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

Abstract

A curable composition comprising alkenylphenol (A), epoxy-modified silicone (B), an epoxy compound (C) other than the epoxy-modified silicone (B), and aminotriazine novolac resin (D).

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 Art

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

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

[0004] Patent Document 2 discloses a method for producing a semiconductor encapsulating resin by reacting a polymaleimide with an addition polymer of a diglycidyl polysiloxane represented by the following formula (I) and a diallylbisphenol represented by the following formula (II) with an allylated phenolic resin represented by the following formula (III) in a specified ratio and under specified conditions. This document discloses that the polymaleimide used in the semiconductor encapsulating resin obtained by the above-mentioned production method has excellent compatibility with the above-mentioned addition polymer. Furthermore, the composition using the semiconductor encapsulating resin has excellent cured product properties (e.g., high glass transition temperature, moisture resistance, and heat strength), and is highly reliable as a semiconductor encapsulating resin composition. This document discloses that component b in the following formula (III) reacts with a maleimide group during the resin formation reaction with the polymaleimide, and is an important component for improving the compatibility of the polymaleimide with the polysiloxane.

[0005]

[0006] (Where R 1 represents an alkylene group or a phenylene group, R 2 Each independently represents an alkyl group or a phenyl group, and n represents an integer of 1 to 100.

[0007]

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

[0009]

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

[0011] Prior art documents

[0012] Patent documents

[0013] Patent document 1: Japanese Unexamined Patent Application Publication No. 2012 - 149154

[0014] Patent document 2: Japanese Unexamined Patent Application Publication No. 4 - 4213 Summary of the invention

[0015] Problems to be solved by the invention

[0016] As described in Patent Document 1, a resin composition containing a thermosetting resin such as a silicone compound having an epoxy group in its molecular structure and a maleimide compound has excellent low thermal expansion properties. However, the inventors have found that in the above resin composition, due to the insufficient compatibility between the silicone compound and the thermosetting resin, there are problems in terms of moldability. In addition, the inventors have found that the metal foil peeling strength (for example, copper foil peeling strength) when the above resin composition is made into a metal-clad laminate is insufficient.

[0017] On the other hand, the resin composition described in Patent Document 2 is for semiconductor sealing and has not been studied for the copper foil peeling strength required for the characteristics of printed circuit boards. 7]

[0018] The present invention has been made in view of the above problems, and an object thereof is to provide a curable composition, a prepreg, a resin sheet, a metal-clad laminate, and a printed circuit board having excellent copper foil peeling strength.

[0019] Solutions to solve the problems

[0020] The inventors have repeatedly and intensively studied to solve the above problems. As a result, it has been found that if it is a curable composition containing an alkenyl phenol, an epoxy-modified silicone, an epoxy compound other than the epoxy-modified silicone, and an amino triazine phenolic resin, or a curable composition containing a polymer having these components as constituent units, the above problems can be solved, and the present invention has been completed.

[0021] That is, the present invention is as follows. [1]

[0023] A curable composition comprising: an alkenyl phenol A, an epoxy-modified silicone B, an epoxy compound C other than the aforementioned epoxy-modified silicone B, and an amino triazine phenolic resin D. [2]

[0025] The curable composition according to the above [1], wherein the average number of phenol groups per molecule of the alkenylphenol A is 1 or more and less than 3, the average number of epoxy groups per molecule of the epoxy-modified silicone B is 1 or more and less than 3, and the average number of epoxy groups per molecule of the epoxy compound C is 1 or more and less than 3. [3]

[0027] The curable composition according to the above-mentioned [1] or [2], wherein the alkenylphenol A contains diallylbisphenol and / or dipropylenebisphenol. [4]

[0029] The curable composition according to any one of [1] to [3] above, wherein the epoxy-modified silicone B comprises an epoxy-modified silicone having an epoxy equivalent of 140 to 250 g / mol. [5]

[0031] The curable composition according to any one of the above-mentioned [1] to [4], wherein the epoxy-modified silicone B comprises an epoxy-modified silicone represented by the following formula (1).

[0032]

[0033] (Where R 1 Each independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 0 to 100. [6]

[0035] The cured product composition according to any one of the above-mentioned [1] to [5], wherein the epoxy compound C contains a compound represented by the following formula (b2).

[0036]

[0037] (Where R a Each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.) [7]

[0039] The curable composition according to any one of the above [1] to [6], wherein the content of the epoxy compound C is 20 to 50% by mass relative to 100% by mass of the total amount of the epoxy-modified silicone B and the epoxy compound C. [8]

[0041] The curable composition according to any one of the above-mentioned [1] to [7], wherein the aminotriazine novolac resin D is a novolac resin having 2 to 20 phenolic hydroxyl groups per one triazine skeleton in the molecule. [9]

[0043] A curable composition includes a polymer E containing a structural unit derived from an alkenylphenol A, a structural unit derived from an epoxy-modified silicone B, a structural unit derived from an epoxy compound C, and a structural unit derived from an aminotriazine novolac resin D.

[10]

[0045] The curable composition according to the above-mentioned [9], wherein the weight average molecular weight of the polymer E is 3.0×10 3 ~5.0×10 4 .

[11]

[0047] The curable composition according to [9] or

[10] , wherein the content of the structural unit derived from the epoxy-modified silicone B in the polymer E is 20 to 60% by mass relative to the total mass of the polymer E.

[12]

[0049] The curable composition according to any one of [9] to

[11] above, wherein the polymer E has an alkenyl equivalent weight of 300 to 1500 g / mol.

[13]

[0051] The curable composition according to any one of [9] to

[12] , wherein the content of the structural unit derived from the aminotriazine novolac resin D in the polymer E is 3 to 20% by mass relative to the total mass of the polymer E.

[14]

[0053] The curable composition according to any one of the above-mentioned [9] to

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

[15]

[0055] The curable composition according to any one of [9] to

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

[16]

[0057] The curable composition according to any one of [9] to

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

[17]

[0059] The curable composition according to any one of the above-mentioned [9] to

[16] , wherein the epoxy-modified silicone B comprises an epoxy-modified silicone represented by the following formula (1).

[0060]

[0061] (Where R 1 Each independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 0 to 100.

[18]

[0063] The curable composition according to any one of the above-mentioned [9] to

[17] , wherein the epoxy compound C contains a compound represented by the following formula (b2).

[0064]

[0065] (Where R a Each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)

[19]

[0067] The curable composition according to any one of [9] to

[18] above, wherein the aminotriazine novolac resin D is a novolac resin having 2 to 20 phenolic hydroxyl groups per one triazine skeleton in the molecule.

[20]

[0069] The curable composition according to any one of the above [9] to

[19] , further comprising an epoxy compound C, wherein the epoxy compound C comprises a compound represented by the following formula (3-3) or a compound represented by the following formula (3-4).

[0070]

[0071] (Where 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.)

[0072]

[0073] (Where 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.) [twenty one]

[0075] The curable composition according to any one of the above [1] to

[20] , further comprising at least one compound F selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound A' other than alkenylphenol A, and an alkenyl-substituted nadic imide compound. [twenty two]

[0077] The curable composition according to the above-mentioned

[21] , wherein the maleimide compound comprises at least one selected from the group consisting of bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, a maleimide compound represented by the following formula (3) and a maleimide compound represented by the following formula (3').

[0078]

[0079] (In the formula, R5 each independently represents a hydrogen atom or a methyl group, and n1 represents an integer greater than 1.)

[0080]

[0081] (In formula (3'), R 13 Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, n 4 represents an integer greater than or equal to 1 and less than or equal to 10.) [twenty three]

[0083] The curable composition according to

[21] or

[22] , wherein the cyanate compound comprises a compound represented by the following formula (4) and / or a compound represented by the following formula (5) other than the compound represented by the following formula (4).

[0084]

[0085] (In the formula, R6 each independently represents a hydrogen atom or a methyl group, and n2 represents an integer greater than 1.)

[0086]

[0087] (Where R ya Each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, and R yb Each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and R yc Each independently represents an aromatic ring having 4 to 12 carbon atoms, R yc Optionally form a condensed structure with a benzene ring, R yc Optional presence or absence, A 1aEach 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, and R yc When not present, one benzene ring may optionally have two or more R ya and / or R yb , n represents an integer of 1 to 20. ) [twenty four]

[0089] The curable composition according to any one of the above-mentioned

[21] to

[23] , wherein the phenol compound A' contains a compound represented by the following formula (8).

[0090]

[0091] (In the formula, R7 each independently represents a hydrogen atom or a methyl group, and n3 represents an integer greater than 1.)

[25]

[0093] The curable composition according to any one of the above [1] to

[24] , further comprising an inorganic filler, wherein the content of the inorganic filler is 50 to 1000 parts by mass based on 100 parts by mass of the resin solid content.

[26]

[0095] The curable composition according to the above-mentioned

[25] , wherein the inorganic filler comprises one or more selected from the group consisting of silicas, boehmite, and alumina.

[27]

[0097] The curable composition according to any one of [1] to

[21] , which is used for a printed wiring board.

[28]

[0099] A prepreg comprising a substrate and the curable composition according to any one of [1] to

[27] above, which is impregnated into or coated on the substrate.

[29]

[0101] A resin sheet comprising a support and the curable composition according to any one of [1] to

[27] above, which is disposed on a surface of the support.

[30]

[0103] A metal foil-clad laminate comprising:

[0104] A laminate formed using one or more selected from the group consisting of the prepreg described in

[28] and the resin sheet described in

[29] ; and

[0105] A metal foil is disposed on one or both sides of the laminate.

[31]

[0107] A printed circuit board comprising:

[0108] An insulating layer formed using one or more selected from the group consisting of the prepreg described in

[28] and the resin sheet described in

[29] ; and

[0109] A conductive layer is formed on the surface of the insulating layer.

[32]

[0111] A method for producing the curable composition according to any one of [1] to

[27] , comprising:

[0112] a step of obtaining a prepolymer, wherein the prepolymer is obtained by polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C; and

[0113] A step of reacting the aminotriazine novolac resin D with the prepolymer.

[0114] Effects of the Invention

[0115] According to the present invention, a curable composition, a prepreg, a resin sheet, a metal foil-clad laminate, and a printed wiring board having excellent copper foil peel strength can be provided. DETAILED DESCRIPTION

[0116] Hereinafter, a mode for carrying out the present invention (hereinafter referred to as “this embodiment”) will be described in detail. However, the present invention is not limited thereto and various modifications are possible without departing from the spirit and scope of the present invention.

[0117] As used herein, "resin solids" refers to the components of the curable composition of this embodiment excluding the solvent and filler, unless otherwise specified. "100 parts by mass of resin solids" means the total of the components of the curable composition excluding the solvent and filler is 100 parts by mass. Furthermore, "100% by mass of resin solids" means the total of the components of the curable composition excluding the solvent and filler is 100% by mass.

[0118] In the curable composition of the first embodiment described below, “excellent compatibility” means that liquid phase separation does not occur in the state of a mixture (eg, varnish) containing alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and aminotriazine novolac resin D.

[0119] In the curable composition of the second embodiment described below, “excellent compatibility” means that liquid phase separation does not occur in the state of a mixture (eg, varnish) containing the polymer E and other components.

[0120] The curable composition of this embodiment has excellent compatibility, thus suppressing liquid phase separation during the molding process, enabling the production of molded products with excellent appearance. Furthermore, the resulting molded products tend to have excellent isotropy of physical properties. It should be noted that, in this specification, the term "curable composition of this embodiment" encompasses both the "curable composition of the first embodiment" and the "curable composition of the second embodiment," unless otherwise specified.

[0121] [First embodiment: curable composition]

[0122] The curable composition of the first embodiment contains alkenylphenol A, epoxy-modified silicone B, epoxy compound C other than epoxy-modified silicone B (hereinafter also referred to as "epoxy compound C"), and aminotriazine novolac resin D. The curable composition containing these components tends to have better compatibility with thermosetting resins (hereinafter also referred to as "thermosetting resins") that are insufficiently compatible with epoxy-modified silicone B. Therefore, the curable composition of the first embodiment can exhibit better compatibility and excellent copper foil peel strength. In addition, in the curable composition, if a part of each of these components is reacted (polymerized) and used, further better compatibility can be exhibited, and better copper foil peel strength can be exhibited (curable composition of the second embodiment).

[0123] [Alkenylphenol A]

[0124] There are no particular limitations on the alkenylphenol A as long as it is a compound having a structure in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. The curable composition of the present embodiment can exhibit excellent compatibility by containing alkenylphenol A.

