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

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

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

[0005]

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

[0007]

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

[0009]

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

[0011] Prior art literature

[0012] Patent Literature

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

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

[0015] Problems to be solved by the invention

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

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

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

[0019] Solutions for solving problems

[0020] The present inventors have conducted intensive research to solve the above-mentioned problems. As a result, they have discovered that a curable composition containing an alkenylphenol, an epoxy-modified silicone, an epoxy compound other than an epoxy-modified silicone, and an acid anhydride, or a curable composition containing a polymer having these as structural units, can solve the above-mentioned problems, thereby completing the present invention.

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

[0023] A curable composition comprising alkenylphenol A, epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, and an acid anhydride 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 contains 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 curable 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 [1] to [7], wherein the acid anhydride D is one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, and cis-4-cyclohexene-1,2-dicarboxylic anhydride. [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 acid anhydride (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 acid anhydride 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 contains 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] , wherein the acid anhydride D is one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, and cis-4-cyclohexene-1,2-dicarboxylic anhydride.

[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 maleimide compounds, cyanate compounds, phenol compounds A' other than alkenylphenol A, and alkenyl-substituted nadic imide compounds. [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 absent, a benzene ring can 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

[25] , wherein the inorganic filler contains 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

[26] above, which is a curable composition 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 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 polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C to obtain a prepolymer; and

[0113] A step of reacting the acid anhydride 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 low thermal expansion and copper foil peel strength can be provided. DETAILED DESCRIPTION

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

[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 a state of a mixture (eg, varnish) containing alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and acid anhydride D.

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

[0120] The curable composition of this embodiment has excellent compatibility, which suppresses liquid phase separation during the molding process, resulting in a molded article with excellent appearance. The obtained molded article also tends 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 acid anhydride D. The curable composition containing these ingredients 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 has excellent low thermal expansion and copper foil peeling strength. In addition, in the curable composition, if a part of each of these components is reacted (polymerized) and used, it can exhibit better compatibility and can exhibit better low thermal expansion and copper foil peeling strength (curable composition of the second embodiment).

[0123] [Alkenylphenol A]

[0124] There are no particular limitations on 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 are no particular limitations on the alkenyl group, and examples thereof include alkenyl groups having 2 to 30 carbon atoms, such as vinyl, allyl, propenyl, butenyl, and hexenyl. Among them, from the viewpoint of more effectively and reliably exerting the effects of the present invention, the alkenyl group is preferably an allyl group and / or propenyl, and more preferably an allyl group. The number of alkenyl groups directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1 to 4. From the viewpoint of more effectively and reliably exerting the effects of the present invention, the number of alkenyl groups directly bonded to one phenolic aromatic ring is preferably 1 to 2, and more preferably 1. In addition, the bonding position of the alkenyl group on the phenolic aromatic ring is not particularly limited, and is preferably the ortho position (2, 6 positions).

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

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

[0128] The alkenylphenol A may have one or more structures in which one or more alkenyl groups are directly bonded to the phenolic aromatic ring. From the perspective of more effectively and reliably exerting the effects of the present invention, the alkenylphenol A preferably has one or two structures in which one or more alkenyl groups are directly bonded to the 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 form a condensed structure with a benzene ring, and Rxc may be present or absent, and A represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, a sulfur atom, or a direct bond (single bond). When Rxc is absent, one benzene ring may contain two or more groups of Rxa and / or Rxb.)

[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, and Rxf represents an aromatic ring having 4 to 12 carbon atoms. Rxf may form a condensed structure with a benzene ring. Rxf may or may not be present. When Rxf is absent, one benzene ring may contain two or more groups of Rxd and / or Rxe.)

[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 the case where the groups represented by Rxc and Rxf in formula (1A) and formula (1B) form a condensed structure with a benzene ring, for example, a compound containing a naphthol ring as a phenolic aromatic ring can be given. In addition, in the case where the groups represented by Rxc and Rxf are not present in formula (1A) and formula (1B), for example, a compound containing a phenol ring as a phenolic aromatic ring can be given.

[0136] The C1-10 alkyl groups represented by Rxb and Rxe in formula (1A) and formula (1B) are not particularly limited, and examples thereof include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, and hexyl, and branched alkyl groups such as isopropyl, isobutyl, and tert-butyl.

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

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

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

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

[0142]

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

[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 the present 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 reticular skeleton. Among them, a linear skeleton is preferred for 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 and tends to further improve low thermal expansion and copper foil peel strength in a well-balanced manner. For the same reason, the epoxy equivalent weight is more preferably 145 to 245 g / mol, and even more preferably 150 to 240 g / mol.

[0152] Epoxy-modified silicone B preferably contains two or more epoxy-modified silicones from the perspective of achieving better compatibility with thermosetting resins and further improving low thermal expansion properties and copper foil peel strength in a well-balanced manner. In this case, the two or more epoxy-modified silicones preferably have different epoxy equivalents, more preferably including an epoxy-modified silicone with an epoxy equivalent of 50 to 350 g / mol (hereinafter also referred to as "low-equivalent-weight epoxy-modified silicone B1") and an epoxy-modified silicone with an epoxy equivalent of 400 to 4000 g / mol (hereinafter also 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, and Wi represents the ratio of the above epoxy-modified silicones in the epoxy-modified silicone (B), which is W1+W2+…W n =1.)

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

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

[0160] In formula (1), R1 The arylene group shown may also have a substituent. The number of carbon atoms in the arylene group is preferably 6 to 40, more preferably 6 to 20. Examples of the arylene group include phenylene, cyclohexylphenylene, hydroxyphenylene, cyanophenylene, nitrophenylene, naphthylene, biphenylene, anthrylene, pyrenylene, and fluorenylene. These groups may also contain an ether bond, a ketone bond, or an ester bond.

[0161] In formula (1), R 1 The number of carbon atoms in the aralkylene group 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 a connecting bond.)

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

[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 also have substituents. The alkyl group having 1 to 10 carbon atoms may be linear, branched, or cyclic. There are no particular restrictions on the alkyl group, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, and cyclohexyl. Among these, R 2 Preferred is methyl or phenyl.

[0166] In formula (1), n ​​represents an integer greater than or equal to 0, for example, 0 to 100. From the viewpoint of achieving better compatibility with the thermosetting resin and further improving low thermal expansion properties 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 perspective of achieving better compatibility with thermosetting resins and further improving low thermal expansion properties 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] To more effectively and reliably exhibit 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 exhibiting more excellent low thermal expansion and chemical resistance, the content of the epoxy-modified silicone B is preferably 5 to 95 mass %, more preferably 10 to 90 mass %, further preferably 40 to 85 mass %, and even more preferably 50 to 80 mass % relative to 100 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 of this embodiment can exhibit excellent compatibility, heat resistance, chemical resistance, copper foil peel strength, and insulation reliability by containing epoxy compound C.

