TW202006039A - Resin composition, prepreg, metal foil-clad laminate, resin sheet and printed wiring board - Google Patents

Abstract

無。

Description

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

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

In recent years, high integration and miniaturization of semiconductors used in electronic equipment, communication equipment, personal computers, etc. have accelerated. Along with this, various characteristics required for a laminated board for semiconductor packages (for example, a metal-clad laminated board) used in a printed wiring board have become increasingly strict. Examples of required properties include high glass transition temperature, heat resistance, high copper foil peel strength, low dielectric constant, low dielectric loss tangent, low thermal expansion, and low water absorption. Among them, insulator materials with large dielectric tangent and dielectric loss tangent will degrade reliability due to electrical signal attenuation, so materials with small dielectric tangent and dielectric loss tangent are needed. In addition, the multilayer printed wiring board has a problem of warpage expansion, so the low thermal expansion of the insulator material is also important.

In order to obtain a printed wiring board with improved various characteristics, the resin composition used as the material of the printed wiring board has been discussed. For example, Patent Document 1 discloses a film composed of a saturated thermoplastic elastomer having a styrene unit and containing Resin components of at least one type of thermosetting resin and curing agent and curing accelerator in the group consisting of epoxy resin, cyanate resin, polybutadiene resin and maleimide compound , And combined in a predetermined ratio.

Patent Document 2 discloses a vinyl compound with a specific structure and a specific structure for a resin composition exhibiting a high adhesion strength for a resin composition exhibiting a high dielectric strength and a low dielectric loss tangent. The bismaleimide resin of the structure and the polyolefin elastomer as constituent components are combined in a predetermined ratio. [Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 5724503 [Patent Document 2] Japanese Patent Laid-Open No. 2016-117554

[Problems to be solved by the invention]

The examples of Patent Document 1 disclose that by using a saturated thermoplastic elastomer having a styrene unit, and a compound selected from the group consisting of epoxy resin, cyanate resin, polybutadiene resin and maleimide The resin composition of at least one thermosetting resin in the group is formed into a thin film by a predetermined method, and a thin film with excellent dielectric properties in a high-frequency region can be provided. However, the elastomer ratio is high, and there is no description about the glass transition temperature.

On the other hand, the examples of Patent Document 2 describe the use of an adhesive containing a resin composition containing a vinyl compound having a specific structure, a bismaleimide resin having a specific structure, and a polyolefin-based elastomer Examples also show that copper foil has excellent peel strength, low dielectric constant and low dielectric loss tangent. However, there is no description about the glass transition temperature in this document.

Therefore, the object of the present invention is to provide excellent low dielectric constant, low dielectric loss tangent, high glass transition temperature, etc. when used in printed wiring board materials (eg, metal-clad laminates), etc. High metal foil (copper foil) peel strength resin composition, prepreg, metal foil-clad laminate, resin sheet, and printed wiring board. [Means to solve the problem]

The inventors of the present case conducted intensive studies on the above-mentioned subject and found that the maleimide compound (A) containing no siloxane bond, the unmodified cyanate compound (B), and the styrene content were selected. At least one of the group consisting of an elastomer (C1) with a mass of 17% by mass and having a styrene structure at both ends and a polysiloxane (C2) having a maleimide structure at both ends of a specific structure, and When the sum of the masses of (C1) and (C2) is 5 to 25 parts by mass with respect to 100 parts by mass of the resin solid content, the obtained resin composition is used for materials for printed wiring boards (for example, lamination Board, metal-clad laminate), etc., at the same time, it will achieve excellent low dielectric properties, low dielectric loss tangent, high glass transition temperature, high metal foil (copper foil) peel strength, and completed the present invention .

上式(4)中，R₅ 各自獨立地表示碳數1～12之未經取代或經取代之1價烴基，在全部R₅ 中之表示甲基之R₅ 的比例為50莫耳%以上，n₃ 表示0～2之整數。 ［2］如［1］之樹脂組成物，其中，前述不具有矽氧烷鍵之馬來醯亞胺化合物(A)，含有選自由下式(1)表示之馬來醯亞胺化合物、下式(2)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2］

上式(1)中，R₁ 各自獨立地表示氫原子或甲基，n₁ 表示1以上之整數。 ［化3］

上式(2)中，R₂ 各自獨立地表示氫原子、碳數1～8之烷基或苯基，n₂ 表示1以上且10以下之整數。 ［化4］

上式(3)中，R₃ 各自獨立地表示氫原子、甲基或乙基，R₄ 各自獨立地表示氫原子或甲基。 ［3］如［1］或［2］之樹脂組成物，其中，前述未經改性之氰酸酯化合物(B)含有選自由苯酚酚醛清漆型氰酸酯化合物、萘酚芳烷基型氰酸酯化合物、伸萘基醚型氰酸酯化合物、雙酚A型氰酸酯化合物、雙酚M型氰酸酯化合物及二烯丙基雙酚A型氰酸酯化合物構成之群組中之至少1種。 ［4］如［1］～［3］中任一項之樹脂組成物，其中，前述苯乙烯含量為17質量%以上且兩末端具有苯乙烯結構之彈性體(C1)，含有選自由苯乙烯-丁二烯嵌段共聚物、苯乙烯-異戊二烯嵌段共聚物、苯乙烯-氫化丁二烯嵌段共聚物、苯乙烯-氫化異戊二烯嵌段共聚物及苯乙烯-氫化(異戊二烯/丁二烯)嵌段共聚物構成之群組中之至少1種。 ［5］如［1］～［4］中任一項之樹脂組成物，更含有填充材(D)。 ［6］如［5］之樹脂組成物，其中，前述填充材(D)之含量，相對於樹脂組成物中之樹脂固體成分100質量份為50～300質量份。 ［7］一種預浸體，係由基材、與如［1］～［6］中任一項之樹脂組成物形成。 ［8］一種覆金屬箔疊層板，包含：1片以上的彼此重疊之如［7］之預浸體；及配置於前述預浸體之單面或兩面的金屬箔。 ［9］一種樹脂片，包含：支持體；及配置於前述支持體之表面的由如［1］～［6］中任一項之樹脂組成物形成之層。 ［10］一種印刷配線板，包含：絕緣層，及配置於前述絕緣層之表面的導體層；前述絕緣層包含由如［1］～［6］中任一項之樹脂組成物形成之層。 ［發明之效果］That is, the present invention is as follows. [1] A resin composition containing: a maleimide compound (A) without a siloxane bond, an unmodified cyanate compound (B), and a styrene content of 17% by mass At least one of the above group consisting of an elastomer with a styrene structure at both ends (C1) and a polysiloxane with a maleimide structure at both ends (C2); (C1) and (C2) The sum of the masses is 5 to 25 parts by mass relative to 100 parts by mass of the resin solid content; the polysiloxane (C2) having a maleimide structure at both ends, including the maleimide expressed by the following formula (4) Amine-terminated polysiloxane. [Chem 1]

In the above formula (4), R ₅ each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbons, and the ratio of R ₅ representing a methyl group in all R ₅ is 50 mol% or more , N ₃ represents an integer from 0 to 2. [2] The resin composition according to [1], wherein the maleimide compound (A) having no siloxane bond contains a maleimide compound selected from the following formula (1), the following At least one of the group consisting of the maleimide compound represented by the formula (2) and the maleimide compound represented by the following formula (3). [Chem 2]

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

In the above formula (2), R ₂ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbons or a phenyl group, and n ₂ represents an integer of 1 or more and 10 or less. [Chemical 4]

In the above formula (3), R ₃ each independently represents a hydrogen atom, a methyl group or an ethyl group, and R ₄ each independently represents a hydrogen atom or a methyl group. [3] The resin composition according to [1] or [2], wherein the unmodified cyanate compound (B) contains a phenol novolak type cyanate compound, a naphthol aralkyl type cyanide Ester compound, naphthyl ether cyanate compound, bisphenol A cyanate compound, bisphenol M cyanate compound and diallyl bisphenol A cyanate compound At least 1 kind. [4] The resin composition according to any one of [1] to [3], wherein the elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends, contains a resin selected from the group consisting of styrene -Butadiene block copolymer, styrene-isoprene block copolymer, styrene-hydrogenated butadiene block copolymer, styrene-hydrogenated isoprene block copolymer and styrene-hydrogenated At least one member of the group consisting of (isoprene/butadiene) block copolymers. [5] The resin composition according to any one of [1] to [4] further contains a filler (D). [6] The resin composition according to [5], wherein the content of the filler (D) is 50 to 300 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition. [7] A prepreg formed of a base material and the resin composition according to any one of [1] to [6]. [8] A metal foil-clad laminate, comprising: one or more prepregs overlapping each other as in [7]; and metal foil disposed on one or both sides of the prepreg. [9] A resin sheet comprising: a support; and a layer formed of the resin composition according to any one of [1] to [6] disposed on the surface of the support. [10] A printed wiring board, comprising: an insulating layer and a conductor layer disposed on the surface of the insulating layer; the insulating layer includes a layer formed of the resin composition according to any one of [1] to [6]. [Effect of invention]

When the resin composition of the present invention is used as a material for printed wiring boards (for example, laminates, metal-clad laminates), etc., excellent low dielectric constant, low dielectric loss tangent, and High glass transition temperature, high metal foil (copper foil) peel strength prepregs, metal foil-clad laminates, resin sheets, and printed wiring boards have extremely high industrial applicability.

Hereinafter, an embodiment of the present invention (hereinafter referred to as "this embodiment") will be described in detail. In addition, the following embodiments are examples for explaining the present invention, and the present invention is not limited to the embodiments.

[Resin composition] The resin composition of this embodiment contains a maleimide compound (A) having no siloxane bond, an unmodified cyanate compound (B), and a styrene content of 17% by mass or more and At least one of the group consisting of an elastomer with a styrene structure at both ends (C1) and a polysiloxane with a maleimide structure at both ends (C2), the quality of the aforementioned (C1) and (C2) And 5 to 25 parts by mass relative to 100 parts by mass of the resin solid content, the polysiloxane (C2) having a maleimide structure at both ends, including the maleimide terminal polymer represented by formula (4) Silicon Oxygen. The resin composition of the present embodiment is provided with the above-mentioned structure, and when it is used as a material for printed wiring boards (for example, laminates, metal-clad laminates), etc., excellent low dielectric properties and low dielectrics can be achieved at the same time Electric loss tangent, high glass transition temperature, high metal foil (copper foil) peel strength.

[Maleimide compound (A) without a siloxane bond] The resin composition of this embodiment contains a maleimide compound (A) having no siloxane bond. The maleimide compound (A) of this embodiment that does not have a siloxane bond, as long as it has one or more maleimide groups in the molecule and does not have a siloxane bond The compound is not particularly limited, and specific examples thereof include N-phenylmaleimide, N-hydroxyphenylmaleimide, bis(4-maleimidephenyl)methane, 2 ,2-bis[4-(4-maleimidephenoxy)-phenyl]propane, 4,4'-diphenylmethanebismaleimide, bis(3,5-dimethyl -4-maleimide phenyl)methane, bis(3,5-diethyl-4-maleimide phenyl)methane, phenylmethane maleimide, o-phenylene diima Lemethylene imine, m-phenylene bismaleimide, p-phenylene bismaleimide, o-phenylene bis-citraconimide, m-phenylene bis-citraconimide, para Phenyl bis-citramide imidate, 2,2-bis(4-(4-maleimidophenoxy)-phenyl)propane, 3,3'-dimethyl-5,5'- Diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 1,6-bismaleimide- (2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylene bismaleimide, 1,3-bis( 3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidephenoxy)benzene, 4,4'-diphenylmethanebiscitraconimide, 2, 2-bis[4-(4-citraconimidephenoxy)phenyl]propane, bis(3,5-dimethyl-4-citraconimidephenyl)methane, bis(3-ethyl Yl-5-methyl-4-citraconimide phenyl)methane, bis(3,5-diethyl-4-citraconimide phenyl)methane, the aforementioned formulas (1), (2) , And the maleimide compounds represented by (3). Among these, the aspects considering the improvement of low thermal expansion and heat resistance are particularly preferably the maleimide compounds represented by the aforementioned formulas (1), (2) and (3), and the Malay represented by the formula (1) Amidimide compounds are better. The maleimide compound can be used alone or in combination of two or more.

In the aforementioned formula (1), R ₁ each independently represents a hydrogen atom or a methyl group, preferably a hydrogen atom. In addition, in formula (1), n ₁ represents an integer of 1 or more, and the upper limit of n ₁ is usually 10. In view of the solubility with respect to the organic solvent, it is preferably 7 and more preferably 5. The maleimide compound (A) having no siloxane bond may also be a mixture of two or more compounds with different n ₁ .

