition to a support such as copper foil and then semi-curing it by heating it in a dryer at 100 to 200°C for 1 to 60 minutes. The amount of curable composition adhered to the support is preferably in the range of 1.0 μm to 300 μm in terms of the resin thickness of the resin sheet. The resin sheet of this embodiment can be used as a build-up material for printed wiring boards.

[0164] [Metal foil-clad laminate] The metal foil-clad laminate of this embodiment includes a laminate formed from one or more selected from the group consisting of the prepreg and resin sheet of this embodiment, and metal foil arranged on one or both sides of the laminate. The laminate may be formed from one prepreg or resin sheet, or may be formed from multiple prepregs and / or resin sheets.

[0165] The metal foil (conductor layer) may be any metal foil used in various printed wiring board materials, such as copper, aluminum, etc. Examples of copper foil include rolled copper foil, electrolytic copper foil, etc. The thickness of the conductor layer is, for example, 1 to 70 μm, and preferably 1.5 to 35 μm.

[0166] The molding method and molding conditions for the metal foil-clad laminate are not particularly limited, and general techniques and conditions for laminates and multilayer boards for printed wiring boards can be applied. For example, when molding a laminate or metal foil-clad laminate, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, etc. can be used. In addition, when molding a laminate or metal foil-clad laminate (lamination molding), the temperature is 100 to 300°C, and the pressure is a surface pressure of 2 to 100 kgf / cm. 2 The heating time is generally in the range of 0.05 to 5 hours. Furthermore, if necessary, post-curing can be carried out at a temperature of 150 to 300°C. In particular, when a multi-stage press is used, in order to sufficiently promote the curing of the prepreg, the temperature is set to 200 to 250°C and the pressure to 10 to 40 kgf / cm. 2 The heating time is preferably 80 to 130 minutes, the temperature is 215 to 235°C, and the pressure is 25 to 35 kgf / cm 2 The heating time is more preferably 90 to 120 minutes. It is also possible to form a multilayer board by combining the above prepreg with a separately prepared wiring board for an inner layer and laminating and molding it.

[0167] [Printed wiring board] The printed wiring board of this embodiment has an insulating layer formed of one or more materials selected from the group consisting of the prepreg of this embodiment and the resin sheet of this embodiment, and a conductor layer formed on the surface of the insulating layer. The printed wiring board of this embodiment can be formed, for example, by etching the metal foil of the metal foil-clad laminate of this embodiment into a predetermined wiring pattern to form the conductor layer.

[0168] Specifically, the printed wiring board of this embodiment can be manufactured, for example, by the following method. First, a metal foil-clad laminate of this embodiment is prepared. The metal foil of the metal foil-clad laminate is etched into a predetermined wiring pattern to create an inner layer substrate having a conductor layer (inner layer circuit). Next, a predetermined number of insulating layers and metal foil for an outer layer circuit are laminated in this order on the surface of the conductor layer (interior circuit) of the inner layer substrate, and the laminate is integrally molded (laminate molding) by heating and pressing, to obtain a laminate. The laminate molding method and molding conditions are the same as those for the laminate and metal foil-clad laminate described above. Next, the laminate is drilled for through holes and via holes, and a plated metal film is formed on the wall surfaces of the holes to electrically connect the conductor layer (interior circuit) and the metal foil for the outer layer circuit. Next, the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to create an outer layer substrate having a conductor layer (external layer circuit). In this manner, a printed wiring board is manufactured.

[0169] In addition, when a metal foil-clad laminate is not used, a printed wiring board may be produced by forming a conductor layer that will become a circuit on the insulating layer. In this case, the conductor layer may be formed by electroless plating. [Example]

[0170] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples.