[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 bifunctional 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 exhibiting superior compatibility, heat resistance, chemical resistance, copper foil peel strength, and insulation reliability, the epoxy compound C preferably includes a bifunctional epoxy compound and / or a polyfunctional epoxy compound.

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

[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, and the substituents may be glycidyloxy groups not shown in the figure, or other substituents, such as alkyl groups having 1 to 5 carbon atoms, phenyl groups, etc.

[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 bifunctional epoxy compounds 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, and the substituents may be, for example, alkyl groups having 1 to 5 carbon atoms, phenyl groups, or other substituents other than glycidyloxy groups.

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

[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 polyfunctional 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, and each ring may have a substituent other than a glycidyloxy group (for example, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a phenyl group), Ar 31 and Ar 41 At least one of 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-type epoxy resin is not particularly limited, but is preferably, for example, a cresol / naphthol novolac-type epoxy resin represented by the following formula (NE). It should be noted that the compound represented by the following formula (NE) is a random copolymer of a cresol novolac epoxy structural unit and a naphthol novolac epoxy structural unit, and both the cresol epoxy and the naphthol epoxy can be terminal.

[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 the ratio thereof are not particularly limited, but from the viewpoint of low thermal expansion, m:n (here, m+n=100) is preferably 30-50:70-50, and more preferably 45-55:55-45.

[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 belong to the above-mentioned phenol novolac-type epoxy resin (hereinafter also referred to as "aralkyl-type epoxy resin").

[0197] As the aralkyl type epoxy resin, Ar in formula (3a) is preferably 3 is a naphthalene ring and Ar4 A compound having a benzene ring (also called a "naphthol aralkyl type epoxy resin"), and Ar in formula (3a) 3 is a benzene ring and Ar 4 The compound is a biphenyl ring compound (also referred to as a "biphenyl aralkyl type epoxy resin"), and more preferably a biphenyl aralkyl type epoxy resin.

[0198] As the naphthol aralkyl type epoxy resin, commercially available products or products produced by known methods 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 Co., Ltd.

[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 compounds represented by formula (3a)) is preferably used. As the naphthalene-type epoxy resin, a naphthyl ether-type epoxy resin is preferred from the viewpoint of further improving heat resistance, chemical resistance, copper foil peel strength, and insulation reliability.

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

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

[0211] Examples of naphthalene-type epoxy resins other than the above-mentioned ones include, but are not limited to, 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 compounds represented by the formula (b3) include "HP-4032" (n=0 in the formula (b3)) and "HP-4710" (n=0, R in the formula (b3)) manufactured by DIC Corporation. 3b is a naphthylmethyl group containing at least one glycidyl ether oxy group) and the like.

[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 those belonging to the above-mentioned 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. Examples of the alkyl group include, but are not limited to, 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 in the form of a mixture of compounds b2 having different numbers of alkyl groups, i.e., R. Specifically, a mixture of biphenyl-type epoxy resins having different numbers of alkyl groups, i.e., R. is preferably a mixture, and more preferably a mixture of compound b2 having 0 alkyl groups, i.e., R., and compound b2 having 4 alkyl groups, i.e., R.

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

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

[0229] Among these, for epoxy compound C, from the viewpoint of exhibiting better heat resistance, chemical resistance, copper foil peel strength and insulation reliability, it is preferred that one or more selected from the group consisting of epoxy compounds represented by formula (3a), naphthalene-type epoxy resins and biphenyl-type epoxy compounds be used. In this case, it is preferred that the epoxy compound represented by formula (3a) include a naphthol novolac-type epoxy resin, and the naphthalene-type epoxy resin include a naphthyl ether-type epoxy resin.

[0230] The epoxy compound C may contain other epoxy compounds that do not belong to the above-mentioned epoxy compounds.

[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 composed of bisphenol A-type structural units and hydrocarbon-based structural units.

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

[0233] As the epoxy compound C, among the aforementioned epoxy compounds and epoxy resins, one type may be used alone or two or more types may be used in combination.

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

[0235] The average number of epoxy groups was calculated by the following formula.

[0236]

[0237] (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 compound, Z1+Z2+…Z n =1.)

[0238] From the viewpoint of exhibiting superior 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.

[0239] [anhydride D]

[0240] The curable composition of this embodiment contains an acid anhydride D. The acid anhydride D reacts with the terminal hydroxyl groups and epoxy groups generated by the reaction of the alkenylphenol A, the epoxy-modified silicone B, and the epoxy compound C other than the epoxy-modified silicone B to generate terminal carboxyl groups. This results in the presence of a large number of carboxyl groups highly reactive with the thermosetting resin, thereby improving compatibility and crosslinking density, and also improving low thermal expansion properties.

[0241] The acid anhydride D is not particularly limited, and is not particularly limited if it has a cyclic structure. From the viewpoint of the tendency for further excellent compatibility with the thermosetting resin, an acid anhydride having 4 to 20 carbon atoms is preferred, an acid anhydride having 4 to 16 carbon atoms is more preferred, and an acid anhydride having 4 to 10 carbon atoms is further preferred.

[0242] Examples of the acid anhydride D include one or more selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, and cis-4-cyclohexene-1,2-dicarboxylic anhydride. Among these, phthalic anhydride and succinic anhydride are more preferred from the viewpoint of further improving the compatibility with the thermosetting resin and the balance between low thermal expansion and copper foil peel strength.

[0243] From the viewpoint of achieving further excellent compatibility with thermosetting resins and further improving low thermal expansion properties and copper foil peel strength in a well-balanced manner, the content of acid anhydride D is preferably 0.8 to 15% by mass, more preferably 0.9 to 10% by mass, and even more preferably 1 to 5% by mass, relative to 100% by mass of the resin solids.

[0244] [Compound F]

[0245] 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 a maleimide compound, a cyanate ester compound, a phenol compound A' other than the aforementioned alkenylphenol A, and an alkenyl-substituted nadic imide compound. Compound F is not particularly limited, but is preferably difunctional or higher, and may be polyfunctional or higher.

[0246] 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.

[0247] (Maleimide compound)

[0248] From the viewpoint of further improving the low thermal expansion property and the copper foil peeling strength, it is preferred to contain a maleimide compound as compound F. The maleimide compound is not particularly limited as long as it is a compound having one or more maleimide groups in one molecule, and examples thereof include monomaleimide compounds having one maleimide group in one molecule (e.g., N-phenylmaleimide, N-hydroxyphenylmaleimide, etc.), polymaleimide compounds having two or more maleimide groups in one molecule (e.g., bis(4-maleimidephenyl)methane, 2,2-bis{4-(4-maleimidephenoxy)-phenyl}propane, bis(3-ethyl-5-(1,2-dimethylamino)-1,2-diol)-1,2-diol)-1,2-diol)-2 ... -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.

[0249]

[0250] (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.)