In the aforementioned formula (2), R ₂ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms (for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, Third butyl, n-pentyl, etc.), or phenyl. Among these, in view of improving the flame resistance and the peel strength of the metal foil (copper foil), it is preferably a group selected from the group consisting of a hydrogen atom, a methyl group, and a phenyl group, which is a hydrogen atom and a methyl group. Either is better, especially a hydrogen atom.

In the above formula (2), 1≦n ₂ ≦10. From the viewpoint of more excellent solvent solubility, n _{2 is} preferably 4 or less, more preferably 3 or less, and particularly preferably 2 or less. In addition, the maleimide compound (A) which does not have a siloxane bond may be a mixture of two or more compounds with different n ₂ .

In the aforementioned formula (3), R ₃ each independently represents a hydrogen atom, a methyl group or an ethyl group, and R ₄ each independently represents a hydrogen atom or a methyl group. Considering the viewpoint that low dielectric constant and low dielectric loss tangent are more excellent, R _{3 is} preferably methyl or ethyl.

The maleimide compound (A) that does not have a siloxane bond used in this embodiment can also be a commercially available product. For example, the maleimide compound represented by formula (1) can be preferably used in Yamato Chemical Industry (BMI-2300), a maleimide compound represented by formula (2), can be used ideally, "MIR-3000", a maleimide compound represented by formula (3), manufactured by Nippon Kayaku Co., Ltd. As the imine compound, "BMI-70" manufactured by Yamato Chemical Industry Co., Ltd. is preferably used.

The content of the maleimide compound (A) that does not have a siloxane bond in the resin composition of this embodiment can be appropriately set according to the desired characteristics, and is not particularly limited. Regarding the content of the maleimide compound (A) that does not have a siloxane bond, when the resin solid content in the resin composition is 100 parts by mass, it is preferably 1 part by mass or more and 5 parts by mass or more Preferably, it is more preferably 10 parts by mass or more, and may also be 15 parts by mass or more and 20 parts by mass or more. Moreover, the upper limit of the content of the maleimide compound (A) having no siloxane bond is preferably 90 parts by mass or less, more preferably 60 parts by mass or less, particularly preferably 40 parts by mass or less, or 35 parts by mass or less and 30 parts by mass or less. By setting it within the above range, high heat resistance and low water absorption tend to be more improved. In the resin composition of this embodiment, the maleimide compound (A) which does not have a siloxane bond may contain only one kind, or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

Here, "resin solid content in the resin composition" refers to components other than the solvent and the filler (D) in the resin composition unless otherwise stated, and 100 parts by mass of the resin solid content refers to the resin The total amount of components in the composition excluding the solvent and the filler (D) is 100 parts by mass.

[Unmodified cyanate compound (B)] The resin composition of this embodiment contains an unmodified cyanate compound (B). The unmodified cyanate compound (B) used in this embodiment is a compound or resin having an aromatic part substituted with at least one cyanooxy group (cyanate group) in the molecule, and in the molecule It does not have a group derived from the reaction of other functional groups (such as maleimide) other than cyanooxy, cyanoxy and phenolic hydroxyl groups. That is, "unmodified" means a group that does not have a cyanooxy group and a functional group other than cyanooxy group and phenolic hydroxyl group (such as maleimide group) in the molecule. In addition, an example of the resin composition of this embodiment is a varnish. When the varnish is used to make a prepreg or the like to semi-harden or harden the resin composition of this embodiment, part or all of the cyanooxy group may of course be combined with other cyanates. The cyanooxy group of compound (B) molecule reacts with the functional group possessed by other resin components. In addition, the unmodified cyanate compound (B) of this embodiment may contain a small amount of cyanooxy group and other cyanate compound (B) molecules of cyanide within the scope of not departing from the gist of the present invention Oxygen or the phenolic hydroxyl group of the raw material phenol compound. We believe that according to this embodiment, the resin composition contains a polymer selected from an elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends, and a polymer having a maleimide structure at both ends. At least one of the group consisting of silicone (C2), such as thermal hardening in maleimide compounds (A) without siloxane bonds and unmodified cyanate compounds (B) The reaction becomes easy. Therefore, it is speculated that even when the unmodified cyanate compound (B) is used, a high glass transition temperature can be achieved.

式(5)中，Ar₁ 各自獨立地表示亦可具有取代基之伸苯基、亦可具有取代基之伸萘基或亦可具有取代基之伸聯苯基。R₆ 各自獨立地選自於氫原子、亦可具有取代基之碳數1～6之烷基、亦可具有取代基之碳數6～12之芳基、亦可具有取代基之碳數1～4之烷氧基、碳數1～6之烷基與碳數6～12之芳基鍵結而成的亦可具有取代基之芳烷基、或碳數1～6之烷基與碳數6～12之芳基鍵結而成的亦可具有取代基之烷基芳基中之任1種。n₄ 表示鍵結於Ar₁ 之氰氧基的數目，為1～3之整數。n₅ 表示鍵結於Ar₁ 之R₆ 的數目，Ar₁ 為伸苯基時係4-n₄ ，為伸萘基時係6-n₄ ，為伸聯苯基時係8-n₄ 。n₆ 表示平均重複數，為0～50之整數。未經改性之氰酸酯化合物(B)也可為n₅ 及/或n₆ 不同的化合物之混合物。Z各自獨立地選自於單鍵、碳數1～50之2價有機基(氫原子也可取代為雜原子)、氮數1～10之2價有機基(-N-R-N-等)、羰基(-CO-)、羧基(-C(＝O)O-)、二氧化羰基(carbonyl dioxide)(-OC(＝O)O-)、磺醯基(-SO₂ -)、及2價硫原子或2價氧原子中之任1種。Examples of the unmodified cyanate compound (B) of this embodiment include those represented by the following formula (5). [Chem 5]

In Formula (5), Ar ₁ each independently represents a phenylene group which may have a substituent, a naphthyl group which may have a substituent, or a biphenylene group which may also have a substituent. R _{6 is} independently selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms that may have a substituent, an aryl group having 6 to 12 carbon atoms that may have a substituent, and 1 carbon atom that may also have a substituent ～4 alkoxy group, C 1～6 alkyl group and C 6～12 aryl group can be substituted with aralkyl group, or C 1-6 alkyl group and carbon Any one of the alkylaryl groups which may be substituted with the aryl groups of 6 to 12 may be substituted. n ₄ represents the number of cyanooxy groups bonded to Ar ₁ and is an integer of 1 to 3. n ₅ represents the number of R ₆ bonded to Ar _{1. When} Ar ₁ is phenylene, it is 4-n ₄ , when it is naphthyl, it is 6-n ₄ , and when it is biphenylene, it is 8-n ₄ . n ₆ represents the average number of repetitions and is an integer from 0 to 50. The unmodified cyanate compound (B) may also be a mixture of n ₅ and/or n ₆ different compounds. Z is independently selected from a single bond, a divalent organic group having 1 to 50 carbon atoms (a hydrogen atom may be substituted with a hetero atom), a divalent organic group having 1 to 10 nitrogen atoms (-NRN-, etc.), and a carbonyl group ( -CO-), carboxyl group (-C(=O)O-), carbonyl dioxide (-OC(=O)O-), sulfonyl group (-SO ₂ -), and divalent sulfur atom Or any one of the divalent oxygen atoms.

The alkyl group in R ₆ of formula (5) may also have a linear structure, a branched structure, or a cyclic structure (cycloalkyl group, etc.). In addition, the hydrogen atom in the alkyl group of the formula (5) and the aryl group of R ₆ may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, or a cyano group. Specific examples of alkyl groups include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tertiary butyl, n-pentyl, 1-ethylpropyl, 2,2-bis Methylpropyl, cyclopentyl, hexyl, cyclohexyl, trifluoromethyl, etc. Specific examples of aryl groups include: phenyl, xylyl, tricresyl, naphthyl, phenoxyphenyl, ethylphenyl, o-, m- or p-fluorophenyl, dichlorophenyl, dicyano Phenyl, trifluorophenyl, methoxyphenyl, o-, m- or p-tolyl, etc. Specific examples of alkoxy include methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, and third butoxy. Specific examples of the divalent organic group in Z of formula (5) include: methylene, ethylidene, trimethylene, cyclopentylidene, cyclohexylidene, trimethylcyclohexylidene, and biphenylidene Methyl, dimethylmethylene-phenylene-dimethylmethylene, stilbene, phthalidiyl, etc. The hydrogen atom in the aforementioned divalent organic group may be substituted with a halogen atom such as a fluorine atom or a chlorine atom, an alkoxy group such as a methoxy group or a phenoxy group, or a cyano group. Examples of the divalent organic group having a nitrogen number of 1 to 10 in Z of formula (5) include imine groups and polyimide groups.

式(6)中，Ar₂ 選自於伸苯基、伸萘基及伸聯苯基中之任1種。R₇ 、R₈ 、R₁₁ 、R₁₂ 各自獨立地選自於氫原子、碳數1～6之烷基、碳數6～12之芳基、以及經三氟甲基及苯酚性羥基中之至少1者取代的芳基中之任1種。R₉ 、R₁₀ 各自獨立地選自於氫原子、碳數1～6之烷基、碳數6～12之芳基、碳數1～4之烷氧基及羥基中之任1種。n₇ 表示0～5之整數，未經改性之氰酸酯化合物(B)也可為具有n₇ 不同的式(6)表示之基的化合物之混合物。 ［化7］

式(7)中，Ar₃ 選自於伸苯基、伸萘基或伸聯苯基中之任1種。R₁₃ 、R₁₄ 各自獨立地選自於氫原子、碳數1～6之烷基、碳數6～12之芳基、苄基、碳數1～4之烷氧基、以及經羥基、三氟甲基及氰氧基中之至少1者取代的芳基中之任1種。n₈ 表示0～5之整數，未經改性之氰酸酯化合物(B)也可為具有n₈ 不同的式(7)表示之基的化合物之混合物。In addition, Z in the formula (5) may include a structure represented by the following formula (6) or the following formula (7). [Chem 6]

In formula (6), Ar _{2 is} selected from any one of phenylene, naphthyl and biphenylene. R ₇ , R ₈ , R ₁₁ , and R ₁₂ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, and a trifluoromethyl group and a phenolic hydroxyl group. Any one of the aryl groups substituted by at least one. R ₉ and R ₁₀ are each independently selected from any one of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and a hydroxyl group. n ₇ represents an integer of 0 to 5, and the unmodified cyanate compound (B) may be a mixture of compounds having groups represented by formula (6) different from n ₇ . [Chem. 7]

In formula (7), Ar _{3 is} selected from any one of phenylene, naphthyl, and biphenylene. R ₁₃ and R ₁₄ are each independently selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 12 carbon atoms, a benzyl group, an alkoxy group having 1 to 4 carbon atoms, and Any one of the aryl groups substituted with at least one of fluoromethyl and cyanooxy. n ₈ represents an integer of 0 to 5, and the unmodified cyanate compound (B) may be a mixture of compounds having groups represented by formula (7) different from n ₈ .

式中，n₉ 表示4～7之整數。R₁₅ 各自獨立地表示氫原子或碳數1～6之烷基。 式(6)之Ar₂ 及式(7)之Ar₃ 之具體例可列舉：1,4-伸苯基、1,3-伸苯基、4,4’-伸聯苯基、2,4’-伸聯苯基、2,2’-伸聯苯基、2,3’-伸聯苯基、3,3’-伸聯苯基、3,4’-伸聯苯基、2,6-伸萘基、1,5-伸萘基、1,6-伸萘基、1,8-伸萘基、1,3-伸萘基、1,4-伸萘基等。式(6)之R₇ ～R₁₂ 及式(7)之R₁₃ 、R₁₄ 中之烷基及芳基和式(5)記載者同樣。In addition, Z in formula (5) may include a divalent group represented by the following formula. [Chem 8]

In the formula, n ₉ represents an integer of 4-7. R ₁₅ each independently represents a hydrogen atom or a C 1-6 alkyl group. Specific examples of Ar ₂ of formula (6) and Ar ₃ of formula (7) include: 1,4-phenylene, 1,3-phenylene, 4,4′-biphenylene, 2,4 '-Biphenylene, 2,2'-biphenylene, 2,3'-biphenylene, 3,3'-biphenylene, 3,4'-biphenylene, 2,6 -Naphthyl, 1,5-naphthyl, 1,6-naphthyl, 1,8-naphthyl, 1,3-naphthyl, 1,4-naphthyl and the like. The alkyl and aryl groups in R ₇ to R ₁₂ of formula (6) and R ₁₃ and R ₁₄ of formula (7) are the same as those described in formula (5).

Examples of the cyanate compound represented by formula (5) include phenol novolak type cyanate compounds, naphthol aralkyl type cyanate compounds, biphenyl aralkyl type cyanate compounds, and naphthyl groups Ether type cyanate compound, xylene resin type cyanate compound, adamantane skeleton type cyanate compound, bisphenol A type cyanate compound, bisphenol M type cyanate compound, diallyl bisphenol A Type cyanate compounds, etc.

