TW202313755A - Curable composition, prepreg, resin sheet, metal foil clad laminate, and printed wiring board - Google Patents

Abstract

A curable composition, containing an alkenylphenol A, an epoxy modified silicone B, an epoxy compound C other than the epoxy modified silicone B, and an acid anhydride D.

Description

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

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

In recent years, along with the high-performance and miniaturization of semiconductor packages widely used in electronic equipment, communication equipment, and personal computers, the high-integration and high-density mounting of various parts for semiconductor packaging has also been accelerated in recent years. Along with this, many characteristics required for printed wiring boards for semiconductor packaging have become more and more stringent. The characteristics required for such a printed wiring board include, for example, low thermal expansion, chemical resistance, peel strength, and the like.

Patent Document 1 discloses a thermosetting resin composition containing a specific maleimide compound, a polysiloxane compound having an epoxy group in the molecular structure, and a compound having a phenolic hydroxyl group, which is excellent in heat resistance and low thermal expansion , can be ideally used in metal foil-clad laminates and multilayer printed wiring boards.

Patent Document 2 discloses an addition polymer of polymaleimide, dipoxypropyl polysiloxane represented by the following formula (I), and diallyl bisphenols represented by the following formula (II), and A method for producing a resin for encapsulating semiconductors by reacting an allylated phenolic resin represented by the following formula (III) in a predetermined ratio and conditions. According to this document, the resin for semiconductor sealing obtained by the above-mentioned production method has excellent compatibility between polymaleimide and the above-mentioned addition polymer, and furthermore, the cured product characteristics of the composition using the resin for semiconductor sealing (such as high glass transition temperature, moisture resistance, and strength during heating) are excellent, and they have high reliability as a resin composition for sealing semiconductors. This document reveals that in the following formula (III), component b reacts with maleimide groups during the resin formation reaction with polymaleimide, which improves polymaleimide and polysiloxane important component of compatibility.

[chemical 1]

In the formula, ^R1 represents an alkylene or a phenylene group, ^R2 each independently represents an alkyl group or a phenylene group, and n represents an integer of 1 to 100.

[Chem 2]

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

[Chem 3]

In the above formula, a, b, and c respectively represent the percentage of each composition, 0<a, b, c<100 and a+b+c=100. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Unexamined Patent Publication No. 2012-149154 [Patent Document 2] Japanese Patent Application Laid-Open No. 4-4213

[Problem to be Solved by the Invention]

As in Patent Document 1, a resin composition containing a thermosetting resin such as a polysiloxane compound having an epoxy group in its molecular structure and a maleimide compound is excellent in low thermal expansion. However, the present inventors have found that in the above resin composition, there is a problem in moldability due to insufficient compatibility between the above polysiloxane compound and the thermosetting resin. In addition, the inventors of the present invention have found that the above-mentioned resin composition has insufficient metal foil peel strength (for example, copper foil peel strength) when used as a metal foil-clad laminate.

On the other hand, the resin composition described in Patent Document 2 is used for encapsulation of semiconductors, and has not considered low thermal expansion and copper foil peel strength required as characteristics of printed wiring boards.

The present invention is made in view of the above-mentioned problems, and an object thereof 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. [Means to solve the problem]

The inventors of the present invention have made intensive studies repeatedly in order to solve the above-mentioned problems. As a result, it was found that if it is a curable composition containing alkenylphenol, epoxy-modified polysiloxane, epoxy compound other than epoxy-modified polysiloxane, and acid anhydride, or contains these components as The curable composition of the polymer constituting the units can solve the above-mentioned problems, leading to the completion of the present invention.

式中，R ¹各自獨立地表示單鍵、伸烷基、伸芳基或伸芳烷基，R ²各自獨立地表示碳數1~10之烷基或苯基，n表示0~100之整數。 [6] 如上述[1]~[5]中任一項記載之硬化性組成物，其中，前述環氧化合物C包含下式(b2)表示之化合物。 [化5]

式中，R ^a各自獨立地表示碳數1~10之烷基或氫原子。 [7] 如上述[1]~[6]中任一項記載之硬化性組成物，其中，前述環氧化合物C的含量，相對於前述環氧改性聚矽氧B及前述環氧化合物C之合計量100質量%，為20~50質量%。 [8] 如上述[1]~[7]中任一項記載之硬化性組成物，其中，前述酸酐D為選自由苯二甲酸酐、琥珀酸酐、馬來酸酐、納迪克酸酐(nadic anhydride)及順4-環己烯-1,2-二甲酸酐構成之群組中之1種以上。 [9] 一種硬化性組成物，含有： 聚合物E，包含：來自烯基酚A之構成單元、來自環氧改性聚矽氧B之構成單元、來自環氧化合物C之構成單元、及來自酸酐D之構成單元。 [10] 如上述[9]所記載之硬化性組成物，其中，前述聚合物E的重量平均分子量為3.0×10 ³~5.0×10 ⁴。 [11] 如上述[9]或[10]所記載之硬化性組成物，其中，前述聚合物E中之前述來自環氧改性聚矽氧B之構成單元的含量，相對於前述聚合物E之總質量，為20~60質量%。 [12] 如上述[9]~[11]中任一項記載之硬化性組成物，其中，前述聚合物E的烯基當量為300~1500g/mol。 [13] 如上述[9]~[12]中任一項記載之硬化性組成物，其中，前述聚合物E中之前述來自酸酐D之構成單元的含量，相對於前述聚合物E之總質量，為3~20質量%。 [14] 如上述[9]~[13]中任一項記載之硬化性組成物，其中，前述聚合物E的含量，相對於樹脂固體成分100質量%，為5~50質量%。 [15] 如上述[9]~[14]中任一項記載之硬化性組成物，其中，前述烯基酚A包含二烯丙基雙酚及/或二丙烯基雙酚。 [16] 如上述[9]~[15]中任一項記載之硬化性組成物，其中，前述環氧改性聚矽氧B包含具有140~250g/mol之環氧當量的環氧改性聚矽氧。 [17] 如上述[9]~[16]中任一項記載之硬化性組成物，其中，前述環氧改性聚矽氧B包含下式(1)表示之環氧改性聚矽氧。 [化6]

式中，R ¹各自獨立地表示單鍵、伸烷基、伸芳基或伸芳烷基，R ²各自獨立地表示碳數1~10之烷基或苯基，n表示0~100之整數。 [18] 如上述[9]~[17]中任一項記載之硬化性組成物，其中，前述環氧化合物C包含下式(b2)表示之化合物。 [化7]

式中，R ^a各自獨立地表示碳數1~10之烷基或氫原子。 [19] 如上述[9]~[18]中任一項記載之硬化性組成物，其中，前述酸酐D為選自由苯二甲酸酐、琥珀酸酐、馬來酸酐、納迪克酸酐及順4-環己烯-1,2-二甲酸酐構成之群組中之1種以上。 [20] 如上述[9]~[19]中任一項記載之硬化性組成物，更含有環氧化合物C，前述環氧化合物C包含下式(3-3)表示之化合物或下式(3-4)表示之化合物。 [化8]

式中，R ₁₃各自獨立地表示氫原子、碳數1~3之烷基或碳數2~3之烯基。 [化9]

式中，R ₁₄各自獨立地表示氫原子、碳數1~3之烷基或碳數2~3之烯基。 [21] 如上述[1]~[20]中任一項記載之硬化性組成物，更含有選自由馬來醯亞胺化合物、氰酸酯化合物、烯基酚A以外的酚化合物A’及經烯基取代之納迪克醯亞胺(nadiimide)化合物構成之群組中之至少1種之化合物F。 [22] 如上述[21]所記載之硬化性組成物，其中，前述馬來醯亞胺化合物包含選自由雙(4-馬來醯亞胺基苯基)甲烷、2,2-雙(4-(4-馬來醯亞胺基苯氧基)苯基)丙烷、雙(3-乙基-5-甲基-4-馬來醯亞胺基苯基)甲烷、下式(3)表示之馬來醯亞胺化合物及下式(3’)表示之馬來醯亞胺化合物構成之群組中之至少1種。 [化10]

式中，R ₅各自獨立地表示氫原子或甲基，n ₁表示1以上之整數。 [化11]

式(3’)中，R ¹³各自獨立地表示氫原子、碳數1~5之烷基、或苯基，n ⁴表示1以上且10以下之整數。 [23] 如上述[21]或[22]所記載之硬化性組成物，其中，前述氰酸酯化合物包含下式(4)表示之化合物及/或下式(4)表示之化合物之外的下式(5)表示之化合物。 [化12]

式中，R ₆各自獨立地表示氫原子或甲基，n ₂表示1以上之整數。 [化13]

式中，R _ya各自獨立地表示碳數2~8之烯基或氫原子，R _yb各自獨立地表示碳數1~10之烷基或氫原子，R _yc各自獨立地表示碳數4~12之芳香環，R _yc也可和苯環形成縮合結構，R _yc可存在也可不存在，A ^1a各自獨立地表示碳數1~6之伸烷基、碳數7~16之伸芳烷基、碳數6~10之伸芳基、亞茀基、磺醯基、氧原子、硫原子或單鍵，R _yc不存在時，1個苯環中也可具有2個以上之R _ya及/或R _yb之基，n表示1~20之整數。 [24] 如上述[21]~[23]中任一項記載之硬化性組成物，其中，前述酚化合物A’包含下式(8)表示之化合物。 [化14]

式中，R ₇各自獨立地表示氫原子或甲基，n ₃表示1以上之整數。 [25] 如上述[1]~[24]中任一項記載之硬化性組成物，更含有無機填充材，前述無機填充材的含量，相對於樹脂固體成分100質量份，為50~1000質量份。 [26] 如上述[25]所記載之硬化性組成物，其中，前述無機填充材包含選自由二氧化矽類、軟水鋁石(boehmite)及氧化鋁構成之群組中之1種以上。 [27] 如上述[1]~[26]中任一項記載之硬化性組成物，其係用於印刷配線板。 [28] 一種預浸體，含有： 基材，及 含浸或塗佈於前述基材之上述[1]~[27]中任一項記載之硬化性組成物。 [29] 一種樹脂片，含有： 支持體，及 配置於前述支持體的表面之上述[1]~[27]中任一項記載之硬化性組成物。 [30] 一種覆金屬箔疊層板，含有： 使用選自由上述[28]所記載之預浸體及上述[29]所記載之樹脂片構成之群組中之1種以上而形成的疊層體，及 配置於前述疊層體的單面或雙面之金屬箔。 [31] 一種印刷配線板，具有： 以選自由上述[28]所記載之預浸體及上述[29]所記載之樹脂片構成之群組中之1種以上來形成的絕緣層，及 形成於前述絕緣層的表面之導體層。 [32] 一種硬化性組成物之製造方法，係如上述[1]~[27]中任一項所記載之硬化性組成物之製造方法，包含下列步驟： 獲得將烯基酚A、環氧改性聚矽氧B、環氧化合物C進行聚合而得的預聚物，及 使酸酐D與前述預聚物進行反應。 [發明之效果] That is, the present invention is as follows. [1] A curable composition comprising: alkenylphenol A, epoxy-modified polysiloxane B, epoxy compound C other than the aforementioned epoxy-modified polysiloxane B, and acid anhydride D. [2] The curable composition as described in [1] above, wherein the alkenylphenol A has an average number of phenolic groups per molecule of 1 to less than 3, and the epoxy-modified polysiloxane B has an average number of phenol groups per molecule. The average number of epoxy groups per molecule is 1 to less than 3, and the average number of epoxy groups per molecule of the aforementioned epoxy compound C is 1 to less than 3. [3] The curable composition according to the above [1] or [2], wherein the alkenylphenol A includes diallyl bisphenol and/or diallyl bisphenol. [4] The curable composition according to any one of the above [1] to [3], wherein the epoxy-modified polysiloxane B contains an epoxy-modified polysiloxane having an epoxy equivalent of 140 to 250 g/mol. Polysiloxane. [5] The curable composition according to any one of the above [1] to [4], wherein the epoxy-modified polysiloxane B includes an epoxy-modified polysiloxane represented by the following formula (1). [chemical 4]

In the formula, R ¹ each independently represent a single bond, alkylene, aryl or aralkylene, R ² each independently represent an alkyl or phenyl group with 1 to 10 carbons, and n represents an integer of 0 to 100 . [6] The curable composition according to any one of the above [1] to [5], wherein the epoxy compound C includes a compound represented by the following formula (b2). [chemical 5]