[0171] (Synthesis Example 1) Synthesis of 1-naphthol aralkyl cyanate ester compound (SN495V-CN) R in the above formula (2b) 2a300 g (1.28 mol of OH groups) of an α-naphthol aralkyl phenolic resin (SN495V, OH group equivalent: 236 g / eq., manufactured by Nippon Steel Chemical Co., Ltd.) in which all OH groups are hydrogen atoms and 194.6 g (1.92 mol) of triethylamine (1.5 mol per mol of hydroxyl groups) were dissolved in 1800 g of dichloromethane to prepare Solution 1. 125.9 g (2.05 mol) of cyanogen chloride (1.6 mol per mol of hydroxyl groups), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol per mol of hydroxyl groups), and 1205.9 g of water were added over 30 minutes while stirring, while maintaining the liquid temperature at -2 to -0.5°C. After the addition of Solution 1, the mixture was stirred at the same temperature for 30 minutes, and then a solution (Solution 2) prepared by dissolving 65 g (0.64 mol) of triethylamine (0.5 mol per mol of hydroxyl group) in 65 g of dichloromethane was added over 10 minutes. After the addition of Solution 2, the mixture was stirred at the same temperature for 30 minutes to complete the reaction. The reaction mixture was then allowed to stand, and the organic and aqueous phases were separated. The resulting organic phase was washed five times with 1300 g of water. The electrical conductivity of the wastewater from the fifth wash was 5 μS / cm, confirming that the ionic compounds were sufficiently removed by washing with water. The organic phase after washing was concentrated under reduced pressure and finally concentrated to dryness at 90°C for 1 hour to obtain 331 g of the desired naphthol aralkyl cyanate ester compound (SN495V-CN, cyanate ester group equivalent: 261 g / eq.) (orange viscous material). The infrared absorption spectrum of the resulting SN495V-CN was measured at 2250 cm. -1 The absorption of the cyanate ester group was observed, and the absorption of the hydroxyl group was not observed.

[0172] Example 1 A three-neck flask equipped with a thermometer and a Dimroth trap was charged with 5.3 parts by mass of diallyl bisphenol A (DABPA, Daiwa Chemical Industry Co., Ltd.), 5.8 parts by mass of biscresol fluorene (BCF, Osaka Gas Chemical Co., Ltd.), 4.4 parts by mass of epoxy-modified silicone b1 (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent: 200 g / mol), 8.7 parts by mass of epoxy-modified silicone b2 (KF-105, Shin-Etsu Chemical Co., Ltd., functional group equivalent: 490 g / mol), 5.8 parts by mass of biphenyl-type epoxy compound c1 (YL-6121H, Mitsubishi Chemical Corporation), and 30 parts by mass of propylene glycol monomethyl ether acetate (DOWANOL PMA, Dow Chemical Japan Co., Ltd.) as a solvent, and the mixture was 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 Chemical Industry Co., Ltd.) was added and the temperature was raised to 140°C, followed by stirring for 5 hours. After cooling, a phenoxy polymer solution (solid content 50% by mass) was obtained (polymer production process).

[0173] Diallyl bisphenol A corresponds to "alkenyl phenol A," epoxy-modified silicone b1 and epoxy-modified silicone b2 correspond to "epoxy-modified silicone B," and biphenyl-type epoxy compound c1 corresponds to "epoxy compound C." The phenoxy polymer solution also contains polymer D, which contains structural units derived from alkenyl phenol A, structural units derived from epoxy-modified silicone B, and structural units derived from epoxy compound C. Hereinafter, polymer D will also be referred to as phenoxy polymer.

[0174] 30 parts by weight (solids content) of this phenoxy polymer solution was mixed with 26 parts by weight of the α-naphthol aralkyl cyanate ester compound obtained in Synthesis Example 1, 17 parts by weight of a novolak maleimide compound (BMI-2300, Daiwa Chemical Industry Co., Ltd.), 27 parts by weight of a naphthylene ether epoxy compound (HP-6000, DIC Corporation), 100 parts by weight of spherical silica (SFP-130MC, Denka Co., Ltd.), 40 parts by weight of spherical silica (SC-4500SQ, Admatechs Co., Ltd.), 1 part by weight of a wetting and dispersing agent (DISPERBYK-161, BYK Japan KK), and 5 parts by weight of a silane coupling agent (KMB-403, Shin-Etsu Chemical Co., Ltd.) to obtain a varnish (varnish production step). This varnish was applied to an S-glass woven fabric (thickness 100 μm) by impregnation, and then dried by heating at 150° C. for 3 minutes to obtain a prepreg having a resin composition solid content (including filler) of 46 mass % (prepreg production step).

[0175] Example 2 A prepreg having a resin composition solids (including filler) content of 46 mass% was obtained in the same manner as in Example 1, except that in the polymer production step, the amount of imidazole catalyst g1 added was changed from 0.3 mass parts to 1.2 mass parts.