[0125] There is no particular limitation on the alkenyl group, and examples thereof include alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl. Among them, from the viewpoint of more effectively and surely exerting the effects of the present invention, the alkenyl group is preferably an allyl group and / or propenyl, and more preferably an allyl group. The number of alkenyl groups directly bonded to a phenolic aromatic ring is not particularly limited, and for example, it is 1 to 4. From the viewpoint of more effectively and surely exerting the effects of the present invention, the number of alkenyl groups directly bonded to a phenolic aromatic ring is preferably 1 to 2, and more preferably 1. In addition, the bonding position of the alkenyl group to the phenolic aromatic ring is not particularly limited, and is preferably the ortho position (2, 6 positions).

[0126] The phenolic aromatic ring is one in which one or more hydroxyl groups are directly bonded to the aromatic ring, and examples thereof include a phenol ring and a naphthol ring. The number of hydroxyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 2, and preferably 1.

[0127] The phenolic aromatic ring may have a substituent other than an alkenyl group. Examples of such substituents include a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, a cyclic alkoxy group having 3 to 10 carbon atoms, and a halogen atom. When the phenolic aromatic ring has a substituent other than an alkenyl group, the number of such substituents directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 2. In addition, the bonding position of such a substituent on the phenolic aromatic ring is not particularly limited.

[0128] Alkenylphenol A may have a structure in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. From the viewpoint of more effectively and reliably exerting the effects of the present invention, alkenylphenol A preferably has a structure in which one or two alkenyl groups are directly bonded to a phenolic aromatic ring, and preferably has two alkenyl groups.

[0129] The alkenylphenol A may be, for example, a compound represented by the following formula (1A) or the following formula (1B).

[0130]

[0131] (In the formula, Rxa each independently represents an alkenyl group having 2 to 8 carbon atoms, Rxb each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, Rxc each independently represents an aromatic ring having 4 to 12 carbon atoms, Rxc may optionally form a condensed structure with a benzene ring, Rxc may be present or absent, 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 optionally have two or more groups of Rxa and / or Rxb.)

[0132]

[0133] (In the formula, Rxd each independently represents an alkenyl group having 2 to 8 carbon atoms, Rxe each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, Rxf represents an aromatic ring having 4 to 12 carbon atoms, Rxf optionally forms a condensed structure with a benzene ring, Rxf is optionally present or absent, and when Rxf is absent, one benzene ring optionally has two or more groups of Rxd and / or Rxe.)

[0134] In formula (1A) and formula (1B), the alkenyl group having 2 to 8 carbon atoms represented by Rxa and Rxd is not particularly limited, and examples thereof include vinyl, allyl, propenyl, butenyl, and hexenyl.

[0135] In formula (1A) and formula (1B), when the groups represented by Rxc and Rxf form a condensed structure with a benzene ring, examples include compounds containing a naphthol ring as a phenolic aromatic ring. Furthermore, in formula (1A) and formula (1B), when the groups represented by Rxc and Rxf do not exist, examples include compounds containing a phenol ring as a phenolic aromatic ring.

[0136] 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 straight-chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; and branched-chain alkyl groups such as isopropyl, isobutyl, and tert-butyl.

[0137] In formula (1A), the alkylene group having 1 to 6 carbon atoms represented by A is not particularly limited, and examples thereof include methylene, ethylene, trimethylene, and propylene. The aralkylene group having 7 to 16 carbon atoms represented by A is not particularly limited, and examples thereof include groups represented by the formula: -CH2-Ar-CH2-, -CH2-CH2-Ar-CH2-CH2-, or -CH2-Ar-CH2-CH2- (wherein Ar represents a phenylene group, a naphthylene group, or a biphenylene group). The arylene group having 6 to 10 carbon atoms represented by A is not particularly limited, and examples thereof include a phenylene ring.

[0138] In the compound represented by formula (1B), from the viewpoint of more effectively and reliably exhibiting the effects of the present invention, it is preferred that Rxf is a benzene ring (preferably a compound containing a dihydroxynaphthalene skeleton).

[0139] From the viewpoint of further improving compatibility, the alkenylphenol A is preferably an alkenylbisphenol in which one alkenyl group is bonded to each of the two phenolic aromatic rings of the bisphenol. From the same viewpoint, the alkenylbisphenol is preferably a diallylbisphenol in which one allyl group is bonded to each of the two phenolic aromatic rings of the bisphenol and / or a diallylbisphenol in which one propenyl group is bonded to each of the two phenolic aromatic rings of the bisphenol.

[0140] The diallyl bisphenol is not particularly limited, and examples thereof include o,o'-diallyl bisphenol A ("DABPA" manufactured by Yamato Chemical Industry Co., Ltd.), o,o'-diallyl bisphenol F, o,o'-diallyl bisphenol S, and o,o'-diallyl bisphenol fluorene. The dipropylene bisphenol is not particularly limited, and examples thereof include o,o'-dipropylene bisphenol A ("PBA01" manufactured by Gunei Chemical Industry Co., Ltd.), o,o'-dipropylene bisphenol F, o,o'-dipropylene bisphenol S, and o,o'-dipropylene bisphenol fluorene.

[0141] From the viewpoint of more effectively and reliably exhibiting the effects of the present invention, the average number of phenol groups per molecule of alkenylphenol A is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less. The average number of phenol groups is calculated by the following formula.

[0142]

[0143] Wherein, Ai represents the number of phenol groups of the alkenylphenol having i phenol groups in the molecule, Xi represents the ratio of the alkenylphenol having i phenol groups in the molecule to the total alkenylphenols, X1+X2+…X n =1.

[0144] [Epoxy modified silicone B]

[0145] The epoxy-modified silicone B is not particularly limited as long as it is a silicone compound or resin modified with an epoxy-containing group. The curable composition of this embodiment can exhibit excellent low thermal expansion and copper foil peel strength by containing the epoxy-modified silicone B.

[0146] The silicone compound or resin is not particularly limited as long as it is a compound having a polysiloxane skeleton formed by repeated siloxane bonds. The polysiloxane skeleton may be a linear skeleton, a cyclic skeleton, or a lattice-like skeleton. Among them, a linear skeleton is preferred from the viewpoint of more effectively and reliably exerting the effects of the present invention.

[0147] The epoxy group-containing group is not particularly limited, and examples thereof include groups represented by the following formula (a1).

[0148] -R 0 -X (a1)

[0149] (Where R 0 represents an alkylene group (for example, an alkylene group having 1 to 5 carbon atoms, such as methylene, ethylene, and propylene), and X represents a monovalent group represented by the following formula (a2) or a monovalent group represented by the following formula (a3).

[0150]

[0151] Epoxy-modified silicone B preferably contains an epoxy-modified silicone with an epoxy equivalent weight of 140 to 250 g / mol. By containing an epoxy-modified silicone with an epoxy equivalent weight within this range, epoxy-modified silicone B exhibits excellent compatibility with thermosetting resins, tending to achieve a well-balanced and further improved low thermal expansion and copper foil peel strength. From the same perspective, the epoxy equivalent weight is more preferably 145 to 245 g / mol, and even more preferably 150 to 240 g / mol.

[0152] From the perspective of further improving compatibility with thermosetting resins and achieving a well-balanced and further improved low thermal expansion and copper foil peel strength, the epoxy-modified silicone B preferably contains two or more epoxy-modified silicones. In this case, the two or more epoxy-modified silicones preferably have different epoxy equivalents, more preferably including an epoxy-modified silicone with an epoxy equivalent of 50 to 350 g / mol (hereinafter referred to as "low-equivalent-weight epoxy-modified silicone B1") and an epoxy-modified silicone with an epoxy equivalent of 400 to 4000 g / mol (hereinafter referred to as "high-equivalent-weight epoxy-modified silicone B2"), and even more preferably including an epoxy-modified silicone with an epoxy equivalent of 140 to 250 g / mol (low-equivalent-weight epoxy-modified silicone B1') and an epoxy-modified silicone with an epoxy equivalent of 450 to 3000 g / mol (high-equivalent-weight epoxy-modified silicone B2').

[0153] When the epoxy-modified silicone B contains two or more epoxy-modified silicones, the average epoxy equivalent of the epoxy-modified silicone B is preferably 140 to 3000 g / mol, more preferably 250 to 2000 g / mol, and even more preferably 300 to 1000 g / mol. The average epoxy equivalent is calculated by the following formula.

[0154]

[0155] (wherein, Ei represents the epoxy equivalent of one of the two or more epoxy-modified silicones, Wi represents the ratio of the above epoxy-modified silicones in epoxy-modified silicone B, W1+W2+…W n =1.)

[0156] From the viewpoint of further improving compatibility with thermosetting resins and further improving low thermal expansion and copper foil peeling strength in a well-balanced manner, the epoxy-modified silicone B preferably contains an epoxy-modified silicone represented by the following formula (1).

[0157]

[0158] In formula (1), R 1 Each independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 0 to 100.

[0159] In formula (1), R 1 The alkylene group represented by may be any of linear, branched or cyclic. The number of carbon atoms in the alkylene group is preferably 1 to 12, more preferably 1 to 4. Examples of the alkylene group include methylene, ethylene or propylene. Among these, R 1 Preferred is propylene.

[0160] In formula (1), R 1 The arylene group represented by may have a substituent. The number of carbon atoms in the arylene group is preferably 6 to 40, more preferably 6 to 20. Examples of the arylene group include phenylene, cyclohexylphenylene, hydroxyphenylene, cyanophenylene, nitrophenylene, naphthylene, biphenylene, anthrylene, pyrenylene, and fluorenylene. These groups may contain an ether bond, a ketone bond, or an ester bond.

[0161] In formula (1), R 1 The carbon number of the aralkylene group represented by is preferably 7 to 30, more preferably 7 to 13. Examples of the aralkylene group include groups represented by the following formula (XI).

[0162]

[0163] (In formula (XI), * represents an atomic bond.)

[0164] In formula (1), R 1 The group represented by may further have a substituent, and examples of the substituent include a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a cyclic alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, a branched alkoxy group having 3 to 10 carbon atoms, and a cyclic alkoxy group having 3 to 10 carbon atoms. Among these, R 1 A propylene group is particularly preferred.

[0165] In formula (1), R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group. The above alkyl groups and phenyl groups may have a substituent. The alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic. There are no particular limitations on the alkyl group, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl. Among these, R 2 Preferred is methyl or phenyl.

[0166] In formula (1), n represents an integer greater than or equal to 0, for example, 0 to 100. From the viewpoint of further improving compatibility with the thermosetting resin and further improving low thermal expansion and copper foil peel strength in a well-balanced manner, n is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less.

[0167] From the viewpoint of further improving compatibility with thermosetting resins and further improving low thermal expansion and copper foil peel strength in a well-balanced manner, the epoxy-modified silicone B preferably contains two or more epoxy-modified silicones represented by formula (1). In this case, the two or more epoxy-modified silicones preferably have different n, and more preferably contain an epoxy-modified silicone in which n in formula (1) is 1 to 2 and an epoxy-modified silicone in which n in formula (1) is 5 to 20.

[0168] From the viewpoint of more effectively and reliably exhibiting the effects of the present invention, the average number of epoxy groups per molecule of epoxy-modified silicone B is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less. The average number of epoxy groups is calculated by the following formula.

[0169]

[0170] (where Bi represents the number of epoxy groups in the epoxy-modified silicone having i epoxy groups in the molecule, Yi represents the ratio of the epoxy-modified silicone having i epoxy groups in the molecule to the total epoxy-modified silicone, Y1+Y2+…Y n =1.)

[0171] From the viewpoint of achieving further excellent low thermal expansion and chemical resistance, the content of the epoxy-modified silicone B is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, further preferably 40 to 85% by mass, and even more preferably 50 to 80% by mass, relative to 100% by mass of the total of the epoxy-modified silicone B and the epoxy compound C.

[0172] A commercially available product or a product produced by a known method may be used as the epoxy-modified silicone B. Examples of commercially available products include "X-22-163" and "KF-105" manufactured by Shin-Etsu Chemical Co., Ltd.

[0173] [Epoxy compound C]

[0174] Epoxy compound C is an epoxy compound other than epoxy-modified silicone B, more specifically, an epoxy compound without a polysiloxane skeleton. The curable composition in this embodiment, by containing epoxy compound C, can exhibit excellent compatibility, heat resistance, chemical resistance, copper foil peel strength, and insulation reliability. It should be noted that in this embodiment, "copper foil adhesion" and "copper foil peel strength" are synonymous.

[0175] The epoxy compound C is not particularly limited as long as it is an epoxy compound other than the epoxy-modified silicone B. The epoxy compound C in the curable composition of this embodiment typically includes a difunctional epoxy compound having two epoxy groups per molecule and a polyfunctional epoxy compound having three or more epoxy groups per molecule. From the perspective of achieving even better compatibility, heat resistance, chemical resistance, copper foil adhesion, and insulation reliability, the epoxy compound C preferably includes a difunctional epoxy compound and / or a polyfunctional epoxy compound.