[0251] n1 is 1 or more, preferably 1-100, and more preferably 1-10.

[0252]

[0253] (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.)

[0254] These maleimide compounds may be used alone or in combination of two or more. Among them, from the viewpoint of further improving low thermal expansion and 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').

[0255] The maleimide compound may be a commercially available product or a product produced by a known method. Examples of commercially available maleimide compounds include "BMI-70", "BMI-80", and "BMI-1000P" manufactured by K.I. Chemical Industry Co., Ltd., "BMI-3000", "BMI-4000", "BMI-5100", "BMI-7000", and "BMI-2300" manufactured by Daiwa Kasei Industry Co., Ltd., and "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. (R in formula (3') is α-Hydroxy-1 ... 13 All are hydrogen atoms, n 4 A mixture of 1 to 10. ) etc.

[0256] 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.

[0257] (Cyanate ester compound)

[0258] From the viewpoint of further improving the low thermal expansion property and the copper foil peeling strength, it is preferable to contain a cyanate compound as the compound F. 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 、1,3-dicyanobenzene, 1,4-dicyanobenzene, 1,3,5-tricyanobenzene, 1,3-dicyanonaphthalene, 1,4-dicyanonaphthalene, 1,6-dicyanonaphthalene, 1,8-dicyanonaphthalene, 2,6-dicyanonaphthalene, 2,7-dicyanonaphthalene, 1,3,6-tricyanonaphthalene, 4,4'-dicyanobiphenyl, bis(4-cyanophenyl)ether, bis(4-cyanophenyl)sulfide, bis(4-cyanophenyl)sulfone, 2,2-bis(4-cyanophenyl)propane. These cyanate compounds can be used alone or in combination of two or more. In the present embodiment, from the viewpoint of heat resistance, low thermal expansion and copper foil peel strength, the cyanate compound preferably includes a polyfunctional cyanate compound such as a naphthol aralkyl type cyanate compound and / or a novolac type cyanate compound.

[0259]

[0260] (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.)

[0261]

[0262] (In formula (5), Rya each independently represents an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, Ryb each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, Ryc each independently represents an aromatic ring having 4 to 12 carbon atoms, Ryc may form a condensed structure with a benzene ring, and Ryc may or may not exist, A 1a Each independently represents an alkylene group having 1 to 6 carbon atoms, an aralkylene group having 7 to 16 carbon atoms, an arylene group having 6 to 10 carbon atoms, a fluorenylidene group, a sulfonyl group, an oxygen atom, a sulfur atom, or a direct bond (single bond). When Ryc is absent, two or more Rya and / or Ryb groups may be present on one benzene ring. n represents an integer of 1 to 20.

[0263] Among them, the cyanate compound preferably contains a compound represented by formula (4) and / or formula (5) from the viewpoint of further improving heat resistance, low thermal expansion properties, and copper foil peeling strength.

[0264] 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.

[0265] In formula (5), the alkenyl group having 2 to 8 carbon atoms represented by Rya is not particularly limited, and examples thereof include vinyl, allyl, propenyl, butenyl, and hexenyl.

[0266] 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.

[0267] In formula (5), as A 1a The alkylene group having 1 to 6 carbon atoms is not particularly limited, and examples thereof include methylene, ethylene, trimethylene, and propylene. 1a The aralkylene group having 7 to 16 carbon atoms is not particularly limited, and examples thereof include groups represented by the formula: -CH2-Ar-CH2-, -CH2-CH2-Ar-CH2-CH2-, or -CH2-Ar-CH2-CH2- (wherein Ar represents a phenylene group, a naphthylene group, or a biphenylene group). 1a The arylene group having 6 to 10 carbon atoms is not particularly limited, and examples thereof include a phenylene ring.

[0268] 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.

[0269] The compound represented by formula (5) is preferably a compound represented by the following formula (c1).

[0270]

[0271] (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.)

[0272] These cyanate compounds can also be produced according to known methods. As a specific production method, for example, the method described in Japanese Patent Application Laid-Open No. 2017-195334 (particularly paragraphs 0052 to 0057) can be mentioned.

[0273] From the viewpoint of further improving low thermal expansion properties 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.

[0274] (Phenolic compound A' other than alkenylphenol A)

[0275] As compound F, from the viewpoint of being able to exhibit even better copper foil peel strength, a phenol compound A' other than alkenylphenol A may be contained. As phenol compound A', there are no particular limitations, 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.

[0276] Among them, the phenol compound A′ preferably contains a bifunctional phenol compound having two phenolic hydroxyl groups in one molecule from the viewpoint of expressing more excellent compatibility and copper foil peeling strength.

[0277] The bifunctional phenol compound is not particularly limited, and examples thereof include bisphenol, biscresol, bisphenols having a fluorene skeleton (e.g., bisphenol having a fluorene skeleton, biscresol having a fluorene skeleton), biphenols (e.g., p,p'-biphenol), dihydroxydiphenyl ethers (e.g., 4,4'-dihydroxydiphenyl ether), dihydroxydiphenyl ketones (e.g., 4,4'-dihydroxydiphenyl ketone), dihydroxydiphenyl sulfides (e.g., 4,4'-dihydroxydiphenyl sulfide), and dihydroxyaromatic hydrocarbons (e.g., hydroquinone). These bifunctional phenol compounds can be used alone or in combination of two or more. Among these, from the perspective of exhibiting superior copper foil peel strength, the bifunctional phenol compound preferably includes at least one selected from the group consisting of bisphenol, biscresol, and bisphenols having a fluorene skeleton. From the same perspective as above, biscresol fluorene is preferred as the bisphenol having a fluorene skeleton.

[0278] Examples of the aralkyl-type phenol resin include compounds represented by the following formula (c2).

[0279]

[0280] (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).

[0281] From the viewpoint of further improving the peel strength of the copper foil, the compound represented by formula (c2) is preferably 1 is a naphthalene ring and Ar 2 A compound having a benzene ring (hereinafter also referred to as "naphthol aralkyl type phenolic resin"), and Ar in formula (c2) 1 is a benzene ring and Ar 2 A compound containing a biphenyl ring (hereinafter also referred to as a "biphenyl aralkyl type phenol resin").

[0282] The naphthol aralkyl type phenol resin is preferably a compound represented by the following formula (8).

[0283]

[0284] (In the formula, R7 each independently represents a hydrogen atom or a methyl group, and n3 represents an integer greater than 1.)

[0285] 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.

[0286] The biphenyl aralkyl phenol resin is preferably a compound represented by the following formula (2c).

[0287]

[0288] (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).

[0289] From the viewpoint of further improving the low thermal expansion property and the copper foil peeling strength, the phenol compound A' preferably contains a compound represented by the above formula (8).