[0176] Example 3 A prepreg having a resin composition solids (including filler) content of 46% by mass was obtained in the same manner as in Example 1, except that in the polymer production step, the amount of diallyl bisphenol A added was changed from 5.3 parts by mass to 5.0 parts by mass, the amount of biscresol fluorene added was changed from 5.8 parts by mass to 5.5 parts by mass, the amount of epoxy-modified silicone b1 added was changed from 4.4 parts by mass to 3.7 parts by mass, the amount of epoxy-modified silicone b2 added was changed from 8.7 parts by mass to 11 parts by mass, the amount of biphenyl-type epoxy compound c1 added was changed from 5.8 parts by mass to 4.9 parts by mass, and the amount of imidazole catalyst g1 added was changed from 0.30 parts by mass to 1.2 parts by mass.

[0177] Example 4 A prepreg having a resin composition solids (including filler) content of 46% by mass was obtained in the same manner as in Example 1, except that in the polymer production step, 1.2 parts by mass of imidazole catalyst g2 (TPIZ, Tokyo Chemical Industry Co., Ltd.) was added instead of 0.3 parts by mass of imidazole catalyst g1.

[0178] Example 5 A prepreg having a resin composition solids content (including filler) of 46 mass% was obtained in the same manner as in Example 1, except that 5.8 mass parts of biphenyl-type epoxy compound c2 (YX-4000, Mitsubishi Chemical Corporation) was added instead of 5.8 mass parts of biphenyl-type epoxy compound c1 in the polymer production step. Note that biphenyl-type epoxy compound c2 corresponds to "epoxy compound C."

[0179] Example 6 A prepreg having a resin composition solids (including filler) content of 46% by mass was obtained in the same manner as in Example 1, except that in the polymer production step, the amount of diallyl bisphenol A added was changed from 5.3 parts by mass to 10 parts by mass, biscresol fluorene was not added, the amount of epoxy-modified silicone b1 added was changed from 4.4 parts by mass to 4.5 parts by mass, the amount of epoxy-modified silicone b2 added was changed from 8.7 parts by mass to 9.1 parts by mass, the amount of biphenyl-type epoxy compound c1 added was changed from 5.8 parts by mass to 6.0 parts by mass, and the amount of imidazole catalyst g1 added was changed from 0.3 parts by mass to 1.2 parts by mass.

[0180] Example 7 A prepreg with a resin composition solids (including filler) content of 46 mass% was obtained in the same manner as in Example 3, except that in the polymer production step, the amount of epoxy-modified silicone b2 added was changed from 11 mass parts to 7.0 mass parts, and 4.0 mass parts of epoxy-modified silicone b3 (X-22-163A, Shin-Etsu Chemical Co., Ltd., functional group equivalent 1000 g / mol) was added. Note that epoxy-modified silicone b3 corresponds to "epoxy-modified silicone B."

[0181] Example 8 In the polymer production step, the amount of diallyl bisphenol A added was changed from 5.3 parts by mass to 1.7 parts by mass, the amount of biscresol fluorene added was changed from 5.8 parts by mass to 1.8 parts by mass, the amount of epoxy-modified silicone b1 added was changed from 4.4 parts by mass to 1.2 parts by mass, the amount of epoxy-modified silicone b2 added was changed from 8.7 parts by mass to 3.7 parts by mass, the amount of biphenyl-type epoxy compound c1 added was changed from 5.8 parts by mass to 1.6 parts by mass, the amount of solvent added was changed from 30 parts by mass to 10 parts by mass, and the amount of imidazole catalyst g1 added was changed from 0.3 parts by mass to 0.4 parts by mass, except that a phenoxy polymer solution (solid content 50% by mass) was obtained in the same manner as in Example 1. A prepreg with a resin composition solids (including filler) content of 46% by mass was obtained in the same manner as in Example 1, except that in the varnish production process and the prepreg production process, the amount of the α-naphthol aralkyl cyanate ester compound added was changed from 26 parts by mass to 33 parts by mass, the amount of the novolac maleimide compound added was changed from 17 parts by mass to 22 parts by mass, and the amount of the naphthylene ether epoxy compound added was changed from 27 parts by mass to 35 parts by mass.