[0176] The epoxy compound C in the curable resin composition of the present embodiment is not particularly limited, and a compound represented by the following formula (3a) can be used.

[0177]

[0178] (In formula (3a), Ar 3 Each independently represents a benzene ring or a naphthalene ring, Ar 4 represents a benzene ring, a naphthalene ring or a biphenyl ring, R 3a Each independently represents a hydrogen atom or a methyl group, k represents an integer of 1 to 50,

[0179] Here, Ar 3 The benzene ring or naphthalene ring in the ring may further have one or more substituents, which may be glycidyloxy groups (not shown), or other substituents, such as alkyl groups having 1 to 5 carbon atoms, phenyl groups, etc.

[0180] Ar 4 The benzene ring, naphthalene ring or biphenyl ring in the ring may further have one or more substituents, which may be glycidyloxy groups or other substituents, such as alkyl groups having 1 to 5 carbon atoms, phenyl groups, etc.

[0181] Among the compounds represented by the above formula (3a), examples of the bifunctional epoxy compound include compounds represented by the following formula (b1).

[0182]

[0183] (In formula (b1), Ar 3 Each independently represents a benzene ring or a naphthalene ring, Ar 4 represents a benzene ring, a naphthalene ring or a biphenyl ring, R 3a each independently represents a hydrogen atom or a methyl group,

[0184] Here, Ar 3 The benzene ring or naphthalene ring in the may further have one or more substituents, such as alkyl groups having 1 to 5 carbon atoms, phenyl groups, etc., excluding glycidyloxy groups.

[0185] Ar 4 The benzene ring, naphthalene ring or biphenyl ring in the ring may further have one or more substituents, and the substituents may be, for example, alkyl groups having 1 to 5 carbon atoms, phenyl groups, etc., excluding glycidyloxy groups.

[0186] The compound represented by formula (3a) is preferably wherein Ar 4 A phenolic novolac-type epoxy resin substituted with at least one glycidyl ether oxy group. The phenolic novolac-type epoxy resin is not particularly limited, and examples thereof include a compound having a structure represented by the following formula (3-1) (a naphthalene skeleton-containing multifunctional epoxy resin) and a naphthylcresol novolac-type epoxy resin.

[0187]

[0188] (where Ar 31 Each independently represents a benzene ring or a naphthalene ring, Ar 41 Each independently represents a benzene ring, a naphthalene ring or a biphenyl ring, R 31a Each independently represents a hydrogen atom or a methyl group, p represents 1, kz represents an integer of 1 to 50, each ring may have a substituent other than a glycidyloxy group (e.g., an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group), Ar 31 and Ar 41 At least one of them represents a naphthalene ring.)

[0189] Examples of the compound having a structure represented by formula (3-1) include compounds having a structure represented by formula (3-2).

[0190]

[0191] (In the formula, R represents a methyl group, and kz has the same meaning as kz in the above formula (3-1).)

[0192] The naphthol cresol novolac epoxy resin is not particularly limited, but is preferably a cresol / naphthol novolac epoxy resin represented by the following formula (NE). It should be noted that the compound represented by the following formula (NE) is a random copolymer of cresol novolac epoxy constituent units and naphthol novolac epoxy constituent units, and the termini may be either cresol epoxy or naphthol epoxy.

[0193]

[0194] In the above formula (NE), m and n each represent an integer greater than 1. The upper limits of m and n and their ratio are not particularly limited, but from the viewpoint of low thermal expansion, m:n (herein, m+n=100) is preferably 30-50:70-50, and more preferably 45-55:55-45.

[0195] As the naphthyl cresol novolac-type epoxy resin, a commercially available product or a product produced by a known method may be used. Examples of commercially available products include "NC-7000," "NC-7300," and "NC-7300L" manufactured by Nippon Kayaku Co., Ltd., and "HP-9540" and "HP-9500" manufactured by DIC Corporation. "HP-9540" is particularly preferred.

[0196] The compound represented by formula (3a) may be a compound that does not correspond to the above-mentioned phenol novolac-type epoxy resin (hereinafter also referred to as "aralkyl-type epoxy resin").

[0197] The aralkyl epoxy resin is preferably Ar in formula (3a). 3 For naphthalene ring, Ar 4 A compound having a benzene ring (also called a "naphthol aralkyl type epoxy resin") and Ar in formula (3a) 3 For benzene ring, Ar 4 The compound is a biphenyl ring compound (also referred to as a "biphenyl aralkyl type epoxy resin"), and more preferably a biphenyl aralkyl type epoxy resin.

[0198] As the naphthol aralkyl type epoxy resin, a commercially available product or a product produced by a known method may be used. Examples of commercially available products include "HP-5000" and "HP-9900" manufactured by DIC Corporation, and "ESN-375" and "ESN-475" manufactured by Nippon Steel Chemical Corporation.

[0199] The biphenyl aralkyl type epoxy resin is preferably a compound represented by the following formula (3b).

[0200]

[0201] (In the formula, ka represents an integer greater than or equal to 1, preferably 1 to 20, and more preferably 1 to 6.)

[0202] Among the compounds represented by the above formula (3b), examples of the bifunctional epoxy compound include compounds wherein ka in the formula (3b) is 1.

[0203] As the biphenyl aralkyl type epoxy resin, a commercial product or a product produced by a known method may be used. Examples of commercial products include "NC-3000," "NC-3000L," and "NC-3000FH" manufactured by Nippon Kayaku Co., Ltd.

[0204] Furthermore, as the epoxy compound C in the curable composition of this embodiment, a naphthalene-type epoxy resin (excluding the compound represented by formula (3a)) is preferably used. From the viewpoint of further improving heat resistance, chemical resistance, copper foil adhesion, and insulation reliability, the naphthalene-type epoxy resin is preferably a naphthylene ether-type epoxy resin.

[0205] From the viewpoint of further improving heat resistance, chemical resistance, copper foil adhesion, and insulation reliability, the naphthylene ether-type epoxy resin is preferably a difunctional epoxy compound represented by the following formula (3-3) or a polyfunctional epoxy compound represented by the following formula (3-4), or a mixture thereof.

[0206]

[0207] (Where R 13Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., methyl or ethyl), or an alkenyl group having 2 to 3 carbon atoms (e.g., vinyl, allyl, or propenyl).

[0208]

[0209] (Where R 14 Each independently represents a hydrogen atom, an alkyl group having 1 to 3 carbon atoms (e.g., methyl or ethyl), or an alkenyl group having 2 to 3 carbon atoms (e.g., vinyl, allyl, or propenyl).

[0210] A commercially available naphthylene ether epoxy resin may be used, or a product produced by a known method may be used. Examples of commercially available naphthylene ether epoxy resins include "HP-6000," "EXA-7300," "EXA-7310," "EXA-7311," "EXA-7311L," "EXA7311-G3," "EXA7311-G4," "EXA-7311G4S," and "EXA-7311G5" manufactured by DIC Corporation. HP-6000 is particularly preferred.

[0211] Examples of the naphthalene-type epoxy resin other than those described above are not limited to the following, but include compounds represented by the following formula (b3).

[0212]

[0213] (In formula (b3), R 3b Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms (e.g., methyl or ethyl), an aralkyl group, a benzyl group, a naphthyl group, a naphthyl group containing at least one glycidyloxy group, or a naphthylmethyl group containing at least one glycidyloxy group, and n represents an integer greater than 0 (e.g., 0 to 2).

[0214] Examples of commercially available products of the compound represented by the above formula (b3) include "HP-4032" (n=0 in the above formula (b3)) and "HP-4710" (n=0, R in the above formula (b3)) manufactured by DIC Corporation. 3b is a naphthylmethyl group containing at least one glycidyl ether oxy group) and the like.

[0215] Furthermore, as the epoxy compound C in the curable composition of the present embodiment, it is preferable to use a biphenyl type epoxy compound (excluding compounds corresponding to the above epoxy compound C).

[0216] The biphenyl-type epoxy compound is not particularly limited, and examples thereof include a compound represented by the following formula (b2) (compound b2).

[0217]

[0218] (In formula (b2), each Ra independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.)

[0219] 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, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl.

[0220] When the biphenyl-type epoxy compound is compound b2, the biphenyl-type epoxy compound may be a mixture of compounds b2 having different numbers of alkyl groups Ra. Specifically, a mixture of biphenyl-type epoxy compounds having different numbers of alkyl groups Ra is preferred, and a mixture of compound b2 having 0 alkyl groups Ra and compound b2 having 4 alkyl groups Ra is more preferred.

[0221] Furthermore, as the epoxy compound C in the curable composition of the present embodiment, a dicyclopentadiene-type epoxy resin (excluding compounds corresponding to the above-mentioned epoxy compound C) can be used.

[0222] The dicyclopentadiene-type epoxy resin is not particularly limited, and examples thereof include compounds represented by the following formula (3-5).

[0223]

[0224] (Where R 3c Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and k2 represents an integer from 0 to 10.

[0225] The compound represented by the above formula (3-5) is not particularly limited, and may be, for example, a compound represented by the following formula (b4).

[0226]

[0227] (In formula (b4), R 3c Each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms (e.g., a methyl group or an ethyl group).

[0228] Commercially available dicyclopentadiene epoxy resins or those manufactured by known methods may be used. Examples of commercially available dicyclopentadiene epoxy resins include "EPICRON HP-7200L," "EPICRON HP-7200," "EPICRON HP-7200H," and "EPICRON HP-7000HH" manufactured by Dainippon Ink and Chemicals, Incorporated.

[0229] From the viewpoint of being able to exhibit further excellent heat resistance, chemical resistance, copper foil adhesion and insulation reliability, among these, the epoxy compound C is preferably one or more selected from the group consisting of the epoxy compound represented by formula (3a), naphthalene-type epoxy resin and biphenyl-type epoxy compound. In this case, it is preferred that the epoxy compound represented by formula (3a) includes a naphthol novolac-type epoxy resin and the naphthalene-type epoxy resin includes a naphthylene ether-type epoxy resin.

[0230] As the epoxy compound C, other epoxy compounds which do not correspond to the aforementioned epoxy compounds may be contained.

[0231] Other epoxy compounds are not particularly limited, and examples thereof include bisphenol-type epoxy resins, trisphenol methane-type epoxy resins, anthracene-type epoxy resins, glycidyl ester-type epoxy resins, polyol-type epoxy resins, isocyanurate ring-containing epoxy resins, fluorene-type epoxy resins, and epoxy resins containing bisphenol A-type structural units and hydrocarbon-based structural units.

[0232] From the viewpoint of further improving heat resistance, chemical resistance, copper foil adhesion and insulation reliability, among the above, other epoxy compounds may include bisphenol-type epoxy resins. As bisphenol-type epoxy resins, for example, diallyl bisphenol-type epoxy resins (such as diallyl bisphenol A epoxy resin, diallyl bisphenol E epoxy resin, diallyl bisphenol F epoxy resin, diallyl bisphenol S epoxy resin, etc.) can be used.

[0233] As the epoxy compound C, one of the above-mentioned epoxy compounds and epoxy resins may be used alone or in combination of two or more.

[0234] From the viewpoint of more effectively and reliably exhibiting the effects of this embodiment, the average number of epoxy groups per molecule of epoxy compound C is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less. The average number of epoxy groups is calculated by the following formula.

[0235]

[0236] (In the above formula, Ci represents the number of epoxy groups in the epoxy compound having i epoxy groups in the molecule, Zi represents the ratio of the epoxy compound having i epoxy groups in the molecule to the total epoxy compounds, Z1+Z2+…Z n =1.)

[0237] From the viewpoint of achieving further excellent heat resistance, chemical resistance, copper foil peel strength, and insulation reliability, the content of the epoxy compound C is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, further preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass, relative to 100% by mass of the total amount of the epoxy-modified silicone B and the epoxy compound C.

[0238] [Aminotriazine novolac resin D]

[0239] The curable composition of this embodiment includes an aminotriazine novolac resin D. The aminotriazine novolac resin D reacts with the terminal hydroxyl groups and / or epoxy groups generated by the reaction of alkenylphenol A, epoxy-modified silicone B, and an epoxy compound C other than epoxy-modified silicone B, thereby increasing the number of terminal functional groups such as hydroxyl groups and / or amino groups. This results in the presence of a large number of terminal functional groups highly reactive with the thermosetting resin, thereby improving compatibility and crosslinking density, and enhancing copper foil peel strength.

[0240] The aminotriazine novolac resin D is not particularly limited. However, from the viewpoint of exhibiting further excellent compatibility and copper foil peel strength, a novolac resin having 2 to 20 phenolic hydroxyl groups per triazine skeleton in the molecule is preferred, a novolac resin having 2 to 15 phenolic hydroxyl groups per triazine skeleton in the molecule is more preferred, and a novolac resin having 2 to 10 phenolic hydroxyl groups per triazine skeleton in the molecule is further preferred.