In the formula, R ^a each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom. [7] The curable composition according to any one of the above [1] to [6], wherein the content of the epoxy compound C is equal to that of the epoxy-modified polysiloxane B and the epoxy compound C The total amount of 100% by mass is 20 to 50% by mass. [8] The curable composition according to any one of the above [1] to [7], wherein the acid anhydride D is selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, and nadic anhydride. and one or more species from the group consisting of cis-4-cyclohexene-1,2-dicarboxylic anhydride. [9] A curable composition comprising: a polymer E comprising: a constituent unit derived from alkenylphenol A, a constituent unit derived from epoxy-modified polysiloxane B, a constituent unit derived from epoxy compound C, and a constituent unit derived from The constituent unit of acid anhydride D. [10] The curable composition according to the above [9], wherein the polymer E has a weight average molecular weight of 3.0×10 ³ to 5.0×10 ⁴ . [11] The curable composition according to the above [9] or [10], wherein the content of the constituent unit derived from the epoxy-modified polysiloxane B in the polymer E is greater than that of the polymer E The total mass is 20~60% by mass. [12] 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] The curable composition according to any one of the above [9] to [12], wherein the content of the structural unit derived from the acid anhydride D in the polymer E is relative to the total mass of the polymer E , is 3~20% by mass. [14] The curable composition according to any one of [9] to [13] above, wherein the content of the polymer E is 5 to 50% by mass relative to 100% by mass of the resin solid content. [15] The curable composition according to any one of [9] to [14] above, wherein the alkenylphenol A includes diallyl bisphenol and/or diallyl bisphenol. [16] The curable composition according to any one of the above [9] to [15], wherein the epoxy-modified polysiloxane B contains an epoxy-modified polysiloxane having an epoxy equivalent of 140 to 250 g/mol. Polysiloxane. [17] The curable composition according to any one of [9] to [16] above, wherein the epoxy-modified polysiloxane B includes an epoxy-modified polysiloxane represented by the following formula (1). [chemical 6]

In the formula, R ¹ each independently represent a single bond, alkylene, aryl or aralkylene, R ² each independently represent an alkyl or phenyl group with 1 to 10 carbons, and n represents an integer of 0 to 100 . [18] The curable composition according to any one of [9] to [17] above, wherein the epoxy compound C includes a compound represented by the following formula (b2). [chemical 7]

In the formula, R ^a each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom. [19] The curable composition according to any one of the above [9] to [18], wherein the acid anhydride D is selected from the group consisting of phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride, and cis-4- One or more species from the group consisting of cyclohexene-1,2-dicarboxylic anhydride. [20] The curable composition described in any one of the above [9] to [19] further contains an epoxy compound C, and the aforementioned epoxy compound C includes a compound represented by the following formula (3-3) or the following formula ( 3-4) Compounds represented. [chemical 8]

In the formula, R ₁₃ each independently represent a hydrogen atom, an alkyl group having 1 to 3 carbons, or an alkenyl group having 2 to 3 carbons. [chemical 9]

In the formula, R ₁₄ each independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons, or an alkenyl group with 2 to 3 carbons. [21] The curable composition described in any one of [1] to [20] above, further comprising a phenolic compound A' other than a maleimide compound, a cyanate compound, and alkenylphenol A; and At least one compound F of the group consisting of alkenyl-substituted nadiimide compounds. [22] The curable composition as described in [21] above, wherein the maleimide compound is selected from the group consisting of bis(4-maleimidophenyl)methane, 2,2-bis(4 -(4-maleimidophenoxy)phenyl)propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, represented by the following formula (3) At least one of the group consisting of a maleimide compound and a maleimide compound represented by the following formula (3'). [chemical 10]

In the formula, R ₅ each independently represent a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more. [chemical 11]

In formula (3′), R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbons, or a phenyl group, and n ⁴ represents an integer of 1 to 10. [23] The curable composition according to the above [21] or [22], wherein the cyanate compound includes a compound represented by the following formula (4) and/or a compound other than the compound represented by the following formula (4) A compound represented by the following formula (5). [chemical 12]

In the formula, R ₆ each independently represent a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more. [chemical 13]

In the formula, R _ya each independently represent an alkenyl group with 2 to 8 carbons or a hydrogen atom, R _yb each independently represent an alkyl group with 1 to 10 carbons or a hydrogen atom, and R _yc each independently represent an alkyl group with 4 to 12 carbons The aromatic ring, R _yc can also form a condensation structure with the benzene ring, R _yc may or may not exist, and A ^1a each independently represent an alkylene group with 1 to 6 carbons, an aralkylene group with 7 to 16 carbons, Arylylene group, fenylene group, sulfonyl group, oxygen atom, sulfur atom or single bond with 6~10 carbons, when R _yc does not exist, one benzene ring may have two or more R _ya and/or The base of R _yb , n represents an integer from 1 to 20. [24] The curable composition according to any one of the above [21] to [23], wherein the phenolic compound A' includes a compound represented by the following formula (8). [chemical 14]

In the formula, R ₇ each independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 or more. [25] The curable composition described in any one of [1] to [24] above, further comprising an inorganic filler, the content of the inorganic filler being 50 to 1000 parts by mass relative to 100 parts by mass of the resin solid content share. [26] The curable composition as described in [25] above, wherein the inorganic filler contains at least one selected from the group consisting of silica, boehmite, and alumina. [27] The curable composition according to any one of [1] to [26] above, which is used for a printed wiring board. [28] A prepreg comprising: a substrate, and the curable composition described in any one of the above [1] to [27] impregnated or coated on the substrate. [29] A resin sheet comprising: a support, and the curable composition according to any one of the above [1] to [27] disposed on the surface of the support. [30] A metal foil-clad laminate comprising: a laminate formed using one or more members selected from the group consisting of the prepreg described in [28] above and the resin sheet described in [29] above body, and the metal foil arranged on one or both sides of the above-mentioned laminated body. [31] A printed wiring board comprising: an insulating layer formed of at least one type selected from the group consisting of the prepreg described in [28] above and the resin sheet described in [29] above, and A conductive layer on the surface of the aforementioned insulating layer. [32] A method for producing a curable composition, which is the method for producing a curable composition as described in any one of [1] to [27] above, comprising the following steps: obtaining alkenylphenol A, epoxy A prepolymer obtained by polymerizing the modified polysiloxane B and the epoxy compound C, and reacting the anhydride D with the prepolymer. [Effect of Invention]

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.

Hereinafter, the form for implementing 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 changes can be made without departing from the gist thereof.

The so-called "resin solid content" in this specification refers to the curable composition of this embodiment after excluding the solvent and the filler, unless otherwise specified, and 100 parts by mass of the resin solid content refers to the curable composition excluding the solvent and the filler. The total of the components after the filler is 100 parts by mass. In addition, 100% by mass of the resin solid content means that the total of components excluding the solvent and the filler in the curable composition is 100% by mass.

In addition, in the curable composition of the first embodiment described later, "excellent compatibility" refers to a mixture containing alkenylphenol A, epoxy-modified polysiloxane B, epoxy compound C, and acid anhydride D ( For example, in the state of varnish), no liquid phase separation will occur. In addition, in the curable composition of the second embodiment described later, "excellent compatibility" means that liquid phase separation does not occur in the state of a mixture (such as varnish) containing the polymer E and other components. The curable composition of this embodiment is excellent in compatibility, so liquid phase separation during molding can be suppressed, a molded article with excellent appearance can be obtained, and the physical properties of the obtained molded article are also excellent in isotropy. tendency. In addition, in this specification, when referring to "the curable composition of the present embodiment", it is defined to include "the curable composition of the first embodiment" and "the curable composition of the second embodiment" unless otherwise specified. "both sides.

[First Embodiment: Curable Composition] The curable composition of the first embodiment contains alkenylphenol A, epoxy-modified silicone B, and epoxy compound C other than epoxy-modified silicone B (hereinafter also referred to as "epoxy compound C") , and anhydride D. Curable compositions containing these components tend to have better compatibility with thermosetting resins that have insufficient compatibility with epoxy-modified silicone B (hereinafter also referred to as "thermosetting resins") . Therefore, the curable composition of the first embodiment can exhibit better compatibility, and has excellent low thermal expansion and copper foil peel strength. In addition, in the curable composition, if these components are partially reacted (polymerized) and used, more excellent compatibility can be exhibited, and more excellent low thermal expansion and copper foil peel strength can be exhibited (second embodiment sclerosing composition).

[Alkenylphenol A] The alkenylphenol A is not particularly limited as long as it is a compound having a structure in which one or more alkenyl groups are directly bonded to a phenolic aromatic ring. The curable composition of this embodiment can exhibit excellent compatibility by containing alkenylphenol A.

The alkenyl group is not particularly limited, and examples thereof include alkenyl groups having 2 to 30 carbon atoms such as vinyl, allyl, propenyl, butenyl, and hexenyl. Among them, the alkenyl group is preferably an allyl group and/or a propenyl group, and is more preferably an allyl group, 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 not particularly limited, and is, for example, 1-4. 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 1-2, more preferably 1. Also, the position where the alkenyl group is bonded to the phenolic aromatic ring is not particularly limited, and the ortho position (2, 6 positions) is preferable.

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

The phenolic aromatic ring may have substituents other than alkenyl. Examples of such substituents include straight-chain alkyl groups with 1 to 10 carbons, branched alkyl groups with 3 to 10 carbons, cyclic alkyl groups with 3 to 10 carbons, and straight-chain alkyl groups with 1 to 10 carbons. Shaped alkoxy, branched alkoxy with 3 to 10 carbons, cyclic alkoxy with 3 to 10 carbons, and halogen atoms. When the phenolic aromatic ring has a substituent other than an alkenyl group, the number of the substituents directly bonded to one phenolic aromatic ring is not particularly limited, and is, for example, 1-2. Also, the position where the substituent is bonded to the phenolic aromatic ring is not particularly limited.

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

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

[chemical 15]

In the formula, R _xa each independently represents an alkenyl group having 2 to 8 carbons, R _xb independently represents an alkyl group or a hydrogen atom having 1 to 10 carbons, and R _xc independently represents an aromatic ring having 4 to 12 carbons , R _xc can also form a condensation structure with the benzene ring, R _xc may or may not exist, A represents an alkylene group with 1 to 6 carbons, an aralkylene group with 7 to 16 carbons, and an extended alkyl group with 6 to 10 carbons Aryl group, borylene group, sulfonyl group, oxygen atom, sulfur atom or direct bond (single bond), when R _xc does not exist, one benzene ring may have two or more of R _xa and/or R _xb base.

[chemical 16]

In the formula, _Rxd each independently represents an alkenyl group with 2 to 8 carbons, _Rxe independently represents an alkyl group with 1 to 10 carbons or a hydrogen atom, _Rxf represents an aromatic ring with 4 to 12 carbons, _Rxf It can also form a condensed structure with a benzene ring. _Rxf may or may not exist. When _Rxf does not exist, one benzene ring may have two or more _Rxd and/or _Rxe groups.

In formula (1A) and formula (1B), the alkenyl group with 2 to 8 carbon numbers represented by _Rxa and _Rxd is not particularly limited, for example: vinyl, allyl, propenyl, butenyl, hexyl alkenyl etc.

In formula (1A) and formula (1B), when the groups represented by R _xc and R _xf form a condensed structure with a benzene ring, for example, a compound containing a naphthol ring as a phenolic aromatic ring is mentioned. Moreover, in formula (1A) and formula (1B), when the group represented by R _xc and R _xf does not exist, for example, the compound which contains a phenol ring as a phenolic aromatic ring is mentioned.

In formula (1A) and formula (1B), the alkyl group of carbon number 1～10 represented by _Rxb and _Rxe is not particularly limited, for example: methyl, ethyl, propyl, butyl, pentyl, Straight-chain alkyl groups such as hexyl; branched alkyl groups such as isopropyl, isobutyl, and tertiary butyl.

In formula (1A), the alkylene group having 1 to 6 carbon atoms represented by A is not particularly limited, and examples thereof include methylene, ethylidene, trimethylene, and propylidene. The aralkylene group with 7 to 16 carbons represented by A is not particularly limited, and examples include the formula: -CH ₂ -Ar-CH ₂ -, -CH ₂ -CH ₂ -Ar-CH ₂ -CH ₂ -, or Formula: -CH ₂ -Ar-CH ₂ -CH ₂ -(wherein, Ar represents a group represented by phenylene, naphthylene, or biphenylene), and A represents an arylylene group with 6 to 10 carbon atoms It is not particularly limited, and examples thereof include phenylene rings.

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

The alkenyl phenol A is preferably an alkenyl bisphenol in which one alkenyl group is bonded to each of two phenolic aromatic rings of bisphenols from the viewpoint of further improving compatibility. Considering the same point of view, alkenyl bisphenols should be diallyl bisphenols with one allyl group bonded to the two phenolic aromatic rings of bisphenols, and/or two phenolic aromatic rings in bisphenols. Dipropenylbisphenol in which one propenyl group is bonded to each aromatic ring.

Diallyl bisphenol is not particularly limited, and examples include: o,o'-diallyl bisphenol A ("DABPA" produced by Daiwa Chemical Industry Co., Ltd.), o,o'-diallyl Bisphenol F, o,o'-diallyl bisphenol S, o,o'-diallyl bisphenol terpene. Dipropenyl bisphenol is not particularly limited, examples include: o,o'-dipropenyl bisphenol A ("PBA01" of Qunying Chemical Industry Co., Ltd.), o,o'-dipropenyl bisphenol F , o, o'-dipropenyl bisphenol S, o, o'-dipropenyl bisphenol S.

The average number of phenolic 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, from the viewpoint of more effectively and reliably exerting the effects of the present invention. The average number of phenol groups was calculated using the following formula.