[0182] Example 9 A prepreg with a resin composition solids (including filler) content of 46% by mass was obtained in the same manner as in Example 3, except that in the varnish production process, the amount of α-naphthol aralkyl cyanate ester compound added was changed from 26 parts by mass to 50 parts by mass, no novolac maleimide compound was added, and the amount of naphthylene ether epoxy compound added was changed from 27 parts by mass to 50 parts by mass.

[0183] Example 10 A prepreg with a resin composition solids (including filler) content of 46% by mass was obtained in the same manner as in Example 3, except that in the varnish production step, no α-naphthol aralkyl cyanate ester compound was added, the amount of novolac maleimide compound added was changed from 17 parts by mass to 40 parts by mass, no naphthylene ether epoxy compound was added, and 30 parts by mass of alkenyl-substituted nadiimide (BANI-M, Maruzen Petrochemical Co., Ltd.) was added.

[0184] Example 11 A prepreg with a resin composition solids (including filler) content of 46% by mass was obtained in the same manner as in Example 3, except that in the varnish production process, no α-naphthol aralkyl cyanate ester compound was added, the amount of novolac maleimide compound added was changed from 17 parts by mass to 18 parts by mass, the amount of naphthylene ether epoxy compound added was changed from 27 parts by mass to 26 parts by mass, and 26 parts by mass of a phenol compound (GPH-103, Nippon Kayaku Co., Ltd.) was added.

[0185] (Comparative Example 1) A varnish was obtained by mixing 37 parts by weight of the α-naphthol aralkyl cyanate ester compound obtained in Synthesis Example 1, 24 parts by weight of a novolac maleimide compound (BMI-2300, Daiwa Chemical Industry Co., Ltd.), 39 parts by weight of a naphthylene ether epoxy compound (HP-6000, DIC Corporation), 100 parts by weight of spherical silica (SFP-130MC, Denka Co., Ltd.), 40 parts by weight of spherical silica (SC-4500SQ, Admatechs Co., Ltd.), 1 part by weight of a wetting and dispersing agent (DISPERBYK-161, BYK Japan Co., Ltd.), and 5 parts by weight of a silane coupling agent (KMB-403, Shin-Etsu Chemical Co., Ltd.). This varnish was impregnated and coated onto an S-glass woven fabric (100 μm thick) and dried at 150°C for 3 minutes to obtain a prepreg with a resin composition solids content (including filler) of 46% by weight.

[0186] (Comparative Example 2) A prepreg with a resin composition solids (including filler) content of 46% by mass was obtained in the same manner as in Example 1, except that in the polymer production step, the amount of diallyl bisphenol A added was changed from 5.3 parts by mass to 10 parts by mass, biscresol fluorene and epoxy-modified silicone b1 were not added, the amount of epoxy-modified silicone b2 added was changed from 8.7 parts by mass to 20 parts by mass, biphenyl-type epoxy compound c1 was not added, and the amount of imidazole catalyst g1 added was changed from 0.3 parts by mass to 1.2 parts by mass.

[0187] (Comparative Example 3) A prepreg with a resin composition solids (including filler) content of 46% by mass was obtained in the same manner as in Example 1, except that in the polymer production step, the amount of diallyl bisphenol A added was changed from 5.3 parts by mass to 17 parts by mass, biscresol fluorene was not added, the amount of epoxy-modified silicone b1 added was changed from 4.4 parts by mass to 4.5 parts by mass, the amount of epoxy-modified silicone b2 added was changed from 8.7 parts by mass to 9.0 parts by mass, biphenyl-type epoxy compound c1 was not added, and the amount of imidazole catalyst g1 added was changed from 0.3 parts by mass to 1.2 parts by mass.

[0188] Comparative Example 4 A prepreg having a resin composition solids content (including filler) of 46% by mass was obtained in the same manner as in Example 4, except that in the polymer production step, 5.8 parts by mass of a maleimide compound (BMI-70, K.I. Chemical Co., Ltd.) was added instead of 5.8 parts by mass of biphenyl-type epoxy compound c1.

[0189] (Comparative Example 5) A prepreg with a resin composition solids (including filler) content of 46% by mass was obtained in the same manner as in Example 1, except that in the polymer production step, the amount of diallyl bisphenol A added was changed from 5.3 parts by mass to 15 parts by mass, biscresol fluorene, epoxy-modified silicone b1, and epoxy-modified silicone b2 were not added, the amount of biphenyl-type epoxy compound c1 added was changed from 5.8 parts by mass to 15 parts by mass, and the amount of imidazole catalyst g1 added was changed from 0.3 parts by mass to 1.2 parts by mass.