[0290] The aralkyl phenolic resin may be a commercially available product or a product produced by a known method. Examples of commercially available aralkyl phenolic resins include "KAYAHARD GPH-65," "KAYAHARD GPH-78," and "KAYAHARD GPH-103" (biphenyl aralkyl phenolic resins) manufactured by Nippon Kayaku Co., Ltd., and "SN-495" (naphthol aralkyl phenolic resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.

[0291] From the viewpoint of exhibiting more 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'.

[0292] From the viewpoint of achieving a well-balanced expression of excellent low thermal expansion and copper foil peel strength, the content of the epoxy-modified silicone B in the curable composition of the present embodiment is preferably 5 to 70 parts by mass, more preferably 10 to 60 parts by mass, and even more preferably 20 to 55 parts by mass, relative to 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and phenol compound A'.

[0293] From the viewpoint of exhibiting better compatibility, heat resistance, chemical resistance, copper foil peel strength and insulation reliability, the content of the epoxy compound C in the curable composition of the present embodiment is preferably 5 to 50 parts by mass, more preferably 10 to 30 parts by mass, and even more preferably 15 to 25 parts by mass, relative to 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C and phenol compound A'.

[0294] From the viewpoint of exhibiting better copper foil peel strength, the content of the phenol compound A' in the curable composition of the present embodiment is preferably 5 to 30 parts by mass, more preferably 10 to 25 parts by mass, and even more preferably 15 to 20 parts by mass, relative to 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and phenol compound A'.

[0295] 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.

[0296] (Alkenyl-substituted nadic imide compound)

[0297] Compound F preferably contains an alkenyl-substituted nadic imide compound from the viewpoint of further improving heat resistance. The alkenyl-substituted nadic imide compound is not particularly limited as long as it has one or more alkenyl-substituted nadic imide groups per molecule, and examples thereof include the compound represented by the following formula (2d).

[0298]

[0299] (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).)

[0300]

[0301] (In formula (6), R3 represents methylene, isopropylidene, CO, O, S or SO2.)

[0302]

[0303] (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.)

[0304] The alkenyl-substituted nadic acid imide compound represented by formula (2d) may be a commercially available product or a product produced by a known method. Examples of commercially available products include "BANI-M" and "BANI-X" manufactured by Maruzen Petrochemical Co., Ltd.

[0305] 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.

[0306] [Second embodiment: curable composition]

[0307] The curable composition of the second embodiment 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 other than the epoxy-modified silicone B, and a structural unit derived from an acid anhydride D. The alkenylphenol A, the epoxy-modified silicone B, the epoxy compound C, and the acid anhydride D are as described above. Hereinafter, the curable resin composition of the second embodiment containing the polymer E, which contains the structural unit derived from the alkenylphenol A, the structural unit derived from the epoxy-modified silicone B, the structural unit derived from the epoxy compound C, and the structural unit derived from the acid anhydride D, is distinguished from the curable composition of the first embodiment described above, which does not contain the polymer E.

[0308] Polymer E exhibits sufficient compatibility even when mixed with thermosetting resins that lack compatibility with silicone compounds. Consequently, curable compositions containing polymer E and thermosetting resins can produce uniform varnishes and cured products. Cured products such as prepregs produced using this curable composition exhibit uniform compatibility among the components, suppressing any uneven physical properties caused by uneven composition.

[0309] 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 acid anhydride D. In this case, the alkenylphenol A, epoxy-modified silicone B, epoxy compound C, and acid anhydride 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 newly added to the already synthesized polymer E.

[0310] 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 maleimide compound, the cyanate compound, the phenol compound A' other than the alkenylphenol A, and the alkenyl-substituted nadic imide compound, as needed. The compound F may be an unreacted component remaining after the polymerization of the polymer E, or a component newly added to the already synthesized polymer E.

[0311] [Polymer E]

[0312] The polymer E contains a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, a structural unit derived from epoxy compound C, and a structural unit derived from acid anhydride D. It may also contain a structural unit derived from at least one compound F selected from the group consisting of a maleimide compound, a cyanate compound, a phenol compound A' other than the aforementioned alkenylphenol A, and an alkenyl-substituted nadic imide compound as needed. When the polymer E has a structural unit derived from compound F, compound F is preferably a bifunctional compound. It should be noted that in this specification, "structural unit derived from alkenylphenol A", "structural unit derived from epoxy-modified silicone B", "structural unit derived from epoxy compound C", "structural unit derived from acid anhydride D", and "structural unit derived from compound F" are defined as structural units contained in the polymer E after polymerizing the components of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, acid anhydride D, and compound F, and structural units formed by reactions that can provide the same structural units. Hereinafter, each structural unit will also be referred to as structural unit A, B, C, D, F, respectively. By using the polymer E, the curable composition of the second embodiment has further excellent compatibility, and further excellent heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability.

[0313] The weight average molecular weight of polymer E is preferably 3.0×10 3 ~5.0×10 4 , more preferably 3.0×10 3 ~2.0×10 4 By making the weight average molecular weight 3.0×103 As described above, the curable composition of the second embodiment tends to exhibit more excellent heat resistance, chemical resistance, low thermal expansion, copper foil peeling strength and insulation reliability. 4 Hereinafter, the curable composition of the second embodiment tends to exhibit more excellent compatibility.

[0314] 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. By setting the content of the structural unit A within this range, the curable composition of the second embodiment tends to exhibit better compatibility. From the same viewpoint, the content of the structural unit A is preferably 10 to 45% by mass, and more preferably 15 to 40% by mass.

[0315] 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. By setting the content of the structural unit B within this range, the curable composition of the second embodiment tends to exhibit a well-balanced low thermal expansion and copper foil peel strength. From the same perspective, the content of the structural unit B is more preferably 25 to 55% by mass, and even more preferably 30 to 50% by mass.

[0316] Structural unit B preferably comprises structural units derived from an epoxy-modified silicone having an epoxy equivalent weight of 50 to 350 g / mol (low-equivalent epoxy-modified silicone B1) and an epoxy-modified silicone having an epoxy equivalent weight of 400 to 4000 g / mol (high-equivalent epoxy-modified silicone B2). Low-equivalent epoxy-modified silicone B1 and high-equivalent epoxy-modified silicone B2 are more preferably epoxy-modified silicone having an epoxy equivalent weight of 140 to 250 g / mol (low-equivalent epoxy-modified silicone B1') and epoxy-modified silicone having an epoxy equivalent weight of 450 to 3000 g / mol (high-equivalent epoxy-modified silicone B2'), respectively.

[0317] 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.

[0318] 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.

[0319] The mass ratio of the content of structural unit B2 to the content of structural unit B1 is preferably 1.5 to 4, more preferably 1.7 to 3.5, and even more preferably 1.9 to 3.1. By having the above relationship between the contents of structural unit B1 and structural unit B2, the curable composition of the second embodiment tends to have further improved low thermal expansion properties and copper foil peel strength.

[0320] 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).