[0241] From the viewpoint of exhibiting further excellent compatibility and copper foil peel strength, the content of the aminotriazine novolac resin D is preferably 0.8 to 10% by mass, more preferably 0.9 to 8% by mass, further preferably 1 to 7% by mass, and particularly preferably 1 to 3% by mass, relative to 100% by mass of the resin solids.

[0242] As the aminotriazine novolac resin D, any phenol-formaldehyde resin (phenolic resin) having a triazine ring in the molecule can be used, and known resins can be used. Such aminotriazine novolac resin D can be produced by known methods, for example, by modifying a phenolic resin with a nitrogen compound such as melamine. The aminotriazine novolac resin D can be used alone or in combination of two or more.

[0243] The aminotriazine novolac resin D preferably has a weight average molecular weight of 300 to 9,500, more preferably 500 to 5,000, and even more preferably 1,000 to 3,500, due to its tendency to exhibit superior reactivity and solubility. The weight average molecular weight herein is a value calculated in terms of standard polystyrene as determined by GPC (gel permeation chromatography).

[0244] The aminotriazine novolac resin D has a nitrogen content of preferably 5 to 25% by mass, more preferably 7 to 22% by mass, and even more preferably 10 to 20% by mass relative to 100% by mass of the aminotriazine novolac resin D, because it tends to have excellent reactivity and solubility.

[0245] The aminotriazine novolac resin D has a hydroxyl equivalent weight of preferably 100 to 200 g / eq., more preferably 110 to 180 g / eq., even more preferably 120 to 170 g / eq., and even more preferably 125 to 160 g / eq., due to its tendency to exhibit excellent reactivity and solubility. It should be noted that in this embodiment, the hydroxyl equivalent weight represents the number of milligrams of potassium hydroxide required to acetylate the hydroxyl groups contained in 1 g of the aminotriazine novolac resin. Specifically, it is measured in accordance with JIS K 0070.

[0246] The aminotriazine novolac resin D preferably contains one or more selected from the group consisting of compounds represented by the following formula (1) and compounds represented by the following formula (2), since reactivity and solubility tend to be more excellent.

[0247]

[0248] In formula (1), R1 each independently represents a hydrogen atom, a methyl group or an ethyl group.

[0249] From the perspective of further excellent reactivity and solubility, R1 is preferably each independently a hydrogen atom or a methyl group. l, m and n each independently represent an integer of 0 to 10. From the perspective of further excellent reactivity and solubility, l, m and n are preferably each independently an integer of 1 to 6. (l+m+n) represents an integer of 1 to 20. From the perspective of further excellent reactivity and solubility, (l+m+n) is preferably an integer of 3 to 18. It should be noted that the compound represented by formula (1) may be a mixture containing, for example, compounds having different groups and / or different numbers of R1 in formula (1), compounds having different numbers of l, m and n, compounds having different numbers of (l+m+n), etc.

[0250]

[0251] In formula (2), R2 each independently represents a hydrogen atom, a methyl group or an ethyl group.

[0252] From the perspective of further excellent reactivity and solubility, R2 is preferably each independently a hydrogen atom or a methyl group. o, p, q, r and s each independently represent an integer of 0 to 10. From the perspective of further excellent reactivity and solubility, o, p, q, r and s each independently represent an integer of 1 to 4. (o+p+q+r+s) represents an integer of 1 to 20. From the perspective of further excellent reactivity and solubility, (o+p+q+r+s) is preferably an integer of 5 to 20. It should be noted that the compound represented by formula (2) may be a mixture containing, for example, compounds having different groups and / or different numbers of R2 in formula (2), compounds having different numbers of o, p, q, r and s, compounds having different numbers of (o+p+q+r+s), etc.

[0253] From the perspective of having further improved reactivity and solubility, a mixture of the compound represented by formula (1) and the compound represented by formula (2) is more preferred as the aminotriazine novolac resin D. In such a mixture, the mass ratio of the compound represented by formula (1) to the compound represented by formula (2) (compound represented by formula (1) (parts by mass):compound represented by formula (2) (parts by mass)) is preferably 50:50 to 90:10, and more preferably 60:40 to 85:15.

[0254] As the aminotriazine novolac resin D, commercially available products can be used. Examples thereof include LA-1356 (trade name), LA-3018-50P (trade name), LA-7052 (trade name), LA-7054 (trade name), and LA-7751 (trade name) manufactured by DIC Corporation.

[0255] [Compound F]

[0256] From the perspective of further improving heat resistance, chemical resistance, low thermal expansion, and copper foil peel strength, the curable composition of this embodiment preferably further contains at least one compound F selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds A' other than the aforementioned alkenylphenol A, and alkenyl-substituted nadic imide compounds. Compound F is not particularly limited, but is preferably difunctional or higher, and may be polyfunctional, trifunctional or higher.

[0257] The content of compound F in the curable composition of the present embodiment is preferably 10 to 80 mass %, more preferably 20 to 60 mass %, and even more preferably 30 to 50 mass %, relative to 100 mass % of the resin solid content.

[0258] (Maleimide compound)

[0259] From the viewpoint of further improving the low thermal expansion and copper foil peeling strength, compound F preferably contains a maleimide compound. The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule. Examples thereof include monomaleimide compounds having one maleimide group in one molecule (e.g., N-phenylmaleimide, N-hydroxyphenylmaleimide, etc.), polymaleimide compounds having two or more maleimide groups in one molecule (e.g., bis(4-maleimidophenyl)methane, 2,2-bis{4-(4-maleimidophenoxy)-phenyl}propane, bis(3-ethyl- 5-methyl-4-maleimidephenyl)methane, bis(3,5-dimethyl-4-maleimidephenyl)methane, bis(3,5-diethyl-4-maleimidephenyl)methane), m-phenylenebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, a maleimide compound represented by the following formula (3), a maleimide compound represented by the following formula (3'), a prepolymer of these maleimide compounds and an amine compound, etc.

[0260]

[0261] (In formula (3), R5 each independently represents a hydrogen atom or a methyl group, and n1 represents an integer greater than or equal to 1.)

[0262] n1 is 1 or more, preferably 1-100, and more preferably 1-10.

[0263]

[0264] (In formula (3'), R 13 Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, n 4 represents an integer greater than or equal to 1 and less than or equal to 10. ).

[0265] These maleimide compounds can be used alone or in combination of two or more. From the viewpoint of further improving low thermal expansion and copper foil peel strength, the maleimide compound preferably includes at least one selected from the group consisting of bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, the maleimide compound represented by formula (3), and the maleimide compound represented by formula (3').

[0266] The maleimide compound can be a commercially available product or a product produced by a known method. Commercially available maleimide compounds include "BMI-70", "BMI-80", and "BMI-1000P" manufactured by K.I. Chemical Industry Co., Ltd., "BMI-3000", "BMI-4000", "BMI-5100", "BMI-7000", and "BMI-2300" manufactured by Yamato Chemical Industry Co., Ltd., and "MIR-3000" manufactured by Nippon Kayaku Co., Ltd. (R in formula (3') is α-Hydroxy-1,1-dimethyl-1-oxo ... 13 All hydrogen atoms, n 4 A mixture of 1 to 10. ) etc.

[0267] From the viewpoint of further improving low thermal expansion and copper foil peel strength, the content of the maleimide compound is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, and even more preferably 10 to 40 parts by mass per 100 parts by mass of the resin solids.

[0268] (Cyanate ester compound)

[0269] From the viewpoint of further improving the low thermal expansion and copper foil peeling strength, compound F preferably contains a cyanate compound. The cyanate compound is not particularly limited as long as it is a compound having two or more cyanooxy groups (cyanate groups) in one molecule, and examples thereof include naphthol aralkyl type cyanate compounds such as the compound represented by the following formula (4), novolac type cyanate compounds such as the compound represented by the following formula (5) other than the compound represented by the following formula (4), biphenyl aralkyl type cyanate, diallyl bisphenol type cyanate, bis(3,3-dimethyl-4-cyanophenyl)methane, bis(4-cyanophenyl)methane, Alkane, 1,3-dicyanobenzene, 1,4-dicyanobenzene, 1,3,5-tricyanobenzene, 1,3-dicyanonaphthalene, 1,4-dicyanonaphthalene, 1,6-dicyanonaphthalene, 1,8-dicyanonaphthalene, 2,6-dicyanonaphthalene, 2,7-dicyanonaphthalene, 1,3,6-tricyanonaphthalene, 4,4'-dicyanobiphenyl, bis(4-cyanophenyl)ether, bis(4-cyanophenyl)sulfide, bis(4-cyanophenyl)sulfone, 2,2-bis(4-cyanophenyl)propane. These cyanate compounds can be used alone or in combination of two or more. From the viewpoint of heat resistance, low thermal expansion and copper foil peel strength, the cyanate compound in the present embodiment preferably includes a polyfunctional cyanate compound such as a naphthol aralkyl type cyanate compound and / or a novolac type cyanate compound.

[0270]

[0271] (In formula (4), R6 each independently represents a hydrogen atom or a methyl group, and n2 represents an integer greater than or equal to 1.)

[0272]

[0273] (In formula (5), R ya Each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, and R yb Each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and R yc Each independently represents an aromatic ring having 4 to 12 carbon atoms, R yc Optionally form a condensed structure with a benzene ring, R yc Optional presence or absence, A 1a Each independently represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, a sulfur atom or a direct bond (single bond), and R yc When not present, one benzene ring may optionally have two or more R ya and / or R yb n represents an integer from 1 to 20.

[0274] From the viewpoint of further improving heat resistance, low thermal expansion, and copper foil peeling strength, the cyanate ester compound preferably contains a compound represented by formula (4) and / or formula (5) among these.

[0275] In formula (4), n2 represents an integer of 1 or greater, preferably an integer of 1 to 20, and more preferably an integer of 1 to 10.

[0276] In formula (5), as R ya The alkenyl group having 2 to 8 carbon atoms represented by is not particularly limited, and examples thereof include vinyl, allyl, propenyl, butenyl, and hexenyl.

[0277] In formula (5), the C1-10 alkyl group represented by Ryb is not particularly limited, and examples thereof include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl; and branched alkyl groups such as isopropyl, isobutyl, and tert-butyl.

[0278] In formula (5), as A 1a The alkylene group having 1 to 6 carbon atoms represented by is not particularly limited, and examples thereof include methylene, ethylene, trimethylene, and propylene. 1a The aralkylene group having 7 to 16 carbon atoms is not particularly limited, and examples thereof include groups represented by the formula: -CH2-Ar-CH2-, -CH2-CH2-Ar-CH2-CH2-, or -CH2-Ar-CH2-CH2- (wherein Ar represents a phenylene group, a naphthylene group, or a biphenylene group).1a The arylene group having 6 to 10 carbon atoms is not particularly limited, and examples thereof include a phenylene ring.

[0279] In formula (5), n represents an integer of 1 to 20, preferably an integer of 1 to 15, and more preferably an integer of 1 to 10.

[0280] The compound represented by formula (5) is preferably a compound represented by the following formula (c1).

[0281]

[0282] (In formula (c1), Rx each independently represents a hydrogen atom or a methyl group, R each independently represents an alkenyl group having 2 to 8 carbon atoms, an alkyl group having 1 to 10 carbon atoms, or a hydrogen atom, and n represents an integer of 1 to 10.)

[0283] These cyanate compounds can be produced by known methods. Specific production methods include, for example, methods described in Japanese Patent Application Laid-Open No. 2017-195334 (particularly paragraphs 0052 to 0057).

[0284] From the viewpoint of further improving low thermal expansion and copper foil peel strength, the content of the cyanate compound as compound F is preferably 10 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 10 to 40 parts by mass, relative to 100 parts by mass of the resin solids.

[0285] (Phenolic compound A' other than alkenylphenol A)

[0286] From the viewpoint of exhibiting further excellent copper foil peel strength, the compound F may contain a phenol compound A' other than alkenylphenol A. The phenol compound A' is not particularly limited, and examples thereof include bisphenol-type phenolic resins (e.g., bisphenol A-type resins, bisphenol E-type resins, bisphenol F-type resins, bisphenol S-type resins, etc.), phenolic novolac resins (e.g., phenol novolac resins, naphthol novolac resins, cresol novolac resins, 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, fluorene-type phenolic resins, etc. These phenolic compounds may be used alone or in combination of two or more.

[0287] From the viewpoint of expressing more excellent compatibility and copper foil peeling strength, the phenol compound A′ preferably includes a bifunctional phenol compound having two phenolic hydroxyl groups in one molecule among these.