[0190] (Comparative Example 6) A varnish was obtained by mixing 30 parts by weight of epoxy-modified silicone b1, 26 parts by weight of the α-naphthol aralkyl cyanate ester compound obtained in Synthesis Example 1, 17 parts by weight of a novolac maleimide compound (BMI-2300, Daiwa Chemical Industry Co., Ltd.), 27 parts by weight of a naphthylene ether epoxy compound (HP-6000, DIC Corporation), 100 parts by weight of spherical silica (SFP-130MC, Denka Co., Ltd.), 40 parts by weight of spherical silica (SC-4500SQ, Admatechs Co., Ltd.), 1 part by weight of a wetting and dispersing agent (DISPERBYK-161, BYK Japan KK), and 5 parts by weight of a silane coupling agent (KMB-403, Shin-Etsu Chemical Co., Ltd.). This varnish was applied to an S-glass woven fabric (thickness 100 μm) by impregnation, and then dried by heating at 150° C. for 3 minutes to obtain a prepreg having a resin composition solid content (including filler) of 46 mass %.

[0191] (Comparative Example 7) A prepreg with a resin composition solids (including filler) content of 46 mass% was obtained in the same manner as in Comparative Example 6, except that 30 mass parts of epoxy-modified silicone b2 (KF-105, Shin-Etsu Chemical Co., Ltd., functional group equivalent: 490 g / mol) was added instead of 30 mass parts of epoxy-modified silicone b1.

[0192] (Comparative Example 8) A prepreg with a resin composition solids (including filler) content of 46 mass% was obtained in the same manner as in Comparative Example 6, except that 30 mass parts of epoxy-modified silicone b3 (X-22-163A, Shin-Etsu Chemical Co., Ltd., functional group equivalent 1000 g / mol) was added instead of 30 mass parts of epoxy-modified silicone b1.

[0193] Various physical properties of the phenoxy polymers obtained in each of the Examples and Comparative Examples are shown in Table 1. The weight average molecular weights shown in Table 1 were determined by the GPC method using polystyrene as a standard substance.

[0194] [Appearance evaluation of phenoxy polymer solution] When the phenoxy polymer solutions obtained in each of Examples 1 to 11 and Comparative Examples 1 to 5 were visually inspected, the phenoxy polymer solutions of Examples 1 to 11 and Comparative Examples 1 and 5 were homogeneous, whereas the phenoxy polymer solutions of Comparative Examples 2 and 3 had become two-phase, and the phenoxy polymer solution of Comparative Example 4 had gelled.

[0195] [Appearance evaluation of varnish and prepreg] The appearance of the varnish and prepreg of each of Examples 1 to 11 and Comparative Examples 1 to 8 was visually evaluated according to the following evaluation criteria. ○: It had a uniform appearance. ×: The appearance was uneven.

[0196] [Production of metal foil-clad laminates] Two or eight prepregs obtained in Examples 1 to 11 and Comparative Examples 1 to 8 were stacked, and electrolytic copper foils (3EC-M2S-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) having a thickness of 12 μm were placed on top and bottom of the prepregs. A pressure of 30 kgf / cm was applied. 2 Lamination molding was performed at a temperature of 220°C for 120 minutes to obtain copper-clad laminates containing an insulating layer with a thickness of 0.2 mm or 0.8 mm as metal foil-clad laminates. Note that copper-clad laminates could not be produced for Comparative Examples 4 and 6 to 8. The properties of the obtained copper-clad laminates were evaluated by the methods described below. The evaluation results are shown in Table 1.

[0197] [Coefficient of thermal expansion] The linear thermal expansion coefficient of the glass cloth in the longitudinal direction of the insulating layer of the laminate was measured according to the thermomechanical analysis (TMA) method specified in JIS C 6481. Specifically, the copper foil on both sides of the copper-clad laminate (5 mm × 5 mm × 0.8 mm) obtained above was removed by etching, and then the laminate was heated in a constant temperature bath at 220°C for 2 hours to remove stress due to molding. The linear thermal expansion coefficient (CTE) (ppm / °C) was then measured from 60°C to 260°C using a thermomechanical analyzer (TA Instruments) by increasing the temperature from 40°C to 320°C at a rate of 10°C per minute.