、2,4-雙(N-甲基-4-氰氧基苯胺基)-6-(N-甲基苯胺基)-1,3,5-三

、雙(N-4-氰氧基-2-甲基苯基)-4,4’-氧基二鄰苯二甲醯亞胺、雙(N-3-氰氧基-4-甲基苯基)-4,4’-氧基二鄰苯二甲醯亞胺、雙(N-4-氰氧基苯基)-4,4’-氧基二鄰苯二甲醯亞胺、雙(N-4-氰氧基-2-甲基苯基)-4,4’-(六氟異亞丙基)二鄰苯二甲醯亞胺、參(3,5-二甲基-4-氰氧基苄基)異氰尿酸酯、2-苯基-3,3-雙(4-氰氧基苯基)苄甲內醯胺、2-(4-甲基苯基)-3,3-雙(4-氰氧基苯基)苄甲內醯胺、2-苯基-3,3-雙(4-氰氧基-3-甲基苯基)苄甲內醯胺、1-甲基-3,3-雙(4-氰氧基苯基)吲哚啉-2-酮、2-苯基-3,3-雙(4-氰氧基苯基)吲哚啉-2-酮、苯酚酚醛清漆樹脂或甲酚酚醛清漆樹脂(利用公知的方法使苯酚、經烷基取代之苯酚或經鹵素取代之苯酚、與福馬林或多聚甲醛等甲醛化合物在酸性溶液中反應而得者)、參苯酚酚醛清漆樹脂(使羥基苯甲醛與苯酚在酸性觸媒的存在下反應而得者)、茀酚醛清漆樹脂(使茀酮化合物與9,9-雙(羥基芳基)茀類在酸性觸媒的存在下反應而得者)、苯酚芳烷基樹脂、甲酚芳烷基樹脂、萘酚芳烷基樹脂或聯苯芳烷基樹脂(利用公知的方法使如Ar₄ -(CH₂ Z’)₂ 表示之雙鹵代甲基化合物與苯酚化合物於酸性觸媒或無觸媒之條件下反應而得者、使如Ar₄ -(CH₂ OR)₂ 表示之雙(烷氧基甲基)化合物或如Ar₄ -(CH₂ OH)₂ 表示之雙(羥基甲基)化合物與苯酚化合物在酸性觸媒的存在下反應而得者、或使芳香族醛化合物、芳烷基化合物、苯酚化合物縮聚而得者)、苯酚改性二甲苯甲醛樹脂(利用公知的方法使二甲苯甲醛樹脂與苯酚化合物在酸性觸媒的存在下反應而得者)、改性萘甲醛樹脂(利用公知的方法使萘甲醛樹脂與經羥基取代之芳香族化合物在酸性觸媒的存在下反應而得者)、苯酚改性二環戊二烯樹脂、具有聚伸萘基醚結構之酚醛樹脂(利用公知的方法使1分子中具有2個以上之苯酚性羥基的多元羥基萘化合物在鹼性觸媒的存在下進行脫水縮合而得者)等將酚醛樹脂利用與上述同樣之方法予以氰酸酯化而得者等，並無特別限制。該等氰酸酯化合物可單獨使用，亦可將2種以上倂用。Specific examples of the cyanate ester compound represented by formula (5) include: cyanoxybenzene, 1-cyanoxy-2-, 1-cyanoxy-3-, or 1-cyanoxy-4-methyl Benzene, 1-cyanoxy-2-, 1-cyanoxy-3-, or 1-cyanoxy-4-methoxybenzene, 1-cyanoxy-2,3-, 1-cyanoxy -2,4-, 1-cyanooxy-2,5-, 1-cyanooxy-2,6-, 1-cyanooxy-3,4- or 1-cyanooxy-3,5-di Methylbenzene, cyanoxyethylbenzene, cyanoxybutylbenzene, cyanoxyoctylbenzene, cyanoxynonylbenzene, 2-(4-cyanooxyphenyl)-2-phenylpropane ( 4-α-cumyl phenol cyanate), 1-cyanoxy-4-cyclohexylbenzene, 1-cyanoxy-4-vinylbenzene, 1-cyanoxy-2- or 1- Cyanoxy-3-chlorobenzene, 1-cyanoxy-2,6-dichlorobenzene, 1-cyanoxy-2-methyl-3-chlorobenzene, cyanoxynitrobenzene, 1-cyanooxy 4-Nitro-2-ethylbenzene, 1-cyano-2-methoxy-4-allylbenzene (cyanate of eugenol), methyl (4-cyanophenyl ) Thioether, 1-cyanooxy-3-trifluoromethylbenzene, 4-cyanooxybiphenyl, 1-cyanooxy-2- or 1-cyanooxy-4-ethyl benzene, 4- Cyanoxybenzaldehyde, methyl 4-cyanoxybenzoate, phenyl 4-cyanoxybenzoate, 1-cyanoxy-4-ethylaminoaminobenzene, 4-cyanoxybenzophenone , 1-cyano-2,6-di-tert-butylbenzene, 1,2-dicyanooxybenzene, 1,3-dicyanooxybenzene, 1,4-dicyanooxybenzene, 1 ,4-dicyano-2-tert-butylbenzene, 1,4-dicyano-2,4-dimethylbenzene, 1,4-dicyano-2,3,4-tricyano Methylbenzene, 1,3-dicyanooxy-2,4,6-trimethylbenzene, 1,3-dicyano-5-methylbenzene, 1-cyanooxy or 2-cyanooxy Naphthalene, 1-cyano-4-methoxynaphthalene, 2-cyano-6-methylnaphthalene, 2-cyano-7-methoxynaphthalene, 2,2'-dicyanooxy- 1,1'-binaphthalene, 1,3-, 1,4-, 1,5-, 1,6-, 1,7-, 2,3-, 2,6- or 2,7-dicyanox Naphthalene, 2,2'- or 4,4'-dicyanooxybiphenyl, 4,4'-dicyanooxyoctafluorobiphenyl, 2,4'- or 4,4'-dicyanooxy Diphenylmethane, bis(4-cyanooxy-3,5-dimethylphenyl)methane, 1,1-bis(4-cyanooxyphenyl)ethane, 1,1-bis(4- Cyanoxyphenyl)propane, 2,2-bis(4-cyanoxyphenyl)propane, 2,2-bis(3-allyl-4-cyanoxyphenyl)propane, 2,2- Bis(4-cyanooxy-3-methylphenyl)propane, 2,2-bis(2-cyanooxy-5-biphenyl)propane, 2,2-bis(4-cyanooxyphenyl ) Hexafluoropropane, 2,2-bis(4-cyanooxy-3,5-dimethylphenyl)propane, 1,1-bis(4-cyanooxyphenyl)butane, 1,1- Bis(4-cyanooxyphenyl) isobutane, 1,1-bis(4-cyanooxyphenyl) Pentane, 1,1-bis(4-cyanoxyphenyl)-3-methylbutane, 1,1-bis(4-cyanoxyphenyl)-2-methylbutane, 1,1 -Bis(4-cyanooxyphenyl)-2,2-dimethylpropane, 2,2-bis(4-cyanooxyphenyl)butane, 2,2-bis(4-cyanooxybenzene Group) pentane, 2,2-bis(4-cyanooxyphenyl)hexane, 2,2-bis(4-cyanooxyphenyl)-3-methylbutane, 2,2-bis( 4-cyanophenyl)-4-methylpentane, 2,2-bis(4-cyanooxyphenyl)-3,3-dimethylbutane, 3,3-bis(4-cyano Oxyphenyl)hexane, 3,3-bis(4-cyanooxyphenyl)heptane, 3,3-bis(4-cyanooxyphenyl)octane, 3,3-bis(4- Cyanoxyphenyl)-2-methylpentane, 3,3-bis(4-cyanoxyphenyl)-2-methylhexane, 3,3-bis(4-cyanoxyphenyl) -2,2-dimethylpentane, 4,4-bis(4-cyanoxyphenyl)-3-methylheptane, 3,3-bis(4-cyanoxyphenyl)-2- Methylheptane, 3,3-bis(4-cyanooxyphenyl)-2,2-dimethylhexane, 3,3-bis(4-cyanooxyphenyl)-2,4-bis Methylhexane, 3,3-bis(4-cyanooxyphenyl)-2,2,4-trimethylpentane, 2,2-bis(4-cyanooxyphenyl)-1,1 ,1,3,3,3-hexafluoropropane, bis(4-cyanooxyphenyl)phenylmethane, 1,1-bis(4-cyanooxyphenyl)-1-phenylethane, bis (4-cyanoxyphenyl)biphenylmethane, 1,1-bis(4-cyanoxyphenyl)cyclopentane, 1,1-bis(4-cyanoxyphenyl)cyclohexane, 2 ,2-bis(4-cyanooxy-3-isopropylphenyl)propane, 1,1-bis(3-cyclohexyl-4-cyanooxyphenyl)cyclohexane, bis(4-cyanooxy Phenyl)diphenylmethane, bis(4-cyanooxyphenyl)-2,2-dichloroethylene, 1,3-bis[2-(4-cyanooxyphenyl)-2-propyl ]Benzene, 1,4-bis[2-(4-cyanooxyphenyl)-2-propyl]benzene, 1,1-bis(4-cyanooxyphenyl)-3,3,5-tri Methylcyclohexane, 4-[bis(4-cyanooxyphenyl)methyl]biphenyl, 4,4-dicyanooxybenzophenone, 1,3-bis(4-cyanooxybenzene Yl)-2-propen-1-one, bis(4-cyanooxyphenyl) ether, bis(4-cyanooxyphenyl) sulfide, bis(4-cyanooxyphenyl) sulfone, 4- Cyanoxybenzoic acid-4-cyanoxyphenyl ester (4-cyanoxyphenyl-4-cyanoxybenzoate), bis-(4-cyanoxyphenyl) carbonate, 1,3 -Bis(4-cyanooxyphenyl)adamantane, 1,3-bis(4-cyanooxyphenyl)-5,7-dimethyladamantane, 3,3-bis(4-cyanooxy Phenyl) m-benzofuran-1(3H)-one (phenolphthalein cyanate), 3,3-bis(4-cyanooxy-3-methylphenyl) m-benzofuran-1(3H) -Ketone (cyanate of o-cresolphthalein), 9,9-bis(4-cyanooxyphenyl) stilbene, 9,9 -Bis(4-cyanoxy-3-methylphenyl) stilbene, 9,9-bis(2-cyanoxy-5-biphenyl) stilbene, ginseng (4-cyanoxyphenyl)methane, 1,1,1-ginseng (4-cyanoxyphenyl)ethane, 1,1,3-ginseng (4-cyanoxyphenyl)propane, α,α,α'-ginseng (4-cyanooxy Phenyl)-1-ethyl-4-cumene, 1,1,2,2-(4-cyanooxyphenyl)ethane, (4-cyanophenyl)methane, 2 ,4,6-ginseng (N-methyl-4-cyanooxyanilino)-1,3,5-tris

, 2,4-bis(N-methyl-4-cyanooxyanilinyl)-6-(N-methylanilinyl)-1,3,5-tri

, Bis(N-4-cyanooxy-2-methylphenyl)-4,4'-oxydiphthalimide, bis(N-3-cyanooxy-4-methylbenzene Group)-4,4'-oxydiphthalimide, bis(N-4-cyanooxyphenyl)-4,4'-oxydiphthalimide, bis( N-4-cyanooxy-2-methylphenyl)-4,4'-(hexafluoroisopropylidene) diphthalimide, ginseng (3,5-dimethyl-4- Cyanoxybenzyl)isocyanurate, 2-phenyl-3,3-bis(4-cyanooxyphenyl)benzyllactam, 2-(4-methylphenyl)-3, 3-bis(4-cyanooxyphenyl)benzylmethanamide, 2-phenyl-3,3-bis(4-cyanooxy-3-methylphenyl)benzylmethanamide, 1- Methyl-3,3-bis(4-cyanooxyphenyl) indoline-2-one, 2-phenyl-3,3-bis(4-cyanooxyphenyl) indoline-2- Ketone, phenol novolak resin or cresol novolak resin (using known methods to react phenol, alkyl-substituted phenol or halogen-substituted phenol, and formalin or paraformaldehyde and other formaldehyde compounds in acidic solution ), phenol phenol novolak resin (the one obtained by reacting hydroxybenzaldehyde and phenol in the presence of an acid catalyst), phenol phenol novolak resin (the one obtained by making a stilbene compound and 9,9-bis(hydroxyaryl) stilbene Obtained by reacting in the presence of an acid catalyst), phenol aralkyl resin, cresol aralkyl resin, naphthol aralkyl resin or biphenyl aralkyl resin (using known methods such as Ar ₄ -( CH ₂ Z') ₂ represents a dihalomethyl compound and a phenol compound reacted under acidic catalyst or catalyst-free conditions, such as Ar ₄ -(CH ₂ OR) ₂ represented by bis(alkoxy Methyl group) compounds or bis(hydroxymethyl) compounds represented by Ar ₄ -(CH ₂ OH) ₂ and phenol compounds in the presence of an acid catalyst, or the aromatic aldehyde compound, aralkyl group Compounds, phenol compounds obtained by polycondensation), phenol-modified xylene formaldehyde resins (obtained by using known methods to react xylene formaldehyde resins and phenol compounds in the presence of acidic catalysts), modified naphthalene formaldehyde resins (utilized A well-known method is obtained by reacting a naphthalene formaldehyde resin with a hydroxy-substituted aromatic compound in the presence of an acid catalyst), a phenol-modified dicyclopentadiene resin, a phenol resin with a polynaphthyl ether structure (utilization A well-known method is obtained by dehydrating and condensing a polyhydric hydroxynaphthalene compound having two or more phenolic hydroxyl groups in one molecule in the presence of an alkaline catalyst), etc. The phenol resin is cyanated by the same method as above There are no special restrictions for the winners. These cyanate compounds can be used alone or in combination of two or more.