[0288] The difunctional phenol compound is not particularly limited, and examples thereof include bisphenol, biscresol, bisphenols having a fluorene skeleton (e.g., bisphenol having a fluorene skeleton, biscresol having a fluorene skeleton), biphenols (e.g., p,p'-biphenol), dihydroxydiphenyl ethers (e.g., 4,4'-dihydroxydiphenyl ether), dihydroxydiphenyl ketones (e.g., 4,4'-dihydroxydiphenyl ketone), dihydroxydiphenyl sulfides (e.g., 4,4'-dihydroxydiphenyl sulfide), and dihydroxyaromatic hydrocarbons (e.g., hydroquinone). These difunctional phenol compounds can be used alone or in combination of two or more. From the perspective of achieving even better copper foil peel strength, the difunctional phenol compound preferably includes at least one selected from the group consisting of bisphenol, biscresol, and bisphenols having a fluorene skeleton. From the same perspective as above, biscresol fluorene is preferably used as the bisphenol having a fluorene skeleton.

[0289] Examples of the aralkyl-type phenol resin include compounds represented by the following formula (c2).

[0290]

[0291] (where Ar 1 Each independently represents a benzene ring or a naphthalene ring, Ar 2 represents a benzene ring, a naphthalene ring or a biphenyl ring, R 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).

[0292] From the viewpoint of further improving the adhesion of copper foil, the compound represented by formula (c2) is preferably 1 For naphthalene ring, Ar 2 A compound having a benzene ring (hereinafter also referred to as "naphthol aralkyl type phenolic resin") and Ar in formula (c2) 1 For benzene ring, Ar 2 A compound containing a biphenyl ring (hereinafter also referred to as a "biphenyl aralkyl type phenol resin").

[0293] The naphthol aralkyl type phenol resin is preferably a compound represented by the following formula (8).

[0294]

[0295] (In the formula, R7 each independently represents a hydrogen atom or a methyl group, and n3 represents an integer greater than 1.)

[0296] In formula (8), n3 represents an integer of 1 or greater, preferably an integer of 1 to 10, and more preferably an integer of 1 to 6.

[0297] The biphenyl aralkyl phenol resin is preferably a compound represented by the following formula (2c).

[0298]

[0299] (Where R 2b Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group (preferably a hydrogen atom), and m1 represents an integer of 1 to 20 (preferably an integer of 1 to 6).

[0300] From the viewpoint of further improving low thermal expansion properties and copper foil peeling strength, the phenol compound A′ preferably contains a compound represented by the above formula (8).

[0301] The aralkyl phenolic resin may be a commercially available product or a product produced by a known method. Examples of commercially available aralkyl phenolic resins include "KAYAHARD GPH-65," "KAYAHARD GPH-78," and "KAYAHARD GPH-103" (biphenyl aralkyl phenolic resins) manufactured by Nippon Kayaku Co., Ltd., and "SN-495" (naphthol aralkyl phenolic resin) manufactured by Nippon Steel Chemical Co., Ltd.

[0302] From the viewpoint of exhibiting further excellent compatibility, the content of alkenylphenol A as compound F is preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, and even more preferably 5 to 20 parts by mass, relative to 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and phenol compound A'.

[0303] From the viewpoint of being able to exhibit further excellent low thermal expansion and copper foil peel strength in a well-balanced manner, the content of the epoxy-modified silicone B in the curable composition of this embodiment is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 55 parts by mass, relative to 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and phenol compound A'.

[0304] From the viewpoint of being able to exhibit further excellent compatibility, heat resistance, chemical resistance, copper foil peel strength and insulation reliability, the content of the epoxy compound C in the curable composition of this embodiment is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 15 to 25 parts by mass, relative to 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C and phenol compound A'.

[0305] From the viewpoint of being able to exhibit further excellent copper foil peel strength, the content of the phenol compound A' in the curable composition of this embodiment is preferably 5 to 30 parts by mass, more preferably 10 to 25 parts by mass, and even more preferably 15 to 20 parts by mass, relative to 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C and phenol compound A'.

[0306] When the curable composition does not contain the phenol compound A′, the contents of the alkenylphenol A, epoxy-modified silicone B, and epoxy compound C are expressed relative to 100 parts by mass of the total amount of the alkenylphenol A, epoxy-modified silicone B, and epoxy compound C.

[0307] (Alkenyl-substituted nadic imide compound)

[0308] From the viewpoint of further improving heat resistance, it is preferred that compound F contain an alkenyl-substituted nadic imide compound. The alkenyl-substituted nadic imide compound is not particularly limited as long as it has one or more alkenyl-substituted nadic imide groups in one molecule, and examples thereof include compounds represented by the following formula (2d).

[0309]

[0310] (In formula (2d), R1 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms (e.g., a methyl group or an ethyl group), and R2 represents an alkylene group having 1 to 6 carbon atoms, a phenylene group, a biphenylene group, a naphthylene group, or a group represented by the following formula (6) or the following formula (7).)

[0311]

[0312] (In formula (6), R3 represents methylene, isopropylidene, CO, O, S or SO2.)

[0313]

[0314] (In formula (7), R4 each independently represents an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms.)

[0315] The alkenyl-substituted nadic imide compound represented by formula (2d) may be a commercially available product or one produced by a known method. Examples of commercially available products include "BANI-M" and "BANI-X" manufactured by Maruzen Petrochemical Co., Ltd.

[0316] From the viewpoint of improving heat resistance, the content of the alkenyl-substituted nadic imide compound as compound F is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass, and even more preferably 10 to 30 parts by mass per 100 parts by mass of the resin solids.

[0317] [Second embodiment: Curable composition]

[0318] The curable composition of the second embodiment includes a polymer E containing structural units derived from an alkenylphenol A, structural units derived from an epoxy-modified silicone B, structural units derived from an epoxy compound C other than the epoxy-modified silicone B, and structural units derived from an aminotriazine novolac resin D. The alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and aminotriazine novolac resin D are as described above. Hereinafter, the curable resin composition of the second embodiment containing the polymer E, which contains structural units derived from an alkenylphenol A, structural units derived from an epoxy-modified silicone B, structural units derived from an epoxy compound C, and structural units derived from an aminotriazine novolac resin D, is distinguished from the curable composition of the first embodiment described above, which does not contain the polymer E.

[0319] Polymer E exhibits sufficient compatibility even when mixed with thermosetting resins that lack sufficient compatibility with silicone compounds. Consequently, curable compositions containing polymer E and thermosetting resins can provide uniform varnishes and cured products. Cured products such as prepregs obtained using this curable composition exhibit uniform compatibility among their components, minimizing variations in physical properties caused by component inhomogeneities.

[0320] It should be noted that the curable composition of the second embodiment may contain, in addition to the polymer E, one or more selected from the group consisting of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and aminotriazine novolac resin D. In this case, the alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and aminotriazine novolac resin D contained in the curable composition of the second embodiment may be unreacted components remaining after the polymerization of the polymer E, or may be components added separately to the purified polymer E.

[0321] Furthermore, the curable composition of the second embodiment may contain, in addition to the polymer E, at least one compound F selected from the group consisting of the aforementioned maleimide compounds, cyanate ester compounds, phenol compounds A' other than the aforementioned alkenylphenol A, and alkenyl-substituted nadic imide compounds, as needed. Compound F may be an unreacted component remaining after polymerization of the polymer E, or may be a component added separately to the synthesized polymer E.

[0322] [Polymer E]

[0323] Polymer E contains constituent units derived from alkenylphenol A, constituent units derived from epoxy-modified silicone B, constituent units derived from epoxy compound C, and constituent units derived from aminotriazine novolac resin D. If necessary, it may further contain constituent units derived from at least one compound F selected from the group consisting of a maleimide compound, a cyanate ester compound, a phenol compound A' other than the aforementioned alkenylphenol A, and an alkenyl-substituted nadic imide compound. When polymer E contains constituent units derived from compound F, compound F is preferably a difunctional compound. It should be noted that in this specification, "constituent units derived from alkenylphenol A," "constituent units derived from epoxy-modified silicone B," "constituent units derived from epoxy compound C," "constituent units derived from aminotriazine novolac resin D," and "constituent units derived from compound F" refer to constituent units in polymer E formed by polymerizing the components alkenylphenol A, epoxy-modified silicone B, epoxy compound C, aminotriazine novolac resin D, and compound F, as well as constituent units formed by reactions that can provide the same constituent units. Hereinafter, each structural unit is also referred to as structural unit A, B, C, D, and F. By using polymer E, the curable composition of the second embodiment has further excellent compatibility, and further excellent heat resistance, chemical resistance, copper foil peel strength, and insulation reliability.

[0324] The weight average molecular weight of the polymer E is preferably 3.0×10 3 ~5.0×10 4 , more preferably 3.0×10 3 ~2.0×10 4 The weight average molecular weight is 3.0×10 3 As described above, the curable composition of the second embodiment tends to exhibit further excellent heat resistance, chemical resistance, copper foil peeling strength and insulation reliability. 4 Hereinafter, the curable composition of the second embodiment tends to be able to express further excellent compatibility.

[0325] The content of the structural unit A in the polymer E is preferably 5 to 50% by mass relative to the total mass of the polymer E. When the content of the structural unit A is within the above range, the curable composition of the second embodiment tends to exhibit further excellent compatibility. From the same viewpoint, the content of the structural unit A is more preferably 10 to 45% by mass, and even more preferably 15 to 40% by mass.

[0326] The content of the structural unit B in the polymer E is preferably 20 to 60% by mass relative to the total mass of the polymer E. When the content of the structural unit B is within this range, the curable composition of the second embodiment tends to exhibit further excellent low thermal expansion and copper foil peel strength in a well-balanced manner. From the same viewpoint, the content of the structural unit B is more preferably 25 to 55% by mass, and even more preferably 30 to 50% by mass.

[0327] Structural unit B preferably comprises structural units derived from an epoxy-modified silicone having an epoxy equivalent weight of 50 to 350 g / mol (low-equivalent-weight epoxy-modified silicone B1) and an epoxy-modified silicone having an epoxy equivalent weight of 400 to 4000 g / mol (high-equivalent-weight epoxy-modified silicone B2). Low-equivalent-weight epoxy-modified silicone B1 and high-equivalent-weight epoxy-modified silicone B2 are more preferably epoxy-modified silicone having an epoxy equivalent weight of 140 to 250 g / mol (low-equivalent-weight epoxy-modified silicone B1') and epoxy-modified silicone having an epoxy equivalent weight of 450 to 3000 g / mol (high-equivalent-weight epoxy-modified silicone B2'), respectively.

[0328] The content of the structural unit B1 derived from the low equivalent weight epoxy-modified silicone B1 in the polymer E is preferably 5 to 25 mass %, more preferably 7.5 to 20 mass %, and even more preferably 10 to 17 mass % relative to the total mass of the polymer E.

[0329] The content of the structural unit B2 derived from the high equivalent weight epoxy-modified silicone B2 in the polymer E is preferably 15 to 55% by mass, more preferably 20 to 52.5% by mass, and even more preferably 25 to 50% by mass, relative to the total mass of the polymer E.

[0330] The mass ratio of the content of constitutional unit B2 to the content of constitutional unit B1 is preferably 1.5 to 4, more preferably 1.7 to 3.5, and even more preferably 1.9 to 3.1. By having the above relationship between the contents of constitutional unit B1 and constitutional unit B2, the curable composition of the second embodiment tends to have further improved low thermal expansion and copper foil peel strength.

[0331] The structural unit C in the polymer E is preferably a unit derived from at least one selected from the group consisting of the compound represented by the above formula (b1), the compound represented by the above formula (b2), the compound represented by the above formula (b3), and the compound represented by the above formula (b4).

[0332] The content of the structural unit C in the polymer E is preferably 5 to 40 mass% relative to the total mass of the polymer E. When the content of the structural unit C is within the above range, the curable composition of the second embodiment has further improved compatibility and tends to exhibit further improved heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. From the same viewpoint, the content of the structural unit C is preferably 10 to 30 mass%, more preferably 15 to 25 mass%.

[0333] Furthermore, the content of constitutional unit C is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, even more preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass, relative to the total mass of constitutional units B and constitutional units C. Due to the aforementioned relationship between the contents of constitutional units B and constitutional units C, the curable composition of the second embodiment has further improved compatibility and tends to have further improved heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability.

[0334] The content of the structural unit D in the polymer E is preferably 3 to 20% by mass relative to the total mass of the polymer E. When the content of the structural unit D is within this range, the curable composition of the second embodiment tends to exhibit even better copper foil peel strength. From the same viewpoint, the content of the structural unit D is more preferably 3 to 15% by mass, and even more preferably 4 to 10% by mass.