[0198] [Copper foil peel strength (copper foil adhesion)] Using the copper foil-clad laminate (30 mm × 150 mm × 0.8 mm) obtained by the above method, the copper foil peel strength (copper foil adhesion) was measured in accordance with JIS C 6481. Note that for Comparative Example 2, peeling occurred during the measurement, making it impossible to measure.

[0199] [Desmear resistance] The copper foil on both sides of the copper foil-clad laminate (50 mm × 50 mm × 0.2 mm) obtained by the above method was removed by etching, and then the laminate was immersed in a swelling solution, Swelling Dip Securiganth P (Atotech Japan Co., Ltd.), at 80°C for 10 minutes. It was then immersed in a roughening solution, Concentrate Compact CP (Atotech Japan Co., Ltd.), at 80°C for 5 minutes. Finally, it was immersed in a neutralizing solution, Reduction Conditioner Securiganth P500 (Atotech Japan Co., Ltd.), at 45°C for 10 minutes. This treatment was repeated three times. The mass of the metal foil-clad laminate was measured before and after treatment to determine the mass loss. A smaller absolute value of the mass loss indicates better desmear resistance.

[0200] [Insulation reliability] The insulation reliability was evaluated by a line-to-line insulation reliability test using HAST (Highly Accelerated Life Test). First, a printed wiring board (line and space (L / S = 100 / 100 μm)) was formed from the copper-clad laminate (insulation layer thickness 0.2 mm) obtained above using a subtractive method. Next, a power supply was connected to the wiring, and continuous humidity insulation resistance was evaluated under conditions of a temperature of 130°C, humidity of 85%, and an applied voltage of 5 VDC. The resistance value was 1.0 × 10 8 A value of Ω or less was deemed to be a failure. The evaluation criteria were as follows: ○: No failures for over 500 hours ×: Failure within 500 hours

[0201] [Table 1] *In the table, "Number of epoxy groups / Number of phenol groups" refers to the total number of epoxy groups in epoxy-modified silicone B and epoxy compound C relative to the number of phenol groups in alkenylphenol A used in preparing polymer D. *In the table, "B / D" represents the content (mass%) of structural units derived from epoxy-modified silicone B relative to polymer D in the phenoxy polymer solution; polymer D does not include the imidazole catalyst or solvent. *In the table, "C / (B+C)" represents the content (mass%) of structural units derived from epoxy compound C relative to the total amount of structural units derived from epoxy-modified silicone B and structural units derived from epoxy compound C.

[0202] [Table 2] *In the table, "unpreparable" means that a prepreg worthy of evaluation could not be produced because the phenoxy polymer solution had become two-phased or gelled (Comparative Examples 2 to 4), or because the epoxy-modified silicone B used was incompatible with other thermosetting resins.

[0203] This application is based on a Japanese patent application (Patent Application No. 2018-140494) filed with the Japan Patent Office on July 26, 2018, the contents of which are incorporated herein by reference. [Industrial Applicability]

[0204] The present invention has industrial applicability as a curable composition used as a material for prepregs, resin sheets, metal foil-clad laminates, printed wiring boards, etc.

Claims

1. The composition contains an alkenylphenol A, an epoxy-modified silicone B, and an epoxy compound C other than the epoxy-modified silicone B, the alkenylphenol A has an average number of phenol groups per molecule of 1 or more and less than 3, the epoxy-modified silicone B has an average number of epoxy groups per molecule of 1.5 or more and less than 3, and the epoxy compound C has an average number of epoxy groups per molecule of 1.5 or more and less than 3, The alkenylphenol A comprises diallyl bisphenol and / or dipropenyl bisphenol. the epoxy-modified silicone B contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g / mol, the content of the alkenylphenol A is 1 to 50 parts by mass relative to 100 parts by mass of the total amount of the alkenylphenol A, the epoxy-modified silicone B, and the epoxy compound C; Curable composition.

2. The epoxy-modified silicone B contains an epoxy-modified silicone represented by the following formula (1): The curable composition of claim 1. 【Chemistry 1】 (In the formula, R 1 each independently represents an alkylene group, a phenylene 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 1 or greater.