[number 1]

In the formula, Ai represents the number of phenolic groups of alkenylphenols with i phenolic groups in the molecule, Xi represents the proportion of alkenylphenols with i phenolic groups in the molecule to the total alkenylphenols, X ₁ +X ₂ +…X _n =1.

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

The polysiloxane compound or resin is not particularly limited as long as it has a polysiloxane skeleton formed by repeating siloxane bonds. The polysiloxane skeleton may be a linear skeleton, a cyclic skeleton, or a network skeleton. Among them, a linear skeleton is preferable from the viewpoint of more effectively and reliably exerting the effect of the present invention.

The group containing an epoxy group is not specifically limited, For example, the group represented by following formula (a1) is mentioned.

[chemical 17]

In the formula, ^R represents an alkylene group (for example, an alkylene group with 1 to 5 carbons such as methylene, ethylene, and propylidene), and X represents a monovalent group represented by the following formula (a2) or the following formula ( a3) represents a monovalent group.

[chemical 18]

[chemical 19]

Epoxy-modified polysiloxane B preferably contains epoxy-modified polysiloxane with an epoxy equivalent of 140-250 g/mol. Epoxy-modified polysiloxane B contains epoxy-modified polysiloxane having an epoxy equivalent within the above-mentioned range, which has excellent compatibility with thermosetting resins and can further improve low thermal expansion And the tendency to balance the peel strength of copper foil. Considering the same point of view, the above-mentioned epoxy equivalent is more preferably 145-245 g/mol, and even more preferably 150-240 g/mol.

Epoxy-modified polysiloxane B should contain more than two kinds of epoxy-modified polysiloxane B, considering that it has better compatibility with thermosetting resins, and can further improve the balance between low thermal expansion and copper foil peel strength. Polysiloxane. At this time, two or more epoxy-modified polysiloxanes preferably have different epoxy equivalents, and epoxy-modified polysiloxanes with an epoxy equivalent of 50 to 350 g/mol (hereinafter also referred to as "low-equivalent rings") Oxygen-modified polysiloxane B1") and epoxy-modified polysiloxane with an epoxy equivalent of 400~4000g/mol (hereinafter also referred to as "high-equivalent epoxy-modified polysiloxane B2") are more preferred, containing Epoxy-modified polysiloxane with an epoxy equivalent of 140~250g/mol (low-equivalent epoxy-modified polysiloxane B1') and epoxy-modified polysiloxane with an epoxy equivalent of 450~3000g/mol ( High-equivalent epoxy-modified polysiloxane B2') is even better.

When epoxy-modified polysiloxane B contains two or more epoxy-modified polysiloxanes, the average epoxy equivalent of epoxy-modified polysiloxane B should be 140~3000g/mol, preferably 250~2000g/mol Preferably, 300~1000g/mol is even better. The average epoxy equivalent was calculated using the following formula.

[number 2]

In the formula, Ei represents the epoxy equivalent of one epoxy-modified polysiloxane in more than two epoxy-modified polysiloxanes, and Wi represents the above-mentioned epoxy-modified polysiloxane in epoxy-modified polysiloxane B. The ratio of silicon to oxygen, W ₁ +W ₂ +...W _n =1.

Epoxy-modified polysiloxane B is considered to have better compatibility with thermosetting resins, and can further improve the balance between low thermal expansion and copper foil peel strength. It is preferable to contain epoxy represented by the following formula (1): Modified polysiloxane. [chemical 20]

In formula (1), R ¹ each independently represent a single bond, alkylene, aryl or aralkylene, R ² each independently represent an alkyl or phenyl group with 1 to 10 carbon atoms, and n represents 0 to 10 An integer of 100.

In formula (1), the alkylene group represented by R ¹ may be linear, branched or cyclic. The carbon number of the alkylene group is preferably 1-12, more preferably 1-4. As an alkylene group, a methylene group, an ethylene group, or a propylene group is mentioned, for example. Among them, R ¹ is preferably a propylene group.

In formula (1), the arylylene group represented by R ¹ may have a substituent. The carbon number of the extended aryl group is preferably 6-40, more preferably 6-20. Examples of the arylylene group include: phenylene, cyclohexylphenylene, hydroxyphenylene, cyanophenylene, nitrophenylene, naphthylene, biphenylene, anthracenyl, pyrenyl, pyrene Fuji and so on. These groups may contain an ether bond, a ketone bond, or an ester bond.

式(X-I)中，*表示原子鍵。 In formula (1), the carbon number of the aralkylene group represented by R is preferably ^7-30 , more preferably 7-13. As an aralkylene group, the group represented by following formula (XI) is mentioned, for example. [chem 21]

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

In the formula (1), the group represented by ^R1 may further have a substituent, and the substituents may include, for example: a linear alkyl group having 1 to 10 carbons, a branched alkyl group having 3 to 10 carbons, a branched alkyl group having 3 carbons, Cyclic alkyl with ~10 carbons, linear alkoxy with 1 to 10 carbons, branched alkoxy with 3 to 10 carbons, cyclic alkoxy with 3 to 10 carbons. Among them, R ¹ is particularly preferably a propylene group.

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

In formula (1), n represents an integer of 0 or more, for example, 0-100. In consideration of better compatibility with thermosetting resins and further improvement of the balance between low thermal expansion and copper foil peel strength, n is preferably 50 or less, more preferably 30 or less, and even more preferably 20 or less.

Epoxy-modified polysiloxane B should contain two or more types of formula (1) in consideration of the further excellent compatibility with thermosetting resins, and can further improve the balance between low thermal expansion and copper foil peel strength Epoxy-modified polysiloxane. At this time, the two or more epoxy-modified polysiloxanes contained should have different n respectively, including epoxy-modified polysiloxanes in which n is 1~2 in formula (1) and n in formula (1) is 5~20 epoxy modified polysiloxane is better.

The average number of epoxy groups per molecule of epoxy-modified polysiloxane B is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less, in view of more effectively and reliably exerting the effect of the present invention. The average number of epoxy groups was calculated by the following formula.

[number 3]

In the formula, Bi represents the number of epoxy groups of the epoxy-modified polysiloxane with i epoxy groups in the molecule, and Yi represents the epoxy-modified polysiloxane with i epoxy groups in the molecule. The proportion of the whole modified polysiloxane, Y ₁ +Y ₂ +...Y _n =1.

The content of epoxy-modified polysiloxane B is preferably 100% by mass of the total of epoxy-modified polysiloxane B and epoxy compound C from the viewpoint of exhibiting further excellent low thermal expansion and chemical resistance. It is 5 to 95% by mass, more preferably 10 to 90% by mass, still more preferably 40 to 85% by mass, and still more preferably 50 to 80% by mass.

Epoxy-modified polysiloxane B can also use a commercial item, and the thing manufactured by a well-known method can also be used. Commercially available products include, for example, "X-22-163" and "KF-105" of Shin-Etsu Chemical Co., Ltd.

[Epoxy compound C] The epoxy compound C is an epoxy compound other than the epoxy-modified polysiloxane B, and more specifically, is an epoxy compound not having a polysiloxane skeleton. By containing the epoxy compound C, the curable composition of this embodiment can exhibit excellent compatibility, heat resistance, chemical resistance, copper foil peel strength and insulation reliability.

The epoxy compound C is not particularly limited as long as it is an epoxy compound other than epoxy-modified polysiloxane B. As the epoxy compound C in the curable composition of this embodiment, typically, a bifunctional epoxy compound having two epoxy groups in one molecule, and a bifunctional epoxy compound having three or more epoxy groups in one molecule can be used. multifunctional epoxy compounds. The epoxy compound C preferably contains a bifunctional epoxy compound and/or a polyfunctional epoxy compound from the viewpoint of exhibiting further excellent compatibility, heat resistance, chemical resistance, copper foil peel strength, and insulation reliability.

式(3a)中，Ar ³各自獨立地表示苯環或萘環，Ar ⁴表示苯環、萘環或聯苯環，R ^3a各自獨立地表示氫原子或甲基，k表示1~50之整數， 在此，Ar ³中的苯環或萘環也可更具有一個或多個取代基，該取代基也可為未圖示之環氧丙氧基，其它取代基例如也可為碳數1~5之烷基、苯基等， Ar ⁴中的苯環、萘環或聯苯環也可更具有一個或多個取代基，該取代基也可為環氧丙氧基，其它取代基例如也可為碳數1~5之烷基、苯基等。 The epoxy compound C in the curable composition of this embodiment is not particularly limited, and a compound represented by the following formula (3a) can be used. [chem 22]

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 represent a hydrogen atom or a methyl group, and k represents an integer of 1 to 50 , Here, the benzene ring or naphthalene ring in Ar ³ can also have one or more substituents, and the substituents can also be unillustrated glycidyloxy groups, and other substituents can also be, for example, carbon number 1 ~5 alkyl, phenyl, etc., Ar ⁴ in the benzene ring, naphthalene ring or biphenyl ring can also have one or more substituents, the substituents can also be glycidyloxy, other substituents such as It can also be an alkyl group, phenyl group, etc. with 1 to 5 carbon atoms.

式(b1)中，Ar ³各自獨立地表示苯環或萘環，Ar ⁴表示苯環、萘環或聯苯環，R ^3a各自獨立地表示氫原子或甲基， 在此，Ar ³中的苯環或萘環也可更具有一個或多個取代基，該取代基例如也可為碳數1~5之烷基、苯基等之環氧丙氧基以外的取代基， Ar ⁴中的苯環、萘環或聯苯環也可更具有一個或多個取代基，該取代基例如也可為碳數1~5之烷基、苯基等之環氧丙氧基以外的取代基。 Among the compounds represented by the above-mentioned formula (3a), examples of the bifunctional epoxy compound include compounds represented by the following formula (b1). [chem 23]

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 represent a hydrogen atom or a methyl group, and here, in Ar ³ The benzene ring or the naphthalene ring can also have one or more substituents, such as substituents other than glycidoxy groups such as alkyl groups with 1 to 5 carbon atoms, phenyl groups, etc., Ar in ⁴ A benzene ring, a naphthalene ring or a biphenyl ring may further have one or more substituents, for example, a substituent other than glycidoxy such as an alkyl group having 1 to 5 carbon atoms or a phenyl group.

The compound represented by formula (3a) is preferably a phenolic novolac epoxy resin in which Ar ⁴ is at least substituted by glycidoxy in formula (3a). Phenolic novolak type epoxy resins are not particularly limited, and examples thereof include compounds having a structure represented by the following formula (3-1) (polyfunctional epoxy resins containing a naphthalene skeleton), naphthalene cresol novolak Varnish type epoxy resin.

式中，Ar ³¹各自獨立地表示苯環或萘環，Ar ⁴¹各自獨立地表示苯環、萘環或聯苯環，R ^31a各自獨立地表示氫原子或甲基，p表示1，kz表示1~50之整數，各環也可具有環氧丙氧基以外的取代基(例如碳數1~5之烷基、碳數1~5之烷氧基或苯基)，Ar ³¹及Ar ⁴¹中至少一者表示萘環。 [chem 24]

In the formula, Ar ³¹ each independently represent a benzene ring or a naphthalene ring, Ar ⁴¹ each independently represent a benzene ring, a naphthalene ring or a biphenyl ring, R ^31a each independently represent a hydrogen atom or a methyl group, p represents 1, and kz represents 1 An integer of ~50, each ring may also have a substituent other than glycidoxy (such as an alkyl group with 1 to 5 carbons, an alkoxy group with 1 to 5 carbons, or a phenyl group), Ar ³¹ and Ar ⁴¹ At least one of them represents a naphthalene ring.

式中，R表示甲基，kz和上述式(3-1)中之kz同義。 Examples of the compound having a structure represented by formula (3-1) include compounds having a structure represented by formula (3-2). [chem 25]

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

The naphthyl cresol novolak type epoxy resin is not particularly limited, for example, a cresol/naphthol novolak type epoxy resin represented by the following formula (NE) is preferable. In addition, the compound represented by the following formula (NE) is a random copolymer of a constituent unit of a cresol novolak resin epoxy and a constituent unit of a naphthol novolac resin epoxy, and the cresol epoxy and the naphthol ring Any of the oxides may serve as the terminal. [chem 26]

m and n in the aforementioned formula (NE) each represent an integer of 1 or more. The upper limit and ratio of m and n are not particularly limited. Considering low thermal expansion, m:n (here, m+n=100) should be 30~50:70~50, 45~55:55~ 45 is better.

As the naphthylcresol novolak-type epoxy resin, a commercially available product may be used, or a product manufactured by a known method may be used. Commercially available products include, for example: "NC-7000", "NC-7300", and "NC-7300L" produced by Nippon Kayaku Co., Ltd., or "HP-9540" and "HP-9500L" produced by DIC Co., Ltd. ", etc., especially "HP-9540".

The compound represented by formula (3a) may be a compound other than the aforementioned phenolic novolac epoxy resin (hereinafter also referred to as "aralkyl epoxy resin"). The aralkyl type epoxy resin is preferably Ar in the formula (3a) ³ is a naphthalene ring, and Ar ⁴ is a compound of a benzene ring (also known as "naphthol aralkyl type epoxy resin"), and the formula (3a) Among them, Ar ³ is a benzene ring, and Ar ⁴ is a compound of a biphenyl ring (also called "biphenyl aralkyl type epoxy resin"), preferably a biphenyl aralkyl type epoxy resin.