[0335] When polymer E includes structural units derived from compound F, the content of structural units F in polymer E is preferably 3 to 40% by mass relative to the total mass of polymer E. When the content of structural units F is within this range, the curable composition of the second embodiment tends to exhibit further excellent heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. From the same viewpoint, the content of structural units F is preferably 5 to 35% by mass, and more preferably 10 to 30% by mass.

[0336] When polymer E includes a structural unit derived from a phenol compound A' other than alkenylphenol A (hereinafter also referred to as "structural unit A'"), the content of structural unit A' in polymer E is preferably 5 to 30% by mass relative to the total mass of polymer E. When the content of structural unit A' is within the above range, the curable composition of the second embodiment tends to exhibit further excellent heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. From the same viewpoint, the content of structural unit A' is preferably 10 to 27.5% by mass, and more preferably 10 to 25% by mass.

[0337] The alkenyl equivalent in polymer E is preferably 300 to 1500 g / mol. When the alkenyl equivalent is 300 g / mol or more, the elastic modulus of the cured product of the curable composition of the second embodiment tends to be further reduced, and as a result, the thermal expansion coefficient of the substrate etc. obtained using the cured product tends to be further reduced. When the alkenyl equivalent is 1500 g / mol or less, the compatibility, heat resistance, chemical resistance, low thermal expansion, copper foil peel strength and insulation reliability of the curable composition of the second embodiment tend to be further improved. From the same viewpoint, the alkenyl equivalent is preferably 350 to 1200 g / mol, and more preferably 400 to 1000 g / mol.

[0338] The content of polymer E in the curable composition of the second embodiment is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 15 to 40% by mass relative to 100% by mass of the resin solids. When the content is within this range, the curable composition tends to exhibit better compatibility, low thermal expansion, and copper foil peel strength in a well-balanced manner.

[0339] The polymer E can be obtained, for example, by reacting alkenylphenol A, epoxy-modified silicone B, epoxy compound C, aminotriazine novolac resin D, and, if necessary, compound F in the presence of a polymerization catalyst G. This reaction can be carried out in the presence of an organic solvent.

[0340] More specifically, in the above steps, polymer E can be obtained by performing an addition reaction between the epoxy groups of epoxy-modified silicone B and epoxy compound C and the hydroxyl groups of alkenylphenol A, and performing an addition reaction between the hydroxyl groups of the obtained addition reaction product and the epoxy groups of epoxy-modified silicone B and epoxy compound C, and then performing an addition reaction between the terminal hydroxyl groups and epoxy groups and aminotriazine novolac resin D.

[0341] The method for producing the curable composition of the present embodiment (particularly the curable composition of the second embodiment) preferably includes:

[0342] a step of obtaining a prepolymer, wherein the prepolymer is obtained by polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C; and

[0343] A step of reacting the aminotriazine novolac resin D with the prepolymer.

[0344] By forming a prepolymer obtained by polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C, and then reacting the prepolymer with aminotriazine novolac resin D, a curable composition having even better copper foil peel strength tends to be obtained.

[0345] [Polymerization Catalyst G]

[0346] The polymerization catalyst G is not particularly limited, and examples thereof include any one or more of an imidazole compound and an organic phosphorus compound. These catalysts may be used alone or in combination of two or more. Among these, an imidazole compound is preferred.

[0347] The imidazole compound is not particularly limited, and examples thereof include imidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole ("TBZ" manufactured by Shikoku Chemicals Co., Ltd.), and 2,4,5-triphenylimidazole ("TPIZ" manufactured by Tokyo Chemical Industry Co., Ltd.). Among these, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and / or 2,4,5-triphenylimidazole are preferred from the viewpoint of preventing homopolymerization of the epoxy component.

[0348] The amount of polymerization catalyst G (preferably an imidazole compound) used is not particularly limited. For example, it is 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, aminotriazine novolac resin D and compound F. From the viewpoint of increasing the weight-average molecular weight of polymer E, the amount of polymerization catalyst G used is preferably 0.5 parts by mass or more, and more preferably 4.0 parts by mass or less.

[0349] [Organic solvents]

[0350] There are no particular limitations on the organic solvent; for example, polar solvents or non-polar solvents can be used. Polar solvents are not particularly limited; examples include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; and amides such as dimethylacetamide and dimethylformamide. Non-polar solvents are not particularly limited; examples include aromatic hydrocarbons such as toluene and xylene. These solvents can be used alone or in combination of two or more.

[0351] The amount of the organic solvent used is not particularly limited, and is, for example, 50 to 150 parts by mass based on 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, aminotriazine novolac resin D, and compound F.

[0352] The reaction temperature is not particularly limited and may be, for example, 100 to 170° C. The reaction time is also not particularly limited and may be, for example, 3 to 8 hours.

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

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

[0355] When the curable composition of the second embodiment contains polymer E and compound F, the content of polymer E in the curable composition of the second embodiment is preferably 5 to 60 mass%, more preferably 10 to 55 mass%, and even more preferably 20 to 50 mass%, relative to 100 mass% of the total of polymer E and compound F. When the content is within this range, the curable composition has further improved compatibility and tends to have low thermal expansion and excellent copper foil peel strength.

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

[0357] The curable composition in this embodiment may further contain other resins as long as they do not hinder the effects of this embodiment. Examples of other resins include oxetane resins, benzoxazine compounds, and compounds having polymerizable unsaturated groups. These resins may be used alone or in combination of two or more.

[0358] Examples of the oxetane resin include oxetane, alkyloxetanes such as 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3'-bis(trifluoromethyl)perfluorooxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetanes, and "OXT-101" and "OXT-121" manufactured by Toagosei Co., Ltd.

[0359] As used herein, a "benzoxazine compound" refers to a compound having two or more dihydrobenzoxazine rings in one molecule. Examples of benzoxazine compounds include "Bisphenol F-type benzoxazine BF-BXZ" and "Bisphenol S-type benzoxazine BS-BXZ," both available from Konishi Chemical Co., Ltd.

[0360] Examples of the compound having a polymerizable unsaturated group include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; (meth)acrylates of monohydric or polyhydric alcohols such as methyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol hexa(meth)acrylate; epoxy (meth)acrylates such as bisphenol A epoxy (meth)acrylate and bisphenol F epoxy (meth)acrylate; and benzocyclobutene resins.

[0361] [Inorganic fillers]

[0362] From the viewpoint of further improving the low thermal expansion property, the curable composition in the present embodiment preferably further contains an inorganic filler. The inorganic filler is not particularly limited, and examples thereof include silica, silicon compounds (e.g., white carbon), metal oxides (e.g., aluminum oxide, titanium dioxide, zinc oxide, magnesium oxide, zirconium oxide), metal nitrides (e.g., boron nitride, condensed boron nitride, silicon nitride, aluminum nitride), metal sulfates (e.g., barium sulfate), metal hydroxides (e.g., aluminum hydroxide, heat-treated aluminum hydroxide (e.g., aluminum hydroxide subjected to heat treatment to remove a portion of crystalline water), boehmite, magnesium hydroxide), molybdenum compounds (e.g., molybdenum oxide, zinc molybdate), zinc compounds (e.g., zinc borate, zinc stannate), clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fibers (including fine glass powders such as E-glass, T-glass, D-glass, S-glass, and Q-glass), hollow glass, spherical glass, and the like. These inorganic fillers can be used alone or in combination of two or more. Among these, from the viewpoint of further improving low thermal expansion, the inorganic filler is preferably at least one selected from the group consisting of metal hydroxides and metal oxides, more preferably at least one selected from the group consisting of silica, boehmite and alumina, and further preferably silica.

[0363] Examples of silicas include natural silica, fused silica, synthetic silica, AEROSIL, and hollow silica. These silicas may be used alone or in combination of two or more. Of these, fused silica is preferred from the perspective of dispersibility, and two or more fused silicas having different particle sizes are more preferred from the perspective of filling properties and fluidity.

[0364] From the viewpoint of further improving low thermal expansion properties, the content of the inorganic filler is preferably 50 to 1000 parts by mass, more preferably 70 to 500 parts by mass, and even more preferably 100 to 300 parts by mass per 100 parts by mass of the resin solid content.

[0365] [Silane coupling agent]

[0366] The curable composition of this embodiment may further contain a silane coupling agent. By containing a silane coupling agent, the curable composition of this embodiment tends to further improve the dispersibility of the inorganic filler or further improve the bonding strength between the components of the curable composition of this embodiment and the substrate described below.

[0367] The silane coupling agent is not particularly limited, and examples thereof include those commonly used in surface treatment of inorganic materials, such as aminosilane compounds (e.g., γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (e.g., γ-glycidoxypropyltrimethoxysilane, etc.), acrylic silane compounds (e.g., γ-acryloxypropyltrimethoxysilane, etc.), cationic silane compounds (e.g., N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), styrylsilane compounds, and phenylsilane compounds. Silane coupling agents may be used alone or in combination of two or more. Among these, epoxysilane compounds are preferred. Examples of the epoxysilane-based compound include "KBM-403," "KBM-303," "KBM-402," and "KBE-403," all of which are products of Shin-Etsu Chemical Co., Ltd.

[0368] 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.

[0369] [Wetting and dispersing agent]

[0370] The curable composition in this embodiment may further contain a wetting dispersant. The curable composition in this embodiment tends to further improve the dispersibility of the filler by containing a wetting dispersant.

[0371] The wetting dispersant may be any known dispersant (dispersion stabilizer) for dispersing fillers, and examples thereof include DISPER BYK-110, 111, 118, 180, 161, BYK-W996, W9010, and W903 manufactured by BYK JAPAN CO., LTD.

[0372] The content of the wetting and dispersing agent is not particularly limited, but is preferably 0.5 parts by mass or more and 5.0 parts by mass or less relative to 100 parts by mass of the resin solid content.

[0373] [Solvent]

[0374] The curable composition of this embodiment may further contain a solvent. The curable composition of this embodiment contains a solvent, which tends to reduce viscosity during preparation of the curable composition, further improve workability (handling properties), or further improve penetration into a substrate.

[0375] The solvent is not particularly limited as long as it can dissolve part or all of the components in the curable composition, and examples thereof include ketones (acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (such as toluene, xylene, etc.), amides (such as dimethyl formaldehyde, etc.), propylene glycol monomethyl ether and its acetate, etc. These solvents can be used alone or in combination of two or more.

[0376] The method for producing the curable composition of the present embodiment is not particularly limited, and examples thereof include a method in which the above-mentioned components are mixed with a solvent once or in portions and stirred. In this case, in order to uniformly dissolve or disperse the components, known processes such as stirring, mixing, and kneading can be used.

[0377] [use]

[0378] As described above, the curable composition of this embodiment has excellent compatibility and can exhibit even better copper foil peel strength. Therefore, the curable composition of this embodiment is suitable for metal foil-clad laminates and printed circuit boards. In other words, the curable composition of this embodiment can be suitably used as a curable composition for printed circuit boards.

[0379] In particular, in the above-mentioned applications, the curable composition of the second embodiment preferably contains at least an epoxy compound C (an epoxy compound C existing separately from the structural unit C in the polymer E) in addition to the polymer E.

[0380] In this case, as the unit derived from the epoxy compound C, the polymer E preferably has a unit derived from the aforementioned bifunctional epoxy compound, more preferably has a unit derived from the aforementioned biphenyl type epoxy compound, further preferably has a unit derived from the compound represented by the above formula (b2) (compound b2), and even more preferably has a unit derived from R a The number of compounds b2 is 0 and the alkyl group R a The number of units of compound b2 (commercially available product, for example, trade name "YL-6121HA" manufactured by Mitsubishi Chemical Corporation) is 4.

[0381] In addition, as an epoxy compound C that exists separately from the structural unit C in the polymer E, it is preferred to include the aforementioned naphthylene ether type epoxy resin (as a commercial product, for example, "HP-6000" produced by DIC Corporation, etc.) and / or naphthylphenol novolac type epoxy resin (as a commercial product, for example, "HP-9540" produced by DIC Corporation, etc.).

[0382] [Prepreg]

[0383] The prepreg of this embodiment comprises a substrate and the curable composition of this embodiment impregnated or coated on the substrate. As described above, the prepreg can be obtained by a known method. Specifically, it is obtained by impregnating or coating the substrate with the curable composition of this embodiment and then heating and drying it at 100-200°C to semi-cure (B-stage).

[0384] The prepreg of the present embodiment also includes a cured product obtained by thermally curing a semi-cured prepreg at a heating temperature of 180 to 230° C. and a heating time of 60 to 180 minutes.