3. The epoxy compound C contains an epoxy compound represented by the following formula (2): The curable composition according to claim 1 or 2. 【Chemistry 2】 (In the formula, R a each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.

4. the content of the epoxy compound C is 5 to 50% by mass relative to 100% by mass of the total amount of the epoxy-modified silicone B and the epoxy compound C; The curable composition according to any one of claims 1 to 3.

5. Further containing a thermosetting resin E, The curable composition according to any one of claims 1 to 4.

6. the thermosetting resin E contains one or more compounds selected from the group consisting of maleimide compounds, cyanate ester compounds, phenolic compounds other than the alkenylphenol A, and alkenyl-substituted nadimide compounds; The curable composition according to claim 5.

7. a polymer D containing 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; the alkenylphenol A has an average number of phenol groups per molecule of 1 or more and less than 3, the epoxy-modified silicone B has an average number of epoxy groups per molecule of 1.5 or more and less than 3, and the epoxy compound C has an average number of epoxy groups per molecule of 1.5 or more and less than 3, The alkenylphenol A comprises diallyl bisphenol and / or dipropenyl bisphenol. the epoxy-modified silicone B contains an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g / mol, The content of the alkenylphenol A is 5 to 50 mass% based on the total mass of the polymer D. Curable composition.

8. The weight average molecular weight of the polymer D is 3.0 × 10 3 ~5.0 x 10 4 That is, The curable composition of claim 7.

9. the content of the structural units derived from the epoxy-modified silicone B in the polymer D is 20 to 60% by mass relative to the total mass of the polymer D; The curable composition according to claim 7 or 8.

10. The alkenyl group equivalent weight of the polymer D is 300 to 1500 g / mol. The curable composition according to any one of claims 7 to 9.

11. The content of the polymer D is 5 to 50% by mass relative to 100% by mass of the resin solid content. The curable composition according to any one of claims 7 to 10.

12. Further containing a thermosetting resin E, The curable composition according to any one of claims 7 to 11.

13. the thermosetting resin E contains one or more compounds selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds, alkenyl-substituted nadimide compounds, and epoxy compounds; The curable composition of claim 12.

14. The maleimide compound 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, and a maleimide compound represented by the following formula (3): The curable composition according to claim 6 or 13. 【Transformation 3】 (In the formula, R 5 each independently represents a hydrogen atom or a methyl group; n 1 represents an integer of 1 or more.)

15. The cyanate ester compound includes a compound represented by the following formula (4) and / or a compound represented by the following formula (5) excluding the compound represented by the following formula (4): The curable composition according to any one of claims 6, 13 and 14. 【Chemistry 4】 (In the formula, R 6 each independently represents a hydrogen atom or a methyl group, n 2 represents an integer of 1 or more.) 【Transformation 5】 (In the formula, R ya each independently represents an alkenyl group having 2 to 8 carbon atoms; R yb each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom; R yc each independently represents an aromatic ring having 4 to 12 carbon atoms; R yc may form a condensed structure with a benzene ring, and R yc may or may not be present, and 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 single bond; R yc When R is not present, one benzene ring ya and / or R yb and n represents an integer of 1 to 10.)

16. The epoxy compound includes a compound represented by the following formula (6) or a compound represented by the following formula (7): The curable composition according to any one of claims 13 to 15. 【Transformation 6】 (In the formula, R 13 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms. 【Transformation 7】 (In the formula, R 14 each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, or an alkenyl group having 2 to 3 carbon atoms.

17. Further containing an inorganic filler, The content of the inorganic filler is 50 to 1000 parts by mass per 100 parts by mass of the resin solid content. The curable composition according to any one of claims 1 to 16.

18. For printed wiring boards, The curable composition according to any one of claims 1 to 17.

19. A substrate; The curable composition according to any one of claims 1 to 18 impregnated or coated on the substrate. Prepreg.

20. A support; and the curable composition according to any one of claims 1 to 18 disposed on the surface of the support. Resin sheet.

21. A laminate formed of one or more selected from the group consisting of the prepreg according to claim 19 and the resin sheet according to claim 20; A metal foil disposed on one or both sides of the laminate, Metal foil laminate.

22. An insulating layer formed of at least one material selected from the group consisting of the prepreg according to claim 19 and the resin sheet according to claim 20; a conductor layer formed on the surface of the insulating layer, Printed wiring board.

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