Among them, phenol novolac type cyanate compounds, naphthol aralkyl type cyanate compounds, naphthyl ether type cyanate compounds, bisphenol A type cyanate compounds, and bisphenol M type cyanate are preferred The compound and diallyl bisphenol cyanate are particularly preferred as naphthol aralkyl cyanate compounds.

The cured product of the resin composition using these cyanate compounds has excellent characteristics such as heat resistance and low dielectric properties (low dielectric properties, low dielectric loss tangent).

The content of the unmodified cyanate compound (B) in the resin composition of this embodiment can be appropriately set according to the desired characteristics, and is not particularly limited. Regarding the content of the unmodified cyanate compound (B), when the resin solid content in the resin composition is 100 parts by mass, it is preferably 1 part by mass or more, more preferably 10 parts by mass or more, and 30 More than mass parts is particularly preferable, and it may be more than 50 mass parts. In addition, when the upper limit of the content of the unmodified cyanate compound (B) is such that the resin solid content in the resin composition is 100 parts by mass, it is preferably 90 parts by mass or less, more preferably 70 parts by mass or less . By setting it within such a range, more excellent low-dielectricity and low-tangent dielectric loss can be achieved.

[An elastomer with a styrene content of 17% by mass or more and a styrene structure at both ends (C1)] The resin composition of this embodiment contains an elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends. Such a styrene content (also called "styrene ratio") is preferable in terms of solvent solubility and compatibility with other compounds. Here, in terms of styrene content, let the mass of the styrene unit contained in the elastomer (C1) having a styrene structure at both ends be (a) g, and the entire elastomer (C1) having a styrene structure at both ends When the mass is (b)g, it is expressed as (a)/(b)×100 (unit: %). The elastomer (C1) with a styrene structure at both ends used in this embodiment usually has two ends, and when there are more than three, two of the ends may have a styrene structure, and more than 90% of the ends should have Styrene structure, it is better to have styrene structure at all ends. Examples of the elastomer (C1) having a styrene content of 17% by mass or more and a styrene structure at both ends used in the resin composition of the present embodiment include styrene-butadiene-styrene block copolymer, Styrene-isoprene-styrene block copolymer, styrene-hydrogenated butadiene-styrene block copolymer, styrene-hydrogenated isoprene-styrene block copolymer, styrene-hydrogenated (Isoprene/butadiene)-styrene block copolymer. These elastomers can be used alone or two or more types can be used. By using these elastomers, excellent low dielectric constant, excellent low dielectric loss tangent, and high glass transition temperature can be achieved at the same time.

As for the styrene structure of the elastomer (C1) having a styrene content of 17% by mass or more and having styrene structures at both ends, styrene may have a substituent. Specifically, styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene can be used.

The upper limit of the styrene content in the elastomer (C1) having a styrene content of 17% by mass or more and having styrene structures at both ends is preferably 99% by mass or less, more preferably 90% by mass or less, and 70% by mass The following is particularly preferred, which is 60% by mass or less and even better, 50% by mass or less is even better, and 45% by mass or less is even better.

The elastomer (C1) having a styrene content of 17% by mass or more and a styrene structure at both ends of the present embodiment can also be a commercially available product. For example, styrene-butadiene-styrene block copolymers include TR2630 ( (JSR (share) system), TR2003 (JSR (share) system). In addition, as the styrene-isoprene-styrene block copolymer, SIS5250 (manufactured by JSR) can be mentioned. Examples of the styrene-hydrogenated isoprene-styrene block copolymer include SEPTON 2104 (manufactured by Kuraray Co., Ltd.).

As for the content of the elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends in this embodiment, as long as the sum of the masses of (C1) and (C2) described later is relative to the resin solid content 100 The mass part is 5-25 mass parts, there is no particular limitation, considering the viewpoint of the dielectric constant, dielectric loss tangent, and peel strength of the metal foil (copper foil), (C1) is preferably 5-20 mass parts, 5-15 Excellent quality. Moreover, (C1) and (C2) can be mixed and used suitably.

[Polysilicone with maleimide structure at both ends (C2)] The polysiloxane (C2) having a maleimide structure at both ends of the present embodiment, as long as the polysiloxane structure has a maleimide structure at both ends and is a compound represented by formula (4), there is no Specially limited. By using polysilicone (C2) having a maleimide structure at both ends of the present embodiment, it is possible to improve low dielectric constant, low dielectric loss tangent, and glass transition temperature while maintaining high flame resistance.

In formula (4), R ₅ each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms, preferably an unsubstituted monovalent hydrocarbon group.

The unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbon atoms is not particularly limited, and examples include methyl, ethyl, propyl, butyl, isopropyl, isobutyl, and tertiary butyl. Alkyl such as pentyl, hexyl, heptyl, octyl, 2-ethylhexyl; vinyl, allyl, butenyl, pentenyl, hexenyl and other alkenyl; phenyl, tolyl, xylene Aryl groups such as alkyl, naphthyl and biphenyl; aralkyl groups such as benzyl and phenethyl. Among these, for industrial reasons, it is preferably methyl, ethyl, phenyl or benzyl, more preferably methyl or phenyl, especially methyl.

Formula (4), R ₅ represents all of the methyl groups in the ratio of R ₅ is 50 mole%, 65 mole% or more is desirable, on the grounds of industrial considerations, more preferably not less than 70 mole%. The upper limit is not particularly limited, and it is preferably 100 mol%, that is, all of them are preferably methyl groups.

The viewpoint of considering the solubility of the solvent and the compatibility with the aforementioned maleimide compound (A) having no siloxane bond and the unmodified cyanate compound (B), formula (4) In the formula, n ₃ represents an integer of 0 to 2. n _{3 is} preferably 0 to 1, more preferably 0. The compound represented by formula (4) may be a mixture of two or more compounds with different n ₃ .

In this embodiment, the polysiloxane (C2) having a maleimide structure at both ends can be used in the form of a powder, and can be used alone or two or more types can be used.

The production method of polysilicone (C2) having a maleimide structure at both ends is not particularly limited. For example, an acid anhydride-based compound and a siloxane compound may be mixed in an organic solvent that can dissolve these raw materials. Its reaction method. During the reaction, catalysts can also be used as needed. Also, the reaction is preferably carried out at low temperature.

The acid anhydride-based compound is not particularly limited, and examples thereof include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Methyl nadic anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, etc. Considering the industrial point of view, maleic anhydride is preferred. These acid anhydride-based compounds may be used alone or in combination of two or more.

The siloxane compound is not particularly limited, and examples include 1,3-bis(3-aminopropyl)tetramethyldisilaxane, bis(3-aminobutyl)tetramethyldisilaxane, Bis(3-aminopropyl)tetraphenyldisilaxane, bis(3-aminobutyl)tetraphenyldisilaxane, bis(4-aminophenyl)tetramethyldisilaxane , Bis(4-amino-3-methylphenyl)tetramethyldisilaxane, bis(4-aminophenyl)tetraphenyldisilaxane, etc. Considering the industrial point of view, 1,3-bis(3-aminopropyl)tetramethyldisilaxane is preferred. These siloxane compounds can be used alone or in combination of two or more.

The organic solvent is not particularly limited, and examples include dimethyl sulfone, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl -2-imidazolidinone, N-methylpyrrolidone and other aprotic polar solvents; tetramethylene stilts and other stilts; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol, propylene glycol monomethyl ether, Ether solvents such as propylene glycol monomethyl ether monoacetate and propylene glycol monobutyl ether; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; aromatic solvents such as toluene and xylene. Among them, from the viewpoint of reactivity, it is preferably an aprotic polar solvent. These organic solvents can be used alone or in combination of two or more.

The catalyst is not particularly limited, and examples include organic metal salts such as tin octoate, zinc octoate, dibutyltin dimaleate, zinc naphthenate, cobalt naphthenate, and tin oleate; zinc chloride, aluminum chloride, and chlorine Chloride and other metal chlorides. Among them, from the viewpoint of reactivity, cobalt naphthenate is preferable. These catalysts can be used alone or two or more types can be used.

The content of polysiloxane (C2) having a maleimide structure at both ends in the resin composition of the present embodiment, as long as the sum of the masses of (C1) and (C2) is relative to 100 masses of the resin solid content The part is 5 to 25 parts by mass, and is not particularly limited. (C2) is particularly preferably 10 to 20 parts by mass in view of the permittivity, dielectric loss tangent, and flame resistance. Moreover, (C1) and (C2) can be mixed and used suitably.

[Filling material (D)] The resin composition of this embodiment preferably contains a filler (D) in order to improve low dielectric constant, low dielectric loss tangent, flame resistance, and low thermal expansion. The filler (D) used in the present embodiment can be appropriately used a known one, and its type is not particularly limited, and can be preferably used by ordinary users in this field. Specific examples include natural silica, fused silica, synthetic silica, amorphous silica, silica aerosol (AEROSIL), hollow silica, and other silicas; white carbon black , Titanium white, zinc oxide, magnesium oxide, zirconium oxide, boron nitride, condensed boron nitride, silicon nitride, aluminum nitride, barium sulfate, aluminum hydroxide, aluminum hydroxide heat treatment products (heating aluminum hydroxide Treatment to remove part of the crystal water), metal hydrates such as boehmite, magnesium hydroxide, molybdenum compounds such as molybdenum oxide, zinc molybdate, zinc borate, zinc stannate, alumina, 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 Inorganic fillers such as glass, T glass, D glass, S glass, Q glass, etc.), insulating glass, spherical glass, etc. Other examples include styrene type, butadiene type, acrylic type, etc. Organic fillers such as rubber powder, core-shell type rubber powder, polysiloxane resin powder, polysiloxane rubber powder, polysiloxane composite powder, etc. These fillers can be used alone or two or more types can be used. Among these, one or more selected from the group consisting of silicon dioxide, aluminum hydroxide, boehmite, magnesium oxide, and magnesium hydroxide is preferable. By using these fillers, the thermal expansion characteristics, dimensional stability, and flame resistance of the resin composition are improved.

The content of the filler (D) in the resin composition of this embodiment can be appropriately set according to the desired characteristics, and is not particularly limited. When the resin solid content in the resin composition is 100 parts by mass, it is preferably 50 to 1600 The part by mass is more preferably 50 to 500 parts by mass, and particularly preferably 50 to 300 parts by mass. The filler (D) may be 75 to 250 parts by mass, or 100 to 200 parts by mass. By setting the content of the filler within this range, the moldability of the resin composition becomes good.

The resin composition may contain only one kind of filler (D), or two or more kinds. When two or more kinds are contained, the total amount is preferably within the above range.

Here, when the filler (D) is used, at least one selected from the group consisting of a silane coupling agent and a wetting and dispersing agent is preferably used. The silane coupling agent can be ideally used for surface treatment of inorganic substances, and its type is not particularly limited. Specific examples include: aminosilane series such as γ-aminopropyltriethoxysilane and N-β-(aminoethyl)-γ-aminopropyltrimethoxysilane; γ-epoxy Propoxypropyl trimethoxy silane, β-(3,4-epoxycyclohexyl) ethyl trimethoxy silane and other epoxy silane systems; γ-methacryl propyl propyl trimethoxy silane, ethylene Vinyl silanes such as tris(β-methoxyethoxy) silane; N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltrimethoxysilane hydrochloride Such as cationic silane series; phenyl silane series. The silane coupling agent can be used alone or in combination of two or more. In addition, the wetting and dispersing agent can be preferably used for those who are generally used for coatings, and the type is not particularly limited. It is preferable to use a copolymer-based wetting and dispersing agent. Specific examples thereof include Disperbyk-110, 111, 161, 180, 2009, 2152, BYK-W996, BYK-W9010, BYK-W903, and BYK-made by BYK Japan. W940 etc. The wetting and dispersing agent can be used alone or in combination of two or more.