[0385] The content of the curable composition in the prepreg is preferably 30 to 90 volume % relative to the total amount of the prepreg, more preferably 35 to 85 volume %, and further preferably 40 to 80 volume % based on the solid content of the prepreg. By the content of the curable composition being within the above range, formability tends to be further improved. It should be noted that the cured product of the curable composition of the present embodiment is also included in the content calculation of the curable composition mentioned herein. In addition, the solid content of the prepreg mentioned herein refers to the component after excluding the solvent from the prepreg, such as the filling material is included in the prepreg solid content.

[0386] As substrate, it is not particularly limited, for example, the known substrate used in the material of various printed circuit boards can be enumerated. As the specific example of substrate, a glass substrate, an inorganic substrate other than glass (for example, an inorganic substrate consisting of inorganic fibers other than glass such as quartz), an organic substrate (for example, an organic substrate consisting of organic fibers such as wholly aromatic polyamide, polyester, poly(p-phenylene benzobisoxazole), polyimide) etc. can be enumerated. These substrates can be used alone or in combination of two or more. From the viewpoint of being more excellent in heating dimensional stability, a glass substrate is preferably used among these.

[0387] Examples of the fibers constituting the glass substrate include fibers of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. Among these, the fibers constituting the glass substrate are preferably fibers of one or more types selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass, from the viewpoint of superior strength and low water absorption.

[0388] The form of the substrate is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, chopped strand mats, and surface mats. The weaving method of the woven fabric is not particularly limited, and examples thereof include plain weave, basket weave, and twill weave. These can be appropriately selected and used from among these known fabrics according to the intended use and performance. In addition, glass fabrics obtained by subjecting these fabrics to fiber opening treatment or surface treatment with a silane coupling agent are preferably used. The thickness and mass of the substrate are not particularly limited, and a substrate of about 0.01 to 0.1 mm is generally suitable.

[0389] [Resin sheet]

[0390] The resin sheet of this embodiment comprises a support and a curable composition of this embodiment disposed on a surface of the support. The resin sheet of this embodiment can be formed, for example, by applying the curable composition of this embodiment to one or both surfaces of the support. The resin sheet of this embodiment can be produced, for example, by directly applying a curable composition used in prepregs, etc., onto a support such as a metal foil or film and drying the resulting composition.

[0391] The support is not particularly limited; for example, known materials used for various printed circuit board materials can be used, preferably resin sheets or metal foils. Examples of resin sheets or metal foils include polyimide films, polyamide films, polyester films, polyethylene terephthalate (PET) films, polybutylene terephthalate (PBT) films, polypropylene (PP) films, polyethylene (PE) films, and metal foils such as aluminum foil, copper foil, and gold foil. Among these, the support is preferably electrolytic copper foil or PET film.

[0392] The resin sheet of the present embodiment can be obtained, for example, by applying the curable composition of the present embodiment to a support and semi-curing it (B-stage). The method for manufacturing the resin sheet of the present embodiment is preferably a method for generally manufacturing a composite of a B-stage resin and a support. Specifically, for example, a method for manufacturing a resin sheet by applying the above-mentioned curable composition to a support such as copper foil and then heating it in a dryer at 100 to 200°C for 1 to 60 minutes can be cited. The amount of curable composition attached to the support is preferably in the range of 1.0 μm or more and 300 μm or less based on the resin thickness of the resin sheet. The resin sheet of the present embodiment can be used as a laminate material for a printed circuit board.

[0393] [Metal foil-clad laminate]

[0394] The metal foil-clad laminate of this embodiment comprises a laminate formed using one or more selected from the group consisting of the prepregs and resin sheets of this embodiment, and metal foil disposed on one or both sides of the laminate. The laminate may be formed from a single prepreg or resin sheet, or may be formed from multiple prepregs and / or resin sheets.

[0395] The metal foil (conductor layer) can be any metal foil used in various printed circuit board materials. Examples include copper and aluminum foils. Examples of copper foil include rolled copper foil and electrolytic copper foil. The thickness of the conductor layer is, for example, 1 to 70 μm, preferably 1.5 to 35 μm.

[0396] The forming method and forming conditions of the metal foil-clad laminate are not particularly limited, and the methods and conditions for conventional printed circuit board laminates and multilayer boards can be applied. For example, a multistage press, a multistage vacuum press, a continuous forming machine, an autoclave forming machine, etc. can be used to form the laminate (the above-mentioned laminate) or the metal foil-clad laminate. In addition, in the forming (laminate forming) of the laminate (the above-mentioned laminate) or the metal foil-clad laminate, the temperature is usually 100 to 300°C and the pressure is a surface pressure of 2 to 100 kgf / cm 2 , the heating time is in the range of 0.05 to 5 hours. In addition, if necessary, post-curing can also be carried out at a temperature of 150 to 300°C. In particular, when using a multi-stage press, from the perspective of fully promoting the curing of the prepreg, the temperature is preferably 200 to 250°C and the pressure is 10 to 40 kgf / cm 2 , heating time 80 minutes to 130 minutes, more preferably temperature 215 to 235 ° C, pressure 25 to 35 kgf / cm 2 , heating time 90 minutes to 120 minutes. In addition, by combining the above-mentioned prepreg with a separately produced inner layer circuit board and laminating them, a multilayer board can also be produced.

[0397] [Printed Circuit Board]

[0398] The printed wiring board of this embodiment comprises an insulating layer formed from one or more selected from the group consisting of the prepreg and resin sheet of this embodiment, and a conductive 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-clad laminate of this embodiment into a predetermined circuit pattern to form the conductive layer.

[0399] The printed circuit board of the present embodiment can be specifically manufactured by the following method, for example. First, prepare the metal foil clad laminate of the present embodiment. The metal foil of the metal foil clad laminate is etched into a specified wiring pattern to form an inner substrate with a conductor layer (inner circuit). Then, a specified number of insulating layers and metal foil for the outer layer circuit are sequentially stacked on the surface of the conductor layer (built-in circuit) of the inner substrate, and heated and pressed to form an integral body (laminate molding), thereby obtaining a laminate. It should be noted that the method of laminate molding and its molding conditions are the same as the method of laminate molding and its molding conditions in the above-mentioned laminate and metal foil clad laminate. Then, drilling processing for through holes and vias is performed on the laminate, and a metal-plated coating for conducting the metal foil for the conductor layer (built-in circuit) and the outer layer circuit is formed on the wall surface of the hole formed by this. Then, the metal foil for the outer layer circuit is etched into a specified wiring pattern to make an outer substrate with a conductor layer (outer layer circuit). In this way, a printed circuit board is manufactured.

[0400] In addition, when a metal foil-clad laminate is not used, a conductor layer forming a circuit can be formed on the insulating layer to produce a printed wiring board. In this case, the conductor layer can also be formed by chemical plating.

[0401] Example

[0402] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0403] (Example 1)

[0404] In a three-necked flask equipped with a thermometer and a condenser coil, 5.1 parts by mass of diallylbisphenol A (DABPA, Yamato Kasei Kogyo Co., Ltd.), 5.6 parts by mass of biscresol fluorene (BCF, Osaka Gas Chemical Co., Ltd.), 4.2 parts by mass of epoxy-modified silicone compound A (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent of 200 g / eq.), 8.5 parts by mass of epoxy-modified silicone compound B (KF-105, Shin-Etsu Chemical Co., Ltd., functional group equivalent of 500 g / eq.), 5.6 parts by mass of biphenyl-type epoxy compound A (YL-6121HA, Mitsubishi Chemical Corporation), and 30.0 parts by mass of propylene glycol monomethyl ether acetate (DOWANOL PMA, Dow Chemical Japan Co., Ltd.) as a solvent were added, and the mixture was heated to 120° C. in an oil bath and stirred. After confirming that the raw materials have dissolved in the solvent, 0.3 parts by mass of imidazole catalyst A (TBZ, Shikoku Chemicals Co., Ltd.) is added, the temperature is raised to 140°C, and the mixture is stirred for 5 hours. The mixture is then cooled to obtain a phenoxy polymer solution (solid content 50% by mass) (polymer formation step). It should be noted that diallyl bisphenol A corresponds to "alkenylphenol A", epoxy-modified silicone compound A and epoxy-modified silicone compound B correspond to "epoxy-modified silicone B", and biphenyl-type epoxy resin A corresponds to "epoxy compound C". The phenoxy polymer solution contains a polymer containing constituent units derived from alkenylphenol A, constituent units derived from epoxy-modified silicone B, and constituent units derived from epoxy compound C.

[0405] After heating the phenoxy polymer solution to 80°C in an oil bath, 1.0 part by mass (based on solid content) of aminotriazine novolac resin D (LA-3018-50P, DIC Corporation, weight-average molecular weight: 1,400, nitrogen content: 18% by mass, hydroxyl equivalent: 151 g / eq.) was added. The mixture was stirred for 2 hours and cooled to obtain a modified phenoxy polymer solution (solid content: 50% by mass) (polymer modification step). The modified phenoxy polymer solution contains a polymer comprising constituent units derived from alkenylphenol A, constituent units derived from epoxy-modified silicone B, constituent units derived from epoxy compound C, and constituent units derived from aminotriazine novolac resin D. The polymer modification step may also be performed continuously with the polymer production step.

[0406] It should be noted that LA-3018-50P, which is an aminotriazine novolac resin D, is a mixture of a compound represented by formula (1) (which is a mixture of compounds represented by formula (1), and the mixture contains a compound group in which R1 is each independently a hydrogen atom or a methyl group, l, m, and n are each independently an integer of 1 to 6, and (l+m+n) is an integer of 3 to 18) and a compound represented by formula (2) (which is a mixture of compounds represented by formula (2), and the mixture contains a compound group in which R2 is each independently a hydrogen atom or a methyl group, o, p, q, r, and s are each independently an integer of 1 to 4, and (o+p+q+r+s) is an integer of 5 to 20).

[0407] [Method for measuring weight average molecular weight Mw]

[0408] The weight average molecular weight Mw of the modified phenoxy polymer obtained as described above was measured by the following method. 20 μL of the solution obtained by dissolving 0.5 g of the modified phenoxy polymer solution in 2 g of THF was injected into a high performance liquid chromatograph (manufactured by Shimadzu Corporation, pump: LC-20AD) for analysis. Four columns were used: Shodex GPC KF-804 (length 30 cm × inner diameter 8 mm), Shodex GPC KF-803 (length 30 cm × inner diameter 8 mm), Shodex GPC KF-802 (length 30 cm × inner diameter 8 mm), and Shodex GPC KF-801 (length 30 cm × inner diameter 8 mm) manufactured by Showa Denko. THF (solvent) was used as the mobile phase, the flow rate was set to 1 mL / min, and the detector used was RID-10A. The weight average molecular weight Mw was obtained by GPC method using standard polystyrene as a standard substance.

[0409] The weight average molecular weight Mw of the modified phenoxy polymer measured in the above manner was 12,000.

[0410] The modified phenoxy polymer solution was mixed with 25 parts by mass of a naphthol aralkyl type phenol compound (SN-495V, Nippon Steel Chemicals Co., Ltd.), 9 parts by mass of a novolac type maleimide compound (BMI-2300, Yamato Chemicals Co., Ltd.), 9 parts by mass of a phenylene ether type maleimide compound (BMI-80, Yamato Chemicals Co., Ltd.), 27 parts by mass of a naphthylene ether type epoxy compound (HP-6000, DIC Corporation), 200 parts by mass of spherical silica (SC-2050MB, Admatechs Co., Ltd.), 1 part by mass of a wetting and dispersing agent (DISPERBYK-161, BYK Corporation), and 5 parts by mass of a silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) to obtain a varnish (varnish forming step). The varnish was applied to S glass woven fabric (thickness 100 μm) by impregnation, and dried by heating at 150° C. for 3 minutes to obtain a prepreg having a resin composition solid content (including filler) of 58.2 vol % (prepreg production process).

[0411] (Example 2)

[0412] A prepreg having a resin composition solid content (including filler) of 58.2% by volume was obtained in the same manner as in Example 1, except that the amount of diallylbisphenol A added in the polymer production step was changed from 5.1 parts by mass to 5.0 parts by mass, the amount of biscresol fluorene added was changed from 5.6 parts by mass to 5.5 parts by mass, the amount of epoxy-modified silicone A added was changed from 4.2 parts by mass to 4.1 parts by mass, the amount of epoxy-modified silicone B added was changed from 8.5 parts by mass to 8.4 parts by mass, and the amount of biphenyl-type epoxy compound A added was changed from 5.6 parts by mass to 5.5 parts by mass. In the polymer modification step, the amount of aminotriazine novolac resin D added was changed from 1.0 parts by mass to 1.5 parts by mass (based on solid content).

[0413] The modified phenoxy polymer solution contains a polymer having a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, a structural unit derived from an epoxy compound C, and a structural unit derived from aminotriazine novolac resin D.