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

式中，ka表示1以上之整數，宜為1~20，為1~6更佳。 The biphenyl aralkyl type epoxy resin is preferably a compound represented by the following formula (3b). [chem 27]

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

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

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

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

式中，R ₁₃各自獨立地表示氫原子、碳數1~3之烷基(例如甲基或乙基)、或碳數2~3之烯基(例如乙烯基、烯丙基或丙烯基)。 [化29]

式中，R ₁₄各自獨立地表示氫原子、碳數1~3之烷基(例如甲基或乙基)、或碳數2~3之烯基(例如乙烯基、烯丙基或丙烯基)。 In view of further improving heat resistance, chemical resistance, copper foil peel strength and insulation reliability, naphthyl ether type epoxy resin is preferably a bifunctional epoxy compound represented by the following formula (3-3) or the following formula ( 3-4) The polyfunctional epoxy compound represented, or their mixture. [chem 28]

In the formula, R ₁₃ each independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons (such as methyl or ethyl), or an alkenyl with 2 to 3 carbons (such as vinyl, allyl or propenyl) . [chem 29]

In the formula, _R14 each independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons (such as methyl or ethyl), or an alkenyl with 2 to 3 carbons (such as vinyl, allyl or propenyl) .

As the naphthyl ether type epoxy resin, a commercial item may be used, or a product manufactured by a known method may be used. Commercially available naphthyl ether type epoxy resins include, for example, "HP-6000", "EXA-7300", "EXA-7310", "EXA-7311", "EXA-7311L" of DIC Co., Ltd. ", "EXA7311-G3", "EXA7311-G4", "EXA-7311G4S", "EXA-7311G5", etc., are especially good for HP-6000.

式(b3)中，R ^3b各自獨立地表示氫原子、碳數1~5之烷基(例如甲基或乙基)、芳烷基、苄基、萘基、至少含有1個環氧丙氧基之萘基或至少含有1個環氧丙氧基之萘甲基，n表示0以上之整數(例如0~2)。 Examples of naphthalene-type epoxy resins other than the above are not limited to the following, and compounds represented by the following formula (b3) are exemplified. [chem 30]

In formula (b3), R ^3b each independently represent a hydrogen atom, an alkyl group (such as methyl or ethyl) with 1 to 5 carbons, an aralkyl group, a benzyl group, a naphthyl group, a glycidyl group containing at least one Naphthyl group or naphthylmethyl group containing at least one glycidoxy group, n represents an integer of 0 or more (for example, 0~2).

Commercial products of the compound represented by the above formula (b3) include, for example, "HP-4032" (n=0 in the above formula (b3)) and "HP-4710" (the above formula (b3) Among them, n=0, and R ^3b is a naphthylmethyl group containing at least one glycidoxyl group) and the like.

式(b2)中，Ra各自獨立地表示碳數1~10之烷基或氫原子。 Also, the epoxy compound C in the curable composition of this embodiment is preferably a biphenyl-type epoxy compound (excluding those belonging to the above-mentioned epoxy compound C). The biphenyl type epoxy compound is not particularly limited, and examples thereof include compounds represented by the following formula (b2) (compound b2). [chem 31]

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

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

When the biphenyl type epoxy compound is the compound b2, the biphenyl type epoxy compound may be in the form of a mixture of compounds b2 in which the number of Ra of the alkyl group is different. Specifically, it is preferable to be a mixture of biphenyl type epoxy compounds having a different number of Ra in the alkyl group, a mixture of compound b2 in which the Ra in the alkyl group is 0 and a compound b2 in which the Ra in the alkyl group is 4. good.

式中，R ^3c各自獨立地表示氫原子或碳數1~5之烷基，k2表示0~10之整數。 In addition, as the epoxy compound C in the curable composition of this embodiment, dicyclopentadiene type epoxy resins (those belonging to the above-mentioned epoxy compound C are excluded) can be used. The dicyclopentadiene type epoxy resin is not particularly limited, and examples thereof include compounds represented by the following formula (3-5). [chem 32]

In the formula, R ^3c each independently represent a hydrogen atom or an alkyl group with 1 to 5 carbons, and k2 represents an integer of 0 to 10.

式(b4)中，R ^3c各自獨立地表示氫原子或碳數1~5之烷基(例如甲基或乙基)。 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). [chem 33]

In formula (b4), R ^3c each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbons (such as methyl or ethyl).

As the dicyclopentadiene type epoxy resin, a commercial item may be used, or a product manufactured by a known method may be used. Commercially available dicyclopentadiene type epoxy resins include "EPICRON HP-7200L", "EPICRON HP-7200", "EPICRON HP-7200H", "EPICRON HP- 7000HH", etc.

Among them, the epoxy compound C is preferably selected from the epoxy compound represented by the formula (3a), naphthalene-type epoxy compound in view of exhibiting further excellent heat resistance, chemical resistance, copper foil peel strength and insulation reliability. One or more of the group consisting of resin and biphenyl type epoxy compound, at this time, the epoxy compound represented by formula (3a) should contain naphthyl cresol novolak type epoxy resin, and the naphthalene type epoxy resin should contain Naphthyl ether type epoxy resin.

The epoxy compound C may contain other epoxy compounds other than the aforementioned epoxy compounds. Other epoxy compounds are not particularly limited, and examples include: bisphenol-type epoxy resins, paraphenolmethane-type epoxy resins, anthracene-type epoxy resins, glycidyl ester-type epoxy resins, polyol-type epoxy resins, Epoxy resins containing isocyanurate rings, fennel-type epoxy resins, epoxy resins composed of bisphenol A-type structural units and hydrocarbon-based structural units, etc. Other epoxy compounds, among the above, may contain bisphenol-type epoxy resins from the viewpoint of further improving heat resistance, chemical resistance, copper foil peel strength, and insulation reliability. Bisphenol-type epoxy resins can be used such as : Diallyl bisphenol type epoxy resin (such as diallyl bisphenol A type epoxy resin, diallyl bisphenol E type epoxy resin, diallyl bisphenol F type epoxy resin, diallyl bisphenol type epoxy resin, Allyl bisphenol S-type epoxy resin, etc.), etc.

Epoxy compound C can be used individually by 1 type or in combination of 2 or more types among the said epoxy compound and epoxy resin.

上述式中，Ci表示分子中具有i個之環氧基之環氧化合物之環氧基數，Zi表示分子中具有i個之環氧基之環氧化合物所佔環氧化合物整體之比例，Z ₁+Z ₂+…Z _n=1。 The average number of epoxy groups per molecule of the epoxy compound C is preferably 1 or more and less than 3, more preferably 1.5 or more and 2.5 or less, from the viewpoint of more effectively and reliably exerting the effects of the present embodiment. The average number of epoxy groups was calculated by the following formula. [number 4]

In the above formula, Ci represents the number of epoxy groups in the epoxy compound with i epoxy groups in the molecule, Zi represents the ratio of the epoxy compound with i epoxy groups in the molecule to the overall epoxy compound, Z ₁ + Z ₂ + . . . Z _n =1.

The content of epoxy compound C is based on the total amount of epoxy-modified polysiloxane B and epoxy compound C 100 from the viewpoint of exhibiting further excellent heat resistance, chemical resistance, copper foil peel strength, and insulation reliability. The mass % is preferably 5-95 mass %, more preferably 10-90 mass %, more preferably 15-60 mass %, especially preferably 20-50 mass %.

[Anhydride D] The curable composition of this embodiment contains acid anhydride D. The acid anhydride D reacts with the terminal hydroxyl group and epoxy group generated by the reaction of alkenylphenol A, epoxy-modified polysiloxane B, and epoxy compound C other than epoxy-modified polysiloxane B to form terminal carboxyl. Thereby, since a large number of carboxyl groups having high reactivity with thermosetting resins are present, compatibility and crosslink density are improved, and low thermal expansion properties are improved.

The acid anhydride D is not particularly limited, or has a cyclic structure, but it is preferably an acid anhydride with 4 to 20 carbon atoms, preferably an acid anhydride with 4 to 16 carbon atoms, in view of the tendency to further improve compatibility with thermosetting resins. The acid anhydride is more preferred, and the acid anhydride with 4-10 carbon atoms is even more preferred.

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. Considering that the compatibility with the thermosetting resin is further excellent, and the balance between low thermal expansion and copper foil peel strength can be further improved, phthalic anhydride and succinic anhydride are more preferable.

The content of acid anhydride D is preferably 0.8~ 15% by mass, more preferably 0.9-10% by mass, more preferably 1-5% by mass.

[Compound F] The curable composition of this embodiment preferably further contains a compound selected from maleimide compounds, cyanate compounds, and At least one compound F of the group consisting of phenolic compound A' other than alkenylphenol A and alkenyl-substituted nadicimide compound. Compound F is not particularly limited, and it is preferably bifunctional or higher, and may be trifunctional or higher.

The content of compound F in the curable composition of this embodiment is preferably 10 to 80 mass %, more preferably 20 to 60 mass %, and even more preferably 30 to 50 mass % with respect to 100 mass % of resin solid content. .

式(3)中，R ₅各自獨立地表示氫原子或甲基，n ₁表示1以上之整數。 (Maleimide Compound) Compound F preferably contains a maleimide compound from the viewpoint of further improving low thermal expansion and copper foil peel strength. 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. Amide compounds (such as N-phenylmaleimide, N-hydroxyphenylmaleimide, etc.), polymaleimides having two or more maleimide groups in one molecule Compounds (such as bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimidophenoxy)phenyl)propane, bis(3-ethyl -5-methyl-4-maleiminophenyl)methane, bis(3,5-dimethyl-4-maleiminophenyl)methane, bis(3,5-diethyl Base-4-maleimidophenyl) methane), m-phenylene bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 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') , Prepolymers of these maleimide compounds and amine compounds, etc. [chem 34]

In formula (3), R ₅ each independently represents a hydrogen atom or a methyl group, and n ₁ represents an integer of 1 or more.

n ₁ is 1 or more, preferably 1-100, more preferably 1-10.

式(3’)中，R ¹³各自獨立地表示氫原子、碳數1~5之烷基、或苯基，n ⁴表示1以上且10以下之整數。 [chem 35]

In formula (3′), R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbons, or a phenyl group, and n ⁴ represents an integer of 1 to 10.

These maleimide compounds may be used alone or in combination of two or more. Among them, in view of further improving low thermal expansion and copper foil peel strength, the maleimide compound preferably contains a compound selected from bis(4-maleimidophenyl)methane, 2,2-bis (4-(4-maleimidophenoxy)phenyl)propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, formula (3) At least one selected from the group consisting of the maleimide compound represented by the formula (3′) and the maleimide compound represented by the formula (3′).

As the maleimide compound, a commercially available product may be used, or a product produced by a known method may be used. Commercially available maleimide compounds include "BMI-70", "BMI-80", and "BMI-1000P" produced by K･I Chemicals Co., Ltd., and "BMI-1000P" produced by Daiwa Chemical Industry Co., Ltd. -3000", "BMI-4000", "BMI-5100", "BMI-7000", "BMI-2300", "MIR-3000-70MT" of Nippon Kayaku Co., Ltd. (Formula (3') R ¹³ are all hydrogen atoms, and n ⁴ is a mixture of 1 to 10), etc.

The content of the maleimide compound is preferably 1 to 50 parts by mass, more preferably 5 to 40 parts by mass, based on 100 parts by mass of resin solids, in view of further improving low thermal expansion and copper foil peel strength. More preferably, it is 10 to 40 parts by mass.