The content of the silane coupling agent is not particularly limited, and may be about 1 to 5 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. The content of the dispersant (especially the wet dispersant) is not particularly limited, and may be, for example, about 0.5 to 5 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

化合物、聚苯醚化合物、苯乙烯低聚物(排除相當於(C1)者)、阻燃劑、硬化促進劑、有機溶劑等。藉由倂用該等，可改善將樹脂組成物硬化得到的硬化物之耐燃性、高金屬箔(銅箔)剝離強度、低介電性等期望之特性。 就本實施形態之樹脂組成物而言，上述不具有矽氧烷鍵之馬來醯亞胺化合物(A)以外之馬來醯亞胺化合物、上述未經改性之氰酸酯化合物(B)以外之氰酸酯化合物、上述苯乙烯含量為17質量%以上且兩末端具有苯乙烯結構之彈性體(C1)以外之彈性體、及上述兩末端具有馬來醯亞胺結構之聚矽氧(C2)以外之聚矽氧之總量，宜為樹脂固體成分之3質量%以下，為1質量%以下更佳。藉由為如此之構成，可更有效地發揮本發明之效果。[Other components] In addition, the resin composition of the present embodiment may contain males other than the maleimide compound (A) having no siloxane bond as long as the expected properties are not impaired. Amidimide compounds, cyanate compounds other than the above unmodified cyanate compound (B), elasticity other than the elastomer (C1) having a styrene content of 17% by mass or more and having styrene structures at both ends Polysiloxane, epoxy resin, phenolic resin, oxetane resin, benzo㗁 other than polysiloxane (C2) with maleimide structure at both ends

Compounds, polyphenylene ether compounds, styrene oligomers (excluding those corresponding to (C1)), flame retardants, hardening accelerators, organic solvents, etc. By using these, it is possible to improve desired characteristics such as flame resistance of the cured product obtained by curing the resin composition, high metal foil (copper foil) peel strength, and low dielectric properties. In the resin composition of this embodiment, the maleimide compound other than the above-mentioned maleimide compound (A) having no siloxane bond, and the above-mentioned unmodified cyanate compound (B) Other than the cyanate compound, the elastomer other than the elastomer having the styrene content of 17% by mass or more and having styrene structures at both ends (C1), and the polysiloxane having the maleimide structure at both ends ( C2) The total amount of polysilicon other than 3% by mass of the resin solid content is preferably less than 1% by mass. With such a structure, the effect of the present invention can be more effectively exerted.

[Epoxy resin] The epoxy resin is not particularly limited as long as it is a compound or resin having two or more epoxy groups in one molecule, and examples include bisphenol A epoxy resin, bisphenol E epoxy resin, Bisphenol F epoxy resin, bisphenol S epoxy resin, phenol novolac epoxy resin, bisphenol A novolac epoxy resin, glycidyl epoxy resin, aralkyl novolac epoxy ring Oxygen resin, biphenyl aralkyl type epoxy resin, naphthyl ether type epoxy resin, cresol novolac type epoxy resin, multifunctional phenol type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin , Naphthalene skeleton modified novolac epoxy resin, phenol aralkyl epoxy resin, naphthol aralkyl epoxy resin, dicyclopentadiene epoxy resin, biphenyl epoxy resin, alicyclic Group epoxy resin, polyol type epoxy resin, phosphorus-containing epoxy resin, glycidylamine, glycidyl ester, butadiene and other double bond epoxidized compounds, by hydroxyl-containing polysilicon Compounds obtained by the reaction of oxygen resins and epichlorohydrin. These epoxy resins can be used alone or two or more types can be used. Among these, in view of further improving flame resistance and heat resistance, biphenyl aralkyl type epoxy resin, naphthyl ether type epoxy resin, multifunctional phenol type epoxy resin, naphthalene type epoxy resin are preferable .

[Phenolic Resin] The phenol resin is not particularly limited as long as it is a compound or resin having two or more phenolic hydroxyl groups in one molecule, and examples include bisphenol A phenol resin, bisphenol E phenol resin, and bisphenol F Type phenolic resin, bisphenol S type phenolic resin, phenol novolac resin, bisphenol A novolac type phenolic resin, glycidyl ester type phenolic resin, aralkyl novolac phenolic resin, biphenyl aralkyl type phenolic resin, Cresol novolac phenolic resin, multifunctional phenolic resin, naphthol resin, naphthol novolac resin, multifunctional naphthol resin, anthracene phenolic resin, naphthalene skeleton modified novolac phenolic resin, phenol aralkyl phenolic resin Resin, naphthol aralkyl type phenolic resin, dicyclopentadiene type phenolic resin, biphenyl type phenolic resin, alicyclic phenolic resin, polyol type phenolic resin, phosphorus-containing phenolic resin, hydroxyl-containing polysiloxane Resin etc. These phenolic resins can be used alone or two or more types can be used. Among these, in view of further improving the flame resistance, it is preferably selected from the group consisting of biphenyl aralkyl phenol resin, naphthol aralkyl phenol resin, phosphorus-containing phenol resin, and hydroxyl-containing polysiloxane resin At least one of the group.

[Oxetane Resin] The oxetane resin is not particularly limited, and examples thereof include oxetane, alkyloxetane (for example, 2-methyloxetane, 2,2-dimethyloxane (Cyclobutane, 3-methyloxetane, 3,3-dimethyloxetane, etc.), 3-methyl-3-methoxymethyloxetane, 3,3 -Di(trifluoromethyl)perfluorooxetane, 2-chloromethyloxetane, 3,3-bis(chloromethyl)oxetane, biphenyl oxetane Alkanes, OXT-101 (East Asian synthetic products), OXT-121 (East Asian synthetic products), etc. These oxetane resins can be used alone or in combination of two or more.

化合物］ 就苯并㗁

化合物而言，只要是1分子中具有2個以上之二氫苯并㗁

環的化合物，則無特別限定，例如可列舉雙酚A型苯并㗁

BA-BXZ(小西化學(股)製品)、雙酚F型苯并㗁

BF-BXZ(小西化學(股)製品)、雙酚S型苯并㗁

BS-BXZ(小西化學(股)製品)等。該等苯并㗁

化合物可單獨使用，亦可將2種以上倂用。[Benzo㗁

Compound] Benzene

As far as the compound is concerned, as long as it has two or more dihydrobenzobenzenes in one molecule

The ring compound is not particularly limited, and examples thereof include bisphenol A-type benzoxanthene

BA-BXZ (Xiaoxi Chemical Co., Ltd. product), bisphenol F-type benzo㗁

BF-BXZ (Xiaoxi Chemical Co., Ltd. product), bisphenol S type benzo㗁

BS-BXZ (Xiaoxi Chemical Co., Ltd. products), etc. Benzo

The compounds can be used alone or in combination of two or more.

式(8)中，R₁₆ 、R₁₇ 、R₁₈ 、及R₁₉ 各自獨立地表示碳數6以下之烷基、芳基、鹵素原子、或氫原子。 前述化合物亦可更含有選自由式(9)表示之結構、及式(10)表示之結構構成之群組中之至少1種： ［化10］

式(9)中，R₂₀ 、R₂₁ 、R₂₂ 、R₂₆ 、R₂₇ 各自獨立地表示碳數6以下之烷基或苯基。R₂₃ 、R₂₄ 、R₂₅ 各自獨立地表示氫原子、碳數6以下之烷基或苯基。 ［化11］

式(10)中，R₂₈ 、R₂₉ 、R₃₀ 、R₃₁ 、R₃₂ 、R₃₃ 、R₃₄ 、R₃₅ 各自獨立地表示氫原子、碳數6以下之烷基或苯基。-A-為碳數20以下之直鏈狀、分支狀或環狀之2價烴基。[Polyphenylene ether compound] For the polyphenylene ether compound, a compound containing a polymer of the structural unit represented by formula (8) can be used: [Chem 9]

In formula (8), R ₁₆ , R ₁₇ , R ₁₈ , and R ₁₉ each independently represent an alkyl group having 6 or less carbon atoms, an aryl group, a halogen atom, or a hydrogen atom. The aforementioned compound may further contain at least one selected from the group consisting of the structure represented by formula (9) and the structure represented by formula (10): [Chem. 10]

In formula (9), R ₂₀ , R ₂₁ , R ₂₂ , R ₂₆ , and R ₂₇ each independently represent an alkyl group or a phenyl group having 6 or less carbon atoms. R ₂₃ , R ₂₄ and R ₂₅ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms or a phenyl group. [Chem. 11]

In formula (10), R ₂₈ , R ₂₉ , R ₃₀ , R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , and R ₃₅ each independently represent a hydrogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group. -A- is a linear, branched or cyclic divalent hydrocarbon group with a carbon number of 20 or less.

As for the polyphenylene ether compound, a part or all of the terminal can also be given by ethylenic unsaturated groups such as vinylbenzyl group, epoxy group, amine group, hydroxyl group, mercapto group, carboxyl group, methacrylic group and silyl group etc. Functionalized modified polyphenylene ether. These can be used alone or in combination of two or more. Examples of modified polyphenylene ethers having hydroxyl groups at the end include SA90 manufactured by SABIC Innovative Plastics. In addition, the modified polyphenylene ether having a methacrylic group at the end includes, for example, SA9000 manufactured by SABIC Innovative Plastics.

The method for producing the modified polyphenylene ether is not particularly limited as long as the effect of the present invention can be obtained. For example, it can be manufactured by the method described in Japanese Patent No. 4591665.

The modified polyphenylene ether preferably contains a modified polyphenylene ether having an ethylenically unsaturated group at the terminal. Examples of the ethylenically unsaturated group include vinyl groups, allyl groups, acrylic groups, methacrylic groups, propenyl groups, butenyl groups, hexenyl groups, and octenyl groups. Alkenyl aryl groups such as cycloalkenyl such as hexenyl, vinyl benzyl and vinyl naphthyl are preferably vinyl benzyl. The terminal ethylenic unsaturated group may be one or more types, and may be the same functional group or different functional groups.

式(11)中，X表示芳基(芳香族基)，-(Y-O)n₁₀ -表示聚苯醚部分。R₃₆ 、R₃₇ 、R₃₈ 各自獨立地表示氫原子、烷基、烯基或炔基，n₁₀ 表示1～100之整數，n₁₁ 表示1～6之整數，n₁₂ 表示1～4之整數。宜為n₁₁ 係1以上且4以下之整數，更佳為n₁₁ 係1或2，理想為n₁₁ 係1。又，宜為n₁₂ 係1以上且3以下之整數，更佳為n₁₂ 係1或2，理想為n₁₂ 係2。 也可為n₁₀ 、n₁₁ 及n₁₂ 中之至少1者不同的2種以上之化合物之混合物。As for the modified polyphenylene ether having an ethylenically unsaturated group at the end, the compound represented by formula (11) may be cited; [Chem 12]

In formula (11), X represents an aryl group (aromatic group), and -(YO)n ₁₀ -represents a polyphenylene ether moiety. R ₃₆ , R ₃₇ and R ₃₈ each independently represent a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, n ₁₀ represents an integer from 1 to 100, n ₁₁ represents an integer from 1 to 6 and n ₁₂ represents an integer from 1 to 4 . It is preferably an integer of n ₁₁ series 1 or more and 4 or less, more preferably n ₁₁ series 1 or 2, and ideally n ₁₁ series 1. Furthermore, it is preferably an integer of n ₁₂ series 1 or more and 3 or less, more preferably n ₁₂ series 1 or 2, and ideally n ₁₂ series 2. It may be a mixture of two or more compounds in which at least one of n ₁₀ , n ₁₁ and n ₁₂ is different.

Examples of the aryl group represented by X in formula (11) include one obtained by removing n ₁₂ hydrogen atoms from one ring structure selected from the group consisting of benzene ring structure, biphenyl structure, indene ring structure, and naphthalene ring structure. The radical (for example, phenyl, biphenyl, indenyl, and naphthyl) is preferably biphenyl. Here, the aryl group represented by X may also include a diphenyl ether group obtained by bonding the aryl group with an oxygen atom, a benzophenone group obtained by bonding the aryl group with a carbonyl group, and the aryl group 2,2-diphenylpropane and the like obtained by alkylene bonding. In addition, the aryl group may be substituted with a general substituent such as an alkyl group (ideally an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group), an alkenyl group, an alkynyl group, and a halogen atom. However, the aforementioned "aryl group" is substituted with a polyphenylene ether moiety through an oxygen atom, so the limit of the number of general substituents depends on the number of polyphenylene ether moieties.