[0321] The content of structural unit C in polymer E is preferably 5 to 40% by mass relative to the total mass of polymer E. When the content of structural unit C is within this range, the curable composition of the second embodiment tends to have better compatibility and exhibit better heat resistance, chemical resistance, copper foil peel strength, and insulation reliability. From the same perspective, the content of structural unit C is preferably 10 to 30% by mass, and more preferably 15 to 25% by mass.

[0322] Furthermore, the content of structural unit C is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, further preferably 15 to 60% by mass, and particularly preferably 20 to 50% by mass, relative to the total mass of structural unit B and structural unit C. By maintaining the above relationship between the contents of structural unit B and structural unit C, the curable composition of the second embodiment tends to have better compatibility, and further improved heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability.

[0323] The content of structural unit D in polymer E is preferably 3 to 20% by mass relative to the total mass of polymer E. By setting the content of structural unit D 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 perspective, the content of structural unit D is more preferably 5 to 15% by mass, and even more preferably 5 to 10% by mass.

[0324] When polymer E includes a structural unit derived from compound F, the content of structural unit F in polymer E is preferably 3 to 40% by mass relative to the total mass of polymer E. By setting the content of structural unit F within this range, the curable composition of the second embodiment tends to exhibit superior heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. From the same perspective, the content of structural unit F is preferably 5 to 35% by mass, and more preferably 10 to 30% by mass.

[0325] 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. By setting the content of structural unit A' within this range, the curable composition of the second embodiment tends to exhibit superior heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. From the same perspective, the content of structural unit A' is more preferably 10 to 27.5% by mass, and even more preferably 10 to 25% by mass.

[0326] The alkenyl equivalent weight in polymer E is preferably 300 to 1500 g / mol. By setting the alkenyl equivalent weight to 300 g / mol or more, the cured product of the curable composition of the second embodiment tends to have a further reduced elastic modulus, resulting in a tendency to further reduce the thermal expansion coefficient of the substrate, etc. obtained using the cured product. By setting the alkenyl equivalent weight to 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 weight is preferably 350 to 1200 g / mol, and more preferably 400 to 1000 g / mol.

[0327] 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 have better compatibility and exhibit a well-balanced low thermal expansion and copper foil peel strength.

[0328] The polymer E can be obtained, for example, by reacting alkenylphenol A, epoxy-modified silicone B, epoxy compound C, acid anhydride D, and, if necessary, compound F in the presence of a polymerization catalyst G. This reaction can also be carried out in the presence of an organic solvent.

[0329] More specifically, in the above step, after carrying out an addition reaction between the epoxy groups of the epoxy-modified silicone B and the epoxy compound C and the hydroxyl groups of the alkenylphenol A, and an addition reaction between the hydroxyl groups of the resulting addition reaction product and the epoxy groups of the epoxy-modified silicone B and the epoxy compound C, an addition reaction between the terminal hydroxyl groups and the epoxy groups and the acid anhydride D is further carried out, thereby obtaining the polymer E.

[0330] The method for producing the curable composition of the present embodiment (particularly the curable composition of the second embodiment) preferably includes:

[0331] a step of polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C to obtain a prepolymer; and

[0332] A step of reacting the prepolymer with an acid anhydride D.

[0333] By forming a prepolymer by polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C, and then reacting the prepolymer with acid anhydride D, a curable composition having even better low thermal expansion and copper foil peel strength tends to be obtained.

[0334] [Polymerization Catalyst G]

[0335] The polymerization catalyst G is not particularly limited, and examples thereof include any one or more of imidazole compounds and organophosphorus compounds. These catalysts may be used alone or in combination of two or more. Among them, imidazole compounds are preferred.

[0336] 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 Chemical Industry Co., Ltd.), and 2,4,5-triphenylimidazole ("TPIZ" manufactured by Tokyo Chemical Industry Co., Ltd.). Among these, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and / or 2,4,5-triphenylimidazole are preferred from the viewpoint of preventing the epoxy component from polymerizing independently.

[0337] The amount of polymerization catalyst G (preferably an imidazole compound) used is not particularly limited, but is, for example, 0.1 to 10 parts by mass relative to 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified silicone B, epoxy compound C, acid anhydride D, and compound F. From the perspective 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.

[0338] [Organic solvents]

[0339] There are no particular limitations on the organic solvent, and for example, polar solvents or non-polar solvents can be used. There are no particular limitations on the polar solvent, and examples include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; Cellosolve solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ester solvents such as ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, and methyl hydroxyisobutyrate; and amides such as dimethylacetamide and dimethylformamide. There are no particular limitations on the non-polar solvent, and examples include aromatic hydrocarbons such as toluene and xylene. These solvents can be used alone or in combination of two or more.

[0340] 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, acid anhydride D, and compound F.

[0341] 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.

[0342] After the reaction in this step is completed, the polymer E can be isolated and purified from the reaction mixture by a conventional method.

[0343] As described above, the curable composition of the second embodiment may further contain a compound F as needed in addition to the polymer E. By containing the compound F in addition to the polymer E, the curable composition of the second embodiment tends to have further improved heat resistance, chemical resistance, low thermal expansion properties, and copper foil peel strength.

[0344] 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% by mass, more preferably 10 to 55% by mass, and even more preferably 20 to 50% by mass, relative to 100% by mass of the total of polymer E and compound F. When the content is within this range, the curable composition tends to have better compatibility and exhibit a well-balanced low thermal expansion and copper foil peel strength.

[0345] 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.

[0346] The curable composition of this embodiment may further contain other resins without impairing 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.

[0347] Examples of the oxetane resin include oxetane, alkyloxetanes such as 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, and 3,3-dimethyloxetane, 3-methyl-3-methoxymethyloxetane, 3,3′-bis(trifluoromethyl)perfluorooxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl-type oxetanes, and “OXT-101” and “OXT-121” manufactured by Toagose Co., Ltd.

[0348] As used herein, a "benzoxazine compound" refers to a compound having two or more dihydrobenzoxazine rings in one molecule. Examples of benzoxazine compounds include "Bisphenol F-type benzoxazine BF-BXZ" and "Bisphenol S-type benzoxazine BS-BXZ" manufactured by KONISHI CHEMICAL INDCO., LTD.

[0349] 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.

[0350] [Inorganic fillers]

[0351] 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, etc.), metal nitrides (e.g., boron nitride, condensed boron nitride, silicon nitride, aluminum nitride, etc.), metal sulfates (e.g., barium sulfate, etc.), metal hydroxides (e.g., aluminum hydroxide, heat-treated aluminum hydroxide (e.g., aluminum hydroxide subjected to heat treatment to remove some of the crystalline water), boehmite, magnesium hydroxide, etc.), molybdenum compounds (e.g., molybdenum oxide, zinc molybdate, etc.), zinc compounds (e.g., zinc borate, zinc stannate, etc.), clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass, S-glass, M-glass G20, short glass fibers (including fine glass powders such as E-glass, T-glass, D-glass, S-glass, and Q-glass), hollow glass, spherical glass, etc. These inorganic fillers can be used alone or in combination of two or more. Among these, from the viewpoint of further improving low thermal expansion, the inorganic filler is preferably at least one selected from the group consisting of silica, metal hydroxides, and metal oxides, more preferably at least one selected from the group consisting of silica, boehmite, and alumina, and further preferably silica.