式(4)中，R ₆各自獨立地表示氫原子或甲基，n ₂表示1以上之整數。 [化37]

式(5)中，R _ya各自獨立地表示碳數2~8之烯基或氫原子，R _yb各自獨立地表示碳數1~10之烷基或氫原子，R _yc各自獨立地表示碳數4~12之芳香環，R _yc也可和苯環形成縮合結構，R _yc可存在也可不存在，A ^1a各自獨立地表示碳數1~6之伸烷基、碳數7~16之伸芳烷基、碳數6~10之伸芳基、亞茀基、磺醯基、氧原子、硫原子或直接鍵結(單鍵)，R _yc不存在時，1個苯環中也可具有2個以上之R _ya及/或R _yb之基。n表示1~20之整數。 (Cyanate compound) Compound F preferably contains a cyanate compound from the viewpoint of further improving low thermal expansion and copper foil peel strength. 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 compounds such as compounds represented by the following formula (4). Cyanate compounds, compounds represented by the following formula (5) other than compounds represented by formula (4), novolak type cyanate compounds, biphenyl aralkyl type cyanate esters, diallyl bisphenol type cyanide compounds Ester compounds, bis(3,3-dimethyl-4-cyanooxyphenyl)methane, bis(4-cyanooxyphenyl)methane, 1,3-dicyanooxybenzene, 1,4- Dicyanoxybenzene, 1,3,5-tricyanoxybenzene, 1,3-dicyanoxynaphthalene, 1,4-dicyanoxynaphthalene, 1,6-dicyanoxynaphthalene, 1, 8-dicyanoxynaphthalene, 2,6-dicyanoxynaphthalene, 2,7-dicyanoxynaphthalene, 1,3,6-tricyanoxynaphthalene, 4,4'-dicyanoxynaphthalene Benzene, bis(4-cyanoxyphenyl) ether, bis(4-cyanoxyphenyl)sulfide, bis(4-cyanoxyphenyl)sulfide, 2,2-bis(4-cyanoxyphenyl) phenyl) propane. These cyanate compounds may be used alone or in combination of two or more. In this embodiment, the cyanate compound preferably includes polyfunctional cyanate compounds such as naphthol aralkyl type cyanate compounds and/or novolak type cyanate compounds in consideration of heat resistance, low thermal expansion, and copper foil peel strength. ester compounds. [chem 36]

In formula (4), R ₆ each independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more. [chem 37]

In the formula (5), R _ya each independently represent an alkenyl group having 2 to 8 carbon atoms or a hydrogen atom, R _yb each independently represent an alkyl group having 1 to 10 carbon atoms or a hydrogen atom, and R _yc each independently represent a carbon number 4~12 aromatic rings, R _yc can also form a condensed structure with a benzene ring, R _yc may or may not exist, and A ^1a each independently represent an alkylene group with 1 to 6 carbons and an aromatic chain with 7 to 16 carbons Alkyl group, aryl group with 6~10 carbons, fenylene group, sulfonyl group, oxygen atom, sulfur atom or direct bond (single bond), when R _yc does not exist, there may be 2 in 1 benzene ring More than one base of R _ya and/or R _yb . n represents an integer from 1 to 20.

Among them, the cyanate compound preferably includes compounds represented by formula (4) and/or formula (5) from the viewpoint of further improving heat resistance, low thermal expansion, and copper foil peel strength.

In formula (4), n ₂ represents an integer of 1 or more, preferably an integer of 1 to 20, more preferably an integer of 1 to 10.

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

In formula (5), the alkyl group with 1 to 10 carbons represented by _R is not particularly limited, for example: methyl, ethyl, propyl, butyl, pentyl, hexyl and other linear alkyl groups; Branched alkyl groups such as isopropyl, isobutyl, and tertiary butyl.

In formula (5), the alkylene group having 1 to 6 carbon atoms represented by A ^1a is not particularly limited, and examples thereof include methylene, ethylene, trimethylene, and propylidene. In addition, in formula (5), the aralkylene group having 7 to 16 carbon atoms represented by A ^1a is not particularly limited, and examples thereof include the formula: -CH ₂ -Ar-CH ₂ -, -CH ₂ -CH ₂ -Ar -CH ₂ -CH ₂ -, or a group represented by the formula: -CH ₂ -Ar-CH ₂ -CH ₂ - (wherein Ar represents phenylene, naphthylene, or biphenylene). In addition, the arylylene group having 6 to 10 carbon atoms represented by A ^1a is not particularly limited, and examples thereof include a phenylene ring.

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

式(c1)中，Rx各自獨立地表示氫原子或甲基，R各自獨立地表示碳數2~8之烯基、碳數1~10之烷基或氫原子，n表示1~10之整數。 The compound represented by the formula (5) is preferably a compound represented by the following formula (c1). [chem 38]

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

These cyanate compounds can also be produced according to known methods. The specific production method can be, for example, the method described in JP-A-2017-195334 (particularly paragraphs 0052-0057).

The content of the cyanate compound of Compound F is preferably 10 to 70 parts by mass, more preferably 10 to 60 parts by mass, based on 100 parts by mass of resin solids, in consideration of further improving low thermal expansion and copper foil peel strength. Best, more preferably 10 to 40 parts by mass.

(Phenolic compound A' other than alkenylphenol A) Compound F may contain phenolic compound A' other than alkenylphenol A from the viewpoint of exhibiting further excellent copper foil peel strength. The phenolic compound A' is not particularly limited, and examples thereof include bisphenol-type phenolic resins (such as bisphenol-A type resins, bisphenol-E type resins, bisphenol-F-type resins, bisphenol-S-type resins, etc.), phenolic novolac resins, etc. (such as phenol novolac resin, naphthol novolac resin, cresol novolak resin, etc.), glycidyl ester type phenolic resin, naphthalene type phenolic resin, anthracene type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl Type phenolic resin, alicyclic phenolic resin, polyol type phenolic resin, aralkyl type phenolic resin, phenol modified aromatic hydrocarbon formaldehyde resin, fennel type phenolic resin, etc. These phenolic compounds may be used alone or in combination of two or more.

Among them, the phenolic compound A' preferably contains a bifunctional phenolic compound having two phenolic hydroxyl groups in one molecule from the viewpoint of exhibiting further excellent compatibility and copper foil peel strength.

The bifunctional phenolic compound is not particularly limited, and examples include: bisphenol, biscresol, bisphenols with a fennel skeleton (such as bisphenol with a fennel skeleton, biscresol with a fennel skeleton, etc.), biphenols (such as p , p'-biphenol, etc.), dihydroxy diphenyl ether (such as 4,4'-dihydroxy diphenyl ether, etc.), dihydroxy diphenyl ketone (such as 4,4'-dihydroxy diphenyl ketone etc.), dihydroxydiphenyl sulfide (such as 4,4'-dihydroxydiphenylsulfide, etc.), dihydroxyaromatic hydrocarbons (such as hydroquinone, etc.). These bifunctional phenol compounds may be used alone or in combination of two or more. Among them, the bifunctional phenol compound preferably contains at least one selected from the group consisting of bisphenol, biscresol, and bisphenols having a fennel skeleton from the viewpoint of exhibiting further excellent copper foil peel strength. Considering the same point of view as above, the bisphenols having a fennel skeleton are preferably biscresol fennel.

As an aralkyl type phenolic resin, the compound represented by following formula (c2) is mentioned, for example.

[chem 39]

In the formula, Ar ¹ each independently represents a benzene ring or a naphthalene ring, Ar ² represents a benzene ring, a naphthalene ring, or a biphenyl ring, R ^2a each independently represent a hydrogen atom or a methyl group, m represents an integer of 1 to 50, each The ring may have a substituent other than a hydroxyl group (for example, an alkyl group having 1 to 5 carbon atoms, a phenyl group, etc.).

The compound represented by the formula (c2) is preferably a compound in which Ar ¹ is a naphthalene ring and Ar ² is a benzene ring in the formula (c2) from the viewpoint of further improving the peel strength of the copper foil (hereinafter also referred to as "naphthol aralkyl group"). Type phenolic resin"), and a compound in which Ar ¹ is a benzene ring and Ar ² is a biphenyl ring in formula (c2) (hereinafter also referred to as "biphenyl aralkyl type phenolic resin").

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

[chemical 40]

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

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

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

[chem 41]

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

From the viewpoint of further improving low thermal expansion and copper foil peel strength, the phenolic compound A' preferably includes a compound represented by the above formula (8).

As the aralkyl type phenolic resin, a commercial item may be used, or a product manufactured by a known method may be used. Commercially available aralkyl type phenolic resins include: "KAYAHARD GPH-65", "KAYAHARD GPH-78", "KAYAHARD GPH-103" (biphenyl aralkyl type phenolic resins) manufactured by Nippon Kayaku Co., Ltd. ), "SN-495" (naphthol aralkyl type phenolic resin) produced by Nippon Steel Chemical Co., Ltd.

As the content of alkenylphenol A in compound F, in consideration of the viewpoint that further excellent compatibility can be exhibited, relative to the total of alkenylphenol A, epoxy-modified polysiloxane B, epoxy compound C, and phenolic compound A' 100 parts by mass, preferably 1 to 50 parts by mass, more preferably 3 to 30 parts by mass, more preferably 5 to 20 parts by mass.

The content of epoxy-modified polysiloxane B in the curable composition of this embodiment is considered to be able to exhibit a further excellent balance between low thermal expansion and copper foil peel strength. The total amount of polysiloxane B, epoxy compound C and phenolic compound A' is 100 parts by mass, preferably 5-70 parts by mass, more preferably 10-60 parts by mass, and even more preferably 20-55 parts by mass.

The content of the epoxy compound C in the curable composition of this embodiment is considered to be able to exhibit further excellent compatibility, heat resistance, chemical resistance, copper foil peel strength and insulation reliability. Compared with alkenylphenol A. The total amount of epoxy-modified polysiloxane B, epoxy compound C and phenolic compound A' is 100 parts by mass, preferably 5-50 parts by mass, more preferably 10-30 parts by mass, and 15-25 parts by mass Even better.

The content of the phenolic compound A' in the curable composition of this embodiment is considered to be able to exhibit a further excellent copper foil peel strength. And the total amount of phenol compound A' is 100 parts by mass, preferably 5-30 parts by mass, more preferably 10-25 parts by mass, even more preferably 15-20 parts by mass.

In addition, when the curable composition does not contain phenolic compound A', the respective contents of the above-mentioned alkenylphenol A, epoxy-modified polysiloxane B, and epoxy compound C represent relative to alkenylphenol A, epoxy-modified polysiloxane Content of 100 mass parts of total amounts of oxygen B and epoxy compound C.

式(2d)中，R ₁各自獨立地表示氫原子、或碳數1~6之烷基(例如甲基或乙基)，R ₂表示碳數1~6之伸烷基、伸苯基、伸聯苯基、伸萘基、或下式(6)或下式(7)表示之基。 [化43]

式(6)中，R ₃表示亞甲基、亞異丙基、CO、O、S或SO ₂。 [化44]

式(7)中，R ₄各自獨立地表示碳數1~4之伸烷基、或碳數5~8之伸環烷基。 (Nadic imide compound substituted with alkenyl group) From the viewpoint of further improving heat resistance, compound F preferably contains an alkenyl substituted nadic imide compound. The alkenyl-substituted nadicimide compound is not particularly limited if it is a compound having one or more alkenyl-substituted nadicimide groups in one molecule, and examples thereof include the following formula (2d): compound. [chem 42]

In formula (2d), R ₁ each independently represents a hydrogen atom, or an alkyl group (such as methyl or ethyl) with 1 to 6 carbons, and R ₂ represents an alkylene group, phenylene group, or phenylene group with 1 to 6 carbons. A biphenylene group, a naphthylene group, or a group represented by the following formula (6) or the following formula (7). [chem 43]

In formula (6), R ₃ represents methylene, isopropylidene, CO, O, S or SO ₂ . [chem 44]

In the formula (7), R ₄ each independently represent an alkylene group having 1 to 4 carbon atoms, or a cycloalkylene group having 5 to 8 carbon atoms.

The alkenyl-substituted nadicimide compound represented by the formula (2d) may be a commercially available product, or a product produced by a known method may be used. Commercially available products include "BANI-M" and "BANI-X" produced by Maruzen Petrochemical Co., Ltd.

The content of the alkenyl-substituted nadicimide compound of the compound F is preferably 1 to 40 parts by mass, more preferably 5 to 35 parts by mass, based on 100 parts by mass of the solid content of the resin in consideration of improving heat resistance. Best, more preferably 10-30 parts by mass.

[Second Embodiment: Curable Composition] The curable composition of the second embodiment contains a constituent unit derived from alkenylphenol A, a constituent unit derived from epoxy-modified polysiloxane B, and an epoxy compound C derived from epoxy-modified polysiloxane B. Structural unit and polymer E derived from the structural unit of acid anhydride D. Alkenylphenol A, epoxy-modified polysiloxane B, epoxy compound C and acid anhydride D are as described above. The following is a second embodiment of polymer E containing a constituent unit derived from alkenylphenol A, a constituent unit derived from epoxy-modified polysiloxane B, a constituent unit derived from epoxy compound C, and a constituent unit derived from acid anhydride D The curable resin composition differs from the curable composition of the above-mentioned first embodiment related to the aspect that does not contain the polymer E.

Polymer E exhibits sufficient compatibility even when mixed with a thermosetting resin that lacks compatibility with polysiloxane compounds. Thereby, a curable composition containing polymer E and a thermosetting resin can provide a uniform varnish and cured product. A cured product such as a prepreg obtained by using this curable composition has components uniformly compatible, and variations in physical properties due to uneven components are suppressed.

In addition, the curable composition of the second embodiment may contain, in addition to the polymer E, a compound selected from the group consisting of alkenylphenol A, epoxy-modified polysiloxane B, epoxy compound C, and acid anhydride D. One or more species in the group. In this case, alkenylphenol A, epoxy-modified polysiloxane B, epoxy compound C, and acid anhydride D contained in the curable composition of the second embodiment may be unreacted components remaining after polymerization of polymer E , It is also possible to re-add ingredients to the synthesized polymer E.

Also, in the curable composition of the second embodiment, in addition to the polymer E, a phenol selected from the above-mentioned maleimide compound, cyanate compound, and the above-mentioned alkenylphenol A may be further contained as needed. At least one compound F of the group consisting of compound A' and an alkenyl-substituted nadicimide compound. The compound F may be an unreacted component remaining after the polymerization of the polymer E, or a component newly added to the synthesized polymer E.