The polyphenylene ether portion in formula (11) may use the structural unit represented by formula (8), (9), or (10), and particularly preferably contains the structural unit represented by formula (8).

In addition, the number average molecular weight of the modified polyphenylene ether represented by formula (11) is preferably 1,000 or more and 7,000 or less. In addition, in formula (11), those with a minimum melt viscosity of 50,000 Pa·s or less can be used. In particular, in formula (11), the number average molecular weight is preferably 1,000 or more and 7,000 or less, and the lowest melt viscosity is 50,000 Pa·s or less. The number average molecular weight is measured using a gel permeation chromatography according to a conventional method. The number average molecular weight is preferably 1,000 to 3,000. By setting the number average molecular weight to be 1,000 or more and 7,000 or less, the effect of achieving both formability and electrical characteristics (low dielectric constant, low dielectric loss tangent) can be more effectively exerted. The lowest melt viscosity is measured using a dynamic viscoelasticity measuring device according to a conventional method. The lowest melt viscosity is better from 500 to 50,000 Pa･s. By setting the minimum melt viscosity to 50,000 Pa·s or less, it is possible to more effectively achieve the effect of taking into account the formability and electrical characteristics.

式(12)中，X為芳基(芳香族基)，-(Y-O)_n13 -各自獨立地表示聚苯醚部分，n₁₃ 各自獨立地表示1～100之整數。 X係式(11)之X中之2價基，除此以外為同義。連接基-(Y-O)_n13 -與式(11)中之-(Y-O)_n10 -為同義。又，式(12)表示之化合物也可為X或n₁₃ 不同的2種以上之化合物之混合物。As for the modified polyphenylene ether, among the compounds represented by the formula (11), the compounds represented by the following formula (12) are preferable. [Chem. 13]

In formula (12), X is an aryl group (aromatic group), -(YO) _n13 -each independently represents a polyphenylene ether moiety, and n ₁₃ each independently represents an integer of 1 to 100. X is a divalent group in X of formula (11), and is synonymous otherwise. The _linker- (YO) _n13 -is synonymous _with- (YO) _n10 -in formula (11). In addition, the compound represented by the formula (12) may be a mixture of two or more compounds with different X or n ₁₃ .

X in formula (11) and formula (12) is formula (13), formula (14), or formula (15),-(YO)n ₁₀ -in formula (11) and-in formula (12)- (YO)n ₁₃ -It is a structure in which formula (16) or formula (17) is arranged, or a structure in which formula (16) and formula (17) are randomly arranged is better.

[Chem. 14]

式(14)中，R₃₉ 、R₄₀ 、R₄₁ 及R₄₂ 各自獨立地表示氫原子或甲基。-B-為碳數20以下之直鏈狀、分支狀或環狀之2價烴基。[Chem. 15]

In formula (14), R ₃₉ , R ₄₀ , R ₄₁ and R ₄₂ each independently represent a hydrogen atom or a methyl group. -B- is a linear, branched or cyclic divalent hydrocarbon group with a carbon number of 20 or less.

式(15)中，-B-為碳數20以下之直鏈狀、分支狀或環狀之2價烴基。[Chem 16]

In formula (15), -B- is a linear, branched, or cyclic divalent hydrocarbon group having 20 or less carbon atoms.

[Chem. 17]

[Chem. 18]

The method for producing the modified polyphenylene ether having the structure represented by formula (12) is not particularly limited, and for example, a difunctional phenylene ether oligomer obtained by oxidatively coupling a difunctional phenol compound and a monofunctional phenol compound The terminal phenolic hydroxyl group is produced by etherification of vinyl benzyl. In addition, as such modified polyphenylene ether, a commercially available product can be used, for example, OPE-2St1200 and OPE-2st2200 manufactured by Mitsubishi Gas Chemical Co., Ltd. can be preferably used.

[Styrene oligomer] The styrene oligomer is different from the elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends. The styrene oligomer is obtained by polymerizing any one or more of the group consisting of styrene, styrene derivatives, and vinyl toluene. The average molecular weight of the coefficient is 178 to 1600, and the average number of aromatic rings is 2 to 14. The compound with an aromatic ring number of 2 to 14 is 50% by mass or more and has a branching structure with a boiling point of 300°C or more. The styrene derivatives specifically refer to styrene derivatives such as α-methylstyrene, 3-methylstyrene, 4-propylstyrene, and 4-cyclohexylstyrene.

Examples of styrene oligomers include styrene polymers, vinyl toluene polymers, α-methylstyrene polymers, vinyl toluene-α-methylstyrene polymers, and styrene-α- Styrene polymer, etc. Commercial products can also be used for the styrene polymer, for example, Piccolastic A5 (manufactured by Eastman Chemical), Piccolastic A-75 (manufactured by Eastman Chemical), Piccotex 75 (manufactured by Eastman Chemical), FTR-8100 (Mitsui Chemical ( Co., Ltd.), FTR-8120 (Mitsui Chemical Co., Ltd.). The vinyl toluene-α-methylstyrene polymer may be Piccotex LC (manufactured by Eastman Chemical Co., Ltd.). Examples of the α-methylstyrene polymer include Kristalex 3070 (manufactured by Eastman Chemical), Kristalex 3085 (manufactured by Eastman Chemical), Kristalex (3100), Kristalex 5140 (manufactured by Eastman Chemical), and FMR-0100 (Mitsui Chemical (Stock) system), FMR-0150 (Mitsui Chemicals (stock) system). In addition, examples of the styrene-α-styrene polymer include FTR-2120 (Mitsui Chemical Co., Ltd.). These styrene oligomers can be used alone or in combination of two or more.

Considering the viewpoint of low dielectric constant, low dielectric loss tangent and chemical resistance, the content of styrene oligomer is preferably 1 to 30 parts by mass relative to 100 parts by mass of the resin solid content of the resin composition, which is 5 ~15 parts by mass is particularly good.

[Flame retardant] Known flame retardants can be used, and examples include brominated epoxy resin, brominated polycarbonate, brominated polystyrene, brominated styrene, brominated phthalimide, and tetrabromobisphenol A. , Pentabromobenzyl (meth)acrylate, pentabromotoluene, tribromophenol, hexabromobenzene, decabromodiphenyl ether, bis-1,2-pentabromophenylethane, chlorinated polystyrene, chlorinated Halogen flame retardants such as paraffin wax; red phosphorus, tricresyl phosphate, triphenyl phosphate, toluene diphenyl phosphate, tricresyl phosphate, trialkyl phosphate, dialkyl phosphate, ginseng phosphate (chloroethyl phosphate Group) ester, phosphazene, 1,3-phenylene bis(2,6-bis(xylene) phosphate), 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10 -Phosphorus phenanthrene-10-oxide and other phosphorus-based flame retardants; aluminum hydroxide, magnesium hydroxide, some boehmite, boehmite, zinc borate, antimony trioxide and other inorganic flame retardants; polysiloxane rubber , Polysiloxane resin and other polysiloxane-based flame retardants. These flame retardants can be used alone or in combination of two or more. Among these, 1,3-benzyl bis(2,6-bis(xylene) phosphate) should be considered in terms of not easily damaging and low dielectric properties. The phosphorus content in the resin composition is preferably 0.1 to 5% by mass.

[Hardening accelerator] The resin composition of this embodiment may contain a hardening accelerator for appropriately adjusting the hardening speed. Examples of hardening accelerators include those commonly used as hardening accelerator users of maleimide compounds, cyanate ester compounds, epoxy resins, etc., and organic metal salts (for example, zinc octoate, naphthenic acid) Zinc, cobalt naphthenate, copper naphthenate, iron acetone, nickel octoate, manganese octoate, etc.), phenol compounds (for example, phenol, xylenol, cresol, resorcinol, catechol, octyl Phenol, nonylphenol, etc.), alcohols (for example, 1-butanol, 2-ethylhexanol, etc.), imidazoles (for example, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2- Phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, etc.), derivatives of such imidazole carboxylic acids or their anhydrides, amines (for example, dicyandiamide ), benzyldimethylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), phosphorus compounds (for example, phosphine compounds, phosphine oxide compounds, phosphonium salt compounds, diphosphine compounds Etc.), epoxy-imidazole adducts, peroxides (for example, benzoyl peroxide, p-chlorobenzoyl peroxide, di-tertiary butyl peroxide, diisopropyl carbonate) , Di-2-ethylhexyl peroxycarbonate, etc.), azo compounds (for example, azobisisobutyronitrile, etc.). The hardening accelerator may be used alone, or two or more types may be used.

The content of the hardening accelerator is usually about 0.005 to 10 parts by mass with respect to 100 parts by mass of the resin solid content in the resin composition.

The resin composition of this embodiment may contain various polymer compounds and various additives such as thermosetting resins, thermoplastic resins, and oligomers other than the above components. Additives can be exemplified by ultraviolet absorbers, antioxidants, photopolymerization initiators, fluorescent whitening agents, light sensitizers, dyes, pigments, tackifiers, flow regulators, lubricants, defoamers, dispersants, additives Flat agent, gloss agent, polymerization inhibitor, etc. These additives can be used alone or in combination of two or more.

[Organic solvents] The resin composition of this embodiment may contain an organic solvent. At this time, the resin composition of the present embodiment is at least a part of the above-mentioned various resin components, and it is preferably a form (solution or varnish) in which all of them are dissolved in or compatible with the organic solvent. The organic solvent is not particularly limited as long as it is a polar organic solvent or a nonpolar organic solvent in which at least a part of the above various resin components can be dissolved or compatible, and examples of the polar organic solvent include, for example, : Ketones (for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), celluloids (for example, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, etc.), esters (for example, ethyl lactate, Methyl acetate, ethyl acetate, butyl acetate, isoamyl acetate, methyl methoxypropionate, methyl hydroxyisobutyrate, etc.), amides (for example, dimethoxyacetamide, dimethyl Carboxamides, etc.), as non-polar organic solvents, aromatic hydrocarbons (for example, toluene, xylene, etc.) may be mentioned. These organic solvents can be used alone or in combination of two or more.

[Resin composition] The resin composition of this embodiment can be prepared according to an ordinary method, as long as the maleimide compound (A), unmodified cyanate compound (B), which does not contain a siloxane bond, can be uniformly contained, At least one kind selected from the group consisting of an elastomer (C1) having a styrene content of 17% by mass or more and having a styrene structure at both ends, and a polysiloxane (C2) having a maleimide structure at both ends. And the method of adding the resin composition of the other optional components as required, the preparation method is not particularly limited. For example, by combining a maleimide compound (A) that does not have a siloxane bond, an unmodified cyanate compound (B), and a styrene content of 17% by mass or more and having both ends At least one of the group consisting of a styrene-structured elastomer (C1) and a polysiloxane (C2) having a maleimide structure at both ends is blended into the solvent in order and fully stirred, which can be easily stirred The resin composition of this embodiment is prepared.

For the resin composition of this embodiment, the maleimide compound (A) having no siloxane bond, unmodified cyanate compound (B), elastomer (C1), and polysilicon The mass of oxygen (C2) should preferably account for 90% by mass or more of the resin solid content contained in the resin composition, preferably 95% by mass or more, or 98% by mass or more.

[use] The resin composition of this embodiment can be suitably used as an insulating layer of a printed wiring board and a material for a semiconductor package. The resin composition of the present embodiment can be preferably used as a material constituting a prepreg, a metal foil-clad laminate using a prepreg, a resin sheet, and a printed wiring board.

[Prepreg] The prepreg system of this embodiment is formed of a base material and the resin composition of this embodiment. The prepreg of this embodiment can be obtained, for example, by impregnating or coating the resin composition of this embodiment on a substrate and then semi-hardening it by drying at 120 to 220°C for about 2 to 15 minutes. At this time, the adhesion amount of the resin composition to the substrate, that is, the amount of the resin composition (including the filler (D).) is preferably 20 to 99% by mass relative to the total amount of the semi-hardened prepreg. Scope.

The substrate is not particularly limited as long as it is used for various printed wiring board materials. Examples of the material of the substrate include glass fiber (for example, E-glass, D-glass, L-glass, S-glass, T-glass, Q-glass, UN-glass, NE-glass, and spherical glass) Etc.), inorganic fibers other than glass (for example, quartz, etc.), organic fibers (for example, polyimide, polyamide, polyester, liquid crystal polyester, polytetrafluoroethylene, etc.). The form of the base material is not particularly limited, and examples thereof include woven fabric, non-woven fabric, roving, cut strand felt, and surface felt. These substrates can be used alone or two or more types can be used. Among these substrates, the viewpoint of dimensional stability is preferably a woven fabric subjected to super open fiber treatment and pore clogging treatment, and the viewpoint of strength and water absorption is considered. The substrate is preferably a thickness of 200 μm or less and a mass of 250 g The glass woven fabric with a surface area of less than /m ^{2 is} preferably a glass woven fabric subjected to surface treatment with a silane coupling agent, such as epoxy silane treatment, aminosilane treatment, etc. in consideration of moisture absorption and heat resistance. In view of electrical characteristics, a low-dielectric glass cloth composed of glass fibers such as L-glass, NE-glass, and Q-glass that exhibits low dielectric properties and low dielectric loss tangent is better.