[0352] Examples of silicas include natural silica, fused silica, synthetic silica, AEROSIL, and hollow silica. These silicas may be used alone or in combination of two or more. Of these, fused silica is preferred for dispersibility, and two or more fused silicas having different particle sizes are more preferred for filling properties and fluidity.

[0353] 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.

[0354] [Silane coupling agent]

[0355] The curable composition of this embodiment may further contain a silane coupling agent. The inclusion of a silane coupling agent in the curable composition of this embodiment tends to further improve the dispersibility of the inorganic filler and the bonding strength between the components of the curable composition of this embodiment and the substrate described below.

[0356] The silane coupling agent is not particularly limited, and examples thereof include those generally used for surface treatment of inorganic materials, such as aminosilane compounds (e.g., γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxysilane compounds (e.g., γ-glycidoxypropyltrimethoxysilane, etc.), acrylic silane compounds (e.g., γ-acryloxypropyltrimethoxysilane, etc.), cationic silane compounds (e.g., N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride, etc.), styrylsilane compounds, and phenylsilane compounds. Silane coupling agents may be used alone or in combination of two or more. Among these, epoxysilane compounds are preferred. Examples of the epoxysilane-based compound include "KBM-403," "KBM-303," "KBM-402," and "KBE-403" manufactured by Shin-Etsu Chemical Co., Ltd.

[0357] 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.

[0358] [Wetting and dispersing agent]

[0359] The curable composition of this embodiment may further contain a wetting and dispersing agent. When the curable composition contains a wetting and dispersing agent, the dispersibility of the filler tends to be further improved.

[0360] The wetting dispersant may be any known dispersant (dispersion stabilizer) for dispersing fillers, and examples thereof include DISPER BYK-110, 111, 118, 180, 161, BYK-W996, W9010, and W903 manufactured by BYK JAPAN KK.

[0361] 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.

[0362] [Solvent]

[0363] The curable composition of this embodiment may further contain a solvent. The curable composition of this embodiment contains a solvent, which tends to reduce viscosity during preparation of the curable composition, further improve workability (handling properties), or further improve impregnation properties into a substrate.

[0364] 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.

[0365] The method for producing the curable composition of the present embodiment is not particularly limited, and examples thereof include a method of mixing the above-mentioned components into a solvent at once or in portions and stirring. In this case, in order to uniformly dissolve or disperse the components, known treatments such as stirring, mixing, and kneading can be used.

[0366] [use]

[0367] As described above, the curable composition of this embodiment has excellent compatibility and can exhibit even better low thermal expansion and copper foil peel strength. Therefore, the curable composition of this embodiment is suitable for use in metal foil-clad laminates and printed circuit boards. In other words, the cured product of this embodiment can be suitably used as a curing composition for printed circuit boards.

[0368] In particular, in the above-mentioned applications, the curable composition of the second embodiment preferably contains at least an epoxy compound C in addition to the polymer E (an epoxy compound C existing separately from the structural unit C in the polymer E).

[0369] In this case, the polymer E preferably has, as the unit derived from the epoxy compound C, a unit derived from the above-mentioned bifunctional epoxy compound, more preferably a unit derived from the above-mentioned biphenyl-type epoxy compound, more preferably a unit derived from the compound represented by the above formula (b2) (compound b2), and further preferably a unit derived from R a The number of compounds b2 is 0, and the alkyl group R a The number of units of compound b2 is 4 (commercially available, for example, trade name "YL-6121HA" manufactured by Mitsubishi Chemical Corporation).

[0370] In addition, as an epoxy compound C that exists separately from the structural unit C in the polymer E, it is preferred to contain the aforementioned naphthyl ether type epoxy resin (as a commercial product, for example, "HP-6000" produced by DIC Corporation, etc.) and / or naphthyl phenol formaldehyde varnish type epoxy resin (as a commercial product, for example, "HP-9540" produced by DIC Corporation, etc.).

[0371] [Prepreg]

[0372] The prepreg of this embodiment comprises a substrate and the curable composition of this embodiment impregnated or coated on the substrate. As described above, the prepreg can be obtained by a known method. Specifically, it can be obtained by impregnating or coating the substrate with the curable composition of this embodiment and then heating and drying it at 100-200°C to semi-cure (B-stage).

[0373] 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.

[0374] Relative to the total amount of prepreg, the content of the curable composition in the prepreg is preferably 30 to 90 volume %, more preferably 35 to 85 volume %, and further preferably 40 to 80 volume % based on the solid content of the prepreg. By making the content of the curable composition within the above range, there is a tendency to further improve formability. It should be noted that the content of the curable composition described herein is calculated to also include the cured product of the curable composition of the present embodiment. In addition, the solid content of the prepreg described herein refers to the component after excluding the solvent from the prepreg, such as the filling material contained in the solid content of the prepreg.

[0375] As base material, it is not particularly limited, and the known base material used in the material of various printed circuit boards can be enumerated. As the specific example of base material, inorganic base materials other than glass base material, glass (for example, inorganic base materials consisting of inorganic fibers other than glass such as quartz), organic base materials (for example, organic base materials consisting of organic fibers such as wholly aromatic polyamide, polyester, poly-p-phenylene benzoxazole, polyimide) etc. can be enumerated. These base materials can be used alone as one or in combination as two or more. Among them, for the viewpoint that heating dimensional stability is more excellent, preferably glass base material.

[0376] Examples of the fiber constituting the glass substrate include fibers such as E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. Among these, the fiber constituting the glass substrate is preferably one or more fibers selected from the group consisting of E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass, from the viewpoint of superior strength and low water absorption.

[0377] The form of the substrate is not particularly limited, and examples thereof include woven fabrics, non-woven fabrics, rovings, short glass fiber mats, and surfacing mats. The weaving method of the woven fabric is not particularly limited, and examples thereof include plain weaves, basket weaves, and twill weaves. These can be appropriately selected from among these known fabrics according to the intended use and performance. Furthermore, glass fabrics obtained by fiberizing these fabrics or surface-treating them with a silane coupling agent or the like are suitable. The thickness and mass of the substrate are not particularly limited, and those of approximately 0.01 to 0.1 mm are generally suitable.

[0378] [Resin sheet]

[0379] The resin sheet of this embodiment includes a support and a curable composition of this embodiment disposed on the surface of the support. The resin sheet of this embodiment may be formed, for example, by applying the curable composition of this embodiment to one or both sides of the support. The resin sheet of this embodiment may be produced, for example, by directly applying and drying the curable composition used in prepregs, etc., onto a support such as a metal foil or film.