[Polymer E] Polymer E contains constituent units derived from alkenylphenol A, constituent units derived from epoxy-modified polysiloxane B, constituent units derived from epoxy compound C, and constituent units derived from acid anhydride D, and may further contain Compound F of at least one selected from the group consisting of maleimide compounds, cyanate compounds, phenolic compounds A' other than alkenylphenol A', and alkenyl-substituted nadicimide compounds the constituent unit. When polymer E has constituent units derived from compound F, compound F is preferably a bifunctional compound. In addition, in this specification, "constitutive unit derived from alkenyl phenol A", "constitutive unit derived from epoxy-modified polysiloxane B", "constitutive unit derived from epoxy compound C", "constitutive unit derived from acid anhydride D " and "constituent unit derived from compound F" are defined as polymer E containing alkenylphenol A, epoxy-modified polysiloxane B, epoxy compound C, acid anhydride D, and compound F. unit, and the polymer E contains a structural unit formed by a reaction that can provide the same structural unit. Hereinafter, each structural unit is also called a structural unit A, B, C, D, and 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.

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

The content of the constituent unit A in the polymer E is preferably 5 to 50% by mass relative to the total mass of the polymer E. When the content of the structural unit A falls within the above range, the curable composition of the second embodiment tends to exhibit further excellent compatibility. Considering the same point of view, the content of the constituent unit A is more preferably 10 to 45% by mass, more preferably 15 to 40% by mass.

The content of the constituent unit B in the polymer E is preferably 20 to 60% by mass relative to the total mass of the polymer E. When the content of the structural unit B falls within the above range, the curable composition of the second embodiment tends to exhibit a balance between further excellent low thermal expansion properties and copper foil peel strength. Considering the same point of view, the content of the constituent unit B is more preferably 25 to 55% by mass, and more preferably 30 to 50% by mass.

Constituent unit B preferably contains epoxy-modified polysiloxane (low-equivalent epoxy-modified polysiloxane B1) with an epoxy equivalent of 50-350 g/mol and epoxy resin with an epoxy equivalent of 400-4000 g/mol. The constituent unit of modified polysiloxane (high-equivalent epoxy-modified polysiloxane B2). Low-equivalent epoxy-modified polysiloxane B1 and high-equivalent epoxy-modified polysiloxane B2 are epoxy-modified polysiloxanes (low-equivalent epoxy-modified polysiloxane) with an epoxy equivalent of 140-250 g/mol respectively. Oxygen B1'), epoxy-modified polysiloxane with an epoxy equivalent of 450-3000 g/mol (high-equivalent epoxy-modified polysiloxane B2') is more preferred.

The content of the constituent unit B1 derived from the low-equivalent epoxy-modified polysiloxane B1 in the polymer E is preferably 5 to 25% by mass, more preferably 7.5 to 20% by mass, and 10% to the total mass of the polymer E. ~17% by mass is even better.

The content of the constituent unit B2 derived from the high-equivalent epoxy-modified polysiloxane B2 in the polymer E is preferably 15-55% by mass, more preferably 20-52.5% by mass, and 25% by mass relative to the total mass of the polymer E. ~50% by mass is even better.

The mass ratio of the content of the constituent unit B2 to the content of the constituent unit B1 is preferably 1.5-4, more preferably 1.7-3.5, and even more preferably 1.9-3.1. When the content of the structural unit B1 and the structural unit B2 has the above-mentioned relationship, the low thermal expansion property and the copper foil peel strength of the curable composition of the second embodiment tend to be further improved.

The constituent unit C in the polymer E is preferably a compound selected from 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). At least one type of unit in the group.

The content of the constituent unit C in the polymer E is preferably 5 to 40% by mass relative to the total mass of the polymer E. If the content of the constituent unit C falls within the above range, the curable composition of the second embodiment will have further excellent compatibility, and can exhibit further excellent heat resistance, chemical resistance, low thermal expansion, copper foil Tendency to peel strength and insulation reliability. Considering the same point of view, the content of the constituent unit C is more preferably 10 to 30% by mass, more preferably 15 to 25% by mass.

In addition, the content of the constituent unit C is preferably 5 to 95% by mass, more preferably 10 to 90% by mass, more preferably 15 to 60% by mass, and even more preferably 20 to 60% by mass relative to the total mass of the constituent unit B and the constituent unit C. 50% by mass is preferred. Since the contents of the constituent unit B and the constituent unit C have the above relationship, the curable composition of the second embodiment has further excellent compatibility, and further improves heat resistance, chemical resistance, low thermal expansion, copper Tendency for foil peel strength and insulation reliability.

The content of the constituent unit D in the polymer E is preferably 3 to 20% by mass relative to the total mass of the polymer E. When the content of the structural unit D falls within the above range, the curable composition of the second embodiment tends to exhibit a further excellent balance between low thermal expansion and copper foil peel strength. Considering the same point of view, the content of the constituent unit D is more preferably 5 to 15% by mass, and even more preferably 5 to 10% by mass.

When the polymer E has a structural unit derived from the compound F, the content of the structural unit F in the polymer E is preferably 3 to 40% by mass relative to the total mass of the polymer E. When the content of the constituent unit F falls within the above range, the curable composition of the second embodiment tends to exhibit further excellent heat resistance, chemical resistance, low thermal expansion, copper foil peel strength, and insulation reliability. . Considering the same point of view, the content of the constituent unit F is more preferably 5 to 35% by mass, more preferably 10 to 30% by mass.

When the polymer E has a structural unit derived from a phenolic compound A' other than alkenylphenol A (hereinafter also referred to as "constituent unit A'"), the content of the structural unit A' in the polymer E is relative to the total amount of the polymer E. The mass should be 5-30% by mass. With the content of the constituent unit A' falling within the above range, the curable composition of the second embodiment can exhibit further excellent heat resistance, chemical resistance, low thermal expansion, copper foil peel strength and insulation reliability. tendency. Considering the same point of view, the content of the constituent unit A' is more preferably 10 to 27.5% by mass, more preferably 10 to 25% by mass.

The alkenyl equivalent weight in the polymer E is preferably 300-1500 g/mol. When the alkenyl equivalent is 300 g/mol or more, the elastic modulus of the cured product of the curable composition of the second embodiment tends to be further reduced, and as a result, the substrate obtained by using the cured product can be further reduced. Tendency to equal thermal expansion rate. When the alkenyl equivalent is 1500 g/mol or less, the compatibility, heat resistance, chemical resistance, low thermal expansion, copper foil peel strength and insulation reliability of the curable composition of the second embodiment tend to be further improved . Considering the same point of view, the alkenyl equivalent is more preferably 350 to 1200 g/mol, and even more preferably 400 to 1000 g/mol.

The content of the polymer E in the curable composition of the second embodiment is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, more preferably 15 to 40% by mass based on 100% by mass of the resin solid content. better. If the content falls within the above range, the curable composition tends to have further excellent compatibility and exhibit a balance between low thermal expansion and copper foil peel strength.

Polymer E, for example, can be produced by reacting alkenylphenol A, epoxy-modified polysiloxane B, epoxy compound C, acid anhydride D, and compound F as needed in the presence of polymerization catalyst G. get. This reaction can also be carried out in the presence of an organic solvent. More specifically, in the above steps, the addition reaction between the epoxy group possessed by the epoxy-modified polysiloxane B and the epoxy compound C and the hydroxyl group possessed by the alkenylphenol A, and the obtained addition reaction After the addition reaction between the hydroxyl group of the reaction product and the epoxy group of the epoxy-modified polysiloxane B and the epoxy compound C, etc., the addition reaction of the terminal hydroxyl group and the epoxy group and the acid anhydride D is carried out. This affords polymer E.

The manufacturing method of the curable composition of this embodiment (especially the curable composition of the second embodiment) preferably includes the following steps: A step of obtaining a prepolymer obtained by polymerizing alkenylphenol A, epoxy-modified polysiloxane B, and epoxy compound C, and A step of reacting the acid anhydride D with the aforementioned prepolymer. By producing a prepolymer obtained by polymerizing alkenylphenol A, epoxy-modified polysiloxane B, and epoxy compound C, and then reacting the anhydride D with the prepolymer, low thermal expansion can be obtained. Tendency of curable composition with further excellent performance and copper foil peel strength.

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

The imidazole compound is not particularly limited, for example: 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl -2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dimethylolimidazole, 2-phenyl-4-methyl-5 -Hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole ("TBZ" of Shikoku Chemical Industry Co., Ltd.), 2,4,5-triphenyl Imidazoles such as kiimidazole ("TPIZ" produced by Tokyo Chemical Industry Co., Ltd.). Among them, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole and/or 2,4,5-triphenylimidazole are preferable from the viewpoint of preventing homopolymerization of the epoxy component.

The amount of polymerization catalyst G (preferably imidazole compound) is not particularly limited, for example, relative to the total amount of alkenylphenol A, epoxy-modified polysiloxane B, epoxy compound C, acid anhydride D and compound F 100 mass Parts are 0.1 to 10 parts by mass. From the viewpoint of increasing the weight average molecular weight of the polymer E, the amount of the polymerization catalyst G used is preferably at least 0.5 parts by mass, more preferably at most 4.0 parts by mass.

[Organic solvents] The organic solvent is not particularly limited, and for example, a polar solvent or a nonpolar solvent can be used. The polar solvent is not particularly limited, and examples thereof include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; celluloid-based solvents such as propylene glycol monomethyl ether and propylene glycol monomethyl ether acetate; ethyl lactate, methyl acetate, and the like; Esters, ethyl acetate, butyl acetate, isoamyl acetate, ethyl lactate, methyl methoxypropionate, methyl hydroxyisobutyrate and other ester solvents; dimethylacetamide, dimethylformamide Amides such as amines, etc. The nonpolar solvent is not particularly limited, and examples thereof include aromatic hydrocarbons such as toluene and xylene. These solvents may be used alone or in combination of two or more.

The amount of the organic solvent used is not particularly limited, for example, 50 to 150 parts by mass relative to 100 parts by mass of the total amount of alkenylphenol A, epoxy-modified polysiloxane B, epoxy compound C, acid anhydride D, and compound F .

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

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

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

When the curable composition of the second embodiment contains the polymer E and the compound F, the content of the polymer E in the curable composition of the second embodiment is preferably 100% by mass of the total of the polymer E and the compound F. 5-60% by mass, more preferably 10-55% by mass, more preferably 20-50% by mass. If the content falls within the above range, the curable composition tends to have further excellent compatibility and exhibit a balance between low thermal expansion and copper foil peel strength.

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

The curable composition in this embodiment may further contain other resins as long as the effects of this embodiment are not inhibited. Other resins include, for example, oxetane resins, benzodiazepine compounds, compounds having polymerizable unsaturated groups, and the like. These resins may be used alone or in combination of two or more.

Oxetane resins include, for example: oxetane, 2-methyloxetane, 2,2-dimethyloxetane, 3-methyloxetane, 3 ,3-Dimethyloxetane and other alkyloxetanes, 3-methyl-3-methoxymethyloxetane, 3,3'-bis(trifluoromethyl) Perfluorooxetane, 2-chloromethyl oxetane, 3,3-bis(chloromethyl) oxetane, biphenyl type oxetane, product of Toa Gosei Co., Ltd. "OXT-101", "OXT-121" and so on.

The term "benzohexacompound" in this specification refers to a compound having two or more dihydrobenzoxaha rings in one molecule. Examples of the benzo㗁𠯤 compound include "Bisphenol F-type benzo㗁𠯤 BF-BXZ" and "Bisphenol S-type benzo㗁𠯤BS-BXZ" produced by Konishi Chemical Co., Ltd.

Examples of compounds having polymerizable unsaturated groups include vinyl compounds such as ethylene, propylene, styrene, divinylbenzene, and divinylbiphenyl; methyl (meth)acrylate, (meth)acrylic acid-2 -Hydroxyethyl ester, -2-Hydroxypropyl (meth)acrylate, Polypropylene glycol di(meth)acrylate, Trimethylolpropane di(meth)acrylate, Trimethylolpropane tri(methyl) Acrylic ester, neopentylthritol tetra(meth)acrylate, dipentynerythritol hexa(meth)acrylate and other units or (meth)acrylates of polyols; bisphenol A epoxy (methyl) ) acrylate, bisphenol F epoxy (meth)acrylate and other epoxy (meth)acrylates; benzocyclobutene resin, etc.

[Inorganic Filler] In the curable composition in this embodiment, it is preferable to further contain an inorganic filler from the viewpoint of further improving low thermal expansion properties. Inorganic fillers are not particularly limited, and examples include: silicon dioxide, silicon compounds (such as white carbon, etc.), metal oxides (such as alumina, titanium dioxide, zinc oxide, magnesium oxide, zirconia, etc.), metal nitrogen Compounds (such as boron nitride, condensed boron nitride, silicon nitride, aluminum nitride, etc.), metal oxysulfides (such as barium sulfate, etc.), metal hydroxides (such as aluminum hydroxide, aluminum hydroxide heat-treated products ( For example, aluminum hydroxide is heat-treated and part of the water of crystallization is subtracted), boehmite, magnesium hydroxide, etc.), molybdenum compounds (such as molybdenum oxide, zinc molybdate, etc.), zinc compounds (such as zinc borate, stannic acid zinc, etc.), clay, kaolin, talc, calcined clay, calcined kaolin, calcined talc, mica, E-glass, A-glass, NE-glass, C-glass, L-glass, D-glass , S-glass, M-glass G20, glass short fiber (including E glass, T glass, D glass, S glass, Q glass and other glass powders), hollow glass, spherical glass, etc. These inorganic fillers may be used alone or in combination of two or more. Among them, the inorganic filler is preferably at least one selected from the group consisting of silicon dioxide, metal hydroxides, and metal oxides, including silicon dioxide More preferably at least one of the group consisting of silicon dioxide, boehmite and alumina, and even more preferably silicon dioxide.