[Metal foil-clad laminate] The metal foil-clad laminate of this embodiment includes at least one or more prepregs of this embodiment that overlap each other, and metal foils disposed on one or both sides of the prepreg . The metal foil-clad laminate of this embodiment includes, for example, a method of stacking at least one or more prepregs of this embodiment, disposing metal foil on one or both sides, and performing lamination molding. It can be produced by arranging metal foils such as copper and aluminum on one side or both sides and laminating them. The metal foil is not particularly limited as long as it is used as a material for printed wiring boards, and examples include copper foil such as rolled copper foil and electrolytic copper foil. The thickness of the metal foil (copper foil) is not particularly limited, and may be about 1.5 to 70 μm. Examples of the molding method include methods generally used for molding laminated and multilayer boards for printed wiring boards, and more detailed examples include the use of multi-layer laminators, multi-layer vacuum presses, continuous molding machines, and autoclaves. A molding machine or the like is a method of lamination molding under conditions of a temperature of about 180 to 350°C, a heating time of about 100 to 300 minutes, and a surface pressure of about 20 to 100 kg/cm ² . In addition, by combining the prepreg of the present embodiment and a wiring board for an inner layer prepared separately and laminating and molding, a multilayer board can also be produced. As for the manufacturing method of the multilayer board, for example, by arranging a metal foil (copper foil) of about 35 μm on both sides of one prepreg of the present embodiment, lamination is formed by the above-mentioned forming method, and then an inner layer circuit is formed, The circuit is blackened to form an inner layer circuit board, and then the inner layer circuit board and the prepreg of the present embodiment are alternately arranged one by one, and a metal foil (copper foil) is further arranged on the outermost layer, Under the above conditions, it is preferable to form a multilayer board by laminating under vacuum. The metal foil-clad laminate of this embodiment can be preferably used as a printed wiring board.

[Printed wiring board] The printed wiring board of this embodiment includes an insulating layer and a conductor layer disposed on the surface of the insulating layer. The insulating layer includes a layer formed of the resin composition of this embodiment. Such a printed wiring board can be manufactured according to an ordinary method, and its manufacturing method is not particularly limited. The following shows an example of a method of manufacturing a printed wiring board. First, a metal foil-clad laminate such as the copper-clad laminate described above is prepared. Then, the surface of the metal foil-clad laminate is etched to form an inner layer circuit, and an inner layer substrate is produced. The surface of the inner layer circuit of the inner layer substrate is optionally subjected to surface treatment to improve the bonding strength, and then the required number of prepregs are superimposed on the surface of the inner layer circuit, and the outer layer circuit is further laminated on the outer side thereof The metal foil is heated and pressed and formed into a whole. In this way, a multi-layer laminate in which an insulating layer composed of a cured material of a base material and a thermosetting resin composition is formed between the inner layer circuit and the metal foil for the outer layer circuit is produced. Then, after the through-hole (via hole) and the via hole (via hole) are applied to the multilayer laminated board, a metal for the inner layer circuit and the outer layer circuit is formed on the wall surface of the hole The foil-plated metal film is further etched to form an outer layer circuit, thereby forming a printed circuit board.

The printed wiring board obtained in the above manufacturing example has the following structure: it has an insulating layer and a conductor layer formed on the surface of the insulating layer, and the insulating layer includes at least any one of the resin composition of the present embodiment and its cured product . That is, the prepreg of the present embodiment described above (including at least one of the base material and the resin composition of the present embodiment impregnated or coated on the base material and its hardened material), the metal-clad foil of the present embodiment described above The layer of the resin composition of the laminate (layer containing at least one of the resin composition of this embodiment and its hardened) is composed of at least any of the resin composition of this embodiment and its cured One of the insulating layers.

[Resin Sheet] The resin sheet of this embodiment includes a support and a layer formed of the resin composition of this embodiment disposed on the surface of the support. The resin sheet can be used as a build-up film or dry film solder resist. The manufacturing method of the resin sheet is not particularly limited, and examples thereof include a method of applying (coating) a solution obtained by dissolving the resin composition of the present embodiment in a solvent to a support and drying it to obtain a resin sheet.

Examples of the support used here include polyethylene films, polypropylene films, polycarbonate films, polyethylene terephthalate films, ethylene tetrafluoroethylene copolymer films, and the The organic film base material such as a mold release film and a polyimide film obtained by applying a mold release agent on the surface, conductor foils such as copper foil and aluminum foil, and plate shapes such as glass plates, SUS plates, and FRP are not particularly limited.

As for the coating method (coating method), for example, a solution obtained by dissolving the resin composition of the present embodiment in a solvent using a coating bar, die coater, blade coater, or baker applicator, etc. can be applied to a support Physical method. Furthermore, after drying, the support can be peeled or etched from the resin sheet formed by laminating the support and the resin composition, whereby a single-layer sheet (resin sheet) can also be produced. In addition, a solution obtained by dissolving the resin composition of the present embodiment described above in a solvent can be supplied into a mold having a sheet-shaped cavity, dried, etc., and formed into a sheet to obtain a support-free structure. Single layer sheet (resin sheet).

In addition, when manufacturing the single-layer sheet or the resin sheet of this embodiment, the drying conditions when removing the solvent are not particularly limited. It is considered that when the temperature is low, the resin composition is likely to have residual solvent, and when the temperature is high, the curing of the resin composition will proceed. In respect of this, it is suitable to carry out at a temperature of 20 to 200°C for 1 to 90 minutes. In addition, in the single-layer sheet or the resin sheet, the resin composition can be used in an uncured state after only drying the solvent, and if necessary, it can be used in a semi-cured (B-staged) state. In addition, the thickness of the single layer or the resin layer of the resin sheet of this embodiment can be adjusted by the solution concentration and coating thickness of the resin composition of this embodiment, and is not particularly limited. Considering that when the coating thickness becomes thicker, the solvent during drying From the standpoint of remaining easily, it is preferably 0.1 to 500 μm. [Example]

(Synthesis Example 1) Synthesis of naphthol aralkyl cyanate compound (SNCN): 300 g of 1-naphthol aralkyl resin (manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd.) (equivalent to 1.28 mol of OH group) 194.6 g (1.92 mol) of triethylamine (1.5 mol relative to 1 mol of hydroxyl group) was dissolved in 1800 g of dichloromethane, and this was used as the solution 1. 125.9 g (2.05 mol) of cyanogen chloride (1.6 mol relative to 1 mol of hydroxyl group), 293.8 g of dichloromethane, 194.5 g (1.92 mol) of 36% hydrochloric acid (1.5 mol relative to 1 mol of hydroxyl group), and water 1205.9 g. Keep the liquid temperature from -2 to -0.5°C under stirring, and inject solution 1 over 30 minutes. After the injection of solution 1 was completed, after stirring at the same temperature for 30 minutes, a solution was obtained by dissolving 65 g (0.64 mol) of triethylamine (0.5 mol relative to 1 mol of hydroxyl group) in 65 g of dichloromethane over 10 minutes (solution 2) . After the solution 2 injection was completed, the reaction was completed by stirring at the same temperature for 30 minutes. After that, the reaction solution was allowed to stand to separate the organic phase from the aqueous phase. The organic phase obtained was washed 5 times with 1300 g of water. The conductivity of the wastewater in the fifth water wash was 5 μS/cm, and it was confirmed that the ionic compounds to be removed can be sufficiently removed by washing with water. The organic phase after washing with water was concentrated under reduced pressure, and finally concentrated and dried at 90°C for 1 hour to obtain 331 g of the desired naphthol aralkyl cyanate compound (SNCN) (orange sticky substance). The weight average molecular weight Mw of the obtained SNCN was 600. Moreover, the IR spectrum of SNCN showed absorption of 2250 cm ^-1 (cyanate group), and did not show absorption of hydroxyl groups.

(Synthesis Example 2) Synthesis of polysiloxane (C2) having maleimide structure at both ends represented by formula (18) In a reaction vessel equipped with a stirrer, thermometer and condenser, add 50.5 parts of maleic anhydride and 125 parts of N-methylpyrrolidone, while maintaining the temperature below 10°C, add 1,3-bismuth made by Toray-Dow Corning A solution of 15 parts of (3-aminopropyl)tetramethyldisilazane (trade name: BY16-871) dissolved in 100 parts of N-methylpyrrolidone. After the dropwise addition was completed, the reaction mixture was stirred at room temperature for 6 hours. Then, 11 parts of cobalt naphthenate and 102 parts of acetic anhydride were added to the reaction mixture, and reacted at 80°C for 4 hours.

While keeping the reaction mixture at a temperature below 5°C, 500 parts of water was added, and the deposited precipitate was separated by filtration. The obtained solid is further washed with water and dried to obtain a compound of formula (18) in formula (4) in which R _{5 is} all methyl and n ₃ is 0, namely 1,1′-((1,1,3,3 -13 parts of tetramethyldisilaxane-1,3-diyl)bis(propane-3,1-diyl))bis(1H-pyrrole-2,5-dione). The yield is 53%.

[Chem 19]

(Example 1) As a maleimide compound (A) that does not have a siloxane bond, a maleimide containing a mixture in which all R ₁ in formula (1) are hydrogen atoms and n ₁ is 1 to 3 Amine compound (BMI-2300, manufactured by Yamato Chemical Industry Co., Ltd.) 27 parts by mass, 2,2-bis(4-cyanophenyl)propane (CYTESTER) as an unmodified cyanate compound (B) (Registered trademark), manufactured by Mitsubishi Gas Chemical Co., Ltd.) 63 parts by mass of styrene-butadiene-styrene embedded as an elastomer (C1) having a styrene content of 17% by mass or more and a styrene structure at both ends Segment copolymer (TR2003, manufactured by JSR (share), styrene ratio: 40% by mass), 10 parts by mass, spherical silica (SC2050-MB, manufactured by Admatechs (share)) as filler (D), average particle size 0.5 μm) 150 parts by mass were mixed, and the solid content was diluted to 65% by mass with methyl ethyl ketone to obtain a varnish.

The obtained varnish was impregnated and coated on a low-dielectric glass cloth with a thickness of 0.069 mm, and heated and dried at 165°C for 5 minutes using a dryer (pressure-resistant explosion-proof steam dryer, manufactured by Takasugi Co., Ltd.). To obtain a prepreg with a resin composition content of 60% by mass. In a state where 1 piece and 4 pieces of the prepreg are superimposed, 12 μm copper foil (3EC-M3-VLP, manufactured by Mitsui Metal Mining Co., Ltd.) is arranged on both sides, and the pressure is 30 kg/cm ² and the temperature is 210°C. Vacuum pressing for one minute to obtain a 12 μm-coated copper laminate (metal-clad laminate) with thicknesses of 0.1 mm and 0.4 mm. The obtained copper-clad laminate was used for evaluation of dielectric constant, dielectric loss tangent, glass transition temperature, copper foil peel strength, and flame resistance. The results are shown in Table 1.

(Example 2) Using 10 parts by mass of styrene-isoprene-styrene block copolymer (SIS5250, manufactured by JSR Co., Ltd., styrene ratio 20% by mass) instead of styrene-butadiene-styrene used in Example 1 The block copolymer (TR2003, manufactured by JSR (share), styrene ratio 40% by mass) is 10 parts by mass as an elastomer (C1) having a styrene content of 17% by mass or more and a styrene structure at both ends. In the same manner as in Example 1, copper-clad laminates with thicknesses of 0.1 mm and 0.4 mm were obtained. The evaluation results of the obtained copper-clad laminates are shown in Table 1.

(Example 3) The styrene-butadiene-styrene block copolymer (TR2003, manufactured by JSR (share), styrene ratio 40% by mass) in Example 1 was not used, and 1,1'-( (1,1,3,3-tetramethyldisilaxane-1,3-diyl)bis(propane-3,1-diyl))bis(1H-pyrrole-2,5-dione)10 The mass part was polysilicone (C2) which has a maleimide structure at both ends, and it carried out similarly to Example 1, and obtained the copper-clad laminated board of thickness 0.1mm and 0.4mm. The evaluation results of the obtained copper-clad laminates are shown in Table 2.