[0380] The support is not particularly limited, and for example, known materials used in various printed circuit board materials can be used, preferably resin sheets or metal foils. Examples of resin sheets and metal foils include polyimide films, polyamide films, polyester films, polyethylene terephthalate (PET) films, polybutylene terephthalate (PBT) films, polypropylene (PP) films, polyethylene (PE) films, and other resin sheets, and metal foils such as aluminum foil, copper foil, and gold foil. Among these, the support is preferably electrolytic copper foil or PET film.

[0381] 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 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.

[0382] [Metal foil-clad laminate]

[0383] 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.

[0384] The metal foil (conductor layer) may be any metal foil used in various printed circuit board materials, and examples thereof include copper and aluminum foils. Examples of copper foil include rolled copper foil and electrolytic copper foil. The thickness of the conductor layer is, for example, 1 to 70 μm, preferably 1.5 to 35 μm.

[0385] The forming method and forming conditions of the metal foil-clad laminate are not particularly limited, and the methods and conditions for forming laminates and multilayer boards for general printed circuit boards can be used. For example, a multi-stage press, a multi-stage vacuum press, a continuous forming machine, an autoclave forming machine, etc. can be used when forming the laminate (the above-mentioned laminate) or the metal foil-clad laminate. In addition, in the forming (laminate forming) of the laminate (the above-mentioned laminate) or the metal foil-clad laminate, the temperature is generally 100 to 300°C and the pressure is 2 to 100 kgf / cm2. 2 , the heating time is in the range of 0.05 to 5 hours. Furthermore, post-curing can be performed at a temperature of 150 to 300°C as needed. In particular, when a multi-stage press is used, the temperature is preferably 200 to 250°C and the pressure is preferably 10 to 40 kgf / cm 2 , heating time 80 minutes to 130 minutes, more preferably temperature 215 ℃ to 235 ℃, pressure 25 to 35 kgf / cm 2 , heating time 90 minutes to 120 minutes. In addition, a multilayer board can also be produced by combining the above-mentioned prepreg and a separately produced inner layer wiring board and laminating them.

[0386] [Printed Circuit Board]

[0387] The printed wiring board of this embodiment comprises an insulating layer formed from one or more materials 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. For example, the printed wiring board of this embodiment can be formed by etching the metal foil of the metal-clad laminate of this embodiment into a predetermined wiring pattern to form the conductive layer.

[0388] Specifically, the printed circuit board of the present embodiment can be manufactured by the following method, for example. First, prepare the metal foil clad laminate of the present embodiment. Etch the metal foil of the metal foil clad laminate into a specified wiring pattern to produce an inner substrate with a conductor layer (inner circuit). Then, on the surface of the conductor layer (built-in circuit) of the inner substrate, a specified number of insulating layers and metal foil for the outer layer circuit are sequentially stacked, heated and pressed to form an integral body (laminate forming), thereby obtaining a laminate. It should be noted that the method of laminate forming and its forming conditions are the same as the method of laminate forming and its forming conditions in the above-mentioned laminate and metal foil clad laminate. Then, a through hole (through hole) and a via hole (via hole) are formed on the laminate, and a plated metal film for conducting the metal foil for the conductor layer (built-in circuit) and the outer layer circuit is formed on the wall surface of the hole thus formed. Then, the metal foil for the outer layer circuit is etched into a specified wiring pattern to produce an outer substrate with a conductor layer (outer layer circuit). In this way, a printed circuit board is manufactured.

[0389] Furthermore, when a metal foil-clad laminate is not used, a conductor layer forming a circuit can be formed on the insulating layer to produce a printed wiring board. In this case, the conductor layer can also be formed by chemical plating.

[0390] Example

[0391] Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

[0392] (Example 1)

[0393] In a three-necked flask equipped with a thermometer and a Dimrod condenser, 5.0 parts by mass of diallylbisphenol A (DABPA, Daiwa Kasei Industry Co., Ltd.), 5.5 parts by mass of biscresol fluorene (BCF, Osaka Gas Chemicals Co., Ltd.), 4.1 parts by mass of epoxy-modified silicone compound A (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent 200 g / eq.), 8.4 parts by mass of epoxy-modified silicone compound B (KF-105, Shin-Etsu Chemical Co., Ltd., functional group equivalent 500 g / eq.), 5.5 parts by mass of biphenyl epoxy compound A (YL-6121HA, Mitsubishi Chemical Corporation), and propylene glycol monomethyl ether acetate (DOWANOL PMA, Dow Chemical) as a solvent were added. Japan) 30.0 parts by mass, and heated with stirring in an oil bath to 120°C. After confirming that the raw materials have been dissolved in the solvent, 0.3 parts by mass of imidazole catalyst A (TBZ, Shikoku Chemicals Co., Ltd.) is added and the temperature is raised to 140°C, followed by stirring for 5 hours and cooling to obtain a phenoxy polymer solution (solid content 50% by mass) (polymer formation process). It should be noted that diallyl bisphenol A is equivalent to "alkenylphenol A", epoxy-modified silicone compound A and epoxy-modified silicone compound B are equivalent to "epoxy-modified silicone B", and biphenyl-type epoxy compound A is equivalent to "epoxy compound C". The phenoxy polymer solution contains a polymer, and the polymer contains a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, and a structural unit derived from epoxy compound C.

[0394] After heating the phenoxy polymer solution to 100°C in an oil bath, 1.5 parts by mass of succinic anhydride as acid anhydride D was added, stirred for 2 hours, and cooled to obtain a modified phenoxy polymer solution (solids content 50% by mass) (polymer modification step). The modified phenoxy polymer solution contains a polymer comprising a structural unit derived from alkenylphenol A, a structural unit derived from epoxy-modified silicone B, a structural unit derived from epoxy compound C, and a structural unit derived from acid anhydride D. The polymer modification step can also be carried out continuously with the polymer production step.

[0395] [Method for measuring weight average molecular weight Mw]

[0396] The weight average molecular weight (Mw) of the modified phenoxy polymer obtained in the above manner was measured by the following method. 20 μL of a 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 determined by GPC using standard polystyrene as a standard substance.

[0397] The weight average molecular weight Mw of the modified phenoxy polymer measured in the above manner was 12,000.