Silicas include, for example, natural silica, fused silica, synthetic silica, fumed silica (AEROSIL), hollow silica, and the like. These silicas may be used alone or in combination of two or more. Among them, fused silica is preferable in view of dispersibility, and fused silica having two or more kinds of different particle sizes is more preferable in view of filling property and fluidity.

The content of the inorganic filler is preferably 50-1000 parts by mass, more preferably 70-500 parts by mass, more preferably 100-300 parts by mass relative to 100 parts by mass of the solid content of the resin, in view of further improving the low thermal expansion property. good.

[Silane coupling agent] The curable composition of this embodiment may further contain a silane coupling agent. By containing the silane coupling agent in the curable composition of this embodiment, the dispersibility of the inorganic filler can be further improved, or the components of the curable composition of this embodiment can be further improved and the adhesive strength of the substrate described later Propensity.

The silane coupling agent is not particularly limited, and examples include silane coupling agents commonly used in surface treatment of inorganic substances, and examples include: aminosilane compounds (such as γ-aminopropyltriethoxysilane, N-β- (aminoethyl)-γ-aminopropyltrimethoxysilane, etc.), epoxy silane compounds (such as γ-glycidoxypropyltrimethoxysilane, etc.), acrylic silane compounds (such as γ-acryloxypropyltrimethoxysilane, etc.), cationic silane compounds (such as N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride salts, etc.), styrene silane compounds, phenyl silane compounds, etc. A silane coupling agent can be used individually by 1 type, or in combination of 2 or more types. Among them, the silane coupling agent is preferably an epoxy silane compound. Examples of the epoxysilane compound include "KBM-403", "KBM-303", "KBM-402", and "KBE-403" produced by Shin-Etsu Chemical Co., Ltd.

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

[Wetting and dispersing agent] 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.

As long as the wetting and dispersing agent is a known dispersing agent (dispersion stabilizer) used to disperse the filler, examples include DISPER BYK-110, 111, 118, 180, 161, BYK- W996, W9010, W903, etc.

The content of the wetting and dispersing agent is not particularly limited, but is preferably not less than 0.5 parts by mass and not more than 5.0 parts by mass relative to 100 parts by mass of resin solids.

[solvent] The curable composition of this embodiment may further contain a solvent. The curable composition of this embodiment tends to further improve handleability (workability) by lowering the viscosity during preparation of the curable composition by containing a solvent, or to further improve the impregnation property to the base material.

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

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 in a solvent one at a time or one by one and stirring them. At this time, well-known treatments such as stirring, mixing, and kneading can be used in order to dissolve or disperse each component uniformly.

[use] As described above, the curable composition of this embodiment has excellent compatibility, and can exhibit further excellent low thermal expansion and copper foil peel strength. Therefore, the curable composition of this embodiment can be used ideally for metal foil-clad laminates and printed wiring boards. That is, the curable composition of this embodiment can be used ideally as a hardening composition used for a printed wiring board.

In addition, especially in the above application, the curable composition of the second embodiment preferably contains polymer E and at least epoxy compound C (and epoxy compound C that is separately present as the constituent unit C in polymer E). At this time, in the polymer E, the unit derived from the epoxy compound C preferably has a unit derived from the aforementioned bifunctional epoxy compound, more preferably has a unit derived from the aforementioned biphenyl type epoxy compound, and has a unit derived from the above-mentioned formula (b2) The unit of the compound (compound b2) is more preferably, the compound b2 having the number of R ^a derived from 0 and the number of R ^a of the alkyl group being 4 (commercially available products such as those manufactured by Mitsubishi Chemical Co., Ltd. Units named "YL-6121HA", etc.) are even better. In addition, the epoxy compound C that exists separately from the constituent unit C in the polymer E preferably includes the aforementioned naphthyl ether type epoxy resin (commercially available such as "HP-6000" produced by DIC Co., Ltd., etc.) And/or naphthalene cresol novolac epoxy resin (commercially available such as "HP-9540" of DIC Co., Ltd., etc.).

[Prepreg] The prepreg of this embodiment includes: a base material, and the curable composition of this embodiment impregnated or coated on the base material. As mentioned above, the prepreg can also be obtained by a known method. Specifically, after impregnating or coating the curable composition of this embodiment on the substrate, the prepreg can be prepared at a temperature of 100 to 200 It can be heated and dried under the condition of ℃, and can be obtained by making it semi-hardened (B-staged).

The prepreg of the present embodiment also includes the form of 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.

The content of the curable composition in the prepreg relative to the total amount of the prepreg is preferably 30~90% by volume, more preferably 35~85% by volume, and 40~ 80% by volume is even better. When the content of the curable composition falls within the above range, formability tends to be further improved. In addition, the calculation of the content of the curable composition here also includes the cured product of the curable composition of this embodiment. In addition, the solid content of the prepreg here is a component obtained by removing the solvent from the prepreg, for example, a filler is included in the solid content of the prepreg.

The base material is not particularly limited, and examples thereof include known base materials used as materials for various printed wiring boards. Specific examples of substrates include: glass substrates, inorganic substrates other than glass (such as inorganic substrates made of inorganic fibers other than glass such as quartz), organic substrates (such as wholly aromatic polyamide, polyester , organic substrates composed of organic fibers such as polyparaphenylene benzobisoxazole, polyimide), etc. These base materials may be used alone or in combination of two or more. Among them, a glass substrate is preferable from the viewpoint of further improving heating dimensional stability.

Examples of fibers constituting the glass substrate include fibers such as E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass. Among them, the fiber constituting the glass substrate is preferably selected from E glass, D glass, S glass, T glass, Q glass, L glass, NE glass, and HME glass from the viewpoint of further excellent strength and low water absorption. One or more fibers in the group.

The form of the base material is not particularly limited, and examples thereof include forms such as woven fabrics, nonwoven fabrics, rovings, cut strand mats, and surface-treated mats. The weaving method of the woven fabric is not particularly limited, and known examples include plain weave, diagonal weave, and twill weave, and can be appropriately selected from among these known ones depending on the intended use and performance. In addition, glass woven fabrics subjected to fiber opening treatment or surface-treated with a silane coupling agent or the like can be preferably used. The thickness and mass of the base material are not particularly limited, and generally, those of about 0.01 to 0.1 mm can be ideally used.

[resin sheet] The resin sheet of this embodiment contains: a support body, and the curable composition of this embodiment arrange|positioned on the surface of a support body. The resin sheet of the present embodiment may be formed, for example, by applying the curable composition of the present embodiment to one or both sides of a support. The resin sheet of the present embodiment can be produced by directly coating and drying a curable composition used in a prepreg or the like on a support such as a metal foil or a film, for example.

The support is not particularly limited, and for example, known materials used in various printed wiring 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, Resin sheets such as polypropylene (PP) film and polyethylene (PE) film, and metal foils such as aluminum foil, copper foil, and gold foil. Among them, the support is preferably electrolytic copper foil or PET film.

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 then semi-hardening (B-staging). The method for producing the resin sheet of this embodiment is preferably a method for producing a composite of a B-stage resin and a support in general. Specifically, for example, a method of applying the above-mentioned curable composition to a support such as copper foil and then heating it in a dryer at 100 to 200°C for 1 to 60 minutes to semi-harden and A method of manufacturing a resin sheet, etc. The adhesion amount of the curable composition to the support is preferably in the range of 1.0 μm or more and 300 μm or less in terms of the resin thickness of the resin sheet. The resin sheet of this embodiment can be used as a build-up material of a printed wiring board.

[Metal Foil Clad Laminates] The metal foil-clad laminate of this embodiment includes: a laminate formed using one or more types selected from the group consisting of the prepreg and the resin sheet of this embodiment; and a unit arranged on the laminate. Metal foil on one or both sides. This laminated body may be formed with one prepreg or resin sheet, or may be formed with a plurality of prepregs and/or resin sheets.

The metal foil (conductor layer) may be any metal foil used for various printed wiring board materials, for example, metal foils such as copper and aluminum, and copper foils include copper foils such as 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.

The forming method and forming conditions of the metal foil-clad laminate are not particularly limited, and methods and conditions generally used for laminates and multilayer boards of printed wiring boards can be used. For example, a multilayer press, multilayer vacuum press, continuous molding machine, high temperature and high pressure (autoclave) molding machine, etc. can be used for forming a laminate (the above-mentioned laminate) or a metal foil-clad laminate. In addition, in the forming of the laminate (the above-mentioned laminate) or the metal foil-clad laminate (lamination forming), the temperature is 100~300°C, the pressure is 2~100kgf/cm ² , and the heating time is 0.05~ The range of 5 hours is normal. In addition, post-hardening can also be performed at a temperature of 150~300°C as required. Especially when using a multi-layer press machine, considering the viewpoint of fully accelerating the hardening of the prepreg, the temperature is 200°C~250°C, the pressure is 10~40kgf/cm ² , the heating time is 80 minutes~130 minutes, and the temperature is 215°C~235 ℃, pressure 25~35kgf/cm ² , and heating time 90 minutes~120 minutes are more preferable. Furthermore, a multilayer board can also be produced by combining the above-mentioned prepreg with a wiring board for an inner layer produced separately and performing lamination molding.

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

The printed wiring board of this embodiment can be manufactured specifically, for example by the following method. First, the metal foil-clad laminate of this embodiment is prepared. The metal foil of the metal foil-clad laminate is etched into a predetermined wiring pattern to produce an inner substrate having a conductor layer (inner circuit). Then, on the surface of the conductor layer (inner layer circuit) of the inner layer substrate, a predetermined number of insulating layers and metal foils for the outer layer circuit are laminated in order, and heated and pressed to form an integral body (lamination molding). Obtain a stack. In addition, the lamination forming method and its forming conditions are the same as the lamination forming method and its forming conditions of the above-mentioned laminated board and metal foil-clad laminated board. Then, the laminated body is provided with through-holes and hole-drilling processing for guide holes, and plating metal is formed on the walls of the holes formed to conduct conduction between the conductor layer (inner layer circuit) and the metal foil for outer layer circuits. film. Then, the metal foil for the outer layer circuit is etched into a predetermined wiring pattern to produce an outer layer substrate having a conductor layer (outer layer circuit). A printed wiring board is manufactured in this way.

In addition, when the metal foil-clad laminate is not used, a conductor layer as a circuit may be formed on the above-mentioned insulating layer to produce a printed wiring board. In this case, electroless plating can also be used for the formation of the conductor layer. [Example]

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

(Example 1) In a three-necked flask equipped with a thermometer and a Dimroth, add 5.0 parts by mass of diallyl bisphenol A (DABPA, Daiwa Chemical Industry Co., Ltd.), biscresol (BCF, Osaka Gas Chemical ( stock)) 5.5 parts by mass, epoxy-modified polysiloxane compound A (X-22-163, Shin-Etsu Chemical Co., Ltd., functional group equivalent 200g/eq.) 4.1 parts by mass, epoxy-modified polysiloxane compound B (KF-105, Shin-Etsu Chemical Co., Ltd., functional group equivalent 500g/eq.) 8.4 parts by mass, biphenyl type epoxy compound A (YL-6121HA, Mitsubishi Chemical Co., Ltd.) 5.5 parts by mass, as solvent 30.0 parts by mass of propylene glycol monomethyl ether acetate (DOWANOL PMA, Dow Chemical Japan Co., Ltd.) was heated and stirred in an oil bath to 120° C. After confirming that the raw material is dissolved in the solvent, add 0.3 parts by mass of imidazole catalyst A (TBZ, Shikoku Chemical Industry Co., Ltd.) and heat up to 140° C., stir for 5 hours, and cool to obtain a phenoxy polymer solution (solid content 50 mass%) (polymer generation step). In addition, diallyl bisphenol A is equivalent to "alkenylphenol A", epoxy-modified polysiloxane compound A and epoxy-modified polysiloxane compound B are equivalent to "epoxy-modified polysiloxane B", Biphenyl type epoxy compound A corresponds to "epoxy compound C". The phenoxy polymer solution contains a polymer containing a constituent unit derived from alkenylphenol A, a constituent unit derived from epoxy-modified polysiloxane B, and a constituent unit derived from epoxy compound C.

After heating this 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 (solid content 50 mass % ) (polymer modification step). The modified phenoxy polymer solution contains the constituent units derived from alkenylphenol A, the constituent units derived from epoxy-modified polysiloxane B, the constituent units derived from epoxy compound C, and the constituent units derived from acid anhydride D polymer. The polymer modification step can also be carried out continuously with the polymer generation step.