(Example 4) In the formula (1) which is a maleimide compound (A) which does not have a siloxane bond, all of R ₁ is a hydrogen atom and n ₁ is 1 to 3 of a maleimide compound ( BMI-2300, manufactured by Daiwa Chemical Industry Co., Ltd.) 28.5 parts by mass and 66.5 parts by mass of SNCN obtained as Synthesis Example 1 of the unmodified cyanate compound (B), with a styrene content of 17% by mass or more 5 parts by mass of styrene-butadiene-styrene block copolymer (TR2630, JSR (share), styrene ratio 32% by mass) with an elastomer (C1) having styrene structure at both ends (D) 150 parts by mass of spherical silica (D) (SC2050-MB, manufactured by Admatechs Co., Ltd., average particle diameter 0.5 μm) was mixed, and the solid content was diluted to 65% by mass with methyl ethyl ketone to obtain a varnish. Then, it carried out similarly to Example 1, and obtained the copper clad laminated board of thickness 0.1mm and 0.4mm. The evaluation results of the obtained copper-clad laminates are shown in Table 1.

(Example 5) 27 parts by mass of BMI-2300 used in Example 4 as the maleimide compound (A) having no siloxane bond in Example 4 and 63 parts by mass as unmodified cyanic acid SNCN used in Example 4 of the ester compound (B), 10 parts by mass of TR2630 used in Example 4 of an elastomer (C1) having a styrene content of 17% by mass or more and a styrene structure at both ends After that, in the same manner as in Example 4, copper-clad laminates with thicknesses of 0.1 mm and 0.4 mm were obtained. The evaluation results of the obtained copper-clad laminates are shown in Table 1.

(Example 6) 24 parts by mass of BMI-2300 used in Example 4 as the maleimide compound (A) having no siloxane bond in Example 4 and 56 parts by mass as unmodified cyanic acid were used SNCN used in Example 4 of the ester compound (B), 20 parts by mass of TR2630 used in Example 4 of an elastomer (C1) having a styrene content of 17% by mass or more and a styrene structure at both ends After that, in the same manner as in Example 4, copper-clad laminates with thicknesses of 0.1 mm and 0.4 mm were obtained. The evaluation results of the obtained copper-clad laminates are shown in Table 1.

(Comparative Example 1) In the formula (1), which is a maleimide compound (A) that does not have a siloxane bond, R ₁ is a hydrogen atom and n ₁ is a maleimide compound (n 1 to 3). BMI-2300, manufactured by Daiwa Chemical Industry Co., Ltd.) 30 parts by mass, 2,2-bis(4-cyanophenyl)propane (CYTESTER (registered trademark) as an unmodified cyanate compound (B) ), Mitsubishi Gas Chemicals Co., Ltd.) 70 parts by mass, spherical silica (SC2050-MB, Admatechs Co., Ltd., average particle size 0.5 μm) as a filler (D), 150 parts by mass, and then mixed In the same manner as in Example 1, copper-clad laminates with thicknesses of 0.1 mm and 0.4 mm were obtained. The evaluation results of the obtained copper-clad laminates are shown in Tables 1 and 2.

(Comparative example 2) Using 70 parts by mass of SNCN obtained in Synthesis Example 1 instead of 2,2-bis(4-cyanooxyphenyl)propane (CYTESTER (registered trademark), manufactured by Mitsubishi Gas Chemical Co., Ltd.) in Comparative Example 1 as Except for the modified cyanate compound (B), the same procedure as in Comparative Example 1 was carried out to obtain copper-clad laminates with thicknesses of 0.1 mm and 0.4 mm. The evaluation results of the obtained copper-clad laminates are shown in Table 1.

(Comparative example 3) Polysiloxane (C2)1,1'-((1,1,3,3-tetramethyldisilazane with maleimide structure obtained at both ends obtained in Synthesis Example 2 in Example 3 is not used -1,3-diyl)bis(propane-3,1-diyl))bis(1H-pyrrole-2,5-dione) 10 parts by mass, and acrylic polymer (weight average molecular weight: 2900, East Asia) Except for 10 parts by mass of ARUFON (registered trademark) US-6170 manufactured by Synthetic Co., Ltd., the same procedure as in Example 3 was carried out to obtain copper-clad laminates with thicknesses of 0.1 mm and 0.4 mm. The evaluation results of the obtained copper-clad laminates are shown in Table 2.

(Comparative example 4) Polysiloxane (C2)1,1'-((1,1,3,3-tetramethyldisilazane with maleimide structure obtained at both ends obtained in Synthesis Example 2 in Example 3 is not used -1,3-diyl)bis(propane-3,1-diyl))bis(1H-pyrrole-2,5-dione) 10 parts by mass, and acrylic polymer (weight average molecular weight: 10000, East Asia) Except for 10 parts by mass of ARUFON (registered trademark) UC-3000 made by Synthetic Co., Ltd., the same procedure as in Example 3 was carried out to obtain copper-clad laminates with thicknesses of 0.1 mm and 0.4 mm. The evaluation results of the obtained copper-clad laminates are shown in Table 2.

(Comparative example 5) The styrene-butadiene-styrene block copolymer (TR2003, JSR (share)) in which the elastomer having a styrene content of 17% by mass or more and an elastomer (C1) having a styrene structure at both ends in Example 1 is not used System, the styrene ratio is 40% by mass), and styrene butadiene rubber (L-SBR-820, manufactured by Kuraray Co., Ltd., with a weight average molecular weight of 8000) of 10 parts by mass at both ends or butadiene at one end Except this, it carried out similarly to Example 1, and obtained the copper clad laminated board of thickness 0.1mm and 0.4mm. The evaluation results of the obtained copper-clad laminates are shown in Table 1.

(Comparative example 6) 21 parts by mass of BMI-2300 used in Example 4 as the maleimide compound (A) having no siloxane bond in Example 4 and 49 parts by mass as unmodified cyanic acid SNCN used in Example 4 of the ester compound (B), 30 parts by mass of TR2630 used in Example 4 of an elastomer (C1) having a styrene content of 17% by mass or more and a styrene structure at both ends After that, in the same manner as in Example 4, copper-clad laminates with thicknesses of 0.1 mm and 0.4 mm were obtained. The evaluation results of the obtained copper-clad laminates are shown in Table 1.

(Comparative example 7) The styrene-butadiene-styrene block copolymer (TR2630, manufactured by JSR (Co., Ltd.) which does not use an elastomer (C1) having a styrene content of 17% or more and a styrene structure at both ends in Example 5 is not used , Styrene rate 32% by mass) 10 parts by mass, and 10 parts by mass of styrene-isoprene-styrene block copolymer (SIS5229, manufactured by JSR (share), styrene rate 15% by mass), except this Except this, it carried out similarly to Example 5, and obtained the copper clad laminated board of thickness 0.1mm and 0.4mm. In Comparative Example 7, phase separation was observed between the components of the resin composition, and a uniform copper-clad laminate could not be obtained, so values for various physical properties could not be obtained.

(Comparative Example 8) In the formula (1), which is a maleimide compound (A) having no siloxane bond, R ₁ is a hydrogen atom and n ₁ is a maleimide compound (n 1 to 3). BMI-2300, manufactured by Daiwa Chemical Industry Co., Ltd.) 27 parts by mass, 63 parts by mass of SNCN obtained in Synthesis Example 1 of unmodified cyanate compound (B), R _{5 in} formula (4) is A ₃ corresponds to the portion of the group and n is two and the end 7 of silicon oxide having a polyethylene imine 10 parts by mass of maleic acyl, as filler (D) is a spherical silicon dioxide (D) (SC2050-MB, Admatechs ( Co., Ltd., with an average particle size of 0.5 μm) 150 parts by mass are mixed, and the solid content is diluted to 65% by mass with methyl ethyl ketone to obtain a varnish. Then, it carried out similarly to Example 1, and obtained the copper clad laminated board of thickness 0.1mm and 0.4mm. In Comparative Example 8, phase separation was observed between the components of the resin composition, and a uniform copper-clad laminate was not obtained, so the values of various physical properties could not be obtained.

[Table 1]

[Table 2]

(Measurement method and evaluation method) (1) Dielectric rate (Dk) and dielectric loss tangent (Df): Using a sample obtained by removing the copper foil of the copper clad laminate with a thickness of 0.4 mm obtained in each example and each comparative example by etching, 10 GHz was measured using a perturbation method cavity resonator (Agilent product, Agilent8722ES) The dielectric constant and dielectric loss are tangent. (2) Glass transition temperature: Using a sample obtained by removing the copper foil of the copper clad laminate with a thickness of 0.1 mm obtained in each example and each comparative example by etching, it was measured with a dynamic viscoelasticity analyzer (manufactured by TA Instruments) in accordance with JIS C6481:1996 . (3) Copper foil peel strength: Using the copper clad laminate having a thickness of 0.4 mm obtained in each example and each comparative example, the peel strength of the copper foil was measured in accordance with JIS　C6481:1996. A result of 0.5 kN/m or more is indicated as ○, and a result of less than 0.5 kN/m is indicated as ×. (4) Flame resistance: The sample obtained by removing the copper foil of the copper clad laminate with a thickness of 0.4 mm obtained in Example 3, Comparative Example 1, Comparative Example 3, and Comparative Example 4 by etching was evaluated according to the UL94 vertical combustion test method. [Industrial utilization]

As described above, the resin composition of the present invention can be widely and effectively used as, for example, electrical insulating materials, semiconductor plastic packages, sealing materials, adhesives in various applications such as electrical-electronic materials, machine tool materials, aviation materials, etc. , Laminated materials, photoresist, stacked laminated board materials, etc., can be effectively used as printed wiring board materials for information terminal equipment and communication equipment in recent years in response to high integration and high density. In addition, the laminate and metal-clad laminate of the present invention, in particular, can simultaneously achieve excellent low dielectric properties, low dielectric loss tangent, high glass transition temperature, and high copper foil peel strength, so their industrial The practicality is extremely high.

From Table 1, it can be confirmed that by using the resin composition of the present invention, it is possible to achieve a prepreg with excellent low dielectric property, low dielectric loss tangent, high glass transition temperature, and high copper foil peel strength Printed wiring boards, etc.

Claims (10)

A resin composition containing: a maleimide compound (A) having no siloxane bond, an unmodified cyanate compound (B), and selected from a styrene content of 17% by mass or more At least one of the group consisting of an elastomer with a styrene structure at the end (C1) and a polysiloxane with a maleimide structure at both ends (C2); the mass of the (C1) and (C2) And, relative to 100 parts by mass of the resin solid content, 5 to 25 parts by mass; the polysiloxane (C2) having a maleimide structure at both ends, including the maleimide terminal polymer represented by the following formula (4) Silica

In the above formula (4), R ₅ each independently represents an unsubstituted or substituted monovalent hydrocarbon group having 1 to 12 carbons, and the ratio of R ₅ representing a methyl group in all R ₅ is 50 mol% or more , N ₃ represents an integer from 0 to 2. The resin composition as claimed in item 1 of the patent application, wherein the maleimide compound (A) having no siloxane bond contains a maleimide compound selected from the following formula (1), the following At least one of the group consisting of the maleimide compound represented by the formula (2) and the maleimide compound represented by the following formula (3);

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

In the above formula (2), R ₂ each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbons or a phenyl group, and n ₂ represents an integer of 1 or more and 10 or less;

In the above formula (3), R ₃ each independently represents a hydrogen atom, a methyl group or an ethyl group, and R ₄ each independently represents a hydrogen atom or a methyl group. The resin composition according to item 1 or 2 of the patent application scope, wherein the unmodified cyanate compound (B) contains a phenol novolak type cyanate compound, a naphthol aralkyl type cyanate At least 1 of the group consisting of compounds, naphthyl ether cyanate compounds, bisphenol A cyanate compounds, bisphenol M cyanate compounds, and diallyl bisphenol A cyanate compounds Species. A resin composition according to item 1 or 2 of the patent application scope, wherein the styrene content is 17% by mass or more and the elastomer (C1) having a styrene structure at both ends contains a block selected from the group consisting of styrene-butadiene blocks Copolymer, styrene-isoprene block copolymer, styrene-hydrogenated butadiene block copolymer, styrene-hydrogenated isoprene block copolymer and styrene-hydrogenated (isoprene/ At least one of the group consisting of butadiene) block copolymers. For example, the resin composition according to item 1 or 2 of the patent application scope further contains filler (D). For example, in the resin composition of claim 5, the content of the filler (D) is 50 to 300 parts by mass relative to 100 parts by mass of the resin solid content in the resin composition. A prepreg is formed from a base material and a resin composition as described in any one of patent application items 1 to 6. A metal foil-clad laminated board, comprising: At least one or more prepregs that overlap with each other as in claim 7; and Metal foils arranged on one or both sides of the prepreg. A resin sheet containing: Support; and A layer formed of the resin composition as described in any one of patent application items 1 to 6 is disposed on the surface of the support. A printed wiring board, including: Insulation, and Conductor layer arranged on the surface of the insulating layer; The insulating layer includes a layer formed of the resin composition as described in any one of the patent application items 1 to 6.