[0398] To the modified phenoxy polymer solution were mixed 25 parts by mass of a naphthol aralkyl type phenol compound (SN-495V, NIPPONSTEEL Chemical & Material Co., Ltd.), 9 parts by mass of a novolac type maleimide compound (BMI-2300, Daiwa Kasei Industry Co., Ltd.), 9 parts by mass of a phenylene ether type maleimide compound (BMI-80, Daiwa Kasei Industry Co., Ltd.), 27 parts by mass of a naphthol ether type epoxy compound (HP-6000, DIC Corporation), 200 parts by mass of spherical silica (SC-2050MB, ADMATECHS COMPANY LIMITED), 1 part by mass of a wetting and dispersing agent (DISPERBYK-161, BYK Japan), and 1 part by mass of a silane coupling agent (KBM-403, Shin-Etsu Chemical Co., Ltd.). Co., Ltd.) to obtain a varnish (varnish production step). The varnish was dip-coated onto S-glass woven fabric (thickness 100 μm) and dried by heating at 150°C for 3 minutes to obtain a prepreg having a curable composition solid content (including filler) of 58.2% by volume (prepreg production step).

[0399] (Example 2)

[0400] A prepreg having a curable 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 formation step was changed from 5.0 parts by mass to 4.7 parts by mass, the amount of biscresol fluorene added in the polymer formation step was changed from 5.5 parts by mass to 5.2 parts by mass, the amount of epoxy-modified silicone A added in the polymer formation step was changed from 4.1 parts by mass to 3.8 parts by mass, the amount of epoxy-modified silicone B added in the polymer formation step was changed from 8.4 parts by mass to 8.1 parts by mass, and the amount of biphenyl-type epoxy compound A added in the polymer modification step was changed from 1.5 parts by mass to 3.0 parts by mass.

[0401] 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 epoxy compound C, and a structural unit derived from acid anhydride D.

[0402] The weight average molecular weight Mw of the modified phenoxy polymer in Example 2 measured by the aforementioned method was 12,000.

[0403] (Example 3)

[0404] A prepreg having a curable composition solid content (including filler) of 58.2 vol % was obtained in the same manner as in Example 2 except that the acid anhydride D was changed from 3.0 parts by mass of succinic anhydride to 3.0 parts by mass of phthalic anhydride.

[0405] 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 epoxy compound C, and a structural unit derived from acid anhydride D.

[0406] The weight average molecular weight Mw of the modified phenoxy polymer in Example 3 measured by the aforementioned method was 12,000.

[0407] (Comparative Example 1)

[0408] In the polymer formation step, the amount of diallylbisphenol A added was changed from 5.0 parts by mass to 5.3 parts by mass, the amount of biscresol fluorene added was changed from 5.5 parts by mass to 5.8 parts by mass, the amount of epoxy-modified silicone A added was changed from 4.1 parts by mass to 4.4 parts by mass, the amount of epoxy-modified silicone B added was changed from 8.4 parts by mass to 8.7 parts by mass, the amount of biphenyl-type epoxy compound A added was changed from 5.5 parts by mass to 5.8 parts by mass, and the amount of imidazole catalyst A added was changed from 0.30 parts by mass to 1.2 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.

[0409] The weight average molecular weight Mw of the phenoxy polymer in Comparative Example 1 measured by the aforementioned method was 12,000.

[0410] Two prepregs obtained in Examples 1 to 3 and Comparative Example 1 were stacked, and electrolytic copper foils (3EC-M2S-VLP, manufactured by Mitsui Mining & Smelting Co., Ltd.) with a thickness of 12 μm were placed above and below them. 2 Lamination molding was performed at a temperature of 220°C for 120 minutes to obtain a copper-clad laminate having an insulating layer with a thickness of 0.2 mm as a metal-clad laminate. The properties of the obtained copper-clad laminate were evaluated by the following methods. The evaluation results are shown in Table 1.

[0411] [Copper foil peel strength]

[0412] Using the copper-clad laminate (10 mm×150 mm×0.2 mm) obtained by the above method, the copper foil peel strength (unit: kN / m) was measured in accordance with JIS C6481.

[0413] [Coefficient of linear thermal expansion (CTE)]

[0414] The linear thermal expansion coefficient of the glass cloth in the insulating layer of the laminate was measured. Specifically, the copper foil on both sides of the copper-clad laminate (10 mm × 6 mm × 0.2 mm) obtained by the above method was removed by etching. The laminate was then heated in a thermostat at 220°C for 2 hours to remove stress caused by forming. Subsequently, the temperature was increased from 40°C to 320°C at a rate of 10°C per minute using a thermal expansion coefficient measuring device (horizontal dilatometer manufactured by LINSEIS). The linear thermal expansion coefficient (CTE) was measured (unit: ppm / °C) from 60°C to 260°C.

[0415] [Table 1]

[0416]

[0417] As shown in Table 1 above, the copper-clad laminates (Examples 1 to 3) using the curable composition of the present embodiment have excellent low thermal expansion and copper foil peeling strength.

[0418] This application is based on Japanese patent application (Japanese Patent Application No. 2021-128743) filed with the Japan Patent Office on August 5, 2021, the contents of which are incorporated herein by reference.

Claims

1. A curable composition comprising an alkenylphenol A, an epoxy-modified silicone B, an epoxy compound C other than the epoxy-modified silicone B, and an acid anhydride D, wherein the acid anhydride D is phthalic anhydride or succinic anhydride. The content of the acid anhydride D is 0.8 to 15% by mass relative to 100% by mass of the resin solid content. The resin solid content is the content of the curable composition excluding the solvent and the filler.

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 contains diallyl bisphenol and / or dipropylene 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 contains epoxy-modified silicone represented by the following formula (1): 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. The curable composition according to claim 1 or 2, wherein The epoxy compound C contains a compound represented by the following formula (b2), Where R a Each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.

7. 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.

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, and a structural unit derived from an acid anhydride D, wherein the acid anhydride D is phthalic anhydride or succinic anhydride. The content of the acid anhydride D is 0.8 to 15% by mass relative to 100% by mass of the resin solid content. The resin solid content is the content of the curable composition excluding the solvent and the filler.

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 acid anhydride 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 contains diallyl bisphenol and / or dipropylene 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 contains epoxy-modified silicone represented by the following formula (1): Where R 1 Each independently represents a single bond, an alkylene group, an arylene group or an aralkylene group, R 2 Each independently represents an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n represents an integer of 0 to 100.

17. The curable composition according to claim 8 or 9, wherein The epoxy compound C contains a compound represented by the following formula (b2), Where R a Each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom.

18. The curable composition according to claim 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). 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, 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. 19 . The curable composition according to claim 1 , further comprising at least one compound F selected from the group consisting of maleimide compounds, cyanate ester compounds, phenol compounds A′ other than alkenylphenol A, 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 the formula, 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 the formula, R6 each independently represents a hydrogen atom or a methyl group, n2 represents an integer greater than 1, 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 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 absent, a benzene ring can 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 19, wherein The phenol compound A' comprises a compound represented by the following formula (8): In the formula, 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 a curable composition for a printed wiring 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 polymerizing alkenylphenol A, epoxy-modified silicone B, and epoxy compound C to obtain a prepolymer; and A step of reacting the acid anhydride D with the prepolymer.

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