[Measuring method of weight average molecular weight Mw] The weight average molecular weight Mw of the modified phenoxy polymer obtained as above was measured as follows. 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) and analyzed. Shodex GPC KF-804 (length 30cm×inner diameter 8mm), Shodex GPC KF-803 (length 30cm×inner diameter 8mm), Shodex GPC KF-802 (length 30cm×inner diameter 8mm) and Shodex GPC made by Showa Denko were used as columns. There are 4 KF-801 (length 30cm×inner diameter 8mm) in total. The mobile phase uses THF (solvent), the flow rate is set to 1mL/min, and the detector uses RID-10A. The weight average molecular weight Mw was calculated|required by the GPC method using standard polystyrene as a standard substance. The weight average molecular weight Mw of the modified phenoxy polymer measured as above was 12,000.

In this modified phenoxy polymer solution, 25 parts by mass of a naphthol aralkyl type phenol compound (SN-495V, Nippon Steel Chemical Materials Co., Ltd.) and a novolak type maleimide compound (BMI-2300 , Daiwa Chemical Industry (stock)) 9 mass parts, phenylene ether type maleimide compound (BMI-80, Daiwa Chemical Industry (stock)) 9 mass parts, naphthyl ether type epoxy compound (HP- 6000, DIC (stock)) 27 parts by mass, spherical silica (SC-2050MB, Admatechs (stock)) 200 parts by mass, wetting and dispersing agent (DISPERBYK-161, BYK (stock)) 1 mass part, silane coupling Agent (KBM-403, Shin-Etsu Chemical Co., Ltd.) 5 parts by mass to obtain a varnish (varnish production step). This varnish was dip-coated on S glass woven fabric (thickness 100 μm), and heated and dried at 150°C for 3 minutes to obtain a prepreg (prepreg) with a curable composition solid content (including filler) of 58.2% by volume. manufacturing steps).

(Example 2) In the polymer generation step, the addition amount of diallyl bisphenol A was set from 5.0 mass parts to 4.7 mass parts, the addition amount of biscresol was set to 5.2 mass parts from 5.5 mass parts, and the epoxy modified The amount of added polysiloxane A was set from 4.1 parts by mass to 3.8 parts by mass, the amount of epoxy-modified polysiloxane B was set from 8.4 parts by mass to 8.1 parts by mass, and the addition of biphenyl-type epoxy compound A The amount is set from 5.5 parts by mass to 5.2 parts by mass, and in the polymer modification step, the amount of anhydride D added is replaced from 1.5 parts by mass to 3.0 parts by mass, except that it is carried out in the same manner as in Example 1 to obtain A prepreg with a curable composition solid content (including filler) of 58.2% by volume. The modified phenoxy polymer solution contains the constituent units derived from alkenylphenol A, the constituent units derived from epoxy-modified polysiloxane B, the constituent units derived from epoxy compound C, and the constituent units derived from acid anhydride D polymer. Moreover, the weight average molecular weight Mw of the modified phenoxy polymer in Example 2 measured by the method mentioned above was 12,000.

(Example 3) In the polymer modification step, except that the acid anhydride D was replaced by 3.0 parts by mass of phthalic anhydride from 3.0 parts by mass of succinic anhydride, the same procedure as in Example 2 was carried out to obtain the solid content of the curable composition (including filled material) with a content of 58.2% by volume. The modified phenoxy polymer solution contains the constituent units derived from alkenylphenol A, the constituent units derived from epoxy-modified polysiloxane B, the constituent units derived from epoxy compound C, and the constituent units derived from acid anhydride D polymer. Moreover, the weight average molecular weight Mw of the modified phenoxy polymer in Example 3 measured by the method mentioned above was 12,000.

(comparative example 1) In the polymer generation step, the addition amount of diallyl bisphenol A was set from 5.0 mass parts to 5.3 mass parts, the addition amount of biscresol was set to 5.8 mass parts from 5.5 mass parts, and the epoxy modified The addition amount of polysiloxane A was set from 4.1 parts by mass to 4.4 parts by mass, the addition amount of epoxy-modified polysiloxane B was set from 8.4 parts by mass to 8.7 parts by mass, and the addition of biphenyl epoxy compound A Amount is set to 5.8 mass parts from 5.5 mass parts, and the addition amount of imidazole catalyst A is set to 1.2 mass parts from 0.30 mass parts, and do not implement polymer modification step, except that, carry out similarly with embodiment 1 A prepreg having a resin composition solid content (including filler) content of 58.2% by volume was obtained. The weight average molecular weight Mw of the phenoxy polymer in Comparative Example 1 measured by the aforementioned method was 12,000.

Two prepregs obtained in Examples 1 to 3 and Comparative Example 1 were stacked, and electrolytic copper foil (3EC-M2S-VLP, manufactured by Mitsui Metal Mining Co., Ltd.) with a thickness of 12 μm was placed on top and bottom of it. Lamination molding was performed at a pressure of 30 kgf/cm ² and a temperature of 220° C. for 120 minutes to obtain a copper clad laminate including an insulating layer having a thickness of 0.2 mm as a metal foil clad laminate. The properties of the obtained copper-clad laminate were evaluated by the methods shown below. The evaluation results are shown in Table 1.

[Copper foil peel strength] Copper foil peel strength (unit: kN/m) was measured based on JIS C6481 using the copper clad laminated board (10mmx150mmx0.2m) obtained by the said method.

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

[Table 1] Example 1 Example 2 Example 3 Comparative example 1 characteristic CTE(60~260℃) 5.9 6.0 6.0 6.5 Copper foil peel strength 0.51 0.64 0.60 0.39

As shown in Table 1 above, the copper clad laminates (Examples 1 to 3) using the curable composition of this embodiment have excellent low thermal expansion properties and copper foil peel strength.

This application is based on a Japanese patent application (Japanese Patent Application No. 2021-128743) filed with the Japan Patent Office (JPO) on August 5, 2021, and the contents thereof are incorporated herein by reference.

Claims (34)

A sclerosing composition comprising: Alkenylphenol A, Epoxy modified polysiloxane B, Epoxy compounds C other than the epoxy-modified polysiloxane B, and Anhydride D. The curable composition according to claim 1, wherein the average number of phenolic groups per molecule of the alkenylphenol A is not less than 1 and less than 3, and the average number of epoxy groups per molecule of the epoxy-modified polysiloxane B is The number of bases is from 1 to less than 3, and the average number of epoxy groups per molecule of the epoxy compound C is from 1 to less than 3. The curable composition according to claim 1 or 2, wherein the alkenylphenol A includes diallyl bisphenol and/or diallyl bisphenol. The curable composition according to claim 1 or 2, wherein the epoxy-modified polysiloxane B includes epoxy-modified polysiloxane with an epoxy equivalent of 140-250 g/mol. The curable composition according to claim 1 or 2, wherein the epoxy-modified polysiloxane B comprises epoxy-modified polysiloxane represented by the following formula (1);

(1) In the formula, R ¹ each independently represent a single bond, alkylene, aryl or aralkylene, R ² each independently represent an alkyl or phenyl group with 1 to 10 carbons, and n represents 0 to 10 An integer of 100. The curable composition according to claim 1 or 2, wherein the epoxy compound C comprises a compound represented by the following formula (b2);

In the formula, R ^a each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom. 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 the total amount of the epoxy-modified polysiloxane B and the epoxy compound C (100% by mass). quality%. The curable composition of claim 1 or 2, wherein the acid anhydride D is selected from phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and cis-4-cyclohexene-1,2 - One or more species from the group consisting of diacid anhydride. A sclerosing composition comprising: Polymer E includes: a constituent unit derived from alkenylphenol A, a constituent unit derived from epoxy-modified polysiloxane B, a constituent unit derived from epoxy compound C, and a constituent unit derived from acid anhydride D. The curable composition according to claim 9, wherein the weight average molecular weight of the polymer E is 3.0×10 ³ to 5.0×10 ⁴ . The curable composition according to claim 9 or 10, wherein the content of the constituent units derived from epoxy-modified polysiloxane B in the polymer E is 20 to 60% relative to the total mass of the polymer E quality%. The curable composition according to claim 9 or 10, wherein the polymer E has an alkenyl equivalent weight of 300-1500 g/mol. The curable composition according to claim 9 or 10, 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. The curable composition according to claim 9 or 10, wherein the content of the polymer E is 5 to 50% by mass relative to 100% by mass of the resin solid content. The curable composition according to claim 9 or 10, wherein the alkenylphenol A includes diallyl bisphenol and/or diallyl bisphenol. The curable composition according to claim 9 or 10, wherein the epoxy-modified polysiloxane B includes epoxy-modified polysiloxane with an epoxy equivalent of 140-250 g/mol. The curable composition according to claim 9 or 10, wherein the epoxy-modified polysiloxane B comprises epoxy-modified polysiloxane represented by the following formula (1);

(1) In the formula, R ¹ each independently represent a single bond, alkylene, aryl or aralkylene, R ² each independently represent an alkyl or phenyl group with 1 to 10 carbons, and n represents 0 to 10 An integer of 100. The curable composition according to claim 9 or 10, wherein the epoxy compound C comprises a compound represented by the following formula (b2);

In the formula, R ^a each independently represents an alkyl group having 1 to 10 carbon atoms or a hydrogen atom. The hardening composition according to claim 9 or 10, wherein the acid anhydride D is selected from phthalic anhydride, succinic anhydride, maleic anhydride, nadic anhydride and maleic 4-cyclohexene-1,2-dicarboxylic anhydride One or more of the groups formed. The curable composition as claimed in claim 9 or 10 further contains an epoxy compound C, and the epoxy compound C includes a compound represented by the following formula (3-3) or a compound represented by the following formula (3-4);

In the formula, R ₁₃ each independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons, or an alkenyl group with 2 to 3 carbons;

In the formula, R ₁₄ each independently represent a hydrogen atom, an alkyl group with 1 to 3 carbons, or an alkenyl group with 2 to 3 carbons. Such as the curable composition of claim 1 or 9, further containing phenolic compound A' selected from maleimide compound, cyanate compound, alkenylphenol A' and alkenyl-substituted nadicamide ( At least one compound F of the group consisting of nadiimide) compounds. The curable composition according to claim 21, wherein the maleimide compound comprises bis(4-maleimidophenyl)methane, 2,2-bis(4-(4-maleimide Iminophenoxy)phenyl)propane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, maleimide represented by the following formula (3) At least one of the group consisting of a compound and a maleimide compound represented by the following formula (3');

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

In formula (3′), R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 5 carbons, or a phenyl group, and n ⁴ represents an integer of 1 to 10. The curable composition according to claim 21, 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, R ₆ each independently represents a hydrogen atom or a methyl group, and n ₂ represents an integer of 1 or more;

In the formula, R _ya each independently represent an alkenyl group with 2 to 8 carbons or a hydrogen atom, R _yb each independently represent an alkyl group with 1 to 10 carbons or a hydrogen atom, and R _yc each independently represent an alkyl group with 4 to 12 carbons The aromatic ring, R _yc can also form a condensation structure with the benzene ring, R _yc may or may not exist, and A ^1a each independently represent an alkylene group with 1 to 6 carbons, an aralkylene group with 7 to 16 carbons, Arylylene group, fenylene group, sulfonyl group, oxygen atom, sulfur atom or single bond with 6~10 carbons, when R _yc does not exist, one benzene ring may have two or more R _ya and/or The base of R _yb , n represents an integer from 1 to 20. The curable composition according to claim 21, wherein the phenolic compound A' comprises a compound represented by the following formula (8);

(8) In the formula, R ₇ each independently represents a hydrogen atom or a methyl group, and n ₃ represents an integer of 1 or more. The curable composition of claim 1 or 9 further contains an inorganic filler, and the content of the inorganic filler is 50 to 1000 parts by mass relative to 100 parts by mass of the solid content of the resin. The curable composition according to claim 25, wherein the inorganic filler contains at least one selected from the group consisting of silica, boehmite, and alumina. The curable composition according to claim 1 or 9, which is used for printed wiring boards. A prepreg comprising: base material, and The curable composition according to any one of claims 1 to 27 impregnated or coated on the substrate. A resin tablet containing: support, and The curable composition according to any one of Claims 1 to 27 arranged on the surface of the support. A metal foil-clad laminate comprising: A laminate formed using a prepreg according to claim 28, and Metal foil arranged on one or both sides of the laminate. A metal foil-clad laminate comprising: A laminate formed using the resin sheet according to claim 29, and Metal foil arranged on one or both sides of the laminate. A printed wiring board having: An insulating layer formed using a prepreg according to claim 28, and A conductive layer formed on the surface of the insulating layer. A printed wiring board having: An insulating layer formed using the resin sheet according to claim 29, and A conductive layer formed on the surface of the insulating layer. A method for manufacturing a curable composition is a method for manufacturing a curable composition according to any one of Claims 1 to 27, comprising the following steps: obtaining a prepolymer obtained by polymerizing alkenylphenol A, epoxy-modified polysiloxane B, and epoxy compound C; and Anhydride D is reacted with the prepolymer.