[0414] The weight average molecular weight Mw of the modified phenoxy polymer in Example 2 measured by the aforementioned method was 12,000.

[0415] (Example 3)

[0416] A prepreg having a resin composition solid content (including filler) of 58.2% by volume was obtained in the same manner as in Example 1, except that the amount of diallylbisphenol A added in the polymer production step was changed from 5.1 parts by mass to 4.7 parts by mass, the amount of biscresol fluorene added was changed from 5.6 parts by mass to 5.2 parts by mass, the amount of epoxy-modified silicone A added was changed from 4.2 parts by mass to 3.8 parts by mass, the amount of epoxy-modified silicone B added was changed from 8.5 parts by mass to 8.1 parts by mass, and the amount of biphenyl-type epoxy compound A added was changed from 5.6 parts by mass to 5.2 parts by mass. In the polymer modification step, the amount of aminotriazine novolac resin D added was changed from 1.0 parts by mass to 3.0 parts by mass (based on solid content).

[0417] The modified phenoxy polymer solution contains a polymer having a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, a structural unit derived from an epoxy compound C, and a structural unit derived from aminotriazine novolac resin D.

[0418] The weight average molecular weight Mw of the modified phenoxy polymer in Example 3 measured by the aforementioned method was 12,000.

[0419] (Example 4)

[0420] In the polymer production step, the amount of diallylbisphenol A added was changed from 5.1 parts by mass to 4.9 parts by mass, the amount of biscresol fluorene added was changed from 5.6 parts by mass to 5.4 parts by mass, the amount of epoxy-modified silicone A added was changed from 4.2 parts by mass to 4.0 parts by mass, the amount of epoxy-modified silicone B added was changed from 8.5 parts by mass to 8.3 parts by mass, and the amount of biphenyl-type epoxy compound A added was changed from 5.6 parts by mass to 5.4 parts by mass. In the polymer modification step, 2.0 parts by mass (solids content conversion) of LA-7054 (DIC Corporation, weight average molecular weight: 2,400, nitrogen content: 12% by mass, hydroxyl equivalent: 125 g / eq.) was added instead of 1.0 parts by mass of LA-3018 as the aminotriazine novolac resin D. A prepreg having a resin composition solid content (including filler) of 58.2% by volume was obtained.

[0421] The modified phenoxy polymer solution contains a polymer having a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, a structural unit derived from an epoxy compound C, and a structural unit derived from aminotriazine novolac resin D.

[0422] The weight average molecular weight Mw of the modified phenoxy polymer in Example 4 measured by the aforementioned method was 12,000.

[0423] It should be noted that LA-7054, which is the aminotriazine novolac resin D, is a mixture of a compound represented by formula (1) (which is a mixture of compounds represented by formula (1), and the mixture contains a compound group in which R1 is each independently a hydrogen atom or a methyl group, l, m, and n are each independently an integer of 1 to 6, and (l+m+n) is an integer of 3 to 18) and a compound represented by formula (2) (which is a mixture of compounds represented by formula (2), and the mixture contains a compound group in which R2 is each independently a hydrogen atom or a methyl group, o, p, q, r, and s are each independently an integer of 1 to 4, and (o+p+q+r+s) is an integer of 5 to 20).

[0424] (Example 5)

[0425] In the polymer modification step, except that 3.0 parts by mass of LA-7052 (DIC Corporation, nitrogen content: 8% by mass, hydroxyl equivalent: 120 g / eq.) was added instead of 3.0 parts by mass of LA-3018 (based on solid content), a prepreg having a resin composition solid content (including filler) of 58.2% by volume was obtained in the same manner as in Example 3.

[0426] It should be noted that LA-7052, which is the aminotriazine novolac resin D, is a mixture of a compound represented by formula (1) (which is a mixture of compounds represented by formula (1), and the mixture contains a compound group in which R1 is each independently a hydrogen atom or a methyl group, l, m, and n are each independently an integer of 1 to 6, and (l+m+n) is an integer of 3 to 18) and a compound represented by formula (2) (which is a mixture of compounds represented by formula (2), and the mixture contains a compound group in which R2 is each independently a hydrogen atom or a methyl group, o, p, q, r, and s are each independently an integer of 1 to 4, and (o+p+q+r+s) is an integer of 5 to 20).

[0427] (Comparative Example 1)

[0428] In the polymer formation step, the amount of diallylbisphenol A added was changed from 5.1 parts by mass to 5.3 parts by mass, the amount of biscresol fluorene added was changed from 5.6 parts by mass to 5.8 parts by mass, the amount of epoxy-modified silicone A added was changed from 4.2 parts by mass to 4.4 parts by mass, the amount of epoxy-modified silicone B added was changed from 8.5 parts by mass to 8.7 parts by mass, and the amount of biphenyl-type epoxy compound A added was changed from 5.6 parts by mass to 5.8 parts by mass. A prepreg having a resin composition solid content (including filler) of 58.2% by volume was obtained in the same manner as in Example 1, except that the polymer modification step was not performed.

[0429] The weight average molecular weight Mw of the phenoxy polymer in Comparative Example 1 measured by the aforementioned method was 12,000.

[0430] (Comparative Example 2)

[0431] A prepreg having a resin composition solid content (including filler) of 58.2% by volume was obtained in the same manner as in Example 2, except that 1.5 parts by mass of TD-2090 (DIC Corporation) as a phenol novolac was added in place of 1.5 parts by mass of LA-3018 in the polymer modification step.

[0432] The weight average molecular weight Mw of the modified phenoxy polymer in Comparative Example 2 measured by the aforementioned method was 12,000.

[0433] Two sheets of prepreg obtained in Examples 1 to 5 and Comparative Examples 1 to 2 were stacked, and electrolytic copper foils (3EC-M2S-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) with a thickness of 12 μm were placed on top and bottom. 2 Lamination molding was performed at 220°C for 120 minutes to obtain a copper-clad laminate including a 0.2 mm thick insulating layer as a metal-clad laminate. The properties of the obtained copper-clad laminate were evaluated using the following methods. The evaluation results are shown in Table 1.

[0434] [Copper foil peel strength]

[0435] The copper foil peel strength was measured in accordance with JIS C6481 using the copper-clad laminate (10 mm×150 mm×0.2 mm) obtained by the above method.

[0436] [Table 1]

[0437]

[0438] As shown in Table 1 above, the copper-clad laminates (Examples 1 to 5) using the curable composition according to the present embodiment have excellent copper foil peeling strength.

[0439] This application is based on Japanese patent application No. 2021-128728 filed with the Japan Patent Office on August 5, 2021, the contents of which are incorporated herein by reference.

Claims

1. A curable composition comprising: an alkenylphenol A, an epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, an aminotriazine novolac resin D, and a phenol compound A′ other than the alkenylphenol A. in, The epoxy compound C includes a compound represented by the following formula (b2), In formula (b2), R a each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, The content of the epoxy compound C is 5 to 50 parts by mass based on 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 A′.

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

3. The curable composition according to claim 1 or 2, wherein The alkenylphenol A comprises diallyl bisphenol and / or diallyl bisphenol.

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

5. The curable composition according to claim 1 or 2, wherein The epoxy-modified silicone B comprises epoxy-modified silicone represented by the following formula (1): In formula (1), R 1 Each independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 0 to 100.

6. The curable composition according to claim 1 or 2, wherein The content of the epoxy compound C is 20 to 50% by mass relative to 100% by mass of the total amount of the epoxy-modified silicone B and the epoxy compound C.

7. The curable composition according to claim 1 or 2, wherein The aminotriazine novolac resin D is a novolac resin having 2 to 20 phenolic hydroxyl groups per one triazine skeleton in the molecule.

8. A curable composition comprising a polymer E, wherein the polymer E comprises a structural unit derived from an alkenylphenol A, a structural unit derived from an epoxy-modified silicone B, a structural unit derived from an epoxy compound C other than the epoxy-modified silicone B, a structural unit derived from an aminotriazine novolac resin D, and a structural unit derived from a phenol compound A′ other than the alkenylphenol A. in, The epoxy compound C includes a compound represented by the following formula (b2), In formula (b2), R a each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, The content of the epoxy compound C is 5 to 50 parts by mass based on 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 A′.

9. The curable composition according to claim 8, wherein The weight average molecular weight of the polymer E is 3.0×10 3 ~5.0×10 4 .

10. The curable composition according to claim 8 or 9, wherein The content of the structural unit derived from the epoxy-modified silicone B in the polymer E is 20 to 60% by mass relative to the total mass of the polymer E.

11. The curable composition according to claim 8 or 9, wherein The alkenyl equivalent weight of the polymer E is 300 to 1500 g / mol.

12. The curable composition according to claim 8 or 9, wherein The content of the structural unit derived from the aminotriazine novolac resin D in the polymer E is 3 to 20% by mass relative to the total mass of the polymer E.

13. The curable composition according to claim 8 or 9, wherein The content of the polymer E is 5 to 50% by mass relative to 100% by mass of the resin solid content.

14. The curable composition according to claim 8 or 9, wherein The alkenylphenol A comprises diallyl bisphenol and / or diallyl bisphenol.

15. The curable composition according to claim 8 or 9, wherein The epoxy-modified silicone B includes epoxy-modified silicone having an epoxy equivalent weight of 140 to 250 g / mol.

16. The curable composition according to claim 8 or 9, wherein The epoxy-modified silicone B comprises epoxy-modified silicone represented by the following formula (1): In formula (1), R 1 Each independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 0 to 100.

17. The curable composition according to claim 8 or 9, wherein The aminotriazine novolac resin D is a novolac resin having 2 to 20 phenolic hydroxyl groups per one triazine skeleton in the molecule.

18. The curable composition according to claim 8 or 9, further comprising an epoxy compound C, wherein the epoxy compound C comprises a compound represented by the following formula (3-3) or a compound represented by the following formula (3-4). In formula (3-3), 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, In formula (3-4), 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. 19 . The curable composition according to claim 1 , further comprising at least one compound F selected from the group consisting of maleimide compounds, cyanate compounds, and alkenyl-substituted nadic imide compounds.

20. The curable composition according to claim 19, wherein The maleimide compound comprises at least one selected from the group consisting of bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)phenyl}propane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, a maleimide compound represented by the following formula (3), and a maleimide compound represented by the following formula (3′). In formula (3), R5 each independently represents a hydrogen atom or a methyl group, n1 represents an integer greater than 1, In formula (3'), R 13 Each independently represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group, n 4 It represents an integer greater than or equal to 1 and less than or equal to 10.

21. The curable composition according to claim 19, wherein The cyanate compound includes a compound represented by the following formula (4) and / or a compound represented by the following formula (5) other than the compound represented by the following formula (4). In formula (4), R6 each independently represents a hydrogen atom or a methyl group, n2 represents an integer greater than 1, In formula (5), R ya Each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, and R yb Each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and R yc Each independently represents an aromatic ring having 4 to 12 carbon atoms, R yc Optionally form a condensed structure with a benzene ring, R yc Optional presence or absence, 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, and R yc When not present, one benzene ring may optionally have two or more R ya and / or R yb wherein n represents an integer of 1 to 20.

22. The curable composition according to claim 1 or 8, wherein The phenol compound A' comprises a compound represented by the following formula (8): In formula (8), R7 each independently represents a hydrogen atom or a methyl group, and n3 represents an integer of 1 or greater. 23 . The curable composition according to claim 1 , further comprising an inorganic filler, wherein the content of the inorganic filler is 50 to 1000 parts by mass based on 100 parts by mass of the resin solid content.

24. The curable composition according to claim 23, wherein The inorganic filler includes one or more selected from the group consisting of silica, boehmite, and alumina.

25. The curable composition according to claim 1 or 8, which is used for a printed circuit board.

26. A prepreg comprising a substrate and the curable composition according to claim 1 or 8 impregnated or coated on the substrate. 27 . A resin sheet comprising a support and the curable composition according to claim 1 or 8 disposed on a surface of the support.

28. A metal foil-clad laminate comprising: A laminate formed using the prepreg according to claim 26; and A metal foil is disposed on one or both sides of the laminate.

29. A metal foil-clad laminate comprising: A laminate formed using the resin sheet according to claim 27; and A metal foil is disposed on one or both sides of the laminate.

30. A printed circuit board comprising: An insulating layer formed using the prepreg according to claim 26; and A conductive layer is formed on the surface of the insulating layer.

31. A printed circuit board comprising: An insulating layer formed using the resin sheet according to claim 27; and A conductive layer is formed on the surface of the insulating layer.

32. A method for producing the curable composition according to claim 1 or 8, comprising: a step of obtaining a prepolymer obtained by polymerizing an alkenylphenol A, an epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, and a phenol compound A′ other than the alkenylphenol A; and A step of reacting the aminotriazine novolac resin D with the prepolymer.

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